JP2012210785A - Gas barrier film and method for manufacturing the same - Google Patents
Gas barrier film and method for manufacturing the same Download PDFInfo
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- JP2012210785A JP2012210785A JP2011078506A JP2011078506A JP2012210785A JP 2012210785 A JP2012210785 A JP 2012210785A JP 2011078506 A JP2011078506 A JP 2011078506A JP 2011078506 A JP2011078506 A JP 2011078506A JP 2012210785 A JP2012210785 A JP 2012210785A
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- 230000004888 barrier function Effects 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 title description 10
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000007789 gas Substances 0.000 claims abstract description 155
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 59
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 58
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 28
- 239000010410 layer Substances 0.000 claims abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 16
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- 239000011248 coating agent Substances 0.000 claims description 114
- 239000007787 solid Substances 0.000 claims description 71
- 229920001444 polymaleic acid Polymers 0.000 claims description 43
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 30
- 230000035699 permeability Effects 0.000 claims description 25
- -1 polypropylene Polymers 0.000 claims description 16
- UPBDXRPQPOWRKR-UHFFFAOYSA-N furan-2,5-dione;methoxyethene Chemical compound COC=C.O=C1OC(=O)C=C1 UPBDXRPQPOWRKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- 229920006255 plastic film Polymers 0.000 claims description 8
- 239000002985 plastic film Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 229920006267 polyester film Polymers 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 61
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 26
- 239000007864 aqueous solution Substances 0.000 abstract description 15
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000005022 packaging material Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 55
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 229920002125 Sokalan® Polymers 0.000 description 19
- 239000004584 polyacrylic acid Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 18
- 238000000576 coating method Methods 0.000 description 17
- 230000007062 hydrolysis Effects 0.000 description 14
- 238000006460 hydrolysis reaction Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 229920005862 polyol Polymers 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
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- 239000003513 alkali Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
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- 229920005749 polyurethane resin Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229920000298 Cellophane Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 238000007127 saponification reaction Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920006284 nylon film Polymers 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- WOZHZOLFFPSEAM-UHFFFAOYSA-N 3-butene-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(=C)C(O)=O WOZHZOLFFPSEAM-UHFFFAOYSA-N 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- KOPGXQBFEROLEQ-UHFFFAOYSA-N benzhydrylbenzene;isocyanic acid Chemical compound N=C=O.C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 KOPGXQBFEROLEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- DTGRIEIJTWNZQF-UHFFFAOYSA-N cyclohexane-1,2,3,4,5,6-hexacarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C(C(O)=O)C(C(O)=O)C1C(O)=O DTGRIEIJTWNZQF-UHFFFAOYSA-N 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- RPOCFUQMSVZQLH-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-1-ene Chemical compound CC(C)=C.O=C1OC(=O)C=C1 RPOCFUQMSVZQLH-UHFFFAOYSA-N 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical group C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
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- UFOIOXZLTXNHQH-UHFFFAOYSA-N oxolane-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1OC(C(O)=O)C(C(O)=O)C1C(O)=O UFOIOXZLTXNHQH-UHFFFAOYSA-N 0.000 description 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
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- 229920006254 polymer film Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
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- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
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- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
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- 239000004416 thermosoftening plastic Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
Abstract
Description
本発明は食品、医薬品、精密電子部品等の包装分野等に用いられる、特に、透明性を有するガスバリア性積層体に関する TECHNICAL FIELD The present invention relates to a gas barrier laminate having transparency, particularly used in the packaging field of foods, pharmaceuticals, precision electronic components and the like.
近年、食品、医薬品、精密電子部品等の包装分野に用いられる包装材料は、内容物の変質、特に食品においては油脂の酸化や蛋白質の変質等を抑制して味や鮮度を保持するために、また医薬品においては有効成分の変質を抑制して効能を維持するために、さらに精密電子部品においては金属部分の腐食を抑制して絶縁不良等を防ぐために、包装材料を透過する酸素による影響を防止する必要があり、気体（ガス）を遮断するガスバリア性を備えることが求められている。 In recent years, packaging materials used in the packaging field of foods, pharmaceuticals, precision electronic components, etc. are used to maintain the taste and freshness by suppressing the alteration of contents, especially the oxidation of fats and oils and the alteration of proteins in foods. In addition, in pharmaceuticals, the effects of oxygen permeating through packaging materials are prevented in order to suppress the deterioration of active ingredients and maintain their efficacy, and in precision electronic parts, to suppress the corrosion of metal parts and prevent poor insulation. Therefore, it is required to have a gas barrier property to block gas (gas).
そのために、従来から塩化ビニリデン樹脂をコートしたポリプロピレン（ＫＯＰ）やポリエチレンテレフタレート（ＫＰＥＴ）或いはエチレンビニルアルコール共重合体（ＥＶＯＨ）など一般にガスバリア性が比較的高いと言われる高分子フィルムをガスバリア性フィルムとして用いた包装フィルム、あるいは酸化珪素（ＳｉＯｘ）などの珪素酸化物薄膜を透明高分子からなる基材上に真空蒸着などの手段によって設けた蒸着フィルムをガスバリア性フィルムとして用いた包装フィルムが一般的に使用されてきた。 For this purpose, polymer films that are generally said to have a relatively high gas barrier property such as polypropylene (KOP), polyethylene terephthalate (KPET), or ethylene vinyl alcohol copolymer (EVOH) coated with vinylidene chloride resin are used as gas barrier films. Generally used is a packaging film or a packaging film using, as a gas barrier film, a vapor deposition film in which a silicon oxide thin film such as silicon oxide (SiOx) is provided on a transparent polymer substrate by means of vacuum vapor deposition or the like. Have been used.
ところが、ＫＯＰやＫＰＥＴ等の塩化ビニリデン樹脂を用いた包装フィルムは、使用後の廃棄において焼却処理すると塩素ガスを発生するため、これが酸性雨の原因の一つになると言われ、最近では敬遠される傾向があった。さらに上述のＥＶＯＨを用いた包装フィルムは、温度や湿度の影響を受け易く、その変化によっては更にガスバリア性が低下することがあった。
また、珪素酸化物薄膜を透明高分子からなる基材上に真空蒸着などの手段によって設けた蒸着フィルムは、屈曲等によって蒸着膜にクラックが入りやすく、結果としてガスバリア性が低下することがある。
However, packaging films using vinylidene chloride resins such as KOP and KPET are said to be one of the causes of acid rain because they generate chlorine gas when incinerated in disposal after use. There was a trend. Furthermore, the packaging film using the above-mentioned EVOH is easily affected by temperature and humidity, and the gas barrier property may be further lowered depending on the change.
In addition, a deposited film in which a silicon oxide thin film is provided on a substrate made of a transparent polymer by means such as vacuum deposition may easily crack the deposited film due to bending or the like, and as a result, gas barrier properties may be lowered.
そこでこれらの欠点を克服した包装フィルムとして、水溶性の無機物もしくはポリマーからなる液状組成物をフィルムにコートし、高いガスバリア性を発現させる方法として、ポリビニルアルコール（ＰＶＡ）等の親水性高分子溶液と金属アルコキシドの加水分解溶液を混合し、フィルムにコート後乾燥、熱処理し親水性高分子と金属アルコキシド間で相互に作用させることによりガスバリア性の付与を行う方法が提案されている（特許文献１）。これらの方法は金属酸化物が有する優れたガスバリア性と高分子が有する柔軟性を兼ね備えており、高いガスバリア性と屈曲するような乱暴な取扱いにも耐えうる実用性を有している。
しかしながらこのようにして作られたコートフィルムのコート層は、インキとの接着性が低下し、フリーロールにインキがとられる等、耐スクラッチ性が劣るという問題がある
Therefore, as a packaging film that overcomes these drawbacks, as a method for coating a film with a liquid composition comprising a water-soluble inorganic substance or polymer and developing a high gas barrier property, a hydrophilic polymer solution such as polyvinyl alcohol (PVA) A method of imparting gas barrier properties by mixing a hydrolyzed solution of metal alkoxide, coating the film, drying and heat-treating the polymer to interact between the hydrophilic polymer and the metal alkoxide has been proposed (Patent Document 1). . These methods combine the excellent gas barrier properties of metal oxides with the flexibility of polymers, and have high gas barrier properties and practicality that can withstand rough handling such as bending.
However, the coating layer of the coating film thus produced has a problem that the adhesion to the ink is lowered and the scratch resistance is inferior, for example, the ink is taken on the free roll.
今回発明したコート膜組成と類似の酸素バリアコート剤として、ポリビニルアルコール、ケイ素アルコキドの加水分解液、カルボン酸化合物を使用し、シール層の剥離強度に優れたガスバリア性フィルム作製方法が提案されている（特許文献２）が、本発明のコート剤組成の場合、カルボン酸を１０％以上中和しないと、ガスバリア性が発現しない。また、使用されるカルボン酸化合物の一般式は本発明で使用している分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物（化１）とは異なる。
（化１中のＲ１、Ｒ２、Ｒ３、Ｒ４はＯＨ、ＣＯＯＨ、ＣＨ２ＣＯＯＨのいずれかを示し、αは１以上の整数を示す。）
As an oxygen barrier coating agent similar to the coating film composition invented this time, a method for producing a gas barrier film using a polyvinyl alcohol, a hydrolyzed silicon alkoxide, and a carboxylic acid compound and having excellent peel strength of the sealing layer has been proposed. In the case of the coating agent composition of the present invention (Patent Document 2), gas barrier properties are not exhibited unless the carboxylic acid is neutralized by 10% or more. The general formula of the carboxylic acid compound used is a compound in which at least one carboxyl group is bonded to each of two or more consecutive carbon atoms in the molecule used in the present invention (Chemical Formula 1). Is different.
