CN107000405A - 聚合物‑玻璃‑聚合物气体阻挡层压体 - Google Patents
聚合物‑玻璃‑聚合物气体阻挡层压体 Download PDFInfo
- Publication number
- CN107000405A CN107000405A CN201580038499.8A CN201580038499A CN107000405A CN 107000405 A CN107000405 A CN 107000405A CN 201580038499 A CN201580038499 A CN 201580038499A CN 107000405 A CN107000405 A CN 107000405A
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- Prior art keywords
- polymer
- glass
- ink
- silicate
- laminated
- Prior art date
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- Pending
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- 239000011521 glass Substances 0.000 title claims abstract description 31
- 229920000642 polymer Polymers 0.000 title claims abstract description 31
- 239000010410 layer Substances 0.000 claims abstract description 46
- 229920006254 polymer film Polymers 0.000 claims abstract description 40
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 27
- 230000004888 barrier function Effects 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000004593 Epoxy Substances 0.000 claims abstract description 22
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000004678 hydrides Chemical class 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000013047 polymeric layer Substances 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000005368 silicate glass Substances 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 230000005540 biological transmission Effects 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 34
- -1 PTPP Chemical compound 0.000 claims description 26
- 239000004115 Sodium Silicate Substances 0.000 claims description 22
- 235000019795 sodium metasilicate Nutrition 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 22
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000004698 Polyethylene Substances 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 13
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 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 claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 238000007639 printing Methods 0.000 claims description 10
