WO2011036670A1 - A multilayer thermoformable packaging laminate - Google Patents
A multilayer thermoformable packaging laminate Download PDFInfo
- Publication number
- WO2011036670A1 WO2011036670A1 PCT/IN2009/000522 IN2009000522W WO2011036670A1 WO 2011036670 A1 WO2011036670 A1 WO 2011036670A1 IN 2009000522 W IN2009000522 W IN 2009000522W WO 2011036670 A1 WO2011036670 A1 WO 2011036670A1
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- WO
- WIPO (PCT)
- Prior art keywords
- substrate
- film
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- thickness
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- Prior art date
Links
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 53
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 20
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 17
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 36
- 239000000853 adhesive Substances 0.000 claims description 31
- 230000001070 adhesive effect Effects 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 29
- 239000004800 polyvinyl chloride Substances 0.000 claims description 28
- 238000004049 embossing Methods 0.000 claims description 22
- 229910003460 diamond Inorganic materials 0.000 claims description 17
- 239000010432 diamond Substances 0.000 claims description 17
- 239000004922 lacquer Substances 0.000 claims description 12
- 230000004888 barrier function Effects 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 238000001771 vacuum deposition Methods 0.000 claims description 6
- -1 Polypropylene Polymers 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004040 coloring Methods 0.000 claims description 3
- 239000013047 polymeric layer Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 241000284156 Clerodendrum quadriloculare Species 0.000 claims description 2
- 241000264877 Hippospongia communis Species 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000002952 polymeric resin Substances 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 239000010408 film Substances 0.000 description 129
- 238000003856 thermoforming Methods 0.000 description 32
- 229920000915 polyvinyl chloride Polymers 0.000 description 25
- 238000012360 testing method Methods 0.000 description 18
- 239000011104 metalized film Substances 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 238000007756 gravure coating Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 229920006254 polymer film Polymers 0.000 description 5
- 239000005083 Zinc sulfide Substances 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000005001 laminate film Substances 0.000 description 3
- 238000003698 laser cutting Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- 229920008790 Amorphous Polyethylene terephthalate Polymers 0.000 description 2
- 229920000134 Metallised film Polymers 0.000 description 2
- 241000385223 Villosa iris Species 0.000 description 2
- 239000005025 cast polypropylene Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012941 solvent-based polyurethane adhesive Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/28—Multiple coating on one surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4023—Coloured on the layer surface, e.g. ink
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/80—Medical packaging
Definitions
- the present invention relates to multi-layer film laminates. Particularly, the present invention relates to multi-layer film laminates suitable for use in the pharmaceutical packaging industry.
- blister packaging offers convenience in terms of portability and also helps to protect the packaged drug over a longer shelf life.
- One way to form blisters is by thermoforming a rigid polymer film.
- Blister packaging has proven to be a highly effective and successful packaging form for the pharmaceutical industry. Not only does it instill confidence regarding the quality and purity of a product, it also provides the manufacturer with a surface upon which information may be provided to the consumer.
- Blister packaging which is prone to counterfeiting, appears to be losing its 'sheen'. It can be a viable proposition if it evolves such that it is impossible for a counterfeiter to duplicate.
- the present invention therefore has as an object a packaging film which will help against counterfeiting.
- Another object of this invention is to provide a packaging film which will act as a protective authentication and by which a lay person can easily indentify the product at a display counter and distinguish it from a fake.
- thermoformable packaging laminate comprising (i) a pharmaceutical grade polymeric film substrate, devoid of plasticizer, and having vinyl monomer content less than 60 ppm, said substrate, having thickness in the range of 10 to 150 microns,
- a metallic compound layer the metallic compound being selected from a group consisting of a metal sulphide and a metal oxide of non uniform thickness between 0.001 to 0.3 micron deposited on said coat and embossed with a predetermined pattern;
- the polymeric substrate consists of at least one polymeric resin selected from a group of resins consisting of polyvinyl chloride (PVC), Polypropylene (PP), Polyethylene (PE), polyethylene terepthalate (PET) and co-polymers of theses resins.
- PVC polyvinyl chloride
- PP Polypropylene
- PE Polyethylene
- PET polyethylene terepthalate
- the polymeric substrate is transparent , translucent or coloured.
- the substrate is colored and coloring of the polymeric substrate is done by using a colored lacquer or a pigment.
- the base is multilayered and is laminated to the substrate after the patterns is embossed.
- the sulphide of metal is (ZnS).
- the metal oxide is silicon (SiO x and SiO x-n N x ) which provides transparent coating on the surface of the polymer laminate and which can provide better adhesion for the nonuniform embossed differential grating pattern on the substrate.
- the base is multilayered, having a plurality of polymeric layers bonded together, by adhesive bonding, thermal bonding or co-extrusion.
- the substrate is multilayered having at least one transparent layer and at least one colored layer.
- the substrate is multilayered, consisting of polymeric layers adhesive bonded to each other, the adhesive between the layers being pigmented.
- the metal used for sulphide or oxide coating is at least 99% pure metal selected from zinc and silicon.
- the film includes at least one colored or colorless lacquer layer having thickness of 0.5 to 8 microns applied between the substrate and the coat, between the coat and the metal sulphide or metal oxide layer or above the metal sulphide or metal oxide layer.
- the laminate may include an optional polymeric layer 0.5 to 250 microns thick.
- the substrate or base includes at least one polymeric layer selected from a group consisting of a moisture barrier layer, an oxygen barrier layer, a gas barrier, and a vapor barrier layer, said optional layer being provided operably within the substrate, on the substrate and below the coat 5 or below the substrate, or within the base.
- the embossed pattern is a diamond pattern, a broken glass pattern, a square pattern, a honey comb pattern, a triangular pattern, a wavy line pattern, a star burst pattern; a circular pattern a striation pattern or a combination of patterns and includes text matter.
- thermoformable packaging laminate comprising the following steps:
- the metal sulphide or metal oxide layer is deposited on the primer coat by vacuum deposition.
- the process includes a step of applying a lacquer coat, typically a colored lacquer coat either on the film or on the primer coat.
- the multilayer thermoformable non uniform embossed film may be coated with a suitable adhesive selected from the group of Polyurethanes, Waterborne acrylic dispersion-type coatings, UV-curable formulations, and unsaturated polyesters (peroxide cured).
- the present invention provides a multilayered thermoformable transparent non uniform metal sulphide or metal oxide coated polymeric laminate.
- a multilayer thermoformable laminate of thickness between 10 - 150 microns comprising a non uniform embossed metal sulphide or metal oxide coated polymeric film having first and second surfaces and at least one rigid thermoformable polymeric base of thickness between 50 - 1000 microns laminated to the non uniform embossed metallized film.
- a multi-layer laminate as used in the present text includes applying, layering and pressing or deposition of metal by vacuum evaporation process.
- a multi-layer laminate as used in the present invention includes a multi-layer laminate comprising a thermoformable non uniform embossed metal sulphide or metal oxide coated polymer based laminate.
- the expression "a multi-layer laminate” as used in the present invention also includes a laminate comprising a thermoformable non uniform embossed metallised film laminated with at least one rigid thermoformable polymer with the help of a suitable polymeric adhesive.
- the thickness of individual layers in the multi-layer laminate can vary depending on specific intended use and also on the ease of operation. Also, the multi-layer laminate may additionally comprise additional layers of polymer, resin or other substances, if desired.
- the rigid thermoformable polymeric film Before coating adhesive to the first surface of the rigid polymeric substrate, the rigid thermoformable polymeric film can be pretreated, to impart uniformity or improve the adhesion of the coated material.