(R1, R2, R3, and R4 in Chemical Formula 1 represent OH, COOH, or CH 2 COOH, and α represents an integer of 1 or more.)
本発明は上記欠点を解決するものであり、インキ接着性の良好なガスバリア性フィルム及びその製造方法を提供するものである。 This invention solves the said fault, and provides the gas barrier property film with favorable ink adhesiveness, and its manufacturing method.
本発明者らは、ガスバリア層に分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物の１０〜３０％中和物を添加することで課題を解決できることを見出し、本発明を完成させるに至った。
すなわち、本発明は、
（１）プラスチックフィルムからなる基材の少なくとも片面に接着層を設け、該接着層の上に下記ガスバリアコート剤を塗布することによってガスバリア層を形成するガスバリアフィルムであって、
前記ガスバリアコート剤が、アルコキシシラン及び／又はアルコキシシラン重縮合物の加水分解物（Ａ）と、ポリビニルアルコール（アルコキシシラン及び／又はアルコキシシランの重縮合物の加水分解物から生成する珪素酸化物と、ポリビニルアルコールの重量比が５０／５０〜８０／２０）と下記一般式（１）を満たす、分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている中和度１０〜３０％の中和物からなる、インキ接着性の良好なガスバリア性フィルム。
（化１中のＲ１、Ｒ２、Ｒ３、Ｒ４はＯＨ、ＣＯＯＨ、ＣＨ２ＣＯＯＨのいずれかを示し、αは１以上の整数を示す。）
（２）前記ガスバリアフィルムの酸素透過度が１０ｃｃ／ｍ２ ・ａｔｍ・２４ｈ以下である請求項１記載のガスバリア性フィルム
（３）ガスバリア層に存在する固形分１００重量部に対して、分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物の部分中和物のカルボニル基が１．２〜１１．５ｍｏｌ／１００重量部の割合でガスバリア層に存在する上記（１）記載のフィルム積層体の製造方法、
（４）分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物が、ポリマレイン酸、メチルビニルエーテル無水マレイン酸、１，２，３，４−ブタンテトラカルボン酸であるガスバリアフィルム、
（５）プラスチックフィルムが、延伸ポリアミドフィルム、延伸ポリプロピレンフィルムあるいは延伸ポリエステルフィルムであるガスバリア性フィルム、
である。
The inventors have solved the problem by adding a 10 to 30% neutralized product of a compound in which at least one carboxyl group is bonded to each of two or more consecutive carbon atoms in the molecule to the gas barrier layer. The inventors have found that this can be solved, and have completed the present invention.
That is, the present invention
(1) A gas barrier film in which an adhesive layer is provided on at least one surface of a substrate made of a plastic film, and a gas barrier layer is formed by applying the following gas barrier coating agent on the adhesive layer,
The gas barrier coating agent comprises an alkoxysilane and / or alkoxysilane polycondensate hydrolyzate (A), and polyvinyl alcohol (alkoxysilane and / or alkoxysilane polycondensate hydrolyzate generated from the hydrolyzate , At least one carboxyl group is bonded to each of two or more consecutive carbon atoms in the molecule satisfying the following general formula (1): 50/50 to 80/20) A gas barrier film having good ink adhesion and comprising a neutralized product having a neutralization degree of 10 to 30%.
(R1, R2, R3, and R4 in Chemical Formula 1 represent OH, COOH, or CH 2 COOH, and α represents an integer of 1 or more.)
(2) The oxygen permeability of the gas barrier film is 10 cc / m 2 · atm · 24 h or less. The gas barrier film according to claim 1 (3) with respect to 100 parts by weight of the solid content present in the gas barrier layer, The carbonyl group of the partially neutralized compound having at least one carboxyl group bonded to each of two or more consecutive carbon atoms is present in the gas barrier layer at a ratio of 1.2 to 11.5 mol / 100 parts by weight. The method for producing a film laminate according to the above (1),
(4) A compound in which at least one carboxyl group is bonded to each of two or more consecutive carbon atoms in the molecule is polymaleic acid, methyl vinyl ether maleic anhydride, 1,2,3,4-butanetetra A gas barrier film which is a carboxylic acid,
(5) a gas barrier film in which the plastic film is a stretched polyamide film, a stretched polypropylene film or a stretched polyester film;
It is.
本発明によると、オーバーコート層を設けなくても高湿度下で長時間ガスバリア性を維持し、かつ一般的な包装材料として使用可能な衝撃強度を有し、インキ接着性が向上したガスバリア性フィルムが得られる。
According to the present invention, a gas barrier film that has an impact strength that can be used as a general packaging material and has improved ink adhesiveness, maintains gas barrier properties under high humidity for a long time without providing an overcoat layer. Is obtained.
本発明で使用されるアルコキシシランおよびその重縮合物は下記一般式（２）で表わされる。
（式中のＲは同一又は異なってもよい炭素数１〜４のアルキル基を示し、ｎは０〜１０の整数を示す。）
The alkoxysilane and its polycondensate used in the present invention are represented by the following general formula (2).
(R in a formula shows the same or different C1-C4 alkyl group, and n shows the integer of 0-10.)
本発明のガスバリアコート剤は、アルコキシシランおよび／またはアルコキシシラン重縮合物の加水分解物と親水性ポリマーと一般式（１）を満たす、分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物の１０〜３０％中和物を添加した水性溶液をｐＨ３．５以下に調整したものである。本発明で用いられるアルコキシシランおよび／またはアルコキシシラン重縮合物としては通常、上記一般式（２）で表される化合物が用いられる。 The gas barrier coating agent of the present invention contains at least each of two or more continuous carbon atoms in the molecule satisfying the hydrolyzate of alkoxysilane and / or alkoxysilane polycondensate, hydrophilic polymer, and general formula (1). An aqueous solution to which 10 to 30% neutralized product of a compound having one carboxyl group is added is adjusted to pH 3.5 or less. As the alkoxysilane and / or alkoxysilane polycondensate used in the present invention, a compound represented by the above general formula (2) is usually used.
親水性ポリマーとしては、バリア性や可撓性の面から、ポリビニルアルコール類が望ましい。ポリビニルアルコール類は、ポリビニルアルコール、もしくはエチレン含有率が３〜３０％の変性ポリビニルアルコールを使用しても良いが、水溶液を調製するにあたってポリビニルアルコールが好ましい。けん化度は８０％以上が好ましく、より好ましくは完全けん化物が用いられる。完全けん化物の方がアルコキシシランの加水分解物との相溶性が良く、より緻密なバリア層を形成する。ポリビニルアルコールの重合度は２００から３，５００が好ましい。 As the hydrophilic polymer, polyvinyl alcohols are desirable from the viewpoint of barrier properties and flexibility. As the polyvinyl alcohol, polyvinyl alcohol or modified polyvinyl alcohol having an ethylene content of 3 to 30% may be used, but polyvinyl alcohol is preferable in preparing an aqueous solution. The saponification degree is preferably 80% or more, and more preferably a complete saponification product is used. The completely saponified product is more compatible with the hydrolyzate of alkoxysilane and forms a denser barrier layer. The degree of polymerization of polyvinyl alcohol is preferably 200 to 3,500.
アルコキシシランは、好ましくは加水分解率９０％以上に加水分解された後、ポリビニルアルコール溶液と混合される。アルコキシシランの加水分解は、アルコキシシランを水、無機酸（もしくは、無機塩、有機酸）及び、有機溶媒を含む溶液中で加温することにより実施される。このときアルコキシシラン加水分解物の重縮合も同時に起こる。用いられる水の量は、アルコキシシランの珪素１原子に対し６〜１０モルである。１０モルより多いと加水分解したシリケートの重縮合が進行しすぎて溶液がゲル化する。ゲル化した液はポリビニルアルコール溶液と均一に混合することができない。また６モルより少ないとアルコキシシランの加水分解率９０％以上を達成することが実質上困難である。 The alkoxysilane is preferably hydrolyzed to a hydrolysis rate of 90% or more and then mixed with the polyvinyl alcohol solution. Hydrolysis of alkoxysilane is carried out by heating alkoxysilane in a solution containing water, an inorganic acid (or inorganic salt, organic acid) and an organic solvent. At this time, polycondensation of the alkoxysilane hydrolyzate also occurs simultaneously. The amount of water used is 6 to 10 moles per silicon atom of alkoxysilane. When the amount is more than 10 mol, polycondensation of the hydrolyzed silicate proceeds too much and the solution gels. The gelled liquid cannot be uniformly mixed with the polyvinyl alcohol solution. On the other hand, when the amount is less than 6 mol, it is substantially difficult to achieve a hydrolysis rate of 90% or more of alkoxysilane.
添加される無機酸（もしくは、無機塩、有機酸）は、アルコキシシランの加水分解および重縮合の触媒として作用する。用いられる酸は、塩酸、硝酸等の鉱酸や乳酸等が用いられる。加水分解時のｐＨは、０．５〜３．５、好ましくは２．０〜３．０である。ｐＨが３．５より大きいと加水分解が進行しない。ｐＨが０．５より小さいと加水分解は十分に進行するものの同時に重縮合の進行も著しく、溶液がゲル化する。 The added inorganic acid (or inorganic salt, organic acid) acts as a catalyst for hydrolysis and polycondensation of alkoxysilane. Examples of the acid used include mineral acids such as hydrochloric acid and nitric acid, and lactic acid. The pH during hydrolysis is 0.5 to 3.5, preferably 2.0 to 3.0. If the pH is greater than 3.5, hydrolysis does not proceed. When the pH is less than 0.5, hydrolysis proceeds sufficiently, but at the same time, polycondensation proceeds remarkably and the solution gels.
