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CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application is related to: U.S. Ser. No. 09/803,505 filed on Mar. 9, 2001 entitled: Opposing Spring Resilient Tension Suspension System. [0002] U.S. Ser. No. 10/033,016 filed on Oct. 26, 2001 entitled: Opposing Spring Rebound Tension Suspension System. [0003] U.S. Ser. No. 10/100,313 filed on Mar. 16, 2002 entitled: Method and Apparatus for Rebound Control. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT [0004] Not Applicable REFERENCE TO A “MICROFICHE APPENDIX” [0005] Not Applicable BACKGROUND OF THE INVENTION [0006] 1. Field Of The Invention [0007] The present invention relates to and, in particular, to improvements in the methods and apparatus for using a rebound spring carried on a shock absorber that is intended to utilize the unsprung weight of the wheel/axle system during rebound. More particularly, it is to resist rollover, sway, yaw and other chassis motion. [0008] 2. Description Of Related Art Including Information Disclosed Under 37 CFR 1.97 and 1.98 [0009] In the past ten years the numbers of sport utility vehicles “SUV” and pickup trucks have increased dramatically to the point where those vehicles are more popular than the millions of passenger cars on the road. The SUV and trucks inherently have a higher center of gravity (CG) than normal passenger cars due to the need for higher ground clearance for bad weather travel (snow and ice), off-road use and/or for pickup truck payloads. Vehicles with a higher CG have a greater propensity to sway or even rollover during abrupt lane changes and evasive steering maneuvers than the lower normal passenger cars. One important arrangement of all these vehicles is the method of suspension used. Except for the use of hydraulic shock absorber damping resistance to rebound, all vehicle chassis and body loads are supported on the vehicle axles with various types of suspensions that have springs that resist primarily load and jounce of each wheel axle. No existing suspensions using coil springs, load leaf springs, air springs, torsion bars or rubber blocks suspensions have any other provision for rebound control of the forces due to inertia or gravity type negative suspension loads. Particularly, those rebound forces occurring at the inside wheel during hard cornering or if a wheel drops into a pothole. Typically, changes in suspension loads while driving straight along a road are caused generally by reactions to bumps, potholes, and roughness encountered by the vehicle wheels during their interaction with the road surface. Thus the suspension springs and associated shock absorbers quell the harshness and movements being transmitted to the body/chassis. The sway or side to side rolling motions that vehicles experience due to cornering forces, also cause vehicle springs to be loaded or unloaded, depending which way the vehicle is rolling during cornering. Many vehicles have an anti- sway/roll bar installed to help the vehicle body resist the rolling actions. These devices help the vehicle partially resist roll but only as it relates to the body lean, because they are fixed to the sprung mass and leaning with the body. Thus, they can actually reduce the load on the unloaded side of the vehicle. They use the body as a structure to support the torsion bar of the anti sway system transferring wheel jounce motion across to the opposite side. The disclosure herein will obviate the need for anti-sway bars, saving the cost of providing and installing them. Shock absorbers only dampen the bouncing movement of the vehicle wheels and suspension caused by the reaction to road surface, cornering and braking. Thus, the rate of sway may be affected only to a minor degree. A floating aluminum piston is placed between the fluid moving piston and the end of the shock body. The floating piston has nitrogen gas behind it that is at a preset pressure. This piston is used in racing shocks and other lift type shocks to do two things, first to pressurize the fluid at all times and second to raise the vehicle ride height. It is not practical to fill the entire shock body with fluid on both sides of the fluid piston. This ensures that as the fluid moving piston moves away from the end of the cavity as it would during extension or “rebound” travel, it does not permit a vacuum to form behind the fluid piston and sucking against the shock travel. It maintains a pressure front against the fluid to ensure that it is induced to pass the fluid piston during jounce travel. The fluid piston has holes in it to allow the fluid to pass by it and flexible shims on both sides of the fluid piston are adjusted in strength to set the resistance to flow through the piston during normal movement. Stiffer shims result in higher resistance to the fluid being compressed against them. All this and the use of nitrogen pressure against the piston are typical of existing shock absorber design. The basic tubular shock absorber is well known to skilled artisans, and is a commodity and is disclosed in numerous patents. The typical shock absorber is designed to dampen motion and with coil over springs adjust the ride height and/or spring stiffness. [0010] U.S. Pat. No. 2,160,541 has a paired spring suspension connected in series to only support load and jounce with the added spring coupled in line with the main spring for increasing the effective spring constant at the extremes of suspension travel. The techniques disclosed in the various embodiments of ′541 are in the nature of an overload spring that engages and changes the spring constant at the extremes of wheel travel. There is no spring in ′541 connected to specifically resist rebound forces due to diverging motion of the sprung weight to unsprung weight. The disclosure of ′541 specifically states that the higher spring constant results in less flex (on page 2 column 1 at lines 6 to 8 ), “. . . which opposes any tendency of the vehicle to overturn laterally when negotiating a curve.” In each embodiment of ′541 the springs act in unison to control primarily load and jounce and there is no teaching of a particular connection to directly apply rebound reaction of unsprung weight to one of the springs. The graph in ′541 showing wheel travel verses spring forces verifies these conclusions. U.S. Pat. No. 5,263,695 discloses a refinement of the ′541 teaching that includes a shock absorber for damping motion and an elastic block to ameliorate the transition between first and second springs for carrying the load. In addition to many disclosures in ′695 of prior paired spring configurations there is a specific explanation in column 5 , lines 1 through 5 as follows: [0011] “The suspension according to the invention produces a comfort level which is higher the more the transition from one stiffness to the other takes place progressively (see the patents cited in the state of the art).” The state of the art referred to includes prior patents of the same inventor and the acknowledgements of those prior patents clearly identifies the teachings as merely two springs of different stiffness in series. Even in FIG. 7 of ′695 the springs are concentrically mounted but act in series, see column 4 , lines 8 through 12 . At best the structures for multiple springs shown in these patents have differing spring rates to give an allegedly more comfortable ride but do not specifically disclose rebound control. [0012] U.S. Pat. No. 3,830,517 is a motorcycle rear wheel spring suspension wherein a top spring is longer and absorbs upward road shock and a bottom spring absorbs the rider's weight. Nothing is disclosed about resisting rebound with either the top or bottom spring and no attachment of the springs is shown or described that would operate to control rebound of the sprung weight. [0013] U.S. Pat. No. 3,049,359 has a pair of coaxial coil springs designed to maintain ride height by automatic screw adjustment of the smaller and lighter inner tension coil spring. No disclosure of rebound control of sprung weight is made and the inner tension coil spring loadings are varied only in so far as the ride height is less or more than required as such the size and strength of the inner tension spring would be insufficient to transfer the unsprung weight to the chassis and resist rebound. Moreover the working travel of both springs appears to be the same; thus, no rebound control is possible. No existing suspension system suspends the chassis and/or body between opposing springs to counter load and jounce and reaction and rebound along different portions of the axle and wheel travel. An opposing spring suspension as disclosed herein can have little effect on the ride stiffness, but stabilizes cornering and evasive maneuvering sway by utilizing the unsprung weight of the axle system thus helping the vehicle to resist roll while maintaining the general ride quality. [0014] U.S. Pat. No. 3,297,312 has a combination shock absorber and spring for automobile suspensions. Close examination reveals that a main rod connects between a top cap and a nut to bottom tube. It appears that the rod will bottom out against the tube end when the springs are compressed because rod 52 is of set length and incompressible. The four springs stacked, as a unit, abut each other to act as one continuous variable rate spring. Specifically, the upper two springs have a disc that separates them that shifts up and down with the movement of the springs. The disc has valve holes in it to permit the movement of fluid to each side of the disc to act as a shock absorber. This appears to have minimal effect or use. [0015] U.S. Pat. No. 5,183,285 has a suspension of a stiffness that is greater between the operating load position and the suspended wheels position than between the operating load position and the collapsed position. It is a suspension and a suspension process that uses a greater stiffness in the region of “rebound” than in the region of “bump” with means for smoothing the stiffness from the passage of one region to the other, and means for varying the reference position for “operating load” as a function of the number of persons and the load in the vehicle. A suspension wherein the stiffness is greater in the region between the position “operating load” and a position “suspended wheels” than in the range between the position “operating load” and a position “collapsed suspension” up to shock abutment. The suspension has stiffness greater in the region of “rebound” than in the region of “bump”; if these are graphically represented, a change of thickness represented by a break in the slope appears. FIGS. 13, 14 and 16 in U.S. Pat. No. 5,183,285 have a rebound spring around a shock positioned by a jack for varying the reference position for “operating load” as a function of the number of persons and the load in the vehicle. The jack varies the preload position so there is no gap between rebound and bump. [0016] U.S. Pat. No. 6,273,441 has a load leaf spring suspension system with an elongated stabilizing spring mounted there above the axle. The added spring communicates roll resistance to the vehicle axle at its top center section. Force is concurrently applied at the ends of the stabilizing spring to the leaf spring of the vehicle by shackles. Adjustment of the device is achieved by use of a plurality of mounting apertures for the shackles located at varying distances from the center of the stabilizing spring thereby allowing for adjustment by the user for desired performance characteristics. Further force adjustment is achieved with one or a combination of an optional axle spacer located at the center section of the stabilizing spring to communicate with the axle. This stabilizer system does not employ opposing spring technology. An influence is delivered on the vehicle center of gravity by opposing spring. The center of gravity of the unsprung mass relative to the center of gravity of the sprung mass is affected during the cornering maneuvers. Without a tension or opposing spring to “tether” the sprung mass to the unsprung mass the unsprung mass does not initially help resist the movement upwards of the sprung mass. This resistance is best appreciated in a vehicle with very heavy unsprung mass relative to a lighter sprung mass during cornering versus a vehicle with light unsprung mass relative to a heavy sprung mass. The former is recognized as undesirable and the latter is greatly preferred and sought after in design of vehicles. Often the physical limits of the vehicle components determine the practical boundaries of the sprung weight to unsprung weight ratio. The disclosure herein has an approach to ameliorate the dynamics of that relationship. [0017] U.S. Pat. 6,017,044 has as it's main thrust regulation of spring rebound and bound. Vertical downward jacking-force characteristics of the front suspension is set to be stronger relatively with respect to vertical downward jacking-force characteristics of the rear suspension during cornering. This is achieved by two means. The first is the use of a very strong bump rubber 25 in FIG. 3 of U.S. Pat. No. 6,017,044 that comes into play at the extreme end of the front jounce travel. This bump rubber is not needed in our disclosure. Second, a short “spring” item in FIG. 4 of U.S. Pat. No. 6,017,044 is intended to help control “jack up” of the rear suspension occurring near the extreme end of the roll. The working distance traveled is very short. [0018] U.S. Pat. No. 6,220,406 discloses a damper for reducing sway. It discloses background on various types of shock absorbers used in connection with motor vehicle suspension systems to absorb unwanted vibrations that occur during various driving conditions. To dampen the unwanted vibrations, shock absorbers are generally connected between the sprung portion (i.e., the vehicle body) and the unsprung portion (i.e., the suspension) of the vehicle. A piston assembly is located within the working chamber of the shock absorber and is connected to the body of the motor vehicle through a piston rod. Generally, the piston assembly includes a primary valve arranged to limit the flow of damping fluid within the working chamber when the shock absorber is compressed or extended. As such, the shock absorber is able to generate a damping force to smooth or dampen the vibrations transmitted from the suspension to the vehicle body. Typically, these vibrations occur from forces generated in a vertical direction between the vehicle body and the driving surface. [0019] The greater the degree to which the flow of damping fluid within the working chamber is restricted across the piston assembly, the greater the damping forces that are generated by the shock absorber. It is also possible to implement a primary valve arrangement that produces one magnitude of damping on the compression stroke, and a second magnitude of damping on the rebound stroke. These different damping rates are typically constant as varying the sizes of the compression and rebound bypass orifices produces them. While these shock absorbers produce ride comfort levels ranging from “soft” to “firm,” few, if any, of the known shock absorbers produce varying degrees of damping in a passive manner. The shock absorber systems in use are capable of producing varying degrees of damping force; typically achieve this through the use of active control systems. These systems generally react to the vertically generated forces placed upon the vehicle suspension. [0020] Accordingly, in ′406 a shock absorber that includes a primary damping mechanism for counteracting the vertical forces placed upon the vehicle, and a secondary damping mechanism which is capable of providing varying damping in response to horizontal and lateral forces that are placed upon the vehicle suspension. Secondary and variable damping is provided in proportion to the lateral force encountered by a passive control or valves arranged to implement a passive anti-roll system for enhancing the control to the vehicle provided by the vehicle suspension. While such a passive damping system also eliminates the need for complicated and expensive controls to actively provide the varying degrees of damping, it is not easily adapted to the large variety of vehicles and their suspensions. [0021] The problem of the lateral forces placed upon the vehicle suspension is they are generated during high-speed cornering. As the suspension and tires counteract these lateral forces, a rolling action on the vehicle body is produced. When these rolling forces exceed the limit for the vehicle, a rollover condition may be created wherein the vehicle is literally flipped over on its side. Accordingly, it is desirable to provide a shock absorber that provides increased resistance in response to these lateral and horizontal forces for counteracting or at least minimizing these rolling forces and the lift associated therewith. BRIEF SUMMARY OF THE INVENTION [0022] In the disclosed device and method, a rebound spring is placed to resist the lengthening of the shock absorber from a position that starts one inch into jounce travel from normal ride height to the full rebound suspension travel position. This rebound spring is opposing and resisting the forces that are generated when the suspension is unloading as for example during comering. Namely the forces caused by the vehicle suspension spring trying to return to its free position and the centrifugal forces naturally resulting during cornering. [0023] Using an additional coil spring mounted about the shock absorber to resist the rebound motion of the sprung weight applied by movement thereof away from the design height reduces chassis roll. The shock absorber thus reduces the initiation of rebound travel between the sprung and unsprung weights as the vehicle becomes lighter due to dynamic forces inducing roll or lift of the chassis and vehicle body. [0024] The transitory effects of body roll during cornering flex the load springs on the side of the vehicle following the outside of the turn due to increased transfer weight to that side. Meanwhile the springs on the side of the vehicle, following the inside of the turn, unload extending toward their free position using the axle as a location for inducing lift of the sprung weight on that side resulting in increased body roll. Roll or sway during sudden cornering or evasive maneuvers rotates the vehicle and its center of gravity “CG” around the Roll Center axis. [0025] The Roll Center axis is a function of the particular, vehicle's suspension geometry. Roll or sway is increased if the vehicle center of gravity is raised as in a SUV, four-wheel drive vehicle or truck. A sudden turn opposite the direction of vehicle travel can cause momentum to continue the sway of the vehicle forcing its center of gravity to move laterally past its maximum upright position, and so the vehicle continues on rolling and overturns. [0026] The solution, as disclosed herein, may include an added rebound spring mounted coaxial about the shock absorber tube to act primarily to resist rebound of the suspension from the design height position and thereby apply resistive force to the chassis via the shock absorber to reduce lift. The coil rebound spring can also be added to a strut type suspension for exactly the same purpose. It is an advantage of the present invention that it can be easily and inexpensively added as an after market supplement to either the front or rear of an existing vehicle suspension with tubular shock absorbers. It is a further advantage of the present invention that the coil rebound spring has very little influence on ride height and/or ride stiffness. [0027] The coil rebound spring works from one inch of jounce travel all the way to full rebound travel of the shock absorber. It works to prevent the onset of roll from the design height, rather than limiting the roll to a certain amount after it has rolled a certain amount. Limiting the roll from the design height position serves to reduce the momentum or inertial weight gain that occurs at the initiation of roll and continues after roll has begun. In other words, we seek to eliminate as much roll as possible from the outset. Rebound control overlaps the jounce control; therefore the disclosed system is truly bi-linear, a preferred embodiment. BRIEF DESCRIPTION OF THE DRAWING [0028] FIG. 1 is a side view in cross section of a shock absorber having a coil rebound spring thereabout. [0029] FIG. 2 is a schematic perspective view of a vehicle rounding a comer with roll depicted about its longitudinal axis A-A. [0030] FIG. 3 is a side view in cross section of a typical combined shock absorber and strut type suspension unit, having a load spring but with the addition of the disclosed coil rebound spring thereabout. [0031] FIG. 4 is a graph showing the travel relative to the jounce and rebound loads of the combined shock absorber and strut depicted in FIG. 3 . DETAILED DESCRIPTION OF THE INVENTION [0032] FIG. 1 shows a cross section view of a vehicle rebound control shock absorber 10 with a special suspension coil rebound spring 11 arrangement. It is to be used to replace a standard shock absorber installation independent of the vehicle spring system, as is commonly found in both vehicles with leaf type and coil type suspension spring systems. Commonly a shock absorber connects the sprung mass to the un-sprung mass and is used only to dampen unsprung mass oscillations induced by bumpy roads and sometimes with helper load springs for preloaded height and jounce improvement. The sprung mass is carried on vehicle chassis and body and herein after will be referred to structurally as chassis 16 . The unsprung weight is that which is not supported by the vehicle suspension spring system, i.e. axles 15 , wheels, tires, brake assemblies and suspension components that hang downwardly if the body is lifted. Typically, the passenger vehicle has four wheels with associated suspension with two at the front and two at the rear. The disclosure herein is to cover any number of axle 15 and wheel combinations so long as there is roll to be restrained. FIG. 1 shows a coil spring mounted about a rebound control shock absorber 10 for exerting force to resist upper rebound control shock absorber 10 movement from the normal design height or preloaded ride position of chassis 16 . When both ends of the rebound control shock absorber 10 are pulled apart, as experienced by chassis 16 when it lifts during rebound of the axle 15 . It is called coil rebound spring 11 because it is intended to counter the lifting action of the vehicle suspension during roll due to cornering maneuvers. When a vehicle corners, its chassis 16 rolls about its longitudinal axis A-A in FIG. 2 relative to axles 15 . Load carrying coil springs 14 on the outside of chassis 16 become compressed as they assume jounce and the coil load springs 14 located on the inside of the turning chassis 16 during cornering become extended while experiencing rebound see FIG. 2 . Coil load springs 14 on the unloading inside side of the cornering vehicle are trying to return to their free state as they extend. Thus coil load springs 14 as they extend exert a lifting force to chassis 16 which is exacerbating the roll angle of the body mass. The lifting force is exactly what is not desired and is resisted by the coil rebound springs 11 herein disclosed. The whole purpose of using coil rebound springs 11 is to reduce chassis 16 roll at initiation of and during cornering because rebound movement at any axle 15 will likewise be resisted. [0033] FIG. 3 shows another rebound control shock absorber 10 having coil rebound spring 11 thereabout, but with the addition of a compression type suspension coil load spring 14 . The additional compression coil load spring 14 carries the sprung weight and is intended to replace or supplement chassis 16 existing original equipment manufacturer suspension load spring 14 , if any. If load spring 14 is carried on the rebound control shock absorber 10 and no separate load spring 14 is used the vehicle suspension would be fully self-contained. Thus the rebound control shock absorber 10 with an integral coil load spring 14 as per FIG. 3 would be able to serve as a replacement assembly providing that the vehicle mounting points for such an assembly is sufficient to respond and carry the loadings expected. Typically, strut mountings that are prevalent on modern cars and trucks are adequate for operation with the assembly shown in FIG. 3 . It is important to note that coil rebound spring 11 seeks to control the sprung weight and the coil load spring 14 if original equipment manufacturer and/or on the rebound control shock absorber 10 as in FIG. 3 supports the sprung weight. [0034] A rebound control shock absorber 10 for placement between axle 15 and chassis 16 is shown in FIGS. 1, 2 and 3 . The rebound control shock absorber 10 is for additionally controlling the vehicle dynamics with increasing resistance under motion between a preloaded vehicle ride height position to a fully extended position of rebound control shock absorber 10 during rebound movement of chassis 16 away from axle 15 along an axis B-B through the rebound control shock absorber 10 . It is rebound control shock absorber 10 that applies the unsprung weight of the wheels, brake and axle 15 to chassis 16 through coil rebound spring 11 . The goal is not to lift the axle, wheel and its tire from the ground, if possible, during cornering but to apply the unsprung weight of those components at the lifting side of chassis 16 to resist roll of the chassis and body. [0035] An axle mount 17 on axle 15 is provided to connect to rebound control shock absorber 10 . A chassis attachment 18 on chassis 16 of the vehicle connects to the depending rebound control shock absorber 10 so that it may operate along axis B-B between axle mount 17 and chassis attachment 18 . An elongated rod 19 has opposite ends 20 and 21 carried and aligned along the axis B-B. End 20 connects to chassis attachment 18 in FIGS. 1 or 3 . While rebound control shock absorber 10 is shown with elongated rod 19 and end 20 at the top in FIGS. 1 and 3 , skilled artisans will understand that it can be inverted so that elongated rod 19 connects to axle mount 17 . A fluid displacement piston 22 is located on end 21 . If rebound control shock absorber 10 is inverted (not shown) then attention to how coil rebound spring 11 carries the unsprung weight must be addressed; again this is within the skill of artisans. Fluid displacement piston 22 is carried on the elongated rod 19 opposite its connection end 20 . Likewise a tube 23 is aligned along the axis B-B and connects to the axle mount 17 when the end 20 is connected to the chassis attachment 18 ; alternatively, the tube 23 connects to chassis attachment 18 when the end 20 is connected to the axle mount 17 . [0036] Tube 23 has inside and outside cylindrical surfaces 24 and 25 . Inside cylindrical surface 24 is sized diametrically for surrounding the fluid displacement piston 22 for sliding sealing circumferential engagement there between with reciprocation along the axis B-B. A chamber 26 is defined by the inside cylindrical surface 24 and chamber 26 carries damping fluid (not shown) about fluid displacement piston 22 for controlled resistance to sliding reciprocal movement of the fluid displacement piston 22 within tube 23 against the inside cylindrical surface 24 and along the axis B-B. [0037] Coil rebound spring 11 is carried about outside cylindrical surface 25 of tube 23 coaxial thereto and for expansion and contraction along the axis B-B as in FIGS. 1 and 3 . Coil rebound spring 11 is mounted to restrain expansion along the axis B-B of the rebound control shock absorber 10 between axle 15 and chassis 16 of the vehicle. Restraint is from at least the preloaded vehicle ride height position to the coil rebound spring 11 fully extended position during rebound motion of the axle 15 away from the chassis 16 as in FIG. 2 . [0038] Tube 23 is elongated along the axis B-B with a top 27 and a bottom 28 separated from each other. A flanged retainer 29 affixes about the outside cylindrical surface 25 of tube 23 . Flanged retainer 29 is located between the top 27 and bottom 28 for applying axial rebound loads to tube 23 from rebound spring 11 during motion along axis B-B of the axle 15 away from chassis 16 . A tube cap 30 mounts in the top 27 and extends from tube 23 to a seat 31 overhanging tube cap radially from the outside cylindrical surface 25 as shown in FIGS. 1 and 3 . [0039] A bore 32 positioned in and passing through tube cap 30 is coaxial with axis B-B and bore 32 allows elongated rod 19 to pass there through and reciprocate therein. Tube cap 30 connects axially to tube top 27 to capture coil rebound spring 11 between flanged retainer 29 and seat 31 . The coil rebound spring is thereby supported for coaxially circumscribing tube 23 between top 27 and bottom 28 thereof. Rebound is resisted during expansion of rebound control shock absorber 10 from its preloaded height to full extension along the axis B-B with motion of axle 15 away from chassis 16 . A cylindrical housing 33 in FIGS. 1 and 3 is affixed to the end 20 connected to either chassis 16 or axle 15 depending on the orientation of rebound control shock absorber 10 . Cylindrical housing 33 extends from its affixed connection along the axis B-B to engage flanged retainer 29 . Cylindrical housing 33 has a circular cross section sized diametrically for surrounding coil rebound spring 11 with a clearance there between. In FIG. 3 the cylindrical housing 33 is shown with external threads. A fastener 34 on tube cap 30 adjacent seat 31 is shaped to retain coil rebound spring 11 to seat 31 during movement of coil rebound spring 11 along the axis B-B with motion of axle 15 away from chassis 16 . The coil rebound spring 11 is preloaded by the flanged retainer when the coil rebound spring is captured between flanged retainer 29 and seat 31 . During expansion of the rebound control shock absorber 10 from its preloaded position, the coil rebound spring resists expansion under motion of axle 15 away from chassis 16 . [0040] Coil load spring 14 mounts co-axially about cylindrical housing 33 for carrying chassis 16 of the vehicle from the preloaded ride height position to a full jounce position compressing the coil load spring 14 as shown graphically in FIG. 2 . An upper collar 35 about cylindrical housing 33 is near connection end 20 and a lower collar 36 at tube bottom 28 capture coil load spring 14 so rebound spring 11 substantially resists expansion after coil load spring 14 substantially resists compression during rebound and jounce, respectively. The term, “after” is used in the preceding sentence because rebound spring 11 and coil load spring 14 operate independently to control (resist) different loads. [0041] A method for rebound control by rebound control shock absorber 10 placed between axle 15 and chassis 16 of a vehicle is operable at least between a preloaded vehicle ride height position to a fully extended position during rebound movement of axle 15 away from chassis 16 along axis B-B. The method of rebound control has the steps of mounting rebound control shock absorber 10 to axle mount 17 , and attaching rebound control shock absorber 10 to chassis attachment 18 along axis B-B there between. Another step connects elongated rod 19 having opposite ends 20 and 21 so end 20 connects to either axle mount 17 or chassis attachment 18 . Locating piston 22 at the opposite end and connecting tube 23 to axle mount 17 if the elongated rod 19 is connected to chassis attachment 18 or connecting tube 23 to chassis attachment 18 if the elongated rod 19 is connected to the axle mount 17 are steps. The step of sizing tube 23 with a cross section to surround piston 22 for sliding sealing circumferential engagement within tube 23 due to motion of axle 15 away from chassis 16 is performed. Carrying damping fluid about piston 22 in chamber 26 defined by tube 23 is a step. The steps of controlling resistance to sliding reciprocal movement of piston 22 in tube 23 with the damping fluid, and carrying rebound spring 11 about tube 23 for restraining expansion of the rebound control shock absorber 10 . Restraining is between axle 15 and chassis 16 of the vehicle from the preloaded vehicle ride height position to the fully extend position along the axis B-B during rebound movement of axle 15 away from chassis 16 are followed. [0042] The step of supporting rebound spring 11 coaxially circumscribing tube 23 so that rebound is resisted during expansion of rebound control shock absorber 10 from its preloaded height to full extension along the axis B-B with motion of axle 15 away from chassis 16 is done. The step of supporting load spring 14 relative to rebound spring 11 coaxial to one another and along the axis B-B with a clearance there between occurs. During expansion of rebound control shock absorber 10 from its preloaded vehicle height to full extension along the axis B-B there is motion of axle 15 away from chassis 16 load spring 14 and the rebound spring 11 operate substantially independent of one another to resist jounce and rebound, respectively. The method for rebound control by rebound control shock absorber 10 with the step of supporting rebound spring 11 and load spring 14 at the preloaded vehicle height so that the working force application travel there between is overlapping. Thus, about one inch of travel overlap during movement of the rebound spring 11 along the axis B-B with motion of axle 15 away from chassis 16 from the preloaded vehicle height is thus preformed. FIG. 4 shows in graphic form the resultant of overlap for rebound spring 11 and the load spring 14 combined. In the graph of FIG. 4 the load paths at a rate of 320 pound per inch compression jounce spring and a rate of 160 pounds per inch rebound counter spring are shown. The affect on the rebound travel spring of the suspension if engaged at one inch of jounce is no curve at the transition point. [0043] The step of having the ratio of the spring constants of coil rebound spring 11 to the spring constant of load spring 14 be less than one. So that during expansion of rebound control shock absorber 10 from its preloaded position coil rebound spring 11 happens to resist expansion under motion of axle 15 away from chassis 16 to a lesser extent than load spring 14 resists jounce. The step of coil rebound spring 11 applying force to resist rebound of the axle 15 occurs. [0044] The method for rebound control by rebound control shock absorber 10 has the step of locating coil rebound spring 11 to substantially resist expansion of rebound control shock absorber 10 . The step of co-axially positioning coil load spring 14 to substantially resist compression of rebound control shock absorber 10 during rebound and jounce is performed independently. [0045] While the examples illustrating rebound control shock absorber 10 and rebound spring 11 are disclosed and described, skilled artisans will appreciate that many variations for the addition of rebound spring 11 will be possible. The specific examples should not be considered limiting and the particular arrangements shown in FIGS. 1 and 2 are merely for depiction of but some examples of form. In that regard, in the claims that follow the orientation of rebound control shock absorber 10 is either up or down and angled mounting thereof is also within the scope of the claims.
A stabilizing apparatus and method that replaces the existing shock absorber of a road vehicle that works to resist the initiation of body roll during comering. It seeks to counter act the forces being generated by the vehicle suspension springs that exacerbate the rollover propensity of vehicles during certain steering maneuvers.
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CROSS REFERENCE TO RELATED APPLICATION [0001] This application claims the benefit of U.S. Provisional Application No. 61/730,396, entitled BALER UNLOADING RAMP RETURN MECHANISM filed Nov. 27, 2012, which is hereby incorporated by reference in its entirety. BACKGROUND OF THE INVENTION [0002] 1. Field of Invention [0003] This invention relates to the field of round balers and, more particularly, to a passive, spring-loaded bale discharge ramp for such machines. [0004] 2. Description of Related Art [0005] Passive unloading ramps for guiding bales to the ground as they leave the baling chamber have been known and used for many years on round balers. Such ramps are spring-biased to a raised, standby position during normal baling operations but are forced down into a lowered, deployed position by the weight of the bale as it discharges from the baling chamber. The spring returns the ramp to its raised position once the bale rolls off the ramp. [0006] Conventional designs utilize exposed compression or extension springs as the return mechanism for the ramp. However, such arrangements are highly susceptible to the accumulation of crop residue and dirt that fill up and clog the springs. Additionally, the pivots for the ramps are typically metal on metal and can be noisy or bind up. Lubrication added to the pivots has a tendency to attract and retain even more dirt and residue, which causes the pivots to bind up, work hard, and wear prematurely. Furthermore, assembly of the spring and pivot mechanism can be difficult. OVERVIEW OF THE INVENTION [0007] The present invention provides a combination pivot and internal spring assembly for the ramp wherein the spring is housed protectively inside the pivot mechanism. Thus, the spring components are not exposed to the deleterious effects of the elements and do not collect trash and dirt. Furthermore, the spring components are so positioned that they help seal off and close opposite, otherwise open ends of a tubular member of the pivot to resist the ingress of harmful trash and dirt, as well as moisture, into the interior of the pivot. Moreover, the spring components support the rotatable part of the pivot in such a manner that no bearings are needed and there is no metal-to-metal contact of any kind within the pivot. In one preferred embodiment of the invention resilient rubber-like or elastomeric spring pads within the tubular outer member of the pivot assembly are compressed when the outer member is rotated relative to a stationary inner member as a discharging bale swings the ramp down to the ground, thereby torsionally loading the pivot assembly to effect automatic return of the ramp to its raised position once the bale rolls off the ramp. [0008] In one embodiment, the invention is directed to a round baler having a mobile chassis, a bale-forming chamber supported on the chassis and including a tailgate that can be raised for discharging a bale from the chamber and a bale discharge ramp. A combination pivot and spring assembly attaches the ramp to the chassis below the chamber for movement of the ramp from a raised, standby position to a lowered, unloading position for guiding a bale down to the ground as the bale leaves the chamber. The combination pivot and spring assembly includes an internal spring for yieldably maintaining the ramp in its raised position until a bale exiting the chamber engages the ramp and overcomes the force of the spring to swing the ramp down to its lowered position. In one embodiment, the combination pivot and spring assembly further include a stationary member fixed to the chassis and a rotatable member fixed to the ramp for rotational movement relative to the stationary member when the ramp moves between the raised and lowered positions, and the spring is operatively disposed between the members. [0009] These and other features and advantages of this invention are described in, or are apparent from, the following detailed description of various exemplary embodiments of the systems and methods according to this invention. BRIEF DESCRIPTION OF THE DRAWINGS [0010] The above mentioned and other features of this invention will become more apparent and the invention itself will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein: [0011] FIG. 1 is a left side elevational view of a round baler incorporating a spring-loaded, passive unloading ramp in accordance with the principles of the present invention, the ramp being shown in the raised position; [0012] FIG. 2 is a left side elevational view similar to FIG. 1 but showing the tailgate raised and the ramp forced down to its lowered position by a discharging bale; [0013] FIG. 3 is a left, rear isometric view of the baler with the tailgate closed and the ramp in the raised position corresponding to FIG. 1 ; [0014] FIG. 4 is a left, rear isometric view of the baler with the tailgate raised and the ramp in the lowered position corresponding to FIG. 2 ; [0015] FIG. 5 is an enlarged, fragmentary, left rear isometric view of the ramp in the raised position with parts broken away to review details of construction; [0016] FIG. 6 is an enlarged, fragmentary, right, rear, bottom isometric view of the ramp in the raised position; [0017] FIG. 7 is an enlarged, left rear isometric view of the ramp and its associated pivot assembly; [0018] FIG. 8 is an enlarged, left, front, bottom isometric view of the ramp and its associated pivot assembly; [0019] FIG. 9 is an enlarged, fragmentary top plan view of the left end of the ramp and associated pivot assembly with parts broken away to reveal details of construction; [0020] FIG. 10 is an enlarged, fragmentary cross-sectional view through the ramp and associated pivot assembly illustrating the condition of things when the ramp is in its raised position; [0021] FIG. 11 is a view of the ramp and associated pivot assembly similar to FIG. 10 but showing the condition of things when the ramp is in the lowered position; and [0022] FIG. 12 is an exploded, left front isometric view of the ramp and associated pivot assembly. [0023] Corresponding reference characters indicate corresponding parts throughout the views of the drawings. DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS [0024] The invention will now be described in the following detailed description with reference to the drawings, wherein preferred embodiments are described in detail to enable practice of the invention. Although the invention is described with reference to these specific preferred embodiments, it will be understood that the invention is not limited to these preferred embodiments. But to the contrary, the invention includes numerous alternatives, modifications and equivalents as will become apparent from consideration of the following detailed description. [0025] A round baler 10 has a wheeled mobile chassis 12 that supports a baling chamber 14 for forming a round bale from crop materials picked up from a field as the baler is towed across the field. At the completion of a bale-forming cycle, a tailgate 16 that comprises the rear half of baling chamber 14 is raised to allow a finished bale 17 to roll out of the chamber by gravity and onto the ground. A passive, spring-loaded unloading ramp 18 is provided to guide bale 17 to the ground as it discharges from chamber 14 . During baling operations, ramp 18 is disposed in a raised position as shown, for example, in FIGS. 1 and 3 , but as bale 17 engages ramp 18 during discharge, the weight of the discharging bale forces ramp 18 down to a lowered position as shown, for example, in FIGS. 2 and 4 in which the rear end of ramp 18 engages the ground. After the bale has rolled off ramp 18 , the ramp automatically returns by spring force to its raised position, and tailgate 16 is reclosed by the operator. [0026] In accordance with the present invention, ramp 18 is attached to chassis 12 below baling chamber 14 by a combination pivot and spring assembly 20 wherein spring components of the assembly are internally disposed. Ramp 18 may be constructed in a number of different ways without departing from the principles of the present invention, but in the particular embodiment disclosed herein it comprises three fore-and-aft extending, laterally spaced apart and transversely U-shaped, inverted channels 22 that are interconnected across their rear ends by a common transverse pipe 24 . At their front ends channels 22 are interconnected by a common, inverted L-shaped beam 26 having a vertical rear leg 28 and a horizontal top leg 30 . Three pairs of generally C-shaped, upright mounting lugs 32 project forwardly from vertical leg 28 beneath horizontal leg 30 for use in attaching ramp 18 to combination pivot and spring assembly 20 as hereinafter described. [0027] Combination pivot and spring assembly 20 includes a hollow outer pivot member, preferably in the form of an elongated tube 36 , that rotates with ramp 18 during movement of the ramp between its raised and lowered positions. In the particular illustrated embodiment, tube 36 has a four-sided, rectangular cross-sectional configuration, although it will be appreciated that tube 36 may have a lesser or greater number of sides and need not necessarily be polygonal in cross-section. Tube 36 extends parallel to beam 26 and is complementally received within the forwardly facing mouths of mounting lugs 32 , while a pair of U-bolts 38 fixedly secure tube 36 and beam 26 together. Opposite ends of tube 36 project slightly outwardly beyond the outermost mounting lugs 32 as shown, for example, in FIGS. 7 , 8 and 9 . [0028] Combination pivot and spring assembly 20 further includes a stationary inner pivot member, preferably in the form of a pair of axially aligned, longitudinally spaced apart, rectangular stub shafts 42 that project into opposite ends of outer tube 36 . Like tube 36 , stub shafts 42 may each have fewer or greater than four sides and need not necessarily be polygonal in cross-section, although it is advantageous in any event for the sake of simplicity for stub shafts 42 to match the polygonal cross-sectional configuration of outer tube 36 . Outer tube 36 has a somewhat larger cross-sectional configuration than stub shafts 42 and, in the illustrated embodiment, is rotatively offset by approximately 45 from stub shafts 42 when ramp 18 is in its raised position as illustrated, for example, in FIG. 10 . Consequently, when ramp 18 is in its raised position, a number of generally triangular-shaped voids 44 ( FIG. 10 are presented at the internal corners of tube 36 between flat internal surfaces 45 of tube 36 and opposing flat external surfaces 47 of stub shafts 42 (see also FIG. 12 . [0029] An internal spring is provided within tube 36 to interact with tube 36 and stub shafts 42 to form another part of combination pivot and spring assembly 20 . Such internal spring preferably comprises a plurality of resilient, rubber, rubber-like, or elastomeric spring pads or “cords” 46 that occupy the voids 44 . Preferably, the pads 46 are each generally triangular in cross-sectional configuration to match the triangular shape of voids 44 , although other cross-sectional shapes may also be acceptable. As will be seen, the closer the pads 46 match the shape of the voids 44 , the more completely stub shafts 42 and pads 46 will serve to plug and close the otherwise open ends of tube 36 . As illustrated in FIG. 9 , pads 46 have outermost ends 46 a that are substantially flush with the corresponding end edges 36 a of tube 36 at its opposite ends. [0030] Combination pivot and spring assembly 20 additionally includes a pair of fore-and-aft mounting arms 48 fixed to and projecting forwardly from the outer ends of stub shafts 42 . Mounting arms 48 are spaced a short distance outwardly from the opposite end edges 36 a (see FIG. 9 so as to avoid metal-to-metal contact between arms 48 and tube 36 as ramp 18 pivots about the common longitudinal axis of stub shafts 42 and tube 36 during movement between its raised and lowered positions. Mounting arms 48 are, in turn, rigidly attached by bolts 50 ( FIGS. 5 , 6 to a corresponding pair of generally U-shaped brackets 52 that are affixed by welding or the like to a fixed, transverse axle tube 54 forming part of chassis 12 . [0031] It should be apparent from the foregoing description that ramp 18 and outer tube 36 pivot about stub shafts 42 during movement between the raised and lowered positions as stub shafts 42 remain stationary. Spring pads 46 , operating against flat surfaces 45 and 47 of tube 36 and stub shafts 42 respectively, yieldably bias ramp 18 toward its raised position and maintain it in such position throughout baling operations. However, when a bale ejects from chamber 14 and engages ramp 18 , the weight of the bale causes ramp 18 and outer tube 34 to rotate downwardly about stub shafts 42 ( FIG. 11 , causing flat surfaces 45 of tube 36 to move in such a direction relative to flat surfaces 47 of stub shafts 42 that spring pads 46 are rolled and significantly compressed. The spring rate of pads 46 is such that they cannot prevent the bale from pushing ramp 18 all the way down to the ground, but once the bale has reached the ground and rolled away from the ramp, the pads 46 overcome the weight of the ramp alone and return it to the raised position as they seek to restore themselves to their less stressed condition. [0032] Having the spring components for ramp 18 housed internally within the pivot structure for the ramp provides several important benefits. For one thing, it provides a simple, clean and uncluttered design for the ramp. For another, it protects the spring components from the harmful effects of the elements and keeps them free of dirt and residue to avoid the problem of trash accumulation on prior exposed compaction and extension springs. In this respect, having pads 46 essentially flush with the end edges 36 a of tube 36 , rather than recessed deeply within tube 36 , helps keep materials and moisture from entering into tube 36 in significant amounts. Depending upon the cross-sectional shape selected for pads 46 , the cross-section of tube 36 at end edges 36 a may essentially completely close that region. Moreover, even though there are no bearings or lubricant as part of the pivot mechanism, there is still no harmful metal-to-metal contact of the component parts. The pads 46 effectively serve not only as return spring mechanism for the ramp, but also as a means of physically isolating the outer tube 36 from stub shafts 42 while allowing the pivoting action to take place. [0033] One suitable commercially available product for use as the combination pivot and spring assembly 20 is a “Torflex” rubber torsion suspension axle product obtainable from Dexter Axle Company of Elkhart, Ind. Another suitable commercially available product may be obtained from Axis Products, Inc. of Elkhart, Ind. as part of their torsion spring product line. [0034] In selecting the spring rate for the pads 46 that make up part of assembly 20 , a number of factors are considered. The primary consideration is that the spring must be strong enough to support the weight of the ramp and minimize bouncing of the ramp while the baler travels over a rough field, yet not be so strong that the bale cannot deflect the ramp down to the ground when leaving the baler. If the spring is too strong, the bale will not be allowed to leave the baler. While in many crops this is not a problem because the bales have significant mass, in some crops such as wheat straw, the bales are not as heavy. Thus, the spring rate is selected to be such that the spring is strong enough to hold the ramp in the raised position with a minimal amount of bouncing, but not much stronger than that. [0035] The foregoing has broadly outlined some of the more pertinent aspects and features of the present invention. These should be construed to be merely illustrative of some of the more prominent features and applications of the invention. Other beneficial results can be obtained by applying the disclosed information in a different manner or by modifying the disclosed embodiments. Accordingly, other aspects and a more comprehensive understanding of the invention may be obtained by referring to the detailed description of the exemplary embodiments taken in conjunction with the accompanying drawings.
A round baler having a mobile chassis, a bale-forming chamber supported on the chassis and including a tailgate that can be raised for discharging a bale from the chamber and a bale discharge ramp. A combination pivot and spring assembly attaches the ramp to the chassis below the chamber for movement of the ramp from a raised, standby position to a lowered, unloading position for guiding a bale down to the ground as the bale leaves the chamber. The combination pivot and spring assembly includes an internal spring for yieldably maintaining the ramp in its raised position until a bale exiting the chamber engages the ramp and overcomes the force of the spring to swing the ramp down to its lowered position.
0
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is the National Phase entry of PCT/EP2006/011602, filed Dec. 4, 2006, which claims priority to German patent application number DE 102006010663.6, filed Mar. 8, 2006, each of which are incorporated herein by reference in their entireties. FIELD OF THE INVENTION [0002] This invention relates generally to processes for the production of phytosterol-containing compositions, preferably powders, and to the compositions produced by such processes and to preparations, more especially foods, containing these formulations. BACKGROUND OF THE INVENTION [0003] The literature offers numerous formulation options for enabling poorly soluble phytosterols and phytostanols, which are known to lower cholesterol, to be incorporated in food preparations, cosmetic or pharmaceutical products. Besides leading to poor dispersibility, the unfavorable solubility behavior of the substances reduces their bioavailability and adversely affects the stability of the food preparations. [0004] Numerous patent applications describe how the availability of sterols can be improved by reducing the particle sizes, mainly by micronization. Thus, DE 102 53 111 A1 describes powder-form phytosterol formulations with a mean particle size of 0.01 to 100 μm which can readily be redispersed in water. Hydrophilic auxiliaries are preferably used as protective colloids. Organic solvents are used in the production of the powders to the detriment of ecology and compatibility. [0005] Another process for the production of a sterol dispersion, in which the sterols have a particle size distribution of 0.1 to 30 μm, is described in International patent application WO 03/105611 A2. As in this process, the micronization of the sterol particles is often not sufficient on its own to facilitate uniform incorporation. Although the bioavailability of the finely dispersed particles can be increased by enlarging the surface area, the wettability of the micronized particles is so poor that they readily aggregate and generally float on water-containing surfaces. In many cases, the ground sterol can only be dispersed in a beverage by special methods which involve intensive mixing. However, corresponding mixers are not normally available to the end user, the food manufacturer. [0006] Accordingly, many manufacturers combine the micronization of the sterols with the additional use of emulsifiers. One example of this is represented by the preparations claimed in European patent EP 0897671 B1 which contain sterols and sterol esters with a particle size of at most 15 μm in the form of a mixture with selected emulsifiers, the ratio by weight of emulsifier to sterol in the aqueous phase being less than 1:2. [0007] International patent application WO 03/086468 A1 describes powder-form sterol ester formulations having a low protein content and containing mono- and diglycerides as emulsifiers. Even though these formulations are distinguished by good compatibility and have already been known for some time as food emulsifiers, efforts are being made to reduce the quantity of emulsifiers or even to avoid them altogether because emulsifiers can also influence the bioavailability of other substances present in the foods or can adversely affect the stability of the formulations. [0008] Many other methods for improving solubility and dispersibility, such as formulation as emulsions, microemulsions, dispersions, suspensions or complexing with cyclodextrins or bile salts, are mentioned in International patent application WO 99163841 A1, including formulation in the form of preparations. PEG, PVP, copolymers, cellulose ethers and esters are proposed as carriers. The direct use of food bases as carriers for powder-form sterols in the form of a premix is also known, see EP 1 003 388 B1. The choice of proteins as carriers for unesterified sterols and stanols is disclosed in WO 01/37681. [0009] The processing of unesterified sterols and stanols, which are far more hydrophobic than their esterified derivatives, imposes particularly stringent demands on the production process. One possible process for the production of sterol-containing microparticles is described in European patent EP 1148793 B1. It is based on high-energy homogenization. However, a powder subsequently produced on the basis of water-containing suspension media shows unsatisfactory homogeneity and is difficult to redisperse. [0010] One object of certain aspects of the present invention is to provide compositions free from one or more of the disadvantages mentioned at the beginning, and/or which would enable unesterified sterols and/or stanols to be more easily and uniformly dispersed in foods, and/or which would provide the foods with favorable sensory and organoleptic properties. DETAILED DESCRIPTION OF THE EMBODIMENTS [0011] The present invention relates in preferred embodiments to processes for the production of coated sterol-containing powders in which a) a carbohydrate and/or a protein and/or a protein-containing auxiliary is dissolved and/or dispersed in water and/or in a water-containing suspension medium, b) sterol and/or stanol particles are added to the resulting solution/dispersion, c) the suspension thus form is homogenized, preferably by circulation through a slot homogenizer or a colloid mill, d) at least part of the homogenizate is removed from the circuit, preferably continuously, and e) is introduced, preferably by being directly delivered, to a spray dryer and spray-dried. [0017] It is possible according to preferred processes according to the invention to produce powders even containing free unesterified sterols and stanols which enable the lipophilic active components to be more readily further processed in foods, more especially beverages. The preferred powders exhibit little tendency to agglomerate and, hence, have good flow properties. The preferred powders are distinguished by good homogeneity and, by virtue of their improved wettability, can be in many cases, further processed without major investment in equipment. In addition, the preferred powders can be uniformly distributed very quickly in the final formulation. The preferred coating greatly improves the organoleptic properties and the sensory impression. The coated powder does not stick to teeth or oral mucous membranes, so that the unpleasant sterol taste, which leads to serious losses of taste in foods containing the active components, is substantially suppressed in preferred embodiments. [0018] In accordance with preferred aspects, coating the present powder compositions with hydrophilic auxiliaries, such as carbohydrates, proteins or protein-containing additives, not only improves solubilization properties and dispersion properties, the powders surprisingly also show increased storage stability in relation to ground sterols which have a strong tendency to agglomerate. [0019] When it comes to the processing of unesterified sterols and stanols in the aqueous medium, the preferred processes reduce, and preferably eliminate, the need to use highly surface-active emulsifiers, such as lecithins, monoglycerides, diglycerides, polysorbates, sodium stearyl lactylate, glycerol monostearate, lactic acid esters and polyglycerol esters. The minimal emulsifier properties of the auxiliaries that impart hydrophilicity, more particularly the proteins, caseinates and protein-rich auxiliaries, are in many embodiments sufficient to enhance the homogeneity of the powder produced and to improve redispersibility and processability. The absence of other emulsifiers simplifies further processing by reducing possible incompatibilities with other food ingredients and reduces the occurrence of incompatibilities at the end user. The need for highly active emulsifiers, such as lecithins, monoglycerides, diglycerides, polysorbates, sodium stearyl lactylate, glycerol monostearate, lactic acid esters and polyglycerol esters, can be greatly reduces in many embodiments by use of the preferred continuous homogenization and direct removal and delivery of the homogenized suspension to the spray dryer. Such preferred processes according to the invention enable powders having a very high sterol content and the favorable properties described above to be produced without any need whatever to use organic solvents. The coated sterol formulations preferably contain at least about 50% by weight, more preferably at least about 55% by weight and most preferably at least about 65% by weight sterols, including sterol derivatives, such as stanols, based on the weight of the powder. [0020] The sterol-containing formulations produced by the present processes may readily be incorporated in foods, more particularly in milk, milk beverages, whey and yogurt beverages, margarine, fruit juices, fruit juice mixtures, fruit juice beverages, vegetable beverages, still and sparkling beverages, soya milk beverages and protein-rich liquid food substitute beverages and fermented milk preparations, yogurt, drinking yogurt, or cheese preparations, cereals and nutrition bars, and also in cosmetic or pharmaceutical preparations. [0021] In the first step of the preferred production process, in which a carbohydrate and/or a protein and/or a protein-containing auxiliary is dissolved or dispersed in water or a water-containing suspension medium, the hydrophilic auxiliaries serving as subsequent coating materials are dissolved or dispersed. To this end, the water or the water-containing suspension medium is preferably heated to a temperature of about 50° C. to about 80° C., and more preferably to a temperature of about 65 to about 75° C. In this first step, the other auxiliaries are also preferably added as required to the aqueous phase or to the water-containing suspension medium. [0022] In a preferred embodiment, glucose and casein or caseinates are used as auxiliaries. It has proved to be particularly effective in certain embodimentsto use casein (acid casein) which is only converted into sodium caseinate after dispersion in heated water by the addition of sodium hydroxide to a pH of about 6.5 to about 7.5 in the dispersion medium. Surprisingly, the process with this in situ formation of sodium caseinate results in a better dispersible end formulation by comparison with a process in which sodium caseinate is directly added. [0023] In another preferred embodiment, glucose and milk powder are used as auxiliaries. It has proved to be particularly effective to use skim milk powder because this auxiliary is the best at masking the typical unpleasant sterol taste and formulations containing skim milk powder have improved sensory properties in relation to other auxiliaries. [0024] Instead of and/or in addition to pure water, it is also possible to use water-containing suspension media which form the basis of the sterol-containing food to be subsequently produced. Thus, beverages such as, for example, milk, milk beverages, whey and yogurt beverages, fruit juices, fruit juice mixtures, fruit juice beverages, vegetable beverages, soya milk beverages and protein-rich liquid food substitute beverages and fermented milk preparations, but preferably fruit and vegetable beverages, may be directly used as the suspension medium in step a). The sterol-containing powder obtained after spray drying may then readily be redispersed with water to give a sterol-containing beverage ready for drinking. [0025] This solution or dispersion of the hydrophilic auxiliaries is preferably heated to about 75° C. to about 95° C. and preferably to about 80° C. to about 85° C., and sterol and/or stanol particles are preferably added to the system with stirring. It has proved to be particularly effective to use ground sterols and/or stanols having a small particle size with a D 90% of at most about 50 μm (as measured with a Beckman Coulter LS 320 laser diffractometer, expressed as volume distribution). The measurement is conducted in a suspension containing 10% Lamegin ZE 609 (Citrem®) in the process. The addition of larger particles in turn leads to end formulations with larger particle sizes which reduce bioavailability and are therefore undesirable in many embodiments. Sterols and/or stanols having a particle size distribution with a D 90% of at most about 30 μm are preferably used. [0026] The suspension thus formed is then homogenized by circulation through a slot homogenizer or a colloid mill. The Fryma mill used is based on the rotor-stator principle. The homogenization of the sterol-containing suspension merely leads to size reduction of the agglomerates, the sterol particles themselves undergoing no further size reduction during the treatment. Where skim milk powder is used as the auxiliary to impart hydrophilicity, homogenization with the colloid mill is sufficient to guarantee uniform distribution of the sterol particles before introduction into the spray drying tower. [0027] At least a portion of the homogenizate is preferably continuously removed from the volume stream and delivered to the spray drying tower. Without the addition of highly surface-active emulsifiers, it is difficult to maintain the strongly lipophilic unesterified sterol and stanol particles with sufficient homogeneity in the suspension medium. The suspension thus homogenized generally does not have good physical stability. Accordingly, it is highly preferred for at least a portion, and in certain embodiments only a portion, of the suspension homogenized in the slot homogenizer to be directly and continuously removed and delivered to the spray drying tower. [0028] The actual coating of the particles preferably takes place through the immediate spray drying in the spray drying tower. Because the particles are spray dried from a water-containing medium, the hydrophilic auxiliaries remain on the surface of the lipophilic sterol particles after evaporation of the water and form a hydrophilic coating which significantly improves the properties of the powder formed. Besides their lipophilic properties, generally the ground sterol particles used in the process have uneven surfaces which easily become entangled with one another. The hydrophilic coating preferably provides substantially round particles which have much better flow properties and hence better processability. [0029] By virtue of the evaporation coldness of the water during spray drying, the suspended sterol or stanol particles do not melt, even at high feed air temperatures. The particles thus comprise a core which contains the original sterol or stanol particle and a coating of the hydrophilic auxiliaries. [0030] It is expected and understood that those skilled in the art will be able to readily adapt the spray drying conditions to the particular formulation by routine variations. In the preferred embodiment of the process, in which glucose and casein or caseinate are used as hydrophilic auxiliaries in a quantity of from about 40% to about 80% by weight sterols and/or stanols, from about 3% to about 30% by weight glucose and from about 10% to about 30% by weight casein and/or caseinate, based on the formulation as a whole, good results have been obtained with a feed air temperature of from about 170° C. to about 190° C., a waste air temperature of 90±15° C. and an atomizer speed of from about 20,000 to about 30,000 r.p.m. [0000] Sterol and/or Stanol [0031] Sterols obtained from plants and vegetable raw materials—so-called phytosterols and phytostanols—are used in the present invention. Known examples are ergosterol, brassica sterol, campesterol, avenasterol, desmosterol, clionasterol, stigmasterol, poriferasterol, chalinosterol, sitosterol and mixtures thereof. Of these, β-sitosterol and campesterol are preferably used. Hydrogenated saturated forms of the sterols, known as stanols, are also included among the compounds used. Again, β-sitostanol and campestanol are preferred. Vegetable raw material sources include inter alia seeds and oils of soybeans, canola, palm kernels, corn, coconut, rape, sugar cane, sunflower, olive, cotton, soya, peanut or products from the production of tall oil. [0032] The preparations according to the invention contain from about 10% to about 90% by weight, preferably from about 30% to about 70% by weight and, in a particularly preferred embodiment, from about 35% to about 65% by weight sterols and/or stanols, based on the powder-form coated preparations. [0033] The present invention also relates in certain aspects to food preparations containing sterol/stanol formulations with the composition mentioned above. They are preferably used in beverages and milk products which then contain from about 0.1% to about 50% by weight and preferably from about 1% to about 20% by weight of the powder-form coated preparations, based on the total weight of the food. [0000] Protein-Containing Auxiliaries and/or Proteins [0034] The protein-containing auxiliaries preferably used are milk powders, such as commercially available whole milk and skim milk powders, which have been obtained from corresponding types of milk by drying. They may be used in the form of mixtures with other proteins or as sole carrier. If other proteins are added or if proteins instead of milk powder are used as the carrier, these proteins are understood to be isolated proteins which are obtained from natural animal and vegetable sources and which are added in the production of the powder-form preparations. Possible sources of proteins are plants, such as wheat, soya, lupins, corn or sources of animal origin, such as eggs or milk. [0035] Milk powders or milk-derived proteins, such as casein and casein salts, sodium and/or calcium caseinates are preferably used. Skim milk powder and/or casein and caseinates are particularly preferred for the purposes of the invention because, on the one hand, they have emulsifying properties without, at the same time, showing the disadvantages mentioned at the beginning of the food emulsifiers otherwise normally used specifically for the production of beverages and milk products, more particularly fermentation products, such as yogurt. [0036] The preparations according to the invention preferably contain from about 5% to about 90% by weight, preferably from about 5% to about 70% by weight, more preferably from about 10% to about 40% by weight and most preferably from about 12% to about 35% by weight milk powder and/or proteins, preferably in the form of skim milk powder or casein and/or sodium caseinate and/or calcium caseinate, based on the coated powder-form preparation. Carbohydrates [0037] The compounds used as carbohydrates preferably all contain food-compatible sugars selected from the group consisting of glucose, sucrose, fructose, trehalose, maltose, maltodextrin, cyclodextrin, invert sugar, palatinose and lactose. Glucose in the form of glucose syrup is preferably used as the carbohydrate. With the dispersibility and stability of the preparation in mind, it has proved to be particularly effective to use from about 0% to about 40% by weight, preferably from about 10% to about 35% by weight and, in a particularly preferred embodiment, from about 15% to about 30% by weight carbohydrates, based on the weight of powder-form sterol/stanol formulation. Other Auxiliaries [0038] The preparations according to preferred aspects of the invention contain antioxidants, preservatives and flow promoters as further auxiliaries. Examples of possible antioxidants or preservatives are tocopherols, lecithins, ascorbic acid, parabens, butyl hydroxytoluene or anisole, sorbic acid or benzoic acid and salts thereof. Tocopherols are preferably used as antioxidants. Silicon dioxide may be used as a flow regulator and promoter. Powder-Form Coated Sterol Preparations [0039] From their production, the preferred powder-form coated sterol formulations have a lipophilic core of sterols and/or stanols, optionally with other lipophilic auxiliaries, which is covered with a coating of hydrophilic auxiliaries. They preferably comprise a) from about 10% to about 97% by weight unesterified sterols and/or stanols, b) from about 3% to about 70% by weight sodium and/or calcium caseinate and/or milk powder, c) from about 0% to about 40% by weight carbohydrates, preferably a) from about 10% to about 90% by weight unesterified sterols and/or stanols, b) from about 5% to about 70% by weight sodium and/or calcium caseinate and/or milk powder, c) from about 0% to about 40% by weight carbohydrates and (a) from about 30% to about 70% by weight unesterified sterols and/or stanols, (b) from about 10% to about 40% by weight sodium and/or calcium caseinate and/or milk powder, (c) from about 10% to about 35% by weight glucose, [0049] In particularly preferred embodiments, the compositions comprise (a) from about 35% to about 65% by weight unesterified sterols and/or stanols, (b) from about 12% to about 35% by weight sodium and/or calcium caseinate, (c) from about 10% to about 35% by weight glucose, and, more especially, (a) from about 50% to about 65% by weight unesterified sterols and/or stanols, (b) from about 12% to about 35% by weight sodium and/or calcium caseinate and/or skim milk powder, (c) from about 15% to about 30% by weight glucose, or (a) from about 65% to about 75% by weight unesterified sterols and/or stanols, (b) from about 25% to about 35% by weight skim milk powder, or (a) from about 90% to about 97% by weight unesterified sterols and/or stanols, (b) from about 3% to about 10% by weight skim milk powder based on the total weight of the powder, provided that they are substantially free from highly surface-active emulsifiers selected from the group consisting of lecithins, monoglycerides, diglycerides, polysorbates, sodium stearyl lactylate, glycerol monostearate, lactic acid esters and polyglycerol esters. EXAMPLES Example 1 [0060] 129.2 g casein (from Meggle, Nährcasein 30/60 mesh) were added to 1160 g cold water and heated to ca. 72° C. During this heating phase, the pH was adjusted to 7.0 by addition of NaOH. 132.5 g glucose syrup were then added, followed by heating to 80-85° C. The ground sterol (250 g Vegapure® FTE) having a particle size distribution with a D 90% of at most 30 μm (laser diffractometry, Beckman Coulter LS 320) was then added in portions. The suspension was passed through a Fryma mill (from Fryma Rheinfelden, type MZ 80 R, slot width: 240 μm) and then homogenized by circulation through an APV homogenizer (220/30 bar). Ca. 30% of the product stream was then fed continuously from the circuit to a spray dryer (APV Anhydro, type 3 S) and spray dried. The remaining suspension was kept circulating and gradually fed to the spray drying tower. Spray Drying Conditions: [0000] inlet air temperature: 180±5° C. outlet air temperature: 90±5° C. atomizer speed: 24,000 r.p.m. [0064] The particle size distribution of the powder was then measured by laser diffractometry (Beckman Coulter LS 320): D 50% 5 μm, D 90% 29 μm. Example 2 [0065] 150 g skim milk powder (spray-dried skim milk powder, ADPI grade, supplier: Almil Bad Homburg) were added to water (1280 g) and heated to ca. 80° C. The ground sterol (350 g Vegapure FTE) was then added in portions. The suspension was repeatedly circulated through a Fryma mill (slot width: 240 μm). Ca. 30% of the product stream was then fed continuously from the circuit to a spray dryer (APV Anhydro, type 3 S) and spray dried. The remaining suspension was kept circulating and gradually fed to the spray drying tower. Spray Drying Conditions: [0000] inlet air temperature: 185±5° C. outlet air temperature: 90±5° C. atomizer speed: 24,000 r.p.m. Example 3 [0069] 15 g skim milk powder (spray-dried skim milk powder, ADPI grade, supplier: Almil Bad Homburg) were added to water (1000 g) and heated to ca. 80° C. The ground sterol (485 g Vegapure FTE) was then added in portions. The suspension was repeatedly circulated through a Fryma mill (slot width: 240 μm). Ca. 30% of the product stream was then fed continuously from the circuit to a spray dryer (APV Anhydro, type 3 S) and spray dried. The remaining suspension was kept circulating and gradually fed to the spray drying tower. Spray Drying Conditions: [0000] inlet air temperature: 185±5° C. outlet air temperature: 90±5° C. atomizer speed: 24,000 r.p.m. Dispersion Test [0073] The powders thus obtained were dispersed in milk and water in comparison with ground sterols comparable in their particle size distribution. To this end, ca. 250 ml of the liquid to be tested were poured into a glass beaker and stirred (ca. 100 r.p.m.). 2.5 g of the powders respectively containing 50% by weight and 70% by weight sterol were added to the stirred liquid and evaluated for dispersion behavior. [0074] The encapsulated sterol could be very uniformly dispersed in cold water (15° C.) and hot water (60° C.) and in milk (18° C.) whereas the untreated sterol was poorly dispersed and, owing to the hydrophobic surface, remained on the liquid surface. Even a preparation containing only 3% milk powder could be dispersed far more uniformly than the pure sterol powder. [0075] Sensory evaluation showed that the encapsulated sterols tasted neutral in water and did not stick to the gums or mouth whereas the untreated powder stuck to the oral mucous membrane and, besides a typical negative sterol taste, left behind an unpleasant sensory impression. Whereas the casein-containing powder could be dispersed somewhat better than the powder containing skim milk, the latter showed improved taste properties in relation to the casein-containing powder.
The invention relates to a method for producing coated sterol powder, wherein a) a carbohydrate and/or a protein and/or a protein-containing auxiliary agent is dissolved or dispersed in water or in an aqueous suspension medium, b) said sterol and/or stanol particles are added to the solution/dispersion, c) the thus obtained solution is homogenised in a homogeniser or a colloid mill in the circuit, d) one part of the homogenate is extracted in a continuous manner from the circuit and directly e) introduced into a dry-spraying system by pulverisation and spraying. The coated sterol-containing particles produced according to said method are incorporated into food based due to their good wettability and without using complex equipment, and display, in particular, good organoleptic and sensory properties in drinks.
0
This is a Rule 60 Divisional of U.S. Ser. No. 222,524, filed Jun. 19, 1988, now abandoned which is a Rule 60 Continuation of U.S. Ser. No. 832,461, filed Feb. 21, 1986, now abandoned which is a Continuation-in-Part of U.S. Ser. No. 688,236, filed Jan. 2, 1985, now U.S. Pat. No. 4,607,076, issued Aug. 19, 1986, which is based on Pm 82-CL-119. BACKGROUND OF THE INVENTION Poly(sodium acrylamidomethyl propane sulfonate) P(NaAMPS), hydrolyzed polyacrylamide, and poly(vinylpyrrolidone) and copolymers thereof are water soluble polymers that have been previously disclosed in the literature and have found application in the viscosification of aqueous solutions which is achieved through a combination of high molecular weight and chain expansion due to repulsion of pendant ionic groups along the polymer chain or H-bonding. These polymers are salt-sensitive, thereby limiting their application in highly saline systems. The betaines are a special class of zwitterions. These materials are self neutralized and contain no counterions. Moreover, the positive and negative charges are separated by alkyl groups. Carboxymethacrylate betaine monomers (I) and polymers (II) are well-known and disclosed in U.S. Pat. No. 2,777,872 (Jan. 15, 1957), U.S. Pat. No. 2,834,758 (May 13, 1958) and U.S. Pat. No. 2,846,417 (Aug. 5, 1958). ##STR2## Carboxyvinylpyridine betaine monomers and homopolymers (III) have also been reported [H. Ladenheim and H. Morawetz, J. Poly. Sci. 26, 251 (1957)]. ##STR3## Sulfovinylpyridine betaine monomers and homopolymers (IV) are known [R. Hart and D. Timmerman, J. Poly. Sci. 28, 118 (1958)] and Ger. Auglegeschrift 1,207,630 and Galin, et al., Polymers 25, 121,254 (1984). ##STR4## The butylsulfobetaine of poly(2-vinylpyridine) is soluble in water, but the butylsulfobetaine of poly(4-vinylypyridine) is not. Both betaines are soluble in salt solution. Methacrylate based sulfobetaine monomers and homopolymers (V) are described by Galin Polymer 25, 121,254 (1984) and Ger. Auslegeshrift 1,207,630. ##STR5## More recently, reports of vinylimidazolium sulfobetaine homopolymers (VI) have appeared [J. C. Salamone, et al Polymer 18, 1058 (1977); Polymer 19, 1157 (1978)]. ##STR6## These homopolymers are insoluble in water, but soluble in certain salt solutions. In contrast to normal polyelectrolytes, the reduced viscosity of the soluble imidazolium sulfobetaine polymers increase with increasing salt concentration. SUMMARY OF THE INVENTION The present invention relates to unique and novel betaine copolymers which are copolymers of N-vinyl pyrolidone and ester-, amide- and vinyl pyridine-based betaine monomers. Such polymers contain both positive and negative charges and are represented by the following structures: ##STR7## wherein x is about 99 to about 1 mole percent and y is about 1 to about 99 mole percent. R 1 is methyl or hydrogen, R 2 is alkyl group of 1-5 carbons and R 3 is an alkyl group from 3-4 carbons, R 4 is an alkyl group of 1-5 carbon atoms. Thus, the structures are different from conventional polyelectrolytes, which contain either positive or negative charges. In addition, unlike conventional polyelectrolytes, the aqueous viscosities of the instant materials are unaffected or may actually increase in the presence of salts like sodium chloride. The present invention is distinguished from the carboxymethacrylate betaine homopolymers and copolyers (U.S. Pat. Nos. 2,777,872, 2,834,758, 2,846,417) because sulfonate vs. carboxylate anions and low vs. high charge densities are used. Furthermore, carboxylate anions are limited by their known susceptibility to precipitation by polyvalent cations (e.g. Ca ++ ); the latter species are often found in geological formations [F. J. Glaris in "Water Soluble Resins " 2nd Ed, R. L. Davidson and M. Sittig, Eds. Rheinhold, N.Y., p. 168]. Sulfonate anions are not so limited. The present invention is distinguished from the previous sulfobetaine work because it involves NVP copolymers rather than homopolymers. These NVP-betaine copolymers show superior viscosities in salt compared with conventional NVP-ionic copolymers. GENERAL DESCRIPTION OF THE INVENTION The present invention relates to a method for increasing the viscosity of an aqueous solution which comprises the step of dissolving about 0.1 to about 5.0 wt. % of a water soluble NVP-betaine copolymer in the aqueous solution, wherein the aqueous solution is selected from the group consisting of water, a brine solution, an acid solution or a base solution, and the concentration of the salt, acid or brine in the aqueous solution is about 0.01 to about 20.0 wt. % The viscosity agents for aqueous and saline solutions of the present invention are betaine copolymers formed by a homogeneous, free radical, copolymerization, wherein the water soluble copolymers are characterized by the formulae: ##STR8## wherein x is about 99 to about 1 mole percent, more preferably about 80 to about 20 mole percent, and most preferably about 70 to about 30 mole percent, y is about 1 to about 99 mole percent, more preferably about 20 to about 80 mole percent, and most preferably about 30 to about 70 mole percent. R 1 is methyl or hydrogen, R 2 is an alkyl group of 1-5 carbon atoms, R 3 is an alkyl group of 3-4 carbon atoms, and R 4 is an alkyl group of 1-5 carbon atoms. The viscosities of aqueous solutions of these betaine copolymers were measured by means of a Contraves™ low shear viscometer model LS30 using a No. 1 cup and No. 1 bob. Temperatures were controlled to +1° C., and measurements were made at a rotational speed that gave a shear rate of 1.28 s -1 . The homogeneous copolymerization process of the instant invention comprises the steps of forming a mixture of N-vinylpyridine and betaine monomer under a nitrogen atmosphere; adding deoxygenated water to said mixture to form a reaction solution; heating said reaction solution to at least 50° C.; adding a free radical initiator to said reaction solution to initiate the copolymerization of the acrylamide monomer and the betaine monomer; polymerizing the monomers at a sufficient temperature and for a sufficient time to form the water soluble copolymer of N-vinyl pyrrolidone and betaine monomer; and recovering the water soluble copolymer from the reaction solution. Suitable free radical initiators for the instant free radical-copolymerization process are potassium persulfate; sodium thiosulfate, potassium persulfate mixture; benzoyl peroxide, and other common free radical initiators. The concentration of the free radical initiator is about 0.02 to about 0.50 grams per 100 grams of total monomer. Polymerization of the N-vinyl pyrrolidone monomer and M-3(3-sulfopropyl)-N-methacryal-oxyethyl-N,N-dimethyl-ammoniabetaine monomer is effective at a temperature of about 25° to about 90° C., more preferably at about 30° to about 65° C., and most preferably at about 45° to about 55° C. for a period of about 1 to about 48 hours, more preferably at about 2 to about 36, and most preferably at about 4 to about 24. A suitable method for recovery of the formed copolymer from the reaction solution comprises precipitation by means of acetone. DESCRIPTION OF THE PREFERRED EMBODIMENTS The following examples illustrate the present invention without, however, limiting the same hereto. EXAMPLE 1 Copolymers of NVP and Ester-Based Betaine (SPE) A 2,000 ml resin flask was set up with a condenser, a thermometer, a stirring rod with feed and N 2 inlet and outlet. The reaction flask was flushed in N 2 over night. Acrylamide used in this experiment was recyrstallized from acetone. SPE, N-(3-sulfopropyl)-N-methacroyloxyethyl-N,N-dimethyl ammonium betaine, was supplied by Howard Hall International. AIBN, the initiator, was recrystallized from methanol. Water was boiled under N 2 and cooled under N 2 . ______________________________________.sub.M/I 1/2 = 1590/10 mole % Poly (NVP-Co-SPE)______________________________________ ##STR9## ##STR10##23.45 g 65 g .0833 g AIBN 470 g H.sub.2 O 18 hours______________________________________ Both monomers were mixed in water inside the reaction flask. The monomers mixture was clear. The mixture was heated to 60° C. and AIBN (0.0833 g ) was added as solid in the reaction mixture. The polymerization was continued for 18 hours and the final product was precipitated in acetone. Elemental analysis of the product was 2.28% S, 5.94% C, 8.35% H, 9.48% N. Similar experiments were run at a ratio of 10/90 and 5050 NVP/SPE. EXAMPLE 2 Salt Sensitivity of NVP-Ester Based Copolymers Fifteen weight percent was dissolved in the following salt solutions: ______________________________________ % NaCl η CPS______________________________________90/10 NVP/SPE1.5% 0 3.131.5% 2 4.201.5% 5 4.711.5% 10 5.521.5% 20 6.5010/90 NVP/SPE1.5% 0 Cloudy1.5% 2 3.711.5% 5 4.691.5% 10 6.191.5% 20 9.1650/50 NVP/SPE1.5% 0 Cloudy1.5% 2 3.961.5% 5 5.381.5% 10 6.701.5% 20 9.34______________________________________ In contrast, the viscosity of a copolymer NVP with a simple ionic monomer (NaAMPS)® declined in salt. ______________________________________50/50 NVP/NaAmps % NaCl η CPS______________________________________1.5% 0 6.51.5% 2 2.21.5% 5 2.11.5% 10 2.21.5% 20 2.3______________________________________ This Example shows the superior salt response of the instant copolymer with conventional ionic copolymers of NVP. EXAMPLE 3 Copolymers of NVP and Amide Based Betaines (SPP) NVP/SPP copolymers were prepared in 150 ml H 2 O at 16.7% total solids level, at a M/I 1/2 =15.0 at 60° C. with AIDN as initiator. The NVP/SPP ratio was varied from 0/80 to 80/20. Product compositions were determined by elemental analysis. SPP is N-(3 sulfopropyl)-N-methacramidopropyl-N-N-dimethylammonium betaine, available from Howard Hall Company. EXAMPLE 4 Copolymer of NVP and Vinyl Pyridine-Based Betaine (SPV) A NVP/SPV copolymer was prepared in 150 ml of H 2 O at 16.7% total solids, at a M/I 1/2 =15.0 at 60° C. with AIBN as the initiator. SPV is a sulfopropyl betaine of 2-vinyl pyridine, available from Howard Hall Company. The NVP/SPV ratio was 50/50. The polymerization reached 15% conversion in 6 hours.
A water soluble copolymer having the structure: ##STR1## wherein X is about 1 to about 99 mole percent and y is about 99 to about 1 mole percent.
2
FIELD OF THE INVENTION The present invention relates to a folding apparatus and more particularly, relates to a quarter folder for signatures. BACKGROUND OF THE INVENTION The folding of paper signatures or like objects is known in the art. Generally, such folders operate at a relatively slow throughput compared to the speed of the press from which the signatures come. In view of this limitation, either the press speed is slowed down to meet that of the folding apparatus or alternatively, a plurality of the folder machines for a single press is required. Presses conventionally include folding units which bring out multiple sheet single folded assemblies in an overlapped running shingle. The assemblies are called signatures and their folded edges are called spines. The signatures in a running shingle usually move with the spines as the leading edge and with each signature set back slightly from the one which precedes it so that it travels in a shingled relationship. The single folded signature is often called a half folded signature and it often is desirable to fold the same to become a quarter folded signature. By cutting the original spine edge, a quarter folded signature may be turned into a booklet where each page is one-quarter of the original sheet of paper. Generally, the quarter folding is done on an individual signature. This operation presents an inherent limitation on the speed at which it can be done since each sheet must be individually handled and then quarter-folded. SUMMARY OF THE INVENTION It is an object of the present invention to provide a folder for signatures which can operate at a high through-put. It is a further object of the present invention to provide a mobile inline quarter folder which is able to keep up with the printing speed of a relatively fast web press. According to one aspect of the present invention, there is provided a folder comprising an input conveyor for receiving a shingled stream of signatures, means for aligning the shingled stream of signatures, means for folding the shingled stream of signatures to form a folded stream of shingled signatures, means for singulating the folded stream of shingled signatures into individual folded signatures, means for re-shingling the individual folded shingled signatures into a stream. According to a further aspect of the present invention, there is provided a method for folding signatures, the method comprising the steps of providing a line of shingled signatures, aligning the shingled signatures, folding the shingled signatures, singulating the folded shingled signatures and re-shingling the singulated signatures to form shingled folded signatures. The apparatus of the present invention includes a number of different stations which operate together to provide an inline folder which can operate at high speeds. As utilized herein, the word signatures is used to designate any paper which is to be folded. In a preferred embodiment, the apparatus of the present invention is used as a quarter folder—i.e. it takes an already folded signature and further folds the same. However, it will be understood that the present invention can also be used for performing a half folded signature. The description of the preferred embodiment will generally relate to the quarter folder configuration. The first station preferably includes a crusher roller which is designed to reinforce the original half fold on the signature as well as to eliminate any air pockets to ensure proper handling of the signature throughout the apparatus. The crusher roller is preferably provided with a quick release for security purposes. The first station in a preferred embodiment also comes with a drop down air-actuated conveyor which works when a make-ready switch is turned off. In the off position, copies entering the machine are immediately diverted downwards under the machine where they may be placed into a scrap bin or alternatively, fall onto a separate conveyor which carries the product away from the machine. When the pressman is ready to commence the quarter folding operation, the make-ready switch is turned on and copies are immediately allowed to proceed to the subsequent stations. Incorporated with the drop down conveyor are sensors to detect signatures which are sufficiently out of line so as to pose a problem for further processing. When such signatures are detected, the conveyor will immediately drop down. The second station comprises an aligning station wherein there is provided a high-speed belt jogger which will accurately position the copies entering therein. The jogger includes a slightly elastic belt which is entrained about rollers. At least some of the rollers are of a non-circular configuration so as to provide a vibratory action to the stream of shingled signatures. In preferred embodiments, a tensioning arrangement is provided for the belting forming the jogger to ensure that the belt as it passes over the non-circular roller is not slipping and provides constant vibration. Furthermore, the rollers for the belt preferably are provided with a double crown arrangement to prevent the belts from derailing. A third station comprises a section for pinning the signatures and forming the pre-folding configuration. Wings of the paper entering the third section are guided to prevent subsequent problems with the handling of the signatures. In this section, the signatures are formed and folded into the desired configuration and each copy is scored to ensure a clean final fold. The fourth station is operative to finish the fold which forms the new spine of the signatures. In this regard, spring steel is used immediately after the creasing wheel to ensure a satisfactory fold. The bottom section of the folder is open so that the signature can now move without any friction on the sides which would otherwise create an uneven quarter folded copy. In the fifth station, the copies are turned through 90° so that they are in a desirable horizontal position for the subsequent operations. The arrangement is such that the subsequent high-speed section does not prematurely pull the copies out ahead of time. The sixth station is a singulating station which individually separates a stream of signatures in preparation for the re-shingling operation. The seventh station is a re-shingling operation and provides a catching and braking system which re-shingles each copy to be the same distance apart as when the signatures first entered the apparatus. Preferably, the section also has a drop down conveyor of the type discussed with respect to the first station. BRIEF DESCRIPTION OF THE DRAWINGS Having thus generally described the invention, reference will be made to the accompanying drawings illustrating embodiments thereof, in which: FIG. 1 is a top plan view illustrating the sequence of operation for the transformation of a half fold signature into a quarter fold signature; FIG. 2 is a side elevational view thereof; FIG. 3 is a top plan view of the apparatus; FIGS. 3A and 3B are top plan views of the front and rear portions of FIG. 3 ; FIGS. 4A and 4B are side elevational views thereof; FIG. 5 is a top plan view of one of the belts in a jogger section of the apparatus; FIG. 6 is a view taken along the lines 6 - 6 of FIG. 5 ; FIG. 7 is a top plan view of the former section of the apparatus; FIG. 8 is a sectional view taken along the lines 8 - 8 of the FIG. 7 ; FIG. 9 is a cross sectional view taken along the lines 9 - 9 of FIG. 7 ; FIG. 10 is a cross sectional view taken along the lines 10 - 10 of FIG. 7 ; FIG. 11 is an expanded top plan view of the turning of the quarter folded signatures through 90 degrees; and, FIG. 12 is a side elevational view thereof. DETAILED DESCRIPTION OF THE INVENTION Referring to the drawings in greater detail and by reference characters thereto, there is illustrated in FIG. 3A the first portion of a quarter folder apparatus which is generally designated by reference numeral 10 . Quarter folder apparatus 10 is designed to receive a plurality of half fold signatures 12 coming from any suitable source of the same, including a printing press. Half fold signatures 12 are delivered to a conveyor section generally designated by reference numeral 14 and which conveyor section 14 includes a first roll 16 , a second roll 18 , and a third roll 20 . A plurality of drive belts 22 are entrained about first rolls 16 and 18 , with other drive belts 24 being entrained about second roll 18 and third roll 20 . Mounted above first roll 16 is a crusher roll 26 which is designed to reinforce the crease forming the spine of half fold signatures 12 . As may be seen in FIG. 4A , a pneumatic cylinder 28 is mounted to a frame post 32 and to a bracket 30 on which third roll 20 is journalled. Thus, the conveyor can be moved from a normal operational position to a drop down position (as shown in dotted lines) wherein any signatures there are discharged into a container 34 situated therebelow. The subsequent section of apparatus 10 is a jogger section and to which reference will now be had. The jogger includes a plurality of rolls 46 about which belts 48 are entrained. The aligning of the signatures is accomplished by having a pair of end rolls 38 about which a jogger belt 44 is entrained. As will be seen in FIGS. 5 and 6 , there is also provided a plurality of hexagonal rolls 40 to impart a vibratory action to jogger belt 44 . There are also a plurality of pressure rolls 42 which are designed to maintain pressure on jogger belt 44 such that a good vibratory action is achieved without any slippage of the belt 44 . The jogger belts converge in a downstream direction. Subsequently, the half folded signatures pass to a forming and folding section. In this section, there are provided a pair of lower end rolls 52 , 54 about which a small diameter belt 58 is entrained. Between lower end rolls 52 , 54 there are also provided a plurality of support rolls 56 . There is also provided a pair of top end rolls 60 and 62 along with a plurality of top support rolls 64 which are pressure adjustable. A relatively narrow top belt 66 is entrained about the rolls. At the entrance to the forming and folding section, there are provided a pair of guide bars 68 and 70 ( FIG. 9 ), one being situated on each side of the apparatus. Each of the guide bars is designed to gently guide the ends of the half folded signatures with the guiding surface being convex in configuration as may be seen in FIG. 9 . Situated further downstream are a second pair of guiding members 72 , 73 . A pair of spring steel members 74 , 76 are arranged to finalize the fold in the signatures. Immediately preceding spring steel members 74 , 76 is a creasing roll 78 designed to impart a sharp crease in the signatures. At the next section, there are provided a pair of belt mounting assemblies 80 , 80 ′. A belt 88 is entrained a roll in belt mounting assembly 80 thereabout as well as a roll 82 at the other end thereof. Mounted intermediate the rolls is a guide roller 84 . As may be seen in FIG. 3 , a pneumatic cylinder 86 is provided for moving belt mounting assembly 80 is provided. As shown be seen in FIG. 3 , belts 88 , 88 ′ are twisted such that they take the signatures from a vertical direction to 90° to a horizontal direction. During all this time, the belts maintain a secure grip on the spine of the signatures. Following the folding operation, the signatures are fed to a singulating mechanism which comprises an upper conveyor 92 and a lower conveyor 102 . Upper conveyor 92 comprises a pair of end rolls 94 about which belts 100 are entrained. Mounted centrally between end rolls 94 , 96 is a pressure roll 98 . Lower conveyor 102 includes end rolls 104 , 106 about which belts 108 are entrained. The above arrangement is such that as signatures are fed, a nip is created between belts 100 , 108 by means of pressure roll 98 . This section is running at a substantially higher speed than the previous section and a single signature is withdrawn from the shingled stream. In this regard, the spacing is such that the next signature is securely retained by the preceding section. The re-shingling section comprises an upper conveyor 110 which includes a pair of end rolls 112 , 114 and adjustable pressure rolls 116 , 118 with belts 126 entrained thereabout. A lower conveyor 120 comprises a pair of end rolls 122 , 124 having belts 128 entrained thereabout. As may be seen from FIG. 4B , there is also provided a pneumatic cylinder 130 mounted on bracket 132 of the frame and a bracket 134 of lower conveyor 120 . Thus, the conveyor can be dropped down or lowered to deposit undesired product in container 136 . As the signatures are travelling at an extremely high rate of speed as they exit the singulating section, the geometry of the upper conveyor 110 and lower conveyor 120 is important. As may be seen, lower conveyor 120 has a slight upward angle while there is a convergence between belts 122 , 124 to guide the singulated shingles. Preferably, the lower conveyor is at an angle of between 4° and 6° with respect to the horizontal. Referring to FIGS. 1 and 2 , the operation of the machine on the signatures is illustrated. As designated by reference numeral 12 , originally the signatures enter as half fold signatures and typically slightly misaligned. The signatures then go through the crusher roll and the jogger section as illustrated in reference numeral 202 where they are aligned and flattened. As shown by reference numeral 204 , as they exit the aligned or jogging section, they are in a proper shingled position. Subsequently, as indicated by reference numeral 206 , the signatures have their wings guided downwardly until, as they pass through the end of the forming section, they are as shown by reference numeral 208 with a final folding being indicated by arrows 210 . As indicated by reference numeral 212 , the shingles are then rotated through 90° to lie flat as indicated by reference numeral 214 where they pass to be singulated as indicated by reference numeral 216 . It will be understood that the above described embodiment is for purposes of illustration only and that changes and modifications may be made thereto without departing from the spirit and scope of the invention.
A quarter folder comprising an input conveyer for receiving a shingled stream of half folded signatures, an aligning section for aligning the signatures, a folding section for folding the shingled stream to thereby form a quarter folded shingled stream, a singulating section to separate the shingled signatures into individual folded signatures and a re-shingling section. The quarter folder of the present invention can operate at a high speed and receive copies directly from a press.
1
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] The present application is a continuation of pending International Patent Application PCT/FR2010/000726 filed on Nov. 2, 2010 which designates the United States and claims priority from French Patent Application 0905366 filed on Nov. 6, 2009, the content of which is incorporated herein by reference. FIELD OF THE INVENTION [0002] The invention relates to a push-button for a system for dispensing a product under pressure, as well as such a dispensing system. BACKGROUND OF THE INVENTION [0003] In a particular application, the dispensing system is intended to be provided on bottles used in perfumery, in cosmetics or for pharmaceutical treatments. Indeed, this type of bottle contains a product which is returned by a dispensing system comprising a device for sampling under pressure of said product, said system being actuated by a push-button in order to allow for the spraying of the product. In particular, the system for sampling comprises a pump or a valve with manual actuation by the intermediary of the push-button. [0004] Such push-buttons are conventionally carried out in two portions: an actuator body and a spray nozzle for the product which are associated together to form a vortex unit comprising a vortex chamber provided with a dispensing orifice as well as with at least one supply channel of said chamber. [0005] In particular, the supply channels exit tangentially in the vortex chamber which is cylindrical of revolution in order to rotate the product very rapidly, the dispensing orifice having a reduced diameter in relation to that of said chamber so that the product in rotation escapes through said orifice with a speed that is sufficient to be broken up into droplets forming the aerosol. [0006] However, as this breaking up takes place in an uncontrolled manner, the aerosol is constituted of droplets of highly varied size. For example, for a pump or a valve supplying a push-button with a flow of alcohol under a pressure of 5 bars, and an outlet orifice of 0.3 mm, the aerosol is commonly constituted of droplets of a diameter between 5 μm and 300 μm. [0007] However, the large droplets are heavier than the smallest ones and follow a different dispensing trajectory, which can cause indelible stains in the case of perfumes. Also, the small droplets are the lightest and can be inhaled, which may be the objective sought in the case of medications, but which can be an undesirable effect in the case of toxic products. Furthermore, in the case of medications which must be dispensed according to a precise dosage, the location of application, for example inside the respiratory system, depends on the size of the droplets, and the high disparity of sizes misrepresents the treatment. [0008] Moreover, the size of the droplets coming from a vortex chamber depends in part on the force and on the speed with which the user actuates the pump by pressing on the push-button with his finger, as the induced pressure depends on this. [0009] Furthermore, in particular due to the effects of the centrifugal force at the outlet of the vortex chamber, the aerosol has a tendency to be hollow with a substantially tapered shell which is constituted of most of the droplets although there are few inside the cone. In particular, this distribution of droplets can be detrimental for dermal applications. [0010] It is known moreover, in particular from document FR-2 915 470, a push-button comprising a dispensing chamber which is provided with channels each converging towards an outlet orifice, said converging channels being arranged in order to allow for the impaction of the streams of product dispensed by said orifices. As such, during the impaction of the streams dispensed at high speed, an aerosol is formed without having recourse to a vortex chamber. [0011] However, to produce such an aerosol by satisfactorily controlling the calibration and the spatial distribution of the droplets, it is necessary to form identical streams and of which the convergence is perfect, which is very difficult to carry out industrially at the interface between the actuator body and the nozzle mounted in said body. This results in that the streams can cross without impacting one another or in impacting one another only partially, which degrades the calibration and the spatial distribution of the droplets formed. [0012] Moreover, the supply of the converging conduits or of the vortex chamber according to prior art does not allow for a breaking up of the dose of product to be dispensed, i.e. to return only a portion of the dose provided by the pump. Indeed, the travel of the pressing of the push-button is carried out too quickly, in particular by a magnitude of 0.2 seconds for 120 μl, to be able to be interrupted by the user. SUMMARY OF THE INVENTION [0013] The invention aims to resolve the problems of prior art by proposing in particular a push-button making it possible to dispense an aerosol formed of droplets having an improved calibration and spatial distribution, and this by increasing the duration of the production of said aerosol. [0014] To this effect, and according to a first aspect, the invention proposes a push-button for a system for dispensing a product under pressure, said push-button comprising a body having a mounting well on a feed tube for the product under pressure and a housing in communication with said well, said housing being provided with an anvil around which a spray nozzle is mounted in such a way as to form a dispensing path for the product between said housing and a vortex unit comprising a vortex chamber provided with a dispensing orifice as well as least one supply channel of said chamber, said vortex chamber being delimited by a lateral surface having a tapered geometry in relation to which the supply channel or channels extend in a transversal plane, said lateral surface converging from an upstream end wherein tangentially exits the downstream end of the supply channel or channels towards a downstream opening for supplying the dispensing orifice, said dispensing orifice has an outlet dimension which is equal to the internal dimension of said downstream opening. [0015] According to a second aspect, the invention proposes a dispensing system for a product under pressure, comprising a system for sampling provided with a feed tube for the product under pressure whereon the well of a push-button is mounted to allow for the spraying of the product. BRIEF DESCRIPTION OF THE DRAWINGS [0016] Other objectives and advantages of the invention shall appear in the following description, provided in reference to the annexed figures wherein: [0017] FIG. 1 is a partial longitudinal section view of a bottle provided with a dispensing system according to an embodiment of the invention; [0018] FIG. 2 is a partial longitudinal section view of the push-button of FIG. 1 ; and [0019] FIG. 3 are views of the nozzle of the push-button according to the FIG. 2 , respectively as a cutaway view ( FIG. 3 a ) and of the internal portion ( FIG. 3 b ). DETAILED DESCRIPTION OF THE INVENTION [0020] In relation with the figures, a push-button for a dispensing system for a product in particular liquid under pressure is described hereinbelow, said product able to be of any nature, in particular used in perfumery, in cosmetics or for pharmaceutical treatments. [0021] The push-button comprises a body 1 having an annular skirt 2 which surrounds a well 3 for the mounting of the push-button on a feed tube 4 of the product under pressure. Moreover, the push-button comprises an upper zone 5 allowing the user to exert a finger press on said push-button in order to be able to displace it axially. In the embodiment shown, the push-button is provided with a trim 6 for aspect that surrounds the body 1 and whereon is formed the upper zone 5 for pressing. [0022] In relation with FIG. 1 , the dispensing system comprises a system for sampling 6 provided with a feed tube 4 of the product under pressure which is inserted in a sealed manner in the well 3 . In a known manner, the dispensing system further comprises means for mounting 7 on a bottle 8 containing the product and means for sampling 9 the product inside of said bottle which are arranged to supply the feed tube 4 with product under pressure. [0023] The system for sampling 6 can include a pump with manual actuation or, in the case where the product is conditioned under pressure in the bottle 8 , a valve with manual actuation. As such, during a manual displacement of the push-button, the pump or the valve is actuated to supply the feed tube 4 with product under pressure. [0024] The body 1 also has an annular housing 10 which is in communication with the well 3 . In the embodiment shown, the housing 10 has an axis perpendicular to that of the mounting well 3 in order to make possible a lateral spraying of the product relatively to the body 1 of the push-button. In an alternative not shown, the housing 10 can be collinear to the well 3 , in particular for a push-button forming a nasal spray tip. [0025] The housing 10 is provided with an anvil 11 around which a spray nozzle 12 is mounted in such a way as to form a dispensing path for the product under pressure between said housing and a vortex unit. To do this, the anvil 11 extends from the bottom of the housing 10 by leaving a communication channel 13 between the well 3 and said housing. [0026] In the embodiment shown, the nozzle 12 has a cylindrical lateral wall 14 of revolution which is closed towards the front by a proximal wall 15 . The association of the nozzle 12 in the housing 10 is carried out by press fitting of the external face of the lateral wall 14 , the rear edge of said external face being furthermore provided with a radial protrusion 16 for anchoring the nozzle 12 in said housing. [0027] Furthermore, a print of the vortex unit is formed in a hollow in the proximal wall 15 and the anvil 11 has a planar distal wall 17 whereon the proximal wall 15 of the nozzle 12 is pressing against in order to delimit the vortex unit between them. In an alternative not shown, a print of the vortex unit can be formed directly on a wall of the housing 10 , in particular for a nasal spray tip. In another alternative not shown, the distal wall 17 can have a convexity turned towards the interior of the vortex unit. [0028] Advantageously, the nozzle 12 and the body 1 are carried out by moulding, in particular from a different thermoplastic material. Furthermore, the material forming the nozzle 12 has a rigidity which is higher than the rigidity of the material forming the body 1 . As such, the substantial stiffness of the nozzle 12 makes it possible to prevent it from deforming when it is mounted in the housing 10 in such a way as to guarantee the geometry of the vortex unit. Furthermore, the less substantial stiffness of the body 1 allows for an improved seal between the well 3 for mounting and the feed tube 4 . [0029] In the example embodiment, the body 1 is made of polyolefin and the nozzle 12 is made of cycloolefin copolymer (COC), poly(oxymethylene) or poly(butylene terephthalate). [0030] In the embodiment shown, the dispensing path has successively in communication from upstream to downstream: an upstream annular conduit 30 in communication with the channel 13 , said annual conduit being formed between the rear portion of the internal face of the lateral wall 14 of the nozzle 12 and the portion of the external face of the lateral wall of the anvil 11 which is arranged across from it; four axial conduits 18 formed between four spacers 19 which extend over the internal face of the lateral wall 14 of the nozzle 12 , said spacers having a free wall 20 which is press-fit on the external face of the lateral wall of the anvil 11 ; a downstream annular conduit 21 formed between the proximal wall 15 of the nozzle 12 and the distal wall 17 of the anvil 11 . [0034] On the downstream side, the dispensing path supplies with product under pressure the vortex unit which comprises a vortex chamber 22 provided with a dispensing orifice 23 as well as with at least one supply channel 24 of said chamber. More precisely, in the embodiment shown, the supply channels 24 communicate with the downstream annular conduit 21 . In particular, this embodiment makes it possible to limit the length of the supply channels 24 in order to reduce the induced head losses. [0035] The vortex chamber 22 is delimited by a lateral surface 25 having a tapered geometry which extends along a dispensing axis D, the dispensing channels 24 extending in a transversal plane in relation to said dispensing axis. In the description, the terms of positioning in space are defined in relation to the dispensing axis. [0036] In the embodiment shown, the tapered geometry is of revolution around the dispensing axis D, an internal dimension of said geometry thus corresponding to a diameter. In an alternative not shown, the tapered geometry can be of polygonal section, an internal dimension of said geometry thus corresponding to a diameter of the shell inscribed in said geometry. [0037] The lateral surface 25 converges from an upstream end 26 wherein exits tangentially the downstream end of the supply channels 24 towards a downstream opening 27 for supplying the dispensing orifice 23 . Furthermore, the dispensing orifice 23 has an outlet dimension which is equal to the internal dimension of the downstream opening 27 . Advantageously, the angle of convergence of the lateral surface 25 can be between 30° and 50°, in particular of a magnitude of 45°. Moreover, in the embodiment shown, the upstream end 26 has a cylindrical geometry of revolution wherein the downstream end of the supply channels 24 exits tangentially. [0038] As such, during the dispensing of the product under pressure, the tangential supply of the vortex chamber 22 makes it possible to put the product into rotation in the upstream end 26 of said chamber, the product is then thrust and pushed in rotation along the lateral surface 25 of said chamber by forming a pool of product of which the speed of rotation increases and which converges towards the downstream opening 27 , then said converging pool can escape through the dispensing orifice 23 without being deformed in such a way as to be able to be impacted to form the aerosol. [0039] This embodiment therefore makes it possible to combine the advantages of the use of a vortex chamber 22 with that of the impaction of the product, without having the disadvantages therein, in particular relatively to the dispersion of sizes of droplets and to the risks of non-impaction of the product. The impaction of the swirling pool makes possible in particular the carrying out of an aerosol formed from a uniform spatial distribution of droplets in suspension in the air, the size of said droplets being small and uniform. In particular, the aerosol can then have the appearance of a plume of smoke with droplet sizes between 10 μm and 60 μm with an average of 35 μm for an alcoholic product, and this regardless of the pressing force that the user exerts on the push-button. [0040] In the embodiment shown, the vortex unit has two supply channels 24 of the vortex chamber 22 , said channels being arranged symmetrically in relation to the dispensing axis D. [0041] Moreover, to tangentially supply the vortex chamber 22 by causing the product to turn along its lateral surface 25 , each channel 24 has a U-shaped section which is delimited between an exterior wall 28 and an interior wall 29 . The exterior wall 28 is tangent to the upstream end 26 and the interior wall 29 is offset from it by a distance less than 30% of the internal dimension of the upstream end 26 in such a way as to avoid an impaction of the product in said upstream end. [0042] In the embodiment shown, the interior wall 29 is parallel to the exterior wall 28 . In an alternative not shown, the interior wall 29 has an angle of convergence with the exterior wall 28 in the upstream-downstream direction, the offset between said walls then being measured on the section of exiting of the channels 24 in the upstream end 26 . [0043] Alternatively, more than two supply channels 24 can be provided, in particular three channels 24 arranged symmetrically in relation to the dispensing axis D, or a single channel 24 can be provided to tangentially supply the vortex chamber 22 . [0044] Moreover, the downstream end of the supply channel 24 or all of the downstream ends of each of the supply channels 24 forms a supply section of the vortex chamber 22 . In order to increase the duration of dispensing of a dose of product on the actuating stroke of the push-button, it can be provided that this supply section be low relatively to the interior surface of the upstream end 26 . In particular, the surface of the supply section can be less than 10% of the interior surface of the upstream end 26 . [0045] Preferentially, the surface of the supply section can be between 0.01 mm 2 and 0.03 mm 2 . In an example embodiment, the internal dimension of the upstream end 26 is 0.6 mm, or an interior surface of 0.28 mm 2 , and each channel 24 has a width and a depth of 0.1 mm, or a surface of 0.02 mm 2 for the supply section. Alternatively, the channels 24 can have a width of 70 μm and a depth of 130 μm. [0046] Furthermore, the fact of the passing of the product in a reduced supply section, the duration of dispensing is increased. For example, for a dose of 120 μl the duration of dispensing can be between 0.5 and 2 seconds in such a way as to allow the possibility for the user to interrupt the dispensing of the aerosol during actuation. [0047] In the embodiment shown, the downstream opening 27 of the vortex chamber is surmounted by a dispensing orifice 23 having a cylindrical geometry of revolution around the dispensing axis D, the internal dimension of said orifice being equal to the internal dimension of the downstream opening 27 . [0048] Advantageously, the axial dimension of the dispensing orifice 23 is low in relation to its internal dimension, in such a way as to not disturb the convergence of the swirling pool. In particular, the axial dimension of the dispensing orifice 23 can be less than 50% of its internal dimension. [0049] In an alternative not shown, the downstream opening 27 of the vortex chamber 22 can form a dispensing orifice 23 . [0050] The creating of the aerosol is particularly satisfactory when the internal dimension of the downstream opening 27 is low relatively to the internal dimension of the upstream end 26 , in such a way that the impaction of the pool is carried out as close as possible to the dispensing orifice 23 . In particular, the internal dimension of the downstream opening 27 can be less than 50% of the internal dimension of the upstream end 26 , more precisely by being between 20% and 40% of said internal dimension. [0051] Preferentially, the axial dimension of the vortex chamber 22 is relatively substantial, in particular of a magnitude of or greater than the internal dimension of the upstream end 26 , in such a way as to allow for the establishment of the swirling pool along the lateral surface 25 of said vortex chamber and to confer a progressive convergence. In particular, the axial dimension of the vortex chamber 22 is at least equal to 80% of the internal dimension of the upstream end 26 , more precisely being between 90% and 200% of said internal dimension. [0052] According to a particular embodiment in relation with a product of which the dispensing pressure is between 5 and 7 bars, the internal dimension of the upstream end 26 is 0.6 mm, the internal dimension of the downstream end 27 is less than or equal to 0.24 mm by being in particular between 0.15 mm and 0.24 mm, the axial dimension of the vortex chamber 22 is at least equal to 0.55 mm, the axial dimension of the dispensing orifice 23 is less than 0.10 mm.
A pushbutton for a system for dispensing a pressurized substance, the pushbutton including a body having a housing provided with an anvil around which a spray nozzle is mounted so as to form a substance dispensing path between the housing and a swirl array including a swirl chamber provided with a dispensing port as well as at least one supply duct for the chamber, the swirl chamber being defined by a side surface having a frusto-conical shape relative to which the supply duct(s) extend(s) in a transverse plane, the side surface tapering from an upstream end into which the downstream end of the supply duct(s) tangentially extends, to a downstream supply opening of the dispensing port, the dispensing port having an outlet size that is equal to the internal size of the downstream opening.
1
BACKGROUND OF THE INVENTION The present invention relates to sports training devices and, more particularly, to a device for exercising, strengthening and developing the lower leg muscles. Heretofore, a fairly wide variety of specialized exercising equipment have been proposed for exercising particular muscle groups used in a particular sport. Such equipment, for example, has been developed for sports such as golf, baseball and football. Development of specific muscles or muscle groups is particularly helpful in increasing proficiency and avoiding injury. Skiing, in particular, is a sport which requires development of specific muscle groups to increase proficiency and prevent injury. Downhill and cross-country skiing are sports which continue to grow in popularity. Downhill or Alpine skiers are exposed to and suffer sprains and breaks of the ankle, breaks of the lower leg bones, that is the fibula and tibia, and torn ligaments or cartilage at the knee and ankle joints. These types of injuries typically occur when the mechanical safety bindings holding the boot to the ski fail to operate properly. These bindings typically include a lateral or side-to-side toe release and vertical heel release. The settings are variable to accommodate the weight of the skier as well as the proficiency level of the skier. The bindings may be improperly adjusted or may operate improperly due to dirt and/or ice which can collect thereon and increase the load on the leg prior to release. It is, therefore, important for the skier to develop strong muscles of the lower leg to reduce the chance of and occurrence of injury. Further, the muscles of the lower leg are primarily used to initiate turns for both the recreational and competition skier. A competition skier, especially when competing in the slalom, may execute frequent step turns which require rotation of the ski about a vertical axis. The lower leg muscles are primarily used to accomplish such rotation. The muscles used to accomplish these turns are the same which are used to resist the forces involved in a lateral ski boot/binding release. Heretofore, exercising equipment has not been developed to strengthen the lower leg muscles and, therefore, to assist in preventing injury to skiers and to increase proficiency. Presently available exercising devices are primarily directed for use by invalids or for physical therapy. Examples of such devices may be found in U.S. Pat. No. 2,645,482, entitled FOOT ACTUATED EXERCISING DEVICE, and issued on July 14, 1953 to Magida, and U.S. Pat. No. 3,022,071, entitled FOOT ACTUATED EXERCISING DEVICE and issued on Feb. 20, 1962 to Malone, et al. These devices are not capable of subjecting the lower leg muscles to the stresses or the loads necessary to properly develop them and strengthen them for skiing. A need, therefore, exists for an exercising apparatus capable of developing and strengthening the lower leg muscles by subjecting them to the same stresses and loads encountered while skiing. Such a device would greatly assist in the prevention of injury to skiers as well as increase their proficiency by increasing quickness and ski control. SUMMARY OF THE INVENTION In accordance with the present invention, a lower leg muscle exercising apparatus is provided which accommodates the needs of the recreational and competition skier, and whereby the shortcomings of presently available leg exercising devices are substantially overcome. Essentially, the device includes a foot retaining means and a base. Provision is made for supporting the foot retaining means on the base for multi-axis movement to thereby accommodate flextion and extension of the ankle as well as rotation of the lower leg. Provision is made for applying a force opposing movement of the foot retaining means and which constantly biases the foot retaining means to an initial position. In narrower aspects of the invention, the force exerted on the foot retaining means in resisting movement thereof increases with motion of the foot retaining means. The apparatus permits both dynamic and isometric exercising of the lower leg muscles and simulates the loads imposed in resisting boot/binding release and during normal skiing motions. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a lower leg muscle developing apparatus in accordance with the present invention; FIG. 2 is a front, elevational view thereof; FIG. 3 is a right, elevational view thereof; and FIG. 4 is a perspective view of an alternative embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT A preferred embodiment of the apparatus in accordance with the present invention is illustrated in FIG. 1 and generally designated 10. Apparatus 10 includes a generally rectangular, horizontally positioned base 12 and a foot retaining means or foot holder 14 supported on base 12 by a joint structure 16 in a normally vertical orientaton with respect to the base. Extending generally vertically from or perpendicular to an upper surface 18 of base 12 is a post 20. A bracket or spring attachment rod 22 extends outwardly from a face 24 of post 20 adjacent the top end 26 thereof. Foot retaining or holding means 14 is a generally box-like structure including a bottom wall 30, opposed, parallel, spaced sides 32, 34, and an end wall or heel abutting portion 36. Holder 14 is open at the end opposite end wall 36. Extending between sidewalls 32, 34, adjacent the open end of the holder is a toe retainer or restrainer rod or bar 38. As illustrated in FIG. 1, holder 14 is dimensioned to receive the foot 40 of the user. The heel 42 of the user will abut wall 36 and the foot is retained by contact with bar 38. The holder is constructed to permit movement thereof by flexion, extension and rotation of the ankle and lower leg about multiple axes. Joint means 16 supports the holder 14 on base 18 for movement about a vertical or pitch axis, generally designated 50 in FIG. 2, and about a lateral or yaw axis, generally designated 52 in FIG. 3. The joint permits simultaneous movement about both axes to permit compound rotational movement of the holder. In the embodiment illustrated in FIGS. 1, 2 and 3, joint 16 includes a first hinge 60 and a second hinge 62. Hinge 60 includes a first hinge plate 64 secured to base 12, a second hinge plate 66 and a hinge pin 68 which defines the pivot axis 52. Hinge 62 similarly includes a first hinge plate 70 which is welded or otherwise suitably secured to hinge plate 66 of hinge 60. Hinge 62 further includes a second hinge plate 72 connected to plate 70 by a pivot or hinge pin 76. Plate 72 is secured by suitable fasteners 78 to outer surface 80 of bottom wall 36. A yaw or lateral spring 82 extends between rod 22 and an attachment in the form of an eye bolt 84 secured to wall 30 of holder 14 adjacent the top thereof. Spring 82 is preferably a coil spring having one end 85 extending through an aperture 86 formed in post bracket 22. The opposite end 87 of the spring extends through the eye of attachment 84. Spring 82 provides a restoring force which increases upon lateral or yawing movement of the holder, as seen in FIG. 2, for example. The force exerted on a holder by the spring resists movement serving to exercise and develop the lower leg muscles. Another spring 90 extends between an aperture 92 formed in the second plate 66 of hinge 60 and a bracket 94 secured to wall 30. This is best seen in FIG. 3. Spring 90 provides an increasing force or resistance to movement of the foot holder 14 in a vertical plane about pitch axis 50. Spring 90 also is preferably a coil spring. The resistance to movement exerted on the box by the springs 82, 90 exercises the lower leg muscle as the foot is moved about the multi-axis joint 16. The force which the foot must oppose is easily and readily changed merely by substitution of springs having greater or lower spring rates. The springs 82, 90 bias the foot holder 14 to an initial or at rest position, which is illustrated in FIG. 1. The restoring force increases in a generally linear fashion as a function of distance of movement of the holder 14 from the initial position. In use, the apparatus 10 will be placed on the floor or any suitable level surface. The box or foot holder 14 is held in a generally vertical or perpendicular orientation by the springs 82, 90 and by the hinge means or joint 16. The user assumes a seated position in front of the holder 14 and inserts his foot into the holder as shown in FIG. 1. The lower leg muscles are exercised and developed by flexion and extension of the foot and by rotation of the lower leg. Compound motion is obtained by the multi-axis joint 16. Movement of the holder 14 by the user creates a dynamic load on the ankle and leg muscles. The holder can be rotated as far as possible by the user and then held in the rotated position for a suitable period of time, five to ten seconds, for example. When holding the box, a static load is placed on the muscles and the benefits of isometric exercise are obtained. The apparatus, by permitting lateral or side-to-side movement of the foot and vertical movement about the pitch axis, simulates the forces exerted on the leg during ski boot/binding release or when the ski is rotated during turning. Lateral movement and vertical movement can be performed independently or done together in a compound motion. Some ski bindings permit simultaneous toe and heel release. Also, some bindings allow side-to-side motion of both the toe and heel. The present invention is capable of simulating the loads of all of these bindings. An alternative embodiment of an apparatus in accordance with the present invention is illustrated in FIG. 4 and generally designated 10'. Embodiment 10' similarly includes a base 112 having an upper surface 114. Secured to the base 112 is a lower, generally cylindrical, cup-shaped spring retainer 116. Spring retainer 116 includes a base or bottom wall 118 and a peripheral skirt 120. Supported above retainer 116 is the foot holder or foot retaining means 14. In embodiment 10', foot retaining means 14 is secured by suitable fasteners 122 extending through end wall 36 and to an upper spring retainer 126. Upper spring retainer is superimposed on lower spring retainer 116. Positioned between the spring retainers and supporting foot holer 14 is a joint structure 128. Joint structure 128 includes a rod-like lower member 130 having an elongated, generally cylindrical rod-like portion 132 which is secured at a lower end 134 to the lower spring retainer 116 and hence the base 112. An upper end 136 of member 130 defines a concave, socket-like member 138. Joint 128 further includes another rod-like member 140 having an elongated portion 142 secured at its upper end to the upper spring retainer 126. A lower end 144 of member 140 defines a ball element 146 having a spherical bearing surface 148. Ball element 146 is snapped within socket portion 136 and held thereby. Joint 128 permits multi-axis movement of foot holder 14 in a semihemispherical plane. Resistance to movement is accomplished by a coil spring 150, schematically shown in FIG. 4. Coil spring 150 is preferably in compression and is held between upper retainer 126 and lower retainer 116 by joint 128. Spring 150 is dimensioned so as to be held in place by the peripheral skirt 120 of retainer 116 and peripheral skirt 120 of upper retainer 126. The longitudinal axis of member 130 is coincident with the longitudinal axis of spring 150. The operation of the embodiment illustrated in FIG. 4 is essentially the same as that of the FIG. 1 embodiment. The user places his or her foot within the foot holder 14 which is secured to the upper retainer 126. The foot may now be moved in almost any direction with the heel pivoting or rotating approximately about the ball and socket joint 128. The foot may be moved in a lateral or side-to-side motion in a vertical plane or in any one of a number of circular motions. Resistance, dynamic and static loading of the leg muscles are accomplished by the compression spring 150. A device in accordance with either of the preferred embodiments of the present invention allows the lower leg muscles to be stressed, exercised and developed in the same manner that they are stressed during a ski boot/binding release or attempted release. The muscles are exercised as they would during during normal skiing. The invention permits development to achieve increased proficiency and quick and controlled foot-ski rotation. Although developed primarily to assist a skier in increasing lower leg strength, the device in accordance with the present invention could be used by any athlete involved in an activity requiring lower leg strength. The present invention, therefore, provides for the exercise and strengthening of the lower leg in both dynamic and static modes and is useful in preventing injury and increasing proficiency in a variety of athletic endeavors. In view of the foregoing description, those of ordinary skill in the art will undoubtedly envision various modifications which would not depart from the inventive concepts disclosed herein. For example, instead of a single compression, coil spring 150 in the FIG. 4 embodiment, a plurality of smaller diameter springs could be arranged in a circular array and compressed between the upper and lower spring retainers. Further, it is believed that a joint other than the ball and socket joint or the double hinge joint structure illustrated could be used. The primary consideration is that multi-axis or compound movement of the foot holder be provided. Therefore, it is expressly intended that the above description should be considered as that of the preferred embodiment. The true spirit and scope of the present invention may be determined by reference to the appended claims.
An apparatus for developing the lower leg muscles used while skiing includes a base and a foot holder. A joint interconnects the foot holder with the base and permits multi-axis, compound motion of the holder. A flexible force applying member engages the foot holder substantially at the terminal free end of the foot holder opposite the heel receiving portion to bias the holder to the initial position which is generally vertical with respect to the base and to oppose movement of the holder from an initial position.
0
CROSS-REFERENCE TO RELATED APPLICATION [0001] This application is a continuation-in-part of U.S. nonprovisional patent application Ser. No. 12/576,035 filed on Oct. 8, 2009, which is a continuation-in-part application of U.S. nonprovisional patent application Ser. No. 12/120,765 filed on May 15, 2008, which claims the priority of U.S. provisional patent application Ser. No. 60/942,122 filed on Jun. 5, 2007. FIELD OF THE INVENTION [0002] This invention relates to nutritional supplements. More particularly, the invention relates to compositions and methods for supplementing the diet for improving health and preventing disease. BACKGROUND [0003] Chronically elevated blood levels of cholesterol lead to cardiovascular disease as the cholesterol finds its way into the walls of blood vessels and damages them. This ultimately results in symptoms of chronic arterial insufficiency such as angina and claudication on the one hand, and acute vascular insufficiency, such as heart attack and stroke on the other. [0004] Over $120 billion dollars is spent on direct and indirect costs associated with cardiovascular disease annually in the United States alone. Cardiovascular disease incidence increases with serum LDL cholesterol in a log linear fashion and more importantly declines with treatment-induced reduction of serum LDL cholesterol. [0005] Conventional therapy for elevated blood cholesterol levels takes the form of four classes of FDA approved medications: statins, bioresins, fibrates, and niacin. [0006] Of these, statins are the most widely used with greater than $20 billion in annual sales; however, all the classes, including statins, have side effects and at higher doses, that are necessary to achieve targets, result in side effects that limit their utility. This is especially so of niacin and statins. [0007] Recently, it has been appreciated that in attempting to lower cholesterol, two or more drugs with different mechanisms of action can lower toxicity and produce synergy in the cholesterol lowering effect. Vytorin, a recently introduced combination of Zetia and Simvastatin, has been shown to decrease cholesterol absorption and synthesis and reduce cholesterol better than the sum of the expected reduction of either drug alone. This is explained by a phenomenon I refer to as “escape homeostasis.” When one pathway to cholesterol elevation is blocked, an alternative pathway is often enhanced by the body, so that the overall cholesterol levels are maintained. There is, thus, a built-in or automatic drug resistance that can only be overcome with multiple active agents working simultaneous at different sites. It is noteworthy that evidence exists that even homeopathic, previously felt sub-therapeutic amounts of biologically active cholesterol lowering compounds can exert powerful efficacy with minimal side effects when combined with other agents that work by alternative pathways. SUMMARY [0008] The invention is based on the development of a cholesterol lowering nutritional supplement that utilizes multiple mechanisms and sites of action to reduce cholesterol and also has ingredients that reduce toxicity, increase the rate of metabolism both on a general and a cellular level and, finally stimulate compliance by causing a sense of mild euphoria and well-being, as well as enhancing metabolism. [0009] Accordingly, in one aspect, the invention features a nutritional supplement that includes at least two active ingredients selected from among the following: niacin, a phytosterol component, red yeast rice, coenzyme Q10, L-carnitine, and ascorbic acid. [0010] In another aspect, the invention can feature the nutritional supplement further including water, juice, or juice concentrate. [0011] In another aspect, the invention can feature the nutritional supplement prepared as a baked good, a concentrate, or a powder. [0012] In another aspect, the invention can feature each serving of the nutritional supplement including about 5 to 100 mg of niacin. [0013] In another aspect, the invention can feature each serving of the nutritional supplement including about 400 to 3,000 mg of the phytosterol component. [0014] In another aspect, the invention can feature each serving of the nutritional supplement including about 300 to 3,000 mg of red yeast rice. [0015] In another aspect, the invention can feature each serving of the nutritional supplement including about 50 to 250 mg of L-carnitine. [0016] In another aspect, the invention can feature each serving of the nutritional supplement including about 300 to 1,200 mg of ascorbic acid. [0017] In another aspect, the invention can feature each serving of the nutritional supplement including about 10 to 200 mg of coenzyme Q10. [0018] In another aspect, the invention can feature each serving of the nutritional supplement including less than about 50 mg of niacin. [0019] In another aspect, the invention can feature the phytosterol component including at least one phytosterol ester. [0020] In another aspect, the invention can feature the nutritional supplement including at least three active ingredients selected from among the following: niacin, a phytosterol component, red yeast rice, coenzyme Q10, L-carnitine, and ascorbic acid. [0021] In another aspect, the invention can feature the nutritional supplement including at least four active ingredients selected from among the following: niacin, a phytosterol component, red yeast rice, coenzyme Q10, L-carnitine, and ascorbic acid. [0022] In another aspect, the invention can feature the nutritional supplement including at least five active ingredients selected from among the following: niacin, a phytosterol component, red yeast rice, coenzyme Q10, L-carnitine, and ascorbic acid. [0023] In another aspect, the invention can feature the nutritional supplement including niacin, a phytosterol component, red yeast rice, coenzyme Q10, L-carnitine, and ascorbic acid. [0024] In another aspect, the invention features the nutritional supplement including malto dextrin. [0025] In another aspect, the invention can feature the nutritional supplement including two daily servings. Each serving can include as ingredients water or juice, about 5 to 50 mg of niacin, about 500 to 1,500 mg of at least one phytosterol ester, about 300 to 1,500 mg of red yeast rice, about 10 to 200 mg of coenzyme Q10, about 50 to 250 mg of L-carnitine, and about 300 to 1,200 mg of ascorbic acid. [0026] In another aspect, the invention can feature two servings of the nutritional supplement being packaged in a container. [0027] The invention also features a method that includes the step of administering to a subject for at least 7 days a nutritional supplement comprising at least two active ingredients selected from among the following: niacin, a phytosterol component, red yeast rice, coenzyme Q10, L-carnitine, and ascorbic acid. [0028] In another aspect, the method can also feature the step of administering the nutritional supplement to the subject twice daily. [0029] In another aspect, the method can also feature the step of preparing the nutritional supplement in a form selected from among a baked good, a concentrate, or a powder. [0030] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. In the case of conflict, the present specification, including definitions will control. DETAILED DESCRIPTION [0031] The invention provides an aqueous composition of ingredients and dietary supplements to yield a cholesterol lowering drink. The composition is typically contained within a two-serving container such as a can or bottle and includes water and a combination of at least two of niacin, a phytosterol component, red yeast rice, coenzyme Q10, L-carnitine, and ascorbic acid in amount effective to reduce serum cholesterol levels in a subject who drinks the composition on a regular basis (e.g., once a day, twice a day, every two days, or every three days). [0032] The active ingredients are preferably included at a concentration effective to reduce a subject's serum cholesterol by at least 10% (e.g., at least 20, 30, 40, or 50%) when included in combination with each other and administered to the subject on a regular basis (e.g., twice a day or once a day for at least 2, 3, 4, 5, 6, 12, or 24 weeks). In an exemplary embodiment, the composition can be administered twice daily to the subject in the form of and as part of a beverage, e.g., as a nutritional drink. [0033] Niacin lowers cholesterol by inhibiting lipoprotein formation or release in the liver. Phytosterols lower cholesterol by competing for absorption in the intestines. Red Yeast Rice is a dietary supplement and coloring agent that has been used in Chinese food and medicines for centuries. It decreases synthesis and absorption of cholesterol, produces red coloration which stimulates appetite, compliance, and metabolism. On a cellular level, L-carnitine and coenzyme Q10 enhance transport of fatty acids to the mitochondria and enhance the burning of fatty acids respectively. L-carnitine can also cause a mild sense of euphoria, a beneficial effect that may result in greater compliances with the preparation containing it. Ascorbic acid changes the constitution of bile to decrease cholesterol absorption and inhibit the HMG-CoA reductase pathway, the rate-limiting step in cholesterol biosynthesis. [0034] In an exemplary embodiment, the phytosterol component can include one or more phytosterol esters. [0035] In one embodiment, the beverage can include 6.9 g of a composition in a 8-ounce container. The beverage can be packaged in a bottle or other container that contains two servings, e.g., two 4-ounce servings in an 8-ounce container. The composition can include the following ingredients in each 4-ounce serving: about 12.5 mg of niacin (niacinamide), about 500 mg of vitamin C (ascorbic acid), about 150 mg of L-carnitine (L-carnitine-L-tartrate), about 25 mg of coenzyme Q10, about 660 mg of phytosterol esters, and q.s. maltodextrin. Servings of the beverage can be consumed twice daily, for example, one serving in the morning and one serving at night. [0036] In another embodiment, the beverage can include 8.2 g of a composition in an 8-ounce container. The beverage can be packaged in a bottle or other container that contains two servings, e.g., two 4-ounce servings in an 8-ounce container. The composition can include the following ingredients in each 4-ounce serving: about 600 mg of red yeast rice powder, about 12.5 mg of niacin (niacinamide), about 500 mg of vitamin C (ascorbic acid), about 150 mg of L-carnitine (L-carnitine-L-tartrate), about 25 mg of coenzyme Q10, about 660 mg of phytosterol esters, and q.s. maltodextrin. Servings of the beverage can be consumed twice daily, for example, one serving in the morning and one serving at night. [0037] Although 4-ounce servings and 8-ounce containers are described herein, the serving size and container size can be different as long as the amounts of each ingredient remain consistent. For example, each serving can be 3.5, 4.5, 5, 6, 7, 7.5, 8.5, 9, 10, 12, 13, 14, or 16 ounces. [0038] Each serving of the composition can include niacin in the amounts of about 4.5, 5, 6, 6.1, 6.5, 6.6, 6.9, 7, 7.5, 8, 9, 9.9, 10, 10.1, 10.5, 11, 11.5, 11.9, 12, 12.1, 12.5, 12.6, 12.9, 13, 15, 19, 20, 25, 30, 40, 50, 60, 70, 75, 80, 90, 99, 100, 101, or 110 mg or more. In exemplary embodiments, each serving of the composition can contain less than about 50 mg of niacin. In one exemplary embodiment, each serving of the composition can contain about 12.5 mg of niacin. [0039] Each serving of the composition can include phytosterol esters in the amounts of about 300, 400, 500, 550, 600, 625, 640, 649, 651, 660, 675, 700, 800, 900, 1,000, 1,250, 1,320, 1,500, 1,800, 1,900, 1,950, 1,999, 2,000, 2,001, 2,050, or 2,100 mg or more. In exemplary embodiments, each serving of the composition can contain about 660 mg of phytosterol esters. [0040] Each serving of the composition can include coenzyme Q in the amounts of about 8, 9, 10, 13, 15, 17, 19, 20, 22.5, 24, 24.5, 24.9, 25, 25.1, 25.5, 26, 27, 27.5, 28, 29, 30, 35, 40, 45, 50, 55, 75, 90, 100, 150, 200, 250, or 300 mg or more. In exemplary embodiments, each serving of the composition can contain about 25 mg of coenzyme Q. [0041] Each serving of the composition can include L-carnitine in the amounts of about 90, 95, 100, 110, 115, 125, 135, 140, 145, 149, 149.1, 149.9, 150, 150.1, 150.5, 151, 153, 155, 160, 170, 175, 180, 190, 200, 250, 300, 400, or 500 mg or more. In exemplary embodiments, each serving of the composition can contain about 75-150 mg of L-carnitine. In one exemplary embodiment, each serving of the composition can contain about 150 mg of L-carnitine. [0042] Each serving of the composition can include ascorbic acid in the amounts of about 50, 100, 200, 250, 300, 400, 450, 475, 490, 499, 499.1, 500, 500.1, 500.5, 501, 510, 520, 535, 550, 600, 625, 640, 649, 651, 660, 675, 700, 800, 900, 1,000, 1,500, or 2,000 mg or more. In exemplary embodiments, each serving of the composition can contain about 500 mg of ascorbic acid. [0043] Each serving of the composition can include red yeast rice in the amounts of about 300, 400, 500, 550, 575, 590, 595, 599, 599.1, 599.9, 600, 600.1, 600.5, 601, 610, 620, 625, 640, 650, 660, 675, 700, 800, 900, 1,000, 1,250, 1,500, 1,800, 1,900, 1,950, 1,999, 2,000, 2,001, 2,050, 2,100, or 2,400 mg or more. In exemplary embodiments, each serving of the composition can contain about 600 mg of red yeast rice. [0044] The composition can also feature maltodextrin making up the remainder of any 6.9 g, 8.2 g, or other amount of the composition premixture before the addition of water to create the beverage. The beverage may also contain artificial or natural flavorings and colorings. EXAMPLE 1 [0045] A beverage for administration twice daily to a human subject can include two servings stored in a container such as, for example, a bottle. Each serving of the beverage can include water (100-500 ml) and 6.9 g of the composition. The composition can include as ingredients phytosterol esters (about 660 mg), niacin (less than about 50 mg), coenzyme Q10 (about 25 mg), ascorbic acid (about 500 mg), L-carnitine (about 75-150 mg), and maltodextrin (q.s.). EXAMPLE 2 [0046] A beverage for administration twice daily can include two servings stored in a container such as, for example, a bottle or can. Each serving of the beverage can include water (about 100 to 500 ml) and 8.2 g of the composition. As ingredients, the composition can feature phytosterol esters (about 660 mg), niacin (less than about 50 mg), red yeast rice (about 600 mg), coenzyme Q10 (about 25 mg), ascorbic acid (about 500 mg), L-carnitine (about 75-150 mg), and maltodextrin (q.s.). [0047] In an exemplary method of the invention, the composition can be administered to a human subject at least twice daily in the form of a beverage or nutritional drink. The two daily doses of the beverage can be contained within a single container such as, for example, a bottle or can. In another embodiment, each serving of the beverage can be packaged in a separate bottle or container. The beverage can be administered twice daily for at least 7 days. The beverage can include water and at least two active ingredients selected from among the following: niacin, a phytosterol component, red yeast rice, coenzyme Q10, L-carnitine, and ascorbic acid. [0048] In another method of the invention, the composition may be administered at an interval different than twice daily, e.g., once, three times, or four times daily. [0049] In still another method of the invention, the composition can be administered to a human subject to reduce the subject's blood cholesterol levels. [0050] The invention can also include a nutritional supplement that can be created as a powder that can be added to food items, as a baked good (e.g., as cookies and brownies), and as a concentrate. The concentrate can be added to water or another ingestible liquid to create a nutritional beverage. Thus, the nutritional supplement can be provided in an ingestible form that can lower cholesterol in human subjects. The nutritional supplement is typically contained within a two-serving container such as a package, box, carton, wrapper, bottle or can. Where the nutritional supplement is prepared in the form of a concentrate that can be added to and mixed with a beverage, a bottle or can be used for packaging the concentrate. The nutritional supplement can include a combination of at least two of niacin, a phytosterol component, red yeast rice, coenzyme Q10, L-carnitine, and ascorbic acid in amounts effective to reduce serum cholesterol levels in a subject who ingest the composition on a regular basis (e.g., once a day, twice a day, every two days, or every three days). The nutritional supplement can also include water. [0051] As with the nutritional beverage, the active ingredients of the nutritional supplement are preferably included at a concentration effective to reduce a subject's serum cholesterol by at least 10% (e.g., at least 20, 30, 40, or 50%) when included in combination with each other and administered to the subject on a regular basis (e.g., twice a day or once a day for at least 2, 3, 4, 5, 6, 12, or 24 weeks). In an exemplary embodiment, the composition can be administered twice daily to the subject in the form of and as part of a powder that can be added to food items, incorporated into a baked good (e.g., as a snack bar, a cookie or a brownie), or as a concentrate mixed with water or another beverage. [0052] In an exemplary embodiment, the phytosterol component can include one or more phyto sterol esters. [0053] In one embodiment, the nutritional supplement can include 6.9 g of a composition in an 8-ounce container. The nutritional supplement can be packaged in a container that contains two servings, e.g., two 4-ounce servings in an 8-ounce container. The composition of this embodiment of the nutritional supplement can include the following ingredients in each 4-ounce serving: about 12.5 mg of niacin (niacinamide), about 500 mg of vitamin C (ascorbic acid), about 150 mg of L-carnitine (L-carnitine-L-tartrate), about 25 mg of coenzyme Q10, about 660 mg of phytosterol esters, and q.s. maltodextrin. Servings of the nutritional supplement can be consumed twice daily, for example, one serving in the morning and one serving at night. [0054] In another embodiment, the nutritional supplement can include 8.2 g of a composition in an 8-ounce container. The beverage can be packaged in a bottle or other container that contains two servings, e.g., two 4-ounce servings in an 8-ounce container. The composition of this embodiment of the nutritional supplement can include the following ingredients in each 4-ounce serving: about 600 mg of red yeast rice powder, about 12.5 mg of niacin (niacinamide), about 500 mg of vitamin C (ascorbic acid), about 150 mg of L-carnitine (L-carnitine-L-tartrate), about 25 mg of coenzyme Q10, about 660 mg of phytosterol esters, and q.s. maltodextrin. Servings of the nutritional supplement can be consumed twice daily, for example, one serving in the morning and one serving at night. [0055] Although 4-ounce servings and 8-ounce containers are described herein, the serving size and container size can be different as long as the amounts of each ingredient remain consistent. For example, each serving can be 3.5, 4.5, 5, 6, 7, 7.5, 8.5, 9, 10, 12, 13, 14, or 16 ounces. [0056] Each serving of the nutritional supplement can include niacin in the amounts of about 4.5, 5, 6, 6.1, 6.5, 6.6, 6.9, 7, 7.5, 8, 9, 9.9, 10, 10.1, 10.5, 11, 11.5, 11.9, 12, 12.1, 12.5, 12.6, 12.9, 13, 15, 19, 20, 25, 30, 40, 50, 60, 70, 75, 80, 90, 99, 100, 101, or 110 mg or more. In exemplary embodiments, each serving of the nutritional supplement can contain less than about 50 mg of niacin. In one exemplary embodiment, each serving of the nutritional supplement can contain about 12.5 mg of niacin. [0057] Each serving of the nutritional supplement can include phytosterol esters in the amounts of about 300, 400, 500, 550, 600, 625, 640, 649, 651, 660, 675, 700, 800, 900, 1,000, 1,250, 1,320, 1,500, 1,800, 1,900, 1,950, 1,999, 2,000, 2,001, 2,050, or 2,100 mg or more. In exemplary embodiments, each serving of the nutritional supplement can contain about 660 mg of phytosterol esters. [0058] Each serving of the nutritional supplement can include coenzyme Q in the amounts of about 8, 9, 10, 13, 15, 17, 19, 20, 22.5, 24, 24.5, 24.9, 25, 25.1, 25.5, 26, 27, 27.5, 28, 29, 30, 35, 40, 45, 50, 55, 75, 90, 100, 150, 200, 250, or 300 mg or more. In exemplary embodiments, each serving of the nutritional supplement can contain about 25 mg of coenzyme Q. [0059] Each serving of the nutritional supplement can include L-carnitine in the amounts of about 90, 95, 100, 110, 115, 125, 135, 140, 145, 149, 149.1, 149.9, 150, 150.1, 150.5, 151, 153, 155, 160, 170, 175, 180, 190, 200, 250, 300, 400, or 500 mg or more. In exemplary embodiments, each serving of the nutritional supplement can contain about 75-150 mg of L-carnitine. In one exemplary embodiment, each serving of the nutritional supplement can contain about 150 mg of L-carnitine. [0060] Each serving of the nutritional supplement can include ascorbic acid in the amounts of about 50, 100, 200, 250, 300, 400, 450, 475, 490, 499, 499.1, 500, 500.1, 500.5, 501, 510, 520, 535, 550, 600, 625, 640, 649, 651, 660, 675, 700, 800, 900, 1,000, 1,500, or 2,000 mg or more. In exemplary embodiments, each serving of the nutritional supplement can contain about 500 mg of ascorbic acid. [0061] Each serving of the nutritional supplement can include red yeast rice in the amounts of about 300, 400, 500, 550, 575, 590, 595, 599, 599.1, 599.9, 600, 600.1, 600.5, 601, 610, 620, 625, 640, 650, 660, 675, 700, 800, 900, 1,000, 1,250, 1,500, 1,800, 1,900, 1,950, 1,999, 2,000, 2,001, 2,050, 2,100, or 2,400 mg or more. In exemplary embodiments, each serving of the nutritional supplement can contain about 600 mg of red yeast rice. [0062] The nutritional supplement can also feature maltodextrin making up the remainder of any 6.9 g, 8.2 g, or other amount of the nutritional supplement premixture before the addition of water or other food ingredients. The nutritional supplement may also contain artificial or natural flavorings and colorings. [0063] The invention can also include a method in which the composition can be administered to a human subject at least twice daily in the form of a nutritional supplement. The nutritional supplement can be created as a solid such as, for example, a powder that can be added to food items or as a baked good (e.g., as cookies and brownies). The method can also include the nutritional supplement being a concentrate that can be added to water or another ingestible liquid to create a nutritional beverage. The two daily doses of the nutritional supplement can be contained within a single container such as, for example, a package, box, carton, wrapper, bottle or can. In another embodiment, each serving of the nutritional supplement can be packaged in a separate bottle or container. The nutritional supplement can be administered twice daily for at least 7 days. The nutritional supplement can include at least two active ingredients selected from among the following: niacin, a phytosterol component, red yeast rice, coenzyme Q10, L-carnitine, and ascorbic acid. [0064] In another method of the invention, the nutritional supplement composition may be administered at an interval different than twice daily, e.g., once, three times, or four times daily. For example, the nutritional supplement can be ingested by the human subject in the form of a cookie, brownie, or snack bar. In another example, the nutritional supplement can be provided in the form of a powder, which can be mixed in or sprinkled onto other food items and ingested by the human subject. In still another example, the nutritional supplement can be provided in the form of a concentrate that can be mixed with a beverage selected by the human subject and then imbibed by the human subject. [0065] In still another method of the invention, the composition can be administered to a human subject in the nutritional supplement to reduce the subject's blood cholesterol levels. OTHER EMBODIMENTS [0066] It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims.
A nutritional supplement specifically designed to lower cholesterol that addresses multiple mechanisms including hepatic synthesis and release, intestinal absorption of cholesterol, while, at the same time, including ingredients that mitigate the side effects of the constituents and increase their efficacy by affecting emotional factors that influence compliance such as a sense of well-being and euphoria on the one hand, or an increased overall metabolism and desire for the product stemming from its coloration on the other hand. The nutritional supplement can be prepared as a powder that can be added to a food item by a human subject, a concentrate that can be mixed with water or another beverage, or incorporated into a baked good for ingestion by the human subject.
0
FIELD OF THE INVENTION [0001] This invention relates generally to a pair of pants in which the seat is modified to allow insertion of cushioning means positioned to provide cushioned comfort for the seated derriere of a wearer of the slacks. The term “pants” is used to define a pair of trousers, whether “long” trousers or “shorts”, such as is commonly used as an outer garment by either men or women in everyday usage. THE PROBLEM [0002] In the particular instance where the pants are to be worn to a sporting event such as a game or race, or other event such as a concert or festive rally, to be held in an arena such as a stadium in which the wearer is to sit on a hard seat, whether a bench or chair, for an extended period, there is a need for a pair of pants, usually worn as an outer garment, which can be worn, as if they were merely fashionably patched, but not modified for any other purpose than being worn as patched pants. Thus, the wearer may wear the pants, as he would any other pair of patched pants, then, modify the pants and go to an arena to watch an event. The pants may be modified while being worn. After having been modified, the wearer will be seated comfortably on a hard surface because the area under the wearer's hip bone is protected with cushioning means. BACKGROUND OF INVENTION [0003] Pants of all kinds have been modified to provide their wearer with protection. Protection of various parts of the lower body is afforded in specialty pants used for sports such as ice hockey, American football, ice fishing, and the like. Such clothing, and such pants in particular, would attract undue attention if worn in every day use. The invention disclosed herein is narrowly directed to a dual purpose pair of pants which can be worn during the course of a wearer's day or night, as routinely worn by the wearer, then modified by him/her to watch an event, whether a festive celebration, a game or a race, in comfort. [0004] It is found that the weight of a seated human body is supported mainly by the hip bone, and more particularly by the lower tuberosities of the left and right ischiums of the hip bone. Since the pants are narrowly directed to providing a modicum of comfort when seated on a hard surface there is no reason to provide cushioning for more area under a wearer's derriere than the area under the left and right ischiums which typically support at least 75% if not essentially the weight of the wearer. [0005] It is well known (and documented in U.S. Pat. No. 5,365,610) that if a protective pad is merely inserted into a pocket having a configuration similar to that of the pocket without the pad being sewn or otherwise attached to the pocket or the garment, the pad often has a tendency to wad and fold up within the pocket as the pocket and pad are subjected to movement and stresses imposed upon the garment during sporting activities. [0006] There can be little argument about the effectiveness of pants padded as disclosed in U.S. Pat. No. 6,874,168, to provide seated comfort, but the padding extends partially through the thigh area, being deliberately oversized. In contrast, the pads in the invention disclosed herein, are most preferably deliberately minimally sized so as to protect only the limited area under the ischiums of the wearer, are not placed in use until required, and when so placed attract no undue attention with respect to the pants being in any way different, except for a pair of vertical lines, from conventional pants. [0007] Though the prior art discloses pouches in which a protective pad may be inserted, a panel forming a non-pleated pouch, as shown in U.S. Pat. No. 5,365,610, is clearly visible and noticeable as it loosely overlies the pants when the pad is not inserted. Moreover, prior art padded pants have been modified in such a manner that they are obviously designed and constructed for the specified purpose. They cannot be used for everyday wear without attracting undue attention. SUMMARY OF THE INVENTION [0008] A pair of pants is provided with generally rectangular panels mimicking a fashionably patched pants' seat, except for a vertical line centrally disposed in each panel evidencing the presence of a hidden box pleat. Each panel is symmetrically disposed in spaced-apart mirror-image relationship with the centerline of the pants' seat and secured thereto to form expansible pouches with defined openings, each opening distally disposed relative to the vertical center line of its pouch so as to be openable and closeable in those locations only. Maximum expansibility at the center of a pouch is no more than 5.08 cm (2″). [0009] The pants are uniquely adapted to accommodate a pair of removably insertable cushioning means in pouches provided in the seat of the pants. [0010] The pouches are provided with the specific purpose of not altering or interfering with the normal or usual shape of the user's buttocks or rear end in any manner whatsoever, until the user is about to be seated on a hard seating surface to watch an event. Except for a pair of oppositely disposed spaced apart vertical lines, each left by a disappearing box pleat, the pants appear to be a conventional pair of pants. A box pleat in the panel is found unexpectedly to hide the underlying pouch, at the same time providing an expandable panel without which a pouch could not accommodate a protective pad. [0011] A pair of pants is provided with a single pair of critically positioned pleated pouches, each disposed in mirror image relationship about the center seam (or centerline) of the pants, and in laterally spaced apart relationship with the center seam. The positioning of each pouch is most preferably determined by the location of each ischium of the wearer, and more specifically, the lower tuberosity of each ischium which is the lower posterior portion of the hip bone on which the body rests when sitting. [0012] Each pouch is formed with a panel of non-stretchable fabric which is visually matched to the fabric of the pants so as to be unobtrusive. By “non-stretchable” is meant that the fabric is not stretched noticeably when pulled upon by human hands. The choice of non-stretchable fabric is based on the finding that a stretchable fabric is unsuited for ready insertion and removal of a pad while the wearer is wearing the pants. Moreover, stretchable pants are not typically fashionably patched in the seat. [0013] Each panel is uniquely shaped for its intended purpose, and secured along its edges by being sewn or stitched to the fabric to form a pouch in a particular manner so as not to be visually obtrusive when the wearer does not have pads inserted; and yet sewn to accommodate a pad snugly though it may be readily inserted and removed. [0014] It is critical that each panel be provided with at least one box pleat, preferably only one, so that the pouch formed between the seat fabric and the overlying panel, may have an ischium-cushioning means removably inserted into it. The ischium-cushioning means, may be an elastomeric synthetic resinous foam, a bubble-wrap or an inflated pillow, each of which, singly or collectively, for ease and convenience, are referred to hereinafter as a “pad”. Each pad is removably insertable into each pouch, by lifting its overlying panel which is openable and closeable, most preferably along a portion of each of two adjacent edges of a panel, so that, when open, only the outer upper corner of the panel is raised to open the pouch sufficiently to allow insertion and removal of the pad while the pants are being worn. [0015] A vertical box pleat in the midportion of each panel is a critical feature of the pouch because it provides the panel of the pouch with requisite expansibility to accommodate a pad snugly and immovably after the pad is inserted in the pouch. The vertical line formed by adjacent edges of the two back-to-back knife-edge pleats which form the box pleat, effectively negates any visually discernible effect on shaping the contour of the wearer's derriere, yet unexpectedly and effectively hides the presence of each pouch under an unobtrusive vertical line on the seat of the pants. [0016] A pouch is critically dimensioned so as to hold a pad in the range from about 12.7 mm (0.5″) to 5.08 cm (2″) thick, and an area in the range from about 103.23 cm 2 (16 in 2 ) to 709.7 cm 2 (110 in 2 ), depending upon the size of the pants. The dimensions of the pouch are determined by those of the pad it is to hold, the location and dimensions of which pad are determined by the size of the wearer for whom the pants are made. [0017] It is essential that each of the two pouches be openable and closeable in such a manner as to enable the wearer readily to open and close them, to insert and remove a pad, while the wearer is wearing the pants. BRIEF DESCRIPTION OF THE DRAWING [0018] The foregoing and additional objects and advantages of the invention will best be understood by reference to the following detailed description, accompanied with schematic illustrations of preferred embodiments of the invention, in which illustrations like reference numerals refer to like elements, and in which: [0019] FIG. 1 is a perspective view illustrating the pads placed in pouches on the seat of the trousers, which pouches will lie directly beneath the left and right ischiums of the wearer when he/she is seated, without protecting any other portion of the wearer's derriere, and so as to fail to support the wearer's thighs and lower back; [0020] FIG. 2 is a plan view of the right seat portion of the pants which have been pulled apart from both sides to allow the pants to be spread flat so as to show a pouch positioned to protect only that portion of the derriere which will directly overlie the pouch when the wearer is seated, and protect no other portion of the derriere or thigh. The upper outer corner of the pouch is openable for insertion of a pad, and the corner is closeable with mating hook and loop fasteners. [0021] FIG. 3 is a cross-sectional view, along the line 3 - 3 , of the box pleat. [0022] FIG. 4 is a detail of a pouch in a view analogous to that shown in FIG. 3 above, except that the pouch is secured along the entire length of the upper, lower and interior edges, leaving only an outer edge which may be raised to insert a pad. A small portion, in the range from 1% to 10% of the length of the outer edge, near its upper and lower portions, is sewn to the fabric of the seat to provide strength at each corner. [0023] FIG. 5 is a perspective view of a rectangular parallelepiped of synthetic resinous foam having a thickness of from about 2.54 cm (1″) but no more than 5.08 cm (1″). [0024] FIG. 6 is a perspective view of a pad which has angulated sides, each having a short vertical height then being inclined to meet the pad's upper surface. [0025] FIG. 7 is a perspective view of a pad which is a frustum of a pyramid, also referred to as a truncated pyramid. [0026] FIG. 8 is a perspective view of a pad which is a frustum of a cone. [0027] FIG. 9 is a perspective view of a pad which is an inflatable valved pad formed from ribbed laminar sheets less than 50.8 μm (2 mils or 0.002″) thick, of a synthetic resin which is essentially impermeable to air. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS [0028] The problem referred to above is best addressed by scaling a pair of pouches adapted to snugly accommodate pads scaled to the derriere of the wearer. The larger the pants, the larger the pouches and the pads. It will be recognized that pants for a relatively small wearer may be provided with pouches which are far too large snugly to accommodate small pads sufficient to cushion the relatively small derriere of the wearer, but the resulting effect would be visually displeasing. [0029] It will also be recognized that a pouch dimensioned to hold a contoured pad of relatively soft, that is, readily compressible foam, having a maximum thickness of 5.08 cm at its center, will also readily hold a rectangular parallelepiped of firmer plastic foam or bubble wrap no thicker than 2.54 cm and still provide adequate seating comfort, because the foam or bubble-wrap is less compressible than the softer foam. [0030] The term “foam” is used in its broader sense to refer to a compressible material of synthetic resin (“plastic”), or of natural rubber or other material such as a sponge, whether open cell with interconnected pores, or closed cell with air trapped in cells which are not interconnected. Since “bubble wrap” is air trapped in bubbles, it is also broadly referred to herein as a “foam”. [0031] By “contoured pad” is meant a pad, symmetric or asymmetric about one or more axial planes, shaped generally to be readily insertable into a pouch. Such a shape is conveniently a truncated pyramid or cone which provides an upper surface having an area smaller than its lower surface, and each (pyramid or cone) may have a base portion with vertical walls extending a short distance before inclining to form the sides, the base portion providing the edges of the pad with requisite durability while they are inserted and removed from a pouch. The sides of the pyramid may be different in area, one from another, and the cone may be asymmetrical, having one portion thinner than the other, the thinner portion being inserted into the pouch first. [0032] Referring to FIGS. 1 and 2 there is illustrated a perspective view of a pair of pants, referred to generally by reference numeral 10 , which are provided with a pair of pouches formed by panels 20 and 20 ′ symmetrically disposed about the rear centerline C and rear center seam (only the upper portion is visible) of the seat of the pants. Each panel, preferably formed of the same fabric as the pants' so as to visually blend therewith, is provided with a vertical box pleat 30 and 30 ′ respectively which allows the pouch to be expanded to accommodate a protective pad. Though an additional vertical box pleat may be provided in the panel of each pouch, so as to more easily accommodate the pad, the cost of providing an additional box pleat cannot be justified as it does not produce a benefit corresponding to the cost. A single vertical box pleat in each panel functions as well as two parallel vertical box pleats for the maximum thickness of the pad held in the pouch. [0033] Each upper, lower and outer edge of the panel is generally linear and the three edges are approximately rectangularly disposed relative to each other. [0034] For the least obtrusive visual effect, and to mimic a pair of conventionally patched pants, a panel 20 is sewn, with suitable thread 35 , to the fabric of the seat along the entire length of the panel's lower edge 22 ; and also along the entire length of inner vertical edge 23 adjacent the rear center line C of the pants. Most preferably, the line of the edge 23 corresponds to line of the center seam of the seat of the pants, so as to provide visual compatibility of edge and seam. In addition to the sewn inner 23 and lower 22 edges , either the entire length of the upper edge 21 , or, the entire length of the outer vertical edge 24 of the panel, but not both, may be sewn to the fabric of the seat so that the side of the pouch not sewn shut, is left open for insertion of a pad. [0035] Each panel 20 and 20 ′ of each pouch is thus positioned so that its upper edge 21 and 21 ′ respectively, are essentially parallel to the upper edges of hip pockets 29 and 29 ′ so as to present a pleasing visual effect. Lower edges 22 and 22 ′ are likewise essentially parallel to the upper edges 21 and 21 ′ respectively, and to the upper edges of hip pockets 29 and 29 ′ so that each pouch is positioned on each cheek of the derriere but fails to extend over the upper portion of each thigh. [0036] In this configuration of a pouch, a pad may be inserted from above, or from the side, depending which edge 21 or 24 is sewn shut, or partially shut, while a wearer is wearing the pants. [0037] Preferably, a portion, most preferably, a minor portion of the length of the upper edge 21 of the panel, and, a minor portion of the adjacent length of the outer vertical edge 24 , are both left open so as to form a pouch with an openable and closeable corner 26 . The dimensions of each panel are scaled to the size of the pants. The dimensions of each pad are necessarily deliberately restricted so as to correspond to an area not more than about 50% larger than the area of the derriere directly beneath the lower surfaces of the tuberosity of the respective left or right ischium, so that neither pad provides padded protection for any portion of the wearer's thigh, and no protection for the area of the derriere between the pouches. [0038] The area under the ischiums of a seated wearer is best measured by noting the laterally spaced apart distance between indentations on a compressible foam pad, and the area of each indentation. A pad for the area of the indentation is then at least 10% but no more than 50% larger than the area of the indentation; preferably the pad is in the range from 10% to 25% larger than the area of the indentation. [0039] Referring particularly to FIG. 2 there is shown a portion of the seat of the pants in which a pouch is formed by a panel 20 having a box pleat 30 . The shape of the panel is generally rectangular, but is preferably provided with its inner edge 23 corresponding in curvature to the adjacent center seam C of the seat of the pants, so that the edge may be arcuate, or the edge may be angulated to present a shape which is approximately trapezoidal. The panel 20 is sewn with thread 35 to the fabric of the seat along the entire length of the panel's lower and inner edges 22 and 23 respectively. Though inner edge 23 may appear angulated, so as to provide an obtuse angle greater than 135° formed by intersecting upper and lower lines, edge 23 is preferably an arcuate edge, as shown by smoothly arcuate dotted line 23 ′. Whatever the precise geometry of the center seam C, for a pleasing visual appearance, the curve of inner vertical edge 23 preferably corresponds to and is in parallel spaced-apart relationship with, the rear center seam of the seat of the pants. [0040] In addition, the upper edge 21 is sewn to a location just past the vertical line of the box pleat 30 so that the upper end of the box pleat is anchored to the fabric of the seat; and, outer edge 24 is sewn for a portion of its vertical length, preferably a major portion of its vertical length, to a location just past the horizontal center line H of the panel 20 . Thus, most preferably, a minor portion of the length of the upper edge 21 of the panel 20 , and, a minor portion of the adjacent length of the outer vertical edge 24 , are not sewn to the fabric of the seat, leaving the upper corner 26 to be opened for insertion of a pad. [0041] For easy opening and closing of the pouch formed by panel 20 , at least a portion of the unsewn, that is, unsecured to the fabric of the seat, portion of the upper edge 21 , and at least a portion of the unsewn portion of the outer vertical edge 24 are each provided with one mating part 27 of a Velcro mating hook and loop fastener, the other mating part 27 ′ (not shown) being secured to the fabric of the seat. [0042] Referring to FIG. 3 , there is shown a cross-section of the box pleat formed by two back-to-back knife-edge pleats 31 and 32 with a common base 33 . A box pleat with a base of 5.08 cm (2″), the pleat formed in a panel of a pair of pants for a large adult male, allows insertion and removal of a pad up to 5.08 cm (2″) thick at its center. In a pouch having maximum dimensions for a relatively large human, the width of the base of the box pleat is no more than about 5.08 cm (2″), and the minimum width for a child or relatively small adult human is about 1.9 cm (0.75″). [0043] Referring to FIG. 4 there is shown a detail of a portion of the seat of the pants in which a pouch is formed by a panel 40 having a box pleat 30 . The panel is sewn with thread 35 to the fabric of the seat at the panel's upper, lower and inner edges 41 , 42 and 43 respectively, and as before, inner edge 43 may be arcuate to correspond to the center seam C. A small portion, in the range from 1% to 10% of the length of the outer vertical edge 44 , near its upper portion, is also sewn, with thread 35 , to the fabric of the seat; and, analogously, a small portion, in the range from 1% to 10% of the length of the outer vertical edge 44 , near its lower portion, is sewn to the fabric of the seat, so that the opening of the pouch formed, is provided with strength at both, the upper outer, and the lower outer corners of the pouch. Thus, the opening formed, and left open for insertion and removal of a pad, is at least 80% of the vertical length of the outer edge 44 . [0044] For easy opening and closing of the pouch formed by panel 40 , at least a portion of the unsewn portion of the outer vertical edge 44 is provided with one mating part 28 of a Velcro mating hook and loop fastener, the other mating part 28 ′ (not shown) being secured to the fabric of the seat. [0045] As shown in FIGS. 1 , 2 and 4 each panel is generally rectangular in which the inner edge is generally arcuate, whether smoothly arcuate or obtusely angulated, and generally parallel to the rear center seam of the pants, while the other three sides are the sides of a rectangle. The panel most preferably has a single vertical box pleat to minimize the obtrusiveness of a vertical line through the mimicked patch. [0046] Referring to FIG. 5 there is shown a rectangular parallelepiped of synthetic resinous, relatively difficultly compressible foam 50 having a thickness of from about 1.27 cm (0.5″) but no more than 5.08 cm (1″). A suitable foam for the purpose, preferably of a homogeneous closed cell or open cell foam of an elastomer is commonly referred to as a “foam rubber pad”. It is exemplified by a synthetic resinous material having a hardness in the range from about Shore OO 15-95 (ASTM D-2240), and having a resilience measured as compressive pressure required to make an indentation 25% of the thickness of the pad, the pressure being in the range from 6.89-344.5 KPa (1-50 psi). Particularly suitable foams are exemplified by those having a negative Poisson's ratio and used for seat cushion material. Such foams are disclosed in “Negative Poisson's Ratio Foam as Seat Cushion Material” by A. Lowe and R. S. Lake, Cellular Polymers, 19, 157-167, July 2000, which is incorporated herein by reference. Another suitable foam is Evalite ethylene vinyl acetate foam having a density of 32 Kg/cu meter (2 lb/cu ft) and requiring 34.5 KPa (5 psi) for 25% deflection. Other suitable pads may be made from “Ultimate” rebound polyurethane foam (from Leggett & Platt Inc.); Poron cellular polyurethane foam (from Rogers Corporation); and, white melamine foam having a density of 11.2 kg/cu meter (0.7 lb/cu ft) having a resilience measured as requiring 12 KPa (1.74 psi) to provide compression of 25% (also referred to as a 25% deflection). [0047] Referring to FIG. 6 there is shown a contoured pad 60 the lower portion 61 of which is rectangular, providing short vertical distances in the range from 1.59 mm (0.0625″) to 6.35 mm (0.25″), while the upper portion 62 has angulated sides so that the upper portion is the frustum of a pyramid. The short vertical distance of the lower portion 61 is less than 50%, preferably less than 20% of the overall thickness of the pad which is typically in the range from 12.5 mm (0.5″) to 3.2 cm (1.25″). Each short vertical distance, at its top, is upwardly inclined at an angle in the range from about 10°-80°, to meet the pad's upper surface, the inclination, preferably in the range from about 40°-65°, depending upon the compressibility of the foam and the thickness of the desired pad. A suitable foam for a pad 60 having what is commonly referred to as “graded compressibility” is of the type used in seats of automobiles and sofas and in pillows and mattresses. A preferred such foam in a pad is initially more readily compressible than after it is compressed to make an indentation 25% of the thickness of the pad. Such a foam is exemplified by foam supplied by Carpenter Foam Products of Elkart Ind. and is similar to Tempur® foam used in Tempur-Pedic® pressure relieving Swedish mattresses and pillows. [0048] If desired, in lieu of the contoured pad of FIG. 6 of suitable foam, one may use a combination of separate pads, one a rectangular parallelepiped pad, the other a truncated pyramid positioned on the rectangular pad. [0049] FIG. 7 is a perspective view of a pad 70 which is a frustum of a pyramid made of relatively compressible foam such as is used in the embodiment shown in FIG. 6 . [0050] FIG. 8 is a perspective view of a readily insertable pad 80 which shaped as a frustum of a cone made of relatively compressible foam such as is used in the embodiment shown in FIG. 6 . The sides of the frustoconical pad are inclined at an angle in the range from about 10°-80°, preferably in the range from about 40°-65°, to meet the pad's upper surface 81 , the inclination, depending upon the compressibility of the foam and the thickness of the desired pad. The lower surface 82 is sized to be slidably inserted and removed from a pouch. [0051] FIG. 9 is a perspective view of an inflatable pad 90 which may be inserted in a deflated condition, into the pouch formed by a panel 20 or 40 . The pad is provided with a conventional self-sealing air valve 91 such as is disclosed in U.S. Pat. No. 4,080,751 and well-known in numerous inflatable articles. After the pad 90 is inserted in the pouch, and prior to the wearer of the pants being seated, the pad 90 is inflated by attaching one end 92 of a tube over the valve 91 , the other end (not shown) being placed in the wearer's mouth to inflate the pad. The pad is shown, only slightly inflated, to illustrate that it is preferably formed from an extruded envelope 93 with at least one of its opposed sides 94 , 95 , preferably both, provided with one or more ribs 96 . The ribs 96 allow the pad to form, when inflated to the pressure desired, a generally rectangular pad (instead of an ellipsoid) to support the derriere of the wearer of the pants.
A pair of pants is modified to mimic a pair of fashionably patched pants except that the “patches” are panels which forms pouches on the seat of the pants. Each panel is provided with a vertical box pleat which allows the pouch, formed by securing the panel to the fabric of the seat, to be expanded sufficiently to hold a cushioning means located directly beneath the lower tuberosity of each ischium of the wearer. The cushioning means is typically a pad of chosen compressibility which can be inserted and removed from its pouch by the wearer while the pants are being worn. The protective pads are effective to provide cushioning for only the area under each ischium and not for any portion of the thighs or lower back.
0
CROSS-REFERENCES TO RELATED APPLICATIONS [0001] Not Applicable. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH [0002] Not Applicable. BACKGROUND OF THE INVENTION [0003] 1. Field of the Invention [0004] This invention relates to a combination suction retraction instrument for surgery. [0005] 2. Description of the Related Art [0006] When oral surgery is being performed in a patient's mouth, it is necessary that the working area of the mouth be kept free of fluids and debris. These fluids may include saliva, blood, liquid used with drilling, and/or rinsing liquids, and the debris may be drilling dust and/or broken pieces of teeth. It is important for the patient's comfort to keep fluids from accumulating in the patient's mouth so that the fluids and debris are not swallowed and the patient can, if necessary, breath through his or her mouth. [0007] Suction devices are used to keep the oral surgery work area clean and the patient's mouth relatively clear of fluids and debris. Such suction devices typically comprise a suction tube, which is connected to a long flexible hose, which is, in turn, connected to a vacuum source. When an oral surgeon is working on a tooth, an assistant is often required to manipulate the suction tube so as to maintain a clean work area and enable good visibility for the oral surgeon of the tooth being worked on. This procedure is problematic in that the assistant may be unable to anticipate the oral surgeon's moves in the patient's mouth and may thus be unable to keep the end of the suction tube out of the oral surgeon's way. As a consequence, the oral surgeon may prefer to do the evacuation of fluids and debris from the patient's mouth himself or herself. [0008] During oral surgery, it is usually also necessary for the oral surgeon to use a retractor to push or pull soft tissue regions of the patient's mouth away from the work area. This may be necessary to provide a more unrestricted view of the work area. However, it is reported in U.S. Pat. No. 4,883,426 that problems can result when both tissue retraction and fluid evacuation are needed. For example, the working area of a patient's mouth may become crowded with dental implements to an extent that the oral surgeon's task becomes very difficult to perform. Moreover, it may be necessary for the oral surgeon to frequently and repeatedly shift between tissue retraction and fluid evacuation implements, thereby requiring a longer time for the surgery being performed. U.S. Pat. No. 4,883,426 seeks to solve this problem by providing a single dental implement which combines the features of a fluid evacuation device and a soft tissue retraction device. Combination suction retraction instruments have also been proposed in U.S. Pat. Nos. 6,875,173, 5,281,134, 5,123,403 and 4,049,000. [0009] However, these devices do have drawbacks. When using these instruments, tissue, root tips, and bone may be drawn in to clog suction. For example, when an oral surgeon wishes to do deep socket exploration with an inseparable suction retraction device during surgery, the suction piece of the instrument can clog with tissue and debris thereby prolonging the surgical procedure. [0010] Therefore, there is a need for a combination suction retraction instrument that serves the functions of: (1) minimizing the number of instruments in the surgeon's field of view, (2) maintaining a clear surgical field free from bone slurry, blood, saliva and irrigant, and (3) providing the utility for rapid separation of suction from retraction for independent suction use during deep socket exploration. SUMMARY OF THE INVENTION [0011] The foregoing needs are met by the present invention which provides a combination suction retraction instrument. The instrument includes a retractor having a body, a suction nozzle secured to a distal end of the body, and means for retaining a suction tube adjacent to the retractor. The means for retaining the suction tube is secured to the body of the retractor. The means for retaining the suction tube is structured to allow the suction tube to slide within the means for retaining the suction tube upon manual pulling of the suction tube by a surgeon. Also, the means for retaining the suction tube is structured such that the suction tube does not slide within the means for retaining the suction tube when manual pulling force is not exerted on the suction tube. In the instrument, a proximal end of the suction nozzle is dimensioned to engage a distal end of the suction tube in a sealing relationship thereby providing a suction flow path from an opening of the suction nozzle into the suction tube. [0012] In one aspect of the invention, the means for retaining the suction tube may comprise a first round collar on the body of the retractor, and in another aspect of the invention, the means for retaining the suction tube further comprises a second round collar on the body of the retractor. The first collar may have a longitudinal axis colinear with a longitudinal axis of the proximal end of the suction nozzle, and the second collar may have a longitudinal axis colinear with the longitudinal axis of the proximal end of the suction nozzle. With this configuration of the first collar and the second collar, the suction tube may be threaded in a straight line though the first collar and the second collar into sealing interference fit engagement with the suction nozzle. [0013] The distal end of the body of the retractor may have a curved tip region for retraction of tissue. The body of the retractor may have a curved proximal end opposite the distal end of the body for grasping of the proximal end by the surgeon. The suction nozzle may have a distal end opposite the proximal end of the suction nozzle, and the distal end of the suction nozzle may terminate inward from the curved tip region of the distal end of the body to slightly separate the suction and retraction regions of the instrument. The suction nozzle may have an outwardly flared distal end for improved suction of fluid and debris. [0014] The invention also provides a suction retraction instrument including a suction tube having a distal end and having a proximal end suitable for attachment to a suction hose that is connected to a vacuum source. The instrument includes a retractor including a body, a suction nozzle secured to a distal end of the body, and means for retaining the suction tube adjacent the retractor. The means for retaining the suction tube is secured to the body. The means for retaining the suction tube is structured to allow the suction tube to slide within the means for retaining the suction tube upon manual pulling of the suction tube by a surgeon. Also, the means for retaining the suction tube is structured such that the suction tube does not slide within the means for retaining the suction tube when manual pulling force is not exerted on the suction tube. In the instrument, a proximal end of the suction nozzle is dimensioned to engage a distal end of the suction tube in a sealing relationship thereby providing a suction flow path from an opening of the suction nozzle into the suction tube. In one form, the distal end of the suction tube terminates in an opening, and an outer surface of the distal end of the suction tube tapers inward toward the opening. This provides for easier insertion of the suction tube into the proximal end of the suction nozzle. [0015] Thus, it is an advantage of the present invention to provide an improved combination suction retraction instrument that may be used for deep socket exploration during oral surgery. [0016] These and other features, aspects, and advantages of the present invention will become better understood upon consideration of the following detailed description, drawings, and appended claims. BRIEF DESCRIPTION OF THE DRAWINGS [0017] FIG. 1 is a right side elevational view of a combination suction retraction instrument according to the invention. [0018] FIG. 2 is a front elevational view of the instrument of FIG. 1 . [0019] FIG. 3 is a partial cross-sectional view of the instrument of FIG. 1 taken along line 3 - 3 of FIG. 1 . [0020] FIG. 4 is a front elevational view of a combination suction retraction instrument according to a second embodiment of the invention. [0021] FIG. 5 is a left side elevational view of the instrument of FIG. 4 . [0022] Like reference numerals will be used to refer to like parts from Figure to Figure in the following description of the drawings. DETAILED DESCRIPTION [0023] Turning to FIGS. 1 to 3 , there is shown a combination suction retraction instrument 10 according to the invention. The instrument 10 includes a retractor 20 having a body 22 . Preferably, the retractor 20 is formed from stainless steel. However, other metallic materials, ceramic materials, composite materials or polymeric materials would also be suitable for forming the retractor 20 . The body 22 has a first generally flat section 24 , a second generally flat section 26 , and an angled junction 25 that joins the first section 24 and the second section 26 in an offset configuration. A transverse cross section of each of the first section 24 , the angled junction 25 and the second section 26 is typically rectangular. It can be seen from FIG. 2 that the second section 26 has a reduced width compared to the first section 24 . In one embodiment, the width of the first section 24 is about 0.5 inches, the overall length of the retractor is about 6.3125 inches, and the thickness of the retractor is about 0.242 inches. [0024] The body 22 of the retractor 20 has a distal end 30 that terminates in a curved tip region 32 that has a distal arcuate edge 34 . The curved tip region 32 and distal arcuate edge 34 allow the surgeon to retract tissue during surgery. The second section 26 of the body 22 of the retractor 20 terminates in a proximal end 28 that is curved in an approximately 90 degree arc that provides a convenient grasping surface for the surgeon. [0025] The retractor 20 includes means for retaining a suction tube 50 adjacent the retractor 20 . An example means for retaining the suction tube is shown in FIGS. 1 and 2 . The means for retaining the suction tube includes a first round collar 36 and a second round collar 38 that are secured to a surface of the body 22 of the retractor 20 . The first collar 36 has a longitudinal axis 37 and the second collar 38 has a longitudinal axis 39 . The first collar 36 and the second collar 38 retain the suction tube 50 adjacent the retractor 20 as described below. In certain embodiments, the second collar 38 is not present. Other structures, such as opposed arcs, may be used for retaining the suction tube. [0026] The retractor 20 also includes a suction nozzle 40 secured to the distal end 30 of the body 22 of the retractor 20 . The suction nozzle 40 may be permanently or removably secured to the body 22 of the retractor 20 . The suction nozzle 40 has a tubular body 42 with an outer surface 43 . The suction nozzle 40 has a proximal end 45 with an inside surface 46 and a longitudinal axis 47 . The suction nozzle 40 also has a distal flared end 48 with an opening 49 for keep the oral surgery work area clean and the patient's mouth relatively clear of fluids and debris. In the embodiment shown, the distal end 48 of the suction nozzle 40 terminates inward from the curved tip region 32 of the distal end 30 of the body 22 of the retractor 20 . Thus, the suction nozzle 40 is secured to a flat section of the retractor 20 . Also, in the embodiment shown the suction nozzle 40 is formed from stainless steel. However, polymeric materials, ceramic materials or composite materials are also suitable for forming the nozzle 40 . [0027] The suction retraction instrument 10 also includes a suction tube 50 having a tubular body 52 . The suction tube 50 is preferably formed from stainless steel. The suction tube 50 has a central section 54 , a distal end 56 with an outer surface 57 and an opening 55 , and proximal end 58 . A fitting 59 is secured to the proximal end 58 of the suction tube 50 . The fitting 59 is secured to a suction hose fitting 64 of a flexible suction hose 66 that is connected to a conventional vacuum source (not shown). [0028] The suction tube 50 is removably attached to the retractor 20 as follows. First, the distal end 56 of the suction tube 50 is inserted into the second collar 38 of the retractor 20 . Second, the distal end 56 of the suction tube 50 is inserted into the first collar 36 of the retractor 20 . Third, the distal end 56 of the suction tube 50 is inserted into the proximal end 45 of the suction nozzle 40 to create a friction (interference) fit seal between the outer surface 57 of the distal end 56 of the suction tube 50 and the inside surface 46 of the proximal end 45 of the suction nozzle 40 . [0029] In one preferred embodiment, the longitudinal axis 39 of the second collar 38 and the longitudinal axis 37 of the first collar 36 are colinear with the longitudinal axis 47 of the proximal end 45 of the suction nozzle 40 such that insertion of the suction tube 50 in the second collar 38 , the first collar 36 and the proximal end 45 of the suction nozzle 40 proceeds along a linear path. In another preferred embodiment, the outer surface 57 of the distal end 56 of the suction tube 50 tapers inward toward the distal opening 55 of the suction tube 50 . The reduced outside diameter at the outer surface 57 of the distal end 56 of the suction tube 50 near the distal opening 55 provides for easier insertion of the distal end 56 of the suction tube 50 into the proximal end 45 of the suction nozzle 40 . [0030] The first collar 36 , the second collar 38 and the proximal end 45 of the suction nozzle 40 each have internal dimensions such that a friction (interference) fit is formed between the first collar 36 , the second collar 38 and the proximal end 45 of the suction nozzle 40 . However, upon application of a manual pulling force on the suction tube 50 or the fitting 59 of the suction tube 50 directed away from the retractor 20 by the surgeon, the suction tube 50 may slide in the first collar 36 , the second collar 38 and the proximal end 45 of the suction nozzle 40 . [0031] An oral surgeon may use the combination suction retraction instrument 10 as follows. First, the suction tube 50 is attached to the suction hose fitting 64 of the suction hose 66 that is connected to a conventional vacuum source. The suction tube 50 is then threaded through the second collar 38 (if present) and the first collar 36 and into the proximal end 45 of the suction nozzle 40 . The oral surgeon may then use the suction retraction instrument 10 (i) for removal of fluids and debris from a patient's mouth through the suction nozzle 40 and (ii) for retraction of tissue with the curved tip region 32 and distal arcuate edge 34 of the retractor 20 . [0032] If the oral surgeon wishes to perform only retraction and avoid suctioning vital structures such as nerve, muscle and fat, the oral surgeon pulls on the suction tube 50 or the fitting 59 of the suction tube 50 in a direction away from the retractor 20 . The suction tube 50 then slides out of the suction nozzle 40 in direction “A” of FIGS. 1 and 2 . The suction tube 50 may be pulled away from the suction nozzle 40 any distance desired. For example, the opening 55 of the distal end 56 of the suction tube 50 may be pulled back to near the first collar 36 . Suction is therefore interrupted through the suction nozzle 40 and retraction without suction can be performed. [0033] After completion of deep socket exploration, the oral surgeon may wish to perform suction again. The suction tube 50 is therefore reinserted into the proximal end 45 of the suction nozzle 40 . The oral surgeon may then use the suction retraction instrument 10 (i) for removal of fluids and debris from a patient's mouth through the suction nozzle 40 and (ii) for retraction of tissue with the curved tip region 32 and distal arcuate edge 34 of the retractor 20 . [0034] Turning to FIGS. 4 and 5 , there is shown a second embodiment of a combination suction retraction instrument 110 according to the invention. The instrument 110 includes a retractor 120 having a body 122 . Preferably, the retractor 120 is formed from stainless steel. However, other metallic materials, ceramic materials, composite materials or polymeric materials would also be suitable for forming the retractor 120 . The body 122 has a generally flat section 124 with a transverse cross section that is typically rectangular. It can be seen from FIG. 4 that the section 124 has a reduced width at its lower end. [0035] The body 122 of the retractor 120 has a distal end 130 that terminates in a curved tip region 132 that has a distal arcuate edge 134 . The curved tip region 132 and distal arcuate edge 134 allow the surgeon to retract tissue during surgery. The upper section of the body 122 of the retractor 120 terminates in a proximal end 128 that is curved in an approximately 90 degree arc that provides a convenient grasping surface for the surgeon. [0036] The retractor 120 includes means for retaining a suction tube 150 adjacent the retractor 120 . An example means for retaining the suction tube is shown in FIGS. 4 and 5 . The means for retaining the suction tube includes a tubular collar 136 that is secured to a surface of the body 122 of the retractor 120 . The collar 136 retains the suction tube 150 adjacent the retractor 120 as described below. [0037] The retractor 120 also includes a suction nozzle 140 secured to the distal end 130 of the body 122 of the retractor 120 . The suction nozzle 140 may be permanently or removably secured to the body 122 of the retractor 120 . The suction nozzle 140 has a proximal end 145 . The suction nozzle 140 also has a distal end 148 with an opening 149 for keep the oral surgery work area clean and the patient's mouth relatively clear of fluids and debris. In the embodiment shown, the distal end 148 of the suction nozzle 140 terminates inward from the curved tip region 132 of the distal end 130 of the body 122 of the retractor 120 . Thus, the suction nozzle 140 is secured to a flat section of the retractor 120 . Also, in the embodiment shown the suction nozzle 140 is formed from stainless steel. However, polymeric materials, ceramic materials or composite materials are also suitable for forming the nozzle 140 . [0038] The suction retraction instrument 110 also includes a suction tube 150 (shown in FIG. 5 ) having a tubular body 152 . The suction tube 150 is preferably formed from stainless steel. The suction tube 150 is removably attached to the retractor 120 as follows. First, the distal end 156 of the suction tube 150 is inserted into the collar 136 of the retractor 120 . Second, the distal end 156 of the suction tube 150 is inserted into the proximal end 145 of the suction nozzle 140 to create a friction (interference) fit seal between the outer surface of the distal end 156 of the suction tube 150 and the inside surface of the proximal end 145 of the suction nozzle 140 . The collar 136 and the proximal end 145 of the suction nozzle 140 each have internal dimensions such that a friction (interference) fit is formed between the collar 136 and the proximal end 145 of the suction nozzle 140 . However, upon application of a manual pulling force on the suction tube 150 directed away from the retractor 120 by the surgeon, the suction tube 150 may slide in the collar 136 and the proximal end 145 of the suction nozzle 140 . [0039] Thus, the present invention provides a combination suction retraction instrument that may be used for oral surgery. When using the instrument, an assistant need not provide suction during the surgery. If the oral surgeon wishes to perform only retraction and avoid suctioning vital structures such as nerve, muscle and fat, the suction and retraction components can be quickly separated. [0040] Although the present invention has been described with reference to certain embodiments, one skilled in the art will appreciate that the present invention can be practiced by other than the described embodiments, which have been presented for purposes of illustration and not of limitation. Therefore, the scope of the appended claims should not be limited to the description of the embodiments contained herein.
A combination suction retraction instrument for surgery is disclosed. The suction retraction instrument includes a retractor including a body, a suction nozzle secured to a distal end of the body, and means for retaining a suction tube adjacent the retractor. The suction tube is connected to a vacuum source for removing fluids and debris from a surgical site. The means for retaining the suction tube is secured to the body. The means for retaining the suction tube is structured to allow the suction tube to slide within the means for retaining the suction tube upon manual pulling of the suction tube by a surgeon. A proximal end of the suction nozzle is dimensioned to engage a distal end of the suction tube in a sealing relationship thereby providing a suction flow path from an opening of the suction nozzle into the suction tube.
0
BACKGROUND The field of the invention is a device for producing a thin-walled elongate body, such as a pipette or a tip. When producing thin-walled elongate bodies, such as particularly pipettes or tips, the problem arises that no rotary symmetrical parts are produced due to off-setting and tolerances in the tool. This means that during automatic pipetting the outlet opening for the liquid to be pipetted is not located at the predetermined position. Such unsymmetric pipettes may lead to problems and/or they represent rejects. SUMMARY An objective of the present invention comprises to provide a device, which allows the production of thin-walled elongate bodies, with their wall thicknesses being constant, i.e. after the production their tip is located on the geometric axis of symmetry of the body. Another objective of the invention comprises to embody the device such that deviations determined can be corrected in a simple fashion directly at the injection molding tool. This objective is attained in a device according to the invention. Advantageous embodiments of the device are described below. This is achieved by the eccentric embodiment of the eccentric bush and the removable sleeve engaging each other such that the position of the core can be aligned by a simple rotary motion of one of the two elements. BRIEF DESCRIPTION OF THE DRAWINGS Based on an illustrated exemplary embodiment the invention is explained in greater detail. It shows: FIG. 1 is a perspective view of a thin-walled elongate body based on a pipette, FIG. 2 is a cross-sectional view through an injection tool for a pipette, FIG. 3 is a perspective view of the core of the tool, FIG. 4 is a perspective view of a removable sleeve, FIG. 5 a is a perspective view of a bush, FIG. 5 b is a view of a bush seen from a different angle, FIG. 6 is a detail of the first mold halves—ejection side, and FIG. 7 is a perspective view of a fastening plate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In FIG. 1 , a pipette is marked with the reference character 1 as an example for a thin-walled elongate body. It is embodied conically tapering at the right side, i.e. as a hollow, acute-angled frustum 3 . The front end shows a diameter of 0.75 mm, for example, and an outlet opening 5 of 0.45 mm. In other words the wall thickness (thickness of the wall) amounts to only 0.15 mm. At the left side, a flange 7 is discernible at the frustum 3 , which is intended to connect the pipette 1 to and/or with a pipetting device. Instead of a conically extending pipette 1 , of course a body with a cylindrical sleeve can also be used. FIG. 2 shows at the left side details of a first mold half (ejection side) of the injection mold 9 , mold half 9 for short, and on the right side the second mold half (nozzle side) of the injection mold 11 , mold half 11 for short. The second mold half 11 includes a matrix 13 , which forms the exterior contour of the pipette 1 , i.e. of the work piece. The first mold half 9 (left) carries the core 15 , which forms the interior contour of the pipette 1 and comprises several parts. The molding part, i.e. the core 15 , is shown in FIG. 3 in an enlarged fashion. At the top it comprises a tip 45 and subsequently an acute frustum 17 , which forms the interior space of the acutely tapering area of the pipette 1 . Here, a cylindrical or conical section 19 follows, which forms the rear section of the pipette 1 . The section 21 located at the bottom in FIG. 3 ends in a flange 23 , by which the core 15 is fastened at the first mold half 9 of the tool 9 . The core 15 is surrounded by a removable sleeve 25 . The removable sleeve 25 comprises an axially symmetrical bore 27 , with its diameter exhibiting a diameter in the rear part which is greater than the exterior diameter of the core 15 . In the front part, the bore 27 extends conically and essentially contacts the core 15 at the rear at the conical section 18 . The core 15 is consequently connected on the one side by the flange 23 at the section 21 with the mold half 9 and at its conical section at the rear 18 via the removable sleeve 25 without any play. The casing 29 of the removable sleeve 25 is not embodied axially symmetrical but exhibits eccentricity, which for example may amount to 0.08 mm. The eccentricity comprises the cylindrical section of the removable sleeve 25 as well as the conically progressing section. At the front of the removable sleeve 25 an eccentric bush is provided, called bush 33 for short, with its bore 31 being embodied congruent in reference to the casing 29 of the removable sleeve 25 . The bore 31 of the bush 33 is also embodied eccentric in reference to the casing surface 35 of the bush 33 , i.e. the casing surface 35 is located symmetrically in reference to the axis of symmetry of the bush 3 ; the bore 31 is eccentrically in reference to the axis of symmetry A. The bush 33 is supported in an axial fashion with its rear end 39 , embodied as a flange, on a circumferential flange-like web 37 of the removable sleeve 25 . The cylindrical base 30 of the removable sleeve 25 can be inserted into the first mold half 9 in a cylindrical receiving bore 32 . The removable sleeve 25 and the bush 33 are engaged on each other and protected from rotation in reference to each other by a fastening plate 41 , on which the mold half 9 rests. The fastening plate 41 is held by at least one screw 43 . By the eccentric embodiment of the casing 29 on the removable sleeve 25 and the eccentric embodiment of the bore 31 in the bush 33 , by a mutual rotation of the removable sleeve 25 and the bush 33 , the position of the core 15 can be determined in a radial displacement, radially displaced by a predetermined range and simultaneously here the angular displacement. In other words, the conical area at the rear 18 of the core 15 is displaced from the axis of symmetry A by the removable sleeve 25 and the bush 33 . Markings 49 are provided on the surface 47 of the flange-like web 37 at the removable sleeve 25 , e.g., in the form of bumps or grooves. These markings 49 may be provided with numbers in order to allow identification. As an alternative to the bumps, bores may also be provided as markers, penetrating partially or entirely. Further, on the periphery of the circumferential web 37 at “0” a marking 51 is inserted or applied. Another marking 52 is applied at the widest position of the facial area. A marking 53 is also inserted or applied at the bush 33 ( FIG. 5 ) on the top of the flange-like rear end 39 . Between the key areas 57 of the bush 33 another marking 50 is applied. It is arranged with the marking 53 at the bush 33 in an alignment. Another marking 54 is applied at the widest point of the facial end. Further, at the bottom a pin 55 is inserted, intended and suitable to engage and/or latch in the markings 49 at the removable sleeve 25 in order to determine the adjusted angular rotary position between the removable sleeve 25 and the bush 33 . Further, an option is provided at the bush 33 to attach an open-end wrench. For this purpose, at the perimeter key flanges 57 are provided similar to a hex nut. FIGS. 6 and 7 show perspective illustrations of the fastening plate 41 ( FIG. 7 ) as well as the mold plate (ejection side) 59 . Receiving bores 61 are formed in the mold plate 49 , into which the removable sleeves 25 can be inserted axially. Scales from +180° to −180° are respectively engraved at the edges 63 of the accepting bores 61 . These scales 65 serve to position the removable sleeve 25 during the assembly and to fixate it in a new position upon correction thereof. Holes 67 are in turn embodied on the fastening plate 41 ( FIG. 7 ) aligned to the receiving bores 61 of the molding plate 59 and also markings of +/−180° are applied on its periphery. During the assembly of the core 15 in the mold halves 9 the removable sleeve 25 and the bush 33 are assembled in each other such that the core 15 is subjected to a displacement/deflection known from experience. However, if it is now detected that either the amount of the displacement of the injection molded parts, here the pipette 1 , deviates from the target value and/or its angular position from the target value, in an open injection mold (mold halves 9 and 11 spaced apart as in FIG. 2 ) the screw 43 can be released and the fastening plate 41 can be disassembled and the mutual position of the removable sleeve 25 and the bush 33 as well as the angular position of the two elements 25 , 33 can be adjusted in reference to the molding plate AS 59 . The adjustment can occur based on a table deducted from experiments. Such a readjustment of a core 15 can be performed within a few minutes and it is not required for the injection mold to be disassembled from the injection molding machine, here.
A device for producing a thin-walled elongate body from thermoplastic material includes a removable sleeve ( 25 ) and a bush ( 33 ), the casing of the removable sleeve ( 25 ) and the bore ( 31 ) in the bush ( 33 ) are arranged eccentrically with respect to the axis of symmetry of the core and, by rotation relative to one another, a displacement of the core can be achieved both in terms of magnitude and also in relation to a deflection angle.
1
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is related to a continuous shear deformation device, in particular, which is capable of mass-producing shear deformed metallic materials by continuously supplying the metallic materials to a sharply bent channel type mold. 2. Description of the Background Art When a metal billet is pushed into a sharply bent channel type mold by punch, shear deformation occurs while the metal is passing through the sharply bent zone of the mold, which is generally known as ECAP (Equal Channel Angular Pressing). The inlet and the outlet of an ECAP mold have the same shape and cross-sectional area. Fine grain structure is obtained by ECAP and thus stiffness and plasticity of materials are improved (Metals and Materials, Vol. 4, No. 6, 1998, pp. 1181˜1190). However, in a shear deformation device using a punch in the conventional art, there is a limitation on the size of a supplied billet, so that only a shear-deformed material of a limited length can be obtained. Moreover, once the billet is extruded, the next billet can be extruded only after extracting the punch from the mold. Thus, shear-deformed material has to be intermittently produced by small amounts. In addition, when the punch is overloaded in the shear deformation device in the conventional art, there is another problem that the overload is directly transferred to the punch and thus the punch and the punch driving apparatus can be damaged or break down. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a device which is capable of continuously mass-producing shear deformed materials, with no limitation on the length of material, by continuously supplying the metallic materials to an ECAP mold. In addition, it is another object of the present invention to provide a continuous shear deformation device which is capable of continuing to operate smoothly though an apparatus for supplying materials into a mold is unintentionally overloaded. Meanwhile, it is still another object of the present invention to provide a continuous shear deformation device which is capable of reducing friction between a mold and materials, accordingly increasing the life span of the mold, decreasing the force required for press-fitting materials, and thereby reducing the whole operating costs In addition, it is yet still another object of the present invention to provide a continuous shear deformation device which can be compatibly used according to materials, in particular, materials of different thickness from thin sheet to thick plate material. In order to achieve the above objects, there is provided a continuous shear deformation device in accordance with the present invention, including: a sharply bent shear deformation mold; and a rotary guide apparatus installed at the inlet of the mold for guiding materials into the mold by frictional contact with the material. In accordance with a preferred embodiment of the present invention, rotary type rolls such as a single rotary roll, a pair of rotary rolls and plurality of rotary rolls, etc. are used as the above inlet guide apparatus. Instead of rotary type rolls, belts of various shapes, including a loop in which a plurality of polyhedral blocks are sequentially connected or a belt having an inner side of chain form, etc. can be used. In addition, guide apparatuses of the preferred embodiment can be used in combination with each other. For example, rotary type rolls are used at one side and a belt transmission are used at the other side. Even in case of employing a belt transmission, belts of various forms can be used in combination. In addition, a plurality of guide apparatuses can be used according to design objective such as required friction force. The description in this paragraph will be directly applied to an outlet guide to be mentioned later. In addition, in the present invention, an outlet rotary guide for exiting materials after shear deformation can be provided additionally. In accordance with another preferred embodiment of the present invention, a transmission belt can be used as a guide for exiting materials, immediately after shear deformation, to the outside of the mold inlet by frictional contact between the belt and the shear-deformed materials. In addition, in accordance with another embodiment, the guide can be a rotary roll or a transmission belt installed at the outside of the outlet which feeds discharged materials and winds or flattens materials. In addition, in accordance with another preferred embodiment of the present invention, the mold can be provided with an inclined or a curved inlet in order to increase the amount of contact between the guide apparatus and materials. In addition, the thickness of materials prior to passing through the guide apparatus of the present invention may be greater than that of materials after passing through the guide apparatus. In this case, the material is rolled according to the clearance space of its supply path, and thereby it is possible to provide a shear deformation device which can be compatibly used according to materials, for example, materials of different thickness from thin sheet materials less than 0.5 mm to thick plate materials, with no limitation on thickness. In a case where there is a wide difference between the thickness of materials and the thickness of a molding path, the material can be provided to a mold by gradually reducing the thickness of the material using several pairs of rolls and/or other guide apparatuses. In addition, in accordance with another embodiment of the present invention, a frictional contact can be provided with a groove corresponding to the cross-sectional shape of materials in order to increase the frictional contact force between the guide apparatus or guide feeder and the materials. And, it can be covered with any particular material of high friction coefficient, its surface roughness can be increased, or materials of high friction coefficient can be directly used as a body of a guide apparatus. Additional advantages, objects and features of the invention will become more apparent from the description which follows. BRIEF DESCRIPTION OF THE DRAWINGS The present invention will become better understood with reference to the accompanying drawings which are given only by way of illustration and thus are not limitative of the present invention, wherein: FIG. 1 is a schematic view illustrating a continuous shear deformation device using a pair of rotary rolls as a guide apparatus in accordance with one embodiment of the present invention; FIG. 2 is a schematic view illustrating a continuous shear deformation device using a belt transmission as a guide apparatus in accordance with another embodiment of the present invention; FIG. 3 illustrates a guide apparatus using a loop type belt in which a plurality of polyhedral blocks are sequentially connected in accordance with another embodiment in conjunction with the belt type guide apparatus of FIG. 2; FIG. 4 is a schematic view illustrating a shear deformation device using a mold having an inclined inlet in accordance with another embodiment of the present invention; FIG. 5 is a view illustrating a shear deformation device using a guide apparatus of a single roll in accordance with another embodiment of the present invention; FIG. 6 is a schematic view illustrating a shear deformation device in which the thickness of the materials is reduced by the guide apparatus in accordance with another embodiment of the present invention; FIG. 7A is a schematic view of a shear deformation device, and FIGS. 7B and 7C are cross-sectional views of a rotary roll, each in accordance with one embodiment of a guide apparatus for increasing the area of contact with materials; and FIGS. 8A and 8B each are a lateral view and a front view illustrating a guide for feeding material after shear deformation in accordance with one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention will now be described with reference to the accompanying drawings. FIG. 1 is a schematic view illustrating a continuous shear deformation device using a pair of rotary rolls as a guide apparatus 2 in accordance with one embodiment of the present invention. As illustrated therein, material 3 is continuously supplied into a mold 1 by installing the pair of rotary rolls at the inlet of the shear deformation device and then using the frictional contact force between the material 3 and the device. The supplied material 3 passing through the mold 1 is shear-deformed, and thereafter discharged to the outlet. If the material 3 is thick and outside angle of the mold 1 is large, the force required for shear deformation is increased and accordingly a strong press fit force is required. In this case, several pairs of rotary rolls can be installed at the inlet of the shear deformation device. In addition, materials can be supplied easily by covering the rotary rolls with material of high friction coefficient or roughing their surfaces while reducing the mold contact path 8 , smoothly processing a molding path 8 and supplying the same with lubricant. If the material 3 is thin and its bending angle is small, the force required for shear deformation is reduced and accordingly the material 3 is well supplied into the mold 1 without slipping on the rotary rolls. However, if the distance between the rotary rolls and the inlet of the mold is wide when the material 3 is thin, there is a possibility that the material 3 could be buckled without being smoothly supplied into the mold 1 . Thus, the guide apparatus 2 needs to be installed at a position close to the mold 1 , if possible. In accordance with one embodiment of the present invention, the material 3 passing through the mold 1 to be discharged to the out let can be cut at an appropriate size by installing a cutter (not shown) at the outlet of the mold 1 . In the shear deformation device of the present invention, in the case that the guide apparatus 2 is overloaded, a slip is occurred between the guide apparatus 2 and the material 3 and thus it serves as a safety equipment, thereby preventing damage to the guide apparatus 2 due to unintentional overload. FIG. 2 is a schematic view illustrating a continuous shear deformation device using a belt transmission as a guide apparatus 2 in accordance with another embodiment of the present invention. As illustrated therein, in the guide apparatus 2 of this embodiment continuously feeds material 3 by frictional contact between the belt 5 and the material 3 by installing a rotary belt 5 with a plurality of rotary rolls 6 surrounded by rubber or a metal. In this apparatus, a very high press fit force is generated because the area of contact between the rotary belt 5 and the material 3 is wide. Thus, the guide apparatus 2 is particularly useful when the material 3 is thick and its bending angle is large. In accordance with another embodiment of the present invention, when there is a necessity for surely acquiring a transmission between the belt 5 and the rotary rolls 6 for driving the belt, a belt 5 having an inner side of chain shape and rotary rolls 6 of sprocket shape are used for thereby making them engaged with each other. FIG. 3 illustrates a guide apparatus using a loop type belt in which a plurality of polyhedral blocks are sequentially connected in accordance with another embodiment in conjunction with the belt type guide apparatus 2 of FIG. 2 . Since the apparatus of FIG. 3 also has a wide area of contact between the guide apparatus 2 and the material 3 , it can push the material 3 continuously with a very high press fit force. FIG. 4 is a schematic view illustrating a shear deformation device using a mold having a curved and inclined inlet in accordance with another embodiment of the present invention. As illustrated therein, since the material 3 travels between the two guide apparatuses 2 , that is, the two rotary rolls, and then is supplied into the inlet of the mold while continuously being contact with one of the rotary rolls for a fairly long distance, the area of friction between the rotary roll and the material 3 is increased thereby to obtain a high press fit force. FIG. 5 is a view illustrating a shear deformation device using a guide apparatus 2 in accordance with another embodiment of the present invention. In a case that the material 3 is sufficiently guided by a relatively small press fit force, as illustrated in FIG. 5, the material can be guided by using only one guide apparatus 2 . In this embodiment, as illustrated therein, it is preferable that the mold 1 has an inclined path with short contact area of outlet. FIG. 6 is a schematic view illustrating a shear deformation device in which the thickness of materials is reduced by the guide apparatus 2 in accordance with another embodiment of the present invention. As illustrated therein, the thick material 3 is made thin by the rotary rolls, and then supplied into the mold 1 . Since this apparatus has a wide area of contact between the roll and the material 3 and pushes the material while firmly pressing the same, a high press fit can be generated without covering the rotary roll with a rubber film or roughing the surfaces of the rolls. In addition, there is an advantage that since a variety of materials 3 can be used in this apparatus, any particular process for obtaining a material of a thickness corresponding to the mold 2 is not required. In the case that the thickness of an initial material 3 is very thick, the material can be supplied into the mold 1 by gradually reducing the thickness while passing through a several pairs of rotary rolls. FIG. 7A is a schematic view of a shear deformation device, and FIGS. 7B and 7C are cross-sectional views of a rotary roll, each in accordance with one embodiment of a guide apparatus for increasing the area of contact with material. As illustrated therein, a square groove (FIG. 7B) 10 or a round groove (FIG. 7C) 11 corresponding to the cross-sectional shape of the material 3 is engraved on the surfaces of the rotary rolls, and accordingly the area of contact between the rotary rolls and the material 3 is very large so that a high press fit force is generated. If the material 3 is compressed and pushed as in the embodiment of FIG. 6 when passing through the rotary rolls, a much higher press fit force can be obtained. FIGS. 8A and 8B each are a lateral view and a front view illustrating a guide 13 for exiting material after shear deformation in accordance with one embodiment of the present invention. As illustrated therein, a belt type guide 13 for exiting material is installed from the curve point of the molding path 8 to the outside of the outlet, thereby reducing the frictional resistance. Belts of various structures and shapes including a belt 15 made by connecting metal plates or pieces of material of high stiffness and a loop type belt in which polyhedral blocks are sequentially connected can be used for the above belt type guide 13 . Because the guide 13 continuously moves with the material 3 , it serves to reduce the area of friction between the material 3 and the mold 1 for thereby increasing the life of the mold and decrease the force required for press-fitting the material. Meanwhile, in accordance with another embodiment of the guide 13 , feeding of the materials can be performed by installing the rotary rolls outside the outlet of the mold 1 . This guide serves to not only reduce the force required for press-fitting the material, but also wind the discharged material or flatten the surfaces. As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, unless otherwise specified, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims. For example, the guide apparatus 2 and the guide 13 as well as the mold in accordance with the present invention can have a variety of shapes and structures, and the components constructing the present invention, each of which having been described in its embodiment, can be used in combination with each other. In accordance with the present invention thus described, it is possible to continuously mass-produce shear deformed materials, with no limitation on material, by continuously supplying a curved shear deformation mold with material. In addition, in the present invention, it is possible to continue to operate smoothly though a supply apparatus for supplying material into a mold is unintentionally overloaded, with no influence on the device according to the overload. Meanwhile, in the present invention, it is possible to reduce friction between a mold and materials, accordingly increase the life of the mold, decrease the force required for press-fitting material, and thereby reduce the whole operating costs In addition, the present invention can be compatibly used according to materials, in particular, materials of different thickness from thin sheet materials to thick plate materials.
The present invention relates to a continuous shear deformation device, in particular, which is capable of mass-producing shear deformed materials by continuously supplying a sharply bent channel type mold with materials, particularly, which have a variety of thickness from thin sheet to thick plate. The continuous shear deformation device in accordance with the present invention includes a sharply bent channel type mold and a rotary guide apparatus installed at the inlet of the mold for guiding materials into the mold by frictional contact with the materials. In addition, the present invention can additionally include a rotary guide for exiting the shear-deformed material.
1
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of the US national phase designation of International application PCT/EP02/07162 filed Jun. 28, 2002, the content of which is expressly incorporated herein by reference thereto. BACKGROUND ART The present invention relates to a novel carboxypeptidase gene and the polypeptide encoded thereby. In particular, the present invention relates to the use of the present carboxypeptidase in the manufacture of cocoa flavor and/or chocolate. It is known that in processing cacao beans the generation of the typical cocoa flavor requires two steps—a fermentation step, which includes air-drying of the fermented material, and a roasting step. During fermentation two major activities may be observed. First, the pulp surrounding the beans is degraded by micro-organisms with the sugars contained in the pulp being largely transformed to acids, especially acetic acid (Quesnel et al., J. Sci. Food. Agric. 16 (1965), 441–447; Ostovar and Keeney, J. Food. Sci. 39 (1973), 611–617). The acids then slowly diffuse into the beans and eventually cause an acidification of the cellular material. Second, fermentation also results in a release of peptides exhibiting differing sizes and a generation of a high level of hydrophobic free amino acids. This latter finding led to the hypothesis that proteolysis occurring during the fermentation step is not due to a random protein hydrolysis but seems to be rather based on the activity of specific endoproteinases (Kirchhoff et al., Food Chem 31 (1989), 295–311). This specific mixture of peptides and hydrophobic amino acids is deemed to represent cocoa-specific flavor precursors. Until now several proteolytic enzyme activities have been investigated in cacao beans and studied for their putative role in the generation of cocoa flavor precursors during fermentation. An aspartic endoproteinase activity, which is optimal at a very low pH (pH 3.5) and inhibited by pepstatin A has been identified. A polypeptide described to have this activity has been isolated and is described to consist of two peptides (29 and 13 kDa) which are deemed to be derived by self-digestion from a 42 kDa pro-peptide (Voigt et al., J. Plant Physiol. 145 (1995), 299–307). The enzyme cleaves protein substrates between hydrophobic amino acid residues to produce oligopeptides with hydrophobic amino acid residues at the ends (Voigt et al., Food Chem. 49 (1994), 173–180). The enzyme accumulates with the vicilin-class (7S) globulin during bean ripening. Its activity remains constant during the first days of germination and does not decrease before the onset of globulin degradation (Voigt et al., J. Plant Physiol. 145 (1995), 299–307). Also a cysteine endoproteinase activity had been isolated which is optimal at a pH of about 5. This enzymatic activity is believed not to split native storage proteins in ungerminated seeds. Cysteine endoproteinase activity increases during the germination process when degradation of globular storage protein occurs. To date, no significant role for this enzyme in the generation of cocoa flavor has been reported (Biehl et al., Cocoa Research Conference, Salvador, Bahia, Brasil, Nov. 17–23, 1996). Moreover, a carboxypeptidase activity has been identified which is inhibited by PMSF and thus belongs to the class of serine proteases. It is stable over a broad pH range with a maximum activity at pH 5.8. This enzyme does not degrade native proteins but preferentially splits hydrophobic amino acids from the carboxy-terminus of peptides (Bytof et al., Food Chem. 54 (1995), 15–21). During the second step of cocoa flavor production—the roasting step—the oligopeptides and amino acids generated at the stage of fermentation are obviously subjected to a Maillard reaction with reducing sugars present in fermented beans eventually yielding substances responsible for the cocoa flavor as such. In the art there have been many attempts to artificially produce cocoa flavor. Cocoa-specific aroma has been obtained in experiments wherein acetone dry powder (AcDP) prepared from unfermented ripe cacao beans was subjected to autolysis at a pH of 5.2 followed by roasting in the presence of reducing sugars. It was conceived that under these conditions preferentially free hydrophobic amino acids and hydrophilic peptides should be generated and the peptide pattern thus obtained was found to be similar to that of extracts from fermented cacao beans. An analysis of free amino acids revealed that Leu, Ala, Phe and Val were the predominant amino acids liberated in fermented beans or autolysis (Voigt et al., Food Chem. 49 (1994), 173–180). In contrast to these findings, no cocoa-specific aroma could be detected when AcDP was subjected to autolysis at a pH of as low as 3.5 (optimum pH for the aspartic endoproteinase). Only few free amino acids were found to be released but a large number of hydrophobic peptides were formed. When peptides obtained after the autolysis of AcDP at a pH of 3.5 were treated with carboxypeptidase A from porcine pancreas at pH 7.5, hydrophobic amino acids were preferentially released. The pattern of free amino acids and peptides was similar to that found in fermented cacao beans and to the proteolysis products obtained by autolysis of AcDP at pH 5.2. After roasting of the amino acids and peptides mixture as above, a cocoa aroma could be generated. It has also been shown that, a synthetic mixture of free amino acids alone with a similar composition to that of the spectrum found in fermented beans, was incapable of generating cocoa aroma after roasting, indicating that both the peptides and the amino acids are important for this purpose (Voigt et al., Food Chem. 49 (1994), 173–180. In view of the above data a hypothetical model for the generation, during fermentation, of the said mixture of peptides and amino acids, i.e. the cocoa flavor precursors, had been devised ( FIG. 1 ), where in a first step peptides having a hydrophobic amino acid at their end, are formed from storage proteins, which peptides are then further degraded to smaller peptides and free amino acids. To produce the said peptides having C-terminal hydrophobic amino acids, an aspartic endoproteinase activity related to that mentioned above seems to be involved. Yet, for splitting off hydrophobic amino acids from peptides formed in the preceding step the only known enzymatic activity, which might be considered in this respect, is that of a carboxypeptidase. However, such enzyme has not been isolated and studied in detail in cacao and it is therefore still questionable, which cacao enzyme might be responsible for the generation of hydrophobic amino acids required for cocoa flavor. Though some aspects of cocoa flavor production have been elucidated so far there is still a need in the art to fully understand the processes involved, so that the manufacture of cocoa flavor may eventually be optimized. SUMMARY OF THE INVENTION The present invention provides means for further elucidating the processes involved in the formation of cocoa-specific aroma precursors during the fermentation of cacao seeds, to improve the formation of cocoa flavor during processing and manufacturing and eventually providing means assisting in the artificial production of cocoa flavor. This problem has been solved by providing a nucleotide sequence encoding a novel carboxypeptidase from cacao beans (termed cacao CP-III), which is identified by SEQ. ID. No. 1, or functional derivatives thereof having a degree of homology that is greater than 80%, preferably greater than 90% and more preferably greater than 95%. It will be appreciated by the skilled person that a gene encoding a specific polypeptide may differ from a given sequence according to the Wobble hypothesis, in that nucleotides are exchanged that do not lead to an alteration in the amino acid sequence. Yet, according to the present invention also nucleotide sequences shall be embraced, which exhibit a nucleotide exchange leading to an alteration of the amino acid sequence, such that the functionality of the resulting polypeptide is not essentially disturbed. This nucleotide sequence may be used to synthesise a corresponding polypeptide by means of recombinant gene technology, in particular a polypeptide as identified by SEQ. ID. No. 2. As has been shown in a comparison with other carboxypeptidases from other plants the present enzyme does not show a substantial homology to any of the carboxypeptidases known so far. Since it is assumed, that cocoa may furthermore contain additional carboxypeptidases that might exhibit a higher homology to the carboxypeptidases known so far it must be considered as a surprising fact that this very enzyme has been detected. For producing the polypeptide by recombinant means, the nucleotide of the present invention is included in an expression vector downstream of a suitable promoter and is subsequently incorporated into a suitable cell, which may be cultured to yield the polypeptide of interest. Suitable cells for expressing the present polypeptide include bacterial cells, such as e.g. E. coli, or yeast, insect, mammalian or plant cells. The present DNA sequence may also be incorporated directly into the genome of the corresponding cell by techniques well known in the art, such as e.g. homologous recombination. Proceeding accordingly will provide a higher stability of the system and may include integration of a number of said DNA-sequences into a cell's genome. The cells thus obtained may in consequence be utilized to produce the polypeptide in batch culture or using continuous procedures, with the resulting polypeptide being isolated according to conventional methods. The recombinant carboxypeptidase obtained may be used for the manufacture of cocoa flavor. To this end, the enzyme described herein may be utilized in an artificial trial run, wherein a mixture of different proteins, such as cacao storage proteins, or protein hydrolysates of other resources, are subjected to enzymatic degradation by means of enzymes, known to be involved in proteolytic degradation to eventually assist in the production of flavor precursors. The enzyme may likewise also be utilized in the production of cocoa liquor, and in the manufacture of chocolate. Yet, the present invention also provides plants, in particular cacao plants, comprising a recombinant cell, containing one or more additional copies of the carboxypeptidase of the present invention. Such a cacao plant will produce beans, which will exhibit a modified degradation of storage proteins when subjected to the fermentation process, allowing a more rapid degradation or a pattern of hydrolysis that yields a higher level of cocoa flavor precursor, since a higher amount of carboxypeptidase will be present. The carboxypeptidase of the present invention may also be used to produce other transgenic plants such as soybean and rice, producing seeds with this new protein modifying enzyme. BRIEF DESCRIPTION OF THE DRAWING FIGURES In the figures, FIG. 1 shows a scheme illustrating a potential process for the proteolytic formation of cocoa-specific aroma; FIG. 2 shows the cloning strategy used for the isolation of a cDNA encoding a carboxypeptidase from Theobroma cacao; FIG. 3 shows a comparison of the hydrophilicity Plot-Kyte-Doolittle for the cacao CP-III sequence with Barley CP-MI, CP-MII and CP-MIII; and FIGS. 4A , 4 B and 4 C shows a Northern blot analysis of cacao CP-III. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, it was suggested that a carboxypeptidase could be involved in the production of cocoa flavor precursors during cacao fermentation. However it was not known in the art which cacao carboxypeptidase carried out this function considering that five classes of carboxypeptidases (Type I-V) have been identified in different plants by references to differences in substrate specificities, molecular weights and chromatographic profiles. Furthermore 50 sequences having homologies with serine carboxypeptidases exist in the completed Arabidopsis genome. The proteolytic formation of cocoa-specific aroma according to the invention is illustrated in FIG. 1 . The following examples illustrate the invention further without limiting it thereto. In the examples the following abbreviations have been used: PCR: Polymerase Chain Reaction RACE: Rapid Amplification cDNA Ends cDNA: complementary deoxyribonucleic acid mRNA: messenger ribonucleic acid DEPC: Diethyl pyrocarbonate 3,4-DCI: 3,4-dichloroisocoumarin EXAMPLES Materials Cacao ( Theobroma cacao L. ) seeds (male parent unknown) from ripe pods of clone ICS 95 were provided by Nestlé ex-R&D Center Quito (Ecuador). The seeds were taken from the pods immediately after arrival at Nestle Research Center Tours (4–5 days after harvesting). The pulp and the seed coat were eliminated and the cotyledons were frozen in liquid nitrogen and stored at −80° C. until use. Preparation of mRNA Total RNA was prepared using the following method. Two seeds were ground in liquid nitrogen to a fine powder and extraction was directly performed with a lysis buffer containing 25 mM Tris HCl pH8, 25 mM EDTA, 75 mM NaCl, 1% SDS and 1M β-mercaptoethanol. RNA was extracted with one volume of phenol/chloroform/isoamylalcohol (25/24/1) and centrifuged at 8000 rpm, 10 min at 4° C. The aqueous phase was extracted a second time with one volume of phenol/chloroform/isoamylalcohol (25/24/1). RNA was precipitated with 2M lithium chloride at 4° C. overnight. The RNA pellet obtained after centrifugation was resuspended in DEPC treated water and a second precipitation with 3M sodium acetate pH 5.2 was performed in presence of two volumes of ethanol. The RNA pellet was washed with 70% ethanol and resuspended in DEPC treated water. Total RNA was further purified using the Rneasy Mini kit from Qiagen®. Cloning of a carboxypeptidase cDNA Cloning Strategy A 1.5 kb 5′ end fragment of a carboxypeptidase from cacao seed was amplified by RT-PCR using a degenerate oligonucleotide. Based on the sequence of this fragment, a primer was designed to amplify a 3′-end fragment. Finally, a full-length cDNA (cacao CP-III) was amplified using primers specific to both extremities. The cloning strategy used for isolation of a cDNA encoding a carboxypeptidase from Theobroma cacao , clone ICS 95 is shown in FIG. 2 . Primer Design A search for carboxypeptidase sequences in the GenBank database lead to the identification of several plant sequences. A multiple alignment of these sequences revealed the presence of conserved regions. The conserved sequence MVPMDQP located near the histidine catalytic site has been used to design a degenerate oligonucleotide in the antisense orientation: pCP2r (5′-GGYTGRTCCATNGGNACCAT) (SEQ ID No. 3). Synthesis of cDNA Total RNA (see above) was used to synthesise first strand 3′ and 5′ cDNAs with the SMART™ RACE cDNA Amplification Kit (Clontech, USA). Synthesis has been performed exactly as described in the kit instructions using 1 μg of total RNA and the Superscript™ II MMLV reverse transcriptase (Gibco BRL, USA). After synthesis, cDNAs were used directly for PCR or kept at −20° C. 5′ RACE Amplification Specific cDNA amplification was performed with 2.5 μl of the first strand 5′ cDNA in 50 μl buffer containing: 40 mM Tricine-KOH pH 8.7, 15 mM KOAc, 3.5 mMMg(OAc) 2 , 3.75 μg/ml BSA, 0.005% Tween-20, 0.005% Noninet-P40, 0.2 mM dNTP's, 14 pmoles of pCP2r primer, 5 μl of 10× Universal primer Mix (UPM) and 1 μl 50× Advantage 2 polymerase Mix (Clontech, USA). Amplification was performed in a Bio-med thermocycler 60 (B. Braun). A first denaturation step (94° C., 2 min) was followed by 35 cycles of denaturation (94° C., 1 min), primer annealing (55° C., 1.5 min) and extension (72° C., 2 min). The extension time was increased by 3 sec at each cycle. Amplification was ended by a final extension step (72° C., 10 min). The amplified fragment was cloned in pGEM®-T vector and sequenced. 3′ RACE PCR The sequence information obtained after the sequencing of the 5′ end fragment was used to design a specific oligonucleotide pCP5 (5′-GCTTTTGCTGCCCGAGTCCACC) (SEQ ID No. 4), which was used for 3′-RACE amplification. 3′-RACE PCR was performed with 2.5 μl of SMART single strand 3′ cDNA in 50 μl buffer containing 40 mM Tricine-KOH pH 8.7, 15 mM KOAc, 3.5 mM Mg(OAc) 2 , 3.75 μg/ml BSA, 0.005% Tween-20, 0.005% Nonidet-P40, 0.2 mM dNTP's, 10 pmoles of pCP5 primer, 10 μl of 10× Universal primer Mix (UPM) and 1 μl 50 × Advantage 2 polymerase Mix (Clontech, USA). Amplification was performed via touchdown PCR, in a Bio-med thermocycler 60 (B. Braun). A first denaturation step (94° C., 1 min) was followed by: 5 cycles including denaturation at 94° C. for 30 sec and annealing/extension at 72° C. for 3 min 5 cycles including denaturation at 94° C. for 30 sec and annealing/extension at 70° C. for 30 sec and 72° C. for 3 min 30 cycles including denaturation at 94° C. for 30 sec and annealing/extension at 68° C. for 30 sec and 72° C. for 3 min. The amplified fragment was cloned in PGEM®-T vector and sequenced. Full Length cDNA The sequence information obtained after the sequencing of 5′-and 3′-RACE fragments was used to design two specific oligonucleotides. pCP8: A sense primer (5′-CAAAGAGAAAAAGAAAAGATGGC) (SEQ ID No. 5) pCP7r: A reverse primer (5′-CCCCAGAGCTTTACGATACGG) (SEQ ID No. 6). PCR reaction was performed with 2.5 μl first strand cDNA in 50 μl buffer containing: 40 mM Tricine-KOH pH 8.7, 15 mM KOAc, 3.5 mM Mg(OAc) 2 , 3.75 μg/ml BSA, 0.005% Tween-20, 0.005% Noninet-P40, 0.2 mM dNTP's, 10 pmoles of pCP8 primer, 10 pmoles of pCP7r primer and 1 μl 50× Advantage 2 polymerase Mix (Clontech, USA). Amplification was performed in a Bio-med thermocycler 60 (B. Braun). A first denaturation step (94° C., 1 min) was followed by 35 cycles of denaturation (94° C., 30 sec), primer annealing (63° C., 1 min) and extension (72° C., 2 min). The extension time was increased by 3 see at each cycle. Amplification was ended by a final extension step (72° C., 10 min). The amplified fragment was cloned in pGEM®-T Easy vector and sequenced. Sequencing and Analysis of DNA Sequences cDNA sequencing has been performed by Eurogentech (Belgium) and ESGS (France). Sequence analysis and comparison were performed with Lion's software bioScout, Lasergene software (DNAStar) and Genedoc programme. The cacao CP-III cDNA sequence is 1768 bp long. A putative initiation start codon was assigned by comparison with other carboxypeptidase sequences. It is located 25 bp from the 5′ end. The open reading frame is broken by a stop codon (TGA) at position 1549, followed by a putative polyadenylation signal (TATAAA) at position 1725. Cacao CP-III encodes a 508 amino acid type III carboxypeptidase C with a predicted molecular weight of 56 kDa and a pI of 5.04. The catalytic amino acids are present at position Ser 228 , Asp 416 and His 473 . A hydrophilicity analysis was performed using a Lasergene program (DNASTAR) and a window of 9. The results of a comparison of the hydrophilicity Plot-Kyte-Doolittle for the cacao CP-III sequence with Barley CP-ML CP-MII and CP-MIII ( FIG. 3 ) reveals that cacao CP-III encodes a hydrophilic protein with a very hydrophobic N-terminal end, indicating the presence of a signal peptide. Northern Blot Analysis Total RNA samples were separated on 1.5% agarose gel containing 6% formaldehyde. RNA was separated on agarose gels, then transferred to a nylon membrane and probed with radiolabelled cacao CP-III cDNA under stringent hybridization conditions. An equal loading of the RNA samples was confirmed by ethidium bromide straining of ribosomal RNA in the gel before transfer to the membrane ( FIG. 4 ). After electrophoresis, RNA was blotted onto nylon membranes (Appligene) and hybridized with 32 P-labeled cacao CP-III probe at 65° C. in 250 mM Na-phosphate buffer pH 7.2, 6.6% SDS, 1 mM EDTA and 1% BSA. Cacao CP-III cDNA fragment was amplified by PCR using pCP8 and pCP7R primers and labelled by the random priming procedure (rediprime™ II, Amersham Pharmacia Biotech). Membranes were washed three times at 65° C. for 30 mm in 2×SSC, 0.1%SDS, in 1×SSC, 0.1% SDS and in 0.5×SSC, 0.1%SDS. FIG. 4A illustrates the total RNA (15 μg per lane) from seed and leaf. FIG. 4B illustrates the total mature seed (15 μg per lane)from different T. cacao clones while FIG. 4C illustrates total RNA (15 μg per lane) from seed at different stages of germination.
The present invention relates to a novel carboxypeptidase gene and the polypeptide encoded thereby. In particular, the present invention relates to the use of the present carboxypeptidase and polypeptide in the manufacture of cocoa flavor and/or chocolate.
2
This is a continuation-in-part of this inventor's earlier patent application Ser. No. 923,612 filed 10/27/86, now abandoned. BACKGROUND AND PURPOSE The purpose of this patent application is to provide the snow skier, primarily when speeding downhill, with a pair of handlebars for his/her hands while in a tucked-in or semi-squatted position. In this tucked-in position, the skier becomes more aerodynamic than upright, thus achieving faster speeds, but having less control of the ski with little torque for turns, he/she having to rely solely on knee rotation for turning (as opposed to the hip rotation that is possible in the erect position). This invention provides the skier with a direct hand-control of the turning via a pair of uprightand-curved handles (i.e. "skigrips") that are attached to the ski (one per ski) in the position where the ordinary ski-bindings go; that is just slightly behind the mid-point of the ski length. In this inventor's earlier mentioned application for Handles for Tucked-in Skiing, now abandoned, the skier was locked in position by his/her feet at the ordinary place of the ski-bindings, thus the proposed handles had to be positioned way up front in the ski. The result, on extensive testing, was that such handles added little real maneuverability of the ski over what the foot alone had since the pivoting or turning/torque point of the ski especially a long, downhill ski is near its center. The so placed front handles permitted great speeds when pulled up (by better skimming the snow), but reducing the turning ability of the ski when bearing down. Such front placed handles had obvious limitations in practical terms for the average skier and average ski slope where for safety, control is emphasized over speed. Those handles would thus be limited to ad-hoc chutes and very straight downhill courses under very restricted circumstances. In contrast to the abandoned application, this application places a similar type of upright handlebar, not in the front of the ski, but in the very place where one would normally place one's foot: between the ski-bindings and locked in position (thus removably) by them. With the handlebars locked between the regular ski-bindings the skier now places his/her feet immediately behind the standard heel-piece of the bindings, this invention providing a pocket-shaped hold for the skier's boot-tip. In this way the skier's weight is all in the rear half of the ski, thus the front of the ski can better skim over the snow, and at the same time with the skier/leaning forward and grabbing the proposed handles the turning/torque point of the ski is kept at best possible point, that is, near its center. Extensive review of earlier prior art has been shown in the mentioned application. Additional prior art that specifically relates to handlebar attachments for skis include: The Ski Steering Apparatus of G.L. Parkinson (U.S. Pat. No. 4,643,444) which connects the front of the skis together with a handlebar attchment with telescoping and pivoting provisions, which in no way approaches this invention. The R.P. Brown's Ski Apparatus (U.S. Pat. No. 2,564,420) that consists of a rigid, tiltable frame with handlebars that are attached to the front tip of the skis, and is, in no way similar to this invention either. K.A. Henson's Sloping-Terrain Vehicle (U.S. Pat. No. 4,363,495) consists of a pair of handles attached together and holding the skis together by way of an articulated bridge; this device of his in no way accomplishes the purpose and versatility of this invention either. BRIEF DESCRIPTION OF THE INVENTION This paired sporting device is aimed at sliding on slippery slopes atop a pair of standard skis for snow or ice. Each skigrip or handlebar consists of a curved tubular inverted-L frame that goes attached upright to the ski near its center. This tubular frame is held in position via a special, rounded-and-rectangular specially shaped sole identical in thickness, shape and size, to the ski-boot sole of the user-skier. Such sole with its upright tubular frame or handle is locked in position by the ordinary ski-bindings. The skier places his/her feet on the ski behind the standard location, immediately behing the heel-pice of the regular binding and held firmly there by simply stepping into a pocket-shaped boot-toe hold. With the skier's boots held in this toe-hold and semisquatted or bent over (i.e. "tucked-in") the skier grabs with his/her hands the upright tubular handles or "skigrips" and skis downhill. A provision is made for these paired handlebars or skigrips to be directly attached to skis without a lockable ski-boot sole and thus without bindings. Various forms of attachment plates (i.e. male, female locking and side-to side parallel locking) are depicted. A provision is also made for some adjustability of the height of the handlebars and for a direct attachment to the ski without a ski-boot sole and bindings. Another provision is made for the special sole that locks into the ski bindings to have a length-adjusting mechanism so one sole can be locked into several lengths of permanently screwed-in bindings. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 Depicts a left lateral view of the instant invention, positioned in place on the skis and locked to them by the special sole. The rear toe hold is also shown and the tucked-in skier is drawn in dashed lines. FIG. 2 Depicts one handle bar or skigrip separated from its sole and position so it is mounted with its upper curved portion facing rearward. FIG. 3 Depicts a single handlebar or skigrip with its upper curved portion facing forward and each attachable/lockable element separated, but lined up in position from the ski and bindings to the skigrip and toe hold. The bottom of the handlebar acts as a female part over the plate. FIG. 4 Depicts the toe hold lined up over the ski behind the standard heel pice of the bindings. FIG. 5 Depicts the bottom end of the handlebar or skigrip as a male-fitting lined up over the female attachment plate and sole. FIG. 6 Depicts a direct attachment of the plate and its handlebar onto the ski without a special sole and without the need for bindings. FIG. 7 Depicts a special angle-attachment-plate for parallel, side-to-side bolted connection of the handlebar to such plate. FIG. 8 Depicts a single handlebar with a push-button telescopic heightadjusting mechanism. FIG. 9 Depicts the ski bindings-lockable special attachment sole herewith provided with a length-adjusting bolt. FIG. 10 Depicts a partial view of the rear of the ski with a simple elastic/adjustable strap as a toe hold fot the user's boot instead of the formed-pocket toe hold of FIG. 4. DETAILED DESCRIPTION OF THE INVENTION This paired recreational/sporting device is intended to aid the snow skier in balancing and in controlling the skis by providing means of direct hand control of the center portion of the ski as the skier leans forward or "tucks-in". To accomplish this purpose, the skier 1 stands with his/her feet on the rear of the skis 2, wearing either his/her own regular boots or standard ski-boots 3. The skier's weight goes just behind the heel piece of the standard ski bindings 4. To keep the skier's boot firmly in place, this invention provides a simple step-in toe hold 5. This toe hold 5 is made of light weight plastic sheeting material molded into a concavity that provides a semi-snug fit for the tip of the skier's boot. This plastic toe hold 5 has the concavity 6 or toe hold proper, a rectangular and horizontal plate 7 and an elastic strap 8. The concavity 6 and the plate 7 are all one piece. The plate 7 is firmly screwed in position, behind the heel piece of the standard binding 4 with the concavity obviously facing rearward, and left thus permanently attached to the ski. The elastic/adjustable strap 8 holds the skier's heel so his/her foot will remain in position even in a bumpy downhill ride, but can easily dislodge and free the skier in a tumble. The handlebars 9 of the paired device, being identical to one another, consist each of a rounded, light weight tubular frame, 1/2" to 1" in cross sectional diameter, in the approximate shape of an inverted letter L with a rounded angle. The horizontal upper portion 10 of the handle bar is horizontally flattened at its free tip. This horizontal portion 10 is provided with a rubberized non-slip padding 11 that covers as a continuous sheath the horizontal portion and the rounded angle 12 of the handlebar 9. The vertical portion of the handlebar(s) 9 has a horizontal perforation 13 approximately 21/2" from its bottom free end. This through-perforation accomodates a perforating and securing bolt/wing nut arrangement 14. The bottom free end 15 of the handlebar fits snuggly as a female component over the short, 3" tall vertical stem, with a matching perforation of the attachement plate 16. This plate 16 is a rectangular, 2" to 21/2" wide by 3" to 4" long by 1/8" to 1/4" thick sheet of metal with a short, 3" tall vertical stem in its center identified by the numeral 17. A provision is made in FIG. 5 to show the same described connection of bottom of handlebar 9 to attachment plate 16, but wherein the short vertical stem of the plate is here wider than the handlebar so in this fitting, the handlebar becomes the male part inside the short stem 18 of the attachment plate 16, being the perforation and bolt similar for both types of fitting. A provision is also made in FIG. 7 for the fitting between the bottom of the handlebar and the attachment plate to be a bolted, parallel and side-by-side fitting. The attachment plate here is identified by the numeral 19, plate that is a square-angled piece wherein its horizontal portion has an approximately rectangular/trapezoidal shape with 3 to 4 perforation to accomodate fastening screws, portion marked as 20. The vertical portion 21 of this plate 19 has two vertically lined up perforations 22 aimed at accomodating 1" to 11/2" bolts 23. These two bolts 23 hold together the plate 19 and, vertically, the handlebar 9. In a situation where the skier (or ski jumper) may desire to have the handlebars tilt forward or backward, only the top bolt of the two marked as number 23 would be used as a fastened, and at the same time, as a pivoting point for the handlebar. While the preliminary optimal height of the described handlebars would seem the mid-thigh level of the skier, personal preference, the skier's flexibility, the shoe-wear used and the level of speed and competition, may dictate lower or higher hand-grip position. Thus this invention, as per FIG. 8, makes a provision for the handlebars to have a height adjustment mechanism: The vertical portion of the handlebar 9 has two tubular segments telescoped into one anpther, one of them having a series 24 of vertically lined up holes, destined to lock the inner segment in position at a particular desired height, via a spring-loaded push-button located in the inner and thinner segment 25. While the attachment plates 16 (with male or female stem) or 19 can be directly fastened to the mid-section of the ski 2 as in FIG. 6, this invention looks particularly at making the described handlebars 9 and their use, totally compatible with an ordinary, standard set of skis with an attached set of standard ski bindings. For this purpose, FIGS. 1, 2, 3, 5 and 7 depict the said handlebars 9 attached to their attachment plate (numerals 16 and 19), and the attachment plate in turn being fastened over a rectangular, rounded board 26 shaped and sized identical to the size of the skier's standard ski-boot sole. This means that this board or sole 26 has front and rear rounded edges, being thicker in the rear and perfectly fitting into the strong lock provided by the standard ski bindings with their heel piece 4 and their toe piece 27. The material of the sole 26 can be either wood or plastic as in current use in the ski boot industry. This important sole 26 makes this handlebar very versatile as it allows marketing of the device to those already in posession of standard skis, plus it allows skiers to use their skis either in a standard fashion or in the herewith proposed tucked-in-with-handlebars position. It also allows skiers to "stand" normally on their skis locked into the bindings to take the chair-lift (carrying this device on their back pack) and to decide at the top of the slope which way to ski downhill. A provision is made by this invention to allow the skier the placement of the described handlebars 9 with their padded top horizontal portion 10 facing frontward or the direction of travel, or rearward as in FIG. 2, this depending on the skier's height, preference, etc. The tip of the horizontal portion 10 is horizontally flattened to allow the skier the simultaneous hand-grip of ski pole (if he/she carries them) and of these handlebars in such a way that the handle of the ski pole rests directly above the flattened portion 10 of the handlebar(s) 9. A string-like leather or plastic loop 28 is fastened to the handlebar so the skier can pass his/her hand through it and thus retain a hold of the handlebar(s) in a tumble. This item is also important: In a tumble at low speeds, the skier is likely to fall to the side while continuing to hold on to the described handlebars 9 and thus nothing runs off to get lost down hill or to hit others; in a tumble at greater speeds the skier may let go of the handlebars, so skis and handlebars together could run off unattended, but now with the safety loop 28, the handlebars stay with the skier; if in this case the ski bindings do not release the described sole 26, then the whole apparatus stays with the skier, but if the bindings do release, the skier keeps only the handlebars-and-sole device and the unattended skis with their built-in automatic brakes 29 come by themselves to a quick stop. This brake device is commonly required by current regulations in ski resorts. A provision is made, as shown in FIG. 9, to have the ski boot sole-shaped special sole 26 adjustable to different lengths, so the device can be used by different skiers of different boot size. This may be important as a ski-rental item where the separate pieces of the ski gear are used (rented) by many subjects. For this purpose, the described sole 26, with its specially thinner front and thicker back is cut off into two separate pieces, front 30 and rear 31, the front piece 30 having attached with screws the attachment plate 16 provided in turn either with a vertical male stem 17, or a female stem 18. Both front and rear pieces of this sole, 30 and 31 respectively, are interconnected by a built-in bolt 31. This bolt 31 is glued firmly into a single block to front piece 30 and then put in position by entering the matching threaded opening lined up in rear piece 31. No torsion-locking device is necessary as torsion and dislodging will be prevented by the sole 26 being locked into the ski bindings when in use. While the main practical and marketable point of this invention may be its locking-in-position-on-the-ski sole shaped identical to the sole of standard ski boots, which makes the device (and thus the bindings) versatile and accesible to those who already have skis, its major argument and key point for mechanical advantage over the author's prior applications Ser. Nos. 890,029 and 923,612 (both abandoned) and over the earlier prior art of others, is the placement of the handles over the center of mid-point of the ski. In those inventions, the steering handles, shaped or mechanically connected one way or another to one or to both skis, are mounted on the front part of the ski(s). Extensive testing indicates that the more forward on the skis the handles or steering devices are, the less steerable the skis are. Indeed, pulling up on the handles and trying to turn the whole thing makes the front of the skis skim the snow, thus speeding down too fast beyond easy control to turn them; pushing on them or bearing weight on them makes the skis "track" or run down in parallel, again making turning very difficult. In contrast, in this invention, the handlebars are placed in the center of the ski in the spot where on standard skis with standard bindings the skier's weight is located, thus leaving free the front of the skis to quickly respond to the torque applied to their center portion. A provision is also made for the toe hold 5 to consist simply of an elastic/adjustable transverse strap 32 as shown in FIG. 10.
This sporting, mechanical, paired, ski-steering device consists of a pair of upright curved, sturdy, handlebars attached straight up to the center of a snow ski (one per ski) in the area where standard ski bindings are mounted. The skier stands in the rear of the skis, one foot on each ski and with each foot maintained in position by a toe hold, and bends over or "tucks-in" grabbing with his/her hands these handlebars to provide control and steering. The handlebars can be directly attached to the center of the ski, but as a more convenient and versatile advantage, can also be locked on the ski by the ordinary ski bindings via a special sole that is sized and shaped at its two ends identical to the sole of the user's ski boots sole.
0
CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation, and claims priority, of co-pending U.S application Ser. No. 12/753,524, filed Apr. 2, 2010, which claims priority to U.S. Provisional Application Ser. No. 61/212,104, filed Apr. 7, 2009. The contents of all the prior applications are incorporated herein by reference in their entirety. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to body-implantable devices. More particularly, the present invention relates to a percutaneously insertable and expandable inter-vertebral disc prosthesis. Specifically, the present invention comprises a novel nuclear prosthesis, a specially designed delivery apparatus, and a loading apparatus for loading the nuclear prosthesis within the delivery apparatus. 2. Description of the Related Art The role of the inter-vertebral disc in spine biomechanics has been the subject of extensive research and is generally well understood. A typical native spinal unit is shown for exemplary purposes in FIG. 22A . The functional spinal unit, or spinal motion segment 500 consists of two adjacent vertebrae 502 and 504 , the inter-vertebral disc 506 and the adjacent ligaments (not shown). The components of the disc are the nucleus pulposus 506 a , the annulus fibrosis 506 b , and the vertebral end-plates 506 c . These components act in synchrony and their integrity is crucial for optimal disc function. During axial loading of the normal native disc 506 , the pressure of the nucleus pulposus 506 a rises, transmitting vertical force on the end plates 506 c and outward radial stress on the annulus fibrosis 506 b , as shown by the direction arrows in FIG. 22A . The vertical stress is transformed to tensile forces in the fibers of the annulus fibrosis 506 b . Because the gelatinous nucleus pulposus 506 a is deformable but noncompressible, it flattens radially, and the annulus fibrosis 506 b bulges and stretches uniformly. Flexion of the spine involves the compression of the anterior annulus fibrosis 506 b , as well as the nucleus pulposus 506 a . The nucleus pulposus 506 a deforms and migrates, posteriorly stretching the annular fibers and expanding radially. Thus, the nucleus pulposus 506 a and annulus fibrosis 506 b function synergistically as a cushion by reorienting vertical forces radially in a centrifugal direction. The native vertebral end plate 506 c prevents the nucleus pulposus from bulging into the adjacent vertebral body by absorbing considerable hydrostatic pressure that develops from mechanical loading of the spine. The end plate 506 c is a thin layer of hyaline fibrocartilage with subchondral bone plate, typically around 1 millimeter thick. The outer 30% of the end plate 506 c consists of dense cortical bone and is the strongest area of the end plate 506 c . The end plate 506 c is thinnest and weakest in the central region adjacent to the nucleus pulposus. With aging and repetitive trauma, the components of the inter-vertebral disc 506 undergo biochemical and biomechanical changes and can no longer function effectively, resulting in a weakened inter-vertebral disc 506 . As the disc 506 desiccates and becomes less deformable, the physical and functional distinction between the nucleus pulposus 506 a and the annulus fibrosis 506 b becomes less apparent. Disc desiccation is associated with loss of disc space height and pressure. The annulus fibrosis 506 b loses its elasticity. The apparent strength of the vertebral end-plates 506 c decreases and vertebral bone density and strength are diminished. This leads the end-plates 506 c to bow into the vertebral body, imparting a biconcave configuration to the vertebral body. Uneven stresses are created on the end plates 506 c , annulus fibrosis 506 b , ligaments (not shown), and facet joints (not shown), leading to back pain. At this point, the annulus fibrosis 506 b assumes an inordinate burden of tensile loading and stress, and this further accelerates the process of degeneration of the annulus fibrosis 506 b . Fissuring of the annulus fibrosis 506 b further diminishes its elastic recoil, preventing the annulus fibrosis 506 b from functioning as a shock absorber. Leakage of the nuclear material can cause irritation of the nerve roots by both mechanical and biochemical means. Eventually, degenerative instability is created, leading to both spinal canal and neuroforaminal stenosis. Historically, spine surgery consisted of simple decompressive procedures. The advent of spinal fusion and the proliferation of surgical instrumentation and implants has led to an exponential utilization of expensive new technologies. As an alternative to open surgical discectomy and fusion, Minimally Invasive Spinal Surgery (MISS) has been advocated. Thus far, the primary rationale for favoring the MISS approach has been to lessen postoperative pain, limit the collateral damage to the surrounding tissues, and hasten the recovery process rather than affect long term outcomes. Despite the lack of clear superiority and outcome data, these technologies have continued to flourish. However, many spinal surgeons remain skeptical about the positive claims regarding MISS, citing certain drawbacks, including increase in operating room time, requirement for expensive proprietary instruments, increased cost, and the technically demanding nature of the procedure. Despite the advantage of a minimal incision approach, MISS requires an adequate decompression and/or fusion procedure in order to have results comparable to traditional open surgical approaches. Ideally, a nuclectomy and implant insertion would be performed through a percutaneous posterolateral approach. Advantages of the percutaneous posterolateral approach over conventional open surgery and MISS include obviating the need for surgically exposing, excising, removing, or injuring interposed tissues; preservation of epidural fat; avoiding epidural scarring, blood loss, and nerve root trauma. Other advantages include minimizing “access surgery” and hospitalization costs, and accelerating recovery. A percutaneous procedure may be expeditiously used on an outpatient basis in selected patients. On the other hand, percutaneous insertion imposes a number of stringent requirements on the nuclear prosthesis and its method of delivery. Several devices have been used to fill the inter-vertebral space void following discectomy in order to prevent disc space collapse. These devices generally fall into two categories: fusion prostheses and motion prostheses. Fusion prostheses intended for MISS insertion offer few if any advantages over those for open surgical technique. While these types of implants eliminate pathological motion, they also prevent normal biomechanical motion at the treated segment. Greater degrees of stress are transmitted above and below the treated segment, often leading to accelerated degeneration of adjacent discs, facet joints, and ligaments (adjacent level degeneration). Motion prostheses generally aim at restoring disc height, shock absorption, and range of motion, thus alleviating pain. Artificial motion prostheses may be divided into two general types: the total disc prosthesis and the nucleus prosthesis. The total disc prosthesis is designed for surgical insertion, replacing the entire disc, while the nucleus prosthesis is designed for replacing only the nucleus pulposus, and generally may be inserted by open surgical or MISS methods. Prior designs of motion nucleus prostheses include enclosures that are filled with a diverse variety of materials to restore and preserve disc space height while permitting natural motion. However, there are several shortcomings of prior nucleus motion prostheses designs. Some of the prior nucleus motion prostheses require surgical approaches for insertion that involve removal of a significant amount of structural spinal elements including the annulus fibrosis. Removal of these structural spinal elements causes destabilization of the spinal segment. Prior nuclear motion prosthesis designs also fail to provide the outer margin of the nuclear prosthesis with surface and structural properties that encourage native tissue ingrowth. Instead, such prostheses are made from generally non-porous materials that impede full incorporation of the nuclear prosthesis into the surrounding annular margin. Some prior designs have annular bands along the outer periphery of the nucleus motion prostheses. However, prior annular bands are non-compliant. This is disadvantageous because it reduces the radial outer expansion required for load dampening. Thus, the load is transferred to the end plates of the vertebrae, which can withstand only limited deformation. The result is that the end plates eventually fail, resulting in loss of intradiscal pressure, accelerated degeneration, and subsidence of the nuclear prosthesis. Other prostheses do not have an annular band. These prostheses tend to exert untoward pressure on an already weakened armulus fibrosis. Particularly, such a prosthesis tends to protrude into a pre-existing annular tear. Other designs fail to incorporate or use a central gas cushion with a valve system or assembly that does not leak. Still others concentrate the harder load bearing component of the nuclear prosthesis in the central aspect of the disc, predisposing the nuclear prosthesis to subsidence. Another problem with prior nuclear motion prostheses is the imprecise sizing and tailoring of the nuclear prosthesis. Over sizing places unnecessary stress on the already damages and degenerated annulus fibrosis, while under sizing of the nuclear prosthesis may result in inadequate contact with the inner wall of the annulus fibrosis, and possibly non-integration and migration of the nuclear prosthesis. Other designs of nucleus motion prostheses suffer draw backs such as bulkiness, inelasticity, inability to fold and pack the nuclear prosthesis into a delivery cannula or apparatus for percutaneous implantation into a patient. In fact, percutaneous delivery of a motion nucleus prosthesis heretofore, has been unavailable. Applicants here propose to overcome the disadvantages of the prior designs of nucleus motion prostheses by providing a multi-compartment nuclear prosthesis having a semi-compliant annular reinforcement band disposed adjacent or contiguously around the periphery of a rubber filled annular enclosure. The annular enclosure nests a central, gas cushioned nuclear enclosure and an integrated sealing valve assembly. The nuclear prosthesis of the present invention is foldable to fit within a delivery apparatus, and is intended for percutaneous insertion into a nuclear space void following percutaneous total nuclectomy. Once percutaneously inserted, the nuclear prosthesis is expandable by an inflation-assisting device to provide cushioning and stability to a spinal segment weakened by degeneration. SUMMARY OF THE INVENTION The present invention overcomes the deficiencies of prior nuclear motion prostheses, offers several advantageous properties, and provides a system for sizing, forming, delivering, and deploying a nuclear prosthesis into the inter-vertebral disc space. The percutaneously implantable nuclear prosthesis, formed in accordance with the present invention, utilizes the advantages of both a textile prosthesis and a polymer prosthesis to create a compartmentalized composite structure, having characteristics closely resembling the properties of a healthy native inter-vertebral disc. The nuclear prosthesis is comprised of an annular structure and a nuclear structure. The annular structure comprises an annular enclosing layer which defines an annular enclosure, an annular reinforcement band adjacent the periphery of the annular enclosing layer, a sealing valve core disposed within the annular enclosure and adjacently attached to the annular enclosing layer, and in-situ curable rubber, which is injected into the annular enclosure. The nuclear structure comprises a nuclear enclosing layer which defines a nuclear enclosure and an indwelling catheter mounted and bonded to a neck portion of the nuclear enclosing layer, and extends distally into, and is enclosed within the nuclear enclosure. Referring to FIG. 22B the structure of the nuclear prosthesis comprising the annular structure 11 filled with the deformable, but not compressible in-situ curable rubber and the nuclear structure 21 centrally located within the annular structure 11 and being filled with a compressible gas allows for the vertical and horizontal load stresses placed on the inter-vertebral disc space to be redirected inward, centrally toward the nuclear structure 21 (see direction arrows of FIG. 22B ), instead of outward. Moreover, annular structure 11 has a biocompatible outer annular reinforcement band that encourages tissue in-growth of the native annulus fibrosis 506 b , thereby providing reinforcement to the native annulus fibrosis. According to the present invention, there is provided a percutaneously insertable and detachable nuclear prosthesis having an annular enclosing layer that defines an annular enclosure. The annular enclosing layer is made of an annular tubular elastomeric membrane, is contiguous along its outer periphery with a textile annular reinforcement band, and incorporates a sealing valve core. Central to the annular enclosing layer is a nuclear enclosing layer defining a nuclear enclosure. The nuclear enclosing layer has a neck region. The neck region of the nuclear enclosing layer defines an open mouth that receives an indwelling catheter. The neck region is mounted on the indwelling catheter. The indwelling catheter is a tube that defines a lumen. The indwelling catheter is coupled to a sealing valve core which is disposed within the annular enclosure, and has its lumen plugged by a sealing plug after inflation within the inter-vertebral disc space. The nuclear prosthesis is detachably mounted to a distal end of an inflation stylus and is loaded within a distal end of a delivery apparatus. The inflation stylus has three inflation tubes projecting from the distal end of the inflation stylus and slidably insertable through the sealing valve core of the sealing valve assembly. The sealing valve core is formed of a resilient material and has three pathways being defined by three parallel channels extended through the sealing valve core. Upon insertion of the three inflation tubes of the inflation stylus through the channels of the sealing valve core, the pathways take the form of cylindrical apertures in precise mating alignment with the inflation tubes of the inflation stylus to provide fluid-tight seal against and around the outer surfaces of the inflation tubes. The central inflation tube is a nuclear access tube that provides pressurized fluid to the nuclear enclosure. One of the outer tubes is an annular inlet tube that provides pressurized fluid to the annular enclosure through an inlet port provided in the sealing valve core. The other outer tube is an annular outlet tube that receives pressurized fluid from the annular enclosure through an outlet port provided in the sealing valve core. The annular inlet tube and the annular outlet tube have side pores in the walls of the tubes adjacent the closed tips of the tubes whereby in-situ vulcanizing rubber flows through the side pore in the annular inlet tube into one end of the annular enclosure and back through the side pore of the annular outlet tube, and into the inflation stylus. After inflation of the annular enclosure and nuclear enclosure, the inflation stylus can be efficiently disengaged from the sealing valve core, and upon withdrawal thereof, the pathways return to an elongated slit or channel configuration to provide a fluid tight seal for the inflated nuclear prosthesis. It is, therefore, a general object of the present invention to provide a nuclear prosthesis which exhibits an optimal overall combination of physical, viscoelastic, and other properties superior to previous designs of motion nucleus prostheses. It is another object of the present invention to provide a nuclear prosthesis that is fundamentally reliable and durable, and utilizes the latest in surface modification technology to enhance the bio-compatibility, bio-durability, infection resistance, and other aspects of performance. It is another object of the present invention to provide a nuclear prosthesis that reduces stress on the vulnerable central portions of the native vertebral end plates. It is another object of the present invention to reduce the stress on the vulnerable central portions of the native vertebral end plates by providing a nuclear prosthesis that redirects the vector of forces caused by load stress inward, toward the core or center of the nuclear prosthesis. In this regard, the present invention provides a gas-filled central enclosure to aide in load bearing, cushioning, shock absorption and stabilization by directing the vector of forces toward the gas-filled central enclosure. The present invention redirects both lateral and vertical forces toward the gas-filled central enclosure, thereby providing protection to the vertebral end plates. The present invention accomplishes the redirection of vector forces by having a non-compliant annular reinforcement band along the outer periphery of the nuclear prosthesis, and a compressible gas filled central nuclear enclosure. It is yet another object of the present invention to provide a nuclear prosthesis that provides reinforcement and structural support to the native annulus fibrosis. The annular reinforcement band of the present invention encourages native tissue in-growth of the native annulus fibrosis to provide added stabilization and reinforcement. It is still another object of the present invention to provide a nuclear prosthesis wherein the compliance of the nuclear prosthesis increases progressively toward the center of the nuclear prosthesis. Each component of the nuclear prosthesis is tailored to provide suitable viscoelastic properties that contribute to the overall performance of the nuclear prosthesis. This arrangement is intended to relieve the stress on the native annulus fibrosis by redirecting the radial outer vector of forces centrally toward the nuclear enclosure. The nuclear prosthesis is thus rendered iso-elastic with respect to the spinal segment. Yet another object of the present invention is to provide a nuclear prosthesis that has expansion tailorability. The nuclear prosthesis can be expanded to variable sizes to accommodate the dimensions of the evacuated nuclear space. The nuclear enclosing layer, annular enclosing layer and annular reinforcement band possess the ability to be first inflated or stretched to its unextended or working profile and then, there-beyond to a limited extent and/or controlled extent by the application of greater pressure. The controlled flexibility of the textile annular reinforcement band and the expansion of the annular and nuclear enclosures can accommodate a wider range of nuclear space dimensions, reducing the need to precisely match the nuclear prosthesis to the nuclear space as to size. It is yet a further object of the present invention to provide an inflation-assisted expandable nuclear prosthesis that distracts the disc space, and supports and reinforces the annulus fibrosis while keeping the ligaments and facet joints in a taut condition. It is another object of the present invention to provide a novel sealing valve assembly which has a sealing valve core integrally bonded to the annular enclosing layer within the annular enclosure, having a mounting region adapted on its inner margin for fluid tight bonding to an indwelling catheter lying within the nuclear enclosure. The sealing valve core of the sealing valve assembly is detachably connected to the tip of the delivery apparatus and is self-sealing upon removal of the inflation stylus. It is another object of the present invention to provide a nuclear prosthesis which can be geometrically and elastically deformed to reduce its axial and transverse diameter through radial elongation, into a minimal profile for ease of insertion into the delivery apparatus, while minimizing the risks that could be associated with such flexibility. This is achieved by the components of the nuclear prosthesis being suitably configured and dimensioned to form a perfect mating fit to each other and to the nuclear enclosing layer. The annular reinforcement layer, annular enclosing layer and nuclear enclosing layer must cooperate in a synchronized fashion to achieve a precise folded and wrapped configuration. The folding of the nuclear prosthesis is further achieved by minimizing the combined thicknesses of the annular enclosing layer and nuclear enclosing layer and optimizing the longitudinal flexibility and radial compliance of the annular reinforcement band by careful selection of the type of bio-compatible yarn, the number of layers, the heat set conditions, and the angles at which braids are formed. The folding of the nuclear prosthesis is also aided by the selection and use of a semi-compliant medical balloon material for the annular and nuclear enclosing layers. It is further an object of the present invention to provide a nuclear prosthesis that has a porous outer margin thereby facilitating the incorporation of the nuclear prosthesis into the nuclear space. It is yet another object of the present invention to provide a delivery apparatus having an assembly of coaxial telescoping cannulas with the nuclear prosthesis disposed therein, and a method of delivering the nuclear prosthesis percutaneously to the nuclear space. The delivery apparatus houses and carries the folded nuclear prosthesis within its delivery cannula. The delivery cannula also houses and incorporates an inflation stylus defining three tubes in fluid communication with the three chambers or pathways of the sealing valve core of the nuclear prosthesis. Within the delivery cannula is a specially designed release cannula adjacent the sealing valve core to release the inflation stylus from the nuclear prosthesis. A typical procedure for implantation of the nuclear prosthesis involves performing an initial percutaneous nuclectomy through a percutaneous access device, insertion of the delivery apparatus within the percutaneous access device, insertion of the delivery cannula carrying the nuclear prosthesis and deploying the nuclear prosthesis within the nuclear space void. In deployment, the annular and nuclear enclosures are expanded using any suitable fluid delivery system, allowing the nuclear prosthesis to assume a substantially discoid shape as the nuclear prosthesis radially and axially expands and substantially conforms to the shape of the nuclear space void. The annular and nuclear enclosures are inflated simultaneously with a pressurized liquid until adequate disc space distraction is achieved and a predetermined pressure level within the nuclear prosthesis is achieved. The annular enclosure is inflated with an in-situ curable rubber, and the nuclear enclosure is inflated with a liquid such as saline. After curing of the in-situ curable rubber within the annular enclosure occurs, the liquid within the nuclear enclosure is replaced with a compressible gas. Nitrogen, carbon dioxide, or many other suitable gases can be used within the nuclear enclosure. At this point, the indwelling catheter is plugged with a sealing plug introduced into the indwelling catheter and pushed therein. The delivery cannula is detached from the sealing valve core by the release cannula, and the delivery apparatus is then removed. These and other objects, aspects, features and advantages of the present invention will be clearly understood and explained with reference to the accompanying drawings and through consideration of the following detailed description. DESCRIPTION OF THE DRAWINGS FIG. 1 is a sectional side view of the annular structure of the nuclear prosthesis of the present invention; FIG. 1A is a sectional side view of the loading apparatus of the present invention with an inflated nuclear prosthesis of the present invention therein; FIG. 1B is a sectional side view of an inflated annular enclosing layer of the nuclear prosthesis of the present invention; FIG. 1C is a sectional side view of an inflated annular enclosing layer of the nuclear prosthesis of the present invention; FIG. 1D is a sectional top view of the delivery apparatus of the present invention with the nuclear prosthesis of the present invention loaded therein; FIG. 2 is a sectional side view of an inflated annular enclosing layer and deflated nuclear enclosing layer of the nuclear prosthesis of the present invention; FIG. 2A is a sectional side view of the loading apparatus of the present invention with a partially deflated nuclear prosthesis of the present invention therein; FIG. 2B is a sectional side view of the annular enclosing layer of the nuclear prosthesis of the present invention in a partially stretched position during loading into the delivery apparatus; FIG. 2C is a sectional side view of the nuclear prosthesis of the present invention in a partially deflated state; FIG. 2D is a sectional top view of the delivery apparatus of the present invention with the nuclear prosthesis of the present invention loaded thereon; FIG. 3 is a sectional side view of the nuclear prosthesis and the inflation stylus of the present invention; FIG. 3A is a sectional side view of the loading apparatus of the present invention showing the loading of a deflated nuclear prosthesis of the present invention onto the delivery apparatus of the present invention; FIG. 3B is a sectional side view of the annular enclosing layer of the nuclear prosthesis of the present invention in a fully stretched position during loading onto the delivery apparatus; FIG. 3C is a sectional side view of the nuclear prosthesis showing the folding of the annular enclosing layer around the nuclear enclosing layer when the nuclear prosthesis is deflated; FIG. 3D is a sectional top view of the delivery apparatus of the present invention with the nuclear prosthesis of the present invention loaded thereon and retracted therein, with the delivery apparatus disposed within an access cannula; FIG. 4 is a sectional top view of the nuclear prosthesis and the inflation stylus of the present invention; FIG. 5 is a sectional top partially exploded view of the sealing valve core of the sealing valve assembly of the nuclear prosthesis of the present invention; FIG. 6 is a sectional top view of the sealing valve core of the sealing valve assembly of the nuclear prosthesis of the present invention; FIG. 7 is a sectional top view of the sealing valve core of the sealing valve assembly of the nuclear prosthesis of the present invention; FIG. 8 is a side view of the indwelling catheter and the mounting region of the nuclear enclosing layer of the nuclear prosthesis of the present invention; FIG. 9 is a sectional side view of the annular enclosing layer, retaining ring and the layers of the annular reinforcement band of the nuclear prosthesis of the present invention; FIG. 10 is a sectional side view of the inflation stylus of the present invention and the of the nuclear prosthesis of the present invention showing interaction of the nuclear access tube with the indwelling catheter; FIG. 11 is a sectional top view of the inflation stylus of the present invention; FIG. 11A is a sectional top view of the inflation stylus of the present invention and the of the nuclear prosthesis of the present invention showing interaction of the tubes of the inflation stylus with the ports and pathways of the sealing valve core; FIG. 11B is a sectional top view of the inflation stylus of the present invention and the of the nuclear prosthesis of the present invention showing interaction of the tubes of the inflation stylus with the ports and pathways of the sealing valve core; FIG. 12 is a side view of the release cannula of the delivery apparatus of the present invention interacting with the annular enclosing layer of the nuclear prosthesis of the present invention; FIG. 13 is a side view along line 12 - 12 of FIG. 12 showing the connection of the inflation stylus to the of the nuclear prosthesis of the present invention; FIG. 14 is a sectional side view showing the connection of the inflation stylus to the of the nuclear prosthesis of the present invention; FIG. 15 is a sectional side view showing the connection of the inflation stylus to the of the nuclear prosthesis of the present invention; FIG. 16 is a sectional side view showing the annular enclosing layer folded around the nuclear enclosing layer when the is a sectional side view showing the connection of the inflation stylus to the of the nuclear prosthesis of the present invention is deflated; FIG. 17 is a perspective view of the outer layer of the annular reinforcement band of the nuclear prosthesis of the present invention; FIG. 18 is a perspective view of one of the middle layers of the annular reinforcement band of the nuclear prosthesis of the present invention; FIG. 19 is a perspective view of the inner layer of the annular reinforcement band of the nuclear prosthesis of the present invention; FIG. 20 is a sectional side view of the nuclear prosthesis of the present invention after delivery and inflation with fluid within the patient; FIG. 21 is a sectional side view of the nuclear prosthesis of the present invention after delivery and inflation with fluid within the patient; FIG. 22A is a rear view of a native inter-vertebral disc space showing the direction of dispersion of typical horizontal and vertical load forces; and FIG. 22B is a rear view of an inter-vertebral disc space with the nuclear prosthesis of the present invention therein, showing redirection of dispersion of typical horizontal and vertical load forces by the nuclear prosthesis of the present invention. DESCRIPTION OF THE INVENTION Referring to FIGS. 1 through 4 the nuclear prosthesis 10 of the present invention is disclosed. Nuclear prosthesis 10 comprises an annular structure 11 and a nuclear structure 21 . Annular structure 11 comprises an annular enclosing layer 12 defining an annular enclosure 14 , and nuclear structure 21 comprises a nuclear enclosing layer 22 defining a nuclear enclosure 24 . Nuclear enclosing layer 22 is disposed adjacent annular enclosing layer 12 in the central space defined by annular enclosing layer 12 , along an inner margin 16 thereof. Annular structure 11 of nuclear prosthesis 10 further comprises an annular reinforcement band 20 contiguous with or adjacent a peripheral or outer margin 18 of the inflatable annular enclosing layer 12 and a sealing valve core 28 of a sealing valve assembly 26 . Annular enclosing layer 12 incorporates the sealing valve core 28 and annular enclosure 14 filled in-situ with curable rubber. In its inflated state, nuclear prosthesis 10 is substantially discoid in shape, as shown in FIGS. 20 and 21 . Annular enclosure 14 is in communication with an inlet port 36 a and an outlet port 38 a of sealing valve core 28 . Nuclear structure 21 comprises nuclear enclosing layer 22 , which defines a discoid inflatable nuclear enclosure 24 , and an indwelling catheter 32 . A neck portion 22 a of nuclear enclosing layer 22 is mounted on indwelling catheter 32 , which has a side-pore 32 a and a closed tip 32 d (see FIG. 8 ). Nuclear enclosing layer 22 is filled in-situ with compressible gas and converges on a neck portion 22 a adapted for fluid-tight bonding to indwelling catheter 32 (see FIG. 8 ). Returning to FIGS. 1 through 4 , indwelling catheter 32 includes a bulbous portion 32 b on the proximal end thereof, which is adapted to be coupled within a sealing valve core 28 of sealing valve assembly 26 to a pressurized fluid for inflation of nuclear enclosure 24 . Bulbous portion 32 b of indwelling catheter 32 is snap-secured and adhesively bonded to sealing valve core 28 so that a fluid-tight connection will be achieved. Referring to FIGS. 1D, 2D and 3D , a delivery apparatus 200 is disclosed. Delivery apparatus 200 is coaxially and telescopically slidable within an access cannula 202 . A distal delivery cannula 204 of delivery apparatus 200 coaxially encloses a release cannula 206 (see FIGS. 10, 11A, 11B and 12 ) and an inflation stylus 100 . Referring to FIGS. 4, 11, 11A and 11B , inflation stylus 100 is a rigid tube with a triple lumen that terminates in three inflation tubes 102 , 104 and 106 . Inflation tubes 102 , 104 and 106 define inflation lumens therein, and are in fluid communication with annular enclosure 14 and nuclear enclosure 24 via sealing valve core 28 . The three inflation tubes are an annular inlet tube 102 , an annular outlet tube 104 and a nuclear access tube 106 . Annular inlet tube 102 , annular outlet tube 104 and nuclear access tube 106 project from the distal end of inflation stylus 100 and are detachably secured to three corresponding pathways 36 b , 38 b and 40 , respectively, within sealing valve core 28 . Inflation tubes 102 , 104 and 106 are adapted to mate with the three corresponding pathways 36 b , 38 b and 40 , respectively, of sealing valve core 28 . In order to couple inflation stylus 100 to sealing valve core 28 , inflation tubes 102 , 104 and 106 are inserted through the inflation bores 36 c , 38 c and 40 a , respectively, which are disposed on the outer margin of sealing valve core 28 (see FIGS. 12 through 14 ). Inflation tubes 102 , 104 and 106 then extend into the slit-like pathways 36 b , 38 b and 40 , respectively. A fluid-tight communication is formed between annular enclosure 14 through inlet port 36 a and outlet port 38 a , and through annular inlet tube 102 and annular outlet tube 104 . Annular inlet tube 102 has a side pore 102 a , and annular outlet tube 104 has a side pore 104 a . Side pores 102 a and 104 a are located towards the closed distal ends of the annular inlet tube 102 and annular outlet tube 104 , respectively. Side pore 102 a provides a fluid-tight communication with inlet port 36 a , and side pore 104 a provides a fluid-tight communication with outlet port 38 a of sealing valve core 28 . A third fluid-tight communication is formed between nuclear enclosure 24 and inflation stylus 100 , through nuclear access tube 106 , which terminates with an end bore 106 a . Nuclear access tube 106 slides through passage 40 a and engages a proximal end 32 c of indwelling catheter 32 . Referring to FIGS. 4 through 9, 11A and 11B , the design of sealing valve assembly 26 is disclosed. Sealing valve assembly 26 employs sealing valve core 28 which permits the passage of fluid through inlet port 36 a , outlet port 38 a and indwelling catheter 32 , but prevents the flow of fluid through sealing valve core 28 when tubes 102 , 104 and 106 are removed from pathways 36 b , 38 b and 40 , respectively. Sealing valve core 28 is formed of a resilient material and contains the three constricted slit-like pathways 36 b , 38 b and 40 for frictionally engaging the outer surfaces of inflation tubes 102 , 104 and 106 , respectively, so that a predetermined force is required to withdraw inflation stylus 100 from sealing valve core 28 . Pathways 36 b , 38 b and 40 define passageways through which inflation tubes 102 , 104 and 106 , respectively, may be inserted without imparting damage to sealing valve core 28 . Sealing valve assembly 26 comprises sealing valve core 28 , indwelling catheter 32 , and a sealing plug (not shown). Sealing valve core 28 has the general cross-sectional configuration as inflated annular enclosure 14 , and is substantially concentric with inflated annular enclosing layer 12 . Sealing valve core 28 has an outside diameter which is slightly smaller than the diameter of inflated annular enclosure 14 , allowing for additional thickness contributed by annular enclosing layer 12 adjacently enclosing sealing valve core 28 . The additional thickness is crucial during loading nuclear prosthesis 10 onto delivery apparatus 200 . Sealing valve core 28 is preferably fabricated by molding from implantable grade elastomeric material (not shown), such that when an in-situ curable rubber such as RTV liquid silicon or other suitable RTV liquid elastomer is injected in-situ into annular enclosure 14 , a strong bond is formed between the thermoset silicon of sealing valve core 28 and in the in-situ cured rubber to create a unified load-bearing cushion. Preferably, both sealing valve core 28 and the in-situ curable rubber have a similar modulus of elasticity. Referring to FIGS. 11A and 11B , sealing valve core 28 detachably mounted on the distal end of inflation stylus 100 is shown. Inflation tubes 102 , 104 and 106 at the distal end of inflation stylus 100 are inserted through pathways 36 b , 38 b and 40 , respectively, of sealing valve core 28 . In this configuration, side pore 102 a of annular inlet tube 102 and side pore 104 a of annular outlet tube 104 are in alignment with inlet port 36 a and outlet port 38 a , respectively, of the sealing valve core 28 . Pathways 36 b , 38 b and 40 in sealing valve core 28 are substantially collapsible such that they take the form of three elongated slits prior to insertion of inflation tubes 102 , 104 and 106 therein. Upon insertion of inflation tubes 102 , 104 and 106 through pathways 36 b , 38 b and 40 , respectively, detachable fluid-tight engagement is achieved between inflation tubes 102 , 104 and 106 of inflation stylus 100 , and annular enclosing layer 12 and nuclear enclosing layer 22 . Pathways 36 b , 38 b and 40 frictionally engage the outer surfaces of inflation tubes 102 , 104 and 106 , obviating the danger of leakage or dislodgement during the pressuring and inflation of nuclear prosthesis 10 , as will discussed in more detail hereinafter. Referring to FIGS. 5 through 9, 11A and 11B , sealing valve core 28 forms an annular slot 28 b , which extends the outer radial circumference of sealing valve core 28 . Therefore, annular slot 28 b is adjacent both inner margin 16 of annular enclosing layer 12 and outer margin 18 of annular enclosing layer 12 . Sealing valve core 28 further forms a nuclear slot 28 a within annular slot 28 b along the surface of sealing valve core 28 adjacent inner margin 16 of enclosing layer 12 . Annular slot 28 b and nuclear slot 28 a are adapted to receive and retain inner margin 16 of annular enclosing layer 12 , respectively, as well as a surrounding retaining ring 30 . Thus, along inner margin 16 , annular slot 28 b and nuclear slot 28 a define a nuclear mounting region 28 d , which receives annular enclosing layer 12 and retaining ring 30 therein Annular slot 28 b is adapted to receive and retain outer margin 18 of annular enclosing layer, as well as retaining ring 30 . Therefore, along outer margin 18 , annular slot 28 b defines an annular mounting region 28 c for receiving and retaining outer margin 18 of enclosing layer and retaining ring 30 . The lateral ridges of annular slot 28 b along outer margin 18 of annular enclosing layer 12 mate with a flat distal tip of release cannula 206 of delivery apparatus 200 such that when release cannula 206 is held stationary and inflation stylus 100 is retracted, release cannula 206 urges sealing valve core 28 to detach from inflation stylus 100 . Referring to FIGS. 2, 3, 4, and 8 , nuclear structure 21 comprises nuclear enclosing layer 12 , nuclear enclosure 24 and indwelling catheter 32 . Nuclear enclosure 24 is defined by the inflatable nuclear enclosing layer 22 , which is bonded about the periphery of indwelling catheter 32 . Indwelling catheter 32 is comprised of a catheter body having a bulbous portion 32 b disposed on the proximal end 32 c of indwelling catheter 32 , which is affixed to inner margin 16 of annular enclosing layer 12 , and extends within sealing valve core 28 . Nuclear enclosing layer 22 is bonded to indwelling catheter 32 at a connector terminal 22 b . Connector terminal 22 b is defined by neck portion 22 a receiving and tightly bonding to the body of indwelling catheter 32 at a predetermined distance from proximal end 32 c and bulbous portion 32 b of indwelling catheter 32 , and a retaining collar 22 c receiving and crimping to neck portion 22 a and indwelling catheter 32 to provide a fluid-tight seal to nuclear enclosing layer 22 . A fluid-tight seal is formed between indwelling catheter 32 and neck portion 22 a of the nuclear enclosing layer 22 by applying a layer of adhesive material (not shown) between indwelling catheter 32 and neck portion 22 a of nuclear enclosing layer 22 and crimping retaining collar 22 c over indwelling catheter 32 and neck portion 22 a to form the sealed connector terminal 22 b . Preferably, indwelling catheter 32 and the inner surface of neck portion 22 a are thermally and chemically similar, allowing a permanent bond to be performed. In a preferred embodiment, a polymeric insert (not shown) formed of a mutually bondable material may be interposed between the outer surface of indwelling catheter 32 and inner surface of neck portion 22 a of nuclear enclosing layer 22 during the manufacturing process; thus providing for a more durable structural integrity of the attachment. The entire connector terminal 22 b including retaining collar 22 c , which is placed around neck portion 22 a of nuclear enclosing layer 22 , is then thermally processed and crimped to sealably bond neck portion 22 a of nuclear enclosing layer 22 to indwelling catheter 32 . Retaining collar 22 c tapers proximally for ease of insertion and bonding into nuclear slot 28 a of nuclear mounting region 28 b . Indwelling catheter 32 is relatively stiff and may be formed from polyurethane or polyethylene material (not shown) and may include a braided or helically wound wire reinforcing layer (not shown) to resist kinking. In a preferred embodiment, indwelling catheter 32 is formed by extruding a plurality of layers (not shown), including a suitably bondable outer layer (not shown) into a tubular form. A seal plug (not shown) is inserted into indwelling catheter 32 for obstructing the lumen of indwelling catheter 32 after inflation of nuclear enclosure 24 is complete. The seal plug is prevented from being dislodged from the lumen of indwelling catheter 32 by the constriction of the slit-like pathway 40 of sealing valve core 28 following retraction of inflation stylus 100 . Referring to FIGS. 1 through 3 , and FIGS. 1B through 3C , annular enclosing layer 12 has a doughnut-configuration with a substantially concave inner margin 16 and a substantially convex outer margin 18 , providing for inward folding of the concave inner margin 16 , forming a substantially “C” shaped flat band upon deflation of nuclear prosthesis 10 . The substantially “C” shaped flat band configuration of the deflated annular enclosing layer 12 facilitates wrapping annular enclosing layer 12 around the collapsed nuclear enclosing layer 22 and indwelling catheter 32 . This configuration also provides for interlocking of nuclear enclosing layer 22 within annular enclosing layer 22 when nuclear prosthesis 10 is inflated. Annular enclosing layer 12 is preferably made from a polymeric material and defines a fluid-tight annular enclosure 14 , which is inflatable with an in-situ curable rubber. Annular enclosing layer 12 is preferably semi-compliant. Desirable attributes of annular enclosing layer 12 are not necessarily identical to desirable attributes for medical balloon catheters (not shown), which are used extensively in medical applications such as angioplasty, valvuloplasty, urological procedures and tracheal or gastric intubation. For example, non-compliance and high tensile strength are less crucial in the case of the present invention's annular enclosing layer 12 of nuclear prosthesis 10 . Annular enclosing layer 12 is not expected to be subjected to high bursting pressures because annular enclosing layer 12 is filled with curable in-situ rubber that is deformable, and because nuclear prosthesis 10 is contained within the confines of a closed space bordered by the native vertebral end-plates of the patient. Furthermore, annular enclosing layer 12 is disposed between annular reinforcement band 20 and nuclear enclosing layer 22 , which restrain over-inflation of annular enclosing layer 12 , thus further making non-compliance and high tensile strength less crucial. The thickness of the membrane (not shown) of which annular enclosing layer 12 is made need only be thick enough to provide a fluid-tight barrier to leakage of in-situ cured rubber. Accordingly, a thin membrane of 20 to 60 microns may be used to construct annular enclosing layer 12 . On the other hand, long-term structural integrity, moisture resistance (to avoid degeneration and to provide some protection to the rubber within annular enclosure 14 ) is of paramount importance to ensure durability. Other desirable attributes include kink resistance, low wall thickness, low tendency for pinholing, and ease of bonding and coating to other compounds. Referring to FIGS. 4 through 9, 11A and 11B , sealing valve core 28 of the present invention is adapted to be disposed within annular enclosure 14 and is bondable to annular enclosing layer 12 by heat fusion, ultrasonic welding, hot mold bonding, crimping, or other similar bonding methods known in the art. Adhesive layers (not shown) may be used advantageously in combination to bond sealing valve core 28 of sealing valve assembly 26 to annular enclosing layer 12 , although when the polymer material (not shown) of which sealing valve core 28 of sealing valve assembly 26 and annular enclosing layer 12 are made are similar, adhesives may be unnecessary. As annular enclosing layer 12 is made from semi-compliant material (not shown), inflating annular enclosure 14 tends to exert a peel-away force on the bond between annular enclosing layer 12 and sealing valve core 28 of sealing valve assembly 26 . To avoid this potential problem, nuclear slot 28 a and annular slot 28 b are formed along the surface of sealing valve core 28 adjacent inner margin 16 of annular enclosing layer 12 , and are adapted to receive a portion of inner margin 16 of annular enclosing layer 12 and a portion of inner layer 30 a of retaining ring 30 . Annular slot 28 b extends the radial circumference of sealing valve core 28 . On the surface of sealing valve core 28 adjacent outer margin 18 of annular enclosing layer 12 , annular slot 28 b receives a portion of outer margin 18 and a portion of outer layer 30 b of retaining ring 30 . In a preferred embodiment, the method of securing sealing valve core 28 of sealing valve assembly 26 to annular enclosing layer 12 includes the use of retaining ring 30 positioned over and crimped tightly around annular enclosing layer 12 such that inner layer 30 a of retaining ring 30 is adjacent nuclear slot 28 a , and outer layer 30 b of retaining ring 30 is adjacent annular slot 28 b . The entire connection of sealing valve core 28 , annular enclosing layer 12 and retaining ring 30 is then thermally pressed to form a sealably bonded sealing valve core 28 within annular enclosure 14 resistant to separation from annular enclosing layer 12 during inflation. Preferably, both sealing valve core 28 and the in-situ curable rubber injected into annular enclosure 14 are comprised of the same rubber material. When the in-situ curable rubber injected in annular enclosure 14 during inflation of nuclear prosthesis 10 solidifies, it bonds to sealing valve core 28 . The result is that the distinction between sealing valve core 28 and the curable rubber disappears, and an integral annular enclosure 14 of unitary construction is created. Referring to FIGS. 4, 9, 10 and 17 through 19 , annular reinforcement band 20 is disclosed. Annular reinforcement band 20 of the present invention is preferably a semi-compliant multi-layered bio-compatible textile structure that provides a detent to maximal stretching of the circumference of nuclear prosthesis 10 . Various parameters and properties of annular reinforcement band 20 may be adjusted to provide longitudinal flexibility and stretch, radial compliance, and kink resistance of annular reinforcement band 20 . Such variations include varying the materials from which the fibers making up the layers 20 a , 20 b and 20 c of annular reinforcement band 20 are formed, varying fiber density, varying fiber denier, varying braiding angles, varying the number of strands per filament, and varying heat-set conditions. These parameters are tailored to provide the desirable function required of a particular layer of annular reinforcement band 20 , depending on the layer's position in annular reinforcement band 20 . Generally, outer layers 20 a should be substantially less compliant, and compliance the annular reinforcement band 20 should increase through intermediate layers 20 b and inner layer 20 c. In a preferred embodiment, annular reinforcement band 20 is a three-dimensional structure that is formed by extending and interlocking at least one yarn of each layer of annular reinforcement band 20 with the adjacent layers. The multi-layered textile annular reinforcement band 20 shows a gradation of properties between its inner layers and outer layers. Referring to FIG. 9 and FIGS. 17 through 19 , at least one, and preferably more than one outer layers 20 a are preferably made of a warp knitted pattern of biocompatible fibers. This gives outer layers 20 a of annular reinforcement band 20 the advantage of velour, high porosity surface, enhancing tissue in-growth, as well as resisting unraveling. The fibers of outer layers 20 a may be of low denier and may be textured or non-textured. At least one, and preferably more than one intermediate layers 20 b may be formed from biocompatible fibers forming a plurality of loops which follow helical or spiral paths, which may also be wavy or serpentine, contributing to the compliance of annular reinforcement band 20 . The fibers of intermediate layers 20 b preferably include monofilaments of larger denier formed of durable material, such as polyethylene teraphthlate in braided or jersey patterns providing a load-bearing component, resistant to torsion and overstretching. The fibers in intermediate layers 20 b may be chosen to perform a gradation of properties between the mid or equatorial region of annular reinforcement band 20 towards the upper and lower axial margins thereof. In a preferred embodiment, the equatorial section of annular reinforcement band 20 is formed of monofilaments that are thicker, stronger and less compliant filaments, with tapering of these properties towards the upper and lower margins of annular reinforcement band 20 . This renders annular reinforcement band 20 more resistant to kinking during stretching and radial compression of nuclear prosthesis 10 necessary to load nuclear prosthesis 10 within delivery apparatus 200 . Inner layer 20 c of annular reinforcement band 20 is formed from more compliant and thinner biocompatible yarn. In one embodiment, inner layer 20 c may include a fusible fiber (not shown) having a low melting temperature, heat-fusing annular reinforcement band 20 to an innermost layer of intermediate layers 20 b and annular enclosing layer 12 , enhancing ravel and fray resistance. In the preferred embodiment, annular reinforcement band 20 is not bonded to annular enclosing layer 12 . In the preferred embodiment of the present invention, synthetic yarns (not shown) which are not degraded by the body are used to form the textile annular reinforcement band 20 . The yarns may be of the monofilament, multifilament or spun type, used in different combinations. Monofilaments are preferred in intermediate layers 20 b , providing for a lower volume structure with comparable strength to the fiber bundles of the multifilament fibers. Multifilaments are preferred along inner layer 20 c and outer layers 20 a to increase flexibility. The yarns may be flat, textured, twisted, shrunk, or pre-shrunk. As discussed above, the yarn type and yarn denier for a particular layer of the textile annular reinforcement band 20 may be chosen to meet the design requirements of annular reinforcement band 20 . Referring to FIGS. 2, 3 and 4 , nuclear enclosing layer 22 is essentially a discoid multilayered medical balloon which is fabricated by forming a plurality of polymeric layers (not shown) that converge on neck portion 22 a of connector terminal 22 b , adapted for fluid-tight bonding to indwelling catheter 32 . Conventional balloon fabricating techniques are utilized to form a composite nuclear enclosing layer 22 of different polymeric materials (not shown) that are subjected to a stretch blow-molding operation in a heated mold (not shown). The resulting nuclear enclosing layer 22 of the present invention provides superior burst strength, superior abrasion resistance, and superior structural integrity, without significantly impairing the overall compressibility and gas-cushioning function of nuclear prosthesis 10 . Long-term maintenance of a gas cushion in an inflated state is perhaps the most demanding requirement of nuclear enclosure 24 . Various approaches may be taken, including melt-blending the materials making up nuclear enclosing layer 22 and the use of multilayer fiber reinforced balloon structures (not shown) to make nuclear enclosing layer 22 . Referring to FIGS. 2, 3, 4 and 8 , nuclear enclosing layer 22 has a neck portion 22 a which is bonded to indwelling catheter 32 , forming a secure connector terminal 22 b . Indwelling catheter 32 has a proximal end 32 c including bulbous portion 32 b which is adapted to be coupled to nuclear access tube 106 inflation stylus 100 , which is inserted through pathway 40 in sealing valve core 28 of sealing valve assembly 26 . Bulbous portion 32 b defines a bulbous portion that snaps into a corresponding bulbous region 32 e in sealing valve core 28 . Bulbous portion 32 b is sealingly affixed to the corresponding bulbous portion 32 e of sealing valve core 28 , forming a fluid-tight bond with sealing valve core 28 . Proximal end 32 c of indwelling catheter 32 is in fluid communication with the distal end of nuclear access tube 106 , within sealing valve core 28 . Nuclear enclosing layer 22 is sealingly mounted on the shaft of indwelling catheter 32 . Preferably, neck portion 22 a of nuclear enclosing layer 22 is thermally or meltably bonded to indwelling catheter 32 . Connector terminal 22 b and indwelling catheter 32 are all preferably made of melt compatible material. Connector terminal 22 b may utilize a fie layer or “retaining collar” 22 c formed of mutually bondable material that is slipped over neck portion 22 a of nuclear enclosing layer 22 . Retaining collar 22 c is heated and crimped to simultaneously meltably join neck portion 22 a of nuclear enclosing layer 22 , retaining collar 22 c , and indwelling catheter 32 , making connector terminal 22 b a permanent fluid-tight seal. Indwelling catheter 32 defines a lumen with side pore 32 a therein located proximal to closed tip 32 d of indwelling catheter 32 . After inflating nuclear prosthesis 10 within the nuclear space void of a patient, the lumen of indwelling catheter 32 can be permanently obstructed by a small sealing plug (not shown) introduced through proximal end 32 c of indwelling catheter 32 , and pushed into position with a guidewire (not shown) or other suitable positioning device. Pathway 40 of sealing valve core 28 collapses upon removal of inflation stylus 100 , preventing back-up of the sealing plug within indwelling catheter 32 . Referring to FIGS. 1D, 2D and 3D , delivery apparatus 200 is disclosed. Prior to insertion of delivery apparatus 200 into the patient, a percutaneous access device (not shown) provides an access way or annular fenestration(not shown) into the inter-vertebral disc space of the patient, which is held open by an access cannula 202 . Any percutaneous access device used for minimally invasive percutaneous procedures can be used to create the annular fenestration. Generally, such percutaneous access devices comprise a plurality of telescopically arranged cannulas (not shown). After creation of the annular fenestration, delivery apparatus 200 can be delivered within access cannula 202 . Delivery apparatus 200 comprises a delivery cannula 204 with nuclear prosthesis 10 loaded therein, and a release cannula 206 . Delivery apparatus 200 , including nuclear prosthesis 10 and delivery cannula 204 which houses nuclear prosthesis 10 is provided, assembled and hermetically sealed so that loading or handling of nuclear prosthesis 10 is unnecessary during insertion and inflation thereof within the nuclear space void of the patient. Still referring to FIGS. 1D, 2D, and 3D , delivery apparatus 200 of the present invention has oval inner and outer cross-section conforming to the cross sections of access cannula 202 . Delivery apparatus 200 comprises a delivery cannula 204 having a wall of uniform thickness defining a cylindrical inner passage having a substantially oval cross section, and a substantially oval release cannula 206 located within the oval, cylindrical inner passage of delivery cannula 204 . Inflation stylus 100 is slidably received within the oval release cannula 206 . Delivery apparatus 200 is slidably received internally of the access cannula 202 , and is selectively extendible and retractable relative to access cannula 202 to facilitate proper placement of nuclear prosthesis 10 through the annular fenestration into the disc space void. Referring to FIGS. 10 through 11B , delivery cannula 204 of delivery apparatus 200 encloses release cannula 206 , which is telescopically slidable over inflation stylus 100 . As previously discussed, inflation stylus 100 includes three inflation tubes 102 , 104 and 106 extending from its tip. Inflation tubes 102 , 104 and 106 are frictionally engaged to pathways 36 b 38 b and 40 (respectively) of sealing valve core 28 . In a preferred embodiment, nuclear access tube 106 has a bulbous ridge 106 b formed at its mid aspect that mates with a corresponding bulbous region 40 b formed along passageway 40 . The frictional engagement, as well as the engagement of bulbous ridge 106 b with the bulbous region 40 b provides a firm attachment of inflation stylus 100 to sealing valve core 28 , while allowing inflation tubes 102 , 104 and 106 to be withdrawn when sufficient force is applied to it. The amount of force required to withdraw inflation stylus 100 from nuclear prosthesis 10 may be chosen by selecting the rigidity and modulus of elasticity forming sealing valve core 28 as well as selecting the size and geometry of the pathways 36 b , 38 b and 40 and bulbous ridge 106 b . Generally, the amount of force required to release inflation stylus 100 from sealing valve core 28 must be more than the maximum inflation pressure experienced at the connection during inflation of nuclear prosthesis 10 . It may be difficult to precisely control the force required to withdraw inflation stylus 100 from sealing valve core 28 . As may be appreciated, if this force is too great, sealing valve core 28 may be dislodged through the annulotomy, possibly causing tearing of the native annulus fibrosis. If the force required to withdraw inflation stylus 100 from sealing valve core 28 is too small, inflation stylus 100 may become prematurely detached from sealing valve core 28 during pressurizing and inflation of nuclear prosthesis 10 . Referring to FIGS. 10 through 12 , in a preferred embodiment, the release of inflation stylus 100 from sealing valve core 28 is obtained by utilizing release cannula 206 placed coaxially around inflation stylus 100 . Release cannula 206 has a thick wall and a diameter smaller than the outer diameter of sealing valve core 28 , such that its distal end engages sealing valve core 28 to, in effect, push sealing valve core 28 away from inflation stylus 100 . A screw drive mechanism (not shown) is threadedly engaged with and coupled to the proximal end (not shown) of inflation stylus 100 and release cannula 206 to achieve smooth, efficient, and predictable disengagement of inflation stylus 100 from the sealing valve core 28 . The screw drive mechanism provides a mechanical advantage for withdrawing inflation stylus 100 from sealing valve core 28 at a controlled rate. A coupler (not shown) at the proximal end of inflation stylus 100 is adapted to engage the proximal end (not shown) of release cannula 206 to controllably extend and retract inflation stylus 100 and control its maximum travel. This can be done while the tip of release cannula 206 holds sealing valve core 28 stationary within annular enclosure 14 . The extension and retraction capabilities of inflation stylus 100 (in unison or independent of release cannula 206 ) facilitate proper deployment and detachment of nuclear prosthesis 10 within the nuclear space void. Withdrawal of inflation stylus 100 may be achieved by merely turning a knob (not shown) on the screw drive mechanism, which causes inflation stylus 100 to retract axially with respect to release cannula 206 , while sealing valve core 28 is held in place by the tip of release cannula 206 , thereby selectively screw-engaging or disengaging release cannula 206 . The retracting motion continues until inflation tubes 102 , 104 and 106 are completely disengaged from pathways 36 b , 38 b and 40 , respectively, of sealing valve core 28 . The screw drive mechanism may include a worm drive (not shown) that mates with teeth (not shown) formed on the exterior surface of inflation stylus 100 and release cannula 206 . Clearly, a wide variety of mechanical linkages are available to extend and retract inflation stylus 100 and release cannula 206 . It is particularly advantageous to provide a mechanism which allows independent, as well as linked and coordinated movements. The knob may also be rotationally twisted in one direction during the loading of nuclear prosthesis 10 into delivery apparatus 200 . In this case, release cannula 206 and inflation stylus 100 are retracted as one unit into delivery apparatus 200 , pulling nuclear prosthesis 10 through a loading apparatus 300 and progressively radially compressing nuclear prosthesis 10 to a reduced-radius state until it is fully loaded within delivery cannula 204 of delivery apparatus 200 . When the knob is rotationally twisted in the opposite direction, release cannula 206 and inflation stylus 100 extend as one unit extruding nuclear prosthesis 10 from the tip of delivery cannula 204 to achieve predictable and controlled incremental deployment within the nuclear space void. Referring to FIGS. 1A, 2A and 3A , loading apparatus 300 has a first loading block 302 and a second loading block 304 traversed by mirror-image funnel-shaped passageways 306 and 308 , respectively. The distal end of delivery apparatus 200 fits snugly but slidably within loading port 316 at a front end of first loading block 302 . The apposing ends of first loading block 302 and second loading block 204 have the general size and configuration of an inflated nuclear prosthesis 10 . Each funnel shaped passageway 306 and 308 of first loading block 302 and second loading block 304 , respectively tapers down within each loading block 302 and 304 to a second, smaller configuration which has the general cross-sectional oblong configuration of delivery cannula 204 of delivery apparatus 200 , and runs for a short distance in loading blocks 302 and 304 , forming a smooth transition with the inner margin of delivery cannula 204 at the loading port 316 of first loading block 302 . Funnel passageways 306 and 308 of loading apparatus 300 define a tapered diamond-shaped space that geometrically and plastically deforms nuclear prosthesis 10 from a generally round, inflated configuration, as it is being deflated and pulled in opposing directions (as indicated by direction arrows 400 and 402 ) of the radial axis through the tapered funnel shaped passageways 306 and 308 , and then loaded into delivery cannula 204 of delivery apparatus 200 , which has been inserted into loading port 316 of first loading block 302 . Referring to FIGS. 1A through 3C , as nuclear prosthesis 10 is pulled and stretched in opposing directions 400 and 402 within the diamond-shaped passageway defined by funnel shaped passageways 306 and 308 , nuclear prosthesis is progressively radially approximated to a reduced-radius state. Simultaneously, annular enclosure 14 is deflated, approximating inner margin 16 and outer margin 18 of annular enclosing layer 12 into the thin substantially “C” shaped configuration, which assumes a more acute curvature as nuclear prosthesis 10 is stretched. Annular enclosing layer 12 is stretched in a radial direction diametrically opposite to loading port 316 and delivery apparatus 200 by a traction band 322 removably wrapped around annular enclosing layer 12 at a position diametrically opposite the position of loading port 316 . In one embodiment, removable traction band 322 is a rubber band. However, any suitable band made of any suitable material can be used as traction band 322 , so long as it allows for removable attachment to annular enclosing layer 12 and is capable of stretching nuclear prosthesis 10 in a direction diametrically opposite the direction delivery apparatus 200 stretches nuclear prosthesis 10 . As nuclear prosthesis 10 reaches the small end of the diamond-shaped passageway defined by funnel shaped passageways 306 and 308 , annular enclosing layer 12 is wrapped tightly and folded compactly around nuclear enclosing layer 22 and indwelling catheter 32 , into the smallest possible cross-section, and is withdrawn into delivery cannula 204 of delivery apparatus 200 . The folded nuclear prosthesis 10 fits loosely within delivery cannula 204 , allowing achievement of unhindered deployment into the nuclear space void. The inner surfaces of loading blocks 302 and 304 are preferably lined with a water-soluble lubricious hydrophilic coating (not shown) to lubricate the contact surfaces between loading blocks 302 and 304 and nuclear prosthesis 10 during loading thereof onto delivery apparatus 200 . During the loading process, nuclear prosthesis 10 is deflated, stretched and radially compressed so as to adopt a low-profile configuration within the delivery cannula. Referring to FIGS. 3A and 3D , folded nuclear prosthesis 10 is shown releasably attached to the distal end of inflation stylus 100 , which is surrounded by release cannula 206 and housed within the delivery cannula 204 . Delivery apparatus 200 passes through access cannula 202 . As previously discussed, nuclear prosthesis 10 is secured to inflation stylus 100 , by way of inflation tubes 102 , 104 and 106 projecting from the distal tip of inflation stylus 100 and inserted into corresponding passageways 36 b , 38 b and 40 , respectively, in sealing valve core 28 of nuclear prosthesis 10 . When the inflation stylus 100 —release cannula 206 assembly is retracted within delivery cannula 204 , the loaded nuclear prosthesis 10 is pulled into the delivery cannula 204 . It should be appreciated by one skilled in the art that once the deflated nuclear prosthesis 10 is delivered into the nuclear space void, an inflation-assisting device (not shown) or fluid delivery apparatus (not shown) introduces the in-situ curable rubber into annular enclosure 14 and the liquid and/or gas into nuclear enclosure 24 . It should be understood to one of ordinary skill in the art that any device, apparatus and/or system suitable for injecting fluid can be used to inflate nuclear prosthesis 10 could be used. Furthermore, fluid can be injected into nuclear prosthesis 10 manually using a syringe (not shown) connected to the tubes 102 , 104 and 106 of inflation stylus 100 . Although the invention has been described with reference to specific embodiments, this description is not meant to be construed in a limited sense. Various modifications of the disclosed embodiments, as well as alternative embodiments of the invention will become apparent to persons skilled in the art upon the reference to the description of the invention. It is therefore contemplated that the appended claims will cover such modifications that fall within the scope of the invention.
An inter-vertebral disc prosthesis intended for percutaneous deployment comprises an expandable annular enclosure and an expandable nuclear enclosure. The expandable annular enclosure incorporates a reinforcing annular band along its periphery and is filled with in-situ curable rubber. The expandable nuclear enclosure is filled with a gas. The nuclear prosthesis further incorporates a novel, integrally molded sealing valve assembly and is stretchable and collapsible into a minimal profile for ease of insertion into a specially designed delivery cannula, and is inflation-assisted expandable into an inter-vertebral disc in which complete percutaneous nuclectomy has been performed.