- 238000009472 formulation Methods 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 239000004425 Makrolon Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 229920000515 polycarbonate Polymers 0.000 claims description 8
- 239000005077 polysulfide Substances 0.000 claims description 8
- 229920001021 polysulfide Polymers 0.000 claims description 8
- 150000008117 polysulfides Polymers 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 6
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 5
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims description 5
- 238000003475 lamination Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000001506 calcium phosphate Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000001282 organosilanes Chemical class 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 4
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 4
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 4
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 4
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 4
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 4
- 239000004568 cement Substances 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 230000003595 spectral effect Effects 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000007766 curtain coating Methods 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- DIFFLMNDXWOKQJ-UHFFFAOYSA-N [K].O[Si](O)(O)O Chemical compound [K].O[Si](O)(O)O DIFFLMNDXWOKQJ-UHFFFAOYSA-N 0.000 claims 1
- 238000003618 dip coating Methods 0.000 claims 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims 1
- 150000002632 lipids Chemical class 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 125000000962 organic group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000004111 Potassium silicate Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 208000030770 patent ductus arteriosus 3 Diseases 0.000 description 8
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 8
- 229910052913 potassium silicate Inorganic materials 0.000 description 8
- 235000019353 potassium silicate Nutrition 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 6
- 229910052912 lithium silicate Inorganic materials 0.000 description 6
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 229910052914 metal silicate Inorganic materials 0.000 description 5
- 150000003376 silicon Chemical class 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 229920005989 resin Polymers 0.000 description 3
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- UQJIGSKKIVHXJB-UHFFFAOYSA-N (4-aminophenyl)silicon Chemical compound NC1=CC=C([Si])C=C1 UQJIGSKKIVHXJB-UHFFFAOYSA-N 0.000 description 1
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical class OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 241001016380 Reseda luteola Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 241000656145 Thyrsites atun Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002508 contact lithography Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
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- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
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- 235000015424 sodium Nutrition 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
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- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- 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
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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Abstract
本发明提供一种透明的气体阻挡聚合物‑玻璃‑聚合物层压膜及其生产方法,所述层压膜包括第一聚合物膜基底;在所述第一聚合物膜基底上层压的硅酸盐玻璃层,其包括与选自有机基‑硅酸盐或环氧基硅烷前体中的至少一种添加剂结合的氧化硅和除了锂以外的单价阳离子的盐;和在所述玻璃层上层压的第二聚合物膜;其中经层压聚合物‑玻璃‑聚合物膜的透氧速率低于0.2cc/m2/天。
Description
技术领域
本发明涉及透明气体阻挡聚合物-玻璃-聚合物层压膜及其生产方法。更特别地,本发明涉及透明的气体阻挡聚合物-玻璃-聚合物层压膜,其中经聚合物-玻璃-聚合物层压膜的透氧速率低于0.2cc/m2/天。
背景技术
继续要求改进聚合物材料的不可渗透性,以便减少气体,蒸汽和液体的渗透性。食品包装工业要求聚合物膜应当对氧气,湿气和香味渗透提供确定的阻挡,即应当具有非常低的OTR。OTR(透氧速率)是在规定的温度和相对湿度条件下,氧气气体经膜渗透时的稳定状态。OTR值在十进制(SI)单位中以cc/m2/天表达。标准试验条件是23℃和0%RH。空气由约21%氧气和79%氮气,和非常小浓度的其他气体,例如二氧化碳和氩气组成。氧气气体是造成食品腐败的反应性化合物。许多化学和生物反应要求氧气,以便发生反应。在食品包装中,减少氧气暴露将延长氧敏产品的货架期。
