GB2447221A - Acrylic polymer containing metal silicate - Google Patents
Acrylic polymer containing metal silicate Download PDFInfo
- Publication number
- GB2447221A GB2447221A GB0704632A GB0704632A GB2447221A GB 2447221 A GB2447221 A GB 2447221A GB 0704632 A GB0704632 A GB 0704632A GB 0704632 A GB0704632 A GB 0704632A GB 2447221 A GB2447221 A GB 2447221A
- Authority
- GB
- United Kingdom
- Prior art keywords
- composition according
- silicate
- styrene
- solution polymer
- metal silicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229910052914 metal silicate Inorganic materials 0.000 title claims abstract description 18
- 229920000058 polyacrylate Polymers 0.000 title description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 230000004888 barrier function Effects 0.000 claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 18
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 9
- 229920001577 copolymer Chemical compound 0.000 claims abstract description 8
- 229910052913 potassium silicate Inorganic materials 0.000 claims abstract description 8
- 239000006184 cosolvent Substances 0.000 claims abstract description 7
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 22
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 10
- 235000019353 potassium silicate Nutrition 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 239000004111 Potassium silicate Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 2
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 9
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 238000004806 packaging method and process Methods 0.000 abstract description 4
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- 239000011591 potassium Substances 0.000 abstract 1
- GBFLZEXEOZUWRN-VKHMYHEASA-N S-carboxymethyl-L-cysteine Chemical compound OC(=O)[C@@H](N)CSCC(O)=O GBFLZEXEOZUWRN-VKHMYHEASA-N 0.000 description 27
- 229960004399 carbocisteine Drugs 0.000 description 27
- 239000000243 solution Substances 0.000 description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 22
- 239000001301 oxygen Substances 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 22
- 239000007789 gas Substances 0.000 description 21
- 239000010408 film Substances 0.000 description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 description 18
- -1 silicon oxides Chemical class 0.000 description 15
- 239000010410 layer Substances 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000008199 coating composition Substances 0.000 description 6
- 235000013305 food Nutrition 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004908 Emulsion polymer Substances 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229910012506 LiSi Inorganic materials 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- RJLZSKYNYLYCNY-UHFFFAOYSA-N ethyl carbamate;isocyanic acid Chemical compound N=C=O.CCOC(N)=O RJLZSKYNYLYCNY-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000009424 underpinning Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
A composition comprises a metal silicate dispersed throughout a film of a water-soluble, film-forming acrylic solution polymer. The metal silicate is preferably an alkali metal silicate, such as sodium, potassium, or lithium silicate. The acrylic solution polymer may have a molecular weight below 20000 and is especially styrene-co-methyl methacrylate, styrene-co-butyl acrylate, styrene-co-methyl acrylate, or styrene-co-ethylhexyl acrylate. The ratio of metal silicate to acrylic solution polymer may be 99:1 to 4:1. A composition for forming a gas barrier coating is also disclosed, which comprises a solution of a metal silicate and a water-soluble, film-forming acrylic solution polymer in a solvent. The solvent is typically aqueous and may contain a co-solvent, such as an alcohol. The composition may be applied to a plastics substrate and may be used to form a gas barrier film for packaging foodstuffs, pharmaceuticals, and other materials sensitive to the atmosphere.
Description
OXYGEN BARRIER COATINGS
The present invention relates to a coating composition having gas barrier properties, particularly the ability to block the passage of oxygen, and which may be used to coat and impart gas barrier properties to a variety of materials, notably packaging for foods and pharmaceuticals, where exposure to oxygen needs to be eliminated or restricted.