- the non uniform embossed metallised film of thickness between 10-150 microns having first and second surfaces is first prepared.
- the first surface of the substrate is coated with metal sulphide or metal oxide by vacuum evaporation/deposition technique.
- the non uniform embossed metal sulphide or metal oxide coated film is initially coated with suitable primer for assuring uniform coating and proper adhesion of the metal oxide/sulphide on the polymeric film during vacuum evaporation.
- the metallized thermoformable film is then subjected to non uniform embossing with a desired art work and design.
- coloring of the metallized film can be done to get a coloured metallized non uniform embossed metallized film.
- the former film is coated with a desired coloured lacquer of thickness 0.5 to 1.5 microns.
- the application of the colored lacquer can be done before the metallization process or after the metallization process of the polymeric film.
- the coloured/ without colour metallized polymeric film is subjected to non uniform embossing with a predetermined art work design.
- the other side of this film is coated with a suitable adhesive of thickness between 0.5 - 8 microns and laminated with a rigid polymeric base having thickness between 50 to 1000 micron.
- the adhesive helps to fix the coloured/ without coloured metallized non uniform embossed metallized film to the rigid polymeric base on the second surface of the non uniform embossed metallized polymeric film efficiently.
- the adhesive comprises a polymeric substance capable of undergoing polymerization at higher temperatures.
- the adhesive coat can be applied by several methods typically known to a person skilled in the art and includes coating and spraying. The wet adhesive coat is then pressed with the desired polymer film. If desired s before applying the colored/ without coloured non uniform embossed metallized film, the adhesive coat is partially dried. Such partial drying at elevated temperature removes volatile components.
- the laminate may further be subjected to heat treatment.
- the adhesive coat comprises a polymerizable substance
- the curing of this polymerizable substance occurs through further polymerization, thereby imparting further adhesive strength.
- the post-heat treatment is optional and entirely depends on several parameters such as the nature of the individual constituents and the final properties desired.
- a wide variety of polymer films can be used for the thermoformable non uniform embossed metallized film according to the present invention.
- metallized color film such as a metallized polyvinyl chloride (PVC) film or high density polyethylene (HDPE) or low density polyethylene (LDPE) or polypropylene (PP) or amorphous polyethylene terephthalate (APET) and co-polymer of PET with glycol (PETg).
- PVC metallized polyvinyl chloride
- HDPE high density polyethylene
- LDPE low density polyethylene
- PP polypropylene
- APET amorphous polyethylene terephthalate
- PETg co-polymer of PET with glycol
- the colored film may be obtained commercially or prepared by metallizing a desired polymer film with a suitable metal like aluminum, silver, gold, through known a metallization process, such as for example, vacuum deposition.
- the obtained multi-layer laminate having a colored film which is metallized and embossed with a pre determined pattern and having non uniform thickness is laminated with the rigid thermoformable polymeric base .
- the thickness of individual layers, including those of the rigid polymeric base, adhesive coat and colored metallized non uniform embossed metallized film can be selected from within a wide range, depending on the specific intended use and/or operational ease.
- the multi-layer laminates according to the present invention have excellent bursting strength, barrier properties and deformation resistance.
- the laminates according to the present invention have high abrasion resistance and also can withstand thermoforming processes without any damage to the non uniform embossed metallized design during the process of thermoforming the film in to blisters packaging.
- the multilayered thermofromable non uniform embossed metallized film can act against counterfeiting effectively.
- a 35 micron pharmaceutical grade PVC film devoid of plasticizer having 600 mm width was subjected to an unwinder of a gravure coating machine.
- Ester— acrylic based primer from Magma Polymers Private Limited having viscosity of 26 to 32 sec. was applied using the gravure roller to the PVC film and extra primer was removed by doctoring process. Deposition of this primer had a thickness of 0.8 microns.
- this film was allowed to travel through on-line ovens via a conveyer. The oven temperature was set at a temperature of 75° C and the speed of 30 m/min for drying the primer on the film was maintained. The drying of the primer on the film was confirmed by non tackiness and by non blocking of the rewinding at the rewinder roller.
- the two layer film formed above was then transferred to a vacuum deposition machine.
- This machine had an in situ plasma device and was fitted with an evaporation boat in which the material to be deposited was placed.
- the primer coated surface of the laminated film was first treated with plasma and thereafter was deposited with zinc silphide having 99.99% purity. Thickness of this deposited layer was 0.025 microns. The thickness was achieved by adjusting the speed, height of the gun and the vacuum level.
- This three layer film was exposed to a differential embossing grating process.
- a custom built machine was used for the embossing process.
- the three layered film was placed on an unwinder of this custom made machine, the film was passed through the roller having temperature of 130 to 150° C by which the film was softened.
- a diamond pattern shim was pressed on the metallized side of the film to create a diffraction grating embossed effect on the film.
- the shim made for the above purpose was cut with a diamond pattern by using a computerized laser cutting mechanism to avoid duplication of the pattern by any one else.
- the other side of this film was then laminated to a 250 micron rigid PVC base by applying an adhesive between 0.5 to 8 microns through the gravure lamination technique.
- Blisters packs were formed from this laminate by the thermoforming process which showed excellent thermoforming performance and showed the fine diamond non uniform embossed metallized pattern even after the thermoforming process.
- Adhesion of embossed pattern with scotch tape test passes
- a film was produced as per example 1 except thickness of the PVC film was 50 microns and pattern used for embossing was a rain-bow pattern.
- the three layer film was laminated to a 250 micron rigid PVC base.,
- This laminate demonstrated the following properties
- Adhesion of embossed pattern with scotch tape test passes
- a film was produced as per example 1 except thickness of the PVC film was 100 microns and pattern used for embossing was fine grains pattern.
- the resulting multilayer film substrate was then laminated to a thermoformable, pharmaceutical grade PVC film of 250 microns devoid of plasticizer, using dry adhesion technology.
- Solvent based polyurethane adhesive of 4 microns was applied to the latter PVC mono layer film by using gravure coating process.
- the adhesive suspension that was applied had a viscosity of 24 sec, and was dried at 75° at a machine speed of 30 m/min.
- the multilayer film demonstrated the following properties.
- Adhesion of differentially grated laminated with scotch tape test passes Thermoforming performance Excellent Impact strength>950 g
- a film was produced as per the example 1 except thickness of the PVC film which was 120 microns and pattern used for embossing was square pattern.
- the resulting multilayer film substrate was then laminated to a base consisting of three PVC films of thicloiess 300 microns bounded to each other by using polyurethane based adhesive of thickness 4 microns via gravure coating technique, using dry adhesion technology as per example 3.
- the multilayer film demonstrated the following properties.
- a film was produced as per the example 2 in which a blue coloured pigmented 50 micron PVC film with text used for embossing with a flower like pattern.
- the resulting multilayered laminated demonstrated following properties:
- a film was produced as per example 5 in which a blue coloured pigmented PVC film of thickness 75 microns and pattern used for embossmg was broken glass pattern.
- the resulting multilayered laminated demonstrated the following properties:
- a film was produced as per example 1 except that the thickness of the PVC film was 50 microns and the pattern used for embossing was a square pattern.
- the resulting multilayered film was laminated with a blue coloured tinted 250 micron thick pharmaceutical grade, thermoformable rigid PVC base devoid of plasticizer with the help of gravure coating process using a polyurethane based adhesive of thickness 4 microns .
- the lamination was effected at 75°C.