迄今为止市场上可获得的透明或半透明的气体阻挡膜是Saran的涂覆PET膜(OTR~3-15cc/m2/天),金属化的铝聚合物膜(OTR~0.1-0.2cc/m2/天),EVOH涂覆膜(OTR~0.2cc/m2/天),在聚合物膜上电子束涂布的SiO2(OTR~0.05-0.2cc/m2/天)和用粘土纳米颗粒包埋的聚合物涂覆膜(OTR~0.4-0.8cc/m2/天)。透明聚合物膜是对波长在390至700nm的特殊范围内的光透过的聚合物片材。
可溶硅酸盐,例如硅酸钠,硅酸钾,硅酸锂和硅酸铵是化学物质玻璃或玻璃的水溶液,其来自于各种比例的碱金属氧化物或氢氧化铵和氧化硅的组合。所有上述可溶的硅酸盐是碱金属类物质(浓缩产品的pH值通常为10-13)。可溶硅酸盐以水溶液形式生产。
当液体硅酸盐的pH下降到低于pH-11时,硅酸盐快速反应。硅酸盐物种交联,形成硅酸盐聚合物。采用酸性物种和二氧化碳,反应快速地进行,形成硅酸盐聚合物和碳酸盐。其实例是酸性盐,有机酸,酯或碳酸盐。所形成的碳酸盐倾向于散射光,因为在干燥工艺过程中它结晶(晶霜(efflorescence))。
硅酸盐的特征在于氧化硅对氧化物的重量比。例如,溶解的硅酸钠商业上以1.5至3.2的比值范围(SiO2:Na2O)生产。这一比值代表各种分子量硅酸盐物种(例如,单体,三聚体,四聚体等)的平均。较高的比值(例如3.2)具有比较容易中和并允许比较快速聚合/聚集的低碱金属含量。
在聚合物制品上的玻璃涂层可提供改进气体和液体阻挡性能的方式。在聚合物上沉积玻璃所使用的方法之一是使用化学或物理蒸汽沉积,离子束,溶胶-凝胶化学和碱金属硅酸盐化学品的化学路线。碱金属聚硅酸盐作为改性聚合物膜和其他制品的表面性能的保护性涂层是已知的;参见例如GB1007482;GB1424425;US1949914;US3102038;US3130061;US3180747;US3492137;US3522066;US3533816和US3706603。
碱金属硅酸盐与二氧化碳反应,形成碱金属碳酸盐。硅酸钠倾向于与二氧化碳反应,形成碳酸钠且逐渐变得水溶性较小,而硅酸钾膜与硅酸钠相比,不那么可能形成碳酸盐起霜(bloom)或碱金属碳酸盐的白色晶霜涂层。
还已知在硅酸盐涂层掺入其内时,聚合物制品变得发雾。作为大气暴露的结果,硅酸钠(Na)涂层倾向于晶霜或者被粉状结晶材料覆盖是在文献中充分地记载的(参见,例如Properties of soluble silicates(可溶硅酸盐的性能),Weldes H.Helmut和K.RobertLange,Industrial and Engineering Chemistry,第61卷(4),第28-44页,1969)。
若干专利提出了对于各种聚合物表面来说,使用硅酸锂基气体阻挡涂层。例如,Hecht和Iler的加拿大专利No.993,738描述了用于聚合物基底的气体和液体不可渗透的涂层,它包括SiO2对Li2O的某种原子比为约1.6至4.6的聚硅酸锂。
US2998328公开了添加二氧化钛颜料并描述了一种饰面漆(finish)或罩面涂层,它包括含碱金属硅酸盐的水溶液的反应性液体组分和着色共混组分。该反应性液体组分在水中溶解碱金属硅酸盐,例如硅酸钠,硅酸钾,硅酸锂或这种硅酸盐的混合物。
US5882798和US6071624(A)公开了碱金属硅酸盐的混合物组合物,以便使用化学式为(M2O)(SiO2)y的锂和钾的共聚硅酸盐涂层,来改进涂布层的特征,其中M2O是(Li2O)x(K2O)1-x和其中x的范围为0.5至小于1,和y的范围为1至约10,所述溶液包括最多约15%的全部固体含量,以便改进渗透性。
US6071624公开了一种用于聚合物基底的水性阻挡涂料组合物。这一专利描述了要求与硅酸锂和硅酸钠一起使用硅酸钾,因为作为大气暴露的结果,硅酸锂和硅酸钠涂层倾向于晶霜,即被粉状结晶材料覆盖。这一专利还描述了在0.1N水性氢氧化锂中使用聚(对羟基苯乙烯)作为打底溶液。
然而,在待包装的物质是食品或药品的情况下,通常优选塑料膜或其他基底应当是食品级塑料。锂涂层可限制在这种应用中使用。例如,联邦监管指南(Union Guidelineson Regulation)(EU)No 10/2011中对拟与食品接触的塑料材料和制品列出的欧洲法规限制锂的迁移极限为0.6mg/Kg材料。
GB2447221(A)公开了一种组合物,它包括在水溶性成膜丙烯酸类溶液聚合物的膜当中分散的金属硅酸盐。金属硅酸盐对丙烯酸类溶液聚合物之比可以是99:1至4:1。还公开了形成气体阻挡涂层的组合物,它包括金属硅酸盐和水溶性成膜丙烯酸类溶液聚合物在溶剂中的溶液。然而,在聚合物基底上的已知玻璃膜的问题是这些公开的涂层中的无机硅酸盐层发脆且倾向于龟裂或脱层,当聚合物弯曲时,这主要是因为对聚合物基底的粘结力差,从而导致差的气体和蒸汽不可渗透性能。
为克服脆度问题提出的路线是将纳米颗粒和/或聚合物溶液或乳液引入到硅酸盐涂层内。