Synthetic plastics materials have long been used for the packaging of foods and other materials which need protection from handling and from moisture. However, in recent years, it has become appreciated that, in addition, many foods and other sensitive materials benefit from being protected from atmospheric oxygen. A wide variety of multilayer laminate structures has been developed to provide barrier properties and other performance characteristics suited to a pack's purpose. These laminates may be any combination of plastic, metal or cellulosic substrates, and may include one or more coating or adhesive layers. Laminates which include polymeric films having metals or inorganic compounds, such as silicon oxides, deposited thereon have been found to give good general barrier properties and are widely used. However, their properties tend to be very temperature dependent and they may lose their ability to prevent the ingress of oxygen altogether at high tempçratures, for example when the packaged material is retorted in order to sterilise and/or cook it. Moreover, the inorganic layer of these types of laminate is rather brittle and may crack or break when the laminate is flexed, resulting in a loss of the gas barrier properties.
As a result, a number of other laminated films have been proposed for this purpose. For example, EP 0 878 495 describes and claims a gas barrier laminated material comprising a substrate, an inorganic compound thin-film layer and a protective layer which are laminated in that order, where the protective layer is formed by coating on the inorganic compound thin-film layer a water-based coating composition containing a water-soluble polymer and at least one of (a) a metal alkoxide or a hydrolysate thereof and (b) a tin chloride, followed by heat drying. Other patents using similar techniques include EP 1 211 295 (JSR), EP 0 960 901 (Nakato) and US 6,337,370. Although good oxygen barrier performance is achieved, there are a number of drawbacks with this technology. These drawbacks include having to prepare the hydrolysed silane press-side (due to poor long term stability), the exothermic nature of the hydrolysis reaction and the potential hazards associated with having to handle the silane and hydrochloric acid or other acid. Furthermore, the water resistance of these coatings can be insufficient.
JP 2003170522 discloses a two-layer barrier, in which a polyethylene terephthalate film is first coated with a solution of lithium or sodium silicate and then with a solution of polyvinyl alcohol (PVA). This achieves an oxygen barrier of cc/m2/day at 40 C and 90% relative humidity (RH). JP 2002316381 also discloses a multi-layer barrier coating, which, in this instance, comprises: (a) an anchor coat (e.g. a urethane isocyanate): (b) a barrier coat comprising a metal silicate (e.g. lithium silicate) as well as, optionally, a nitrogen-containing compound and a water-soluble polymer (e.g. silicon-modified PVA); and (c) a top coat comprising a hydroxy-containing water-soluble polymer (e.g. PVA). However, because PVA is very hydrophilic, it can absorb large amounts of water and so, even if good gas barrier properties are achieved at the beginning, these properties soon deteriorate. Moreover, several layers are required in these cases, including at least a primer (anchor) layer, to ensure good adhesion of the gas barrier coating to the substrate.
JP 2006159801 A2 reports that BOPP (Biaxially Orientated PolyPropylene) films were coated with a polyethyleneimine based primer which was over coated with lithium silicate solution coating. Oxygen permeability of 11 cc/m2/day at 23 C at 90% RH was reported.
US 6649235 32 reports a similar process by coextruding polypropylene and polypropylene modified with maleic anhydride followed by corona treatment of the maleated side and over coating this surface with a barrier layer of polysilicates. In WO 9747678 Al, BOPP was primed with PVA and EVOH (Ethylene Vinyl Alcohol polymer) prior to application of the lithium potassium silicate layer. An oxygen
I
transmission rate of 61 cc/m2/day at 23 c and 60% RH was recorded. Thus, the majority of the prior art deals with primer use and pure silicate coatings.
US 6071624 discloses that potassium silicate was required with lithium and sodium silicate coatings because lithium and sodium silicate coatings tend to effloresce, i.e., become covered by powdery crystalline material as a result of atmospheric exposure. In contrast, pure potassium silicate coatings do not effloresce, but suffer severe loss of barrier performance above 50% relative humidity. Pure lithium silicate coatings, on the other hand, exhibit little or no loss of barrier performance over the same relative humidity range.
JP 2003170522 A2 reported a modification to the above mentioned approach.