- the resulting film demonstrated the following properties
- thermoformable pharmaceutical grade gold pigmented PVC film with zinc sulphide metallization layer thickness of .033 microns was made to undergo differential grating embossing procedure as per example 1 and further was laminated with a thermoformable pharmaceutical grade PVC film of thiclmess 300 microns with the help of polyurethane based adhesive coat via gravure coating * process.
- the resultant film demonstrated the following properties Total thickness 340 micron
- a laminate was produced as per example 1 except that the polymeric film was used from the class of co-polymer of polyethylene terepthalate and glycol (PETg) film having 50 micron thickness and the pattern used for embossing was a rain-bow pattern.
- PETg polyethylene terepthalate and glycol
- Adhesion of non uniform embossed pattern with scotch tape test passes
- a laminate was produced as per example 1 except that the polymeric film was used from the class of co-polymer of polyethylene terepthalate and glycol (PETg) film having thickness 100 microns and pattern used for embossing was diamond pattern.
- PETg polyethylene terepthalate and glycol
- Adhesion of non uniform embossed pattern with scotch tape test passes
- a laminate was produced as per example 1 except that the polymeric film was used from the class of co-polymer of polyethylene terepthalate and glycol (PETg) film of thickness 12 microns and pattern used for embossing was a square pattern.
- PETg polyethylene terepthalate and glycol
- Adhesion of non uniform embossed pattern with scotch tape test passes
- a laminate was produced as per example 1 except that a cast polypropylene film was used as a base having thickness of 300 microns and pattern used for embossing was a diamond pattern.
- the three layer laminate demonstrated the following properties
- Adhesion of non uniform embossed pattern with scotch tape test passes
- a film was produced as per example 1 except that the thickness of the PVC film was 3 microns and the pattern used was a broken glass pattern.
- the three layer film was further laminated with a 300 micron thick cast polypropylene film by using polyurethane based adhesive of thickness 5 microns with the help of gravure coating process.
- the resulting laminate demonstrated the following properties
- a laminate was produced as per example 1 except thickness of the PVC film was 100 microns and pattern used was a broken glass pattern.
- the three layer film was further laminated with a 250 micron thick co-polymer of polyethylene terepthalate and glycol (PETg) film base using a polyurethane based adhesive with the help of gravure coating process.
- PETg polyethylene terepthalate and glycol
- Adhesion of non uniform embossed pattern with scotch tape test passes Thermoforming performance Excellent
- a 50 micron pharmaceutical grade PVC film roll devoid of plasticizer having 600 mm width was subjected to un winder of gravure coating machine .
- a coloured lacquer was then applied to this film having thickness of 4 micron with the help of gravure technology then after second pass the Ester -acrylic based special primer from Magma Polymers Private Limited having viscosity of 26 to 32 sec. was applied using gravure roller to this PVC film and extra primer was removed by doctoring process. Deposition of this primer had a thickness of 0.8 microns.
- this film was allowed to travel through on line ovens via a conveyer at a temperature of 75° C at the speed of 30 m/min. The drying of the film was ensured by oii tacky and non blocking rewinding at the rewinder roller.
- the two layer laminate film formed above was then transferred to a vacuum deposition machine.
- This machine had an in situ plasma device and was fitted with an evaporating boat in which the material to be deposited was placed.
- the primer coated surface of above laminated film was first treated with plasma and thereafter deposited with a zinc sulphide layer having 99.99% purity, thickness of this deposited layer was 0.020 microns. The thickness was achieved by adjusting the speed, height of gun and vacuum level.
- this three layer laminated film was exposed to differential embossing grating process.
- Custom made machine was used for embossing process.
- the three layered laminated film was then placed on un winder of this custom made machine, the film then was passed through a roller having temperature of 130 to 150° C by which the film was getting soften, then diamond pattern shim was pressed on the metallized side of the laminate to create a diffraction grating on the film.
- the shim made for the above purpose was cut with a diamond pattern by using computerized laser cutting mechanism to avoid duplication of the pattern by any one else.
- this film was laminated to 200 micron PVC base devoid of plasticizer and having a vinyl chloride monomer concentration of less than 1 ppm and global migration less than 60 ppm.
- Blister packs were formed from this film by thermoforming process which showed excellent thermoforming performance and showed a fine diamond non uniform embossed metallized pattern even after the thermoforming process.
- This laminate exhibited the following properties,
- Adhesion of non uniform embossed pattern with scotch tape test passes
- a 50 micron pharmaceutical grade PVC film roll devoid of plasticizer having 600 mm width was subjected to the un winder of a gravure coating machine .
- Ester -acrylic based special primer from Magma Polymers Private Limited having viscosity of 26 to 32 sec. was applied using gravure roller to this PVC film and extra primer was removed by doctoring process. Deposition of this primer had thickness of 0.8 microns.
- this film was allowed to travel through in line ovens via a conveyer at a temperature of 75° C at a speed of 30 m/min. The drying of the film was ensured by non tacky and non blocking rewinding at rewinder roller. Colour lacquer was then applied to this film with the help of the gravure.
- the three layer laminate film formed above was then transferred to a vacuum deposition machine.
- the primer coated surface of above laminated film was first treated with plasma and zinc sulphide having 99.99% purity, thickness of this deposited layer was 0.1 micron. The thickness was achieved by adjusting the speed, height of gun and vacuum level.
- this three layer laminated film was exposed to differential embossing grating process.
- Custom made machine was used for the embossing process.
- the three layered laminated film was then placed on un winder of this custom made machine, the film was passed through a roller having temperature of 130 to 150° C by which the film was softened, then a diamond pattern shim was pressed on the metallized side of the laminate to create a diamond pattern on the film. Then this film was laminated as per example 17.
- Blister packs were formed from this film by a thermoforming process which showed excellent thermoforming performance and showed the fine diamond non uniform embossed metallized pattern even after thermoforming process.
- the laminate exhibited the following properties,
- Adhesion of non uniform embossed pattern with scotch tape test passes
- a 50 micron pharmaceutical grade PVC film roll devoid of plasticizer having 600 mm width was subjected to a un winder of gravure coating machine.
- Ester -acrylic based special primer with blue pigment in it from Magma Polymers Private Limited having viscosity of 26 to 32 sec. was applied using gravure . roller to this PVC film and extra primer was removed by doctoring process. Deposition of this primer had a thickness of 0.8 microns.
- This film was allowed to travel through in line ovens via a conveyer at a temperature of 75° C at the speed of 30 m/min. The drying of the film was ensured by non tacky and non blocking rewinding at rewinder roller.
- This two layer laminate film formed above was deposited with a zinc sulphide layer of 0.025 microns as per the previous examples.
- the thickness was achieved by adjusting the speed, height of gun and vacuum level.
- this three layer film was exposed to a differential embossing grating process.
- Custom made machine was used for embossing process.
- the three " layered laminated film was then placed on un winder of this custom made machine, the film then was passed through a roller having temperature of 130 to > 150° C by which the film was softened, then a diamond pattern shim was pressed on the metallized side of film to create a diamond pattern diffraction grating on the film as per the previous examples.
- the shim made for the above purpose was cut with a diamond pattern by using computerized laser cutting mechanism to avoid duplication of the pattern by any one else. Then this film was laminated as per example 17 to a base.
- blister packs were formed from this film by thermoforming process which showed excellent thermoforming performance and showed the fine diamond non uniform embossed metallized pattern even after the thermoforming process, the laminate exhibited the following properties,
- Adhesion of non uniform embossed pattern with scotch tape test passes
- Laminate made as per example 1 was coated with a PVDC coating on the other side of the diffraction grating with help of dispersion coating techniques to enhance the barrier properties of the laminate .