加水分解時の温度は、３０〜６０℃、好ましくは４０〜５５℃である。６０℃より高いと重縮合が進行し溶液がゲル化する。また３０℃より低いと加水分解が十分に進行せず、より長い時間を要し実用的でない。加水分解時間は溶液のｐＨおよび温度によって異なるが、概ね３０〜４００分である。 The temperature at the time of hydrolysis is 30 to 60 ° C, preferably 40 to 55 ° C. If it is higher than 60 ° C., polycondensation proceeds and the solution gels. On the other hand, if the temperature is lower than 30 ° C., hydrolysis does not proceed sufficiently, and a longer time is required, which is not practical. The hydrolysis time varies depending on the pH and temperature of the solution, but is generally 30 to 400 minutes.
用いられる有機溶媒としては、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブタノールなどが挙げられるが、特にエチルアルコールおよびイソプロピルアルコールが好適に用いられる。有機溶媒の量は加水分解に使用する水の重量に対し１０〜１００重量％、より好ましくは３０〜７０重量％である。１００重量％より多いと有機溶媒を回収するのに困難であり、１０重量％より少ないとアルコキシシランの加水分解時に溶液がゲル化を起こす。以上の方法により、アルコキシシラン９０％以上の加水分解率にも関わらず、ゲル化しない溶液を得ることができる。 Examples of the organic solvent to be used include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like, and ethyl alcohol and isopropyl alcohol are particularly preferably used. The amount of the organic solvent is 10 to 100% by weight, more preferably 30 to 70% by weight, based on the weight of water used for hydrolysis. If the amount is more than 100% by weight, it is difficult to recover the organic solvent, and if it is less than 10% by weight, the solution gels during hydrolysis of the alkoxysilane. By the above method, it is possible to obtain a solution that does not gel despite the hydrolysis rate of 90% or more of alkoxysilane.
アルコキシシランの加水分解液とポリビニルアルコール溶液との混合は、アルコキシシラン及び／又はアルコキシシランの重縮合物の加水分解物から生成する珪素酸化物（ＳｉＯ２換算）と、ポリビニルアルコールの重量比が５０／５０〜８０／２０、好ましくは５０／５０〜６２．５／３７．５である。
ポリビニルアルコールの重量比が２０％より低い場合、バリア層の柔軟性が十分でなくクラックを生じやすいばかりでなく、ガスバリア性も低下する。５０重量％より大きい場合もガスバリア性が低下し、好ましくない。該加水分解液とポリビニルアルコール水溶液とを混合したときのｐＨは１．５〜３．５が好ましく、２．０〜３．０がより好ましい。ｐＨが１．５より低いと、基材のナイロンフィルムの耐衝撃性を著しく低下させてしまう。ｐＨが３．５より高いとコート剤が高粘度となりゲル化しやすく、塗布の作業が困難となるし、十分なポットライフが得られない。このため、該加水分解液とポリビニルアルコールを混合したときｐＨが３．５より高ければポットライフ安定化のために塩酸や硝酸等の鉱酸やその他の酸を添加し、ｐＨを調整してもよい。
The mixing of the alkoxysilane hydrolyzate and the polyvinyl alcohol solution is performed by mixing the silicon oxide (in terms of SiO2) generated from the hydrolyzate of alkoxysilane and / or the polycondensate of alkoxysilane with a weight ratio of polyvinyl alcohol of 50 / 50-80 / 20, preferably 50 / 50-62.5 / 37.5.
When the weight ratio of polyvinyl alcohol is lower than 20%, not only the flexibility of the barrier layer is sufficient and cracks are easily generated, but also the gas barrier property is lowered. When it is larger than 50% by weight, the gas barrier property is lowered, which is not preferable. The pH when the hydrolyzed solution and the aqueous polyvinyl alcohol solution are mixed is preferably 1.5 to 3.5, more preferably 2.0 to 3.0. When the pH is lower than 1.5, the impact resistance of the nylon film as the base material is remarkably lowered. If the pH is higher than 3.5, the coating agent becomes highly viscous and easily gelled, the coating operation becomes difficult, and a sufficient pot life cannot be obtained. Therefore, when the hydrolyzate and polyvinyl alcohol are mixed, if the pH is higher than 3.5, a mineral acid such as hydrochloric acid or nitric acid or other acid may be added to stabilize the pot life, and the pH may be adjusted. Good.
分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物の部分中和物はガスバリア層に存在する固形分１００重量部に対して、分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物の部分中和物のカルボニル基が１．２〜１１．５ｍｏｌ／１００重量部、好ましくは１．７〜１０．３ｍｏｌ／１００重量部が好ましい。１．２ｍｏｌ／１００重量部未満だと十分なインキ接着性を得られず、１１．５ｍｏｌ／１００重量部以上だと充分なガスバリア性が発現しない。 The partially neutralized product of a compound in which at least one carboxyl group is bonded to each of two or more consecutive carbon atoms in the molecule is continuous in the molecule with respect to 100 parts by weight of the solid content present in the gas barrier layer. The carbonyl group of the partially neutralized product of the compound in which at least one carboxyl group is bonded to each of two or more carbon atoms is 1.2 to 11.5 mol / 100 parts by weight, preferably 1.7 to 10 .3 mol / 100 parts by weight is preferred. When the amount is less than 1.2 mol / 100 parts by weight, sufficient ink adhesion cannot be obtained, and when the amount is 11.5 mol / 100 parts by weight or more, sufficient gas barrier properties are not exhibited.
本発明における分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物としては、例えば、分子内に下記構造式で表される構造を含む化合物（１）が挙げられる。
（化１中のＲ１、Ｒ２、Ｒ３、Ｒ４はＯＨ、ＣＯＯＨ、ＣＨ２ＣＯＯＨのいずれかを示し、αは１以上の整数を示す。）
Examples of the compound in which at least one carboxyl group is bonded to each of two or more consecutive carbon atoms in the molecule of the present invention include, for example, a compound having a structure represented by the following structural formula in the molecule (1 ).
(R1, R2, R3, and R4 in Chemical Formula 1 represent OH, COOH, or CH 2 COOH, and α represents an integer of 1 or more.)
また、化合物（化１）は環状になっていてもよく、化合物（化１）の分子内の連続する２個の炭素原子が芳香環の一部を形成してもよい。また芳香環を有するものであってもよい。そのような場合には、構造式（化１）におけるＲの数が少なくなることもある。また、化合物（化１）のカルボキシル基のうち、２つのカルボキシル基の間で無水物構造が少なくとも１つ作られている化合物も、本発明においては、上記構造式で表される化合物（化１）と同様の効果を発現する。 Further, the compound (Chemical Formula 1) may be cyclic, and two consecutive carbon atoms in the molecule of the compound (Chemical Formula 1) may form a part of the aromatic ring. Moreover, you may have an aromatic ring. In such a case, the number of R in the structural formula (Formula 1) may be reduced. In addition, among the carboxyl groups of the compound (Chemical Formula 1), a compound in which at least one anhydride structure is formed between two carboxyl groups is also a compound represented by the above structural formula (Chemical Formula 1). ).
この様な化合物としては、高分子、オリゴマー、低分子化合物の何れでもよい。高分子やオリゴマーとしては、ポリマレイン酸やポリマレイン酸無水物、メチルビニルエーテル無水マレイン酸、イソブチレン無水マレイン酸およびこれらの共重合体が挙げられる。なお、これらの化合物を後述のようにコーティング剤として使用する場合には、粘度が低い方が取り扱いやすいため、数平均分子量が１０，０００未満であるオリゴマーが好ましい。また、低分子化合物としては、１，２，３−プロパントリカルボン酸、１，２，３，４−ブタンテトラカルボン酸、クエン酸、１，２，３−ベンゼントリカルボン酸、３−ブテン−１，２，３−トリカルボン酸、１，２，３，４−ブタンテトラカルボン酸、１，２，３，４−シクロペンタンテトラカルボン酸、テトラヒドロフラン−２，３，４，５−テトラカルボン酸、ベンゼンペンタカルボン酸、ベンゼンヘキサカルボン酸、１，２，３，４，５，６−シクロヘキサンヘキサカルボン酸、あるいはこれら化合物の無水物などが挙げられる。 Such a compound may be a polymer, an oligomer, or a low molecular compound. Examples of the polymer and oligomer include polymaleic acid, polymaleic anhydride, methyl vinyl ether maleic anhydride, isobutylene maleic anhydride, and copolymers thereof. In addition, when these compounds are used as a coating agent as will be described later, an oligomer having a number average molecular weight of less than 10,000 is preferable because a lower viscosity is easier to handle. Examples of the low molecular weight compound include 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, citric acid, 1,2,3-benzenetricarboxylic acid, 3-butene-1, 2,3-tricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, tetrahydrofuran-2,3,4,5-tetracarboxylic acid, benzenepenta Examples thereof include carboxylic acid, benzenehexacarboxylic acid, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid, and anhydrides of these compounds.
分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物の部分中和物としては、分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物のカルボキシル基をアルカリで部分的に中和することにより得ることができる。アルカリとしては、例えば、水酸化ナトリウム、水酸化リチウム、水酸化カリウム、アンモニア（アンモニア水を含む）などが挙げられる。部分中和物は、通常、分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物の水溶液にアルカリを添加することにより得ることができる。分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物とアルカリの量比を調節することにより、所望の中和度とすることができる。 As a partially neutralized product of a compound in which at least one carboxyl group is bonded to each of two or more consecutive carbon atoms in the molecule, at least 1 to each of two or more consecutive carbon atoms in the molecule. It can be obtained by partially neutralizing a carboxyl group of a compound to which a plurality of carboxyl groups are bonded with an alkali. Examples of the alkali include sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia (including ammonia water) and the like. The partially neutralized product can be usually obtained by adding an alkali to an aqueous solution of a compound in which at least one carboxyl group is bonded to each of two or more consecutive carbon atoms in the molecule. A desired degree of neutralization can be achieved by adjusting the amount ratio of the compound having at least one carboxyl group bonded to each of two or more consecutive carbon atoms in the molecule and the alkali.
