Title of Invention

POLYVINYLYIDENE CHLORIDE COATING, PROCESS FOR PRODUCING A COATING AND USE THEREOF

Abstract

Coating on the basis of polyvinylidene chloride, process for the manufacture of a coating and its use A coating 8 made of polyvinylidene chloride contains particle 12 made of HDPE. Other particles which can also be embedded are polymers from the group LDPE, LLDPE, PP, PVDC, PVC, polyamides, polyurethanes, polyacrylates, polystyrenes, acrylonitrile butadiene styrene polymerizates (ABS), PTFE, hard waxes, synthetic resins, as well as mixtures and copolymerizates thereof. The coating 8 is applied to a film 9 of a composite which features a carrier film 11, to which film 9 is laminated by means of an adhesion promoter 10. (Fig. 2)

Full Text

Polyvinylidene chloride coating, process for producing a coating and use thereof The invention relates to a film on the basis of polyvinylidene chloride sheet-formed materials, a process for the manufacture of a coating and its use. Multi-layer composites, below designated as "composites" or "composite films," are used for such things as packaging foods and pharmaceutical products. Frequently the top film or layer of such composites is coated with vinylidene chloride polymer- or copolymer dispersions. For example for the packaging of pharmaceutical products, PVC films or PVC-PE composite films are coated with vinylidene chloride copolymer dispersions and subsequently processed in a thermoforming process into blisters, which are then filled with packing products and are sealed shut with an aluminum foil or a thin polymer cover film. Vinylidene chloride monomers are usually polymerized into copolymers with methacrylates, acrylates, vinyl chloride or acrylonitrile. The purpose of the vinylidene chloride copolymer coating is to form a sealable coating and/or formation of a barrier layer against vapor, oxygen and aromas. Vinylidene chloride copolymer dispersions form plastic films which feature, when in a fresh condition, and especially if they contain no wax or other lubricant additive, for one a blocking tendency, i.e. a tendency to adhere to a smooth surface, such as the nearest wrap of a film roll, and, for another, very high coefficients of static friction and sliding friction in relation to metals, plastics and organic materials. The coefficients of sliding friction may be reduced after the surface of the PVDC coating has become harder due to more or less quickly on-setting and progressing crystallization. But a tendency to adhere to machine parts, or to poor sliding characteristics when being filled with packing goods, especially with gelatin capsules, remains undiminished. A tendency to unwanted sticking of the PVDC layer to hot machine parts, for example in the heating zone of thermoforming machines, has also been observed. After the composite film is wrapped the blocking tendency results in the creation of dabbing spots on the soft PVDC surface caused by contact with the adjacent wrap of film. If the PVDC surface is very smooth, as in the case of the screen cylinder or tri-helix roller coating systems Usually used for PVDC dispersion coating, if no counteractive measures are taken, the air wrapped over results in large zones with a glossy surface, since the contact with the adjacent wrap is prevented by enclosed air bubbles. Adjacent to these are zones with a matt surface which are in contact with the adjacent wrap and in which, as a result, dabbing spots occur. The dabbing images themselves do not result in a technical fault in the PVDC coating, but such composites are frequently not accepted on aesthetic grounds. However, in many cases, PVDC coated films can also develop an unwanted film deformation, possibly leading to secondary faults due to the wrapped over air bubbles. Generally this air-enclosure effect is reduced by applying a specific surface structure permitting the air to escape from the sides. Also the dabbing spots, due to the fact that they basically always appear on the wave crests of the surface structure, are distributed evenly across the whole surface of the film, and the film acquires in this manner a more homogenous appearance. The specific generation of such a surface structure determines the use of additional equipment in a coating machine. The quality of the structure, i.e. the roughness height, appearance, the mean layer thickness of the top layer of the composite, must be controlled by machine settings and, in general, in comparison to a smooth film surface, the generation of a surface structure is accompanied by a loss in film thickness and, thus, by a possible loss in productivity. Due to the surface unevenness, the application of a surface structure onto a PVDC coated film is a disadvantage, or even impossible, if the coated composite is subjected to an additional lamination or coating step on the PVDC side. Freshly coated and wrapped composite film rolls relax over a period of a few hours or days, in that they collapse somewhat in those sections which are wrapped less