- Adhesion of non unifonn embossed pattern with scotch tape test passes
Abstract
A multilayer thermoformable packaging laminate comprising a pharmaceutical grade polymeric film substrate, devoid of plasticizer, and having vinyl monomer content less than 60 ppm, said substrate, having thickness in the range of 10 to 150 microns; a coat of an ester acrylic based primer, having thickness in the range of 0.1 to 1 micron provided on a first surface of said substrate; a metallic compound layer the metallic compound being selected from a group consisting of a metal sulphide and a metal oxide of non uniform thickness between 0.001 to 0.3 micron deposited on said coat and embossed with a predetermined pattern; and a polymeric base of thickness between 50 to 1000 micron laminated on the second surface of said substrate.
Description
A MULTILAYER THERMOFORMABLE PACKAGING LAMINATE
Field of the invention
The present invention relates to multi-layer film laminates. Particularly, the present invention relates to multi-layer film laminates suitable for use in the pharmaceutical packaging industry.
Background of the invention
Today, a significant fraction of healthcare products are packed in blisters. Amongst many other advantages, blister packaging offers convenience in terms of portability and also helps to protect the packaged drug over a longer shelf life. One way to form blisters is by thermoforming a rigid polymer film.
Blister packaging has proven to be a highly effective and successful packaging form for the pharmaceutical industry. Not only does it instill confidence regarding the quality and purity of a product, it also provides the manufacturer with a surface upon which information may be provided to the consumer.
Counterfeiting is a severe problem, for all industries including the pharmaceutical industry. Legitimate businesses are losing millions due to counterfeit activity. The International chamber of commerce estimates that US $ 900 Billion are lost by businesses worldwide. This translates to 10-30 % of the sales being lost to counterfeiters, forgers and duplicators. In some countries the figure in percentage is much higher.
Counterfeiting is the fastest growing crime in the world. Studies show that consumers would prefer to buy products that are in tamper evident
authenticated packaging so as to reduce the chance of buying imitation products.
However, with the growing counterfeiting problem, that the pharmaceutical industry has to tackle (research by the World Health Organization shows that approximately 5% of the world's medicines are counterfeit, and in some areas this percentage can be as high as 50%), leading brands are prone to be attacked by unscrupulous individuals. It is the responsibility of the manufacturer or brand owner to ensure that a genuine unadulterated product reaches the consumer.
Blister packaging, which is prone to counterfeiting, appears to be losing its 'sheen'. It can be a viable proposition if it evolves such that it is impossible for a counterfeiter to duplicate.
Objects of the invention
The present invention therefore has as an object a packaging film which will help against counterfeiting. Another object of this invention is to provide a packaging film which will act as a protective authentication and by which a lay person can easily indentify the product at a display counter and distinguish it from a fake.
Summary of the invention
According to this invention there is provided a multilayer thermoformable packaging laminate comprising
(i) a pharmaceutical grade polymeric film substrate, devoid of plasticizer, and having vinyl monomer content less than 60 ppm, said substrate, having thickness in the range of 10 to 150 microns,
(ii) a coat of an ester acrylic based primer, having thickness in the range of 0.1 to 1 micron provided on a first surface of said substrate,
(iii) a metallic compound layer the metallic compound being selected from a group consisting of a metal sulphide and a metal oxide of non uniform thickness between 0.001 to 0.3 micron deposited on said coat and embossed with a predetermined pattern; and
(iv) a polymeric base of thickness between 50 to 1000 micron laminated on the second surface of said substrate.
Typically, the polymeric substrate consists of at least one polymeric resin selected from a group of resins consisting of polyvinyl chloride (PVC), Polypropylene (PP), Polyethylene (PE), polyethylene terepthalate (PET) and co-polymers of theses resins.
Typically , the polymeric substrate is transparent , translucent or coloured.
In one embodiment of the invention, the substrate is colored and coloring of the polymeric substrate is done by using a colored lacquer or a pigment.
Preferabely, the base is multilayered and is laminated to the substrate after the patterns is embossed.
Preferably the sulphide of metal is (ZnS). Preferably, the metal oxide is silicon (SiOx and SiOx-nNx) which provides transparent coating on the surface of the
polymer laminate and which can provide better adhesion for the nonuniform embossed differential grating pattern on the substrate.]
Typically, the base is multilayered, having a plurality of polymeric layers bonded together, by adhesive bonding, thermal bonding or co-extrusion.
In one embodiment, the substrate is multilayered having at least one transparent layer and at least one colored layer.
In another embodiment, the substrate is multilayered, consisting of polymeric layers adhesive bonded to each other, the adhesive between the layers being pigmented.
In accordance with this invention, the metal used for sulphide or oxide coating is at least 99% pure metal selected from zinc and silicon.
In yet another embodiment, the film includes at least one colored or colorless lacquer layer having thickness of 0.5 to 8 microns applied between the substrate and the coat, between the coat and the metal sulphide or metal oxide layer or above the metal sulphide or metal oxide layer.
The laminate may include an optional polymeric layer 0.5 to 250 microns thick.
In yet another embodiment, the substrate or base includes at least one polymeric layer selected from a group consisting of a moisture barrier layer, an oxygen barrier layer, a gas barrier, and a vapor barrier layer, said optional layer being
provided operably within the substrate, on the substrate and below the coat5 or below the substrate, or within the base.
Typically, the embossed pattern is a diamond pattern, a broken glass pattern, a square pattern, a honey comb pattern, a triangular pattern, a wavy line pattern, a star burst pattern; a circular pattern a striation pattern or a combination of patterns and includes text matter.
In accordance with another aspect of this invention, there is provided a process for preparation of a multilayer thermoformable packaging laminate comprising the following steps:
(i) applying a coat of an ester acrylic based primer, upto a thickness in the range of 0.1 to 1 micron upon a pharmaceutical grade polymeric film substrate, devoid of plasticizer, and having vinyl monomer content less than 60 ppm, said substrate, having thickness in the range of 10 to 150 microns;
(ii) partially drying the said primer coat;
(iii) depositing a metal compound selected from sulphide or metal oxide on the said partially dried primer coat to form a metal sulphide or metal oxide layer of thickness between .001 to 0.3 microns; and
(iv) embossing the metalized layer with a shim to form an embossed pattern on the metal compound layer and to make the thickness of the metal compound layer non uniform;
(v) laminating other side of the substrate with a polymeric base of thickness 50 to 1000 microns.
Typically the metal sulphide or metal oxide layer is deposited on the primer coat by vacuum deposition.
In accordance with another aspect of the process of the invention the process includes a step of applying a lacquer coat, typically a colored lacquer coat either on the film or on the primer coat.
The multilayer thermoformable non uniform embossed film may be coated with a suitable adhesive selected from the group of Polyurethanes, Waterborne acrylic dispersion-type coatings, UV-curable formulations, and unsaturated polyesters (peroxide cured).
Detailed description of the invention
The present invention provides a multilayered thermoformable transparent non uniform metal sulphide or metal oxide coated polymeric laminate. A multilayer thermoformable laminate of thickness between 10 - 150 microns comprising a non uniform embossed metal sulphide or metal oxide coated polymeric film having first and second surfaces and at least one rigid thermoformable polymeric base of thickness between 50 - 1000 microns laminated to the non uniform embossed metallized film.
The present invention is now described with reference to various specific and preferred embodiments and techniques. However, it should be understood that many variations and modifications may be made while remaining within the spirit and scope of the invention. In the case of any inconsistencies, the present disclosure, including any definitions therein will prevail.