0
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a polycylic diol by using carbon monoxide, hydrogen and a polycyclic bridged ring olefinic compound having another double bond, formyl or methylol group (at the other side of bridgehead carbon). 2. Description of the Prior Arts Polycyclic diols are useful as intermediates for non-solvent type lacquers having excellent hardness, polyurethanes having heat resistance and chemical resistance and hardeners for epoxy resins etc. The typical polycylic diol is tricyclodecanedimethylol and accordingly, the process for producing tricyclodecanedimethylol by a hydroformylation of dicyclopentadiene will be mainly described. The oxo reaction of dicyclopentadiene is carried out in the presence of a cobalt compound, a diluent, a polymerization inhibitor and a stabilizer at 120° to 150° C. under a pressure of 180 kg/cm 2 to obtain tricyclodecanedimethylal and then, the tricyclodecanedimethylal is hydrogenated in the presence of a nickel catalyst to obtain tricyclodecanedimethylol in G.B. Pat. No. 750,144. The oxo reaction of dicyclopentadiene is carried out in the presence of a rhodium compound and a diluent at 125° to 140° C. under the pressure of 200 to 250 kg/cm 2 to obtain tricyclodecanedimethylal and then, the hydrogenation of the product is carried out in the presence of the same catalyst than 180° C. to obtain tricyclodecanedimethylol in G.B. Pat. No. 1,170,226. Thus, in these processes, two steps for the reactions are required and high pressure should be applied. In the latter process using the rhodium catalyst, the catalyst is disadvantageously expensive. Both processes are not satisfactory. On the other hand, it has been known to carry out a hydroformylation of an olefin compound in the presence of a catalyst of a cobalt compound and a phosphine. In accordance with this process, the catalyst is economical and the reaction pressure is lower and the alcohol is obtained by one step reaction. This process is employed as an industrial processes for producing n-butanol or a higher alcohol as a detergent source. It has not found to apply this process to dicyclopentadiene. The hydroformylation using a cobalt compound and a phosphine as catalyst is usually carried out at a temperature of higher than 160° C. especially about 200° C. whereby the alcohol can be obtained in one reaction step. On the other hand, dicyclopentadiene is usually decomposed into cyclopentadiene by a reverse Diels Alder reaction at higher than 150° C. Therefore, in the conventional hydroformylation at such high temperature, an yield of tricyclodecanedimethylol is lower and an inactivation of the catalyst caused by cyclopentadiene is found as described in Chem. Prum. 19, 359(1969) C.A. 72, 11777. This phenomenon may be considered in the conventional processes since it is carried out at lower than 160° C. In order to produce tricyclodecanedimethylol by the hydroformylation using a cobalt compound and a phosphine as a catalyst, it may be necessary to find a special method for performing predominant hydroformylation under preventing the decomposition of dicyclopentadiene. It has been expected to attain a remarkably effective process for producing tricyclodecanedimethylol if said ideal conditions can be found. SUMMARY OF THE INVENTION It is an object of the present invention to produce a polycyclic diol at high yield by a hydroformylation of a polycyclic bridged ring olefinic compound having another double bond, formyl or methylol group (at the other side of bridgehead carbon) at high temperature in an economical one step reaction. It is another object of the present invention to produce a polycyclic diol at high yield in the presence of a cobalt carbonylphosphine complex as a catalyst and to reuse the catalyst components by an advantageous manner. The foregoing and other objects of the present invention have been attained by producing a polycyclic diol by a hydroformylation of a polycyclic bridged ring olefinic compound having another double bond, formyl or methylol group (at the other side of bridgehead carbon) in the presence of a cobalt compound and a phosphine as a catalyst in the presence of a saturated hydrocarbon or aromatic hydrocarbon solvent and the reaction mixture is cooled to result a phase separation into a solvent phase containing the catalyst and a polycyclic diol phase and the solvent phase is recycled into the reaction system. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The process of the present invention is remarkably advantageous because the hydroformylation of the polycyclic bridged ring olefinic compound having another double bond, formyl or methylol group can be predominantly performed at a high temperature for causing a decomposition of said starting material. In the industrial process using a cobalt compound and a phosphine as the catalyst, it is advantageous to separate the catalyst from the product and to reuse the separated catalyst in the hydroformylation. Certain processes have been proposed to separate the catalyst and the solvent from tricyclodecanedimethylal produced by the hydroformylation or from tricyclodecanedimethylol produced by the hydrogenation of said dimethylal. The hydroformylation is carried out by using cobalt naphthenate as the catalyst and using hexane as the solvent and the reaction mixture is cooled to separate it into a solvent phase and a tricyclodecanedimethylal phase and the solvent phase is recycled into the reactor and the cobalt component is separated by a thermal decomposition from the tricyclodecanedimethylal phase in G.B. Pat. No. 728,913. The hydroformylation is carried out by using cobalt sulfate as the catalyst and using heptane as the solvent and the reaction mixture is cooled to separate it into three phases of a heptane phase, an aqueous phase and a tricyclodecanedimethylal phase. The cobalt component is allotted to about 10%, about 53% and about 37% respectively in said phases. A new catalyst for hydrogenation is added to the tricyclodecanedimethylal phase and the hydrogenation is carried out at an elevated temperature to convert it into tricyclodecanedimethylol and also to remove the cobalt component in G.B. Pat. No. 765,742. When the cobalt-magnesium oxide-thorium oxide-diatomaceous earth is used as the catalyst and heptane is used as the solvent, the reaction mixture is separated into a heptane phase and a tricyclodecanedimethylal phase. The catalyst is suspended in the tricyclodecanedimethylal phase and is removed by the same manner. Two step reactions are carried out by using rhodium oxide as the catalyst and benzene as the solvent to obtain tricyclodecanedimethylol and the rhodium component is separated by a thermal decomposition in G.B. Pat. No. 1,170,226. In these processes, the phase separation is carried out by selecting the solvent. Most of the catalyst is remained in the product phase and the catalyst is separated from the product by the thermal decomposition. In these processes, when a cobalt compound is used, the metallic cobalt is adhered on the wall of the reactor and accordingly, it is not advantageous for the recycling of the catalyst component. Moreover, these processes are not employed for the separation of the catalyst containing the phosphine. On the other hand, in an industrial process of hydrofomylation using a phosphine with a cobalt compound or a rhodium compound, the reaction mixture is distilled to separate it into the product and a complex of the phosphine and the metal carbonyl since the metal carbonyl-phosphine complex is stable. However, tricyclodecanedimethylol has remarkably high boiling point (about 170° C./1 mmHg) and accordingly, the cobalt carbonyl-phosphine complex is not stable at the temperature for the distillation. This process is not also advantageous. The inventors have further studied to dissolve these problems and have found the following fact. When the hydroformylation is carried out by using a cobalt compound and a phosphine as the catalyst and using a hydrocarbon as the solvent, the solvent phase is separated from the product of tricyclodecanedimethylol by a phase separation caused by cooling the reaction mixture. Most of the cobalt component and the phosphine are included in the solvent phase and accordingly, the catalyst can be easily separated from the product. In the conventional process for producing tricyclodecanedimethylal by using only a cobalt compound as the catalyst, the phase separation of the solvent phase and the product phase is carried out, most of the catalyst is included in the product phase and accordingly, the separation of the catalyst from the product could not be succeeded. On the contrary, in the process for producing tricyclodecanedimethylol by using the cobalt compound and the phosphine as the catalyst most of the catalyst is included in the solvent phase whereby the separation of the catalyst from the product can be easily attained by the phase separation. This reason is considered as follows. The product is different as tricyclodecanedimethylal is produced in the former whereas tricyclodecanedimethylol is produced in the latter and the catalyst is different as a cobalt carbonyl complex is used in the former whereas a cobalt carbonyl-phosphine complex is used in the latter and affinities of the product, the solvent and the catalyst are different. It has not been expected that the distributions of the catalyst in the solvent phase and the product phase are opposite by said slight differences of the reaction conditions. In the conventional process, only a saturated hydrocarbon is used as the solvent for the phase separation. In the process of the present invention, it has been found that an aromatic hydrocarbon can be also effectively used. In accordance with the present invention, the hydroformylation of a polycyclic bridged ring olefinic compound having another double bond, formyl or methylol group (the starting material) is carried out in the presence of a cobalt compound and a phosphine as the catalyst and a saturated hydrocarbon and/or an aromatic hydrocarbon as the solvent and the resulting reaction mixture is cooled to separate it into a solvent phase containing the catalyst and a product phase and the solvent phase is recycled into the hydroformylation reaction system. The present invention can be applied for the production of various polycyclic diols from the polycyclic bridged ring olefinic compound having another double bond, formyl or methylol group under the similar reaction condition. In order to simplify the description of the process of the present invention, the production of tricyclodecanedimethylol from dicyclopentadiene will be illustrated as the typical example. The starting material can be varied to obtain the corresponding product. 1. MATERIALS USED IN THE REACTION (1) Polycyclic bridged ring olefinic compound having another double bond, formyl or methylol group. The polycyclic bridged ring olefinic compound having another double bond, formyl or methylol group (at the other side of bridgehead carbon) include the compounds having the formula ##STR1## (i) tricyclo[5.2.1.0 2 ,6 ]deca-3,8-diene, (this is usually called as dicyclopentadiene), (ii) bicyclo[2.2.1]hepta-2,5-diene, (iii) bicyclo[2.2.1]hept-5-ene-2-carboxaldehyde, (iv) bicyclo[2.2.1]hept-5-ene-2-methylol, (v) 5-vinyl-bicyclo[2.2.1]hept-2-ene, (vi) 5-isopropenyl-bicyclo[2.2.1]hept-2-ene, (vii) 5-propenyl-bicyclo[2.2.1]hept-2-ene, (viii) tetracyclo[6.2.1.1 3 ,6.0 2 ,7 ]dodeca-4,9-diene, (xi) bicyclo[2.2.2]octa-2,5-diene, (x) 5-vinyl bicyclo[2.2.2]oct-2-ene, (xi) pentacyclo[9.2.1.1 3 ,9.0 2 ,10.0 4 ,8 ]pentadeca-5,12-diene, (xii) tricyclo[6.2.1.0 2 ,7 ]undeca-4,9-diene. The typical starting material is dicyclopentadiene and accordingly, the present invention will be described in detail on the process for producing tricyclodecanedimethylol from said starting material. Products (polycyclic diols) The following polycyclic diols are produced by using the polycyclic bridged ring olefinic compounds (i) to (xii). (The references are corresponding with the starting materials.) ##STR2## Dicyclopentadiene as the starting material can be produced by Diels Alder reaction of cyclopentadiene. The industrial product of cyclopentadiene obtained by the naphtha cracking as a C 5 -fraction can be used. (2) Synthesis gas The synthesis gas contains CO and H 2 at a molar ratio of CO/H 2 of 5:95 to 95:5 preferably 2:1 to 1:2. It is possible to mix an inert gas such as nitrogen, argon, carbon dioxide and methane as far as it does not adversely affected to the reaction. 2. CATALYST (1) Cobalt compound The cobalt compounds are preferably cobalt carbonyl complexes such as dicobalt octacarbonyl or hydro cobalt tetracarbonyl. The precursors such as compounds which form carbonyl complexes in the reaction, such as metallic cobalt; cobalt oxide, cobalt halides, cobalt acetates, cobalt octanoates and cobalt naphthenates can be used. (2) Phosphine The phosphines having the formula R.sub.3 P wherein R is the same or different and respectively represent hydrocarbon moiety, can be used. It is especially preferable to use the phosphines having saturated aliphatic group or alicyclic hydrocarbon group as the hydrocarbon moiety. Suitable phosphines include tri-n-butylphosphine, tri-n-octylphosphine, tri-n-dodecylphosphine and tricyclohexylphosphine. Bicyclic heterocyclic phosphines such as 9-eicosyl-9-phosphabicyclo [4.2.1]nonane, 9-eicosyl-9-phosphabicyclo 3.3.1 nonane, 8-eicosyl8-phosphabicyclo[3.2.1]octane and 8-octadecyl-8-phosphabicyclo [3.2.1]octane, are also suitable. Polydentate-phosphines such as 1,2-bisdiethylphosphinoethane, octamethylene-P,P'-bis(9-phosphabicyclo[4.2.1]nonane can be also used. A mixture thereof can be also used. 3. SOLVENT The solvents used in the reaction can be saturated aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and mixtures thereof. It is preferably to use the solvent which have 6 or more carbon atoms and is liquid at the separation temperature. Suitable solvents include n-hexane, n-octane, n-dodecane, n-tetradecane, cyclohexane, methylcyclohexane, decalin, "liquid paraffin" made of alkyl naphthenes, benzene, toluene, butylbenzene, dodecylbenzene and mixtures thereof. It is possible to use a mixed solvent containing a compound having polar group with the hydrocarbon if it does not adversely affected. 4. CONDITIONS FOR REACTION The conditions for reaction are selected as follows. The reaction temperature is usually in a range of 100° to 250° C. preferably 150° to 200° C. The pressure in the reaction is usually in a range of 10 to 200 kg/cm 2 preferably 30 to 150 kg/cm 2 . The reaction time is 0.5 to 10 hours preferably 1 to 7 hours. The molar ratio of olefinic compound to cobalt is 10 to 1000 preferably 30 to 300. The atomic ratio of phosphorous to cobalt is 1 to 10 preferably 1 to 2. The concentration of cobalt in the reaction mixture is in a range of 0.005 to 1 wt. % preferably 0.03 to 0.3 wt. %. The selection of the conditions for the reaction of dicyclopentadiene is especially important in the process of the present invention. In the conventional hydroformylation of monoolefin or diolefin which are not decomposed, the variation of the condition for reaction affects only for a reaction velocity and a distribution of isomers of the products except a special condition for preventing stable action of the catalyst. On the other hand, in the hydroformylation of dicyclopentadiene, when the condition for reaction is not suitable, an yield of the object products is low and sometimes, the reaction is stopped. This reason is not clear, however, it is considered that the reverse Diels Alder reaction of dicyclopentadiene is predominant and the resulting cyclopentadiene is selectively coordinated to the catalyst, vacant coordination sites required for the hydroformylation are lost. In order to perform smoothly the reaction and to obtain the object product at high yield, it is necessary to select suitable conditions. Thus, the effects of the conditions for reaction are complicate and are related each others. The selection of the conditions for reaction is not simple. The conditions for reaction which highly affect to the smooth reaction among these conditions are the pressure in the reaction, the ratio of dicyclopentadiene to cobalt and the concentration of cobalt in the reaction mixture. The pressure in the reaction is usually in a range of 50 kg/cm 2 to 200 kg/cm 2 preferably 70 kg/cm 2 to 150 kg/cm 2 . The higher pressure is advantageous for the reaction. The molar ratio of dicyclopentadiene to cobalt is usually in a range of 20 to 300 preferably 40 to 200. The lower ratio is advantageous for the reaction. The concentration of cobalt in the reaction mixture is in a range of 0.01 to 0.5% by weight preferably 0.03 to 0.3% by weight. The higher concentration of cobalt is advantageous for the reaction. The three conditions affect to the reaction with relations each other. The effect can be shown as a whole by a factor for oxonation F as the parameter. ##EQU1## In the condition for reaction to give the factor F of higher than 5, the reaction performs smoothly to produce tricyclodecanedimethylol in the yield of higher than about 50%. Moreover, byproducts are mainly cyclopentyl carbinol and tricyclodecanemonomethylol which are effectively utilized. When the factor F is less than 5, the reaction is stopped to give the yield of tricyclodecanedimethylol of less than about 15%. The most of the by-products are heavy materials which may be produced by condensations of the starting materials and/or the intermediates. The utilization of the heavy materials is not expected. As discussed, the feature of the reaction is remarkably different at the factor F of higher or lower than 5. The feature of the reaction is not varied at the factor F of higher than 5, however, the selectivity of the product is different depending upon the difference of the condition for reaction. The yield of tricyclodecanedimethylol in this region is related to the factor F and is increased depending upon the increase of the factor F. The yield is varied depending upon the kind of the phosphine and other conditions for reaction and is usually higher than about 70% at the factor F of higher than about 10. The other conditions for reaction are selected as follows. The reaction temperature is usually in a range of 160° to 220° C. preferably 180° to 200° C. The reaction time is usually in a range of 2 to 10 hours preferably 3 to 7 hours. The atomic ratio of phosphorus to cobalt is usually in a range of 1 to 10 preferably 1.1 to 2. These conditions mainly affect to the reaction velocity and the stability of the catalyst, but does not substantially affect to the selectivity for the products. If desired, the reaction can be carried out after adding a desired additive such as polymerization inhibitor and a base. 5. SEPARATION AND PURIFICATION When a hydrocarbon is used as the solvent, the solvent can be separated from the products by cooling the reaction mixture after the hydroformylation. The lower temperature is preferable for the separation. At the lower temperature, the viscosity of some polycyclic diol is higher whereby the handling in the processing is not easy. Thus, the separation is carried out at room temperature to 100° C. It is possible to carry out the separation under the pressures of carbon monoxide and hydrogen as those of the reaction. In usual, excess of carbon monoxide and hydrogen are removed and the separation is carried out under a pressure of from the atmospheric pressure to 10 kg/cm 2 in the mixed gas of carbon monoxide and hydrogen or an inert gas. In accordance with the separation, most of the cobalt component and the phosphine are included in the solvent phase in a form of an active complex. Therefore, the solvent phase containing them can be recycled to the reaction system for hydroformylation to reuse them. If necessary, it is preferable to remove impurities which are accumulated during the recyclings. The process of the present invention can be applied as a process for extracting the catalyst from polycyclic diol containing the catalyst of the cobalt carbonyl complex and the phosphine; with a hydrocarbon to recover the catalyst and to purify polycyclic diol. That is, the polycyclic diol phase obtained by the above-mentioned operation includes a small amount of the catalyst. The content of the catalyst can be further decreased by extracting it with a hydrocarbon solvent. The solvent used in the extraction is preferably a saturated hydrocarbon or an aromatic hydrocarbon as those of the reaction. It is not always necessary to use the same solvent as that of the reaction. A lower boiling solvent which is easily recovered can be used. Moreover, the extraction can be carried out for two or more times. When the extraction is carried out, the extracted solvent containing the catalyst is combined to a part of the solvent for reaction and the mixture is distilled to recover the solvent for extraction and to transfer the catalyst into the solvent for reaction and the solvent containing the catalyst can be recycled into the reaction system. This process can be also applied for a purification of polycyclic diol containing the catalyst of the cobalt carbonyl complex and the phosphine obtained by the other process. The polycyclic diol phase is treated by a desired treatment, for example, hydrogen treatment to decompose the remaining catalyst complex, if necessary, and then, it is distilled to remove the by-products and the product of polycyclic diol can be obtained. The present invention has been mainly illustrated as the hydroformylation of dicyclopentadiene to produce tricyclodecanedimethylol and the separation of the catalyst of the cobalt carbonyl-phosphine complex. Thus, the process can be applied for the other starting materials as the polycyclic bridged ring olefinic compound having another double bond or formyl or methylol group as described above. The present invention will be further illustrated by certain examples which are provided for purposes of illustration only and are not intended to be limiting the present invention. EXAMPLE 1 In a 100 ml. autoclave made of Hastelloy equipped with an electromagnetic stirrer, 6.6 g. of dicyclopentadiene, 0.197 g. of dicobalt octacarbonyl as a cobalt compound, 0.871 g. of tri-n-octylphosphine as a phosphine and 24 g. of n-dodecane as a solvent were charged and a reaction was carried out at 200° C. under a pressure of synthesis gas at a molar ratio of CO/H 2 of 1:1 under a pressure of 150 kg/cm 2 for 5 hours. A factor for oxonation F was 95.2. After the reaction, the product was cooled and discharged at about 90° C. from the reactor and cooled to a room temperature. It was separated into a solvent phase and tricyclodecanedimethylol phase. The tricyclodecanedimethylol phase was extracted for two times with 24 g. of n-dodecane. The compounds included in the phases were analyzed, for example, organic compounds were analyzed by a gas chromatography, a cobalt was analyzed by an atomic absorption method and a phosphine was analyzed by a gas chromatography or a colorimetric method. As a result, it was found that a conversion of dicyclopentadiene (DCP) in a hydroformylation was 100%; an yield of tricyclodecanedimethylol (TCDDM) was 69.2%; an yield of tricyclodecanemonomethylol (TCDMM) was 11.7% and an yield of cyclopentyl carbinol (CPC) was 14.6%. In a phase separation of the reaction, 92.9% TCDDM, 72.1% of TCDMM and 76.4% of CPC (based on each component) were included in TCDDM phase whereas only 8.1% of the cobalt component and 5.9% of the phosphine (based on each component) were included in TCDDM phase. In the extracted TCDDM phase obtained by extracted by n-dodecane for one time, 86.7% of TCDDM, 43.0% of TCDMM and 46.5% of CPC (based on each component) were included whereas only 4.3% of the cobalt component and 3.5% of the phosphine were remained. In the extracted TCDDM phase obtained by the second extraction method, 79.2% of TCDDM, 20% of TCDMM and 27.3% of CPC were included whereas only 2.8% of the cobalt component and 2.2% of the phosphine were remained. EXAMPLE 2 In accordance with the process of Example 1 except using 0.515 g. of tri-n-butylphosphine as the phosphine, the reaction, the separation and the extraction were carried out. The factor F in this condition was 92.5. As a result, a conversion of DCP was 100%, an yield of TCDDM was 66.7%, an yield of TCDMM was 12.3% and an yield of CPC was 9.3%. After the reaction, the reaction product was separated and extracted for two times and the ratios of the products and the catalyst components (based on each component) included in TCDDM phases were measured. The results are as follows. ______________________________________ Separation (unit %)Operation after reaction 1st Extraction 2nd Extraction______________________________________TCDDM 93.9 90.4 79.4TCDMM 77.4 54.9 30.4CPC 85.0 58.4 33.3Cobalt -- -- 5.6Phosphine 9.1 3.1 2.5______________________________________ EXAMPLE 3 In accordance with the process of Example 1 except using 0.401 g. of cobalt octanoate and 1.003 g. of a mixture of 9-eicosyl9-phosphabicyclo-[4.2.1]nonane and 9-eicosyl-9-phosphabicyclo[3.3.1]nonane and reacting under the pressure of 70 kg./cm 2 , the reaction, the separation and the analyses were carried out without an extraction. The factor F in this condition was 62.1. As a result, a conversion of DCP was 100%, an yield of TCDDM was 80.0%, an yield of TCDMM was 14.4% and an yield of CPC was 3.6%. The ratios of the products and the catalyst components (based on each component) included in the TCDDM phase were measured. The results are as follows. ______________________________________ SeparationOperation after reaction______________________________________TCDDM 83.2TCDMM 64.4CPC 85.3Cobalt 7.2Phosphine 7.8______________________________________ EXAMPLE 4 In accordance with the process of Example 3 except using 24 g. of dodecylbenzene as the solvent and 0.198 g. of cobalt octanoate, the reaction, and the separation were carried out. The separated TCDDM phase was extracted with 24g. of dodecylbenzene and analyzed. As a result, a conversion of DCP was 100%, an yield of TCDDM was 61.7% and an yield of CPC was 4.9%. The ratios of the products and the catalyst components (based on each component) included in the TCDDM phase were measured. The results are as follows. ______________________________________ SeparationOperation after reaction 1st Extraction______________________________________TCDDM 94.1 85.8TCDMM -- --CPC 74.7 30.4Cobalt 5.7 3.7Phosphine 4.8 1.0______________________________________ EXAMPLE 5 In accordance with the process of Example 4 except using 24 g. of decalin as the medium for the reaction and 24 g. of decalin for the extraction, the reaction, the separation, the extraction and the analyses were carried out. As a result, a conversion of DCP was 100%, an yield of TCDDM was 66.3%, an yield of TCDMM was 14.3% and an yield of CPC was 4.7%. The ratios of the products and the catalyst components (based on each component) included in the TCDDM phase were measured. The results are as follows. ______________________________________ SeparationOperation after reaction 1st Extraction______________________________________TCDDM 87.8 80.8TCDMM 71.9 31CPC 90.4 51.8Cobalt 4.5 3.0Phosphine 1.5 0.5______________________________________ EXAMPLE 6 In a 100 ml. autoclave made of Hastelloy C equipped with an electromagnetic stirrer, 6.6 g. of dicyclopentadiene, 0.427 g. of cobalt octanoate, 0.420 g. of a mixture of 9-eicosyl-9-phosphabicyclo[4.2.1]nonane and 9-eicosyl-9-phosphabicyclo-[3.3.1]nonane and 15 ml. of n-dodecane were charged, and a reaction was carried out with a synthesis gas at a molar ratio of CO/H 2 of 1:1 under a pressure of 70 kg/cm 2 G at 200° C. for 5 hours. The autoclave was cooled to 90° C. to separate the reaction mixture into a solvent phase and a tricyclodecanedimethylol phase. After the removal of the solvent phase, hydrogen was fed under a hydrogen pressure of 70 kg/cm 2 G to carry out a hydrogenation at 250° C. for 3 hours. The treated product was dissolved into 23 ml. of dioxane and then, metallic cobalt in the suspension was separated by a filtration. The wall of the autoclave was washed with 20 g. of 3% nitric acid to dissolve the cobalt component adhered on the wall. Amounts of the suspended cobalt components, and cobalt components adhered on the wall and remained in the solution were respectively measured by an atomic absorption method to give respectively 6.3%, 3.2% and 3.4% based on the charged cobalt. A carbonyl value (mg. of CO group in 1 kg. of the product) was 6200. When, only oxonation of this example was carried out, the carbonyl value of the product was 10,300. EXAMPLE 7 In a 100 ml. autoclave made of Hastelloy equipped with an electromagnetic stirrer, 7.20 g. of 5-vinyl bicyclo[2.2.1]hept-2ene, 0.103 g. of dicobalt octacarbonyl as a cobalt compound, 0.646 g. of tri-n-dodecylphosphine as a phosphine and 15 ml. of n-dodecane as a solvent were charged and a reaction was carried out at 200° C. under a pressure of a synthesis gas at a molar ratio of CO/H 2 1:1 under a pressure of 70 kg./cm 2 for 5 hours. After the reaction, the product was cooled and discharged at about 90° C. from the reactor and cooled to a room temperature. It was separated into a solvent phase and a product phase. The compounds included in the phases were analyzed, for example, the product was analyzed by a gas chromatography, a cobalt was analyzed by an atomic absorption method and a phosphine was analyzed by a colorimetric method. As a result, an yield of the product of the corresponding diol was 53.1% and 98.1% of the product was included in the product phase. Ratios of the cobalt compound and the phosphine included in the product phase were respectively 3.8% and 6.9% based on the total cobalt component and the total phosphine. EXAMPLE 8 In accordance with the process of Example 7 except using 0.508 g. of a mixture of 9-eicosyl-9-phosphabicyclo-[4.2.1]nonane and 9-eicosyl-9-phosphabicyclo-[3.3.1]nonane, the reaction, the separation and the analysis were carried out without an extraction. As a result, an yield of the product of the corresponding diol was 67.2% and ratios of the product, the cobalt component and the phosphine included in the product phase were respectively 98.2%, 14.6% and 26.0% based on the total product, the total cobalt and the total phosphine. EXAMPLES 9 AND 10 In accordance with the process of Example 8 except using each olefin shown in the following table as the starting material, the reaction, the separation and the analysis were carried out. The results are shown in the following table. TABLE______________________________________Example 9 10______________________________________Starting material olefin ##STR3## ##STR4##Amount (g.) 7.44 11.88Yield of productdiol (%) 78.2 75.3Ratio of each compo-nent in product phaseto total of eachcomponentProduct diol (%) 98.9 95.8Cobalt (%) 9.8 28.6Phosphine (%) 17.5 30.5______________________________________
A polycyclic diol is produced by a hydroformylation of a polycyclic bridged ring olefinic compound having another double bond, formyl or methylol group, in the presence of a cobalt compound and a phosphine as a catalyst in the presence of a saturated hydrocarbon or aromatic hydrocarbon. Polycyclic diols such as tricyclodecanedimethylol are useful for hardeners for non-solvent type lacquers polyurethanes having heat resistant and chemical resistance or epoxy resins.
2
BACKGROUND OF THE INVENTION With the increasing popularity of billiards, many people have become interested not only in the various games that may be played with the equipment, but also with a number of interesting things which can be done with the balls in predetermined configurations. These ballistic exercises, or "trick" shots, generally involve shooting one or more of the billiard balls into predetermined pockets on the table. However, as might be expected, even with detailed instruction, many people find it impossible to perform some of the more involved and esoteric shots. Such problems are especially acute when the shot involves a number of impacts or putting a plurality of balls into a number of predetermined pockets. In uses such as this, the placement of the balls on the table is particularly acute, though some tolerance in their placement is permissable, and must be done with a degree of accuracy. In accordance with the present invention, a method and apparatus is provided that allows an individual to repeatedly and reliably perform such "trick" shots with a minimum of instruction and direction. Besides being simple to use and reliable, the apparatus of the present invention also has the advantage of being easy and inexpensive to manufacture. SUMMARY OF THE INVENTION In accordance with the apparatus of the present invention, a flat planar member for facilitating the placement of the billiard balls on the plane surface of the billiard table is provided. The planar member includes means for properly orienting and positioning the member. The member also has means for indicating the position of the billiard balls. In accordance with the method of the present invention, a plurality of billiard balls may be driven into a plurality of predetermined pockets on a billiard table by orienting the planar member with respect to the playing surface of the billiard table. The planar member is then placed on the table at a predetermined position. A plurality of billiard balls are then placed on the planar member at positions indicated by information on the planar member. The cue ball is then placed on the billiard table at a predetermined position. The billiard cue is put in the proper position and the cue ball is struck with the tip of the cue in order to drive the various other billiard balls into the desired predetermined pockets. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a top plan view of an embodiment of the apparatus of the present invention; FIG. 2 shows how the method of the present invention is used with the apparatus illustrated in FIG. 1; FIG. 3 is an alternative embodiment of the apparatus of the present invention; FIG. 4 shows how the apparatus of FIG. 3 is used; FIG. 5 is a top plan view of still another embodiment of the apparatus of the present invention; and FIG. 6 shows how the apparatus of FIG. 5 is used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Turning to FIG. 1, a template 10 constructed in accordance with the present invention is illustrated. The template comprises a thin flat planar member which may be made of plastic or any other suitable materials such as paper, metal, or fabric. In accordance with the preferred embodiment, it is the same color as the playing surface of the table. Template 10 includes a plurality of holes 12. These serve as indications for the placement of balls when one wishes to do a "trick" shot. Although they may be printed on the template, the fact that they are an actual physical feature of the template allows them to serve the additional purpose of guiding the position of the billiard balls. If this template is to be used with standard billiard balls, which have a diameter of 21/4 inches, then the centers of the holes 12 should be 2 3/16 inches apart. The holes should also all lie on the same line. In accordance with the preferred embodiment template 10 is made of stiff green or clear plastic that is 20 mils thick. When it is desired to put four balls into predetermined pockets on the billiard table, template 10 is put on the playing surface. It is positioned between the two side-pockets of the billiard table and adjacent one of its side-pockets. The table for which this embodiment is designed, as well as that for the embodiments of FIGS. 3-6, is a standard 41/2 feet by 9 feet table. Template 10 is oriented with holes 12 in line with the centers of the two side-pockets 14 and 15 of table 16. A cue ball 18 is then put on the playing surface of the table in line with an imaginary perpendicular extending from the center of the template 12 as is illustrated in FIG. 2. Four balls 20, 22, 24 and 26 are then put on template 10 at holes 12. Cue ball 18 is then struck hard with a cue to move the cue ball in the direction indicated by arrow 28. When the cue ball strikes the balls in template 10, ball 20 moves into side-pocket 14, ball 22 moves into pocket 30, ball 24 bounces off the rim 32 of the table and goes into pocket 34 and ball 26 goes into pocket 15. Referring to FIGS. 3-4, an alternative template 36 is illustrated. This template includes a pair of medial holes 38, a pair of head holes 40 and a pair of tail holes 42. Centers of medial holes 38 are separated from each other by 31/4 inches. Centers of head holes 40 are separated from each other by 4 9/16 inches. Centers of tail holes 42 are separated from each other by 5 9/32 inches. The distance between the center of each medial hole 38 and head hole 40 on the same side of arrow 44, which is printed on template 36, is 2 3/16 inches. The distance between the center of each medial hole 38 and each tail hole 42 on the same side of arrow 44 is 2 3/16 inches. Arrow 44 is, in turn, centered on a line which lies centered between each of the two holes of the pairs of medial, head and tail holes. Each of the pairs of holes thus define lines perpendicular to arrow 44. When it is desired to make the desired trick shot with template 36, template 36 is positioned and oriented on the playing surface, as shown in FIG. 4, with its center lying along a line defined by the two "spots" 46 and 48 on the table. This may be facilitated by using a cue 50 and lining template 36 up with its arrow 44 centered underneath cue 50 when cue is laid over spots 46 and 48, as is illustrated in phantom in FIG. 4. Table 16 has the standard six pairs of side diamonds which are numbered 1-6 in standard form on the drawings. The lateral position of the template is determined by lining up arrows 52 printed on template 36 with the three-diamonds, indicated by the numeral "3" in FIG. 4. The proper positioning of arrows 52 is assured by the following procedure. When two billiard balls 54 and 56 are put in medial holes 38 and a plane perpendicular to the plane of template 36 is positioned tangent to the surfaces of the two billiard balls on their sides that are adjacent the tail holes 42, the line defined by the intersection of the two planes should be 1/2 inch removed from the line defined by the centers of the two tail holes 42 and displaced toward the center of the table. When template 36 is in the desired position, balls 54, 56, 58, 60, 62 and 64 are placed on template 36. Cue ball 18 is then placed on head spot 46. A cue is then used to advance cue ball 18 toward the center of the configuration of billiard balls on template 36. Ball 54 then enters pocket 14; ball 56 enters pocket 15; ball 58 enters pocket 30; ball 60 enters pocket 66; ball 62 enters pocket 34; and ball 64 enter pocket 68. Referring to FIGS. 5 and 6, still another alternative embodiment of the present invention is illustrated. The template 70 illustrated in FIG. 5 has a pair of medial holes 72, a pair of head holes 74, a pair of tail holes 76 and a central hole 78. The head holes 74 lie along a line perpendicular to printed arrow 80, as do pairs of medial holes 72 and tail holes 76. The lines defined by each of the pairs of holes are also all parallel to sides 82 and 84 of the rectangular template. The distance between the centers of each of the head holes 74 and tail holes 76 and the center of central hole 78 is 21/2 inches. The center of medial holes 72 are separated from the centers of the central hole 78 by 2 3/16 inches. The center of each medial hole 72 is separated from the centers of both the head hole 74 and tail hole 76 on the same side of arrow 80 that the medial hole occupies by a distance of 2 3/16 inches. When it is desired to make the shot, template 70 is put on the playing surface of the table as illustrated in FIG. 6 with central hole 78 over head spot 46 and side 82 parallel to side 32 of the table 16. Balls 86, 88, 90, 92, 94, 96 and 98 are then placed on the template. If one wants to put ball 86 into pocket 15, a cue ball 100 is put at a point along a path 102 defined by the centers of balls 94, 86 and 96. Cue ball 100 is then struck hard, driven along path 102 and ball 86 follows path 104. If one wants to put ball 86 into pocket 14, a cue ball 106 is put at a point along a path 108 defined by the centers of balls 92, 86 and 98. Cue ball 106 is then struck hard, driven along path 108 and ball 86 follows path 110. If one wants to put ball 86 into pocket 34, a cue ball 112 is put at a point along a path 114 defined by the centers of balls 96, 86 and 94. Cue ball 112 is then struck hard, driven along path 114 and ball 86 follows path 116. If one wants to put ball 86 into pocket 68, a cue ball 118 is put at a point along a path 120 defined by the centers of balls 98, 86 and 92. Cue ball 118 is then struck hard, driven along path 120 and ball 86 follows path 122. While several illustrative embodiments of the invention have been disclosed, it is understood that various modifications will be obvious to those of ordinary skill in the art. For example, for balls of smaller diameter the dimensions of the templates would all be reduced in the same proportion. Such modifications are within the spirit and scope of the invention which is limited and defined only by the appended claims.
An accessory for billiard shooting is disclosed. The accessory comprises a planar element that is oriented and positioned on the billiard table playing surface. It includes marks for positioning a number of billiard ball at desired positions on the playing surface of the table. The cue ball is then put on the playing surface and driven by the cue into striking contact with the other balls, driving them into a plurality of predetermined pockets. Different "trick" shots can be performed by using differently constructed planar members.
0
CROSS-REFERENCES TO RELATED APPLICATIONS [0001] This application claims the benefit of Provisional Application No. 61/759560, filed Feb. 1, 2013, and Provisional Application No. 61/710610, filed Oct. 5, 2012, the disclosures of which are hereby expressly incorporated by reference herein. BACKGROUND [0002] The present invention pertains to an improved irrigator-aspirator tip component of the type inserted into the lens capsule of an eye, such as for removing cortical material, washing, cleaning and/or polishing. SUMMARY [0003] This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This summary is not intended to identify key features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter. [0004] In accordance with the present invention, a unitary, one-piece sleeve is provided for an ophthalmic irrigator-aspirator instrument of the type having a handpiece with an aspiration opening through the distal end thereof and one or more irrigation openings adjacent to the aspiration opening. The instrument includes an elongated, narrow tip projecting from the handpiece distal end, such tip having an internal bore communicating with the handpiece aspiration opening and an aspiration port at or adjacent to a distal end of the tip. The novel sleeve has a proximate annular hub portion constructed and arranged to be manually connected to a distal end portion of the handpiece in a watertight fit, with the sleeve surrounding the full extent of the tip and the aspiration and irrigation openings of the handpiece. An intermediate portion of the sleeve forms a channel for an irrigation fluid between the exterior of the tip and the interior portion of the sleeve. The channel is in communication with the handpiece irrigation opening and an irrigation port adjacent to the distal end of the sleeve, for conveying the irrigation fluid through the channel and ejecting it from the irrigation port of the sleeve. The distal end portion of the sleeve is sized for manual connection over the distal portion of the tip in a watertight fit at a location between the sleeve irrigation port and the aspiration port of the tip. Such distal end portion of the sleeve has an aspiration port located to be in communication with the tip aspiration port. The sleeve proximate, intermediate, and distal portions are integral with each other and are formed of a resilient material that allows the sleeve to be manually stretched onto the handpiece and tip. [0005] The sleeve is intended to be a single use item for an ophthalmic procedure, but the tip is protected by the sleeve during use and can be reused. DESCRIPTION OF THE DRAWINGS [0006] The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein: [0007] FIG. 1 is a top front perspective of an intraocular irrigator-aspirator tip component in accordance with the present invention with parts shown in exploded relationship; [0008] FIG. 2 is a corresponding perspective thereof on a somewhat larger scale showing some parts assembled; [0009] FIG. 3 is a vertical axial section thereof with the parts shown in the positions of FIG. 2 ; [0010] FIG. 4 is a section corresponding to FIG. 3 but on a larger scale and with parts fully assembled; [0011] FIG. 4A is a further enlarged, fragmentary, vertical section of the intraocular irrigator-aspirator tip component of FIGS. 1-4 ; [0012] FIG. 5 is a top front perspective of a second embodiment of an intraocular irrigator-aspirator tip component in accordance with the present invention with parts shown in exploded relationship; [0013] FIG. 6 is a corresponding perspective thereof on a somewhat larger scale showing some parts assembled; [0014] FIG. 7 is a vertical axial section thereof with the parts shown in the positions of FIG. 6 ; [0015] FIG. 8 is a section corresponding to FIG. 3 but on a larger scale and with parts fully assembled; [0016] FIG. 8A is a further enlarged, fragmentary, vertical section of the intraocular irrigator-aspirator tip component of FIGS. 5-8 ; [0017] FIG. 9 is a top front perspective of a modified form of an intraocular irrigator-aspirator tip component in accordance with the present invention with parts shown in exploded relationship; [0018] FIG. 10 is a fragmentary, enlarged, top plan thereof with the parts assembled; [0019] FIG. 11 is a vertical axial section thereof with the parts shown in the positions of FIG. 10 ; [0020] FIG. 12 is a top front perspective of another modified form of an intraocular irrigator-aspirator tip component in accordance with the present invention with parts shown in exploded relationship; [0021] FIG. 13 is a corresponding perspective thereof on a somewhat larger scale showing some parts assembled; [0022] FIG. 14 is a vertical axial section thereof with the parts shown in the positions of FIG. 13 ; [0023] FIG. 15 is a section corresponding to FIG. 14 but on a larger scale and with parts fully assembled; and [0024] FIG. 15A is a further enlarged, fragmentary, vertical section of the intraocular irrigator-aspirator tip component of FIGS. 12-15 . DETAILED DESCRIPTION [0025] With reference to FIG. 1 , an irrigation-aspiration handpiece 10 has a distal portion 12 adapted to receive a separate tip 14 which typically is surgical grade stainless steel or titanium. In a representative embodiment, tip 14 is reusable and has an externally threaded proximate stem 16 for reception in the internally threaded bore 18 that opens at the distal end of the handpiece. FIGS. 2-4 show the tip 14 after it has been joined to the handpiece 10 . In FIG. 3 it can be seen that the tip 14 has an internal bore 17 that communicates with the central longitudinal bore 18 of the handpiece 10 . At the proximate end, the handpiece is connected to a low pressure or vacuum source, such that aspiration is achieved through the distal end port 20 of the tip 16 as controlled by the user (typically a surgeon). In addition, the handpiece has an annular channel 22 for discharge of an irrigation liquid, such as to compensate for material aspirated through the tip 14 . [0026] In accordance with the present invention, a one-piece or unitary sleeve 24 of a soft, resilient material, such as silicone rubber, is provided for fitting tightly over the tip 14 and the distal end portion of the handpiece 10 to which the tip has been joined. [0027] With reference to FIG. 4 , the resilient sleeve 24 has a distal hub portion 26 with a wall diameter somewhat greater than the remainder of the sleeve for increased rigidity adjacent to a lip 28 in the area where the sleeve would typically be grasped by the surgeon or technician assembling the apparatus. At the proximate end, on the internal face 30 , the sleeve is tapered for ease in fitting the sleeve on and over the distal tip portion of the handpiece. The handpiece can be formed with an external thread 32 or a series of ribs to achieve a watertight fit of the sleeve on the handpiece. [0028] The diameter of an intermediate portion of the sleeve 24 gradually decreases along the length of the tip 14 , being sized to form an annular channel 34 which is in communication with the handpiece irrigation channel 22 . Moving still farther in a distal direction, the wall thickness of the sleeve lessens to increase the overall flexibility of the sleeve in the area where it will protrude through a corneal incision. [0029] The details of the distal-most portion of the sleeve 24 and inner tip 14 are best seen in FIG. 4A . In this embodiment, the distal end of the tip 14 has the end port 20 . The sleeve 24 has a distal end portion 36 that projects beyond the end port 20 , with an internal aspiration cavity 38 in communication therewith. In the embodiment shown, the end portion 36 of the sleeve has an annular shoulder 40 to butt against the distal end of the tip 14 when the sleeve is inserted fully over the tip. An external aspiration port 42 is formed in the distal sleeve part 36 . In the illustrated embodiment, port 42 extends obliquely, which is preferred, but it can be positioned at any desired location around the sleeve portion 36 . The wall thickness at the distal portion 36 is greater than the thickness where the sleeve fits over the tip 14 , for a somewhat less flexible but still soft tip that can be manipulated by the surgeon to a desired location. The fit of the sleeve around the distal end of the tip is very snug and watertight. [0030] Still referring to FIG. 4A , one or more ports 44 are provided for expulsion of irrigation liquid close to the aspiration port but nevertheless spaced proximate therefrom. Typically, during an intraocular procedure both ports will be positioned inside the cornea and usually inside the lens capsule. The distal part 36 of the sleeve is unsupported and should have sufficient rigidity that it does not collapse so as to block aspiration. Nevertheless, the part of the sleeve 24 proximate to the irrigation port 44 will be fitted through a small corneal slit, and should be sufficiently flexible to conform to the shape of the slit without unduly stretching or tearing the cornea. Whereas the tip 14 itself is very rigid and can have sharp edges that could tear delicate eye tissue with which they come into engagement, the sleeve is soft enough that the risk of tearing, cutting, or abrasion of eye tissue is reduced significantly. In addition, the sleeve protects the tip 14 from being damaged, such as by contact with other instruments during surgery. The sleeve can be a single-use item, allowing the aspiration tip to be used multiple times. [0031] FIGS. 5 to 8A correspond, respectively, to FIGS. 1 to 4A , but for a second representative embodiment of the present invention. The handpiece 10 is the same, including the distal portion 12 , central aspiration bore 18 , and annular irrigation channel 22 . The separate tip 14 ′ has the same threaded stem 16 for joining to the handpiece, but the distal end portion of the tip 14 ′ and the distal end portion of the sleeve 24 ′ are a little different. [0032] As best seen in FIG. 8A , the distal end of the tip 14 ′ is closed, and the aspiration port 20 ′ opens through the side, very close to the distal end. The distal end portion 36 ′ of the resilient sleeve tightly embraces the closed end of the tip 14 ′ and the end portion on both sides of the port 20 ′ in a watertight fit. The sleeve 24 ′ has an aspiration port 42 ′ located to register with the tip port 20 ′ when the parts are assembled. Port 42 ′ can be smaller than port 20 ′ so that the hard and potentially sharp metal inner tip will not come in contact with delicate eye tissue during use. [0033] For both illustrated embodiments it is important that the sleeve 24 / 24 ′ be fully inserted on the tip 14 / 14 ′, and for both embodiments it is important that the sleeve be correctly aligned or registered with the tip. FIGS. 9-11 illustrate modifications that can be used with both embodiments to assist in obtaining the correct relative orientation. [0034] The tip 14 / 14 ′ is “clocked” to the handpiece 10 ′ so that the relative orientation will be the same each time one of the aspiration tips is connected. For example, in FIG. 9 the bend of the tip toward its distal end would always be oriented vertically upward. A registration mark (arrow 50 ) is formed on the exterior of the handpiece for reference, preferably on an enlarged extension 52 . Extension 52 has a flat annular face 54 from which the distal portion 12 ′ extends. Such portion 12 ′ has a pair of longitudinally spaced, circumferential ribs 32 ′ adjacent to the distal end of the handpiece. The sleeve 24 ″ also has a registration mark (arrow 54 ) formed thereon. During assembly, the surgeon or technical assistant can manually pull the sleeve over the aspirator tip 14 / 14 ′ while keeping the registration marks in alignment, thereby assuring the correct relative orientation. [0035] In addition, the construction of the modified sleeve 24 ″ and handpiece 10 ′ help assure that the sleeve will be fully stretched over the tip and handpiece to the desired degree, and no more. The proximate end of the sleeve will abut against the face 54 of the handpiece extension 52 , and, as seen in FIG. 11 , an internal rib 56 of the sleeve 24 ″ is snugly received between the handpiece ribs 32 ′ when the desired fit is achieved. [0036] FIGS. 12 to 15A correspond, respectively, to FIGS. 1 to 4A , but for a third representative embodiment of the present invention. The handpiece 10 ′ is the same as previously described except for the distal portion 12 ′″. For example, the handpiece of the third embodiment still has the central aspiration bore 18 (see FIGS. 14 and 15 ) and annular irrigation channel 22 , and the bore and channel open through the distal end of the distal portion 12 ′″. The outer periphery of the distal portion 12 ′″ is configured for connection to a composite rigid tip component 60 . Tip component 60 has an internally threaded hub or base 62 for joining to the handpiece, such as by mating threads (external on the handpiece distal portion 12 ′″ and internal in the hub or base 62 ). FIGS. 13 , 14 , and 15 show the hub or base 62 connected to the handpiece. [0037] The hub or base 62 can be formed of a rigid plastic material. The composite tip 60 includes a rigid (preferably surgical grade stainless steel or titanium) cannula 64 projecting distally from the hub or base 62 . The cannula is fixed in the base, such as by overmolding during manufacturing. As seen in FIG. 15 , the bore 66 of the cannula communicates with the aspiration bore 18 of the handpiece and can terminate at or near a distal port 68 . [0038] As best seen in FIGS. 13 and 14 , the hub or base 62 includes a distal protrusion or stem 70 . As seen in FIGS. 14 and 15 , stem 70 has longitudinal passages 72 that communicate with the annular irrigation channel 20 of the handpiece. [0039] This embodiment includes a thin-walled resilient sleeve 24 ′″ similar to the sleeves previously described. The proximate end portion (hub) 74 of sleeve 24 ′″ can be fitted tightly over the stem 70 of the composite tip component 60 . As best seen in FIG. 15 , an interior rib 76 at the proximate end of the sleeve can be received in a groove 78 at the proximate end of the stem for a reliable connection of the sleeve to the stem. For registration purposes, the outer periphery of the stem can be a shape other than cylindrical and the proximate portion of the sleeve shaped the same. In the illustrated embodiment the stem and sleeve are approximately triangular in transverse cross section so the sleeve will be oriented correctly as it is slid on the stem prior to use of the IA instrument. [0040] As best seen in FIG. 15A , the distal end of the rigid cannula opens through an end port 88 . The distal end portion of the resilient sleeve 24 ′″ tightly embraces the tip of the cannula in a watertight fit. The sleeve 24 ′″ has an aspiration port 80 in fluid communication with the bore of the cannula, and a nearby irrigation port 82 that communicates with the annular passage for irrigation liquid that flows from the handpiece. [0041] Although this embodiment shows an end port for the cannula, the cannula and sleeve can be modified similar to the embodiment of FIGS. 6 to 8A for a side port application. Either way, it is intended that this embodiment of a composite tip and one-piece or unitary resilient sleeve be sold preassembled as a single use item for quick and reliable connection to a reusable handpiece. Both aspiration and irrigation are supported, and sterility is assured because the tip and sleeve are discarded after one use. [0042] While illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.
An ophthalmic irrigator-aspirator has a handpiece with aspiration and irrigation openings through its distal end; and a narrow aspiration tip projecting distally. A flexible sleeve has an annular hub for watertight connection to the handpiece. The sleeve surrounds the full extent of the tip. An intermediate portion of the sleeve forms a channel for an irrigation fluid along the exterior of the tip to a port in the sleeve. The distal end of the sleeve is sized for a watertight connection over the distal portion of the tip. Such distal end of the sleeve has an aspiration port in communication with the tip aspiration port. The sleeve proximate, intermediate, and distal portions are integral with each other and are formed of a resilient material that allows the sleeve to be manually stretched onto the handpiece and tip.
0
CROSS-REFERENCE TO RELATED APPLICATION [0001] This application claims priority from U.S. Provisional Application Ser. No. 60/832,897, filed Jul. 24, 2006, which is incorporated by reference herein in its entirety. GOVERNMENT INTERESTS [0002] This invention was made with government support under Grant No. R01DK054257-08A1 awarded by the National Institutes of Health. The government has certain rights in this invention. FIELD OF THE INVENTION [0003] Disclosed herein are novel antagonists of the androgen receptor and mutant forms of the androgen receptor associated with clinical failure of currently prescribed anti-androgens. BACKGROUND OF THE INVENTION [0004] Thirty to forty percent of prostate cancer patients become androgen independent (resistant to anti-androgen treatment) within five years. In many instances, androgen receptor mutations in androgen-independent prostate cancer cells cause anti-androgens to act as agonists or change receptor specificity. In these cases, alternative treatment regimes are needed. Exemplary treatments can be found in U.S. Pat. No. 4,636,505, which discloses acylanilides that have anti-androgenic properties, and U.S. Pat. No. 7,057,048, which discloses 6-sulfonamido-quinolin-2-one and 6-sulfonamido-2-oxo-chromeme derivatives and their use as androgen antagonists. [0005] Androgen receptor mutations are found in as many as 50% of metastatic, hormone refractory prostate cancer tumors. Studies suggest that 12-24% of hormone refractory tumors treated with flutamide contain the same T877A mutation. [0006] Applicants herein disclose anti-androgens that are uniquely designed to target mutant forms of the androgen receptor that are known to impart resistance to known anti-androgens used in cancer chemotherapy. As such, these novel anti-androgens are believed to have the potential to delay the occurrence of anti-androgen resistance/anti-androgen withdrawal syndrome and to serve as a second line of defense in anti-androgen therapy when mutations to the androgen receptor give rise to anti-androgen withdrawal. SUMMARY OF THE INVENTION [0007] One aspect relates to a compound of the formula: wherein R 1 is hydrogen, fluorine, chlorine, bromine, cyano, hydroxy, methyl acrylate, or C 1 -C 6 alkyl optionally substituted with hydroxy; R 2 is hydrogen, hydroxy, fluoro, chloro, cyano, C 1 -C 5 alkanoate, C 1 -C 5 alkylamino, or C 1 -C 6 alkyl optionally substituted with hydroxy or acrylate; and R 3 is hydrogen, C 1 -C 6 alkyl, fluoro, chloro, bromo, or cyano. [0008] Another aspect relates to a compound of the formula: wherein R 4 is phenyl optionally substituted with hydroxy; C 1 -C 6 phenylalkyl; C 1 -C 8 alkoxy; or benzyl optionally substituted with hydroxy, C 1 -C 6 alkoxy optionally substituted with methoxy or cyano, C 1 -C 6 alkyl, C 1 -C 5 alkanoate, or C 1 -C 5 alkylamine. [0009] A further aspect is for a method for the treatment of a mammal suffering from an androgen-dependent disorder comprising administering to the mammal in need thereof a therapeutically effective amount of a compound of Formula (I) or (II). [0010] An additional aspect relates to a method for the treatment of a mammal suffering from an androgen-dependent disorder comprising administering to the mammal in need thereof a therapeutically effective amount of a compound of Formula (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), (XIX), (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV) or a combination thereof. [0011] A further aspect is for a method for monitoring the effectiveness of treatment of a subject with a compound of Formula (I) or (II) comprising the steps of (i) obtaining a pre-administration sample from a subject prior to administration of the compound; (ii) detecting the level of androgen receptor activity in the pre-administration sample; (iii) obtaining one or more post-administration samples from the subject; (iv) detecting the level of androgen receptor activity in the post-administration samples; comparing the level of androgen receptor activity in the pre-administration sample with the post administration sample or samples; and altering the administration of the compound to the subject accordingly. [0012] Another aspect is for a method for monitoring the effectiveness of treatment of a subject with a compound of Formula (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), (XIX), (XX), (XXI), (XXII), (XXIII), (XXIV), (XXV) or a combination thereof comprising the steps of (i) obtaining a pre-administration sample from a subject prior to administration of the compound; (ii) detecting the level of androgen receptor activity in the pre-administration sample; (iii) obtaining one or more post-administration samples from the subject; (iv) detecting the level of androgen receptor activity in the post-administration samples; (v) comparing the level of androgen receptor activity in the pre-administration sample with the post administration sample or samples; and (vi) altering the administration of the compound to the subject accordingly. [0013] Other objects and advantages will become apparent to those skilled in the art upon reference to the detailed description that hereinafter follows. BRIEF DESCRIPTION OF THE FIGURES [0014] FIG. 1 . Cellular transcriptional activity with AR(wild-type). RLU: relative light units of luciferase reporter gene wherein maximal activity of AR(wild-type) with dihydrotestosterone (DHT) is assigned a value of 100. [0015] FIG. 2 . Cellular transcriptional activity with mutant androgen receptor, AR(T877A). RLU: relative light units of luciferase reporter gene wherein maximal activity of AR(wild-type) with DHT is assigned a value of 100. [0016] FIG. 3 . Cellular transcriptional activity with mutant androgen receptor, AR(W741C). RLU: relative light units of luciferase reporter gene wherein maximal activity of AR(wild-type) with DHT is assigned a value of 100. [0017] FIG. 4 . Cellular transcriptional activity with mutant androgen receptor, AR(W741 L). RLU: relative light units of luciferase reporter gene wherein maximal activity of AR(wild-type) with DHT is assigned a value of 100. [0018] FIG. 5 . Inhibition of DHT induced transcription with mutant androgen receptor, AR(W741L), in cell based assays. RLU: relative light units of luciferase reporter gene wherein maximal activity of AR(wild-type) with DHT is assigned a value of 100. [0019] FIG. 6 . Inhibition of DHT induced transcription with mutant androgen receptor, AR(W741C), in cell based assays. RLU: relative light units of luciferase reporter gene wherein maximal activity of AR(wild-type) with DHT is assigned a value of 100. [0020] FIG. 7 . Inhibition of DHT induced transcription with (wild-type) androgen receptor, AR(wt), in cell based assays. RLU: relative light units of luciferase reporter gene wherein maximal activity of AR(wild-type) with DHT is assigned a value of 100. [0021] FIG. 8 . Inhibition of DHT induced transcription with mutant androgen receptor, AR(T877A), in cell based assays. RLU: relative light units of luciferase reporter gene wherein maximal activity of AR(wild-type) with DHT is assigned a value of 100. [0022] FIG. 9 . LNCaP cell proliferation (CyQuant) after 8 day ligand treatment±R1881. Relative Fluorescence ±SEM. (R1881±ligand; P<0.05, one-way ANOVA). [0023] FIG. 10 . In vitro selections of LnCaP cells with 20 μM bicalutamide: A. week 1, B. Week 4, C. Week 20; 20 μM Formula III: D. week 1, E. week 4, F. week 12; 20 μM Formula VII: G. week 1, H. Week 4, I. Week 10 (note: no colonies detected in two of three experiments). [0024] FIG. 11 . Synthetic scheme for construction of precursors for PAN41, PAN51, PAN61. [0025] FIG. 12 . General strategy for synthesis of PAN41, PAN51, PAN61. [0026] FIG. 13 . General strategy for synthesis of PAN11. [0027] FIG. 14 . General strategy for synthesis of PAN21. [0028] FIG. 15 . General strategy for synthesis of PAN31. [0029] FIG. 16 . General strategy for synthesis of PAN71. DETAILED DESCRIPTION OF THE INVENTION [0030] Applicants specifically incorporate the entire content of all cited references in this disclosure. Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range. I. DEFINITIONS [0031] In the context of this disclosure, a number of terms shall be utilized. [0032] The term “androgen” includes all known compounds with androgenic activity. Androgenic activity of compounds may be determined in a variety of ways including in cell-based AR transcription assays and in biological activity assays where a compound can be demonstrated to have activity that is similar to the activity of known androgens. These assays can be performed using animals or tissues. For example, compounds with androgen activity in the prostate are able to stimulate prostate growth in rodents. Natural androgen metabolites that have biological activity can be used and include, for example, testosterone, and rostened ione, and rostanedione, and dihydrotestosterone (DHT). [0033] The term “androgen-dependent disorder” refers to any disorder that can benefit from a decrease in androgen stimulation and includes pathological conditions that depend on androgen stimulation. An “androgen-dependent disorder” can result from an excessive accumulation of testosterone or other androgenic hormone, increased sensitivity of androgen receptors to androgen, or an increase in androgen-stimulated transcription. Examples of “androgen-dependent disorders” include prostate cancer and skin disorders such as, for example, acne, seborrhea, hirsutism, alopecia, or hidradenitis suppurativa. [0034] The term “androgen receptor” or “AR” refers to the androgen receptor protein as defined by its conserved amino acid coding sequence in an active or native structural conformation. Nucleic acid sequences encoding androgen receptors have been cloned and sequenced from numerous organisms. Representative organisms and GenBank® accession numbers for androgen receptor sequences therefrom include the following: frog ( Xenopus levis ; U67129), mouse ( Mus musculus, 109558), rat ( Rattus norvegicus, 292896), human ( Homo sapiens, 105325), rabbit ( Oryctolagus cuniculus, 577829), cow ( Bos taurus , Z75313, Z75314, Z75315), canary ( Serinus canaria, 414734), whiptail lizard ( Cnemidophous uniparens, 1195596), and canine ( Canis familiaris , AF197950). [0035] The term “anti-androgen” as used herein refers to Formula I or Formula II compounds that specifically block the entry of androgens into cells of the body. Anti-androgens are believed to act by competitively inhibiting the action of androgens by binding to androgen receptors and/or mutant forms of the androgen receptor, and preventing androgens from binding to the receptors and entering the cell nucleus. [0036] The terms “effective amount”, “therapeutically effective amount”, and “effective dosage” as used herein, refer to the amount of a Formula I or II compound that, when administered to a mammal in need, is effective to at least partially ameliorate a condition from which the mammal is suspected to suffer. [0037] The term “mammal” refers to a human, a non-human primate, canine, feline, bovine, ovine, porcine, murine, or other veterinary or laboratory mammal. Those skilled in the art recognize that a therapy which reduces the severity of a pathology in one species of mammal is predictive of the effect of the therapy on another species of mammal. The skilled person also appreciates that credible animal models of human prostate cancer pathologies are known. II. ANTI-ANDROGEN COMPOUNDS [0038] One aspect is for a compound of the formula: wherein R 1 is hydrogen, fluorine, chlorine, bromine, cyano, hydroxy, methyl acrylate, or C 1 -C 6 alkyl optionally substituted with hydroxy; R 2 is hydrogen, hydroxy, fluoro, chloro, cyano, C 1 -C 5 alkanoate, C 1 -C 5 alkylamino, or C 1 -C 6 alkyl optionally substituted with hydroxy or acrylate; and R 3 is hydrogen, C 1 -C 6 alkyl, fluoro, chloro, bromo, or cyano. [0039] Formula I compounds of particular interest include, for example, [0040] Another aspect is for a compound of the formula: wherein R 4 is phenyl optionally substituted with hydroxy; C 1 -C 6 phenylalkyl; C 1 -C 8 alkoxy; or benzyl optionally substituted with hydroxy, C 1 -C 6 alkoxy optionally substituted with methoxy or cyano, C 1 -C 6 alkyl, C 1 -C 5 alkanoate, or C 1 -C 5 alkylamine. [0041] Formula II compounds of particular interest include, for example, III. GENERAL FORMULA I AND II COMPOUND SYNTHETIC SCHEME [0042] Thiols were synthesized from their corresponding anilines or amines, when not commercially available. Briefly, concentrated hydrochloric acid was added to a cooled solution of amine or aniline dissolved in water. A cooled solution of sodium nitrite in water was added slowly and the reaction stirred for 30 minutes. This solution was then added to a solution of potassium ethyl xanthate in water warmed to 45° C. and stirred for a further 30 minutes. Diethyl ether was added and the organic layer was washed with 10% sodium hydroxide and water until neutral. The organic layer was dried over magnesium sulfate, filtered and evaporated. The crude product was then dissolved in ethanol and heated to reflux. Potassium hydroxide pellets were added and refluxing was continued overnight. The ethanol was evaporated. The residue was diluted with water and extracted with diethyl ether. The aqueous layer was acidified with 2 N HCl and extracted with diethyl ether. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated to yield the crude thiol, which could be further purified by column chromatography if necessary. Alternatively, thiols can be generated by transition metal mediated cross coupling with aryl halides or aryl triflates (see, for example: Buchwald et al., Tetrahedron, 2004, 60, 7397, and Zheng et al., J. Organic Chemistry, 1998, 63, 9606). [0043] Aryl and alkyl amines can be derived directly from their corresponding nitro compounds. Briefly, the nitro compound and 10% palladium on carbon were dissolved in methanol and purged with nitrogen then placed under an atmosphere of hydrogen overnight or until the reaction was complete. The reaction mixture was filtered and solvent evaporated to yield the desired amine. [0044] The thiols were added to the epoxide, N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide, to form the sulfide intermediate. This epoxide was synthesized following published procedures. (For example: Chen et al., J. Organic Chemistry, 2003, 68, 10181 and Tucker, H., Crook, J. W. and Chesterson, J. W., J. Med. Chem. 1988, 31, 954.) [0045] The epoxide ring opening was achieved using a base and the appropriate thiol in a suitable solvent. For example, sodium hydride (60% dispersed in mineral oil) was suspended in THF (tetrahydrofuran) and cooled to 0° C. A solution of the thiol in THF was added via syringe and stirred for 5 minutes. N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide dissolved in THF was added slowly. The reaction was allowed to warm to room temperature and stirred overnight. The solvent was evaporated. The residue was diluted with water and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over magnesium sulfate, filtered and evaporated. The compound was purified by column chromatography. [0046] The sulfide intermediate was oxidized to give the final desired sulfone compounds. Briefly, the sulfide was dissolved in dichloromethane and cooled to −78° C. 30% hydrogen peroxide was added followed by the slow addition of trifluoroacetic anhydride. The reaction was stirred at room temperature for 16 h. The reaction was diluted with dichloromethane and cold water and brine were added. The reaction was stirred for 20 minutes. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated. The compound was purified by column chromatography. [0047] Some of the compounds of Formulas I and II will exist as optical isomers. Any reference in this application to one of the compounds represented by Formula I or II is meant to encompass either a specific optical isomer or a mixture of optical isomers (unless it is expressly excluded). The specific optical isomers can be separated and recovered by techniques known in the art such as chromatography on chiral stationary phases or resolution via chiral salt formation and subsequent separation by selective crystallization. Alternatively, utilization of a specific optical isomer as the starting material will produce the corresponding isomer as the final product. IV. ADMINISTRATION OF ANTI-ANDROGENS [0048] Formula I or II compounds can be administered to subjects in a biologically compatible form suitable for pharmaceutical administration in vivo. By “biologically compatible form suitable for administration in vivo” is meant a form of the Formula I or II compound to be administered in which any toxic effects are outweighed by the therapeutic effects of the compound. The term subject is intended to include living organisms in which an immune response can be elicited, for example, mammals. Administration of a Formula I or II compound as described herein can be in any pharmacological form including a therapeutically active amount of a Formula I or II compound alone or in combination with a pharmaceutically acceptable carrier. [0049] A therapeutically effective amount of a Formula I or II compound may vary according to factors such as the disease state, age, sex, and weight of the individual, and the ability of the compound to elicit a desired response in the individual. Dosage regime may be adjusted to provide the optimum therapeutic response. For example, several divided doses may be administered daily, or the dose may be proportionally reduced as indicated by the exigencies of the therapeutic situation. [0050] The therapeutic or pharmaceutical compositions can be administered by any suitable route known in the art including, for example, intravenous, subcutaneous, intramuscular, transdermal, intrathecal, or intracerebral or administration to cells in ex vivo treatment protocols. Administration can be either rapid as by injection or over a period of time as by slow infusion or administration of slow release formulation. For treating prostate cancer, administration of the therapeutic or pharmaceutical compositions of the present invention can be performed, for example, orally or subcutaneously. For skin disorders, administration of the therapeutic or pharmaceutical compositions of the present invention can be performed, for example, topical or oral administration. [0051] Formula I or II compounds can also be linked or conjugated with agents that provide desirable pharmaceutical or pharmacodynamic properties. For example, Formula I or II compounds can be coupled to any substance known in the art to promote penetration or transport across the blood-brain barrier such as an antibody to the transferrin receptor, and administered by intravenous injection (see, e.g., Friden P M et al., Science 259:373-77 (1993)). Furthermore, Formula I or II compounds can be stably linked to a polymer such as polyethylene glycol to obtain desirable properties of solubility, stability, half-life, and other pharmaceutically advantageous properties (see, e.g., Davis et al., Enzyme Eng. 4:169-73 (1978); Burnham N L, Am. J. Hosp. Pharm. 51:210-18 (1994)). [0052] Furthermore, Formula I or II compounds can be in a composition which aids in delivery into the cytosol of a cell. For example, a Formula I or II compound may be conjugated with a carrier moiety such as a liposome that is capable of delivering the compound into the cytosol of a cell. Such methods are well known in the art (see, e.g., Amselem S et al., Chem. Phys. Lipids 64:219-37 (1993)). Alternatively, the compound can be delivered directly into a cell by microinjection. [0053] The Formula I or II compounds are usefully employed in the form of pharmaceutical preparations. Such preparations are made in a manner well known in the pharmaceutical art. One preferred preparation utilizes a vehicle of physiological saline solution, but it is contemplated that other pharmaceutically acceptable carriers such as physiological concentrations of other non-toxic salts, five percent aqueous glucose solution, sterile water or the like may also be used. As used herein “pharmaceutically acceptable carrier” includes any and all solvents, dispersion media, coatings, antibacterial and antifungal agents, isotonic and absorption delaying agents, and the like. The use of such media and agents for pharmaceutically active substances is well known in the art. Except insofar as any conventional media or agent is incompatible with the active compound, use thereof in the therapeutic compositions is contemplated. Supplementary active compounds can also be incorporated into the compositions. It may also be desirable that a suitable buffer be present in the composition. Such solutions can, if desired, be lyophilized and stored in a sterile ampoule ready for reconstitution by the addition of sterile water for ready injection. The primary solvent can be aqueous or alternatively non-aqueous. Formula I or II compounds can also be incorporated into a solid or semi-solid biologically compatible matrix which can be implanted into tissues requiring treatment. [0054] The carrier can also contain other pharmaceutically-acceptable excipients for modifying or maintaining the pH, osmolarity, viscosity, clarity, color, sterility, stability, rate of dissolution, or odor of the formulation. Similarly, the carrier may contain still other pharmaceutically-acceptable excipients for modifying or maintaining release or absorption or penetration across the blood-brain barrier. Such excipients are those substances usually and customarily employed to formulate dosages for parenteral administration in either unit dosage or multi-dose form or for direct infusion by continuous or periodic infusion. [0055] Formula I or II compounds may be used individually or in combination and with other anti-androgens or other treatments, such as flutamide, bicalutamide, and nilutamide; irradiation; heat; luteinizing hormone-releasing hormone or luteinizing hormone-releasing hormone analog, such as goserelin; or the like, as may be conventionally employed and as may be moderated for use in conjunction with the Formula I or II compounds. [0056] Dose administration can be repeated depending upon the pharmacokinetic parameters of the dosage formulation and the route of administration used. [0057] It is also provided that certain formulations containing the Formula I or II compounds are to be administered orally. Such formulations are preferably encapsulated and formulated with suitable carriers in solid dosage forms. Some examples of suitable carriers, excipients, and diluents include lactose, dextrose, sucrose, sorbitol, mannitol, starches, gum acacia, calcium phosphate, alginates, calcium silicate, microcrystalline cellulose, polyvinylpyrrolidone, cellulose, gelatin, syrup, methyl cellulose, methyl- and propylhydroxybenzoates, talc, magnesium, stearate, water, mineral oil, and the like. The formulations can additionally include lubricating agents, wetting agents, emulsifying and suspending agents, preserving agents, sweetening agents, or flavoring agents. The compositions may be formulated so as to provide rapid, sustained, or delayed release of the active ingredients after administration to the patient by employing procedures well known in the art. The formulations can also contain substances that diminish proteolytic degradation and/or substances which promote absorption such as, for example, surface active agents. [0058] In some embodiments, Formula I or II compounds are utilized for the treatment of androgen-related diseases of the skin such as, for example, acne, seborrhea, hirsutism, alopecia, or hidradenitis suppurativa. When used for any of these purposes, the Formula I or II compounds are preferably administered topically together with a conventional topical carrier or diluent. When used topically, it is preferred that the diluent or carrier does not promote transdermal penetration of the active ingredients into the blood stream or other tissues where they might cause unwanted systemic effects. [0059] It is especially advantageous to formulate compositions in dosage unit form for ease of administration and uniformity of dosage. Dosage unit form as used herein refers to physically discrete units suited as unitary dosages for the mammalian subjects to be treated; each unit containing a predetermined quantity of active compound calculated to produce the desired therapeutic effect in association with the required pharmaceutical carrier. The specification for the dosage unit forms of the invention are dictated by and directly dependent on (a) the unique characteristics of the active compound and the particular therapeutic effect to be achieved and (b) the limitations inherent in the art of compounding such an active compound for the treatment of sensitivity in individuals. The specific dose can be readily calculated by one of ordinary skill in the art, e.g., according to the approximate body weight or body surface area of the patient or the volume of body space to be occupied. The dose will also be calculated dependent upon the particular route of administration selected. Further refinement of the calculations necessary to determine the appropriate dosage for treatment is routinely made by those of ordinary skill in the art. Such calculations can be made without undue experimentation by one skilled in the art in light of the anti-androgen activity disclosed herein in assay preparations of target cells. Exact dosages are determined in conjunction with standard dose-response studies. It will be understood that the amount of the composition actually administered will be determined by a practitioner, in the light of the relevant circumstances including the condition or conditions to be treated, the choice of composition to be administered, the age, weight, and response of the individual patient, the severity of the patient's symptoms, and the chosen route of administration. [0060] Toxicity and therapeutic efficacy of such compounds can be determined by standard pharmaceutical procedures in cell cultures or experimental animals, for example, for determining the LD 50 (the dose lethal to 50% of the population) and the ED 50 (the dose therapeutically effective in 50% of the population). The dose ratio between toxic and therapeutic effects is the therapeutic index and it can be expressed as the ratio LD 50 /ED 50 . Compounds which exhibit large therapeutic indices are preferred. While compounds that exhibit toxic side effects may be used, care should be taken to design a delivery system that targets such compounds to the site of affected tissue in order to minimize potential damage to uninfected cells and, thereby, reduce side effects. [0061] The data obtained from the cell culture assays and animal studies can be used in formulating a range of dosage for use in humans. The dosage of such compounds lies preferably within a range of circulating concentrations that include the ED 50 with little or no toxicity. The dosage may vary within this range depending upon the dosage form employed and the route of administration utilized. For any compound used in the method of the invention, the therapeutically effective dose can be estimated initially from cell culture assays. A dose may be formulated in animal models to achieve a circulating plasma concentration range that includes the IC 50 (i.e., the concentration of the test compound which achieves a half-maximal inhibition of symptoms) as determined in cell culture. Such information can be used to more accurately determine useful doses in humans. Levels in plasma may be measured, for example, by high performance liquid chromatography. [0062] In one embodiment, the present invention provides a method for monitoring the effectiveness of treatment of a subject with a Formula I or II compound comprising the steps of (i) obtaining a pre-administration sample from a subject prior to administration of the compound; (ii) detecting the level of androgen receptor activity in the pre-administration sample; (iii) obtaining one or more post-administration samples from the subject; (iv) detecting the level of androgen receptor activity in the post-administration samples; (v) comparing the level of androgen receptor activity in the pre-administration sample with the post administration sample or samples; and (vi) altering the administration of the compound to the subject accordingly. For example, increased administration of the Formula I or II compound may be desirable to decrease the activity of androgen receptor to lower levels than detected, that is, to increase the effectiveness of the compound. Alternatively, decreased administration of the compound may be desirable to increase androgen receptor activity to higher levels than detected, that is, to decrease the effectiveness of the compound. [0063] In another embodiment, the ability of a Formula I or II compound to modulate androgen receptor activity in a subject that would benefit from modulation of the activity of the androgen receptor can be measured by detecting an improvement in the condition of the patient after the administration of the compound. Such improvement can be readily measured by one of ordinary skill in the art using indicators appropriate for the specific condition of the patient. Monitoring the response of the patient by measuring changes in the condition of the patient is preferred in situations were the collection of biopsy materials would pose an increased risk and/or detriment to the patient. [0064] Furthermore, in the treatment of disease conditions, compositions containing Formula I or II compounds can be administered exogenously and it would likely be desirable to achieve certain target levels of Formula I or II compounds in sera, in any desired tissue compartment, or in the affected tissue. It would, therefore, be advantageous to be able to monitor the levels of Formula I or II compounds in a patient or in a biological sample including a tissue biopsy sample obtained from a patient. Accordingly, the present invention also provides methods for detecting the presence of Formula I or II compounds in a sample from a patient. [0065] All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. It will be apparent to those of skill in the art that variations may be applied to the compositions and methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit, and scope of the invention. More specifically, it will be apparent that certain agents which are chemically or biologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the invention as defined by the appended claims. EXAMPLES [0066] The present invention is further defined in the following Examples. It should be understood that these Examples are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the preferred features of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various uses and conditions. [0067] The following abbreviations are here defined: PLM1: N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methyl-3-(naphthalen-1-ylsulfonyl)propanamide; PLM2: 3-(2-benzylphenylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide; PLM3: 3-(3-benzylphenylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide; PLM4: 3-(2-phenylphenylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide; PLM5: 3-(3-methoxyphenylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide; PLM21: 3-(1-hydroxynaphthalen-5-ylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide; PLM9: 3-(1-bromonaphthalen-4-ylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide; PLM13: 3-(1-chloronaphthalen-4-ylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide; PLM11: 3-(2-methylnaphthalen-1-ylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide; PLM12: 3-(1-cyanonaphthalen-4-ylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide; PLM54: 3-(1-phenylphenylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide; PLM55: N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methyl-3-(naphthalen-2-ylsulfonyl)propanamide; PLM14: N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(4-(3-hydroxypropyl)naphthalen-1-ylsulfonyl)-2-methylpropanamide; PLM15: N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(5-(3-hydroxypropyl)naphthalen-1-ylsulfonyl)-2-methylpropanamide; PLM16: (E)-methyl 3-(4-(3-(4-cyano-3-(trifluoromethyl)phenylamino)-2-hydroxy-2-methyl-3-oxopropylsulfonyl)naphthalen-1-yl)acrylate; PLM18: (E)-methyl 3-(5-(3-(4-cyano-3-(trifluoromethyl)phenylamino)-2-hydroxy-2-methyl-3-oxopropylsulfonyl)naphthalen-1-yl)acrylate; PAN71: N-(4-cyano-3-(trifluoromethyl)phenyl)-3-(2-(2,5-dimethylbenzyl)phenylsulfonyl)-2-hydroxy-2-methylpropanamide; PAN11: N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2-(2-hydroxybenzyl)phenylsulfonyl)-2-methylpropanamide; PAN21: N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2-(3-hydroxybenzyl)phenylsulfonyl)-2-methylpropanamide; PAN31: N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2-(4-hydroxybenzyl)phenylsulfonyl)-2-methylpropanamide; PAN32: N-(4-cyano-3-(trifluoromethyl)phenyl)-3-(2-(4-(cyanomethoxy)benzyl)phenylsulfonyl)-2-hydroxy-2-methylpropanamide; PAN33: N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2-(4-methoxybenzyl)phenylsulfonyl)-2-methylpropanamide; PAN37: N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2-(4-(methoxymethoxy)benzyl)phenylsulfonyl)-2-methylpropanamide; PAN41: N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2′-hydroxybiphenyl-2-ylsulfonyl)-2-methylpropanamide; PAN51: N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(3′-hydroxybiphenyl-2-ylsulfonyl)-2-methylpropanamide; PAN61: N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(4′-hydroxybiphenyl-2-ylsulfonyl)-2-methylpropanamide. Example 1 N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methyl-3-(naphthalen-1-ylthio)propanamide [0068] To a stirred suspension of sodium hydride (60% dispersed in mineral oil, 9.7 mg, 0.242 mmol) in THF (0.1 mL) was added a solution of 1-naphthalenethiol (36.9 mg, 0.23 mmol) in THF (0.07 mL) at 0° C. The mixture was stirred for 5 minutes. A solution of N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide (50 mg, 0.185 mmol) in THF (0.25 mL) was added slowly. The reaction was allowed to warm to room temperature and stirred overnight. The reaction mixture was concentrated and then diluted with water and extracted with ethyl acetate (50 mL). The organic extract was washed with water (25 mL) and brine (25 mL), dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 31 mg of desired product. Production of N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methyl-3-(naphthalen-1-ylthio)propanamide was confirmed by 1-H NMR, 13-C NMR, and mass spectral analysis. Example 2 N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methyl-3-(naphthalen-1-ylsulfonyl)propanamide (PLM1) [0069] N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methyl-3-(naphthalen-1-ylthio)propanamide (31 mg, 0.072 mmol) was dissolved in dichloromethane (0.2 mL) and cooled to −78° C. 30% hydrogen peroxide (16.7 μL, 0.58 mmol) was added followed by the slow addition of trifluoroacetic anhydride (62 μL, 0.43 mmol). The reaction was stirred at room temperature for 16 h. The reaction was diluted with dichloromethane. Cold water and brine were added and the reaction was stirred for 20 minutes. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 25 mg of desired product. Production of PLM1 was confirmed by 1-H NMR, 13-C NMR, and mass spectral analysis. Example 3 S-2-benzylphenyl-O-ethyl carbonodithioate [0070] Concentrated hydrochloric acid (0.4 mL) was added slowly to a solution of 2-benzylaniline (500 mg, 2.73 mmol) in water (7.3 mL) at 0° C. A cooled solution of sodium nitrite (188 mg, 2.73 mmol) in water (1.5 mL) was added, and the mixture was stirred for 30 minutes. This solution was then added to a solution of potassium ethyl xanthate (525 mg, 3.28 mmol) in water (0.65 mL) warmed to 45° C. The reaction mixture was stirred for an additional 30 minutes. Diethyl ether (25 mL) was added, and the organic layer was washed with 10% sodium hydroxide solution until neutral. The organic layer was dried over magnesium sulfate, filtered and evaporated. The product was used directly in Example 4. Example 4 2-benzylthiophenol [0071] S-2-benzylphenyl-O-ethyl carbonodithioate (787 mg, 2.72 mmol) was dissolved in ethanol (8.2 mL) and heated to reflux. Potassium hydroxide pellets (654 mg, 11.65 mmol) were added slowly, and the solution was refluxed overnight. The solution was concentrated, and the residue was diluted with water (10 mL) and washed with diethyl ether (10 mL). The aqueous layer was acidified with 2 N HCl and extracted with diethyl ether. The organic extract was separated, dried over magnesium sulfate, filtered and evaporated to yield 289 mg of the crude thiol, which was used directly in Example 5. Example 5 3-(2-benzylphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide [0072] To a stirred suspension of sodium hydride (60% dispersed in mineral oil, 11 mg, 0.26 mmol) in THF (0.11 mL) was added slowly a solution of 2-benzylbenzenethiol (51 mg, 0.25 mmol) in THF (0.08 mL) at 0° C. After stirring the mixture for 5 minutes, a solution of N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide (55 mg, 0.202 mmol) in THF (0.28 mL) was added slowly. The reaction was allowed to warm to room temperature and stirred overnight. The THF was evaporated. The mixture was diluted with water and extracted with ethyl acetate (50 mL). The organic layer was washed with water (25 mL) and brine (25 mL), dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 32 mg of desired product. Production of 3-(2-benzylphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide was confirmed by 1-H NMR, 13-C NMR, and mass spectral analysis. Example 6 3-(2-benzylphenylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide (PLM2) [0073] 3-(2-benzylphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide (32 mg, 0.068 mmol) was dissolved in dichloromethane (0.1 mL) and cooled to −78° C. 30% hydrogen peroxide (12 μL, 0.4 mmol) was added followed by the slow addition of trifluoroacetic anhydride (48 μL, 0.34 mmol). The reaction was stirred at room temperature for 16 h. The reaction was diluted with dichloromethane. Cold water and brine were added, and the reaction was stirred for 20 minutes. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 14 mg of desired product. Production of PLM2 was confirmed by 13-C NMR and mass spectral analysis. Example 7 S-3-benzylphenyl-O-ethyl carbonodithioate [0074] Concentrated hydrochloric acid (0.2 mL) was added slowly to a solution of 3-benzylaniline (250 mg, 1.36 mmol) in water (3.7 mL) at 0° C. A cooled solution of sodium nitrite (94 mg, 1.36 mmol) in water (0.73 mL) was added, and the mixture was stirred for 30 minutes. This solution was then added to a solution of potassium ethyl xanthate (261 mg, 1.63 mmol) in water (0.33 mL) at 45° C. The reaction mixture was stirred for an additional 30 minutes. Diethyl ether (25 mL) was added, and the organic layer was washed with 10% sodium hydroxide solution until neutral. The organic layer was dried over magnesium sulfate, filtered and evaporated to afford the crude product, which was used directly in Example 8. Example 8 3-benzylbenzenethiol [0075] S-3-benzylphenyl-O-ethyl carbonodithioate (392 mg, 1.36 mmol) was dissolved in ethanol (4.1 mL) and heated to reflux. Once refluxing, potassium hydroxide pellets (326 mg, 5.81 mmol) were added slowly and refluxing was continued overnight. The ethanol was evaporated. The residue was diluted with water (10 mL) and washed with diethyl ether (10 mL). The aqueous layer was acidified with 2 N HCl and extracted with diethyl ether. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 95:5) yielded 44 mg of desired product, which was used directly in Example 9. Example 9 3-(3-benzylphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide [0076] To a stirred suspension of sodium hydride (60% dispersed in mineral oil, 11 mg, 0.26 mmol) in THF (0.11 mL) was added a solution of 3-benzylbenzenethiol (52 mg, 0.26 mmol) in THF (0.08 mL) at 0° C. The mixture was stirred for 5 minutes. A solution of N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide (56 mg, 0.207 mmol) in THF (0.28 mL) was added slowly. The reaction was allowed to warm to room temperature and stirred overnight. The THF was evaporated. The mixture was diluted with water and extracted with ethyl acetate (50 mL). The organic layer was washed with water (25 mL) and brine (25 mL), dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 15.5 mg of desired product. Production of 3-(3-benzylphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide was confirmed by 1-H NMR, 13-C NMR, and mass spectral analysis. Example 10 3-(3-benzylphenylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide (PLM3) [0077] 3-(3-benzylphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide (15 mg, 0.033 mmol) was dissolved in dichloromethane (0.05 mL) and cooled to −78° C. 30% hydrogen peroxide (5.7 μL, 0.2 mmol) was added followed by the slow addition of trifluoroacetic anhydride (23 μL, 0.17 mmol). The reaction was stirred at room temperature for 16 h. The reaction was diluted with dichloromethane. Cold water and brine were added, and the reaction was stirred for 20 minutes. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 11 mg of desired product. Production of PLM3 was confirmed by 1-H NMR, 13-C NMR, and mass spectral analysis. Example 11 3-aminobiphenyl [0078] 3-nitrobiphenyl (500 mg, 2.5 mmol) and 10% palladium on carbon (267 mg, 2.5 mmol) were dissolved in methanol (1 mL) and purged with nitrogen and placed under an atmosphere of hydrogen overnight. The reaction mixture was filtered and evaporated to yield 326 mg of the desired amine, which was used directly in Example 12. Example 12 S-3-phenylphenyl-O-ethyl carbonodithioate [0079] Concentrated hydrochloric acid (0.26 mL) was added to a solution of 3-aminobiphenyl (326 mg, 1.82 mmol) in water (4.9 mL) at 0° C. A cooled solution of sodium nitrite (125 mg, 1.82 mmol) in water (0.98 mL) was added, and the mixture was stirred for 30 minutes. This solution was then added to a solution of potassium ethyl xanthate (350 mg, 2.18 mmol) in water (0.44 mL) warmed to 45° C. The reaction mixture was stirred for an additional 30 minutes. Diethyl ether (25 mL) was added, and the organic layer was washed with 10% sodium hydroxide solution followed by water until neutral. The organic layer was dried over magnesium sulfate, filtered and evaporated. The crude product was used directly in Example 13. Example 13 3-phenylbenzenethiol [0080] To a refluxing solution of S-3-phenylphenyl-O-ethyl carbonodithioate (543 mg, 1.82 mmol) in ethanol (5.5 mL) was added slowly potassium hydroxide pellets (436 mg, 7.77 mmol). After refluxing overnight, the solvent was evaporated. The residue was diluted with water (10 mL) and washed with diethyl ether (10 mL). The aqueous layer was acidified with 2 N HCl and extracted with diethyl ether. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated to yield 171 mg of the crude thiol that was used directly in Example 14. Example 14 3-(2-phenylphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide [0081] To a stirred suspension of sodium hydride (60% dispersed in mineral oil, 9.7 mg, 0.24 mmol) in THF (0.1 mL) was added a solution of 3-phenylbenzenethiol (46 mg, 0.23 mmol) in THF (0.08 mL) at 0° C. The mixture was stirred for 5 minutes. N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide (50 mg, 0.185 mmol) was dissolved in THF (0.25 mL) and added slowly. The reaction was allowed to warm to room temperature and stirred overnight. The THF was evaporated. The mixture was diluted with water and extracted with ethyl acetate (50 mL). The organic layer was washed with water (25 mL) and brine (25 mL), dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 41 mg of desired product. Production of 3-(2-phenylphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide was confirmed by 1-H NMR, 13-C NMR, and mass spectral analysis. Example 15 3-(2-phenylphenylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide, (PLM4) [0082] To a solution of 3-(2-phenylphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide (41 mg, 0.093 mmol) in dichloromethane (0.13 mL) at −78° C. was added 30% hydrogen peroxide (15.5 μL, 0.54 mmol) followed by the slow addition of trifluoroacetic anhydride (63 μL, 0.45 mmol). The reaction was stirred at room temperature for 16 h. The reaction was diluted with dichloromethane. Cold water and brine were added, and the reaction was stirred for 20 minutes. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 23 mg of desired product. Production of PLM4 was confirmed by 1-H NMR and 13-C NMR. Example 16 3-(3-methoxyphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide [0083] To a stirred suspension of sodium hydride (60% dispersed in mineral oil, 17 mg, 0.43 mmol) in THF (0.18 mL) was added a solution of 3-methoxythiophenol (51 μL, 0.41 mmol) in THF (0.13 mL) at 0° C. After 5 minutes, a solution of N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide (88 mg, 0.33 mmol) in THF (0.45 mL) was added slowly. The reaction was allowed to warm to room temperature and stirred overnight. The solvent was evaporated. The residue was diluted with water and extracted with ethyl acetate (50 mL). The organic layer was washed with water (25 mL) and brine (25 mL), dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 55 mg of desired product. Production of 3-(3-methoxyphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide was confirmed by 1-H NMR and mass spectral analysis. Example 17 3-(3-methoxyphenylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide, (PLM5) [0084] To a solution of 3-(3-methoxyphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide (29 mg, 0.07 mmol) in dichloromethane (0.18 mL) at −78° C. was added 30% hydrogen peroxide (16 μL, 0.57 mmol) followed by the slow addition of trifluoroacetic anhydride (60 μL, 0.45 mmol). The reaction was stirred at room temperature for 16 h. The reaction was diluted with dichloromethane. Cold water and brine were added, and the reaction was stirred for 20 minutes. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 19 mg of desired product. Production of PLM5 was confirmed by 1-H NMR, 13-C NMR, and mass spectral analysis. Example 18 S-2-phenylphenyl-O-ethyl Carbonodithioate [0085] To a solution of 2-aminobiphenyl (250 mg, 1.47 mmol) in water (3.9 mL) at 0° C. was added concentrated hydrochloric acid (0.2 mL). A solution of sodium nitrite (102 mg, 1.47 mmol) in water (0.8 mL) at 0° C. was added, and the mixture was stirred for 30 minutes. This solution was then added to a solution of potassium ethyl xanthate (284 mg, 1.8 mmol) in water (0.36 mL) at 45° C. The reaction mixture was stirred for an additional 30 minutes. Diethyl ether (25 mL) was added, and the organic layer was washed with 10% sodium hydroxide solution followed by water until neutral. The organic layer was dried over magnesium sulfate, filtered and evaporated. The crude product was used directly in Example 19. Example 19 2-phenylbenzenethiol [0086] To a refluxing solution of S-2-benzylphenyl-O-ethyl carbonodithioate (405 mg, 1.47 mmol) in ethanol (4.5 mL) was added slowly potassium hydroxide pellets (354 mg, 6.3 mmol). After refluxing overnight, the solvent was evaporated. The residue was diluted with water (10 mL) and extracted with diethyl ether (10 mL). The aqueous layer was acidified with 2 N HCl and washed with diethyl ether. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated to yield 105 mg of the crude thiol that was used directly in Example 20. Example 20 3-(1-phenylphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide [0087] To a stirred suspension of sodium hydride (60% dispersed in mineral oil, 12 mg, 0.31 mmol) in THF (0.1 mL) was added a solution of 2-phenylbenzenethiol (38 mg, 0.3 mmol) in THF (0.1 mL) at 0° C. After 5 minutes, a solution of N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide (64 mg, 0.24 mmol) in THF (0.33 mL) was added slowly. The reaction was allowed to warm to room temperature and stirred overnight. The solvent was evaporated. The residue was diluted with water and extracted with ethyl acetate (50 mL). The organic layer was washed with water (25 mL) and brine (25 mL), dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 85 mg of desired product. Example 21 3-(1-phenylphenylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide, (PLM54) [0088] To a solution of 3-(1-phenylphenylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide (85 mg, 0.21 mmol) in dichloromethane (0.3 mL) at −78° C. was added 30% hydrogen peroxide (0.036 mL, 1.26 mmol) followed by the slow addition of trifluoroacetic anhydride (0.151 mL, 1.07 mmol). The reaction was stirred at room temperature for 16 h. The reaction was diluted with dichloromethane. Cold water and brine were added, and the reaction was stirred for 20 minutes. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 41 mg of desired product. Example 22 N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methyl-3-(naphthalen-2-ylthio)propanamide [0089] To a stirred suspension of sodium hydride (60% dispersed in mineral oil, 26 mg, 0.65 mmol) in THF (0.27 mL) was added a solution of 2-naphthalenethiol (100 mg, 0.62 mmol) in THF (0.2 mL) at 0° C. After 5 minutes, a solution of N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide (134 mg, 0.50 mmol) in THF (0.7 mL) was added slowly. The reaction was allowed to warm to room temperature and stirred overnight. The solvent was evaporated. The residue was diluted with water and extracted with ethyl acetate (50 mL). The organic layer was washed with water (25 mL) and brine (25 mL), dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 63 mg of desired product. Production of N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methyl-3-(naphthalen-2-ylthio)propanamide was confirmed by 1-H NMR and 13-C NMR. Example 23 N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methyl-3-(naphthalen-2-ylsulfonyl)propanamide, (PLM55) [0090] To a solution of N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methyl-3-(naphthalen-3-ylsulfonyl)propanamide (63 mg, 0.15 mmol) in dichloromethane (0.4 mL) and at −78° C. was added 30% hydrogen peroxide (25 μL, 0.88 mmol) followed by the slow addition of trifluoroacetic anhydride (0.1 mL, 0.74 mmol). The reaction was stirred at room temperature for 16 h and then diluted with dichloromethane. Cold water and brine were added, and the reaction was stirred for 20 minutes. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 22 mg of desired product. Example 24 S-1-bromonaphthalen-4-yl-O-ethyl Carbonodithioate [0091] To a solution of 1-amino-4-bromonaphthalene (150 mg, 0.68 mmol) in water (1.8 mL) at 0° C. was added concentrated hydrochloric acid (0.1 mL). A solution of sodium nitrite (47 mg, 0.68 mmol) in water (0.36 mL) at 0° C. was added, and the mixture was stirred for 30 minutes. This solution was then added to a solution of potassium ethyl xanthate (130 mg, 0.81 mmol) in water (0.16 mL) at 45° C. The reaction mixture was stirred for an additional 30 minutes. Diethyl ether (25 mL) was added, and the organic layer was washed with 10% sodium hydroxide solution followed by water until neutral. The organic layer was dried over magnesium sulfate, filtered and evaporated. The crude product was used directly in Example 25. Example 25 4-bromonaphthalene-1-thiol [0092] To a refluxing solution of S-1-bromonaphthalen-4-yl-O-ethyl carbonodithioate (188 mg, 0.57 mmol) in ethanol (1.7 mL) was added slowly potassium hydroxide pellets (138 mg, 2.4 mmol). After refluxing overnight, the solvent was evaporated. The residue was diluted with water (10 mL) and extracted with diethyl ether (10 mL). The aqueous layer was acidified with 2 N HCl and washed with diethyl ether. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated to yield 75 mg of the crude thiol that was used directly in Example 26. Example 26 3-(1-bromonaphthalen-4-ylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide [0093] To a stirred suspension of sodium hydride (60% dispersed in mineral oil, 2.8 mg, 0.07 mmol) in THF (0.03 mL) was added a solution of 4-bromonaphthalene-1-thiol (16 mg, 0.07 mmol) in THF (0.2 mL) at 0° C. The mixture was stirred for 5 minutes before a solution of N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide (14 mg, 0.05 mmol) dissolved in THF (0.07 mL) was added slowly. The reaction was allowed to warm to room temperature and stirred overnight. The solvent was evaporated. The mixture was diluted with water and extracted with ethyl acetate (50 mL). The organic layer was washed with water (25 mL) and brine (25 mL), dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 13 mg of desired product. Example 27 3-(1-bromonaphthalen-4-ylsulfonyl)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide, (PLM9) [0094] To a solution of 3-(1-bromonaphthalen-4-ylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide (13 mg, 0.025 mmol) in dichloromethane (0.06 mL) at −78° C. was added 30% hydrogen peroxide (4.4 μL, 0.155 mmol) followed by the slow addition of trifluoroacetic anhydride (18 μL, 0.13 mmol). The reaction was stirred at room temperature for 16 h before the reaction was diluted with dichloromethane. Cold water and brine were added, and the reaction was stirred for 20 minutes. The organic layer was separated, dried over magnesium sulfate, filtered and evaporated. Purification by column chromatography (hexane:EtOAc 50:50) yielded 9 mg of desired product. Example 28 N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-((1-(3-hydroxypropyl)naphthalene-4-yl)sulfonyl)-2-methylpropanamide (PLM14) [0095] The precursor 3-(1-aminonaphthalen-4-yl)propan-1-ol was first prepared as follows: To a 0° C. solution of 4-allylnaphthalen-1-amine (1830 mg, 9.73 mmol), (derived from palladium catalyzed allylation of 1-amino bromonapthalene with allyl tributyl tin) in 19 mL of THF was added 1 M BH 3 (14.6 mL, 14.6 mMol). The reaction mixture was stirred at 0° C. for 30 min, warmed to room temperature and stirred for an additional 2 h. The reaction mixture was cooled to 0° C. and 3M NaOH (3.6 mL) and 30% H 2 O 2 (1.14 mL) were added. The reaction mixture was stirred for 30 min at 0° C. and then heated to 60° C. and stirred for an additional 1 h. The solvent was evaporated under reduced pressure and the resulting residue was diluted with water and extracted with EtOAc (2×40 mL). The combined organic extracts were washed with water (50 mL) and brine (50 mL), dried over MgSO 4 , filtered and evaporated under reduced pressure. The product was purified by flash column chromatography on silica gel (5% EtOAC→70% EtOAc/Hexanes) to yield 5 (1040 mg, 52%) as a colorless oil. HRMS (Cl) calculated for [C 13 H 15 NO+H] 202.1232, found 202.1228. 1 H NMR (CDCl 3 , 400 MHz): δ 8.03 (d, J=8.0 Hz, 1H), 7.87 (d, J=7.2 Hz, 1H), 7.54-7.45 (m, 2H), 7.14 (d, J=7.6 Hz, 1H), 6.71 (d, J=7.6 Hz, 1H), 4.07 (bs, 2H), 3.70, (t, J=6.4 Hz, 2H), 3.05 (t, J=7.6 Hz, 2H), 2.14 (bs, OH), 1.96 (p, J=6.4 Hz, 2H). 13 C NMR (CDCl 3 , 400 MHz): δ 140.4, 132.3, 128.5, 126.2, 125.6, 124.4, 124.4, 124.2, 121.4, 109.6, 62.3, 33.5, 28.7. [0096] 3-(1-aminonaphthalen-4-yl)propan-1-ol was then converted to 3-(1-mercaptonaphthalen-4-yl)propan-1-ol by diazotization followed by substitution with ethylxanthate and subsequent hydrolysis as following the general procedure described in Examples 12 and 13. [0097] To a stirred suspension of 1.31 equiv. of sodium hydride (60% dispersed in mineral oil) in THF at 0° C. was added a solution of 1.26 equiv. of 3-(1-mercaptonaphthalen-4-yl)propan-1-ol dissolved in THF and stirred for 5 minutes. A solution of 1 equiv. of N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide in THF was added to the reaction mixture. The reaction was allowed to warm to room temperature and stir overnight. The solvent was evaporated. The residue was diluted with water and extracted with EtOAc (3×50 mL). The organic extracts were washed with water, brine, dried over MgSO 4 , filtered and evaporated under reduced pressure. The resulting crude product was purified by flash column chromatography on silica gel (50% EtOAc/Hexane) to yield (42%) of N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-((1-(3-hydroxypropyl) naphthalene-4-yl)sulfanyl)-2-methylpropanamide as a colorless oil. [0098] PLM14 was made from the oxidation of N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-((1-(3-hydroxypropyl)naphthalene-4-yl)sulfanyl)-2-methylpropanamide following the general procedure for PLM1 to give 11 mg (44%) of desired product as a white solid. HRMS (ESI) calculated for [C 25 H 23 F 3 N 2 O 5 S+Na] 543.1178, found 543.1179. 1 H NMR (CDCl 3 , 400 MHz): δ 9.24 (bs, NH), 8.71 (d, J=8.4 Hz, 1H), 8.17-8.12 (m, 2H), 7.97 (s, 1H), 7.81-7.70 (m, 4H), 7.32 (d, J=7.6 Hz, 1H), 5.23 (s, OH), 4.42 (t, J=6.4 Hz, 2H), 4.24 (d, J=14.4 Hz, 1H), 3.64 (d, J=14.4 Hz, 1H), 3.22 (dp, J=42.4, 7.6 Hz, 2H), 2.18 (p, J=6.4 Hz, 2H), 1.59 (s, 3H). 13 C NMR (CDCl 3 , 400 MHz): δ 171.6, 145.6, 141.3, 135.6, 132.8, 132.3, 130.1, 129.0, 128.9, 127.6, 124.6, 124.4, 124.3, 123.4, 121.9, 120.7, 117.2, 115.4, 104.5, 74.6, 67.0, 61.1, 29.3, 28.6, 27.7. Example 29 N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-((1-(3-hydroxypropyl)naphthalene-5-yl)sulfonyl)-2-methylpropanamide (PLM15) [0099] The precursor N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-((1-(3-hydroxypropyl)naphthalene-5-yl)sulfanyl)-2-methylpropanamide was prepared as follows: To a solution of 1.31 equiv. of sodium hydride (60% dispersed in mineral oil) in THF at 0° C. was added a solution of 1.26 equiv. of 3-(1-mercaptonaphthalen-5-yl)propan-1-ol (prepared analogously to 3-(1-aminonaphthalen-4-yl)propan-1-ol in example 28) dissolved in THF (0.2 mL) and stirred for 5 minutes. A solution of 1 equiv. of N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide (50 mg, 0.185 mmol) in THF (0.7 ml) was added to the reaction mixture. The reaction was allowed to warm to room temperature and stir overnight. Standard workup afforded the desired product in 37% yield. HRMS (ESI) calculated for [C 25 H 23 F 3 N 2 O 3 S+Na] 511.1279, found 511.1278. 1 H NMR (CDCl 3 , 400 MHz): δ 8.99 (bs, NH), 8.30 (d, J=8.8 Hz, 1H), 7.85 (d, J=8.4 Hz, 1H), 7.72 (s, 1H), 7.68 (d, J=7.2 Hz, 1H), 7.57 (d, J=8.4 Hz, 1H), 7.50 (d, J=8.4 Hz, 1H), 7.39 (t, J=7.6 Hz, 1H), 7.30-7.26 (m, 2H), 4.14 (s, OH), 3.85 (d, J=13.6 Hz, 1H), 3.70 (t, J=6.4 Hz, 2H), 3.18 (d, J=14.4 Hz, 1H), 3.01 (sent, J=8.0 Hz, 2H), 2.14 (bs, OH), 1.90 (p, J=2.8 Hz, 2H), 1.52 (s, 3H). 13 C NMR (CDCl 3 , 400 MHz): δ 173.1, 141.0, 138.8, 135.3, 133.6, 132.2, 131.5, 130.6, 126.4, 126.3, 125.2, 124.2, 123.3, 123.3, 121.3, 120.6, 116.8, 115.6, 103.7, 75.3, 62.1, 45.4, 33.2, 29.1, 26.1. [0100] PLM15 was made from the oxidation of N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-((1-(3-hydroxypropyl)naphthalene-5-yl)sulfanyl)-2-methylpropanamide following the general procedure for PLM1 to give 42 mg (40%) of desired product as a white solid. HRMS (ESI) calculated for [C 25 H 23 F 3 N 2 O 5 S+Na] 543.1178, found 543.1186. 1 H NMR (CDCl 3 , 400 MHz): δ 9.15 (bs, NH), 8.59 (d, J=8.4 Hz, 1H), 8.29 (d, J=8.4 Hz, 1H), 8.23 (d, J=7.2 Hz, 1H), 7.93 (s, 1H), 7.79-7.70 (m, 3H), 7.53 (d, J=7.2 Hz, 1H), 7.47 (t, J=8.0 Hz, 1H), 5.29 (s, OH), 4.44 (t, J=6.4 Hz, 2H), 4.24 (d, J=14.4 Hz, 1H), 3.64 (d, J=14.4 Hz, 1H), 3.25 (t, J=7.2 Hz, 2H), 2.21 (p, J=6.8 Hz, 2H), 1.59 (s, 3H). 13 C NMR (CDCl 3 , 400 MHz): δ 173.4, 141.1, 138.1, 135.7, 134.8, 132.5, 131.2, 130.0, 129.3, 129.0, 127.9, 124.2, 123.3, 122.4, 121.8, 120.7, 117.3, 115.4, 104.9, 74.6, 67.1, 60.8, 29.2, 29.1, 27.7. Example 30 (E)-methyl 3-(1-(2-(4-cyano-3-(trifluoromethyl)phenylcarbamoyl)-2-hydroxypropylsulfonyl)naphthalene-4-yl)acrylate (PLM16) [0101] The precursor 1-amino-4-bromonaphthalene was converted to 1-thiol-4-bromonaphthalene by diazotization followed by substitution with ethylxanthate and subsequent hydrolysis following the general proceedure described in Examples 12 and 13. [0102] The precursor (E)-methyl 3-(1-(2-(4-cyano-3-(trifluoromethyl)phenylcarbamoyl)-2-hydroxypropylthio)naphthalene-4-yl)acrylate was prepared as follows: To a solution of 1-thiol-4-bromonaphthalene (40 mg, 0.079 mmol), triphenylphosphine (3.4 mg, 0.013 mmol), palladium (II) acetate (1 mg, 0.0044 mmol) and triethylamine (36 μL, 0.26 mmol) in 0.5 mL DMF was added methyl acrylate (9.2 μL, 0.1 mmol). The reaction was heated to 90° C. overnight. The reaction mixture was cooled to room temperature, diluted with water (10 mL) and extracted with EtOAc (2×10 mL). The combined organic extracts were washed with water (10 mL) and brine (10 mL), dried over MgSO 4 , filtered and evaporated. The resulting crude product was purified by flash column chromatography on silica gel (10%→50% EtOAc/Hexanes) to yield 21 mg (53%) of desired product as a brown oil. HRMS (ESI) calculated for [C 26 H 21 F 3 N 2 O 4 S+Na] 537.1072, found 537.1072. 1 H NMR (CDCl 3 , 400 MHz): δ 8.83 (bs, NH), 8.44 (d, J=8.0 Hz, 1H), 8.30 (d, J=15.6 Hz, 1H), 8.06 (d, J=7.6 Hz, 1H), 7.70-7.50 (m, 7H), 6.33 (d, J=15.6 Hz, 1H), 3.94 (d, J=14.0 Hz, 1H), 3.87 (s, 3H), 3.22 (d, J=14.0 Hz, 1H), 2.45 (s, OH), 1.55 (s, 3H). 13 C NMR (CDCl 3 , 400 MHz): δ 172.8, 166.9, 140.9, 140.6, 135.5, 133.5, 133.2, 132.1, 131.6, 130.0, 127.2, 127.1, 125.3, 124.2, 124.2, 123.3, 121.2, 121.0, 120.6, 116.7, 115.3, 104.3, 75.3, 51.9, 44.9, 26.3. [0103] PLM16 was made from the oxidation of (E)-methyl 3-(1-(2-(4-cyano-3-(trifluoromethyl)phenylcarbamoyl)-2-hydroxypropylthio)naphthalene-4-yl)acrylate following the general procedure for PLM1 to give 14 mg (64%) of desired product as a brown oil. HRMS (ESI) calculated for [C 26 H 21 F 3 N 2 O 6 S+Na] 569.0970, found 569.0990. 1 H NMR (CDCl 3 , 400 MHz): δ 9.02 (bs, NH), 8.73 (d, J=8.4 Hz, 1H), 8.40 (d, 15.6 Hz, 1H), 8.29 (d, J=8.4 Hz, 1H), 8.24 (d, J=8.0 Hz, 1H), 7.89-7.77 (m, 4H), 7.67 (d, J=8.4 Hz, 1H), 7.59 (d, J=8.0 Hz, 1H), 6.37 (d, J=15.6 Hz, 1H), 5.25 (s, OH), 4.29 (d, J=14.4 Hz, 1H), 3.92 (s, 3H), 3.63 (d, J=15.6 Hz, 1H), 1.60 (s, 3H). 13 C NMR (CDCl 3 , 400 MHz): δ 171.1, 161.1, 140.9, 140.0, 139.9, 135.7, 134.6, 132.0, 129.8, 129.6, 129.0, 128.2, 125.1, 124.5, 124.1, 123.3, 122.7, 121.6, 120.6, 117.0, 115.2, 105.1, 74.4, 60.6, 52.2, 27.9. Example 31 (E)-methyl 3-(1-(2-(4-cyano-3-(trifluoromethyl)phenylcarbamoyl)-2-hydroxypropylsulfonyl)naphthalene-5-yl)acrylate (PLM18) [0104] The precursor 3-(1-bromonaphthalen-5-ylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide) was prepared as follows: To a suspension of 1.31 equiv. of sodium hydride (60% dispersed in mineral oil) in THF at 0° C. was added a solution of 1.26 equiv. of 5-bromonaphthalen-1-thiol dissolved in THF and stirred for 5 minutes. A solution of 1 equiv. of N-(4-Cyano-3-trifluorophenyl)methacrylamide epoxide in THF was added to the reaction mixture. The reaction was allowed to warm to room temperature and was stirred overnight. Standard workup followed by chromatography afforded (29 mg, (71%) 3-(1-bromonaphthalen-5-ylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide), as a brown oil. HRMS (ESI) calculated for [C 22 H 16 BrF 3 N 2 O 2 S+Na] 530.9966, found 530.9981. 1 H NMR (CDCl 3 , 400 MHz): δ 8.78 (bs, NH), 8.30 (d, J=8.4 Hz, 1H), 8.03 (d, J=7.6 Hz, 1H), 7.77 (d, J=7.2 Hz, 1H), 7.69 (d, J=7.2 Hz, 1H), 7.60-7.52 (m, 2H), 7.42-7.32 (m, 3H), 3.92 (d, J=14.0 Hz, 1H), 3.71 (s, OH), 3.15 (d, J=14.4 Hz, 1H), 1.52 (s, 3H). 13 C NMR (d6-Acetone, 400 MHz): δ 174.7, 134.5, 136.7, 135.2, 135.0, 132.9, 131.4, 131.2, 127.9, 127.5, 126.8, 126.1, 124.9, 123.5, 122.9, 122.1, 117.9, 116.3, 104.0, 76.5, 46.1, 26.5. [0105] The precursor (E)-methyl 3-(1-(2-(4-cyano-3-(trifluoromethyl)phenylcarbamoyl)-2-hydroxypropylth io)naphthalene-5-yl)acrylate was prepared as follows: To a solution of 3-(1-bromonaphthalen-5-ylthio)-N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-2-methylpropanamide), triphenylphosphine, palladium (II) acetate and triethylamine in DMF was added methyl acrylate. The reaction was heated to 90° C. overnight. The reaction mixture was cooled to room temperature, diluted with water and extracted with EtOAc. The combined organic extracts were washed with water and brine, dried over MgSO 4 , filtered and evaporated. The resulting crude product was purified by flash column chromatography on silica gel (10%→50% EtOAc/Hexanes) to yield 21 mg (51%) of desired product as a brown oil. HRMS (ESI) calculated for [C 26 H 21 F 3 N 2 O 4 S+Na] 537.1072, found 537.1098. 1 H NMR (CDCl 3 , 400 MHz): δ 8.83 (bs, NH), 8.50 (d, J=8.0 Hz, 1H), 8.34 (d, J=15.6 Hz, 1H), 8.00 (d, J=8.4 Hz, 1H), 7.78 (d, J=6.8 Hz, 1H), 7.67-7.61 (m, 3H), 7.53 (t, J=8.0 Hz, 2H), 7.39 (t, J=8.0 Hz, 1H), 6.45 (d, J=15.6 Hz, 1H), 3.90 (d, J=14.0 Hz, 1H), 3.87 (s, 3H), 3.69 (s, OH), 3.19 (d, J=14.0 Hz, 1H), 1.53 (s, 3H). 13 C NMR (CDCl 3 , 400 MHz): δ 172.7, 166.9, 141.0, 140.8, 135.4, 133.6, 132.7, 131.9, 131.8, 131.5, 127.0, 126.4, 126.2, 125.3, 124.2, 123.3, 121.3, 121.2, 120.6, 116.7, 115.3, 104.3, 75.3, 52.0, 45.6, 26.2. [0106] PLM18 was made from the oxidation of (E)-methyl 3-(1-(2-(4-cyano-3-(trifluoromethyl)phenylcarbamoyl)-2-hydroxypropylthio)naphthalene-5-yl)acrylate following the general procedure for PLM1 to give 25 mg (54%) of desired product as a brown oil. HRMS (ESI) calculated for [C 26 H 21 F 3 N 2 O 6 S+Na] 569.0970, found 569.0989. 1 H NMR (CDCl 3 , 400 MHz): δ 9.06 (bs, NH), 8.73 (d, J=8.8 Hz, 1H), 8.46 (s, 1H), 8.44 (d, J=15.6 Hz, 1H), 8.27 (d, J=7.2 Hz, 1H), 7.89-7.70 (m, 5H), 7.52 (t, J=8.0 Hz, 1H), 6.72 (d, J=15.6 Hz, 1H), 5.19 (bs, OH), 4.22 (d, J=14.4 Hz, 1H), 3.89 (s, 3H), 3.63 (d, J=14.4 Hz, 1H), 1.59 (s, 3H). 13 C NMR (CDCl 3 , 400 MHz): δ 171.3, 166.7, 140.9, 140.7, 135.8, 134.7, 133.7, 132.1, 131.5, 130.6, 129.4, 129.0, 126.4, 125.3, 124.9, 123.3, 122.8, 121.8, 120.7, 117.2, 115.3, 105.1, 74.6, 60.9, 52.0, 27.7. Example 32 (2-bromophenyl)(2,4,6-trimethoxybenzyl)sulfane [0107] To a solution of 30.8 g (2,4,6-trimethoxyphenyl)methanol (155.4 mmol) and 29.2 g 2-bromobenzenethiol (155.4 mmol) in 150 ml DCM at 0° C. was added dropwise 1.3 eq TFA. The reaction was stirred 15 minutes at room temperature before saturated NaHCO 3 was added until neutral. The organic volatiles were removed under reduced pressure and the aqueous residue was extracted with ethyl acetate (3×150 ml). The organic layer was collected, washed with brine and dried over magnesium sulfate, filtered, and concentrated under reduced pressure afforded a yellowish solid. The solid was washed with ethyl acetate to yield 51.3 g white solid (2-bromophenyl)(2,4,6-trimethoxybenzyl)sulfane (13.9 mmol, 89% yield). Example 33 2-(2,4,6-trimethoxybenzylthio)phenylboronic Acid [0108] To a solution of 4.22 g (2-bromophenyl)(2,4,6-trimethoxybenzyl)sulfane (11.56 mmol) in 150 ml dry THF at −78° C. was added slowly 5.6 ml 2.5M n-BuLi. The solution was stirred at −78° C. for 25 minutes. 1.6 ml B(OMe) 3 was added at −78° C. The reaction was stirred 2 hours at RT. 100 ml water was added, stirred overnight. The mixture was extracted with ethyl acetate (2×100 ml). The organic layer was washed with brine, dried over magnesium sulfate, filtered and concentrated. Purification by gradient chromatography (hexane:ethyl acetate 60:40) yielded 1.762 g product (5.3 mmol, 46% yield). Example 34 2′-(2,4,6-trimethoxybenzylthio)biphenyl-3-ol [0109] To a mixture of 1.05 g 2-(2,4,6-trimethoxybenzylthio)phenylboronic acid (3.14 mmol), 1.07 g 3-iodophenol (4.9 mmol) and 0.195 g Pd catalyst was added 40 ml toluene followed by 15 ml 2M Na 2 CO 3 . The mixture was refluxed under nitrogen overnight. The mixture was extracted with ethyl acetate. The organic was washed with water, brine, dried over magnesium sulfate, and concentrated. The residue was purified by silica flash chromatography (hexane:ethyl acetate 80:20) to afford 0.948 g product (2.48 mmol, 79% yield). Example 35 2′-mercaptobiphenyl-3-ol [0110] 2′-(2,4,6-trimethoxybenzylthio)biphenyl-3-ol (0.948 g, 2.48 mmol) was treated with TFA:triethylsilane:DCM (8 ml:3 ml:80 ml). The solution was stirred 30 min. before 40 ml water was added and the mixture was extracted with DCM (2×80 ml). The organic was washed with water, brine, dried over magnesium sulfate and concentrated. The residue was purified by silica flash chromatography (hexane:ethyl acetate 80:20) to afford 0.335 g product (1.66 mmol, 67% yield). Example 36 N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2′-hydroxybiphenyl-2-ylsulfonyl)-2-methylpropanamide (PAN41) [0111] To a solution of 0.335 g 2′-mercaptobiphenyl-3-ol (1.66 mmol), 0.432 g N-(4-cyano-3-(trifluoromethyl)phenyl)-2-methyloxirane-2-carboxamide (1.59 mmol) in 4 ml ethanol was added 0.6 ml triethylamine. The mixture was stirred overnight at ambient temperature before concentrating under reduced pressure. The residue was dissolved in ethyl acetate, washed with water, brine, dried over magnesium sulfate and concentrated. A solution of the unrefined product in 10 mL of DCM was treated with 0.77 g mCPBA (3.1 mmol). The mixture was stirred overnight and concentrated. The residue was dissolved in ethyl acetate, washed with water, brine, dried over magnesium sulfate and concentrated. Purification by flash chromatography (hexane:ethyl acetate 50:50) to afford 0.389 g product (0.77 mmol, 46% yield for two steps). Production of PAN41 was confirmed by 1-H NMR and 13-C NMR. See FIG. 11 for general synthesis scheme for precursors of PAN41, PAN51, and PAN61. See FIG. 12 for the general PAN41, PAN51, and PAN61 synthesis strategy. Production of both PAN51 and PAN61 was confirmed by 1-H NMR and 13-C NMR. Example 37 (2-methoxyphenyl)(2-(methylthio)phenyl)methanone (G) [0112] To a solution of 5.4 g 2-bromoanisole in 200 ml THF at −78° C. was added dropwise 1.2 eq of n-BuLi. 1.2 eq of N-methoxy-N-methyl-2-(methylthio)benzamide in THF was added and the reaction was warmed to RT and stirred for an additional 1 h. Water (100 ml) was added, and the mixture was extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulfate and concentrated. Silica flash chromatography (hexane:ethyl acetate 80:20) afforded 7.2 g of a pale yellow solid product (27.9 mmol, 96% yield). Example 38 (2-hydroxyphenyl)(2-(methylthio)phenyl)methanone (H) [0113] To a mixture of 1.45 g (2-methoxyphenyl)(2-(methylthio)phenyl)methanone (G) and 1.437 g AlCl 3 was added slowly 5 mL 1-dodecanethiol. The reaction was stirred overnight before 30 ml water was added. The mixture was extracted with ethyl acetate and the combined organic extracts were washed with brine, dried over magnesium sulfate, and the volatiles removed by distillation under nitrogen. Flash silica chromatography (hexane:ethyl acetate 80:20) afforded 0.807 g product (3.31 mmol, 60% yield). Example 39 2-(2-(methylthio)benzyl)phenol (I) [0114] To a mixture of 0.337 g (2-hydroxyphenyl)(2-(methylthio)phenyl)methanone [0115] (H) (1.38 mmol) and 0.5 ml triethylsilane was added 2 ml TFA. After 1 h, water was added and the mixture was extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulfate, and concentrated. Flash silica chromatography (hexane:ethyl acetate 80:20) afforded 0.235 g product (1.02 mmol, 74% yield). Example 40 2-(2-mercaptobenzyl)phenol (J) [0116] To a solution of 0.68 g 2-(2-(methylthio)benzyl)phenol (I) (2.96 mmol) in 4 ml freshly distilled THF at −78° C. was added 8 mL condensed ammonia followed by 0.15 g sodium. The blue solution was stirred for 2 hours at −78° C. before the mixture was warmed to ambient temperature. The reaction was allowed to stir overnight before NH 4 Cl was added until neutral. The mixture was extracted with ethyl acetate and the combined organic extracts washed with brine, dried over magnesium sulfate and concentrated. Flash silica chromatography (hexane:ethyl acetate 80:20) afforded 0.457 g product (2.12 mmol, 71% yield). Example 41 N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2-(2-hydroxybenzyl)phenylsulfonyl)-2-methylpropanamide, (PAN11) [0117] To a solution of 0.237 g 2-(2-mercaptobenzyl)phenol (J) and (1.1 mmol) 0.284 g N-(4-cyano-3-(trifluoromethyl)phenyl)-2-methyloxirane-2-carboxamide (1.05 mmol) in 4 ml ethanol was added 0.2 ml triethylamine. The reaction was stirred overnight and then concentrated. The residue was dissolved in ethyl acetate, washed with water, brine, dried over magnesium sulfate and concentrated. Without further purification, the residue was treated with 0.6 g mCPBA (2.4 mmol) in 10 ml DCM. The mixture was stirred overnight and concentrated. The residue was dissolved in ethyl acetate, washed with water, brine, dried over magnesium sulfate and concentrated. Purification by silica flash chromatography (hexane:ethyl acetate 50:50) afforded 0.204 g product (0.39 mmol, 39% yield for two steps). Production of PAN11 was confirmed by 1-H NMR and 13-C NMR. See FIG. 13 for the general PAN11 synthesis strategy. Example 42 (3-methoxyphenyl)(2-(2,4,6-trimethoxybenzylthio)phenyl)methanol (K) [0118] To a solution of 0.35 g (2-bromophenyl)(2,4,6-trimethoxybenzyl)sulfane (0.96 mmol) in dry THF was added slowly 1.2 eq n-BuLi. The reaction was stirred 25 minutes at −78° C. before 1.2 eq 3-methoxybenzaldehyde was added slowly. The reaction was warmed to ambient temperature and stirred for one additional hour before the addition of water. The mixture was extracted with ethyl acetate. The combined organic extracts were washed with brine, dried over magnesium sulfate, filtered and concentrated. Flash silica chromatography (hexane:ethyl acetate 80:20) afforded 0.288 g product (0.68 mmol, 70% yield). Example 43 2-(3-methoxybenzyl)benzenethiol (L) [0119] 0.288 g (3-methoxyphenyl)(2-(2,4,6-trimethoxybenzylthio)phenyl)methanol (K) (0.68 mmol) was treated with a solution of triethylsilane:TFA:DCM 0.3 ml:1 ml:10 ml. The mixture was stirred overnight at ambient temperature before the addition of water. The mixture was extracted with DCM, brine, dried over magnesium sulfate and concentrated. Flash silica chromatography (hexane:ethyl acetate 90:10) afforded 0.12 g product (0.52 mmol, 77% yield). Example 44 3-(2-mercaptobenzyl)phenol (M) [0120] To a mixture of 0.61 g 2-(3-methoxybenzyl)benzenethiol (L) (2.65 mmol) and 1.94 g AlCl 3 was added slowly 1.2 eq n-BuLi. The reaction was stirred overnight before 30 ml water was added. The mixture was extracted with ethyl acetate. The combined organic extracts were washed with brine and dried over magnesium sulfate. The volatiles were removed by distillation under nitrogen. Flash silica chromatography (hexane:ethyl acetate 80:20) afforded 0.23 g product (1.06 mmol, 40% yield). Example 45 N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2-(3-hydroxybenzyl)phenylsulfonyl)-2-methylpropanamide, (PAN21) [0121] To a solution of 0.23 g 3-(2-mercaptobenzyl)phenol (M) (1.0 mmol), 0.26 g N-(4-cyano-3-(trifluoromethyl)phenyl)-2-methyloxirane-2-carboxamide (0.95 mmol) in 4 ml ethanol was added, 0.2 ml triethylamine. The reaction was stirred overnight before concentrating. The residue was dissolved in ethyl acetate, washed with water, brine, dried over magnesium sulfate and concentrated. The crude product was dissolved in 10 ml DCM and treated with 0.3 g mCPBA (1.8 mmol). The mixture was stirred overnight and concentrated. The residue was dissolved in ethyl acetate, washed with water, brine, dried over magnesium sulfate and concentrated. Purification by chromatography (hexane:ethyl acetate 50:50) to afford 0.18 g product (0.35 mmol, 35% yield for two steps). Production of PAN21 was confirmed by 1-H NMR and 13-C NMR. See FIG. 14 for the general PAN21 synthesis strategy. Example 46 (4-methoxyphenyl)(2-(methylthio)phenyl)methanone (C) [0122] To a mixture of 1.788 g 2-(methylthio)benzoyl chloride (B) (9.58 mmol) and 1.6 g AlCl 3 at 0° C. was added slowly 20 ml DCM. The mixture was stirred 5 minutes at ambient temperature before 2 g anisole was added slowly. The reaction was stirred 30 minutes at ambient temperature and before water was added slowly. The mixture was extracted with DCM (2×50 ml). The combined organic extracts were washed with brine, dried over magnesium sulfate and concentrated. Flash silica chromatography (hexane:ethyl acetate 85:15) afforded 1.85 g pale yellow solid product (7.17 mmol, 75% yield). Example 47 (4-hydroxyphenyl)(2-mercaptophenyl)methanone (D) [0123] To a nitrogen flushed mixture of 1.415 g (4-methoxyphenyl)(2-(methylthio)phenyl)methanone (C) (5.48 mmol) and 3 g sodium thiolate (26.6 mmol) was added 40 ml anhydrous DMF. The mixture was refluxed under nitrogen. After the mixture turned to black, the reaction was refluxed for two more hours cooled to RT and quenched with water. The mixture was washed ethyl acetate (2×100 ml). The combined organic was brined, dried over magnesium sulfate, filtered and concentrated. Flash column (hexane:ethyl acetate 80:20) yield 0.954 g product (4.0 mmol, 73% yield). Example 48 4-(2-mercaptobenzyl)phenol (E) [0124] To a mixture of 0.954 g (4-hydroxyphenyl)(2-mercaptophenyl)methanone (D) (4.0 mmol), 1 ml triethylsilane was added 5 ml TFA. The mixture was stirred at ambient temperature for 1 hour before water was added. The reaction mixture was extracted with ethyl acetate (2×70 ml), brine, dried over magnesium sulfate, filtered and concentrated. Flash silica chromatography (hexane:ethyl acetate 80:20) afforded 0.786 g product (3.5 mmol, 88% yield). Example 49 N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2-(4-hydroxybenzyl)phenylsulfonyl)-2-methylpropanamide, (PAN31) [0125] A solution of 1.12 g 4-(2-mercaptobenzyl)phenol (E) (5.18 mmol), 1.34 g N-(4-cyano-3-(trifluoromethyl)phenyl)-2-methyloxirane-2-carboxamide (4.9 mmol) in 8 ml ethanol was treated with 1 ml triethylamine. After reaction at ambient temperature overnight, the mixture was concentrated and the residue was dissolved in ethyl acetate, washed with water, brine, dried over magnesium sulfate and concentrated. Without further purification, the residue was dissolved in 30 ml DCM and treated with 3.85 g mCPBA (15.5 mmol). The mixture was stirred overnight and concentrated. The residue was dissolved in ethyl acetate, washed with water, brine, dried over magnesium sulfate and concentrated. Purification by silica flash chromatography (hexane:ethyl acetate 50:50) afforded 0.47 g product (0.91 mmol, 18% yield for two steps). Production of PAN31 was confirmed by 1-H NMR and 13-C NMR. See FIG. 15 for the general PAN31 synthesis strategy. Example 50 N-(4-cyano-3-(trifluoromethyl)phenyl)-3-(2-(4-(cyanomethoxy)benzyl)phenylsulfonyl)-2-hydroxy-2-methylpropanamide, (PAN32) [0126] To a mixture of 0.115 g PAN31 and 50 mg potassium carbonate in 2 ml dry DMF was added 0.2 ml ClCH 2 CN was stirred overnight at RT. Water was added. The mixture was washed with ethyl acetate, brine, dried over magnesium sulfate, filtered and concentrated. Flash silica chromatography (hexane:ethyl acetate 40:60) afforded 77 mg product. Production of PAN32 was confirmed by 1-H NMR and 13-C NMR. Example 51 N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2-(4-methoxybenzyl)phenylsulfonyl)-2-methylpropanamide, (PAN33) [0127] To a mixture of 0.1 g PAN31 and 50 mg potassium carbonate in 2 ml dry DMF was added 0.2 ml methyl iodide. The reaction mixture was stirred overnight at ambient temperature before water was added. The mixture was washed with ethyl acetate and brine, dried over magnesium sulfate, filtered and concentrated. Flash silica chromatography (hexane:ethyl acetate 40:60) afforded 65 mg product. Production of PAN33 was confirmed by 1-H NMR and 13-C NMR. Example 52 N-(4-cyano-3-(trifluoromethyl)phenyl)-2-hydroxy-3-(2-(4-(methoxymethoxy)benzyl)phenylsulfonyl)-2-methylpropanamide, (PAN37) [0128] The mixture of 0.1 g PAN31, 50 mg potassium carbonate in 2 ml dry DMF was treated with 0.1 ml methoxymethylchloride. The reaction mixture was stirred overnight at ambient temperature before water was added. The mixture was washed with ethyl acetate and brine, dried over magnesium sulfate, filtered and concentrated. Flash silica chromatography (hexane:ethyl acetate 40:60) afforded 21 mg product. Production of PAN37 was confirmed by 1-H NMR and 13-C NMR. Example 53 (2,5-dimethylphenyl)(2-(methylthio)phenyl)methanone [0129] To a mixture of 1.2 g 2-(methylthio)benzoyl chloride (B) and 1.55 g AlCl 3 at 0° C. was added slowly 20 ml DCM. The mixture was stirred 5 minutes at ambient temperature before 7.8 g p-xylene was added slowly. The reaction was stirred 30 minutes at ambient temperature before water was added slowly. The mixture was extracted with DCM (2×50 ml). The combined organic layer was washed with brine, dried over magnesium sulfate, filtered and concentrated. Flash silica chromatography (hexane:ethyl acetate 85:15) afforded 0.758 g product. Example 54 (2-(2,5-dimethylbenzyl)phenyl)(methyl)sulfane [0130] To a solution of 0.758 g (2,5-dimethylphenyl)(2-(methylthio)phenyl)methanone and 1 ml triethylsilane was added 5 ml TFA. The reaction mixture was stirred at RT for 1 hour before water was added. The reaction mixture was extracted with ethyl acetate (2×70 ml) and the combined organic extracts were washed with brine, dried over magnesium sulfate, filtered and concentrated. Flash silica chromatography (hexane:ethyl acetate 80:20) yielded 0.666 g product. Example 55 2-(2,5-dimethylbenzyl)benzenethiol [0131] To a nitrogen flushed mixture of 0.666 g (2-(2,5-dimethylbenzyl)phenyl)(methyl)sulfane and 0.6 g sodium thiolate was added 15 ml anhydrous DMF. The mixture was refluxed under nitrogen until the mixture turned black. The mixture was refluxed for an additional two hours before being cooled to ambient temperature and the addition of water. The mixture was washed with ethyl acetate (2×50 ml). The combined organic extracts were washed with brine, dried over magnesium sulfate, filtered and concentrated. Flash silica chromatography (hexane:ethyl acetate 80:20) afforded 0.51 g product. Example 56 N-(4-cyano-3-(trifluoromethyl)phenyl)-3-(2-(2,5-dimethylbenzyl)phenylsulfonyl)-2-hydroxy-2-methylpropanamide, (PAN71) [0132] The mixture of 0.51 g 2-(2,5-dimethylbenzyl)benzenethiol (2.24 mmol), 0.609 g N-(4-cyano-3-(trifluoromethyl)phenyl)-2-methyloxirane-2-carboxamide (2.24 mmol), 0.5 ml triethylamine, 6 ml ethanol was stirred overnight and concentrated. The residue was dissolved in ethyl acetate, washed with water, brine, dried over magnesium sulfate and concentrated. Without further purification, the residue was mixed with 3.85 g mCPBA (15.5 mmol), 30 ml DCM. The mixture was stirred overnight and concentrated. The residue was dissolved in ethyl acetate, washed with water, brine, dried over magnesium sulfate and concentrated. Purification by chromatography (hexane:ethyl acetate 50:50) yield 0.228 g product (0.43 mmol, 19% yield for two steps). Production of PAN71 was confirmed by 1-H NMR and 13-C NMR. See FIG. 16 for the general PAN71 synthesis strategy. Example 57 Transcription Assays [0133] Twenty-four hours prior to transfection, CV-1 cells were seeded at a density of 45,000 cells per well in 24-well cell culture plates and grown in phenol red free Dulbecco's Modified Eagle Medium (DMEM) supplemented with 10% cosmic calf serum (CCS). ARE-luciferase reporter and Renilla-Luc as the internal standard and a prokaryotic expression vector encoding the wild-type androgen receptor or mutant androgen receptor were transfected with Lipofectamine (Invitrogen) following manufacturer's protocol. Five hours after transfection, media was added containing the appropriate concentrations of ligands. The cells were allowed to incubate for 38 hours before harvesting by passive lysis buffer. Cell extracts were immediately assayed using the Dual Luciferase Assay (Promega). See FIGS. 1-8 and Table 1 for results. Example 58 Competitive Binding Assays [0134] Twenty-four hours prior to transfection, COS-7 cells were seeded at a density of 70,000 cells per well in 24-well cell culture plates and grown in phenol red free Dulbecco's Modified Eagle Medium (DMEM) supplement with 10% cosmic calf serum (CCS). The cells were transfected with a prokaryotic expression vector encoding the wild-type androgen receptor or mutant androgen receptor using Lipofectamine (Invitrogen) following manufacturer's protocol. The cells were allowed to grow for 30 hours and then labeled for 2 hours at 37° C. with [ 3 H]DHT and the appropriate concentration of ligands. Cells were washed with PBS and harvested in 2% SDS, 10% glycerol, and 10 mM Tris, pH 6.8, and radioactivity determined by scintillation counting. See Table 1 for results. TABLE 1 Cellular transcription response (EC 50 /IC 50 ) and Competitive Binding assays for DHT bicalutamide and analogs as agonists and antagonists of AR(wild-type), AR(W741L), AR(W741L) and AR(T877A). hAR(wt) hAR(W741L) hAR(W741C) hAR(T877A) IC50 EC50 K i IC50 EC50 K i IC50 EC50 K i IC50 EC50 mM nM mM mM nM mM mM nM mM mM nM Bic   1 ± 0.08 — 0.4 —  52 ± 14.6 0.2 ± 0   — 107 ± 23  0.7 ± 0.5 1.9 ± 0.4 — 82% 74% PLM1 3.8 ± 0.7 — 0.5 9.7 ± 1.9 — 2.1 ± 2.2 3.3 ± 1.1 — 5.9 ± 6.2   6 ± 0.4 — PLM2 12.5 ± 2.2  — 6.3  23 ± 6.2 — 2.9 ± 1.1 11.6 ± 1.2  — 2.8 ± 1.6 16.5 ± 4.6  — PLM3 12.9 ± 3.6  — 1.6 — — — — 630 ± 67  nd — — 65% PLM4 7.4 ± 2.5 — 2.7 — — — —  33 ± 9.8 2.7 ± 2.9 — — 66% PLM6 21.4 ± 9.9  — 2.1 7.9 ± 1.9 —   1 ± 0.4 7.4 ± 0.9 —  0.2 ± 0.03 5.4 ± 1.7 — (PLM54) PLM7 — — — — — — — — — — — (PLM55) PLM8 4.4 ± 0.7 — 1.1 ± 0.6 — — — — — — 7.7 ± 1.2 — PLM10 — — — — — — — — — — — PLM11 — — — — — — — — — — — PLM12 — — — — — — — — — — — PLM9 7.2 ± 2.3 — 1.8 ± 1.1 9.5 ± 4.7 nd — — — — 7.6 ± 3.4 426 ± 72 48.00% PLM13 40.8 ± 15.7 — nd — — — — — — — — PLM14  12 ± 2.4 — 3.1 ± 0.4 — — — — — — 5.5 ± 1.3 nd PLM15 4.4 ± 1.0 — 0.7 ± 0.3  17 ± 4.5 nd — — — — 4.9 ± 0.9 nd PLM16   8 ± 2.7 — 15.8 ± 11   — — — — — — 15.4 ± 1.8  nd PLM18 8.6 ± 2.4 — 4.4 ± 0.8 — — — — — — — nd PLM19 — — — — — — — — —   9 ± 1.6 nd PAN71 3 — nd nd nd nd nd nd nd nd nd PAN11 2.5 — nd nd nd nd 0.18 0 nd — 1.9 PAN21 1.7 1.8 nd nd nd nd 2.3 — nd 2.5 — PAN31 8.8 — nd nd nd nd 14 — nd 20 — PAN32 0.6 — nd nd nd nd nd nd nd nd nd PAN33 3.7 — nd nd nd nd nd nd nd nd nd PAN37 11 — nd nd nd nd nd nd nd nd nd PAN41 1.7 — nd nd nd nd nd nd nd nd nd PAN51 10 — nd nd nd nd nd nd nd nd nd PAN61 12 — nd nd nd nd nd nd nd nd nd ‘bic’ = bicalutamide. EC 50 = effective concentration for half maximal activation of reporter gene expression. IC 50 = 50% inhibitory concentration of cellular reporter gene expression induced by 3 nM, 250 nM, 200 nM or 10 nM DHT for wild-type, W741L, W741C and T877A respectively. Competitive binding assays (Ki) were measured in the presence of 8 nM, 100 nM and 75 nM [ 3 H]-DHT for AR(wild-type), AR(W741L) and AR(W741C) respectively. ‘nd’ indicates values were not determined, and ‘—’ indicates no effect. Example 59 Cell Proliferation Assays [0135] Further evidence that formulae such as PLM1 can act to limit androgen dependent proliferation of prostate cells was obtained by cell proliferation assays as determined using CyQuant® assays, according to manufacturer's instructions (Invitrogen). Compounds such as PLM1 were found to be at least as potent as biclutamide itself at inhibiting androgen (R1881) induced proliferation of LNCaP cells (see FIG. 9 ). Example 60 In Vitro Selections [0136] Additional evidence that the formulae possess potential to evade anti-androgen withdraw phenotype is demonstrated by in vitro selection assays in LnCAP cells following the method of Hara et al. as described in Cancer Research, 63, 149-153 (2003). LnCAP cells grown in the presence of 20 μM bicalutamide result he selection of antagonist resistant colonies in 20 weeks. Parallel studies starting from 40,000 cells per 3.2 cm dishes show that compounds such as Formula VII, reduce the formation of resistant colonies (see FIG. 10 ).
Disclosed herein are novel antagonists of the androgen receptor and androgen receptor mutations associated with clinical failure of currently prescribed anti-androgens and use of said antagonists in the treatment of conditions associated with inappropriate activation of the androgen receptor.
2
CROSS REFERENCE TO RELATED APPLICATIONS This application is the National Stage of International Application No. PCT/CN2015/074360, filed on Mar. 17, 2015, which claims priority to Chinese Application No. 201410100523.3, filed on Mar. 18, 2014. The contents of both applications are hereby incorporated by reference in their entirety. TECHNICAL FIELD This invention pertains to the technical field of photoinitiators, and particularly to a bisoxime ester photoinitiator and a preparation method and a use thereof. BACKGROUND ART The use of compounds having an oxime ester structure as photoinitiators has been well known in the art, and for example, patent documents having Publication Nos. CN1241562A, CN101508744A, CN101565472A, CN103293855A, etc., have disclosed different carbazole oxime ester photoinitiators and ketoxime ester photoinitiators. These disclosed photoinitiators can satisfy normal application requirements in the current field of photocuring such as display panels, color filters, etc., to different extents. However, since the development of electronic technologies changes rapidly, the existing products started to exhibit deficiencies in some application fields, and the requirements for photoinitiators are higher due to replacement and upgrade of products. At present, for example, most of photoresists used for space control materials do not have good heat resistance, collapse is prone to occur in the process of baking or packaging to result in the shrinkage of space materials, whereas intended increase of the height of the space control material in the process of coating, development by exposure, or the like will result in increased cost, and small molecules melted out upon collapse due to heating will cause contamination of liquid crystal. Furthermore, for example, in the production of premium color filters, the photoinitiator has to meet basic requirements of having high solubility and good thermal stability on the one hand, and its high color quality performance requires a highly colored resist on the other hand. However, as the content of pigments increases, the curing of color resist becomes more difficult, and there are also relatively high requirements for the clarity and the integrity of images after curing. This requires an initiator having a higher photosensitivity to solve the problems described above. In the field of photocuring, a photoinitiator, which has a high photosensitivity and a high stability and is easy to be prepared, is still the first choice in the development of this field, and the research and development of a photoinitiator having higher performances is always a key task in this field. SUMMARY OF THE INVENTION An object of this invention is to provide a bisoxime ester photoinitiator having excellent application performances. By introducing a bisoxime ester group into the chemical structure, this photoinitiator not only has excellent performance in aspects of storage stability, photosensitivity, developability, pattern integrity, and the like, but also exhibits obviously improved photosensitivity and thermal stability compared to similar photoinitiators. In order to achieve the technical effect described above, a technical solution used in this invention is as follows: a bisoxime ester photoinitiator, having a structure represented by general formula (I): wherein, R 1 is wherein * represents a binding position, and X is blank (i.e., two benzene rings on the left and on the right are connected with each other only by Y), a single bond, or a C 1 -C 5 alkylene group; and Y is O, S, or a R 5 N— group, wherein R 5 is hydrogen, a C 1 -C 20 linear or branched alkyl group, a C 3 -C 20 cycloalkyl group, a C 4 -C 20 cycloalkylalkyl group, or a C 4 -C 20 alkylcycloalkyl group; R 2 and R 3 each independently represents a C 1 -C 20 linear or branched alkyl group, a C 3 -C 20 cycloalkyl group, a C 4 -C 20 cycloalkylalkyl group, a C 4 -C 20 alkylcycloalkyl group, and optionally, hydrogen in the above groups may be substituted with a group selected from the group consisting of halogen, a nitro group, a hydroxy group, a carboxyl group, a sulfonic acid group, an amino group, a cyano group, and an alkoxy group; provided that at least one of R 2 and R 3 is a cycloalkylalkyl group which is unsubstituted or substituted with one or more group selected from the group consisting of halogen, a nitro group, a hydroxy group, a carboxyl group, a sulfonic acid group, an amino group, a cyano group, and an alkoxy group, and the structure of said cycloalkylalkyl group is wherein n is an integer of 1-5 and m is an integer of 1-6; R 4 represents a C 1 -C 20 linear or branched alkyl group, a C 3 -C 20 cycloalkyl group, a C 4 -C 20 cycloalkylalkyl group, a C 4 -C 20 alkylcycloalkyl group, a C 3 -C 20 heteroaryl group, and a C 6 -C 20 aryl group, and optionally, hydrogen in the above groups may be substituted with a group selected from the group consisting of halogen, a phenyl group, a nitro group, a hydroxy group, a carboxyl group, a sulfonic acid group, an amino group, a cyano group, and an alkoxy group. As a preferable option of this invention, in the bisoxime ester photoinitiator represented by the general formula (I) described above: in R 1 , X is blank, a single bond, a methylene group, an ethylene group, or a propylene group; and Y is O, S, or a R 5 N— group, wherein R 5 is hydrogen or a C 1 -C 10 linear or branched alkyl group; R 2 and R 3 each independently represent a C 1 -C 5 linear or branched alkyl group or a C 4 -C 15 cycloalkylalkyl group, and optionally, hydrogen in the above groups may be substituted with a group selected from the group consisting of halogen, a nitro group, a cyano group, and an alkoxy group; provided that at least one of R 2 and R 3 is a cycloalkylalkyl group which is unsubstituted or substituted with one or more group selected from the group consisting of halogen, a nitro group, a cyano group, and an alkoxy group, and the structure of said cycloalkylalkyl group is wherein n is an integer of 1-5 and m is an integer of 1-3; R 4 represents a C 1 -C 5 linear or branched alkyl group, a C 3 -C 8 cycloalkyl group, a C 4 -C 8 cycloalkylalkyl group, a C 4 -C 8 alkylcycloalkyl group, a C 3 -C 5 heteroaryl group, and a C 6 -C 10 aryl group, and optionally, hydrogen in the above groups may be substituted with a group selected from the group consisting of halogen, a nitro group, and an alkoxy group. Further preferably, R 1 is selected from the group consisting of the following structures: This invention also relates to a preparation method of the bisoxime ester photoinitiator represented by the general formula (I) described above, comprising the steps of: (1) synthesis of an intermediate 1, wherein: as a starting material and an acid halide compound containing a R 2 group and a R 3 group are used to synthesize the intermediate 1 through a Friedel-Crafts reaction under the action of aluminum trichloride or zinc chloride, and the reaction formula is as follows: wherein Z represents halogen, such as F, Cl, Br, or I; (2) synthesis of an intermediate 2, wherein: an oximation reaction is performed between the intermediate 1 and a nitrite ester (such as ethyl nitrite, isopentyl nitrite, isooctyl nitrite, etc.) or a nitrite salt (such as sodium nitrite, potassium nitrite, etc.) under the action of hydrogen chloride, sodium alkoxide, or potassium alkoxide to generate an intermediate 2, and the reaction formula is as follows: (3) synthesis of the bisoxime ester photoinitiator, wherein: an esterification reaction is performed between the intermediate 2 and an acid halide compound or an acid anhydride containing a R 4 group to synthesize a bisoxime ester photoinitiator product, and the reaction formula is as follows: wherein Z represents halogen, such as F, Cl, Br, or I. All of the raw materials used in the preparation method described above are compounds which are known in the prior art, commercially available, or prepared by known synthetic methods. This preparation method is simple, does not produce polluted wastes in the preparation process thereof, has high product purity, and is suitable for industrial batch production. This invention also relates to use of the bisoxime ester photoinitiator represented by the general formula (I) described above in a photocurable composition (i.e., a photosensitive composition). Without limitation, this photoinitiator may be used in aspects such as color photoresists (RGB), black photoresists (BM), photo-spacers, dry films, semiconductor photoresists, inks, etc. DESCRIPTION OF EMBODIMENTS Hereafter, this invention will be further illustrated in conjunction with specific Examples, but it is not to be understood that the scope of this invention is limited thereto. PREPARATION EXAMPLE Example 1 Preparation of bis-{[4-(3-cyclopentyl-1,2-dione-2-oxime-O-propionate)propyl]phenylene}-sulfide Step (1): preparation of bis-{[4-(3-cyclopentyl-1-one)propyl]phenylene}-sulfide 18.6 g of diphenyl sulfide, 29.4 g of AlCl 3 (finely ground), and 100 mL of dichloromethane were charged into a 500 mL four-neck flask, stirred, and cooled in an ice bath. When the temperature decreased to 0° C., a mixed liquid of 33.7 g of cyclopentylpropionyl chloride and 50 g of dichloromethane were begun to be dropped for about 1.5 h with the temperature being controlled at 10° C. or less, stirring was continued for 2 h, and then the reaction was stopped. The reaction liquid was poured into a diluted hydrochloric acid formulated with 400 g of ice and 65 mL of concentrated hydrochloric acid, the liquid in the lower layer was separated using a separation funnel, and the upper layer was extracted with 50 mL of dichloromethane. The extract and the liquid were combined with each other, washed with a NaHCO 3 solution formulated with 10 g of NaHCO 3 and 200 g of water, and were further washed with 200 mL of water for 3 times until pH value become neutral. Water was removed by drying with 30 g of anhydrous MgSO 4 , and dichloromethane was evaporated by rotation. After evaporation, the crude product in a rotary evaporation flask presented the form of light yellow liquid and was poured into 200 mL of petroleum ether evaporated under normal pressure to obtain a white powdery solid upon stirring and suction filtration, and a product of 39.1 g was obtained after drying in an oven at 50° C. for 5 h, with a yield of 90% and a purity of 96.2%. The structure of the product in step (1) was determined by hydrogen nuclear magnetic resonance spectroscopy, and the specific characteristic result is as follows: 1 H-NMR(CDCl 3 , 500 MHz): 1.4274-1.5412 (22H, m), 2.5214-2.6276 (4H, t), 7.2738-7.3818 (4H, d), 7.7908-7.9824 (4H, d). Step (2): preparation of bis-{[4-(3-cyclopentyl-1,2-dione-2-oxime)propyl]phenylene}-sulfide 21.7 g of the product of step (1), 100 mL of tetrahydrofuran, 13.2 g of concentrated hydrochloric acid, and 11.8 g of isopentyl nitrite were added into a 250 mL four-neck flask, stirred at normal temperature for 5 h, and then the reaction was stopped. Materials were poured into a 2000 mL large beaker and stirred after 1000 mL of water was added, and 200 g of dichloromethane was used for extraction. The extract was dried by adding 50 g of anhydrous MgSO 4 , followed by suction filtration. The solvent was removed by rotary evaporation of the filtrate under reduced pressure, and an oily viscous matter was obtained in a rotary bottle. The viscous matter was poured into 150 mL of petroleum ether and was precipitated with stirring, followed by suction filtration, a white powdery solid was obtained, and after drying at 60° C. for 5 h, a product of 20.9 g was obtained with a yield of 85% and a relative purity of 95.2%. The structure of the product in step (2) was determined by hydrogen nuclear magnetic resonance spectroscopy, and the specific characteristic result is as follows: 1 H-NMR(CDCl 3 , 500 MHz): 1.4037-1.5431 (18H, m), 2.0321-2.1735 (2H, s), 2.5001-2.7221 (4H, d), 7.3034-7.3241 (4H, d), 7.8002-7.9922 (4H, m). Step (3): preparation of bis-{[4-(3-cyclopentyl-1,2-dione-2-oxime-O-propionate) propyl]phenylene}-sulfide 19.7 g of the product of step (2), 100 g of dichloromethane, and 4.1 g of triethylamine were added into a 250 mL four-neck flask and were stirred at room temperature for 5 min, and then 7.8 g of propionyl chloride was dropped within about 30 min. Stirring was continued for 2 h, and then 5% NaHCO 3 aqueous solution was added to adjust pH value to become neutral. An organic layer was separated with a separation funnel, followed by washing twice with 200 mL of water and drying with 50 g of anhydrous MgSO 4 , and the solvent was evaporated by rotation to obtain a viscous liquid. Recrystallization with methanol obtained a white solid powder, which was filtered to obtain a product of 23.1 g with a purity of 99%. The structure of the final product was determined by hydrogen nuclear magnetic resonance spectroscopy, and the specific characteristic result is as follows: 1 H-NMR(CDCl 3 , 500 MHz): 0.9351-1.1213 (6H, t), 1.3351-1.4913 (18H, m), 2.1737-2.2923 (4H, m), 2.6981-2.8821 (4H, m), 7.3201-8.1241 (8H, d). Example 2 Preparation of [2-(3-cyclopropyl-1,2-dione-2-oxime-O-propionate)propyl]-[7-(4-cyclopentyl-1,2-dione-2-oxime-O-propionate)butyl]-thioxanthene Step (1): preparation of [2-(3-cyclopropyl-1-one)propyl]-[7-(4-cyclopentyl-1-one)butyl]-thioxanthene 19.8 g of thioxanthene, 14.7 g of AlCl 3 (finely ground), and 100 mL of dichloromethane were charged into a 500 mL four-neck flask, stirred, and cooled in an ice bath. When the temperature decreased to 0° C., a mixed liquid of 13.5 g of cyclopropylpropionyl chloride and 25 g of dichloromethane were begun to be dropped for about 1.5 h with the temperature being controlled at 10° C. or less, and stirring was continued for 2 h. 14.7 g of AlCl 3 (finely ground) was then added into the four-neck flask, a mixed liquid of 17.8 g of cyclopentylbutanoyl chloride and 25 g of dichloromethane was dropped for about 1.5 h with the temperature being controlled at 10° C. or less, the temperature was raised to 15° C., stirring was continued for 2 h, and then the reaction was stopped. The reaction liquid was poured into diluted hydrochloric acid formulated with 400 g of ice and 65 mL of concentrated hydrochloric acid, the liquid in the lower layer was separated using a separation funnel, and the upper layer was extracted with 50 mL of dichloromethane. The extract and the liquid were combined with each other, washed with NaHCO 3 solution formulated with 10 g of NaHCO 3 and 200 g of water, and were further washed with 200 mL of water for 3 times until pH value become neutral. Water was removed by drying with 30 g of anhydrous MgSO 4 , and dichloromethane was evaporated by rotation. After evaporation, the crude product in a rotary evaporation flask presented the form of light yellow liquid and was poured into 200 mL of petroleum ether evaporated under normal pressure to obtain a white powdery solid upon stirring and suction filtration, and a product of 38.1 g was obtained after drying in an oven at 50° C. for 5 h, with a yield of 88% and a purity of 96.2%. The structure of the product in step (1) was determined by hydrogen nuclear magnetic resonance spectroscopy, and the specific characteristic result is as follows: 1 H-NMR(CDCl 3 , 500 MHz): 0.19366-0.2114 (5H, m), 1.2744-1.5831 (15H, m), 2.5762-2.6144 (4H, t), 3.7659-3.8407 (2H, s), 7.1908-7.2824 (2H, d), 7.4457-7.5763 (4H, m). Step (2): preparation of [2-(3-cyclopropyl-1,2-dione-2-oxime)propyl]-[7-(4-cyclopentyl-1,2-dione-2-oxime)butyl]-thioxanthene 21.6 g of the product of step (1), 100 mL of tetrahydrofuran, 13.2 g of concentrated hydrochloric acid, and 11.8 g of isopentyl nitrite were added into a 250 mL four-neck flask, stirred at normal temperature for 5 h, and then the reaction was stopped. Materials were poured into a 2000 mL large beaker and stirred after 1000 mL of water was added, and 200 g of dichloromethane was used for extraction. The extract was dried by adding 50 g of anhydrous MgSO 4 , followed by suction filtration. The filtrate was removed by rotary evaporation under reduced pressure, and an oily viscous matter was obtained in a rotary bottle. The viscous matter was poured into 150 mL of petroleum ether and was precipitated with stirring, followed by suction filtration, a white powdery solid was obtained, and after drying at 60° C. for 5 h, a product of 21.1 g was obtained with a yield of 86% and a relative purity of 95.2%. The structure of the product in step (2) was determined by hydrogen nuclear magnetic resonance spectroscopy, and the specific characteristic result is as follows: 1H-NMR(CDCl 3 , 500 MHz): 0.2037-0.2431 (5H, m), 1.4355-1.5032 (11H, m), 2.0117-2.1349 (2H, s), 2.5132-2.7065 (4H, m), 3.8002 (2H, s), 7.3034-7.5241 (6H, d). Step (3): preparation of [2-(3-cyclopropyl-1,2-dione-2-oxime-O-propionate) propyl]-[7-(4-cyclopentyl-1,2-dione-2-oxime-O-propionate) butyl]-thioxanthene 19.6 g of the product of step (2), 100 g of dichloromethane, and 4.1 g of triethylamine were added into a 250 ml four-neck flask and were stirred at room temperature for 5 min, and then 7.6 g of propionyl chloride was dropped within about 30 min. Stirring was continued for 2 h, and then 5% NaHCO 3 aqueous solution was added to adjust pH value to become neutral. An organic layer was separated with a separation funnel, followed by washing twice with 200 mL of water and drying with 50 g of anhydrous MgSO 4 , and the solvent was evaporated by rotation to obtain a viscous liquid. Recrystallization with methanol obtained a white solid powder, which was filtered to obtain a product of 22.1 g with a purity of 99%. The structure of the final product was determined by hydrogen nuclear magnetic resonance spectroscopy, and the specific characteristic result is as follows: 1 H-NMR(CDCl 3 , 500 MHz): 0.1981-0.2209 (5H, m), 1.1038-1.2004 (6H, m), 1.498-1.5703 (11H, m), 2.2765-2.3951 (4H, m), 2.5964-2.7123 (4H, m), 3.8678 (2H, s), 7.2854-7.3409 (2H, d), 7.3988-7.5028 (4H, m). Examples 3-13 Referring to the method illustrated in Example 1 or 2, compounds shown in Examples 3-13 were prepared from and corresponding acylating agents. The structures of compounds of interest and 1 H-NMR data thereof were listed in Table 1. TABLE 1 Examples Compounds (3-13) 1 H NMR δ[ppm] Example 3 0.1771-0.2134(5H, m) 2.2191-2.2721(6H, s) 2.3176-2.4481(2H, d) 3.0211-3.3113(2H, s) 7.2853-7.9062(8H, d) Example 4 0.1801-0.2068(5H, m) 1.1067-1.2024(6H, s) 1.4431-1.5199(11H, m) 2.3308-2.4542(4H, m) 2.7150-2.8604(4H, t) 7.2743-8.0032(8H, m) Example 5 0.1799-0.2134(5H, m) 1.0056-1.1387(9H, m) 1.4500-1.6583(10H, m) 2.2165-2.3566(4H, s) 2.7381-2.8436(4H, t) 3.8655(2H, s) 7.2433-7.5741(6H, m) Example 6 0.1801-0.2104(5H, m) 0.9560-1.0801(6H, t) 1.4991-1.6630(13H, m) 2.2001-2.3708(4H, m) 2.6754-2.8318(4H, m) 7.3093-8.1061(6H, m) Example 7 1.0016-1.1023(9H, t) 1.4128-1.5319(11H, m) 2.2100-2.3106(4H, m) 2.6128-2.8012(4H, m) 7.2098-7.9531(8H, m) Example 8 1.3921-1.5129(11H, m) 2.0309-2.2237(6H, s) 2.5998-2.6879(2H, t) 3.2231-3.2456(3H, s) 3.4002-3.5023(2H, s) 3.8001-3.9123(2H, s) 6.9618-7.7239(6H, m) Example 9 1.0239-1.1123(3H, t) 1.3906-1.5248(11H, m) 2.6540-2.8761(H, m) 5.3501-5.3501(H, s) 7.6681-8.2871(6H, m) Example 10 0.9981-1.1031(3H, t) 1.3909-1.5216(11H, m) 2.1659-2.8192(16H, m) 3.5602-3.9768(2H, t) 7.3982-8.0007(6H, m) Example 11 0.9567-1.0389(9H, t) 1.2908-1.5345(18H, m) 1.8665-2.0954(2H, m) 2.1981-2.3041(4H, s) 2.6260-2.7893(8H, m) 3.6782-3.9348(4H, m) 7.5562-8.1008(6H, m) Example 12 0.9217-1.1129(6H, t) 1.3781-1.7961(15H, m) 2.6981-2.8045(4H, m) 3.8109-3.9861(2H, m) 7.4723-8.4018(16H, m) Example 13 0.9549-1.0036(3H, t) 1.4029-1.5632(17H, m) 2.6102-2.8982(4H, m) 3.9651-4.1071(1H, m) 7.3031-8.4089(16H, m) Performance Evaluation By formulating exemplary photocurable compositions, respective application performances of the photoinitiators represented by the general formula (I) of this invention, were evaluated, including aspects of storage stability, photosensitivity, developability, pattern integrity, thermal stability, etc. 1. Formulation of Photocurable Compositions (1) Uncolored Photocurable Composition A Acrylate copolymer 100 (Benzyl methacrylate/methacrylic acid/hydroxyethyl methacrylate (molar ratio of 70/10/20) copolymer (Mw: 10,000)) Trimethylolpropane triacrylate (TMPTA) 100 Photoinitiator 2 Butanone (solvent) 25 (2) Colored Photocurable Composition B Acrylate copolymer 100 (Benzyl methacrylate/methacrylic acid/methyl methacrylate (molar ratio of 50/15/30) copolymer (Mw: 15,000)) Dipentaerythritol hexaacrylate 100 Photoinitiator 2 Butanone (solvent) 25 Dye blue 15 5 In the compositions A and B described above, the photoinitiator was a bisoxime ester compound represented by the general formula (I) disclosed by this invention or a photoinitiator known in the prior art as a comparison, and the respective components were represented in parts by mass. 2. Development by Exposure The photocurable compositions A and B described above were stirred, respectively, under protection from light. Materials were taken on a PET template and film coating was performed with a wire bar, the solvent was removed by drying at 90° C. for 5 min, and a coating film with a film thickness of about 2 μm was formed. The substrate on which the coating film was formed was cooled to room temperature, a mask plate was attached thereon, and a long wavelength irradiation was achieved with a high pressure mercury lamp 1PCS light source through a FWHM color filter. Exposure was performed on the coating film through a seam of the mask plate under an ultraviolet having a wavelength of 370-420 nm. Subsequently, development was performed by soaking in a 2.5% sodium carbonate solution at 25° C. for 20 s, followed by washing with ultra-pure water and air drying. The pattern was fixed by hard baking at 220° C. for 30 min, and the obtained pattern was evaluated. 3. Performance Evaluation of Photocurable Compositions (1) Storage Stability After naturally storing a liquid-state photocurable composition at room temperature for 1 month, the degree of precipitation of substances was visually evaluated according to the following criteria: A: No precipitation was observed; B: Precipitation was slightly observed; C: Significant precipitation was observed. (2) Photosensitivity Upon exposure, the minimum exposure amount of the irradiated region having a residual film rate of 90% or more after development in the step of exposure was evaluated as the demand of exposure. A smaller exposure demand represents a higher sensitivity. (3) Developability and Pattern Integrity The pattern on the substrate was observed using a scanning electron microscope (SEM) to evaluate the developability and the pattern integrity. The developability was evaluated according to the following criteria: ∘: No residue was observed in unexposed portions; ⊚: A small amount of residue was observed in unexposed portions, but the residue is acceptable; •: Significant residue was observed in unexposed portions. The pattern integrity was evaluated according to the following criteria: ⋄: No pattern defects were observed; □: A few defects were observed in some portions of the pattern; ♦: A number of defects were significantly observed in the pattern. (4) Thermal Stability The change of the film thickness before and after hard baking was measured using a thickness measurer to evaluate the thermal stability of the material. Evaluation results were as shown in Table 2 and Table 3: TABLE 2 Photocurable composition A Demand Thickness Thickness of before after Change Storage exposure Pattern hard hard of film Photoinitiator stability mJ/cm 2 Developability integrity baking baking thickness Example Compound 1 A 55 ◯ ⋄ 2.1 2.0 4.8%  Compound 3 A 53 ◯ ⋄ 2.0 1.9  5% Compound 5 A 51 ◯ ⋄ 2.0 1.9  5% Compound A 48 ◯ ⋄ 1.9 1.8 5.2%  10 Compound A 40 ◯ ⋄ 2.1 2.0 4.8%  12 Compound A 32 ◯ ⋄ 2.0 1.9  5% 13 Comparative PBG-304 A 70 ⊚ □ 2.0 1.7 15% Example OXE-01 B 105 ⊚ ♦ 2.0 1.6 20% OXE-02 B 85 ⊚ ♦ 2.0 1.6 20% Irgacure907 C 160 ● ♦ 2.1 1.4 33% TABLE 3 Photocurable composition B Demand Thickness Thickness of before after Change Storage exposure Pattern hard hard of film Photoinitiator stability mJ/cm 2 Developability integrity baking baking thickness Example Compound 1 A 60 ◯ ⋄ 2.0 1.9  5% Compound 3 A 58 ◯ ⋄ 2.0 1.9  5% Compound 5 A 56 ◯ ⋄ 2.1 2.0 4.8%  Compound A 53 ◯ ⋄ 2.0 1.9  5% 10 Compound A 46 ◯ ⋄ 2.1 2.0 4.8%  12 Compound A 40 ◯ ⋄ 2.0 1.9  5% 13 Comparative PBG-304 A 88 ⊚ □ 2.1 1.9 9.5%  Example OXE-01 B 117 ⊚ ♦ 1.9 1.6 21% OXE-02 B 98 ⊚ ♦ 2.0 1.8 10% Irgacure907 C 176 ● ♦ 2.1 1.6 24% In Table 2 and Table 3, PBG-304 represents a photoinitiator, 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentylacetone)-1-oxime-acetate, disclosed in CN101508744A; OXE-01 represents 1-(4-phenylthio-phenyl)-octan-1,2-dione-2-oxime-O-benzoate; OXE-02 represents 1-(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-ethanone)-1-oxime-acetate; and Irgacure907 represents 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-propane-1-one. It can be seen from the results of Table 2 and Table 3 that the photocurable composition comprising the bisoxime ester photoinitiator represented by the general formula (I) of this invention has good storage stability, exhibits extremely good photosensitivity, developability, and pattern integrity in both colorless systems and pigment systems, and has a thermal stability obviously superior to those of existing photoinitiators. By comparison, there are significant shortages for PBG-304, OXE-01, OXE-02, and Irgacure 907 in aspects of storage stability, photosensitivity, developability, pattern integrity, and thermal stability. In summary, the bisoxime ester photoinitiator represented by the general formula (I) disclosed by this invention has excellent application performances, and can greatly improve the performances of photocured products when used in photocurable compositions.
A bisoxime ester photoinitiator as represented by general formula (I). By introducing a bisoxime ester group and a cycloalkylalkyl group into the chemical structure, this photoinitiator not only has excellent performance in aspects of storage stability, photosensitivity, developability, pattern integrity, and the like, but also exhibits obviously improved photosensitivity and thermal stability compared to similar photoinitiators.
2
BACKGROUND OF THE INVENTION The present invention relates to a new and improved construction of centrifugal casting arrangement for a centrifugal casting machine, especially for dental applications, as well as to an improved construction of housing structure for use in such centrifugal casting machine. Centrifugal casting machines of the aforementioned general type are well known in the art. For instance, centrifugal casting machines suitable for use in dentistry have been disclosed, for instance, in German Patent Publication No. 2,020,910, published Nov. 18, 1971, German Patent Publication No. 2,932,543, published Feb. 14, 1980, and the published brochure of the well known German company Degussa Corporation, entitled "Tiegelschleuder Ts 3". Such type of centrifugal casting machines are typically used in dental laboratories for fabricating artificial dentures or parts thereof, such as prosthesis and cast parts formed of noble metals or replacement materials. Seated upon a centrifuge or centrifugal arm of such centrifugal casting machine is a muffle or retort holder which can be elevationally adjusted and serving for supporting casting muffles or retorts of different sizes. Also seated upon such centrifuge arm is a compensation or balancing mass which can be locked at appropriate positions upon the centrifuge arm in accordance with the momentarily employed muffle mass. Additionally, such type of centrifugal casting equipment uses a melting crucible or a melting trough. Both the muffle holder and the compensation mass or weight, depending upon the size of the muffle or retort, must be placed in a correct position, in order to eliminate as far as possible any imbalance during the centrifugal casting operation. With such state-of-the-art equipment the centrifuge or centrifugal arm is secured in horizontal position upon a vertical shaft or axle of a drive element, for instance a spiral spring or a drive motor and optionally accommodated within a housing. Such known constructions of centrifugal casting machine no longer fulfil the present day requirements as concerns protection against accidents and ease in operation. The tightening of the drive spring of the centrifuge arm, the manipulations carried out at such centrifuge arm when the spring is tensioned as well as the operation of the centrifugal casting machine, is dangerous. Additionally, particularly in the case of motor-driven centrifugal casting machines, the compensation or balancing mass is not adjusted by the operating personnel to the size of the momentarily employed muffle or retort. Hence, due to the high circumferential velocity of the centrifuge arm the entire centrifugal casting machine is markedly mechanically loaded because of the prevailing imbalance, and hence must be mounted in an extremely solid or sturdy fashion in order to avoid the production of faulty castings due to the vibrations which arise. SUMMARY OF THE INVENTION Therefore, with the foregoing in mind it is a primary object of the present invention to provide a new and improved construction of centrifugal casting arrangement for a centrifugal casting machine which is not associated with the aforementioned drawbacks and limitations of the prior art proposals. Another and more specific object of the present invention aims at the provision of a new and improved construction of centrifugal casting arrangement, especially for use in dentistry, which avoids the previously explained disadvantages. Yet a further important object of the present invention is concerned with the provision of a new and improved construction of centrifugal casting machine which allows use by the operating personnel without any danger thereto as well as good accessibility and ease of handling the centrifugal casting machine. A further important object of the present invention is directed to a new and improved construction of housing structure for use in such centrifugal casting machine. Another noteworthy object of the present invention is directed to a new and improved construction of centrifugal casting machine, especially for dental applications, which is relatively simple in construction and design, quite economical to manufacture, extremely reliable in operation, not readily subject to breakdown or malfunction, requires a minimum of maintenance and servicing, and can be easily and safely used by the operator. Now in order to implement these and still further objects of the invention, which will become more readily apparent as the description proceeds, the centrigual casting arrangement for a centrifugal casting machine as contemplated in the present development, especially for use in dental applications, is manifested by the features that there is provided a drive shaft, at the end or end region of which there is secured a centrifuge or centrifugal arm. A muffle or retort holder is arranged at one end or end region of the centrifuge arm so as to be movable essentially in vertical direction. A compensation or balancing mass or weight is arranged for displacement along the other end or end region of the centrifuge arm. This compensation or balancing mass serves to compensate for imbalances which may arise when working with different sizes of casting muffles or retorts. There is also provided a melting crucible which is arranged upon the centrifuge arm and cooperates with the casting muffle or retort. Importantly, the muffle holder or support and the balancing mass are drivingly interconnected with one another by drive connection means in such a manner that during the adjustment or setting of the muffle holder to the size of the momentarily used or mounted casting muffle along an essentially vertically disposed rod member for the purpose of accommodation to the position of a casting opening or orifice of the melting crucible, the balancing mass or weight is synchronously displaced to a location of the centrifuge arm which compensates for the mass or weight of the muffle. As already mentioned previously, the present invention is not only concerned with such improved centrifugal casting arrangement for a centrifugal casting machine but also relates to a new and improved housing structure for such centrifugal casting machine. This housing or housing structure contains a cover member and a drive for the centrifugal casting arrangement of the centrifugal casting machine. The centrifugal casting arrangement and its drive or drive means are operatively coupled with the cover member by means of a timing element or time-switching mechanism arranged in a control cabinet in such a manner that by closing the cover member the drive of the centrifugal casting arrangement is placed into operation for a predetermined adjustable time and after expiration of such time there must first expire an additional amount of time during which there is completely stopped the centrifugal casting arrangement and following which the cover member can be raised to permit access to the centrifugal casting arrangement located in the housing structure of the centrifugal casting machine. The drive connection means which establishes an operative interconnection between the elevational adjustment of the muffle or retort holder for accommodation of the muffle size and the balancing mass located at the opposite end of the centrifuge arm, precludes the occurrence of errors which could otherwise cause damage to parts of the drive and require a rigid attachment or mounting of the centrifugal casting machine. Due to the inclined arrangement of the centrifuge or centrifugal arm, according to a preferred embodiment of the invention, there is obviated the need to resort to further complicated measures for preventing the aforementioned imbalance. A further advantage in terms of reducing such imbalance is obtained by the infinite adjustability of the holder and which can be accomplished in synchronism and automatically with the adjustment of the balancing mass or weight. The operative coupling of the centrifuge arm drive and the cover member, upon closure thereof, prevents access of the operating personnel to the rotating centrifuge arm. The timing element or a standstill monitor, for instance a centrifugal force switch, also prevents opening of the cover member during the slowing-down or run-out of the centrifuge arm. The infeed of the measuring and energy lines or conductors to the heating element of the melting crucible and through the motor shaft is of advantage, because following the heating operation it is unnecessary to remove the connections before there can be initiated the centrifugal casting operation. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be better understood and objects other than those set forth above, will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein: FIG. 1 illustrates, partially in section view, a preferred embodiment of centrifugal casting arrangement for a centrifugal casting machine and containing a centrifuge or centrifugal arm equipped with a muffle or retort holder and a compensation or balancing mass; and FIG. 2 is a schematic view, partially in section, depicting essentially the complete arrangement of centrifugal casting machine containing the centrifugal casting arrangement illustrated in FIG. 1 and the novel housing structure therefor. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Describing now the drawings, it is to be understood that only enough of the construction of the centrifugal casting machine has been depicted in the drawings as needed for those skilled in the art to readily understand the underlying principles and concepts of the present development, while simplifying the illustration of the drawings. Turning attention now to FIG. 1, there is shown a centrifugal casting arrangement 33 for use in a centrifugal casting machine, especially for dental applications. The centrifugal casting arrangement 33 is secured upon a rotatable drive shaft 1 which serves to rotatably drive such centrifugal casting arrangement 33. The drive shaft 1 may be hollow, so that there can extend therethrough power or heating lines for a melting crucible or vat 16 and appropriate measuring elements, as generally schematically indicated by reference character 35 in FIG. 1. A centrifuge or centrifugal arm 2 in the form of a tubular member or pipe 3 of such centrifugal casting arrangement 33 is mounted in a plane which is inclined with respect to the horizontal. At the higher situated end or end region 4 of the tubular member or pipe 3 there is provided a balancing or compensation mass or weight 5. This balancing mass or weight 5 is secured to a drive rod or rod member 6 which is rotatably mounted within the tubular member 3 and is composed of different rod sections, as will be explained more fully hereinafter. In particular, it will be observed that at the tube end 4 the drive rod member 6 is provided with a threaded portion or section 7 which engages with internal threads 8 provided within the related end portion of the tubular member or pipe 3. The external threads 7 at the drive rod 6 and the coacting internal threads 8 within the tubular member 3 provide a lengthwise displaceable connection of the drive rod member 6 together with the balancing mass or weight 5. At the oppositely located end 9 of the centrifuge arm 2 the drive rod member 6 is provided with continuous gaps or recesses 10 which define tooth spaces with which mesh the teeth of a gear or pinion 11 mounted upon the centrifuge arm 2. There is also displaceably arranged with respect to the centrifuge arm 2, again at the arm end 9, a rod in the form of a gear rack 12 which can be displaced transversely, if desired at an inclination, with respect to the centrifuge arm 2. This gear rack 12 meshes with the gear or pinion 11. At the upper end of the gear rack 12, which is guided so as to be laterally offset with respect to the drive rod member 6 there is located an essentially horizontally positioned muffle or retort holder or support 13. At the end 9 of the centrifuge arm 2 there is also mounted a holder member 14. As has been schematically shown in broken or phantom lines in FIG. 1 a heating element 15 along with the melting crucible or vat 16 having an outlet or pouring opening or orifice 17 and a heating coil or winding 18 are provided. Additionally, there will be observed that a casting muffle or retort 20 having an infeed or filling opening or orifice 20 is arranged upon the muffle or retort holder 13. These elements are basically conventional and do not constitute part of the invention as such, and therefore need not here be further explained. The described centrifugal casting arrangement 33 of FIG. 1 is incorporated into a centrifugal casting machine 21, details of which have been depicted in FIG. 2. It will be observed that the centrifugal casting machine 21 comprises a housing structure containing a housing 22 and a cover member 23 for protectively closing the housing 22. At the intermediate floor or false bottom 24 of the housing 22 there is arranged a drive motor 25, to whose drive or output shaft there is flanged the drive shaft 1 of the centrifuge arm or arm member 2. The cover member 23, which is hingedly connected at the hinge or pivot joint structure 26, is operatively associated with a suitable cover opening facility, for instance a magnetic lock or latching mechanism 27 powered by alternating-current and delivering a signal indicating to an operator that the cover member can be opened. Extending from a control cabinet or box 28, which contains a suitable timing element or time-switching mechanism 28a, for instance a timing relay or timer mechanism, and the requisite relay means 28b or the drive motor 25, and which control cabinet 28 is also operatively associated with the magnetic lock mechanism 27 for the cover member 23, are the feed or supply lines 40 leading to the aforementioned drive means as well as to a primary switch 29 having suitable control lamps or indicators and arranged at the front side of the centrifugal casting machine 21. There also can be arranged upon the drive shaft 1 a ventilator impeller or vane arrangement 30, and in the housing 22 there can be provided air slots 32 for circulating air through such housing 22. The cover member 23 preferably does not sealingly close the housing or housing member 22, and thus, leaves free an air gap or space 31. In the description to follow there will now be considered the mode of operation of the centrifugal casting machine 21 and its centrifugal casting arrangement 33 as previously described. An empty muffle or retort 19 is placed upon the muffle holder or support 13 and the balancing mass or weight 5 is rotated for such length of time until the muffle 19 assumes the requisite elevational position where its inlet or filling opening 20 registers with the outlet or pouring opening 17 of the melting crucible 16. During rotation of the balancing mass or weight 5 such either moves outwardly, if there has been mounted a large-size muffle or retort 19, or inwardly if there is being used a smaller size muffle or retort 19. The pitch of the external threads 7 and internal threads 8 of the drive rod member 6 and tubular member 3 as well as also the tooth pitch at the gear or pinion 11 and the pitch of the tooth gaps or spaces 10 at the other end of such drive rod member 6 and the pitch of the teeth at the gear rack 12 are, of course, designed such that the mass of the momentarily mounted muffle or retort 19 is opposed by a corresponding balancing mass which prevents or markedly reduces any imbalance in the centrifuge arm 2. The slight inclination of the centrifuge arm 2 ensures that the center of gravity of the mass of the muffle or retort 19 essentially comes to lie or revolve in the same rotational plane as the center of gravity of the balancing mass or weight 5. Consequently, there can be obtained not only a static, but especially also a dynamic equilibrium. The centrifugal casting machine 21 depicted in FIG. 2 along with the therein mounted centrifugal casting arrangement 33 as previously described in detail with reference to FIG. 1 operates in the following manner: While the cover member 23 is open the heating coil or winding 18 melts the metallic material located in the melting crucible 16. If the operator or, in fact, a suitable measuring element determines that there has been reached the required temperature, then the cover member 23 is closed. Immediately after closure of the cover member 23 the drive motor 25 places into rotation the centrifuge arm 2 for a time period or interval t 1 which can be adjusted by the control cabinet or arrangement 28. After starting the rotational movement of the centrifuge arm 2 the liquid metal is propelled through the infeed opening or orifice 20 into the casting muffle or retort 19 and is then solidified therein. After expiration of the set or adjusted time t 1 the drive motor 25 is switched-off and after a further previously predetermined set time interval or time t 2 or by means of a conventional and therefore not particularly shown standstill indicator, the cover member 23 is opened by the magnetic lock or locking mechanism 27. The opening operation can be optionally indicated either acoustically or optically if desired. By prior experimentation and the application of suitable markings it is possible to determine and readily indicate the appropriate position for the balancing mass or weight 5 for the momentarily selected muffle or retort size (mass). While there are shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims. Accordingly,
Due to the inclination of a centrifuge arm of a centrifugal casting arrangement the mass of a muffle or retort and a compensation or balancing mass come to lie essentially in the same rotational plane. The infinite adjustment of a muffle or retort holder and the compensation or balancing mass is accomplished by a drive rod movably arranged within the centrifuge arm as well as by a gear rack driven by the drive rod and upon which there is seated the muffle holder. A housing structure containing a cover member prevents access to the centrifugal casting arrangement during operation of the centrifugal casting machine.
1
TECHNICAL FIELD [0001] The present invention relates to an accessory of a power tool, in particular to a cutting accessory detachably mounted on an oscillating power tool. The present invention also relates to an oscillating power tool using the cutting accessory. BACKGROUND OF THE INVENTION [0002] An Oscillation tool is a common oscillating power tool. Its output shaft rotates and swings around the axis, so with different accessory tool bits installed on the output shaft, many different operation functions can be realized, such as sawing, cutting, grinding and scraping, thus meeting different working demands. [0003] However, many oscillation tools do not currently have a special accessory tool bit for realizing shearing and cutting operations, and if they use the existing accessory tool bit, such as the saw blade, they achieve an undesirable cutting effect. Therefore, other tools, such as electric scissors, are required to meet the shearing and cutting demands of the user. [0004] At present, common electric scissors comprise two knives, one of which usually is a fixed knife, while the other is a moving knife which moves relative to the fixed knife. The moving knife is connected with the transmission shaft and can generate reciprocating oscillation by the action of the motor, while the fixed knife is kept still. Thus, by means of the reciprocating movement of the moving knife, the shearing and cutting functions of the scissors are realized. [0005] In the field, a cutting accessory capable of being applied to the oscillating power tool is needed to expand the application scope of the oscillation tool. To meet this demand, a publicized German patent application DE102008030024A1 discloses a cutting accessory capable of being applied to the oscillation tool. The structure of this cutting accessory is similar to that of the electric scissors, also comprising a fixed knife and a moving knife driven by the output shaft of the oscillation tool to oscillate reciprocatingly. [0006] However, when the cutting accessory applied to the oscillating power tool cuts an object, only the moving knife imposes a cutting force onto the object, so the cutting force is not enough and the cutting efficiency is low. [0007] Thus, it is truly necessary to provide an improved cutting accessory to overcome the shortcomings of the cutting accessory applied to the oscillating power tool. SUMMARY OF THE INVENTION [0008] The object of the invention is to disclose a cutting accessory which is capable to detachably mount on an oscillating power tool and has an improved efficiency. [0009] A cutting accessory detachably mounted on an oscillating power tool, the oscillating power tool includes a head housing and an output shaft extending from the head housing. The output shaft reciprocatingly rotates along the axis of the output shaft. The cutting accessory includes a housing adapted to the head housing, two movable blades partly received in the housing, and a driving element adapted to the output shaft. The driving element reciprocatingly rotates driven by the output shaft and simultaneously drive the two moving knives moving in the opposite directions to cut a workpiece. [0010] In a preferred embodiment, the driving element includes a mounting portion adapted to the output shaft and two driving portions symmetrically disposed relative the mounting portion. The two driving portions adapt to the two movable blades respectively. [0011] In a preferred embodiment, in each pair of one driving portions of the driving element and one movable blade, one of the driving portion and the movable blade includes a groove and the other includes a roller configured to be received and rolled in the groove. [0012] In a preferred embodiment, each groove includes two straight sections which are located in the middle part of the groove and are parallel to each other. [0013] In a preferred embodiment, the angle of the straight sections of one of the grooves relative to the line of the centers of the grooves is different from the angle of the straight sections of the other groove relative to the line of the centers of the grooves. [0014] In a preferred embodiment, the grooves are formed at the driving portions respectively, and the centers of the two grooves and the center of mounting portion are located in a line. [0015] In a preferred embodiment, the two movable blades pivotably connect to the same pivoting shaft. The axis of the pivoting shaft is substantially parallel to the longitudinal axis of the output shaft. [0016] In a preferred embodiment, the centers of the rollers are equidistant from the center of the pivoting shaft. [0017] In a preferred embodiment, the housing includes an upper cover and a lower cover adapted to the upper cover. The driving element and two movable blades disposed between the upper cover and the lower cover. [0018] In a preferred embodiment, the housing includes an opening and a fixing portion adapted to the head housing. The output shaft configured to pass through the opening. [0019] In a preferred embodiment, the housing includes a slot configured for receiving the driving element, and the driving element configured to rotate oscillatingly in the slot [0020] In a preferred embodiment, the two movable blades each include a head portion, a cutting portion and a connecting portion between the head portion and the cutting portion. The head portions cooperate with the driving element respectively. The connecting portions pivotably connect to the housing. The driving element is configured to drive the cutting portions of the movable blades to move in the opposite directions. [0021] In a preferred embodiment, the cutting accessory further includes a guide element fixed with the head housing. The movable blades each includes a head portion cooperating with the driving element, a cutting portion and a guiding portion cooperating with the guide element. The cutting portions each have cutting teeth. The cutting teeth of the cutting portion of one of the movable blades are opposite to the cutting teeth of the cutting portion of the other movable blade. The driving element is configured to drive the two movable blades to move in the opposite directions by the engagement of the guide element and the guide portion. [0022] In a preferred embodiment, the plane defined by the two movable blades is substantially perpendicular to the longitudinal axis of the output shaft and the cutting portions of the movable blades each include the cutting teeth at both sides thereof. [0023] Another object of the invention is providing an oscillating power tool having capable of cutting and improved cutting efficiency. [0024] To achieve the object, the solution of the invention is as below: An oscillating power tool includes a head housing, an output shaft protruding out of the head housing and a cutting accessory mounted on the output shaft. The output shaft rotates oscillatingly about a longitudinal axis thereof. The cutting accessory includes two movable blades which move relative to the head housing, and a driving element adapted to the output shaft. The driving element is configured to oscillate by the actuation of the output shaft and to simultaneously drive the two movable blades to move in opposite directions to cut a workpiece. [0025] To achieve the object, another solution of the invention is as below: An oscillating power tool includes a head housing, an output shaft protruding out of the head housing and a cutting accessory mounted on the output shaft. The output shaft rotates oscillatingly about a longitudinal axis thereof. The cutting accessory includes a housing adapted to the head housing, two movable blades partly received in the housing and a driving element adapted to the output shaft. The two movable blades both have head portions, cutting portions and connecting portions between the head portions and the cutting portions. The two head portions cooperate with the driving element respectively. The two connecting portion pivotably connect to the housing and the driving element drive the two movable blades to move in the opposite directions. [0026] To achieve the object, another solution of the invention is as below: An oscillating power tool includes a head housing, an output shaft protruding out of the head housing and a cutting accessory mounted on the output shaft. The output shaft rotates oscillatingly about a longitudinal axis thereof. The cutting accessory includes a driving element adapted to the output shaft, two movable blades extending longitudinal and a guide portion adapted to the guide element. The cutting portions are both disposed of corresponding cutting teeth, the driving element drives the two movable blades to move in the opposite directions by the guide element. [0027] The advantage of the invention is: the cutting accessory is capable of detachably mounting on an oscillating power tool, the two movable blades move in the opposite direction driven by the driving element to realize cutting movements, the two movable blades are both capable of imposing cutting force on the cutting object for improving cutting efficiency. BRIEF DESCRIPTION OF THE DRAWINGS [0028] FIG. 1 is a solid view of an oscillating power tool mounted on a cutting accessory in a preferred embodiment. [0029] FIG. 2 is a solid view in another direction of the oscillating power tool shown in FIG. 1 . [0030] FIG. 3 is an illustration of part of structure of the oscillating power tool shown in FIG. 1 . [0031] FIG. 4 is a solid view of the cutting accessory shown in FIG. 1 (in face). [0032] FIG. 5 is a solid view of the cutting accessory shown in FIG. 1 (in back). [0033] FIG. 6 is a solid exploded view of the cutting accessory shown in FIG. 3 . [0034] FIG. 7 is a solid exploded view in another direction of the cutting accessory shown in FIG. 3 [0035] FIG. 8 is an illustration of structure of the cutting accessory shown FIG. 3 released the cover. [0036] FIG. 9 is a using status illustration of the cutting accessory shown in FIG. 4 , which the angle of the two moving knives is α 1 . [0037] FIG. 10 is a using status illustration of the cutting accessory shown in FIG. 4 , which the angle of the two moving knives is α 2 . [0038] FIG. 11 is a using status illustration of the cutting accessory shown in FIG. 4 , which the angle of the two moving knives is α 3 . [0039] FIG. 12 is a solid view of an oscillating power tool in a second embodiment. [0040] FIG. 13 is a solid exploded view of the oscillating power tool shown in FIG. 12 . [0041] FIG. 14 is a solid exploded view in another direction of the oscillating power tool shown in FIG. 12 . [0042] FIG. 15 is a using status illustration of the cutting accessory shown in FIG. 12 , which the driving element is in a horizontal position. [0043] FIG. 16 is a using status illustration of the cutting accessory shown in FIG. 12 , which the driving element rotate to an ultimate position in clockwise. [0044] FIG. 17 is a using status illustration of the cutting accessory shown in FIG. 12 , which the driving element rotate to an ultimate position in counterclockwise. DETAILED DESCRIPTION OF THE INVENTION [0045] The present invention is further described in detail with reference to the attached drawings and the specific embodiments. [0046] First, the first embodiment of the present invention is described in detail with references from FIG. 1 to FIG. 11 . [0047] See FIGS. 1 to 3 . The first embodiment of the present invention provides an oscillating power tool 100 , comprising an oscillation body 1 and a cutting accessory 2 installed on the body 1 . The body 1 drives the cutting accessory 2 to realize a shearing function similar to that of the scissors, capable of being used to shear articles such as thin iron sheets and blankets. [0048] In the full text of the description, the right side of the oscillating power tool 100 as shown in FIG. 1 is defined as “front”, and the left side “rear”. The body 1 comprises a housing 10 , a motor (not shown in the figure) and a transmission mechanism (not shown in the figure) that are received in the housing 10 , and an output shaft 11 driven by the transmission mechanism. Wherein, the housing 10 extending along the lengthwise direction comprises a head housing 12 located in the front portion of the body 1 and a flange plate 13 located in the rear portion of the head housing 10 . The motor is arranged in the flange plate 13 . The transmission mechanism is arranged in the head housing 12 . The motor shaft extends forward to be adapted to the transmission mechanism. The transmission mechanism converts the rotation motion output by the motor shaft into the reciprocating rotation motion of the output shaft 11 around its own X-axis. The cutting accessory 2 is arranged below the head housing 12 of the body 1 , approximately parallel to the flange plate 13 of the body 1 , and is axially connected to the output shaft 11 through a fastener 3 . [0049] The body 1 also comprises a cable 14 connected to the rear portion of the flange plate 13 and providing power for the motor, and a switch 15 controlling the power transmission. When the switch 15 is turned on, the motor drives the cutting accessory 2 to cut; when the switch 15 is turned off, the motor stops rotation, and then the cutting accessory 2 stops working. [0050] The head housing 12 is approximately “L” shaped, with one end connected to the flange plate 13 and the other end approximately shaped as an increasingly contracting circular truncated cone. The output shaft 11 is received in the head housing 12 , with one end adapted to said transmission mechanism and the other end extending outwards from the free end of the head housing 12 ; and the extension direction of the output shaft 11 approximately vertical to that of the flange plate 13 . The tail end of the output shaft 11 is provided with an orthohexagonal casing 111 . The middle portion of the casing 111 is provided with a thread hole 112 for receiving and fixing the fastener 3 . The free end of the output shaft 11 is also provided with a ring-shaped flange 113 around the casing 111 . The upper surface of the flange 113 is lower than that of the casing 111 so as to radially support the cutting tool 2 . [0051] See FIG. 4 and FIG. 5 . In this embodiment, the cutting accessory 2 and the body 1 are detachably and separately designed. The cutting accessory 2 , as an independent accessory, is installed on the body 1 through the fastener 3 . The cutting accessory 2 comprises a housing 27 , a driving element 22 received in the housing 27 , a first moving knife 23 and a second moving knife 24 partly extending out of the housing 27 . In this embodiment, the housing 27 comprises an upper cover 20 and a lower cover 21 adapted to the upper cover 20 . The driving element 22 , the first moving knife 23 and a second moving knife 24 are respectively received in the space formed by the upper cover 20 and the lower cover 21 . The first moving knife 23 and a second moving knife 24 are connected to the two ends of the driving elements 22 . The first moving knife 23 and a second moving knife 24 are crossly pivoted together and are arranged pivotally relative to the upper cover 20 . With the cutting accessory 2 installed on the body 1 , when the body 1 works, the motor drives the output shaft 11 to reciprocatingly rotate so as to drive the driving element 22 adapted to the output shaft 11 to reciprocatingly rotate, and then the driving element 22 drives the first moving knife 23 and the second moving knife 24 to relatively and reciprocatingly rotate so as to realize the cutting function. [0052] See FIG. 6 and FIG. 7 . The structure of the cutting accessory 2 will be described in detail. Wherein, the upper and lower covers 20 , 21 both are made from plastic materials through injection molding. The lower cover 21 is approximately square shaped, and the edges on four sides thereof are uniformly formed with three throughholes 211 ; while the upper cover 20 is formed with three thread holes 201 corresponding to said throughholes 211 . Three bolts 25 respectively penetrate through the three throughholes 211 of the lower cover 21 into the three thread holes 201 of the upper cover 20 so as to fix the lower cover 21 and the upper cover 20 together. [0053] The upper cover 20 is hollow, comprising an approximately square base 202 and a fixed portion 203 connected to the base 202 . The plane where the base 202 exists is vertical to the X-axis of the output shaft 11 , and the middle portion is provided with a round opening 204 . The shape of the fixing portion 203 is approximately similar to that of said head housing 12 and can just be in tight fit with the head housing 12 . The fixing portion 203 is formed by extending from one side of the base 202 to the output shaft 11 , comprising a hollow, cylindrical receiving portion 205 surrounding the opening 204 and a “U” shaped fixing section 206 formed by extending from one side of the receiving portion 205 to the flange plate 13 . In this way, the fixing portion 203 can be coated on the lower side of the head housing 12 . By the common action of the receiving portion 205 and the fixing section 206 , the cutting accessory 2 can be conveniently and quickly installed on the body 1 and is not easily moved while working. [0054] The upper cover 20 is also equipped with a metal reinforcement 26 . The reinforcement 26 is a narrow strip; one end thereof is provided with an annular sleeve 261 extending into the opening 204 of the upper cover 20 , while the other end is provided with a pivoting shaft 262 extending downwards along the lower cover 21 along the X-axis of the output shaft 11 , which means that the axis of the pivoting shaft 262 is parallel to the X-axis of the output shaft 11 . Wherein, the inner diameter of the sleeve 261 is equivalent to the outer diameter of the flange 113 on the output shaft 11 such that the flange 113 can be completely received in the sleeve 261 , which means that the two are in tight contact. To install the reinforcement 26 , the bottom of the upper cover 20 is provided with a first groove 207 adapted to the shape of the reinforcement 26 towards the lower cover 21 . The pivoting shaft 262 is shaped as a hollow cylinder. Said first moving knife 23 and said second moving knife 24 are crossly arranged on the pivoting shaft 262 and can pivot relative to each other around the pivoting shaft 262 . The reinforcement 26 also comprises a screw 263 received in the pivoting shaft 262 for axially fixing the first moving knife 23 and the second moving knife 24 . [0055] The lower cover 21 is installed on the base 202 of the upper cover 20 , so the driving element 22 , the first moving knife 23 and the second moving knife 24 are received in the space formed by the upper and lower covers 20 , 21 . Through installing the lower cover 21 , on one hand, the structure of the whole cutting accessory 2 is more stable and compact, and on the other hand, it performs dust prevention to guard the driving element 22 and the two moving knives 23 , 24 in the space against dust. The lower cover 21 is similar to the shape of the base 202 of the upper cover 20 , and the middle portion thereof is provided with a hole 212 corresponding to the opening 204 of the upper cover 20 . The inner diameter of the hole 212 is bigger than the maximum outer diameter of the fastener 3 such that the fastener 3 can pass through the hole 212 of the lower cover 21 to be adapted to the driving element 22 . [0056] The two moving knives 23 , 24 are approximately “L” shaped, crossly pivoted on the pivoting shaft 262 of the reinforcement 26 , and both are made of metal. The first moving knife 23 has a first head portion 231 , a first cutting portion 232 arranged opposite to the first head portion 231 , and a first connecting portion 233 located between the first head portion 231 and the first cutting portion 232 , and the first connecting portion 233 is provided with a first bore 234 ; correspondingly, the second moving knife 24 has a second head portion 241 , a second cutting portion 242 arranged opposite to the second head portion 241 , and a second connecting portion 243 located between the second head portion 241 and the second cutting portion 242 , and the second connecting portion 243 is provided with a second bore 244 . The first moving knife 23 and the second moving knife 24 respectively pass through the first bore 234 and the second bore 244 and then are sleeved on the pivoting shaft 262 of the reinforcement 26 in turn and cascaded together; moreover, the first cutting portion 232 and the second cutting portion 242 extend out of the housing 27 for convenient cutting. In addition, to be adapted to the driving element 22 , the first moving knife 23 is provided with a first roller 235 installed on the free end of the first head portion 231 , and the second moving knife 23 is provided with a second roller 245 installed on the free end of the second head portion 241 . To facilitate cutting, the included angles formed between the head portions of the two moving knives and the cutting portion are different. In this embodiment, the included angle between the first head portion 231 of the first moving knife 23 and the first cutting portion 232 is an approximately right angle, while the included angle between the second head portion 241 of the second moving knife 24 and the second cutting portion 242 is an approximately obtuse angle. The first cutting portion 232 and the second cutting portion 242 form an opening at a certain angle. During cutting, an object can first enter the opening between the first cutting portion 232 and the second cutting portion 242 , thus the object can be cut conveniently. [0057] The driving element 22 is adapted to the output shaft 11 and driven by the output shaft 11 to actuate the two cutting knives 23 , 24 to reciprocatingly rotate so as to realize cutting operation. The side, facing the lower cover 21 , of the upper cover 20 is provided with a second groove 208 for receiving the driving element 22 . The second groove 208 is vertically crossed with the first groove 207 . The shape of the second groove 208 is similar to the driving element 22 , but bigger than the driving element 22 , so the driving element 22 can reciprocatingly rotate around the X-axis of the output shaft 11 by a certain angle in the second groove 208 and avoid mutual interference. The driving element 22 is made of metal, approximately oval; the middle portion is provided with a throughhole 221 through which the fastener 3 passes; and the two ends are symmetrically provided with a first driving portion 222 and a second driving portion 223 . The driving element 22 has a first side face 224 facing the upper cover 20 and a second side face 225 facing the lower cover 21 , wherein, the first side face 224 is provided with a mounting portion 226 adapted to the casing 111 of the output shaft 11 ; the mounting portion 226 is a dodecagonal recess; the second side face 225 is provided with a first groove 227 and a second groove 228 which are respectively located on the first driving portion 222 and the second driving portion 223 . The mounting portion 226 is located in the centre of the driving element 22 , and the throughhole 221 passes through the mounting portion 226 from the right centre. The first groove 227 is used for receiving the first roller 235 of the first moving knife 23 , and the second groove 228 is used for receiving the second roller 245 of the second moving knife 24 . The first groove 227 and the second groove 228 both are long-waist shaped and identical in size. The first roller 235 and the second roller 245 can respectively slide in the first groove 227 and the second groove 228 . [0058] As shown in FIG. 8 , the centre of the driving element 2 is A; moreover, in the state as shown in this figure, the centers of the first groove 227 and the first roller 235 are superimposed at B; the centers of the second groove 228 and the second roller 245 are superimposed at C; and the centre of the pivoting shaft 262 is D. The first groove 227 comprises two first straight sections 2271 located in the middle portion in parallel and the first arc sections 2272 symmetrically located at the two ends. Correspondingly, the second groove 228 comprises two second straight sections 2281 located in the middle portion in parallel and second arc section 2282 symmetrically located at two ends. The included angle between the first straight section 2271 and the central line BC of the first groove 227 and the second groove 228 is γ 1 , and the included angle between the second straight section 2281 and the central line BC of the first groove 227 and the second groove 228 is γ 2 . In addition, the distances from the centers of the first roller 235 and the second roller 245 to the centre of the pivoting shaft 262 are equal, namely BD=CD, so the two moving knives 23 , 24 can synchronously rotate while working, thereby improving the cutting efficiency. [0059] In this embodiment, the assembly process of the cutting accessory 2 is as follows: first, install the reinforcement 26 in the first slot 207 of the upper cover 20 , in which the pivoting shaft 262 faces the lower cover 21 ; next, press the driving element 22 on the reinforcement 26 and place in the second slot 208 of the upper cover 20 ; then, cascade and sleeve the first moving knife 23 and the second moving knife 24 on the pivoting shaft 26 of the reinforcement 26 in turn, receive and fix the screw 263 in the pivoting shaft 262 ; next, receive the first roller 235 of the first moving knife 23 in the first groove 227 of the driving element 22 , receive the second roller 245 of the second moving knife 24 in the second groove 228 of the driving element; at last, fasten the lower cover 21 on the upper cover 20 , and fix the upper and lower covers 20 and 21 together through three bolts 25 . Through the above steps, the assembly of the cutting accessory 2 is completed. During use, the cutting accessory 2 is adapted to and fixed on the head housing 12 of the body 1 ; the fastener 3 passes through the hole 212 of the lower cover 21 and the throughole 221 of the driving element 22 and is connected into the thread hole 112 of the output shaft 2 so as to axially fix the driving element 22 relative to output shaft 11 , so the cutting accessory 2 is fixed with the body 1 and driven by the body 1 to realize the cutting function. [0060] The following is a detailed description of the cutting principle of the cutting accessory 2 with reference to the FIGS. 2 , 5 , 9 to 11 . The mounting portion 226 of the driving element 22 is adapted to the casing 111 of the output shaft 11 . The first roller 235 on the first head portion 231 of the first moving knife 23 is received in the first groove 227 of the driving element 22 . The second roller 245 on the second head portion 241 of the second moving knife 24 is received in the second groove 228 of the driving element 22 . The first moving knife 23 and the second moving knife 24 are pivotally, crossly sleeved on the pivoting shaft 262 of the reinforcement 26 , and axially limited through the screw 263 . [0061] When the oscillating power tool 100 works, the motor shaft of the body 1 drivers the output shaft 11 through the transmission mechanism to reciprocatingly rotate, and then the output shaft 11 drives the driving element 22 to reciprocatingly rotate through the fit between the casing 111 and the mounting portion 226 of the driving element 22 . The sizes of the first groove 227 and the second groove 228 of the driving element 22 are respectively approximately equivalent to those of the first roller 235 corresponding to the first moving knife 23 and the second roller 245 corresponding to the second moving knife 24 . The first roller 235 and the second roller 245 can rotate in the corresponding first slot 227 and second slot 228 and meanwhile can slide relative to the inside walls of the first slot 227 and the second slot 228 . [0062] In this embodiment, the oscillating angle of the output shaft 11 of the oscillating power tool 100 is 2β, namely the value of the angle between the clockwise oscillating limit position and the anticlockwise oscillating limit position of the output shaft 11 , wherein 2β=0.5°-10°, which means that the oscillating frequency of the output shaft 11 is 500-250,000 times/min Obviously, the oscillating angle and oscillating frequency of the oscillating power tool 100 in the present invention are not limited in the above scope, and may be other numerical values. [0063] As shown in FIG. 9 , the output shaft 11 drives the driving element 22 to anticlockwise oscillate to the limit position. At this moment, the included angle between the first cutting portion 232 of the first moving knife 23 and the second cutting portion 242 of the second moving knife 24 is α 1 . [0064] As shown in FIG. 10 , the output shaft 11 drives the driving element 22 to rotate β clockwise, oscillating to the initial position of the driving element 22 . In this process, the driving element 22 drives the first moving knife 23 to rotate clockwise around the pivoting shaft 262 through the fit between the first slot 227 and the first roller 235 , and meanwhile drives the second moving knife 24 anticlockwise around the pivoting shaft 262 through the fit between the second slot 228 and the second roller 245 , thus reducing the distance between the first head portion 231 and the second head portion 241 and finally increasing the included angle between the first cutting portion 232 and the second cutting portion 242 from α 1 to α 2 . [0065] As shown in FIG. 11 , the output shaft 11 drives the driving element 22 to rotate β clockwise, oscillating to the clockwise limit position. In this process, the driving element 22 drives the first moving knife 23 to continuously rotate clockwise around the pivoting shaft 262 through the fit between the first slot 227 and the first roller 235 , and meanwhile drives the second moving knife 24 continuously anticlockwise around the pivoting shaft 262 through the fit between the second slot 228 and the second roller 245 , thus reducing the distance between the first head portion 231 and the second head portion 241 and finally increasing the included angle between the first cutting portion 232 and the second cutting portion 242 from α 2 to α 3 . [0066] Therefore, the included cutting angle between the first cutting knife 23 and the second cutting knife 24 increases from α 1 to α 3 , thus completing the opening operation of the scissors accessory; on the contrary, when the driving element 22 rotates β anticlockwise, the included cutting angle between the first cutting knife 23 and the second cutting knife 2 decreases from α 3 to α 1 , thus completing the closing operation of the scissors accessory. Repeatedly, the first cutting portion 232 of the first moving knife 23 reciprocatingly rotates relative to the second cutting portion 242 of the second moving knife 24 , thereby realizing the object cutting function. [0067] It should be pointed out that the present invention is not limited to the separated design of the cutting accessory and body disclosed in the above embodiment, in which the cutting accessory is installed on the body. Those skilled in this field can easily think that the cutting accessory of the present invention can also be integrated with the body through processing. [0068] In the above embodiment, the casing of the output shaft is orthohexagonal, while the mounting portion of the driving element is dodecagonal, so the casing can be adapted to the mounting portion to realize that the output shaft can drive the driving element instead of generating relative sliding when reciprocatingly rotating, and meanwhile limit the driving element at many different angular positions according to demands. Those skilled in this field can think that the casing of the output shaft and the mounting portion of the driving element can also be combined in other way, for example, the mounting portion of the driving element is also processed to be orthohexagonal; the plural column-shaped projections on the output shaft are inserted into the corresponding holes on the driving element, or projections in other shapes (such as the star shape) on the output shaft are inserted into the holes in corresponding shapes on the driving element. [0069] Compared with the prior art, the first embodiment of the present invention provides an oscillating power tool with a cutting accessory, wherein the output shaft drives the driving element to reciprocatingly rotate, and then the driving element drives the two moving knives to relatively reciprocatingly rotate so as to realize the cutting function. In the related art, the cutting accessory applied to the oscillating power tool realizes cutting through a movable blade and a fixed blade. Therefore, compared with the cutting accessory disclosed in the related art, the cutting accessory of the present invention can provide bigger cutting force and therefore greatly improves the cutting efficiency. [0070] The following are detailed descriptions of the second embodiment of the present invention with reference to the FIGS. 12 to 17 . [0071] As shown in FIG. 12 , the oscillating power tool 200 in this embodiment is identical with that in the first embodiment in the body 1 , but different in the cutting accessory 4 . The cutting accessory 4 is also detachably and separately designed. The cutting accessory 4 as an independent accessory is installed on the body 1 through the fastener 5 . The cutting accessory 4 comprises an upper cover 40 , a lower cover 41 adapted to the upper cover, a driving element 44 received between the upper and lower covers 40 , 41 , and a first moving knife 43 and a second moving knife 44 respectively connected to the driving element 42 . The first and second moving knives 43 , 44 are cascaded together and can reciprocatingly translate relative to the upper cover 40 . With the cutting accessory 4 installed on the body 1 , when the body 1 works, the motor drives the output shaft 11 to reciprocatingly rotate so as to drive the driving element 42 adapted to the output shaft 11 to reciprocatingly rotate, and then the driving element 42 drives the first moving knife 43 and the second moving knife 44 to relatively and reciprocatingly translate so as to realize the cutting function. [0072] See FIG. 13 and FIG. 14 . The structure of the cutting accessory 4 will be described in detail. The lower cover 41 is an approximately rectangular flat plate, provided with four througholes 411 in a scattered way. The upper cover 40 is also provided with four througholes 401 corresponding to the throughholes 411 . Between the upper cover 40 and the lower cover 41 are four hollow supporting posts 45 located between the througholes 401 and the througholes 411 . Four bolts 46 respectively pass through the throughholes 411 of the lower cover 41 , the supporting posts 45 and the througholes 401 of the upper cover 40 and finally are fixed through four nuts, so the lower cover 41 and the upper cover 40 are fixed together. Through installing the supporting posts 45 , a large enough space is formed between the upper and lower covers 40 , 41 to receive the driving element 40 and the upper and lower moving knives 43 , 44 and enable the upper and lower moving knives 43 to freely and reciprocatingly translate. [0073] Wherein, the upper cover 40 comprises an approximately flat plate-shaped supporting element 402 and a fixing portion 403 on the supporting element 402 . The plane where the supporting element 402 exists is vertical to the X-axis of the output shaft 11 and is approximately parallel to the lower cover 41 . The fixing portion 403 is formed by extending from one side of the supporting element 402 , approximately similar to the shape of the head housing 12 , and just can be tightly sleeved on the head housing 12 . One side, away from the head housing 12 , of the supporting element 402 projects and extends to form a guide element 404 along the direction parallel to the X-axis of the output shaft 11 . The guide element 404 is step-like, comprising a bigger first lug 405 and a smaller second lug 406 . The two lugs both are cuboid shaped, wherein the second lug 406 extends from the middle portion of the first lug 405 and away from the output shaft 11 . [0074] The lower cover 41 is installed on the supporting element 402 of the upper cover 40 , so the driving element 42 , the first moving knife 43 and the second moving knife 44 are received in the space formed by the upper and lower covers 40 , 41 . One side of the lower cover 41 is provided with an opening 412 corresponding to the fixed portion 403 of the upper cover 40 . The size of the opening 412 is bigger than the maximum outer diameter of the fastener 5 , so the fastener 5 can penetrate through the opening 412 of the lower cover 41 to be adapted to the driving element 42 . The other side of the lower cover 41 , corresponding to the guide element 404 of the upper cover 40 , is provided with a stop hole 413 capable of being sleeved on the second lug 406 of the guide element 404 , so the first moving knife 43 and the second moving knife 44 are axially limited on the guide element 404 of the upper cover 40 . [0075] The two moving knives 43 , 44 both are approximately flat plate shaped, and the plane where the two exist is vertical to the X-axis of the output shaft 11 . The two moving knives 43 and 44 are symmetrically shaped, and extend lengthwise along the direction approximately vertical to the driving element 42 . The first moving knife 43 has an approximately “L”-shaped first head portion 431 and a linear first cutting portion 432 vertically extending from the first head portion and away from one end of the driving element 42 . The second moving knife 44 has a second head portion 441 shaped symmetric to the first head portion 431 of the first moving knife 43 and a second cutting portion 442 vertically extending from the second head portion 441 and away from one end of the driving element 42 . One end, away from the first cutting portion 432 , of the first head portion 431 of the first moving knife 43 is provided with a first roller 433 projecting towards the driving element 42 ; correspondingly, the second head portion 441 of the second moving knife 44 is provided with a second roller 443 . The two moving knives 43 , 44 are respectively connected to the driving element 42 through the first roller 433 and the second roller 443 so as to be driven by the driving element 42 . The first cutting portion 432 of the first moving knife 43 and the second cutting portion 442 of the second moving knife 44 are superimposed together. The first cutting portion 432 and the second cutting portion 442 respectively extend towards two sides to form plural first cutting teeth 434 and second cutting teeth 444 . The first cutting portion 432 and the second cutting portion 442 relatively and reciprocatingly translate, and then the opposite cutting teeth 434 and 444 perform cutting. The first cutting portion 432 of the first moving knife 43 is also provided with a first track 435 matched with the guide element 404 of the upper cover 40 , and the second cutting portion 442 of the second moving knife 44 is correspondingly provided with a second track 445 . The first track 435 and the second track 445 both are long strip-shaped openings, mutually run through and just have enough size to receive the second lug 406 of the guide element 404 , so the second lug 406 can slide in the first track 435 and the second track 445 . [0076] It should be pointed out that, those skilled in this field can easily think that the first track and the second track in this embodiment can also be provided with projections, and correspondingly the guide element of the upper cover is formed with long strip-shaped openings by processing. [0077] The driving element 42 is adapted to the output shaft 11 and driven by the output shaft 11 to actuate the two cutting knives 43 , 44 to reciprocatingly translate so as to realize cutting operation. The driving element 42 is made of metal, approximately rectangular; the middle portion thereof is provided with a mounting portion 421 adapted to the casing 111 of the output shaft 11 ; and the two ends are symmetrically provided with a first driving portion 422 and a second driving portion 423 . Wherein, the mounting portion 421 is an orthohexagonal opening, equivalent to the casing 111 of the output shaft 11 in size, and can just receive the casing 111 . The first driving portion 422 is provided with a first groove 424 , and the second driving portion 423 is correspondingly provided with a second groove 425 . The central line of the two grooves passes through the centre of the mounting portion 421 . The middle portion of the first groove 424 is provided with two parallel and opposite first straight sections 4241 , while middle portion of the second groove 425 is also provided with two parallel and opposite second straight sections 4251 . The first groove 424 is used for receiving the first roller 433 of the first moving knife 43 , and the second groove 425 is used for receiving the second roller 443 of the second moving knife 44 . The first groove 424 and the second groove 425 both are long waist-shaped, identical in size, and a little bigger than the first roller 433 and the second roller 443 . The first roller 433 and the second roller 443 can respectively slide on the first groove 424 and the second groove 425 . [0078] In this embodiment, the assembly process of the cutting accessory 4 is as follows: first, place on the driving element 42 on the supporting element 402 of the upper cover 40 ; then, superpose and install the first moving knife 43 and the second moving knife 44 on the supporting element 402 of the upper cover 40 such that the first track 435 of the first moving knife 43 and the second track 445 of the second moving knife 44 are respectively sleeved on the second lug 406 of the guide element 404 of the upper cover 40 ; meanwhile, receive the first roller 433 of the first moving knife 43 in the first groove 424 of the driving element 42 , receive the second roller 443 of the second moving knife 44 in the second groove 425 of the driving element 42 ; next, respectively place the four supporting posts 45 corresponding to the four througholes 401 on the supporting element 402 of the upper cover 40 , fasten the lower cover 41 on the upper cover 40 such that the stop hole 413 of the lower cover 41 is sleeved on the guide element 404 of the upper cover 40 ; at last, respectively penetrate through four bolts 46 through the througholes 411 of the lower cover 41 , the supporting posts 45 and the througholes 401 of the upper cover 40 , and fix with nuts 47 . [0079] Through the above steps, the assembly of the cutting accessory 4 is completed. During use, the cutting accessory 4 is adapted to and fixed on the head housing 12 of the body 1 , so the mounting portion 421 of the driving element 42 is adapted to the casing 111 of the output shaft 11 , and the fastener 3 is connected to the thread hole 112 of the output shaft 11 to axially fix the driving element 42 relative to the output shaft 1 . Therefore, the cutting accessory 4 is fixed with the body 1 and driven by the body 1 to realize the cutting function. [0080] The following is the detailed description of the cutting principle of the cutting accessory 4 with reference to the FIGS. 12 , 13 , 15 to 17 . The mounting portion 421 of the driving element 42 is adapted to the casing 111 of the output shaft 11 . The first roller 433 on the first head portion 431 of the first moving knife 43 is received in the first groove 424 of the driving element 42 . The second roller 443 on the second head portion 441 of the second moving knife 44 is received in the second groove 425 of the driving element 42 . The first moving knife 43 and the second moving knife 44 can relatively and reciprocatingly translate and are crossly sleeved on the guide element 404 of the upper cover 40 . When the oscillating power tool 200 works, the motor shaft of the body 1 drivers the output shaft 11 through the transmission mechanism to reciprocatingly rotate, and then the output shaft 11 drives the driving element 42 to reciprocatingly rotate through the fit between the casing 111 and the mounting portion 421 of the driving element 42 . By the action of the guide element 404 of the upper cover 40 , the driving element 42 drives the first moving knife 43 and the second moving knife 44 to relatively and reciprocatingly translate, so the cutting teeth 434 , 444 of the first cutting portion 432 and the second cutting portion 442 perform cutting. [0081] In this embodiment, the oscillating angle of the output shaft 11 of the oscillating power tool 200 is 2β, namely the value of the angle between the clockwise oscillating limit position and the anticlockwise oscillating limit position of the output shaft 11 , wherein 2β=0.5°-10°, which means that the oscillating frequency of the output shaft 11 is 500-250,000 times/min Obviously, the oscillating angle and oscillating frequency of the oscillating power tool 200 in this embodiment are not limited in the above scope, and may be other numerical values. [0082] As shown in FIG. 15 , the driving element 42 is located at an approximately level position; the first cutting portion 432 of the first moving knife 43 and the second cutting portion 442 of the second moving knife 44 are approximately superimposed; the distance between the adjacent cutting teeth 43 , 44 in the vertical direction is D 1 . [0083] As shown in FIG. 16 , the output shaft 11 drives the driving element 42 to rotate β clockwise. In this process, through the fit between the first roller 433 and the first groove 424 and the guiding of the guide element 404 of the upper cover 40 and the first track 435 , the driving element 42 drives the first moving knife 43 to vertically downward translate at a certain distance; meanwhile, through the fit between the second groove 425 and the second roller 443 and the guiding of the guide element 404 of the upper cover 40 and the second track 445 , the driving element 42 drives the second moving knife 44 to vertically upward translate at a certain distance. This results in that the first cutting portion 432 and the second cutting portion 442 are staggered at a certain distance after reciprocating translation, and the distance between the cutting teeth 43 , 44 in the vertical direction is decreased from D 1 to D 2 , and thus, cutting of the object placed between the cutting teeth 43 , 44 , such as twigs, can be realized. [0084] As shown in FIG. 17 , contrary to that as shown in FIG. 16 , the output shaft 11 drives the driving element 42 to rotate β anticlockwise, oscillating to the anticlockwise limit position. In this process, the driving element 42 drives the first moving knife 43 to vertically upward translate at a certain distance and meanwhile drives the second moving knife 44 to vertically downward translate at a certain distance, which results in that the first cutting portion 432 and the second cutting portion 442 are staggered at a certain distance after reciprocating translation, and that the distance between the cutting teeth 43 , 44 in the vertical direction is decreased from D 1 to D 2 , and thus, cutting of the object placed between the cutting teeth 43 , 44 , such as twigs, can be realized. [0085] Compared with the prior art, this embodiment provides an oscillating power tool with a cutting accessory; the output shaft drives the driving element to reciprocatingly rotate; then the driving element drives the two moving knives to relatively and reciprocatingly translate so as to realize the cutting function. It can be used to prune plants in the garden, has high cutting efficiency than the common electric pruning shears, and therefore widens the application scope of the oscillation tool.
A cutting accessory detachably mounted on an oscillating power tool is disclosed. The oscillating power tool includes a head housing and an output shaft extending from the head housing. The output shaft rotates oscillatingly about a longitudinal axis thereof. The cutting accessory includes a housing adapted to the head housing, two movable blades partly received in the housing, and a driving element adapted to the output shaft. The driving element is configured to oscillate by the actuation of the output shaft and simultaneously drives the two movable blades to move in the opposite directions to cut a workpiece.
1
BACKGROUND OF THE INVENTION [0001] The present invention relates generally to elevator systems and, in particular, to equipment for ascertaining the absolute position of a rail-guided elevator car in an elevator shaft. [0002] Such position transmitting equipment is known. In elevator installations, these are used for the purpose of determining the absolute position of an elevator car and deriving therefrom data signals for control of the elevator installation. The position information is applied in a coded form in fixed location along the entire travel path of the elevator car and is read off in the coded form by means of a code reading device and processed in evaluating equipment to be comprehensible to the control. [0003] For example, equipment is known from German Utility Model G 92 10 996.9 in which a magnetic strip functioning as a code carrier is laterally fastened to a car guide rail. The magnetic strip contains, in the displacement direction of the elevator car, a length coding and coded data about stopping points or the like. A magnet head fastened to the elevator car and movable in common therewith relative to the magnetic strip in the reading direction of the coding reads off the coded data and passes on the data for evaluation. [0004] Disadvantages of the known equipment consist in the previously usual application of the magnetic strip at or on the car guide rail and also in the construction of the magnetic strip itself. The magnetic strip has to be mounted at the guide rail in positionally exact manner and without overstretching in order to avoid misalignment of the coding with the corresponding position and inaccuracies, which result therefrom, for the positioning of the elevator car. Moreover, unequal thermal expansions of the magnetic strip relative to the car guide rail occur, which has the consequence of a displacement of the coding relative to the guide rail. In addition, the exposed position of the magnetic strip laterally at the guide rail involves the risk of mechanical damage to the magnetic strip by parts moved in the shaft, such as, for example, the magnet head in the case of horizontal movements of the elevator car. The known magnetic strip clogs with lubricating oil and dust particles swirled up in the shaft, which impairs reading of the coding. SUMMARY OF THE INVENTION [0005] The present invention concerns equipment for ascertaining the absolute position of a elevator car movable along guide rails over a travel path in an elevator installation comprising: a code carrier adapted to extend along the travel path of the elevator car and having code marks of different permeability alternately in succession extending in the direction of travel of the elevator car; and a non-magnetic cover attached to the code carrier and externally covering the code marks. The non-magnetic cover is formed of a metallic material and the code carrier is adapted to be retained in location on at least one of the guide rails along which the elevator car moves. A receiving groove is formed in the at least one guide rail, the code carrier being inserted into the receiving groove and being externally covered by the non-magnetic cover. [0006] It is the object of the present invention to provide position transmitting equipment for elevators, which is favorable with respect to maintenance and which ensures a permanently precise reading of the absolute coding. [0007] According to the present invention the attainment of this object is by equipment for ascertaining the position of the elevator car, which is distinguished particularly by the fact that the code carrier is fixedly connected with a non-magnetic cover, wherein the code marks are externally covered by means of the non-magnetic cover. [0008] The advantages achieved by the present invention are that the code carrier and thus the coding is protected against mechanical damage by parts moved in the shaft. The non-magnetic cover moreover acts as a mechanical reinforcement for the code carrier and thereby prevents, during mounting, misalignment of the coding by non-uniform stretching of the code carrier in the direction of reading. [0009] A further increase in the reliability and accuracy of the positional determination is to be achieved with a code carrier which is constructed as a magnetic strip carrying the code and a non-magnetizable cover, in the form of a metallic cover strip, fixedly connected therewith. Apart from high mechanical strength, a more favorable thermal balance between the code carrier and the guide rail is achieved with such a code carrier. This counteracts temperature-induced unequal thermal expansions, which occur over the length of the code carrier, relative to the guide rail or evens out the occurring difference in expansion. [0010] In a further development of the present invention it is provided that the code carrier together with the outwardly facing cover is inserted into a receiving groove of the guide rail. The receiving groove enables a simple and precise mounting of the code carrier, because this merely has to be inserted without additional aids into the constructionally provided receiving groove. The magnetic strip carrying the coding is protectively covered towards all sides. The code carrier inserted into the receiving groove is embedded in the guide rail and covered towards the outside by the cover and accordingly substantially adopts the temperature thereof. Temperature-induced differences in expansion between the code carrier and the guide rail accordingly do not occur. [0011] Particularly in the case of a receiving groove, which is shaped to be complementary to the code carrier and in which the code carrier is inserted to be flush relative to the surface of the guide rail, the code carrier is prevented from being erroneously displaced or bent—whereby the coding would be misaligned or unreadable—by parts moved in the shaft or by, for example, an engineer during maintenance operations. [0012] In an advantageous manner the receiving groove is formed at the end face at a guide flange of the car guide rail. The production of the receiving groove is simple and the code carrier is readily accessible to the code reading device for reading the code. [0013] A contact and space-saving mode of construction of the elevator is possible in the case of an embodiment in which the receiving groove is formed laterally at a guide flange of the car guide rail. This arrangement in addition favors accurate reading of the code with the assistance of the code reading device. [0014] Advantages with respect to a quick and accurate mounting of the code carrier and the production of the equipment according to the present invention are offered by an embodiment in which the cover is formed as a strip with substantially two mutually parallel surfaces and lateral boundaries, wherein at least the lateral boundaries laterally project beyond the code carrier and the groove flanks of the receiving groove are formed to be complementary to the lateral boundaries of the cover strip. [0015] The code carrier is preferably fastened to the guide rail in magnetic self-adhering manner. This enables a simple and timesaving mounting. At the same time, the code carrier bears directly against the guide rail and favors thermal transmission between the two. The code carrier follows every movement of the guide rail without the bond loosening or the code carrier experiencing local buckling. [0016] In forms of embodiment with the code carrier arranged laterally at the guide flange of the car guide rail, the receiving groove lies in a region of the guide flange which is dynamically highly loaded when the elevator car is travelling. In order to avoid stress concentrations stemming from the receiving groove in this region it is advantageous to treat the foot region of the guide flange by hot-rolling. DESCRIPTION OF THE DRAWINGS [0017] The above, as well as other advantages of the present invention, will become readily apparent to those skilled in the art from the following detailed description of a preferred embodiment when considered in the light of the accompanying drawings in which: [0018] [0018]FIG. 1 schematically shows an elevator with a first embodiment of the position transmitting equipment according to the present invention; [0019] [0019]FIG. 2 a shows a first embodiment of the magnetic strip according to the present invention and its application to the guide rail in an enlarged section taken along the section line II-II in FIG. 1; [0020] [0020]FIG. 2 b shows a second embodiment of the magnetic strip according to the present invention and its application laterally to the guide rail in an enlarged section as if taken along the section line II-II in FIG. 1; [0021] [0021]FIG. 3 a shows a detail view of the end face of the guide flange in a circle IIIa shown in FIG. 2 a; [0022] [0022]FIG. 3 b shows a detail view of the embodiment of FIG. 2 b in a circle IIIb; [0023] [0023]FIG. 3 c shows a third embodiment of the magnetic strip according to the present invention and its application to the guide rail; [0024] [0024]FIG. 4 a shows a fourth embodiment of a receiving groove laterally at the guide rail according to the present invention; [0025] [0025]FIG. 4 b shows a fifth embodiment of the receiving groove laterally at the guide rail according to the present invention; and [0026] [0026]FIG. 5 shows a detail view V of the receiving groove from FIG. 4 b in a circle V. DESCRIPTION OF THE PREFERRED EMBODIMENT [0027] [0027]FIG. 1 shows an elevator installation with a shaft 1 in which an elevator car 2 and a counterweight 3 are suspended on a common support cable 4 . The support cable 4 is guided over a non-driven deflecting roller 5 and a driven drive pulley 6 and is driven by the latter. The drive pulley 6 transmits the drive forces of a drive motor, which is not illustrated here, for raising and lowering the elevator car 2 and the counterweight 3 on the support cable 4 driven by it. The elevator car 2 is vertically displaceable along a guide rail 7 . A code strip 9 is mounted along the guide rail 7 parallel to a direction 8 of movement of the elevator car 2 . The code strip 9 contains, in the direction 8 of movement of the elevator car 2 , coded length or position details and coded data about stopping points or the like. The coded data are read off by a sensor head 10 and passed on to the evaluating unit 11 . [0028] The sensor head 10 is arranged at the elevator car 2 and moved together therewith along the code strip 9 . For reading off the coding of the magnetic strip the sensor head 10 is equipped with correspondingly suitable sensors. Suitable for this purpose are, for example, Hall sensors, induction transmitters or—as in the illustrated embodiment—magnetoresistive sensors, so-called MR sensors, detecting the magnetic field direction. Of each of these types of sensors, there can be provided several individual sensors and/or one group of different sensors. [0029] The coded information read off by the sensor head 10 is passed on to an evaluating unit 11 . The evaluating unit 11 translates the coded information into a form comprehensible for an elevator control 12 before it is passed on, for example by way of a hanging cable 13 as shown, to the elevator control 12 for positioning the elevator car 2 . [0030] In a horizontal section, which is illustrated in FIG. 2 a , of the guide rail 7 the code strip 9 consists of a magnetic strip 14 and a metallic cover strip 15 . Suitable for this purpose is basically any material which offers mechanical protection for the magnetic strip 14 or the code marks. The magnetic strip 14 is centrally glued onto the metallic cover strip 15 , wherein the cover strip 15 projects at both sides beyond the magnetic strip 14 . The magnetic strip 14 is inserted into a receiving groove 16 at an end face 17 of a guide flange 18 of the guide rail 7 and is covered relative to the shaft 1 by the metallic cover strip 15 . [0031] The magnetic strip 14 consists of vulcanized nitrile rubber as binder, in which aligned barium ferrite is embedded. In general, the magnetic strip can be formed from a synthetic material or rubber material in which any magnetizable material can be embedded. The magnetizable material is magnetized either as a magnetic north pole or as a magnetic south pole in alternating sequence in the form of sections extending transversely to the length direction of the magnetic strip. The magnetized sections form magnetic fields appropriately oriented outwards and represent the code marks of the magnetic strip 14 . According to the respective polarity of the code marks, thus two different values “0” and “1” can be represented as basic components of the coding. [0032] The non-magnetized metallic cover strip 15 serves for protection of the magnetic strip 14 against mechanical damage by parts moved in the shaft 1 , for example the sensor head 10 , and for compensation for unequal thermal expansions, which occur over the strip length, of the magnetic strip 14 relative to the guide rail 7 . As mechanical reinforcement of the magnetic strip 14 it prevents a non-uniform expansion of the magnetic strip 14 and thus misalignment of the coding during mounting. Due to its non-magnetic property the magnetic code marks of the magnetic strip 14 also remain readable through the cover strip 15 by the sensor head 10 . [0033] The receiving groove 16 is machined over the entire length of the end surface 17 of the guide flange 18 and has a cross-section—here rectangular—complementary to the shape of the magnetic strip 14 . The code strip 9 is retained in fixed location in the receiving groove 16 in magnetic self-adhering manner with the aid of the magnetic coding of the magnetic strip 14 . A fixed bonding, for example by means of a screw connection at the upper end of the guide path, serves as a positional security for the magnetic strip 14 . In addition, glue points at uniform spacings over the length of the receiving groove 16 serve for fixing the magnetic strip (not illustrated). However, in the case of a sufficient magnetic self-adhesion of the magnetic strip, gluing is not absolutely necessary. [0034] [0034]FIG. 2 b shows an alternate embodiment of the equipment according to the present invention in which a code strip 19 is inserted, so as to be flush, in a receiving groove 23 formed laterally at a foot 20 of a guide flange 21 of a guide rail 22 . A sensor head 24 is moved together with the elevator car 2 in the vertical direction 8 . There is again arranged at a carrier 26 of the sensor head 24 a sensor 27 which reads off the coded information of the code strip 19 , which is then passed on to an evaluating unit 28 . [0035] [0035]FIG. 3 b illustrates a detail view IIb of the embodiment of FIG. 2 b . The code strip 19 with substantially rectangular cross-section is inserted, together with a metallic non-magnetic cover strip 29 , to face outwardly and be flush in the complementary receiving groove 23 of the guide flange. A magnetic strip 30 is fixedly attached or adhered to the code strip 19 by the metallic non-magnetic cover strip 29 . [0036] In FIG. 3 c there is illustrated a third embodiment of the code carrier as a code strip 31 and its application to a guide rail 32 . The code strip 31 consists, as in the previously described embodiment, again of a magnetic strip 33 and a cover strip 34 fixedly attached or glued thereto. The magnetic strip 33 corresponds in construction and function to the magnetic strip 14 of the embodiment illustrated in FIG. 3 a . The cover strip 34 has a trapezium-shaped cross-section and projects symmetrically at both sides beyond the magnetic strip 33 . Lateral boundaries 35 , 36 of the cover strip 34 are beveled towards the magnetic strip 33 . [0037] A groove depth 37 of a receiving groove 38 is greater than a thickness 39 of the code strip 34 . A width 40 of the receiving groove 38 is selected to be greater than a width 41 of the magnetic strip 33 , whilst a width 42 of the cover strip 34 is basically the clear width 40 of the receiving groove 38 . Side surfaces 43 , 44 of the receiving groove 38 and the lateral boundaries 35 , 36 of the cover strip 34 are formed to be complementary to one another. In the mounted state, the cover strip 34 is flush with the surface of the guide rail 32 . The position of the magnetic strip 33 is specifically predetermined by the fixedly connected cover strip 34 . The receiving groove 38 can be economically produced with large production tolerances, because merely the side surfaces 43 , 44 at the readily accessible upper edge of the receiving groove 38 have to be formed to be complementary with the lateral boundaries 35 , 36 of the cover strip 34 . [0038] In the case of embodiments with code carriers arranged laterally at the guide flange of the car guide rail, the receiving groove lies in a region of the guide flange which is dynamically highly loaded when the elevator car is moving. In order to avoid stress concentrations, which stem from the receiving groove, in this region, the foot region of he guide flange can be pretreated by hot-rolling. [0039] According to FIG. 4 a , a bead 48 with stress-accommodating transitions 49 is formed in a foot region 45 of a guide flange 46 over a length of a guide rail 47 . A receiving groove 50 is then machined into the bead 48 by metal cutting. [0040] An embodiment, which is alternative to the bead 48 , without weakening the foot region 45 proposes compensation for the receiving groove laterally by a rolled-on rib at least on one side. [0041] [0041]FIG. 4 b shows a receiving groove 51 with radiussed transitions of groove flanks 52 , 53 , which is formed in a guide flange 54 by rolling. In a detail view V according to FIG. 5 it can be recognized that two mutually spaced-apart and parallel channels 55 , 56 are formed over the length of the guide rail by rolling. A region 57 between the channels 55 , 56 is processed by metal cutting, for example milled, and forms a planar support surface for a code strip (not illustrated). [0042] In accordance with the provisions of the patent statutes, the present invention has been described in what is considered to represent its preferred embodiment. However, it should be noted that the invention can be practiced otherwise than as specifically illustrated and described without departing from its spirit or scope.
Position transmitting equipment for ascertaining the position of a rail-guided elevator car includes a code carrier, which is arranged over the car travel path in fixed location on a guide rail with code marks of different permeability. A permanently precise reading of the coding is ensured by the fact that the code carrier is fixedly connected with a non-magnetic cover externally covering the code marks. The code carrier together with the outwardly facing non-magnetic cover are inserted into a receiving groove of the car guide rail, whereby a simple and reliable mounting is achieved and, in addition, temperature-dependent differences in expansion between the code carrier and the guide rail are avoided.
1
FIELD OF THE INVENTION [0001] The present invention relates to a tangential indexable cutting insert for use in metal cutting processes in general and for radial and axial turning of a stepped square shoulder in particular. BACKGROUND OF THE INVENTION [0002] Tangential cutting inserts, also known as on-edge, or lay down, cutting inserts, are oriented in an insert holder in such a manner that during a cutting operation on a workpiece the cutting forces are directed along a major (thicker) dimension of the cutting insert. An advantage of such an arrangement being that the cutting insert can withstand greater cutting forces than when oriented in such a manner that the cutting forces are directed along a minor (thinner) dimension of the cutting insert. Another advantage of such an arrangement is that with the minor dimension directed perpendicular to the cutting forces it is possible to manoeuvre the cutting insert between obstacles close to the workpiece. [0003] For turning a stepped square shoulder on a workpiece, a cutting tool assembly requires a cutting insert with an acute operative insert cutting corner, a tool back clearance angle along its inoperative cutting edge and an obtuse entering angle along its operative cutting edge. Such an entering angle enables an outwardly directed feed out movement to square out a shoulder, in particular, an outwardly directed radial feed out movement in the case of external axial turning operations and an outwardly directed axial feed out movement in the case of radial turning operations. [0004] In view of these restrictions, cutting inserts for turning stepped square shoulders are usually either rhomboidal or triangular; thereby having respectively, two or three indexable insert cutting corners for single-sided cutting inserts. Such cutting inserts are, for example, as illustrated and described in U.S. Pat. No. 4,632,608, each insert cutting corner being formed as a protruding nose portion at the junction between centrally depressed insert sides. The cutting inserts are preferably double sided so as to be respectively formed with four or six indexable insert cutting corners. [0005] With a view to increasing the number of cutting corners, a fully indexable non-tangential cutting insert is described in U.S. Pat. No. 6,074,137. The cutting insert comprises four substantially concave side edges extending between substantially square opposing upper and lower surfaces. Adjacent side edges meet at a cutting corner having an angle in the range of about 83°±5°. Although the cutting insert is substantially square and although it offers eight cutting corners, its depth of cut is limited. In fact, the maximal depth of cut is limited to less than the length of a side of an imaginary square, in which the insert is inscribed, in a top view of the insert. Furthermore, it is not a tangential cutting insert. [0006] [0006]FIGS. 1 and 2, show a cutting tool 20 with a tangentially seated cutting insert 22 for both axial and radial turning operations, also known as longitudinal and face turning operations. The cutting insert 22 is oriented with relief angles γ 1 and γ 2 for radial and axial turning operations, respectively. The cutting insert 22 has one operative cutting corner 24 , a first trailing non-operative cutting corner 26 during axial turning operations and a second trailing non-operative cutting corner 28 during radial turning operations. Major and minor cutting edges 30 , 32 extend between the operative cutting corner 24 and non-operative cutting corners 28 , 26 . [0007] [0007]FIG. 3 is an illustrative drawing showing the cutting tool 20 during either radial or axial turning operations of a workpiece 33 . Dashed lines 34 show an ideal square shoulder and the dash-dot line 35 is an imaginary extension of the worked face 36 of the workpiece 33 . As can be seen, for a radial turning operation, the second trailing non-operative cutting corner 28 and a portion of the major cutting edge 30 are oriented such that they “extend beyond” the imaginary extension 35 of the worked face 36 and would engage the workpiece 33 if an attempt were made to increase the depth of cut beyond a depth of cut, d, where the dashed line intersects the major cutting edge 30 . Thus, the depth of cut is limited during radial turning of a square shoulder. For axial turning in the configuration shown in FIG. 3, the depth of cut is also limited to d. Any increase in the depth of cut would lead to a non-square shoulder. Similarly, the insert could be configured with an orientation such that for an axial turning operation, the first trailing non-operative cutting corner 26 and a portion of the minor cutting edge 32 are disposed such that they have a limited depth of cut. Likewise, the insert could be configured with an orientation so that it has a limited depth of cut for both axial and radial turning operations due both to the first trailing non-operative cutting corner 26 and a portion of the minor cutting edge 32 and also to the second trailing non-operative cutting corner 28 and a portion of the major cutting edge 30 . SUMMARY OF THE INVENTION [0008] In accordance with the present invention there is provided an indexable cutting insert, for use in a cutting tool for turning operations, comprising: [0009] two identical opposing end surfaces having 180° rotational symmetry about a first axis passing therethrough, [0010] a peripheral side surface extending between the two opposing end surfaces, and [0011] a peripheral edge formed at the intersection of each end surface and the peripheral side surface, at least two sections of each peripheral edge constituting cutting edges; [0012] the peripheral side surface comprising: [0013] two identical opposing major side surfaces having 180° rotational symmetry about a second axis passing therethrough, the second axis being perpendicular to the first axis; [0014] two identical opposing minor side surfaces having 180° rotational symmetry about a third axis passing therethrough, the third axis being perpendicular to the first axis and the second axis; [0015] a major plane defined by the first axis and the second axis; [0016] a minor plane defined by the first axis and the third axis; [0017] a median plane being defined by the second axis and the third axis; [0018] each end surface having four corners, two lowered corners and two raised corners, the lowered corners being closer to the median plane than the raised corners; [0019] in a side view of one of the minor side surfaces, all four corners are equidistant from the minor plane; [0020] in a side view of one of the major side surfaces, all four corners are equidistant from the major plane. [0021] In accordance with the present invention, the cutting insert has a maximum distance D1 between the minor side surfaces that is greater than a maximum distance D2 between the major side surfaces. [0022] In accordance with the present invention, in an end view of the cutting insert, each major side surface is recessed. [0023] In accordance with the preferred embodiment of the present invention, in an end view, the distance between the opposing major side surfaces varies from the maximum distance D2 adjacent the corners of the cutting insert to a minimum distance d2 at the intersection of the major side surfaces with the major plane. [0024] In accordance with a specific application of the present invention, the minimum distance d2 is given by d2=D2−t, where the value t is given by 0.3 mm≦t≦0.4 mm. [0025] In accordance with the present invention, in an end view of the cutting insert, each minor side surface is recessed. [0026] In accordance with the preferred embodiment of the present invention, in an end view, the distance between the opposing minor side surfaces varies from the maximum distance D1 adjacent the corners of the cutting insert to a minimum distance d1 at the intersection of the minor side surfaces with the minor plane. [0027] In accordance with a specific application of the present invention, the minimum distance d1 is given by d1=D1−s, where the value s is given by 0.05mm≦s≦0.25 mm. [0028] In accordance with the present invention, each minor side surface merges with an adjacent major side surface at a corner side surface, wherein each corner side surface extends between a given raised corner of one of the two opposing end surfaces and a given lowered corner of the other of one of the two opposing end surfaces. [0029] In accordance with the preferred embodiment of the present invention, each cutting edge comprises a major edge, a minor edge and a corner edge, therebetween. [0030] In accordance with the present invention, each major edge, corner edge, and minor edge is formed at the intersection of adjacent major side surface, corner side surface, and minor side surface, respectively with an adjacent end surface. [0031] In accordance with the preferred embodiment of the present invention, the major edges are recessed in an end view. [0032] In accordance with the preferred embodiment of the present invention, the distance between the opposing major edges varies from the maximum distance D2 adjacent the corner edges to the minimum distance d2 at the intersection of the major edges with the major plane. [0033] In accordance with the preferred embodiment of the present invention, the minor edges are recessed in an end view. [0034] In accordance with the preferred embodiment of the present invention, the distance between the opposing minor edges varies from the maximum distance D1 adjacent the corner edges to the minimum distance d1 at the intersection of the minor edges with the minor plane. [0035] In accordance with the preferred embodiment of the invention, each raised corner forms a corner cutting edge and adjacent major and minor edges form major and minor cutting edges, respectively. [0036] Generally, the major cutting edge has a length L1 that is greater than half the distance D1. [0037] Generally, the minor cutting edge has a length L2 that is approximately half the distance D2. [0038] In accordance with the preferred embodiment of the present invention, the cutting insert further comprises an insert through bore extending between the major side surfaces and having a bore axis coinciding with the second axis. [0039] In accordance with the present invention there is provided a cutting tool comprising: the cutting insert in accordance with the present invention, a shim, and an insert holder having an insert pocket in which the shim and the cutting insert are securely retained. [0040] In the cutting tool, the insert pocket comprises: a base surface, the base surface being abutted by a given major side surface of the cutting insert, a first side wall extending uprightly from the base surface, the first side wall being abutted by a given minor side surface of the cutting insert, and a second side wall extending uprightly from the base surface, the first side wall being adjacent the major side surface and transverse thereto; [0041] the shim comprises a top surface that is abutted by a non-operative end surface of the cutting insert, an opposing bottom surface that abuts the first side wall, and a perimeter surface extending therebetween; [0042] a shim screw, extending through the shim through bore and threadingly engaged with a threaded second bore of the second side wall, secures the shim to the insert pocket; and [0043] a securing screw, extending through the insert through bore, threadingly engaged with a threaded receiving bore of the base surface, secures the cutting insert to the insert pocket, the securing screw. [0044] If desired, each end surface of the cutting insert further comprises two frustums extending away from the median plane located on either side of the major plane, and the top surface of the shim, in accordance with the present invention, further comprises a raised area being a portion of the top surface of the shim protruding from the top surface of the shim; wherein [0045] the two frustums of the non-operative end surface abut the raised area of the top surface of the shim. BRIEF DESCRIPTION OF THE DRAWINGS [0046] For a better understanding, the invention will now be described, by way of example only, with reference to the accompanying drawings in which: [0047] [0047]FIG. 1 is of a side view of a typical prior art cutting tool; [0048] [0048]FIG. 2 is an end view of the cutting tool in FIG. 1; [0049] [0049]FIG. 3 is a plan view of the cutting tool in FIG. 1 in a turning operation. [0050] [0050]FIG. 4 is a perspective view of the cutting insert in accordance with the present invention; [0051] [0051]FIG. 5 is a first side view of the cutting insert in FIG. 4; [0052] [0052]FIG. 6 is a second side view of the cutting insert shown in FIG. 4; [0053] [0053]FIG. 7 is a cross-sectional view of the cutting insert shown in FIG. 6 taken along C-C; [0054] [0054]FIG. 8 is an end view of the cutting insert shown in FIG. 4; [0055] [0055]FIG. 9 is a side view of a cutting tool in accordance with the present invention; [0056] [0056]FIG. 10 is an end view of the cutting tool in FIG. 9; [0057] [0057]FIG. 11 is a plan view of the cutting tool in accordance with the present invention in an axial turning operation; [0058] [0058]FIG. 12 is a detailed view of FIG. 11; [0059] [0059]FIG. 13 is a plan view of the cutting tool in accordance with the present invention in a radial turning operation; [0060] [0060]FIG. 14 is a detailed view of FIG. 13; [0061] [0061]FIG. 15 is a perspective exploded view of cutting tool in accordance with the present invention; and [0062] [0062]FIG. 16 is an end view of a cutting insert shown insert in accordance with the present invention. DETAILED DESCRIPTION OF THE INVENTION [0063] Attention is first drawn to FIGS. 4 to 8 , showing a tangential indexable cutting insert 38 in accordance with present invention. The cutting insert 38 is generally manufactured by form pressing and sintering a cemented carbide, such as tungsten carbide, and can be coated or uncoated. The cutting insert 38 is generally rectangular in an end view and comprises two identical end surfaces 40 , and a peripheral side surface 42 extending between the end surfaces 40 . The cutting insert 38 and the end surfaces 40 have 180° rotational symmetry about a first axis R 1 that passes through the end surfaces 40 . Since the end surfaces 40 are identical, only one will be described, it being understood that the other end surface 40 has identical structure. [0064] The peripheral side surface 42 comprises two opposed identical minor side surfaces 44 , two opposed identical major side surfaces 46 , and four opposed corner side surfaces 48 . Adjacent major and minor side surfaces 46 , 44 merge at a common corner side surface 48 . The cutting insert 38 and the major side surface 46 have 180° rotational symmetry about a second axis R 2 perpendicular to the first axis of rotational symmetry RI and passing through the major side surfaces 46 . The cutting insert 38 and the minor side surface 44 also has 180° rotational symmetry about a third axis R 3 that passes through the minor side surfaces 44 and is perpendicular to both the first and second axis of 180° rotational symmetry R 1 , R 2 . [0065] The peripheral side surface 42 intersects each end surface 40 at a peripheral edge 50 . The peripheral edge 50 comprises two identical opposed major edges 52 , two identical opposed minor edges 54 , and four opposed corner edges 56 . Adjacent major and minor edges 52 , 54 merge at a common corner edge 56 . The major edges 52 are formed at the intersection of the major side surfaces 46 with the end surfaces 40 , the minor edges 54 are formed at the intersection of the minor side surfaces 44 with the end surfaces 40 , and the corner edges 56 are formed at the intersection of the corner side surfaces 48 with the end surfaces 40 . [0066] For further description of the geometrical properties of the cutting insert 38 , a minor plane P 1 , to which the major edges 52 are generally parallel in an end view of the cutting insert 38 , is defined by the first and third axis of rotational symmetry R 1 , R 3 . A major plane P 2 , to which the minor edges 54 are generally parallel in an end view of the cutting insert 38 , is defined by the first and second axis of rotational symmetry R 1 , R 2 . A median plane M, which is perpendicular to both the first and major plane P 1 , P 2 , is defined by the second and third axis of rotational symmetry R 2 , R 3 . A width dimension D1 of the cutting insert 38 is defined as a maximum distance dimension between the minor side surfaces 44 measured parallel to the third axis R 3 . A length dimension D2 of the cutting insert 38 is defined as a maximum distance dimension between the major side surfaces 46 measured parallel to the second axis R 2 . For the tangential cutting insert 38 , the width dimension D1 is greater than the length dimension D2. [0067] Associated with each of the four corner edges 56 of a given end surface are four corners comprising two diametrically opposed raised corners 58 and two diametrically opposed lowered corners 60 . The lowered corners 60 are closer to the median plane M than are the raised corners 58 . In a side view of either of the minor side surfaces 44 , all four corners 58 , 60 are equidistant from the minor plane P 1 . In a side view of either of the major side surfaces 46 , all four corners 58 , 60 are equidistant from the major plane P 2 . Each corner side surfaces 48 extends between a given raised corner 58 of one end surface 40 and an adjacent lowered corner 60 on the opposing end surface 40 . Each corner side surface 48 has uniform radius of curvature along its length, and typically forms an arc angle of 95°±3°. The alternating raised and lowered corners 58 , 60 enable the cutting insert 38 to have four same-handed raised corners 58 for indexing. [0068] Adjacent major and minor edges 52 , 54 extend from the corner edge 56 of a given raised corner 58 with a variable slope to a respective lowered corner 60 . In a side view of the cutting insert 38 , adjacent each raised corner 58 , the slope of each major edge 52 (see FIG. 6) is generally constant with the major edge 52 substantially parallel to the median plane M. Moving along the major edge 52 towards an adjacent lowered corner 60 , the slope gradually increases and finally decreases adjacent the lowered corner 60 . As can be seen in FIG. 5 each minor edge 54 has a generally similar form to that of the major edges 52 . Thus in a respective side view, each major and minor edge 52 , 54 , has a similar wavy elongated “S”-shape. [0069] In an end view of the cutting insert 38 , the major edges 52 are concave. In other words, the major edges 52 are recessed in an end view wherein, the distance between the opposed major edges 52 varies from approximately D2 adjacent the corner edges 56 to a minimum distance d2 at the intersection of the major edges 52 with the major plane P 2 . The minimum distance d2 is defined by D2−t. In a non-binding example, t is greater than or equal to 0.3 mm and less than or equal 0.4 mm. In an end view of the cutting insert 38 , each major side surface 46 is also concave, being recessed in the same manner as its associated major edge 52 . It should be noted that the variation of the distance between the opposed major edges 52 (and likewise the opposed major side surfaces 46 ) need not decrease uniformly from the maximum value D2 to the minimum value d2. [0070] In an end view of the cutting insert 38 , the minor edges 54 are also concave, in a similar manner to the major edges 52 . The distance between the opposed minor edges 54 in an end view, varies from approximately D1 adjacent the corner edges 56 to a minimum distance d1 at the intersection of the minor edges 54 with the minor plane P 1 . The minimum distance d1 is defined by D1−s. In a non-binding example, s is greater than or equal to 0.05 mm and less than or equal 0.25 mm. Likewise, in an end view of the cutting insert 38 , each minor side surface 44 is concave, being recessed in the same manner as its associated minor edge 54 . The variation of the distance between the opposed minor edges 54 (and likewise the opposed minor side surfaces 44 ) need not decrease uniformly from the maximum value D1 to the minimum value d1. [0071] It will be appreciated that whereas the whole of the peripheral edge 50 can function as a cutting edge, in practice, sections of the peripheral edge 50 adjacent the lowered corners 60 will not function as cutting edges. In a accordance with a specific application of the present invention, each given peripheral edge 50 has an effective major cutting edge 66 that extends from an associated given raised corner 58 along the given corner edge 56 and the given major edge 52 for a given major cutting edge length L1, which is greater than one half of the width dimension D1. Additionally, in accordance with the specific application of the present invention, each peripheral edge 50 has an effective minor cutting edge 68 that extends from an associated given raised corner 58 along the given corner edge 56 and the given minor edge 54 for a given minor cutting edge length, L2, which is approximately one half of the length dimension D2. [0072] Attention is now drawn to FIGS. 9 and 10, showing side views of a cutting tool 70 in accordance with the present invention. The cutting insert 38 has relief angles γ1, γ2 and presents an operative raised corner 58 ′ outwardy projecting from the cutting tool 70 . [0073] Attention is now drawn to FIGS. 11 and 12, showing the cutting insert 38 in an insert holder 72 in a plan view during an axial turning operation of a stepped square shoulder 74 of a workpiece 76 rotating about an axis A. Adjacent the stepped square shoulder 74 is an operative major edge 52 ′, an operative corner edge 56 ′ of an operative raised corner 58 ′ an operative minor edge 54 ′, and a trailing lowered corner edge 78 ′. It will be appreciated that an operative minor edge 54 ′ constitutes a secondary cutting edge or wiper and that only a small section of it adjacent the operative corner edge 56 ′ contacts the workpiece 76 . Due to the relief angles γ1, γ2 and any other required orientation of the cutting insert 38 , an entering angle K is formed between the major edge 52 and the feed direction F 1 , and a back clearance angle Kn is formed between the operative minor edge 54 ′ and a cylindrical surface 80 of the workpiece 76 . As can be seen, the trailing lowered corner edge 78 ′ is completely relieved from the cylindrical surface 80 of the workpiece 76 , whereby the depth of cut for axial turning is unlimited. [0074] Attention is now drawn to FIGS. 13 and 14, showing the cutting insert 38 in an insert holder 72 in a plan view during an radial turning operation of a cylindrical surface 80 of a workpiece 76 rotating about an axis A. Adjacent the cylindrical surface 80 is an operative major edge 52 ′, an operative corner edge 56 ′ of the operative corner edge 58 ′ an operative minor edge 54 ′, and a trailing lowered corner edge 78 ″. It will be appreciated that that an operative major edge 52 ′ constitutes a secondary cutting edge or wiper and that only a small section of it adjacent the operative corner edge 56 ′ contacts the workpiece 76 . Due to the relief angles γ1, γ2 and any other required orientation of the cutting insert 38 , an entering angle K is formed between the operative minor edge 54 ′ and the feed direction F 2 , and a back clearance angle Kn is formed between the operative major edge 52 ′ and a stepped square shoulder 74 of the workpiece 76 . As can be seen, the trailing lowered corner edge 78 ″ is completely relieved from the stepped square shoulder 74 of the workpiece 76 , whereby the depth of cut for radial turning is unlimited. [0075] The seating and securing of the cutting insert 38 will now be described with reference to FIG. 15, showing various elements not mentioned above. These elements include two frustums 82 on each end surface 40 , an insert pocket 84 of the insert holder 72 , an insert through bore 86 , a securing screw 88 , a shim 90 , and a shim screw 92 . [0076] The insert pocket 84 comprises first and second side walls 94 , 96 uprightly extending from a base surface 98 of the insert pocket 84 . The shim 90 comprises a top surface 100 , a flat opposing bottom surface 102 , and a perimeter surface 104 extending therebetween. The top surface 100 of the shim 90 comprises a raised area 106 extending away from the bottom surface 102 of the shim 90 . A shim through bore 108 extends between the top surface 100 and the bottom surface 102 . The two frustums 82 of each end surface 40 extend away from the median plane M and are located on either side of the major plane P 2 . The frustums 82 are likely to impede chip flow, thereby limiting the lengths L1, L2 of the major and minor cutting edges 66 , 68 . [0077] The shim 90 is secured in the insert pocket 84 with its bottom surface 102 abutting the second side wall 96 . The shim screw 92 , extends through the shim through bore 108 and threadingly engages with a threaded second bore 110 passing through the second side wall 96 , securing the shim 90 to the insert pocket 84 . The cutting insert 38 is secured in the insert pocket 84 with a non-operative end surface 40 adjacent the top surface 100 of the shim 90 . The first side wall 94 abuts the minor side surface 44 of the cutting insert 38 , and the base surface 98 abuts the major side surface 46 . The two frustums 82 of a non-operative end surface 40 abut the raised area 106 of the top surface 100 of the shim 90 . The securing screw 88 extends through the insert through bore 86 and threadingly engages a threaded receiving bore 112 in the base surface 98 of the insert pocket 84 . [0078] It will be appreciated that the particular form of the end surfaces 40 will depend on the design factors that take into account various working conditions. For example, in order to increase the effective cutting wedge angle, a land 114 is provided adjacent the peripheral edge 50 (see FIG. 7). A rake surface 116 slopes downwardly and inwardly from the land 114 . If desired the rake surface can be provided with suitable chip control elements. [0079] It is advantageous to have recessed side surfaces and side edges to take into consideration manufacturing tolerances so that the sides will not become convex or partially convex, when viewed in an end view, and interfere with the workpiece. It is possible to use straight side edges, i.e., the major side surface 46 and the major edges 52 could be straight, as in FIG. 16, either by tight manufacturing tolerances during pressing and sintering or by additional steps of grinding. [0080] Although the present invention has been described to a certain degree of particularity, it should be understood that various alterations and modifications could be made without departing from the spirit or scope of the invention as hereinafter claimed.
A tangential indexable cutting insert can be used for metal cutting processes in general and for radial and axial turning of a stepped square shoulder in particular. The cutting insert exhibits 180° rotational symmetry about three mutually perpendicular axes. The cutting insert has generally “S”-shaped cutting edges extending between raised and lowered corners. The cutting edges and side surfaces are concave in an end view of the cutting insert. The cutting insert enables radial and axial turning operations of a square shoulder with unlimited depth of cut.
1
REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of Applicant's; earlier-filed U.S. patent application U.S. Ser. No. 08/404,108 filed on Mar. 13, 1995, now abandon the priority of which is hereby claimed. That application and the earlier patents on which it relies, including Applicant's; earlier U.S. patents identified below, are all incorporated herein by reference. This application is also related to commonly-owned U.S. patent application entitled "Filtered Blood Collection Device" which is being filed at the same time as this patent application. That patent application is also incorporated herein by reference. BACKGROUND The present invention relates to blood collection or autoinfusion devices such as are used for postoperative and intraoperative blood collection to collect bleeding and fluid loss from a patient. These devices have evolved over the last several decades from two basic lines of medical instruments. The first form of device, a cardiotomy reservoir, is a bottle or bucket assembly operating much like a vacuum cleaner, and used to collect blood during cardiac surgery. These devices are generally large unobstructed covered vessels which connect to a vacuum supply and have a suction wand to suck up loose pools of blood within the operating arena. The second form of device, generally referred to as a chest drain, is a relatively compact bedside vessel used to collect fluids postoperatively from a closed surgical site, e.g., from a drain tube implanted in the patient's; chest. These latter devices generally operate with a much smaller magnitude of suction, in the range of -15 to -25 cm. H 2 O, and typically include either a dry or wet suction regulator mechanism, as well as a water seal or one-way valve which prevents direct entry of atmospheric air into the blood collection chamber of the drain device. Since these devices apply their suction to the chest cavity and may be acted on by, or may affect motion of the lungs within the chest cavity, they generally also contain various forms of release valve to prevent excessive levels of either pressure or suction from occurring in the collection portion of the vessel or being applied to patient drain line. Chest drain mechanisms, whether wet or dry, pose several special design problems. In general, since they apply suction directly to a patient's; chest cavity, they must be capable of providing a low and consistent suction level compatible with human breathing cycles. On the other hand, the thoracotomy tube which connects them to a drainage site in a patient's; chest may draw air through the tube due to a perforation in the lungs or a leaky closure of the wound site to which it is attached. Air leakage from these additional sources provides a challenge in designing a suction regulator capable of sufficiently accurate low level long term regulation. A typical wet suction drain employing a water column of the desired 15 to 20centimeter height to bleed down the level of suction available at a regulated or unregulated hospital vacuum wall fitting, may experience drift due to evaporation of the water column. These wet drains are also prone to spillage of the water column and loss of pressure when the drain is tipped. Traditional multi-stage suction regulators which rely on a number of small passages in series have little application to these devices since they are adapted to static suction situations in which there is relatively little flow. Instead, poppet, flap or diaphragm-type valves have generally been more effective in implementing dry suction regulator assemblies for chest drains of this type. A number of such constructions are known from the patents or products of workers in this field, such as Leonard Kurtz, Sueshiro Akiyama, the present inventors and others, as well as from non-patent medical publications. However, beyond the problem of providing a regulator structure capable of accommodating the extreme variation in conditions which occur in a hospital setting, other common nonphysical considerations related more to industrial design than to simple engineering have not been effectively addressed in these prior art structures. Thus, for example, it would be desirable to produce a dry suction regulator which does not require special skill, training or attentiveness to set up. It would also be desirable to produce a dry suction regulator in which the various components provide both a proper suction operation and metered confirmation of proper operation. It would further be desirable to provide such a dry suction device of low complexity and of great ease of assembly or manufacture. SUMMARY OF THE INVENTION These and other desirable features are obtained in a dry suction regulation device in accordance with the present invention, such as a chest drain, wherein a large air entryway or manifold in a side wall of the device conducts air to a spring loaded poppet valve to bleed down a higher level of suction which is applied at a suction port at the top of the device. The poppet valve is adjustable and is mounted within an open-ended threaded canister in which radial fins allow air approaching laterally through the manifold to pass axially past the poppet, forming a direct, high conductance path to the suction outlet. Below the poppet valve, a water seal chamber prevents migration of outside air to the collection chamber proper, while an expansion bellows is positioned to indicate operating levels of suction in the seal chamber. The expansion bellows is also located below the level of the poppet and it expands proximate to a curved graduation contour that compensates for parallax and perspective defects encountered in the hospital room placement of the device below observation level. In a preferred embodiment, the poppet valve drops into a cup-shaped recess in the body of the device wherein it seals laterally against protruding walls to form an internal entry channel directing the admitted air to the suction connection. A filter within the canister filters air as it enters, and a face plate assembled over a broad front surface of the collection device shields or masks the inlet assembly from direct contact or from being draped over or blocked by dangling sheets or the like. The major part of the drain vessel is given over to a collection chamber, with the poppet valve, water seal, and collection chamber being compactly arranged to provide a low and generally centered center of gravity that rises slowly as the collection chamber is filled. This compact arrangement allows the maintenance of a uniform and low level of suction while still achieving a collection volume comparable to prior art devices in a container having dimensions as much as ten or twenty percent smaller. The resulting reduction in size is considered a significant safety factor in view of the high incidence of knocking over that occurs in a clinical setting. BRIEF DESCRIPTION OF THE DRAWINGS These and other features of the invention will be understood from the description and claims below, taken together with the drawings, wherein FIG. 1 is a face view of a chest drain in accordance with the present invention; FIG. 1A and 1B show other embodiments; FIG. 2 is a detail of the housing portion of the chest drain of FIG. 1; FIG. 3 is a detail of a poppet suction valve employed in the drain of FIGS. 1 and 2; FIG. 4 is an exploded view showing construction of the poppet valve of FIG. 3; FIG. 5 shows an internal element of the poppet assembly; FIG. 6 and 6A illustrate details of a suction meter; and FIGS. 7 and 7A show further details of regulator mounting and operation. DETAILED DESCRIPTION The embodiment of FIG. 1 is a so-called dry drain, in which the suction assembly 8 includes a suction setting valve 30 fitted within a recess 35 that controls the amount air entering the chamber to an amount which reduces to a user-set level of minus 15-20 cm H 2 O, the amount of suction applied by a wall-fitting suction port 40. A water seal column 50 operates in a conventional manner as a one-way valve between the suction regulator and the fluid collection chamber 22. Water seal 50 includes a first or large column 51 and a second or narrow column 52 in which a pooling region 55 of approximately several centimeters of water act as a one way check valve for flow of air out of the collection chamber. In this embodiment, a float ball 56 rides up and down in the column 52 to indicate the level of excess suction prevailing in chamber 22. Briefly when suction in chamber 22 exceeds the level of suction applied by the suction regulator 30, the water level in column 52 rises and the position of the float ball 56 thus warns an attendant of dangerous conditions of excessive negativity. At the top of column 52, a check ball 58 positioned below a non-mating aperture 57 (FIG. 2) rises on the water and impedes the further rise of water level so that the pool of sealing water 55 cannot become entirely depleted, while water leaking past the check ball harmlessly collects above the ball and ultimately returns to the column when suction again reaches normal levels. Preferably, the leaky check ball 58 is configured to self-release after a short time interval, as described in commonly-owned earlier U. S. Pat. No. 5,114,416. The water seal chamber 50 maybe filled directly through the suction inlet 40 which, as illustrated, is located directly above column 51. The upper region of column 51 curves around as shown at 51a about the portion of the housing which receives the suction regulator mechanism. While only a centimeter or two of water is required in the pooling region 55 to form an effective seal, the indicator ball 56 employs a column 7 to 8 inches high to meter the exact level of excess negativity in the chamber, up to 20 centimeters, requiring a height of about 10 inches to accommodate the illustrated column, and this constraint results in the vessel having a more or less conventional size and shape, although it may be smaller than a prior art drain of the same collection capacity. This is due, in part, to the compact transverse regulator location with the over/under seal configuration, allowing a relatively wider and lower collection volume. In other embodiments, the water seal and float valve may be replaced by an entirely dry flap assembly of valves or similar controls making the suction regulation unit even more compact, than illustrated for example in FIG. 1. In other embodiments, however, the dry suction regulator may be replaced by a water column set up to provide regulation of suction to a level set by the height of the water column, as illustrated in greater detail in each of applicant's; aforesaid U.S. patents, or applications identified herein and their respective parent or grandparent applications. Other features appearing in the drawing include a positive pressure relief valve 62, which is a simple check valve at the top of the large water seal arm 51, and an excess negativity valve 64 which provides a compensating air inlet via a valved filtered passageway to the atmosphere through the top wall above the water seal small arm portion 52. Each of these assemblies are described in greater detail in Applicant's; commonly-owned U.S. Pat. No. 5,397,299. Pierceable septa 59, 59a allow one to conveniently sample or refill the water seal, and to sample collected fluid, respectively. A handle 66 is formed integrally with the body, and like the rest of the body extends to a common plane lying at the front face of the vessel, which is sealed to a transparent face plate that closes the assembly. The handle 66 is thus secured to the body by its vertical edges 66a and 66b, as well as welded to the face plate along both of those edges and along its upper horizontally-oriented face 66c thus forming an open rectangular box closed on five of its six sides. This forms an exceptionally secure and strong handle assembly which is relatively immune to snagging on dangling sheets or straps. A removable plug or grommet 72 in the upper surface of the vessel allows one to readily empty residual contents for separate disposal of the device and of the biological waste contained therein, after use. A bellows-type pressure indicator 70 is located in the water seal U-column, above the pooling region of the water seal chamber in column 51, and has its interior communicating with the surrounding atmosphere, so that it expands in length as the level of suction increases in the column 51. The device further includes a blood filter located below the inlet which isolates the clots so they cannot reach an infusion outlet of the collection chamber. The filter may be a basket-like large area filter assembly, a coarse screen which extends as a barrier in the collected fluid to segregate clots, or may be another filter arrangement. Examples of such embodiments are give in the aforesaid contemporaneously-filed patent application for Filtered Blood Collection Device, as well as in the aforesaid patents. In general, the filter is both large in area, and is "non-traumatic" in its action on the collected blood cells. FIGS. 1A and 1B show alternative embodiments with the filter locations being denoted by "F" . These filters include drop-through and overflow paths, or vent arrangements or other configurations to avoid trauma to or drying of blood cells from impact, pressure differentials, closed accumulation stagnation or the like. A face plate is joined to the front of a substantially single-piece molded body to form the overall device, with the face plate lying substantially in a plane contacting each raised wall of the molded body, covering and closing the various columns, chambers and the like to form distinct subcompartments of the collection vessel. This face plate, while not specifically illustrated in FIG. 1, extends generally coincident with or slightly beyond the edges of the body portion, extending up to or above the highest surface 66c of the handle, to which it is joined, and extending on the left to the line marked "FP" which covers and generally shields the suction regulator 30 from inadvertent rotation. Further details of the mechanical and structural arrangements in this region are discussed later below, in connection with FIGS. 7 and 7A. Initially, however, it bears noting that the molded housing or body portion 1 (FIG. 1) curves inwardly on its left side to form a cup-shaped recess 35 behind the face plate, which has a generally cylindrical shape with a floor 35a and a raised rim or bezel 35b into and against which the suction valve 30 fits. A plurality of thin V-channels 35c extend parallel to the axis of the cylindrical recess, and corresponding knife-edge ridges 31a, 31b and 31c protrude from the suction regulator body and fit into the channels to align and seal the regulator in the recess. The regulator, together with the adjacent upper and lower portions of the left wall of the device, combine to form the outer surface of the vessel, the volume inside of which communicates along a direct passage with the suction connector 40. The regulator thus drops transversely into the body, and in normal operation is oriented horizontally, with the various columns 51, 52 extending substantially vertically and curving around the regulator to reach to the top the vessel. As best seen in the exploded view, FIG. 4, the principal elements of suction regulator 30 include the body 132, the poppet 142 which is shaped generally like a top hat with a brim 143 extending about an inverted cup-shaped member 144, an upper body sleeve 152 and a control knob 162 which are arranged one above the other in the order described. The poppet 142 fits over a spring 141 held on a centering post 131 at the bottom of the body, which in turn is supported and centered by a skeletal frame formed of braces 131a, of which one is visible in the FIGURE. Thus the poppet is held in space across the generally open cylinder defined by the regulator as a whole. The top 144 of the poppet 143 rides as a piston within a bore 154a defined by a centering cup 154 which extends above the lower end of sleeve 153, with the cup 154, like pin 131, being centrally supported by a screen, grid work or, as shown, a perforated plate 156 (FIG. 5). The poppet is thus axially suspended to respond to suction such that the brim 143 is normally urged by the compressed spring against the rim 153 of the sleeve, and is drawn down against the spring force to open a peripheral passageway which accommodates a large airflow to bleed down the suction in the vessel. Continuing with a description of the suction regulator, the upper sleeve portion has a coarse external screw thread 155 about its periphery that mates with a corresponding internal screw thread 135 formed in the body 132, so that the rotational angle of sleeve 152 with respect to body 132 determines its height in the assembly. Since the sleeve bears against the brim 143 of the poppet, this also determines the resting state spring compression force, hence the suction response, of the assembly. The inside surface of sleeve 152 is provided with a regular series of vertical ridges 157 which mate with a corresponding plurality of splines 167 on the cylindrical exterior of knob 162. Thus, knob 162 may be dropped into the sleeve at a desired angular orientation, and thereafter grips the sleeve firmly to transmit rotational torque thereto. Turning the knob 162 therefore adjusts the poppet release force. Knob 162 has a plurality of radially oriented vanes or gripping teeth 165 disposed at its upper portion about a generally hub-like central plate 166 and a lower ring-like body annulus 168 from which a generally cylindrical key body 169 bearing the splines 167 extends. Adjacent pairs of teeth 165 define corresponding entryways leading directly into the hollow center 164 of the cylindrical body 169, so that the entire assembly 162, 152, and 132 form an open or porous body, except for the solid poppet which seats against the rim 153 of the cylindrical side wall of sleeve 152. Thus, as the poppet moves, air enters with little resistance and the suction level is immediately and dependably modulated by the floating poppet assembly. A stop 163 is positioned on the annulus 168 and extends radially beyond the teeth 165 to abut against a protruding lip 133 of the body 132, thus limiting the total rotation of the knob 162 when it is inserted in the threaded sleeve 152 to slightly less than one full revolution. This defines the limits of the range of operation of the device on either side of the set point initially set by threading the sleeve into the body to compress the spring. If calibrated operation is desired, once the regulator has been assembled, a marker or arrow 161 may be adhesively affixed to the central plate 166 to point to a fixed circumferential set of graduations printed on the face plate of the drain device. FIGS. 7 and 7A indicate the air entry paths through the regulator 30. A broad recessed area 110 in the generally vertically oriented left side wall 102 of the device curves inwardly toward the suction regulator 30 and is generally shielded form occlusion by the protruding left edge of the face plate 10 as well as the portions of wall 102 above and below the recess. Thus air readily enters between vanes 165 into the hollow center 164. A porous foam filter body may be fitted in region 164 to filter incoming air and assure that liquid or solid matter do not fall into the device or reach into the poppet assembly. Where suction level is lower than the set point, the poppet allows air through the cylindrical assembly along air entry path P, continuing by direct route along P 2 (FIG. 2) to the suction connection. This dependably maintains the net applied suction level at the set point in the 10-50 cm H 2 O range. The level of suction prevailing in the water seal assembly is shown by a nonmechanical meter formed by the passively-operated bellows 70 (FIG. 1). As shown in greater detail in FIG. 6 the bellows 70 is a pleated polymer tube which has one end-the right end as shown-closed, and its open end 71 sealably affixed to an opening in side wall 102 by a grommet 73. The outside of the bellows thus experiences the suction prevailing in seal 50, and it extends along a substantially horizontal line B behind the face plate in a left-right direction with its extension increasing as a greater degree of suction is applied. Applicants have found that this bellows meter, while providing a repeatable and accurate response, suffers from a low degree of "readability" due to factors such relative parallax effects, the jagged nature of its wall geometry, glare of the face plate as well as the generally oblique perspective occasioned by such chest drains being normally located well below eye level near or on a bedside or floor. The visibility problem is addressed in accordance with another aspect of the invention by providing a graduation pattern on the face plate which intersects the expanding bellows 70. One such pattern 80 is shown in FIG. 6 employing an elbow-shaped clear space in the face plate 100 and having suction readings 82 arrayed along its curving edge. The bellows 70 advances along a straight portion of the visible path, and as it advances further the graduations are swept across the bellows, which is colored a contrasting color to the face graduations. The intersection of the bellows right end with a crossing line thus defines more accurately and visibly the prevailing degree of suction. Another pattern 85 is shown in FIG. 6A. Here an elbow-shaped space above the bellows curves down into the bellows extension path. At lesser suctions a small side fragment or wedge of the bellows tip is visible while an increasingly broader vertical width of the bellows becomes visible as higher degrees of suction are reached. The bellows cross the vertical graduation line at saturation, i.e., at the highest degree of suction, corresponding to -40 cm H 2 O with the illustrated scale. Notably, the vertical line is less prone to parallax errors when viewed aslant from above in normal operation. Other curved or oblique graduation patterns adjacent the extension path B are also contemplated to provide a shaped display or oblique edge crossing effect. This allows the simple expansion bellows to reliably indicate the degree of suction set on and achieved by the regulator 30. The invention has been described with reference to several particular embodiments; however, it may take other forms which will occur to those skilled in the art, and all such forms are encompassed within the spirit and scope of the present invention, and its equivalent, as defined by the claims appended hereto.
A blood collection device has a modular suction regulator assembly in the form of an adjustable negative pressure relief valve which controls the level of suction in a collection chamber by admitting air to a short bleed-in passage proximate to a suction connection. The modular assembly is a canister which drops into a receptacle oriented transversely in the collection vessel, and defines a laterally-directed intake manifold which resists blockage. The intake passes centrally through the canister along a path spanned by a filter, past a hat-shaped poppet supported on a compression spring. Fluted and threaded members control the scale and range of poppet response so that the assembly may be calibrated before installation. A face plate covers the installed canister, and radial vanes in the intake manifold double as gripping elements for manual adjustment of the assembly. A bellows meter provides refined suction resolution by linearly advancing across an oblique or curved reference line. Other improvements include a compact and balanced layout of suction canister, seal chamber and collection chamber, and a rigid handle assembly having five faces integral with the device.
0
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The invention relates to a process for producing a highly purified food ingredient from the extract of the Stevia rebaudiana Bertoni plant and its use in various food products and beverages. [0003] 2. Description of the Related Art [0004] Sugar alternatives are receiving increasing attention due to the awareness of many diseases associated with the consumption of high-sugar foods and beverages. However, many artificial sweeteners such as dulcin, sodium cyclamate and saccharin have been banned or restricted in some countries due to concerns about their safety. As a result, non-caloric sweeteners of natural origin are becoming increasingly popular. The sweet herb Stevia rebaudiana Bertoni produces a number of diterpene glycosides which feature high intensity sweetness and sensory properties superior to those of many other high potency sweeteners. [0005] The above-mentioned sweet glycosides, have a common aglycon, steviol, and differ by the number and type of carbohydrate residues at the C13 and C19 positions. The leaves of Stevia are able to accumulate up to 10-20% (on dry weight basis) steviol glycosides. The major glycosides found in Stevia leaves are rebaudioside A (2-10%), stevioside (2-10%), and rebaudioside C (1-2%). Other glycosides such as rebaudioside B, D, E, and F, steviolbioside and rubusoside are found at much lower levels (approx. 0-0.2%). [0006] Two major glycosides—stevioside and rebaudioside A (reb A), were extensively studied and characterized in terms of their suitability as commercial high intensity sweeteners. Stability studies in carbonated beverages confirmed their heat and pH stability (Chang S. S., Cook, J. M. (1983) Stability studies of stevioside and rebaudioside A in carbonated beverages. J. Agric. Food Chem. 31: 409-412.) [0007] Steviol glycosides differ from each other not only in their molecular structures, but also by their taste properties. Usually stevioside is found to be 110-270 times sweeter than sucrose, rebaudioside A between 150 and 320 times sweeter than sucrose, and rebaudioside C between 40-60 times sweeter than sucrose. Dulcoside A is 30 times sweeter than sucrose. Rebaudioside A has the least astringent, the least bitter, and the least persistent aftertaste, thus possessing the most favorable sensory attributes in major steviol glycosides (Tanaka O. (1987) Improvement of taste of natural sweetners. Pure Appl. Chem. 69:675-683; Phillips K. C. (1989) Stevia : steps in developing a new sweetener. In: Grenby T. H. ed. Developments in sweeteners, vol. 3. Elsevier Applied Science, London. 1-43.) The chemical structure of rebaudioside A is shown in FIG. 1 . [0008] Methods for the extraction and purification of sweet glycosides from the Stevia rebaudiana plant using water or organic solvents are described in, for example, U.S. Pat. Nos. 4,361,697; 4,082,858; 4,892,938; 5,972,120; 5,962,678; 7,838,044 and 7,862,845. [0009] However, even in a highly purified state, steviol glycosides still possess undesirable taste attributes such as bitterness, sweet aftertaste, licorice flavor, etc. One of the main obstacles for the successful commercialization of stevia sweeteners are these undesirable taste attributes. It was shown that these flavor notes become more prominent as the concentration of steviol glycosides increases (Prakash I., DuBois G. E., Clos J. F., Wilkens K. L., Fosdick L. E. (2008) Development of rebiana, a natural, non-caloric sweetener. Food Chem. Toxicol., 46, S75-S82.). [0010] Rebaudioside B (CAS No: 58543-17-2), or reb B, also known as stevioside A 4 (Kennelly E. J. (2002) Constituents of Stevia rebaudiana In Stevia : The genus Stevia , Kinghorn A. D. (Ed), Taylor & Francis, London, p. 71), is one of the sweet glycosides found in Stevia rebaudiana . Sensory evaluations show that reb B was approximately 300-350 times sweeter than sucrose, while for reb A this value was approximately 350-450 (Crammer, B. and Ikan, R. (1986) Sweet glycosides from the Stevia plant. Chemistry in Britain 22, 915-916, and 918). The chemical structure of rebaudioside B is shown in FIG. 2 . [0011] It was believed that reb B forms from the partial hydrolysis of rebaudioside A during the extraction process (Kobayashi, M., Horikawa, S., Degrandi, I. H., Ueno, J. and Mitsuhashi, H. (1977) Dulcosides A and B, new diterpene glycosides from Stevia rebaudiana . Phytochemistry 16, 1405-1408). However, further research has shown that reb B occurs naturally in the leaves of Stevia rebaudiana and is currently one of nine steviol glycosides recognized by FAO/JECFA (United Nations' Food and Agriculture Organization/Joint Expert Committee on Food Additives) in calculating total steviol glycosides' content in commercial steviol glycoside preparations (FAO JECFA (2010) Steviol Glycosides, Compendium of Food Additive Specifications, FAO JECFA Monographs 10, 17-21). [0012] Only a few methods are described in literature for preparing reb B. [0013] Kohda et al., (1976) prepared reb B by hydrolysis of reb A with hesperidinase. Reb B was also prepared by alkaline saponification of reb A. The said saponification was conducted in 10% potassium hydroxide-ethanol. The solution was acidified with acetic acid, and extracted with n-butanol. The butanol layer was washed with water and concentrated at low temperature in vacuo. The residue was crystallized from methanol to give reb B. (Kohda, H., Kasai, R., Yamasaki, K., Murakami, K. and Tanaka, O. (1976) New sweet diterpene glucosides from Stevia rebaudiana . Phytochemistry 15, 981-983). The described processes might be suitable for laboratory scale preparation of reb B, but are not suitable for any large scale or commercial reb B preparation. [0014] Ahmed et al., used mild alkaline hydrolysis of reb A to prepare reb B. According to the described procedure, reb A was hydrolyzed to reb B by refluxing with 10% aqueous KOH at 100° C. for 1 hr. After neutralization with glacial acetic acid, the precipitated substance was recrystallized twice from methanol (Ahmed M. S., Dobberstein R. H., and Farnsworth N. R. (1980) Stevia rebaudiana : I. Use of p-bromophenacyl bromide to enhance ultraviolet detection of water-soluble organic acids (steviolbioside and rebaudioside B) in high-performance liquid chromatographic analysis, J. Chromatogr., 192, 387-393). [0015] The use of methanol as recrystallization media as described in the literature will require its subsequent removal from the product. It is noted that handling of toxic substances such as methanol requires specialized manufacturing installations and, when applied in food processing, sophisticated food safety measures. [0016] It is also noted that no significant work has been conducted to determine the potential of reb B as a sweetener or food ingredient. Moreover, reb B is often viewed as process artifact and unnecessary impurity in commercial steviol glycosides preparations. No significant evaluation of the influence of reb B on the overall taste profile of steviol glycoside preparations has been conducted. [0017] The water solubility of reb B is reported to be about 0.1% (Kinghorn A. D. (2002) Constituents of Stevia rebaudiana In Stevia : The genus Stevia , Kinghorn A. D. (Ed), Taylor & Francis, London, p. 8). In many food processes where highly concentrated ingredients are used, a highly soluble form of reb B will be necessary. [0018] Considering the facts mentioned above, there is a need to evaluate reb B as a sweetener and food ingredient and to develop a simple and efficient process for food grade reb B preparations suitable for food and other applications. [0019] Within the description of this invention we will show that, when applied in specific manner, reb B may impact the taste profile and offer significant advantages for the use of stevia sweeteners in various applications. SUMMARY OF THE INVENTION [0020] The present invention is aimed to overcome the disadvantages of existing Stevia sweeteners. The invention describes a process for producing a high purity food ingredient from the extract of the Stevia rebaudiana Bertoni plant and use thereof in various food products and beverages as a sweetness and flavor modifier. [0021] The invention, in part, pertains to an ingredient comprising steviol glycosides of Stevia rebaudiana Bertoni plant. The steviol glycodsides are selected from the group consisting of stevioside, rebaudioside A ( FIG. 1 ), rebaudioside B ( FIG. 2 ), rebaudioside C, rebaudioside D, rebaudioside E, rebaudioside F, dulcoside A, steviolbioside, rubusoside, as well as other steviol glycosides found in Stevia rebaudiana Bertoni plant and mixtures thereof. [0022] The invention, in part, pertains to a process for producing an ingredient containing rebaudioside B, and stevioside, rebaudioside A, rebaudioside C, rebaudioside D, rebaudioside E, rebaudioside F, dulcoside A, steviolbioside, rubusoside, as well as other steviol glycosides found in Stevia rebaudiana Bertoni plant and mixtures thereof. [0023] In the invention, rebaudioside A commercialized by PureCircle Sdn. Bhd. (Malaysia), containing, rebaudioside A (about 95-100%), stevioside (about 0-1%), rebaudioside C (about 0-1%), rebaudioside F (about 0-1%), rebaudioside B (about 0.1-0.8%), rebaudioside D (about 0-1%), and other glycosides amounting to total steviol glycosides' content of at least 95%, may be used as a starting material. Alternatively stevia extracts with different ratios of steviol glycosides may be used as starting materials. [0024] The starting material is subjected to complete or partial conversion into reb B using a biocatalyst capable of hydrolyzing β-glucosyl ester bonds. The obtained glycoside mixtures can be used “as-is” as well as by recovering reb B from the mixture and using it as a pure ingredient. [0025] The low solubility reb B may be subjected to additional thermal treatment to increase solubility. [0026] The obtained products were applied in various foods and beverages as sweeteners, sweetener enhancers and flavor modifiers, including soft drinks, ice cream, cookies, bread, fruit juices, milk products, baked goods and confectionery products. [0027] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. BRIEF DESCRIPTION OF THE DRAWINGS [0028] The accompanying drawings are included to provide a further understanding of the invention. The drawings illustrate embodiments of the invention and together with the description serve to explain the principles of the embodiments of the invention. [0029] FIG. 1 shows the chemical structure of rebaudioside A. [0030] FIG. 2 shows the chemical structure of rebaudioside B [0031] FIG. 3 shows an HPLC chromatogram of a stevia composition comprising rebaudioside A and rebaudioside B. DETAILED DESCRIPTION OF THE INVENTION [0032] Advantages of the present invention will become more apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. [0033] Rebaudioside A commercialized by PureCircle Sdn. Bhd. (Malaysia), containing, rebaudioside A (about 95-100%), stevioside (about 0-1%), rebaudioside C (about 0-1%), rebaudioside D (about 0-1%), rebaudioside F (about 0-1%), rebaudioside B (about 0.1-0.8%) and other glycosides amounting to total steviol glycosides' content of at least about 95%, may be used as a starting material. Alternatively stevia extracts with different ratios of steviol glycosides may be used as starting materials. [0034] The HPLC analysis of the raw materials and products can be performed on an Agilent Technologies 1200 Series (USA) liquid chromatograph, equipped with Phenomenex Prodigy ODS3, 5 μm (4.6×250 mm) column at 40° C. The mobile phase was 32:68 mixture of acetonitrile and 10 mmol/L sodium phosphate buffer (about pH 2.6) at 1 mL/min. A diode array detector set at 210 nm can be used as the detector. One example of an HPLC chromatogram thus obtained is shown in FIG. 3 . [0035] As used herein, unless specified further, “reb 13 ” and “reb B composition” shall be used interchangeably to refer to purified rebaudioside B or rebaudioside B in combination with any other chemical entity. Preparation of Reb B 1. Biocatalytic Conversion [0036] In one embodiment of the invention, reb A is dispersed in water to form solution. The concentration of reb A is about 0-50% (w/v) preferably about 10-25%. An enzyme preparation selected from group of esterases, lipases, cellulases, hemicellulases, hesperidinases, lactases and β-glucosidases, or any enzyme capable of hydrolyzing β-glucosyl ester bonds, or free or immobilized cells, or any other biocatalysts capable of hydrolyzing β-glucosyl ester bonds (the enzyme preparations, enzymes, free or immobilized cells, and other biocatalysts hereinafter collectively referred to as “biocatalysts”) are added to reb A solution to form the reaction mixture. The mixture is incubated at about 10-150° C., preferably about 30-100° C., for a period of about 0.5-72 hrs, preferably about 1-48 hrs. As a result reb A is hydrolyzed to reb B. The molar yield of conversion of reb B is about 5-100%, preferably about 90-100%. [0037] After the reaction, the biocatalyst is inactivated by heating or removal from the reaction mixture. The pH of obtained mixture is adjusted by an acid, preferably by sulfuric acid or ortho-phosphoric acid, until a pH of about 3.0-5.0 is reached, preferably until a pH of about 3.0-4.0 is reached. Upon acidification, a precipitate is formed. The precipitate is separated by any method known in the art such as filtration or centrifugation and washed with water until the water reaches a pH of about 4.0-5.0. The obtained crystalline material is dried under vacuum at about 60-105° C. to yield a mixture of reb A and reb B having a ratio of about 1%:99% to about 99%:1% (w/w), preferably about 5%:95% to about 1%:99% (w/w). 2. Optional Post-Conversion Purification [0038] To obtain purified reb B, in one embodiment the separated precipitate described above is suspended in water and the mixture is subjected to continuous agitation over about 0.5-24 hrs, preferably about 1-3 hours, at about 50-100° C., preferably about 60-80° C. The ratio of precipitate to water (w/v) is about 1:5 to about 1:20, preferably about 1:10 to about 1:15. The washed crystals are separated and dried under vacuum at about 60-105° C. to yield reb B with about 99% purity. 3. Optional Post-Conversion Solubility Enhancement [0039] The following procedure can be used to increase the water solubility of reb B or any reb B composition. The obtained compositions generally have a water solubility of less than about 0.2% (w/v). In order to increase the solubility of these compositions, the compositions were combined with the water at ratio of about 1:1 (w/w) and the obtained mixture was further subjected to a gradient heat treatment which resulted in a high stability and high concentration solution. The gradient of about 1° C. per minute was used in heating the mixture. The mixture was heated to the temperature of about 110-140° C., preferably about 118-125° C. and was held at maximum temperature for about 0-120 min, preferably about 50-70 min. After the heat treatment, the solution was cooled down to room temperature at gradient of about 1° C. per minute. The solution was spray dried by a laboratory spray drier operating at about 175° C. inlet and about 100° C. outlet temperatures. An amorphous form of the composition was obtained with greater than about 20% solubility in water at room temperature. Use of Reb B Compositions [0040] The reb B compositions described above can be used as a sweetness enhancer, a flavor enhancer and/or a sweetener in various food and beverage products. Non-limiting examples of food and beverage products include carbonated soft drinks, ready to drink beverages, energy drinks, isotonic drinks, low-calorie drinks, zero-calorie drinks, sports drinks, teas, fruit and vegetable juices, juice drinks, dairy drinks, yoghurt drinks, alcohol beverages, powdered beverages, bakery products, cookies, biscuits, baking mixes, cereals, confectioneries, candies, toffees, chewing gum, dairy products, flavored milk, yoghurts, flavored yoghurts, cultured milk, soy sauce and other soy base products, salad dressings, mayonnaise, vinegar, frozen-desserts, meat products, fish-meat products, bottled and canned foods, tabletop sweeteners, fruits and vegetables. [0041] Additionally the compositions can be used in drug or pharmaceutical preparations and cosmetics, including but not limited to toothpaste, mouthwash, cough syrup, chewable tablets, lozenges, vitamin preparations, and the like. [0042] The compositions can be used “as-is” or in combination with other sweeteners, flavors and food ingredients. [0043] Non-limiting examples of sweeteners include steviol glycosides, stevioside, rebaudioside A, rebaudioside B, rebaudioside C, rebaudioside D, rebaudioside E, rebaudioside F, dulcoside A, steviolbioside, rubusoside, as well as other steviol glycosides found in Stevia rebaudiana Bertoni plant and mixtures thereof, stevia extract, Luo Han Guo extract, mogrosides, high-fructose corn syrup, corn syrup, invert sugar, fructooligosaccharides, inulin, inulooligosaccharides, coupling sugar, maltooligosaccharides, maltodextins, corn syrup solids, glucose, maltose, sucrose, lactose, aspartame, saccharin, sucralose, sugar alcohols. [0044] Non-limiting examples of flavors include lemon, orange, fruit, banana, grape, pear, pineapple, bitter almond, cola, cinnamon, sugar, cotton candy, vanilla flavors. [0045] Non-limiting examples of other food ingredients include flavors, acidulants, mineral, organic and amino acids, coloring agents, bulking agents, modified starches, gums, texturizers, preservatives, antioxidants, emulsifiers, stabilisers, thickeners, gelling agents. [0046] The following examples illustrate various embodiments of the invention. It will be understood that the invention is not limited to the materials, proportions, conditions and procedures set forth in the examples, which are only illustrative. Example 1 Preparation of Stevia Composition [0047] 1 g of rebaudioside A produced by PureCircle Sdn. Bhd. (Malaysia), containing, 98.1% rebaudioside A, 0.3% stevioside, 0.2 rebaudioside C, 0.2% rebaudioside F, 0.4% rebaudioside B and 0.6% rebaudioside D was dissolved in 10 mL 0.1M phosphate buffer (pH 7.0) and about 0.1 mL of commercial lactase preparation—Maxilact® obtained from DSM Food Specialties B.V. (Netherlands), was added. The mixture was incubated at 37° C. for 36 hours. Then the mixture was boiled at 100° C. for 15 min and filtered through the layer of activated carbon. The filtrate temperature was adjusted to 20° C. and the pH was adjusted to pH 4.0 with ortho-phosphoric acid. The solution was held under moderate agitation conditions for 4 hours and a precipitate was formed. The precipitate was filtered and washed on the filter with 2000 mL of water. The washed crystals were dried under vacuum to yield 0.9 g material containing about 80% reb A and 20% reb B. The water solubility (at 25° C.) of obtained material was about 0.16% (w/v). Example 2 Preparation of Biocatalyst [0048] A strain of Kluyveromyces lactis St-3010 (PureCircle Sdn Bhd Collection of Industrial Microorganisms—Malaysia) was inoculated in 8 liters of sterilized culture medium containing 1.5% lactose, 0.5% rebaudioside A, 1.0% peptone, 0.5% yeast extract, and 0.5% (NH 4 ) 2 HPO 4 (pH 6.0) at 28° C. for 48 hrs with continuous aeration (8 L/min) and agitation (300 rpm). The obtained culture broth was centrifuged at 4,500 g for 20 min on a Sigma 3-16 K (Germany) centrifuge to separate the cells. The cells were subsequently washed with deionized water to obtain 250 mL of biocatalyst. Example 3 Preparation of Stevia Composition [0049] 1 g of rebaudioside A produced by PureCircle Sdn. Bhd. (Malaysia), containing, 98.1% rebaudioside A, 0.3% stevioside, 0.2 rebaudioside C, 0.2% rebaudioside F, 0.4% rebaudioside B and 0.6% rebaudioside D was dissolved in 10 mL 0.1M phosphate buffer (pH 7.0) and about 0.5 mL of biocatalyst prepared according to EXAMPLE 2 was added. The mixture was incubated at 37° C. for 36 hours. Then the mixture was boiled at 100° C. for 15 min and filtered through the layer of activated carbon. The filtrate temperature was adjusted to 20° C. and the pH was adjusted to pH 4.0 with ortho-phosphoric acid. The solution was held under moderate agitation conditions for 4 hours and a precipitate was formed. The precipitate was filtered and washed on the filter with 2000 mL of water. The washed crystals were dried under vacuum to yield about 0.79 g material containing about 2% reb A and about 98% reb B. The water solubility (at 25° C.) of obtained material was about 0.1% (w/v). Example 4 Preparation of Soluble Stevia Composition [0050] 50 g material prepared according to EXAMPLE 1 was mixed with 50 g of water and incubated in thermostatted oil bath. The temperature was increased at 1° C. per minute to 121° C. The mixture was maintained at 121° C. for 1 hour and then the temperature was decreased to room temperature (25° C.) at 1° C. per minute. The solution was dried using YC-015 laboratory spray drier (Shanghai Pilotech Instrument & Equipment Co. Ltd., China) operating at 175° C. inlet and 100° C. outlet temperature. About 45 g of an amorphous powder was obtained with about 25% (w/v) solubility in water (at 25° C.). Example 5 Preparation of Soluble Stevia Composition [0051] 42 g of reb A produced by PureCircle Sdn. Bhd. (Malaysia) with purity of 99.2% (dry basis) and 8 g of reb B prepared according to EXAMPLE 3 were mixed with 50 g of water and incubated in thermostatted oil bath. The temperature was increased at 1° C. per minute to 121° C. The mixture was maintained at 121° C. for 1 hour and then the temperature was decreased to room temperature (25° C.) at 1° C. per minute. The solution was dried using YC-015 laboratory spray drier (Shanghai Pilotech Instrument & Equipment Co. Ltd., China) operating at 175° C. inlet and 100° C. outlet temperature. About 47 g of an amorphous powder was obtained with about 1.5% (w/v) solubility in water (at 25° C.). Example 6 Low-Calorie Orange Juice Drink [0052] Orange concentrate (35%), citric acid (0.35%), ascorbic acid (0.05%), orange red color (0.01%), orange flavor (0.20%), and 0.05% stevia composition, were blended and dissolved completely in water (up to 100%) and pasteurized. The stevia composition was selected from a commercial stevia extract (containing stevioside 26%, rebaudioside A 55%, and 16% of other glycosides), a commercial rebaudioside A (containing 98.2% reb A) or material obtained according to EXAMPLE 5. [0053] The sensory evaluations of the samples are summarized in Table 1. The data shows that the best results can be obtained by using the composition obtained according to EXAMPLE 5. Particularly the drinks prepared with said composition exhibited a rounded and complete flavor profile and mouthfeel. [0000] TABLE 1 Evaluation of orange juice drink samples Comments Sample Flavor Aftertaste Mouthfeel Stevia Extract Sweet, licorice notes Bitterness and Not aftertaste acceptable Reb A Sweet, slight licorice Slight bitterness and Not notes aftertaste acceptable EXAMPLE 5 High quality Clean, no bitterness Full sweetness, pleasant and no aftertaste taste similar to sucrose, rounded and balanced flavor [0054] The same method can be used to prepare juices and juice drinks from other fruits, such as apples, lemons, apricots, cherries, pineapples, mangoes, etc. Example 7 Zero-Calorie Carbonated Beverage [0055] Carbonated beverages according to the formulas presented in Table 2 were prepared. [0000] TABLE 2 Carbonated Beverage Formulas Quantity, % Ingredients Stevia Extract Reb A EXAMPLE 5 Cola flavor 0.340 0.340 0.340 ortho-Phosphoric acid 0.100 0.100 0.100 Sodium citrate 0.310 0.310 0.310 Sodium benzoate 0.018 0.018 0.018 Citric acid 0.018 0.018 0.018 Stevia composition 0.050 0.050 0.050 Carbonated water to 100 to 100 to 100 [0056] The sensory properties were evaluated by 20 panelists. The results are summarized in Table 3. [0000] TABLE 3 Evaluation of zero-calorie carbonated beverage samples Number of panelists detected the attribute Taste attribute Stevia Extract Reb A EXAMPLE 5 Bitter taste 15 10 0 Astringent taste 16  9 0 Aftertaste 14 12 0 Comments Quality of sweet taste Bitter aftertaste Bitter aftertaste Clean (15 of 20) (10 of 20) (20 of 20) Overall evaluation Satisfactory Satisfactory Satisfactory (1 of 20) (5 of 20) (20 of 20) [0057] The above results show that the beverages prepared using the composition obtained according to EXAMPLE 5 possessed the best organoleptic characteristics. Example 8 Diet Cookies [0058] Flour (50.0%), margarine (30.0%) fructose (10.0%), maltitol (8.0%), whole milk (1.0%), salt (0.2%), baking powder (0.15%), vanillin (0.1%) and different stevia compositions (0.03%) were kneaded well in dough-mixing machine. The obtained dough was molded and baked in oven at 200° C. for 15 minutes. The stevia compositions were selected from a commercial stevia extract (containing stevioside 26%, rebaudioside A 55%, and 16% of other glycosides), a commercial rebaudioside A (containing 98.2% reb A) and material obtained according to EXAMPLE 5. [0059] The sensory properties were evaluated by 20 panelists. The best results were obtained in samples containing the composition obtained according to EXAMPLE 5. The panelists noted a rounded and complete flavor profile and mouthfeel. Example 9 Yoghurt [0060] Different stevia compositions (0.03%) and sucrose (4%) were dissolved in low fat milk. The stevia compositions were selected from a commercial stevia extract (containing stevioside 26%, rebaudioside A 55%, and 16% of other glycosides), a commercial rebaudioside A (containing 98.2% reb A) and the material obtained according to EXAMPLE 5. After pasteurizing at 82° C. for 20 minutes, the milk was cooled to 37° C. A starter culture (3%) was added and the mixture was incubated at 37° C. for 6 hours then at 5° C. for 12 hours. [0061] The sensory properties were evaluated by 20 panelists. The best results were obtained in samples containing the composition obtained according to EXAMPLE 5. The panelists noted a rounded and complete flavor profile and mouthfeel. [0062] It is to be understood that the foregoing descriptions and specific embodiments shown herein are merely illustrative of the best mode of the invention and the principles thereof, and that modifications and additions may be easily made by those skilled in the art without departing for the spirit and scope of the invention, which is therefore understood to be limited only by the scope of the appended claims.
Stevia compositions are prepared from steviol glycosides of Stevia rebaudiana Bertoni. The compositions are able to provide a superior taste profile and can be used as sweetness enhancers, flavor enhancers and sweeteners in foods, beverages, cosmetics and pharmaceuticals.
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[0001] This application claims the benefit of U.S. Provisional Application No. 61/443,006, filed Feb. 15, 2011. SUMMARY [0002] The present disclosure is directed to an ice pop making apparatus. More particularly, the disclosure relates to an apparatus to facilitate and speed the freezing of an edible material on a stick via a refrigerant media. The apparatus and method also comprises the subsequent removal of one or more mold inserts containing the frozen edible material from the apparatus. The independent, selectively removable mold insert permits the ready removal of the frozen edible material from the apparatus thereby simplifying operation of the apparatus and providing a sanitary and easy-to-clean unit. The mold insert can then be exposed to ambient conditions or a fluid bath or stream to release the edible material from the mold insert. BACKGROUND [0003] Ice cream and ice pops are commercially-made, frozen confections. There has been an on-going interest in producing home-made ice cream. However, there have been very few products to effectively produce ice pops in the home in an expedited manner. Conventional ice pop makers require a user to leave a fluid drink or mixture in a freezer for an extended period of time. These conventional ice pop makers do not provide instantaneous or near instantaneous gratification. It can take hours for the desired product to freeze into the desired ice pop. In other words, they are not “on demand” or quick ice pop makers. [0004] There are a number of technical challenges to providing ice pops in mere minutes that have yet to be effectively solved. For instance, even where known equipment can quickly produce an ice pop, it can be very difficult to remove the ice pop from the ice pop-making apparatus. In fact, one item of conventional wisdom is that an extraction tool is needed in order to get the frozen material out of the ice pop making apparatus. [0005] Known devices could also be more sanitary and easier to clean. Currently, the edible product that is to be frozen in a quick freeze ice pop maker is placed directly into the apparatus. Residue of the ice pop remains in the apparatus even after the ice pop is removed for consumption. As such, it is necessary to clean the apparatus after each use if the user does not wish to contaminate a second batch of ice pops with the residue of an earlier batch. However, cleaning and washing the apparatus raises the temperature of the apparatus so that the ice pop maker is not, at least temporarily, suitable for its intended purpose. The ice pop maker would have to be returned to a freezer for an extended period thereby defeating the “on demand” operation expected in a quick pop maker. In other words, there is at least a need for an apparatus that has the ability to make consecutive batches of uncontaminated ice pops in an expedited manner. An ice pop maker that would allow an ice pop to be removed in the absence of an extraction tool or release coating would also be desired. [0006] An ice pop maker in accordance with the following disclosure addresses these and/or other shortcomings of conventional quick ice pop makers and otherwise overcomes the disadvantages presented by existing technologies. SUMMARY [0007] The present disclosure is directed to an ice pop maker and method of operating the same wherein a selectively removable ice pop mold insert is employed. For the purposes of this disclosure, an ice pop is a frozen comestible on a stick. The subject ice pop maker makes it surprisingly easy to remove the ice pop from the ice pop maker. A hidden release mechanism may also be employed to facilitate the release of an ice pop mold insert from the ice pop maker apparatus. [0008] The ice pop maker, in accordance with one embodiment of the disclosure, comprises an outer shell, an inner sleeve, refrigerant media, an ice pop stick, a combination stick holder and fluid funnel, and a selectively removable ice pop mold insert. The refrigerant media is stored between the outer shell and inner sleeve. The refrigerant media would typically be some product that freezes below 32 degrees Fahrenheit, such as salt water, propylene glycol, ammonia solution, or the like, although many other fluids could be employed. The refrigerant solution stores sufficient energy to freeze a fluid product placed in the ice pop maker via the mold insert within a matter of minutes. The refrigerant solution is cooled by storing the apparatus in a refrigerated space, such as a freezer, for a period of time. [0009] In one embodiment, the inner sleeve may employ cooling fins that extend from the inner sleeve into the refrigerant media as a heat exchanger. The increased surface area aids the energy transfer between the refrigerant media to the inner sleeve, as further explained below. In at least one of the embodiments, the inner sleeve has one or more apertures extending all the way therethrough. The removable mold insert can be supported in each of the apertures. [0010] The independent, selectively removable ice pop mold insert is sized to fit and nest within the inner sleeve so that the outer walls of the mold insert are in close contact with the walls forming the apertures through the inner sleeve. The ice pop stick is placed in the mold insert and can be held in place by the combination ice pop stick holder and fluid funnel. The mold insert is filled with an edible liquid product either before or after the mold insert is placed in the inner sleeve of the ice pop maker. [0011] The refrigerant media creates a thermal transfer through the inner sleeve and mold insert. When the refrigerant media is properly conditioned, the contents of the mold insert freeze on the ice pop stick in a matter of minutes. Depending on many variables including the starting temperature of the fluid in the mold insert, the storage temperature and length of time the ice pop maker was chilled, and the like, the mold insert contents will generally freeze in about 7 to 15 minutes. Generally, the comestible fluid or mixture freezes in 10 minutes or less. The ice pop (i.e., the frozen material and the stick) is then removed from the mold insert in order to consume the frozen comestible product. [0012] If the product is sufficiently frozen, the ice pop will not automatically separate from the mold insert. Instead, the user can grasp the mold insert to pull the insert with the ice pop in it from the ice pop maker. It is possible that the mold insert can be frozen or bonded to the sleeve or otherwise hard to grasp. A hidden release mechanism, as discussed further below, can be employed to cause a relative motion between the ice pop maker inner sleeve and the mold insert. The relative motion force is sufficient to release the mold insert from the inner sleeve and to extend a portion of the mold insert above the inner sleeve so that the user can grasp and easily remove the mold insert via the ice pop stick or by grasping and pulling the mold insert. [0013] Once the mold insert is removed from the apparatus, the ice pop can be released from the mold insert by subjecting the mold insert to ambient air conditions or, more efficiently, by exposing the exterior surface of the mold insert to a fluid bath or stream. This releases the bond between the ice pop and the inner surface of the mold insert so that the ice pop is easily extracted from the mold insert by hand. A user simply grasps the ice pop stick and retracts it from the mold insert. No extraction tool is needed to remove the ice pop from the mold insert, which simplifies the method of operating the apparatus and lowers costs. A release coating on the mold insert is also not needed, further lowering costs. The composition, texture, etc. of the interior surface of the mold insert is not critical as the temperature differential between the inner surface and outer surface can be used to release the ice pop. [0014] The construction and operation of the subject quick pop maker eliminates any concerns about the ice pop sticking, breaking, or otherwise being damaged in the quick pop maker when trying to remove it via an extraction tool. The subject construction provides a simpler, more cost effective solution to the known problem of removing an ice pop from a quick ice pop maker. [0015] The construction of the inner sleeve, which has an aperture entirely therethrough (i.e., open at both ends), requires two seals with the outer shell. The first seal is located proximate the top end of the ice pop maker. A second seal adjacent the lower edges or bottom end of outer shell and inner sleeve to contain the refrigerant media inside the cavity formed by the inner sleeve and outer shell. Manufacturing tolerances require the careful arrangement and selection of seals. In one embodiment, a flat seal is employed at the top end and a radial seal is used adjacent the connection at the bottom end. [0016] An additional problem is presented by maximizing the surface-to-surface contact between the inner sleeve and mold insert. Any gap between the two surfaces acts as an insulator or decreases thermal conductivity between the two parts. Maximum surface contact is desired for heat transfer purposes. In one embodiment, the inner sleeve is to a final shape and the mold insert is created via spin forming and then lathe finished to a final shape. Tolerances between the two parts can be problematic, but deep drawing or other manufacturing methods could be employed. [0017] As briefly noted above, a hidden release mechanism for the mold insert can be employed. To accomplish one embodiment of the release mechanism, the housing and an inner sleeve are supported upon a base but are spaced apart from the base via post-supported springs. The springs bias the inner sleeve and outer shell away from the base. Downward force on the outer shell or inner sleeve overcomes the spring bias. The inner sleeve and outer shell have a downward range of motion towards the apparatus' base. The mold insert, however, is supported on an upward projecting member of the base or otherwise have a more limited range of downward motion. The upward projecting members are axially aligned with the aperture in the inner sleeve and limit the downward motion of the mold insert. In other words, the upward projecting members act as a “stop” and do allow the mold insert to move downwards to the same extent that the inner shell can move. [0018] Since the mold insert has a more limited range of motion, or none at all, the downward force on the outer shell causes relative movement between the inner sleeve and the mold insert. As a result, surface tension or bonding between the mold insert and inner sleeve that might impede the removal of the mold insert from the inner sleeve is overcome. A portion of the mold insert is also exposed. A user can then easily remove the mold insert from the ice pop maker apparatus by pulling the ice pop stick or directly grasping and retracting the mold insert. [0019] An ice pop maker in accordance with the present disclosure is easy to operate and clean and is relatively inexpensive to make and own. The ice pop maker does not require an extraction tool or any specialized release coatings. Moreover, the maker is more sanitary than known ice pop makers in that the portion of the apparatus that contacts the edible material (i.e., the mold insert) is independently removable. Any remnants of the edible material can easily be cleaned from the mold insert without having to wash the inner sleeve or outer shell that house the refrigerant media. As such, cleaning the mold inserts does not dissipate the energy stored in the refrigerant solution as it would if one were required to wash the reside directly off the apparatus itself. Overall, the subject ice pop maker is relatively easy to clean, is more sanitary, is easier to operate, and should cost less to manufacture than known ice pop makers. [0020] Further features and advantages of the present invention will become apparent to those of skill in the art from the following detailed description of a preferred embodiment taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0021] FIG. 1 depicts one embodiment of the subject ice pop making apparatus with removable mold insert as disclosed herein; [0022] FIG. 2 is a top view thereof; [0023] FIG. 3 is an exploded view thereof; [0024] FIG. 4 is an exploded, side, cross-sectional view thereof; [0025] FIG. 5A is a cross-sectional view from one end of the apparatus as disclosed herein; [0026] FIG. 5B is an additional cross-section side view thereof; [0027] FIG. 6 is a close up cross-sectional view thereof; and [0028] FIG. 7 is a perspective view from the bottom and one end of the subject apparatus as disclosed herein. DETAILED DESCRIPTION [0029] The present disclosure is directed to an ice pop maker and the method of using the same. The ice pop maker is described in terms of various embodiments disclosed and illustrated herein. The subject ice pop maker comprises a novel construction and method of operation. The ice pop maker includes various components including a selectively removable ice pop mold insert that provides for a more sanitary apparatus with easier operation than known devices. A release mechanism can facilitate the removal of the mold insert. The subject apparatus will freeze a comestible fluid or mixture in a very short period of time, typically in 10 minutes or less. Of course, the present invention is not limited to the specific embodiments as follows but also includes variations and equivalent structures that would be apparent to one of skill in the art upon review of the disclosure as a whole. [0030] As illustrated herein, and with specific reference to FIGS. 1 and 2 , the quick pop making apparatus 10 comprises, in at least one embodiment, an outer shell 12 and an inner sleeve 14 that are joined together to create a sealed cavity therebetween. A refrigerant media (not illustrated) is stored between outer shell 12 and inner sleeve 14 in the cavity. The refrigerant media would typically be some product that freezes below 32 degrees Fahrenheit, such as salt water, propylene glycol, ammonia solution, or the like, although many other fluids could be employed. Ice pop maker 10 is stored in a freezer for a period of time to lower the temperature of the refrigerant media. This thermal energy is stored in the refrigerant media for a period of time when ice pop maker 10 is removed from the freezer. [0031] Outer shell 12 can be plastic, metal, or any suitable fluid-tight material. Outer shell 12 forms the outer and lower walls of the refrigerant media cavity. For cost savings and to prevent energy loss of the refrigerant media though outer shell 12 , a plastic shell is preferred but not required. A bezel 13 is snap-fit or otherwise secured to the upper edge of shell 12 . Bezel 13 can be formed from plastic or other suitable material, although it is thought a material with low thermal conductivity is preferred so as to protect a user from a cold surface. To that end, bezel 13 can further include handles 15 to facilitate handling and operation of ice pop maker 10 . [0032] Outer shell 12 is fastened to inner sleeve 14 by screws or other known fasteners or fastening mechanism. Inner sleeve 14 forms the upper wall of the refrigerant media cavity as well as at least one passageway therethrough. [0033] For reasons elaborated on below, inner sleeve 14 is preferably a material with a relatively high rate of thermal conductivity, such as a metal. A plurality of cooling fins 17 (see, in particular, FIG. 5A-6 ) extends from inner sleeve 14 into the refrigerant media cavity created by inner sleeve 14 and outer shell 12 . Cooling fins 17 also exhibit a high rate of thermal conductivity and are submerged in the refrigerant media. Fins 17 provide a greater surface area of contact between inner sleeve 14 and the refrigerant media. [0034] Referencing also FIGS. 3 and 4 , and as briefly noted above, inner sleeve 14 comprises at least one aperture 16 extending therethrough from an upper end of inner sleeve 14 to a bottom end of inner sleeve 14 . The upper end of aperture 16 is chamfered outwardly. Sleeve 14 may be mechanically stamped, deep-drawn, die-cast or produced by other suitable means. A die-cast aluminum construction is preferred but not required. [0035] An independent and selectively removable mold insert 18 can be inserted into inner sleeve 14 via aperture 16 . Mold insert 18 is sized to nest within inner sleeve 14 and includes a first open end and a second closed end. While mold insert 18 is illustrated herein as having a circular cross section and a tapered body from the open end to the closed end, which corresponds to the shape of aperture 16 , the specific shapes of aperture 16 and mold insert 18 are not critical. For the most efficient operation of ice pop maker 10 , the outer dimensions of mold insert 18 should closely conform to the dimensions of aperture 16 so as to maximize the surface contact between the two. Mold insert 18 can rest on the chamfered portion of aperture 16 (i.e., it is suspended within aperture 16 ) or stand on or be supported by an optional base projection 40 adjacent the lower end of aperture 16 . [0036] An upper seal 20 is placed between inner sleeve 14 and outer shell 12 to hold the two components together more securely and to prevent the escape of any refrigerant media from the cavity. Upper seal 20 can be a known gasket or seal, such as a flat seal. Aperture 16 through inner sleeve 14 requires there be an additional seal at the lower end of inner sleeve 14 . It has been found that a radial seal 22 effectively joins the bottom end of inner sleeve 14 to outer shell 12 and also prevents the escape of the refrigerant media from the cavity created by outer shell 12 and inner sleeve 14 . Other types of seals or gaskets may be suitable for lower seal 22 . [0037] Mold insert 18 can be filled with an edible liquid material before or after being inserted into aperture 16 of inner sleeve 14 . A funnel 24 can nest in the upper opening of mold insert 18 to guide a fluid into mold insert 18 . Funnel 24 includes an opening therethrough and a tapered cross-sectional shape. A bridge 26 extends across the funnel opening and includes a stick opening. An ice pop stick 28 is supported in the stick opening to retain stick 28 in position in mold insert 18 . The stick opening can accommodate molded plastic sticks, conventional wooden ice pop sticks (i.e., Popsicle™ sticks), and the like. [0038] The chilled refrigerant media extracts thermal energy from the fluid or mixture in mold insert 18 through inner sleeve 14 and mold insert 18 . The media has enough stored energy to freeze the fluid or mixture on stick 28 to form an ice pop. Mold insert 18 may be plastic, metal or other viable material. A metal mold insert 18 is thought to effectively allow the rapid transfer of thermal energy between the refrigerant media and the interior of the removable mold insert 18 . In addition, in the event mold insert 18 is removed from the apparatus while containing an ice pop, exposing a metal mold insert 18 to a warm environment (e.g., running tap water, warm air, or the like) will quickly cause the frozen material in mold insert 18 to loosen from mold insert 18 due to the effective heat transfer provided by metal and, in part, due to the expansion and contraction of the metal. In any event, no extraction tool is required to remove the resulting ice pop. A release coating is also not needed. The independent, selectively removable mold insert 18 provides for the easy operation of ice pop maker 10 , easy cleaning of the same, and facilitates the removal of the ice pop from ice pop maker 10 . [0039] By this removable mold insert construction, the liquid or material used to create the ice pop does not touch inner sleeve 14 . Consequently, inner sleeve 14 is not contaminated with foodstuff at any point. In fact, inner sleeve 14 cannot independently retain any fluid introduced via aperture 16 as inner aperture 16 is open on both ends of inner sleeve 14 . In other words, inner sleeve 14 cannot act as a reservoir. [0040] Stick 28 is envisioned as a one-piece, injection-molded plastic stick, which would be reusable and machine washable. Funnel 24 can be independent of stick 28 so that it is operable with a variety of different stick types including traditional, wooden ice pop sticks. Funnel 24 could alternatively be a molded collar proximate to and integral with one end of stick 28 . [0041] Overall, the removal of the ice pop from ice pop maker 10 is facilitated by the use of a removable mold insert 18 . While the thermal exchange between the refrigerant media and fluid or mixture to be frozen occurs through two intervening layers (i.e., the wall of inner sleeve 14 and mold insert 18 ), it was surprisingly found that the rapid freezing of the edible product could be achieved. Removing the ice pop and mold insert 18 from ice pop maker 10 aided the cleaning of the ice pop making apparatus 10 and made it possible to produce consecutive batches of ice pops without any cross-contamination issues. [0042] A removable mold insert, as disclosed herein, produces a method of using the subject apparatus that is unique to quick ice pop makers. To operate the ice pop maker 10 , a user would place ice pop maker in a freezer for an amount of time sufficient to chill and condition the refrigerant solution. The apparatus is removed from the freezer. Ice pop mold insert 18 , with or without any contents, is placed in the upper end of aperture 16 of inner sleeve 14 . The combination funnel and stick holder 24 and ice pop stick 28 are placed in ice pop mold insert 18 . Unless already completed, a fluid or mixture is added to ice pop mold insert 18 . Advantageously, the fluid can be added to mold insert 18 prior to mold insert 18 being placed in quick pop maker 10 so that any spills do not contaminate or freeze to ice pop maker 10 . [0043] In a period of minutes, the fluid or mixture in mold insert 18 will be frozen to stick 28 . A user can grasp mold insert 18 and remove mold insert 18 from ice pop maker 10 . The exposure to ambient air conditions or a bath or stream of fluid will release the ice pop from mold insert 18 . If a second or subsequent ice pops are desired, a user can clean mold insert 18 , dry it off, and reinsert mold insert 18 for further use. Cross contamination between ice pop batches is prevented and it is not necessary or suggested to clean outer shell 12 or inner sleeve 14 between batches, which would dissipate the energy stored in the refrigerant media. [0044] It is possible for mold insert 18 to create sufficient surface bonding or otherwise freeze to inner sleeve 14 such that an optional mold insert release mechanism might be employed. In one embodiment, the mold insert release mechanism comprises a relative motion system between inner sleeve 14 and mold insert 18 . [0045] In further detail, and with reference to the figures, including FIGS. 4-7 , outer shell 12 and inner sleeve 14 are supported upon a base 38 but spaced apart from base 38 via post-supported springs 39 . Springs 39 bias inner sleeve 14 and outer shell 12 away from base 38 . Downward force on outer shell 12 or inner sleeve 14 overcomes the spring bias thereby allowing inner sleeve 14 and outer shell 12 a range of downward motion. Mold insert 18 , however, is either suspended in aperture 16 of sleeve 14 or is supported by base 38 in a manner that does not permit the same, or any, range of downward motion. Therefore, the downward movement of outer shell 12 and inner sleeve 14 causes relative movement between inner sleeve 14 and mold insert 18 . As a result, surface tension, bonding or any other binding force that might impede the removal of mold insert 18 from inner sleeve 14 is overcome. In addition, the downward movement of inner sleeve 14 relative to mold insert 18 can physically present or expose mold insert 18 above the top wall of inner sleeve 14 so that mold insert 18 can be more easily grasped by a user. The user then easily removes mold insert 18 from ice pop maker 10 . The ice pop is released from mold insert 18 in the manner described above. [0046] In still further detail, as perhaps best illustrated in the close-up, sectional illustration of FIG. 6 , outer shell 12 includes a circumferential lower lip 50 that fits within a groove 52 provided by base 38 . A plurality of posts 54 extend down from the bottom side of outer shell 12 . Posts 54 are received by pockets 56 of base 38 and extend through apertures in the pockets. Fasteners are attached to the distal end of posts 54 . The fasteners do not fit through the pocket openings so that outer shell 12 and inner sleeve 14 are secured to base 38 . Posts 54 can move down through the pocket apertures. However, posts 54 are naturally biased to the uppermost position by the bias force of springs 39 on outer shell 12 . The post fasteners limit the upward range of motion. [0047] Springs 39 can comprise coil or other suitable types of springs that are situated around some or all of posts 54 . Springs 39 bias shell 12 and sleeve 14 away from base 38 . As a result, the fasteners are brought into contact with base 38 . In this position, lip 50 is positioned in groove 52 but there is downward range of motion. A user pushes down on outer shell 12 or inner sleeve 14 . The spring bias is defeated and posts 54 move down through the pocket apertures. Lip 50 also moves down within groove 52 until it abuts base 38 . [0048] Base 38 further includes upwardly extending base projections 40 that limit the downward motion of mold insert 18 relative to inner sleeve 14 . Mold insert 18 is either in contact with projections 40 at all times or are suspended in aperture 16 just above base projections 40 . Therefore, mold inserts 18 have little to no downward range of motion and specifically less of a downward range of motion relative to the base than do the outer shell 12 and/or inner sleeve 14 . Therefore, pushing down on outer shell 12 ‘releases’ mold insert 18 from inner sleeve 14 . A user grasps and removes mold insert 18 from ice pop maker 10 . [0049] While the present disclosure has been described with reference to specific embodiments thereof, it will be understood that numerous variations, modifications and additional embodiments are possible, and all such variations, modifications, and embodiments are to be regarded as being within the spirit and scope of the invention.