tightly, or at places where the film is less thick, and draw tight at places characterized by greater film thickness. One result of the block tendency of the freshly coated PVDCs consists in the fact that, due to the insufficient sliding capacity between the film wraps and to the simultaneous relaxing, tension arises along the film surface which, if the block tendency is too pronounced, can even lead to material destruction caused by the breaking of the composite films into the individual films or layers. In DE 100 64 800 Al micronized polyethylene waxes are described which are manufactured by the co-polymerization of ethylene under high-pressure conditions using an aliphatic or aliclycic ketone as molecular weight regulator and subsequent micronization. What is meant by micronization is the breaking up of substances into particle sizes ranging from 1 jam to a maximum of 100 |im. The substances are rendered into the desired morphology by grinding or spraying. There are numerous applications known for micronized polyethylene waxes, for example as carriers for printing inks, coatings, abrasive for toothpastes, and additive for cosmetic preparations such as eyeshadows, lipsticks, or blusher. DE 43 16 025 Al relates to micronized polyethylene wax of a mean particle size of 1 to 30 jam, suitable as a solvent to detackify the surface of sticky granulates. The micronized polyethylene wax develops its effect even in small quantities of 0.01 to 2 % by weight of the granulate. The micronized polyethylene waxes are made by spraying a relevant polyethylene melt with gases in a two-stage nozzle. EP 0 403 542 Bl discloses a polymer composition which comprises a vinylidene chloride interpolymer formed from a monomer mixture. The monomer mixture contains 60 to 99 % by weight vinylidene chloride and 40 to 1 % by weight of at least one ethylene-type unsaturated comonomer which is copolymerizable with it. The vinylidene chloride interpolymer is mixed with a formulation package which contains 0.1 to 95 % by weight in relation to the total weight of the formulation package, an alkali metal salt or an alkaline earth metal salt of a weak acid, an ethylene homopolymer and at least one plasticizer and one lubricant. The vinylidene chloride interpolymer can be used to make objects by casting, blowing, extrusion molding, coextrusion, laminating, or calendering of the polymer compound. EP 0 736 067 Bl describes a process of stabilizing polyolefin mixtures containing PVDC, and stabilized polyolefin mixtures containing PVDC. The plastic mixture comprises polyolefms and 0.05 to 20 % by weight PVDC and at least one organic phosphite or phosphonite as well as at least one metal salt of a fatty acid. DE 198 32 500 Al relates to a thermoformable composite film which comprises a film containing at least one cycloolefin eopolymer and a thermoplastic film laminated onto at least one side of it. The thermoformable film is laminated to the film containing cycloolefin eopolymer by a solvent-free, single-component adhesive. The thermoplastic film contains PVDC. The thickness of the film as a whole is 100 to 500 µm, the thickness of the PVC film ranges from 5 to 150 jam, and the thickness of the COC film is 50 to 400 jam. This thermoformable composite film is used to make blister packs. The thermoplastic film can also be selected from polyolefin, polyamide, polyester, polycarbonate, polystyrene, polyvinyl chloride, and polyurethane. The object of the invention is to create a coating for composites, especially for composite films, which feature low coefficients of static friction and sliding friction for the improvement of the sliding characteristics of the composite film, and to facilitate handling of the composite films to be coated in machines and their finishing in corresponding machines. This object is achieved by a coating on the basis of polyvinylidene chloride for sheet-formed materials in such a manner that particles made of polymers, natural substances, modified natural substances, anorganic materials or mixtures thereof are contained in the polyvinylidene chloride. The density of the particles in this case is in the range of 0.1 to 2.0 g/cm and the mean particle diameter in the range of 1 µm to 100 µm. For this purpose the largest particle diameter is equal to/greater than the thickness of the PVDC layer. In one embodiment of the invention the particles are selected from a group comprising HDPE, LDPE, LLDPE, polypropylene, PVDC, PVC, polyamides, polyurethanes, polyacrylates, polystyrenes, polyacrylonitriles, acrylonitrile butadiene styrene (ABS), polytetrafluoroethylene (PTFE), synthetic resins, hard waxes as well as mixtures and copolymerizates thereof. In further development of the invention the particles have a surface coating made of one of the polymers selected from a group comprising HDPE, LDPE, LLDPE, polypropylene, PVDC, PVC, polyamides, polyurethanes, polyacrylates, polystyrenes, polyacrylonitriles, acrylonitrile butadiene styrene polymerizates (ABS), polytetrafluoroethylene (PTFE), synthetic resins, hard waxes as well as mixtures and copolymerizates thereof. The further embodiment of the invention follows from the features contained in patent claims 7 to 13. The process for the manufacture of such a coating on the basis of polyvinylidene chloride for sheet-formed materials is characterized in that a PVDC dispersion is provided into which the particles are fed directly or into which a particle dispersion is fed while stirring. For this purpose the particle dispersion is prepared by stirring a particle powder into water without, or with one or several emulsifying agents. The particle dispersion preferably has pigment dispersers or other dispersion-promoting additives added to it. In a further embodiment of the process the mixture of PVDC and particle dispersion is applied and dried as the top layer onto a sheet-formed material. In particular a PVDC dispersion, containing 5 to 80 % by weight PVDC, and a particle dispersion, containing 10 to 95 % by weight particles, are mixed together. The further embodiment of the process follows from patent claims 19 to 21. The coating according to the invention is used to coat plastic films, paper sheets, and metal foils. In particular the coating is used to coat PVC mono-films, multi-layer composites made of PVC and PE, made of PVC-PE composite films and one metal foil, mono-films made of cycloolefin copolymers, as well as composite films made of cycloolefin copolymers with PVC and/or other polymers. Composite films of the kind listed, which are refined after being coated with PVDC by laminating and/or coating, are also used. All the usual polymer films such as PET, PP, PE, acrylates, ABS, PS, cellophane, cellulose acetates, polyamides, polyacrylonitriles, PCTFE etc., and the respective composites made of two or more of the listed polymer films can be outfitted With the coating specified by the invention. Especially preferred is the coating for coating a PVDC layer of a multi-layer composite made of PVDC film, adhesion promoter and carrier film as well as a multi-layer composite made of PVDC film, adhesion promoter, polyethylene, adhesion promoter, and carrier film. By PVDC film is meant a PVDC film onto which PVDC dispersion was already applied as a primer during earlier work steps. Other multi-layer composites with PVDC coated films are PVC/PE/PVDC/PVDC+HDPE/PE/PVC; PVC/COC/PVDC/-PVDC+HDPE; PVC/PVDC/PVDC+HDPE/PE. The coating according to the invention can also be applied to metal foils as well as onto composites made of metal foils and polymer films coated in this manner. In all these applications it is also possible to use the coating according to the invention without a previous coating of primer with unmodified PVDC. Films like these are used in such applications as the manufacture of blister packs. By embedding polymer particles, preferably of HDPE micronizates, in the top polyvinylidene chloride copolymer layer of composite films, the above described difficulties are eliminated or greatly reduced and the manufacturing process for these composite films is simplified and more efficient. These polymer particles act as spacers between the wraps of a film and improve the sliding characteristics of the PVDC surface of the film sheet. Polymers in liquid and powder form considered suitable for these particles are those which are highly compatible with the specific PVDC dispersion, are not abrasive, and in particular are not essentially harder than the PVDC coating or the underside of the carrier or base film on which the PVDC coating is applied. If the particles are harder than the other film surfaces of a composite, the surface of the particles must be as smooth as possible and, ideally, spherical. Ideally the particles have as low coefficients of static friction and sliding friction as possible. The particles should not be film-forming at drying temperatures up to 100 °C customary for PVDC drying, and should not "melt" with the PVDC during drying, i.e. should not form a homogenous PVDC/particle polymer film. Instead, the polymer particles from the PVDC layer should protrude and, by doing so, fulfill their function as spacers. In addition, the particle material should be characterized by a refractive index similar to that of PVDC, so that as little clouding as possible occurs in the PVDC particle layer. The density of the particle material is in the range from 0.1 to 1 -1 2.0 g/cm , especially in the range of smaller than/equal to 1.30 g/cm and it is preferred as smaller than 1 g/cm , so that its migration to the surface in the particle dispersion, and thus its protrusion out of the PVDC surface, is promoted. For this purpose the largest particle diameter is equal to/larger than the thickness of the coating. The mean particle diameter of the particles must also be made compatible with the application system so that irregularities in the particle contents related to oversized particles or inhomogeneous application cannot arise. So as to not have a negative impact on the barrier