The term "coating" as used in the present text includes applying, layering and pressing or deposition of metal by vacuum evaporation process.
The expression "a multi-layer laminate" as used in the present invention includes a multi-layer laminate comprising a thermoformable non uniform embossed metal sulphide or metal oxide coated polymer based laminate. The expression "a multi-layer laminate" as used in the present invention also includes a laminate comprising a thermoformable non uniform embossed metallised film laminated with at least one rigid thermoformable polymer with the help of a suitable polymeric adhesive.
The thickness of individual layers in the multi-layer laminate can vary depending on specific intended use and also on the ease of operation. Also, the multi-layer laminate may additionally comprise additional layers of polymer, resin or other substances, if desired.
Before coating adhesive to the first surface of the rigid polymeric substrate, the rigid thermoformable polymeric film can be pretreated, to impart uniformity or improve the adhesion of the coated material.
In a typical process for preparation of a multi-layer laminate according to the present invention, the non uniform embossed metallised film of thickness between 10-150 microns having first and second surfaces is first prepared. The first surface of the substrate is coated with metal sulphide or metal oxide by vacuum evaporation/deposition technique. The non uniform embossed metal sulphide or metal oxide coated film is initially coated with suitable primer for assuring uniform coating and proper adhesion of the metal oxide/sulphide on the polymeric film during vacuum evaporation. The metallized thermoformable film is then subjected to non uniform embossing with a desired art work and design. Optionally coloring of the metallized film can be done to get a coloured
metallized non uniform embossed metallized film. To achieve coloration of the metallized film, the former film is coated with a desired coloured lacquer of thickness 0.5 to 1.5 microns. The application of the colored lacquer can be done before the metallization process or after the metallization process of the polymeric film. Then, the coloured/ without colour metallized polymeric film is subjected to non uniform embossing with a predetermined art work design. The other side of this film is coated with a suitable adhesive of thickness between 0.5 - 8 microns and laminated with a rigid polymeric base having thickness between 50 to 1000 micron. The adhesive helps to fix the coloured/ without coloured metallized non uniform embossed metallized film to the rigid polymeric base on the second surface of the non uniform embossed metallized polymeric film efficiently. A wide variety of adhesives can be advantageously used according to the present invention. Preferably, the adhesive comprises a polymeric substance capable of undergoing polymerization at higher temperatures. The adhesive coat can be applied by several methods typically known to a person skilled in the art and includes coating and spraying. The wet adhesive coat is then pressed with the desired polymer film. If desireds before applying the colored/ without coloured non uniform embossed metallized film, the adhesive coat is partially dried. Such partial drying at elevated temperature removes volatile components. Once the desired polymer film is applied on the adhesive coat, say by pressing, the laminate may further be subjected to heat treatment. When the adhesive coat comprises a polymerizable substance, the curing of this polymerizable substance occurs through further polymerization, thereby imparting further adhesive strength. However, the post-heat treatment is optional and entirely depends on several parameters such as the nature of the individual constituents and the final properties desired.
A wide variety of polymer films can be used for the thermoformable non uniform embossed metallized film according to the present invention. Typical non-limiting examples of such film include metallized color film such as a metallized polyvinyl chloride (PVC) film or high density polyethylene (HDPE) or low density polyethylene (LDPE) or polypropylene (PP) or amorphous polyethylene terephthalate (APET) and co-polymer of PET with glycol (PETg). The colored film may be obtained commercially or prepared by metallizing a desired polymer film with a suitable metal like aluminum, silver, gold, through known a metallization process, such as for example, vacuum deposition.
Thus the obtained multi-layer laminate having a colored film which is metallized and embossed with a pre determined pattern and having non uniform thickness is laminated with the rigid thermoformable polymeric base .. As mentioned earlier, the thickness of individual layers, including those of the rigid polymeric base, adhesive coat and colored metallized non uniform embossed metallized film can be selected from within a wide range, depending on the specific intended use and/or operational ease.
The multi-layer laminates according to the present invention have excellent bursting strength, barrier properties and deformation resistance. Advantageously, the laminates according to the present invention have high abrasion resistance and also can withstand thermoforming processes without any damage to the non uniform embossed metallized design during the process of thermoforming the film in to blisters packaging. Further, the multilayered thermofromable non uniform embossed metallized film can act against counterfeiting effectively.
From the foregoing description, it will thus be evident that the present invention provides novel multi-layer laminates comprising thermoformable ed non uniform embossed metallized layered polymeric films and at least one rigid polymeric base and a method for their preparation. While certain embodiments of the invention have been described, these embodiments have been presented by way of examples only, and are not intended to limit the scope of the inventions. Variations or modifications to the design and construction of this invention, within the scope of the invention, may occur to those skilled in the art upon reviewing the disclosure herein. Such variations or modifications are well within the spirit of this invention. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the invention.
The invention will now be described with reference to the accompanying examples
Example 1
A 35 micron pharmaceutical grade PVC film devoid of plasticizer having 600 mm width was subjected to an unwinder of a gravure coating machine. Ester— acrylic based primer from Magma Polymers Private Limited having viscosity of 26 to 32 sec. was applied using the gravure roller to the PVC film and extra primer was removed by doctoring process. Deposition of this primer had a thickness of 0.8 microns. Then this film was allowed to travel through on-line ovens via a conveyer. The oven temperature was set at a temperature of 75° C and the speed of 30 m/min for drying the primer on the film was maintained. The drying of the primer on the film was confirmed by non tackiness and by non blocking of the rewinding at the rewinder roller.
The two layer film formed above was then transferred to a vacuum deposition machine. This machine had an in situ plasma device and was fitted with an evaporation boat in which the material to be deposited was placed. The primer coated surface of the laminated film was first treated with plasma and thereafter was deposited with zinc silphide having 99.99% purity. Thickness of this deposited layer was 0.025 microns. The thickness was achieved by adjusting the speed, height of the gun and the vacuum level.
This three layer film was exposed to a differential embossing grating process. A custom built machine was used for the embossing process. The three layered film was placed on an unwinder of this custom made machine, the film was passed through the roller having temperature of 130 to 150° C by which the film was softened. A diamond pattern shim was pressed on the metallized side of the film to create a diffraction grating embossed effect on the film. The shim made for the above purpose was cut with a diamond pattern by using a computerized laser cutting mechanism to avoid duplication of the pattern by any one else. The other side of this film was then laminated to a 250 micron rigid PVC base by applying an adhesive between 0.5 to 8 microns through the gravure lamination technique.
Blisters packs were formed from this laminate by the thermoforming process which showed excellent thermoforming performance and showed the fine diamond non uniform embossed metallized pattern even after the thermoforming process.
Specification of the film was as follows:
Total thickness 287 micron
Adhesion of embossed pattern with scotch tape test: passes
Thermoforming performance Excellent
impact strength 955 g
Tensile strength - Longitudinal 13.5 kg/cm2
-Transverse 13.7 Kg/cm2
Elongation - Longitudinal 5.9%
- Transverse 5.8%
Heat seal strength 0.65 kg/cm
WVTR of the blister 8 g/m2/day
Example 2
A film was produced as per example 1 except thickness of the PVC film was 50 microns and pattern used for embossing was a rain-bow pattern. The three layer film was laminated to a 250 micron rigid PVC base., |This laminate demonstrated the following properties
Total thickness 304 micron
Adhesion of embossed pattern with scotch tape test: passes
Thermoforming performance ^ Excellent
Impact strength > 950 g
Tensile strength - Longitudinal 14.05 kg/cm2
-Transverse 14.13 Kg/cm2
Elongation - Longitudinal 6.2 %
- Transverse 6.15 %
Heat seal strength 0.65 kg/cm2
Example 3
A film was produced as per example 1 except thickness of the PVC film was 100 microns and pattern used for embossing was fine grains pattern. The
resulting multilayer film substrate was then laminated to a thermoformable, pharmaceutical grade PVC film of 250 microns devoid of plasticizer, using dry adhesion technology. Solvent based polyurethane adhesive of 4 microns was applied to the latter PVC mono layer film by using gravure coating process. The adhesive suspension that was applied had a viscosity of 24 sec, and was dried at 75° at a machine speed of 30 m/min. The multilayer film demonstrated the following properties.