PET (PolyEthylene Teraphthalate) films were coated with a solution of lithium silicate and sodium silicate followed by an overcoat of PVA and Li2HPO4, which were then heat dried. An oxygen permeation value of 18 cc/m2/day was reported at 23 C and 90% RH. In similar patents, JP 2002316381 A2 and JP 2002283492 A2, a multilayer approach, with an anchor coat underpinning gas barrier coatings of alkali metal silicates and top coats of PVA containing composition were reported. As an example, PP (polypropylene) substrate was coated with an isocyanate anchor coat, followed by a coat of lithium silicate composition containing aminosilane and silane modified PVA and subsequently a final coat of PVA and clay composition. Oxygen permeation of 10.8 cc/m2/day was recorded.
Use of clay in combination with the metal silicates was also reported in JP 2001260264. BOPP substrate was coated with aminoethylated resin followed by coating with a 50:50 blend of lithium silicate and Na montmorillonite to dry film thickness of about 0.8 micron. This was thermally treated to provide a barrier film with good resistance to surface cracking.
None of these approaches appears to have achieved very low gas, especially oxygen, permeabilities and they all require the application of several coats.
JP2000 1 04020A2 discloses a gas barrier coating forming composition comprising (A) an aqueous dispersible polymer selected from a polyester polymer, an acrylic polymer and a polyurethane polymer, with (B) at least one or two water glass selected from sodium silicate, potassium silicate, lithium silicate, and ammonium silicate in certain weight ratios. The acrylic polymers used are acrylic emulsion polymers and, using these, we have found that the gas barrier properties are poor.
JP 20001 03986A2 discloses a composition for preparing a gas barrier coating comprising an aqueous solution containing (A) a water-soluble polymer having an amino group or a hydroxy group in the molecule (preferably a polyamide or polyvinyl alcohol-based polymer) and (B) a water glass (preferably lithium silicate). Although such a gas barrier coating does have improved barrier properties, we have found that the aqueous solution is rather unstable and that the gas barrier properties deteriorate significantly as the relative humidity increases.
We have now surprisingly discovered that these disadvantages may be overcome and a good gas barrier coating achieved in a single layer by applying a metal silicate in admixture with a water-soluble film-forming acrylic solution polymer.
Thus, the present invention consists in a composition comprising a metal silicate dispersed throughout a film of a water-soluble film-forming acrylic solution polymer.
The invention further consists in a composition for forming a gas barrier coating, comprising a solution of a metal silicate and a water-soluble film-forming acrylic solution polymer in a solvent. -The metal silicate employed is preferably a water-soluble silicate, for example an alkali metal silicate or polysilicate, such as lithium silicate, sodium silicate or potassium silicate. Commercially available silicates generally have a molar ratio of alkali metal oxide:silicon dioxide that varies, in some instances quite considerably, from the stoichiometric. This molar ratio can affect the properties of the silicate to a large extent and thus may affect the properties of the gas barrier coating of the present invention. Although the optimum molar ratio for any particular composition may be found by the person skilled in the art by simple experiment, in general, we prefer that the molar ratio of alkali metal oxide:silicon dioxide should be from 0.1 1 to 0.4:1, more preferably from 0.2:1 to 0.3:1 and most preferably around 0.25:1.
The other essential component of the composition of the present invention is a water-soluble film-forming acrylic solution polymer. It is important to note that these are very different in nature from the acrylic emulsion polymers used in JP2000104020A2, which, unlike the solution polymers used in the present invention, result in poor gas barrier performance. Examples of suitable acrylic solution polymers include copolymers of one or more ethylenically unsaturated hydrocarbons, such as styrene, with one or more hydrocarbyl, e.g. alkyl, acrylates, for example styrene-co- methyl methacrylate, styrene-co-butyl acrylate, styrene-co-methyl acrylate, and styrene-co-ethyl hexyl acrylate. These solution polymers preferably have a relatively low molecular weight, e.g. below 20,000. They are commonly prepared, as is well known in the art, in a solvent-based medium using solvent soluble free radical initiators.