EP2195390A1涉及气体阻挡涂层,其尤其具有阻挡氧气穿过的能力,所述组合物包括水溶性金属硅酸盐;粘土;和聚合物乳液;该硅酸盐包括组合物内至少70%重量的固体,和粘土与聚合物各自包括组合物内全部固体的至少1%重量。还在JP2001260264和GB2452718中报道了与金属硅酸盐结合使用粘土。
GB1068584公开了一种水性含硅涂料组合物,它包括SiO2/M2O摩尔比为至少3和组合的水含量为至少18wt%的至少一种水溶性碱金属硅酸盐,其中M是K或Na,至少一种填料和/或一种颜料,和在硅酸盐溶液中可溶的至少一种成膜胶体粘合剂。
US2002168477(A1)公开了一种硅酸盐涂料组合物,它包括含锌粒的含水分散体。用于该组合物的粘合剂是硅酸钠或硅酸钾与足量聚硅酸锂的混合物。
EP0906374 B1公开了一种用于聚合物制品的透明阻挡涂层,它包括具有无机阻挡层的聚(对苯二甲酸乙二酯)聚合物基底,所述无机阻挡层在小于500nm的厚度时基本上透明且由含碱金属聚硅酸盐和纳米晶体二氧化钛的溶液制备。U.S5853830还提到一种涂料溶液,它包括金属聚硅酸盐溶液和纳米晶体二氧化钛。
EP2252652 A1公开了一种亲水抗雾组合物,它包括碱金属硅酸盐,润湿剂和亲水抗雾剂。
本领域也还仍需要用于涂料组合物和方法的阻挡涂层,它克服了上述缺陷并对聚合物包装产品提供良好的蒸汽,气体和/或香味阻挡。
发明内容
在这一现有技术状态下,现根据本发明提供一种透明的气体阻挡聚合物-玻璃-聚合物层压膜,它包括:
a.第一聚合物膜基底;
b.在所述第一聚合物膜基底上层压的硅酸盐玻璃层,其包括与选自有机基-硅烷或环氧基硅烷前体中的至少一种添加剂结合的氧化硅和除了锂以外的单价阳离子的盐;和
c.在所述玻璃层上层压的第二聚合物膜;
其中经层压聚合物-玻璃-聚合物膜的透氧速率低于0.2cc/m2/天。
具体实施方式
优选地,层压聚合物-玻璃-聚合物膜的雾度低于1%。
在优选的实施方案中,通过在所述第一聚合物膜基底上印刷并固化至少两层硅酸盐油墨,形成所述硅酸盐玻璃层;
优选地,所述单价阳离子选自钠,钾,铵及其任何组合。
在优选的实施方案中,所述透明的气体阻挡聚合物-玻璃-聚合物层压膜进一步包括选自磷酸单钾,磷酸单钠,磷酸单铵,磷酸二钾,磷酸二钠,磷酸三钾,磷酸三钠,六偏磷酸钠,三聚磷酸钠,三聚磷酸铵,三聚磷酸钾,焦磷酸钠,磷酸三钙及其组合中的无机磷酸盐。
优选地,在390-700nm的可见光谱区域内,聚合物-玻璃-聚合物层压膜的透明度高于60%。
在本发明的优选实施方案中,对于在390-700nm的可见光谱区域内的光来说,聚合物-玻璃-聚合物层压体的透明度高于80%。
在优选的实施方案中,所述单价阳离子的盐选自碳酸盐,乙酸盐,富马酸盐或其任何组合。
优选地,第二聚合物膜包括选自聚酯,聚碳酸酯,聚丙烯酸酯,聚烯烃,聚氨酯,聚丙烯酸类,聚酰胺,环氧树脂,硅类,聚硫化物,氯化橡胶,酚树脂,聚乙烯基类及其共聚物中的至少一种热塑性聚合物。
在本发明的另一方面中,提供生产聚合物-玻璃-聚合物层压气体阻挡膜的方法,该方法包括:
■在第一聚合物膜基底上印刷并干燥玻璃油墨配方至少2层,所述玻璃油墨配方包括含除了锂以外的单价阳离子的硅酸盐;
■固化在第一聚合物膜基底上的所述印刷的玻璃层,在所述第一聚合物膜基底上形成硅酸盐玻璃涂层;和
■层压固化的玻璃涂布的聚合物基底与第二聚合物膜,形成所述聚合物-玻璃-聚合物层压气体阻挡膜;
其中经聚合物-玻璃-聚合物层压膜的透氧速率低于0.2cc/m2/天。
优选地,直接印刷玻璃层。
任选地,玻璃层或者通过使用非接触或者接触印刷方法直接印刷。
在另一实施方案中,印刷的玻璃层的厚度和粘结到聚合物基底上能获得挠性层压体。
在本发明的优选实施方案中,所述印刷方法选自筛网印刷,辊涂,喷涂,幕涂,浸涂,照相凹版涂布,喷墨印刷或柔版印刷及其组合。
在另一实施方案中,按照已知且常规的方式,例如通过火焰,等离子体,或电晕放电处理聚合物基底,改进其对油墨的接受度和/或它的适合性以供这种随后的制造操作,例如层压。
在优选的实施方案中,玻璃层的厚度小于30微米,优选小于20,更优选小于10微米,和甚至更优选小于5微米。
在另一实施方案中,在印刷循环之间,在干燥下,至少两次印刷玻璃层。在再一实施方案中,在印刷循环之间,在干燥和固化下,至少两次印刷玻璃层。
在另一实施方案中,在富含二氧化碳的氛围或者有机或无机酸性氛围内固化玻璃层。
在优选的实施方案中,将有机基硅烷或环氧基硅烷加入到配方中,以便减少龟裂并降低硅酸盐层固化之后的透气性。有机基硅烷或环氧基硅烷选自3-氨丙基-三乙氧基-硅烷,3-环氧丙氧-丙基-三甲氧基硅烷,对氨基苯基-硅烷,烯丙基三甲氧基硅烷,n-(2-氨乙基)-3-氨基-丙基-三-甲氧基-硅烷,3-氨基-丙基-三-乙氧基-硅烷,3-氨基-丙基-三甲氧基-硅烷,3-环氧丙氧-丙基-二异丙基-乙氧基-硅烷,(3-环氧丙氧丙基)甲基-二-乙氧基-硅烷,3-巯基-丙基-三甲氧基-硅烷,3-巯基-丙基-三乙氧基-硅烷,3-甲基丙烯酰氧基-丙基-甲基-二-乙氧基-硅烷,3-甲基丙烯酰氧基-丙基-甲基-二-甲氧基-硅烷,3-甲基丙烯酰氧基-丙基三-甲氧基-硅烷,正苯基-氨基-丙基-三-甲氧基-硅烷,乙烯基-甲基-二-乙氧基-硅烷,乙烯基-三-乙氧基-硅烷,乙烯基-三-甲氧基-硅烷,3-环氧丙氧丙基-三甲氧基硅烷,β-(3,4-环氧基-环己基)-乙基-三-甲氧基-硅烷,3-环氧丙氧-丙基-甲基-二-乙氧基-硅烷和2-环氧丙氧-丙基-三-甲氧基-硅烷及其混合物。