Total thicloiess 354 micron
Differentially grated laminated film thickness 100 micron
Adhesive coat 4 microns
Adhesion to substrate & differentially grated laminated film 200 gm/cm
Adhesion of differentially grated laminated with scotch tape test: passes Thermoforming performance Excellent Impact strength>950 g
Tensile strength - Longitudinal 20.85 kg/cm2
-Transverse 20.6 kg/cm
Elongation Longitudinal 6.6 %
i ransverse 6.7 %
Example 4
A film was produced as per the example 1 except thickness of the PVC film which was 120 microns and pattern used for embossing was square pattern. The resulting multilayer film substrate was then laminated to a base consisting of three PVC films of thicloiess 300 microns bounded to each other by using polyurethane based adhesive of thickness 4 microns via gravure coating
technique, using dry adhesion technology as per example 3. The multilayer film demonstrated the following properties.
Total thickness 1050 micron
Differentially grated laminated film thickness 120 micron
Adhesive coat 12 microns
Adhesion to substrate & differentially grated laminated film 200 gm/cm Adhesion of differentially grated laminated with scotch tape test: passes Thermoforming performance not possible
Impact strength > 900 g
Tensile strength - Longitudinal 50.66 kg/cm
-Transverse 45.44 kg/cm2
Elongation - Longitudinal 8.5 %
- Transverse 7.6 %
Example 5
A film was produced as per the example 2 in which a blue coloured pigmented 50 micron PVC film with text used for embossing with a flower like pattern. The resulting multilayered laminated demonstrated following properties:
Total thickness 304 micron
Differentially grated laminated film thickness 50 micron
Adhesive coat 4 microns
Adhesion to substrate & differentially grated laminated film 200 gm/cm Adhesion of differentially grated laminated with scotch tape test: passes Thermoforming performance Excellent Impact strength > 950 g
Tensile strength - Longitudinal 14.05 kg/cm2
-Transverse 14.13 kg/cm2
Elongation - Longitudinal 6.2 %
- Transverse 6.15 %
Example 6
A film was produced as per example 5 in which a blue coloured pigmented PVC film of thickness 75 microns and pattern used for embossmg was broken glass pattern. The resulting multilayered laminated demonstrated the following properties:
Total thickness 330 micron blue tinted differentially grated laminated film thickness 75 micron
Adhesive coat 5 microns
Adhesion to substrate & differentially grated laminated film 200 gm/cm Adhesion of differentially grated laminated with scotch tape test: passes Thermoforming performance Excellent Impact strength > 950 g
Tensile strength - Longitudinal 15.5 kg/cm2
-Transverse 15.2 kg/cm2
Elongation - Longitudinal 7.2 %
- Transverse 7.15%
Example 7
A film was produced as per example 1 except that the thickness of the PVC film was 50 microns and the pattern used for embossing was a square pattern. The resulting multilayered film was laminated with a blue coloured tinted 250
micron thick pharmaceutical grade, thermoformable rigid PVC base devoid of plasticizer with the help of gravure coating process using a polyurethane based adhesive of thickness 4 microns . The lamination was effected at 75°C. The resulting film demonstrated the following properties
Total thickness 304 micron
Differentially grated laminated film thickness 50 micron
Adhesive coat 4 microns
Colour Blue
Adhesion to substrate & differentially grated laminated film 200 gm/cm Adhesion of differentially grated laminated with scotch tape test: passes Thermo forming performance Excellent Impact strength > 950 g
Tensile strength - Longitudinal 14.1 kg/cm
-Transverse 14.0 kg/cm
Elongation - Longitudinal 6.2 %
- Transverse 6.15 %
Example 8
A 35 micron thick thermoformable pharmaceutical grade gold pigmented PVC film with zinc sulphide metallization layer thickness of .033 microns was made to undergo differential grating embossing procedure as per example 1 and further was laminated with a thermoformable pharmaceutical grade PVC film of thiclmess 300 microns with the help of polyurethane based adhesive coat via gravure coating* process. The resultant film demonstrated the following properties
Total thickness 340 micron
Gold tinted differentially grated laminated film thickness 35 micron
Adhesive coat 5 microns
Adhesion to substrate & di ferentially grated laminated Film 200 gm/cm Adhesion of differentially grated laminated with scotch tape test: passes Thermoforming performance Excellent Impact strength . > 950 g
Tensile strength - Longitudinal 15.1 kg/cm
-Transverse 15.0 kg/cm2
Elongation - Longitudinal 6.2%
- Transverse 6.1%
Example 9
A laminate was produced as per example 1 except that the polymeric film was used from the class of co-polymer of polyethylene terepthalate and glycol (PETg) film having 50 micron thickness and the pattern used for embossing was a rain-bow pattern. The resultant laminate demonstrated the following properties
Total thickness 300 micron
Adhesion of non uniform embossed pattern with scotch tape test: passes
Thermoforming performance Excellent
Impact strength >950 g
Tensile strength - Longitudinal 12 kg/cm2
-Transverse 12.1 Kg/cm2
Elongation - Longitudinal 5.5%
- Transverse 5.1%
Example 10
A laminate was produced as per example 1 except that the polymeric film was used from the class of co-polymer of polyethylene terepthalate and glycol (PETg) film having thickness 100 microns and pattern used for embossing was diamond pattern. The resultant laminate demonstrated the following properties
Total thickness 354 micron
Adhesion of non uniform embossed pattern with scotch tape test: passes
Thermofonning performance Excellent
Impact strength 950 g
Tensile strength - Longitudinal 12.5 kg/cm2
-Transverse 12.4 Kg/cm2
Elongation - Longitudinal 5.9 %
- Transverse 5.8 %
Heat seal strength 0.65 kg/cm
Example 11
A laminate was produced as per example 1 except that the polymeric film was used from the class of co-polymer of polyethylene terepthalate and glycol (PETg) film of thickness 12 microns and pattern used for embossing was a square pattern. The laminate demonstrated the following properties
Total thickness 267 micron
Adhesion of non uniform embossed pattern with scotch tape test: passes
Thermoforming performance excellent
Impact strength >950 g
Tensile strength - Longitudinal 6.5 kg/cm
-Transverse 5.75 kg/cm
Elongation - Longitudinal 5.5 %
- Transverse 5.1 %
Example 14
A laminate was produced as per example 1 except that a cast polypropylene film was used as a base having thickness of 300 microns and pattern used for embossing was a diamond pattern. The three layer laminate demonstrated the following properties
Total thickness 335 micron
Adhesion of non uniform embossed pattern with scotch tape test: passes
Thermoforming performance Excellent
Impact strength > 50 g
Tensile strength - Longitudinal 2.36 kg/cm2
-Transverse 2.2 Kg/cm2
Elongation - Longitudinal 11.2%
- Transverse 11%
Example 15
A film was produced as per example 1 except that the thickness of the PVC film was 3 microns and the pattern used was a broken glass pattern. The three layer film was further laminated with a 300 micron thick cast polypropylene film by using polyurethane based adhesive of thickness 5 microns with the help of gravure coating process. The resulting laminate demonstrated the following properties
Total thickness 340 micron
Adhesion of non uniform embossed pattern with scotch tape test: passes Thermo forming performance Excellent
Impact strength >953 g
Tensile strength - Longitudinal 17.39 kg/cm2
-Transverse 16.78 Kg/cm2
Elongation - Longitudinal 6.4%
-Transverse 6.5%
Example 16
A laminate was produced as per example 1 except thickness of the PVC film was 100 microns and pattern used was a broken glass pattern. The three layer film was further laminated with a 250 micron thick co-polymer of polyethylene terepthalate and glycol (PETg) film base using a polyurethane based adhesive with the help of gravure coating process. The resulting film demonstrated the following properties
Total thickness 360 micron
Adhesion of non uniform embossed pattern with scotch tape test: passes Thermoforming performance Excellent
Impact strength >953 g
Tensile strength - Longitudinal 17.39 kg/cm.2
-Transverse 16.78 Kg/cm2
Elongation - Longitudinal 6.4%
-Transverse 6.5%
Example 17
A 50 micron pharmaceutical grade PVC film roll devoid of plasticizer having 600 mm width was subjected to un winder of gravure coating machine . A coloured lacquer was then applied to this film having thickness of 4 micron
with the help of gravure technology then after second pass the Ester -acrylic based special primer from Magma Polymers Private Limited having viscosity of 26 to 32 sec. was applied using gravure roller to this PVC film and extra primer was removed by doctoring process. Deposition of this primer had a thickness of 0.8 microns. Then this film was allowed to travel through on line ovens via a conveyer at a temperature of 75° C at the speed of 30 m/min. The drying of the film was ensured by oii tacky and non blocking rewinding at the rewinder roller.