Sufficient acid will be included so that, when the acid groups are neutralised with e.g. ammonia solution, the polymer becomes sufficiently hydrophilic for it to dissolve.
Thus, an acrylic solution is a homophasic system. Anionic solution polymers prepared in a similar way may also be used in the present invention.
Where the coating composition of the present invention is to be used in an environment of high relative humidity, the use of an acrylic solution polymer in accordance with the present invention is especially beneficial. Although other polymers, such as vinyl alcohol-based polymers, may give good barrier properties at low or moderate relative humidities, acrylic solution polymers maintain these properties in high relative humidity environments. Moreover, acrylic solution polymer-based compositions appear to exhibit greater stability than, for example those based on PVA, and so are preferred from this viewpoint also.
The coating composition of the present invention is usually and preferably applied in the form of a solution of the silicate and the polymer in a suitable solvent.
The solvent is preferably aqueous, and is more preferably water, optionally containing a small quantity of a miscible co-solvent, such as an alcohol (for example ethanol, n-propanol or isopropanol) or a ketone (such as acetone). Where a co-solvent is present, this is preferably no more than 10% by weight of the entire composition, still more preferably no more than 5%. The preferred co-solvent is an alcohol, preferably ethanol.
The amount of acrylic solution polymer in the coating composition is preferably from I to 20% of the total solids comprising polymer and silicate, in other words, the ratio of silicate to polymer is preferably from 99:1 to 4:1, more preferably from 19:1 to 4:1. The concentration of silicate and polymer in the solution will depend on their solubility, the amount of solvent employed preferably being the minimum needed to achieve sufficient flowability to coat the substrate adequately. In general, the silicate will be employed in the form of a 3-25% by weight solution in water or water+co-solvent, and this will dictate the contents of the remaining components.
The coating composition of the present invention comprising the silicate, the acrylic solution polymer and a solvent therefor may be applied to a substrate by any conventional means. The solvent may then be removed, e.g. by heating, leaving a film comprising the silicate dispersed through the polymer on the substrate. The resulting gas barrier film may be a single ply film, or it may form part of more complex multilayer laminate structure which can include one or more additional substrates, adhesive coatings, layers of inks and varnishes, etc., as is well-known to those skilled in the art. It is preferred that the film of the present invention should be adhered to a further flexible plastics sheet.
There is no particular restriction on the nature of the flexible substrate, although it is preferably a plastics film, and any material suitable for the intended use may be employed. However, where the matter being packaged with the coating film of the present invention is a foodstuff or pharmaceutical, it will normally be preferred that the plastics film or other substrate should be food grade. Examples of suitable materials include: polyolefins, such as polyethylene or polypropylene; polyesters, such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthenate; polyamides, such as nylon-6 or nylon-66; and other polymers, such as polyvinyl chloride, polyimides, acrylic polymers, polystyrenes, celluloses, or polyvinylidene chloride,. It is also possible to use copolymers of any compatible two or more of the monomers used to produce these polymers. We especially prefer the polyesters.
Where there is a further plastics sheet, this, too, should be flexible and may be selected from any of the materials exemplified in the preceding paragraph.
The thickness of the coating of the present invention will depend in part on the ability of the silicate to form a continuous, coherent coating layer. However, in general, we prefer that the coating should be from 50 nm to 3000 rim thick, more preferably from 200 to 2000 nm thick.
The invention thus also provides a process for forming a gas barrier film, which comprises applying to a substrate a composition comprising a solution of a metal silicate and a water-soluble film- forming acrylic solution polymer in a solvent, and removing the solvent.
The invention still further provides a packaged foodstuff, pharmaceutical or other material sensitive to the atmosphere, wherein the packaging comprises a gas barrier coating of the present invention.
The invention is further illustrated by the following non-limiting Examples.