在优选的实施方案中,所述第一聚合物膜包括选自聚酯,聚碳酸酯,聚丙烯酸酯,聚烯烃,聚氨酯,聚丙烯酸类,聚酰胺,环氧树脂,硅类,聚硫化物,氯化橡胶,酚树脂,聚乙烯基类及其共聚物中的至少一种热塑性聚合物。
优选地,通过在玻璃层和第二聚合物膜中的至少一个上沉积粘合剂树脂层,制造层压体。
在优选的实施方案中,第二聚合物膜包括选自聚酯,聚碳酸酯,聚丙烯酸酯,聚烯烃,聚氨酯,聚丙烯酸类,聚酰胺,环氧树脂,硅类,聚硫化物,氯化橡胶,酚树脂,聚乙烯基类及其共聚物中的至少一种热塑性聚合物。
优选地,粘合剂基于聚乙烯,聚氨酯,丙烯酸类,甲基丙烯酸类,环氧树脂,乙烯基缩丁醛(PVB),乙烯乙酸乙烯酯(EVA)或乙烯氢氧化乙烯基(ethylene vinyl hydroxide)(EVOH)。
在本发明进一步的方面中,提供制备以上定义的层压膜所使用的玻璃油墨,其中所述硅酸盐选自硅酸钠,硅酸钾,硅酸铵及其组合。
优选地,玻璃油墨进一步包括选自无机磷酸盐,有机基-硅烷,环氧基硅烷前体及其组合中的至少一种添加剂。
在优选的实施方案中,所述有机基硅烷或环氧基硅烷添加剂在加入到油墨配方中之前或之后被热水解。
在本发明的优选实施方案中,所述玻璃油墨包括至少20wt%硅酸盐,其中油墨的表面张力低于40dynes/cm。
在特别优选的实施方案中,油墨的表面张力低于35dynes/cm。
优选地,所述玻璃油墨进一步包括选自磷酸单钾,磷酸单钠,磷酸单铵,磷酸二钾,磷酸二钠,磷酸三钾,磷酸三钠,六偏磷酸钠,三聚磷酸钠,三聚磷酸铵,三聚磷酸钾,焦磷酸钠,磷酸三钙及其组合中的磷酸盐。
在本发明特别优选的实施方案中,油墨的浊度在600nm(1cm光程)下低于0.2。
在本发明的优选实施方案中,第一聚合物膜包括选自聚酯,聚碳酸酯,聚丙烯酸酯,聚烯烃,聚氨酯,聚丙烯酸类,聚酰胺,环氧树脂,硅类,聚硫化物,氯化橡胶,酚树脂,聚乙烯基类或其共聚物中的一种或多种热塑性聚合物。
在优选的实施方案中,通过在玻璃层上,在第二聚合物膜上或者在二者上沉积粘合剂树脂层,制造层压体。
在另一实施方案中,在印刷的玻璃层上作为聚合物树脂的形式就地沉积第二聚合物膜,从而形成第二聚合物膜。
在另一实施方案中,层压膜的透氧速率低于0.05cc/m2/天,和甚至更优选低于0.01cc/m2/天,和最优选0.001cc/m2/天,或甚至更低。
在另一实施方案中,印刷玻璃层大于三次,大于四次或大于五次,以便降低透气率到甚至更低的数值。
在本发明的另一实施方案中,第二聚合物膜包括选自聚酯,聚碳酸酯,聚丙烯酸酯,聚烯烃,聚氨酯,聚丙烯酸类,聚酰胺,环氧树脂,硅类,聚硫化物,氯化橡胶,酚树脂,聚乙烯基类或其共聚物中的一种或多种热塑性聚合物。
优选地,所述第二聚合物膜包括聚乙烯,聚乳酸,聚酯或其组合。
在另一实施方案中,添加剂基于聚乙烯,聚氨酯,丙烯酸类,环氧树脂,乙烯基缩丁醛(PVB),乙烯乙酸乙烯酯(EVA)或乙烯氢氧化乙烯基(EVOH)。
在另一实施方案中,硅酸盐玻璃涂层进一步包括金属氧化物纳米颗粒。
在另一实施方案中,玻璃层的折射指数在小于0.1折射指数单位到第一聚合物基底的折射指数以内。
任选地,硅酸盐玻璃层进一步包括至少一种颜料或着色物质。
尽管在下述实施例中,现结合某些特定实施方案进一步描述了本发明,以便本发明的方面可以更加充分地了解并理解,但并不打算限制本发明到这些特定实施方案上。相反,打算覆盖如可以包括在所附权利要求定义的本发明的范围内的所有备选方案,改性和等价方案。因此,下述实施例将起到阐述本发明实践的作用,要理解,所示的特定细节作为实例和为的是仅仅本发明特定实施方案的示意性讨论且为提供认为最有用和容易理解配方工序以及本发明的原理和概念方面的说明而列出。
实施例
现参考下述实施例,所述实施例与上述说明一起以非限制性方式阐述本发明。
实施例中所使用的材料
在以下如本文的实施例所描述的例举配方中使用下述材料:36微米(SH37),45微米(SP18A),50微米(SG55C),75微米P.P.C.PET膜和100微米P.P.C.PET膜由SKC(Skyrolbrand,SKC co.Ltd.,韩国)和Jolybar ltd.(以色列)供应。硅溶胶以在水中30%胶态分散体供应,获自Alfa Aesar;ST-40是获自Nissan Chemical,AmericaCorporation,Houston,TX USA的胶态氧化硅颗粒分散体;PVA是指获自Sigma Aldrich的4-98Mw~27,000;环氧基硅烷是指获自Dow corning的Z-6040 Silane环氧丙氧丙基三甲氧基硅烷;磷酸钠获自Sigma Aldrich;PEI是指聚乙烯亚胺,其获自Bio lab Ltd,Israel;乙二醇获自Bio lab Ltd,以色列;十六烷基三甲基溴化铵,甘油二者获自SigmaAldrich;硅酸钾和硅酸钠获自Provetrogruppe,SchloβHolte,德国。