effect of the PVDC coating, the particles must not be porous. The barrier effect must be as high as possible in the application area of the composite film or composite. In principle, as particles, all polymers come into consideration which meet the above conditions either completely or partially, for example: HDPE, LDPE, LLDPE, PP, PVDC, PVC, polyamides, polyurethanes, polyacrylates, polystyrenes, polyacrylonitriles, ABS, PTFE, hard waxes, synthetic resins and others, as well as mixtures and copolymerizates thereof. Particles can also be used which have a suitable surface coating. The core materials of such coated particles are, for example, polymers from the above list as well as natural substances such as cellulose, natural waxes, poly(hydroxyalkanoic acids), shellac, modified natural substances such as casein derivatives and casein condensate, cellulose derivatives such as cellulose acetate and cellulose nitrate or anorganic substances such as silicon dioxide, silicate, aluminum oxide, titanium dioxide. As coating materials the above listed polymers can be used or other, correspondingly suitable surface coatings such as silane, siloxane, ormocer (organically modified ceramic), ceramic materials. Particles can also be used which are of a purely anorganic nature, such as silicon dioxide, silicate, aluminum oxide, titanium dioxide, and which possess the above listed characteristics. If the particles have a polymer origin, they can be made by polymerization, polycondensation, polyaddition, polymer analogous implementation or a mixture of prefabricated polymers. The particle form and splitting is normally performed either directly during polymerization, i.e. suspension or emulsion polymerizations, or by a later mechanical splitting and/or suspension and stabilization in a carrier liquid. Anorganic particles can, for example, be ground from natural substances or be made synthetically. Particles like these can be given surface coatings. When using particles, the particle's proportion of the dry coating is usually in the range of 0.1 % by weight to 10 % by weight. For particles in the form of HDPE micronizates, for example, a dry percentage of approx. 0.2 to 2 % micronizates by weight of dry coating mass proves to be especially effective. To manufacture such PVDC coatings containing particles the PVDC dispersion is mixed while stirring before application to a sheet-formed material with a corresponding quantity of particle suspension or dispersion until the suspension or dispersion is homogenously mixed with the PVDC dispersion. For this purpose a commercially available non-shearing stirrer is used, for example a propeller stirrer. Subsequently the mixture is applied with an application tool customarily used for PVDC coatings on the material to be coated, and dried. If the particle size has been correctly selected and the compatibility with the PVDC dispersion is given, no difference to the unmodified PVDC dispersion can be identified in terms of coating and/or drying behavior. The finished coated material features the following substantial process and product advantages: The static and sliding friction of the surface of the coated material is, especially in a freshly coated condition, substantially less than of the unmodified PVDC coating. The blocking tendency of freshly coated material is, although the PVDC surface is not structured, clearly reduced. In this context what is meant by "non-structured" is a surface from which particles protrude but the surface neither shape or form wave troughs or crests. Block spotting caused by imprints on the back side of the adjacent film wrap on the film roll are heavily reduced or completely absent. Despite the absence of surface structuring, the spacer effect of the particles assures that air can escape from the film or material reel. Enclosed air can lead to film or material Deformations and, due to the blocking tendency of fresh PVDCs, to an irregularly matt surface of films. Due to the reduced static friction of the PVDC surface, the shearing forces created by the relaxation movements of the freshly coated roll material, acting parallel to the material surface, can better relax by the sliding of the PVDC surface facing the adjacent film wrap. This prevents material destruction which is brought about on less well sliding PVDC surfaces by the delaminations generated by the shear forces between the PVDC layer and the base carrier. The frictional resistance of PVDC coated flat films is reduced against the machine parts of thermoforming machines used to manufacture blisters from flat films. This reduces or completely eliminates film constrictions caused by excessive sheet tensions. The filling of tablet or capsule form packaging goods is substantially improved, since they can slide into the blister cavities better thanks to the heavily reduced coefficients of static friction and sliding friction. Especially gelatin capsules tend not to slide into the cavity when unmodified PVDC is used, to stand on end in the