An ice pop making apparatus for rapid or “on demand” ice pop production involves an apparatus and method whereby one or more mold inserts are removable from the ice pop making apparatus subsequent to an edible product being frozen in the mold insert. The mold insert is exposed to ambient conditions or a fluid bath or stream to release the edible material from the mold insert. The mold insert may be cleaned and/or filled remotely from the ice pop making apparatus so that the ice pop making apparatus will be kept clean and there is no cross-contamination of edible products or flavors between consecutive batches of ice pops.
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BACKGROUND INFORMATION 1. Field of the Invention The invention relates to the field of harvesting berry harvesters. More particularly, the invention relates to a walk-behind harvester. More particularly yet, the invention relates to blueberry harvester for use in small-scale fields. 2. Description of the Prior Art Blueberry harvesting has traditionally been done by handpickers or rakers who walk along a row and rake through the bushes. The work is tedious and back-breaking, particularly when harvesting wild blueberries, as the bushes are low to the ground and the picker works in a bent-over position. Handpickers, being paid by the box of berries picked, often leave berries hanging on the bush if they feel that the amount of berries is meager, and wander on to more lucrative areas, resulting in a loss to the landowner. Many attempts have been made to construct a mechanical harvester to rake blueberry bushes in a manner that removes all or most of the berries, without damaging the bush. In addition to raking the berries from the bush, the harvester also has to transport the berries into a container. Other considerations for a mechanical harvester are that it have a motorized ground travel, be lightweight enough not create ruts in the ground, and be safe to operate. The prior art discloses many walk-behind harvesting machines, designed primarily for harvesting cranberries. Because these harvesters must travel over sandy bog, good traction on sandy ground is a major concern. For that reason, they are heavy and have drive rollers that extend across the width of the harvester and that roll right over the vines. The berry-harvesting head of these harvesters has a system of rotating rakes and a pruning mechanism. The rotating rakes lift the cranberry vines from the ground and collect the berries onto the rakes, and simultaneously, the pruning mechanism prunes the vines. The machines are heavy and cumbersome and require extensive adaptation if they are to be used in blueberry fields. Also, due to the density of cranberries on the vines, the harvesting head rotates at a speed that is too slow for efficient blueberry raking. A typical conventional cranberry harvester that has, in the past, been used in blueberry fields is the Darlington harvester as disclosed in U.S. Pat. No. 2,780,905 (1957). The Darlington harvester picks only about 100-150 boxes of blueberries in a day, not much more than a handpicker. It is not possible to adapt the speed of the head to blueberry raking conditions because the mechanical action controlling the rakes through a rotation of the head is complex, and increasing the speed results in serious damage to the harvesting head. Furthermore, the diameter of harvesting head of the Darlington machine is too small for effective blueberry raking. For example, as a result of the small diameter, when the rakes come down into the blueberry bush, they are below the top of the bush and, therefore, they miss the blueberries growing in the upper portion of the bush. An additional disadvantage of the Darlington harvester is that it does not have a safety shut-off that effectively shuts off the harvester when the operator relinquishes control. The harvester is only switched off when the off switch is actuated. This presents a safety hazard to the operator and to others working nearby in the field, and a source of property damage to the owner of the blueberry fields, because it will continue on in ground travel even after the operator has completely let go of it. For safety reasons, it is critical that, when the operator relinquish control of the machine, it shut down immediately. What is needed, therefore, is a walk-behind berry harvester that is lightweight and easily maneuverable. What is further needed is such a harvester that effectively removes berries from a bush and transports the berries to a container, without damaging the bush or the berries. What is yet further needed is such a harvester that is operable at speeds that are determined by the harvesting conditions of the bushes in a section of a field. What is still yet further needed is such a harvester that is safe to operate. BRIEF SUMMARY OF THE INVENTION For the reasons cited above, it is an object of the present invention to provide a berry harvester that is lightweight and easily maneuverable. It is a further object to provide such a harvester that effectively rakes berries from a bush and deposits the berries in a container provided on the harvester. It is a yet further object to provide such a harvester that is operable at various speeds, adaptable to the berry harvesting conditions in a particular field or area of the field. What is still yet further needed is such a harvester on which the ground travel will shut off automatically when the operator relinquishes control of the harvester. The objects of the invention are achieved by providing a walk-behind berry harvester having a rotatable rake head, a conveyor, and a single drive means for controlling the travel speed of the harvester and the conveyor, the speed of rotation of the rake head. The harvester according to the invention is suitable for raking any type of berry that grows on a relatively low bush. The application that was initially envisioned for the harvester according to the invention was that of a blueberry harvester, and thus, reference is often made herein to blueberries. It should be understood, however, the term “blueberry” is representative of any type of berry that can be raked from a bush. The berry harvester according to the invention is a walk-behind wheeled vehicle, with a rock guard extending from the forward end of the harvester, close to the ground, and a rake head mounted on the frame of the vehicle above the rock guard. A conveyor is mounted rearward of the rake head, and a container support rearward of the conveyor. The wheels, the conveyor, and the rake head are driven by a motor mounted on the frame of the harvester. Control devices that control the drive mechanisms for the wheels and rake head are mounted on a handle. The operator of the harvester can independently switch the ground travel and/or the rake head on or off. The drive for the conveyor is coupled with that of the rake head. Thus, when drive for the rake head is enabled, the conveyor is operating. The speed of rotation of the rake head is linked to the ground travel speed of the harvester, as is the speed of the conveyor. When in operation, the rake head rotates through the bushes and rakes up berries. The berries are flung from the rakes into a conveyor, which carries them away and drops them into a berry container that is provided beneath the upper edge of the conveyor. A mount for additional berry containers is provided on the frame, for easy access by the operator. The heart of the invention is the rake head, which extends across the entire forward end of the harvester. The rake head comprises a rake-head shaft with flanges mounted at each end. A plurality of rakes or combs are mounted on the flanges and extend parallel to the rake-head shaft, evenly spaced on the flanges, equidistant from the rake-head shaft. Thus, as the rake head rotates, each individual rake travels through a circular path defined by its distance from the rake-head shaft. Each individual rake includes a rake bar that contains a row of teeth. Each rake is rotatably mounted on the rake head and the rotation of the rake is controlled so that it maintains a particular orientation throughout a complete rotation of the rake head. In the harvester according to the present invention, the orientation is a sloping downward angle, relative to the vertical, to facilitate discharge of the berries from the rake. As the harvester travels forward, the rotation direction of the forward edge of the rake head is in the direction of travel and the rake at the forward edge is travelling through a downward arc around the forward edge of the rake head. As the rake head rotates, it brings that rake down into the blueberry bush from above and draws it through the bush, from the forward side of the bush, relative to the direction of travel of the harvester, to the rearward side, collecting raked berries on the rake. As the rake head continues to rotate, that rake reverses its direction of travel, now traveling through an upward arc. The raked berries that are collected on the rake are then flung from the rake onto the conveyor, which transports them upward and drops them into a berry collection box. Ideally, the diameter of the rake head is large enough so that the individual rake, as it rotates through the highest point in the rotation cycle, comes down toward the bush and enters at the top of the bush. The conveyor is an endless conveyor that travels upward away from a lower section of the rake head toward the rear of the harvester. The uppermost part of the conveyor extends rearward over a berry collection box that is supported on the frame beneath it. The conveyor collects the berries as they are flung from the individual rake and dumps them into the berry collection box as the particular section of conveyor passes the highest point of the conveyor and begins its downward travel. A single drive means with a main drive shaft provides the power to drive the wheels of the harvester, the conveyor, the rake head and the individual rakes. Power is applied simultaneously or selectively to the wheels and/or the rake head and conveyor. It is sometimes desirable to selectively apply power to the conveyor when the harvester is at a standstill, for example, when berry raking is completed, but some berries are have not completed the travel into the berry collection box. For this reason, the single drive means allows the operator to selectively apply power to the conveyor and the rake head, but not to the wheels, and vice versa. Thus, it is possible to operate the rake head and conveyor when the harvester is not traveling forward and also to drive the harvester forward without operating the conveyor. This selective application of power is accomplished by a two-belt drive system, with both belts driven by the main drive shaft. The belt pulley for the drive wheels is mounted directly on the shaft; the belt pulley for the rake head and conveyor is mounted on a bushing. The drive wheel pulley and the bushing for the rake head spin idly on the shaft when the respective belt is not tightened. Power is applied to the respective belt by tightening the belt. The harvester is provided with operator handles for maneuvering the harvester. A lever is provided on each handle that controls a belt tightener. Thus, one handle has a lever for tightening the belt around the drive wheel pulley; the other handle a lever for tightening the belt around the rake head pulley. By gripping both handles and levers, drive is applied to both the drive wheels and the rake head and conveyor. By releasing one or the other lever, the corresponding belt is loosened and, depending on the particular setup, the corresponding pulley then spins idly about the main drive shaft (which is still being driven by the motor). During normal operation, the rake head and the individual rakes rotate at a speed that is relative to the speed of the ground travel, that is, the head makes one complete rotation over a certain distance of ground travel. Thus, if the harvester is traveling forward at a rapid rate, the head and the rakes rotate at a correspondingly rapid rate. Similarly, if the harvester is traveling forward at a slow rate, the head and rakes rotate at a correspondingly slow rate. Control of the rate of rotation of the rake head and the rakes is provided by a suitable mechanical system, such as a planetary gear system or an analogous chain and sprocket assembly. A central gear or sprocket, referred to hereinafter as a rake-head gear, is mounted at one end of the central head shaft. A planetary gear or sprocket, referred to hereinafter as a rake drive means, is mounted at the end of each individual rake and chains or gears that mesh with the rake-head gear couple the individual rake with the central head shaft. A belt-pulley link is provided between the rake head and the conveyor. The rake-head drive means, as mentioned above, is a belt-pulley drive mounted on the main drive shaft and coupled with a pulley on the central head shaft. Assuming the rake-head drive belt is tightened, as the main drive shaft rotates, the conveyor and the central head shaft, as well as the individual rakes, are in operation. An additional useful feature of the apparatus according to the invention is a supplemental-box mount that is provided on the frame. The berry boxes used for collecting berries have a particular standardized contour on the bottom, which allows the boxes to be stacked. The supplemental-box mount is a support bar that is adapted to receive and securely support a berry box in a manner that does not interfere with operation of the harvester, yet provides convenient access to the operator. Several boxes are stackable on the supplemental-box mount. This allows the operator to fill a box and deposit it for pick-up, and to quickly replace it with an empty berry box so that raking can continue with a minimum of interruption. This is of advantage to harvester operators, because conventional harvesters do not allow them to carry along extra berry boxes and they normally have to return to some particular location at the perimeter of the field to deposit the filled berry box and pick up an empty box. This may be time-consuming if the harvester operator is in the middle of a large field when the berry box is full. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of the apparatus according to the invention. FIG. 2 is a perspective view of the rake head. FIG. 3A is a perspective view of the rake head, illustrating its mounting on the frame and the system of power transfer to the rake head and the rakes. FIG. 3B is a side view of the power-drive end of the rake head, illustrating the interconnected drive means for the center head shaft and the individual rakes. FIG. 3C is a side view of the harvester, illustrating the transfer of power from the rake-head drive shaft to the rake head. FIG. 4 is a perspective view of the harvester, ullustrating power transfer to the conveyor. FIG. 5 is a schematic illustration of power transfer from the motor to the rake head and to the ground-travel wheels. FIG. 6 is a perspective view of the harvester, from the rear, illustrating the belt-tensioner cables and actuators, the support area for the berry collection box, and the supplemental-box mount. DETAILED DESCRIPTION OF THE INVENTION FIG. 1 is a schematic illustration of the major components of a walk-behind berry harvester 100 according to the invention. A forward end of the harvester 100 is designated as 100 A, and a rearward end as 100 B. The berry harvester 100 comprises a rake head 20 and a conveyor system 40 , both of which are mounted on a frame 2 . The rake head 20 comprises one or more rakes 22 . The drive system will be discussed in detail below, but for now, understand that the harvester 100 is propelled forward on motor-driven drive wheels 4 . Also mounted on the frame 2 at the forward end 100 A beneath the rake head 20 is a rock guard 5 . Just above the upper edge of the rock guard 5 is a baffle 7 that curves rearward and upward toward a lower end 40 B of the conveyor 40 . Both the rock guard 5 and the baffle 7 have a curvature that corresponds to that of the outer perimeter 21 of the rake head 20 . Beneath the baffle 7 is a ground roller 6 that rolls along the ground surface G. A support area 8 for a berry collection box B is provided at the rearward end 100 B of the harvester 100 and a chute 9 is mounted between an upper end 40 A of the conveyor 40 and the berry collection box B. As the harvester 100 travels across the ground G in berry harvesting mode, the rake head 20 rotates in the direction indicated by head rotation arrow H, scoops berries from the bushes and drops them onto the conveyor 40 , which carries them upward and drops them over the upper end 40 A of the conveyor so that they land in the berry collection box B. The rock guard 5 protects the rake head 20 from hitting rocks and the baffle 7 serves to collect stray berries that don't make it onto the conveyor 40 when they are initially dropped from the rake 22 . The stray berries are then picked up the by next following rake 22 . FIG. 2 is a perspective view of the rake head 20 ready for assembly onto the harvester 100 . The rake head 20 is bounded at each end by a head flange 28 . Extending between the two head flanges 28 are a center head shaft 30 and, in the embodiment shown, four rakes 22 , each rake 22 constructed of a rake bar 24 having a plurality of rake teeth 26 . Depending on the ideal speed with which the harvester 100 is setup to run, any number of rakes 22 , including one rake 22 , may be assembled on the rake head 20 for most efficient operation of the harvester 100 . FIGS. 3A-3C illustrate a rake-head drive 20 A means for driving the rake head 20 and the rake bars 22 . In these illustrations, the frame 2 is shown either not at all or only incompletely for purposes of illustration. The rake head 20 is mounted on the frame 2 by means of the center head shaft 30 . The rake-head drive means 20 A comprises gear and/or chain-and-sprocket assemblies to drive the rotation of the rake head 20 as well as control the orientation of the rakes 22 . In the embodiment shown, chain-and-sprocket assemblies are used, although it is understood that a system of gears or gears with chains may also be used. As shown in FIG. 3A , the center head shaft 30 and the rake bars 24 are mounted in the end flange 28 . The rake bars are differentiated now as 24 A- 24 D. A double-track sprocket 32 is mounted on the end of the center head shaft 30 and two of the rake bars 24 B and 24 D, whereby the sprocket assembled at the end of rake bar 24 D is not visible. A first rake-bar drive chain 34 is assembled on a first track of the double-track sprockets 32 . Single sprockets 33 are mounted on rake bars 22 A and 22 C. A second rake-bar drive chain 36 A is assembled on a second track of the double-track sprocket 32 on rake bar 24 B and on the single sprocket 33 at the end of rake bar 22 C. Similarly, a third rake-bar drive chain 36 B is assembled on the second track of the double-track sprocket 32 at the end of rake bar 24 D and on the single sprocket 33 of rake bar 24 A. FIG. 3B is a side view of the end flange 28 , showing the interconnected arrangement of the chains 34 , 36 A, 36 B. FIG. 3C is a side view of the rake head 20 , mounted on the frame 2 , showing the power transmission from a rake-head drive shaft 12 to the rake-head drive means 20 A. As shown, a gear 38 is mounted on the end of the center head shaft 30 and a rake-head drive chain 39 is assembled on the gear 38 and a first rake-head sprocket or gear 37 mounted on the end of the rake-head drive shaft 12 . The rake-head drive shaft 12 will be discussed in greater detail below. As mentioned earlier, the rake bar 24 is constructed to rotate about its longitudinal axis so as to maintain a constant sloping angle of the rake teeth 26 , regardless of the instantaneous circumferential location of the rake bar 24 in the rotational cycle of the rake head 20 . Ideally, if more than one rake 22 is mounted on the rake head 20 , the teeth on each rake 22 deflect from the vertical to the same degree and direction. This parallel orientation of the rake teeth 26 of the individual rakes 22 is best seen in FIG. 3 A. As the center head shaft 30 is rotated by means of the rake-head drive chain 39 and the gear 38 , the rake bars 24 are each forced to rotate about their longitudinal axes by means of the interconnected arrangement of the rake-head drive means 20 A described above. FIG. 4 shows the conveyor 40 and a conveyor drive means 42 that controls the operation of the conveyor 40 and its operating speed. The conveyor 40 , a wide, flexible, ridged belt made of a rigid synthetic material, is mounted just rearward of the rake head 20 . A conveyor-drive shaft 44 that is splined or toothed over at least a portion of it extends into the conveyor 40 at its upper end 40 A, meshes with a mating geometry of the inside of the upper end 40 A, and drives the conveyor 40 directly. The rake-head drive shaft 12 , as well as the rake head 20 and rakes 22 rotate in a forward direction, while the conveyor travels in a rearward direction. Thus, the direction of rotation of the conveyor-drive shaft 44 has to be opposite the direction of rotation of the rake-head drive shaft 12 . This is accomplished by running a conveyor-drive chain 45 around a direction-reversing sprocket assembly 48 , which includes a first sprocket 48 A and a second sprocket 48 B, and around the first rake-head gear 37 , as shown in FIG. 4 . With the arrangement shown, the drive power to the rake head 20 and the conveyor 40 is provided by the rotation of the first rake-head gear 37 . Thus, the speed of the conveyor 40 is attuned to the rotational speed of the rake head 20 ; the faster the rake head 20 rotates, the faster the conveyor 40 runs. FIG. 5 is a schematic illustration of the power take-off from the motor M. The motor M is mounted on a support attached to the frame 2 , neither of which is shown in this FIG. A power shaft 50 comes off the motor M and provides the force to drive the wheels 4 , the rake head 20 , and the conveyor 40 . In the embodiment shown, a first belt-and-pulley assembly 52 provides the power to the rake head 20 and the conveyor 40 , and a second belt-and-pulley assembly 54 provides power to the ground-travel drive wheels 4 . Mounted on the power shaft 50 are two driver pulleys 52 A, 54 A. A central drive shaft 64 extends across a substantial portion of the width of the berry harvester 100 , parallel to the power shaft 50 . Mounted on one end of the central drive shaft 64 is a first transfer pulley 52 B. A second transfer pulley 54 B is mounted on a second end 12 B of the rake head drive shaft 12 , which is mounted on the central drive shaft 64 . The transfer pulleys 52 B, 54 B are drivably linked to the driver pulleys 52 A and 54 A by corresponding pulley belts 52 C, 54 C. With continued reference to FIG. 5 , an axle 60 connects the two drives wheels 4 . The axle 60 runs parallel to the central drive shaft 64 . Mounted on the central drive shaft 64 is a first gear 62 A; mounted on the axle is a second gear 62 B. A gear chain 62 C links the first and second gears 62 A, 62 B and selectively engages the second gear 62 B. When the second gear 62 B is engaged, power is transmitted to the drive wheels 4 . When the motor M is turned on, the central drive shaft 64 rotates at a constant speed. Tightening one or both of the pulley belts 52 C, 54 C causes the corresponding transfer pulleys 52 B, 54 B to rotate. Each of the two driver pulleys 52 A, 54 A is drivable, independent of the other. Thus, it is possible to engage the first belt-and-pulley assembly 52 , ie., to operate the rake head 20 and the conveyor 40 , while leaving the second belt-and-pulley assembly 54 that engages the ground-travel drive wheels 4 disengaged. The opposite is also the case. It is possible to engage the ground-travel drive wheels 4 , so as to maneuver the harvester 100 across the ground surface, while leaving the rake head 20 and conveyor 40 disengaged. FIG. 6 is a perspective view of the berry harvester 100 , as seen from the rearward end 100 B. Extending upward from the frame 2 are handles 2 H. Mounted on one handle 2 H is a first belt tensioner mechanism 57 and on the other handle 2 H a second belt tensioner 67 . The first belt tensioner mechanism 57 serves to engage the first belt-and-pulley assembly 52 and the second belt tensioner mechanism 67 engages the second belt-and-pulley assembly 54 . The first belt tensioner mechanism 57 includes a first pulley cable 56 that is attached to the first belt-and-pulley assembly 52 and when the belt tensioner mechanism 57 is depressed, the belt 52 C is tightened on the belt-and-pulley assembly 52 and power is transmitted to the rake-head 20 and the conveyor 40 . The second belt-tensioner mechanism 67 includes a second pulley cable 66 that is attached to the second belt-and-pulley assembly 54 and, when depressed, the belt 54 C is tightened on the second belt-and-pulley assembly 54 and power is transmitted to the ground-travel drive wheels 4 . The first and second belt tensioner mechanisms 57 , 67 are designed such that they are easy to use when the operator is handling the harvester 100 . By simply letting go of one or the other belt tensioner mechanism on the handle, the corresponding belt-and-pulley assembly is immediately disengaged, resulting in immediate stopping of the corresponding rake head and/or ground-travel drive wheels. Thus, to interrupt all operation of the harvester 100 , both the first and second belt-and-pulley assemblies 52 , 54 are immediately disengaged when the operator lets go of both handles 2 H. This is a strong safety feature, as it prevents operation of the harvester 100 without operator control. Also shown in FIG. 6 is the chute 9 that aids in guiding berries from the conveyor 40 into a berry collection box that is positionable on the support area 8 . In the embodiment shown, the support area 8 is constructed as a metal frame that holds the conventional berry collection box, which has a contoured bottom. Divider plates 8 A are provided in the support area 8 that jut into the contours on the bottom of the box. The support area 8 shown here is designed to firmly and securely hold the berry collection box yet not add any more weight than necessary to the harvester 100 . For that reason, it is constructed of metal tubing, although it is understood other designs and constructions of the support area 8 may well be suitable for holding a berry collection box and are included within the scope of the present invention. A supplemental-box mount 80 that is attached to the frame 2 of the harvester 100 is also shown in FIG. 6 . Again, the supplemental-box mount 80 is designed to add as little weight as possible to the harvester 100 and other designs are possible. The particular embodiment of the supplemental-box mount 80 shown is a simple structure designed to fit into the contours on the bottom of the conventional berry collection box. The berry collection boxes are stackable upon each other, and any number of berry collection boxes is stackable on the box mount 80 . The box mount 80 provides a simple and convenient means for the operator of the berry harvester 100 to carry extra berry collection boxes while processing a field. This allows the operator to set aside a full berry collection box for later pick-up and quickly and easily replace it with a fresh box. It is understood that the embodiments described herein are merely illustrative of the present invention. Variations in the construction of the harvester may be contemplated by one skilled in the art without limiting the intended scope of the invention herein disclosed and as defined by the following claims.
Apparatus for raking berries, particularly blueberries. The apparatus has a frame supported on wheels, a rake head, a berry conveyor, support for a berry box, and a side support for stacking additional empty berry boxes. The motor-driven apparatus provides independent operation of ground travel and berry collecting operation. The rakes maintain a constant orientation relative to the vertical throughout the rotation of the rake head.
0
This is a continuation of U.S. application Ser. No. 10/146,934 filed May 17, 2002 now U.S. Pat. No. 7,037,426, which is a continuation-in-part of U.S. Ser. No. 09/889,352 filed Jul. 17, 2001, issued as U.S. Pat. No. 6,790,360 on Sep. 14, 2004, which is a National Stage entry of PCT/CA00/01359 filed Nov. 15, 2000. All of the applications listed above are incorporated herein, in their entirety, by this reference to them. FIELD OF THE INVENTION This invention relates to filtering membranes and particularly to modules of immersed, suction driven, ultrafiltration or microfiltration membranes used to filter water or wastewater. BACKGROUND OF THE INVENTION Submerged membranes are used to treat liquids containing solids to produce a filtered liquid lean in solids and an unfiltered retentate rich in solids. For example, submerged membranes are used to withdraw substantially clean water from wastewater and to withdraw potable water from well water or surface water. Immersed membranes are generally arranged in modules which comprise the membranes and headers attached to the membranes. The modules are immersed in a tank of water containing solids. A transmembrane pressure (“TMP”) is applied across the membrane walls which causes filtered water to permeate through the membrane walls. Solids are rejected by the membranes and remain in the tank water to be biologically or chemically treated or drained from the tank. U.S. Pat. No. 5,639,373, issued to Zenon Environmental Inc. on Jun. 17, 1997, describes one such module using hollow fibre membranes. In this module, hollow fibre membranes are held in fluid communication with a pair of vertically spaced headers. TMP is provided by suction on the lumens of the fibres through the headers. Other modules are shown in U.S. Pat. No. 5,783,083 issued to Zenon Environmental Inc. on Jul. 21, 1998, PCT Publication No. WO 98/28066 filed on Dec. 18, 1997 by Memtec America Corporation and European Patent Application No. EP 0 931 582 filed Aug. 22, 1997 by Mitsubishi Rayon Co., Ltd. As discussed in these documents, various means are provided for fixing modules together generally permanently into larger units. SUMMARY OF THE INVENTION It is an object of the present invention to improve on the prior art. It is another object of the present invention to provide a filtration apparatus comprising a plurality of elements, for example, elements of immersed, suction driven, hollow fibre membranes, mounted to a frame. Embodiments of the invention provide few components to interfere with the flow of tank water through the apparatus, efficient permeate pipe connections, elements that may be removed easily and without interfering with adjacent elements, elements that may be economically manufactured to a wide range of sizes, an apparatus that may be assembled with variable spacing between elements, and a distance between headers of the elements that can be altered to account for membrane shrinkage in use. The objects of the invention are met by the combinations of features, steps or both described in the claims. The following summary may not describe all necessary features of the invention which may reside in a sub-combination of the following features or in a combination of some or all of the following features and features described in other parts of this document. In various aspects of the invention, the invention is directed at an apparatus for filtering a liquid in a tank having a plurality of elements, and a frame for holding the elements while they are immersed in the liquid. The elements have a plurality of hollow fibre membranes attached to and suspended between an upper header and a lower header. The membranes are in fluid communication with one or more permeate channels in one or more of the headers. Releasable attachments between the headers and the frame allow the frame to releasably hold the elements by their headers. While the frame is holding the elements, the elements themselves do not have any means for holding the headers in position relative to each other. For example, if the frame were removed, the headers would be free to move out of position relative to each other. As a result, the size and configuration of the frame determines the positions of the upper and lower headers of each element relative to each other. When out of the frame, the elements may be inserted into a separate carrying frame, if desired, for transport or handling. An assembled filtration apparatus, which may be called a cassette, has a plurality of elements held such that the membranes are generally vertical when immersed in the liquid in the tank. The headers may be elongated in shape and held in a generally horizontal orientation when the membranes are immersed in the tank. The frame holds the elements so as to provide a spacing between adjacent elements and allows tank water to rise vertically through the frame and past the elements. To assemble a filtration apparatus, the upper headers are slid into the frame, for example, through track and slider mechanism that may support the element whenever about one quarter of the length of the upper header is inserted into the frame. The lower header may similarly slide into the frame, for example through another track and slider mechanism. Or, while the element is supported by the upper header, the lower header may be swung into position to attach to releasable supports which engage with the ends of the lower header. The frame holds or restrains the elements in place, but the restraint provided by the frame may be released for a selected element individually. The selected element may be removed by reversing the steps for assembly without disassembling the remainder of the module. Connections between the permeate channels and one or more permeate collection tubes attached to the frame are releasable and resealable connections which are made or broken automatically by the movements involved in inserting or removing an element into or out of the frame. The frame may have cross bars located on uprights, the cross bars holding the elements. The vertical location of the cross bars may be changed from time to time to maintain the membranes in a slightly slackened condition although their length may decrease in use. Aerators are mounted generally below the elements and supply scouring bubbles to the cassette and circulate tank water. The elements may be narrow, each element being a rectangular skein of hollow fibres having an effective thickness of between 4 and 8 rows of hollow fibres. The headers, which may be extruded, may be thin to not greatly increase the width of the element. The attachments between the frame and the elements are positioned to provide horizontal spaces between adjacent elements, preferably at least one third of the width of the headers measured in the direction of the horizontal spacing, to promote penetration of the bubbles and tank water into the elements. Elements may be placed back to back in pairs separated by permeate pipes. The connections between the permeate pipes and the elements release when an element is pulled out of the cassette and reseal when the element is replaced in the cassette. Thus a single element can be removed for maintenance without disconnecting other parts of the permeate pipe network. A large permeate collector may be connected to a small group of elements by a short local permeate pipe with a valve that permits the small group of elements to be isolated. Thus, while waiting for repair, permeation can continue with the remaining elements. The large permeate collector may be located above the water surface and connect to an even larger collector which may be located on the edges of a tank. The headers may be made of an extrusion which may be cut to any desired length and capped with caps. The horizontal distance between the cross bars of the frame can be altered by changing the dimensions of the frame or the location of the cross bars relative to the frame. Longer or shorter cross bars can be used which hold fewer or more elements. The vertical distance between cross bars can be altered by changing the dimensions of the frame or the location of the cross bars relative to the frame. Accordingly, a cassette may be produced in a variety of sizes by altering the length of cut of one or more of the header extrusion, the cross bars or the frame members. BRIEF DESCRIPTION OF THE DRAWINGS Preferred embodiments of the present invention will now be described with reference to the following figures. FIG. 1 is a somewhat schematic front elevation of a filtering element. FIG. 2 is a somewhat schematic side elevation of the filtering element of FIG. 1 . FIG. 3 is an isometric view of a header of an element of a first embodiment. FIG. 4 is an elevation of the end of 4 adjacent headers of FIG. 3 . FIG. 5 is an isometric view of a frame for a cassette with headers attached. FIG. 6 is a close up of the top of FIG. 5 . FIG. 7 is a diagrammatic drawing of part of two elements placed back to back and connected to a permeate pipe. FIG. 8A is a perspective view of a header and releasable attachment of a second embodiment. FIG. 8B is a side view of the header of FIG. 8A . FIGS. 9 and 10 are assembled and exploded views of a component of the releasable attachment of FIG. 8 . FIG. 11 is a perspective view of parts of a frame and releasable attachments of the second embodiment. FIGS. 12 , 13 and 14 are perspective, front and side views of a frame and parts of releasable attachments of the second embodiment. FIG. 15A is a perspective view of an element of a third embodiment. FIG. 15B is a close up view of part of FIG. 15A . FIGS. 16A , 16 B and 16 C are schematic views of elements and permeate connections of a third embodiment. FIG. 17 is a perspective view of a header and parts of a releasable attachment of the third embodiment. FIGS. 18A and 18B are side views of the releasable attachment between a lower header and frame of the third embodiment. DETAILED DESCRIPTION OF THE INVENTION A First Embodiment The following paragraphs describe a first embodiment that is shown in FIGS. 1 to 7 . Although the description below may at times refer to specific figures, some components discussed may be shown only in others of FIGS. 1 to 7 . FIGS. 1 and 2 show simplified front and side elevations respectively of a filtering element 10 . The element 10 has a plurality of hollow fibre membranes 12 in the form of a rectangular skein 14 suspended between an upper header 16 and a lower header 18 . The rectangular skeins 14 may be between four and eight layers of membranes 12 deep (five layers being shown in FIG. 2 ), optionally up to 12 layers deep, and are in the range of several tens of membranes 12 wide. The element 10 itself does not include any permanently attached means for holding the headers 16 , 18 in position relative to each other but the element 10 may be connected to a carrying frame if required for transport or handling. The lack of means for holding the headers 16 , 18 in position relative to each other improves the flow of tank water about the element 10 and avoids a possible source of damage to the membranes 12 . The membranes 12 typically have an outside diameter between 0.4 mm and 4.0 mm. The length of the membranes 12 is chosen to maximize flux for a given cost according to relationships known in the art and is typically between 400 mm and 1,800 mm. The membranes 12 have an average pore size in the microfiltration or ultrafiltration range, preferably between 0.003 microns and 10 microns and more preferably between 0.02 microns and 1 micron. The upper header 16 has a permeate channel 20 in fluid communication with the lumens of the membranes 12 . The membranes 12 in FIGS. 1 and 2 are sealed in the lower header 18 , but the lower header 18 may also have a permeate channel in fluid communication with the lumens of the membranes 12 to permit permeation from both ends of the membranes 12 . The membranes 12 are potted into the upper header 16 (and any other permeating header) such that the membranes 12 are all closely spaced apart from each other. Potting resin completely surrounds the outsides of the end of each membrane 12 to provide a watertight seal so that water can only enter the permeate channel after first flowing though the membranes 12 . Suitable potting resins include polyurethane, epoxy, rubberized epoxy and silicone resin. One or more resins may also be used in combination to meet objectives of strength and providing a soft interface with the membranes 12 and avoiding cutting edges. A potting method like that described in U.S. Pat. No. 5,639,373, which is incorporated herein by this reference, may be used to pot layers of membranes 12 . Other potting methods known in the art, include methods that produce non-layered or random arrangements of the membranes, may also be used. In particular, the methods described in Canadian Patent Application No. 2,308,234, filed May 5, 2000 by Zenon Environmental Inc., and in U.S. application Ser. No. 09/847,338, filed on May 3, 2001 by Rabie et al., both of which are incorporated herein by this reference, may be used. The thickness of the assembled mass of membranes 12 may be between 18 and 40 mm. Headers 16 , 18 to accommodate such masses of membranes may be 40 to 50 mm wide, typically 40 mm. The potting densities may be between 10% and 40%. For example, an element 10 may use membranes 12 as used in commercially available ZW 500 (TM) modules made by Zenon Environmental Inc. which have an outside diameter of about 2 mm, an un-potted length (meaning the unsupported length of membrane 12 between the upper header 16 and lower header 18 ) of 1,600 to 1,900 mm, and a pore size of approximately 0.1 microns. Referring to FIG. 3 , the upper header 16 is shown. The lower header 18 is the same would be mounted in an inverted position. The upper header 16 includes a body 22 preferably extruded from a suitable plastic such as PVC or ABS. The extrusion can be cut to a wide range of sizes as desired. A back cap 24 is attached to the body 22 by gluing or welding. The body 22 includes a key 26 running the length of the top of the upper header 16 . The back cap 24 is shaped to extend the key 26 . The key 26 fits into slots in cross bars 30 of which only short sections are shown. The back cap 24 has an upper wing 32 and a lower wing 34 . The back cap 24 and the body 22 each have an upper channel 36 and a lower channel 38 . A front cap is attached to the front of the body 22 but has been omitted from FIG. 3 to show the cross-section of the body 22 . The front cap need not have any wings 32 , 34 but it does have channels 36 , 38 , Referring to FIG. 4 , four upper headers 16 are attached to a section of cross bar 30 spaced to leave about 20 to 25 mm between adjacent upper header 16 . The lower headers 18 are similarly attached to another crossbar 30 but in an inverted position. The cross bar 30 can be cut to any desired length. To avoid the need to cut slots 28 into a long cross bar, the one piece cross bar 30 shown can be replaced with a standard extruded section, such as an inverted “C” channel, which supports any suitable hanger containing a slot 28 . In that case, the standard extrusion is cut to a desired length and an appropriate number of hangers are attached or slid into it which allows the number of elements 10 to be easily varied. The upper headers 16 and their associated upper wings 32 , lower wings 34 , upper channels 36 and lower channels 38 are all designated a, b, c, d to indicate which of those parts is associated with which upper header 16 . As shown, the upper wing 32 of a first upper header 16 engages the upper channel 36 of an adjacent upper header 16 and the lower wing 34 of the first upper header 16 engages the lower channel 38 of an adjacent upper header 16 on the other side. But, the upper wings 32 and lower wings 34 do not interfere with each other in the direction of the length of the upper headers 16 . Accordingly, each upper header 16 can be moved into or out of its position in a direction parallel to the upper header 16 . Further, although the cross bar 30 provides support at only one point, a moving upper header 16 is supported and vertically positioned by its adjacent upper headers 16 aong its travel. This makes it much easier to insert or withdraw an element 10 despite the lack of (a) means within the element 10 itself for maintaining separation between the headers 16 , 18 or (b) continuous frame channels paralleling the length of each header 16 , 18 which would add many parts, add to the overall cost and manufacturing time, as well as interfere with bubbles and tank water moving past the headers 16 , 18 . A releasable catch can be incorporated into the slot 28 and key 26 structure, typically at the front only, to provide a releasable restraint in the direction of the headers 16 , 18 . Referring to FIGS. 5 and 6 , a cassette 50 includes a frame 40 for holding several elements 10 . The frame 40 includes top and bottom, front and back cross bars 30 , uprights 42 and struts 44 as shown. Three elements 10 (with membranes 12 removed for clarity) are shown being withdrawn from the frame 40 . Extra blank (ie. unpotted) headers 48 are optionally included between the uprights 42 to provide support for the wings 32 , 34 of the first element 10 on each side. An element 10 may be completely withdrawn and then supported by hand or a single element carrying frame (not shown) may be placed against the frame 40 . The element 10 is then slid into the carrying frame which may allow the element 10 to be more easily worked with. The length of the uprights 42 is chosen as appropriate for any desired length of membranes 12 . The vertical distance between cross bars 30 is chosen so that the membranes 12 will be slightly slacked, their free length being, for example, 0.1% to 2% more than the distance between proximal faces of the headers 16 , 18 . Particularly in wastewater applications where the tank water will be warm, ie. 30-50 C, the membranes 12 may shrink within the first few weeks or months of operation. To account for this shrinkage, the uprights 42 may be provided with a series of mounting holes 46 which allow at least one set of the upper or lower cross bars 30 to be moved to maintain the membranes 12 in a slightly slackened position. Although not shown, a suitable aerator (designs are known in the art) may be mounted to the frame 40 or placed on a tank floor below the frame 40 to provide bubbles from below the cassette 50 . The aerator is designed and positioned to encourage bubbles and tank water to flow upwards through the frame 40 and past the elements 10 , through the spaces between adjacent elements 10 and between the membranes 12 within the elements 10 . To connect the headers 16 , 18 to permeate pipes, the back of any permeating headers 16 , 18 are fitted with header permeate connections 52 that can be released and resealed to a permeate pipe located behind the headers 16 , 18 and permit movement of the element 10 parallel to the headers 16 , 18 . For example, FIGS. 5 and 6 show commercially available clip on adapters sold under the trade mark UNI-SPRAY. These connectors 52 , however, require a clip to be released at the back of the element 10 which is difficult to do if the elements 10 are placed back to back to share common permeate pipes. Referring to FIG. 7 , pairs of cassettes 50 (partially shown, frames 40 omitted, for example) are placed back to back with a local permeate pipe 60 in between them. The frames 40 (not shown) of the two cassettes 50 are tied together to maintain a fixed distance between them. The upper headers 16 (and lower headers 18 if they are permeating) include male fittings 54 which releasably form a seal with a female fitting 56 attached to the local permeate pipe 60 . The seal is made by means of O-rings 58 fitted into O-ring grooves 66 in the male fittings 54 . The male fittings 54 are thus connected to a local permeate pipe 60 which may service a small number of elements 10 , ie. 2-6 elements 10 . The local permeate pipe 60 has an isolation valve 62 , for example a ball valve located above the water line, which permits the small group of elements 10 to be isolated from the rest of the cassette 50 . The local permeate pipes 60 connect into a larger permeate collector 64 which may be located at the level of even larger collector which may be located at the edge of a tank. Thus, the necessary connections may be made simply and without expensive flexible pipes. If the bottom headers 18 are also permeating, appropriate male fittings 54 are attached to the bottom headers 18 at the level of female fittings 56 on or in communication with a local permeate pipe extension 68 which may be an extension of the local permeate pipe 60 . If the bottom headers 18 are permeating headers, then the top headers may not be. A Second Embodiment The following paragraphs describe a second embodiment, parts of which are shown in FIGS. 8 to 14 . Although the description below may at times refer to specific figures, some components discussed may be shown only in others of FIGS. 8 to 14 or in figures discussed with other embodiments. The second embodiment is similar to the first embodiment in many respects. Aspects of the second embodiment that do not differ substantially from the first embodiment may not be described in the following paragraphs which will concentrate on the features of the second embodiment which differ from the first. A second lower header 118 is shown in FIGS. 8A and 8B . A second upper header 116 (not shown in this figure) is similar, but mounted in an inverted position. The second lower header 118 has a second key 126 on its lower surface that may be continuous like that of the second header 18 . Optionally, the second key 126 may be segmented, for example as shown in FIG. 8B , which helps prevent the second key 126 from sticking in the second slot 128 , which will be described below. The second lower header 118 does not have an upper channel 36 or a lower channel 38 . A second back cap 124 of the second lower header 188 also does not have an upper wing 32 or a lower wing 34 , but rather is of a similar section as the second body 122 of the second lower header. A second front cap 125 is fitted to the front of the second body and has a pull tool fitting 180 adapted to allow a tool to pull on the second lower header 118 for removal. FIG. 8A also shows a track piece 182 located below the second lower header 118 . A similar track piece 182 would be located above the second upper header 116 . The track piece 182 provides part of a continuous second slot 128 that the second keys 126 may slide into and be supported by. The track piece 182 is supported at both ends by the cross bars 30 . For example, in the embodiment shown, one end of the track piece 182 fits over and is supported by an abutment 184 attached to the side of a permeate pipe stub 186 resting on a cross bar 30 . The permeate pipe stub 186 is sealed at its lower end and ready to be connected to a local permeate pipe extension 68 (not shown in FIG. 8A , refer to FIG. 7 ) at its upper end. The permeate pipe stub 186 also has female fittings 56 in fluid communication with the inside of the permeate pipe stub 186 . The female fittings 56 are located and oriented so that when the second lower header 118 is fully inserted in the second slot 128 , a male fitting 54 (not visible) is sealingly connected to the female fitting 56 . The other end of the track piece 182 in the embodiment shown is supported by a locking clip 188 which both supports the track piece 182 relative to the cross bar 30 , but also completes the second slot 128 and releasably locks the second lower header 118 in position when the second lower header 118 is fully inserted in the second slot 128 . The locking clip 188 is held in place by fitting into a cross bar channel 192 and is located along the length of the cross bar 30 by interaction with a positioning hole 190 . The description above also applies, but with inverted orientation, for the second upper headers 116 . FIGS. 9 and 10 show the locking clip 188 in greater detail. A locking clip abutment 194 is sized and shaped to fit into and support the track piece 182 . A peg 196 fits into a peg slot 198 to provide a means for locating the locking clip 188 over a positioning hole 190 . A catch 200 fits over the body of the locking clip 188 and, in an unbent position, fills a part of the second slot 128 . However, the catch 200 has tapered faces so that the catch 200 can move out of the second slot when a second key 126 is slid into the second slot 128 . After the end of a second key 126 , or series of discontinuous second keys 126 passes the catch 200 , they are prevented from moving back out of the second slot 126 . However, a release hole 202 also provides access to the tapered faces of the catch 200 . By inserting a rod into the release hole 202 , the catch 200 can be held open to allow a second key 126 to be pulled back out of the second slot 128 . The locking clip 188 also has a foot 204 sized to engage with the cross bar channel 192 . FIG. 11 shows how the bottom part of a frame 40 ready to receive second elements 110 . As shown, a pair of struts 44 are attached to a central cross bar 30 a and two end cross bars 30 b , only one visible. Four brackets 206 are provided to attach to uprights 42 . The central cross bar 30 a supports a number of permeate pipe stubs 186 which in turn have abutments 184 holding track pieces 182 . The end cross bars 30 b support locking clips 188 which support the other ends of the track pieces 182 . If the second lower headers 118 were not permeating headers, then the central cross bar 30 a would also be used to support locking clips 188 . FIGS. 12 to 14 show a more fully assembled frame 40 forming part of a second cassette 150 . A second assembly like that shown in FIG. 11 is inverted and placed over the assembly of FIG. 11 . Uprights 42 hold the two assemblies together. The connection between the uprights 42 and one or both of the assemblies may be made though slots 208 which allow the distance between the two assemblies to be adjusted to fit the second elements 110 . The distance between the two assemblies may also be adjusted after the membranes 12 have been used, for example, to account for shrinking. The upper track pieces 182 are held at the central cross bar 30 a by flow through permeate stubs 210 which connect the local permeate pipe extensions 68 to local permeate pipes 60 which are in turn connected to a permeate collector 64 mounted to upper mounting tabs 212 at the top of the frame. Lower mounting tabs 214 at the bottom of the frame 40 may be used to mount an aerator grid below the second cassette 150 . Only one of various components, such as second elements 110 , local permeate pipe extensions 68 , local permeate pipes 60 and isolation valves 62 , are shown for clarity, but these components would be repeated across the second cassette 150 . Also, although the second cassette 150 is shown as configured to collect permeate from second upper headers 116 and second lower headers 118 , it may be adapted for use with permeating second upper headers 116 only by replacing the permeate pipe stubs 186 shown on the lower central cross bar 30 a with locking clips 188 and replacing the flow through permeate stubs 210 shown at the upper central cross bar 30 b with permeate pipe stubs 186 . For use with permeating second lower headers 118 only, the female fittings 56 of the flow through permeate stubs 210 are plugged up or altered flow through permeate stubs not having female fittings 56 are provided. A Third Embodiment The following paragraphs describe a third embodiment, parts of which are shown in FIGS. 15 to 18 , or in figures discussed with other embodiments. The third embodiment is similar to the first and second embodiments in many respects. Aspects of the third embodiment that do not differ substantially from the first or second embodiment may not be described in the following paragraphs which will concentrate on the features of the third embodiment which differ from the first or second. FIGS. 15A and 15B show a third element 310 . The third element 310 has a third lower header 318 and a third upper header 316 which are similar to the second lower header 118 and second upper header 116 . However, the third headers 316 , 318 differ, for example, in having third keys 326 , third back caps 324 and third front caps 325 unlike related components of the second headers 116 , 118 . The third element 310 shown has two permeating third headers 316 , 318 , but like previous elements may be made with either the third lower header 318 not a permeating header or the third upper header 316 not a permeating header. Referring to FIGS. 15 B and 16 A,B,C, the third headers 316 , 318 have third back end caps 324 with male fittings 54 that are offset from the center of the third back end caps 324 . Third back end caps 324 A (shown schematically in FIGS. 16 A,B,C as having truncated tops) have a male fittings 54 offset to one side of the center while third back end caps 324 B (shown schematically in FIG. 16 A,B,C as having rounded tops) have a male fitting 54 offset to the other side of the center. By placing one of third back end cap 324 A and one third back end cap 324 B on the third headers 316 , 318 , third elements 310 I and 310 II can be made have male fittings 54 offset to opposite sides. If both of the third headers 316 , 318 are permeating, then separate third elements 310 I and 310 II need not be made, as one will be an inverted version of the other. In conjunction with third permeate pipe stubs 386 having female fittings 56 on either side, a variable horizontal spacing between third elements 310 I and 310 II can be achieved with a single design of third permeate pipe stub 386 and without needing a third permeate pipe stub 386 for each third element 310 . In particular, as shown in FIGS. 16A and 16C , swapping third element 310 I for third element 310 II (or turning each third element 310 I or 310 II over if both third headers 316 , 318 are permeating) significantly alters the space between third elements 310 I and 310 II. By using third permeate pipe stubs 386 that can be mounted at various positions along a cross bar 30 , two different spacings of all of the third elements 310 of a third cassette 350 can be achieved without requiring a separate local permeate pipe 60 and local permeate pipe extension 68 for each third element 310 and with only one small component, the third back caps 324 , manufactured in two versions. The ability to have variable spacing is useful, for example, because a wider spacing can be chosen for wastewater applications and a narrower spacing chosen for drinking water filtration. As shown in FIG. 16B , an intermediate spacing may also be achieved by using a pair of third elements 310 II. The same intermediate spacing may also be achieved by using a pair of third elements 310 I. The comments made in the paragraph above regarding the third permeate pipe stubs 386 similarly apply to third flow through permeate stubs 310 . The third permeate stubs 310 also have a pair of mounting pins 220 on each side to support the end of the third track piece 382 (to be described below) at either spacing. Similar pairs of mounting pins 220 may also be provided on the third permeate pipe stubs 386 if they will also be used to support the ends of third track pieces 383 , although this is optional as will be described further below. FIGS. 15B and 17 show a third key 326 that which has a key ridge 224 . Although FIGS. 15B and 17 show only a third upper header 316 , the third lower header 318 is the same, but is mounted in an inverted orientation. Similarly, other components of FIG. 17 may all be used in inverted orientation at the bottom of a third cassette 350 . The key ridge 324 provides a line of contact between the distal surface of the third key 326 and the third track piece 382 . Similarly, the edges of the third track piece 382 curl inwards to provide a line of contact with the proximal surfaces of the third key 326 . These lines of contact are less prone to fouling than planes of contact. FIG. 17 also shows the connection between one end of the third track pieces 382 and a cross bar 30 . The connection between the other end of the third track piece 382 and the third permeate pipe stubs 386 , or third flow through permeate stubs 310 , was discussed above. The end shown in FIGS. 15B and 17 is supported on a pin (not visible) one a track mounting plate 226 mounted on a cross bar 30 . The track mounting plate 226 also supports a third lock 388 that assists in keeping the third track piece 382 in position. The third lock 388 also mates with a twist knob 228 to allow the third upper header 316 to be releasably secured when it has been fully inserted into the third slot 328 . As an alternative to using an inverted version of the components shown in FIG. 17 to releasably attach the third lower header 318 , FIGS. 18A and 18B show how the third lower header 318 may be Releasably attached to the frame 40 without using a third track piece 382 . Referring to FIG. 18A , the third top header 316 (not shown) is partially inserted, for example between about one half to three quarters of the way, into the third track piece 382 (not shown). At this point, the third lower header 318 hangs from the membranes 12 . The third lower header 318 is then pushed into its final position which is shown in FIG. 18B . Because the third upper header 316 was only partially inserted, the third lower header 318 arcs upwards slightly. Through trial and error or measurement and calculation, a position of the third upper header 316 can be determined at which the upward movement of the third lower header 318 , despite the excess length of the membranes 12 required to produce slackened membranes 12 when the third element 310 is fully installed, allows the male fitting 54 to meet the female fitting 56 and allows the twist knob 228 to meet and be releasably connected to the third lock 388 . The third upper header 318 is then fully inserted which restores the slack in the membranes 12 . The twist knob 228 of the third upper header 316 is then engaged with the third lock 388 of the upper part of the frame 40 . The embodiments described above are examples of the invention only. Modifications and other embodiments within the scope of the invention will be apparent to those skilled in the art. The scope of the invention is defined by the following claims.
An apparatus for filtering a liquid in a tank has a plurality of elements and a frame for holding the elements while they are immersed in the liquid. The elements have a plurality of hollow fibre membranes attached to and suspended between an upper header and a lower header. The membranes are in fluid communication with one or more permeate channels in one or more of the headers. Releasable attachments between the headers and the frame allow the frame to releasably hold the elements by their headers. The size and configuration of the frame determines the positions of the upper and lower headers of each element relative to each other. Connections between the permeate channels and one or more permeate collection tubes attached to the frame are releasable and resealable connections which are made or broken automatically by the movements involved in inserting or removing an element into or out of the frame.
1
FIELD OF THE INVENTION [0001] The present application is generally related to a video game controller, and specifically to one that detects the movement of a player's feet optically. BACKGROUND OF THE INVENTION [0002] Video games are an enjoyable diversion and the video game industry enjoys ever increasing sales and penetration. Some time ago, video games that make a player physically dance were developed. In particular, an arcade game console called Dance Dance Revolution is extremely popular in Japanese arcades. Dancing games are now available for home video game systems and are gaining in popularity. [0003] Some prior controllers for use with dancing games generally involve a large mat that covers the full game play area. A player dances on top of the mat and the mat transmits the user's position to the game system. These dance mats tend to wear out quickly when used by zealous gamers that frequently and vigorously dance upon them. Furthermore, they are bulky and inconvenient to use and transport. Other prior controllers detect the movement of the player by sensing when an optical or other type of beam is interrupted on a path from a transmitter to a receiver. In these devices, when the beam is not received by the receiver, the player's position is determined to be in the path from transmitter to receiver. [0004] There exists a need for a reliable, accurate, and portable game controller for use with dancing and other games that does not deteriorate with regular gaming usage. SUMMARY OF INVENTION [0005] The present invention comprises a corded or cordless game controller that detects a player's foot position. It can be used with any game that requires a user to move his feet around from position to position, but is especially useful in dancing related video games. It can be used with any home video gaming system. [0006] The controller is a small unit that fits in between a player's feet. The player then dances around it, rather than on it. Although the player may stand on the platform, and in some embodiments, game control buttons are activated from the top of the platform, the dance steps are performed and detected outside of the perimeter of the controller. Unlike in dance pads or mats where the user plays within the footprint of the mat and lands on it repeatedly, the present invention utilizes non-impact position detection, and is therefore more durable as it does not wear out due to repeated impact. Furthermore, it is significantly more compact than those designs. [0007] The controller of the present invention transmits a beam from a detection unit of the controller, which is reflected off the user or player's foot back towards the controller. It is then sensed by a receiver of the given detection unit. The use of this reflective technique allows the controller to have a small footprint. Two or more signals that overlap, each sent from different locations and received by the receiver, identify the location of an object (e.g. a foot). A single receiver, or receiving module is used in each detection unit of the preferred embodiment. This is achieved with time division modulation as several beams can be sent and received well within the time a foot is in a given location. The time sent and/or received indicates which beam was reflected and the position of the foot. However, some embodiments may utilize more than one receiver per detection unit. [0008] In a preferred embodiment a detection unit is located on each of the left, right, top and bottom sides of the controller, for a total of four detection units. Game control buttons that allow a user to navigate and select from menus of the game are located at one or more of the corners of the controller. In other embodiments they may be otherwise distributed. They can be activated from above or from the side, but are preferably activated from the side as it is more convenient for a user during play, and lessens inadvertent strikes that tend to occur with a top activated switch when a user's foot travels over the top of the controller in the heat of game play. [0009] In a preferred embodiment, the detection modules will sense an object at the left, right, top and bottom of the controller, but not at the corners. This eliminates inadvertent detection of a move (at or near a corner) when a player's foot sweeps from one side to another, for instance from a position near the top of the controller to position at the right of the controller. [0010] In a preferred embodiment, not all pairs of overlapping signals indicate a game location, and therefore, those that do not are ignored. This improves accuracy of the controller by minimizing the detection of unwanted reflections from an object other than a player's foot or from the player's foot when it is in a location outside of the area meant to define a position of the controller and the game being played. For example, inadvertent reflections from nearby walls or other objects are not interpreted as steps of the player's feet. In some embodiments, the optical emitters are directed substantially parallel to the ground while in others they are angled toward the ground such that they hit the ground near the controller. In such an embodiment, a foot can be detected before the beam hits the ground, or by the weakened signal after it has been reflected by the ground, so long as it is reflected back to the controller a short enough distance thereafter that it will have sufficient energy at the detector. Otherwise, in the case of a ground reflected signal reflected far from the controller, it will not have the proper trajectory back to the receiver, or will otherwise have insufficient energy to be deemed a foot position or dance step. BRIEF DESCRIPTION OF THE DRAWINGS [0011] FIG. 1A is top view of game controller 100 , an embodiment of the present invention. [0012] FIG. 1B is a profile elevation of game controller 100 . [0013] FIG. 1C is a diagram illustrating the game play zones 112 surrounding game controller 100 . [0014] FIG. 1D is a diagram illustrating activation of foot activated game control switches/buttons 104 in directions 105 . [0015] FIG. 1E is an exploded view of game controller 100 . [0016] FIG. 2A is an illustration of a position detection unit 120 of game controller 100 , and the footprint of a detection area or game play zone 112 . [0017] FIG. 2B is an illustration of the areas defined by the overlap of beams created by position detection unit 120 . [0018] FIG. 2C is reproduction of Table 1, a table of the areas defined by the overlap of the beams shown in FIG. 2B . [0019] FIG. 3 is an illustration of reflection from an object inside a predefined detection area. [0020] FIG. 4 is an illustration of reflection from objects outside the predefined detection areas. [0021] FIG. 5 is an illustration of a reflection from a nearby object 150 outside of the game play zones 112 shown in FIG. 1C . [0022] FIG. 6 is a side view elevation of position detection unit 120 illustrating the path of signals emitted and received by the unit, relative to the ground and bottom of game controller 100 . DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0023] FIG. 1A is a top view of game controller 100 , an embodiment of the present invention. A game player can stand on controller 100 and steps around the platform of controller 100 to play the game. For example, if the game instructs the player to step to the player's right the player will then step on the ground to the right side of controller 100 . Likewise, the position of the player's feet will be detected relative to controller 100 for actions required in front, back or to the left of the player's relative position. Arrows 110 A, B, C, and D serve to indicate to a user that the controller is sensitive to positions at the front side, right side, back side, and left side respectively. In some embodiments the arrows may be of translucent material and will illuminate in sync with the user's detected movements. [0024] Game control buttons or switches 104 A, B, C, and D are located at the corners of the controller 100 . The preferred embodiment of controller 100 is substantially rectangular as shown, with the corner clipped or rounded. Other embodiments may have other shapes. The game control buttons may in certain embodiments be activated from the top of the controller platform, or, as illustrated, may be activated with a motion and in a direction parallel to the ground. This way, a user can touch the switch with either his toe or heel from around the perimeter of the controller. For example, a user may choose to back her heel into button 104 A, while it may be more convenient for a user to kick or touch button 104 B with the front of her foot. [0025] FIG. 1B is a profile elevation of game controller 100 seen in FIG. 1B . Controller 106 comprises a housing with a top plate 106 and a base plate 108 . The electronic components (not shown) are generally between top plate 106 and base plate 108 . Controller 100 preferably communicates wirelessly to a video game system, although corded communication is provided in certain embodiments. Logic of the controller is accomplished either with a microprocessor or other logic circuitry. Wireless communication is preferably according to the well known Bluetooth radio specification 2.0, although any RF transmission spectrum and protocol can be utilized. The controller also preferably interfaces as a human interface device regardless of the transmission frequency and protocol. Base plate 108 rests upon the floor during game play or otherwise. [0026] FIG. 1C is a diagram illustrating the game play zones 112 surrounding game controller 100 . In the preferred embodiments, game play is detected at the front, right, back and left sides of the controller 100 , as represented by zones 112 A, 112 B, 112 C, and 112 D respectively. As seen by the axes, the front of the controller may also be thought of as the north side, or the zero degree point of the axes. For simplicity the zones are depicted in FIG. 1C as rectangular, although in reality the geometry of the zones is more complex, as will be described later. Many different positions can be determined within each of the zones. In the preferred embodiment, a user's position will not be detected in areas 114 , adjacent to the corners of the controller. In games that do not require position detection location in those areas, this reduces false detection as the user's feet pass though the areas 114 . In other embodiments, position may be detected all around the controller, including locations at or near the corners. [0027] FIG. 1D is a diagram illustrating activation of foot activated game control switches or buttons 104 in directions 105 . Button 104 A may be activated by a stroke in direction 105 A. Direction 105 A a can be anywhere from 0 to 90 degrees but is preferably between 30 and 60 degrees. Likewise, button 104 B may be activated by a stroke in direction 105 B, which can be anywhere from 90 to 180 degrees, but is preferably between 120 and 150 degrees, button 104 C may be activated by a stroke in direction 105 C, which can be anywhere from 180 to 270 degrees, but is preferably between 210 and 240 degrees, and button 104 D may be activated by a stroke in direction 105 D, which can be anywhere from 270 to 360 degrees but is preferably between 300 and 330 degrees. [0028] FIG. 1E is an exploded view of game controller 100 . In addition to the components previously described, position detection units 120 A, 120 B, 120 C, and 120 D can be seen. These serve to detect the position of the user's feet around the game controller. Of course, greater or fewer position detection units may be utilized depending on the embodiment and geometry of controller 100 . [0029] FIG. 2A is an illustration of a position detection unit 120 ( 120 A, B, C, or D) of game controller 100 , and the footprint of game play zone 112 , where the position of a user's foot will be detected. Each position detection unit 120 comprises two optical illumination modules 122 and 126 . Each optical illumination module comprises a group of 2 or more of illumination chambers. Module 122 comprises illumination chambers 124 A, 124 B, and 124 C. Module 126 comprises chambers 124 D, 124 E, and 124 F. Each illumination chamber 124 comprises a source or emitter, which is preferably an IR emitting LED, and other optical components such as lenses and optical guides to shape and direct the IR light emitted by the LED. Position detection unit 120 also comprises optical receiver 128 . [0030] FIG. 2B is an illustration of the areas defined by the overlap of beams created by position detection unit 120 . Each of the illumination chambers 124 produces a beam. The beams are positioned such that pairs of beams overlap in a given area. These are shown as position detection areas 131 - 136 . Each pair is comprised of a beam from a chamber of module 122 and a beam from a chamber of module 126 . When a signal transmitted from each chamber of the pair is sensed as having been reflected by an object, the position of the object is within the corresponding position detection area. The pairs used for each detection area are as shown in Table 1 below, which is also reproduced as FIG. 2C . [0000] TABLE 1 Module Module Position 122 126 detection area 124A 124F 131 124C 124D 132 124C 124F 133 124B 124F 134 124C 124E 135 124B 124E 136 [0031] The detection signals from the different chambers are distributed in time. Only one chamber emits the detection signal during a given period or moment of time. Each position detection signal comprises a plurality of bursts, preferably 4 or 5, and each burst in turn comprises a plurality of pulses, preferably between 15-25 pulses. The emitted signal preferably comprises IR light of approximately 880 nm wavelength, and the frequency of the pulses is approximately 455 kHz. The period between bursts is approximately 150 us. [0032] If receiver 128 receives a signal with an energy level above a minimum threshold, it provides an output signal to the processing circuitry of the controller. In one preferred embodiment, the output signal comprises pulses of output voltage. In such a case, the receiver provides one pulse per burst of received light. This modulation filters out ambient noise such as sun light, light from nearby lamps, and from IR remote controls, that may otherwise contain sufficient energy to be interpreted as position data. [0033] In the games with the fastest action or changing of foot positions, the minimum time a foot may be in a given position is about 120 milliseconds, although in the vast majority of situations a foot will be present in a given position for much longer. With the preferred embodiment, a foot can be detected within about 16 milliseconds. That is to say that position detection unit 120 can sequence though one cycle where all the illumination chambers of a given detection unit emit a signal in about 16 milliseconds. In certain embodiments the cycle can be repeated to increase accuracy. For example, if four cycles are performed, this will require about 60-65 milliseconds. This means that about 7 or 8 cycles could be performed within the minimum detection window. All position detection units 120 may cycle simultaneously, or may alternatively be sequenced to cycle at different times. [0034] FIG. 3 is an illustration of reflection from an object inside a predefined detection area. Object 140 can be seen within area 131 . As seen in Table 1, this means that a signal emitted from chambers 124 A and 124 F has been reflected to and received by receiver 128 . Signal 144 is emitted by chamber 124 A, and the directly emitted portion is shown as 144 D, while the portion reflected from object 140 is shown as 144 R. Likewise, signal 142 is emitted by chamber 124 F, and the directly emitted portion is shown as 142 D, while the portion reflected from object 144 is shown as 142 R. Receiver 128 has a field of view sufficient to receive signals from any of the predefined position detection areas. [0035] FIG. 4 is an illustration of reflection from objects outside the predefined detection areas. In this figure, two different objects 146 and 148 are located outside of the predefined areas. Object 146 reflects a signal 145 from chamber 124 F, but not from any other chamber. It is therefore not indicative of a user position. Object 148 reflects signals 147 and 149 from chambers 124 B and 124 D. However, since this pair of signals does not correlate with a desired detection area, it does not indicate a user position. Again, as mentioned previously, this selectivity and rejection aids in eliminating erroneous position detection. [0036] FIG. 5 is an illustration of a reflection from a nearby object 150 outside of the game play zones 112 shown in FIG. 1C . The field of view of the various chambers and the resulting detection areas is potentially vulnerable to unwanted detection of “ghost” objects that are not actually within one of the detection areas, as touched upon earlier. In some cases, the surrounding obstacles could simulate or “ghost” an object in a position detection area due to reflections from paired chambers. In FIG. 5 , the wall or other distant object 150 would indicate a ghost object 149 in area 132 . In the aforementioned embodiments, the emitted beams are transmitted in a direction substantially parallel to the ground. [0037] One solution employed in other embodiments in order to minimize unwanted reflections involves angling the beams from illumination chambers 124 towards the ground, as seen in FIG. 6 . FIG. 6 is a side view elevation of position detection unit 120 illustrating the path of signals emitted and received by the unit, relative to the ground and bottom of game controller 100 . The furthest distance for game play is significantly less than the nearest recommended distance from potential obstacles. For example, a player's feet may be detected within about 3 feet, and the player will be instructed to keep objects approximately 4-6 feet away from controller 100 . Theses distances can of course vary, as can the strength of the LED's and the minimum energy levels at the receiver used to indicate a detected position, all of which factor into the size and geometry of the game play zones and detection areas, and the minimum distance in relation to obstacles. [0038] In FIG. 6 , beam 152 , created by one of chambers 124 , is shown as having a direct component 152 D and a component reflected from the floor, 152 F. Angling the beam 152 reduces the chance that it will be reflected from a nearby obstacle. A reflection of either the direct component 152 D or the reflected component 152 F may be sensed by receiver 128 when it is within the field of view 160 of receiver 128 , if it has sufficient energy and the proper trajectory. The component reflected from the floor will in most circumstances be of a diffused nature and will have significantly less energy than the direct component. Thus, any subsequent reflection from a foot or any other object will have much less energy than a reflection of direct component 152 D and it is preferable that reflections from reflected component 152 F not be used for position data. This is accomplished by selecting the strength and trajectory of the LED's and the minimum energy levels at the receiver such that the reflections of component 152 F will not indicate position data. Such an embodiment is effective at limiting unwanted detection of obstacles and ghosting. [0039] While the preferred embodiments have been described with regard to dancing games, many different types of games can be played with a controller according to the present invention. Although the various aspects of the present invention have been described with respect to exemplary embodiments thereof, it will be understood that the present invention is entitled to protection within the full scope of the appended claims.
A video game controller for home video game systems is situated between a player's feet and is used to detect positions outside the footprint of the controller. The controller transmits the position data to the video game system and enables game play. In dance games, the controller detects dance steps when the player dances around the controller. A signal is transmitted from locations at the perimeter of the controller, reflected by the player's foot, and then received back at the controller. In a preferred embodiment the location is detected as a function of the time the signal is transmitted/received and by the matrix of signals received. Modulation of the transmission and reception minimizes detection of noise and distant reflections and therefore minimizes or eliminates false position detection.
0
BACKGROUND OF THE INVENTION Many child's toys are provided with wind-up spring motors, or flywheel/friction motors which are actuated by repeatedly rapidly rolling the wheels of the toy against the floor, then letting go of the toy. Especially for those of these types of toys as are intended to roll along the ground rather than to fly through the air, powering-up the toy and letting it go requires that the child position himself or herself in close proximity to the surface on which the toy is to be released. Sometimes the child is tempted, then, to play on a table top, with the attendant possibilities that the table top may be dirtied, scuffed or scratched, and that the toy may fall off the edge and break. Or the child may get right down on the floor or on the ground, with the result that his or her clothes become dirty or torn as the child moves about on the floor or ground while absorbed in powering-up the toy, releasing it and retrieving it. SUMMARY OF THE INVENTION For use in conjunction with a toy of the kind that includes a body having a motor of the flywheel/friction motor type, or of the wind-up spring motor type, a powering-up and releasing device is provided. This device includes an elongated wand which the user temporarily connects to the toy, may use to wind the toy up where the toy has a spring motor, and then uses to release the powered-up toy, by pushing a button, trigger or the like. This actuator is especially useful where the toy is a model race car or other wheeled toy meant to scoot along the floor or ground or along a track. The principles of the invention will be further discussed with reference to the drawing wherein a preferred embodiment is shown. The specifics illustrated in the drawing are intended to exemplify, rather than limit, aspects of the invention as defined in the claims. BRIEF DESCRIPTION OF THE DRAWING In the Drawing FIG. 1 is a longitudinal sectional view of the device of the invention connected in actuating relation to a toy racing car; and FIG. 2 is a fragmentary longitudinal sectional view on a larger scale illustrating how the rack pull rod housing is held fixed to the toy until the activator rod is thrust forwards to simultaneously activate the wound mechanical motor of the car and separate the car from the rack pull rod housing. DETAILED DESCRIPTION As an example of a mechanical motored toy which may be operated using the actuator 10 of the present invention, there is shown a wheeled race car 12 having free wheels 14, powered wheels 16 and a motor 18, which may be for instance, a spring motor or a conventional friction/flywheel type of mechanical motor. The toy 12 and its motor 18 may be utterly conventional. To that end, the motor 18 is provided with a ratchet-type of wind-up device, e.g. a gear 20 which, when rotated in one direction, e.g. in the direction of the arrow 22, winds-up the motor 18, which continues to be receptive to being further wound-up and not to run, until a conventional trigger 24 is actuated, e.g. by being pressed longitudinally forwards. The race car 12 is shown having a body 26 with a rear end wall 28 that is provided with a power rack insertion slot 30, a motor activator plunger insertion slot 32 and a plurality, e.g. a pair of locking jaw insertion slots 34 spacedly flanking the motor activator plunger insertion slot 32. The actuator 10 may be thought of as being an elongated, wand-type wind-up and trigger-released actuator for the motorized toy 12. To that end the actuator 10 typically includes an elongated tubular housing 36 which is at least a couple of inches long and which, indeed, may be two, three, four or several feet long. The housing 36 preferably is straight, but it may be serpentine or simply arcuate or the like, generally so as to have a lower forward end and an upper rear end. The housing 36 has at least one throughbore 38. It may have a second one parallel to the first, or simply a common throughbore for the two elements which are to pass along the length of the housing 36. The lower/front end of the tubular housing 36 is shown provided with a fitting in the form of a rack pull rod housing 40 and the upper/rear end of the tubular housing 36 is shown provided with a fitting in the form of a handle housing 42. Conceivably in some instances, the structure 36, 40, 42 could be molded of synthetic plastic resin or otherwise integrally formed as a unit. Preferably, however, the tubular portion 36 is separately formed, e.g. of extruded tubing, and the two terminal portions 40, 42 are molded, e.g. injection molded all of conventional plastics materials, and by conventional extruding and molding techniques. Polystyrene, polyvinylchloride and polyethylene are typical materials. When the structure 36, 40, 42 is made in three pieces, these may be united by jam fitting of the ends 44 of the housing 36 into respective sockets 46, 48 in the parts 40, 42, with or without the aid of adhesive securement, solvent welding, ultrasonic welding, spin-welding or the like, conventionally employed. Accordingly, there is provided a unitary actuator housing structure including a tubular central portion 36 with a head end 40 and a tail end 42. The forward end 50 of the rack pull rod housing 40 is shown shaped to engage the rear end wall 28 of the body 26 of the toy 12 at least in the vicinity of the motor activator insertion slot 32. Further, the forward end 50 of the rack pull rod housing 40 is shown provided with a rack pull rod opening 52 and a motor activator rod opening 54. The handle housing 42 is shown including a longitudinal bore 56 continuing axially from the upper end of the socket 48, and a rearwardly-extending stationary handle portion 58. The housing 42 is hollowed at 60 under the stationary handle portion to provide for the pivotal mounting at 62 of a squeezable grip-type movable handle portion in the nature of a drive lever 64. A rack pull rod 66 which may be formed of flexible resilient metal or plastic is shown longitudinally reciprocably received in the bore 38 in the actuator 10. The rack pull rod 66 has an exposed forward portion 67 which projects forwardly beyond the surface 50, out of the rack pull rod opening 52. With in the handle housing 42, the upper, read end portion of the rack pull rod 66 is longitudinally reciprocably received in the longitudinal bore 56. Within the hollow 60 of the handle housing 42 a rearwardly oriented opening 68 provides lateral access to the longitudinal bore 56. At this same level, a slot, notch, tab or the like 70 is shown provided on the rack pull rod 66, near the rear, upper extent of the latter. A toggle lever 72 is shown pivotally mounted at 74 in the hollow 60 of the handle housing 42 so as to have one toggle arm 77 engaged under a protuberance 76 of the drive lever 64 and an opposite toggle arm 78 engaged with the rack pull rod feature 70. Down close to the opening 52, the rack pull rod housing bore 80 is provided with an enlarged compartment 82 through which rack pull rod 66 coaxially longitudinally passes. This compartment has an annular rear wall 84 and opposite that, an annular front wall 86. An annular collar 88 fixed on the rod 66 and disposed within the compartment 82 limits longitudinal projection of the rack pull rod 66 by engagement with the front wall 86. A compression coil spring 90 is received in the compartment 82 coaxially surrounding the rod 66, with its forward end pressing against the rear of the collar 88 and its rear end pressing against the annular rear end wall 84 of the compartment 82. Accordingly, the spring 90 normally keeps the rack pull rod fully projected. However, if the user grips the handle stationary portion 58 and the drive lever 64 and squeezes, the drive lever is temporarily pivoted up to adjacency with the underside of the portion 58. This pushes down the rear arm 77 of the toggle lever 72, correspondingly pushes up the forward arm 78 of the toggle lever 72, causing the rack pull rod to be correspondingly longitudinally reciprocated upwards in a sense which partially retracts the exposed forward portion 67 of the rack pull rod 66. As the user lets-up on his or her squeezing action, the spring 90 which has become compressed, recovers, and in doing so again fully projects the rack pull rod exposed forward portion 67 and returns the drive lever 64 to the full-line position shown. The user may repeatedly perform this squeezing maneuver, each squeeze resulting in a correspondingly rapid retraction and projection of the rack pull rod exposed forward portion 67. It should now be noticed that the rack pull rod 66 exposed forward portion 67 is provided with a longitudinally extending series of rack gear teeth 92. This series 92 of the rack gear teeth is constructed and arranged to drivingly mesh with the ratcheted wind-up gear 20 for the motor 18 of the toy 12. Accordingly, when the rack gear 67 is inserted through the insertion slot 30 and engaged with the gear 20, provided the actuator 10 is fixed to the toy 12, each time the drive lever 64 is squeezed, the rack gear turns the gear 20 to correspondingly wind the motor 18. Each time the drive lever 64 is released, the spring 90 projects the rack gear, spinning the ratcheted gear 20 without affecting the motor 18. The remainder of the actuator 10 has to do with a means for releasably holding the actuator 10 secured to the toy 12, and for simultaneously releasing the actuator 10 from the toy and pushing the trigger 24 of the wound-up motor 18. To these ends, the upper side 96 of the stationary portion of the handle is shown provided toward the front with a slot 98 through which there upwardly projects a drive actuator slide button 100. The slide button 100 is shown mounted with the aid of an interdigitated slot and groove arrangement 102 which permits the slide button 100 to be slid forward in the slot 98. Within the hollow of the handle housing a tension coil spring 104 is shown anchored at one end and secured at the other to the slide button 100 for pulling the slide button back to the full line position shown after the slide button has been pushed forward and released. Also within the actuator housing a flexible motor activator rod or wire 106 is shown secured at one end to the slide button 100, longitudinally slidably supported in passageways 108, 110, and having a forward end portion 112 which projects out of the actuator housing through the motor activator rod opening 54. Accordingly, as the slide button 100 is pushed forwards and released, the motor activator rod 106 is correspondingly reciprocated longitudinally forwards to greater protraction, then retracted to the full line position shown. (As indicated hereinabove, that amount of forward projection is sufficient to release the conventional trigger 24 of the wound-up conventional spring motor or friction/flywheel motor 18.) With particular attention to FIG. 2, it should be noted that the rack pull rod housing is coaxially provided about the motor activator rod opening 54 with an annular groove 114 which defines a spring finger collet structure 116 perimetrically surrounding the opening 54. A plurality of respective slots split the structure 116 into a respective plurality of individual resilient fingers 118, each based on the rack pull rod housing and normally disposed to have the respective positions shown in full lines in FIG. 2. Each finger 116 is provided on its outer end with a tapered internal surface 119 which converges, barb-fashion to an abrupt shoulder 120 which faces the housing interior from a location somewhat beyond the level of the rack pull rod housing forward end surface 50. Within the housing, each finger is provided with a tapered ramp surface 122 which decreases in diameter toward the forward end surface 50. The activator rod 106 is, centrally among the ramps 122, provided with a complementarily tapered surface 124 which usually lies radially inwardly and longitudinally upstream from the ramp surfaces 122. The actuator 10 is used in association with the car by simply urging the toy body rear wall 28 into confronting relation with the front end wall of the actuator 10. As these two units are urged together, the rack gear 67 of the rack pull rod enters the corresponding opening of the toy and its teeth 92 become drivingly engaged with the ratcheted wind-up gear 20 of the motor 18, and the forward end of the motor activator rod enters the corresponding opening of the toy and becomes poised in juxtaposition with the release trigger 24 of the motor 18. Finally, during the performance of this docking procedure, the tapered surfaces 118 on the actuator engage the slot edge surfaces 130 on the car and the outer ends of the fingers 116 are thereby resiliently deflected until the shoulders 120 enter and latch behind the wall 28. The toy and the actuator now are locked together. The user may then wind or otherwise mechanically power-up the toy motor as much as is desired, by squeezing the handle of the actuator one or a succession of times as is described hereinabove. When the user wishes the toy to be released and begin operation, the user simply pushes the slide button 100 forwards momentarily. As the motor activator rod 106 is thereby advanced, two events are nearly simultaneously caused to occur. The forward end 132 of the activator rod triggers the catch on the wound motor 18 so that the motor begins to wind-down, e.g. powering the toys's driving wheels, and the surface 124 on the activator rod engages the ramp surfaces 122 on the spring fingers 116, causing the spring fingers 116 to be resiliently deflected radially outwards sufficiently to release the catches at 120, 130, so that the toy separates from the actuator and speeds away. The actuator is ready and available for immediate reuse with the same toy or one having like powering, coupling and release provisions. It should now be apparent that the elongated wand-type wind-up and trigger-released separable actuator for motorized toy as described hereinabove, possesses each of the attributes set forth in the specification under the heading "Summary of the Invention" hereinbefore. Because it can be modified to some extent without departing from the principles thereof as they have been outlined and explained in this specification, the present invention should be understood as encompassing all such modifications as are within the spirit and scope of the following claims.
For use in conjunction with a toy of the kind that includes a body having a motor of the flywheel/friction motor type, or of the wind-up spring motor type, a powering-up and releasing device is provided. This device includes an elongated wand which the user temporarily connects to the toy, may use to wind the toy up where the toy has a spring motor, and then uses to release the powered-up toy, by pushing a button, trigger or the like. This actuator is especially useful where the toy is a model race car or other wheeled toy meant to scoot along the floor or ground or along a track.
0
CROSS-REFERENCE TO RELATED INVENTIONS [0001] This Application relates to and claims priority from U.S. Provisional Application Ser. No. 60/668,114 filed Apr. 4, 2005. FIELD OF THE INVENTION [0002] The present invention relates generally to products and methods for improving the nutritional, textural and functional properties of sugars, sugar syrups and products made therefrom. BACKGROUND OF THE INVENTION [0003] The flavor characteristic of sweetness is one of the most pleasing taste experiences to humans. Sadly, we have found that this pleasure comes with many associated physiological maladies. For more than thirty years, the high simple sugar content of the North American diet has been recognized as creating or contributing to a variety of health challenges, including dental caries, diabetes, and obesity. Consequently, alternatives have been desired and sought. Alternative sweeteners, such as fructose, fruit syrups and the less common sugars such as erythritol, isomaltitol, and trehalose as well as high-intensity sweeteners, each seem to offer certain health benefits. Unfortunately, the functional properties of these alternative sugars and sweeteners are so different from those of sucrose, that it has not been possible to replicate the traditional flavor and textural characteristics in foodstuff made with these alternative sweeteners. [0004] During this same time period, the significance of dietary fiber has become well recognized, as has the generalized deficiency of dietary fiber in most dietary regimens. This deficiency has also produced negative consequences for general health, including constipation, irritable bowel syndrome (IBS), diverticular disease, Crohn's Disease, ulcerative colitis, and gastrointestinal cancers. It is generally understood and accepted by medical practitioners in this field that gastrointestinal health is promoted by a moderately high rate of fecal transfer which is greatly facilitated by sufficient daily levels of dietary fiber. [0005] While many consumable products based on dietary fiber have been introduced in recent years, they are characteristically lacking in taste and palatability and less than pleasant to consume, making routine consumption of such unpalatable products the exception rather than the rule. Consequently, the problem persists. For example, some dietary fiber supplements dissolve slowly and/or incompletely, so that the freshly-prepared slurry is gritty and unpleasant to ingest. If this preparation is allowed to stand, the grittiness decreases, but the viscosity increases, again producing an unpleasant experience. Other dietary fiber supplements produce very high viscosities when concentrated, such as occurs in the colon, thereby retarding the rate of fecal passage, a condition which is opposite to the desired acceleration of fecal transfer rate. Still other such products are fermented in the colon, producing gas which is not only uncomfortable and frequently embarassing, but which can also drive urgency for bowel evacuation. [0006] It is therefore an objective of this invention to provide a product and method by which a range of food products may be produced which are very pleasant in taste and texture, and therefore, pleasant to eat, and which contain a sufficiency of soluble dietary fiber to effectively supplement the typically low fiber dietary intake, without compromising the overall objective of promoting a healthy fecal transfer rate and without flatulence or gaseous effulgence. [0007] Currently, the best-known dietary fiber supplement products available in the market include; psillium seed extract (“METAMUCIL”), methyl cellulose (“CITRUCEL”), and partially hydrolyzed guar gum (“BENEFIBER”). However, other entrants into this arena have also made their appearance in the last decade. As an example, a little more than a decade ago, the Matsutani Company introduced a novel indigestible dextrin (synonymously referred to herein also as “dextrin”) derived form corn marketed under the trademark FIBERSOL 2. FIBERSOL-2 is a soluble dietary fiber (90% min DSB) and is produced from cornstarch by pyrolysis and subsequent enzymatic treatment to purposefully convert a portion of the normal alpha-1,4 glucose linkages to random 1,2-, 1,3-, and 1,4-alpha or beta linkages. The human digestive system effectively digests only alpha 1,4-linkages; therefore the other linkages render the molecules resistant to digestion. Thus, FIBERSOL-2 is GRAS (21CFR §170.30) as maltodextrin, resistant to human digestion, and conforms to all working industrial and scientific definitions of dietary fiber. It is an off-white powder which is clear and transparent in 10% solution and resists both enzymatic and non-enzymatic browning. It is water soluble up to 70% (w/w) at 20 degrees Centigrade. FIBERSOL-2 brand of maltodextrin has excellent dispersibility, very low hygroscopicity, and is stable in acid, heat/retort processing and freeze/thaw stable. It has very low viscosity of 15 cps in 30% solution at 20 degrees Centigrade. Its sweetness is low, on the range of <10% of sucrose at 30% T.S. Typical chemical properties of FIBERSOL-2 brand of maltodextrin include dietary fiber, 90% minimum DSB in accordance with AOAC method 2001.03, a moisture content of 5% maximum, no protein, no fat, DE between 8-12.5, pH 4.0-6.0 and 4.0 calories per gram (U.S.). [0008] The FIBERSOL-2 brand of dextrin is described in several patents assigned to Matsutani, including: U.S. Pat. Nos. 5,358,729, 5,364,652, 5,380,717, 5,410,035, 5,472,732, 5,519,011, 5,595,773, 5,629,036, 5,698,437, which are hereby incorporated by reference as describing indigestible dextrin useful with the present invention. [0009] While the FIBERSOL-2 brand of indigestible dextrin is provided as an example of a low viscosity dietary fiber (LVDF) and the embodiments of the present invention are set forth in their best mode with reference to the FIBERSOL-2 brand of dextrin, it is intended that any LVDF will exhibit utility in the present invention. By “any LVDF” we mean any material that has physical, functional and biological properties substantially to those describe in the Matsutani references, incorporated herein by reference. [0010] In all of this, they not only detail the means of its manufacture, and describe its several claimed health and functional benefits, including: 90% Dietary Fiber, high solubility, low viscosity, absence of taste or flavor, moderates post-prandial rise in serum glucose, increases fecal volume, increases fecal frequency from about 0.5 to about 1 time per day, increases the population of the beneficial Bifidus bacteria in the colon, reduces serum triglyceride and cholesterol levels and produces freeze-thaw stable solutions. [0011] In addition to describing the health and functional benefits, the foregoing patents provide a comprehensive list of foodstuffs with which dextrin may be used, including: black tea, cola drinks, orange juice, sports drinks, milk shakes, ice cream, fermented skimmed milk, hard yogurt, coffee whitener powder, candy, chewing gum, sweet chocolate (bar type), custard cream (panna-cotta type), orange jelly, strawberry jam, apple jam, bean jam, sweet jelly of beans, cereals, spaghetti, white bread, American donuts, wheat flower replacer, butter cookies, pound cake, sponge cake, apple pie, corn cream soup, retorted pouch curry, beef stew, non-oil dressing, dressing (MIRACLEWHIP type), mayonnaise, peanut butter, cheese powder, cream cheese, white sauce, meat sauce, beef and pork sausage, corned beef, hamburger steak, hamburger patty, liver paste, pizza, omelets, filing of meat pie, filling of Chinese dumpling, kamaboko, black berry liquor, dog food, cat food, pig feed, feed for broiler poultry or feed for laboratory rodent. SUMMARY OF THE INVENTION [0012] However, in all of these product descriptions, they seem to have been focused upon demonstrating that their novel material could be added to foods (as a means of adding dietary fiber) without jeopardy. This rigid focus seems to have prevented them from seeing several surprising attributes of this material that can actually add new values to foods and other products. This discovery forms the foundation of the set of related inventions described herein. [0013] For example, we found that, when low viscosity dietary fiber (“LVDF”) in the form of dextrin (Matsutani, FIBERSOL-2) was prepared as a high solids syrup (hereinafter referred to synonymously as “LVDF syrup” or “HSS”), this LVDF syrup was found to demonstrate surprising new properties. Most especially interesting is that the inventive syrup, prepared in the manner described below, displays a remarkable set of functional attributes, including a low viscosity (even at very high concentrations), the capacity to confer pleasing mouth-feel, (this consideration includes both the consistency and mouth-feeling factors of liquid syrups and the crunchy textures and mouth feeling factors of dry, solid matrices). As well, its surprisingly low Equilibrium Relative Humidity (ERH) contributes characteristics to dry sugar matrices to which it is added. By “low Equilibrium Relative Humidity (ERH)” is meant that set of physical properties which, at any given moisture content, causes such syrups (or dry products prepared therefrom) to tend to loose, rather than hold onto or pick up moisture, in comparison to conventional syrup materials. This surprising attribute has been found to be remarkably versatile in its usefulness. [0014] The simplest new utility we found in the character of the syrup itself. That is, we found that when an LVDF syrup is prepared (65 to 70% solids content), it has a pouring character and mouthfeel that was almost identical to those of maple syrup. [0015] When their long list of foods in the cited Matsutani patents is reviewed, no “syrup” product can be found. Therefore, no advantage of such a syrup can have been discovered by that inventor. [0016] Further, Matsutani did not see the possibility (let alone the attractiveness) of a syrup that would have the sensory character of maple syrup, yet be high in fiber and virtually non-glycemic. Such products have been prepared by the inventor, using the inventive syrup alone, as well as blends of Erythritol, fructose and LVDF syrup. [0017] Then we found that when the inventive syrup was used (in lieu of corn syrup) to stabilize a sucrose hard candy, the resulting candy is superior to conventional corn-syrup doctored hard candies. [0000] Candy ‘Doctors’: [0018] It has long been known that when a sucrose solution is boiled, its solids content increases, and consequently, the temperature at which it boils also increases, and that, further, as the solids content increases, the physical character of the cooled product also changes in predictable ways. Standard curves are available in the industry relating temperature of boiling to solids content of the boiling syrup, and to the resulting character of the cooled product. It is generally taken that at a temperature of about 300° F., the moisture content is below about 2%. At this level of dryness, the syrup, when cooled will form a crisp glass known as “hard candy”. However, it will shortly thereafter spontaneously degrade to a mass of “sandy” granules. That is, the glass will crystallize. Long ago it was found that this product disaster can be averted by the replacement in the original syrup of about 20 to 30% of the sucrose by corn syrup. The corn syrup was called a “Candy Doctor”. The use of corn syrup (or sometimes “invert sugar”—that is sucrose that has been hydrolyzed to its component simple sugars, glucose and fructose) has, since that early time, been standard practice in the candy industry. The ‘penalty’ of this standard practice (a certain stickiness, especially to the teeth) is a factor to which the industry has become accommodated that is, it seems to have become ignored. [0019] It should be noted that, while Matsutani's U.S. Pat. No. 5,364,652 does mention the use of their dextrin in the manufacture of a “candy”, this product does not teach the utility we have found. In that example, they seemed to have focused their attention on replacing sucrose and so repeated the conventional practice of including corn syrup in its preparation. As well, the resulting mixture was cooked only to “Bx 80” (“Bx” stands for “Brix”, a measure of total solids in solution) before cooling. Thus, the candy still contained 20% moisture, and, would therefore have had the character of a caramel rather than a hard candy, which has a typical moisture content of which is in the range of 0 to 3%. Therefore we conclude that the utility we found had not been found by Matsutani. [0020] Even more significantly, in none of the Matsutani references is there the suggestion or teaching that their indigestible dextrin could serve as a corn syrup (or invert sugar) replacement or as an alternative “Candy Doctor” to lend new dietary properties to the foodstuffs. [0021] We subsequently evaluated the effects produced by adding the inventive syrup, or dry dextrin to a variety of beverages and confections. We were surprised to find that, when added even at low levels (0.5 to 10%) to all of these products, the amended products tended to show the same qualitative improvements, namely, the flavors in the LVDF-added products displayed a mellower flavor, with a more well-blended aroma than the original product. This kind of qualitative enhancement is very highly prized. It is conventionally found in only the most costly teas, and the finer wines and chocolates. This novel finding, therefore, has great economic potential. [0022] The following is a partial list, intended to be illustrative of the utility of the present invention: As an ingredient in edible syrup, of solids content sufficiently high to be stable at room temperature, and that has a fluid character and a mouthfeel virtually identical to maple syrup. Such syrups being prepared from either the inventive syrup alone, or blends of uncommon sugars and the inventive syrup. As a novel ‘Candy Doctor’ for sucrose-based confections; producing a cleaner-biting (less sticking-to-the-teeth) candy ‘glass’ than found in conventional hard candy preparations. As a ‘doctor’ for such highly hygroscopic sugars as erythritol, palatinate, Fructose, the inventive syrup dominates this property, enabling (for the first time) toffees and hard candies (and hard candy shells) from this group of desirable but still uncommon sugars. As a ‘doctor’ that confers a certain ‘shortness’ of texture usually encountered in confections that have a high intrinsic fat content, such as pralines, nut brittles and fried bananas. As a ‘doctor’ that induces a rapid set to hard candies and hard candy coatings. As an enhancer for the flavors of a wide range of beverages; creating a mellowness and blendedness that is highly-prized and usually found only at the peak of fruit ripeness, or after long aging. As an enhancer for the flavors of a wide range of confections; creating a mellowness and blendedness that is highly-prized and usually found in only the highest priced products. As a carrier for fragile flavors, (and other heat-labile biological materials) that then can be dried far more readily and more gently than with conventional carriers or supports, while retaining rapid, facile dissolution. [0031] It can be seen in their U.S. Pat. No. 5,358,729 that Matsutani's consideration of solids content vs Viscosity was rather narrow, as demonstrated in FIG. 1 of that document: BRIEF DESCRIPTION OF THE FIGURES [0032] FIG. 1 is table identifying the different stages of sugar syrup in candy making. [0033] FIG. 2 is a graph showing the correlation of viscosity to temperature for gum Arabic, maltodextrin (DE10), FIBERSOL-2 and sucrose. [0034] FIG. 3 is a graph showing the correlation of concentration with viscosity derived for FIBERSOL-2. DETAILED DESCRIPTION OF THE INVENTION [0035] Simply, we found that it was possible to prepare a syrup consisting of 60 to 70% FibersSol solids and water, and that this syrup is shelf stable, and it has a fluid character virtually identical to a high quality maple syrup. Further, the mouthfeel of these syrups were virtually identical to the conventional syrups that they simulated. The flavor of these syrups was so mild that they were easily ‘morphed into’ the flavor profile of the targeted conventional syrup by the facile addition of an intense sweetener and an appropriate, available commercial flavoring. EXAMPLE 1 High Fiber, High Solids Syrup (“LVDF Syrup”) [0036] LVDF (FIBERSOL, Matsutani, 65 parts by weight) was dispersed in (distilled) water (35 parts by weight), sheared to disperse, and heated to 60° C., and held, with agitation at this temperature until it cleared. The composition was prepared in accordance with Table 1, below, with all percentages given in weight percentages. A significant decrease in viscosity was seen as the turbidity disappeared. It was then ready for use as described herein. It should be noted that this heating could also function as a pasteurization or sterilization. TABLE 1 Ingredient Supplier Wt. % LVDF Matsutani 65.0 Water n/a 33.7 Aspartame NutraSweet 0.3 Maple Flavor McCormick 1.0 Total 100% [0037] A serving of this syrup (two tablespoons) provides the nutritional profile, as compared with real maple syrup as indicated in Table 2, below: TABLE 2 Product Carbohydrates (g) Calories Fiber (g) Vermont Maple 19.5 78 0 Syrup Product of 4.1 16.4 15 Example 6 [0038] The fact that a syrup of such high solids content can be made, which is yet pourable, is quite unexpected. The copious product listings in Matsutani's patents makes it clear that they had not foreseen it. If they had, since it is so unexpected in a substance with a molecular weight from about 510 to 965, and since such a physical property would have such broad practical utility, they would surely have described it and claimed it, had they seen it. Therefore, we take their silence as proof of the novelty of our finding. [0039] For example, Matsutani U.S. Pat. No. 5,358,729 (the only one providing any viscosity data) shows the viscosity of their product in comparison with sucrose, maltodextrin (presumably Dextrose Equivalent (DE) 10, as identified on www.matsutani.com), and gum Arabic. FIG. 1. However, this comparison shows these viscosities at a dextrin concentration of only 30%, (strangely, the concentrations of the other materials are not identified). This same graphic evidence is reproduced on their website. Nowhere in their data have I been able to find a definition of the viscosity versus concentration of the disclosed dextrin solutions. FIG. 3 represents the viscosity data obtained from a viscosity assay of the dextrin disclosed in the Matsutani references, at about 20° C. [0040] In Matsutani's listing of food products (referenced earlierset forth in the Matsutani references), every one of the products contains the “Indigestible dextrin” at a relatively low level (3 to 50% of the dry substance of the foodstuff) or at levels thatwhat might be called a “fiber additive”. In contrast, what we have seen is that this dietary fiber can be concentrated enough to afford osmotic preservation, while at the same time, remaining fluid enough to be pourable, in traditional terms. Further, the flavor and mouthfeel of this syrup is so very pleasing that it can readily be colored and flavored to be indistinguishable from conventional maple syrup. Alternatively, it can be formulated to provide a convincing honey syrup, or any of a variety of traditional sensory impressions. The resulting ‘syrups’ are then such as can be added to conventional foods as a means of simultaneously enhancing both the flavor and mouthfeel of that food as well as adding a substantial portion of the recommended daily intake of dietary fiber. This combination of convenience, sensory enhancement and dietary advantage has not heretofore been achieved in the field of high fiber products. [0041] As this graph shows, the viscosity of Fibersol is, in fact, very low, at concentrations below about 55%, but thereafter rises sharply. That the high end of the relationship was not identified by the supplier, conjecture can only have been the result of their concern over the implied inutility of these higher viscosities, as this portion of the concentration/viscosity curve would seem to detract from their “Low viscosity” positioning. However, we have found that, while this curve does indeed rise sharply, the solutions remain fluid, and in fact, distinctly pourable. For reference, points “1” and “2” indicate the viscosities of commercial brands of Maple Syrup, and Honey, respectively. Thus, this portion of the curve, (which fortunately embraces the region of osmotic microbial stability) is in fact a region of great practical utility. It is this fortuitous combination of high solids (and therefore osmotic microbial stability) coupled with pourability to which we claim proprietary ownership. [0042] We further found that this prepared FiberSol syrup (FSS) can be used to great advantage to replace corn syrup in the manufacture of a variety of confections. [0043] The simplest example is the preparation of a LVDF-Doctored hard candy. EXAMPLE 2 A High-Fiber Candy Doctor [0044] A high fiber candy doctor was compounded by mixing sucrose, low viscosity dietary fiber (FIBERSOL 2, Matsutani) and maple flavor set forth in Table 3, below. TABLE 3 Ingredient Wt. % Sucrose 69.0 LVDF (Matsutani) 30.00 Maple Flavor (McCormick) 1.0 [0045] These proportions are calculated as final composition, after initial syrup preparation and boiling to ‘dryness’. The flavoring is added after cooking and partial cooling to avoid aroma waste. [0046] The mixture was filled into round molds, about 1″ diameter. When cooled, the attractive candies easily de-molded. When placed in the mouth, they were glass-smooth, slow to dissolve, pleasantly sweet, with an attractive maple flavor. There was no aftertaste, and no residual mouth feelings. Each such candy weighed about 7 grams, of which about 2 g were soluble dietary fiber. Therefore, the consumption of about 6 such candies would provide about 12 g dietary fiber, an amount that would, on average, bring the US dietary fiber intake up to the level recommended for good intestinal health. [0047] In a manner similar to conventional practice with traditional hard candy formulations, such candy can also be used as a glaze. [0048] We found a unique application by wrapping a thin, hard candy shell (made from a compound sucrose/fibersol syrup) around a freeze-dried fruit such as strawberries. Of course, many other fruits could also be used in this way, including other freeze-dried berries, cherries, freeze-dried balls cut from apple, melon, papaya, mango, etc. or freeze-dried slices of banana. These non-berry fruits can also be cut into shapes such as julienne or flakes, (before drying and coating) in which forms they would be especially attractive as garnishes for cake-decorating and food service. [0049] Using the product of Example 2, a glaze was prepared with the same ratio of dietary fiber to sugar as is found in the fruit itself: i.e. 30%. Thus, regardless of the weight of glaze added to the strawberries, the final ‘Proximate Composition’ of the product remains “Fiber, 30% of total carbohydrates”. This claim has not heretofore been possible. [0050] Of course, a similar product can also be prepared using conventional hard candy formulas, but while it will also be novel, and will have the improved appearance, much of the improved texture and flavor, it will lack the improved mouth feel, the non-hygroscopicity as well as the contribution of dietary fiber. Nonetheless, it will still be found to be of interest in certain market segments. EXAMPLE 3 Glazed Dry Fruits [0051] The syrup of Example 1, (30 parts by weight) was combined with a sugar (sucrose) syrup of the same solids content (70 parts by weight) and cooked to a boiling temperature of 160-170° C. and held at about 150° C. while it was used to coat freeze-dried strawberries, by dipping the fruit (held on a fondue fork that had been modified by removing the barb) into the hot syrup and spreading the coating with a small spatula onto all portions of the surface of the berry. Immediately after coating, the coated fruit was lightly sprayed with a lecithinated oil and rotated under a stream of air hot enough, and for a sufficient time to anneal the coating. The coated berries were then allowed to cool. When cooled to 25° C., the coated fruit was seen to be bright, glossy (fresh-looking) and to have a pleasing crisp, crunchy clean texture, and a distinctly improved flavor as compared to the uncoated dry fruit. By “distinctly improved flavor” we refer to a more intense strawberry aroma, a more balanced sugar-acid ratio, and a crisp clean texture and clean mouthfeel rather than the dry-foam texture and powdery, drying mouth-feel of the original freeze dried fruit. [0052] Further, the coated fruit pieces demonstrated vastly superior resistance to breakage and crushing. Further still, unlike un-coated fruit which is well-known to be highly hygroscopic, the coated fruit was not. [0053] While these coatings can be applied by means of the type of equipment that is used to apply ‘caramel’ coatings onto popped corn, sugar frostings onto breakfast cereals, and candy shells onto chocolate, freeze-dried fruit embodies combinations of characteristics that are unlike any of these other individual food materials. For example, freeze dried fruits are both readily-hydratable (like pop corn) and thermoplastic, (like chocolate). Thus, special consideration must be given to the design of conditions and coating equipment so that neither of these frailties are invoked. [0054] Another surprising aspect of this work is the finding that, while it is made without any added fat, it has the sort of “short” texture one would normally only get with a fatty candy (e.g. peanut brittle, praline). Therefore, this new form of hard candy holds considerable promise in the preparation of products with high sensory qualities, and low fat levels. EXAMPLE 4 Non-Fat Banana Chips [0055] The hard candy glaze of Ex. 3 was used to coat Freeze Dried Banana Slices. When cooled, they had a rich banana flavor and a crisp clean texture very similar to conventional “Banana Chips”. However, conventional “Banana Chips” are prepared by frying slices of plantain (a starchy relative of banana with a low level of banana flavor). They therefore carry a burden of about 20 to 35% fat. In contradistinction, the product of Ex. No. 4 is fat free, yet is at least as pleasing to the palate as the full-fat conventional product. [0056] Sugar syrups (and sugar alcohols) have been used since quite ancient times to provide a sufficiently high osmotic effect to retard or obviate the growth of micro-organisms. Examples of such classically-produced osmotically-protected products would include: fruit preserves, glacé fruits, fruit leathers, meat jerkys, sugar-cured ham or mincemeat. [0057] However, in each case, the sweetness of the sugar plays a prominent, even dominating role in the product's flavor. The sugar also contributes prominently to both caloric content and glycemic index. [0058] These burdens limit the breadth of utility for this approach to protecting food from spoilage. [0059] Therefore, it seemed to us that a non-sweet, low-glycemic means of obtaining this effect would have a real appeal considering current consumer awarenesses and sensitivities. EXAMPLE 5 Non-Sweet Osmotic Protection [0060] Subsequently, we found that the inventive LVDF composition has a range of utility broader than the production of simple syrups and confections. Analogous to conventional practice, with common sugars (typically sucrose, glucose and/or fructose) the present invention can be used as aids to food preservation, wherein, in addition to enabling the attainment of a solids content sufficiently high to inhibit bacterial growth, Employing the inventive LVDF composition will deliver certain novel properties in addition to supplying needed supplemental dietary fiber. Examples of this class of application include: Jams, jellies, preserves, Fruit ‘butters’, Fruit leathers, Snack meat products, such as beef jerky or dried sausages such as SLIM JIMS, mincemeat, gum candies, caramels or marshmallows. EXAMPLE 6 Non-Sweet Cryoprotection [0061] In more recent times, sugars, and sugar alcohols have been used to protect foods from the physical damages produced by freezing. In the course of freezing a biological tissue (either plant or animal) for use as food, the water in such tissues freezes. It is in the nature of ice crystals that the larger ones grow at the expense of the smaller. As the ice crystals grow, they pierce cell walls, and over time compress the non-aqueous components of the tissues which become compressed ever more tightly between the advancing ice “plates”. When such tissue is allowed to defrost, the ice plates melt, forming ‘puddles’ of almost pure water amongst the debris that previously had been the organized tissue structure. When such food material is eaten, it is experienced as having been significantly changed in texture. The exact nature of this textural change will depend upon the food material in question. It will be either tough and watery or simply ‘mushy’. In a well-known classical case, when un-protected egg yolk is frozen and defrosted it is found to have become tightly gelled. The addition of about 20% sucrose to the yolk before freezing is known to be sufficient to prevent this unwanted change. In an analogous fashion, sugars or sugar alcohols have been mixed into or infused into a variety of food materials to prevent unwanted textural changes caused by freezing. Once again, the sugar contributes a prominent sweetness and a glycemic burden that limit the breadth of usefulness of this approach. [0062] Therefore, we explored the possibility of using LVDF syrup in lieu of sugars or sugar alcohols to accomplish this ‘cryoprotection’. [0063] LVDF was blended into freshly-separated egg yolks, at levels ranging from 0.1 to 20%. The prepared samples were frozen, held frozen for 2 days, defrosted at room temperature and examined. A sample of un-treated yolk was used as control, and a sample into which had been blended 20% sucrose (as experimental control) were also frozen and defrosted in the same way. We found that gellation was prevented by the incorporation of 20, 15 and 10% LVDF. While the apparent viscosity of the LVDF/yolk was higher than that for the sugar/yolk, the LFDF/yolk was still fluid enough to be pumpable. When a spatula was drawn through it, to make a groove, the walls of the groove sagged, flowed downwards. Whereas, when the same was done to the untreated yolk, the walls of the groove remained in place. [0064] This same protection may be afforded to other food materials as well, including: surimi (i.e., mechanically-de-boned raw fish meat pate), lunch meats, pates or fruits. [0065] We have now shown that LVDF or the inventive LVDF syrup can replace sugars and sugar alcohols as the means to preserve textural integrity through the freezing process. [0066] There is currently a ground-swell of discontent with high-intensity sweeteners. This seems to grow out of recent findings that point to their health hazards as well as to their limited shelf stability (as in the case of aspartame), and their inutility for replacing high sugar levels (as is the case with chlorinated sucrose) or the presence of bitterness (as is the case with stevia). Therefore, we sought to discover if it were also possible to formulate a syrup without the need for high-intensity sweeteners. As shown in the following example, that was indeed possible. EXAMPLE 7 Low Glycemic, High Fiber Flavored Syrup [0067] A high fiber flavored syrup having a low glycemic index was compounded by mixing fructose, erythritol, FIBERSOL 2, water and maple flavor set forth in Table 4, below. TABLE 4 Ingredient Wt. % Fructose 28.6 Erythritol 16.2 LVDF (FIBERSOL-2, Matsutani) 19.5 Distilled Water 45.0 Maple Flavor 1.0 [0068] The fructose, erythritol, LVDF and water were mixed and heated with stirring to the boiling point. Boiling was sustained until a solids content of 65% was attained, whereupon the pot was removed from the heat, the flavor blended in, covered, and cooled to about 150° F., whereupon it was filled into bottles, which were then capped and inverted. The resulting product was shelf stable, had a pleasing level of sweetness and maple flavor, a very desirable viscosity, a natural pouring character and a satisfying mouthfeel. [0069] A serving of 2 tablespoons weighed 37 g, of which 6.5 g was dietary fiber, supplying about half the average fiber supplement reported to be needed in this country. [0070] The choice of fructose and erythritol as the contributors of both sweetness and soluble solids assures that the product also has a very low glycemic index. EXAMPLE 8 Low Glycemic, High Fiber Hard Candy [0071] A high fiber, low glycemic index hard candy was made by compounding LVDF (FIBERSOL-2, Matsutani) (22.2 wt %) with Isomaltitol (44.4 wt %), erythritol (7.4 wt %) as a sweetener, and water 26.0 wt %) and boiling the mixture until it reached 170° C. After being allowed to cool to 150° C. at which temperature, a maple syrup flavoring (McCormick, 1 wt. %) was mixed in. The hot LVDF syrup was poured intomolds and allowed to cool. The candy was smooth, pleasingly sweet, non-sticky, and left no aftertaste. After cooking, the final composition was Isomaltitol (60 wt. %), LVDF (30 wt. %) and erythritol (10 wt. %). EXAMPLE 9 Low Glycemic, High Fiber Glazed Fruit [0072] The LVDF syrup of Example No. 8 was prepared, cooled to about 150° C. and maintained while various dried fruit was coated. The coated fruit pieces were sprayed with a lecithinated oil and and rotated under a stream of air hot enough, and for a sufficient time to anneal the coating. The sensory qualities of the resulting product were essentially the same as found in the sucrose-based product described in Example 3. The product of this Example, however, would be considered to have a low glycemic index. [0073] Thus, those of ordinary skill in the art will understand and appreciate that the foregoing describes a product and method for formulating a low viscosity dietary fiber syrup that is capable of multiple uses to make and treat foodstuff. The product and method of the present invention permits the making of foodstuffs which exhibit both excellent levels of dietary fiber, while, at the same time preserving or enhancing the taste or palatability of the foodstuff. Additionally, foodstuffs having both high levels of dietary fiber and low glycemic index values may be made with product and method of the present invention. [0074] It will be understood, therefore, that the present invention may include the following products and methods: [0075] a. Syrups: LVDF syrup is useful with flavoring and sweeteners as a syrup topping as with any conventional syrup such as maple syrup, caramel or honey. The inventive LVDF syrup may be flavored for use as a variegating syrup in frozen confections. Since the simple unsweetened LVDF syrup is not sweet, it may be used as a base for savory syrup-form condiments. [0076] b. Hard Candy: Hard candies having improved sensory character and high fiber content. [0077] c. Confectionery Glaze: The LVDF syrup is useful when made into consistencies ranging from caramel through to toffee and hard-crack confections and used may be applied as a coating to baked confections, or coated onto fresh or dried fruits to provide a range of confections with a high content of dietary fiber. [0078] d. Low-Fat versions of Fatty Confections: Classical confections, such as Pralines and Nut Brittles have a shorter cleaner-biting texture than conventional hard candies, which is understood to be a consequence of their high fat content. This character is believed to have contributed to their long popularity. We have found that comparably attractive textures can be created, at much lower or near zero fat contents by doctoring the sucrose in such reduced fat content formulas with LVDF. [0079] e. Carrier (or “support”) for Drying Heat Labile Flavors and Biologicals; Many flavors and biologicals become changed in undesirable ways when they are dried. This is believed to be a consequence of the large amount of energy (usually heat and especially when in the presence of oxygen in the air used to heat the product and carry away the moisture) that must be applied in order to drive off enough moisture to render the composite mass dry, and to confer stability to the material when stored. The inventive LVDF syrup readily looses moisture, resulting in less heat-exposure to the heat labile burden, and consequently greater conservation of its desirable properties. [0080] f. Sucrose-Replacement: The sucrose component of the LVDF syrups may be replaced by a variety of other sugars, including fructose, trehalose, erythritol, other sugar alcohols, “Palatinate” and de-colored, de-flavored fruit syrups. The addition of LVDF syrup to each of these produces characteristic shifts in the functional properties of the resulting compound syrup that bring them closer to the character of sucrose-based products, the utilities of which will be obvious to one skilled in the confectionary arts, once the teachings contained herein are understood. [0081] While it will be understood by those of ordinary skill in the art, that the foregoing embodiments are described with reference to their preferred embodiments, it will be understood that the Examples provided are intended merely to illustrate particular formulations and uses of the present invention, and are not limiting of the present invention, which is limited only by the scope of the claims appended hereto.
A product and method by which a range of foodstuff products may be produced which are very pleasant in taste and texture, and therefore, pleasant to eat, and which contain a sufficiency of soluble dietary fiber to effectively supplement the typically low fiber dietary intake. By adding a low viscosity, non-digestible fiber either along or in a syrup composition, foodstuffs may be amended in such a manner as to increase dietary fiber intake without adversely affecting the palatability of the foodstuffs.
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RELATED PATENT INFORMATION This Patent Application is based upon U.S. Provisional Patent Application, Ser. No. 60/225,401, filed Aug. 15, 2000. BACKGROUND OF THE INVENTION 1. Field of the Invention The subject portable lighting fixture assembly is generally directed to a portable assembly for adaptive use in numerous settings and applications. More specifically, the portable lighting fixture assembly is directed to an assembly that may easily and conveniently yet in a highly secure and adaptive manner be mounted to a structural frame member of, for instance, a space partition. A common problem encountered by those utilizing temporary structures such as display booths, compartmentalized work cubicles, and the like is the unavailability of ready means for amply lighting the given area. The partitioned area is, in most cases, defined simply by a plurality of standing wall or partitioning members. Without a ceiling or other overhead member on which to suspend overhead lamps or other lighting fixtures, the user is relegated to securing the required lighting fixtures somehow on the standing partition structure. Freestanding lamps may be employed; however, space limitations in most applications do not afford such use of freestanding lamp structures, at least not in both safe and effective manner. Accordingly, designs of lighting fixtures and brackets attachable to various portions of partitioning members abound. As partitioning members invariably include a plurality of elongate frame members; known lighting fixture/bracket designs seek to yield a secure coupling to such frame members for adequate positioning and orientation of the required lighting source. Many designs, for instance, employ a bracket that adjustably clamps onto either a vertical or horizontal partition frame member, suspending a light source therefrom via an extension arm. Other designs employ in similar manner brackets which either hang or are secured by fastener to a partition frame member. Numerous practical drawbacks result from such known designs. First, the strength and stability of the coupling of bracket and frame members is in each design far from secure, particularly since the frame members tend to be configured with a cylindrical, tubular contour. Among other things, this poses a potentially dangerous situation, for high intensity lamps of wattages on the order of 300 are typically used in many applications. An unintentional decoupling of the bracket from a frame member would then permit an intensely hot lamp to contact and burn persons or items in the immediate vicinity. What is more, without reinforcing the coupling with extraneous fastening hardware or, simply, with a cumbersome and unsightly wrap of tape, the type, configuration, and number of lighting sources that may be adequately supported from any one given bracket becomes prohibitively limiting. A great number of individual lighting fixtures, along with their respective brackets and reinforcing measures, must tediously be coupled individually to appropriate frame members in order to obtain adequate lighting. This significantly burdens not only the user's set-up and take-down efforts, it burdens him or her with the need to manage a great number of discrete, misplaceable parts. There is, therefore, significant need for a portable lighting fixture that may be quickly, conveniently—yet securely—coupled to one or more frame members of a partition structure. There is a significant need, moreover, for such a portable lighting fixture assembly having one or more light sources that may be readily adapted in position and orientation to a given application. There is a further need for such a portable lighting fixture assembly that may be coupled to a partition frame member with sufficient stability to support lighting sources quite varied in type, configuration, and number. 2. Prior Art Lighting fixture assemblies for use in illuminating a display area defined by a partition frame system are known in the art. The best prior art known to Applicant includes U.S. Pat. Nos. 6,036,337; 6,042,251; 6,079,851; 6,079,992; 5,967,649; 6,068,381; 5,436,811; and, 5,483,432. The known prior art also includes a family of lights, light fixtures, and brackets marketed by LIGHT CRAFT MANUFACTURING, INC. of Fremont, Ohio, such as the dual arm extension fixture Model No. SL-514. Such known devices, however, are either affixed to partition frame members by bolt-down or other such permanent fastening means, or else lack security and stability in coupling to the given partition system. For instance, the dual arm extension fixture Model No. SL-514 includes a pair of arms, the free ends of which together support a bulb light source. The other ends of the arms are mounted to a mounting bracket whose bolt-down plate is, in turn, fastened by bolts to an intermediate portion of a horizontally extended cross frame member. This and other such lighting assemblies known in the art fail to provide the combination of flexibility, convenience, stability, and safety that enables a user to quickly and confidently couple the assembly in adaptive manner to a given partition system for adequate lighting of the desired display area. SUMMARY OF THE INVENTION It is a primary object of the present invention to provide a portable lighting fixture assembly having one or more light sources that may be detachably yet securely coupled to a frame member to illuminate a display area about the frame member in highly effective manner. It is another object of the present invention to provide a portable lighting fixture assembly which secures detachably to one or more frame members of a partitioned system to adjustably illuminate a display area defined by the partition system. These and other objects are attained by a portable lighting fixture assembly formed in accordance with the present invention. The subject portable lighting fixture assembly generally comprises a base portion adapted for detachable coupling to a frame member, and a lighting portion coupled thereto for illuminating a display area. The base portion includes a deck member and an elongate coupling member extending transversely from the deck member for telescopically engaging a frame member. The lighting portion includes at least one lighting fixture having an extension arm projecting from the deck member. Each lighting fixture terminates at a lighting source coupled to a free end of its extension arm. Preferably, at least a portion of the extension arm of a lighting fixture is malleable in configuration, being formed in one preferred embodiment with a metallic flex configuration. The base portion preferably defines a substantially planar platform, and each extension arm of a lighting fixture projects from that platform. The base portion's coupling member is preferably formed with a substantially tubular contour defmed by a side wall part that extends longitudinally downward, and has formed therein at least one longitudinal slot for receiving therethrough a hooking element of a cross frame member. In certain embodiments, the base portion's coupling member is configured for telescopically receiving therein an upper portion of a vertical frame member. In other embodiments, the base portion's coupling member is configured for telescopic insert into an upper portion of a vertical frame member. Where the given vertical frame member is formed with a side wall portion having a longitudinal slot therein to engage the hooking element of a cross frame member, the longitudinal slot formed in the side wall part of the base portion's coupling member is disposed in alignment therewith. DESCRIPTION OF THE DRAWINGS FIG. 1 is an illustrative perspective view of one embodiment of the present invention; FIG. 2 is an illustrative perspective view of a vertical partition frame member known in the prior art; FIG. 3 is an illustrative perspective view illustrating the coupling of the embodiment of the present invention shown in FIG. 1 with the vertical partition frame member; FIG. 4 is an illustrative perspective view, partially cut-away, of the embodiment of the present invention shown in FIG. 1 coupled to a vertical partition frame member; FIG. 5 is an illustrative perspective view of a first exemplary application of the embodiment of the present invention shown in FIG. 1; FIG. 6 is an illustrative perspective view of a second exemplary application of the embodiment of the present invention shown in FIG. 1; and, FIGS. 7-16 are graphic reproductions showing various portions of a second embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring now to FIG. 1, there is illustrated an exemplary embodiment of a portable lighting fixture assembly 10 formed in accordance with the present invention. For purposes of clarity, details such as electric cords that may be necessary for any non-battery powered light sources utilized and details identically replicated in each of the lighting source extensions are not shown. Portable lighting fixture assembly 10 generally comprises a base portion 100 and a lighting portion 200 supported thereby. Base portion 100 preferably includes a deck member 110 from which extends an elongate coupling member 120 . Deck member 110 preferably provides a substantially planar platform 112 on which lighting portion 200 may be amply supported in stable manner. Deck member 10 also defines a shoulder 114 disposed radially about the upper end of coupling member 120 to, in certain embodiments, abut and engage portions of the partition frame member to which coupling member 120 may be coupled, as described in following paragraphs. Coupling member 120 is formed with a suitable configuration to realize substantially flush telescopic engagement with a partition frame member (shown in FIG. 2 ). So as to accommodate any connecting holes in the partition frame member to which it is telescopically engaged, coupling member 120 includes one or more slots 122 configured and positioned as required for the particular configuration of the partition frame member employed in the intended application. Preferably, deck member 110 and coupling member 120 are each formed of a metallic material and coupled one to the other in fixedly secured manner. One or both of the deck and coupling members 110 , 120 may alternatively be formed of other materials having the sufficient strength, rigidity, and durability to withstand the mechanical and thermal loads to which they may be subjected during use in the intended application(s). In addition, coupling member 120 may be formed with a contour and configuration other than that shown in the exemplary embodiment, so long as it forms a sufficiently stable telescopic engagement with the given partition frame member. For example, coupling member 120 may be formed with a rectangular, oblong, or other sectional contour, depending on the given frame member's contour and configuration. Depending on the intended application(s), it may be formed with either the tubular configuration shown or a non-tubular configuration. Deck member 110 may, likewise, be formed with any other suitable contour and configuration than that shown, so long as it forms a sufficient structural foundation for the coupling of lighting portion 200 thereto. Lighting portion 200 includes one or more lighting fixtures 210 . Each lighting fixture 210 preferably includes an extension arm 212 securely coupled at one end to base member 110 and having coupled at another end thereof—terminal end 214 —an incandescent lamp bulb, or any other suitable lighting source 216 (fluorescent, halogen, etc.). For enhanced adjustability, extension arm 212 is preferably embodied in malleable form using any suitable measures known in the art. Note, however, extension arm 212 of one or more lighting fixtures 210 may alternatively be embodied in rigid form. In certain embodiments, of course, a plurality of lighting fixtures 210 may be employed respectively having various combinations of both rigid and malleable extension arms 212 . Similarly, a plurality of lighting fixtures 210 may be employed in certain embodiments wherein varying combinations of type and configuration for lighting source 216 are be used. If the lighting source 216 employed in a particular lighting fixture 210 is driven via an electric power cord, that power cord (not shown) may be internally routed through the given extension arm 212 , and base portion 100 . The electric power cord may alternatively be, simply, routed (and fastened) along the outer surface of the given extension arm 212 and appropriate sections of base portion 100 (as shown in FIGS. 7 - 16 ). Although the extension arm 212 and terminal end 214 of each lighting fixture 210 are preferably formed of a metallic material, they may alternatively be formed of any other suitable material known in the art, such as plastic, dense rubber, or the like having the mechanical and/or electrical properties required for the intended application. Also, the sectioned, metallic flex configuration of extension arm 212 in the embodiment shown may be substituted by any other configuration known in the art suitable for the requirements of the intended application. Turning now to FIG. 2, there is illustrated an exemplary partition frame member 1 commonly employed in the prior art to form freestanding partitions for temporary exhibition booths used at conventions, trade shows, and the like. This vertical, or upright, frame member 1 is typically formed with a connection slot 1 a which accomodates a hooking element extending axially from the end of a horizontal, or cross, frame member 2 (FIG. 4) that extends between a pair of vertical frame members 1 to form a partition wall frame. Referring to FIGS. 3-4, the coupling of the subject portable lighting fixture assembly 10 to a vertical partition frame member 1 is illustrated. As shown, coupling member 120 of assembly 10 is configured with a cylindrical, substantially tubular contour appropriately dimensioned such that when coaxially coupled to an upper portion of partition frame member 1 (as indicated by the directional arrow 50 ), coupling member 120 fits telescopically about that upper portion of the partition frame member 1 . Slot 122 may then be aligned with the partition frame member's slot 1 a, such that the coupling of the partition cross frame member's hook element 2 a to the vertical partition frame member 1 (indicated by the directional arrow 55 ) may not be obstructed. Thus engaged to the partition frame members, the subject assembly 10 is firmly and securely seated—obviating the need for any extraneous fastening or securing hardware. If malleable extension arms 212 are employed, the user may then adjust the positions and orientations of the individual lighting fixtures 210 to direct the light sources coupled thereto in the desired manner without fear of disturbing or de-stabilizing the assembly's coupling to the partition frame. One or more portable lighting fixture assemblies 10 may be employed to yield the required lighting. The extremely secure coupling of assembly 10 to the partition frame members permits a relatively great number of lighting fixtures 210 to be supported on a common base portion 100 . The user is able, therefore, to set up and establish ample lighting without the excessive investment of time and effort, and without the handling of numerous individual hardware components that would invariably be required otherwise. Turning now to FIGS. 5 and 6, there are shown exemplary applications in which one or more of the subject portable lighting fixture assemblies 10 may be employed. As shown, the lighting sources of each assembly 10 are securely retained well out of the way of any person or item within a booth 5 , 5 ′ established as shown. The individual lighting fixtures 210 may then be directed as needed to provide the desired illumination. Referring to FIGS. 7-16, there are shown various views of the subject portable lighting fixture assembly 10 ′ formed in accordance with another embodiment of the present invention. For the purposes of clarity, some of the elements shown in the embodiment of FIGS. 1-6 which remain unchanged in this embodiment have not been separately marked with their reference numbers. Note, however, that the electric cords leading from each of the lighting sources of lighting fixtures 210 are shown routed along and clipped to their respective extension arms 212 . As shown most clearly in FIGS. 7 and 9, coupling member 120 ′ of the assembly's base portion 100 is contoured and dimensioned in this embodiment to coaxially insert within an upper portion of a vertical partition frame member 1 , with shoulder 114 abutting the terminal end of that frame member's upper portion. Coupling member 120 ′ is formed with a slot 122 ′ which aligns with the vertical partition frame member's connecting slot 1 a. As before, this enables the hooking element 2 a of a horizontal partition frame member 2 to engage the connecting slot 1 a of the vertical partition frame member 1 unobstructed. Note that use of the subject portable lighting fixture assembly 10 is not limited to the exemplary frame structures of the type shown in FIG. 2 . Rather, assembly 10 may be conveniently engaged telescopically to any number of suitable frame structure types known in the art. In the embodiment of FIG. 12, for instance, lighting fixture assembly 10 ′ is telescopically engaged to an upper portion of a vertical frame member 1 equipped with its own freestanding structure formed by a set of radiating legs 1 ′, 1 ″, 1 ′″. Although not shown, other such frame structures may be employed, as may additional extraneous measures—like reinforcing/securing hardware—where the intended application so requires. Although this invention has been described in connection with specific forms and embodiments thereof, it will be appreciated that various modifications other than those discussed above may be resorted to without departing from the spirit or scope of the invention. For example, equivalent elements may be substituted for those specifically shown and described, and certain features may be used independently of other features, all without departing from the spirit or scope of the invention as defined in the appended Claims.
A portable lighting fixture assembly ( 10 ) for detachably coupling to a frame member of a partition or other such structural system is provided. The portable lighting fixture assembly ( 10 ) generally comprises a base portion ( 100 ) and a lighting portion ( 200 ) coupled thereto for illuminating a display area defined by the partition system. The base portion ( 100 ) includes a deck member ( 110 ) and an elongate coupling member ( 20 ) extending transversely from that deck member ( 110 ) for telescopically engaging the frame member. The lighting portion ( 200 ) includes at least one lighting fixture ( 210 ) having an extension arm ( 212 ) projecting from the deck member ( 110 ). Each lighting fixture ( 210 ) terminates at a lighting source ( 216 ) coupled to a free end ( 214 ) of its extension arm ( 212 ). The portable lighting fixture assembly ( 10 ) is thereby securely seated on the frame member to illuminate the display area.
0
TECHNICAL FIELD OF THE INVENTION [0001] The present invention generally relates to a modeling compound for use as a play material suitable for young children. In particular the present intervention provides a non-toxic, malleable modeling compound for molding, extruding, or sculpting shapes or figures, and the modeling compound can be utilized as a crayon upon air drying. BACKGROUND OF THE INVENTION [0002] Generations of children have been amused by modeling compounds that are important tools for aiding in the development of manual dexterity, fine motor skills and creativity. There are a number of specialty modeling compounds on the market today. The continuing need for improved and varied modeling compositions has prompted the development of a great variety of such modeling compounds with special features. For example, U.S. Pat. No. 5,498,645 discloses an improved water-based modeling dough which forms a solid, lightweight, durable product upon drying, U.S. Pat. No. 6,444,728 discloses a modeling lightweight dough which is excellent in lightweight, formability, shape preservation of the modeled shape, and bending deformation resistance of the modeled product obtained by modeling and drying. U.S. Pat. No. 5,873,933 discloses a Malleable play material compound resembling loose soil, which is formed by mixing a soluble cellulose, a polyvinyl alcohol, propylene glycol, water, sodium tetraborate, sodium carbonate and a light mineral oil. U.S. Pat. No. 5,506,290 discloses a plastic moldable composition which can be moldable, extrudable, stretchable, and inflated into bubbles for use as a play activity. [0003] Accordingly, it is a general object of the present invention to provide an improved modeling composition with special features due to the continuing need in the art. More specifically, the present presentation provides a non-toxic, malleable modeling compound for molding, extruding, or sculpting shapes or figures, and the modeling compound can be utilized as a crayon upon air drying. Children can create their own crayons in different shapes easily. This provides additional play value to conventional modeling compound. BRIEF SUMMARY OF THE INVENTION [0004] The present invention relates generally modeling composition. More particularly, the invention relates to a non-toxic, malleable modeling compound for molding, extruding, or sculpting shapes or figures, and the modeling compound can be utilized as a crayon upon air drying. The present composition comprises generally wax, water, starch, filler, emulsifier, lubricant and colorant. In one preferred form, the composition of the invention includes 20-80% wax, 10-60% water, 5-30% starch, 5-30% filler, 1-10% emulsifier, 1-10% lubricant and 0.1-10% colorant. BRIEF DESCRIPTION OF DRAWINGS [0005] Table 1 is a general formulation for one embodiment. DESCRIPTION OF THE PREFERRED EMBODIMENTS [0006] While the present invention is susceptible of embodiment in many different forms, as will be described herein in detail specific embodiments thereof with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated. [0007] To achieve the foregoing and other objects in accordance with the purposes of the present invention, as embodied and broadly claimed herein, the modeling compositions disclosed in the present invention comprises 20-80% wax, 10-60% water, 5-30% starch, 5-30% filler, 1-10% emulsifier, 1-10% lubricant and 0.1-10% colorant. [0008] In a preferred embodiment, paraffin wax having a melting point of about 130° F.-150° F. is used in the present composition. Paraffin wax is a white and crystalline solid produced by refining and de-oiling the wax with the help of hydrogeneration refining equipments. Commercial paraffin wax is composed principally of normal paraffin of the C n H 2n+2 series and is a mixture of hydrocarbon with a average molecular weight of 300 to 500. It should be understood by those skilled in the art that other waxes may be utilized. For example, microcrystalline wax, carnauba wax, candelilla wax, beeswax or other petroleum derived waxes, mineral, vegetable, animal, synthetic waxes and their mixture thereof. [0009] Starch is preferably added in the present composition from about 5% to about 30%. Starch is used as a binder and gives the present composition malleability, making the modeling compound feasible for molding, extruding, or sculpting shapes or figures. The starch-based binder can be selected from cornstarch, potato starch, tapioca starch, rice starch, glutinous rice starch, wheat flour, rye flour and their mixture thereof. Other water-soluble polymeric resin may also be utilized. [0010] Talc in an amount from 5-30% is preferably added as filler in the present composition. Other fillers such as calcium carbonate clay, talc, barium sulfate, silica, aluminum oxide, titanium oxide and diatomaceous earth may be utilized. The lubricant can be selected from mineral spirits, mineral oil, and vegetable oil. [0011] Emulsifier is preferably added in the present composition from about 1% to about 10%. This can help the dispersion of wax phase into the aqueous phase, yielding a modeling composition with smooth consistency and improved stability. Various emulsifiers that can be used in the present composition will be known to persons skilled in the art. Some examples of suitable emulsifiers include the group consisting of salts of saturated fatty acids, salts of straight-chain fatty acids, alkyl sulfosuccinates, alkyl phosphates, ethoxylated alcohols and polyoxyethylenesorbitan monostearate. [0012] The present composition comprises a colorant, from about 0.1% to about 10% by weight, so that upon drying, the composition can be utilized as a marking device having various colors on a writing surface. A pigment is preferably used than a dye. For examples, phthalocyanine pigment, an indigo pigment, a quinacridone pigment, an anthraquinone pigment, a dioxazine pigment, a thioindigo pigment, a perinone pigment, a perylene pigment, an indolenone pigment, and an azo-azomethine pigment, titanium oxide and carbon black etc. However, the colorant used is not limited to the above. [0013] Also, other additive, such as preservatives, fragrance material and embittering agent may be added to the formulation to enhance the function and the quality of the resulted modeling composition. [0014] A general formulation of this disclosure is shown in Table 1. [0015] Although several embodiments described above and by the claims serve to illustrate various concepts, components and techniques which are the subject of this patent, it is apparent to those of ordinary skill in the art that other embodiments incorporating these concepts, components and techniques may be used. It is understood that the scope of the following claims are not limited to the described embodiments and that many modifications and embodiments are intended to be included within the scope of the following claims. In addition the specific terms utilized in the disclosure and claims are used in a generic and descriptive sense and not for the purpose of limiting the invention described in the following claims.
A modeling composition which is a non-toxic, malleable modeling compound for molding, extruding or sculpting use. Composition generally comprises wax, water, starch, filler, emulsifier, lubricant and coloring. When dried this modeling composition also creates a crayon.
2
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a doll having elements for producing soap bubbles, and more particularly to a doll which can be used by young children safely and with minimal risk of spilling the bubble-making liquid while keeping user interest high. 2. Description of the Related Art Many types of bubble blowing toys and devices have been developed for children. Children have a fascination with the creation of bubbles out of liquid. Examples of bubble blowing toys directed to children are disclosed in U.S. Pat. Nos. 1,733,478 (bubble blowing elephant); 2,842,894 (bubble blowing toy figure); 3,228,136 (electrical bubble blowing toy); 3,388,498 (bubble making toy figure); and 4,556,392 (bubbling self-propelled toy). For the most part, these devices are one dimensional, in that the only function they serve is that of a bubble blowing apparatus. Further, many of the devices are too complicated for younger children, thereby requiring adult supervision or assistance. Due to these restrictions, it is often difficult for bubble blowing devices to hold the interest of younger users. SUMMARY OF THE INVENTION Accordingly, an objective of this invention is to provide a doll capable of blowing bubbles. Another object of this invention is to provide a bubble blowing device which has an independent use as a doll. A further object of this invention is to provide a doll having elements for producing bubbles which is easily manufactured at a low cost. Additional objects and advantages of the invention will be set forth in part of the description which follows, and, in part, will be obvious from the description or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the appended claims. To achieve the foregoing objects and in accordance with the purpose of the present invention, the doll includes: a toy body of human configuration having a trunk portion bearing a receptacle for containing a mixture of water and soap necessary for the production of the bubbles, as well as a head portion within which there is housed an electronically actuated air impeller device which is functionally connected to a mouth opening present in said head portion; upper extremities or arms, at least one of which is pivotally mounted on said trunk portion and, operatively connected to a switch element for controlling the electric circuit for the actuation of said air impeller device; a tool for forming the bubbles, having a handle portion for attachment to the movable arm or arms and a ring-shaped portion for forming the actual bubbles. Furthermore, the mouth opening of the aforesaid head portion and the trunk portion on which the receptacle for the soapy solution is arranged are disposed along a circumferential arc which has its center at the point of articulation between the arm and trunk and a radius corresponding to the effective length of the arm and tool for the production of bubbles. In this way, by manually moving said pivoted arm it is possible to introduce the bubble-producing tool into the corresponding receptacle and then position the tool, in front of the mouth opening of said head portion. Air is then impelled from the mouth toward the tool, whereby a bubble is made. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a front view illustrating the doll of the present invention; FIG. 2 is a side view showing the pivotal motion of the arms of the doll; FIG. 3 is a side view, partially in section, of the doll of the present invention, in which the arrow A shows the movement effected by the pivoted arm thereof; FIGS. 4A and 4B are views illustrating the tool for producing the bubbles; FIG. 5 is a side view illustrating the receptacle which contains the soapy solution; FIG. 6 is a side, cross-sectional view of the air impeller device; FIG. 7 is a top, partial cross-sectional view of the air impeller device, and FIGS. 8 and 9 illustrate an alternative embodiment in which the arm movement is motor driven. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The structure of the present invention is illustrated in FIGS. 1 and 2. A doll 1 is formed of a body having a head portion 2, a trunk portion 3, a lower limbs portion 22 (legs and feet), and a pair of arms 4, at least one of which is articulated, e.g., swinging on the aforementioned trunk portion 3, as is illustrated in FIG. 2. Attached to the trunk portion 3 is a receptacle 15 for holding bubble making liquid. Attached to the pivoting arm 4 is a hand 21 which holds a tool 16 which can be dipped in the bubble making liquid contained in the receptacle 15 and then moved directly opposite an opening 5, which imitates a mouth, in the head portion 2 so that bubbles can be formed utilizing air forced through the opening 5, as discussed in detail below. At least the arm 4 holding the tool 16 is pivotally mounted. The second arm may also be pivotally mounted on a single axis through the trunk portion 3 so that the arms 4 ascend and descend together. The bubble making elements can be seen more easily in FIGS. 3, 6 and 7. An air impeller device 6, which will be described in greater detail below, has an outlet nozzle 7 which is coupled to said mouth opening 5 in such a manner that the stream of air generated thereby will emerge through the mouth opening 5 via the nozzle 7. The air impeller device 6 consists of an electric motor 8 which is powered by a battery 23, the live terminal of which is connected to a rotor 9 having a plurality of transverse vanes 10 which is fitted in the interior of a cylindrical body 11 in which said outlet nozzle 7 is tangentially conformed. In addition, in said cylindrical body 11 there are formed a plurality of holes 12 which serve as suction intakes of the device 6. Referring still to FIG. 3, the arm 4 which is articulated on the trunk portion 3 has, in a region within said trunk portion 3 a stem or lug 13 which is operatively connected to a switch 14, for instance a blade switch 14, arranged in a feed circuit of the motor 8 of the air impeller device 6. The arrangement of the stem or lug 13 is such that in a position of rest of the doll 1, the switch 14 is in its open position, while in an active position of the doll, that is to say with the arm raised upward by the manual action of the user or mechanical action, the stem or lug 13 effects the closing of the switch 14 with the consequent production of a tream of air by the impeller device 6 through the opening 5. Referring now to FIG. 5, the receptacle 15 is formed of inner upper and outer portions 15' and 15', respectively. The inner upper portion 15' has a downward directed concavity of a volumetric capacity approximately equal to that of the portion 15' so that even in the event that the receptacle 15 is tipped sideways or turned upside down, no loss of the liquid contained therein would take place since it would remain contained within the said concavity of the upper portion 15'. As shown in FIGS. 4A and 4B the tool 16 for the forming of the bubbles is formed of a handle portion 16' for attachment to the hand 21 of the arm 4 and a ring-shaped portion 16' for picking up and holding a film of bubble-making liquid for the forming of the bubbles. The ring-shaped portion 16' is provided on its inner periphery with a plurality of projections 17, whereas the outer periphery includes a plurality of indentations 18, both of which contribute to facilitating the formation of the film of bubble making liquid which is necessary for the forming of the bubbles. The fastening of the receptacle 15 to the corresponding region of the trunk portion 3 can be effected in a variety of different ways. For instance, as shown in FIG. 3 protruding portion 19 may extend from the trunk portion 3 on which the handle 20 of the said receptacle 15 can be engaged. The handle 20 may be removable from the protruding portion 19 or may be permanently attached to protruding portion 19 during manufacture. As will be easily understood by those skilled in this art, for the proper operation of the doll, it is necessary said receptacle 15 and said mouth opening 5 be arranged in the circumferential arc. More particularly, the bubble-forming tool 16, in order to ascend and descend as indicated by the arrow A in FIGS. 2 and 3 must be alternately brought opposite the mouth opening 5 and then introduced at the ring-shaped portion 16' into the inside of the receptacle 15 which contains the bubble making liquid, by the movable arm 4. The center of the circumferential arc is at the point of rotation of the arm 4 on the body and the radius of the arc is equal to the distance between said point and the ring-shaped portion 16 of the bubble-forming tool 16. In this way, by the manual or mechanical actuation of the descent and ascent of the arm 4, the tool 16 becomes wetted with the bubble making liquid contained in the receptacle 15, with the consequent formation of a soapy film in the ring-shaped portion 16'. The ring-shaped portion 16' is then brought opposite the opening 5 of the head 2. A stream of air is then generated by the impeller device 6, and the desired bubble or bubbles are produced. As previously mentioned, the position of the stem or lug 13 of the arm 4 only acts on the switch 15 so as to cause the closing thereof to activate the impeller device 6, when said tool 16 has reached the vicinity of the opening 5. In the embodiment illustrated in FIG. 3, the arm 4 holding the bubble-forming tool 16 is manually moved from the receptacle 15 to the opening 5. This allows for the manufacture of a simple and low cost embodiment of the present invention. FIGS. 8 and 9 illustrates an alternate embodiment according to the present invention, whereby an electrically-driven mechanical device is introduced into the doll, for automatically moving the arm 4 to move the tool 16 from the receptacle 15 to the opening 5 and back again. This mechanical motion can be carried out by pushing a button 25 situated on the doll 1 above a battery compartment door 29 which closes a circuit thereby energizing a motor 26 which in turn activates a gear train 27 operatively connected between the motor 26 and the arm 4 portion, which causes the arm 4 and connected tool 16 to ascend and descend. The gear train 27 and motor 26 required for causing the ascending and descending motion of the arm 4 are well known to those in the art, and therefore, will not be further described herein. The rest of the structure of the doll is the same as is contained in the first embodiment. That is, when the arm 4 has ascended to a position such that the tool 16 is close to the opening 5, a circuit is closed by the contact of the stem or lug 13 and the blade switch 14, causing the air impeller device 6 to generate a stream of air through the opening 5 and the ring-shaped portion 16' of the tool 16, thereby producing bubbles. A wide variety of embodiments are foreseeable from the basic embodiments that have been described above. The device can be noise actuated, such that a particular voice or noise command such as the clapping of hands can cause the ascending motion of the arm 3 and accompanying tool 16 to the opening 5 which would cause the air impeller 6 to generate air through the ring-shaped portion 16' of the tool 16, thereby producing bubbles. As described above, the present invention has an added dimension in that it serves a dual purpose. Not only can the device be used for making bubbles, upon the removal of the receptacle 15 and tool 16, the device also serves as an ordinary doll for the user. The idolation of baby dolls by young children is of course well known. This also distinguishes the present invention from the above described single dimensional bubble blowing apparatuses. The foregoing is considered illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described. Accordingly, all suitable modifications and equivalents may be resorted to that fall within the scope of the invention and the appended claims.
A doll is provided capable of blowing bubbles. The doll has a receptacle for holding bubble making liquid attached to the doll's trunk. A bubble making tool having a ring-shaped end is attached to a moveable arm of the doll. The arm is able to pivot about the trunk so that the tool may be dipped in the liquid and raised up to a mouth opening formed in the doll. An air impeller is located in the doll's head and forces air out of the doll's mouth when a circuit is closed by the motion of the arm in bringing the tool close to the mouth opening. Bubbles are produced when the air flows through the ring-shaped end of the tool coated with a liquid film.
0
CROSS REFERENCE TO RELATED APPLICATIONS [0001] The present application claims priority from earlier filed U.S. Provisional Patent Application Ser. No. 60/573,259, filed May 21,2004 and entitled “Easily Opened Tamper Evident Shrink Band.” BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present invention relates generally to a tamper-evident band for attachment to a container in order to indicate if the container has been tampered with after the band has been attached and to a method of applying a heat-shrinkable band to an associated container for making the container tamper proof. [0004] 2. Description of the Prior Art [0005] Tamper-evident bands are useful for alerting consumers of products marketed in bottles and containers that the product might have been opened prior to retail sale. These type bands have been placed on prescription and over-the-counter pharmaceutical products such as eye drops, cosmetics, alcoholic beverages, and many other products. Generally, this type of band will show signs of breakage or distortion when the container cap is rotated relative to the container body. This type of breakage or distortion of the band provides a visual indication to a consumer that the product might have been opened or tampered with prior to sale. [0006] There are a variety of tamper-evident and resistant bands shown in the prior art. One type of tamper-evident seal that has been used in the past is a heat-shrinkable member, usually comprising heat-shrinkable thermoplastic material. This type of heat-shrinkable member is usually applied to an associated container in a generally cylindrical form, with heat thereafter applied to the member so that it shrinks and conforms to the associated container. The material from which the member is formed and the manner in which it is applied are selected such that upon attempted opening or opening of the container, the member is visually and permanently deformed to indicate tampering. [0007] While generally cylindrical heat-shrinkable bands are effective in providing a tamper proof container, they can be difficult for the consumer to remove in the ordinary course of opening the container, e.g., to dispense medicine held in the container. As a result, various types of tear away strip arrangements have been used in the past. These have still generally failed to provide and easy opening tamper-evident band. [0008] Also, since the application of the tamper band is typically performed attendant to high speed packaging of products, it is frequently impractical or impossible to sufficiently control and monitor tamper band application to assure the desired interaction of the bands with their associated containers. Additionally, in the case of heat shrink bands, it was often difficult to locate the tear strip once the material had shrunk so that the tear stip or associated pull tab could be grasped by the user. [0009] Thus, it is desirable to provide a tamper proof container having a pull tab which is easily grasped by a consumer in order to remove the tamper-evident band. [0010] It is also desirable to provide a method of applying heat-shrinkable tamper bands or like members to containers so that it is possible to more easily identify and locate the pull tab or strip. SUMMARY OF THE INVENTION [0011] The tamper-evident band of the invention can be utilized with a wide variety of containers which hold goods of various descriptions. It is especially suitable for attachment to a container and cap assembly. In such an assembly, the cap is removably attached to the container, the container having a bottom, side walls, a mouth, and top edge adjacent to the mouth, the cap having a top, side walls, and bottom edge adjacent to the mouth of the container. The band is formed from a planar sheet of material having at least one tear strip defined by two parallel perforated lines there through which terminate in a die cut. The planar sheet also has a pair of seam regions which allow the sheet to be folded and joined to make a continuous tube of material which can then be cut in desired lengths. [0012] A series of registration marks are provided on the planar sheet of material for aligning a cut tube of material on an assembled container and cap. The registration marks insure that the tear strip overlays the top edge of the container and bottom edge of the cap when in place on the container. The tear strip also extends over the top edge of the cap so that the die cut is positioned on the top of the cap. [0013] The preferred planar sheet of material is a thermoplastic material which can be heat shrunk in a desired position on the container and cap assembly to thereby form a band of material. The heat shrinkage of the sheet of material, as well as the proper registration of the material on the container by means of the registration marks, causes the die cut to separate and form a tab which protrudes from the planar surface of the sheet of material and which can be grasped by a user in order to more easily separate the band from the container. [0014] Tampering with or removing the band from the assembly by way of pulling on the tear strip, or removing or repositioning the cap from the container, causes the perforated lines of the tear strip to deform or rupture, thereby serving as visible and physical evidence of tampering with the assembly. [0015] In the preferred form of the invention, the tube of material has a central vertical axis with the tear strip being arranged on the sheet of material generally parallel to the central vertical axis. Most preferably, the planar sheet of material has a pair of tear strips defined by two parallel perforated lines there through, each of the tear strips terminating in a die cut. The tear strips are generally equidistantly spaced about the circumference of the continuous tube of material on opposite sides thereof. [0016] In the preferred method of practicing the invention, a planar sheet of thermoplastic material is provided as previously described having at least one tear strip defined by two parallel perforated lines there through which terminate in a series of evenly spaced die cuts, the planar sheet also having a pair of seam regions. The planar sheet is folded at the seam regions with the seam regions being joined to make a continuous tube of material which can then be cut in desired lengths. A series of registration marks are provided on the planar sheet of material for aligning a cut tube of material on an assembled container and cap, whereby the tear strip overlays the top edge of the container and bottom edge of the cap when in place on the container, the tear strip also extending over the top edge of the cap so that the die cut is positioned on the top of the cap. The tube of material is then heat shrunk in a desired position on the container and cap assembly to thereby form a band of material. The step of heat shrinking, as well as the proper registration of the material on the container by means of the registration marks, causes a selected die cut to separate and form a tab which protrudes from the planar surface of the sheet of material and which can be grasped by a user in order to more easily separate the band from the container. [0017] The application of the registration marks is preferably accomplished by the operation of a printing machine. Similarly, the die cuts are preferably made by the operation of a cutting machine, the printing and cutting operations being synchronized in order to properly determine the cut length of the bands. In a preferred embodiment of the invention, the printing machine includes a printing cylinder and the die cutting machine includes a cutting cylinder. The printing cylinder and cutting cylinder are chained together or otherwise linked in order to synchronize the operations and properly determine the cut lengths of the bands. [0018] Additional objects, features and advantages will be apparent in the written description which follows. BRIEF DESCRIPTION OF THE DRAWINGS [0019] FIG. 1 is a perspective view of a container assembly of the type used in the practice of the invention showing the cap thereof in exploded fashion prior to assembly. [0020] FIG. 2 is an isolated view of the cap and container top showing the placement of the tamper-evident band on the assembly. [0021] FIG. 3 is an isolated view of a tube of thermoplastic material prior to being placed on the container assembly and heat shrunk into position. [0022] FIG. 4 is a plan view of the sheet of thermoplastic material used to make the tube of FIG. 2 showing the lines of perforations, die cuts and registration marks used in the manufacture of the tamper-evident band of the invention. [0023] FIG. 5 is a simplified, schematic view of the printing cylinder and die cutting cylinders used in the method of the invention. DETAILED DESCRIPTION OF THE INVENTION [0024] The present invention is directed to a novel, tamper-evident band for use in various packaging applications. That is, if the container and cap assembly to which the band is adhered is opened or has been tampered with, the label will show signs of wrinkling, distortion or breakage along the tear strips present on the band. The nature of the improved tamper-evident band of the invention may be better understood by reviewing the attached figures in view of the following written description. [0025] Turning first to FIG. 1 , there is shown a perspective view of a container and cap assembly of the type commonly used for marketing pharmaceutical and over-the-counter products prior to having the tamper-evident band of the present invention attached thereto. For example, the container assembly might comprise an eye drop container and associated cap for dispensing eye drop medication. Container and cap assembly 11 is typically fabricated from a thermoplastic material, although glass, metal, or a combination thereof might be employed, as well. The container body portion 13 , typically exhibits a rectangular, polygon, elliptical or oval shape. Cap 15 , typically, exhibits an identical or complimentary shape to the top of the container, and will be have a twist- or screw-off design. The container 13 has a bottom 17 , generally cylindrical side walls 19 , a mouth 21 , a top edge 23 and a throat region 24 adjacent to the mouth. The cap of the assembly has a top 25 , side walls 27 , and bottom edge 29 which encloses the mouth 21 and is located adjacent the throat region 24 of the container when the cap is in place on the container. [0026] As shown in FIG. 2 , the container body and cap have applied thereto a tamper-evident band 10 . The band 10 is preferably formed from a heat-shrinkable thermoplastic material, such as expanded polystyrene, polypropylene, polyethylene, or polyvinyl chloride. The container shown in the Figures is intended to be illustrative of a typical container construction, since it will be appreciated that the present invention can be readily practiced for applying heat-shrinkable bands to containers of almost an endless variety of configurations. After the band has been positioned on the container, it is shrunk by the application of heat, which is typically accomplished by passing the container through a heat tunnel or like heat source so that the heat-shrinkable bands are substantially entirely heated and shrunk into conformance with the shape of the containers. The attempted opening or opening of the container 11 by removal of its cap aor lid portion 15 requires permanent visible deformation of the heat-shrinkable member for tamper-indicating. However, the invention can also be employed for application of other than a tamper-indicating means, such as protective sleeves that are sometimes fitted to containers. [0027] As perhaps best understood with reference to FIG. 4 , the finished band 10 is made from a beginning stock of thermoplastic sheet material 31 . The sheet material is preferably a heat shrinkable thermoplastic such as a commercially available polyolefin. The planar sheet of material 31 has at least one, and preferably two, tear strips 33 , 35 defined by two parallel perforated lines (i.e., lines 37 , 39 , in FIG. 4 ) there-through which terminate in a plurality of evenly spaced die cuts 41 . There are actually three die cuts in each column of perforations in the particular embodiment of the invention illustrated in FIG. 4 . The planar sheet 31 also has a pair of seam regions 43 , 45 whereby the sheet can be folded and joined to make a continuous tube of material which can then be cut in desired lengths. The tear strips and seam regions are generally parallel to the central vertical axis ( 49 in FIG. 3 ) of the tube of material and are generally equidistantly spaced about the circumference of the tube. FIG. 3 shows a portion of a continuous tube of material 47 which will be cut at three locations to provide three bands of the invention. While the member 47 is generally cylindrical as illustrated, it will be understood that it can assume other configurations as long as it is configured so as to be predominantly heat-shrinkable in a radial direction relative to a central vertical axis 49 . [0028] Returning to FIG. 4 , there is shown a series of registration marks (i.e., marks 51 , 53 , 55 ) on the planar sheet of material for aligning a cut tube of material on an assembled container and cap. The registration marks shown in FIG. 4 are a series of parallel lines arranged generally perpendicular to the central vertical axis ( 49 in FIG. 3 ) of the container. It is important for purposes of the invention that the tear strip overlay the top edge ( 21 in FIG. 1 ) and neck region 24 of the container 13 and bottom edge 29 of the cap 15 when the cap is in place on the container. As perhaps best seen with respect to FIG. 2 , the tear strip 28 also preferably extends over the top edge 30 of the cap so that the die cut is positioned at least partly on the top of the cap. Note the die cut 57 in FIG. 2 of the drawings. With the band in this position tampering with or removing the band from the assembly by way of pulling on the tear strip, or removing or repositioning the cap from the container, causes the perforated lines of the tear strip to deform or rupture, thereby serving as visible and physical evidence of tampering with the assembly. [0029] Table I below shows the typical dimensions for location of the tear strips, die cuts, seam regions and registration marks to allow the band to be properly printed, cut and positioned on the container assembly illustrated in the drawings. These dimensions are intended to be exemplary of one embodiment of the invention, it being understood that the dimensions can be varied, depending in part upon the shape of the container and cap. TABLE I Reference Character Dimension in mm   1 1  7   1 2  25   1 3  25   1 4  7   1 5  35   1 6  35   1 7  7   1 8  1   1 9  7 1 10 14 1 11 7 1 12 57 1 13 94 1 14 122 [0030] As best seen in FIG. 2 , heat shrinking the tube of material ( 47 in FIG. 3 ) in a desired position on the container and cap assembly as determined by the registration marks, causes the die cut to separate and form the tab 57 which protrudes from the planar surface of the sheet of material and which can be grasped by a user in order to more easily separate the band from the container. Applicant's tab is already exposed after the heat shrinking step, so that it can be easily located by the user and more easily grasped. That is, the tab 57 protrudes above the plane or contour of the remainder of the exterior surface of the band 10 . Preferably, the registration marks ( 51 , 53 , 55 in FIG. 4 ) are applied by the operation of a printing machine and the die cuts are made by the operation of a cutting machine, the printing and cutting operations being synchronized in order to properly determine the cut length of the bands. [0031] FIG. 5 is intended to be a schematic illustration of the printing and cutting steps. Any number of commercially available machines can be utilized to perform these operations and such machines will be well familiar to those skilled in the relevant packaging arts. The printing machine preferably includes a pair of mating printing plate cylinders 59 and the die cutting machine preferably includes a pair of mating die cutting cylinders or wheels 61 . The printing and cutting cylinders are preferably chained together in order to synchronize the operations and properly determine the cut lengths of the bands. In FIG. 5 , the printing and cutting cylinders are shown physically chained by the loop mechanism 63 in order to illustrate the principle involved in simplified fashion. [0032] As will be evident from FIG. 4 , the printing machine can also conveniently include an indicia printing function or station for printing brand indicia, or other useful information, onto the tube of material. For example, the term “Brand” in FIG. 4 could be replaced by a manufacturer's trademarked brand or logo. As shown in FIG. 4 , the brand indicia, “Brand”, is also synchronously registered with die cuts 41 and registration marks 53 , 55 , in this case evenly spaced columns. [0033] For example, with reference to FIG. 5 , for each revolution of the printing plate cylinder 59 , there is one corresponding revolution of the die cutting wheel 61 . For a 1½ repeat pattern on the cylinder of material, 4 tabs would be produced per revolution of the printing plate cylinder. It will be understood, however, that the printing and cutting operations could also be synchronized by means of ultrasonic sensors, optic sensors, or other sensing means which would detect the presence of the registration marks 55 , 57 . A modem packaging line can produce on the order of 300 bands per minute in the fashion described. [0034] An invention has been described with several advantages. The tamper-evident band of the invention produces a tab which protrudes from the planar surface of the sheet of heat shrunk thermoplastic material, making the tab easy to locate and easy to pull. In this way, a user can more easily identify the pull tab and more easily remove the band to access the contents of the container. The tab is pulled in a longitudinal direction generally aligned with or parallel to the longitudinal axis of the container being sealed. The tamper-evident band, when in place, assures the consumer that the package has not been violated, since tampering with or removing the band from the assembly by way of pulling on the tear strip, or removing or repositioning the cap from the container, causes the perforated lines of the tear strip to deform or rupture, thereby serving as visible and physical evidence of tampering with the assembly. The tamper band of the invention is simple in design and economical to manufacture and is well adapted for implementation in an automated packaging line.
A tamper-evident band is provided which includes a pull tab which is more easily located and more easily grasped by a consumer for removing the tamper-evident band from a container. A method is also disclosed for applying a heat-shrinkable band to a container such that the band is correctly conformed to the configuration of the container with the pull tab properly located for ease of identification and ease of removal.
1
FIELD OF THE INVENTION [0001] A workstation for the preparer of scrapbook pages. BACKGROUND OF THE INVENTION [0002] A good scrapbook page needs to look good in the sense of orderliness and balance. This means skill and artistry in arrangement of often irregularly shaped items, which in turn require a stable support that provides dimensional and angular alignment information, means to dispose quickly of scrap material, and ready availability of instruments and tools. All of this must be accomplished on a rather small surface which must be usefully smooth, but also permit easy sliding movement along the surface, and easy pick-up from it. [0003] It is the objective of this invention to provide such a workstation. BRIEF DESCRIPTION OF THE INVENTION [0004] A scrapbook accessory according to this invention includes a rigid base having a top planar work surface. The work surface is bounded by an edge which bears on a plurality of its sides linear measurement indicia. The surface itself is lightly patterned by reliefs which discourage adherence of items to the surface. [0005] A waste aperture extends from the surface through the base to pass a receptacle so that scrap material can readily be dumped from the surface into the receptacle simply by scraping it into the receptacle. [0006] According to a preferred but optional feature of the invention, the aperture is located adjacent to the edge of the base near where a user will be located. [0007] According to yet another feature of the invention, a collection groove extends adjacent to an edge of the base so as to hold tools and accessories such as clips and knives. [0008] According to yet another optional feature of the invention, the bottom side of the base (from the work surface) is provided with a skid-resistant layer that can serve to restrain the workstation from sliding off of the lap of a user or on a table. [0009] The above and other features of this invention will be fully understood from the following detailed description and the accompanying drawings, in which: BRIEF DESCRIPTION OF THE DRAWINGS [0010] FIG. 1 is an isometric view looking at the top of a workstation according to this invention with a collective receptacle installed; [0011] FIG. 2 is an exploded view of FIG. 1 ; [0012] FIG. 3 is a top view of the device of FIG. 1 ; [0013] FIG. 4 is a bottom view of FIG. 3 ; and [0014] FIG. 5 is a cross-section taken at line 5 - 5 in FIG. 3 . DETAILED DESCRIPTION OF THE INVENTION [0015] Scrapbook workstation 10 comprises a rigid base 11 which is preferably generally rectangular. Three of its edges 12 , 13 and 14 have straight edges. Edge 15 , which will be closest to the user, is also preferably straight, but could instead be shaped so as to conform to the user's body. [0016] Edges 12 , 13 and 14 have linear measurement indicia 16 , 17 , 18 respectively so the user can conveniently measure, align and orient the various items he wishes to incorporate in the scrapbook page. Edges 12 and 14 are parallel. Edge 13 is normal to them. The indicia may be in any unit of measurements, but usually inches or centimeters will be the scale. [0017] A collection groove 20 may be aligned with any of the edges, but usually will be located along edge 13 inwardly of indicia 17 . This groove can be used to collect small scrap, or to hold small useful items such as clips, clamps, brushes, or staples. It may be relatively shallow, but deep enough to hold desired articles. Such a groove can also be provided along any of the other edges, also. [0018] A waste aperture 25 is formed through the base, preferably adjacent to one of the sides. Most conveniently it will be located adjacent to side 15 , closest to the user. As best shown in FIG. 5 , a recessed step 26 is formed around it, beneath top surface 27 of the base. [0019] A bag 28 with a flange 29 (or merely extra material) may be passed through aperture 25 . The flange or material will be held by a retainer 30 pressed into the aperture and upon the flange or material. Thus, the bag hangs below the base and receives scrap. It will be observed that retainer 30 also has a flange 31 that fairs neatly onto the top surface so as not to impede scrap as it pushed toward the aperture. [0020] The bag is thereby readily installed, removed, and replaced. [0021] As best shown in FIG. 4 , the bottom side 32 of the base can be faced with friction type material such as rubber or a plastic foam to prevent the device from skidding around. [0022] The top side of the base may advantageously be mildly roughened or relieved to facilitate lifting of flat items, especially pictures and flat paper items which would tend to be difficult to raise off of a perfectly flat (mirror flat) surface. It is necessary that what could be considered roughness not be so rough as to impede smooth writing and smoothing of articles to be mounted. Very light “pebbling.” or shallow grooving are suitable examples. [0023] There results a very convenient scrapbook workstation, convenient to use and service, with provisions for accuracy of work, accessibility of tooling and supplies, and convenient in disposed of scrap. [0024] This invention is not to be limited by the embodiment shown in the drawings and described in the description, which is given by way of example and not of limitation, but only in accordance with the scope of the appended claims.
A scrapbook workstation having a planar work surface accommodating storage, providing dimensional and alignment references, and ready disposal of scrap.
0
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a paper-based container, the devices for its implementation and the containers thus obtained. 2. Description of Background and Material Information Containers generally designed for containing liquids are known, FIGS. 1 and 2 illustrating an example having a rectangular front surface 1 and a rectangular rear surface 2, having the same width and height, and a bottom 3 formed from a rectangular sheet having the same width and a substantially lower height than the front 1 and rear 2 surfaces, and folded in half along its width to form a bellows. The complex film constituting the front 1 and rear 2 surfaces has, on the outside, a film made of a plastic material that is rendered semi-rigid by using it in a more substantial thickness than strictly required and, on the inside, a glued film that is adapted for welding at a substantially lower temperature than the fusion temperature of the outside film. On the contrary, the complex film composing the bellows is very flexible but has a similar structure with an outside film supporting a glued film for welding. The front 1 and rear 2 surfaces are bound together by the welding of their lateral parts 4 either directly at their upper portion, or indirectly at their lower portion via the bottom 3 forming the bellows. The edges 14 of the bellows forming the bottom 3 laterally have, in the width of the lateral welds 4, cutouts 5 (FIG. 5) that correspond to one another such that the front 1 and rear 2 surfaces come into contact directly at the level of the bottom 3 and are welded together so as to laterally block the opening of the bellows formed by the bottom 3. Each side of the bellows of the bottom 3 is furthermore bound to the front 1 and rear 2 surfaces facing it respectively, in the middle part located between the lateral parts 4 on the surface of a binding zone 13 extending from the support base 6 to a "U"-shaped curve 7 that starts at the upper fold 8 of the bottom 3 forming the bellows, at the level of the left lateral part 4, to end back at the upper fold 8 of the bottom 3 forming the bellows, but at the level of the right lateral part 4, the middle part 9 of the curve 7 being a few millimeters away from the support base 6. When such a small bag is unfolded, the front 1 and rear 2 surfaces (FIG. 2) are spaced from each other by bending in the shape of a half cylinder having vertical generatrices and a cross-section predetermined by the previously described "U"-shaped curve 7 limiting the binding zone 13 of the bottom 3 forming the bellows which is bound to the front 1 and rear 2 surfaces. The bottom 3 forming the bellows is unfolded until its free part 10 is stretched, which provides a maximum spacing in the middle part 9 of the curve 7 which is also the middle part of the front 1 and rear 2 surfaces. In this zone, the free part 10 of the bottom 3 is near the support base 6, and the spacing of the front 1 and rear 2 surfaces is gradually reduced as it nears the edges, and the free part 10 of the bottom 3 progressively rises to the level of the fold 12 of the bottom 3 where the front 1 and rear 2 surfaces come together to be welded. The support base 6 is formed by the base of the front 1 and rear 2 surfaces, welded to the walls of the bottom 3 forming the bellows, which provides a sufficient rigidity so that the container stands upright. This container is generally filled, especially with a liquid, and the front 1 and rear 2 surfaces are welded together at their top so as to seal the container. The welding of this container's inside film is achieved by a high frequency radiation to which the outside film is not susceptible. SUMMARY OF THE INVENTION An object of the invention is a method for manufacturing a container of the aforementioned type but in which the outside film is replaced with paper bound through gluing paper onto paper by coating only the areas of the previously described lateral parts 4 and binding zone 13 with glue. In another version, the container can have a plastic film on the inside, such as polyethylene, which allows welding as described previously by means of thermal electrodes that weld through paper. As for the binding of the edges 14 of the bellows to the lateral edges of the front 1 and rear 2 surfaces, it can be done through cutouts 5 (FIG. 5), as described previously, but also by gluing paper onto paper along a rectangular zone 41 which allows binding the bellows laterally. Given that paper has the ability of binding itself to molten polyethylene, the paper constituting the bottom 3 forming the bellows could be without an internal polyethylene film and be bound nonetheless to the front 1 and rear 2 surfaces which are coated with a polyethylene film. In a preferred version of the invention, and by way of non-limiting example, the container serves for packaging a quantity of French fries, of about 100 grams to 150 grams. The rear surface 2 (FIG. 2) is higher than the front surface 1, by 10 millimeters to 25 millimeters, to facilitate the manual opening of the container. The bellows of the bottom 3 (FIG. 1) has a depth 21, of 25 millimeters to 50 millimeters, which increases with the width of the container. The paper covering the outside of the front 1 and rear 2 surfaces has preferably the same thickness, between 35 grams and 50 grams per square meter, whereas the paper constituting the bottom 3 forming the bellows has a smaller thickness, preferably of about 20 grains to 30 grains per square meter. When the papers are coated with polyethylene on their internal surface, the coating is done at the rate of 6 grains to 10 grains per square meter. BRIEF DESCRIPTION OF DRAWINGS The invention will be more clearly understood and other characteristics thereof will become apparent with reference to the following description and the annexed drawings, in which: FIGS. 1 and 2 illustrate an example of the known prior art container described above; FIG. 3 schematically shows a device according to the invention producing two containers simultaneously and using paper plastic-coated on one surface; FIG. 4 schematically shows a device using papers bound together by glue; FIG. 5 shows the detail of a lateral binding means of the bottom forming the bellows; FIG. 6 shows, schematically and in a partial perspective, a device that allows obtaining the folding of a container to reinforce its support base; FIG. 7 shows a container whose support base is reinforced by means of the folding obtained with the device shown in FIG. 6; FIG. 8 shows, in a cross-section and in perspective, the reinforcement folding of the support base of the container; FIG. 9 shows in perspective and in a transverse cross-section the folding device; FIG. 10 shows a cross-section of the folding obtained in FIG. 8 and assembled to the sheath serving as the bellows for the container; FIG. 11 shows a partial cross-section of the reinforced support base of the container. DETAILED DESCRIPTION OF THE INVENTION A first device according to the invention allows manufacturing two containers 15 and 16 simultaneously, connected together at their base and which are then separated by cutting; these containers 15 and 16 which have the same width can have different heights. Hereinafter, the simplest of cases is described. which consists of simultaneously manufacturing two identical containers 15 and 16 with papers coated, over the whole area of one of their surfaces, with a polyolefin-based plastic material or equivalent product for welding. One starts with three coils, the first of which delivers a lower strip 17 (FIG. 3) of coated paper with a width 18 corresponding to the sum of the heights of the rear surface 2 (FIG. 1) of the containers 15 and 16, and is positioned so as to unwind the lower strip 17 of paper in a horizontal direction, for example, with the coated surface facing upward. The second coil delivers an intermediate strip 19 (FIG. 3) with a width 20 substantially equal to four times the depth 21 (FIG. 1) of the bellows, and is positioned to unwind the intermediate strip 19 horizontally with the coating facing downward and which, after being shaped, as will be described hereinafter, will position itself, with its axial plane of symmetry located in the axial plane of symmetry of the lower strip 18, above and in contact with the latter. The third coil delivers an upper strip 22 with a width 23 equal to the sum of the heights of the front surface 1 (FIG. 1) of the containers 15 and 16, and is positioned so as to be capable of unwinding the upper strip 22 above the other two strips with its axial plane of symmetry merged with that of the other two. As for the intermediate strip 19, a coating is made in the form of a rectangle of glue 24, for example, used for binding the edges 14 of the bellows to the surface of paper located on top in the example chosen, at regular intervals and corresponding to the width 25 of a container, on a rectangular surface arranged coaxially with the intermediate strip 19 over a width perpendicular to the axis of the intermediate strip 19, of about 2 to 4 centimeters, and over a length preferably less than or equal to twice the width 28 of the lateral parts 4 (FIG. 1). A sheath is formed to have a shape of a sailor's collar, for example, by bringing the lateral edges 26 (FIG. 3) of the intermediate strip 19 to touch one another above the middle part of the latter and in the axial plane of symmetry so that the plastic film is on the outside of the sheath. Next, the sheath is crushed so that the lateral edges 26 are in the axis 27 of the intermediate strip 19 and are bound step by step to the rectangles of glue 24 previously laid on the middle part of the intermediate strip and which are on the inside of the sheath. The same result can be obtained by turning each of the two lateral edges 26 with guides appropriately spaced so as to form a longitudinal fold on each side with a depth corresponding to the depth of the bellows such that the lateral edges 26 come together on the axis 27, as described previously. The intermediate strip 19 thus shaped is laid on the lower strip 17, and then it is covered by the upper strip 22. In an alternative embodiment of the invention, the lateral edges 26 that close the tube along the axis 27 can overlap each other by 1 to 2 centimeters, which simplifies the adjustments and, as will be seen later, reinforces the vertical resistance of the container. Preferably, the axial part of the overlapping zone is substantially in the axial plane of symmetry of the lower 17, intermediate 19 and upper 22 strips; in this case, the overlapping parts are preferably bound over their whole length. When an intermediate strip 19 of paper coated with a heat-sealing plastic film is used, no special precautions need to be taken; however, if the intermediate strip is not coated, it is preferred to put a coating of glue on the upper part of the lateral strip 26 of the intermediate strip which will cover the other lateral strip 26 at the same time that the previously described rectangles of glue 24 are laid. The assembly of the three superimposed strips then passes between a hot electrode and a counter electrode (not shown in FIG. 3), or two hot electrodes (only one of which is shown in FIG. 3) which are cylinders rotating around electrically heated horizontal axles. The heating cylinder(s) present the zone 29 to be welded, in the form of an "H", successively laid over a distance corresponding to the width 25 of the container, the vertical arms 30 of the "H" making the lateral welds 31 of two consecutive containers. The horizontal part 32 of the "H" allows making the bottoms simultaneously in welding zones 33 of the two containers placed opposite each other at their bottom. The rectangle of glue 24 must be laid on the intermediate strip so that, during welding by the heating cylinder(s), it is placed at the level of the vertical arms 30 of the "H" corresponding to the lateral welds 31. What remains is cutting in the axial plane of the three welded strips in order to separate the bottoms of the opposing containers, for example, by means of a cutting disk 34 whose main plane is in the axis of the strips, then making a transverse cut to separate the successive containers connected by their lateral welds 31 with at least one cutting bar 35 perpendicular to the axis of the strips attached to a rotating cylinder 36. In an alternative embodiment of the invention, when the paper used is not coated with plastic over its whole surface, the upper part of the lower strip 37 (FIG. 4) is coated with glue as is the lower part of the upper strip 38, before they are assembled to the shaped intermediate strip 39, on a surface identical to the previously described welding surface, due to gluing cylinders 42 and 43. The three strips are pressed between two cylinders 40 (only one of which is represented in FIG. 4), heated or non-heated, depending upon whether the glue is hot or cold. As was previously specified, when the intermediate strip 39 has an overlapping zone for the lateral edges after being shaped, the lateral edges that overlap each other are preferably bound together. One can proceed with the longitudinal and transverse cuttings, as described previously. In the case where there is an overlapping of the lateral parts of the intermediate strip during its shaping, this overlapping is found in the form of a third thickness of paper at the base 6 (FIG. 2) of the front surface 1, which significantly increases the container's rigidity. An improvement to the container made by means of the device that has just been described consists of reinforcing the container base without increasing the thickness of the front and rear surfaces. To this end, the container is made from three strips of paper (FIG. 6) which are coated either with a heat-sealing material over their whole surface, or with glue at the level of the zones that must be glued together. There is a lower strip 44 to make the rear surface 2 (FIG. 7) of the container, an upper strip 45 (FIG. 6) to make the front surface 1 (FIG. 7) of the container, and between then an intermediate strip 46 (FIG. 6) folded to form a sheath and make the container's bellows. After assembly of the strips 44, 45, 46, in order to manufacture containers opposing each other at their support base 6 (FIG. 7) two by two, the containers are separated at the level of their support base 6 by an axial cutting of the assembled strips 44, 45, 46, and at the lateral level by a transverse cutting of the strips. Hereinafter, it is supposed that the two containers connected at their base are identical, but they can also have different heights. A device for manufacturing this container allows making, on each of the lower 44 and upper 45 strips, two longitudinal folds 47 and 48 (FIG. 8), laid opposite one another symmetrically, on both sides of the axial line 49 and 50 (FIG. 6) of the lower 44 and upper 45 strips, so as to form a dovetail outline with two folds 51 and 52 facing each other and two folds 53 and 54 opposing each other. These folds 47 and 48 are preferably made with the dovetail turned inwardly so as not to be visible from the outside of the container, and these folds 47 and 48 have a width 55 and 56 preferably identical and preferably substantially equal to the distance 57 (FIG. 7) separating the support base 6 from the lower part 58 of the bottom of the container when it is unfolded; the edges of the folds 51 and 52 (FIG. 8) facing each other are separated by 1 to 2 millimeters. There are numerous means for making this longitudinal dovetail shaped fold according to FIG. 8; one means for making it is to use a folding device 79 (FIG. 6) constituted of slides, this example being non-limiting. This folding device 79 is constituted of a middle slide 60 (FIGS. 6 and 9), having a width 78 corresponding substantially to the width of the strip portion 67 (FIG. 8) located between the opposing folds 53 and 54, and placed on the lower 44 and upper 45 strips (FIG. 6). On the outside of the future container, oriented coaxially to the corresponding strip. The folding device 79 is then constituted of two lateral slides 61 and 62 (FIG. 9), placed on the inside of the corresponding strip 44 or 45 (FIG. 6) on both sides of the middle slide 60, having a form that varies depending on tile distance considered from the origin 63 or 64 of the lateral slide 61 or 62 considered. They progressively take on a "C" shape so as to draw the middle part of the strip to cap the wings 65 (FIG. 9) of the middle slide 60. What remains, for example, is to pass the lower 44 and upper 45 strips (FIG. 6) between two pressure cylinders 66 to mark the folds. The strip portion 67 (FIGS. 8 and 10) joining the two opposing folds 53 and 54 is bound to the sheath constituted of the intermediate strip 46. The strip portions 80 and 68, located on both sides of the axis of the related lower or upper strip 69 (FIG. 10), are pressed against the latter at least by their edges; on the one hand, by their facing folds 51 and 52 (FIG. 10) and, on the other hand, by the intermediate strip 46 serving to form the bellows, which is also directly bound to the corresponding lower or upper strip 69 beyond the opposing folds 53 and 54. It is possible, according to certain dimensions, that the opposing folds 53 and 54 open out inside the lower part 58 (FIG. 7) of the bottom 59 of the container and therefore are not held by the binding on the intermediate strip 46 which is no longer bound in this zone to the related lower or upper strip 69 (FIG. 10); but that is a small proportion of the length of the support base 6 (FIG. 7) which is not bound and is of no consequence, especially as when lower or upper strips 69 (FIG. 10) coated over their whole surface with a heat-sealing material are used for manufacturing the container, each strip portion 80 and 68 is heat-sealed over part or its entire surface to the corresponding lower or upper strip 69. In these conditions, after the longitudinal and transverse cutting of the strips assembled together, containers are obtained whose zone near to the support base 6 (FIG. 11) of the front and rear surfaces has a reinforcing device 70 with three times the thickness 72 of the paper forming the surfaces 71 of the container, and at least one time the thickness 73 of the paper forming the bellows. This gives a weight by the square meter in this zone 70 of between 135 grams and 180 grams per square meter for one surface, and 165 grams and 210 grams per square meter for the other surface. In these conditions, a support base 6 is obtained that no longer bends under the weight of the container's load. In an alternative embodiment of the invention, the lateral edges (FIG. 6) of the upper 45 and lower 44 strips are folded over a width of 5 millimeters to 10 millimeters on the inside, and they are bound by welding or gluing in order to dull the upper edges 75 and 76 (FIG. 7) of the container. The lateral edges can be folded due to a folding device composed of slides similar to those previously described and which are commonly used.
Manufacturing method to make simultaneously two paper containers having a front surface and a rear surface, opposed at their support base by three superimposed strips of paper, the intermediate strip being shaped like a sheath sandwiched between the other two strips on which longitudinal folds are formed which, after the containers are separated, serve as a reinforcement of their support base. The invention also includes the device for implementing the method, as well as the containers thus obtained.
1
BACKGROUND [0001] 1. Field of the Invention [0002] The invention is in the area of animal noise protectors. [0003] 2. Description of the Related Art [0004] Ear coverings for animals are known in the art; however, most of these are not capable of hearing/noise protection, but instead are designed to protect the outer ear flap, keep out insects, keep the ears out of the animal's food, cover an ear wound, or keep the ear warm. The physical structure of these devices, and their ability to block noise, is thus markedly different from that of the invention. [0005] U.S. Pat. No. D417,315 to Lowry shows a protective ear covering that uses two ear pockets separated by a strap across the top of a dog's head. However, the ear pockets are made of a mesh material having a grid-like appearance, which will not block sound. Moreover, Lowry's strap is not easily adjustable via hook and loop (Velcro) attachment points. [0006] U.S. Pat. No. 5,163,272 to Finley; U.S. Pat. No. 4,233,942 to Williams; and U.S. Pat. No. 4,964,264 to Adams all show dog ear protectors. However, these are designed to either block insects from entering the ear canal or prevent the dog's ears from becoming soiled by food while eating. Accordingly, the physical structures of these devices are significantly different than that of the invention, and none of them will serve to protect the dog from bothersome noises. These devices also lack important elements of the physical structure of the invention—e.g., the adjustable hook and loop straps that hold the invention on the animal's head. [0007] U.S. Pat. No. 6,502,532 to Sjolin discloses an animal bandage device that fits over the ears; however, this device does not cover the ears and thus will not block noise. [0008] U.S. Pat. No. 5,540,189 to Masson and U.S. Pat. No. 5,456,215 to Deutscher show cattle ear covers which are designed to keep the animal's ears warm. Deutscher's device is a whole-head cover which differs markedly in structure from the invention. Masson's device would not adequately block out noise, because the bottom of the ear covers do not seal tightly against the animal's head. Further, Masson's device adjusts in a very different manner than the invention—it does not have hook and loop material directly on the ear covers to allow fast and easy adjustment as in the invention. [0009] U.S. Pat. No. 3,942,306 to Kulka discloses various animal noise protection devices. However, the head band shown in this patent differs markedly in structure from the invention. SUMMARY OF THE INVENTION [0010] The invention is an animal noise protector that is placed on the animal's head, over the ears. Two noise-blocking members, suitably sized so as fit comfortably and snugly over the animal's ears and against the sides of the animal's head, are joined by at least one connecting strap that is easily adjustable via hook or loop material located on the noise-blocking members. An adjustable neck strap is also attached between the noise-blocking members. [0011] Several objects and advantages of the invention are: [0012] It is an object of the invention to provide an easy-to-install animal noise protector that will effectively block undesirable noise from reaching an animal's ears, thereby preventing the animal from being distracted, fearful, or even in pain due to the noise. [0013] It is a further object of the invention to provide a device that can be worn by many different animals, including but not limited to pets, farm animals, etc. [0014] It is a further object of the invention to provide a device that can be quickly and easily adjusted to optimally fit the animal's head, so that the animal will be comfortable wearing it. [0015] It is a further object of the invention to provide a device that has a relatively simple construction, and a relatively low cost. [0016] Further objects and advantages of the invention will become apparent from a consideration of the ensuing description and drawings. DESCRIPTION OF THE DRAWINGS [0017] FIG. 1 is a perspective view of the animal noise protector, illustrating the ear covers and connecting straps. [0018] FIG. 2 further illustrates an ear cover and the hook attachment patches located thereon. [0019] FIG. 3 further illustrates a connecting strap and the loop attachment patches located thereon. For clarity and convenience, the full length of the connecting strap is not shown. [0020] FIG. 4 is a side view of the animal noise protector installed on an animal. [0021] FIG. 5 illustrates an alternative embodiment, wherein the entire connecting strap is made of loop material. For clarity and convenience, the full length of the connecting strap is not shown. [0022] FIG. 6 illustrates an alternative embodiment, wherein the neck strap has a buckle located between its two ends. For clarity and convenience, the full length of the connecting strap is not shown. DETAILED DESCRIPTION OF THE INVENTION [0023] The following provides a list of the reference characters used in the drawings: 10 . First ear cover 11 . Second ear cover 12 . Foam ring 13 . First connecting strap 14 . Second connecting strap 15 . Neck strap 16 . Hook material 17 . Loop material 18 . Buckle [0033] As shown in FIG. 1 , the invention comprises a first ear cover 10 and a second ear cover 11 . First ear cover 10 and second ear cover 11 are connected by a first connecting strap 13 , a second connecting strap 14 , and a neck strap 15 . First ear cover 10 and a second ear cover 11 are constructed of a substantially rigid noise-blocking material formed in a shell shape, and have a foam ring 12 around the inner periphery thereof. Foam ring 12 , together with the shell shape of first ear cover 10 and second ear cover 11 , form cavities on the inner (head-contacting) sides of the device, and the animal's ears fits into these cavities when the device is on the animal's head. Foam ring 12 compresses against the animal's head, and the shell/foam ring construction effectively blocks undesirable sound from entering the animal's ears. [0034] FIG. 2 further illustrates first ear cover 10 , which has three patches of hook material 16 located thereon. Hook material 16 comprises one half of the mating attachment material commonly referred to by the trade name Velcro®. It should be understood that second ear cover 11 also has three patches of hook material 16 located thereon, and that a mirror image of FIG. 2 would generally illustrate the position of the patches of hook material 16 on second ear cover 11 . Referring back to FIG. 1 , it can be appreciated that these patches of hook material 16 are covered by, and attach to, the ends of first connecting strap 13 , second connecting strap 14 , and neck strap 15 . [0035] FIG. 3 is a view of the bottom (hook-material-contacting) surface of first connecting strap 13 . First connecting strap 13 has a patch of loop material 17 located at each end thereof. Loop material 17 comprises the other half of the mating attachment material commonly referred to by the trade name Velcro®. It is these patches of loop material 17 that mate with the patches of hook material 16 on first ear cover 10 and second ear cover 11 . It should be understood that although for specificity the connecting strap shown in FIG. 3 is labeled as first connecting strap 13 , it can also represent second connecting strap 14 and/or neck strap 15 . The main bodies of first connecting strap 13 , second connecting strap 14 , and neck strap 15 are made from elastic material, such that they are able to stretch along their length and provide a further degree of adaptability of the device to differently sized and shaped animal heads. [0036] FIG. 4 is a side view of the animal noise protector installed on an animal, here a dog. First connecting strap 13 is positioned substantially across the top of the animal's head, second connecting strap 14 is positioned substantially across the back of the animal's head, and neck strap 15 is positioned substantially across the front of the animal's neck, under the chin. [0037] FIG. 5 shows an alternative embodiment, wherein the bottom (hook-material-contacting) surface of first connecting strap 13 is made completely of loop material 17 . In this embodiment, first connecting strap 13 is essentially a strip of loop material 17 . This allows for a greater degree of adjustment of the device on the animal's head than is allowed by patches of loop material merely on the ends of first connecting strap 13 . It should be understood that although for specificity the connecting strap shown in FIG. 5 is labeled as first connecting strap 13 , it can also represent an alternative embodiment of second connecting strap 14 or neck strap 15 , with loop material located over the length of the strap. [0038] FIG. 6 shows another alternative embodiment, wherein neck strap 15 has a buckle 18 located between its two ends. Buckle 18 allows for easier connection and disconnection of neck strap 15 once the basic fit of neck strap 15 on the animal—that is, neck strap 15 's connection to first ear cover 10 and second ear cover 11 —has been established. It also allows for connection and disconnection of neck strap 15 in versions where the ends of neck strap 15 are permanently and non-adjustably attached to first ear cover 10 and second ear cover 11 . [0039] While the above descriptions contain many specificities, these shall not be construed as limitations on the scope of the invention, but rather as exemplifications of embodiments thereof. Many other variations are possible without departing from the spirit of the invention. Examples of just a few of the possible variations follow: [0040] The patches of hook material on the ear covers can instead be patches of loop material. [0041] Correspondingly, the connecting straps and neck strap can have patches of hook material on their ends instead of patches of loop material. In an alternative embodiment used with the above variant, the connecting strap or neck strap could have hook material along its length rather than just patches (i.e, FIG. 5 but with hook material instead of loop material). [0042] The adjustability of the device can be only on one side—i.e., on one ear cover. In such an embodiment, the connecting straps would be permanently/non-adjustably attached to one ear cover, while the other ear cover would have the patches of hook or loop material that allow for removable attachment. Alternatively, both ends of the connecting straps and/or neck strap can be permanently attached to the ear covers. In this variant, the elasticity of the strap material would provide the necessary flexibility in placing the device on the animal's head. [0043] The location of the hook or loop patches on the ear covers, and thus the position of the connecting straps around the animal's head, can be different than that shown. The number of connecting straps can also be different than that shown. [0044] The size and shape of the hook or loop patches on the ear covers can be different than that show. By way of non-limiting example, the patches could be circular, oval, rectangular, or any other suitable shape. In fact, a portion of the ear cover, or the entire ear cover, could be sheathed in hook or loop material, which would increase the degree of adjustability of the connecting straps about the animal's head. [0045] The neck strap, although referred to separately from the other connecting straps, can also of course be considered to be a “connecting strap” since it connects the two ear covers as well. [0046] The strap material may be non-elastic, versus the elastic material described and shown in the various figures. [0047] The ear cover construction may be different than the substantially rigid shell with foam ring construction described and shown in the various figures. Al that is required is that the ear cover material be suitably noise-blocking. The foam ring can be of different material, although some degree of compressibility is desired for optimal noise-blocking. The foam ring can also be eliminated, as long as the ear cover material is sufficiently flexible to conform to the animal's head around the ear area. [0048] The size, shape, depth, and other dimensions of the ear covers can vary, to fit ears of different animals or animals of different sizes. [0049] Accordingly, the scope of the invention should be determined not by the embodiments illustrated, but by the appended claims and their legal equivalents.
An animal noise protector is disclosed, suitable for placement on the animal's head, over the ears. Two noise-blocking members, suitably sized so as fit comfortably and snugly over the animal's ears and against the sides of the animal's head, are joined by at least one connecting strap that is easily adjustable via hook or loop material located on the noise-blocking members. An adjustable neck strap also connects the noise-blocking members.
0
BACKGROUND OF THE INVENTION [0001] The invention relates to a novel polyamino acid-catalyzed process for the enantioselective epoxidation of α,β-unsaturated enones and α,β-unsaturated sulfones under two-phase conditions in the presence of specific cocatalysts. [0002] Chiral, nonracemic epoxides are known as valuable synthons for preparing optically active drugs and materials (for example (a) Bioorg. Med. Chem., 1999, 7, 2145-2156; and (b) Tetrahedron Left., 1999, 40, 5421-5424). These epoxides can be prepared by enantioselective epoxidation of double bonds. In this case, two stereocenters are produced in one synthetic step. It is therefore not surprising that a large number of methods have been developed for the enantioselective epoxidation of double bonds. However, there is still a great need for novel, improved methods for enantioselective epoxidation. [0003] The epoxidation methods limited to the specific substrates in each case include methods for the enantioselective epoxidation of α,β-unsaturated enones. [0004] Thus, for example, the use of chiral, nonracemic alkaloid-based phase-transfer catalysts for the epoxidation of enones is described in Tetrahedron Lett., 1998, 39, 7563-7566, Tetrahedron Left., 1998, 39, 1599-1602, and Tetrahedron Left., 1976, 21, 1831-1834. [0005] Tetrahedron Left., 1998, 39, 7353-7356, Tetrahedron Left., 1998, 39, 7321-7322, and Angew. Chem., Int. Ed. Engl., 1997, 36, 410-412 furthermore describe possibilities for the metal-catalyzed asymmetric epoxidation of enones using organic hydroperoxides. [0006] WO-A 99/52886 further describes the possibility of enantioselective epoxidation of enones in the presence of catalysts based on sugars. Another method for epoxidation using Zn organyls and oxygen in the presence of an ephedrine derivative has been published in Liebigs Ann./Recueil, 1997, 1101-1113. [0007] Angew. Chem., Int. Ed. Engl., 1980, 19, 929-930, Tetrahedron, 1984, 40, 5207-5211, and J. Chem. Soc. Perkin Trans. 1, 1982, 1317-24 describe what is known as the classical three-phase Juliá epoxidation method. In this method, the enantioselective epoxidation of α,β-unsaturated enones is carried out with the addition of enantiomer- and diastereomer-enriched polyamino acids in the presence of aqueous hydrogen peroxide and NaOH solution and of an aromatic or halogenated hydrocarbon as solvent. Further developments of these so-called three-phase conditions are to be found in Org. Synth.; Mod. Trends, Proc. IUPAC Symp. 6th., 1986, 275. The method is now generally referred to as the Juliá-Colonna epoxidation. [0008] According to EP-A 403,252, it is possible also to employ aliphatic hydrocarbons advantageously in this Juliá-Colonna epoxidation in place of the original solvents. [0009] According to WO-A 96/33183 it is furthermore possible in the presence of the phase-transfer catalyst Aliquat® 336 ([(CH 3 )(C 8 H 17 ) 3 N + ]Cl − ) and using at the same time sodium perborate, which is of low solubility in water, instead of hydrogen peroxide, for the required amount of base (NaOH) to be reduced, compared with the original conditions of Juliá and Colonna ( Tetrahedron, 1984, 40, 5207-5211), from about 3.7 to 1 equivalent. [0010] Despite these improvements, the three-phase conditions have distinct disadvantages. The reaction times under the original conditions are in the region of days even for reactive substrates. For example, 1-6 days are required for trans-chalcone, depending on the polyamino acid used ( Tetrahedron, 1984, 40, 5207-5211). A preactivation of the polyamino acid carried out in the reaction vessel, by stirring in the solvent with the addition of NaOH solution for 12 to 48 hours, shortens the reaction time for many substrates to 1 to 3 days. In this case, no intermediate workup of the catalyst is necessary (EP-A 403,252). The preactivation can be reduced to a minimum of 6 h in the presence of the NaOH/hydrogen peroxide system ( J. Chem. Soc. Perkin Trans. 1, 1995, 1467-1468). [0011] Despite this improvement, the three-phase method cannot be applied to substrates which are sensitive to hydroxide ions ( J. Chem. Soc., Perkin Trans. 1, 1997, 3501-3507). A further disadvantage of these classical conditions is that the polyamino acid forms a gel during the reaction (or even during the preactivation). This restricts the required mixing during the reaction and impedes the working up of the reaction mixture. [0012] Tetrahedron Lett., 2001, 42, 3741-43 discloses that under the three-phase conditions the addition of the phase-transfer catalyst (PTC) Aliquat 336 in the epoxidation of phenyl-E-styryl sulfone leads to only a slow reaction rate (reaction time: 4 days) and a poor enantiomeric excess (21% ee). To date, no example of the use of PTCs for the epoxidation of α,β-unsaturated enones under the classical three-phase Juliá-Colonna conditions has been disclosed. [0013] The Juliá-Colonna epoxidation has been improved further by a change in the reaction procedure. According to Chem. Commun., 1997, 739-740, (pseudo)-anhydrous reaction conditions can be implemented by using THF, 1,2 dimethoxyethane, tert-butyl methyl ether, or ethyl acetate as solvent, a non-nucleophilic base (for example, DBU), and a urea/hydrogen peroxide complex as oxidant. The epoxidation takes place distinctly more quickly under these so-called two-phase reaction conditions. According to J. Chem. Soc., Perkin Trans. 1, 1997, 3501-3507, therefore, the enantioselective epoxidation of hydroxide-sensitive enones under the Juliá-Colonna conditions is also possible for the first time in this way. [0014] However, the observation that, on use of the two-phase conditions, the polyamino acid must be preactivated in a separate process in order to achieve rapid reaction times and high enantiomeric excesses proves to be a distinct disadvantage. Several days are needed for this preactivation, which takes place by stirring the polyamino acid in a toluene/NaOH solution. According to Tetrahedron Lett., 1998, 39, 9297-9300, the required preactivated catalyst is then obtained after a washing and drying procedure. However, the polyamino acid activated in this way forms a paste under the two-phase conditions, which impedes mixing during the reaction and the subsequent workup. According to EP-A 1,006,127, this problem can be solved by adsorbing the activated polyamino acid onto a solid support. Polyamino acids supported on silica gel are referred to as SCAT (silica adsorbed catalysts). [0015] According to EP-A 1,006,111, a further variant of the Juliá-Colonna epoxidation is catalysis of the enantioselective epoxidation by the activated polyamino acid in the presence of water, a water-miscible solvent (for example, 1,2-dimethoxyethane), and sodium percarbonate. However, the use of water-miscible solvents complicates the workup (extraction) in this process. [0016] In the Juliá-Colonna epoxidation, the reaction rate and the enantiomeric excess (ee) that can be achieved depend greatly on the polyamino acid used and the mode of preparation thereof ( Chirality, 1997, 9, 198-202). In order to obtain approximately comparable results, a standard system with poly- L -leucine (pII) as catalyst and trans-chalcone as precursor is used throughout for the development and description of novel methods in the literature. However, besides D - or L -polyleucine, other polyamino acids such as, for example D - or L -neopentylglycine are also used successfully (EP-A 1,006,127). [0017] The object of the present invention was to provide a process that makes the homo-polyamino acid-catalyzed enantioselective epoxidation of α,β-unsaturated enones and α,β-unsaturated sulfones possible but is not subject to the disadvantages of the above-described variants of the Juliá-Colonna epoxidation. It was intended in particular to find a rapid and broadly applicable method that avoids the separate, time-consuming and complicated preactivation of the polyamino acid. At the same time, it was intended that the process have advantages in relation to the space/time yield, handling, economics, and ecology on the industrial scale. [0018] It has now been found, surprisingly, that the epoxidation of α,β-unsaturated enones and α,β-unsaturated sulfones can be carried out under two-phase conditions in the presence of a polyamino acid, as catalyst, that has not been subjected to previous separate activation when the epoxidation takes place in the presence of a phase-transfer catalyst. This procedure surprisingly makes it possible for the reaction times to be very short with, at the same time, high enantiomeric excesses. SUMMARY OF THE INVENTION [0019] The invention thus relates to a process for the epoxidation of α,β-unsaturated enones or α,β-unsaturated sulfones in the presence of (1) an organic solvent, (2) a base, (3) an oxidant, (4) a diastereomer- and enantiomer-enriched homo-polyamino acid as catalyst that has not been separately preactivated, and (5) a phase-transfer catalyst, but without addition of water. DETAILED DESCRIPTION OF THE INVENTION [0026] It is crucial that the process according to the invention be carried out in the presence of a phase-transfer catalyst. Examples that can be used are quaternary ammonium salts, quaternary phosphonium salts, onium compounds, or pyridinium salts. [0027] Phase-transfer catalysts that have proved particularly suitable are quaternary ammonium or phosphonium salts of the general formula (I) (R 1 R 2 R 3 R 4 A) + X −   (I) in which A is N or P, X − is an inorganic or organic anion, R 1 and R 2 are identical or different and are alkyl, aryl, aralkyl, cycloalkyl, or heteroaryl radicals that are optionally substituted by one or more identical or different halogen radicals, and R 3 and R 4 are identical or different and are alkyl, aryl, aralkyl, cycloalkyl, or heteroaryl radicals that are optionally substituted by one or more identical or different halogen radicals, or R 3 and R 4 together form a C 4 -C 6 -cycloalkyl ring with A. [0033] Phase-transfer catalysts of the general formula (I) that have proved suitable are those in which A and X − have the above-mentioned meanings, and R 1 , R 2 , R 3 , and R 4 are identical or different and are C 1 -C 18 -alkyl, C 6 -C 18 -aryl, C 7 -C 19 -aralkyl, C 5 -C 7 -cycloalkyl, or C 3 -C 18 -heteroaryl. [0034] Particularly suitable phase-transfer catalysts are ((C 4 H 9 ) 4 N) + Hal − (particularly ((C 4 H 9 ) 4 N) + Br − ), ((C 4 H 9 ) 4 P) + Hal − (particularly ((C 4 H 9 ) 4 P) + Br − ), ((C 4 H 9 ) 4 N) + HSO 4 − , ((C 8 H 17 ) 4 N) + Br − , [(CH 3 )(C 8 H 17 ) 3 N + ]Cl − , and [(CH 3 )(C 4 H 9 ) 3 N + ]Cl − . [0035] X − in the general formula (I) is an inorganic or organic cation, preferably F − , Cl − , Br − , I − , OH − , HSO 4 − , SO 4 − , NO 3 − , CH 3 COO − , CF 3 COO − , C 2 H 5 COO − , C 3 H 7 COO − , CF 3 SO 3 − , or C 4 F 9 SO 3 − . [0036] The phase-transfer catalysts to be employed according to the invention are normally commercially available or else can be prepared by methods familiar to the skilled person. [0037] The amount of added phase-transfer catalyst is not critical and is normally in the range 0.1 to 20 mol % (preferably in the range 0.5 to 15 mol %, particularly preferably in the range 0.5 to 11 mol %), in each case based on the α,β-unsaturated enones or α,β-unsaturated sulfone employed. However, it is to be observed with amounts that are even lower than 0.1 mol % that the reaction rate decreases markedly, while the high enantiomeric excess is unchanged. [0038] It is possible to employ as α,β-unsaturated enones or α,β-unsaturated sulfones the compounds of the general formula (II) in which X is (C═O) or (SO 2 ), and R 5 and R 6 are identical or different and are (C 1 -C 18 )-alkyl, (C 2 -C 18 )-alkenyl, (C 2 -C 18 )-alkynyl, (C 3 -C 8 )-cycloalkyl, (C 6 -C 18 )-aryl, (C 7 -C 19 )-aralkyl, (C 1 -C 18 )-heteroaryl or (C 2 -C 19 )-heteroaralkyl, each of which radicals is optionally substituted once or more than once by identical or different radicals R 7 , halogen, NO 2 , NR 7 R 8 , PO 0-3 R 7 R 8 , SO 0-3 R 7 , OR 7 , CO 2 R 7 , CONHR 7 , or COR 7 , and where optionally one or more CH 2 groups in the radicals R 5 and R 6 are replaced by O, SO 0-2 , NR 7 , or PO 0-2 R 7 , where R 7 and R 8 are identical or different and are H, (C 1 -C 18 )-alkyl, (C 2 -C 18 )-alkenyl, (C 2 -C 18 )-alkynyl, (C 3 -C 8 )-cycloalkyl, (C 6 -C 18 )-aryl, (C 1 -C 18 )-heteroaryl, (C 1 -C 8 )-alkyl-(C 6 -C 8 )-aryl, (C 1 -C 8 )-alkyl-(C 1 -C 19 )-heteroaryl, or (C 1 -C 8 )-alkyl-(C 3 -C 8 )-cycloalkyl, each of which radicals R 7 and R 8 is optionally substituted once or more than once by identical or different halogen radicals. [0043] A (C 1 -C 18 )-alkyl radical means for the purpose of the invention a radical that has 1 to 18 saturated carbon atoms and that may have branches anywhere. It is possible to include in this group in particular the radicals methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl. [0044] A (C 2 -C 18 )-alkenyl radical has the features mentioned for the (C 1 -C 18 )-alkyl radical, with the necessity for at least one carbon-carbon double bond to be present within the radical. [0045] A (C 2 -C 18 )-alkynyl radical has the features mentioned for the (C 1 -C 18 )-alkyl radical, with the necessity for at least one carbon-carbon triple bond to be present within the radical. [0046] A (C 3 -C 8 )-cycloalkyl radical means a cyclic alkyl radical having 3 to 8 carbon atoms and, where appropriate, a branch anywhere. Included are, particularly, radicals such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. One or more double bonds may be present in this radical. [0047] A (C 6 -C 18 )-aryl radical means an aromatic radical having 6 to 18 carbon atoms. Included are, particularly, radicals such as phenyl, naphthyl, anthryl, and phenanthryl. [0048] A (C 7 -C 19 )-aralkyl radical means a (C 6 -C 18 )-aryl radical linked via a (C 1 -C 8 )-alkyl radical to the molecule. [0049] A (C 1 -C 18 )-heteroaryl radical designates for the purpose of the invention a five-, six-, or seven-membered aromatic ring system that has 1 to 18 carbon atoms and that has one or more heteroatoms (preferably N, O, or S) in the ring. These heteroaryl radicals include, for example, 2- or 3-furyl, 1-, 2-, and 3-pyrrolyl, 2- and 3-thienyl, 2-, 3-, and 4-pyridyl, 2-, 3-, 4-, 5-, 6-, and 7-indolyl, 3-, 4-, and 5-pyrazolyl, 2-, 4-, and 5-imidazolyl, 1-, 3-, 4-, and 5-triazolyl, 1-, 4-, and 5-tetrazolyl, acridinyl, quinolinyl, phenanthridinyl, 2-, 4-, 5-, and 6-pyrimidinyl, and 4-, 5-, 6-, and 7-(1-aza)-indolizinyl. [0050] A (C 2 -C 19 )-heteroaralkyl radical means a heteroaromatic system corresponding to the (C 7 -C 19 )-aralkyl radical. [0051] Halogen or Hal means in the context of this invention fluorine, chlorine, bromine, and iodine. [0052] The substrates preferably employed in the process according to the invention are preferably α,β-unsaturated enones or α,β-unsaturated sulfones of the general formula (II) in which R 5 and R 6 are identical or different and are (C 1 -C 12 )-alkyl, (C 2 -C 12 )-alkenyl, (C 2 -C 12 )-alkynyl, (C 5 -C 8 )-cycloalkyl, (C 6 -C 12 )-aryl, or (C 1 -C 12 )-heteroaryl, each of which radicals is optionally substituted once or more than once by identical or different radicals R 7 , halogen, NO 2 , NR 7 R 8 , PO 0-3 R 7 R 8 , or OR 7 , and R 7 and R 8 have the meanings indicated above for the general formula (II). [0053] Substrates particularly preferably employed in the process according to the invention are α,β-unsaturated enones or α,β-unsaturated sulfones of the general formula (II) in which R 5 and R 6 are identical or different and are (C 1 -C 12 )-alkyl, (C 2 -C 12 )-alkenyl, (C 2 -C 12 )-alkynyl, (C 5 -C 8 )-cycloalkyl, (C 6 -C 12 )-aryl, or (C 1 -C 12 )-heteroaryl, each of which radicals is optionally substituted once or more than once by identical or different radicals R 7 , halogen, NO 2 , NR 7 R 8 , PO 0-3 R 7 R 8 , or OR 7 , and R 7 and R 8 have the meanings indicated above for the general formula (II), with the proviso that at least one of the radicals R 5 or R 6 is a (C 2 -C 12 )-alkenyl, (C 2 -C 12 )-alkynyl, (C 6 -C 12 )-aryl-, or (C 1 -C 12 )-heteroaryl radical. [0054] It is particularly preferred to subject substrates of the general formula (III) to the epoxidation according to the invention: where n and m are identical or different and are the numbers 0, 1, 2 or 3, R 9 and R 10 are identical or different and are NR 7 R 8 , NO 2 , OR 7 , (C 1 -C 12 )-alkyl, (C 2 -C 12 )-alkenyl, (C 2 -C 12 )-alkynyl, (C 5 -C 8 )-cycloalkyl, (C 6 -C 12 )-aryl, or (C 1 -C 12 )-heteroaryl, each of which radicals R 9 and R 10 is optionally substituted once or more than once by identical or different halogen radicals, and R 7 and R 8 have the meanings mentioned previously for formula (II). [0059] A decisive advantage of the process according to the invention is the fact that homo-polyamino acids that are not preactivated separately are employed as catalysts. [0060] It is possible to use for the process according to the invention a wide variety of diastereomer- and enantiomer-enriched homo-polyamino acids. Preference is given, however, to the use of homo-polyamino acids selected from the group consisting of polyneopentylglycine, polyleucine, polyisoleucine, polyvaline, polyalanine, and polyphenylalanine. The most preferred from this group are polyneopentylglycine and polyleucine. [0061] The chain length of the polyamino acids will be chosen so that, on the one hand, the chiral induction in the reaction is not impaired and, on the other hand, the costs of synthesizing the polyamino acids are not too great. The chain length of the homo-polyamino acids is preferably between 5 and 100 (preferably 7 to 50) amino acids. A chain length of 10 to 40 amino acids is very particularly preferred. [0062] The homo-polyamino acids can be prepared by state of the art methods ( J. Org. Chem., 1993, 58, 6247 and Chirality, 1997, 9, 198-202). The method is to be applied to both optical antipodes of the amino acids. The use of a particular antipode of a polyamino acid correlates with the stereochemistry of the epoxide. That is to say, a poly-L-amino acid leads to the optical antipode of the epoxide that is obtained with a poly-D-amino acid. [0063] The homo-polyamino acids can be either employed as such unchanged in the epoxidation or previously crosslinked with polyfunctional amines or chain-extended by other organic polymers. The crosslinking amines advantageously employed for a crosslinking are diaminoalkanes (preferably 1,3-diaminopropane) or crosslinked hydroxy- or aminopoly-styrene (CLAMPS, commercially available). Suitable polymer enlargers are preferably nucleophiles based on polyethylene glycol or polystyrene. Polyamino acids modified in this way are described in Chem. Commun., 1998, 1159-1160, and Tetrahedron: Asymmetry, 1997, 8, 3163-3173. [0064] The amount of the homo-polyamino acid employed is not critical and is normally in the range 0.0001 to 40 mol % (preferably in the range 0.001 to 20 mol %, particularly preferably in the range 0.01 to 15 mol %, and especially in the range 1 to 15 mol %), in each case based on the α,β-unsaturated enone or α,β-unsaturated sulfone employed. [0065] It is also possible to employ the homo-polyamino acids in a form bound to a support, which may be advantageous in relation to the recoverability of the catalyst and the increase in the optical and chemical yield. [0066] For this purpose, the homo-polyamino acids are bound by adsorption to an insoluble support material. The insoluble support materials preferably employed are those based on silica or zeolite, such as, for example, molecular sieves, silica gels, Celite® 521, Celite® Hyflo Super Cell, or Wessalith® DayP. Silica gels with defined pore sizes such as, for example, CPC I or CPC II are also advantageous. Further preferred support materials are activated carbon or sugar derivatives such as, for example, nitrocellulose and cellulose. [0067] The ratio of support material to polyamino acid is given by two limits. On the one hand, only a certain number of polyamino acids can be adsorbed on the insoluble support, and on the other hand, there is a decline in chiral induction with less than 10% by weight of polyamino acid relative to the support onwards. The ratio of homo-polyamino acid to support material is preferably in the range from 1:7 to 2:1 parts by weight, particularly preferably in the range from 1:1 to 1:4 parts by weight. [0068] The method for application to a support is described in detail in EP-A 1,006,127, to which express reference is hereby made. For this purpose, initially a mixture of the appropriate homo-polyamino acid and the support material is suspended in an organic solvent such as an ether (for example THF) and then stirred for a prolonged period, preferably up to 48 hours. The solid is then filtered off and dried. [0069] If such supported catalysts are to be employed, then a particularly suitable device for the epoxidation process is one capable of retaining only the catalyst. This device is preferably an enzyme membrane reactor (C. Wandrey in Enzymes as Catalysts in Organic Synthesis; Ed. M. Schneider, Dordrecht Riedel 1986, 263-284). Preference is likewise given to a simple fixed bed reactor such as, for example, a chromatography column. [0070] The oxidants usually employed are hydrogen peroxide complexes with inorganic carbonates, tertiary amines, amino oxides, amides, phosphanes, or phosphane oxides. The urea/hydrogen peroxide complex has proved particularly suitable. [0071] The amount of the oxidant employed may be varied within the wide limits of 1 to 10 equivalents. Surprisingly, furthermore, short reaction times and high enantiomeric excesses can be achieved even with very small amounts of oxidant in the range 1 to 5 equivalents, preferably 1 to 3 equivalents, and particularly 1 to 2 equivalents. [0072] The process according to the invention is carried out in the presence of a base that may be organic or inorganic. However, organic, non-nucleophilic bases are preferably employed, particularly DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), DBN (1,5-diazabicyclo[4.3.0]non-5-ene), or DABCO (1,4-diazabicyclo[2.2.2]octane). [0073] The amount of the base employed may be varied within the wide limits of 0.1 to 10 equivalents. The reaction according to the invention still takes place with short reaction times and high enantiomeric excesses even with amounts of from 0.5 to 5 equivalents, preferably of from 0.8 to 2 equivalents. [0074] The process according to the invention is carried out using an organic solvent Suitable organic solvents are in general ethers (preferably THF, diethyl ether, or tert-butyl methyl ether), esters (preferably ethyl acetate), amides (preferably dimethylformamide), or sulfoxides (preferably dimethyl sulfoxide). [0075] The temperature used in the epoxidation is generally in the range from −10 to +50° C., preferably in the range from 0 to +40° C., and particularly at +10 to +30° C. [0076] In relation to the procedure for the reaction, normally all the components apart from the base are mixed and then the base is added. However, it is also possible to stir the polyamino acid in the presence of the oxidant, of the base, of the solvent, and of the phase-transfer catalyst for 15 min to 2 hours, and thus preactivate it, and then, without intermediate isolation of the preactivated homo-polyamino acid, to add the substrate to be epoxidized. [0077] The two-phase process according to the invention for the enantio-selective epoxidation of α,β-unsaturated enones and α,β-unsaturated sulfones is distinguished by the possibility of using homo-polyamino acids that have not been preactivated separately. It is possible with this process, because of the presence of a phase-transfer catalyst, to dispense with the normally necessary time-consuming (3 to 5 days) and laborious separate preactivation with intermediate isolation. Substantially higher enantiomeric excesses are usually achieved with the process according to the invention. [0078] The following examples further illustrate details for the process of this invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions of the following procedures can be used. Unless otherwise noted, all temperatures are degrees Celsius and all percentages are percentages by weight. EXAMPLES [0079] The process for preparing polyamino acids often provides catalysts for the Juliá-Colonna epoxidation which vary widely in catalytic activity ( Chirality, 1997, 9, 198-202). The conversion per unit time and the enantiomeric excess can be compared for a particular substrate only if the same polyamino acid batch is used for the epoxidation reaction. For this reason, direct comparison of new results with results published in the literature is impossible, simply because different catalyst batches are inevitably used. For this reason, a uniform polyleucine batch was used in each of the subsequent examples and comparative examples. [0080] In all the following examples, the conversion and the enantiomeric excess (ee) were determined by methods known from the literature using HPLC on a chiral, nonracemic phase (UV detection). Examples 1 and 3 and Comparative Examples 2 and 4 [0081] Epoxidation of Trans-Chalcone (1) to Epoxychalcone (2) Under Two-Phase and SCAT Conditions Example 1 [heading-0082] 2-Phase Conditions with PTC [0083] 50 mg of trans-chalcone, 35 mg of urea/hydrogen peroxide complex (UHP, 0.36 mmol, 1.5 equivalents), 8.5 mg of [(C 4 H 9 ) 4 N + ]Br − , and 100 mg of pII that had not been separately preactivated (11 mol %) were mixed and, after suspending in 1.5 ml of anhydrous THF, 55 μl of DBU (1.5 equivalents) were added. The reaction mixture was allowed to react at room temperature with stirring. After a reaction time of 30 minutes, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. Comparative Example CE 2 [heading-0084] 2-Phase Conditions Without PTC [0085] 50 mg of trans-chalcone, 35 mg of urea/hydrogen peroxide complex (UHP, 0.36 mmol, 1.5 equivalents), and 100 μg of pII that had not been separately preactivated (11 mol %) were mixed and, after suspending with 1.5 ml of anhydrous THF, 55 μl of DBU (1.5 equivalents) were added. The reaction mixture was allowed to react with stirring at room temperature. After a reaction time of 30 min, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. Example 3 [heading-0086] SCAT Conditions [heading-0087] a) Preparation of SCAT [0088] 1 g of pII that had not been separately preactivated and 3.4 g of silica gel 60 (230-400 mesh, Merck) were mixed, suspended in 30 ml of anhydrous THF, and stirred slowly for 48 h with exclusion of light. The suspension was filtered and the residue was washed twice with 10 ml of anhydrous THF each time. The material (SCAT) was dried in vacuo over P 2 O 5 . [heading-0089] b) Epoxidation Under SCAT Conditions with PTC [0090] 50 mg of trans-chalcone, 35 mg of urea/hydrogen peroxide complex (UHP, 0.36 mmol, 1.5 equivalents), 8.5 mg of [(C 4 H 9 ) 4 N + ]Br − , and 100 mg of SCAT (11 mol %) were mixed and, after suspending with 1.5 ml of anhydrous THF, 55 μl of DBU (1.5 equivalents) were added. The reaction mixture was allowed to react with stirring at room temperature. After a reaction time of 30 min, the reaction mixture was filtered and concentrated under reduced pressure. Comparative Example CE 4 [heading-0091] SCAT Conditions Without PTC [heading-0092] a) Preparation of SCAT [0093] 1 g of non-separately preactivated pII and 3.4 g of silica gel 60 (230-400 mesh, Merck) were mixed, suspended in 30 ml of anhydrous THF, and stirred slowly for 48 h with exclusion of light. The suspension was filtered and the residue was washed twice with 10 ml of anhydrous THF each time. The material (SCAT) was dried in vacuo over P 2 O 5 . [heading-0094] b) Epoxidation Under SCAT Conditions Without PTC [0095] 50 mg of trans-chalcone, 35 mg of urea/hydrogen peroxide complex (UHP, 0.36 mmol, 1.5 equivalents), and 100 mg of SCAT (11 mol %) were mixed and, after suspending with 1.5 ml of anhydrous THF, 55 μl of DBU (1.5 equivalents) were added. The reaction mixture was allowed to react with stirring at room temperature. After a reaction time of 30 min, the reaction mixture was filtered and concentrated under reduced pressure. [0096] The results of Examples 1 and 3 and of Comparative Examples CE 2 and 4 are compiled in the table below. TABLE Reaction Conver- Exam- time sion ee ple Conditions PTC [min] [%] [%] 1 according to the [(C 4 H 9 ) 4 N + ]Br − 30 >99 78 invention CE 2 2-phase; not — 30 >99 53 according to the invention 3 according to the [(C 4 H 9 ) 4 N + ]Br − 30 >99 92 invention CE 4 2-phase, SCAT; — 30 >99 86 not according to the invention
The invention relates to a novel process that makes it possible to epoxidize α,β-unsaturated enones or α,β-unsaturated sulfones with high conversions and enantiomeric excesses in a two-phase system without addition of water in the presence of an organic solvent, a base, an oxidant, a diastereomer- and enantiomer-enriched homo-polyamino acid that has not been separately preactivated as catalyst, and a specific phase-transfer catalyst as cocatalyst.
2
TECHNICAL FIELD [0001] The present invention relates to a hand-retaining device, such as for example a glove or a hand strap which can be fastened on the hand, which hand-retaining device has, between the thumb and forefinger, a coupling element for coupling to a pole grip, in particular for walking sticks, trekking poles, downhill ski poles, cross-country ski poles and Nordic walking poles. Such a hand-retaining device is preferably suitable for fastening in a releasable and self-latching manner on a pole grip with a grip body with a hook-like device. PRIOR ART [0002] A pole grip as is known, for example, from U.S. Pat. No. 5,516,150, has a hook provided on it, and a rigid bow-like device formed from a curved metal element is provided on the associated glove, in the region between the thumb and forefinger. The bow has its long leg introduced into a narrow slot of the hook, and the hook-like device fixes the bow, and thus the glove, on the pole grip. [0003] Provision is made here for the slot to be widened slightly at the bottom of the hook, which means that, when the bow is moved into the hook, it initially forces the two legs of the hook apart from one another to a slight extent, and that it is only when the bow has been pushed into the widened portion that the legs spring back into the original position. [0004] Elastic deformation of the hook-like device is thus used in order to fix the bow easily in the hook and to avoid the situation where the bow can easily slide out of the hook. [0005] One of the problems with such devices is the fact that repeated deformation of such components, which are usually formed from plastic or metal, is undesirable on account of signs of fatigue. [0006] There is also the particular problem of the elastic deformation behavior of materials being highly dependent on temperature. It is thus also the case that the fixing action which is achieved by the deformation is neither adjustable nor constant for different temperatures. [0007] This is absolutely unacceptable in the sporting arena in particular, since very large differences in temperature are unavoidable, on the one hand, on account of different weather conditions and, on the other hand, as a result of heating or warming up during use. DESCRIPTION OF THE INVENTION [0008] This is where the invention comes in. The object of the invention is thus to provide a hand-retaining device which has improvements over the prior art and is intended for fastening in a releasable and, in particular preferably, self-latching manner on a pole grip with a hook-like device. The concern here in particular is to improve such a hand-retaining device for use in conjunction with a pole grip for walking sticks, trekking poles, downhill ski poles, cross-country ski poles and Nordic walking poles, these having a grip body with a hook-like device for fastening a hand-retaining device in particular in the form of a hand strap or of a glove. This object is achieved in that the hand-retaining device, for example a glove or a hand strap which can be fastened on the hand, has as a coupling element, between the thumb and forefinger, a movable, that is to say inherently flexible, loop which is suitable for fastening the hand-retaining device on a hook-like device of a pole grip. Such a hand-retaining device proves to be successful, in particular, when used in conjunction with pole grips in which displaceable or rotatable latching-in means are arranged in the region of the hook-like device such that a loop-like, ring-like or eyelet-like device, which is inserted or pushed into the hook-like device preferably essentially from above and is provided on the hand-retaining device, is fixed in the hook-like device with self-latching action. [0009] Rather than, as has usually been deemed absolutely necessary in the prior art, providing a stiff element as the coupling element, in order that this element can be pushed at all over the hook-like device without the aid, for example, of the other hand, the core of the invention thus consists in providing an inherently flexible, that is to say movable, element in the form of a simple loop. This means that the coupling element is considerably less troublesome both during use, when the hand-retaining device is fastened on the pole grip, and when the hand-retaining device is not fastened on the pole grip. Surprisingly, such a movable loop is nevertheless readily capable of absorbing the high forces which occur and, in addition, it allows optimum guidance even when the pole grip is not actively being gripped. The loop here is preferably fastened on the hand-retaining device such that, as a result of its remaining inherent rigidity, it projects between the thumb and forefinger such that it can easily be pushed over the hook-like device. [0010] Hand-retaining devices which are particularly well suited for being used together with an above-mentioned pole grip are therefore those which have a movable loop or eyelet in the V region between the thumb and forefinger. Such a hand-retaining device interacts with a pole grip as described above in the manner of a key and lock or plug and socket. The small loop is particularly comfortable and is not obtrusive, in which case such a glove or such a hand-retaining device is also suitable for biathlon or the like. [0011] The loop, in particular, is a loop which is made of a flexible material with a sufficient level of inherent rigidity to stabilize it in a position in the space between the thumb and forefinger, which allows it to be introduced straightforwardly over the hook or retaining peg and which, conversely, cannot be felt, or can only barely be felt, during use. Possible examples of loops are those made of a cable or wire, which may be surface-coated. Examples of other elements which are basically also suitable to be used as material for such loops are textile fibers which are encased in a woven-fabric sheath, have limited expansion capability and are stable in relation to tension, or retaining elements which are braided in a cord-like or cable-like manner, using corresponding materials such as for example Aramid, Kevlar, Dyneema, etc. If use is made of such materials for the loop, cords with a thickness of 1-5 mm are most suitable, a thickness of 2-3 mm being preferred. In order to impart a sufficient level of inherent rigidity to the loop, such cords may be provided with stiffening elements, for example a “core” made of monofilament nylon or in-woven fibers consisting of a relatively stiff material, for example nylon or thin metal wires. It has been found that a cable with a thickness in the range of 0.5-2.5 mm, preferably in the range of 1-2 mm, is particularly suitable. [0012] The, for example, braided or twisted cable can be coated with another material, for example copper or plastic. As an alternative, it is possible to produce the loop from a plastic material, also, for example, in band form, preferably from a fiber-reinforced plastic, for example polyamide, PE, PP or the like being suitable, in which case combined materials with a layered construction are also possible, and in particular preferably reinforcements with fibers for example made of Aramid may be provided. [0013] The loop preferably projects by between 5-20 mm, in particular by between 5-10 mm, beyond the V region between the forefinger and thumb. In this case, the direction of the loop, to a certain extent, runs essentially along the angle bisector between the thumb and forefinger. [0014] It is possible for the loop to be adjustable, this adjustability being provided, on the one hand, in order to adjust the length specifically to the user, but also, when the loop is not required, in order to retract the same so that it cannot be felt during use. It is also possible for the loop to be stowed, when not in use, in a small pocket, which is provided for this purpose in the hand-retaining device, likewise in the V region between the forefinger and thumb. This latter possibility is particularly straightforward in design terms and, as far as the inherent rigidity of the loop is concerned, on the one hand, the loop can be accommodated in such a pocket and, on the other hand, if not specifically manipulated, it remains concealed, essentially without any special measures having to be taken in the pocket, during use of the hand-retaining device. [0015] In order to ensure that the forces which act on the loop are coupled as well as possible to the hand-retaining device, the wire/the cable of the loop can be guided in the direction of the wrist, at least in part, in or on the hand-retaining device. It is also possible to provide a combination with an adjustable device like that described in DE 19751978 C2, the disclosure of which is expressly included in this respect. Instead of the rigid connecting element cited in this document, a flexible loop is simply provided. The loop is considerably less troublesome in particular when the glove is used without the pole. [0016] The hand-retaining device according to a first embodiment is thus preferably characterized in that the loop comprises an inherently movable cable or bow or a flexible plastic cord with inherent rigidity. It is preferably here for the loop to be fastened in an essentially non-movable manner on the hand-retaining device, but the loop is itself of movable design. [0017] As has already been mentioned, the hand-retaining device may be a glove, or else a hand strap which has three openings and which can be fastened on the hand in particular preferably with the aid of a touch-and-close fastener, a first opening being provided for the thumb, a second opening being provided for the other fingers or the back of the hand, and a third opening of the hand strap being provided for the wrist. [0018] In order to allow the loop to be introduced as easily as possible onto the hook-like device, and in order to ensure ideal force transmission, it proves to be advantageous if the projecting part of the loop on the hand-retaining device is arranged essentially in the plane which, when the hand is open and stretched out, is defined by the thumb and forefinger. [0019] As has already been mentioned, the loop is preferably a loop made of a plastic material, preferably a plastic fiber which is oriented and/or has limited expansion capability, in particular preferably based on polyethylene, in particular preferably oriented polyethylene, e.g. Dyneema®, polyamide, polypropylene, Aramid or a combination of these materials. Preferred combinations are ones in which a core made of, for example, oriented polyethylene fibers is enclosed by braided synthetic fibers in the manner of a braided sleeve. [0020] A further preferred embodiment of the hand-retaining device according to the invention is characterized in that the length of the loop is adjustable, it being possible, in particular preferably, for the loop to be recessed essentially fully into or on the glove when not in use. As an alternative, it is possible for the hand-retaining device to contain a niche or pocket into which the loop can be inserted when not in use. [0021] In order to allow the loop to be fastened as well as possible on the hand-retaining device, in particular on the glove, it proves to be advantageous if, at least over a length of 2-15 cm, in particular preferably of at least 5 cm, the non-exposed region of the material of the loop, at both ends, is adhesively bonded, sewn or woven in or on the hand-retaining device, and/or in the form of an intermediate layer of the hand-retaining device, or is fastened in some other way between the outer layers of the hand-retaining device. [0022] The material of the loop is also fastened on the hand-retaining device, for example, via a band strip, in particular made of woven plastic-based textile material with a width of between 3-30 mm, this band strip being sewn in particular preferably on the outside of the hand-retaining device, or being adhesively bonded or sewn to the glove, and the band strip, further preferably, being arranged in the V between the thumb and forefinger so as to encircle the back of the hand and the palm of the hand. [0023] A further preferred embodiment is characterized in that a hand strap may be integrated, to a certain extent, in a glove, in which case the hand strap itself with the movable loop can be used without the glove and the glove can be used with the hand strap embedded in it. The hand-retaining device may thus be configured as a glove in which is arranged, in one or more corresponding recesses, a hand strap which preferably has three openings and which can be fastened on the hand, or on/in the glove, in particular preferably with the aid of a touch-and-close fastener, a first opening being provided for the thumb, a second opening being provided for the other fingers or the back of the hand, and a third opening of the hand strap being provided for the wrist. The hand strap, in particular preferably, is arranged in the glove such that it can be adjusted from the outside via a touch-and-close fastener arranged in the region of the back of the hand. The hand strap can advantageously be removed altogether from the glove and can be used without the glove. [0024] A further preferred embodiment of the hand-retaining device is distinguished in that, in the rest position, the loop is of essentially semi-circular or semi-oval form, in particular preferably with a diameter in the range of 3-10 mm. [0025] Further preferred embodiments of the hand-retaining device according to the invention are described in the dependent claims. [0026] As has already been mentioned, such a hand-retaining device can be used, in particular preferably, in conjunction with a pole grip which has a hook-like device into which the loop can be pushed with self-latching action. If use is made here, for latching-in purposes, of a rotatable or displaceable element, there is essentially no material deformation on the hook in the case of a self-latching mechanism for fastening a hand-retaining device on the pole grip; so preferably mechanisms are used in which, when a loop-like, ring-like or eyelet-like device is pushed into a latched-in position, a corresponding latching-in means is either displaced or rotated. It is thus possible correspondingly to provide a specific elastic mounting arrangement for these latching-in means, the arrangement, in particular, being less susceptible to wear, being adjustable, if appropriate, and having a low level of temperature dependence in respect of the forces. The hook-like device is arranged in the top region of the pole grip, e.g. on the hand side, it being the case that the hook-like device comprises a retaining pin or retaining peg which is arranged preferably essentially parallel to the pole axis (although a specific amount of inclination may also be present) and is offset in the direction of the hand side from the grip body to form an introduction slot, the depth of the introduction slot being greater than the width and the thickness of the retaining peg or retaining pin. Offset does not necessarily mean that the retaining peg or retaining pin has to project beyond the contour of the grip body; it is also possible for the retaining peg or retaining pin to be positioned in a recess which is open toward the top and rear and is provided specifically for this purpose in the grip body. It has typically been found that the hook-like device advantageously has a width in the range of 3-15 mm, preferably in the range of 4-10 mm, the hook-like device having an essentially oval or rectangular (possibly with rounded edges) cross section, in particular preferably at least in certain sections perpendicular to the pole axis, in which case preferably the short main axis is directed toward the grip body. The introduction slot typically has a depth in the range of 5-30 mm, preferably in the range of 10-15 mm. It is possible here, for example, to provide a slight convexity in the hook-like device directly opposite the latching-in means. [0027] The hook-like device may be integrally formed on the grip body. In particular in combination with the mechanism which is described hereinbelow, and in the case of which a recess is provided in the pole grip for accommodating the mechanism, it preferably proves to be expedient to design the hook-like device as a separate component. This is then fastened on the grip body via fastening means, preferably once the mechanism has been inserted into the recess of the grip body. This can be realized, for example, by the hook-like device having, beneath the hook, a fastening plate by means of which the hook-like device can be fastened on the grip body (for example by means of a screw or rivet or via a clip mechanism) from the hand side. [0028] As has already been explained, the grip body is provided, from the hand side, for example with a recess which accommodates a displaceably mounted element, in particular preferably in the form of an arresting block, on or in which latching-in means are arranged, it being possible for these latching-in means to be formed either integrally with the arresting block or as a separate component, and in the latter case this separate component, for example in the form of a restraining nose, can be connected to the arresting block either in a fixed manner or via a movable mechanism. [0029] The arresting block is advantageously guided such that it can be displaced parallel to the direction of the recess, but it is also possible to mount it for rotation. The arresting block is braced against the hook-like device, which is arranged in front of the recess, via a spring (this also covering, in general, resiliently elastic elements), in particular preferably via a helical spring. This results in the above-mentioned self-latching mechanism. [0030] In order that the hand-retaining device can also be separated from the pole grip again, means should be provided in order to push the latching-in means back and release the hand-retaining device from the hook. This is possible, for example, by it being possible for the arresting block to be displaced from the outside, counter to the spring force, via at least one actuating button, the self-latching mechanism being released in the process, in which case, for this purpose, slots are provided laterally, in particular preferably in the grip body in relation to the recess and, via these slots, actuating buttons arranged on both sides are operatively connected to the arresting block, for example by a fixed connection being created between these two elements via a crosspiece or pin. [0031] It is basically possible for the arresting block to be fitted in a rotatable or displaceable manner on the grip body by a wide variety of different methods. It is thus possible, for example, to design the uppermost region in its entirety, that is to say, as it were, the head region of the pole grip, as the arresting block, in which case, to a certain extent behind the same and fixedly connected to the bottom part of the pole grip, or formed integrally therewith, the hook-like device is provided so as to allow a loop of a hand-retaining device to be fixed between the arresting block and the hook-like device. [0032] It is possible to provide, in or on the arresting block, at least one activating button by way of which the retaining means arranged in the arresting block, preferably in the form of a pin, can be displaced counter to the spring force, the self-latching mechanism being released in the process. It is also possible for the grip body to be provided from the hand side, and from above, with a recess which accommodates a displaceably and/or rotatably mounted element in the form of an arresting block in which latching-in means are arranged, the arresting block being braced in the downward direction for emergency activation via an axial helical spring which is arranged in a cavity of the pole grip and the stressing of which can be adjusted preferably via an adjusting nut. [0033] The grip body may be provided, from the top side, with a recess which accommodates a displaceably and/or rotatably mounted element, in particular preferably in the form of an arresting block, on which latching-in means are arranged. If the recess is provided from above, it is then possible, without obstructing assembly or installation, to form the hook-like device, for example, integrally with the grip body, for example in the form of a simple slot or cutout arranged in the grip body on the hand side. The arresting block here can be mounted in a rotatable manner about a horizontal axial element, which is arranged between the hook-like device and grip body preferably essentially parallel to the plane of the slot, and it can be braced against the hook-like device, arranged on the hand side, via a spring, in particular preferably via a helical spring or a leaf spring. The arresting block can then be tilted from the outside, counter to the spring force, via at least one actuating button, the self-latching mechanism being released in the process, in which case, for example, the actuating button is provided essentially on the top side of the pole grip, that is to say the arresting block is exposed, to a certain extent, from above and a part or portion, or a sub-surface, of the arresting block forms the actuating button. [0034] The latching-in means may be designed in the form of a restraining nose which has a beveled flank toward the top, in particular preferably as seen in the direction of introduction, and which, in the position in which it is braced against the hook-like device, defines, in the downward direction, a region for the loop-like, ring-like or eyelet-like device which is restricted in respect of a preferably adjustable force. It is possible here for this retaining nose to be arranged either on the arresting block or, as it were opposite, on the hook-like device. [0035] The latching-in means may preferably be designed in the manner of a safety mechanism such that, in the event of loading in the direction of the opening of the hook-like device which goes beyond a normal usage force, emergency release of the loop-like, ring-like or eyelet-like device takes place, this being similar to a mechanism which is also known in respect of ski bindings. This can be realized either via elastic deformation of this nose, or in the region of this nose, or else, and this is the preferred variant because it can be much better controlled and possibly even adjusted, by the restraining nose being mounted in a rotatable manner about a preferably horizontal axial element arranged essentially perpendicularly to the opening direction of the recess. Rotation in the upward direction, to release the region in the upward direction, is only possible here counter to a defined and, as has already been mentioned, preferably adjustable force. The restraining nose may be braced by way of a leg spring, by way of an elastomer spring or by way of a helical spring, or by way of a combination of such resilient elements, into the rotary position in which it closes off the region, this bracing in particular preferably being adjustable, in which case safety activation takes place only under a force of more than 80-250 N. A further analogous embodiment of the pole grip is characterized in that the restraining nose is mounted in a displaceable manner, in which case displacement in the upward direction to release the region is possible counter to a defined and preferably adjustable force, as specified above, and the force is preferably ensured via a spring or a resilient element. [0036] Moreover, safety activation can also be realized via a yielding action in the region of the hook-like device. For this purpose, the hook-like device may be configured such that it can be displaced or tilted about an axial element, counter to an elastic force, in the direction of the hand side to release the region. As an alternative, or in addition, it is possible to provide a resilient region on the hook-like device on the slot side. This resilient region can be realized, for example, via a leaf spring or an elastic portion (specifically a soft elastic polymer portion or the like). BRIEF EXPLANATION OF THE FIGURES [0037] The invention will be explained in more detail below with reference to exemplary embodiments, in conjunction with the drawings, in which: [0038] FIG. 1 shows different views of a pole grip, a) illustrating a lateral, partially transparent, view, b) illustrating a view from behind (hand side), c) illustrating an exploded view from the side, d) illustrating a section along line A-A in FIG. 1 c ), e) illustrating an exploded view in a section along line A-A in FIG. 1 c ), f) illustrating a perspective exploded view, and g) illustrating an alternative hook-like device with safety-activation element on the hook; [0039] FIG. 2 shows a hand-retaining device with a loop between the thumb and forefinger; [0040] FIG. 3 a )- c ) show different exemplary embodiments of hand-retaining devices with loops between the thumb and forefinger; [0041] FIG. 4 shows different views of a pole grip, a) illustrating a lateral view with arresting block inserted, b) illustrating a lateral view without an arresting block, and c) illustrating an arresting block on its own; [0042] FIG. 5 shows different variants of a pole grip analogous to FIG. 4 , a) illustrating a safety-activation means without a separate safety-activation element, b) illustrating a safety-activation means with a displaceably mounted safety-activation element, c) illustrating a safety-activation means with a rotatably mounted safety-activation element, d) illustrating a safety-activation means with a safety-activation element which can be elastically deformed as a whole, e) illustrating a safety-activation means in which the safety-activation element is arranged on the inside of the hook-like device, and f) illustrating a safety-activation means with a hook-like device which can be tilted as a whole; [0043] FIG. 6 shows the entire pole grip 1 , a) illustrating a view from the side, b) illustrating a view from the rear, c) illustrating an axial section along line B-B from b), and d) illustrating a view of the pole grip from above; and [0044] FIG. 7 a ) shows a view from the side of the arresting block 6 together with the elements fastening this arresting block 6 in the pole grip 1 , b) shows a view from the rear, c) shows a section along line A-A in b), and d), finally, shows a view from above. WAYS OF IMPLEMENTING THE INVENTION [0045] FIGS. 1 a )- f ) illustrate different views of a pole grip. The pole grip 1 comprises a grip body 3 , which is usually produced from a plastic material by injection molding. As seen from beneath, the grip body 3 has a recess or a cavity 5 into which the pole, which is formed, for example, from an aluminum shaft or a carbon-fiber or glass-fiber shaft, can be pushed and fastened therein. [0046] At its top end, the pole grip 1 has a recess 4 which is designed from the hand side 43 , as it were, as a blind hole. An arresting block 6 is provided in this recess 4 , which typically has a height in the range of 10-30 mm and a width in the range of 3-20 mm. This arresting block 6 is guided in a displaceable manner in the recess 4 , and is braced in the direction of the opening of the recess 4 via a spring 7 . The spring 7 is a helical spring which is guided, at one end, in the recess, in a stop bore 8 which is configured as a cylindrical blind hole, and, at the other end, on a guide peg 19 on the arresting block 6 . [0047] The recess 4 additionally has two through-slots 17 which lead laterally out of the grip body 3 . The arresting block 6 for its part, in these regions, has bores in which a respective actuating button 9 can be fastened on each side. The actuating button 9 has in each case a crosspiece 20 directed toward the arresting block 6 and, when the arresting block 6 is pushed in, it is fastened in the arresting block 6 from the outside through the abovementioned lateral slots 17 , for which purpose a screw or fastening pin 21 can be used in each case. This means that the actuating button 9 can be displaced from the outside via manipulations of the actuating buttons, this being such that, in the normal position, the arresting block 6 is located to the maximum possible extent in the direction of the hand side as a result of the force of the spring 7 , this maximum position preferably being determined by the hand-side end of the slot 17 . The arresting block 6 can be pushed into the recess 4 , counter to the force of the spring, from the outside, this releasing the arresting mechanism for the hand-retaining device. [0048] A hook-like device ensures that the hand-retaining device is actually secured on such a pole grip. This hook-like device comprises a retaining peg 14 which is arranged on the hand side. The retaining peg 14 is offset slightly in the direction of the hand from the actual pole grip, a slot which typically has a depth of at least 10 mm being formed therebetween. [0049] For easier assembly, the retaining peg 14 is connected to a fastening plate 16 or formed integrally therewith. The fastening plate 16 is located beneath the retaining peg 14 and can be inserted in a recess provided for this purpose in the pole grip 3 , and fastened therein. This modular construction is preferred since it is thus possible for the retaining peg 14 , which is naturally arranged in front of the recess 4 , to be placed in position once the elements which have to be arranged in the recess 4 have been inserted into the recess 4 . [0050] The arresting block 6 , for its part, likewise has a recess 24 , which is bounded laterally and at the bottom but is open at the top. The safety-activation element 12 is mounted in a movable manner in the recess 24 . For this purpose, the safety-activation element 12 is mounted in the arresting block 6 such that it can be rotated by way of an axial pin 22 . This rotatable mounting, in turn, is counter to a spring force, a leg spring 10 being provided in this case. This leg spring, on the one hand, rests on the base of the recess 24 and, on the other hand, rests on the rear side of the safety-activation element 12 . The spring force thus retains the safety-activation element 12 in its closed position, that is to say in that position in which the restraining nose 11 of the safety-activation element 12 , together with the retaining peg 14 , defines a closed-off region 15 , in which the loop of the hand-retaining device ends up located. It is also possible, instead of the leg spring 10 , to use a helical spring or an elastomer spring or the like, or combinations of such resilient elements, which is then for example in operative connection with the rear wall of the recess 24 . Use of a helical spring may be advantageous, in particular, at low temperatures and, moreover, allows the restraining force of the nose 11 to be adjusted. The safety-activation element 12 may have in the downward direction, as can be seen in FIG. 1 c ) and f) in particular, a notch, in order that the cable can be arrested to better effect in the region 15 . [0051] As has already been mentioned, the hand-retaining device has a loop 33 , which is guided over the retaining peg 14 . If the loop 33 is guided over the retaining peg from above and pulled downward, then the entire arresting block 6 is displaced into the recess 4 because, in the case of pressure being exerted from top to bottom, the oblique top flank of the safety-activation element 12 pushes the arresting block 6 rearward, counter to the spring force, and the gap between the retaining peg and grip body is released. Once the loop has reached the region 15 , the entire arresting block springs back again toward the retaining peg 14 , as a result of the spring force of the spring 7 , and the region 15 is closed. The hand-retaining device is thus automatically fastened/latched in on the grip body without any further manipulations being necessary. [0052] If the loop of the hand-retaining device is to be removed again from the slot between the retaining peg and grip body, then the entire arresting block 6 can be displaced upward, counter to the spring force, via the actuating buttons 9 , in which case the nose 11 releases the region 15 . [0053] In addition to this means of automatically fastening the hand-retaining device on the grip body, a safety-activation mechanism is provided. For this purpose, the safety-activation element 12 can be opened upward counter to a spring force, this being done with the arresting block pushed all the way up to the retaining peg. If the loop is subjected to a pronounced force in the upward direction (for example in the event of a fall), then the safety-activation element 12 rotates about the axial element 13 such that the region 15 is released and thus the loop, and correspondingly the hand-retaining device, is released from the grip body. [0054] As is illustrated in FIG. 1 g ), the safety mechanism may also be provided on the retaining peg. For this purpose, the retaining peg has a recess 41 in which the safety-activation element 12 is mounted such that it can be rotated about an axial element 13 . A spring 7 is again provided, in this case a helical spring, which defines the necessary activating force. In this case, it is possible, for example, to adjust the restoring force of the spring 7 via a screw which can be actuated on the retaining peg from the outside, on the hand side. The screw can be screwed in, for example, to shorten the spring, and the restoring force of the spring is thus increased. [0055] FIG. 2 shows a hand-retaining device which is configured according to the invention. The hand-retaining device is configured as a glove 25 , and this glove 25 basically has a fastening guide such as that described in DE 19751978 C2. In respect of the details of this fastening guide, which comprises, inter alia, an encircling fastening device 31 as well as adjusting means 32 which may be designed, for example, as a touch-and-close fastener, reference is made to DE 19751978 C2. [0056] Instead of the hook-like connecting element which is portrayed in DE 19751978, however, a loop 33 is arranged in the V region between the thumb 26 and forefinger 27 in this case. The loop is produced from cable, for example stainless steel, encased synthetic fibers such as Aramid, Dyneema® or the like with a thickness of 1.5 mm, the cable being a twisted cable which may be provided, if appropriate, with a coating made of plastic or metal or may have a tube of brass positioned around it or has a sheath made of, for example, thermoplastically integrally formed or braided polymer material. [0057] The loop 33 should be fastened on the hand-retaining device such that the forces which occur during use of the pole are distributed to good effect over the hand. This is ensured in the case of a hand-retaining device according to FIG. 2 . Alternative options are illustrated in FIG. 3 . In FIG. 3 a ), a cable 35 is fixed, in the first instance, at one end at a fastening 36 in the palm of the hand. It is then guided through a guide sleeve 34 to the V between the forefinger and thumb 26 . The actual loop 33 is exposed there and the cable 35 is guided downward, once again, through the guide 34 . Provided at the bottom end of the guide sleeve 34 are a deflecting means 37 and a fastening 38 , at which the cable 35 can be adjusted in a variable manner (cf. arrow). The length of the loop 33 can thus be adjusted in adaptation to the user, and the forces which occur are distributed to good effect over the glove. It is further possible for the cable 35 to be fully retracted, in which case there is no loop 33 projecting outward. This is advantageous, in particular, when the glove is not to be used in conjunction with the pole grip. In contrast to other solutions, in which connecting elements have to be removed from the glove, this solution is advantageous because the connecting element, in other words the loop, is concealed in the hand-retaining device rather than having to be removed therefrom. [0058] Another option is illustrated in FIG. 3 b ). In this case, the cable 35 is configured as an encircling cable which is adjusted in length at its bottom end, at a button 39 . It is possible to provide a further button 40 , which is arranged further below and via which the cable 35 can be retracted if the loop is to be concealed. [0059] Finally, FIG. 3 c ) illustrates an option in which the cable is fixed at the bottom via the means 36 . The loop 33 cannot be adjusted in length here. In order, nevertheless, for it to be possible for the loop to be concealed when not in use, a small pocket is provided in the V region between the thumb and forefinger. When not in use, the loop 33 can be pushed into this pocket 41 , which has an opening at the bottom, and it is thus kept out of the way. [0060] It is also possible for the hand-retaining device 25 to be in the form of a hand strap which is worn over a glove, or over the bare hands, and has a loop 33 . If a conventional hand strap is used, then the mechanism serves as a safety-activation means; if use is made of a hand strap which is fastened on the hand (usually by the hand strap being guided both over the wrist and between the thumb and forefinger and being fastened, for example, with a touch-and-close fastener), then the use is equivalent to the glove solution like that indicated above. [0061] A further exemplary embodiment is illustrated in FIG. 4 , although this figure illustrates a cross-country ski pole grip or a Nordic walking pole grip rather than a downhill ski pole grip. In this case, rather than being formed separately from the grip body 3 , the hook-like device 14 forms a constituent part of the grip body. The hook-like device is realized by a slot which is provided in the grip body 3 . Correspondingly, the recess 4 , which is provided for accommodating the arresting block 6 , is made from above. In this exemplary embodiment, then, it is additionally the case that the arresting block 6 , rather than being displaceable, is mounted in a rotatable manner, about an axial element 44 . Correspondingly, the actuating button 9 is arranged at the top, and tilting of the arresting block 6 results in the enclosed region 15 being released. In the exemplary embodiment according to FIG. 4 , for the purpose of bracing the arresting block 6 , a leaf spring 7 is provided in a corresponding recess 46 in the arresting block 6 . A restraining nose 11 is formed integrally on the arresting block 6 , this nose 11 having an undercut in the case of the exemplary embodiment according to FIG. 4 . Correspondingly, this exemplary embodiment does not have any safety-activation means; rather, when the loop is subjected to pronounced pulling in the upward direction out of the slot, the loop takes a firm hold in the device. [0062] It should be pointed out that it is also possible for the entire top region of the pole grip 1 to be of a rotatable or displaceable configuration, as long as the possibility of automatic latching-in is provided. There is therefore no need to provide a recess, as is the case in the exemplary embodiment according to FIG. 4 (but equally also in the exemplary embodiment according to FIG. 1 ); rather, it is also possible for the entire arresting block 6 to be designed as the uppermost region, or as the head, of the pole grip and for this to be mounted either in a displaceable or rotatable manner. [0063] FIG. 5 illustrates other exemplary embodiments based on the exemplary embodiment according to FIG. 4 . [0064] FIG. 5 a ) illustrates the option of providing the nose 11 with an upwardly directed flank. If, in the case of this exemplary embodiment, the loop is subjected to pronounced pulling in the upward direction out of the slot, then the arresting block 6 will rotate, and this ensures safety activation. [0065] A more specific safety-activation means is illustrated in FIG. 5 b ). In this case, the safety-activation element 12 is designed as a displaceable nose which is guided in a bore in the arresting block 6 and is braced against a helical spring 49 . Here, in the case of the loop being subjected to pronounced pulling out of the slot, the entire safety-activation element 12 , on which the nose 11 is integrally formed, is displaced into the arresting block 6 and thus releases the region 15 . [0066] An alternative safety-activation means is illustrated in FIG. 5 c ). In this case, the safety-activation element 12 is mounted such that it can be rotated about an axial element 13 and is braced against a spring 49 . Here, when a loop is subjected to pronounced pulling out of the slot, the entire safety-activation element 12 , on which the nose 11 is integrally formed, tilts into the arresting block 6 and releases the region 15 in the process. [0067] A further alternative is illustrated in FIG. 5 d ). In this case, the safety-activation element 12 is designed as a leaf-spring-like element, although it may also be an elastomeric element. This element can be moved as a whole, and the region 15 is released by the nose 11 , which is formed by this element, as a result of the entire element 12 being deformed when a loop is subjected to pronounced pulling out of the slot. [0068] Another approach is used in the exemplary embodiment according to FIG. 5 e ). In this case, the safety-activation means is provided on the hook-like device 14 . For this purpose, the hook-like device 14 has an internal clearance in which, once again, a leaf-spring-like element 12 is arranged. In the case of a pronounced force being exerted, this element yields in relation to the hook-like device 14 and thus likewise releases the region 15 in the manner of a safety-activation means. [0069] A further approach is illustrated in FIG. 5 f ). In this case, the entire hook-like device 14 is mounted such that it can be rotated about an axial element 50 . If a pronounced force emanates from the slot, then the entire hook-like device 14 rotates in the direction of the arrow illustrated and thus releases the region 15 . The rotatable mounting of the hook-like device 14 is likewise ensured, for example, via a helical spring, counter to an adjustable force. [0070] FIGS. 6 and 7 illustrate a further exemplary embodiment according to the invention. FIG. 6 illustrates the entire pole grip 1 , FIG. 6 a ) illustrating a view from the side, and FIG. 6 b ) illustrating a view from the rear, that is to say from the hand side (arrow 43 in FIG. 6 a )). FIG. 6 c ) illustrates an axial section along line B-B from FIG. 6 b ), and FIG. 6 d ) shows a view of the pole grip from above. [0071] The pole grip 1 for a downhill ski pole, in turn, has a grip body 3 and a cavity 5 , which serves for accommodating the pole shaft (not illustrated). [0072] In this case, the retaining peg 14 is formed integrally with the grip body 3 , as can be seen from FIG. 6 c ). It is also possible here, however, for the retaining peg 14 to be in the form of a separate element, in the manner of FIG. 1 f ) and of the elements 14 and 16 illustrated therein. [0073] The grip body 3 has a recess 4 which is open at the top and in which an arresting block 6 is arranged. The arresting block 6 is illustrated in detail in FIG. 7 . [0074] On the top side, the arresting block 6 has an activating button 61 , which will be described hereinbelow. The ergonomic shaping on the rear side of the top region of the pole grip 1 in this case is likewise formed by the arresting block 6 , since the latter has, to the sides of the hook 14 , two protrusions 59 which, as it were, surround the retaining peg 14 in the top region. [0075] The retaining peg 14 is thus optimally embedded in the outer contour of the pole grip 1 , as is not perceived as disturbing and it is possible for injuries to be avoided. Nevertheless, an ideal introduction opening remains from above for a cable loop 33 , as illustrated in FIG. 2 . [0076] The arresting block 6 contains a pin 57 which is used for the automatic latching in, for example, of a cable loop 33 . The pin 57 is arranged essentially horizontally and parallel to the direction of the arrow 43 . It is mounted in a displaceable manner in the arresting block 6 , in a recess 60 provided specifically for this purpose, the pin 57 being braced against the retaining peg 14 via a helical spring 58 . The pin 57 has a restraining nose 11 , which is preferably beveled from above and is of essentially horizontal design in the downward direction, in which case for example an eyelet or cable loop 33 which is introduced from above displaces the pin 57 in the rearward direction, counter to the stressing of the helical spring 58 , and the cable loop is arrested beneath the pin 57 in the region 15 . [0077] FIG. 7 a ) shows an overall view from the side of the arresting block 6 together with the elements fastening this arresting block 6 in the pole grip 1 . FIG. 7 b ) shows a view from the rear, that is to say from the direction of the arrow 43 in FIG. 6 a ), and FIG. 7 c ) shows a section along line A-A in FIG. 7 b ). FIG. 7 d ), finally, shows a view from above. [0078] The entire arresting block 6 is retained in the recess 4 , which is open at the top, in the pole grip 1 . For this purpose, the recess 4 has a through-bore to the cavity 5 . A securing pin 54 is attached to the arresting block 6 via an axial element 56 , which projects through this through-bore into the cavity 5 . On the top side, the securing pin 54 has an eye 55 , for fastening the securing pin on the arresting block 6 in a rotatable manner by way of the axial element 56 . At its bottom end, the securing pin 54 is provided with a thread. [0079] The securing pin 54 or the arresting block 6 fastened thereon is braced in the downward direction, with the aid of a stop element 52 butting against the top of the cavity 5 , by way of a helical spring 51 which, at one end, rests from beneath on a correspondingly provided shoulder on the stop element 52 and, at the other end, rests from above on a washer 64 , which via an adjusting nut 53 which is screwed onto the thread of the securing pin 54 from beneath. [0080] This design has, inter alia, the following advantages: First of all, the arresting block 6 , which is produced as an entire unit, is very straight-forward to assemble or install. It can be pushed into the recess 4 in the pole grip 1 from above, in which case the securing pin 54 , which is provided on the arresting block 6 , is pushed through the through-bore between the recess 4 and the cavity 5 . It is subsequently possible for, in the first instance, the stop element 52 , and then the helical spring 51 , to be pushed over the securing pin 54 in the cavity 5 , from beneath, and, finally, the washer and the adjusting nut 53 can be screwed onto the thread of the securing pin 54 . The resiliently elastic securing force in the downward direction to which the arresting block 6 is subjected via the helical spring 51 can be adjusted by the adjusting nut 53 being screwed upward to a greater or lesser extent or by the installation of different springs with a different spring constant or by virtue of the prestressing being changed by spacers. Finally, a rotary axial element 44 can be pushed in laterally through the bore 45 of the grip body, or through the bore 48 of the arresting block 6 , as a result of which the arresting block 6 is then mounted in the recess 4 such that it can be rotated about the rotary axial element 44 . Secondly, this design provides for adjustable emergency activation of the entire arresting block 6 . This is because, if the restraining nose 11 is subjected to excessive force from beneath by a cable loop 33 or an eyelet (for example in the event of a fall), then the entire arresting block 6 rotates about the rotary axial element 44 , for example in the counterclockwise direction in FIG. 6 c ) and in FIG. 7 c ). This takes place until the region 15 is released and the cable loop 33 or the eyelet is released from the hook. This design then has the advantage, inter alia, that the activating force can be adjusted very straightforwardly by, for example, the pole shaft being removed from the cavity 5 and the adjusting nut 53 being adjusted from beneath, in accordance with requirements, by a corresponding tool. It is also conceivable for the spring to be adjusted via an adjusting device which is incorporated in, or beneath, the grip region and is, for example, in the form of a partially exposed knurled nut, in which case there is no need for the grip to be dismantled in order for the activating force to be changed. The use of a helical spring 51 also ensures this safety activation under a wide range of different temperature conditions and, moreover, the helical spring 51 is concealed to such good effect in the interior of the pole grip 1 that it is possible to avoid soiling, icing-up or the like. [0083] If the eyelet or cable loop pushed over the retaining peg 14 is to be released from the region 15 under normal conditions, then an activating button 61 is provided, for this purpose, on the top side of the arresting block 6 . A rotary axial element 62 is arranged horizontally, and transversely to the direction of the pin 57 , in the arresting block 6 . The element which forms the activating button 61 is mounted within the arresting block 6 such that it can be tilted about this axial element (in the clockwise direction in FIG. 6 c )). Furthermore, a guide pin 63 is arranged in the pin 57 , likewise horizontally and transversely to the pin 57 . This guide pin 63 is likewise mounted in the element which forms the activating button 61 . [0084] If the activating button 61 , which is formed integrally with the lateral protrusions 59 , is pushed downward either in the region 61 or at the protrusions 59 , for example by the thumb of the hand which is gripping the pole, then the element which forms the activating button tilts slightly downward as a whole and thus, upon rotation about the rotary axial element 62 , pushes the pin 57 inward via the guide pin 63 , counter to the force of the helical spring 58 , consequently releases the region 15 in the upward direction and thus also releases a loop which has been arrested in this region. [0085] This design is highly advantageous insofar as the protrusions 59 are ideally positioned for the desired activation, but undesired activation can nevertheless be fully avoided. LIST OF DESIGNATIONS [0000] 1 Pole grip 3 Grip body 4 Recess in 3 5 Cavity in 3 for pole shaft 6 Arresting block 7 Spring 8 Stop bore for 7 9 Actuating button 10 Leg spring 11 Restraining nose 12 Safety-activation element 13 Axial element of 12 14 Retaining peg 15 Region for fastened loop/eyelet 16 Fastening plate 17 Slot for guide of 9 19 Guide peg for 7 20 Crosspiece 21 Fastening pin/screw 22 Axial pin 23 Bore in 6 for 22 24 Recess in 6 25 Glove 26 Thumb 27 Forefinger 28 Middle finger 29 Ring finger 30 Little finger 31 Encircling fastening device 32 Adjusting means for 31 33 Cable loop 34 Guide sleeve 35 Cable 36 Fastening for 35 37 Deflecting means for 35 38 Variable-length fastening for 35 39 Button for extended position 40 Button for retracted position 41 Pocket for 33 42 Recess in 14 43 Hand side 44 Rotary axial element of 6 45 Bore in 3 for 44 46 Recess for spring 47 Guide slot for spring 48 Bore in 6 for 44 49 Helical spring 50 Rotary axial element of 14 51 Helical spring 52 Stop element 53 Adjusting nut 54 Securing pin 55 Eye of 54 56 Axial element 57 Pin 58 Helical spring 59 Lateral protrusions of 6 60 Recess in 6 for 57 61 Activating button 62 Rotary axial element for 61 63 Guide pin for 57 64 Washer
Disclosed is a hand-retaining device ( 25 ), such as a hand strap that can be fastened to the hand or a glove, comprising a movable loop ( 33 ) between the thumb and the index which is used for fixing the hand-retaining device to a hook-type mechanism ( 14 ) of a pole grip. Such a hand-retaining device ( 25 ) is most preferably suitable for use with a pole grip ( 1 ), particularly for walking canes, trekking poles, downhill ski poles, cross-country ski poles, Nordic walking poles, which is equipped with a grip member ( 3 ) and a hook-type mechanism ( 14 ) for attaching a hand-retaining device especially in the form of a hand strap or a glove. Locking means ( 6, 11 ) are disposed in the area of the hook-type mechanism ( 14 ) such that a loop-shaped, annular, or eye-shaped device ( 33 ) that is provided on the hand-retaining device and is inserted into the hook-type mechanism ( 14 ) from above is fixed in a self-locking manner in the hook-type mechanism ( 14 ).
0
BACKGROUND OF THE INVENTION The invention relates to an implantation system for locking nails used in fracture fixation. Locking nails for the operative repairs of fractures of tubular bones are widely used. For example, application is described in “The Journal of Trauma” of 1993, Vol. 35 No. 5, p. 772 to 775. Typical for such locking nails is the arrangement of two transverse bores, i.e. cross-bores at one end (the distal end, for instance) and at least one transversal bore on the other end (the proximal end, for instance). Bone screws are guided through the transverse bores, which are screwed in at opposing sides into the cortical substance of the bone. Through this, the locking nail is secured axially and against rotation. When using such locking nails, the position of the transverse bores or locking holes in the locking nail has to be identified, so that the cortical substance of the bone is drilled from the right place from the outside. To do this, a series of aiming or targeting devices has become known, which conveniently operate with X-rays in order to determine the position of the transverse bores with respect to the aiming device. In this case, the bone is drilled in the proper place with the aid of the aiming device and a so-called drilling or aiming sleeve, so that the bone screws can be screwed in. Known aiming devices are conveniently connected to one end (for example, the proximal end) of the nail. In this way, the correspondence of the locking holes to aiming bores in the aiming device is approximately determined. However, it has to be taken into account that by reason of the bone's curvature and possible rotation of the nail upon it being driven into the bone, the expected position of the locking holes does not coincide with the actual one. For this reason, it has been difficult to perform an accurate identification of the position of the locking holes only by mechanical procedures. From WO 01/60272 A1, published Aug. 23, 2001 (U.S. Ser. No. 10/203,492 filed Nov. 15, 2002, which is assigned to the Assignee of the present invention, the teachings of which are incorporated herein by reference), a locking nail is disclosed in which a groove parallel to the nail axis is formed in the nail shaft only in the distal portion in the region of the locking holes. The leading axis of the groove cuts the axis of the bore approximately perpendicularly. In the mentioned document, an aiming device is also described, the aiming arm of which is provided with two aiming bores. The aiming bores are formed in a portion of the aiming arm of the aiming device which is elastically yielding. With the aid of a thin rod-like feeler, the actual position of the nail in the bone is determined with the aid of the locking holes and the groove between them. By turning the nail and by axial displacement it can be detected when the feeler is in the region of a locking hole. It has been found that this purely mechanical method still poses problems for the surgeon, because he cannot always determine in a sufficiently accurate manner the actual position of the nail by actuating the feeler. SUMMARY OF THE INVENTION The invention therefore has as one objective to provide an implantation system and an aiming device, respectively, by which the position of the locking holes can be determined in a simple manner and the bores in the bone can be seated at the proper place. This and other objects are provided by an implantation system which has at least one locking nail and an aiming or targeting device wherein the locking nail is attached to the aiming device at one end thereof. The nail has at least two locking holes on an opposite second end and has an exterior surface element, such as a groove, adjacent the locking holes. The aiming device has a rigid aiming arm with a free end aiming or guide portion having at least two and preferably at least three aiming bores arranged in a plane parallel to or in a plane including the longitudinal axis of the nail. In any case, the axes of the aiming bores can be aligned with the corresponding axes of the locking nail bores. The outer two aiming bores are spaced at a distance from each other which corresponds to the distance between the two locking holes of the locking nail. The aiming arm has a connecting piece movable on the aiming arm and being attachable thereto, wherein the connecting piece has an aperture for accommodating a detachable nail adapter which can be attached to one end, usually the exposed end, of the locking nail. The free end aiming portion of the mounting arm is rotatably mounted around an axis perpendicular to the longitudinal axis of the aiming arm and includes a first locking element for locking the free end portion in a predetermined rotational position. The rotational axis may coincide with the axis of the interior aiming bore of the at least three bores. The aiming portion is divided in the region of the aiming bores into a narrower portion and a broader portion by a recess parallel to an axis perpendicular to the axis of the aiming bores. The nail adapter may be rotatably mounted in the connecting piece and include a locking element to set the rotational position of the nail adapter and the connecting piece in relation to each other. An adjustor may be provided between the connecting piece and the nail adapter to adjust the relative rotational position therebetween. The aiming arm may be formed as a bar with a noncircular cross-section, which bars extends through a complimentary aperture in the connecting piece and wherein one wall of the aperture is formed by a clamping element which can be actuated by a clamping screw. The invention also relates to a method for locating a pair of axially spaced cross-bores in the first end of a locking nail implanted in a bone canal using the apparatus of the present invention. The method includes mounting the aiming device on a second end of the nail, the aiming device having an arm portion extending generally parallel to the longitudinal axially extent of the nail and having a guide bore portion swivel mounted on a free end of the aiming arm for movement at least in a direction perpendicular to the axially extent of the arm. The guide bore portion has at least two axially spaced bores therein and preferably three axially spaced bores. The outer bores of said at least two bores and preferably three bores are spaced at a distance equal to the axial distance between the cross-bores and the first end of the locking nail. A bore in the bone adjacent one of the cross-bores is drilled by using one of the axially spaced bores on the aiming arm preferably the middle hole. After the bore is drilled, the guide bore portion is removed to allow access to the drilled hole. Alternatively, if the guide bore portion is coupled to the aiming arm, the entire aiming arm/guide bore portion can be removed. If the guide portion is modular, it, alone, may be removed. Using the hole drilled in the bone as an access port, one of the nail cross-bores is located by feel, if necessary, by manipulating the axial and rotational position of the nail. To facilitate this, the nail is either initially inserted a distance greater than its required distance or a distance less than its required distance to enable the surgeon to determine whether the cross-bore found is closer to the first or second ends of the nail. A location pin is then placed in the located nail cross-bore and the guide bore portion is remounted by aligning the corresponding bore and the guide bore portion with the location pin mounted in the cross-bore. The other nail cross-bore can then be drilled. A connecting element may be placed between the second end of the nail and the aiming arm, which connecting element allows for universal movement of the aiming arm and, therefore, the guide bore portion at its free end, with respect to the nail so that the bores in the guide bore portion may be accurately aligned in any desired position. The locking nail in the inventive implantation system is provided with an apparatus with the aid of which the position of the locking holes can be detected. For instance, one means consists in disposing a groove parallel to the axis between the locking holes. Another means consists in providing perimeter grooves in the region of the locking holes or alternatively suitable stops, which can be detected with the aid of a feeler. However, one feature of the present aiming system is that the aiming arm is rigid and has an aiming or guide bore portion, in which three aiming bores are preferably provided. The axes of the aiming bores are situated in a plane which runs in the longitudinal axis of the aiming arm or parallel to it. The distance of the outer aiming bores corresponds to the distance of the locking holes. The middle aiming bore may be placed anywhere between the outer aiming bores, for example, at half the distance of their separation. The locking nail is detachably connectable to a nail adapter, for example, by a suitable threaded joint. The nail adapter is detachably connectable with a connecting piece, which on its part is detachably connectable with the rigid aiming arm. The detachable connection of the nail adapter with the aiming arm makes the use of the inventive aiming device possible for a plurality of different locking nails, without requiring a separate aiming device for each type of locking nail. Through the adjustment between the adapter at the one side and aiming arm on the other side, the nail can be adjusted in relation to the aiming arm before implantation. This takes place in a simple manner by, for example, aligning the outer aiming bores of the aiming portion of the aiming arm with the locking holes of the nail with the aid of a calibrating pin. Consecutively, the nail can be implanted, the nail adapter being allowed to remain fixed on the nail. The locking nail is now either hammered in farther than its required end position or less far than the desired end position. Next, the aiming device is reassembled and the cortical substance of the bone on the near side is drilled via the middle of the three aiming bores. Thereafter, the aiming device is detached from the nail adapter again and a rod-like feeler is put through the bone bore. The feeler will impinge against the closed wall of the locking nail and in the most favorable case into the groove which connects the locking holes. By turning the nail the groove may be found, for example, and it can be confirmed that it is in fact engaged by the feeler. Then, the nail is drawn out or is driven in farther, until the feeler cooperates with the respective locking hole. Next, the aiming device is mounted again, and one of the outer aiming bores is aligned with the detected locking hole. To do this, several possibilities may be contemplated. Preferably, an attachment sleeve is used, which is provided with a nearer portion with a diameter which corresponds to the diameter of the of the locking hole, and another portion, with a diameter corresponding to that of the aiming bore. The interior diameter of the attachment sleeve is dimensioned such that it can be pushed on the rod-like feeler, which is still present in the locking hole and the bone bore. Thus, a rather accurate alignment of an aiming bore with a locking hole can be achieved, by mounting the aiming arm again and pushing the one of its aiming bores onto the fixing sleeve. When this has been done, the second aiming bore in the aiming arm is also aligned with the second locking hole, and the cortical substance of the bone can be drilled above the second locking hole in the known manner, so that consecutively the seating of the locking screw can occur. When the first locking has been performed, the second locking can take place also, by drilling the cortical substance of the bone via that aiming bore, by which alignment had previously occurred, in order to seat the second locking screw. As already mentioned, the locking nail is provided with means, such as a groove, in the region of the locking holes by which the feeling and the detection of a locking hole is facilitated. It is also theoretically conceivable, however, to get along without such means, assuming only the locking nail has not been rotated around the diameter of the locking hole upon driving in. If this is the case, the surgeon knows the rotational position of the holes best, the surgeon does not know how far the nail has to be pulled out or driven in, until the axial position of the locking hole is reached. For calibration, in the spirit of the invention, it is preferred that the aiming portion be rotatably mounted around an axis perpendicular to the longitudinal axis of the aiming arm and be provided with first attachment means for fixing the aiming portion in a predetermined swiveling position. Preferably, the swiveling axis is situated on the axis of that aiming bore, which is nearest to the other end of the nail. According to another embodiment of the invention, the aiming portion is provided with a slit parallel to the axis in the region of the aiming bores, which extends perpendicular to the axes of the aiming bores and subdivides the aiming portion into a narrower and a broader portion. In this way, a clamping effect is achieved upon seating in of the calibrating pin, drilling sleeve or the like, so that these parts do not unintentionally slip or fall out. According to another embodiment of the invention, the calibration is further facilitated if the nail adapter is mounted rotabably around it longitudinal axis in the connecting piece and second attachment means is provided to fix the relative swiveling position. According to another form of the invention, an adjustor is provided between the connecting piece and the nail adapter for the adjustment of the relative swiveling position. The adjustor may contain an adjustment screw or the like for example. The rigid aiming arm of the inventive aiming device is preferably formed as an oblong bar with noncircular cross-section, which is inserted into a complementary aperture of the connecting piece, one wall of the aperture being formed by a clamping element, which can be actuated by a clamping screw. Thus, the connecting piece can be axially adjusted continuously on the aiming arm, the angular position remaining unchanged. These and other objects and advantages of the present invention will become apparent from the following description of the accompanying drawings, which disclose several embodiments of the invention. It is to be understood that the drawings are to be used for the purposes of illustration only and not as a definition of the invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows an aiming device according to the invention in a lateral view; FIG. 2 shows a lateral view rotated at 90° from the aiming device shown in FIG. 1 ; FIG. 3 shows the aiming device according to FIGS. 1 and 2 in a perspective representation; FIG. 4 shows the end of an aiming arm of the aiming device according to FIGS. 1 to 3 ; FIG. 5 shows an end view of an aiming portion of the aiming device according to FIGS. 1 to 3 ; FIG. 6 shows a section through the end view of FIG. 5 , along the line 6 — 6 ; FIG. 7 shows the end view of the aiming portion according to FIG. 5 rotated at 90°; FIG. 8 shows in perspective the connecting and the calibrating piece of the aiming device according to FIGS. 1 to 3 ; FIG. 9 shows the connecting piece of the structure according to FIG. 8 ; FIG. 10 shows a section through the connecting piece according to FIG. 9 ; FIG. 11 shows a side view of the connecting and calibrating piece according to FIG. 8 ; FIG. 12 shows a detail of the arrangement according to FIG. 11 ; FIG. 13 shows the side view of a calibrating pin; FIG. 14 shows the side view of a feeler; FIG. 15 shows a side view, of the feeler according to FIG. 14 rotated 90°; FIG. 16 shows the lateral view of a fixing sleeve; FIG. 17 shows the lateral view of a locking nail, as well as a nail adapter attached thereto; FIG. 18 shows a second embodiment for the end of a nail; FIG. 19 shows yet another embodiment for the end of the locking nail; and FIG. 20 shows the lateral view of a nail adapter for the system according to the preceding figures. DETAILED DESCRIPTION Referring to FIGS. 1 to 3 , there is shown an aiming arm 10 , which, in the preferred embodiment, has a square cross-section. On the left end of aiming arm 10 in FIG. 1 , a calibrating and connecting piece 12 is seated, and on the right end an aiming portion 14 is shown. Aiming portion 14 is rotatably mounted on a suitable bearing portion 16 on the right end of aiming arm 10 . Locking nails for which the aiming device according to FIGS. 1 to 3 is applicable are represented in FIGS. 17 to 19 . In FIG. 17 a locking nail 20 is shown, for instance a femoral nail. Nail 20 is provided with two axially spaced apart locking holes or cross-bores 22 , 24 on the distal end, and a locking hole or cross-bore 26 on the proximal end. A groove 28 extends parallel to the nail axis and in the preferred embodiment has a U- or V-shaped cross-section between the locking holes 22 , 24 . The outer diameter of locking nail 20 is connected to an oblong nail adapter 30 , preferably with the aid of a screw 32 , which is screwable into the proximal end of nail 20 . On the other end, nail adapter 30 is provided with flat portions 34 facing each other. In FIG. 18 , a second embodiment of the end of a locking nail 43 is shown, with locking holes 40 , 41 and diametric grooves 50 , 52 in the region of the locking holes 40 , 41 . In FIG. 19 locking holes 40 a , 41 a are shown, which are formed in a distal end portion reduced in diameter of the locking nail 43 a . On the left side of the locking holes 40 a , 41 a , respectively, radial collars 56 , 58 are formed, the collar 58 being chamfered towards the left end. The function of the nail forms shown can also be used in the process set forth below. Grooves 50 , 52 and flanges 56 , 58 can be used to detect the location of the cross-bores. As may especially be seen from the FIGS. 5 to 7 , the preferred aiming portion 14 is provided with at least two and preferably three aiming bores 60 , 62 , 64 , the axes of which are situated in a plane which goes through the longitudinal axis of aiming arm 10 or runs parallel to it. The axial separation of the outer aiming bores 60 , 64 corresponds to the distance of the locking holes 22 , 24 or 40 , 41 or 40 a , 41 a , respectively. As follows from FIGS. 6 and 7 , the aiming portion 14 is provided with a first relatively broad recess 66 , with a width marginally larger than the width of bearing portion 16 . As follows from FIG. 4 , bearing portion 16 is formed fork-like with arms 70 , 71 , which have an extension 72 adjacent and between the ends of the arms 70 , 71 , which have an extension 72 near to the ends of the arms 70 , 71 and an arcuate slit 74 running transversely on the end of the arms 70 , 71 . From FIGS. 6 and 7 , it follows that the recess 66 is traversed by the shank of a fixing screw 76 , the diameter of the shank being somewhat smaller than the width of arcuate slit 74 of bearing portion 16 . On the inner end, the recess 66 is traversed by a bearing sleeve 68 . It is possible that recess 66 could be made solid such as by using a pivot pin leaving only the two outer bores 60 , 64 . When bearing portion 16 is introduced into the slit, the shank of the fixing screw 76 is placed in the arcuate slit 74 and the sleeve 68 in the extension 72 . Thus, the aiming portion 14 is rotatably mounted around the axis of the sleeve 68 in the bearing portion 16 . The relative swiveling position is fixed by the fixing screw 76 . The aiming portion 14 is also subdivided by a relatively narrower slit 78 , which is introduced from the direction of the free end of the aiming portion 14 , into a relatively broad portion 80 which is provided with recess 66 , and a relatively narrower portion 82 . The latter is flexible in a limited degree in relation to the former and has bores, which are aligned with the aiming bores 60 , 62 and 64 . In FIGS. 8 to 10 , a preferred connecting piece 84 is represented, with the aid of which the nail adapter can be maintained movable and detachable on the aiming arm 10 , for instance, according to FIG. 17 . In the preferred embodiment, connecting piece 84 is provided with a square aperture 86 of a cross-section corresponding to the cross-section of the aiming arm 10 . A clamping portion 88 is movably mounted in the connecting piece 84 and forms a corner portion of the aperture 86 . The portion 88 is actuated by a clamping screw 90 , which acts upon a relatively thin portion 92 of the portion 88 , which is separated from the remaining portion 88 by a slit similar in form to portion 82 and slit 78 of portion 14 , in order to obtain a spring-like effect. A pin 94 , which seats in a groove of portion 88 , limits the adjustment of portion 88 . Connecting piece 84 additionally is provided with a bearing sleeve 96 , the axis of which runs perpendicular to the axis of the accommodation aperture 86 . A slot 98 is formed in the bearing sleeve 96 which slit has an extension in the diametral direction. Further, a pin 100 is press fit in bearing sleeve 96 , which pin protrudes somewhat from the interior of the bearing sleeve 96 . In FIG. 11 , the other side of the calibrating and connecting piece as shown in FIG. 8 is represented in a lateral view. In FIG. 12 , a preferred sleeve portion 102 is shown which is provided with a slot 104 partially extending into the diametral direction. The sleeve portion 102 is dimensioned such that it can be inserted into the bearing sleeve 96 , the slots 98 and 104 at least partially allowed to come into congruence. On one end of the sleeve portion is attached an arm 106 on which is pivotally mounted an adjustment screw 110 at point 108 . Screw 110 is provided with a cylindrical locking bolt 112 which is provided with an internal thread. The operation of the screw 110 takes place via a rotary knob 114 , which, upon rotation, acts to move bolt 112 . An arm 116 opposite the arm 106 is formed on the sleeve portion 102 at the same cylindrical end surface, which arm has a bent flange 118 open towards the one side. In the sleeve portion 102 there is situated an additional sleeve portion 120 , on which an arm 122 is formed. On the free end of the arm 122 a circular recess 124 is formed, which accommodates the cylindrical locking bolt 112 . Thus, upon a rotation of the knob 114 a relative swiveling between the arms 106 and 122 takes place. With a knob 126 a fixing screw 128 is actuated, which engages into a thread bore (not shown) of the sleeve portion 120 . The shank of the screw 128 extends through the slots 98 and 104 of bearing sleeve 96 and sleeve portion 102 . The sleeve portion 102 has a noncircular aperture 130 for the accommodation of the end portion of the nail adapter 30 . With the aid of fixing screw 128 the axial position of the nail adapter in the aperture 130 can be fixed. By swiveling the arm 122 in relation to the connecting piece 84 , the nail adapter can be turned around its axis and, by doing so, can perform a swiveling of the nail 20 . The relative swiveling position of the sleeve portion 102 and the arms 106 and 116 , respectively, with respect to the connecting piece 84 is effected by the fixing screw 90 , the shank of which extends through the bent flange 118 . In FIG. 13 , a calibrating pin 132 is shown, with a left portion 134 of smaller diameter and a relatively long portion 136 of larger diameter. The diameter of the portion 134 corresponds to the diameter of locking holes 26 , 24 and 40 , 41 and 40 a , 41 a , respectively. The diameter of portion 136 corresponds to the diameter of aiming bores 60 , 62 and 64 , respectively. In FIGS. 14 and 15 a feeler or location 138 is shown, which has a circular cross-section of a relatively small diameter over its length, which is significantly smaller than the diameter of the locking holes. On one end the feeler 138 is chamfered, as shown at 140 , for the formation of a kind of cutting edge. On the other end, the feeler pin or location pin 138 has opposing flats 142 , for the purpose of clamping into a grip or handle portion (not shown). In FIG. 16 a fixing sleeve 144 is represented with a portion 146 , the exterior diameter of which corresponds to the diameter of the locking holes 22 , 24 and 41 , 40 , 41 a , 40 a , respectively. A portion 148 has a larger diameter, which corresponds to the diameter of the aiming bores 60 to 64 . On the right end, the aiming sleeve 144 is provided with a clamping portion 150 for the purposes of a detachable connection with a handle. The aiming sleeve 144 has a continuous axial bore with a diameter roughly matching that of pin 138 such that the feeler pin 138 can be pushed through it. The nail adapter 160 shown in FIG. 20 has a shaft 162 , the cross-section of which is complementary to the cross-section of the aperture 130 in the connecting piece 84 (see for example FIG. 8 ). On the left end of the shaft 162 , an adapter portion 164 is attached to shaft 162 with the aid of a screw connection (not shown). Adapter portion 164 has two protrusions 166 on the free end, which engage in corresponding recesses of the nail (not shown), in order to predetermine its angular position. The nail is then fixed on the adapter 160 with the aid of a screw connection which extends through the hollow portion 164 in a known manner. At 168 and 170 , respectively, bores through the shaft 162 are indicated, which can also be used as aiming or alignment bores. The described implantation system is employed as follows. Firstly, a calibration is performed. The nail to be implanted, for example, nail 20 in FIG. 17 , is connected with the nail adapter 30 . Nail adapter 30 is inserted into aperture 130 of the connecting piece and is fixed with the aid of clamping screw 126 . By axially adjusting connecting piece 84 on aiming arm 10 and, as the case may be, by swiveling the nail by actuating the adjustment screw 114 , locking holes 22 , 24 are aligned with aiming bores 60 , 64 . At first, an alignment with respect to the aiming bore 60 takes place by inserting a calibrating pin according to FIG. 13 . Optionally, a drill bit guiding sleeve and a drill may be used for this purpose. In that, the portion 134 of calibrating pin 132 arrives in the locking hole 22 . Subsequently, aiming portion 14 is swiveled so far until the aiming bore 64 is also aligned with the locking hole 24 , which can be detected with the aid of the calibration pin. Thereafter, a fixing of the aiming portion 14 in the actual swiveling position with the aid of the fixing screw 76 takes place. The position of the nail had been previously adjusted by the clamping screw 126 , fixing screw 90 and adjustment screw 114 . Subsequently, the nail adapter 30 is removed by disengaging clamping screw 126 , and locking nail 20 is driven into the bone in the conventional manner, for example, from the proximal position into the femur channel. The nail adapter 30 remains attached on locking nail 20 . Locking nail 20 is driven in for a certain distance somewhat farther than the desired end position. This oversize corresponds to a distance which is smaller than the separation of locking holes 22 , 24 . After the nail has been driven in, a fixing of aiming arm 10 on nail adapter 30 takes place in the already described way. Now, a hole is drilled into the cortical substance on the near side of the bone through middle aiming bore 72 with the aid of a suitable drilling sleeve and, as the case may be, a tissue protection sleeve. In doing this, care must be taken to avoid the drill coming into contact with the nail 20 . After this hole is drilled, the aiming device is subsequently removed from the nail adapter, and an attempt is made to feel the groove 28 with the aid of the feeler 138 , which is pushed through the bone bore. If this fails, the groove 28 can be detected by feel by slightly turning the nail 20 in the bone channel. As soon as this occurs, the nail 20 is somewhat pulled out, until the feeler 22 detects the locking hole 24 by feel. When this is done, the fixing sleeve 144 is placed over the feeler 138 . In this, the portion 146 arrives in the locking hole 24 through the bone bore. The aiming device is subsequently mounted anew with the fixing sleeve 144 seated in this way, the aiming bore 64 being aligned to the fixing sleeve 144 . When the fixing of the aiming device has taken place, the inner aiming bore 60 is automatically aligned to the inner locking hole 22 . Now the bone can be drilled on opposing sides of the locking hole 22 with the aid of the conventional methods and a locking screw can be inserted, in order to fix the nail in the bone. When this has taken place, the cortical substance of the bone can be drilled also on the other side by also removing the fixing sleeve 144 and with the aid of the conventional methods, in order to incorporate a locking screw also into this region. As soon as the distal locking is ended, a locking in the region of the proximal locking hole 26 can also take place in known manner. Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims.
An implantation system for a locking nail has an aiming device, wherein the locking nail is formed for detachable attachment to the aiming device at the one end thereof. The nail has two locking holes on the other end and has an exterior feature such as a groove connecting the locking holes which groove is parallel to the axis, or indentations or elevations running in the perimeter direction in the region of the locking holes. The aiming device has a rigid aiming arm with a free end portion having three aiming bores arranged in a plane generally parallel to the axis. The outer two of the aiming bores are located at a distance from each other which corresponds to the distance of the distal locking holes of the locking nail. The system further has a connecting piece universally movable on the aiming arm. The connecting piece has an accommodation aperture for selective detachable attachment to a rod-like nail adapter which, on its part, has a coupling for detachable attachment of the locking nail.