EXAMPLES
Coatings were prepared in an aqueous solution with 5% (w/w) of ethanol. The oxygen transmission rates of the coated samples were determined on a Mocon Oxtran 2/21 gas permeability tester at 23 C and 50% relative humidity (few values at 80%).
The substrates used were Nuroll PET (a 12pm gauge polyethylene terephthalate substrate), OPP and OPA (Orientated polyamide). The coatings were applied with a No.2 K-bar unless otherwise mentioned and were dried in a warm flow of air (lab prints were dried with a hair dryer).
The laminates were prepared by applying an adhesive to the surface of a substrate film (e.g. PE -polyethylene) and applying the barrier coating to another substrate (e.g. PET) and bonding them together. The adhesive used was supplied by Henkel, UR 3855 along with catalyst hR 6055, and was prepared according to the manufacturers instructions and applied so as to achieve a final dry film weight of 4 gsm.
The laminates were then stored for 2 days at 50 C to ensure full cure of the isocyanate-based adhesive. The laminates were then tested for bond strength (NIl 5mm) and oxygen barrier as earlier described.
Substrate films were tested for the oxygen transmission rates through them at 23 C and at 50% RH. Values of 100 and 32 cc/m2/day were recorded for the PET and OPA substrates, whereas the transmission through OPP and PE was too high to be detected.
Pure polymer matrix (SCX 8082) was also drawn on the PET substrate and a value of 95 cc/m2/day was recorded at 23 C and 50% RH.
EXAMPLES 1 TO 31 & COMPARATIVE EXAMPLES 1 & 2 Oxygen transmission values of the coatings drawn with formulations carrying varibus silicates & polymers along with clay & wetting agent, drawn on different substrates & with different K bars and characterized at different relative humidity values. The results are shown in Tables I and 2.
EXAMPLES 32 TO 35
Oxygen transmission and the bond strength values of the laminates prepared with the inside coating of the barrier formulation. The results are shown in Table 3.
Table 1
Example Polymer Silicate Silicate! Total Substrate Bar Oxygen %RH No. polymer solids wt permeation ratio _________ cc/m2/day ______ I SCX 8082 LiSil L29 9 10 PET 2K 0.7 50 2 SCX 8082 LiSil L40 9 10 PET 2K 0. 1 50 3 SCX 8082 LiSil 665 9 10 PET 2K 0.6 50 4 SCX 8082 NaSil NaO 106 9 10 PET 2K 0.6 50 SCX 8082 NaSil Na0052 9 10 PET 2K 0.3 50 6 SCX 8082 KSiI K78 9 10 PET 2K 2 50 7 SCX 8085 LiSi! L29 9 10 PET 2K 2.5 50 8 SCX 8085 LiSil L40 9 10 PET 2K 0.1 50 9 SCX 8085 LiSil 665 9 10 PET 2K 2.3 50 SCX 8085 NaSilNaOlO6 9 10 PET 2K 0.2 50 11 SCX 8085 NaSil Na0052 9 10 PET 2K 1.2 50 12 SCX 8085 KSiI K78 9 10 PET 2K 2.5 50 13 DFC 3025 LiSil L29 9 10 PET 2K 3.2 50 14 DFC 3025 LiSil L40 9 10 PET 2K <0.1 50 DFC 3025 LiSil 665 9 10 PET 2K 0.6 50 16 DFC 3025 NaSilNaOlO6 9 10 PET 2K 0.3 50 17 DFC 3025 NaSjlNaOO52 9 10 PET 2K 0.6 50 18 DFC 3025 KSiI K78 9 10 PET 2K 3.6 50 19 SCX 8082 LiSil L40 4 10 PET 2K 2.2 50
Table 2