cavity, or even to jump out of the cavity. At the sealing station immediately downstream from the filling station, this leads to gumming up with squashed packing goods and, as a consequence, to long cleaning procedures. Furthermore, it is advantageous that, on the machine end, additional equipment and special working steps are not necessary for structuring the surface. The surface characteristics are exclusively dependent on the composition, and therefore can be safely adapted and easily reproducible. By means of the coating, a smooth, flat surface is generated which is aesthetically more attractive than a structured surface. The flat surface permits setting a larger layer volume for the top PVDC layer than in a structured surface, since the maximum dryable layer thickness in a structured layer is predetermined by highest points of the structure, i.e. the peaks of the wave crests, while in a flat surface, the dryable layer thickness is equally large as the maximum dryable thickness of the structurable layer, but in contrast to this does not have any wave troughs, but possesses a homogenously constant layer thickness. It is also advantageous that a surface modified in this way proves to slide very easily against the back side of the coated film and against the cavities of the form tool. This leads to the possibility, for one, of depiling with visibly less resistance/expenditure of energy unfilled, completely formed blister films whose cavities interlock, e.g. in the form of trimmed blister format pieces, or for another, the removal of the freshly formed blister cups out of the deep draw tool, under the condition that the modified PVDC side is used on the exterior side of the blister cup. In the first case, this results in faster depiling and thus in an increase in productivity, in the second case it results in disruption-free operation of the blister machine and thus to an increase in output. The invention is explained in greater detail with regard to the drawings. Fig. 1 shows in a schematic sectional view a customary PVDC coating of a composite film consisting of PVDC film/carrier film with structured PVDC surface, and Fig. 2 shows in a schematic sectional view a coating, according to the invention, consisting of PVDC, mixed with particles, on a composite film made of PVDC film/carrier film. The cross-section of the composite film 6 shown in Figure 1 comprises a carrier or base film 4, an adhesion promoter 3, and a PVDC film 2. The adhesion promoter 3 laminates the PVDC film 2 to the carrier film 4. On the top side of the PVDC film 2 a PVDC coating 7 is applied which features a structured surface 5 so that the layer thickness of the PVDC coating is uneven across the width of the composite film 6 and contains wave crests and wave troughs. The cross-section of composite film 1 shown in Figure 2 consists of a carrier or base film 11, an adhesion promoter 10, a PVDC film 9 and a coating 8 made of PVDC in which particles 12 made of HDPE are embedded. The particles 12 have different particle diameters, the average particle size is 6 to 8 µm and is suitable for a HDPE dispersion which leads to a coating with a thickness of up to 6 µm. The largest particles have a diameter of approx. 12µm. For a layer thickness of 12 µm the mean particle size is from 12 to 13 vm. The largest particles are approx. 17µm large. A number of particles 12 protrude out of the flat surface 13 of the coating 8 and act as spacers between the adjacent wraps of a wrapped composite film 1. Mixture of a PVDC dispersion with a HDPE dispersion The purpose of the following examples is to explain the invention in greater detail without meaning to imply that this restricts the protective scope of the invention characterized in the claims. In each case 1000 1 of coating consisting of PVDC dispersion are mixed with a HDPE dispersion, commercially available or freshly prepared. The PVDC dispersion has proportion of 55 % by weight PVDC, in relation to the total mass of PVDC dispersion, and a density of 1.29 g/cm3. In the HDPE dispersion, the HDPE portion is 65 % by weight of the total mass of HDPE dispersion and the density is 0.96 g/cm3. The desired amount of PVDC dispersion is put into a 1000 1 capacity container and stirred uniformly. The calculated amount of HDPE dispersion is added in a thin stream as the PVDC dispersion is being stirred in a non-foaming manner, and the mixture is stirred for a further 5 to 10 minutes. The HDPE dispersion used can be a ready-made, commercially available dispersion or a freshly prepared dispersing agent of HDPE powder that by corresponding stirring in of the particle power in water, with or without the help of one or several emulsifying agents, of pigment disperser or other disperser additives, of anionic tensides. It is also possible to directly add a HDPE powder into the PVDC dispersion, whereby special attention must be given to the prevention of clump formation which can result in uneven coating thicknesses. Example 2 The portion of HDPE dispersion was 2 % by volume of the total volume (in liters) of the coating Below the measured coefficients of static friction and sliding friction of a commonly known composite film with a pure PVDC coating, as described with the help of Figure 1, are juxtaposed with those of the film according to examples 1 and 2. The frictional force is measured with a test probe made of aluminum coated with hard gelatin. The measurement conditions were as follows: Test probe speed: 5 mm/min Mass of test probe: 200 g Material: aluminum, anodized Coating on test probe: ' hard gelatin Air humidity: 50 % RH Method: analogous ASTM D 1894 Age of PVDC coatings of three films each: 10 days A strong indirect dependency is visible of the coefficients of static friction on the portion of HDPE in the coating according to the invention. As the portion of HDPE increases, the coefficient of static friction drops. With the formula ((HRKOp - HRKP)/HRKOp) x 100 %, in which HRKOP is the coefficient of static friction of the composite film coated with PVDC without particles in the PVDC coating, and HRKp is the coefficient of static friction of the composite film coated with PVDC with particles in the PVDC coating, the coefficients of static friction HRKp are reduced by 61 % and 72 % with a HDPE portion by volume of 1 % and/or 2 %. Processing the composite films During processing the following advantages are achieved in comparison to PVDC coatings which contain no particles: Better removal of the blister from the deep draw mold when the PVDC-coated composite Film with PVDC coating is processed from the outside. Less constriction of the film sheet due to low frictional resistance against machine parts. Better filling characteristics of gelatin capsules in blister packs made from the composite films (PVDC side towards the packing goods). Lesser tendency of the composite films to stick fast to hot machine parts. Patent claims 1. Coating on the basis of polyvinylidene chloride which contains particles made of polymers, natural substances, modified natural substances, anorganic materials or mixtures thereof, characterized in that a number of particles protrudes out of the coating and forms spacers and that the density of the particles is in the range of 0.1 to 2.0 g/cm3. 2. Coating according to claim 1, characterized in that the mean particle diameter is in the range from 1 µm to 100 | µm. 3. Coating according to claim 2, characterized in that the density of the particles is smaller than/equal to 1.30 g/cm , especially smaller than/equal to 1 g/cm . 4. Coating according to claim 2, characterized in that the largest particle diameter is equal to/larger than the thickness of the coating. 5. Coating according to claim 1, characterized in that the particles are selected from a group comprising HDPE, LDPE, LLDPE, polypropylene, PVC, PVDC, polyamides, polyurethanes, polyacrylates, polystyrenes, polyacrylonitriles, acrylonitrile butadiene styrene polymerizates (ABS), polytetrafluoroethylene (PTFE), synthetic resins, hard waxes, as well as mixtures and copolymerizates thereof. 6. Coating according to claim 5, characterized in that the particles have a surface coating made of one of the polymers of the group HDPE, LDPE, LLDPE, polypropylene, PVC, PVDC, polyamides, polyurethanes, polyacrylates, polystyrenes, polyacrylonitriles, acrylonitrile butadiene styrene polymerizates (ABS), polytetrafluoroethylene (PTFE), synthetic resins, hard waxes, as well as mixtures and copolymerizates thereof. 7. Coating according to claim 6, characterized in that the particles have a dry portion from 0.1 to 10 wt% of the PVDC dry weight. Amended sheet (Article 19) 8. Coating according to claim 7, characterized in that the particles have a dry portion of 0.3 to 8 wt% of the PVDC dry weight. 9. Coating according to claim 7, characterized in that the particles feature a dry portion of 0.2 to 2 wt% of the PVDC dry weight. 10. Coating according to claim 1, characterized in that the particles in powder form are added to the PVDC. 11. Coating according to claim 1, characterized in that it is liquid and consists of a mixture of an anionic PVDC dispersion and an anionic dispersion made of micronized particles. 12. Coating according to claim 11, characterized in that the anionic dispersion consists of micronized particles, one or several emulsifying agents, anionic tensides, pigment dispersers and dispersion additives. 13. Coating according to claim 5, characterized in that the particles consist of HDPE. 14. Process for the manufacture of a coating on the basis of polyvinylidene chloride for sheet-formed materials, characterized in that a PVDC dispersion is provided into which particles are fed directly or into which a particle dispersion is fed while stirring and that the particles migrate within the coating to the surface or not, depending on their density. 15. Process according to claim 14, characterized in that the particle dispersion is prepared by stirring a particle powder into water without, or with one or several emulsifying agents.