0
CROSS-REFERENCE TO A RELATED APPLICATION [0001] The subject application claims priority to U.S. provisional application Ser. No. 61/502,065, filed on Jun. 28, 2011, the entire contents of which are hereby incorporated by reference. FIELD OF THE INVENTION [0002] This invention relates to methods and compositions for improving solubility and the safety profile of pharmaceutical compounds. More particularly, the present invention relates to employing Polymer-carbohydrate-lipid conjugates, such as PEG-carbohydrate-lipid conjugates, for formulating drug compositions having increased solubility or dispersivity and enhanced stability. BACKGROUND OF THE INVENTION [0003] Delivery of hydrophobic drug compounds to the site of action is an ongoing challenge in clinical research. It has been reported that 60-90% of new chemical entities in clinical and development are water insoluble or poorly soluble [A. M. Thayer (2010), Chemical & Engineering News, 88(22): 13-18; C. A. Lipinski, J Pharmacol Toxicol Method 44 (2000) 235-2490 and N. Gursoy and S. Benita, Biomed. Pharmacother. 58 (2004) 173-182]. For example, Propofol is insoluble in water and is only slightly soluble in solutions having solubilizers commonly used in preparing parenteral formulations such as propylene glycol, glycerin and PEG 400. Cyclodextrins, drug-lipid complexes, liposomes, and other solubilizing agents such as Cremophor® and various PEG-lipid conjugates have been tested as the delivery vehicles for Propofol. However, little or substantially no significantly improvement in solubility and stability profiles may be achieved in these vehicles. What is needed are new compositions and methods for formulating poor water soluble drugs in various parenteral dosage forms. SUMMARY OF THE INVENTION [0004] In at least one aspect of the present disclosure, a pharmaceutical composition for parenteral administration of a pharmaceutical active ingredient is provided. The composition comprises: a) an aqueous solution or mixture; b) a pharmaceutical active ingredient; and c) a solubility enhancer comprising a Polymer-carbohydrate-lipid represented by at least one of chemical structures a) and b), wherein a) and b) are: [0000] [0000] wherein: X 1 , X 2 , X 3 and X, are the same or different linking groups; B is a central backbone; L is a lipid; S is carbohydrate; P is PEG; and D is lipid, carbohydrate or polymer. [0005] In at least one other aspect of the present disclosure, a pharmaceutical composition for parenteral administration of a pharmaceutical active ingredient is provided. The composition comprises: i) an aqueous solution or mixture; ii) a solubility enhancer comprising at least one Polymer-carbohydrate-lipid; and iii) a pharmaceutical active ingredient. [0006] In at least one aspect of the present disclosure, a process for making a pharmaceutical composition for parenteral administration of a pharmaceutical active ingredient is provided. The process comprises the steps of: adding an aqueous solution of PEG-carbohydrate-lipids to a vessel; adding a pharmaceutical active ingredient in liquid or Slurry form to the vessel; mixing until the pharmaceutical active ingredient is visually dispersed in the aqueous solution of PEG-carbohydrate-lipids; adding pre-dissolved excipients to the vessel; and mixing until a homogenous solution is achieved. BRIEF DESCRIPTION OF THE INVENTION [0007] The invention comprises various aqueous and PEG-carbohydrate-lipid based formulations of poorly water soluble drugs including compositions for parenteral preparations such as intravenous injection. In one aspect the invention comprises a solution of lipophilic compound and PEG-carbohydrate-lipid (s) to enhance the solubility or dispersivity of lipophilic compounds in aqueous solutions. [0008] In at least one aspect of the present disclosure, a pharmaceutical composition for parenteral administration of a pharmaceutical active ingredient is provided. The composition comprises: an aqueous solution or mixture; a solubility enhancer comprising at least one polymer-carbohydrate-lipid; and a pharmaceutical active ingredient. BRIEF DESCRIPTION OF THE DRAWINGS [0009] The accompanying drawings, which are incorporated into and constitute a part of this specification, illustrate one or more embodiments of the present invention and, together with the detailed description, serve to explain the principles and implementations of the invention. [0010] In the drawings: [0011] FIG. 1 shows a representation of the chemical structures of Lipid-carbohydrate-PEG conjugates; and [0012] FIG. 2 shows mouse pharmacokinetic profiles of propofol formulations after IV dosing. DETAILED DESCRIPTION [0013] Embodiments of the present invention are described herein in the context of lipid-carbohydrate-polymer conjugates for increasing the solubility and enhancing the delivery of lipophilic drug molecules. Those of ordinary skill in the art will realize that the following detailed description of the present invention is illustrative only and is not intended to be in any way limiting. Other embodiments of the present invention will readily suggest themselves to such skilled persons having the benefit of this disclosure. Reference will now be made in detail to implementations of the present invention as illustrated in the accompanying drawings. [0014] In the interest of clarity, not all of the routine features of the implementations described herein are shown and described. It will, of course, be appreciated that in the development of any such actual implementation, numerous implementation-specific decisions may need be made in order to achieve specific goals, such as compliance with application and business related constraints, and that these specific goals may vary from one implementation to another and from one developer to another. However, development and implementation of the disclosed may be a routine undertaking of engineering for those of ordinary skill in the art having the benefit of this disclosure. [0015] U.S. patent application Ser. No. 13/364,967 and 13/354,726, which are hereby incorporated by reference, may teach the formation of spontaneous liposomes by employing certain lipid-carbohydrate-polyethleneglycol (LCP) conjugates. They may describe how to prepare the PEG-carbohydrate-lipid conjugates and its applications by simply adding the conjugate to an aqueous solution. It has been demonstrated that LCPs may be useful for solubilizing hydrophobic drugs without the formation of liposomes or microemulsions. [0016] Over last three decades, some of promising drug carriers that have been investigated in systemic delivery systems includes liposomes, polymeric nanoparticles, polymeric micelles, ceramic nanoparticles and dendrimers (Cheman et al. Drug. Dev. Ind. Pharm, 26: (2000) 459-463; Lian and Ho. J. Pharm. Sci, 90 (2001) 667-680; Adams et al. Pharm. Sci, 92 (2003) 1343-1355; Na et al. Eur. J. Med. Chem., 41 (2006) 670-674; Kaur et al. J. Control. Rel, 127 (2008) 97-109). Systemic drug delivery may be achieved by intravenous or intraperipheral injection and therefore is non-invasive. The drugs may be administered repeatedly as needed. However, in order to achieve therapeutic concentrations at the target site, systemic administration may require large dosages with relatively high vehicle contents which may cause side effects such as allergic reactions [“Cremophor-based paclitaxel ‘chemo’ drug triggers fatal allergic reactions,” The Medical News. 9 Jun. 2009]. [0017] Polyethylenglycol (PEG) is widely used as a water soluble carrier for polymer-drug conjugates. PEG may undoubtedly be the most studied and applied synthetic polymer in the biomedical field [Duncan, R. Nature Rev. Drug Discov. 2003, 2, 347-360]. As an uncharged, water-soluble, nontoxic, nonimmunogenic polymer, PEG may be an ideal material for biomedical applications. Covalent attachment of PEG to biologically active compounds is often useful as a technique for alteration and control of biodistribution and pharmacokinetics, minimizing toxicity of these compounds [Duncan, R. and Kopecek, J., Adv. Polym. Sci. 57 (1984), 53-101]. PEG possesses several beneficial properties: very low toxicity [Pang, S. N. J., J. Am. Coil. Toxicol, 12 (1993), 429-456], excellent solubility in aqueous solutions [Powell, G. M., Handbook of Water Soluble Gums and Resins, R. L. Davidson (Ed.), Ch. 18 (1980), MGraw-Hill, New York], and extremely low immunogenicity and antigenicity [Dreborg, S, Crit. Rev. Ther. Drug Carrier Syst., 6 (1990), 315-365]. The polymer is known to be non-biodegradable, yet it is readily excretable after administration into living organisms. In vitro study showed that its presence in aqueous solutions has shown no deleterious effect on protein conformation or activities of enzymes. PEG also exhibits excellent pharmacokinetic and biodistribution behavior. [Yamaoka, T., Tabata, Y. and Ikada, Y., J. Pharm. Sci. 83 (1994), 601-606]. [0018] When used as a delivery vehicle, polymer-lipid conjugates may have the capacity to improve the pharmacology profile and solubility of lipophilic drugs. The novel polymer-carbohydrate-lipid conjugates disclosed in the earlier inventions may also provide other potential advantages over conventional polymer-lipids, i.e., PEG-lipids, such as minimizing side effects and toxicities associated with therapeutic treatments. [0019] The important role of sugars in many specific interactions in living systems is well recognized. Large molecular weight carriers such as proteins or liposomes may be modified with sugars for specific drug delivery (Monsigny M, Roche A C, Midoux P and Mayer R., Adv Drug Delivery Rev., 14 (1994):1-24; Palomino E. Adv Drug Delivery Rev., 13 (1994)311-323]. Lipid—sugar particles have been used for drug delivery to the brain for providing prolonged duration local anesthesia when injected at the sciatic nerve in rats [Kohane D S, Lipp M, Kinney R., Lotan N, Langer R., Pharm. Res. 17 (2000) 1243-1249]. Since sugar-lipids are composed of materials that occur naturally in the human body suggests potential advantages over some other polymer-based controlled-release terms of biocompatibility [Kohane D S, Lipp M, Kinney R, Anthony D, Lotan N, Langer R., J. Biomed. Mat. Res. 59 (2002) 450-459; Menei P, Daniel V, Montero-Menei C, Brouillard M, Pouplard-Barthelaix A, Benoit J P., Biomaterials, 14 (1993) 470-478]. Lipid-sugars may have a good biocompatibility as shown by the results of the in vitro and in vivo studies [Kohane D S, Lipp M, Kinney R, Anthony D, Lotan N, Langer R., J. Biomed. Mat. Res. 59 (2002) 450-459]. [0020] A preferred embodiment of the present disclosure may comprise an aqueous-based, injectable drug solution including and not limited to olcoyltri-ethylenetetramine-polyethyleneglycol lactobionate (OTL-PEG) or oleoyldiethylenetetramine-dodecaethylene glycol lactobionate (ODL-PEG). In at least one aspect of the present disclosure, the solution includes a drug molecule in concentrations ranging from 0.05 mg/mL to 50 mg/mL and the ratio of PEG-lipid to the drug ranges from 0.2 to 25. In at least one other aspect of the present disclosure, the concentration of drug molecule ranges from 0.5 mg/mL to 50 mg/mL. In at least one additional aspect of the present disclosure, the concentration of drug molecule ranges from 0.5 mg/mL to 10 mg/mL and the percent of PEG-carbohydrate-lipid ranges from 0.5 to 10 (w/v) of the total solution. [0021] Further aspects of the present disclosure may provide aqueous, injectable drug solutions in which the diluent consists of 0.5 to 25 percent (w/v) of the PEG-carbohydrate-lipid and 75 to 99.5 percent (v/v) of water or a buffer or saline or dextrose solution. Also preferable are aqueous, injectable drug solutions of this invention in which 85 to 99 percent (v/v) of the total solution is water or a buffer or saline or dextrose solution. [0022] In at least one aspect of the present disclosure, aqueous injectable drug solutions according to the present invention comprise lipophilic drug compound in LCP lipids including and not limited to OTL-PEG or ODL-PEG plus aqueous media at concentrations of a drug ranging from 0.5 mg/mL to 50 mg/mL, 0.5 to 25 percent (w/v) of PEG-carbohydrate lipid, and 75 to 99.5 percent (v/v) water, wherein the concentration of drug in the combined solution ranges from 0.5% to 5%. [0023] The aqueous injectable drug solutions of the present disclosure may be administrated by bolus injection or by infusion. Infusion may be preferable for such solutions where the concentration of drug in is greater than 0.01 mg/mL. In case of an infusion, the length of an infusion may be preferable 30 minutes to 6 hours and may not be more than 24 hours. [0024] Aspects of the present disclosure involve solubilizing a drug or drugs, by using one or more amphipathic PEG conjugates. A combination of LCPs and polysorbates may be preferred solubilizing agents, in which acyl chains comprise the lipophilic portion of the conjugate. Examples of LCPs are shown in FIG. 1 . [0025] A branched PEG-carbohydrate-lipid may also be an excellent solubilizing agent, in which the polymer comprises the more than single PEG chains of the conjugate. Similarly, branched-PEG-carbohydrate-lipids may also be used as solubilizing agents. As with LCP solubilizing agents, these compounds typically are waxy solid or semisolids at the temperature of solubilization, these PEG-carbohydrate-lipids typically have melting points above about 25 degrees Centigrade. Such solubilizing agents may also be used to prepare IV formulations and oral or topical liquids. [0026] A first step for solubilization may comprise combining the drug compound(s), with an amphipathic PEG conjugate(s) which may be semisolid or solid at the temperature of solubilization. For formulating a drug solution at room temperature (which may be preferred), a concentrated solution of a conjugate may be desired. Such solubilization may be done by first adding the liquid form of a drug to the concentrated solution of the conjugates. The aqueous solution may be further diluted with water or a buffer. Alternatively, the drug compound(s) may be pre-dissolved in a small amount of acid, base or alcohol, then mix with the PEG-carbohydrate-lipids in aqueous solution. [0027] By performing solubilization at elevated temperatures, conjugates with higher melting temperatures may be used as solubilizing agents. When forming aqueous solutions, the aqueous solution may also be preferably added at an elevated temperature. [0028] The LCP lipids shown in Table 1 may be suitable for use in various aspects of the present disclosure. LCPs with oxy or amide or succinyl linkers (X=oxygen or carbonyl or succinyl) may be preferred, though LCPs with other linkers may be used. [0029] The lipid-carbohydrate polymer conjugates shown in FIG. 1 may be suitable for use in various aspects of the present disclosure. Where X 1 , X 2 , X 3 and X, are the same or different linking groups; “B” is a central backbone; “L” is a lipid; “S” is carbohydrate; “P” is a polymer; and “D” is lipid (the same or different than “L”) or carbohydrate (the same or different than “S”) or polymer (the same or different than “P”). [0030] Backbone (B) may comprise glycerol or glycerol-like analogues or linear amines (tri- or tetra-amines) or amino acids having three available binding sites; where the lipid (L) may comprise carboxylic acids including and not limited to diacylglycerol or fatty acids or bile acids; sugar (C) may comprise a carbohydrate including monosaccharides or disaccharides or oligosaccharides; X 1 , X 2 and X 3 and X, are the same or different linkers and X represents an oxy or single or replicate linkers or combination of two or more molecules in between the backbone and one of functional groups. The General Structure is meant to include all racemers or structural isomers of the structure, as they may be functionally equivalent. The PEG chain (P) may be a single PEG or a branched PEG chains consisting of 5 to 45 subunits. There may be a terminal group (R) on the PEG chain which may comprise a wide variety of chemical moieties. In at least one aspect of the present disclosure, R has a molecular weight of less than about 650. D may comprise a secondary sugar or lipid or PEG. The Lipid-carbohydrate-PEG conjugates may be useful for applications other than liposomes, e.g., as a solvent. [0031] If a terminal group is attached to the PEG chain in FIG. 1 , it may comprise a wide variety of chemical moieties. Such moieties may have a molecular weight of less than 650. Such moieties include —NH 2 , —COOH, —OCH 2 CH 3 , —OCH 2 CH 2 OH, —COCH═CH 2 , —OCH 2 CH 2 NH 2 , —OSO 2 CH 3 , —OCH 2 C 6 H 6 , —OCH 2 COCH 2 CH 2 COONC 4 H 4 O 2 , —CH 2 CH 2 —CH 2 , C 10 H 16 N 2 O 3 S and —OC 6 H 6 . The terminal group may be a functional group that facilitates linking of therapeutic or targeting agents to the surface of lipid vesicle aggregates. Amino acids, amino alkyl esters, biotins, maleimide, diglycidyl ether, maleinimido propionate, methylcarbamate, tosylhydrazone salts, azide, propargyl-amine, propargyl alcohol, NHS esters (e.g., propargyl NHS ester, NHS-biotin, sulfo-NHS-LC-biotin, or NHS carbonate), hydrazide, succinimidyl ester, succinimidyl tartrate, succinimidyl succinate, and toluenesulfonate salt may be useful for such linking. Linked therapeutic and targeting agents may include Fab fragments (fragment antigen-binding), cell surface binding agents, and the like. Additionally, the terminal group may include functional cell-targeting ligands such as folate, transferrin and molecules such as monoclonal antibodies, ligands for cellular receptors or specific peptide sequences may be attached to the liposomal surface to provide specific binding sites. The terminal group may be neutral or include either negatively or positively charged head-groups such as decanolamine, octadecylolamine, octanolamine, butanolamine, dodecanolamine, hexanolamine, tetradecanolamine, hexadecanolamine, oleylamine, decanoltrimethylaminium, octadecyloltrimethylaminium, octanoltrimethyl-aminium, butanoltrimethylaminium, dodecanoltrimethylaminium, hexanoltrimethylaminium, tetradecanoltrimethylaminium, hexadecanoltrimethylaminium, oleyltrimethylaminium, for example. Other useful R groups include alkyl groups such as alkoxy moieties, amino acids, and sugars including monosaccharides, disaccharides, trisaccharides and the oligosaccharides—containing 1, 2, 3, and 4 or more monosaccharide units respectively. Additionally, targeting moieties such as antibody fragments and vitamins may also be used as R groups. Generally, the R group may be highly soluble in water. The molecular weight of the R group may be less than about 650, and for most applications the R group may be easily polarized, in order to increase the binding and interaction with proteins at the targeted sites. [0000] TABLE 1 PEG-lipid (Lipid-carbohydrate-polyethyleneglycols) and/or Shorthand name Name MAGC-PEGs monoacylglycerol-carbohydrate-polyethylene glycols MAPC-PEGs monoacylpolyamine-carbohydrate-polyethylene glycols MAAC-PEGs monoacylamino acid-carbohydrate-polyethylene glycol ODL-TrpPEGs oleoyldiethylenetriamine-tryptophanyl PEG LOS-PEGs N-lactobionyloleoyl-mPEG serinate LOS-bioPEGs N-lactobionyloleoyl-biotinylated PEG serinate OAPDL-11 oleoyl-N-(3-aminopropyl)propane-1,3-diamine- Undecaethylene glycol methyl ether Lactobionate GDODL-12: dioleoylglyceroldiethylenetriamine-monomethoxyl dodecaethylene glycol ether lactobionate GMODL-12 dimyristoylglycerol diethylenetriamine-monomethoxyl dodecaethylene glycol ether lactobionate GML-12 myristoylglycerol-dodecaethylene glycol lactobionate GOL-12 oleoylglycerol-dodecaethylene glycol lactobionate MDTL-12 myristoyldiethylenetetramine-dodecaethylene glycol lactobionate ODL-12 oleoyldiethylenetriamine-dodecaethylene glycol lactobionate ODL-15 oleoyldiethylenetriamine-pentadecaethylene glycol lactobionate ODTL-12 oleoyldiethylenetetramine-dodecaethylene glycol lactobionate ODTL-15 oleoyldiethylenetetramine-pentadecaethylene glycol lactobionate MTL-12 myristoyltriehylenetetramine-dodecaethylene glycol lactobionate OTL-12 oleoyltriethylenetetramine-dodecaethylene glycol lactobionate OTL-15 oleoyltriethylenetetramine-pentadecaethylene glycol lactobionate GDODL-12 dioleoylglycerol-diethylenetriamine-monomethoxyl polyethylene glycol ether lactobionate OAPEL-PEG oleoyl(aminopropylamino)ethanoyl-mPEG Lactobionate LOS-bioPEG N-lactobionyloleoyl-biotinylated PEG Serinate LOL-bioPEG N-lactobionyloleoyl-biotinylated PEG Lycinate DCAL-PEG N-desoxycholylaspartate-mPEG lactobionate OAL-mPEG oleoylaminopropanediol-mPEG lactobionate OAL-bioPEG oleoylaminopropanediol-biotinylated PEG lactobionate ODL-ThrPEG oleoyldiethylenetriamine-threoninyl PEG lactobionate ODL-bioPEG oleoyldiethylenetriamine-biotinylated PEG lactobionate ODL-PEG oleoyldiethylenetriamine-PEG lactobionate X 1 , X 2 and X 3 represent linkers which may be oxy or thiol or carbonyl, amino or succinyl or the like may not be distinguished in the following name and detailed in the preceding sections. X 1 , X 2 and X 3 may be the same or different. The number of subunits in the PEG polymer ranges from 6 to 16. [0032] Mixtures of PEG-carbohydrate-lipids may be used in the present disclosure in the place where combinations of PEG-carbohydrate-lipids are used, the properties of the lipid mixture (e.g., melting point or average size of the PEG chain) may be calculated by known methods or determined empirically. [0033] The manufacture of parenteral solution may comprise first adding a drug to a concentrated PEG-carbohydrate-lipid solution and mixing until homogenous, which may be accomplished at room temperatures. Next, premixed aqueous integrants may be added to the lipid-drug mixture and mixed until a homogenous solution is obtained. The solution may then be filtered for sterility while maintaining an overlay of sterile-filtered nitrogen during the process. Appropriate volumes of the solution may be filled into ampules and sealed using aseptic technique. Sterile conditions may be maintained throughout the filtering, filling, and sealing operations in accordance with standard manufacturing procedures for injectables. While the formulated product may be stable at room temperature, it may be preferably stored under refrigeration for extended shelf life. [0034] A preservative may be desired when the sterile-filtered process is prevented by high concentrations of PEG-carbohydrate-lipids, the possible preservatives may be selected from a group of antimicrobial agents consisting of benzyl alcohol, chlorobutanol, methylparaben, propylparaben, phenol, ethylenediaminetetraacetic acid, and m-cresol. [0035] In one aspect of the present disclosure, a pharmaceutical composition for administration by intravenous injection is provided. The composition comprises an aqueous solution; a PEG-carbohydrate-lipid or combination of PEG-carbohydrate-lipids; and a drug at a concentration between about 0.05 mg/mL and about 50 mg/mL. The weight ratio of the PEG-carbohydrate-lipids to the drug may be between about 0.2 and 25. The average MW of PEG chains in the PEG-carbohydrate-lipid or mixture of PEG-carbohydrate-lipids may be less than about 1500. The concentration of a drug may preferably be between about 0.2 mg/ml to 50 mg/ml. The concentration of PEG-carbohydrate-lipids (s) may preferably be between about 0.5 to 25 percent (w/v) of the total solution. [0036] In another aspect, the disclosure provides a method of making a pharmaceutical composition suitable for administration by intravenous injection. The method comprises mixing a PEG-carbohydrate-lipid or combination of PEG-carbohydrate-lipids with a drug and adding an aqueous solution while mixing to create a suspension. The final concentration of the drug may preferably be between about 0.05 mg/ml and about 50 mg/ml. The weight ratio of the total PEG-lipid to the drug compound may preferably be between about 0.2 and 25. The average MW of PEG chains in the PEG-carbohydrate-lipids or combination of PEG-carbohydrate-lipids may preferably be less than about 1500. The method may further comprise sealing the aqueous suspension in a sterile container or adding antimicrobial preservatives. [0037] In another aspect of the present disclosure, a method of treating a disease in a mammal is provided. The method comprises preparing a composition comprising an aqueous solution, a PEG-carbohydrate-lipid or combination of PEG-carbohydrate-lipids, and drug compound at a concentration between about 0.05 mg/mL and about 50 mg/mL. The weight ratio of the PEG-carbohydrate-lipids to the drug may be between about 0.2 and 25. The composition may be administered to the mammal intravenously. The average MW of single PEG chains in the PEG-carbohydrate-lipid or combination of PEG-carbohydrate-lipids is preferably less than about 1500. The concentration of drug may be between about 0.2 mg/mL to 25 mg/mL. The concentration of PEG-carbohydrate-lipids may be between about 0.5 to 25 percent (w/v) of the total solution. The composition may further comprise antimicrobial preservatives, where the concentration of antimicrobial preservatives may be between about 0.1 to 2%. The disease being treated may be a cancer or a fungal infection, for example. The method may also be used to provide for general anesthesia for surgical procedures or where hypnotic agents are desired. [0038] The following examples intend to further illustrate the practice of the present invention. Example 1 Preparation of Propofol Solution for Injection [0039] A propofol solution suitable for intravenous delivery was prepared as described in following Scheme 1. [0040] Scheme 1 shows a manufacturing flow chart for Propofol Solution for Injection. [0041] An aqueous solution of PEG-carbohydrate-lipids was added to a vessel equipped with a mixer propeller. The drug substance was added with constant mixing. Mixing was continued until the drug is visually dispersed. Pre-dissolved excipients in water were slowly added to the vessel with adequate mixing. Mixing continued until a homogenous solution was achieved. Sterile conditions should be maintained throughout the process for producing clinical supplies. A sample formulation is described in Table 2. [0000] TABLE 2 Ingredient mg/mL Propofol 10.0 PEG-carbohydrate-lipid 30   Glucose 1 50   Purified Water qs 1 mL 1 optional [0042] PEG-carbohydrate-lipid may be selected from Table 1, where n=8 or higher (i.e., the molecular weight of the PEG chain is greater than about 350) or lipid-carbohydrate-PEG, where PEG chain contains 8 to 16 subunits. The targeted pH is in a range of 4.0 to 7.5. Diluted NaOH (i.e., 10N) or HCl solution (i.e., 6N) may be used to adjust pH if necessary. Example 2 Preparation of Propofol Solution for Injection [0043] A propofol solution suitable for intravenous delivery of propofol was prepared the same as in Example 1. A concentrated PEG-carbohydrate-lipid was charged to a vessel equipped with a mixer propeller. The drug substance was added with constant mixing. Mixing continued until the drug was visually dispersed in the lipid solution. Pre-dissolved excipients in water were slowly added to the vessel with adequate mixing. Sterile conditions should be maintained throughout the process for producing clinical supplies. Mixing continued until fully a homogenous solution was achieved. A sample formulation is described in Table 3. [0000] TABLE 3 Ingredient mg/mL Propofol 10.0 PEG-carbohydrate-lipid 30.0 Sodium Chloride  9.0 Sodium Hydroxide See below Hydrochloric Acid See below Purified Water qs 1 mL [0044] The lipid-carbohydrate-PEG may be selected from Table 1, where PEG chain contains between 8 to 16 subunits. Sodium hydroxide was used to prepare a 10% w/w solution in purified water. The targeted pH was in a range of 4.0 to 7.5. The NaOH solution or HCl (6N) was used to adjust pH as necessary. Example 3 Preparation of Propofol Solution or Suspension for Injection [0045] A propofol solution suitable for intravenous delivery of propofol was prepared the same as in Example 1. A concentrated solution of PEG-carbohydrate-lipid was charged to a vessel equipped with a mixer propeller. The drug substance was added with constant mixing. Mixing continued until the drug was visually dispersed in the lipid. Pre-dissolved excipients in water were slowly added to the vessel with adequate mixing. Mixing continued until fully a homogenous solution was achieved. Sterile conditions should be maintained throughout the process for producing clinical supplies. A sample formulation is described in Table 4. [0000] TABLE 4 Ingredient mg/mL Propofol 10.0 PEG-carbohydrate-lipid 15.0 Sodium Chloride 9.0 Sodium Hydroxide See below Hydrochloric Acid See below Sodium Benzoate 20.0 1 Purified Water qs 1 mL 1 preservative is not needed if sterile-filtered is used. [0046] The PEG-carbohydrate-lipid may be selected from Table 1, where PEG chain contains 8 to 16 subunits. Sodium hydroxide was used to prepare a 10% w/w solution in purified water. The targeted pH was in a range of 4.0 to 7.5. The NaOH solution or HCl (6N) was used to adjust pH as necessary. Example 4 Cisplatin IV Injectable Solution [0047] The IV solution is prepared as in Example 1. A sample formulation is described in Table 5. [0000] TABLE 5 Ingredient mg/mL Cisplatin 20.0 PEG-carbohydrate-lipid 20.0 Sodium Chloride  9.0 Sodium Hydroxide See below Hydrochloric Acid See below Purified Water qs 1 mL [0048] The PEG-carbohydrate-lipid may be selected from Table 1, where PEG chain contains between 8 to 16 subunits. Sodium hydroxide was used to prepare a 10% w/w solution in purified water. The targeted pH was in a range of 4.0 to 7.5. The NaOH or HCl (6N) solution was used to adjust pH as necessary. Example 5 Docetaxel IV Injectable Solution [0049] The drug substance was charged into a vessel equipped with a mixer propeller. Dehydrated alcohol was added with constant mixing. Mixing continued until the drug was visually disappeared in the Alcohol. Pre-dissolved lipid and excipients in water were slowly added to the vessel with adequate mixing. Mixing continued until fully a homogenous solution was achieved. Sterile conditions should be maintained throughout the process for producing clinical supplies. A sample formulation is described in Table 6. [0000] TABLE 6 Ingredient mg/mL Docetaxel 10.0 PEG-carbohydrate-lipid 25   Dehydrated Alcohol 10.0 Sodium Chloride  9.0 Sodium Hydroxide See below Hydrochloric Acid See below Purified Water qs 1 mL [0050] The PEG-carbohydrate-lipid may be selected from Table 1, where PEG chain contains 8 to 16 subunits. Sodium hydroxide was used to prepare a 10% w/w solution in purified water. The targeted pH was in a range of 4.0 to 7.5. The NaOH or HCl (6N) solution was used to adjust pH as necessary. Example 6 Paclitaxel IV Injectable Solution [0051] The IV solution was prepared as in Example 5, except that the dehydrated alcohol contained 5% of sodium hydroxide (v/v). A sample formulation is described in Table 7. [0000] TABLE 7 Ingredient mg/mL Paclitaxel 12.0 PEG-carbohydrate-lipid 30.0 Dehydrated Alcohol 10.0 Sodium Chloride  9.0 Sodium Hydroxide See below Hydrochloric Acid See below Purified Water qs 1 mL [0052] The PEG-carbohydrate-lipid may be selected from Table 1, where PEG chain contains 8 to 16 subunits. Sodium hydroxide was used to prepare a 10% w/w solution in purified water. The targeted pH was in a range of 4.0 to 7.5. The NaOH or HCl (6N) solution was used to adjust pH as necessary. Example 7 Triazole Fungicide IV Injectable Solution or Suspension [0053] The IV solution was prepared as in Example 5. A sample formulation is described in Table 8. [0000] TABLE 8 Ingredient mg/mL Active 10.0 PEG-carbohydrate-lipid 30.0 Dehydrated alcohol 20.0 Sodium Hydroxide See below Hydrochloric Acid See below Sodium Benzoate 20.0 Purified Water qs 1 mL [0054] The active is voriconazole or posaconazole. PEG-carbohydrate-lipid may be selected from Table 1, where PEG chain contains 8 to 16 subunits. Sodium hydroxide was used to prepare a 10% w/w solution in purified water. The targeted pH was in a range of 4.0 to 7.5. The NaOH or HCl (6N) solution was used to adjust pH as necessary. Example 8 Pharmacokinetic Profile of Propofol formulations [0055] Groups of three male mice (B6D2F1, 4 weeks old and weights of 20 to 28 grams were used for the studies. Pharmacokinetics (PK) were performed on heparinized mouse plasma samples obtained typically at after the bolus IV injection at 1, 3, 8, 12, 15, 20, 30, 45 and 60 minutes for Propofol. Samples were analyzed using a HPLC-MS method. To determine the level of the drug, the drug was first isolated from plasma with a sample pre-treatment. Acetonitrile were used to remove proteins in samples. An isocratic HPLC-MS/MS method was then used to separate the drugs from any potential interference. Drug levels were measured by MS detection with a multiple reaction monitoring (MRM) mode. PK data was analyzed using the WinNonlin program (ver. 5.3, Pharsight) compartmental models of analysis. [0056] FIG. 2 shows mouse PK profiles of propofol formulations with (1) 1% of Propofol in a formulation consisting of 2.5% of OAPDL-12 in saline solution and (2) a commercial product of 1% Propofol The drug was administered intravenously and the dosing strength was 15 mg/kg. From the 2-compartmental calculations, the AUC were 101.6 mg·hr/L with a distribution half-life of 0.68 minutes and elimination half-life of 6.03 minutes for formulation (1) and 71.4 mg·hr/L with a distribution half-life of 0.69 minutes and elimination half-life of 9.3 minutes for the formulation (2), respectively. From the non-compartmental calculations, the AUC were 184.2 mg·hr/L with a half-life of 49.45 minutes for formulation (1) and 133.8 mg·hr/L with a half-life of 19.25 minutes for formulation (2), respectively. [0057] While preferred aspects and embodiments of the present invention have been described, those skilled in the art will recognize that other and further changes and modifications can be made without departing from the spirit of the invention, and all such changes and modifications should be understood to fall within the scope of the invention.
The invention comprises various aqueous PEG-carbohydrate-lipid based formulations of pharmaceutical active ingredients including compositions for intravenous injections. This invention relates to methods and compositions for improving solubility and the safety profile of pharmaceutical compounds. More particularly, the present invention relates to employing PEG-carbohydrate-lipid conjugates for formulating drug compositions having increased solubility or dispersivity and enhanced stability.
0
BACKGROUND OF THE INVENTION [0001] 1. Technical Field of the Invention [0002] The present invention relates to a method of using a catalytic heat sink with alcohol. More specifically, the invention is drawn toward using the heat sink in mobile applications that generate an abundance of heat from onboard electronics. [0003] 2. Background of the Invention [0004] Significant amount of heat is generated from on-board electronics and equipment in mobile applications. In the case of high-speed mobile applications, such as aircraft and other vehicles, this waste heat could be transferred to the fuel itself, which is eventually combusted. However, such heat rejection (heat sink) becomes a challenge when the fuel flow rate is low (e.g. idling). If the fuel temperature exceeds a certain temperature, the electronics can become damaged. [0005] An alternative heat removal technique is to transfer excess heat into the vehicle's liquid fuel. Aircraft, for example, typically have a large amount of fuel on-board, thus making it convenient to transfer heat to the fuel before the fuel is consumed by the engine. Heating the fuel may also improve the fuel efficiency of the jet engine. However, the heat capacity of the fuel is limited. Components that come into contact with the fuel, such as seals, valves, and electronic components, may be damaged if the fuel is too hot. Furthermore, the fuel itself has a finite capacity for heat. In some circumstances, aircraft missions must end early, not because of lack of fuel, but because of lack of available heat sink capacity. Therefore, an alternative technique to remove excess heat from an aircraft, without increasing the thermal signature of the aircraft, is desirable. [0006] Modern aircraft also contain advanced insulation systems, which further exacerbates the problem of easily dissipating internally generated heat. As noted above, methods known prior generally rely on the vehicle's liquid fuel; however, it is typically infeasible to use the liquid fuel while an aircraft is idling. [0007] Therefore, it would be beneficial to have a method and apparatus that advantageously addresses at least one of these needs. SUMMARY OF THE INVENTION [0008] The present invention is directed to a method that satisfies at least one of these needs. One embodiment of the present invention provides for an apparatus for use as a catalytic alcohol dehydrogenation heat sink for a mobile vehicle. In one embodiment, the apparatus can include a first vessel, a second vessel, a heat source, a reaction zone, and a catalyst disposed within the reaction zone. The first vessel being operable to have a volume of alcohol contained therein, and the second vessel being operable to have a volume of jet fuel contained therein. The heat source preferably includes onboard electronics for generating heat. The reaction zone can be in fluid communication with the first vessel and can be in thermal communication with the heat source. The catalyst can be operable to promote an endothermic dehydrogenation reaction of the alcohol to create a reaction fluid that includes unreacted alcohol, hydrogen, and a dehydrogenated hydrocarbon product. Depending on the type of alcohol, the dehydrogenated hydrocarbon product can be an aldehyde or a ketone. [0009] In another embodiment, the reaction zone is not in fluid communication with the second vessel. In a preferred embodiment, the catalyst is operable to dehydrogenate at least a portion of the alcohol at a temperature within the range from 0° C. to 150° C. Exemplary alcohols include isopropanol, butanol, pentanol, and combinations thereof. [0010] In another embodiment, the apparatus can also include a separator that is operable to remove the unreacted alcohol from the reaction fluid, such that the unreacted alcohol can be recycled back to the first vessel, or to some other advantageous point within the apparatus. In another embodiment, the apparatus can also include a burner that is in fluid communication with the second vessel and the reaction zone. The burner is preferably part of a jet engine, and can be operable to burn jet fuel, unreacted alcohol, the dehydrogenated product, and hydrogen. [0011] In one embodiment, the catalyst can include an active metal component and a support component. Preferred active metal components include rhodium, ruthenium, and combinations thereof, with rhodium being most preferred. Preferred support components include alumina, activated carbon, and combinations thereof, with alumina being most preferred. In one embodiment, the weight ratio of the active metal component to the total weight of the catalyst is 1:20. [0012] In another embodiment, the present invention provides an apparatus for use as a catalytic alcohol dehydrogenation heat sink for a mobile vehicle. In this embodiment, the apparatus can include a first vessel, a second vessel, onboard electronics, a heat exchanger and a volume of catalyst. The first vessel is operable to have a volume of isopropanol contained therein, and the second vessel is operable to have a volume of jet fuel contained therein. The onboard electronics can generate the heat that is useful for promoting an endothermic reaction. The heat exchanger can be disposed within the mobile vehicle, and includes a hot side and a cold side. The hot side can be in thermal communication with the heat from the onboard electronics, and the cold side can be in fluid communication with the first vessel, such that the cold side is adaptable for receiving at least a portion of the volume of the isopropanol from the first vessel. The volume of catalyst can be operable to promote the dehydrogenation of isopropanol. [0013] In another embodiment, the apparatus can further include a third vessel having a thermal fluid in thermal communication with the onboard electronics and the heat exchanger. The thermal fluid can transfer the heat from the onboard electronics to the hot side of the heat exchanger in order to provide the heat required to initiate a dehydrogenation reaction with isopropanol in the presence of the catalyst. Exemplary thermal fluids include jet fuel, oil, water, polyalpha-olefin (PAO), and air. [0014] In yet another embodiment, the present invention provides a method for using a catalytic heat sink using isopropanol to cool a vehicle. The method includes the steps of providing a catalyst to a reaction, generating heat from a heat source, feeding the alcohol from a first vessel to the reaction zone, heating the alcohol to a reaction temperature, and dehydrogenating the alcohol in an endothermic reaction to create a reaction product. The reaction product can include hydrogen, unreacted alcohol, and a dehydrogenated product. The dehydrogenated product can be a ketone or an aldehyde depending on the type of alcohol used. The reaction zone is in thermal communication with the heat source such that the reaction zone is operable to transfer heat from the heat source to the reaction zone. The alcohol is heated to the reaction temperature using the heat removed from the heat source. An exemplary reaction temperature is within a range between 0° C. and 80° C. In another embodiment, the temperature is within a range between 25° C. and 65° C. In one embodiment, the method is operable to provide heat removal from the heat source while the mobile vehicle is idle. [0015] In one embodiment, the heat source includes onboard electronics. In another embodiment, the method can also include vaporizing the dehydrogenated hydrocarbon product following the dehydrogenating step, such that additional heat is removed from the heat source. In another embodiment, the method can further include the step of removing the dehydrogenated hydrocarbon product and hydrogen from the reaction zone and feeding at least a portion of the dehydrogenated hydrocarbon product and hydrogen to a burner for use as a secondary fuel. Any unreacted alcohol can also be removed from the reaction zone, and sent to the burner or recycled back to the first vessel. Exemplary separating means can include a flash vessel, combination of vapor/liquid separation in combination with membrane separation, pressure swing adsorption, and the like. [0016] Exemplary alcohols include isopropanol, butanol, and pentanol, with isopropanol being preferred. [0017] The catalyst is operable to promote the endothermic dehydrogenation reaction of the alcohol. The catalyst has an active metal on a support. Preferred active metal components include rhodium, ruthenium, and combinations thereof, with rhodium being most preferred. Preferred support components include alumina, activated carbon, and combinations thereof, with alumina being most preferred. In one embodiment, the weight ratio of the active metal component to the total weight of the catalyst is from 1:1000 to 1:20. In one embodiment, the reaction zone can include a catalyst loading system. Exemplary catalyst loading systems include a catalyst packed bed, a catalyst fluidized bed, and a catalyst washcoat. BRIEF DESCRIPTION OF THE DRAWINGS [0018] So that the manner in which the above-recited features, advantages, and objectives of the invention, as well as others that will become apparent, are attained and can be understood in detail, more particular description of the invention briefly summarized above may be had by reference to the embodiments thereof that are illustrated in the drawings that form a part of this specification. It is to be noted, however, that the appended drawings illustrate only several embodiments of the invention and are, therefore, not to be considered limiting of the invention's scope, for the invention may admit to other equally effective embodiments. [0019] FIG. 1 is an illustration displaying an embodiment of the present invention. [0020] FIG. 2 is an illustration displaying an embodiment of the present invention. [0021] FIG. 3 is an illustration displaying an embodiment of the present invention. DETAILED DESCRIPTION [0022] Although the following detailed description contains many specific details for purposes of illustration, one of ordinary skill in the art will appreciate that many variations and alterations to the following details are within the scope and spirit of the invention. Accordingly, any exemplary embodiments of the invention described herein are set forth without any loss of generality to, and without imposing limitations thereon, the present invention. [0023] Alcohols are generally classified into primary, secondary and tertiary, based upon the number of carbon atoms connected to the carbon atom that bears the hydroxyl group. Namely, the primary alcohols have general formulas RCH 2 —OH; secondary alcohols are RR′CH—OH; and tertiary alcohols are RR′R″C—OH, where R, R′ and R″ stand for alkyl groups. Ethanol and n-propyl alcohol are primary alcohols, and isopropyl alcohol is a secondary alcohol. [0024] In a typical dehydrogenation reaction of alcohol, the alcohol combines with heat in the presence of a suitable catalyst to yield hydrogen gas and either a ketone or an aldehyde. The generic dehydrogenation reaction of an alcohol is expressed below: [0000] [0025] Primary alcohols (R—CH 2 —OH) are dehydrogenized to aldehydes (R—CHO), whereas secondary alcohols (RR′CH—OH) are dehydrogenized to ketones (RR′C—OH). In a preferred embodiment, isopropanol (“IPA”) can be dehydrogenized to form acetone and hydrogen according to the following reaction: [0000] [0026] In this reaction, IPA is heated from room temperature to a reaction temperature. When the IPA reaches this temperature and is in the presence of an acceptable catalyst, the IPA converts to acetone and hydrogen while also absorbing energy, thereby lowering the temperature. Additional heat can be absorbed by vaporizing the acetone and any unreacted IPA. Exemplary catalyst include, for example, an activated metal of rhodium or ruthenium on a support of alumina or activated carbon. Preferred catalyst include ruthenium on carbon and rhodium on alumina, with rhodium on alumina being most preferred. [0027] In one embodiment, a synthesized ruthenium catalyst can be prepared by making an aqueous solution of ruthenium chloride, adding the solution to activated carbon, and then adding sodium borohydride. A 5% metal to total mass of the catalyst is preferred. In various embodiments of the present invention, the catalyst can be placed inside a heat exchanger, a separate reaction zone, or added with the alcohol at various points within the apparatus. [0028] The advantage of using of IPA, as opposed to using jet fuel as described in the Background, can be seen in Table I below: [0000] TABLE I Heat Sink Capacity for Various Fluids at Different Temperatures Heat Sink (J/g) Fluid 64° C. 80° C. Jet Fuel 78 110 IPA 107 156 IPA (2.1% 147 — conversion) IPA (3.9% 183 — conversion) [0029] Generally speaking, IPA provides an additional heat sink capability of approximately 40% over jet fuel even without any conversion. Furthermore, with every 2% conversion of IPA, an additional 40 J/g of heat can be absorbed. However, the dehydrogenation of IPA is equilibrium limited. Therefore, removal of the reaction products from reaction zone can greatly increase the efficiency of the overall reaction, leading to additional removal of heat. [0030] Now referring to FIG. 1 , catalytic alcohol dehydrogenation heat sink (“CADHS”) may be used to absorb or transfer heat from various heat sources. CADHS may be used, for example, to reduce heat in a vehicle such as an aircraft or an automobile. Exemplary aircraft include airplanes, jets, helicopters, space shuttles, and rockets. Furthermore, CADHS may be used in any other equipment requiring a heat sink. Sources of heat on an aircraft may include, for example, electronics, and the like. Electronics can include avionics or any other electrical or electronic equipment located on an aircraft. [0031] The CADHS can include first vessel [ 10 ], which contains alcohol, and second vessel [ 20 ], which contains fuel. The CADHS also can include heat source [ 30 ], reaction zone [ 40 ], and burner [ 50 ]. First vessel [ 10 ] is in fluid communication with reaction zone [ 40 ] via line [12] and second vessel [ 20 ] is in fluid communication with burner [ 50 ] via line [ 22 ]. Second vessel [ 20 ] contains fuel that is sent to burner [ 50 ] for use as a primary fuel. The CADHS can optionally include separator [ 60 ]. [0032] In one embodiment, heat source [ 30 ] includes electrical equipment located on the vehicle. In an aircraft this would include, for example, avionics; communications, navigation and monitoring hardware; collision-avoidance systems; weather systems and radar; electro-optics; electronic support measures and defensive aids systems and the like. When the vehicle is operational, the electrical equipment within heat source [ 30 ] produces heat. At certain temperatures, the electrical equipment can become damaged. In an embodiment of the present invention, heat source [ 30 ] is in thermal communication [ 32 ] with reaction zone [ 40 ] such that heat energy is transferred from heat source [ 30 ] to reaction zone [ 40 ]. This advantageously lowers the temperature within heat source [ 30 ], while also increasing the temperature within reaction zone [ 40 ] in order to enable a catalytic dehydrogenation reaction when alcohol from first vessel [ 10 ] is fed into reaction zone [ 40 ] in the presence of a catalyst. This reaction is an endothermic reaction, thereby reducing the temperature within reaction zone [ 40 ] and allowing additional heat energy to be transferred from heat source [ 30 ]. [0033] The endothermic reaction creates a reaction fluid that includes hydrogen and either an aldehyde or a ketone. The reaction fluid can also include unreacted alcohol. This reaction fluid can then be sent to burner [ 50 ] via line [ 42 ] to be burned and used as a supplementary fuel. In an optional embodiment, at least a portion of the reaction fluid can be sent to separator [ 60 ] via line [ 44 ]. At least a portion of the unreacted alcohol can be separated from the reaction fluid and recycled to first vessel [ 10 ] via line [ 64 ] or reintroduced directly to reaction zone [ 40 ] via line [ 66 ]. The remaining components of the reaction fluid can then be sent to burner [ 50 ] via line [ 62 ] to be used as a supplementary fuel. [0034] In an additional embodiment not shown, separator [ 60 ] can separate the reaction fluid into three separate component streams, sending the hydrogen to burner [ 50 ], sending unreacted alcohol to first vessel [ 10 ] or reaction zone [ 40 ], and vaporizing the aldehyde/ketone in order to absorb additional heat energy from heat source [ 30 ]. Vaporization can be accomplished by absorption of additional heat energy from heat source such that the temperature rises above the respective boiling point. Additionally, in embodiments in which the CADHS is operating under increased pressures, vaporization can also be accomplished by reducing the pressure of the system. [0035] Referring to FIG. 2 , a thermal fluid is contained within third vessel [ 15 ]. The thermal fluid is used to absorb heat from heat source [ 30 ] via line [ 17 ]. The heated thermal fluid then passes through the hot side of heat exchanger [ 25 ] and transfers its heat energy to the alcohol from first vessel [ 10 ] that enters the cold side of heat exchanger [ 25 ] via line [ 12 ]. The alcohol is now heated to a temperature that enables an endothermic reaction, such that once the alcohol is introduced to reaction zone [ 40 ] in the presence of the suitable catalyst, the alcohol undergoes an endothermic dehydrogenation reaction. While FIG. 2 shows an embodiment in which heat exchanger [ 25 ] and reaction zone [ 40 ] are separate units, reaction zone [ 40 ] and heat exchanger [ 25 ] can be combined into one unit. [0036] The endothermic reaction creates a reaction fluid that includes hydrogen and either an aldehyde or a ketone. The reaction fluid can also include unreacted alcohol. This reaction fluid can then be sent to burner [ 50 ] via line [ 42 ] to be burned and used as a supplementary fuel. In an optional embodiment, at least a portion of the reaction fluid can be sent to separator [ 60 ] via line [ 44 ]. At least a portion of the unreacted alcohol can be separated from the reaction fluid and recycled to first vessel [ 10 ] via line [ 64 ] or reintroduced directly to reaction zone [ 40 ] via line [ 66 ]. The remaining components of the reaction fluid can then be sent to burner [ 50 ] via line [ 62 ] to be used as a supplementary fuel. [0037] In an additional embodiment not shown, separator [ 60 ] can separate the reaction fluid into three separate component streams, sending the hydrogen to burner [ 50 ], sending unreacted alcohol to first vessel [ 10 ] or reaction zone [ 40 ], and vaporizing the aldehyde/ketone in order to absorb additional heat energy from heat source [ 30 ]. Vaporization can be accomplished by absorption of additional heat energy from heat source such that the temperature rises above the respective boiling point. Additionally, in embodiments in which the CADHS is operating under increased pressures, vaporization can also be accomplished by reducing the pressure of the system. [0038] FIG. 3 represents a simplified CADHS system in which fuel from second vessel [ 20 ] is used as the thermal fluid. In this embodiment, the fuel is used to transfer the heat energy from heat source [ 30 ] to the alcohol before the fuel is sent to burner [ 50 ]. Additionally, a portion of the fuel may be recycled back to second vessel [ 20 ] via line [ 23 ]. While FIG. 3 does not show separator [ 60 ], those of ordinary skill in the art will recognize that separator [ 60 ] could be easily incorporated into the design. Additionally, like FIG. 2 , reaction zone [ 40 ] and heat exchanger [ 25 ] can be combined into one unit. [0039] As will be readily apparent to those skilled in the art, the present invention may easily be produced in other specific forms without departing from its spirit or essential characteristics. The presented embodiments are, therefore, to be considered as merely illustrative and not restrictive, the scope of the invention being indicated by the claims rather than the foregoing description, and all changes which come within the meaning and range of equivalence of the claims are therefore intended to be embraced therein. The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed.
A heat sink is used to absorb heat produced by a vehicle. The heat sink uses an endothermic catalytic alcohol dehydrogenation reaction to assist with the absorption of excess heat produced in the electronics of the vehicle. In some embodiments, the alcohol can be pre-heated by absorbing heat from various components of the vehicle. Excess heat from the various components or from the vehicle engine can be used to vaporize the reaction fluids in order to further absorb additional heat. Reaction fluids can also be sent to the vehicle's engine/burner for use as a supplemental fuel.
1
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of application Ser. No. 11/196,690, filed Aug. 3, 2005, now U.S. Pat. No. 7,686,021; which is a continuation of Ser. No. 10/066,967, filed Feb. 4, 2002, now U.S. Pat. No. 7,146,981; which applications are incorporated herein by reference. BACKGROUND 1. Field of the Invention This invention is directed to methods and apparatuses for treating the pharyngeal wall of a patient. More particularly, this invention pertains to method and apparatus for treating a pharyngeal wall area as part of a sleep apnea treatment. 2. Description of the Prior Art Sleep apnea and snoring are complex phenomena. Commonly assigned U.S. Pat. No. 6,250,307 describes various prior techniques and discloses a novel treatment for such conditions (including a permanent palatal implant). These prior art teachings include Huang, et al., “Biomechanics of Snoring”, Endeavour , p. 96-100, Vol. 19, No. 3 (1995). That publication estimates that up to 20% of the adult population snores habitually. Snoring can be a serious cause of marital discord. In addition, snoring can present a serious health risk to the snorer. In 10% of habitual snorers, collapse of the airway during sleep can lead to obstructive sleep apnea syndrome. Id. In addition to describing a model for palatal flutter, that publication also describes a model for collapse of the pharyngeal wall. Notwithstanding efforts have been made to treat snoring and sleep apnea. These include palatal treatments such as electrical stimulation of the soft palate. See, e.g., Schwartz, et al., “Effects of electrical stimulation to the soft palate on snoring and obstructive sleep apnea”, J. Prosthetic Dentistry , pp. 273-281 (1996). Devices to apply such stimulation are described in U.S. Pat. Nos. 5,284,161 and 5,792,067. Such devices are appliances requiring patient adherence to a regimen of use as well as subjecting the patient to discomfort during sleep. Electrical stimulation to treat sleep apnea is discussed in Wiltfang, et al., “First results on daytime submandibular electrostimulation of suprahyoidal muscles to prevent night-time hypopharyngeal collapse in obstructive sleep apnea syndrome”, International Journal of Oral & Maxillofacial Surgery , pp. 21-25 (1999). Surgical treatments for the soft palate have also been employed. One such treatment is uvulopalatopharyngoplasty (UPPP) where about 2 cm of the trailing edge of the soft palate is removed to reduce the soft palate's ability to flutter between the tongue and the pharyngeal wall of the throat. See, Huang, et al., supra at 99 and Harries, et al., “The Surgical treatment of snoring”, Journal of Laryngology and Otology , pp. 1105-1106 (1996) which describes removal of up to 1.5 cm of the soft palate. Assessment of snoring treatment is discussed in Cole, et al., “Snoring: A review and a Reassessment”, Journal of Otolaryngology , pp. 303-306 (1995). Huang, et al., propose an alternative to UPPP which proposal includes using a surgical laser to create scar tissue on the surface of the soft palate. The scar is to reduce flexibility of the soft palate to reduce palatal flutter. RF ablation (so-called Somnoplasty as advocated by Somnus Technologies) is also suggested to, treat the soft palate. RF ablation has also been suggested for ablation of the tongue base. In pharyngeal snoring and sleep apnea, the pharyngeal airway collapses in an area between the soft palate and the larynx. One technique for treating airway collapse is continuous positive airway pressure (CPAP). In CPAP air is passed under pressure to maintain a patent airway. However, such equipment is bulky, expensive and generally restricted to patients with obstructive sleep apnea severe enough to threaten general health. Huang, et al. at p. 97. Treatments of the pharyngeal wall include electrical stimulation is suggested in U.S. Pat. No. 6,240,316 to Richmond et al. issued May 29, 2001, U.S. Pat. No. 4,830,008 to Meer issued May 16, 1989, U.S. Pat. No. 5,158,080 to Kallok issued Oct. 27, 1992, U.S. Pat. No. 5,591,216 to Testerman et al. issued Jan. 7, 1997 and PCT International Publication No. WO 01/23039 published Apr. 5, 2001 (on PCT International Application No. PCT/US00/26616 filed Sep. 28, 2000 with priority to U.S. Ser. No. 09/409,018 filed Sep. 29, 1999). U.S. Pat. No. 5,979,456 to Magovern dated Nov. 9, 1999 teaches an apparatus for modifying the shape of a pharynx. These teachings include a shape-memory structure having an activated shape and a quiescent shape. Dreher et al., “Influence of nasal obstruction on sleep-associated breathing disorders”, So. Laryngo-Rhino-Otologie, pp. 313-317 (June 1999), suggests using nasal stents to treat sleep associated breathing disorders involving nasal obstruction. Upper airway dilating drug treatment is suggested in Aboubakr, et al., “Long-term facilitation in obstructive sleep apnea patients during NREM sleep”, J. Applied Physiology, pp. 2751-2757 (December 2001). Surgical treatments for sleep apnea are described in Sher et al., “The Efficacy of Surgical Modifications of the Upper Airway in Adults with Obstructive Sleep Apnea Syndrome”, Sleep , Vol. 19, No. 2, pp. 156-177 (1996). Anatomical evaluation of patients with sleep apnea or other sleep disordered breathing are described in Schwab, et al., “Upper Airway and Soft Tissue Anatomy in Normal Subjects and Patients with Sleep-Disordered Breathing”, Am. J. Respir. Crit. Care Med ., Vol. 152, pp. 1673-1689 (1995) (“Schwab I”) and Schwab et al., “Dynamic Upper Airway Imaging During Awake Respiration in Normal Subjects and Patients with Sleep Disordered Breathing”, Am. Rev. Respir. Dis ., Vol. 148, pp. 1385-1400 (1993) (“Schwab II). In Schwab I, it is noted that apneic patients have a smaller airway size and width and a thicker lateral pharyngeal wall. For reviews of pharyngeal wall thickness and other structure and obstructive sleep apnea, see, also, Wheatley, et al., “Mechanical Properties of the Upper Airway”, Current Opinion in Pulmonary Medicine, pp. 363-369 (November 1998); Schwartz et al., “Pharyngeal airway obstruction in obstructive sleep apnea: pathophysiology and clinical implication”, Otolaryngologic Clinics of N. Amer., pp. 911-918 (December 1998); Collard, et al., “Why should we enlarge the pharynx in obstructive sleep apnea?”, Sleep, (9 Suppl.) pp. S85-S87 (November 1996); Winter, et al., “Enlargement of the lateral pharyngeal fat pad space in pigs increases upper airway resistance”, J. Applied Physiology, pp. 726-731 (September 1995); and Stauffer, et al., “Pharyngeal Size and Resistance in Obstructive Sleep Apnea”, Amer. Review of Respiratory Disease, pp. 623-627 (September 1987) SUMMARY OF THE INVENTION According to one aspect of the present invention, methods and apparatuses are disclosed for treating a pharyngeal airway having a pharyngeal wall of a patient at least partially surrounding and defining said airway. The method includes inserting an expander member into the airway and positioning an active portion of the expander member in opposition to portions of the wall to be treated. The expander member is activated to urge the wall portions outwardly to an outwardly displaced position. The expander member is then deactivated while leaving the wall portions in the outwardly placed position and the expander member is removed from said airway. A further aspect of the invention includes stabilization of at least a portion of the pharyngeal wall in the outwardly placed position after compression of portions of the wall. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows, in cross-section, a naso-pharyngeal area of an untreated patient; FIG. 2 is the view of FIG. 1 with the soft palate containing an implant in the form of a bolus of micro-beads deposited in a linear path; FIG. 3 is a frontal view of the patient of FIG. 3 showing an alternative embodiment with micro-beads deposited as spherical deposits; FIG. 4 is a schematic representation showing a patch for delivering a bolus of micro-beads through a plurality of needles; FIG. 5 is a schematic cross-sectional view (taken generally along line 5 - 5 in FIG. 2 ) of a pharyngeal airway at a position in a person with the airway defined by opposing portions of a pharyngeal wall and a base of a tongue; FIG. 6 is the view of FIG. 5 with a first embodiment of an expander member in position prior to activation; FIG. 7 is the view of FIG. 6 following activation of the expander member to compress portions of the pharyngeal wall; FIG. 8 is a side-sectional view of compression pads used in the expander member of FIG. 7 ; FIG. 9 is the view of FIG. 7 following deactivation and removal of the expander member and showing retention of the pharyngeal wall in an expanded state; FIG. 10 is the view of FIG. 6 showing an alternative embodiment of the invention; FIG. 11 is the view of FIG. 6 showing a further alternative embodiment of the invention; FIG. 12 is the view of FIG. 6 showing a still further alternative embodiment of the invention; FIG. 13 is a schematic cross-sectional view (taken generally along line 13 - 13 in FIG. 2 ) of a pharyngeal airway at a position in a person distal to the base of the tongue and with the airway defined by the pharyngeal wall; FIG. 14 is the view of FIG. 13 with a further embodiment of an expander member positioned in the airway in a deactivated state; FIG. 15 is the view of FIG. 14 with the expander member shown activated compressing the pharyngeal wall; FIG. 16 is the view of FIG. 15 following deactivation and removal of the expander member and showing retention of the pharyngeal wall in an expanded state; FIG. 17 is a sectional schematic view of a compressed portion of tissue defining, in part, a pharyngeal airway and stabilized by a biocompatible material in the tissue of the compressed portion; FIG. 18 is the view of FIG. 17 with the compressed tissue stabilized by suture material; FIG. 19 is the view of FIG. 17 but with the tissue not being compressed and being stabilized by a suture material; FIG. 20 is a side-sectional schematic view of a suture material having resorbable and non-resorbable portions; FIG. 21 is the view of FIG. 18 with the suture material of FIG. 20 prior to resorption of the resorbable portions of the suture material; and FIG. 22 is the view of FIG. 21 with the suture material of FIG. 20 following resorption of the resorbable portions of the suture material. DESCRIPTION OF THE PREFERRED EMBODIMENT A. Physiology Background Referring now to the several drawing figures, in which identical elements are numbered identically throughout, a description of a preferred embodiment of the present invention will now be provided. The disclosures of U.S. Pat. No. 6,250,307 and PCT International Publication No. WO 01/19301 (PCT/US00/40830) are incorporated herein by reference. FIG. 1 shows, in cross-section, a naso-pharyngeal area of an untreated patient. FIG. 1 shows the nose N, mouth M and throat TH. The tongue T is shown in an oral cavity OC of the mouth. A hard palate HP (containing a bone B) separates the oral cavity OC from the nasal cavity NC. The nasal concha C (soft tissue which defines, in part, the nasal sinus—not shown) resides in the nasal cavity NC. The soft palate SP (a muscle activated soft tissue not supported by bone) depends in cantilevered manner at a leading end LE from the hard palate HP and terminates at a trailing end TE. Below the soft palate SP, the pharyngeal wall PW defines the throat passage TP. A nasal passage NP connects the nasal cavity NC to the pharyngeal wall PW. Below an epiglottis EP, the throat passage TP divides into a trachea TR for passing air to the lungs and an esophagus ES for passing food and drink to the stomach. The soft palate SP is operated by muscles (not separately shown and labeled) to lift the soft palate SP to urge the trailing edge TE against the rear area of the pharyngeal wall PW. This seals the nasal cavity NC from the oral cavity OC during swallowing. The epiglottis EP closes the trachea TR during swallowing and drinking and opens for breathing. For purposes of this disclosure, the nasal cavity NC, oral cavity OC and throat passage TP are collectively referred to as the naso-pharyngeal area of the patient (defining, in part, the pharyngeal airway PA in FIGS. 5 and 13 ) with the area including the various body surfaces which cooperate to define the nasal cavity NC, oral cavity OC and throat passage TP. These body surfaces include outer surfaces of the nasal concha C, the upper and lower surfaces of the soft palate SP and outer surfaces of the pharyngeal wall PW. Outer surfaces means surfaces exposed to air. Both the upper and lower surfaces of the soft palate SP are outer surfaces. Snoring can result from vibration of any one of a number of surfaces or structures of the naso-pharyngeal area. Most commonly, snoring is attributable to vibration of the soft palate SP. However, vibratory action of the nasal concha C and the pharyngeal wall PW can also contribute to snoring sounds. It is not uncommon for vibratory action from more than one region of the naso-pharyngeal area to contribute to snoring sounds. Sleep apnea can result from partial or full collapse of the naso-pharyngeal wall during sleep. FIG. 5 shows a schematic representation of a cross-section of a throat with the pharyngeal airway PA defined by the pharyngeal wall PW and the tongue T. The anterior-posterior axis is labeled AP to assist in discerning the orientation. The pharyngeal wall PW is shown as including the left lateral pharyngeal wall LLPW, right lateral pharyngeal wall RLPW and posterior pharyngeal wall PPW. B. Disclosure of Prior Application In addition to disclosing the teachings of U.S. Pat. No. 6,250,307 and the teachings of selected embodiments of PCT International Publication No. WO 01/19301 (both incorporated herein by reference), commonly assigned and co-pending patent application U.S. Ser. No. 09/636,803, filed Aug. 10, 2000, which is hereby incorporated by reference in its entirety, describes techniques for stiffening tissue of the pharyngeal airway with a bolus of particulate matter. FIGS. 2 and 3 show are taken from the '803 application and show an implant 10 as a bolus of particulate matter. An example of such particulate matter would be micro-beads. An example of such is taught in U.S. Pat. Nos. 5,792,478 and 5,421,406. These patents teach carbon-coated metallic or ceramic particles having cross-sectional dimensions of between 100 and 1,000 microns. The particles are carried in a fluid or gel. These patents state that upon insertion into body tissue, the particles do not migrate significantly and, apparently due to fibrotic response, the tissue into which the particles are injected stiffens. The particles of U.S. Pat. Nos. 5,792,478 and 5,421,406 are one example of particles for stiffening injection. Such particles can also include ceramic particles or pure carbon or other bio-compatible particles. The particles can be carried in a liquid or gel medium. The particles can have multi-modal particle size distributions (i.e., a mix of two or more sizes of particles with the smaller particles filling interstitial spaces between larger particles). The bolus 10 of particles can be applied by a needle to inject the bolus 10 into the soft palate SP. The bolus can be the same volume as the volume of the implants 20 of FIGS. 8 and 9 of U.S. Pat. No. 6,250,307. With reference to FIG. 3 , a multiple of bolus injections can be made in the soft palate resulting in deposition of generally spherical deposits 10 ′ of particles. Alternatively, an injecting needle can be withdrawn while simultaneously ejecting particles for the bolus 10 ( FIG. 2 ) to be deposited in a line similar in dimensions to the implants 20 of FIGS. 8 and 9 of U.S. Pat. No. 6,250,307. The foregoing emphasizes the use of implants to stiffen the soft palate SP. Implants 10 can be placed in any of the tissue of the naso-pharyngeal area (e.g., the concha C, soft palate SP or pharyngeal wall PW) to treat snoring. Also, such a treatment can stiffen the tissue of the throat and treat sleep apnea resulting from airway collapse by stiffening the airway. While a needle deposition of a bolus of particles may be preferred, the bolus can be applied in other manners. FIG. 4 (which is a reproduction of FIG. 16 of the '803 application) illustrates deposition of particulates through a patch 12 having a volume 14 containing such micro-beads 16 . One side 12 a of the patch 12 contains an array of micro-needles 18 communicating with the volume 14 . The needles 18 may be small diameter, shallow penetration needles to minimize pain and blood. Examples of shallow, small diameter needles are shown in U.S. Pat. No. 5,582,184 to Erickson et al. Placing the surface 12 a against the tissue (e.g., the pharyngeal wall PW as shown in FIG. 4 ), the needles 18 penetrate the outer surface of the tissue PW. The patch 12 can then be compressed (by finger pressure, roller or the like) to eject the beads 16 from the volume 14 through the plurality of needles 18 . The patch 12 can be provided with interior dividing walls (not shown) so that some of the volume of beads 16 is ejected through each needle 18 . The side 12 a acts as a stop surface to ensure control over the penetration depth of the needles 18 to reduce risk of undesired puncture of underlying structures. Stiffening of the naso-pharyngeal tissue provides structure to reduce vibration and snoring. Such structure reduces airway collapse as a treatment for sleep apnea. C. Pharyngeal Wall Compression FIGS. 5-16 show various methods and apparatus for enlarging the pharyngeal airway PA. As will be described, further disclosure is made for stiffening the tissue or maintaining the enlarged airway size. FIG. 6 is the view of FIG. 5 showing an expander member 20 positioned within the pharyngeal airway PA for the purpose of treating the pharyngeal wall PW. As will become apparent, the treatment includes enlargement of the pharyngeal airway PA by urging at least portions of the pharyngeal wall PW outwardly. In the embodiment of FIG. 6 , the right and left lateral pharyngeal wall portions RLPW, LLPW are being urged outwardly to increase the area of the airway PA. The expander member 20 includes left and right supports 22 positioned opposing the right and left lateral pharyngeal wall portions RLPW, LLPW. Compression pads 24 are carried on the supports 22 and in direct opposition to the right and left lateral pharyngeal wall portions RLPW, LLPW. The supports 22 are maintained in fixed spaced apart relation by a spacer bar 26 . While not shown in the drawings, the spacer bar 26 can be adjustable to permit a physician to modify the spacing between the supports 22 and to permit narrowing the spacing between the supports 22 to facilitate ease of placement of the expander member 20 in the airway PA at a desired treatment area. Preferably, the pads 24 and supports 22 have a length (distance parallel to the longitudinal axis of the airway PA) greater than a width (distance parallel to the opposing surface of the wall PW as indicated by W in FIG. 6 ) to treat an extended length of the wall PW. For example, the pads 24 and supports 22 could be about two centimeters long. The compression pads 24 are inflatable bladders connected by a tube 28 ( FIG. 8 ) to a source of a pressurized fluid (not shown). Admission of pressurized fluid into the bladders 24 causes the bladders to enlarge urging the right and left lateral pharyngeal wall portions RLPW, LLPW outwardly as illustrated in FIG. 7 . The compression of the to tissue of the patient could be compression of the pharyngeal wall PW or compression of tissue surrounding the pharyngeal wall PW (for example, fatty pads). After the compression, the pads 24 are deflated and the expander member 20 is removed from the airway PA as illustrated in FIG. 9 leaving compressed right and left lateral pharyngeal wall portions RLPW, LLPW and an enlarged cross-sectional area of the pharyngeal airway PA. In addition to compressing the walls of the pharyngeal airway PA, the compressed walls may be stabilized in a compressed state to ensure longer lasting retention of the therapeutic benefits of the enlarged airway PA. This stabilization can include injecting a bio-adhesive or bio-sealants into the tissue adjacent the treated portions of the pharyngeal wall. An example of bio-adhesives includes cyanoacrylates. Without intending to be a limiting example, these include 2-octyl cyanoacrylate and 2-butyl cyanoacrylate. The 2-octyl cyanoacrylate is developed by Closure Medical Corp., Raleigh, N.C., USA for use to treat topical skin wounds, oral cancers and periodontal disease. It may last 1-2 weeks with faster absorbing products in development. The 2-butyl cyanoacrylate is used as a skin protectant and dental cement and is available from GluStitch, Inc., Delta, BC, Canada Biocompatible adhesives also include surgical adhesives such as those developed by CryoLife International, Inc., Kennesaw, Ga., USA whose product is composed of purified bovine serum albumin (45%) and cross-linking agent glutaraldehyde (10%). Similar formulations include natural proteins (e.g., collagen, gelatin) with aldehyde or other cross-link agents. Such bio-sealants may be fibrin sealants. Examples include blood-derived products (e.g., Tisseel™ distributed by Baxter Corp., Deerfield, Ill., USA). Other examples of coatings include hydrogel coatings. An example of these include a photo-curing synthetic sealant developed by Focal, Inc., Lexington, Mass., USA which can adhere to moist or dry tissue and is highly flexible and elastic. This sealant may be absorbable over short or long terms. The sealant is currently used to treat air leaks associated with lung surgery. Other coatings include denture adhesives approved for use in humans. From the foregoing, it can be seen there are a wide variety of adhesives and other coatings suitable for use with the present invention. The foregoing lists are intended to be illustrative and not exhaustive. With the description given with respect to FIGS. 6-9 , the bio-stabilizer can be injected into the compressed regions of tissue adjacent the right and left pharyngeal wall. For example, the material can be injected into the compressed portions of the right and left lateral pharyngeal wall portions RLPW, LLPW (mucosal or sub-mucosal or muscular tissue) or into compressed tissue behind the right and left pharyngeal walls, such as compressed fatty tissues. The expander 20 can be left in place while the adhesive as least partially sets such that when the expander 20 is removed, the adhesive helps retain the compressed right and left lateral pharyngeal wall portions RLPW, LLPW in a compressed state. Bio-adhesives degrade and the therapeutic benefit of the bio-adhesives can be lost over time. Accordingly, a still further embodiment of the present invention includes injecting a fibrosis-inducing agent into the compressed tissue. The fibrosis-inducing agent induces a fibrotic response of the tissue to stiffen the tissue and helping to retain the tissue in a compressed state. It will be appreciated that the fibrosis-inducing agent may be used in conjunction with the bio-adhesive or the bio-adhesive and fibrosis-inducing agents can be used separately. In the preferred embodiment the fibrosis-inducing agent will be substantially non-biodegradable so as to provide a long lasting, chronic effect maintaining the compressed state of the pharyngeal wall PW. By way of non-limiting example, a fibrosis-inducing material may be microbeads as described above. While microbeads may be a preferred embodiment, alternative techniques for inducing fibrosis can be in the form of placement in the compressed tissue of polyester material or other foreign bodies which induce a fibrotic response. In addition to the adhesives or fibrosis-inducing agents, drugs may be admitted into the tissue. Drugs may be injected directly or in microspheres. FIG. 8 illustrates an embodiment for injecting adhesives or microbeads into the compressed tissue by the use and placement of micro needles 30 on a side of the bladder 24 opposing the tissue similar to the embodiment of FIG. 4 . The fluid from the bladder 24 through the needles 30 contains the bio-adhesives and the microbeads. The micro needles 30 can be of various lengths to vary the depth of distribution of the adhesives and the microbeads. FIGS. 10-12 show alternative embodiments of the present invention. Elements having functions in common with the fore-going embodiment are numbered identically with the addition of a suffix (“a”, “b” or “c”) to distinguish the embodiments. In FIGS. 6 and 7 , compression members 24 are shown only opposing the right and left lateral pharyngeal wall portions RLPW, LLPW. In FIG. 12 , four compression members 24 a are shown to cover a wider area of the right and left lateral pharyngeal wall portions RLPW, LLPW. In FIG. 11 , three compression members 24 b are shown for compressing not only the right and left lateral pharyngeal wall portions RLPW, LLPW but also the posterior pharyngeal wall PPW. In FIG. 10 , an arcuate and continuous compression member 24 c is shown for compressing the entire pharyngeal wall PW. FIGS. 13-15 illustrate use of the method of the present invention in a different region of the pharyngeal airway PA. With respect to FIGS. 6-12 , the embodiments of the invention are shown in use in that portion of the pharyngeal airway PA which is defined in part by the base of the tongue T. Further distal into the pharyngeal airway PA, the pharyngeal airway PA is defined by the pharyngeal wall PW as illustrated in FIG. 13 . The present invention is also applicable to treatment of the naso-pharynx NP ( FIG. 1 ) in which case the airway is defined by lateral and posterior pharyngeal walls and opposing surfaces of the palate. Since this is similar to the shown applications, separate illustrations need not be provided. FIG. 14 shows a circular airway expander member 20 ′ having a circular support 22 ′ and a circular bladder 24 ′. Since the support 22 ′ is annular-shaped, an unobstructed airway PA remains to permit respiration by the patient during treatment. FIG. 15 shows the device with the bladder 22 ′ in an expanded state to cause compression of the pharyngeal wall PW. FIG. 16 shows the compressed pharyngeal wall following removal of the expander member 20 ′. FIGS. 17-22 illustrate various examples of techniques for stabilizing the pharyngeal wall PW. FIG. 17 illustrates a region of compressed tissue CT impregnated with a stabilizing material 40 (e.g., adhesive, sealant or microbeads). The compressed tissue CT may be compressed mucosal tissue or may be compressed muscular tissue. Also, the compressed tissue CT may be compressed fatty pads adjacent the pharyngeal wall PW. Stabilization could result from a chemical agent (e.g., a sclerosing agent) or by application of energy (e.g., radiofrequency ablation) or any other means (e.g., cryogenic ablation). It will be appreciated that not all of these techniques need provide a permanent stabilization and some of these techniques may result in remodeling over time. Subsequent treatments may then be provided. FIG. 18 illustrates a mechanical stabilization using suture material 42 to hold the compressed tissue in a compressed state. The suture material may be resorbable or non-resorbable. FIG. 19 is similar to FIG. 18 but the pharyngeal wall is not compressed. Instead, the pharyngeal wall is stabilized by sutures 44 to underlying structure US (e.g., to underlying bucco-pharyngeal fascia, prevertebral fascia, anterior longitudinal ligament or vertebral bodies). Attachment to such bodies may also occur following compression. Stabilization can result from tacking to any sub-mucosal area surrounding the pharyngeal airway. FIGS. 20-22 illustrate a variation of FIG. 18 where the suture material 46 includes a short non-resorbable core 48 (e.g., poly ester tetrapthalate—PET) covered by a longer outer coating 50 of resorbable suture material. Immediately after the implantation, only the resorbable ends extend out of the pharyngeal wall PW into the airway PA and are tied off (see FIG. 21 ). Following resorption, the non-resorbable portion 48 is fully recessed behind the wall PW as shown in FIG. 22 to limit possibility of later migration of the non-resorbable core 48 into the airway PA. In the foregoing, the term “suture” is not intended to be limited to a thread-like material but can include clips or any other closure mechanism. The foregoing describes numerous embodiments of a method and apparatus to treat a pharyngeal wall. Having described the invention, alternatives and embodiments may occur to one of skill in the art. For example, a physician may stabilize all or a portion of the pharyngeal wall within the teachings of the foregoing with conventional surgical instruments. It is intended that such modifications and equivalents shall be included within the scope of the following claims.
A patient's pharyngeal wall is treated by inserting an expander member into the airway and positioning an active portion of the expander member in opposition to portions of the pharyngeal wall to be treated. The expander member is activated to urge the wall portions outwardly to an outwardly displaced position. The expander member is then deactivated while leaving the wall portions in the outwardly placed position and the expander member is removed from said airway. A further aspect of the treatment includes stabilization of at least a portion of the pharyngeal wall after compression of portions of the wall.
0
This application is a continuation of U.S. patent application Ser. No. 09/767,611, filed Jan. 22, 2001 now U.S. Pat. No. 6,420,570, which is a continuation of U.S. patent application Ser. No. 09/375,340, filed Aug. 16, 1999, which is a continuation of U.S. patent application Ser. No. 09/050,882, filed Mar. 30, 1998 now U.S. Pat. No. 5,972,593, which is a continuation of U.S. patent application Ser. No. 08/342,366, filed Nov. 18, 1994, now abandoned which is a divisional application of U.S. Application Ser. No. 08/083,459, filed Jun. 28, 1993, now issued U.S. Pat. No. 5,399,719. FIELD OF THE INVENTION The present invention also provides methods of using new and known compounds to inactivate pathogens in health related products to be used in vivo and in vitro, and in particular, blood products. BACKGROUND Although improved testing methods for hepatitis B (HBV), hepatitis C (HCV), and human immunodeficiency virus (HIV) have markedly reduced the incidence of transfusion associated diseases, other viral, bacterial, and protozoal agents are not routinely tested for, and remain a potential threat to transfusion safety. Schmunis, G. A., Transfusion 31:547-557 (1992). In addition, testing will not insure the safety of the blood supply against future unknown pathogens that may enter the donor population resulting in transfusion associated transmission before sensitive tests can be implemented. The recent introduction of a blood test for HCV will reduce transmission of this virus; however, it has a sensitivity of only 67% for detection of probable infectious blood units. HCV is responsible for 90% of transfusion associated hepatitis. It is estimated that, with the test in place, the risk of infection is 1 out of 3300 units transfused. Further, while more sensitive seriological assays are in place for HIV-1 and HBV, these agents can nonetheless be transmitted by seronegative blood donors. International Forum: Vox Sang 32:346 (1977). Ward, J. W., et al., N. Engl. J. Med., 318:473 (1988). Up to 10% of total transfusion-related hepatitis and 25% of severe icteric cases are due to the HBV transmitted by hepatitis B surface antigen (HBasAg) negative donors. Vox Sang 32:346 (1977). To date, fifteen castes of transfusion-associated HIV infections have been reported by the Center for Disease Control (CDC) among recipients of blood pretested negative for antibody to HIV-1. Even if seroconversion tests were a sufficient screen, they may not be practical in application. For example, CMV (a herpes virus) and parvo B19 virus in humans are common. When they occur in healthy, immunocompetent adults, they nearly always result in asymptomatic seroconversion. Because such a large part of the population is seropositive, exclusion of positive units would result in substantial limitation of the blood supply. An alternative approach to eliminate transmission of viral diseases through blood products is to develop a means to inactivate pathogens in transfusion products. Development of an effective technology to inactivate infectious pathogens in blood products offers the potential to improve the safety of the blood supply, and perhaps to slow the introduction of new tests, such as the HIV-2 test, for low frequency pathogens. Ultimately, decontamination technology could significantly reduce the cost of blood products and increase the availability of scarce blood products. Furthermore, decontamination may extend the storage life of platelet concentrates which, according to Goldman M. and M. A Blajchman, Transfusion Medicine Reviews. V: 73-83 (1991), are currently limited by potential bacterial contamination. Several methods have been reported for the inactivation or elimination of viral agents in erythrocyte-free blood products. Some of these techniques, such as heat (Hilfenhous, J., et al., J. Biol. Std . 70:589 (1987)), solvent/detergent treatment (Horowitz, B., et al., Transfusion 25:516 (1985)), gamma-irradiation (Moroff, G., et al., Transfusion 26:453 (1986)), UV radiation combined with beta propriolactone, (Prince A. M., et al., Reviews of Infect Diseases 5:92-107 (1983) Prince A. M., et al., Reviews of Infect Diseases 5:92-107 (1983)), visible laser light in combination with hematoporphyrins (Matthews J. L., et al., Transfusion 28:81-83 (1988): North J., et al., Transfusion 32:121-128 (1992)), use of the photoactive dyes aluminum phthalocyananine and merocyanine 540 (Sieber F., et al. Blood 73:345-350 (1989); Rywkin S., et al., Blood 78 (Suppl 1):352a (Abstract) (1991)) or UV alone (Proudouz, K. N., et al., Blood 70:589 (1987)) are completely incomparable with maintainance of platelet function. Other methods inactivate viral agents by using known furocoumarins, such as psoralens, in the presence of ultra-violet light. Psoralens are tricyclic compounds formed by the linear fusion of a furan ring with a coumarin. Psoralens can intercalate between the base pairs of double-stranded nucleic acids, forming covalent adducts to pyrimidine bases upon absorption of long wave ultraviolet light (UVA). G. D. Cimino et al., Ann. Rev. Biochem . 54:1151 (1985); Hearst et al., Quart. Rev. Biophys . 17:1 (1984). If there is a second pyrimidine adjacent to a psoralen-pyrimidine monoadduct and on the opposite strand, absorption of a second photon can lead to formation of a diadduct which functions as an interstrand crosslink. S. T. Isaacs et al., Biochemistry 16:1058 (1977); S. T. Isaacs et al., Trends in Photobiology (Plenum) pp. 279-294 (1982); J. Tessman et al., Biochem . 24:1669 (1985); Hearst et al., U.S. Pat. Nos. 4,124,598, 4,169,204, and 4,196,281, hereby incorporated by reference. The covalently bonded psoralens act as inhibitors of DNA replication and thus have the potential to stop the replication process. Due to this DNA binding capability, psoralens are of particular interest in relation to solving the problems of creating and maintaining a safe blood supply. Some known psoralens have been shown to inactivate viruses in some blood products. H. J. Alter et al., The Lancet (ii:1446) (1988); L. Lin et al., Blood 74:517 (1989) (decontaminating platelet concentrates); G. P. Wiesehahn et al., U.S. Pat. Nos. 4,727,027 and 4,748,120, hereby incorporated by reference, describe the use of a combination of 8-methoxypsoralen (8-MOP) and irradiation. P. Morel et al., Blood Cells 18:27 (1992) show that 300 μg/mL of 8-MOP together with ten hours of irradiation with ultraviolet light can effectively inactivate viruses in human serum. Similar studies using 8-MOP and aminomethyltrimethyl psoralen (AMT) have been reported by other investigators. Dodd R. Y, et al., Transfusion 31:483-490 (1991): Margolis-Nunno, H., et al., Thromb Haemostas 65:1162 (Abstract) (1991). Indeed, the photoinactivation of a broad spectrum of microorganisms was been established, including HBV, HCV, and HIV. [Hanson C. V. Blood Cells : 18:7-24 (1992); Alter, H. J., et al., The Lancet ii :1446 (1988); Margolis-Nunno H. et al., Thromb Haemostas 65:1162 (Abstract) (1991).] Psoralen photoinactivation is only feasible if the ability of the psoralen to inactivate viruses is sufficient to ensure a safety margin in which complete inactivation will occur. On the other hand, the psoralen must not be such that it will cause damage to blood cells. Previous compounds and protocols have necessitated the removal of molecular oxygen from the reaction before exposure to light, to prevent damage to blood products from oxygen radicals produced during irradiation. See L. Lin et al., Blood 74:517 (1989); U.S. Pat. No. 4,727,027, to Wiesehahn. This is a costly and time consuming procedure. Finally, some commonly known compounds used in PCD cause undesirable mutagenic effects which appears to increase with increased ability to kill virus. In other words, the more effective the known compounds are at inactivating viruses, the more mutagenic the compounds are, and thus, the less useful they at any point in an inactivation system of products for in vivo use. A new psoralen compound is needed which displays improved ability to inactivate pathogens and low mutagenicity, thereby ensuring safe and complete inactivation of pathogens in blood decontamination methods. SUMMARY OF THE INVENTION The present invention provides new psoralens and methods of synthesis of new psoralens having enhanced ability to inactivate pathogens in the presence of ultraviolet light which is not linked to mutagenicity. The present invention also provides methods of using new and known compounds to inactivate pathogens in health related products to be used in viva and in vitro, and particularly, in blood products and blood products in synthetic media. With respect to new compounds, the present invention contemplates psoralen compounds, comprising a) a substituent R 1 on the 4′ carbon atom selected from the group comprising: —(CH 3 ) u —NH 2 , —(CH 2 ) w —R 2 —(CH 2 ) z —NH 2 , —(CH 2 ) w —R 2 —(CH 2 ) x —R 3 —(CH 2 ) z —NH 2 , and —(CH 2 ) w —R 2 —(CH 2 ) x —R 3 —(CH 2 ) y —R 4 —(CH 2 ) z —NH 2 ; wherein R 2 , R 3 , and R 4 are independently selected from the group comprising O and NH, in which u is a whole number from 1 to 10, w is a whole number from 1 and 5, x is a whole number from 2 and 5, y is a whole number from 2 and 5, and z is a whole number from 2 and 6; and b) substituents R 5 , R 6 , and R 7 on the 4, 5′, and 8 carbon atoms respectively, independently selected from the group comprising H and (CH 2 ) v CH 3 , where v is a whole number from 0 to 5; or a salt thereof. Where an element is “independently selected” from a group, it means that the element need not be the same as other elements chosen from the same group. The invention contemplates specific compounds of the above structure, wherein R 1 is —CH 2 —O—(CH 2 ) 2 —NH 2 , and wherein R 5 , R 6 , and R 7 are all CH 3 , wherein R 1 is —CH 2 —O—(CH 2 ) 2 —O—(CH 2 ) 2 —NH 2 , and R 5 , R 6 , and R 7 are all CH 3 , wherein R 1 is —CH 2 —O—(CH 2 ) 2 —O—(CH 2 ) 2 —NH—(CH 2 ) 4 —NH 2 , and R 5 , R 6 , and R 7 are all CH 3 , wherein R 1 is CH 2 —NH—(CH 2 ) 4 —NH 2 , and R 5 , R 6 , and R 7 are all CH 3 , and wherein R 1 is CH 2 —NH—(CH 2 ) 3 —NH—(CH 2 ) 4 —NH—(CH 2 ) 3 —NH 2 , and R 5 , R 6 , and R 7 are all CH 3 . The present invention also contemplates psoralen compounds, comprising: a) a substituent R 1 on the 5′ carbon atom, selected from the group comprising: —(CH 2 ) u —NH 2 —(CH 2 ) w —R 2 —(CH 2 ) z —NH 2 , —(CH 2 ) w —R 2 —(CH 2 ) x —R 3 —(CH 2 ) z —NH 2 , and —(CH 2 ) w —R 2 —(CH 2 ) x —R 3 —(CH 2 ) y —R 4 —(CH 2 ) z —NH 2 ; wherein R 2 , R 3 , and R 4 are independently selected from the group comprising O and NH, and in which u is a whole number from 1 to 10, w is a whole number from 1 to 5, x is a whole number from 2 to 5, y is a whole number from 2 to 5, and z is a whole number from 2 to 6; and, b) substituents R 5 , R 6 , and R 7 on the 4, 4′, and 8 carbon atoms respectively, independently selected from the group comprising H and (CH 2 ) v CH 3 where v is a whole number from 0 to 5, and where when R 1 is —(CH 2 ) u —NH 2 , R 6 is H; or a salt thereof. The present invention contemplate a specific compound having the above structure, wherein R 1 is —CH 2 —NH—(CH 2 ) 4 —NH 2 , and R 5 , R 6 , and R 7 are all CH 3 . The present invention also contemplates psoralen compounds, comprising: a) a substituent R 1 on the 5′ carbon atom, selected from the group comprising: —(CH 2 ) u —NH 2 , —(CH 2 ) w —R 2 —(CH 2 ) z —NH 2 , —(CH 2 ) w —R 2 —(CH 2 ) x —R 3 —(CH 2 ) z —NH 2 , and —(CH 2 ) w —R 2 —(CH 2 ) x —R 3 —(CH 2 ) y —R 4 —(CH 2 ) z —NH 2 ; wherein R 2 , R 3 , and R 4 are independently selected from the group comprising O and NH, and in which u is a whole number from 3 to 10, w is a whole number from 1 to 5, x is a whole number from 2 to 5, y is a whole number from 2 to 5, and z is a whole number from 2 to 6; and, b) substituents R 5 , R 6 , and R 7 on the 4, 4′, and 8 carbon atoms respectively, independently selected from the group comprising H and (CH 2 ) v CH 3 , where v is a whole number from 0 to 5; or a salt thereof. The present invention contemplates a specific compound having the above structure, wherein R 1 is —CH 2 —NH—(CH 2 ) 4 —NH 2 , and R 5 , R 6 , and R 7 are all CH 3 . With respect to methods for synthesizing new compounds substituted at the 4′ position of the psoralen, the present invention contemplates a method of synthesizing 4′-(w-amino-2-oxa)alkyl-4,5′,8-trimethylpsoralen, comprising the steps: a) providing 4′-(w-hydroxy-2-oxa)alkyl-4,5′,8-trimethylpsoralen; b) treating 4′-(w-hydroxy-2-oxa)alkyl-4,5′,8-trimethylpsoralen with a base and methanesulfonyl chloride so that 4′-(w-methanesulfonyloxy-2-oxa)alkyl-4,5′,8-trimethylpsoralen is produced; c) treating 4′-(w-methanesulfonyloxy-2-oxa)alkyl-4,5′,8-trimethylpsoralen with sodium azide, so that 4′-(w-azido-2-oxa)alkyl-4,5′,8-trimethylpsoralen is produced, and d) reducing 4′-[(w-azido-2-oxa)alkyl-4,5′,8-trimethylpsoralen so that 4′-[(w-amino-2-oxa)alkyl-4,5′,8-trimethylpsoralen is produced. The present invention further contemplates a method of synthesizing a compound of the structure which has a substituent R 1 on the 4′ position of the psoralen, described above, where R 1 comprises —(CH 2 )—O—(CH 2 ) x —O—(CH 2 ) z —NH 2 , where x=z, comprising the steps: a) providing a 4′-halomethyl-4,5′,8-trimethylpsoralen selected from the group comprising 4′-chloromethyl-4,5′,8-trimethylpsoralen, 4′-bromomethyl-4,5′,8-trimethylpsoralen, and 4′-iodomethyl-4,5′,8-trimethylpsoralen; b) treating said 4′-halomethyl-4,5′,8-trimethylpsoralen with HO(CH 2 ) x O(CH 2 ) z OH so that 4′-(w-hydroxy-2,n-dioxa)alkyl-4,5′,8-trimethylpsoralen is produced, where n=x+3; c) treating said 4′-(w-hydroxy-2,n-dioxa)alkyl-4,5′,8-trimethylpsoralen with a base and methanesulfonyl chloride so that 4′-(w-methanesulfonyloxy-2,n-dioxa)alkyl-4,5′,8-trimethylpsoralen is produced; d) treating 4′-(w-methanesulfonyloxy-2,n-dioxa)alkyl-4,5′,8-trimethylpsoralen with sodium azide so that 4′-(w-aziduo-2,n-dioxa)alkyl-4,5′,8-trimethylpsoralen is produced; and e) reducing 4′-(w-azido-2,n-dioxa)alkyl-4,5′,8-trimethylpsoralen so that 4′-(w-amino-2,n-dioxa)alkyl-4,5′,8-trimethylpsoralen is produced. The present invention also contemplates a method of synthesizing 4′-(12-amino-8-aza-2,5-dioxa)dodecyl-4,5′,8-trimethylpsoralen, comprising the steps: a) providing a 4′-halomethyl-4,5′,8-trimethylpsoralen, selected from the group comprising 4′-chloromethyl-4,5′,8-trimethylpsoralen, 4′-bromomethyl-4,5′,8-trimethylpsoralen, and 4′-iodomethyl-4,5′,8-trimethylpsoralen; b) treating said 4′-halomethyl-4,5′,8-trimethylpsoralen with diethylene glycol so that 4′-(7-hydroxy-2,5-dioxa)heptyl-4,5′,8-trimethylpsoralen is produced; c) treating 4′-(7-hydroxy-2,5-dioxa)heptyl-1,5′,8-trimethylpsoralen with a base and methanesulfonyl chloride so that 4′-(7-methanesulfonyloxy-2,5-dioxa)heptyl-4,5′,8-trimethylpsoralen is produced; d) treating 4′-(7-methanesulfonyloxy-2,5-dioxa)heptyl-4,5′,8-trimethylpsoralen with 1,4-diaminobutane so that 4′-(12-amino-8-aza-2,5-dioxa)dodecyl-4,5′,8-trimethylpsoralen is produced. The present invention contemplates a method of synthesizing 4′-(w-amino-2-aza)alkyl-4,5′,8-trimethylpsoralen, comprising: a) providing 4′-halomethyl-4,5′,8-trimethylpsoralen, selected from the group comprising 4′-chloromethyl-4,5′,8-trimethylpsoralen, 4′-bromomethyl-4,5′,8-trimethylpsoralen, and 4′-iodomethyl-4,5′,8-trimethylpsoralen; b) treating said 4′-halomethyl-4,5′,8-trimethylpsoralen with 1,w-aminoalkane to produce 4-(w-diamino-2-aza)alkyl-4,5′,8-trimethylpsoralen. The present invention additionally contemplates a method of synthesizing 4′-(14-amino-2,6,11-triaza)tetradecyl-4,5′,8-trimethylpsoralen, comprising: a) providing 4,5′,8-trimethylpsoralen-4′-carboxaldehyde; b) treating 4,5′,8-trimethylpsoralen-4′-carboxaldehyde with spermine and a reducing agent to produce 4′-(14-amino-2,6,11-triaza)tetradecane-4,5′,8-trimethylpsoralen. Finally, the present invention contemplates the following method of synthesizing 5′-(w-amino-2-aza)alklyl-4,4′,8-trimethylpsoralen comprising: a) providing a 5′-halomethyl-4,4′,8-trimethylpsoralen, selected from the group comprising 5′-chloromethyl-4,4′,8-trimethylpsoralen, 5′-bromomethyl-4,4′,8-trimethylpsoralen, and 5′-iodomethyl-4,4′,8-trimethylpsoralen; b) treating said 5′-halomethyl-4,4′,8-trimethylpsoralen with a 1,w-diaminoalkane to produce 5′-(w-amino-2-aza)alkyl-4,4′,8-trimethylpsoralen. The present invention contemplates methods of inactivating microorganisms in blood preparations, comprising, in the following order: a) providing, in any order, i) a compound from the group comprising 4′-primaryamino-substituted psoralens and 5′-primaryamino-substituted psoralens; ii) photoactivating means for photoactivating said compounds; and iii) a blood preparation suspected of being contaminated with a pathogen having nucleic acid; b) adding said compound to said blood preparation; and c) photoactivating said compound, so as to inactivate said pathogen. The pathogen can be single cell or multicellular organisms, such as bacteria, fungi, mycoplasma and protozoa, or viruses. The pathogen can comprise either DNA or RNA, and this nucleic acid can be single stranded or double stranded. In one embodiment, the blood preparation is either platelets or plasma. The present invention contemplates that the photoactivating means comprises a photoactivation device capable of emitting a given intensity of a spectrum of electromagnetic radiation comprising wavelengths between 180 nm and 400 nm, and in particular, between 320 nm and 380 nm. It is preferred that the intensity is between 1 and 30 mW/cm 2 (e.g., between 10 and 20 mW/cm 2 ) and that the mixture is exposed to this intensity for between one second and thirty minutes (e.g., ten minutes). The present invention contemplates embodiments wherein said blood preparation is in a synthetic media. In one embodiment, the concentration of compound is between 1 and 250 μM. In a preferred embodiment, the compound is added to said blood preparation at a concentration of between 10 and 150 μM. The present invention contemplates embodiments of the methods where inactivation is performed without limiting, the concentration of molecular oxygen. Furthermore, there is no need for the use of cosolvents (e.g., dimethyl sulphoxide (DMSO)) to increase compound solubility. In one embodiment, the present invention contemplates methods of inactivating microorganisms in blood preparations, wherein the compound is a 4-primaryamino-substituted psoralen, comprising: a) a substituent R 1 on the 4′ carbon atom, selected from the group comprising: —(CH 2 ) u —NH 2 , —(CH 2 ) w —R 2 —(CH 2 ) z —NH 2 , —(CH 2 ) w —R 2 —(CH 2 ) x —R 3 —(CH 2 ) z —NH 2 , and —(CH 2 ) w —R 2 —(CH 2 ) x —R 3 —(CH 2 ) y —R 4 —(CH 2 ) z —NH, wherein R 2 , R 3 , and R 4 are independently selected from the group comprising O and NH, in which u is a whole number from 1 to 10, w is a whole number from 1 to 5, x is a whole number from 2 to 5, y is a whole number from 2 to 5, and z is a whole number from 2 to 6; and b) substituents R 5 , R 6 , and R 7 on the 4, 5′, and 8 carbon atoms respectively, independently selected from the group comprising H and (CH 2 ) v CH 3 , where v is a whole number from 0 to 5; or a salt thereof. Alternatively, the present invention contemplates embodiments of the method of inactivation, wherein the compound is a 5′-primaryamino-substituted psoralen comprising: a) a substituent R 1 on the 5′ carbon atom, selected from the group comprising: —(CH 2 ) u —NH 2 , —(CH 2 ) w —R 2 —(CH 2 ) z —NH 2 , —(CH 2 ) w —R 2 —(CH 2 ) x —R 3 —(CH 2 ) z —NH 2 , and —(CH 2 ) w —R 2 —(CH 2 ) x —R 3 —(CH 2 ) y —R 4 —(CH 2 ) z —NH 2 ; wherein R 2 , R 3 , and R 4 are independently selected from the group comprising O and NH, and in which u is a whole number from 1 to 10, w is a whole number from 1 to 5, x is a whole number from 2 to 5, y is a whole number from 2 to 5, and z is a whole number from 2 to 6; and, b) substituents R 5 , R 6 , and R 7 on the 4, 4′, and 8 carbon atoms respectively, independently selected from the group comprising H and (CH 2 ) v CH 3 , where v is a whole number from 0 to 5, and where when R 1 is selected from the group comprising —(CH 2 ) u —NH 2 , R 6 is H; or a salt thereof. Alternatively, the present invention contemplates embodiments of the method of inactivation, wherein the compound is a 5′-primaryamino-substituted psoralen comprising: a) a substituent R 1 on the 5′ carbon atom, selected from the group comprising: —(CH 2 ) u —NH 2 , —(CH 2 ) w —R 2 —(CH 2 ) z —NH 2 , —(CH 2 ) w —R 2 —(CH 2 ) x —R 3 —(CH 2 ) z —NH 2 , and —(CH 2 ) w —R 2 —(CH 2 ) x —R 3 —(CH 2 ) y —R 4 —(CH 2 ) z —NH 2 ; wherein R 2 , R 3 , and R 4 are independently selected from the group comprising O and NH, and in which u is a whole number from 3 to 10, w is a whole number from 1 to 5, x is a whole number from 2 to 5, y is a whole number from 2 to 5, and z is a whole number from 2 to 6; and, b) substituents R 5 , R 6 , and R 7 on the 4, 4′, and 8 carbon atoms respectively, independently selected from the group comprising H and (CH 2 ) v CH 3 where v is a whole number from 0 to 5; or a salt thereof. In one embodiment of the method of inactivation, at least two of the compounds are present. The present invention contemplates embodiments where the compound is introduced either in solution, such as water, saline, or a synthetic media, or in a dry formulation. The present invention also contemplates that the nucleic acid may be DNA or RNA, single stranded or double stranded. DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of one embodiment of the device of the present invention. FIG. 2 is a cross-sectional view of the device shown in FIG. 1 along the lines of 2 — 2 . FIG. 3 is a cross-sectional view of the device shown in FIG. 1 along the lines of 3 — 3 . FIG. 4 is a cross-sectional view of the device shown in FIG. 1 along the lines of 4 — 4 . FIG. 5A is a diagram of the-synthesis pathways and chemical structures of compounds 8 , 13 , and 14 of the present invention. FIG. 5B is a diagram of the synthesis pathways and chemical structures of compounds 2 , 4 , and 7 of the present invention. FIG. 5C is a diagram of the synthesis pathways and chemical structures of compounds 1 , 5 , 6 , 9 , and 10 of the present invention. FIG. 5D is a diagram of the synthesis pathways and chemical structures of compounds 12 and 15 of the present invention. FIG. 5E is a diagram of a synthesis pathways and the chemical structure of compound 3 of the present invention. FIG. 5F is al diagram of a synthesis pathways and the chemical structure of compounds 16 and 17 of the present invention. FIG. 6 shows the impact of concentration on the log kill of R17 when Compounds 1-3 of the present invention are photoactivated. FIG. 7 shows the impact of concentration on the log kill of R17 when Compounds 3-6 of the present invention are photoactivated. FIG. 8 shows the impact of concentration on the log kill of R17 when Compounds 2 and 6 of the present invention are photoactivated. FIG. 9 shows the impact of concentration on the log kill of R17 when Compounds 6 and 18 of the present invention are photoactivated. FIG. 10 shows the impact of concentration on the log kill of R17 when Compound 16 of the present invention is photoactivated. FIG. 11 shows the impact of varying Joules of irradiation on the log titer of R17 for Compound 6 of the present invention. FIG. 12 shows the impact of varying Joules of irradiation on the log titer of R17 for Compounds 7, 9 and 10 of the present invention. FIG. 13 shows the impact of varying Joules of irradiation on the log titer of R17 for Compounds 7 and 12 of the present invention. FIG. 14 shows the impact of varying Joules of irradiation on the log titer of R17 for Compound 15 of the present invention. FIG. 15 shows the impact of varying Joules of irradiation on the log titer of R17 for Compound 17 of the present invention. FIG. 16 shows the impact of varying Joules of irradiation on the log titer of R17 for Compounds 6 and 17 of the present invention. FIG. 17 shows the impact of varying Joules of irradiation on the log titer of R17 for Compounds 6 and 15 of the present invention. FIG. 18 shows the effect of varying the concentration of Compounds 2 and 6 of the present invention, in plasma. FIG. 19 shows the effect of varying the concentration of Compounds 2 and 6 of the present invention, in synthetic medium. FIG. 20A schematically shows the standard blood product separation approach used presently in blood banks. FIG. 20B schematically shows an embodiment of the present invention whereby synthetic media is introduced to platelet concentrate prepared as in FIG. 20 A. FIG. 20C schematically shows one embodiment of the decontamination approach of the present invention applied specifically to platelet concentrate diluted with synthetic media as in FIG. 20 B. DESCRIPTION OF THE INVENTION The present invention provides new psoralens and methods of synthesis of new psoralens having enhanced ability to inactivate pathogens in the presence of ultraviolet light, which is not linked to mutagenicity. The new psoralens are effective against a wide variety of pathogens. The present invention also provides methods of using new and known compounds to inactivate pathogens in health related products to be used in vivo and in vitro, and in particular, blood products. The inactivation methods of the present invention provide methods of inactivating pathogens, and in particular, viruses, in blood products prior to use in vitro or in vivo. In contrast with previous approaches, the method requires only short irradiation times and there is no need to limit the concentration of molecular oxygen. The description of the invention is divided into the following sections: I) Photoactivation Devices, II) Compound Synthesis, III) Binding of Compounds to Nucleic Acid, IV) Inactivation of Contaminants, and V) Preservation of Biochemical Properties of Material Treated. I. Photoactivation Devices The present invention contemplates devices and methods for photoactivation and specifically, for photoactivation of photoreactive nucleic acid binding compounds. The present invention contemplates devices having an inexpensive source of electromagnetic radiation that is integrated into a unit. In general, the present invention contemplates a photoactivation device for treating photoreactive compounds, comprising: a) means for providing appropriate wavelengths of electromagnetic radiation to cause photoactivation of at least one photoreactive compound; b) means for supporting a plurality of samples in a fixed relationship with the radiation providing means during photoactivation; and c) means for maintaining the temperature of the samples within a desired temperature range during photoactivation. The present invention also contemplates methods, comprising: a) supporting a plurality of sample containers, containing one or more photoreactive compounds, in a fixed relationship with a fluorescent source of electromagnetic radiation; b) irradiating the plurality of sample containers simultaneously with electromagnetic radiation to cause photoactivation of at least one photoreactive compound; and c) maintaining the temperature of the sample within a desired temperature range during photoactivation. The major features of one embodiment of the device of the present invention involve: A) an inexpensive source of ultraviolet radiation in a fixed relationship with the means for supporting the sample containers, B) rapid photoactivation, C) large sample processing, D) temperature control of the irradiated samples, and E) inherent safety. A. Electromagnetic Radiation Source Many sources of ultraviolet radiation can be successfully used in decontamination protocols with psoralens. For example, some groups have irradiated sample from above and below by General Electric type F20T12-BLB fluorescent UVA. bulbs with an electric fan blowing gently across the lights to cool the area Alter, H. J., et al., The Lancet , 24:1446 (1988). Another group used Type A405-TLGW/05 long wavelength ultraviolet lamp manufactured by P. W. Allen Co., London placed above the virus samples in direct contact with the covers of petri dishes containing the samples, and was run at room temperature. The total intensity delivered to the samples under these conditions was 1.3×10 15 photons/sec cm 2 or 0.7 mW/cm 2 in the petri dish. Hearst. J. E., and Thiry, L., Nucleic Acids Research, 4:1339 (1977). However, without intending to be limited to any type of photoactivation device, the present invention contemplates several preferred arrangements for the photoactivation device as follows. A preferred photoactivation device of the present invention has an inexpensive source of ultraviolet radiation in a fixed relationship with the means for supporting the sample vessels. Ultraviolet radiation is a form of energy that occupies a portion of the electromagnetic radiation spectrum (the electromagnetic radiation spectrum ranges from cosmic rays to radio waves). Ultraviolet radiation can come from many natural and artificial sources. Depending on the source of ultraviolet radiation, it may be accompanied by other (non-ultraviolet) types of electromagnetic radiation (e.g., visible light). Particular types of ultraviolet radiation are herein described in terms of ti wavelength. Wavelength is herein described in terms of nanometers (“nm”; 10 −9 meters). For purposes herein, ultraviolet radiation extends from approximately 180 nm to 400 nm. When a radiation source, by virtue of filters or other means, does not allow radiation below a particular wavelength (e.g., 320 nm), it is said to have a low end “cutoff” at that wavelength (e.g, “a wavelength cutoff at 300 nanometers”). Similarly, when a radiation source allows only radiation below a particular wavelength (e.g., 360 nm), it is said to have a high end “cutoff” at that wavelength (e.g., “a wavelength cutoff at 360 nanometers”). For any photochemical reaction it is desired to eliminate or least minimize any deleterious side reactions. Some of these side reactions can be caused by the excitation of endogenous chromophores that may be present during the photoactivation procedure. In a system where only nucleic acid and psoralen are present, the endogenous chromophores are the nucleic acid bases themselves. Restricting the photoactivation process to wavelengths greater than 320 nm minimizes direct nucleic acid damage since there is very little absorption by nucleic acids above 313 nm. In human serum or plasma, for example, the nucleic acid is typically present together with additional biological constituent. If the biological fluid is just protein, the 320 nm cutoff will be adequate for minimizing side reactions (aromatic amino acids (to not absorb above 320 nm). If the biological fluid includes other analytes, there may be constituents that are sensitive to particular wavelengths of light. In view of the presence of these endogenous constituents, it is intended that the device of the present invention be designed to allow for irradiation within a small range of specific and desirable wavelengths, and thus avoid damage blood components. The preferred range of desirable wavelengths is between 320 and 350 nm. Some selectivity can be achieved by choice of commercial irradiation sources. For example, while typical fluorescent tubes emit wavelengths ranging from 300 nm to above 400 nm (with a broad peak centered around 360 nm), BLB type fluorescent lamps are designed to remove wavelengths above 400 nm. This, however, only provides an upper end cutoff. In a preferred embodiment, the device of the present invention comprises an additional filtering means. In one embodiment, the filtering means comprises a glass cut-off filter, such as a piece of Cobalt glass. In another embodiment, the filtering means comprises a liquid filter solution that transmits only a specific region of the electromagnetic spectrum, such as an aqueous solution of Co(No3)2. This salt solution yields a transmission window of 320-400 nm. In a preferred embodiment, the aqueous solution of Co(No3)2 is used in combination with NiSO4 to remove the 365 nm component of the emission spectrum of the fluorescent or are source employed. The Co—Ni solution preserves its initial transmission remarkably well even after tens of hours of exposure to the direct light of high energy sources. It is not intended that the present invention be limited by the particular filter employed. Several inorganic salts and glasses satisfy the necessary requirements. For example, cupric sulfate is a most useful general filter for removing the infra-red, when only the ultraviolet is to be isolated. Its stability in intense sources is quite good. Other salts are known to one skilled in the art. Aperture or reflector lamps may also be used to achieve specific wavelengths and intensities. When ultraviolet radiation is herein described in terms of irradiation, it is expressed in terms of intensity flux (milliwatts per square centimeter or “mW cm-2”). “Output” is herein defined to encompass both the emission of radiation (yes or no; on or off) as well as the level of irradiation. In a preferred embodiment, intensity is monitored at 4 locations: 2 for each side of the plane of irradiation. A preferred source of ultraviolet radiation is a fluorescent source. Fluorescence is a special case of luminescence. Luminescence involves the absorption of electromagnetic radiation by a substance and the conversion of the energy into radiation of a different wavelength. With fluorescence, the substance that is excited by the electromagnetic radiation returns to its ground state by emitting a quantum of electromagnetic radiation. While fluorescent sources have heretofore been thought to be of too low intensity to be useful for photoactivation, in one embodiment the present invention employs fluorescent sources to achieve results thus far achievable on only expensive equipment. As used here, fixed relationship is defined as comprising a fixed distance and geometry between the sample and the light source during the sample irradiation. Distance relates to the distance between the source and the sample as it is supported. It is known that light intensity from a point source is inversely related to the square of the distance from the point source. Thus, small changes in the distance from the source can have a drastic impact on intensity. Since changes in intensity can impact photoactivation results, changes in distance are avoided in the devices of the present invention. This provides reproducibility and repeatability. Geometry relates to the positioning of the light source. For example, it can be imagined that light sources could be placed around the sample holder in many ways (on the sides, on the bottom, in a circle; etc.). The geometry used in a preferred embodiment of the present invention allows for uniform light exposure of appropriate intensity for rapid photoactivation. The geometry of a preferred device of the present invention involves multiple sources of linear lamps as opposed to single point sources. In addition, there are several reflective surfaces and several absorptive surfaces. Because of this complicated geometry, changes in the location or number of the lamps relative to the position of the samples to be irradiated are to be avoided in that such changes will result in intensity changes. B. Rapid Photoactivation The light source of the preferred embodiment of the present invention allows for rapid photoactivation. The intensity characteristics of the irradiation device have been selected to be convenient with the anticipation that many sets of multiple samples may need to be processed. With this anticipation, a fifteen minute exposure time or less is a practical goal. In designing the devices of the present invention, relative position of the elements of the preferred device have been optimized to allow for fifteen minutes of irradiation time, so that, when measured for the wavelengths between 320 and 350 nanometers, an intensity flux, greater than approximately 1 mW cm-2 is provided to the sample vessels. C. Processing of Large Numbers of Samples As noted, another important feature of the photoactivation devices of the present invention is that they provide for the processing of large numbers of samples. In this regard, one element of the devices of the present invention is a means for supporting a plurality of sample containers. In the preferred embodiment of the present invention the supporting means comprises a tube rack placed between two banks of lights. By accepting commonly used commercially available tubes, the device of the present invention allows for convenient processing of large numbers of samples. D. Temperature Control As noted, one of the important features of the photoactivation devices of the present invention is temperature control. Temperature control is important because the temperature of the sample in the sample at the time of exposure to light can dramatically impact the results. For example, conditions that promote secondary structure in nucleic acids also enhance the affinity constants of many psoralen derivatives for nucleic acids. Hyde and Hearst, Biochemistry, 17, 1251 (1978). These conditions are a mix of both solvent composition and temperature. With single stranded 5S ribosomal RNA, irradiation at low temperatures enhances the covalent addition of HMT to 5S rRNA by two told at 4° C. compared to 20° C. Thompson et al., J. Mol. Biol . 147:417 (1981). Even further temperature induced enhancements of psoralen binding have been reported with synthetic polynucleotides. Thompson et al., Biochemistry 21:1363 (1982). E. Inherent Safety Ultraviolet radiation can cause severe burns. Depending on the nature of the exposure, it may also be carcinogenic. The light source of a preferred embodiment of the present invention is shielded from the user. This is in contrast to the commercial hand-held ultraviolet sources as well as the large, high intensity sources. In a preferred embodiment, the irradiation source is contained within a housing made of material that obstructs the transmission of radiant energy (i.e., an opaque housing). No irradiation is allowed to pass to the user. This allows for inherent safety for the user. II. Compound Synthesis A. Photoactivation Compounds in General “Photoactivation compounds” (or “photoreactive compounds”) defines a family of compounds that undergo chemical change in response to electromagnetic radiation. Table 1 is a partial list of photoactivation compounds. TABLE 1 Photoactivation Compounds Actinomycins Anthracyclinones Anthramycin Benzodipyrones Fluorenes And Fluorenones Furocoumarins Mitomycin Monostral Fast Blue Norphillin A Many Organic Dyes Not Specifically Listed Phenanthridines Phenazathionium Salts Phenazines Phenothiazines Phenylazides Quinolines Thiaxanthenones The species of photoreactive compounds described herein is commonly referred to as the furocoumarins. In particular, the present invention contemplates those compounds described as psoralens: [7H-furo(3,2-g)-(1)-benzopyran-7-one, or b-lactone of 6-hydroxy-5-benzofuranacrylic acid], which are linear: and in which the two oxygen residues appended to the central aromatic moiety have a 1, 3 orientation, and further in which the furan ring moiety is linked to the 6 position of the two ring coumarin system. Psoralen derivatives are derived from substitution of the linear furocoumarin at the 3, 4, 5, 8, 4′, or 5′ positions. 8-Methoxypsoralen (known in the literature under various named, e.g., xanthotoxin, methoxsalen, 8-MOP) is a naturally occuring psoralen with relatively low photoactivated binding to nucleic acids and low mutagenicity in the Ames assay, described in the following experimental section. 4′-Aminomethyl-4,5′,8-trimethylpsoralen (AMT) is one of most reactive nucleic acid binding psoralen derivatives, providing up to 1. AMT adduct per 3.5 DNA base pairs. S. T. Isaacs, G. Wiesehahn and L. M. Hallick, NCI Monograph 66:21 (1984). However, AMT also exhibits significant levels of mutagenicity. A new group of psoralens was desired which would have the best characteristics of both. 8-MOP and AMT: low mutagenicity and high nucleic acid binding affinity, to ensure safe and thorough inactivation of pathogens. The compounds of the present invention were designed to be such compounds. “4′-primaryamino-substituted psoralens” are defined as psoralen compounds which have an NH 2 group linked to the 4′-position of the psoralen by a hydrocarbon chain having a total length of 2 to 20 carbons, where 0 to 6 of those carbons are independently replaced by NH or O, and each point of replacement is separated from each other point of replacement by at least two carbons, and is separated from the psoralen by at least one carbon. “5′-primaryamino-substituted psoralens” are defined as psoralen compounds which have an NH 2 group linked to the 5′-position of the psoralen by a hydrocarbon chain having a total length of 1 to 20 carbons, where 0 to 6 of those carbons are independently replaced by NH or O, and each point of replacement is separated from each other point of replacement by at least two carbons, and is separated from the psoralen by at least one carbon. B. Synthesis of the Psoralens The present invention contemplates synthesis methods for the novel compounds of the present invention. Several specific examples of the schemes discussed in this section are shown in FIGS. 5A-5F. For ease of reference, the compounds in these figures have been numbered from Compound 1 to Compound 17. For the subclass of the linear psoralens, 4,5′,8-trialkylpsoralens can be made as follows. The 4,8-dialkylcoumarins are prepared from 2-alkylresorcinols and a 3-oxoalkanoate ester by the Pechmann reaction (Organic Reactions Vol VII, Chap 1, ed. Adams et al., Wiley, N.Y., 1953)). The hydroxy group is treated with an allylating reagent, CH 2 ═CHX—CH(R 8 )—Y, where X is a halide or hydrogen, Y is a halide or sulfonate, and R 8 is H or (CH 2) v CH 3 , where v is a whole number from 0 to 4. Claisen rearrangement of the resultant allyl ether gives 4,8-dialkyl-6-allyl-7-hydroxycoumarin. The coumarins are converted to the 4,5′,8-trialkylpsoralens using one of the procedures previously described (i.e., see, Bender et al., J. Org. Chem . 44:2176 (1979); Kaufman, U.S. Pat. Nos. 4,235,781 and 4,216,154, hereby incorporated by reference). 4,5′,8-Trimethylpsoralen is a natural product and is commercially available (Aldrich Chemical Co., Milwaukee, Wis.). Halomethylation of the 4,5′,8-trialkylpsoralens with chloromethyl methyl ether or bromomethyl methyl ether is described in U.S. Pat. No. 4,124,598, to Hearst. Longer chain 4′-(w-haloalkyl)psoralens (herein referred to as 4′-HATP) where alkyl is (CH 2 ) 2 to (CH 2) 10 can be prepared under Freidel-Crafts conditions as discussed elsewhere (Olah and Kuhn, J. Org. Chem ., 1964, 29, 2317; Friedel-Crafts and Related Reactions, Vol. II, Part 2, Olah, ed., Interscience, NY, 1964, p 749). While reactions of these halomethyl- intermediates with amines (Hearst et al., U.S. Pat. No. 4,124,598, and alcohols (Kaufman, U.S. Pat. No. 4,269,852) have been described, there are no literature reports on the formation of extended chain primary amines, especially those in which the terminal amine is linked to the psoralen by a bridge containing one or more oxygen or nitrogen atoms. Further, the properties of the latter materials, such as decreased mutagenicity are unexpected based on what is known about previously prepared compounds, such as AMT. Starting from the 4′-HATP, reaction with an excess of a bis-hydroxy compound, HO—(B)—OH, where B is either an alkyl chain (e.g., HO—(B)—OH is 1,3-propanediol) or a monoether (e.g., diethylene glycol) or a polyether (e.g., tetraethylene glycol), either neat or with a solvent such as acetone at 20-80° C., and a base for the carbon chains longer than halomethyl, gives compound I. The terminal hydroxy group of compound 1 can be transformed to an amino group under a variety of conditions (for example see Larock; “Comprehensive Organic Transformations”,VCH Publishers, NY, 1989). Particularly, the hydroxy group can be converted to the ester of methanesulfonic acid (structure II). This can subsequently be converted to the azide in refluxing ethanol and the azide reduced to the final amine structure III. The method described herein utilizes triphenylphosphine and water in THF for the reduction but other methods are contemplated. Conversely, compound II can be reacted with diamines, H2N—(B′)—NH2 (IV) where B′ is an alkyl chain (e.g., 1,4,-butanediamine), a monoether (e.g., 3-oxo-1,5-pentanediamine) or a polyether (e.g., 3,6-dioxa-1,8-octanediamine) to give the final product, compound V. This reaction is carried out with an excess of diamine in acetonitrile at reflux, but other solvents and temperatures are equally possible. It is recognized that alternate preparations for structures III and V are possible, for example where a linear primary alcohol is prepared which already contains the amines in a protected form and subsequently reacted with 4′-HATP in the presence of a suitable base. Some final compounds are desired which contain an NH group in the carbon chain between the primary amino group and the psoralen ring. When the linkage between this nitrogen and the terminating nitrogen contains only CH 2 subunits and oxygen but no other nitrogens (structure VI), the product can conveniently be prepared from the (haloalkyl)psoralen and the appropriate diamine of structure IV. This method is also applicable to final products that contain more than two nitrogens in the chain (structure IX) starting from polyamines of structure VIII (e.g., norspermidine or spermine [commercially available from Aldrich, Milwaukee, Wis.]), however, in this case isomeric structures are also formed in considerable amounts. The more preferred method for the preparation of structure IX is reductive amination of the psoralen-4′-alkanal. (VII) with a polyamine of structure VIII and a reducing agent such as sodium cyanoborohydride. This reductive amination is applicable to the synthesis of compounds VI as well. The carboxaldehydes (structure VII, n=0) are known (Isaacs et al., J. Labelled Cmpds. Radiopharm ., 1982, 19, 345) and other members of this group can be prepared from the 4′-HATP compounds by conversion of the terminal halo group to an aldehyde functionality (for example, Durst, Adv. Org. Chem. 6:285 (1969)). Other final products have a terminal amine linked to the psoralen by an alkyl chain. These are prepared either by reaction of the 4′-HATP with potassium phthalimide and subsequent liberation of the desired amine with hydrazine, or conversion of the 4′-HATP to the cyanide compound, followed by reduction, for example with NaBH 4 —CF 3 CO 2 H. The discussion of the conversion of 4,5′,8-trialkylpsoralens to 4′-aminofunctionalized-4,5′,8-trialkylpsoralens applies equally well when the 4- and/or 8-position is substituted with only a hydrogen, thus providing 4′-primaryamino-substituted-5′, (4 or 8)- dialkylpsoralens and 4′-primaryamino-substituted-5′-alkylpsoralens. The 4,4′,8-trialkylpsoralens can be prepared in two steps starting from the 4,8-dialkyl-7-hydroxycoumarins discussed above. The coumarin is treated with an a-chloro ketone under basic conditions to give the 4,8-dialkyl-7-(2-oxoalkoxy)coumarin. Cyclization of this intermediate to the 4,4′,8-trialkylcoumarin occurs by heating in aqueous base. Under identical conditions to those described above for introducing a primaryamino-substituted side chain, the 4,4′,8-trialkylpsoralens can be converted to the 5′-(w-haloalkyl)-4,4′,8′trialkylpsoralens, (herein called 5′-HATP), (Kaufman, U.S. Pat. No. 4,294,822 and U.S. Pat. No. 4,298,614). Again, this formation of extended-chain primary amines in which the terminal amine is linked to the psoralen by a bridge containing one or more oxygen or nitrogen atoms is a novel approach. The discussion of the conversion of 4,4′,8-trialkylpsoraleis to 5′-primaryamino-substituted-4,4′,8-trialkylpsoralens applies equally well when the 4- and/or 8-position is just substituted with a hydrogen, thus providing 5′-primaryamino-substituted-4′, (4 or 8)- dialkylpsoralents and 5′-primaryamino-substituted-4′-alkylpsoralens. Referring back to the synthesis of 4′ (or 5′)-halomethyl-4, 5′ (or 4′),8-trialkyl psoralens, the preparation of these critical intermediates in the synthesis of several compounds presents difficult challenges. The known method of preparation involves treatment of the starting psoralen with 50-200 equivalents of highly toxic, and volatile chloromethyl methyl ether or bromomethyl methyl ether. Yields of only 30-60% of the desired intermediate are obtained. Described herein, is a much improved procedure which allows for the synthesis of either isomer of the bromomethyl-trialkylpsoralens by careful control of reaction conditions. Reaction of the 4,8-dialkyl-7-hydroxycoumarin with 2-chloro-3-butanone under typical basic conditions, provides 4,8-dialkyl-7-(1-methyl-2-oxopropyloxy)coumarin (XV). This material is heated in aqueous NaOH to provide 4,8-dialkyl-4′,5′-dimethylpsoralen (XVI). The tetrasubstituted psoralen and N-bromosuccinimide are then refluxed in a solvent, preferably with a catalyst such as benzoyl peroxide. If the solvent used is carbon tetrachloride, 4,8-dialkyl-5′-bromomethyl-4′-methylpsoralen (XVIII) is obtained in greater than 66% yield. If methylene chloride is used, only 4,8-dialkyl-4′-bromomethyl-5′-methylpsoralen (XVII) is obtained in ≧80% yield. Benzylic bromination in other solvents can also be done, generating one of the isomeric products alone or in a mixture. These solvents include, but are not limited to, chloroform, bromotrichloromethane and benzene. The discussion above of the syntheses of 4′-primaryamino- and 5′-primaryamino-psoralens can be extended to the non-linear coumarins, specifically the isopsoralens or angelicins. Thus, the 4′-chloromethylangelicins (IXX) and the 5′-chloromethylangelicins (XX) can be prepared in a similar manner to their linear counterparts. By analogy with the synthetic pathways presented above one can envision the synthesis of 4′-(w-amino)alkylangelicins and 5′-(w-amino)alkylangelicins where the alkyl linkage can contain one or more oxygen or nitrogen atoms. III. Binding of Compounds to Nucleic Acid The present invention contemplates binding new and known compounds to nucleic acid, including (but not limited to) viral nucleic acid and bacterial nucleic acid. One approach of the present invention to binding photoactivation compounds to nucleic acid is photobinding. Photobinding is defined as the binding of photobinding compounds in the presence of photoactivating wavelengths of light. Photobinding compounds are compounds that bind to nucleic acid in the presence of photoactivating wavelengths of light. The present invention contemplates methods of photobinding with photobinding compounds of the present invention. One embodiment of the method of the present invention for photobinding involves the steps: a) providing a photobinding compound of the present invention; and b) mixing the photobinding compound with nucleic acid in the presence of photoactivation wavelengths of electromagnetic radiation. The invention further contemplates a method for modifying nucleic acid, comprising the steps: a) providing photobinding compound of the present invention and nucleic acid; and b) photobinding the photobinding compound to the nucleic acid, so that a compound:nucleic acid complex is formed. IV. Inactivation of Pathogens The present invention contemplates treating a blood product with a photoactivation compound and irradiating to inactivate contaminating pathogen nucleic acid sequences before using the blood product. A. Inactivation in General The term “inactivation” is here defined as the altering of the nucleic acid of a unit of pathogen so as to render the unit of pathogen incapable of replication. This is distinct from “total inactivation”, where all pathogen units present in a given sample are rendered incapable of replication, or “substantial inactivation,” where most of the pathogen units present are rendered incapable of replication. “Inactivation efficiency” of a compound is defined as the level of inactivation the compound can achieve at a given concentration of compound or dose of irradiation. For example, if 100 μM of a hypothetical compound X inactivated 5 logs of HIV virus whereas under the same experimental conditions, the same concentration of compound Y inactivated only 1 log of virus, then compound X would have a better “inactivation efficiency” than compound Y. To appreciate that an “inactivation” method may or may not achieve “total inactivation,” it is useful to consider a specific example. A bacterial culture is said to be inactivated if an aliquot of the culture, when transferred to a fresh culture plate and permitted to grow, is undetectable after a certain time period. A minimal number of viable bacteria must be applied to the plate for a signal to be detectable. With the optimum detection method, this minimal number is 1 bacterial cell. With a suboptimal detection method, the minimal number of bacterial cells applied so that a signal is observed may be much greater than 1. The detection method determines a “threshold” below which the “inactivation method” appears to be completely effective (and above which “inactivation” is, in fact, only partially effective). B. Inactivation of Potential Pathogens The same considerations of detection method and threshold are present when determining the sensitivity limit of an inactivation method for nucleic acid. Again, by “inactivation” it is meant that a unit of pathogen is rendered incapable of replication. In the case of inactivation methods for material to be used by humans, whether in vivo or in vitro, the detection method can theoretically be taken to be the measurement of the level of infection with a disease as a result of exposure to the material. The threshold below which the inactivation method is complete is then taken to be the level of inactivation which is sufficient to prevent disease from occuring due to contact with the material. It is recognized that in this practical scenario, it is not essential that the methods of the present invention result in “total inactivation”. That is to say, “substantial inactivation” will be adequate as long as the viable portion is insufficient to cause disease. The inactivation method of the present invention renders nucleic acid in pathogens substantially inactivated. In one embodiment, the inactivation method renders pathogen nucleic acid in blood preparations substantially inactivated. Without intending to be limited to any method by which the compounds of the to present invention inactivate pathogens, it is believed that inactivation results from light induced binding of psoralens to pathogen nucleic acid. Further, while it is not intended that the inactivation method of the present invention be limited by the nature of the nucleic acid; it is contemplated that the inactivation method render all forms of nucleic acid (whether DNA, mRNA, etc.) substantially inactivated. In the case of photoactivation compounds modifying nucleic acid, it is preferred that interaction of the pathogen nucleic acid (whether DNA, mRNA, etc.) with the photoactivation compound causes the pathogen to be unable to replicate, such that, should a human be exposed to the treated pathogen, infection will not result. “Synthetic media” is herein defined as an aqueous synthetic blood or blood product storage media. In one embodiment, the present invention contemplates inactivating blood products in synthetic media. This method reduces harm to blood products and permits the use of much lower concentrations of photoactivation compounds. The psoralen photoinactivation method inactivates nucleic acid based pathogens present in blood through a single procedure. Thus, it has the potential to eliminate bacteria, protozoa, and viruses as well. Had an effective decontamination method been available prior to the advent of the AIDS pandemic, no transfusion associated HIV transmission would have occurred. Psoralen-based decontamination has the potential to eliminate all infectious agents from the blood supply, regardless of the pathogen involved. Additionally, psoralen-based decontamination has the ability to sterilize blood products after collection and processing, which in the case of platelet concentrates could solve the problem of low level bacterial contamination and result in extended storage life. Morrow J. F., et al., JAMA 266:555-558 (1991); Bertolini F., et al, Transfusion 32:152-156 (1992). TABLE 2 Viruses Photochemically Inactivated by Psoralens Family Virus Adeno Adenovirus 2 Canine Hepatitis Arena Pichinde Lassa Bunya Turlock California Encephalitis Herpes Herpes Simplex 1 Herpes Simplex 2 Cytomegalovirus Pseudorabies Orothomyxo Influenza Papova SV-40 Paramyxo Measles Mumps Parainfluenza 2 and 3 Picorna 1 Poliovirus 1 and 2 Coxsackie A-9 Echo 11 Pox Vaccinia Fowl Pox Reo Reovirus 3 Blue Tongue Colorado Tick Fever HIV Retro Avian Sarcoma Murine Sarcome Murine Leukemia Rhabdo Vesticular Stomatitis Virus Toga Western Equine Encephalitis Dengue 2 Dengue 4 St. Louis Encephalitis Hepadna Hepatitis B Bacteriophage Lambda T2 (Rickettsia) R. Akari (Rickettsialpox) 1 In the article, it was pointed out that Piconaviruses were photoinactivated only if psoralens were present during virus growth. A list of viruses which have been photochemically inactivated by one or more psoralen derivatives appears in Table 2. (From Table 1 of Hanson, C. V., Blood Cells 18:7 (1992)). This list is not exhaustive, and is merely representative of the great variety of pathogens psoralens can inactivate. The present invention contemplates the inactivation of these and other viruses by the compounds described herein. The compounds of the present invention are particularly well suited for inactivating envelope viruses, such as the HIV virus. C. Selecting Photoctivation Compounds for Inactivation of Pathogens In order to evaluate a compound to decide if it would be useful in the methods of the present invention, two important properties should be considered: the compound's ability to inactivate pathogens and its mutagenicity. The ability of a compound to inactivate pathogens may be determined by several methods. One technique is to perform a bacteriophage screen; an assay which determines nucleic acid binding of test compounds. A screen of this type, an R17 screen, is described in detail in EXAMPLE 9, below. Another technique is to perform a viral screen, as shown in detail in EXAMPLE 10 or HIV, and EXAMPLE 11 for Duck Hepatitis B Virus. The R17 bacteriophage screen is believed to be predictive of HIV inactivation efficiency, as well as the efficiency of compounds against many other viruses. R17 was chosen because it was expected to be a very difficult pathogen to inactivate. It is a small, single stranded RNA phage. Without intending to be limited to any means by which the present invention operates, it is expected that shorter pieces of nucleic acid are harder to inactivate because they require a higher frequency of formation of psoralen adducts than do longer pieces of nucleic acid. Further, single stranded RNA pathogens are more difficult to inactivate because psoralens can neither intercalate between base pairs, as with double-stranded nucleic acids, nor form diadducts which function as interstrand crosslinks. Thus it is expected that when inactivation of R17 is achieved, these same conditions will cause the inactivation of many viruses and bacteria. The second property that is important in testing a compound for use in methods it of the present invention is mutagenicity. The most widely used mutagen/carcinogen screening assay is the Ames test. This assay is described by D. M. Maron and B. N. Ames in Mutation Research 113:173 (1983). The Ames test utilizes several unique strains of Salmonella typhimurium that are histidine-dependent for growth and that lack the usual DNA repair enzymes. The frequency of normal mutations that render the bacteria independent of histidine (i.e., the frequency of spontaneous revertants) is low. Thus, the test can evaluate the impact of a compound on this revertant, frequency. Because some substances are not mutagenic by themselves, but are converted to a mutagen by metabolic action, the compound to be tested is mixed with the bacteria on agar plates along with the liver extract. The liver extract serves to mimic metabolic action in an animal. Control plates have only the bacteria and the extract. The mixtures are allowed to incubate. Growth of bacteria (if any) is checked by counting colonies. A positive Ames test is one where the number of colonies on the plates with mixtures containing the compound significantly exceeds the number on the corresponding control plates. When known carcinogens are screened in this manner with the Ames test, approximately ninety percent are positive. When known noncarcinogens are similarly tested, approximately ninety percent are negative. By performing these screens, a person skilled in the art can quickly determine which compounds would be appropriate for use in methods of the present invention. D. Delivery of Compounds for Photoinactivation The present invention contemplates several different formulations and routes by which the compounds described herein can be delivered in an inactivation method. This section is merely illustrative, and not intended to limit the invention to any form or method of introducing the compound. The compounds of the present invention may be introduced in an inactivation method in several forms. The compounds may be introduced as an aqueous solution in water, saline, a synthetic media such as “Sterilyte™”, or a variety of other solvents. The compounds can further be provided as dry formulations, with or without adjuvants. The new compounds may also be provided by many different routes. For example, the compound may be introduced to the reaction vessel, such as a blood bag, at the point of manufacture. Alternatively, the compound may be added to the material to be sterilized after the material has been placed in the reaction vessel. Further, the compounds may be introduced alone, or in a “cocktail” or mixture of several different compounds. V. Preservation of Biochemical Properties of Material Treated Psoralens are useful in inactivation procedures, because the reaction can be carried out at temperatures compatible with retaining biochemical properties of blood and blood products. Hanson, C. V., Blood Cells 18:7 (1992). The inactivation compounds and methods of the present invention are especially useful because they display the unlinking of pathogen inactivation efficiency from mutagenicity. The compounds exhibit powerful pathogenic inactivation without a concomitant rise in mutagenicity. The commonly known compounds tested in photoinactivation protocols, such as AMT, appear to exhibit a link between pathogen inactivation efficiency and mutagenetic action that until now seemed indivisible. While it is not intended that the present invention be limited to any theory by which pathogen inactivation efficiency is unlinked from mutagenicity, it is postulated that unlinking occurs as a result of the length of the groups substituted on the psoralen, and the location of charges on the compounds. It is postulated that positive charges on one or both ends of mutagenic compounds have non-covalent interactions with the phosphate backbone of DNA. These interactions are presumed to occur independents of the presence of light (called “dark binding”). In theory, the psoralen thereby sterically blocks polymerase from opening up the DNA, causing mutagenicity. In contrast, compounds of the present invention carry a positive or neutral charge on a long substitute group. These substituted groups form a steric barrier during dark binding that is much easier to free from the DNA, permitting polymerase to pass. Thus no mutagenicity results. EXPERIMENTAL The following examples serve to illustrate certain preferred embodiments and aspects of the present invention and are not to be construed as limiting the scope thereof. In the experimental disclosure which follows, the following abbreviations apply: eq (equivalents); M (Molar); μM (micromolar); N (Normal); mol (moles); mmol (millimoles); μmol (micromoles); nmol (nanomoles); g (grams); mg (milligrams); μg (micrograms); Kg (kilograms); L (liters); mL (milliliters); μL (microliters); cm (centimeters); mm (millimeters); μm (micrometers); nm (nanometers); J (Joules, note that in FIGS. 6, 8 - 17 , Joules or J refers to Joules/cm 2 ); ° C. (degrees Centigrade); TLC (Thin Layer Chromatography); EAA (ethyl-acetoacetate); EtOH (ethanol); HOAc (acetic acid); W (watts); mW (milliwatts); NMR (Nuclear Magnetic Resonance; spectra obtained at room temperature on a Varian Gemini 200 MHz Fourier Transform Spectrometer); m.p. (melting point); UV (ultraviolet light); THF (tetrahydrofuran); DMEM (Dulbecco's Modified Eagles Medium); FBS (fetal bovine serum); LB (Luria Broth); EDTA (ethelene diamine tetracidic acid). For ease of reference, some compounds of the present invention have been assigned a number from 1-17. The reference numbers are assigned in FIGS. 5A-5F and appear below the structure of each compound. These reference numbers are used throughout the experimental section. When isolating compounds of the present invention in the form of an acid addition salt, the acid is preferably selected so as to contain an anion which is non-toxic and pharmacologically acceptable, at least in usual therapeutic doses. Representative salts which are included in this preferred group are the hydrochlorides, hydrobromides, sulphates, acetates, phosphates, nitrates, methanesulphonates, ethanesulphonates, lactates, citrates, tartrates or bitartrates, and maleates. Other acids are likewise suitable and may be employed as desired. For example, fumaric, benzoic, ascorbic, succinic, salicylic, bismethylenesalicylic, propionic, gluconic, malic, malonic, mandelic, cinnamic, citraconic, stearic, palmitic, itaconic, glycolic, benzenesulphonic, and sulphamic acids may also be employed as acid addition salt-forming acids. In one of the examples below, phosphate buffered synthetic media is formulated for platelet treatment. This can be formulated in one step, resulting in a pH balanced solution (e.g., pH 7.2), by combining the following reagents in 2 liters of distilled water: Preparation of Sterilyte ™ 3.0 Formula W. mMolarity Grams/2 Liters Na Acetate * 3 H 2 O 136.08 20 5.443 Glucose 180.16 2 0.721 D-mannitol 182.17 20 7.287 KCl 74.56 4 0.596 NaCl 58.44 100 11.688 Na 3 Citrate 294.10 10 5.882 Na 2 HPO 4 * 7 H 2 O 268.07 14.46 7.752 Na 2 HPO 4 * H 2 O 137.99 5.54 1.529 MgCl 2 * 6 H 2 O 203.3 2 0.813 The solution is then mixed, sterile filtered (0.2 micron filter) and refrigerated. The Polymerase Chain Reaction (PCR) is used in one of the examples to measure whether viral inactivation by some compounds was complete. PCR is a method for increasing the concentration of a segment of a target sequence in a mixture of genomic DNA without cloning or purification. See K. B. Mullis et al., U.S. Pat. Nos. 4,683,195 and 4,683,202, hereby incorporated by reference. This process for amplifying the target sequence consists of introducing a large excess of two oligonucleotide primers to the DNA mixture containing the desired target sequence, followed by a precise sequence of thermal cycling in the presence of a DNA polymerase. The two primers are complementary to their respective strands of the double stranded target sequence. To effect amplification, the mixture is denatured and the primers then to annealed to their complementary sequences within the target molecule. Following annealing, the primers are extended with a polymerase so as to form a new pair of complementary strands. The steps of denaturation, primer annealing, and polymerase extension can be repeated many times (i.e., denaturation, annealing and extension constitute one “cycle”; there can be numerous “cycles”) to obtain a high concentration of an amplified segment of the desired target sequence. The length of the amplified segment of the desired target sequence is determined by the relative positions of the primers with respect to each other, and therefore, this length is a controllable parameter. By virtue of the repeating aspect of the process, the method is referred to by the inventors as the “Polymerase Chain Reaction”. Because the desired amplified segments of the target sequence become the predominant sequences (in terms of concentration) in the mixture, they are said to be “PCR amplified”. With PCR, it is possible to amplify a single copy of a specific target sequence in genomic DNA to a level detectable by several different methodologies (e.g., hybridization with a labelled probe; incorporation of biotinylated primers followed by avidin-enzyme conjugate detection; incorporation of 32 P labelled deoxynucleotide triphosphates, e.g., dCTP or dATP, into the amplified segment). In addition to genomic DNA, any oligonucleotide sequence can be amplified with the appropriate set of primer molecules. The PCR amplification process is known to reach a plateau concentration of specific target sequences of approximately 10 −8 M. A typical reaction volume is 100 μl, which corresponds to a yield of 6×10 −11 double stranded product molecules. PCR is a polynucleotide amplification protocol. The amplification factor that is observed is related to the number (n) of cycles of PCR that have occurred and the efficiency of replication at each cycle (E), which in turn is a function of the priming and extension efficiencies during each cycle. Amplification has been observed to follow the form E n , until high concentrations of PCR product are made. At these high concentrations (approximately 10 −8 M/l) the efficiency of replication falls off drastically. This is probably due to the displacement of the short oligonucleotide primers by the longer complementary strands of PCR product. At concentrations in excess of 10 −8 M, the rate of the two complementary PCR amplified product strands finding each other during the priming reactions become sufficiently fast that this occurs before or concomitant with the extension step of the PCR procedure. This ultimately leads to a reduced priming efficiency, and therefore, a reduced cycle efficiency. Continued cycles of PCR lead to declining increases of PCR product molecules. PCR product eventually reaches a plateau concentration. The sequences of the polynuclcotide primers used in this experimental section are as follows: DCD03: 5′ ACT AGA AAA CCT CGT GGA CT 3′ DCD05: 5′ GGG AGA GGG GAG CCC GCA CG 3′ DCD06: 5′ CAA TTT CGG GAA GGG CAC TC 3′ DCD07: 5′ GCT AGT ATT CCC CCG AAG GT 3′ With DCD03 as a common forward primer, the pairs generate amplicons of length 127, 327, and 1072 bp. These oligos were selected from regions that are absolutely conserved between 5 different dHBV isolates (DHBV1, DHBV3, DHBV16, DHBV22, and DHBV26) as well as from heron HBV (HHBV4). The following examples serve to illustrate certain preferred embodiments and aspects of the present invention and are not to be construed as limiting the scope thereof. EXAMPLE 1 As noted above, the present invention contemplates devices and methods for the photoactivation of photoreactive nucleic acid binding compounds. In this example, a photoactivation device is described for decontaminating blood products according to the method of the present invention. This device comprises: a) means for providing appropriate wavelengths of electromagnetic radiation to cause photoactivation of at least one photoreactive compound; b) means for supporting a plurality of blood products in a fixed relationship with the radiation providing means during photoactivation; and c) means for maintaining the temperature of the blood products within a desired temperature range during photoactivation. FIG. 1 is a perspective view of one embodiment of the device integrating the above-named features. The figure shows an opaque housing, ( 100 ) with a portion of it removed, containing an array) of bulbs ( 101 ) above and below a plurality of representative blood product containing means ( 102 ) placed between plate assemblies ( 103 , 104 ). The plate assemblies ( 103 , 104 ) are described more fully, subsequently. The bulbs ( 101 ), which are connectable to a power source (not shown), serve as a source of electromagnetic radiation. While not limited to the particular bulb type, the embodiment is configured to accept an industry standard, dual bipin lamp. The housing ( 100 ) can be opened via a latch ( 105 ) so that the blood product can be placed appropriately. As shown in FIG. 1, the housing ( 100 ), when closed, completely contains the irradiation from the bulbs ( 101 ). During irradiation, the user can confirm that the device is operating by looking through a safety viewport ( 106 ) which does not allow transmission of ultraviolet light to the user. The housing ( 100 ) also serves as a mount for several electronic components on a control board ( 107 ), including, by way of example, a main power switch, a count down timer, and an hour meter. For convenience, the power switch can be wired to the count down timer which in turn is wired in parallel to an hour meter and to the source of the electromagnetic radiation. The count down timer permits a user to preset the irradiation time to a desired level of exposure. The hour meter maintains a record of the total number of radiation hours that are provided by the source of electromagnetic radiation. This feature permits the bulbs ( 101 ) to be monitored and changed before their output diminishes below a minimum level necessary for rapid photoactivation. FIG. 2 is a cross-sectional view of the device shown in FIG. 1 along the lines of 2 — 2 . FIG. 2 shows the arrangement of the bulbs ( 101 ) with the housing ( 100 ) opened. A reflector ( 108 A, 108 B) completely surrounds each array of bulbs ( 101 ). Blood product containing means ( 102 ) are placed between upper ( 103 ) and lower ( 104 ) plate assemblies. Each plate assembly is comprised of an upper ( 103 A, 104 A) and lower ( 103 B, 1048 ) plates. The plate assemblies ( 103 , 104 ) are connected via a hinge ( 109 ) which is designed to accommodate the space created by the blood product containing means ( 102 ). The upper plate assembly ( 103 ) is brought to rest gently on top of the blood product containing means ( 102 ) supported by the lower plate ( 104 B) of the lower plate assembly ( 104 ). Detectors ( 110 A, 110 B, 110 C, 110 D) may be conveniently placed between the plates ( 103 A, 103 B, 104 A, 1048 ) of the plate assemblies ( 103 , 104 ). They can be wired to a printed circuit board ( 111 ) which in turn is wired to the control board ( 107 ). FIG. 3 is a cross-sectional view of the device shown in FIG. 1 along the lines of 3 — 3 . Six blood product containing means ( 102 ) (e.g., Teflon™ platelet unit bags) are placed in a fixed relationship above an array of bulbs ( 101 ). The temperature of the blood product can be controlled via a fan ( 112 ) alone or, more preferably, by employing a heat exchanger ( 113 ) having cooling inlet ( 114 ) and outlet ( 115 ) ports connected to a cooling source (not shown). FIG. 4 is a cross-sectional view of the device shown in FIG. 1 along the lines of 4 — 4 . FIG. 4 more clearly shows the temperature control approach of a preferred embodiment of the device. Upper plate assembly plates ( 103 A, 103 B) and lower plate assembly plates ( 104 A, 104 B) each create a temperature control chamber ( 103 C, 104 C), respectively. The fan ( 112 ) can circulate air within and between the chambers ( 103 C, 104 C). When the heat exchanger ( 113 ) is employed, the circulating air is cooled and passed between the plates ( 103 A, 103 B, 104 A, 1048 ). EXAMPLE 2 Synthesis of 4′-(4-Amino-2-Oxa)Butyl-4,5′,8-Trimethylpsoralen Hydrochloride (Compound 2) and Related Compounds (Compound 4) The preparation of 4′-chloromethyl-4,5′,8-trimethylpsoralen from commercially available 4,5′,8-trimethylpsoralen has been previously described. (U.S. Pat. No. 4,124,598; Isaacs et al., Biochem . 16:1058 (1977)). Reaction of the chloromethyl compound with alcohols (U.S. Pat. No. 4,124,598), pyridine (U.S. Pat. No. 4,169,204), glycol and aminoethanol (U.S. Pat. No. 4,269,852) have all been previously reported. However, compounds in which the 4′-position is substituted with a group, CH 2 —X—NH 2 , where X=alkyl or (poly)aza- or oxaalkyl have not been described. The synthesis of 4′-(4-amino-2-oxa)butyl-4,5′,8-trimethylpsoralen hydrochloride is achieved in four (4) steps: STEP 1: 4′-Chloromethyl-4,5′,8-trimethylpsoralen (550 mg, 1.99 mmol) and ethylene glycol (6.8 ml, 121.9 mmol) were heated in acetone (6 mL) to 50-60° C. for 3.5 hrs. After 2 hrs heating, the white suspension had turned to a clear light yellow solution. The acetone and ethylene glycol were removed on the rotoevaporator and water (50 mL) was added to the residue. The resultant suspension was filtered, washed with cold water then dried in the vacuum oven to (give 574 mg (96%) of 4′-(4-hydroxy-2-oxa)butyl-4,5′,8-trimethylpsoralen; NMR (CDCl 3 ) d: 2.51 (s, 6H); 258 (s, 3H); 3.62 (t, J=4.5 Hz, 2H); 3.78 (t, J=4.9 Hz, 2H); 4.70 (s, 2H); 6.26 (d, J=1.1 Hz, 1H); 7.61 (s, 1H). STEP 2: 4′-(4-hydroxy-2-oxa)butyl-4,5′,8-trimethylpsoralen (574 mg, 1.9 mmol) was dissolved in CH 2 Cl 2 (6 mL) under N 2 at ≦10° C. Triethylamine (359 mg, 3.55 mmol) was added. Methanesulfonyl chloride (305 mg, 266 mmol) was dropped in slowly keeping the temperature below 10° C. After addition was completed the mixture was stirred for 15 more minutes and then it was stirred at room temperature for 10 hours. To the reacted suspension CH 2 Cl 2 (45 mL) was added and the mixture was washed with water (20×3 mL), then dried over anhydrous Na 2 SO 4 . Concentration at ≦30° C. followed by vacuum drying gave 4′-[(4-methanesulfonyloxy-2-oxa)butyl-4,5′,8-trimethylpsoralen as a yellow solid (706 mg, 98%), mp 138-140° C. NMR d 2.51 (s, 3H); 2.52 (d, 3H); 2.58 (s, 3H); 2.99 (s, 3H); 3 . 77 (m ,2H); 4.39 (m, 2H); 4.71 (s, 2H); 6.26 (s, 1H); 7.62 (s, 1H). STEP 3: 4′-[(4-Methanesulfonyloxy-2-oxa)butyl-4,5′,8-trimethylpsoralen (706 mg, 1.86 mmol) and sodium azide (241 mg, 3.71 mmol) were refluxed in 95% ethyl alcohol (5 mL) for 8 hours. The reaction solution was cooled and cold water (55 mL) was added. The off-white solid was filtered and washed with cold water. Upon vacuum drying, the azide was obtained as a light yellowish solid (575 mg, 95%), mp 105-106° C. NMR: d 2.51 (s, 6H); 2.58 (s, 3H); 3.41 (t, J=4.9 Hz, 2H); 3.67 (apparent t, J=4.9 Hz, 2H); 4.70 (s, 2H); 6.26 (s, 1H); 7.66 (s, 1H). STEP 4: 4′-(4-Azido-2-oxa)butyl-4,5′,8-trimethylpsoralen (1.65 g, 5.03 mmol) was dissolved in tetrahydrofuran (10 mL). Triphenylphospine (1.59 g, 6.08 mmol) and six drops of water were added to the foregoing solution. After stirring at room temperature overnight, the light yellow solution was concentrated. The residue was dissolved in CHCl 3 (90 mL) and extracted with 0.3N aqueous HCl (30 mL, then 2×5 mL). Combined HCl layers was carefully treated with K 2 CO 3 until saturated. The base solution was extracted with CHCl 3 (3×60 mL). Combined CHCl 3 layers were washed with 60 mL of water, 60 mL of brine and dried over anhydrous Na 2 SO 4 . Upon concentration and vacuum drying the amine was obtained as a yellow solid (1.25 g, 82%), mp 139-141° C.; NMR d 2.48 (s, 6H); 2.53 (s, 3H); 2.89 (t, J=6 Hz, 2H); 3.52 (t, J=6 Hz, 2H); 4.64 (s, 2H); 6.22 (s, 1H); 7.59 (s, 1H). The amine was dissolved in absolute ethanol (40 mL) and 20 mL of 1N HCl in ethyl ether was added. After sitting at 5° C. overnight, the precipitate was filtered and rinsed with ether to give 1.25 g of Compound 2, mp 236° C. (decomp). Anal. Calculated for C 17 H 20 ClNO 4 : C, 60.45: H, 5.97; N, 4.15. Found: C, 60.27; H, 5.88; N, 4.10. Similarly prepared was 4′-(5-amino-2-oxa)pentyl-4,5′,8-trimethylpsoralen, (Compound 4), m.p. 212-214° C. (decomposed). NMR of the free base: d 1.73 (pent, J=6.4 Hz, 2H), 2.45(s, 6H), 2.51 (s, 3H), 2.78 (t, J=6.8 Hz, 2H), 3.54 (t,J=6.2 Hz, 2H), 4.59 (s, 2H), 6.18 (s, 1H), 7.54 (s, 1H). EXAMPLE 3 Synthesis of 4′-(7-Amino-2,5-oxa)Heptyl-4,5′,8-trimethylpsoralen Hydrochloride (Compound 7) The synthesis of 4′-(7-amino-2,5-oxa)heptyl-4,5′,8-trimethylpsoralen hydrochloride proceeds in four (4) steps: STEP 1: 4′-Chloromethyl-4,5′,8-trimethylpsoralen (589 mg, 2.13 mmol), diethylene glycol (15.4 g, 145 mmol) and acetone (13 mL) were refluxed for 11.5 hours. The reaction solution was concentrated to remove acetone and part of the diethylene glycol. To the resulting light brown solution was added CHCl 3 (40 mL), then washed with water several times. The CHCl 3 layer was dried over anhydrous Na 2 SO 4 and concentrated to give 781 mg of product. (˜100%). NMR d 2.46 (d, 3H), 2.47 (s, 3H ), 2.51 (s, 3H), 3.58-3.67 (m, 8H), 4.67 (s, 2H), 6.18 (s, 1H), 7.57 (s, 1H). STEP 2: 4-(7-Hydroxy-2,5-oxa)heptyl-4,5′,8-trimethylpsoralen (781 mg, 2.25 mmol) was dissolved in CH 2 Cl 2 , (2.5 mL) under a N 2 stream at <10° C. Triethylamine (363 mg, 3.59 mmol) was added. Methanesulfonyl chloride (362 mg, 3.16 mmol) was slowly dropped in to keep the temperature below 10° C. After addition was completed, the mixture was kept below 10° C. for 15 more minutes. The mixture was stirred at room temperature overnight then CH 2 Cl 2 (50 mL) was added. The solution was washed with water (3×60 mL), dried over anhydrous Na 2 SO 4 and concentrated at <30° C. Upon vacuum drying, a light brown syrup was obtained; 437 mg (76%). NMR d 2.50 (s, 3H), 2.51 (s, 3H), 2.58 (s, 3H), 3.01 (s, 3H), 3.66 (m, 4H), 3.77 (t, J=4.6 Hz, 2H), 4.37 (t, J=6 Hz, 2H), 4.69 (s, 2H), 6.25 (s, 1H), 7.61 (s, 1H). STEP 3: 4′-(7-Methanesulfonyloxy-2,5-oxa)heptyl-4,5′,8-trimethylpsoralen (288 mg, 0.678 mmol) and sodium azide (88.2 mg, 1.36 mmol) were refluxed in 3 mL of 95% ethyl alcohol for 8 hours. The reaction solution was let cool and cold water (50 mL) was added. The water layer was poured away. The crude material was purified by chromatography on (Silica gel with chloroform eluent) a Chromatotron (Harrison Research, Inc., Palo Alto, Calif.) and vacuum dried to give a light yellow syrup, (123 mg, 49%). NMR d 2.50 (s, 6H), 2.57 (s, 3H), 3.39 (t, J=5.2 Hz, 2H), 3.68 (m, 6H), 4.70 (s, 2H), 6.24 (s, 1H), 7.62 (s, 1H). STEP 4: 4′-(7-Azido-2,5-oxa)heptyl-4,5′,8-trimethylpsoralen (122 mg, 0.33 mmol), triphenylphosphine (129 mg, 0.49 mmol) and several drops of water were dissolved in tetrahydrofuran (2 mL). The light yellow clear solution was stirred at room temperature over a weekend; no starting material was detected by TLC. The reaction solution was concentrated and the residue was dissolved in CHCl 3 (20 mL). The solution was extracted with 0.15 N aqueous HCl solution (10 mL then 2×5 mL) and the HCl layers was taken to pH 13 by addition of 20% aqueous NaOH solution. The basic solution was extracted with CHC 3 (3×15 mL). The combined CHCl 3 layers were washed with water, dried over anhydrous Na 2 SO 4 , concentrated, and vacuum dried to give 63.9 mg of product (56%). TLC showed only one spot. NMR d 2.50 (s, 3H); 2.50 (s, 3H); 2.57 (s, 3H); 2.86 (t, J=5.3 Hz, 2H); 3.50 (t, J=5.3 Hz, 2H); 3.63 (s, 4H); 4.70 (s, 2H); 6.24 (s, 1H); 7.62 (s, 1H). m.p. 170-173° C. The solid was dissolved in absolute ethanol, then 1M HCl in ethyl ether was added, the suspension was filtered and the product rinsed with ether and dried. EXAMPLE 4 Synthesis of 4′-(12-Amino-8-Aza-2,5-Dioxa)dodecyl-4,5′,8-Trimethylpsoralen Dihydrochloride (Compound 8) The synthesis of 4′-(12-amino-8-aza-2,5-dioxa)dodecyl-4,5′,8-trimethylpsoralen dihydrochloride proceeds in one (1) step from the product of Example 3, step 2: A solution of 4′-(7-methanesulfonyloxy-2,5-oxa)heptyl-4,5′,8-trimethylpsoralen (108 mg, 0.253 mmol) in 8 mL of acetonitrile was slowly added to a solution of 1,4-diaminobutane (132 mg, 1.49 mmol) in 2.8 mL of acetonitrile. After refluxing for 8 hours, no starting material remained by TLC. The reaction mixture was cooled to room temperature and CHCl 3 (25 mL) and 1 N aqueous NaOH (25 mL) solution were added. The layers were separated and CHCl 3 (2×10 mL) was used to wash the aqueous layer. Aqueous HCl (0.3 N, 3×10 mL) was used to extract the product from the combined organics layers. The HCl layers was treated with 20% aqueous NaOH solution until pH 13. The combined basic layers were then extracted with CHCl 3 (3×20 mL). The CHCl 3 layer was washed with saturated NaCl aqueous solution (10 mL) then dried over anhydrous Na 2 SO 4 . After concentration and vacuum drying, 63 mg of product was obtained (60%). NMR d 1.45 (m, 2H), 2.49 (s, 6H), 2.55 (s, 3H), 2.58 (t, 2H), 2.66 (t. J=5.6 Hz, 2H), 2.76 (m, 4H), 3.55-3.61 (m, 6H), 4.68 (s, 2H), 6.22 (s, 1H), 7.61 (s, 1H). EXAMPLE 5 Synthesis of 4′-(2-Aminoethyl)4,5′,8-Trimethylpsoralen Hydrochloride (Compound 3) The synthesis of 4′-(2-aminoethyl)-4,5′,8-trimethylpsoralen proceeds in one (1) step: sodium trifluoroacetoxyborohydride was made by adding trifluoroacetic acid (296 mg, 2.60 mmol) in 2 mL of THF to a stirred suspension of sodium borohydride (175 mg, 4.63 mmol) in 2 mL of THF over a period of 10 minutes at room temperature. The resultant suspension was added to a suspension of 4′-cyanomethyl-4,5′,8-trimethylpsoralen (Kaufman et al., J. Heterocyclic Chem . 19:1051 (1982)) (188 mg, 0.703 mmol) in 2 mL of THF. The mixture was stirred overnight at room temperature. Several drops of water were added to the reacted light yellow clear solution to decompose the excess reagent under 10° C. The resulting mixture was concentrated and 1 N aqueous NaOH solution (30 mL) was added. Chloroform (30 mL then 10 mL, 5 mL)) was used to extract the resultant amine. Combined CHCl 3 layers were washed with saturated NaCl solution. The amine was then extracted into aqueous 0.3 N HCl (10, 5, 5 mL) and the acid layers were taken to pH 13 with 20% aqueous NaOH. CHCl 3 (3×10 mL) was used to extract the amine from the combined base layers then washed with water (2 mL) and dried over anhydrous Na 2 SO 4 . Upon concentration and vacuum drying the amine was obtained as a solid, >95% pure by NMR. NMR d 2.45 (s, 3H); 2.47 (s, 3H); 2.53 (s, 3H); 2.78 (t, J=6.6 Hz, 2H); 3.00 (t, J=6.5 Hz, 2H); 6.20 (s, 1H); 7.44 (s, 1H). The solid was dissolved in absolute ethanol. A solution of hydrogen chloride in diethyl ether (1 N, 1 mL) was added. TABLE 10(B) AMT TA102 TA102 TA1537 TA1537 TA1538 TA1538 Dose STRAIN μg/plate −S9 +S9 −S9 +S9 −S9 +S9  0 346 404  9  9  15  19  n = 26  n = 41  n = 30  n = 45  n = 30  n = 42   0.1  27 −20  0  2  3  3 n = 3 n = 6 n = 3 n = 6 n = 3 n = 6   0.5  47  5  3  2  4  13 n = 3 n = 6 n = 9  n = 12 n = 9  n = 12  1  88 −17  5  3  4  37 n = 3 n = 6 n = 9  n = 12 n = 9  n = 12  5 266  51  44  22  13 177 n = 3 n = 6 n = 9  n = 12  n = 18  n = 21 10  52  30  14 255 n = 9 n = 9 n = 9 n = 9 50 2688   94 n = 9 n = 9 100  2058  686 n = 9 n = 9 250  434 3738  n = 9  n = 12 100 μg/pl 10 μg/plt 10 μg/plt 5 μg/plate Positive hydrogen 9-Amino 2-Amino- 2- Amino- Control peroxide acridine fluorene fluorene 660 284  73 1064   n = 23 n = 6  n = 24  n = 30 TABLE 11(A) 8-MOP TA102 TA102 TA1537 TA1537 Dose STRAIN μg/plate −S9 +S9 −S9 −S9  0 346 404 9 9 n = 26 n = 41 n = 30 n = 45  1 −55 −46 n = 14 n = 17 10 −57 −27 n = 14 n = 17 30 5 1 n = 3  n = 6  60 3 1 n = 3  n = 6  90 −1  −4  n = 3  n = 6  100  217 290 n = 14 n = 17 500  781 1179  n = 11 n = 11 100 μg/plt 10 μg/plt 10 μg/plt Positive hydrogen 9-Amino- 2-Amino- Control peroxide Acridine fluorene 660 284  73  n = 23 n = 6  n = 24 TABLE 11(B) 8-MOP TA102 TA102 TA1537 TA1537 Dose STRAIN μg/plate −S9 +S9 −S9 +S9  0 346 404 9 9 n = 26 n = 41 n = 30 n = 45  1 −55 −46 n = 14 n = 17 10 −57 −27 n = 14 n = 17 30 5 1 n = 3  n = 6  60 3 1 n = 3  n = 6  90 −1  −4  n = 3  n = 6  100  217 290 n = 14 n = 17 500  781 1179  n = 11 n = 11 100 μg/plt 10 μg/plt 10 μg/plt Positive hydrogen 9-Amino- 2-Amino- Control peroxide Acridine fluorene 660 284  73  n = 23 n = 6  n = 24 TABLE 12 Compound I TA100 TA100 TA1538 TA1538 Dose STRAIN μg/plate −S9 +S9 −S9 +S9 0 126 123 15 19 n = 41 n = 56 n = 30 n = 42 5 292 −24 10 21 n = 3  n = 3  n = 3  n = 3  10  337 −22 12 22 n = 3  n = 3  n = 3  n = 3  Positive 1.5 μg/ 5 μg/plate plate Control Sodium 2-Amino- Azide fluorene 965 1064  n = 38 n = 30 TABLE 13(A) Compound 2 TA1537 TA1537 TA1538 TA1538 Dose STRAIN μg/plate −S9 +S9 −S9 +S9  0  9  9 15 19 n = 30 n = 45 n = 30 n = 42  5 −8  2 n = 3  n = 3  10  36  5 −13   4 n = 3 n = 3 n = 3  n = 3  50 282  40 n = 3 n = 3 100  258 88 n = 3 n = 3 250  176 744 n = 3 n = 3 500  114 395 n = 3 n = 3 10 μg/plt 10 μg/plt 5 μg/plate Positive 9-Amino- 2-Amino- 2-Amino- Control acridine fluorene fluorene 284  73 1064  n = 6  n = 24 n = 30 TABLE 13(B) Compound 2 TA1537 TA1537 TA1538 TA1538 Dose STRAIN μg/plate −S9 +S9 −S9 +S9  0  9  9 15 19  n = 30  n = 45  n = 30  n = 42  5 −8  2 n = 3 n = 3 10 36 5 −13   4 n = 3 n = 3 n = 3 n = 3 50 282 40 n = 3 n = 3 100  258 88 n = 3 n = 3 250  176 744  n = 3 n = 3 500  114 395  n = 3 n = 3 10 μg/plt 10 μg/plt 5 μg/plate Positive 9-Amino- 2-Amino- 2-Amino- Control acridine fluorene fluorene 284 73 1064  n = 6  n = 24  n = 30 TABLE 14 Compound 3 TA100 TA100 TA1538 TA1538 Dose STRAIN μg/plate −S9 +S9 −S9 +S9  0 126 123 15 19 n = 41  n = 56  n = 30 n = 42  5  47 −19  0  1 n = 3  n = 3 n = 3 n = 3  10  47  8 −6  9 n = 3  n = 3 n = 3 n = 3  1.5 μg/plt 5 μg/plt Positive Sodium 2-Amino- Control Azide fluorene 965 1064  n = 38 n = 30 TABLE 15 Compound 4 TA100 TA100 TA1538 TA1538 Dose STRAIN μg/plate −S9 +S9 −S9 +S9  0 126 123  15 19  n = 41  n = 56  n = 30  n = 42  5 −41 −10  −2  7 n = 3 n = 3 n = 3 n = 3 10  3 −3 −2 −2 n = 3 n = 3 n = 3 n = 3 1.5 μg/ 5 μg/plate plate Positive Sodium 2-Amino- Control Azide fluorene 965 1064   n = 38  n = 30 TABLE 16(A) Compound 6 TA98 TA98 TA100 TA100 Dose STRAIN μg/plate −S9 +S9 −S9 +S9  0 20 25 126 123   n = 38  n = 53  n = 41  n = 56  5 −32 12 n = 3 n = 3 10 12 −5  3 −5 n = 3 n = 3 n = 9 n = 9 50 12  2  2 24 n = 3 n = 3 n = 6 n = 6 100  22 20 −18 −2 n = 6 n = 6 n = 6 n = 6 250  12 40 −38  n = 3 n = 3 n = 3 500   9 52 n = 3 n = 3 5 μg/plate 1.5 μg/plate Positive 2-Amino- Sodium Control fluorene Azide 1154  965  n = 35  n = 38 TABLE 16(B) Compound 6 TA1537 TA1537 TA1538 TA1538 Dose STRAIN −S9 +S9 −S9 +S9  0  9  9 15 19  n = 30  n = 45  n = 30 n = 42  5 −5  0 n = 3 n = 3 10 141 −1 −2  8 n = 6 n = 6 n = 3 n = 3  50 2010  17 n = 6 n = 6 100  795 35 n = 6 n = 6 250  228 99 n = 6 n = 6 500   43 369  n = 3 n = 3 10 μg/plate 10 μg/plate 5 μg/plate Positive 9-Amino- 2-Amino- 2-Amino- Control acridine fluorene fluorene 284 73 1064  n = 6  n = 24 n = 30 Maron and Aimes (1983) describe the conflicting views with regard to the statistical treatment of data generated from the test. In light of this, this example adopts the simple model of mutagenicity being characterized by a two-fold or greater increase in the number of revertants above background (in bold in the tables), as well as dose dependent mutagenic response to drug. With regard to 8-MOP, the only mutagenic response detected was a weak base-substitution mutagen in TA102 at 500 μg/plate (TABLE 14 (B)). In sharp contrast, AMT (TABLE 13 (A) and 13 (B)) showed frameshift mutagenicity at between 5 and 10 μg/plate in TA97a and TA98, at 5 μg/plate in TA1537 and at 1 μg/plate in TA1538. AMT showed no significant base-substitution mutations. Looking at Compound 1, the only mutagenic response detected was a weak frameshift mutagen in TA1538 at 5 μg/plate in the presence of S9. Compound 1 also displayed mutation in the TA100 strain, but only in the absence of S9. Compound 2 also showed weak frameshift mutagenicity in the presence of S9 in TA98 and TA1537. Compounds 3 and 4 showed no mutagenicity. Compound 6 had no base substitution mutagenicity, but showed a frameshift response in TA98 in the presence of S9 at concentrations of 250 μg/plate, and above. It also showed a response at 50 μg/plate in TA1537 in the presence of S9. Both responses are significantly below that of AMT, which displayed mutagenicity at much lower concentrations (5 μg/plate). From this data it is clear that the compounds of the present invention are less mutagenic than AMT, as defined by the Ames test. At the same time; these compounds show much higher inactivation efficiency than 8-MOP, as shown in Examples 9 and 13. These two factors support that the compounds of the present invention combine the best features of both AMT and 8-MOP, high inactivation efficiency and low mutagenicity. EXAMPLE 15 In Example 12, the compounds of the present invention exhibited the ability to inactivate pathogens in synthetic media. This example describes methods by which synthetic media and compounds of the present invention may be introduced and used for inactivating pathogens in blood. FIG. 20A schematically shows the standard blood product separation approach used presently in blood banks. Three bags are integrated by flexible tubing to create a blood transfer set ( 200 ) (e.g. commercially available from Baxter, Deerfield, Ill.). After blood is drawn into the first bag ( 201 ), the entire set is processed by centrifugation (e.g., Sorvall™ swing bucket centrifuge, Dupont), resulting in packed red cells and platelet rich plasma in the first bag ( 201 ). The plasma is expressed off of the first bag ( 201 ) (e.g., using a Fenwall™ device for plasma expression), through the tubing and into the second bag ( 202 ). The first bag ( 201 ) is then detached and the two bagset is centrifuged to create platelet concentrate and platelet-poor plasma; the latter is expressed off of the second bag ( 202 ) into the third bag ( 203 ). FIG. 20B schematically shows an embodiment of the present invention by which synthetic media and photoactivation compound are introduced to platelet concentrate prepared as in FIG. 20A. A two bag set ( 300 ) is sterile docked with the platelet concentrate bag ( 202 ) (indicated as “P.C.”). Sterile docking is well-known to the art. See e.g., U.S. Pat. No. 4,412,835 to D. W. C. Spencer, hereby incorporated by reference. See also U.S. Pat. Nos. 4,157,723 and 4,265,280, hereby incorporated by reference. Sterile docking devices are commercially available (e.g., Terumo, Japan). One of the bags ( 301 ) of the two bag set ( 300 ) contains a synthetic media formulation of the present invention (indicated as “STERILYTE”). In the second step shown in FIG. 20B, the platelet concentrate is mixed with the synthetic media by transferring the platelet concentrate to the synthetic media bag ( 301 ). The photoactivation compound can be in the bag containing synthetic media ( 301 ), added at the point of manufacture. Alternatively, the compound can be mixed with the blood at the point of collection, if the compound is added to the blood collection bag (FIG. 20A, 201 ) at the point of manufacture. The compound may be either in dry form or in a solution compatable with the maintainance of blood. FIG. 20C schematically shows one embodiment of the decontamination approach of the present invention applied specifically to platelet concentrate diluted with synthetic media as in FIG. 20 B. In this embodiment, platelets have been transferred to a synthetic media bag ( 301 ). The photoactivation compound either has already been introduced in the blood collection bag ( 201 ) or is present in the synthetic media bag ( 301 ) to which the platelets are now transferred. This bag ( 301 ), which has UV light transmission properties and other characteristics suited for the present invention, is then placed in a device (such as that described in Example 1, above) and illuminated. Following phototreatment, the decontaminated platelets are transferred from the synthetic media bag ( 301 ) into the storage bag ( 302 ) of the two bag set ( 300 ). The storage bag can be a commercially available storage bag (e.g., CLX bag from Cutter). It is to be understood that the invention is not to be limited to the exact details of operation or exact compounds, composition, methods, or procedures shown and described, as modifications and equivalents will be apparent to one skilled in the art.
Psoralen compound compositions are synthesized which have substitutions on the 4, 4′, 5′, and 8 positions of the psoralen, which yet permit their binding to nucleic acid of pathogens. Reaction conditions that photoactivate these bound psoralens result in covalent crosslinking to nucleic acid, thereby inactivating the pathogen. Higher psoralen binding levels and lower mutagenicity results in safer, more efficient, and reliable inactivation of pathogens. In addition to the psoralen compositions, the invention contemplates inactivating methods using the new psoralens.
0
BACKGROUND INFORMATION [0001] The present invention relates generally to offset printing and more specifically to a plate cylinder for an offset printing press and related plate bender. [0002] U.S. Pat. No. 4,487,122 discloses a system for compensating for roll deflection to provide contact pressure across the width of a web disposed between a pair of counter rollers. U.S. Pat. No. 5,094,163 discloses a rotogravure press with electrically conductive layers. U.S. Pat. No. 5,913,266 and U.S. Patent Publication No. 2003/0061955 disclose plate cylinders, and are hereby incorporated by reference herein. U.S. Pat. Nos. 6,283,027 and 6,105,498 disclose varying profile blankets, including printing blankets with concave and convex profiles. A concave blanket cylinder is also disclosed. [0003] U.S. Pat. No. 5,987,949 discloses a plate bender and is hereby incorporated by reference herein. BRIEF SUMMARY OF THE INVENTION [0004] Especially with multi-image width printing presses, deflection at the middle of the plate and blanket cylinders can provide problems with printing a web. For example, the middle of the web may be printed too lightly. [0005] U.S. patent application Ser. No. 10/617,639, filed Jul. 11, 2003 and hereby incorporated by reference herein, discloses a printing blanket comprising a carrier sleeve layer having at least one axially convex surface when disposed on a blanket cylinder and a print layer disposed over the carrier sleeve layer. In this application, the convexity of the carrier sleeve layer may be provided, for example, by having the carrier sleeve layer have a uniform inner diameter and a convex outer diameter. The carrier sleeve layer itself is thus thicker in an axial middle than at the ends. Alternately, the carrier sleeve can be of uniform thickness, and the blanket cylinder or a shim may provide the surface convexity. [0006] Crowning of blankets or a blanket cylinder to have a larger diameter can result to fan-in, i.e. a lateral squeezing together of the web and thus the print, during printing. [0007] The present invention provides a plate cylinder comprising a cylinder body, a first image area at one end of the cylinder body, the first image area having a first average diameter, a second image area at the other end of the cylinder body having a second average diameter, and a third image area between the first and second image areas, the third image area having a third average diameter, the third average diameter being larger than the first and second average diameters. [0008] By having a larger diameter image area in the middle of the plate cylinder, print pressure or squeeze can be increased at the center of the web. [0009] Each image area may comprise two side-by side images, so that the plate cylinder is six images wide. Preferably, each image area supports a single image in the circumferential direction. A one-by-six plate cylinder thus may be provided. However, any ratio of one-by-three or greater plate cylinder may be provided, for example a two-by-six plate cylinder. Ratios of one-by-four or greater are preferred, as increased widths create more need for increased print pressure. A ratio of one-to-six is possible, and a ratio of one-to-six or greater may be most preferable. [0010] One or more printing plates may be attached at each image area. [0011] The first and second image areas may have a constant diameter, as may the third image area. However, the image areas may be of non-constant diameter, for example crowned or conically shaped to provide the different average diameters. [0012] The cylinder body may have a larger diameter middle section so that the third average diameter is larger than the end section. [0013] Alternatively, packing may be applied to increase the diameter of a printing plate or plates in the third image area. As another alternative, the plates used in the third image area may be thicker than plates used in the first and second image areas. In these cases, the cylinder body may have a uniform diameter. [0014] An offset printing press comprising the plate cylinder and a blanket cylinder is also provided. Preferably, the blanket cylinder has an effective blanket diameter which is uniform to reduce fan-in. [0015] A plate bender for printing plates for use on the plate cylinder of the present invention is also provided, the plate bender including a movable section for altering the effective post-bending length of the plate as a function of an intended axial position of the plate on the plate cylinder. [0016] The present invention also provides a plate bender for printing plates having a movable section skewable with respect to the plate. The movable section may be curved to fit with a crowned plate cylinder. [0017] Plate cylinder as defined herein includes a directly imaged cylinder where images are written directly on the outer surface of the cylinder, for example by a laser. While the printing plates preferably are flat lithographic printing plates, for certain embodiments, the printing plates may also be tubular in nature. BRIEF DESCRIPTION OF THE DRAWINGS [0018] The present invention will be further described with respect the following Figures, in which: [0019] FIG. 1 shows schematically a first embodiment of the printing press of the present invention with a plate cylinder having a larger diameter cylinder body middle image area; [0020] FIGS. 2 and 3 show an alternate plate cylinders with a uniform diameter cylinder body, FIG. 2 having packing underneath the middle image area and FIG. 3 having thicker plates in the middle image area; [0021] FIGS. 4 and 5 show crowned and conical plate cylinder image areas, respectively; [0022] FIG. 6 shows a schematic top view of a plate bender according to the present invention; and [0023] FIGS. 7 and 8 show two partial side views of the plate bender. DETAILED DESCRIPTION [0024] FIG. 1 shows schematically a print unit 5 of an exemplary offset lithographic web printing press 1 with a blanket cylinder 10 having a uniform radius outer surface 11 for printing a web 8 . A compressible blanket 20 fits over blanket cylinder 10 , for example by sliding axially. The blanket or blanket cylinder may have a uniform or profiled outer surface. [0025] A one-by-six plate cylinder 22 may have an image area 24 having two side-by-side images E, F, an image area 28 having two side-by-side images A, B and a middle image area 26 having two side-by-side images C, D, all of which are transferred via the blanket cylinder 20 to the web 8 as shown. The plate cylinder body, which may be made for example of steel and have axially-extending plate lock-up gaps 32 , has a larger diameter at image area 26 . This can be achieved for example through milling the cylinder body at areas 24 , 28 to reduce the diameter. Six flat lithographic printing plates may be attached to the respective image areas via gaps 32 , the plates having images A, B, C, D, E, F respectively. Alternately the images can be directly imaged on the plate cylinder. [0026] Circumferential and/or lateral registration for each plate or image area may be provided, for example via a mechanism as disclosed in U.S. Pat. No. 6,559,908, which is hereby incorporated by reference herein. [0027] A similar blanket 40 and plate cylinder 42 may be provided for the opposite side of web 8 . [0028] The diameter difference is exaggerated for clarity in FIG. 1 . The larger diameter of image area 26 increases print pressure at the center of blankets 20 , 40 . Although some part of images B, E close to images C, D face reduced pressure due to the raised nature of the area 26 , the increased diameter of section 26 may be selected so that the compressible nature of blanket 20 and print pressure variation of the entire width provide adequate print pressure for all of images B and E. It is also noted that non-printed lateral areas typically extend between the image areas A, B, C, D, E, F. [0029] FIG. 2 shows an alternate embodiment of a plate cylinder 50 having a plate cylinder body 52 with a uniform outer diameter. Plates 54 , 55 , 58 and 59 all have a same diameter while plates 56 , 57 have a larger effective diameter when placed on cylinder body 52 via packing materials 51 , 53 . MYLAR for example in tape or sheet form may be used as a packing material. The plates may be directly imaged on the cylinder 50 . [0030] FIG. 3 shows an alternate embodiment of a plate cylinder 60 having a plate cylinder body 62 with a uniform outer diameter. Plates 64 , 65 , 66 , 67 , 68 and 69 all have a same inner diameter while plates 66 and 67 have a larger outer diameter than plates 64 , 65 , 68 , 69 due to an increased thickness. The plates 64 , 65 , 66 , 67 , 68 , 69 , while preferably flat, could also be manufactured as tubes and slid axially onto the plate cylinder body 62 . The plates may be directly imaged on the cylinder 50 . [0031] FIG. 4 shows a crowned plate cylinder 70 , the crowning being exaggerated for clarity. Plates 74 , 75 , 76 , 77 , 78 and 79 can be attached to the plate cylinder, although direct imaging is also possible. [0032] FIG. 5 shows a conically-sectioned plate cylinder, the conical sections being angled in an exaggerated manner for clarity. Image areas 84 , 85 , 86 , 86 , 88 and 89 may be provided for example by plates attached to the image areas or by direct imaging. [0033] The crowning or conical shape may be achieved for example through milling. [0034] FIG. 6 shows a plate bender 90 according to the present invention. Images may be imaged in a prepress imaging station 92 on the plates for the plate cylinder 22 , and the images may all have a similar size. [0035] Through prepress 92 , the desired axial location for each plate on the plate cylinder 22 is known, i.e. whether the plate is to print image A, B, C, D, E or F for one color. [0036] A processor 94 then controls the plate bender 90 so that a distance DI is altered. Pistons 96 , 98 for example can move a base bar 110 with respect to a plate base 100 via tracks 102 , 104 . As shown in exaggerated fashion in FIGS. 7 and 8 , for a plate carrying image C the distance DI is larger than for the plate carrying image A, which is on a smaller diameter section of plate 22 . The axially-extending lock-up gaps 32 in the plate cylinder 22 hold the bent section of the plate and thus fasten the plates to the plate cylinder 22 . An overhead anvil may be provided to bend the plate edge about the base bar 110 . [0037] For the embodiment of FIG. 5 , the plate bender 90 may have an extra base bar opposite the base bar 110 and also controlled by the processor 94 . Hinges 106 , 108 may be provided between track 102 , 104 and the base bar 110 to permit a skewing of the base bar 110 with respect to base 100 to create a skew angle SA, which can correspond to the conical angle for a section 84 , 85 , 86 , 87 or 88 on plate cylinder 80 . [0038] For the embodiment of FIG. 4 , the base bar 110 and the bar opposite base 100 may be rounded at the bend edge to match the crowning curvature. [0039] “Crowned” as defined herein means to have an outer surface curved convexly with respect to a cylinder rotational axis.
A plate cylinder has a cylinder body, a first image area at one end of the cylinder body, the first image area having a first average diameter, a second image area at the other end of the cylinder body having a second average diameter, and a third image area between the first and second image areas. The third image area has a third average diameter larger than the first and second average diameters. A print unit, web offset printing press and a plate bender are also provided.
1
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a practice racket especially adapted for practice of a tennis service, as well as other tennis strokes, and also for warm-up exercises. 2. Description of the Prior Art One of the more difficult maneuvers to execute in a tennis game is an effective service. In serving the tennis ball, the ball is tossed a moderate distance above the player's head, and the player swings the racket in an overhead arc to impact the ball as the racket is traveling through the uppermost portion of the arc. The usual method of practicing a service is to actually "serve" the ball on a conventional tennis court or against a wall or other barrier spaced some distance away from the server. Unfortunately, a tennis court may not always be available, or when available a number of balls must be used and chased after each serve, or when a barrier is used there is often not sufficient room to engage in such practice. Thus, quite often the only alternative is for the player to simply swing his racket through the serving motion. However, this does not permit the player to coordinate the tossing up of the ball and striking the ball as a continuous serving motion. In the prior art there are a number of practice rackets for a variety of purposes. For example, U.S. Pat. No. 3,503,611, McPherson, shows a practice racket in which the strings of the racket are removed and a pouch is mounted over the racket frame. This pouch has a central ball port through which the tennis ball can enter into the interior of the pouch, and also a double bottom at the backside of the pouch to receive the impact of the tennis ball. When the racket is swung at the ball in a manner that the ball passes through the entry port, the ball is then retained in the pouch for a subsequent stroke. One of the problems with this device is that for the pouch to properly perform its retaining function, the entry port must be made sufficiently small so that there is little margin for error in the player's serving motion. In other words, if the server strikes the ball at a location spaced moderately from the center area of the racket, the ball is not able to pass through the entry port, and is thus propelled away from the server. Furthermore, the pouch material and construction presents a different weight and stroke air resistence when compared to a conventional tennis racket. U.S. Pat. No. 1,540,823, Mairhofen, illustrates a ball catching device mounted to a racket where there are two plates having retaining teeth thereon. When a ball strikes the area between the plates, these two plates close on the ball with the teeth causing the ball to be retained in the racket. This apparatus also requires that the ball be impacted at a precise location quite close to the centerline of the racket. Unlike the present invention, this device is designed to be used in a new game and not for the practice of conventional tennis. U.S. Pat. No. 2,738,976, Vallieres, and also British Patent Specification No. 2042, Greenham, having an acceptance date of May 22, 1902, disclose rackets having cords for retaining stationary tennis balls, shoes or the like when the racket is not being used. U.S. Pat. No. 1,364,331, Vaile, discloses a tennis racket in which the impact strings are made somewhat looser than usual to permit a game similar to tennis to be played with a dead ball in an area of smaller dimensions than the conventional tennis court. U.S. Pat. No. 2,080,642, Timpe, shows a racket having resilient rubber strings and edge mounting, the intended purpose of which is to provide greater resiliency in play and to improve the durability of the racket. U.S. Pat. No. 3,078,099, Hyman, illustrates a combined ball paddle and catching receptacle. One surface of the paddle is used to strike the ball, while the other side of the paddle has a semirigid woven material in the general configuration of a basket. When the ball strikes the basket, it becomes enmeshed therein so as to be retained by the woven material. U.S. Pat. No. 3,206,195, Myers, shows a baseball batting aid comprising a handle and a peripheral frame to which is attached a net. The particular purpose of this batting aid is to teach the user to properly position his wrists during the batting stroke. If the peripheral frame is properly positioned during the stroke, and if the ball is engaged within the area of the peripheral frame, the ball enters the net and is retained thereby. Also representative of the prior art are U.S. Pat. No. 2,025,995 and U.S. Pat. No. 3,845,953. While the prior art known to the applicant does permit a ball to be engaged and retained by a racket in a variety of ways, there still remains a need for a practice racket that closely resembles the configuration, weight and handling characteristics of a conventional tennis racket by which a tennis stroke, particularly a tennis service stroke, can be practiced in a manner to closely simulate an actual game stroke or service and allow the ball to be struck anywhere on the playing surface from different angles such as is experienced in actual play to accommodate the entire range of player ability, while retaining the ball in the racket so that such practice can be conducted in a relatively confined area. Thus, it is an object of the present invention to fulfill such a need. SUMMARY OF THE INVENTION The present invention is a practice racket for a game such as tennis, by which a player can execute a stroke against a game ball in a manner similar to a stroke executed with a conventional game racket, while retaining the ball in the practice racket. In the preferred form, the practice racket has the over all configuration of a conventional tennis racket and comprises a handle adapted to be grasped by the player to execute the practice stroke, and a peripheral frame attached to the handle. This frame defines an impact area in the plane occupied by the frame, this impact area corresponding to the area of a game racket where the ball is normally struck in actual game play. Attached to the peripheral frame and extending across the impact area is a flexible net means which is sufficiently large in area relative to the impact area, so that the net means can deflect at least moderately from the plane of the impact area upon engaging the ball. Also connected to the frame and extending across the impact area is a string retaining means. The string retaining means is sufficiently yielding to permit the ball to pass therethrough into the net means, and yet has sufficient tension to retain the ball in the net after the ball has passed through the string means. In the preferred form of the present invention, the string means comprises a plurality of strings arranged in a grid. As shown herein, one set of strings is parallel to the longitudinal axis of the racket, and a second set of strings is transverse to the longitudinal axis. Thus, the strings that form the grid separate the impact area of the racket into a plurality of impact zones arranged in a rectangular pattern. Desirably the strings are positioned on both sides of the retaining net. when the racket is swung at the ball, the ball passes through the retaining strings into one of the impact zones and is retained by the combination of the net and the retaining strings in that particular zone. This permits the player to determine at what part of the impact area the ball was engaged so that the player can ascertain if he is striking the ball correctly. In the actual construction of the particular embodiment shown herein, a conventional tennis racket was used. The strings of the racket were removed; an auxiliary mounting frame was positioned and secured within the conventional racket frame; and the retaining strings and net were mounted to the auxiliary mounting frame. This particular arrangement is well adapted for construction of a single racket or a small number of rackets with readily available components. It is to be understood, however, that for large scale production it is likely that certain changes in structural details, configuration and/or materials would be desirable, and it is intended that these be considered within the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view taken from a position in front of the frame of the practice racket of the present invention; FIG. 2 is a sectional view through the longitudinal center line of the racket, taken along line 2--2 of FIG. 1; FIG. 3 is a sectional view taken along line 3--3 of FIG. 1, and illustrating a portion of the auxiliary mounting frame; FIG. 4 is a view similar to FIG. 3, taken along line 4--4 of FIG. 1; FIGS. 5A through 5D are four longitudinal sectional views illustrating the practice racket being swung through a service stroke, and illustrating particularly the manner in which the tennis ball is engaged and retained by the practice racket. DESCRIPTION OF THE PREFERRED EMBODIMENT The preferred embodiment of the present invention shown in the accompanying drawing is a practice tennis racket 10 particularly adapted for practice of a tennis service. However, it should be understood that the broader aspects of the present invention are not confined to this particular use or precise physical arrangement. The racket 10 has the overall configuration of a conventional tennis racket, and thus comprises a generally oval frame 12 and an elongate handle 14. (For convenience of illustration, only a portion of the handle 14 is shown in FIG. 1.) By having the dimensions, weight and balance of the racket 10 being substantially the same as or at least very close to that of an actual game racket which the player uses, the serving motion employing the practice racket will more closely simulate the serving motion in actual game play. This practice racket 10 can be made quite conveniently through a modification of a conventional tennis racket, by removing the existing strings that are connected in a grid-like pattern across the frame 12 and substituting the components of the present invention. In describing this racket 10, the longitudinal axis shall be considered coincident with the lengthwise axis of the handle 14, and the transverse axis is considered perpendicular to the longitudinal axis and lying in the plane of the frame 12. The term "lower" denotes proximity to the terminal end of the handle 14, and the term "upper" denotes proximity to the opposite end of the racket 10, i.e. near the end of the frame opposite the handle. The term "inner" or "inside" denotes proximity to the center area of the frame 12. The term "forward" denotes the face of the racket which is traveling towards the ball, and the term "rearward" quite obviously denotes the opposite face of the racket 10. In this practice racket 10, the two main functional components are a flexible barrier net 16 and a retaining string means 18. The barrier net 16 reaches across the area within the perimeter of the frame 12, this area being the "impact" area where a game ball is normally struck with the racket. As its name implies, this barrier net 16 functions to engage the ball, indicated at 19, and prevent it from passing through the racket 10. The retaining string means 18 also extends across the impact area of the racket 10. As shown herein, there are two sets of retaining strings, a forward set 18' and a rearward set 18", these two sets 18' and 18" both being parallel to the plane of the impact area of the frame 12 and spaced between the forward and rearward faces of the frame 12 (in the particular configuration herein, about one-half inch from each other). While only one of the sets 18' or 18" is necessary, by so providing two sets of strings 18' and 18", the ball can be engaged by either face of the racket in a practice stroke. In the particular arrangement shown herein, each set of strings 18' and 18" comprises four longitudinal strings 18a and two transverse strings 18b, arranged in a grid-like pattern so that the strings 18a and 18b divide the impact area of the racket 10 into a plurality of impact zones (specifically, fifteen impact zones arranged in three transverse rows of five each). The string sets 18' and 18" and the barrier net 16 are mounted to the frame 12 by means of an auxiliary mounting frame 20, with the barrier net 16 being positioned between the two string sets 18' and 18". The particular auxiliary mounting frame shown herein, was constructed for an actual working prototype and is made from commonly available components. However, as indicated previously herein, it is to be understood that the specific construction of this auxiliary mounting frame 20 as well as other components would quite likely be modified for a racket that is manufactured on a large scale production basis. The auxiliary mounting frame 20 is connected to the main racket frame 12 just inside the inner perimeter thereof. The auxiliary frame 20 is made up of a first outer rigid frame portion 22 and a resilient frame portion 24 mounted within the outer portion 22. For convenience of fabrication, assembly and adjustment, the rigid frame portion 22 is made up of four segments 22a, secured to the main racket frame 12 by means of a cord 26 which is strung through the existing holes in the racket frame 12 normally used for mounting the conventional strings of a playing racket. The inner auxiliary frame portion 24 is made up of a moderately resilient material, such as rubber surgical hose, and is secured to the inside of the frame portion 22 at regularly spaced intervals (approximately an inch apart) along its entire length. A convenient way of accomplishing this is to wrap a cord 28 through the frame portions 22 and around the frame portion 24 in spiral fashion along the entire length thereof. The retaining strings 18a and 18b are secured to the outer auxiliary frame portion 22. It will be noted that the longitudinal strings 18a are strung directly through the upper and lower frame segments 22a, and the transverse strings 18b are connected by their end portions to resilient cords 30, each of which is in turn connected to their related side frame segment 22a. The particular reason for this arrangement is to enhance the ability of these strings 18a and 18b to perform their function of deflecting to permit the ball to initially pass through the strings 18a and 18b, and then reliably retain the ball. In this particular arrangement of the retaining string means 18, the longitudinal strings 18a are made of a resilient rubber-like material whose surface has a relatively high coefficient of friction. The transverse strings 18b are made of a relatively low friction material (e.g. Teflon), which is less resilient than the material of the longitudinal strings 18a. To permit the transverse strings 18b to deflect properly upon impact with the ball, their connection to the auxiliary frame portion 22 is made through these resilient cords 30. It has been found that if both sets of strings 18a and 18b are made of a higher friction material, the ball is less able to pass through the strings 18a and 18b, and in some instances the ball when engaged will bounce away from the racket 10. However, by making the transverse strings 18b of a low friction material, the ball upon initial engagement is able to pass through the strings 18a and 18b. While this particular arrangement has been found to work effectively, it will be obvious to those skilled in the art that modifications could be made in this arrangement. The barrier net 16 is made of a relatively light weight flexible net material. A suitable net material is a nylon material used in a conventional fish net for small game fish. If the net material is made too heavy, it provides unwanted resistance against the air during the racket stroke, and also tends to hang up on the retaining strings and provide more inertia in forming a pocket which creates more of a tendancy for the ball when engaged to rebound away from the racket 10. The barrier net 16 is secured to the resilient frame portion 24 around the entire perimeter of the net 16 by a number of strands 32 placed about one inch apart. This resilient mounting 24 permits the net 16 to yield moderately upon impact with the ball, to reduce the force of initial impact, thus allowing the use of lighter net material to enhance the ball retaining function of the racket 10. The resilient mounting 24 will also prolong the life of the barrier net 24. An alternate means of mounting the net 16 is to attach it directly to the strings 18a and 18b. To describe the operation of the present invention, reference is now made to FIGS. 5A through 5D. As indicated previously, the normal serving motion in a game of tennis is for the player to toss the ball 19 into the air and then swing the racket 10 in an upward arc to engage the ball 19 as the racket 10 is passing through the uppermost part of its arc. In FIG. 5A, the racket 10 is seen approaching the uppermost portion of its arcuate path of travel and is about to engage the ball 19. In FIG. 5B, the racket 10 is just passing beyond its uppermost arcuate portion of travel and has engaged the ball 19. The ball 19 has deflected the forward and rearward retaining strings 18a and 18b which it engages to the side and is engaging the barrier net 16, to carry it through the rearward retaining strings 18a and 18b. Since the area of the barrier net 16 is moderately greater than the total impact area within the racket frame 12, the barrier net 16 is able to deflect moderately in a rearward direction from the impact zone due to the force caused by engaging the ball 19. As the racket 10 continues through its arcuate path of travel with the ball 19 engaged in the net 16, there is an upward centrifugal force which tends to move the ball upwardly relative to the racket 10. This is illustrated in FIG. 5C, where it can be seen that the ball tends to pull the barrier net 16 toward the upper part of the racket 10 against the upper rear retaining string 18b. The ball remains in this same general position relative to the racket 10, until completion of the stroke. Upon completion of the stroke, the ball 19 remains in its retained position in the net 16 in the impact zone at which it entered the racket, as shown in FIG. 5D. The player is then able to simply pull the ball back through the retaining strings 18 in preparation for another practice stroke. By observing which impact zone the ball entered during the service stroke, the player is able to determine if the ball is being engaged at the proper location of the impact area of the racket 10. In addition to permitting the coordinated action of tossing the ball 19 into the air and swinging the racket through a service stroke in one coordinated motion, the player is able to get the "feel" of impact with the ball 19. This is due to the fact that the ball 19, in being engaged by the barrier net 16 and retaining strings 18 just rearwardly of the plane of the impact area of the racket, exerts a rearward force on the racket 10.
A practice tennis racket having a handle and peripheral frame corresponding to a conventional tennis racket. Extending across the frame is a flexible barrier net and a gridwork of yielding retaining strings. When a tennis ball is struck with the racket, the retaining strings permit the ball to pass therethrough to be caught in the net, with the strings retaining the ball in the net.
0
TECHNICAL FIELD [0001] The present invention relates to a chain block for use in a load hoisting work. BACKGROUND ART [0002] In order to move a load in an up-down direction, a chain block is generally used. The chain block includes a hand wheel, a wheel cover, a main body portion, and the like. The main body portion is provided with a load sheave around which a load chain is wound. Then, when a hand chain wound around the hand wheel is wound up, the hand wheel rotates, and the rotation of the hand wheel is transmitted to the load sheave through a predetermined transmission mechanism including gears and the like. Thereby, the load hung on a lower hook are moved in an upward direction. Conversely, when the hand chain is wound down in a state where the load is positioned in the upper side, the load is moved in a downward direction. Such a chain block is disclosed in, for example, Patent Literature 1. [0003] In the chain block described in Patent Literature 1, a wheel cover (refer to FIG. 19 ) is mounted to a second main frame, but the wheel cover is provided in a shape following the contours of a first main frame and the second main frame. CITATION LIST Patent Literature [0004] [PLT 1] Japanese Patent Laid-open Publication No. 2011-201637 SUMMARY OF INVENTION Technical Problem [0005] Now, in order to resist impact or external force acting on a wheel cover, there is a need to improve the strength of the wheel cover. However, in a case where the thickness of a steel plate is increased, a separate reinforcement member is added, or additional work is required so as to improve the strength of the wheel cover, a cost is increased accordingly. Thus, there is a need to improve the strength of the wheel cover while suppressing an increase in weight or cost with no need for a separate reinforcement member. Solution to Problem [0006] The present invention has been made under the above-described circumstances, and an object of the present invention is to provide a chain block with which the strength of a wheel cover can be improved while suppressing an increase in weight or cost with no need to increase the thickness of a steel plate nor need for a separate reinforcement member. Advantageous Effects of Invention [0007] In order to solve the above-described problem, according to a first aspect of the present invention, is provided a chain block including a wheel cover that is mounted to a frame member and covers a hand wheel over which a hand chain is wound, wherein a plurality of fixation holes into which fixation members are inserted during mounting to the frame member is provided in a peripheral edge portion on an end surface side arranged facing the frame member of the wheel cover, and a wrap-around portion formed surrounding a fixation hole at an angle exceeding 90 degrees in a peripheral direction of the fixation hole is provided in a side surface of the wheel cover, which intersects the end surface. [0008] Furthermore, according to another aspect of the present invention, it is preferable that in the above-described invention the wheel cover be provided with a chain guide portion that prevents the hand chain looped over the hand wheel from coming off, and the chain guide portion be provided adjacent to the wrap-around portion, and integrally provided in a continuous state with the wrap-around portion. [0009] Further, according to another aspect of the present invention, it is preferable that in the above-described invention the wheel cover be provided with a chain guide portion that prevents the hand chain looped over the hand wheel from coming off, and the chain guide portion be provided adjacent to the wrap-around portion, and provided separately from the wrap-around portion without being continuous with the wrap-around portion. [0010] Furthermore, according to another aspect of the present invention, it is preferable that in the above-described invention an outer peripheral edge portion of the frame member be provided with at least a pair of concave portions passing through a center side thereof with a drooping direction interposed therebetween, the drooping direction be a direction in which the hand chain droops when used, and the pair of concave portions be recessed toward the center side of the frame member more than the outer peripheral edge portion of the frame member adjacent to the concave portions. [0011] Further, according to another aspect of the present invention, it is preferable that in the above-described invention a tip side spaced apart from the end surface of the chain guide portion be provided with a protruding tip that is inserted into an insertion hole of the frame member. [0012] Furthermore, according to another aspect of the present invention, it is preferable that in the above-described invention an outer edge portion on a side spaced apart from the wrap-around portion of the chain guide portion be provided with a folded-back portion formed by hemming processing. Advantageous Effects of Invention [0013] According to the present invention, the strength of a wheel cover can be improved while suppressing an increase in weight or cost with no need to increase the thickness of a steel plate in a chain block nor need for a separate reinforcement member. BRIEF DESCRIPTION OF DRAWINGS [0014] FIG. 1 is a front view illustrating an appearance of a chain block according to an embodiment of the present invention. [0015] FIG. 2 is a side view illustrating the appearance of the chain block of FIG. 1 . [0016] FIG. 3 is a rear view illustrating the appearance of the chain block of FIG. 1 . [0017] FIG. 4 is a side cross-sectional view illustrating a state in which the chain block has been cut along the line A-A in FIG. 1 . [0018] FIG. 5 is a side cross-sectional view illustrating a state in which the chain block has been cut along the line B-B in FIG. 2 . [0019] FIG. 6 is a front view illustrating the shapes of a first frame and an auxiliary plate in a state where a reduction gear member and a load gear are removed from the chain block in FIG. 1 . [0020] FIG. 7A is a perspective view illustrating the shape of the auxiliary plate in the chain block in FIG. 1 , when seen from the front side. [0021] FIG. 7B is a perspective view illustrating the shape of the auxiliary plate in the chain block in FIG. 1 , when seen from the rear side. [0022] FIG. 8 is a diagram illustrating the positional relation of attaching positions of a fixation member and a guide roller with respect to a first frame in the chain block in FIG. 1 . [0023] FIG. 9 is a diagram illustrating an arrangement of a reduction gear member and a load gear with respect to the first frame in the chain block in FIG. 1 . [0024] FIG. 10A is a perspective view illustrating the shape of the reduction gear member in the chain block in FIG. 1 , when seen from the front side. [0025] FIG. 10B is a perspective view illustrating the shape of the reduction gear member in the chain block in FIG. 1 , when seen from the rear side. [0026] FIG. 11A is a perspective view illustrating the shape of a drive shaft in the chain block in FIG. 1 , when seen from the front side. [0027] FIG. 11B is a perspective view illustrating the shape of the drive shaft in the chain block in FIG. 1 , when seen from the rear side. [0028] FIG. 11C is a partial expanded side cross-sectional view of the drive shaft in the chain block in FIG. 1 , illustrating the shape of the vicinity of a flange portion. [0029] FIG. 12A illustrates an engagement state between a pinion gear and a large-diameter gear according to the present embodiment. [0030] FIG. 12B illustrates an engagement state between a pinion gear and a large-diameter gear according to a configuration of the related art. [0031] FIG. 13A is a diagram illustrating the relation in tooth thickness between the pinion gear and the large-diameter gear according to the present embodiment. [0032] FIG. 13B is a diagram illustrating the relation in tooth thickness between the pinion gear and the large-diameter gear according to the configuration of the related art. [0033] FIG. 14 is a diagram illustrating an arrangement of a ratchet wheel and pawl members in the chain block in FIG. 1 . [0034] FIG. 15 is a perspective view illustrating the shape of a wheel cover in the chain block in FIG. 1 . [0035] FIG. 16 is a partial expanded plan view of the shape of the vicinity of a protruding portion of an end surface of the wheel cover in FIG. 15 . [0036] FIG. 17A is a diagram illustrating an image when a force acts on a side surface of a wheel cover according to the configuration of the related art. [0037] FIG. 17B is a diagram illustrating an image when a force acts on a wrap-around portion. [0038] FIG. 18 is a partial cross-sectional view illustrating a configuration in the vicinity of a folded-back portion of a chain guide portion of the wheel cover in FIG. 15 . [0039] FIG. 19 is a side view illustrating the shape of a wheel cover according to a modification of the present invention. [0040] FIG. 20 is a plan view illustrating the shape of a wheel cover according to the modification of the present invention. [0041] FIG. 21 is a perspective view illustrating the shape of the wheel cover according to the related art. DESCRIPTION OF EMBODIMENTS [0042] Hereinafter, a chain block 10 according to an embodiment of the present invention will be described with reference to the drawings. <1. Regarding Configuration of Chain Block> [0043] As illustrated in FIGS. 1 to 5 and the like, the chain block 10 includes a first frame 11 , a second frame 12 , a gear case 13 , a wheel cover 14 , a load-sheave hollow shaft 20 , and a speed reducing mechanism 30 , and these are fixed via stud bolts SB (corresponding to a fixation member)and nuts N. Then, between the first and second frames 11 and 12 , between the first frame 11 and the gear case 13 , and between the second frame 12 and the wheel cover 14 , respective members are mounted; however, a part of the members protrude from therebetween. Hereinafter, the respective members will be described. [0044] Between the first and second frames 11 and 12 , a part of the load-sheave hollow shaft 20 , an upper hook 40 , a guide roller 42 , a metal fastener 43 , a stripper 44 , and the like are positioned. As illustrated in FIGS. 4 and 5 , the load-sheave hollow shaft 20 is supported by the first and second frames 11 and 12 through bearings B 1 and B 2 such as ball bearings, which are fitted into insertion holes 11 a and 12 a of the first and second frames 11 and 12 , respectively. That is, the bearings B 1 and B 2 are positioned in outer peripheries of bearing fitting portions 21 a and 21 b of the load-sheave hollow shaft 20 , and further the bearings B 1 and B 2 are positioned in the insertion holes 11 a and 12 a. Thereby, the load-sheave hollow shaft 20 is supported by the first and second frames 11 and 12 . [0045] As illustrated in FIGS. 6 and 9 , the first frame 11 has a circular portion 110 having a circular contour and a frame protruding portion 111 protruding from the circular portion 110 . Total three frame protruding portions 111 , two frame protruding portions on the upper side (Z1 side) and one frame protruding portion on the lower side (Z2 side) are provided. Furthermore, each of the frame protruding portions 111 is provided with an insertion hole 112 into which the stud bolt SB is inserted. Then, insertion holes are provided in such a manner that when the total three insertion holes 112 are connected to each other, an isosceles triangle is formed; however, the insertion holes may be provided in such a manner that an equilateral triangle or an approximately equilateral triangle is formed. Furthermore, the insertion holes may be provided in such a manner that when the total three insertion holes 112 are connected to each other, other triangle shapes than the isosceles triangle shape are formed. [0046] As illustrated in FIGS. 6 and 9 , a pair of frame protruding portions 111 a positioned on the upper side (Z1 side) among the above-described frame protruding portions 111 are arranged along the Y direction. Then, a concave portion 113 is formed by a site on the lower side (Z2 side) of an outer peripheral edge portion of each of the pair of the frame protruding portions 111 a and an outer peripheral edge portion of the circular portion. The concave portion 113 serves as a portion that reduces the width dimension of the first frame 11 between the circular portion 110 and the side of the lower side (Z2 side) of a frame protruding portion 111 a . Thus, the chain block 10 can be grasped by, for example, positioning different fingers or the like in a pair of concave portions 113 , respectively. That is, the chain block 10 can be grasped or held by the concave portion 113 , in addition to the upper hook 40 . Note that a separate grasping member or holding member can be positioned in each of the pair of concave portions 113 instead of fingers to grasp or hold the chain block 10 for the purpose of carrying and storing or packing. [0047] Note that the frame protruding portion 111 existing on the lower side (Z2 side) is referred to as a frame protruding portion 111 b, as necessary. An end surface on the Z2 side of the frame protruding portion 111 b is a flat portion 111 b 1 parallel to the Y axis. The existence of the flat portion 111 b 1 enables the chain block 10 to stand alone without falling down. Thereby, the chain block 10 is easy to carry and store or pack. [0048] Furthermore, as illustrated in FIG. 8 , the second frame 12 is also provided with a circular portion 120 , a frame protruding portion 121 ( 121 a and 121 b ), an insertion hole 222 , and a concave portion 123 , which are similar to those of the above-described first frame 11 . Since these have similar configurations to the configurations of the respective sites in the first frame 11 , the description of each site is omitted. Furthermore, the second frame 12 corresponds to a frame member. However, the first frame 11 may correspond to a frame member, and both of the first and second frames 11 and 12 may correspond to frame members. [0049] Furthermore, as illustrated in FIGS. 4 and 5 , a gear fitting portion 22 is provided closer to the gear case 13 side than the bearing fitting portion 21 a on the first frame 11 side of the load-sheave hollow shaft 20 , and a load gear 31 forming the speed reducing mechanism 30 is held in a spline-coupled state by the gear fitting portion 22 . Note that the gear case 13 side of the gear fitting portion 22 is provided with a groove portion 22 a to which a snap ring E is mounted. By the snap ring E mounted to the groove portion 22 a, the load gear 31 is restricted from moving toward the X2 side of the load gear 31 . On the other hand, a clearance groove 22 b for a spline process is formed at a site on the bearing fitting portion 21 a side of the gear fitting portion 22 , and further a fixation stepped portion 22 c having a larger diameter than that of the gear fitting portion 22 is provided at a site closer to the bearing fitting portion 21 a side than the clearance groove 22 b. The fixation stepped portion 22 c restricts the load gear 31 from moving toward the X1 side. [0050] Here, the load gear 31 is provided with a central hole 31 a into which the above-described gear fitting portion 22 is inserted. In addition, as illustrated in FIGS. 4 and 5 , concave portions 31 b are provided around the central hole 31 a on each end side of the load gear 31 . The concave portions 31 b are provided in the shape of recessing each end surface of the load gear 31 by a predetermined depth. That is, as illustrated in FIGS. 4 and 5 , a concave portion 31 b 1 recessed from the end surface on the X1 side of the load gear 31 faces the bearing B 1 . However, the existence of the concave portion 31 b 1 can increase clearance between the load gear 31 and the bearing B 1 . Thereby, when the load gear 31 rotates in a state where machine oil (grease) exists between the load gear 31 and the bearing B 1 , a mechanical loss caused by the viscosity of the machine oil (grease) when the load gear 31 rotates can be reduced, and the fluidity of machine oil (grease) can be improved. Similarly, a concave portion 31 b 2 recessed from the end surface on the X2 side of the load gear 31 faces a large-diameter gear 61 of a reduction gear member 60 . However, the existence of the concave portion 31 b 2 can increase clearance between the load gear 31 and the large-diameter gear 61 . Also in this case, when the load gear 31 rotates, a mechanical loss caused by the viscosity of machine oil (grease) when the load gear 31 rotates can be reduced, and the fluidity of the machine oil (grease) can be improved. [0051] Furthermore, the load-sheave hollow shaft 20 has a pair of flange portions 23 a forming the load sheave 23 , and further has a chain pocket 23 b (refer to FIG. 4 ) forming the load sheave 23 between the pair of flange portions 23 a. The chain pocket 23 b is a portion into which a metal hoop C 1 a of a load chain C 1 is fitted, and has a horizontal pocket (not illustrated) into which the metal hoop C 1 a is fitted in a state where the direction in which the metal hoop C 1 a becomes flat is parallel to the axial direction (X direction), and a vertical pocket (not illustrated) which has a deeper groove shape than the horizontal pocket and into which the metal hoop C 1 a is fitted in a state where the direction in which the metal hoop C 1 a becomes flat crosses the axial direction (X direction). [0052] Furthermore, the load-sheave hollow shaft 20 is provided with a hollow hole 24 . A drive shaft 70 is inserted into the hollow hole 24 , and an end portion on the second frame 12 side of the hollow hole 24 is provided with a bearing stepped portion 26 for receiving a bearing B 3 which shaft-supports the drive shaft 70 . Here, an end portion on the gear fitting portion 22 side of the hollow hole 24 is provided with a receiving concave portion 27 for receiving a flange portion 71 of the drive shaft 70 . By the flange portion 71 of the drive shaft 70 positioned in the receiving concave portion 27 , the length along the axial direction (X direction) of the drive shaft 70 can be reduced, and the dimension along the X direction (the axial direction of the drive shaft 70 ) of the chain block 10 can be reduced. Furthermore, By the reduced length along the axial direction of the drive shaft 70 , the strength of the drive shaft 70 can be improved. [0053] As illustrated in FIGS. 1 to 6 , the upper hook 40 is mounted to the first and second frames 11 and 12 through a connecting shaft 41 (refer to FIGS. 6 and 8 ), and mounted in a rotatable state with respect to the connecting shaft 41 . A hook latch 40 a which is biased in a closing direction by a basing unit (not illustrated) is mounted to the upper hook 40 . [0054] One end side and the other end side of the guide roller 42 illustrated in FIGS. 2 and 8 are shaft-supported rotatably with respect to the first frame 11 and the second frame 12 , respectively. For example, a pair of guide rollers 42 are provided at an interval of 180 degrees with the center of the load-sheave hollow shaft 20 interposed therebetween. The guide roller 42 is a member which rotates as the load chain C 1 is wound up or the like, and mounted facing the load sheave 23 and being separated by a distance to prevent the load chain C 1 from coming off the chain pocket 23 b. [0055] The metal fastener 43 illustrated in FIGS. 1 to 4 and 9 is a portion to which a metal fitting pin 43 a is mounted, and the metal fitting pin is inserted into the metal hoop C 1 a in an end portion of the load chain C 1 , which is opposite to the side to which the lower hook 45 is mounted. One end side and the other end side of the metal fastener 43 are also shaft-supported rotatably with respect to the first frame 11 and the second frame 12 , respectively. [0056] The stripper 44 illustrated in FIG. 4 is a member that prevents the occurrence of a lock state in which the load chain C 1 looped over the load sheave 23 follows the load sheave 23 more than necessary and the load sheave 23 is stuck. Respective end portions on one end side and the other end side of the stripper 44 are inserted into respective support holes 11 b and 12 b existing in the first and second frames 11 and 12 , and thus the stripper 44 is mounted to the first and second frames 11 and 12 . [0057] Furthermore, as illustrated in FIGS. 4 to 6 , an auxiliary plate 50 illustrated in FIGS. 7A and 7B is mounted to an end surface on the side facing the gear case 13 of the first frame 11 . The auxiliary plate 50 is provided with a flange portion 51 and a drawing portion 52 . The flange portion 51 is a portion that comes in contact with the end surface of the first frame 11 , and the flange portion 51 is provided with a fixation hole 53 . Then, the auxiliary plate 50 is mounted to the first frame 11 by inserting a fixation member 55 such as a rivet (refer to FIG. 5 ) into the fixation hole 53 and a mounting hole 11 c provided in the first frame 11 . Furthermore, the drawing portion 52 is a portion positioned closer to the center side than the flange portion 51 , and is a portion formed by, for example, drawing the center side of the auxiliary plate 50 so as to be spaced by a predetermined distance from the end surface of the first frame 11 . In the present embodiment, the drawing portion 52 has a recessed portion existing on the outer peripheral side thereof due to the existence of the fixation hole 53 in the configuration illustrated in FIGS. 6 , 7 A, and 7 B; however, the drawing portion 52 has a corner formed in an R-shaped approximately rhombic shape, except the recessed portion. [0058] Here, the mounting positions of the above-described fixation member 55 and the guide roller 42 with respect to the first frame 11 are in a positional relation illustrated in FIG. 8 . That is, the pair of guide rollers 42 are mounted adjacent to respective fixation members 55 , and arranged at symmetrical positions with the center interposed between the guide rollers 42 . Furthermore, the guide rollers 42 are provided adjacent to the fixation members 55 ( 55 a ) separated from the rotation center of the load sheave 23 or the like, and are also provided at positions spaced apart from the fixation members 55 ( 55 b ) close to the center with the Y direction interposed therebetween. In such an arrangement, when the load chain C 1 is wound up, the entire chain block 10 tends to rotate along a rotation direction M of FIG. 8 such that a direction F of a force received from the load chain C 1 becomes a direction orthogonal to a line L connecting the fixation members 55 adjacent to each other. In such rotation, when the guide rollers 42 are arranged as illustrated in FIG. 8 , a line connecting the pair of guide rollers 42 approaches the horizontal state, and a guide property of the load chain can favorably be maintained. [0059] Furthermore, as illustrated in FIGS. 6 , 7 A, and 7 B, a central hole 56 is provided on the center side of the drawing portion 52 . The central hole 56 is provided on the same axis as the above-described insertion hole 11 a, and has the same diameter as that of the insertion hole 11 a . Then, the above-described bearing B 1 is positioned in the central hole 56 to support the load-sheave hollow shaft 20 . Furthermore, the drawing portion 52 is provided with a bearing hole 57 along a diagonal in the longitudinal direction of the approximately rhombic shape thereof. For example, a pair of bearing holes 57 are provided at positions by an equal distance from the center of the central hole 56 , and are each formed in a shape having a rising portion 57 a by burring processing, for example. A shaft support portion 63 on one end side of the reduction gear member 60 (X1 side in FIG. 5 ) is inserted into the bearing hole 57 , and the reduction gear member 60 is shaft-supported by the bearing hole. Note that a shaft support portion 64 on the other end side of the reduction gear member 60 (X2 side in FIG. 5 ) is inserted into a bearing hole 13 a of the gear case 13 through a bearing B 4 such as a bush, and the reduction gear member 60 is shaft-supported by the bearing hole 13 a. [0060] As illustrated in FIGS. 5 , 10 A, and 10 B, each of a pair of reduction gear members 60 (the arrangement of the pair of reduction gear members 60 is also illustrated in FIG. 9 ) is provided with the large-diameter gear 61 (corresponding to a first reduction gear member) and a small-diameter gear 62 (corresponding to a second reduction gear member), and is also provided with the shaft support portion 63 inserted into the bearing hole 57 and the shaft support portion 64 inserted into the bearing hole 13 a as described above. The large-diameter gear 61 engages with a pinion gear 72 of the drive shaft 70 , and a driving force is transferred from the drive shaft 70 to the reduction gear member 60 at a first reduction gear ratio. Furthermore, the large-diameter gear 61 is provided with a chamfered surface portion 61 a. The chamfered surface portion 61 a is provided at a site on the X1 side of the outer peripheral side of the large-diameter gear 61 , and is provided having a smaller diameter than that of another site of the large-diameter gear 61 . The existence of the chamfered surface portion 61 a prevents the large-diameter gear 61 from interfering with an inclined portion 73 and a curved surface portion 74 of the drive shaft 70 . [0061] Furthermore, the small-diameter gear 62 engages with the load gear 31 , and the driving force transferred to the reduction gear members 60 is transferred to the load gear 31 at a second reduction gear ratio. Note that the small-diameter gear 62 and the above-described large-diameter gear 61 are integrally formed by cold forging, for example. However, the small-diameter gear 62 and the large-diameter gear 61 may be integrally formed by a combination of other processing such as precise forging and cutting, and may be separately formed by a combination of the above-described processing and thereafter coupled to each other. [0062] As illustrated in FIG. 10A , a swelling portion 65 is provided closer to the large-diameter gear 61 side (X1 side) than the shaft support portion 64 of the reduction gear member 60 . The swelling portion 65 is provided in a concave portion 60 a provided in a central portion of an end surface of the reduction gear member 60 , but the swelling portion 65 is a portion swelling toward the outside in the radial direction so as to have a larger diameter than that of the shaft support portion 64 , and is intermittently swelling along the peripheral direction (in FIG. 10A , three swelling portions 65 are provided). Then, a recessed portion 66 having a relatively smaller diameter than that of the swelling portion 65 exists between the adjacent swelling portions 65 . Furthermore, the outer peripheral side of the shaft support portion 64 is provided with an oil groove 64 a along the axial direction (X direction) of the reduction gear member 60 , and the oil groove 64 a is in communication with any one of recessed portions 66 . Thereby, machine oil (grease) can be supplied to the bearing B 4 such as a bush through the concave portion 60 a and the oil groove 64 a. Furthermore, the existence of the above-described swelling portion 65 can make the large-diameter gear 61 spaced apart from the bearing B 4 , and the existence of the concave portion 60 a and the oil groove 64 a can reduce a mechanical loss caused by the viscosity of the machine oil (grease) between the large-diameter gear 61 and bearings B 4 and B 5 , and improve the fluidity of the machine oil (grease). [0063] As illustrated in FIGS. 4 and 5 , the drive shaft 70 (refer to FIGS. 11A to 11C ) is a member extending from the gear case 13 side to the hand wheel 80 side along the X direction. The drive shaft 70 is inserted into the hollow hole 24 of the load-sheave hollow shaft 20 as described above, and provided rotatably with respect to the load sheave 23 through the bearing B 3 at the bearing stepped portion 26 . Furthermore, the drive shaft 70 is provided with the flange portion 71 , and the flange portion 71 is positioned in the receiving concave portion 27 . Then, by the flange portion 71 received in a bottom portion 27 a of the receiving concave portion 27 , the drive shaft 70 is restricted from moving toward the hand wheel 80 side, and the dimension in the axial direction of the drive shaft 70 can be reduced. [0064] A portion protruding from the hollow hole 24 toward the gear case 13 side (X2 side) of the drive shaft 70 is provided with the pinion gear 72 (corresponding to a first gear) engaging with the above-described large-diameter gear 61 . In FIG. 12A , the pinion gear 72 has five teeth 721 . A thickness Da of each tooth 721 of the pinion gear 72 is set to be different from a thickness Db of a tooth 721 H of a pinion gear 72 H according to the related art as illustrated in FIG. 13B . That is, in the pinion gear 72 according to the present embodiment, the thickness Da of a tooth tip 722 of each tooth 721 (hereinafter, the thickness Da of the tooth tip 722 is referred to as a thickness Da2 as illustrated in FIG. 13A ) is provided to be larger than the thickness Db of a tooth tip 722 H of each tooth 721 H according to the related art (hereinafter, the thickness Db of the tooth tip 722 H is referred to as a thickness Db2 as illustrated in FIG. 13B ). [0065] Note that, as described above, when the thickness Da2 of the tooth tip 722 is made larger than the thickness Db2 of the tooth tip 722 H according to the related art, the thickness Da of each tooth 721 can be made as follows. That is, in the pinion gear 72 according to the present embodiment, a dimension Ba (not illustrated) of a tooth bottom 723 existing between the neighboring teeth 721 is provided to be smaller than a dimension Bb (not illustrated) of a tooth bottom 723 H of the pinion gear 72 H according to the related art. Thus, on the tooth bottom 723 side, the thickness Da of the tooth 721 (hereinafter, the thickness Da on the tooth bottom 723 side is referred to as a thickness Da1 as illustrated in FIG. 13A ) is provided to be larger than the thickness Db of the tooth 721 according to the related art (hereinafter, the thickness Db on the tooth bottom 723 H side is referred to as a thickness Db1 as illustrated in FIG. 13B ). [0066] In addition, the thicknesses Da and Db at each site of the teeth 721 and 712 H are considered as illustrated in FIGS. 13A and 13B . In this case, in the configuration illustrated in FIG. 13A , the ratio of a thickened portion 724 in the tooth thickness Da of the tooth 721 in the present embodiment is set to increase from the side of the tooth bottom 723 to a side of the tooth tip 722 , as compared with the tooth thickness Db of the tooth 721 H in the related art. Accordingly, since the ratio of the thickened portion 724 is larger on the side of the tooth tip 723 , strength of the tooth 721 on the side of the tooth tip 723 can be improved significantly. [0067] Note that the thickness Da of each tooth 721 may be set as follows. That is, the thickness Da1 on the tooth bottom 723 side may be set to be equal to the thickness Dbl on the tooth bottom 723 H side of the tooth 721 H according to the related art. In this case, however, it is necessary to prevent an undercut from occurring on the tooth bottom 723 side. Note that, when the thickness Da1 on the tooth bottom 723 side is provided as described above to be equal to the thickness Db1 on the tooth bottom 723 H side of the tooth 721 H according to the related art, the dimension of the thickened portion 724 may be set to become large from the tooth bottom 723 toward the tooth tip 722 . [0068] Furthermore, each tooth 611 of the large-diameter gear 61 engaging with the pinion gear 72 as described above is thinned by an amount corresponding to thickening of the thickened portion 724 of the tooth 721 . That is, in the large-diameter gear 61 , a tooth thickness Dc (refer to FIG. 13A ) of the tooth 611 is smaller than a tooth thickness Dd (refer to FIG. 13D ) of the tooth 611 H according to the related art as much as the increasing amount from the tooth thickness Db of the tooth 721 H of the pinion gear 72 H according to the related art to the tooth thickness Da of the tooth 721 of the pinion gear 72 . At this time, the thickness Da2 of the tooth tip 722 of the pinion gear 72 is provided to be larger than the thickness Dc1 of the tooth tip 612 of the large-diameter gear 61 . Here, in a portion where the tooth 721 and the tooth 611 come in contact with each other, the change in the thickness Da of the tooth 721 from the tooth bottom 723 side to the tooth tip 722 side in the pinion gear 72 (the thickened portion 724 ) corresponds to the change in the thickness Dc of the tooth 611 from the tooth tip 612 side to the tooth bottom 613 side in the large-diameter gear 61 . Thereby, the favorable engagement between the pinion gear 72 and the large-diameter gear 61 is realized. [0069] Note that, in the configurations illustrated in FIGS. 12A , 12 B, 13 A, and 13 B, the pinion gear 72 is provided with the five teeth 721 , and the large-diameter gear 61 is provided with 35 teeth 611 . Moreover, a pair of large-diameter gears 61 (reduction gear member 60 ) are arranged at symmetrical positions with the pinion gear 72 interposed therebetween, and the pinion gear 72 is engaged with both of the pair of large-diameter gears 61 . Thus, when the tooth 611 of the large-diameter gear 61 rotates once, the tooth 611 of the large-diameter gear 61 comes in contact with the tooth 721 of the pinion gear 72 only once; however, during one rotation of the large-diameter gear 61 , the tooth 721 of the pinion gear 72 comes in contact with the tooth 611 of the large-diameter gear 61 fourteen times. [0070] Furthermore, each of the reduction gear member 60 and the drive shaft 70 is made of a metal and is preferably made of an iron-based metal from a viewpoint of abrasion resistance. Furthermore, the reduction gear member 60 and the drive shaft 70 are preferably made of similar materials. However, at least the pinion gear 72 of the drive shaft 70 may be made of a material having wear resistance more excellent than that of the large-diameter gear 61 of the reduction gear member 60 . [0071] A portion protruding from the hollow hole 24 toward the gear case 13 side (X2 side) of the drive shaft 70 is provided with the pinion gear 72 (corresponding to a gear portion) engaging with the above-described large-diameter gear 61 . As illustrated in FIGS. 11A and 11C , a base portion of the pinion gear 72 with respect to the flange portion 71 is provided with the inclined portion 73 . Further, the predetermined curved surface portion 74 is provided between each tooth of the pinion gear 72 and the inclined portion 73 . The curved surface portion 74 is formed in a round shape, for example. Then, the existence of the inclined portion 73 and the curved surface portion 74 can prevent concentration of stress from occurring in a boundary portion between the pinion gear 72 and the flange portion 71 . It is to be noted that the curved surface portion 74 has only to be 1/10 or larger of the inclined portion 73 , and by setting the ratio thereof in the inclined portion 73 to 1/10 or larger, the stress concentration can be prevented favorably. [0072] Here, the thickness on the tip side of the tooth of the pinion gear 72 is provided to be larger than the thickness on the tip side of the large-diameter gear 61 engaging with the pinion gear 72 . Thus, the lifetime of the pinion gear 72 can be prolonged. That is, since the number of teeth of the pinion gear 72 is smaller than the number of teeth of the large-diameter gear 61 , each tooth of the pinion gear 72 slides more times than each tooth of the large-diameter gear 61 . Thereby, each tooth of the pinion gear 72 wears earlier than each tooth of the large-diameter gear 61 . However, by setting the tooth thickness on the tip end side of the tooth of the pinion gear 72 to be larger than the tooth thickness on the tip end side of the large-diameter gear 61 and setting the tooth width to be larger, lifetime of the pinion gear 72 can be prolonged. [0073] Furthermore, the drive shaft 70 is provided with a shaft support portion 75 closer to the gear case 13 side (X2 side) than the pinion gear 72 . The shaft support portion 75 is a portion to which the bearing B 5 is mounted on the outer peripheral side thereof, and the bearing B 5 is mounted to a bearing mounting portion 13 b provided in the gear case 13 . Thereby, an end portion on the X2 side of the drive shaft 70 is rotatably supported by the gear case 13 through the bearing B 5 . Further, a male screw portion 76 is provided on the hand wheel 80 side of the drive shaft 70 . The male screw portion 76 is a portion to which a female screw portion 81 of the hand wheel 80 or a female screw portion 91 a of a brake receiver 91 , which will be described below, are screwed. Note that an end portion on the X2 side of the male screw portion 76 is provided with a stepped portion 77 , and the brake receiver 91 to be described below is locked by the stepped portion 77 . Furthermore, a stopper receiving portion 78 having a pin hole 78 a is provided closer to the X1 side than the male screw portion 76 , and a wheel stopper 84 to be described below is arranged in the stopper receiving portion 78 and retained by a stopper pin 79 . [0074] Note that the gear case 13 is a member that covers the speed reducing mechanism 30 such as the reduction gear member 60 and the load gear 31 , and the gear case 13 is fixed to the first frame 11 via the stud bolt SB and the nut N. [0075] As illustrated in FIGS. 4 and 5 , an end surface of the second frame 12 on the side not facing the first frame 11 is provided with the hand wheel 80 and a brake mechanism 90 . The hand wheel 80 has the female screw portion 81 on the center side thereof, and the female screw portion 81 is screwed to the male screw portion 76 of the drive shaft 70 . Furthermore, a chain pocket 82 similar to the above-described load sheave 23 is provided between sites of the outer peripheral side of the hand wheel 80 , facing a pair of flange portions 80 a. The chain pocket 82 is a portion into which a metal hoop C 2 a of a hand chain C 2 is fitted, and has a horizontal pocket (not illustrated) into which the metal hoop C 2 a is fitted in a state where the direction in which the metal hoop C 2 a becomes flat is parallel to the axial direction, and a vertical pocket (not illustrated) which has a deeper groove shape than the horizontal pocket and into which the metal hoop C 2 a is fitted in a state where the direction in which the metal hoop C 2 a becomes flat crosses the axial direction. Note that the wheel stopper 84 is provided closer to the tip side of the male screw portion 76 (X1 side) than the hand wheel 80 via a collar 83 or the like. The wheel stopper 84 is a ring-shaped member and has a through-hole 84 a along the radial direction. Then, by inserting a stopper pin 85 into the through-hole 84 a and the pin hole 78 a of the stopper receiving portion 78 , the wheel stopper 84 is restricted from moving in the X direction of the drive shaft 70 . The existence of the wheel stopper 84 restricts the hand wheel 80 from moving to the X1 side. [0076] Furthermore, the brake mechanism 90 includes the brake receiver 91 , a brake plate 92 , a ratchet wheel 94 , a pawl member 95 , and like as main components. As illustrated in FIGS. 4 and 5 , the brake receiver 91 is arranged on the second frame 12 side of the male screw portion 76 of the drive shaft 70 . The brake receiver 91 has the female screw portion 91 a on the center side thereof, and further has a flange portion 91 b and a hollow boss portion 91 c. The female screw portion 91 a is a portion that is screwed to the male screw portion 76 of the drive shaft 70 , and the flange portion 91 b of the brake receiver 91 is locked by the stepped portion 77 by the screwing of the female screw portion. The flange portion 91 b is provided to have a larger diameter than that of the hollow boss portion 91 c, and can receive the brake plate 92 to be described below. The hollow boss portion 91 c is positioned closer to the hand wheel 80 side (X1 side) than the flange portion 91 b, and supports the ratchet wheel 94 via a bush 93 to be described below. [0077] The brake plate 92 ( 92 a ) is positioned between the flange portion 91 b and the ratchet wheel 94 to be described below. When pressurized from the hand wheel 80 side, the brake plate applies a large frictional force between the flange portion 91 b and the ratchet wheel 94 to be described below, and the brake receiver 91 integrally rotates with the ratchet wheel 94 by the large frictional force. Note that the brake plate 92 ( 92 b ) is also arranged between the ratchet wheel 94 and the hand wheel 80 and applies a large frictional force between the ratchet wheel 94 and the hand wheel 80 by being pressurized from the hand wheel 80 , and the hand wheel 80 integrally rotates with the ratchet wheel 94 by the large frictional force. [0078] As illustrated in FIGS. 4 and 5 , the bush 93 is mounted to the hollow boss portion 91 c of the brake receiver 91 , and the ratchet wheel 94 is provided on the outer peripheral side of the bush 93 . Thereby, the ratchet wheel 94 is provided rotatably with respect to the brake receiver 91 . As illustrated in FIG. 14 , a tip end of each pawl member 95 engages with a tooth portion 94 a of the ratchet wheel 94 , and the engagement thereof forms a ratchet wheel mechanism which prevents the ratchet wheel 94 from rotating in the opposite direction (rotating in the winding-up direction). Note that the pawl member 95 is rotatably provided through a pawl shaft 95 a, and one end of a biasing spring 95 b is attached to the pawl member 95 , so that a basing force is applied such that the tip of the pawl member 95 always engages with the tooth portion 94 a of the ratchet wheel 94 . [0079] Furthermore, a pair of pawl member 95 are provided. In the configuration illustrated in FIG. 14 , one pawl member 95 is arranged at a position where the pawl member is inclined at a predetermined angle such as 30 degrees to the vertical direction. Furthermore, the other pawl member 95 is provided at a position adjacent to the one pawl member 95 . However, the arrangement mode thereof is an arrangement where the pair of pawl member 95 are both fitted into the same quadrant such as the first quadrant of the orthogonal coordinate system. Thereby, a space S is formed at a position corresponding to the third quadrant with respect to the first quadrant of the orthogonal coordinate system (a position on the Z2 side and the Y2 side in FIG. 14 ), and when the load chain C 1 a is wound up, the lower hook 45 can be positioned in the space S. However, other arrangements may be employed as the arrangement of the pair of pawl member 95 , and for example, a configuration of arranging each of the pair of pawl members in a diagonal direction with the rotation center of the ratchet wheel 94 interposed therebetween may be employed. [0080] The wheel cover 14 is a member that covers the upper side of the hand wheel 80 and the upper side of the brake mechanism 90 (refer to FIGS. 1 to 3 and the like), and the wheel cover 14 is fixed to the second frame 12 through the stud bolt SB and the nut N. The wheel cover 14 is formed by plastic working such as press working, and includes, as illustrated in FIG. 15 , a flange portion 141 , a side surface 142 , and an end surface 143 , which are formed by the plastic working. The flange portion 141 is a portion that abuts against the second frame 12 . The flange portion 141 is surface-bonded to the second frame 12 , and thereby provided in a state of favorably resisting a tightening force between the stud bolt SB and the nut B. In order to realize such surface-bonding, the flange portion 141 is formed to expand outward with respect to the side surface 142 in parallel to the second frame 12 toward the tip side (X2 side) spaced apart from the end surface 143 . [0081] Note that the flange portion 141 is bent at an angle nearly perpendicular to the side surface 142 ; however, in a state where the wheel cover 14 is mounted, the side surface 142 is not necessarily perpendicular to the second frame 12 . Thus, the flange portion 141 may be bent at an angle perpendicular to the side surface 142 , but not necessarily bent perpendicularly. [0082] Furthermore, the wheel cover 14 illustrated in FIG. 15 and the like may be formed by deep-drawing a steel plate or the like. [0083] The side surface 142 is a portion that connects between the flange portion 141 and an outer periphery edge portion of the end surface 143 , and is formed as illustrated in FIG. 1 so as to have a large dimension in the approaching and separating direction (X direction) relative to the second frame 12 . Furthermore, the side surface 142 is not provided over the entire outer peripheral edge portion of the end surface 143 . That is, the side surface 142 has a portion positioned on the upper side (hereinafter, referred to as an upper side surface 142 a as necessary) and a portion positioned on the lower side (hereinafter, referred to as a lower side surface 142 b as necessary). Note that a pair of sets of stud bolts SB and nuts N are provided on the upper side of the wheel cover 14 (Z1 side) along the Y direction. On the other hand, only one set of the stud bolt SB and the nut B exists on the lower side (Z2 side) of the wheel cover 14 . Thus, the upper side surface 142 a is provided to have a larger dimension in the Y direction than the lower side surface 142 b, and a pair of wrap-around portions 148 (described below) also exist in the upper side surface 142 a. [0084] Note that the hand chain C 2 can extends from a notched portion 144 between the upper side surface 142 a and the lower side surface 142 b. Furthermore, a left-right side surface 145 is provided at a site closer to the end surface 143 side than the notched portion 144 . The left-right side surface 145 is a portion extending toward the second frame 12 more than the end surface 143 in a similar manner to the upper side surface 142 a and the lower side surface 142 b; however, the left-right side surface 145 is provided to have the length toward the second frame 12 significantly smaller than those of the upper side surface 142 a and the lower side surface 142 b, due to the existence of the notched portion 144 . [0085] Furthermore, the end surface 143 is a portion facing to the hand wheel 80 of the wheel cover 14 . The end surface 143 is provided so as to be continuous with the upper side surface 142 a, the lower side surface 142 b, and the left-right side surface 145 in the outer peripheral edge portion thereof. Furthermore, the end surface 143 has large dimensions in the Y direction and the Z direction (corresponding to the drooping direction) in FIG. 15 . The end surface 143 may be provided in a planar shape; however, as illustrated in FIG. 15 , a configuration where unevenness exists may be employed in order to improve the designability and improve the strength of the wheel cover 14 . [0086] Furthermore, as illustrated in FIGS. 3 and 15 , in the present embodiment, the end surface 143 is provided with a circular portion T1 having a circular shape where the radius from the center to the edge portion is R1 (in FIGS. 3 and 15 , the circular shaped portion has a partially circular shape of which a portion on the upper side is cut; however, such a partially circular shape is described hereinafter being included in the circular shape) overlapping a triangular portion T2 having a triangle shape where the distance from the same center to the edge portion is R2. Here, the radius R1 and the distance R2 has the relation of R2>R1. Thereby, the corner sides of the triangular portion T2 are provided to protrude from the circular portion T1. Hereinafter, the portion protruding from the circular portion T1 is referred to as a protruding portion 146 . [0087] Furthermore, in the present embodiment, the triangular portion T2 is provided in an isosceles triangle shape of which the base is positioned on the upper side and of which the vertex is positioned on the lower side; however, the triangular portion may be provided in an equilateral triangle shape or an approximately equilateral triangle shape. Furthermore, the triangular shaped portion may be provided in other triangle shapes than the isosceles triangle shape. [0088] As illustrated in FIGS. 3 and 15 , the protruding portion 146 is provided with a bolt hole 147 (corresponding to the fixation hole). Since the bolt hole 147 is provided in the protruding portion 146 , three bolt holes 147 are provided on the outer peripheral edge portion side of the wheel cover 14 , and two of the bolt holes are provided along the Y direction on the upper side (Z1 side). [0089] As illustrated in FIGS. 3 , 15 , and 16 , the upper side surface 142 a is provided with a wrap-around portion 148 . The wrap-around portion 148 is provided in such a manner that the upper edge side thereof (an edge portion on the Z1 side) is continuous with the protruding portion 146 . Furthermore, in the wrap-around portion 148 , an angle θ formed by a tangential line A 1 (may be set to a planar tangential surface A 1 ) and a tangential line A 2 (may be set to a planar tangential surface A 2 ) in FIG. 16 is provided to become an acute angle. [0090] In the configuration illustrated in FIG. 16 , the angle formed by the tangential line A 1 (tangential surface A 1 ) and the tangential line A 2 (tangential surface A 2 ) is provided to be approximately 60 degrees. Furthermore, a line connecting the intersection between the tangential line A 1 (tangential surface A 1 ) and the tangential line A 2 (tangential surface A 2 ) to the center is a bisector A 3 or approximates the bisector A 3 of the angle formed by the tangential line A 1 (tangential surface A 1 ) and the tangential line A 2 (tangential surface A 2 ). [0091] Here, in the wheel cover 14 H according to the related art, an angle a formed by the tangential line A 1 (tangential surface A 1 ) and the tangential line A 2 (tangential surface A 2 ) in the upper side surface 142 H is provided to become an obtuse angle, as illustrated in FIGS. 17A , 17 B, and 21 . Thus, when the wrap-around portion 148 of the wheel cover 14 according to the present embodiment is compared to the vicinity of the mounting site of the stud bolt SB of the wheel cover 14 H according to the related art (a portion corresponding to the wrap-around portion 148 ; hereinafter referred to as a corner portion 148 H), the wheel cover 14 according to the present embodiment has characteristics of larger strength. [0092] Specifically, the corner portion 148 H in the configuration illustrated in FIG. 21 is provided so as to be separated from the stud bolt SB and the bolt hole 147 , compared to the wrap-around portion 148 according to the present embodiment as illustrated in FIGS. 15 and 16 . Thus, when a load acts, the end surface 143 around the bolt hole 147 is easier to deform than the case where the wrap-around portion 148 according to the present embodiment exists. In contrast, in the present embodiment, the wrap-around portion 148 is positioned inside the end surface 143 and provided adjacent to the stud bolt SB and the bolt hole 147 , compared to the configuration of the related art as illustrated in FIG. 21 . Thus, even when a load acts on the end surface 143 around the bolt hole 147 , the end surface 143 and the wrap-around portion 148 become difficult to deform. [0093] Here, FIGS. 17A and 17B illustrate images when an external force acts on the wrap-around portion 148 and the end surface 143 . A case where as illustrated in FIG. 17A , ‘F’ going toward the rotation center acts on a portion corresponding to the wrap-around portion 148 according to the configuration of the related art, and similarly, as illustrated in FIG. 17B , ‘F’ going toward the rotation center also acts on the wrap-around portion 148 according to the present embodiment is considered. As apparent from FIGS. 17A and 17B , a component of a force along the upper side surface 142 a becomes larger in the configuration of the related art. Thereby, when the wrap-around portion 148 according to the present embodiment exists, the strength becomes larger than in the configuration of the related art as illustrated in FIGS. 17A and 21 . [0094] Furthermore, as illustrated in FIGS. 2 and 15 , the wrap-around portion 148 is provided with a chain guide portion 149 in a continuous state. The chain guide portion 149 is a portion provided adjacent to the hand chain C 2 , and is a portion for preventing the hand chain C 2 from coming off the chain pocket 82 even when the hand chain C 2 significantly moves (even when the hand chain C 2 “rages”). The chain guide portion 149 is provided so as to be positioned on the lower side (Z2 side) of the wrap-around portion 148 , and the chain guide portion 149 has a guide bent portion 149 a, a leg portion 149 b, and a protruding tip 149 c. The guide bent portion 149 a is a portion facing the chain pocket 82 of the hand wheel 80 . An end portion along the X direction of the guide bent portion 149 a is provided facing each flange portion 80 a. [0095] Note that clearance between the end portion of the guide bent portion 149 a and the flange portion 80 a is preferably smaller than the diameter of the metal hoop C 2 a of the hand chain C 2 . In such a configuration, even when the hand chain C 2 significantly moves (even when the hand chain C 2 rages), the hand chain C 2 is prevented from coming off the chain pocket 82 . [0096] Furthermore, an end portion on the X2 side of the leg portion 149 b is provided at the same position as the flange portion 141 , and an end surface of the leg portion 149 b can abut against the second frame 12 . Furthermore, the end surface of the leg portion 149 b is provided with the protruding tip 149 c . The protruding tip 149 c is a portion inserted into an insertion hole 124 (refer to FIG. 14 ) provided in the second frame 12 . By the protruding tip 149 c inserted into the insertion hole 124 , the strength of the chain guide portion 149 can be improved. [0097] Here, as illustrated in FIG. 18 , a folded-back portion 150 formed by hemming processing exists in an outer edge portion on the lower side of the chain guide portion 149 . The folded-back portion 150 is provided over the entire part of the guide bent portion 149 a and the leg portion 149 b. Then, the existence of the folded-back portion 150 can improve the strength of the chain guide portion 149 . Furthermore, the existence of the folded-back portion 150 can increase safety when a site such as hands comes in contact with the folded-back portion 150 . However, the folded-back portion 150 is not necessarily provided over the entire part of the guide bent portion 149 a and the leg portion 149 b, and a configuration where the folded-back portion 150 does not exist in a site of at least a part of the guide bent portion and the leg portion may be employed. <2. Regarding Action of Chain Block> [0098] In the chain block 10 of the above-described configuration, when the hand chain C 2 is operated in the winding-up direction in a state where load is hung on the lower hook 45 , the hand wheel 80 rotates; however, at this time, due to the engagement of the female screw portion 81 with the male screw portion 76 of the drive shaft 70 , the hand wheel 80 travels in the direction to pressurize the brake plate 92 ( 92 b ) (direction toward X2 in FIGS. 3 and 4 ) and strongly pressurizes the brake plate 92 ( 92 b ). Subsequently, the hand wheel 80 and the drive shaft 70 integrally rotate, and a driving force caused by the rotation is transferred to the load gear 31 through the pinion gear 72 , the large-diameter gear 61 , and the small-diameter gear 62 to rotate the load-sheave hollow shaft 20 . Thereby, the load chain C 1 is wound up and the load is lifted. [0099] Conversely, when the lifted load is lowered, the hand chain C 2 is driven in the opposite direction to when the load is lifted. Then, the hand wheel 80 releases the pressurization on the brake plate 92 b. The drive shaft 70 rotates in the opposite direction to the winding-up direction of the load by an amount of the releasing. Thereby, the load is gradually lowered. [0100] Note that, in a stopped state of the ratchet wheel 94 , the tip of the pawl member 95 engages with the tooth portion 94 a of the ratchet wheel 94 . Moreover, even when the hands are released from the hand chain C 2 at the time of winding-up to rotate the drive shaft 70 in the opposite direction by the action of gravity from the load, the brake plate 92 b is pressed against the ratchet wheel 94 by the hand wheel 80 in a state where the hand wheel 80 does not rotate, and further the brake plate 92 a is pressed against the flange portion 91 a of the brake receiver 91 by the ratchet wheel 94 . Thereby, a brake force resisting the gravity of the load is applied to prevent the load from being lowered. <3. Regarding Effect> [0101] According to the chain block 10 of the above-described configuration, the side surface 142 of the wheel cover 14 is provided with the wrap-around portion 148 illustrated in FIGS. 3 , 15 , and the like. Thus, due to the existence of the wrap-around portion 148 , the end surface 143 around the bolt hole 147 is difficult to deform, compared to the configuration of the related art as illustrated in FIG. 21 . Thereby, the strength of the wheel cover 14 can be improved. [0102] Furthermore, when the wrap-around portion 148 exists in the wheel cover 14 as illustrated in FIG. 17B , a force acting on the upper side surface 142 a (wrap-around portion 148 ) can be made small, compared to the configuration of the related art as illustrated in FIG. 17A . In addition, in the present embodiment, when an external force acts as illustrated in FIG. 17A , the existence of the wrap-around portion 148 decreases a component of the force involving flexural deformation of the upper side surface 142 a (wrap-around portion 148 ), and increases a component of the force involving shear deformation of the upper side surface 142 a (wrap-around portion 148 ), compared to the configuration of the related art in which the wrap-around portion 148 does not exist. Thereby, in the present embodiment, the strength of the wheel cover 14 can also be improved. [0103] Furthermore, in the present embodiment, the chain guide portion 149 is provided adjacent to the wrap-around portion 148 . Here, due to the existence of the wrap-around portion 148 , a portion toward the rotation center is formed in the side surface 142 of the wheel cover 14 , and thereby, the chain guide portion 149 can be integrally formed in a continuous state with the wrap-around portion 148 . [0104] Furthermore, by integrally forming the chain guide portion 149 in a continuous state with the wrap-around portion 148 in the above-described manner, a site on the wrap-around portion 148 side (a site on the upper side) of the chain guide portion 149 is supported by the wrap-around portion 148 . Thereby, the strength of the chain guide portion 149 can be improved. Furthermore, when the chain guide portion 149 is integrally provided in a continuous state with the wrap-around portion 148 , the number of processes when the wheel cover 14 is formed can be reduced. That is, in the configuration of the related art, as illustrated in FIG. 21 , the chain guide portion 149 H is separately provided, and the separate chain guide portion 149 H is mounted to the wheel cover by welding. In the present embodiment, however, the wheel cover 14 and the chain guide portion 149 can be integrally formed by plastic working such as press working or deep-drawing working. Thereby, work such as welding becomes unnecessary, and the number of processes required for the welding and the like can be reduced. [0105] Furthermore, in the present embodiment, the outer peripheral edge portion of the first frame 11 is provided with the pair of concave portions 113 passing through the center side thereof with the vertical direction (Z direction) interposed therebetween. The concave portions 113 are recessed toward the center side of the first frame 11 more than the outer peripheral edge portion of the first frame 11 adjacent to the concave portions 113 . Similarly, the outer peripheral edge portion of the second frame 12 is also provided with the pair of concave portions 123 passing through the center side thereof with the vertical direction (Z direction) interposed therebetween. The concave portions 123 are recessed toward the center side of the second frame 12 more than the outer peripheral edge portion of the second frame 12 adjacent to the concave portions 123 . Thus, for example, by positioning different fingers in the pair of concave portions 113 and/or the pair of concave portions 123 , respectively, the chain block 10 can be grasped. That is, the chain block 10 can be grasped or held by fingers or a grasping member or holding member, using the concave portions 113 , in addition to the upper hook 40 , and the convenience such as carrying and storing or packing can be improved. [0106] Further, in the present embodiment, the tip side (X2 side) spaced apart from the end surface 143 of the chain guide portion 149 is provided with the protruding tip 149 c which is inserted into the insertion hole 124 of the second frame 12 . Thus, the strength of the chain guide portion 149 can be improved. That is, when the protruding tip 149 c is inserted into the insertion hole 124 , the chain guide portion 149 is supported on the second frame 12 side. Thereby, the strength of the chain guide portion 149 can be improved. [0107] Furthermore, in the present embodiment, the outer peripheral portion on the side spaced apart from the wrap-around portion 148 of the chain guide portion 149 (lower side; Z2 side) is provided with the folded-back portion 150 formed by hemming processing. Thus, the thickness on the lower side (Z2 side) of the chain guide portion 149 can be increased by the existence of the folded-back portion 150 . In addition, the folded-back portion 150 is provided with the bent portion. Thus, when the other portions than the folded-back portion 150 of the chain guide portion 149 flexibly deform, the bent portion is shear-deformed. Thus, when the folded-back portion 150 exists, a large force becomes necessary. Thereby, the strength of the chain guide portion 149 can be improved. [0108] Furthermore, in the present embodiment, the thickness Da2 of the tooth tip 722 of the pinion gear 72 is provided to be larger than the thickness Dc1 of the tooth tip 612 of the large-diameter gear 61 . Thereby, the strength of the tooth 721 of the pinion gear 72 can be improved, and the durability of the pinion gear 72 can also be improved. That is, since the number of the teeth 721 of the pinion gear 72 is smaller than the number of the teeth 611 of the large-diameter gear 61 , the teeth 721 of the pinion gear 72 are easy to wear. Thus, in the pinion gear 72 H according to related art, the tooth tip 722 side of the tooth 721 H is easy to break due to the wear of the tooth 721 H. [0109] However, when the thickness Da2 of the tooth tip 722 of the pinion gear 72 is made larger than the thickness Db2 of the tooth tip 722 H of the pinion gear 72 H according to the related art and further the thickness Da2 of the tooth tip 722 of the pinion gear 72 is made larger than the thickness Dc1 of the tooth tip 612 of the large-diameter gear 61 , the durability of the tooth 721 against wear can be improved. Thereby, the lifetime of the chain block 10 can be prolonged. Furthermore, the reliability of the chain block 10 can be improved. [0110] Furthermore, in the present embodiment, the thickness Da of the tooth 721 of the pinion gear 72 is made larger than the thickness Db according to the related art, and the thickness Dc of the tooth 611 of the large-diameter gear 61 is made smaller than the thickness Dd according to the related art. Thereby, the tooth tip 722 of the tooth 721 of the pinion gear 72 can be effectively prevented from breaking and the like. [0111] Further, in the present embodiment, the base side (X1 side) of the pinion gear 72 is provided with the flange portion 71 , and the flange portion 71 and the teeth 721 are provided in a continuous manner. Thus, the strength of each tooth 721 of the pinion gear 72 can be increased. [0112] Further, in the present embodiment, the pair of reduction gear members 60 are provided, and the pinion gear 72 is engaged with both the pair of reduction gear members 60 . Then, the pair of reduction gear members 60 are arranged at symmetrical positions with the pinion gear 72 interposed therebetween. In such a case, the teeth 721 of the pinion gear 72 wear earlier; however, even in such a case, by making the thickness Da of the tooth tip 722 large as described above, the tooth tips 722 of the teeth 721 of the pinion gear 72 can be effectively prevented from breaking and the like. <4. Modification> [0113] Hereinabove, the embodiment of the present invention has been described, but the present invention can be modified in various manners other than the above-described embodiment. Hereinafter, the modifications will be described. [0114] In the above-described embodiment, the chain guide portion 149 is integrally provided in a continuous state with the wrap-around portion 148 . As illustrated in FIGS. 19 and 20 , however, a configuration of separately providing chain guide portion 149 without being continuous with wrap-around portion 148 may be employed. That is, a configuration of providing the chain guide portion 149 separately from the wrap-around portion 148 by mounting the chain guide portion 149 to an end surface 143 by a technique such as welding may be employed. [0115] In such a configuration, the degree of freedom in an arrangement position of the chain guide portion 149 with respect to the end surface 143 can be improved. Furthermore, even in such a configuration, since the wrap-around portion 148 exists in a side surface 142 , the existence of the wrap-around portion 148 can improve the strength of a wheel cover 14 . [0116] Furthermore, the above-described embodiment describes the configuration of fixing the auxiliary plate 50 to the first frame 11 through the fixation hole 53 and the fixation member 55 . However, for example, at least one combination of a boss hole and a boss may be used in place of the combination of the fixation hole 53 and the fixation member 55 . In addition, an auxiliary plate 53 may be fixed to a first frame 11 by welding or the like. REFERENCE SIGNS LIST [0117] 10 chain block [0118] 11 first frame [0119] 12 second frame (corresponding to frame member) [0120] 13 gear case [0121] 14 wheel cover [0122] 20 load-sheave hollow axis [0123] 23 load sheave [0124] 30 reduction member mechanism [0125] 31 load gear [0126] 31 b, 31 b 1 , 31 b 2 concave portion [0127] 40 upper hook [0128] 42 guide roller [0129] 45 lower hook [0130] 50 auxiliary plate [0131] 52 drawing portion [0132] 53 fixation hole [0133] 57 bearing hole [0134] 60 reduction gear member [0135] 61 large-diameter gear [0136] 61 a chamfered surface portion [0137] 62 small-diameter gear [0138] 64 a oil groove [0139] 65 swelling portion [0140] 66 recessed portion [0141] 70 diving shaft [0142] 72 pinion gear [0143] 73 inclined portion [0144] 74 curved surface portion [0145] 80 hand wheel [0146] 90 brake mechanism [0147] 91 brake receiver [0148] 92 brake plate [0149] 94 ratchet wheel [0150] 95 pawl member [0151] 110 , 120 circular portion [0152] 111 , 121 frame protruding portion [0153] 112 , 122 insertion hole [0154] 113 , 123 concave portion [0155] 124 insertion hole [0156] 141 flange portion [0157] 142 side surface [0158] 142 a upper side surface [0159] 142 b lower side surface [0160] 143 end surface [0161] 144 notched portion [0162] 145 left-right side surface [0163] 146 protruding portion [0164] 147 bolt hole (corresponding to fixation hole) [0165] 148 wrap-around portion [0166] 149 chain guide portion [0167] 149 a guide bent portion [0168] 149 b leg portion [0169] 149 c protruding tip [0170] 150 folded-back portion [0171] A 1 , A 2 tangential line (tangential surface) [0172] A 3 bisector [0173] B 1 to B 5 bearing [0174] C 1 , C 2 load chain N nut [0175] S space [0176] SB stud bolt (corresponding to fixation member)
Provided is a chain block with which wheel cover strength can be improved while inhibiting an increase in cost, without the need for separate reinforcement members. A chain block is provided with a wheel cover which is attached to a frame member, and which covers a hand-chain wheel having a hand chain looped thereover. A plurality of fixation holes for having fixation members inserted therethrough during attachment to the frame member are provided in peripheral edge sections of end-surface sides of the wheel cover, said end-surface sides being disposed facing the frame member. Wrap-around portions are provided to wheel-cover side surfaces which intersect the end surfaces, said wrap-around portions being formed so as to surround, at an angle exceeding 90, the fixation holes in the peripheral direction of the fixation holes.
1
REFERENCE TO RELATED APPLICATION This is a continuation-in-part of U.S. application Ser. No. 08/216,914, filed Mar. 23, 1994, entitled "Athletic Glove for Bat, Club and Racquet Sports", now abandoned. BACKGROUND OF THE INVENTION The present invention relates generally to athletic gloves and, more particularly, to gloves of the type used by baseball batters, golfers, tennis and racquetball players, and similar participants in other bat, club and racquet sports. Gloves are commonly worn by athletes participating in various sports, particularly bat, club and racquet sports, to enhance the participant's grip. For example, for many years, baseball players have commonly worn specially designed thin leather gloves while batting to improve and enhance the batter's grip on the bat handle and, in turn, to optimize the batter's power and control in swinging the bat. Conventional wisdom holds that the optimal gripping disposition of the baseball bat handle within a batter's hands is to allow the handle to be cradled loosely within the fingers in contact with the heel of the hand but otherwise at a spacing from the batter's palms so that the middle, ring and small fingers of the hands are used to exert the principal gripping force on the handle rather than the batter's forefingers and thumbs. Unfortunately, the natural tendency of most baseball players is to hold the bat handle with a significant gripping force with the handle firmly pressed into the palms of the hands and into the crotch region between the thumb and forefinger of each hand. However, rather than improving the batter's power and control, this improper gripping technique causes the muscles in the batter's wrist and forearms to be tensioned and therefore detracts from the batter's ability to exert optimal force when swinging the bat. Also, the disposition of the bat handle against the batter's palms, together with the tension exerted in the wrists and forearms, resists the tendency of the batter's upper hand to turn or "roll over" the lower hand as the swing is completed, which is considered to be necessary and desirable to optimize the traveling speed of the bat at its outer hitting end. SUMMARY OF THE INVENTION It is accordingly an object of the present invention to provide an improved athletic glove for use by players in bat, club and racquet sports which is configured to induce the player to grip the handle of the bat, club or racquet in optimal disposition within the fingers of the player's hands rather than pressed against the palms of the hands. Briefly summarized, in its most basic aspect, the glove of the present invention comprises a main glove body having a palm portion to overlay the palm of the athlete's hand when worn and a spacing member integrally affixed to the palm portion of the glove body for engagement with the handle portion of the bat, club or racquet when gripped in the athlete's hand. In this manner, the handle portion is maintained at a spacing from the palm of the hand so as to induce the athlete to cradle the handle portion within the fingers of the hand. In the preferred embodiment adapted particularly for use by baseball batters in gripping the handle of a baseball bat, the glove body defines an interior hand receiving area for the batter's hand, a wrist opening for insertion of the hand into the interior area, and a plurality of tubular portions defining thumb and finger openings for receiving respectively the thumb and fingers of the batter's hand. The palm portion of the main glove body includes a crotch area for overlaying a crotch region of the batter's palm between the thumb and forefinger and a heel area for overlaying a heel region of the batter's palm adjacent the wrist. The spacing member, preferably in the form of a pad, is affixed to the palm portion substantially only in the crotch area of the glove body, thereby terminating at a sufficient spacing from the heel area to maintain the handle portion of the bat spaced from the crotch region of the batter's palm while permitting the handle portion to rest against the heel area of the batter's hand for maximizing the gripping force exerted on the handle portion by the batter's middle, ring and small fingers. In an alternate embodiment, a secondary spacing member may be affixed to the tubular portion for the forefinger of the batter's hand immediately adjacent the inward knuckle to also maintain the handle portion of the bat spaced from the batter's forefinger. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of the palm side of a baseball batting glove according to the preferred embodiment of the present invention; FIG. 2 is a perspective view of the backhand side of the baseball glove of FIG. 1; FIG. 3 is an exploded perspective view of the glove of FIG. 1; FIG. 4 is a diagrammatic view of a baseball batter's hand gripping the handle portion of a baseball bat while wearing the glove of the present invention; and FIG. 5 is a perspective view like FIG. 1 showing an alternative embodiment of a baseball batting glove. DESCRIPTION OF THE PREFERRED EMBODIMENT Referring now to the accompanying drawings and initially to FIGS. 1 and 2, a baseball batting glove according to the preferred embodiment of the present invention is indicated generally at 10. The glove 10 is preferably fabricated from relatively thin tanned leather, a textile fabric material, or a combination thereof, such as the materials from which conventional batting gloves are constructed. The batting glove 10 comprises a main glove body 12 having a palm portion 14 and a backhand portion 16 with individual tubular thumb, forefinger, middle finger, ring finger, and little finger portions 18,20,22,24,26, respectively, sewn or otherwise secured together to provide an interior hand pocket with individual thumb and finger pockets, respectively. The palm and backhand portions 14,16 define a wrist opening 40 for insertion of a batter's hand into the interior hand pocket. A wristband 42 encircles the wrist opening 40 and comprises mating closures (not shown), typically hook-and-loop fastener components such as Velcro closure components, to selectively enlarge and close the wrist opening 40 for the wearer's ease in inserting and removing the hand into and from the hand pocket and securing the glove 10 snugly on the hand during wearing. Those persons knowledgeable in the art will recognize and understand that the wristband 42 is optional and that the present invention is equally adaptable to gloves having no such wristband 42. In accordance with the present invention, a spacing member 48 (FIG. 3) of a generally rectangular shape is affixed to the palm portion 14 of the glove body 12 in the crotch region 50 spanning the area between the thumb and forefinger portions 18,20 and extends a short distance therefrom across the palm portion 14, terminating short of the center of the palm portion 14 and therefore at a substantial spacing from the opposite heel region 52 of the palm portion 14 adjacent the wrist opening 40. The opposite sides of the spacing member 48 adjacent the thumb and forefinger portions 18,20 may be slightly concave in shape to conform to the base of the wearer's thumb and forefinger when curled with the other fingers of the hand into a bat gripping disposition. A rectangular leather patch 51 is sewn to the palm portion 14 and partially overlapping to the backhand portion 16, in covering relation to the spacing member 48 to secure it in place in its described disposition. The spacing member 48 preferably is in the form of a pad having a sufficient degree of compressibility and resiliency to provide a comfortable feel to the wearer's palm but being sufficiently firm to resist substantial compression under the normal gripping forces exerted by a baseball batter's hands. For this purpose, the pad may preferably be fabricated of various conventional resilient foam materials. The use and function of the batting glove of the present invention may thus be understood with particular reference to FIG. 4. In FIG. 4, one hand of a baseball batter is shown to be in gripping disposition with the handle portion 54 of a conventional baseball bat, while the hand is wearing a glove 10 in accordance with the present invention. Of course, although FIG. 4 depicts only one hand of the batter, it will be understood that the optimal benefits of the present invention will be realized by wearing a glove of the invention on each hand while batting. As will be seen, the padded spacing member 48, being located substantially only in the crotch region 50 of the palm portion 14, serves to maintain a spacing between the handle portion 14 and the wearer's palm underlying the crotch region 50, while the termination of the spacing member 48 at a distance away from the heel region 52 allows the handle portion 54 to rest against the underlying heel of the batter's hand. In this manner, the batter is induced and constrained to cradle the handle portion within the fingers of the hand and to utilize the middle, ring and small fingers to exert the principal gripping force on the handle portion 54. In turn, the batter's wrist and forearm will naturally remain relatively relaxed. Since the batter is thereby caused to hold the handle portion 54 in the optimal griping disposition according to conventional teachings, the batter is enabled to exert an optimal swinging force on the handle portion 54 of the bat through the batter's wrist and forearm muscles and to achieve an optimal "rollover" of the upper hand at the completion of the swing so as to maximize the traveling speed of the outer hitting end of the bat. An additional, but equally if not more important, advantage of the batting glove of the present invention is that, unlike substantially all prior art gloves having any form of grip-altering means, the glove of the present invention does not create an unnatural feel to the wearer when gripping a bat. On the contrary, because of the precise location of the padded spacing member 48 substantially only in the crotch region 50 of the palm portion 14 of the glove, the bat rests in the fingers and against the heel of the hands, which is the most natural manner of gripping a bat for most players, thereby creating an entirely natural feel when wearing the present glove. Within these natural gripping areas of the hands, i.e., within the fingers, the palm and the heel of the hands, the glove of the present invention includes no additonal pad or other "foreign" device which would alter the natural feel of the wearer in gripping a bat. Rather than altering a player's natural feel in gripping a bat, the spacing member 48 essentially only prevents a batter from consciously or subconsciously departing from such natural gripping style by forcing the bat handle into the crotch areas of the hands. In FIG. 5, an alternative embodiment of batting glove 110 is shown, the glove 110 being substantially identical to the glove 10 of FIGS. 1-4 except that, in addition to the spacing member 48, a second spacing member 49 of a generally rectangular or oblong shape is affixed to the palm side of the forefinger portion 20 immediately adjacent the palm portion 14, the spacing member 49 being of a sufficiently abbreviated length to terminate short of the first knuckle of the wearer's hand. Likewise another rectangular patch 53 is sewn to the forefinger portion 20 to cover and secure the spacing member 49 in place. As will be understood, by the placement of the spacing members 48,49 of the glove 110 only in the crotch region 50 and on the base of the forefinger portion 20, a hitter is similarly constrained to grip a baseball bat in the fingers of the hand, leaving the muscles of the arm relaxed for optimal swinging force and wrist "rollover." It will therefore be readily understood by those persons skilled in the art that the present invention is susceptible of broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications and equivalent arrangements will be apparent from or reasonably suggested by the present invention and the foregoing description thereof, without departing from the substance or scope of the present invention. For example, persons skilled in the art will recognize that the glove of the present invention is equally adapted to embodiments for use by golfers, tennis and racquetball players, and other athletes participating in similar bat, club or racquet sports and the like wherein a sports implement or accessory is swung while gripped in the participant's hand. Accordingly, while the present invention has been described herein in detail in relation to its preferred embodiment, it is to be understood that this disclosure is only illustrative and exemplary of the present invention and is made merely for purposes of providing a full and enabling disclosure of the invention. The foregoing disclosure is not intended or to be construed to limit the present invention or otherwise to exclude any such other embodiments, adaptations, variations, modifications and equivalent arrangements, the present invention being limited only by the claims appended hereto and the equivalents thereof.
An athletic glove to be worn by baseball batters (as well as other participants in bat, club and racquet sports) promotes proper gripping disposition of the handle portion of a baseball bat by providing a spacing member integrally airfixed to the crotch area of the palm of the glove body for engagement with the handle portion of the bat when gripped in the batter's hand so as to maintain the handle portion at a spacing from the palm of the hand and induce the batter to cradle the handle portion within the fingers.
0
BACKGROUND OF THE INVENTION [0001] 1. Field of the Invention [0002] The invention relates generally to an oral composition having a function in lubricating the mouth and preventing the formation of stains on the surfaces of the teeth. The active ingredients of the composition are a polyvinyl alcohol and a metal chelating agent. [0003] The invention also encompasses a method of treating xerostomia comprising of administering to an affected individual a lubricant composition containing an alcoholic polymer and a metal chelating agent in an orally acceptable vehicle. [0004] 2. The Prior Art [0005] Xerostomia commonly known as “dry mouth” is a condition in which the salivary glands do not produce sufficient quantities of saliva. This causes discomfort that can in some cases be quite severe. Without saliva, the mouth burns and the throat and tongue can undergo physiological changes. Teeth can also decay rapidly and the tongue can become smooth, cracked and vulnerable to infection. [0006] The mouth is one of the body areas most exposed to the external environment. Normally, mucous forms a continuous protective layer in the nose, mouth and throat. A patient suffering from xerostomia not only has decreased fluid in the mouth, but also an insufficient quantity of mucoproteins and mucopolysaccharides to hold fluid in contact with the cells and create a barrier to irritation and infection. [0007] Cases of xerostomia may vary from the mild, in which only slight dryness is experienced, to severe cases in which the patient will have serious problems with mastication, swallowing, digestion, speech, and the like. As noted in U.S. Pat. No. 4,438,100 to Balslev et al., there is a number of causes of xerostomia, including the physiological (e.g., age, menopause, postoperative conditions, dehydration), as well as the psychological (nervousness). The reasons for mouth dryness may also be pharmacological (e.g., as a common side effect of many medications, including anti hypertensives, diuretics, anti-arthritics and anti-depressants) or as a result of radiotherapy. The most severe cases of xerostomia are caused by radiation therapy after head and neck surgery and by autoimmune diseases such as lupus, Sjogrens Syndrome, and rheumatoid arthritis. [0008] Until recently, the treatments for xerostomia have had significant drawbacks. For example, symptoms of mild xerostomia can be somewhat alleviated by consumption of fluids, hard candy and throat lozenges. Because of the susceptibility of xerostomia patients to tooth decay and gum disease, however, the increased sugar intake associated with conventional candy and lozenges is of real concern. In addition, fluids or candy are typically not effective with more severe cases of xerostomia, nor do they provide long-lasting relief with mild cases. [0009] Artificial saliva and salivary substitutes have been proposed as palliative treatments for the symptoms of xerostomia, which preparations have physical and chemical properties that simulate those of natural (human) saliva. [0010] Artificial salvias of the prior art include compositions, which contain ions that mimic those found in natural saliva; glycerin, as well as carboxymethylcellulose-based preparations to provide the proper level of viscosity. Fluoride ions are sometimes included to prevent demineralization of tooth enamel. These compositions have not found wide acceptance as many patients find, that such preparations are irritating or distasteful, and that their lubricating effect is of relatively short duration. This lack of wide acceptance is believed due, at least in part to the fact that the artificial saliva preparations of the prior art do not fully possess the rheological characteristics of natural saliva which are responsible for natural saliva's lubricating effect. An article entitled “Lubrication and Viscosity Features of Human Saliva and Commercially Available Saliva Substitutes”, M. N. Hatton et al, J. Oral Maxillotac. Surg. 45, 496-499 (1987), contains a full discussion of the problems associated with the presently available commercial saliva substitutes in the treatment of individuals with diminished salivary gland function. [0011] In view of the problems, which occur when salivary secretion is deficient, it will be understood that it would be most desirable to have an oral lubricating composition for human use, to relieve the above-mentioned discomforts and inconveniences incurred by xerostomia or by a greater or lesser tendency to dryness of the mouth. Such a composition should have lubricating properties which are as close to the properties of the natural saliva so as to provide to the patient long-term relief from the symptoms of xerostomia or dry mouth. [0012] The uses of lubricating polymers are well known the ophthalmic area. For example, U.S. Pat. No. 4,529,535 to Sherman discloses a rewetting solution that is particularly useful for rigid silicone copolymer contact lenses, including extended wear lenses. In one embodiment, the rewetting solution contains the combination of hydroxyethylcellulose, polyvinyl alcohol, and polyvinylpyrrolidone. U.S. Pat. No. 4,748,189 to Su et al. discloses ophthalmic solutions for improving the exchange of fluid in the area outside a hydrogel contact lens in the area underneath the hydrogel contact lens, in order to permit tear exchange to occur, thereby preventing the accumulation of waste matter and debris under the lens. The solution contains a hydrogel-flattening agent, for example urea, glycerin, propylene glycol, sorbitol, or an amino-ethanol. Surfactants that are useful in the solution include poloxamer and tyloxapol. Suitable lubricants include hydroxylethylcellulose, polyvinylalchol, and polyvinylpyrrolidone. [0013] For a lubricating polymer to be useful in the oral cavity it should be non-irritating and have adhesive properties. Various polymers have been proposed for use in establishing adhesive contact with mucosal surfaces. See, for example, Biegajski, U.S. Pat. No. 5,700,478 to Lowey, U.S. Pat. No. 4,259,314 to Lowey, U.S. Pat. No. 4,680,323 to Yukimatsu et al., U.S. Pat. No. 4,740,365 to Kwiatek et al., U.S. Pat. No. 4,573,996 to Suzuki el al., U.S. Pat. No. 4,292,299 to Suzuki et al., U.S. Pat. No. 4,715,369 to Mizobuchi et al., U.S. Pat. No. 4,876,092 to Fankhauser et al, U.S. Pat. No. 4,855,142; Nagai et al., U.S. Pat. No. 4,250,163 to Nagai et al., U.S. Pat. No. 4,226,848 to Browning, U.S. Pat. No. 4,948,580 to Schiraldi et al Typically, these adhesives consist of a matrix of a hydrophilic, e.g., water soluble or swell able, polymer or mixture of polymers which can adhere to wet mucosal surfaces. Such polymers are inclusive of hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxy ethylcellulose, ethylcellulose, carboxymethyl cellulose, dextran, gaur-gum, polyvinyl pyrrolidone, pectins, starches, gelatin, casein, acrylic acid, acrylic acid esters, acrylic acid copolymers, vinyl polymers, vinyl copolymers, vinyl alcohols, alkoxy polymers, polyethylene oxide polymers, polyethers, and the like. These adhesives may be formulated as ointments, thin films, tablets, troches, and other forms. Often, these adhesives have had medicaments mixed therewith to effectuate slow release or local delivery of a drug rather then treat xerostomia or dry mouth. [0014] Some of the polymers described above have several drawbacks. For example materials such as Carbopol (carboxyvinyl polymers), are not water soluble thus leave a tacky, greasy residue in the oral cavity of the wearer, and can cause sustained oral irritation and some forms of adhesives remain in the oral cavity for only short periods of time, e.g. generally not more than about 10 or 20 minutes, and therefore cannot provide for delivery of a substance over an extended period of time. [0015] U.S. Pat. No. 5,886,054 discloses a composition to treat xerostomia, which comprises of an aqueous solution of at least one polymer and at least one electrolyte, wherein the aqueous solution is preferably buffered and optionally contains at least one mucin. The polymer can be chosen for instance from the group which consists of scleroglucan, guar gum, xanthan gum, sodium carboxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid and polyvinyl alcohol. The therapeutic composition according to the invention can serve as saliva substitution agent, artificial tear water, in a mouth rinse or in a toothpaste. The aforementioned patient teaches that the mucin is critical because saliva mucins can adhere to both the surface of the teeth and to the oral mucosa and polyacrylic acid subsequently binds to the mucin in order to form a protective layer. [0016] For a lubricant to be effective, it has to interact with the surfaces it is protecting. Referring to U.S. Pat. No. 5,886,054, the disadvantage of combining polyvinyl alcohol with an electrolyte is that the cation may interact with the polymer and cause precipitation of polyvinyl alcohol. Further, saliva is known to contain high concentrations of electrolytes, which may cause further precipitation of polyvinyl alcohol thus leaving a granular feeling in the mouth. Hence, the addition of a metal chelating agent to a formulation containing polyvinyl alcohol will aid in its anti-xerostomia properties. Further inclusion of salivary mucins have other disadvantages including; the mucins are biopolymers which are difficult to obtain in sufficient quantities and suitable purity, they are expensive and they may be obtained from animal salivary glands which may make the use of mucin unsuitable for some consumers and patients. Hence, there is a need to develop products that will retain moisture in the oral cavity that will be inexpensive, and will be acceptable to a majority of consumers. It will also be beneficial to develop products that have added benefits such as prevention of dental stains or accumulation of unaesthetic materials on tooth surfaces and also to prevent irritation/inflammation occurring as a result of dry mouth. SUMMARY OF THE INVENTION [0017] Polyvinyl alcohols also referred to as polyhydroxy polymers are well known for their excellent adhesion to hydrophilic materials. Currently, as indicated above they are used for lubricating eyes. The use of polyvinyl alcohols for treating dry eyes has been detailed in U.S. Pat. No. 4,883,658, which teaches that polyvinyl alcohols interact with corneal surfaces and adsorbs fairly tenaciously so that it cannot be easily rinsed off from solid surfaces, related to the eyes. Further, U.S. Pat. No. 4,883,658 teaches that two types of polyvinyl alcohols are necessary to provide a stable lubricating film. Polyvinyl alcohol with high acetate content (but not more than 27%) is quite surface active and is capable of lowering the surface tension of water from 72 to 42 mN/m. On the other hand, polyvinyl alcohol that is fully hydrolyzed exhibits almost no surface activity at the water-air interface. In general, the lower the surface tension of a liquid, the more it will wet a given solid surface. It has now surprisingly been found that formulations containing a polyhydroxy polymer are effective in lubricating the mouth and have an added benefit of preventing the accumulation of stain on tooth surfaces. [0018] It is not understood why the inventive compositions are effective at both lubricating the mouth and preventing the accumulation of dental stain. Without being bound to a particular theory it is thought that polyhydroxy polymer coats the surfaces of the teeth thus providing a physical barrier onto which stains may adhere. This is in contrast to the normal stain formation mechanism whereby the materials directly adhere to the surfaces of the teeth. The lubricating action of the inventive composition my also be related to the adsorption of the polyvinyl alcohol to the mucosal surfaces. [0019] Thus, the object of the present invention is to provide a composition and a method for lubricating the tissues of the mouth and at the same time preventing the accumulation of stain on tooth surfaces. The composition consists of formulating of a polyvinyl alcohol, metal chelating agents and a fat soluble vitamin. Surface active materials are also included aid in the solubilization of surface debrie and to further reduce the surface tension in order to assist in the formation of a lubricating and a protective film on the surfaces of the teeth and the mucosal surfaces. [0020] Anti-inflammatory agents can also be added to the composition to provide relief from irritation arising from mouth dryness. [0021] The inventive composition may be administered in any orally acceptable vehicle e.g., tooth paste or mouth wash. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0022] Polyvinyl alcohol (PVA) is a known, commercially available polymer prepared by replacing acetate groups of polyvinyl acetates with hydroxyl groups. The alcoholysis reaction proceeds most rapidly in a mixture of methanol and methyl acetate in the presence of catalytic amounts of alkali or mineral acids. The polyvinyl alcohol and the synthesis thereof are described in greater detail by D. L. Cincera in Kirk-Othmer ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, Third Edition, John Wiley & Sons, New York (1983), Volume 23, pages 848-865. [0023] The Air Products and Chemicals Inc sell the polyvinyl alcohol used in the composition described herein under the trademark Airvol.RTM. It is to be understood, however, that the invention is not limited to the use of any specific polyvinyl alcohol, and that any equivalent polyvinyl alcohol of pharmaceutical grade can be used to achieve equivalent results. [0024] The polyvinyl alcohol used in this invention composition may be either fully hydrolyzed or partially hydrolyzed material having average molecular weight ranging from 2,000 to 125,000. It is preferred to use polyvinyl alcohol having an average molecular weight of about 30,000 to 110,000. The concentration of the polyvinyl alcohol will vary according to the type of the oral care composition. [0025] In mouth rinses and tooth paste compositions a concentration of about 0.1% to 5% w/w is preferred, whereas in a tooth gel formulations i.e. dentifrices without the abrasives a concentration of 2% to 20% is preferred. Lozenges and chewing gums may have concentrations of 0.1% to 20%. [0026] Agents, which chelate metal ions, are essential ingredients of the present invention. The purpose of the chelating agents is to prevent sequester the metal ions which may bind to the polyvinyl alcohol and promote its precipitation and therefore interfere with the film forming capabilities. The metal chelating agents include a condensed pyrophosphate compound. For purposes of this invention “condensed phosphate,” relates to an inorganic phosphate composition containing two or more phosphate species in a linear or cyclic pyrophosphate form. The preferred condensed phosphate comprises of sodium pyrophosphate but can also include tripolyphosphate, hexametaphosphate, cyclic condensed phosphate or other similar phosphates well known in the field. The metal chelating agent may also include an organic chelating agent. The tem “organic phosphate” includes phosphonic acid, di and tri phosphonoc acid compound or its salts, oxalic acid and or its salts. The preferred phosphonic acid is sold under the trade name of Dequest 2010 and is called 1-hydroxyethylidene-1,1-diphosphonic acid. The chelating agents are incorporated individually or in any combination in the oral care compositions of the present invention in an amount within the range of 0.01 to about 10.0% by weight and preferably from about 0.25% to about 3.0% by weight. [0027] Lipophilic materials are also included in the composition. U.S. Pat. No. detailed in U.S. Pat. No. 4,883,658 teaches that polyvinyl alcohols the polymer adsorbs fairly tenaciously and can be removed by the shear action when the formation contaminated with lipids. For a surface film to be stable the shear action is important because it enables the film to move with the movement of the mucosal tissues. Hence, in order to promote the mobility of the film formed over the mucosal surfaces a safe lipophilic material is included in the composition. It is well known that people with dry mouth have irritated or inflamed mucosal tissues. The irritation may be due to oxidative damage hence; it is preferred to include lipophilic materials with anti-oxidant properties to the composition. These materials may be anti-oxidants such as butyrated hydroxy toluene or fat-soluble vitamins such as Vitamins A, D and E. The preferred lipophilic material with anti-oxidation properties is Vitamin E. The term “vitamin E” as used herein includes tocopherol (vitamin E) and derivatives thereof, for example dl-.alpha. -tocopherol, tocopherol acetate (vitamin E acetate ester), tocopherol succinate (vitamin E succinate ester), etc. As extrapharmacopoeial species, there may be mentioned, for example, alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta-tocopherol, tocopherol nicotinate (vitamin E nicotinate ester), tocopherol phosphate (vitamin E phosphate ester) and tocopherol linolenate (vitamin E linolenate ester). Vitamin E is incorporated in the formulation from about 0.01% to 3% (w/w). [0028] Other lipophilic materials with anti-inflammatory and anti microbial activities may also be included in the composition. The purpose of adding these ingredients are that they act as preservatives of the composition due to their anti-microbial action and they can also act to control inflammation occurring as a result of mouth dryness. These agents may be selected from the following group, which includes halogenated diphenyl ethers, halogenated salicylanilides, benzoic esters, halogenated carbanalides, and phenolic compounds. The most preferred anti-inflammatory agents are substantially water-insoluble members of either the halogenated diphenyl ether group or the phenolic group, in particular those compounds described in detail in U.S. Pat. Nos. 4,894,220 and 5,800,803, which are incorporated herein by reference. [0029] The most preferred water-insoluble or lipophilic agent (herein defined as a compound having a solubility in distilled water at 25.degree. C. of less than 1000 ppm) is triclosan (trade name Irgasan DP300). Triclosan (2,4,4′-trichloro-2′-hydroxydiphenyl ether, CAS No. 338034-5) is a broad spectrum antimicrobial/anti inflammatory agent with a molecular weight of 289.5, having very limited water solubility at physiological temperatures (20 ppm in distilled water at 20.degree. C. and 40 ppm in distilled water at 50.degree. C.). The safety of triclosan has been well established and its use in oral care products, primarily water-based toothpastes in which the triclosan, typically at a concentration of about 0.30 percent by weight, has been solubilized. [0030] According to one embodiment of the present invention, the concentration of triclosan will be at least about 0.10% percent by weight of the ingredients formulating the composition, depending upon the solubility of the antimicrobial compound in the composition. According to an alternate embodiment, the concentration of the antimicrobial agent is 0.3%. The concentration of the water-lipophilic anti-inflammatory compound will be in the range of between about 0.05 percent and about 2%. [0031] Surfactants are also included in the inventive composition. The purpose of the surfactant is to aid in the solubilization of surface debrie and to further reduce the surface tension in order to assist in the formation of a lubricating and a protective film on the surfaces of the teeth and the mucosal surfaces. The surfactant also assists in achieving thorough and complete dispersion of ingredients throughout the oral cavity and renders the compositions more cosmetically acceptable. Non-ionic surfactants also maintain the flavoring materials in solution. In addition, non-ionic surfactants are compatible with the polyvinyl alcohol polymers of its invention, providing for a stable, homogeneous composition. [0032] The surfactants are included from about 0.5 to 50% of the weight of the composition and preferably from about 1% to about 33% by weight of the composition. [0033] Surfactants useful in the practice of the present invention include non-ionic organic surface-active polymers such as polyoxyethylene-polyoxypropylene block copolymers such as Pluronic 108 and Pluronic F-127 marketed by BASF. Pluronic 108 has a molecular weight of 3200 and contains 80% of the hydrophilic polyoxyethylene moiety and Pluronic F127 has a molecular weight of 4000 and contains 70% polyoxyethylene. Other surfactants include alkali metal alkyl sulfates of 8 to 20 carbon atoms, preferably of 10 to 18 and more preferably of 12 to 16 carbon atoms in the alkyls thereof such as Tween 20, which is a and sodium lauryl phosphate. The surfactants may also include sodium cocomonoglyceride sulfate, sodium linear tridecylbenzene sulfonate, N-lauroyl N-methyl taurate and nonionic surfactants such as a water soluble polyoxyethylene monoester of sorbitol with a C 10-18 fatty acid ester of sorbitol (and sorbitol anhydrides), consisting predominantly of the monoester, condensed with about 10-30, preferably about 20, moles of ethyleneoxide. The fatty acid (aliphatic hydrocarbon-monocarboxylic acid) may be saturated or unsaturated, e.g. lauric, palmitic, stearic, oleic acids. A mixed surfactant system consisting of polyoxyethylene-polyoxypropylene block copolymers (Pluronic F-108 and Pluronic F-127), polyoxyethylene (20) sorbitan monolaurate (Tween 20) and sodium lauryl sulfate is preferred however the surfactants can be used individually or in any combination thereof. [0034] Humectants used to prepare the aqueous vehicle include glycerin, sorbitol and polyethylene glycol of molecular weight 400-2000. [0035] Examples of preservatives useful in the practice of the present invention include benzoic acid, sodium benzoate cetylpyridinium chloride, thymol etc. Triclosan is preferred because it has been shown to have anti-inflammatory properties in addition to its anti-microbial properties. [0036] Alcohol such as ethanol can also be included in the composition as a preservative and a flavor enhancement. [0037] Materials that prevent dental caries such as sodium fluoride, stannous fluoride and sodium monofluorophosphate can also be included. Sweeteners suitable for use in the composition include xylitol, saccharin and sorbitol. Other compounds which provide beneficial effects such as potassium nitrate which prevents dental hypersensitivity, compounds of zinc or barium which prevent halitosis and compounds which release active oxygen such as hydrogen peroxide, carbamide peroxide and metal peroxides can also be incorporated into the composition. [0038] A typical mouth rinse or spray prepared in accordance with the practice of the present invention contains the following ingredients in percent by weight based on the weight of the total formulation. Ingredient % by Weight Water 77.74 Glycerin 8 Xylitol 4 Polyethylene glycol 600 3 Pluronic F-108 3 Pluronic F-127 1.3 Polyvinyl alcohol 0.66 Sodium pyrophosphate 0.5 Oxalic Acid 0.5 Dequest 2010 0.4 Tween 20 0.4 Sodium Lauryl Sulfate 0.2 Vitamin E (dl-alpha-tocopheryl acetate) 0.1 Triclosan 0.1 Flavor 0.1 [0039] The mouth rinse was prepared by dispersing the polyvinyl alcohol (average molecular weight 100,000; degree of hydrolysation 86-90 mol %) in cold water with vigorous agitation. The mixture was then heated to boiling with agitation until a clear solution was obtained. Then glycerin, sodium pyrophosphate, oxalic acid and Dequest 2010 were added. After the materials were dissolved the Pluronics were added and the mixture stirred until a clear homogenous solution was obtained. Then xylitol and SLS were added. In a separate container a second mixture was prepared which contained Tween 20, polyethylene glycol, triclosan, Vitamin E and flavor. The mixture was added to the first container. To prevent excessive foaming, a safe antifoaming agent e.g., antifoam A can be added to the mixture. Further alcohol e.g., ethanol can be added if desired to improve consumer acceptability. [0040] To examine the moisturizing effects of the mouth rinse detailed above, six subjects who complained of dry mouth were recruited to participate in the study. All subjects brushed their teeth with a leading fluoridated toothpaste, rinsed with water and then rinsed with the mouth wash shown in table 1. The subjects were then asked if their mouth felt lubricated and moisturized at 5 minutes after rinsing, 30 minutes after rinsing and one hour after rinsing. All subjects reported that their mouth felt lubricated and moisturized. Further the subjects also reported that their mouths felt cleaner. The study was then repeated using a leading mouth rinse. All the subjects reported that their mouth felt cleaner but did not have an effect on the lubricity or the “dryness” of their mouth. The data therefore, indicates that the inventive composition lubricates and moisturizes the mouth. [0041] The mouth rinse was then tested to examine the stain prevention capabilities. Extracted human teeth were soaked in 30% hydrogen peroxide to remove all the stain. Baseline color was then measured using the Minolta chromameter. Color readings were obtained in the L*,a*, b* color coordinates. The teeth were then soaked for seven minutes in the mouth rinse described in the table above. The teeth were then incubated in stimulated saliva for five minutes and the color re-measured to determine if the mouthwash would prevent accumulation of pellicle and keep the teeth white. The teeth were then transferred to a chromogenic mixture containing 10% coffee, 10% tea and 2% non-dairy creamer. The incubation was performed for one hour in order to determine if the rinse would prevent stain accumulation. The teeth were then removed, placed in distilled water and the color was measured. The change in color was calculated using the standard CIE L*a*b* color difference equation. The results indicated that the inventive composition prevented accumulation of stain on tooth surfaces. The results are as follows: TABLE 1 Demonstration of prevention of pellicle accumulation E (color after incubation in E (whitened teeth) mouth-rinse and saliva) Delta E Control 76.88 75.86 1.02 Treated 79.52 79.20 0.32 [0042] In the table above control refers to treatment with a commercial mouth rinse, and treated refers to the inventive mouth rinse. The data shows that the inventive mouthwash accumulates less pellicle and keeps the teeth whiter. TABLE 2 Demonstration of prevention of stain accumulation E (color after incubation in E (whitened teeth) mouth-rinse and stain broth) Delta E Control 76.88 73.92 2.96 Treated 79.52 77.90 1.62 [0043] The delta E of the treated sample is lower when compared to the delta E of the control sample indicating that the inventive composition will prevent stain accumulation. [0044] A study was then performed to examine the stain removal capability of the mouth rinse. The stained teeth above were then soaked in a commercial mouth rinse or the inventive composition for one minute and color was measured. The calculations in color change were performed using the CIE L*a*b* color difference equation. TABLE 3 Demonstration of stain removal E (color after mouth-rinse E (color after incubation and stain broth incubation) in rinse) Delta E Control 73.92 73.48 0.42 Treated 77.90 78.59 −0.69 [0045] The table above shows a delta E of −0.69 of teeth after incubation in the inventive rinse indication that the rinse removes stain when compared to a popular mouth rinse. [0046] A typical dentifrice such as a toothpaste or gel can be prepared in accordance with the practice of the present invention contains the following ingredients: Ingredient % by Weight Water 54.6 Polishing agent 14 Glycerin 10 Xylitol 4 Polyethylene glycol 600 3 Pluronic F-108 3 Silica thickener 3 Sodium Lauryl Sulfate 1.5 Carrageenan gum 1.5 Pluronic F-127 1.3 Sodium pyrophosphate 1 Polyvinyl alcohol 0.66 Dequest 2010 0.4 Tween 20 0.4 Sodium Fluoride 0.24 Vitamin E (dl-alpha-tocopheryl acetate) 0.1 Triclosan 0.3 Flavor 1.0 [0047] Abrasives or polishing agents useful to prepare the dentifrice compositions of the present invention include finely divided silica, dicalcium phosphate, calcium pyrophosphate, sodium bicarbonate, insoluble sodium metaphosphate and tricalcium phosphate. [0048] Thickeners include silica thickeners, carob bean gum, carrageenan gum, hydroxymethyl cellulose, hydroxypropyl cellulose alginates, gantrez, polyvinyl pyrolidine and various carbopols [0049] Humectants include glycerol, sorbitol, propylene glycol, polypropylene glycol and/or mannitol. [0050] Aspartame or saccharin may be used as the artificial sweetener, and the flavor may be based principally or partially on limonene and may contain menthol or other physiologically cooling agent to give it a special appeal.
An oral lubricant having usefulness for alleviating the symptoms of dry mouth and preventing accumulation of dental stains based on a polyvinyl alcohol polymer containing composition in an orally acceptable carrier or vehicle. The invention relates generally to an oral composition having a function in lubricating the mouth and preventing the formation of stains on the surfaces of the teeth. The active ingredients of the composition are a polyvinyl alcohol, a metal chelating agent, lipophilic vitamin, surface active material and a phenolic anti microbial agent with anti-inflammatory properties.
0
BACKGROUND OF THE INVENTION 1. Technical Field This invention relates to a reformer in which fuel gas (raw material gas) is reformed to product gas and supplied to anodes (fuel electrodes) of cells in fuel cell systems, in particular, relates to a plate type reformer in which reforming reaction is conducted while the fuel gas is indirectly heated by burning gas which is supplied to cathodes (air electrodes) of the cells. 2. Background Art A fuel cell system is an electricity generating system using reversed electro-chemical reaction of an electrolysis of water in electrolytes including carbonates, phosphates, etc. with hydrogen gas being supplied to an anodes (fuel electrodes) and buring gas (O 2 , CO 2 ) to a cathodes (air electrodes) in the cells. The hydrogen gas, which is supplied to the anode, is obtained by supplying fuel gas, such as methane as raw material gas with steam to the reformer, in accordance with reforming reaction which is given by the following chemical equations with use of catalysts. CH.sub.4 +H.sub.2 O→CO+3H.sub.2 CO+H.sub.2 O→CO.sub.2 +H.sub.2 To maintain reforming temperature in the reformer, remaining hydrogen or carbon monoxide in the anode gas is supplied into the reformer and burned there to heat up indirectly the fuel gas to be reformed. In such a reformer, however, air and fuel flow into a combustor of the reformer to be burned together, so that volume of the combustor has to be large, and the reformer is often too large in size. Temperature of burned gas was as high as 1300 degrees C. until heat was transferred to the reforming gas and it is structurally impossible to decrease temperature of the burnt gas in order to match temperature of heat receiving gas (between 550 and 750 degrees C.). To solve these problems, plate type reformers which are compact in size, and in which uniform combustion all over the combustor is possible to achieve effective reforming were recently proposed (for example, Japanese Patent Application Laid Open No. Sho. 62-160136 (160136/1987). SUMMARY OF THE INVENTION A primary object of this invention is to provide a plate type reformer which enables effective heat exchanging between burning gas and raw material gas to be reformed. Another object of this invention is to provide a plate type reformer which is capable of suppressing combustion temperature when fuel gas is burned with air in the combustor. A further object of this invention is to provide a plate type reformer which enables uniform fuel supply to the combustor as well as step-by-step combustion. This invention provides a plate type reformer comprising plural main units which include a combustor filled with combustion catalyst and a reforming reactor filled with reforming catalyst, piled together putting a heat conductive separator between the combustor and the reactor, and plural auxiliary units to supply fuel to the combustors of respective main units. Further this invention provides a plate type reformer in which each combustor-side surface of a main unit faces each other, sandwiching an auxiliary unit therebetween, thus the main units and the auxiliary unit are piled together, and this pile has a passage to supply air for combustion to the above mentioned combustor, a passage to exhaust out burnt gas from the combustor, a passage to supply raw material gas to be reformed into reforming reactor, a passage to draw off reformed gas, and a passage to supply fuel to the above mentioned distance plate. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view showing a part of an embodiment of this invention prior to assembling thereof; FIG. 2 is a cross sectional view of FIG. 1 as assembled; FIG. 3 and FIG. 4 illustrate temperature distributions of combustion gas and reforming gas between the inlet and the outlet of reforming reactor during heat-exchange, respectively; FIG. 5 is a sectional view of another embodiment at the central part according to this invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS As described in FIG. 1 and FIG. 2, a single segment of a plate type reformer of this invention mainly comprises two main units I, in which reforming reaction and combustion take place, and one auxiliary unit II, through which fuel for combustion is supplied to the main units I, with the auxiliary unit sandwiched by the main units I, and the main units being symmetrical to each other. Holders 10 and 12 are located on the exposed sides of the main units I, respectively. The main unit I includes a reforming plate 14 in which a reforming reactor 16 is formed, a combustion plate 18 in which a combustor 20 is formed, and a heat conductive separator or a heat conductive partition wall 22 located between two plates 14 and 18. Central portion of the reforming plate 14 is hollowed out and the hollow or space 16a is filled with reforming catalyst 24, so as to form the reforming reactor 16. Similarly to the reforming plate, central portion of the combustion plate 18 is hollowed out, and the hollow 20a defined within the combustion plate 18 is filled with combustion catalyst 26, so as to form the combustor 20. The auxiliary unit II comprises of a distance plate 30 which has a scooped space 28, and two dispersion plates 34 which have many pores 32 to supply fuel from the scooped space 28 to the combustors 20 in the main units I, with the dispersion plates being stacked onto the distance plate. In the pile of these main units I and the auxiliary unit II, the combustion plates 18 of the main units I are located to contact with the upper and lower dispersion plates 34 of the auxiliary unit II respectively, with the upper holder 10 and the lower holder 12 for the sandwich of the main unit I, the auxiliary unit II, and the main unit I being fastened by bolts and nuts, or the like (not shown). The upper holder 10 has an inlet opening 35 for raw material gas to be reformed (CH 4 +H 2 O), and an outlet opening 38 for the reformed gas (H 2 , CO 2 ). The inlet 36 communicates with the reforming reactor 16 in the reforming plate 14 located thereunder, and the raw material gas to be reformed is supplied to the reforming reactor 16 in the lower main unit 1 through bores 40 formed within the partition plate 22, the combustion plate 18, the dispersion plate 34, and the distance plate 30. The gas so reformed flows through openings 42 formed within the partition plate 22, the combustion plate 18, the dispersion plate 34, and the distance plate 30 so that it encounters the gas reformed in the reforming reactor 16 in the upper main unit I and proceeds to the outlet opening 38 at the upper holder 10. The lower holder 12 has an air inlet 44, a fuel inlet 46, and a burnt gas outlet 48. Air through the air inlet 44 is supplied to the combustion chamber 20 in the combustion plate 18 through openings 50 bored within the reforming plate 14 and the separator 22 of the lower main unit I, and then from that combustion chamber 20 the air is supplied to another combustion chamber 20 in the upper main unit I through openings 50 of the upper and lower dispersion plates 34 and the distance plate 30. Fuel through the fuel inlet 46 is supplied tot he scooped space 28 of the distance plate 30 via openings 52 bored within the reforming plate 14, the partition plate 22, the combustion plate 18, and the dispersion plate 34 of the main unit I. Exhaust gas generated in the combustor 20 in the upper main unit I flows through holes 54 formed in the dispersion plate 34 and the distance plate 30 and encounters the exhaust gas generated upon combustion in the combustion chamber 20 of the lower main unit I. After that, those exhaust gases are discharged from an exhaust opening 48 through holes 54 made in the partition plate 22 and the reforming plate 14. In the above mentioned system, air is supplied from the air inlet 44 while fuel is supplied from the fuel inlet 46 in the lower holder 12, and raw material gas to be reformed (CH 4 +H 2 O) is supplied from the gas inlet 36 in the upper holder 10. Air flows from the air inlet 44 through the holes 50 into the combustors 20 in the upper and lower main unit I. Fuel flows into the scooped space 28 in the distance plate 30 from the fuel inlet 46 of the lower holder 12 through the fuel passage 52 of the main unit I, and then the fuel flows out of the scooped space 28, proceeding through the pores 32 of the upper and lower dispersion plates 34 into the upper and lower combustors 20 next to the dispersion plates 34. The fuel is burned with the combustion catalyst 26 in the combustors 20, the resulting exhaust gas is discharged from the exhaust gas outlet 48 of the holder 12 through the holes 54. On the other hand, raw material gas to be reformed supplied from the inlet 36 of the upper holder 10 flows into the reforming reactor 16 of the upper main unit I, and a part of the gas further flows into the reforming reactor 16 of the lower main unit I through the holes 40. This fuel gas is heated by the gas which has been burned in the combustor 20 and reaches the reaction chamber 16 through the separator 22, and reformed to H 2 and CO 2 with the reforming catalyst 26 in the reforming chamber 16. The gas thusly reformed is delivered outside the unit from the reformed gas outlet 38 of the upper holder 10 via the openings 42. In the reforming process mentioned above, this system can be made compact because the reforming reactor 16 is located adjacent to the combustor 20 with the separator 22 disposed between the reforming reactor 16 and the combustor 20 so that the reforming reactor 16 may be heated up by the burned gas generated in the combustor 20. Since the fuel flows through the scooped space 28 of the distance plate 30 and the pores 32 of the dispersion plate 34, it spreads uniformly throughout the combustor 20, combustion of the fuel takes place gradually or step by step, lowering the combustion temperature compared with conventional systems. It is possible to adjust the combustion temperature required by the heat receiving gas, by controlling size and pitch of the pores 32 in the dispersion plate 34. FIG. 3 and FIG. 4 depict temperature distribution curves of burnt gas and heat-receiving reformed gas between the entrance and the exit of reforming reactor, in which "X" indicates a temperature distribution curve of combusted gas, and "Y" indicates the distribution curve of the reformed gas according to the present invention while "Z" is the temperature distribution curve of the combusted gas in a conventional system. FIG. 3 depicts distribution curves of the case where heat exchange of combusted gas and heat receiving (reforming) gas are performed by parallel gas flow (co-flow), and FIG. 4 depicts the case of counter flow. As indicated by the curve Z, the temperature of the combusted gas in the conventional system is as high as 1300° C. (degrees C.) at the entrance while according to the present invention, burned gas temperature is 650° C. at the entrance and 850° C. at the exit as illustrated by the temperature distribution curve X. This means that lowering of temperature can be accomplished by the present invention. FIG. 5 shows another embodiment of this invention. This embodiment, basically identical to the reforming system illustrated in FIGS. 1 and 2, further includes two porous plates 60, each mounted on the combustor 20 side dispersion plate 34. In this embodiment, function of each porous plate 60 is to further disperse the fuel flowing into the combstom 20 through the pores 32 of the dispersion plate 34. In other words, when the size and pitch of the pores 32 in the dispersion plate 34 are determined in a manner such that fluctuation of the fuel pressure may not affect on reforming reaction, the pitch has to be considerably large, and therefore uniform fuel dispersion is difficult to realize. For such a case, the porous plate 60 effectively serves to make the fuel much finer. It is recognized, of course, that those skilled in the art may make various modifications or additions to the preferred embodiments without departing from the scope of the present invention and that the present invention is not limited to those embodiments. For instance, positions of the passages for air, fuel, etc and each inlet/outlet opening for fuel, reformed gas etc., may be changed from the positions shown in the figures. Also, the numbers of layers of the main unit may be more than two, and in accordance with increased layers, number of auxiliary unit will be increased.
Main units which includes a reforming reactor and a combustor, both piled together having a heat conductive, partition wall therebetween, are located in a manner such that the combustor sides thereof face each other, with an auxiliary unit for supplying fuel to each combustor being put between the main units. Raw material gas to be reformed is supplied to the reforming reactor through a passage formed in each unit, and then discharged through another passage formed in each unit. Fuel is supplied to the auxiliary unit through yet another passage formed in the main unit, so that it may flow uniformly dispersing in the combustor via the auxiliary unit.