Example Polymer Silicate Silicate! Total Substrate Bar Oxygen %RH No. polymer solids wt permeation ratio _________ _________ cc/m2/day _____ SCX 8082 LiSil L40 2.3 10 PET 2K 79 50 21 SCX 8082 LiSil L40 1 10 PET 2K Gel 50 22 SCX 8082 NaSil Na0052 4 10 PET 2K 2.2 50 23 SCX 8082 NaSil Na0052 2.3 10 PET 2K 79 50 24 SCX 8082 NaSil Na0052 1 10 PET 2K Gel 50 SCX 8082 LiSil L40 9 10 PET OK 0.2 50 26 SCX 8082 LiSil L40 9 10 PET 1K 0.2 50 27 SCX 8082 LiSil L40 9 10 OPP 2K 5 50 28 SCX 8082 LiSil L40 9 10 OPP 2K 3.8 80 29 DFC 3025 LiSil L40 9 10 OPP 2K 9 50 SCX 8082 LiSiIL4O 9 10 OPA 2K 3.1 50 31 DFC 3025 LiSil L40 9 10 OPA 2K 5 50 Comp 1 SCX 1630 LiSil L40 18 10 PET 2K 47 50 Comp 2 DSM A2092 LiSil DIC 18 10 PET 2K 70 50 Note: (1) LiSil L29, LiSil L40, LiSil 665, NaSil NaO 106, NaSil Na0052, KSi1 K78 are silicates supplied by Ineos Silicas.
(2) LiSil DIC is a lithium silicate supplied by DIC.
(3) SCX 8082 and SCX 8085 are solution acrylics from Johnson Polymer.
(4) DFC 3025 is a direct food contact solution acrylic from Johnson Polymer.
(5) SCX 1630 is an emulsion acrylic from Johnson Polymer.
(6) DSM A2092 is an emulsion acrylic from DSM Neoresins.
Table 3
Example Polymer Silicate Silicate! Total Laminate structure Bar Oxygen permeability % Bond No. polymer solids cc!m2!day RH strength N __________ __________ __________ ratio wt % ____________________ 32 SCX 8082 LiSil L40 9 10 OPAlBarrier/OPP 2K 0.6 (27)1 50 0.8 33 SCX 8082 LiSil L40 9 10 OPA/Barrier/PE 2K 1.4 (28) 50 2.6 34 SCX 8082 LiSil L40 9 10 PET/Barrier/PE 2K 0.2 (98) 50 1.5 SCX 8082 LiSil L40 9 10 PETfBarrier!OPP 2K 0.1 (91) 50 1.5 Note: (1) The values in brackets are the permeation values through the laminates made without any barrier film.
S
EXAMPLE 36
A formulation comprising 90% lithium silicate L40 and 10% polymer was prepared and coated onto a PET substrate as described in the above Examples. When using acrylic polymer SCX 8082, the system had a permeation of 0.10 cc/m2.day at 50% RH. A comparable system using PVA 396 in place of the SCX 8082 had an oxygen permeation of 0.14 cc/m2.day at 50% RH. At 75% RH, however, the acrylic system had a permeation of 1.8 cc/m2.day and the PVA system had a value of 3.7 cc/m2.day.
The PVA formulation also contained a large number of flakes, whereas the acrylic formulation was a substantially homogenous mixture.
EXAMPLE 37
The procedure described in Example 36 was repeated, but using a formulation comprising 80% lithium silicate L40 and 20% polymer. The acrylic system had a permeation of 2.2 cc/m2.day and the PVA system had an oxygen permeation of 0.32 cc/m2.ciay at 50% RH. At 75% RH, however, the acrylic system had a permeation of 8.3 ccfm2.day and the PVA system had a value of 28 cc/m2.day.
The PVA formulation also contained a large number of flakes, whereas the acrylic formulation was a substantially homogenous mixture.
Claims (23)
- CLAIMS: I. A composition comprising a metal silicate dispersedthroughout a film of a water-soluble film-forming acrylic solution polymer.
- 2. A composition according to Claim 1, in which the metal silicate is an alkali metal silicate.
- 3. A composition according to Claim 2, in which the metal silicate is sodium silicate, potassium silicate or lithium silicate.