Documents:

4753-CHENP-2006 EXAMINATION REPORT REPLY RECEIVED 22-11-2012.pdf

4753-CHENP-2006 POWER OF ATTORNEY 22-11-2012.pdf

4753-CHENP-2006 AMENDED PAGES OF SPECIFICATION 22-11-2012.pdf

4753-CHENP-2006 AMENDED CLAIMS 22-11-2012.pdf

4753-CHENP-2006 AMENDED CLAIMS 25-07-2013.pdf

4753-CHENP-2006 AMENDED PAGES OF SPECIFICATION 25-07-2013.pdf

4753-CHENP-2006 CORRESPONDENCE OTHERS 25-07-2013.pdf

4753-CHENP-2006 CORRESPONDENCE OTHERS 22-07-2013.pdf

4753-CHENP-2006 CORRESPONDENCE OTHERS 19-06-2013.pdf

4753-CHENP-2006 CORRESPONDENCE OTHERS 23-11-2012.pdf

4753-CHENP-2006 FORM-3 23-11-2012.pdf

4753-CHENP-2006 OTHER PATENT DOCUMENT 23-11-2012.pdf

4753-CHENP-2006 CORRESPONDENCE OTHERS 27-05-2013.pdf

4753-CHENP-2006 CORRESPONDENCE OTHERS 03-07-2013.pdf

4753-CHENP-2006 CORRESPONDENCE OTHERS 11-01-2012.pdf

4753-chenp-2006-abstract.pdf

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4753-chenp-2006-claims.pdf

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4753-chenp-2006-description(complete).pdf

4753-chenp-2006-drawings.pdf

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