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CROSS-REFERENCE TO RELATED APPLICATION [0001] 60/480,319/DATED Jun. 23, 2003 Title: Animated/Vision Testing System BACKGROUND FIELD OF INVENTION [0002] This invention relates to field of Visual Acuity Testing, specifically to animated/slide computerized vision testing system and a new “Digital Formula” in the measurement of visual acuity for vision testing on not one but three cross-platform computer systems to achieve accurate and consistent results. BACKGROUND [0003] This invention relates to eye testing, specifically using a pre-programmed database computer/portable laptop/tablet PC/Unix based computer server, controlled by an active matrix touch screen (kiosk), electronic personal data assistance (PDA) Keyboard to display an animated eye chart testing system on a high-resolution computer monitor, television or plasma screen for the purpose of testing visual acuity in humans. With the iQueVision: Animated/Vision Testing System (A/VTS) a skilled doctor can quickly check visual acuity with a larger variety of tests then any other projection or computerized system in use today. iQueVision: A/VTS gives any doctor instant access via kiosk/touch screen computer/laptop/tablet PC/palm pilot/computer keyboard and mouse and voice recognition to any number of product materials, educational tools, visual tests and testing methods. These methods include animated eye charts, slide charts, instructional slides and videos, educational slides and videos as well as HTML/XML internet access and patient files all in one pre-programmed computer/portable laptop/tablet PC/Unix based computer server or PDA. Also unique in this design is the ability to give the doctor control over the same software using a wired or wireless network with touch screen capabilities. Another bonus feature is that a patient can also have access to key testing at home using any computer that fits the testing standard through this internet home vision therapy system. BACKGROUND—HISTORY or DESCRIPTION OF PRIOR ART [0004] Vision testing today is based on individual paper charts, pictures, slide projection systems and a few computer software programs. While each of these methods address a specific vision screening area they all have to be constantly replaced or updated due to wear and tear under general use. The most frustrating aspect of each of these vision testing methods is that they are all independent of each other and can not be incorporated together because of their design or hardware limitation. The idea behind all of these testing methods is that everyone should be able to see and identify a 3½″ letter using Dr. Snellen's measurements at 20 ft. in distance. Some computerized vision testing systems may appear to present a bigger problem for non-computer literate doctors; however, many doctors who don't like the idea of using complex computer systems might be more inclined to use this low tech method for testing that gives them instant access via a pre-programed database controlled by a touch screen (kiosk) and linked with a computer/server, tablet pc, PDA or keyboard/mouse. The only operational knowledge requirement for iQueVision ANTS is an average household push button appliance that also uses touch screen or touch pad technology, thus eliminating the need to understand complex computer/laptop/Unix server systems. This is a low tech answer of building a touch screen program using one active and one passive monitor system puts 21st century technology into doctor's hands without the wear and tear and technical problems associated with existing products. In a closed looped program (kiosk) the doctor simply turns on the system and is presented with a touch screen set of buttons to choose from. A custom designed menu allows the doctor to instantly pull up any acuity test they desire. [0005] After 2 years of research it has become quite apparent that the current vision testing tools, projection systems and testing methods are out dated and over 60 years old. The same bulb system used in the old projection systems patented in 1922 (see FIG. A) and updated in 1948 are still being used today with one exception—brighter bulbs and the current projection systems also use an illuminated hand held remote. What sets the iQueVision: A/VTS system apart from other projection systems today is the doctor can turn the room lights back on because of a digital discovery called: “Contrast Sensitivity” or contrast ratio. This has been a key issue of controversy since the late 40s and one we would like to change, where doctors have been forced to dim the lights in order to administer a visual acuity test. As mentioned “Contrast Sensitivity” on a normal bulb projection system is well below 250:1. Even with modern improvements such as the halogen bulbs it may reach a full light ratio of 250:1 but nothing higher. These bulb systems burn at 3000 -3500 K. (Kelvin) while normal room fluorescent lighting start at 4000 up to 6500 K.(see FIG. D) This is the key reason doctors have been forced to work with the lights dimmed and the key reason projectors have lead to inconsistent diagnosis when being tested, as this is not what we call “Real World Testing”. [0006] The second reason—there are problems with projection systems because they are built with a major flaw in their design in regarding the distance a 1″ image has to be projected. (See FIG. O) On average this 1″ slide image has to be projected some 13.5-20 ft for visual acuity testing. The resulting flaw is that these letters, when designed to be in scale on that slide, appear fuzzy when projected at the required distance. The diffusion of the light waves with this projected light refraction will always creates fuzzy letters. In a resent test is was discovered that letters projected even at 10 ft also appeared fuzzy on the silver-oxide screen—even when a person stood as close as 2 ft away from the screen. This creates a new problem in regard to the loss of “1° (degree) of true resolution” as required in the Snellen visual acuity formula of 1862. The third reason—is deformed letters. Projection systems suffer from uneven illumination and non-symmetrical trapezoidal-shaped letters due to the angles projection systems are installed. The projector is placed 4-6 ft on either side the patient. This angle of attack distorts the shapes of the letters. It's not uncommon for some patients to report seeing fuzzy letters when being tested and a practice that many doctors have accepted because there's nothing better—until now. This is why there is no consistency in visual acuity testing from doctor to doctor. How would you feel knowing that your eyes were being tested with 60 year old ideas and technology. Every projector is different and there is are no regulation or governing laws concerning the accuracy and measurement in visual acuity letters on “certified ” projectors, there is only the formula that many companies and doctors have taken for granted at the consumers expense. The consumer is not getting the best eye exam possible and many may have overpowered glasses or contacts because of the old technology. As stated, all projection systems are inherently flawed and will not display a clinically accurate acuity letter with a 1° (degree) of true resolution that should be in the design of each letter for vision testing. This is not true for iQueVision testing system and the key reason for building the system. The iQueVision System will allow doctors to leave the lights on and produce a text book optotype with 1° (degree) of true resolution for each and letter with each and every test. LCD monitors burn a 400:1 or higher, almost double when compared to the silver-oxide screens of 250:1. [0007] Using iQueVision A/VTS database program will create new testing procedures and a paradigm shift in the ideology, teaching and testing methods that are better than any other visual acuity testing systems to date. It should also be noted that with the resent development of plasma screens this has open door for iQueVision and a whole new way of thinking about vision testing for the future. The Plasma screen system will help in the design potential for “Real World Testing” under real lighting conditions. With contrast ratios of 3000:1, for better shadow detail and color depth INTRODUCTION—“DIGITAL FORMULA” [0008] Under this patent I would also like to submit the discovery of this “Digital Acuity Vision Testing Formula” (DAVTF) as a minimum standard in visual acuity testing with computer testing systems. (See FIG. A) [0009] The digital minimum formula is: 400:1 Contrast Sensitivity @1° true rez visual acuity letters @min screen resolution of 1024×768>4500 K ambient light. [0010] While this formula sets a minimum standard for all digital visual testing systems it would certainly not preclude the use of any configuration built with a higher standard. Under these guidelines any computer using a touch screen/touch pad or kiosk system with this digital formula for the purpose of visual acuity testing would be in violation of this patent. Anyone thinking that their formula is better would be in direct violation of minimum standard set in this patented when using the “DAVTF.” [0011] Example: the system we are currently testing exceeds the minimum formula and reads: 700:1CS @1° true rez @1280×1024>6500 K. ambient light! (700:1 Contrast Sensitivity with 1° true rez visual acuity letters @min. screen resolution of 1280×1024 with 6500K ambient light.) [0013] (Note: High contrast, contrast sensitivity or contrast ratio does not mean brightness. High contrast is the measurement of gray scale or degrees of shade with the reference point of difference being the brightest white in relation to the darkest black on any given monitor. The higher the contrast sensitivity ads in the levels of gray scale detail that can been seen on the monitor. This contrast sensitivity translates into a better display monitor for viewing color testing when using 256 shades of color for each channel every monitor displays—Red, Blue & Green or (RGB) and gray scale or shadow detail. Also the 1° degree of true resolution is measurement in the distance between the white and black areas that define the spacing of each letter for each size used in any given test for each size of the letter used in the acuity testing. None of the slide projection systems on the market today offer a clinically accurate 1° of true resolution used as defined in the original 20/20 formula of 1862 by Dr. Snellen for testing visual acuity. In fact the small the letter the less detail the projected letter has. Fuzzy letters and a great lose in that 1° of resolution.) [0014] The iQueVision: ANTS will also provide doctors with a first in animated eye testing procedures in a format that is better than any paper or slide chart systems in use today. For example, the letters of each animated chart can fade in and out as needed for each test procedure; letters can be moved across the screen at different speeds to test eye movement; color patterns can be generated for a detailed analysis of color blindness on impaired color vision; hue, density, saturation, and gray scale testing can all be built using an animation process to assist doctors in obtaining a better overall analysis of the patient's current eye or vision limitations. The system will also allow three-dimensional prospective with or without the use of colored red and green or polarized glasses using a 3D monitor LCD or Plasma screen. This system takes advantage of making it easy to access and use new technology as part of the continued development in visual acuity systems. It utilizes a pre-programmed database on any computer/Tablet PC/laptop/Unix computer server. It is controlled by an active matrix touch screen (kiosk), electronic personal data assistance (PDA) and or keyboard/mouse remotely or wirelessly linked to high resolution monitors, TV systems, plasma screens and or the new 3D monitor systems. Not only will all of the tests be incorporated onto pre-programed database computer or Unix server, but it will also be designed to provide doctors with instant access to information on general eye care—helping their patients become more aware of problems by using the visual ads and information designed into the vision testing package. [0015] One of the newest tests developed because of the iQueVision A/VTS is the “Dynamic Letter” Test. (As listed among the tests on FIG. K) This letter or set of letters is a scalable letter controlled by the doctor. Just by holding a slider the doctor can scale a letter up until the patient can tell the doctor what that letter is. A numerical read-out displays at what point the patient can see the letter. From 20/10 all the way to 20/200 in 1 degree increments the doctor can take an exact reading and log them in to the patients records as a new measurement testing tool. As a new claim—no other projector can duplicate the: Dynamic Letter test. SUMMARY [0016] Imagine for a moment your last eye examination . . . the doctor had you look at a projected slide on a gray or silver flat surface some twenty feet away and toggled through various static letters as a testing systems. The doctor dimmed the lights and told you to look at this dimly lit screen illuminated by a single projector. So there you are in the dark trying to focus on this letters some 20 ft away and the letters are fuzzy. Suddenly the doctor can't find the special test he or she needs and begins to takes you from room looking for that one test. The doctor may have even taken you to a special room for color or 3D specialized computer testing. Another obvious problem is the 20 feet of office space required for performing an eye examination adding to the cost of overhead. [0017] Now, imagine being in a room half as long, looking at high resolution, high contrast flat screen 17-20″ monitor or a 32-72″ inch Plasma Screen (depending on the configuration purchased) and taking a new animated eye test—interactive and fun—viewing an educational slide show, educational video and even an instructional slide show or instructional video about your particular problem or procedure, all from that same monitor. As the doctor touches the active screen linked to a computer the passive screen, at the other end of the room, changes and displays different tests. Each time the doctor uses the touch screen active monitor a new and different test is shown. With the iQueVision: A/VTS, the distance factor can be simulated on a monitor or TV screen. Using the right monitor with the pre-configured computer system, the testing room would only require half distance in size, 10 feet. Now image a plasma screen being used to project real world images, a street with trees and houses. As the test proceeds you're asked if you can see the various signs posted to simulate different views—not realizing that your also being tested with visual acuity letters on each sign at different points and sizes along that street. This system would help not only in the initial testing phase but would also help in the prescription phase during a follow up where the patient should be re-tested with their prescription glasses on. This system would also replace computerized auto refractors. These machines measure the light refraction automatically in order to find the right prescription, however the same auto-refractor can't be used when wearing the prescribed glasses. The plasma screen system would add in the follow-up exam to ensure the lenses were correct in “Real World Vision Testing”. Plasma screen testing has never been used—by anyone. [0018] The iQueVision: A/VTS would include animated tests and slide test with letters, numbers, pictures in 2D and 3D, symbols, graphs, charts, color testing, gray density, depth perception, 2D and 3D animation, hue and density. (See FIG. K) On the same a pre-programmed computer system, doctors who purchased the system, would have access via the Internet using browser technology such as Netscape, Internet Explorer, Safari or any other web browsing tool to download the latest up dates and new animated computer testing methods, (see FIG. H) if and when the doctor wants to purchase another test. (See FIG. 5 ) At the core of iQueVision system a software tech with an internet connection to the server itself can quickly be accessed for on sight trouble shooting before sending in a hardware tech to fix the problem. Using a portable laptop computer or Tablet PC, the same testing system is design for 10 ft or 40 cm testing in off-site or remote locations. The general scope of using this new iQueVision: A/VTS is endless in order to achieve better testing results with all of the primary tests this system can offer technically accurate, more consistent results and surpasses any other projection based technology in use today. [0019] Research indicates that nothing else like the iQueVision: Animated/Vision Testing System exists for testing visual acuity today. The new “Digital Formula” (see FIG. A) raises the bar and sets a new standard for displaying, animated vision tests, slide tests and visual acuity letters. When it is viewed on any high resolution TV, computer monitor screen, laptop, tablet pc or plasma screen this system allows for greater flexibility, portability with wired or wireless ease of use. (See FIG. L 4 ) This system will improve with new technology to help keep testing procedures current for every doctor who purchases the system but will always remain a kiosk, touchscreen, keyboard/mouse or voice recognition driven system. DESCRIPTION [0020] The level of difficulty in designing a system such as this far exceeds the capabilities of most computer users. A thorough knowledge of Unix operating systems and many software programs and the ability to integrate the use of the programs to produce the final product is required Creation of this Animated/Vision Testing System involved the use and integration of the following programs: 1. Adobe Photoshop 2. Adobe LiveMotion 3. Adobe Illustrator 4. SketchUp 5. Adobe GoLive (HTML, XML) 6. Adobe Dimensions 7. Adobe AfterEffects 8. Apple iMovie 9. FinalCut Pro 10. iDVD 11. DVD Studio Pro 12. Maya or similar 3D software 13. Unix Operating systems and Unix programing software 14. FileMaker Pro (the database) 15. Macromedia's Flash 16. Macromedia's Fireworks 17. Macromedia's Dreamweaver [0021] Other technologies include: Apple Computer's QuickTime technology for the conversion process. The equipment required includes the iQueVision: A/VTS software, a Computer/Tablet PC/Laptop/Unix based Computer Server (consumer, portable, or other computer-related product), a hi-definition television, computer monitor or plasma screen. The system can be modified to the size of the screen required in order to properly administrator a visual acuity test using the iQueVision: ANTS. The technology will also allow for the use of royalty-free video, photos and or venders commercial products as may be requested by a doctor to produce a customized version of the iQueVision: Animated/Vision Testing System using any of the touch screen (kiosk) computer, Tablet PC, PDA and or Keyboard/Mouse input devices. This system would also include a web browsing interface to access the internet for product or research, information or patient information. This system would also include an optional wired or wireless keyboard/mouse and/or a wired or wireless monitor/plasma integrated system as an up grade. All of these features combined in a cross platform operation with internet access from an examination room using the iQueVision: Animated/Vision Testing System can not be found in any other vision testing system to date. SCIENCE [0022] Each animated/slide letter is based on a mathematical formula for 20/20 visual acuity testing established in 1862 by Dr. Hermann Snellen. (See FIG. A) As previously stated the “Digital Acuity Visual Testing Formula” or “Digital Minimums” is the key to making this paradigm shift in science work. It takes Dr. Snellen formula from 1862 and modifies/updates it using 21st century technology. Other testing modules include, but are not limited to, the following: color—density—dot—2D and 3D art animation, all designed to work seemlessly on the iQueVision A/VTS. (See FIG. K) Once all the tests are approved in design and functionality by clinical trials, the system will be marketed to doctors and/or their patients for treatment and therapy. As mentioned other uses include a home based therapy system that doctors can either sell or give to patients who have internet access to improve their vision with home testing and therapy sessions. The process for designing a new iQueVision: ANTS is complex, but the end result is a system that any doctor can use and every patient benefits with a standardized testing system that replaces out dated systems. [0023] While most testing system are restricted to one platform or operating system, iQueVision: A/VTS is not. As mentioned in the title of the this patent the programs used to build this vision testing system will work on not just one but three different platforms. (see FIG. E) This programed (database) is designed to work on the three operating systems Macintosh/Unix, Windows and Linux. This versatility of being the only cross-platform system distinguishes the iQueVision A/VTS as a very unique, one of a kind vision testing programs among the stand-alone systems currently on the market today. This is the core attraction to operating the iQueVision Testing system and another feature that no other system can claim. The entire testing program can be ported or used with your favorite operating system or one that may already has in place. The materials used to make the iQueVision: A/VTS product include all formats of computer based systems, touch screen technology, keyboard, mouse, tablet PC, PDA or even voice control. [0024] FIG. 1 : Shows the Stand Alone Configuration of the iQueVision: Animated/Vision Testing System, the design to use with computer/Unix based computer server via remote control with a touch screen (kiosk), PDA and or Keyboard with a Hi-resolution monitor or TV screen in a clinic. [0025] FIG. 2 : Shows Multiple Operating Systems on a Unix Server iQueVision: Animated/Vision Testing System with a computer/touch screen (kiosk), PDA and or Keyboard with an internet connection and Hi-resolution monitor or TV screen. This is also the cross-platform configuration showing the Macintosh/Unix, Windows and Linux platforms. [0026] FIG. 3 . Shows the Multiple OS with the total number of uses and host files that can be accessed using the iQueVision: Animated/Vision Testing System with a portable laptop 17″ computer and or Hi-resolution monitor or TV screen with wireless or hard-line internet connection. [0027] FIG. 4 . Shows the Portable or Wireless Connections to a Unix Server iQueVision: Animated/Vision Testing System on both touch screen computers and monitors. [0028] FIG. 5 . Shows the iQueVision: Animated/Vision Testing System with home therapy application for vision care with a computer connection via the internet on different browsers. [0029] FIG. 6 . Show the subcategories listed for different configurations and uses, but is not limited to these specific fields of vision care. [0030] FIG. 7 . Shows the iQueVision: Animated/Vision Testing System functionality and menu control. Along with a list of categories that can be added to the system as its being developed. [0031] FIG. A. Shows the Measurement Formula for 20/20 Vision as it has been used over the past 60 years in the development of projection systems. However, it also shows the new Digital Acuity Vision Testing Formula (DAVTF) that was discovered during the building of the iQueVision: Animated/Vision Testing System. [0032] FIGS. B 1 , B 2 , B 3 , show the three top competitors in this field and the projection systems they currently sell, [0033] FIG. C. Show a sample image of the what the current projection system (on the left) are providing as compared to the quality of the same size letter (E @20/20) the new iQueVision Test (on the right) can produce. [0034] FIG. D. In the course of study general “Observations” came to light with regard to Bulb life, Room Lighting, and the Slides used in testing. I have also included an image of the first slide projector patented in 1922, [0035] FIG. E. Shows the iQueVision ANTS cross—platform configurations showing the same vision testing system can be accessed by all three operating systems. [0036] FIG. F. Shows the number of Optional Tools available to the doctor in order to use the same iQueVision A/VTS. [0037] FIG. G. Not only does the doctor has a choice of tools but also the choice of options that can be added as needed or upgraded to the iQueVision Testing System. [0038] FIG. H. Shows the “Backdoor” terminal connection iQueVision would have in servicing and maintaining each unix server sold to a clinic. Using a command line system an tech can literally access the system, fix the problem and restart the system via a simple internet connection. [0039] FIG. I 1 , I 2 , I 3 . The next three sections show the choices that are available to the doctors who purchase this system. I 1 —Basic Menus, I 2 —Clinical Menus and I 3 —Custom Menus. This is also unique to iQueVision Testing System as it leads the way in personalization for each and every doctor or clinic. [0040] FIG. J, A custom button can also be added to the menu system for each doctor. Each doctor has his or her own operating method. Using the custom button organizes the test in the pre programmed order in which the doctor would like to use them. This is a time saving functions as all the entire testing process flows from one test to another without having to return to the main menu. [0041] FIG. K, Show a list of the top 15 test that can be accessed by the doctor in both Slide and Animated form. You average slide projector can only handle 30 test. The new Snellen Test alone has 81 slides which is more than double then the current test. Bring the total number of slides to over 300. [0042] FIGS. L 1 . L 2 . L 3 . L 4 . L 5 . [0043] These are the collective configuration L 1 , “Stand Alone” Mac/Unix. L 2 , “Stand Alone” PC Configuration. L 3 , “Cross Platform with Server Connection”. L 4 , Portable Systems” and L 5 , “Server Combinations” In the “Stand Alone” configuration this show another important aspect of this system in having a choice between DVI and VGA. DVI simple put is an extension of this the same screen, where VGA, if you look carefully, is a mirrored image of the same picture on both screens. This will be come more clear with FIGS. M 1 and M 2 . [0044] FIG. M 1 . & M 2 . M 1 —shows the mirrored connection or VGA connection between the active and passive monitor. Meaning that what the patient will be able to see the control panel at the bottom of the screen, even thought it will be too small to read at 20 ft. M 2 .—of the two systems the DVI system is better as you can see the control panel only appears on the doctors portable laptop and the patients screen shows only the test that is displayed [0045] FIGS. N 1 . N 2 . & N 3 . These represent a general idea of what the interface may look like when completed. Demos have already been made using the images from N 1 . and N 2 . N 3 —is the newest addition to the menu system with a general idea of it's control function and features. [0046] FIG. O. This is where it all comes together, here you can visual see the different types of rooms currently being used by doctors today. The first two rooms show the angle of distortion from projection systems and the last room with iQueVision A/VTS direct, line of sight viewing on a bright monitor. [0047] FIG. P. This show Photo 1 and Photo 2 . In Photo 1 you can see a slide projector in the dark trying to project an image 20 ft across the room. The is a great representation of the just how dim the letters are at the opposite end of the room and just how hard it is to read them. In Photo 2 the rooms lights have been turned on and yet using a large monitor screen you can easily read the letters on the test chart This also show how a doctor using the touch screen system would be able to change or display any letter in any size or call up any other test needed during the examination process just by pushing the touch screen kiosk. EXAMPLE [0048] The technical equipment could be, but is not limited to, a system such as the Apple Unix Server or Laptop, Tablet PC, PDA, a Planar 19″ wide TTF LCD Flat Panel monitor, or the Actual Depth 15bx 3D LCD monitor. As long as the iQueVision A/VTS computer/laptop/Unix server, High resolution monitor and computer system are capable of providing the right control, specific resolution and contrast ratio while meeting the minimum requirements of the “Digital Minimums,” the choice of hardware equipment is entirely up to the user. OPERATION [0049] In day to day operation, the iQueVision: A/VTS is accessed via a local area wired or wireless network to a computer/laptop/tablet pc/PDA/or Unix based computer server. (see FIG. 1 ) [0050] 1. Turning on any one of the system mentioned will activate a passive monitor at the other end of the room and directly opposite from the patient sitting in the exam chair. An active display monitor, used by the doctor, would display a control panel of animated/slide tests from his touch screen (kiosk), PDA or Keyboard/mouse located next to them. (see FIG. P) Using the touch screen system the doctor would choose a test that is displayed on the passive monitor in front of the patient. [0051] 2 Using the touch screen (kiosk), PDA and or Keyboard/mouse along with the equipment listed above, the doctor would then pick one of the general test menus. Once the appropriate test category was located, the doctor would administer the animated/slide vision test. The doctor would have full control over each animated/slide test, being able to start, stop, reverse, pause and return to the main menu as desired at the touch of an on screen button. [0052] 3. Using the remote touch screen (kiosk), PDA and or keyboard/mouse each sub-menu category would give the doctor better options and single out the testing process he or she believes would assist in making the best diagnosis. Having “all” the test in one system either animated or in slide form speeds up the process and avoids the need to take the patient to another room looking for a tests. Using the iQueVision: A/VTS allows the doctor a freedom of choice, instant access, and operational ease of use. [0053] 4. Using the remote touch screen (kiosk), PDA and or Keyboard/mouse the doctor would also have access to education videos, charts, graphs or any teaching or training tool also design to be quickly access using this system. [0054] 5. Turning on the computer/laptop/tablet pc/Unix based server with the optional keyboard and internet access the doctor can quickly call up any reference material, product or training tool to help the doctor/patient relationship. This addition also allows the doctor to monitor and support a home therapy system given to the patient. The doctor would also be able to demonstration how to use, access and apply the home therapy system. [0055] (Note: Custom interface—While the sample pages are designed to give better clarification, they are not intended to represent the only style that can be designed into this iQueVision: A/VTS. This architecture also lends itself to customizing for individual doctors who want to show their own company name or logo, style or preference in mind. While the general appearance of the menus in the computer may appear different according to a doctors preference, the basic science and functionality that goes into creating this iQueVision: Animated-Vision Testing System will be the same on every computer/laptop/Unix based computer system with touch screen or keyboard/mouse.
This invention relates to field of Visual Acuity Testing, specifically to animated/slide computerized vision testing system and a new “Digital Formula” for the measurement of visual acuity and vision testing for humans. This system was also designed to be the first system to work on not one but three computer platform systems to achieve accurate and consistent vision testing results. Formulated to work on any digital screen this system was designed to replace a 60 year old idea (projection systems) that are still in use today. Todays vision testing methods are out dated and not ceritified in quality. With iQue A/VTS a doctor, if desired may pull up the same testing system on a 17″ LCD monitor all the way up to and including a 50″ Plasma system under the guidelines of the “Digial Formula”. Using Plasma Screen or the new OLED technology offers every patient a testing envoirnment with static or motion images design with a mathamatical formula for vision acuity testing under “RealWorld” condistion. iQueVision's goal is bring vision testing into the 21st Century.
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BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in cookware and, more particularly, to a cooking utensil cover having a means for mounting the cover in an approximate upright position on the utensil rim. 2. Description of the Prior Art During the preparation of foodstuffs in a skillet, saucepan, dutch oven or the like, it is frequently necessary to remove the cooking utensil cover and stir or baste the items being cooked therein. Quite often the cover interior is spattered with liquid exuded from the foodstuff during the cooking process or the interior surfaces are covered with condensate. As such, it is undesirable to place the cover on a counter top and allow the fluids to accumulate thereon. Likewise, such placement is undesirable because the cover is generally quite hot and could cause a burn by an unwary user. Still further the stirring or basting of foodstuffs in a cooking utensil may require the use of both hands. In such a case, the cover will have to be placed upon a counter top or the like with the aforementioned inherent disadvantages. SUMMARY OF THE INVENTION The present invention provides a support means secured to a sidewall of a cooking utensil cover which allows the cover to be engaged in a somewhat upright position upon the top rim or edge of the utensil. This frees both of the user's hands for use in stirring or basting the foodstuffs cooking in the utensil. It further eliminates potential hazards incumbent with placing the hot cover on a counter top or the like. Additionally, by locating the cover in a somewhat upright position on the edge of the cooking utensil, the savory fluids exuded during the cooking process will flow from the interior surfaces of the cover back into the cooking utensil. This, of course, enhances the flavor and nutritional value of the foodstuff and also prevents it from becoming overly dry. The lid mount of the present invention includes fastener means for affixing the mount to the utensil cover and includes a slot extending across the outer surface thereof. The slot may take the shape of the sidewall edge contour and is of a width slightly larger than the thickness thereof. It is desirable that the slot extend laterally at an acute angle with respect to the sidewall surface of the cover. In this way when the mount is engaged with the utensil rim the cover will assume a tilted position over the utensil. In this manner the condensate and cooking fluids will more readily drain back into the cooking utensil and there will be less tendency for the cover to become unbalanced or dislodged. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a cooking utensil and cover having the lid mount of the present invention. FIG. 2 is the cover and utensil of FIG. 1 with the cover engaged with the rim of the utensil by connection with the lid mount. FIG. 3 is an enlarged view taken along line 3 of FIG. 1. FIG. 4 is a fragmentary enlarged cross-section view of the lid mount engaged with the utensil rim shown in FIG. 2. FIG. 5 is a cross section taken along lines 5-5 of FIG. 3. FIG. 6 is a front elevation view of the lid mount shown in FIG. 1. FIG. 7 is a top plan view of the mount shown in FIG. 1. FIG. 8 is a back elevation view of the lid mount of FIG. 1. DESCRIPTION OF THE PREFERRED EMBODIMENT Referring now to the drawings, a cooking utensil 10 is shown comprising a pan 12 and cover 14. The particular illustrative embodiment shown in FIGS. 1 and 2 is an electric skillet having a thermostat means 16 and leg handles 18. Of course, these features form no part of the invention, but are included to show a suitable combination in which the mounting means 20 may be utilized. The mounting means 20 is secured to the cooking utensil cover 14 adjacent the peripheral edge 22. In the embodiment shown, the mounting means is secured to sidewalls 24 of the cover proximate the midpoint between the lateral ends or corners 27. In this manner the cover will attain a stable posture when mounted in the position shown in FIG. 2. As best shown in FIGS. 3-5, the mounting means 20 includes an opening 30 adapted to engage a portion of the rim 34 of the pan 12. The opening 30 is disposed in the mounting means in a manner to orient the cover 14 in an inclined position above the pan 12 when the opening is in engagement with the pan rim 34. In the particular embodiment shown, the mounting means is a block of molded insulative material and includes a first surface 38 which contacts the cover sidewall 24 in a flush manner. With such a large area of contact a more stable connection is obtained thereby resulting in a strong stable connection. The mounting means is secured against the sidewalls with a pair of screws shown by reference numeral 40 engaging corresponding threaded openings 41. Of course, other fastening means may be used such as adhesion, spot welding, bolts, or the like. It is also contemplated that the mounting means may be formed integral with the utensil cover and/or sidewall. The block 20 includes a second surface 42 which is the outermost surface of the block generally opposite the first surface. This second surface 42 contains the opening 30, which, in this embodiment, is a slot extending across the second surface. The lateral extent of the slot is inclined at an acute angle α relative to the surface of the sidewall. In this manner when the cover and mounting means are positioned upon the edge of the rim 34, the cover will be disposed in an inclined somewhat upright position over the pan. This, of course, allows for any condensates or cooking fluids accumulated on the interior surfaces of the cover to drain down and flow into the pan itself. Additionally, the cover is less likely to wobble into a more vertical position whereby it would be unstable and cause a possible imbalance of the pan 12. It will be understood that the present invention includes a mounting means on utensil covers that are without sidewalls. Such covers are typically used with saucepans or dutch ovens and may be slightly convex in cross-sectional shape with a flat peripheral rim. With such covers the opening 30 would be disposed in the mounting block to orient the cover in an upright position when engaged with the utensil rim. In many instances the opening may extend almost parallel to the cover rim to effect the desired inclination between the cover and pan. To further enhance the firm connection between the opening 30 and skillet rim 34 it will be understood that the opening preferably conforms to the shape of the rim. In the particular embodiment shown, the pan 12 is an electric skillet wherein the rim 34 is substantially straight. The slot 30 likewise is substantially straight. Of course, it will also be noted that the width of the slot is slightly larger than the width of the rim 34. It will be further understood that the slot opening 30 may take other configurations depending on the type of rim structure of the cooking utensil itself. While the invention has been described with respect to a preferred embodiment, it will be apparent to those skilled in the art that various other modifications and improvements may be made without departing from the scope and spirit of the invention. Accordingly, it is to be understood that the invention is not to be limited by the specific illustrative embodiments, but only by the scope of the appended claims.
A support block is affixed to the sidewall of a cooking utensil cover. The block is provided with a slot across its outer face adapted to engage the top rim of the utensil. The slot is oriented in the block to cause the cover to assume an approximate upright position over the utensil when the slot is engaged with the utensil rim.
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BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to household coffee brewing apparatus and more particularly to such apparatus which provides an indication of sufficient calcification that cleaning is desirable or necessary. 2. Description of the Prior Art Coffee brewing apparatus incorporating a throughflow heater of the kind to which the present invention relates is well known. Such a heater, which serves for electrically heating water to be passed to a brew station including a brew basket supporting a filter filled with fresh coffee grounds, is included in the flowthrough path of a water conduit extending from a water reservoir to the brew station. The present invention is concerned with the safeguarding of such a throughflow heater from the effects of mineral deposits. Water pollution is a virtually universal problem, and in areas with so-called hard water, the deposition of minerals, primarily calcium carbonate, in apparatus in which tap water is heated to temperatures above 68° C., is inevitable. Such deposition occurs on the inside of the water conduit, so that electrical heating coils customarily mounted on the outside, are thus able to transmit less and less heat to the water within the conduit owing to the heat insulating layer of the mineral deposits. Therefore, such coffee brewing apparatus is commonly accompanied with instructions to the effect that, if hard tap water is used, the apparatus must be periodically cleansed, for example, with vinegar. In practice, such cleaning is often times not effected, or at least not on a timely or routine basis. In the long run, therefore, a thick layer of scale will have formed within the water conduit, with the result that the heating coils cannot dispose of their heat to the water, at least not to a sufficient extent, and become overheated and ultimately may burn out. Apart from being a potential fire hazard, this may cause permanent damage to the apparatus, possibly requiring its replacement. In order to remedy this drawback, coffee brewing apparatus of the kind referred to have sometimes been provided with safety devices in the form of fuses connected in series with the heating coil. When a given temperature is exceeded, these break the circuit. Nevertheless there is the drawback in this instance that, before the circuit is broken, the heating coil may already have become so hot as to burn out, or the temperature may already have become so elevated that the coil loses its tension, thereby interfering with proper heat transfer in future operations. Many prior proposals for safeguarding the heater mechanism of coffee brewing apparatus from overheating due to excessive mineral deposits in the water conduit and thereby resulting in damage to the mechanism and to the housing, have been based on the sensing of temperature in the space surrounding the heater and within the housing of the apparatus. Thus, it is known to provide a thermoswitch on the outside of the coil windings which, when a threshold temperature is exceeded, either actuates an alarm lamp or operates a re-settable switch which can be manually reinstated after cooling. However, these devices. did not usually indicate specifically that the inoperative condition resulted from excessive mineral deposits in the water conduit. In other instances, an indicator informing the operator of the need to clean the unit would be energized after an arbitrary period of time had elapsed or after the machine had been operated for an arbitrary number of brew cycles. Again, these expedients sometimes proved to be unreliable in actual practice. A number of other expedients have been devised and patented. In the instance of U.S. Pat. No. 4,141,286 to Smit, for example, at least a portion of a flowthrough heater is made of transparent material enabling scale deposits to be visually observed by a user. U.S. Pat. No. 4,292,499 to Kleinschmidt et al discloses a calcification indicator in a system utilizing PTC resistors for heating. With one resistor element located at a water entry region and another located at a water exit region, electronic circuitry is provided for determining when a difference of current flow in the exit heating element compared to the entry heating element exceeds a given value indicative of the need for cleaning. An indicator is triggered when cleaning is required. In U.S. Pat. No. 4,139,761 to Obrowski, a thermally responsive switch and calcification indicator are together provided electrically in parallel to a water heater and an associated heater thermostat. The thermally responsive switch is subject to opening at a temperature much higher than the thermostat such that when the heater thermostat opens, the thermally responsive switch remains closed. This enables the heater to continue to be energized but the calcification indicator to turn on to indicate that cleaning is desirable. Another indicating system is disclosed in U.S. Pat. No. 4,214,148 to Fleischhauer which utilizes first and second temperature dependent switches in series with the heater resistor. The switching temperature of the first switch is below that of the second switch but both temperatures are in the range which occur with calcification in the water heating operation. A time delay member actuates an indicating lamp after a predetermined time but operates only when the first switch is open. The time delay is for the purpose of preventing a false indication which can occur due to temperature fluctuations in the heating operation. The time delay member ceases operation and returns to its original state when both switches are both either open or closed. The foregoing systems were known to the applicants when they conceived the present invention. It was their intent to improve upon the reliability of the known systems by obtaining a more accurate indication of a calcified condition. At the same time, they sought to achieve this goal with a system exhibiting a simplified construction and operation resulting in its being less expensive to manufacture and maintain. They believe the present invention achieves all of these goals. SUMMARY OF THE INVENTION To this end, an indicating system is disclosed for a coffee brewing machine which operates to notify the user when it is time to clean the water supply conduit of accumulated mineral deposits. When a self contained removable reservoir is inserted into its operative position connecting to the water supply conduit, it closes the contacts of a temperature sensitive switch. During normal operation, the switch opens when water is depleted from the reservoir and the brewing cycle is completed. However, if the switch opens while water remains in the supply conduit upstream of the heater mechanism, this is a sure indication that there is a substantial accumulation of mineral deposits in the supply conduit. Thus, a sensing mechanism is employed to detect the presence of water in the supply conduit after the temperature sensitive switch opens, and a lamp is energized to indicate the condition. In one embodiment,, the sensing operation is performed by an electromechanical device, and in another embodiment by logic circuitry. The invention is of simplified design resulting in economies of construction and operation. It lends itself to existing designs enabling it to be readily applied to coffee brewing machines presently being manufactured. Furthermore, by reason of its simplicity, it is highly reliable in use and therefore of substantial benefit to the domestic user. Other and further features, objects, advantages, and benefits of the invention will become apparent from the following description taken in conjunction with the following drawings. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory but not restrictive of the invention. The accompanying drawings, which are incorporated in and constitute a part of this invention, illustrate one embodiment of the invention, and, together with the description, serve to explain the principles of the invention in general terms. Throughout the disclosure, like numerals refer to like parts. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a coffee brewing system which embodies the present invention; FIG. 1A is an escutcheon intended for the face of the coffee brewing system illustrated in FIG. 1; FIG. 2 is an exploded view of portions of the coffee brewing system of FIG. 1 as seen from the rear thereof; FIG. 3 is a rear elevation view of the coffee brewing system illustrated in FIG. 1; FIG. 4 is a cross section view taken generally along line 4--4 in FIG. 3; FIG. 5 is a cross section view, similar to FIG. 4, illustrating another position of components therein; FIG. 6 is a cross section view taken generally along line 6--6 in FIG. 3; FIG. 7 is a detail elevation view, in section, illustrating a sensing component of the invention; FIG. 8 is a cross section view taken generally along line 8--8 in FIG. 7; FIG. 9 is an electromechanical schematic view illustrating one embodiment of the invention; and FIG. 10 is an electronic schematic view of another embodiment of the invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS Turn now to the drawings and initially to FIG. 1 which illustrates a coffee brewing system 20 embodying the present invention. While the system 20 is illustrated as being of the type intended for mounting beneath a cabinet 22, this is only by way of example and the invention need not be so limited. An escutcheon 23 as illustrated in FIG. 1A is provided on the face of the housing to indicate a number of operating conditions pertaining to the system 20. As seen in FIGS. 1, 2, and 3, the system includes a fresh water reservoir 24 which is a self contained unit in the form of a drawer which is selectively movable on a housing 26 between a withdrawn position (FIG. 4) and an operative position (FIGS. 5 and 6) for connection to a water supply conduit 28. Prior to operation of the system 20, the user may fill the water reservoir 24 with any desired amount of water up to the limit of its capacity. Of course, the amount of water would be consistent with the amount of ground coffee to be placed in a brew basket 30 which also shall have been inserted by the user in an operative position on the housing 26. The brew basket 30, taken together with an outlet conduit 31 downstream from an electrically energizable heater 32, and a shower plate 34 for receiving heated water from the outlet conduit and directing it into the brew basket 30 are all collectively referred to as a brew station 35. As water flows from the reservoir 24 through the upstream supply conduit 28, then through an intermediate conduit 36 adjacent the heater 32, the water is heated to a sufficient extent to form a heated vapor which flows through the outlet conduit 31, then through the shower plate 34 into the brew basket 30 at the brew station 35. The heated water and vapor mixture which flows from the shower plate 34 at the brew station 35 flow through an appropriate amount of fresh coffee grounds 38 previously deposited by the user into a filter 40 supported in known fashion within the brew basket 30. In this manner, newly brewed coffee flows through the filter 40 and through suitable apertures (not shown) in the bottom of the brew basket 30 and into a waiting insulated carafe 42. The carafe is slidably received on the housing 26 and suspended from spaced apart parallel rails 44 integral with the housing 26 which slidably receive an annular rim 46 of the carafe. At the outset of a normal operation of the coffee brewing. system 20, a master switch 48 (FIG. 1) is moved to the "start" position. Additionally, the reservoir 24 is moved to an operative position (FIGS. 2 and 6) at which a male fitting 50 thereon in communication with the interior of the reservoir is connected with a female fitting 52 and an upstream extremity of the water supply conduit 28. It is supported on spaced apart parallel runners 24A which are slidably supported on a horizontal shelf 26A of the housing. However, it will be appreciated that operation of the brewing system 20 will not proceed until the carafe 42 and reservoir 24 are fully inserted into the housing 26. As seen in FIG. 3, when the carafe is fully inserted, a projecting surface 53 thereon engages an actuating pin 54 slidably received on the housing and effective to close a carafe limit switch 58. Similarly, when the reservoir 24 is fully inserted, its rear wall engages a toggle 56 which is effective to close a reservoir limit switch 59. A primary reason for this construction is to assure that a brewing cycle will not commence until there is a firm, sealed, connection between the male fitting 50 and the female fitting 52. Otherwise, it would be possible for a brew cycle to commence with leakage of water from the male and female fitting interface, the result being an incomplete brew. When the reservoir 24 is in its operative position (FIG. 5), an actuating tab 60 integral therewith is caused to engage a rocker cam 62 pivotally mounted on a stub shaft 64 which extends between and is supported by spaced apart ears 66 of a U-shaped support member ultimately mounted on a chassis 68 which also mounts the heater mechanism 32 and intermediate conduit 36. In turn, the chassis 68 is mounted to the housing 26 in any suitable manner, as by means of fasteners 70. A first end 72 of the rocker cam 62 is thereby engaged by the actuating tab 60, and when the reservoir 24 is in its operative position, causes a second end 74 of the cam 62 to engage an actuating button 76 of a temperature sensitive switch mechanism 78 (see FIG. 5). The switch mechanism 78 is of the well known so called "manual" variety which is manually closed before the beginning of a heating operation and which, subsequently, when the temperature exceeds a predetermined magnitude is caused to open and remain open thereafter regardless of any subsequent reduction in temperature of the sensed structure. One typical example of such a switch mechanism is Model No. 1NT08L manufactured by Texas Instruments, Inc. of Austin, Tex. Turn now to FIG. 2 and, more particularly, to FIGS. 7 and 8, which illustrate a sensing mechanism 80 for detecting the presence of water in the upstream supply conduit 2 after the temperature sensitive switch mechanism 78 moves to the open position. It was previously mentioned that the presence of water in the upstream supply conduit 28 after the switch mechanism 78 opens is indicative of the presence of substantial mineral deposits located in the intermediate conduit 36 which thereby prevent all the water initially in the reservoir from being received at the brewing station 34 prior to completion of the brew cycle. The sensing mechanism 80 includes a sensing chamber 82 which defines a cavity 84 in communication with the supply conduit 28. A ball 86 and cooperating valve seat 88 immediately downstream of the sensing mechanism 80 operate as a check valve to prevent heated water from the intermediate conduit 36 from flowing back into the reservoir 24 during the brewing operation. The sensing chamber 82 has a generally planar ceiling 90 and a generally planar floor 92. However, the floor 92 is inclined downwardly in the direction of the supply conduit 28. As seen especially well in FIGS. 7 and 8, a pair of spaced. apart pins 94 are upstanding from the floor 92 and extend into the cavity 84. An elongated float member 96 of any suitable floatable material is provided with a pair of spaced apart bores 98 adjacent one end thereof extending transversely through the member and adapted to freely receive the pins 94 therethrough. This construction allows the float member 96 to move between a raised inoperative position as illustrated by solid lines in FIG. 7 and a lowered operative position as illustrated in phantom in that same figure. A magnet 100 is mounted as by being embedded within the float member 96 at a location distant from the end with the bores 98 therein. It will further be appreciated that the float member 96 has upper and lower opposed parallel faces 102, 104, respectively. The upper face 102 has a plurality of upper feet 106 integral therewith and projecting outwardly therefrom. Similarly, the lower face 104 has a plurality of lower feet 107 projecting outwardly therefrom and integral therewith. Opposed gripping fingers 108 serve to protectively and firmly support a reed switch 110 on the under surface of the floor 92 at a region proximate to the magnet 100 when the float member 96 is in its dotted line position (FIG. 7). As seen in FIG. 9, the reed switch 110, which is normally closed, is. electrically in series with a source 112 of electrical power and with the heater mechanism 32. When the float member 96 moves to the dotted line position illustrated in FIG. 7, the magnet 100 causes the reed switch 110 to open. Thus, when water is flowing through the supply conduit 28, it fills the cavity 84 of the sensing chamber 82 and causes the float member 96 to move to the solid line position as illustrated in FIG. 7. In this position, the upper feet 106 serve to hold the float member proximately spaced from the ceiling. The spacing between the upper face 102 and the lower surface of the ceiling 90 is to prevent the adhesion of the float member 96 and the ceiling 90 which may otherwise occur by reason of the capillary action of the water. In a similar fashion, the lower feet 107 which project outwardly from the lower face 104 of the float member similarly hold the float member proximately spaced from the floor 92 when the float member is in the active or dotted line position as illustrated in FIG. 7. This latter position occurs when water is no longer flowing through the supply conduit 98 and is drained from the cavity 84. As in the instance of the feet 106, the feet 107 prevent the adhesion of the float member 96 and the floor 92 when the cavity 84 is being filled since the mutually opposed surfaces on the float member 96 and on the floor 92 seldom become dry. Hence, the presence of water in the cavity 84 causes the reed switch 110 to close and the absence of water causes the reed switch to open. Other components illustrated in FIG. 9 include a primary fuse 114 and a secondary fuse 116 which are electrically in series between the power source 112 and the heater 32. It is desirable that the fuses 114, 116 be of staggered rupture values within the range of safety so as to assure that both fuses could not originate from the same bad lot and thereby minimizing the possibility that a product failure would occur. Additionally, a brewing lamp 118, which may be of the neon variety, is disposed on the front face of the housing 26 and indicates that a brew cycle is in process. In a similar fashion a "clean" lamp 120, which may also be of the neon variety, is electrically in parallel with the reed switch 110 and is mounted on the front face of the housing 26. The purpose of the lamp 120 is to indicate that it has become desirable to clean the conduit 36 in a customary manner to remove the accumulated mineral deposits. The operation of the brewing system 20 as it embodies the present invention will now be described. In order to proceed with a brewing cycle, the master switch 48 is closed and the carafe 48 is moved to its operative position thereby closing the limit switch 58. The water reservoir 24 will have been filled with the appropriate amount of water to obtain the desired number of cups of coffee and move to its operative position to initially close the temperature sensitive switch 78 and close its limit switch 59. If the intermediate conduit 36 adjacent the heater mechanism 32 is substantially devoid of mineral deposits, all of the water in the reservoir 24 will have passed through the system and been converted into the coffee contained within the carafe 42. After the last of the water has passed through the intermediate conduit 36, the temperature therein rises rapidly to the point at which the switch 78 opens causing the heater 32 to completely deenergize. This is for the reason that there is no longer any water present to carry away the heat created by the heater mechanism 32. Simultaneously, the float member 96 will have moved to its active, dotted line, position (FIG. 7). Because of the absence of water in the cavity 84, the reed switch will have similarly opened. The lamp 118 turns off to indicate that the brewing cycle has been completed and the lamp 120 remains off because the brewing cycle was complete with no water remaining in the sensing chamber 82 which, if it were present, would indicate mineral deposits in the intermediate conduit 36. However, in the event water remains in the cavity at a time when the temperature sensitive switch is open, the reed switch 110 will remain open because the water within the sensing chamber 82 will hold the magnet 100 away from the reed switch. In this instance, the lamp 120 is energized and is thereby indicative of the condition in the brewing system 20 requiring appropriate cleansing of the intermediate conduit 36. Turn now to FIG. 10 for a description of another embodiment of the invention. In this instance, the presence or absence of water in the supply conduit 28 after the determination that the temperature sensitive switch 78 is open is performed by logic circuitry 122. The circuitry 122 serves to cause the "clean" lamp 120 to be energized only in the event both conditions are met. To this end, a logic gate 124 which is depicted as a NOR gate is arranged to receive a first input from a first energized circuit 126 at an input pin 128 and a second input from a second energized circuit 130 at an input pin 132. The circuit 126 includes a pair of electrodes 134, 136 which may be suitably mounted at diametrically opposed locations on an inner wall of the conduit 28. So long as water is present in the conduit 28, the normal impurities present in the water enable electrical current flow between the electrodes thereby completing the circuit between a D.C. voltage source 138 and ground 140 across a transistor 142. When water is present in the conduit, the transistor 142 is switched on, and the resulting signal is inverted before presentation at the input pin 128. However, the transistor 142 remains off in the absence of water. The second circuit 130 derives its energy from an A.C. source 144, typically 120 v., the source which energizes the entire system 20. Included in the circuit 130 is the heater mechanism 32 and its associated temperature sensitive switch 78. A suitable rectifier 146 alters the incoming signal to pulsating D.C. and, thus modified, is filtered by a suitable capacitor 148 and regulated by a zener diode 150 for presentation at the input pin 132. Upon receiving the input signals at the pins 128, 132, the NOR gate 124 transmits an output signal via an output pin 152 across a transistor 154 to the lamp 120. Among other functions, the transistor 154 serves as a protective buffer between the lamp and the NOR gate. During normal operation of the coffee brewing system 20 utilizing the circuitry 122, water from the reservoir 124 travels through the intermediate conduit 36, then to the brew station 34 and ends up as coffee in the carafe 42. By the time the. temperature sensitive switch 78 opens, all of the water in the reservoir is depleted. Therefore, the sensor transistor does not turn on with the result that the "clean" lamp 120 remains unlighted. However, when a mineral buildup occurs in the intermediate conduit 36, eventually water flow through the conduits 28, 36, and through the brew station 34 into the carafe 42 slows down with at least some water remaining in the reservoir after the temperature sensitive switch 78 has opened. When this occurs, the NOR gate 124 will output a high signal to the LED transistor 154, turning it on and causing the lamp 120 to be lighted. While preferred embodiments of the invention have been disclosed in detail, it should be understood by those skilled in the art that various modifications may be made to the illustrated embodiments without departing from the scope as described in the specification and defined in the appended claims.
For a coffee brewing machine, an indicating system which operates to notify the user when it is time to clean the water supply conduit of accumulated mineral deposits. When a self contained removable reservoir is inserted into its operative position connecting to the water supply conduit, it closes the contacts of a temperature sensitive switch. During normal operation, the switch opens when water is depleted from the reservoir and the brewing cycle is completed. However, if the switch opens while water remains in the supply conduit upstream of the heater mechanism, this is a sure indication that there is a substantial accumulation of mineral deposits in the supply conduit. Thus, a sensing mechanism is employed to detect the presence of water in the supply conduit after the temperature sensitive switch opens, and a lamp is energized to indicate the condition. In one embodiment, the sensing operation is performed by an electromechanical device, and in another embodiment by logic circuitry.
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CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of application Ser. No. 512,120, filed Oct. 4, 1974. DESCRIPTION OF THE PRIOR ART Alkali Metal Hydride Processes One known method of preparing alkali metal hydrides utilizes the reaction of alkali metal and hydrogen in the presence of alkali metal hydride. In such operation, the alkali metal hydride may expedite the reaction but the effect is not truly catalytic being more a matter of surface effect since other particulate solid dispersants such as sand, clay, or the like, are about as effective. Even in such systems, it is considered desirable to operate with close control of the balance between alkali metal and hydrogen fed to prevent the existence of a liquid phase which may stop the reaction and cause rapid build-up of scale. Another factor involved in the use of alkali metal hydride as a dispersant is the problem of residual moisture in the reactants fed and in the reactor in start-up and the need to avoid water presence of the violent reaction with moisture characteristic of alkali metals and their hydrides. In another method, alkali metal hydrides are prepared by reacting alkali metal and hydrogen in a heavy hydrocarbon oil diluent. Such processing usually provides a slurry type product that is no more than about 50 percent alkali metal hydride. It is difficult to remove the heavy hydrocarbon by vaporization or filtration which generally dictates the use of expensive solvent or extraction removal procedures or the shipment and use of the alkali metal hydride in the form of a dispersion in oil. Even these procedures have the disadvantage that the mineral oil diluent and extractant used must be water free. Alkali Metal Aluminum Dihydrocarbon Dihydride Processes Previously known processes for the preparation of alkali metal aluminum dihydrocarbon dihydrides have suffered from several disadvantages. German Pat. No. 918,928 describes the preparation of sodium or lithium aluminum dialkyl dihydrides by reacting dialkyl aluminum hydrides or dialkyl aluminum halides with sodium hydride or lithium hydride. These reactions preferably are conducted with oil-free alkali metal hydride to avoid the need for subsequent removal of the oil present with oil-dispersion alkali metal hydride. The dialkyl aluminum halide reaction further suffers from the disadvantages that it requires the preparation of the halide material and that in the process some of the alkali metal value is converted to alkali metal halide salt of low value. Another process for producing alkali metal aluminum dihydrocarbon dihydrides is shown in German Pat. 1,116,664 wherein trialkyl aluminum is reacted with alkali metal and hydrogen. This process suffers from the disadvantage that one of the three alkyl groups on the starting trialkyl aluminum is lost by conversion thereof to hydrocarbon. Another process for producing alkali metal aluminum dihydrocarbon dihydrides is described in U.S. Pat. 3,686,248. Although this is an excellent process for producing the desired product in high yield, further improvement is desirable since at times there may be a tendency toward the deposition of aluminum on reactor surfaces. SUMMARY OF THE INVENTION The present process avoids much of the prior art difficulty associated with the preparation of alkali metal hydrides as well as with the preparation of alkali metal aluminum dihydrocarbon dihydrides. The present process provides a catalyzed process for producing alkali metal hydride at a high rate, in a high level of safety, and without contamination by heavy oil or other materials that are not desired in alkali metal aluminum dihydrocarbon dihydrides or other materials produced from the alkali metal hydrides. Accordingly, the present invention relates to a process for producing alkali metal hydrides which comprises reacting alkali metal and hydrogen in the presence of a catalytic amount of at least about 0.001 percent by weight of alkali metal aluminum dihydrocarbon dihydride based on the alkali metal reactant fed to the process and in the presence of an inert solvent for the alkali metal aluminum dihydrocarbon dihydride. The reaction is performed under conditions suitable to form alkali metal hydride. As a result of performing the process, alkali metal hydride is produced which is useful in various ways. For example, it is highly desirable for the production of alkali metal aluminum dihydrocarbon dihydrides. Thus, the alkali metal hydride process is advantageously used in a novel process for producing alkali metal aluminum dihydrocarbon hydride. In one aspect therefore, the present invention provides a process for producing alkali metal aluminum dihydrocarbon dihydrides which comprises reacting alkali metal and hydrogen in the presence of an inert aromatic hydrocarbon solvent for the alkali metal aluminum dihydrocarbon dihydride and a catalytic amount of at least about 0.001 percent by weight of alkali metal aluminum dihydrocarbon dihydride, under conditions suitable to form alkali metal hydride, thereby producing alkali metal hydride, and then reacting the alkali metal hydride with trihydrocarbon aluminum, aluminum and hydrogen, in the presence of said solvent under conditions suitable to form alkali metal aluminum dihydrocarbon dihydride thereby producing alkali metal aluminum dihydrocarbon dihydride. In another aspect, the present invention provides a process for producing an alkali metal aluminum dihydrocarbon dihydride which comprises reacting alkali metal and hydrogen in the presence of an inert aromatic hydrocarbon solvent for the alkali metal aluminum dihydrocation dihydride and a catalytic amount of at least about 0.001 percent by weight of alkali metal aluminum dihydrocarbon dihydride based on the alkali metal fed to the process, and in the substantial absence of free aluminum, at a temperature of from about 100° to about 325° C; and a pressure of from about 50 to about 5000 psig for a period of time of from about 0.01 to about 12 hours, thereby producing alkali metal hydride, and then reacting the mixture of alkali metal hydride with aluminum, trihydrocarbon aluminum and hydrogen, in the presence of said solvent at a temperature of from about 100 to about 325° C and a pressure of from about 50 to about 5000 psig for a period of time of from about 0.01 to about 12 hours, thereby producing alkali metal aluminum dihydrocarbon dihydride. In another aspect, the present invention provides a process for producing an alkali metal aluminum dihydrocarbon dihydride which comprises reacting alkali metal and hydrogen in the presence of aluminum and an inert aromatic hydrocarbon solvent for the alkali metal aluminum dihydrocarbon dihydride and a catalytic amount of at least about 0.001 percent by weight of alkali metal aluminum dihydrocarbon dihydride based on the alkali metal fed to the process, at a temperature of from about 180° to about 325° C; and a pressure of from about 50 to about 5000 psig for a period of time of from about 0.01 to about 12 hours, thereby producing alkali metal hydride, and then reacting the alkali metal hydride and the aluminum with trihydrocarbon aluminum and hydrogen, in the presence of said solvent at a temperature of from about 100° to about 325° C and a pressure of from about 50 to about 5000 psig for a period of time of from about 0.01 to about 12 hours, thereby producing alkali metal aluminum dihydrocarbon dihydride. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 of the drawings shows a group of three curves of pressure versus reaction time for the sodium hydride formation step of Examples I, II, and IV. FIG. 2 of the drawings shows a group of two curves of pressure versus reaction time for the sodium hydride formation step of Examples V, VI and VII. DESCRIPTION OF THE PREFERRED EMBODIMENTS The present process provides a way to avoid the foregoing and other problems of the prior art and at the same time provides a catalytic effect to enhance the rate of reaction of alkali metal and hydrogen in the formation of alkali metal hydride. Preferably alkali metal used as reactant or in catalyst as well as that in product alkali metal hydride or product alkali metal aluminum dihydrocarbon dihydride is an alkali metal of Group I-A of the Periodic Table (Fischer Scientific Co., 1955), especially sodium, potassium or lithium, more preferably, sodium because of its excellent reactivity and availability at low cost. The alkali metal M of the alkali metal aluminum dihydrocarbon dihydride (MAlR 2 H 2 ) used in the process as catalyst or produced in the process is preferably the same as the alkali metal reacted with hydrogen to produce the alkali metal hydride. This preference is directed toward securing a greater uniformity of product. In other instances, the alkali metal of the alkali metal aluminum dihydrocarbon dihydride is different from the alkali metal fed for the reaction with hydrogen. Thus, for example, one may use lithium, potassium, or sodium aluminum diethyl dihydride as catalyst in the preparation of sodium hydride or potassium hydride or lithium hydride. Mixtures of two or more alkali metals may be used as reactants or as catalyst components and the alkali metal reactants are suitably the same as the catalyst components or different therefrom. Hydrocarbon groups in catalyst as well as in trihydrocarbon aluminum reactant R 3 Al where used in the processes of the present invention can be any suitable organic radicals or groups determined on a basis of reactivity, compatibility to the processing and desirability in the product, especially where alkali metal aluminum dihydrocarbon dihydride (MAIR 2 H 2 ) is a desired product. Since the R hydrocarbon groups in alkali metal aluminum dihydrocarbon dihydride are largely of a "carrier" nature, the Al--H bonds usually being the desired aspects, it is usually preferred to have the simplest practical R groups which in most instances are ethyl groups. In general, R of R 3 Al or NaAlR 2 H 2 is one or a mixture of two or more alkyl groups having from about 2 to about 30 carbon atoms per alkyl group. More preferably, R is similar or different alkyl group having from about 2 to about 6 carbon atoms per alkyl group. Preferably, the alkali metal aluminum dihydrocarbon dihydride is sodium aluminum diethyl dihydride or sodium aluminum diisobutyl hydride, especially the former. Thus, preferably the trihydrocarbon aluminum reactant R 3 Al used in the present process is triethyl aluminum or triisobutyl aluminum. Although the R groups are preferably essentially straight chain alkyl groups, where desired, other hydrocarbon groups, preferably other alkyl groups, including groups with olefinic unsaturation, branching, linkage to aluminum through secondary carbon atoms, etc., as well as groups with innocuous substitution may be used. In general, one does not desire to use groups containing adversely reactive constituents such as halogens and the like. Other typical preferred R groups are propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-lauryl, and the like. The amount of catalyst to be used in the catalyzed reaction of alkali metal and hydrogen to produce alkali metal hydride is not critical. In general, at least a catalytic amount is used. The minimum practical catalytic amount added as well as the optimum amount in toto is readily determined for specific cases by simple routine experimentation using the procedures described herein and used in the appended examples. In general, the minimum catalytic amount is about 0.001 percent by weight based upon the alkali metal fed for reaction with the hydrogen. On the other hand, since the present invention discloses the basic catalysis, the term "effective amount" includes any amount deliberately added or retained to achieve catalysis. Although there is no upper limit upon the amount of catalyst that can be used, generally there is no particular need to feed more catalyst than about 50 percent by weight based upon the alkali metal fed for the reaction and above this amount, reactor capacity is needlessly monopolized by catalyst. Of course, if one wishes to use more catalyst, the fundamental process is admirably suited to such in most instances since preferred catalysts are soluble in aromatic hydrocarbons such as toluene and others recited herein while the reactant sodium and product sodium hydride are virtually insoluble in such hydrocarbons. Thus simple decantation or filtration operations can readily separate the catalyst. Furthermore, since the most preferred catalysts are materials that are also especially desirable products readily manufactured as disclosed herein from alkali metal hydride, the separation of catalyst from the alkali metal hydride is frequently entirely unnecessary leaving the reactor monopolization factor as the principal reason for specifying an upper limit upon the amount of catalyst to use. Accordingly, the preferred amount of catalyst is from about 0.1 percent to about 50 percent by weight based on the alkali metal fed to the process for the reaction with hydrogen, especially from about 1 percent to about 20 percent by weight, particularly from about 10 to about 15 percent by weight. The solvents suitable for the present invention are quite limited. In the first place it is obvious that any solvent or diluent used must be inert, that is, not adversely reactive with any of the materials present or itself adversely degraded under the conditions used. Secondly, the solvent or diluent is desired to be a solvent for the catalyst used in the preparation of the alkali metal hydride or at least for the minimum effective amount of catalyst. The solvent or diluent is suitably merely a diluent in regard to the alkali metal reactant or alkali metal hydride product. In general, suitable solvents or diluents are readily identified from solubility data and reactivity properties so that candidates are readily revealed by routine experimentation following the appended examples. Suitable solvents or diluents are inert aromatic hydrocarbon solvents including toluene, benzene, xylene, ethylbenzene. As noted hereinbefore, the amount of solvent or diluent used is not critical. In general, one desires to use enough solvent to solubilize at least the minimum effective amount of catalyst. Usually, it is preferred to use enough solvent to maintain a fluid system which can be agitated effectively during the respective reactions by conventional propeller or turbine stirrers for both the production of alkali metal hydride and for the production of the alkali metal aluminum dihydrocarbon dihydride. Where the production of alkali metal hydride is for the purpose of converting it to alkali metal aluminum dihydrocarbon dihydride, it is usually preferred to feed at the step of production of the alkali metal hydride an amount of from about one-quarter to about 100 percent of the solvent required to solubilize all of the final product alkali metal aluminum dihydrocarbon dihydride. In this range, but especially with about one-half of the required solvent for the product alkali metal aluminum dihydrocarbon dihydride final product, one obtains a good compromise between fluidity of the reaction masses and avoidance of excessive monopolization of reactor volume by solvent. Where less than the total solvent required to solubilize the product alkali metal aluminum dihydrocarbon dihydride is fed during the reactions, it is usually desired to add the balance of the needed solvent to the reaction mass after the reaction to facilitate product removal from the reactor; however, such may not be desirable where a heel of the product alkali metal aluminum dihydrocarbon dihydride is retained in the reactor as catalyst for a subsequent run. The preferred alkali metal aluminum dihydrocarbon dihydride products are soluble to at most to only about 30 percent by weight in the solvents. Normally this is not of any particular problem except where the production of the most concentrated product alkali metal aluminum dihydrocarbon dihydride is desired, for example, to minimize shipping costs. In such instances, the solubility of alkali metal aluminum dihydrocarbon dihydride can be enchanced considerably through the use of suitable innocuous Lewis bases as co-solvents as described in U.S. Pat. No. 3,696,047, the disclosure of which, like the disclosure of U.S. Pat. No. 3,686,248, is herewith incorporated herein by reference. Thus, for example, as shown by Example V, one can add such Lewis bases as tetrahydrofuran after the final step reaction. In general, it is preferred to avoid the presence of the Lewis bases during the hydriding reactions so that where a heel of the alkali metal aluminum dihydrocarbon dihydride is to be retained in the reactor or a portion withdrawn and returned as catalyst, it is preferred to add the Lewis base to the product system after provision has been made for the retention of catalyst material. The reaction to produce alkali metal aluminum dihydrocarbon dihydride from alkali metal hydride requires the feed not only of trihydrocarbon aluminum and hydrogen but also the feed of aluminum, preferably of a reactive or activated type, preferably in the form of powder. Preferred aluminum powder contains an alloying agent such as titanium or zirconium to enhance the reactivity. It is believed that the reactions proceed as indicated hereinafter: 3 NaH + 2 R.sub.3 Al → 2 NaAlR.sub.3 H + NaH 2 naAlR.sub.3 H + NaH + Al + 11/2 H.sub.2 → 3 NaAlR.sub.2 H.sub.2 the addition of the extra aluminum to the NaH or to the combined NaH and R 3 Al system is not particularly convenient. Thus frequently it is preferred to add the required amount of aluminum to the reactor prior to the reaction which produces the alkali metal hydride and to carry it on through to the point where it reacts. The presence of the aluminum does not adversely affect the production of the alkali metal hydride when the temperature of the first step of the reaction is above about 180° C. Below this temperature, in the presence of free aluminum, the first step produces trialkali metal aluminum hexahydride. Thus where one wishes to operate the first step of the present process to produce alkali metal hydride at temperatures from about 100° C to about 180° C, one preferably does not add the free aluminum until after the formation of the alkali metal hydride is concluded. Alternatively where it is desired to feed the aluminum at the first stage and operate at from about 100° C to about 180° C, and also use a ratio of alkali metal to hydrogen at the first step equivalent to that in alkali metal hydride, one limits the amount of hydrogen accordingly and does not feed the extra hydrogen required for complete conversion of all alkali metal to the trialkali metal aluminum hexahydride at the first hydriding step. In any event, the amount of aluminum fed overall is usually at least the amount required for conversion of the alkali metal hydride and trihydrocarbon aluminum to alkali metal aluminum dihydrocarbon dihydride at the last stage. The feed of an excess of aluminum, e.g. from about stoichiometric to about 50 percent excess above stoichiometric, is usually desirable to insure complete reaction at a rapid rate. The feed of an excess of aluminum normally presents no problem since the excess left unreacted is readily retained in the reactor or separated and returned to it for use in a subsequent batch. The temperature of the reactions is critical to some extent but in view of the present disclosure, one skilled in the art does not require undue experimentation in finding optimum conditions for any particular situation. In general, the present process is suitably conducted at a temperature of from about 100° C to about 325° C. To achieve good reaction rates and avoid by-product formation and other high temperature problems, a narrower temperature range of from about 150° C to about 275° C is preferred, especially the range of from about 175° C to about 225° C. Several typical temperatures are 125° C, 150° C, 160° C, 175° C, 180° C, 200° C and 225° C. As noted in the foregoing, there is an important consideration of the present process in regard to temperature. At temperatures below about 180° C, the reaction of alkali metal and hydrogen forms trialkali metal aluminum hexahydride rather than alkali metal hydride making it necessary to avoid the presence of aluminum in the reactor when the desired product is alkali metal hydride and it is desired to use temperatures of from about 100° C to about 180° C in the first step of the reaction. Thus where aluminum is present in the reactor when the alkali metal and hydrogen are reacted to produce alkali metal hydride, a preferred temperature range of operation is from about 180° C to about 325° C, preferably from about 190° C to about 275° C, especially from about 200° C to about 225° C, typically 225° C. When a two-step process is used to first produce alkali metal hydride and then secondly the alkali metal hydride thus formed is reacted with aluminum, trihydrocarbon aluminum and hydrogen to produce alkali metal aluminum dihydrocarbon dihydride, the two steps can be at the same temperature or at different temperatures, the same temperature ranges as set forth heretofore being applicable to both of the steps. In general, however, there is no need to maintain such temperature during any time interval between such steps. Thus the alkali metal hydride system from the first step can be cooled, stored, transported, etc. before being used in the latter step. Usually it is preferred to add the trihydrocarbon aluminum to the alkali metal hydride system when the two are at substantially room temperature and atmospheric pressure or only slightly elevated in regard to room temperature and atmospheric pressure. In a preferred aspect of the present invention, the temperature is from about 190° C to about 275° C, the pressure is from about 500 to about 1250 pounds per square inch gage and the catalytic quantity of alkali metal aluminum dihydrocarbon dihydride is from about 10 to about 15 percent by weight based on the sodium fed to the process for reaction with hydrogen. Preferably the temperature of the reaction of alkali metal and hydrogen in the presence of aluminum is about 225° C, the temperature at the addition of the trihydrocarbon aluminum is from about room temperature to about 225° C and the temperature at the reaction of alkali metal hydride, trihydrocarbon aluminum, aluminum and hydrogen is about 175° C. Although the present process can be performed over the pressure range of from about 50 psig to about 5000 psig, generally the lower pressures are less desired because of low rates while the higher pressures are less desired because of equipment expense and are not really necessary for good reaction rate. Thus intermediate pressures of from about 100 psig to about 2000 psig are preferred with a narrower more preferred range being from about 250 psig to about 1750 psig, a still narrower range being from about 500 psig to about 1250 psig, with about 1000 psig being typical. These ranges apply in general where there is a reaction involving the addition of hydrogen to alkali metal or aluminum or mixed compounds or to such compounds containing other groups such as the R groups. Such hydrogen reaction is frequently termed a hydriding reaction. Thus these pressures are involved in the formation of alkali metal hydride according to the present process as well as to the conversion of alkali metal hydride into alkali metal aluminum dihydrocarbon dihydride. In general, suitable or desirable pressures are readily determind or optimized by one skilled in the art following the reaction procedures described herein in detail. Reaction time is not critical. Normally, one uses a reaction time which is at least adequate to produce substantially complete reaction at the different stages, that is, for the production of alkali metal hydride as well as for the production of alkali metal aluminum dihydrocarbon dihydride. Normally, there is no need to prolong the reaction period and one prefers to use as short a reaction time as is possible to achieve the degree of conversion desired. Any longer reaction time represents a reduction in the production capability of a given autoclave; hence usually it is undesired. In general, useful reaction times range from about 0.01 to about 12 hours. Preferred reaction times range from about 1/2 hour to about 2 hours for each of the steps (1) producing the alkali metal hydride and of (2) producing the alkali metal aluminum dihydrocarbon dihydride from the alkali metal hydride. The physical conditions used for the reaction are not critical except as indicated and have been disclosed herein to an extent which is ample to permit optimization in any respect by routine experimentation by one of ordinary skill in the art. The present examples illustrate the effect of various factors, seeking substantially complete reaction of the limiting reactant or reactants to the product of each respective stage. Thus the aluminum and hydrogen are usually fed in excess above the stoichiometric amount required for the various reactions, the limiting reactant being the alkali metal in the case of the production of alkali metal hydride and either the alkali metal hydride or the trihydrocarbon aluminum in the case of the preparation of alkali metal aluminum dihydrocarbon dihydride from the alkali metal hydride. Normally, however, one prefers to use about stoichiometric proportions of three mols of alkali metal hydride and two mols of trihydrocarbon aluminum in the conversion of the alkali metal hydride to alkali metal aluminum dihydrocarbon dihydride. For the examples, the reactor and all reactants fed are preferably placed in an anhydrous condition; however, residual moisture is readily removed where necessary by a preliminary contacting of the materials, for example, the toluene with alkali metal aluminum dihydrocarbon dihydride such as sodium aluminum diethyl dihydride or feeding the alkali metal last or bubbling the hydrogen through alkali metal aluminum dihydrocarbon dihydride. This material reacts readily but gently with water avoiding the violent reactions experienced where the water is contacted first with trihydrocarbon aluminum, alkali metal or alkali metal hydride. From the foregoing and from the appended examples and claims, it is apparent to those skilled in the art that numerous arrangements can be made of the teachings, features and aspects of the present invention and that the invention is not to be limited except in accordance with the appended claims. EXAMPLES I-IV A 2-liter stainless steel Parr reactor equipped with external electric heater, internal cooling coils, baffles and twin-turbine air driven stirrer, thermometer, pressure gage and hydrogen feed system was used for Examples I-IV. EXAMPLE I The 2-liter reactor was charged with 800 ml of toluene, 81.5 grams of sodium and 8.15 grams of sodium aluminum diethyl dihydride, the latter in a 25 wt. percent solution in toluene. The system was purged with hydrogen and approximately 100 psig hydrogen pressure allowed to remain in the reactor as heating was begun. The stirrer was turned on when the temperature reached 125° C. (The melting point of sodium is 97.5° C.) When the temperature reached 220° C, the reactor was pressurized with hydrogen to about 1000 psig and the hydrogen supply valve closed. After two minutes, the pressure had dropped 160 psig and the reactor was again pressurized with hydrogen to about 1000 psig and the hydrogen supply again closed. After five minutes from the start of operation at 1000 psig, the pressure gage was again read. This time the pressure had dropped 140 psig. Again the reactor was quickly pressured to about 1000 psig following which a drop of 120 psig was observed at the 8 minute point. The procedure was continued with measurement and rapid repressurization to about 1000 psig at the 13, 20, 23, 28 and 41 minute points. The pressure drop results are tabulated hereinafter in the column, the consecutive pressure drops being added together in sequence to provide the Σ pressure drop figures which are those used in plotting Curve A of FIG. 1. Throughout the procedure the reactor temperature was held at about 220° C. The foregoing procedure is a simple way to determine reaction rate without requiring exact flow rate measurement for the pressurized hydrogen. ______________________________________Time Pressure (psig)(Minutes) Δ Ε______________________________________0 -- --2 160 1605 140 3008 120 42013 130 55020 80 63023 20 65028 5 65541 5 660______________________________________ After the reaction, the vessel was cooled, the hydrogen pressure released and the dispersion of NaH in toluene discharged into a receiver. The dispersion was filtered to separate the sodium hydride from the toluene solution of sodium aluminum diethyl dihydride catalyst. The solid remaining was analyzed and shown to be NaH of purity higher than 95 percent. EXAMPLE II Example I was repeated at 225° C using 100 grams of sodium, 50 grams of powdered aluminum, 5 grams of sodium aluminum diethyl dihydride, and 500 ml of toluene. ______________________________________Time Pressure (psig)(Minutes) Δ Σ______________________________________0 -- --3 100 1009 150 25015 140 39021 130 52030 120 64041 60 70057 20 720______________________________________ The reaction rates of Examples I and II are comparable showing that the presence of the aluminum in Example II does not significantly affect reaction rate. EXAMPLE III Example I was repeated at 270° C but using 100 grams of sodium, 50 grams of aluminum powder, and 500 ml of toluene but without the NaAl(C 2 H 5 ) 2 H 2 . ______________________________________Time Pressure (psig)(Minutes) Δ Σ______________________________________0 -- --5 140 14010 100 24021 110 35035 70 42065 90 510______________________________________ EXAMPLE IV Example I was repeated at 225° C with 490 ml toluene and 106.5 grams of sodium, but without the NaAl(C 2 H 5 ) 2 H 2 . ______________________________________Time Pressure (psig)(Minutes) Δ Σ______________________________________0 -- --7 105 10518 80 18525 60 24537 100 34552 100 44573 105 550102 110 660182 30 690______________________________________ The preceding examples show a significantly higher reaction rate when the reaction is conducted in the presence of catalyst as specified and indicate that the presence of the aluminum powder does not significantly affect the reaction rate. Thus where the sodium hydride is subsequently reacted with triethyl aluminum and hydrogen to produce sodium aluminum diethyl dihydride, the aluminum powder needed for the latter reaction is suitably and conveniently added to the reactor prior to the formation of the sodium hydride. EXAMPLES V-VII These examples were conducted in a 5-gallon stainless steel pressure vessel, jacketed for heating externally. The vessel was equipped with pressure gage, thermometer, a hydrogen feed system, internal cooling coil for temperature maintenance and rapid cooling after the reaction. The reactor was baffled and equipped with an electrically driven twin turbine stirrer. Pressuring with hydrogen was periodic to 1000 psig as in Examples I-IV. EXAMPLE V The 5-gallon reactor was charged with 5800 grams toluene, 270 grams aluminum powder, 644 grams sodium, and 340 grams of 25 percent solution of sodium aluminum diethyl dihydride in toluene. (85 grams of contained NaAlEt 2 H 2 , 13.2 percent on the sodium fed for the reaction with hydrogen). The reactor was purged with hydrogen, leaving 100 psig residual hydrogen pressure. The heater was turned on and the stirrer started when the temperature reached 150° C. Reactor heating was continued until a temperature of 220° C was reached, which temperature was subsequently maintained during the course of the reaction. Hydrogen was then fed for a 43 minute total reaction time. ______________________________________Time Pressure (psig)(Minutes) Δ Σ______________________________________0 -- --4 160 16010 170 33016 130 46027 70 53036 30 56043 10 570______________________________________ The reactor was then cooled to 50° C, hydrogen pressure vented off and 2240 grams of liquid triethyl aluminum pressured into the reactor from a cylinder of triethyl aluminum. The reactor was then heated to 170° C under hydrogen and then hydrogen was fed for a reaction time of 52 minutes at 170° C. Pressuring with hydrogen was periodic to 1000 psig as in the preceding sodium hydride preparation. ______________________________________Time Pressure (psig)(Minutes) Δ Σ______________________________________0 -- --1 160 1604 140 30013 140 44022 90 53033 90 62044 100 72052 80 800______________________________________ The reactor was again cooled to 50° C and hydrogen pressure vented off. 300 grams of tetrahydrofuran and 2125 grams of toluene was then pressured into the reactor. The reactor was then discharged and the product solution filtered yielding 11425 grams of solution. The solution was analyzed and found to contain 26.8 wt. percent NaAlEt 2 H 2 in a yield of 98 percent based on sodium, 100 percent based on triethyl aluminum. EXAMPLE VI Example V was repeated feeding 5950 grams of toluene, 300 grams of aluminum powder, 675 grams of sodium, and 240 grams of the 25 percent toluene solution of sodium aluminum diethyl dihydride. (60 grams of contained sodium aluminum diethyl dihydride, 8.9 percent on the sodium fed for the reaction with hydrogen). The time for the first reaction was 42 minutes. ______________________________________Time Pressure (psig)(Minutes) Δ Σ______________________________________0 -- --5 130 1309 130 26012 120 38018 110 49027 40 53042 30 560______________________________________ The amount of triethyl aluminum fed was 2330 grams. The time for the subsequent or second reaction with hydrogen was 71 minutes. ______________________________________Time Pressure (psig)(Minutes) Δ Σ______________________________________0 -- --1 140 1403 110 2508 150 40015 120 52023 90 61036 60 67050 80 75065 60 81071 10 820______________________________________ EXAMPLE VII A residual heel of several hundred milliliters retained from Example VI was used instead of feeding sodium aluminum diethyl dihydride. 670 grams of sodium, 300 grams of aluminum and 5000 grams of toluene were charged to the reactor. The reactor was heated to 220° C as in Example VI and then hydrogen fed for a 50 minute reaction at that temperature. ______________________________________Time Pressure (psig)(Minutes) Δ Σ______________________________________0 -- --4 170 1709 141 31018 100 41029 40 45038 20 47050 10 480______________________________________ Data from the Examples are plotted as follows. ______________________________________ Example Fig.______________________________________I 1-AII 1-B -IIIIV 1-CV 2-AVI 2-AVII 2-B______________________________________
This invention relates to the preparation of alkali metal hydrides and of alkali metal aluminum dihydrocarbon dihydrides and in particular to such compounds of sodium, potassium or lithium having in the case of the dihydrocarbon compounds hydrocarbon radicals containing from 2 to about 30 carbon atoms per radical. Such dihydrocarbon materials, as typified by sodium aluminum diethyl dihydride, and by the potassium or lithium counterparts, either singly or in mixtures with respect to alkali metals and/or hydrocarbon groups, are soluble and useful in inert aromatic hydrocarbon solutions and have excellent mild reducing properties for various functional groups such as carbonyl groups in various organic compounds. The alkali metal hydrides are useful in many known ways such as in condensation and alkylation reactions and as chemical intermediates such as in the preparation of the alkali metal aluminum dihydrocarbon dihydrides.
2
BACKGROUND OF THE INVENTION 1. Field of the Invention This invention refers to an apparatus for integrating an optical character generator into a printer housing. 2. Description of the Related Art The integration of optical character generators of non-mechanical printers in a corresponding printer housing is always accompanied by adjustments. The necessity for such adjustments is thereby explained based on the fact that the optical images generated by the character generator are projected onto a transfer printing drum through an imaging optics. The typical imaging scale of imaging optics that are employed lies at a ratio of 1:1. Since the imaging optics is preferably integrated fixed in the character generator, the distance of the surface of the imaging optics from the surface of the transfer printing drum must be optimally set so that the imaging quality is not inadmissably deteriorated by transgressing the depth of field of the imaging optics. Assuming that the character generator can be manufactured rather precisely, the setting of this distance, however, is greatly dependent on how exact the distance between the seating point of the character generator in the printer housing and the rotational axis of the transfer printing drum can be set. This setting precision is deteriorated by a statically changing untrue spindle running of the transfer printing drum. Since this untrue spindle running cannot be avoided, the depth of field of the imaging optics constantly varies within a certain range of tolerances. So that the quality losses are not further increased when imaging the optical images onto the surface of the transfer printing drum, the distance between the seating point of the character generator in the printer housing and the rotational axis of the transfer printing drum should be kept constant. This, however, the device including proves problematical when the character generator, for example in case of maintenance, is taken out of the printer housing and is then subsequently reintroduced thereinto. A possibility of avoiding the problem is conceivable in that the distance is again re-adjusted after every integration of the character generator into the printer housing. What is especially disadvantageous given this type of procedure is that an individual adjustment error possibly deriving from constant adjustments will additionally deteriorate the imaging quality. WO 88/00 739 discloses a fastening and setting mechanism for the exact arrangement of a character generator relative to a light-sensitive surface. What are characteristic of the fastening and setting mechanism are, first, a plurality of fixing or, respectively, locking elements with which a light emission arrangement arranged on a carrier element at both long sides of the character generator is detachably secured at a prescribed spacing from the light-sensitive surface. Over and above this, on the other hand, fastening and adjustment elements are also provided on the carrier element with which an imaging optics of the character generator can be adjusted between the light-sensitive surface and the light emission arrangement for an optimum imaging characteristic, for example resolution and depth of field of the latent electrostatic image on the light-sensitive surface. SUMMARY OF THE INVENTION The present invention is therefore based on the object of creating an apparatus of the species initially cited with which the adjustment of an optical character generator after the integration thereof in a printer housing is eliminated. In an apparatus of the species initially cited, this object is inventively achieved in a device for the integration of the optical character generator, the device including guide rails provided in the printer housing via which guide rails the character generator is guided up to a first fastening element adjustably arranged in the printer housing that serves as a seat for the character generator; the first fastening element comprises a ramp via which the character generator proceeds to its seating position and comprises a guide slot for the acceptance of a guide pin allocated to the character generator; a second fastening element is adjustably arranged in the printer housing lying opposite the first fastening element, the character generator inserted into the printer housing being fixed on the second fastening element. The solution is thereby particularly distinguished in that the optical character generator, when maintenance is required, can be integrated in functionally reliable fashion in the printer housing without additional adjustment and can even be replaced by a new character generator. This adjustment-free integration is guaranteed by two fastening elements arranged in the printer housing. The special characteristic of these fastening elements lies therein that they are adjusted such with a gauge during the assembly of the apparatus that the integrated character generator has a constant spacing from a transfer printing drum. With respect to this spacing, care must be exercised to see that manufacturing and assembly tolerances that arise do not exceed the available depth of field of an imaging optics of the character generator so that the imaging quality of optical images projected onto the transfer printing drum is not deteriorated in a lasting way. This is particularly true cf an untrue spindle running produced by the rotational motion of the transfer printing drum. Compared to manufacturing tolerances that occur in the internal structure of the character generator, the untrue spindle running can hardly be influenced despite an excellent seating of the transfer printing drum and is therefore unavoidable. The solution is further distinguished particularly in that the character generator is additionally secured parallel to the axis of the transfer printing drum in the adjusted position with reference to the transfer printing drum. Characteristically for this, guide pins of the character generator are provided that are arranged with form fit in guide slots of the fastening elements upon assembly. Further advantages and developments of the invention include an apparatus in which the character generator comprises seating surfaces in a longitudinal direction at both of its ends. The apparatus is characterized in that a plate-shaped fixing element that projects out at both long sides of the character generator is secured on a seating surface in a recess. The apparatus may also include the character generator comprising running rollers that roll on the guide rails when the character generator is inserted into the printer housing. The advantages of the invention are evident from the following description of an exemplary embodiment with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 a cross section through a fundamental sub-structure of an electrophotographic printer for generating a latent, electrostatic image; FIG. 2 a perspective, axonometric illustration of the structure of a character generator that generates latent, electrostatic images; FIG. 3 a perspective view of a first fastening element for fixing the character generator; FIG. 4 the plan view onto an exposure module of the character generator that is required for generating latent, electrostatic images; and FIG. 5 a section through the character generator. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows how a character generator 1 and a transfer printing drum 2 are built into a printer housing 3 of a printer. To that end, the transfer printing drum 2 is axially fixed on a spindle 20 that is rotatably seated in the printer housing 3. The character generator 1 is secured in the printer housing 3 under the rotatably seated transfer printing drum 2 at a variable spacing z3. To that end, the character generator 1 has both its ends mounted fixed on adjustable first and second fastening elements 31, 30. The first and second fastening elements 31, 30 that are annular in cross section are integrated such in the printer housing 3 that the position of the fastening planes 310 or, respectively, 300 of the first and second fastening elements 31, 30 with reference to the rotational axis of the transfer printing drum 2 can be adjusted to the spacing z3 with a gauge. The spacing z3 that is thus set is thereby composed of two different individual dimensions z1 and z2. It is indispensable for a faultless operation of the printer that an overall tolerance that is prescribed and must also be observed for the spacing z3 that has been set is not exceeded by manufacturing and mounting tolerances that occur for the two dimensions z1 and z2. The overall tolerance is essentially defined by an imaging optics 10 of the character generator 1. For the sake of a good imaging quality, thus, the depth of field of the imaging optics 10 dare not be varied by the addressed tolerances. This may be explained based on the fact that picture elements of light sources, for example light-emitting diodes (LEDs) are reproduced on the transfer printing drum 2 by the imaging optics 10. These light sources are respectively arranged on an exposure module 11 that is connected with a positive lock to the web of a module carrier 13 that is fashioned T-shaped. Detent elements 12 that prevent a displacement of the exposure modules 11 in the x-direction during the operating condition of the character generator 1 are also provided on the web of the module carrier 13. The flange of the T-shaped module carrier 13 also comprises running rollers 130 that are respectively secured in pairs at the two long end face sides of the flange diametrically opposite one another. Over and above this, the base area of the flange is divided into two seating surfaces 132, 131 as well as into a step surface 133 offset from these two seating surfaces 132, 131 and on which a plurality of cooling plates 140 that form a cooling member 14 are secured, for example by being soldered. For the operation of the printer, the character generator is thrust into the printer housing 3 as a result thereof that the running rollers 130 are movable in the x-direction in guide rails 32 of the printer housing 3, being thrust thereinto until the character generator 1 has its seating surfaces 131, 132 lying on the first and second fastening elements 31, 30 in the fastening planes 310, 300. The character generator 1 that is built in such fashion forms a structural unit together with the transfer printing drum 2 with respect to the dimensions z1 through z3 entered in FIG. 1, this structural unit only changing again given constantly changing, different manufacturing and assembling tolerances. Thus deriving, for example, with respect to a tangential spacing z4 between the transfer printing drum 2 and the imaging optics 10 are manufacturing tolerances that are based on a variable untrue spindle running of the transfer printing drum 2. When, for example, the overall tolerance to be demanded for the spacing z3 amounts to 0.1 mm and when, as a consequence of the untrue spindle running, a tolerance of likewise 0.1 mm is taken into consideration for the dimension z4 given what is the high-precision manufacture of the transfer printing drum 2 at the same time, then the character generator 1 must be manufactured with a precision of at least 0.01 mm in order to guarantee a faultless imaging of the picture elements of the light sources onto the transfer printing drum 2. Extremely high demands made of the structural design of the character generator 1 in the direction of the z-coordinate derive therefrom, these to be discussed below in the description of FIGS. 2 through 5. To that end, FIG. 2 shows a perspective, axonometric illustration of the fundamental structure of the character generator 1. In longitudinal direction, the four exposure modules 11 indicated in FIG. 1 are arranged on the web of the module carrier 13 positively or non-positively locked thereon. For this purpose, both contacting surfaces, both that of the module carrier 13 as well as that of the exposure modules 11, are mechanically processed to an extremely high precision in a separate manufacturing cycle in order to achieve an air gap of less than 2 μm between the two contacting surfaces in the assembled condition. The exposure modules 11 arranged in this fashion abut one another at respect joining surfaces 116 that are fabricated with the utmost precision. Thus, the air gap between the adjoining surfaces 116 is likewise less than 2 μm. The abutting of the modules 11, however, occurs only in a very narrow region. The reasons for this shall be set forth in greater detail during the description of FIG. 3. So that this congruent adjacency of the respective modules 11 against one another is also preserved during the operating condition, the position of the exposure modules 11 on the module carrier 13 is fixed for all three coordinate directions. For the x-direction, the detent elements 12 have already been pointed out in the description of FIG. 1. A bore 120 is respectively let into the detent elements 12 in order to secure the detent elements 12 at a prescribed location on the web of the module carrier 13 with, for example, the assistance of fastening screws 121. In the mounted condition of the detent elements 12, the spacing of the bores 120 is dimensioned such that the modules 11 lying between the detent elements 12 are clamped with a positive lock in the x-direction. The form-fit fixing of the modules 11 in the y-direction and the z-direction is also achieved by seating pins 117 and by fastening devices which are not shown in FIG. 2. Over and above this, a printed circuit board 17 that is likewise fixed with the fastening screw 121 lies on the one detent element 12. FIG. 2 also shows that the imaging optics 10 is arranged at a distance z4' above the module surface and that the exposure modules 11 comprise a flexible, electrical ribbon lead 4 at their end faces 117 that are respectively still free, being supplied with power for the light-emitting diodes and drive electronics via this ribbon lead 4. To that end, every flexible ribbon lead 4 is connected to a planar electrical lead line 5 via a screwed connection 40, this lead line 5 extending at both long sides of the module carrier web past all exposure modules 11 arranged on the module carrier 13, extending in the x-direction. The necessity of a lead line 5 designed in such a large-area way may be explained on the basis of the fact that currents of 80 through 100 A are not unusual due to the great number of light-emitting diodes integrated on the modules 11 of the character generator 1. The drive of the light-emitting diodes is undertaken via data and control lines 60 by a microprocessor-controlled means 6 that, among other things, contains a central processor 61 and a memory 62 for this purpose. This microprocessor-controlled means 6 is followed by an analog-to-digital converter 63 as well as by a plurality of amplifying driver modules 64 that are arranged on the printed circuit board 17. The signals are forwarded to the light-emitting diodes amplified on the data and control lines by the driver modules 64. Under the seating surface 131, the character generator 1 also comprises a fixing element 16 fashioned plate-shaped and, under the seating surfaces 132 and 131, comprises a guide pin 15 that respectively projects from the module carrier 13. When, for integration into the printer housing 3, the character generator 1 is now inserted along the guide rail 32 with its guide rollers 130, then the guide pin 15 that thereby centrally projects under the seating surface 132 is brought along a ramp 311 of the first fastening element 31 into the detent shown in FIG. 3 of a guide slot 312 that tapers toward the detent. The taper of the guide slot 312 is dimensioned such that the guide pin 15 that projects under the seating surface 132 is fixed play-free in the y-direction. The positional fixing of the character generator 1 in the x-direction is effected by a plate-shaped fixing element 16. To that end, the fixing element 16 is secured in a recess 161 of the seating surface 131 with which it forms a flush surface such that a part of the fixing element 16 that is of the respectively same size projects out at both long sides of the character generator 1. A bore 160 is respectively let into the middle in this projecting part. When the character generator 1 has its seating surface 132 lying in the contacting plane 310 on the first fastening element 31 and when the character generator 1 likewise has its seating surface 131 in the contacting plane 300 lying on the second fastening element 30, then this is fixed in the x-direction by two fastening screws 162 that are let into a corresponding threaded bore 301 according to the illustration in FIG. 1. The character generator 1 or, respectively, the module carrier 13 is thus clearly fixed in all three coordinate directions with respect to the transfer printing drum 2 shown in FIG. 1. In order to be able to subsequently generate latent, electrostatic images on the transfer printing drum 2 with the character generator 1 positioned in this fashion and in order to thereby ultimately be able to print arbitrary characters on the recording medium, the light-emitting light sources 113 are monolithically integrated on the exposure modules 11 in common as shown in FIG. 4, in an exposure line 114 at a regular spacing, being integrated thereon as chips 112 having paired parallel sides and, dependent on the printing grid, containing 64 or 128 LEDs. Points are entered in FIG. 4 as LEDs to represent this. Moreover, the number 64 or, respectively, 128 for the number of LEDs 113 per chip 112 on the modules 11 of the character generator 1 is not arbitrarily selected; rather, it is based on conditions that are related to the digital drive of the LEDs 113. As may be seen in FIG. 4, an integrated circuit 111 is provided for this digital drive for every LED row of the chip 112 on the module 11. Each of these integrated circuits 111 is connected via a bus system 110 both to the flexible ribbon lead 4 as well as via the driver modules 64 on the printed circuit boards 17 to data and control lines 60 and, thus, each thereof is connected to the power supply or, respectively, to the microprocessor-controlled means 6. All printing data of the light-emitting diodes 113 in the exposure line 114 are stored and edited in this means 6. In a section through the character generator 1, FIG. 5 shows how this character generator is fixed in the y-direction in the printer housing 3. To that end, it is particularly shown how the guide pins 15 are let into the web of the module carrier 13. It is also shown how the imaging optics 10 is arranged in the z-direction and the y-direction with respect to the transfer printing drum 2 and the light sources 113 on the chip 112 of the exposure modules 11. With respect to its imaging geometry, the imaging optics 10 is of such a nature that the light points generated in the exposure line 114 of the exposure module 11 are respectively projected onto the transfer printing drum 2 in an imaging scale of 1:1. In order to achieve an extremely good imaging quality of the light points, the entered spacings z4 and z4' must be identical. To that end, the imaging optics 10 is integrated in a covering 8 and is centrally positioned with this over the exposure line 114 or, respectively, the chips 112. The covering 8 is in turn fixed relative to the exposure modules 11 by spacers 9. Over and above this, the covering 8 is designed such that the character generator 1 is protected against external contamination up to the running rollers 130, this external contamination particularly occurring when developing the latent, electrostatic images on the transfer printing drum 2. The imaging optics 10, which, according to FIG. 2, extends over the entire imaging line 114 of the character generator 1 and thereby projects every light point of the light-emitting diodes 113 onto the transfer printing drum 2 in the same imaging scale, is in turn protected against contamination by the closure mechanism 90 that does not cover the imaging optics 10 during the imaging process. To that end, the closure mechanism 90 is seated displaceable in the y-direction on the covering 8. Although other modifications and changes may be suggested by those skilled in the art, it is the intention of the inventors to embody within the patent warranted hereon all changes and modifications as reasonably and properly come within the scope of their contribution to the art.
For projecting optical images onto a transfer printing drum of a non-mechanical printer, an apparatus is used with which the optical character generators can be introduced and removed adjustment-free. To that end, two fastening elements are provided in the printer housing and are adjusted at a constant spacing from the transfer printing drum. For the acceptance of the character generator these fastening elements comprise tapering guide slots that are each respectively fashioned ramp-shaped and into which guide pins of the character generator can be inserted, the character generator being fixed parallel to the rotational axis of the transfer printing drum as a result thereof. The apparatus provides for the adjustment-free integration of optical character generators, particularly for non-mechanical printers.
1
REFERENCE TO PENDING PRIOR PATENT APPLICATION [0001] This patent application claims benefit of pending prior U.S. Provisional Patent Application Ser. No. 61/727,436, filed Nov. 16, 2012 by Andrew Tybinkowski et al. for COMPUTERIZED TOMOGRAPHY (CT) IMAGING SYSTEM WITH MULTI-SLIT ROTATABLE COLLIMATOR (Attorney's Docket No. NEUROLOGICA-4349 PROV), which patent application is hereby incorporated herein by reference. FIELD OF THE INVENTION [0002] This invention relates to imaging systems in general, and more particularly to computerized tomography (CT) imaging systems. BACKGROUND OF THE INVENTION [0003] In many situations, it can be desirable to image the interior of opaque objects. By way of example but not limitation, in the medical field, it can be desirable to image the interior of a patient's body so as to allow viewing of internal body structures without physically penetrating the skin. [0004] Computerized Tomography (CT) has emerged as a key imaging modality in the medical field. CT imaging systems generally operate by directing X-rays into the body from a variety of positions, detecting the X-rays passing through the body, and then processing the detected X-rays so as to build a three-dimensional (3D) data set and a 3D computer model of the patient's anatomy. The 3D data set and 3D computer model can then be visualized so as to provide images (e.g., slice images, 3D computer images, etc.) of the patient's anatomy. [0005] By way of example but not limitation, and looking now at FIGS. 1 and 2 , there is shown a mobile CT imaging system 5 of the sort disclosed in U.S. Pat. No. 7,397,895, issued Jul. 8, 2008 to Eric M. Bailey et al. for MOBILE COMPUTERIZED TOMOGRAPHY (CT) IMAGING SYSTEM WITH CORDLESS AND WIRELESS CAPABILITIES (Attorney's Docket No. NEUROLOGICA-7), which patent is hereby incorporated herein by reference. Mobile CT imaging system 5 generally comprises a torus 10 which is supported by a base 15 . Torus 10 and base 15 together comprise a frame for mobile CT imaging system 5 . A center opening 20 is formed in torus 10 . Center opening 20 receives the patient anatomy which is to be scanned. [0006] Looking next at FIG. 3 , torus 10 generally comprises an X-ray tube assembly 25 , an X-ray detector assembly 30 , and a rotating drum assembly 35 . X-ray tube assembly 25 and X-ray detector assembly 30 are mounted to rotating drum assembly 35 in diametrically-opposing relation, such that an X-ray beam 40 (generated by X-ray tube assembly 25 and detected by X-ray detector assembly 30 ) is passed through the patient anatomy disposed in center opening 20 . Furthermore, since X-ray tube assembly 25 and X-ray detector assembly 30 are mounted on rotating drum assembly 35 so that they are rotated concentrically about center opening 20 , X-ray beam 40 will be passed through the patient's anatomy along a full range of radial positions, so as to enable mobile CT imaging system 5 to create a “slice” image of the anatomy penetrated by the X-ray beam. Furthermore, by moving mobile CT imaging system 5 relative to the patient during scanning, a series of slice images can be acquired, and thereafter appropriately processed, so as to create a 3D computer model of the scanned anatomy. [0007] The various electronic hardware and software for controlling the operation of X-ray tube assembly 25 , X-ray detector assembly 30 , and rotating drum assembly 35 , as well as for processing the acquired scan data so as to generate the desired slice images and 3D computer model, may be of the sort well known in the art and may be located in torus 10 and/or base 15 . [0008] Still looking now at FIG. 3 , base 15 comprises a transport assembly 50 for moving mobile CT imaging system 5 relative to the patient. More particularly, as disclosed in the aforementioned U.S. Pat. No. 7,397,895, transport assembly 50 preferably comprises (i) a gross movement mechanism 55 for moving mobile CT imaging system 5 relatively quickly across room distances, so that the mobile CT imaging system can be quickly and easily brought to the “bedside” of the patient, and (ii) a fine movement mechanism 60 for moving the mobile CT imaging system precisely, relative to the patient, during scanning, so that the patient can be scanned at their bedside, without being moved. As discussed in U.S. Pat. No. 7,397,895, gross movement mechanism 55 preferably comprises a plurality of free-rolling casters, and fine movement mechanism 60 preferably comprises a plurality of centipede belt drives (which can be configured for either stepped or continuous motion, whereby to provide either stepped or continuous scanning). Hydraulic apparatus 65 permits either gross movement mechanism 55 or fine movement mechanism 60 to be engaged with the floor, whereby to facilitate appropriate movement of mobile CT imaging system 5 . [0009] Looking next at FIGS. 4 and 5 , there is shown another mobile CT imaging system 105 of the sort disclosed in U.S. patent application Ser. No. 13/304,006, filed Nov. 23, 2011 by Eric M. Bailey et al. for ANATOMICAL IMAGING SYSTEM WITH CENTIPEDE SCANNING DRIVE, BOTTOM NOTCH TO ACCOMMODATE BASE OF PATIENT SUPPORT, AND MOTORIZED DRIVE FOR TRANSPORTING THE SYSTEM BETWEEN SCANNING LOCATIONS (Attorney's Docket No. NEUROLOGICA-3337), which patent application is hereby incorporated herein by reference. Mobile CT imaging system 105 is generally similar to mobile CT imaging system 5 disclosed above, except that (i) mobile CT imaging system 105 is generally “scaled up” in size relative to mobile CT imaging system 5 , (ii) a bottom notch 170 is provided in skirt 175 of mobile CT imaging system 105 , and (iii) the casters of gross movement mechanism 55 of mobile CT imaging system 5 may be replaced by a pair of drive wheels 180 A, 180 B and a pair of casters 185 A, 185 B, and each of the centipede belt drives of fine movement mechanism 60 of mobile CT imaging system 5 may be replaced by a pair of parallel belt drives 190 A, 190 B disposed in side-by-side relation. Additional differences between mobile CT imaging system 105 of FIGS. 4 and 5 and mobile CT imaging system 5 of FIGS. 1-3 are disclosed in the aforementioned U.S. patent application Ser. No. 13/304,006. [0010] For the purposes of the present invention, it is generally immaterial whether the present invention is used in conjunction with the aforementioned mobile CT imaging system 5 , the aforementioned mobile CT imaging system 105 or another CT imaging system (e.g., a fixed position CT imaging system). [0011] With all CT imaging systems (i.e., with the aforementioned mobile CT imaging system 5 , the aforementioned mobile CT imaging system 105 , or another CT imaging system such as a fixed position CT imaging system), it is generally necessary to collimate the X-ray beam emitted by the X-ray tube assembly before the X-ray beam passes through the body. More particularly, X-ray tube assemblies generally emit their X-rays in a broad, relatively unfocused pattern, and the anatomy is imaged in a slice fashion, so it is generally desirable to restrict the X-rays reaching the patient to only those X-rays which are actually used for the slices being imaged, and to block the remaining X-rays emitted by the X-ray tube assemblies. This is typically done with a collimator, which is essentially an X-ray shield having a slit formed therein, which is interposed between the X-ray tube assembly and the patient. In this way, the slit permits the “useful” X-rays (i.e., those being used for the slices being imaged) to reach the patient, while the body of the collimator blocks the remainder of the X-rays emitted by the X-ray tube assembly. [0012] In addition to the foregoing, with “modern” CT imaging systems, it is possible to conduct multi-slice scanning of a patient by using a collimator having a slit wide enough to provide an X-ray beam which simultaneously encompasses multiple scan slices. In general, scanning with a wider X-ray beam (i.e., a higher slice count) yields faster scanning of a patient than scanning with a narrower X-ray beam (i.e., a lower slice count), but this is generally at the expense of subjecting the patient to a higher X-ray dose. For this reason, in some situations it may be desirable to make a high slice scan (e.g., a 32 slice scan) of a patient, whereas in other circumstances it may be desirable to make a low slice scan (e.g., an 8 slice scan) of a patient. [0013] Since the width of the X-ray beam is determined by the width of the slit in the collimator, varying the slice count of the scan requires the use of a plurality of collimator slits each having different widths. [0014] Thus there is a need for a fast, simple and reliable way to change collimator slits when the slice count of the scan is to be changed. SUMMARY OF THE INVENTION [0015] The present invention provides a fast, simple and reliable way to change collimator slits when the slice count of the scan is to be changed. [0016] More particularly, the present invention comprises the provision and use of a novel multi-slit rotatable collimator, wherein each of the slits of the multi-slit rotatable collimator has a different size opening (i.e., each slit has a different width), and wherein the multi-slit collimator is rotated about an axis so as to selectively interpose a given slit between the X-ray tube assembly and the patient, whereby to allow scans of different slice counts to be made. In this way, the present invention provides a fast, simple and reliable way to change collimator slits when the slice count of the scan is to be changed. [0017] Additionally, the multi-slit rotatable collimator may be rotated about an axis so as to not interpose a given slit between the X-ray tube assembly and the patient, whereby to selectively shield the patient from the X-rays generated by the X-ray tube assembly. In this way, the present invention provides a fast, simple and reliable way to shield the patient from the X-rays generated by the X-ray tube assembly. [0018] In one preferred form of the invention, there is provided apparatus for collimating an X-ray beam, the apparatus comprising: a multi-slit rotatable collimator comprising: a semi-tubular structure extending coaxially along a longitudinal axis, the semi-tubular structure being formed out of an X-ray impermeable material; at least one slit formed in the semi-tubular structure, wherein the at least one slit extends parallel to the longitudinal axis of the semi-tubular structure; a mount for rotatably supporting the semi-tubular structure in the path of an X-ray beam; and a drive mechanism for selectively rotating the semi-tubular structure about the longitudinal axis of the semi-tubular structure, whereby to selectively (i) position the at least one slit in the path of the X-ray beam so as to tailor the X-ray beam to the width of the at least one slit, and (ii) position a solid portion of the semi-tubular structure in the path of an X-ray beam so as to block an X-ray beam. [0024] In another preferred form of the invention, there is provided apparatus for imaging a patient, the apparatus comprising: a CT machine comprising an X-ray source; and a multi-slit rotatable collimator comprising: a semi-tubular structure extending coaxially along a longitudinal axis, the semi-tubular structure being formed out of an X-ray impermeable material; at least one slit formed in the semi-tubular structure, wherein the at least one slit extends parallel to the longitudinal axis of the semi-tubular structure; a mount for rotatably supporting the semi-tubular structure in the path of the X-ray beam; and a drive mechanism for selectively rotating the semi-tubular structure about the longitudinal axis of the semi-tubular structure, whereby to selectively (i) position the at least one slit in the path of the X-ray beam so as to tailor the X-ray beam to the width of the at least one slit, and (ii) position a solid portion of the semi-tubular structure in the path of an X-ray beam so as to block an X-ray beam. [0031] In another preferred form of the invention, there is provided a method for collimating an X-ray beam, the method comprising: providing a multi-slit rotatable collimator comprising: a semi-tubular structure extending coaxially along a longitudinal axis, the semi-tubular structure being formed out of an X-ray impermeable material; at least one slit formed in the semi-tubular structure, wherein the at least one slit extends parallel to the longitudinal axis of the semi-tubular structure; a mount for rotatably supporting the semi-tubular structure in the path of an X-ray beam; and a drive mechanism for selectively rotating the semi-tubular structure about the longitudinal axis of the semi-tubular structure, whereby to selectively (i) position the at least one slit in the path of the X-ray beam so as to tailor the X-ray beam to the width of the at least one slit, and (ii) position a solid portion of the semi-tubular structure in the path of an X-ray beam so as to block an X-ray beam; providing an X-ray beam; and using the drive mechanism to selectively rotate the semi-tubular structure about the longitudinal axis of the semi-tubular structure. [0039] In another preferred form of the invention, there is provided a method for imaging a patient, the method comprising: providing a CT machine comprising an X-ray source, and a multi-slit rotatable collimator comprising a semi-tubular structure extending coaxially along a longitudinal axis, the semi-tubular structure being formed out of an X-ray impermeable material; at least one slit formed in the semi-tubular structure, wherein the at least one slit extends parallel to the longitudinal axis of the semi-tubular structure; a mount for rotatably supporting the semi-tubular structure in the path of the X-ray beam; and a drive mechanism for selectively rotating the semi-tubular structure about the longitudinal axis of the semi-tubular structure, whereby to selectively (i) position the at least one slit in the path of the X-ray beam so as to tailor the X-ray beam to the width of the at least one slit, and (ii) position a solid portion of the semi-tubular structure in the path of an X-ray beam so as to block an X-ray beam; using the drive mechanism to selectively rotate the semi-tubular structure about the longitudinal axis of the semi-tubular structure; and scanning the patient using the CT machine. BRIEF DESCRIPTION OF THE DRAWINGS [0043] These and other features and advantages of the present invention will become more readily apparent during the following detailed description of the preferred embodiments of the invention, which is to be considered in conjunction with the accompanying drawings wherein like numbers refer to like parts and further wherein: [0044] FIGS. 1-3 are schematic views showing an exemplary mobile CT imaging system; [0045] FIGS. 4 and 5 are schematic views showing another exemplary mobile CT imaging system; and [0046] FIGS. 6-23 are schematic views showing a novel multi-slit rotatable collimator assembly formed in accordance with the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [0047] The present invention provides a fast, simple and reliable way to change collimator slits when the slice count of the scan is to be changed. [0048] More particularly, the present invention comprises the provision and use of a novel multi-slit rotatable collimator, wherein each of the slits of the multi-slit rotatable collimator has a different size opening (i.e., each slit has a different width), and wherein the multi-slit collimator is rotated about an axis so as to selectively interpose a given slit between the X-ray tube assembly and the patient, whereby to allow scans of different slice counts to be made. In this way, the present invention provides a fast, simple and reliable way to change collimator slits when the slice count of the scan is to be changed. [0049] Additionally, the multi-slit rotatable collimator may be rotated about an axis so as to not interpose a given slit between the X-ray tube assembly and the patient, whereby to selectively shield the patient from the X-rays generated by the X-ray tube assembly. In this way, the present invention provides a fast, simple and reliable way to shield the patient from the X-rays generated by the X-ray tube assembly. [0050] In one preferred form of the invention, and looking now at FIGS. 6-23 , there is provided a novel multi-slit rotatable collimator assembly 205 which generally comprises a base 210 having an opening 215 , a pair of spaced supports 220 , 225 mounted to base 210 , a multi-slit rotatable collimator 230 rotatably mounted to supports 220 , 225 so as to be movably disposed in front of opening 215 , a drive mechanism 235 for rotating multi-slit rotatable collimator 230 , and a position detector 240 for detecting the rotational disposition of multi-slit rotatable collimator 230 . Preferably, multi-slit rotatable collimator assembly 205 is covered with a housing 242 having an opening 243 , e.g., by securing housing 242 to base 210 , with opening 243 in housing 242 being aligned with opening 215 in base 210 . [0051] More particularly, base 210 generally comprises a plate-like structure having an inner surface 245 and an outer surface 250 . Opening 215 extends through base 210 , opening on inner surface 245 and outer surface 250 . A mounting plate 255 is preferably secured to outer surface 250 of base 210 , whereby base 210 may be secured to the X-ray tube assembly of a CT imaging system, e.g., the X-ray tube assembly 25 of the aforementioned mobile CT imaging system 5 , or the X-ray tube assembly of the aforementioned CT imaging system 105 , or another CT imaging system such as a fixed position CT imaging system. Mounting plate 255 comprises an opening 260 ( FIG. 14 ) aligned with opening 215 in base 210 , whereby X-rays emitted from X-ray tube assembly 25 may pass through opening 260 in mounting plate 255 and through opening 215 in base 210 . [0052] Spaced supports 220 , 225 are mounted to inner surface 245 of base 210 so that they reside on either end of opening 215 . Spaced support 220 comprises an opening 265 ( FIGS. 15 and 16 ), and spaced support 225 comprises an opening 270 , wherein opening 265 in spaced support 220 is axially aligned with opening 270 in spaced support 225 . [0053] Multi-slit rotatable collimator 230 is rotatably mounted to supports 220 , 225 so as to be movably disposed in front of opening 215 . More particularly, multi-slit rotatable collimator 230 comprises a semi-tubular structure 275 (e.g., a 120 degree arc segment of a tube) formed out of an X-ray impermeable material (e.g., a high density material such as tungsten, molybdenum, etc.) having a plurality of longitudinal slits 280 A, 280 B, etc. formed therein, wherein each slit 280 A, 280 B, etc. has a different width (e.g., one slit 280 A sized for a 32 slice scan, another slit 280 B sized for an 8 slice scan, etc.). The two ends of semi-tubular structure 275 are movably mounted to spaced supports 220 , 225 (e.g., by fitting axles 285 , 290 through openings 265 , 270 in spaced supports 220 , 225 , respectively) so that multi-slit rotatable collimator 230 may be rotated about its longitudinal axis, whereby to selectively position one of the slits 280 A, 280 B, etc. between X-ray tube assembly 25 and the patient, whereby to permit scans of different slice counts (e.g., 32 slice scans, 8 slice scans, etc.) to be made. Additionally, multi-slit rotatable collimator 230 may be rotated about its axis so as to not interpose a given slit 280 A, 280 B, etc. between the X-ray tube assembly and the patient, whereby to selectively shield the patient from the X-rays generated by the X-ray tube assembly. [0054] Drive mechanism 235 is provided to selectively rotate multi-slit rotatable collimator 230 about its axis. Preferably semi-tubular structure 275 of multi-slit rotatable collimator 230 is rotated about its longitudinal axis using a Geneva drive mechanism, e.g., such as of the sort shown in FIG. 17-23 . More particularly, drive mechanism 235 preferably comprises a drive shaft 295 which turns a gear 300 , which in turn rotates a drive wheel 305 carrying a pin 310 , which in turn rotates a driven wheel 315 having slots 320 therein. Driven wheel 315 is mounted to axle 285 extending through opening 265 in spaced support 220 . Preferably the number and location of slots 320 in driven wheel 315 are coordinated with the number and location of slits 280 A, 280 B, etc. in semi-tubular structure 275 , such that rotation of drive shaft 295 can selectively align a particular slit 280 A, 280 B, etc. with the X-ray beam emitted from X-ray tube assembly 25 , whereby to selectively tailor the X-ray beam to a desired width. Furthermore, the number and location of slots 320 in driven wheel 315 are coordinated with the “solid” portions of semi-tubular structure 275 , such that rotation of drive shaft 295 can selectively interpose a solid portion of semi-tubular structure 275 with the X-ray beam emitted from X-ray tube assembly 25 , whereby to selectively block the X-ray beam emitted by X-ray tube assembly 25 . [0055] By way of example but not limitation, where semi-tubular structure 275 comprises a first slit 280 A, a second slit 280 B and a solid portion disposed between first slit 280 A and second slit 280 B, the Geneva drive mechanism may comprise a drive wheel 305 carrying a pin 310 , which in turn rotates a driven wheel 315 having slots 320 therein, such that (i) the solid portion disposed between first slit 280 A and second slit 280 B will be presented to the X-ray beam when drive wheel 305 and driven wheel 315 are in the position shown in FIG. 17 , (ii) slit 280 A will be presented to the X-ray beam when drive wheel 305 and driven wheel 315 move through the positions shown in FIGS. 18-20 , and (iii) slit 280 B will be presented to the X-ray beam when drive wheel 305 and driven wheel 315 move through the positions shown in FIGS. 21-23 . [0056] Position detector 240 is provided for detecting the rotational disposition of multi-slit rotatable collimator 230 . More particularly, position detector 240 comprises a sensor element 325 mounted to base 210 , and a sensed element 330 mounted to axle 290 of multi-slit rotatable collimator 230 , such that the rotational disposition of multi-slit rotatable collimator 230 can be determined using position detector 240 . [0057] As noted above, multi-slit rotatable collimator assembly 205 is preferably covered with housing 242 having opening 243 therein, e.g., by securing housing 242 to base 210 , with opening 243 in housing 242 being aligned with opening 215 in base 210 . [0058] On account of the foregoing, when multi-slit rotatable collimator assembly 205 is mounted in front of the X-ray tube assembly of a CT imaging system so that X-rays emitted by the X-ray tube assembly pass through multi-slit rotatable collimator assembly 205 , and when it is desired to scan a patient with an X-ray beam of a first slice width (e.g., a high slice scan such as a 32 slice scan), drive mechanism 235 is activated so as to turn multi-slit rotatable collimator 230 about its axis so as to position a first slit between X-ray assembly 25 and the patient (e.g., slit 280 A). In this way multi-slit rotatable collimator 230 will tailor the width of the X-ray beam delivered to the patient to the desired first slice width. [0059] Correspondingly, when it is desired to scan a patient with an X-ray beam of a second slice width (e.g., a low slice scan such as an 8 slice scan), drive mechanism 235 is activated so as to turn multi-slit rotatable collimator 230 about its axis so as to position a second slit between X-ray assembly 25 and the patient (e.g., slit 280 B). In this way multi-slit rotatable collimator 230 will tailor the width of the X-ray beam delivered to the patient to the desired second slice width. [0060] Furthermore, when it is desired to shield the patient from the X-ray beam emitted by X-ray assembly 25 , drive mechanism 235 is activated so as to turn multi-slit rotatable collimator 230 about its axis so as to position a solid portion of semi-tubular structure 275 between X-ray assembly 25 and the patient. In this way multi-slit rotatable collimator 230 will block the X-ray beam from being delivered to the patient. [0061] In one preferred form of the invention, multi-slit rotatable collimator 230 comprises two slits 280 A, 280 B, wherein slit 280 A is sized to provide a 32 slice scan and slit 280 B is sized to provide an 8 slice scan. However, if desired, more or less slits may be provided, and/or the widths of the slits may be varied. By way of example but not limitation, three slits 280 A, 280 B, 280 C may be provided, with slit 280 A being sized to provide a 64 slice scan, slit 280 B being sized to provide an 32 slice scan and slit 280 C being sized to provide an 8 slice scan. Still other configurations will be readily apparent to one skilled in the art in view of the present disclosure. [0062] If desired, a filter may be interposed between X-ray assembly 25 and semi-tubular structure 275 of multi-slit rotatable collimator 230 . By way of example but not limitation, a bow-tie filter 335 may be interposed between X-ray assembly 25 and semi-tubular structure 275 of multi-slit rotatable collimator 230 . In one preferred form of the invention, bow-tie filter 335 ( FIG. 12 ) is mounted to base 210 in front of opening 215 and within the volume defined by semi-tubular structure 275 , such that X-rays emitted from X-ray assembly 25 are filtered prior to passing through a slit 280 A, 280 B, etc. in semi-tubular structure 275 or encountering a solid portion of semi-tubular structure 275 . Modifications of the Preferred Embodiments [0063] It should be understood that many additional changes in the details, materials, steps and arrangements of parts, which have been herein described and illustrated in order to explain the nature of the present invention, may be made by those skilled in the art while still remaining within the principles and scope of the invention.
Apparatus for collimating an X-ray beam, the apparatus comprising: a multi-slit rotatable collimator comprising: a semi-tubular structure extending coaxially along a longitudinal axis, the semi-tubular structure being formed out of an X-ray impermeable material; at least one slit formed in the semi-tubular structure, wherein the at least one slit extends parallel to the longitudinal axis of the semi-tubular structure; a mount for rotatably supporting the semi-tubular structure in the path of an X-ray beam; and a drive mechanism for selectively rotating the semi-tubular structure about the longitudinal axis of the semi-tubular structure, whereby to selectively (i) position the at least one slit in the path of the X-ray beam so as to tailor the X-ray beam to the width of the at least one slit, and (ii) position a solid portion of the semi-tubular structure in the path of an X-ray beam so as to block an X-ray beam.
0
This application is based on Japanese Patent Application No. 2006-149483 filed on May 30, 2006, the content of which is hereby incorporated by reference. BACKGROUND OF THE INVENTION The present invention relates to a decurl device which detects a curl of a sheet and uncurls the sheet, and an image forming apparatus provided with the decurl device. An electrophotographic image forming apparatus, i.e., a copy machine, a printer, a facsimile or a multi-functional machine having the functions thereof, performs image formation by transferring a toner image, obtained by developing an electrostatic latent image formed on an image carrier, with a developing device, on a sheet directly or via an intermediate transfer member, then feeding the sheet through a pressuring position between a heat roller for fixing or a fixing belt and a pressure roller to fix the image. In a fixing process, dehydration of a sheet causes so-called curling, a phenomenon such that the sheet after fixing warps upward or downward in a wavy form. Particularly, such curling of a sheet tends to noticeably occur due to increased amounts of toners supplied to the sheet at the time of forming a color image, the use of multifarious kinds of sheets, etc. A curl of a sheet raises a problem particularly in a case of forming images on both sides of a sheet or a case of making an article bound by bookbinding or so in a finisher. There is a case where a decurl member for correcting a curl of a sheet which occurs after fixing is used to avoid reduction in image quality or so originating from paper jamming, reduced sheet storability in a sheet ejecting section, a transfer failure at the time of double-side image formation, or the like all caused by such a curl. A sheet curl control apparatus described in Unexamined Japanese Patent Application No. 05-238624 (FIG. 4) has a decurler and adjusting means which adjusts the decurling action of the decurler, detects the amount of curling by measuring a time interval between the first interruption of an infrared ray irradiated from one light source by passing of the leading edge of a sheet and the next interruption of the infrared ray using infrared sensors at two locations, and changes the decurling action according to the curling amount. In above-mentioned sheet curl control apparatus, as the sensors are disposed downstream of a sheet in the sheet conveying direction, the sensors detect a curl at the leading edge of a sheet in the sheet conveying direction but cannot detect a curl which occurs on the entire surface of the sheet. Because a curl is detected by a horizontal sheet conveying section, the curling amount changes due to the dead weight of the sheet, disabling detection of the accurate curling amount. A sheet conveying device described in Unexamined Japanese Patent Application No. 2002-60112 (FIG. 1) detects a curling amount with a reflection type displacement sensor, and performs such control as to change the sheet suction force generated by a suction fan according to the detected sheet curling amount. Because the sheet conveying device also has the sensor disposed at an end portion of a sheet to detect the amount of displacement of the leading edge of the sheet in the sheet conveying direction at the horizontal sheet conveying section, it also cannot detect an accurate curling amount. A decurl system described in Unexamined Japanese Patent Application No. 2002-80158 comprises decurl devices, curling amount measuring devices and correction amount modifying means, and detects a curling amount by the displacement of an actuator or a reflection type displacement sensor. In this system, a curl is detected in the vicinity of the decurl device on the downstream side in the sheet conveying direction to detect the curling amount after the sheet is uncurled. SUMMARY OF THE INVENTION One aspect of the present invention is a decurl device including a curl detecting section having a plurality of toothed wheels which detect a curling amount and a curling direction of a curled sheet, and a plurality of uncurling sections which are disposed downstream of the curl detecting section in a sheet conveying direction and uncurls the sheet by warping the curled sheet in the opposite direction to the direction of curling, whereby the uncurling section that reduces the curl is selected from the plurality of uncurling sections to uncurl the sheet based on the curling amount and the curling direction detected by the curl detecting section. Another aspect of the invention is an image forming apparatus including an image forming apparatus main body which forms an image on a sheet, a decurl device as recited above, and a sheet finisher which performing a finishing process on the sheet ejected from the decurl device. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a general view of an image forming apparatus according to an embodiment of the present invention; FIG. 2 is a cross-sectional view of a decurl device according to an embodiment of the present invention; FIG. 3 is a plan view of a curl detecting section; FIG. 4 is a front view of a detecting plate and a sensor; FIG. 5( a )- 5 ( c ) are perspective views showing various curls of a sheet; FIG. 6 is a cross-sectional view showing layout positions of toothed wheels of the curl detecting section; and FIG. 7 is a block diagram showing control of the curl detecting section, a first uncurling section and a second uncurling section. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT While a preferred embodiment of the present invention will be described below, the invention is not limited to the embodiment. FIG. 1 is a general view of an image forming apparatus according to an embodiment of the present invention. The image forming apparatus includes an image forming apparatus main body A, a decurl device B and a sheet finisher FS. [Image Forming Apparatus] The image forming apparatus main body A has an automatic document feeder 1 and an image reading section 2 at an upper portion, and a printer section constituting a lower portion. Reference numeral “3” denotes a sheet storing section which stores sheets S. A printer engine 5 forms an image on a photoreceptor 4 by an electrophotographic process of charging, exposing the photoreceptor 4 and developing. The printer engine 5 forms an image on a sheet S, and the image is fixed in a fixing unit 6 . The fixing unit 6 forms a nip with a heat roller 6 b with a built-in heat source 6 a , and a pressure roller 6 c , and heats and presses the sheet S while conveying the sheet S to melt toners, and fixes the image on the sheet S. The sheet S is fed by a first sheet feeder 3 a and is temporarily stopped and then fed by a second sheet feeder 3 b to have an image formed thereon. The image-formed sheet S is ejected from sheet ejection ports by ejection rollers 8 . As conveyance paths for the sheet S, a sheet feeding path 7 from the sheet storing section 3 to the printer engine 5 , a conveyance path 9 a which extends from the printer engine 5 to a sheet ejection port passing through the fixing unit 6 and the ejection rollers 8 , and a rear surface conveyance path 9 b which effects a flipped-over conveyance. Image forming modes include a one-side face-down ejection mode, a one-side face-up ejection mode and a two-side mode. In one-side face-down ejection mode, an image is formed on one side of a sheet S, and the sheet S having passed the fixing unit 6 is flipped over by the flip-over process, and then conveyed and ejected by the ejection rollers 8 . In one-side face-up ejection mode, an image is formed on one side of a sheet S, and the sheet S conveyed to the conveyance path 9 a is directly conveyed and ejected by the ejection rollers 8 . In two-side mode, an image is formed on one side of a sheet S, and the sheet S having passed the fixing unit 6 is conveyed downward to the rear surface conveyance path 9 b , is flipped over, and then fed again to the sheet feeding path 7 . The printer engine 5 forms a back image on the bottom side of the sheet S fed again, and the sheet S having the back image formed thereon passes through the fixing unit 6 , and is conveyed and ejected by the ejection rollers 8 . Reference numeral “10” denotes an operation section, and various modes of the image forming apparatus main body A and the output mode using the sheet finisher FS can be set by operating the operation section 10 . A controller C 1 provided in the image forming apparatus main body A is connected to a controller C 2 of the decurl device B and a controller C 3 of the sheet finisher FS via a communication section C 4 . The sheet S ejected from the image forming apparatus main body A is conveyed to the sheet finisher FS through the decurl device B. The decurl device B will be described later. [Sheet Finisher] The sheet finisher FS, which performs various finishing processes on the sheet S ejected from the image forming apparatus main body A, is the generic term of a puncher, a folder, a flat binder, a center-binder, a pasting and bookbinding machine, a cutting machine and the like. A pasting and bookbinding machine as a typified example will be explained as one embodiment of the sheet finisher FS. The pasting and bookbinding machine is provided with a sheet take-in section 21 , an ejection section 22 , a sheet bundle storing section 23 , a sheet bundle conveying section 24 , a paste coating section 25 , a cover sheet feeding section 26 , a cover sheet cutting section 27 , a cover sheet wrapping section (wrapping and bookbinding section) 28 , and an aligning section 29 . Those sections are disposed in the pasting and bookbinding machine nearly in the vertical direction. The sheet S supplied to the sheet take-in section 21 is conveyed to either the ejection section 22 or the sheet bundle storing section 23 by a switching gate 210 . When sheet conveyance to the ejection section 22 is set, the switching gate 210 blocks a conveyance path 211 to the sheet bundle conveying section 24 and releases a conveyance path 212 to the ejection section 22 . The sheets S, which pass along the conveyance path 212 to the ejection section 22 , are conveyed upward to be stored on a fixed sheet ejection tray 221 located at the topmost portion of the sheet finisher FS. The sheets S, which are branched leftward and conveyed in the illustration, at the downstream of the sheet conveying direction, by the switching gate 210 , are stored and stacked in the sheet bundle storing section 23 at a predetermined position in order, and are aligned widthwise and vertically to form a sheet bundle Sa containing a predetermined number of sheets S. The sheet bundle Sa stacked on a sheet placing table 231 of the sheet bundle storing section 23 is conveyed obliquely downward, held by a holding member 241 of the sheet bundle conveying section 24 , and is rotated so that the side (spine portion) where a paste coating process is performed on the sheet bundle Sa while holding the sheet bundle Sa faces down, and is stopped at a predetermined position. The paste coating section 25 includes a paste coating roller 251 , a paste container 252 , and a moving body 253 which can move to a paste coating position on the front side from the initial position of the spine side of the pasting and bookbinding machine while supporting the paste container 252 . A cover sheet K stored in the cover sheet feeding section 26 is conveyed to the cover sheet wrapping section 28 along a sheet conveyance path 261 through the cover sheet cutting section 27 , and then has the trailing edge cut to have a predetermined length by the cover sheet cutting section 27 . The cut length of the cover sheet K is the length of two sheets S in the moving direction plus the length of the spine of the sheet bundle Sa. The cover sheet wrapping section 28 receives and conveys the cover sheet K supplied from the cover sheet feeding section 26 , stops the cover sheet K at a predetermined position and performs widthwise positioning thereof by the aligning section 29 . The cover sheet wrapping section 28 moves a moving case 282 upward by a rise-and-fall section 281 , so that the center portion of the cover sheet K placed on a pressure member 283 is pressed against, and adhered to, a paste coated surface N of the sheet bundle Sa at the lift-up position. The downward movement of the pressure member 283 facing the spine of the sheet bundle Sa and the movement of a pair of horizontally symmetrical folding members 284 disposed at the upper portion of the cover sheet wrapping section 28 causes the cover sheet K to be folded along the side edge of the paste coated surface N of the sheet bundle Sa, thus forming a sheet bundle Sa having the cover sheet K attached to the top and bottom sides of the sheet bundle Sa. After the process of folding the cover sheet K, the cover sheet wrapping section 28 moves downward with the downward driving by the rise-and-fall section 281 , after which an ejection belt 285 which has been retracted outward in the widthwise direction of the cover sheet K with the retraction of the aligning section 29 moves into the widthwise internal space under the sheet bundle Sa and stops there. When holding by the holding member 241 is released thereafter, the sheet bundle Sa moves downward and stops at a position where the lower spine of the sheet bundle Sa abuts on the top surface of the ejection belt 285 . The rotating ejection belt 285 ejects a booklet wrapped and bookbound with the cover sheet K pasted adhered thereto outside the finisher. [Decurl Device] FIG. 2 is a cross-sectional view of the decurl device B according to an embodiment of the present invention. The decurl device B is provided with a sheet introducing section 100 , a decurl and conveying section 110 , a curl detecting section 120 , an uncurling and conveying section 130 , a first uncurling section 140 , and a second uncurling section 150 . The sheet S having an image formed thereon by the image forming section of the image forming apparatus main body A is ejected through the fixing unit 6 and the ejection rollers 8 , is introduced to the sheet introducing section 100 of the decurl device B, and is conveyed while being held by conveyance rollers 101 . A fan F disposed near the conveyance rollers 101 drops the temperature of the sheet S to be ejected from the image forming apparatus. A switching gate 102 disposed downstream of the conveyance rollers 101 in the sheet conveying direction selectively switches the conveyance of the sheet S to a conveyance path 103 below or a bypass conveyance path 104 above. The sheet S to be introduced to the conveyance path 103 is interposed and conveyed to the decurl and conveying section 110 by conveyance rollers 105 , 107 along a conveyance path 106 . The sheet S conveyed into the decurl and conveying section 110 passes through a guide plate 111 , is interposed by conveyance rollers 112 , is conveyed in U-turn by a guide plate 113 , is held vertically upward by conveyance rollers 114 and is conveyed to the curl detecting section 120 interposed by conveyance rollers 116 , passing through a guide plate 115 . A sensor PS 1 which detects the passing of the leading edge of the sheet S is disposed upstream of conveyance rollers 116 in the sheet conveying direction. The curl detecting section 120 will be described later referring to FIGS. 3 and 4 . After the curling amount and the curling direction of the sheet S are detected by the curl detecting section 120 , the sheet S passes between a pair of guide plates 124 A, 124 B and is interposed and ejected from the decurl and conveying section 110 by conveyance rollers 117 . The sheet S ejected from the decurl and conveying section 110 passes along a conveyance path 108 , and is interposed and supplied to conveyance rollers 131 of the uncurling and conveying section 130 by conveyance rollers 109 . Either the sheet S which passes along the bypass conveyance path 104 or the sheet S which is ejected from the curl detecting section 120 through the decurl and conveying section 110 and passes along the conveyance path 108 is supplied to the conveyance rollers 131 of the uncurling and conveying section 130 . The sheet S conveyed by the conveyance rollers 131 passes along a conveyance path 132 , and is branched to either one of an upper conveyance path 135 A and a lower conveyance path 135 B formed by a switching gate 134 which is actuated by an unillustrated drive member. After a concave curl upward of the sheet S conveyed by the upper conveyance rollers 135 A is uncurled by the first uncurling section 140 to be described later, the sheet S is conveyed downward by conveyance rollers 136 along a vertically underlying conveyance path 135 C. The sheet S which does not need uncurling is conveyed downward by the conveyance rollers 136 along the lower conveyance path 135 B by path switching carried out by the switching gate 134 . The sheet S conveyed by the conveyance rollers 136 is branched to either one of a rightward conveyance path 138 A and a leftward conveyance path 138 B formed by a switching gate 137 which is actuated by an unillustrated drive member. After a convex curl upward of the sheet S conveyed by the rightward conveyance rollers 138 A is uncurled by the second uncurling section 150 to be described later, the sheet S is ejected out of the apparatus by ejection rollers 139 along a conveyance path 138 C. The sheet S which does not need uncurling is ejected out of the apparatus by the ejection rollers 139 along the leftward conveyance path 138 B. Selection of uncurling of the sheet S by the first uncurling section 140 and the second uncurling section 150 and whether uncurling is needed or not, are carried out based on the curling direction and the curling amount which are detected by the curl detecting section 120 , that will be described later. [Uncurling Section] Because the first uncurling section 140 and the second uncurling section 150 have substantially the same configuration, the first uncurling section 140 will be described as a typified example. The first uncurling section 140 has a drive roller 141 which is rotated by an unillustrated drive member, a belt 143 wound around the drive roller 141 and drive roller 142 , a pressure roller 144 which is rotated pressed against the belt 143 , and a drive member which selectively presses the pressure roller 144 against the belt 143 . As the sheet S conveyed along the conveyance path 135 A passes through the pressing position where the pressure roller 144 is pressed against the belt 143 , the sheet is uncurled. The pressure of the pressure roller 144 applied to the belt 143 is variably adjusted according to the curling amount of the sheet by an unillustrated drive member. [Curl Detecting Section] FIG. 3 is a plan view of the curl detecting section 120 . Because the curl detecting section 120 is arranged symmetrically with respect to a vertical sheet conveyance path “p” in FIG. 2 , the curl detecting member shown on the left will be described. Each of the conveyance rollers 116 , 117 having a drive roller and a driven roller which convey the sheet S interposed therebetween are disposed upstream and downstream of the curl detecting section 120 has an integrated elastic layer in an axial direction longer by the maximum sheet width. The elastic layers of the drive roller and the driven roller of the conveyance rollers 116 , 117 are made of the same material having the same rubber hardness. For example, the elastic layers of the drive roller and the driven roller of the conveyance rollers 116 , 117 are made of ethylene propylene rubber (EPDM) or urethane rubber or the like. Toothed wheels 122 A, 123 A rotatably supported on a support plate 121 A are disposed at predetermined intervals, for example, 15 toothed wheels are disposed at equal intervals of about 15 mm, in the axial direction of a rotational shaft 127 A. A disk-shaped detecting plate 125 A is fixed to one axial end of the rotational shaft 127 A which has a plurality of toothed wheels 122 A fixed thereto and is rotatably supported on the support plate 121 A. The rotational angle of the detecting plate 125 A is detected by a sensor PS 2 . A disk-shaped detecting plate 126 A is fixed to one axial end of a rotational shaft 128 A which has a plurality of toothed wheels 123 A fixed thereto and is rotatably supported on the support plate 121 A. The rotational angle of the detecting plate 126 A is detected by a sensor PS 3 . The curl detecting member having a support plate 121 B and toothed wheels 122 B, 123 B of the curl detecting section 120 on the right-hand side in FIG. 2 has a configuration similar to that of the curl detecting member having the support plate 121 A and toothed wheels 122 A, 123 A on the left-hand side in the diagram, and both members are arranged line-symmetrical to the vertical sheet conveyance path “p”. The toothed wheels 122 A, 123 A, 122 B, 123 B which detect a curl at the leading edge portion of the sheet are disposed across the entire sheet in the widthwise direction, and detect the curling amount and the curling direction with respect to various sizes of sheets to be conveyed. The toothed wheels can detect a curl at a corner portion of the sheet and curls generated at both widthwise edge portions of the sheet besides a curl at the leading edge portion of the sheet. FIG. 4 is a front view of the detecting plate 125 A and the sensor PS 2 . A plurality of elliptical holes (slits) are bored through the disk-shaped detecting plate 125 A fixed to the axial end of the rotational shaft 127 A, and the rotational angle of the detecting plate 125 A is detected by the translucent sensor PS 2 . The detecting plate 126 A disposed at the axial end of the rotational shaft 128 A and the sensor PS 3 , and the unillustrated detecting plate and sensor of the toothed wheels 122 B, 123 B likewise have the same shapes as the detecting plate 125 A and the sensor PS 2 . FIGS. 5( a )- 5 ( c ) are perspective views showing various curls of the sheet S. FIG. 5( a ) shows a lead-edge curl and a trail-edge curl generated in the sheet conveying direction. FIG. 5( b ) shows a corner curl generated at a corner of the leading edge in the sheet conveying direction. FIG. 5( c ) shows a side curl generated on the side-edge portion in parallel to the sheet conveying direction. FIG. 6 is a cross-sectional view showing layout positions of the toothed wheels 122 A, 123 A, 122 B, 123 B of the curl detecting section 120 . FIG. 7 is a block diagram showing control of the curl detecting section 120 , the first uncurling section 140 and the second uncurling section 150 . The toothed wheels 122 A, 122 B disposed horizontally symmetrically facing each other with the vertical sheet conveyance path “p” in between detect a large curl of 10 mm or larger on the sheet S. The toothed wheels 123 A, 123 B detect a small curl of 5 to 10 mm on the sheet S. A distance L 1 at which the vertical sheet conveyance path “p” connecting the nip position of the conveyance rollers 116 to the nip position of the conveyance rollers 117 faces the outside diameter of the toothed wheels 122 A is set to 10 mm. The distance L 1 at which the vertical sheet conveyance path “p” faces the outside diameter of the toothed wheels 122 B is also set to 10 mm. A distance L 2 at which the vertical sheet conveyance path “p” faces the outside diameter of the toothed wheels 123 A is set to 5 mm. The distance L 2 at which the vertical sheet conveyance path “p” faces the outside diameter of the toothed wheels 123 B is also set to 5 mm. When the sensor PS 2 detects that the leading edge portion of the sheet S which is interposed and conveyed to the vertical sheet conveyance path “p” by the conveyance rollers 114 , 116 abuts on any of the toothed wheels 122 A, 122 B and rotates, a large curl of 10 mm or larger on the sheet S and the curling direction are detected. Likewise, when the sensor PS 3 detects that the leading edge portion of the sheet S abuts on any of the toothed wheels 123 A, 123 B and rotates, a small curl of 5 to 10 mm on the sheet S and the curling direction are detected. Based on the curling amount and the curling direction detected by the curl detecting section 120 , one of the first uncurling section 140 and the second uncurling section 150 which reduces curling is selected to uncurl the sheet S. The sensor PS 1 disposed upstream of the conveyance rollers 116 in the sheet conveying direction detects passing of the leading edge portion of the sheet S passing along the vertical sheet conveyance path “p”. A predetermined time from the arrival of the leading edge portion of the sheet at the curl detecting section 120 and completion of the passing is preset, and the control is executed in such a way that the rotation of the toothed wheels 122 A, 122 B, 123 A, 123 B originating from the abutment of the leading edge portion of the sheet S within the predetermined time is detected by the sensor PS 2 , PS 3 . Although the foregoing description of the embodiment has been given of an image forming apparatus which has the decurl device B and the sheet finisher FS connected to a copy machine, the invention can be adapted to an image forming apparatus which has the decurl device B and the sheet finisher FS connected to the image forming apparatus main body A of a printer, a facsimile, a digital multi-functional machine or the like. The invention can be used as a single decurl device B. The toothed wheels of the curl detecting section which detect the amount of curling at the leading edge portion of a curled sheet and the curling direction are disposed across the entire sheet in the widthwise direction, and detect the curling amount and the curling direction with respect to various sizes of sheets to be conveyed. The toothed wheels can detect a curl at a corner portion of the sheet and curls generated at both widthwise edge portions of the sheet as well as a curl at the leading edge portion of the sheet. Based on the curling amount and the curling direction detected by the curl detecting section, one of a plurality of uncurling sections which reduces curling is selected to uncurl a curl of a sheet. In the image forming apparatus having the image forming apparatus main body, the decurl device and the sheet finisher connected together, the decurl device cancels curling, waving or the like of a sheet to be ejected from the image forming apparatus main body, and sheets with a good flatness are fed to the sheet finisher, and a high-quality booklet is made after the finishing process.
A decurl device includes: a curl detecting section having a plurality of toothed wheels each which detects a curling amount and a curling direction of a sheet having a curl; and a plurality of uncurling sections each arranged downstream of the curl detecting section in a conveyance direction of the sheet having the curl, which uncurls the sheet by bending and transforming the sheet in a direction reverse to a curling direction thereof. One of the uncurling sections, which reduces the curl, is selected on the basis of the curling amount and the curling direction that have been detected by the curl detecting section, thereby uncurling the sheet.
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TECHNICAL FIELD The present invention relates to a system and process for the monitoring of physiological vital life signs, and particularly to a non-invasive system and process. Background of the Invention It is well known that the initial encounter with a physician involves the physician evaluating various physiological vital signs such as heart rate, heart sounds, respiration rate, respiration sounds, blood flow, digestive processes and other parameters which can create acoustical movement and/or vibrations. This information is even taken when a person is reasonably well for later use as a frame of reference because these physiological vital signs are regarded as a general measure of the state of a person's health. During treatment in a hospital, these physiological vital signs are monitored closely, particularly if a patient is severely sick or the status of the patient such as an infant may be critical. Thus, the collection of information relating to physiological vital signs is regarded as essential for competent medical care. Typically, physiological vital signs are collected through the use of devices in direct contact with a person's body. It is well known that the acoustical information is very weak, that is, it has a very low signal to noise value so that direct contact of the pickup device is used to minimize external noise and to have the pickup device close to the source of the acoustical vibrations. Some medical information requires many direct contacts to the skin such as ECG systems. Very weak sounds require highly specialized equipment designed for a specific task of collecting a limited class of data. The acquisition of the physiological vital signs from the many patients in a hospital is time consuming and is an inefficient use of talented personnel. Even if the data being collected is minimal, the effort remains significant because the medical specialist must encounter each patient personally and physically contact the patient with an instrument. In addition, the use of a direct contact pickup on patients is uncomfortable for many patients, especially if the patent is very sick and requires frequent monitoring. The difficulty in using a device attached to a patient for monitoring physiological vital signs is compounded not only by the movement of the patient in the bed but by a patient who wants to move from a bed to a chair, or to a wheelchair, or to another location. Accordingly, it is seen that a need exists for a simple and effective system and method to monitor physiological vital signs. There is also a need for a non-invasive system which allows the movement of patients from a bed to some other place without terminating the monitoring activities. Furthermore, there is a need for a system which is adaptable to a variety of situations such as chairs, beds, wheelchairs, etc. and is relatively inexpensive. SUMMARY OF THE INVENTION The present invention overcomes the disadvantages of the prior art by providing a monitor which allows the monitoring of manifold physiological vital signs and is adaptable to a wide variety of settings including chairs, beds, wheelchairs, and other environments. The invention also provides a non-invasive monitor which adapts to be responsive to a patient's particular vital signs being monitored. The present invention in one embodiment enables the monitoring of physiological vital signs without contacting the subject. The invention includes a sensing means operable to transform movements and/or acoustical waves into an electrical signal, signal processing means coupled to the sensing means and operable to receive the electrical signal from the sensing means and to process the electrical signal adaptively using wavelet correlator analysis techniques. The signal processing means has an output indicative of the movement and/or acoustical wave producing the electrical signal. As used herein, a "wave correlator analysis" is a coherent matched filtering performed in real time between the conditioned data and the range of wavelets from the `master wavelet filtering` as described herein. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram showing a system according to the invention. FIG. 2 is a flow diagram showing the main elements used in carrying out the invention shown in FIG. 1. FIG. 3 is a flow diagram showing the flow of information for the initialization algorithm used in the invention shown in FIG. 2. FIG. 4 is a flow diagram showing the main processor flow of information in carrying out the invention shown in FIG. 1. FIG. 5 shows a front view of a typical operating system display set incorporating the invention. FIG. 6 is a block diagram showing the collection of sensing data used in the invention as shown in FIG. 1. FIG. 7 is a top sectional view of a mattress showing embedded sensors for carrying out the invention according to FIG. 1. FIG. 8 is a side elevational sectional view of the mattress shown in FIG. 6. FIGS. 9a and 9b show the block diagram and flow diagram, respectively, of the patient presence determination system according to the invention. FIG. 10 shows a time display for defining a parameter of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS General Description FIG. 1 shows an overall view of one embodiment of the invention being used to monitor the physiological vital signs of a subject 1. The subject 1 is positioned in a wheelchair or bed not shown and resting on cushion 2. Sensors such as piezoelectric sensors 3, or fiber optic pressure or motion sensors, or air or liquid diaphragm or the like are used to transform acoustical waves or motion into an electrical signal. Suitable devices are available commercially and need not be highly sensitive because the invention enables the detection and analysis of physiological vital signs represented by weak electrical signals with relatively poor signal to noise. Thus, one of the advantages of the invention is that relatively inexpensive sensors can be used, thereby avoiding large expenses to equip numerous chairs, beds, wheelchairs and the like with sensors so that the subject is not only free to move in bed, but can move from bed to chair or any convenient place without concern of contact devices. The electrical signal from the piezoelectric sensor 3 is coupled to an analog to digital converter 4 which has an output signal coupled to a processor 6 according to the invention. The output signal from the processor 6 is coupled to a post processor 7 which provides an interface between the processor 6 and device being used for communicating the information from processor 6 to another device or person. The embodiment shown in FIG. 1 communicates the output signal of the post processor 7 to a receiver 8 which displays the information for use by a medical attendant 9. The output signal of the post processor 7 can be hardwired or can transmit the information to a remote location such as a nurse's station. FIG. 2 shows the main functional elements of the algorithm used in the processor of the invention. The following is a general description of the operation. Typically, the medical attendant indicates at block 20 that there is a new patient to be monitored or analyzed and the start is indicated in block 21. The initialization sequence in block 22 has signals from sensors not shown and establishes matched filters or wavelets corresponding to selected parameters such as the last heart beat and the heart rate. The initialization can take several seconds, typically less than 5 seconds. During the initialization, a built in test is performed to instruct the algorithm to repeat or continue to the next stage. The sensors also provide data to the health monitoring block 23. The output signals from the block 23 are formatted and transmitted as required and various interrupts are serviced. More details of the operation will be provided in connection with other Figures herein. FIG. 3 shows the main functional elements of the initialization algorithm carried out in block 22 in FIG. 2. The sensor data is subjected to band pass filtering in block 31 to improve the signal to noise ratio and eliminate aliasing. That is, errors which may be introduced in subsequent operations which include a fast Fourier transform. The output signal from block 31 is coherently detected in block 32 through the use of an energy detector, a bank of potential wavelet basis functions. Block 33 provides low pass filtering of the output of block 32 along with decimating the signal at a sample rate of typically 10 Hz. The sampling in block 32 results in a sequence of peaks at a periodic interval corresponding to a 5 second sequence of initial detections. Block 33 is coupled to block 34 where a zero filled Fourier transform is used to detect the period and location of the peaks from the phase. Blocks 35-38 analyze the signal from block 34 to provide the starting parameters for the processor algorithm. If the vital sign being monitored is the heart beat, then the location in time and the rate of the heart beat are used to focus the windowing function. The detected image of the heart beat wavelet is focussed in block 36 by coherently averaging the 5 seconds of data used in the initialization processing. The processor also extracts the typical power levels of the signal of interest while minimizing the noise background in blocks 37 and 38. FIG. 4 shows the flow of information in the main processor during the steady state operation of the invention. Sensor data is introduced into block 41 which provides a first order time window based on the initialization. Block 41 is coupled to blocks 42 and 43. Block 42 carries out processing to determine if there is a "flat line" condition, or excessive interference, or if detection is even possible. Block 42 is coupled to block 44 which carries out a built in test (BIT). Actually, part of the test is performed in block 42. The BIT is performed continuously and instructs the algorithm to repeat, continue to its next stage, or signal the attendant. During monitoring, however, the input signals are formatted and transmitted as required and various interrupts are serviced. Block 43 is a coherent matched filtering performed in real time on the conditioned input data using the range of wavelets from the master wavelets filtering from block 45. Block 46 peak detects the signal from block 43. The peak signal is evaluated after normalization. The peak signal is used to extract information to update the temporal filtering in block 47 adaptively to estimate the event location and rate update. The peak signal is also used to update the master wavelet filtering adaptively to estimate the master wavelet spectral content and time image. Any or all of the information in block 45 and block 47 can be selectively outputted to the user. The gain and feedback loops should be selected to maintain the proper balance between estimators and output event declarations. FIG. 5 shows the front panel 51 of experimental equipment based on one embodiment of the invention for monitoring a person's heart. The lower center of the panel 51 contains switches and buttons for controlling the operation and displays. The lower left has an elapsed time clock 53 and the upper left has status signal lights 54 for alerting the medical attendant. At the start of monitoring, start 55 is depressed and after about 5 seconds, the initialization light turns off and the monitor "on" light goes on. The monitor light remains on until either the stop or restart buttons are depressed, or if the BIT in FIG. 4 is failed. Heart rate deviations are evident by the heart rate light and the lack of detected heart beats is evident by the missed beat light. The light "on" conditions are accompanied by audio alarms. These responses are programmable and depend on the quality of the filter states and the BIT as well as preset conditions determined by the operator. The area on the left labeled as "SENSOR VALUES" allows the invention to be used to read instantaneous physiological vital signs either at the location of the instrument or remotely through telephone lines, or hard wiring, or a transmission. The upper right portion entitled `HISTORY" can be selectively displayed to show the latest 100 seconds of the heart beat at a 1 second rate. This display can be selected to be a selected previous time such as the previous 4 hours. Another possible display is the missed beat activity. Appropriate programming allows a wide range of possible displays depending on the desired information. The lower right hand portion of the panel 51 labeled "DIAGNOSTICS" can show the first heart beats as averaged over the last 2 minutes, or if the beat display 56 is selected to be "single", the real time beats are shown. The display can be altered to show the time or the spectral representation and used to aid a physician to diagnose ailments in a manner similar to the use of the EKG electrical signal. Detailed Description FIGS. 6-9 show more detail of preferred embodiments of the invention. FIG. 6 is a block diagram of the arrangement of the collection of data. A plurality of sensors 61 such as eight separate sensors are coupled to a multiplexer unit 62 and are grounded through 1 megohm resistors as shown. The typical sample rate of the multiplexer unit 62 is 20 Hz. It is convenient to use a laptop computer (not shown) for carrying out data processing. The multiplexer unit 62 is coupled to a differential analog to digital converter 63. The differential analog to digital converter 63 can be implemented using a software controlled DAQCARD-700 available from National Instruments Corporation. The DAQCARD-700 allows up to 8 analog input signals for differential analog to digital conversion which is digitized by time multiplexing to a single output signal. FIGS. 7 and 8 show a typical arrangement of the sensors 61 in a foam mattress. In FIG. 7, the top row of the sensors 61 is spaced about 4 inches from the bottom row and each of the sensors 61 in the middle row is spaced about 2 inches from the nearest sensor 61 in the top and bottom rows. The DAQCARD-700 digitizes each input channel in sequence and produce an average signal as follows: v(t)=1/NΣv.sub.i (t.sub.i) as each voltage is sampled at 20 Hz, the effective sampling rate is 160 Hz. The processing is performed using standard double buffering in which a block of data is digitized while a prior block of data is being processed. Any spatially out of phase signals to the sensors 61 are suppress through the processing. The real time averaging in the differential analog to digital converter 63 is effectively a low pass filter. For the parameters being used, namely a sampling rate of 20 Hz and N=8, the attenuation of the amplitude at the frequency of interest, 5 Hz, is about 10% and the half power (3 db) is at about 8 Hz. The bandwidth can be modified by averaging with weighted coefficients to create an effective band pass filter, rather than a low pass filter. It is also possible to increase the sample rate and then decimate to effect a bandwidth change. Utilizing the invention to detect heart beats requires consideration of the expected characteristics of the signals generated by heart beats. Heart beat detected in a bed primarily through the upper body cavity are characterized by having most of the energy centered in the frequency range of 20 Hz to 30 Hz. Generally, the frequency width is about 10 Hz and it can have a center frequency as low as 15 Hz or as high as 45 Hz. Accordingly, the system parameters include the sampling rate, low pass filter, etc. must be scaled to suit the physiological vital signs being measured. The typical sampling rate is in the range of 150 Hz to 200 Hz range. In stead of the low pass filter operation described above, a sampling rate of as high as high as 320 Hz can be used followed by a fast fourier transform (FFT) which is decimated to a sampling rate of 40 Hz. The FFT acts as a bank of band pass filters and the resulting complex time series has an improved signal to noise ratio at a lower sampling rate. FIGS. 9a and 9b show an overall block diagram and corresponding detailed flow diagram, respectively. One important algorithm is to determine whether or not a patient is present. The (occupied) algorithm makes this determination and can have the filters in the system "coast" or predict ahead to enable a suitable re-start when the patient returns. For this algorithm, the sensors being used measure acceleration, have a long time constant, and low level, high frequency noise. As these are inexpensive sensors compensations in the processing are made to compensate for the deficiencies of these sensors. When the initialization algorithm is started, it is assumed that the chair or bed is occupied by a patient. If desired, the start of the algorithm can be made even if the bed or chair is unoccupied. In FIG. 9b, the symbol "z -1 " is the conventional symbol for a lag-1 (dt) operator in digital signal processing analysis (z-transforms). Generally, the corresponding portions in FIGS. 9a and 9b relating to the high pass filter and integrators is indicated. The basic equation corresponding to the high pass filter is as follows: g=0.999 vo(t)=vo(t-dt)+g*[v(t)-vo(t-dt)] xdd(t)=v(t)-vo(t) The "g" term is a time constant determined by calculation to minimize the response to unwanted low frequencies associated with the heart and breathing. The term "dt" corresponds to the sample interval. The term "xdd(t)" is the detected acceleration of the cushion or bed. The term "xd(t)" is the rate and "x(t)" is the flex of the sensor. The integrators can be represented as follows: xd(t)=xd(t-dt)+xdd(t)*dt x(t)=x(t-dt)+xd(t)*dt+xdd(t)*dt*dt/2 where xd(o)=0 vo(0)=0 x(o)=0.0008 dt=1/20 sec. The correction calculation resets the threshold. Correction to reset x(t) ed=0.00001 e=0.0005 (for the detector) If [(xd<ed) and (xdd<ed)] then {if (x<e),then x=0} The decision is made in the detector through a comparator. Detector Logic ##EQU1## Equations corresponding to the flow diagram shown in FIG. 3 for the Initialization follow: For a high signal to noise (SNR>3 dB), the first three blocks 31, 32 33 can be replaced with an energy (or variance) detector (where t=n*dt is replaced by n): ##EQU2## where v.sub.o =(1/L)*Σv(n) L=the length of a `filter`, wavelet, or heart beat, typically 8-10 points for the embodiment (with sample rate 20 Hz) and n refers to the time sample index. Therefore ##EQU3## where w=(1/L)*[v(n+L.sub.o)-v.sub.o] or w=matched filter or wavelet function the function pow which corresponds to the variance or power is sampled at 10 Hz over all potential wavelets over the first 5 seconds of data (i.e. 50 points per wavelet). The subscript for the wavelets will be suppressed for convenience. The best match for period and wavelet is found. The following variables are computed for later use: max=the maximum value squared of pow ##EQU4## c1=(cn*cn)/L*L) The following is an example of an implementation: After zero filling to 512 points and DC (mean) removal, an FFT is computed and the peak amplitude located at `loc` corresponding to a potential heart beat frequency of 40 bpm-90 bpm. Zero filling is a standard technique in FFT processing to evaluate the spectrum at additional frequency values, basically interpolating, between the normal values. Then ##EQU5## where φ (loc) is the phase of the FFT at loc (corresponding to the phase of the heart beat location), and spot is the time (pointer value) of the first heart beat. Using spot and dtau, the time of the next heart beat (after the first 5 seconds) is estimated (tau). Also, if the energy detection is used instead of wavelet basis functions, then the master wavelet can be computed via coherent stacking over the initial 5 seconds of all heart beats, taking care of the time weighted normalization required. The algorithm uses pointers for the state vector tau and dtau where tau is the time array pointer and dtau is the number of points between beats. (For a typical embodiment, 1 second is 20 points.) As to FIG. 4 which involves a real time processor algorithm, the following equations are relevant. From the set-up and initialization: ##EQU6## The variables and notations used herein follow the definitions and conventions of any standard text on Kalman Filtering such as Brown, R. G., Introduction to Random Signal Analysis and Kalman filtering, John Wiley and Sons, 1983. The values are the result of system and performance modeling as per the text and standard practice. The `window` parameter is defined in connection with FIG. 10 as wnd=[P(O)=R].sup.1/2 *4 and the data to be analyzed is (First Order Time Window) N=L+2*wnd points in length `centered` on tau are shown in FIG. 10. This window is real time adaptive in length and location though it is never longer than the initial window as shown below. Let dat(n)=v(n') where the N points are selected via the window function. Signal Analysis Function ##EQU7## The following is an analysis of a narrow `power` window. For the a typical embodiment, if sigdat is 6 dB below nominal, (sigavg) is then the status is defined as `no activity` if sigdat is 6 dB above nominal, (sigavg) is then the status is defined as `excessive activity` if sigdat is within 6 dB of nominal then Wavelet Correlator Analysis is computed via a frequency domain equivalent of: ##EQU8## The correlator array is searched for a peak of amplitude (max) at location (loc) where loc is within tau+/-wnd If max>0.125, then z=loc (with the proper care of pointer indices. The search for the peak is over the set of wavelet functions in the neighborhood of the nominal (master)wavelet. Temporal Filtering Update (via a Kalman-like Filter) ##EQU9## then K=P*H.sup.T /(H*P*H.sup.T +R) Y+Y+K*eps P=(I-K*H)*P Y=Φ*Y P=Φ*P*Φ.sup.T +Q and wnd=4*[P(O)+R].sup.1/2 The maximum wnd allowed is initial wnd. Master Wavelet Filtering if max>0.125 then let w={dat.sub.LOC, dat.sub.LOC+1, . . . , dat.sub.LOC+L-1 } ##EQU10## G=(0.05-0.01)*(max-0.125)/(1.0-0.125)+0.01 W.sub.n =W'.sub.n +G*(w.sub.n w-w'.sub.n) is the update filter and w' refers to the previous values. The spectrum is computed for use in the correlator block. The following are additional system parameters relative to FIG. 5 with respect to the displays and alarms. In an operating embodiment, the display is updated each second and incorporated in the Toshiba Laptop (Model T1910 series). (See below) Most of the alarms are triggered via a running average of an `M out of N` counter of the form ctr(t)=ctr(t-dt)+g* {value (t)-ctr(t-dt)} where a typical g is 0.1 and thresholds are 0.6-0.9. `agitated` patient--uses the excessive power variable from the signal analysis `heart beat` missed--value is 1 if low power or adequate power and low correlation. heart rate--alert requirements can be set by the operator as upper and lower bounds or a band around the nominal from the initialization or over some nominal time history. Display of the heart beat--can be averaged=wavelet (w n ) or single=real time data array (dat n ) Receiver/Alerts to the Attendant The implemented embodiment uses simulated LED's and audio signals. The implementation can use any wired or wireless, telephone, pager, etc. system. A preferred implementation is to interface this smart sensor system to an existing emergency call system. A valuable option is to store the history internally and down load via a modem or hard wired connection to a main work station or hand carried nurse's logging device or recorder. There has been described a novel non-invasive medical monitor system. It is evident that those skilled in the art may now make numerous uses and modifications of and departures from the specific embodiments described herein without departing from the inventive concepts. Consequently, the invention is to be construed as embracing each and every feature and novel combination of features present or possessed by the accessory herein disclosed and limited solely by the spirit and scope of the appended claims.
An apparatus operable for monitoring physiological vital signs of a human body without physically contacting the body is disclosed. The apparatus includes a sensor operable to transform a movement and/or acoustical wave produced by the body into an electrical signal, a signal processor coupled to the sensor and operable to receive the electrical signal from the sensor and to process the electrical signal adaptively using wavelet correlator analysis. The signal processor provides an output signal indicative of the movement and/or acoustical wave producing the electrical signal. Typically, the apparatus can be used to monitor heart rate, respiration rate and related sounds, digestive system sounds as well as other physiological vital signs considered both essential and desirable for the evaluation of the health of a person.
0
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] The present invention is related to co-pending application entitled “OXYGEN CONCENTRATOR SYSTEM”, Ser. No. ______, filed in the U.S. Patent and Trademark Office concurrently with the present application. BACKGROUND OF THE INVENTION [0002] 1. Field of the Invention [0003] The present invention relates to oxygen concentrator systems, and more particularly, to a patient ventilator oxygen concentrator system having altitude compensation to improve performance at higher altitudes. [0004] 2. Description of the Related Art [0005] Many medical applications exist that require either oxygen-enriched air or medical grade air. Both are widely used in respiratory care treatments, for example. Furthermore, both oxygen-enriched air and medical grade air are used to power various pneumatically driven medical devices. [0006] Hospitals and other medical care facilities have a need for both oxygen-enriched air and medical grade air. In military hospitals and in hospitals in Europe, for example, these needs may be met by using oxygen concentration systems to provide oxygen-enriched air and by using a filtration system for providing medical grade air. On the other hand, hospitals and other medical care facilities in the United States often use high-pressure gas systems or liquid oxygen to gaseous conversion systems to provide oxygen-enriched air. [0007] Commonly used oxygen concentration systems often employ a pressure swing adsorption (PSA) process to remove nitrogen from a given volume of air to produce oxygen-enriched air. Such a process is disclosed in U.S. Pat. No. 4,948,391 to Noguchi and this patent is incorporated herein by reference in its entirety. [0008] In such oxygen concentration systems, as the plenum pressure is increased, the product flow, that is, the oxygen-enriched air, is decreased and the oxygen concentration increased. Accordingly, at low plenum pressures, the oxygen concentration of the oxygen-enriched air may be insufficient and at high plenum pressures the product flow output may be insufficient. [0009] The co-pending related application discloses an oxygen concentration system which obviates many of the disadvantages noted above. However, the oxygen concentration system of the co-pending related application suffers from performance degradation at higher altitudes. SUMMARY OF THE INVENTION [0010] It is an object of the present invention to provide an oxygen concentrator system which utilizes at least one oxygen concentrator subsystem having altitude compensation and a plenum to provide an oxygen-enriched air output. [0011] It is a further object of the present invention to provide an oxygen concentrator system as above and including a plenum charging system to meter and to control the flow of oxygen enriched air between the at least one oxygen concentrator subsystem and the plenum and to allow the flow of oxygen enriched air only from the at least one oxygen concentrator subsystem to the plenum. [0012] It is another object of the present invention to provide an oxygen concentrator system as above and further including a discharging check valve to selectively allow the plenum reserve capacity to flow out only during a high demand oxygen flow. [0013] It is yet another object of the present invention to provide an oxygen concentrator system as above and further including a plenum bypass valve to make the transient response faster and to avoid overdrawing the at least one oxygen concentrator subsystem so as to keep the oxygen concentration of the oxygen-enriched air above a predetermined minimum value. [0014] These and other objects of the present invention may be achieved by providing an oxygen concentrator system with altitude compensation, the system comprising: a system air inlet to receive supply air; at least one system outlet to output oxygen-enriched air; at least one oxygen concentrator subsystem comprising a pair of oxygen PSA (Pressure Swing Adsorption) beds and including an input to receive supply air from the system air inlet and an output to output oxygen-enriched air to the at least one system outlet; a plenum and a plenum charging system located between the output of the at least one oxygen concentrator subsystem and the at least one system outlet, the plenum charging system selectively enabling oxygen-enriched air to flow from the at least one oxygen concentrator subsystem to the plenum; an optional plenum bypass valve to selectively bypass the plenum so as to enable oxygen-enriched air to flow from the at least one oxygen concentrator subsystem to the at least one system outlet; an absolute pressure transducer to provide an electrical signal indicative of a measured ambient barometric pressure; and a monitor/controller to receive the electrical signal from the absolute pressure transducer and to control cycle times of the pair of oxygen PSA beds based on the measured ambient barometric pressure. [0015] The foregoing and other objects may be achieved by providing a method of increasing oxygen concentration, the method comprising: receiving supply air from a system air inlet at an input of at least one oxygen concentrator subsystem comprising a pair of PSA (Pressure Swing Adsorption) oxygen beds and outputting oxygen-enriched air to at least one system outlet; selectively enabling oxygen-enriched air to flow from the at least one oxygen concentrator subsystem to the plenum; optionally selectively bypassing the plenum to enable oxygen-enriched air to flow from the at least one oxygen concentrator system to the at least one system outlet; measuring ambient barometric pressure and providing an electrical signal indicative of the measured ambient barometric pressure; and controlling cycle times of the pair of PSA oxygen beds with a monitor/controller based on the signal representative of the ambient barometric pressure. [0016] The foregoing and a better understanding of the present invention will become apparent from the following detailed description of an example embodiment and the claims when read in connection with the accompanying drawings, all forming a part of the disclosure of this invention. While the foregoing and following written and illustrated disclosure focuses on disclosing an example embodiment of the invention, it should be clearly understood that the same is by way of illustration and example only and that the invention is not limited thereto. This spirit and scope of the present invention are limited only by the terms of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS [0017] The following represents brief descriptions of the drawings, wherein: [0018] [0018]FIG. 1 is a pneumatic diagram of a patient ventilator oxygen concentrator system in accordance with an example embodiment of the invention disclosed in the co-pending related application. [0019] [0019]FIG. 2 is a simplified pneumatic diagram of the patient ventilator oxygen concentrator system of FIG. 1. [0020] [0020]FIG. 3 is a timing diagram illustrating the timing cycles for the oxygen beds of FIG. 1. [0021] [0021]FIG. 4 is a timing diagram illustrating the synchronization between the oxygen beds and air beds of FIG. 1. [0022] [0022]FIG. 5 is a simplified pneumatic diagram of the patient ventilator oxygen concentrator system in accordance with an example embodiment of the present invention. [0023] [0023]FIGS. 6 and 7 respectively illustrate oxygen bed timing diagrams for the low altitude and high altitude cases. [0024] [0024]FIG. 8 is a graph illustrating a comparison in the flow performance of the oxygen concentrator system in accordance with an embodiment of the co-pending related application and the oxygen concentrator system in accordance with an example embodiment of the present invention versus altitude. DETAILED DESCRIPTION [0025] Before beginning a detailed description of the subject invention, mention of the following is in order. When appropriate, like reference numerals and characters may be used to designate identical, corresponding, or similar components in differing drawing figures. Furthermore, in the detailed description to follow, example sizes/models/value/ranges may be given, although the present invention is not limited thereto. Still furthermore, any clock or timing signals in the drawing figures are not drawn to scale but rather, exemplary and critical time values are mentioned when appropriate. When specific details are set forth in order to describe example embodiment of the invention, it should be apparent to one skilled in the art that the invention can be practiced without, or with variations of, these specific details. Lastly, it should be apparent that differing combinations of hard-wired control circuitry and software instructions may be used to implement embodiments of the present invention, that is, the present invention is not limited to any specific combination of hardware and software. [0026] As noted above, while the patient ventilator oxygen concentrator system disclosed in the co-pending related application offers numerous advantages over prior art concentrator systems, it nevertheless has a problem in that its performance is degraded at higher altitudes, particularly above 6000 feet. By the addition of an absolute pressure transducer, the present invention enables the oxygen concentrator system to maintain its performance at higher altitudes, namely, between 6000 and 13,000 feet. [0027] [0027]FIG. 1 is a pneumatic diagram of a patient ventilator oxygen concentrator system in accordance with an example embodiment of the invention disclosed in the co-pending related application and FIG. 2 is a simplified pneumatic diagram of the patient ventilator oxygen concentrator system of FIG. 1. The following discussion refers both to FIG. 1 and FIG. 2. [0028] As illustrated in FIG. 1, the oxygen concentrator system 100 includes three main elements, namely, a plenum system 30 , a front panel assembly 40 , and a bed module 50 . A fourth element of the oxygen concentrator system 100 includes a monitor/controller 200 and input/output electrical panel 210 having switches and indicators and a display. For simplicity, the fourth element of the oxygen concentrator system has been omitted from FIG. 1 but is illustrated in FIG. 2. [0029] As illustrated in FIG. 1, supply air is input into the plenum system 30 . Relief valve RV 1 is provided to protect the system from overpressures. Similarly, relief valves RV 2 -RV 4 are also included in the system to protect against overpressures. After passing through filters FLTR 1 and FLTR 2 , and pressure regulator REG 1 , the supply air is fed to solenoid valves SV 1 , SV 2 , and SV 7 . [0030] The three two-way solenoid valves SV 1 , SV 7 , and SV 2 respectively control the inputting of the supply air to the medical air modules AIR- 1 and AIR- 2 and to the oxygen PSA modules O 2 - 1 and O 2 - 2 , O 2 - 3 and 02 - 4 of the bed module 50 . Each of the medical air modules AIR- 1 and AIR- 2 includes its own two-way solenoid valve SV 12 and SV 13 which allows the supply air to selectively enter and exit respective air beds 1 and 2 . [0031] Similarly, each of the oxygen and PSA modules O 2 - 1 to O 2 - 4 includes its own three-way solenoid valve SV 8 -SV 11 which allows the supply air to selectively enter and exit oxygen beds 1 - 4 . The other connection of all of the two-way solenoid valves SV 8 -SV 13 are connected together to a muffler MUF whose output is connected to an exhaust output of the plenum system 30 . Orifices ORF 5 - 0 RF 7 are respectively disposed between oxygen beds 1 and 2 and between oxygen beds 3 and 4 and between air beds 1 and 2 . Check valves CV 1 -CV 6 are respectively connected to the air beds 1 and 2 and the oxygen beds 1 - 4 . [0032] The output of air beds 1 and 2 are connected via check valves CV 1 and CV 2 to serially connected filters FLTR 3 and FLTR 4 whose output is in turn connected via solenoid valve SV 6 and regulator REG 4 to a medical air line which is connected to the front panel assembly 40 . A source of backup medical air, for example, a compressed air tank, is connected to the solenoid valve SV 6 so as to provide a continuous source of medical air should the oxygen concentrator system fail. [0033] Various monitoring devices, such as: a carbon monoxide monitor 120 connected to the medical air line via the orifice ORF 4 and having an output connected to a vent, a dewpoint monitor 130 connected to the medical air line, the relief valve RV 2 connected to the monitor air line, a pressure switch PSW 2 for detecting a low-pressure in the medical air line, and a gauge G 3 located on the front panel assembly 40 to indicate the actual medical air line pressure, have been provided. [0034] The medical air line is connected to a solenoid valve SV 5 so as to be selectively connected to an oxygen sensor 140 which includes a regulator REG 5 to control the pressure therethrough. The medical air line is also connected to a manifold having 4 valves V 5 -V 8 whose outputs are respectively connected to AIR OUT 1 - 4 . [0035] The outputs of oxygen enriched air beds 1 and 2 are connected together to orifice 0 RF 1 while the outputs of oxygen enriched air beds 3 and 4 are connected together to orifice 0 RF 2 . The outputs of orifice ORF 1 and orifice 0 RF 2 are connected together to the plenum 110 via back pressure regulator REG 2 and filter FLTR 5 . The output of the plenum 110 is connected via solenoid valve SV 4 and regulator REG 3 to an oxygen line on the front panel assembly 40 and via a filter FLTR 6 and regulator REG 5 to a low-pressure oxygen line on the front panel assembly 40 . [0036] The oxygen line on the front panel assembly 40 is connected to a manifold having four valves V 1 -V 4 whose outputs are respectively connected to O 2 OUT 1 - 4 . A gauge G 2 is located on the front panel assembly 40 and is connected to the oxygen line so as to indicate the actual oxygen line pressure. A plenum pressure gauge G 1 and a pressure switch PSW 4 as well as orifice 0 RF 3 are also connected to the output of the plenum 110 . [0037] The output of the orifice 0 RF 3 is connected via solenoid valve SV 3 and valve V 9 to the exhaust of the system so as to allow the purging of the contents of the plenum 110 . A source of backup oxygen, such as a tank of compressed oxygen, is connected to the solenoid valve SV 4 to provide a continuous source of oxygen should be oxygen concentrator system fail. Pressure switch PSW 1 and relief valves RV 3 and RV 4 are also provided. [0038] Lastly, the low-pressure oxygen line is respectively connected via check valves CV 1 and CV 2 to flow meters FLM 1 and FLM 2 whose outputs are respectively connected to LOW P O 2 OUT 1 - 2 . [0039] Referring to FIG. 2, which is a simplified pneumatic diagram of the patient ventilator oxygen concentrator system of FIG. 1, some elements have been consolidated for simplicity and other elements, such as the relief valves, have not been shown so as not to obscure the features of the system. Similarly, other elements, such as the monitor/controller 200 , were not shown in FIG. 1 but are shown in FIG. 2. [0040] The operation of the concentrator system illustrated in FIGS. 1 and 2 is as follows. Air is supplied to the supply air inlet where it is received by the inlet pressure regulator and filter assembly REG 1 , FLTR 1 and FLTR 2 . The pressure regulator REG 1 regulates the air pressure of the air supplied to the air inlet so as to be at a constant value, for example, 80 PSIG. The filters FLTR 1 and FLTR 2 remove particulate matter and water which may be present in the air supplied to the air inlet. A line labeled DRAIN is used to convey the remove water to the EXHAUST via an element labeled EXHAUST SUM which may be a manifold, for example. [0041] The oxygen PSA sub-systems 1 and 2 respectively include oxygen beds 1 and 2 and oxygen beds 3 and 4 . Each bed comprises a molecular sieve bed which generates an oxygen product gas by the pressure-swing-adsorption method. Quantitatively, each subsystem may be designed to generate up to 10 liters per minute of oxygen product at an oxygen concentration of 93+/−3%. [0042] The medical air sub-system consists of air beds 1 and 2 which may each include an activated alumina air dryer bed which operates in the pressure-swing-adsorption mode, a micron filter to remove particulates and an odor removal filter, such as activated charcoal. Quantitatively, the medical grade air sub-system may be designed to generate up to 150 liters per minute of medical air, for example. [0043] As illustrated in FIG. 3, oxygen beds 1 - 4 are each cycled between a charging cycle and a flushing cycle. PSA beds typically have a charging cycle equal to 55% of the total cycle time and a flushing cycle equal to 45% of the total cycle time. As illustrated in FIG. 3, beds 1 and 2 have an overlap and beds 3 and 4 also have an overlap. As an example, the total cycle time may be on the order of 12 seconds with the overlap time being on the order of 0.5 seconds. By having two sets of oxygen PSA sub-systems, it is possible to operate one oxygen PSA sub-system when the demand for oxygen is below a preset amount and to operate both PSA sub-systems when the demand for oxygen exceeds the preset amount. [0044] In a similar fashion, air beds 1 and 2 also cycle between a charging cycle and a flushing cycle. As an example, the total cycle time for the air beds may be four times that of the oxygen beds. Accordingly, the total cycle time may be on the order of 48 seconds and the default overlap time may be on the order of 3 seconds with the PSA time being 21 seconds. [0045] [0045]FIG. 4 is a timing diagram illustrating the synchronization between the air beds and the oxygen beds. While it is not absolutely necessary for the sets of air beds and oxygen beds to be in synchronization with each other, the synchronization therebetween can simplify the monitor controller/ 200 . [0046] The monitor/controller 200 , in conjunction with the input/output panel 210 , is used to activate and switch the various valves utilized in the system. Furthermore, in conjunction with the carbon monoxide sensor 120 , dew point sensor 130 and oxygen sensor 140 and self-test valve SV 5 , the monitor/controller monitors the oxygen concentration in the oxygen product gas, as well as monitoring the dewpoint level and carbon monoxide level and the oxygen concentration in the medical grade air. Based on the status of the system, as a monitored by the monitor/controller 200 , status indications may be displayed on the input/output panel 210 utilizing a digital display or LED indicators, for example. [0047] Since the oxygen sensor 140 output varies with altitude, the absolute pressure regulator REG 5 is provided to keep the pressure of the oxygen sensor's chamber at a relatively constant value, for example, 16 PSIA so as to allow the system to operate at various altitudes without requiring the recalibration of the oxygen sensor 140 . [0048] The muffler MUF has been provided so has to reduce the noise caused by the exhausts from the oxygen PSA sub-systems 1 and 2 and the medical air sub-system since it is common to utilize oxygen concentrator systems in hospital environments requiring low noise levels. [0049] Initially, during startup of the system, and particularly when there is no pressure in the plenum 110 , the monitor/controller 200 activates, that is, allows gas to flow therethrough, the dump valve SV 3 and deactivates, that is, prevents gas from flowing therethrough, the plenum bypass valve BPV so as to flush the plenum 110 of any residual gas contained therein. [0050] Alternatively, on start-up, we flow gas through SV 3 until the oxygen is above 90%. Then SV 3 closes to the vent line and the plenum pressure will increase to normal operating pressure. [0051] The oxygen PSA sub-systems 1 and 2 are then operated so as to produce the output oxygen product which flows through the charging check valves CV 1 - 4 and charging control orifices ORF 1 and ORF 2 and the flow control regulator REG 2 into the plenum 110 . The oxygen concentration of the oxygen product leaving the plenum 110 is measured by the oxygen sensor 140 . [0052] When the oxygen concentration exceeds a predetermined amount, for example, 90%, as measured by the oxygen sensor 140 , the dump valve SV 3 is opened so as to allow the oxygen product from the oxygen PSA sub-systems 1 and 2 to charge the plenum 110 via a charging control circuit including the charging check valves CV 1 - 4 , the charging control orifices 0 RF 1 and 0 RF 2 , and the flow control regulator REG 2 . The charging control circuit limits the charging rate to a level which is less than a maximum output from the oxygen PSA sub-systems 1 and 2 when the plenum pressure is below the switch point of the plenum pressure switch PSW 4 , for example, 65 PSIG so as not to overdraw the oxygen PSA sub-systems 1 and 2 . [0053] When the plenum pressure switch PSW 4 changes state to indicate to the monitor/controller 200 that the pressure at the output of the plenum 110 is above its setpoint, the monitor/controller 200 opens the plenum bypass valve BPV to allow the oxygen product to flow directly to the various oxygen outlets. The direct flow of the oxygen product to the oxygen outlets rather than flowing through the plenum 110 enables the system to respond faster to transients such as line pressure changes or output flow changes. [0054] When the system is in a high oxygen flow mode, for example, a 65 liters per minute purge flow, the discharging check valve DCV opens to the pressure drop downstream of the check valve DCV to discharge the plenum 10 and thereby allow the high-pressure purge. The reserve capacity of the plenum 110 is mainly used for purging for short periods of time, such as 18 seconds, for example. Upon the completion of the purging, the charging control circuit trickle charges the plenum 110 when the output pressure of PSA sub-systems 1 and 2 is higher than the plenum pressure. That is, excess capacity of the PSA sub-systems 1 and 2 are used to recharge the plenum to maintain its reserve capacity. [0055] Unfortunately, as illustrated in FIG. 8 by the points labeled with triangles, the oxygen concentrator system noted above suffers performance degradation above a certain altitude, for example, at altitudes above 6000 feet. [0056] [0056]FIG. 5 is a simplified pneumatic diagram of the patient ventilator oxygen concentrator system in accordance with an example embodiment of the present invention. The system of FIG. 5 differs from that of FIG. 2 in that an absolute pressure transducer 666 has been added. [0057] The absolute pressure transducer 666 has an electrical output signal which is inputted to the monitor/controller 200 , the electrical output signal being indicative of the measured absolute pressure, that is, the measured barometric pressure. During the startup of the oxygen concentrator system, the monitor/controller 200 utilizes the electrical output signal to determine the suitable cycle times for the oxygen beds at the measured barometric pressure. If the system is at a fixed location, the cycle times can remain fixed after startup of the oxygen concentrator system. On the other hand, if the oxygen concentrator system is located in a moving vehicle or aircraft which can change altitudes, then the monitor/controller 200 can be programmed to again determine the suitable cycle times for the oxygen beds at either periodic time intervals or if the measured barometric pressure changes by more than a predetermined amount. [0058] The suitable cycle times for the oxygen beds, and for the air beds, versus barometric pressure are most easily determined empirically utilizing prototype oxygen and air beds. The then determined suitable cycle times for the oxygen beds and for the air beds versus barometric pressure may then be stored in a look-up table for the monitor/controller 200 and then retrieved by the monitor/controller 200 to set the most suitable cycle times for the oxygen beds and for the air beds. Table I is an example of the cycle times (in seconds) of both the oxygen bed cycles and the air beds cycles for both low flow and high flow versus barometric pressure (in mm of mercury). Barometric Oxygen Bed pressure Cycle Air Bed Cycle (mmHg) Low Flow High Flow Low Flow High Flow >620 11 s 11 s 44 s 44 s 600-620 11 s 12 s 44 s 48 s 580-600 11 s 13 s 44 s 52 s 560-580 11 s 14 s 44 s 56 s 540-560 11 s 15 s 44 s 60 s 520-540 11 s 16 s 44 s 64 s 490-520 11 s 17 s 44 s 68 s <490 11 s 18 s 44 s 78 s [0059] [0059]FIGS. 6 and 7 respectively illustrate oxygen bed timing diagrams for the low altitude and high altitude cases. FIG. 6 illustrates the low altitude case, for example, at a barometric pressure greater than 620 mm of mercury. The upper waveform illustrates the timing cycle for oxygen bed 1 while the lower waveform illustrates the timing cycle for oxygen bed 2 . A “high” level indicates that the bed is charging while a “low” level indicates that the bed is flushing. [0060] For exemplary purposes, the cycle times of oxygen beds 1 - 4 are shown at a 55% charging/45% flushing duty cycle. The present invention is not limited thereto. Furthermore, a cycle time is defined to be equal to a charging cycle and a flushing cycle of a bed. [0061] Similarly, FIG. 7 illustrates the high altitude case, for example, at a barometric pressure less than 490 mm of mercury. The upper waveform illustrates the timing cycle for oxygen bed 1 while the lower waveform illustrates the timing cycle for oxygen bed 2 . [0062] As illustrated in FIGS. 6 and 7, the cycle time at a low altitude is 11 seconds whereas at a high altitude, the cycle time increases to 18 seconds. This reflects the decreased amount of available oxygen at a high altitude as compared with the amount of oxygen available at a low altitude. That is, it requires a greater period of time to increase the oxygen concentration of a supply of a air when the supply of a air initially has a lower oxygen partial pressure (which is the case at higher altitudes). [0063] [0063]FIG. 8 is a graph illustrating a comparison in the flow performance of the oxygen concentrator system of the co-pending related application and the oxygen concentrator system of the present invention versus altitude. As shown therein, in comparing the oxygen concentrator system of the co-pending related application having a fixed 12 second cycle time for all altitudes with the oxygen concentrator system of the present invention having a variable cycle time in the range of 11-18 seconds, it is clear that both systems operate effectively, that is, maintain a flow of 20 liters per minute up to an altitude of 6000 feet. Above 6000 feet, the system in accordance with the present invention maintains a flow of 20 liters per minute up to an altitude of 13,000 feet. On the other hand, the system of the co-pending related application reduces its flow as the altitude increases such that its flow is reduced to below 5 liters per minute at an altitude of 13,000 feet. [0064] This concludes the description of the example embodiment. Although the present invention has been described with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this invention. More particularly, reasonable variations and modifications are possible in the component parts and/or arrangements of the subject combination arrangements within the scope of the foregoing disclosure, the drawings, and the appended claims without departing from the spirit of the invention. In additions to variations and modifications in the component parts and/or arrangements, alternative uses will also be apparent to those skilled in the art. [0065] For example, the number of oxygen beds and oxygen PSA sub-systems is not limited to the number shown in the illustrative embodiment. Furthermore, the present invention is not limited to the exact arrangement of solenoid valves, check valves, relief valves, pressure switches, and pressure regulators shown in the illustrative embodiment. Still furthermore, the bypass valve and discharge check valve may be omitted in some configurations.
An oxygen concentrator system with altitude compensation includes at least one oxygen concentrator sub-system and a plenum subsystem. The at least one oxygen concentrator sub-system produces oxygen-enriched air which is outputted to both the oxygen concentrator system output and to a plenum chamber within the plenum subsystem. The plenum chamber is trickle charged with the oxygen-enriched air when the at least one oxygen concentrator sub-system produces an excess amount of oxygen-enriched air. Should the demand for oxygen-enriched air exceed the capability of the at least one oxygen concentrator sub-system, additional oxygen-enriched air is provided by the plenum chamber until such time that the capability of the at least one oxygen concentrator sub-system exceeds the demand for oxygen-enriched air. At that time, oxygen-enriched air is no longer provided by the plenum chamber, but rather the plenum chamber is again trickle charged. A monitor/controller having an absolute pressure transducer controls the cycle times of the oxygen concentrator subsystem in accordance with an ambient barometric pressure measured by the absolute pressure transducer.
1
FIELD OF THE INVENTION [0001] The field of the invention is the O-alkylation of dianhydrohexitols. [0002] In particular, the present invention relates to the preparation of ether derivatives of 1,4:3,6-dianhydrohexitol such as isosorbide, isoidide or isomannide. [0003] More precisely, the invention targets a novel industrial process for etherification of these dianhydrohexitols by means of light alcohols such as methanol or ethanol, by acidic catalysis or bifunctional acid-metal catalysis, preferably in the gas phase. TECHNOLOGICAL BACKGROUND AND PRIOR ART [0004] The known 1,4:3,6-dianhydrohexitols are in particular: isosorbide, isomannide and isoidide of formula: [0000] [0005] Also known are derivatives of isosorbide, isomannide and isoidide wherein the reactive —OH functions are replaced by reactive amine, acid or ether functions. [0000] [0000] is an example of an ether derivative of isosorbide. DMI is a recommended solvent in pharmaceutical and cosmetic compositions such as self-tanning, oral hygiene or anti-acne compositions, skin care creams, ointments and lotions. DMI is also a viscosity control agent. It can be used as a fluxing agent for bitumens. [0006] The use of DMI in many fields other than the pharmaceutical and cosmetic industry is in particular described in the Applicant's international applications WO 2006/120342 and WO 2006/120343. [0007] DMI is typically prepared by methylation of isosorbide with a methylating agent such as dimethyl sulfate or methyl chloride, in the presence of an alkaline agent such as soda. For economic reasons, methyl chloride is a particularly advantageous methylating agent. It is in fact available on the market in large quantities and at a cost lower than that of the brominated or iodinated equivalents. Thus the patent application EP 0 092 998 describes the methylation of isosorbide with methyl chloride (MeC1) in the presence of sodium or potassium hydroxide. The reaction described is performed in a water/aprotic organic solvent (DMSO or toluene) dispersion, bubbling in the gaseous methylating agent. [0008] Although it affords high yields of DMI (90-95%), this methylation in an aqueous medium nonetheless poses the following problems: (i) hydrolysis of the methylating agent. In fact, this undesirable side reaction reduces the ratio [MeC1 bound/MeCl introduced], hereinafter referred to as the MeCl binding ratio, and leads to the formation of considerable quantities of salts, generally sodium chloride or potassium chloride, which must be removed at the end of the process (ii) gaseous reagent difficult to use (iii) toxicity of the methyl chloride reagent (iv) toxicity of the solvent (DMSO or toluene). [0013] The use of dialkyl carbonate (dimethyl or diethyl) to obtain DMI from isosorbide does not involve these disadvantages (i), (ii), (iii) and (iv). This methylating agent is used both as reagent and “green” solvent. It is used in the presence of a basic catalyst. The reaction takes place at high temperatures and pressures and utilizes only one methyl group of the dimethyl carbonate, which adversely affects the economics of the process (U.S. Pat. No. 4,770,871; WO 2009/120703). In particular, this latter international patent application WO 2009/120703 describes a process for etherification of the dianhydrohexitol sugars in the presence of an O-alkylating agent which is a dialkyl carbonate. [0014] There is thus a need for a clean method for synthesis of DMI and more generally of di, without generation of salts in particular, with an inexpensive and efficient methylating agent (without loss of carbon). [0015] It must be noted that the prior art does not meet this need. OBJECTIVES [0016] In this context, the present invention aims to meet at least one of the objectives stated below. [0017] One of the essential objectives of the present invention is to provide a novel improved process for preparing a composition based on dialkyloxydianhydrohexitols by etherification of dianhydrohexitols with at least one alkylating agent. [0018] Another essential objective of the invention is to provide a novel, improved, simple and economical process for preparing a composition based on dialkyloxydianhydro-hexitols by etherification of dianhydrohexitols with at least one alkylating agent. [0019] Another essential objective of the invention is to provide a novel improved process for preparing a composition based on dialkyloxydianhydrohexitols by etherification of dianhydrohexitols with at least one alkylating agent, said process not generating any troublesome side product. [0020] Another essential objective of the invention is to provide a novel improved process for preparing a composition based on dialkyloxydianhydrohexitols by etherification of dianhydrohexitols with at least one inexpensive alkylating agent. [0021] Another essential objective of the invention is to provide a novel improved process for preparing a composition based on dialkyloxydianhydrohexitols by etherification of dianhydrohexitols with at least one non-toxic, non-hazardous and ecologically compatible alkylating agent. [0022] Another essential objective of the invention is to provide a novel improved process for preparing a composition based on dialkyloxydianhydrohexitols by etherification of dianhydrohexitols with at least one alkylating agent, said process being easy to industrialize and hence for example capable of being operated continuously. [0023] Another essential objective of the invention is to provide a novel improved process for preparing a composition based on dialkyloxydianhydrohexitols by etherification of dianhydrohexitols with at least one alkylating agent, said process having favorable thermodynamics and hence good reaction kinetics. [0024] Another essential objective of the invention is to provide a novel improved process for preparing a composition based on dialkyloxydianhydrohexitols by etherification of dianhydrohexitols with at least one alkylating agent, with good yields and good selectivity for dialkyloxydianhydrohexitols. [0025] Another essential objective of the invention is to provide a novel improved process for preparing a composition based on dimethyl isosorbide by etherification of isosorbide with methanol, said process meeting at least one of the aforesaid objectives. BRIEF DESCRIPTION OF THE INVENTION [0026] These objectives, among others, are attained by the present invention which first of all relates to a method for preparing a composition based on dialkyloxydianhydrohexitols by etherification of dianhydrohexitols with at least one alkylating agent, in the presence of a solid catalyst, preferably a catalyst exhibiting Lewis acid or Brønsted acid properties, the etherification agent being selected from the group comprising, and better still consisting of: alcohols, preferably linear or branched aliphatic alcohols and, more preferably still, C1-C20 alcohols, better still methanol, ethanol, isopropanol or tert-butanol, methanol being particularly preferred, olefinic precursors of these alcohols, and mixtures thereof. [0030] This efficient novel method is perfectly suited to industrial utilization. It enables the synthesis of methyl isosorbide ethers by reaction of isosorbide with methanol (or ethanol) in the presence of a solid acidic catalyst. [0031] The method according to the invention is “clean”, it circumvents the use of a methylating agent such as dimethyl sulfate or methyl chloride which generates stoichiometric quantities of salts. It also avoids the use of dialkyl carbonate, a more expensive methylating agent only one of whose two methyl groups is involved in the obtention of the mixed ethers of isosorbide. DEFINITIONS [0032] In the present description, any singular designates equally a singular and a plural and vice versa, unless otherwise stated. [0033] The following definitions are given as examples for the understanding of the present description. “dialkyloxydianhydrohexitol” is understood to mean a derivative of 1,4:3,6-dianhydrohexitol of formula III: [0000] wherein: R 10 and R 20 is an —OR 30 radical, the radicals R 30 being identical or different and each corresponding to an alkyl, preferably a linear or branched aliphatic alkyl and, still more preferably, a C1-C20 alkyl, better still methyl, ethyl, isopropyl or tert-butyl, methyl being particularly preferred, which corresponds to dimethyl isosorbide (DMI) as the compound of formula (III). “O-alkylation” is understood to mean grafting of an alkyl onto a product by an ether bond. “between x and y” is understood to mean a range or ranges of values the limits whereof are closed: [x,y]. “solid catalyst” is understood to mean a solid chemical compound which constitutes a distinct phase of the reaction phase capable of exerting an accelerating effect and a directing effect on the progress of a thermodynamically possible conversion and remaining unchanged at the end of the reaction and not being capable of modifying the thermodynamic equilibrium (“Catalyse de contact” [Contact Catalysis]—J. P. Le Page—Editions Technip, 1978, pages 1-2). “supported solid catalyst” is understood to mean a solid catalyst consisting of an inert support of large specific area on which a catalytically active chemical compound is dispersed (“Catalyse de contact”—J. P. Le Page—Editions Technip, 1978, page 133). “conversion”, in particular “isosorbide conversion” (also written as “Isosorbide cony.”) is understood to mean: Isosorbide cony. (%)=100*(initial number of mole(s) of isosorbide−final number of mole(s) of isosorbide)/initial number of mole(s) of isosorbide. “selectivity” (also written as sel.) is understood to mean: Product i Sel. (mole %)=(100*No. moles of product i)/(sum No. moles of products i), i designating the isosorbide derivatives: DMI or MMI A or MMI B. In the present application, the selectivity are thus calculated by normalization to 100 molar % for the isosorbide derivatives. DETAILED DESCRIPTION OF THE INVENTION Preferences Preferred Embodiment Gas Phase [0046] In this preferred embodiment, the etherification is at least partly effected in the gas phase. [0047] Performing the reaction in the gas phase enables in particular the obtention of colorless reaction products. [0048] Catalyst [0049] The catalyst is preferably selected from the group comprising and, better still, consisting of: 1. salts of heteropolyacids or polyoxometallates of general formula: [0000] H k X j M m O n .y H 2 O  (I) wherein, X represents a heteroatom selected from the group consisting of the following elements: P, Si, Ge, B and As, M represents a peripheral metallic element selected from the group consisting of W, Mo and V, j is the number of heteroatoms and represents 1 or 2, k is the number of hydrogen atoms and is between 0.5 and 10, m is the number of peripheral metal atoms W, Mo and V and is between 1 and 18, n is the number of oxygen atoms and is between 2 and 62, y is the number of molecules of water of hydration and is between 0 and 40, preferably between 6 and 30, and mixtures thereof; 2. salts of alkali metals Cs + , K + , Rb + and ammonium (NH 4 + ) salts, the latter being preferred, and mixtures thereof, 3. acidic catalysts based on zirconium oxide modified with oxo anions of the sulfate or tungstate type referred to as ZrS or ZrW possibly containing transition metals such as Fe, Mn and mixtures thereof, 4. zeolites, preferably selected from the group comprising and, better still, consisting of: H-beta, H-ZSM-5, MCM-22, H-USY, and mixtures thereof, 5. acidic clays of the montmorillonite type, phosphates such as Nb or zirconium phosphate, functionalized carbons, in particular carbons functionalized with sulfonic groups, 6. and mixtures thereof. [0064] Preferably, for the catalyst, the salts of the heteropoly-acids (polyoxometallates) of general formula (I) are selected from the group comprising and, better still, consisting of: H 3 PW 12 O 40 .21H 2 O, H 4 SiW 12 O 40 . 24H 2 O, H 6 P 2 W 18 O 62 .24H 2 O, H 5 BW 12 O 40 .30H 2 O, H 5 PW 10 V 2 O 40 .yH 2 O, H 3 PMo 12 O 40 .28H 2 O, H 4 SiMo 12 O 40 .13H 2 O, H 3 PMo 6 V 6 O 40 .yH 2 O and H 5 PMo 10 V 2 O 40 .yH 2 O, and mixtures thereof. [0065] Advantageously, the solid catalyst is a supported catalyst. [0066] Bifunctional Catalyst [0067] According to an advantageous possibility afforded by the invention, the catalyst is a bifunctional metal-acid catalyst, that is to say that: (i) the catalyst comprises a noble metal (preferably selected from the group comprising and, better still, consisting of gold, platinum, palladium and ruthenium, possibly modified by the addition of rhenium, osmium and iridium, titanium, zirconium, tantalum, or mixtures or alloys thereof), (ii) and the etherification is at least partly effected under a stream of hydrogen. [0070] The use of a bifunctional metal-acid catalyst and the addition of hydrogen to the reagents stream, in particular when these are gaseous, makes it possible to stabilize the catalytic activity. This thus combats the loss of activity of the catalyst due for example to poisoning of the acidic sites by strong adsorption of oligomers. The bifunctional metal-acid catalyst enables the in situ hydrogenation of the precursors of these oligomers. [0071] According to one possibility, the solid catalyst is selected from those having a differential heat of adsorption of ammonia (in kJ/mole) greater than or equal to 100, preferably 120 or, better still, between 120 and 200. [0072] “Differential heat of adsorption of ammonia Qdiff” is understood to mean, for example, the quantity of heat dQ released by the adsorption of an infinitely small quantity of gaseous ammonia do at constant temperature on the catalyst initially under vacuum Qdiff=dQ/dn expressed in kJ/mole according to “Les techniques physiques d′etude des catalyseurs” [Physical techniques for the study of catalysts]—Editions Technip—Editors B. Imelik and J. C. Vedrine, 1988, as hereinafter defined in the examples. [0073] Catalyst Regeneration [0074] Another advantageous means of combating the loss of activity of the catalyst is to include a solid catalyst regeneration stage, preferably by treatment under O 2 at high temperature, in the process. [0075] “High regeneration temperature” for example refers to temperatures (° C.) of between, in increasing order of preference, 400 and 600° C. or better still 450 and 500° C. [0076] Cycles of regeneration of the used catalyst by treatment under oxygen at high temperature make it possible to regenerate its activity and endow it with resistance to poisoning. [0077] Reagents [0078] According to a preferred embodiment of the invention, the dianhydrohexitols comprise a derivative of 1,4:3,6-dianhydrohexitol of formula II: [0000] [0080] wherein: R 1 and R 2 is an —OR 3 radical, the radicals R 3 being identical or different and each corresponding to H or an alkyl, and the dialkyloxydianhydrohexitols comprise a derivative of 1,4:3,6-dianhydrohexitol of formula III: [0000] [0083] wherein: R 10 and R 20 is an —OR 30 radical, the radicals R 30 being identical or different and each corresponding to an alkyl, preferably a linear or branched aliphatic alkyl and, still more preferably, a C1-C20 alkyl, better still methyl, ethyl, isopropyl or tert-butyl, methyl being particularly preferred, which corresponds to dimethyl isosorbide (DMI) as the compound of formula (III). [0085] The etherification agent is selected from the group comprising or, better still, consisting of: alcohols, preferably linear or branched aliphatic alcohols, more preferably still C1-C20 alcohols, better still methanol, ethanol, isopropanol or tert-butanol, methanol being particularly preferred, the olefinic precursors of these alcohols, and mixtures thereof. [0089] Quantitative Data [0090] According to another outstanding characteristic of the invention, the [alkylating agent/dianhydrohexitol] mole ratio is less than or equal to, in increasing order of preference: 30, 25, 20, 10, 5, 4, 3, 2 or better still between 2 and 20. [0091] Methodology [0092] The process is preferably implemented according to a continuous or semi-continuous mode. The reaction is advantageously performed in a continuous reactor and in the gas phase at high temperature. “High reaction temperature” for example refers to temperatures (° C.) superior or equal to between, in increasing order of preference, 160-300 and better still between 180-240. Operating in a continuous reactor has the advantage of giving a colorless reaction product in contrast to operation in a batch reactor in the liquid phase, which is characterized by longer contact times, favorable to the formation of generally colored side products, probably oligomers of the dianhydrohexitols (e.g. isosorbide). [0093] As regards the heating, it is advantageous that: 1. in a first stage, the dianhydrohexitol(s) is/are vaporized at a temperature of T1 (in ° C.) greater than or equal to 170, preferably 180, T1 still more preferably being between 190 and 300, 2. and in a second stage the etherification is effected with the alkylating agent at a temperature T2 (in ° C.) greater than or equal to T1, preferably greater than or equal to 180, T2 still more preferably being between 200 and 300. [0096] According to an outstanding characteristic of the invention, the starting dianhydrohexitol(s) is/are melted in solution and/or derive(s) directly from the synthesis of dianhydrohexitol(s) from hexitol(s). The starting dianhydrohexitol(s) advantageously derive(s) directly from a purification stage performed during the synthesis of dianhydrohexitol(s) from hexitol(s), in particular a distillation stage. The dehydration of the hexitol can be catalyzed by the etherification catalyst in a single stage combining the dehydration of the hexitol to dianhydrohexitol and the etherification of the dianhydrohexitol. [0097] Moreover, given that the reaction of etherification of dianhydrohexitols (e.g. isosorbide) is a consecutive reaction leading to the obtention of monoalkyl ethers (e.g. monomethyl ethers or monoethyl ethers) A and B and dialkyl ethers (e.g. dimethyl ether or diethyl ethers of isosorbide), it seemed advantageous, according to a particular embodiment of the invention, to install a loop for recycling reaction products in order to favor the obtention of the final products, namely the dialkyloxydianhydrohexitols (e.g. dimethyl isosorbide). [0098] Applications [0099] The method according to the invention is an industrial process utilizable by producers of hexitols such as sorbitol or of anhydrohexitol such as isosorbide. This process results in a composition based on dialkyloxydianhydrohexitols (e.g. ethers of isosorbide such as the dimethyl ether or the diethyl ether). These products have uses in particular as fluxing agents for bitumen, as solvent, or in pharmaceutical or cosmetic compositions. [0100] Other details of the invention will appear more clearly in the light of the examples given below for illustration. Examples 1. Apparatus [0101] 1.1 Liquid Phase [0102] The reactor used is an autoclave equipped with a magnetic stirrer. The liquid reagents are introduced, the alcohol then the isosorbide, and finally the solid catalyst. The autoclave is inerted under 20 bar of argon. It is raised to the reaction temperature by means of electrical resistance heaters. [0103] 1.2 Gas Phase—Continuous Mode [0104] This apparatus, shown on the appended FIG. 1 , comprises: 1. a vaporization oven 2. a reaction oven in the extension of the vaporization oven 1 3. an inlet (duct and pump) for mixing the reagents 4. a nitrogen feed to inert the jackets of the vaporization oven 1 and reaction oven 2 5. a coil in the vaporization oven 1 6. a reaction chamber positioned in the reaction oven 2 and containing the catalyst 6 7. a condenser downstream of the reaction oven 2 8. a cooling bath associated with the condenser 7 9. and an outlet duct for the O-methylated isosorbide. 2. Reagents [0114] The isosorbide (ROQUETTE FRERES) is stored in the refrigerator under an inert atmosphere. The methanol and ethanol are obtained from the supplier Aldrich. 3. Characterization Techniques Used [0115] The analysis of the reaction products is performed by gas phase chromatography equipped with a DB1 30 m×0.32 mm column, after silylation by means of BSTFA (N,O-bis-(trimethylsilyltrifluoroacetamide)). Example 1 O-Methylation of Isosorbide by Methanol in the Presence of an Acidic Potassium Salt of 12-Tungsto-Phosphoric Acid: K 2 HPW 12 O 40 in Batch Reactor, Liquid Phase [0116] The following quantities are introduced into the autoclave: catalyst=2 g, isosorbide=36 g, MeOH/isosorbide mole ratio=5. The catalyst is the acidic cesium salt of 12-tungstophosphoric acid: K 2 HPW 12 O 40 . [0117] At the start of the reaction, the atmosphere in the autoclave consists of 20 bar of Ar. [0118] The reaction mixture is raised to two different temperatures: 180° C. or 200° C. The reaction time is 6 hrs. [0119] At the end of the reaction, the reaction medium is cooled by means of an ice bath. [0120] The liquid reaction products are separated from the reaction medium and analyzed by gas chromatography. The isosorbide conversion and selectivity are calculated in mole % (standardization to 100 mole % of the conversions and selectivity for the isosorbide derivatives). [0121] The results are shown in table 1. [0000] TABLE 1 Conversion and selectivity of the etherification reaction of isosorbide with methanol catalyzed by K 2 HPW 12 O 40 in batch reactor, in liquid phase. Effect of the reaction temperature. Isosorbide conversion Selectivity (mole %) T (° C.) (%) DMI MMI B MMI A 180 26 7 46 35 200 34 9 35 37 [0122] Formation of the monomethylated compounds A and B (MMI A and MMI B) and of dimethyl isosorbide (DMI) is observed at 180° C. and 200° C. with the catalyst K 2 HPW 12 O 40 . However, the selectivity for DMI is low, in particular lower than 10%. [0123] In the liquid phase, the reaction mixtures obtained at both temperatures 180 and 200° C. are strongly colored. [0124] The coloration intensifies with the increase in the reaction temperature. Example 2 O-Methylation of Isosorbide by Methanol Catalyzed by an Acid Potassium Salt of 12-Tungstophosphoric acid: K 2 HPW 12 O 40 in Continuous Reactor, in Gas Phase [0125] The reaction is performed in the apparatus of FIG. 1 . [0126] The following experimental protocol was adopted: sampling of the condensate at the end of one hour (1 hr) and four hours (4 hrs) of reaction, cessation of pumping of the reaction mixture at the end of four hours of reaction. [0129] The experimental conditions were as follows: [0130] Catalyst: K 2 HPW 12 O 40 , m cata =2 g D liq =0.06 ml.min −1 D N2 =8 ml.min −1 P methanol =600 torr P isosorbide =28 torr T vaporization =225° C. T reaction =225° C. Methanol/isosorbide mole ratio=20 ppH iso (hr −1 )=isosorbide mass flow (g.hr −1 )/mass of catalyst (g)=0.26 hr −1 . [0139] The results obtained are shown in table 2. [0000] TABLE 2 O-methylation of isosorbide with methanol catalyzed by K 2 HPW 12 O 40 in continuous reactor, in gas phase. K 2 HPW 12 O 40 Sampling (hrs of reaction) 1 hr 4 hrs Isosorbide conv. (%) 57 32 DMI Sel. (mole %) 62 60 MMI B Sel. (mole %) 30 22 MMI A Sel. (mole %)  8 18 MMI = monomethyl isosorbide [0140] After one hour of reaction, the isosorbide conversion (isosorbide cony.) is 57% with predominant formation of DMI. The selectivity for DMI (DMI Sel.) is 62%. Between hr and 4 hrs, the activity stabilizes at an isosorbide conversion level of about 32%. [0141] Very good conversion of isosorbide to DMI is thus obtained in the gas phase compared to that obtained in the liquid phase (example 1). Moreover, no coloration of the reaction medium occurred in the gas phase reaction. This in particular indicates the absence of degradation of the reaction products in spite of a high reaction temperature. Example 3 O-Methylation of Isosorbide by Methanol Catalyzed by Solid Acidic Zeolite Catalysts in Continuous Reactor, in Gas Phase, at High Temperature [0142] The reaction is performed in the same apparatus as that of example 2. [0143] The following experimental protocol was adopted: sampling of the condensate at the end of one hour and four hours of reaction, cessation of pumping of the reaction mixture at the end of four hours of reaction, with maintenance of the nitrogen flow for 30 minutes. [0146] The experimental conditions were as follows: m cata =2 g D lig =0.06 ml.min −1 D N2 =8 ml.min −1 P methanol =600 torr P isosorbide =28 torr T vaporization =225° C. T reaction =205° C. Methanol/isosorbide mole ratio=20 ppH iso (hr −1 )=isosorbide mass flow (g.hr −1 )/mass of catalyst (g)=0.26 hr −1 . [0156] The results obtained after 1 hr and 4 hrs of reaction are shown in tables 3 and 4 respectively. [0000] TABLE 3 O-methylation of isosorbide with methanol catalyzed by solid acidic zeolite catalysts in continuous reactor in gas phase. Results after 1 hr of reaction. Isosorbide conversion Selectivity (mole %) Catalysts (%) DMI MMI B MMI A Beta 78 34 54 12 ZSM5 76 33 54 13 MCM-22 51 9 73 18 USY 70 35 47 18 [0157] The zeolites catalyze the etherification of isosorbide by MeOH. The proportion of dimethyl ether formed by intramolecular dehydration depends on the zeolite. [0000] TABLE 4 O-methylation of isosorbide with methanol catalyzed by soild acidic zeolite catalysts in continuous reactor in gas phase. Results after 4 hrs of reaction. Isosorbide conversion Selectivity (mole %) Catalysts (%) DMI MMI B MMI A Beta 42 16 51 33 ZSM5 31 14 47 39 MCM-22 8 2 50 48 USY 35 28 43 37 [0158] After 4 hrs of reaction, the acidic zeolite catalysts exhibit lower activity which is accompanied by a decrease in the selectivity for dimethyl isosorbide. However, the Applicant has sought to remedy these disadvantages by increasing the residence time in the catalytic bed (example 5) and/or by using bifunctional metal-acid catalysts. Example 4 O-Methylation of Isosorbide by Methanol Catalyzed by Solid Acidic Non-Zeolite Catalysts in Continuous Reactor in Gas Phase at High Temperature [0159] The following catalysts are evaluated: tungstized zirconia: ZrW sulfated zirconia: ZrS sulfeted zirconia doped with Fe and Mn: ZMFS [0163] The reaction is performed in the apparatus described in example 2. [0164] The following experimental protocol was adopted: sampling of the condensate at the end of 1 hr and 4 hrs of reaction, cessation of pumping of the reaction mixture at the end of four hours of reaction, with maintenance of the nitrogen flow for 30 minutes. [0167] The experimental conditions are the same as those of example 3. [0168] The results obtained after 1 hr and 4 hrs of reaction are shown in tables 5 and 6 respectively. [0000] TABLE 5 O-methylation of isosorbide with methanol catalyzed by solid acidic catalysts ZrS, ZrW and ZMFS in continuous reactor in gas phase. Results after 1 hr of reaction. Isosorbide conversion Selectivity (mole %) Catalysts (%) DMI MMI B MMI A ZrS 42 38 43 19 ZMFS 68 20 55 25 ZrW 63 37 42 21 [0169] The Zr-based acidic catalysts catalyze the etherification of isosorbide by MeOH to methyl ethers. [0000] TABLE 6 O-methylation of isosorbide with methanol catalyzed by solid acidic catalysts ZrS, ZrW and ZMFS in continuous reactor in gas phase. Results after 4 hrs of reaction. Isosorbide conversion Selectivity (mole %) Catalysts (%) DMI MMI B MMI A ZrS 25 13 52 35 ZMFS 9 0 47 53 ZrW 38 11 52 37 [0170] As in the case of the zeolite catalysts, the zirconia-based acidic catalysts appear to exhibit deactivation during their functioning, and this is also accompanied by a decrease in the selectivity for dimethyl isosorbide. Example 5 O-Methylation of Isosorbide by Methanol Catalyzed by H-ZSM5 Zeolite in Continuous Reactor in Gas Phase at High Temperature. Recycling of the Products [0171] The products of isosorbide etherification with methanol obtained at the end of a reaction of 4 hrs conducted under the conditions of example 3 are introduced into the reactor for a new reaction cycle under identical conditions. The reaction conditions are the same as those described in example 3. [0172] The results obtained are shown in table 7. [0000] TABLE 7 Composition of the reaction medium after a first pass then a second pass (recycling of the products) over the catalytic bed. Mole % MMI B MMI A DMI Isosorbide 1 st pass 25 13 6 56 2 nd pass 32 14 19 35 [0173] The recycling of the reaction products over the catalytic bed makes it possible to increase the conversion of the isosorbide and, in particular, the formation of DMI. [0174] The conversion is thus only limited by the residence time in the reactor. A first improvement to be considered would consist in multiplying the catalytic bed in order to increase the residence time of the reagents in the catalytic bed and thus to increase the conversion level. Industrially, it would be a matter of using columns with a greater content of catalyst in order to achieve higher, in particular near quantitative, conversion levels. Example 6 O-Methylation of Isosorbide by Methanol Catalyzed by H-ZSM5, ZrS and ZrW, Variation in Catalytic Activity with Time [0175] The experimental conditions are as follows: m cata =2 g P isosorbide =14 torr T vaporization =185° C. T reaction =200° C. Methanol/isosorbide mole ratio=20 ppH iso (hr −1 )=0.39 g iso.g cata −1 .hr −1 . [0182] The reaction time is 8 hrs with sampling every 2 hrs. [0000] TABLE 8 Variation in isosorbide conversion with time. Isosorbide conversion % Catalysts 2 hrs 4 hrs 6 hrs 8 hrs ZrS 61 30 13 5 ZSM5 53 30 21 17 ZrW 25 13 1 0 [0183] Whatever the catalyst, the activity decreases with the reaction time. However, ZSM5 exhibits significantly higher activity than ZrS and ZrW. Moreover, the activity of ZSM5 stabilizes around 20% isosorbide conversion after 6 hrs of reaction. Example 7 O-Methylation of Isosorbide by Methanol Catalyzed by a Bifunctional Metal-Acid Catalyst: Pt Dispersed on H-ZSM5 in the Presence of Hydrogen [0184] The bifunctional catalyst is prepared by nascent humidity impregnation of 1% Pt by weight onto the H-ZSM-5. [0185] The reaction conditions are the same as those of example 6. [0186] The results are shown in table 9. [0000] TABLE 9 O-methylation of isosorbite by methanol catalyzed by Pt/H-ZSM-5 in the presence of hydrogen. Isosorbide conversion % Mole % 2 hrs 4 hrs 6 hrs 8 hrs Conversion 83 72 61 55 DMI Sel. 32 27 21 18 MMI B Sel. 59 54 50 49 MMI A Sel. 9 19 29 33 [0187] Compared to the monofunctional acidic catalyst H-ZSM-5 (example 6), the addition of Pt to the H-ZSM-5 catalyst coupled with the presence of H 2 in the stream makes it possible to limit the rate of deactivation of the catalyst with time while limiting the decrease in the selectivity for DMI. Moreover, it is probable that optimization of the acidic function/metallic function balance of the catalyst, as well as optimization of the pph iso , could make it possible to limit the deactivation and stabilize the activity. Example 8 O-Ethylation of Isosorbide by Ethanol in Gas Phase Catalyzed by H-ZSM-5 [0188] The reaction conditions are the same as those of example 3. The ethanol/isosorbide mole ratio is 20. The results are shown in table 10. [0000] TABLE 10 O-ethylation of isosorbide by ethanol catalyzed by Pt/H-ZSM-5 in the presence of hydrogen. Isosorbide conversion Selectivity (mole %) Time (%) DEI MEI B MEI A 0 hrs-1 hr 47 23 55 22   1 hr-4 hrs 40 15 57 28 [0189] The O-ethylation of isosorbide by ethanol can be performed in a continuous reactor in the gas phase at high temperature in the presence of the catalyst H-ZSM5. The results obtained at the end of one hour demonstrate the formation of diethyl isosorbide (DEI) and of monoethylated compounds. A decrease in the activity and the selectivity for DEI appears with time. However, the deactivation is less pronounced than in the presence of MeOH.
A method for preparing a dialkyloxydianhyrohexitol (dimethylisosorbide) composition by etherification of dianhydrohexitol (isosorbide). The aim is to achieve a “clean” method that avoids the use of a methylation agent such as dimethyl sulfate or methyl chloride, which generates stoechiometric quantities of salts, or expensive dialkyl-carbonates, wherein only one of the two methyl groups participates in the preparation of mixed isosorbide ethers. The method involves using at least one O-alkylation agent and a catalyst including an acid or an acid salt, preferably a catalyst having Lewis or BrØnsted acid properties. A device for carrying out the method wherein the device includes a vaporization oven and a reaction oven is also described.
2
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims priority of United States Provisional Patent Application filed Sep. 5, 2008 having Ser. No. 61/094,478. FIELD OF THE INVENTION [0002] This invention is related to massagers and more particularly to a user manipulated foot massaging device. BACKGROUND AND SUMMARY OF THE INVENTION [0003] Massage is a well-known technique to increase blood flow and ease muscle tension in a person's body. Typically, in a massage, pressure is applied to a location on the body either by direct hand/finger manipulation or through a device that aids in the application of pressure. [0004] Such devices include both user-manipulated tools and motorized devices which vibrate, knead, and/or rotate to manipulate a desired body part. These massage tools may either be used by the individual receiving the massage or by another person (e.g., a masseuse). [0005] One area of the body that frequently needs the therapeutic effects of massage is the foot, particularly the sole or bottom of the foot. Typical foot massagers have one or more sets of rollers rotatably mounted within a fixed frame. A user rolls his feet across the fixed rollers to apply massaging pressure to the bottom of his foot. These massagers, however, do not allow the user to change the location of the roller(s) in the frame and therefore cannot be configured to optimize the rollers position to target a particular part of the foot. [0006] The broad purpose of the present disclosure is to provide a foot massaging device that has a plurality of foot contacting rollers which can be adjusted to massage various parts of the foot. The massager is adjustable by seating the rearwardly disposed rollers between a raised and lowered position to configure the massager to contact different portions of a user's foot. [0007] The preferred massager includes a frame having opposed vertical walls. Three rollers are adjustably mounted in-parallel between the opposed walls. The rollers are mounted in a spaced relationship such that they present a front, middle and rear roller to a user. The middle and rear rollers being adjustable vertically within channels formed in each wall. In this manner, the middle and rear rollers can be selectively placed in a raised position (relative to the front roller) or in a lowered position where the axis(es) of rotation of the adjustable roller(s) are co-planar with the rotational axis of the front roller. [0008] It is an advantage of the present disclosure that the massaging device allows a user to configure the device to massage a particular part of the foot. [0009] The massager has a first position which aligns all of the rollers in-parallel allowing a user to roll his foot or feet across a substantially horizontal row of spaced massaging rollers. The second position sets the middle roller in the elevated position, while the rear roller is lowered. The second position allows the user to roll his foot along a curved profile to better follow the curvature of the foot's arch. A third position is possible by setting the rear roller in the elevated position, while the middle roller is lowered. In this third position, the front two rollers contact a user's foot bottom, while the rear roller contacts the top of the foot. A fourth position has both the middle and rear rollers in the elevated position, in this fourth position, the massager presents a substantially flat row of rollers that are at an angle relative to the ground (from front to back roller), in this fourth position a user can roll his feet across the rollers while sitting down in substantially the same way as the first position. [0010] It is another advantage of the present disclosure that the rollers can be supplemented with a textured outer surface to further increase and vary the pressure exhibited on the user's feet when rolled across the device. [0011] It is still another advantage of the present disclosure that each of the rollers is comprised of two axially aligned rollers which are independently rotatable about a common axis of rotation. In this manner, a user can roll both feet simultaneously across the rollers at different speeds and/or in opposite directions. [0012] Still further objects and advantages of this disclosure will become readily apparent to those skilled in the art to which the invention pertains upon reference to the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS [0013] The description refers to the accompanying drawings in which like reference characters refer to like parts throughout the several views and in which: [0014] FIG. 1 is a perspective view illustrating a massaging device embodying the invention; [0015] FIG. 2 is a front view of the massaging device; [0016] FIG. 3 is a side view of one of the frame walls, illustrating the roller seat channels; [0017] FIG. 4 is perspective, partially exploded view of a roller assembly; [0018] FIG. 5 is a side schematic view showing the massaging device in a first roller configuration; [0019] FIG. 6 is a side schematic view showing the massaging device in a second roller configuration; [0020] FIG. 7 is a side schematic view showing the massaging device in a third roller configuration; [0021] FIG. 8 is a side schematic view showing the massaging device in a fourth roller configuration; [0022] FIG. 9 is a perspective, partially exploded view of a roller sleeve; and [0023] FIG. 10 is a side, partial cut-away view showing an alternate embodiment of the roller assembly. DETAILED DESCRIPTION OF THE INVENTION [0024] Referring now to FIGS. 1-4 , a preferred foot massaging device or massager 10 is illustrated. Massager 10 includes a frame 12 which supports a plurality of rollers, denoted 14 , 14 a , and 14 b when mounted in frame 12 . [0025] Frame 12 includes a pair of opposed vertical walls 16 which are interconnected by support bars 18 adjacent to the bottom ends of the walls. Each wall 16 is generally triangular in shape, angling from a lower-most front end 16 a to an upper-most rear end 16 b . Frame 12 is preferably formed from a rigid and durable material, such as metal or plastic. Resilient feet members 20 are mounted to the underside of frame 12 . [0026] As best shown in FIG. 3 , each wall 16 includes three roller mounting apertures passing between the outer and inner surfaces of the wall. Each mounting aperture has at least one roller receiving or bearing surface that is equally spaced apart from the adjacent mounting aperture. In the preferred embodiment, the front aperture 22 has a cylindrical through bore. The other two roller mounting apertures 24 and 26 are formed having two roller bearing surfaces or seats formed by a slot or groove passing through the wall. Each slot 24 , 26 has a substantially constant opening width 28 that is equal to the diameter of front aperture 22 . [0027] Both mounting slots 24 , 26 have the same general “question-mark” shape, with a lower seat 24 a , 26 a at the bottom of the slot and an upper seat 24 b , 26 b in an upper portion of the slot. The upper seats 24 b , 26 b are vertically aligned with their respective lower seat 24 a , 26 a . To interconnect the two seats 24 a , 24 b and 26 a , 26 b , each slot has an elongated vertical portion 30 that is offset from the vertically aligned seats. Each portion 30 is preferably offset away from the seats in the direction of the front aperture 22 . As shown, the vertical portion of the rear slot 26 is longer than the vertical portion of middle slot 24 to ensure that the upper seats 24 b and 26 b cooperate with front aperture 22 to form a substantially straight line. [0028] The slot seats 24 a , 24 b and 26 a , 26 b all have a generally semi-circular bottom surface 34 . The lower portion of each slot starts at the lower seat 24 a , 26 a , then rises vertically a distance that is two to fours times the slot width 28 , then turns horizontally to the offset vertical slot portion 30 . The upper portion of each slot 24 , 26 curves up and away from vertical portion 30 returning back to a generally vertical orientation and then terminating at upper seat 26 . [0029] In the preferred embodiment, lower seats 24 a and 26 a are horizontally aligned with front aperture 22 , while the upper seats 24 b and 26 b are also aligned with front aperture 22 at an acute angle to the horizontal. In the preferred embodiment, this angle is in the range of fifteen to sixty degrees. It should be appreciated that each of the respective apertures 22 , 24 , 26 is aligned with an identical aperture formed in the opposing wall. In this manner, the paired roller bearing surfaces (i.e., apertures 22 , seats 24 a and seats 24 b in the opposing walls 16 ) are aligned and are substantially parallel to the ground. [0030] Referring now to FIG. 4 , a roller assembly 14 is shown having a tubular body 36 that concentrically receives an elongated axle 38 . Body 36 rotates about axle 38 via roller bearings 40 (e.g., ball bearings). The outer surface 36 a of the body is generally smooth allowing a user's feet to roll over the surface. [0031] As shown in FIGS. 1 and 2 , the outer ends 42 of the axle passes through the apertures 22 , 24 , 26 and are held within frame 12 by conventional fasteners 44 . Three rollers 14 are mounted between the paired apertures 22 , 24 and 26 wherein each roller body 36 is bounded by the opposing walls 16 and are substantially parallel to each other. The front roller 14 a is mounted within front apertures 22 , the middle roller 14 b is mounted within middle apertures 24 , and the rear roller 14 c is mounted within the rear apertures 26 . It should be appreciated that axle 38 is sized to fit within and slide along the circuitous shape of slots 24 , 26 and is selectively positioned in either of the lower seats 24 a , 26 a or the upper seats 24 b , 26 b (as shown in FIGS. 1 and 2 ). [0032] Referring now to FIGS. 3 and 5 - 8 , the various roller configurations of the massager 10 are illustrated in schematic form depicting each roller's relative position when seated within a particular seat 24 a , 24 b , 26 a , 26 b. [0033] FIG. 5 shows the middle roller 14 b and the rear roller 14 c positioned in the lower seats 24 a and 26 a , respectively, to present a substantially flat rolling surface to the bottom 48 of a user's foot 50 allowing the foot (or feet) to follow a substantially flat motion as shown in arrow 51 . [0034] FIG. 6 shows the middle roller 14 b positioned in the upper seats 24 b , while the rear roller 14 c is in the lower seats 26 a to present a convex curved surface, which follows the arch shape of a the bottom 48 of the foot as shown in arrow 52 . [0035] FIG. 7 shows the middle roller 14 b positioned in the lower seats 24 a , while the rear roller 14 c is in the upper seats 26 b to allow a user to roll both the top 49 of his foot (along arrow 53 ) and the bottom 48 of his foot (along arrow 51 ) against the massager. [0036] FIG. 8 shows both the middle and rear rollers positioned in the upper seats 24 b , 26 b to present a flat angled massaging surface to the user's foot/feet in the directions of arrow 54 . It is contemplated that this configuration is best used while the user is seated to reduce leg or knee strain during use. [0037] Referring now to FIG. 9 , massager 10 may optionally include a textured sleeve 60 having an internal bore sized to frictionally slide over the outer surface 36 a of the roller body 36 . Sleeve 60 is preferably formed from a tough, but pliable, material such as silicone or plastic and has a plurality of raised massaging ridges or nodes 62 covering the its outer surface. In other embodiments, the shape, size, and number of the ridges disposed on the outer surface can vary. [0038] Referring now to FIG. 10 , an alternate embodiment of the rollers is illustrated. In this embodiment, the roller, denoted 114 , has separate tubular bodies 136 a , 136 b which independently rotate about the axle 38 on their own set of roller bearings 40 . In this configuration, a user can roll both feet upon the massager 10 simultaneously in the opposite direction and/or at different speeds. [0039] It should be appreciated that the adjustable slots 24 , 26 may include various means to retain their respective rollers within a selected seat. In still other embodiments, the seats may be eliminated or supplemented where the rollers 14 are vertically adjustable along slots in the walls 16 and fixed in a desired location/height by placing the axle 38 in tension through hand-tightening fasteners, e.g., nuts 44 , against the walls 16 . [0040] From the foregoing description, one skilled in the art will readily recognize that the present disclosure is directed to a foot massager having a plurality of rollers. While the present disclosure has been described with particular reference to various preferred embodiments, one skilled in the art will recognize from the foregoing discussion and accompanying drawing and claims that changes, modifications and variations can be made in the present disclosure without departing from the spirit and scope thereof. [0041] For example and without limitation, while the present disclosure is shown having three roller receiving apertures in each wall, it should be appreciated that any number of apertures and rollers can be used accordingly. Further, while only two seats are disclosed in each adjustment slot, these slots can include any number of seats providing for greater adjustability in roller configuration/angle.
A foot massaging device having a plurality of parallel cylindrical rollers mounted within a frame. The frame includes adjustment slots allowing the rollers to be relocated within the frame to present various massaging configurations. The foot massaging device is adjustable by seating the rearwardly disposed rollers between a raised and lowered position to configure the rollers to contact different portions of a user's foot.
0
FIELD OF THE INVENTION The present invention relates to compositions for making cationic radiodiagnostic agents and, in particular, to accelerators for labelling such cationic radiodiagnostic agents, kits for preparing such 99m Tc-labelled cationic radiodiagnostic agents with technetium, and methods for labelling such cationic radiodiagnostic agents with technetium. BACKGROUND OF THE INVENTION Various complexes of monodentate and bidentate ligands with technetium have been made and studied. These complexes generally were made for use in studies to determine the various oxidation states of technetium and for other research regarding the structure of such complexes and metal-coordination chemistry. Such studies have been reported in, for instance, Chemistry and Industry, pp. 347-8 Mar. 26, 1960); J. Inorg. Nucl. Chem., Vol. 28, pp 2293-96 (1966); Aust. J. Chem., 23, pp 453-61 (1970); Inorganic Chem., vol. 16, No. 5, pp. 1041-48 (1977), J. Inorg. Nucl. Chem., Vol. 39, pp. 1090-92 (1977); and J. C. S. Dalton, pp. 125-30 (1976). Recently, in a presentation to the American Pharmaceutical Association, E. A. Deutsch disclosed that certain complexes of DIARS, i.e. ##STR1## and Tc-99m, and certain complexes of DMPE, i.e. (CH 3 ) 2 PCH 2 CH 2 P(CH 3 ) 2 , and Tc-99m may be useful as radiodiagnostic agents for myocardial or hepatobiliary imaging. [ 99m Tc-(DMPE) 2 Cl 2 ] + and [ 99m Tc-(DIARS) 2 Br 2 ] + were prepared by Deutsch by heating in an open flask a reaction mixture containing the appropriate hydrogen halide in aqueous alcohol solution, 99m Tc-sodium pertechnetate, and ortho-phenylenebis(dimethylarsine), i.e. DIARS, or bis-(1,2-dimethylphosphino)ethane, i.e. DMPE. The reaction was reported to take about 30 minutes. The labelled complex was then purified by chromatographic methods involving ion exchange columns. The labelled complex produced according to the procedure of Deutsch has several practical disadvantages. The procedure requires handling several ingredients including an organic solvent to make the reaction mixture and then purifying the resulting radiolabelled complex by chromatography. Each of these handling steps can contaminate the system and final product. The purification step further requires additional time for preparation of the final product. These steps require a stilled technician and are performed at the site of use, just prior to use. Thus, a complex, time consuming chemical preparation is required during which sterility of ingredients and containers is difficult to maintain. Thus, to assure freedom from contamination, a final sterilization step is required, which further adds to preparation time. Because Tc-99m has a short half-life, lengthy preparation methods are undesirable. Thus, the complexity of the preparation, both with regard to maintaining sterile conditions and to purification of the 99m Tc-labelled complex make the Deutsch procedure undesirable. It would be highly desirable to have a sterilized kit with all the necessary materials prepared by the manufacturer, to which only the Tc-99m need be added at the site of use to produce the desired labelled complex directly in high enough yield to obviate the need for purification. It would also be desirable for the kit materials to be in a closed container or vial, pre-sterilized, so that the only step to be performed at the site of use would be the addition of the radionuclide. To increase stability and shelf-life of the kit, it would be highly desirable that the materials be readily lyophilized, preferably from an aqueous solution. By achieving the desirable features outlined above, a convenient-to-use heart imaging radiopharmaceutical agent would be provided that is capable of concentrating in healthy heart tissue to provide a negative image of an infarct, or damaged or ischemic tissue. A copending application, Ser. No. 311,770, filed Oct. 15, 1981 in the name of Vinayakam Subramanyam, which is hereby incorporated by reference, describes an acid salt of a mono or polydentate ligand that is water soluble, stable in a lyophilized state, and is capable of binding with Tc-99m to form a cationic complex. The acid salt may be generally represented by the formula: ##STR2## wherein: i is an integer from 1 to 6; R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from hydrogen or substituted or unsubstituted alkyl, aryl, alkylaryl, arylalkyl, monocycloalkyl, polycycloalkyl, heterocyclic and carbocyclic groups, and R plus R i may be taken together to form a cyclic compound or separately to form a linear compound; Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are independently selected from substituted or unsubstituted alkyl, aryl, alkylaryl, arylalkyl, monocycloalkyl, polycycloalkyl, heterocyclic and carbocyclic groups; A 1 , A 2 , A 3 , A 4 , A 5 and A 6 are the same or different neutral donor atoms, each having a free-electron pair available for accepting a proton to provide a charged ligand or for complexing with Tc-99m or Tc-99 to form a cationic complex; Z is preferably a parenterally acceptable anion; k 1 , k 2 , k 3 , k 4 , k 5 and k 6 are each independently zero or one; n 1 , n 2 , n 3 , n 4 , n 5 and n 6 are independently 0 or 1; and n 7 and n 8 are integers from 1 to 6 where ##EQU1## and the charge represented by n 8 Z is equal in magnitude and opposite in sign to +n 7 ; or ##STR3## wherein: R, R' and R" are independently selected from hydrogen or substituted or unsubstituted alkyl, aryl, alkylaryl, arylalkyl, monocylcloalkyl, polycycloalkyl, heterocyclic and carbocyclic groups; A, A' and A" are independently selected from the group of neutral donor atoms having a pair of electrons available for accepting a proton to provide a charged ligand or for complexing with Tc-99m or Tc-99 to form a cationic complex; j, j' and j" are independently 0 or 1; n, n' and n" are independently the integer 1 or 2; Z is the same as defined above n 9 and n 10 are integers selected from 1 to about 3, where n 9 =j+j'+j" and the charge represented by n 10 Z is equal in magnitude and opposite in sign to +n 9 . These acid salts are normally solid compounds, water-soluble, readily lyophilized, and capable of reducing pertechnetate and binding with technetium to form stable cationic complexes. Cationic technetium complexes of these acid salts, useful for radiodiagnostic treatments, are prepared for mixing the acid salt and 99m Tc-pertechnetate in an aqueous or alcoholic solution and heating the mixture to form the cationic complex. Preferably, the ligand is provided as a lyophilized ligand acid salt as described by V. Subramanyam in copending application Ser. No. 311,770 and is contained in a sealed, sterilized vial prior to adding the pertechnetate. The pertechnetate solution can then be injected into the vial under aspetic conditions to maintain sterility. To obtain high yields, the vial is generally heated and maintained at an elevated temperature for sufficient time to form a complex of the ligand with technetium. The vial should preferably be heated to at least 80° C. for a suitable length of time, i.e. about 30 minutes or more at 80° C. Preferably, the vial is heated to 100° C. or more, and more preferably to a temperature in the range of from about 130° C. to about 150° C. At about 150° C., the reaction can be completed in about five to ten minutes, depending upon the choice and concentrations of the reactants. After cooling, the resulting radiopharmaceutical preparation may be adjusted for pH and is ready for use. Typically, when the pH is adjusted, it is adjusted into the range of from about 4.0 to about 9.0, and preferably to physiological pH. It is desirable to obtain high yields of the cationic technetium complexes for radiodiagnostic uses in one step without the need for purification of the labelled compound. It is also desirable to obtain these high yields using temperatures of 100° C. or less because constant temperature water baths are readily available in clinical laboratories. SUMMARY OF THE INVENTION The present invention provides compositions and kits for preparing cationic technetium labelled complexes using ordinary laboratory water baths for heating. The composition and kits of this invention comprise (1) an accelerator compound selected from the group of bidentate ligands capable of forming a stable four to six member ring with technetium and (2) a target-seeking ligand having the structural formula: ##STR4## wherein i is an integer from 1 to 6; R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from hydrogen or substituted or unsubstituted alkyl, aryl, alkylaryl, arylalkyl, monocycloalkyl, polycycloalkyl, heterocyclic and carbocyclic groups, and R plus R i may be taken together to form a cyclic compound or separately to form a linear compound; Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are independently selected from substituted or unsubstituted alkyl, aryl, alkylaryl, arylalkyl, monocycloalkyl, polycycloalkyl, heterocyclic and carbocyclic groups; A 1 , A 2 , A 3 , A 4 , A 5 and A 6 are the same or different neutral donor atoms, each having a free-electron pair available for complexing with Tc-99m or Tc-99 to form a cationic complex; and k 1 , k 2 , k 3 , k 4 , k 5 and k 6 are each independently zero or one; ##STR5## wherein: R, R' and R" are independently selected from hydrogen or substituted or usubstituted alkyl, aryl, alkylaryl, arylalkyl, monocylcloalkyl, polycycloalkyl, heterocyclic and carbocyclic groups; A, A' and A" are independently selected from the group of neutral donor atoms having a pair of electrons available for complexing with Tc-99m or Tc-99 to form a cationic complex; and n, n' and n" are independently the integer 1 or 2; or ##STR6## wherein R, R', R" and R'" are independently selected from hydrogen or substituted or unsubstituted alkyl, aryl, alkylaryl, arylalkyl, monocylcloalkyl, polycycloalkyl, heterocyclic and carbocyclic groups; A', A" and A'" are independently selected from the group of neutral donor atoms having a pair of electrons available for complexing with Tc-99m or Tc-99 to form a cationic complex; B is an atom selected from the group of neutral donor atoms having a pair of electrons available for complexing with Tc-99m or Tc-99 or from the elements listed in Group IV A of the periodic table (i.e. C, Si, Ge, Sn, and Pb); m is 0 is 1; n', n" and n'" are independently the integer 1 or 2; wherein the technetium coordinate bond with said bidentate accelerator ligand is weaker than the technetium coordinate bond with said target-seeking ligand. Preferably the bidentate accelerator ligand is capable of reducing technetium. In one embodiment, the bidentate ligand is capable of forming coordinate bonds with technetium through oxygen atoms. In a preferred embodiment of this invention, the composition and kit are useful for preparing technetium labelled complexes in yield high enough to be useful for radiodiagnostic agents using ordinary water baths for heating and without the need for purification. The compositions of this invention comprising the accelerator compound and target-seeking ligand are preferably supplied as a kit as lyophilized solids in a pre-sterilized vial. Useful cationic technetium complexes are prepared in accord with this invention, for example, by adding 99m Tc-pertechnetate solution to the vial and heating in a water bath to obtain high yields of the desired complexes. The R's in formulas I, II and III are preferably alkyl radicals having 1 to about 6 carbon atoms such as methyl, ethyl, etc., and the like, and aryl radicals such as benzyl, phenyl, etc., and the like. The cationic complexes formed from compositions and kits of this invention, when radiolabelled are useful for radiodiagnostic tests in connection with myocardial and hepatobiliary tissues. DETAILED DESCRIPTION OF THE INVENTION The compositions and kits of the present invention can be prepared from a wide variety of monodentate and polydentate target-seeking ligands. Typical examples of such ligands include, for instance, aryl compounds having arsenic, phosphorus, nitrogen, sulfur, oxygen, selenium, tellurium, or any combination of them, substituted ortho to each other. For example, o-phenylene compounds having the structure: ##STR7## in which M and M' are arsenic, phosphorus, nitrogen, sulfur, oxygen, selenium, tellurium, or any combination of them, and R and R' are independently hydrogen, or an organic group, preferably an alkyl group having 1 to 6 carbon atoms, an aryl group such as phenyl, or the like, and substituted such groups. Additional examples of suitable target-seeking ligands include bidentate cis-tetraethylene ligands of the formula: R'.sub.2 M'--CX'.sub.2 CX.sub.2 --MR.sub.2 V in which M, M', R, and R' are as defined above and X and X' are independently selected from hydrogen, halide, or substituted or unsubstituted lower alkyl groups having 1 to about 6 carbon atoms. Further examples of suitable target-seeking ligands include those having the formula: ##STR8## where M, M', R, and R', are as defined above, M" is independently selected from arsenic, phosphorous, nitrogen, sulfur, oxygen, selenium, and tellurium, and R" is independently selected from hydrogen, halide or an organic radical, preferably an alkyl radical having 1 to about 6 carbon atoms, an aryl radical such as phenyl, or the like, and substituted such groups. Particularly preferred target-seeking ligands for the practice of this invention are the bis-dialkylphosphinoethanes and their substituted derivatives, including, for example, 1,2-bis(dimethylphosphino)ethane, 1,2-bis(di(trifluoromethyl)phosphino)ethane, 1,2-bis(dimethylphosphino)-1,1-difluoroethane, 1,2-bis(dimethylphosphino)-1-fluoroethane, 1,2-bis(dimethylphosphino)propane, 1,2-bis(di(trifluoromethyl)phosphino)-1,1,2,2-tetrafluoroethane, 1,2-bis(di(trifluoromethyl)phosphino)propane, 2,3-bis(di(trifluoromethyl)phosphino)butane, 1,2-bis(di(trifluoromethyl)phosphino)butane, 1,3-bis(dimethylphosphino)butane, 1,3-bis(dimethylphosphino)propane, 1,3-bis(di(trifluoromethyl)phosphino)propane, 1,2-bis(dimethylphosphino)-1,1-dichloro-2,2-difluoroethane, and similar compounds wherein the phosphorus is replaced by nitrogen, arsenic, sulfur, oxygen, selenium, tellurium, or any other atom having a free electron pair, and the like. Other useful target-seeking ligands include the alkylaminobis(difluorophosphine), i.e., RN(PF 2 ) 2 , ligands and the like where R is an organic group, preferably an alkyl group having 1 to about 6 carbon atoms, an aryl group as phenyl, or the like, and substituted such groups; and the o-phenylene compounds such as, for example, orthophenylenebis(diarsine), orthophenylenebis(dimethylarsine), orthophenylenebis(diamine), orthophenylenebis(dimethylamine), orthophenylenebis(diphosphine), orthophenylenebis(dimethylphosphine), and the like. Additional target-seeking ligands suitable for use in the present invention are those described by Nozzo et al., in J. Amer. Chem. Soc., 101, p. 3683 (1979) and by Wilson et al., J. Amer. Chem. Soc., 100, p. 2269 (1978), which are hereby incorporated by reference. Any donor element can be used in the target-seeking ligand in accord with this invention provided that it is a neutral donor atom having a free-electron pair available for accepting a proton to provide a charged ligand and further provided that it has the capability of complexing with technetium (Tc-99 or Tc-99m) to form a cationic complex in the presence of suitable anions. Suitable such elements include, for instance, phosphorous (P), arsenic (As), nitrogen (N), oxygen (O), sulfur (S), antimony (Sb), selenium (Se), tellurium (Te), and the like. Preferred elements are P and As. Accelerator compounds useful in the practice of the present invention are selected from the group of bidentate ligands capable of forming a four to six, preferably five member chelate ring with technetium. Preferably, such bidentate ligands also have the capability of reducing technetium. Bidentate ligands suitable as accelators for the practice of this invention include dicarboxylic acids, diphosphonic acids, enols, acidic 1,2-dihydroxy compounds, particularly 1,2-dihydroxy compounds having a nearby strongly electron-withdrawing group, alpha-hydroxycarboxylic acids, alpha-hydroxyphosphonic acids, and the like, etc. Specific examples of such accelerators include, for instance, catechol, oxalic acid, ascorbic acid, tartaric acid, hydroxymethylenediphosphonic acid, methylene diphosphonic acid, and the like, etc. Examples of electron-withdrawing groups suitable for use in such 1,2-dihydroxy compounds are --NO 2 , --Cl, --Br, --F, --I, or --CF 3 . The compositions of this invention are useful for preparing radiodiagnostic agents wherein the target-seeking ligand is labelled with technetium. Labelling is accomplished by mixing a suitable quantity of 99m Tc-pertechnetate in solution with the accelerator compound and target-seeking ligand, and heating the admixture for a suitable length of time at a temperature attainable with a constant temperature water bath. Preferably, the heating step is performed at 100° C. for thirty minutes or less. An aqueous physiological saline solution is typically the solution of choice for labelling the target-seeking ligand because it is readily administered to the patient. The compositions of this invention are preferably contained in a kit, such as a presterilized vial. The presterilized vial, such as a glass vial, containing the compositions of this invention is ready for use for preparing cationic technetium complexes for radiodiagnostic use. More preferably, the compositions are lyophilized in such kits to increase storage stability of the compositions. In such lyophilized kits, the target-seeking ligand is generally present as a water-soluble acid salt of the ligand. The lyophilized kits are used by reconsituting with a suitable quantity of 99m Tc-pertechnetate in saline solution. The reconstituted compositions are then placed in a constant temperature water bath for a sufficient time to form labelled technetium complexes with the target-seeking ligand. Preferably, the reaction time is about 30 minutes or less at a temperature of about 100° C. It has been found that lyophilized compositions for the preparation of cationic technetium complexes can be improved by the addition of a polyhydroxy-compound to the reaction mixture. The use of the polyhydroxy-compound, for reasons not fully understood, results in a more consistent yield of the cationic technetium complex. Preferred polyhydroxy-compounds include, for example, Hetastarch (hydroxyethyl starch), mannitol, glycerol, D-mannose, sorbitol, and the like. To image the heart of a mannal, in-vivo, a radiopharmaceutical preparation in accord with the invention, having a suitable quantity of radioactivity for the particular mammal, is injected intravenously into the mammal. The mammal is positioned under a scintillation camera in such a way that the heart is covered by the field of view. High quality images of the heart are obtained analogous to those seen in clinical studies using Thallium-201. In order to obtain high quality images the yield of radioactive labelled cationic technetium complex should preferably be greater than 70% after reconstituting the lyophilized mixture and labelling. Lower yields will result in poorer image quality and undesirable purification steps will be required to produce high quality images. This invention will be further illustrated by the examples that follow: PREPARATION OF 1,2-BIS(DIMETHYLPHOSPHINO)ETHANE BIS-BISULFATE, i.e. DMPEH 2 2+ . 2HSO - 4 or DMPE.2H 2 SO 4 Dissolve 470 mg of DMPE in 10 ml of ethanol in a 50 ml round-bottomed flask maintained under a nitrogen atmosphere. From a glass syringe, add, with stirring, 0.34 ml of concentrated sulfuric acid. After 10 minutes, filter the precipitate and recrystallize it from 10 ml. of methanol. Filter and dry under vacuum. 920 mg of a crystalline solid is obtained, which melts at 135-136.5° C. Structure and purity of the compound was confirmed by its infra-red and nuclear magnetic resonance spectra and elemental analysis. COMPARATIVE EXAMPLE A Dissolve 1 g mannitol, 150 mg sodium chloride, and 46 mg DMPE-bis(bisulfate) in 10 ml deoxyugenated physiological saline solution (0.15 Molar). Adjust the pH of the solution to 1.4 by adding the required volume of 2 N hydrochloric acid. Dispense 1 ml of the solution into each of several 10 cc vials, flushing each with nitrogen gas for 20 seconds, closing with a teflon-coated stopper and crimp-sealing it. LABELLING PROCEDURE I Inject 50 mCi of 99m Tc-pertechnetate in 0.5 ml physiological saline into each of several vials and place them in an oil bath, preheated and maintained at 150°±5° C., for 5-10 minutes. HPLC analyses show yields of 90 to 100%. LABELLING PROCEDURE II Inject 50 mCi of 99m Tc-pertechnetate in 0.5 ml physiological saline into each of several vials and place them in a steam autoclave preheated to 100° C. Set the temperature control to 135° C., and when that temperature is achieved, maintain it for 20 minutes. Allow the system to cool to 100° C. and remove the vials. HPLC analyses show yields of 95 to 100%. COMPARATIVE EXAMPLE B Dissolve 5 g mannitol and 230 mg DMPE-bis(bisulfate) in about 35 ml low-oxygen distilled water, and adjust the pH of the solution to 1.0 with 3 N sulfuric acid. Under cover of nitrogen, and with stirring, add low-oxygen distilled water gravimetrically, to a solution weight of 50 g. Dispense 1 ml of this solution into each of several 10 cc vials. Freeze-dry in keeping with procedures well-known to those skilled in the art, stoppering under nitrogen. Reconstitute each vial with 1 ml of physiological saline containing about 10-20 mCi 99m Tc-pertechnetate. Utilizing techniques similar to those of Example A above, autoclave for 30 minutes at 135° C. Thin layer chromatography (TLC) analyses show yields consistently greater than 95%. COMPARATIVE EXAMPLE C The procedure of Example B, above, was followed to prepare several vials except that the pH was adjusted to 2.0 and the amounts of reagents were changed so that each vial contained 0.336 mg DMPE.2H 2 SO 4 and 20 mg mannitol. The vials were used to label the DMPE.2H 2 SO 4 according to the following procedures: (1) Labelling with 99m Tc-pertechnetate as in Example A, above, but at 133° C. for 40 minutes yielded 90-95% labelled product. (2) Labelling with 99m Tc-pertechnetate in 100° C. water bath for 30 minutes yielded ≦2% labelled product. EXAMPLE 1 Oxalic Acid Dihydrate--DMPE.2H 2 SO 4 Dissolve 1 g mannitol, 350 mg oxalic acid dihydrate, and 15.0 mg DMPE.2H 2 SO 4 in 45 ml of low-oxygen distilled water and adjust the pH to 1.7 with 2N NaOH. Under cover of nitrogen, and with stirring, add low-oxygen distilled water gravemetrically to a solution weight of 50 g. Dispense 1 ml of this solution into each of several 3 cc vials. Freeze-dry in keeping with procedures well-known to those skilled in the art, stoppering under nitrogen. Reconstitute each vial with 1 ml of physiological saline containing 10-50 mCi 99m Tc-pertechnetate. Place labelled vials in a boiling water bath at 100° C. for 30 minutes. TLC analyses show yields greater than 90%. EXAMPLES 2-6 A formulation similar to example 1 but containing, per vial, 0.317 mg DMPE.2H 2 SO 4 , 8.5 mg oxalic acid dihydrate, 19.5 mg mannitol at pH=1.8 before lyophilization is labelled with 1.0 ml of physiological saline containing 55 mCi of 99m Tc-pertechnetate. After heating for 30 minutes at various temperatures, the yield of product analyzed by TLC was as shown in the following table. ______________________________________Example No. Heating Temperature % Product ± 10%______________________________________2 60° C. 233 70° C. 684 80° C. 895 90° C. 966 100° C. 97______________________________________ EXAMPLE 7 Ascorbic Acid--DMPE.2H 2 SO 4 A liquid formulation was prepared in physiological saline containing, per ml, 100 mg ascorbic acid, 1 mg DMPE.2H 2 SO 4 at pH of 1.80. After labeling with 99m Tc-pertechnetate and heating 15 minutes at 100° C. the yield of product was 87%. EXAMPLE 8 Imaging of Rabbit Heart Using Tl-201 (Prior Art) 2 mCi of Thallium-201 (as thallous chloride in physiological saline containing 0.9% benzyl alcohol) is injected intravenously into a 2.5 Kg male New Zealand Albino rabbit. The rabbit is positioned under a Searle Pho-Gamma scintillation camera in such a way that the heart and lung area are covered by the field of view. Approximately 10 minutes after injection, sufficient counts are accumulated to produce an image of the heart analogous to that seen in clinical studies of humans. EXAMPLE 9 Imaging of Rabbit Heart Using 99m Tc-labelled Products with ≧80% Yield of Desired Labelled Complex Greater than 1 mCi of the 99m Tc-labelled product of Example 1 or 7 is injected into a rabbit and imaged as in Example 8. The quality and appearance of the heart image is similar to that obtained in Example 8. EXAMPLE 10 Imaging of Baboon Heart Using 99m Tc-labelled Products with ≧80% of Desired Labelled Complex Greater than 10 mCi of the 99m Tc-labelled product of Example 1 or 7 is injected intravenously into an adult baboon positioned under a scintillation camera as was the rabbit in Example 8. Excellent quality images of the heart are obtained, which are equivalent to those characteristically obtained with Tl-201 in humans. EXAMPLE 11 Visualization of Hepatobiliary Transit with 99m Tc-labelled Disofenin (Prior Art) A lyophylized vial of HEPATOLITE™ (New England Nuclear Corporation's brand of Technetium Tc99m Disofenin) is labelled with 99m Tc-pertechnetate in accordance with manufacturer's directions. At least 1 mCi of the labelled preparation is injected intravenously into a 2.5 Kg male New Zealand Albino rabbit. The rabbit is positioned under a Searle Pho-Gamma scintillation camera in such a way that the liver and gastro-intestinal tract are within the field of view. Sequential images taken from the time of injection demonstrate an initial liver uptake with gradual visualization of the gall bladder and gastro-intestinal tract, analogous to the diagnostically efficacious results obtained in clinical studies of normal healthy humans. EXAMPLE 12 Visualization of Hepatobiliary Transit with 99m Tc-Labelled Products Greater than 1 mCi of the 99m Tc-labelled product of Example 1 or 7 is injected into a rabbit as in Example 11. Sequential images of hepatobiliary transit reveals passage similar to that in Example 11, with comparable image quality of the liver and gall bladder. EXAMPLE 13 Tartaric Acid--DMPE.2H 2 SO 4 Lyophilized kits each consisting of a sealed vial containing 336 micrograms DMPE.2H 2 SO 4 and 20 mg mannitol were used in this example. The kits were adjusted for pH so that when reconstituted with 1 ml physiological saline, they had a pH of 2.0 . To each freeze-dried kit was added 0.5 ml of physiological saline containing 15 mCi of 99m Tc-pertechnetate and 0.5 ml of physiological saline or 0.5 ml of physiological saline containing 0.2 M tartaric acid. After heating the kits for 30 minutes in a 100° C. water bath, TLC analysis showed the following yield of product, i.e. [ 99m TC(DMPE) 2 Cl 2 ] + , and TcO 2 . ______________________________________Tartaric Acid % TcO.sub.2 % Product______________________________________0 0 20.10 M 0 20______________________________________ EXAMPLE 14 Freeze-dried kits containing 1 mg of DMPE.2H 2 SO 4 are reconstituted as in Example 13 except that catechol or methylenediphosphonic acid (MDP) are added to the reconstituted solution and the pH of the composition when reconstituted is 1.7. The kits are reconstituted with 10 mCi of 99m Tc-pertechnetate in saline, with accelerator added, and placed in a 100° C. water bath for 30 minutes and the yield of [ 99m TC(DMPE) 2 Cl 2 ] + is as follows. ______________________________________Accelerator % Product______________________________________Catechol (1 mg/ml) 24MDP (10 mg/ml) 30______________________________________ EXAMPLE 15 50 microliters of (CH 3 ) 2 PCH 2 CH 2 As(CH 3 ) 2 (ASP) was added to 50 ml of deoxygenated physiological saline having a pH adjusted to 1.0 with 1 N HCl. After the ASP was dissolved and 0.5 g oxalic acid added, the pH was adjusted to 1.5 with 1 N NaOH. One milliliter of the resulting solution was injected into each of several 5 cc vials which had been purged of oxygen and crimp-sealed. The ASP was labelled with 0.1 ml of saline containing 10 mCi of 99m Tc-pertechnetate, in a 100° C. water bath for 30 minutes. TLC analysis showed a yield of about 96% Tc-labelled ASP. This invention has been described in detail with particular reference to the preferred embodiments thereof. However, it will be appreciated that those skilled in the art, upon reading this disclosure, may make modifications and improvements within the spirit and scope of the invention.
A composition for preparing cationic lipophilic technetium complexes is described. The composition comprises an admixture of (a) an accelerator compound selected from the group of water-soluble organic bidentate ligands that are capable of coordinating with technetium to form a 4 to 6 member ring and (b) a target-seeking ligand, or aqueous salt thereof, having the structure indicated in formulas I, II or III. The accelerator compound has a weaker coordinating bond with technetium than the target-seeking ligand has with technetium.
0
FIELD [0001] This disclosure is in the field of cookery. BACKGROUND [0002] When cooking outdoors, such as over an open fire,, it is common to turn the food manually. For instance, when cooking a hot dog on a stick, the stick must be turned manually to ensure the meat is cooked evenly. This evenness is hard to achieve because it is difficult to continuously rotate a stick manually and is usually rotated step-wise. Further, the proximity of a hand to an open fire presents a possible danger for burns. Prior art devices generally have a manual rotation method, such as turning a crank like a fishing rod without convenient push button or battery operation. [0003] U.S. Patent Application No. US 2006/0076789 A1 to Herbert, discusses a cook out food roaster. The rotisserie device may be turned at a predetermined speed and includes a coupler for attaching extendable cooking attachments to the device. [0004] U.S. Pat. No. 6,754,966 B2 to Holzer discusses a hot dog roaster with adjustable prongs. The prongs may be folded back to prevent injury or to prevent damage to other objects. When cooking, the food may be manually rotated in a mostly continuous way basis or alternatively, the food may be rotated intermittently when cooking. [0005] U.S. Pat. No. 6,701,827 B1 to Longbrake, discusses a manual hot dog roaster for cooking outdoors. The apparatus is designed to help the user cook a hot dog more evenly. When cooking, the food may be manually rotated in a mostly continuous way basis or alternatively, the food may be rotated intermittently. SUMMARY [0006] In the view of the foregoing disadvantages inherent in the known types of rotisserie devices for heating food, such as hot dogs, that is now present in the prior art, the present disclosure provides an improved and automated rotisserie stick (hotdog stick) that rotates and evenly cooks food. As such, the general purpose of the present disclosure, which will be described subsequently in greater detail, is to provide a new and improved battery operated rotisserie stick. [0007] The inventive aspect described in the specification can be embodied in an apparatus for holding and rotating food, such as a hot dog. The apparatus may further include an extendible arm configured to removably attach a fork or a like device for piercing and holding food. The further inventive aspects can be embodied in a motor configured to be coupled to the fork to rotate the fork. Thus, the motorized device may rotate the food over an open fire while the user simply holds the device. [0008] The other inventive aspects can be embodied in a system for a height adjustable support for the extendible arm. Thus, a user may adjust the distance to an open fire for holding and rotating food. Yet other inventive aspects cart be embodied in the system for holding and rotating food wherein the prongs of the fork are U shaped, wherein distal ends of the prongs may be bent backward and include wave or zig-zag portion. The further inventive aspects can be embodied in the apparatus for holding and rotating food, wherein a lamp is attached to the arm and is configured to shine light, such as to shine light on the prongs. This may help make the food visible in darkened outdoor conditions. The other inventive aspects may be embodied in wherein the rotation of the fork or prong is automated and may be remotely controlled by a user. Such automation may include a battery power source. [0009] In this respect, before explaining at least one embodiment of the disclosure in detail, it is to be understood that the disclosure is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The disclosure is capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting. [0010] These together with other objects of the disclosure, along with the various features of novelty which characterize the disclosure, are pointed out with particularity in the disclosure. For a better understanding of the disclosure, its operating advantages and the specific objects attuned by its uses, reference should be made to the accompanying drawings and descriptive matter in which there are illustrated preferred embodiments of the disclosure. BRIEF DESCRIPTION OF THE DRAWINGS [0011] The example embodiments of the inventive concept will be better understood from the following brief description taken in conjunction with the accompanying drawings. The drawing. FIGS. 1-6 represent non-limiting, example embodiments. [0012] FIG. 1 shows a handle for an automatic food rotisserie, in accordance with an example embodiment. [0013] FIG. 2 shows a set of prongs and securing mechanism for an automatic food rotisserie, in accordance with an example embodiment. [0014] FIG. 3 shows a rod coupler configured to couple to a handle of an automatic food rotisserie, in accordance with an example embodiment. [0015] FIG. 4 shows a rod coupler connected to a plastic handle, in accordance with an example embodiment. [0016] FIG. 5 shows a rotisserie cooking apparatus, in accordance with an example embodiment. [0017] FIG. 6 shows height adjustable rotisserie cooking apparatus, in accordance with an example embodiment. DETAILED DESCRIPTION [0018] In the following description, reference is made to the accompanying drawings which form a part hereof, and in which is shown by way of illustration specific embodiments in which the inventive concept may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the inventive concept, and it is to be understood that the embodiments may be combined, or that other embodiments may be utilized and that structural and logical changes inns be made without departing from the spirit and scope of the present inventive concept. The following description is, therefore, not to be taken in a limiting sense. [0019] Example embodiments of the inventive concepts may be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will convey the concept of example embodiments to those of ordinary skill in the art. In the drawings, some dimensions are exaggerated for clarity. [0020] It will be understood that when an element is referred to as being “connected” or “coupled” to another element, it can be directly connected or coupled to the other element or intervening elements may be present. [0021] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments of the inventive concepts. As used herein, the singular forms “a,” “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises”, “comprising”, “includes” and/or “including,” if used herein, specify the presence of stated features, integers, steps, operations, elements and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and/or groups thereof. [0022] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which example embodiments of the inventive concepts belong. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein. [0023] The current disclosure is battery operated to allow the stick to rotate continuously and uniformly for even cooking, and thus obviates the need to manually turn the hotdog stick. [0024] In one embodiment, the automatic rotisserie allows even cooking over an open fire without the need for manual intervention. In another embodiment, the automatic rotisserie includes at least one prong with a shape and/or geometry to ensure the food, such as a hotdog is secure and will not rotate with respect to the prong. Such a geometry may include a spiral, corkscrew, zigzags or wave shape to ensure the food is secure through 360 degrees of rotation. [0025] In one embodiment, the automated rotisserie is batters operated and thus turns the food without using a manual mechanism. In one embodiment, the automated rotisserie allows the user to prop up the stick and allow the food to cook automatically. [0026] FIG. 1 shows a diagram that that includes the components for the automatic rotisserie that may include: ⅛″ thick stainless reverse skewers ( 101 ), 3/16″ thick stainless rod ( 103 ) spot welded to the skewers, a 1.5″ PVC cap with a 3/16″ hole to accept the rod ( 103 ), a 12 inch long and 1.5 inch diameter PVC pipe ( 105 ) with a rod support 8 inches from cap to accept the rod, and a 1.5″ PVC coupling. The apparatus may also include a flexible coupling ( 107 ) to connect the rod to a motor, and a 5 inch long 1.5 inch diameter PVC pipe with flexible mounted motor battery compartment and switch mechanism. [0027] FIG. 2 shows a stainless steel rod with reverse skewers or prongs. In one embodiment, the skewers ( 201 ) may include a wave (as shown), spiral, corkscrew, curve, or other like geometer that secures the food while the food is rotated and cooked. Thus, the food will not rotate on the skewer and cook unevenly. The skewers may be bent in a U and attached to a stainless steel rod ( 203 ). [0028] FIG. 3 shows a rod coupler for providing a handle of an automatic food rotisserie, in accordance with an example embodiment. In one embodiment, the rod coupler ( 301 ) is matched with a threaded component of a stainless steel rod ( 303 ) of skewers. In one embodiment, the rod coupler piece ( 305 ) will connect through a PVC pipe to a motor, which will power the rotation of the rotisserie apparatus. The motor may be controlled with one or more automatic controls and may be battery powered. In an example embodiment, the rotation of the rotisserie may be remotely controlled. [0029] FIG. 4 shows an illustration of a rod coupler connected to a plastic handle, in accordance with an example embodiment. In one embodiment, the rod coupler ( 401 ) is connected with a threaded component of a stainless steel rod of skewers ( 403 ). In one embodiment, the rod coupler piece ( 405 ) is passed through the PVC pipe ( 407 ) to connect with a motor, which will power the rotation of the rotisserie apparatus. The motor may be controlled with one or mote automatic controls and may be battery powered. [0030] FIG. 5 shows an illustration of a rotisserie cooking apparatus, in accordance with an example embodiment. The apparatus includes a skewer ( 501 ) connected to a stainless steel rod ( 503 ), which is attached to a motor through the PVC pipe ( 505 ). The body of the pipe includes a push button ( 507 ) to start and stop the rotation of the skewer. [0031] In one embodiment, the manufacture of the automatic rotisserie may include a number of steps including: Step 1: obtain the ⅛″ stainless reverse skewers. Step 2: spot weld the skewers to a stainless steel rod. Step 3: a 3/16″ hole is drilled in the 1.5″ diameter PVC cap, to accept the stainless steel rod. Step 4: obtain a 12″ piece of 1.5″ diameter PVC and include another support 8″ from the cap as the rod passes through this support to eliminate stress on the motor. Step 5: obtain a 1.5″ diameter PVC coupling, Step 6: the rod is inserted into a flexible coupling which is connected to the motor. Step 7: obtain a 5″ piece of 1.5″ diameter PVC containing the flexible mourned motor and a battery compartment for 3 AAA batteries controlled by a push button switch. [0032] In one embodiment, the disclosure may be implemented as follows: The ⅛″ stainless steel skewers with five off-sets or waves on each of the two skewers prevent the hotdogs from spinning or falling off during the cooking process. In one embodiment, the skewers are welded to a 36″ stainless steel rod while pointed inward and toward the power source. In one embodiment, the 1.5″ diameter PVC cap with the 3/16″ hole is pressed onto the 12″ piece of PVC with the rod support 8 inches from the cap. The rod support also has a 3/16″ hole which is aligned with the hole in the cap so the rod will be perfectly aligned with the motor. [0033] In one embodiment, the disclosure mare be further implemented using a 5″ piece of PVC that is machined to hold the motor on one side and machined on the other side to allow access to the battery compartment and to place and protect the push button switch. In one embodiment, the aluminum battery compartment and switch combo are pressed into the end opposite the motor and additionally secured with a sealing adhesive. In one embodiment, the motor wires are soldered to the wires on the battery compartment already in place. Furthermore, a 3″ piece of flexible tubing is attached to the motor shaft and held with a wire clamp. The motor may be placed into the machined slots and held temporarily in position with a small piece of glass tape. In one embodiment, the 1.5″ diameter PVC coupling is now pressed on the 5″ piece, on the motor side, to permanently hold the motor in place. [0034] In one embodiment, the disclosure may be further implemented by sliding the assembled stainless steel skewer and rod through a 3/16″ hole in the PVC cap and the rod support. Further, the rod is then slid into a flexible coupling on the motor and held in place with a wire clamp. In one embodiment, the 12″ inch piece of PVC with the cap and rod assembly may be pressed into the 1.5″ diameter coupling, so that the rod and motor shaft are perfectly aligned to complete the assembly. In one embodiment, the apparatus may be powered with three AAA batteries and controlled by a push button switch in conjunction with a DC worm gear motor. In one embodiment, the motor may spin the rod at approximately 4 RPM's. [0035] In one embodiment, the disclosure may be made using a motor with a targeted speed in revolutions per minute (RPM) as deemed appropriate. Furthermore, the components may also include a targeted DC voltage, torque, and output shaft length and diameter. In one embodiment, the motor may include mounting tabs to attach to the PBC housing. In one embodiment, the turbine worm gear box motor includes the specs of 3-12 volts DC, 16 RPM, a 5.2 mm total length, a 27 mm axis length, a 2.5 mm screw hole, and a 125 mm cable length. Further, the motor may be tested for reliability and also fit well into the PVC housing. In one embodiment, a power supply is required that adapts to the 1.5″ diameter PVC pipe to house the motor and battery/switch compartment. [0036] In one embodiment, one side of the pipe is machined with two ¼″ diameter by ⅛″ deep half round slots for the motor mounting tabs to fit into. The other end of the pipe is machined with two ⅞″ wide by ½″ deep slots on opposite sides of the pipe. These slots allow the battery/switch compartment to slide, far enough, into the pipe to prevent the switch from dropping, but also allow the unscrewing of the compartment to change a battery. In one embodiment, a piece of PVC is cut to 1.5″ by 2.25″ long, then out length wise into 6 even pieces, approximately ¾″ wide. In one embodiment, the power supply is assembled by first holding the 1″×2.5″, with 3/16″ slot and cutting two pieces of PVC with the slot facing straight up. Then, two shims may be held on opposite sides of the slotted piece, which are 90 degrees from the slot, and then, 3 pieces are loosely clamped into a vice with 1″ of length protruding. [0037] In one embodiment, the battery/switch compartment is slid with the switch end placed first into the 1″ slotted pipe until flush with the end sticking out of the vice. Then, the vice may be tightened until the 1″ pipe compresses tightly onto the battery/switch compartment. In one embodiment, the end of the 5″ piece of 1.5″ diameter PVC with the 7/18″ wide by ½″ deep slots are pressed with the 3 pieces by clamping in the vice. The vice may then be opened and the remaining length of the battery/switch compartment pressed, with shims, fully it to the 5″ piece 1/16″ past the end. In one embodiment, adhesive/sealer may be used to hold the components firmly in place and to seal the compartment. Then, the motor may be added by soldering the motor leads to the battery compartment and then securing the connections. In one embodiment, the motor is slid into the end of the 5″ long piece with the ¼″ diameter and ½″ deep half round slots. [0038] In one embodiment, the motor is set into the slots, so the output shaft is closest to the PVC. Next, a 2.5″ by 0.5″ piece of glass tape is used to tape the motor to temporarily hold it into place. In one embodiment, a piece of flexible tubing 3″ long with 0.170″ I.D×¼ O.D. is cut and pressed into the motor shaft. The tubing may then be secured to the shaft with a wire clamp and a 1.5″ PVC coupling pressed into the motor end of the piece, which permanently holds the motor in place. In one embodiment, a 12″ piece of PVC may be cut and a hole drilled of 5/16″ and placed 8″ from either end of the pipe. Then, a hole is tapped with a ⅜″×16″ tap. Then, using a ⅜″ bolt that is 1″ long, drill a 3/16″ hole that is ½″ below the bolt head. The bolt may be threaded into the tapped hole as far as it will go, but while still allowing the hole to be aligned with the hole in the pipe. [0039] In one embodiment, the bolt acts as a rod support to protect the motor from stress. In one embodiment, a 1.5″ PVC pipe cap may be drilled with a 3/16″ hole that is ½″ from the inside edge of the cap flange. in one embodiment, the cap may be pressed onto the 12″ piece and kept 8″ away from the ⅜″ bolt. The holes in the cap and bolt must line up exactly to accept the 3/16″ cooking rod. Then, a 12″ piece of ⅛″ stainless steel rod that is 12″ long may be used to make two 90 degree bends that are 4.5″ from each end to form a “U” shape. Next, each 4.5″ side may be put into a jig. A set of five offsets, waves, zigzags, corkscrews, or curves are added that are 5/16″ deep on each side. This shape ensures the food, such as a hot dog will be secured when rotating over an open fire. [0040] In one embodiment, a 3 foot long piece of 3/16″ stainless steel rod may be spot welded into a “U” shape to make a roasting stick. Then, the roasting stick may be slid through the holes in the pipe cap, in the 12″ piece, and through the hole in the threaded bolt. Furthermore, the rod may be slid into the flexible coupling, which is already clamped to the motor and secured with a wire clamp. As a next step, the 12″ section may be pressed with the roasting rod into the 1½″ coupling already pressed on the 5″ motor and battery section. Thus, ensuring a proper alignment between the rod and motor shaft. Add three AAA batteries and the apparatus is may be used. [0041] In one embodiment, the unit can be used as described, and as such, may be set by a fire and/or propped up on a rock or log. It is also envisioned that a removable clamp on the legs can be used on just the front or on both the front and back to allow the apparatus to function like a mini spit. Furthermore, adjustable legs and/or fold up legs may be permanently mounted. [0042] In one embodiment, the stainless steel rod and skewers could be substituted with chrome plated steel to reduce the cost. [0043] In another example embodiment, fold up legs could be added to simplify the desired cooking height at a reduced cost. Also, a detachable rod coupler could be added to make cleaning easier and to shorten the product for easier packaging and shipping. [0044] In one embodiment, the skewers at the end of the 3/16″ rod can be attached and pointed toward the unit for added safest. In an example embodiment, the 5″ cut from the 3/16″ rod allows a proper ballast for the unit. Thus, the unit may be secured and the weight of the food, such as hot dogs will not teeter toward the hot coals or flames. [0045] FIG. 6 shows a height adjustable rotisserie cooking apparatus 700 , in accordance with an example embodiment. The height adjustable stands 701 are configured to be attached to the arm of the rotisserie. The arm 505 of the rotisserie may be extended or retracted while the apparatus is standing on the stands 507 . Stand 701 and arm 505 are retractable for compact size and portability. The rotisserie cooking apparatus 700 is a self-contained standalone apparatus. [0046] It is to be understood that the above description is intended to be illustrative, and not restrictive. For example, the above-discussed embodiments may be used in combination with each other. Many other embodiments will be apparent to those of skill in the art upon reviewing the above description. [0047] The benefits and advantages which may be provided by the present inventive concept have been described above with regard to specific embodiments. These benefits and advantages, and any elements or limitations that may cause them to occur or to become more pronounced are not to be construed as critical, required, or essential features of any or all of the embodiments. [0048] While this specification contains many specific implementation details, these should not be construed as limitations on the scope of any inventive concept of what may be claimed, but rather as descriptions of features that may be specific to particular embodiments of particular inventive concept. Certain features that are described in this specification in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable sub combination.
An apparatus for holding and rotating food, the apparatus comprising a fork, an extendible arm configured to removably attach the fork, a motor configured to be coupled to the fork to rotate the fork and a height adjustable support for the arm. The fork includes prongs that are U shaped, wherein the distal ends of the prongs are bent backward and include a wave or zig-zag portions.
0
FIELD OF THE INVENTION [0001] The present invention relates generally to molds required to cure large radial pneumatic tires. BACKGROUND OF THE INVENTION [0002] It is well known that conventional radial tires run cooler and therefore provide longer service hours than conventional bias-ply tires. The superiority of a conventional radial tire, as compared to a bias-ply tire, results from the provision in a radial tire of substantially inextensible cables arranged in generally radial planes of the tire from one bead to the other bead, with a circumferential belt package of low angle cords (e.g., 5-7 degrees relative to a radial plane of the tire) being secured radially outwardly of such cables. The provision of the cables and the belt package restrains circumferential expansion of a radial tire, and accordingly, the belt package cords do not scissor relative to one another. The radial tire therefore operates at a lower temperature. The conventional bias-ply tire does not utilize a circumferential belt package and instead employs a plurality of cris-crossed plies which extend at relatively large angles relative to a radial plane of the tire. This construction subjects the tire to a heat build-up generated by the tendency of the plies to undergo scissoring relative to one another, and it is well known that excess heat tends to cause delamination and rapid tread wear resulting in a reduced service life. [0003] Tire molds for curing complete tires are generally of two types: full circle molds and segmental molds. In the case of segmented molds, heated exterior components of the mold are moved into contact position with the tread and sidewall portions of the uncured tire and cure the tire from the outside, while a bladder is inflated to contact the inner surface of the tire to help shape the tire, and heating fluids are injected into the inside of the bladder to cure the tire from the inside. An example of a full circle clamshell mold is shown in U.S. Pat. No. 4,957,676 to Greenwood. Full circle clamshell molds are proven, reliable, and lower in cost than segmental molds to manufacture. Another benefit of conventional clamshell molds is that a significant portion of the mold, typically the bottom half, may remain stationary as only the top half needs to be raised and lowered with respect thereto by a molding press, along an axis of rotation of the tire, to open and close the mold. However, clamshell molds are not appropriate for molding radial tires because a radial tire will not expand or contract in diameter and the inner molding surface of the clamshell mold cannot move radially outwardly to receive an uncured tire and radially inwardly to close around a tire casing. [0004] Another type of mold for curing tires is the segmental mold, examples of which are shown in U.S. Pat. No. 5,676,980, to Gulka et al. U.S. Pat. No. 3,787,155 to Zangl, and U.S. Pat. No. 3,806,288 to Materick. Unlike clamshell molds, which are split about the centerline of the tread pattern, segmental molds are radially segmented into a plurality of arcuate tread segments about the circumference of the mold. Each of the segments is attached to a top section of a mold container so that when the top section is lowered and raised by a press in which the container is installed, the mold section correspondingly moves up and down along the axis of tire rotation. In this direction, movement of the top mold section corresponds generally to that of the top portion of a clamshell mold. The fact that a radial tire is not radially expandable or contractible creates serious manufacturing problems when attempting to mold an uncured radial tire in a conventional segmental mold. Segmented molds such as shown in Gulka 5,676,980, are indicated as being openable to the full outside diameter of a radial tire, but present a serious problem to curing a satisfactory large diameter radial tire (e.g., about 50 inches in diameter), particularly a heavy tire for use on large off-the road vehicles, i.e., unless the mold is used in conjunction with a molding press that maintains the uncured tire in a centered position as the mold closes, when the mold is opened to receive a heavy uncured tire there exists a vertical and horizontal gap between the radially outer edge of the lower mold sections' sidewall plate and the radially inner edge of the lower tread segments. Accordingly, as the uncured tire is lowered into the cavity of the lower mold section, the heavy weight of the tire causes the cords of the belt package tire to flex which in turn causes the tire's belt package to be deformed relative to the uncured rubber in which the cords are encased as they encounter the aforementioned gap. Because of such deformation, discontinuities between the belt package cords and the uncured rubber are created, precluding the formation of an integral bond between the cords and the rubber when the tire is cured. As a result, there is a likelihood that delamination of the belt package cords relative to the tire body will occur seriously reducing the service life of the tire. The deformation can be even severe enough to render the cured tire unusable. SUMMARY OF THE INVENTION [0005] The present invention provides an improved method and apparatus for curing a radial tire within a segmental mold in a conventional autoclave without deforming the cords of the belt package relative to the uncured ruber of the tire. The segmental mold of the present invention includes a top mold section and a bottom mold section. The top mold section is movable with respect to the bottom mold section between a raised open position and a lower closed position. The top and bottom mold sections each contain a plurality of like tread segments arranged in a circular pattern. Each segment is slidably coupled to its mold section by a slanted alignment pin, and two compression springs are positioned on either side of the alignment pin to bias the treads segments outwardly with respect to their respective mold sections. Each of the tread sections is formed with radially inwardly extending tread groove-defining lugs. The bottom mold section is so configured that when the top mold section is in its open raised position, the tread segments of the bottom mold section are arranged radially outwardly of the outer diameter of the uncured tire to be molded. When the top mold section is moved to its closed lower position, the tread segments of both the top and bottom mold sections are automatically moved radially inwardly so that the tread-defining lugs of the segments engage the uncured crown of the tire during curing of the tire. When the tire has been cured, the top mold section is raised and the upper and lower tread segments automatically move outwardly away from the cured tire so such tire can be freely withdrawn from the bottom mold section without the tread segments tearing the tire. [0006] It is a particular feature of the present invention that an uncured tire can be cured in a mold without any deformation taking place between the cords of the bead package and the uncured rubber of the tire thereby precluding the formation of discontinuities between the cords and the uncured rubber surrounding such cords. This feature is accomplished by extending the lower sidewall of the bottom mold section substantially the entire distance from the tire bead area to the tread portion of the uncured tire. With this arrangement, the complete sidewall of the uncured tire is supported by the lower sidewall of the bottom mold section and the latter provides a firm platform for the uncured tire without causing a deformation of the belt package of such tire. Additionally, the radially outer portion of the lower sidewall of the bottom mold section is formed with auxiliary lugs that define the lower outer sidewall portion of the treads of a cured tire. The lugs of the tread segments and the lower mold sidewall auxiliary lugs cooperate to form a complete lower tread pattern of a cured tire. The lugs of the upper mold section tread segments and the upper mold sidewall cooperate to form the upper tread pattern of a cured tire. [0007] It is another feature of the present invention that a plurality of the aforementioned molds each containing an uncured tire may be arranged in a conventional autoclave for concurrent curing of the tires. After the tires have been cured the molds are removed from the autoclave and the cured tires withdrawn from their respective molds. [0008] Yet another feature of the present invention is that a single size mold may be utilized to cure tires of varying width. [0009] Further advantages afforded by the method and apparatus of the present invention will become apparent from the following detailed description, when taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0010] [0010]FIG. 1 is a perspective view of a tire mold embodying the present invention showing the top mold section thereof in a raised open position with respect to the bottom mold section of such apparatus; [0011] [0011]FIG. 1 a is a broken side elevation view showing tread segments supported by the top and bottom mold sections. [0012] [0012]FIG. 2 is a vertical sectional view taken in enlarged scale along line 2 - 2 of FIG. 1 when a tire to be cured is being lowered into the confines of the bottom mold section; [0013] [0013]FIG. 3 is a view similar to FIG. 2, showing the uncured tire disposed in the bottom mold section; [0014] [0014]FIG. 4 is a view similar to FIGS. 2 and 3 showing the top mold section being lowered towards its closed position above the bottom mold section; [0015] [0015]FIG. 5 shows the top mold section in a further lowered position with respect to FIG. 4; [0016] [0016]FIG. 6 shows the top mold section in a still further lowered position with respect to the bottom mold section with the mold sections ready to be positioned within an autoclave to cure the tire; [0017] [0017]FIG. 7 is a side elevational view showing an autoclave utilized to cure a tire disposed within the mold of FIGS. 1 - 6 , with one of such molds being lowered into the autoclave. [0018] [0018]FIG. 8 is a view similar to FIG. 7 showing a plurality of the aforedescribed molds as the tires contained within such molds are being cured. [0019] [0019]FIG. 9 is a vertical sectional view of two of the molds as a tire is being cured in the autoclave; [0020] [0020]FIG. 10 shows a top mold section being removed from a bottom mold section after the mold has been removed from the autoclave and the tire has been cured; [0021] [0021]FIGS. 11 and 12 show the top mold section removed and the cured tire being lifted out of the lower mold section while the tread segments are opened radially; [0022] [0022]FIG. 13 is a perspective view showing a cured tire made in accordance with the present invention; [0023] [0023]FIG. 14 is a sectional view taken in enlarged scale along line 14 - 14 of FIG. 13; [0024] [0024]FIG. 15 is a vertical sectional view of a second embodiment of a mold embodying the present invention which may be utilized to cure tires of differing widths; and [0025] [0025]FIG. 16 is an enlarged view of the encircled area designated 16 in FIG. 15. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS [0026] Referring to FIG. 1, there is shown a perspective view of a preferred form of tire mold M embodying the present invention for use in curing a radial tire R shown in FIGS. 13 and 14. The entire molding apparatus is generally toroidal in shape, corresponding to the shape of the tire R to be cured therein, and includes a bottom mold section B and a top mold section T. As shown in FIGS. 2 and 3, the bottom mold section B includes a horizontally extending base plate 20 integrally formed with an outwardly and upwardly extending peripheral bowl 22 . The bowl 22 encompasses a plurality of bottom tread segments BS of like configuration. Each bottom tread segment is supported by an upwardly and outwardly extending guide rod 24 which is anchored to the base plate 20 , as indicated at 26 . Guide rods 24 are slidably received in complementary passages 27 in their respective tread segment. A pair of coil compression springs 30 and 31 are disposed on either side of each guide rod, with the upper portion of such coil spring being supported within a cylindrical cavity 33 that is coaxial with its respective spring by a support pin 35 . The lower end of each rod is anchored to the mold base plate 20 . The radially inner surface of each bottom tread segment is formed with a radially inwardly extending male lug 36 which is adapted to mold the generally horizontally extending portion of the groove 38 defining the left side of the tread pattern of a cured tire R shown in FIGS. 13 and 14. [0027] Referring now to FIG. 4, the top mold section T includes a top plate 39 formed with an integral downwardly and outwardly extending peripheral bowl 40 . Bowl 40 supports a plurality of upper tread segments US similar to but mirror images of the bottom tread segments BS. Each upper tread segment is supported for vertical and horizontal movement by a downwardly and outwardly extending guide pin 41 , having its upper end anchored to the top plate 39 , as indicated at 42 . A pair of coil compression springs 43 and 44 are disposed on either side of guide pins 41 , with the lower portion of each of such springs being supported within a cylindrical cavity 45 , by a rod 50 . The lower end of each is secured to the top plate 39 . The radially inner facing surface of each upper tread segment US is formed with a radially inwardly extending male lug 51 which is adapted to mold the horizontally extending portion of the groove 53 defining the right side of the tread pattern of cured tire R. The upper and lower mold sections are guided for vertical reciprocal movement by means of a plurality of vertically extending guide bars 54 . The upper end of each guide bar is rigidly secured to the bowl 40 of the top plate 39 , with the lower end of each guide bar being slidably disposed within a vertically extending bore 55 formed in a peripheral flange 56 a of the bottom mold section bowl 22 . The top and bottom tread segments US and BS are arcuate and collectively form a circular pattern corresponding to the shape of the tire to be cured when positioned abutting one another. The upwardly-facing side wall surfaces 56 of plate 20 and the downwardly-facing side wall surfaces 62 of top plate 39 form the upper and lower side walls 63 and 64 of the tire to be cured when the top mold is closed on the bottom mold section. Preferably, the mold top and bottom sections are constructed of steel and the top and bottom tread segments are constructed of aluminum. [0028] Referring to FIGS. 1 - 6 , it is important to note that base plate 20 is formed at its outer portion with a plurality of auxiliary lugs 66 that define a downward extension of lugs 36 of each bottom tread segment BS. Similarly, the top plate 39 is formed at its outer portion with a plurality of auxiliary lugs 68 that define an upward extension of lugs 51 of the upper tread segments US. The purpose of such auxiliary lugs is set forth hereinafter. [0029] As indicated in FIG. 2, a tire UR to be cured is supported during the curing process by an annular tire carrier C having complimentary upper and lower bead rings 66 and 67 formed with opposed mirror-image surfaces 70 and 71 that conform to the shape of the bead and inner sidewall portions of a tire to be cured. A conventional inflatable curing bladder BL is sealingly clamped between the bead rings and a vertically extending sleeve 74 that connects the bead rings 66 and 67 . Sleeve 74 is provided with a fluid inlet and outlet fitting 68 in a conventional manner. [0030] In the operation of the aforedescribed apparatus, referring first to FIG. 2, with the top mold section T removed, a conventional hoist (not shown) lowers the uncured tire body UR into the bottom mold section B by a disengageable connector 76 . The uncured tire body is maintained partially inflated at a pressure of about 3 to 6 pounds during the loading process in a conventional manner as by water or air forced into bladder B through fitting 68 . At this time, the bottom tread segments BS will be maintained in their uppermost position by springs 31 . In this position of the bottom tread segments, the lugs 36 thereof are spaced radially outwardly of the extreme periphery of the uncured tire. Referring now to FIG. 3, the uncured tire body UR is shown resting upon sidewall surfaces 56 of the base plate 20 , with the tire lifter 76 removed. In FIG. 4, the top mold section T is shown spaced above the bottom mold section BL, and being lowered towards such bottom section as by a three-leg lifting arm 77 supported by a hoist hook 78 . The ends of the bar 77 are each connected to a cable 81 , the lower ends of which are releasably attachable to lifting lugs 82 (FIG. 1) formed on the top mold section. Referring to FIG. 5, as the top mold section continues its downward movement the flat lower end 83 of each of the upper tread segments US will engage the flat upper end 84 of each of the bottom tread segments BS. Such engagement causes the top and bottom tread segments to be cammed radially inwardly by the slanted camming surfaces 85 and 86 formed on the bowls 22 and 40 of the top and bottom mold sections. Such radially inward movement of the tread segments forces the lugs 36 and 51 partially into the uncured rubber of the tread portion 58 of the uncured tire. It should be understood that the pliable uncured rubber permits the lugs 36 and 51 to move the uncured casing inwardly while partially forming grooves in the uncured rubber. In FIG. 6, the top mold section T has been further lowered into the confines of the bottom mold section B. It will be noted that the tread segment lugs 36 and 51 have been urged deeper into the uncured rubber of the tread pattern. At this time the complete mold M comprising the top and bottom mold sections will be transferred to the autoclave A shown in FIGS. 7 and 8. [0031] Referring now to FIG. 7, there is shown a conventional autoclave A having a heater shell 90 provided with a removable dome 92 . Steam for curing tires in the heater shell is provided by piping 94 . A vertically movable fluid-actuated ram 95 arranged within the heater shell is provided at its upper end with a mold support platform 96 . A pressurized liquid such as water for operating the ram is provided by piping 97 . In FIG. 7, the ram 95 is disposed in its uppermost position to receive one of the aforedescribed complete molds, designated M- 1 . Mold M- 1 is placed upon mold support platform 96 by a three-leg lifting bar 77 such as described hereinbefore, with the three cables 81 having their lower ends releasably attached to lifting lugs 98 formed on bottom mold section B (FIG. 1). Lifting bar 77 is connected to a crane hook 99 . [0032] Referring now to FIG. 8, a plurality, such as two additional molds M- 2 and M- 3 , have been positioned upon mold M- 1 after ram 95 has been lowered within heater shell 90 . Piping 100 from a hot water source has been connected to the interior of the bladder B of each mold. Dome 92 is then closed and steam at about 125 psi is admitted to the heater shell to heat the molds which effect curing of the uncured tires. Concurrently, hot water at about 350 psi is forced into the bladders to urge the uncured tires firmly against the confines of the mold sections' cavities and also to cure the tires from inside out. Nitrogen can be utilized to increase the pressure within the bladders to about 450 psi. After the tires have been cured (usually about 11 hours), the steam pressure in the heater shell and the water pressure in the bladders is reduced to zero. Cool water can then be sprayed inside the heater shell by piping 101 to reduce the temperature within the molds. Dome 92 is then opened and the ram 95 actuated to lift the molds out of the heater shell. [0033] Referring now to FIG. 9, it should be noted that the top mold section T of the lowermost mold M- 1 will be urged downwardly towards its closed position of this figure by the weight of the second mold M- 2 as the latter is positioned upon mold M- 1 within the autoclave A. In a similar fashion the weight of the third mold M- 3 will partially or completely close the top mold section of the second mold section when mold M- 2 is lowered onto mold M- 1 within autoclave A. [0034] Final closing of the molds M- 1 , M- 2 , and M- 3 is effected, however, when the mold sections have been moved upwardly by ram 95 until the top of the uppermost mold M- 3 is moved into engagement with the bolster plate 106 formed on the bottom of dome 22 . The ram will then squeeze each of the mold sections tightly together under great pressure. This squeezing causes the top mold sections to cam the upper and lower tread segments to US and BS to their radially innermost positions whereby lugs 36 and 51 will be forced into the uncured tread portion 58 of each tire, as shown in FIG. 9, with respect to mold M- 1 . At the same time the auxiliary lugs 66 and 68 will be forced into the side portions of the tread grooves. Simultaneously, the highly pressurized bladders BL will urge the inside of the uncured tire tightly against the cavities of the top and bottom mold sections while curing the tire from the inside out. In this manner the tread grooves will be formed as the tire cures. [0035] Referring now to FIG. 10, after each mold M has been lifted out of the heater shell 90 , its top mold section T will be lifted clear of its bottom mold section B. At this time the weight of the cured tire R and tire carrier C will cause the bottom tread segments BS to remain in their radially innermost position, while the upper tread segments US will retract radially under the influence of springs 43 to the extent that the radially inner surfaces of the lugs 51 will be clear of the outer periphery of the tire tread portion 5 8 . Referring now to FIGS. 11 and 12, connector 76 now raises the cured tire R out of the bottom mold section B. As the tire is moved upwardly, the bottom tread segments BS will be urged radially outwardly and upwardly by springs 31 until the radially inner surfaces of the lugs 32 completely clear the outer periphery of the tire tread portion. Lugs 32 will have formed the horizontal portions 38 of one side of the grooves of the tires tread pattern, while the auxiliary lugs 66 have formed the lower portions of such grooves. It is an important advantage that the upper and lower lugs 36 and 51 will be moved radially out of the tire grooves preventing stripping which could cause the tire rubber to pull loose from the tires' belt package. The cured tire R is then removed from the bladder BL and tire carrier C in a conventional manner and the water allowed to drain from the bladder. [0036] Referring now to FIG. 15, there is shown a second embodiment of a mold M′ embodying the present invention. Like parts in FIG. 15 to those of the aforedescribed embodiment of FIGS. 1 - 12 bear primed reference numerals. The difference between mold M′ and mold M is that a plurality of like spacer plates SP are interposed between the top and bottom mold sections T′ and B′. Each spacer plate is releasably secured to bottom mold section B′ by a cap screw 110 . When spacer plates SP are interposed between the top and bottom mold sections the mold M′ can be utilized to cure a tire having a greater width than mold sections T and B of FIGS. 1 - 12 . For example, by interposing the spacer plates between mold sections T′ and B′, the same mold sections can be converted to cure a wider low profile tire, as compared to a more conventional radial tire. It should be noted that opening 112 permits access to cap screw 114 and its stop-washer for easy removal and cleaning of tread segments BS′. [0037] It should be noted that conventional clamshell molds can be converted to molds embodying the present invention, thereby effecting important cost savings for owners of clamshell molds. [0038] Various modifications and changes may be made with respect to the foregoing description without departing from the scope of the present invention.
A method and apparatus for curing large radial pneumatic tires using a plurality of like molds each having top and bottom mold sections provided with radially movable groove-defining tread segments which are automatically extended into a tire to be cured when the molds are positioned within an autoclave and which are automatically retracted when the molds are withdrawn from the autoclave to free the cured tire from its respective mold.
1
FIELD OF THE INVENTION This invention pertains to the area of biological purification of waste water, especially city water, industrial water and distribution water to be made into drinking water. It specifically pertains to a purification process wherein the water to be treated and oxygenated gas are sent in ascending co-currents in the same reactor or biological filter equipped with expanded mineral or plastic materials less dense than water as a filtering material. BACKGROUND OF THE INVENTION It is known that the biological treatment, for example, of water, consists of breaking down organic impurities through the action of a free or fixed purifying biomass housing various microorganisms; bacteria, yeast, protozoans, metazoans, etc. In the free biomass process, using activated sludge, it is impossible to concentrate a great number of different species of microorganisms, which are difficult to decant to the extent that the concentration of the biomass is formed by decanting. The process is thus limited in terms of the applicable load in BOD (biological oxygen demand) and COD (chemical oxygen demand). In a fixed biomass system, the biomass (with bacteria) is concentrated using a collection medium. Suitability for decantation in this case is no longer of vital importance, and the purifying potential of this technique is far superior to the conventional processes. Among the most efficient processes based on the fixed biomass purification principle, those patented and developed by the present inventor can be cited, including the "Biocarbone" (registered trademark) process, and the technique of using a granular bed composed of two areas having different granulometric and biological characteristics in one ascending water current reactor (French Pat. No. 76.21246 published under No. 2 358 362; No. 78.30282 published under No. 2 439 749; No. 86.13675 published under No. 2 604 990). In the "free biomass" techniques, in this case, we will refer primarily to fluidized bed processes, wherein products having a density less than 1 are used for the biofilter material, such as, for example, expanded polymers, according to processes now in the public domain (French Pat. No. 1 363 510 of 1963; English Pat. No. 1 034 076 of 1962) whose various embodiments have yielded numerous patents (French Pat. Nos. 2 330 652; No. 2 406 664; No. 2 538 800; U.S. Pat. No. 4,256,573; Japanese Pat. No. 58-153 590, etc.). The implementation of said floating materials and fluidized granular beds is advantageous in and of itself but involves certain problems and often presents disadvantages, several of which were brought to light by lengthy tests conducted by the present inventor. For example, in a biofilter with ascending water current on balls or granules less dense than water, if air is injected into the base of the filtering bed, filtration cycle lengths are unacceptable and the surface layer is quickly consolidated by suspended materials blocking the passage of the air bubbles; in this case, frequent washings are necessary. Moreover, when materials heavier than water (sand or similar materials) are fluidized, a considerable energy supply is required to pump the liquid, and it is difficult to keep the material inside the reactor. To correct this energy consumption problem, it was proposed to use a fluidized bed of light materials with air intake at the base of the bed, but with a descending water feed (U.S. Pat. No. 4,256,573 and Japanese Pat. No. 58.153590 cited above). However, beginning at certain descending water speeds, air bubbles become trapped inside the material or are carried by the flux of liquid, and the reactor cannot be aerated properly. To remedy the aforementioned problems, the present inventor conducted extensive experiments in order to use all the advantages of a floating or fluidized bed, while attempting to eliminate the phenomena of the trapping of bubbles at the surface, the consolidation of the bed, energy expenditures, problems in washing the filtering bed, etc. SUMMARY OF THE INVENTION These problems were solved through the discovery and subsequent development of a system wherein, in a single reactor or biological filter with ascending co-currents of water and oxygenated gas, the following is used as a means of filtration and bacterial medium, in two adjacent areas: a lower layer consisting of a fluidized bed of particles less dense than water, and an upper layer made of a fixed bed of particles also less dense than 1, but smaller and lighter. In practice, according to one advantageous embodiment, our goal is to satisfy the following equation on a general basis: ##EQU1## Where D1, S1 correspond respectively to the average diameter of the particles and the volume mass of the lower bed. D2, S2: the same definitions as above, but for the upper bed, with SL being the volume mass of the liquid. For the combination of the two aforementioned superposed beds, the process according to the invention thus implements materials that are lighter than water but whose properties of granulometry, density, bed height (as explained in the description below) are different to obtain on the one hand a fluidization of the lower bed during the injection of the oxygenated gas without appreciable perturbation of the upper bed, and, on the other hand, an "automatic" reclassification of the two layers or beds during the phase in which the light materials expand when washed with a countercurrent. Said functions are substantially fulfilled when equation (1) above is satisfied. At rest, these two layers of materials lighter than water stick together because of their different densities. This classification is maintained while the filter is washed with the countercurrent. When air is introduced into the base of the filter by a diffusion device, the air and water mixture passing through the materials has a similar density to the particles in the aforementioned lower layer. The lower bed in this case is fluidized by the ascending movement of the oxygenated gas bubbles, which causes an intensive exchange between the gasses, the water to be treated and the "biofilm" which adheres to the particles of the bed. According to one advantageous arrangement of the invention, the upper surface of the upper fixed bed as defined above is overmounted by a support layer of particles also made of a light material whose characteristics are defined below. In practice, the parameters and characteristics of the different layers of beds can be defined advantageously as follows: for the lower fluidized bed, the granulometry (D1) can vary from 3 to 15 mm, the volume mass is generally between 300 and 800 g/l and the height of the bed ranges from 0.2 to 2 meters depending on the type of reactor used; in the upper fixed bed, the average diameter of the light particles (D2) is from 1 to 10 mm, while the volume mass (S2) varies from 20 to 100 G/l and the height can vary from 0.5 to 3 meters. Finally, in the case of the aforementioned variation, the upper layer overmounting the upper bed comprises particles from 3 to 20 mm in size, having a volume mass of 10 to 50 g/l and a height or thickness of 0.10 to 0.50 meters. The particles of light materials that can be used as a filtering medium/bacterial support covered by the invention are products known in and of themselves. To this end, we can use: expanded plastic materials, closed-cell materials from polyolefins, polystyrene, synthetic rubber polymers and copolymers, etc.; light mineral materials such as clay or expanded shale, or cellulosic products such as wood particles, for example. The granulates of these materials can be in various forms, such as, advantageously: balls, cylindrical pods, etc. In practice, for the effective execution of the process, it is important for the densities of the light particles used within the context of the invention to be increasingly low as we move from the lower layer (fluidized bed) to the upper layer, and then to the aforementioned support layer. For example, the density ranges can respectively be: 0.5 to 0.8 (fluidized bed); 0.3 to 0.1 (fixed bed) and 0.005 to 0.08 (upper support bed). Additional characteristics of the process will be brought to light in the rest of this description. The invention also has as an object a reactor or biological filter comprising the following from bottom to top: an area for the thickening and removal of purification sludge; an air injection device; a filtering material area composed of a first layer of light particles (fluidized bed) and a second layer of less-dense light particles (fixed bed), which is overmounted by a support layer of even lighter particles; a ceiling made of concrete or another perforated material; and, finally, at the top of the reactor, a wash water reserve area having the treated effluent outlet at its top. BRIEF DESCRIPTION OF THE DRAWINGS A non-restrictive embodiment of a water treatment facility is illustrated in the skeleton diagram in FIG. 1 annexed below. FIG. 2 shows another embodiment of the water treatment facility according to the present invention. FIG. 3 shows another embodiment of the water treatment facility according to the present invention. DETAILED DESCRIPTION OF THE INVENTION Reactor 1 thus comprises in its lower part space 2 for the thickening and removal of sludge, then oxygenated fluid injection system 3, the bed 4 which operates under fluidization, part 5 of the fixed bed, then upper support layer 2 held by perforated plate 7 serving as a ceiling; and finally upper free zone 8 serving as a washing reserve where treated water is removed through pipe 9 and collected in 10. The liquid to be treated arrives through pipe 11 and is introduced into area 2 under oxygenated gas injection device 3; the latter can be under bed 4 as indicated in the figure, or in the lower part of said bed. As explained above: at rest, layers or beds 4, 5 and 6 remain one on top of the other because of their different densities; when air (or oxygenated gas) is introduced into the base via 3, the mixture of air and water fluidizes the particles of bed 4 through the movement of the bubbles, which permits an intensive exchange between the gas, the water to be treated and the biofilm that adheres to the particles. During said operation, bed 5 and upper layer 6 remain in a non-turbulent mode (thus the expression "fixed bed" used in this description). Because of the accumulation of suspended materials and the biological growth inside the filtering bed, the material progressively consolidates. The increase in load loss can be monitored by manometric measurements or by the increase in the level of liquid in the column 12 for loading or measuring the load loss. Particle retention can be improved by adding a flocculent. When a pre-defined load loss value is reached, the washing of the bed is triggered. For this purpose, a flush valve 13 is opened until the desired washing speed is reached. The rapid flow of the countercurrent of liquid treated and stored in the upper part 8 of the reactor allows the material to expand. For each granulometry and density of the material, the washing speed can be selected as a function of the desired expansion of the material. The rapid passage of the countercurrent makes it possible to move the stored materials into the interstitial spaces and to disengage the excess biomass accumulated on the surface of the material, but the wash speed can be selected to maintain an active biofilm on the material. After reserve 8 is drained and valve 13 is closed, this makes it possible to restart the feed with a load similar to the load before washing. The injection of the effluent 11 supply at the top of decantation compartment 2 permits the sludge to be thickened as the purification process occurs in the granular bed. The sludge itself is collected in compartment 15 and removed by pump 16. Purified effluent is recycled by a pump 14 making it possible to improve distribution or to add nitrates in the pre-filtering area, if applicable. To extend the periods between washings, very brief flushes of water can be produced periodically by opening valve 13 in order to deconsolidate the material and permit impurities to penetrate more deeply into the filtering bed. These mini-washings will further deconsolidate the lower part of the filter, which is more heavily loaded with suspended materials. Rapid flushes can be triggered to ensure a balanced load loss over the entire height of the filtration medium. This makes it possible to dispense with adjustment components for the equal division of oxygenated gas and water. In order to prevent excessive compression of the bed by continuous intake, a pulsation of air or oxygenated gas can be provided. The air intake can be maintained during the washing operation, pulsed or otherwise, to promote the deconsolidation of the bed. According to one advantageous embodiment of the process, a set of filters can be combined. A common water supply feeds the individual loading columns for each filter. The loading columns prevent the excess pressure created by any accidental consolidation that may occur, while offsetting the consolidation on a continuous basis. With this gravitational feed, the flow can be easily measured and regulated using downspouts. The wash water storage compartments for a set of filters are hydraulically connected. In this way, purified water in the operating filters feeds the wash flow for the filter being deconsolidated, which makes it possible to produce the height and volume of the storage compartments superposed over the filtering bed, the dimensions being calculated as a function of the flow and the number of filters. Another water treatment facility according to the invention but comprising different variations in the embodiment and implementation of the single rector is illustrated in FIG. 2 of the attached drawings. According to a first variation, the oxygenated gas (or air) sprayer 3 can be replaced with an introduction of "white" water, i.e., water saturated with air bubbles, produced in the known manner by spraying air into water under pressure. If desired, this water can be composed of part of the treated water coming out in 9 through the upper part of the reactor. According to a second characteristic, packing 17 advantageously composed of textile materials, for example, crossed filaments of geotextiles or equivalent products, is introduced into the lower part of reactor 1 at the base of the bed 4 to be fluidized. Said packing, designed to allow air and water to pass through it, serves as a medium for fixed bacteria and serves to extract part of the impurities in the water to be treated when it reaches reactor 1 (through 11). According to another variation, we installed equally-divided compartments 18 at the material-water interface level. These compartments, in grid or grate form, permit the oxygenation fluid, the feed water to be treated and the wash flow to be distributed and channeled uniformly. It also makes it possible to break up the compact mass or plug formed by the filtration material during the final wash in the form of a water flush. According to another characteristic, a second injection rack 19 can be installed at the level of fixed bed 5, designed to stir the material-water interface area. The injection can consist either of oxygenated fluid (or white water) or of pressurized sweeping water. In this way, surface consolidation can be avoided and more effectively disengaged when it occurs. Finally, according to another variation also illustrated in FIG. 2, another compartmentalization 20 can be provided under ceiling 7 of the reactor. This compartmentalization, of the same type as the one 18 described above serves especially to promote the equal division of treated effluent and oxygenation fluid. In order to highlight the advantages of the process and facility according to the invention, we will describe excerpts from some sample embodiments, on an illustrative basis. EXAMPLE 1 Using the process according to the invention, various types of waste water were treated in a pilot facility of the same type as in FIG. 1 in the attached drawings, according to two variations of reactors whose characteristics are listed below: TABLE 1______________________________________Bed Parameter Reactor 1 Reactor 2______________________________________Retention system (7) metal sieve with roughened ceiling 2-mm slits openings of 2 mmSupport layer (6) expanded poly- expanded poly- styrene styreneDensity 0.01 0.02Granulometry (mm) 6 to 10 3 to 5Height (m) 0.20 0.30Filtration layer (5) expanded polyethy- expanded poly- lene ethyleneDensity 0.03 0.03Granulometry 3 to 5 2 to 3Height (m) 1.5 2.5Fluidized bed layer (4) lightened poly- expanded shale propyleneDensity 0.8 0.6Granulometry (mm) 10 to 15 5 to 6Height (m) 1.5 0.5______________________________________ The other main characteristics and primary performances obtained are summarized in the table below: TABLE 2______________________________________Flows of water to be treated (1/hr) 120 120Air 250 1500Filter surface (m.sup.2) 0.03 0.5Treatment temperature (°C.) 15 15Volume loads applied (Kg/m.sup.3 -day)COD 15 5BOD 7.5 2.5NTKInput effluent (mg/l)COD 500 500BOD 250 250MES 200 200NTK 50 50Output effluent (mg/l)COD 70 50BOD 20 10MES 20 10NTK 30 5______________________________________ Note: The volume load applied corresponds to the amount of COD, BOD and NTK treated per m.sup.3 of filter in 24 hours. Yield (%) Reactor 1 Reactor 2COD 86 90BOD 92 96NTK 40 90MES = Suspended materialsNTK = Kjeldahl organic nitrogen. EXAMPLE 2 The tests described below concern processing surface water to be made into drinking water, especially for biological nitrification, in a reactor of the same type as in FIG. 1. The material in the fluidized bed was composed of expanded shale having a density of 0.5, a granulometry of approximately 2 mm over a height of 0.50 m. The filtering layer or fixed bed was composed of expanded polystyrene having a density of 0.03 and a granulometry of 1 mm, over a height of 0.5 m. In this case, there was no support layer over the fixed bed. The operating temperature was approximately 10° C. with a filtering speed of 10 m/hour, an aeration speed of 5 m/hour, using air. It was found that the NH 4 content decreased an average of 3.5 to 0.1 mg/l from input (effluent to be treated) to output (denitrified water). Of course, within the context of the invention, one or more variations of the embodiments illustrated in FIG. 2 can be implemented. Moreover, the feed of effluent and/or oxygenated gas may be intermittent. According to an advantageous arrangement illustrated in FIG. 3 of the drawings, the retention device or ceiling (7) can be equipped with sieves, making it possible to create a sufficiently low load loss during washing to prevent the height of water needed from rising above the ceiling (7). According to a particularly advantageous embodiment, these sieves are designed to be screwed directly in decreasing diameters (21, 22, 23) with a protective grid over 24, if necessary, at the top of the reactor at the ceiling (7) level. This makes it possible to prevent any manipulation of the beds. The foregoing description of the specific embodiments will so fully reveal the general nature of the invention that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and therefore such adaptations and modifications are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology herein is for the purpose of description and not of limitation.