Thus the two layer laminate film formed above was then transferred to a vacuum deposition machine. This machine had an in situ plasma device and was fitted with an evaporating boat in which the material to be deposited was placed. The primer coated surface of above laminated film was first treated with plasma and thereafter deposited with a zinc sulphide layer having 99.99% purity, thickness of this deposited layer was 0.020 microns. The thickness was achieved by adjusting the speed, height of gun and vacuum level.
Further, this three layer laminated film was exposed to differential embossing grating process. Custom made machine was used for embossing process. The three layered laminated film was then placed on un winder of this custom made machine, the film then was passed through a roller having temperature of 130 to 150° C by which the film was getting soften, then diamond pattern shim was pressed on the metallized side of the laminate to create a diffraction grating on the film. The shim made for the above purpose was cut with a diamond pattern by using computerized laser cutting mechanism to avoid duplication of the pattern by any one else. Then this film was laminated to 200 micron PVC base devoid of plasticizer and having a vinyl chloride monomer concentration of less than 1 ppm and global migration less than 60 ppm.
Blister packs were formed from this film by thermoforming process which showed excellent thermoforming performance and showed a fine diamond non uniform embossed metallized pattern even after the thermoforming process. This laminate exhibited the following properties,
Total thickness 256 microns
Adhesion of non uniform embossed pattern with scotch tape test: passes
Thermoforming performance Excellent
Impact strength 953 g
Tensile strength - Longitudinal 5.11 kg/cm2
-Transverse 4.88 Kg/cm2
Elongation - Longitudinal 5%
- Transverse 4.8%
Heat seal strength 0.65 kg/cm
Example 18
A 50 micron pharmaceutical grade PVC film roll devoid of plasticizer having 600 mm width was subjected to the un winder of a gravure coating machine .Ester -acrylic based special primer from Magma Polymers Private Limited having viscosity of 26 to 32 sec. was applied using gravure roller to this PVC film and extra primer was removed by doctoring process. Deposition of this primer had thickness of 0.8 microns. Then this film was allowed to travel through in line ovens via a conveyer at a temperature of 75° C at a speed of 30 m/min. The drying of the film was ensured by non tacky and non blocking rewinding at rewinder roller. Colour lacquer was then applied to this film with the help of the gravure.
Thus the three layer laminate film formed above was then transferred to a vacuum deposition machine. The primer coated surface of above laminated film
was first treated with plasma and zinc sulphide having 99.99% purity, thickness of this deposited layer was 0.1 micron. The thickness was achieved by adjusting the speed, height of gun and vacuum level.
Further, this three layer laminated film was exposed to differential embossing grating process. Custom made machine was used for the embossing process. The three layered laminated film was then placed on un winder of this custom made machine, the film was passed through a roller having temperature of 130 to 150° C by which the film was softened, then a diamond pattern shim was pressed on the metallized side of the laminate to create a diamond pattern on the film. Then this film was laminated as per example 17.
Blister packs were formed from this film by a thermoforming process which showed excellent thermoforming performance and showed the fine diamond non uniform embossed metallized pattern even after thermoforming process. The laminate exhibited the following properties,
Total thickness 256 micron
Adhesion of non uniform embossed pattern with scotch tape test: passes
Thermoforming performance Excellent
Impact strength 953 g
Tensile strength - Longitudinal 5.11 kg/cm2
-Transverse 4.88 Kg/cm2
Elongation - Longitudinal 5%
- Transverse 4.8%
Heat seal strength 0.65 kg/cm
Example 19
A 50 micron pharmaceutical grade PVC film roll devoid of plasticizer having 600 mm width was subjected to a un winder of gravure coating machine. Ester
-acrylic based special primer with blue pigment in it from Magma Polymers Private Limited having viscosity of 26 to 32 sec. was applied using gravure. roller to this PVC film and extra primer was removed by doctoring process. Deposition of this primer had a thickness of 0.8 microns. This film was allowed to travel through in line ovens via a conveyer at a temperature of 75° C at the speed of 30 m/min. The drying of the film was ensured by non tacky and non blocking rewinding at rewinder roller.
This two layer laminate film formed above was deposited with a zinc sulphide layer of 0.025 microns as per the previous examples. The thickness was achieved by adjusting the speed, height of gun and vacuum level.
Further, this three layer film was exposed to a differential embossing grating process. Custom made machine was used for embossing process. The three" layered laminated film was then placed on un winder of this custom made machine, the film then was passed through a roller having temperature of 130 to > 150° C by which the film was softened, then a diamond pattern shim was pressed on the metallized side of film to create a diamond pattern diffraction grating on the film as per the previous examples. The shim made for the above purpose was cut with a diamond pattern by using computerized laser cutting mechanism to avoid duplication of the pattern by any one else. Then this film was laminated as per example 17 to a base.
blister packs were formed from this film by thermoforming process which showed excellent thermoforming performance and showed the fine diamond non uniform embossed metallized pattern even after the thermoforming process, the laminate exhibited the following properties,
Total thickness 256 micron
Adhesion of non uniform embossed pattern with scotch tape test: passes
Thermoforming performance Excellent
Impact strength 953 g
Tensile strength - Longitudinal 5.11 kg/cm2
-Transverse 4.88 Kg/cm2
Elongation - Longitudinal 5%
- Transverse 4.8%
Heat seal strength 0.65 kg/cm
Example 20
Laminate made as per example 1 was coated with a PVDC coating on the other side of the diffraction grating with help of dispersion coating techniques to enhance the barrier properties of the laminate .
the laminate exhibited the following properties,
Total thickness 280 micron
Adhesion of non unifonn embossed pattern with scotch tape test: passes
Thermoforming performance Excellent
Impact strength 953 g
Tensile strength - Longitudinal 5.11 kg/cm2
-Transverse 4.88 Kg/cm2
Elongation - Longitudinal 5%
- Transverse 4.8%
Heat seal strength 0.65 kg/cm
WVT 0.1 gm/cm2/day
Claims
[1] A multilayer thermoformable packaging laminate comprising
(i) a pharmaceutical grade polymeric film substrate, devoid of plasticizer, and having vinyl monomer content less than 60 ppm, said substrate, having thicloiess in the range of 10 to 150 microns,
(ii) a coat of an ester acrylic based primer, having thickness in the range of 0.1 to 1 micron provided on a first surface of said substrate,
(iii) a metallic compound layer the metallic compound being selected from a group consisting of a metal sulphide and a metal oxide of non uniform thicloiess between 0.001 to 0.3 micron deposited on said coat and embossed with a predetermined pattern; and
(iv) a polymeric base of thickness between 50 to 1000 micron laminated on the second surface of said substrate.