- 4. A composition according to Claim 2 or Claim 3, in which the molar ratio of alkali metal oxide:silicon dioxide is from 0.1:1 to 0.4:1.
- 5. A composition according to Claim 4, in which the molar ratio is from 0.2:1 to 0.3:1, preferably around 0.25:1.
- 6. A composition according to any one of the preceding Claims, in which the acrylic solution polymer is a copolymer of one or more ethylenically unsaturated hydrocarbons with one or more alkyl acrylates.
- 7. A composition according to Claim 6, in which the acrylic solution polymer is styrene-co-methyl methacrylate, styrene-co-butyl acrylate, styrene-co-methyl acrylate, or styrene-co-ethyl hexyl acrylate.
- 8. A composition according to any one of the preceding Claims, in which the acrylic solution polymer has a molecular weight below 20,000.
- 9. A composition according to any one of the preceding Claims, in which the weight ratio of silicate to acrylic solution polymer is from 99:1 to 4:1.
- 10. A composition according to Claim 9, in which the weight ratio of silicate to acrylic solutionpolymer is from 19:1 to 4:1.
- 11. A composition for forming a gas barrier coating, comprising a solution of a metal silicate and a water-soluble film-forming acrylic solution polymer in a solvent.
- 12. A composition according to Claim 11, in which the metal silicate is an alkali metal silicate.
- 13. A composition according to Claim 12, in which the metal silicate is sodium silicate, potassium silicate or lithium silicate.
- 14. A composition according to Claim 12 or Claim 13, in which the molar ratio of alkali metal oxjde:sjl icon dioxide is from 0.1:1 to 0.4:1.
- 15. A composition according to Claim 14, in which the molar ratio is from 0.2:1 to 0.3:1,preferably around 0.25:1.
- 16. A composition according to any one of Claims ii to 15, in which the acrylic solution polymer is a copolymer of one or more ethylenically unsaturated hydrocarbons with one or more alkyl acrylates.
- 17. A composition according to Claim 16, in which the acrylic solution polymer is styrene-co-methyl methacrylate, styrene-co-butyl acrylate, styrene-co-methyl acrylate, or styrene-co-ethyl hexyl acrylate.
- 18. A composition according to any one of Claims 11 to 17, in which the acrylic solution polymer has a molecular weight below 20,000.
- 19. A composition according to any one of Claims II to 18, in which the weight ratio of silicate to acrylic solution polymer is from 99:1 to 4:1.
- 20. A composition according to Claim 19, in which the weight ratio of silicate to acrylic solution polymer is from 19:1 to 4:1.
- 21. A composition according to any one of Claims 11 to 20, in which the solvent is aqueous.
- 22. A composition according to Claim 21, in which the solvent is water containing up to 10% by volume of a co-solvent.