A process and apparatus for biological purification of waste water wherein waste water and oxygenated gas are introduced into a reactor using ascending cocurrents. The reactor is equipped with a lower fluidized bed and an upper fixed bed for filtration. The particles in the beds are composed of expanded materials having a density less than 1. The particles in the fixed bed are both smaller and lighter than those of the fluidized bed.
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This application claims the benefit of provisional application No. 60/182,002 filed Feb. 11, 2000 and Ser. No. 60/224,314, filed Aug. 10, 2000, both abandoned. FIELD OF THE INVENTION The invention relates to games involving the use of miniatures to represent characters in the games, and to apparatus for use in such games. BACKGROUND OF THE INVENTION A degree of realism can be added to games, especially war and fantasy games, through the use of miniature figures to represent characters in the games. Each participant in the game manipulates characters, each represented by a miniature figure and each being endowed with certain characteristics, e.g., strength and range of movement, that enter into the resolution of a given event, such as a battle or other interface between characters. As the complexity of each character and each scenario grows, and as the number of characters increases, the complexity of the game increases. Traditionally, miniature figures are made of metal and sold individually or in sets. Typically, the packaging of the figures is at least partially transparent allowing the consumer to view the shape and identity of each figure prior to purchasing. Alternatively, when the packaging is not transparent, the contents of the package are clearly identified. Therefore, because purchasers are allowed to choose a specific figure for their collection, the potential market for trading these figures is minimized. SUMMARY OF THE INVENTION The more complicated prior art games require voluminous rules of play manuals. These manuals include massive amounts of rules and statistics for all of the figures in the game. The number of included statistics makes it difficult for a player to find a specific figure's statistics. In addition, a player is limited to figures included in their specific manual. Further, the rules often entail detailed record keeping by the players, which are often recorded on miscellaneous slips of paper that can become misplaced or disorganized. One challenge of miniature games for a broad audience has always been the size and complication of the rules and the need for record keeping for each figure within the game. In addition, due to the nature of the packaging, the manufacturer of the figures has little control over the collectibility of the figures. The solution to these problems is to: (i) take both the statistics pertaining to a specific character and the recording of game effects upon that character and incorporate them within each figure; and (ii) modify the packaging to conceal the randomly inserted figures to encourage the collectability of the figures. Accordingly, the invention described herein provides a method and an apparatus by which rules and record keeping are incorporated onto the game piece base of the miniature figures themselves with a self-contained record-keeping device. Therefore, a player can use the purchased figures immediately in a game, as opposed to first finding the correct statistics book for that specific character. This device includes counter-wheels having numbers, colors, or other indicia that reflect the nature and values of a character's characteristics and how they change as a game progresses. Values can be customized for each character by providing differently-numbered wheels for the game piece bases. According to the present invention, the game pieces are preferably molded in plastic, pre-painted, and randomly inserted into opaque packages. The packaging is designed to conceal the identity of the figure from the purchaser. These game pieces are produced in different quantities. As a result, some are designed to be rare and very collectible. The players buy packages of game pieces to try to collect the army that the player wants to amass and play with. Typically, the rareness of a game piece corresponds to the value of that game piece. In other words, a rarer game piece is more effective in the game. This method of packaging, selling, and collecting game piece miniatures has the advantage of being unique. The game playing, manufacturing, packaging, selling, and collecting may be performed using game piece bases with or without an attached figure. Other features and advantages of the invention will become apparent to those skilled in the art upon review of the following detailed description, claims, and drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an exploded schematic representation of a game piece base embodying the invention. FIG. 2 is a perspective view of the game piece base illustrated in FIG. 1 . FIG. 3 is a plan bottom view of a base disk of the game piece base illustrated in FIG. 1 . FIG. 4 is a plan top view of a selector disk of the game piece base illustrated in FIG. 1 . FIG. 5 is a cross-section view taken along line 5 — 5 in FIG. 2 . FIG. 6 is a cross-section view taken along line 6 — 6 in FIG. 2 . FIG. 7 is a perspective view of alternate embodiment of the game piece base illustrated in FIG. 1 , including a representational figure. FIG. 8 is a sample of combat data for a selection of human characters to be represented by such game piece bases as illustrated in FIG. 1 . FIG. 9 is an exploded perspective view of a method of packaging a game piece base such as that illustrated in FIG. 7 . FIG. 10 is a sample of a special abilities card to be used in conjunction with a game piece base such as that illustrated in FIG. 1 . Before one embodiment of the invention is explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced or being carried out in various ways. Also, it is understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including” and “comprising” and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Miniature figures are often used in games, especially war and fantasy games, to represent characters in the games. These characters, for example, can be a Roman legionnaire, a Civil War Union soldier, a magician, or a mythical beast, depending on the game. Games can be played to re-enact historical battles, such as the Spartan defense of Thermopylae against the invading Persian army under King Xerxes, or to create a fantastical battle such as one pitting elves and humans against trolls and orcs. Each participant in the game commands an army of characters, each represented by a miniature figure. Each character is endowed with certain strengths and weaknesses, all of which enter into the resolution of a given battle. To add interest to the battle, other factors such as magic and terrain can also be included. As the complexity of each character and each scenario grows, and as the number of characters increases, the complexity of the game increases. The challenge of miniature games for players is the extensive and complicated nature of the rules and the need for record keeping for each figure within the game. In this description, the terms warrior and game piece are used interchangeably to describe the invention. FIG. 1 illustrates a game piece base 10 designed to ease the complexity of such games. Each game piece base 10 is a self-contained record-keeping device that includes a base disk 20 , a label 25 , and a selector disk 30 . The selector disk 30 includes an upper surface 34 , a post 38 mounted in the center of the selector disk 30 , and a plurality of fingers 42 mounted at the periphery of the selector disk 30 . The plurality of fingers 42 includes six short fingers 46 alternating with six long fingers 50 . In alternate embodiments, any other suitable number or sizing of fingers may be used. One of the short fingers 46 includes a button 54 formed therewith and rising vertically from the upper surface 34 . The label 25 including an aperture 58 is attached to the upper surface 34 of the selector disk 30 such that the aperture 58 aligns with the post 38 . A series of numbers in twelve columns of three appears on the label (not shown). Each column is spaced at approximately thirty-degree intervals around the label. In alternate embodiments, any other suitable arrangement of numbers can be used. The base disk 20 includes an L-shaped stat slot or aperture 62 that allows one column of numbers and additional data from the label 25 to be seen at a given position of the base disk 20 relative to the selector disk 30 . As illustrated in FIG. 3 , the base disk 20 also includes a bottom surface 66 , and a plurality of indentations 70 in the periphery of the bottom surface 66 . The number of indentations should match the number of fingers 42 on the selector disk 30 . The base disk 20 also includes an upper surface 74 . When assembled, as illustrated in FIGS. 5 and 6 , the label 25 is applied to the upper surface 34 of the selector disk 30 , and the base disk 20 fits within and is captured by the fingers 42 of the selector disk 30 . The center of the bottom surface 66 of the base disk 20 is supported by the post 38 . This arrangement allows the selector disk 30 to be rotated relative to the base disk 20 . The button 54 interacts with the indentations 70 such that the button 54 resides partially within an indentation 70 when that indentation 70 is aligned with the button 54 . The fingers are sufficiently flexible to allow the button 54 to snap into and out of an indentation 70 as the selector disk 20 is rotated relative to the base disk 20 . Such an arrangement ensures that the base disk 20 will only occupy a given number of discrete indexed positions relative to the selector disk 30 , where the given number of discrete positions is equal to the number of indentations 70 , and where each discrete position allows a player to look through the slot 62 to see whatever numbers, symbols, or colors may appear on the label 25 at that location. In other words, the two disks 20 , 30 are typically aligned such that a column of numbers appears in the slot 62 . The fingers 42 provide a gripping surface such that a player can manually rotate the selector disk 30 relative to the base disk 20 . As illustrated in FIG. 7 , a figure 80 may be attached to the upper surface 74 of the base disk 20 to form a game piece or warrior 90 . The figure 80 may be any representational figure representing a character in a game. In other embodiments (not shown), the described game piece base 10 may be any record-keeping device, such as mechanical and electronic counters that are suitable for recording and conveying information. Specifically, the game piece base 10 allows for the variation of indicia during the course of play. In still other embodiments, the figure 80 may be any suitable type of figure, including humans, animals, and mythical, mechanical, or fantastical creatures. The game piece base 10 may be made available in conjunction with or separately from the figure 80 to allow for interchangeability between figures 80 and bases, or to allow one to acquire a base to match a figure 80 one already has. As is described in more detail below, the design of the game piece base 10 means that each game piece base 10 carries with it a complex two dimensional table that reflects a character's performance statistics at up to twelve stages of damage, where each discrete location of the base disk 20 with respect to the selector disk 30 represents a stage of damage. In alternate embodiments, other numbers of discrete locations can indicate other stages of damage. Examples of such tables are shown in FIG. 8 for a selection of human characters. Thus, the game piece base 10 provides both the table and the current performance of the character, eliminating voluminous rulebooks and record keeping. The game pieces 90 are preferably molded in plastic, pre-painted, and randomly inserted into opaque packages 94 that are preferably glued closed or shrink wrapped to prevent opening. The package 94 is designed to conceal the identity of the warrior 90 from the purchaser. These game pieces 90 are produced in different quantities. As a result, some are designed to be rare and very collectible. The players buy packages 94 to try to collect the game pieces 90 that the player wants to amass and play with. Typically, the rareness of a game piece 90 corresponds to the value of that game piece 90 . In other words, a rarer game piece 90 is more effective in the game. This method of packaging, selling, and collecting game piece miniatures has the advantage of being unique. These packages 94 can either include a single warrior 90 , as shown in FIG. 9 with a plastic insert 98 , or multiple warriors 90 . Preferably, the figures 80 are supplied in sets of five (booster packs) or ten (starter sets) because it improves the purchaser's chances of getting a desired figure 80 . When the multiple figures 80 are sold in a single package, retailers are more likely to carrying the product line because consumers are more likely to buy in volume. Retailers also appreciate that the concealing packages use minimal shelf space and only require a single stock keeping unit (“SKU”) as opposed to the one hundred and sixty SKU's (i.e., one for each character) that would be necessary if the warriors were sold in individual non-concealing packages. The booster pack includes five figures 80 and five stickers to place on the bottom of each figure 80 on which the owner can write their name. The starter set includes ten figures 80 , a rulebook, a comic book to explain the fiction of the game world, a pair of dice, a flexible ruler for measuring distances, and 10 identifying stickers. The purpose for each of these items will be discussed in more detail below. Alternatively, the packages can be configured to reveal the identity of the warrior 90 to allow the purchaser to select specific characters for their collection. But to facilitate trading of such figures 80 , the individual characteristics printed on the label 25 can be concealed by the packaging and varied between identical characters. These different printed labels 25 can be produced in varied quantities. As a result, some can be designed to be rare and very collectible. For example, identical characters can have different indicia printed on the label 25 making one figure 80 faster, stronger, and less susceptible to injury than another according to the rules of the game. Therefore, the more valuable warriors 90 of this embodiment would be those with more favorable numerical characteristics. The purchaser would then have the opportunity to more easily acquire the different warriors 90 and still be encouraged to trade for those warriors 90 that possess superior numerical characteristics. Although the invention described herein may be used for a wide variety of games, a game called MAGE KNIGHT REBELLION will be used as an example to illustrate the invention. In MAGE KNIGHT REBELLION, a player takes on the role of a powerful warlord, king, baron, or high wizard who sends his warriors 90 out to do battle with opposing armies. MAGE KNIGHT REBELLION is a game of tabletop combat using collectible MAGE KNIGHT REBELLION figures 80 . Each figure 80 is called a warrior 90 , and is a member of one of eight different factions: Atlantis Guild, Elemental League, Necropolis Sect, Black Powder Rebels, Knights Immortal, Orc Raiders, Draconum, or Mage Spawn. A player builds an army from his or her collection of warriors 90 . A game may be played using game piece bases 10 with or without an attached figure 80 . A warrior 90 is composed of two main pieces, the figure 80 and the game piece base 10 . The game piece base 10 shows sets of numbers that tell a player how good a warrior 90 is at doing certain things. Each time a warrior 90 takes a point of damage during a game, the player clicks the selector disk 30 clockwise to the next set of numbers. Each point of damage taken by a warrior 90 changes the warrior's game piece base numbers, reducing the warrior's effectiveness. Each time a warrior 90 takes a click of healing during the game, the player clicks the selector disk 20 counter-clockwise to the previous set of numbers. When three skulls show up on the game piece base, the warrior 90 has been eliminated and is removed from the battlefield. Each warrior's game piece base 10 contains important information. This information includes the warrior's: a) name, b) point value ( 1 - 50 ), c) rank (weak, standard, tough), d) front arc (white), e) rear arc (gray), f) collector's number ( 1 - 160 ), g) faction symbol, and h) combat values. Each warrior's base also has a stat slot (to see numbers on the label 25 ). If a warrior 90 does not have a rank, then it is a unique figure 80 . Each warrior 90 has five combat values, four that change during the game and one that stays the same. The four values that change are speed, attack, defense, and damage. These four values are on the game piece base 10 , and can be seen through the warrior's stat slot 62 . The fifth value, range, never changes and is printed on the base 10 . Game Items: In addition to a player's MAGE KNIGHT REBELLION warriors 90 and a rules sheet, a player needs the following items to play a MAGE KNIGHT REBELLION game: a) an eighteen inch flexible ruler and b) two six-sided dice. Additionally, a two-foot-long piece of string and a few pennies (used as tokens during the game) may be used as will be further discussed below. Optionally, a player may also collect simple terrain items. Blank stickers are provided with each pack of MAGE KNIGHT REBELLION warriors 90 for ownership identification. A player writes their initials on the stickers and places them on the bottom of each of that player's warriors 90 . This helps a player to sort out which warriors 90 are that player's at the end of each battle. Building A Player's Army: All of the players must agree to a build total of each player's army. The build total is the total of a player's point values and is always in multiples of 100 points. Each MAGE KNIGHT REBELLION warrior 90 has a point value printed on its game piece base 10 . Once a player knows how many points that player has to build an army, that player chooses which of that player's warriors 90 will participate in the game. A player's army may contain two or more of the same figure 80 , unless that figure 80 is unique. However, the same unique figure 80 can appear in opposing armies. The total of the player's warriors' point values cannot exceed the build total value. Beginning the Game: MAGE KNIGHT REBELLION can be played on a flat tabletop. The players designate a square area to play that is at least three feet long on each side. A game can be played with any number of people, but the game is best when there are two, three, or four different armies. Each player selects one edge of the battlefield to be the player's, and then the game piece bases 10 of each warrior 90 are manipulated such that a green square is showing through the stat slot 62 . Each player places up to two terrain items in a pile off to the side of the battlefield. The purpose of the terrain will be described in greater detail below. Next, each player rolls two six-sided dice where the highest roll determines the first player. The first player places a terrain item from the pile onto the battlefield in a desired location. This continues in clockwise order until all of the terrain items are positioned on the battlefield. Each player then places a warriors 90 on the battlefield within three inches of the player's edge and at least 8 inches away from any other edge of the battlefield, starting with the first player and rotating clockwise until all of the players are positioned. Turns and Actions: In MAGE KNIGHT REBELLION, players alternate moving their warriors 90 and attacking opposing figures 80 to win the battle. At the beginning of a players turn, the player has a certain number of actions. This number is set for the entire game and is dependent upon the build total of the armies. A player gets one action for every one hundred points of that person's build total. For example, if the build total is 200 points, the player receives 2 actions per turn. During each players turn, that player decides which warriors 90 to give actions, however, the same warrior 90 may not be given two actions in the same turn. Actions include moving one warrior 90 , performing ranged combat with one warrior 90 , performing close combat with one warrior 90 , or passing. Once a player has completed their allotted actions, it becomes the next player's turn, and the next player gets the same number of actions. Play proceeds with each player taking a turn. If a player gives an action (other than pass) to the same warrior 90 on two consecutive turns, that warrior 90 takes one point of damage after completing its subsequent action. This damage represents the fatigue caused by taking actions on two consecutive turns. A player may not give any warrior 90 an action (other than pass) on three consecutive turns. If a player has trouble remembering which warrior 90 that player has given an action to on a previous turn, that player can mark that warrior 90 with a token, such as a penny, to remind that player. Game Concepts: Distances measured for set-up, movement, or ranged combat, are always measured from the center of the game piece base 10 . Two or more warriors 90 are in base contact when the bases of each are touching. Friendly figures 80 are warriors 90 that are controlled by the same player or allied teammates, and cannot target other friendly figures 80 . Opposing figures 80 are any warriors 90 that are controlled by an opponent. Status of friendly and opposing figures 80 are set at the beginning of the game and cannot change by treaties or agreements. Special Abilities: There are special colored blocks on each warrior's game piece base 10 . These colors represent special abilities that warrior 90 has while they are displayed. There are four areas in which a player can find colored blocks representing the warrior's special abilities. These four areas are: 1) behind the move value, 2) behind the attack value, 3) behind the defense value, and 4) behind the damage value through the stat slot 62 on the warrior's game piece base 10 . Descriptions of these special abilities appear on the MAGE KNIGHT REBELLION Special Abilities Card, an example of which is shown in FIG. 10 . If a special ability is described as optional, the owning player decides if the ability is, or is not, used for the turn. Movement: A warrior's speed value is shown on its game piece base 10 . This is the maximum number of inches the warrior 90 may move when given a move action. When a player moves a warrior 90 , the player physically moves the warrior 90 across the battlefield along the exact movement path. This distance can be measured by the flexible ruler. The game piece bases 10 of other warriors 90 block movement, so a player's warrior 90 may not touch or cross the game piece base 10 of any other warriors 90 during its move. When a player finishes moving a warrior 90 , the figure 80 may be faced in any direction. The direction that the figure 80 is facing is important because the warrior 90 may only attack (ranged combat and close combat) out of its front arc and it is at a disadvantage when attacked in close combat through its rear arc. If a player gives a move action to a warrior 90 that is in contact with the game piece base 10 of an opposing warrior 90 , the player must break away from the contact. To break away, the player must roll a six-sided die. If the player rolls a 1, 2 or 3, the warrior 90 fails to break away and may not move this turn, although the warrior 90 may be rotated if desired. If the player rolls a 4, 5, or 6, the player warrior 90 has successfully broken away and may move normally. If a player's warrior's movement takes it into base contact with one or more opposing figures 80 , those opposing figures 80 immediately have the option to spin in place to bring any portion of their front arcs into contact with the moving warrior 90 . Ranged Combat: Ranged combat attacks represent everything from bows and gunfire, to magical spells and mind attacks. Each warrior 90 has a range value printed on its game piece base 10 . If this value is greater than zero and the warrior 90 is not in contact with the game piece base 10 of an opposing warrior 90 , then a player may give that warrior 90 a ranged combat action. This number represents the maximum number of inches that the warriors 90 ranged attack can reach. The number of arrow symbols shown with the warrior's range value is the maximum number of different targets the warrior 90 may attack with each ranged combat action. Certain special abilities allow ranged combat to be resolved against an increased number of targets. When a player gives a ranged combat action to one of the player's warriors 90 , the player marks the warrior's range in inches on a string with a pen or marker (or just holds it with a player's fingers). The player places the end of the string at the center of the figure's game piece base 10 and extends the string to the center of the target's game piece base 10 . The path of the string is called the line of fire. If a player is firing at more than one target, the player must draw a line of fire to each of them. The line of fire must pass through the attacking warrior's front arc, and each target must be within the range a player has marked on the string. The line of fire is blocked if it crosses any warrior's game piece base 10 (friend or foe) other than a target. If the line of fire is blocked, a player may not attack the target warrior 90 . A player may check to see if a line of fire is blocked at any time. The attacking player rolls two six-sided dice and adds their values to the warrior's attack value. If the result is equal to or greater than the target's defense value, as shown on its game piece base 10 , then the target is hit and damaged. When a player's warrior 90 hits a target with an attack, the target must take a number of clicks of damage equal to the attacker's damage value. When a warrior 90 is attacking more than one target with a ranged combat attack, which is allowed when the warrior's range value is shown with more than one arrow, a player only rolls the dice once. The total of the dice plus the warrior's attack value is compared to every target's defensive value. Some targets with low defensive values may be damaged by the attack, while others with high defensive values may not be. Whenever a ranged combat action is used to attack more than one single target, the damage value of the attack, if successful, is always one, despite the warrior's normal damage value. Close Combat: Close combat represents hand-to-hand and melee weapon attacks. If a player gives the close combat action to a warrior 90 , the front arc of the warrior's game piece base 10 must be touching the target's game piece base 10 . The attacking player rolls two six-sided dice and adds their values to the warrior's attack value. If the result is equal to or greater than the target's defense value as shown on its game piece base 10 , then the target is hit and damaged. The player adds one to the dice roll if the warrior 90 is in contact with the rear arc of the target warrior's game piece base 10 . Damage: When a warrior 90 hits a target with a ranged or close combat attack, the warrior 90 inflicts damage in the amount of the warrior's damage value. This is the number of clicks of damage the warrior 90 has delivered to the target. The opposing player must click the target's game piece base 10 clockwise that number of clicks. The damage inflicted reduces the target's abilities, and may even eliminate the target from the game. Rolling a “2” or a “12”: Whenever a warrior 90 is making a ranged or close combat attack and rolls a “2,” the warrior 90 automatically misses the target. This is called a critical miss, and-the warrior 90 must take one click of damage representing a self-inflicted wound caused by the miss. If a player rolls a “12,” the warrior 90 has automatically hit the target and does one extra click of damage. Alternatively, if a player is trying to heal a warrior 90 and rolls a “12,” then the healing is automatically successful and delivers one extra click of healing. Healing: By using special abilities such as magic healing, regeneration, and vampirism, a player may repair clicks on a figure's base 10 . When repairing, click the selector disk 30 counter-clockwise, but never past the figure's starting position. Capturing: A player has the option in close combat of capturing a target instead of damaging the target. A player must declare a capture attempt before rolling the close combat dice. The defense value of the target warrior 90 is increased by two if a player is attempting to capture it. If a player hits the target, the player doesn't damage the target, but the target is captured and a player's opponent may no longer give the target an action. Each warrior 90 may only have one captured figure 80 under that warrior's control. The capture is shown by keeping the captured figure's game piece base 10 in contact with the controlling warrior's game piece base 10 at all times. No warrior 90 , friend or foe, may target a captured figure 80 for any purpose. The captured figure 80 always moves with the captured figure's controlling warrior 90 using the lowest of the two figures' movement values. The controlling warrior 90 may only be assigned a move action or a pass action; it may not initiate any further combat. The controlling warrior 90 may not be the target of an opponent's capture attempt. If a warrior 90 with a captured target is eliminated, the captured target may immediately begin operating normally. Formations: An action that a player gives to one of the player's warriors 90 can affect other warriors 90 in a player's army of the same race by using formations. Note that a player can never be forced to use a formation if the player does not want to. A formation may never contain figures 80 from different factions, although a player may use different figures 80 from the same faction in a formation. Mage spawn figures 80 may never use formations. Movement Formation: If three to five of a player's warriors 90 are grouped so that each one's game piece base 10 is touching the game piece base 10 of another, then the player can call this group a movement formation. When a player gives a move action to just one of these warriors 90 , all of the warriors 90 in the movement formation may move at the same time and as part of that same action. At the end of the move, each warrior's game piece base 10 must still be touching the game piece base 10 of another warrior 90 in the formation. Therefore, the speed value of the slowest warrior 90 in the movement formation will restrict how far a player's warriors 90 will move. Movement formations are good because one move action allows a player to move several warriors 90 instead of just one. If any figure 80 in a movement formation fails to break away, that figure 80 may not move individually other than rotating to a new direction. Ranged Combat Formations: If three to five of a player's warriors 90 have their game piece bases 10 touching, a player may declare a ranged combat formation. When a player gives a ranged combat action to just one of these warriors 90 , all of the warriors 90 in the ranged combat formation contribute to the attack. The target figure 80 must be within the range value of each of a player's warriors 90 , and no line of fire may be blocked. The warrior 90 that a player gives the ranged combat action to is called the primary firer. To resolve the attack, a player uses the primary firer's attack value and damage value. Each additional warrior 90 in the ranged combat formation adds one to the attack dice roll. There is no damage bonus. Ranged combat formations are good because they allow a player to hit and at least do some damage to target warriors 90 with very high defensive values. Even if only one warrior 90 in the formation is given the ranged combat action, all warriors 90 are considered to have performed an action. Close Combat Formations: If two or three of a player's warriors 90 have their game piece bases 10 touching each other and a game piece base 10 of a single opposing warrior 90 , a player may declare a close combat formation against that opposing warrior 90 . When the player gives a close combat action to just one of a player's warriors 90 , all of the warriors 90 in the close combat formation contribute to the attack. The warrior 90 that the player gives the close combat action to is called the primary attacker. To resolve the attack, the player uses the primary attacker's attack value and damage value. Each additional figure 80 in the close combat formation adds one to the combat dice roll. There is no damage bonus. Close combat formations are good because they help overcome the difficulty in capturing an opponent's warrior 90 or damaging a warrior 90 with a high defensive value. Similar to ranged combat formations, if one warrior 90 in the formation is given the close combat action, all warriors 90 are considered to have performed an action. If a “2” is rolled during a close combat or ranged combat formation, only the primary attacker rotates his base clockwise one click. Tabletop Terrain: Players are not required to use terrain when fighting a MAGE KNIGHT REBELLION battle, but adding terrain to the tabletop will make the game more challenging and interesting. There are four types of terrain in MAGE KNIGHT REBELLION: a) clear, b) hindering, c) blocking, and d) elevated. An empty tabletop is considered to be clear terrain. Hindering Terrain: Examples of hindering terrain are brush, low walls, and debris. A player can represent these with construction paper, pieces of felt, fabric, or scale models. Hindering terrain should lie flat on the table so that the terrain does not interfere with the placement of a player's warriors' game piece bases 10 . If a line of fire passes through any amount of hindering terrain or any number of hindering terrain features, one is added to the target's defensive value, this is called a hindering terrain modifier. Close combat attacks are not affected by hindering terrain. A player's warriors 90 can move into and through hindering terrain, but there are restrictions. If a player's warrior 90 begins a move with any part of the warrior's game piece base 10 touching clear terrain, the warrior's movement must end immediately when the warrior's game piece base 10 crosses completely into a hindering terrain feature. If a player's warrior 90 begins a move with any part of the warrior's game piece base 10 touching hindering terrain, the warrior's speed value is cut in half for the turn. A firer in hindering terrain is not penalized by the modifier if its front arc lies entirely outside of the hindering terrain boundary and the line of fire does not pass into or through any other hindering terrain features. This represents use of the hindering terrain as protection while firing from the edge of the hindering terrain. Blocking Terrain: Examples of blocking terrain are large trees, high walls, and buildings. A player can represent them with common items such as salt shakers, cups, and stacks of books, or the player can use scale models. Blocking terrain blocks movement, so a warrior 90 may not move through it. Also, blocking terrain blocks any line of fire crossing it. Elevated Terrain: All elevated terrain is assumed to represent the same level of height above the battlefield. Elevated terrain features include hills and low plateaus. Elevated terrain may include areas of hindering and/or blocking terrain, but is otherwise assumed to contain clear terrain. Players can represent elevated terrain with stacks of books and magazines, or use scale models. All figures 80 must stop as soon as they move up into elevated terrain, or down out of elevated terrain (as if they were entering a hindering terrain feature). When measuring a player's move, don't measure any vertical distance traveled, just the horizontal portion of the warrior's 90 move along the tabletop or elevated terrain feature. Elevated terrain features block lines of fire unless the firer or target or both are on the elevated terrain. If both the firer and target are on elevated terrain, nothing affects the line of fire except elevated hindering and blocking terrain features and other elevated figure 80 bases. If the firer or target is on elevated terrain, but the other is not, the line of fire is blocked if it crosses a different elevated terrain feature. Intervening blocking terrain features also block the line of fire, whether elevated or not. Intervening elevated figure 80 bases will also block these lines of fire, but those off of elevated terrain can be ignored. Hindering terrain modifies the attack only if either the firer or target is in hindering terrain, otherwise it too can be ignored. Special Terrain: Shallow water features like streams, fords, and ponds are treated as hindering terrain for movement, but have no effect on ranged combat actions. Deep water features like rivers and lakes are treated as blocking terrain for movement, but have no effect on ranged combat actions. Low walls are special types of hindering terrain. Movement stops when a player's warrior 90 reaches the far side of a low wall, and speed is never halved on subsequent turns when that player's warrior 90 moves away from a low wall. Ranged combat attacks use the hindering terrain modifier for crossing the low wall, except if the firer is in base contact with the low wall. Close combat attacks are allowed between adjacent figures 80 on opposite sides of a low wall as if they were in base contact. Abrupt elevated terrain such as raised parapets, flat rooftops, and plateaus flanked by cliffs are treated like normal elevated terrain except that close combat attacks are not allowed. Formations are also not allowed to be broken between levels of an abrupt elevated terrain. Figures 80 may only move onto or off of such terrain if they have special abilities or a ladder or stairway exists. Height Advantage: When a firer that is not on elevated terrain makes a ranged combat attack against an elevated target, the target's defense value is increased by one. This is the height advantage modifier. When using a ranged combat formation, only the primary attacker's line of fire is subject to the height advantage modifier and the hindering terrain modifier. Close combat between figures 80 at different elevations is allowed if the bases 10 would be in contact if not for the height difference. If the target of a close combat attack is elevated while the attacking warrior 90 is not, the target gets the height advantage modifier. Ending the Game: The game ends when any of the following occur: a) Only one player remains with a warrior 90 on the battlefield; b) A predetermined time limit for the game expires; or c) All remaining players agree to end the game. A player may also decide to withdraw during their turn. If a player decides to withdraw, the player removes all of the player's remaining warriors 90 from the game. The winner of the game is determined by the player with the highest number of victory points. Victory points are accumulated by eliminating opposing warriors 90 , maintaining captured warriors 90 , and by one's own surviving warriors 90 . The points awarded for eliminating an opposing warrior 90 is the point value of that warrior 90 . The points awarded for holding a warrior 90 captive at the end of the game is twice the point value of the captured warrior 90 . The points accumulated for each surviving warrior 90 is equal to that warrior's point value. After the game, all players retrieve their eliminated and captured figures 80 . Various features of the invention are set forth in the following claims.
A method and an apparatus by which rules and record keeping in games employing miniature figures as game pieces are incorporated onto the base of the miniature figures themselves. Counters or wheels keep track of a character's characteristics and how they change as a game progresses. Values can be customized for each character by providing differently numbered wheels for the bases. Also, a method for providing collectable game pieces with varied features by providing them to the consumer concealed in packaging.
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RELATED APPLICATIONS [0001] This application claims priority to European Application No. EP 04 004 054.5, filed Feb. 23, 2004, which is hereby incorporated by reference. BACKGROUND OF THE INVENTION [0002] 1. Technical Field [0003] The invention relates to the use of meloxicam or a pharmaceutically acceptable salt thereof for preparing a pharmaceutical composition for the treatment or prevention of respiratory diseases in pigs. [0004] 2. Background Information [0005] Respiratory disease in pigs belongs to the most important health problems in swine production. Porcine respiratory disease is primarily caused by infectious agents, but environmental factors have a strong influence. The relevant pathogens include mycoplasmas, bacteria, and viruses (e.g., G. Christensen, V. Sorensen, and J. Mousing, Diseases of the Respiratory System, In: Diseases of Swine, B. E. Straw, S. D'Allaire, W. L. Mengeling, & D. J. Taylor (eds), Iowa State University Press, Ames, Iowa (1999) pp. 913-940). [0006] The most important measures for the control of porcine respiratory disease are to improve herd management and housing conditions and introduce a vaccination program. However, if pigs have developed respiratory disease, they have to be treated. [0007] Current therapy of porcine respiratory disease includes treatment with antibiotics. The successful use of various types of antibiotics is described, including β-lactams, quinolones, and tetracyclines (e.g., I. Lang, M. Rose, E. Thomas, & E. Zschiesche, A Field Study of Cefquinome for the Treatment of Pigs with Respiratory Disease, Revue Med Vet 8-9, (2002) pp. 575-580). [0008] It is known that cyclooxygenase-2 (COX-2) plays a relevant role in the pathophysiology of porcine pleuropneumonia caused by Actinobacillus pleuropneumoniae. Isolated porcine alveolar macrophages increase their COX-2 activity after exposure to Actinobacillus pleuropneumoniae (W. S. Cho & C. Chae, In vitro Effects of Actinobacillus pleuropneumoniae on Inducible Nitric Oxide Synthase and Cyclooxygenase- 2 in Porcine Alveolar Macrophages, Am J Vet Res 64, (2003) pp. 1514-1518). Moreover, in situ hybridization (W. S. Cho & C. Chae, Expression of Cyclooxygenase- 2 in Swine Naturally Infected with Actinobacillus pleuropneumoniae, Vet Pathol 40, (2003) pp. 25-31) and immunohistochemistry (W. S. Cho & C. Chae, Immunohistochemical Detection of Cyclooxygenase- 2 in Lungs of Pigs Naturally Infected with Actinobacillus pleuropneumoniae, J Comp Pathol 127, (2002) pp. 274-279) showed increased COX-2 expression in lungs of pigs naturally infected with Actinobacillus pleuropneumoniae. [0009] Moreover, it is well-known that acetylsalicylic acid (aspirin) can be used for the treatment of pigs with respiratory disease. However, little information on controlled clinical studies is available: for a review, see A. Laval, Utilisation des Anti - inflammatoires chez le Porc, Rec Méd Vét 168 (8/9) (1992) pp. 733-744. Ketoprofen, and, to a lesser extent, flunixin decrease fever induced by experimental infection with Actinobacillus pleuropneumoniae (J. M. Swinkels, A. Pijpers, J. C. Vernooy, A. Van Nes, & J. H. Verheijden, Effects of Ketoprofen and Flunixin in Pigs Experimentally Infected with Actinobacillus pleuropneumoniae, J Vet Pharmacol Ther 17, (1994) pp. 299-303). However, no effects on lung lesions were observed. Ketoprofen was further tested in a controlled, blinded clinical field study (M. F. De Jong, O. Sampimon, J. P. Arnaud, G. Theunissen, G. Groenland, & P. J. Werf, A Clinical Study with a Non Steroid Antiinflammatory Drug, 14, (1996) 659 IPVS). In this study, ketoprofen had no effect on clinical score, relapse, or cure rate. [0010] Indomethacin alleviated experimental endotoxin-induced respiratory failure in pigs (N. C. Olson, T. T. Brown, J. R. Anderson, & D. L. Anderson, Dexamethasone and Indomethacin Modify Endotoxin - Induced Respiratory Failure in Pigs, J Appl Physiol 58, (1985) pp. 274-284). [0011] Meloxicam is a non-steroidal anti-inflammatory compound that belongs to the oxicam class and exerts potent anti-inflammatory, anti-exudative, and anti-pyretic activity. The efficacy of meloxicam as an adjunctive therapy in the treatment of respiratory infections in cattle has been widely proven. Recently meloxicam was approved for the treatment of MMA (A. Hirsch et al., J Vet Pharmacol Therap 26 (2003) pp. 355-360) and locomotor disorders in pigs (G. Friton et al., Berl Münch Tierärztl Wschr 116 (2003) pp. 421-426). [0012] A review article (P. Lees, The Pharmacokinetics of Drugs Used in the Treatment of Respiratory Diseases in Cattle and Pigs, (1991) pp. 67-74, Hatfield, U.K. Proc. Royal Vet. Coll.) focuses on pharmacokinetics used in the treatment of respiratory disease in cattle and pigs; however, non-steroidal anti-inflammatory drugs data for pigs was almost entirely lacking and only lists data for cattle including meloxicam. [0013] The use of meloxicam in conjunction with antibiotics in bovine respiratory disease is well-established (H. Schmidt, H. Philipp, E. Salomon, & K. Okkinga, Effekte der zusätzlichen Gabe von Metacam ( Meloxicam ) auf den Krankheitsverlauf bei Rindern mit Atemwegserkrankungen, Der praktische Tierarzt 81 (2000) pp. 240-244) and registered in the EU. However, to date no information on the use of meloxicam in pigs with respiratory disease is publicly available. [0014] Since the pharmacokinetics in pigs and cattle differ substantially for meloxicam (plasma half-time in cattle is 26 hours whereas it is 2.5 hours in pigs), there is no expectation that the successful use of meloxicam in cattle should also be beneficial for pigs. Moreover, the causative agents for bovine and porcine respiratory disease differ substantially. [0015] The problem underlying the present invention was to provide a medication for the prevention or treatment of respiratory diseases in pigs, one of the most important health problems in swine production. BRIEF DESCRIPTION OF THE INVENTION [0016] It has been found surprisingly that meloxicam can be used for the treatment or prevention of respiratory diseases in pigs. [0017] Accordingly, the invention relates to the use of meloxicam or a pharmaceutically acceptable salt thereof for preparing a pharmaceutical composition for the treatment or prevention of respiratory diseases in pigs. [0018] Moreover, the invention relates to a method of treating or preventing respiratory diseases in pigs, which method comprises administering an effective amount of meloxicam to the pigs in need thereof. [0019] Furthermore, the invention relates to veterinary preparation containing meloxicam as well as at least one antibiotic selected from the group consisting of β-lactams, quinolones, tetracyclines, sulfonamides, fenicoles, and macrolides. [0020] Another aspect of the invention is a ready-to-use two-component system for the treatment of respiratory diseases in pigs, wherein: (a) one component contains meloxicam and a pharmaceutically acceptable carrier; and (b) the other component contains at least one antibiotic selected from the group consisting of β-lactams, quinolones, tetracyclines, sulfonamides, fenicoles, and macrolides and a pharmaceutically acceptable carrier. [0023] Still another aspect of the invention is an article of manufacture comprising packaging material contained within which is a composition consisting of meloxicam and a pharmaceutically acceptable carrier, and a label which indicates that the composition can be used to treat or prevent respiratory diseases in pigs. BRIEF DESCRIPTION OF THE DRAWINGS [0024] FIG. 1 shows the incidence of fever (rectal temperature ≧40.56° C.) in percent following the first treatment in a group of pigs treated with oxytetracycline and meloxicam (♦), in a group of pigs treated with oxytetracycline alone (∘), and in the untreated control (Δ). [0025] FIG. 2 shows the efficacy of meloxicam in drinking water in reducing lung lesions caused by experimental Swine Influenza Virus (SIV) infection on study days 7 and 14. DETAILED DESCRIPTION OF THE INVENTION [0026] Preferably the invention relates to the use of meloxicam or a pharmaceutically acceptable salt thereof for preparing a pharmaceutical composition in a form suitable for systemic or oral administration for the treatment or prevention of respiratory diseases in pigs. Meloxicam (4-hydroxy-2-methyl-N-(5-methyl-2-thiazolyl)-2H- 1,2-benzothiazine-3-carboxamide-1,1-dioxide) of formula is an active substance which belongs to the group of NSAIDs (non-steroidal-anti-inflammatory drugs). Meloxicam and the sodium and meglumine salt thereof (N-methyl-D-glucamine salt) are described in EP-A-0 002 482 (corresponding to U.S. Pat. No. 4,233,299), each of which is hereby incorporated by reference. [0027] Meloxicam may be used according to the invention in the form of a physiologically acceptable acid addition salt. By physiologically acceptable acid addition salts are meant, according to the invention, the meglumine, sodium, potassium, or ammonium salt, preferably the meloxicam meglumine salt. [0028] In a further preferred embodiment, the pharmaceutical composition is administered corresponding to a daily dose of meloxicam ranging from 0.01 mg/kg to 5.0 mg/kg, preferably from 0.1 mg/kg to 3.5 mg/kg, in particular from 0.2 mg/kg to 2.0 mg/kg. [0029] The pharmaceutical composition is preferably administered in a form suitable for injection, in particular for intramuscular injection, or in form of water soluble granules for administration via drinking water or as top dressing on feed. [0030] A suitable injection formulation is disclosed, for example, in Example 25 of EP-A-0 002 482. Furthermore, such injection solutions may additionally contain excipients selected from among citric acid, lecithin, gluconic acid, tartaric acid, phosphoric acid and EDTA or the salts thereof as disclosed in the Examples 1 to 5 of the International Patent Application WO 01/97813 (corresponding to U.S. Patent App. Pub No. 2002/0035107), each of which is hereby incorporated by reference. Moreover, an injection solution of meloxicam for needleless injections is disclosed in the International Patent Application WO 03/049733 (corresponding to U.S. Patent App. Pub No. 2003/0119825), each of which is hereby incorporated by reference. [0031] Suitable water soluble granules for administration via drinking water or as top dressing on feed are, for example, disclosed in the International Patent Application PCT/EP03/11802 (corresponding to U.S. Patent App. Pub No. 2004/0234596), each of which is hereby incorporated by reference. [0032] In a preferred embodiment of the invention, the meloxicam granules contain a binder which may be selected from among hydroxypropylmethylcellulose, polyvinylpyrrolidone, gelatine, starch, and polyethylene glycol ether, preferably hydroxypropylmethylcellulose, polyvinylpyrrolidone, and polyethylene glycol ether, and most preferably hydroxypropylmethylcellulose and polyvinylpyrrolidone. [0033] In another preferred embodiment of the invention, meloxicam granules contain a sweetener, which may be selected from among sodium saccharine, aspartame, and SUNETT® (acesulfame K), preferably sodium saccharine or aspartame. [0034] Particularly preferred according to the invention are meloxicam granules containing a flavoring agent which may be selected from among vanilla, honey flavoring, apple flavoring, and contramarum, preferably honey flavoring and apple flavoring. [0035] Also particularly preferred are meloxicam granules in which the carrier is selected from among lactose, glucose, mannitol, xylitol, sucrose, and sorbitol, preferably glucose, lactose, or sorbitol, more preferably glucose or lactose, and most preferably glucose. [0036] Most preferred are the following granules of meloxicam recipes: EXAMPLE A 0.6% Meloxicam Granules [0037] g/100 g Meloxicam 0.6 Meglumine 0.42 Hydroxypropylmethylcellulose 3.00 Povidone 2.00 Glucose monohydrate 93.98 EXAMPLE B 1.2% Meloxicam Granules [0038] g/100 g Meloxicam 1.2 Meglumine 0.84 Hydroxypropylmethylcellulose 3.00 Collidone 25 2.0 Glucose Monohydrate 92.96 EXAMPLE C 0.6% Meloxicam Granules [0039] g/100 g Meloxicam 0.6 Meglumine 0.42 Pharmacoat 606 4.0 Macrogol 6000 1.0 Acesulfame K 0.3 Lactose 93.68 EXAMPLE D 0.6% Meloxicam Granules [0040] g/100 g Meloxicam 0.6 Meglumine 0.42 Pharmacoat 606 4.75 Macrogol 6000 0.25 Acesulfame K 0.3 Liquid vanilla flavoring 0.05 Lactose 93.63 [0041] Particularly preferred are meloxicam granules in which the content of meloxicam is between 0.05% and 4%, preferably between 0.1% and 2%, preferably between 0.3% and 1.8%, more preferably between 0.4% and 1.5%, and most preferably 1.2%. Also particularly preferred are meloxicam granules which contain meglumine and meloxicam in a molar ratio of about 9:8 to 12:8, preferably 10:8. [0042] Meloxicam can be used according to the invention to treat or prevent respiratory diseases in any breed of swines. Preferably pigs selected from the swine breeds American Landrace, American Yorkshire, Angeln Saddleback, Arapawa Island, Ba Xuyen, Bantu, Bazna, Beijing Black, Belarus Black Pied, Belgian Landrace, Bentheim Black Pied, Berkshire, Black Slavonian, British Landrace, British Lop, Bulgarian White, Cantonese, Chester White, Czech Improved White, Danish Landrace, Dermantsi Pied, Duroc, Dutch Landrace, Fengjing, Finnish Landrace, French Landrace, German Landrace, Gloucestershire Old Spots, Guinea Hog, Hampshire, Hereford, Hezuo, Iberian, Italian Landrace, Jinhua, Kele, Krskopolje, Kunekune, Lacombe, Large Black, Large Black-white, Large White, Lithuanian Native, Mangalitsa, Meishan, Middle White, Minzhu, Mong Cai, Mukota, Mora Romagnola, Moura, Mulefoot, Neijiang, Ningxiang, Norwegian Landrace, Ossabaw Island, Oxford Sandy and Black, Philippine Native, Pietrain, Poland China, Red Wattle, Saddleback, Spots, Swabian-Hall, Swedish Landrace, Tamworth, Thuoc Nhieu, Tibetan, Turopolje, Vietnamese Potbelly, Welsh, and Wuzhishan, in particular American Landrace, Belgian Landrace, British Landrace, Danish Landrace, Dutch Landrace Finnish Landrace, French Landrace, German Landrace, Italian Landrace, and Pietrain can be treated with meloxicam according to the present invention. [0043] Furthermore preferred is the administration of meloxicam is in conjunction with an antibiotic, preferably selected from the group consisting of β-lactams, quinolones, tetracyclines, sulfonamides, fenicoles, and macrolides. Most preferred are amoxicillin, oxytetracycline, florfenicol, tylosin, tilmicosin, and sulfamethazine. [0044] The dose of antibiotic is not critical per se and depends strongly on the different efficacies of the antibiotics used. As a rule up to 150.0 mg/kg, preferably from 0.1 mg/kg to 120 mg/kg, in particular from 10 mg/kg to 110 mg/kg of an antibiotic are co-administered together with meloxicam. [0045] The following dose ranges are most preferred: Amoxicillin:  5 mg/kg to 30 mg/kg, in particular about 10 mg/kg; Oxytetracycline: 20 mg/kg to 70 mg/kg, in particular about 30 mg/kg; Florfenicol: 10 mg/kg to 20 mg/kg, in particular about 15 mg/kg; Tylosin: 10 mg/kg to 25 mg/kg, in particular about 16 mg/kg; Tilmicosin:  5 mg/kg to 30 mg/kg, in particular 10 mg/kg to 20 mg/kg; and Sulfamethazine: 80 mg/kg to 150 mg/kg, in particular about 100 mg/kg. [0046] The phrase “co-administration” (or “administration in conjunction with”), in defining use of meloxicam and an antibiotic, is intended to embrace administration of each agent in a sequential manner in a regimen that will provide beneficial effects, in particular, reduction of the symptoms of the respiratory disease in the affected pig of the drug combination. The phrase also is intended to embrace co-administration of these agents in a substantially simultaneous manner, such as in a single capsule or injection solution having a fixed ratio of these active agents or in multiple, separate capsules for each agent. [0047] Accordingly, meloxicam and the antibiotic may be co-administered in a combined form, or separately or separately and sequentially wherein the sequential administration is preferably close in time. [0048] Preferably the medicament according to this invention is used for the prevention or treatment of Porcine Respiratory Disease Complex in growing or fattening pigs; or for the prevention or treatment of respiratory diseases in pigs caused by mycoplasmas, in particular Mycoplasma hyopneumoniae, Mycoplasma hyorhinis, for the prevention or treatment of respiratory diseases in pigs caused by bacteria in particular Actinobacillus spp., in particular Actinobacillus pleuropneumoniae, Bordetella bronchiseptica, Pasteurella multocida, Arcanobacterium pyogenes, Streptococcus spp., and Staphylococcus spp., or for the prevention or treatment of respiratory diseases in pigs caused by viruses, in particular Swine Influenza Virus, Aujetzky's Virus, Porcine Reproductive and Respiratory Syndrome Virus, Porcine Circovirus, and Transmissible Gastroenteritis and Porcine Respiratory Coronavirus. [0049] Most preferably the medicament according to this invention is used for the prevention or treatment of respiratory diseases in pigs caused by Mycoplasma hyopneumoniae, Actinobacillus pleuropneumoniae, Bordetella bronchiseptica, Pasteurella multocida, Streptococcus suis, Swine Influenza Virus, and Porcine Reproductive and Respiratory Syndrome Virus. [0050] The Examples that follow serve to illustrate the use of meloxicam according to the invention. They are intended solely as possible procedures described by way of example, without restricting the invention to their content. EXAMPLE 1 Efficacy of Meloxicam in Pigs with Experimental Actinobacillus Pleuropneumoniae Infection [0051] The study was a controlled, randomized, and blinded exploratory study under experimental conditions with a parallel group design. [0052] Crossbred pigs of about 10 weeks of age were challenged with a single intranasal inoculation of Actinobacillus pleuropneumoniae. The next day, pigs were included in the study and treated if they fulfilled the following inclusion criteria: rectal temperature ≧40° C. and clinical symptoms of acute or subacute infectious respiratory disease. [0053] Twenty-four (12 castrated male and 12 female) pigs were included and randomly allocated to three treatment groups with 8 pigs per group. The treatment groups were: Group Treatment 1 untreated 2 oxytetracycline 3 oxytetracycline and meloxicam [0054] Meloxicam was administered as 0.5% solution, at 0.5 mg/kg daily on three consecutive days, oxytetracycline as 20% long-acting solution (OXYTET® 200) at 20 mg/kg as single injection. [0055] Relevant criteria for the evaluation of efficacy were incidence of fever, clinical parameters of respiratory disease, deaths, and lung lesions at necropsy 10 days after first treatment or after spontaneous death. The percentage of affected lung tissue was calculated by lobe and averaged for the total lung. [0056] Challenge with Actinobacillus pleuropneumoniae lead to severe pleuropneumonia within 12 hours. [0057] The incidence of fever (rectal temperature ≧40.56° C.) following the first treatment was lower in group 3 (♦) than in groups 1 (Δ), and 2 (∘) (cp. FIG. 1 ). [0058] The best treatment response in clinical parameters was observed in group 3. [0059] The number of pigs which died during the three days following first treatment is displayed below. Group (n = 8 per group) Deaths 1 7 2 1 3 0 [0060] The mean extent of lung lesions was less severe in group 3 than in the other groups (see below). Group Lung lesions (%) 1 60 2 35 3 14 [0061] Meloxicam in addition to antibiotic treatment effectively reduced fever, clinical symptoms of respiratory disease, deaths, and the extent of lung lesions in pigs with experimental Actinobacillus pleuropneumoniae -infection. EXAMPLE 2 Efficacy of Meloxicam in Drinking Water in Experimental Swine Influenza Virus Infection [0062] The aim of this study was to test the efficacy of meloxicam granules dissolved in drinking water in pigs experimentally infected with Swine Influenza Virus (SIV). [0063] The study was an open, negative controlled randomized laboratory study carried out according to GCP at one site. [0064] Meloxicam granules containing 6 mg meloxicam per gram were offered to the pigs in the treatment groups (A+B) via drinking water in a concentration of 1 g granules per liter drinking water ad libitum for 7 consecutive days. This resulted in an actual meloxicam uptake of 0.8 mg per kg body weight per day. The pigs in the control group (C) received municipal drinking water ad libitum. [0065] 30 pigs were infected with SIV on study day 0. 10 pigs were allocated to each of the three groups A, B, and C. Treatment (groups A and B) started after SIV challenge on the same day. [0066] The study animals were clinically examined daily on study days 0 to 7 and 14. They were weighed on study days 7 and 14. All animals of group A and 5 animals of group C were euthanized and necropsied on study day 7; the remaining study animals, group B and 5 study animals of group C, on study day 14. [0067] It is the major finding of this study that meloxicam granules administered continuously in the drinking water at an approximate daily dose of 0.8 mg/kg body weight significantly alleviated the development of lung lesions caused by experimental infection with SIV during the first week after challenge. FIG. 2 shows the quantity of lung lesions by lung lobe on study days 7 and 14. [0068] On study day 7 the percentage of lung tissue affected with SIV-related lesions (median value) was 8.9% in meloxicam group A and 23.8% in the control group (5 study animals of group C). [0069] Moreover, meloxicam-treated pigs reached significantly higher weight gains during the two weeks following infection than untreated controls. Mean daily weight gain in the interval study day 0 to 7 was 557 g in meloxicam group A and 257 g in the control (5 study animals of group C). In the interval study day 0 to 14, mean daily weight gain was 629 g in meloxicam group B and 486 g in the control (5 study animals of group C). [0070] The area under the curve of the clinical index score (CIS), a sum of the relevant clinical parameters, over study days 0 to 7 was significantly smaller in groups A and B than in group C. [0071] Thus oral treatment with meloxicam granules at a dose of 0.8 mg meloxicam per kg body weight per day for 7 consecutive was an efficacious treatment for SIV infection. EXAMPLE 3 Field Trial Regarding the Effect of Meloxicam in the Porcine Respiratory Disease Complex (PRDC) in Growing/Fattening Pigs [0000] Materials and Methods [0072] A medium scale farm (560 sows) with a previous history of recurring PRDC episodes was selected. A double-blinded randomized study was carried out with the selection of 162 growing animals with a mean age of 90 days at the onset of PRDC clinical signs. Animals were randomly allocated to 8 pens and divided into two treatment groups, with respect to equal sex ratio, same housing and feeding conditions and genetic background. Group 1 (PC) received 800 ppm chlorotetracycline in the feed over 8 consecutive days plus a single IM injection of a placebo (isotonic saline) at d 0 (start of the trial, n=82). Group 2 (M) received 800 ppm chlorotetracycline in the feed over 8 consecutive days plus a single IM injection of 0.4 mg/kg bodyweight meloxicam (METACAM® 2%, Boehringer Ingelheim GmbH) at d 0 (n=80). Clinical parameters were assessed as the daily Respiratory Score (RS), using a 3 point score (0=absence of signs to 3=abdominal breathing and disordered general condition) over 8 consecutive days and the total number of additional required injectable medications (AIM). Growth performance data for each group included the Average Daily Gain (ADG) for the following trial periods: d90 to d117, d117 to d170 (slaughtering), and d90 to d170 of age. Mortality was also calculated for these time periods. Slaughterhouse records per group, included the percentage of each lung surface (LS) affected by chronic and acute respiratory lesions. [0073] Student's t-Test and Pearson's Chi-Square Test were used for the consequent comparisons of means and frequencies between trial groups. [0000] Results and Discussion [0074] RS and AIM in the meloxicam group were significantly lower (p<0.05) compared to the control group. Same applies for LS affected by acute lesions (p<0.01), while no differences were observed for LS in chronic cases (Table 1). TABLE 1 RS, LS: Mean (SD); AIM number (%) Treatment Group PC M Significance RS  0.70 (0.63) a 0.50 (0.51) b p = 0.0289 AIM (%) 10/82 (12.2%) a 2/80 (2.5%) b x 2 = 4.226 LS (chronic)  5.96 (2.28) a 5.91 (2.32) a p = 0.893 LS (acute)  3.71 (1.81) a 2.64 (2.03) b p = 0.0007 a,b Values in a row with different superscripts differ significantly [0075] The analysis of growth performance data revealed significant differences between groups at d 90 to d 117 (p<0.05, Table 2). TABLE 2 ADG: Mean (SD) Trial Period Group d90 to d117 d117 to d170 d90 to d170 PC 0.64 (0.09) a 0.89 (0.06) a 0.81 (0.03) a M 0.67 (0.10) b 0.89 (0.06) a 0.82 (0.03) a a,b Values in a column with different superscripts differ significantly (p < 0.05) [0076] TABLE 3 Mortality: Number of animals/group (%) Trial Period Group d90 to d117 d117 to d170 d90 to d170 PC 6/82 (7.32%) a 1/76 (1.22%) 7/82 (8.54%) M 0/80 (0.00%) b 1/80 (1.25%) 1/80 (1.25%) a,b Values in a column with different superscripts differ significantly (p < 0.05) [0077] Under the conditions of this study, the reduction of the prevalence of respiratory signs as well as the reduced overall number of required injectable antibiotic medications are indicative for the potent anti-inflammatory activity of meloxicam. The latter could become a valuable adjunctive measure, especially when respiratory distress is associated with remarkable reduction of the feed intake. The initial differences in growth performance and in mortality rate could be explained by the fact that meloxicam, when combined with proper antimicrobial medication, contributes to faster recovery from a respiratory inflammation and faster restoring of the distorted growth rate of affected animals. Further research on the evaluation of feed intake and the use of meloxicam in PRDC recurring episodes is required.
A method of treating or preventing a respiratory disease in a pig, the method comprising administering to the pig in need thereof an effective amount of meloxicam or a pharmaceutically acceptable salt thereof.
0
This application is a 371 of PCT application No. PCT/EP98/05500, filed on Aug. 26, 1998. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a device for absorbing moisture from the air. 2. Description of the Prior Art A known device for absorbing moisture from the air includes a form-retaining housing manufactured from plastic and consisting of two parts connected releasably to each other. The upper part of the housing herein forms a receptacle part intended for receiving one or more cassettes filled with an absorbent material. The lower part of the housing forms a collecting part in which the moisture collects which is extracted from the air by the absorbent material in the cassettes. The cassettes with the absorbent material can have a fixed, standardized size whereby they are easily exchangeable between many different types of absorption devices. The known absorption device has the drawback that it requires a relatively large amount of material. The device is thereby relatively expensive and, furthermore, there remains much waste when the device is scrapped. The cassettes used in the known device also represent a relatively large quantity of plastic material, and therefore a high value. This is a particular drawback because these cassettes are replaced after the absorbent material present therein is no longer active. While the cassettes can be embodied such that they can be opened and refilled with absorbent material, this is relatively labour-intensive. SUMMARY OF THE INVENTION The invention therefore has for its object to provide an absorption device of the above described type wherein the stated drawbacks do not occur. This is achieved according to the invention with an absorption device which is provided with at least one support and at least one flexible packing connected thereto and filled with absorbent material. By making use of a flexible packing for the absorbent material, for instance a bag, the material consumption associated therewith is low. The support preferably has means for accommodation thereof in a form-retaining container of standardized dimensions. In this way the absorption device according to the invention can also be used instead of a conventional exchangeable cassette. When the support has means for suspending thereof, for instance in the form of a hook releasably connected to a bottom of the support, the absorption device can be used independently without the housing of the classic absorption device. The device can then be suspended for instance in a wardrobe. In preference the or each packing is releasably connected to the support so that it can be easily replaced when the absorbent material arranged therein is no longer active. The support can for instance have means for clamping thereon of the or each packing. A robust and easily releasable embodiment of the support is obtained when the clamping means comprise at least one, but preferably two, wings connected hingedly to the bottom of the support. In order to enable use of the absorption device without a separate collecting vessel placed thereunder, it preferably has at least one reservoir for collecting moisture connected on the underside to the or each packing. The or each collecting reservoir can herein be manufactured from a flexible material, for instance in that it is manufactured integrally with the or each packing. The invention also relates to the support and packing for use in the above described absorption device. BRIEF DESCRIPTION OF THE DRAWING The invention will now be elucidated on the basis of a number of embodiments, wherein reference is made to the annexed drawing, in which: FIG. 1 shows a cross-section through a first embodiment of a conventional absorption device, FIG. 2 shows a longitudinal section along the line II—II in FIG. 1, FIG. 3 is a side view of the collecting part of the absorption device shown in FIGS. 1 and 2, FIG. 4 is a top view of the receptacle part of this absorption device, FIG. 5 is a front view of the holding means of this device, FIG. 6 shows a longitudinal section through a second embodiment of the conventional absorption device, FIG. 7 shows a cross-section through this device along the line VII—VII in FIG. 6, FIG. 8 is a top view of a conventional exchangeable packing for the absorption device of FIGS. 1-7, FIGS. 9 and 10 show respectively a front view and a side view of the packing depicted in FIG. 8, FIG. 11 is a perspective view of a support of the absorption device according to the invention before use thereof, FIG. 12 is a perspective view of a first embodiment of the absorption device according to the invention formed by the support of FIG. 11 and a flexible packing suspended therefrom, and FIG. 13 shows a second embodiment of the absorption device according to the invention provided with a suspension hook and a collecting reservoir. DESCRIPTION OF THE PREFERRED EMBODIMENTS A conventional absorption device 1 (FIG. 1) has a container 2 in which is arranged an exchangeable cassette 3 . Container 2 is formed by a collecting part 4 and a receptacle part 5 which is placed thereon and which actually accommodates cassette 3 and secures it using holding means 6 . Collecting part 4 is intended to collect moisture or water which is removed from the air by the absorbent material present in cassette 3 . The collecting part therefore has in one of its side walls 34 a transparent part 23 through which it is possible to observe whether liquid is already present therein, and is further provided with discharge means in the form of a pouring spout 20 arranged in the vicinity of upper edge 27 in a side wall 21 of collecting vessel 4 . In order to enable rigid placing of absorption device 1 on a ground despite its relatively high and slim shape without the risk of the device tipping over and the moisture collected therein draining away, it is provided on its underside with a detachable foot 24 which extends in transverse direction of absorption device 1 and protrudes outside it on either side. This foot 24 is provided with a number of pins 37 which are received in recesses 36 in the base 35 of collecting part 4 . Receptacle part 5 is connected releasably to collecting part 4 . In the shown embodiment the receptacle part 5 is provided for this purpose in the proximity of its underside 13 with two apertures 33 in the transverse edges 31 thereof. Into these apertures engage resiliently flexible hooking arms 32 which are arranged on the upper edge 27 of collecting part 4 . In order to allow the moisture-containing air to come into contact with the absorbent material in cassettes 3 the receptacle part 5 is provided in its long walls 62 with a large number of slit-like apertures 40 . Each cassette 3 is also provided in its long side walls 38 with slit-like apertures 39 through which the moist air can penetrate into cassette 3 and come into contact with the absorbent material present therein. For arranging of the cassettes 3 the receptacle part 5 is provided on its side 14 remote from collecting part 4 with an opening 15 , the form and dimensions of which are chosen in the shown embodiment such that two cassettes 3 can be accommodated adjacently of each other in longitudinal direction. These cassettes 3 herein rest with their protruding peripheral edge 28 on the peripheral edge 16 of receptacle part 5 protruding in opening 15 . Cassettes 3 are fixed in receptacle part 5 by holding means 6 . In the shown embodiment these holding means 6 are formed by a locking member 17 which extends over the whole receiving opening 15 and is provided on its outer ends with resiliently flexible hooking arms 29 (FIG. 5 ). These hooking arms 29 can engage in apertures 30 on the top part of receptacle part S. Both cassettes 3 are thus fixedly clamped between the edge 16 of receptacle part 5 and locking member 17 . In this embodiment of absorption device 1 it would otherwise also be possible to suffice with a single cassette 3 when for instance the air is temporarily relatively dry. This could also be held properly in place by locking member 17 . When only a single cassette with absorbent material is used, it is also possible however to apply therefor a different embodiment of the conventional absorption device 1 (FIG. 6 ), whereof the form and dimensions of the receiving opening 15 in receptacle part 5 are exactly adapted to a single cassette 3 . No use is herein made of a separate locking member to secure the cassette 3 in receptacle part 5 but receptacle part 5 is instead provided in its short sides with hooking edges 41 behind which a resiliently flexible hook member 42 of cassette 3 can be clamped in each case. Although in the shown embodiment this smaller absorption device 1 is likewise provided with a foot 24 , it is also suitable for suspending, for instance in a wardrobe where clothing is stored. A detachable hook 25 is arranged for this purpose on the top of device 1 . In the shown embodiment this hook is connected to the top part 26 of cassette 3 , which is connected in turn to the top side 14 of receptacle part 5 which in its turn is connected to collecting part 4 . For this latter connection use is made in the shown embodiment of hooking arms 22 on the underside of receptacle part 5 which engage under hooking edges 32 of collecting part 4 . Hook 25 is clamped fixedly in a recess 45 in cover 8 of cassette 3 by means of resiliently flexible hooking arms 43 which engage behind hooking edges 44 of the recess. In the shown embodiment the hook 25 is a closed hook with a hinged closing part 46 which can engage behind a closing edge 47 . The suspended absorption device 1 , in which a relatively large amount of liquid will accumulate in the course of time, is in this way prevented from coming loose and falling. The conventional cassette 3 applied in the embodiments of the classic absorption device 1 shown heretofore is form-retaining with a body 7 which is open at the top 9 and closed by a cover 8 . Cover 8 is connected to body 7 by means of hinges 48 . The absorbent material can be received in body 7 which, as stated, is provided with slit-like apertures 39 for admitting moist air. After filling of the body 7 the cover 8 can herein be snapped fixedly thereon so that it is easy to re-open at a later stage and-the absorbent material can thus be replaced, although the shown embodiment provides for cover 8 to be welded on container body 7 after filling thereof. Arranged for this purpose in cover 8 are a number of orifices 49 which, when cover 8 is closed, drop over pins 50 arranged on the edge 28 of container body 7 . By then briefly heating the protruding parts of these pins 50 the cover 8 is welded onto container body 7 . Although the above described variants of the conventional absorption device and the cassettes used therein are very satisfactory in practice, they require a relatively large amount of material, so that they are also quite costly. The invention therefore proposes an absorption device which can not only be used independently but which can also serve as replacement for the conventional exchangeable cassette filled with absorbent material for the conventional form-retaining plastic absorption devices. The absorption device 1 according to the present invention is characterized for this purpose by its flexible character. The device comprises a support 10 and, connected thereto, a flexible packing 11 in which the absorbent material is arranged. The flexible packing 11 is herein suspended from support 10 (FIG. 11 ). In the shown embodiment the support 10 consists of a bridge piece 51 , the form and dimensions of which correspond with the (standardized) form and dimensions of the form-retaining cassette 3 shown above. The absorption device according to the invention can hereby be used to replace such a cassette in a conventional absorption device. Bridge piece 51 is provided with means for fixedly clamping the flexible packing 11 thereon. These clamping means are formed in the shown embodiment by clamping wings 53 which are arranged on the long sides of the bridge piece and which are connected thereto by means of hinges 52 . Each wing 53 is embodied in an L-shape and has a leg, the width of which amounts practically to half the width of bridge piece 51 , and an end flange 55 arranged transversely thereof. One of the end flanges 55 is herein provided with protruding pins 56 , while the other flange 55 has apertures 57 corresponding therewith. By now holding the flexible packing 11 between wings 53 and subsequently moving the wings towards each other until the pins 56 snap fixedly into apertures 57 , the flexible packing 11 is fixed to support 10 . Packing 11 is thus connected releasably to support 10 and can be exchanged when the absorbent material arranged therein is no longer active. The quantity of waste packing material generated herein is then minimal. Packing 11 can however also be fixed permanently to support 10 , for instance by welding, whereby support 10 with packing 11 has to be replaced integrally. After packing 11 has been suspended from support 10 by means of the resilient hooking arms 42 , support 10 can be snapped fixedly into the conventional absorption device as shown in FIGS. 6 and 7 or be suspended in the conventional absorption device of FIGS. 1 and 2 and fixed therein by locking member 17 . An outer packaging 58 must herein also be removed before use of the packing 3 , which packaging serves to prevent the absorbent material in packing 3 already becoming active during transport and storage thereof and thus being practically inactive by the time packing 3 reaches the end-user. Support 10 can likewise be provided with a recessed part 45 with hooking edges 44 whereby absorption device 1 can likewise be connected on its top 26 to a suspension hook 25 (FIG. 13 ). Absorption device 1 can in this manner also be used without the container 2 . In this case a collecting reservoir 12 for water formed integrally with the flexible packing 11 can further be arranged on the underside thereof, which reservoir is in communication with the flexible packing 11 via apertures 61 on the underside thereof. This prevents a separate collecting vessel having to be placed under the device. Instead of outer packaging 58 of FIG. 12, the flexible packing 11 can herein be provided with a detachable foil 60 covering an air-permeable part 59 of packing 11 . This foil 60 can be removed prior to use, whereafter the flexible packing 11 filled with absorbent material and the collecting reservoir 12 arranged thereunder form in combination with support 10 a complete absorption device. Although the invention is elucidated above on the basis of a number of embodiments, it will be apparent to the skilled person that it is not limited thereto. The scope of the invention is defined solely by the following claims.
A device is disclosed for absorbing moisture from the air. The device is made of flexible packaging material attached to a support. The packaging is filled with an absorption material. The support may have parts for holding the same in a rigid standard size holding device and/or parts for suspension. The packaging can be separately joined e.g. cramped to the support. A receptacle for collecting the moisture can be provided on the underside of the packaging. The receptacle can also be made of flexible material. The invention also relates to a support and a packaging which are used in such an absorption device.
1
BACKGROUND OF THE INVENTION The invention relates to a paste extruder for making hollow articles (profiles), for example, plastic pipes or tubes, particularly of polytetrafluorethylene (PTFE). The extruder includes a machine stand to which are attached an extrusion cylinder having an extrusion mouthpiece to receive a preform composed of the plastic to be extruded; and an extrusion drive for an extrusion piston that can be driven into the extrusion cylinder and thus effects the extrusion of the plastic material. The extruder further includes a mandrel pulling rod that is axially displaceably mounted within the extrusion piston and is movable by a mandrel positioning drive for positioning a mandrel that is fixed to the rod end and cooperates with the extrusion mouthpiece to form the hollow article. Because of their structural length, such paste extruders require a significant amount of space. A substantial structural length for the paste extruder is needed, because the preforms may have a length of up to 2 m, and the stroke of the extrusion piston must correspond to this length. If additionally the extrusion cylinder is to be charged in the advantageous manner of a breechloader, the extrusion piston must be pulled out of the extrusion cylinder to such an extent during the charging process that sufficient space for the introduction of the preform exists between its pressure face and the extrusion cylinder. This space must generally be significantly larger than the length of the preform because in preferred configurations of such extruders the mandrel shaping the interior profile of the article projects beyond the pressure face of the extrusion piston. Because of the resulting structural lengths of such extruders, they are frequently designed for a vertical extrusion direction. This, however, requires a correspondingly tall operating space which is in part inconsistent with the multi-purpose use of such extruders. Such extruders require considerable pressures of up to, for example, 1000 bar to drive the extrusion piston. The drives for the extrusion piston must be dimensioned correspondingly large. It is thus customary to have several cooperating drive assemblies act jointly on the extrusion piston. Furthermore, a drive assembly required to axially position the mandrel must be added to the drive assemblies. Thus, the prior art paste extruders of the above-mentioned type, in addition to the significant great structural length, also have a considerable structural width and height. SUMMARY OF THE INVENTION It is an object of the invention to provide an improved paste extruder of the above-discussed type which has reduced spatial requirements compared to prior art structures. This object and others to become apparent as the specification progresses, are accomplished by the invention, according to which, briefly stated, the mandrel positioning drive is surrounded (encapsulated) by the extrusion drive and both drives are disposed in a common housing. The compact configuration according to the invention is of increased significance if additional drive and positioning means are present. It is generally important that the paste extruder does not project far radially with respect to its longitudinal axis extending in the extrusion direction. According to a further feature of the invention, if the extrusion piston is retracted from the extrusion cylinder, the common housing together with its drives is pivotal about a pivot axis that is disposed approximately at a right angle to the longitudinal axis of the extrusion piston. Such an arrangement additionally provides for a short structural length in spite of the fact that the extrusion cylinder is recharged as a breechloader. The small structural width or height also favorably affects the space requirement of the paste extruder if its components, when pivoted out, do not project significantly beyond the dimensions in the operating position. In order to make available the axially effective space required to reload the preform from the rear into the extrusion cylinder, the extrusion piston has to be pulled out of the extrusion cylinder only to the extent that the mandrel lies just outside the extrusion cylinder. Then a comparatively slight pivoting movement of the entire drive unit is sufficient to make available the space required for reloading a preform from the drive side. According to yet another feature of the invention, the pivot axis is disposed midway between the axial ends of the housing. This arrangement ensures that, in the outwardly pivoted position, the ends of the drive unit have been swung out of the center position by about the same radial extent. In a further feature of the invention the pivot axis is oriented approximately horizontally and so positioned that the weight of the masses of the housing and the drives disposed on both sides of the pivot axis is in equilibrium. Such an arrangement permits the use of a comparatively weak (low-power) pivot drive. Moreover, this facilitates a precise adjustment of the extrusion piston before it is re-introduced into the extrusion cylinder at the beginning of a new extrusion process. The fact that such a precise adjustment is at all possible, is of particular significance for a continuous operation of such a paste extruder. The compact configuration of the subject matter of the invention is of particular significance for this important, precise adjustability. Thus the masses that need to be moved for adjustment purposes are arranged in an advantageous proximity of the pivot axis. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a side elevational view of a preferred embodiment of a paste extruder in which the extrusion piston advances in the horizontal direction and which has an extrusion piston drive unit that is shown in the extruding position and, in phantom lines, in an outwardly pivoted position. FIG. 2 is an axial sectional view of the paste extruder shown in FIG. 1. FIG. 2a is an enlarged view of the circular inset in FIG. 2. FIG. 3 is a sectional view taken along line III--III of FIG. 2. FIG. 4 is an axial sectional view of another preferred embodiment of the invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS Turning to FIG. 1, the paste extruder is essentially composed of an extrusion cylinder 2 that is fixed within a machine stand 1 to receive a preform 3 to be extruded and an extrusion piston 4 which can be driven into extrusion cylinder 2. The entrance and advancing direction 5 of extrusion piston 4 extends parallel to its central longitudinal axis 6 and the central longitudinal axis 7 of extrusion cylinder 2. Extrusion piston 4 is driven by a drive unit which, as a whole, is designated at 8 and is disposed behind the extrusion piston 4 facing away from extrusion cylinder 2. The drive unit 8 is pivotal in machine stand 1 about a pivot shaft 9 which extends approximately horizontally and approximately perpendicularly to the axis 6 of extrusion piston 4. The pivot shaft is positioned approximately midway between the front end 11 and the rear end 12 of the drive unit 8 so that the latter and extrusion piston 4 together act as a two-armed lever or rocker. A pressure cylinder 10 is provided to apply a force to the drive unit 8 to cause pivotal motions thereof. The pressure cylinder 10 whose fixed end is attached to machine stand 1 radially engages the front end 11 of drive unit 8. The piston rod 13 of pressure cylinder 10 is connected with drive unit 8 by way of an eyelet joint 14. Machine stand 1 is essentially composed of two spaced parallel and approximately square frame stands 15 and 16 that are arranged at a right angle to the axis 6 of extrusion piston 4 and are each supported by a base stand 17 and 18. Frame stands 15 and 16 are connected with one another by means of four longitudinal transverse members 19, 20 that are disposed at the respective frame stand corners. The rear end of extrusion cylinder 2 facing extrusion piston 4 is disposed centrally in the front frame stand 16 and is affixed thereto. An extrusion mouthpiece 21 and an extrusion nozzle 22 which determines the outer diameter of the hollow article to be extruded are disposed at the front end of the extrusion cylinder 2. Also referring to FIG. 3, drive unit 8 is disposed in the rear frame stand 15 approximately midway between the front and rear ends 11, 12. The pivot shaft 9, having a pivot axis 9a is supported in bearings 23 in the stand 15. Bearings 23 are fastened to the exterior of frame stand 15 and, for adjustment of pivot shaft 9, are configured as eccentric rings. To fasten the pivot shaft 9, which is composed of two halves 9' and 9'', to housing 30, an annular flange 29 is formed on its periphery. The annular flange is provided with two diametrally oppositely disposed blind-bore-like recesses 37 and 38 in which the ends of shaft halves 9' and 9'' facing housing 30 are fixed. A mandrel pulling rod 24 is mounted centrally within extrusion piston 4 so as to be coaxially displaceable. The front end of the rod 24 projects from the frontal pressure face 25 of extrusion piston 4 and is, at that location, releasably connected with a mandrel 26. A sealing disc 28 which cooperates with the interior surface 27 of extrusion cylinder 2 is disposed on the pressure face 25 of extrusion piston 4. The structure of drive unit 8 will now be described in greater detail with reference to FIGS. 2, 2a and 3. Drive unit 8 includes a housing 30 which accommodates the extrusion drive for extrusion cylinder 4 and the positioning drive for the axially displaceable mandrel pulling rod 24 and a mandrel 26 disposed at the front end of the rod 24. The positioning drive for mandrel pulling rod 24 and mandrel 26 is a hydraulic cylinder 31 which is disposed centrally within housing 30 and coaxially with the longitudinal axis 6 of extrusion cylinder 4. The driven member for the extrusion drive is a hollow cylinder 32 coaxially surrounding hydraulic cylinder 31 and connected at its front end with extrusion piston 4. A hollow spindle 34 which is provided with an external thread 33 is disposed between hydraulic cylinder 31 and hollow cylinder 32. The rear end 35 of hollow cylinder 32 facing away from extrusion piston 4 is provided with an internal thread 36 that is in engagement with the external thread 33 of hollow spindle 34 to form a spindle drive. The front and rear ends of hollow spindle 34 are supported by means of roller bearings 39 and 40 which are supported at the housing of hydraulic cylinder 31. A spur gear 42 projects radially from the circumference of the rear end of the hollow spindle 34 and is in driving engagement with a spur gear 43. Through the intermediary of a gear assembly 47 and by way of a drive shaft 46 projecting from the housing 30, the spur gear 43 is connected with an electric motor 48. Gear assembly 47 and electric motor 48 are fixed to the exterior of housing 30 in a longitudinal axial orientation. The piston 49 of hydraulic cylinder 31 is hollow and coaxially and displaceably receives a rod 50. The front end 51 of the rod 50 facing extrusion cylinder 2 is provided with an abutment face 52 that cooperates with a drive-side interior ring collar 53 of piston 49. The adjustment end 54 of rod 50 facing away from abutment face 52 is provided with an external thread 55 and projects from housing 30. The adjustment drive 56 for rod 50 is flanged to the rear end face of housing 30 and includes an electric motor 57 and a gear assembly 58 which cooperates with the external thread 55 of rod 50 as a screw drive. The hollow cylinder 32 constituting the driven member of the extrusion drive is provided at its rear end 35 with two diametrally oppositely disposed, radially outwardly extending projections 60 and 61 which are guided in guide rails 63 and 64 that are disposed in the interior wall 62 of housing 30 and extend parallel to the axis 6 of extrusion piston 4. Projections 60 and 61 are supported by means of roller bearings 65 and 66 in guide rails 63 and 64. FIG. 4 shows an embodiment of a paste extruder in which the hollow cylinder 32, constituting the driven member of extrusion piston 4 is driven hydraulically, rather than by a spindle drive as in the earlier-described embodiment. For this purpose, the rear end 35 of hollow cylinder 32 is provided with an annular flange 68 that projects radially from its outer circumference. The flange 68 is sealingly fitted into the cross-sectionally circular housing 30 for acting as a hydraulic piston. To advance extrusion piston 4, the rear end face 69 of annular flange 68 is charged with hydraulic oil through conduit 70. For the return stroke, the inner ring face 71 of annular flange 68 facing away from end face 69 is charged with hydraulic oil through a conduit 72. A control plate 73 for controlling the hydraulic drive is disposed between adjustment drive 56 and housing 30. Such a control plate 73 is also provided in the embodiment shown in FIGS. 1-3. The outer circumferential surface of hydraulic cylinder 31, which serves as the positioning drive for mandrel pulling rod 24, and the inner circumferential face of hollow cylinder 32 cooperate as a slide bearing. To recharge a preform 3 in extrusion cylinder 2 in the apparatus according to the invention, the extrusion piston 4 is initially retracted into its rearward starting position in which the front end of extrusion piston 4 is disposed outside of extrusion cylinder 2. Thereafter, or simultaneously with the retraction of extrusion piston 4, mandrel pulling rod 24 and mandrel 26 are also retracted to such an extent that mandrel 26 is disposed outside of extrusion cylinder 2. Then pressure cylinder 10 is actuated, whereupon its piston rod 13 extends and pivots drive unit 8 together with extrusion piston 4 about pivot shaft 9 so that drive unit 8 and extrusion piston 4 assume an outwardly-pivoted position shown in dashed lines in FIG. 1. The pivoting motion occurs about an angle of approximately 20. Such an angle is sufficient to make available sufficient space in the rear region of extrusion cylinder 2 for the preform 3 that is to be introduced into extrusion cylinder 2 in a breechloading manner. After insertion of preform 3 into extrusion cylinder 2, retraction of piston rod 13 of pressure cylinder 10 causes drive unit 8 and extrusion piston 4 to be returned to the extrusion position. In this position, extrusion piston 4 must be aligned in such a manner that its central longitudinal axis 6 is in a linear alignment with the central longitudinal axis 7 of extrusion cylinder 2. A subsequent adjustment in the vertical direction required, for example, due to a slight bend in extrusion piston 4 may be effected by means of a vertical adjustment device 67 that is disposed at machine stand 1 near pressure cylinder 10. It will be understood that the paste extruder according to the invention may be operated to extrude in the horizontal as well as the vertical direction. It will be understood that the above description of the present invention is susceptible to various modifications, changes and adaptations, and the same are intended to be comprehended within the meaning and range of equivalents of the appended claims.
An apparatus for extruding plastic tubing includes a machine stand; an extrusion cylinder supported by the machine stand; a housing supported on the machine stand; a hollow extrusion piston introducible into and withdrawable from the extrusion cylinder; an extrusion drive accommodated in the housing and connected to the extrusion piston for advancing the extrusion piston into and for withdrawing the extrusion piston from the extrusion cycliner; an mandrel pulling rod mounted in, and axially displaceable relative to, the hollow extrusion piston; a mandrel affixed to the mandrel pulling rod and moving as a unit with the mandrel pulling rod for introduction into and withdrawal from the extrusion cylinder; and a mandrel actuating drive circumferentially surrounded by a sleeve-shaped component of the extrusion drive in the housing and connected to the mandrel pulling rod for axially displacing the mandrel pulling rod.
1
FIELD OF THE INVENTION [0001] The present invention relates to conopeptides and analogs thereof that can control or otherwise affect behavior of voltage-gated sodium channels, such as Nav 1.1-1.7 channels. Many conopeptides are found in minute amounts in the venom of cone snails (genus Conus ). As such, the present invention involves the fields of chemistry, biochemistry, molecular biology, and medicine among others. BACKGROUND OF THE INVENTION [0002] All publications, patents, and other materials used herein are incorporated by reference. [0003] The venom of marine gastropods in the genus Conus has yielded numerous structurally and functionally diverse peptidic components. The increasing variety of bioactive peptides identified in cone snail venoms has provided insight into the seemingly endless variety of directions taken by Conus species in evolving neuroactive molecules to suit their diverse biological purposes. [0004] The bioactive peptides in Conus (“conopeptides”) are classified into two broad groups: the non-disulfide-rich and the disulfide-rich. The latter are conventionally called conotoxins. The non-disulfide-rich class includes conopeptides with no cysteines (contulakins and conorfamides), and conopeptides with two cysteines forming a single disulfide bond (conopressins and contryphans). The conopeptides that comprise the disulfide-rich class have two or more disulfide bonds. Among the major classes of molecular targets identified for these structurally diverse conopeptides are members of the voltage-gated and ligand-gated ion channel superfamilies. [0005] The structure and function of a number of these peptides have been determined. Three classes of targets have been elucidated: voltage-gated ion channels; ligand-gated ion channels, and G-protein-linked receptors. [0006] Conus peptides which target voltage-gated ion channels include those that delay the inactivation of sodium channels, as well as blockers specific for sodium channels, calcium channels and potassium channels. Peptides that target ligand-gated ion channels include antagonists of NMDA and serotonin receptors, as well as competitive and noncompetitive nicotinic receptor antagonists. Peptides which act on G-protein receptors include neurotensin and vasopressin receptor agonists. The pharmaceutical selectivity of conotoxins is at least in part defined by specific disulfide bond frameworks combined with hypervariable amino acids within disulfide loops. [0007] Voltage-gated sodium channels are found in all excitable cells including myocytes of muscle and neurons of the central and peripheral nervous system. In neuronal cells, sodium channels are primarily responsible for generating the rapid upstroke of the action potential. In this manner sodium channels are essential to the initiation and propagation of electrical signals in the nervous system. Proper and appropriate function of sodium channels is therefore necessary for normal function of the neuron. Consequently, aberrant sodium channel function is thought to underlie a variety of medical disorders including epilepsy, arrhythmia, myotonia, and pain. [0008] There are currently at least nine known members of the family of voltage-gated sodium channel (VGSC) alpha subunits. Names for this family include SCNx, SCNAx, and Navx.x. The VGSC family has been phylogenetically divided into two subfamilies Nav1.x (all but SCN6A) and Nav2.x (SCN6A). The Nav1.x subfamily can be functionally subdivided into two groups, those which are sensitive to blocking by tetrodotoxin (TTX-sensitive or TTX-s) and those which are resistant to blocking by tetrodotoxin (TTX-resistant or TTX-r). [0009] The Nav1.7, alternatively written as NaV1.7, (PN1, SCN9A) VGSC is sensitive to blocking by tetrodotoxin and is preferentially expressed in peripheral sympathetic and sensory neurons. The SCN9A gene has been cloned from a number of species, including human, rat, and rabbit and shows about 90% amino acid identity between the human and rat genes. BRIEF DESCRIPTION OF THE DRAWINGS [0010] FIGS. 1A and 1B show concentration response curves for C. geo 1 analogs against hNaV1.7. FIG. 1A : IC 50 value for the internally-truncated synthetic peptide C. geo 1[des-Ser34] was calculated as 1.8 μM. FIG. 1B : Concentration-response curves were repeated on the full-length peptide, in addition to the analog containing the amino-butyric acid isosteric replacement at position 24 ( C. geo 1[C24Abu]). DETAILED DESCRIPTION [0011] In describing and claiming the present invention, the following terminology will be used in accordance with the definitions set forth below. [0012] The singular forms “a,” “an,” and, “the” can include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a peptide” can include reference to one or more of such peptides, and reference to “the analog” can include reference to one or more of such analogs. [0013] As used herein, “subject” refers to a mammal that may benefit from the administration of a composition or method according to aspects of the present disclosure. Examples of subjects include humans, and may also include other animals such as horses, pigs, cattle, dogs, cats, rabbits, and aquatic mammals. [0014] As used herein, the term “peptide” may be used to refer to a natural or synthetic molecule comprising two or more amino acids linked by the carboxyl group of one amino acid to the alpha amino group of another. A peptide of the present invention is not limited by length, and thus “peptide” can include polypeptides and proteins. Amino acid sequences are written left to right in amino to carboxy orientation, respectively. [0015] As used herein, the term “isolated,” with respect to peptides, refers to material that has been removed from its original environment, if the material is naturally occurring. For example, a naturally-occurring peptide present in a living animal is not isolated, but the same peptide, which is separated from some or all of the coexisting materials in the natural system, is isolated. Such isolated peptide could be part of a composition and still be isolated in that the composition is not part of its natural environment. An “isolated” peptide also includes material that is synthesized or produced by recombinant DNA technology or that is synthetically created. [0016] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which the invention belongs. [0017] As used herein, the term “substantially” refers to the complete or nearly complete extent or degree of an action, characteristic, property, state, structure, item, or result. For example, an object that is “substantially” enclosed would mean that the object is either completely enclosed or nearly completely enclosed. The exact allowable degree of deviation from absolute completeness may in some cases depend on the specific context. However, generally speaking the nearness of completion will be so as to have the same overall result as if absolute and total completion were obtained. The use of “substantially” is equally applicable when used in a negative connotation to refer to the complete or near complete lack of an action, characteristic, property, state, structure, item, or result. For example, a composition that is “substantially free of” particles would either completely lack particles, or so nearly completely lack particles that the effect would be the same as if it completely lacked particles. In other words, a composition that is “substantially free of” an ingredient or element may still actually contain such item as long as there is no measurable effect thereof. [0018] As used herein, the term “about” is used to provide flexibility to a numerical range endpoint by providing that a given value may be “a little above” or “a little below” the endpoint without affecting the desired result. [0019] As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though each member of the list is individually identified as a separate and unique member. Thus, no individual member of such list should be construed as a de facto equivalent of any other member of the same list solely based on their presentation in a common group without indications to the contrary. [0020] Concentrations, amounts, and other numerical data may be expressed or presented herein in a range format. It is to be understood that such a range format is used merely for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. As an illustration, a numerical range of “about 1 to about 5” should be interpreted to include not only the explicitly recited values of about 1 to about 5, but also include individual values and sub-ranges within the indicated range. Thus, included in this numerical range are individual values such as 2, 3, and 4 and sub-ranges such as from 1-3, from 2-4, and from 3-5, etc., as well as 1, 2, 3, 4, and 5, individually. [0021] This same principle applies to ranges reciting only one numerical value as a minimum or a maximum. Furthermore, such an interpretation should apply regardless of the breadth of the range or the characteristics being described. DETAILED DESCRIPTION [0022] The present disclosure provides novel peptides showing activity in blocking sodium channels, including various associated compositions and methods. More particularly, these peptides block at least voltage-gated sodium channels. Much of the description herein pertains to NaV1.7 sodium channels; however it is understood that the present scope includes any sodium channels, voltage-gated or otherwise, that are affected by the present peptides. It is noted that these peptides are derived from the venom of Conus geographus snails using a combination of venom fractionation, sequencing, cloning and transcriptomics, and that the present scope additionally includes the naturally occurring peptides, completely or partially synthesized peptides, and related analogues thereof. [0023] The present peptides can be identified by isolation from Conus venom. Additionally, the present peptides can be identified using recombinant DNA techniques by screening cDNA libraries of various Conus species using conventional techniques such as the use of reverse-transcriptase polymerase chain reaction (RT-PCR) or the use of degenerate probes. Primers for RT-PCR are based on conserved sequences in the signal sequence and 3′ untranslated region of the propeller peptide genes. Clones that hybridize to these probes can be analyzed to identify those which meet minimal size requirements, i.e., clones having approximately 300 nucleotides (for a precursor peptide), as determined using PCR primers that flank the cDNA cloning sites for the specific cDNA library being examined. These minimal-sized clones can then be sequenced. The sequences are then examined for the presence of a peptide having the characteristics noted above for peptides. The biological activity of the peptides identified by this method is tested as described herein, in U.S. Pat. No. 5,635,347, or conventionally in the art. [0024] The present peptides are sufficiently small to be chemically synthesized by techniques well known in the art. The peptides are synthesized by a suitable method, such as by exclusively solid-phase techniques (Merrifield solid-phase synthesis), by partial solid-phase techniques, by fragment condensation or by classical solution couplings. Suitable techniques are exemplified by the disclosures of U.S. Pat. Nos. 4,105,603; 3,972,859; 3,842,067; 3,862,925; 4,447,356; 5,514,774; 5,591,821 and 7,115,708, each incorporated herein by reference. In one non-limiting aspect, a solid peptide synthesis protocol can be optimized using a low preloaded Wang resin in combination with pseudoproline Fmoc-Tyr(tBu)-Thr(ψ Me,Me pro)-OH to obtain enhanced purity for the crude linear products. [0025] Various of the peptides described herein can also be obtained by isolation and purification from specific Conus species using the techniques described in U.S. Pat. Nos. 4,447,356; 5,514,774 and 5,591,821, the disclosures of which are incorporated herein by reference. The peptides described herein can also be produced by recombinant DNA techniques well known in the art. [0026] Peptides produced by chemical synthesis or recombinant DNA techniques can be isolated, reduced if necessary, and oxidized to form disulfide bonds. One method of forming disulfide bonds is the air oxidation of the linear peptides for prolonged periods under cold room temperatures or at room temperature. This procedure results in the creation of a substantial amount of the bioactive, disulfide-linked peptides. The oxidized peptides can be fractionated using reverse-phase high performance liquid chromatography (HPLC) or the like, to separate peptides having different linked configurations. Thereafter, either by comparing these fractions with the elution of the native material or by using an assay, the particular fraction having the correct linkage for maximum biological potency can be determined. However, because of the dilution resulting from the presence of other fractions of less biopotency, a somewhat higher dosage may be beneficial. [0027] Muteins, analogs, or active fragments of the peptides described herein are also contemplated. Derivative muteins, analogs or active fragments of the present peptides can be synthesized according to known techniques, including conservative amino acid substitutions, such as outlined in U.S. Pat. No. 5,545,723 (see particularly col. 2, line 50 to col. 3, line 8); U.S. Pat. No. 5,534,615 (see particularly col. 19, line 45 to col. 22, line 33); and U.S. Pat. No. 5,364,769 (see particularly col. 4, line 55 to col. 7, line 26), each incorporated herein by reference. [0028] In one aspect of this invention, a novel peptide having 7 cysteine residues is provided, where the peptide has a sequence of X 1 X 2 C X 4 X 5 X 6 X 7 X 8 X 9 C X 11 X 12 X 13 X 14 X 15 X 16 CCX 19 X 20 X 21 C X 23 C 24 X 25 X 26 X 27 X 28 Ĉ (SEQ ID 033). It is noted that X 1-2 , X 4-9 , X 11-16 , X 19-21 , X 23 , and X 25-28 can each independently be any amino acid that allows functionality of the resulting peptide, and that the spacing of the cysteine residues is preserved. C 24 is cysteine or a substituted cysteine, and ̂ is a carboxylated C-terminus, as is discussed further herein. [0029] In one aspect, X 27 can be lysine or glycine. In another aspect, X 6 can be hydroxyproline or alanine. In yet another aspect, X 23 can be aspartic acid, gamma-carboxyglutamic acid, or asparagine. In a further aspect, X 25 can be tyrosine or aspartic acid. [0030] In one aspect, this invention provides peptides having a sequence GWCGDOGATC GKLRLYCCSG FCX 23 C 24 X 25 TKTC-X 30 ̂ (SEQ ID 001), where O is hydroxyproline, X 23 is aspartic acid, asparagine, or carboxyglutamic acid, C 24 is cysteine or a substituted cysteine, X 25 is tyrosine or aspartic acid, X 30 is a peptide from 0 to 6 amino acids, and ̂ is a carboxylated C-terminus. In one aspect, the peptide can be an isolated peptide. In another aspect, the peptide can be a synthetic peptide. Numerous synthesis protocols and techniques are known, and any such technique that can be utilized to generate synthetic peptides is considered to be within the present scope. For example, in one aspect solid peptide synthesis can be utilized. [0031] A variety of substitutions and/or variations are contemplated that allow variability in the degree of modulation of sodium channels. The following substitutions and/or variations are thus intended to be merely exemplary of embodiments of this invention, and should not be seen as limiting. Table 1, for example, shows non-limiting examples of peptide analogs obtained in the context of this invention to demonstrate a few of the contemplated moieties. C 24 from SEQ ID 001 is a free-thiol substituted cysteine in some embodiments. C 24 is replaced by an alternative amino acid residue in other embodiments. [0032] In other embodiments the C 24 residue of SEQ ID 001 forms a dimer with a variety of useful peptides. In one aspect, for example, the dimer can be a second peptide according to SEQ ID 001, as is shown in Table 1 as SEQ ID 015. It is noted that the second peptide can have the exact sequence of SEQ ID 001, a substantially similar sequence at to SEQ ID 001, or any degree of modification that allows beneficial functionality of the peptide. [0033] In other embodiments, C 24 is reversibly modified with a molecule through a disulfide linkage. Numerous disulfide linkages are known, and any such linkage that can be utilized that allows sufficient functionality of the peptide is considered to be within the present scope. Non-limiting examples of such substitution molecules can include glutathione, cysteine, cysteamine, DTNB, selenocysteine, selenoglutathione, and any product of a reaction of C 24 with an alkanethiosulfonate reagent or a thiosulfate reagent, and combinations thereof. A few examples from Table 1 showing reversible substitutions include SEQ ID 003, SEQ ID 008, SEQ ID 009, SEQ ID 011, SEQ ID 012, SEQ ID 013, SEQ ID 015, SEQ ID 019, SEQ ID 020, and SEQ ID 021. [0034] In other aspects, C 24 is irreversibly substituted with a molecule. Numerous irreversible substitutions are contemplated, and any such substitution that allows sufficient functionality of the peptide is considered to be within the present scope. Non-liming examples of irreversibly substituted molecules include acetamidomethyl, products of a reaction of C 24 with maleimides, vinyl sulfones and related α,β-unsaturated systems, β-haloethylamine, α-halocarbonyls, or a combination thereof. On example from Table 1 showing irreversible substitutions is SEQ ID 014. [0035] In another aspect, a peptide is provided having a sequence of SEQ ID 001, wherein X 23 is aspartic acid, C 24 is an un-substituted cysteine, and X 25 is tyrosine, where such a sequence is GWCGDOGATC GKLRLYCCSG FCDCYTKTC-X 30 ̂ (SEQ ID 022). In a more specific aspect, X 30 can be SEQ ID 002, where the resulting peptide would be GWCGDOGATC GKLRLYCCSG FCDCYTKTCK DKSSA (SEQ ID 023). [0036] In a further aspect, a peptide is provided having a sequence of SEQ ID 001, wherein X 23 is aspartic acid, C 24 is substituted with cystamine, and X 25 is tyrosine. In a more specific aspect, X 30 can be SEQ ID 002, where the resulting peptide can have a sequence of SEQ ID 011. [0037] It is also noted that in some aspects, a peptide according to aspects of the present invention can further include a label, such as, for example, a fluorescent label. Such a labeled peptide can be used to probe libraries, such as small molecule libraries. [0000] TABLE 1 rNa v 1.7 hNa V 1.7 % block IC 50 or peptide Peptide Sequence % block concentration C.geo1[1-35] SEQ ID 003  1.4 μM 70% C.geo1[C24Abu] SEQ ID 004   >10 μM 20% (33 μM) C.geo1[C24S] SEQ ID 005   >10 μM 20% (33 μM) C.geo1[C24K] SEQ ID 006   >10 μM 20% (33 μM) C.geo1[C24E] SEQ ID 007   >10 μM 15% (33 μM) C.geeo1[K27G] SEQ ID 008  1.6 μM 60% (33 μM) C.geo1[O6A] SEQ ID 009   >10 μM 60% (33 μM) C.geo1[desGSH] SEQ ID 010   71 nM 70% C.geo1[cystamine] SEQ ID 011   72 nM 70% C.geo1[cystine] SEQ ID 012 925.8 nM not tested C.geo1[DTNB] SEQ ID 013   >3 μM not tested C.geo1[C24Cys(Acm)] SEQ ID 014   >1 uM 70% (33 μM) C.geo1[dimer] SEQ ID 015   437 nM 70% (30 μM) C.geo1[C24D-Cys] SEQ ID 016  2.86 μM not tested C.geo1[C24HoCys] SEQ ID 017  1.5 μM not tested C.geo1[C24Pen] SEQ ID 018   >1 μM not tested C.geo1[D23Gla; cystamine] SEQ ID 019 77.9% block at 3 μM not tested C.geo1[D23N; cystamine] SEQ ID 020 23.8% block at 300 nM not tested C.geo1[Y25D; cystamine] SEQ ID 021 16.2% block at 300 nM not tested [0038] It is noted that a variety of oxidative folding methods can be utilized to generate peptide analogs, and that any useful folding technique is considered to be within the present scope. Various folding methods utilized to generate the exemplary peptides of Table 1 can be as follows: folding in the presence of a 1:1 mixture of GSSH:GSH can be used to generate SEQ IDs 003-009 and SEQ ID 014; folding in the presence of cystamine can be used to generate SEQ ID 011 and SEQ IDs 019-021; folding in the presence of cystine can be used to generate SEQ ID 012; and folding in the presence of copper ions can be used to generate SEQ ID 010 and SEQ IDs 016-018. As other examples, SEQ ID 015 and SEQ ID 013 can be prepared from SEQ ID 010 by reacting it with DMSO and Ellman's reagent (DTNB) respectively. Peptides can subsequently be purified by, for example, RP HPLC, and masses can be confirmed by MALDI mass spectrometry. [0039] In another aspect of the present invention, a peptide is provided having a sequence of DWCGDAGDAC GTLKLRCCSG LCNQYSGTCTĜ (SEQ ID 24), where ̂ is a carboxylated C-terminus. In yet another aspect, a peptide is provided having a sequence of CVGRDSKCGP PPCCMGMTCN YERVRKCT̂ (SEQ ID 25), where ̂ is a carboxylated C-terminus. [0040] Table 2 shows a selectivity profile for various active peptide analogs against subtypes of hNa V 1s given as IC 50 data. The data in this Table show that all three peptides are potent inhibitors of hNa v 1.7. They also showed similarity in hNa v 1.7 potency between C. geo 1[desGSH] (SEQ ID 010) and C. geo 1[cystamine] (SEQ ID 011), which indicated that the second analog could be used as a substitute for the less stable C. geo 1[desGSH] (SEQ ID 003). These data reveal that analogs did not block TTX-resistant hNa V 1.5. [0000] TABLE 2 C.geo1[1-35] C.geo1[desGSH] C.geo1 [cystamine] hNa v SEQ ID 003 SEQ ID 010 SEQ ID 011 1.1 760 28 89 1.2 1110 52 51 1.3 >10000 126 336 1.4 1091 14 14 1.5 >10000 >10000 >10000 1.6 757 21 89 1.7 1396 71 72 [0041] It is noted that many amino acids in a given peptide can be variable, and such variations are considered within the present scope. For example, Pro residues may be substituted with hydroxy-Pro; hydroxy-Pro residues may be substituted with Pro residues; Arg residues may be substituted by Lys, ornithine, homoargine, nor-Lys, N-methyl-Lys, N,N-dimethyl-Lys, N,N,N-trimethyl-Lys or any synthetic basic amino acid; Lys residues may be substituted by Arg, ornithine, homoargine, nor-Lys, or any synthetic basic amino acid; Tyr residues may be substituted with any synthetic hydroxy containing amino acid; Ser residues may be substituted with Thr or any synthetic hydroxylated amino acid; Thr residues may be substituted with Ser or any synthetic hydroxylated amino acid; Phe and Trp residues may be substituted with any synthetic aromatic amino acid; and Asn, Ser, Thr or Hyp residues may be glycosylated. Tyr residues may also be substituted with the 3-hydroxyl or 2-hydroxyl isomers (meta-Tyr or ortho-Tyr, respectively) and corresponding O-sulpho- and O-phospho-derivatives or may be substituted with nor-Tyr, nitro-Tyr, mono-iodo-Tyr or di-iodo-Tyr. Aliphatic amino acids may be substituted by synthetic derivatives bearing non-natural aliphatic branched or linear side chains C n H 2n+2 up to and including n=8. Leu residues may be substituted with Leu(D). Trp residues may be substituted with halo-Trp, Trp(D) or halo-Trp(D). The halogen is iodo, chloro, fluoro or bromo; preferably iodo for halogen substituted-Tyr and bromo for halogen-substituted Trp. In addition, the halogen can be radiolabeled, e.g., 125 I-Tyr. [0042] Examples of synthetic aromatic amino acids include, but are not limited to, nitro-Phe, 4-substituted-Phe wherein the substituent is C 1 -C 3 alkyl, carboxyl, hyrdroxymethyl, sulphomethyl, halo, phenyl, —CHO, —CN, —SO 3 H and —NHAc. Examples of synthetic hydroxy containing amino acids, include, but are not limited to, 4-hydroxymethyl-Phe, 4-hydroxyphenyl-Gly, 2,6-dimethyl-Tyr and 5-amino-Tyr. Examples of synthetic basic amino acids include, but are not limited to, N-1-(2-pyrazolinyl)-Arg, 2-(4-piperinyl)-Gly, 2-(4-piperinyl)-Ala, 2-[3-(2S)pyrrolininyl)-Gly and 2-[3-(2S)pyrrolininyl)-Ala. These and other synthetic basic amino acids, synthetic hydroxy containing amino acids or synthetic aromatic amino acids are described in Building Block Index, Version 3.0 (1999 Catalog, pages 4-47 for hydroxy containing amino acids and aromatic amino acids and pages 66-87 for basic amino acids; see also the website “amino-acids dot com”), incorporated herein by reference, by and available from RSP Amino Acid Analogues, Inc., Worcester, Mass. [0043] In other aspects, Asn residues may be modified to contain an N-glycan and the Ser, Thr and Hyp residues may be modified to contain an O-glycan (e.g., g-N, g-S, g-T and g-Hyp). A glycan can refer to any N-, S- or O-linked mono-, di-, tri-, poly- or oligosaccharide that can be attached to any hydroxy, amino or thiol group of natural or modified amino acids by synthetic or enzymatic methodologies known in the art. The monosaccharides making up the glycan can include D-allose, D-altrose, D-glucose, D-mannose, D-gulose, D-idose, D-galactose, D-talose, D-galactosamine, D-glucosamine, D-N-acetyl-glucosamine (GlcNAc), D-N-acetyl-galactosamine (GalNAc), D-fucose or D-arabinose. These saccharides may be structurally modified, e.g., with one or more O-sulfate, O-phosphate, O-acetyl or acidic groups, such as sialic acid, including combinations thereof. The glycan may also include similar polyhydroxy groups, such as D-penicillamine 2,5 and halogenated derivatives thereof or polypropylene glycol derivatives. The glycosidic linkage is β and 1-4 or 1-3, preferably 1-3. The linkage between the glycan and the amino acid may be α or β, preferably α and is 1-. [0044] Mucin type O-linked oligosaccharides are attached to Ser or Thr (or other hydroxylated residues of the present peptides) by a GalNAc residue. The monosaccharide building blocks and the linkage attached to this first GalNAc residue define the “core glycans,” of which eight have been identified. The type of glycosidic linkage (orientation and connectivities) are defined for each core glycan. Suitable glycans and glycan analogs are described further in U.S. Pat. No. 6,369,193 and in International Publication No. WO 00/23092, each incorporated herein by reference. In one aspect, a glycan can be Gal(β1→3)GalNAc(α1→). [0045] The present peptides can be pharmacologically beneficial because they exhibit activity in animals, for example, in Nav1.7 channel blocking or inhibition. As such, compounds incorporating such peptides can be of use in the treatment of disorders for which a blocker or inhibitor for sodium channels (e.g. Nav1.7) is indicated. [0046] In one aspect, pharmaceutical compositions are contemplated including a peptide having at least 95% sequence identity to SEQ ID 001, including pharmaceutically acceptable salts or solvates thereof, in a pharmaceutically acceptable carrier. In another aspect, the peptide can have a sequence of SEQ ID 001. In yet another aspect, X 23 can be aspartic acid, C 24 can be an un-substituted cysteine, and X 25 can be tyrosine. In a further aspect, X 30 can be SEQ ID 002. Additionally, in another aspect, X 23 can be aspartic acid, C 24 can be substituted with cystamine, and X 25 can be tyrosine. In a further aspect, X 30 can be SEQ ID 002. [0047] Pharmaceutical compositions containing a compound, such as a peptide as an active ingredient can be prepared according to conventional pharmaceutical compounding techniques. See, for example, Remington: The Science and Practice of Pharmacy, 21st Ed., Lippincott Williams & Wilkins, Philadelphia, 2005. Typically, an therapeutically effective amount of active ingredient can be admixed with a pharmaceutically acceptable carrier. The carrier can take a wide variety of forms depending on the form of preparation desired for administration, e.g., intravenous, oral, parenteral or intrathecally. For examples of delivery methods see U.S. Pat. No. 5,844,077, incorporated herein by reference. [0048] For oral administration, compound can be formulated into solid or liquid preparations such as capsules, pills, tablets, lozenges, melts, powders, suspensions or emulsions. In preparing the compositions in oral dosage form, any of the usual pharmaceutical media may be employed, such as, for example, water, glycols, oils, alcohols, flavoring agents, preservatives, coloring agents, suspending agents, and the like in the case of oral liquid preparations (such as, for example, suspensions, elixirs and solutions); or carriers such as starches, sugars, diluents, granulating agents, lubricants, binders, disintegrating agents and the like in the case of oral solid preparations (such as, for example, powders, capsules and tablets). Because of their ease in administration, tablets and capsules represent the most advantageous oral dosage unit form, in which case solid pharmaceutical carriers are obviously employed. If desired, tablets may be sugar-coated or enteric-coated by standard techniques. The active agent can be encapsulated to make it stable to passage through the gastrointestinal tract while at the same time allowing for passage across the blood brain barrier. [0049] For parenteral administration, compounds can be dissolved in a pharmaceutical carrier and administered as either a solution or a suspension. Illustrative of suitable carriers are water, saline, dextrose solutions, fructose solutions, ethanol, or oils of animal, vegetative or synthetic origin. The carrier may also contain other ingredients, for example, preservatives, suspending agents, solubilizing agents, buffers and the like. When the compounds are being administered intrathecally, they may also be dissolved in cerebrospinal fluid. [0050] A variety of administration routes are available. The particular mode selected will depend of course, upon the particular drug selected, the severity of the condition being treated and the dosage required for therapeutic efficacy. The methods of this disclosure, generally speaking, can be practiced using any mode of administration that is medically acceptable, meaning any mode that produces effective levels of the active compounds without causing clinically unacceptable adverse effects. Such modes of administration include oral, rectal, sublingual, topical, nasal, transdermal or parenteral routes. The term “parenteral” includes subcutaneous, intravenous, epidural, irrigation, intramuscular, release pumps, or infusion. For example, administration of the active agent according to this invention may be achieved using any suitable delivery means, including those described in U.S. Pat. No. 5,844,077, incorporated herein by reference. [0051] Alternatively, targeting therapies can be used to deliver the peptide composition more specifically to certain types of cell, by the use of targeting systems such as antibodies or cell specific ligands. Targeting may be desirable for a variety of reasons, e.g. if the agent is unacceptably toxic, or if it would otherwise require too high a dosage, or if it would not otherwise be able to enter the target cells. [0052] The active agents, which are peptides, can also be administered in a cell based delivery system in which a DNA sequence encoding an active agent is introduced into cells designed for implantation in the body of the patient, especially in the spinal cord region. Suitable delivery systems are described in U.S. Pat. No. 5,550,050 and published PCT Application Nos. WO 92/19195, WO 94/25503, WO 95/01203, WO 95/05452, WO 96/02286, WO 96/02646, WO 96/40871, WO 96/40959 and WO 97/12635. Suitable DNA sequences can be prepared synthetically for each active agent on the basis of the developed sequences and the known genetic code. [0053] In some aspects, an active agent can be administered in a therapeutically effective amount. A “therapeutically effective amount” or simply “effective amount” of an active compound refers to a sufficient amount of the compound to treat the desired condition at a reasonable benefit/risk ratio applicable to any medical treatment. The actual amount administered, and the rate and time-course of administration, may depend on the nature and severity of the condition being treated. Prescription of treatment, e.g. decisions on dosage, timing, etc., is within the responsibility of general practitioners or specialists, and typically takes account of the disorder to be treated, the condition of the individual patient, the site of delivery, the method of administration and other factors known to practitioners. Examples of techniques and protocols can be found in Remington: The Science and Practice of Pharmacy. [0054] Dosage can be adjusted appropriately to achieve desired drug levels, locally or systemically. Typically the active agents of the present disclosure exhibit their effect at a dosage range from about 0.001 mg/kg to about 250 mg/kg, preferably from about 0.01 mg/kg to about 100 mg/kg of the active ingredient, more preferably from about 0.05 mg/kg to about 75 mg/kg. A suitable dose can be administered in multiple sub-doses per day. Typically, a dose or sub-dose may contain from about 0.1 mg to about 500 mg of the active ingredient per unit dosage form. Another dosage can contain from about 0.5 mg to about 100 mg of active ingredient per unit dosage form. Dosages are generally initiated at lower levels and increased until desired effects are achieved. In the event that the response in a subject is insufficient at such doses, even higher doses (or effective higher doses by a different, more localized delivery route) may be employed to the extent that patient tolerance permits. Continuous dosing over, for example, 24 hours or multiple doses per day are contemplated to achieve appropriate systemic levels of compounds. [0055] Advantageously, the compositions are formulated as dosage units, each unit being adapted to supply a fixed dose of active ingredients. Tablets, coated tablets, capsules, ampoules and suppositories are examples of dosage forms according to the invention. [0056] It is noted that exact individual dosages, as well as daily dosages, can be determined according to standard medical principles under the direction of a physician or veterinarian for use humans or animals. [0057] The pharmaceutical compositions will generally contain from about 0.0001 to 99 wt. %, or about 0.001 to 50 wt. %, or about 0.01 to 10 wt. % of the active ingredient by weight of the total composition. In addition to the active peptide, the pharmaceutical compositions and medicaments can also contain other pharmaceutically active compounds. Examples of other pharmaceutically active compounds include, but are not limited to, analgesic agents, cytokines and therapeutic agents in all of the major areas of clinical medicine. When used with other pharmaceutically active compounds, the peptides of the present invention may be delivered in the form of drug cocktails. A cocktail is a mixture of any one of the compounds useful with this invention with another drug or agent. In this embodiment, a common administration vehicle (e.g., pill, tablet, implant, pump, injectable solution, etc.) would contain both the instant composition in combination with a supplementary potentiating agent. The individual drugs of the cocktail are each administered in therapeutically effective amounts. A therapeutically effective amount will be determined by the parameters described above; but, in any event, is that amount which establishes a level of the drugs in the area of body where the drugs are required for a period of time which is effective in attaining the desired effects. [0058] A Nav1.7 blocker or inhibitor can thus be usefully combined with another pharmacologically active compound, or with two or more other pharmacologically active compounds, particularly in the treatment of pain. Such combinations offer the possibility of significant advantages, including patient compliance, ease of dosing and synergistic activity. In such combinations, a conopeptide described herein can be administered simultaneously, sequentially or separately in combination with the other therapeutic agent or agents. Agents which may be administered with a conopeptide described herein include agents described in US 2012/0010207, which is incorporated herein by reference. [0059] The term “pharmaceutical composition” refers to physically discrete coherent portions suitable for medical administration. “Pharmaceutical composition in dosage unit form” refers to physically discrete coherent units suitable for medical administration, each containing a daily dose or a multiple (up to four times) or a sub-multiple (down to a fortieth) of a daily dose of the active compound in association with a carrier and/or enclosed within an envelope. Whether the composition contains a daily dose, or for example, a half, a third or a quarter of a daily dose, will depend on whether the pharmaceutical composition is to be administered once or, for example, twice, three times or four times a day, respectively. [0060] The term “salt”, as used herein, denotes acidic and/or basic salts, formed with inorganic or organic acids and/or bases, preferably basic salts. While pharmaceutically acceptable salts are preferred, particularly when employing the compounds of the invention as medicaments, other salts find utility, for example, in processing these compounds, or where non-medicament-type uses are contemplated. Salts of these compounds may be prepared by art-recognized techniques. [0061] Examples of such pharmaceutically acceptable salts include, but are not limited to, inorganic and organic addition salts, such as hydrochloride, sulphates, nitrates or phosphates and acetates, trifluoroacetates, propionates, succinates, benzoates, citrates, tartrates, fumarates, maleates, methane-sulfonates, isothionates, theophylline acetates, salicylates, respectively, or the like. Lower alkyl quaternary ammonium salts and the like are suitable, as well. [0062] As used herein, the term “pharmaceutically acceptable” carrier means a non-toxic, inert solid, semi-solid liquid filler, diluent, encapsulating material, formulation auxiliary of any type, or simply a sterile aqueous medium, such as saline. Some examples of the materials that can serve as pharmaceutically acceptable carriers are sugars, such as lactose, glucose and sucrose, starches such as corn starch and potato starch, cellulose and its derivatives such as sodium carboxymethyl cellulose, ethyl cellulose and cellulose acetate; powdered tragacanth; malt, gelatin, talc; excipients such as cocoa butter and suppository waxes; oils such as peanut oil, cottonseed oil, safflower oil, sesame oil, olive oil, corn oil and soybean oil; glycols, such as propylene glycol, polyols such as glycerin, sorbitol, mannitol and polyethylene glycol; esters such as ethyl oleate and ethyl laurate, agar; buffering agents such as magnesium hydroxide and aluminum hydroxide; alginic acid; pyrogen-free water; isotonic saline, Ringer's solution; ethyl alcohol and phosphate buffer solutions, as well as other non-toxic compatible substances used in pharmaceutical formulations. [0063] Wetting agents, emulsifiers and lubricants such as sodium lauryl sulfate and magnesium stearate, as well as coloring agents, releasing agents, coating agents, sweetening, flavoring and perfuming agents, preservatives and antioxidants can also be present in the composition, according to the judgment of the formulator. Examples of pharmaceutically acceptable antioxidants include, but are not limited to, water soluble antioxidants such as ascorbic acid, cysteine hydrochloride, sodium bisulfite, sodium metabisulfite, sodium sulfite, and the like; oil soluble antioxidants, such as ascorbyl palmitate, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), lecithin, propyl gallate, alpha tocopherol and the like; and the metal chelating agents such as citric acid, ethylenediamine tetraacetic acid (EDTA), sorbitol, tartaric acid, phosphoric acid and the like. [0064] Sodium channels such as Nav1.7 may play a role in various pain states, including acute, inflammatory and/or neuropathic pain. Deletion of the SCN9A gene in nociceptive neurons of mice led to a reduction in mechanical and thermal pain thresholds and reduction or abolition of inflammatory pain responses. In humans, Nav1.7 protein has been shown to accumulate in neuromas, particularly painful neuromas. Gain of function mutations of Nav1.7, both familial and sporadic, have been linked to primary erythermalgia, a disease characterized by burning pain and inflammation of the extremities, and paroxysmal extreme pain disorder. Further, non-selective sodium channel blockers lidocaine and mexiletine can provide symptomatic relief in cases of familial erythermalgia and carbamazepine is effective in reducing the number and severity of attacks in PEPD. Further evidence of the role of Nav1.7 in pain is found in the phenotype of loss of function mutations of the SCN9A gene. [0065] As such, in another aspect of the present disclosure, a method of treating a condition or treating effects of a condition in a subject where sodium channels exhibit increased activity is provided. Such a method can include administering to the subject a therapeutically effective amount of a composition as has been described herein to modulate the activity of the sodium channels. Non-limiting examples of such conditions can include, acute pain, chronic pain, neuropathic pain, cancer pain, diabetic neuropathy, inflammatory pain, trigeminal pain, perioperative pain, visceral pain, nociceptive pain including post-surgical pain, and mixed pain types involving the viscera, gastrointestinal tract, cranial structures, musculoskeletal system, spine, urogenital system, cardiovascular system and CNS, including cancer pain, back and orofacial pain, or a combination thereof. It is also contemplated that such a condition can be a neurological condition, including spinal cord injury, traumatic brain injury, peripheral nerve injury, and the like. [0066] Peptides of the invention can be tested for their effect in reducing or alleviating pain using animal models, such as the SNL (spinal nerve ligation) rat model of neuropathic pain, carageenan induced hyperalgesia model, the Freund's complete adjuvant (CFA)-induced hyperalgesia model, the thermal injury model, the formalin model and the Bennett Model and other modes as described in U.S. Pat. Appl. No. 2011/0124711A1 and U.S. Pat. No. 7,998,980. Carageenan induced hyperalgesia and (CFA)-induced hyperalgesia are models of inflammatory pain. The Bennett model provides an animal model for chronic pain. [0067] Any of the foregoing animal models may be used to evaluate the efficacy of peptides of the invention in treating pain. The efficacy can be compared to a no treatment or placebo control. Additionally or alternatively, efficacy can be evaluated in comparison to one or more known pain relieving medicaments. [0068] Generally, physiological pain is an important protective mechanism designed to warn a subject of danger from potentially injurious stimuli. The pain system operates through a specific set of primary sensory neurons, and in some cases is activated by noxious stimuli via peripheral transducing mechanisms. These sensory fibers are known in the art as nociceptors, and they are characteristically small diameter axons with slow conduction velocities. Nociceptors can encode the intensity, duration, and quality of noxious stimuli; topographical organization of nociceptor projections to the spinal cord also allows stimuli location to be encoded. [0069] Nociceptors are found on nociceptive nerve fibers of which there are two main types, A-delta fibers (myelinated) and C fibers (non-myelinated). The activity generated by nociceptor input is transferred, after complex processing in the dorsal horn, either directly, or via brain stem relay nuclei, to the ventrobasal thalamus and then on to the cortex, where the sensation of pain is generated. [0070] Pain may generally be classified as acute or chronic. Acute pain begins suddenly and is short-lived (usually twelve weeks or less). It is usually associated with a specific cause such as a specific injury and is often sharp and severe. It is the kind of pain that can occur after specific injuries resulting from surgery, dental work, a strain or a sprain. Acute pain does not generally result in any persistent psychological response. In contrast, chronic pain is long-term pain, typically persisting for more than three months and leading to significant psychological and emotional problems. Common examples of chronic pain are neuropathic pain (e.g. painful diabetic neuropathy, postherpetic neuralgia), carpal tunnel syndrome, back pain, headache, cancer pain, arthritic pain and chronic post-surgical pain. [0071] When a substantial injury occurs to body tissue, via disease or trauma, the characteristics of nociceptor activation are altered and there is sensitization in the periphery, locally around the injury and centrally where the nociceptors terminate. These effects lead to a heightened sensation of pain. In acute pain these mechanisms can be useful, in promoting protective behaviors which may better enable repair processes to take place. The normal expectation would be that sensitivity returns to normal once the injury has healed. However, in many chronic pain states, the hypersensitivity far outlasts the healing process and is often due to nervous system injury. This injury often leads to abnormalities in sensory nerve fibers associated with maladaptation and aberrant activity. [0072] Clinical pain is present when discomfort and abnormal sensitivity feature among the patient's symptoms. Patients tend to be quite heterogeneous and may present with various pain symptoms. Such symptoms include: 1) spontaneous pain which may be dull, burning, or stabbing; 2) exaggerated pain responses to noxious stimuli (hyperalgesia); and 3) pain produced by normally innocuous stimuli (allodynia). Although patients suffering from various forms of acute and chronic pain may have similar symptoms, the underlying mechanisms may be different and may, therefore, require different treatment strategies. Pain can also therefore be divided into a number of different subtypes according to differing pathophysiology, including nociceptive, inflammatory and neuropathic pain. [0073] Nociceptive pain is induced by tissue injury or by intense stimuli with the potential to cause injury. Pain afferents are activated by transduction of stimuli by nociceptors at the site of injury and activate neurons in the spinal cord at the level of their termination. This is then relayed up the spinal tracts to the brain where pain is perceived (Meyer et al., 1994). The activation of nociceptors activates two types of afferent nerve fibers. Myelinated A-delta fibers transmit rapidly and are responsible for sharp and stabbing pain sensations, whilst unmyelinated C fibers transmit at a slower rate and convey a dull or aching pain. Moderate to severe acute nociceptive pain is a prominent feature of pain from central nervous system trauma, strains/sprains, burns, myocardial infarction and acute pancreatitis, post-operative pain (pain following any type of surgical procedure), posttraumatic pain, renal colic, cancer pain and back pain. Cancer pain may be chronic pain such as tumor related pain (e.g. bone pain, headache, facial pain or visceral pain) or pain associated with cancer therapy (e.g. post-chemotherapy syndrome, chronic postsurgical pain syndrome or post radiation syndrome). Cancer pain may also occur in response to chemotherapy, immunotherapy, hormonal therapy or radiotherapy. Back pain may be due to herniated or ruptured intervertebral discs or abnormalities of the lumber facet joints, sacroiliac joints, paraspinal muscles or the posterior longitudinal ligament. Back pain may resolve naturally but in some patients, where it lasts over 12 weeks, it becomes a chronic condition which can be particularly debilitating. [0074] Neuropathic pain is currently defined as pain initiated or caused by a primary lesion or dysfunction in the nervous system. Nerve damage can be caused by trauma and disease and thus the term ‘neuropathic pain’ encompasses many disorders with diverse aetiologies. These include, but are not limited to, peripheral neuropathy, diabetic neuropathy, post herpetic neuralgia, trigeminal neuralgia, back pain, cancer neuropathy, HIV neuropathy, phantom limb pain, carpal tunnel syndrome, central post-stroke pain and pain associated with chronic alcoholism, hypothyroidism, uremia, multiple sclerosis, spinal cord injury, Parkinson's disease, epilepsy and vitamin deficiency. Neuropathic pain is pathological as it has no protective role. It is often present well after the original cause has dissipated, commonly lasting for years, significantly decreasing a patient's quality of life. The symptoms of neuropathic pain are difficult to treat, as they are often heterogeneous even between patients with the same disease. They include spontaneous pain, which can be continuous, and paroxysmal or abnormal evoked pain, such as hyperalgesia (increased sensitivity to a noxious stimulus) and allodynia (sensitivity to a normally innocuous stimulus). [0075] The inflammatory process is a complex series of biochemical and cellular events, activated in response to tissue injury or the presence of foreign substances, which results in swelling and pain. Arthritic pain is the most common inflammatory pain. Rheumatoid disease is one of the commonest chronic inflammatory conditions in developed countries and rheumatoid arthritis is a common cause of disability. The exact aetiology of rheumatoid arthritis is unknown, but current hypotheses suggest that both genetic and microbiological factors may be important. It has been estimated that almost 16 million Americans have symptomatic osteoarthritis (OA) or degenerative joint disease, most of who are over 60 years of age, and this is expected to increase to 40 million as the age of the population increases, making this a public health problem of enormous magnitude. Most patients with osteoarthritis seek medical attention because of the associated pain. Arthritis has a significant impact on psychosocial and physical function and is known to be the leading cause of disability in later life. Ankylosing spondylitis is also a rheumatic disease that causes arthritis of the spine and sacroiliac joints. It varies from intermittent episodes of back pain that occur throughout life to a severe chronic disease that attacks the spine, peripheral joints and other body organs. [0076] Another type of inflammatory pain is visceral pain which includes pain associated with inflammatory bowel disease (IBD). Visceral pain is pain associated with the viscera, which encompass the organs of the abdominal cavity. These organs include the sex organs, spleen and part of the digestive system. Pain associated with the viscera can be divided into digestive visceral pain and non-digestive visceral pain. Commonly encountered gastrointestinal (GI) disorders that cause pain includes functional bowel disorder (FBD) and inflammatory bowel disease (IBD). These GI disorders include a wide range of disease states that are currently only moderately controlled, including, in respect of FBD, gastro-esophageal reflux, dyspepsia, irritable bowel syndrome (IBS) and functional abdominal pain syndrome (FAPS), and, in respect of IBD, Crohn's disease, ileitis and ulcerative colitis, all of which regularly produce visceral pain. Other types of visceral pain include the pain associated with dysmenorrhea, cystitis and pancreatitis and pelvic pain. [0077] It should be noted that some types of pain have multiple aetiologies and thus can be classified in more than one area, e.g. back pain and cancer pain have both nociceptive and neuropathic components. Other types of pain include: (a) pain resulting from musculo-skeletal disorders, including myalgia, fibromyalgia, spondylitis, sero-negative (non-rheumatoid) arthropathies, non-articular rheumatism, dystrophinopathy, glycogenolysis, polymyositis and pyomyositis; (b) heart and vascular pain, including pain caused by angina, myocardical infarction, mitral stenosis, pericarditis, Raynaud's phenomenon, scleredoma and skeletal muscle ischemia; (c) head pain, such as migraine (including migraine with aura and migraine without aura), cluster headache, tension-type headache mixed headache and headache associated with vascular disorders; (d) erythermalgia; and (e) orofacial pain, including dental pain, otic pain, burning mouth syndrome and temporomandibular myofascial pain. EXAMPLES Example 1 Venom Screening [0078] Material from 10 Conus species has been extracted, fractionated, and screened for block of hNaV1.7 using the QPatch assay. A summary of Conus species and fractionation data is provided in Table 1. Based on initial efforts, a total of 393 fractions have been collected and screened for activity. Of these initial crude fractions, 29 fractions were identified as ‘hits’, exhibiting ≧30% block of hNaV1.7 (˜9.2% of fractions were found to be active) (Table 3). [0000] TABLE 3 Overview of Screening Venom Libraries Fractionation Number of ‘hits’ Species (block ≧ 30%) C. miles 2 C. vexillum 2 C. geographus 11 C. betulinus 0 C. textile 2 C. striatus 9 C. magus 0 C. marmoreus 1 C. distans 1 C. quercinas 1 Example 2 Screening of Conpeptide Fractions [0079] From screening and deconvolution of venom fractions, we identified Conus geographus as one promising species in possessing conopeptide components that block hNaV1.7. Initial screening results of C. geographus venom are summarized in Table 4. [0000] TABLE 4 Initial QPatch Results From the Crude Fractionation of C. geographus . Fraction 1 2 3 4 5 6 7 8 9 10 % Inh.   24 a 32 21 42 27 37 28   41 a 23   59 a Fraction 11 12 13 14 15 16 17 18 19 20 % Inh. 11 31 15  6 22  8 21  2   10 a 15 Fraction 21 22 23 24 25 26 27 28 29 30 % Inh. 18 26  5  5  9  5  9 15 10 10 Fraction 31 32 33 34 34 36 37 38 39 40 % Inh. −14   20 42 27  6  3 −1  7 18 13 Fraction 41 42 43 44 45 46 47 48 49 50 % Inh.  3  2 20  8 37 40 28   24 b   33 a   41 a Fraction 51 52 53 54 55 % Inh.   17 a 22 −1  5 −7 Conopeptide material extracted from approximately 600 mg lyophilized C. geographus ducts and was screened against hNaV1.7. Fraction amounts corresponding to approximately 6 mg equivalents of total conopeptide material were re-suspended in 200 μL volume. a denotes shorter exposure due to seal breakdown. b n = 2 Fractions exhibiting ≧30% block of hNaV1.7 are indicated in bold Example 3 Deconvolution and Identification of Hits [0080] Initial screening of C. geographus crude fractions revealed two major groupings of fractions that blocked the hNaV1.7 response (See Table 4). Further purification of these fractions resulted in sub-fractions that exhibited hNaV1.7 block greater than 30%: SubFr 34.4 (69%), SubFr 34.5 (69% block), SubFr 33.5 (34% block), SubFr 33.6 (40% block), SubFr 33.7 (31% block) (Table 5). [0000] TABLE 5 QPatch Results From Sub-fractionation of C. geographus Fractions Fraction 32 32.2 32.3 32.4 32.5 32.6 32.7 % Inh. 20 15 18 18 25 26 29 Fraction 33 33.3 33.4 33.5 33.6 33.7 33.8 % Inh. 42 31 23 34 40 31 20 Fraction 34 34.3 34.4 34.5 34.6 Inh. 27 33 69 69 18 Fraction 45 45.4 45.5 45.6 45.7 % Inh. 37   22 a 13 30  8 Fraction 46 46.3 46.4 % Inh. 40 11 22 Fraction 47 47.4 47.5 % Inh. 28 23 23 Fractions exhibiting ≧30% block of hNaV1.7 are indicated in bold Example 4 Characterization of the Nav1.7 Active Peptides from C. Geographus [0081] Initial sequencing efforts of the C. geographus active peptide identified in SubFr 33.6 revealed an incomplete peptide sequence (GXCCGDOGATC KLRLYCCSGF CDCYTcTc . . . ) where X denotes ambiguity in the amino acid sequence SEQ ID 026. To elucidate the complete sequence of this peptide, both mass spectrometry methods and molecular biology techniques were employed in parallel. [0082] Molecular Biology Methods. Due to limited quantities of the native active peptide, RACE-PCR experiments were conducted in an attempt to elucidate the entire peptide sequence. From PCR experiments, the entire sequence was identified [0000] SEQ ID 027 (GWCGDPGATC GKLRLYCCSG FCDCYTKTCK DKSSA). Furthermore, transcriptome information confirmed this sequence in multiple locations using RNA isolated from C. geographus ducts. [0083] Mass Spectrometry Analysis. The calculated mass (3739.2 Da), based upon the sequence obtained from PCR experiments, and the experimentally-determined mass (3934.4 Da) differed by 195.3 Da suggesting the presence of modified residues within the sequence. [0084] Solid Phase Peptide Synthesis. Based on the unmodified sequence obtained from the PCR and transcriptome data, analogs of the C. geographus peptide were designed and synthesized by SPPS using standard Fmoc-protocols. Initial syntheses lacked Ser-34 (below). Synthesis of the active peptide was repeated successfully resulting in analogs C. geo 1[1-35] (SEQ ID 003) and C. geo 1[C24Abu] (SEQ ID 004). [0000] C. geo1[des-Ser34]: SEQ ID 028 GWCGDOGATCGKLRLYCCSGFCDCYTKTCKDKS_A{circumflex over ( )} C. geo1[C24Abu,des-Ser34]: SEQ ID 029 GWCGDOGATCGKLRLYCCSGFCD(Abu)YTKTCKDKS_A{circumflex over ( )} C. geo1[1-35]: SEQ ID 003 GWCGDOGATCGKLRLYCCSGFCDCYTKTCKDKSSA{circumflex over ( )} C. geo1[C24Abu]: SEQ ID 004 GWCGDOGATCGKLRLYCCSGFCD(Abu)YTKTCKDKSSA{circumflex over ( )} *Note:  Abu = Fmoc-aminobutyric acid; {circumflex over ( )}denotes carboxylated C-terminus [0085] Synthetic peptides were folded using both air oxidation and glutathione-assisted oxidation methods. Folding mixtures were purified by semi-preparative RP-HPLC and the molecular masses of the folding products were confirmed by MALDI-TOF mass spec. [0086] Electrophysiology. Folded peptide analogs were first tested for activity at the University of Utah against NaV1.7 from rat. C. geo 1[des-Ser34] (SEQ ID 028) exhibited very slow reversibility and resulted in 70% block using 3.3 μM peptide. Isosteric replacement of Cys24 with aminobutyric acid (Abu) in C. geo 1[C24Abu,des-Ser34] (SEQ ID 004) decreased NaV1.7 block to 20% at 10 μM and was quickly reversible (data not shown). These data suggest that Cys24 is integral for efficient block of NaV1.7. As such, 10 nmols of C. geo 1[des-Ser34] (SEQ ID 028) was subsequently used for testing against human NaV1.7 in the QPatch assay ( FIG. 1 ). [0087] RACE-PCR: RACE-PCR was employed to capture the entire sequence (unmodified; SEQ ID 030): [0000] GGTQHRALRS TIKLSLLRQH RGWCGDPGAT CGKLRLYCCS GFCDCYTKTC KDKSSASSPS VLYPFLPES. Δmass between unmodified sequence and MALDI-ToF data was +197.1 Da suggesting modification of the sequence. [0088] MALDI-ToF analysis: MALDI-ToF analysis of C. geo[ 1-35, des-Ser34] (SEQ ID 028) and C. geo 1[1-35] (SEQ ID 003) showed the peptide to be ‘heavy’ by 305 Da indicating peptide-GSH adduct formed at Cys-24. Peptide-adducts may suggest bulky modification of Cys-24, e.g. S-linked glycosylation. Example 5 Verification of which Cys (Cys22 or Cys24) is the Free Cys Residue in Synthetic, Folded C. Geo 1 [0089] The free cysteine of folded C. geo 1[desGSH] (SEQ ID 010) was alkylated with 4-vinylpyridine (VP) and then the peptide was reduced and all remaining cysteines were alkylated with iodoacetamide (IAM-iodoacetamide). Peptide treated this way was then digested with Endoproteinase AspN, subjected to analytical reversed phase (RP) HPLC, and all products were collected and analyzed by MALDI-TOF. The mass of peak 1 (17.16 min, analytical HPLC; [M+H]+=1123.56) was found to be the same as expected mass ([M+H]+=1123.93) for a peptide fragment DC(VP)YTKTC(IAM)K (SEQ ID 031) of digested C. geo 1. The results show that the Cys24 is the one with a free thiol and likely (disulfide) linked to GSH in synthetic C. geo 1. Example 6 Connectivity of Cys Residues in Synthetic C. Geo 1 [0090] For this example C. geo 1[desGSH] (SEQ ID 010) was used. The peptide was treated with 4-vinylpyridine and purified by HPLC. Next, it was treated with tris(2-carboxyethyl)phosphine (TCEP) for 45 min, which caused partial reduction of the peptide. Finally, the mixture was treated with N-ethylmaleimide (NEM), and purified by analytical RP-HPLC. Masses of collected peaks 1 through 5 were analyzed by MALDI-TOF. Following results were obtained: a) Peak 1 [M+H] + found =3842.37, which corresponds to 3 disulfide closed and alkylated Cys 24 ; b) Peak 2 [M+H] + found =4093.56, 2 disulfide bridges closed, 1 disulfide alkylated with NEM; c) Peak 3 [M+H] + found =4345.69, 1 disulfide bridge closed, 2 disulfide alkylated with NEM; d) Peak 4 [M+H] + found =4345.66, 1 disulfide bridge closed, 2 disulfide alkylated with NEM; e) Peak 5 [M+H] + found =4598.60, 3 disulfide bonds alkylated with NEM. Intermediates labeled as Peak 1, 2 and 3 were treated with TCEP for 1 h and then reacted with IAM. The resulting material was purified by RP-HPLC and then treated with modified trypsin for 3 h. This material was next analyzed by MALDI-TOF. Based on the overall data, it was determined that the connectivity in synthetic C. geo 1[desGSH] (SEQ ID 010) is: Cys3-Cys18, Cys10-Cys22 and Cys17-Cys29, which falls into a predicted VI/VII cysteine framework. It was also an additional confirmation that Cys24 was not involved in disulfide-bond formation but nevertheless involved in the functional activity of the synthetic C. geo 1. Example 7 Discovery of C. Geo 2 [0096] In addition to the biologically-active C. geo 1 peptide isolated from Conus geographus, a second active peptide has been identified from sub-fraction 34.5 ( C. geo 2). QPatch assay of the isolated peptide resulted in 69% block of hNaV1.7. The isolated native peptide was reduced and alkylated by treatment with dithiothreitol and 4-vinylpyridine in preparation for sequencing by Edman degradation at the University of Utah. Sequencing efforts revealed the partial peptide sequence of XXCGDAGDA CGTLKLRCCS GLCNQYSGTC S . . . , (SEQ ID 032) where X denotes ambiguity in the amino acid sequence. Using the partial sequence, the complete peptide sequence was retrieved by searching C. geographus transcriptome data as described previously. The complete sequence of C. geo 2 exhibits the canonical ω-conopeptide cysteine framework and shares a fair amount of sequence identity with C. geo 1 (˜55% homologous); however, C. geo 2 lacks the additional cysteine (Cys-24) observed in C. geo 1 (See alignment below). [0000] C. geo1 (SEQ ID 003) G WCGD O G AT CG K L R L Y CCSG F C D CY TK TC KDKSSA{circumflex over ( )} C. geo2 (SEQ ID 024) D WCGD A G DA CG T L K L R CCSG L C NQ Y SG TC TG{circumflex over ( )} *Note:  Bold represents homology between sequences; {circumflex over ( )}denotes carboxylated C-terminus [0097] Of particular interest is that members of the ω-conopeptide family typically possess a C-terminal [Ser-Ser-Ala] tripeptide following the stop codon. However, C. geo 1 (SEQ ID 003) has incorporated the tripeptide into the mature sequence, thereby increasing the C-terminal diversity of this peptide family. Example 8 Discovery of C. Geo 3 [0098] A mass of 3094.35 Da was identified in an active SubFr 33.6 of conus geographus (40% block of hNav1.7). A sequence of a peptide was identified (SEQ ID 025) in the transcriptome data for Conus geographus, characterized by the same mass. It was then synthesized and folded in the presence of reduced and oxidized gluthatione. Three peaks of the same, desired mass were collected and tested against hNav1.7 and rNav1.7. In both cases peptide was not active. [0099] It is to be understood that the above-described compositions and modes of application are only illustrative of preferred embodiments of the present invention. Numerous modifications and alternative arrangements may be devised by those skilled in the art without departing from the spirit and scope of the present invention and the appended claims are intended to cover such modifications and arrangements. Thus, while the present invention has been described above with particularity and detail in connection with what is presently deemed to be the most practical and preferred embodiments of the invention, it will be apparent to those of ordinary skill in the art that numerous modifications, including, but not limited to, variations in size, materials, shape, form, function and manner of operation, assembly and use may be made without departing from the principles and concepts set forth herein.
The present invention relates to conopeptides that are naturally available in minute amounts in the venom of the cone snails or analogous to the naturally available peptides, and which block the sodium channels.
0
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. Ser. No. 12/398,753, filed Mar. 5, 2009, entitled “Patient Selectable Joint Arthroplasty Devices and Surgical Tools”, which in turn claims priority from U.S. Provisional Application Ser. No. 61/034,048, filed Mar. 5, 2008, entitled “Patient Selectable Joint Arthroplasty Devices and Surgical Tools,” and U.S. Provisional Application Ser. No. 61/052,430, filed May 12, 2008, entitled “Patient Selectable Joint Arthroplasty Devices and Surgical Tools.” U.S. Ser. No. 12/398,753 is also a continuation in part of U.S. Ser. No. 11/671,745, filed Feb. 6, 2007, entitled “Patient Selectable Joint Arthroplasty Devices and Surgical Tools”, which issued Nov. 29, 2011 as U.S. Pat. No. 8,066,708, which in turn claims the benefit of U.S. Ser. No. 60/765,592 entitled “S URGICAL T OOLS FOR P ERFORMING J OINT A RTHROPLASTY ” filed Feb. 6, 2006; U.S. Ser. No. 60/785,168, entitled “S URGICAL T OOLS FOR P ERFORMING J OINT A RTHROPLASTY ” filed Mar. 23, 2006; and U.S. Ser. No. 60/788,339, entitled “S URGICAL T OOLS FOR P ERFORMING J OINT A RTHROPLASTY ” filed Mar. 31, 2006. Each of the above-described applications is hereby incorporated by reference in their entirety. FIELD OF THE INVENTION The present invention relates to orthopedic methods, systems and prosthetic devices and more particularly relates to surgical templates designed to achieve optimal cut planes in a joint in preparation for installation of a joint implant. BACKGROUND OF THE INVENTION There are various types of cartilage, e.g., hyaline cartilage and fibrocartilage. Hyaline cartilage is found at the articular surfaces of bones, e.g., in the joints, and is responsible for providing the smooth gliding motion characteristic of moveable joints. Articular cartilage is firmly attached to the underlying bones and measures typically less than 5 mm in thickness in human joints, with considerable variation depending on joint and site within the joint. In addition, articular cartilage is aneural, avascular, and alymphatic. In adult humans, this cartilage derives its nutrition by a double diffusion system through the synovial membrane and through the dense matrix of the cartilage to reach the chondrocyte, the cells that are found in the connective tissue of cartilage. Adult cartilage has a limited ability of repair; thus, damage to cartilage produced by disease, such as rheumatoid and/or osteoarthritis, or trauma can lead to serious physical deformity and debilitation. Furthermore, as human articular cartilage ages, its tensile properties change. The superficial zone of the knee articular cartilage exhibits an increase in tensile strength up to the third decade of life, after which it decreases markedly with age as detectable damage to type II collagen occurs at the articular surface. The deep zone cartilage also exhibits a progressive decrease in tensile strength with increasing age, although collagen content does not appear to decrease. These observations indicate that there are changes in mechanical and, hence, structural organization of cartilage with aging that, if sufficiently developed, can predispose cartilage to traumatic damage. For example, the superficial zone of the knee articular cartilage exhibits an increase in tensile strength up to the third decade of life, after which it decreases markedly with age as detectable damage to type II collagen occurs at the articular surface. The deep zone cartilage also exhibits a progressive decrease in tensile strength with increasing age, although collagen content does not appear to decrease. These observations indicate that there are changes in mechanical and, hence, structural organization of cartilage with aging that, if sufficiently developed, can predispose cartilage to traumatic damage. Once damage occurs, joint repair can be addressed through a number of approaches. One approach includes the use of matrices, tissue scaffolds or other carriers implanted with cells (e.g., chondrocytes, chondrocyte progenitors, stromal cells, mesenchymal stem cells, etc.). However, clinical outcomes with biologic replacement materials such as allograft and autograft systems and tissue scaffolds have been uncertain since most of these materials cannot achieve a morphologic arrangement or structure similar to or identical to that of normal, disease-free human tissue it is intended to replace. Moreover, the mechanical durability of these biologic replacement materials remains uncertain. Usually, severe damage or loss of cartilage is treated by replacement of the joint with a prosthetic material, for example, silicone, e.g. for cosmetic repairs, or metal alloys. Implantation of these prosthetic devices is usually associated with loss of underlying tissue and bone without recovery of the full function allowed by the original cartilage and, with some devices, serious long-term complications associated with the loss of significant amount of tissue and bone can include infection, osteolysis and also loosening of the implant. As can be appreciated, joint arthroplasties are highly invasive and require surgical resection of the entire, or a majority of the, articular surface of one or more bones involved in the repair. Typically with these procedures, the marrow space is fairly extensively reamed in order to fit the stem of the prosthesis within the bone. Reaming results in a loss of the patient's bone stock and over time subsequent osteolysis will frequently lead to loosening of the prosthesis. Further, the area where the implant and the bone mate degrades over time requiring the prosthesis to eventually be replaced. Since the patient's bone stock is limited, the number of possible replacement surgeries is also limited for joint arthroplasty. In short, over the course of 15 to 20 years, and in some cases even shorter time periods, the patient can run out of therapeutic options ultimately resulting in a painful, non-functional joint. A variety of tools, such as a guide for making one or more surgical cuts, are currently available to assist surgeons. However, these devices are not designed to substantially conform to the actual shape (contour) of the remaining cartilage in vivo and/or the underlying bone. Thus, use and proper alignment of the tool and integration of the implant can be extremely difficult due to differences in thickness and curvature between the patient's surrounding cartilage and/or the underlying subchondral bone and the prosthesis. Thus, there remains a need for tools that increase the accuracy of cuts made to the bone in a joint in preparation for surgical implantation of, for example, an artificial joint. SUMMARY OF THE INVENTION The present invention provides novel surgical tools and methods. In accordance with one embodiment of the invention, a surgical tool includes a template. The template has at least one contact surface for engaging a surface associated with a joint. The at least one contact surface substantially conforms with the surface. The template further includes at least one guide aperture for directing movement of a surgical instrument. One embodiment is a system for articular repair that includes a first template having a first surface and a second surface, the first surface conforming with, and substantially a negative of, at least a portion of first side of a joint; a second template having a third surface that conforms with, and is substantially a negative of, a portion of the first side of the joint, the second template including at least one guide for guiding a surgical instrument in making a cut on the first side of the joint; and an attachment mechanism for attaching the second template to the first template. Other embodiments may include one or more of the following. The first or second template can include a guide for making a vertical cut. The second surface can be at least one of substantially flat, substantially concave, substantially convex, and matched to one of the first or second sides of the joint. The system can include at least one other template, and each of the other templates can be capable of attaching to the second template. The templates can vary in thickness. At least a portion of the first surface can substantially conforms to at least one of uncut subchondral bone, uncut cartilage, and uncut bone of a first or second side of the joint. At least a portion of the second surface can substantially conform to at least one of uncut subchondral bone, uncut cartilage, and uncut bone of a first or second side of a joint. At least a portion of the third surface can substantially conforms to at least one of uncut subchondral bone, uncut cartilage, and uncut bone of a first or second side of a joint. The attachment mechanism can include at least one of a snapfit, dovetail and a cross-pin. The attachment mechanism can allow for rotation relative to one of an anatomical and a biomechanical axis. The joint can be at least one of a hip, knee, ankle, toe joint, shoulder, elbow, wrist, finger joint, spine or spinal joint. Another embodiment is a system for articular joint repair that includes: a first template having a first surface and a second surface, the first surface substantially a negative of at least a portion of the tibial plateau; a second template having a third surface that is substantially a negative of a portion of the tibia, the second template including at least one guide for guiding a surgical instrument in making a cut on the tibia; and an attachment mechanism for attaching the second template to the first template. Other aspects of this embodiment may include one or more of the following. The first or second template can include a guide for making a vertical tibial cut. The second surface can be at least one of substantially flat, substantially concave, substantially convex, and matched to one of the tibia and the femur. The system can include at least one other template can have a first surface and a second surface. The first surface can conform with, and be substantially a negative of, at least a portion of the tibial plateau. Each of the other templates can be capable of attaching to the second template, wherein the first template and each of the other templates vary in thickness. At least a portion of the first surface can be substantially a negative of at least one of uncut subchondral bone, uncut cartilage, and uncut bone of a tibia. At least a portion of the second surface can be substantially a negative of at least one of uncut subchondral bone, uncut cartilage, and uncut bone of a tibia. At least a portion of the third surface can be substantially a negative of at least one of uncut subchondral bone, uncut cartilage, and uncut bone of a tibia. The attachment mechanism can include at least one of a snapfit, dovetail and a cross-pin. The attachment mechanism can allow for rotation relative to one of an anatomical and a biomechanical axis. At least one guide can guides a surgical instrument in making a cut on the tibia having a desired slope relative to at least one of a biomechanical and an anatomical axis. The articular joint repair can be a joint resurfacing, including a knee joint resurfacing, a joint replacement or other procedure. Another embodiment is a system for articular repair that includes a first template having a first surface substantially matching at least a portion of the tibial plateau. The first template can include a medial edge that corresponds to a predetermined location for a vertical tibial cut. Other embodiments may have one or more of the following. A second template can have a surface substantially matching at least a portion of the tibia, and can include at least one guide for guiding a surgical instrument. The second template can also have an attachment mechanism for attaching the second template to the first template. The first template can include a guide for guiding a surgical instrument. The medial edge can be adapted as a guide for making a vertical tibial cut. The system can have at least one other template having a first surface and a second surface. The first surface can substantially match at least a portion of the tibial plateau. The first template and each of the other templates can vary in thickness. At least a portion of the first surface can substantially match at least one of uncut subchondral bone, uncut cartilage, and uncut bone. Another embodiment is a kit for testing at least one of ligament balancing and ligament tension, which includes a first template that has at least one surface substantially conforming with at least a portion of a first articular joint surface. The template is configured for placement on the first articular joint surface and between the first articular joint surface and a second articular joint surface, and it has a predefined thickness configured to provide a physical spacer for assessing at least one of ligament balance and ligament tension during a surgical procedure. Other embodiments can include one or more of the following. The kit can include a second template that has at least one surface substantially conforming with at least the portion of the first articular joint surface. The template can be configured for placement on the first articular joint surface and between the first articular joint surface and the second articular joint surface. The template can have a second predefined thickness configured to provide a physical spacer for assessing at least one of ligament balance and ligament tension during a surgical procedure. The kit can also include additional templates of varying thicknesses. The second template can also have at least one guide for guiding a surgical instrument, and an attachment mechanism for attaching the second template to at least one of the first template and the at least one other template. The kit can be used for articular joints, including a knee joint, a hip joint, a shoulder joint, an elbow joint, a wrist joint, a finger joint, a toe joint, and an ankle joint. At least a portion of the surface can substantially conforms to at least one of uncut subchondral bone, uncut cartilage, and uncut bone. Another embodiment is a method of partial or total knee replacement or resurfacing that includes: positioning a first surface of a first instrument onto at least a portion of the tibial plateau, the first surface being substantially a negative of at least a portion of the tibial plateau; cross-referencing a second instrument to the first instrument to align position of the second instrument on the tibia, the second instrument including at least one surgical cut guide; and directing a cut using the at least one surgical guide of the second of the second instrument. Other embodiments can have one or more of the following. The cut can be a tibial cut. The instruments can be templates, surgical tools or other devices. The first instrument can include a guide for making a cut, which can be a vertical or horizontal cut, e.g., on the tibia. The first instrument can include a medial edge that corresponds to a predetermined location for a vertical tibial cut, the method further comprising confirming the proper location of the vertical tibial cut based on the medial edge. At least a portion of the first surface can substantially conform to at least one of uncut subchondral bone, uncut cartilage, and uncut bone. The first surface of the instrument is based, at least in part, on electronic image data of the tibial plateau. Cross-referencing can include attaching the first instrument to the second instrument. The at least one guide of the second instrument can guide a surgical instrument in making a cut on the tibia having a desired slope relative to at least one of a biomechanical and an anatomical axis. Another embodiment is a method for testing at least one of ligament balancing and ligament tension of a joint that includes: inserting a first template having a first surface onto a first joint surface, the first surface substantially conforming to the first joint surface; and inserting a second template onto the first joint surface, the second template having a first surface that conforms with, and is substantially a negative of, the first joint surface, the second template having a thickness that varies from the first template. Other embodiments can include one or more of the following. The method can further include selecting one of the first and second templates based on at least one of ligament balancing and ligament tension. The method can also include attaching a third template to the selected template, the third template, including at least one guide for guiding a surgical instrument; positioning the first surface of the selected template onto the first joint surface; and guiding the surgical instrument using the at least one guide. The joint can be one of a knee joint, a hip joint, a shoulder joint, an elbow joint, a wrist joint, a finger joint, a toe joint, and an ankle joint. Another embodiment is a system for articular repair that includes first and second templates having a first surface that conforms with, and substantially is a negative of, at least a portion of a distal femur. It also includes a second template that has a third surface that conforms with, and is substantially a negative of, a portion of the distal femur. The second template can include at least one guide for guiding a surgical instrument in making a cut on the distal femur, and an attachment mechanism for attaching the second template to the first template. Other embodiments can include one or more of the following. The first or second templates can include a guide for making a vertical femoral cut. The second surface can be at least one of substantially flat, substantially concave, substantially convex, and matched to one of the tibia and the femur. At least one other template can have a first surface that conforms with, and substantially is a negative of, the at least a portion of the distal femur. Each of the other templates can be capable of attaching to the second template. The first template and each of the other templates can vary in thickness. At least a portion of the first surface can substantially conform to at least one of uncut subchondral bone, uncut cartilage, and uncut bone of a distal femur. At least a portion of the second surface can substantially conform to at least one of uncut subchondral bone, uncut cartilage, and uncut bone of a distal femur. At least a portion of the third surface can substantially conform to at least one of uncut subchondral bone, uncut cartilage, and uncut bone of a tibia. The attachment mechanism can include at least one of a snapfit, dovetail and a cross-pin. The attachment mechanism can allow for rotation relative to one of an anatomical and a biomechanical axis. Another embodiment is a system for articular repair that includes a first template having a first surface and a second surface, the first surface substantially conforming to at least a portion of the distal femur. The first template includes a medial edge that corresponds to a predetermined location for a vertical femoral or tibial cut. Other embodiments can have one or more of the following. A second template can have a third surface substantially conforming to at least a portion of the distal femur or tibial plateau. The second template can include at least one guide for guiding a surgical instrument. There can also be an attachment mechanism for attaching the second template to the first template. The first template can include a guide for guiding a surgical instrument. The medial edge can be adapted as a guide for making a vertical tibial or femoral cut. At least one other template can have a first surface and a second surface. The first surface can substantially conform to at least a portion of the tibial plateau. The first template and each of the other templates can vary in thickness. At least a portion of the first surface can substantially conforms to at least one of uncut subchondral bone, uncut cartilage, and uncut bone. Some embodiments can be used for a partial joint replacement, a total joint replacement, a partial joint resurfacing and a total joint resurfacing. Templates can vary in thickness or curvatures or can be made available in multiple different thicknesses or curvatures. The thickness of the other template can be selected to improve or optimize the position of a bone cut for ligament balancing. BRIEF DESCRIPTION OF THE DRAWINGS The foregoing features of the invention will be more readily understood by reference to the following detailed description, taken with reference to the accompanying drawings, in which: FIG. 1A illustrates a femur, tibia and fibula along with the mechanical and anatomic axes. FIGS. 1B-E illustrate the tibia with the anatomic and mechanical axis used to create a cutting plane along with a cut femur and tibia. FIG. 1F illustrates the proximal end of the femur including the head of the femur. FIG. 2 shows an example of a surgical tool having one surface matching the geometry of an articular surface of the joint, in accordance with one embodiment of the invention. Also shown is an aperture in the tool capable of controlling drill depth and width of the hole and allowing implantation of an insertion of implant having a press-fit design. FIG. 3 is a flow chart depicting various methods of the invention used to create a mold for preparing a patient's joint for arthroscopic surgery, in accordance with one embodiment of the invention. FIG. 4A depicts, in cross-section, an example of a surgical tool containing an aperture through which a surgical drill or saw can fit, in accordance with one embodiment of the invention. The aperture guides the drill or saw to make the proper hole or cut in the underlying bone. Dotted lines represent where the cut corresponding to the aperture will be made in bone. FIG. 4B depicts, in cross-section, an example of a surgical tool containing apertures through which a surgical drill or saw can fit and which guide the drill or saw to make cuts or holes in the bone, in accordance with one embodiment of the invention. Dotted lines represent where the cuts corresponding to the apertures will be made in bone. FIGS. 5A-R illustrate tibial cutting blocks and molds used to create a surface perpendicular to the anatomic axis for receiving the tibial portion of a knee implant, in accordance with various embodiments of the invention. FIGS. 6A-O illustrate femur cutting blocks and molds used to create a surface for receiving the femoral portion of a knee implant, in accordance with various embodiments of the invention. FIG. 6P illustrates an axis defined by the center of the tibial plateau and the center of the distal tibia. FIG. 6 q shows an axis defining the center of the tibial plateau to the femoral head. FIGS. 6R and 6S show isometric views of a femoral template and a tibial template, respectively, in accordance with various embodiments of the invention. FIG. 6T illustrates a femoral guide reference tool attached to the femoral template, in accordance with an embodiment of the invention. FIG. 6U illustrates a sample implant template positioned on the chondyle, in accordance with an embodiment of the invention. FIG. 6V is an isometric view of the interior surface of the sample implant template, in accordance with an embodiment of the invention. FIG. 6W is an isometric view of the tibial template attached to the sample implant, in accordance with an embodiment of the invention. FIG. 6X shows a tibial template that may be used, after the tibial cut has been made, to further guide surgical tools, in accordance with an embodiment of the invention. FIG. 6Y shows a tibial implant and femoral implant inserted onto the tibia and femur, respectively, after the above-described cuts have been made, in accordance with an embodiment of the invention. FIG. 7 illustrates a femoral balancing template on a femur, in accordance with one embodiment of the invention. FIG. 8 illustrates a knee in balanced extension with femoral balancing template fitted on the femoral condyle, in accordance with an embodiment of the invention. FIG. 9 illustrates a tibial cutting guide fitted to the tibia when balanced in extension, in accordance with an embodiment of the invention. FIGS. 10 and 11 illustrate the tibial cutting guide pinned in place, in accordance with an embodiment of the invention. FIG. 12 illustrates the tibial cutting guide with femoral balancing template removed, in accordance with an embodiment of the invention. FIG. 13 illustrates the coronal tibial cut being made, in accordance with an embodiment of the invention. FIGS. 14 and 15 illustrate the use of a patient-specific vertical cut alignment tool to place the vertical tibial cut, in accordance with an embodiment of the invention. FIGS. 16-23 illustrate the procedure and tools for installing the femoral implant FIG. 24 shows the femoral guide removed, and a trough for the anterior margin of the femoral implant, in accordance with an embodiment of the invention. FIGS. 25-27 illustrate a procedure and tools for installing the tibial implant, in accordance with an embodiment. FIG. 28 illustrates a fin created using an osteotome, in accordance with an embodiment of the invention. FIG. 29 shows a tibial cut guide pinned in extension, in accordance with one embodiment of the invention. FIG. 30 shows the femoral balancing template removed, the patient specific alignment tool positioned on the tibial plateau, and a cutting guide attached to the tibia, in accordance with one embodiment of the invention. FIG. 31 shows a kit that may be provided with the resurfacing implants and disposable instrumentation in a single sterile tray, in accordance with one embodiment of the invention. FIG. 32 shows cartilage removal on the condyle, in accordance with one embodiment of the invention. FIG. 33 shows cartilage removal on the condyle, in accordance with one embodiment of the invention. FIG. 34 shows an exemplary navigation chip, in accordance with one embodiment of the invention. FIG. 35 shows a navigation chip in-situ, in accordance with one embodiment of the invention. FIG. 36 shows the tibial ijig placed in the knee, in accordance with one embodiment of the invention. FIG. 37 shows confirmation of the tibial cut planes, in accordance with one embodiment of the invention. FIG. 38 shows the tibial axial cut, in accordance with one embodiment of the invention. FIG. 39 shows the femoral jig placed on the distal femur, in accordance with one embodiment of the invention. FIG. 40 shows the posterior femoral cut performed, in accordance with one embodiment of the invention. FIGS. 41-42 show flexion and extension balance verification, in accordance with one embodiment of the invention. FIG. 43 shows tibial template placement, in accordance with one embodiment of the invention. FIG. 44 shows the implants being cemented, in accordance with one embodiment of the invention. FIG. 45 shows the implants cemented in place, in accordance with one embodiment of the invention. DETAILED DESCRIPTION OF THE INVENTION The following description is presented to enable any person skilled in the art to make and use the invention. Various modifications to the embodiments described will be readily apparent to those skilled in the art, and the generic principles defined herein can be applied to other embodiments and applications without departing from the spirit and scope of the present invention as defined by the appended claims. Thus, the present invention is not intended to be limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein. To the extent necessary to achieve a complete understanding of the invention disclosed, the specification and drawings of all issued patents, patent publications, and patent applications cited in this application are incorporated herein by reference. 3D guidance surgical tools, referred to herein as a 3D guidance surgical templates, that may be used for surgical assistance may include, without limitation, using templates, jigs and/or molds, including 3D guidance molds. It is to be understood that the terms “template,” “jig,” “mold,” “3D guidance mold,” and “3D guidance template,” shall be used interchangeably within the detailed description and appended claims to describe the tool unless the context indicates otherwise. 3D guidance surgical tools that may be used may include guide apertures. It is to be understood that the term guide aperture shall be used interchangeably within the detailed description and appended claims to describe both guide surface and guide elements. As will be appreciated by those of skill in the art, the practice of the present invention employs, unless otherwise indicated, conventional methods of x-ray imaging and processing, x-ray tomosynthesis, ultrasound including A-scan, B-scan and C-scan, computed tomography (CT scan), magnetic resonance imaging (MRI), optical coherence tomography, single photon emission tomography (SPECT) and positron emission tomography (PET) within the skill of the art. Such techniques are explained fully in the literature and need not be described herein. See, e.g., X-Ray Structure Determination: A Practical Guide, 2nd Edition, editors Stout and Jensen, 1989, John Wiley & Sons, publisher; Body CT: A Practical Approach, editor Slone, 1999, McGraw-Hill publisher; X-ray Diagnosis: A Physician's Approach, editor Lam, 1998 Springer-Verlag, publisher; and Dental Radiology: Understanding the X-Ray Image, editor Laetitia Brocklebank 1997, Oxford University Press publisher. See also, The Essential Physics of Medical Imaging (2 nd Ed.), Jerrold T. Bushberg, et al. A. The Joint Replacement Procedure The present invention may be applied to all joints, such as, without limitation, the knee, hip, shoulder, elbow, wrist, finger, toe, and ankle. Illustratively, the knee and hip joint procedures are discussed below, so as to teach the concept of the design as it would then apply to other joints in the body. All of the embodiments described herein are applicable partial joint replacement, total joint replacement, and hemiarthroplasty. The embodiments may be combined with standard instrumentation known in the art as well as surgical techniques and robotics known in the art. i. Knee Joint Performing a total knee arthroplasty is a complicated procedure. In replacing the knee with an artificial knee, it is important to get the anatomical and mechanical axes of the lower extremity aligned correctly to ensure optimal functioning of the implanted knee. As shown in FIG. 1A , the center of the hip 1902 (located at the head 1930 of the femur 1932 ), the center of the knee 1904 (located at the notch where the intercondular tubercle 1934 of the tibia 1936 meet the femur) and ankle 1906 lie approximately in a straight line 1910 which defines the mechanical axis of the lower extremity. The anatomic axis 1920 aligns 5-7° offset θ from the mechanical axis in the valgus, or outward, direction. The long axis of the tibia 1936 is collinear with the mechanical axis of the lower extremity 1910 . From a three-dimensional perspective, the lower extremity of the body ideally functions within a single plane known as the median anterior-posterior plane (MAP-plane) throughout the flexion-extension arc. In order to accomplish this, the femoral head 1930 , the mechanical axis of the femur, the patellar groove, the intercondylar notch, the patellar articular crest, the tibia and the ankle remain within the MAP-plane during the flexion-extension movement. During movement, the tibia rotates as the knee flexes and extends in the epicondylar axis which is perpendicular to the MAP-plane. A variety of image slices can be taken at each individual joint, e.g., the knee joint 1950 - 1950 n , and the hip joint 1952 - 1950 n . These image slices can be used as described above in Section I along with an image of the full leg to ascertain the axis. With disease and malfunction of the knee, alignment of the anatomic axis is altered. Performing a total knee arthroplasty is one solution for correcting a diseased knee. Implanting a total knee joint, such as the PFC Sigma RP Knee System by Johnson & Johnson, requires that a series of resections be made to the surfaces forming the knee joint in order to facilitate installation of the artificial knee. The resections should be made to enable the installed artificial knee to achieve flexion-extension movement within the MAP-plane and to optimize the patient's anatomical and mechanical axis of the lower extremity. First, the tibia 1930 is resected to create a flat surface to accept the tibial component of the implant. In most cases, the tibial surface is resected perpendicular to the long axis of the tibia in the coronal plane, but is typically sloped 4-7° posteriorly in the sagittal plane to match the normal slope of the tibia. As will be appreciated by those of skill in the art, the sagittal slope can be 0° where the device to be implanted does not require a sloped tibial cut. The resection line 1958 is perpendicular to the mechanical axis 1910 , but the angle between the resection line and the surface plane of the plateau 1960 varies depending on the amount of damage to the knee. FIGS. 1B-D illustrate an anterior view of a resection of an anatomically normal tibial component, a tibial component in a varus knee, and a tibial component in a valgus knee, respectively. In each figure, the mechanical axis 1910 extends vertically through the bone and the resection line 1958 is perpendicular to the mechanical axis 1910 in the coronal plane, varying from the surface line formed by the joint depending on the amount of damage to the joint. FIG. 1B illustrates a normal knee wherein the line corresponding to the surface of the joint 1960 is parallel to the resection line 1958 . FIG. 1C illustrates a varus knee wherein the line corresponding to the surface of the joint 1960 is not parallel to the resection line 1958 . FIG. 1D illustrates a valgus knee wherein the line corresponding to the surface of the joint 1960 is not parallel to the resection line 1958 . Once the tibial surface has been prepared, the surgeon turns to preparing the femoral condyle. The plateau of the femur 1970 is resected to provide flat surfaces that communicate with the interior of the femoral prosthesis. The cuts made to the femur are based on the overall height of the gap to be created between the tibia and the femur. Typically, a 20 mm gap is desirable to provide the implanted prosthesis adequate room to achieve full range of motion. The bone is resected at a 5-7° angle valgus to the mechanical axis of the femur. Resected surface 1972 forms a flat plane with an angular relationship to adjoining surfaces 1974 , 1976 . The angle θ′, θ″ between the surfaces 1972 - 1974 , and 1972 - 1976 varies according to the design of the implant. ii. Hip Joint As illustrated in FIG. 1F , the external geometry of the proximal femur includes the head 1980 , the neck 1982 , the lesser trochanter 1984 , the greater trochanter 1986 and the proximal femoral diaphysis. The relative positions of the trochanters 1984 , 1986 , the femoral head center 1902 and the femoral shaft 1988 are correlated with the inclination of the neck-shaft angle. The mechanical axis 1910 and anatomic axis 1920 are also shown. Assessment of these relationships can change the reaming direction to achieve neutral alignment of the prosthesis with the femoral canal. Using anteroposterior and lateral radiographs, measurements are made of the proximal and distal geometry to determine the size and optimal design of the implant. Typically, after obtaining surgical access to the hip joint, the femoral neck 1982 is resected, e.g. along the line 1990 . Once the neck is resected, the medullary canal is reamed. Reaming can be accomplished, for example, with a conical or straight reamer, or a flexible reamer. The depth of reaming is dictated by the specific design of the implant. Once the canal has been reamed, the proximal reamer is prepared by serial rasping, with the rasp directed down into the canal. B. Surgical Tools Surgical assistance can be provided by using a device, referred to also herein as a surgical tool or template, applied to the outer surface of the articular cartilage or the bone, including the subchondral bone, in order to match the alignment of the articular repair system and the recipient site or the joint. The template may be round, circular, oval, ellipsoid, curved or irregular in shape. The shape can be selected or adjusted to match or enclose an area of diseased cartilage or an area slightly larger than the area of diseased cartilage or substantially larger than the diseased cartilage. The area can encompass the entire articular surface or the weight bearing surface. Such devices are typically preferred when replacement of a majority or an entire articular surface is contemplated. The template may include at least one guide for guiding a surgical instrument. The at least one guide may direct the surgical instrument in at least one of a cut, a milling, and a drilling. The at least one guide may be, without limitation, a drill hole, a cut planes, a saw plane and the like. The guide may be oriented in a predefined location relative to, without limitation, the contact surface of the template with the articular cartilage or bone, and may be adapted in shape, size or orientation to an implant shape. Typically, a position of the guide will be chosen that will result in an anatomically desirable cut plane, drill hole, or general instrument orientation for subsequent placement of an articular repair system or for facilitating placement of the articular repair system. Moreover, the template may be designed so that the depth of the drill, reamer or other surgical instrument can be controlled, e.g., the drill cannot go any deeper into the tissue than defined by the device, and the size of the hole in the block can be designed to essentially match the size of the implant. Information about other joints or axis and alignment information of a joint or extremity can be included when selecting the position of these slots or holes. Alternatively, the openings in the template may be made larger than needed to accommodate these instruments. The template may also be configured to conform to the articular shape. The apertures, or openings, provided can be wide enough to allow for varying the position or angle of the surgical instrument, e.g., reamers, saws, drills, curettes and other surgical instruments. An instrument guide, typically comprised of a relatively hard material, can then be applied to the device. The device helps orient the instrument guide relative to the three-dimensional anatomy of the joint. The template may be a mold that can be made of a plastic or polymer. The template may be produced by rapid prototyping technology, in which successive layers of plastic are laid down, as know in the art. In other embodiments, the template or portions of the template can be made of metal. The template can be milled or made using laser based manufacturing techniques. The template may be casted using rapid prototyping and, for example, lost wax technique. It may also be milled. For example, a preformed template with a generic shape can be used at the outset, which can then be milled to the patient specific dimensions. The milling may only occur on one surface of the template, preferably the surface that faces the articular surface. Milling and rapid prototyping techniques may be combined. Curable materials may be used which can be poured into forms that are, for example, generated using rapid prototyping. For example, liquid metal may be used. Cured materials may optionally be milled or the surface can be further refined using other techniques. Metal inserts may be applied to plastic components. For example, a plastic mold may have at least one guide aperture to accept a reaming device or a saw. A metal insert may be used to provide a hard wall to accept the reamer or saw. Using this or similar designs can be useful to avoid the accumulation of plastic or other debris in the joint when the saw or other surgical instruments may get in contact with the mold. Other hard materials can be used to serve as inserts. These can also include, for example, hard plastics or ceramics. In another embodiment, the template does not have metallic inserts to accept a reaming device or saw. The metal inserts or guides may be part of an attached device that is typically in contact with the template. A metallic drill guide or a metallic saw guide may thus, for example, have metallic or hard extenders that reach through the mold thereby, for example, also stabilizing any devices applied to the mold against the physical body of the mold. One or more templates can be used during the surgery. For example, in the hip, a template can be initially applied to the proximal femur that closely approximates the 3D anatomy prior to the resection of the femoral head. The template can include an opening to accommodate a saw. The opening is positioned to achieve an optimally placed surgical cut for subsequent reaming and placement of the prosthesis. A second template can then be applied to the proximal femur after the surgical cut has been made. The second template can be useful for guiding the direction of a reamer prior to placement of the prosthesis. As can be seen in this, as well as in other examples, templates can be made for joints prior to any surgical intervention. However, it is also possible to make templates that are designed to fit to a bone or portions of a joint after the surgeon has already performed selected surgical procedures, such as cutting, reaming, drilling, etc. The template can account for the shape of the bone or the joint resulting from these procedures. Upon imaging, a physical template of a joint, such as a knee joint, or hip joint, or ankle joint or shoulder joint is generated, in accordance with an embodiment of the invention. The template can be used to perform image guided surgical procedures such as partial or complete joint replacement, articular resurfacing, or ligament repair. The template may include reference points or opening or apertures for surgical instruments such as drills, saws, burrs and the like. In order to derive the preferred orientation of drill holes, cut planes, saw planes and the like, openings or receptacles in said template or attachments will be adjusted to account for at least one axis. The axis can be anatomic or biomechanical, for example, for a knee joint, a hip joint, an ankle joint, a shoulder joint or an elbow joint. In one embodiment, only a single axis is used for placing and optimizing such drill holes, saw planes, cut planes, and or other surgical interventions. This axis may be, for example, an anatomical or biomechanical axis. In a preferred embodiment, a combination of axis and/or planes can be used for optimizing the placement of the drill holes, saw planes, cut planes or other surgical interventions. For example, two axes (e.g., one anatomical and one biomechanical) can be factored into the position, shape or orientation of the 3D guided template and related attachments or linkages. For example, two axes, (e.g., one anatomical and biomechanical) and one plane (e.g., the top plane defined by the tibial plateau), can be used. Alternatively, two or more planes can be used (e.g., a coronal and a sagittal plane), as defined by the image or by the patients anatomy. Angle and distance measurements and surface topography measurements may be performed in these one or more, preferably two or more, preferably three or more multiple planes, as necessary. These angle measurements can, for example, yield information on varus or valgus deformity, flexion or extension deficit, hyper or hypo-flexion or hyper- or hypo-extension, abduction, adduction, internal or external rotation deficit, or hyper- or hypo-abduction, hyper- or hypo-adduction, hyper- or hypo-internal or external rotation. Single or multi-axis line or plane measurements can then be utilized to determine preferred angles of correction, e.g., by adjusting surgical cut or saw planes or other surgical interventions. Typically, two axis corrections will be preferred over a single axis correction, a two plane correction will be preferred over a single plane correction and so forth. In accordance with another embodiment of the invention, more than one drilling, cut, boring and/or reaming or other surgical intervention is performed for a particular treatment such as the placement of a joint resurfacing or replacing implant, or components thereof. These two or more surgical interventions (e.g., drilling, cutting, reaming, sawing) are made in relationship to a biomechanical axis, and/or an anatomical axis and/or an implant axis. The 3D guidance template or attachments or linkages thereto include two or more openings, guides, apertures or reference planes to make at least two or more drillings, reamings, borings, sawings or cuts in relationship to a biomechanical axis, an anatomical axis, an implant axis or other axis derived therefrom or related thereto. While in simple embodiments it is possible that only a single cut or drilling will be made in relationship to a biomechanical axis, an anatomical axis, an implant axis and/or an axis related thereto, in most meaningful implementations, two or more drillings, borings, reamings, cutting and/or sawings will be performed or combinations thereof in relationship to a biomechanical, anatomical and/or implant axis. FIG. 2 shows an example of a surgical tool 410 having one surface 400 matching the geometry of an articular surface of the joint. Also shown is an aperture 415 in the tool 410 capable of controlling drill depth and width of the hole and allowing implantation or insertion of implant 420 having a press-fit design. FIG. 3 is a flow chart illustrating the steps involved in designing a template for use in preparing a joint surface. Illustratively, the template is, without limitation, a mold. Optionally, the first step can be to measure the size of the area of the diseased cartilage or cartilage loss 2100 , Once the size of the cartilage loss has been measured, the user can measure the thickness of the adjacent cartilage 2120 , prior to measuring the curvature of the articular surface and/or the subchondral bone 2130 . Alternatively, the user can skip the step of measuring the thickness of the adjacent cartilage 2102 . Once an understanding and determination of the shape of the subchondral bone is determined, either a mold can be selected from a library of molds 3132 or a patient specific mold can be generated 2134 . In either event, the implantation site is then prepared 2140 and implantation is performed 2142 . Any of these steps can be repeated by the optional repeat steps 2101 , 2121 , 2131 , 2133 , 2135 , 2141 . Instead of a mold, it is to be understood that the surgical tool may be made in a variety of ways, including, without limitation, machining and rapid prototyping. Rapid prototyping is a technique for fabricating a three-dimensional object from a computer model of the object. Typically, a special printer is used to fabricate the prototype from a plurality of two-dimensional layers. Computer software sections the representations of the object into a plurality of distinct two-dimensional layers and then a three-dimensional printer fabricates a layer of material for each layer sectioned by the software. Together the various fabricated layers form the desired prototype. More information about rapid prototyping techniques is available in US Patent Publication No 2002/0079601A1 to Russell et al., published Jun. 27, 2002, which is incorporated herein by reference. An advantage to using rapid prototyping is that it enables the use of free form fabrication techniques that use toxic or potent compounds safely. These compounds can be safely incorporated in an excipient envelope, which reduces worker exposure A variety of techniques can be used to derive the shape of the template, as described above. For example, a few selected CT slices through the hip joint, along with a full spiral CT through the knee joint and a few selected slices through the ankle joint can be used to help define the axes if surgery is contemplated of the knee joint. Once the axes are defined, the shape of the subchondral bone can be derived, followed by applying standardized cartilage loss. Methodologies for stabilizing the 3D guidance templates will now be described. The 3D guide template may be stabilized using multiple surgical tools such as, without limitation: K-wires; a drill bit anchored into the bone and left within the template to stabilize it against the bone; one or more convexities or cavities on the surface facing the cartilage; bone stabilization against intra/extra articular surfaces, optionally with extenders, for example, from an articular surface onto an extra-articular surface; and/or stabilization against newly placed cuts or other surgical interventions. Specific anatomic landmarks may be selected in the design and make of the 3D guide template in order to further optimize the anatomic stabilization. For example, a 3D guidance template may be designed to cover portions or all off an osteophyte or bone spur in order to enhance anchoring of the 3D guide template against the underlying articular anatomy. The 3D guidance template may be designed to the shape of a trochlear or intercondylar notch and can encompass multiple anatomic areas such as a trochlea, a medial and a lateral femoral condyle at the same time. In the tibia, a 3D guide template may be designed to encompass a medial and lateral tibial plateau at the same time and it can optionally include the tibial spine for optimized stabilization and cross-referencing. In a hip, the fovea capitis may be utilized in order to stabilize a 3D guide template. Optionally, the surgeon may elect to resect the ligamentum capitis femoris in order to improve the stabilization. Also in the hip, an acetabular mold can be designed to extend into the region of the tri-radiate cartilage, the medial, lateral, superior, inferior, anterior and posterior acetabular wall or ring. By having these extensions and additional features for stabilization, a more reproducible position of the 3D template can be achieved with resulted improvement in accuracy of the surgical procedure. Typically, a template with more than one convexity or concavity or multiple convexities or concavities will provide better cross-referencing in the anatomic surface and higher accuracy and higher stabilization than compared to a mold that has only few surface features such as a singular convexity. Thus, in order to improve the implementation and intraoperative accuracy, careful surgical planning and preoperative planning is desired, that encompasses preferably more than one convexity, more preferred more than two convexities and even more preferred more than three convexities, or that encompasses more than one concavity, more preferred more than two concavities or even more preferred more than three concavities on an articular surface or adjoined surface, including bone and cartilage outside the weight-bearing surface. In an even more preferred embodiment, more than one convexity and concavity, more preferred more than two convexities and concavities and even more preferred more then three convexities and concavities are included in the surface of the mold in order to optimize the interoperative cross-referencing and in order to stabilize the mold prior to any surgical intervention. Turning now to a particular 3D surgical template configuration for a specific joint application (knee joint), which is intended to teach the concept of the design as it would then apply to other joints in the body: When a total knee arthroplasty is contemplated, the patient can undergo an imaging test, that will demonstrate the articular anatomy of a knee joint, e.g. width of the femoral condyles, the tibial plateau etc. Additionally, other joints can be included in the imaging test thereby yielding information on femoral and tibial axes, deformities such as varus and valgus and other articular alignment. The imaging test may be, without limitation, an x-ray image, preferably in standing, load-bearing position, a CT or spiral CT scan or an MRI scan or combinations thereof. A spiral CT scan may be advantageous over a standard CT scan due to its improved spatial resolution in z-direction in addition to x and y resolution. The articular surface and shape as well as alignment information generated with the imaging test can be used to shape the surgical assistance device, to select the surgical assistance device from a library of different devices with pre-made shapes and sizes, or can be entered into the surgical assistance device and can be used to define the preferred location and orientation of saw guides or drill holes or guides for reaming devices or other surgical instruments. Intraoperatively, the surgical assistance device is applied to the tibial plateau and subsequently the femoral condyle(s) by matching its surface with the articular surface or by attaching it to anatomic reference points on the bone or cartilage. The surgeon can then introduce a reamer or saw through the guides and prepare the joint for the implantation. By cutting the cartilage and bone along anatomically defined planes, a more reproducible placement of the implant can be achieved. This can ultimately result in improved postoperative results by optimizing biomechanical stresses applied to the implant and surrounding bone for the patient's anatomy and by minimizing axis malalignment of the implant. In addition, the surgical assistance device can greatly reduce the number of surgical instruments needed for total or unicompartmental knee arthroplasty. Thus, the use of one or more surgical assistance devices can help make joint arthroplasty more accurate, improve postoperative results, improve long-term implant survival, reduce cost by reducing the number of surgical instruments used. Moreover, the use of one or more surgical assistance device can help lower the technical difficulty of the procedure and can help decrease operating room (“OR”) times. Thus, surgical tools described herein can also be designed and used to control drill alignment, depth and width, for example when preparing a site to receive an implant. For example, the tools described herein, which typically conform to the joint surface, can provide for improved drill alignment and more accurate placement of any implant. An anatomically correct tool can be constructed by a number of methods and can be made of any material, preferably a substantially translucent and/or transparent material such as plastic, Lucite, silastic, SLA or the like, and typically is a block-like shape prior to molding. FIG. 4A depicts, in cross-section, an example of a template 600 for use on the tibial surface having an upper surface 620 . The template 600 includes an aperture 625 through which a surgical drill or saw can fit. The aperture guides the drill or saw to make the proper hole or cut in the underlying bone 610 as illustrated in FIGS. 1B-D . In various embodiments, the template may include a guide aperture, a reaming aperture, a drill aperture and a cut plane for guiding a surgical tool. Dotted lines 632 illustrate where the cut corresponding to the aperture will be made in bone. FIG. 4B depicts, a template 608 suitable for use on the femur. As can be appreciated from this perspective, additional apertures are provided to enable additional cuts to the bone surface. The apertures 605 enable cuts 606 to the surface of the femur. The resulting shape of the femur corresponds to the shape of the interior surface of the femoral implant, typically as shown in FIG. 1E . Additional shapes can be achieved, if desired, by changing the size, orientation and placement of the apertures. Such changes would be desired where, for example, the interior shape of the femoral component of the implant requires a different shape of the prepared femur surface. Turning now to FIG. 5 , a variety of illustrations are provided showing a template that includes a tibial cutting block and mold system. FIG. 5A illustrates the tibial cutting block 2300 in conjunction with a tibia 2302 that has not been resected. In this depiction, the cutting block 2300 consists of at least two pieces. The first piece is a patient specific interior piece 2310 or mold that is designed on its inferior surface 2312 to mate, or substantially mate, with the existing geography of the patient's tibia 2302 . The superior surface 2314 and side surfaces 2316 of the first piece 2310 are configured to mate within the interior of an exterior piece 2320 . The reusable exterior piece 2320 fits over the interior piece 2310 . The system can be configured to hold the mold onto the bone. The reusable exterior piece has a superior surface 2322 and an inferior surface 2324 that mates with the first piece 2310 . The reusable exterior piece 2320 includes cutting guides 2328 , to assist the surgeon in performing the tibial surface cut described above. As shown herein a plurality of cutting guides can be provided to provide the surgeon a variety of locations to choose from in making the tibial cut. If necessary, additional spacers can be provided that fit between the first patient configured, or molded, piece 2310 and the second reusable exterior piece, or cutting block, 2320 . Clearly, the mold may be a single component or multiple components. In a preferred embodiment, one or more components are patient specific while other components such as spacers or connectors to surgical instruments are generic. In one embodiment, the mold can rest on portions of the joint on the articular surface or external to the articular surface. Other surgical tools then may connect to the mold. For example, a standard surgical cut block as described for standard implants, for example in the knee the J&J PFC Sigma system, the Zimmer Nexgen system or the Stryker Duracon system, can be connected or placed on the mold. In this manner, the patient specific component can be minimized and can be made compatible with standard surgical instruments. The mold may include receptacles for standard surgical instruments including alignment tools or guides. For example, a tibial mold for use in knee surgery may have an extender or a receptacle or an opening to receive a tibial alignment rod. In this manner, the position of the mold can be checked against the standard alignment tools and methods. Moreover, the combined use of molds and standard alignment tools including also surgical navigation techniques can help improve the accuracy of or optimize component placement in joint arthroplasty, such as hip or knee arthroplasty. For example, the mold can help define the depth of a horizontal tibial cut for placement of a tibial component. A tibial alignment guide, for example an extramedullary or intramedullary alignment guide, used in conjunction with a tibial mold can help find the optimal anteroposterior angulation, posterior slope, tibial slant, or varus-valgus angle of the tibial cut. The mold may be designed to work in conjunction with traditional alignment tools known in the art. The template may include markers, e.g. optoelectronic or radiofrequency, for surgical navigation. The template may have receptacles to which such markers can be attached, either directly or via a linking member. The templates can be used in combination with a surgical navigation system. They can be used to register the bones associated with a joint into the coordinate system of the surgical navigation system. For example, if a mold for a joint surface includes tracking markers for surgical navigation, the exact position and orientation of the bone can be detected by the surgical navigation system after placement of the mold in its unique position. This helps to avoid the time-consuming need to acquire the coordinates of tens to hundreds of points on the joint surface for registration. Referring back to FIG. 5 , the variable nature of the interior piece facilitates obtaining the most accurate cut despite the level of disease of the joint because it positions the exterior piece 2320 such that it can achieve a cut that is perpendicular to the mechanical axis. Either the interior piece 2310 or the exterior piece 2320 can be formed out of any of the materials discussed above in Section II, or any other suitable material. Additionally, a person of skill in the art will appreciate that the invention is not limited to the two piece configuration described herein. The reusable exterior piece 2320 and the patient specific interior piece 2310 can be a single piece that is either patient specific (where manufacturing costs of materials support such a product) or is reusable based on a library of substantially defect conforming shapes developed in response to known or common tibial surface sizes and defects. The interior piece 2310 is typically molded to the tibia including the subchondral bone and/or the cartilage. The surgeon will typically remove any residual meniscal tissue prior to applying the mold. Optionally, the interior surface 2312 of the mold can include shape information of portions or all of the menisci. Turning now to FIG. 5B-D , a variety of views of the removable exterior piece 2320 . The top surface 2322 of the exterior piece can be relatively flat. The lower surface 2324 which abuts the interior piece conforms to the shape of the upper surface of the interior piece. In this illustration the upper surface of the interior piece is flat, therefore the lower surface 2324 of the reusable exterior surface is also flat to provide an optimal mating surface. A guide plate 2326 is provided that extends along the side of at least a portion of the exterior piece 2320 . The guide plate 2326 provides one or more slots or guides 2328 through which a saw blade can be inserted to achieve the cut desired of the tibial surface. Additionally, the slot, or guide, can be configured so that the saw blade cuts at a line perpendicular to the mechanical axis, or so that it cuts at a line that is perpendicular to the mechanical axis, but has a 4-7° slope in the sagittal plane to match the normal slope of the tibia. Optionally, a central bore 2330 can be provided that, for example, enables a drill to ream a hole into the bone for the stem of the tibial component of the knee implant. FIGS. 5E-H illustrate the interior, patient specific, piece 2310 from a variety of perspectives. FIG. 5E shows a side view of the piece showing the uniform superior surface 2314 and the uniform side surfaces 2316 along with the irregular inferior surface 2316 . The inferior surface mates with the irregular surface of the tibia 2302 . FIG. 5F illustrates a superior view of the interior, patient, specific piece of the mold 2310 . Optionally having an aperture 2330 . FIG. 5G illustrates an inferior view of the interior patient specific mold piece 2310 further illustrating the irregular surface which includes convex and concave portions to the surface, as necessary to achieve optimal mating with the surface of the tibia. FIG. 5H illustrates cross-sectional views of the interior patient specific mold piece 2310 . As can be seen in the cross-sections, the surface of the interior surface changes along its length. As is evident from the views shown in FIGS. 5B and D, the length of the guide plate 2326 can be such that it extends along all or part of the tibial plateau, e.g. where the guide plate 2326 is asymmetrically positioned as shown in FIG. 5B or symmetrical as in FIG. 3D . If total knee arthroplasty is contemplated, the length of the guide plate 2326 typically extends along all of the tibial plateau. If unicompartmental arthroplasty is contemplated, the length of the guide plate typically extends along the length of the compartment that the surgeon will operate on. Similarly, if total knee arthroplasty is contemplated, the length of the molded, interior piece 2310 typically extends along all of the tibial plateau; it can include one or both tibial spines. If unicompartmental arthroplasty is contemplated, the length of the molded interior piece typically extends along the length of the compartment that the surgeon will operate on; it can optionally include a tibial spine. Turning now to FIG. 5I , an alternative embodiment is depicted of the aperture 2330 . In this embodiment, the aperture features lateral protrusions to accommodate using a reamer or punch to create an opening in the bone that accepts a stem having flanges. FIGS. 5J and M depict alternative embodiments of the invention designed to control the movement and rotation of the cutting block 2320 relative to the mold 2310 . As shown in FIG. 5J a series of protrusions, illustrated as pegs 2340 , are provided that extend from the superior surface of the mold. As will be appreciated by those of skill in the art, one or more pegs or protrusions can be used without departing from the scope of the invention. For purposes of illustration, two pegs have been shown in FIG. 5J . Depending on the control desired, the pegs 2340 are configured to fit within, for example, a curved slot 2342 that enables rotational adjustment as illustrated in FIG. 3K or within a recess 2344 that conforms in shape to the peg 2340 as shown in FIG. 5L . As will be appreciated by those of skill in the art, the recess 2344 can be sized to snugly encompass the peg or can be sized larger than the peg to allow limited lateral and rotational movement. The recess can be composed of a metal or other hard insert 544 . As illustrated in FIG. 5M the surface of the mold 2310 can be configured such that the upper surface forms a convex dome 2350 that fits within a concave well 2352 provided on the interior surface of the cutting block 2320 . This configuration enables greater rotational movement about the mechanical axis while limiting lateral movement or translation. Other embodiments and configurations could be used to achieve these results without departing from the scope of the invention. As will be appreciated by those of skill in the art, more than two pieces can be used, where appropriate, to comprise the system. For example, the patient specific interior piece 2310 can be two pieces that are configured to form a single piece when placed on the tibia. Additionally, the exterior piece 2320 can be two components. The first component can have, for example, the cutting guide apertures 2328 . After the resection using the cutting guide aperture 2328 is made, the exterior piece 2320 can be removed and a secondary exterior piece 2320 ′ can be used which does not have the guide plate 2326 with the cutting guide apertures 2328 , but has the aperture 2330 which facilitates boring into the tibial surface an aperture to receive a stem of the tibial component of the knee implant. Any of these designs could also feature the surface configurations shown in FIGS. 5J-M , if desired. FIG. 5N illustrates an alternative design of the cutting block 2320 that provides additional structures 2360 to protect, for example, the cruciate ligaments, from being cut during the preparation of the tibial plateau. These additional structures can be in the form of indented guides 2360 , as shown in FIG. 5N or other suitable structures. FIG. 5O illustrates a cross-section of a system having anchoring pegs 2362 on the surface of the interior piece 2310 that anchor the interior piece 2310 into the cartilage or meniscal area. FIGS. 5P AND Q illustrate a device 2300 configured to cover half of a tibial plateau such that it is unicompartmental. FIG. 5R illustrates an interior piece 2310 that has multiple contact surfaces 2312 with the tibial 2302 , in accordance with one embodiment of the invention. As opposed to one large contact surface, the interior piece 2310 includes a plurality of smaller contact surfaces 2312 . In various embodiments, the multiple contact surfaces 2312 are not on the sample plane and are at angles relative to each other to ensure proper positioning on the tibia 2302 . Two or three contact surfaces 2312 may be required to ensure proper positioning. In various embodiments, only the contact surfaces 2312 of the interior piece may be molded, the molds attached to the rest of the template using methodologies known in the art, such as adhesives. The molds may be removably attached to the template. It is to be understood that multiple contact surfaces 2312 may be utilized in template embodiments that include one or a plurality of pieces. Turning now to FIG. 6 , a femoral template/mold system is depicted that facilitates preparing the surface of the femur such that the finally implanted femoral implant will achieve optimal mechanical and anatomical axis alignment. FIG. 6A illustrates the femur 2400 with a first portion 2410 of the mold placed thereon. In this depiction, the top surface of the mold 2412 is provided with a plurality of apertures. In this instance the apertures consist of a pair of rectangular apertures 2414 , a pair of square apertures 2416 , a central bore aperture 2418 and a long rectangular aperture 2420 . The side surface 2422 of the first portion 2410 also has a rectangular aperture 2424 . Each of the apertures is larger than the eventual cuts to be made on the femur so that, in the event the material the first portion of the mold is manufactured from a soft material, such as plastic, it will not be inadvertently cut during the joint surface preparation process. Additionally, the shapes can be adjusted, e.g., rectangular shapes made trapezoidal, to give a greater flexibility to the cut length along one area, without increasing flexibility in another area. As will be appreciated by those of skill in the art, other shapes for the apertures, or orifices, can be changed without departing from the scope of the invention. FIG. 6B illustrates a side view of the first portion 2410 from the perspective of the side surface 2422 illustrating the aperture 2424 . As illustrated, the exterior surface 2411 has a uniform surface which is flat, or relatively flat configuration while the interior surface 2413 has an irregular surface that conforms, or substantially conforms, with the surface of the femur. FIG. 6C illustrates another side view of the first, patient specific molded, portion 2410 , more particularly illustrating the irregular surface 2413 of the interior. FIG. 6D illustrates the first portion 2410 from a top view. The center bore aperture 2418 is optionally provided to facilitate positioning the first piece and to prevent central rotation. FIG. 6D illustrates a top view of the first portion 2410 . The bottom of the illustration corresponds to an anterior location relative to the knee joint. From the top view, each of the apertures is illustrated as described above. As will be appreciated by those of skill in the art, the apertures can be shaped differently without departing from the scope of the invention. Turning now to FIG. 6E , the femur 2400 with a first portion 2410 of the cutting block placed on the femur and a second, exterior, portion 2440 placed over the first portion 2410 is illustrated. The second, exterior, portion 2440 features a series of rectangular grooves ( 2442 - 2450 ) that facilitate inserting a saw blade therethrough to make the cuts necessary to achieve the femur shape illustrated in FIG. 1E . These grooves can enable the blade to access at a 90° angle to the surface of the exterior portion, or, for example, at a 45° angle. Other angles are also possible without departing from the scope of the invention. As shown by the dashed lines, the grooves ( 2442 - 2450 ) of the second portion 2440 , overlay the apertures of the first layer. FIG. 6F illustrates a side view of the second, exterior, cutting block portion 2440 . From the side view a single aperture 2450 is provided to access the femur cut. FIG. 26G is another side view of the second, exterior, portion 2440 showing the location and relative angles of the rectangular grooves. As evidenced from this view, the orientation of the grooves 2442 , 2448 and 2450 is perpendicular to at least one surface of the second, exterior, portion 2440 . The orientation of the grooves 2444 , 2446 is at an angle that is not perpendicular to at least one surface of the second, exterior portion 2440 . These grooves ( 2444 , 2446 ) facilitate making the angled chamfer cuts to the femur. FIG. 6H is a top view of the second, exterior portion 2440 . As will be appreciated by those of skill in the art, the location and orientation of the grooves will change depending upon the design of the femoral implant and the shape required of the femur to communicate with the implant. FIG. 6I illustrates a spacer 2401 for use between the first portion 2410 and the second portion 2440 . The spacer 2401 raises the second portion relative to the first portion, thus raising the area at which the cut through groove 2424 is made relative to the surface of the femur. As will be appreciated by those of skill in the art, more than one spacer can be employed without departing from the scope of the invention. Spacers can also be used for making the tibial cuts. Optional grooves or channels 2403 can be provided to accommodate, for example, pins 2460 shown in FIG. 6J . Similar to the designs discussed above with respect to FIG. 5 , alternative designs can be used to control the movement and rotation of the cutting block 2440 relative to the mold 2410 . As shown in FIG. 6J a series of protrusions, illustrated as pegs 2460 , are provided that extend from the superior surface of the mold. These pegs or protrusions can be telescoping to facilitate the use of molds if necessary. As will be appreciated by those of skill in the art, one or more pegs or protrusions can be used without departing from the scope of the invention. For purposes of illustration, two pegs have been shown in FIG. 6J . Depending on the control desired, the pegs 2460 are configured to fit within, for example, a curved slot that enables rotational adjustment similar to the slots illustrated in FIG. 5K or within a recess that conforms in shape to the peg, similar to that shown in FIG. 5L and described with respect to the tibial cutting system. As will be appreciated by those of skill in the art, the recess 2462 can be sized to snugly encompass the peg or can be sized larger than the peg to allow limited lateral and rotational movement. As illustrated in FIG. 6K the surface of the mold 2410 can be configured such that the upper surface forms a convex dome 2464 that fits within a concave well 2466 provided on the interior surface of the cutting block 2440 . This configuration enables greater rotational movement about the mechanical axis while limiting lateral movement or translation. In installing an implant, first the tibial surface is cut using a tibial block, such as those shown in FIG. 6 . The patient specific mold is placed on the femur. The knee is then placed in extension and spacers 2401 , such as those shown in FIG. 6M , or shims are used, if required, until the joint optimal function is achieved in both extension and flexion. The spacers, or shims, are typically of an incremental size, e.g., 5 mm thick to provide increasing distance as the leg is placed in extension and flexion. A tensiometer can be used to assist in this determination or can be incorporated into the mold or spacers in order to provide optimal results. The design of tensiometers are known in the art and are not included herein to avoid obscuring the invention. Suitable designs include, for example, those described in U.S. Pat. No. 5,630,820 to Todd issued May 20, 1997. As illustrated in FIGS. 6N (sagittal view) and 6 O (coronal view), the interior surface 2413 of the mold 2410 can include small teeth 2465 or extensions that can help stabilize the mold against the cartilage 2466 or subchondral bone 2467 . 3D guidance templates may be used to create more that one cut on the same and/or on the opposite articular surface or opposite articular bone, in accordance with an embodiment of the invention. These cuts may be cross-referenced with other cuts using one or more guidance template(s). In accordance with one embodiment of the invention, the 3D guidance template(s) are utilized to perform more than one cut on the same articular side such as the femoral side of a knee joint. In another embodiment, a 3D guidance template may be utilized to cross reference surgical interventions on an opposing articular surface. In a knee, for example, the first articular surface can be the femoral surface. The opposing articular surface can be the tibial surface or the patella surface. In a hip, the first articular surface can be the acetabulum. The opposing articular surface or the opposing bone can be the proximal femur. Thus, in a knee, a horizontal femur cut can be cross-referenced with an anterior or posterior femur cut or optionally also chamfer, oblique cuts. Similarly, a tibial horizontal cut can be cross-referenced with any tibial oblique or vertical cuts on the same articular side or surface. In accordance with another embodiment, one or more femur cuts can be crossed-referenced with one or more tibial cuts. Or, in a hip, one or more acetabular cuts or surgical interventions can be cross-referenced with one or more femoral cuts or surgical interventions such as drilling, reaming or boring. Similarly, in a knee again, one or more femur cuts can be cross-referenced with one or more patella cuts. Any combination and order is possible. The cross-referencing can occur via attachments or linkages including spacers or hinge or ratchet like devices from a first articular bone and/or cartilage surface, to a second articular, bone and/or cartilage surface. The resulting positioning of the cut on the opposing articular, bone or cartilage surface can be optimized by testing the cut for multiple pose angles or joint positions such as flexion, extension, internal or external rotation, abduction or adduction. Thus, for example, in a knee a distal femur cut can be performed with a mold. Via a linkage or an attachment, a tibial template may be attached thereto or to the cut or other surgical intervention, thus a cross-reference can be related from the femoral cut to a tibial cut or other surgical intervention. Cross-referencing from a first articular surface to a second articular surface via, without limitation, attachments or linkages to a template has the advantage of insuring an optimal alignment between the implant or other therapeutic device components of the first articular surface to that on a second articular surface. Moreover, by cross-referencing surgical interventions on a first articular surface to a second articular surface, improved efficiencies and time savings can be obtained with the resulted surgical procedure. Cross-referencing the first, the second and, optionally a third or more articular surface, such as in a knee joint, may be performed with a single linkage or attachment or multiple linkages or attachments. A single pose angle or position of a joint or multiple pose angles or positions of a joint may be tested and optimized during the entire surgical intervention. Moreover, any resulting surgical interventions on the opposite, second articular surface, bone or cartilage may be further optimized by optionally cross-referencing to additional measurement tools such as standard alignment guides. For example, in a knee joint, a 3D template may be utilized to perform one or more surgical interventions on the femoral side, such as a femoral cut. This can then be utilized via a linkage, an attachment or via indirect cross-referencing directly onto the site of surgical intervention, to guide a surgical intervention such as a cut of the tibial side. Prior to performing the surgical intervention on the tibial side, a traditional tibial alignment guide with cross-reference to the medial and lateral malleolus of the ankle turn may be used to optimize the position, orientation and/or depth and extent of the planned surgical intervention such as the cut. For example, cross-referencing to the femoral cut can aid in defining the relative superior inferior height of the tibial cut, while cross-referencing a tibial alignment guide can optionally be utilized to determine the slant of the cut in the interior posterior direction. An exemplary system and methodology is now described in which a femoral template is used to make a cut on the femur, which is then cross-referenced to properly align a tibial template for making a cut on the tibial plateau. Initially, an electronic image(s) of the leg is obtained using imaging techniques elaborated in above-described embodiments. For example, a pre-operative CT scan of a patient's leg may be obtained to obtain electronic image data. Image processing is then applied to the image data to derive, without limitation, relevant joint surfaces, axis, and/or cut planes. Image processing techniques may include, without limitation, segmentation and propagation of point clouds. Relevant biomechanical and/or anatomical axis data may be obtained by identifying, for example, the central femoral head, central knee joint and center of the distal tibia. The cutting planes may then be defined based on at least one of these axis. For example, the tibial implant bearing surface may be defined as being perpendicular to the axis defined by the center of the tibial plateau 2496 and the center of the distal tibia 2497 , as illustrated in FIG. 6P ; the tibial implant's medial margin may project towards the femoral head, as illustrated in FIG. 6Q ; and the anterior to posterior slope of the tibia may be approximated by the natural anatomical slope (alternatively, excessive tibial slope may be corrected). The tibial and femoral templates and implants may be designed based, at least in part, on the derived joint surfaces, axis and/or cut planes. FIGS. 6R and 6S show isometric views of a femoral template 2470 and a tibial template 2480 , respectively, in accordance with an embodiment of the invention. The femoral template 2470 has an interior surface that, in various embodiments, conforms, or substantially conforms, with the anatomic surface (bone and/or cartilage) of the femur 2475 . Furthermore, the interior surface of the femoral template may extend a desired amount around the anatomical boney surfaces of the condyle to further ensure proper fixation. The interior surface of the tibial cutting block 2480 may conform, or substantially conform to the surface (bone and/or cartilage) of the tibia 2481 . In an exemplary use, the femoral template 2470 is placed on the femoral condyle 2475 , for example, when the knee is flexed. The femoral template 2470 may be fixed to the femoral condyle 2475 using, without limitation, anchoring screws/drill pins inserted through drill bushing holes 2471 and 2472 . The position of holes 2471 and 2472 on the condyle may be the same used to anchor the final implant to the femur. In various embodiments, the holes 2471 and 2472 may include metal inserts/bushings to prevent degradation when drilling. Fixing the template 2470 to the femoral condyle 2475 advantageously prevents movement of the template during subsequent cutting or other surgical interventions thereby ensuring the accuracy of the resultant surgical cuts. To assist in accurately positioning the femoral template 2470 , a femoral guide reference tool 2473 may be attached to the femoral template 2470 , as shown in FIG. 6T . The femoral guide reference tool 2473 may, without limitation, attach to one of holes 2471 and 2472 . The femoral guide reference tool 2473 may reference off the tangential margin of the posterior condyle, and aid, for example, in correct anterior-posterior positioning of the femoral template 2470 . Upon proper fixation of the femoral template 2470 to the femoral condyle 2475 , a cut to the femoral condyle is made using cut guide surface or element 2474 . The cut guide surface or element 2474 may be integral to the femoral template 2470 , or may be an attachment to the femoral template 2470 , with the attachment made of a harder material than the femoral template 2470 . For example, the cut guide surface or element 2474 may be a metal tab that slides onto the femoral template 2470 , which may be made, without limitation, of a softer, plastic material. Upon making the femoral cut and removing the femoral template 2475 , a sample implant template 2476 (not the final implant) is optionally positioned on the condyle, as shown in FIG. 6U , in accordance with an embodiment of the invention. The sample implant template 2474 may be attached to the condyle by using without limitation, anchoring screws/drill pins inserted through the same holes used to anchor the final implant to the femur. The sample implant template 2476 includes an attachment mechanism 2494 for attaching the tibial template 2480 , thereby cross-referencing the placement of the distal tibial cut with respect to the femoral cut/implant's placement. The attachment mechanism 2494 may be, without limitation, a boss, as shown in FIG. 6U , or other attachment mechanism known in the art, such as a snap-fit mechanism. Note that in alternative embodiments, a sample implant template 2476 is not required. For example, the tibial template 2480 may attach directly to the femoral template 2470 . However, in the subject embodiment, the drill bushing features of the femoral template 2475 will interfere with the knee going into extension, preventing the tibial cut. In illustrative embodiments, the thickness of the sample implant template 2476 may not only include the thickness of the final femoral implant, but may include an additional thickness that corresponds to a preferred joint space between tibial and femoral implants. For example, the additional thickness may advantageously provide a desired joint space identified for proper ligament balancing or for flexion, extension, rotation, abduction, adduction, anteversion, retroversion and other joint or bone positions and motion. FIG. 6V is an isometric view of the interior surface of the sample implant template 2476 , in accordance with an embodiment of the invention. In various embodiments, the femoral implant often rests on subchondral bone, with the cartilage being excised. In embodiments where the sample implant template 2474 extends beyond the dimensions of the femoral implant such that portions of the sample implant template 2476 rests on cartilage, an offset 2477 in the interior surface of the sample implant template 2476 may be provided. FIG. 6W is an isometric view of the tibial template 2480 attached to the sample implant 2476 when the knee is in extension, in accordance with an embodiment of the invention. A crosspin 2478 inserted through boss 2494 fixes the tibial template 2480 to the sample implant template 2474 . Of course, other attachment mechanisms may be used, as described above. In preferred embodiments, the tibial template 2480 may also be fixed to the tibia 2481 using, without limitation, anchoring screws/drill pins inserted through drill bushing hole 2479 . In various embodiments, the holes 2479 include metal inserts (or other hard material) to prevent degradation when drilling. As with the femoral template 2475 , the cut guide surface or element of the tibial template 2480 may be integral to the tibial template 2475 , or may be an attachment to the tibial template 2480 , the attachment made of a harder material than the tibial template 2480 . Upon fixing the position of the tibial template 2480 , the cut guide of the tibial template 2475 assists in guiding the desired cut on the tibia. FIG. 6X shows a tibial template 2490 that may be used, after the tibial cut has been made, to further guide surgical tools in forming anchoring apertures in the tibia for utilization by the tibial implant (e.g., the tibial implant may include pegs and/or keels that are used to anchor the tibial implant into the tibia), in accordance with an embodiment of the invention. The outer perimeter of a portion of the tibial template 2490 may mimic the perimeter of the tibial implant. Guide apertures in the tibial template 2490 correspond to the tibial implants fixation features. A portion of the tibial template 2490 conforms to, without limitation, the anterior surface of the tibia to facilitate positioning and anchoring of the template 2490 . FIG. 6Y shows a tibial implant 2425 and femoral implant 2426 inserted onto the tibia and femur, respectively, after the above-described cuts have been made, in accordance with an embodiment of the invention. Thus, the tibial template 2480 used on the tibia can be cross-referenced to the femoral template 2476 , femoral cut and/or sample implant 2474 . Similarly, in the hip, femoral templates can be placed in reference to an acetabular mold or vice versa. In general, when two or more articular surfaces will be repaired or replaced, a template can be placed on one or more of them and surgical procedures including cutting, drilling, sawing or rasping can be performed on the other surface or other surfaces in reference to said first surface(s). An alternative embodiment of a knee implant, system and method is presented herein below. In this embodiment, a library of patient-specific femoral spacing templates are utilized to provide accurate and anatomically-correct ligament balancing, and patient-specific templates, including an alignment tool for placing the vertical cut for the medial edge of the tibial component on tibial plateau, provide precise positioning of the femoral and tibial implants. In a procedure for installing an implant, the joint surfaces are first prepared to receive the templates and the implants. A line may desirably drawn on the femoral end, using, e.g., a marker or electrosurgical pencil, to mark the anterior sulcus. Thereafter, soft tissue cartilage is desirably removed from the anterior sulcus, e.g., using a curved elevator/osteotome, and posterior cartilage is removed also, e.g., using a, e.g., 10 mm blade. Anterior cartilage removal is desirably started in this procedure a small distance, e.g., 1 or 2 mm, below the sulcus line. Cartilage removal may be completed using, e.g., a 5 mm ringed/open curette. Next, the knee is placed into extension and patient-specific femoral balancing templates are used to properly balance the ligaments in the knee, and in so doing determine the correct locations for the femoral and tibial components. The design (e.g., surface contours, outer geometry) of the femoral balancing templates is desirably derived from patient-specific data, e.g., a CT image of the joint in question. Desirably a plurality of femoral balancing templates, each with a characteristically larger thickness, is provided to enable convenient but accurate ligament balancing. A greater number of femoral balancing templates (i.e., smaller incremental thickness from one template to the next) provides more control over ligament balancing, but fewer femoral balancing templates may be sufficient and also will have the advantage of a less-complex tool set for the surgeon to deal with. A representation of a femoral balancing template 5101 on a femur, featuring split lug 5102 , and through-holes 5103 and 5104 , is depicted in FIG. 7 . The design of the femoral balancing template may desirably mimic that of the permanent femoral implant. The surgeon determines the appropriate femoral balancing template to achieve the desired ligament tensioning in extension, from the choices at hand, and the template is placed on the condylar surface for which it is intended, while the knee is in flexion. Once the femoral balancing template is securely placed in its intended location on the condylar surface (which may include bone and/or cartilage), the knee is placed into extension. Some cartilage may be removed from the tibia if the fit in extension is too tight. FIG. 8 shows a view of a knee in balanced extension with femoral balancing template 5101 fitted on femoral condyle 5201 and between femoral condyle 5201 and tibial plateau 5202 . Once the knee has been balanced in extension, a tibial cutting guide 5301 , having an interface surface 5302 which conforms to an anterior surface of the tibia 5303 , is fitted to the tibia, as shown in FIG. 9 . Interface surface 5302 is desirably derived from patient-specific data. Locking arm 5304 is designed to fit tab 5305 into the slot of split lug 5102 . Horizontal cutting guide 5306 and stop 5310 are provided to enable the horizontal cut for the tibial implant, and pin holes 5307 and 5308 are provided so guide 5301 may be secured to the anterior tibial face. Tab 5305 is fitted into the slot of split lug 5102 , and secured to femoral balancing template 5101 with cross-pin 5309 . A tibial alignment guide (not shown) may be desirably attached to the tibial cutting guide at this point in time to confirm slope (tibial axial alignment). Such a tibial alignment guide comprises an ankle clamping means at one end of the alignment guide, distal to the knee; a rod attached to and spanning from the ankle clamping means to the tibial cutting guide; and attachment means to attach the rod to the tibial cutting guide. Once proper alignment of tibial cutting guide 5301 is confirmed, drill holes are made through pin holes 5307 and 5308 , and the guide is pinned in place by inserting pins 5401 and 5402 into the drill holes, as seen in FIGS. 10 and 11 . Next, the horizontal tibial cut for the tibial implant is made. Cross-pin 5309 is removed, the knee is brought into flexion, and femoral balancing template 5101 is removed, as depicted in FIG. 12 . The coronal tibial cut is made by guiding oscillating saw blade 5701 ( FIG. 13 ) against horizontal cutting guide 5306 ; stop 5310 keeps the horizontal cut from proceeding past the desired end. Once the horizontal cut is made, the tibial cutting guide is removed. FIGS. 14 and 15 illustrate the use of a patient-specific cut alignment tool 5801 (also referred to herein as a navigation chip) to precisely place, without limitation, at least one of a vertical tibial cut or a horizontal tibial cut. Tool 5801 may have a straight medial edge 5802 that may correspond to the line where the vertical cut for the tibial implant is to be placed, and patient-specific surface 5803 that is a mirror image of the tibial surface (which may include bone and/or cartilage) to which it is to mate. The patient-specific surface 5803 may be substantially a mirror image of the articular of the articular cartilage, including normal or diseased cartilage, the subchondral bone, or, optionally, exposed endosteal bone or bone marrow, or combinations thereof. In other words, when surface 5803 is fitted to the tibial plateau, the desired location for the vertical cut, and, by extension, the external edge of the tibial implant, is precisely determined. For example, in a medial unicompartmental implant, the external edge can include the medial aspect of the tibial cortical bone. In a lateral unicompartmental implant, the external edge can include the lateral aspect of the tibial cortical bone. In various embodiments, the patient-specific cut alignment tool 5801 may conform to a weight bearing surface, a non-weight bearing surface, and/or an anatomical landmark. In further embodiments, the patient patient-specific cut alignment tool 5801 may have a periphery or an outer edge that matches the rim or outer periphery of the surface it contacts (e.g., the outer periphery of the tibial plateau), allowing, for example, further visual confirmation of proper alignment. In still further embodiments, the tibial cut alignment tools disclosed herein have the benefit of ensuring that the outer edge of the tibial implant to does not overhang or underhang the cut edge of the tibial plateau. In still further embodiments the patient specific alignment tools can rest on the articular surface, but can also extend to or include cortical bone and can even rest against soft-tissue including ligamentous structures. In various embodiments, the top surface of the alignment tool 5801 may be flat, convex, or concave or combinations thereof. The top surface may be, at least in part, patient matched to the tibia or the femur. For example, the top surface may be, at least in part, a copy or near copy of the tibial surface. Alternatively, the top surface of the alignment tool may be, at least in part, a mirror image of one or more femoral condyles. In all of these embodiments, the top surface of the tibial alignment tool 5801 may be derived from the articular cartilage, including normal or diseased cartilage, the subchondral bone, or, optionally, exposed endosteal bone or bone marrow, or combinations thereof. In another embodiment, the top surface of the alignment tool 5801 may be a mirror image of, at least in part, a femoral implant bearing surface. The femoral implant bearing surface can be a standard (off-the-shelf) bearing surface or can be patient individualized, e.g. to the patient's bone or cartilage or combinations thereof. The top surface of the alignment tool 5801 may be a mirror image to, at least in part, a femoral implant bearing surface in at least one of a coronal plane, a sagittal plane, or combinations thereof, Before the alignment tool 5801 is placed on the plateau of FIGS. 14 and 15 , cartilage may be optionally removed from the plateau, e.g., the anterior two thirds of the tibia. The alignment tool 5801 is placed on the plateau, and a vertical cut is made as illustrated in FIG. 15 . Alternatively, the tool 5801 may be kept in place, a line made along edge 5802 with an electrosurgical pencil, and the cut may be made along the pencil line with the tool 5801 removed. The profile of the tibial cut may be confirmed using a spacer block as described below. In still other embodiments, the patient-specific cut alignment tool 5801 may be used to simply visually confirm the location of a cut, with another cut guide used to actually direct the surgical instrument in making the cut. FIG. 29 shows a tibial cut guide pinned in extension, in accordance with one embodiment of the invention. FIG. 30 shows the femoral balancing template removed, the patient specific alignment tool 5801 positioned on the tibial plateau, and a cutting guide attached to the tibia. The cutting guide may be used to make both the horizontal and vertical cuts on the tibial plateau, in accordance with one embodiment of the invention. In FIG. 29 , the cutting guide is secured to the tibia using, in part, an optional pin hole or a linkage or joint that is shaped so as to allow limited or direct movement of the cutting guide when the femoral balancing template is removed. The patient-specific cut alignment tool 5801 is used to confirm the location of the cut, and the position of the cutting guide is adjusted to align with the confirmed location. Once in the proper position, the cutting guide can be fixed in position via another pin/pin hole, as shown in FIG. 29 , and the cut can be made. In yet other embodiments, the patient-specific cut alignment tool 5801 may be used to properly balance the ligaments in the knee, with or without, for example, the use of the femoral balancing template(s). A plurality of patient-specific cut alignment tools 5801 may be provided, each with a characteristically larger thickness. The top surface of the patient-specific cut alignment tools 5801 may be flat to allow for easier balancing. It may also have a slight curvature to it, which may be convex or concave. Various chips may be inserted, with a chip selected that provides the desired ligament tensioning. For example, each chip may be inserted in turn from, without limitation, thinnest to thickest with the knee in flexion or extension and then taken through the desired range of motion. The anatomic shape of the balancer allows for simplified balancing without the typical complexity of most balancing procedures. Thus, the patient-specific alignment tool 5801 may fulfill multiple functions: It may be used for guiding a vertical tibial cut, if a partial tibial replacement is contemplated. It may be used for referencing a horizontal tibial cut, when a partial or total knee system is contemplated. In this case, it may be combined it with spacer blocks or femoral balancing tools. It may be used for ligament balancing. Moreover, the patient specific alignment tool 5801 may be made available in various thicknesses, e.g. 1, 2, 3 or 4 mm for testing ligament tension in at least one of flexion or extension or combinations thereof for achieving optimal ligament balancing or soft-tissue or ligament tensioning. The thickness of the balancing chip that is inserted will determine the level at which the horizontal tibial cut is made. For example, with a thicker balancing or navigation chip, the tibial cut will be more superior, i.e. more tibial bone is preserved. With a thinner navigation chip, the tibial cut will be more inferior, i.e. more tibial bone is resected. In various embodiments, the tibial cut guide may connect to, a selected patient-specific cut alignment tool 5801 , which may be applied to one or both articular sides, instead of, or in addition to, the femoral balancing template 5101 . For example, a tibial cut guide may include, without limitation, a dovetail feature or other linkage or joint that slides into the patient-specific cut alignment tool 5801 . Other interface/connector means known in the art may be used, such as, without limitation, a snap-fit, joints, and/or cross-pins. Any linkage known in the art may be utilized. Some of these joints or linkages may allow for movement or adjustment in one or more directions. The connection between the patient-specific cut alignment tool 5801 and a tibial cut guide may be made at a set distance from, for example, the top of each of the patient-specific cut alignment tools 5801 . Subsequently, the thicker the patient-specific cut alignment tool 5801 , the less bone is resected off the tibia. The tibial cutting guide may be used to make either or both the horizontal and vertical cuts on the tibial plateau. Thus, the patient specific alignment tool is used to not only determine the location and orientation of the vertical cut, but also the location and height of the horizontal cut. The thickness of the selected patient-specific cut alignment tool 5801 , combined with the set position of the connected tibial cut guide relative to the patient-specific cut alignment tool 5801 , correctly positions the horizontal cut on the tibia with regard to ligament balancing or ligament tension or soft-tissue tension, taking into account the thickness of the femoral and/or tibial implants to be inserted. In illustrative embodiments, the interface between the patient-specific cut alignment tool 5801 and the tibial cut guide may impart a desired slope on the cut guide. For example, the top surface of the patient-specific cut alignment tool 5801 to which the tibial cut guide may dovetail into, may be sloped (with the slope determined via patient specific information), such that, without limitation, the tibial surface is resected perpendicular to the long axis of the tibia in the coronal plane, but sloped posteriorly in the sagittal plane to match the normal slope of the tibia. The slope may be imposed by the patient specific cut alignment tool 5801 , with the slope transferred into the cut guide via a linkage. The slope may also be set in the tibial cut guide based on patient specific information included in and/or derived from the patient specific cut alignment tool 5801 . For example, the slope of the tibial cut guide may be adjustable based on the configuration or other information associated with the patient specific cut alignment tool 5801 . The patient specific information can be derived from a preoperative scan or an intraoperative measurement. It will typically be the slope that the patient's tibia showed on the preoperative scan. The scan may be of the same joint or a contra lateral healthy joint. An offset or a threshold may be applied. For example, if the anteroposterior slope in a patient exceeds 7 mm, the maximum allowable value of slope determined by the patient specific alignment tool may be set at 7 mm, i.e. the selected maximum. The maximum can optionally be derived as a function of the measured slope in that patient. If a patient has a preoperative tibial slope of less than 7 degrees, e.g. 4 degrees, the tibial slope in the patient specific alignment tool may be set at a number corresponding to the measured slope, i.e. in this example 4 degrees. Thus, the patient specific alignment tool may not only yield a reference for the orientation of the vertical cut and optionally horizontal cuts of a tibia, but also on the anteroposterior slope desirable in a patient. If a patient has a preoperative tibial slope of greater than 7 degrees, 7 degrees may be set as the maximum and the horizontal tibial cut may be made at a slope of 7 degrees. Other thresholds may be used, e.g. 6 degrees, 8 degrees, etc. All of the embodiments pertaining to the balancing chip and all other embodiments may be applied to partial knee systems, e.g. medial or lateral unicompartmental tibiofemoral implants, as well as to total knee arthroplasty systems. The embodiments may be used in the context of a femur first technique, i.e. the femur is prepared prior to preparing the tibia, or a tibia first technique, i.e. the tibia is prepared prior to preparing the femur, or combinations thereof. For example, the alignment tool 5801 may be used initially to balance the joint and to place a horizontal tibial cut, while then moving to the femoral preparation, and finishing the tibia at the end. All of the embodiments pertaining to the balancing chip and all other embodiments may be applied to a knee joint, but also any other joint in the body. The terms “femur” or “femoral” and “tibia” and “tibial” are strictly illustrative and can also represent other bone or joint geometries. For example, the embodiments and the navigation chip can be applied in a hip (in which case the terms “tibia” and “tibial” can be replaced with “acetabulum” and “acetabular”, and “femur” and “femoral” can be replaced with “femoral head” and “femoral”). The embodiments may be applied in a shoulder (in which case the terms “tibia” and “tibial” can be replaced with “glenoid” and “glenoid”, and “femur” and “femoral” can be replaced with “humeral head” and “humeral”). The same analogies apply to other joints including the elbow, wrist, ankle, foot and hand. All of the embodiments pertaining to the balancing chip and all other embodiments may be applied to hemiarthroplasty. All of the embodiments pertaining to the balancing chip and all other embodiments may be used in combination with surgical navigation or robotic surgery. For example, radiofrequency and optical markers may be used for planning femoral and tibial bone cuts, while a balancing chip as described above may be used for ligament balancing or soft-tissue or ligament tensioning. The markers may optionally be connected, directly or via a linkage, to the balancing chip. Moreover, in another example, a robot may be used for planning or directing tibial or femoral bone cuts, while a balancing chip as described above may be used for ligament balancing or soft-tissue or ligament tensioning. The robot may optionally be connected, directly or via a linkage, to the balancing chip or to any other patient specific alignment tool. FIGS. 16-23 illustrate the procedure and tools for installing the femoral implant of this embodiment. FIG. 16 illustrates femoral guide 6001 and removable L guide 6002 which has a short pin which fits into lower pin hole 6004 , and around which L guide 6002 may rotate for alignment purposes. The knee is placed into flexion. Guides 6001 and 6002 are assembled, and patient-specific surface 6005 is mated to the femoral surface. Spacer block 6010 , which has a patient-specific outer edge, i.e., the horizontal geometry replicates the area of the cut tibial plateau, is placed onto the cut tibial surface 6002 . Spacer block 6010 may be provided in a number of thicknesses to ensure proper spacing with the knee in flexion. L guide 6002 is adjusted to sit flat on spacer block with knee in flexion ( FIG. 18 ), adjusting the flexion angle if necessary to facilitate this. A drill hole in the femur is made through pin hole 6003 ( FIG. 19 ), and a pin 6401 is inserted to fix guide 6001 to the femur ( FIG. 20 ). L guide 6002 is removed, and a drill hole in the femur is made through pin hole 6004 ( FIG. 21 ), and a pin 6601 is inserted in pin hole 6004 of guide 6001 ( FIG. 22 ). With the femoral guide 6001 thus pinned to the femur, a posterior femoral cut in preparation for receiving a femoral implant is made; oscillating saw blade 6701 is moved against horizontal cutting guide 6702 to remove bone in the posterior portion of the condyle ( FIG. 22 .) The femoral guide 6001 is removed, and a trough for the anterior margin of the femoral implant is made. FIGS. 24-27 illustrate a procedure and tools for installing the tibial implant of this embodiment, wherein patient-specific template 6901 , having drill holes 6902 and 6903 is placed in the cut tibial area, holes are drilled, and pins 7302 and 7301 are inserted to fix the template in place. In FIG. 28 , a fin is created using an osteotome (e.g., about 5 mm in width), using guide slot 7303 . Template 6901 can then be removed to widen and finish the fin hole preparation. The implants may now be installed. In illustrative embodiments, three-dimensional guidance templates may be utilized to determine an optimized implant rotation. Examples are provided below with reference to the knee, however it is to be understood that optimizing implant rotation may be applied to other joints as well. Femoral Rotation: The optimal rotation of a femoral component or femoral implant for a uni-compartmental, patello femoral replacement or total knee replacement may be ascertained in a number of different ways. Implant rotation is typically defined using various anatomic axes or planes. These anatomic axes may include, without limitation, the transepicondylar axis; the Whiteside line, i.e. the trochlea anteroposterior axis, which is typically perpendicular to at least one of the cuts; and/or the posterior condylar axis. Other axes include but are not limited to Blumensaat's line, femoral shaft axis, femoral neck axis, acetabular angle, lines tangent to the superior and inferior acetabular margin, lines tangent to the anterior or posterior acetabular margin, femoral shaft axis, tibial shaft axis, transmalleolar axis, posterior condylar line, tangent(s) to the trochlea of the knee joint, tangents to the medial or lateral patellar facet, lines tangent or perpendicular to the medial and lateral posterior condyles, lines tangent or perpendicular to central weight-bearing zone of the medial and lateral femoral condyles, lines transsecting the medial and lateral posterior condyles, for example through their respective centerpoints, lines tangent or perpendicular to the tibial tuberosity, lines vertical or at an angle to any of said lines, lines tangent to or intersecting the cortical bone of any bone adjacent to or enclosed in a joint. Another approach for optimizing femoral component rotation is a so-called balancing gap technique. With the balancing gap technique, a femoral cut is made parallel to the tibia, i.e. the tibia is cut first typically. Prior to performing the femoral cut, the femoral cut plate is optimized so that the medial and lateral ligament and soft tissue tension are approximately equal. By measuring the relevant anatomic axis or planes, the optimal implant rotation may be determined. The measurement may be factored into the shape, position or orientation of the 3D guidance template, in accordance with an embodiment of the invention. Any resultant surgical interventions including cuts, drilling, or sawings are then made incorporating this measurement, thereby achieving an optimal femoral component rotation. Moreover in order to achieve an optimal balancing, the rotation of the template may be changed so that the cuts are parallel to the tibial cut with substantially equal tension medially and laterally applied. Tibial Rotation: A 3D guidance template may also be utilized to optimize tibial component rotation for uni-compartmental or total knee replacements, in accordance with an embodiment of the invention. Tibial component rotation may be measured using a number of different approaches known in the art. In one example of a tibial component rotation measurement, the anteroposterior axis of the tibia is determined. For a total knee replacement, the tibial component can be placed so that the axis of the implant coincides with the medial one-third of the tibial tuberosity. This approach can work well when the tibia is symmetrical. In another embodiment, the symmetrical tibial component is placed as far as possible posterolateral and externally rotated so that the posteromedial corner of the tibial plateau is uncovered to an extent of between three (3) and five (5) millimeters. The above examples are only representative of the different approaches that have been developed in the literature. Clearly, other various anatomic, biomechanical axis, plane and area measurements may be performed in order to optimize implant rotation. In illustrative embodiments, these measurements may be factored into the design of a 3D guidance template and the position, shape or orientation of the 3D guidance template may be optimized utilizing this information. Thus, any subsequent surgical intervention such as cutting, sawing and/or drilling will result in an optimized implant rotation, for example, in the horizontal or in a near horizontal plane. Example 1 below is included to more fully illustrate the present invention. Additionally, this example provides a single embodiment of the invention and is not meant to limit the scope thereof. Example 1 Unicompartmental Knee Resurfacing Using Patient-Specific Implants and Instrumentation An exemplary surgical technique for use in implanting a novel partial knee resurfacing UKA using customized, single-use instrumentation is described below, in accordance with one embodiment of the invention. CT scans of a patient's knee and partial scans of the hip and ankle are utilized to create patient-specific implants and instrumentation. Based on the CT images, the knee anatomy is digitally recreated, the surface topography of the femur and tibia are mapped, and axis deformity is corrected. The same data is used to create cutting and placement guides that are pre-sized and pre-navigated to work with the patient's anatomy and custom implants. A kit may be provided with the resurfacing implants and disposable instrumentation in a single sterile tray, as shown in FIG. 31 , in accordance with one embodiment of the invention. The various instruments in the kit may be patient-specific instruments or non-patient specific instruments, for example, standardized tools, templates and other devices that may be used during the course of the surgery and in conjunction with other patient-specific instruments and other devices. The surgical technique may illustratively include the following steps, described in more detail below: patient positioning and preparation; balancing of the knee; axial & sagittal tibial cuts; femoral preparation; balancing verification & tibial preparation; and trialing & cementing of implant. Patient Positioning and Preparation The patient is positioned supine on the table with the leg resting on a foot support around 90 degrees flexion. After a standard short midline skin incision, a medial or lateral parapatellar arthrotomy is performed. The medial (or lateral) sleeve is not released, but typically all femoral and tibial osteophytes, including those in the intercondylar notch are removed. In extension the sulcus terminalis is marked with a marking pen, where the anterior tibial lip hits the femoral condyle. The femoral cutting block, which is shaped to substantially fit the condyle and represents the size and geometry of the femoral implant is placed on the femoral condyle. Typically, the anterior edge of the femoral cutting block seats about 2-3 mm inferior to the Sulcus terminalis. The round anterior silhouette of the femoral cutting block is marked on the femoral condyle. The implant is typically designed to the surface of the subchondral bone with a thickness of 3.5 mm. Since it resurfaces the bone plate, substantially all cartilage posterior to the sulcus terminalis, including the posterior condyle, is removed. This may be facilitated, for example, using a 10 millimeter blade, curved elevator, osteotome or a ring-currette, as shown in FIGS. 32 and 33 , in accordance with one embodiment of the invention. That the femoral jig conforms to the condyle after cartilage removal is then confirmed. Once removal of all residual cartilage on the femur has been concluded, residual cartilage is scraped off the tibial plateau and balancing of the knee is started. Balancing of the Knee Four navigation “chips” of varying thicknesses in 1 mm increasing increments are included in the instrument tray. Each chip has an underside that substantially matches the shape and topography of the patient's tibial surface. When inserted into the compartment, the chip will self-seat into a stable position due to its conformity with the anatomic landmarks on the tibia. The top surface of this chip is flat to allow referencing off the distal femor condylar surface during balancing. FIG. 34 shows an exemplary navigation chip, in accordance with one embodiment of the invention. Each chip may be inserted in turn, from thinnest to thickest, with the knee in flexion and then taken through the desired range of motion. A chip is then selected that provides the desired ligament tensioning. FIG. 35 shows a navigation chip in-situ, in accordance with one embodiment of the invention. Illustratively, an opening under valgus stress of about 1 mm is recommended medially in extension and 90 degrees flexion and about 1-3 mm under varus stress laterally in extension and about 3-5 mm in 90 degrees flexion. The thicker the chip, the less bone is resected off the tibia. Axial & Sagittal Tibial Cuts The selected navigation chip connects to a tibial cutting block (also referred herein as the tibial jig). The tibial jig may also optionally connect to an extramedullary alignment guide. The alignment guide may be placed on the leg and the tibial jig is attached to the navigation chip to establish its placement. The tibial jig may then be pinned flush to the anterior tibia. FIG. 36 shows the tibial jig placed in the knee, in accordance with one embodiment of the invention. The tibial cut planes are confirmed with the navigation chip, as shown in FIG. 37 , in accordance with one embodiment of the invention: the sagittal cut, the axial cut—90 degrees relative to the tibial mechanical axis—, and the posterior slope. The tibial cutting block may be repositioned if necessary, whereupon the tibial cutting block is pinned in place. The sagittal tibial cut is performed using the tibial cutting block. The reciprocating saw blade may be left in as shown in FIG. 34 to protect the ACL while performing the axial cut. The axial tibial cut is performed referencing off the tibial jig. FIG. 38 shows the tibial axial cut, in accordance with one embodiment of the invention. The Alignment Guide and the Tibial Jig may then be removed. Femoral Preparation The femoral jig is placed on the distal femur and its position is verified. The femoral jig is designed to conform to the femur in only one location so as to aid in proper positioning. FIG. 39 shows the femoral jig placed on the distal femur, in accordance with one embodiment of the invention. Any additional cartilage or osteophytes that were missed previously are removed until the fit is snug and secure. Illustratively, the peg-holes may be drilled in 15 degrees flexion relative to the sagittal anatomical femoral axis and the amount to be removed off the posterior condyle may be 3-5 mm. The femoral jig is then drilled and pinned in place and the posterior femoral cut is performed, as shown in FIG. 40 in accordance with one embodiment of the invention. In various embodiments, this is the only bone resection required on the femur. To complete femoral preparation, an anterior recess may be prepared using a curved osteotome or a 5 mm burr. Illustratively, the most anterior edge of the component submerges 3.5 mm below the subchondral bone plate. The taper starts 10 mm inferior to it. Also the transition from the subchondral bone to the anterior edge of the posterior cut may be rounded, using either a file, burr or osteotome. Smoothening of the edge and placement and depth of recess may then be verified with a femoral trial implant. Balancing Verification & Tibial Preparation With the femoral trial implant in place, a spacer block is inserted, such as an 8 mm spacer block, and balance in flexion and extension is evaluated. FIG. 41 shows flexion and extension balance verification, in accordance with one embodiment of the invention. If the knee is too tight, an additional 1 to 2 millimeters may be resected from the tibia. If too loose, the 10 millimeter spacer block may be inserted, with balance in flexion and extension reevaluated. The Tibial Template is placed on the tibia and both holes are drilled, pinning the anterior hole only to accommodate instruments for the upcoming fin hole preparation. FIG. 42 shows tibial template placement, in accordance with one embodiment of the invention. Next, the fin hole is created using, for example, a 5 millimeter osteotome. The tibial implant is designed to match the patient anatomy and should cover the tibia cortex without overhang or undercoverage. The outline of the tibial template provides visual confirmation of the match. Trialing & Cementing of Implant Multiple 1.5 to 2 mm cement holes may be drilled to enhance cement interdigitation with the femoral cortical surface, and the joint is thoroughly irrigated. FIG. 43 shows the femoral cement holes, in accordance with one embodiment of the invention. Next, the metal implants are placed into position and the trial poly is inserted which provides optimal balancing. Illustratively, two different thicknesses may be provided, 6 mm or 8 mm. Combined with the 2 millimeter thickness of the tibial tray, the 6 and 8 mm trials will correspond to the 8 and 10 millimeter Spacer Blocks used to confirm proper balance. The tibial tray may be cemented first, with all extruded cement removed and then the femoral component may be inserted. FIG. 44 shows the implants being cemented, in accordance with one embodiment of the invention. The knee is brought in 45 degrees and the trial tibial insert is inserted, allowing equal pressurization of the femoral component in flexion and in extension. All extruded cement is removed and the cement is allowed to harden. FIG. 45 shows the implants cemented in place, in accordance with one embodiment of the invention. The trial insert is removed along with any residual extruded cement and the real polyethylene insert is inserted. Wound closure of the arthrotomy is recommended in flexion and multiple layers. The foregoing description of embodiments of the present invention has been provided for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations will be apparent to the practitioner skilled in the art. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application, thereby enabling others skilled in the art to understand the invention and the various embodiments and with various modifications that are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the following claims equivalents thereof.
Disclosed herein are tools for repairing articular surfaces repair materials and for repairing an articular surface. The surgical tools are designed to be customizable or highly selectable by patient to increase the speed, accuracy and simplicity of performing total or partial arthroplasty.
0
RELATED APPLICATION This application is related to U.S. Pat. No. 4,942,529 issued to Isaac Avitan et al on Jul. 17, 1990, for Lift Truck Control Systems, bearing a common assignee, and whose teachings are hereby incorporated by reference. FIELD OF THE INVENTION The invention relates to a method and apparatus for measuring the height of a carriage of a forklift truck, and, more particularly, to determining the absolute and/or relative carriage height for a lift truck of the "order picker" type having an extendable mast. BACKGROUND OF THE INVENTION The measurement of carriage height in forklift vehicles is a critical parameter affecting speed and stability. In the aforementioned U.S. Pat. No. 4,942,529, it is disclosed that the height of the carriage of a forklift truck can be determined by measuring the hydraulic flow or displacement necessary to lift and lower the mast supporting the carriage. The fluid flow measurement is converted into electrical signals that are used to determine the height of the carriage of the lift truck from a home position. While the disclosure provides a viable means to accomplish the objectives outlined therein, the measurement of fluid flow comprises many complexities that were not addressed by the patent. These complexities affect the precision of the measurement and could in an extreme situation lead to an erroneous result. The present invention has as one of its objectives to provide a method and apparatus for obtaining a more precise hydraulic flow measurement, and hence for determining the proper height of the carriage of the forklift vehicle. One of the deficiencies of the fluid measurement was the failure to account for the variations introduced by reason of viscosity changes in the hydraulic fluid. Viscosity is a function primarily of temperature of the fluid. It was also observed that the flow sensor output frequency will differ, depending on the rate and direction of the fluid flow. This is due to the mechanical construction of the sensor itself. In other words, the sensor is not truly bidirectional in its characteristics with regard to fluid flow. The present invention seeks to compensate for changes of viscosity based on fluid temperature and for flow rate based on flow sensor frequency output. The present invention also seeks to correct for the non-symmetrical operating characteristics of the fluid sensor itself. It is an object of the present invention to determine absolute carriage height accurately by means of a flow sensor. SUMMARY OF THE INVENTION In accordance with the present invention, there is provided a method and apparatus of determining the absolute and/or relative carriage height of a forklift truck having an extendable mast. The hydraulic fluid displacement or flow rate through the flow sensor is converted to electrical signals to obtain the carriage height. A hydraulic flow sensing means comprises two proximity sensors to detect motion (speed and direction) of the fluid. The sensors are located at an electrical phase angle of 90° with respect to each other. This results in an electrical sine wave pulse train pair (leading and lagging). The leading and lagging pulse signals are used to determine an instantaneous elevation reading for the carriage. The pulse train phase relationship of the sensors provides a determination of the fluid flow direction. The fluid flow direction influences the elevation reading, corrected by a conversion factor that precisely determines the carriage height, which is dependent on oil viscosity and flow sensor frequency output. The apparatus also includes a temperature sensor located in the hydraulic fluid to measure the temperature of the hydraulic fluid and to provide a compensatory factor in determining the kinematic viscosity of the pumped liquid. Two spaced-apart reference switches are also provided along the path defining the carriage travel (i.e., along the extendable mast). These reference switches provide the means for recalibrating or synchronizing the lift height. In the learning mode, the reference switches are used to determine the appropriate conversion factor(s) in both directions for later use in actual measurements for the specific oil type and vehicle characteristics. The method of the invention comprises the first step of reading the absolute height last determined by the apparatus. Next, the temperature of the hydraulic fluid is measured to determine the kinematic viscosity of the fluid. The flow sensors are read next to obtain a quadrature increment indicative of flow rate and flow direction. The ratio of pulse rate to kinematic viscosity is then computed. The flow direction indicates whether the carriage is ascending/descending along the mast. A conversion factor is then computed or looked up to obtain the relative incremental/decremental height. The incremental/decremental height is then added or subtracted from the initial height reading to obtain a new absolute height value. The new value is stored, and the routine is exited until further notice. BRIEF DESCRIPTION OF THE DRAWINGS A complete understanding of the present invention may be obtained by reference to the accompanying drawings, when considered in conjunction with the subsequent detailed description, in which: FIG. 1 is a schematic view of the hydraulic circuit of the invention; FIG. 2 is a block diagram schematic view of the flow sensor control module used in conjunction with the hydraulic circuit of FIG. 1 to calculate the relative height of the carriage; FIG. 3 is a more detailed block diagram of the internal components of the flow sensor control module shown in FIG. 2; FIG. 4 is a temperature vs. kinematic viscosity chart of a specified oil used in the preferred embodiment; FIG. 5 is a frequency/viscosity ratio vs. conversion factor chart for ascending and descending curves; and FIG. 6 is the flow chart for the method of the invention. For the purposes of brevity and clarity, similar elements and components will bear the same designation throughout the figures. DESCRIPTION OF THE PREFERRED EMBODIMENT Generally speaking, the invention features a method and apparatus for determining the height of a carriage of a material handling vehicle of the "order picking" type. It has been previously demonstrated in the aforementioned U.S. Pat. No. 4,942,529 that the height of a carriage of such a material handling vehicle can be determined by measuring the hydraulic fluid flow rate in raising and lowering the carriage. The prior teaching, while suggesting a viable means to accomplish the result, nevertheless had neglected to consider some of the parameters for making the height determination more accurate. The present invention addresses the additional parameter of fluid viscosity variation with respect to oil temperature. Another parameter utilized in the present invention relates to flow sensor frequency variation with respect to the hydraulic flow rate of oil, compensating for the non-linearity in the frequency of the flow sensor. A third parameter of the present invention addresses and compensates for the asymmetry of the flow sensor as a function of the direction of fluid flow with respect thereto. In addition, the present invention also incorporates the learning technique, disclosed in the aforementioned patent, for referencing a unit distance-per-pulse by representing a predetermined volume of fluid. The foregoing parameters all directly affect the precision of the calculation of the carriage height. Now referring to FIG. 1, a schematic hydraulic circuit 10 for accomplishing the vertical movement of the carriage 11 is shown. The carriage 11 is disposed upon the end of a vertical mast 12 that is connected to the piston 14 of a hydraulic cylinder 15. Fluid for moving the piston enters the fluid chamber 16 of the cylinder 15 through hydraulic line 18. The fluid is pumped through line 18 to cylinder 15 by means of a hydraulic pump 20. The pump 20 draws the hydraulic fluid from reservoir 19 when the carriage 11 is to be lifted. The fluid is forced out of cylinder 15 back into reservoir 19 when the carriage 11 is lowered. The fluid returns to the reservoir 19 via two pathways 21 and 22, respectively. A filter 23 cleans the returning fluid. A pressure relief valve 24 in line 21 allows the fluid to return to the reservoir 19 when hydraulic pressure exceeds design threshold conditions. The fluid normally returns to reservoir 19 via line 22 when the carriage 11 is to be lowered. Normally returning fluid will pass through the load holding valve 26 and the proportional lowering valve 25, which are opened for returned fluid. A flow sensor 30 disposed in flow line 18 monitors the fluid flow into and out of the cylinder 15, in order to calculate the height of the carriage 11. A fluid temperature sensor 31 is associated with the flow sensor 30 for determining the kinematic viscosity of the fluid. Check valves 17 and 19, respectively, are disposed in line 18 to prevent backflow of the fluid within the line. Flow restriction 27 limits the maximum allowable lowering speed of carriage 11. Two reference switches 34 and 36, respectively, are located along the path of travel 35 of the mast 12 of cylinder 15. The distance between reference switches 34 and 36 is known and fixed. These two mast reference points are used to reference the unit distance-per-pulse of a specified oil and vehicle type by representing a predetermined amount of pumped fluid between them, proportional to a given number of electrical pulses. These two switches 34 and 36 also provide a means by which the height measurement can be recalibrated or synchronized with the carriage height. Referring now also to FIG. 2, a flow sensor control module 37 is illustrated. The flow sensor control module 37 converts the readings from the flow sensor 30 and the temperature sensor 31 into electrical signals for calculating the height of carriage 11 (FIG. 1). The signals from the flow sensor 30 are distinguished by leading 38 and lagging 39 signals, which indicate whether the carriage is moving up or down. The calculation for the height of the carriage 11 depends upon the direction of movement of the fluid. The conversion factor for determining the carriage height is non-linear and will vary with the temperature, the direction and the velocity of the fluid flow. The flow sensor 30 comprises two proximity sensors having a phase angle of 90° therebetween. The flow sensor 30 measures the leading and lagging flow rate, to indicate whether the carriage 11 is being raised or lowered. The electrical pulses, provided by control module 37 as a function of the fluid flow, are counted and the value is correlated by means of the conversion factor, to accurately determine the height of the carriage 11. The mast 12 of cylinder 15 (FIG. 1) has a known cross-sectional area, which is used together with the volumetric capacity determination to calculate carriage height. The temperature sensor 31 is used to correct for changes in kinematic viscosity of the fluid, as aforementioned. One type of temperature sensor that can be used for this purpose is a Model TD4A sensor, available from the Micro Switch Corporation. The two reference switches 34 and 36 (FIG. 1), disposed along the path 35 of the mast travel provide signals 34a and 36a, respectively (FIG. 2). These signals are used in two ways: in the learn mode to determine the accumulated flow sensor pulses between the switches having known displacement from one another and reference the particular fluid/vehicle characteristics; and to recalibrate or synchronize height measurement during normal operation. Power is provided by means of lines 40, which provide a 12 volt and a ground potential. Control module 37 is adapted to interface to a host, not shown, over bidirectional communications receive and transmit channel 42 configured in the form of an RS-485 or an RS-422 serial communications bus. The receiver portion of communications channel 42 can be used to interrogate control module 37 as to status of control module 37 itself or of any flow sensor 30, temperature sensor 31, limit switches 34 and 36 (FIG. 1), or any other components attached to control module 37. Responses to such interrogations can be provided over the transmit portion of communications channel 42. The carriage height reported over communications channel 42 is in absolute form, directly usable downstream in further processing, as hereinbelow described. It should be understood that flow sensor control module 37 can also serve as a feedback mechanism servicing closed-loop velocity and/or position controllers in appropriate applications. Referring now also to FIG. 3, a block diagram depicts the internal components of control module 37 (FIG. 2) in greater detail. A microcontroller 44 such as manufactured by Motorola Company as Model Nos. 68HC811E2 or 68HC711D3 can be used to control the flow sensor control module 37. The advantage of using the first mentioned microcontroller relates to its electrically erasable characteristics. The latter mentioned microcontroller is not reprogrammable. Referring now to FIG. 4, there is shown a temperature vs. kinematic viscosity chart for the two types & oils: hydraulic fluid MIL G-5606 and SAE 10, which are intended to cover the broad range of applications for this type of vehicle. FIG. 4 is depicted on a log-log scale where temperature (°F.) is shown on the horizontal scale and kinematic viscosity (Cst) is shown on the vertical scale. Given the measured fluid temperature, kinematic viscosity can be either computed or looked up in accordance with the characteristic Cst vs. temperature relationship shown in FIG. 4. The system is provided with the specific operating oil curve (e.g., SAE 10) upon initialization until and unless a new oil is introduced into the system. Referring now to FIG. 5, a linear-log scale is used to represent the relationship between frequency/kinematic viscosity (Hz/Cst) and conversion factor (K) representing pulses/gallon. A pair of characteristic curves is shown: one for forward flow 50 and the other for reverse flow 52. These two curves are due to the asymmetrical mechanical characteristics of the flow sensor 30 (FIG. 1), which results in dissimilar sensor response characteristics. Given a specific frequency/kinematic viscosity ratio (Hz/Cst), the conversion factor (K) can be either computed or looked up in accordance with the Hz/Cst vs. K curve for the particular fluid flow direction (e.g., forward). Depending upon the hydraulic orientation of the sensor with respect to fluid flow, "forward" could imply ascending and "reverse" could imply descending, with respect to overall computation. Referring now also to FIG. 6, a flow chart is depicted that illustrates the method used herein for calculating the carriage height. The subroutine of the vehicle control program for calculating the carriage height is entered and the absolute height (H old ) is read from storage memory, step 101. Next, a reading of the oil temperature is obtained, step 102. Data representative of FIG. 4 is used to compute or look up the oil kinematic viscosity (Cst), step 103. The incremental quadrature (pulses) of the flow sensor 30 (FIG. 1) is determined at step 104. Sensor turbine rotating frequency (Hz) is computed, step 105, as follows: ##EQU1## The ratio of Hz/Cst is then computed, step 106. The decision is then made as to whether the pulse train is leading (lifting) or lagging (lowering) via decision step 107. If lowering, the "down" conversion factor (K) compensating for Hz/Cst is computed or looked up relative to data representative of FIG. 5, step 108. Having obtained the conversion factor (K), a decremented height value (ΔH d ) is obtained, step 109, for subtraction from the absolute height (H old ) determined in step 101. On the other hand, if lifting, the "up" conversion factor (K), [step 110], and subsequent incremented height value step (ΔH i ), [step 111], are similarly computed. The incremental height value (ΔH d or ΔH i ) is added to the absolute height (H old ) determined at step 101, in order to obtain the new absolute height value (H new ), step 112. The new absolute height value is stored, step 113. The flow sensor increment memory location is cleared, step 114, to make room for future data. The program is terminated and awaits re-entry. The current invention provides a more accurate and precise calculation of the carriage height. There exists with the present system and method a better coupling between the mechanical sensing and the electrical output, taking into effect and compensating for operational anomalies in the mechanical sensing devices. Also, the effects of temperature-dependent viscosity upon the determination of the carriage height is addressed for the first time. Since other modifications and changes varied to fit particular operating requirements and environments will be apparent to those skilled in the art, the invention is not considered limited to the example chosen for purposes of disclosure, and covers all changes and modifications which do not constitute departures from the true spirit and scope of this invention. Having thus described the invention, what is desired to be protected by Letters Patent is presented by the subsequently appended claims.
The invention features a method and apparatus of determining the absolute and/or relative carriage height of a forklift truck having an extendable mast. The hydraulic fluid displacement is converted to electrical signals to obtain the carriage height. A hydraulic flow sensor has two proximity sensors to detect motion (i.e., the speed and direction) of the fluid and to provide an electrical signal. A conversion factor is applied to the signal to precisely determine the carriage height. The conversion factor compensates for the sensor asymmetrical flow and frequency characteristics, and for the fluid kinematic viscosity characteristics.
1
FIELD OF THE INVENTION [0001] The invention relates to novel compounds of formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI) (hereinafter referred to as “formulae (I)-(VI)”), which more particularly include sulfonylurea derivatives, sulfonylthiourea derivatives, sulfonylguanidine derivatives, sulfonylcyanoguanidine derivatives, thioacylsulfonamide derivatives, and acylsulfonamide derivatives which are effective platelet ADP receptor inhibitors. These derivatives may be used in various pharmaceutical compositions, and are particularly effective for the prevention and/or treatment of cardiovascular diseases, particularly those diseases related to thrombosis. DESCRIPTION OF THE RELATED ART [0002] Thrombotic complications are a major cause of death in the industrialized world. Examples of these complications include acute myocardial infarction, unstable angina, chronic stable angina, transient ischemic attacks, strokes, peripheral vascular disease, preeclampsia/eclampsia, deep venous thrombosis, embolism, disseminated intravascular coagulation and thrombotic cytopenic purpura. Thrombotic and restenotic complications also occur following invasive procedures, e.g., angioplasty, carotid endarterectomy, post CABG (coronary artery bypass graft) surgery, vascular graft surgery, stent placements and insertion of endovascular devices and protheses. It is generally thought that platelet aggregates play a critical role in these events. Blood platelets, which normally circulate freely in the vasculature, become activated and aggregate to form a thrombus with disturbed blood flow caused by ruptured atherosclerotic lesions or by invasive treatments such as angioplasty, resulting in vascular occlusion. Platelet activation can be initiated by a variety of agents, e.g., exposed subendothelial matrix molecules such as collagen, or by thrombin which is formed in the coagulation cascade. [0003] An important mediator of platelet activation and aggregation is ADP (adenosine 5′-diphosphate) which is released from blood platelets in the vasculature upon activation by various agents, such as collagen and thrombin, and from damaged blood cells, endothelium or tissues. Activation by ADP results in the recruitment of more platelets and stabilization of existing platelet aggregates. Platelet ADP receptors mediating aggregation are activated by ADP and some of its derivatives and antagonized by ATP (adenosine 5′-triphosphate) and some of its derivatives (Mills, D. C. B. (1996) Thromb. Hemost. 76:835-856). Therefore, platelet ADP receptors are members of the family of P2 receptors activated by purine and/or pyrimidine nucleotides (King, B. F., Townsend-Nicholson, A. & Burnstock, G. (1998) Trends Pharmacol. Sci. 19:506-514). [0004] Recent pharmacological data using selective antagonists suggests that ADP-dependent platelet aggregation requires activation of at least two ADP receptors (Kunapuli, S. P. (1998), Trends Pharmacol. Sci. 19:391-394; Kunapuli, S. P. & Daniel, J. L. (1998) Biochem. J. 336:513-523; Jantzen, H. M. et al. (1999) Thromb. Hemost. 81:111-117). One receptor appears to be identical to the cloned P2Y 1 receptor, mediates phospholipase C activation and intracellular calcium mobilization and is required for platelet shape change. The second platelet ADP receptor important for aggregation mediates inhibition of adenylyl cyclase. Molecular cloning of the gene or cDNA for this receptor has not yet been reported. Based on its pharmacological and signaling properties this receptor has been provisionally termed P2Y ADP (Fredholm, B. B. et al. (1997) TIPS 18:79-82), P2T AC (Kunapuli, S. P. (1998), Trends Pharmacol. Sci. 19:391-394) or P2Ycyc (Hechler, B. et al. (1998) Blood 92, 152-159). [0005] Various directly or indirectly acting synthetic inhibitors of ADP-dependent platelet aggregation with antithrombotic activity have been reported. The orally active antithrombotic thienopyridines ticlopidine and clopidogrel inhibit ADP-induced platelet aggregation, binding of radiolabeled ADP receptor agonist 2-methylthioadenosine 5′-diphosphate to platelets, and other ADP-dependent events indirectly, probably via formation of an unstable and irreversible acting metabolite (Quinn, M. J. & Fitzgerald, D. J. (1999) Circulation 100:1667-1667). Some purine derivatives of the endogenous antagonist ATP, e.g., AR-C (formerly FPL or ARL) 67085MX and AR-C69931MX, are selective platelet ADP receptor antagonists which inhibit ADP-dependent platelet aggregation and are effective in animal thrombosis models (Humphries et al. (1995), Trends Pharmacol. Sci. 16, 179; Ingall, A. H. et al. (1999) J. Med. Chem. 42, 213-230). Novel triazolo[4,5-d]pyrimidine compounds have been disclosed as P 2T -antagonists (WO 99/05144). Tricyclic compounds as platelet ADP receptor inhibitors have also been disclosed in WO 99/36425. The target of these antithrombotic compounds appears to be the platelet ADP receptor mediating inhibition of adenylyl cyclase. [0006] Despite these compounds, there exists a need for more effective platelet ADP receptor inhibitors. In particular, there is a need for platelet ADP receptor inhibitors having antithrombotic activity that are useful in the prevention and/or treatment of cardiovascular diseases, particularly those related to thrombosis. SUMMARY OF THE INVENTION [0007] The invention provides compounds of formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI): [0000] [0000] A is selected from the group consisting of aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkylaryl, and alkylheteroaryl. W is selected from the group consisting of aryl, substituted aryl, heteroaryl, and substituted heteroaryl. E is selected from the group consisting of H, —C 1 -C 8 alkyl, polyhaloalkyl, —C 3-8 -cycloalkyl, aryl, alkylaryl, substituted aryl, heteroaryl, and substituted heteroaryl. D is selected from the group consisting of NR 1 —(C═O)—R 2 , —O—R 1 ; [0000] [0000] wherein: R 1 is independently selected from the group consisting of: H, C 1 -C 8 alkyl, polyhaloalkyl, —C 3-8 -cycloalkyl, aryl, alkylaryl, substituted aryl, heteroaryl, substituted heteroaryl, —(C═O)—C 1 -C 8 alkyl, —(C═O)-aryl, —(C═O)-substituted aryl, —(C═O)-heteroaryl and —(C═O)-substituted heteroaryl; R 2 is independently selected from the group consisting of aryl, substituted aryl, heteroaryl, substituted heteroaryl, or R 1 and R 2 can be direct linked or can be indirectly linked through a carbon chain that is from 1 to about 8 carbon atoms in length, n is 0-4, m is 0 or 1, y is 0-4 and Q is independently C or N, with the proviso that when Q is a ring carbon atom, each ring carbon atom is independenty substituted by X. X is in each case a member independently selected from the group consisting of: H, halogen, polyhaloalkyl, —OR 3 , —SR 3 , —CN, —NO 2 , —SO 2 R 3 , —C 1-10 -alkyl, —C 3-8 -cycloalkyl, aryl, aryl-substituted by 1-4 R 3 groups, amino, amino-C 1-8 -alkyl, C 1-3 -acylamino, C 1-3 -acylamino-C 1-8 -alkyl, C 1-6 -alkylamino, C 1-6 -alkylamino C 1-8 alkyl, C 1-6 dialkylamino, C 1-6 dialkylamino C 1-8 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 -alkyl, carboxy-C 1-6 -alkyl, C 1-3 -alkoxycarbonyl, C 1-3 -alkoxycarbonyl-C 1-6 -alkyl, carboxy C 1-6 alkyloxy, hydroxy, hydroxy C 1-6 alkyl, and a 5 to 10 membered fused or non-fused aromatic or nonaromatic heterocyclic ring system, having 1 to 4 heteroatoms independently selected from N, O, and S, with the proviso that the carbon and nitrogen atoms, when present in the heterocyclic ring system, are unsubstituted, mono- or di-substituted independently with 0-2 R 4 groups. R 3 and R 4 are each independently selected from the group consisting of: H, halogen, —CN, —NO 2 , —C 1-10 alkyl, C 3-8 -cycloalkyl, aryl, amino, amino-C 1-8 -alkyl, C 1-3 -acylamino, C 1-3 -acylamino-C 1-8 -alkyl, C 1-6 -alkylamino, C 1-6 -alkylamino C 1-8 alkyl, C 1-6 dialkylamino, C 1-6 dialkylamino C 1-8 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 -alkyl, carboxy-C 1-6 -alkyl, C 1-3 -alkoxycarbonyl, C 1-3 -alkoxycarbonyl-C 1-6 -alkyl, carboxy-C 1-6 -alkyloxy, hydroxy, hydroxy-C 1-6 -alkyl, -thio and thio-C 1-6 -alkyl. Y is selected from the group consisting of O, S, N—OR 5 , and NR 5 , wherein R 5 is selected from the group consisting of: H, C 1-10 alkyl, C 3-8 -cycloalkyl, and CN. [0014] The invention also covers all pharmaceutically acceptable salts and prodrugs of the compounds of formulae (I)-(VI). [0015] In another aspect, the invention provides pharmaceutical compositions for preventing or treating thrombosis in a mammal containing a therapeutically effective amount of a compound of formulae (I)-(VI) or a pharmaceutically acceptable salt thereof and a pharmaceutically acceptable carrier. The invention further provides a method for preventing or treating thrombosis in a mammal by administering a therapeutically effective amount of a compound of formulae (I)-(VI) or a pharmaceutically acceptable salt thereof. DETAILED DESCRIPTION OF THE INVENTION Definitions [0016] In accordance with the present invention and as used herein, the following terms are defined with the following meanings, unless explicitly stated otherwise. [0017] The term “alkenyl” refers to a trivalent straight chain or branched chain unsaturated aliphatic radical. The term “alkinyl” (or “alkynyl”) refers to a straight or branched chain aliphatic radical that includes at least two carbons joined by a triple bond. If no number of carbons is specified, alkenyl and alkinyl each refer to radicals having from 2-12 carbon atoms. [0018] The term “alkyl” refers to saturated aliphatic groups including straight-chain, branched-chain and cyclic groups having the number of carbon atoms specified, or if no number is specified, having up to about 12 carbon atoms. The term “cycloalkyl” as used herein refers to a mono-, bi-, or tricyclic aliphatic ring having 3 to about 14 carbon atoms and preferably 3 to about 7 carbon atoms. [0019] The term “C 1 -C 6 alkoxy” as used herein refers to an ether moiety whereby the oxygen is connected to a straight or branched chain of carbon atoms of the number indicated. [0020] The term “mono-C 1 -C 6 alkylamino” as used herein refers to an amino moiety whereby the nitrogen is substituted with one H and one C 1 -C 6 alkyl substituent, the latter being defined as above. [0021] The term “di-C 1 -C 6 alkylamino” as used herein refers to an amino moiety whereby the nitrogen is substituted with two C 1 -C 6 alkyl substituents as defined above. [0022] The term “monoarylamino” as used herein refers to an amino moiety whereby the nitrogen is substituted with one H and one aryl substituent, such as a phenyl, the latter being defined as above. [0023] The term “diarylamino” as used herein refers to an amino moiety whereby the nitrogen is substituted with two aryl substituents, such as phenyl, the latter being defined as above. [0024] The term “C 1 -C 6 alkylsulfonyl” as used herein refers to a dioxosulfur moiety with the sulfur atom also connected to one C 1 -C 6 alkyl substituent, the latter being defined as above. [0025] The term “C 1 -C 6 alkoxycarbonyl” as used herein refers to a hydroxycarbonyl moiety whereby the hydrogen is replaced by a C 1 -C 6 alkyl substituent, the latter being defined as above. [0026] As used herein, the terms “carbocyclic ring structure” and “C 3-16 carbocyclic mono, bicyclic or tricyclic ring structure” or the like are each intended to mean stable ring structures having only carbon atoms as ring atoms wherein the ring structure is a substituted or unsubstituted member selected from the group consisting of: a stable monocyclic ring which is an aromatic ring (“aryl”) having six ring atoms (“phenyl”); a stable monocycle non-aromatic ring having from 3 to about 7 ring atoms in the ring; a stable bicyclic ring structure having a total of from 7 to about 12 ring atoms in the two rings wherein the bicyclic ring structure is selected from the group consisting of ring structures in which both of the rings are aromatic, ring structures in which one of the rings is aromatic and ring structures in which both of the rings are non-aromatic; and a stable tricycle ring structure having a total of from about 10 to about 16 atoms in the three rings wherein the tricyclic ring structure is selected from the group consisting of: ring structures in which three of the rings are aromatic, ring structures in which two of the rings are aromatic and ring structures in which three of the rings are non-aromatic. In each case, the non-aromatic rings when present in the monocycle, bicyclic or tricyclic ring structure may independently be saturated, partially saturated or fully saturated. Examples of such carbocyclic ring structures include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, cyclooctyl, [3.3.0]bicyclooctane, [4.3.0]bicyclononane, [4.4.0]bicyclodecane (decalin), 2.2.2]bicyclooctane, fluorenyl, phenyl, naphthyl, indanyl, adamantyl, or tetrahydronaphthyl (tetralin). Moreover, the ring structures described herein may be attached to one or more indicated pendant groups via any carbon atom which results in a stable structure. The term “substituted” as used in conjunction with carbocyclic ring structures means that hydrogen atoms attached to the ring carbon atoms of ring structures described herein may be substituted by one or more of the substituents indicated for that structure if such substitution(s) would result in a stable compound. [0027] The term “aryl” which is included with the term “carbocyclic ring structure” refers to an unsubstituted or substituted aromatic ring, substituted with one, two or three substituents selected from lower alkoxy, lower alkyl, lower alkylamino, hydroxy, halogen, cyano, hydroxyl, mercapto, nitro, thioalkoxy, carboxaldehyde, carboxyl, carboalkoxy and carboxamide, including but not limited to carbocyclic aryl, heterocyclic aryl, and biaryl groups and the like, all of which may be optionally substituted. Preferred aryl groups include phenyl, halophenyl, loweralkylphenyl, napthyl, biphenyl, phenanthrenyl and naphthacenyl. [0028] The term “arylalkyl” which is included with the term “carbocyclic aryl” refers to one, two, or three aryl groups having the number of carbon atoms designated, appended to an alkyl group having the number of carbon atoms designated. Suitable arylalkyl groups include, but are not limited to, benzyl, picolyl, naphthylmethyl, phenethyl, benzyhydryl, trityl, and the like, all of which may be optionally substituted. [0029] The term “phenyl” as used herein refers to a six carbon containing aromatic ring which can be variously mono- or poly-substituted with H, C 1 -C 6 alkyl, hydroxyl, C 1 -C 6 alkoxy, amino, mono-C 1 -C 6 alkylamino, alkylamino, nitro, fluoro, chloro, bromo, iodo, hydroxycarbonyl, or C 1 -C 6 alkoxycarbonyl. [0030] As used herein, the term “heterocyclic ring” or “heterocyclic ring system” is intended to mean a substituted or unsubstituted member selected from the group consisting of a stable monocyclic ring having from 5-7 members in the ring itself and having from 1 to 4 hetero ring atoms selected from the group consisting of N, O and S; a stable bicyclic ring structure having a total of from 7 to 12 atoms in the two rings wherein at least one of the two rings has from 1 to 4 hetero atoms selected from N, O and S, including bicyclic ring structures wherein any of the described stable monocyclic heterocyclic rings is fused to a hexane or benzene ring; and a stable tricyclic heterocyclic ring structure having a total of from 10 to 16 atoms in the three rings wherein at least one of the three rings has from 1 to 4 hetero atoms selected from the group consisting of N, O and S. Any nitrogen and sulfur atoms present in a heterocyclic ring of such a heterocyclic ring structure may be oxidized. Unless indicated otherwise the terms “heterocyclic ring” or “heterocyclic ring system” include aromatic rings, as well as non-aromatic rings which can be saturated, partially saturated or fully saturated non-aromatic rings. Also, unless indicated otherwise the term “heterocyclic ring system” includes ring structures wherein all of the rings contain at least one hetero atom as well as structures having less than all of the rings in the ring structure containing at least one hetero atom, for example bicyclic ring structures wherein one ring is a benzene ring and one of the rings has one or more hetero atoms are included within the term “heterocyclic ring systems” as well as bicyclic ring structures wherein each of the two rings has at least one hetero atom. Moreover, the ring structures described herein may be attached to one or more indicated pendant groups via any hetero atom or carbon atom which results in a stable structure. Further, the term “substituted” means that one or more of the hydrogen atoms on the ring carbon atom(s) or nitrogen atom(s) of the each of the rings in the ring structures described herein may be replaced by one or more of the indicated substituents if such replacement(s) would result in a stable compound. Nitrogen atoms in a ring structure may be quaternized, but such compounds are specifically indicated or are included within the term “a pharmaceutically acceptable salt” for a particular compound. When the total number of O and S atoms in a single heterocyclic ring is greater than 1, it is preferred that such atoms not be adjacent to one another. Preferably, there are no more that 1 O or S ring atoms in the same ring of a given heterocyclic ring structure. [0031] Examples of monocylic and bicyclic heterocylic ring systems, in alphabetical order, are acridinyl, azocinyl, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl, benzthiazolyl, benztriazolyl, benztetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazalinyl, carbazolyl, 4aH-carbazolyl, carbolinyl, chromanyl, chromenyl, cinnolinyl, decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl, dihydrofuro[2,3-b]tetrahydrofuran, furanyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolinyl, indolizinyl, indolyl, 3H-indolyl, isobenzofuranyl, isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl (benzimidazolyl), isothiazolyl, isoxazolyl, morpholinyl, naphthyridinyl, octahydroisoquinolinyl, oxadiazolyl, 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl, oxazolyl, oxazolidinyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxathiinyl, phenoxazinyl, phthalazinyl, piperazinyl, piperidinyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyroazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pryidooxazole, pyridoimidazole, pyridothiazole, pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, 2H-pyrrolyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, quinuclidinyl, tetrahydrofuranyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, 6H-1,2,5-thiadazinyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, thiophenyl, triazinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,5-triazolyl, 1,3,4-triazolyl and xanthenyl. Preferred heterocyclic ring structures include, but are not limited to, pyridinyl, furanyl, thienyl, pyrrolyl, pyrazolyl, pyrrolidinyl, imidazolyl, indolyl, benzimidazolyl, 1H-indazolyl, oxazolinyl, or isatinoyl. Also included are fused ring and spiro compounds containing, for example, the above heterocylic ring structures. [0032] As used herein the term “aromatic heterocyclic ring system” has essentially the same definition as for the monocyclic and bicyclic ring systems except that at least one ring of the ring system is an aromatic heterocyclic ring or the bicyclic ring has an aromatic or non-aromatic heterocyclic ring fused to an aromatic carbocyclic ring structure. [0033] The terms “halo” or “halogen” as used herein refer to Cl, Br, F or I substituents. The term “haloalkyl”, and the like, refer to an aliphatic carbon radicals having at least one hydrogen atom replaced by a Cl, Br, F or I atom, including mixtures of different halo atoms. Trihaloalkyl includes trifluoromethyl and the like as preferred radicals, for example. [0034] The term “methylene” refers to —CH 2 —. [0035] The term “pharmaceutically acceptable salts” includes salts of compounds derived from the combination of a compound and an organic or inorganic acid. These compounds are useful in both free base and salt form. In practice, the use of the salt form amounts to use of the base form; both acid and base addition salts are within the scope of the present invention. [0036] “Pharmaceutically acceptable acid addition salt” refers to salts retaining the biological effectiveness and properties of the free bases and which are not biologically or otherwise undesirable, formed with inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like, and organic acids such as acetic acid, propionic acid, glycolic acid, pyruvic acid, oxalic acid, maleic acid, malonic acid, succinic acid, fumaric acid, tartaric acid, citric acid, benzoic acid, cinnamic acid, mandelic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, salicyclic acid and the like. [0037] “Pharmaceutically acceptable base addition salts” include those derived from inorganic bases such as sodium, potassium, lithium, ammonium, calcium, magnesium, iron, zinc, copper, manganese, aluminum salts and the like. Particularly preferred are the ammonium, potassium, sodium, calcium and magnesium salts. Salts derived from pharmaceutically acceptable organic nontoxic bases include salts of primary, secondary, and tertiary amines, substituted amines including naturally occurring substituted amines, cyclic amines and basic ion exchange resins, such as isopropylamine, trimethylamine, diethylamine, triethylamine, tripropylamine, ethanolamine, 2-diethylaminoethanol, trimethamine, dicyclohexylamine, lysine, arginine, histidine, caffeine, procaine, hydrabamine, choline, betaine, ethylenediamine, glucosamine, methylglucamine, theobromine, purines, piperizine, piperidine, N-ethylpiperidine, polyamine resins and the like. Particularly preferred organic nontoxic bases are isopropylamine, diethylamine, ethanolamine, trimethamine, dicyclohexylamine, choline, and caffeine. [0038] “Biological property” for the purposes herein means an in vivo effector or antigenic function or activity that is directly or indirectly performed by a compound of this invention that are often shown by in vitro assays. Effector functions include receptor or ligand binding, any enzyme activity or enzyme modulatory activity, any carrier binding activity, any hormonal activity, any activity in promoting or inhibiting adhesion of cells to an extracellular matrix or cell surface molecules, or any structural role. Antigenic functions include possession of an epitope or antigenic site that is capable of reacting with antibodies raised against it. [0039] In the compounds of this invention, carbon atoms bonded to four non-identical substituents are asymmetric. Accordingly, the compounds may exist as diastereoisomers, enantiomers or mixtures thereof. The syntheses described herein may employ racemates, enantiomers or diastereomers as starting materials or intermediates. Diastereomeric products resulting from such syntheses may be separated by chromatographic or crystallization methods, or by other methods known in the art. Likewise, enantiomeric product mixtures may be separated using the same techniques or by other methods known in the art. Each of the asymmetric carbon atoms, when present in the compounds of this invention, may be in one of two configurations (R or S) and both are within the scope of the present invention. Compound Embodiments of the Invention [0040] Compounds of formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI) below represent one embodiment of the invention: [0000] [0000] A is selected from the group consisting of aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkylaryl, and alkylheteroaryl. W is selected from the group consisting of aryl, substituted aryl, heteroaryl, and substituted heteroaryl. E is selected from the group consisting of H, —C 1 -C 8 alkyl, polyhaloalkyl, —C 3-8 -cycloalkyl, aryl, alkylaryl, substituted aryl, heteroaryl, and substituted heteroaryl. D is selected from the group consisting of NR 1 —(C═O)—R 2 , —O—R 1 : [0000] [0000] wherein: R 1 is independently selected from the group consisting of: H, C 1 -C 8 alkyl, polyhaloalkyl, —C 3-8 -cycloalkyl, aryl, alkylaryl, substituted aryl, heteroaryl, substituted heteroaryl, —(C═O)—C 1 -C 8 alkyl, —(C═O)-aryl, —(C═O)-substituted aryl, —(C═O)-heteroaryl and —(C═O)-substituted heteroaryl; R 2 is selected from the group consisting of: aryl, substituted aryl, heteroaryl, substituted heteroaryl, or R 1 and R 2 can be direct linked or can be indirectly linked through a carbon chain that is from 1 to about 8 carbon atoms in length, n is 0-4, m is 0 or 1, y is 0-4 and Q is independently C or N, with the proviso that when Q is a ring carbon atom, each ring carbon atom is independently substituted by X, wherein X is in each case a member independently selected from the group consisting of: H, halogen, polyhaloalkyl, —OR 3 , —SR 3 , —CN, —NO 2 , —SO 2 R 3 , —C 1-10 -alkyl, —C 3-8 -cycloalkyl, aryl, aryl-substituted by 1-4 R 3 groups, amino, amino-C 1-8 -alkyl, C 1-3 -acylamino, C 1-3 -acylamino-C 1-8 -alkyl, C 1-6 -alkylamino, C 1-6 -alkylamino C 1-8 alkyl, C 1-6 dialkylamino, C 1-6 dialkylamino C 1-8 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 -alkyl, carboxy-C 1-6 -alkyl, C 1-3 -alkoxycarbonyl, C 1-3 -alkoxycarbonyl-C 1-6 -alkyl, carboxy C 1-6 alkyloxy, hydroxy, hydroxy C 1-6 alkyl, and a 5 to 10 membered fused or non-fused aromatic or nonaromatic heterocyclic ring system, having 1 to 4 heteroatoms independently selected from N, O, and S, with the proviso that the carbon and nitrogen atoms, when present in the heterocyclic ring system, are unsubstituted, mono- or di-substituted independently with 0-2 R 4 groups, and wherein R 3 and R 4 are each independently selected from the group consisting of: H, halogen, —CN, —NO 2 , —C 1-10 alkyl, C 3-8 -cycloalkyl, aryl, amino, amino-C 1-8 -alkyl, C 1-3 -acylamino, C 1-3 -acylamino-C 1-8 -alkyl, C 1-6 -alkylamino, C 1-4 -alkylamino C 1-6 alkyl, C 1-6 dialkylamino, C 1-6 dialkylamino C 1-8 alkyl, C 1-6 alkoxy, C 1-6 alkoxy-C 1-6 -alkyl, carboxy-C 1-6 -alkyl, C 1-3 -alkoxycarbonyl, C 1-3 -alkoxycarbonyl-C 1-6 -alkyl, carboxy-C 1-6 -alkyloxy, hydroxy, hydroxy-C 1-6 -alkyl, -thio and thio-C 1-6 -alkyl. Y is selected from the group consisting of O, S, N—OR 5 , and NR 5 , wherein R 5 is selected from the group consisting of: H, C 1-10 alkyl, C 3-8 -cycloalkyl, and CN. [0046] The invention also covers all pharmaceutically acceptable salts and prodrugs of the compounds of formula I to formula VI. [0047] In another preferred embodiment of the invention, compounds of formulae (I)-(VI) include the compounds set forth below in Tables 1-4: [0000] TABLE 1 Formula Ia R 2 R 1 W Y A H O H O H S H N—C≡N H O H NH Me NH N—C≡N Me O H O H [0000] TABLE 2 Formula Ib X W Y A 3-Br O 3-Cl NH 4-OMe O H N—C≡N 3,4-diMe NH 3-SO 2 Me O [0000] TABLE 3 Formula Ic Y A O NH O N—C≡N NH O [0000] TABLE 4 Formula Id R 1 R 2 W H Me H H Me H Examples of specific preferred compounds are listed below: [0000] Preparation of Compounds of the Invention [0048] A compound of formulae (I)-(VI) may be prepared by various methods as outlined in the following documents: J. Med. Chem., 33, 23-93-2407 (1990); Biorg. & Med. Chem. Letts., Vol. 2, No. 9, pp. 987-992 (1992); J. Med. Chem., 35, 3012-3016 (1992); U.S. Pat. No. 5,234,955 (1993), U.S. Pat. No. 5,354,778 (1994); U.S. Pat. No. 5,565,494 (1996); U.S. Pat. No. 5,594,028 (1997); U.S. Pat. No. 5,302,724 (1994); and WO 97/08145, which are incorporated herein in their entirety by reference. Other well-known heterocyclic and carbocyclic synthetic procedures as well as modification of the procedures that are incorporated above may be utilized. [0049] Compounds of formulae (I)-(VI) may be isolated using typical isolation and purification techniques known in the art, including, for example, chromatographic and recrystallization methods. [0050] In compounds of formula formulae (I)-(VI) of the invention, carbon atoms to which four non-identical substituents are bonded are asymmetric. Accordingly, a compound of formulae (I)-(VI) may exist as enantiomers, diastereomers or a mixture thereof. The enantiomers and diastereomers may be separated by chromatographic or crystallization methods, or by other methods known in the art. The asymmetric carbon atom when present in a compound of formulae (I)-(VI) of the invention, may be in one of two configurations (R or S) and both are within the scope of the invention. The presence of small amounts of the opposing enantiomer or diastereomer in the final purified product does not affect the therapeutic or diagnostic application of such compounds. [0051] According to the invention, compounds of formulae (I)-(VI) may be further treated to form pharmaceutically acceptable salts. Treatment of a compound of the invention with an acid or base may form, respectively, a pharmaceutically acceptable acid addition salt and a pharmaceutically acceptable base addition salt, each as defined above. Various inorganic and organic acids and bases known in the art including those defined herein may be used to effect the conversion to the salt. [0052] The invention also relates to pharmaceutically acceptable isomers, hydrates, and solvates of compounds of formulae (I)-(VI). Compounds of formulae (I)-(VI) may also exist in various isomeric and tautomeric forms including pharmaceutically acceptable salts, hydrates and solvates of such isomers and tautomers. [0053] This invention also encompasses prodrug derivatives of the compounds of formulae (I)-(VI). The term “prodrug” refers to a pharmacologically inactive derivative of a parent drug molecule that requires biotransformation, either spontaneous or enzymatic, within the organism to release the active drug. Prodrugs are variations or derivatives of the compounds of formulae (I)-(VI) of this invention which have groups cleavable under metabolic conditions. Prodrugs become the compounds of the invention which are pharmaceutically active in vivo when they undergo solvolysis under physiological conditions or undergo enzymatic degradation. Prodrug compounds of this invention may be called single, double, triple, etc., depending on the number of biotransformation steps required to release the active drug within the organism, and indicating the number of functionalities present in a precursor-type form. Prodrug forms often offer advantages of solubility, tissue compatibility, or delayed release in the mammalian organism (Bundgard, Design of Prodrugs, pp. 7-9, 21-24, Elsevier, Amsterdam (1985); Silverman, The Organic Chemistry of Drug Design and Drug Action , pp. 352-401, Academic Press, San Diego, Calif. (1992)). Prodrugs commonly known in the art include acid derivatives well known to practitioners of the art, such as, for example, esters prepared by reaction of the parent acids with a suitable alcohol, or amides prepared by reaction of the parent acid compound with an amine, or basic groups reacted to form an acylated base derivative. Moreover, the prodrug derivatives of this invention may be combined with other features herein taught to enhance bioavailability. Pharmaceutical Compositions and Methods of Treatment [0054] A compound of formulae (I)-(VI) according to the invention may be formulated into pharmaceutical compositions. Accordingly, the invention also relates to a pharmaceutical composition for preventing or treating thrombosis in a mammal, particularly those pathological conditions involving platelet aggregation, containing a therapeutically effective amount of a compound of formulae (I)-(VI) or a pharmaceutically acceptable salt thereof, each as described above, and a pharmaceutically acceptable carrier or agent. Preferably, a pharmaceutical composition of the invention contains a compound of formulae (I)-(VI), or a salt thereof, in an amount effective to inhibit platelet aggregation, more preferably, ADP-dependent aggregation, in a mammal, in particular, a human. Pharmaceutically acceptable carriers or agents include those known in the art and are described below. [0055] Pharmaceutical compositions of the invention may be prepared by mixing the compound of formulae (I)-(VI) with a physiologically acceptable carrier or agent. Pharmaceutical compositions of the invention may further include excipients, stabilizers, diluents and the like and may be provided in sustained release or timed release formulations. Acceptable carriers, agents, excipients, stablilizers, diluents and the like for therapeutic use are well known in the pharmaceutical field, and are described, for example, in Remington's Pharmaceutical Sciences , Mack Publishing Co., ed. A. R. Gennaro (1985). Such materials are nontoxic to the recipients at the dosages and concentrations employed, and include buffers such as phosphate, citrate, acetate and other organic acid salts, antioxidants such as ascorbic acid, low molecular weight (less than about ten residues) peptides such as polyarginine, proteins, such as serum albumin, gelatin, or immunoglobulins, hydrophilic polymers such as polyvinylpyrrolidinone, amino acids such as glycine, glutamic acid, aspartic acid, or arginine, monosaccharides, disaccharides, and other carbohydrates including cellulose or its derivatives, glucose, mannose or dextrins, chelating agents such as EDTA, sugar alcohols such as mannitol or sorbitol, counterions such as sodium and/or nonionic surfactants such as TWEEN, or polyethyleneglycol. [0056] Methods for preventing or treating thrombosis in a mammal embraced by the invention administer a therapeutically effective amount of a compound of formulae (I)-(VI) alone or as part of a pharmaceutical composition of the invention as described above to a mammal, in particular, a human. Compounds of formulae (I)-(VI) and pharmaceutical compositions of the invention containing a compound of formulae (I)-(VI) of the invention are suitable for use alone or as part of a multi-component treatment regimen for the prevention or treatment of cardiovascular diseases, particularly those related to thrombosis. For example, a compound or pharmaceutical composition of the invention may be used as a drug or therapeutic agent for any thrombosis, particularly a platelet-dependent thrombotic indication, including, but not limited to, acute myocardial infarction, unstable angina, chronic stable angina, transient ischemic attacks, strokes, peripheral vascular disease, preeclampsia/eclampsia, deep venous thrombosis, embolism, disseminated intravascular coagulation and thrombotic cytopenic purpura, thrombotic and restenotic complications following invasive procedures, e.g., angioplasty, carotid endarterectomy, post CABG (coronary artery bypass graft) surgery, vascular graft surgery, stent placements and insertion of endovascular devices and protheses. [0057] Compounds and pharmaceutical compositions of the invention may also be used as part of a multi-component treatment regimen in combination with other therapeutic or diagnostic agents in the prevention or treatment of thrombosis in a mammal. In certain preferred embodiments, compounds or pharmaceutical compositions of the invention may be coadministered along with other compounds typically prescribed for these conditions according to generally accepted medical practice such as anticoagulant agents, thrombolytic agents, or other antithrombotics, including platelet aggregation inhibitors, tissue plasminogen activators, urokinase, prourokinase, streptokinase, heparin, aspirin, or warfarin. Coadministration may also allow for application of reduced doses of the thrombolytic agents and therefore minimize potential hemorrhagic side-effects. Compounds and pharmaceutical compositions of the invention may also act in a synergistic fashion to prevent reocclusion following a successful thrombolytic therapy and/or reduce the time to reperfusion. [0058] The compounds and pharmaceutical compositions of the invention may be utilized in vivo, ordinarily in mammals such as primates, (e.g., humans), sheep, horses, cattle, pigs, dogs, cats, rats and mice, or in vitro. The biological properties, as defined above, of a compound or a pharmaceutical composition of the invention can be readily characterized by methods that are well known in the art such as, for example, by in vivo studies to evaluate antithrombotic efficacy, and effects on hemostasis and hematological parameters. [0059] Compounds and pharmaceutical compositions of the invention may be in the form of solutions or suspensions. In the management of thrombotic disorders the compounds or pharmaceutical compositions of the invention may also be in such forms as, for example, tablets, capsules or elixirs for oral administration, suppositories, sterile solutions or suspensions or injectable administration, and the like, or incorporated into shaped articles. Subjects (typically mammalian) in need of treatment using the compounds or pharmaceutical compositions of the invention may be administered dosages that will provide optimal efficacy. The dose and method of administration will vary from subject to subject and be dependent upon such factors as the type of mammal being treated, its sex, weight, diet, concurrent medication, overall clinical condition, the particular compound of formulae (I)-(VI) employed, the specific use for which the compound or pharmaceutical composition is employed, and other factors which those skilled in the medical arts will recognize. [0060] Dosage formulations of compounds of formulae (I)-(VI), or pharmaceutical compositions contain a compound of the invention, to be used for therapeutic administration must be sterile. Sterility is readily accomplished by filtration through sterile membranes such as 0.2 micron membranes, or by other conventional methods. Formulations typically will be stored in a solid form, preferably in a lyophilized form. While the preferred route of administration is orally, the dosage formulations of compounds of formulae (I)-(VI) or pharmaceutical compositions of the invention may also be administered by injection, intravenously (bolus and/or infusion), subcutaneously, intramuscularly, colonically, rectally, nasally, transdermally or intraperitoneally. A variety of dosage forms may be employed as well including, but not limited to, suppositories, implanted pellets or small cylinders, aerosols, oral dosage formulations and topical formulations such as ointments, drops and dermal patches. The compounds of formulae (I)-(VI) and pharmaceutical compositions of the invention may also be incorporated into shapes and articles such as implants which may employ inert materials such biodegradable polymers or synthetic silicones as, for example, SILASTIC, silicone rubber or other polymers commercially available. The compounds and pharmaceutical compositions of the invention may also be administered in the form of liposome delivery systems, such as small unilamellar vesicles, large unilamellar vesicles and multilamellar vesicles. Liposomes can be formed from a variety of lipids, such as cholesterol, stearylamine or phosphatidylcholines. [0061] Therapeutically effective dosages may be determined by either in vitro or in vivo methods. For each particular compound or pharmaceutical composition of the invention, individual determinations may be made to determine the optimal dosage required. The range of therapeutically effective dosages will be influenced by the route of administration, the therapeutic objectives and the condition of the patient. For injection by hypodermic needle, it may be assumed the dosage is delivered into the bodily fluids. For other routes of administration, the absorption efficiency must be individually determined for each compound by methods well known in pharmacology. Accordingly, it may be necessary for the therapist to titer the dosage and modify the route of administration as required to obtain the optimal therapeutic effect. [0062] The determination of effective dosage levels, that is, the dosage levels necessary to achieve the desired result, i.e., platelet ADP receptor inhibition, will be readily determined by one skilled in the art. Typically, applications of a compound or pharmaceutical composition of the invention are commenced at lower dosage levels, with dosage levels being increased until the desired effect is achieved. The compounds and compositions of the invention may be administered orally in an effective amount within the dosage range of about 0.01 to 1000 mg/kg in a regimen of single or several divided daily doses. If a pharmaceutically acceptable carrier is used in a pharmaceutical composition of the invention, typically, about 5 to 500 mg of a compound of formulae (I)-(VI) is compounded with a pharmaceutically acceptable carrier as called for by accepted pharmaceutical practice including, but not limited to, a physiologically acceptable vehicle, carrier, excipient, binder, preservative, stabilizer, dye, flavor, etc. The amount of active ingredient in these compositions is such that a suitable dosage in the range indicated is obtained. [0063] Typical adjuvants which may be incorporated into tablets, capsules and the like include, but are not limited to, binders such as acacia, corn starch or gelatin, and excipients such as microcrystalline cellulose, disintegrating agents like corn starch or alginic acid, lubricants such as magnesium stearate, sweetening agents such as sucrose or lactose, or flavoring agents. When a dosage form is a capsule, in addition to the above materials it may also contain liquid carriers such as water, saline, or a fatty oil. Other materials of various types may be used as coatings or as modifiers of the physical form of the dosage unit. Sterile compositions for injection can be formulated according to conventional pharmaceutical practice. For example, dissolution or suspension of the active compound in a vehicle such as an oil or a synthetic fatty vehicle like ethyl oleate, or into a liposome may be desired. Buffers, preservatives, antioxidants and the like can be incorporated according to accepted pharmaceutical practice. Pharmacological Assays [0064] The pharmacological activity of each of the compounds according to the invention is determined by the following in vitro assays: I. Inhibition of ADP-Mediated Platelet Aggregation In Vitro [0065] The effect of testing the compound according to the invention on ADP-induced human platelet aggregation is preferably assessed in 96-well microtiter assay (see generally the procedures in Jantzen, H. M. et al. (1999) Thromb. Hemost. 81:111-117). Human venous blood is collected from healthy, drug-free volunteers into ACD (85 mM sodium citrate, 111 mM glucose, 71.4 mM citric acid) containing PGI 2 (125 ml ACD containing 1.6 μM PGI 2 /10 ml blood; PGI 2 was from Sigma, St. Louis, Mo.). Platelet-rich plasma (PRP) is prepared by centrifugation at 160×g for 20 minutes at room temperature. Washed platelets are prepared by centrifuging PRP for 10 minutes at 730 g and resuspending the platelet pellet in CGS (13 mM sodium citrate, 30 mM glucose, 120 mM NaCl; 2 ml CGS/10 ml original blood volume) containing 1 U/ml apyrase (grade V, Sigma, St. Louis, Mo.). After incubation at 37° C. for 15 minutes, the platelets are collected by centrifugation at 730 g for 10 minutes and resuspended at a concentration of 3×10 8 platelets/ml in Hepes-Tyrode's buffer (10 mM Hepes, 138 mM NaCl, 5.5 mM glucose, 2.9 mM KCl, 12 mM NaHCO 3 , pH 7.4) containing 0.1% bovine serum albumin, 1 mM CaCl 2 and 1 mM MgCl 2 . This platelet suspension is kept >45 minutes at 37° C. before use in aggregation assays. [0066] Inhibition of ADP-dependent aggregation is preferably determined in 96-well flat-bottom microtiter plates using a microtiter plate shaker and plate reader similar to the procedure described by Frantantoni et al., Am. J. Clin. Pathol. 94, 613 (1990). All steps are performed at room temperature. The total reaction volume of 0.2 ml/well includes in Hepes-Tyrodes buffer/0.1% BSA: 4.5×10 7 apyrase-washed platelets, 0.5 mg/ml human fibrinogen (American Diagnostica, Inc., Greenwich, Conn.), serial dilutions of test compounds (buffer for control wells) in 0.6% DMSO. After about 5 minutes preincubation at room temperature, ADP is added to a final concentration of 2 μM which induces submaximal aggregation. Buffer is added instead of ADP to one set of control wells (ADP − control). The OD of the samples is then determined at 490 nm using a microtiter plate reader (Softmax, Molecular [0000] Devices, Menlo Park, Calif.) resulting in the 0 minute reading. The plates are then agitated for 5 min on a microtiter plate shaker and the 5 minute reading is obtained in the plate reader. Aggregation is calculated from the decrease of OD at 490 nm at t=5 minutes compared to t=0 minutes and is expressed as % of the decrease in the ADP control samples after correcting for changes in the unaggregated control samples. II. Inhibition of [ 3 H]2-MeS-ADP Binding to Platelets [0067] Having first determined that the compounds according to the invention inhibit ADP-dependent platelet aggregation with the above assay, a second assay is used to determine whether such inhibition is mediated by interaction with platelet ADP receptors. Utilizing the second assay the potency of inhibition of such compounds with respect to [ 3 H]2-MeS-ADP binding to whole platelets is determined. [ 3 H]2-MeS-ADP binding experiments are routinely performed with outdated human platelets collected by standard procedures at hospital blood banks. Apyrase-washed outdated platelets are prepared as follows (all steps at room temperature, if not indicated otherwise): [0068] Outdated platelet suspensions are diluted with 1 volume of CGS and platelets pelleted by centrifugation at 1900×g for 45 minutes. Platelet pellets are resuspended at 3−6×10 9 platelets/ml in CGS containing 1 U/ml apyrase (grade V, Sigma, St. Louis, Mo.) and incubated for 15 minutes at 37° C. After centrifugation at 730×g for 20 minutes, pellets are resuspended in Hepes-Tyrode's buffer containing 0.1% BSA (Sigma, St. Louis, Mo.) at a concentration of 6.66×10 8 platelets/ml. Binding experiments are performed after >45 minutes resting of the platelets. [0069] Alternatively, binding experiments are performed with fresh human platelets prepared as described in I. (Inhibition of ADP-Mediated Platelet Aggregation in vitro), except that platelets are resuspended in Hepes-Tyrode's buffer containing 0.1% BSA (Sigma, St. Louis, Mo.) at a concentration of 6.66×10 8 platelets/ml. Very similar results are obtained with fresh and outdated platelets. [0070] A platelet ADP receptor binding assay using the tritiated potent agonist ligand [ 3 H]2-MeS-ADP (Jantzen, H. M. et al. (1999) Thromb. Hemost. 81:111-117) has been adapted to the 96-well microtiter format. In an assay volume of 0.2 ml Hepes-Tyrode's buffer with 0.1% BSA and 0.6% DMSO, 1×10 8 apyrase-washed platelets are preincubated in 96-well flat bottom microtiter plates for 5 minutes with serial dilutions of test compounds before addition of 1 nM [ 3 H]2-MeS-ADP ([ 3 H]2-methylthioadenosine-5′-diphosphate, ammonium salt; specific activity 48-49 Ci/mmole, obtained by custom synthesis from Amersham Life Science, Inc., Arlington Heights, Ill., or NEN Life Science Products, Boston, Mass.). Total binding is determined in the absence of test compounds. Samples for nonspecific binding may contain 10 −5 M unlabelled 2-MeS-ADP (RBI, Natick, Mass.). After incubation for 15 minutes at room temperature, unbound radioligand is separated by rapid filtration and two washes with cold (4-8° C.) Binding Wash Buffer (10 mM Hepes pH 7.4, 138 mM NaCl) using a 96-well cell harvester (Minidisc 96, Skatron Instruments, Sterling, Va.) and 8×12 GF/C glassfiber filtermats (Printed Filtermat A, for 1450 Microbeta, Wallac Inc., Gaithersburg, Md.). The platelet-bound radioactivity on the filtermats is determined in a scintillation counter (Microbeta 1450, Wallac Inc., Gaithersburg, Md.). Specific binding is determined by subtraction of non-specific binding from total binding, and specific binding in the presence of test compounds is expressed as % of specific binding in the absence of test compounds dilutions. [0071] It should be understood that the foregoing discussion, embodiments and examples merely present a detailed description of certain preferred embodiments. It will be apparent to those of ordinary skill in the art that various modifications and equivalents can be made without departing from the spirit and scope of the invention. All the patents, journal articles and other documents discussed or cited above are herein incorporated by reference.
Novel compounds of formula (I) to (VI), which more particularly include sulfonylurea derivatives, sulfonylthiourea derivatives, sulfonylguanidine derivatives, sulfonylcyanoguanidine derivatives, thioacylsulfonamide derivatives, and acylsulfonamide derivatives which are effective platelet ADP receptor inhibitors. These derivatives may be used in various pharmaceutical compositions, and are particularly effective for the prevention and/or treatment of cardiovascular diseases, particularly those diseases related to thrombosis. The invention also relates to a method for preventing or treating thrombosis in a mammal comprising the step of administering a therapeutically effective amount of a compound of formulae (I)-(VI), or a pharmaceutically acceptable salt thereof.