[2] A multilayer thermoformable packaging laminate as claimed in claim 1, in which , the polymeric substrate consists of at least one polymeric resin selected from a group of resins consisting of polyvinyl chloride (PVC), Polypropylene (PP), Polyethylene (PE), polyethylene terepthalate (PET) and co-polymers of theses resins.
[3] A multilayer thermoformable packaging laminate as claimed in claim 1, in which the polymeric substrate is transparent , translucent or coloured.
[4] A multilayer thermoformable packaging laminate as claimed in claim 1, in which the substrate is colored and coloring of the polymeric substrate is done by using a colored lacquer or a pigment.
[5] A multilayer t ermoformable packaging laminate as claimed in claim 1, in which the base is multilayered and is laminated to the substrate after the pattern is embossed.
[6] A multilayer thermoformable packaging laminate as claimed in claim 1, in which the sulphide of metal is (ZnS).
[7] A multilayer thermoformable packaging laminate as claimed in claim 1, in which the metal oxide is silicon (SiOx and SiOx-nNn).
[8] A multilayer thermoformable packaging laminate as claimed in claim 1, in which the base is multilayered, having a plurality of polymeric layers bonded together, by adhesive bonding, thermal bonding or co-extrusion.
[9] A multilayer thermoformable packaging laminate as claimed in claim 1, in which the substrate is multilayered having at least one transparent layer and at least one colored layer.
[10] A multilayer thermoformable packaging laminate as claimed in claim 1, in which the substrate is multilayered, consisting of polymeric layers adhesive bonded to each other, the adhesive between the layers being pigmented.
[11] A multilayer thermoformable packaging laminate as claimed in claim 1, in which the metal used for sulphide or oxide coating is at least 99% pure metal selected from zinc and silicon.
[12] A multilayer thermoformable packaging laminate as claimed in claim 1, in which the film includes at least one colored or colorless lacquer layer having thickness of 0.5 to 8 microns applied between the substrate and the coat, between the coat and the metal sulphide or metal oxide layer or above the metal sulphide or metal oxide layer.
[13] A multilayer thermoformable packaging laminate as claimed in claim 15 in which the substrate or base includes at least one polymeric layer selected from a group consisting of a moisture barrier layer, an oxygen barrier layer, a gas barrier, and a vapor barrier layer, said layer being provided operably within the substrate, on the substrate and below the coat, or below the substrate, or within the base.
[14] A multilayer thermoformable packaging laminate as claimed in claim 1, in which the embossed pattern is a diamond pattern, a broken glass pattern, a square pattern, a honey comb pattern, a triangular pattern, a wavy line pattern, a star burst pattern; a circular pattern a striation pattern or a combination of patterns and includes text matter.
[15] A process for preparation of a multilayer thermoformable packaging laminate as claimed in claim 1 ,comprising the following steps:
(i) applying a coat of an ester acrylic based primer, upto a thickness in the range of 0.1 to 1 micron upon a pharmaceutical grade polymeric film substrate, devoid of plasticizer, and having vinyl monomer content less than 60 ppm, said substrate, having thickness in the range of 10 to 150 microns;
(ii) partially drying the said primer coat;
(iii) depositing a metal compound selected from sulphide or metai oxide on the said partially dried primer coat to form a metal sulphide or metal oxide layer of thickness between .001 to 0.3 microns;and
(iv) embossing the metalized layer with a shim to form an embossed pattern on the metal compound layer and to make the thickness of the metal compound layer non uniform;
(v) laminating other side of the substrate with a polymeric base of thickness 50 to 1000 microns.
[16] A process as claimed in claim 15, in which the metal sulphide or metal oxide layer is deposited on the primer coat by vacuum deposition.
[17] A process as claimed in claim 16, which includes a step of applying a lacquer coat, typically a colored lacquer coat either on the film or on the primer coat.
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PCT/IN2009/000522 WO2011036670A1 (en) | 2009-09-23 | 2009-09-23 | A multilayer thermoformable packaging laminate |
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PCT/IN2009/000522 WO2011036670A1 (en) | 2009-09-23 | 2009-09-23 | A multilayer thermoformable packaging laminate |
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US11753530B2 (en) | 2017-04-25 | 2023-09-12 | William B. Coe | Inter-penetrating elastomer network derived from ground tire rubber particles |
US11781018B2 (en) | 2017-08-04 | 2023-10-10 | William B. Coe | Inter-penetrating elastomer network derived from ground tire rubber particles |
RU2808731C1 (en) * | 2017-08-04 | 2023-12-04 | Уилльям Б. КОУ | Interpenetrating elastomer mesh obtained from grinded tire rubber particles |
US11840622B2 (en) | 2017-04-25 | 2023-12-12 | William B. Coe | Process for regenerating a monolithic, macro-structural, inter-penetrating elastomer network morphology from ground tire rubber particles |
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US20050170161A1 (en) * | 2004-02-03 | 2005-08-04 | Ramchandra Naik P. | Metallized packaging films |
WO2006047695A2 (en) * | 2004-10-27 | 2006-05-04 | Mcneil-Ppc, Inc. | Dosage forms having a microreliefed surface and methods and apparatus for their production |
WO2009157012A2 (en) * | 2008-06-24 | 2009-12-30 | Bilcare Limited | Multilayer film |
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Publication number | Priority date | Publication date | Assignee | Title |
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US20050170161A1 (en) * | 2004-02-03 | 2005-08-04 | Ramchandra Naik P. | Metallized packaging films |
WO2006047695A2 (en) * | 2004-10-27 | 2006-05-04 | Mcneil-Ppc, Inc. | Dosage forms having a microreliefed surface and methods and apparatus for their production |
WO2009157012A2 (en) * | 2008-06-24 | 2009-12-30 | Bilcare Limited | Multilayer film |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11753530B2 (en) | 2017-04-25 | 2023-09-12 | William B. Coe | Inter-penetrating elastomer network derived from ground tire rubber particles |
US11840622B2 (en) | 2017-04-25 | 2023-12-12 | William B. Coe | Process for regenerating a monolithic, macro-structural, inter-penetrating elastomer network morphology from ground tire rubber particles |
US11781018B2 (en) | 2017-08-04 | 2023-10-10 | William B. Coe | Inter-penetrating elastomer network derived from ground tire rubber particles |
RU2808731C1 (en) * | 2017-08-04 | 2023-12-04 | Уилльям Б. КОУ | Interpenetrating elastomer mesh obtained from grinded tire rubber particles |
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