对比例1
使用PE膜(80微米厚),在150℃下,由POUCH LAMINATOR PDA3-330L层压75微米PET膜。其OTR为13.6cc/m2/天。
实施例2
根据下述工序制备油墨配方:将10%环氧基硅烷加入到90%硅酸钠(40%固体)中。通过施涂器棒(绕线棒(Wire-wound Rod),BYK-Gardner,德国),在24微米湿厚度下,将它施加到PET膜上。在对流烘箱内,在90℃下一旦固化,则形成连续膜。在室温下5分钟之后,施加第二层,以及还施加第三层。在150℃下,由POUCH LAMINATOR PDA3-330L层压所得膜与PE膜(80微米厚)。其OTR为0.038cc/m2/天。
实施例3
根据下述工序,采用下述组分,制备油墨配方:4.1%环氧基硅烷,32.7%硅酸钠,2.0%Na5P3O10和余量水。通过施涂器棒(绕线棒,BYK-Gardner,德国),在24微米湿厚度下,在PET膜上施加该油墨。在对流烘箱内,在90℃下一旦固化,则形成连续膜。在室温下5分钟之后,施加第二层,以及还施加第三层。在150℃下,由POUCH LAMINATOR PDA3-330L层压所得膜与PE膜(80微米厚)。其OTR为0.001cc/m2/天。
实施例4
根据下述工序,和采用下述组分,制备油墨配方:1.9%葡萄糖,32.8%硅酸钠,4.1%环氧基硅烷和余量水。在24微米湿厚度下,通过施涂器棒(绕线棒,BYK-Gardner,德国),在PET片材上施加该组合物3层。每一层在对流烘箱内在90℃下固化,形成连续膜。在150℃下,由POUCH LAMINATOR PDA3-330L层压所得膜与PE膜(80微米厚)。OTR=0.06cc/m2/天。
实施例5-8
使用硅酸钠和环氧基硅烷的各种组合物(如表1中所列出的),制备油墨配方。通过施涂器棒(绕线棒,BYK-Gardner,德国),在24微米湿厚度下,在PET膜上施加组合物3层。一旦在对流烘箱内在90℃下固化,则形成连续膜。在150℃下,由POUCH LAMINATOR PDA3-330L层压所得膜与PE膜(80微米厚)。
表1:实施例5-8
硅酸钠,wt% | 环氧基硅烷,wt% | H2O | OTR | |
实施例5 | 39.6 | 0.5 | 59.9 | 0.039 |
实施例6 | 37.9 | 2.6 | 59.5 | 0.014 |
实施例7 | 36.4 | 4.5 | 59.1 | 0.13 |
实施例8 | 32 | 10 | 58 | 0.06 |
实施例9-11
使用硅酸钠,环氧基硅烷和三磷酸钠的各种组合物(如表2中所列出的),制备油墨配方。通过施涂器棒(绕线棒,BYK-Gardner,德国),在24微米湿厚度下,在PET膜上施加组合物3层。一旦在对流烘箱内在90℃下固化,则形成连续膜。在150℃下,由POUCH LAMINATORPDA3-330L层压所得膜与PE膜(80微米厚)。
表2:实施例9-11
硅酸钠,wt% | 环氧基硅烷,wt% | H2O | 三磷酸钠 | OTR | |
实施例9 | 34.5 | 4.3 | 60.1 | 1.0 | 0.285 |
实施例10 | 29.1 | 3.6 | 63.3 | 4.0 | 0.06 |
实施例11 | 32.7 | 4.1 | 61.2 | 2.0 | 0.001 |
实施例12-16
使用硅酸钠,环氧基硅烷和三磷酸钠的组合物,制备油墨配方。通过混合具有3.2和1.6摩尔比的不同液体玻璃,实现硅酸钠的摩尔比。通过施涂器棒(绕线棒,BYK-Gardner,德国),在24微米湿厚度下,在PET膜上施加组合物3层。一旦在对流烘箱内在90℃下固化,则形成连续膜。在150℃下,由POUCH LAMINATOR PDA3-330L层压所得膜与PE膜(80微米厚)。
表3:实施例12-16
实施例16
使用表4中列出的硅酸钠,环氧基硅烷和三磷酸钠的组合物,制备油墨配方。通过施涂器棒(绕线棒,BYK-Gardner,德国),在24微米湿厚度下,在PET膜上施加油墨3层。一旦在对流烘箱内在90℃下固化,则形成连续膜。在150℃下,由POUCH LAMINATOR PDA3-330L层压所得膜与PE膜(80微米厚)。
表4:实施例16
硅酸钠,wt% | 硅酸钾,wt% | H2O | 环氧基硅烷,wt% | OTR | |
实施例16 | 27.9 | 20.3 | 46.8 | 5 | 0.029 |
对于本领域技术人员来说显而易见的是,并不将本发明限制到前面示意性实施例的细节上,和在没有脱离本发明的基本属性情况下,本发明可在其他具体的形式中体现,和因此期望本发明的实施方案和实施例被视为在所有方面为示意性而不是限制的,参考所附权利要求,而不是前述说明,和落在权利要求的等价方案的含义和范围内的所有变化因此拟在其内涵盖。
Claims (22)
1.一种透明的气体阻挡聚合物-玻璃-聚合物层压膜,它包括:
a.第一聚合物膜基底;
b.在所述第一聚合物膜基底上层压的硅酸盐玻璃层,其包括与选自有机基-硅烷或环氧基硅烷前体中的至少一种添加剂结合的氧化硅和除了锂以外的单价阳离子的盐;和
c.在所述玻璃层上层压的第二聚合物膜;
其中经层压聚合物-玻璃-聚合物膜的透氧速率低于0.2cc/m2/天。
2.权利要求1的透明的气体阻挡聚合物-玻璃-聚合物层压膜,其中层压的聚合物-玻璃-聚合物膜的雾度低于1%。
3.权利要求1的透明的气体阻挡聚合物-玻璃-聚合物层压膜,其中通过在所述第一聚合物膜基底上印刷并固化至少两层硅酸盐油墨,形成所述硅酸盐玻璃层。
4.权利要求1的透明的气体阻挡聚合物-玻璃-聚合物层压膜,其中所述单价阳离子选自钠、钾、铵及其任何组合。
5.权利要求1的透明的气体阻挡聚合物-玻璃-聚合物层压膜,进一步包括选自磷酸单钾、磷酸单钠、磷酸单铵、磷酸二钾、磷酸二钠、磷酸三钾、磷酸三钠、六偏磷酸钠、三聚磷酸钠、三聚磷酸铵、三聚磷酸钾、焦磷酸钠、磷酸三钙及其组合中的无机磷酸盐。
6.权利要求1的层压膜,其中在390-700nm的可见光谱区域内,聚合物-玻璃-聚合物层压膜的透明度高于60%。
7.权利要求1的层压膜,其中所述单价阳离子的盐选自碳酸盐,乙酸盐,富马酸盐或其任何组合。
8.权利要求1的层压膜,其中第二聚合物膜包括选自聚酯,聚碳酸酯、聚丙烯酸酯、聚烯烃、聚氨酯、聚丙烯酸类、聚酰胺、环氧树脂、硅类、聚硫化物、氯化橡胶、酚树脂、聚乙烯基类及其共聚物中的至少一种热塑性聚合物。
9.生产聚合物-玻璃-聚合物层压气体阻挡膜的方法,该方法包括:
■在第一聚合物膜基底上印刷并干燥玻璃油墨配方的至少两个层,所述玻璃油墨配方包括含除了锂以外的单价阳离子的硅酸盐;
■固化在第一聚合物膜基底上的所述印刷的玻璃层,在所述第一聚合物膜基底上形成硅酸盐玻璃涂层;和
■层压固化的玻璃涂布的聚合物基底与第二聚合物膜,形成所述聚合物-玻璃-聚合物层压气体阻挡膜;
其中经聚合物-玻璃-聚合物层压膜的透氧速率低于0.2cc/m2/天。
10.权利要求9的方法,其中直接印刷玻璃层。
11.权利要求9的方法,其中所述印刷方法选自丝网印刷、辊涂、喷涂、幕涂、浸涂、照相凹版印刷、喷墨印刷或柔版印刷及其组合。
12.权利要求9的方法,其中玻璃层的厚度小于30微米。
13.权利要求9的方法,其中第一聚合物膜包括选自聚酯、聚碳酸酯、聚丙烯酸酯、聚烯烃、聚氨酯、聚丙烯酸类、聚酰胺、环氧树脂、硅类、聚硫化物、氯化橡胶、酚树脂、聚乙烯基类及其共聚物中的至少一种热塑性聚合物。
14.权利要求9的方法,其中通过在玻璃层和第二聚合物膜的至少一个上沉积粘合剂树脂层,制造层压体。
15.权利要求9的方法,其中第二聚合物膜包括选自聚酯、聚碳酸酯、聚丙烯酸酯、聚烯烃、聚氨酯、聚丙烯酸类、聚酰胺、环氧树脂、硅类、聚硫化物、氯化橡胶、酚树脂、聚乙烯基类及其共聚物中的至少一种热塑性聚合物。
16.权利要求9的方法,其中粘合剂基于聚乙烯、聚氨酯、丙烯酸类、甲基丙烯酸类、环氧树脂、乙烯基缩丁醛(PVB)、乙烯乙酸乙烯酯(EVA)或乙烯乙烯醇(ethylene vinylhydroxide)(EVOH)。
17.用于制备权利要求9-16的层压膜的玻璃油墨,其中所述硅酸盐选自硅酸钠、硅酸钾、硅酸铵及其组合。
18.权利要求17的玻璃油墨,其中玻璃油墨进一步包括选自无机磷酸盐、有机基-硅烷、环氧基硅烷前体及其组合中的至少一种添加剂。
19.权利要求17的玻璃油墨,其中所述有机基硅烷或环氧基硅烷添加剂在加入到油墨配方中之前或之后被热水解。
20.权利要求17的玻璃油墨,它包括至少20wt%硅酸盐,其中该油墨的表面张力低于40达因/cm。
21.用于制备权利要求1的层压体的权利要求17的玻璃油墨,它进一步包括选自磷酸单钾、磷酸单钠、磷酸单铵、磷酸二钾、磷酸二钠、磷酸三钾、磷酸三钠、六偏磷酸钠、三聚磷酸钠、三聚磷酸铵、三聚磷酸钾、焦磷酸钠、磷酸三钙及其组合中的无机磷酸盐。
22.权利要求17的玻璃油墨,其中在600nm(1cm光程)下,油墨的浊度低于0.2。
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US62/053,153 | 2014-09-21 | ||
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