分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物の部分中和物の中和度は、得られるフィルムの酸素ガスバリア性とインキ接着性の程度を基準として選択することが好ましい。この中和度が低いほど、得られるフィルムのインキ接着性の程度は改善されるが、中和度がある程度以上高くないと酸素ガスバリア性が低下する傾向を示す。中和度としては５〜４５％、好ましくは、１０〜３０％が好ましい。なお、中和度は、式：中和度（％）＝（Ｎ／Ｎ０ ）×１００と定義し、求めることができる。ここで、Ｎは分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物１ｇ中の中和されたカルボキシル基のモル数、Ｎ０ は部分中和する前の分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物１ｇ中のカルボキシル基のモル数である。 The degree of neutralization of a partially neutralized product of a compound in which at least one carboxyl group is bonded to each of two or more consecutive carbon atoms in the molecule is the degree of oxygen gas barrier property and ink adhesion of the resulting film. Is preferably selected on the basis of. The lower the degree of neutralization, the better the degree of ink adhesion of the resulting film, but the oxygen gas barrier property tends to decrease unless the degree of neutralization is higher than a certain level. The degree of neutralization is 5 to 45%, preferably 10 to 30%. The degree of neutralization can be determined by defining the formula: degree of neutralization (%) = (N / N0) × 100. Here, N is the number of moles of neutralized carboxyl groups in 1 g of compound in which at least one carboxyl group is bonded to each of two or more consecutive carbon atoms in the molecule, and N0 is partially neutralized. It is the number of moles of carboxyl groups in 1 g of compound in which at least one carboxyl group is bonded to each of two or more consecutive carbon atoms in the previous molecule.
本発明の接着層を形成する接着剤としては、汎用のものであれば問題ないが、好適には主剤にポリオール、硬化剤にポリイソシアナートを用いる２液型ポリウレタン樹脂接着剤がよりよい。 As an adhesive for forming the adhesive layer of the present invention, there is no problem as long as it is a general-purpose one, but a two-component polyurethane resin adhesive using a polyol as a main agent and a polyisocyanate as a curing agent is more preferable.
２液型ポリウレタン樹脂接着剤の主剤に用いられるポリオールは、その分子中にヒドロキシル基（ＯＨ）を２個以上有するポリオール化合物からなるものである。該ポリオールとしては、ポリエーテルポリオール類、ポリエステルポリオール類、ポリエステルポリカーボネートポリオール類、ポリカーボネートポリオール類が挙げられる。これらは混合して使用されてもよい。また、場合によってはシランカップリング剤等の添加剤を添加してもよい。 The polyol used as the main component of the two-component polyurethane resin adhesive is composed of a polyol compound having two or more hydroxyl groups (OH) in the molecule. Examples of the polyol include polyether polyols, polyester polyols, polyester polycarbonate polyols, and polycarbonate polyols. These may be used as a mixture. In some cases, an additive such as a silane coupling agent may be added.
２液型ポリウレタン樹脂接着剤の硬化剤に用いられるポリイソシアナートは、その分子中に２個以上のイソシアネート基（ＮＣＯ）を有する化合物からなるものである。例えば、トリレンジイソシアネート、トリフェニルメタンイソシアネート、テトラメチルキシレンジイソシアネートなどのモノマー類と、これらの重合体、誘導体などがある。 The polyisocyanate used as a curing agent for a two-component polyurethane resin adhesive is composed of a compound having two or more isocyanate groups (NCO) in the molecule. For example, there are monomers such as tolylene diisocyanate, triphenylmethane isocyanate, tetramethylxylene diisocyanate, and polymers and derivatives thereof.
本発明では、上記のようにして調製した接着剤、ガスバリアコート剤を、基材であるプラスチックフィルムの片面に順次塗布して乾燥し、接着層、ガスバリア層を形成する。 In the present invention, the adhesive and gas barrier coating agent prepared as described above are sequentially applied to one side of a plastic film as a substrate and dried to form an adhesive layer and a gas barrier layer.
プラスチックフィルムとしては、ポリエチレン、ポリプロピレンなどのポリオレフィン系樹脂；ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリエチレン−２，６−ナフタレート、ポリブチレンテレフタレートなどのポリエステル系樹脂；ポリオキシメチレンなどのポリエーテル系樹脂；ポリアミド−６、ポリアミド−６，６、ポリメタキシレンアジパミドなどのポリアミド系樹脂；ポリスチレン、ポリ（メタ）アクリル酸エステル、ポリアクリロニトリル、ポリ酢酸ビニルなどのビニル系樹脂；ポリカーボネート系樹脂；セルロースアセテートなどのセルロース系樹脂；ポリイミド；ポリエーテルイミド；ポリフェニレンスルフィド；ポリエーテルスルフォン；ポリスルフォン；ポリエーテルエーテルケトン；ポリエーテルケトンケトンなどの熱可塑性樹脂を主成分とする。これらの熱可塑性樹脂は単独重合体であっても共重合体であってもよい。なお、本発明に用いられるプラスチックフィルムは、上記熱可塑性樹脂に限定されることなく、セロファンに代表される非熱可塑性フィルムも用いることが出来る。本発明の基材とはこれらの樹脂をフィルム状に成型したものが用いられる。未延伸フィルムや一軸または二軸に延伸したものいずれも使用できるが、バリア層をコートするときのコートしやすさ、バリア材の強度の観点から延伸ポリアミドフィルム、延伸ポリプロピレンフィルム、もしくは延伸ポリエステルフィルムが最も好ましい。 Examples of the plastic film include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate and polybutylene terephthalate; polyether resins such as polyoxymethylene; polyamide- 6, polyamide-6,6, polyamide-based resin such as polymetaxylene adipamide; vinyl-based resin such as polystyrene, poly (meth) acrylic ester, polyacrylonitrile, polyvinyl acetate; polycarbonate-based resin; cellulose acetate, etc. Cellulosic resin; Polyimide; Polyetherimide; Polyphenylene sulfide; Polyethersulfone; Polysulfone; Polyetheretherketone; As a main component a thermoplastic resin such as Ketonketon. These thermoplastic resins may be a homopolymer or a copolymer. In addition, the plastic film used for this invention is not limited to the said thermoplastic resin, The non-thermoplastic film represented by the cellophane can also be used. As the base material of the present invention, those obtained by molding these resins into a film shape are used. Either an unstretched film or a uniaxially or biaxially stretched film can be used, but a stretched polyamide film, a stretched polypropylene film, or a stretched polyester film is used from the viewpoint of ease of coating when coating a barrier layer and the strength of the barrier material. Most preferred.
接着剤やガスバリアコート剤の塗布には、通常のコーティング法を用いることができる。例えば、リバースロールコーティング法、ディップコーティング法、メイヤーバーコーティング法、ナイフコート法、ノズルコーティング法、ダイコーティング法、スプレーコーティング法、カーテンコーティング法、スクリーン印刷、グラビアコート、などの各種印刷法などが挙げられる。また、これらを組み合わせてもよい。 A normal coating method can be used for application of the adhesive or the gas barrier coating agent. Examples include reverse roll coating, dip coating, Mayer bar coating, knife coating, nozzle coating, die coating, spray coating, curtain coating, screen printing, gravure coating, and other printing methods. It is done. Moreover, you may combine these.
乾燥後の接着層の厚みは、０．０１〜２．０ｇ／ｍ２、好ましくは０．１〜１ｇ／ｍ２が好ましい。乾燥後の厚みが０．０１ｇ／ｍ２未満であると、基材とバリア層との間で充分な接着強度を示さない。一方、乾燥後の厚みが２．０ｇ／ｍ２を超えると、多くの接着剤を要すためコストが高く、工業的に好ましくない。
乾燥後のガスバリア層厚みは、０．１〜３．０ｇ／ｍ２、好ましくは０．５〜１．５ｇ／ｍ２がよい。乾燥後の厚さが０．１ｇ／ｍ２未満であると、充分なガスバリア性が発現しない。一方、乾燥後のコート層厚さが３．０ｇ／ｍ２を超えると、クラックの発生や不十分な密着強度によって、ガスバリア性が低下するし、コストアップともなるので好ましくない。
The thickness of the adhesive layer after drying is preferably 0.01 to 2.0 g / m2, and more preferably 0.1 to 1 g / m2. When the thickness after drying is less than 0.01 g / m 2, sufficient adhesive strength between the substrate and the barrier layer is not exhibited. On the other hand, if the thickness after drying exceeds 2.0 g / m 2, a large amount of adhesive is required, which is expensive and industrially not preferable.
The thickness of the gas barrier layer after drying is 0.1 to 3.0 g / m2, preferably 0.5 to 1.5 g / m2. If the thickness after drying is less than 0.1 g / m 2, sufficient gas barrier properties are not exhibited. On the other hand, if the thickness of the coating layer after drying exceeds 3.0 g / m 2, the gas barrier property is lowered and the cost is increased due to the occurrence of cracks and insufficient adhesion strength.
塗布後、ガスバリア層の乾燥およびエージングを行い、高湿度下においても高いガスバリア性を有するガスバリア層を形成させる。乾燥は、ドライヤー内温度２００℃以下、好ましくは１００〜１５０℃で１〜３０秒行う。２００℃より高い温度で乾燥した場合、急激な溶媒の揮発によりバリア層に微細なボイドが形成され、ガスバリア性が低下する。乾燥時間が３０秒より長い場合は、塗膜の体積収縮が著しくなりその結果塗膜にクラックが発生する。 After the application, the gas barrier layer is dried and aged to form a gas barrier layer having high gas barrier properties even under high humidity. Drying is performed at a dryer internal temperature of 200 ° C. or lower, preferably 100 to 150 ° C. for 1 to 30 seconds. When dried at a temperature higher than 200 ° C., fine voids are formed in the barrier layer due to rapid volatilization of the solvent, and the gas barrier properties deteriorate. When the drying time is longer than 30 seconds, the volumetric shrinkage of the coating film becomes significant, and as a result, cracks occur in the coating film.
乾燥後、エージングは、雰囲気温度２０〜８０℃で８時間以上実施される。８０℃よりも高いとプラスチックフィルムからなる基材の平面性が損なわれ、印刷適性等の加工適性が悪くなるので好ましくない。また２０℃より低い場合、十分なエージング効果が得られない。 After drying, aging is performed at an ambient temperature of 20 to 80 ° C. for 8 hours or more. When the temperature is higher than 80 ° C., the flatness of the base material made of a plastic film is impaired, and processing suitability such as printability is deteriorated. Moreover, when it is lower than 20 ° C., a sufficient aging effect cannot be obtained.
上記の方法により得られたガスバリア性のフィルム積層体は、ＪＩＳ Ｐ ８１３４で測定した衝撃強度が１０．０ｋｇｆ・ｃｍ以上となる。米袋のような重量物や水物袋など特に耐衝撃性を要する包装袋に用いるフィルムでは、その包装袋製造工程、輸送工程での破袋する確率を低減させるために１０ｋｇｆ・ｃｍ以上が必要であるとされている。
また、上記の方法により得られたガスバリア性のフィルム積層体は、２３℃、９０％ＲＨの条件下でＪＩＳ Ｋ７１２６（等圧法）に基づき測定した酸素透過度が１０ｃｃ／ｍ２ ・ａｔｍ・２４ｈ以下である。一般的に酸素バリア性が必要とされている食品包装では酸素透過度２０ｃｃ／ｍ２・ａｔｍ・２４ｈ以下が必要とされている。
The gas barrier film laminate obtained by the above method has an impact strength measured by JIS P 8134 of 10.0 kgf · cm or more. Films used for packaging bags that require impact resistance, such as heavy bags such as rice bags and water bags, require 10 kgf · cm or more in order to reduce the probability of breakage in the packaging bag manufacturing process and transportation process. It is said that there is.
The gas barrier film laminate obtained by the above method has an oxygen permeability of 10 cc / m 2 · atm · 24 h or less measured under JIS K7126 (isobaric method) under the conditions of 23 ° C. and 90% RH. is there. In general, a food packaging that requires oxygen barrier properties requires an oxygen permeability of 20 cc / m 2 · atm · 24 h or less.
実施例および比較例を用いて、本発明の有用性について具体的に説明する。なお、各物性の測定に用いた装置および条件は以下の通りである。 The usefulness of the present invention will be specifically described using examples and comparative examples. In addition, the apparatus and conditions used for the measurement of each physical property are as follows.
＜酸素透過度測定＞
イリノイ社製酸素透過度測定装置ｍｏｄｅｌ８０００を用いた。測定に際しては、前処理として２４時間水中で浸漬処理を行い水滴を拭き取った後、直ちに２０℃―９０％ＲＨで酸素透過度の測定を行った。
＜インキ接着性評価方法＞
ザーンカップ＃３で１７．００〜１７．５０秒になるようにインキ（東洋インキ製造株式会社製、ファインスターＲ６４１ＡＴ白）を希釈剤（東洋インキ製造株式会社製、ＮＴ６０２−Ｓ０２）で希釈し、乾燥後の塗布量がｇ／ｍ２になるようにコートした。乾燥は乾燥機温度１００℃で３０秒行った。
乾燥後、７５℃の水浴で蒸気にインキ面を３０秒曝し、すぐにセロハンテープ（ニチバン株式会社製、１５ｍｍ幅）を１０ｃｍ貼り付け、空気が抜けるまで擦った。
その後、勢いよくセロハンテープを剥し、インキの剥離量が３０％以上を×、未満を○として評価を行った。
インキの剥離量が３０％未満のコートフィルムで印刷を行った場合、フリーロールにインキがとられる等の問題が起きることはない。
<Oxygen permeability measurement>
An oxygen permeability measuring apparatus model 8000 manufactured by Illinois was used. In the measurement, immersion treatment was carried out in water for 24 hours as a pretreatment to wipe off water droplets, and oxygen permeability was immediately measured at 20 ° C.-90% RH.
<Ink adhesion evaluation method>
The ink (Toyo Ink Manufacturing Co., Ltd., Finestar R641AT White) is diluted with a diluent (Toyo Ink Manufacturing Co., Ltd., NT602-S02) so that it becomes 17.00 to 17.50 seconds in Zaan Cup # 3. Coating was performed so that the coating amount after drying was g / m 2. Drying was performed at a dryer temperature of 100 ° C. for 30 seconds.
After drying, the ink surface was exposed to steam in a 75 ° C. water bath for 30 seconds, and 10 cm of cellophane tape (manufactured by Nichiban Co., Ltd., 15 mm width) was immediately applied and rubbed until the air escaped.
Thereafter, the cellophane tape was peeled off vigorously, and the evaluation was performed with an ink peeling amount of 30% or more as x and a lower value as ○.
When printing is performed with a coat film having an ink peeling amount of less than 30%, there is no problem that ink is taken on the free roll.
＜調液＞
分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている化合物の調液は以下のように行った。
・ポリマレイン酸０％中和物
ノンポール（日油株式会社製、ＰＭＡ−５０Ｗ濃度５０％）１０重量部を６１．４３重量部の純水に溶解し、７重量％のポリマレイン酸０％中和物を得た
・ポリマレイン酸１０％中和物
ノンポール（日油株式会社製、ＰＭＡ−５０Ｗ濃度５０％）１０重量部を５７．９８重量部の純水に溶解し、水酸化ナトリウム水溶液（濃度１０％）３．４５重量部を添加して７重量％のポリマレイン酸１０％中和物を得た。
・ポリマレイン酸３０％中和物
ノンポール（日油株式会社製、ＰＭＡ−５０Ｗ濃度５０％）１０重量部を５１．０９重量部の純水に溶解し、水酸化ナトリウム水溶液（濃度１０％）１０．３４重量部を添加して７重量％のポリマレイン酸３０％中和物を得た。
・ポリマレイン酸５０％中和物
ノンポール（日油株式会社製、ＰＭＡ−５０Ｗ濃度５０％）１０重量部を４４．２０重量部の純水に溶解し、水酸化ナトリウム水溶液（濃度１０％）１７．２３重量部を添加して７重量％のポリマレイン酸５０％中和物を得た。
・１，２，３，４―ブタンテトラカルボン酸０％中和物
１，２，３，４−ブタンテトラカルボン酸（和光純薬株式会社製、濃度９８％）５重量部を６５．０重量部の純水に溶解し、７重量％の１，２，３，４−ブタンテトラカルボン酸０％中和物を得た
・１，２，３，４―ブタンテトラカルボン酸１０％中和物
１，２，３，４−ブタンテトラカルボン酸（和光純薬株式会社製、濃度９８％）５重量部を６１．６５重量部の純水に溶解し、水酸化ナトリウム水溶液（濃度１０％）３．３５重量部を添加して７重量％の１，２，３，４−ブタンテトラカルボン酸１０％中和物を得た。
・１，２，３，４―ブタンテトラカルボン酸３０％中和物
１，２，３，４−ブタンテトラカルボン酸（和光純薬株式会社製、濃度９８％）５重量部を５４．９６重量部の純水に溶解し、水酸化ナトリウム水溶液（濃度１０％）１０．０４重量部を添加して７重量％の１，２，３，４−ブタンテトラカルボン酸３０％中和物を得た。
・１，２，３，４―ブタンテトラカルボン酸５０％中和物
１，２，３，４−ブタンテトラカルボン酸（和光純薬株式会社製、濃度９８％）５重量部を４８．２６重量部の純水に溶解し、水酸化ナトリウム水溶液（濃度１０％）１６．７４重量部を添加して７重量％の１，２，３，４−ブタンテトラカルボン酸５０％中和物を得た。
・メチルビニルエーテル無水マレイン酸１０％中和物
ＧＡＮＴＲＥＺ ＡＮ−１１９（アイエスピー・ジャパン株式会社製、濃度９８％以上）５重量部を６１．６５重量部の純水に溶解し、水酸化ナトリウム水溶液（濃度１０％）３．３５重量部を添加して７重量％のメチルビニルエーテル無水マレイン酸１０％中和物を得た。
・ポリアクリル酸０％中和物
ＡＣ−１０Ｓ（日本純薬株式会社製、濃度４０．２％）１０重量部を４７．４３重量部の純水に溶解し、７重量％のポリアクリル酸０％中和物を得た。
・ポリアクリル酸１０％中和物
ＡＣ−１０Ｓ（日本純薬株式会社製、濃度４０．２％）１０重量部を４５．２重量部の純水に溶解し、水酸化ナトリウム水溶液（濃度１０％）２．２３重量部を添加して７重量％のポリアクリル酸１０％中和物を得た。
<Preparation>
Preparation of a compound in which at least one carboxyl group was bonded to each of two or more consecutive carbon atoms in the molecule was performed as follows.
-10 parts by weight of polymaleic acid 0% neutralized non-pol (manufactured by NOF Corporation, PMA-50W concentration 50%) dissolved in 61.43 parts by weight of pure water, 7% by weight of polymaleic acid 0% neutralized product -10 parts by weight of polymaleic acid 10% neutralized nonpol (manufactured by NOF Corporation, PMA-50W concentration 50%) was dissolved in 57.98 parts by weight of pure water, and an aqueous sodium hydroxide solution (concentration 10%) ) 3.45 parts by weight were added to obtain a 7% polymaleic acid 10% neutralized product.
-10 parts by weight of polymaleic acid 30% neutralized nonpol (manufactured by NOF Corporation, PMA-50W concentration 50%) is dissolved in 51.09 parts by weight of pure water, and an aqueous sodium hydroxide solution (concentration 10%) 34 parts by weight was added to obtain a 7% by weight neutralized product of 30% polymaleic acid.
-10 parts by weight of polymaleic acid 50% neutralized nonpol (manufactured by NOF Corporation, PMA-50W concentration 50%) is dissolved in 44.20 parts by weight of pure water, and an aqueous sodium hydroxide solution (concentration 10%) 17. 23 parts by weight was added to obtain a 50% neutralized product of 7% by weight of polymaleic acid.
6% by weight of 5 parts by weight of 1,2,3,4-butanetetracarboxylic acid 0% neutralized 1,2,3,4-butanetetracarboxylic acid (Wako Pure Chemical Industries, Ltd., concentration 98%) 7% by weight of 1,2,3,4-butanetetracarboxylic acid 0% neutralized product was dissolved in 1 part of pure water. 1,2,3,4-butanetetracarboxylic acid 10% neutralized product 5 parts by weight of 1,2,3,4-butanetetracarboxylic acid (manufactured by Wako Pure Chemical Industries, Ltd., concentration 98%) is dissolved in 61.65 parts by weight of pure water, and an aqueous sodium hydroxide solution (concentration 10%) 3 .35 parts by weight were added to obtain a 10% neutralized product of 7% by weight of 1,2,3,4-butanetetracarboxylic acid.
54.96 parts by weight of 5 parts by weight of 1,2,3,4-butanetetracarboxylic acid 30% neutralized 1,2,3,4-butanetetracarboxylic acid (Wako Pure Chemical Industries, Ltd., concentration 98%) 10 parts by weight of a sodium hydroxide aqueous solution (concentration: 10%) was added to obtain 7% by weight of 1,2,3,4-butanetetracarboxylic acid 30% neutralized product. .
48% by weight of 5 parts by weight of 1,2,3,4-butanetetracarboxylic acid 50% neutralized product 1,2,3,4-butanetetracarboxylic acid (Wako Pure Chemical Industries, Ltd., concentration 98%) 1 part of pure water was dissolved, and 16.74 parts by weight of aqueous sodium hydroxide solution (concentration 10%) was added to obtain 7% by weight of 1,2,3,4-butanetetracarboxylic acid 50% neutralized product. .
-5 parts by weight of methyl vinyl ether maleic anhydride 10% neutralized product GANTREZ AN-119 (manufactured by IPS Japan Co., Ltd., concentration 98% or more) was dissolved in 61.65 parts by weight of pure water, (Concentration 10%) 3.35 parts by weight were added to obtain a 10% neutralized product of 7% by weight of methyl vinyl ether maleic anhydride.
-10% by weight of polyacrylic acid 0% neutralized product AC-10S (manufactured by Nippon Pure Chemical Co., Ltd., concentration 40.2%) was dissolved in 47.43 parts by weight of pure water, and 7% by weight of polyacrylic acid 0 % Neutralized product was obtained.
-10 parts by weight of 10% polyacrylic acid neutralized product AC-10S (Nippon Pure Chemicals Co., Ltd., concentration: 40.2%) was dissolved in 45.2 parts by weight of pure water, and an aqueous sodium hydroxide solution (concentration: 10%) ) 2.23 parts by weight were added to obtain a 10% neutralized product of 7% polyacrylic acid.
＜実施例１＞
エチルシリケート４０（コルコート社製 ＳｉＯ２ 分４０％）に対して１００重量部の純水および５０重量部のイソプロパノールを加え、０．８３重量部の６Ｍ塩酸を混合した後、撹拌しながら５３℃で２００分間加水分解を行った。この溶液を冷却後、該加水分解液と同重量の純水を添加し、珪素酸化物が８重量％の透明な溶液を得た。一方、ポリビニルアルコール（クラレ社製、ＰＶＡ−１１７、ケン化度９８−９９％、平均重合度１７００）１４重量部を２８６重量部の純水に溶解し、７重量％の水溶液を得た。珪素酸化物の固形分と、ポリビニルアルコールの固形分の重量とポリマレイン酸１０％中和物の固形分が５８．４：４０．６：１．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液８９．６７重量部とポリマレイン酸１０％中和物１．９６重量部と純水４．０４重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．９であった。
<Example 1>
100 parts by weight of pure water and 50 parts by weight of isopropanol were added to ethyl silicate 40 (SiO2 40% by Colcoat Co.), and 0.83 parts by weight of 6M hydrochloric acid was mixed. Hydrolysis was performed for minutes. After cooling this solution, pure water having the same weight as that of the hydrolyzed solution was added to obtain a transparent solution containing 8% by weight of silicon oxide. On the other hand, 14 parts by weight of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-117, degree of saponification 98-99%, average degree of polymerization 1700) was dissolved in 286 parts by weight of pure water to obtain a 7% by weight aqueous solution. 100 parts by weight of hydrolyzate so that the solid content of silicon oxide, the solid content of polyvinyl alcohol, and the solid content of 10% neutralized polymaleic acid were 58.4: 40.6: 1.0. On the other hand, 89.67 parts by weight of an aqueous polyvinyl alcohol solution, 1.96 parts by weight of a 10% polymaleic acid neutralized product and 4.04 parts by weight of pure water were mixed at room temperature with stirring to obtain a uniform solution, and a solid content concentration of 7 A weight percent gas barrier coating agent was obtained. The coating agent pH at this time was about 2.9.
２液型ポリウレタン樹脂接着剤の主剤としてポリエステルポリオール（東洋モートン社製、ＡＤ−５０３）１００重量部に対して、硬化剤としてポリイソシアネート（東洋モートン社製、ＣＡＴ−６０）４６．７重量部、溶剤として酢酸エチル６２７重量部、トルエン６２７重量部を室温で撹拌しながら混合し、均一な溶液として接着剤を得た。この接着剤は、固形分濃度５重量％であった。 46.7 parts by weight of a polyisocyanate (Toyo Morton, CAT-60) as a curing agent with respect to 100 parts by weight of a polyester polyol (Toyo Morton, AD-503) as a main component of a two-component polyurethane resin adhesive, As a solvent, 627 parts by weight of ethyl acetate and 627 parts by weight of toluene were mixed with stirring at room temperature to obtain an adhesive as a uniform solution. This adhesive had a solid content concentration of 5% by weight.
調製した接着剤を延伸ナイロンフィルム（興人製二軸延伸ポリアミドフィルム「ボニール」、厚み１５μｍ）上にメイヤーバーで塗布し、２秒後に１００℃の熱風乾燥機中で１５秒乾燥した。このときの接着層の塗布量は約０．２ｇ／ｍ２ であった。
さらにその上から同様の塗布方法で、調製したガスバリアコート剤を塗布し、１００℃、１５秒乾燥した。このときのガスバリア層の塗布量は約１ｇ／ｍ２ であった。
The prepared adhesive was applied onto a stretched nylon film (Kohjin biaxially stretched polyamide film “Bonyl”, thickness 15 μm) with a Mayer bar, and after 2 seconds, dried in a hot air dryer at 100 ° C. for 15 seconds. The coating amount of the adhesive layer at this time was about 0.2 g / m2.
Further, the prepared gas barrier coating agent was applied from above by the same coating method, and dried at 100 ° C. for 15 seconds. The coating amount of the gas barrier layer at this time was about 1 g / m2.
得られたフィルム積層体を一旦室温に戻した後、５５℃で９６時間エージングし、ガスバリア性フィルムを得た。酸素透過度、インキ接着性の評価を行った結果を表１に示す。 The obtained film laminate was once returned to room temperature and then aged at 55 ° C. for 96 hours to obtain a gas barrier film. Table 1 shows the results of evaluation of oxygen permeability and ink adhesion.
＜実施例２＞
ポリマレイン酸１０％中和物の添加量を６％に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分とポリマレイン酸１０％中和物の固形分比率が５５．５：３８．５：６．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部とポリマレイン酸１０％中和物１２．３６重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．７であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Example 2>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the amount of polymaleic acid 10% neutralized product was changed to 6%. The obtained gas barrier coating agent was added so that the solid content ratio of the silicon oxide solid content, the solid content of polyvinyl alcohol and the 10% neutralized product of polymaleic acid was 55.5: 38.5: 6.0. A homogeneous solution obtained by mixing 79.42 parts by weight of a polyvinyl alcohol aqueous solution, 12.36 parts by weight of a 10% polymaleic acid neutralized product, and 14.29 parts by weight of pure water with stirring at room temperature with respect to 100 parts by weight of the decomposition solution. As a result, a gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.7. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜実施例３＞
ポリマレイン酸１０％中和物をポリマレイン酸３０％中和物に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分とポリマレイン酸３０％中和物の固形分比率が５８．４：４０．６：１．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液８９．６７重量部とポリマレイン酸３０％中和物１．９６重量部と純水４．０４重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．９であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Example 3>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the 10% neutralized product of polymaleic acid was changed to a 30% neutralized product of polymaleic acid. The gas barrier coating agent thus obtained was hydrolyzed so that the solid content of the silicon oxide, the solid content of the polyvinyl alcohol and the 30% neutralized polymaleic acid was 58.4: 40.6: 1.0. To 100 parts by weight of the decomposition solution, 89.67 parts by weight of a polyvinyl alcohol aqueous solution, 1.96 parts by weight of a polymaleic acid 30% neutralized product and 4.04 parts by weight of pure water are mixed with stirring at room temperature to obtain a uniform solution. As a result, a gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.9. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜実施例４＞
ポリマレイン酸１０％中和物を１，２，３，４―ブタンテトラカルボン酸１０％中和物に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分と１，２，３，４―ブタンテトラカルボン酸１０％中和物の固形分比率が５８．４：４０．６：１．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部と１，２，３，４―ブタンテトラカルボン酸１０％中和物１．９６重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．８であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Example 4>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the 10% neutralized product of polymaleic acid was changed to a 10% neutralized product of 1,2,3,4-butanetetracarboxylic acid. The solid content ratio of the silicon oxide solid content, the polyvinyl alcohol solid content and the 1,2,3,4-butanetetracarboxylic acid 10% neutralized product of the obtained gas barrier coating agent was 58.4: 40.6. : 79.42 parts by weight of an aqueous polyvinyl alcohol solution and 1.96 parts by weight of a neutralized product of 10% 1,2,3,4-butanetetracarboxylic acid with respect to 100 parts by weight of the hydrolyzed solution And 14.29 parts by weight of pure water were mixed with stirring at room temperature to obtain a uniform solution, whereby a gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.8. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜実施例５＞
ポリマレイン酸１０％中和物を１，２，３，４―ブタンテトラカルボン酸１０％中和物に変更し、添加量を６％に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分と１，２，３，４―ブタンテトラカルボン酸１０％中和物の固形分比率が５５．５：３８．５：６．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部と１，２，３，４―ブタンテトラカルボン酸１０％中和物１２．３６重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．８であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Example 5>
A gas barrier coating agent was prepared in the same manner as in Example 1 except that 10% neutralized product of polymaleic acid was changed to 10% neutralized product of 1,2,3,4-butanetetracarboxylic acid, and the addition amount was changed to 6%. Obtained. The solid content ratio of the solid content of silicon oxide, the solid content of polyvinyl alcohol and the 10% neutralized product of 1,2,3,4-butanetetracarboxylic acid in the obtained gas barrier coating agent was 55.5: 38.5. : 79.42 parts by weight of an aqueous polyvinyl alcohol solution and 12.36 parts by weight of a neutralized 10% 1,2,3,4-butanetetracarboxylic acid with respect to 100 parts by weight of the hydrolyzed solution so that 6.0 And 14.29 parts by weight of pure water were mixed with stirring at room temperature to obtain a uniform solution, whereby a gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.8. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜実施例６＞
ポリマレイン酸１０％中和物を１，２，３，４―ブタンテトラカルボン酸３０％中和物に変更し、添加量を６％に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分と１，２，３，４―ブタンテトラカルボン酸３０％中和物の固形分比率が５５．５：３８．５：６．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部と１，２，３，４―ブタンテトラカルボン酸３０％中和物１２．３６重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．９であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Example 6>
A gas barrier coating agent was prepared in the same manner as in Example 1 except that 10% neutralized product of polymaleic acid was changed to 30% neutralized product of 1,2,3,4-butanetetracarboxylic acid and the addition amount was changed to 6%. Obtained. The solid content ratio of the silicon oxide solid content of the obtained gas barrier coating agent, the solid content of polyvinyl alcohol and the 1,2,3,4-butanetetracarboxylic acid 30% neutralized product was 55.5: 38.5. : 79.42 parts by weight of an aqueous polyvinyl alcohol solution and 12.36 parts by weight of a neutralized 30% 1,2,3,4-butanetetracarboxylic acid with respect to 100 parts by weight of the hydrolyzed solution so that 6.0 is obtained. And 14.29 parts by weight of pure water were mixed with stirring at room temperature to obtain a uniform solution, whereby a gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.9. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜実施例７＞
ポリマレイン酸１０％中和物をメチルビニルエーテル無水マレイン酸１０％中和物に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分とメチルビニルエーテル無水マレイン酸１０％中和物の固形分比率が５８．４：４０．６：１．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部とメチルビニルエーテル無水マレイン酸１０％中和物１．９６重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．７であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Example 7>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the polymaleic acid 10% neutralized product was changed to methyl vinyl ether maleic anhydride 10% neutralized product. The solid content ratio of the silicon oxide solid content of the obtained gas barrier coating agent, the solid content of polyvinyl alcohol, and the 10% neutralized product of methyl vinyl ether maleic anhydride is 58.4: 40.6: 1.0. Further, 79.42 parts by weight of an aqueous polyvinyl alcohol solution, 1.96 parts by weight of a 10% neutralized methyl vinyl ether maleic anhydride and 14.29 parts by weight of pure water were stirred at room temperature with respect to 100 parts by weight of the hydrolyzed solution. A gas barrier coating agent having a solid concentration of 7% by weight was obtained by mixing to obtain a uniform solution. The coating agent pH at this time was about 2.7. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜比較例１＞
ポリマレイン酸１０％中和物を使用しなかった以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化の固形分と、ポリビニルアルコールの固形分比率が５９：４１となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４重量部と純水１４．３重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．９であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Comparative Example 1>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that 10% neutralized polymaleic acid was not used. 79.4 parts by weight of polyvinyl alcohol aqueous solution and pure water with respect to 100 parts by weight of the hydrolyzate so that the solid content ratio of silicon oxide and polyvinyl alcohol in the obtained gas barrier coating agent is 59:41. 14.3 parts by weight was mixed with stirring at room temperature to obtain a uniform solution, thereby obtaining a gas barrier coating agent having a solid content concentration of 7% by weight. The coating agent pH at this time was about 2.9. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜比較例２＞
ポリマレイン酸１０％中和物をポリマレイン酸０％中和物に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分とポリマレイン酸０％中和物の固形分比率が５８．４：４０．６：１．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液８９．６７重量部とポリマレイン酸０％中和物１．９６重量部と純水４．０４重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．９であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Comparative example 2>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the 10% neutralized product of polymaleic acid was changed to a 0% neutralized product of polymaleic acid. The obtained gas barrier coating agent was added so that the solid content of silicon oxide, the solid content of polyvinyl alcohol, and the solid content of 0% neutralized polymaleic acid was 58.4: 40.6: 1.0. To 100 parts by weight of the decomposition solution, 89.67 parts by weight of a polyvinyl alcohol aqueous solution, 1.96 parts by weight of a polymaleic acid 0% neutralized product and 4.04 parts by weight of pure water are mixed at room temperature with stirring to obtain a uniform solution. As a result, a gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.9. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜比較例３＞
ポリマレイン酸１０％中和物の添加量を７％に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分とポリマレイン酸１０％中和物の固形分比率が５４．９：３８．１：７．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部とポリマレイン酸１０％中和物１４．５８重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．９であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Comparative Example 3>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the amount of polymaleic acid 10% neutralized product was changed to 7%. The gas barrier coating agent thus obtained was hydrolyzed so that the solid content ratio of the solid content of silicon oxide, the solid content of polyvinyl alcohol and the 10% neutralized product of polymaleic acid was 54.9: 38.1: 7.0. A homogeneous solution obtained by mixing 79.42 parts by weight of a polyvinyl alcohol aqueous solution, 14.58 parts by weight of a 10% polymaleic acid neutralized product, and 14.29 parts by weight of pure water with stirring at room temperature with respect to 100 parts by weight of the decomposition solution. As a result, a gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.9. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜比較例４＞
ポリマレイン酸１０％中和物をポリマレイン酸５０％中和物に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分とポリマレイン酸５０％中和物の固形分比率が５８．４：４０．６：１．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液８９．６７重量部とポリマレイン酸５０％中和物１．９６重量部と純水４．０４重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．７であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Comparative example 4>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the 10% neutralized product of polymaleic acid was changed to a 50% neutralized product of polymaleic acid. The obtained gas barrier coating agent was added so that the solid content ratio of the silicon oxide solid content, the solid content of polyvinyl alcohol and the 50% neutralized product of polymaleic acid was 58.4: 40.6: 1.0. To 100 parts by weight of the decomposition solution, 89.67 parts by weight of a polyvinyl alcohol aqueous solution, 1.96 parts by weight of a polymaleic acid 50% neutralized product and 4.04 parts by weight of pure water are mixed at room temperature with stirring to obtain a uniform solution. As a result, a gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.7. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜比較例５＞
ポリマレイン酸１０％中和物を１，２，３，４―ブタンテトラカルボン酸０％中和物に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分と１，２，３，４―ブタンテトラカルボン酸０％中和物の固形分比率が５８．４：４０．６：１．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部と１，２，３，４―ブタンテトラカルボン酸０％中和物１．９６重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．８であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Comparative Example 5>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the 10% neutralized product of polymaleic acid was changed to a 0% neutralized product of 1,2,3,4-butanetetracarboxylic acid. The solid content ratio of the silicon oxide solid content, the polyvinyl alcohol solid content, and the 1,2,3,4-butanetetracarboxylic acid 0% neutralized product in the obtained gas barrier coating agent was 58.4: 40.6. : 79.42 parts by weight of an aqueous polyvinyl alcohol solution and 1.96 parts by weight of a 1,2,3,4-butanetetracarboxylic acid 0% neutralized product with respect to 100 parts by weight of the hydrolyzed solution And 14.29 parts by weight of pure water were mixed with stirring at room temperature to obtain a uniform solution, whereby a gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.8. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜比較例６＞
ポリマレイン酸１０％中和物を１，２，３，４―ブタンテトラカルボン酸５０％中和物に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分と１，２，３，４―ブタンテトラカルボン酸５０％中和物の固形分比率が５８．４：４０．６：１．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部と１，２，３，４―ブタンテトラカルボン酸５０％中和物１．９６重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．８であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Comparative Example 6>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the 10% neutralized product of polymaleic acid was changed to a 50% neutralized product of 1,2,3,4-butanetetracarboxylic acid. The solid content ratio of the silicon oxide solid content, the polyvinyl alcohol solid content, and the 1,2,3,4-butanetetracarboxylic acid 50% neutralized product in the obtained gas barrier coating agent was 58.4: 40.6. : 79.42 parts by weight of a polyvinyl alcohol aqueous solution and 1.96 parts by weight of a 1,2,3,4-butanetetracarboxylic acid 50% neutralized product with respect to 100 parts by weight of the hydrolyzed solution. And 14.29 parts by weight of pure water were mixed with stirring at room temperature to obtain a uniform solution, whereby a gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.8. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜比較例７＞
ポリマレイン酸１０％中和物をポリアクリル酸０％中和物に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分とポリアクリル酸０％中和物の固形分比率が５８．４：４０．６：１．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部とポリアクリル酸０％中和物１．９６重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．９であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Comparative Example 7>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the polymaleic acid 10% neutralized product was changed to a polyacrylic acid 0% neutralized product. The solid content of silicon oxide of the obtained gas barrier coating agent, the solid content of polyvinyl alcohol, and the solid content of polyacrylic acid 0% neutralized product was 58.4: 40.6: 1.0. To 100 parts by weight of the hydrolyzed solution, 79.42 parts by weight of an aqueous polyvinyl alcohol solution, 1.96 parts by weight of a polyacrylic acid 0% neutralized product and 14.29 parts by weight of pure water are mixed at room temperature with stirring. A gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.9. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜比較例８＞
ポリマレイン酸１０％中和物をポリアクリル酸０％中和物に変更し、添加量を６％に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分とポリアクリル酸０％中和物の固形分比率が５５．５：３８．５：６．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部とポリアクリル酸０％中和物１２．３６重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．８であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Comparative Example 8>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the 10% neutralized product of polymaleic acid was changed to a 0% neutralized product of polyacrylic acid and the addition amount was changed to 6%. The solid content ratio of the silicon oxide solid content of the obtained gas barrier coating agent, the solid content of polyvinyl alcohol and the 0% neutralized product of polyacrylic acid was 55.5: 38.5: 6.0, To 100 parts by weight of the hydrolyzed solution, 79.42 parts by weight of an aqueous polyvinyl alcohol solution, 12.36 parts by weight of polyacrylic acid 0% neutralized product, and 14.29 parts by weight of pure water are mixed at room temperature with stirring. A gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.8. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜比較例９＞
ポリマレイン酸１０％中和物をポリアクリル酸１０％中和物に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分とポリアクリル酸１０％中和物の固形分比率が５８．４：４０．６：１．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部とポリアクリル酸１０％中和物１．９６重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．８であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Comparative Example 9>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the polymaleic acid 10% neutralized product was changed to a polyacrylic acid 10% neutralized product. The solid content ratio of silicon oxide in the obtained gas barrier coating agent, the solid content of polyvinyl alcohol and the 10% neutralized product of polyacrylic acid was 58.4: 40.6: 1.0. To 100 parts by weight of the hydrolyzed solution, 79.42 parts by weight of an aqueous polyvinyl alcohol solution, 1.96 parts by weight of a 10% neutralized polyacrylic acid and 14.29 parts by weight of pure water are mixed with stirring at room temperature. A gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.8. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜比較例１０＞
ポリマレイン酸１０％中和物をポリアクリル酸１０％中和物に変更し、添加量を６％に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分とポリアクリル酸１０％中和物の固形分比率が５５．５：３８．５：６．０となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部とポリアクリル酸１０％中和物１２．３６重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．９であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Comparative Example 10>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the polymaleic acid 10% neutralized product was changed to a polyacrylic acid 10% neutralized product and the addition amount was changed to 6%. The solid content of silicon oxide in the obtained gas barrier coating agent, the solid content of polyvinyl alcohol and the 10% neutralized product of polyacrylic acid was 55.5: 38.5: 6.0, To 100 parts by weight of the hydrolyzed solution, 79.42 parts by weight of a polyvinyl alcohol aqueous solution, 12.36 parts by weight of a 10% neutralized polyacrylic acid, and 14.29 parts by weight of pure water are mixed with stirring at room temperature. A gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.9. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
＜比較例１１＞
ポリマレイン酸１０％中和物をポリアクリル酸１０％中和物に変更し、添加量を７．４％に変更した以外は実施例１と同様にしてガスバリアコート剤を得た。得られたガスバリアコート剤の珪素酸化物の固形分と、ポリビニルアルコールの固形分とポリアクリル酸１０％中和物の固形分比率が５５．８：３６．８：７．４となるように、加水分解液１００重量部に対して、ポリビニルアルコール水溶液７９．４２重量部とポリアクリル酸１０％中和物１２．３６重量部と純水１４．２９重量部を室温で撹拌しながら混合して均一な溶液とし、固形分濃度７重量％のガスバリアコート剤を得た。このときのコート剤ｐＨは約２．９であった。得られたガスバリアコート剤を使用し実施例１同様にガスバリア性フィルムを作製し酸素透過度、インキ接着性の評価を行った結果を表１に示す。
<Comparative Example 11>
A gas barrier coating agent was obtained in the same manner as in Example 1 except that the polymaleic acid 10% neutralized product was changed to a polyacrylic acid 10% neutralized product and the addition amount was changed to 7.4%. The solid content ratio of the silicon oxide solid content of the obtained gas barrier coating agent, the solid content of polyvinyl alcohol, and the 10% neutralized product of polyacrylic acid was 55.8: 36.8: 7.4. To 100 parts by weight of the hydrolyzed solution, 79.42 parts by weight of a polyvinyl alcohol aqueous solution, 12.36 parts by weight of a 10% neutralized polyacrylic acid, and 14.29 parts by weight of pure water are mixed with stirring at room temperature. A gas barrier coating agent having a solid content concentration of 7% by weight was obtained. The coating agent pH at this time was about 2.9. Table 1 shows the results of using the obtained gas barrier coating agent to produce a gas barrier film in the same manner as in Example 1 and evaluating the oxygen permeability and ink adhesion.
本発明は以上の様に構成されており、ガスバリア性、特に酸素遮断性に優れ、かつ可撓性、透明性、耐湿性、耐薬品性、インキ接着性等に優れたガスバリア層を有する包装用材料を提供することができた。本発明の包装用材料は、あらゆる分野の包装用材料として利用可能である。 The present invention is configured as described above, and has excellent gas barrier properties, particularly oxygen barrier properties, and has a gas barrier layer excellent in flexibility, transparency, moisture resistance, chemical resistance, ink adhesion, and the like. Material could be provided. The packaging material of the present invention can be used as a packaging material in all fields.
Claims (5)
前記ガスバリアコート剤が、アルコキシシラン及び／又はアルコキシシラン重縮合物の加水分解物（Ａ）と、ポリビニルアルコール（アルコキシシラン及び／又はアルコキシシランの重縮合物の加水分解物から生成する珪素酸化物と、ポリビニルアルコールの重量比が５０／５０〜８０／２０）と下記一般式（１）を満たす、分子内の連続する２個以上の炭素原子のそれぞれに少なくとも１個のカルボキシル基が結合されている中和度１０〜３０％の中和物からなる、インキ接着性の良好なガスバリア性フィルム。
The gas barrier coating agent comprises an alkoxysilane and / or alkoxysilane polycondensate hydrolyzate (A), and polyvinyl alcohol (alkoxysilane and / or alkoxysilane polycondensate hydrolyzate generated from the hydrolyzate In addition, at least one carboxyl group is bonded to each of two or more consecutive carbon atoms in the molecule satisfying the following general formula (1), wherein the weight ratio of polyvinyl alcohol is 50/50 to 80/20). A gas barrier film having good ink adhesion and comprising a neutralized product having a neutralization degree of 10 to 30%.
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|---|---|---|---|---|
| JPH09193306A (en) * | 1996-01-23 | 1997-07-29 | Kureha Chem Ind Co Ltd | Laminated film and packaging bag for electronic part |
| JP2004010785A (en) * | 2002-06-07 | 2004-01-15 | Unitika Ltd | Gas barrier coating agent and film |
| WO2006126511A1 (en) * | 2005-05-24 | 2006-11-30 | Mitsui Chemicals, Inc. | Gas barrier composition, coating film, methods for producing those, and multilayer body |
| JP2006334990A (en) * | 2005-06-03 | 2006-12-14 | Kuraray Co Ltd | Oxygen-absorbing laminate and packaging material |
| WO2007034773A1 (en) * | 2005-09-20 | 2007-03-29 | Mitsubishi Plastics, Inc. | Laminated film having gas barrier characteristics |
| JP2007254602A (en) * | 2006-03-23 | 2007-10-04 | Kohjin Co Ltd | Gas barrier film |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09193306A (en) * | 1996-01-23 | 1997-07-29 | Kureha Chem Ind Co Ltd | Laminated film and packaging bag for electronic part |
| JP2004010785A (en) * | 2002-06-07 | 2004-01-15 | Unitika Ltd | Gas barrier coating agent and film |
| WO2006126511A1 (en) * | 2005-05-24 | 2006-11-30 | Mitsui Chemicals, Inc. | Gas barrier composition, coating film, methods for producing those, and multilayer body |
| JP2006334990A (en) * | 2005-06-03 | 2006-12-14 | Kuraray Co Ltd | Oxygen-absorbing laminate and packaging material |
| WO2007034773A1 (en) * | 2005-09-20 | 2007-03-29 | Mitsubishi Plastics, Inc. | Laminated film having gas barrier characteristics |
| JP2007254602A (en) * | 2006-03-23 | 2007-10-04 | Kohjin Co Ltd | Gas barrier film |
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