2
BACKGROUND OF THE INVENTION The present invention relates to selectively colorable compositions and to a method for forming selectively colored polymeric bodies using such compositions. Commonly assigned U.S. Pat. No. 5,942,554 discloses a curable composition containing a color precursor and an onium salt which is both cured and colored upon exposure to actinic radiation. Color precursors disclosed as being useful are those which are capable of reacting with acid or whose excited states are capable of donating an election. Commonly assigned U.S. patent application Ser. No. 09/558,599 filed on Apr. 26, 2000, now U.S. Pat. No. 6,309,797 discloses selectively colorable polymerizable compositions comprising a leucobase color former and a leuconitrile color former. Irradiation of the composition cures and selectively colors the composition. The color at any one location depends on the actinic dose and the interaction of the leucobase and leuconitrile colorformers. In one embodiment, a selectively colorable, polychromic composition is provided wherein low light exposure creates a polymer of one color, intermediate light exposure changes the color of the polymer and a high dosage of light exposure bleaches the color of the polymer. International Publication Number WO 97/09168 to Zeneca discloses a photocurable, photocolorable composition which is irradiated with a low dose of light to cure and a different dose of light, preferably higher, to cause color formation. Color formation or color change occurs as a result of contact between a colorformer and a photochemically generated developer. The colorformers disclosed as being useful include lactones, fluorans, etc. which are acid sensitive compounds. A selectively colorable solid object is an object that can be colored at small individual, but specifically defined, sites by irradiating light of a particular wavelength and specific intensity for a specified duration. The light sources capable of producing the selectively colorable solid object include: (a) a laser interfaced with an XY scanner (for polymer films), (b) a laser interfaced with an XYZ scanner (for 3D parts), (c) digital mirror device, (d) UV and Visible lamps with a masking device, etc. A selectively colorable resin (SCR) system consists of: (a) the matrix (a blend of polymerizable material or a solid polymer), (b) a color former, (c) a color initiator (species that generate other species capable of reacting with color former; may not be needed in some systems); and (d) a chain reaction initiator (radical or cationic or none depending on the system). The conventional method for forming a colored plastic body is to add a dye or pigment to the liquid prepolymer composition. The composition is then cured with actinic radiation. The latter requires that the absorption spectra of the photoinitiator and the dye/pigment differ. If the dye/pigment absorbs actinic radiation at the same wavelength as the photoinitiator, slower or no cure will be achieved. The color formation method is also not selective. The entire plastic is uniformly colored. Still another problem is that the photopolymerization process requires actinic radiation, but the color forming process requires only that the composition be well mixed. Though one of the processes can be controlled by the intensity/wavelength of the actinic radiation, the other is unaffected by it. Thus there is no selectivity of color formation in the plastic body. Accordingly, there is a need for selectively colorable polymerizable compositions and for a method of forming selectively colored polymeric bodies using such compositions wherein the colorization process can be controlled as to the location and intensity of the color formed. SUMMARY OF THE INVENTION The present invention discloses selectively colorable compositions and a method for forming selectively colored polymeric bodies using such compositions. In accordance with the invention, a selectively colorable polymerizable composition comprising a leucobase color former and an oxidizing agent is irradiated with light of a particular wavelength and specific intensity for a specified duration. Exposure to actinic radiation cures the composition and activates the color former which can be optionally deactivated or bleached by further exposure. The irradiation dosage can be varied to selectively color the polymeric body whereby the resultant color of any particular area depends on the exposure dose received at that location. By varying the dose, a polymeric body can be prepared having distinctly colored elements at specific locations. It is believed that, upon irradiation of the polymerizable composition of the present invention containing a polymerizable compound, a leucobase color former and an onium salt, two processes occur for color formation and bleaching. One process generates a dye cation via electron transfer process upon exposure of a leucobase dye precursor in the presence of an oxidizing agent and a second process is the bleaching of the dye cation upon further exposure. Accordingly, the composition of the present invention provides a photopolymerizable selectively colorable system. The bleaching process is efficient only when the starting material is an acid non-sensitive leucobase. The initial color is formed by a photooxidation process which involves electron transfer from the leucodye to the oxidizing agent. The bleaching process is not nearly as efficient in the case when the starting material is a dye or an acid-sensitive dye. Under low dosage, color formation depends primarily on Scheme 1 wherein exposure of a leucobase to light in the presence of a oxidizing agent yields a dye cation. The mechanism is illustrated below for a triarylmethane (TAM) leucobase (TAMH) susceptible to oxidation. Ox represents an oxidizing agent, TAM + represents the colored species and hv represents exposure to actinic radiation. It is anticipated that the scheme below will also be valid for diarylmethane (DAM) and other photooxidizable leucodyes which do not form the color with acid on contact. TAMH+Ox+hνTAM + (colored)  Scheme 1 At higher doses of irradiation, bleaching of TAM + occurs (Scheme 2). Therefore, the color of the polymeric body at higher doses disappears and the contrast is produced. (TAM) + +hν bleaching products (colorless)  Scheme 2 In another embodiment of the present invention, the oxidation process can be inhibited significantly by the introduction of at least one electron-withdrawing group (e.g., halogen, NO 2 , COR, COOR, etc., where R is H, hydrocarbon, etc.) to the TAM-H or DAM-H aromatic structure. In this case, color formation is delayed allowing one to obtain colorless polymer at low doses, colorize the polymer at an intermediate dose and bleach the color by further irradiation. DETAILED DESCRIPTION OF THE INVENTION In accordance with the present invention, a composition which can be selectively colored by exposure to actinic radiation and a method leading to the formation of selectively colored, polymer bodies that can be cured photochemically are provided. The invention is particularly useful for the selective color development and photopolymerization of films using a leucobase color former and an oxidizing agent. The composition of the present invention can be used in a solid or a liquid. Those skilled in the art will appreciate that the color determinative irradiation step can be conducted before, after or simultaneously with the polymerization or crosslinking step. Furthermore, selective coloration of a polymeric body in accordance with the present invention can be carried out using one exposure or light source to polymerize or crosslink the composition and a second exposure or light source to induce the photochromic response, or using a single light source to polymerize the composition at a first intensity and using the same light source at a plurality of intensities to induce the photochromic response. The latter system has the advantage that it involves the use of only one light source and it will be appreciated that this system is easily implemented using highly sensitive photohardenable systems, which can be easily polymerized using a lower intensity light exposure. As a general rule, agents, such as photoinitiators, used to initiate polymerization will be more efficient than the photoresponsive agents described below so more or different energy will be required to color or bleach the selectively colorable composition than to form the polymeric film or body and colorization or bleaching will be induced at higher intensities than polymerization. The present invention involves the interaction of a leucobase color former and an oxidizing agent to generate a photosensitive selectively colorable composition. The color former yields a dye cation upon actinic exposure in the presence of an oxidizing agent via electron-transfer process. The The dye cation is then bleached upon further actinic exposure to yield colorless species. The rate of the initial oxidation process can be decreased and controlled by the introduction of at least one electron-withdrawing group (e.g., halogen, N 2 , COR, COOR, etc., where R is H, hydrocarbon, etc.) to the TAM-H or DAM-H structure. In this case, color formation is delayed allowing one to obtain colorless polymer at low doses, colorize the polymer at an intermediate dose and bleach the color by further irradiation. Examples of leucobases which yield a colored cation upon exposure to actinic radiation in the presence of an oxidizing agent include thiazine, oxazine and phenazine leucobases as well as triarylmethane leucobases (TAM-X), diarylmethane leucobases (DAM-X) and monoarylmethane leucobases (Ar—CR 2 X) wherein X is H, OH, OR, NR 2 , N-heterocycle, and R is hydrogen, a straight chain, branched chain or cyclic alkyl group containing 1 to 20 carbon atoms, aryl (e.g., phenyl) or aralkyl (e.g., a phenylalkyl group in which the alkyl moiety contains 1 to 6 carbon atoms) and the like. Preferably, the color former is a triarylmethane or diarylmethane leucobase susceptible to oxidation, with diarylmethane leucobase (DAM-H) being the most preferred color former. Color formers useful in the present invention are preferably stable in acidic media and do not form color on contact with acid. The term “stable in acidic media” as used herein indicates that the color former will not exhibit more that 0.005% conversion to its colored form in acidic conditions. Stability of the leucobase in acidic media allows it to be used in cationically cured materials for selective color formation. Examples of triarylmethane leucobase color formers include tris(4-(N,N-dimethylamino) phenyl)methane (Leuco Crystal Violet), tris(4-aminophenyl)methane (Leuco Basic Fuchsin), bis(4-(N,N-dimethylamino)phenyl)pentafluorophenylmethane, bis(4-(N,N-dimethylamino)phenyl) -2-fluorophenylmethane, bis(4-(N,N-dimethylamino)phenyl)-3-fluorophenylmethane, bis(4-(N,N-dimethylamino)phenyl)-2,6-difluorophenylmethane, bis(3-(2-methylindyl))phenylmethane, and the like. Examples of diarylmethane leucobase color formers include bis(4-aminophenyl)methane, bis(4-(N,N-dimethylamino)phenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3-chlorophenyl)methane, bis(4-amino-2-chloro-3,5-diethylphenyl)methane, bis(4-aminophenyl)methane, 4-aminophenyl-(4-amino-3-bromophenyl)methane and the like. Oxidizing agents useful in the present invention include compounds which are electron acceptors capable of oxidizing the leuco dye and generating the colored carbocation. Typical photosensitive oxidizing agents include onium salts such as iodonium, sulfonium and the like, transition metals, iron salts, uranyl salts, etc. used in the absence or presence of an oxidizing species such as hydrogen peroxide. The oxidizing agent, to oxidize the leuco dye, will have a photoreduction potential less than the color former. Onium salts such as sulfonium or iodonium salts are particularly preferred for use as oxidizing agents in the invention. It is believed that upon photochemical or thermal decomposition, an iodonium salt generates radicals and cations, either or both of which can be used to initiate polymerization, while oxidizing the color precursor which converts the color precursor into its colored form. Self-coloring photohardenable compositions in accordance with the present invention in their simplest form include a curable compound, an onium salt and a color precursor. In some cases, the compositions may,also include a hydrogen donor, although not essential in the principal embodiments, and for many applications it will also be desirable to include a photoinitiator in the composition. While triarylsulfonium salts such as triarylsulfonium hexafluoroantimonate or mixtures of triarylsulfonium hexafluoroantimonates and the like are preferred onium salts, other sulfonium salts and iodonium salts are also suitable for use in the invention. Decomposition of triarylsulfonium hexafluoroantimonate can be achieved photochemically. Examples of onium salts useful in the present invention include iodonium salts and sulfonium salts and, more particularly, diaryliodonium hexaflurophosphates, diaryliodonium arsenates and diaryliodonium antimonates. The counter ion of the onium salts is usually a nonnucleophilic semimetal complex such as B(C 6 F 5 ) 4 − , Al(C 6 F 5 ) 4 − , Ga(C 6 F 5 ) 4 − , In(C 6 F 5 ) 4 − , Th(C 6 F 5 ) 4 − , SbF 6 − , AsF 6 − , PF 6 − , and BF 4 − . A more complete list of iodonium salts appears in published International Application PCT/US/95/056 13. Representative examples of iodonium salts include salts having the following structures: C n H 2n−1 C 6 H 4 I + (C 6 H 5 ), (C n H 2n−1 C 6 H 4 ) 2 I + , (C n H 2n+1 OC 6 H 4 )I + (C 6 H 5 ) and (C n H 2n+1 OC 6 H 4 ) 2 I + wherein is preferably 1 and typically 8 to 12 and most preferably, the diaryliodonium salts such as 4,4′-dimethyldiphenyliodonium tetrafluoroborate and (4-octyloxyphenyl) phenyliodonium hexafluoroantimonate (OPPI). Representative examples of sulfonium salts include triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, triarylsulfonium tetra(perfluoro)phenylgallate, tetra(perfluoro)phenylborate and the like. Examples of particularly preferred onium salts include 1.) OPPI and 2.) a mixture of triarylsulfonium hexafluoroantimonates (UVI-6974 from Union Carbide). Because decomposition of the onium salt is accompanied by the generation of free radicals and cations, the curable material may be a free radical curable or a cation curable material or a blend of the two. There is a large number of monomers which can be polymerized by cations. These monomers can be classified according to their functionality. They include cyclic ethers, cyclic formals and acetals, vinyl ethers, and epoxy compounds. These monomers can be monofunctional, difunctional and multifunctional. They may also be large molecular weight prepolymers and oligomers. Examples of cationically polymerizable compounds include epoxy compounds, vinyl or allyl monomers, vinyl or allylic prepolymers, vinyl ethers, vinyl ether functional prepolymers, cyclic ethers, cyclic esters, cyclic sulfides, melamineformaldehyde prepolymers, phenol formaldehyde prepolymers, cyclic organosiloxanes, lactams and lactones, cyclic acetals and epoxy functional silicone oligomers. Epoxy monomers are the most important class of cationic polymerizable substrates. These materials are readily available and the resulting cured polymers possess excellent dimensional and thermal stability as well as superior mechanical strength and chemical resistance. They are widely used in the coating, painting and adhesives industry. Examples of cationically polymerizable epoxy compounds described in the literature include any monomeric, dimeric or oligomeric or polymeric epoxy material containing one or a plurality of epoxy functional groups. Examples of polymerizable epoxy compounds include bisphenol-A-diglycidyl ether, trimethylene oxide, 1,3-dioxolane, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexyl carboxylate, phenyl glycidyl ether, 4-vinylcyclohexene dioxide, limonene dioxide, cycloaliphatic epoxides such as 1,2-cyclohexene oxide, epichlorohydrin, glycidyl acrylate, glycidyl methacrylate, styrene oxide, allyl glycidyl ether, etc. Resins which result from the reaction of bisphenol A (4,4-isopropylidenediphenol) and epichlorohydrin, or from the reaction of low molecular weight phenol-formaldehyde resins (Novolak resins) with epichlorohydrin have been used alone or in combination with an epoxy containing compound. In addition, polymerizable epoxy compounds include polymeric materials containing terminal or pendant epoxy groups. Examples of these compounds are vinyl copolymers containing glycidyl acrylate or methacrylate as one of the comonomers. Other classes of epoxy containing polymers amenable to cure have also been described in the literature and include epoxy-siloxane resins, epoxy-polyurethanes and epoxy-polyesters. Such polymers usually have epoxy functional groups at the ends of their chains. Epoxy-siloxane resins and the method for making them are more particularly shown by E. P. Plueddemann and G. Ganger, J. Am. Chem. Soc. 81 632-5 (1959), and in Crivello et al., Proceeding ACS, PMSE, 60, 217 (1989). As described in the literature, epoxy resins can also be modified in a number of standard ways such as reactions with amines, carboxylic acids, thiols, phenols, alcohols, etc. as shown in U.S. Pat. Nos. 2,935,488; 3,235,620; 3,369,055; 3,379,653; 3,398,211; 3,403,199; 3,563,850; 3,567,797; 3,677,995, etc. Further examples of epoxy resins are shown in the Encyclopedia of Polymer Science and Technology, Vol. 6, 1967, Interscience Publishers, New York, pp. 209-271. Examples of vinyl or allyl organic monomers which have been used in the literature in the practice of the cationic polymerization include, for example, styrene, vinyl acetamide, methyl styrene, isobutyl vinyl ether, n-octyl vinylether, acrolein, 1-diphenylethylene. R-pinene; vinyl arenes such as 4-vinyl biphenyl, 1-vinyl pyrene, 2-vinyl fluorene, acenapthylene, 1 and 2-vinyl napthylene; 9-vinyl carbazole, vinyl pyrrolidone, 3-methyl-1-butene; vinyl cycloaliphatics such as vinylcyclohexane, vinylcyclopropane, 1-phenyvinylcyclopropane; dienes such as isobutylene, isoprene, butadiene, 1,4-pentadiene, 2-chloroethyl vinyl ether, etc. Some of the vinyl organic prepolymers which have been described are, for example, CH 2 ═CH—O—(CH 2 O) n —CH═CH 2 , where n is a positive integer having a value up to about 1000 or higher; multi-functional vinylethers, such as 1,2,3-propane trivinyl ether, trimetheylolpropane trivinyl ether, polyethyleneglycol divinylether (PEGDVE), triethyleneglycol divinyl ether (TEGDVE), vinyl ether-polyurethane, vinyl ether-epoxy, vinyl ether-polyester, vinyl ether-polyether and other vinyl ether prepolymers such as 1,4-cyclohexane dimethanol-divinylether, commercially available from GAF and others, and low molecular weight polybutadiene having a viscosity of from 200 to 10,000 centipoises at 25° C., etc. A further category of cationically polymerizable materials are cyclic ethers which are convertible to thermoplastics. Included by such cyclic ethers are, for example, oxetanes such as 3,3-bis-chloromethyloxetane alkoxyoxetanes as shown by U.S. Pat. No. 3,673,216; oxolanes such as tetrahydrofuran, oxepanes, oxygen containing spiro compounds, trioxane, dioxolane, etc. In addition to cyclic ethers, there are also included cyclic esters such as lactones, for example, propiolactone, cyclicamines, such as 1,3,3-trimethylazetidine and cyclic organosiloxanes, for example. Examples of cyclic organosiloxanes include hexamethyl trisiloxane, octamethyl tetrasiloxane, etc. Cyclic acetals may also be used as the cationic polymerizable material. Examples of epoxy functional silicone oligomers are commercially available from General Electric and are described in ACS PMSE Proceeding 1989, Vol. 60, pp. 217, 222. Because the photoinitiator generates both free radicals and cations, it is possible to utilize a combination of free radical polymerizable and cationic polymerizable monomers. Examples of free radical polymerizable monomers include both monomers having one or more ethylenically unsaturated groups, such as vinyl or allyl groups, and polymers having terminal or pendant ethylenic unsaturation. Such compounds are well known in the art and include acrylic and methacrylic esters of polyhydric alcohols such as trimethylolpropane, pentaerythritol and the like, and acrylate or methacrylate terminated epoxy resins, acrylate or methacrylate terminated polyesters, etc. Representative examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate (TMPTA), pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hydroxypentacrylate (DPHPA), hexanediol-1, 6-dimethacrylate, and diethyleneglycol dimethacrylate. Examples of materials which are both cationically and free radically cured include glycidyl methacrylates, epoxy acrylates, acrylated melamine formaldehyde and epoxidized siloxanes. The simultaneous utilization of a cationically and free radical curable system enables rapid curing to be accomplished and provides a wide latitude in the design of product performance. For example, when a solution of acrylate and epoxy acrylate is used as the dual curable composition, film properties ranging from flexible to rigid can be produced and desired adhesive characteristics can be produced by selection of designed ratios of functional groups. The epoxy functionality provides high temperature resistance, excellent adhesion and reduced oxygen sensitivity whereas the acrylate functionality provides rapid curing speed, excellent weatherability, flexibility and desirable viscosity. Other examples of dual curable systems will be envisioned and appreciated by those skilled in the art. It has been found that a mixture of an acrylate and an epoxy compound is particularly desirable for use herein. In accordance with one embodiment of the present invention, a photoinitiator is included in the self coloring photohardenable composition. Some typical examples of photoinitiators which are expected to be useful in the present invention are α-alkoxy phenyl ketones, O-acylated-α-oximinoketones, polycyclic quinones, benzophenones and substituted benzophenones, xanthones, thioxanthones, halogenated compounds such as chlorosulfonyl and chloromethyl polynuclear aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethyl benzophenones and fluorenones, haloalkanes, α-halo-α-phenylacetophenones, halogenated paraffins (e.g., brominated or chlorinated paraffin) and benzoin alkyl ethers. A wide range of xanthene or fluorone dyes may be used as photoinitiators in accordance with the invention. Some examples include Methylene Blue, rhodamine B, Rose Bengal, 3-hydroxy-2,4,5,7-tetraiodo-6-fluorone, 5,7-diiodo-3-butoxy-6-fluorone, erythrosin B, Eosin B, ethyl erythrosin, Acridine Orange, 6′-acetyl-4′,5′,6′,7′-tetraiodofluorescein (RBAX), and the fluorones disclosed in U.S. Pat. No. 5,451,343. For some applications it may be desirable to include a hydrogen donor in the compositions of the invention. Useful hydrogen donors can be selected from among those known in the art and, more particularly, from known hydrogen donating coinitiators. Non-nucleophilic amines such as aromatic amines of low basicity are particularly useful in the invention. The relative efficiency of the hydrogen donor in cationic polymerization not only depends on the efficiency of radical generation, but also on the efficiency of the oxidation of the radicals to cations as well as on the efficiency of the cation to initiate the cationic polymerization. The hydrogen donor must have a low basicity and low nucleophilicity. If the hydrogen donor is too basic, it will deactivate the cationic center responsible for initiation. Only aromatic amines with a hydrogens are capable of initiating ring opening polymerization of cyclohexene oxide. Aliphatic amines, aromatic amines without α-hydrogens and non-amine hydrogen donors are incapable of the initiation with cyclohexene oxide. Representative examples of N,N-dialkylanilines useful in the present invention are 4-cyano-N,N-dimethylaniline, 4-acetyl-N,N-dimethylaniline, 4-bromo-N,N-dimethylaniline, 4-methyl-N,N-dimethylaniline, 4-ethoxy-N N-dimethylaniline, N,N-dimethylthioanicidine, 4-amino-N,N-dimethylaniline, 3-hydroxy-N,N-dimethylaniline, N,N,N′N′-tetramethyl-1,4-dianiline, 4-acetamido-N,N-dimethylaniline, 2,6-diethyl-N,N-dimethylaniline, N,N,2,4,6-pentamethylaniline(PMA) p-t-butyl -N,N-dimethylaniline and N,N-dimethyl-2,6-diisopropyl aniline. Also useful as hydrogen donors are N-phenylglycine and N,N-dimethyltoluidine. However, the invention is not limited to the use of amines or aromatic amines as hydrogen donors. Other compounds present in the composition may be capable of functioning as a hydrogen donor. For example, many monomers are capable of acting as hydrogen donors and compositions containing these compounds may be used effectively with or without amines. Specific examples of such monomers include certain cycloaliphatic epoxides. Solvents may be necessary to dissolve components of the system including the photoinitiator, the color precursor, etc., if they are not sufficiently soluble in the monomer. Some examples of useful solvents are ethyl acetate, etc. Other useful solvents can be identified readily. The nature of the monomer or polymerizable material, the amount of the color precursor and onium salt in curable self-coloring compositions in accordance with the present invention will vary with the particular use of the compositions, the emission characteristics of the exposure sources, the development procedures, the physical properties desired in the polymerized product and other factors. With this understanding, compositions in accordance with the invention will generally fall within the following compositional ranges in parts by weight (based on 100 parts total). Curable compound 60 to 99 Color Precursors 0.001 to 1  Photoinitiator 0 to 10 Onium Salt 0.05 to 15 Compositions in accordance with the invention more typically are anticipated to have the following formulation: Curable compound(s) 85 to 98  Color Precursors 0.02 to 0.2 Photoinitiator 0.5 to 7.0 Onium Salt 0.1 to 7.0 Preferably, the color formers are present in an amount sufficient to provide a contrast ratio of at least 1.5, more preferably at least 10, or provide a contrast ratio of less than 0.7 in the case of reversed contrast. The term “contrast ratio” means the ratio of absorbance maximum values at two doses. These doses are the largest dose and the dose at which the polymer is formed unless specified otherwise. As used herein contrast ratio refers to the absorbance of the colored polymeric film or body at the high irradiation dose divided by the absorbance at the low dose at the specified wavelength. Contrast ratio is a function of a number of variables including, but not limited to, the light source, irradiation dosage, curable compound, photoinitiator and color formers. The number of color formers, type of color formers, the concentration of the color formers, the interaction between the different color formers and the relative concentrations of the color formers influence the contrast ratio. The compositions of the present invention are useful in the following applications: creating color contrast in printing plates such as in flexographic plates, other proofing and identification purposes, end of line manufacturing identification, fraud protection, selective imagewise colorization of a wire or other plastic objects, color printing of relief and 3D images with various light sources, and the like. The photohardenable composition of the invention may also be advantageous for use in the three dimensional modeling process taught in U.S. Pat. No. 4,575,330 to Hull and commonly assigned U.S. Pat. No. 5,514,519, the latter being hereby incorporated by reference. Irradiation of resins consisting of monomers, preferably acrylates or epoxides and most preferably a mixture of acrylates and epoxides, a leucobase color former and a sulfonium salt can result in selectively colored films in which the polymerization process and the color formation occur simultaneously. Alternatively, the polymerization process can be conducted prior to the color formation. In a preferred embodiment of the present invention, a photopolymerizable composition comprising a cationically polymerizable epoxide, a triarylsulfonium salt photoinitiator, an acrylate and a free radical photoinitiator is polymerized in the presence of a diarylmethane leucobase color former (DAMH). Color formation proceeds according to the following mechanisms: DAMH+Ox+hνDAM +   Mechanism 1 The color of the polymeric body at low doses is solely determined by DAM + . At high doses this cation is partially or completely bleached (Mechanism 2), thus, the polymer body has no or little color. DAM + +hνbleaching products (colorless)  Mechanism 2 In another embodiment of the present invention, the oxidation process can alternatively be inhibited significantly by the introduction of at least one electron-withdrawing group (halogen, NO 2 , COR, COOR, etc., where R is H or a hydrocarbon group) to the TAM-H or DAM-H, preferably DAM-H structure. In this case, the color formation is delayed allowing one to obtain colorless polymer at low doses, colorize it at higher doses and bleach the color at even higher doses. Although the present invention has been primarily described by reference to polymerizable compositions, the invention is not so limited. The selectively colorable compositions can be liquids or solids which form color on exposure to actinic radiation and the color so formed can be bleached by further irradiation. The present invention is further illustrated by the following, non-limiting examples: EXAMPLE 1 A selectively colorable photocurable composition can be prepared by including 0.03% bis(4-aminophenyl)methane as a DAM-H color former in Resin 1, a hybrid resin containing cationically polymerizable epoxide(s) (60-90%), triarylsulfonium hexafluoroantimonate photoinitiator(s) (0.5-8%), acrylate esters (5-35%) and free radical initiator(s) (0.5-5.0%). The contrast ratio obtained is close to zero because the blue color is bleached away. The polymer colors are blue and slightly yellow. EXAMPLE 2 A selectively colorable photocurable composition can be prepared by including 0.025% bis(4-amino-3-chlorophenyl) methane as a DAM-H color former with at least one electron-withdrawing group in its structure in Resin 2, a hybrid resin containing cationically polymerizable epoxides(s) (60-90%), triarylsulfonium hexafluoroantimonate photoinitiator(s) (2-10%), acrylate esters (5-25%), and free radical photoinitiators(s) (1-10%). The polymer colors are none (40 mJ/cm 2 ), green (400 mJ/cm 2 ) and yellowish (1 J/cm 2 ). Experimental Procedure for Examples 1 and 2 Samples are prepared as follows: A 200 micron thin layer is drawn down on a glass slide. It is scanned with a He/Cd (325 nm) laser (Example 1) or a NdYAG pulsed (354 nm) laser (Example 2) with a 1.5 mm diameter beam. The dose ranges from 30-1000 mJ/cm 2 with a typical maximum dose being 600 mJ/cm 2 . A low dose of 30 to 80 mJ/cm 2 is employed to polymerize the composition. A contrast ratio is measured at the maximum absorption with the absorbance at the high dose being ratioed to the absorbance at the lowest dose at the specified wavelength. EXAMPLE 3 A selectively colorable photocurable composition can be prepared by including 0.1% bis(4-aminophenyl)methane as a DAM-H color former in tetrahydrofuran (THF) solution containing 50wt % of low molecular weight polyvinylchloride (PVC) and 2-8% of a mixture of triarylsulfonium hexafluoroantimonates (UVI-6974). A 0.5 mm thin polymer film was cast on a glass slide as THF was evaporated. The sample turns blue when irradiated with an H-bulb high pressure mercury lamp at 100 mJ/cm 2 . The blue color faded when the sample was subjected to 1000 mJ/cm 2 from the same light source. Having described the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.
Selectively colorable compositions and a method for forming selectively colored polymeric bodies using such compositions are disclosed. In accordance with the invention, a selectively colorable polymerizable composition comprising a leucobase color former is irradiated with light of a particular wavelength and specific intensity for a specified duration. Exposure to actinic radiation cures the composition and activates the color former. Exposure to higher dosages of actinic radiation can bleach the composition. The irradiation dosage can be varied to selectively color the polymeric body whereby the resultant color of any particular area depends on the exposure dose received at that location. By varying the dose, a polymeric body can be prepared having distinctly colored elements at specific locations.
2
TECHNICAL FIELD The present invention relates to a vehicle cruise control system for automatically maintaining the speed of a vehicle at a fixed level. BACKGROUND OF THE INVENTION Various forms of cruise control systems are known. According to a typical cruise control system for an automobile, after a desired vehicle speed has been reached by manual operation of the throttle pedal, the set switch is activated and the actuator takes over the control of the throttle pedal and automatically maintains the vehicle speed at a constant level without requiring any efforts on the part of the driver. The actuator for such a cruise control system may consist of a vacuum actuator using engine vacuum or a motor driven actuator. A motor driven actuator is highly compact and is capable of performing an accurate control action. Typically, a transistor bridge circuit is used to selectively drive the actuator in either direction according to the need to accelerate or decelerate the vehicle. Such a drive circuit is required to be highly reliable and is desired to be equipped with various protective and fail-safe features. For instance, a CPU consisting of a micro processor used in the control unit for a cruise control system is normally provided with a watch dog timer circuit which keeps producing a certain steady pulse signal as long as the CPU is functioning normally, but produces a certain abnormal DC signal or a high frequency signal when the CPU has ceased to function normally. The abnormal output of this watch dog timer circuit is typically used to disconnect the electromagnetic clutch provided in the output shaft of the actuator to terminate the action of the cruise control. However, when the CPU stops functioning normally, it could produce confused control signals to the drive transistors and, depending on the combination of the confused control signals, some of the drive transistors may short-circuit and may be destroyed in a very short time. Therefore, it is desirable to provide a protective circuit to such a transistor bridge circuit and an example of such a protective circuit is disclosed in Japanese patent laid-open publication No. 57-119682. According to this disclosed protective circuit, a certain interlock circuit is provided to each pair of transistors which are not desired to be in conductive states at the same time so as to prevent them from being brought into conductive states at the same time. However, this solution involves the use of power transistors for conducting large electric current and this prevents compact design of the system and causes an increase in the manufacturing cost. Furthermore, even when no short-circuiting takes place, it is desirable whenever the CPU produces a confused output to disconnect the actuator or to drive the actuator in the direction to decelerate the vehicle according to the principle of fail-safe. However, the above mentioned solution does not offer this advantage. Typically, a cruise control is terminated when a brake pedal is pressed, when a clutch pedal is activated, and when a transmission gear is shifted. Additionally, as safety features, it is desirable to terminate the cruise control and/or to drive the actuator in the direction to decelerate the vehicle when the rotational speed of the engine has exceeded a certain limit, and when the vehicle speed has fallen below the target vehicle speed beyond a certain limit, and when any abnormal condition in the control circuit is detected. However, depending on the speed of the activation of such protective circuits, electric current may continue to be supplied to the drive circuit for a time period between the time point when the cruise control is activated the time point when the cruise control is terminated upon detection of any abnormal condition and this could cause destruction of a part of the circuitry or make the existing abnormal condition even worse. Therefore, it is highly desirable to run a self diagnostic routine before the cruise control is activated in view of improving the fail safe features of the cruise control system. In view of such problems of the prior art, a primary object of the present invention is to provide a vehicle cruise control system which fails in a safe manner whenever the CPU of the cruise control system produces a confused output. Another object of the present invention is to provide a vehicle cruise control system which is reliable and permits a compact design. According to the present invention, these and other objects of the present invention can be accomplished by providing a vehicle cruise control system, comprising a control circuit for producing a control signal for maintaining a speed of a vehicle at a fixed level according to a difference between an actual vehicle speed and a target vehicle speed, and a drive circuit for producing a drive signal for selectively driving an actuator in a direction either to accelerate the vehicle or to decelerate the vehicle according to the control signal from the control circuit, wherein: the drive circuit is provided with a transistor bridge circuit comprising four drive transistors for producing the drive signal while the control circuit is provided with a detection means for detecting an abnormal state of the system and an inhibiting means which brings at least one of the drive transistors into a non-conductive state when any abnormal state is detected by the detecting means. Thus, even when the control circuit produces a confused control signal, the detection means forces one of the drive transistors, typically one of the acceleration drive transistors, into a non-conductive state and not only the short-circuiting of the drive transistors is avoided but also the system is allowed to fail in a safe manner. One of the deceleration drive transistors may be brought into either a conductive state or non-conductive state. The detection means may comprise a circuit for monitoring the state of one of the drive transistors or a watch dog timer circuit for monitoring the action of a micro processor in the control circuit. According to a certain aspect of the present invention, the drive circuit comprises an acceleration drive circuit and a deceleration drive circuit, and the acceleration drive circuit is connected to a power line by way of a brake switch which opens upon pressing of a brake pedal while the deceleration drive circuit is directly connected to a power line as a favorable feature for permitting the system to be shut off and/or to decelerate the vehicle in a reliable manner. According to another aspect of the present invention, by sending a signal to one of the drive transistors to close it after a power switch of the vehicle cruise control system is turned on and before the set switch is activated, the opening capabilities of the transistors which are connected in series with the said closed drive transistor can be tested. In a vehicle cruise control system having a lower limit switch for disconnecting the motor when a limit of a stroke of the motor to decelerate the vehicle has been reached, by sending a deceleration signal to the transistor bridge circuit after a set switch for initiating a cruise control is activated and before the electromagnetic clutch is connected, the opening capabilities of the drive transistors located in a path for accelerating the vehicle can be tested. If an acceleration signal is sent to the transistor bridge circuit, the opening capabilities of the drive transistors in the path for decelerating the vehicle can be tested. Further, by sending a boosted acceleration signal for taking up slack in the linkage existing between the working end of the actuator and a speed control means of a vehicle engine immediately after the electromagnetic clutch is connected, the closing capabilities of the drive transistors located in a path for accelerating the vehicle can be tested. The opening capability of the transistor for driving the electromagnetic clutch can be tested by detecting electric current conducted by the transistor after the set switch for initiating the cruise control is activated and before the electromagnetic clutch is connected, and the closing capability of the transistor for driving the electromagnetic clutch can be tested by detecting electric current conducted by the transistors after the electromagnetic clutch is connected. BRIEF DESCRIPTION OF THE DRAWINGS Now the present invention is described in the following with reference to the appended drawings, in which: FIG. 1 is a circuit diagram of an embodiment of the vehicle cruise control system according to the present invention; FIG. 2 is a time chart for describing the action of the embodiment shown in FIG. 1; FIG. 3 is a simplified circuit diagram of the drive circuits in FIG. 1 for driving the electromagnetic clutch and the motor; and FIG. 4 is a circuit diagram of a part of a second embodiment of the vehicle cruise control system according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT FIG. 1 is a circuit diagram of an embodiment of the cruise control system according to the present invention. The control of this system is provided by a control unit 1 which comprises a voltage-regulator 2, an input control circuit 3, an input/output control circuit 4, an actuator drive circuit 5, an electric current detecting circuit 6 and a CPU 7 which consists of a micro processor. A terminal T1 of the control unit 1 receives a voltage from a battery 8 serving as a power source by way of an ignition switch 9, an over-current fuse 10 and a main switch 11. A main indicator lamp 12 is connected across the control unit end of the main switch 11 and the ground. In the control unit 1, the terminal T1 is connected to an input of the voltage regulator 2 and the regulated voltage which is produced at an output end of the voltage regulator 2 is supplied to the CPU 7. An output signal from a vehicle speed sensor 13 is supplied to an input of the input control circuit 3 by way of a terminal T2 of the control unit 1 and signals from a set switch 15 and a resume switch 16 which are connected to the battery 8 by way of a common fuse 14 are supplied to terminals T3 and T4 of the control unit 1. The signals from the vehicle sensor 13, the set switch 15 and the resume switch 16 are supplied to the CPU 7 by way of terminals T2, T3 and T4, respectively, and the input control circuit 3. Terminal T11G is a ground terminal of the control unit 1. Terminals T5 and T6 of the control unit 1 are connected to contacts S1 and S2 of a brake switch 18 which detects the activation of a brake pedal which is not shown in the drawings. The contact S1 is a normally open contact which connects the terminal T5 to the battery 8 by way of a fuse 17 when the brake pedal is pressed while the contact S2 is a normally closed contact which connects the terminal T6 to the nonregulated power line Vb when the brake pedal is not pressed. Additionally, a terminal T7 of the control unit 1 is connected to a clutch switch 19 which opens when a clutch pedal (not shown in the drawings) is pressed and connects the terminal T7 to the ground when the clutch pedal is not pressed. A brake lamp 20 is connected across the terminal T5 and the ground for the purpose of warning the vehicles running behind of the activation of the brake. A terminal T11 of the control unit 1 which is connected to an output terminal of the input/output control circuit 4 is connected to a cruise lamp 22 having a dimmer circuit 23. The cruise lamp 22 indicates the cruise control is in progress and the dimmer circuit 23 controls the brightness of the cruise lamp 22 depending on whether the illumination lamps of the instrument panel are lighted up or not. Terminals T8 to T10 of the control unit 1 are connected to a motor-driven actuator unit 21. The actuator unit 21 comprises an electric motor 33, an electromagnetic clutch 31 having a solenoid 32 for selectively connecting the output shaft 33' of the motor 33 to a pulley 34 which is connected to a throttle valve 35 of the carburetor of the vehicle engine by way of a control cable 36, and limit switches 37 and 38 for detecting, if either one of the two ends of the stroke of the actuator unit 21 has been reached. A terminal T10 which supplies electric current-for driving the motor 33, in the direction to cause the acceleration of the vehicle, is connected to an end of the motor 33 by way of the limit switch 37 which is a normally closed switch for detecting the end of the acceleration stroke of the actuator unit 21. The diode D7 connected in parallel with the switch 37 conducts electric current in the direction to decelerate the vehicle even when the limit switch 37 is open. The terminal T9 which supplies electric current for driving the motor 33 in the direction to cause the deceleration of the vehicle is connected to the other end of the motor 33 by way of the limit switch 38 which is a normally closed switch for detecting the end of the deceleration stroke of the actuator unit 21. The diode D8 connected in parallel with the limit switch 38 conducts electric current in the direction to accelerate the vehicle even when the limit switch 38 is open. The limit switches 37 and 38 detect two ends of the stroke of the working end of the actuator unit 21 which is directly connected to the linkage system for controlling the throttle valve 35. Here, it should be noted that the working end of the actuator is connected to the linkage system between the throttle pedal and the throttle valve in such a manner that the actuator can depress the throttle pedal as it opens the throttle valve but remains in its original position when the throttle pedal is depressed by the driver. Closing of the throttle valve is effected by return springs provided to the throttle valve and the throttle pedal. Inside the control unit, the terminals T5 to T8 are also connected to the input/output control circuit 4 which is in turn connected to the CPU 7. Thus, the terminals T5 and T6 transmit signals from the brake switch 18 to the CPU 7 by way of the input/output control circuit 4. The terminal T6 is connected to the emitter of a transistor Q1 while the terminal T8 is connected to the collector of the same transistor Q1. A zener diode ZD is connected across the emitter and the collector of the transistor Q1. A resistor R1 is connected across the emitter and the base of the transistor Q1 and the base of this transistor Q1 is connected, by way of a resistor R2 and a diode D1, to the collector of a transistor Q2 having a grounded emitter. The diode D1 permits the flow of electric current from the base of the transistor Q1 to the collector of the transistor Q2. Further, the collector of the transistor Q1 is connected to the line connected from the input/output control circuit 4 to the solenoid 32 of the electromagnetic clutch 31 by way of the terminal T8. This line is connected to a terminal CT8 of the CPU 7 by way of the input/output control circuit 4 for detecting the state of the transistor Q1 as described hereinafter. The base of the transistor Q2 is grounded by way of a resistor R3 and is also connected to a terminal CT1 of the CPU 7 by way of a resistor R4. Depending on the state of the terminal CT1, the transistors Q1 and Q2 turn on and off, thus activating or deactivating the solenoid 32 of the electromagnetic clutch 31. The actuator drive circuit 5 consists of a transistor bridge circuit for driving the motor 33 in either direction as desired according to a control signal from the CPU 7. This bridge circuit comprises a pair of PNP transistors Q3 and Q5 and another pair of NPN transistors Q4 and Q6. As shown in the drawings, the collector of the first transistor Q3 of the transistor bridge circuit is connected to the collector of the second transistor Q4 of the transistor bridge circuit by way of the terminal T10, the limit switch 37, the motor 33, the limit switch 38 and the terminal T9, to selectively supply electric current for acceleration to the motor 33 while the collector of the third transistor Q5 is connected to the collector of the fourth transistor Q6 by way of the terminal T9, the limit switch 38, the motor 33, the limit switch 37 and the terminal T10, to selectively supply electric current for deceleration to the motor 33. Additionally, the collector of the first transistor Q3 is directly connected to the collector of the fourth transistor Q6 while the collector of the third transistor Q5 is directly connected to the third transistor Q4. To supply electric power to the transistor bridge circuit, the terminal T6 is connected to the emitter of the transistor Q3 by way of a diode D2 while the unregulated electric power line Vb is connected to the emitter of the transistor Q5 by way of a diode D3. The emitters of the transistors Q4 and Q6 are connected in common and are grounded by way of a current detection circuit 6 which is also connected to a terminal CT2 of the CPU 7. A diode D4 is connected across the emitter and the collector of the transistor Q3 with its anode end connected to the collector while another diode D6 is connected across the emitter and the collector of the transistor Q5 with its anode end connected to the collector. A diode D5 is connected across the emitter and the collector of the transistor Q4 with its anode end connected to the emitter while the diode D7 is connected across the emitter and the collector of the transistor Q6 with its anode end connected to the emitter. Each resistor R5 to R8 is connected across the emitter and the base of each of these transistor Q3 to Q6, and the base of each of these transistors Q3 to Q6 is connected to the collector of a corresponding driver transistor Q7 to Q10 by way of a resistor R9 to R12. The emitters of the transistors Q7 and Q9 are directly grounded while the bases of the transistors Q7 and Q9 are grounded by way of resistors R13 and R15, respectively. The emitters of the transistors Q8 and Q10 are connected to the regulated power line Vc while the bases of these transistors Q8 and Q10 are also connected to the regulated power terminal Vc, however, in the latter case by way of resistors R14 and R16, respectively. The bases of the driver transistors Q7 to Q10 are connected to corresponding terminals CT3 to CT6 of the CPU 7 by way of individual resistors R17 to R20, respectively. The base of the transistor Q2 for driving the solenoid 32 of the electromagnetic clutch 31 is connected, by way of a diode D8, to the collector of a transistor Q11 having a grounded emitter and forming an output end of a watch dog timer circuit 27 which is described hereinafter. Now the structure of the watch dog timer circuit 27 is described in the following. A terminal CT7 of the CPU 7 normally produces a 4 Hz pulse signal. However, when any abnormal condition is produced in the CPU 7, the terminal CT7 may be kept at 0-volt L level or 5-volt H level indefinitely or may produce a 400 kHz high frequency signal depending on the kind of abnormality which may have occurred in the CPU 7. This terminal CT7 is connected to the base of a transistor Q12 having a grounded emitter by way of a capacitor C1 and a resistor R21 which are connected in series. The base of this transistor Q12 is also grounded by way of a capacitor C2 and a resistor R22 which are connected in parallel. The collector of this transistor Q12 is connected to the base of a transistor Q13. The collector of the transistor Q13 is connected to the regulated power line Vc and a resistor R23 is connected across the collector and the base of the transistor Q13. The emitter of the transistor Q13 is connected to the base of the transistor Q11 as described earlier. In this watch dog timer circuit 27, the capacitor C1, the resistor R2, the capacitor C2 and the resistor 22 form a band-pass filter which allows the passage of the normal 4 Hz pulse signal from the terminal CT7 but shuts off the abnormal DC signal and the abnormal 400 kHz high frequency signal. Therefore, under the normal condition, the transistor Q12 turns on and off at the frequency of 4 Hz and since the time constant of the resistor R23 and the capacitor C3 is sufficiently great, the capacitor C3 is never fully charged, thereby preventing the transistors Q11 and Q13 from attaining a conducting state. On the other hand, under an abnormal condition, the transistor Q12 is held in a non-conducting state, the capacitor C3 gets fully charged and the transistors Q13 and Q11 attain a conducting state. A diode D9 is connected between the base of the transistor Q7 of the acceleration drive circuit 25 and the collector of the transistor Q11 of the watch dog timer circuit 27 to permit the flow of electric current from the base of the transistor Q7 to the collector of the transistor Q11. Another diode D10 is likewise connected between the base of the transistor Q4 and the collector of the transistor Q11. The base of the transistor Q5 of the deceleration drive circuit 26 is connected to the collector of a transistor Q14 by way of a resistor R24 while the emitter of the transistor Q14 is connected to the base of the transistor Q6. The emitter or the transistor Q15 is connected to the unregulated power line Vb and a resistor R26 is connected across the collector of the transistor Q15 and the base of the transistor Q14 which is grounded by way of a resistor R25. A resistor R28 is connected across the emitter and the base of the transistor Q15. Further, the base of the transistor Q15 is connected to the collector of the transistor Q11 by way of a resistor R27 and a diode D11 which permits the flow of electric current from the base of the transistor Q15 to the collector of the transistor Q11. In the actuator drive circuit 5, when any abnormal condition has taken place, the transistor Q11 turns on and the bases of the transistors Q2, Q4 and Q7 are grounded. Therefore, irrespective of the states of the terminals CT1, CT3 and CT4, the transistors Q2, Q4 and Q7 are brought into non-conductive states. Further, since the conductive state of the transistors Q11 causes the transistors Q15 and Q14 to be in conductive states, the transistors Q5 and Q6 are brought into conductive states irrespective of the states of the terminals CT5 and CT6. Therefore, when any abnormal condition is detected in the CPU 7, the transistor Q2 for driving the solenoid 32 of the electromagnetic clutch 31 is turned off and an acceleration drive circuit 25 comprising the transistors Q3 and Q4 is turned off while a deceleration drive circuit 26 comprising the transistors Q5 and Q6 is turned on. Additionally, when the transistor Q11 turns on, the base of the transistor Q2 is grounded by way of the diode D8 and this in turn causes the solenoid 32 to be deactivated by way of the output transistor Q1. Further, according to this embodiment, since the electric power to the acceleration drive circuit 25 comprising the transistors Q3 and Q4 and the electromagnetic clutch drive circuit comprising the transistor Q1 is supplied from the terminal T6 in both cases, when the cruise condition is discontinued by the action of the brake pedal, the power to the acceleration drive circuit 25 and the electromagnetic clutch drive circuit is positively disconnected by the brake switch 18. Thus, the brake switch 18 has the function of overriding the control of the CPU 7 and this feature contributes to improving the reliability of the cruise control system. On the other hand, the deceleration drive circuit 26 is directly connected to the power line Vb, and the capability of the system to decelerate the vehicle is maintained irrespective of the state of the brake switch 18. This is also advantageous according to the principle of fail-safe. Now the action of this cruise control system is described in the following. When the ignition switch 9 and the main switch 11 are both turned on, electric power is supplied to the control unit 1 and the main indicator lamp 12 turns on. If the set switch 15 is closed when the conditions for cruise control, such that the brake switch 18 or the clutch switch 19 is not activated and that the vehicle speed is greater than a certain minimum value, are satisfied, a target vehicle speed is stored in the CPU 7 according to the signal from the vehicle speed sensor 13. Thereafter, the control unit 1 activates the actuator unit 21 as required to maintain the vehicle speed at this set level. When the control unit 1 drives the actuator unit 21 according to the difference between the set level and the actual vehicle speed, a drive signal is supplied from the CPU 7 to the solenoid 32 of the electromagnetic clutch 31 by way of the input/output circuit 4 and engages the electromagnetic clutch 31. When the vehicle speed is less than the target vehicle speed and is required to be increased, signals from the terminals CT3 and CT4 turn on the transistors Q7 and Q8 while signals from the terminals CT5 and CT6 turn off the transistors Q9 and Q10. When the vehicle speed is greater than the target vehicle speed and is required to be decreased, the signals from the terminals CT3 to CT6 reverse the states of the transistor Q7 to Q10. Thus, the electric current supplied to the motor 33 is reversed as required and the actual vehicle speed is controlled to be substantially in agreement with the target vehicle speed. The resume switch 16 is for resetting the preceding target vehicle speed to resume the cruise control after an interruption of the cruise control. The interruption of the cruise control happens when the CPU 7 has detected a cancel signal produced by the activation of the brake switch 18 or the clutch switch 19. When the cruise control is to be interrupted, the CPU 7 sends a deceleration signal to the actuator drive circuit 5 in order to drive the actuator in the direction to close the throttle valve 35 and decelerate the vehicle and the indicator lamp 23 turns off. According to the present embodiment, since the power lines leading to the acceleration drive circuit 25 and the deceleration drive circuit 26 are separately provided and the normally closed contact S2 of the brake switch 21 is interposed in the power line leading to the acceleration drive circuit 25 and the power transistor Q1 for controlling the electromagnetic clutch 31, the supply of electric power to the acceleration drive circuit 31 and the electromagnetic clutch 31 is discontinued as soon as the brake pedal is pressed. This assures the shutting off of the cruise control even when an abnormal condition of any sort has occurred. For instance, even when both the power transistors Q3 and Q4 of the acceleration drive circuit have short-circuited, supply of electric current to both the solenoid 32 of the electromagnetic clutch 31 and the acceleration drive circuit 25 is prevented simply by pressing the brake pedal. In this cruise control system, when the CPU 7 becomes faulty due to reasons which may be related to the software or the hardware of the micro processor, the CPU 7 may produce confused output signals from the terminals CT3 to CT9. For instance, if the terminals CT3 and CT6 were both brought to high levels, the transistors Q3 and Q6 would be both brought to conductive states and could be destroyed due to the state of short-circuiting. However, according to the present invention, since not only the transistor Q11 turns on and the electromagnetic clutch 31 is disconnected but also the transistors Q7 and Q4 of the acceleration drive circuit 25 are both brought into non-conductive states, there will be no short-circuiting between the transistors Q3 and Q6 and the transistors Q4 and Q5 Moreover, the deceleration drive circuit 26 is turned on and the motor 33 is driven in the direction to decelerate the vehicle. Thus, in the case of an abnormal condition of the CPU 7, the actuator is positively driven in the direction to decelerate the vehicle by two different means and this serves as a highly reliable fail safe system. Now the action of the present embodiment, including a self diagnosing action thereof, is described in the following with reference to the time chart given in FIG. 2. Initially, the main switch 11 is on; the set switch 15 is open; the magnetic clutch 31 is disconnected; the lower limit switch 38 is open; and the motor 33 is stationary. This state is mode A. When the set switch 15 is pressed by the driver, the CPU 7 produces a decelerating signal as an initializing signal for a time period t1 (=500 msec) but since the lower limit switch 38 is open the motor 33 remains stationary. This state is mode B. This mode is for the purpose of the self diagnosis of the system as described hereinafter. Mode A occurs again after the motor 33 stops, and lasts until the set switch 15 is released. After a certain time delay upon completion of the initialization of the motor 33 in mode B, the electromagnetic clutch 31 is engaged and the motor 33 is driven in the direction to accelerate the vehicle with a pulse having a width t1 which is greater than that of a normal pulse. The lower limit switch 38 is now closed. This process is mode C and is provided for the purpose of taking up any slack which may be present between the actuator and the throttle valve and preventing any ill effect arising from such a slack from being noticeable to the driver At the same time, the cruise indicator lamp 22 is lighted up. Upon completion of this mode C, the system advances to the step of comparing the current vehicle speed and the target vehicle speed and, in the meantime, the motor 33 remain stationary. This process is mode D. If the current vehicle speed is less than the target vehicle speed a pulse of width t2 for acceleration is generated and if the current vehicle speed becomes greater than the target vehicle speed a similar pulse for decelerator is produced as mode E in the time chart of FIG. 2. In this way, the vehicle speed is adjusted to the target vehicle speed and the pulse width or the pulse frequency may be varied as desired in order to accomplish this control action. If the current vehicle speed becomes excessive and can not be controlled to the target vehicle speed even after the limit switch 38 has been opened with the actuator being turned to its lower limit (this happens when the vehicle runs down a long slope and the vehicle speed cannot be controlled even when the throttle valve is completely closed), the magnetic clutch 31 is disengaged and the throttle pedal is kept at its released condition. Thus, the motor 33 is liberated from any load. When the vehicle speed drops below the target vehicle speed, a pulse of a relatively large width t3 (=t2 +t4) for acceleration is produced and the vehicle speed is again controlled to the target vehicle speed by the cruise control. By providing this boosted acceleration signal, the vehicle speed is prevented from dropping excessively from the target vehicle speed due to the insufficiency of the control action arising from the presence of any slack or play in the linkage system between the actuator and the throttle valve 35. Table 1 summarizes a self diagnosis procedure for the drive transistors Q1 and Q3 to Q6 according to the present invention. TABLE 1__________________________________________________________________________ capabilities to be tested acceleration deceleration clutch drive drive transistors drive transistors transistor Q3 Q4 Q5 Q6 Q1modes close open close open close open close open close open__________________________________________________________________________A: before cruise control X X X X XB: initial deceleration X X drive signalC: initial acceleration X X drive signalD: cruise control with X X X X X actuator in neutralE: deceleration drive X X signal__________________________________________________________________________ In mode A, all the transistors Q1 and Q3 to Q5 are in non-conducting states. According to the present embodiment, the transistors Q3 to Q6 are turned on one by one and the opening capabilities of the transistors connected in series with the transistor which is turned on are tested. For instance, when the transistor Q3 is turned on, no electric current will be detected by the current detection circuit 6. If that is the case, then it follows that the transistors Q4 and Q6 are in non-conductive states as required and the opening capabilities of the transistors Q4 and Q6 are tested. If no electric current is detected at the terminal CT8 of the CPU 7, it shows that the transistor Q1 is in a non-conductive state as required. This proves the opening capability of the transistor Q1. In mode B, the transistors Q5 and Q6 are turned on merely for the purpose of self diagnosis and the motor 33 remains stationary because the lower limit switch 38 is open. Therefore, if the current detecting circuit 6 detects any electric current, it shows that the transistor Q3 or Q4 is permanently closed or, in other words, is incapable of opening. In mode C, the transistors Q3 and Q4 are turned on for the purpose of turning the motor 33 in the direction to accelerate the vehicle. Therefore, if the current detecting circuit 6 detects any electric current, it shows that the transistors Q3 and Q4 are capable of closing or turning into conductive states. In mode D, the opening capabilities of the transistors Q3 to Q6 can be tested in the same way in the mode A. Furthermore, since the transistor Q1 is intended to be closed, if any electric current is detected at the terminal CT8 of the CPU 7, it shows that the transistor Q1 is capable of closing. In mode E, the transistors Q5 and Q6 are turned on for the purpose of turning the motor 33 in the direction to decelerate the vehicle. Therefore, if the current detecting circuit 6 detects any electric current, it shows that the transistors Q5 and Q6 are capable of closing or turning into conductive states. Thus, the closing and opening capabilities of all the drive transistors Q1 and Q3 to Q6 can be checked in an early stage of cruise control, and any possible failure in these drive transistors can be detected so that the system can be shut off before any problem arises. If any failure is detected in the modes A to E, a cancel signal may be produced, thus disabling the function of the set switch 15. FIG. 4 shows a second embodiment of the drive circuit 5 according to the present invention. In this embodiment, output of the watch dog timer circuit 27 is connected only to the bases of the transistors Q7 and Q9 by way of diodes D12 and D13, respectively. In this embodiment, if the transistor Q11 is brought into a conductive state due to any abnormality detected by the watch dog timer circuit 27, the bases of the transistors Q7 and Q8 are pulled down and the transistors Q3 and Q5 are forced into non-conductive states. This prevents any short-circuiting in the transistor bridge circuit of the drive circuit 5. Thus, according to either embodiment of the present invention, even when the CPU 7 produces a signal which may otherwise cause the dead short-circuiting of the drive transistors of the drive circuit, the transistors are protected from destruction and in the case of the first embodiment, the actuator is even driven in the direction to decelerate the vehicle. Although the above embodiments pertained to an actuator drive circuit using a transistor bridge circuit, the present invention can be applied to other forms of transistor drive circuits without departing from the spirit of the present invention.
A vehicle cruise control system, comprising a control circuit for producing a control signal for maintaining a speed of a vehicle at a fixed level according to a difference between an actual vehicle speed and a target vehicle speed, and a drive circuit for producing a drive signal for selectively driving an actuator in a direction either to accelerate the vehicle or to decelerate the vehicle according to the control signal from the control circuit. The drive circuit is provided with a transistor bridge circuit comprising four drive transistors for producing the drive signal. The control circuit is provided with a detection means for detecting an abnormal state of the system and an inhibiting means which brings at least one of the drive transistors into an non-conductive state when any abnormal state is detected by the detecting means. The control circuit may be programmed to perform a certain diagnostic procedure for testing the soundness of the drive transistors. Thus, erratic behavior of the cruise control system and destruction of the drive transistors can be effectively prevented.
1
This is a divisional application of application Ser. No. 08/613,412 filed on Mar. 11, 1996, now U.S. Pat. No. 5,689,935, issued Nov. 25, 1997. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates in general to product packaging and in particular to a plastic material for forming a good product package having a predictable line of failure when the package is opened to prevent tearing of the bag down the body of the bag. This predictable failure path is provided through a coextruded lamination manufacturing process involving specific resins or blends or resins coextruded in three or more layers that do not inhibit processing speed, efficiency, and economy of materials used to provide this reliable openability. 2. Description of Related Art Including Information Disclosed Under 37 CFR 1.97 and 1.98 Laminated films produced for making food packages are based on multiple layers of plastic film each with a specific purpose. An outer web is designed to move across a packaging machine, another web provides heat stability to prevent distortion when the package is sealed, still another provides the ability to obtain a uniform print surface, and yet another provides the ability for the laminated film to be adhered to an adhesive used to bond the laminated film to an adjacent film. When more than two film webs are used to form a laminated film, these core film webs provide additional specific properties such as moisture vapor transfer rate, gas barrier, and appearance. This part of the lamination has nothing to do with the openability of the lamination in package form. The inner web of a lamination can contribute barrier qualities, optics, and sealability, and yet provide openability that varies from “impossible” to “easy open”. Thus, a prior art bag so constructed is illustrated in FIG. 1 wherein the bag 10 is shown filled with product and sealed. It has a longitudinal seal 12 and end seals 14 and 16 . The bag is generally made as indicated in FIG. 2 by forming essentially a cylindrical tube 18 with a longitudinal seal 12 and with a horizontal seal at the lower end thereof along seal 16 as shown in FIG. 3 . The package can then be filled with product when constructed as shown in FIG. 3 and sealed as illustrated in FIG. 4 to form a bag filled with product having upper and lower sealed ends 14 and 16 , respectively, and a longitudinal side seal 12 . The problem with these bags is illustrated in FIG. 5 . When the bag is to be opened and forces are applied in the direction of arrows 24 and 26 to the upper seal 14 , and bag may start to open at 26 and then tear downwardly into the side of the bag as illustrated at 28 . This is not a serious problem for small bags of food products because the contents of the small bag can be eaten entirely. However, with large bags containing large amounts of food products, the tear 28 prevents the bag from being reclosed to protect the contents therein; thus the contents must be transferred to another container that can be sealed to protect the freshness of the product. The reason that such bags tear as shown in FIG. 5 is because of their construction and the interlaminar strength at each interface of the lamination. A history and description of such bag construction is helpful. COATED FILMS Prior to extrusion lamination with a thermoplastic adhesive, adhesives were, and still are, based on a single or two-part adhesive which “cures” to a hard bond that is very difficult to separate. With this type of adhesive, openability of a package had to be built into the inner film. The inner film's primary purpose is sealability in order to provide integrity to the package. Openability was based on either a coating on the inner film that acted as the sealant or a coextrusion film or a thin sealant ply that separated from the inner film when the package was opened. While these methods did provide “openability”, it was inconsistent and varied with the temperature of the sealing jaws, sealant ply thickness when using a coextrusion film, and with the adhesion of the coating to the inner film due to primer or treatment variations. In addition, there was a narrow hot tack (ability to keep end seals together at the hot conditions necessary to obtain a seal) and seal range with coextruded inner films. The same problems occurred with coated film if the film treatment and/or primer weight/drying was too low. OPP FILMS Because of cost competition, the use of coextruded oriented polypropylene films (OPP) began to replace coated films. These new films, which were and are typically two and three-layer coextrusions of homopolymer polypropylene as a core and copolymer/terpolymer skins, did not, and do not, provide consistent openability of packages without tearing of the package when it is opened. As the need for larger packages with multiple usage has expanded, the failure of packages based on laminations with oriented polypropylene coextrusions films as the inner web became unacceptable. Therefore, a solution was needed to provide reliable openability of these larger packages along a predetermined path without tearing of the package down the side when it is opened. With the change from coated sealant films or a dissimilar thermoplastic skin such as Surlyn® coextruded with polypropylene that has some degree of openability due to built-in fracture or delamination lines to a coextruded polypropylene film that has poor openability, tearing the package is a serious problem. The increase in large packages with multiple use needs has made tearing of the package when opening unacceptable. PROBLEMS TO OVERCOME A process to produce a usable (opening without tearing) extrusion based lamination between an inner sealant film and an adjacent outer film in two-ply laminations, or the core film in a three-ply lamination must provide negligible loss in processing efficiency and yield loss and also enable the use of cost effective resin components to be commercially feasible. For example, if an extrusion process typically runs at 1200 ft/min, it is impractical to use a similar extrusion process that, while making a usable product, runs at 300 ft/min. In addition, the ability to produce product that has a flat profile across the web cannot be compromised by a product that meets end use requirements but has poor profile and results in poor machine performance at the end user. Also, extrusion laminating of polypropylene films (typically one web is printed) requires polypropylene films with surface treatment and/or modification with other resins to provide a surface to which polyethylene can obtain adhesion. Polyethylene, when extruded, has a non-polar surface unless it is extruded at a sufficiently high temperature and is exposed sufficiently to air through what is called an air gap (gap between the extrusion die lips and the extrusion nip) in order to provide sites which can be bonded to similar sites on polypropylene film surfaces. In addition, primers are typically used to provide adhesive to the inks on the inner surface of one of the films to be laminated. If any of the polyethylene extrusion parameters are not at a specific level, poor adhesion of the lamination will result. This manifests itself as a delamination at one or both of the film interfaces. Because of the critical nature of the polyethylene extrusion process and the speed at which the lamination process occurs (typically 1000-1500 ft/min) the bond strength at the inner surfaces of the polypropylene films must be strong and flexible to obtain a level of adhesion that provides usable handling during distribution of filled packages. Because of the need for reliable bond strength between the polypropylene films in a polyethylene lamination and the seal strengths of coextruded polypropylene films, it is difficult for a lamination using a polypropylene sealant film to provide consistent, reliable openability within the film layers or interfaces of the lamination. Thus, consider the lamination of a prior art film as shown in FIG. 6 . The lamination consists of outer polypropylene film layer 30 with treated surface 31 , ink layer 32 , primer layer 34 , if needed, polyethylene extrudable adhesive layer 36 , a sealable polypropylene film 38 with treated surface 39 and with copolymer or terpolymer sealant 40 . It should be noted that outer layer 30 can be any acceptable plastic packaging film and that inner layer 38 can be any sealable plastic packaging film such as coex film, coated film, or metallized film. Primer 34 is used to provide strong adhesion of the inks to the outer ply of the extrudate 36 . It also provides additional strength between the treated polypropylene film surface 31 and the extrudate 36 . A primer serves two main functions, i.e., 1) It helps to provide an uncontaminated surface so that the extrudate 36 will rapidly spread and uniformly web out. 2) The primer joins both the ink 32 and substrate 30 to the extrudate 36 by a covalent bond, hydrogen bond, van der Waals force, dipole interaction, or some mixture of these effects. The ability of the primer to increase the number of reactive sites on the substrate and maximize intermolecular attraction is important with non-polar surfaces such as inks, marginally treated surfaces, or treated surfaces that may have some surface interference over the treated areas. There are inks and polypropylene surfaces that do not require a primer for acceptable end product use but a primer is frequently used to maximize adhesion and provide the ability to operate at higher laminator speeds. In the case of the present invention, a primer may or may not be used, but in the preferred product, it is used to maximize adhesion to the inks. Continuing with FIG. 6, the sealable polypropylene film 38 is approximately 0.70 mil and, when this package layer is sealed to the opposing package layer, the 0.70 mil sealant film 38 fuses to the adjacent 0.70 mil film and results in approximately 1.40 mils of film forming the entire seal. When the package is opened, the inner film fractures starting at a point on the lower edge of the seal interface as shown at 42 . The fracture can then proceed through the 0.70 mil polypropylene film layer 38 , through the polyethylene extrudable adhesive layer 36 , the primer 34 (if present), through the ink layer 32 , and into the outer polypropylene film 30 which, of course, allows the bag to split down the side. When the bond strength of the lamination is high enough to provide a usable lamination for normal distribution, the tendency is for the applied force shown by arrows 24 and 26 in FIG. 5 to break to the weakest point and split down the lamination or through the total lamination because of a lack of a consistent failure path within the lamination which, itself, has very low tear strength. Any irregularities in the seal such as a foldover can cause the splitting to occur much easier. FIG. 7 illustrates a second prior art bag lamination structure with the ink on the inside of the film. Again, with this construction, when the package is opened, the inner film 54 fractures starting at a point on the lower edge of the seal interface as shown at 58 . The fracture can then proceed as indicated by arrow 60 through the 0.70 mil oriented polypropylene inner film 54 and treated surface 55 to the ink, and through the ink layer 52 itself, into the polyethylene adhesive 58 and through the primer 50 (if present), into the outer polypropylene treated interface 47 , and then into the outer polypropylene film 46 itself. Again, the interlaminar bond strength of the lamination is high enough to provide a useful lamination for normal distribution, the tendency is for the applied force, shown by the arrows 24 and 26 in FIG. 5, to break to the weakest point and split down the lamination or through the total lamination because of the lack of a consistent failure path within the lamination which itself has a very low tear strength. Because of this, it would be desirable to have a plastic product bag having a seal that includes a predictable line of failure when the package is opened. REQUIREMENTS OF THE INVENTION The present invention discloses a food product package film having a seal to provide a predictable line of failure when a package is opened. This predictable failure path is provided through a coextruded lamination manufacturing process involving specific resins or blends of resins coextruded in three or more layers that do not inhibit processing speed, efficiency, and economy of materials used to provide this reliable openability. In order to obtain strong adhesion, the inner and outer films must have treatment on the inner surfaces facing the polyethylene outer plys of the three ply extrudate. Treatment of the laminating side of the polypropylene film provides bonding sites to which similar bonding sites on the polyethylene outer plys of the extrudate can bond. For example, the outer plys of a three layer extrudate based on polyethylene/polypropylene/polyethylene, provide chemically reactive sites such as carbonyl and hydroxyl groups that will bond to similar groups on the polypropylene treated surface by a mixture of covalent bonds, hydrogen bonds, van der Waals forces, dipole interaction, or a mixture of these effects. The reaction sites on the polyethylene outer surfaces are formed because of the temperature of extrusion (600°-620° F.) and oxygen in the air. However, the inner plys of the extrudate, i.e., polyethylene to polypropylene, because they are not exposed to air have these chemical bonding sites at a negligible level. The result is that bonding at these interfaces is weak and depends upon the flexible nature of the resins used and the mechanical pressure of the lamination process to provide adhesion. This adhesion level with essentially untreated non-polar interfaces is in the 20-50 gms/in range. This would typically be considered non-functional, but in this novel process, the combined lamination with strong functional bonds at all other interfaces provides a finished product capable of withstanding all required finished product needs. 1. The Performance Requirements The resin or resins used to bond inner polypropylene sealant film and the adjacent film (a core in a three-ply lamination and an outer film in a two-ply lamination) must provide inner laminar adhesion comparable to what is attainable with extrudable polyethylene resin. A core layer in a coextrusion process that provides a reliable failure path and opening must be extrudable at normal operational speeds and must provide final coextrusion gauge profile comparable to what is obtainable with a polyethylene resin extrudate. A resin that provides the above predictable failure path in a coextrusion must be extrudable at a temperature that will allow it to be coextruded with a typical extrusion grade polyethylene resin, i.e., 0.917 density/3.5-18 melt index (MI). Finally, this resin must not impart objectionable odor or color and must be stable to extrude. With the understanding that, for a package to be opened, fracture of the inner sealant polypropylene film (oriented or cast) is the initiation of failure, the concept is to insure that a predictable failure mode occurs at a specific interface such as the inner film/ink (when ink is at the inner film interface), within the ink at the inner film/extrudate interface in unprinted areas, at the ink/primer/extrudate interface, within the extrudate, and at the extrudate to outer film interface. 2. Discussion of Potential Problems in Providing a Predictable Failure Mode When a Package is Opened Because of the lack of flexibility of the inks used to print films, failure can and frequently does occur at the ink interface when opening. The same failure may occur within the ink itself. However, over 20 years of production experience demonstrates that this is not a consistent predictable failure path. In order to compensate for the poor-to-fair adhesion of inks to a polyethylene extrudate, a primer is required. Normally this is a polyethyleneimine based primer. It has been shown that the strength obtained at the ink/inner film and within the ink film itself is too high to enable acceptable in-use performance such that a reliable failure path will be provided. The result is that the force applied to open a package fractures the inner film and failure at the ink/inner film or ink interface does not consistently occur because bond strength is not consistent or reliably low. Further, with the existing ink formulation/primers, it is impracticable to obtain adhesion to the ink interface with a polyethylene extrudate that provides openability and handling resistance. Without a primer to provide functional bonds of the ink to the polyethylene extrudate, the package will not withstand in-use handling. An alternative is to use coextrudable adhesive copolymer resins or formulated resins that, because of their chemical nature, will adhere to the ink and film portions of the inner film. However, the nature of these resins is that they are costly, require extrusion at temperatures low enough to prevent degradations of the adhesions promoting resins thus minimizing adhesion of the total extrudate to the outer web of the lamination, do not promote good profile, and have odors that can be unacceptable for food packaging applications. In addition, most of these resins require longer dwell time, that is, they need pressure and time for maximum adhesion, and are thus not suited for extrusions at speeds in the 1000-1500 ft/min range. Another disqualification is that, while they may have what is considered good adhesion to ink or films, they may not withstand handling of the finished package due to a lack of flex resistance at the ink interface. Concerning the polyethylene extrudate, due to the flexible nature of the extrudate, it is impossible to make the failure occur within this ply of the lamination. Further, it is not possible to insure that the failure mode will occur at the interface between the polyethylene extrudate and the outer film because the bond strength of the polyethylene extrudate to the outer film in a lamination must be strong enough to insure handling ability in package form during distribution. Thus the mode of failure can occur at any or a combination of interfaces or through the whole lamination. At any of these points the opening force exerted can cause tear propagation to occur at right angles to the seal as shown in FIGS. 6 and 7. SUMMARY OF THE INVENTION The present invention provides a predictable line or path of failure when the package is opened. This predictable failure path is provided through a manufacturing process involving specific resins or blends of resins coextruded in at least three layers that does not inhibit manufacturing processing speed, efficiency, and economy of materials used to provide reliable openability. A coextrusion extrudate has been developed that will provide substantially consistent failure within the extrudate while at the same time maintaining the economy and performance of polyethylene as the primary extrudate in the lamination manufacturing process. It provides no change in machine performance during the packaging operation and provides substantially consistent openability by the consumer. The novel results are obtained by using a coextrusion based on a polyethylene/polypropylene/polyethylene extrudate. The concept is not limited to the use of high pressure low density polyethylene (LDPE) as one or both of the extrudate layers encapsulating the polypropylene core. Typically the LDPE resins usable in this process have a melt index from 2.0 to 35.0 and a density from 0.88 to 0.965. A preferred polyethylene low density resin has a melt index from 3.5 to 17.0 and densities from 0.914 to 0.926. A polyethylene resin may be manufactured by either a high or low pressure polymerization process. Linear low density polyethylene coating grades similar to Dow 3010 or Quantum GS-550 can be used in this process. The process is not limited to homopolymer polypropylene core resins since different degrees of openability can be obtained by using copolymer polypropylenes or blending homopolymer polypropylene with other polypropylenes or polyethylene as the core resin. The core can also be based on nylon, PET, EVOH, and the like to arrive at the desired opening strength. An essential part of this concept is that the polyethylene can be one or more of the outer plys of the extrudate. The dissimilar melt temperatures of polyethylene and polypropylene (or polypropylene resin and blends with specific other adhesion-enhancing resins) provide the clean mode of failure. The flexible nature of polyethylene provides the handleability needed in the finished lamination for normal handling of the finished package. It is possible to increase the bond strength between the core and the outer polyethylene extrudate layers by blending EMA resins (example Chevron 2207) up to 35% by weight. A significant part of this concept is that it be an extrusion lamination. By using this process it is possible to maintain the seal strength and hot tack of the whole inner film and, when opening the package, drive the failure point to specifically occur at the coextrusion laminate interface. In laminations using curing-type adhesives, this concept is not possible because of the strong bonds that occur between the plys of the lamination. It is possible to provide openability using a coextruded inner sealant film with specific failure points but the limitation in hot tack, seal range, and economics of making the film are not as consistent and reliable as the concept set forth above. The nature of easy-opening interlaminar failure provides for use of sealant films not normally usable for each opening. For example: Cast polypropylene or films with unusual linear characteristics such as high density polyethylene or crystalline high-moisture barrier polypropylene film may be used. Thus it is an object of the present invention to provide an easy-opening product plastic bag that generally does not tear down the side of the bag when a seam is opened. It is another object of the present invention to provide a product bag formed of plastic that has a seal in which is provided a predictable line of failure when the package is opened. It is still another object of the present invention to provide a predictable failure path in a good product package through a coextruded lamination manufacturing process involving specific resins or blends or resins coextruded in three or more layers. It is yet another object of the present invention to provide a good product bag having a predictable line of failure in a seal and which seal can be formed through coextrusion in a manner that does not inhibit processing speed, efficiency, or economics of material sued to provide this reliable openability. Thus the present invention relates to a plastic material for forming a product package having a sealed seam along which a substantially predictable line of failure occurs when the package is opened. The plastic material comprises first and second outer layers of plastic film material and a third extrudate layer of plastic material interposed between and bonded to the first and second outer layers, the third extrudate layer having characteristics such that a line of weakness is formed wholly within the extrudate that tears easier than the first and second outer layers and forms a substantially predictable line of failure wholly within the plastic extrudate material, the line of failure occurring during opening a package when a separating force is applied to the sealed seam. The invention also relates to a product package formed of plastic and having a substantially predictable line of failure along an elongated seam that opens the package when forces are applied to the elongated seam. The package comprises a plastic body portion having a substantially enlarged portion for containing the product. Sealed edges are formed on both ends of the body portion. The body portion is formed of a laminate using an extrudate adhesive layer laminated between an inner sealant plastic film layer and an outer plastic film layer. A sealant is formed on the inner surface of each end of the plastic body portion for joining two edges and closing each end of the package. The extrudate may be formed of polyethylene/polypropylene/polyethylene having different melt temperatures for forming the predictable line of failure along the interface wholly within the extrudate between the polypropylene and the polyethylene without tearing down the side of the bag. The invention also relates to a process for forming a material used to create a product package having edges forming a sealed seam along which a substantially predictable line of failure occurs when force is applied to the edges of the seam. The process comprises the steps of providing first and second outer layers of plastic material and extruding a third layer of plastic extrudate in an interposed relationship between the first and second outer layers of plastic material to form a multilayer lamination, the third layer having specific internal adhesion characteristics such that a line of weakness is formed wholly within the extrudant that tears easier than the first and second outer layers and forms a substantially predictable line of failure along a package seam formed by sealing edges of the plastic material, the line of failure opening the package when a separating force is applied to the sealed edges without tearing the side of the bag under normal opening forces being applied. BRIEF DESCRIPTION OF THE DRAWINGS These and other features of the present invention will be more fully disclosed when taken in conjunction with the following DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS in which like numerals represent like elements and in which: FIG. 1 is a diagrammatical representation of a product package that is sealed on both ends; FIG. 2 is a schematic representation of a plastic film rolled to a cylindrical form preparatory to forming a product bag; FIG. 3 is a schematic representation of the lower end of the cylindrical film illustrated in FIG. 2 being sealed before product is place in the bag; FIG. 4 is a schematic representation of the bag of FIG. 3 having product therein and being sealed at the top portion; FIG. 5 is a schematic representation of a prior art bag tearing down the side when forces are applied to the top seam to open the bag; FIG. 6 is a representation of a prior art laminated package film which is so constructed that a tear may occur through to the outside and down the side of the bag; FIG. 7 is a representation of a prior art film layer similar to that in FIG. 6 except that the ink is on the inside of a polyethylene film; FIG. 8 is a schematic representation of the novel film of the present invention illustrating outer polypropylene layers separated by a multilayer extrudable adhesive composed of polyethylene/polypropylene/polyethylene to form a predictable line of failure wholly within the extrudate when the bag is opened; FIG. 9 is a schematic representation similar to FIG. 8 except that the ink is on the inside of the multilayer extrudable adhesive; and FIGS. 10A and 10B are diagrammatic representations of the extrudation process of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 8 is a schematic representation of a packaging film of the present invention that will allow easy opening of a package by providing a substantially consistent line of failure within the package seal. As can be seen in FIG. 8, the film 62 includes an outer polypropylene film layer 64 and an inner sealable polypropylene film layer 66 . An ink layer 68 and primer layer 70 may be added as needed. The novel ability to provide a substantially consistent failure line is provided by the multilayer separately extrudable adhesive 72 that includes polyethylene layer 74 , polypropylene layer 76 , and polyethylene layer 78 . The dissimilar melt temperature of the polyethylene 74 , 78 and the core polypropylene 76 or polypropylene resin blends (with specific other adhesion enhancing resins such as EMA) provides the clean mode of failure wholly within the extrudate 72 . Further, the flexible nature of polyethylene and polypropylene provides the handling ability needed in the finished lamination for normal handling of the finished package. Thus a tear may begin at the point designated by the numeral 80 and spread into the inner layer 66 along any particular path such as paths 82 or 86 . When the tear following path 82 passes through the polypropylene layer 78 , the line of failure will tend to occur at the weak interface 84 between the polypropylene layer 76 and the polyethylene layer 78 . The interface 84 is weak because of the different melt temperatures of the polypropylene 76 and the polyethylene 78 . Should, however, the tear proceed along a different path 86 and manage to extend through the polypropylene layer 76 , it will encounter the interface 88 between the polypropylene layer 76 and the polyethylene layer 74 which, again, is a weak area along which the tear can occur at interface 88 . Again, the different melting temperatures of the polyethylene 74 and the polypropylene 76 form the weak interface 88 . In either case, the tendency will be for a tear to occur wholly within the extrudate 72 along a substantially consistent line of failure on either side of the polypropylene layer 76 and prevent the tear from proceeding through the polyethylene layer 74 , the primer and ink layers 68 and 70 , and the outer polypropylene film layer 64 . Such, of course, prevents the bag from tearing down the side since the tear never reaches the external surface but follows the substantially predictable lines of failure along interfaces 84 and 88 wholly within the multilayer extrudate 72 . Thus FIG. 8 illustrates the film layer 62 that utilizes a coextrusion lamination having a polyethylene/polypropylene/polyethylene extrudate between an inner sealant film 66 of preferably oriented polypropylene or cast oriented polypropylene and an outer film 64 , preferably a polypropylene, in a three-ply lamination that will provide consistent package openability at a specific failure point wholly confined between the polyethylene and the polypropylene interfaces of the extrudate layer 72 . It should be noted that the invention is not limited to two outer film layers separated by an extrudate layer but could include multiple layer combinations. FIG. 9 is an alternate embodiment in which the multiple layer film 90 comprises an outside polypropylene layer 92 and an inside sealable polypropylene film 94 including sealant 96 . The primer 97 , is needed, and ink 98 may be placed on the sealable polypropylene film 94 as shown. The novel multilayer extrudable adhesive 100 , comprising polyethylene layer 102 , polypropylene layer 104 , and polyethylene layer 106 is extruded between the polypropylene film 92 and the primer 97 . Again, when a tear occurs at a weak spot 108 along the sealable polypropylene film 94 , it may generate along any one of several paths such as 110 and 112 into the interior of the film layer 90 . It may pass through the ink layer 98 , the primer layer 97 , and polyethylene layer 106 as shown by arrow 110 . However, when it reaches the weak interface 114 between the polypropylene layer 104 and polyethylene 106 , it tends to propagate along this interface because it is a specifically designed line of failure because of the different melt temperatures of the polypropylene layer 104 and the polyethylene layer 106 . If the tear does happen to propagate along the path 112 so that it extends through the polypropylene layer 104 , it will again strike a layer 116 of weakness that will cause the separation of the layers to occur along the interface 116 which is the line of weakness or designed line of failure. Thus, again, the predictable line of failure lies wholly within the extrudate 100 . It is to be understood that different degrees of openability can be obtained by using a blend of polypropylene homopolymers and other homopolymer propylene or copolymer polypropylenes, and polyethylene, or other blends of these resins may be formed as the core in the polyethylene/polypropyleneblend/polyethylene coextrusion there by controlling openability of a finished package in a coextrusion lamination. It should also be understood that this concept is not limited to the use of high pressure LDPE as one or both of the extrudate layers encapsulating the polypropylene core. Typically the LDPE resins usable in this process have a melt index from 2.0 to 35.0 and a density from 0.88 to 0.965. The preferred polyethylene low-density resins have a melt index from 3.5 to 17.0 and densities from 0.914 to 0.926. The polyethylene resins may be manufactured by either a high or low-pressure polymerization process. Linear low-density polyethylene coating grades similar to Dow 3010 or Quantum GS-550 can be used in this process. The use of ethylene methyl acrylate copolymers such as Chevron 2207 can be blended into the polyethylene outer ply for selective adhesion to the inner surfaces of the lamination. The EMA copolymer can be blended up to 35% by weight into the polyethylene resin used as the outer plys of the coextrusion. One of the polyethylene skins or layers can be based on a different polyethylene resin or blend to enhance the overall strength of the laminate, i.e., toughness, puncture, and the like. FIG. 10A is a schematic representation of the extrusion process by which the polyethylene/polypropylene/polyethylene extrudate adhesive novel ply in FIG. 8 or in FIG. 9 is formed. The actual resin extruding devices are well known in the art and typically are based on a combining adapter/die 131 where the extrudate melts are combined into one extrudate with specific layers. Thus as can be seen in FIG. 10A, the novel film layer 62 , is composed of two outer polyethylene extrudates 130 and 132 and an inner polypropylene core 138 all of which are extruded and then laminated between the laminating rollers 119 . The extrudate 62 is separately formed of the polyethylene layer 130 and polyethylene layer 132 coming from common (shown) or separate die extruders. The polypropylene layer 138 is coextruded from one extruder (not shown) and is between polyethylene layers 130 and 132 which are produced by another extruder (not shown). The extrudate 62 is then laminated with the polypropylene layers 120 and 122 through lamination rollers 119 . As can be seen in FIG. 10B, other polyethylene resins or blends 140 can be used as one of the polyethylene layers for selected adhesion and for enhancement of the physical properties of the finished lamination such as for instance, a barrier layer, puncture resistance and the like. The use of ethylene methyl acrylate copolymers such as Chevron 2207 can be blended into one or more of the polyethylene outer plys for selective adhesion to the inner surfaces of the lamination. The ethylene methyl acrylate copolymer can be blended up to 35% by weight into the polyethylene resin used as the outer plys of the core. The results of a first test series using the novel film is shown in Table I. It compares package openability without tearing of both prior art laminations and the novel laminated product. The basis of the test is the openability of 100 packages of each test group using typical opening force. The outer film, inner film, and inks are the same on the Prior Art and Novel laminations. The difference between prior art test material I and II is a target of 10 and 7 #/ream total extrudate weight and the gauge of the outer and inner films. The total extrudate weight in the prior art samples is polyethylene. In tests I and II of the novel material of the present invention, a three-layer coextrusion of low density polyethylene is used as the two outer plys with a core of polypropylene in the novel samples. It will be seen that 83 and 87 bags of the prior art tore down the side of the bag while with the present invention, only 2 and 3 bags out of the 100 samples tore down the side of the bag. TABLE I TYPE PRIOR ART PRIOR ART NOVEL NOVEL STRUCTURE I II I II Polypropylene 75 100  75 100  Outer Film (Gauge) Extrudate Outer Layer 10 #/Ream 7 #/Ream 4.0 #/Ream 2.5 #/Ream Total Total Polyethylene Polyethylene Polyethylene Polyethylene Core 10 #/Ream 7 #/Ream 2.0 #/Ream 2.0 #/Ream Total Total Polypropylene Polypropylene Polyethylene Polyethylene Outer Layer 10 #/Ream 7 #/Ream 4.0 #/Ream 4.0 #/Ream Total Total Polyethylene Polyethylene Polyethylene Primer Yes Yes Yes Yes Ink Ink Ink Ink Ink Inner Polypropylene 70 120  70 120  Film (Gauge) # of Packages 83 87  2  3 Tearing # of Packages Not 17 13 98 97 Tearing % of Openability  17%  13%  98%  97% w/o Tearing Concerning the novel I and II structures of the present invention shown in Table I, two pounds/ream is the preferred target polypropylene core weight but weights as low as 1.0 #/ream are acceptable. There is no limit on the upper polypropylene weight as long as a continuous polyethylene layer is present on each side of the polypropylene. The distribution of the outer polyethylene layer does not have to be symmetrical, but it is critical for consistent package durability that a continuous polyethylene layer be present on each side of the polypropylene cord. For example, a polyethylene/polypropylene/polyethylene distribution in #/ream of 1.0/2.0/9.0, 9.0/2.0/1.0, 3.0/2.0/7.0 will all provide acceptable results. If the polyethylene is absent from the side of the extrudate facing the print, the package handling resistance is not acceptable. Table II illustrates the results of a second test series in which comparison of the openability of prior art laminations based on films with tear resistance poorer than those used with the normal prior art product are compared to the same laminations utilizing the novel extrusion lamination process of the present invention. Percent openability is based on 100 packages tested. TABLE II TYPE PRIOR ART PRIOR ART PRIOR ART NOVEL NOVEL NOVEL STRUCTURE I II III I II III Outer Film 80 Ga. High 75 OPP 75 OPP 80 Ga. High 75 OPP 75 OPP (Gauge) Barrier OPP Barrier OPP Total Extrudate 10 #/ream 10 #/ream 10 #/ream 10 #/ream 10 #/rearn 10 #/ream Outer Polyethylene Polyethylene Polyethylene 4 Polyethylene 4 Polyethylene 4 Polyethylene Core Polyethylene Polyethylene Polyethylene 2 Polypropylene 2 Polypropylene 2 Polypropylene Inner Polyethylene Polyethylene Polyethylene 4 Polyethylene 4 Polyethylene 4 Polyethylene Primer Yes Yes Yes Yes Yes Yes Ink Ink Ink Ink Ink Ink Ink Inner Film 70 Sealable 80 Ga. High 1.0 mil 70 Sealable OPP 80 Ga. High 1.0 mil Sealable (Gauge) OPP Barrier Sealable Cast Barrier Sealable Cast Sealable OPP Polypropylene OPP Polypropylene # of Packages 99 100 92 2 2 4 Tearing # of Packages Not 1 0 8 98 98 96 Tearing % Openability w/o 1% 0% 8% 98% 98% 96% Tearing Note that when the standard 80 gauge high barrier film is used as the outer or inner layer in the prior art processes I and II, extremely poor package openability was obtained because of the fragile nature of the high barrier film. Thus, 99 and 100 of the 100 bags in each test tore down the side when opened. Table II shows in novel processes I and II that the same film can be used with the present novel process with an extremely high degree of success. As can be seen, only 2 and 2 of the 100 bags in each test tore down the side. Thus, the novel process allows the use of standard films that normally provide poor performance in bag openability. The prior art process III uses an inner film that make bag opening extremely difficult due to high seal strength. In that test, 92 of the 100 bags tested tore down the side of the bag. Novel process III of the present invention uses the same inner film but provides a line of weakness wholly within the extrudate layer that enables easy opening of the bags without tearing the body of the bag. As can be seen, only 4 of the 100 bags tested tore down the side. Table III shows the results of a third test series that demonstrates the effect of polypropylene core weight on openability and sets forth the weight of polypropylene in the total extrudate. Fifty packages were tested for openability on each test series. Note that excellent results were obtained over a wide range of such weights. However, the worst results were obtained with a polypropylene core weight below 1.0. TABLE III Type Structure 1 2 3 4 5 6 7 8 9 10 Outer 75 OPP 75 OPP 75 OPP 75 OPP 75 OPP 75 OPP 75 OPP 75 OPP 75 OPP 75 OPP Polypropylene Film (Mils) Extrudate 10 # Total 10 # Total 10 # Total 10 # Total 10 # Total 7 #/Ream 7 #/Ream 7 #/Ream 7 #/Ream 7 #/Ream Polyethylene — — — — — — — — — — Outer Polypropylene 0.5-0.7 1.0-1.6 2.0-3.0 4.0-6.5 7.0-8.5 0.5-0.9 1.0-1.6 2.0-3.0 4.0-7.0 8 Core Polyethylene — — — — — — — — — — Outer Primer Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Ink — — — — — — — — — — Inner 70 70 70 70 70 70 70 70 70 70 Polypropylene Film (Mils) # of Packages 10 3 1 0 0 11 2 0 0 1 Tearing # of Packages 40 47 49 50 50 39 49 50 50 50 Not Tearing % Openability 80% 94% 98% 100% 100% 78% 96% 100% 100% 98% While the invention has been described in connection with a preferred embodiment, it is not intended to limit the scope of the invention to the particular form set forth, but, on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the sphere and scope of the invention as defined by the appended claims.
A plastic packaging material which, when formed as a package having seams, will provide a predictable line of failure along a seam when the package is opened to prevent the package from tearing down the side. The predictable failure path is provided through a lamination process involving specific resins or blends of resins laminated in three (or more) layers in which an extruded inner layer forms a weak inner bond wholly within that inner layer to create the predictable line of failure and in which the process of forming the material does not inhibit processing speed, efficiency, and economics of materials used to provide this reliable openability.
1
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transplanter used to plant vegetable seedlings in truck farms or to carry out similar agricultural works, engaging with the ground. 2. Prior Art In general, planting units are mounted on vehicles or trailers hauled by tractors or the like, so as to form the transplanters. The prior art planting units are designed to be displaceable only in a vertical direction. Whenever the transplanting trailers run along ridges, those units are controlled to rock up and down to follow upper surfaces of the ridges so that the seedlings are planted therein at a constant depth. However, the trailers or vehicles often sway sideways relative to ridges. In such an event, the planting units will fail to plant the seedlings in correct, for instance middle, zones of those ridges. This is one of the drawbacks in the prior art planting units. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an advanced transplanter that comprises at least one planting unit mounted on a trailer and displaceable sideways relative thereto, a pair of left and right ridge sensors attached to the planting unit, and a control means for moving the planting unit to slide transversely relative to the trailer, on the basis of signals transmitted from the sensors, so as to automatically adjust position of the planting unit into alignment with zones extending on and along adjacent ridges and having to be planted with seedlings. In operation of this transplanter, an operator need only to drive a tractor in a considerably rough manner to pull the trailer approximately along the ridges. The seedlings will be planted in middle zones of those ridges, without a fear of pushing down those which have been planted and are located near the planting units. The heads of vegetables such as cabbages that are heading up will be protected from the planting units which would otherwise damage them. Adjacent rows of any other vegetables will also be protected from damage when a ground between these rows is cultivated using plows in place of the planting units. Another object of the present invention is to provide a transplanter that comprises at least one planting unit mounted on a trailer and displaceable sideways relative thereto, a pair of left and right inside ridge sensors attached to the planting unit, and the ridge sensors being capable of detecting inner slopes facing one another and belonging to adjacent ridges which have longitudinal zones and extend in parallel with each other, wherein a transverse position of the planting unit is controlled based on signals transmitted from the ridge sensors while the trailer is running, whereby said unit is caused to correctly follow the longitudinal zones where seedlings are to be planted. In operation of the transplanter just summarized above, the planting unit can maintain its correct position with respect to the ridges even if the trailer slightly skews relative thereto while running along same. Seedlings can be planted accurately in any desired zone on each ridge by the planting unit whose position is being controlled using signals from the ridge sensors. In contrast with ridge sensors detecting outer side slopes of adjacent ridges, the ridge sensors in this case make a more moderate response to such a temporary change in position of said unit. The planting unit will not react to said positional change so sharply as to cause `hunting`, but will smoothly follow the ridges to be planted with the seedlings. The ridge sensors in this case are located near the center of the trailer, so that they will be protected well from any obstacles that may be present near the sides of said trailer. Still another object of the present invention is to provide a transplanter that comprises at least one planting unit mounted on a trailer and displaceable sideways relative thereto, a pair of left and right outside ridge sensors attached to the planting unit, and the ridge sensors being capable of detecting outer side slopes located at opposite sides of a plurality of adjacent ridges which have longitudinal zones and extend in parallel with each other, wherein a transverse position of the planting unit is controlled based on signals transmitted from the ridge sensors while the trailer is running, whereby said unit is caused to correctly follow the longitudinal zones where seedlings are to be planted. In operation, the ridge sensors located remote from each other in this case do cooperate with each other to detect even a slight sideways offset of the planting unit. The planting unit in this case makes a so quick response to said offset as to be controlled more sharply in position. Maintenance of those ridge sensors located away from the trailer body is easy. Yet still another object of the present invention is to provide a transplanter that comprises at least one planting unit mounted on a trailer and displaceable sideways relative thereto, a pair of left and right ridge sensors attached to the planting unit; and the ridge sensors being switchable over between one position thereof to detect inner slopes facing one another and belonging to adjacent ridges and another position to detect outer slopes located at opposite sides of the adjacent ridges, which have longitudinal zones and extend in parallel with each other, wherein a transverse position of the planting unit is controlled based on signals transmitted from the ridge sensors while the trailer is running, whereby said unit is caused to correctly follow the longitudinal zones where seedlings are to be planted. Versatility of the ridge sensors is remarkably enhanced in this case, because they may be set selectively in any desired position. In one position, they will detect the inner slopes of two adjacent ridges. In another position, they will detect the outer slopes of two or more adjacent ridges, or alternatively detecting a left and right slopes of one broad ridge covered with two or planting units. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a rear elevation of inside ridge sensors incorporated in a transplanter, provided in an embodiment and shown in use; FIG. 2 is a side elevation of the transplanter shown together with a tractor; FIG. 3 is a plan view the transplanter also shown together with the tractor; FIG. 4 is a rear elevation of the transplanter shown together with the tractor; FIG. 5 is an enlarged side elevation of the transplanter; FIG. 6 is an enlarged plan view of the transplanter; FIG. 7 is a side elevation of a joint that is disposed between the tractor and a trailer pulled thereby to carry the transplanter; FIG. 8 is a plan view of the joint; FIG. 9 is a rear elevation of a transverse hydraulic cylinder accompanying the joint; FIG. 10 is a side elevation of one of planting units incorporated in the transplanter; FIG. 11 is a plan view of the planting units; FIG. 12 is a side elevation of one of ridge sensors attached to transplanter; FIG. 13 is a rear elevation of the ridge sensor; FIG. 14 is a plan view of he ridge sensor; FIG. 15 is a rear elevation of the ridge sensors in another mode of use; FIG. 16 is a block diagram illustrating the relationship between a controller and relevant elements; and FIG. 17 is a flow chart showing the control executed in and by the controller. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Now, the present invention will be described in more detail referring to some embodiments shown in the drawing. In FIGS. 1 to 6 illustrating one embodiment, the reference numeral 1 generally denotes an automotive tractor having front traction wheels 2, rear traction wheels 3, steering wheel 4 and a seat 5. An operator will ride on and maneuver this tractor, usually sitting on its seat 5. Seedling racks 7 are disposed in front of the steering wheel 4 and beside a bonnet 6. An engine installed under the bonnet will drive the traction wheels 2 and 3 in reversible directions, with the front wheels 2 being steered by the steering wheel 4. Those traction wheels on the tractor may be replaced with a pair of left and right endless crawlers. An automatic steering system may be employed in the tractor, which system comprises a navigation sensor, an actuator and a controller receiving signals from the sensor and giving commands to the actuator. In such a case, the tractor will run itself correctly along the ridges. As will be seen in FIGS. 7-9, the rear traction wheels 3 are disposed beside a main transmission housed in a case 8. A pair of left and right fulcrum brackets 9 that have frontal ends bolted to a rear face of the transmission case protrude rearwardly. Short transverse shafts 11 secured to frontal ends of lower links 10 are rotatably held in place by the brackets 9. Each lower link 10 can swing about its shaft 11 so that its rear end is rockable up and down. A T-shaped gear case 12 is attached by a hitch frame 13 to rear ends of the lower links 10, which are connected to a pair of lifting links 13a together with the hitch frame 13. Those lifting links are in turn operatively connected to arms 14a extending rearward from an oil-hydraulic cylinder 14 secured to a top surface of the transmission case 8. Each of linking frames 15 standing upright has a lower end operatively connected to lower links 10. The linking frame 15 has an upper end region operatively connected by a further oil-hydraulic cylinder 16 and its piston rod 17 to a hinge 18 secured to the transmission case 8, wherein said cylinder and rod constitute a top link. A tool bar 19, that is a hollow cylinder of square cross section, is welded to lower sides of intermediate portions of the lower links 10. Such a tool bar 19 extends transversely and horizontally in rear of and between the rear traction wheels 3. As shown also in FIG. 10, a pair of left and right planting units 20 are mounted on the tool bar 19 so as to provide a double-row planter 21 (see FIG. 11). Each planting unit 20 comprises: a unit frame 22; a seedling rack 25; a pair of picking pawls 27 cooperating with each other in a manner like a Japanese table folk (`hashi`) for taking seedling pots out of the rack; a hopper-shaped planting pawl 28 for planting the seedling pots one by one in a ridge 30; a leveling roller 29 disposed in front of the planting pawl; a ridge cutter 31 disposed in front of the roller 29; a smoothing float 32 interposed between the roller 29 and the cutter 31; a pair of covering-up rollers 33 disposed in rear of the planting pawl 28; a auxiliary or branched transmission 34 for driving the planting unit 20; and a train of power-transmitting blocks 35, 36 and 37 (see FIG. 6) operatively connected one to another and also to the transmission 34. The seeding rack 25 is guided along an upper and lower rails 23 and 24 (see FIG. 5) so as to reciprocate fore and aft relative to the frame 22. The picking pawls 27 take the seedling pots one by one from a tray 26 (see FIGS. 4 and 6) formed along an inner side of the seedling rack 25. The leveling roller 29 levels off the ridge surface, before the seedlings are inserted in and along a middle zone in the ridge by the planting pawl 28. The cutter 31 forms a groove in the middle zone, before the latter is scraped with the smoothing float 32 (FIG. 11). The covering-up rollers 33 will put soil towards the planted seedling pots. Power will be transmitted from the branched transmission 34 to all the driven parts so that the pair of the picking pawls 37 as well as the planting pawl 28 move on and along their own looped routes, respectively, to thereby pick up the seedling pots and plant them in the ridge. On the other hand, the seedling rack 25 reciprocates fore and aft, and the seedling tray 26 continues to run obliquely and downwards. Therefore, the seedling pots are caused to move not only fore and aft but also vertically at the same time, thus enabling a continuous planting of them at regular intervals along the ridge. As shown in FIGS. 6 to 9, and as best seen in FIG. 9, two rigid plates each having ends bolted 39 to each other fit on the tool bar 19 to form sleeves 38 slidable therealong. These sleeves will be controlled to take any desired offset or transverse position. Bearing collars 40 each having an ear welded to each sleeve 38, so that a hitch plate 41 (see FIG. 7) as one part of the unit frame 22 is attached to the collars 40 to be rotatable therewith. Each branched transmission 34 is interposed between and fixed to the inner and outer collars 40 (see FIG. 8), also rotatably together with same. The T-shaped gear case 12 and the pairs of the collars 40 are in a coaxial alignment with each other and extend in parallel with the tool bar 19. A transverse power-take-off shaft (viz. PTO shaft) 42 that extends through the gear case 12 and the collars 40 is rotatably supported thereby. A principal PTO shaft 43 protruding rearward from the transmission case 8 is operatively connected to transverse PTO shaft 42, through a universal joint 44 (see FIG. 7). Thus, an output from the engine of tractor 1 will be transmitted to the transverse PTO 42, which in turn drives the branched transmissions 34 for the planting units. A transverse rail 45 is fixed on the linking frames 15 and extends in parallel with the tool bar 19, and rollers 47 are carried by the upper ends of control bars 46. Those bars 46 have feet pivoted to the collars 46, and rollers 47 engaging with the longitudinal cavity of transverse rail 45 are displaceable along same. A tie bar 48 connects the hitch plate 41 to the control bar 46 (see FIGS. 7 and 8), such that the unit frame 22 can rock up and down around the transverse PTO shaft 42 when the piston rod 17 extends from or is retracted into the further hydraulic cylinder 16. On the other hand, the two sleeves 38 each having an ear and respectively corresponding to the left and right ridges are fixed to transverse tie bars 50 (see FIG. 9). Those ears rigidly engage with selected longitudinal portions of those tie bars 50, so that the distance between sleeves 38 is adjustable. Inserted between the tie bars 50 is a sliding frame 49 having opposite ends secured thereto. A transverse hydraulic cylinder 51 and its piston rod 52 operatively intervene between the opposite ends of the sliding frame 49 so as to adjust transverse position thereof. In response to the piston rod 52 extending from or being retracted into the cylinder, the left and right planting units 20 will be forced to the left or to the right in unison with each other and relative to the tool bar. As shown in FIGS. 5, 7 and 8, coiled springs 53 extending fore and aft connect the frontal ends of unit frames 22 to the rear end of tractor 1. A connecting bar 56 is fixed to the rear ends of the unit frames, and a freely rotatable and ground-engaging gauge wheel 55 is attached to the connecting bar. A handle 54 is operable to adjust the vertical distance between the frames 22 and the gauge wheel 55. The branched transmissions 34 fixed to the unit frames 22 have output shafts 57 (see FIG. 10), and the power-transmitting blocks 35 for driving the planting pawls are operatively connected to and rockable about those output shafts 57. Characteristically provided in the present invention are sensor frames 58 extending fore and aft and each having a frontal end secured to said block 35. A leveling frame 60 is connected by parallel links 59 to a frontal end of the sensor frame 58. The leveling roller 29 mentioned above is rotatably carried by an arm 61 protruding rearward from the leveling frame 60. A longitudinal arm 63 extending fore and aft to rotatably carry with its middle portion the pair of covering-up rollers 33 has a frontal end rotatably engaging with a pivot 62. This pivot 62 is attached to the sensor frame 58 at a portion near its rear end. A rod 65 connects the parallel links 59 to the arm 63, and a manual lever 66 is connected to the latter so as to simultaneously lift or simultaneously lower the leveling and covering-up rollers 29 and 33. Thus, a desired depth of planting the seedlings may be selected by changing the planting pawl 28 in its height above the ground. As shown in FIGS. 10 and 15, a sensor arm 67 fixed to a middle portion of the sensor frame 58 holds in place a ridge sensor 68 and a guide roller 69. Also shown in FIG. 10 is a planting depth sensor consisting of a lowering microswitch 70a, a raising microswitch 70 and an upper limit microswitch 71. A sensor arm 73 connected by a vertical rod 72 to the sensor frame 58 will close any one or two of those microswitches. A control lever connected to the arm 73 is operable to select a pressure at which the covering-up rollers 33 will press the soil towards the root of each seedling planted. FIGS. 1, 12 and 15 show that a bracket 75 rigidly secures a sensor supporter 76 to the sensor arm 67, wherein the ridge sensor 68 and the guide roller 69 form an assembly attached to the supporter and integral therewith. As best seen in FIG. 1 compared with FIG. 15, the assemblies of said ridge sensor 68 and guide roller 69 are capable of being arranged either at one of their positions located inside the respective planting units 20a and 20b, or at the other located outside the latter. The sensor frame 58 generally U-shaped (see FIG. 10) to which the sensor arm 67 is secured has an obliquely upright leg fixed to a transverse base 77, which in turn is attached to the lower face of the power-transmitting block 35. Forward seats 78 are disposed symmetrically (see FIG. 10) at outer sides of the middle portions of said the sensor frame 58. Rearward seats 79 are likewise disposed symmetrically at the outer sides of rearward portions of frame 58. Plate members 80 and 81 welded or otherwise secured to the frontal and rear ends of the sensor arm 67 are bolted at 82 to the seats 78 and 79, respectively. The bracket 75 for sensor supporter is fixedly attached to the lower face of the sensor arm 67, as mentioned above (see FIG. 13), and has round holes 84 at proper intervals. Correspondingly, the sensor supporter 76 has elongate apertures 85. Thus, the sensor supporter bolted at 83 to the bracket 75 is adjustable with respect to its transverse position. A roller holding member 86 (FIG. 12) for rotatably holding the guide roller 69 is secured to the rear face of sensor supporter 76. The ridge sensor 68 consists of a ridge detecting shoe 87 and a ridge detecting microswitch 88, both attached to a forwardly protruding bracket 89 secured to the frontal face of said supporter 76. The ridge detecting shoe 87 is generally L-shaped in plan view (FIG. 14), and its forward end is rockably connected by a pivot 90 to the bracket 89 (FIGS. 12 and 14). A ridge contacting plate 91 located outside the free end of the shoe 87 is secured to an end of the sensor supporter 76 in a manner not shown. In operation, the ridge contacting plate 91 will be kept in a sliding contact with an upper region of a side slope of the ridge 30, so that the shoe's free outer end does not directly contact the ridge but is pressed against the inner face of ridge contacting plate 91. The inner end of said shoe 87 is always urged by a coiled spring 92 in a direction such that the ridge detecting microswitch 88 may usually be kept closed to transmit an `OFF` signal. A switch supporter 93 holding the microswitch 88 extends from the bracket 89. As the plate 91 comes into a sliding contact with the ridge 30 (see FIG. 14), the ridge detecting shoe 87 will swing about the pivot 90 in another direction such that the ridge detecting microswitch 88 is opened to transmit an `ON` signal indicating the ridge contacted by said shoe. In one mode of using the transplanter, each of left and right planting units 20a and 20b will plant seedlings in one ridge, as FIG. 1 illustrates. Each pair of the ridge sensor 68 and the guide roller 69 will be arranged inside the planting unit. The left-hand ridge sensor 68a will face and detect the right side slope of left-hand ridge, with the right-hand ridge sensor 68b simultaneously facing and detecting the left side slope of the right-hand ridge. In another mode, both the left and right planting units 20a and 20b will plant seedlings in one and the same ridge, as FIG. 15 illustrates. In this case, each pair of the ridge sensor 68 and the guide roller 69 will be arranged outside the planting unit. The left-hand ridge sensor 68a will face and detect the left side slope of the one ridge, with the right-hand ridge sensor 68b facing and detecting the right side slope of said one ridge. In still another mode, each pair of the ridge sensor 68 and guide roller 69 are disposed outside the left or right planting unit 20a or 20b. Further, three or more planting units 20 may be mounted on the trailer, wherein the side slope of any one ridge, or more than two side slopes of those ridges, may be detected with the sensor(s) and guide roller(s). A controller 95 is provided herein for the transplanter. This controller is designed to give command signals to the transverse hydraulic cylinder 51 and also to an indicator for indicating any offset of the planting units 20a and 20b relative to the ridge 30. The controller 95 comprises a selection switch 96 for converting manual control mode to automatic control mode, or vice versa. An indicator 94 electrically connected to the controller 95 indicates the position of those planting units 20a and 20b offset to the left or offset to the right. Signals from the left-hand ridge sensor 68a and the right-hand one 68b will be input to this controller, together with those from a manual switch 97 for displacement of the transplanter to the left and another manual switch 98 for displacement to the right. The planting units 20 mounted on the trailer pulled by the tractor may be controlled by the controller 95, based on the signals from the ridge sensors 68, as to the transverse position of those units relative to the ridge 30, in any appropriate or desired manner. In the case wherein the left-hand and right-hand ridge sensors 68a and 68b are arranged inside the left right planting units 20a and 20b, respectively, the control of this system will be effected in a manner briefly shown in FIG. 17. When in the automatic control mode the left-hand sensor 68a is turned on by the left side ridge, the planting units 20a and 20b will be displaced to the right. When the right-hand sensor 68b is turned on by the right side ridge, the planting units will be displaced to the left. Thus, the seedlings will be planted automatically in a correct zone, for instance in a middle longitudinal zone of the ridge 30. When in manual control mode the left or right-hand ridge sensor 68a or 68b is turned on due to the displacement of the left and right planting units 20a and 20b to the left or to the right, the indicator 94 will indicate such an offset of those planting units. An operator may maneuver the tractor by the steering wheel 4 so as to correct the position of said units 20a and 20b relative to the ridges. Alternatively, he or she may use the manual switches 97 and 98 to cause the transverse hydraulic cylinder 51 to extend or retract its piston rod, for the same purpose. In summary, the transplanter comprises the planting units 20 mounted on the trailer to be displaceable sideways relative thereto, the pair of left and right ridge sensors 68 attached to the planting units, and the control means 90 for moving the planting units 20 to slide transversely relative to the trailer. The signals from the sensors 68 are used in said means 90 to automatically adjust position of the planting units into alignment with longitudinal ridge zones to be planted with seedlings. In operation, an operator can maneuver the tractor 1 easily to cause the trailer to run approximately along the ridges, whereby the seedlings are planted correctly without pushing down those which have been planted, and without damaging the heads of vegetables such as cabbages. Adjacent rows of any other vegetables will also be protected from damage when a ground between these rows is cultivated using plows in place of the planting units. The transplanter provided herein from another aspect comprises also the planting units 20, the left and right inside ridge sensors 68 attached thereto and capable of detecting inner slopes of adjacent ridges 30. Transverse position of the planting units is controlled based on signals from the ridge sensors so that said units correctly follow the longitudinal ridge zones where seedlings are to be planted, even if the trailer slightly skews. Seedlings can thus be planted accurately in any desired zone on each ridge. In contrast with ridge sensors detecting outer side slopes of adjacent ridges, the ridge sensors in this case make a more moderate response to such a temporary change in position of said unit, thus avoiding the so-called `hunting`. The ridge sensors in this case are located near the center of the trailer, so that they will be protected well from any obstacles that may be present near the sides of said trailer. The transplanter provided herein from still another aspect, the pair of left and right outside ridge sensors 68 are attached to the planting units 20 so as to detect outer side ridge slopes, wherein transverse position of the planting units is also controlled based on the signals from the ridge sensors. In operation, the ridge sensors 68 located remote from each other in this case do cooperate with each other to detect even a slight sideways offset of the planting units. The planting units makes a so quick response as to be controlled more sharply in position. Maintenance of those ridge sensors located away from the trailer body is easy. The transplanter provided herein from yet still another aspect comprises the planting units also mounted on the trailer and displaceable sideways relative thereto. The pair of left and right ridge sensors 68 attached to the planting units are capable of being converted in their position, between one position to detect inner slopes and another position to detect outer slopes of the adjacent ridges. The transverse position of planting units is also controlled based on signals from the ridge sensors, to correctly follow the longitudinal zones where seedlings are to be planted. Versatility of the ridge sensors is remarkably enhanced in this case.
A seedling planter mounted on a trailer is provided with means to sense the side walls of ridges of earth and a means to position the planter over ridges of earth in response to the ridge side wall sensing means by transporting the planter sideways from the for/aft center line of the trailer irrespective of the track of the trailer.
0
FIELD OF INVENTION The invention relates to an apparatus and method for automatically milking animals, comprising a milking robot, provided with one or more arms for carrying robot equipment, said robot equipment including teat cups, as well as a cleaning member for cleaning teats of an animal. BACKGROUND OF THE INVENTION Such an apparatus is known from Dutch Patent Application 9201734. With the cleaning member described in said patent application the teats of the animal to be milked are cleaned by two cleaning rollers rotating in opposite directions between which rollers a teat is cleaned by the rubbing motion of the rollers. Improvements to such apparatus are an object of this invention. SUMMARY OF THE INVENTION According to the invention the apparatus is characterized in that a cleaning member is provided on the robot arm construction so as to be movable relative to the teat cups. In this manner the cleaning member is pivoted together with the robot arm construction and consequently is available at all times for cleaning purposes. This produces a considerable gain of time, while furthermore coupling means are not necessary for coupling the cleaning member to the robot arm construction. In accordance with further inventive feature the cleaning member is pivotally connected with an almost vertical shaft arranged on an outer arm of the robot arm construction. According to again another inventive feature the cleaning member is connected via an arm with the vertical shaft. In order to prevent the arm from sagging, in accordance with a further inventive feature of the arm is supported on a guide means disposed on the robot arm construction. For the purpose of being able to clean the cleaning member or to repair same, according to another aspect of the invention the cleaning member is rotatable about an almost horizontal shaft located near vertical shaft. In accordance with another inventive feature the cleaning member is movable electrically or pneumatically from an inoperative position to an operative position. According to again another aspect of the invention, the cleaning member has a motor driven cleaning element. In a preferred embodiment in accordance with the invention the cleaning element comprises two motor-driven profiled rollers disposed next to each other and at some distance from each other. In order to avoid that during cleaning of the teats dirt gets into the teat cups, according to another inventive feature a cover plate is arranged under the cleaning member. For the purpose of cleaning the cleaning element or moistening the teats or both, according to an inventive feature the cleaning member comprises a spraying device by means of which a cleaning or disinfecting fluid or both can be spread. BRIEF DESCRIPTION OF THE DRAWINGS 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, to the accompanying drawings, in which: FIG. 1 shows a side view of the apparatus according to the invention; FIG. 2 shows, in plan view, the apparatus shown in FIG. 1 in a position in which the cleaning member is brought under an animal present in the milking compartment; and FIG. 3 shows more in detail the cleaning member represented in FIGS. 1 and 2. DESCRIPTION OF THE PREFERRED EMBODIMENTS The apparatus as shown in FIGS. 1 and 2 comprises a milking compartment 1, surrounded by a framework 2 allowing the animal a limited freedom of movement. The animal can enter the milking compartment via a longitudinal side near the rear thereof and leave same via the same longitudinal side near the front thereof. The front side of the milking compartment being provided with a feeding installation, the cow will advance sufficiently far and will come into a position in which she can be milked easily. At the other longitudinal side of the milking compartment, being opposite to the one including the entrance and exit, there is provided a fixed frame 3 constituting part of framework 2, which frame 3 includes a first frame part 4 and a second frame part 5. A first frame part 4 extends parallel to a second frame part 5 and is situated substantially thereabove. First frame part 4 is fixed to the outside of two vertical parts or stands 6 and 7 constituting part of framework 2, while second frame part 5 is fixed therebetween. To first frame part 4, there is movably attached a milking robot 8 for automatically milking animals. This milking robot 8 is supported against second frame part 5 disposed at such a height that arms of the milking robot 8 are movable below same and under the cow present in the milking compartment. Milking robot 8 comprises a carrier frame 9 for its further parts. By designing upper frame part 4 as a rail, the carrier frame 9, and consequently the entire milking robot 8, can easily be moved along this frame part. Carrier frame 9 includes a beam 10 extending substantially parallel to first frame part 4, a beam 11 directed vertically downwardly perpendicular to beam 10 and fixed thereto, and two struts 12. Provided near the ends of the beam 10, are pairs of supporting elements 13. To each pair of supporting elements 13, by means of supporting plates 14 fixed thereto, at an angle of approximately 45° two rollers 16, are provided constituting a rollers pair 15 arranged so that carrier frame is suspended whereby its is easily movable along the upper frame part 4. On beam 10 of carrier frame 9, on both sides, there are provided two carriers 17, to which is attached a motor 19 movable about a pivot shaft 18. Driven by this motor 19 is a roller 20, preferably having a rubber surface, which roller is urged against upper frame part 4 by means of a spring member 21. By this spring member 21 roller 20, driven by motor 19, is continually urged upper frame part 4, so that, when the motor is driven, it is moved along upper frame part 4, and consequently, the entire carrier frame 9 is so moved. To the supporting member 13, is attached a sensor 22 comprising a laser for example. By means of this sensor 22, it is possible to guide the milking robot, in the longitudinal direction of the milking compartment from an inoperative position to a starting position, in which the milking robot arms are moved under the animal present in the milking compartment, and caused to follow the movements of the animal in the longitudinal direction thereof. For that purpose, the sensor 22 cooperates with a supporting member 23 which is movable against the rear side of the animal. By means of a rod system which, in the present embodiment, is constituted by a quadrangle construction and, in particular, by a parallelogram construction 24, this supporting member 23 is pivotally arranged on the milking compartment's floor by means of two rods 25. Supporting member 23 is provided with a plate 26, extending outboard of frame parts 4 and 5 which plate 26 is arranged to reflect a signal transmitted by sensor 22. After sensor 22 receives the reflected signals, it transmits a control signal which is a measure for the actual, i.e. the measured distance between plate 26 and sensor 22. By means of this control signal, motor 19 moves milking robot 8 in the longitudinal directions of the milking compartment so that the distance between plate 26 and sensor 22 is maintained at a predetermined selected value. In its inoperative position, milking robot 8 is moved as far rearwardly as possible relative to frame parts 4 and 5, so that a contact element 27 bears against plate 26 and thus positioning supporting member 23 in its rearmost position. In other words, supporting member 23 is secured in its aftermost location by the milking robot 8 when the latter is in its inoperative position. When, in the longitudinal forward direction of the milking compartment, the milking robot moves from its inoperative position to its starting position, in which its arms are moved under the animal present in the milking compartment then supporting member 23 is no longer secured to the rear of milking compartment 1, and, by means of a compression spring 28 disposed between the parallelogram construction 24 and the framework 2, is resiliently caused to advance so that it bears against the buttocks of the cow then present in the milking compartment. Upon forward of backward movement of the cow, through the continuing pressure imparted by spring 28, supporting member 23 is always bearing against the rear side of the animal, so that the position of the plate 26 determines the longitudinal disposition of the animal in the milking compartment and, by means of sensor 22, while maintaining the predetermined spacing between plate 26 and sensor 22, the milking robot automatically follows the longitudinal movements of the cow in the milking compartment. In the present embodiments, beam 11 of carrier frame 9 extends vertically downwardly to somewhat below the second frame part 5. At the lower side of this beam 11 is disposed a horizontal, rearwardly extending strip 29 which is provided with a freely rotatably roller element 30. Lower frame part 5 is constituted by a rail, in particular one designed as a U-shaped beam, while the freely rotatable roller element 30 is arranged in so that it is movable between the two upright edges of the U-shaped beam. In this manner, milking robot 8 is supported by lower frame part 5 and when being moved by means of the motor over the first frame part 4, moves smoothly along second frame part 5. In addition to carrier frame part 9, the milking robot comprises a robot arm construction designated generally by reference numeral 31 which, by means of a control cylinder and piston unit 32, is movable substantially vertically relative to carrier frame 9. By means of a quadrangle construction 33, the robot arm construction 1 is movably connected with carrier frame 9. In the embodiment shown, the upper arm 34 of this quadrangle construction 33 has a fixed length, while the lower arm 35 thereof is adjustable in length so as to enable the robot arm construction 31 to be adjusted to a limited extent. The robot arm construction 31 comprises a substantially vertical robot arm 36 as well as robot arms 37 that are movable in a substantially horizontal plane. By means of quadrangle construction 33, robot arm 36 is connected with beam 11 of the carrier frame 9. Control cylinder and piston unit 32 is active between carrier frame 9 and robot arm 36. As, by means of the lower arm 35 of the quadrangle construction 33, the orientation of robot arm 36 is slightly adjustable, the spatial position of the action point of control cylinder and piston 32 at unit robot arm 36 is not entirely fixed. For that reason, the housing of the control cylinder and piston unit 32 is provided, at least pivotally to a limited extent, on a carrier plate 38 attached to beam 10 of carrier frame 9. On this carrier plate 38 are disposed supports 39, between which the housing of control cylinder and piston unit 32 is capable of being moved about a pivot shaft 40. In the present embodiment, control cylinder and piston unit 32 is designed as a servo-pneumatic positioning cylinder and piston unit. This means that, at the lower end of its piston rod 41, by means of a plate 42 fixed thereto, there is attached by position feedback rod 43, by means of which, in a connected part of the control cylinder and piston unit, a potentiometer transmits a signal indicating the position of the piston rod relative to the cylinder housing, while, with the aid of that signal, the position of the piston rod 41 relative to the cylinder housing is post-guided to a preset position. Furthermore, control cylinder and piston unit 32 is provided with an overload protection enabling robot arm construction 31 to be moved into its lowest position of an animal present in the milking compartment exerts pressure thereon, such as kicking it. Milking robot 8 includes arms 44, 45 and 46. Arms 44 and 45 are arranged at a fixed angle of 90° relative to each other. Therefore, the latter arms are moved together. Such as by a control cylinder and piston member 47 provided between a supporting plate 48 attached to the robot arm 36 and a connecting plate 49 disposed between the two latter arms. Two arms 44 and 45 are pivotable about a substantially vertical pivot shaft 50 between supporting plate 48 and a supporting plate 48', which latter is also rigidly connected to the robot arm 36, more in particular at lower end thereof. Arm 46 is pivotable relative to the arm 45 about a substantially vertical pivot shaft 51 and is pivoted relative thereto by means of a control cylinder or piston combination 52 which is disposed between arm 46 and part of arm 45 that is situated near the connecting element 49. Near the end of arm 46 are a pair of teat cups 53 and another pair of forward teat cups 54 to be connected to the teats of the cow (see FIG. 1). Between the two teat cups 54 is disposed a slide 55, which is movable on arm 46 and on which is provided a sensor 56, which by a sectorwise scanning movement can accurately determine the position of the teats, so that the control cylinder and piston assemblies 32, 47 and 52 can be computer-controlled whereby the teat cups are connected properly to the teats. The robot arms 44, 45 and 46 having been brought to under the cow, they are in relatively low position, in which sensor 56 has not yet detected teats. By means of the control cylinder and piston members 32, robot arms 44, 45 and 46 are raised stepwise until sensor 55 detects one or more teats of the animal. If, during this upward movement, the robot arms 44, 45 and 46 area raised so that the upper side of sensor 56 bears against the cow's abdomen, then by means of a s switch 56' provided on the upper side of sensor 56, a downward movement of the robot arm is effected, whereafter, by means of sensor 56, while again stepwise raising the robot arm occurs, the procedure for ascertaining the position of the teats can be repeated. For the purpose of cleaning the teats of an animal to be milked, the above-described apparatus is furthermore provided with a cleaning member 58. Cleaning member 58 comprises two juxtaposed profiled rollers 59, the shafts of which are pivotally bearing-supported in a gearbox 60. The profiled rollers 59 are driven by an electric motor 61 attached to a side of gearbox 60 Gearbox 60 is mounted on a cover plate 62 extending to under the profiled rollers 59. Between profiled rollers 59 is disposed a spraying device 63 by means of which profiled rollers 59 or the teats of an animal to be milked can be cleaned. Spraying device 63 includes a line 64 via which the spraying fluid can be supplied. Between profiled rollers 59, the line 64 is provided with a number of perforations 65 via which the spraying fluid is discharged from line 61. Line 64 is provided on cover plate 62. Via a striplike arm 66 the cleaning member 58 is connected with arm 46 of the robot arm construction 31. One end of arm 66 is fixedly connected with cover plate 62 and the other end thereof is connected pivotally about a substantially horizontal shaft 67 with a vertical shaft 68 of an electric motor 69. Motor 69 is disposed in a recess of a hood 70 of arm 46. For the purpose of being able to carry out maintenance work of cleaning member 58, the latter is capable of being pivoted upwards about horizontal shaft 67. With the aid of electric motor 69 cleaning member 58 can be pivoted from an inoperative position, as shown in FIG. 2, to an operative position, as indicated in FIG. 3. In order to prevent arm 66 from sagging, a curvelike guide strip 71 is disposed on a hood 72 which is connected to arm 45. Arm 66 rests permanently on guide strip 71. In order to secure cleaning member 58 both in the inoperative position and in the operative position, there are provided blocking means on guide strip 71. In this manner electric motor 69 does not have to be permanently energized. Hood 72 is provided on the further arm 45 of the robot arm construction 31, above which cleaning member 58 is received in its inoperative position. It is possible to dispose a boxlike housing on hood 72 in which cleaning member 58 can be stored in its inoperative position. This has the advantage that the boxlike housing there may be provided cleaning elements, such as brushes, by means of which the cleaning elements can be cleaned. In order to avoid that, during cleaning of the teats, cleaning fluid supplied through the line 64 via the cover plate 62 gets into teat cups 53 and 54, the edges of the cover plate 62 may be provided with an upright portion and a discharge line for discharging the cleaning fluid. The above-described embodiments of the cleaning member can be applied not only in combination with the apparatus for automatically milking animals, but also separately. Although I have disclosed the preferred embodiment of my invention, it should be understood that it is capable of other adaptations and modifications within the scope of the following claims:
Apparatus for automatically milking animals in a milking compartment by means of teat cups on a robot arm that also includes a sensing device for locating the teats of the animal to be milked. The robot arm is automatically positioned longitudinally under the animal to be milked and includes a cleaning element which is connected thereto by a further arm member that can pivot relative to the robot arm about substantially horizontal and vertical axes. The cleaning member is pivotable from a position for cleaning the animal's teats to a further position displaced therefrom. The cleaning member includes a cover plate thereunder which is disposed under the cleaning member and above the teat cups mounted on the robot arm when in position for cleaning the animal's teats. The cleaning member comprises motor rotated parallel horizontal profiled spaced apart rollers and a spraying device is provided on the cleaning member for moistening the rollers. The cleaning member is pivoted to an inoperative position about the vertical axis and to a position for maintenance about the horizontal axis.
0
BACKGROUND [0001] The present disclosure is related to marking and printing methods and systems, and more specifically to methods and systems for precisely metering a dampening fluid (such as a water-based fountain fluid) in a variable lithography marking or printing system. [0002] Offset lithography is a common method of printing. (For the purposes hereof, the terms “printing” and “marking” are used interchangeably.) In a typical lithographic process the surface of a print image carrier, which may be a flat plate, cylinder, belt, etc., is formed to have “image regions” of hydrophobic and oleophilic material, and “non-image regions” of a hydrophilic material. The image regions correspond to the areas on the final print (i.e., the target substrate) that are occupied by a printing or marking material such as ink, whereas the non-image regions are the regions corresponding to the areas on the final print that are not occupied by said marking material. The hydrophilic regions accept and are readily wetted by a water-based dampening fluid (commonly referred to as a fountain solution, and typically consisting of water and a small amount of alcohol as well as other additives and/or surfactants). The hydrophobic regions repel dampening fluid and accept ink, whereas the dampening fluid formed over the hydrophilic regions forms a fluid “release layer” for rejecting ink. Therefore the hydrophilic regions of the printing plate correspond to unprinted areas, or “non-image areas”, of the final print. [0003] The ink may be transferred directly to a substrate, such as paper, or may be applied to an intermediate surface, such as an offset (or blanket) cylinder in an offset printing system. The offset cylinder is covered with a conformable coating or sleeve with a surface that can conform to the texture of the substrate, which may have surface peak-to-valley depth somewhat greater than the surface peak-to-valley depth of the imaging plate. Sufficient pressure is used to transfer the image from the offset cylinder to the substrate. Pinching the substrate between the offset cylinder and an impression cylinder provides this pressure. [0004] The above-described lithographic and offset printing techniques utilize plates which are permanently patterned, and are therefore useful only when printing a large number of copies of the same image (long print runs), such as magazines, newspapers, and the like. However, they do not permit creating and printing a new pattern from one page to the next without removing and replacing the print cylinder and/or the imaging plate (i.e., the technique cannot accommodate true high speed variable data printing wherein the image changes from impression to impression, for example, as in the case of digital printing systems). Furthermore, the cost of the permanently patterned imaging plates or cylinders is amortized over the number of copies. The cost per printed copy is therefore higher for shorter print runs of the same image than for longer print runs of the same image, as opposed to prints from digital printing systems. [0005] Lithography and the so-called waterless process provide very high quality printing, in part due to the quality and color gamut of the inks used. Furthermore, these inks—which typically have a very high color pigment content (typically in the range of 20-70% by weight)—are very low cost compared to toners and many other types of marking materials. However, while there is a desire to use the lithographic and offset inks for printing in order to take advantage of the high quality and low cost, there is also a desire to print variable data from page to page. Heretofore, there have been a number of hurdles to providing variable data printing using these inks. Furthermore, there is a desire to reduce the cost per copy for shorter print runs of the same image. Ideally, the desire is to incur the same low cost per copy of a long offset or lithographic print run (e.g., more than 100,000 copies), for medium print run (e.g., on the order of 10,000 copies), and short print runs (e.g., on the order of 1,000 copies), ultimately down to a print run length of 1 copy (i.e., true variable data printing). [0006] One problem encountered is that the viscosity of offset inks are generally too high (often well above 50,000 cps) to be useful in nozzle-based inkjet systems. In addition, because of their tacky nature, offset inks have very high surface adhesion forces relative to electrostatic forces and are therefore almost impossible to manipulate onto or off of a surface using electrostatics. (This is in contrast to dry or liquid toner particles used in xerographic/electrographic systems, which have low surface adhesion forces due to their particle shape and the use of tailored surface chemistry and special surface additives.) [0007] Efforts have been made to create lithographic and offset printing systems for variable data in the past. One example is disclosed in U.S. Pat. No. 3,800,699, incorporated herein by reference, in which an intense energy source such as a laser is used to pattern-wise evaporate a dampening fluid. [0008] In another example disclosed in U.S. Pat. No. 7,191,705, incorporated herein by reference, a hydrophilic coating is applied to an imaging belt. A laser selectively heats and evaporates or decomposes regions of the hydrophilic coating. A water based dampening fluid is then applied to these hydrophilic regions, rendering them oleophobic. Ink is then applied and selectively transfers onto the plate only in the areas not covered by dampening fluid, creating an inked pattern that can be transferred to a substrate. Once transferred, the belt is cleaned, a new hydrophilic coating and dampening fluid are deposited, and the patterning, inking, and printing steps are repeated, for example for printing the next batch of images. [0009] In the aforementioned lithographic systems it is very important to have an initial layer of dampening fluid that is of a uniform and desired thickness. To accomplish this, a form roller nip wetting system, which comprises a roller fed by a solution supply, is brought proximate the reimageable surface. Dampening fluid is then transferred from the form roller to the reimageable surface. However, such a system relies on the mechanical integrity of the form roller and the reimageable surface, the surface quality of the form roller and the reimageable surface, the rigidity of the mounting maintaining spacing between the form roller and the reimageable surface, and so on to obtain a uniform layer. Mechanical alignment errors, positional and rotational tolerances, and component wear each contribute to variation in the roller-surface spacing, resulting in deviation of the dampening fluid thickness from ideal. [0010] Furthermore, an artifact known as ribbing instability in the roll-coating process leads to a non-uniform dampening fluid layer thickness. This variable thickness manifests as streaks or continuous lines in a printed image. [0011] Still further, while great efforts are taken to clean the roller after each printing pass, in some systems it is inevitable that contaminants (such as ink from prior passes) remain on the reimageable surface when a layer of dampening fluid is applied. The remaining contaminants can attach themselves to the form roller that deposits the dampening fluid. The roller may thereafter introduce image artifacts from the contaminants into subsequent prints, resulting in an unacceptable final print. [0012] In addition, cavitation may occur on the form roller in the transfer nip due to Taylor instabilities (see, e.g., “An Outline of Rheology in Printing” by W. H. Banks, in the journal Rheologica Acta, pp. 272-275 (1965)), incorporated herein by reference. To avoid these instabilities, systems have been designed with multiple rollers that move back and forth in the axial direction while also moving in rolling contact with the form roller, to break up the rib and streak formation. However, this roller mechanism adds delay in the “steadying out” of the dampening system so printing cannot start until the dampening fluid layer thickness has stabilized on all the roller surfaces. Also, on-the-fly dampening fluid flow control is not possible since the dampening fluid layer is at that point already built up on the form roller and the other dampening system rollers acts as a buffering mechanism. [0013] Accordingly, efforts have been made to develop systems to deposit dampening fluid directly on the offset plate surface as opposed to on intermediate rollers or a form roller. One such system sprays the dampening fluid onto the reimageable offset plate surface. See, e.g., U.S. Pat. No. 6,901,853 and U.S. Pat. No. 6,561,090. However, due to the fact that these dampening systems are used with conventional (pre-patterned) offset plates, the mechanism of transfer of the dampening fluid to the offset plate includes a ‘forming roller’ that is in rolling contact with the offset plate cylinder to transfer the FS to the plate surface in a pattern-wise fashion—since it is the nip action of contact rolling between the form roller and the patterned offset plate surface that squeezes out the fountain solution from the hydrophobic regions of the offset plate, allowing the subsequent ink transfer selectivity mechanism to work as desired. [0014] While these spray dampening systems provide the advantage of metering the flow rate of the dampening fluid through control of the spray system, as well as the ability to manipulate the dampening fluid layer thickness on-the-fly as needed, the requirement of using the dampening system form roller as the final means of transferring the dampening fluid to the plate surface reintroduces the disadvantages of thickness variation, roller contamination, roller cavitation, and so on. Furthermore, while the dampening fluid is typically less than one micron in thickness, such systems are not able to accommodate a relatively wide thickness range of the dampening fluid in this less-than-one micron regime. [0015] For further reference, additional methods of applying dampening fluid to a reimageable surface are disclosed in U.S. patent application Ser. No. 13/204,515, filed on Aug. 5, 2011, which is incorporated herein by reference. SUMMARY [0016] The present disclosure is directed to systems and methods for applying a dampening fluid directly to a reimageable surface of a variable data lithographic system. Selective evaporation of the dampening fluid is then performed to arrive at a desired dampening fluid layer thickness. [0017] Initially, systems and methods are employed to form a dampening fluid layer. Such systems and methods may be virtually any conventional system such as the aforementioned form roller, spray or similar direct application, or other known system and method. The layer of dampening fluid is initially deposited to a thickness greater than the ultimate target thickness. A controlled gas flow is applied over the as-deposited dampening fluid to evaporate a desired amount of the dampening fluid to thereby obtain a desired thickness. A thickness sensor may be associated with the gas flow controller to provide near-real time feedback for precise layer thickness control. [0018] An evaporative thickness control subsystem disclosed herein therefore includes a gas source and a nozzle or array of nozzles for directing the gas from the source to the surface of the dampening fluid over the reimageable surface (gas jet embodiments) or from the source over the surface of the dampening fluid and into the nozzle (vacuum embodiments). Other elements of the evaporative thickness control subsystem may include a pressure source to provide transport pressure to the evaporative gas, a vacuum extraction subsystem for collecting the evaporated dampening fluid, a recycling system for recycling the collected evaporated dampening fluid, shielding elements to prevent evaporated dampening fluid from settling on other subsystems or system components, a dampening fluid thickness measurement subsystem, and controller for controlling various aspects of the conditions (such as the gas flow rate, temperature, and so on) leading to dampening fluid evaporation (optionally responsive to the dampening fluid thickness measurement subsystem). [0019] Various embodiments of an evaporative thickness control subsystem are contemplated herein, which include a plurality of the above-mentioned elements. For example, according to a first embodiment, a gas flow is directed to an open region of the dampening fluid surface uniformly across the width of the reimageable surface. According to a second embodiment, a manifold is positioned over the reimageable surface to define a gap. The evaporative gas is directed into the gap such that evaporation occurs predominantly in the gap. Either the first or second embodiments may operate with a positive gas flow through the nozzle (gas jet embodiments) or a negative gas flow through the nozzle (vacuum embodiments). Evaporation rates may be controlled by controlling the gas flow rate, distance between the gas source and the reimageable surface, the temperature of the gas, the humidity of the gas, the temperature of the reimageable surface (or plate or drum thereunder), the exposure time or distance of the dampening fluid to the gas, and so on. [0020] Various feedback and control systems may be provided to measure the thickness of the layer of dampening fluid applied to the reimageable surface, and control, dynamically or otherwise, aspects of the evaporation process to obtain and maintain a desired layer thickness. [0021] The above is a summary of a number of the unique aspects, features, and advantages of the present disclosure. However, this summary is not exhaustive. Thus, these and other aspects, features, and advantages of the present disclosure will become more apparent from the following detailed description and the appended drawings, when considered in light of the claims provided herein. BRIEF DESCRIPTION OF THE DRAWINGS [0022] In the drawings appended hereto like reference numerals denote like elements between the various drawings. While illustrative, the drawings are not drawn to scale. In the drawings: [0023] FIG. 1 is a side view of a system for variable lithography according to an embodiment of the present disclosure. [0024] FIG. 2 is a side view of a portion of a system for variable lithography including an evaporative thickness control subsystem according to an embodiment of the present disclosure. [0025] FIG. 3 is a cutaway view of a portion of an imaging member with a patterned dampening fluid layer disposed thereover according to an embodiment of the present disclosure. [0026] FIG. 4 is a cutaway view of a portion of an imaging member with an inked patterned dampening fluid layer disposed thereover according to an embodiment of the present disclosure. [0027] FIG. 5 is a side view of a portion of a system for variable lithography including an evaporative thickness control subsystem according to an alternate embodiment of the present disclosure. [0028] FIG. 6 is a side view of a portion of a system for variable lithography including an evaporative thickness control subsystem according to another alternate embodiment of the present disclosure. [0029] FIG. 7 is a side view of a portion of a system for variable lithography including an evaporative thickness control subsystem according to a still further alternate embodiment of the present disclosure. DETAILED DESCRIPTION [0030] We initially point out that description of well-known starting materials, processing techniques, components, equipment, and other established details are merely summarized or are omitted so as not to unnecessarily obscure the details of the present invention. Thus, where details are otherwise well known, we leave it to the application of the present invention to suggest or dictate choices relating to those details. [0031] With reference to FIG. 1 , there is shown therein a system 10 for variable data lithography according to one embodiment of the present disclosure. System 10 comprises an imaging member 12 , in this embodiment a drum, but may equivalently be a plate, belt, etc., surrounded by a direct-application dampening fluid subsystem 14 (although other than direct application subsystems may also be used), an optical patterning subsystem 16 , an inking subsystem 18 , a rheology (complex viscoelastic modulus) control subsystem 20 , transfer subsystem 22 for transferring an inked image from the surface of imaging member 12 to a substrate 24 , and finally a surface cleaning subsystem 26 . Many optional subsystems may also be employed, but are beyond the scope of the present disclosure. Many of these subsystems, as well as operation of the system as a whole, are described in further detail in the U.S. patent application Ser. No. 13/095,714, which is incorporated herein by reference. [0032] The key requirement of dampening fluid subsystem 14 is to deliver a layer of dampening fluid having a relatively uniform and controllable thickness over a reimageable surface layer over imaging member 12 . In one embodiment this layer is in the range of 0.1 μm to 1.0 μm. Due to a variety of causes, this layer may vary in thickness from location to location. Furthermore, given the control of certain deposition subsystems, this layer may be within 0.1 or more microns of the desired target thickness. Therefore, an additional mechanism is required to refine the thickness of the dampening fluid layer prior to optical patterning subsystem 16 . The evaporative thickness control subsystem 28 serves this purpose, and is disclosed in further detail below. [0033] The dampening fluid must have the property that it wets and thus tends to spread out on contact with the reimageable surface. Depending on the surface free energy of the reimageable surface the dampening fluid itself may be composed mainly of water, optionally with small amounts of isopropyl alcohol or ethanol added to reduce its natural surface tension as well as lower the evaporation energy necessary for subsequent laser patterning. In addition, a suitable surfactant may be added in a small percentage by weight, which promotes a high amount of wetting to the reimageable surface layer. In one embodiment, this surfactant consists of silicone glycol copolymer families such as trisiloxane copolyol or dimethicone copolyol compounds which readily promote even spreading and surface tensions below 22 dynes/cm at a small percentage addition by weight. Other fluorosurfactants are also possible surface tension reducers. Optionally the dampening fluid may contain a radiation sensitive dye to partially absorb laser energy in the process of patterning. Optionally the dampening fluid may be non-aqueous consisting of, for example, silicone fluids, polyfluorinated ether or fluorinated silicone fluid. [0034] In the description of embodiments that follow it will be appreciated that as there is no pre-formed hydrophilic-hydrophobic pattern on a printing plate in system 10 . A laser (or other radiation source) is used to form pockets in, and hence pattern, the dampening fluid. The characteristics of the pockets (such as depth and cross-sectional shape), which determine the quality of the ultimate printed image, are in large part a function of the effect that the laser has on the dampening fluid. This effect is to a large degree influenced by the thickness of the dampening fluid at the point of incidence of the laser. Therefore, to obtain a controlled and preferred pocket shape, it is important to control and make uniform the thickness of the dampening fluid layer, and to do so without introducing unwanted artifacts into the printed image. [0035] Accordingly, with reference to FIG. 2 , there is shown therein an evaporative thickness control subsystem 28 according to a first embodiment of the present disclosure. Evaporative thickness control subsystem 28 is disposed proximate an imaging member 12 having a reimageable surface 30 . A dampening fluid deposition subsystem 32 initially deposits a layer of dampening fluid 34 over surface 30 . Layer 34 may in the range of 0.2 μm to 1.0 μm as deposited. Evaporative thickness control subsystem 28 is disposed following fluid deposition subsystem 32 in the direction of motion of imaging member 12 . Evaporative thickness control subsystem 28 comprises an evaporative gas source 36 , which may be a canister or tank (as shown), a gas generation device, an inlet port for collecting ambient gas (such as air, remote from the region of the reimageable surface), or other appropriate source structure. A gas-directing nozzle 38 , or an array of such nozzles, is connected to evaporative gas source 36 by way of a valve 40 and optional pressure source 42 to provide transport pressure to the evaporative gas. [0036] In operation, evaporative gas from source 36 is forced from nozzle 38 towards the surface of layer 34 . This causes evaporation of a portion of layer 34 . Dampening fluid evaporated from layer 34 may form part of the ambient air surrounding the lithographic system, or may be removed from the proximity of layer 34 by a vacuum extraction subsystem 44 . In certain embodiments, extracted dampening fluid may be recycled, stored in a reservoir 46 , and reused by dampening fluid deposition subsystem 32 . [0037] According to certain embodiments, evaporative gas from source 36 forced from nozzle 38 is incident on layer 34 generally radially relative to the surface of imaging member 12 . In other embodiments, the evaporative gas may be directed against the direction of rotation of imaging member 12 (i.e., directed upstream). In still other embodiments, the evaporative gas may be directed with the direction of rotation of imaging member 12 (i.e., directed downstream). The choice of direction will depend on the particular application, but considerations include possible affects on the downstream layer thickness and other subsystems and elements located downstream of evaporative thickness control subsystem 28 . [0038] One level of control of the extent of evaporation resulting from the direction of gas onto the surface of layer 34 by evaporative thickness control subsystem 28 may be provided by controlling the gas flow rate, the distance between the exit port of nozzle 38 and the reimageable surface, the temperature of the gas, the humidity of the gas, the temperature of the ambient, the humidity of the ambient, the temperature of the reimageable surface (or plate or drum thereunder), the exposure time or distance of the dampening fluid to the gas, and so on. Therefore, control of layer thickness to a first-order may be determined based on the conditions listed above, and possibly others, given the application of the present disclosure. Higher-order (more precise) control over layer thickness may be provided by a feedback mechanism discussed further below. [0039] One goal of the present disclosure is to provide a system and method for forming a precise dampening fluid layer thickness for accurate patterning by optical patterning subsystem 16 . In this regard, it is important that dampening fluid evaporated by evaporative gas exiting nozzle 38 not settle on the surface of layer 34 following evaporative thickness control subsystem 28 in the direction of travel of imaging member 12 . It is also important that the gas exiting nozzle 38 not further disturb the surface of layer 34 following evaporative thickness control subsystem 28 in the direction of travel of imaging member 12 . Therefore, in addition to vacuum extraction subsystem 44 a barrier structure 48 may be disposed between optical patterning subsystem 16 and evaporative thickness control subsystem 28 . [0040] According to certain embodiments of the present disclosure, the thickness of the layer 34 is determined by an appropriate method and system, such as an optical thickness measurement device 50 . The measured thickness of layer 34 may be used to confirm that the evaporative thickness control subsystem 28 is operating properly. It may also be used to manually or automatically adjust the operation of evaporative thickness control subsystem 28 to obtain a target thickness for layer 34 . In the later case, the output of optical thickness measurement device 50 is provided to a control device 52 . Control device 52 compares the thickness measurement from device 50 to a target thickness, and sends an appropriate feedback signal, for example to valve 40 (e.g., a servo-operated valve) if needed to increase or decrease the gas flow to obtain the appropriate thickness of layer 34 . Alternatively, or in addition to providing the feedback signal to control device 52 , the feedback signal may be provided to a control device 54 for controlling one or more of the following: an apparatus that controls the distance between the exit port of nozzle 38 and the reimageable surface, an apparatus that controls the temperature of the gas, an apparatus that controls the humidity of the gas, an apparatus that controls the temperature of the ambient, an apparatus that controls the humidity of the ambient, an apparatus that controls the temperature of the reimageable surface (or plate or drum thereunder), an apparatus that controls the exposure time or distance of the dampening fluid to the gas, and so on. This feedback loop may operate continuously and sufficiently rapidly that substantially real-time layer thickness control may be provided, to tenths of a micron or greater accuracy. [0041] Finally, layer 34 is brought past optical patterning subsystem 16 , which is used to selectively form an image in the dampening fluid by image-wise evaporating the dampening fluid layer using laser energy, for example. With reference to FIG. 3 , which is a magnified view of a region of imaging member 12 and reimageable surface 30 having a layer of dampening fluid 34 applied thereover, the application of optical patterning energy (e.g., beam B) from optical patterning subsystem 16 results in selective evaporation of portions of layer 34 . This produces a pattern of ink-receiving wells 56 in the dampening fluid. Relative motion between imaging member 12 and optical patterning subsystem 16 , for example in the direction of arrow A, permits a process-direction patterning of layer 34 . [0042] As shown in FIG. 4 , inking subsystem 18 may then provide ink over the surface of layer 30 . Due to the nature of the ink, surface 30 , dampening fluid comprising layer 34 , and the physical arrangements of the elements of the inking subsystem 18 , ink selectively fills ink-receiving wells 56 (shown in FIG. 3 ). By providing a precisely controlled thickness of layer 34 , the extent, profile, and other attributes of each ink-receiving well are well controlled, the amount of ink filling each ink-receiving well is controlled, and ultimately the quality of the resulting image applied to the substrate is therefore improved and consistent. [0043] FIG. 5 illustrates another embodiment of the present disclosure. According to this embodiment, a plate structure 70 is provided proximate surface 30 of imaging member 12 . Plate structure 70 may be planar and disposed such that its plane is substantially parallel to a tangent line t of imaging member 12 , or may be an arch structure with a radius matching and coaxial with the radius of imaging member 12 . Nozzle 72 is disposed at one end of plate structure 70 , such as the downstream end relative to the direction of travel of imaging member 12 . An evaporative gas is exhausted from nozzle 72 , in this case against the direction of travel of layer 34 . As with the embodiments described above, the evaporative gas causes evaporation of a portion of layer 34 . Dampening fluid evaporated from layer 34 may form part of the ambient air surrounding the lithographic system, or may be removed from the proximity of layer 34 by vacuum extraction subsystem 44 . In certain embodiments, extracted dampening fluid may be recycled, stored in reservoir 46 , and reused by dampening fluid deposition subsystem 32 . [0044] FIG. 6 illustrates yet another embodiment of the present disclosure. According to this embodiment, a manifold is 80 is again provided proximate surface 30 of imaging member 12 . However, in place of a separate nozzle, manifold 80 has formed therein a plurality of vents which act as an array of nozzles. Manifold 80 may be connected to a gas source and controlled by a feedback signal substantially as previously described. [0045] It will be appreciated that while each of the above-disclosed embodiments have operated as a nozzle (or array of nozzles) exhausting an evaporative gas in the direction of the dampening fluid layer, with proper adjust of certain parameters and element locations, each of the above embodiments may operate such that a vacuum is the prime mover of gas—i.e., due to application of a vacuum, a gas passes over the surface of the dampening fluid causing evaporation and resultant thickness control. By way of illustration, FIG. 7 shows a nozzle 82 operating in a vacuum configuration. The draw from nozzle 82 causes a gas (specifically introduced or ambient in the region of layer 34 ) to pass over the surface of layer 34 resulting in evaporation of dampening fluid. The evaporated dampening fluid may travel with the gas into nozzle 82 , and/or be otherwise removed by a supplemental extraction system 44 or the like. [0046] No limitation in the description of the present disclosure or its claims can or should be read as absolute. The limitations of the claims are intended to define the boundaries of the present disclosure, up to and including those limitations. To further highlight this, the term “substantially” may occasionally be used herein in association with a claim limitation (although consideration for variations and imperfections is not restricted to only those limitations used with that term). While as difficult to precisely define as the limitations of the present disclosure themselves, we intend that this term be interpreted as “to a large extent”, “as nearly as practicable”, “within technical limitations”, and the like. [0047] Furthermore, while a plurality of preferred exemplary embodiments have been presented in the foregoing detailed description, it should be understood that a vast number of variations exist, and these preferred exemplary embodiments are merely representative examples, and are not intended to limit the scope, applicability or configuration of the disclosure in any way. Various of the above-disclosed and other features and functions, or alternative thereof, may be desirably combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications variations, or improvements therein or thereon may be subsequently made by those skilled in the art which are also intended to be encompassed by the claims, below. [0048] Therefore, the foregoing description provides those of ordinary skill in the art with a convenient guide for implementation of the disclosure, and contemplates that various changes in the functions and arrangements of the described embodiments may be made without departing from the spirit and scope of the disclosure defined by the claims thereto.
A system and corresponding methods are disclosed for controlling the thickness of a layer of dampening fluid applied to a reimageable surface of an imaging member in a variable data lithography system. Following deposition of the dampening fluid layer, a gas is passed over a region of the fluid layer prior to pattern forming. The gas causes a controlled amount of the dampening fluid layer to evaporate such that the remaining layer is of a desired and controlled thickness. Among other advantages, improved print quality is obtained.
1
TECHNICAL FIELD The invention relates to a lightweight aircraft passenger seat assembly, comprising at least one seat portion and at least one supporting portion for supporting the at least one seat portion relative to an aircraft structure. BACKGROUND Conventional aircraft passenger seat assemblies regularly comprise a support structure with two cross beams extending in the aircraft's widthwise orientation and supported by legs, wherein armrest hangers and passenger seats are alternately attached alongside the two cross beams so as to form an aircraft passenger seat assembly with several seats. Since the legs, the cross beams, the hangers and the framework of the seats are regularly made from heavy metal components, the conventional aircraft passenger seat assemblies significantly contribute to the overall weight of an aircraft, and limit the overall seating capacity and profitability, respectively, of commercially operated aircrafts. A need for having a lightweight aircraft passenger seat with smaller fore-aft dimensions compared to conventional passenger seat designs has been identified and satisfied e.g. by the documents US 2007/267543 A, US 2008/150342 A, US 2008/282523 A or US 2008/290242 A. However, these known solutions still leave room for considerable reductions in weight, size and complexity of the lightweight aircraft passenger seat assembly. A reduction in weight and size of the lightweight aircraft passenger seat assembly may allow the aircraft to carry more passenger seat assemblies and more passengers, respectively, thus increasing the potential profitability of the aircraft. A reduction in complexity of the passenger seat assembly may additionally allow the production and/or maintenance at lower costs, thus rendering the lightweight aircraft passenger seat assembly even more attractive to airlines as compared to the conventional aircraft passenger seat assemblies using heavy metal components. The object of the invention is therefore to provide an improved lightweight aircraft passenger seat assembly having a reduced weight, size and complexity as compared to conventional lightweight passenger seat designs. Likewise it is the object of the invention to reduce the weight, size and complexity of the lightweight aircraft passenger seat assembly on the component level and to provide at least one lightweight aircraft passenger seat assembly component having a reduced weight, size and complexity as compared to conventional lightweight passenger seat assembly components, or to provide at least one lightweight aircraft passenger seat assembly component which allows other components to have a reduced weight, size and complexity as compared to conventional lightweight passenger seat assembly components. SUMMARY In order to solve the above-defined object, the first aspect of the invention provides the lightweight aircraft passenger seat assembly comprising at least one seat portion with at least one seat shell for an aircraft passenger and at least one supporting portion for supporting the at least one seat portion relative to an aircraft structure, wherein the at least one seat shell and the at least one supporting portion are constructed as lightweight components. The expression “lightweight component” as used herein is understood to include components which are designed in a weight and/or material saving manner and/or made from lightweight materials, including, for example, any type of fiber reinforced composite materials, any type of plastic materials and/or any type of light metals, particularly aluminium, with a sufficient inherent stability for use in the aero-space industry. The lightweight aircraft passenger seat assembly according to the invention may particularly be designed as a seat assembly for economy class passengers in short-haul aircrafts. The lightweight seat shell may have a particularly simple design and may preferably be substantially rigid in itself, thus providing limited options of adjustability. In short-haul aircrafts, this drawback is generally acceptable in view of the rather short flight times. However, on the other hand, the limited possibilities of adjustment allow a significant reduction of the complexity of the lightweight aircraft passenger seat assembly. This has been realized by the invention in the form of the simple design of the seat assembly with basically only the seat shell and the support for the seat shell as primary components. Since these primary components are constructed as lightweight components with a simple design, the weight, size and complexity of the inventive lightweight aircraft passenger seat assembly can still be significantly reduced as compared to the conventional lightweight aircraft passenger seat designs. Also, the limited adjustability of the seat shell allows complex adjustment mechanisms to be dispensed with. Moreover, the supporting portion and the seat shell of the inventive lightweight aircraft passenger seat assembly may be coupled together easily so as to allow relative movements of the seat shell and the supporting portion in order to provide sufficient yielding and resilience characteristics for deformation under exceptional load conditions. This is particularly relevant in terms of approval of the inventive lightweight aircraft passenger seat assembly for civil aviation applications according to SAE AS 8049B-2005, which is a qualification for aircraft components and involves dynamic tests under a load of 14G downward and 16G forward. In the description of the invention, terms from the word stems “coupling” or “supporting” will be understood as describing a direct or indirect link between two elements, whereas the terms from the word stems “connecting” or “attaching” or “securing” will be understood as describing a direct link between two elements. In the description of the invention, terms from the word stem “bonding” will be understood as describing any type of connection between two separate components or bodies, including “welding” or “adhesive bonding”. Furthermore, in the description of the invention, terms from the word stem “integral” will be understood as describing any component or body made as “one continuous piece”, whereas different components or bodies or portions thereof may be bonded, in particular, welded together to form an “integral” component or body in the sense of the invention. On the other hand, in the description of the invention, terms from the word stem “one-piece construction” will be understood as describing any component or body originally made as “one piece”, excluding the possibility to bond or weld different components or bodies together to form a “one-piece construction” in the sense of the invention. Further to this, in the description of the invention, terms from the word stem “monolithic” will be understood as describing any component or body made from one “construction material”, whereas fiber reinforced materials, including a fiber material different from a matrix material, will be regarded as one “construction material”, though, any “sandwich constructions” with a core different than the outer sandwich layers may not be regarded as “monolithic” in the sense of the invention. Accordingly, a “monolithic” component or body may be an “integral” component or body or may also be a “one-piece construction” in the sense of the invention. Moreover, in the description of the invention, terms from the word stem “fiber orientation” will be understood as describing the “main fiber orientation” of a component or body made from a fiber reinforced material, wherein the respective component or body may have other fibers with an orientation other than the “main fiber orientation”. Finally, in the description of the invention, terms from the word stem “symmetrical” will be understood as describing any type of components or bodies which are “mostly symmetrical”, thus not being limited to symmetry in a mathematical sense, whereas “symmetrical” may refer to a “mirror symmetrical”, a “rotationally symmetrical” or a “point symmetrical” relation. Preferred embodiments of the lightweight aircraft passenger seat assembly according to the present invention are claimed in the subclaims. In the following, preferred aspects of the invention will be described. Each one of the following aspects of the invention relates to a component for a lightweight aircraft passenger seat assembly, which is disclosed and may thus be claimed individually or in combination with at least another aspect of the invention, in particular in combination with the lightweight aircraft passenger seat assembly according to the first aspect of the invention and/or in combination with at least another lightweight aircraft passenger seat assembly component according to at least another one of the second to the last aspects of the invention. The applicant reserves the right to render each one of the following aspects of the invention the subject of one or more divisional applications. The individual features disclosed for a generic type of a lightweight aircraft passenger seat assembly component (e.g. second aspect; lightweight aircraft passenger seat assembly component) may be seen as disclosed in context with and attributed with any type of lightweight aircraft passenger seat assembly component referred to hereinafter. The individual features disclosed for a specific type of a lightweight aircraft passenger seat assembly component (e.g. supporting portion) in context with the following aspects of the invention (e.g. third aspect: a supporting portion has a leg portion; fifth aspect: a supporting portion has a frame portion) may be seen as disclosed in context with and attributed to the same lightweight aircraft passenger seat assembly component (i.e. the same supporting portion has a leg portion and a frame portion) or to different lightweight aircraft passenger seat assembly components of the same type (a first supporting portion has a leg portion and a second supporting portion has a frame portion). A second aspect of the invention relates to a component for a lightweight aircraft passenger seat assembly, preferably in combination with the first aspect of the invention, wherein the lightweight component satisfies at least one of the following features: The lightweight component forms an integral and/or monolithic body. The lightweight component is a one-piece construction. The lightweight component is made from fiber reinforced composite material, preferably a laminated fiber reinforced composite material. The lightweight component is made from a prepreg. The lightweight component comprises glass fibers, carbon fibers, ceramic fibers, aramid fibers, boron fibers, steel fibers, natural fibers and/or poly-amid fibers. The lightweight component comprises a matrix made from a polymer, preferably from a thermosetting polymer, an elastomer or a thermosoftening plastic, or a ceramic or a metal, preferably a light metal, or carbon. The lightweight component comprises a first fiber layer and a second fiber layer, preferably arranged adjacent to the first fiber layer, wherein the first fiber layer is made from a different material than the second fiber layer. The lightweight component comprises a first fiber layer and a second fiber layer, preferably arranged adjacent to the first fiber layer, wherein the first fiber layer has a smaller thickness than the second fiber layer. The lightweight component comprises a first fiber layer and a second fiber layer, preferably arranged adjacent to the first fiber layer, wherein the first fiber layer is a primary fiber layer and the second fiber layer is an enforcement fiber layer, wherein preferably the enforcement fiber layer has a greater thickness than the primary fiber layer. The lightweight component comprises a first fiber layer and a second fiber layer, preferably arranged adjacent to the first fiber layer, wherein the first and the second fiber layer have the same fiber orientations. The lightweight component comprises a first fiber layer and a second fiber layer, preferably arranged adjacent to the first fiber layer, wherein the first fiber layer has a different fiber orientation than the second fiber layer. The lightweight component comprises a first fiber layer and a second fiber layer, preferably arranged adjacent to the first fiber layer, wherein the fiber orientation of the first layer is arranged at an angle of 30°, 45°, 60°, 75°, 90°, 105°, 120°, 135°, 150° or 165° relative to the fiber orientation of the second layer, in each case with a tolerance of +/−5°, preferably +/−2°. The lightweight component comprises a plurality of fiber layers, wherein the different fiber layers are configured in more than two fiber orientations, preferably three fiber orientations, more preferably in four fiber orientations. The lightweight component comprises a first fiber layer and a second fiber layer, preferably arranged adjacent to the first fiber layer, wherein the second fiber layer covers a smaller area than the first layer. The lightweight component comprises at least three fiber layers, wherein the second fiber layer is arranged between the first and the third fiber layer and wherein the second fiber layer covers the same or a smaller area than the first fiber layer and/or the third fiber layer covers the same or a smaller area than the second fiber layer. The lightweight component comprises a first fiber layer and a second fiber layer, preferably arranged adjacent to the first fiber layer, wherein the fiber layers are made from the same material, have the same thickness and/or cover the same area. The lightweight component comprises a first fiber layer, a second fiber layer, preferably arranged adjacent to the first fiber layer, and at least a force transmission portion for transmitting forces between two layer portions, wherein the force transmission portion is at least partially reinforced by the second fiber layer. The lightweight component comprises a first fiber layer, a second fiber layer, preferably arranged adjacent to the first fiber layer, and at least a force application portion for the application of forces to the lightweight component, wherein the first fiber layer comprises a cut-out in the area of the force application portion and wherein the force application portion is covered by the second fiber layer. The lightweight component comprises a first fiber layer and a second fiber layer, preferably arranged adjacent to the first fiber layer, wherein at least the first fiber layer comprises portions, preferably with different fiber orientations, adjoining each other in a butt-join, wherein the butt-join of the first fiber layer is covered by a continuous portion of the second layer. The lightweight component comprises a first fiber layer and a second fiber layer, preferably arranged adjacent to the first fiber layer, wherein each fiber layer comprises portions, preferably with different fiber orientations, adjoining each other in a butt-join, wherein the butt-join of the first fiber layer is arranged at a distance to the butt-join of the second layer in an orientation parallel to the layers. The lightweight component comprises at least one first fiber layer comprising portions with different or identical fiber orientations, which portions overlap along an adjoining region. The lightweight component comprises a first portion, a second portion and at least one fiber layer, wherein the first portion and the second portion are arranged at an angle to each other and are connected along an edge and wherein the at least one fiber layer is intersected by a butt-join, which runs along the edge between the first and the second portion. The lightweight component comprises a first portion, a second portion and at least one fiber layer, wherein the first portion and the second portion are arranged at an angle to each other and are connected along an edge and wherein the at least one fiber layer is free of intersections in the area of the edge and/or in the area adjacent to the edge. At least one of the above features allows an optimization of a weight vs. stability ratio of the lightweight component and/or a particularly high stability of the component in different load and/or torsion directions and/or a high stability between different portions of the component, particularly in the transition region between different component portions, and/or a strong connection to adjacent components. The expression “fiber reinforced composite material” as used herein and in the following is understood to include at least one fiber reinforced composite material and different fiber reinforced composite materials. A third aspect of the invention relates to a supporting portion for a lightweight aircraft passenger seat assembly, preferably in combination with at least one of the preceding aspects of the invention, wherein the supporting portion comprises at least one leg portion which satisfies at least one of the following features: The leg portion forms an integral and/or monolithic body. The leg portion is a one-piece construction. The leg portion has at least one leg, preferably two or more legs, more preferably four legs. The leg portion has at least one leg which is hollow and/or comprises at least one opening. The leg portion has at least one leg which tapers toward a distal end thereof. The leg portion comprises at least two separate bodies, which are bonded, preferably welded, together to form an integral body, wherein the separate bodies are preferably one piece constructions. The leg portion comprises two symmetrical halves, preferably split down the center plane, which are bonded, preferably welded, together to form an integral body, wherein the symmetrical halves are preferably one piece constructions. The leg portion comprises more than two separate bodies, wherein the separate bodies preferably form integral and/or monolithic bodies and/or wherein the separate bodies are preferably one piece constructions. The leg portion comprises an internal structure body and two symmetrical halves, preferably split down the center plane, which are bonded, preferably bolted and/or welded, together, wherein the internal structure body and/or the symmetrical halves are preferably one piece constructions, wherein the symmetrical halves at least sectionwise encapsulate the internal structure body and/or wherein the two symmetrical halves at least sectionwise form an open profile. The leg portion comprises at least one leg, preferably more than one leg, more preferably exactly four legs, particularly a first leg, a second leg, a third leg and a fourth leg, wherein the at least one leg is at least sectionwise formed by an internal structure body and two symmetrical halves, which at least sectionwise encapsulate the internal structure body. The leg portion comprises two legs which are connected to extend along a continuous line, preferably along a straight line, and preferably to extend between a front frame-side connecting portion and a rear aircraft-side coupling portion. The leg portion comprises at least one leg, which branches-off from another leg, preferably downward to a front aircraft-side coupling portion and/or upward to a rear frame-side connecting portion. The leg portion comprises a first leg, a second leg, a third leg and a fourth leg, wherein the second leg and the third leg are connected to extend along a continuous line, wherein the first leg branches-off from the third leg and wherein the fourth leg branches-off from the second leg. The leg portion comprises a first leg, a second leg, a third leg and a fourth leg, wherein preferably the first leg and the third leg are configured to be oriented forward with respect to the aircraft's longitudinal orientation and the second leg and the fourth leg are configured to be oriented rearward with respect to the aircraft's longitudinal orientation. The leg portion comprises four legs, wherein each leg is at least sectionwise formed by an internal structure body and two symmetrical halves, which at least sectionwise encapsulate the internal structure body, wherein the two symmetrical halves at least sectionwise form an open profile, wherein preferably the symmetrical halves in the area forming the first and/or the third leg and/or encapsulating the portion of the internal structure body of the first and/or the third leg form an open profile being open in the forward direction with respect to the aircraft's longitudinal orientation and/or wherein the symmetrical halves in the area forming the second and/or the fourth leg and/or encapsulating the portion of the internal structure body of the second and/or the fourth leg form an open profile being open in the rearward direction with respect to the aircraft's longitudinal orientation. The leg portion comprises four legs, wherein each leg is at least sectionwise formed by an internal structure body and two symmetrical halves, which at least sectionwise encapsulate the internal structure body, wherein the two symmetrical halves at least sectionwise form an open profile, wherein preferably the symmetrical halves in the area forming the first and/or the third leg and/or encapsulating the internal structure body of the first and/or the third leg form an open profile being closed in the rearward direction with respect to the aircraft's longitudinal orientation and/or wherein the symmetrical halves in the area forming the second and/or the fourth leg and/or encapsulating the portion of the internal structure body of the second and/or the fourth form an open profile being closed in the forward direction with respect to the aircraft's longitudinal orientation. The leg portion comprises four legs, wherein the first leg branches-off from the third leg and the length axis of the first leg and the length axis of the third leg are arranged at an angle of more than 90°, preferably more than 100° and preferably less than 120°, more preferably less than 110°, and/or wherein the fourth leg branches-off from the second leg and the length axis of the second leg and the length axis of the fourth leg are arranged at an angle of more than 90°, preferably more than 100° and preferably less than 120°, more preferably less than 110°. The leg portion has at least one leg to be coupled with an aircraft structure, preferably two legs to be coupled with an aircraft structure, wherein preferably a first leg is configured to be oriented forward with respect to the aircraft's longitudinal orientation and a second leg is configured to be oriented rearward with respect to the aircraft's longitudinal orientation, wherein both legs are preferably configured to be coupled with the same rail installed at an aircraft floor. The leg portion has at least one leg to be engaged with a frame portion, preferably two legs be engaged with a frame portion, wherein preferably a third leg is configured to be oriented forward with respect to the aircraft's longitudinal orientation and a fourth leg is configured to be oriented rearward with respect to the aircraft's longitudinal orientation, wherein preferably both legs are configured to be engaged with the same frame portion. The leg portion is configured to connect to a frame portion of the supporting portion, wherein the leg portion preferably connects to a loop portion of the frame portion and/or to a portion of the frame portion apart from a beam portion. The leg portion comprises at least one male and/or female engagement feature for establishing a form-fit, preferably in an orientation perpendicular to a length orientation of the male and/or female engagement feature, and/or a non-positive connection, preferably in a length orientation of the male and/or female engagement feature, together with at least a corresponding one female and/or male engagement feature of a frame portion, wherein the at least one male and/or female engagement feature is preferably located at the distal end of at least one leg of the leg portion and/or is located on a mating surface of the leg portion which abuts to a mating surface of the frame portion, wherein the mating surface of the leg portion is preferably flat. The leg portion is bonded to a frame portion, preferably at the position of the at least one male and/or at least one female engagement feature and/or at the position of the at least one mating surface of the leg portion. The leg portion comprises at least a recess for receiving a frame coupling element, which is configured to couple the leg portion with the frame portion of the seat assembly, preferably with a leg coupling fixture of the frame portion. The leg portion comprises at least a recess for receiving a foot portion, particularly a floor coupling element, which is configured to couple the leg portion with an aircraft structure, preferably to a rail provided at an aircraft floor. The leg portion comprises more than one recess, preferably four recesses for receiving frame and floor coupling elements, wherein the recesses are preferably formed by the free ends of the legs, wherein preferably a frame and/or floor coupling element is fixedly attached within at least one of the recesses, more preferably within each one of the four recesses, wherein preferably a frame coupling element is fixedly attached within each one of the free ends of the third leg and the fourth leg. The leg portion comprises at least one frame coupling element being fixedly attached within a recess at the free end of at least one of the third and the fourth leg, wherein the at least one frame coupling element preferably comprises a supporting portion, which is inserted into the recess of the respective leg, and a connecting portion with a through hole for a bolt or a screw, wherein the supporting portion preferably has an exterior shape being complementary to an interior shape of the at least one leg, so as to fit snugly into said leg. The leg portion comprises at least one frame coupling element being fixedly attached within a recess at the free end of at least one of the third and the fourth leg, wherein the at least one frame coupling element forms a rotary joint which is configured to rotate the frame portion relative to the leg portion, wherein the axis of rotation of the rotary joint is preferably substantially parallel, including a tolerance of up to 20°, to an aircraft floor, preferably parallel to the aircraft's pitch axis and/or roll axis, wherein the rotary joint preferably enables rotation of the frame portion relative to the frame portion by an angle of up to +10° and/or −10°, preferably at least +5° and/or −5° and preferably of up to +15° and/or −15°, as measured from a regular position. The leg portion is identical to at least another leg portion of the supporting portion. The leg portion has at least one leg, comprising a base section and at least one flank section arranged at an angle to the base section, wherein the base section and the at least one flank section are connected via an edge or a rounded edge and wherein preferably the edge or rounded edge extends substantially along the length axis of the leg, including a deviation of up to 20°, preferably up to 15°, more preferably up to 10°, more preferably up to 5° and more preferably up to 2°. The leg portion has at least one leg, comprising a base section and at least a first and a second flank section each arranged at an angle to the base section, wherein the first and the second flank section are connected to the base section via edges or rounded edges being arranged at opposite ends of the base section in an orientation perpendicular to the length axis of the leg, wherein the flank sections are preferably angled to the same side of the base section. The leg portion has at least one leg, wherein the leg in a cross-section oriented perpendicular to its length axis forms an octagon with two base sections and three flank section pairs, wherein the two base sections are preferably arranged parallel to each other, wherein the flank sections of each flank section pair are preferably arranged parallel to each other, wherein the base sections are preferably arranged perpendicular to one of the flank section pairs and wherein the cross-sectional edge lengths of the base sections are preferably greater than the cross-sectional edge lengths of the flank sections. The leg portion has at least two legs, wherein one of the legs branches-off from another leg at an angle and wherein at least one of the edges between the two legs has a rounded shape. The leg portion has at least one, preferably two, more preferably three baggage restrain bars and/or nets for restraining baggage, wherein the at least one baggage restrain bar and/or net is coupled to at least one leg, preferably to the first leg and/or the third leg, wherein the at least one baggage restrain bar and/or net is preferably configured to extend in an airplane widthwise orientation in an installed state of the leg portion, wherein the at least one baggage restrain bar is preferably configured to extend substantially parallel to an airplane floor in an installed state of the leg portion and wherein the at least one baggage restrain net is preferably configured to extend under an angle to an airplane floor in an installed state of the leg portion. The leg portion has at least one, preferably two, more preferably three baggage restrain bars and/or nets for restraining baggage, wherein a first baggage restrain bar and/or net is coupled to at least one leg and at least one leg of another leg portion, wherein preferably a second baggage restrain bar and/or net is coupled to at least one leg of the leg portion and extending opposite to the first baggage restrain bar and/or net and wherein preferably a third baggage restrain bar and/or net is coupled to at least one leg of the other leg portion and extending opposite to the first baggage restrain bar and/or net. The leg portion has at least one, preferably two, more preferably three baggage restrain bars and/or nets for restraining baggage, wherein the at least one baggage restrain bar and/or net is coupled to the two symmetrical halves of the respective leg. The leg portion has at least one, preferably two, more preferably three footrests, wherein the at least one footrest is coupled to at least one leg, preferably to the second leg and/or the fourth leg, wherein the at least one footrest is preferably configured to extend in an airplane widthwise orientation in an installed state of the leg portion, wherein the at least one footrest is preferably configured to extend substantially parallel to an airplane floor in an installed state of the leg portion and wherein the at least one footrest is preferably configured to be operated by a rearward passenger in an installed state of the leg portion. The leg portion has at least one, preferably two, more preferably three footrests, wherein the at least one footrest is coupled to the two symmetrical halves of the at least one leg. At least one of the above features allows an optimization of a weight vs. stability ratio of the leg portion and/or a particularly strong connection to the adjacent frame portion and/or allows the seat assembly to be operated with high security and sufficient comfort. A fourth aspect of the invention relates to a supporting portion for a lightweight aircraft passenger seat assembly, preferably in combination with at least one of the preceding aspects of the invention, wherein the supporting portion comprises at least one leg portion which satisfies at least one of the following features: The leg portion is made from fiber reinforced composite material, preferably a laminated fiber reinforced composite material. The leg portion has at least one leg, preferably two or more legs, more preferably four legs, wherein at least a portion of at least one fiber layer has a fiber orientation extending in length orientation of the respective leg, including a tolerance of +/−15°, preferably +/−5°, more preferably +/−2°. The leg portion has at least one leg, preferably two or more legs, more preferably four legs, wherein at least a portion of at least one fiber layer has a fiber orientation extending perpendicular to the length orientation of the respective leg, including a tolerance of +/−15°, preferably +/−5°, more preferably +/−2°. The leg portion has at least one leg, preferably two or more legs, more preferably four legs, wherein at least a portion of at least one fiber layer has a fiber orientation which is arranged under an angle of 45° to the length orientation of the respective leg, including a tolerance of +/−15°, preferably +/−5°, more preferably +/−2°. The leg portion has at least two legs, preferably three legs, more preferably four legs, wherein at least a portion of at least one fiber layer extends over at least two legs free of intersections and wherein preferably at least one fiber layer entirely covers four legs free of intersections. The leg portion has at least two legs which are connected to extend along a continuous line, preferably along a straight line, and preferably extend between a front frame-side connecting portion and a rear aircraft-side coupling portion, wherein at least one fiber layer continuously extends along the two legs free of intersections. The leg portion has at least two legs which are connected to extend along a continuous line, preferably along a straight line, and preferably extend between a front frame-side connecting portion and a rear aircraft-side coupling portion, wherein at least one fiber layer has a fiber orientation extending along the continuous line of the two legs, including a tolerance of +/−15°, preferably +/−5°, more preferably +/−2°. The leg portion has at least two legs which are connected to extend along a continuous line, preferably along a straight line, and preferably extend between a front frame-side connecting portion and a rear aircraft-side coupling portion, wherein at least one fiber layer has a fiber orientation extending perpendicular to the continuous line of the two legs, including a tolerance of +/−15°, preferably +/−5°, more preferably +/−2°. The leg portion has at least two legs which are connected to extend along a continuous line, preferably along a straight line, and preferably extend between a front frame-side connecting portion and a rear aircraft-side coupling portion, wherein at least one fiber layer has a fiber orientation arranged under an angle of 45° relative to the continuous line of the two legs, including a tolerance of +/−15°, preferably +/−5°, more preferably +/−2°. The leg portion has at least two legs, preferably three legs, more preferably four legs, wherein at least one fiber layer extending along the legs has portions with different fiber orientations abutting along a butt-join, wherein each layer portion is free of intersections and wherein each layer portion extends at least over a portion of a leg and wherein preferably the butt-join extends along a transition region or adjacent to a transition region between two legs. The leg portion has at least two legs, preferably three legs, more preferably four legs, wherein at least one fiber layer extending along the legs has portions with different fiber orientations abutting along a butt-join, wherein each layer portion is free of intersections, wherein a first layer portion extends at least over a portion of a first leg and over a portion of a third leg, wherein a third layer portion extends at least over a portion of the third leg and wherein a butt-join between the first and the third layer portion extends along the third leg, or wherein a first layer portion extends at least over a portion of a first leg, wherein a third layer portion extends at least over a portion of the third leg and over a portion of the first leg and wherein a butt-join between the first and the third layer portion extends along the first leg. The leg portion has at least two legs, preferably three legs, more preferably four legs, wherein at least one fiber layer extending along the legs has portions with different fiber orientations abutting along a butt-join, wherein each layer portion is free of intersections, wherein a fourth layer portion extends at least over a portion of a fourth leg and over a portion of a second leg, wherein a second layer portion extends at least over a portion of the second leg and wherein a butt-join between the fourth and the second layer portion extends along the second leg, or wherein a fourth layer portion extends at least over a portion of a fourth leg, wherein a second layer portion extends at least over a portion of the second leg and over a portion of a fourth leg and wherein a butt-join between the fourth and the second layer portion extends along the fourth leg. The leg portion has at least two legs, preferably three legs, more preferably four legs, wherein at least a portion of the transition region between at least two legs is reinforced by an enforcement fiber layer. At least one of the above features allows an optimization of a weight vs. stability ratio of the leg portion and/or a particularly high stability of the leg portion in different load and/or torsion orientations and/or a high stability between different portions, particularly legs, of the leg portion, particularly in the transition region between different legs, and/or a strong connection to an adjacent frame portion. A fifth aspect of the invention relates to a supporting portion for a lightweight aircraft passenger seat assembly, preferably in combination with at least one of the preceding aspects of the invention, wherein the supporting portion comprises at least one frame portion which satisfies at least one of the following features: The frame portion forms an integral and/or monolithic body. The frame portion is a one-piece construction. The frame portion is configured to support at least one seat portion, preferably exactly three seat portions. The frame portion defines at least one receptacle for receiving and supporting at least one seat portion or the at least one seat shell. The frame portion is configured to connect to the at least one seat portion by positive connection and/or non-positive connection and/or adhesion bond. The frame portion is configured to connect to the at least one seat shell, preferably to a sitting portion and/or a backrest portion and/or a headrest portion and/or an armrest portion of the at least one seat shell, by positive connection and/or non-positive connection and/or adhesion bond. The frame portion comprises at least one male and/or female engagement feature for establishing a form-fit, preferably in an orientation perpendicular to a length orientation of the male and/or female engagement feature, and/or a non-positive connection, preferably in a length orientation of the male and/or female engagement feature, together with at least a corresponding one female and/or male engagement feature of a leg portion. The frame portion comprises at least one leg coupling fixture, which is configured to couple the frame portion with the leg portion of the seat assembly, preferably with a frame coupling element of the leg portion. The frame portion comprises at least one leg coupling fixture, which is bonded, preferably clinched and/or bolted with the beam portion and/or with the loop portion, preferably with the straight portion of the loop portion. The frame portion comprises more than one leg coupling fixture, preferably four leg coupling fixtures for coupling the frame portion with the leg portion of the seat assembly, wherein preferably two leg coupling fixtures are bonded with the beam portion and two leg coupling fixtures are bonded with the loop portions, wherein preferably each of the loop portions is provided with one of the leg coupling fixtures. The frame portion comprises more than one leg coupling fixture, preferably four leg coupling fixtures for coupling the frame portion with at least one leg portion of the seat assembly, wherein at least one leg coupling fixture is configured to be coupled to a frame coupling element of the leg portion which is inserted in the recess of a third leg and/or wherein at least one leg coupling fixture is configured to be coupled to a frame coupling element of the leg portion which is inserted in the recess of a fourth leg. The frame portion comprises at least one leg coupling fixture, which is configured to couple the frame portion with at least one leg portion of the seat assembly, wherein the leg coupling fixture comprises at least an inlay element and/or a cap element, wherein the inlay element is preferably configured to be inserted into the beam portion and/or the loop portion from the upper side thereof and/or wherein the cap element is preferably configured to be attached to the beam portion and/or the loop portion from the lower side thereof, wherein the cap element is preferably bonded, more preferably clinched and/or bolted to the inlay element, wherein the inlay element and the cap element preferably enclose a section of the beam portion and/or the loop portion to form a sandwich structure. The frame portion comprises at least one leg coupling fixture with an inlay element and a cap element, wherein the cap element preferably comprises a supporting portion and at least a connecting portion, preferably two connecting portions, wherein the supporting portion is configured to support the cap element relative to the beam portion and/or the loop portion and/or wherein the supporting portion preferably has a shape being complementary to an exterior shape of the beam portion and/or the loop portion, so as to fit snugly therein from a lower side, wherein the at least one connecting portion preferably has a through hole for a bolt or a screw, wherein the connecting portion preferably protrudes from the supporting portion through a recess in a cover element, which is configured to cover the cap element, wherein the inlay element preferably has a shape being complementary to an interior shape of the beam portion and/or the loop portion, so as to fit snugly thereon from an upper side. The frame portion comprises at least one leg coupling fixture which forms a rotary joint which is configured to rotate the frame portion relative to the leg portion, wherein the axis of rotation of the rotary joint is preferably substantially parallel, including a tolerance of up to 20°, to an aircraft floor, preferably parallel to the aircraft's pitch axis and/or roll axis, wherein the rotary joint preferably enables rotation of the frame portion relative to the leg structure and/or the respective leg by an angle of up to +10° and/or −10°, preferably at least +5° and/or −5° and preferably of up to +15° and/or −15°, as measured from a regular position. The frame portion comprises at least one beam portion, which preferably extends along a curved and/or straight line, preferably in the aircraft's widthwise orientation, wherein the beam portion is preferably twistable, for example, by a twisting angle of equal or greater than +/−2° or equal or greater than +/−5° or equal or greater than +/−10°, as measured from an untwisted state and/or wherein the beam portion is preferably bendable, for example, by a bending angle of equal to or greater than +/−2° or equal to or greater than +/−5° or equal to or greater than +/−10°, as measured from an unbended state. The frame portion comprises at least one loop portion, preferably exactly two loop portions, wherein at least one loop portion preferably forms a closed loop, wherein preferably two loop portions are arranged at opposite ends of one beam portion, wherein preferably the beam portion and straight sections of two loop portions extend along a straight line. The frame portion comprises at least one loop portion, preferably exactly two loop portions, wherein the at least one loop portion comprises two straight portions and two connecting portions, wherein each connecting portion connects an end of a straight portion with an end of another straight portion and wherein preferably the straight portions extend parallel to each other and/or the connecting portions extend parallel to each other. The frame portion comprises at least one beam portion extending along a curved and/or straight line and configured to be installed in the aircraft's width-wise orientation and at least two spine portions coupled to the beam portion, wherein the spine portions are configured to be moveable relative to each other and/or bendable independently from each other. The frame portion comprises at least one spine portion, preferably exactly three spine portions, wherein preferably at least one spine portion connects to at least one beam portion and/or at least one spine portion connects to at least one loop portion, wherein at least one spine portion is preferably configured to extend upwards relative to an aircraft floor in an installed state, wherein at least one spine portion is preferably curved and/or has a furcated distal end, wherein the spine portion is preferably T-shaped and/or Y-shaped. The frame portion provides at least one passenger safety belt attachment space, preferably a cavity or through-hole, for receiving and fixing at least one passenger safety belt fixture, wherein the passenger safety belt attachment space is preferably integrated into a loop portion and/or provided at the inside and/or provided at the outside of a loop portion. The frame portion comprises at least one spine portion and/or a beam portion and/or at least one loop portion with at least a straight portion and at least a connecting portion, wherein the spine portion and/or the beam portion and/or the straight portion of the loop portion and/or the connecting portion of the loop portion has a base section and at least one flank section arranged at an angle to the base section, wherein the base section and the at least one flank section are connected via an edge or a rounded edge and wherein preferably the edge or rounded edge extends substantially along the length axis of the respective spine portion and/or the beam portion and/or the straight portion of the loop portion and/or the connecting portion of the loop portion, including a deviation of up to 20°, preferably up to 15°, more preferably up to 10°, more preferably up to 5°, more preferably up to 2°. The frame portion comprises at least one spine portion and/or a beam portion and/or at least one loop portion with at least a straight portion and at least a connecting portion, wherein the spine portion and/or the beam portion and/or the straight portion of the loop portion and/or the connecting portion of the loop portion has a base section and at least a first and a second flank section each arranged at an angle to the base section, wherein the first and the second flank section are connected to the base section via edges or a rounded edges being arranged at opposite ends of the base section in an orientation perpendicular to the length axis the respective spine portion and/or the beam portion and/or the straight portion of the loop portion and/or the connecting portion of the loop portion, wherein the flank sections are preferably angled to the same side of the respective base section. The frame portion comprises at least one spine portion and/or a beam portion and/or at least one loop portion with at least a straight portion and at least a connecting portion, wherein the spine portion and/or the beam portion and/or the straight portion of the loop portion and/or the connecting portion of the loop portion has a cross-section perpendicular to its length axis having the shape of on open profile. The frame portion is at least sectionwise covered with a closing panel, wherein the closing panel is preferably bonded, more preferably welded to the frame portion. The frame portion and the closing panel together form a cross-section with the shape of a closed profile, wherein said cross-section is perpendicular to the length axis of the respective section of the frame portion. The frame portion is covered with a closing panel at least in the area of a beam portion and/or in the area of a loop portion with at least a straight portion and at least a connecting portion, wherein the frame portion is preferably free of covering elements in the area of the spine portion. The frame portion has at least one, preferably two, more preferably three baggage restrains bar and/or nets for restraining baggage, wherein the at least one baggage restrain bar and/or net is coupled to at least one loop portion, preferably to two loop portions, wherein at least a portion of the baggage restrain bar and/or net is preferably configured to extend in an airplane widthwise orientation in an installed state of the frame portion, wherein at least a portion of the bag-gage restrain bar is preferably configured to extend substantially parallel to an airplane floor in an installed state of the frame portion and wherein the bag-gage restrain net is preferably configured to extend under an angle, preferably perpendicular, to an airplane floor in an installed state of the frame portion. The frame portion has at least one, preferably two, more preferably three footrests, wherein the at least one footrest is coupled to the beam portion and/or at least one loop portion, wherein the at least one footrest is preferably configured to extend in an airplane widthwise orientation in an installed state of the frame portion, wherein the at least one footrest is preferably configured to extend substantially parallel to an airplane floor in an installed state of the frame portion and wherein the at least one footrest is preferably configured to be operated by a rearward passenger in an installed state of the frame portion. At least one of the above features allows an optimization of a weight vs. stability ratio of the frame portion and/or a particularly strong connection to the adjacent leg portions and/or seat portions and/or allows the seat assembly to be operated with high security and sufficient comfort. In particular, the design of the frame portion with two loop portions arranged at opposite ends of one beam portion forms a twistable torsion box and significantly benefits the passing of the dynamic tests prescribed by SAE AS 8049B-2005. A sixth aspect of the invention relates to a supporting portion for a lightweight aircraft passenger seat assembly, preferably in combination with at least one of the preceding aspects of the invention, wherein the supporting portion comprises at least one frame portion which satisfies at least one of the following features: The frame portion is at least partially, preferably entirely, made from fiber reinforced composite material, preferably a laminated fiber reinforced composite material. The frame portion has at least one fiber layer with a fiber orientation in length orientation of at least one spine portion, including a tolerance of +/−15°, preferably +/−5°, more preferably +/−2°. The frame portion has at least one fiber layer with a fiber orientation perpendicular to the length orientation of at least one spine portion, including a tolerance of +/−15°, preferably +/−5°, more preferably +/−2°. The frame portion has at least one fiber layer with a fiber orientation which is arranged under an angle of 45° to the length orientation of at least one spine portion, including a tolerance of +/−15°, preferably +/−5°, more preferably +/−2°. The frame portion has at least one fiber layer with a fiber orientation in length orientation of the beam portion and/or at least one straight portion of at least one loop portion and/or at least one connecting portion of at least one loop portion, including a tolerance of +/−15°, preferably +/−5°, more preferably +/−2°. The frame portion has at least one fiber layer with a fiber orientation perpendicular to the length orientation of the beam portion and/or at least one straight portion of at least on loop portion and/or at least one connecting portion of at least one loop portion, including a tolerance of +/−15°, preferably +/−5°, more preferably +/−2°. The frame portion has at least one fiber layer with a fiber orientation which is arranged under an angle of 45° to the length orientation of the beam portion and/or at least one straight portion of at least on loop portion and/or at least one connecting portion of at least one loop portion, including a tolerance of +/−15°, preferably +/−5°, more preferably +/−2°. The frame portion has at least one primary fiber layer with cut-outs in the region of the male and/or female engagement features and/or at least one enforcement fiber layer in the region of the male and/or female engagement features. The frame portion has at least one primary fiber layer with cut-outs in a seat belt attachment region and/or at least one enforcement fiber layer in the seat belt attachment region. The frame portion has at least two, preferably a plurality of, enforcement fiber layers in the region of the male and/or female engagement features and/or in the seat belt attachment region, wherein preferably at least one primary fiber layer is arranged between the at least two enforcement fiber layers and wherein preferably a subsequent enforcement fiber layer covers a smaller area than the previous enforcement fiber layer. The frame portion has at least one continuous fiber layer, preferably a plurality of continuous fiber layers, covering at least a portion of the beam portion and adjacent portions of the respective spine portion, wherein preferably a subsequent fiber layer covers the same or a smaller area than the previous fiber layer and wherein preferably a subsequent fiber layer has a fiber orientation perpendicular to the previous fiber layer. The frame portion has at least one continuous fiber layer, preferably a plurality of continuous fiber layers, covering at least a portion of the beam portion, at least a portion of the loop portions and at least a portion of the spine portions, wherein preferably a subsequent fiber layer covers the same or a smaller or a larger area than the previous fiber layer. The frame portion has at least one fiber layer extending along portions of the beam portion, portions of the at least one loop portion and portions of the at least one spine portion, wherein the fiber layer has continuous portions with different fiber orientations abutting along a butt-join and wherein each continuous layer portion is free of intersections, wherein a first layer portion extends at least along portions of the beam portion and/or along portions of the loop portion, wherein a second layer portion extends at least along portions of the spine portion and wherein a butt-join between the first and the second layer portion extends along a transition region or adjacent to a transition region between the at least one spine portion and the beam portion or the respective loop portion. The frame portion has at least one fiber layer extending along portions of the at least one loop portion, wherein the fiber layer has continuous portions with different fiber orientations abutting along a butt-join and wherein each continuous layer portion is free of intersections, wherein a first layer portion extends at least along a base section of the respective loop portion, wherein a second layer portion extends at least along a flank section of the respective loop portion and wherein a butt-join between the first and the second layer portion extends along an edge or rounded edge between the base section and the flank section. At least one of the above features allows an optimization of a weight vs. stability ratio of the frame portion and/or a particularly high stability of the frame portion in different load and/or torsion orientations and/or a high stability between different portions of the frame portion, particularly in the transition region between the spine portions and the beam portion and/or the loop portions, and/or a strong connection to an adjacent leg portion and/or seat portion. A seventh aspect of the invention relates to a supporting portion for a lightweight aircraft passenger seat assembly, preferably in combination with any one of the preceding aspects of the invention, wherein the supporting portion comprises at least one leg portion and at least one frame portion, wherein the leg portion is coupled to the frame portion via at least one rotary joint. The rotary joint preferably satisfies at least one of the following features: The rotary joint comprises at least a frame coupling element of the leg portion and/or a leg coupling fixture of the frame portion and/or a link member, which is configured to couple the frame coupling element and the leg coupling fixture, wherein preferably at least one of the frame coupling element, the leg coupling fixture or the link member is made from a metal material. The rotary joint comprises at least one link member, which is formed by a screw or a bolt, wherein the link member is preferably inserted into the through hole of at least one of the frame coupling element and the leg coupling fixture, wherein the link member is preferably inserted in the through hole of one of the frame coupling elements and in two through holes of the leg coupling fixture being arranged adjacent to the respective frame coupling element, wherein the through hole of the frame coupling element is preferably arranged between the through holes of the respective leg coupling fixtures. The rotary joint comprises at least one nut, which is configured to be screwed onto the respective link member of the rotary joint. The rotary joint comprises at least a washer ring, wherein at least one washer ring is preferably arranged between the head of the link member and a connecting portion of the frame coupling element and/or a connecting portion of the leg coupling fixture and/or wherein at least one washer ring is preferably arranged between the nut and a connecting porting of the frame coupling element and/or a connecting porting of the leg coupling fixture, wherein at least one washer ring is preferably arranged between the connecting portion of the frame coupling element and the connecting portion of the leg coupling fixture. The rotary joint is configured to rotate the frame portion relative to the leg portion, wherein the axis of rotation of the rotary joint is preferably substantially parallel, including a tolerance of up to 20°, to an aircraft floor, preferably parallel to the aircraft's pitch axis and/or roll axis, wherein the rotary joint preferably enables rotation of the frame portion relative to the leg portion by an angle of up to +10° and/or −10°, preferably at least +5° and/or −5° and preferably of up to +15° and/or −15°, as measured from a regular position. The rotary joint is configured to rotate the frame portion relative to the leg portion, wherein the axis of rotation is formed by the length axis of the link member. The rotary joint is configured to rotate the frame portion relative to the leg portion, wherein the link member is inserted into the through holes of the frame coupling element and the leg coupling fixture in a loose tolerance fit and/or wherein the link member is preferably fastened by a nut in a loose tolerance fit to allow a rotation of the frame portion relative to the leg portion around an axis of rotation, which is preferably orthogonal to the length axis of the link member, preferably by an angle of up to +10° and/or −10°, more preferably at least +5° and/or −5° and even more preferably of up to +15° and/or −15°, as measured from a regular position. The rotary joint is configured to rotate the frame portion relative to the leg portion around an axis of rotation, which is orthogonal to the length axis of the link member, wherein the rotation is preferably regularly blocked by at least one blocking element and is only released upon application of an excessive force beyond a predetermined load level to the blocking element, wherein the blocking element preferably fails upon application of the excessive force, wherein the blocking element is preferably formed by a frangible washer. At least one of the above features allows an optimization of a weight vs. stability ratio of the supporting portion and/or a production and maintenance of the supporting portion at considerably low costs. Furthermore, a rotary joint according to one of the above features provides significant stability to the supporting portion, in particular reduces the risk of material failure of the supporting portion, especially in the transition region between frame portion and leg portion, and finally significantly benefits the passing of the dynamic tests prescribed by SAE AS 8049B-2005. An eighth aspect of the invention relates to a seat portion for a lightweight aircraft passenger seat assembly, preferably in combination with any one of the preceding aspects of the invention, wherein the seat portion comprises a seat shell and satisfies at least one of the following features: The seat shell forms an integral and/or monolithic body. The seat shell is a one-piece construction. The seat shell has a concave shape. The seat shell comprises a sitting portion. The seat shell comprises a backrest portion, wherein the backrest portion preferably rigidly connects to the sitting portion, wherein preferably the backrest portion is linear-elastically bendable relative to the sitting portion. The seat shell comprises a backrest portion, wherein the backrest portion and the sitting portion are connected via a continuous material portion, wherein the continuous material portion preferably forms at least a portion of the backrest portion and a portion of the sitting portion. The seat shell comprises a backrest portion, wherein the backrest portion and the sitting portion are connected to each other hinge-free. The seat shell comprises a backrest portion, wherein the backrest portion is coupled to the sitting portion via the frame portion, wherein preferably the sitting portion and the backrest portion are disconnected from each other. The seat shell comprises a headrest portion, wherein the headrest portion preferably rigidly connects to the backrest portion. The seat shell comprises at least one armrest portion, preferably exactly two armrest portions, wherein the armrest portion preferably rigidly connects to the sitting portion and/or to the backrest portion, wherein the armrest portion preferably protrudes from the backrest portion toward the side of the sitting portion and/or protrudes from the sitting portion toward the side of the backrest portion. The seat shell is configured to connect to a frame portion of the supporting portion, wherein preferably the backrest portion is bonded, preferably via at least one bonding portion of the backrest portion, to the spine portion of the frame portion, for example in at least one position including the position of the furcated ends of the spine portion and/or a position of the spine portion between its proximal end and the furcated ends, and/or wherein the sitting portion rests on the beam portion and/or on the loop portion of the frame portion, wherein preferably the sitting portion can slide on the beam portion and/or the loop portion of the frame portion in a guided fashion, preferably so as to be held by friction in individual positions, or wherein the sitting portion is connected, particularly fixedly attached, to the beam portion and/or to the loop portion of the frame portion. The seat shell has at least one bonding portion arranged on the backrest portion, wherein the bonding portion is configured as a shaped element, configured to engage a corresponding shaped element arranged on at least one spine portion for providing a form-fit between the backrest portion and the respective spine portion in a length orientation of the spine portion and/or the backrest portion. The seat portion comprises at least one cushioning pad attached to the sitting portion and/or the backrest portion and/or the headrest portion and/or the armrest portion, wherein the at least one cushioning pad is preferably bonded and/or attached via a Velcro strip to the sitting portion and/or the backrest portion and/or the headrest portion and/or the armrest portion. The seat portion is identical to at least another seat portion. The seat portion and/or the seat shell is configured to be separately attached to the supporting portion. The seat portion and/or the seat shell is disconnected from an adjacent seat portion and/or seat shell of the lightweight aircraft passenger seat assembly, preferably two adjacent backrest portions are disconnected from each other. At least one of the above features allows an optimization of a weight vs. stability ratio of the seat portion and/or a production and maintenance of the seat portion at considerably low costs. Furthermore, an integrated design according to one of the above features provides significant rigidity to the seat shell and significantly benefits the passing of the dynamic tests prescribed by SAE AS 8049B-2005. A ninth aspect of the invention relates to a seat portion for a lightweight aircraft passenger seat assembly, preferably in combination with at least one of the preceding aspects of the invention, wherein the seat portion comprises a seat shell and satisfies at least one of the following features: The seat shell is at least partially, preferably entirely, made from a plastic material, preferably formed by an injection moulding. The seat shell is at least partially, preferably entirely, made from fiber rein-forced composite material, preferably a laminated fiber reinforced composite material. The seat shell is an integral composite sandwich construction. The seat shell comprises a first fiber layer, a second fiber layer and a core material between the first fiber layer and the second fiber layer, preferably a foam core material or a closed cell foam core material in particular, and preferably a rigid reinforcement member between the first fiber layer and the second fiber layer, wherein the first and the second fiber layer are preferably made from the enforcement fiber layer material. The seat shell comprises a first fiber layer, a second fiber layer and a core material between the first fiber layer and the second fiber layer, wherein the core material extends along portions of the sitting portion and/or along portions of the backrest portion and wherein preferably the transition region between the back-rest portion and the sitting portion is free of the core material. The seat shell comprises a first fiber layer and a second fiber layer, wherein the first fiber layer is arranged on the passenger side of the seat shell and the second fiber layer is arranged on the side of the seat shell averted from the passenger side of the seat shell, wherein preferably the second fiber layer is intersected in the transition region or adjacent to the transition region between the sitting portion and the backrest portion of the seat shell and wherein preferably the first fiber layer extends along the sitting portion and the backrest portion free of intersections. The seat shell comprises at least one fiber layer with a fiber orientation in the length orientation of the seat shell, preferably in the length orientation of the sitting portion and/or in the length orientation of the backrest portion, including a tolerance of up to +/−60°, preferably of up to +/−45°, more preferably of up to +/−30 and more preferably of up to +/−15°. The seat shell comprises at least one armrest portion comprising at least one fiber layer, preferably a plurality of fiber layers, with a fiber orientation in length orientation of the armrest portion, including a tolerance of up to +/−60°, preferably of up to +/−45°, more preferably of up to +/−30 and more preferably of up to +/−15°, wherein preferably a plurality of fiber layers of the armrest portion have the same fiber orientation, including a tolerance of up to +/−15°, preferably of up to +/−10°, more preferably of up to +/−5 and more preferably of up to +/−2°, wherein the at least one fiber layer of the armrest portion is preferably a filling ply. The seat shell comprises at least one armrest portion comprising a foam core, wherein preferably two layers subsequent to the foam core have fiber orientations which are arranged perpendicular or at an angle of +/−45° to each other. The seat shell with at least one shaped element arranged at the backrest portion, wherein the at least one shaped element comprises a foam core portion in a corresponding shape, which foam core portion is bonded to the foam core of the backrest portion. At least one of the above features allows an optimization of a weight vs. stability ratio of the seat portion and/or a production and maintenance of the seat portion at considerably low costs. Furthermore, an integrated design and a fiber layer composition according to one of the above features provides significant rigidity to the seat shell and significantly benefits the passing of the dynamic tests prescribed by SAE AS 8049B-2005. A tenth aspect of the invention relates to a foot portion for a lightweight aircraft passenger seat assembly, preferably in combination with at least one of the preceding aspects of the invention, wherein the foot portion satisfies at least one of the following features: The foot portion comprises at least one cap, which caps a part of a leg portion of the supporting portion and is preferably bonded to the leg portion, wherein the cap preferably has a complementary interior shape to an exterior shape of at least one leg of the leg portion, so as to fit snugly onto said leg, wherein the cap preferably wedges two symmetrical bodies of the leg portion together in an orientation perpendicular to the symmetry plane. The foot portion comprises at least one floor coupling element, which is fixedly attached within a recess at the free end of at least one of the first and the second leg, wherein the at least one coupling element preferably comprises a supporting portion, which is inserted into the recess of the respective leg, and a connecting portion with a through hole for a bolt or a screw, wherein the supporting portion preferably has a complementary exterior shape to an interior shape of the at least one leg, so as to fit snugly into said leg. The foot portion is configured to couple the supporting portion with an aircraft structure, preferably to a rail provided at an aircraft floor. The foot portion forms a rotary joint which is configured to rotate the supporting portion relative to an aircraft structure, wherein the axis of rotation of the rotary joint is preferably substantially parallel, including a tolerance of up to 20°, to an aircraft floor, preferably parallel to the aircraft's pitch axis and/or roll axis, wherein the rotary joint preferably enables rotation of the supporting portion relative to the aircraft structure by an angle of up to +10° and/or −10°, preferably at least +5° and/or −5° and preferably of up to +15° and/or −15°, as measured from a regular position. The foot portion forms a rotary joint, wherein the rotation is preferably regularly blocked by at least one blocking element and is only released upon application of an excessive force beyond a predetermined load level to the blocking element, wherein the blocking element preferably fails upon application of the excessive force. The foot portion forms a rotary joint, wherein a barrel nut is received in a cavity of a housing in a rotatable fashion and connected to a bolt to be secured to an aircraft structure, wherein the housing is preferably formed by a cap, wherein the rotation of the barrel nut is preferably blocked in a predetermined angular position relative to the housing by means of at least one shear plate acting as blocking element, wherein the at least one shear plate fails upon application of an excessive force beyond the predetermined load level, so as to allow the barrel nut to rotate relative to the housing. The foot portion comprises at least one housing, wherein the housing is preferably formed by a cap with a free end on its bottom side averted from the respective leg portion and facing the airplane floor in an installed state of the foot portion, which free end comprises at least one chamfer, preferably two chamfers, configured to enable the rotation of the housing relative to the airplane floor in an installed state of the foot portion. The foot portion is identical to at least another foot portion. The foot portion is different to at least another foot portion. The above features allow a safe coupling of the supporting portion with the aircraft structure by the foot portion. Most notably, the foot portion can be designed according to the above features in order to accommodate the required test condition preloads according to SAE AS 8049B-2005. An eleventh aspect of the invention relates to a passenger safety belt fixture for a lightweight aircraft passenger seat assembly, preferably in combination with at least one of the preceding aspects of the invention, wherein the passenger safety belt fixture satisfies at least one of the following features: The passenger safety belt fixture comprises at least one bolt for bolting the passenger safety belt to the supporting portion. The passenger safety belt fixture comprises at least one cover for covering at least one part of the supporting portion, preferably a part of the supporting portion around or in the vicinity of a bolted joint, so as to spread loads induced from a passenger safety belt across a surface around the bolted joint. The passenger safety belt fixture comprises at least one attachment for attaching parts of the passenger safety belt to it, wherein the attachment is preferably bolted by the at least one bolt to the at least one cover. At least one of the above features enables a secure coupling of a passenger safety belt directly to the supporting portion of the inventive lightweight aircraft passenger seat assembly, which is made from a fiber reinforced composite material. Further to the aspects described above, the inventive seat assembly or its inventive components may comprise features for enhancing the comfort of the seat assembly or its components. These features include, for example, pockets for magazines, newspapers, information documents or the like, wherein the pockets may be arranged at the rearward sides of the backrest portions or the rearward side of the spine portions. The pockets may be configured to be resiliently swung open or pulled open and configured to close in a self-acting manner. Also, fixtures for hanging up clothes, such as coat hooks or the like, may be provided at the rearward sides of the backrest portions or the rearward side of the spine portions. Hinged tables and/or cup holders may be provided at the rearward sides of the backrest portions or the rearward side of the spine portions or the rearward sides of the beam portions and/or the loop portions, facilitating the consumption of food and beverages by the respective rearward passenger. The cup holders may be hinged or fixedly attached to the seat portion or the frame portion and/or integrated in the respective table. The table and/or the cup holder may also be arranged inside an armrest, especially in case the respective seat assembly is configured to be positioned in the first passenger line of the respective aircraft. Thereby, the table and/or cup holder may be configured to be folded out of and folded back into the armrest. Furthermore, the armrests and also the headrests may be removable and/or arranged in a swivelling manner, which enhances the comfort of an inventive seat assembly, too. Finally, the seat portion may be configured to be adjusted relative to the supporting portion in order to provide different sitting positions for the aircraft passenger. For example, the seat portion may be configured to swivel relative to the supporting portion. Moreover, the inventive seat assembly or its inventive components may be equipped with entertainment features. In particular, the seat assembly may comprise electrical connectors, such as female connectors for head-phones, mobile phones, handhelds, computers or the like, which may be arranged at any component of the seat assembly, particularly at the rearward side of the seat portion or the rearward side of the frame portion and/or the armrest portion of the respective seat portion. The seat assembly may also comprise monitors or displays arranged at said positions, which monitors or displays may be connected or connectable to an electronic entertainment device or a personal computer or the like. A twelfth aspect of the invention relates to a method for producing a lightweight component for a lightweight aircraft passenger seat assembly, preferably for a lightweight component according to any one of the preceding aspects of the invention, wherein the method comprises at least one of the following steps: Providing a prepreg, preferably comprising a matrix of a thermoplastic composite and fibers, preferably carbon fibers, wherein said prepreg preferably satisfies at least one of the features of the lightweight component according to the second aspect of the present invention. Heating a prepreg, preferably via an infrared heater and/or via an UV lamp. Transporting said prepreg, preferably between a heating device and a forming device. Forming said prepreg, preferably press forming said prepreg, more preferably press forming with matching metal moulds or moulds consisting of a metal and a rubber part or with a fluid bladder on one side, wherein the molds are preferably heated. Removing said press formed prepreg from a forming device, preferably while the press formed prepreg is hot. Cooling said prepreg, preferably said press formed prepreg. Machining said press formed and/or cooled prepreg, preferably CNC machining of said press formed and/or cooled prepreg. At least one of the above method steps enables efficient and reliable production of a lightweight component for a lightweight aircraft passenger seat assembly, which may in particular be conducted with comparably low costs. Other embodiments of the invention result from combinations of the features disclosed in the claims, the specification and the drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1-7 are views of the lightweight aircraft passenger seat assembly according to the present invention, showing two leg portions, one frame portion and three seat portions, wherein FIG. 1 is a perspective front view; FIG. 2 is a perspective rear view; FIG. 3 is a front view; FIG. 4 is a rear view; FIG. 5 is a side view; FIG. 6 is a top view and FIG. 7 is a bottom view of the seating arrangement according to the present invention in an assembled state. FIG. 8 is a perspective view of a leg portion of the lightweight aircraft passenger seat assembly according to the present invention combined with parts of the front and rear foot portions, respectively. FIG. 9 is another perspective view of the leg portion of FIG. 8 . FIG. 10 is a partial perspective exploded view of the leg portion of FIG. 8 , combined with other parts of the front and rear foot portions, respectively, and the corresponding rail. FIG. 11 is another enlarged partial perspective exploded view of the front leg of the leg portion of FIG. 10 , combined with parts of the front foot portion and the corresponding rail. FIG. 12 is a perspective front view of the frame portion of the lightweight aircraft passenger seat assembly according to the present invention. FIG. 13 is a perspective rear view of the frame portion of FIG. 12 . FIG. 14 is an enlarged partial perspective exploded view of the frame portion of FIG. 12 and the leg portion of FIG. 8 combined with parts of passenger safety belt fixtures. FIG. 15 is a highly enlarged partial perspective exploded view of a rear side part of the frame portion of FIG. 12 combined with parts of passenger safety belt fixtures. FIG. 16 is a perspective exploded front view of one of the seat portions of the lightweight aircraft passenger seat assembly according to the present invention. FIG. 17 is a perspective exploded rear view of the seat portion of FIG. 16 . FIG. 18 is a perspective rear view of the seat portion of FIGS. 16 and 17 in an assembled state. FIG. 19 is a perspective exploded front view of the supporting portion comprising the frame portion of FIG. 12 and two leg portions of FIG. 8 . FIG. 20 is a perspective exploded front view of the lightweight aircraft passenger seat assembly according to the present invention, including the supporting portion of FIG. 19 and three seat portions of FIG. 18 . FIG. 21 is a perspective exploded rear view of the lightweight aircraft passenger seat assembly according to FIG. 20 . FIG. 22 is a perspective view of a layer structure of a lightweight component for a lightweight seat assembly. FIG. 23 a -23 f are perspective views of layer structures of a lightweight component for a lightweight seat assembly. FIG. 24 a -24 d are cross-sectional views of layer structures of a lightweight component for a lightweight seat assembly. FIG. 25 is a perspective view of a further layer structure of a lightweight component for a lightweight seat assembly. FIG. 26 is a cross-sectional view of a leg of the leg portion in a length-wise orientation of said leg. FIG. 27 shows a cross-sectional view of a portion of the frame portion perpendicular to a length-wise orientation of the respective portion of the frame portion. FIG. 28 is a perspective rear view of the lightweight aircraft passenger seat assembly according to a second embodiment of the present invention. FIG. 29 is a perspective view of a leg portion of the lightweight aircraft passenger seat assembly according to a second embodiment of the present invention combined with parts of the respective front and rear foot portions. FIG. 30 is a partial perspective exploded view of the leg portion of FIG. 29 , combined with other parts of the respective front and rear foot portions, and the corresponding rail. FIG. 31 is another enlarged partial perspective exploded view of the front leg of the leg portion of FIG. 30 , combined with parts of the respective front foot portion and the corresponding rail. FIG. 32 is an enlarged partial perspective exploded view of the frame portion and the leg portion of the second embodiment of the present invention combined with parts of passenger safety belt fixtures. FIG. 33 is a further enlarged partial perspective exploded view of the frame portion of the second embodiment of the present invention combined with parts of passenger safety belt fixtures. FIG. 34 is a perspective exploded rear view of the lightweight aircraft passenger seat assembly according to a second embodiment of the present invention, including a supporting portion and three seat portions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The preferred embodiment of the claimed invention provides a lightweight aircraft passenger seat assembly 1 , comprising three seat portions 4 , each one having seat shell 40 for an aircraft passenger, and a supporting portion 2 , 3 for supporting the three seat portions 4 relative to an aircraft structure. Although seat assembly 1 is depicted as a triple seat assembly, the invention can be extended to any practical seat configuration, such as a double seat, a quad seat, a single seat, or a seat configured to accommodate any number of passengers. As will be described in the following, the supporting portion 2 , 3 and the three seat shells 40 are constructed as lightweight components using a fiber reinforced composite material. The supporting portion 2 , 3 of the preferred embodiment contains two leg portions 2 and one frame portion 3 . Hence, the lightweight aircraft passenger seat assembly 1 is constructed of three primary components, namely the leg portions 2 , the frame portion 3 and the seat portions 4 . The two leg portions 2 and the three seat shells 40 will be bonded to the one frame portion 3 so as to form an integrated monolithic structure. The primary and secondary lightweight components of the lightweight aircraft passenger seat assembly 1 will be discussed in the following: The supporting portion 2 , 3 of the preferred embodiment comprises two identical leg portions 2 with four legs 23 , 24 ; 25 , 26 each, wherein each leg 23 , 24 ; 25 , 26 is hollow and comprises one opening at a tapered distal end thereof. Each leg portion 2 is composed of two symmetrical halves 21 , 22 made from laminated fiber reinforced composite material, split down the center plane, which are bonded together to form an integral monolithic laminate body. Two legs 24 , 25 of each leg portion 2 extend along a continuous straight line between a front frame-side connecting portion and a rear foot portion 27 . The leg 23 branches-off from the leg 25 to extend downward to a front aircraft-side coupling portion, whereas the leg 26 branches-off from the leg 24 to extend upward to a rear frame-side connecting portion. The legs 23 , 24 are configured to be coupled with an aircraft structure, wherein the first leg 23 is configured to be oriented forward with respect to the aircraft's longitudinal orientation and the second leg 24 is configured to be oriented rearward with respect to the aircraft's longitudinal orientation. Both legs 23 , 24 are configured to be coupled with the same rail 5 installed at an aircraft floor. The third leg 25 is configured to be oriented forward with respect to the aircraft's longitudinal orientation and the fourth leg 26 is configured to be oriented rearward with respect to the aircraft's longitudinal orientation, and both legs 25 , 26 are configured to be joined to the same frame portion 3 . Each one of the third and fourth legs (upper legs) 25 , 26 comprises one male engagement feature 29 a , 29 c at a distal end thereof for establishing a form-fit together with a corresponding one female engagement feature of a frame portion 3 . The male engagement feature 29 a , 29 c is located on a flat mating surface 29 b , 29 d of each leg portion 2 which abuts to a flat mating surface of the frame portion 3 . The leg portion 2 will be bonded to a frame portion 3 at the position of the at least one male engagement feature 29 a , 29 c and at the position of the at least one mating surface 29 b , 29 d. In addition, the supporting portion 2 , 3 of the preferred embodiment comprises one frame portion 3 which is entirely made from a laminated fiber reinforced composite material to form an integral monolithic laminated body. The frame portion 3 is configured to support three seat portions 4 and therefore defines three receptacles for receiving and supporting the three seat shells 40 of the seat portions 4 . The seat shells 40 will be bonded to the frame portion 3 , as will be described below. The frame portion 3 comprises one straight beam portion 31 , which is configured to be oriented in the aircraft's widthwise orientation. This single beam portion 31 forms a torsion box and can be twisted by a twisting angle of e.g. equal to or greater than +/−5° from an untwisted state. Further, the two closed loop portions 32 are arranged at opposite ends of the beam portion 31 , wherein the straight beam portion 31 and straight sections of two closed loop portions 32 extend along a straight line. In addition to that, the frame portion 3 comprises three spine portions 33 , wherein the center spine portion 33 connects to the beam portion 31 and the outer spine portions 33 connect to the closed loop portions 32 . Each one of the spine portions 33 is configured to extend upwards relative to an aircraft floor and is curved with the center of curvature being located roughly above the sitting portion 41 of the seat shell 40 . Moreover, each one of the spine portions 33 has a bifurcated distal end, which is configured to encompass and/or support a backrest portion of a seat shell 40 and to define a receptacle for receiving the seat shell 40 together with the frame portion 3 . Still further, the frame portion 3 provides passenger safety belt attachment spaces 34 , 35 for receiving and fixing the passenger safety belt fixtures 36 , 37 , wherein the passenger safety belt attachment spaces 34 , 35 integrated into a loop portion 32 are embodied as through-holes, and the passenger safety belt attachment spaces 34 , 35 provided at the outside of the loop portions 32 are embodied as cavities. Each one of the three identical seat shells 40 comprises a sitting portion 41 , a backrest portion 42 , a headrest portion as well as two armrest portions 43 arranged on both longitudinal sides of the backrest portion 42 . The seat shell 40 is a one-piece composite sandwich construction and comprises a first side panel, a second side panel and a core material between the first side panel and the second side panel, and preferably a rigid reinforcement member between the first side panel and the second side panel. The core material may be a closed-cell foam. For connecting the seat shell 40 to the frame portion 3 of the supporting portion 2 , 3 , the backrest portion 42 will be bonded to the spine portion 33 of the frame portion 3 in three positions including the furcated ends of the spine portion 33 and a part of the spine portion 33 between its proximal end and the furcated ends. Additionally, the sitting portion 41 is configured to rest on the beam portion 31 and/or the closed loop portions 32 of the frame portion 3 , so as to slide thereon in a guided fashion, wherein it can be held by friction in individual positions. For comfort, the seat portion 4 comprises cushioning pads 45 , 46 , 47 bonded to the sitting portion 41 , the backrest portion 42 and/or the headrest portion and the armrest portions 43 . The cushioning pads 45 , 46 , 47 can be replaced in case of wear in order to renew the appearance of the seat portion 4 . As one of the secondary components, the lightweight aircraft passenger seat assembly 1 further comprises foot portions 27 , 28 for coupling the leg portions 23 , 24 to a rail 5 provided at an aircraft floor. The foot portions 27 , 28 are preferably made from metal and comprise a cap 27 a , 28 a bonded to the leg portion 2 for capping a part of a leg 23 , 24 having a complementary exterior shape. Accordingly, the caps 27 a , 28 a fit snugly onto the legs 23 , 24 and wedge the two symmetrical halves 21 , 22 of the leg portion 2 together in an orientation perpendicular to the symmetry plane. Each one of the foot portions 27 , 28 forms a rotary joint which is configured to rotate the supporting portion 2 , 3 relative to the aircraft structure, wherein the axis of rotation of the rotary joint is roughly parallel to an aircraft floor. The two forward foot portions 27 of the two leg portions 2 are identical to each other and the two rearward foot portions 28 of the two leg portions 2 are identical to each other as well. However, the forward foot portion 27 is different from the rearward foot portion 28 of the same leg portion 2 . The axis of rotation of the rotary joints formed by the forward foot portions 27 is parallel to the aircraft's roll axis. However, the rotation is regularly blocked in one angular position by at least one blocking element 27 c and is only released upon application of an excessive force beyond a predetermined load level to the blocking element 27 c , so that the blocking element 27 c fails upon application of the excessive force. To establish this blocking, a barrel nut 27 b is received in a cavity of the cap 27 a in a rotatable fashion and connects to a bolt 27 e to be secured to the aircraft floor rail 5 . The rotation of the barrel nut 27 b is blocked in the predetermined angular position relative to the cap 27 a by means of two shear plates 27 c acting as blocking elements 27 c , wherein the two shear plates 27 c are designed to fail upon application of the excessive force, so as to allow the barrel nut 27 b to rotate relative to the cap 27 a. As another one of the secondary components, the lightweight aircraft passenger seat assembly 1 further comprises passenger safety belt fixtures 36 , 37 , each one of them comprising a bolt 36 a , 37 a for bolting the passenger safety belt to the supporting portion 2 , 3 , a cover 36 b , 37 b for covering a part of the supporting portion 2 , 3 around the bolted joint, so as to spread loads induced from the passenger safety belt across a surface around the bolted joint, and one or more attachments 36 c , 37 c for attaching parts of the passenger safety belt to it. The attachments 36 c , 37 c will be bolted by a bolt 36 a , 37 a to a cover 36 b , 37 b. The individual components of the lightweight aircraft passenger seat assembly 1 will be assembled and installed in an airframe in order to undergo required test conditions according to SAE AS 8049B-2005 as follows: The leg portions 2 couple the frame portion 3 to the rails 5 supplied and fitted in the air frame. It is geometrically located and bonded to the frame portion 3 via two male boss engagement features 29 a , 29 c at the upper front and upper rear legs 25 , 26 . The two bonded (in shear direction) metallic caps 27 a , 28 a transfer the required test condition preload according to SAE AS 8049B-2005 from the rails 5 into the leg portions 2 . The 10° roll condition according to SAE AS 8049B-2005 on the rear leg 24 is accommodated via deformation of the bolt 28 c in the rear foot portion 28 . The same 10° roll condition according to SAE AS 8049B-2005 on the front leg 23 is accommodated by way of the rotary “fuse” design of the front foot portion 27 as described above. This front foot portion 27 comprises the two shear plates 27 c which are designed such that they fail (shear through) at an angular rotation far higher than standard operational use, yet lower than the required 10° preload according to SAE AS 8049B-2005. This allows for any tensile and fore/aft loads through the front leg 23 to be reacted via the barrel nut 27 b yet considerably lowers residual stresses in the pre-loaded condition. FIG. 11 details the shear bonding characteristic design of the metallic feet 27 . The nut ring 27 d , bolt 27 e and rail 5 shown are airframe standard fit. As mentioned earlier, the leg 23 is moulded in two symmetrical halves 21 , 22 , split down the center plane, and the halves 21 , 22 are bonded together and mechanically encapsulated via the caps 27 a , so as to realize a monolithic laminate design. The frame portion 3 is coupled with the rail 5 via the leg portions 2 and the foot portions 27 , 28 and consists of the actual seating support including the beam portion 31 , two loop portions 32 and three spine portions 33 , which are used to support the three individual seat shells 40 . Again, it is a monolithic laminate design. Having accommodated the roll 10 degree condition according to SAE AS 8049B-2005 with the application of the feet designs, the 10 degree pitch condition is accommodated through the twisting of the single section center beam portion 31 . This area also connects the center seat's spine portion 33 . This torsion box is designed both geometrically and in laminate definition to allow the 10 degree rotation deformation without failure and whilst maintaining structural integrity to continue to pass both the 14G downward and 16G forward dynamic tests prescribed by SAE AS 8049B-2005. The frame portion 3 also carries the coupling points for the passenger seat belts. These are supported internally with the addition of a metallic insert—designed such that it spreads the bearing load of the coupling into the composite structure. The seat shell 40 is a one-piece composite sandwich construction. The core material is a closed cell foam. Pads 45 , 46 , 47 for comfort are bonded onto the front of the seat shell 40 . One important feature in allowing the complete assembly to absorb the 10 degree pitch condition, through the beam portion 31 (torsion box) in the frame portion 3 , is the de-coupled seat shell 40 from the frame portion 3 . The seat shell 40 itself is bonded in only three places to the spine portions 33 of the frame portion 3 . The sitting portion 41 of the seat shell 40 may only rest on the actual seating support including the beam portion 31 and two loop portions 32 of the frame portion 2 without a mechanical or other connection. However, it is also possible to connect, particularly mechanically connect, the sitting portion 41 of the seat shell 40 to the respective seating support including the beam portion 31 and two loop portions 32 . This improves the stability of the respective seat, particular for the case a rearward passenger pulls on the backrest portion 42 in order to stand up. Thereby, it may be desirable to connect the sitting portions 41 of the outer seat shells 40 of the seat assembly 1 to their respective seating supports, but leaving the sitting portion 41 of the center seat shell 40 disconnected and/or decoupled from its seating support, thus, maintaining the flexibility of the frame portion 3 , particularly of the beam portion 31 . The seat shell 40 has two integrated fixed position armrests, one per side. This removes the need to attach the armrest to the traditional “hanger”. FIG. 22 shows a schematic layer structure 50 of a lightweight component. The features of the layer structure 50 may be applied to any lightweight component 2 , 3 , 4 of the lightweight seat assembly 1 , whereas the layers of the layer structure 50 may be shaped in any form desired for the respective application. Layer structure 50 comprises a first layer 51 , a second layer 52 and a third layer 53 , whereas every layer 51 , 52 , 53 may be a fiber layer. First layer 51 may be made of a different material than second layer 52 and second layer 52 may be made from a different layer than third layer 53 . Likewise, it is possible that all three layers 51 , 52 , 53 are made from the same material or only two of the three layers are made from the same material and the remaining layer is made from a different material. Fiber layer 51 may have a smaller or greater thickness than fiber layer 52 , and fiber layer 52 may have a smaller or greater thickness than fiber layer 53 . Likewise, it is possible that all fiber layers 51 , 52 , 53 have the same thickness or only one of the fiber layers 51 , 52 , 53 has a smaller or greater thickness than the remaining two fiber layers. Fiber layer 51 may be a primary fiber layer and fiber layer 52 may be an enforcement fiber layer. The fibers 51 a of fiber layer 51 may have a different orientation than the fibers 52 a of the fiber layer 52 and the fibers 52 a of the fiber layer 52 may have a different orientation than the fibers 53 a of the fiber layer 53 . Likewise, it is possible that the fibers 51 a , 52 a , 53 a of the fiber layers 51 , 52 , 53 have the same orientation, or that only one fiber layer has a different fiber orientation than the remaining two fiber layers. Furthermore, the second fiber layer 52 may cover a smaller area than the first fiber layer 51 and the third fiber layer 53 may cover a smaller area than the second fiber layer 52 . Likewise, it is possible that all fiber layers 51 , 52 , 53 cover the same area, or that only one of the fiber layers 51 , 52 , 53 covers a different area than the remaining two fiber layers. FIGS. 23 a to 23 f depict different layer compositions of a fiber layer structure 50 . According to FIG. 23 a , the fibers 51 a of the first fiber layer 51 have the same orientation as the fibers 52 a of the second fiber layer 52 . According to FIG. 23 b , the fibers 51 a of the first fiber layer 51 have an orientation perpendicular to the fibers 52 a of the second fiber layer 52 . According to FIG. 23 c , the fibers 51 a of the first fiber layer 51 have an orientation which is arranged at an angle of 45° relative to the orientation of the fibers 52 a of the second fiber layer 52 . According to FIG. 23 d , the fibers 51 a of the first fiber layer 51 have an orientation which is arranged at an angle of 45° relative to the orientation of the fibers 52 a of the fiber layer 52 , and the fibers 51 a of the first fiber layer 51 have an orientation perpendicular to the orientation of the fibers 53 a of the third fiber layer 53 . According to FIG. 23 e , the fibers 51 a of the first fiber layer 51 and the fibers 53 a of the third fiber layer 53 have the same orientation, whereas the fibers 52 a of the second fiber layer, which second fiber layer 52 is arranged between the first fiber layer 51 and the third fiber layer 53 , have an orientation which is arranged at an angle of 45° relative to the orientation of the fibers 51 a of the first fiber layer 51 and the fibers 53 a of the third fiber layer 53 . According to FIG. 23 f , the first fiber layer 51 has a first layer portion 51 b and a second layer portion 51 d , whereas the fibers 51 a of the first layer portion 51 b have a different orientation than the fibers 51 c of the second layer portion 51 d . The layer portions 51 b and 51 d abut along a butt-join 51 d . The first fiber layer 51 , with its two layer portions 51 b and 51 d , is covered by a second fiber layer 52 , which may have a fiber orientation identical to the fiber orientation of the first layer portion 51 b or the second layer portion 51 d , or different to the layer portions 51 b and 51 d. FIGS. 24 a to 24 d depict different configurations for fiber layers being separated into different layer portions in a cross-sectional view. According to FIG. 24 a , the first fiber layer 51 comprises a first layer portion 51 b and a second layer portion 51 d , wherein the first layer portion 51 b and the second layer portion 51 d abut along a butt-join 51 e . The second layer 52 is not intersected and therefore continuously covers the butt-join 51 e. According to FIG. 24 b , the second layer 52 is also separated into a first layer portion 52 b and a second layer portion 52 d , whereas the first layer portion 52 b and the second layer portion 52 d abut along a butt-join 52 e . However, the butt-join 52 e is positioned at a distance from the butt-join 51 e in an orientation length-wise to the layers 51 and 52 . The risk of damages to the component in the region of one of the butt-joins 51 e or 52 e is thereby reduced. According to FIG. 24 c , the first layer 51 has a first layer portion 51 b and a second layer portion 51 d , whereas the first layer portion 51 b and the second layer portion 51 d abut along a butt-join 51 e . Furthermore, the first layer portion 51 b and the second layer portion 51 d are arranged at an angle relative to each other. Thereby, the butt-join 51 e extends along the edge between the two angled layer portions 51 b and 51 d . Likewise, the second layer 52 has a first layer portion 52 b and a second layer portion 52 d . Likewise, the two layer portions 52 b and 52 d are arranged at an angle relative to each other, however, the two layer portions 52 b and 52 d are not intersected by a butt-join in the region of the edge but continuously extend along the edge. According to FIG. 24 d , the fiber layer 51 comprises a first layer portion 51 b and a second layer portion 51 d , wherein the first layer portion 51 b and the second layer portion 51 d overlap in an adjoining region 51 f , thereby ensuring a high stability, particularly in the adjoining region 51 f. According to FIG. 25 , the first layer 51 has a first layer portion 51 b and a second layer portion 51 d , whereas the first layer portion 51 b and the second layer portion 51 d are arranged at an angle relative to each other. The edge between the first layer portion 51 b and the second layer portion 51 d is configured as a force transmission portion, as it transmits forces between the first layer portion 51 b and the second layer portion 51 d . However, the force transmission portion may not be limited to the edge but also may comprise portions adjacent to the edge. Likewise, the force transmission portion does not necessarily comprise an edge but may contain any portions of a component, which are configured to transmit significant forces between adjacent component portions during operation of the respective component. Likewise, the second layer 52 comprises a first layer portion 52 b and a second layer portion 52 d , which layer portions are arranged at an angle relative to each other. The second layer 52 , with its two layer portions 52 b and 52 d , at least partially covers the force transmission portion 51 g , in order to reinforce it. Furthermore, the first fiber layer 51 may have a force application portion 51 h , which may be configured for receiving external forces, for example, by connecting the force application portion with another component of the seat assembly. The force application portion 51 h may comprise a cut-out 51 i , whereas the cut-out may extend along the first layer portion 51 b and also the second layer portion 51 d . The cut-out may ensure a stress reduction in the first fiber layer 51 . The force application portion 51 h , with its cut-out 51 i , may be covered by the second layer 52 , in order to sufficiently stabilize the respective component in the region of the force application portion 51 h. FIG. 26 shows a cross-sectional view of leg 23 of the leg portion 2 in a length-wise orientation of leg 23 . The features described in the context of FIG. 26 may likewise be applied to legs 24 , 25 , 26 of the leg portion 2 . The cross-section of leg 23 comprises a first base section 22 a and a second base section 22 b , whereas the first section 23 a and the second base section 23 b may be arranged parallel to each other and the cross-sectional lengths of the base sections 23 a , 23 b may be identical. Further, the cross-section of the leg 23 may comprise three flank sections pairs 23 c , 23 d ; 23 e , 23 f ; 23 g , 23 h , whereas the flank sections of each flank section pair 23 c , 23 d ; 23 e , 23 f ; 23 g , 23 h may be arranged parallel to each other. Thereby, flank section 23 c and flank section 23 g may be connected to base section 23 a at its opposite ends, flank section 23 d and flank section 23 h may be connected to base section 23 b at its opposite ends, flank section 23 f may connect flank section 23 c and flank section 23 h and flank section 23 e may connect flank section 23 d and flank section 23 g . In this arrangement, the cross-section of leg 23 forms an octagon. FIG. 27 shows a cross-sectional view of the beam portion 31 , of a straight section of the loop portion 32 , of a connection portion of the loop portion 32 or of the spine portion 33 perpendicular to a length-wise orientation of the respective beam portion 31 , the respective straight section of the loop portion 32 , the respective connection portion of the loop portion 32 or the respective spine portion 33 . The cross-section of the respective portion 31 , 32 , 33 may have a base section 31 a , 32 a , 33 a and a first flank section 31 b , 32 b , 33 b and a second flank section 31 c , 32 c , 33 c , whereas the flank sections 31 b , 32 b , 33 b , 31 c , 32 c , 33 c may be connected to the base section 31 a , 32 a , 33 a at its opposite ends and under an angle to the base section 31 a , 32 a , 33 a . In this arrangement, the cross-section of the respective beam portion 31 , of the respective straight section of the loop portion 32 , of the respective connection portion of the loop portion 32 or of the respective spine portion 33 forms an open profile. In the following a second preferred embodiment of the claimed invention will be described with reference to FIGS. 28 to 34 , whereas basically the differences to the first embodiment described above will be discussed. Thereby, components identical to the first embodiment of the present invention will be assigned identical reference signs, and components different to those of the first embodiment of the invention will be assigned different reference signs. FIG. 28 shows a lightweight aircraft passenger seat assembly 101 according a second embodiment of the present invention. The lightweight aircraft passenger seat assembly 101 comprises three seat portions 4 , each one having seat shell 40 for an aircraft passenger, and a supporting portion 102 , 103 for supporting the three seat portions 4 relative to an aircraft structure. Although seat assembly 101 is depicted as a triple seat assembly, this embodiment can be extended to any practical seat configuration, such as a double seat, a quad seat, a single seat, or a seat configured to accommodate any number of passengers. As will be described in the following, the supporting portion 102 , 103 and the three seat shells 40 are constructed as lightweight components using a fiber reinforced composite material. The supporting portion 102 , 103 of the preferred embodiment contains two leg portions 102 and one frame portion 103 . Hence, the lightweight aircraft passenger seat assembly 101 is constructed of three primary components, namely the leg portions 102 , the frame portion 103 and the seat portions 4 . The two leg portions 102 and the three seat shells 40 will be connected to the one frame portion 103 . In particular, each leg portion 102 is connected to the frame portion 103 via rotary joints 160 and 170 , which are described in more detail with reference to FIG. 32 . As shown in FIG. 29 , also the leg portions 102 comprise four legs 123 , 124 , 125 , 126 each, wherein each leg 123 , 124 , 125 , 126 is made from a laminated fiber reinforced composite material. Two legs 124 , 125 of each leg portion 102 extend along a continuous straight line between a front frame-side connecting portion and a rear foot portion 128 . The leg 123 branches-off from the leg 125 to extend downward to a front aircraft-side coupling portion, whereas the leg 126 branches-off from the leg 124 to extend upward to a rear frame-side connecting portion. Furthermore, the leg portion 102 comprises three separate bodies, namely an internal structure 120 and two symmetrical halves 121 and 122 , which are split down the center plane, and are bonded, preferably bolted and/or welded, together, in order to at least sectionwise encapsulate the internal structure body 120 . At the same time the two symmetrical halves 121 and 122 form an open profile. In particular, the symmetrical halves 121 and 122 in the area forming the first leg 123 and/or the third leg 125 and/or encapsulating the respective portion of the internal structure body 120 of the first leg 123 and/or the third leg 125 form an open profile being open in the forward direction with respect to the aircraft's longitudinal orientation. Likewise, the symmetrical halves 121 and 122 in the area forming the second leg 124 and/or the fourth leg 126 and/or encapsulating the respective portion of the internal structure body 120 of the second leg 124 and/or the fourth leg 126 form an open profile being open in the rearward direction with respect to the aircraft's longitudinal orientation. Accordingly, the symmetrical halves 121 and 122 in the area forming the first leg 123 and/or the third leg 125 and/or encapsulating the respective portion of the internal structure body 120 of the first leg 123 and/or the third leg 125 form an open profile being closed in the rearward direction with respect to the aircraft's longitudinal orientation. Likewise, the symmetrical halves 121 and 122 in the area forming the second leg 124 and/or the fourth leg 126 and/or encapsulating the respective portion of the internal structure body 120 of the second leg 124 and/or the fourth leg 126 form an open profile being closed in the forward direction with respect to the aircraft's longitudinal orientation. Furthermore as may be seen in FIG. 29 , the leg portion 102 comprises recesses 129 a for receiving frame coupling elements 161 and 171 of the respective rotary joints 160 and 170 . Said frame coupling elements 161 and 171 are configured to couple the leg portion 102 with the frame portion 103 via leg coupling fixtures 162 and 172 of the frame portion 103 , which leg coupling fixtures 162 and 172 are also part of the rotary joints 160 and 170 . Furthermore as may be seen in FIG. 29 , the leg portion 102 comprises recesses 129 b for receiving foot portions 127 and 128 , particularly floor coupling elements 127 a and 128 a , which are configured to couple the leg portion 102 with a rail 5 provided at an aircraft floor. Each of the recesses 129 a and 129 b is formed by the free ends of the legs 123 , 124 , 125 and 126 , wherein the frame coupling elements 161 and 171 and/or the floor coupling elements 127 a and 128 a are each fixedly attached within the respective recesses 129 a and 129 b . Each frame coupling element 161 and 171 comprises a supporting portion, which is inserted into the recess 129 a of the respective leg 125 and 126 , and a connecting portion with a through hole 161 a and 171 a for a bolt or a screw 163 , 173 , wherein the supporting portion has an exterior shape being complementary to an interior shape of the recesses 129 a of the legs 125 and 126 , so as to fit snugly into the respective leg 125 , 126 . As may be comprehended from FIG. 30 and FIG. 31 , the foot portions 127 and 128 of a lightweight aircraft passenger seat assembly according to the second embodiment comprise floor coupling elements 127 a , 128 a , which are each fixedly attached within a recess at the free end of at least one of the first and the second leg 123 and 124 . Each one of the floor coupling elements 127 a and 128 a comprises a supporting portion, which is inserted into the recess 129 b of the respective leg, and a connecting portion with a through hole 127 b , 128 b for a nut, bolt or a screw, wherein the supporting portions preferably have exterior shapes, which are complementary to an interior shape of the recess 129 b of the respective leg 123 , 124 , so as to fit snugly into said leg 123 , 124 . Also, in the case of the second embodiment of the present invention the forward foot portion 127 is different from the rearward foot portion 128 of the same leg portion 102 . The axis of rotation of the rotary joints (provided by the through holes 127 b ) formed by the forward foot portions 127 is parallel to the aircraft's roll axis. However, the rotation is regularly blocked in one angular position by at least one blocking element 27 c and is only released upon application of an excessive force beyond a predetermined load level to the blocking element 27 c , so that the blocking element 27 c fails upon application of the excessive force. To establish this blocking, a barrel nut 27 b is received in a cavity or through hole 127 b of the foot coupling element 127 a in a rotatable fashion and connects to a bolt 27 e to be secured to the aircraft floor rail 5 . The rotation of the barrel nut 27 b is blocked in the predetermined angular position relative to the foot coupling element 127 a by means of two shear plates 27 c acting as blocking elements 27 c , wherein the two shear plates 27 c are designed to fail upon application of the excessive force, so as to allow the barrel nut 27 b to rotate relative to the foot coupling element 127 a. Now referring to FIG. 32 to FIG. 34 the frame portion 103 according to the second embodiment of the present invention comprises at least one leg coupling fixture 162 , 172 , which is configured to couple the frame portion 103 with the leg portion 102 of the seat assembly 101 , in particular with a frame coupling element 161 , 171 of the leg portion 102 . As may be seen in FIGS. 32 and 33 , the leg coupling fixtures 162 and 172 are bolted with the beam portion 31 and/or with the loop portion 32 , particularly with the straight portion of the loop portion 32 . More particularly, the frame portion 103 comprises two leg coupling fixtures 162 and two leg coupling fixtures 172 , wherein the leg coupling fixtures 172 are configured to be coupled to a frame coupling element 171 of the leg portion 102 which is inserted in the recess of a third leg 125 and wherein the leg coupling fixtures 162 are configured to be coupled to a frame coupling element 161 of the leg portion 102 which is inserted in the recess of a fourth leg 126 . Furthermore, as shown in FIGS. 32 and 33 , the leg coupling fixtures 162 and 172 respectively comprise an inlay element 164 , 174 and a cap element 165 , 175 , wherein each inlay element 164 , 174 is configured to be inserted into the beam portion and/or the loop portion of the frame portion 103 from the upper side thereof. Each cap element 165 , 175 is preferably configured to be attached to the beam portion and/or the loop portion of the frame portion 103 from the lower side thereof. Thereby, the respective cap element 165 , 175 is clinched and/or bolted to the respective inlay element 164 , 174 , wherein the respective inlay element 164 , 174 and the respective cap element 165 , 175 enclose a section of the beam portion and/or the loop portion of the frame portion 103 to form sandwich structure. Each cap element 165 , 175 comprises a supporting portion 165 a , 175 a and two connecting portions 165 b , 175 b , respectively, wherein the supporting portions 165 a , 175 a are configured to support the respective cap element 165 , 175 relative to the beam portion and/or the loop portion of the frame portion 103 and, therefore, the supporting portions 165 a , 175 a have a shape complementary to an exterior shape of the beam portion and/or the loop portion of the frame portion 103 , so as to fit snugly thereon from a lower side. The cap elements 165 , 175 may be covered with a cover element 165 c , 175 c , wherein the connecting portions 165 b , 175 b may protrude from the respective supporting portion 165 a , 175 b through a recess in the respective cover element 165 c , 175 c . The connecting portions 165 b , 175 b each have a through hole 165 d , 175 d for a bolt or a screw 163 , 173 , Also, the cover elements 165 c , 175 c have shapes complementary to an exterior shape of the beam portion and/or the loop portion of the frame portion 103 and/or the respective cap element 165 , 175 , so as to fit snugly thereon from a lower side. As already mentioned above, the leg coupling fixtures 162 and 172 are part of the rotary joints 160 and 170 , respectively, and thus form rotary joints 160 and 170 which are configured to rotate the frame portion 103 relative to the leg portion 102 . Thus, the leg portion 102 is coupled to the frame portion 103 via at least one rotary joint 160 , 170 . Though, each rotary joint 160 , 170 comprises a frame coupling element 161 , 171 of the leg portion 102 , a leg coupling fixture 162 , 172 of the frame portion 103 and a link member 163 , 173 , which is configured to couple the frame coupling element 161 , 171 and the respective leg coupling fixture 162 , 172 . At least one of the components of the rotary joints 160 , 170 may be made from a metal material. The link member 163 , 173 may be formed by a screw or a bolt, wherein the link member is inserted into the through hole of the frame coupling element 161 , 171 and the through hole of the leg coupling fixture 162 , 172 . Each of the rotary joints 160 , 170 may also comprise a nut 166 , 176 , which is configured to be screwed onto the respective link member 163 , 173 of the respective rotary joint 160 , 170 . Also, each of the rotary joints 160 , 170 may comprise a washer ring 167 , 177 , wherein said washer ring 167 , 177 may be arranged between the head of the link member 163 , 173 and a connecting portion 165 b , 175 b of the leg coupling fixture 162 , 172 . At least one washer ring 168 , 178 may also be arranged between the nut 166 , 176 and a connecting porting 165 b , 175 b of the leg coupling fixture 162 , 172 . Also, at least one washer ring may respectively be arranged between the connecting portion 165 b , 175 b of the leg coupling fixture 162 , 172 and the connecting portion of the frame coupling element 161 , 171 . It is conceivable that the rotary joint 160 , 170 is configured to rotate the frame portion 103 relative to the leg portion 102 , wherein the axis of rotation is formed by the length axis of the respective link member 163 , 173 . Thereby, the axis of rotation of each of the rotary joints 160 and 170 is preferably substantially parallel, including a tolerance of up to 20°, to an aircraft floor, preferably parallel to the aircraft's pitch axis, wherein the rotary joint preferably enables rotation of the frame portion 103 relative to the frame portion by an angle of up to +10° and/or −10°, preferably at least +5° and/or −5° and preferably of up to +15° and/or −15°, as measured from a regular position. In order to allow according rotation of the frame portion 103 relative around the leg portion 102 around an axis of rotation, which is orthogonal to the length axis of the link members 163 , 173 , by an angle of up to +10° and/or −10°, preferably at least +5° and/or −5° and preferably of up to +15° and/or −15°, as measured from a regular position, each link member 163 , 173 is inserted into the respective through hole of the frame coupling elements 161 , 171 and the leg coupling fixtures 162 , 172 in a loose tolerance fit. Also for this reason the link members 163 , 173 are fastened by the respective nut 166 , 176 in a loose tolerance fit. However, this rotation may regularly blocked by at least one blocking element 169 , 179 and is only released upon application of an excessive force beyond a predetermined load level to the blocking element 169 , 179 , wherein each blocking element 169 , 179 preferably fails upon application of the excessive force, wherein the blocking elements 169 , 179 are preferably formed by a frangible washer. In contrast to the frame portion 3 of the first embodiment, the frame portion of the second embodiment, as shown in FIG. 32 and FIG. 34 , is at least sectionwise covered with a closing panel 103 a , wherein the closing panel 103 a is bonded or welded to the frame portion 103 . Accordingly, the frame portion 103 and the closing panel 103 a together form a cross-section with the shape of a closed profile, said cross-section being perpendicular to the length axis of the respective section of the frame portion 103 . As a secondary component of the second embodiment of the present invention, the lightweight aircraft passenger seat assembly 101 further comprises passenger safety belt fixtures 136 , 37 , whereas the passenger safety belt fixture 37 of the second embodiment may be identical to the passenger safety belt fixture 37 of the first embodiment. On the other hand, passenger safety belt fixtures 136 of the second embodiment may differ to the passenger safety belt fixture 36 of the first embodiment. Passenger safety belt fixtures 136 of the second embodiment may comprise a bolt 36 a for bolting the passenger safety belt to the supporting portion 102 , 103 , a cover portion 136 b for covering a part of the supporting portion 102 , 103 , so as to spread loads induced from the passenger safety belt across a surface of the supporting portion 102 , 103 . In particular, the cover portion 136 b may be integrally connected to or formed together with the respective inlay element 164 of the rotary joint 160 , so that loads induced from the passenger safety belt may directly be absorbed by the leg structure 102 . Furthermore, the passenger safety belt fixtures 136 may comprise one or more attachments 36 c for attaching parts of the passenger safety belt to it. The attachments 36 c will be bolted by a bolt 36 a to the cover portion 136 b. The entire disclosure of European Patent No. 13 000 841.0 filed Feb. 19, 2013 is expressly incorporated by reference herein.
A lightweight aircraft passenger seat assembly comprises at least one seat portion and at least one supporting portion for supporting the at least one seat portion relative to an aircraft structure. In order to provide an improved lightweight aircraft passenger seat assembly having a reduced weight, size and complexity as compared to conventional lightweight passenger seat designs, the invention provides a lightweight aircraft passenger seat assembly, comprising at least one seat portion with at least one seat shell for an aircraft passenger and at least one supporting portion for supporting the at least one seat portion relative to an aircraft structure, wherein the at least one seat shell and the at least one supporting portion are constructed as lightweight components.
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BACKGROUND OF THE INVENTION The present invention relates to methods for removing nitrogen oxides effectively from exhaust gas containing the nitrogen oxides such as exhaust gas from internal combustion engines of automobiles etc, exhaust gas from consumers appliance such as cooking apparatus and the like, and exhaust gas from boilers in factories and thermal power stations. Further, the present invention relates to catalysts for removing nitrogen oxides from the exhaust gas. The catalysts relating to the present invention are preferable for purifying the exhaust gas released from lean burn engines. Nitrogen oxides (NOx) are contained in exhaust gas released from internal combustion engines of automobiles etc. The nitrogen oxides are harmful to human bodies, and become an origin to destroy a global environment by acid rain etc. Therefore, various catalyst s for removing the nitrogen oxides in exhaust gas have been investigated. Most of catalysts for purifying exhaust gas from automobiles which are under developing at present have been aimed at treating exhaust gas from automobiles wherein a ratio of fuel to air, that is air/fuel by weight, is set at approximately stoichiometric ratio, that is theoretical air to fuel ratio (air/fuel=14.7 by weight). Combustion under the stoichiometric condition generates and releases hydrocarbons and carbon monoxide in addition to the nitrogen oxides. The hydrocarbons and carbon monoxide are also environment contaminating material. Therefore, three way catalyst which can treat the above three substances simultaneously have been a main object of the development. The three way catalyst is a general name for catalysts which can simultaneously treat nitrogen oxides, hydrocarbons, and carbon monoxide in exhaust gas. Most of the three way catalysts contain noble metals such as rhodium, palladium, and platinum as for main components. However, currently, lean burn engines which burn fuel under a fuel to air ratio (air/fuel) larger than the theoretical fuel to air ratio are becoming a main current as for automobile engines in view of decreasing fuel consumption. With the lean burning, oxygen content in the exhaust gas increases, and an activity of conventional three way catalyst decreases in the presence of the oxygen. Accordingly, nitrogen oxides in the exhaust gas can not be removed effectively. Therefore, development of catalyst for purifying exhaust gas from lean burn engines becomes necessary. As the catalyst for purifying exhaust gas from lean burn engines, a catalyst which is composed of copper supported by zeolite (JP-A-1-130735 (1989), Proceeding of 68th Meeting for discussing catalyst, 3F108, (1991)), and a catalyst which is composed of cobalt and rare earth metals supported by zeolite and further at least one of copper and rhodium is supported by the zeolite (JP-A-4-219147 (1992)) are disclosed. A catalyst which absorbs NOx under a lean burning condition, desorbs the absorbed NOx under a stoichiometric burning condition, and reduces the NOx is disclosed in JP-A-5-261287 (1993). The catalyst is composed of barium oxides, lanthanum oxides, and platinum, all of which are supported by an alumina supporter. All the above described conventional catalysts for purifying exhaust gas from lean burn engines have such a problem that the catalysts lack a long durability, because all the catalysts contain zeolite. Under the lean burning condition, water is generated approximately 10% by volume by combining hydrocarbons and oxygen in the exhaust gas. Zeolite has such a property that the zeolite loses zeolite structure when it is heated under a condition existing water. Once the zeolite structure is broken, active components supported by the zeolite coagulates, and the catalytic activity decreases. The catalyst which is composed of barium oxides, lanthanum oxides, and platinum, all of which are supported by an alumina supporter has such a problem that the barium oxides which is contained by a high concentration are thermally deteriorated. SUMMARY OF THE INVENTION Accordingly, one of the objects of the present invention is to provide a method for treating exhaust gas to purify effectively the exhaust gas released from lean burning. Other one of the objects of the present invention is to provide a catalyst which can purify the exhaust gas released lean burning effectively, and has preferable durability. The method for treating exhaust gas relating to the present invention comprises the process of contacting the exhaust gas flow containing nitrogen oxides with the catalyst in the presence of at least one of hydrocarbons and carbon monoxide to reduce the nitrogen oxides to nitrogen. The catalyst comprises a structure wherein active components are supported by inorganic oxide supporters, the active components comprises at least one of noble metals selected from rhodium, platinum, and palladium, at least one of rare earth metals, at least one of alkali earth metals, and magnesium. Concentration of the noble metal is in a range of 0.05˜3.5 mol % to the inorganic oxides supporter 100 mol %, the rare earth metal is in a range of 0.7˜20 mol %, the alkali earth metal is in a range of 4˜16 mol %, rhodium is less than 1.9 mol %, platinum is less than 2.6 mol %, palladium is less than 2.8 mol %, the noble metal is contained in a form of metal or oxide, the rare earth metal is contained in a form of oxide, and the alkali earth metal is contained in a form of oxide or carbonic acid salt. As the active component for the catalyst of the present invention, the active component composed of rhodium, platinum, cerium, and magnesium is most preferable, and the catalytic activity is maximum. The catalyst of the present invention is preferably composed of in a manner that the inorganic oxide supporter supports the rare earth metal, the rare earth metal supports the noble metal, and the noble metal supports the alkali earth metal. The catalyst of the above described structure has a preferable dispersibility of noble metal components and a high catalytic activity. The noble metal components are composed of rhodium and platinum, and the rhodium is preferably supported on the platinum. In the catalyst of the present invention, the noble metal gives a reaction field for generating N 2 from nitrogen oxide and hydrocarbon. By containing alkali earth metal and/or rare earth metal, adsorption of nitrogen oxide at surface of the catalyst is enhanced. Further, the alkali earth metal and the rare earth metal have a strong bonding activity with oxygen, and accordingly, the metals can absorb oxygen in NOx and proceed the catalytic reaction to form N 2 even under a condition existing oxygen. Magnesium in the active components has an effect to enhance the reducing reaction of the nitrogen oxides by increasing crystallinity of the noble metal. The crystallinity of the noble metal can be enhanced by supporting magnesium after supporting the noble metal on the supporter. When the catalyst is a mixture of particles composed of an inorganic oxide supporter supporting the noble metal, cerium, and magnesium as the active components and particles composed of an inorganic oxide supporter supporting the noble metal, lanthanum, and barium as the active components, the catalyst has a significantly high catalytic activity under both stoichiometric and lean burning operating conditions. The particles composed of an inorganic oxide supporter supporting the noble metal, cerium, and magnesium have a superior performance for purifying the exhaust gas under both stoichiometric and lean burning conditions, and the particles composed of an inorganic oxide supporter supporting the noble metal, lanthanum, and barium have a property to absorb NOx under the lean burning condition. Therefore, the catalytic performance for purifying the exhaust gas can be enhanced by combining the above two kinds of particles, because NOx is absorbed under the lean burning condition and the NOx is released under the stoichiometric burning condition to be reduced to N 2 . As for the inorganic oxide supporter, porous oxides such as TiO 2 , SiO 2 , ZrO 2 , MgO, and the like can be used. Especially, at least one selected from composite oxide of lanthanum and β-alumina (La. β-Al 2 O 3 ) and β-alumina (β-Al 2 O 3 ) is preferably used. When treating exhaust gas by the catalyst relating to the present invention, it is preferable to make the catalyst contact alternately with a gas flow of low oxygen concentration wherein an oxygen concentration by volume is set in a range of 1.0˜1.7% and a gas flow of high oxygen concentration wherein the oxygen concentration by volume is set higher than that of the gas flow of low oxygen concentration. If the catalyst of the present invention is contacted with the gas flow of high oxygen concentration continuously, an oxide film is generated at surface of the catalyst and activity of the catalyst decreases gradually. Therefore, after contacting the catalyst with the gas flow of high oxygen concentration, subsequently the catalyst is contacted with the gas flow of low oxygen concentration in order to eliminate the oxide film generated at the surface of the catalyst by reacting with hydrocarbon or carbon monoxide. In accordance with the alternate contact with the gas flow of high oxygen concentration and the gas flow of low oxygen concentration, the activity of the catalyst can be maintained at a preferable level for a long time. The time for contacting the catalyst with the gas flow of high oxygen concentration or low oxygen concentration can be respectively from a few tens seconds to a several minutes. The catalyst of the present invention has preferable performance for purifying exhaust gas under both stoichiometric condition and lean burning condition. Concretely saying, the catalyst of the present invention can reduce nitrogen oxides in the exhaust gas released under the above both conditions to nitrogen effectively by using hydrocarbons and carbon monoxide as reducing agents. Therefore, both hydrocarbons and carbon monoxide can be treated simultaneously. In accordance with installing the catalyst of the present invention in an exhaust gas system of an internal combustion engine, release of nitrogen oxides to outside the automobile can be suppressed remarkably. Especially, if lean burning and stoichiometric burning are set to be performed alternately, the releasing amount of the nitrogen oxides can be suppressed small for a long time without changing the catalyst. The catalyst of the present invention is also effective for treating an exhaust gas from diesel engines of diesel automobile and others. The diesel engine is operated with a high air to fuel ratio, that is an oxygen excess condition. However, the catalyst of the present invention has a preferable activity in the presence of oxygen. Therefore, the catalyst of the present invention can remove nitrogen oxides effectively even from an exhaust gas released from a diesel engine. When cerium is contained in the catalyst of the present invention, the contained amount is preferably in a range from 0.7 mol % to 20 mol % per an inorganic supporter 100 mol %. When magnesium is contained in the catalyst of the present invention, the contained amount is preferably in a range from 4 mol % to 16 mol % per an inorganic supporter 100 mol %. The catalyst of the present invention can be used in various shapes such as powder, particles, pellets, honeycomb, and others. Furthermore, the catalyst can be used by supported with porous honeycomb such as cordierite honeycomb and metal honeycomb. The catalyst of the present invention can be prepared by various methods such as impregnation method, kneadering method, coprecipitation method, sol-gel method, and others. When the catalyst is prepared by the impregnation method, the method comprises preferably the steps of immersing an inorganic oxide supporter into a solution containing rare earth metal compounds, calcining the impregnated supporter, immersing the calcined supporter into a solution containing noble metal compounds, calcining the impregnated supporter, immersing the calcined supporter into a solution containing alkali earth metal compounds, and calcining. In accordance with the above steps, the catalyst can be prepared, wherein the rare earth metals are supported on the inorganic supporter, the noble metals are supported on the rare earth metal, and the alkali earth metals are supported on the noble metals. As for the metal compounds, various kinds of compounds such as nitrates, acetates, hydrochloride, sulfates, and carbonates can be used. The catalyst of the present invention has a superior activity in a temperature range from 100° C. to 800° C., especially has a preferable activity in a range of 200° C.˜500° C. Accordingly, the temperature whereat the catalyst is contacted with the gas flow, that is a reaction temperature, must be set in the above described temperature range. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic illustration indicating a composition of an automobile provided with the exhaust gas purifying apparatus relating to the present invention, FIG. 2 is a perspective view of an example of honeycomb supporting the catalyst of the present invention, FIG. 3 is a flow chart for controlling air to fuel ratio of an internal combustion engine provided with the catalyst of the present invention, FIG. 4 is graph indicating a result of releasing experiment of NO adsorbed on surface of the catalyst, FIGS. 5(a), 5(b), and 5(c) indicate results of evaluation on transient response characteristics of the catalyst relating to the present invention, and FIG. 6 is a graph indicating a relationship between oxygen concentration and NOx removal rate. DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 indicates an example of the exhaust gas purifying apparatus of the present invention installed in an automobile. Referring to FIG. 1, the catalyst 3 is installed at an exhaust gas flow path 2 in the downstream of the engine 1, and an oxygen concentration sensor 8 is provided at upstream of the catalyst 3. The catalyst had a honeycomb structure 5 indicated in FIG. 2, for example, and the catalyst portion 7 is supported at surface of a honeycomb portion 6. An output of the oxygen concentration sensor 8 is transmitted to a computer control portion 9, and operational air to fuel ratio of the engine 1 is controlled by an output of the computer control portion 9. Referring to FIG. 3, when the output of the oxygen concentration sensor is less than a preset oxygen concentration by volume (for instance, 1.2% by volume), operation of the engine 1 is performed with a low air to fuel ratio such as oxygen concentration by volume is less than 1.2% during a setting time of a timer T1, and when the output of the oxygen concentration sensor is equal to or larger than a preset oxygen concentration by volume (for instance, 1.2% by volume), operation of the engine 1 is performed with a high air to fuel ratio such as oxygen concentration by volume is equal to or larger than 1.2% during a setting time of a timer T2. Embodiment 1 The catalyst No. 1 of the present embodiment was prepared by a method comprising the following steps; impregnating a solution containing Ce nitrate aqueous solution into γ-Al 2 O 3 having a particle size in a range from 1 mm less than 2 mm, drying at about 100° C. for about 2 hours, calcining at about 600° C. for 2 hours, subsequently impregnating a solution containing magnesium nitrate aqueous solution into the calcined body, drying and calcining in a same manner as above, further orderly impregnating aqueous solutions of rhodium nitrate, and dinitrodiamine platinum nitrate, and drying and calcining in a same manner as above. The catalyst No. 1 of the present embodiment prepared by the above steps contained Rh 0.29 mol % (0.3% by weight), Pt 0.82 mol % (1.6% by weight), Mg 8 mol % (2% by weight), and Ce 16.4 mol % (23% by weight) per γ-Al 2 O 3 100 mol %, respectively. In accordance with the same method except replacing Mg with other alkali earth metals and replacing Ce with other rare earth metals, the catalysts No. 2-9 of the present embodiment were obtained. Compositions of the prepared catalysts are summarized in Table 1. TABLE 1______________________________________Active component (mol %)Catalyst Rarenumber Noble metals Alkali earth metals earth(No.) Rh Pt Mg Others metals______________________________________Cat. No. 1 0.29 0.82 8 Ce 16.4Cat. NO. 2 0.29 0.82 8 La 16.4Cat. No. 3 0.29 0.82 8 Ca 8 La 16.4Cat. NO. 4 0.29 0.82 8 Sr 8 La 16.4Cat. No. 5 0.29 0.82 8 Ba 8 Ce 16.4Cat. NO. 6 0.29 0.82 8 Ba 8 Nd 16.4Cat. No. 7 0.29 0.82 8 Ba 8 La 16.4Cat. NO. 8 0.29 0.82 8 Ba 8 Ce 16.4Cat. NO. 9 0.29 0.82 8 Ba 8 La 16.4______________________________________ Experiment 1 Experiments on nitrogen oxides removing performance of the catalysts No. 1-9 of the present embodiment were performed by the following method. Experimental Method (1) The catalyst 3 cm 3 was filled into a reaction tube made of pylex glass. (2) The reaction tube was inserted into an electric furnace, and heated to 550° C. with a temperature increasing rate of 10° C./min. When the temperature of the catalyst reached at 150° C., flow of stoichiometric model gas (called hereinafter stoichiometric model exhaust gas) was started. Nitrogen oxides (NOx) in the exhaust gas from the reaction tube was determined by chemiluminescence method at every 30 seconds. As for the stoichiometric model exhaust gas, a gas composed of NO 0.1% by volume, C 3 H 6 0.05% by volume, CO 0.6% by volume, O 2 0.6% by volume, steam 10% by volume, and the residual nitrogen was used. Space velocity of the gas was 60,000 h -1 . The determination of the temperature was performed by a thermocouple which was installed at the vicinity of the catalytic layer in the reaction tube. (3) When the temperature of the catalyst reached at 550° C., the flow of the stoichiometric model exhaust gas was stopped. (4) Heating by the electric furnace was stopped, and the catalyst was cooled to 300° C. (5) Subsequently, flow of lean burning model gas (called hereinafter lean model exhaust gas) was started. Nitrogen oxides (NOx) in the exhaust gas from the reaction tube was determined by chemiluminescence method at every 30 seconds. As for the lean model exhaust gas, a gas composed of NO 0.06% by volume, C 3 H 6 0.04% by volume, CO 0.1% by volume, CO 2 10% by volume, O 2 4% by volume, steam 10% by volume, and the residual nitrogen was used. Space velocity of the gas was 60,000 h -1 . (6) After flowing the lean model exhaust gas for 30 minutes, the flow of the gas was stopped and the experiment was completed. NOx removal rates after flowing the lean model exhaust gas for 30 minutes are indicated in Table 2. The NOx removal rate was calculated by the following equation; NOx removal rate=(NOx concentration in the gas at the inlet-NOx concentration in the gas at the outlet)/(NOx concentration in the gas at the inlet) TABLE 2______________________________________ NOx Removal rate (%)______________________________________Catalyst No. 1 40Catalyst No. 2 30Catalyst No. 3 37Catalyst No. 4 18Catalyst No. 5 35Catalyst No. 6 30Catalyst No. 7 15Catalyst No. 8 30Catalyst No. 9 20______________________________________ Experiment 2 Experiments on nitrogen oxides removing performance of the catalysts No. 1-9 of the present embodiment were performed by the following steps. (1) The same steps as the experiment 1 were performed until the flow of the stoichiometric model exhaust gas was stopped. (2) Heating by the electric furnace was stopped, and the catalyst was cooled to 150° C. (3) Flow of the lean model exhaust gas was started, and the heating by the electric furnace was re-started simultaneously. Nitrogen oxides (NOx) in the exhaust gas from the reaction tube was determined by chemiluminescence method when the catalyst temperature reached at 250° C., 300° C., and 400° C., respectively. As for the lean model exhaust gas, the same gas as used in the experiment 1 was used. Space velocity of the gas was 60,000 h -1 . The temperature increasing rate of the reaction tube by the electric furnace was 10° C./min. (4) When the temperature of the catalyst reached at 550° C., the flow of the gas was stopped and the experiment was completed. NOx removal rates at respective measuring temperature are indicated in Table 3. The NOx removal rate was calculated by the same equation as the experiment 1. TABLE 3______________________________________Reaction NOx removal rate (%)temperature (° C.) 250 300 400______________________________________Catalyst No. 1 63 57 20Catalyst No. 2 57 54 33Catalyst No. 3 63 63 32Catalyst No. 4 58 63 35Catalyst No. 5 65 67 25Catalyst No. 6 50 45 20Catalyst No. 7 55 45 28Catalyst No. 8 35 40 40Catalyst No. 9 45 45 40______________________________________ TABLE 4______________________________________ Nox removal rate (%) After heating treatment atTemperature (° C.) 700° C.______________________________________200 5250 70300 58400 18______________________________________ Experiment 3 In order to examine heat resistance of the catalyst of the present invention, the catalyst No. 1 of the present embodiment was heated at 700° C. for 50 hours in a calcining furnace. Subsequently, the catalyst was cooled to room temperature, and was taken out from the furnace. Then, the catalyst was filled into a reaction tube, and the lean model exhaust gas was flown as same as experiment 2. The observed NOx removal rates are shown in Table 4, and durability of the catalyst relating to the present invention was revealed to be preferable at high temperature. Experiment 4 Using the catalyst No. 7 of the present embodiment, an experiment on NO release at an elevated temperature was performed as follows; First, the catalyst 2 cm 3 was filled into a reaction tube, and the reaction tube was heated gradually to 600° C. in CO--He gas flow in order to reduce and eliminate oxygen which was absorbed on the catalyst. Because oxygen was absorbed on the surface of the catalyst which had just been prepared, it was necessary to reduce and eliminate the oxygen at the surface of the catalyst as a pre-treatment. After being kept at 600° C. in He gas flow for 20 minutes, the reaction tube was cooled to 50° C. in O 2 --He gas flow, and kept at 50° C. more than one hour for contacting the catalyst with oxygen. Subsequently, NO was absorbed saturately by flowing NO--He gas flow, then the catalyst was heated to 500° C. in He gas flow for desorbing the absorbed gas. During the desorption, components in the gas flow at outlet of the reaction tube was determined by a quadruple mass spectrometer, and a result shown in FIG. 4 was obtained. Referring to FIG. 4, release of NO is observed at temperature ranges of 100° C.˜250° C. and 370° C.˜470° C., but generation of N 2 is hardly observed. The result indicates that the reactivity of the catalyst with NOx is decreased by covering the surface of the catalyst with oxygen. Furthermore, transient response reaction characteristics was evaluated with the above catalyst. First, the catalyst sample 0.5 grams was filled into a reaction tube, and the reaction tube was heated to 600° C. in CO--He gas flow as same as the previous NO release experiment at an elevated temperature. The reaction tube was kept at 600° C. in He gas flow for 20 minutes, then cooled to 300° C. and maintained the temperature. (a) NO 70 ppm, (b) C 3 H 6 250 ppm, (c) NO 70 ppm were introduced into He gas flow in a pulsing manner, components in the gas flow at outlet of the reaction tube was determined by a quadruple mass spectrometer, and a result shown in FIGS. 5(a), 5(b), and 5(c) was obtained. The result can be summarized as follows; (a) Only N 2 was observed until the 27th NO pulse, and no oxygen (O 2 ) was generated. After the 28th NO pulse, NO was observed. Therefore, it is revealed that reducing the NO to N 2 is started at this point at the surface of the catalyst which is not covered with oxygen, and NO removing performance of the catalyst decreases in accordance with a degree of oxygen accumulation at the surface of the catalyst. (b) In accordance with introducing C 3 H 6 into He gas flow in a pulsing manner, Co was observed. After 4th introduction, C 3 H 6 was observed. The observed result indicates that the surface oxygen reacts with hydrocarbon and active points of the catalyst is recovered. (c) Only generation of N 2 was observed in accordance with introduction of No in a pulsing manner. The result indicates that a reducing reaction of NO to N 2 occurs at the surface of the catalyst, and N 2 is generated. In accordance with the above experimental results, it is revealed that elimination of oxygen from the surface of the catalyst is important for removing NOx. Comparative Example 1 Comparative example catalyst No. 1 containing Rh 0.29 mol % (0.3% by weight), Pt 0.82 mol % (1.6% by weight), and Ce 16.4 mol % per γ-Al 2 O 3 100 mol % was prepared by the same method as the embodiment 1. Nitrogen oxides removing performance of the comparative example catalyst No. 1 was performed by the same method as the experiment 2 in the embodiment 1. The obtained result is indicated in Table 5. Embodiment 2 Embodiment catalyst No. 10 was prepared by the same method as the embodiment 1. Composition of the catalyst was Pd 1.5 mol % (1.6% by weight), Rh 0.29 mol % (0.3% by weight), Mg 8 mol % (2% by weight), and Ce 16.4 mol % (23% by weight). Performance of the catalyst was evaluated by the same method as the experiment 2 in the embodiment 1. The obtained result is indicated in Table 6. Embodiment 3 The catalyst No. 11 of the present embodiment was prepared by a method comprising the following steps; impregnating a solution containing Ce nitrate aqueous solution into γ-Al 2 O 3 having a particle size in a range from 1 mm less than 2 mm, drying at about 100° C. for about 2 hours, calcining at about 600° C. for 2 hours, orderly impregnating aqueous solutions of rhodium nitrate, and dinitrodiamine platinum nitrate, and drying and calcining in a same manner as above. Further, impregnating a solution containing magnesium nitrate aqueous solution, drying at about 100° C. for about 2 hours, and calcining at about 600° C. for 2 hours. That is, Mg was supported at the outermost layer of the components. The catalyst No. 11 of the present embodiment prepared by the above steps contained Rh 0.29 mol % (0.3% by weight), Pt 0.82 mol % (1.6% by weight), Mg 4 mol % (1% by weight), and Ce 8.6 mol % (12% by weight) per γ-Al 2 O 3 100 mol %, respectively. In accordance with the same method as above, comparative example catalyst No. 2 supporting Mg after Ce contained Mg 4 mol % and Ce 8.6 mol % (No Rh nor Pt contained) was prepared. Performance of the above catalysts were evaluated by the same method as the experiment 2 of the embodiment 1. The obtained results on NOx removal rate are indicated in Table 7. The embodiment catalyst No. 11 wherein Mg is supported after noble metal supporting has a higher NOx removal rate than the embodiment catalyst NO. 1. TABLE 5______________________________________Reactiontemperature NOx Removal rate (%)(° C.) 250 300 400______________________________________Comparative 45 45 15examplecatalyst No. 1______________________________________ TABLE 6______________________________________Temperature (° C.) NOx removal rate (%)______________________________________200 30250 35300 24400 15500 5______________________________________ TABLE 7______________________________________ NOx removal rate (%) Comparative Embodiment example catalystTemperature (° C.) catalyst No. 11 No. 2______________________________________200 75 0250 65 0300 53 15400 15 30______________________________________ Embodiment 4 Embodiment catalyst No. 12 was obtained by wash-coating of the embodiment catalyst No. 1 (100 grams per liter) onto cordierite honeycomb (400 cells/in 2 ), and calcining the coated cordierite honeycomb at 600° C. for 2 hours. NOx removal rate of the embodiment catalyst No. 12 having an area of 6 cm 2 (17 mm×21 mm) was determined by inserting the catalyst into a pylex reaction tube of 28 mm inner diameter, and flowing stoichiometric model exhaust gas and lean burning model exhaust gas alternately by the same method as the experiment 1. The space velocity SV of the lean burning model exhaust gas was 30,000 h -1 . A gap between an outer wall of the honeycomb and the reaction tube was closed by packing quartz wool. A thermocouple was provided at upper portion by 1 cm from the upper surface of the honeycomb for measuring temperature. In the present experiments, oxygen concentration in the lean burning model exhaust gas was changed respectively as 0, 0.5, 1.0, 1.2, 1.5, 1.7, 5.0% by volume. FIG. 6 indicates NOx removal rates after flowing the lean burning model exhaust gas for 30 minutes. The NOx removal rate was calculated by the same equation as the embodiment 1. The NOx removal rate when the oxygen concentration was in a range of 1.0˜1.4% by volume was approximately 100%. Embodiment 5 Embodiment catalyst NO. 13 was obtained by coating 300 grams of the embodiment catalyst No. 1 onto cordierite honeycomb of volume 1.7 liters. The honeycomb catalyst was installed under a floor of automobile having an engine of 3000 cm 3 displacement, and NOx removal rate was determined under driving the automobile by 10-15 modes. The NOx removal rate under stoichiometric operation (air/fuel ratio=14.7) was approximately 100%, and the NOx removal rate under lean burning operation (air/fuel ratio=21) was approximately 50%. Subsequently, the embodiment catalyst NO. 13 was inserted into a reaction tube, and heated to 300° C. The NOx removal rate was determined under a condition maintaining the reaction tube at 300° C. and flowing the stoichiometric model exhaust gas and the lean burning model exhaust gas alternately by 3 minutes for one hour totally. Respective of the stoichiometric model exhaust gas and the lean burning model exhaust gas had the same composition as the gases used in the experiment 1. The NOx removal rate under stoichiometric condition was always approximately 100%, and the NOx removal rate under lean burning condition was in a range of 50˜100%. The NOx removal rate soon after alteration from the stoichiometric gas to the lean burning gas was approximately 100%, but the rate decreased to approximately 50% after continuing the lean burning condition for 3 minutes. During the experiment for one hour, the NOx removal rate repeated the above explained change, and no extreme decrease of the NOx removal rate under the stoichiometric condition was observed. Embodiment 6 Embodiment catalyst No. 14 was prepared in accordance with the same method as the embodiment 1, except using a composite oxide (La. β-Al 2 O 3 ) supporter made of β-Al 2 O 3 and Lanthanum in place of γ-Al 2 O 3 supporter. The NOx removal rates were calculated based on NOx which were determined in accordance with the same method as the experiment 2, such as flowing the stoichiometric model exhaust gas and the lean burning model exhaust gas alternately, and measuring the amount of NOx in the gas stream when the lean burning model exhaust gas was flowing and the temperature indicated by the thermocouple reached at respectively 200° C., 250° C., 300° C., 400° C., and 500° C. The same experiment as above was also performed on the catalyst which was obtained by thermal treatment of the embodiment catalyst No. 14 at 700° C. for 50 hours in a calcining furnace. Composition of the embodiment catalyst No. 14 was Rh 0.29 mol % (0.3% by weight), Pt 0.82 mol % (1.6% by weight), Mg 8 mol % (2% by weight), and Ce 16.4 mol % (23% by weight). Table 8 indicates the NOx removal rate of the catalyst No. 14. Embodiment 7 A mixture of γ-Al 2 O 3 of 1 μm in diameter and cerium nitrate was prepared by the steps of wet-kneadering, drying at approximately 100° C. for approximately 2 hours, and calcining at approximately 600° C. for 1 hour. Subsequently, respective aqueous solutions of rhodium nitrate and dinitrodiamine platinum were added to the mixture orderly, and kneadering, drying, and calcining were performed as same as the above procedure. Finally, magnesium nitrate was added to the mixture by wet-kneadering, drying at approximately 100° C. for approximately 2 hours, and calcining at approximately 600° C. for 1 hour. In accordance with the above steps, embodiment catalyst NO. 15 was obtained. Composition of the embodiment catalyst No. 15 was Rh 0.29 mol % (0.3% by weight), Pt 0.82 mol % (1.6% by weight), Mg 4 mol % (1% by weight), and Ce 8.6 mol % (12% by weight) per γ-Al 2 O 3 100 mol %. In accordance with the same method as the embodiment catalyst NO. 15, comparative example catalyst No. 3, wherein γ-Al 2 O 3 of 1 μm in diameter supported Lanthanum, barium, and platinum orderly, was obtained. Composition of the comparative example catalyst No. 3 was La 0.17 mol %, Ba 0.08 mol %, and Pt 1.6 mol %. Furthermore, embodiment catalyst NO. 16 was prepared by the steps of dry-mixing the embodiment catalyst No. 15 and the comparative example catalyst No. 3 in a ratio of 1:1 by weight, fabricating by pressing machine, granulating to particles of 1˜2 mm in diameter, and calcining at approximately 600° C. for 1 hour. Using the three kinds of catalysts obtained by the above described procedure, the amounts of NOx were determined by the same method as the experiment 2, and the NOx removal rates were calculated. The obtained results are shown in Table 9. Embodiment 8 Using the embodiment catalyst No. 11, various catalyst were prepared, wherein content of Ce, Mg, Pt, and Rh were altered respectively to ranges of Ce 0˜25 mol %, Mg 0˜16 mol %, Pt 0˜1.54 mol %, and Rh 0˜0.48 mol %. Then, NOx removal rates were determined by the same method as the experiment 1. The results are shown in Table 10. TABLE 8______________________________________ NOx removal rate (%) Embodiment After heatTemperature (° C.) catalyst No. 14 treatment at 700° C.______________________________________200 45 44250 50 50300 45 40400 20 17500 10 10______________________________________ TABLE 9______________________________________NOx removal rate (%)200° C. 250° C. 300° C. 350° C. 400° C.______________________________________Embod. 40 55 45 35 15catalystNo. 15Compara. 35 40 40 45 40catalystNo. 3Embod. 50 65 83 70 25catalystNo. 16______________________________________ Remarks: Embod.; Embodiment, Compara.; Comparative example TABLE 10______________________________________Rh Pt Mg Ce (mol %)(mol %) (mol %) (mol %) 0 8 17 25______________________________________0 0 0 3 5 7 6 4 5 10 12 10 8 5 12 13 12 16 5 13 13 120.097 0.26 0 15 25 28 20 4 16 31 35 28 8 18 32 36 30 16 15 28 30 250.29 0.82 0 20 36 38 31 4 25 42 38 30 8 25 37 42 30 16 18 31 33 300.48 1.54 0 10 15 18 15 4 15 25 25 20 8 18 24 26 18 16 10 20 22 15______________________________________
Exhaust gas from internal combustion engines is treated with catalyst comprising an inorganic oxide supporter which supports at least one of noble metals selected from Rh, Pt, and Pd, alkali rare earth metals, rare earth metals, and magnesium in order to remove NOx effectively with superior durability of the catalyst notwithstanding the internal combustion engine is under a stoichiometric operation condition or a lean burning operation condition.
1
FIELD OF THE INVENTION [0001] The present invention relates to a master-cylinder primary piston for an automobile and to vehicle master cylinders equipped with such a piston. BACKGROUND INFORMATION [0002] Master cylinders known to the state of the art have a primary piston and a secondary piston generally made of aluminum, both of which are installed in series in an axial bore hole of a brake master-cylinder body, generally made of aluminum and machined. Such a master cylinder is described in French Patent No. 2,827,244. A push rod is used to actuate the displacement of the primary piston. The primary piston serves to pressurize a primary pressure chamber and a secondary piston serves to pressurize a secondary pressure chamber. Primary and secondary springs tend to push the pistons in the direction opposite displacement, thereby ensuring the increase in pressure. [0003] The bore hole of the master cylinder is supplied with brake fluid from two supply access holes that are connected to a brake fluid reservoir. The supply access holes are used to supply the primary and secondary pressure chambers. These holes emerge in annular chambers, annular seals known as “cups” being provided on either side of the annular chambers. [0004] The supply of brake fluid to the pressure chambers occurs when the pistons are at rest. The pistons are then in the position shown in FIG. 1 . Supply occurs by passages provided in the piston walls, which enable the supply access holes and the annular chambers to communicate with the interior of the primary and secondary pistons emerging respectively in the primary and secondary pressure chambers. When the pistons are moved axially forward (direction of arrow D in FIG. 1 ), the piston passages cross the seals, isolating the supply chambers and enabling brake pressure to be established in the primary and secondary pressure chambers. [0005] The master cylinder assembly is capable of being installed on a brake-assist servomotor. When the pistons are displaced along the direction of arrow D by a push rod that exercises a selective force on the primary piston, cup 4 isolates the primary pressure chamber of the primary supply access hole and cup 6 isolates the secondary pressure chamber of the supply access hole. When the force on the push rod is released, the volume of brake fluid accumulated in the brakes and springs of the master cylinder pushes the pistons into rest position. At times, when the push rod is rapidly released, the brake fluid contained in the pressure chambers of the master cylinder can drop below atmospheric pressure due to the action of the springs, which push the pistons more rapidly than the ability of brake fluid to flow through the master cylinder. When the pistons reach rest position, communication between the reservoir at atmospheric pressure and the chambers of the master cylinder is directly established and a sudden surge of brake fluid occurs, which generates noise in the master cylinder, known as a “fluid hammer.” To improve the performance of master cylinders, it is necessary to provide aluminum master-cylinder pistons with specific shapes, which shapes can result in significant additional costs due to the complexity of their production. SUMMARY [0006] An object of the present invention is to provide a plastic primary piston for a master cylinder that is easy to produce, economical, and capable of resisting mechanical stress. [0007] An object of the present invention is a master-cylinder piston installed in a brake master cylinder of the type described above, comprising at least the primary piston and a secondary piston installed in a bore hole of the master cylinder. These pistons allow a pressure to be created in a primary pressure chamber and a secondary pressure chamber, respectively, by the action of a push rod on the primary piston, characterized in that the primary piston is of molded plastic material and equipped with a metal insert situated in a receiving cavity of the push rod, where the push rod exercises a force to displace the primary piston and wherein the insert has a specific shape capable of accommodating, on the one hand, the push rod and, on the other hand, an exterior shape enabling it to be maintained in the receiving cavity of the push rod and wherein the piston is preferably made of a thermoset plastic and, more preferably, of phenolic resin filled with glass fibers. The specific shape and hardness of the insert is capable of accommodating the push rod and of resisting deformation of the push rod due to the application of the brakes. The metal insert provides the primary piston with increased mechanical resistance and helps to reduce the thicknesses of plastic materials and make the primary piston more compact. [0008] Another beneficial characteristic is that the body of the primary piston is easily made by injection molding, which allows complex shapes to be produced, such as: grooves, ribs, non-cylindrical holes. [0009] According to another beneficial characteristic, the body of the piston is easily made by injection molding and the primary piston leaving the mold is ready for assembly without requiring any finishing work, unlike the aluminum piston, which requires additional machining. [0010] According to another beneficial characteristic, the body of the piston is easily made by molding thermoset plastic materials, which allow the surface to be ground by machining to improve the reliability of the master cylinder. [0011] According to another beneficial characteristic, the body of the piston is easily made by injection molding plastic materials, which allow noises caused by the brake fluid to be damped. [0012] According to another beneficial characteristic, the insert is made of magnetizable material so that the piston emits a magnetic field capable of being detected by a magnetic-field sensor. [0013] According to another beneficial characteristic, the exterior shape of the metal insert has at least one protrusion whose exterior shape is of slightly greater dimension for forced insertion into the bottom of the receiving cavity of the push rod. [0014] The thickness of the insert is designed to resist a master-cylinder test pressure of 40 MPa, this thickness taking into account the diameter of the primary piston and the bearing section of the push rod. BRIEF DESCRIPTION OF THE DRAWINGS [0015] FIG. 1 is an axial cutaway of a master cylinder known to the state of the art and previously described, [0016] FIG. 2 is an isometric view with a partial cutaway of an embodiment of a master-cylinder piston according to the invention, with grooves on the front of the piston, [0017] FIG. 3 is a partial axial view of an embodiment of a portion of a master cylinder according to the invention. DETAILED DESCRIPTION [0018] In FIG. 1 , therefore, we find brake master cylinder 100 having bore hole 11 in which primary piston 2 and secondary piston 3 and primary spring 7 and secondary spring 8 have been placed. Pistons 2 and 3 serve to pressurize, respectively, primary pressure chamber 9 and secondary pressure chamber 10 from brake fluid supply access holes 12 and 13 , which are intended to be connected to a brake fluid reservoir (not shown). On either side of access hole 12 , cups 3 and 4 are provided and, on either side of access hole 13 , cups 5 and 6 are provided. Whenever the master cylinder is at rest, the primary piston is in the position shown in FIG. 1 . The exterior piston walls are equipped with passages 14 and 15 and enable holes 12 and 13 to communicate with the interior of the piston and primary pressure chamber 9 and secondary pressure chamber 8 . When at rest, cups 4 and 6 allow communication between access holes 12 and 13 , primary and secondary pressure chambers 9 and 8 then being supplied with brake fluid. [0019] Whenever, under the effect of a braking force exercised in direction D by push rod 16 placed in cavity 17 of primary piston 2 , primary piston 2 is moved in the direction of arrow D, cup 6 blocks passages 15 and cup 4 blocks passages 14 . Because primary and secondary pressure chambers are thereby isolated from holes 12 and 13 , a pressure is established in chambers 9 and 10 , this pressure being proportional to the force exercised in direction D by push rod 16 placed in cavity 17 of primary piston 2 . The external diameter S of primary piston 2 forms a section on which the pressure of the primary chamber acts. In cavity 17 of the primary piston, push rod 16 applies a force to generate a pressure in the master cylinder but on a diameter that is appreciably smaller, at a minimum 4 times smaller. This creates significant stress at the primary piston and requires a minimum thickness of material E between the receiving cavity of push rod 27 and forward cavity 19 , where a primary spring pack is found, including of two spring ends 71 , 72 , rod 73 , and the primary spring. [0020] FIGS. 2 and 3 show a master-cylinder primary piston according to the invention, characterized in that primary piston 20 is of molded plastic material and equipped with a metallic insert 22 situated behind forward cavity 25 of the primary piston and in a receiving cavity of push rod 27 , where the push rod exerts a force to move the primary piston and generate pressure in the master cylinder, and wherein piston 20 has at least one groove 24 and the insert has the shape of a spherical cap capable of accommodating the push rod and an external shape capable of maintaining it in the receiving cavity of push rod 27 . The hardness of insert 22 is capable, on the one hand, of accommodating the push rod and, on the other, of resisting deformation of the push rod due to the application of the brakes. [0021] Grooves 24 are of sufficient length so that, when the master cylinder is at rest, the grooves allow brake fluid to pass beneath seal point 42 of cup 41 and emerge in annular chamber 44 situated between cups 31 and 41 . These grooves 24 form passages between the pressure chamber and the annular chamber connected to the reservoir, not shown, by hole 32 . It would have been possible to realize grooves 24 of aluminum but this would have resulted in significant additional costs. The use of plastic materials helps to reduce costs because the shapes of the grooves can be incorporated into the mold. The use of those same plastic materials requires that thicknesses be increased and additional material be used to overcome the difference in the mechanical resistance of the materials. The plastic body and metallic insert confer upon the primary piston an increased mechanical resistance and allow the thickness E of the plastic materials to be reduced and piston 20 to be more compact and, therefore, the invention, through the placement of the insert between forward cavity 25 and the receiving cavity of push rod 27 , provides the benefits of the mechanical resistance of aluminum and the ease of manufacture of complex shapes such as grooves through the use of plastic materials that can be molded. Moreover, the compactness of the primary piston also allows the master cylinder to be more compact and results in savings on master-cylinder materials. [0022] Another advantageous characteristic is that body 21 of piston 20 is easily made by injection molding, which allows for the realization of complex shapes such as grooves 24 . [0023] According to another advantageous characteristic, the body of the piston is easily made by molding thermoset plastic materials, which allow surface 28 to be ground by machining to improve the reliability of the master cylinder. [0024] According to another characteristic, the exterior surface 30 of metal insert 22 has at least one protrusion whose dimension is slightly greater than its exterior shape for forced insertion into the bottom of the receiving cavity of the push rod and which cooperates with the interior surface 29 of cavity 27 . [0025] According to another characteristic, the exterior surface 30 of metal insert 22 has irregular anchors that cooperate with interior surface 29 of cavity 27 . [0026] According to another advantageous characteristic, insert 22 is cylindrical and its exterior surface 30 has at least one rib cooperating with interior surface 29 of cavity 27 . [0027] According to another advantageous characteristic, the master cylinder has a primary piston 20 and an insert 22 made of magnetizable material so that the piston emits a magnetic field capable of being detected by a magnetic-field sensor.
A primary piston is described of molded plastic and equipped with a functional metallic insert and at least one groove. The primary piston is installed in a master cylinder comprising at least the primary piston and a secondary piston, these being mounted in the bore hole of a master cylinder. These pistons can create pressure in a primary pressure chamber and a secondary pressure chamber, respectively, due to the action of a push rod on the primary piston.
1
BACKGROUND OF THE INVENTION [0001] This invention relates to the field of sampling air from the lungs and specifically to the field of obtaining a sample of a person's air, including alveolar air from the alveoli of the lungs of a person. [0002] Air from the lungs of a person can be used for many different types of testing that would otherwise require the person to undergo an invasive procedure. For example, alveolar air can be analyzed for, but not limited to, the noninvasive diagnosis of a wide variety of conditions including the noninvasive diagnosis of stomach infections related to a high incidence of ulcers, enzymatic deficiencies, and metabolic conditions and/or abnormalities. Crucial to any such testing is the ability to get an accurate sample containing a sufficient volume of air representative of true alveolar air, necessary for specific testing. [0003] Hydrogen and methane are produced in the digestive system primarily only by the bacterial fermentation of carbohydrates (sugars, starches or vegetable fibers), so either of these gases appear in the expired air, it is usually a signal that carbohydrates or carbohydrate fragments have been exposed to bacteria, permitting such fermentation to take place. Levitt, M. D. Production and excretion of hydrogen gas in man. New Engl. J. Med 1968; 281:122 (incorporated herein by reference). The generation of H2 and/or CH4 will result in the reabsorption of some of these gases into the blood stream from the site of their digestion, and they will appear in the expired air. [0004] Bacteria are ordinarily not present in significant numbers in the small intestine, where digestion and absorption of sugars take place. Therefore, when a challenge dose (eg. lactose) is ingested, the level of hydrogen in alveolar air will rise significantly within one to two hours (depending on the intestinal transit time) only if the sugar is not digested and, therefore reaches the colon. [0005] The breath-H2 test is a simple non-invasive procedure which is readily accepted by patients and staff (Metz, G.; Jenkins, D. L.; Peters, T. J,; Newman, A.; Blendis, L. M. Breath hydrogen as a diagnostic method for hypolactasia. Lancet. 1975; 1 (7917) : 1155-7, incorporated herein by reference), and which has greater reliability and acceptability than the blood test, according to most reports in the literature (DiPalma, J. A.; Narvaez, R. M. Prediction of lactose malabsorption in referral patients. Dig Dis Sci. 1988; 33:303, incorporated herein by reference, and Davidson, G. P.; Robb, T. A.. Value of breath hydrogen analysis in management of diarrheal illness in childhood: Comparison with duodenal biopsy. J Ped Gastroenterol Nutr. 1985; 4:381-7; Fernandes, J.; Vos, C. E.; Douwes, A, C,; Slotema, E.; Degenhart, H. J. Respiratory hydrogen excretion as a parameter for lactose malabsorption in children. Amer J Clin Nutr. 1978; 31:597-602; Newcomer, A. D.; McGill, D. B.; Thomas, R. J.; Hofmann, A. F. Prospective comparison of indirect methods for detecting lactase deficiency. New Engl J Med. 1975; 293:1232-6; Douwes, A. C.; Fernandes, J.; Degenhart H. J. Improved accuracy of lactose tolerance test in children, using expired H2 measurement. Arch Dis Child. 1978; 53:939-42; Solomons, N. W.; Garcia-Ibanez, R.; Viteri, F. E. Hydrogen breath test of lactose absorption in adults: The application of physiological doses and whole cow's milk sources. Amer J Clin Nutr. 1980; 33:545-54; each incorporated by reference). [0006] The lower dose of lactose usually does not cause the discomfort and explosive diarrhea frequently seen by malabsorbers who are given the large dose required for the blood test. [0007] A study with over 300 patients showed that G-I symptoms after a lactose challenge are strongly associated with the amount of H2 excreted, and the relationship between blood glucose change and symptom-severity was less evident. Jones, D. V.; Latham, M. C.; Kosikowski, F. V.; Woodward, G. Symptom response to lactosereduced milk in lactose-intolerant adults. Amer J Clin Nutr. 1976; 29(6):633-8, incorporated by reference. [0008] False-positive breath-tests are rare, and when they occur they are usually caused by improperly doing the test—allowing the subject to smoke, to sleep or to eat shortly before or during the test11. Bacterial overgrowth (from the colon retrograde into the small intestine) can also produce a false-positive breath-test, but it is usually preceded by an elevated fasting breath-H2 level and the response is seen soon after the sugar is ingested (within 20-30 minutes). [0009] The incidence of false-negative results with the breath-test is well below that seen with the blood test. False-negative results are reported to be from 5-15% of all lactose malabsorbers. Filali, A.; Ben Hassine, L.; Dhouib, H.; Matri, S.; Ben Ammar, A.; Garoui, H. Study of malabsorption of lactose by the hydrogen breath test in a population of 70 Tunisian adults. Gastroenterol Clin Biol. 1987; 11:554-7; Douwes, A. C.; Schaap, C.; van der Kleivan Moorsel, J. M. Hydrogen breath test in school children. Arch Dis Child. 1985; 60:333-7; Rogerro, P.; Offredi, M. L.; Mosca, F.; Perazzani, M.; Mangiaterra, V.; Ghislanzoni, P.; Marenghi, L.; Careddu, P. Lactose absorption and malabsorption in healthy Italian children: Do the quantity of malabsorbed sugar and the small bowel transit time play roles in symptom production? J Pediatr Gastroenterol Nutr. 1985 (February); 4(1):82-614; each incorporated by reference. This is due to a variety of causes. Many of the false-negative reports can be avoided by measuring methane in addition to hydrogen because some methanogenic flora convert colonic H2 to CH4. Cloarac, D.; Bornet, F.; Gouilloud, S.; Barry, J. Ll.; Salim, B.; Galmiche, J. P. Breath hydrogen response to lactulose in healthy subjects: relationship to methane producing status. Gut. 1990 (March); 31:300-4; incorporated by reference. SUMMARY OF THE INVENTION [0010] In accordance with the present invention, a testing apparatus is provided. A breath collection apparatus comprising a breath entryway or mouthpiece is coupled to a first one-way coupling, which is preferably, but not necessarily, a flutter valve. Breath is expelled into the mouthpiece and through the one-way coupling. A collection chamber is coupled to said breath entryway by said first one-way coupling, and a second one-way coupling, also which is preferably, but not necessarily, a flutter valve coupled to said collection chamber to allow a first waste portion of exhaled breath to escape the collection chamber. When the breath is completed, both one-way couplings will close, trapping an end-expiration breath sample within the collection chamber. A sample transfer assembly coupled to said collection chamber allows for an evacuated air chamber to be selectively coupled to said sample transfer assembly, and the evacuated air chamber recovers a portion of the end-expiration breath sample within the collection chamber. In a preferred embodiment, a discharge chute is coupled to said collection chamber about said sample transfer assembly, said discharge chute comprising a proximal end for coupling to said collection chamber, and a distal end for receiving said evacuated air chamber. BRIEF DESCRIPTION OF THE DRAWINGS [0011] FIG. 1 is a perspective view of a sample collection apparatus of the present invention, with an evacuated air chamber inserted into a distal end of a discharge chute. [0012] FIG. 2 is an exploded perspective view of a sample collection apparatus of the present invention. [0013] FIG. 3 is an in-use side cross-sectional view of a sample collection apparatus, shown collecting a breath sample; [0014] FIG. 4 is a side cross-sectional view of a sample collection apparatus, with an evacuated air chamber being inserted into a distal end of the discharge chute; [0015] FIG. 5 is a side cross-sectional view of a sample collection apparatus, with an evacuated air chamber being inserted onto a discharge needle within the discharge chute; [0016] FIG. 6 shows a collected an end-expiration breath sample. DESCRIPTION OF THE PREFERRED EMBODIMENT [0017] Although the disclosure hereof is detailed and exact to enable those skilled in the art to practice the invention, the physical embodiments herein disclosed merely exemplify the invention which may be embodied in other specific structures. While the preferred embodiment has been described, the details may be changed without departing from the invention. [0018] Referring now to FIG. 1 a perspective view of a sample collection apparatus 10 of the present invention is shown. A mouthpiece 12 comprising a breath entryway is shown, to allow breath to pass to collection chamber 14 . A breath discharge chute 16 receives an evacuated air chamber 100 that receives an end-expiration breath sample (described later) from within the collection chamber 14 . [0019] Referring now to FIG. 2 , an exploded perspective view of a sample collection apparatus 10 of the present invention is shown. Mouthpiece 12 is either integrally formed or coupled with a one-way discharge assembly 26 . Positive pressure from a breath, through the mouthpiece 12 , causes flexible ring 24 to flex, and allow air to pass into collection chamber 14 at an upstream end of collection chamber 14 . Flexible ring 24 , is preferably, but not necessarily, a flutter valve. Another one-way discharge structure 24 , again coupled to a flexible ring 24 (and again preferably, but not necessarily, a flutter valve), is coupled to a downstream end of collection chamber 14 . Coupled to the interior of collection chamber 14 is discharge needle 22 , which provides a selective passageway from breath between collection chamber 14 and ultimately evacuated air chamber 100 , which is coupled to discharge needle 22 through discharge chute 16 . [0020] Referring now to FIG. 3 , an in-use side cross-sectional view of sample collection apparatus 10 is shown. A patient has pressed a mouth to mouthpiece 12 and began exhalation. The first volume of breath 42 evacuates background air from within collection 14 , and first volume of breath 42 , being not the most desirable for alveolar air sampling, is expelled through discharge chute 16 without capture. Positive pressure from the breath sample flexes flexible rings 24 , allowing air to continue to flow through collection chamber 14 , into discharge chute 16 . [0021] As the breath stops, the positive pressure from the breathing stops as well, allowing flexible rings 24 to return to their static position, flush against one-way discharge structures 26 at the upstream and downstream ends of collection chamber 14 . As the flexible rings 24 seal the collection chamber 14 , end-expiration breath sample 40 is captured in collection chamber 14 . To retrieve the end-expiration breath sample 40 for convenient sampling by gas chromatography equipment, it is desirable to collect end-expiration breath sample 40 in an evacuated air chamber 100 (a test tube) . Evacuated air chamber 100 is of a volume V 1 , which is preferably a smaller volume than volume V 2 of the collection chamber 14 , so that evacuated air chamber 100 collects only end-expiration breath sample 40 from the collection chamber 14 , and not outside air drawn through collection chamber 14 . [0022] Evacuated air chamber 100 is inserted into a distal end of the discharge chute 16 as shown in FIG. 4 , and as shown in FIG. 5 , evacuated air chamber 100 is inserted onto discharge needle 22 , piercing a septum 20 (preferably self-sealing) of air chamber 100 . The evacuated air chamber 100 then retrieves end-expiration breath sample 40 from collection chamber 14 . After air chamber 100 has retrieved end-expiration breath sample 40 from collection chamber 14 , the air chamber 100 can be withdrawn from the discharge needle 22 within discharge chute 16 . The air chamber 100 containing end-expiration breath sample 40 can then be processed in a laboratory for target analytes as desired. [0023] The foregoing is considered as illustrative only of the principles of the invention. Furthermore, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described. While the preferred embodiment has been described, the details may be changed without departing from the invention.
A breath testing apparatus is provided with a mouthpiece, a collection chamber, and a discharge chute. A breath sample is captured within the collection chamber and transferred to an evacuated container through the discharge chute by a sample transfer assembly.
0
BACKGROUND OF THE INVENTION Field of the Invention [0001] The present invention relates generally to supports for plants. More specifically, the invention relates to a plant cage formed from a fiber reinforced composite material and having locking clips interconnecting a plurality of horizontal supports to vertical posts. Background & Description of the Related Art [0002] Various types of devices are commonly used in gardening to provide support surfaces for the branches and stems of growing plants and to contain plants to a particular area. For example, trellises are often used to support decorative vine plants, such as ivy, while plant cages are commonly used in vegetable gardens to provide support to plant branches bearing heavy fruit or vegetables. [0003] Tomato cages are ubiquitous in residential vegetable gardens, with cages of varying materials, shapes, and sizes available depending on the type of plant and size of garden. Two common types of tomato cages include a round cage comprising two or more concentric, horizontally-oriented rings connected to three or more support rods, and a rectangular cage comprising two or more horizontally-oriented rectangular supports connected to four or more generally vertical support rods. Variations on the configurations of the tomato cages abound, with some round cages having rings of increasing diameter attached to obliquely oriented support rods, while some rectangular cages include diagonal struts that provide reinforcement to the rectangular supports. [0004] The components of many common tomato cages are made of steel, with the supports welded or soldered to the support rods. Such construction is prone to failure as the steel is quickly subject to corrosion and rust as the cage is constantly exposed to the elements. It is common for such cages to fail at the weld points after less than one season of use. Tomato cages formed from plastic material, such as polyvinyl chloride (PVC) are also widely used, with horizontal supports clipped to vertical rods to form triangular, rectangular, or cages of other shapes. [0005] While plastic or PVC cages avoid the rust and deterioration problems common to steel cages, they have their own shortcomings. For example, the clips used to attach the horizontal supports to the vertical rods are typically “C” shaped clips formed by two oppositely curved fingers extending from the end of the horizontal support. With a horizontally oriented “C” clip positioned at each end of the horizontal support, the clips snap around the circumference of a corresponding vertical rod to secure the horizontal support in place. The integrity of the snap connection, however, relies entirely on the spring tension of the extending curved fingers and the frictional resistance between the clip and the vertical rod. Thus, the clip can be moved with relative ease along the vertical rod. That ease of movement often results in unwanted movement of the horizontal support when, for example under the load of a weighted branch of a plant. Furthermore, because the clips at each end of the horizontal support are similarly oriented, when one clip moves it tends to move the entire support, pulling the clip at the opposite end along. [0006] Thus, it can be seen that there is a need in the art for a plant cage that does not easily deteriorate upon exposure to the elements, yet provides secure connection between horizontal supports and vertical rods so that the cage retains its shape and configuration under load. SUMMARY OF THE INVENTION [0007] The present invention is directed to a plant cage manufactured from a fiber reinforced composite, and having horizontal and vertical supports joined by locking clips with each locking clip having two clamps in orthogonal orientation to each other. [0008] In various exemplary embodiments, the plant cage includes a plurality of horizontal supports and a plurality of vertical rods, with each end of a horizontal support attached to a proximate vertical rod via the locking clip to form a cage of a desired size and shape. [0009] The clamps at each end of the locking clip body each comprise two tabs extending outwardly at oblique angles, forming a generally “V” shaped projection, with each tab having an aperture formed there through. The outwardly extending tabs are resilient and flexible such that the tabs can be moved towards each other, for example by a user grasping the two tabs simultaneously between a thumb and finger and pinching the two together, so that the tabs move towards each other. When released, the resiliency of the material causes the tabs to spring back to their original positions at oblique angles to each other. [0010] With the tabs positioned in close proximity (i.e., pinched together) the apertures in the two tabs align concentrically and in generally parallel planes such that a horizontal support tube or vertical rod can be inserted into and through the aligned apertures with the inserted tube or rod generally perpendicular to the planar orientation of the apertures. [0011] When the tabs are released with a tube or rod inserted, the tabs spring back towards their original positions, away from and at oblique angles to each other, such that the apertures are not aligned and parallel to each other, but are skewed from perpendicular with the inserted tube or rod. With the aperture in the tab skewed against the tube or rod, the edges of the tab surrounding the aperture frictionally engage the tube or rod to securely hold the clamp in position. Because the two tabs forming the clamp extend at opposite oblique angles to each other, each tab and corresponding aperture independently secures the inserted tube or rod at the desired position, effectively locking the tube or rod in place. [0012] In other exemplary embodiments, the horizontal supports and vertical rods are of differing lengths and diameters, so that a plant cage can be configured in various sizes and shapes as desired. BRIEF DESCRIPTION OF THE DRAWINGS [0013] FIG. 1 is a perspective view of a plant cage having horizontal supports and vertical rods interconnected with locking clips in accordance with an exemplary embodiment of the present invention, showing an exemplary configuration in which the rods and locking clips can be assembled. [0014] FIG. 2 is a close up perspective view of a locking clip of the plant cage of FIG. 1 . [0015] FIG. 3 is a fragmentary, close-up side view of a portion of the locking clip of FIG. 2 with the tabs deflected towards each other. [0016] FIG. 4 is a fragmentary, close-up side view of a portion of the locking clip of FIG. 2 with a rod inserted into the apertures and the tabs released. [0017] FIG. 5 is a close-up perspective view of a portion of the plant cage of FIG. 1 . [0018] FIG. 6 is a perspective view of an alternative configuration of a plant cage in which the rods and locking clips can be assembled. DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS [0019] Various embodiments of the present invention are disclosed herein, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Thus, any specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed structure. The drawings constitute a part of this specification and include exemplary embodiments of the present invention and illustrate various objects and features thereof. [0020] Certain terminology used in the following description is for convenience in reference only and is not limiting. For example, the words “vertically”, “horizontally”, “vertical”, “horizontal” and “upwardly”, “downwardly”, “upper”, “lower” all refer to the installed position of the item to which the reference is made. The words “inwardly” and “outwardly” refer to directions toward and away from, respectively, the geometric center of the embodiment being designated and parts thereof. The terminology used herein may include the words specifically mentioned, derivatives thereof and words of a similar import. It is further understood that terminology such as the aforementioned directional phrases may be used to describe exemplary embodiments of the plant cage as shown in the figures herein, specifically with a series of vertical rods interconnected to horizontal supports via locking clips to form generally square tower plant cage. This is for convenience only as it is understood that the exemplary embodiments of the plant cage described may of varying size and shape, and that the supports and rods may be positioned at angles other than specifically horizontal or vertical. [0021] Looking first to FIG. 1 , a plant cage in accordance with an exemplary configuration in which the rods and locking clips of the present invention can be assembled is referenced generally by the numeral 10 . The plant cage 10 configured as shown has been assembled as a generally square-shaped tower, with three support tiers 14 , 18 , 22 arranged from the bottom to the top of the tower. The configuration shown comprises four cylindrical vertical support rods 12 a , 12 b , 12 c , 12 d , positioned and oriented to define the outer corners of the cage. The three generally square support tiers 14 , 18 , 22 are formed by twelve cylindrical horizontal support rods 16 , 20 , 24 of approximately equal length extending between the corner vertical support rods, with four rods used to form each tier. Thus, lower tier 14 comprises horizontal support rods 16 a , 16 b , 16 c , 16 d , middle tier 18 comprises horizontal support rods 20 a , 20 b , 20 c , 20 d , and upper tier 22 comprises horizontal support rods 24 a , 24 b , 24 c , 24 d. [0022] Looking still to FIG. 1 , twenty-four identical locking clips connect the ends of the horizontal support rods 16 , 20 , 24 to the corresponding adjacent vertical support rods 12 . Thus, as shown in the figure, locking clip 26 connects an end of horizontal support rod 24 b to vertical support rod 12 d , while an identical locking clip 28 at the opposite end of horizontal support rod 24 b connects the opposite end of horizontal support rod 24 b to vertical support rod 12 a . That same arrangement of a locking clip at each end of each horizontal support rod 16 , 20 , 24 attached to the proximate vertical support rod 12 repeats throughout the plant cage structure. With the clips attached to the horizontal support rods and corresponding vertical support rods, the cage as shown in FIG. 1 is formed. It should be understood that while in the configuration of a plant cage depicted in FIG. 1 that the horizontal support rods are arranged in a square shape, at ninety-degree angles, the locking clips of the present invention allow the horizontal support rods to be arranged at virtually any angle to each other. For example, each tier 14 , 18 , 22 could be triangular, pentagonal, or other shape with the locking clip allowing placement of adjacent horizontal supports at a desired angle. [0023] Looking to FIG. 2 , a locking clip in accordance with an exemplary embodiment of the present invention, and as identified as one of a plurality of identical locking clips 26 , 28 with respect to FIG. 1 , is depicted generally by the numeral 100 . Locking clip 100 comprises an elongated body 102 with a clamp portion 104 , 106 positioned at opposite ends of the body. The two clamp portions 104 , 106 are essentially identical in structural configuration but are oriented in orthogonal relationship on opposite ends of the body 102 such that clamp 106 is rotated ninety degrees with respect to clamp 104 . [0024] Clamp 106 comprises a pair of tabs 108 a , 108 b extending outwardly from the body 102 at oblique angles. A U-shaped channel 110 is defined at the junction between tabs 108 a and 108 b and the body 102 , with the tabs 108 a , 108 b flaring outwardly at oblique angles away from each other at their distal ends, with the two projecting tabs thus forming an overall “V” shaped extension portion 110 . [0025] As seen in the figure, the thickness t of each tab 108 remains essentially constant along the length of the projecting tab, while the width w of the tab increases toward the distal end. Thus, the tab is 108 narrower at the juncture with body 102 , and wider at the portion where an aperture 114 is formed, near the distal end. The relative thinness of the projecting tabs 108 allow each tab to be deflected from its natural resting positions shown in the figure and towards the complementary tab. A semicircular detent portion 116 a , 116 b formed at the distal end of each tab provides a gripping area allowing a user to grasp the two tabs (e.g., between a thumb and a forefinger) and squeeze to deflect the tabs toward each other. Upon release, the resiliency of the locking clip material causes the tabs to spring back to their original, undeflected, positions. [0026] Circular apertures 114 a and 114 b are formed through each respective tab 108 a and 108 b , the aperture positioned towards the distal end of the corresponding tab. With the tabs 108 in their normal, released position as shown in the figure (i.e., a user is not squeezing the tabs so as to deflect them towards each other) the axis x a , x b of each aperture 114 is generally perpendicular to the surface of the portion of the tab 108 in which it is formed, such that the apertures are at oblique angles to each other, corresponding to the oblique arrangement of the tabs 108 a , 108 b themselves, as previously described [0027] With the tabs 108 a , 108 b positioned in close proximity (i.e., pinched together towards each other) the apertures 114 a , 114 b in the respective tabs 108 a , 108 b align concentrically and in generally parallel planes such that a horizontal support tube or vertical rod can be inserted into and through the aligned apertures with the inserted tube or rod generally perpendicular to the planar orientation of the apertures. Thus, as seen in FIG. 3 , in use, when a user squeezes the two tabs 108 a , 108 b together (e.g., between a thumb and finger) the tabs deflect towards each other so that the apertures 114 a , 114 b in the two respective tabs 108 a , 108 b align concentrically, as indicated in the figure by the alignment of the two axes x a , x b of the respective tabs. [0028] With the tabs 108 thus deflected towards each other and the apertures 114 aligned, it should be apparent that a cylindrical tube or rod having a diameter smaller than the diameter of the apertures 114 can be inserted into and through the aligned pair of apertures 114 . It should also be seen that when the tabs 108 are released with a tube or rod thus inserted, the resiliency of the material causes the tabs towards spring back towards their original, non-deflected positions, away from and at oblique angles to each other. [0029] As seen in the close-up view of FIG. 4 , with a tube 120 inserted into and through the pair of apertures 114 and the tabs released, the tabs 108 return towards their original positions, inhibited from fully returning to that position by the inserted tube 120 or rod. Thus, the apertures 114 are positioned such that they are not aligned axially with the inserted tube 120 , but are skewed. Thus skewed, the edges of the tabs 108 surrounding the apertures 114 frictionally engage against the tube 120 to securely hold the clamp in position against the tube 120 and to prevent the tube 120 from sliding up or down within the apertures 114 . Furthermore, because the two tabs 108 a , 108 b forming the clamp extend at opposite oblique angles to each other, each tab 108 and corresponding aperture 114 independently and oppositely secure the inserted tube 114 at the desired position, effectively locking the tube 120 in place. [0030] The vertical and horizontal support rods are preferably cylindrical in shape and formed from a rigid, durable material. Preferably, the rods and supports are constructed of a composite material having properties that resist deterioration when exposed to moisture, temperature extremes, and sunlight, such as a glass fiber reinforced thermosetting resin or polymer (FRP), sometimes referred to as fiberglass. Most preferably, the rods and supports are formed using a pultrusion process in which reinforcing fibers or matting are pulled through a vat of resin and then through a heated die where the resin is cured or set. The pultrusion process permits the rods to be fabricated to any desired length by cutting as it is being pultruded [0031] Similarly, the locking clip is preferably made from a durable, weather resistant material such as FRP or other composite material, or from a plastic material such as polyvinyl chloride (PVC). Preferably the locking clip is formed by molding the material into the desired configuration comprising a body with tabs extending from each end. Most preferably, the circular apertures in the extending tabs are formed in molding the locking clip, alternatively the apertures may be drilled or cut separately from the molding process. [0032] Other alternative embodiments of the horizontal and vertical support rods and the locking clip than those specifically depicted are within the scope of the present invention. For example, the support rods may be shaped other than cylindrical, and may be square, rectangular, triangular, or other shaped rods in which case the apertures in the tabs of the locking clip would be correspondingly shaped. It is also foreseen that the horizontal and vertical support rods can be formed using other materials or means, such as by injection molding using a thermoplastic material [0033] Turning to FIG. 6 , an alternative configuration of a plant cage in which the rods and locking clips of the present invention can be assembled is referenced generally by the numeral 200 . In this embodiment, the rods and locking clips are arranged to form a plant cage configured as a triangular-shaped tower, with three support tiers 214 , 218 , 222 arranged from the bottom to the top of the tower. The plant cage comprises three cylindrical vertical support rods 212 a , 212 b , 212 c positioned to define the outer corners of the cage. The three support tiers 214 , 218 , 222 are formed by nine cylindrical horizontal support rods of approximately equal length extending between each corner, with three rods used to form each tier. Thus, lower tier 214 comprises horizontal support rods 216 a , 216 b , 216 c , middle tier 218 comprises horizontal support rods 220 a , 220 b , 220 c , and upper tier 222 comprises horizontal support rods 224 a , 224 b , 224 c . Eighteen identical locking clips as previously described connect the ends of the horizontal support rods to the corresponding adjacent vertical support rod. [0034] With reference to the plant cages of FIGS. 1 and 6 , it will be apparent that using the locking clip and horizontal and vertical support rods of the present invention that a plant cage of virtually any size and configuration can be assembled. For example, the square cage of FIG. 1 could be replicated side-by-side and attached to the existing cage using additional locking clips. Similarly, plant cages of various shapes can be configured from a single set of horizontal and vertical support rods and locking clips. [0035] It should be further understood that a plant cage in accordance with the present invention may include more or fewer support tiers than depicted in the exemplary embodiments. These and other variations are contemplated by and are within the scope of the present invention. [0036] With the plant cage assembled as described above using the locking clips and horizontal and vertical supports rods of the present invention, the locking clips secure the rods so that they cannot move or slip horizontally or vertically and are essentially fixed in place until a user physically releases the clips by squeezing the tabs together. The plant cage is thus secure and rigid and resistant to deterioration by moisture, weather, sunlight, and other environmental conditions. [0037] In further exemplary embodiments the clips can be permanently adhered to the support rods using a fiberglass glue or adhesive, such as a cyanoacrylate adhesive, after assembly into the desired configuration. [0038] It should be understood that while certain forms and embodiments have been illustrated and described herein, the present invention is not to be limited to the specific forms or arrangement of parts described and shown, and that the various features described may be combined in ways other than those specifically described without departing from the scope of the present invention. The terms “substantially”, “generally”, “approximately”, or any other qualifying term as used herein may be applied to modify any quantitative representation which could permissibly vary without resulting in a change to the basic function to which it is related. For example, the orientation of the clamp portions at opposite ends of the body of the locking clip are described as being orthogonal, but may permissibly vary from that configuration if the variance does not materially alter the capability of the invention.
A plant cage for supporting growing plants includes horizontal and vertical support rods connected by locking clips to form a cage of a desired size and shape. The locking clip includes a clamp at each end of an elongated body, with each clamp formed of two tabs extending outwardly at oblique angles, with an aperture formed in each tab for receiving a horizontal or vertical support rod. The outwardly extending tabs are resilient and flexible such that the tabs can be moved towards each other to a deflected position so that the apertures align and a support rod can be inserted, the resiliency of the material then biases the tabs away from each other when released so that the apertures become unaligned so that the inserted rod is frictionally captured by the clamp.
0
FIELD OF THE INVENTION This invention relates to ink jet printing apparatus, and more particularly, to multi-nozzle ink jet printing apparatus in which ink drops are generated on demand in response to suitable electrical signals. DESCRIPTION OF THE PRIOR ART There have been known in the prior art ink jet printing systems in which an electromechanical transducer is selectively energized to produce ink drops on demand. U.S. Pat. No. 3,683,212 to Zoltan, U.S. Pat. No. 4,390,886 to Sultan, and U.S. Pat. No. 4,418,356 to Reece, disclose an ink jet drop-on-demand print head in which the electromechanical transducer is a piezoelectric tube. The requirements for a higher print rate and a greater resolution in printing has led to multi-nozzle drop-on-demand ink jet arrays. These arrays require densely packed piezoelectric transducers to minimize the size and weight of the print head, and to enhance print visibility during printing operations. Due to the close proximity of the piezoelectric transducers, wiring for the electrodes on the piezoelectric tubes is extremely difficult. In addition, sealing at both ends of the piezoelectric transducer is particularly difficult since alignment, registration and centering of a large number of individual piezoelectric tubes is not easily accomplished. Conventional methods used in fabricating piezoelectric driver assemblies include standard lead soldering techniques on the electrodes and epoxy bonding materials at both ends of the piezoelectric elements. However, the prior art technique offers little flexibility for repair and replacement in case of broken parts either during fabrication of the print head or in later use. U.S. Pat. No. 4,584,591 to Kindler and U.S. Pat. No. 4,588,999 to Depta et al show an array of piezoelectric tubes which are clipped in place, soldered and incorporated into a molded assembly. None of the prior art patents show an array of piezoelectric tubes which are "floating" inside a body member so that they are self-aligned and self-centered when the array is fixed in position between a manifold section and a fan-in section. SUMMARY OF THE INVENTION It is therefore the principal object of this invention to provide an ink jet drop-on-demand print head of modular design in which the array of piezoelectric transducers are properly aligned and centered when the array is fixed in position between a manifold section and a fan-in section. According to the present invention, there is provided an ink jet drop-on-demand print head comprising a plurality of piezoelectric transducers each having first and second separate electrically conducting coating formed thereon to provide a first and a second electrode. A member is provided for holding the transducers in a spaced apart position and a substrate is provided which includes a plurality of spaced electrical conductors. The substrate is positioned adjacent a plurality of the transducers, and a resilient connector means is provided which is not electrically conductive along one dimension but is electrically conductive across its other dimension. The connector means is positioned to make electrical contact between one of the electrodes on said transducer and one of the electrical conductors on the substrate. In a first embodiment the substrate comprises a flat cable conductor, and in a second embodiment the substrate comprises a printed circuit board. The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of a preferred embodiment of the invention as illustrated in the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of an ink jet drop-on-demand print head embodying the present invention. FIG. 2 is a perspective view of a specific embodiment of the ink jet drop-on-demand print head of the present invention. FIG. 3 is an exploded view of a part of the ink jet drop-on-demand print head of FIG. 2. FIG. 4 is a plan view of a flat gasket member. FIG. 5 is an exploded view of an alternate embodiment of the ink jet drop-on-demand print head of the present invention. FIG. 6 is a partial section view taken along line 6--6 of FIG. 5. FIG. 7 is a partial section view taken along line 7--7 of FIG. 5. FIG. 8 is a partial exploded view of a further embodiment of the ink jet drop-on-demand print head of the present invention. FIG. 9 is a partial front view of the ink jet drop-on-demand print head of FIG. 8. DESCRIPTION OF THE PREFERRED EMBODIMENTS The print head 10 comprises an actuator section 12 to which liquid ink is supplied from ink supply section 14. Actuator section 12 provides the driving force to eject drops of liquid ink from print element section 16. Fan-in section 18 provides ink channels which extend from the actuator section 12 to the print element section 16. The present invention is directed to the actuator section 12, and this section will be described in detail after a brief description of the other components of the print head 10. The ink supply section 14 comprises an ink supply means 11 which supplies a marking fluid such as liquid ink to manifold 13. Manifold 13 feeds the liquid ink to each of the transducers in actuator section 12, and a plurality of openings are provided to feed the liquid ink to a corresponding opening in the actuator section 12. A transducer tube gasket (not shown) is provided to seal the ink path between the ink supply section 14 and the actuator section 12 in fluid tight relation. The fan-in section 18 comprises a plurality of ink channels, one end of which is positioned to mate with one of the transducers in actuator section 12, and this interface is maintained in fluid tight relation by a transducer tube gasket (not shown). As the ink channels move through the fan-in section toward the print element section, the spacing of the ink channels converges from the spacing of the transducers in actuator section 12 to the spacing of the orifices in print element section 16. The print element section comprises an orifice plate substrate 21 into which is formed a plurality of openings in registration with the ink channels in fan-in section 18, and the interface is maintained in fluid tight relation by a gasket member (not shown). An orifice plate 22 which has a plurality of nozzles or orifices 23 in registration with the openings in orifice plate substrate 21. The orifice plate substrate 21 provides support for the fragile orifice plate 22, and the orifice plate 22 is permanently bonded to the orifice plate substrate 21. The diameter of each of the ink channels through the fan-in section 18, the gasket member 20, and the orifice plate substrate is chosen to provide a good acoustic impedance match in order to minimize reflections of the ejection pressure wave in each channel of the drop generator. In the embodiment of the invention shown in the drawings, (FIGS. 2 and 3) actuator section 12 comprises a plurality of piezoelectric tubes 26 which are held in position by a tube housing member 24. Tube housing member 24 can be a molded plastic part, for example, and the housing comprises a plurality of openings into which the piezoelectric tubes 26 provide a close fit. The piezoelectric tubes 26 are coated, both inside and outside, with a conductive material that is resistant to corrosion by the liquid ink. Near each end of the tube 26 a ring 28 is formed on the outside of the tube so that no conductive material is present in the ring area. The ring 28 has the effect of producing two electrodes on the tube. The first electrode 30 is formed on the inside of the tube, around the ends of the tube, and on the outside of the tube near the ends of the tube. The second electrode 32 is produced on the center portion of the outside of the tube between the two rings 28. The first electrode 30 is connected to a reference potential and the second electrode 32 carries the drive signal for each of the piezoelectric tubes 26. The active portion of the tube 26 is the center portion, that is, the portion between the two rings 28. When an electric pulse is applied to the center portion electrode 32 of a piezoelectric tube 26, the tube momentarily contracts and generates a pressure wave in the ink inside the tube. A portion of this pressure wave travels forward in the channel from the center portion of the tube 26 and the forward traveling wave causes the ejection of a drop of ink from the corresponding orifice 23 when the pressure wave reaches the print element section 16. In the embodiment of the print head shown in FIG. 2, the actuator section 12 is divided into two symmetrical halves. The actuator section 12 comprises a supporting frame 34 having two identical halves 36 fastened together and two identical modules 38 of piezoelectric tubes 26. The modular block 38 (FIG. 3) is made of an inexpensive, non-conductive material such as plastic with two columns each having a selected number of holes 40 through its entire length. These holes 40 are made just large enough for free insertion of the piezoelectric tubes 26. Two slots 42, 44 are provided on each side of the blocks 38 to expose the signal electrodes 32 and the reference electrodes 30 of the piezoelectric tubes 26. Electrical connector means 46 are provided to connect a particular signal electrode 32 to a corresponding electrical conductor 48 on flat cable conductor 50. Electrical conductor means 46 comprises a resilient body member 52 which is non-conductive and which has conductive rings 54 at spaced intervals so that electrical contact is made between one of the conductors 48 and one of the electrodes 30 or 32 of the piezoelectric transducers 26. The completed actuator seotion 12 is then fastened to the ink supply section 14 and the fan-in section 18 by suitable screws, clamps or clips. A flat gasket member 56 (FIG. 4) having openings corresponding to holes 40 is placed on each end of the actuator section 12. The control signals to produce the desired printed data are coupled to corresponding ones of conductors 48. The print head design has many advantages both in fabrication and in operation. The design permits easy repair and replacement of all the components of the print head either at the time of fabrication or in later operation of the print head. No soldering is required for electrical contact, and no epoxy or other bonding material is needed to hold the piezoelectric tubes in position since the piezoelectric tubes 26 are essentially floating inside the modular block 38 and are self-aligned and self-centered when the actuator section 12 is fastened in place between the ink supply section 14 and the fan-in section 18. As the number of modules required for a high resolution print head increases, the embodiment of the invention shown in FIGS. 5-7 makes it easier to retain the relative registration among modules. The print head is shown in an exploded view in FIG. 5, and the print head comprises a body member 58 having a plurality of holes 60 which are arranged in a plurality of rows and extend through the entire body member 58. A recess 62 is provided in each end of body member 58 in the face normal to holes 60 to provide a step overhang 64. A printed circuit board 66 is provided with a plurality of holes 68 having the same spacing as holes 60 in body member 58. An electrical conductor 70 is provided on the printed circuit board 66 which extends from one of the holes 68 to the edge of the printed circuit board 66. Piezoelectric tubes 26 are inserted in each of the holes 60 in body member 58, and the ends of the piezoelectric tubes 6 are inserted through one of the holes 68, in the printed circuit board 66. Gasket member 74 has a corresponding plurality of holes and the ends of the piezoelectric tubes 26 are also inserted partially through one of the holes in gasket member 74. One slot 72 is provided along each row of holes 60 within the recessed face of body member 58. When the actuator section is assembled, as shown in FIG. 6, an electrical conductor means 46 is positioned within each slot 72 to make electrical contact between one of the electrodes 30, 32 on piezoelectric tube 26 and the corresponding one of the conductors 70 on printed circuit board 66. As shown in FIG. 7, the step overhangs 64 on top and bottom of body member 58 provide a positive stop when the actuator section 12 is clamped between the manifold section 14 and the fan-in section 18, thereby preventing over-compression of the gasket members 74. In the embodiment shown in FIGS. 5-7, one slot and one conductor means for each column of piezoelectric tubes is needed. However, in the further embodiment of the invention shown in FIGS. 8 and 9, two adjacent columns of piezoelectric tubes can utilize one slot and one conductor means. As shown in FIG. 9, the piezoelectric tubes 26 in adjacent columns are staggered, and a slot 76 is cut in body member 78 which extends between two adjacent columns of piezoelectric tubes 26a and 26b. A conductor means 46w is provided which has the size and shape, when placed in slot 76, to make electrical contact with one of the electrodes 30, 32 on piezoelectric tubes 26a or 26b and the corresponding one of the conductors 82a or 82b on printed circuit board 80. In other respects this embodiment is similar to that shown in FIGS. 5-7. Several embodiments of the invention have been described, each of which has the advantage of modular design, and fabrication advantages which include no soldering operation and no bonding operation. The print head is repairable should one or more components require replacement. The modular design also offers additional advantages in terms of piezoelectric tube registration and alignment. While the invention has been particularly shown and described with reference to a preferred embodiment thereof, it will be understood by those skilled in the art that various other changes in the form and details may be made therein without departing from the spirit and scope of the invention.
An ink jet drop-on-demand print head comprises a plurality of tubular piezoelectric transducers each having two electrodes formed by an electrically conducting coating. A housing member holds the transducers in a position which includes at least one row of transducers. A substrate includes a plurality of electrical conductors, and the substrate is positioned so that each electrical conductor is adjacent one of the electrodes. A resilient connector means is provided which is not conductive along its length but is conductive across its width, and the connector means is positioned to make contact with a selected one of the electrical conductors and only one of the electrodes of one of the transducers. In a specific embodiment, the substrate comprises a flat conductor cable, and in a second embodiment the substrate comprises a printed circuit board.
1
CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of U.S. Provisional Application No. 61/869,583, filed Aug. 23, 2013, which is hereby incorporated by reference herein in its entirety, including but not limited to those portions that specifically appear hereinafter, the incorporation by reference being made with the following exception: In the event that any portion of the above-referenced provisional application is inconsistent with this application, this application supercedes said above-referenced provisional application. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT [0002] Not Applicable. BACKGROUND [0003] 1. The Field of the Present Disclosure [0004] The present disclosure relates generally to packaging, and more particularly, but not necessarily entirely, to packaging for shipping thin, fragile planar members, such as glass, used on electronic devices. [0005] 2. Description of Related Art [0006] The rise of e-commerce websites has led to a dramatic increase of good being shipped by common carrier to consumers. One popular product commonly bought on e-commerce websites is screen protectors for electronic devices. In the past, screen protectors comprised a thin, flexible sheet of plastic. More recently, the use of thin, fragile planar members, such as tempered glass, as screen protectors for electronic devices has become more popular. [0007] Durable and low-cost packaging for shipping glass screen protectors, however, has proven challenging. In particular, tempered glass, while somewhat less prone to breaking than regular glass, may still break or shatter if not handled properly. Thus, it would be an advantage over the prior art to provide a low-cost, durable, and easy-to-manufacture package design for shipping tempered glass. [0008] The features and advantages of the present disclosure will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by the practice of the present disclosure without undue experimentation. The features and advantages of the present disclosure may be realized and obtained by means of the instruments and combinations particularly pointed out in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS [0009] The features and advantages of the disclosure will become apparent from a consideration of the subsequent detailed description presented in connection with the accompanying drawings in which: [0010] FIG. 1 is a front view of a support insert in an unfolded configuration according to an exemplary embodiment of the present disclosure; [0011] FIG. 2 is a rear view of the support insert shown in FIG. 1 in an unfolded configuration according to an exemplary embodiment of the present disclosure; [0012] FIG. 3 is a front view of the support insert shown in FIG. 1 in a folded configuration with its protective front flap in an open configuration and a thin, fragile planar member mounted thereon according to an exemplary embodiment of the present disclosure; [0013] FIG. 4 is a front view of a support insert shown in FIG. 1 in a folded configuration with its protective front flap in a partially open configuration and a thin, fragile planar member mounted thereon according to an exemplary embodiment of the present disclosure; [0014] FIG. 5 is a front view of a support insert in a folded configuration with its protective front flap in a closed configuration according to an exemplary embodiment of the present disclosure; [0015] FIG. 6 is a perspective view of the support insert shown in FIG. 1 partially installed into an interior of a box according to an exemplary embodiment of the present disclosure; and [0016] FIG. 7 is a top view showing the interior of the box showing a top profile of the support insert. DETAILED DESCRIPTION [0017] For the purposes of promoting an understanding of the principles in accordance with the disclosure, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the disclosure is thereby intended. Any alterations and further modifications of the inventive features illustrated herein, and any additional applications of the principles of the disclosure as illustrated herein, which would normally occur to one skilled in the relevant art and having possession of this disclosure, are to be considered within the scope of the disclosure claimed. [0018] In describing and claiming the present disclosure, the following terminology will be used in accordance with the definitions set out below. It must be noted that, as used in this specification and the appended claims, the singular forms “a,”“an,” and “the” include plural referents unless the context clearly dictates otherwise. As used herein, the terms “comprising,” “including,” “having,” “containing,” “characterized by,” and grammatical equivalents thereof are inclusive or open-ended terms that do not exclude additional, unrecited elements or method steps. [0019] Applicants have invented a low cost and durable package for shipping thin, fragile planar members, such as members formed of glass. The applicants' invention is particularly suited for packaging glass screen protectors for electronic devices, such as smart phones. In an embodiment, the applicants' invention comprises a support insert and a box. The support insert may be operable between an unfolded configuration and a folded configuration. In the unfolded configuration, the support insert may be substantially flat. In this regard, the support insert may be formed of paper stock having a thickness less than a millimeter. In the folded configuration, the support insert may define a mounting surface for an object, such as a thin, fragile planar member, and a protective flap having a living hinge interposed between them. The protective flap may be operable between an open configuration and a closed configuration with respect to the mounting surface. [0020] Referring now to FIGS. 1 and 2 , a front and back view, respectively, of a support insert 100 is shown. The support insert 100 may comprise a substantially planar member 102 . In an embodiment, the member 102 is formed of a paper or card stock having a thickness less than 1 millimeter. In an embodiment, the thickness of the member 102 may be about 1 millimeter or greater. [0021] The member 102 may comprise a flap portion 104 and a back portion 106 . In an embodiment, a length, L1, of the flap portion 104 is less than a length, L2, of the back portion 106 . [0022] Interposed between the flap portion 104 and the back portion 106 may be a first portion 110 and a second portion 112 . In particular, the first portion 110 is adjacent the flap portion 104 and the second portion 112 is adjacent the back portion 106 . Interposed between the flap portion 104 and the first portion 110 is a fold 114 as indicated by the dashed line. Interposed between the first portion 110 and the second portion 112 is a fold 116 as indicated by the dashed line. Interposed between the second portion 112 and the back portion 106 is a fold 118 as indicated by the dashed line. As seen in FIG. 1 , the first portion 110 includes a surface A 1 and the second portion 112 includes a surface A 2 . [0023] Disposed along an outside edge of the back portion 106 is a third portion 120 and a fourth portion 122 . Interposed between the back portion 106 and the third portion 120 is a fold 124 as indicated by the dashed line. Interposed between the third portion 120 and the fourth portion is a fold 126 as indicated by the dashed line. As seen in FIG. 1 , the third portion 120 includes a surface B 1 and the fourth portion 122 includes a surface B 2 . [0024] It will be appreciated that the folds 114 , 116 , 118 , 124 , and 126 may include perforations that form fold lines. In an embodiment, the folds 114 , 116 , 118 , 124 , and 126 may be formed by hand or by a machine. In addition, the back portion 106 may include tabs 130 . The tabs 130 may be formed by slits formed in the back portion 106 . [0025] Referring now to FIGS. 1 and 3 , the first portion 110 and the second portion 112 may be folded together along fold 116 such that the surfaces A 1 and A 2 matingly engage to form a double folded portion. In an embodiment, an adhesive is utilized to join the surfaces A 1 and A 2 together. In an embodiment, a mechanical fastener, such as a staple, may be utilized. In an embodiment, the surfaces A 1 and A 2 are not joined together but are held in place due to the stiffness of the member 102 . The third portion 120 and the fourth portion 122 may be folded together along fold 126 such that the surfaces B 1 and B 2 matingly engage. In an embodiment, an adhesive is utilized to join the surfaces B 1 and B 2 together. In an embodiment, a mechanical fastener, such as a staple, may be utilized. In an embodiment, the surfaces B 1 and B 2 are not joined together and are held in place by the stiffness. [0026] Referring now to FIGS. 3-5 , with the surfaces A 1 and A 2 joined, the fold 114 forms a living hinge that allows the flap portion 104 to operate between an open position ( FIG. 3 ), an intermediate position ( FIG. 4 ) and a closed position ( FIG. 5 ). An object, such as a thin, fragile planar member 150 may be installed onto a top surface 152 of the back portion 106 . Two of the tabs 130 may be utilized to hold the planar member 150 in place. As observed in FIG. 5 , with the planar member 150 in place, the flap portion 104 may be closed and secured in place by another one of the tabs 130 . [0027] Referring now to FIGS. 6 and 7 , with the planar member 150 in place and the flap portion 104 in the closed position over the planar member 150 , the insert 100 may be slidably inserted into an interior portion 202 of a box 200 . As seen in FIG. 7 , a horizontal cross section of the interior portion 202 of the box 200 may be rectangular shaped. In an embodiment, the interior portion 202 comprises a pair of opposing sidewalls 204 and 206 . The interior portion 202 further comprises a pair of opposing sidewalls 208 and 210 . In an embodiment, sidewalls 204 and 206 are longer than the sidewalls 208 and 210 . [0028] As perhaps best seen in FIG. 7 , when installed into the interior 202 of the box 200 , the insert 100 may have a Z-shaped horizontal cross section. In particular, the first portion 110 and the second portion 112 , which together may form a double folded sidewall or leg, may extend parallel and adjacent to the sidewall 208 . The third portion 120 and the fourth portion 122 , which together may form a double folded sidewall or leg, may extend parallel and adjacent to the sidewall 210 . The double folded portion created by the first portion 110 and the second portion 112 may be substantially parallel to the double folded portion created by third portion 120 and the fourth portion 122 . [0029] As can be further observed, the back portion 206 and the flap portion 204 , which together may define a middle wall portion, may extend diagonally between an interior corner 212 formed at the intersection of the sidewalls 204 and 208 and an interior corner 214 formed at the intersection of the sidewalls 206 and 210 . [0030] The insert 100 may also include a hang tag 216 for use in retail displays. In an embodiment, the hang tag 216 may be integrally formed with the insert or not. In an embodiment, the hang tag 216 may extend through a slot in the box 200 . [0031] It will be appreciated that the configuration of the insert 100 within the box 200 prevents damage to the planar member 150 . In particular, the insert 100 suspends the planar member 150 between, but away from, the walls of the box 200 . [0032] In an embodiment, the middle wall portion formed by the back portion 206 and the flap portion 204 may intersect the sidewall formed by the first portion 110 and the second portion 112 at an angle between 35 degrees and 60 degrees. In an embodiment, the middle wall portion formed by the back portion 206 and the flap portion 204 may intersect the sidewall formed by the third portion 120 and the fourth portion 122 at an angle of intersection, θ, between 35 degrees and 60 degrees. In an embodiment, the angles of intersection, θ, are about 45 degrees. In an embodiment, the angles of intersection, θ, are greater than 90 degrees. In an embodiment, the angles of intersection, θ, are between 90 degrees and 120 degrees. In an embodiment, the angles of intersection, θ, are between 95 degrees and 105 degrees. In an embodiment, the angles of intersection, θ, is about 100 degrees. [0033] In an embodiment, the support insert 100 is die cut into the shape shown in FIG. 1 . In an embodiment, the support insert 100 and box 200 and the planar member 150 may form a kit for packaging a thin, fragile planar member. In an embodiment, the planar member 150 comprises a thin piece of pre-cut tempered glass that may be applied to a screen of an electronic device, such as a smart phone. [0034] It will be appreciated that the structure and apparatus disclosed herein is merely one example of a means for packaging a thin, fragile planar member, and it should be appreciated that any structure, apparatus or system for a thin, rigid planar member which performs functions the same as, or equivalent to, those disclosed herein are intended to fall within the scope of a means for a thin, rigid planar member, including those structures, apparatus or systems for a thin, rigid planar member which are presently known, or which may become available in the future. Anything which functions the same as, or equivalently to, a means for a thin, rigid planar member falls within the scope of this element. [0035] Those having ordinary skill in the relevant art will appreciate the advantages provide by the features of the present disclosure. For example, it is a feature of the present disclosure to provide a package for use with thin, fragile planar members, such as glass screen protectors for use on electronic devices. Another feature of the present disclosure is to provide a kit for protecting a display of an electronic device. It is a further feature of the present disclosure, in accordance with one aspect thereof, to provide a shipping package for screen protectors for electronic devices. [0036] It will be further appreciated that the support insert may be utilized in packaging for various objects, including thin, fragile planar members. The support insert may be utilized with non-planar members. [0037] In the foregoing Detailed Description, various features of the present disclosure are grouped together in a single embodiment for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed disclosure requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the following claims are hereby incorporated into this Detailed Description of the Disclosure by this reference, with each claim standing on its own as a separate embodiment of the present disclosure. [0038] It is to be understood that the above-described arrangements are only illustrative of the application of the principles of the present disclosure. Numerous modifications and alternative arrangements may be devised by those skilled in the art without departing from the spirit and scope of the present disclosure and the appended claims are intended to cover such modifications and arrangements. Thus, while the present disclosure has been shown in the drawings and described above with particularity and detail, it will be apparent to those of ordinary skill in the art that numerous modifications, including, but not limited to, variations in size, materials, shape, form, function and manner of operation, assembly and use may be made without departing from the principles and concepts set forth herein.
A low cost and durable package for use in shipping thin, fragile planar members, such as protective tempered glass screen protectors for electronic devices. The package may include a rectangular box having a sidewall that defines an interior portion. A support insert having two outer sidewall members and a middle wall portion is configured and adapted to fit within the interior portion of the box. The middle portion may include cutouts for restraining a glass screen protector for an electronic device. A flap configurable between an open position and a closed position may provide further protection.
1
BACKGROUND OF THE INVENTION [0001] The invention relates to a production machine with a hydraulic and/or electric drive, and also measured data acquisition for at least one positional determination and at least two measured variables dependent on the latter in the production machine. [0002] The development of simple, effective and reliable production machines and methods for their open-loop and closed-loop control provides an impetus motivation to improve technical processes. The present invention is such an improved technical process. [0003] EP 0 246 326 B1 discloses a method of controlling an injection mechanism of an injection-molding machine. Measuring force at the load or measuring the injection pressure is used purely and simply for current control of a drive source. [0004] The object of the present invention is to design a production machine of the type referred to above in such a way that, if additional positionally dependent process variables are exceeded, a positionally dependent setpoint input can be influenced by an amount dependent on the degree to which they are exceeded in a counteracting way by simple and effective action. SUMMARY OF THE INVENTION [0005] According to the present invention, this object is achieved by providing a first positionally dependent setpoint determination, which can be influenced in a counteracting way in at least one parallel open-loop or closed-loop control branch, with a setpoint correction being provided on the basis of a further positionally dependent setpoint profile of at least one further positionally dependent measured variable being exceeded. Consequently, a further open-loop or closed-loop control path in the form of a substitutional open-loop or closed-loop control is only utilized if the process profile monitored there is exceeded. [0006] A preferred design of the invention, in which the production machine is a plastic injection-molding machine, is characterized in that the injection pressure and the position of an advancing screw driving the injection action can be registered as measured variables and at least one speed/displacement profile of the advancing screw can be predetermined as a positionally dependent setpoint value, which can be influenced in a counteracting way if a pressure/displacement profile of the injection pressure is exceeded. This advancement has the effect that essential process parameters of a plastic injection-molding machine can be registered in a simple and effective way and can be influenced for the purpose of optimum process control to achieve high-quality plastic injection-molded products. [0007] A further preferred design of the present invention wherein at least two positionally dependent measured variables of a plastic injection mold can be registered, is characterized in that at least one speed/displacement profile of the mold can be predetermined as a positionally dependent setpoint value, which can be influenced in a counteracting way if a closing pressure/displacement profile of the mold is exceeded. Process control and monitoring of the mold in the injection molding cycle enable the early detection and avoidance of any fault damage or even destruction of the injection-molded past during operation. [0008] Yet a further preferred design of the present invention is characterized in that at least two positionally dependent measured variables of an ejection mechanism of a plastic injection mold can be registered and in that at least one speed/displacement profile of the ejection mechanism can be predetermined as a positionally dependent setpoint value, which can be influenced in a counteracting way if an ejecting force/displacement profile of the ejection mechanism is exceeded. Process control and monitoring of the ejection mechanism has the effect that damage to or even destruction of the ejection mechanism or the plastic injection-molded part is detected at an early time and avoided. [0009] Still another preferred design of the present invention is characterized in that, as an alternative or in addition to a speed/ or measured-variable/displacement profile, a speed/ or measured-variable/time profile can be predetermined. Depending on suitability, consequently a displacement or time profile can be used for optimum process monitoring or control. [0010] Another preferred design of the present invention is characterized in that, as an alternative or in addition to a speed/ or measured-variable/displacement or time profile, a physically or technologically linked displacement or time profile can be predetermined. Consequently, depending on suitability, physically or technologically linked process variables can be used for programming or visual representation. [0011] It is further contemplated that the present invention is utilized in an industrial press. In the case of an industrial press, there are process parameters that are technologically similar to those present in a plastic injection-molding machine. These process parameters can be advantageously monitored and controlled in accordance with the present invention. [0012] A preferred method for the open-loop control of a production machine having a hydraulic or electric drive, measured data acquisition for at least one positional determination, and at least two measured variables dependent on the latter, is characterized by the following: [0000] at least one actual position of a movement system is registered, [0000] a setpoint input takes place by means of at least one speed/displacement profile or a displacement profile derived from the speed, and [0000] in a further control branch with at least one further positionally dependent measured-variable/displacement profile, the setpoint input is influenced in a counteracting way if this second profile is exceeded. [0000] Based on this method, measured variables and setpoint inputs of a production machine are monitored with a simple and effective action. [0013] A further preferred method for the open-loop control of a plastic injection-molding machine having a hydraulic or electric drive, measured data acquisition for (i) a positional determination of an advancing screw, (ii) an advancing screw speed (or rate of injection) and (iii) an injection pressure, is characterized by the following: at least one actual position of a movement system is registered; a setpoint input takes place by means of at least one speed/displacement profile or a displacement profile derived from the speed; and in a further control branch with a further positionally dependent measured-variable/displacement profile, the setpoint input is influenced in a counteracting way if this second profile is exceeded. Based on this method, a wide variety of parameters and setpoint inputs of a plastic injection-molding machine can be monitored and predetermined in a simple and effective way. [0017] Yet another preferred method for the open-loop control of a mold of a plastic injection-molding machine having a hydraulic or electric drive, case measured data acquisition for (i) a positional determination of the mold, (ii) a closing and/or opening speed and (iii) an opening and/or closing pressure, is characterized by the following: at least one actual position of a movement system is registered; a setpoint input takes place by means of at least one speed/displacement profile or a displacement profile derived from the speed; and in a further control branch with at least one further positionally dependent measured-variable/displacement profile, the setpoint input is influenced in a counteracting way if this second profile is exceeded. Based on this method, the optimum functional capability of a mold of a plastic injection-molding machine can be controlled and monitored. [0021] Another preferred method for the open-loop control of an ejection mechanism of a mold of a plastic injection-molding machine having a hydraulic or electric drive, measured data acquisition for (i) a positional determination (ii) a speed and (iii) an ejecting force of the ejection mechanism, is characterized by the following: at least one actual position of a movement system is registered; a setpoint input takes place by means of at least one speed/displacement profile or a displacement profile derived from the speed; and in a further control branch with at least one further positionally dependent measured-variable/displacement profile, the setpoint input is influenced in a counteracting way if this second profile is exceeded. Based on this method, an ejection mechanism can be controlled and monitored in a particular way with respect to its optimum operation and a plastic injection-molded part can be controlled and monitored to enable the mold part to be ejected from the mold without being damaged. [0025] Yet another preferred method is characterized in that, as an alternative to or in addition to a speed/or measured-variable/displacement profile, a speed/or measured-variable/time profile is used. Consequently, a favorable profile for simple and clear programming or visual representation can be selected. [0026] A further preferred method of the present invention is characterized in that, as an alternative to or in addition to a speed/ or measured-variable/displacement or time profile, a physically or technologically linked displacement or time profile is predetermined. Consequently, optimally physically or technologically descriptive process variables can be used for the setpoint input, monitoring or else visual representation of measured variables. [0027] The aforesaid method, for the open-loop control of a production machine are equally suited to an industrial press. Accordingly, disclosed in the context of a plastic injection-molding machine due to technological relationships, the method used in the case of a plastic injection-molding machine can also be advantageously transferred to an industrial press. DRAWINGS [0028] An exemplary embodiment of the present invention is explained in more detail below and represented in the following drawings, in which: [0029] FIG. 1 shows a symbolic side view of a plastic injection-molding machine, in which the screw housing and also the mold are shown in a sectional form; [0030] FIG. 2 shows a basic functional block diagram of the production machine control with at least two mutually dependent measured variables; and [0031] FIG. 3 shows by way of example actual and setpoint-value graphs of a plastic injection-molding machine. DETAILED DESCRIPTION OF THE INVENTION [0032] FIG. 1 , shows a side view of a plastic injection-molding machine. Polymer granules, not shown for the sake of overall clarity, pass via hopper T into a screw housing SG and are transported into the mold FW by an advancing screw VS, which is moved by a drive A. Along the screw housing SG there are heating coils H, which heat up the polymer granules allowing their path and make them take the form of a flowable (plastic) polymer material in the space SV in front of the screw. [0033] To achieve a high rate of production of plastic injection-molded parts, it must be endeavored to use a high rate of injection into the mold FW. With the aid of a pressure sensor D, the injection pressure exerted on the plastic material in the space SV in front of the screw is monitored by an open-loop control system ST or, alternatively a closed-loop control system. The pressure monitoring with a pressure sensor D may take place at other suitable positions of the machine, such as for example in the journal bearing of the machine. [0034] If a specific pressure value is exceeded, there is an irreversible and undesired change in the material properties of the plastic material. The injection pressure built up in the space SV in front of the screw is decisively determined by the forward movement of the advancing screw VS induced by the drive A. The drive A may comprise a plurality of motors, which separately induce a rotational and/or forward movement of the advancing screw VS with the aid of a transmission mechanism. [0035] A positional determination P 1 transmits information on the actual position of the advancing screw VS to an open loop control system ST, denoted in FIG. 1 by the term “control”. All measured variables registered by the control system ST are indicated by broken connecting lines. The positional determination P 1 may be realized for example by a rotary transducer or else by a linear displacement sensor. [0036] In a plastic injection-molding machine, monitoring and control of the heating temperature is also of interest, since an overheating of the plastic material also leads to undesired changes in material properties. Monitoring of the heating temperature may also be part of a monitoring process according to the present invention. For example, a temperature/time profile dependent on the production cycle is fed in as the setpoint input of the heating. Therefore, a broken connecting line is shown in FIG. 1 between the heating coils H and the control system ST. [0037] During the injection operation, the plastic material is usually injected into the mold SW at a specific rate. A sustained rate of injection leads to a very steep increase in pressure in the space SV in front of the screw. The invention allows a rapid response to this increase in pressure, in that action is taken to influence the manipulated variable directly in the form of a substitutional closed-loop or open-loop control. [0038] Once the mold FW is filled with plastic material, the solidifying operation begins. Any accompanying shrinkage process can be compensated by forcing further plastic material into the mold. [0039] Once the injecting and solidifying operation has been completed, the mold FW comprising the mold parts FT 1 and FT 2 is moved apart. The mold part FT 1 is fastened to the mold holder FH 1 and is not moved. The mold part FT 2 is fastened to the mold holder FH 2 and can be moved horizontally away from the mold part FT 1 . With the aid of a toggle lever mechanism, the mold holder FH 2 slides on the sliding rails GS 1 and GS 2 horizontally away from the mold part FT 1 . In FIG. 1 , the toggle lever mechanism comprises a toggle lever nut KH and three lever pieces (H 11 to H 13 , and also H 21 to H 23 ), arranged symmetrically in relation to said nut. In further embodiments, the toggle lever mechanism may comprise a multiplicity of lever pieces, and alternatively be hydraulically and/or hydromechanically driven. [0040] A toggle lever motor KM is used to drive a spindle screw SS, which moves the toggle lever nut KH horizontally and thereby takes the lever pieces H 11 to H 23 along with it in such a way that the mold holder FH 2 is moved horizontally. [0041] A positional determination P 2 , which may for example take the form of a linear displacement sensor, transmits the actual position of the mold holder FH 2 to the control system ST. [0042] To determine the position of the toggle lever nut KH, a toggle lever motor KM is fastened to a rotary transducer DG 2 , which passes on its information to the control system ST. [0043] To be able to remove the plastic injection-molded parts from the mold FW after solidifying, there is a molding ejector FA in the mold part FT 2 . This is driven by an ejection mechanism motor AM and presses the plastic product to be ejected out of the mold part FT 2 . Similarly fastened to the ejection mechanism motor AM is a rotary transducer DG 1 , which determines the position of the molding ejector FA. A further ejection mechanism may be located on the mold part FT 1 . [0044] A combination of a motor (KM, AM, A) with a rotary transducer (DG 1 , DG 2 ) or with a positional determination (P 1 , P 2 ) allows various measured variables to be registered. It is possible to register the position, the distance covered during a time, and also the torque of the respective motor KM, AM, A. It is consequently possible, for example, to determine the position of the molding ejector FA, and also the force exerted on the plastic product, obtained by a conversion of the measured torque. [0045] FIG. 2 shows a functional block diagram of the open-loop production-machine control. A machine coordinate, denoted in FIG. 2 by “x”, is fed to a function block FB 1 , which determines a positionally dependent setpoint value. This setpoint value is converted in a function block FB 6 into a machine control parameter (“n nom ”). [0046] In a further function block FB 2 , a likewise positionally dependent setpoint-value profile is output. This setpoint-value profile is passed through a function block FB 4 if, in the case of a displacement-dependent profile, a specific displacement mark “X max ” has not been exceeded. In the function block FB 4 , to which the machine coordinates “x” are also fed, this is identified by a rhombic decision block. If a defined machine position “X max ” is exceeded, the variables or parameters denoted by “2” are passed on to the addition point AS. At this point, a measured parameter is subtracted from a function value of the function block FB 4 . The subtraction at the addition point AS is identified by a minus sign “−”. [0047] The process path associated with the function block FB 3 is associated with a plastic injection-molding machine and does not have to apply in this form to other production machines. A time-dependent setpoint-value profile is stored in it. [0048] At the addition point AS, differential signals, which are formed by a setpoint-value profile and current measured values “Pact”, are passed on to the function block FB 5 . This uses its programmed properties to model the closed-loop or open-loop control system. It receives its closed-loop or open-loop control parameters for the system as a set of parameters from the function block FB 4 . The function block FB 5 outputs a setpoint correction signal to the function block FB 6 . [0049] All the data connections in the representation according to FIG. 2 take the form of arrow connections and symbolize a directed data flow. A time unit signal “t” is available in the function block diagram shown and is passed to the function block FB 3 . A broken-line connection between the time unit signal “t” and the function block FB 4 is intended to indicate that the machine-position-dependent decision in the function block FB 4 may also be substituted by a time-dependent decision. This means that, once a specific time “t” has elapsed, the data denoted by “2” are processed instead of the data denoted by “1”. Similarly, further variables or process parameters may lead to a single-stage or multi-stage changeover of input and/or output data. With a specific weighting or function, these can bring about the changeover point. This is shown in FIG. 2 by arrows represented by dashed lines at the function block FB 4 with the designation “y”, “z”. [0050] The function block diagram just presented is to be applied below to a plastic injection-molding machine. The positional determination PI of the advancing screw VS supplies the input signal “x” for the function block FB 1 . Dependent on the advancing screw VS, this block passes on a speed setpoint value to the function block FB 6 . This block converts the speed setpoint value into a nominal speed “n nom ” for the drive A. [0051] In the function block FB 2 , a positionally dependent pressure setpoint profile is stored and is passed on to the addition point AS as long as a specific position “X max ” is not exceeded. The current injection pressure in the space SV in front of the screw is determined by the pressure sensor D and made available to the control system as “p act ”. At the addition point AS, the current pressure is subtracted from the pressure setpoint profile and the differential signal is passed on to the function block FB 5 . Only if the positionally dependent pressure setpoint profile from the function block FB 2 is exceeded by the current pressure value does the substitutional open-loop control intervene in a correcting manner. In the function block FB 6 , a correction signal is processed and a new setpoint value is provided. The nominal speed of the drive A is in this case reduced. [0052] From a specific displacement mark of the advancing screw VS, the mold FW is filled with plastic material and the rate of injection has to be reduced to avoid an inadmissible increase in pressure in the space SV in front of the screw. If the current position of the advancing screw VS is the same as the position “X max ”, the function block FB 4 changes over to a data path “2”. A time-dependent pressure setpoint profile of the function block FB 3 is then transmitted to the addition point AS. Since the mold FW is filled, the system parameters for the open-loop control ST also change. Now, a set of parameters denoted by “2”, which is identified in FIG. 2 by “Param.Set2”, is similarly transmitted to the function block FB 5 . As a result, a separate setpoint profile is provided for an injection phase and a holding-pressure phase. Further variables or process parameters may be used for determining a changeover point of a plastic injection-molding machine with a specific weighting or function. These variables may be, for example, an actual position of the advancing screw, an injection pressure or a production cycle time. [0053] In to FIG. 3 , actual- and setpoint-value graphs of the aforementioned situation are shown. In this Figure, a horizontal broken line D 1 denotes a setpoint pressure curve and a solid line denotes a measured pressure curve D 2 in a p(x) diagram. The vertical broken lines, which run over further diagrams, confine an x range between x 1 and x 2 . In this range, the pressure curve D 2 runs above the pressure curve D 1 . The area defined by this is shown by broken lines in the p(x) diagram. [0054] A v nom (x) diagram shows a speed setpoint curve G 1 , which is shown by a broken line. [0055] A v act (x) diagram shows a measured speed curve G 2 . This defines a hatched area with a horizontal line shown as a broken line. [0056] In the x range identified by the vertical broken lines, the injection pressure exceeds the predetermined maximum pressure curve D 1 . The speed setpoint profile G 1 is constant in this range. On account of the injection pressure being exceeded, the speed setpoint profile G 1 is corrected in the substitutional control branch described with reference to FIG. 2 and formed by the function blocks FB 2 , FB 4 , FB 5 and the addition point AS. Consequently, the measured variable which exceeds a predetermined profile acts directly on a setpoint value. [0057] Moreover, it should also be mentioned that the setpoint correction described above may also take place when setpoint values are not reached. Similarly, it is conceivable for bands of setpoint values to be predetermined, so that corrective action is taken if measured values leave this band. [0058] Furthermore, it should be mentioned that the methods described can also be suitably used in particular for production machines which have displacement and pressure among their process parameters. An industrial press may be mentioned here by way of example. A press is technologically no different than the injection mechanism of a plastic injection-molding machine, although of course the dimensioning with respect to the forces to be controlled has to be adapted to the respective application.
The invention relates to a production machine with a hydraulic and/or electric drive and also measured data acquisition for at least one positional determination and at least two measured variables dependent on the latter in the production machine. If a further setpoint profile is exceeded, a setpoint input is corrected directly in the form of a substitutional open-loop or closed-loop control.
1
BACKGROUND OF THE INVENTION This invention relates to entrained flow coal gasifiers and in particular to a method and apparatus for obtaining a higher heating value gas therefrom. Gasification of coal is primarily the incomplete combustion of the coal. The maximum heating value is theoretically obtainable by maintaining a minimum air or oxygen to coal ratio. The ability to achieve this, however, is restrained due to the relatively high temperature level required to maintain the endothermic coal gasifying reactions. The entrained flow gasification process involves the suspension of coal or char particles in a hot gas stream formed by combustion of fuel. These particles then flow concurrently with the product gas stream. Since the particles are suspended in the stream, problems with oiliness and stickiness of the particles during the gasification do not cause problems of stickiness in the flow of the coal. In such a process, when the gas temperature drops to the range of 1700° to 2000° F. the rate of gasification of the carbon particles diminishes to such a point that there is no practical value continuing the gasification process. Some of the high temperature level of heat which was available from the initial combustion of the fuel has been used to drive off volatiles and, therefore, is not available for effectuating the gasification of the char particles. While there is still substantial heat content in the gas stream, it is not available for the coal gasification operation and can only be used to generate steam for some other useful purpose. It is an object of the invention to more effectively utilize the heat available so as to increase the heating value of the gas produced. SUMMARY OF THE INVENTION In accordance with the invention a high temperature level of product gas stream is formed by burning primarily char with the existing air supply. Immediately thereafter additional char is introduced into the high temperature stream for gasification of these carbon particles. Thereafter, following the endothermic gasification reaction which cools the gases, the new fresh coal is introduced with this coal being devolatilized at relatively low temperature, thus utilizing low temperature heat. Entrained char particles are thereafter removed from the gas stream and reintroduced into the gasifier. The low temperature devolatilization of the fresh coal is achieved by gas temperatures at a level which is insufficient to effectively continue the carbon gasification process. Accordingly, more of the available heat is used for the basic purpose of the coal gasification operation, which is of course to produce gas having the maximum reasonable heating value. BRIEF DESCRIPTION OF THE DRAWING The FIGURE is a schematic illustration of the coal gasifier arrangement. DESCRIPTION OF THE PREFERRED EMBODIMENT The coal gasifier indicated generally as 10 includes a combustion zone 12, a reductor 14 and a low temperature devolatilization zone 16. Oxygen is supplied to the combustion zone 12 by supplying air through forced draft fan 18 and regulating damper 20. The amount of this air is regulated in accordance with the desired output from the gasifier. Char which is comprised of carbon and ash is supplied through line 22 and regulated by feeder 24. The ratio of char and air is controlled to maintain a preselected temperature at the outlet 26 of the combustion zone. The ratio is maintained in the combustion zone preferably on the fuel rich side of stoichiometric proportions. The maximum temperature (near stoichiometric) is desired consistant with the ability of materials forming the combustion zone to tolerate such temperatures. The temperature should be above 2800° F. to insure slagging of ash in the combustion zone and preferably about 3000° F. The ash contained in the char particles melts in the combustion zone and flows out through slag spout 28. The product gas stream thus formed in the combustion zone passes upwardly into reductor section 14. At this location immediately downstream of the combustion zone additional char is added through line 30 and controlled by feeder 32. These char particles react endothermically with the combustion products leaving the combustion zone 12 forming carbon monoxide and hydrogen by reaction with carbon dioxide and water vapor contained in the gases exiting from the combustor. This reaction continues until the gases reach the outlet 34 of the reduction zone where the gas temperature is preferably 1700° to 2000° F. At these temperature levels the rate of the char gasification reaction is decreasing. Fresh coal is, therefore, added through line 36 and controlled by feeder 38. This coal is added to the low temperature devolatilization zone 16 where the product gas stream is enriched and further cooled primarily because of the heating, and devolatilization of the incoming coal and reaction of the volatiles. At a temperature below 1400° F. and preferably about 1000° F. the gas products leave the low temperature devolatilization zone 16 flowing outwardly through gas outlet 40 to a particle separator 42. The optimum temperature is the minimum, with this being limited to above the temperature at which oils form for the particular coal being gasified. The gas stream continues through line 44 for removal of any contaminants in the gas and for use of the gas. Char particles are removed from the gas stream in the particle separator 42 and returned through line 46 to supply feeders 32 and 24. The purpose of the combustion zone 12 is to supply the heat required for the process and to remove the ash from the system. While stoichiometric temperature is preferred, where this cannot be tolerated some of the gasification is permitted to occur in the combustor for the purpose of holding the temperature down. Since the char being introduced into the combustion zone will contain little volatile matter, it may be necessary to introduce supplementary fuel such as fresh coal, but only in sufficient amounts as required to maintain stability of ignition. The recirculation of char particles to the reductor 14 maintains a relatively high char particle density as compared to a once through scheme and, therefore, can be expected to react relatively rapidly with the gas stream. The gas stream into which they are introduced is also at the maximum temperature level available, thereby favoring the char to gas reaction. It is only after the gas temperatures in the reductor drops to a level at which the gasification is proceeding slowly that it is desirable to introduce the fresh coal for low temperature devolatilization purposes. The heat which is thereby used for devolatilization is the low level heat which would otherwise not be available for the gasification process. With a particular coal, introduction of all of the coal into the low temperature devolatilizer may not be the optimum situation. A portion of the coal may be introduced to the combustor outlet for several reasons. With a given air flow, and all the coal being gasified, the maximum heating value is obtained when the exit gas temperature is minimum, provided that the temperature reduction is due to the gasification process and not to heat exchange to other surfaces. It is essential to the invention that at least some of the fresh coal be introduced to the low temperature devolatilizing zone. Desirable limits on the amount may be established by either the char recirculating load or by the gasifier capacity. With the low temperature devolatilization a very small amount of the char is gasified. It follows that this char must be recirculated to the gasifier, thereby tending toward a high char recirculation load. On the other hand, with high temperature devolatilization conditions at the combustor outlet, a larger portion of the carbon content of any coal introduced at this location is immediately volatilized. Furthermore, the remaining carbon is partially gasified since it passes through the reductor zone. It is noted, however, that the temperature of the gas leaving the combustor is reduced because of the devolatilization of the coal, and this accordingly reduces the gas temperature available for the initial char gasification reactions. With excessive amounts of coal to the low temperature devolatilizer recirculation of char may exceed the capacity of the char handling equipment, or produce excessive draft loss in the gasifier. This may be reduced by diverting a portion of the fresh coal to the reductor section. The net effect of the offsetting phenomena occurring with introduction of a particular coal cannot be predicted at this time. Introduction of coal at the reduction zone inlet reduces the amount of char to be reacted, but also reduces the ability to react the char. With a fixed gasifier size and a particular coal an optimum utilization of the volume is expected with a fixed ratio of coal at the low temperature and high temperature sections. This ratio must be determined by experiment. If the desired limit on introduction of fuel to the low temperature devolatilizer is reached, a portion of the coal supply is diverted through line 48 and controlled by feeder 50 for introduction at the upstream end of the reductor 14. This is introduced immediately after the combustor and before introduction of the char. One method of controlling such introduction involves regulating coal through feeder 50 to maintain a temperature at the reductor outlet 34 and regulating coal through feeder 38 to maintain temperature leaving the low temperature devolatilizer 16. The method of regulating the ratio of recycled char and air to obtain a preselected temperature at the combustor outlet may be carried out by the control apparatus which is schematically illustrated. The temperature sensor 51 emits a control signal through control line 52 which is compared at set point 54 to the desired temperature signal. A control signal representing the error passes through control line 56 to ratio controller 58. One control signal passes through control line 60 to controller 62 which regulates the speed of feeder 24. Another control signal of the opposite direction passes through control lines 64 to controller 66 which regulates the flow of air. The gas temperature leaving the reductor section 14 may be controlled by measuring the exit temperature with temperature sensor 68. A control signal passes through control line 70 and is compared with a desired temperature signal at set point 72. An error signal passes through line 74 to controller 76 which operates to vary the speed of feeder 50 to regulate the introduction of fresh coal into the reductor. In a similar manner, the temperature leaving the low temperature devolatilization zone 16 is sensed by temperature sensor 78 which sends a control signal through control line 80. This signal is compared at set point 82 to the desired temperature signal with an error signal passing through line 84 to controller 86. This controller varies the speed of feeder 38 to regulate the amount of fuel introduced into the low temperature devolatilization zone.
An entrained flow coal gasifier wherein a high temperature product gas stream is essentially formed by burning char with air. Additional char, formed by partial gasification of coal, is added immediately thereafter to obtain the gasification reaction. Fresh coal is thereafter supplied in a lower temperature region thereby obtaining the volatile components driven off at a relatively low temperature.
2
RELATED APPLICATION DATA [0001] This application claims priority of U.S. Provisional Application No. 60/706,176 filed on Aug. 5, 2005, and U.S. Provisional Application No. 60/709,348 filed on Aug. 18, 2005, both of which are incorporated herein by reference in their entirety. FIELD OF THE INVENTION [0002] The present invention relates generally to liquid sensing arrangements and, more specifically, to utilizing thermal energy stored in fuel to maintain a temperature of an area or device. BACKGROUND OF THE INVENTION [0003] On aircraft composed of carbon fiber composite wings, the length of wiring to sensors in wing-mounted fuel tanks is kept as short as possible. This minimizes the threat of a lightning strike conducting a significant quantity of energy into the fuel tank. [0004] To minimize wiring length in the fuel tanks, several fuel level sensors in one or more fuel tanks connect to a local data concentrator device. This device, which is sometimes referred to as a remote data acquisition unit (RDAU) or remote data concentrator (RDC) (hereinafter referred to as an electronics module), is usually mounted just outside of the fuel tank on a spar. The electronics module has a sealed connector that passes through the tank wall, making electrical connections to sensors inside the fuel tank. The electronics module includes active electronic devices (often including a microprocessor) that have temperature ratings typically extending down to about minus forty degrees Celsius. [0005] During flight, the temperature on a wing spar can fall as low as minus seventy degrees Celsius, which is significantly lower than the rating of many electronic devices. When an electronics module, such as the RDAU, is mounted on a spar of an aircraft's wing and connected to sensors within the wing's fuel tank, the electronics module is subjected to the low temperatures encountered during flight (e.g., as low as minus seventy degrees Celsius). [0006] One approach to addressing these low spar temperatures is to add a heating element to the electronics module. The addition of the heating element, however, adds cost and complexity to the electronics module. Another approach has been to test all vulnerable electronic components at the minimum operating temperature seen at the spar. Then, only those components that can satisfactorily operate at these temperatures are used in the electronics module. Often, however, only a very small number of components can pass the test, resulting in low yields and, thus, increased costs. SUMMARY OF THE INVENTION [0007] The present invention provides a system, apparatus and method for maintaining an ambient temperature for a device located within a vehicle, in particular an aircraft. More specifically, thermal energy stored within the vehicle's fuel is utilized to maintain the ambient temperature within safe operating regions of the device. [0008] According to one aspect of the invention, there is provided a mount for coupling a device to a support structure in a vehicle, the vehicle including a fuel tank for storing fuel. The mount device includes a canister having at least one surface exposed to an inner portion of the fuel tank, the canister being impervious to the fuel. A cartridge is located inside the canister, the cartridge being in thermal communication with the at least one surface, wherein the cartridge includes the device. [0009] According to another aspect of the invention, there is provided a system for maintaining an ambient temperature of an area within an operational range of one or more devices located in the area. The system includes a fuel tank for storing fuel, and a heat exchanger operative to extract thermal energy from fuel stored in the fuel tank. [0010] According to another aspect of the invention, there is provided a method of mounting a device in a vehicle so as to maintain an ambient temperature around the device within an operation range of the device. The method includes the steps of: placing at least one surface of a canister in fluid communication with the fuel, wherein said canister is impervious to said fuel; placing a cartridge inside the canister such that the cartridge is in thermal communication with the fuel; and placing the device inside the cartridge. [0011] According to another aspect of the invention, there is provided a method of maintaining an ambient temperature for a device in a vehicle, including using thermal energy of fuel stored in the vehicle to heat or cool the device. [0012] According to another aspect of the invention, there is provided a mount for maintaining an ambient temperature of an area within an operational range of one or more devices located in the area. The mount includes a receptacle (e.g., a container or the like) extending into an interior of a fuel tank and opening to an exterior of the fuel tank, a sealed connector for establishing a through connection from the interior of the fuel tank to the interior of the receptacle, and a cartridge assembly insertable into the receptacle. [0013] To the accomplishment of the foregoing and related ends, the invention, then, comprises the features hereinafter fully described and particularly pointed out in the claims. The following description and the annexed drawings set forth in detail certain illustrative embodiments of the invention. These embodiments are indicative, however, of but a few of the various ways in which the principles of the invention may be employed. BRIEF DESCRIPTION OF THE DRAWINGS [0014] The forgoing and other embodiments of the invention are hereinafter discussed with reference to the drawings. [0015] FIG. 1 is an exemplary aircraft showing the location of fuel tanks and fuel sensors. [0016] FIGS. 2A and 2B are a front view and side view, respectively, of an exemplary canister of a mounting system in accordance with the invention. [0017] FIG. 3 is a side view of an exemplary cartridge in accordance with the invention, wherein an exemplary electronics module is shown inside the cartridge. [0018] FIG. 4 is a side view illustrating the canister, cartridge and electronics module mounted to a wing spar in accordance with the invention. [0019] FIG. 5 is a schematic diagram illustrating an exemplary power source for the electronics module. DETAILED DESCRIPTION [0020] Referring initially to FIG. 1 , an exemplary aircraft 10 includes a plurality of fuel tanks 12 mounted in wings 14 or other locations in the aircraft (not shown). Each fuel tank 12 includes one or more fuel sensors 16 for monitoring a fuel parameter, such as the fuel level or fuel temperature, for example. An electronics module 18 is mounted to a spar (not shown), and communicates to the fuel sensors 16 and other equipment. During flight, the wings 14 and spars within the wings 14 are exposed to extreme temperatures (e.g., about minus seventy degrees Celsius), which can be problematic for the fuel sensor's electronics module 18 . [0021] The present invention provides a system, apparatus and method for maintaining an ambient temperature for a device, such as the fuel sensor's electronics module 18 , so as to shield or isolate the module 18 from the extreme temperatures encountered during flight or while on the ground. Moreover, active heating elements or special testing of the electronics module's components are not required (although such devices and/or techniques may be utilized within the scope of the invention). As described herein, thermal energy of fuel stored in the vehicle is used to maintain the ambient temperature for the device such that it is substantially the same as the fuel (e.g., within about five to ten degrees Celsius). [0022] While the invention is described with respect to maintaining an ambient temperature for an electronics module, it will be appreciated that the invention may be used to maintain the ambient temperature for any device (electronic and non-electronic) or area. Further, while the invention is described in the context of an aircraft, it will be appreciated that it may be employed on any vehicle that utilizes relatively large fuel tanks, such as ships and locomotives, for example. [0023] According to one aspect of the invention, a canister is in contact with the aircraft fuel and impervious to the fuel. The canister operates as a heat exchanger and utilizes the thermal energy stored in the fuel to maintain an ambient temperature within the canister. As will be appreciated, other types of heat exchangers may be used in place of the canister without departing from the scope of the invention (e.g., a shell and tube heat exchanger, a plate heat exchanger, etc.). [0024] A cartridge is located within the canister, and the electronics module 18 is located in or on the cartridge. Both enclosures (i.e., the canister and cartridge) include sealed connectors that enable signals to enter and/or exit the respective enclosures while preventing fuel from entering the enclosures. By utilizing two enclosures, the thermal energy of the fuel can be easily used to maintain the temperature within both enclosures (and thus the electronics module 18 ), yet allow easy removal of the electronics module 18 without concern of fuel leakage or spillage. [0025] As used herein, a canister is defined as a container, such as a box, can, cylinder, or the like. A cartridge is defined as a small modular unit designed to be inserted into a larger piece of equipment, such as a canister. [0026] Referring now to FIGS. 2A and 2B , there is shown a front and side view of an exemplary canister 20 mounted to a wing spar 22 of aircraft 10 . As is conventional, the wing spar 22 defines a portion of a fuel tank 12 for holding fuel 24 . At least a portion of the canister 20 is in contact with the fuel 24 . Preferably, the canister 20 is located near a lower portion of the tank 12 so as to maintain contact with the fuel 24 for as long as possible as the fuel is consumed. Although the canister 20 is shown as a separate unit from the fuel tank 12 , the canister may be integrally formed with the fuel tank. [0027] The canister 20 comprises a cylindrical container having a diameter D and defined by circular bottom wall 20 a and cylindrical side wall 20 b, which also holds the canister 20 to the spar 22 . The canister includes a flange 20 d for interfacing with the spar 22 and is secured to the spare via fasteners 26 (e.g., screws or the like). A cover 20 c may be attached to the open end 20 e of the canister. The canister 20 may be made out of any material that is impervious to the fuel. Preferably, the canister 20 is formed from a light-weight material, such as aluminum, for example. Additionally, an insulation means may be included between the canister 20 and the spar 22 for galvanic or other reasons. [0028] The cover 20 c includes an opening 20 f that enables access into the canister 20 . The flange 20 d and/or cover 20 f provide a means of accepting fasteners 28 , which secure the cartridge 40 when mounted in the canister 20 . [0029] The bottom wall 20 a includes a hermetically sealed connector 30 , such as, for example, an electrical connector or fiber optic connector for communicating signals into and out of the canister 20 . For example, electrical or optical signals from fuel sensor 16 located within the fuel tank 12 can be provided to the interior of the canister 20 through the connector 30 , without fuel entering the canister 20 . [0030] Referring now to FIG. 3 , there is shown an exemplary cartridge 40 . The cartridge 40 is defined by circular top and bottom walls 40 a and 40 b, and cylindrical sidewall 40 c. The cartridge 40 is dimensioned so as to fit within the canister 20 . As will be appreciated, the cylindrical shape of the canister 20 and cartridge 40 is merely exemplary, and any shape may be utilized for the canister 20 and cartridge 40 . For example, the canister 20 may have a cylindrical shape and the cartridge 40 may have a rectangular shape, so long as the cartridge 40 fits within the canister 20 . [0031] Located within the cartridge 40 is an electronics module 18 . The electronics model 18 includes circuitry for performing conventional data acquisition and processing operations. For example, the electronics module 18 may include a number of integrated circuits, resistors, capacitors, etc. mounted on a printed circuit board and operative to exchange data between the fuel sensors 16 and a central controller (not shown) and/or to perform signal conditioning operations (e.g., signal filtering or the like). The electronics module 18 can be mounted to the top, bottom and/or sidewalls 40 a, 40 b or 40 c of the cartridge 40 using one or more mounting members 44 , such as fasteners and standoffs, for example. [0032] It is noted that the cartridge 40 may take on may different forms. For example, and as described above, the cartridge 40 may be a container wherein the electronics module 18 is mounted inside or on cartridge. Alternatively, the cartridge 40 may be a film, coating, or the like surrounding and/or formed over the electronics module 18 (e.g., the electronics module may be encased in an epoxy resin, or a thin coating may be formed over the outer surface of the electronics module 18 ). In another embodiment, the device itself may be the cartridge. [0033] The cartridge 40 also includes a first connector 46 and a second connector 48 . The first and second connectors 46 and 48 preferably are hermetically sealed connectors. This is advantageous, for example, in that if the connector 30 of the canister fails (e.g., it leaks), the fuel 24 will not be able to enter the interior of the cartridge 40 and contact the electronics module 18 . The first and second connectors 46 and 48 are couplable to the electronics module 18 so as to enable signals in/on the electronics module to be provided to other local or remote devices. For example, the first and second connectors 46 and 48 may be edge connectors that mate with corresponding edge portions of the electronics module's printed circuit board so as to provide an electrical connection to/from the electronics module 18 . As will be appreciated, any type of connecting means that enables signals to be transferred to/from the electronics module 18 and the canister 20 and cartridge 40 may be used. [0034] Further, the first connector 46 is couplable to the connector 30 of the canister 20 , thereby enabling signals to be transmitted and received from devices external to the canister 20 and cartridge 40 . For example, the connector 30 of the canister 20 may include a female receptacle (e.g., a fitting equipped to receive a plug or the like for facilitating an electrical connection), and the first connector 46 of the cartridge 40 may include a male plug that corresponds to the female receptacle. When the connectors 30 and 46 are coupled together, a connection (e.g. an electrical or optical connection) is made from the inside of the cartridge 40 to the outside of the canister 20 (e.g., from the electronics module 18 to the fuel sensors 16 located within the fuel tank 12 ). [0035] The second connector 48 extends through the top wall 40 c of the cartridge 40 and is coupled to a wiring harness or the like, which is couplable to the central controller. Via the second connector 48 , signals may be transmitted to and/or received from devices located outside the canister 20 and cartridge 40 . For example, data collected by the electronics module 18 may be communicated to an avionics control system (not shown) or the like. Similarly, data may be communicated from the avionics control system to the electronics module 18 and/or the fuel sensors 12 . Such data may be in the form of feedback signals (e.g., actual fuel temperature, level, etc.) or command signals (e.g., alarm setpoints). [0036] With further reference to FIG. 4 , the electronics module 18 and cartridge 40 are shown mounted in the canister 20 . As described above, the first connector 46 of the cartridge 40 mates with the connector 30 of the canister 20 . This connection provides a communication path from the electronics module 18 (which is inside the cartridge 40 ) to the fuel sensors 16 (which are in the fuel tank 12 outside of the canister 20 ). The cartridge 40 may be removed from and inserted into the canister 20 via opening 20 within the flange 20 d and cover 20 c (if present). [0037] As noted herein, the canister 20 is mounted near a bottom portion of the fuel tank 12 so as to immerse the canister 20 in fuel as long as possible. As the fuel is consumed, portions of the canister may become exposed and, as a result, the temperature of the canister 20 (and thus the cartridge 40 and electronics module 18 ) may approach that of the spar 22 and wing 14 . To slow this process (and keep the electronics module 18 from becoming too cold too quickly) thermal insulation 50 can be placed between the canister 20 and the spar 22 as show in FIG. 4 . Preferably, the thermal insulation 50 is electrically conductive so as provide protection against lighting strikes. Additionally, it is noted that if the canister 20 is mounted near a bottom portion of the fuel tank 12 , exposure of the canister (if at all) occurs when the flight is nearly complete. Thus, the temperatures encountered by the exposed canister 20 will be substantially higher than minus 70 degrees Celsius. [0038] As is known by those skilled in the art, lightning strikes can pose problems for aircraft electronics. To minimize the effects of lightning strikes, the electronics module 18 can be electrically isolated from the aircraft's frame ground, thereby providing enhanced protection against such strikes. For example, the electronics module 18 can be powered by an isolated power source. More specifically, and with reference to FIG. 5 , a high frequency AC power source 52 can be used to power the electronics module 18 . Preferably, the power source 52 operates on a frequency in the region of 10 KHz. The high frequency power source 52 is advantageous, for example, in that it allows the electronics module's power supply 18 a to remain electrically isolated from other aircraft electronics. The electrical isolation can be accomplished, for example, using a small, lightweight ferrite transformer 52 a in or near the power source 52 . Additionally, by utilizing the high frequency power source 52 , the power requirements of the electronics module 18 are simplified, thereby reducing the size and weight of the electronics module 18 . The ferrite transformer 42 a is designed to provide intrinsic safety, and forms part of the intrinsic safety barrier. Intrinsic safety of digital signals can be provided by optical isolation 52 b. The electronics that interface with the in-tank sensors through connectors 46 and 30 are thus completely electrically isolated. Note that direct current power can be used, but additional circuitry would be required to provide the high frequency excitation for the ferrite transformer 52 a. [0039] Accordingly, an ambient temperature can be maintained for a device, such as an electronics module, using thermal energy stored in fuel. The thermal energy may be extracted via a mounting system that includes at least two enclosures, wherein one of the enclosures is in contact with the fuel and the other enclosure is in thermal communication with the fuel. As will be appreciated, other techniques of extracting the thermal energy from the fuel may be employed without departing from the scope of the invention. [0040] Although the invention has been shown and described with respect to a certain preferred embodiment or embodiments, it is obvious that equivalent alterations and modifications will occur to others skilled in the art upon the reading and understanding of this specification and the annexed drawings. In particular regard to the various functions performed by the above described elements (components, assemblies, devices, compositions, etc.), the terms (including a reference to a “means”) used to describe such elements are intended to correspond, unless otherwise indicated, to any element which performs the specified function of the described element (i.e., that is functionally equivalent), even though not structurally equivalent to the disclosed structure which performs the function in the herein illustrated exemplary embodiment or embodiments of the invention. In addition, while a particular feature of the invention may have been described above with respect to only one or more of several illustrated embodiments, such feature may be combined with one or more other features of the other embodiments, as may be desired and advantageous for any given or particular application.
A mount for coupling a device to a support structure in a vehicle, the vehicle including a fuel tank for storing fuel, includes a canister having at least one surface insertable into the fuel tank so as to contact the fuel, the canister being impervious to the fuel. A cartridge is removably insertable into the canister, the cartridge being in thermal communication with the at least one surface, wherein the cartridge includes the device.
1
BACKGROUND OF THE INVENTION A. Field of the Invention The present invention relates to a method for replacing an existing refrigerant in a centrifugal compressor while maintaining or modifying the performance of the centrifugal compressor. B. Description of the Related Art Typically, centrifugal compressors are designed by selecting a gear arrangement which will provide the desired impeller speed and impeller Mach number when used in combination with a predetermined refrigerant. Impeller Mach number is the tip speed of the impeller divided by the acoustical velocity of the refrigerant. The acoustical velocity is the speed of sound in the refrigerant vapor. A current problem which arises with centrifugal compressors is that commonly used refrigerants, such as R11, are fully halogenated chlorofluorocarbons (CFCs). Fully halogenated CFCs are a class of compounds which can adversely affect the environment, such as by depleting the ozone layer. Therefore, it is desirable to replace existing refrigerants, such as R11, with more environmentally acceptable refrigerants. Suitable replacement refrigerants often do not have the same molecular weight as the existing refrigerant. Because the acoustical velocity of the refrigerant is related to the molecular weight of the refrigerant, the impeller Mach number will be altered if a refrigerant having a different molecular weight is utilized in the centrifugal compressor If the replacement refrigerant has a molecular weight higher than that of the existing refrigerant, the acoustical velocity of the replacement refrigerant will be lower than the acoustical velocity of the existing refrigerant. Therefore, the impeller Mach number will be higher with the replacement refrigerant than with the existing refrigerant. Alternatively, if the replacement refrigerant has a molecular weight lower than that of the existing refrigerant, the impeller Mach number of the centrifugal compressor will be lower with the replacement refrigerant. Increasing or decreasing the impeller Mach number of the centrifugal compressor will place the operating point in an inefficient region of the compressor map. In other words, the centrifugal compressor will be placed in an inefficient operating condition. Known ways to maintain centrifugal compressor performance while replacing the existing refrigerant are to alter the gear arrangement to enable the centrifugal compressor to operate efficiently while using the replacement refrigerant, or make structural modifications to the centrifugal compressor. For example, by changing the gear arrangement, the speed of the impeller can be slowed, thereby adjusting the impeller Mach number to provide better efficiency. Such methods are expensive and also have other disadvantages which will be discussed later. There are also circumstances where it would be desirable to modify the performance of an existing centrifugal compressor. Currently, one way of accomplishing this is to make structural modifications to the centrifugal compressor, but, as discussed above in regard to maintaining compressor performance, this is an unsatisfactory method due to the cost, as well as the loss of the availability of the compressor. SUMMARY OF THE INVENTION An object of the invention is to provide a method for replacing the existing refrigerant in a centrifugal compressor without having to change the gear arrangement or make other structural modifications to the centrifugal compressor. Another object of the invention is to provide such a method whereby the performance of the centrifugal compressor can be maintained or modified without having to change the gear arrangement or make other structural modifications to the centrifugal compressor. Additional objects and advantages of the invention will be set forth in part in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention. The objects and advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. To achieve the objects and in accordance with the purpose of the invention, as embodied and broadly described herein, the invention comprises a method for replacing an existing refrigerant in a centrifugal compressor, the method comprising the steps of selecting a desired impeller Mach number for the centrifugal compressor, selecting a base refrigerant constituent, combining at least one additive refrigerant constituent with the base refrigerant constituent to form a replacement refrigerant having at least one physical or chemical difference from the existing refrigerant and providing a desired impeller Mach number in the centrifugal compressor, and replacing the existing refrigerant with the replacement refrigerant. In typical applications, the method of the present invention allows the existing refrigerant to be replaced while maintaining substantially the same impeller Mach number. Instead of altering the gear arrangement or compressor structure to change the centrifugal compressor speed, the acoustical velocity of the refrigerant is changed to give the desired impeller Mach number. This alternative allows the centrifugal compressor performance to be maintained without making expensive changes to the centrifugal compressor. The method of the present invention also allows the performance of the centrifugal compressor to be modified without altering the gear arrangement or requiring other structural modifications to the centrifugal compressor. The present invention also allows for the replacement of the existing refrigerant with a less expensive or a less environmentally damaging replacement refrigerant without altering the performance of the centrifugal compressor. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the invention and together with the description, serve to explain the principles of the invention. FIG. 1 is a graphic illustration of acoustical velocity versus isopentane content for R123/isopentane refrigerant mixtures. FIG. 2 is a compressor map highlighting an embodiment of the invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS Reference will now be made in detail to the presently preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings. The present invention provides a method for replacing an existing refrigerant with a replacement refrigerant while maintaining or modifying centrifugal compressor performance. One aspect of the present invention is formulating the desired composition of the replacement refrigerant to obtain the desired performance. The acoustical velocity (A) of a refrigerant is determined by the following formula: ##EQU1## where C p =the constant pressure specific heat (J/kg.sup.. K) C v =the constant volume specific heat (J/kg.sup.. K) R=the specific gas constant (J/kg.sup.. K) T=the temperature (degrees Kelvin) W=the molecular weight of the refrigerant vapor In accordance with the above equation, the acoustical velocity of the refrigerant operating within a given narrow temperature range is a direct function of the inverse of the square root of the average molecular weight of the refrigerant. Therefore, changing the molecular weight of the refrigerant mixture alters the acoustical velocity of the refrigerant and thus changes the impeller Mach number of the centrifugal compressor. When utilizing the method of the invention, centrifugal compressor performance can be maintained or modified by adjusting the composition of the replacement refrigerant without the necessity of altering the gear arrangement or making other structural modifications to the centrifugal compressor. In order to maintain the centrifugal compressor performance while replacing the existing refrigerant, the predetermined impeller Mach number should be the same as that achieved by the existing refrigerant. Because molecular weight is related to acoustical velocity and acoustical velocity determines impeller Mach number, performance can be maintained by formulating a replacement refrigerant which has the same molecular weight as the existing refrigerant, or which has a molecular weight which theoretically will provide the same impeller Mach number as the original refrigerant. The performance can more accurately be maintained by formulating a replacement refrigerant which has the same acoustical velocity as the original refrigerant, or which has an acoustical velocity which theoretically will provide the same impeller Mach number as the existing refrigerant. The performance can most accurately be maintained by formulating a replacement refrigerant which provides the same impeller Mach number when in use in the centrifugal compressor as the impeller Mach number which was provided by the existing refrigerant. Similar to maintaining original performance, a desired different performance can be achieved by formulating a replacement refrigerant having a molecular weight which theoretically will provide the desired impeller Mach number. The desired results can more accurately be achieved by formulating a replacement refrigerant having an acoustical velocity which theoretically will provide the desired impeller Mach number. The desired results can most accurately be achieved by formulating a replacement refrigerant which actually provides the desired impeller Mach number when in use in the centrifugal compressor. When replacing the existing refrigerant, it is important that the replacement refrigerant is as close as possible to an azeotrope so as to avoid problems associated with fractional distillation. The composition of the replacement refrigerant must be approximately the same in the vapor state and the liquid state. Preferably the replacement refrigerant should be completely azeotropic. However, it is acceptable for the replacement refrigerant to be only substantially azeotropic. If the replacement refrigerant is not completely azeotropic, it is desired that any flammable constituents have a boiling point lower than that of the nonflammable constituents to ensure that any leaks do not eventually result in a flammable mixture. If the nonflammable constituents have a boiling point lower than that of the flammable constituents, the nonflammable constituents will transform into the vapor phase before the flammable constituents, should a leak occur. Therefore, the nonflammable constituents will escape from the centrifugal compressor and be dispersed into the atmosphere, and a higher concentration of flammable constituents will remain in the centrifugal compressor. This will create a safety hazard. On the other hand, if the flammable constituents have a boiling point lower than that of the nonflammable constituents, the flammable constituents will escape into the atmosphere and be safely dispersed. A higher concentration of nonflammable constituents will remain in the centrifugal compressor. The nonflammable constituents will not create a safety hazard. Preferably, the replacement refrigerant is nonflammable, low in toxicity, capable of operating at the pressure at which the centrifugal compressor is to be operated, and is readily available. In addition, the constituents should not chemically react under load conditions. The invention will be further clarified by the following example, which is intended to be purely exemplary of the invention. R11 is an environmentally unacceptable refrigerant because it is a fully halogenated CFC. Therefore, it is necessary to replace the R11 refrigerant with a more environmentally safe replacement refrigerant. In order to maintain the operating condition of the centrifugal compressor, it is necessary to utilize a replacement refrigerant which has a molecular weight close to that of R11. R123 and R123a are suitable replacement refrigerants. Both R123 and R123a are low in toxicity, having projected threshold limit values of 100 ppm and 300 ppm, respectively. R123 and R123a have the same molecular weight, which means the acoustical velocity of each is approximately the same. However, the molecular weights of R123 and R123a are higher than that of R11, and thus the acoustical velocities of R123 and R123a are lower than the acoustical velocity of R11. The lower acoustical velocities of R123 and R123a means that the impeller Mach number of the centrifugal compressor will be higher with R123 or R123a than with R11. Simply replacing R11 with R123 or R123a will place the centrifugal compressor in an inefficient operating condition. In order to prevent inefficient operation of the centrifugal compressor, a small amount of refrigerant material with a lower molecular weight must be added to the R123 or R123a to decrease the molecular weight of the replacement refrigerant, which increases its acoustical velocity, and, thereby, lowers the impeller Mach number of the centrifugal compressor. It is desirable to find an additive constituent to combine with R123 or R123a which has a molecular weight lower than that of R123 and R123a and which, when in combination with R123 or R123a, will form a substantially azeotropic replacement refrigerant over a wide range of possible compositions, so as to avoid problems associated with fractional distillation. There are a variety of materials that have boiling points close to that of R123 and R123a which can be considered for forming a replacement refrigerant. Table 1 lists R11, R123, R123a and other possible additive constituents for forming a replacement refrigerant for R11. TABLE 1__________________________________________________________________________R11 and Possible Constituents ForForming Replacement Refrigerants Vapor Vapor Weight % Weight % R123 Boil- R123 Needed Molec- ing Needed to Give ular Point to Match Non-FlammableMaterial Formula Weight (°C.) R11 Mach Mixture__________________________________________________________________________R11 CCl.sub.3 F 137.5 24 0% 0%R123 CHCl.sub.2 CF.sub.3 153 27.9 -- --R123a CHClFCF.sub.2 Cl 153 29.9 -- --isopentane (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.3 72 27.9 90% ˜90%R141b CH.sub.3 CFCl.sub.2 117 32 63% 30%R152 CFH.sub.2 CFH.sub.2 66 30 91% <75%E143 CFH.sub.2 OCF.sub.2 H 100 30.1 79% <75%__________________________________________________________________________ As shown in Table 1, isopentane, R141b, R152, and E143 each has a molecular weight lower than that of R123 and R123a, and could be combined with R123 or R123a to form a replacement refrigerant with a molecular weight or an acoustical velocity which matches that of R11. A presently preferred replacement for R11 is a mixture of R123 and isopentane. Isopentane has a relatively low toxicity with a threshold limit value of 600 ppm. Therefore, the replacement refrigerant formed by the mixture of R123 and isopentane has a low toxicity with a threshold limit value greater than that of pure R123. Fractional distillation is not a problem because the boiling point of isopentane is the same as that of R123. FIG. 1 shows the acoustical velocity of R123/isopentane mixtures versus the percentage of isopentane in the mixture. A mixture of 92% R123 and 8% isopentane provides a replacement refrigerant having a molecular weight of 140.4 and an acoustical velocity of approximately 431 ft/sec. The flammability of the replacement mixture is an area of concern. It is necessary to provide a sufficient amount of R123 to ensure a nonflammable R123/isopentane mixture. Other CFC/hydrocarbon mixtures are nonflammable only until the CFC reaches a limit of roughly 10% by weight of the hydrocarbon. If this limit holds for R123/isopentane mixtures, the amount of isopentane necessary to raise the acoustical velocity of the replacement refrigerant to that of R11 is very close to the flammability limit. FIG. 2 is a compressor map which plots the head factor versus the capacity factor for an exemplary centrifugal compressor. The dimensionless head factor (Ω) and the dimensionless capacity factor (Θ) are determined by the following equations: ##EQU2## where H=head (ft lbf/lbm) g c =unit conversion constant=32.2 lbm ft/sec 2 /lbf A=the acoustical velocity of the refrigerant (ft/sec) S=volumetric flow rate at compressor suction (ft3/sec) D=the impeller diameter (ft) The original design condition, the operating point of the centrifugal compressor when using R11, is shown at point 1. Point 2 indicates the approximate operating point of the centrifugal compressor when using a pure R123 replacement refrigerant. Point 3 is the approximate operating point when using a 92% R123 and 8% isopentane replacement refrigerant. Point 4 is the approximate operating point when using a pure R123 replacement refrigerant and changing the gear arrangement to give a desired impeller Mach number (M). Table 2 summarizes the results. TABLE 2__________________________________________________________________________Comparison Between R11, Pure R123, And A R123/Isopentane Mixture % of % of design % of % of design A compressor design design chillerPoint Refrigerant rpm (ft/s) % M % Ω % θ eff. tons hp efficiency__________________________________________________________________________1 R11 9330 440 100 100 100 100 100 100 1002 R123 9330 412 107 109 107 89 84 96 873 92% 9330 430 102 109 101 100 83 85 98 R123/8% isopentane4 R123 8940 412 102 109 101 100 80 82 98__________________________________________________________________________ Replacing R11 with pure R123 results in approximately a 16% loss in capacity and a 13% penalty in efficiency. Using a mixture of 92% R123 and 8% isopentane in place of R11, gives approximately a 17% loss in capacity, but maintains substantially the same efficiency. Using pure R123 and changing the gear arrangement to give a desired impeller Mach number provides the same efficiency as the R123/isopentane mixture, but results in 3% less capacity. Therefore, the R123/isopentane mixture provides more capacity, as well as dispensing with the need for costly gear replacement. A preferred embodiment comprises R123 in the range of about 85 to 99% by mass and isopentane in the range of about 1 to 15% by mass. A more preferred embodiment comprises R123 in the range of about 90 to 94% by mass and isopentane in the range of about 6 to 10% by mass. While these results are for a R123/isopentane mixture, similar results would be achieved with any additive to R123 which provides a mixture having the requisite molecular weight as well as satisfying the other requirements. A R123/R141b replacement refrigerant, which satisfies the operating requirements, would contain over two times the amount of R123 as is necessary to make the replacement refrigerant nonflammable. However, R141b is the flammable constituent and its boiling point is higher than that of R123, which means that leaks may eventually result in a flammable mixture in the centrifugal compressor. However, R123a has a boiling point which is closer to R141b, thereby decreasing the possibility of a flammable mixture for R123a/R141b mixtures. Therefore, R123a/R141b is a viable mixture for forming a replacement refrigerant. Another possible replacement refrigerant is a mixture of R152 with either R123 or R123a. A preferred embodiment comprises R123a in the range of about 85 to 99% by mass and R152 in the range of about 1 to 15% by mass. A more preferred embodiment comprises R123a in the range of about 90 to 95% by mass and R152 in the range of about 5 to 10% by mass. Additionally, E143 can be combined with either R123 or R123a to form a replacement refrigerant. R152 and E143 each has a boiling point that is virtually the same as that of R123a, so that fractional distillation will not create a problem. However, neither R152 or E143 is likely to be available in the near future because it would take approximately 10 years to complete toxicity testing and build production facilities. Only very limited toxicity and stability data is available for these materials. The following example, which is intended to be purely exemplary of the invention, illustrates the replacement of the existing refrigerant with a replacement refrigerant in order to modify the performance of the centrifugal compressor. The first step in modifying the performance of a centrifugal chiller is to determine the impeller Mach number which will provide the desired results. Modification of the centrifugal compressor performance can then be achieved without gear replacement by replacing the existing refrigerant with a replacement refrigerant having a molecular weight or acoustical velocity which will provide the desired impeller Mach number when in use in the compressor. Various replacement refrigerant compositions can be tested in the centrifugal compressor to determine which composition actually provides the desired impeller Mach number. Another embodiment of the invention illustrates possible replacements for R12. Table 5 lists R12 and various possible constituents for forming a replacement refrigerant therefor. TABLE 5______________________________________R12 and Possible Constituents ForForming Replacement Refrigerants Vapor Weight % R134a Boiling Needed Molecular Point to MatchMaterial Formula Weight (°C.) R12 Mach______________________________________R12 CF.sub.2 Cl.sub.2 121 -30 0%RC216 CF.sub.2 CF.sub.2 CF.sub.2 150 -31 49R134a CH.sub.2 FCF.sub.3 102 -27 --______________________________________ The method for maintaining or modifying the centrifugal chiller performance while replacing R12 is the same as for R11 and involves the consideration of similar factors to form a suitable replacement refrigerant. One currently preferred replacement for R12 is a mixture of RC216 and R134a. A preferred embodiment comprises R134a in the range of about 30 to 70% by mass and RC216 in the range of about 30 to 70% by mass. A more preferred embodiment comprises R134a in the range of about 45 to 55% by mass and RC216 the range of about 45 to 55% by mass. It will be apparent to those skilled in the art that various modifications and variations can be made in the method of the present invention without departing from the scope or spirit of the invention. For example, the existing refrigerant can be the refrigerant for which the centrifugal compressor was designed or the refrigerant which is actually in use in the centrifugal compressor. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
A method for substituting a replacement refrigerant for an existing refrigerant in a centrifugal compressor includes the steps of selecting a desired impeller Mach number for the centrifugal compressor, selecting a base refrigerant constituent, combining at least one additive refrigerant constituent with the base refrigerant constituent to form a replacement refrigerant having at least one physical or chemical property different from the existing refrigerant and substantially providing the desired impeller Mach number in the centrifugal compressor, and replacing the existing refrigerant with the replacement refrigerant. The existing refrigerant can be replaced by choosing a particular molecular weight or acoustical velocity which will provide the desired impeller Mach number.
2
This application claims the benefit under 35 U.S.C. § 119(e) of the U.S. provisional patent application No. 60/401,369 filed Aug. 6, 2002. TECHNICAL FIELD The present invention relates to sheetmetal forming apparatus and more particularly to apparatus that forms bends in rectangular tubing. BACKGROUND ART Rectangular tube is used, for example, in downspouts connected to rain gutters to selectively transport rain water downward. Such downspouts often bend inwardly to a building wall from the rain gutter at the eave, then bend downwardly to extend down the wall and then bend outwardly from the wall. Downspouts may require additional bends, as for example, when a lower portion of a wall juts out beyond an upper portion of the wall. It is generally possible to fashion most downspout systems from straight sections of tube combined with mass produced elbows. However, more reliable and esthetically pleasing systems can be built by custom bending tube on site. Rectangular tube is typically bent by a plurality of spaced folds on three sides of the tube. Apparatus for creating the folds includes a female die with an annular groove inside the tube and a toggle assembly with male dies that crimp three sides of the tube into the annular groove. A carriage assembly pushes the tube, folding the crimped portion of tube in the annular groove to form the fold. The bend is formed by alternating crimping and advancing steps. Consistent, esthetic bends require uniform advancement of the carriage assembly between folds. Examples of motorized bending apparatus are disclosed in U.S. Pat. No. 3,670,553 to Nothum et al. and U.S. Pat. No. 3,861,184 to Knudson. Nothum et al. uses a rotating cam and a ratchet mechanism with a rack on the carriage assembly to uniformly advance the tube. Knudson uses an eccentric roller, star follower and a pinion that engages a rack on the carriage assembly to uniformly advance the tube. Manually operated apparatus that is simpler and more portable may be more desirable than motorized apparatus for on site tube bending. U.S. Pat. No. 4,198,842 to Pawlaczyk discloses a manually operated tube bending apparatus with a first handle actuating a toggle assembly and a second handle with a ratchet mechanism connected through a series of gears on the frame and a chain to actuate a carriage assembly. Pawlaczyk does not explicitly disclose any means for assuring uniform advancement of the tube and the second handle must be turned through several rotations to return the carriage assembly to the start position after a tube is bent. U.S. Pat. No. 5,836,194 to Micouleau et al. discloses a manually operated tube bending apparatus with a single handle actuating a toggle assembly and a carriage assembly. The carriage assembly is advanced by an advancing ratchet mechanism with a rack on the carriage assembly that is released when the carriage assembly reaches a forward limit. Precise adjustment of the male dies relative to the female was required in the prior known tube bending/crimping apparatus. The rack on the carriage assemblies of Nothum et al., Knudson, and Micouleau et al. makes each carriage assembly relatively long and thereby the apparatus relatively long. Nothum et al., Knudson, and Pawlaczyk each use a mandrel on the carriage assembly that receives the end of a tube. Such mandrels have to be changed or adjusted for each different size and orientation of tube. A simpler, more compact apparatus than the prior known apparatus would be easier to transport to a work site. Manual apparatus with a carriage assembly that advances a consistent distance and that can easily be moved back to the starting position without multiple turns of a handle is more efficient for an operator to use. A receiving element that receives several sizes and orientations of tube without change or adjustment is also desirable. DISCLOSURE OF THE INVENTION Tube crimping/bending apparatus includes a frame, a carriage assembly movably mounted on the frame, and a toggle assembly. The frame has a base, spaced front and rear plates extending up from the base, a rack connected to the rear plate and extending to the front plate, and a female die, with an annular groove, mounted on the front of the rack. The carriage assembly has a receiving element, a laterally extending carriage shaft carried by the receiving element, a carriage handle, a means for coupling the carriage handle to the carriage shaft, and means for limiting rotation of the carriage handle that provides uniform advancement. The receiving element has grooves that receive several sizes and orientations of tube. The rack extends through an aperture in the receiving element and engages a pinion on the carriage shaft. The means for coupling in a first configuration engages the carriage handle to the carriage shaft in one direction and releases the carriage shaft from the carriage handle in the other direction, and in a second configuration allows the carriage shaft to rotate freely in both directions relative to the carriage handle. The toggle assembly mounts on the front plate and includes a top toggle plate, opposed side toggle plates linked to the top toggle plate, a male die on each of the top and side toggle plates, and a toggle handle that actuates the top and side toggle plates to push the male dies into the annular groove of the female die. The male dies have overlapping working tips that taper to form a self-centering wedge. BRIEF DESCRIPTION OF THE DRAWINGS Details of this invention are described in connection with the accompanying drawings that bear similar reference numerals in which: FIG. 1 is a perspective view of a tube crimping/bending apparatus embodying features of the present invention, with the dies removed. FIG. 2 is a front elevation view of the apparatus of FIG. 1 . FIG. 3 is a view side elevation of the apparatus of FIG. 1 . FIG. 4 is a top plan view of the apparatus of FIG. 1 . FIG. 5 is a front perspective view of the carriage assembly of the apparatus of FIG. 1 . FIG. 6 is a rear perspective view of the carriage assembly of the apparatus of FIG. 1 . FIG. 7 is an exploded front perspective view of the carriage assembly of the apparatus of FIG. 1 . FIG. 8 is a perspective view of the dies of the apparatus of FIG. 1 in the open position. FIG. 9 is a front view of the dies of FIG. 8 in the closed position. FIG. 10 is a sectional view taken along line 10 — 10 of FIG. 9 . FIG. 11 is an enlarged partial view of FIG. 10 . DETAILED DESCRIPTION OF THE INVENTION Referring to FIGS. 1 to 4 , tube crimping/bending apparatus 11 embodying features of the present invention includes a frame 14 , a carriage assembly 15 and a toggle assembly 16 . The frame 11 has a rectangular, U shaped, sheet metal base 19 , a substantially rectangular front plate 20 rigidly mounted on and extending upward from the front of the base 19 , and a spaced, substantially rectangular back plate 21 rigidly mounted on and extending upward from the back of the base 19 . Describing the specific embodiments herein chosen for illustrating the invention, certain terminology is used which will be recognized as being employed for convenience and having no limiting significance. For example, the terms “front”, “back”, “right”, “left” “vertical”, “horizontal, “lateral”, “longitudinal”, “upper” and “lower” refer to the illustrated embodiment in its normal position of use. The terms “inward” and “outward” refer to directions toward and away from the geometric center of the apparatus. Further, all of the terminology above-defined includes derivatives of the word specifically mentioned and words of similar import. Side plates 22 extend upward along opposite sides of the base 19 from the front plate 20 to the back plate 21 . A rectangular tube opening 23 , spaced above the base 19 , extends through the front plate 20 and is sized to receive various sizes of tube. An elongated, toothed carriage rack 26 is affixed to the back plate 21 opposite the tube opening 23 , and extends forwardly through the tube opening 23 . A forwardly extending pin 27 and a threaded hole 28 , below the pin 27 , are provided on the front end of the carriage rack 26 , for mounting a female die, as will be described hereinafter. Parallel, spaced, horizontal support rods 30 , on opposite sides of the carriage rack 26 , extend between and are rigidly attached to the front and back plates 20 and 21 . An elongated limit bar 31 is spaced above the carriage rack 26 and rigidly attaches at opposite ends to the front and back plates 20 and 21 . A plurality of uniformly spaced limit holes 32 extend vertically through the limit bar 31 . A limit pin 33 is provided that fits through the limit holes 32 and extends downward below the limit bar 31 . The carriage assembly 15 , as shown in FIGS. 5 , 6 and 7 , includes a receiving element 40 , a carriage shaft 41 , a carriage handle 42 , a means for coupling 43 , that couples the carriage handle 42 to the carriage shaft 41 , and a means for limiting 44 , that limits the stroke of the carriage handle 42 . The receiving element 40 is a substantially rectangular, vertical plate. The receiving element 40 slidably mounts on the frame 14 , under the limit bar 31 , with the carriage rack 26 extending through a horizontal rack aperture 47 that extends through a lower middle portion of the receiving element 40 , and the support rods 30 extending through linear bearings 48 that extend through the receiving element 40 on opposite sides of the rack aperture 47 . A rack guide 50 rigidly mounts to the back of the receiving element 40 below the rack aperture 47 . A plurality of tube receiving grooves 49 , sized and shaped to receive the ends of various sizes and orientations of rectangular tube, are cut into the front of the receiving element 40 around the rack aperture 47 . Spaced, vertical, rearwardly extending right and left carriage side plates 52 and 53 rigidly attach to the back of the receiving element 40 . Aligned carriage shaft bearings 54 extend through the right and left carriage side plates 52 and 53 and aligned stop rod apertures 55 extend through the right and left carriage side plates 52 and 53 , rearward of the carriage shaft bearings 54 . The carriage shaft 41 rotably mounts in the two carriage shaft bearings 54 and extends rightwardly from the right carriage side plate 52 to a carriage shaft right end 57 . A toothed carriage pinion 58 on the carriage shaft 41 , between the right and left carriage side plates 52 and 53 , is keyed or otherwise fixed on the carriage shaft 41 so that the carriage shaft and pinion 41 and 58 rotate together. The carriage pinion 58 is positioned to engage the carriage rack 26 so that when the carriage shaft 41 turns, the carriage assembly 15 moves forwardly or rearwardly on the frame 14 . A cam clutch 60 fits over the carriage shaft 41 , between the right carriage side plate 52 and carriage shaft right end 57 , engaging the carriage shaft 41 when turned in a counter-clockwise direction as viewed from the right side of the tube crimping/bending apparatus 11 while turning freely relative to the carriage shaft 41 when turned clockwise. A hollow, cylindrical cup 61 fits over and is keyed to the cam clutch 60 , and has a right facing, annulus shaped cup face 62 with a plurality of spaced, radially arranged plunger holes 63 that extend into the cup 61 . The carriage handle 42 has a straight, elongated lever arm 65 . A pair of opposed handle bearings 66 extend through the lever arm 65 near one end and a transversely extending hand grip 67 attached to the opposite end of the lever arm 65 . The handle bearings 66 fit onto the carriage shaft 41 , between the cup 61 and carriage shaft right end 57 , so that the carriage handle 42 and carriage shaft 41 rotate freely relative to each other. The handle bearings 66 are secured on the carriage shaft 41 by a fastener 68 on the carriage shaft right end 57 . A cylindrical plunger 69 slidably extends through the lever arm 65 near the handle bearings 66 , and is sized and positioned to fit into the plunger holes 63 , so that when the plunger 69 engages one of the plunger holes 63 , rotation of the carriage handle 42 rotates the cup 61 and the cam clutch 60 . The plunger 69 is biased leftward, toward the cup face 62 , but can be pulled rightward, away from the cup face 62 , to disengage or decouple the carriage handle 42 from the cam clutch 60 . A cylindrical ring 71 fits around the cup 61 , between the right carriage side plate 52 and the lever arm 65 , and rotates freely relative to the cup 61 . The ring 71 has a right face 72 and a spaced left face 73 , with the right face 72 being rigidly attached to the lever arm 65 . A curved stop groove 75 of a selected length extends into the left face 73 and has a first end 77 and a spaced second end 81 . A stop rod 76 extends through the stop rod apertures 55 of the right and left carriage side plates 52 and 53 , and rightwardly from the right carriage side plate 52 into the stop groove 75 , limiting rotation of the carriage handle 42 in the clockwise and counter-clockwise directions. The means for coupling 43 , in the illustrated embodiment, includes the cam clutch 60 , cup 61 , and plunger 69 . When the plunger 69 is engaged, rotation of the carriage handle 42 in the counter-clockwise direction advances the carriage assembly 15 and the carriage handle 42 rotates freely relative to the carriage shaft 41 in the clockwise direction. When the plunger 69 is disengaged, the carriage assembly 15 is easily pushed rearward. Other suitable mechanisms for the means for coupling 43 , may include, by way of example and not as a limitation, a ratchet and sliding gear. The means for limiting 44 , in the illustrated embodiment, includes the stop rod 76 and the stop groove 75 in the ring 71 . Other suitable means for limiting 44 may include, by way of example and not as a limitation, stop pins that directly engage the lever arm 65 at opposite ends of the desired stroke. Referring again to FIGS. 1 to 4 , the toggle assembly 16 includes a top toggle plate 78 , right and left toggle plates 79 and 80 , a top, right and left male dies 82 , 83 and 84 mounted on the top, right and left toggle plates 78 , 79 and 80 , respectively, and a means for actuating 86 , that actuates the top, right and left male dies 82 , 83 and 84 to crimp a tube. The top toggle plate 78 mounts on the front of the front plate 20 of the frame 11 , above the tube opening 23 , in a vertically slidable fashion and is biased upward. The top toggle plate 78 has a laterally elongated, substantially rectangular shape, extending rightward and leftward of the front plate 20 of the frame 11 . An adjustable upper stop 87 , mounted on the front of the front plate 20 of the frame 11 above the top toggle plate 78 limits upward and downward movement of the top toggle plate. The right and left toggle plates 79 and 80 are vertically elongated, substantially rectangular plates pivotally mounted at the lower ends to the lower end of the front plate 20 of the frame 11 on opposite sides of the tube opening 23 . A pair of elongated spaced toggle links 88 pivotally attach to the top toggle plate 78 , extend downwardly and inwardly, and pivotally attach, one each, near the upper ends of the right and left toggle plates 79 and 80 , such that when the top toggle plate 78 moves downward the toggle links 88 pivot the right and left toggle plates 79 and 80 inward. The means for actuating 86 includes a pair of spaced toggle side plates 90 rigidly mounted to the back of the front plate 20 of the frame 11 , above the limit bar 31 , and a rotably mounted toggle shaft 91 that extends laterally through the toggle side plates 90 . A pair of spaced, vertical, toothed toggle racks 93 rigidly mount to the back of the top toggle plate 78 on opposite sides of the front plate 20 of the frame 11 , and mesh with toggle pinions 94 that are rigidly attached to the toggle shaft 91 . Other suitable means for actuating 86 may include a plunger and link arrangement. A toggle handle 96 includes an elongated lever arm 97 that attaches at one end to the left end of the toggle shaft 91 and has a laterally extending hand grip 98 attached to the opposite end. Referring to FIGS. 7 to 10 , the female die 100 is sized and shaped to fit into the tube selected to be bent, having a substantially rectangular frontal profile with radiused corners. The female die includes an annular groove 101 that extends around at least the top and both sides. An alignment aperture 102 and a fastening aperture 103 , below the alignment aperture, each extend through the female die 100 . The female die 100 fastens onto the front end of the carriage rack 26 with the pin 27 extending through the alignment aperture 102 , and with a threaded fastener 104 extending through the fastening aperture 103 into the threaded hole 28 . The top, right and left male dies 82 , 83 and 84 are each a substantially flat plate. The top, right and left male dies 82 , 83 and 84 overlap when mounted in the top, right and left toggle plates 78 , 79 and 80 , with the right and left male dies 83 and 84 behind the top male die 82 . The top male die 82 has a generally downward pointing working tip 105 shaped to crimp the top and upper corners of a tube, and sized and shaped to fit into the annular groove 101 of the female die 100 . The right mail die 83 has a generally leftward pointing working tip, 106 shaped to crimp the right side and right upper corner of a tube, and sized and shaped to fit into the annular groove 101 of the female die 100 . The left male dies 84 has a generally rightward pointing working tip 107 shaped to crimp the left side and left upper corner of a tube, and sized and shaped to fit into the annular groove 101 of the female die 100 . The working tip 105 of the top male die 82 tapers rearwardly while the working tips 106 and 107 of the right and left male dies 83 and 84 taper forwardly so that the overlapping portions form a wedge that self-centers the top, right and left male dies 82 , 83 and 84 in the annular groove 101 of the female die 100 . Operation of the apparatus 11 commences with selection and mounting of the correct female die 100 and top, right and left male dies 82 , 83 and 84 for the size and orientation of the selected tube. The limit pin 33 is inserted into the limit hole 32 in limit bar 31 corresponding to the selected number of folds. The cylindrical plunger 69 on the carriage handle 42 is pulled out and the carriage assembly 15 is pushed back until the limit pin 33 stops the receiving element 40 . A tube is inserted into the tube opening 23 , around the female die 100 , and into the receiving groove 49 on the receiving element 40 . The cylindrical plunger 69 on the carriage handle 42 is released into one of the plunger holes 63 of the cup 61 to couple the carriage handle 42 to the cam clutch 60 , so that actuation of the carriage handle 42 will advance the tube. The toggle handle 96 and the carriage handle 42 are pulled alternately, crimping then advancing and folding the tube, until the receiving element 40 reaches the front plate 20 of the frame 14 to form a plurality of folds and thereby a bend in the tube. The above described tube crimping/bending apparatus 11 , with the carriage rack 26 attached to the frame 14 and the carriage pinion 58 on the carriage assembly 15 , is compact and mechanically simple. The means coupling 43 makes operation easy and the means for limiting 44 assures consistent folds. The receiving grooves 49 on the receiving element 40 eliminate the need to change mandrels. The overlapping, tapered, self-centering working tips 105 , 106 and 107 of the top, right and left male dies 82 minimize the need for precise adjustment of the male dies. Although the present invention has been described with a certain degree of particularity, it is understood that the present disclosure has been made by way of example and that changes in details of structure may be made without departing from the spirit thereof.
Tube bending/crimping apparatus has a frame, a toggle assembly and a carriage assembly. The toggle assembly has overlapping male dies with tapering working tips that form a self-centering wedge. The carriage assembly has a shaft with a pinion that engages a rack on the frame to move the carriage assembly. A handle on the shaft is linked to the shaft by a cam clutch and a plunger, so that when the plunger is engaged, pushing the handle moves the carriage assembly forward. When the plunger is disengaged, the carriage assembly is easily moved back to the starting position. Mechanical stops for the handle assure consistent advancement. A receiving element on the carriage assembly has grooves for several sizes and orientations of tube.
1
CROSS-REFERENCE TO RELATED APPLICATION [0001] Not Applicable STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT [0002] Not Applicable REFERENCE TO SEQUENCE LISTING [0003] Not Applicable BACKGROUND OF THE INVENTION [0004] 1′-Acetoxychavicol acetate, whose structure is shown below, is a natural compound, which is found in some plants in the family Zingiberaceae especially in greater galingale ( Alpinia galanga (Linn.) Sw.) and big galingale ( Alpinia nigra (Gaertn.) B. L. Burtt). It is not found in several of other members of this family, such as Zingiber officinale, Kaempferia galanga and Alpinia officinarum, which is used as medicine in China. Galingales have been used as herb and food in Thailand and other countries in Asia for a long time. [0005] Many investigators reported growth-inhibiting activities of 1-acetoxychavicol acetate against many organisms. It could inhibit the growth of various fungi (Jassen, A. M. and Scheffer, J. J. C. 1985), including many dermatophytic fungi such as Trichophyton mentagrophytes, Trichophyton rubrum, Trichophyton concentricum and Epidermophyton floccosum with the minimal inhibitory concentrations (MIC) between 50-250 μg/ml. It also inhibited the growth of several other fungi such as Rhizopus stolonifer, Penicillium expansum, Aspergilus niger, albeit with higher MIC. This compound could not inhibit the growth of the yeast Candida albicans, and many bacteria, such as Escherichia coli, Pseudomonas aeruginosa and Bacillus subtilis but could slightly inhibit the growth of Staphylococcus aureus. [0006] There has been no existing report on the inhibitory activity against the growth of M. tuberculosis and other mycobacterium of this compound. [0007] 1′-Acetoxychavicol acetate can inhibit the formation of many tumor and cancer in mice experimental models, such as skin cancer (Murakami, A. et.al., 1996), bile duct cancer (Miyauchi, M. et.al. 2000), esophageal cancer (Kawabata, K. et.al. 2000), large intestinal cancer (Tanaka, T. et.al. 1997 and Tanaka, T. et.al. 1997), oral cancer (Ohnishi, M. et.al. 1996) and liver tumor (Kobayashi, Y. et.al. 1998). [0008] The mechanisms of action of the compound were not clear. The compound could inhibit the activation of tumor virus such as Ebstein-Barr virus (Marukami, A. et.al. 2000 and Kondo, A. et.al. 1993), and could inhibit the function of xanthine oxidase and NADPH oxidase (Noro, T. et.al. 1998 and Tanaka, T. et.al. 1997). These enzymes involve in superoxide anion production, which is one of the spontaneously occurring toxic substances in the body (Nakamura, Y. et.al. 1998 and Murakami, A. et.al. 1996). [0009] 1′-Acetoxychavicol acetate can inhibit nitric oxide synthase production in RAW264 (mice macrophage) cell line when stimulated with mice interferon-γ or bacterial lipopolysaccharides (Ohata, T. et.al. 1998). 1′-acetoxychavicol acetate at the concentration of 250 could completely inhibit nitric oxide synthase production when stimulated with 100 ng/ml of bacterial lipopolysaccharide. The enzyme production was 80% inhibited when stimulated with 100 ng/ml of interferon-γ. This compound was about 10 times more potent than the other nitric oxide synthase inhibitors such as curcumin, nonsteroidal anti-inflammatory drugs, genistein and ω-3 polyunsaturated fatty acids. 1′-Acetoxychavicol could inhibit nitric oxide synthase by inhibiting the destruction of IκB-α protein, which is an inhibitor of NF-κB (a transcription factor), leading to the decrease of the NF-κB activity and, consequently, resulting in decreased nitric oxide synthase production. It also inhibited other transcription factors such as AP-1 and Stat-1. It has been suggested that nitric oxide, which is produced by nitric oxide synthase, involves in tumor formation. [0010] Greater galingale ( Alpinia galanga (Linn.) Sw. or Languas galanga (Linn) Stuntz.) and big galingale ( Alpinia nigra (Gaertn.) B.L. Burtt) belong to the family Zingiberaceae. The galingales are found in Asia, from India, Indonesia to Philippines. They are used as food and herb in Thailand. As herb, the galingales are generally used as anti-flatulence, to decrease the gastric discomfort and to treat dermatophytic fungal infection. It was noted in a Thai ethnomedicinal textbook that galingale oil could be used for tuberculosis treatment. [0011] It was reported that greater galingale did not produce acute toxic effects in mice even at the dose as high as 3 g/kg body weight and did not have chronic toxicity when given to mice at the dose of 100 mg/kg bodyweight for 90 days. It was found that it did not affect the body weight or the weights of any organs including heart, lung, liver, spleen, and kidney. It increased the number of red blood cells but not white blood cells. It increased the weight of sex organs in male mice with the increase of sperm number and sperm movement. It was not toxic to sperm (Qureshi, S. et.al. 1992 and Mokkhasmit, M. et.al. 1971). In contrast, it decreased the toxicity of cyclophosphamide in mice (Qureshi, S. et.al. 1994). [0012] 1′-Acetoxychavicol acetate can be found in high concentration, of about 1.5%-2.8% of dry weight, in the greater galingale root (De Pooter, H. L. et.al. 1985), but less in the leaf (Jassen, A. M. and Scheffer, J. J. C. 1985). The configuration of 1′-acetoxychavecol naturally found in the galingale is in S-form. [0013] Many chemicals have been reported in greater galingale. These included galingin, 3-methygalangin (Ramachandran, N. and Gunasegaran, R. 1982), 1′-hydroxychavicol acetate, 1′-acetoxyeuginol acetate (Jassen, A. M. and Scheffer, J. J. C. 1985), p-hydroxycinnamaldehyde, [di-(p-hydroxy-cis-styryl)] methane (Barik, B. R. 1987), galanal A, galanal B, galanolactone, (E)-8(17),12-labddiene-15,16-dial, (E)-8β(17), epoxylabd-12-ene-15,16-dial (Morita, H. and Itokawa, H. 1987). [0014] Tuberculosis, caused by Mycobacterium tuberculosis, is an important communicable disease. Mycobacterium is a genus of bacteria, which have special cell membrane structures different from other bacteria. This renders most antibiotics unable to enter the bacterial cells, leading to failure in inhibiting the growth of the bacteria. Tuberculosis, therefore, requires special drugs for treatment. [0015] Anti-tuberculosis drugs can be divided into two groups. The first line drugs, are highly effective and of relatively low toxicity. The second line drugs, are less effective and/or of relatively high toxicity. The drugs are used when the bacteria resist the first line drugs. [0016] There are 5 first line drugs, which are isoniazid, rifampin, pyrazinamide, ethambutol and streptomycin. Standard tuberculosis treatment requires 4 in the 5 drugs. There must be isoniazid and rifampin with two other drugs, usually pyrazinamide and ethambutol or streptomycin. The 6-month-long treatment starts with these 4 drugs for 2 months, followed by treatment with isoniazid and rifampin for 4 months. This is because only isoniazid and rifampin are highly effective in killing the bacteria. When M. tuberculosis resists to any of pyrazinamide, ethambutol or streptomycin, the treatment requires the switch to second line drugs and still might be able to complete the treatment in 6 months. On the other hand, if the organisms resist to isoniazid or rifampin, even the switch to other effective drugs may not render the treatment being successful in 6 months. The treatment may need to be lengthened up to 18 months especially if the organisms resist rifampin. The M. tuberculosis is, therefore, called multi-drug resistant when resists to both isoniazid and rifampin. Multi-drug resistant tuberculosis is a very serious public health problem because it can not be cured in 6 months or the worst, not at all. This is due to the fact that the bacteria may become gradually resisting other drugs during the treatment. The patients may have no serious symptoms even though the treatment can not eliminate the bacteria because the drugs may control the organisms to some extent. The patients can therefore survive and transmit the resistant strains to the other people. [0017] The presence of limited number of the highly effective drugs is a major problem in tuberculosis control. Although, isoniazid and rifampin have been discovered for 30 years, there have been limited efforts to identify new highly effective drugs. DETAILED DESCRIPTION OF THE INVENTION [0018] The discovery and development of new anti-tuberculous drugs are usually started by showing that a new compound can inhibit the growth of M. tuberculosis in vitro. The method includes culturing the bacteria in artificial medium, which contains the compound and then observing the growth of the bacteria. The compounds with higher activity will inhibit the growth of M. tuberculosis at a lower concentration than the compounds with lower activity. The activity of each drug can be compared by its minimal inhibitory concentration (MIC). [0019] The growth of M. tuberculosis can be measured by several methods such as observing colony formation in solid media or turbidity in liquid media. However, the observation of the slow growing M. tuberculosis is possible only after a long period of incubation. Many investigators tried to find a way to observe the growth in a shorter time. The M. tuberculosis usually grows more rapidly in liquid media than in solid media. Therefore, the tests for drug development are usually done in liquid media. [0020] Several indirect growth observation methods have been developed for clinical use. These include observing the production of radioactive carbon dioxide in BACTEC460 system (Middlebrook, G. et.al. 1997), the oxygen in Mycobacterium Growth Indicator Tube (Pfyffer, G. E. et.al. 1997) or the bioluminescence from the luciferase enzyme that is transducted into M. tuberculosis by a specially-engineered virus (Arain, T. M. et.al.). Most of these methods can decrease the test period from 3-4 weeks to only 7-10 days. [0021] Many of the systems, marketed for clinical use, require high amount of media and consequently high amount of samples. They are, therefore, not suitable for drug development. The methods specifically designed for drug development are usually done in microplate. The small wells allow the use of small amount of culture media and tested compounds. A popular microplate test uses the bacteria containing luciferase enzyme as surrogate host. The growing bacteria produce the luciferase enzyme, rendering it bioluminescent. Another method measures the oxygen content in the microplate by observing the color change of Alamar Blue (Collins, L. and Franzblau, S. G. 1997) or other dyes. [0022] Anti-tuberculous drugs must have low toxicity because the patients need to ingest it for a long time. Primary testing for toxicity is usually done by incubates the candidate compounds with human cells which the cells were cultivated in vitro and then observes the cytopathic effects. In principle, every chemical compound is toxic to human cells at a high enough concentration. The chemical compound that may be used as drug must have the ability to inhibit growth of organisms at a lower concentration and is toxic to human cells at a higher concentration, such as at the concentration more than 10 fold higher than the MIC. The compound can then theoretically be administered to human to achieve concentration between MIC and the toxic concentration. [0023] The appropriate compounds for the 1′-acetoxychavicol acetate may be readily prepared by methods known to those skilled in the art. The preferred method for the preparation of 1′-acetoxychavicol acetate involves the following steps a) to d): [0024] a) Preparation of 1′-acetoxychavicol Acetate from Galingale [0025] Extraction and purification of the compound was done starting from slicing the root of greater galingale ( Alpinia galanga (Linn.) Sw.) or big galingale ( Alpinia nigra (Gaertn) B. L. Burtt). The slices were air-dried and then ground, following by dichloromethane extraction. The extracts were then dried, resolubilized and purified by silica gel column. After elution with dicloromethane:hexane (1:1), the elute was distilled at 170-190° C. to recover pure 1′-acetoxychavicol acetate. The yield of 1′acetoxychavicol acetate was about 60 gm/kg of the galingales. [0026] b) Preparation of Bacteria to Test 1′-acetoxychavicol Acetate Against M. tuberculosis [0027] [0027] Mycobacterium tuberculosis H 37 Ra strain (ATCC 25166) was grown in 100 ml of Middlebrook 7H9 broth supplemented with 0.2% glycerol, 1.0 gm/L of casitone, 10% OADC, and 0.05% Tween 80. The complete medium was referred to as 7H9GC-Tween. The bacteria were incubated in 500-ml flasks on a rotary shaker at 200 rpm and 37° C. until the optical density at 550 nm reached 0.4-0.5. The bacteria were washed twice with phosphate-buffered saline and then suspended in 20 ml of phosphate-buffered saline. The suspension was passed through an 8-μm-pore-size filter to eliminate clumps. The number of the bacteria in the filtrates was counted by plating the bacteria in Middlebrook 7H10 agar. The filtrates were stored at −80° C. [0028] c) Microplate Alamar Blue assays (MABA) [0029] Anti-tuberculous testing was performed in a 96-well microplate as previously described (Collins, L. and Franzblau, S. G. 1997). Outer perimeter wells were filled with sterile water to prevent dehydration of the test wells. Crude extracts were initially diluted in dimethyl sulfoxide, and then were diluted to a concentration of 400 μg/ml in Middlebrook 7H9 medium containing 0.2% V/V glycerol and 1.0 gm/L casitone (7H9GC). The wells in rows B to G in columns 2, 4, 5, 6, 8, 9, 10 of the microplate were inoculated with 100 μl of 7H9GC. The wells in column 11 were inoculated with 200 μl of the medium to serve as media controls (M). Bacteria (only) controls (B) were set-up in column 10. One hundred microliters of each crude extract solution (400 μg/ml) were added to three wells in one row in columns 2 (or 6), 3 (or 7) and 4 (or 8). One hundred microliters was transferred from column 4 (or 8) to column 5 (or 9), the contents of the wells in column 5 (or 9) were mixed well and then 100 μl of mixed medium were discarded. The wells in columns 2 and 6 served as test sample controls. [0030] Frozen bacterial inocula were diluted 1:200 in 7H9GC medium. One hundred microliters of the bacteria were added to the wells in rows B to G in columns 3 (or 7), 4 (or 8), 5 (or 9) and 10 resulting in final bacterial titers of about 5×10 4 CFU/ml. The wells in column 10 served bacteria (only) controls (B). Final concentrations of extracts were 200, 100 and 50 μg/ml in columns 3 (or 7), 4 (or 8) and 5 (or 9), respectively. [0031] The plates were sealed with Parafilm and were incubated at 37° C. for 5 days. At day 6 of incubation, 20 μl of Alamar Blue reagent and 12.5 μl of 20% Tween 80 were added to well B10 (B) and B11 (M). The plates were re-incubated at 37° C. for 24 h. Wells were observed at 24 h for color change from blue to pink. If the B wells became pink by 24 h, reagent was added to the entire plate. If the well remained blue, the additional M and B wells was tested daily until a color change occurred at which time reagents were added to all remaining wells. The microplates were resealed with Parafilm and were then incubated at 37° C. The results were recorded at 24 h post-reagent addition. [0032] A blue color in the well was interpreted as no growth, reflecting the activity of the test compound in the well. A pink color was scored as growth and reflected the lack of activity of the test compound. A few wells appeared violet after 24 h of incubation, but they invariably changed to pink after another day of incubation and thus were scored as growth (while the adjacent blue wells remained blue). [0033] When 1′-acetoxychavicol acetate was found to be active at the concentration of 50 μg/ml, the activity of the compound was tested in the second plate containing the compound at two-fold serially diluted from 50 to 0.025 μg/ml. 1′-acetoxychavicol acetate can inhibit the growth of M. tuberculosis at the concentration of 0.1 μg/ml or higher but not at the concentration of 0.05 μg/ml or lower. The MIC of 1′-acetoxychavicol acetate against M. tuberculosis H 37 Ra was therefore 0.1 μg/ml. [0034] The activity of the compound was also tested for 30 clinical strains of M. tuberculosis isolated from patients in Thailand. The MICs were found to be between 0.1-0.5 μg/ml. The clinical isolates included isoniazid and/or rifampin resistant strains. [0035] d) The Toxicity of 1′-acetoxychavicol Acetate [0036] 1′-acetoxychavicol acetate was tested for toxicity by incubating it with Vero cells (African green monkey kidney cell line from American Type Culture Collection USA). 1′-acetoxychavicol acetate was dissolved with dimethyl sulfoxide and then diluted in the culture medium of the Vero cells (Eagle's minimum essential with 10% heat-inactivated fetal bovine serum and antibiotics). The Vero cells and the compound were incubated together in a 96-well microplate at the cell concentration of 1.9×10 4 cells/ 190 μl/well, in a CO 2 incubator at 37° C. for 3 days. The numbers of the cells in the wells were then determined by a staining method (Skehan, P. 1990). The cells were firstly fixed by 50% cold trichloroacetic acid (TCA) at 4° C. for 30 minutes. The cells were then washed with water 4 times. After drying, the cells were stained with 0.05% sulforhodamine B in 1% acetic acid for 30 minutes, washed with 1% acetic acid 4 times and dried at room temperature. Finally, 10 mM Tris-base pH10 was added. The absorbance at 510 nm of test wells was measured by an ELISA microplate reader. The absorbance was proportionate to the number of the viable cells in the wells. The toxic level of the compound was recorded as the concentration that rendered the number of viable cells being less than half of the negative control wells, which contained the cells with DMSO but not the compound. The test was done at least 3 times per concentration. Ellipticine was used as positive control. The toxic level of 1′-acetoxychavicol acetate against Vero cells was found to be 2.0 μg/ml, which was 20 times higher than the MIC against M. tuberculosis H 37 Ra. [0037] 1-Acetoxychavicol acetate was also tested for toxicity against three other mammalian cell lines, namely L929 (mouse lung cells), BHK21 (hamster kidney cells) and HepG2 (human liver cells) by culturing the cells in microplates together with various concentration of the compounds. The toxic levels were again defined as the concentration that decrease the viability of the cells by half compared to the negative control, which contain no compound. The viability of these cells were determined by adding MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) solution into wells after 48 hours of co-incubation of the cells with the compound. The viable cells converted the soluble MTT to insoluble formazan precipitate. After 4 hours of incubation, aqueous phase of the wells was removed and dimethyl sulfoxide was added to disslove the formazan. Sorensen's glycine buffer pH 10.5 was then added and the absorbance at 570 nm was measured and compared to the absorbance of the negative control wells. [0038] The toxic levels of the compound for L929 and BHK21 cells were found to be 7.0-8.5 μg/ml, while the toxic level against HepG2 cells was 23.4 μg/ml. REFERENCE [0039] 1. Arain, T. M., Resconi, A. E., Hickey, M. J, and Stover, C. K. Bioluminescence screening in vitro (Bio-Siv) assays for high-volume antimycobacterial drug discovery. Antimicrob Agents Chemother. 1996;40:1536-41. [0040] 2. Barik, B. R., Kundu, A. B, and Dey, A. K. Two phenolic constituents from Alpinia galanga rhizome. Phytochemistry 1987;26:2126-2127. [0041] 3. Collins, L., and Franzblau, S. G. Microplate alamar blue assay versus BACTEC 460 system for high- throughput screening of compounds against Mycobacterium tuberculosis and Mycobacterium avium. Antimicrobl Agents Chemother 1997;41:1004-1009. [0042] 4. De Pooter, H. L., Omar, M. N., Coolsaet, B. A., and Schamp, N. M. The essential oil of greater galanga ( Alpinia galanga ) from Malaysia. Phytochemistry 1985;24:93-96. [0043] 5. Jassen, A. M. and Scheffer, J. J. C. Acetoxyhydroxychavicol acetate, an antifungal component of Alpinia galanga. Planta Med 1985;6:507-11. [0044] 6. Kawabata, K., Tanaka, T., Yamamoto, T. et. al. Suppression of N-nitrosomethylbenzylamine-induced rat esophageal tumorigenesis by dietary feeding of 1′-acetoxychavicol acetate. Jpn J. Cancer Res 2000;91:148-155. [0045] 7. Kobayashi, Y., Nakae, D., Akai, H. et. al. Prevention by 1′-acetoxychavicol acetate of the induction but not growth of putative preneoplastic, glutathione-S-transferase placental form-positive, focal lesions in the livers of rats fed a choline-deficient, L-amino acid-defined diet. Carcinogenesis 1998;19:1809-1814. [0046] 8. Kondo, A., Ohigashi, H., Murakami, A., Suratwadee, J., and Koshimizu, K. 1′-Acetoxychavicol acetate as a potent inhibitor of tumor-promoter-induced Epstein-Barr virus activation from Languas galanga, a traditional Thai condiment. Biosci Biotechnol Biochem 1993;57:1344-1345. [0047] 9. Marukami, A., Toyota, K., Ohura, S., Koshimizu, K., and Ohigashi, H. Structure-activity relationships of (1′S)-1′-acetoxychavicol acetate, a major constituent of a Southeast Asian condiment plant Languas galanga, on the inhibition of tumor-promoter-induced Epstein-Barr virus activation. J. Agric Food Chem 2000;48:1518-1523. [0048] 10. Middlebrook, G., Reggiardo, Z., and Tigertt, W.D. Automatable radiometric detection of growth of Mycobacterium tuberculosis in selective media. Am Rev Respir Dis 1977; 115: 1067-1069. [0049] 11. Mitsui, S., Kobayashi, S., Nagahori, H., and Ogiso, A. Constituents from seeds of Alpinia galanga Wild and their anti-ulcer activities. Chem Pharm Bull 1976;24:2377-2382. [0050] 12. Miyauchi, M., Nishikawa, A., Furukawa, F. et. al. Inhibitory effects of 1′acetoxychavicol acetate on N-nitrosobis (2-oxopropyl) amine-induced initiation of cholangiocarcinogenesis in syrian hamsters. Jpn J. Cancer Res 2000;91:477-481. [0051] 13.Mokkhasmit, M., Sawasdimongkol, K., and Satravaha, P. Toxicity study of Thai medicinal plants. Bull Dept Med Sci, Thailand 1971; 12, 2-4: 36-66. [0052] 14. Morita, H. and Itokawa, H. Cytotoxic and antifungal diterpenes from the seed of Alpinia galanga. Planta Med 1988;9:117-120. [0053] 15. Murakami, A., Ohura, S., Nakamura, Y. et. al. 1′acetoxychavicol acetate, a superoxide generator inhibitor, potently inhibits tumor promotion by 12-O-tetradecanoylphorbol-13-acetate in ICR mouse skin. Oncology 1996;53:386-391. [0054] 16.Nakamura, Y., Marukami, A., Ohto, Y., Torikai, K., Tanaka, T., and Ohigashi, H. Suppression of tumor promoter induced oxidative stress and inflammatory responses in mouse skin by a superoxide generator inhibitor 1′-acetoxychavicol acetate. Cancer Res 1998;58:4832-4839. [0055] 17. Noro, T., Sekiya, T., Katoh, M. et. al. Inhibitors of xanthine oxidase from Alpinia galanga. Chem Pharm Bull 1988;36:244-248. [0056] 18. Ohata, T., Fukudal, K., Murakami, A., Ohigashi, H., Sugimural, T., and Wakabashil, K. Inhibition by 1′-acetoxychavicol acetate of lipopolysaccharide- and interferon-gamma-induced nitric oxide production through suppression of inducible nitric oxide synthase gene expression in RAW264 cells. Carcinogenesis 1998;19:1007-1012.
1′-Acetoxychavicol acetate is a compound not known before to possess anti-tuberculous activity. The above data revealed that the compound was active against the standard H37Ra strain as well as several clinical isolates at the concentration well below the toxic concentration against various mammalian cells. The compound is therefore potentially useful as an therapeutic and preventive agent for tuberculosis as well as an antiseptic agent against the bacteria.
0
The benefit of U.S. Provisional Application Serial No. 60/179,136, filed Jan. 31, 2000, claimed and the entire contents of the Provisional Application is incorporated herein by reference. The present invention relates to measurement of flow in blood vessel by thermo-dilution. In particular it relates to an improved method of triggering such measurement in order to improve the measurements. BACKGROUND OF THE INVENTION Devices and methods of flow measurements are disclosed in U.S. Ser. Nos. 09/073,061, 09/117,416, all assigned to Radi Medical Systems AB, Sweden. In particular Ser. No. 09/073,061 relates to a method of flow measurements by thermo-dilution, wherein the time measurements are triggered by a pressure pulse detected as a result of the injection of a bolus dose of saline. The general theory described therein fully applies to the present invention, and therefore the entire disclosure thereof is incorporated herein. Nevertheless, the discussion therein is repeated below for ease of understanding. Application of the thermodilution principle in the coronary sinus was introduced by Ganz (Ganz et al, ”Measurement of coronary sinus blood flow by continuous thermodilution in man, Circulation 44:181-195, 1971). A small catheter is introduced deeply into the coronary sinus and cold saline is delivered at its tip. Theoretically, flow can be calculated from the changes in blood temperature, registered by a thermistor close to the outlet of the coronary sinus. An advantage of this method is that only right heart catheterization is required. The principle of thermo-dilution involves injecting a known amount of cooled liquid, e.g. physiological saline in a blood vessel. After injection the temperature is continuously recorded with a temperature sensor attached to the tip of a guide wire that is inserted in the vessel. A temperature change due to the cold liquid passing the measurement site, i.e. the location of the sensor, will be a function of the flow. There are various methods of evaluating the temperature signal for diagnostic purposes. Either one may attempt to calculate the volume flow, or one may use a relative measure, where the flow in a “rest condition” is compared with a “work condition”, induced by medicaments. The latter is the simpler way, and may be carried out by measuring the width at half height of the temperature change profile in the two situations indicated, and forming a ratio between these quantities. Another way of obtaining a ratio would be to measure the transit time from injection and until the cold liquid passes the sensor, in rest condition and in work condition respectively. The former method, i.e. the utilization of the volume flow parameter as such, requires integration of the temperature profile over time in accordance with the equations given below ( 1 )     Q r     e     s     t    =    V / ∫ t 1 t 0  ( T r ,    m /    T r ,    l )      t    ∝    V / ∫ t 1 t 0  ( T r ,    0    -    T r ,    m )      t ( 3.1 ) ( 2 )     Q w     o     r     k    =    V / ∫ t 1 t 0  ( T w ,    m /    T w ,    l )      t    ∝    V / ∫ t 1 t 0  ( T w ,    0    -    T w ,    m )      t ( 3.2 ) wherein V is the volume of injected liquid T r,m is the measured temperature at rest condition T r,1 is the temperature of injected liquid at rest condition T 0 is the temperature of the blood, i.e. 37° C. T w,m is the measured temperature at work condition T w,1 is the temperature of injected liquid at work condition Q is the volume flow These quantities may then be used directly for assessment of the condition of the coronary vessels and the myocardium of the patient, or they may be ratioed as previously discussed to obtain a CFR, i.e. CFR=Q work /Q rest . The latter method, i.e. determination of the transit time requires an accurate time measurement, in view of the relatively small distances in question, about 10 cm or less from injection to measurement site. To obtain a correct measurement, the time has to be measured with some accuracy. Using a simple stop watch, which is a common means of timing, is far too inaccurate for obtaining reliable transit times. The flow F may be obtained as follows, which is a derivation for a similar technique, namely the indicator dilution technique. This is based on a rapidly injected amount of some kind of indicator, the concentration of which is measured. Suppose that the flow through a branching vascular bed is constant and equals F, and that a certain well-known amount M of indicator is injected into this bed at site A (see FIG. 7 ). After some time, the first particles of indicator will arrive at the measuring site B. The concentration of indicator at B, called c(t), will increase for some time, reach a peak and decrease again. The graphic representation of indicator concentration as a function of time is called the indicator dilution curve. Consider M as a large number of indicator particles (or molecules). The number of particles passing at B during the time interval Δt, between t i and t i+1 , equals the number of particles per unit time multiplied by the length of the time interval, in other words: c(t i )·F·Δt (FIG. 8 ). Because all particles pass at B between t=0 and t=∞, this means that: M = lim Δ     t    →    0  ∑ i    =    0 ∞  ( c  ( t i ) · F · Δ     t )     or   M = ∫ ∞ 0  c  ( t ) · F ·  t     or   F    =    M ∫ ∞ 0     c  ( t ) ·  t ( 3.3 ) and it is the last expression which is used in most methods to calculate systemic flow as outlined above. Essential features of this approach is that the amount M of injected indicator should be known whereas no knowledge about the volume of the vascular compartment is needed. The calculation of volume is more complex. For this purpose, the function h(t) is introduced which is the fraction of indicator, passing per unit of time at a measurement site at time t. In other words, h(t) is the distribution function of transit times of the indicator particles. If it is assumed that the flow of the indicator is representative for flow of the total fluid (complete mixing), h(t) is also the distribution function of transit times of all fluid particles. Suppose the total volume of fluid is made up of a very large number of volume elements dV i which are defined in such a way that dV i contains all fluid particles present in the system at t=0, with transit times between t i and t i+1 . The fraction of fluid particles requiring times between t i and t i+1 to pass the measurement site, is h(t i )·Δt by definition. Because the rate at which the fluid particles pass at the measurement site, equals F, the rate at which the particles making up dV i pass at the measurement site is F·h(t i )·Δt. The total volume of dV i equals the time t i required for all particles segments in dV i to pass at the measurement site multiplied by the rate at which they leave. In other words: dV i =t i ·F·h ( t i )·Δ t   (3.4) and by integration: V = F  ∫ ∞ 0  t · h  ( t )   t ( 3.5 ) The integral in the equation above represents the mean transit time T mn , which is the average time needed by one particle to travel from an injection site to a measurement site. Therefore: V=F·T mn   (3.6) or: F=V/T mn ; T mn =V/F   (3.7) which states the fundamental fact that flow equals volume divided by mean transit time. The mean transit time (T mn ) can now be calculated easily from the indicator or thermo dilution curve in the following way. When looking at the hatched rectangle in FIG. 8, it can be seen that the number of indicator particles passing between t i and t i+1 , equals the number of particles c(t i )·F passing per unit of time, multiplied by the length of the time interval, Δt, in other words: c(t i )·F·Δt. Therefore, the total (summed) transit time of all these indicator particles together equals t i ·c(t i )·F·Δt. The total transit time of all indicator particles together, by integration, is ∫ 0     t · ∞     c  ( t ) · F ·  t ( 3.8 ) and the mean transit time of the indicator particles can be obtained by dividing equation 3.8 by the total number of particles M, resulting in: T m     n = ∫ 0     t · ∞     c  ( t ) · F ·  t M     or ( 3.9 ) T m     n    =    F M     ∫ 0     t · ∞     c  ( t ) ·  t ( 3.10 ) By substitution of equation 3.3 in 3.10, T mn is obtained: T m     n    =    ∫ 0     t · ∞     c  ( t ) ·  t ∫ ∞ 0     c  ( t ) ·  t ( 3.11 ) Equation 3.11 describes how mean transit time T mn can be calculated from the indicator dilution curve c(t). In the assessment of myocardial in which the contrast agent is used as the indicator, because the amount of injected contrast agent is unknown and changing (because of the necessary leakage of the contrast agent into the aorta and the unknown and changing distribution of contrast agent over the different branches of the coronary arterial tree), use of T mn is advantageous because no knowledge about the amount of injected indicator is necessary. Although the above derivation was made for the mentioned indicator dilution technique, the result is the same for thermo-dilution since the same distribution function may be employed, and the skilled man will easily adjust the equations accordingly. The prior art pressure pulse triggering of the time measurements, although improving the method considerably, has some drawbacks. For example, the sensitivity in the pressure measurement may not be adequate due to the magnitude of the pulse being quite low; therefore, the accuracy may be negatively influenced. SUMMARY OF THE INVENTION Thus, there is a need for an improved triggering of the measurement. The inventors have realized that a previous problem acknowledged in connection with thermo-dilution can be used to an advantage for triggering purposes. Namely, when a bolus cold saline is injected into a catheter where a wire carrying the sensor unit and electrical leads for signal transmission is located, the lead resistance will be instantly affected by the cold saline by a change in the resistivity. This is a problem, however, because the change must be countered in order to arrive at a correct output signal. This compensation can be done, and is one of the issues discussed in our pending Swedish application 9901962-2, corresponding to U.S. provisional No. 60/136,401. Thus, in accordance with the present invention, the resistivity change is recorded as a resistance variation curve. Various parts of the recorded curve, or the entire curve, can be mathematically processed to yield a starting point for the determination for a transit time of the injected liquid. In this way, the accuracy in the time measurement is significantly improved. So long as detectable signals are obtained, the method of flow determination according to the invention is advantageous in that it is independent of: (a) the injected amount of bolus liquid and (b) the temperature of the injected liquid. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is an overview that shows a system wherein the novel method is performed; FIGS. 2 a-d are graphs illustrating the resistivity profiles of the electrical leads during measurement; FIG. 3 is a graph showing measurements on a patient during hyperemia; FIG. 4 is a graph showing measurements on a patient during a resting period; FIG. 5 is a graph showing the correlation between measurement data on patients according to the invention and a reference method; FIG. 6 is a graph showing the correlation between another set of patient data according to the invention and a reference method; FIG. 7 illustrates an indicator dilution curve obtained in a vascular network; and FIG. 8 illustrates calculation of flow in an indicator solution; FIG. 9 illustrates a curve used in determining the center of mass. DETAILED DESCRIPTION OF THE INVENTION In FIG. 1 there is disclosed a system suitable for implementation of the present invention. The system comprises a hollow guide catheter insertable into the body of a patient. The distal end of the catheter functions as an outlet for liquid to be passed therethrough. The catheter is located at a point in the artery system where it is desired to know the flow. Inside the catheter a wire is inserted, the distal end of which carries a sensor unit having a temperature sensor and optionally a pressure sensor. Other additional sensors are also conceivable, e.g. pH sensors, ion selective sensors etc. The wire is extended past the distal end of the catheter such that the sensor unit is located at a relatively small distance, e.g. 10 cm, from the catheter outlet. Alternatively, the wire can be inserted as above and positioned in an appropriate position, and then a second catheter can be passed over the wire, inside the guide catheter; the distal end of this second catheter can be positioned in the artery system where it is desired to know the flow. The first catheter will thereby only be used for guiding. This alternative approach can be used if the vessel tree is fairly complex with many narrow blood vessels, making it difficult to position a catheter without the help of the wire. The guide catheter (or the second catheter in the alternative) is provided at the proximal end with an inlet for saline. Preferably a Luer® lock is provided so that a syringe can easily be connected to the catheter. The sensor unit is coupled to a control unit for the processing of the signals from the sensor unit, said signals being transferred via electrical leads running along the wire. The method according to the invention will now be described in some detail with reference to the figures. When the above-mentioned catheter has been positioned appropriately, it will become filled with blood because of the prevailing pressure difference between the interior of the body and the ambient atmosphere (i.e., the pressure inside the vessel is slightly higher than the atmospheric pressure externally of the body, P body −P outside >0). When the wire carrying the sensor has been inserted and the sensor appropriately located at the point of measurement, the operator fills a syringe with a suitable amount of cold saline, say 20° C. The volume to be expelled by the syringe is preferably equal to the volume inside the catheter from the inlet point up to the outlet plus the bolus-dose to be expelled into the flowing blood. The volume of a catheter is commonly about 3 ml, and a suitable bolus-dose could be, for example, 1-3 ml, although the exact volumes will of course differ from case to case. The sensor is connected via the electrical leads to a detection unit which has the capability of switching between measurement of cable resistance and detecting the signal from the sensor. The operator connects the syringe to the inlet port and begins injecting the cold saline at a relatively low rate, such that the time to fill the guide catheter all the way up to the outlet will typically take 1-15, preferably 10-15 seconds, although this can vary substantially from case to case outside this interval. The volume of the catheter is known and thus when the operator has expelled a volume corresponding to the catheter volume during the mentioned time period, he will more rapidly expel the last dose, for example during 0.5 seconds, although this time is not strictly critical. The detection unit operates according to the method disclosed in the previously mentioned U.S. provisional No. 60/136,401. The compensation disclosed therein is based on a switching between measurements of the sensor signal and of the resistance of the leads so as to enable compensation of changes in lead resistance. Thus, when the operator begins injecting the cold saline, the resistivity of the electrical leads will instantly be changed but this will be compensated for so that the detection unit will always deliver a readout of a constant temperature inside the blood vessel at the location of the sensor. For the purpose of the invention, the change in resistance of the leads will not be recorded during the initial phase of filling the catheter with saline. But, immediately prior to or at the same time as the operator injects the last bolus-dose into the catheter, the recording of lead signal will be initiated and monitored and also the sensor signal will be recorded and monitored simultaneously. Because of the rapid injection of the last volume segment of cold saline (from the point t start in FIG. 2 a to the point at which the bolus ends, t stop ), the cable resistivity will abruptly change since it will experience more cold liquid during a shorter period of time and this will be reflected in a drop in the readout signal as shown in FIG. 2 a . The sensor being located at a relatively short distance from the catheter outlet, for example, approximately 10 cm (although this distance is not strictly critical), will be subjected to the cooler bolus-dose of saline a short period of time (on the order of a fraction of a second up to a few seconds) after it has been expelled from the outlet of the catheter. A sensor signal is schematically shown in FIG. 2 b , and this signal is recorded and used as the basis for determining the starting point of time measurement. If it can be assumed that the actual injection of the bolus-dose into the blood-flow will not affect the measurement of the flow at the measurement point, then a calculation as recited under the background of the invention can be performed on the basis of the sensor signal by numeric integration, or by fitting the entire signal from the sensor element to a mathematical function (e.g., natural Log, Gamma), which can be used to calculate the center of mass of the curve defined by the sensor signal shown at C in FIG. 2 ( d ). Also, a combination of numeric integration and curve fitting can be used. In the latter case, the curve fitting is performed at the portion of the curve approaching the base line, after the cut off point D (see FIG. 2 c ). To calculate the center of mass, we assume that it is located at a position x as shown in FIG. 9 . The center of mass is found where the area of A 1 =the area of A 2 . Accordingly, A 1 = ∫ 0 x   - t / τ      t     and ( 3.12 ) A 2 = ∫ x ∞   - t / τ      t ( 3.13 ) and, therefore: A 1 = - τ      - t / τ  | 0 x = - τ      - x / τ + τ     and ( 3.14 ) A 2 = - τ      - t / τ  | x ∞ = 0 + τ      - x / τ ( 3.15 ) and, therefore, as A 1 =A 2 , by substitution of equations 3.6a and 3.6b, it is known that −τ e −x/τ +τ=e −x/τ it follows, therefore, that 2τe −x/τ =τ. Dividing both sides of the equation by τ yields 2 e −x/τ =1 so that e −x/τ =0.5. Taking the natural logarithm of both sides yields: −x/τ=ln(½). It thus follows that: x =−τln(½)=0.7τ  (3.16) However, the starting point for the integration (i.e., t=0) must be determined. This point in time can be determined in different ways, using the recorded resistance variation curve. One way to determine t=0 to register the onset of resistivity reduction. Here the derivative of the curve may be calculated, and if the derivative exceeds a preset value, time measurement is triggered. Another way to determine t=0 is to use the peak value as a starting point for time measurement. Again the derivative, or preferably the second derivative, is calculated and the change in sign is detected. A further usable point is to take the average of the two values, e.g. (t start −t stop )/2. In an alternative embodiment the same “triggering” of the time measurement can be used. For the purposes of this invention, “triggering” is defined as the determination of a starting point for the time measurement, (i.e., the determination of t=0 for the purpose of integration). In this alternative embodiment only the increasing part of the sensor signal (indicated with B′ will be used). For this purpose the mentioned part B′ (shown in FIG. 2 b ) of the sensor signal curve will entirely or partly be fitted to a mathematical function, e.g. e −t/τ , which is an exponential function. The simplest way of doing this is to take the logarithm of the measurement data along B′ and to plot this against time. From the slope of the linear portion of that plot, the time constant, τ of the exponential function can be determined. The point on curve portion B′ corresponding to the point on the time axis at t min, sensor +τ will be center of mass of the exponential curve, which is the point up to which T mn will be calculated from t=0. As derived above, 0.7τ should be used for the identification of the center of mass, but for the purpose of this invention the approximation to τ is adequate. τ can be calculated by fitting the sensor element signal from the point P s in FIG. 2 c up to a point D, where D is the cut-off point, e.g. 10% of the peak value (at P s ). If we assume that t=0 is equidistant from the points t start and t stop , i.e., (t stop −t start )/2, then the total mean transit time T mn will be sum T mn =( t stop −t start )/2 +t min, sensor −t stop +τ  (3.17) The terms of this sum are illustrated in FIG. 2 c as t 1 , t 2 and t 3 respectively, and thus T mn =t 1 +t 2 +t 3   (3.18) wherein τ or 0.7τ can be used for t 3 , as indicated above. Of the above possible approaches to the determination of T mn , the method discussed in connection with FIG. 2 d is the most in a mathematical accurate. However, the initial flank will very easily be affected by the injection, and the curve fitting may, therefore, be incorrect. The other method (FIG. 2 c ), where only the portion after the peak is fitted to a curve is more independent of the injection, because the injection is stopped before any calculations are performed on the curve. In FIG. 3 and 4, respectively, measurement data on a patient are shown for a hyperemic condition and a resting condition respectively. As can be clearly seen in these figures there is a difference in the time between the minimum of the cable signal and the minimum of the temperature sensor response signal for the two cases. In the hyperemic state, the distance is shorter (i.e., the flow is higher) than in the resting condition. It is also clearly visible that the time constant for the increasing portion is slower for the resting condition than for the hypermia condition. The CFR is calculated as CFR=T mn, rest /T mn, hyper   (3.19) Finally in FIGS. 5 and 6, respectively, the method according to the invention has been qualitatively evaluated against a reference method which is a determination of CFR by a doppler-technique. In this case however, it should be noted that the doppler-technique also has its limitations and is not entirely accurate. As previously disclosed in this application, CFR can be obtained by measuring the mean transit time, T mn , for a bolus dose of cold liquid by employing the response curves from lead resistance measurements and a temperature sensor respectively. For the calculation of T mn , the time constant, τ, of an exponential function e −t/τ is calculated. It has also been discovered by the inventors that τ itself is correlated to the flow in a coronary vessel, and, therefore, τ itself can be used to determine a valve of CFR where τ rest is the time constant of the temperature sensor response in a resting condition and τ hyper is the time constant of the temperature sensor in a hyperemic condition. Accordingly, CFR=τ rest /τ hyper .
When a bolus dose of cold saline is injected into a catheter where a wire, carrying a sensor unit and electrical leads for signal transmission, is located, the lead resistance is affected by the cold saline thereby altering the resistivity. However, by countering this effect and measuring the change needed to affect this countermeasure, a resistance variation curve can be generated. An accurate starting point for the determination of a transit time can be derived from the curve. Using conventional flow measurement calculations with the accurate starting point yields a better understanding of the flow profile in an artery based on the transit time.
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CROSS-REFERENCE TO RELATED APPLICATION [0001] This application claims the benefit of and priority to French Patent Application No. 1353777, filed Apr. 25, 2013. French Patent Application No. 1353777 is hereby incorporated by reference in its entirety. BACKGROUND [0002] The invention relates to “active implantable medical devices” as defined by Directive 90/385/EEC of 20 Jun. 1990 the Council of the European Communities. The invention relates to implants for delivering vagus nerve stimulation therapies, which have been called “VNS” therapies (Vagus Nerve Stimulation). [0003] Stimulation of the vagus nerve affects cardiovascular function by reducing the heart rate and myocardial contractility with decreased duration of diastole. These effects can help reduce the progression of cardiac remodeling that may lead heart failure. [0004] In general, the vagus nerve can be stimulated asynchronously or synchronously (e.g., with the heartbeat). In the first case, the device may simply include a lead provided with an electrode implanted on the vagus nerve and of a generator delivering VNS pulses on this electrode. In this configuration there is no possible interference between the VNS electronics and a cardiac lead. [0005] In contrast, in the case of a synchronous stimulation, for example, the device further includes one or more cardiac leads. For example, such a device may include one or more endocardial lead or one or more lead implanted in the coronary network for the collection of the cardiac depolarization waves. Such a device may optionally deliver myocardial stimulation pulses (stimulation of ventricular and/or atrial cavities) using electrodes in the heart, in addition to the VNS stimulation applied separately on the vagus nerve. [0006] U.S. 2012/0303080 A1 and U.S. 2007/0233194 A1 disclose devices for synchronous stimulation of the vagus nerve. In this configuration of synchronous VNS stimulation, pacing should be delivered in a non-vulnerable period of the ventricle. [0007] Particularly, if we consider an electrocardiogram ECG surface or endocardial electrogram EGM, among the different waves representative of the PQRST complex of the cardiac activity, it is known that during the QRS (ventricular depolarization) and the subsequent T wave (ventricular repolarization) the heart is in a refractory period. This ventricular refractory period includes a period called “absolute refractory period” during which no electrical stimulation will have an effect on cardiac cells, followed by a period called “relative refractory period” during which stimulation may excite some heart fibers and induce ventricular arrhythmia. [0008] In the case of stimulation of the vagus nerve and in the case of a system with a ventricular lead, it is commonly accepted that VNS stimulation delivered during the relative refractory period of the ventricle is potentially harmful because charges that could be accumulated on the electrode may trigger ventricular arrhythmias. Stimulation should therefore be avoided during this period. Thus, US 2012/0303080 A1 and US 2007/0233194 A1, cited above disclose synchronizing the application of the VNS pulse burst on the detection of the R wave, in order to apply these pulses during the absolute ventricular refractory period which immediately follows this wave. Despite these prior art devices, it remains challenging and difficult to safely synchronize VNS and heart stimulation treatments. SUMMARY [0009] An embodiment of the invention is a device configured to deliver VNS stimulation in a period other than the absolute ventricular refractory period and yet without risks of arrhythmia. [0010] The device uses a period corresponding to the end of natural the escape interval of the ventricle, located after the T wave (i.e. way beyond ventricular refractory periods) at a time corresponding to appearance of the atrial depolarization wave (P wave) of the next cardiac cycle. This device may operates with success given that i) the spontaneous activity of the vagus nerve is mainly concentrated in the PQ cardiac interval and ii) the area before the natural ventricular depolarization, typically in a window of a few tens of milliseconds before spontaneous activity thereof, may be regarded as a non-vulnerable period, that is to say not capable of generating arrhythmias. [0011] To determine the time of application of the VNS therapy in this temporal window, one solution would be to have a lead for detecting atrial depolarization, to detect the onset of the P wave, and to synchronize the beginning of the delivery of the VNS pulse burst on this detection. Such a solution would, however, be complicated to implement, requiring the implantation of a lead with atrial sensing electrodes, and an adaptation of the generator, with an additional connector, dedicated internal circuits, etc. In other words, this would be a device that is a “dual chamber” stimulator. [0012] One aim of the invention is to provide a solution to this problem, with a VNS pacemaker synchronized to the atrial signal but that does not require physical means for detecting atrial depolarizations, including an additional lead for detecting the P wave on which the VNS stimulation could be synchronized. The invention can thus advantageously be implemented using circuits of a “single chamber” stimulator, supplemented by VNS pulse bursts triggered by appropriate sequencer operating using inputs from a single ventricular sensing lead. [0013] To this end, the invention provides a device including a generator generating VNS pulse bursts. The device further includes a circuit for analyzing the cardiac rhythm collecting a signal representative of the cardiac electrical activity, including analyzing an endocardial electrogram EGM signal and determining the duration of successive cardiac cycles. The device further includes a VNS sequencer configured to determine a moment of application of a VNS pulse burst by the generator. The VNS sequencer may include an estimation module calculating, during a given cycle, an estimate of the temporal position of the R-wave cycle of the following cycle. The sequencer can be configured to set the application time of the VNS pulse burst as being a time corresponding to the calculated estimate of the temporal position of the R-wave, anticipated by an estimated advance delay. [0014] In a particular embodiment, the analysis of the cardiac rhythm further calculates an average duration and optionally a standard deviation, of the cardiac cycles over a predetermined period or over a predetermined number of cycles. The device can use such analysis of the cardiac rhythm to calculate the advance delay from the duration of the previous cardiac cycles. This may help accurately reflect the variability and evolution in the cardiac rhythm. [0015] A module for analyzing the cardiac rhythm may calculate an average duration of the cardiac cycles over a predetermined period or a predetermined number of cycles, and the VNS sequencer may calculate the estimate of the temporal position of the R wave according to both said average duration and advance delay. [0016] The device may further include a module for detecting spontaneous ventricular events, and can interrupt the delivery of pulses produced by the generator in the event of occurrence of a spontaneous ventricular event subsequent to the instant of application of the VNS pulse burst. It is also possible to provide means for delivering a ventricular pacing pulse in the absence of occurrence of a spontaneous ventricular event at the expiration of a predetermined escape interval. [0017] One embodiment relates to a device having a VNS pulse burst generator for stimulation of the vagus nerve, and electronics analyzing cardiac rhythm. It further includes sequencer having an estimation module for calculating, during a given cycle, an estimate (R prev ) of the temporal position of the R wave of the next cycle. The sequencer can then define the moment (TVNS) of application of the VNS pulse burst as an instant corresponding to this estimate (R prev ) adjusted by a predetermined advance delay (Δ VNS ). VNS therapy is thus delivered in a non-vulnerable period, near the end of the period of natural ventricular escape. BRIEF DESCRIPTION OF THE FIGURES [0018] FIG. 1 is an overview presentation of the device, showing the generator, the myocardium, the vagal nerve and the leads used, according to an exemplary embodiment. [0019] FIG. 2 is a schematic block view corresponding to the main features of the generator of the device, according to an exemplary embodiment. [0020] FIG. 3 is a prior art timing diagram showing, in two successive cardiac cycles, the cardiac depolarization wave with its different characteristic periods and the instants of application of the VNS pulse bursts. [0021] FIG. 4 is a counterpart of FIG. 3 , presenting the advantageous technique of the present invention, according to an exemplary embodiment. [0022] FIG. 5 is a timing diagram illustrating the variability in the RR interval in a series of consecutive cardiac cycles. [0023] FIGS. 6 a to 6 c are timing diagrams illustrating the method to determine the instant of application of the VNS stimulation pulses according to the technique of the invention in different situations, respectively: with (a) a normal detection of consecutive R wave, (b) with detection of a premature R wave, and (c) without detection of a consecutive R wave. [0024] FIG. 7 is a flow diagram a method for providing VNS therapy according to an exemplary embodiment. DETAILED DESCRIPTION [0025] According to various exemplary embodiments, a pacemaker includes a programmable microprocessor provided with circuits for shaping and delivering stimulation pulses to implantable electrodes. The pacemaker may include appropriate programming code (e.g., executable code) for adjusting the VNS stimulator according to the activities described herein. In other words, the algorithms described herein may be contained in computer readable media (e.g., non-transient computer readable media) of the pacemaker device and executed by a microcontroller or a digital signal processor of the pacemaker. For the sake of clarity, the various processing applied will be broken down and diagrammed by a number of different functional blocks in the form of interconnected circuits, however this representation is only illustrative, these circuits having common elements and in practice corresponding to a plurality of functions overall performed by a single software. [0026] In FIG. 1 , a device includes a housing of an implantable generator 10 for vagus nerve stimulation. This stimulation is delivered by a lead 12 bearing at its distal portion an electrode implanted on the vagus nerve 14 for stimulation of the latter by application of train pulses produced by the generator 10 . To allow delivery of VNS pulses in synchronism with the cardiac rhythm, the generator 10 also has a cardiac lead 16 provided at its distal end of an electrode 18 for collecting the electrical activity of the myocardium 20 . This lead collects EGM endocardial electrogram signals that will drive the generator 10 so that it delivers to the vagus nerve 14 VNS stimulation pulses at the same rate as the heart beats and at the most appropriate moment of the cardiac depolarization wave. It should be noted that the use of an endocardial EGM may be substituted for other monitoring techniques suitable for obtaining a signal representative of the cardiac electrical activity. [0027] FIG. 2 schematically illustrates the features of the generator 10 of the device of the invention. The generator 10 includes a generator circuit 22 configured to produce bursts of VNS pulses delivered to the vagus nerve via the lead 12 . The generator circuit 22 is controlled by a control circuit 24 . An input to the control circuit is the EGM signal gathered by the lead 16 . [0028] FIG. 3 illustrates a prior art example, on two consecutive cardiac cycles, of the cardiac depolarization wave an EGM collected with successively the different representative waves of the cardiac activity: P-wave (depolarization of the atria), QRS (depolarization of the ventricles) and T wave (repolarization of the ventricles). [0029] During the phase of ventricular activity QRST, the heart is in refractory period with an absolute refractory period PRA during which no excitement, including any electrical stimulation, will act on cardiac cells, followed by a relative refractory period PRR during which an excitation may cause depolarization of certain cardiac fibers. If a VNS therapy has to be delivered in the form of a burst of electrical pulses, the instant T VNS of delivery of this burst, and the number and duration of pulses of the burst are often all delivered during the absolute refractory period PRA. This is to avoid triggering ventricular arrhythmia due to a potential ventricular capture by local current fields that may cause deleterious effects, which could occur if the VNS pulses were delivered during the relative refractory period PRR. To meet this requirement, certain prior art stimulation techniques operate in the manner illustrated in FIG. 3 , in synchronizing the instant T VNS of the beginning of the burst of VNS pulses relative to the detection of the R wave, i.e. the moment when the detection lead collects spontaneous activity having its origin in the ventricle. Specifically, in U.S. 2012/0303080 A1 cited above, the therapy delivery is calculated based on the PP interval, while in U.S. 2007/0233194 A1 also cited above, VNS stimulation is delivered with a predetermined delay calculated based on the R-wave. [0030] The invention proposes to operate differently, delivering VNS therapy during another period of the cardiac cycle, located outside the natural ventricular refractory periods, particularly outside the relative refractory period PRR, and without risk of arrhythmia. [0031] As shown in FIG. 4 , a VNS therapy is caused at the end of the natural escape interval of the ventricle, corresponding to an atrial non vulnerable PNVA period during which the P wave of atrial depolarization happens, well before the activity phase of the ventricle (QRST complex). [0032] Even if the implant does not have the capability to accurately detect the atrial activity, the device may estimate the temporal position of the next ventricular wave and time the delivery of VNS stimulation relative to this estimated position. To do this, as shown in FIG. 5 , the device follows the ventricular activity and determines the moments R of collection of spontaneous ventricular activity. Based on these detections, the device calculates the average ventricular period RR moy and its variability, corresponding to the standard deviation ET RR of the parameter RR. [0033] Depending on RR moy , and optionally also on ET RR , the device calculates an estimate interval RR prev , for example by a function of the type: [0000] RR prev =RR moy −α·ET RR . [0034] If α=1, it is estimated that 85% of the RR cycles are longer than RR prev , in the case of a Gaussian distribution of the RR intervals. This allows obtaining an estimated temporal position R prev of the R wave of the next cycle. [0035] As shown in FIG. 6 a , the instant T VNS of application of the VNS pulse burst will be determined from this estimated R prev , anticipated of an advanced period Δ VNS , typically of the order of ET RR (if α=1). [0036] In the normal case (shown in FIG. 6 a ), the delivery of VNS therapy is followed by the detection of spontaneous activity DetR, in principle close to the estimated position R prev . [0037] In the case (shown in FIG. 6 b ) of a premature spontaneous activity DetR such that it occurs at a time when the VNS pulse burst has not finished being delivered, the device immediately stops this delivery to avoid stimulation during a ventricular refractory period. [0038] In another case (shown in FIG. 6 c ) wherein no spontaneous ventricular event has been detected at the end of the ventricular escape interval IEV (interval counted from the previous R detection), then a ventricular stimulation StimV is delivered by the device. [0039] FIG. 7 is a flowchart describing the sequence of different actions that has just been described. Upon detection of a ventricular activity DetR (test 26 ), the device calculates or recalculates the values of the interval RR moy and of the standard deviation ET RR (block 28 ). [0040] If VNS stimulation should be applied (test 30 ), then the device estimates the expected duration of the next RR interval from the mean and standard deviation of the preceding RR intervals (block 32 ). VNS therapy is then applied, by triggering the delivery of VNS pulse bursts according to the estimated instant, determined in the previous step, of the temporal position of the next R wave (block 34 ). [0041] If during the delivery of the pulse burst ventricular depolarization DetR is detected (test 36 ), then this delivery is interrupted and the method is reset (back to test 26 ). Otherwise, the delivery of the VNS therapy is continued until the last pulse of the burst, and the method is repeated (back to block 28 ). Upon arriving at the end of the VNS therapy (test 38 ), the method may be fully reset (back to test 26 ). In any case, in the absence of detection DetR (test 26 ) at the end of the ventricular escape interval IE (test 40 ), a ventricle stimulation StimV (see FIG. 6( c )) is delivered to the device (block 42 ).
A medical device includes a VNS pulse burst generator for stimulation of the vagus nerve, and a controller for analyzing the cardiac rhythm. It further includes a sequencer that uses an estimator to calculate during a given cycle an estimate of the temporal position of the R wave of the next cycle. The controller is configured to define the moment of application of the VNS pulse burst as an instant corresponding to the estimate minus a predetermined advance delay. VNS therapy is thus delivered in a non-vulnerable period, near the end of the period of natural ventricular escape.
0
RELATED APPLICATIONS [0001] This application claims the benefit of priority from U.S. Provisional Patent Application No. 61/441,007, field on Feb. 9, 2011, the entirety of which is incorporated by reference. FIELD OF THE INVENTION [0002] This application relates to a baffle and baffle system for use in a solids-precipitating clarifier tank. More particularly, the application relates to a baffle and baffle system having a plurality of inte engaged individual baffles secured to the clarifier tank peripheral wall. PRIOR ART DISCUSSION [0003] Passive baffle devices, also known in the art as a lamella gravity separators or settlers, are used in clarifier tanks for aste treatment for gravitationally separating suspended solids from solids containing carrier liquid or fluid suspensions. The clarifier tanks, with which such baffles are typically used, are circular or polygonal in shape in which a centrally mounted radially extending arm is slowly moved or rotated about the tank at or proximate to the surface of the carrier liquid. [0004] Specifically, in wastewater treatment facilities utilizing secondary clarifiers, the clarifier's effectiveness in removing solids is perhaps the most important factor in establishing the final effluent quality of the facility. A major deterrent to effective removal is the presence of sludge density currents that cause hydraulic short circuits within the tank. These short circuits, in turn, allow solids concentrations to unintentionally bypass the tank's clarification volume and enter the effluent. [0005] In the prior art, peripheral density current baffles are attached to the tank wall and directed downward at an angle into the tank. These baffles help to minimize the density currents and properly redirect the flow of solids away from the effluent and into the main clarification volume (center) of the tank. Usually the baffles are inclined at a 45° angle, but other angles ranging from 0° to 60° have been suggested and/or used in certain instances. [0006] In addition to the angle of inclination of the baffle, the horizontal projection of the baffle is another factor that determines the extent to which the baffle can intercept and deflect the density currents in the clarifier tank. If the projection is too small, the baffle may not reach far enough into the path of the density currents to deflect them, regardless of the angle, and thus the currents will continue rising up the clarifier wall and carry lighter solids to the effluent launder. If the baffle projects too far into the tank it may adversely affect the settling of solids in the bottom of the clarifier tank (as desired in normal operations). [0007] In some instances of the prior art, the horizontal projection may be related to the diameter of the clarifier using the following equation: [0000] HP(inches)=18inches+α(Diameter(ft)−30). [0008] The term α in the above equation was originally defined as 0.2 inches per foot, and thus a horizontal projection for a baffle in a 100-foot diameter clarifier tank would be calculated to be 32 inches. This equation is independent of the baffle inclination angle. [0009] Prior art suggestions include modifications to the above equation and suggested that larger projections were beneficial and thus a was increased to 0.3 inches per foot, such that the recommended projection for a 100-foot diameter clarifier was increased to 39 inches. [0010] However, although these density current baffle systems work to significantly reduce solids from entering the effluent, under greater load conditions these baffle systems occasionally fan, allowing for the above described short circuits. SUMMARY [0011] The present arrangement provides an improvement over the prior art in that a density current baffle is constructed for tanks with a greater horizontal projection over the prior art. [0012] In this respect, the present arrangement provides a density current baffle that employs a baffle that is dimensioned to balance the fact that larger horizontal projections of density current baffles improve performance while simultaneously recognizing that an overly large baffle would simply not correctly function, be unnecessarily large and complex and may in fact have a negative impact on the otherwise ordinary operation of flows within the clarifier tank. Thus, the present arrangement provides a baffle that improves performance while satisfying the desire to remain conservative in defining an upper limit for the projection. [0013] To this end, the horizontal projection of the baffle is structured according to the following equation: [0000] HP=24″+0.4inches/foot×(Diameter−30) [0014] With this arrangement for density current baffles, the minimum baffle size is 24 inches. A horizontal projection for a 100-foot clarifier produced by this method is 52 inches (versus 39 inches using the designs of the prior art). Such an arrangement provides up to a 10% improvement in performance over prior art baffle (in reduction in solids reaching the launder channel). Table 1.0 below compares the horizontal projection produced using the current method and NEFCO's method. [0015] The improvement in baffle performance (solids capture) was 5% to 10% or more depending on the size (diameter) of the tank. Expressed as a percentage of tank diameter, the current arrangement uses a projection that ranges from 7% in smaller clarifiers to 4% in large clarifiers, with baffle performance consistently better than that using projections as per the prior art construction. [0016] The present method for determining the horizontal projection of the baffle is independent of the inclination angle, but is most effective when used with a 30° inclination (from down from horizontal—or 60° up from vertical) angle. This angle has been shown to be more effective at solids capture than the prior art 45° angle. An added benefit lies in the fact that the hypotenuse of any resulting baffle is significantly shorter than its 45° counterpart and therefore less expensive to produce. [0017] Table 1.0 Comparison of the Horizontal Projection (HP) under the current arrangement in comparison with prior art projections. [0000] TABLE 1 HP = 18″ + 0.3(D-30) HP = 24″ + 0.4(D-30) Diameter (Ft) Projection (in) Diameter (Ft) Projection (in) 30 18 30 24 40 21 40 28 50 24 50 32 60 27 60 36 70 30 70 40 80 33 80 44 90 36 90 48 100 39 100 52 110 42 110 56 120 45 120 60 130 48 130 64 140 51 140 68 [0018] In another embodiment, the present arrangement takes into account two other factors that affect baffle performance, namely flow rate through the clarifier and the distance between the top of the sludge blanket and the bottom of the baffle. [0019] In one arrangement, the present baffle with a 30 degree inclination (downward from the horizontal or 60 degree upward from the vertical) combined with the extended horizontal projection above, advantageously provide an improving performance as flow rate within the clarifier tank increases. [0020] Moreover, the location of the present baffle relative to the sludge blanket is arranged such that the distance from the top of the blanket to the lower, inboard (center) tip of the baffle, measured vertically, is substantially four feet. This arrangement provides the minimum space necessary for the baffle to intercept and deflect the density currents without creating a “short-circuit” to the launder flow. [0021] Accurately defining the vertical location of the baffle on the wall of the clarifier is difficult because the sludge blanket depth is not fixed and may vary over time. In clarifiers with adequate side water depth, it is best to position the bottom of the baffle midway between the bottom of the weir and the “average” blanket height, or four to six feet above the blanket. In clarifiers that lack sufficient depth, it may be necessary to reduce the horizontal projection of the baffle (and with it, the vertical height of the baffle) to fit the baffle into the space available. In the present arrangement, given the above conditions, the baffle is positioned such that the sludge blanket does not ride up over the baffle. [0022] In another arrangement, in clarifiers with inboard launders, the baffle is usually mounted to the lower inboard corner of the launder trough. It is generally assumed that the bottom of the launder acts as a baffle in intercepting those density currents that rise up the tank wall, while the density current baffle acts to deflect those currents that emerge from beneath the launder down and away from the launder. The present baffle mounted to the launder reduces effluent solids by 15% to 20% over clarifiers with inboard launder and no baffle. [0023] In the case where a baffle is mounted to the launder channel and not the side wall of the clarifier tank, the horizontal projection of a launder-mounted baffle is calculated as though the baffle is to be mounted to the tank wall, and then the width of the launder is subtracted to determine the required projection of the baffle, but in any case with a minimum projection of 24″. [0024] To this end, the present arrangement is directed to a baffle system in a clarifier tank having a tank bottom, a periphery and a substantially vertical peripheral wall bounding the interior of the tank, the tank having an effluent channel. [0025] The baffle system has a plurality of baffles mounted on the clarifier tank, where each baffle has a baffle surface with a lower end and an upper end. The upper end of the baffle surface is coupled to a wall of the clarifier tank. The lower end of the baffle surface is disposed at a substantially 60° angle away from the side wall of the clarifier tank such that the baffle surface slopes downwardly and away from the side wall, where the horizontal projection of the baffle into the center of the tank is determined using the following equation: [0000] HP=24 ″+a ( D −30) D=diameter of the tank in feet; a=coefficient multiplier [0028] with the coefficient “a” is set to 0.4 inches per foot or greater. BRIEF DESCRIPTION OF THE DRAWINGS [0029] The present invention can be best understood through the following description and accompanying drawings, wherein: [0030] FIG. 1 shows a clarifier tank and density current baffle in accordance with one embodiment; [0031] FIG. 2 shows the density current baffle within a clarifier tank in cross section view, in accordance with one embodiment; [0032] FIG. 3 shows a close up view of a density current baffle surface from FIG. 1 in accordance with one embodiment; [0033] FIG. 4 shows a schematic diagram of the baffle of FIG. 1 , in accordance with one embodiment; [0034] FIGS. 5-8 show exemplary test arrangements for the present baffle in various sized clarifier tanks with different sludge blanket conditions; [0035] FIGS. 9-12 show various flow test measurements for the arrangements of FIGS. 5-8 ; [0036] FIGS. 13( a )-( d ) show additional flow test measurements testing the present baffle arrangement against other arrangements; [0037] FIGS. 14( a )-( b ) show additional flow test measurements testing the present baffle arrangement against other arrangements; [0038] FIGS. 15( a )-( b ) show additional flow test measurements testing the present baffle arrangement against other arrangements; [0039] FIGS. 16( a )-( b ) show additional flow test measurements testing the present baffle arrangement against other arrangements; [0040] FIGS. 17( a )-( b ) show additional flow test measurements testing the present baffle arrangement against other arrangements; [0041] FIG. 18 is a graph showing effluent concentration variation over horizontal baffle projections; [0042] FIG. 19 is a graph showing effluent concentration variation over horizontal baffle projections; [0043] FIG. 20 is a graph showing effluent concentration variation over horizontal baffle projections; [0044] FIG. 21 is a graph showing the prior baffle effectiveness over various clarifier diameters; and [0045] FIGS. 22-23 are graphs showing the present baffle compared to the prior baffle effectiveness over various clarifier diameters. DETAILED DESCRIPTION [0046] In one arrangement, as shown in FIG. 1 , a density current baffle 10 is shown attached to a tank wall T. Density current baffle 10 is made from a plurality of connected baffle surfaces 12 , each of which forming a portion of baffle 10 about the circumference of tank wall T. [0047] Bracket elements 14 are positioned under baffle surfaces 12 , preferably at the connection points between adjacent baffle surfaces as shown in FIG. 1 . In one arrangement, an upper mounting flange 18 is located at the top edge of each of baffle surfaces 12 for coupling baffle surfaces 12 to tank wall T. Also as shown in FIG. 1 , an end flange 20 projects downward from each of baffle surfaces 12 , substantially perpendicular to tank wall T. Bracket element 14 and baffle surfaces 12 can be molded as a one piece fiberglass baffle. [0048] FIG. 2 shows a cut away view of baffle 10 within a typically circular type clarifier tank C, having an influent I, tank wall T, a spillway effluent channel and a weir W. Sludge blanket S is shown at the bottom of clarifier tank C, referring to the settled solids. [0049] In one embodiment, as shown in FIG. 3 , a close up view is shown of a single baffle surface 12 of baffle 10 . As shown in FIG. 2 , baffle surface 12 may optionally have one or more vent openings 22 located at the top surface. In one arrangement, vents 22 are formed as convex deformations of upper mounting flange 18 . As noted above, baffle 10 is configured to prevent solids (in the form of density currents) from flowing upwards and out of the clarifier tank and vents 22 are configured to prevent suspended solids from traveling upwards and out into the effluent channel. However, because of the downward sloping design of baffle surfaces 12 , some solids may become trapped, damaging baffle surfaces 12 and possibly reducing their functionality. Vents 22 allow water and solid flow behind baffle surface 12 against tank wall T to prevent the build up of solids. [0050] Using the basic design as set forth above for baffle 10 and baffle surfaces 12 , it has been found by the inventor that by implementing certain advantageous arrangements of baffle surfaces 12 , including the deflection angle of baffle surfaces 12 from tank wall T, the length of projection of the bottom of baffle surfaces 12 from Tank wall T into the center of tank C and the position of baffle surfaces 12 at certain heights on tank wall T, the relative concentration of solids in the effluent may be substantially reduced over the prior art designs. The following description sets forth the salient features of the baffle 10 /baffle surfaces 12 in those respects. [0051] As shown in FIG. 4 , a schematic drawing is shown having various variables for the measurements associated with the size and positioning of baffle surfaces 12 . [0052] D=distance from weir (water level) [0053] L=Length of baffle surface 12 [0054] α=angle from wall T [0055] t=size of end flange [0056] P=Projection distance from wall T (based on α and L) [0057] It is noted that the desired minimum horizontal projection is ideally based on the following equation (s) Or in English Units [0058] Minimum Horizontal Projection=24+α( d [ft]−30), Where Horizontal Projection is in inches α=0.4 inches per foot, and d=tank diameter in feet [0062] In view of the above, an exemplary series or modeling tests were performed to simulate sample baffles (of similar basic design to baffle 10 but with varying dimensions) performance in an exemplary clarifiers C of varying dimensions (e.g. from 70-140 ft diameter), with varying levels of sludge blanket (e.g. from 2-4 foot depth), and with varying distances of baffle tip to sludge blanket (e.g. from 6-10 feet). [0063] Such simulations were carried out for clarifiers with diameters ranging between 70 ft and 140 ft. As shown in the following Table 1, all of the clarifiers were geometrically similar. FIGS. 5 through 8 show typical setups for clarifiers with diameters equal to 70 ft, 100 ft, and 140 ft. [0000] TABLE 1 Distance to Tip of Diameter Side Water Sludge Blanket Baffle from Bottom (ft) Depth (ft) Depth (ft) of Clarifier (ft) 70 10 2 6 80 11.3 2.3 6.3 90 12.6 2.6 6.6 100 14 3 and 7 7 and 9 110 15.5 3.25 7.75 120 17.0 3.5 8.5 130 18.5 3.75 9.25 140 20 4 10 [0064] Using such basic arrangements discussed above, the following table 2 shows nine different high blanket simulations carried out using the 100 ft diameter clarifier setup shown in FIG. 2 . This is a first set of test scenarios that uses a high blanket scenario. [0000] TABLE 2 High Blanket (7.0 ft Deep) Horizontal Case Projection Width SOR Distance between Baffle Number (inches) (inches) (gpd/ft2) Tip and Blanket (ft) 1 39 45 900 2.0 2 46 53 900 2.0 3 53 61 900 2.0 4 60 69 900 2.0 5 46 53 900 1.7 6 53 61 900 1.3 7 46 53 900 2.3 8 53 61 900 2.3 9 60 69 900 2.3 The results of the simulations are shown below in Table 3 (note: relative effluent concentrations have been normalized against the results of scenario 1). Table 2: High Blanket (7.0 ft Deep) [0065] The results of the simulations are shown below in Table 3 (note: relative effluent concentrations have been normalized against the results of scenario 1). [0000] TABLE 3 High-Blanket Study Results Distance between Relative Case Horizontal Baffle Tip and Effluent Number Projection (inches) Blanket (inches) Conc. 1 39 2.0 1 2 46 2.0 .98 3 53 2.0 .97 4 60 2.0 1.2 5 46 1.7 2.3 6 53 1.3 2.5 7 46 2.3 1.3 8 53 2.3 1.6 9 60 2.3 1.9 [0066] According to the results shown above in table 3, increasing baffle projection alone does not necessarily reduce the solids concentration in the effluent entering the launder channel. This may be due to the fact that increasing the horizontal projection of the baffle also increases its vertical dimension and positions the bottom of the baffle too close to the top of the sludge blanket. The space available between the blanket and baffle does not allow the baffle to adequately deflect the current-born solids. For example, FIG. 9 shows the results of a calculation where the projection of a baffle has been increased from 39 inches to 60 inches and the baffle has been positioned 2.3 ft above the blanket (4 inches higher than the standard position in this case). With these changes made, the baffle successfully deflects the density current, but a short-circuiting current forms around the tip of the baffle and more solids are carried into the effluent stream (for this case solids concentrations were about twice what they were for the benchmark case). The “short circuit” may be characterized as a circular eddy of solids that, rather than being deflected towards the center of the tank actually curl around up over the density current baffle. [0067] With hopes of eliminating the short-circuiting current in FIG. 9 , the baffle was lowered 4 inches vertically as shown in FIG. 10 . In this scenario, the short-circuiting current is weakened, however, about 20% more solids are still carried into the launder than in the benchmark case. [0068] To break the short-circuiting current, the projection of the baffle was reduced from 60 inches to 53 inches as shown in FIG. 11 . This change finally reduced effluent solids concentration to values that are similar to the benchmark case. [0069] The results for case numbers 4, 7, 8, and 9 indicate that upper limits for baffle placement exist and that a shorter baffle can sometimes work better than a longer one for conditions where limited space is available for baffle placement. In contrast to this, the results of case numbers 5 and 6 show that lower limits for baffle placement also exist (refer to FIG. 12 where the results of case 6 are shown—here solids are literally plowed up by the baffle and effluent solids concentrations are increased). [0070] In summary, the high blanket scenarios characterize, somewhat atypical, worst-case conditions for baffle sizing, and the best baffle size for this condition is essentially dictated by the space available for its placement with the ideal scenario tested being case 3 of Table 3 shown in FIG. 11 . [0000] TABLE 4 Low Blanket (3.0 ft deep) Horizontal Case Projection Width SOR Distance between Baffle Number (inches) (inches) (gpd/ft2) Tip and Blanket (ft) 1 39 45 900 4.0 2 46 53 900 4.0 3 53 61 900 4.0 4 60 69 900 4.0 [0071] In a next series of testing the present arrangement was again simulated, as shown in Table 4, using four different low blanket simulations using the 100 ft diameter clarifier setup shown in FIG. 7 (note: the low blanket scenarios represent more typical clarifier operations than the high blanket scenarios do). [0072] The results of these simulations are shown in Tables 5 (note: relative effluent concentrations have been normalized against the Case 1 results). [0000] TABLE 5 Low Blanket Study Results Distance between Relative Case Horizontal Baffle Tip and Effluent Number Projection (inches) Blanket Conc. 1 39 4.0 1 2 46 4.0 .97 3 53 4.0 .95 4 60 4.0 .90 [0073] The low-blanket study results were somewhat different than the high-blanket study results. In these scenarios, the blanket was only 3.0 ft deep (compared to 7.0 ft in the high blanket study) and the baffle tips were located about 4.0 ft above the blanket at an elevation of 7.0 ft. [0074] According to the results shown in Table 5, longer baffles reduce effluent solids more than shorter ones do. The maximum improvement was equal to about 10%, and vector plots showing flow around the ends of the baffles in Case Numbers 1 through 4 are all similar. In fact, the flow field shown in FIG. 13( d ) looks to be more prone to short-circuiting than the flow field in FIG. 13( a ) does. If one, for example, plots vectors with the field colored by solids concentrations—it becomes clear why the longer baffle is calculated to reduce more effluent solids concentration. As shown in FIG. 14 , the longer baffle deflects more solids laden flow towards the center of the clarifier and solids concentrations above the baffle are generally less than they are with the shorter baffle. As a result, the longer baffle is calculated to work better than the shorter one in this case. [0075] In a next series of testing the present arrangement was again simulated, as shown in Tables 6(a) and (b), using the effect of surface overflow rates (SOR) on the performance of the present baffle placed in both 70 ft and 100 ft diameter circular clarifiers. These simulations were carried out for conditions with SOR's equal to 600 and 900 gpd/ft 2 . As noted in Tables 6(a) and 6(b), eight simulations were completed. Sketches of the setups for these different study scenarios are provided in FIGS. 5 and 7 , [0000] TABLE 6(a) 70 ft Clarifier Scenarios Horizontal Distance between Case Projection Width SOR Baffle Tip and Number (inches) (inches) (gpd/ft2) Blanket (ft) 1 30 35 600 4.0 2 42 48 600 4.0 3 30 35 900 4.0 4 42 48 900 4.0 [0000] TABLE 6(b) 100 ft Clarifier Scenarios Horizontal Distance between Case Projection Width SOR Baffle Tip and Number (inches) (inches) (gpd/ft2) Blanket (ft) 5 39 45 600 4.0 6 60 69 600 4.0 7 39 45 900 4.0 8 60 69 900 4.0 [0076] The results of the simulation in case Numbers 1 through 8 are shown in Tables 7(a) and 7(b) below (note: relative effluent concentrations have been normalized against the results of scenarios where a standard horizontal projection was used; i.e., scenarios where the horizontal projections equaled 30 inches or 39 inches). [0000] TABLE 7(a) 100 ft Clarifier Distance Horizontal between Baffle Relative Case Projection SOR Tip and Blanket Effluent Number (inches) (gpd/ft2) (ft) Conc. 1 30 600 4.0 1 2 42 600 4.0 .99 3 30 900 4.0 1 4 42 900 4.0 .98 [0000] TABLE 7(b) 100 ft Clarifier Distance Horizontal between Baffle Relative Case Projection SOR Tip and Blanket Effluent Number (inches) (gpd/ft2) (ft) Conc. 5 39 600 4.0 1 6 60 600 4.0 .92 7 39 900 4.0 1 8 60 900 4.0 .90 [0077] According to the 70 ft clarifier study results (Table 7[a]) increasing baffle projection reduces effluent solids concentration slightly, and the reduction of effluent solids is greater for an SOR equal to 900 than it is for an SOR equal to 600. [0078] FIG. 15 shows the results of case numbers 3 and 4 where the field is colored by flow speed. As shown, the longer baffle (right frame) produces a stronger return current; however, the resulting flow pattern reduces effluent solids concentrations only slightly. Similar results were obtained for case numbers 1 and 2, where the SOR was equal to 600, but the results were less dramatic. [0079] According to the results shown in Table 7(b), longer baffles in the 100 ft clarifier reduce effluent solids more than shorter ones do. The percent reduction in effluent solids was calculated to be about 10% maximum. [0080] Vector plots showing flow around the end of the baffles in Case Numbers 7 and 8 are shown in FIGS. 16 and 17 . As before, the longer baffle is calculated to work better than a shorter one (similar to the results obtained from the 70 ft clarifier simulations). [0081] According to the above results, baffles with greater projections show a better ability to reduce effluent solid concentrations more than prior art baffles with smaller projections over the range of conditions tested. Such results also show that the increased effectiveness is greater in larger clarifiers. [0082] Because the above results indicate that longer baffles work better than those sized according to the current (prior art) formulas—additional testing is done to demonstrate the effectiveness of the present baffle arrangement over the prior art. Simulations were carried out in geometrically similar clarifiers with diameters ranging from 70 ft to 140 ft in increments of 10 ft (refer to Table 1). The baffle projections in each case study were varied, and the relative effluent concentration—compared to a baseline condition for each clarifier diameter—was calculated (the baseline condition corresponded to a setup where the baffle was sized according to the formula currently in use today). Then, for each clarifier diameter, the horizontal projection associated with the baffle that reduced effluent solids concentration the most was identified. This data was then plotted and used to develop a new equation for baffle sizing. [0083] The results of modeling in 70 ft, 100 ft, and 140 ft clarifiers are provided in the following sections. The results of modeling carried out in clarifiers with other diameters are not presented; however, the results of the analyses are similar. That is, in all cases, effluent solids concentration was reduced when baffle projection was increased and then at some point the results became inconsistent (i.e., effluent solids concentration was calculated to rise and fall erratically). On the basis of this data, the optimum baffle projection was identified for each clarifier and this information was used to derive a new equation for baffle sizing. This demonstrates that the present invention has identified two competing characteristics regarding effluent solid reduction, namely that longer baffles (than the prior art) work better, but at a certain length and inclination cause circular short circuiting currents. [0084] Table 8 and FIG. 18 show results of clarifier modeling carried out in a 70 foot clarifier operating with an SOR of 900. [0000] TABLE 8 Study results - 70 foot clarifier Relative Horizontal Effluent Projection (inches) Conc. 30 1 42 .98 48 .99 54 .98 [0085] Table 9 and FIG. 19 show results of clarifier modeling carried out in a 100 foot clarifier operating with an SOR of 900. [0000] TABLE 9 study results - 100 ft clarifier Relative Horizontal Effluent Projection (inches) Conc. 39 1 46 .97 53 .95 60 .90 67 .95 74 .92 81 .96 [0086] Table 10 and FIG. 20 show results of clarifier modeling carried out in a 140 foot clarifier operating with an SOR of 900. [0000] TABLE 10 study results - 140 ft clarifier Relative Horizontal Effluent Projection (inches) Conc. 42 1.01 51 1 60 .96 69 1.05 76 1.02 [0087] FIG. 16 shows the results of computations aimed at determining maximum horizontal baffle projection for clarifiers with diameters ranging from 70 ft to 140 ft based on the results presented in sections 4.1 through 4.3. The three points are computed data and the line shows the relationship between clarifier diameter and horizontal projection based on the generally accepted sizing equation below. [0000] Horizontal projections[inches]=18[inches]+0.3[inches/ft]*(clarifier dia.[ft]−30[ft]) [0088] According to the results, effluent solids concentrations are consistently reduced when the horizontal projection of the baffle is increased by as much as 10 inches, regardless of a clarifier's diameter. Projection increases beyond ten inches continue to reduce solids concentrations in larger clarifiers. [0089] As discussed above, similar calculations were also carried out for clarifiers with diameters equal to 80 ft, 90 ft, 110 ft, 130 ft and 140 ft. Although the results of those calculations are not presented herein FIG. 22 provides a summary of all of the computed results (including a representative data point for a simulation where the SOR was equal to 600—note: the error bars show the difference between successive trials with baffles whose projections are different. [0090] Thus, based on the above testing, it is noted that clarifier performance, in general, benefits from the use of baffles with greater horizontal projections; reduction in effluent solids concentration results from the use of longer baffles; longer baffles reduce effluent solids concentration more during model spin-up (when flows in the clarifiers were increased from 0 to 900 SOR); and, as a limit condition, where the sludge blanket is very high relative to a clarifier's side water depth (SWD) baffle length is essentially dictated by the vertical space available for the baffle to be placed. [0091] As a result, the present arrangement uses a density current baffle that employs the horizontal projection based on the following: [0000] Horizontal projections[inches]=24[inches]+0.4[inches/ft]*(clarifier dia.[ft]−30[ft]) [0092] See for example FIG. 23 , which compares the prior art baffle system versus the present baffle arrangement. [0093] While only certain features of the invention have been illustrated and described herein, many modifications, substitutions, changes or equivalents will now occur to those skilled in the art. It is therefore, to be understood that this application is intended to cover all such modifications and changes that fall within the true spirit of the invention.
In this respect, the present arrangement provides a density current baffle that employs a baffle that is dimensioned to balance the fact that larger horizontal projections of density current baffles improve performance while simultaneously recognizing that an overly large baffle would simply not correctly function, be unnecessarily large and complex and may in fact have a negative impact on the otherwise ordinary operation of flows within the clarifier tank. Thus, the present arrangement provides a baffle that improves performance while satisfying the desire to remain conservative in defining an upper limit for the projection. The horizontal projection of the baffle is structured according to the following equation: HP=24″+0.4 inches/foot×(Diameter−30)
1
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a unique method for preparing and applying a lightweight cementitious coating to existing and/or new roof surfaces. By virtue of the method of the present invention, the roof coating provides an extremely durable, light-weight and attractive roof surface. 2. Description of the Prior Art Today, various kinds of coatings or coverings for roof structures are well known. Of course, perhaps the most common type of roof coating or covering material is asphalt-type shingles. Of course, particularly in warm climates, clay and ceramic tiles are also utilized as roof coatings. Another type of roofing material is generally referred to in the building industry as builtup gravel. This type of roofing construction is prepared by the application of a tar, or asphalt base onto which loose gravel is scattered. Finally, more modern structural building techniques have resulted in the construction and application of roofing materials comprising sheets of metal, fiberglass, plastic, or other such synthetic materials. As a result of the energy crisis of recent years, it has also become common practice to apply a coating to existing roof structures for the specific purpose of increasing the insulative capabilities of the roof as well as for the purpose of reflecting the sun's rays. Certain problems have been identified with such roof coatings. In the first place, in order to effectively increase the insulative capabilities of the roof, it is often necessary to add such a heavy coating as to create structural complications. That is to say, it may be necessary to add further reinforcement to the roof construction from within before the coating can be applied. Furthermore, since insulating materials are normally of relatively low density, it is often necessary to add yet a second coating on top of the insulating medium. In the case of roof coatings specifically designed for reflecting the sun's rays, the coating often comprises nothing more than a layer of white, or light-colored paint. In this case, the homeowner is then faced with the requirement of having to maintain a relatively large painted surface. Accordingly, it is clear that there is a great need in the art for a method of coating either existing or new roof structures with a relatively lightweight material such that the roof will be provided with a durable, attractive surface. So that the coating may be utilized in a variety of structural applications, it would be further desirable if it could be applied either manually, as by trowelling or spreading, or by pumping the coating material to the roof sides. Of course, the method for coating the roof must be suitable for use either in new installations or in covering existing roofs. SUMMARY OF THE INVENTION The present invention relates to a unique method for coating either existing or new roof constructions wherein the roof coating mixture comprises a cementitious composition utilizing the lightweight aggregate disclosed and claimed in my U.S. Pat. No. 4,011,355. In accord with the method of the present invention, the lighweight aggregate is admixed with cement, sand and a reinforcing agent such as biferglass strands or steel fibers and water to obtain a suitable consistency. The roof coating mixture is then applied either manually or by pumping onto the prepared roof surface. The roof surface is prepared for application of the coating mixture by first sealing it with felt and tar and applying a reinforcing wire mesh over the felt and tar. The coating mixture is then applied, trowelled, smoothed, and allowed to cure. Once the coating mixture has cured, the surface is ground smooth, and, when appropriate, expansion joints are opened as by cutting. Since the roof coating mixture possesses alkali characteristics, an alkali-resistant resilient material is utilized to fill the expansion joints. Next, a sealant coat is sprayed over the cured, ground roof coating. This sealant may comprise a rubberized coating or a sprayable, hard surfaced cement. Finally, while the sealant is still wet, the coating is dusted with sand having a high silicone content. Accordingly, the method of the present invention provides a relatively lightweight coating which is not only aesthetically pleasing in appearance, but also is extremely durable. The invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others thereof which will be exemplified in the method hereinafter disclosed, and the scope of the invention will be indicated in the Claims. BRIEF DESCRIPTION OF THE DRAWING For a fuller understanding of the nature and objects of the invention, reference should be had to the following detailed description taken in connection with the accompanying drawing, in which: The FIGURE present a flow chart for the roof coating method. DETAILED DESCRIPTION The present invention relates to a method for preparing and applying a coating mixture to a roof structure. As illustrated in the flow chart of the FIGURE, the method first comprises the expansion of polymer beads, such as polystyrene beads, for use as aggregate in the cementitious roof coating mixture once the beads themselves have been coated in accord with the disclosure of my U.S. Pat. No. 4,011,355. Once the polystyrene beads have been coated as described in that patent, the roof coating mixture is obtained by admixing the coated beads to dry cement and sand in the ratio, by volume, of approximately 7 parts coated beads, 2 parts cement and 1/4 part sand. This dry mixture is thoroughly agitated, and while being agitated in its dry state a reinforcing agent such as fiberglass strands or steel fibers is added thereto. This reinforcing agent is preferably added in the ratio of approximately 1%, by weight, with regard to the dry mix. Then, sufficient water is added to obtain a suitable consistency for the completed coating mixture. Meanwhile, the roof structure is prepared for application of the coating mixture by placement of tar and builders felt thereon. The placement of the tar and felt paper is important for its function as a vapor barrier in order to isolate the roof coating from the new or existing roof substructure. Prior to application of the roof mixture it is further desirable to place wire mesh over the felt paper as reinforcement. Having thus prepared the roof, the wet coating mixture is applied. Depending upon the nature of the installation being made, the roof coating mixture may be manually applied or it may be pumped onto the roof. Since the roof coating mixture is a cementitious composition, it is next trowelled to obtain a substantially smooth surface. Furthermore, it should be noted that provision for expansion joints normally associated with relatively large pours of cementitious materials may be desirable. Once the coating mixture has cured, the exposed surface is smoothed by a suitable grinding apparatus. Next, expansion joints, if necessary, are cut and filled with a resilient caulking material. Inasmuch as the roof coating possesses alkali characteristics, the resilient caulking material should be of an alkali-resistant material. Finally, the exposed surface of the roof coating is sealed by spraying thereonto a seal coating in the following preferred example: 1 part alkaline resistant glass 1/32nd. Strand 1 part sand 1 part alumina powder 2 part cement 14 oz. per 100 lbs. weight of water repellent agent 4 lbs. polymeric base 1/2 oz. wetting agent 4 lbs. to 100 lbs. high tensile steel, bronze coated Optional to the steel would be 4 lbs. to 100 lb. mix of 11/2 alkaline resistant glass. Color is optional The dry mixture of sand, glass, alumina, cement, water repellent agent, polymeric and wetting agent is mixed with water to a sprayable consistency. Spray one layer down--if conditions are dry, mist with water before coating. The metal of fiberglass fibers are applied in an even pattern onto the roof area. Then another coating is applied or sprayed onto the fibers, making a finished coating. In order to enhance the final appearance of the roof it may be desirable to lightly dust the wet sealant material with sand of a high silicone content. If so dusted, the new roof will exhibit a clean white appearance much like that of fresh-fallen snow. It is, of course, to be understood that the roof coating method described herein is suitable for use over virtually any type roof construction or substrate. Advantageously, the roof covering does not adhere and is not attached to the roof being covered and therefore does not generate thermal stresses between the roof coating and the roof surface being coated. It is furthermore to be understood that the final appearance of the roof coating may be altered as by the addition of colorants thereto without departing from the scope of the invention. It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained, and since certain changes may be made in carrying out the above method without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense. It is also to be understood that the following Claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween.
A unique method for applying a lightweight cementitious coating to either existing or new roof surfaces. The invention relates to the method of preparing the coating mixture and its manner of application.
2
CROSS REFERENCE TO RELATED APPLICATION This application claims the priority of provisional application Ser. No. 60/063,669, filed Oct. 28, 1997. FIELD OF THE INVENTION This invention relates to a series of novel cyclopentene derivatives, pharmaceutical compositions containing them and intermediates used in their manufacture. The compounds of the invention are useful as non-peptidyl antagonists of the motilin receptor. In addition, the compounds display efficacy and potency which are comparable to known motilin and erythromycin antagonists. BACKGROUND In mammals, the digestion of nutrients and the elimination of waste is controlled by the gastrointestinal system. This system is, to say the least, complicated. There are a number of natural peptides, ligands, enzymes, and receptors which play a vital role in this system and are potential targets for drug discovery. Modifying the production of, or responses to these endogenous substances can have an effect upon the physiological responses such as diarrhea, nausea, and abdominal cramping. One example of an endogenous substance which affects the gastrointestinal system is motilin. Motilin is a peptide of 22 amino acids which is produced in the gastrointestinal system of number of species. Although the sequence of the peptide varies from species to species, there are a great deal of similarities. For example, human motilin and porcine motilin are identical; while motilin isolated from the dog and the rabbit differ by five and four amino acids respectively. Motilin induces smooth muscle contractions in the stomach tissue of dogs, rabbits, and humans as well as in the colon of rabbits. Apart from local gastrointestinal intestinal tissues, motilin and its receptors have been found in other areas. For example motilin has been found in circulating plasma, where a rise in the concentration of motilin has been associated with gastric effects which occur during fasting in dogs and human. Itoh, Z. et al. Scand. J. Gastroenterol. 11:93-110, (1976); Vantrappen, G. et al. Dig. Dis Sci 24, 497-500 (1979). In addition, when motilin was intravenously administered to humans it was found to increase gastric emptying and gut hormone release. Christofides, N. D. et al. Gastroenterology 76:903-907, 1979. Aside from motilin itself, there are other substances which are agonists of the motilin receptor and which elicit gastrointestinal emptying. One of those agents is the antibiotic erythromycin. Even though erythromycin is a useful drug, a great number of patients are affected by the drug's gastrointestinal side effects. Studies have shown that erythromycin elicits biological responses that are comparable to motilin itself and therefore may be useful in the treatment of diseases such as chronic idiopathic intestinal pseudo-obstruction and gastroparesis. Weber, F. et al., The American Journal of Gastroenterology, 88:4, 485-90 (1993). Although motilin and erythromycin are agonists of the mtotilin receptor, there is a need for antagonists of this receptor as well. The nausea, abdominal cramping, and diarrhea which are associated with motilin agonsits are not always welcome physiological events. The increased gut motility induced by motilin has been implicated in diseases such as Irritable Bowel Syndrome and esophageal reflux. Therefore researchers have been searching for motilin antagonists. One such antagonist is OHM-11526. This is a peptide derived from porcine motilin which competes with both motilin and erythromycin for the motilin receptor in a number of species, including rabbits and humans. In addition, this peptide is an antagonist of the contractile smooth muscle response to both erythromycin and motilin in an in vitro rabbit model. Depoortere, I. et al., European Journal of Pharmacology, 286, 241-47, (1995). Although this substance is potent in that model (IC 50 1.0 nm) it is a peptide and as such offers little hope as an oral drug since it is susceptible to the enzymes of the digestive tract. Zen Itoh, Motilin, xvi (1990). Therefore it is desirable to find other agents which are not peptides as potential motilin antagonists. The compounds of this invention are such agents. The compounds of this invention are non-peptidyl motilin antagonists with potencies and activities comparable to known peptidyl motilin antagonists. These compounds compete with motilin and erythromycin for the motilin receptor site in vitro. In addition, these compounds suppress smooth muscle contractions induced by motilin and erythomycin with activities and potencies comparable to OHM 11526 in an in vitro model. SUMMARY OF THE INVENTION The present invention is directed to compounds of Formula I ##STR1## wherein R 1 is hydrogen, C 1-5 alkyl, substituted C 1-5 alkyl (where the alkyl substituents are one or more halogens), aminoC 1-5 alkyl, C 1-5 alkylaminoC 1-5 alkyl; di-C 1-5 -salkylaminoC 1-5 alkyl, R a R b N-C 1-5 alkyl (where the R a and R b are independently selected from hydrogen and C 1-5 alkyl, or are taken together to form a morpholine, piperazine, piperidine, or N-substituted piperidine where the N-substitutent is C 1-5 alkyl or phenylC 1-5 alkyl), C 1-5 alkylcarbonyl, C 1-5 alkoxycarbonyl, aminocarbonyl, C 1-9 alkylaminocarbonyl, cycloC 3-9 alkylaminocarbonyl, pyridinylcarbonyl, substituted pyridinylcarbonyl (where the pyridinyl substituents are selected from the group consisting of one or more halogens and C 1-5 alky), thiophenecarbonyl, substituted thiophenecarbonyl (where the thiophene substituents are) selected from the group consisting of one or more halogens and C 1-5 alkyl), phenyl, phenylC 1-5 alkyl, phenoxycarbonyl, phenylcarbonyl, diphenylmethylcarbonyl, phenylaminocarbonyl, phenylthiocarbonyl, phenylaminothiocarbonyl, substituted phenyl, substituted phenylC 1-5 alkyl, substituted phenoxycarbonyl, substituted phenylcarbonyl, substituted phenylaminocarbonyl, substituted diphenylmethylcarbonyl, substituted phenylthiocarbonyl, and substituted phenylaminothiocarbonyl (where the phenyl substituents are selected from the group consisting of one or more of halogen, C 1-5 alkyl, trihalomethyl, C 1-5 alkoxy, amino, nitrile, nitro, C 1-5 alkylamino, di-C 1-5 salkylamino, if there are more than one substitutents they may be taken together with the phenyl ring to form a fused bicyclic 7-10 membered heterocyclic ring having one to two heteroaloms selected from oxygen, sulfur or nitrogen or the substituents may be taken together to form a fused bicyclic 7-10 membered aromatic ring; R 2 is hydrogen, C 1-5 alkyl, C 1-5 ralkoxy, phenyl, substituted phenyl (where the phenyl substituents are selected from one or more of the group consisting of halogen and C 1-5 alkyl), phenylC 1-5 alkyl, substituted phenylC 1-5 alkyl (where the phenyl substituents are selected from one or more of the group consisting of halogen, C 1-5 alkyl, C 1-5 alkoxy, halo and di-C 1-5 alkylamino) R 3 is hydrogen, C 1-5 alkylcarbonyl, substituted C 1-5 alkylcarbonyl (where the alkyl substituents are selected from one or more halogens), phenylcarbonyl, and substituted phenylcarbonyl (where the phenyl substituents are selected from one or more of the group consisting of halogen, C 1-5 alkyl, C 1-5 alkoxy, amino, C 1-5 alkylamino, and di-C 1-5 alkylamino) R 4 is hydrogen, C 1-5 alkylcarbonyl, substituted C 1-5 alkylcarbonyl (where the alkyl substituents are selected from one or more halogens), phenylcarbonyl, and substituted phenylcarbonyl (where the phenyl substituents are selected from one or more of the group consisting of halogen, C 1-5 alkyl, C 1-5 alkoxy, amino, C 1-5 alkylamino, and di-C 1-5 alkylamino) n is 0-3; m is 1-5 R 5 is ##STR2## where: q is 0-2; t is 0-1; X is oxygen, CH 2 , sulfur, or NR c where R c is hydrogen, C 1-5 alkyl, morpholinoC 1-5 alkyl, piperidinylC 1-5 alkyl, N-phenylmethylpiperidinyl or piperazinylC 1-5 alkyl, with the proviso that if q and t are 0, then X is hydroxy, thiol, or amino, A is C 1-5 salkoxycarbonyl, phenylcarbonyl, or R 7 R 8 N-- where R 7 is independently selected from hydrogen, C 1-5 alkyl, cycloC 3-9 alkyl, or R 7 is taken together with R 8 to form a 5 or 6 membered heterocyclic ring with one or more heteroatoms selected from the group consisting of oxygen, nitrogen or sulfur and N-oxide.s thereof; R 8 is independently selected from hydrogen, C 1-5 alkyl, cycloC 3-9 galkyl or taken together with R 7 to form a 5 or 6 membered heterocyclic ring with one or more heteroatoms selected from the group consisting of oxygen, nitrogen or sulfur, and N-oxides thereof; R 6 is hydrogen, halogen, C 1-5 alkoxy, C 1-5 alkylamino, or di-C 1-5 alkylamino or pharmaceutically acceptable salts thereof. The compounds of formula I are useful in treating gastrointestinal disorders associated with the motilin receptor. The compounds compete with erythromycin and motilin for the motilin receptor. In addition, the compounds are antagonists of the contractile smooth muscle response to those ligands. The present invention also comprises pharmaceutical compositions containing one or more of the compounds of formula I as well as methods for the treatment of disorders related to the gastrointestinal system which are associated with the motilin receptor. Such diseases include Irritable Bowel Syndrome, esophageal reflux, and the gastrointestinal side effects of erythromycin. DETAILED DESCRIPTION OF THE INVENTION The terms used in describing the invention are commonly used and known to those skilled in the art. However, the terms that could have other meanings are defined. "Independently" means that when there are more than one substituent, the substituents may be different. The term "alkyl" refers to straight, cyclic and branched-chain alkyl groups and "alkoxy" refers O-alkyl where alkyl is as defined supra. The symbol "Ph" refers to phenyl, the term "fused bicyclic aromatic" includes fused aromatic rings such as naphthyl and the like. The term "fused bicyclic heterocycle" includes benzodioxoles and the like. Since the compounds of the invention have a chiral center, some of the compounds are isolated as enantiomers. In those cases the determination of absolute stereochemistry is pending. When compounds contain a basic moiety, acid addition salts may be prepared and may be chosen from hydrochloric, hydrobromic, hydroiodic, perchloric, sulfuric, nitric, phosphoric, acetic, propionic, glycolic, lactic, pyruvic, oxalic, malonic, succinic, maleic, fumaric, malic, tartaric, citric, benzoic, cinnamic, mandelic, methanesulfonic, p-toluenesulforlic, cyclohexanesulfamic, salicylic, 2-phenoxybenzoic, 2-acetoxybenzoic, or saccharin, and the like. Such salts can are made by reacting the free base of compounds of formula I with the acid and isolating the salt. The compounds of the invention may be prepared by the following schemes, where some schemes produce more than one embodiment of the invention. In those cases, the choice of scheme is a matter of discretion which is within the capabilities of those skilled in the art. A synthesis of the compounds of the invention is depicted in Scheme 1. Essentially this scheme assembles two halves of the molecule and couples them. For one half, 3-ethoxy-2-cyclohexen-1-one,1a, is the starting material. 1a is treated with a Grignard reagent, 1b, such as 4-fluorobenzyl magnesium bromide at room temperature under an inert atmosphere, using ether as a solvent to give the α,β-unsaturated ketone derivative 1c. Treatment of 1c with a reducing agent such as LAH at 0° C. to room temperature over 16 h gives the alcohol, 1d. This alcohol is treated with a strong base such as NaH and trichloroacetonitrile from 0° C. to room temperature for 16 h to give the amide 1e. This six membered ring amide is sequentially treated with ozone at -78° C., dimethylsulfide, and a catalytic amount of acid such as toluene sulfonic acid. Once addition is complete, the mixture is allowed to warm to room temperature over 24-64 h to give the five membered ring aldehyde 1f, as a racemic mixture. To assemble the other half, an aromatic alcohol 1g, such as 3-hydroxyaniline is treated with a mild base, such as K 2 CO 3 , in a suitable solvent such as EtOH at 60° C. over 4-6 h. This mixture is subsequently treated with a halide derivative 1h, such as 3-chloropropylmorpholine at room temperature to give the amine 1i. This amine is treated with the aldehyde 1f and NaCNBH 3 in MeOH at room temperature over 30 min to give a compound of the invention, 1j as a racemic mixture. If pure enantiomers are desired, they may be obtained in any of three stages of the synthesis. The alcohol 1d, the aldehyde 1f, and the product 1j may all be separated via HPLC using chiral columns or methods known of those skilled in the art. With respect to all three compounds, they may be further manipulated to give other compounds of the invention without sacrificing their enantiomeric purity. This scheme may be used to produce other compounds of the invention. For example, to produce compounds where X is sulfur, simply replace reagent 1h with an aromatic thiol, such as 3-aminothiophenol and carry out the remaining steps of the Scheme. ##STR3## To produce other substitutions at R 3 or R 4 some of the products of Scheme 1 may be used. For example, to produce a compound where R 3 is hydrogen and R 4 is CH 3 C(O)--, the six-membered ring intermediate 1e, is treated with a base, such as barium hydroxide, at reflux in EtoH to give the free amine 2a. The amine is subsequently treated with an acid anhydride, such as trifluoroacetic anhydride to give 2b. This intermediate may be carried through the remaining steps of Scheme 1 to produce the desired compound. ##STR4## The products of Scheme 1 may be used to produce other compounds of the invention. For example, to produce compounds of type 3a, treat compound 1j with a phenyl isocyanate at room temperature over 24 h. To produce compounds of type 3b, 1j may be treated at room temperature with acid chloride derivatives such as benzoyl chloride. In order to produce thiols 3c, compounds of type 1j may be treated with isothiocyanates, such as phenylisothiocyanate at room temperature. As discussed earlier, if pure enantiomers are desired, they may be obtained by chromatography of the reactant, 1j or the products. ##STR5## Yet another scheme (Scheme 4) makes use of the intermediate of Scheme 1. Treatment of the aldehyde, 1f, with a nitroaniline derivative 4a, and NaCNBH 3 at room temperature gives the coupled intermediate 4b. This intermediate may be acylated with benzoyl chloride and a mild base such as triethylamine to give the N-acyl intermediate 4c. 4c may be treated with a reducing agent such as Pd/C to give the aniline compound 4d. This compound may be coupled with a halogen derivative 4e, such as 3-chloropropylpiperidine, using DBU and an alcoholic solvent at reflux over 4 h to give a mixture of mono and di amine products. ##STR6## To prepare compounds of the invention where n is 1-3, products of Scheme 1 are used in Scheme 5. Intermediate 1f is treated with 3-(m-hydroxyphenyl)propylamine, an aromatic amino alcohol derivative 5a, and NaCNBH 3 at room temperature over 16 h to give the amine 5b. Treatment of 5b with a thiocyanate derivative 5c, and a mild base at room temperature gives the substituted thioamide 5d. This compound may be treated with a halide reagent, 5e, and a base such as DBU in an alcoholic solvent at reflux to give the O-substituted compound of the invention. ##STR7## The compounds of the invention were tested for their ability to compete with radiolabeled motilin (porcine) for the motilin receptors located on the colon of mature rabbits. The colon from mature New Zealand rabbits was removed, dissected free from the mucosa and serosa layers, and diced into small pieces. The muscle tissues were homogenized in 10 volumes of buffer (50 mM Tris-Cl, 10 mM MgCl 2 , 0.1 mg/mL bactracin, and 0.25 mM Peflabloc, pH 7.5) in a Polytron (29,000 rpm, 4×15 seconds). The homogenate was centrifuged at 1000×g for 15 min. and the supernatant discarded. The pellet was washed twice before being suspended in homogenizing buffer. This crude homogenate is then passed first through a 19 gauge needle then a 23 gauge needle to further suspend the material and stored as -80° C. In a total volume of 0.50 mL, the binding assay contains the following components added sequentially, buffer (50 mM Tris-Cl, 10 mM MgCl 2 , 1 mM EDTA, 15 mg/mL BSA, 5 μg/mL leupeptin, aprotinin, and pepstatin, and 0.1 mg/mL, bactracin), 1 125 motilin (Amersham, ca 50,000-70,000 cpm, 25-40 pM), the test compound (the initial concentration was 2 mM/100% DMSO, which diluted with H 2 O to a final concentration of 10 μM) and membrane protein (100-300 μg). After 30 min, at 30° C., the material was cooled on ice and centrifuged at 13,000×g for 1 minute. The pellet was washed with 1 mL 0.9% saline and centrifuged at 13,000×g for 15 seconds. The pellet was washed again with cold saline and the supernatant was removed. The pellet was counted in the gamma counter to determine the percentage of unbound motilin and thereby the percent inhibition of the test compound. IC 50s were determined for some compounds by standard techniques. TABLE A__________________________________________________________________________1 #STR8##RWJ/Cpd.R.sub.1 n R.sub.5 R.sub.6 IC.sub.50 /% Inhibition__________________________________________________________________________8 phenylNH--C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 20 nM**9 phenylNH--C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H >300 nM***69 H 0 4-OH H 11% @ 10 μM50 (CH.sub.2).sub.2 NEt.sub.2 0 3-OH H 81% @ 10 μM51 (CH.sub.2).sub.2 NEt.sub.2 0 3-O(CH.sub.2).sub.2 NEt.sub.2 H 0.6% @ 10 μM52 (CH.sub.2).sub.2 NEt.sub.2 0 3-O(CH.sub.2).sub.2 piperidin-1-yl H 0.653 (CH.sub.2).sub.2 NEt.sub.2 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 0.354 (CH.sub.2).sub.2 NEt.sub.2 0 3-O(CH.sub.2).sub.3 piperidin-1-yl H 0.955 (CH.sub.2).sub.2 NEt.sub.2 0 3-O(CH.sub.2).sub.2 pyrrolidin-1-yl H 0.970 (CH.sub.2).sub.2 NEt.sub.2 0 2-O(CH.sub.2).sub.2 morpholin-1-yl H 80% @ 10 μM56 H 0 4-S(CH.sub.2).sub.2 NMe.sub.2 H 1.571 (CH.sub.2).sub.2 NEt.sub.2 0 4-O(CH.sub.2).sub.2 NMe.sub.2 H 85% @ 10 μM58 H 0 4-S(CH.sub.2).sub.2 NEt.sub.2 H 1.857 (CH.sub.2).sub.2 - 1 3-O(CH.sub.2).sub.2 morpholin-1-yl H 0.7morpholin-1-yl72 (CH.sub.2).sub.2 NEt.sub.2 0 2-O(CH.sub.2).sub.2 morpholin-1-yl H 0.973 (CH.sub.2).sub.2 NEt.sub.2 0 2-OH H 84% @ 10 μM74 (CH.sub.2).sub.2 NEt.sub.2 0 4-OH H 81% @ 10 μM75 H 0 3-NH.sub.2 H 41% @ 10 μM76 (CH.sub.2).sub.2 NEt.sub.2 2 4-OH H 84% @ 10 μM77 1-benzylpip- 1 3-O(CH.sub.2).sub.2 NEt.sub.2 H 0.8eridin-4-yl58 H 0 3-S(CH.sub.2).sub.2 NEt.sub.2 H 61% @ 10 μM78 CH.sub.3 C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 1.0310 phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 0.36 H 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 37% @ 10 μM46 phenylC(O) 0 3-OCH.sub.2 CO.sub.2 Et H 51% @ 10 μM79 phenylC(O) 0 3-S(CH.sub.2).sub.2 NEt.sub.2 H 98% @ 10 μM22 phenylNH--C(O) 0 3-S(CH.sub.2).sub.2 morpholin-1-yl H 83% @ 10 μM80 4-F-phenyl-C(O) 0 3-S(CH.sub.2).sub.2 morpholin-1-yl H 79% @ 10 μM81 H 2 3-S(CH.sub.2).sub.2 morpholin-1-yl H 81% @ 10 μM82 phenylC(O) 0 3-S(CH.sub.2).sub.2 morpholin-1-yl H 80% @ 10 μM83 phenylC(O) 1 3-O(CH.sub.2).sub.2 NEt.sub.2 H 100% @ 10 μM84 4-CH.sub.3 O-phenylC(O) 0 3-S(CH.sub.2).sub.2 morpholin-1-yl H 59% @ 10 μM85 (CH.sub.2).sub.2 - 2 3-O--C(O)phenyl H 9% @ 2.0 μMmorpholin-1-yl86 phenylC(O) 0 4-S(CH.sub.2).sub.2 N(CH.sub.3).sub.2 H 49% @ 2.0 μM40 H 0 3-O(CH.sub.2).sub.2 morpholin-1-yl 4-OCH.sub.3 27% @ 10 μM87 H 0 3-OH 4-OCH.sub.3 32% @ 10 μM88 benzyl 1 3-O(CH.sub.2).sub.2 morpholin-1-yl H 94% @ 10 μM89 4-CH.sub.3 O-phenylNH--C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 26% @ 5.0 μM90 3-CH.sub.3 O-phenyl-C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 65% @ 0.5 μM91 phenylC(O) 1 1-benzylpip- H 77% @ 10 μM eridin-4-amino92 (CH.sub.2).sub.2 NEt.sub.2 2 3-O(CH.sub.2).sub.2 morpholin-1-yl H 95% @ 10 μM32 phenylC(O) 1 3-O(CH.sub.2).sub.2 morpholin-1-yl H 70% @ 10 μM59 4-F-phenyl-C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 52 nM60 4-CH.sub.3 O-phenyl-C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 90 nM7 phenylNH--C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 45 nM93 benzyl 0 3-O(CH.sub.2).sub.2 morpholin-1-yl 4-OCH.sub.3 62% @ 10 μM94 H 0 3-O(CH.sub.2).sub.2 morpholin-1-yl 4-OCH.sub.3 48% @ 10 μM34 phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl 4-OCH.sub.3 74% @ 10 μM95 (CH.sub.2).sub.2 - 2 3-O--C(O)phenyl 4-OCH.sub.3 22% @ 2.0 μMmorpholin-1-yl41 phenylC(O) 2 3-O(CH.sub.2).sub.2 morpholin-1-yl H 82% @ 10 μM96 4-CH.sub.3).sub.2 N-phenylC(O) 2 3-O(CH.sub.2).sub.2 morpholin-1-yl H 62% @ 1.0 μM97 3,4-dichlorophenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 260 nM98 4-F-phenylC(O) 0 3-(CH.sub.2).sub.3 morpholin-1-yl H 17% @ 1.0 μM99 3,5-di-CF.sub.3 -phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 28% @ 1.0 μM100 2,3,4,5,6-pentafluoro- 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 1000 nMphenylC(O)19 phenyl-NHC(O) 0 3-(CH.sub.2).sub.3 morpholin-1-yl H 59% @ 1.0 μM61 4-Br-phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 64% @ 0.05 μM101 3-Br-phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 54% @ 0.1 μM102 4-Cl-phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 61% @ 0.1 μM103 3-CF.sub.3 -phenylC(O) 0 3-O(CH.sub.2).sub.3 morpholin-1-yl H 52% @ 0.1 μM104 4-CF.sub.3 -phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 29% @ 0.1 μM105 4-I-phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 59% @ 0.1 μM106 3,5-di-F.sub.2 -phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 78% @ 0.1 μM62 3,4-di-F.sub.2 -phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 50 nM1407 4-(phenyl)phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 58% @ 1.0 μM108 thiophen-2-yl-C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 84% @ 1.0 μM11 phenylNH--C(S) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 45% @ 0.1 μM109 4-NC-phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 98 nM110 4-t-butyl-phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 19% @ 1.0 μM111 pyridin-4-yl-C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 51% @ 1.0 μM63 3-F-phenyl-NHC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 37 nM112 3-Br-phenyl-NHC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 51% @ 1.0 μM38 4-Br-phenyl-C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl 6-Cl 59% @ 1.0 μM113 3-F-phenyl-C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl 6-Cl 59% @ 1.0 μM114 3,4-diF-phenyl-C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl 6-Cl 52% @ 100 μM115 3-Br-thiophen- 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 65% @ 1.0 μM1-yl-C(O)-116 4-NO.sub.2 -phenyl-C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 69% @ 0.1 μM117 di-phenyl-CH--C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 42% @ 1.0 μM118 phenyl-OC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 51% @ 1.0 μM119 cyclohexyl-NHC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 56% @ 1.0 μM__________________________________________________________________________ TABLE B__________________________________________________________________________2 #STR9##Cpd. R.sub.1 n R.sub.2 IC.sub.50 /% Inhibition__________________________________________________________________________120 4-F-phenyl-NH--C(O) 0 3-Cl-benzyl 10 nM121 4-F-phenyl-C(O) 0 3-Cl-benzyl 30 nM65 4-F-phenyl-C(O) 0 4-MeO-benzyl 56 nM66 phenyl-C(O) 0 4-MeO-benzyl 56 nM122 1,3-benzodioxol-5-yl-C(O) 0 benzyl 77% @ 1.0 μM123 phenyl-NH--C(O) 0 (CH.sub.3).sub.2 CH-- 51% @ 1.0 μM124 naphthy-1-yl-C(O) 0 benzyl 40% @ 0.1 μM125 4-F-phenyl-C(O) 0 4-F-benzyl 43% @ 0.04 μM126 3-F-phenyl-C(O) 0 4-F-benzyl 44% @ 0.04 μM67 phenyl-NHC(O) 0 4-F-benzyl 34% @ 0.25 μM127 phenyl-NHC(O) 0 phenyl 33% @ 0.1 μM128 4-F-phenyl-C(O) 0 phenyl 43% @ 0.1 μM68 phenyl-NHC(O) 0 3-Cl-benzyl 70% @ 0.1 μM129 4-Br-phenyl-C(O) 0 3-Cl-benzyl 70% @ 0.1 μM130 3,4-di-F-phenyl-C(O) 0 3-Cl-benzyl 78% @ 0.1 μM__________________________________________________________________________ TABLE C__________________________________________________________________________3 #STR10##Cpd. R.sub.1 R.sub.2 R.sub.3 R.sub.5 IC.sub.50 /% Inhibition__________________________________________________________________________131 H benzyl CF.sub.3 C(O) 3-O(CH.sub.2).sub.2 morpholin-1-yl 25% @ 10 μM132 phenyl-C(O) benzyl CF.sub.3 C(O) 3-O(CH.sub.2).sub.2 morpholin-1-yl 0.73 nM15 phenyl-NH-C(O) benzyl CH.sub.3 C(O) 3-O(CH.sub.2).sub.2 morpholin-1-yl 40% @ 1.0 μM133 4-F-phenyl-C(O) benzyl CH.sub.3 C(O) 3-O(CH.sub.2).sub.2 morpholin-1-yl 51% @ 1.0 μM134 phenyl-NH--C(O) benzyl CF.sub.3 C(O) 3-O(CH.sub.2).sub.2 morpholin-1-yl 69% @ 1.0 μM135 (CH.sub.2).sub.2 NEt.sub.2 (CH.sub.3)CH CCl.sub.3 C(O) 3-O(CH.sub.2).sub.2 N(CH.sub.3).sub.2 1.6 nM__________________________________________________________________________ TABLE D__________________________________________________________________________4 #STR11##Cpd. R.sub.1 IC.sub.50 /% Inhibition__________________________________________________________________________136 phenyl-NH--C(O) 57% @ 1.0 μM137 4-Br-phenyl-C(O) 50% @ 1.0 μM__________________________________________________________________________ Select compounds of the invention were evaluated for their ability to inhibit motilin and erythromycin induced contractions in the rabbit duodenum smooth muscle. Rabbits were fasted 24-48 h and euthanized. The venral midline incision was made approximately 7.5 cm above the umbilicus upto the xyphoid process, exposing the upper peritoneal cavity. The first 8 cm. of the duodenum starting at the pyloric valve was quickly removed and placed in Krebs solution containing NaCl, (120 m), KCl (4.7 mM), MgSO 4 *7 H 2 O (1.2 mM), CaCl 2 *2 H 2 O (2.4 mM), KH 2 PO 4 (1 mM), D-glucose (10 mM), and NaHCO 3 (24 mM). The lumen was flushed with Krebs and excess tissue was removed. The tissue was cut lengthwise, splayed open with the longitudinal muscle layer facing up, and the longitudinal muscle layer was released away from the circular muscle and cut into 3×30 mm strips. A pre-tied 4-0 silk ligature with a loop was placed at the middle of the strip and the strip was folded over the loop so the strip was half its original length. The tissues were mounted in a 10 mL tissue bath (Radnotti Glass Technology, Inc., Monrovia, Calif.) containing Krebs solution gassed with 95% O 2 5% CO 2 at 37° C. The tissues were attached to a force displacement transducer (FT03, Grass Instruments, Quincy, Mass.) and resting tension was slowly increased to 1 g. The tissues were allowed to equilibrate for 60-90 min with 2-3 wash cycles. The tissues were equilibrated with two initial contractions induced by a concentration of acetylcholine (1×10 -4 M) that produced a maximal contraction (0.1 mM), with the highest taken as 100% maximall contraction of that tissue. Base line and response levels are expressed as grams tension developed and as a percent of the response to acetylcholine. The test compounds were dissolved in DMSO (2 mM/100% DMSO) and applied to the prepared strips 5-15 minutes prior to the addition of porcine motilin. After addition, the tension is constantly monitored over 5 min and the maximum tension is recorded. The percent contraction was measured at four ascending concentrations and where appropriate IC 50s were determined. TABLE A__________________________________________________________________________5 #STR12##RWJ/Cpd.R.sub.1 n R.sub.5 R.sub.6 IC.sub.50 /% Inhibition__________________________________________________________________________8 phenylNH--C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 280 nM**9 phenylNH--C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 890 nM***50 (CH.sub.2).sub.2 NEt.sub.2 0 3-OH H 98% @ 20 μM51 (CH.sub.2).sub.2 NEt.sub.2 0 3-O(CH.sub.2).sub.2 NEt.sub.2 H 74% @ 5 μM52 (CH.sub.2).sub.2 NEt.sub.2 0 3-O(CH.sub.2).sub.2 piperidin-1-yl H 70% @ 10 μM53 (CH.sub.2).sub.2 NEt.sub.2 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 3.93 mM54 (CH.sub.2).sub.2 NEt.sub.2 0 3-O(CH.sub.2).sub.3 piperidin-1-yl H 24% @ 5 μM55 (CH.sub.2).sub.2 NEt.sub.2 0 3-O(CH.sub.2).sub.2 pyrrolidin-1-yl H 43% @ 2 μM56 H 0 4-S(CH.sub.2).sub.2 NMe.sub.2 H 24% @ 2 μM57 (CH.sub.2).sub.2 - 1 3-O(CH.sub.2).sub.2 morpholin-1-yl H 1.06morpholin-1-yl58 H 0 4-S(CH.sub.2).sub.2 NEt.sub.2 H 44% @ 2.0 μM10 phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 393 nM59 4-F-phenyl-C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 54% @ 3.0 μM60 4-CH.sub.3 O-phenyl-C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 49% @ 10 μM7 phenylNH--C(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 287 nM61 4-Br-phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 63% @ 1.0 μM62 3,4-di-F.sub.2 -phenylC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 65% @ 1.0 μM63 3-F-phenyl-NHC(O) 0 3-O(CH.sub.2).sub.2 morpholin-1-yl H 63.8% @ 1.0 μM__________________________________________________________________________ TABLE B__________________________________________________________________________2 #STR13##Cpd. R.sub.1 n R.sub.2 IC.sub.50 /% Inhibition__________________________________________________________________________65 4-F-phenyl-C(O) 0 4-MeO-benzyl 72% @ 1.0 μM66 phenyl-C(O) 0 4-MeO-benzyl 58% @ 1.0 μM67 phenyl-NHC(O) 0 4-F-benzyl 25.7% @ 1.0 μM68 phenyl-NHC(O) 0 3-Cl-benzyl 51% @ 1.0 μM__________________________________________________________________________ Although the claimed compounds are useful as modulators of the motilin receptor, some compounds are more active than others. These compounds are particularly preferred. The particularly preferred compounds are those where: R 1 is phenylaminocarbonyl, phenylcarbonyl, substituted phenylaminocarbonyl, substituted phenylcarbonyl, and hydrogen; R 2 is phenylC 1-5 alkyl; R 3 is hydrogen; R 4 is trifluoromethylacetyl; R 5 is O-(CH 2 ) 2 -morpholin-1-yl; R 6 is hydrogen; n is 0; and m is 1. To prepare the pharmaceutical compositions of this invention, one or more compounds or salts thereof, as the active ingredient, is intimately admixed with a pharmaceutical carrier according to conventional pharmaceutical compounding techniques, which carrier may take a wide variety of forms depending on the form of preparation desired for administration, e.g., oral or parenteral. In preparing the compositions in oral dosage form, any of the usual pharmaceutical media may be employed. Thus for liquid oral preparations, such as for example, suspensions, elixirs and solutions, suitable carriers and additives include water, glycols, oils, alcohols, flavoring agents, preservatives, coloring agents and the like; for solid oral preparations such as, for example, powders, capsules and tablets, suitable carriers and additives include starches, sugars, diluents, granulating agents, lubricants, binders, disintegrating agents and the like. Because of their ease in administration, tablets and capsules represent the most advantageous oral dosage form, in which case solid pharmaceutical carriers are obviously employed. If desired, tablets may be sugar coated or enteric coated by standard techniques. For parenterals, the carrier will usually comprise sterile water, though other ingredients, for example, for purposes such as aiding solubility or for preservation, may be included. Injectable suspensions may also be prepared, in which case appropriate liquid carriers, suspending agents and the like may be employed. The pharmaceutical compositions herein will preferably contain per dosage unit, e.g., tablet, capsule, powder, injection, teaspoonful and the like, from about 5 to about 500 mg of the active ingredient, although other unit dosages may be employed. In therapeutic use for treating disorders of the gastrointestinal system in mammals, the compounds of this invention may be administered in an amount of from about 0.5 to 100 mg/kg 1-2 times per day orally. In addition the compounds may be administered via injection at 0.1-10 mg/kg per day. Determination of optimum dosages for a particular situation is within the capabilities of formulators. In order to illustrate the invention, the following examples are included. These examples do not limit the invention. They are meant to illustrate and suggest a method of practicing the invention. Although there are other methods of practicing this invention, those methods are deemed to be within the scope of this invention. EXAMPLES Example 1 ##STR14## A solution of 3-ethoxy-2-cyclohexen-1-one (125 g, 0.89 mol) in ether (500 mL) was added at room temperature to a solution of 2M benzyl magnesium chloride (800 mL) under N 2 and stirred for 6 h. The resulting mixture was poured into a solution of 30% H 2 SO 4 and stirred for 5 h. The resulting organic layer was separated, and the aqueous layer was extracted with several portions of ether. The combined organic layer was dried (MgSO 4 ), and concentrated in vacuo to give compound 1 (161 g) as a colorless oil. NMR(CDCl3): 3.45 (s, 2H, benzylic protons), 5.83 (bs, 1H, olefinic proton), 7.22 (m, 5H, aromatic protons). Example 2 ##STR15## A solution of compound 1 (161 g, 0.87 mol) in ether (700 mL) was slowly added to a suspension of LAH (33 g, 0.87 mol) and ether (100 mL) at 0° C. under N 2 . The resulting mixture was stirred overnight at ambient temperature and cooled to 0° C. Saturated K 2 CO 3 solution was added to quench the excess LAH, the mixture was filtered through Celite and washed with several portions of ether. The combined organic layers were dried (MgSO 4 ) and concentrated in vacuo to give compound 2 (150 g) as a colorless oil. NMR(CDCl3): 3.23 (s, 2H, benzylic protons), 4.20 (bs, 1H, CHCOH), 5.52 (bs, 1H, olefinic proton), 7.22 (m, 5H, aromatic protons). Example 3 ##STR16## A solution of compound 2 (132 g, 0.7 mol) in ether (500 mL) was added to a suspension of hexane washed 60% NaH (27 g, 0.7 mol) in ether (500 mL) at 0° C. under N 2 and stirred for 1 h. Trichloroacetonitrile (115 g, 0.8 mol) was slowly added and the resulting mixture was allowed to warm to ambient temperature and stirred overnight. The solvent was removed in vacuo, hexane (1 L) was added and the mixture was cooled to 0° C. Methanol (150 mL) was added and the resulting solid was filtered through Celite. The organic solvent was removed in vacuo to give a crude intermediate (215 g). This intermediate was dissolved in xylene (1 L) and heated to reflux for 3 h under N 2 . The solvent was removed in vacuo, ether (3 L) and the solid precipitate was filtered to give compound 3 (106 g) as a white crystal: mp 105-06° C.; NMR(CDCl3): 3.20 (Abq, J=8 Hz, 2H), 5.92 (m, 2H, olefinic protons), 6.28 (bs, 1H, NH), 7.22 (m, 5H, aromatic protons). Example 4 ##STR17## A solution of compound 3 (35 g, mmol) in methylene chloride (500 mL) was treated with ozone at -78° C. until the solution turned blue. The excess of ozone was removed with a stream of N 2 , dimethyl sulfide (5 mL) was added and the mixture was allowed to warm to room temperature. TsOH-H 2 O (3.0 g) was added and the resulting mixture was stirred for 48 h. The solvent was removed in vacuo and residue was dissolved in methylene chloride and treated with hexane. The resulting mixture was stirred for 2 h and the resulting solid was filtered. This solid was washed with hexane and dried in vacuum oven overnight to give compound 4 (21.8 g) as a racemic mixture: mp 162° C. NMR(CDCl3): 3.20 (Abq, J=8 Hz, 2H), 6.85 (bs, 1H, NH), 7.05 (s, 1H, olefinic proton), 7.22 (m, 5H, aromatic protons). 9.91 (s, 1H, CHO). Compound 4 was separated into the pure enantiomers 4a, and 4b by using a chiral column. Example 5 ##STR18## A mixture of 3-hydroxyaniline (20.1 g, 190 mmol) K 2 CO 3 (38 g) and EtOH (300 mL) was stirred at 60° C. for 6 h under N 2 . The mixture was cooled to room temperature and 2-chloroethylmorpholine (16 g, mmol) was added. The resulting mixture was heated to reflux for 7 h, cooled to room temperature, filtered and the filtrate was concentrated in vacuo. The residue was purified by column chromatography on silica gel using 3 MeOH/ethyl acetate to give compound 5 as a brown oil (22.5 g). Example 6 ##STR19## NaCNBH 4 (1.0 g) was added in three portions to a solution of compound 4 (7.3 g, 21.0 mmol), compound 5 (6.2 g, 279 mmol) acetic acid (5.5 mL) in methanol (300 mL) at room temperature under N 2 . and stirred for 30 min. Most of methanol was removed in vacuo and the residue was diluted with methylene chloride, washed with 1N. NaOH and dried. The solvent was removed in vacuo and residue was purified by column chromatography on silica gel using ethyl acetate: hexane 9:1 to give compound 6 (10.3 g) as a light brown oil. NMR(CDCl3): 3.20 (Abq, J=8 Hz, 2H), 5.63 (s, 1H, olefinic proton), 6.61 (bs, 1H, NH). This racemic mixture was separated by HPLC using a chiral column (CHIRALCEL®OD™) and isopropanol and hexane (1:1) as an eluent into 6a and 6b. The oxalate salt of racemic 6, mp 90-92° C. MS (MH + =552) Example 7 3-Benzyl-3-trichloroacetylamino-1-(N-phenylaminocarbonyl)-N-[(3-(2-morpholinoethoxy)phenyl)amino]methylcyclopentene ##STR20## To a solution of compound 6 (10.1 g) and triethylamine (0.1 mL) in methylene chloride (300 mL) was added phenyl isocyanate (7.8 g, mmol) at room temperature under N 2 dropwise. The resulting mixture was stirred for 24 h and most of solvent was removed in vacuo. The oily residue was purified by column chromatography on silica gel using ethyl acetate hexane 95:5 as an eluent to give an oil (12.5 g). NMR(CDCl3): 3.17 (Abq, J=8 Hz, 2H), 3.73 (m, 4H,CH2NCH2) 4.08 (t, 2H OCH2--) 5.92 (m, 2H, olefinic protons), 6.28 (bs, 1H, NH), 7.22 (m, 5H, aromatic protons). Treatment of the oil with 1N HCl in ether gives compound 7, the title compound (12.2) as a solid: mp. 70-73(dec.) MS 657(MH + ) Example 8 3-Benzyl-3-trichloroacetylamino-1-(N-phenylaminocart)onyl)-N-[(3-(2-morpholinoethoxy)phenyl)amino]methylcyclopentene ##STR21## To a solution of compound 6b (15 mg) and triethylamine (1 drop) in methylene chloride (5 mL) was added phenyl isocyanate (16 mg) at room temperature under N 2 dropwise. The resulting mixture was stirred for 24 h and most of solvent was removed in vacuo. The oily residue was purified by preparative TLC on silica gel using ethyl acetate hexane 95:5 as an eluent to give an oil. Treatment the oil with oxalic acid (or HCl) in ether gives compound 8, the title compound (15 mg) as a solid: mp 92-94° C. MS (MH + =671) Example 9 3-Benzyl-3-trichloroacetylamino-1-(N-phenylaminocarbonyl)-N-[(3-(2-morpholinoethoxy)phenyl)amino]methylcyclopentene ##STR22## To a solution of compound 6a (14 mg) and triethylamine (1 drop) in methylene chloride (5 mL) was added phenyl isocyanate (14 mg) at room temperature under N 2 dropwise. The resulting mixture was stirred for 24 h and most of solvent was removed in vacuo. The oily residue was purified by preparative TLC on silica gel using ethyl acetate hexane 95:5 as an eluent to give an oil. Treatment the oil with oxalic acid in ether gives compound 9, the title compound (14 mg) as a solid. Example 10 3-Benzyl-3-trichloroacetylamino-1-(N-phenylcarbonyl)-N-[(3-(2-morpholinoethoxy)phenyl)amino]methylcyclopentene ##STR23## Benzoyl chloride (31 mg) was added to a solution of compound 6 (55 mg) and triethylamine (0.3 mL) in methylene chloride (30 mL) at room temperature under N 2 and stirred for 2 hours. Most of solvent was removed in vacuo and the oily residue was purified by column chromatography on silica gel using ethyl acetate as an eluent to give a light brown oil (53 mg). This oil was treated with oxalic acid in ether to give the title compound as an off-white powder (47 mg): mp 79-81° C. MS (MH + =656) Example 11 3-Benzyl-3-trichloroacetylamino-1-(N-phenylaminosulionyl)-N-[(3-(2-morpholinoethoxy)phenyl)amino]methylcyclopentene ##STR24## Phenyl isothiocyanate (15 mg) was added dropwise to a solution of compound 6 (30 mg) and triethylamine (1 drop) in methylene chloride (5 mL) at room temperature under N 2 . The resulting mixture was stirred for 24 h and most of solvent was removed in vacuo. The oily residue was purified by prep TLC on silica gel using ethyl acetate hexane 95:5 as an eluent to give an oil. Treatment the oil with 1N HCl in ether gives compound 11, the title compound (33 mg), as a solid: mp 105-108° C. MS (MH + =687) Example 11 ##STR25## A mixture of compound 3 (3.5 g), barium hydroxide (4 g) and EtOH (100 mL) was heated at reflux overnight. The mixture was cooled to room temperature, filtered and concentrated in vacuo. The residue was purified by column chromatography on silica gel using 1% triethylamine/ethyl acetate as an eluent to give compound 11 as a pale yellow oil (1.1 g). NMR; 2.72 (Abq, J=8 Hz, 2H, benzilic protons), 5.54 (bd, J=9 Hz, 1H, olefinic proton at 2 position), 5.63(dt, 1H, the other olefinic proton), 7.23 (m, 5H, aromatic protons). Example 12 ##STR26## A mixture of compound 9 (should be 11) (350 mg) triethylamine (200 mg), acetic anhydride (200 mg) and methylene chloride (50 mL) was stirred at room temperature under N 2 for 3 h. The mixture was diluted with methylene chloride (50 mL) and poured into ice cold 1 N NaOH (50 mL). The organic layer was separated, dried and the solvent was removed in vacuo to give compound 12 (376 mg) as a pale yellow oil. NMR(CDCl3): 1.94 (s, 3H, acetyl), 3.10 (Abq, J=8 Hz, 2H), 5.92 (m, 2H, olefinic protons), 6.28 (bs, 1H, NH), 7.22 (m, 5H, aromatic protons). Example 13 ##STR27## A solution of compound 12 (376 mg) in methylene chloride (100 mL) was treated with ozone at -78° C. until the solution turned blue. The excess of ozone was removed with a stream of N 2 , dimethyl sulfide (0.5 g) was added and the mixture was allowed to warm to room temperature. TsOH-H 2 O (100 mg) was added and the resulting mixture was stirred for 4 days. The mixture was poured into ice cold 1N NaOH (50 mL) and the resulting organic layer was separated and purified by column chromatography on silica gel using ethyl acetate and hexane (1:5) as an eluent to give compound 13 (273 mg) as an oil. NMR(CDCl3): 1.96 (s, 3H, acetyl), 3.20 (Abq, J=8 Hz, 2H), 6.85 (bs, 1H, NH), 7.03 (s, 1H, olefinic proton), 7.22 (m, 5H, aromatic protons). 9.85 (s, 1H, CHO). Example 14 ##STR28## NaCNBH 4 (150 mg) was added in three portions to a solution of compound 13 (273 mg), compound 5 (297 mg) acetic acid (0.5 mL) in methanol (50 mL) at room temperature under N 2 . and stirred for 30 min. Most of methanol was removed in vacuo and the residue was diluted with methylene chloride, washed with 1N. NaOH and dried. The solvent was removed in vacuo and residue was purified by column chromatography on silica gel using ethyl acetate:MeOH:triethylamine (100:1:0.5) to give compound 14 (303 mg) as a light brown oil NMR; 1.88 (s, 3H. acetyl) 3.13 (Abq, J=8 Hz, 2H, benzilic protons), 4.10 (t, J=6 Hz, 2H, phenoxymethylene protons), 5.62 (bs, 1H, olefinic proton), Example 15 3-Benzyl-3-acetylamino-1-(N-phenylaminocarbonyl)-N-[(3-(2-morpholinoethoxy)phenyl)amino]methylcyclopentene ##STR29## To a solution of compound 14 (25 mg) and triethylamine (1 drop) in methylene chloride (5 mL) was added phenyl isocyanate (14 mg) at room temperature under N 2 . The resulting mixture was stirred for 24 h and most of solvent was removed in vacuo. The oily residue was purified by prep TLC on silica gel using ethyl acetate hexane 95:5 as an eluent to give an oil. Treatment the oil with oxalic acid in ether gives compound 15, the title compound (33 mg) as a solid: mp 85-89° C. MS (MH + =569) Example 16 Preparation of Compound 16 ##STR30## A solution 1N BH 3 /THF (20 mL) was added to a solution of 3-(3-aminophenyl)propionic acid (1.5 g) in THF (15 mL) at 0° C. under N 2 . After addition the mixture was allowed to warm up to room temperature and was stirred overnight. 2N NaOH was carefully added, the resulting mixture was stirred for 4 h and most of the solvent was removed in vacuo. The residue was extracted with methylene chloride (200 mL) and the organic layer was dried and concentrated in vacuo to give compound 16 as a light yellow oil (1.1 g). NMR(CDCl3);3.71 (t, J=6 Hz, 2H, CH2OH), 6.72˜7.13 (m, 4H, aromatic protons). Example 17 Preparation of Compound 17 ##STR31## NaCNBH 4 (30 mg) was added in three portions to a solution of compound 4 (150 mg), compound 16 (100 mg) and acetic acid (10 drops) in methanol (25 mL) at room temperature under N 2 . and stirred for 30 min. Most of methanol was removed in vacuo and the residue was diluted with methylene chloride, washed with 1N. NaOH and dried. The solvent was removed in vacuo and residue was purified by column chromatography on silica gel using ethyl acetate:hexane (1:1) to give compound 15 (201 mg) as a pale yellow oil. NMR(CDCl3); 3.16 (Abq, J=8 Hz, 2H, benzilic protons), 3.72 (t. J=6 Hz, 2H, CH2OH), 3.82 (s, 2H, CH2N), 5.62 (s, 1H, olefinic proton), 6.50˜7.25 (m, 9H, aromatic protons). Example 18 ##STR32## Mesyl chloride (46 mg) was added to a solution of compound 17 (2.01 mg) and triethylamine (0.2 mL)in methylene chloride (50 mL) at -5° C. under N 2 . This mixture was stirred for 5 min and MeOH (2 drops) was added and the resulting mixture was allowed to warm to room temperature and poured into 1N NaOH (10 mL). The organic layer was separated, dried and the solvent was removed in vacuo to give a thick brown oil. This oil was dissolved in THF (10 mL) and morpholine (50 mg) and the resulting mixture was heated at reflux for 16 h. The mixture was cooled to room temperature and the solvent was removed in vacuo. The residue was purified by column chromatography on silica gel using ethyl acetate:triethylamine (100:0.5) to give compound 18 (85 mg) as a pale yellow oil. NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzilic protons), 3.82 (s, 2H, CH2N), 5.62 (s, 1H, olefinic proton), 6.50˜7.25 (m, 9H, aromatic protons). Example 19 3-Benzyl-3-trichloroacetylamino-1-(N-phenylaminocart)onyl)-N-[(3-(3-morpholinopropyl)phenyl)amino]methylcyclopentene ##STR33## To a solution of compound 18 (32 mg) and triethylamine (1 drop) in methylene chloride (5 mL) was added phenyl isocyanate (25 mg) at room temperature under N 2 dropwise. The resulting mixture was stirred for 24 h and most of solvent was removed in vacuo. The oily residue was purified by preparative TLC on silica gel using ethyl acetate hexane 95:5 as an eluent to give an oil (41 mg). Treatment of the oil with oxalic acid in ether gives compound 19, the title compound (40 mg) as a solid: mp 85-88° C. MS (MH + =669) Example 20 ##STR34## A mixture of 3-aminothiophenol (1.25 g, 10.0 mmol), 2-chloroethylmorpholine (2.3 g, 12.0 mmol) and K 2 CO 3 (1.8 g) in THF (150 mL) was heated to reflux for 8 h. The resulting mixture was filtered and partitioned between H 2 O and ethyl actetate. The aqueous layer was washed with several portions of ethyl actetate and the combined organic extracts were dried Na 2 SO 4 and concentrated in vacuo. The residue was purified by column chromatography on silica gel using 10% MeOH/ethyl acetate as an eluent to give compound 20 as an oil (600 mg). NMR(CDCl3); 2.60 (t, J=6 Hz, 2H, CH2N), 3.02 (t, J=6 Hz, 2H, CH2S), 6.44˜7.06 (m, 4H, aromatic protons). Example 21 ##STR35## NaCNBH 4 (300 mg) was added in three portions to a solution of compound 4 (800 mg), compound 20 (600 mg), and acetic acid (2.0 mL) in methanol (100 mL) at room temperature under N 2 . The reaction mixture was stirred for 30 min, most of methanol was removed in vacuo. The residue was diluted with methylene chloride, washed with 1N. NaOH and dried. The solvent was removed in vacuo and residue was purified by column chromatography on silica gel using ethyl acetate: MeOH:triethylamine (100:2:0.1) to give compound 21 (735 mg) as a pale yellow oil. NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzilic protons), 3.82 (s, 2H, CH2N), 5.62 (s, 1H, olefinic proton), 6.50˜7.25 (m, 9H, aromatic protons). MS (MH + =568) Example 22 3-Benzyl-3-trichloroacetylamino-1-(N-phenylaminocarbonyl)-N-[(3-(2-morpholinoethyl)phenyl)thio]methylcyclopentene ##STR36## To a solution of compound 18 (53 mg) and triethylamine (1 drop) in methylene chloride (30 mL) was added phenyl isocyanate (38 mg) at room temperature under N 2 dropwise. The resulting mixture was stirred for 24 h and most of solvent was removed in vacuo. The oily residue was purified by column chromatography on silica gel using ethyl acetate:triethylylamine (100:0.2) as an eluent to give an oil (55 mg). Treatment the oil with oxalic acid in ether gives compound 19, the title compound (57 mg) as a white solid: mp 88-92° C. MS (MH + =687) Example 23 ##STR37## NaCNBH 4 (589 mg) was added in three portions to a solution of compound 4 (2.0 g), 3-nitroaniline (1.59 g, 11.5 mmol) acetic acid (2 mL) in methanol (100 mL) at room temperature under N 2 . and stirred overnight. Most of methanol was removed in vacuo and the residue was diluted with methylene chloride, washed with 1N. NaOH and dried. The solvent was removed in vacuo and residue was purified by column chromatography on silica gel using ethyl acetate:hexane 1:1 to give compound 23 (2.0 g) as a pale yellow oil. NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzylic protons), 3.85 (d, J=6 Hz, 2H, CH2N), 5.62 (s, 1H, olefinic proton), 6.80˜7.44 (m, 9H, aromatic protons). Example 24 ##STR38## Benzoyl chloride (125 mg, 0.89 mmol) was added to a solution of compound 23 (350 mg, 0.748 mmol) and triethylamine (1.3 mg) in methylene chloride (30 mL) at room temperature under N 2 and this mixture was stirred for 2 h. Most of solvent was removed in vacuo and the oily residue was purified by column chromatography on silica gel using ethyl acetate:hexarie (1:4) as an eluent to give compound 24 as a light brown oil (350 mg). NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzylic protons), 4.65 (d, J=8 Hz, 2H, CH2N), 5.62 (s, 1H, olefinic proton), 6.08˜8.01 (m, 14H, aromatic protons). Example 25 ##STR39## A mixture of compound 24 (350 mg, 0.61 mmol), 10% Pd/C (5 mg) and acetic acid (2 drops) in EtOH (20 mL) was hydrogenated at 50 psi at room temperature for 8 h. The resulting mixture was filtered through Celite and concentrated in vacuo. The residue was treated with methylene chloride (300 mL) washed with H 2 O, dried and the solvent was removed in vacuo. The residue was purified by column chromatography on silica gel using ethyl acetate as an eluent to give compound 25 (200 mg) as an oil. NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzylic protons), 4.58 (d, J=8 Hz, 2H, CH2N), 5.62 (s, 1H, olefinic proton), 6.28-7.41 (m, 14H, aromatic protons). Example 26 ##STR40## A solution of compound 25 (160 mg, 0.3 mmol), chloroethylmorpholine (82 mg, 0.44 mmol), and DBU (101 mg) in 2-propanol (25 mL) was heated to reflux for 2 days. The solvent was removed in vacuo and the residue was treated with 0.5 N NaOH (100 mL) and extracted with several portions of ethyl acetate. The organic layer was dried concentrated in vacuo. The residue was purified by column chromatography on silica gel. The bis-alkylated compound (84 mg) was eluted with ethyl acetate:MeOH 95:5. This compound was treated with oxalic acid and ether to give compound 23a (70 mg) as a solid. mp 86-92° C. MS (MH + =655) Continued elution with methylene chloride:MeOH:triethylamine 85:10:5) to give the mono-alkylated product 23b, which was converted to the oxalate salt with oxalic acid and ether (40 mg). mp 88-96° C. MS (MH + =768) Example 27 ##STR41## NaCNBH 4 (146 mg) was added in three portions to a solution of 4-chlorobenzaldehyde (308 mg, 2.2 mmol), 3-aminophenol (200 mg, 1.83 mmol) acetic acid (1.0 mL) in methanol (100 mL) at room temperature under N 2 . and stirred for 30 min. Most of methanol was removed in vacuo and the residue was diluted with methylene chloride, washed with 1N. NaOH and dried. The solvent was removed in vacuo and residue was purified by column chromatography on silica gel using ethyl acetate to give compound 27 (230 mg) as a pale yellow oil. NMR(CDCl3); 4.26 (s, 2H, benzylic protons), 6.10˜7.24 (m, 8H, aromatic protons). MS (MH + =234) Compound 28 ##STR42## NaCNBH 4 (60 mg) was added in three portions to a solution of compound 4 (259 mg), compound 27 (230 mg,) and acetic acid (1.0 mL) in methanol (50 mL) at room temperature under N 2 . and stirred for 16 h. Most of methanol was removed in vacuo and the residue was diluted with methylene chloride, washed with 1N. NaOH and dried. The solvent was removed in vacuo and residue was purified by column chromatography on silica gel to give compound 28 (100 mg) as an oil. NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzylic protons), 4.00 (d, J=8 Hz, 2H, CH2N), 4.42(s, 2H, 4-chlorobenzyl protons), 5.42 (s, 1H, olefinic proton), 6.21˜7.25 (m, 13H, aromatic protons). Example 29 ##STR43## A solution of compound 28 (100 mg, 0.18 mmol), chloroethylmorpholine (100 mg, 0.6 mmol), and DBU (115 mg) in 2-propanol (50 mL) was heated to reflux for 2 days. The solvent was removed in vacuo and the residue was treated with 0.5 N NaOH (100 mL) and extracted with several portions of ethyl acetate. The organic layer was dried concentrated in vacuo. The residue was purified by column chromotography on silica gel using ethyl acetate:hexane (1:1) to give an oil (95 mg). Treatment of the oil with oxalic acid and ether gives compound 29, the title compound as a solid:mp 134-136. MS (MH + =676) Example 30 ##STR44## NaCNBH 4 (35.3 mg) was added in three portions to a solution of compound 4 (150 mg, 0.43 mmol), 3-hydroxybenzylamine (104.8 mg, 0.87 mmol) acetic acid (1.0 mL) in methanol (50 mL) at room temperature under N 2 . and stirred for 16 h. Most of methanol was removed in vacuo and the residue was diluted with methylene chloride, washed with 1N. NaOH and dried. The solvent was removed in vacuo and residue was purified by column chromatography on silica gel to give compound 30 (160 mg) as an oil. NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzylic protons), 3.38 (s,2H, 3-hydroxybenzyl protons), 3.72 (d, J=8 Hz, 2H, CH2N), 5.62 (s, 1H, olefinic proton), 6.68˜7.25 (m, 9H, aromatic protons). Example 31 ##STR45## Benzoyl chloride (69 mg, 0.5 mmol) was added to a solution of compound 30 (150 mg, 0.33 mmol) and triethylamine (1.0 mL) in methylene chloride (20 mL) at room temperature under N 2 and stirred for 16 h. Most of solvent was removed in vacuo and the oily residue was purified by column chromatography on silica gel using ethyl acetate:hexane 1:4 as an eluent to give compound 31 as a light brown oil (220 mg). NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzylic protons), 5.59 and 5.62, (both s, 1H total, olefinic proton, two rotamer?), 6.60˜8.15 (m, 14H, aromatic protons). Example 32 ##STR46## A solution of compound 31 (220 mg, 0.4 mmol), chloroethylmorpholine (280 mg, 1.4 mmol), and DBU (120 mg) in 2-propanol (100 mL) was heated to reflux for 16 h. The solvent was removed in vacuo and the residue was treated with 0.5 N NaOH (100 mL) and extracted with several portions of ethyl acetate. The organic layer was dried concentrated in vacuo. The residue was purified by column chromatography on silica gel using ethyl acetate:MeOH (9:1) to give an oil (95 mg). Treatment of the oil with oxalic acid and ether gives compound 32, the title compound as a solid:mp 90-95. MS (MH + =670) Example 33 ##STR47## Benzoyl chloride (280 mg) was added to a solution of compound 24 (300 mg) and triethylamine (2.0 mL) in methylene chloride (30 mL) at room temperature under N 2 and stirred for 2 hours. Most of solvent was removed in vacuo and the oily residue was purified by column chromatography on silica gel using ethyl acetate:hexane 1:4 as an eluent to give compound 33 as a light brown oil (265 mg). NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzylic protons), 3.35 (s, 2H, allylic methylene protons) 5.61 (s, 1H, olefinic proton) 6.60˜7.23 (m, 9H, aromatic protons). MS (MH + =467) Example 34 (two-step procedure) ##STR48## A solution of compound 33 (265 mg, 0.46 mmol), chloroethylmorpholine (173 mg, 0.8 mmol), and DBU (107 mg) in 2-propanol (50 mL) was heated to reflux for 16 h. The solvent was removed in vacuo and the residue was treated with 0.5 N NaOH (100 mL) and extracted with several portions of ethyl acetate. The organic layer was dried concentrated in vacuo. The residue was purified by column chromatography on silica gel using ethyl acetate:MeOH (95:5) to give an oil (165 mg). Treatment of the oil with oxalic acid and ether gives compound 34, the title compound as a solid:mp 126-28° C. MS (MH + =684) Example 35 ##STR49## A solution of 4-chloro-3-nitrophenol (2.0 g, 11.53 mmol), chloroethylmorpholine (2.57 g, 13.8 mmol), and K 2 CO 3 (5.0 g) in 2-propanol (200 mL) was heated to reflux for 16 h. The solvent was removed in vacuo and the residue was treated with 0.5 N NaOH (100 mL) and extracted with several portions of ethyl acetate. The organic layer was dried and concentrated in vacuo to give compound 35 as an oil. NMR(CDCl3); 4.18 (t, J=6 Hz, 2H, phenoxymethylene protons), 7.09˜7.44 (m, 3H, amomatic protons). Example 36 ##STR50## A mixture of compound 35 (500 mg, 1.84 mmol), 10% Pd/C (5 mg) and acetic acid (2 drops) in EtOH (20 mL) was hydrogenated at 55 psi at room temperature for 16 h. The resulting mixture was filtered through Celite and concentrated in vacuo. The residue was treated with methylene chloride (300 mL) washed with H 2 O, dried and the solvent was removed in vacuo. The residue was purified by column chromatography on silica gel using ethyl acetate:MeOH (95:5) as an eluent to give compound 36 (200 mg) as an oil. NMR(CDCl3); 4.06 (t, J=6 Hz, 2H, phenoxymethylene protons), 6.35˜7.10 (m, 3H, aromatic protons). Example 37 ##STR51## NaCNBH 4 (53 mg) was added in three portions at room temperature under N 2 to a solution of compound 4 (243 mg, 0.7 mmol), compound 36 (200 mg, 0.78 mmol), and acetic acid (2.0 mL) in methanol (75 mL). This mixture was stirred for 16 h and most of methanol was removed in vacuo The residue was diluted with methylene chloride, washed with 1N. NaOH and dried. The solvent was removed in vacuo and residue was purified by column chromatography on silica gel using ethyl acetate:MeOH (95:5) as an eluent to give compound 37 (250 mg) as an oil. NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzylic protons), 4.08 (t, J=6 Hz, 2H, phenoxymethylene protons), 5.62 (s, 1H, olefinic proton), 6.22˜7.30 (m, 8H, aromatic protons). Example 38 ##STR52## 4-Bromobenzoyl chloride (25 mg) was added to a solution of compound 37 (45 mg) and triethylamine (1.0 mL) in methylene chloride (25 mL) at room temperature under N 2 . The reaction mixture was stirred for 16 h and most of solvent was removed in vacuo. The oily residue was purified by preparative TLC using ethyl acetate as an eluent to give an oil (25 mg). Treatment of the oil with oxalic acid in ether gives compound 38 (20 mg). MS (MH + =768) Example 39 ##STR53## NaCNBH 4 (204 mg) was added in three portions to a solution of compound 4 (1.04 g, 3.0 mmol), 3-hydroxy-4-methoxyaniline (835 mg, 6.1 mmol), and acetic acid (2.0 mL) in methanol (100 mL) at room temperature under N 2 . The reaction mixture was stirred for 6 h and most of methanol was removed in vacuo. The residue was diluted with methylene chloride, washed with 1N. NaOH and dried. The solvent was removed in vacuo and residue was purified by column chromatography on silica gel using ethyl acetate:hexane (1:1) as an eluent to give compound 39 (1.2 g) as an oil. NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzylic protons), 4.79 (s, 3H, CH3O), 5.62 (s, 1H, olefinic proton), 6.12˜7.32 (m, 8H, aromatic protons). Example 40 ##STR54## A solution of compound 39 (500 mg, 1.06 mmol), chloroethylrriorpholine (394 mg, 2.12 mmol), and DBU (490 mg) in 2-propanol (100 mL) was heated to reflux for 16 h. The solvent was removed in vacuo and the residue was treated with 0.5 N NaOH (100 mL) and extracted with several portions of ethyl acetate. The organic layer was dried concentrated in vacuo. The residue was purified by column chromatography on silica gel using ethyl acetate:MeOH:triethylamine (85:10:5) to give an oil. Treatment of the oil with oxalic acid and ether gives compound 40, the title compound as a solid:mp 92-95° C. MS (MH + =695) Example 41 ##STR55## Benzoyl chloride (43 mg, 0.3 mmol) was added to a solution of compound 40 (120 mg, 0.26 mmol) and triethylamine (1.0 mL) in methylene chloride (50 mL) at room temperature under N 2 . The mixture was stirred for 6 h, poured into 1N NaOH and extracted with methylene chloride. The organic extracts were combined, dried, and concentrated in vacuo. The oily residue was purified by column chromatography on silica gel using ethyl acetate:hexane (1:1) as an eluent to give compound 41 an oil (100 mg). NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzylic protons), 3.81(S, 3H, CH30), 4.60 (d, J=8 Hz, 2H, CH2N), 5.62 (s, 1H, olefinic proton), 6.60˜7.38 (m, 13H, aromatic protons). Example 42 ##STR56## A solution of compound 41 (100 mg, 0.17 mmol), chloroethylmorpholine (64.7 mg, 0.35 mmol), and DBU (300 mg) in 2-propanol (50 mL) was heated to reflux for 16 h. The solvent was removed in vacuo and the residue was treated with 0.5 N NaOH (100 mL) and extracted with several portions of ethyl acetate. The organic layer was dried concentrated in vacuo. The residue was purified is by column chromatography on silica gel using ethyl acetate:MeOH (9:1) to give an oil. Treatment of the oil with oxalic acid and ether gives compound 42 (81 mg), the title compound as a solid:mp 85-91° C. MS (MH + =686) Example 42 ##STR57## NaCNBH 4 (250 mg) was added in three portions to a solution of compound 4 (510 mg, 1.6 mmol), 3-aminophenol (515 mg, 4.9 mmol) acetic acid (1.0 mL) in methanol (200 mL) at room temperature under N 2 . The reaction mixture was stirred for 30 min and most of the methanol was removed in vacuo. The residue was diluted with methylene chloride, washed with 1N. NaOH, dried and concentrated in vacuo. The residue was purified by column chromatography on silica gel using ethyl acetate:hexane (1:2) as an eluent to give compound 42 (385 mg) as a pale yellow oil. NMR(CDCl3); 3.18 (Abq, J=8 Hz, 2H, benzylic protons), 3.80 (ABq, J=8 Hz, 2H, CH2N), 5.62 (s, 1H, olefinic proton), 6.21˜7.25 (m, 9H, aromatic protons). Example 43 ##STR58## A mixture of compound 42 (251 mg), K 2 CO 3 (1.1 g) ethylbromoacetate (200 mg) THF (70 mL) was heated to 50° C. for 8 h. The resulting mixture was filtered through Celite and concentrated in vacuo. The residue was purified by column chromatography on silica gel using ethyl acetate:hexane (1:3) to give compound 43 a as a pale yellow oil (263 mg). Treatment of the oil with concentrated HCl and MeOH gives compound 43 as a white foam (89 mg): mp 64-66° C. MS (MH + =525) Example 45 ##STR59## A solution of compound 43a (59 mg), 1N NaOH (1mL) in MeOH (5 mL) was stirred at room temperature under N 2 . for 3 h. Most of the MeOH was removed in vacuo and the residue was diluted with H 2 O (10 mL). This mixture was acidified to pH 4 using 0.1N HCl and extracted with methylene chloride. The combined organic extracts were dried and concentrated in vacuo to give compound 45, the title compound as a light brown powder (35 mg): mp 70-73° C. MS (MH + =497) Example 46 ##STR60## Benzoyl chloride (31 mg ) was added to a solution of compound 43a (45 mg) and triethylamine (0.1 mL) in methylene chloride (30 mL) at room temperature under N 2 and stirred for 5 h. The resulting mixture was poured into 1N NaOH and extracted with methylene chloride. The combined organic extracts were combined, dried and concentrated in vacuo. Most of solvent was removed in vacuo and the oily residue was purified by using ethyl acetate:hexane (3:5) as an eluent to give compound 46 as a pale yellow oil (100 mg). MS (MH + =629)
The compounds of formula I are useful in treating gastrointestinal disorders associated with antagonizing the motilin receptor disorders. The compounds compete with erythromycin and motilin for the motilin receptor. In addition the compounds are antagonists of the contractile smooth muscle response to those ligands.
2
BACKGROUND OF THE INVENTION 1. Field This disclosure is concerned generally with a novel cytokine antagonist preparation and specifically with the preparation, characterization, and use of an Interleukin-6 inhibitor which can be isolated from tissue culture fluid and has been found to have in vitro Interleukin-6 antagonist activity. 2. Background The involvement of Interleukin-6 (IL-6) in human health and disease is under intensive investigation. Elevated levels of IL-6 have been found in the bloodstream and/or body fluids of individuals with bacterial and viral infections, trauma, autoimmune disorders, and neoplasias. Correlations of IL-6 levels with severity of symptoms and the beneficial effect of anti-IL-6 antibodies in animal models suggest that the cytokine may play a pathophysiological role in some disease indications. Antagonists of IL-6 may therefore be of therapeutic use. A specific, natural IL-6 antagonist has yet to be described. Portier et al. (Blood, 81(11):3076-82 (1993)) found that γ-interferon (γ-IFN) will inhibit IL-6 dependent myeloma cell growth but γ-IFN does not inhibit IL-6 activity in other types of in vitro assays. Brakenhoff et al. (J. Biol. Chem., 269(1):86-93 (1994)) engineered biologically inactive IL-6 mutants which bound to the 80 kD IL-6R but did not bind to gp130, thus preventing signal transduction. These mutant proteins acted as IL-6 antagonists by preventing native IL-6 from binding to the IL-6 receptor subunits. However, the mutant protein's potential immunogenicity could be a difficulty for therapeutic use. Klein et al. (Blood, 78:1198-1204 (1991)) found that administration of a murine anti-IL-6 antibody to a patient with leukemia blocked myeloma cell proliferation in the bone marrow. Again though, because the murine antibody is a foreign protein, there is the potential for immunogenicity. It has been postulated that bioengineered derivatives of a soluble 80 kD receptor would act as an IL-6 antagonist by binding to circulating IL-6 but not to gp130 thus preventing signal transduction (J. Bauer, Biotechnology Therapeutics, 2(3&4):285-298 (1991)). However, these proteins might have an epitope that could be recognized as foreign and could still be immunogenic if used as a therapeutic. Bauer also stated that clinical trials using human anti-human IL-6 antibodies for the treatment of multiple myelomas have begun (Id.). At this time, the outcome of the clinical trials is unknown. Monocytes/macrophages have been shown to produce both cytokines and cytokine inhibitors, such as the IL-1 inhibitor Roberts et al. found in Respiratory Syncytial Virus (RSV) infected monocytes (J. Exp. Med., 163:511-519 (1986)) and the IL-1 receptor antagonist protein (Janson et al., J. Immunol., 147(12):4218-4223 (1991)). In this invention, we investigated the possibility that such cells may also secrete an IL-6 inhibitor. Since it was difficult to establish a consistent supply of human peripheral blood monocytes, we utilized the human promyelocytic leukemia cell line, HL-60. Treatment of HL-60 with phorbol diesters induces differentiation to cells exhibiting several characteristics of macrophages (Hall et al., Cell. Immunol., 76:58-68 (1983)), while dimethyl sulfoxide (DMSO) or retinoic acid (RA) treatment results in differentiation along the granulocytic pathway (Leftwich et al., Canc. Res., 46:3789-3792)). We found that exposure of HL-60 cells to phorbol diesters specifically induced secretion of an IL-6 inhibitor. It appears that this IL-6 inhibitor is an apparently novel human protein. Because the HL-60 cell line is human, the IL-6 inhibitor should contain the human amino acid sequence and therefore not be immunogenic in vivo. This would be an improvement over the prior examples of IL-6 antagonists. SUMMARY OF THE INVENTION The inhibitor preparation of this disclosure comprises an inhibitor characterized by being obtainable from the HL-60 cell line and having a molecular weight between about 10,000 and 30,000 daltons as determined by gel filtration chromatography. The inhibitor is also bindable and elutible from Blue Sepharose®, bindable and elutible from anion exchange resins and bindable and elutible from reverse phase chromatography resins. The inhibitor suppresses the IL-6-dependent proliferation of the B9 cell line. The inhibitory activity is reduced greater than 50 fold by trypsin digestion, and treatment of the HL-60 cell line with cycloheximide during stimulation completely abrogates the inhibitory activity of the cell supernatant. The activity is resistant to acid and heat treatment. The inhibitor may be partially isolated from stimulated HL-60 supernatants by chromatography on Blue Sepharose®, anion exchange chromatography, and reverse phase chromatography. The inhibitor has been found useful in studying the effect of IL-6 on cellular functions in vitro and may in time be found to be therapeutically useful in treating disorders characterized by increased IL-6 levels. DESCRIPTION OF THE FIGURES FIG. 1: Induction of IL-6 Inhibitor in HL-60 Cells HL-60 cultures were treated with PMA (10 ng/mL), PDBu (130 ng/mL), A23187 (50 ng/mL), DMSO (1.2% v/v), PMA and A23187, or ethanol (EtOH, 1% v/v) for 24 hours. RA (10 nM) was added 5 days prior to 24 hour induction with or without PDBu (130 ng/mL). Cells were washed and resuspended in RPMI-2 at 1×10 6 cells/mL. After 3 days incubation, cell-free culture fluids were prepared by centrifugation at room temperature for 10 minutes at 200 xg and analyzed for inhibition of IL-6 activity in the B9 cell assay. FIG. 2: Effects of IL-6 inhibitor on Proliferation of U373 Cells. HL-60 cells (1×10 6 cells/mL) were treated with PMA (10 ng/mL) for 24 hours. Cells were washed, resuspended in RPMI-2 and incubated for 3 days. Culture fluids were prepared by centrifugation and analyzed in the U373 assay with or without IL-1α. Anti-IL-1 (1 μg/well) was used for comparison. FIGS. 3(A) and 3(B): Optimization of Cell Density and PMA Concentration. HL-60 cultures were established at the indicated cell density and incubated for 24 hours with the indicated concentration of PMA in RPMI-2. Cells were harvested, washed and resuspended at the initial cell density. After 24 hours, cell-free tissue culture fluids were analyzed in the B9 assay in the presence of IL-6. Effect of cell density FIG. 3(A) and PMA concentration FIG. 3(B) on expression of inhibitor are shown. FIG. 4: Superose 12®HR 10/30 Chromatography of HL-60 Supernatant. TCF was concentrated approximately 17 fold with a YM3 membrane and diafiltered into 50 mM Sodium Phosphate pH 7.0 (starting buffer). 0.5 mL of concentrate was applied to the column. The column buffer was 10 mMTris, 150 mM NaCl, pH 7.8. The column flow rate was 0.5 mL/min and 1 mL fractions were collected. Fractions were directly tested for inhibitor activity with the B9 assay. FIG. 5: Mono Q® Chromatography of HL-60 Supernatant. TCF was concentrated approximately 17 fold with a YM3 membrane and diafiltered into starting buffer. The column was equilibrated with 20 mM Tris pH 7.5. The concentrated TCF was diluted 1:2 with the Tris buffer and 0.5 mL was loaded onto the column. Protein was eluted in a linear gradient with the final buffer containing 20 mM Tris, 1M NaCl pH 7.5. 0.5 mL fractions were collected into BSA-containing tubes. To assay for inhibitor activity, 0.4 mL of a fraction was concentrated 4-8 fold and diafiltered with RPMI-1640. FIG. 6: Blue Sepharose® Chromatography of HL-60 Supernatant. TCF was concentrated with a YM10 membrane approximately 87 fold and diafiltered into starting buffer. The concentrated TCF was loaded onto a 50 mL column and the column was washed with starting buffer. A linear gradient of 0 to 1M NaCl in starting buffer was then applied followed by elution with 50% ethylene glycol in 50 mM Sodium Phosphate, 4M NaCl pH 7.0. 10 mL fractions were collected. For use in the B9 assay, samples of the collected fractions were concentrated 4-8 fold and diafiltered into RPMI-1640. FIGS. 7(A) and 7(B): Reverse Phase Chromatography of HL-60 Inhibitory Activity Eluted from Blue Sepharose® Chromatography. Fractions from Blue Sepharose® chromatography containing inhibitor activity were combined into two pools, the first eluting FIG. 7(A) at approximately 900mMNaCl in the linear gradient and the second FIG. 7(B) eluting with 50% ethylene glycol, 4M NaCl. The pools were concentrated approximately 100 fold and applied separately to a 2 mL ProRPC® reverse phase column equilibrated with 0.1% (v/v) trifluoroacetic acid (TFA) in water. The column was washed with the starting buffer and eluted with a 20% (v/v) to 80% (v/v) linear gradient of HPLC grade acetonitrile in 0.1% (v/v) TFA. Fractions (0.3 mL) were collected, evaporated to dryness, and resuspended in 0.1 mL H 2 O for analysis in the B9 assay. FIG. 8: Reverse Phase Chromatography of HL-60 Inhibitory Activity Isolated by Reverse Phase Chromatography. Active fractions from the reverse phase chromatography of Blue Sepharose® pools A and B were combined and rechromatographed on the 2 mL ProRPC® column using a 20 to 80% (v/v) acetonitrile gradient in 0.1% TFA. Fractions were analyzed for IL-6 inhibitor activity as described in FIG. 7. FIG. 9: Heat Treatment of HL-60 Inhibitor. The following samples were heated for 15 min at 100° C. and then tested for inhibitory activity in the B9 assay. (1)Blue Sepharose® Peak 2: undiluted, (2)Blue Sepharose® Peak 2: 1:10, (3)Blue Sepharose® Peak 2: 1:100, (4)Blue Sepharose® Peak 2: 1:1000, (5)Anti IL-6, 5.0 μg/mL, (6)Anti-IL-6, 0.5 μg/mL, (7)Anti-IL-6, 50 ng/mL, (8)Anti-IL-6, 5 ng/mL, (9)RPMI-2: Undiluted, (10)RPMI-2: 1:10, (11)RPMI-2: 1:100, (12)RPMI-2: 1:1000. FIG. 10: Trypsin Digest of HL-60 Inhibitor. Using a 10 kD molecular weight cut-off filter, 500 μL of a Blue Sepharose® pool containing IL-6 inhibitor activity, was diafiltered into 0.1M Ammonium Bicarbonate pH 8.0 (digestion buffer). Samples (250 μL/sample) were added to separate pellets of immobilized trypsin previously washed in digestion buffer and incubated at 37° C. for 3.5 hours. Trypsin digests were recovered by centrifugation, sterile filtered, and compared against untreated samples in the B9 assay. FIG. 11: Acid Treatment of HL-60 Inhibitor. An Blue Sepharose® pool containing IL-6 inhibitor was diluted 1:2 in either 0.1% trifluoroacetic acid/100% acetonitrile, pH≦2 or sterile water. After evaporation to dryness, the samples were reconstituted in 100 μL RPMI, sterile filtered, and analyzed by the B9 assay. FIG. 12: Effect of Cycloheximide on Synthesis of HL-60 Inhibitor. HL-60 cells (10 6 /mL) were treated with PMA (10 ng/mL). After 24 hours adherent cells were washed in RPMI-2 and non-adherent cells were removed. Duplicate cultures were then incubated in either RPMI-2 or RPMI-2 containing 100 μg/mL cycloheximide. After an additional 24 hours, TCF was removed and the cells were washed to remove cycloheximide. Cells were incubated in RPMI-2 for 2 more days at which time TCF was harvested for analysis of inhibitory activity in the B9 assay. All TCF samples were diafiltered prior to assay to ensure removal of cycloheximide. DETAILED DESCRIPTION OF THE INVENTION Reagents Phorbol Myristate Acetate (PMA), Phorbol dibutyrate (PDBu), A23187, all-trans-retinoic acid (RA), and dimethyl sulfoxide (DMSO) were purchased from Sigma Chemical Co. Stock solutions of PMA, PDBu, A23187, and RA were stored in ethanol at -20° C. All reagents were protected from light and diluted into the appropriate medium immediately prior to use. Recombinant human IL-6 was purchased from Genzyme. Anti-IL-6, anti-IL-1α, anti-IL-1β, and recombinant human IL-1α were purchased from R&D Systems. Cell Culture Two HL-60 cell lines (ATCC #CCL-240) were used to generate the inhibitory activity. The first cell line secreted high levels of IL-6 and the second secreted 20 pg/mL or less of IL-6. The cell lines were maintained in RPMI-1640 (Gibco) supplemented with 10% heat inactivated FBS (Hyclone) (RPMI-10). Cells were washed in Ca 2+ and Mg 2+ free Dulbecco's phosphate buffered saline (DPBS-CMF, Gibco) and resuspended in RPMI-1640 containing the appropriate inducing agent(s). Tissue culture fluids (TCF) were harvested and IL-6 inhibitor activity was determined using the B9 assay. Initial experiments to determine optimal inducer and cell concentrations were performed with the IL-6 secreting cell line. Subsequent experiments demonstrated that the non-secreting HL-60 line produced an IL-6 inhibitor after phorbol diester (e.g. PMA, PDBu, etc.) stimulation. By gel filtration, the inhibitor synthesized by the IL-6 non-secretor had the same molecular weight as the inhibitor synthesized by the IL-6 secretor. To avoid aberrant results due to the presence of IL-6, characterization and purification studies were done using the non-secreting cell line which is available from the ATCC. IL-6 Dependent B9 Assay The B9 murine hybridoma cell line (gift from P. Scuderi, Miles Research Center; West Haven, CN) was maintained in RPMI-10 supplemented with at least 1 unit/mL IL-6. For use in the assay, the cells were seeded at 5×10 4 cells/mL in RPMI with 5% FBS (RPMI-5) in 96-well plates (Corning) at 100 μL/well. Volumes of 20 μL (crude TCF) or 10 μL (column fractions) from samples to be tested were added. One-half of the wells received 100 μL of IL-6 at 2 units/mL in RPMI-5 and the other half received 100 μL of RPMI-5. Anti-IL-6 was added to control wells at 0.5-1 μg/well to ensure that IL-6 specific effects were being measured. After a 3-4 day incubation period, cell proliferation was measured by either 3 H-Thymidine ( 3 H-Tdr, DuPont-NEN) incorporation or by conversion of MTS tetrazolium (Promega) into an aqueous soluble formazan. For 3 H-Tdr incorporation, the cells were labelled with 0.5 μCi/well 3 H-Tdr for 5 hours, harvested onto filters using the Tomtec Autotrap and 3 H incorporation was determined using a 1205 BS Betaplate (LKB-Wallac). For non-radioactive detection of cell proliferation, the Cell Titer 96 AQ Non-radioactive Cell Proliferation Assay (Promega) was used. Samples were assayed in triplicate and percent inhibition was calculated from the mean values in the following manner: ##EQU1## To determine percent inhibition in the non-radioactive assay, O.D. values were used instead of CPM in the above equation. IL-1 Dependent U373 Assay The growth promoting effects of IL-1 on the U373 (human astrocytoma/glioblastoma) cell line have been reported by others (Lachman et al., J. Immunol.,138(9):2913-29-6 (1987)). For use in the assay, U373-MG cells (ATCC #HTB 17) were grown to confluence in RPMI-10. One day prior to testing, cells were treated with trypsin and 1×10 4 cells/well were seeded into 96-well plates in RPMI containing 1% FBS (RPMI-1). Test samples, 20 μL of tissue culture fluid (TCF), were then added with or without 5 units/mL of IL-1α in a total volume of 200 μL/well. RPMI-2 was added in the appropriate volume to serve as a negative control. Cells were cultured for 2 days and 0.5 μCi/well of 3 H-Tdr was added for the terminal 5 hours. Cells were harvested and 3 H incorporation was determined. Column Chromatography PMA-induced HL-60 culture supernatants were diafiltered into the indicated buffer and concentrated by ultrafiltration with a YM10 or YM3 membrane (Amicon). The concentrated supernatants were applied to the chromatography resins and eluted as described in the figures. To assay for IL-6 inhibitor activity, the fractions were filtered through a 0.22 μm filter and, if the elution buffer was incompatible with the B9 assay, diafiltered with RPMI-1640. All resins were purchased from Pharmacia unless otherwise noted. SDS-PAGE Samples to be electrophoresed were diluted 1:2 with non-reducing SDS-PAGE buffer and boiled 5-10 min at 100° C. 20 μL of the diluted samples were loaded onto 10-20% gradient SDS-PAGE gels (BioRad) and electrophoresed at 200 V for approximately 45 min. The gels were stained with Coomassie Blue R-250 or silver stained. Example 1 The effects of various compounds known to modulate the differentiation of HL-60 cells in vitro are summarized in FIG. 1. 0.5-2×10 6 HL-60 cells per mL RPMI-1640 were treated with 10 ng/mL PMA or 130 ng/mL PDBu, both of which are known to induce monocytic differentiation. After 24 hours, the cells became adherent, vacuolated and ceased to grow. The cells were transferred into RPMI-2 and 3 days later an IL-6 inhibitor as determined with the B9 assay was found in the culture fluids of the cells treated with either PMA or PDBu, but not in the culture fluids of cells treated with DMSO or RA, which induce granulocytic differentiation. In some cell lines calcium ionophores and phorbol esters synergistically elicit cellular activation. However, we found that co-stimulation with PMA and a calcium ionophore (A23187) did not increase the level of inhibitor over that induced by PMA alone. A23187 alone did not generate a detectable inhibitor. The IL-6 inhibitor was detected in culture fluids within 24 hours of PMA addition and secretion continued for an additional 48 hours after removal of the inducing agent. Despite the fact that PMA alone can stimulate B9 cell growth and the first harvest of HL-60 culture fluids potentially contained 10 ng/mL of residual PMA, inhibitory activity was still observed in the crude supernatant of this harvest. Example 2 In addition to inhibiting the IL-6 stimulated proliferation of B9 cells, the HL-60-derived inhibitor suppressed the endogenous (IL-6 independent) growth of B9 cells. Anti-IL-6 only affected IL-6 stimulated proliferation. To rule out the possibility that the HL-60-derived activity was an inhibitor of thymidine incorporation or a non-specific inhibitor of cell proliferation, the effect on U373 cells was analyzed. Proliferation of U373 cells is stimulated by IL-1 but not by IL-6. See FIG. 2. 1×10 6 HL-60 cells/mL were treated with 10 ng/mL PMA for 24 hours. The cells were transferred into RPMI-2 and incubated for 3 days further. The supernatant was collected and assayed in the U373 assay. No inhibitor of IL-1 stimulated proliferation or non-specific inhibitor of cell growth was detected in the culture fluids of PMA induced HL-60 cells as determined by the U373 assay. In fact, HL-60 culture fluids were found to stimulate proliferation of U373 cells presumably due to the presence of IL-1 in the supernatant. Control experiments using anti-IL-1 gave the expected results. In addition, the HL-60 inhibitor did not inhibit IL-2 dependent or non-specific proliferation of CTLL cells. Results The initial studies were expanded to determine the best conditions for induction of inhibitor. Optimal inhibitor production was observed using HL-60 cell densities ranging from 0.5 to 2.0×10 6 cells/mL and PMA concentrations from 1-10 ng/mL (see FIG. 3). Characterization of the Inhibitor Column Chromatography: The IL-6 non-secreting HL-60 cell line was used to further characterize the inhibitor as well as fractionate the inhibitor activity from contaminating proteins. Size exclusion, anion exchange, Blue Sepharose®, and reverse phase chromatography were utilized. In order to simplify large scale purification, cells were induced in serum-free RPMI-1640. To approximately determine the molecular weight of the inhibitor, the TCF was ultrafiltered through a 30 kD membrane. Activity was found in the filtrate after concentration with a 10 kD membrane indicating that the molecular weight of the inhibitor is less than 30 kD but greater than 10 kD. To further characterize the inhibitor, concentrated and diafiltered TCF was chromatographed on a Superose 12® gel filtration column. See FIG. 4. The activity eluted at a position corresponding approximately to 20 kD. IL-6 was determined by ELISA (R&D Systems). HL-60 TCF was concentrated and applied to a Mono Q® anion exchange column. See FIG. 5. The fractions from the Mono Q® column were assayed for inhibitor activity and activity was found to elute at 175 mMNaCl. From DEAE-Sephacel®, inhibitor activity was found to elute at 150 mM NaCl. Because Blue Sepharose® had been used previously to isolate cytokines, TCF containing the IL-6 inhibitor was chromatographed on this resin. See FIG. 6. Under the conditions used, the bulk of the protein in the TCF did not bind to the column. The inhibitor activity eluted in a broad peak at approximately 900 mMNaCl (Pool A) or in the subsequent 50% ethylene glycol/4M NaCl (Pool B). By SDS-PAGE, the inhibitory peak fractions from Blue Sepharose® contained multiple proteins. C1/C8 reverse phase chromatography (ProRPC®) was used to further purify the inhibitor. See FIG. 7. IL-6 inhibitory activity from either Blue Sepharose® pool A (FIG. 7A) or pool B (FIG. 7B) was found to elute at approximately 40% acetonitrile. The active fractions from these runs were combined and rechromatographed on ProRPC® using a shallower gradient to improve resolution (FIG. 8). Inhibitory activity eluted at approximately 32% acetonitrile. SDS-PAGE analysis (10 to 20% gradient gel) revealed the presence of multiple protein bands. Thus, although significant purification of the inhibitor from TCF has been achieved, the inhibitor has not yet been purified to homogeneity. Characterization: A partially purified pool of inhibitor eluted from Blue Sepharose® was heated at 100° C. for 15 minutes without any significant loss of inhibitory activity in contrast to what was observed with anti-IL-6 (see FIG. 9). Treatment of the Blue Sepharose® pool with immobilized trypsin reduced inhibitor activity 64 fold (see FIG. 10). Treatment of the TCF with 0.1% trifluoroacetic acid in acetonitrile at pH≦2 resulted in a 3 fold loss of activity (see FIG. 11). Incubation of HL-60 cells after PMA stimulation with cycloheximide, a known protein synthesis inhibitor, resulted in the complete suppression of inhibitor activity in the B9 assay (see FIG. 12). The results of the above experiments strongly suggest that the inhibition seen is the result of a protein present in the HL-60 TCF. Discussion An inhibitor of IL-6 stimulated proliferation of B9 hybridoma cells was detected in the culture fluids of HL-60 cells induced to differentiate toward the macrophage lineage. Phorbol myristate acetate (PMA) and the non-lipophilic diester phorbol dibutyrate (PDBu) were effective as inducers of the inhibitory activity. Inducer concentration and cell density were found to be critical parameters for optimization of inhibitor expression, e.g. 1-10 ng/mL PMA and 0.5-2.0×10 6 cells/mL. Differentiation of HL-60 cells along the granulocytic pathway with retinoic acid (RA) and dimethyl sulfoxide (DMSO) did not induce detectable levels of the inhibitor. Exposure of cells to the calcium ionophore A23187 with or without PMA or to combinations of RA and PMA, conditions which have been reported to enhance activation of monocytic cell lines, had no significant effect on expression of inhibitor. The HL-60 derived activity had no inhibitory effect on the IL-1 dependent or spontaneous rate of proliferation of U373 cells. These data suggest that the activity is not an inhibitor of thymidine uptake or IL-1 action, or a non-specific inhibitor of cell proliferation. Nevertheless, the HL-60 inhibitor suppressed the spontaneous rate of B9 cell proliferation observed in the absence of added IL-6, in addition to the stimulated rate induced by exposure of B9 cells to PMA. Although anti-IL-6 had no effect on the spontaneous proliferation of B9 cells, endogenous synthesis of the cytokine may provide an autocrine growth effect and such autocrine effects may be refractory to inhibition by antibodies. The mechanism by which PMA stimulates B9 cell proliferation is unknown, but could also depend upon endogenous synthesis of IL-6, since B9 cells respond to no other known cytokines. We tentatively conclude that the HL-60 derived activity is likely a specific inhibitor of both added and endogenous IL-6. It is interesting to note that the inhibitory activity can be found in HL-60 supernatants that contain rather high concentrations of IL-6. This observation suggests a mechanism distinct from receptor antagonism, which would be consistent with the differential effects of anti-IL-6 and the HL-60 inhibitor on spontaneous and PMA-induced B9 cell proliferation. To the best of our knowledge, no naturally occurring IL-6 inhibitors have been described to date. As used herein, naturally occurring human inhibitor means a non-genetically engineered compound derived from human cells that inhibits the actions of IL-6. Soluble IL-6 receptors have been reported, but have been found to stimulate rather than inhibit IL-6 activity. This is a unique observation, since other soluble cytokine receptors are known to be antagonists. The agonist activity is most likely due to the configuration of the IL-6 receptor; a primarily extracellular 80 kD subunit which binds to IL-6 with low affinity and gp 130, which after binding to the IL-6/80 kD complex, increases the affinity of the 80 kD receptor for IL-6 and causes signal transduction. Presumably a soluble receptor-IL-6 complex is recognized and bound by gp130 and the IL-6 signal is transduced. Overexpression of IL-6 has been documented in autoimmune diseases such as systemic lupus erythematosus and rheumatoid arthritis and the cytokine is known to be a growth factor for neoplastic plasma cells. Although effects of IL-6 antagonists have not been reported for autoimmune diseases, a role for the cytokine in pathogenesis has been proposed on the basis of available data. A short term clinical response was noted using a murine monoclonal antibody in patients with plasma cell leukemia, suggesting that effective blockade of IL-6 function would be a beneficial adjunct to current therapy. The above examples are intended to illustrate the invention and it is thought variations will occur to those skilled in the art. Accordingly, it is intended that the scope of the invention should be limited only by the following claims.
A previously undescribed Interleukin-6 inhibitor activity has been successfully isolated from the supernatant of the human promyelocytic leukemia cell line HL-60. Treatment of the HL-60 cell line with cycloheximide prevents the appearance of the inhibitory activity in the cellular supernatant. Incubation of the HL-60 supernatant with trypsin destroys the activity. The above observations indicate the inhibitor is a protein. Membrane and gel filtration studies indicate the protein has a molecular weight between 10,000 and 30,000 daltons. The inhibitor was partially isolated from other proteins by dye-ligand and reverse phase chromatography.
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