- 23. A composition according to Claim 22, in which the co-solvent is an alcohol.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0704632A GB2447221A (en) | 2007-03-09 | 2007-03-09 | Acrylic polymer containing metal silicate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0704632A GB2447221A (en) | 2007-03-09 | 2007-03-09 | Acrylic polymer containing metal silicate |
Publications (2)
Publication Number | Publication Date |
---|---|
GB0704632D0 GB0704632D0 (en) | 2007-04-18 |
GB2447221A true GB2447221A (en) | 2008-09-10 |
Family
ID=37988724
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB0704632A Withdrawn GB2447221A (en) | 2007-03-09 | 2007-03-09 | Acrylic polymer containing metal silicate |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB2447221A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016009435A1 (en) | 2014-07-16 | 2016-01-21 | Asher Vitner | Polymer-glass-polymer gas barrier laminate |
FR3096051A1 (en) * | 2019-05-17 | 2020-11-20 | Nof Metal Coatings Europe | COMPOSITION OF DEHYDRATED COATING IN SOLID FORM, ITS OBTAINING PROCESS AND ITS REHYDRATION PROCESS |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1068584A (en) * | 1962-11-19 | 1967-05-10 | Nobel Bozel | Improved covering or coating compositions |
JPS50126035A (en) * | 1974-03-26 | 1975-10-03 | ||
JPS62178394A (en) * | 1986-01-31 | 1987-08-05 | Showa Alum Corp | Production of plate material for lithography |
JPH05295299A (en) * | 1992-04-22 | 1993-11-09 | Nippon Shokubai Co Ltd | Liquid composition for forming gas-barrier film and surface-coated formed material |
JP2000239573A (en) * | 1999-02-17 | 2000-09-05 | Nippon Light Metal Co Ltd | Underwater antifouling coating material composition and underwater antifouling film comprising the same composition |
JP2000239572A (en) * | 1999-02-17 | 2000-09-05 | Nippon Light Metal Co Ltd | Underwater antifouling coating material composition and underwater antifouling film comprising the same composition |
-
2007
- 2007-03-09 GB GB0704632A patent/GB2447221A/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1068584A (en) * | 1962-11-19 | 1967-05-10 | Nobel Bozel | Improved covering or coating compositions |
JPS50126035A (en) * | 1974-03-26 | 1975-10-03 | ||
JPS62178394A (en) * | 1986-01-31 | 1987-08-05 | Showa Alum Corp | Production of plate material for lithography |
JPH05295299A (en) * | 1992-04-22 | 1993-11-09 | Nippon Shokubai Co Ltd | Liquid composition for forming gas-barrier film and surface-coated formed material |
JP2000239573A (en) * | 1999-02-17 | 2000-09-05 | Nippon Light Metal Co Ltd | Underwater antifouling coating material composition and underwater antifouling film comprising the same composition |
JP2000239572A (en) * | 1999-02-17 | 2000-09-05 | Nippon Light Metal Co Ltd | Underwater antifouling coating material composition and underwater antifouling film comprising the same composition |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016009435A1 (en) | 2014-07-16 | 2016-01-21 | Asher Vitner | Polymer-glass-polymer gas barrier laminate |
CN107000405A (en) * | 2014-07-16 | 2017-08-01 | 阿舍·维特纳 | Polymer glass polymer gas stops layered product |
FR3096051A1 (en) * | 2019-05-17 | 2020-11-20 | Nof Metal Coatings Europe | COMPOSITION OF DEHYDRATED COATING IN SOLID FORM, ITS OBTAINING PROCESS AND ITS REHYDRATION PROCESS |
WO2020234535A1 (en) * | 2019-05-17 | 2020-11-26 | Nof Metal Coatings Europe | Dehydrated coating composition in solid form, method of obtaining same, and method for rehydrating same |
Also Published As
Publication number | Publication date |
---|---|
GB0704632D0 (en) | 2007-04-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2195390B1 (en) | Gas barrier coatings based on polymer emulsions | |
US8268108B2 (en) | Gas barrier coating having improved bond strength | |
JP5595931B2 (en) | Oxygen barrier coating composition | |
US9598599B2 (en) | Gas barrier coatings | |
JP2003525995A (en) | Barrier coating with bissilane | |
WO2007125741A1 (en) | Coating liquid, gas barrier film, gas barrier laminate and gas barrier multilayer film each using the coating liquid, and their production methods | |
US20100062117A1 (en) | Thermally resistant gas barrier lamellae | |
GB2447221A (en) | Acrylic polymer containing metal silicate | |
US20080248287A1 (en) | Gas Barrier Coating Having High Thermal Resistance | |
EP2613940B1 (en) | A carbon dioxide barrier coating | |
JPH06329821A (en) | Water-resistant gas-barrier packaging material | |
MX2008005482A (en) | Gas barrier coating having high thermal resistance | |
JP2003268184A (en) | Vinyl alcohol polymer composition and its applications | |
JP2000103986A (en) | Composition for forming gas barrier coating film, and film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |