JP2008297527A - Barrier coating composition for lamination, and barrier composite film for lamination - Google Patents
Barrier coating composition for lamination, and barrier composite film for lamination Download PDFInfo
- Publication number
- JP2008297527A JP2008297527A JP2007148412A JP2007148412A JP2008297527A JP 2008297527 A JP2008297527 A JP 2008297527A JP 2007148412 A JP2007148412 A JP 2007148412A JP 2007148412 A JP2007148412 A JP 2007148412A JP 2008297527 A JP2008297527 A JP 2008297527A
- Authority
- JP
- Japan
- Prior art keywords
- barrier
- coating composition
- mass
- laminate
- barrier coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000004888 barrier function Effects 0.000 title claims abstract description 180
- 239000008199 coating composition Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000003475 lamination Methods 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 43
- 150000002978 peroxides Chemical class 0.000 claims abstract description 21
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 14
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 13
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000010030 laminating Methods 0.000 claims description 39
- 238000007639 printing Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 22
- AZOOXWWPWARTFV-UHFFFAOYSA-N zirconium hydrochloride Chemical compound Cl.[Zr] AZOOXWWPWARTFV-UHFFFAOYSA-N 0.000 claims description 12
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- 239000011253 protective coating Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 57
- 239000010410 layer Substances 0.000 description 73
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 54
- 238000003756 stirring Methods 0.000 description 41
- 239000006185 dispersion Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 34
- 239000007787 solid Substances 0.000 description 30
- 239000012046 mixed solvent Substances 0.000 description 28
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 27
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- 238000004806 packaging method and process Methods 0.000 description 24
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 22
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 22
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- 238000000034 method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
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- -1 zirconia compound Chemical class 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 12
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
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- 229920000642 polymer Polymers 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
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- 229920005749 polyurethane resin Polymers 0.000 description 7
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 5
- 239000005001 laminate film Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012775 heat-sealing material Substances 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000012939 laminating adhesive Substances 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 102000016938 Catalase Human genes 0.000 description 2
- 108010053835 Catalase Proteins 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- JSIVLBGUDVQDHZ-UHFFFAOYSA-J [Cl-].[Cl-].[Cl-].O[Zr+3] Chemical compound [Cl-].[Cl-].[Cl-].O[Zr+3] JSIVLBGUDVQDHZ-UHFFFAOYSA-J 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 229910052621 halloysite Inorganic materials 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
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- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- ZKEUVTROUPQVTM-UHFFFAOYSA-N 1-pentylperoxypentane Chemical compound CCCCCOOCCCCC ZKEUVTROUPQVTM-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- LYPJRFIBDHNQLY-UHFFFAOYSA-J 2-hydroxypropanoate;zirconium(4+) Chemical compound [Zr+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O LYPJRFIBDHNQLY-UHFFFAOYSA-J 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
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- 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 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 230000000844 anti-bacterial effect Effects 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 239000010445 mica Substances 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
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- QRTRRDMHGTZPBF-UHFFFAOYSA-L oxygen(2-);zirconium(4+);sulfate Chemical compound [O-2].[Zr+4].[O-]S([O-])(=O)=O QRTRRDMHGTZPBF-UHFFFAOYSA-L 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
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- 239000002985 plastic film Substances 0.000 description 1
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Abstract
Description
本発明は、優れたガスバリア性及びラミネート適性を有するラミネート用バリア性コーティング組成物、及び、その組成物から得られるバリア層を中間層として含むラミネート用バリア性複合フィルムに関するものである。 The present invention relates to a laminating barrier coating composition having excellent gas barrier properties and laminating properties, and to a laminating barrier composite film comprising a barrier layer obtained from the composition as an intermediate layer.
食品包装用途で利用される包装袋は、印刷による内容物表示や装飾の機能が求められ、更に、高い食品衛生性を得るという目的から、印刷層が食品や人の指等に直接触れる事がないよう、印刷層を覆うヒートシール層が積層された複合ラミネートフィルムが利用されている。また、このような複合ラミネートフィルムに熱水処理ができる機能を持たせて、袋ごと内容物の調理も簡単にできる包装袋が製造される場合が多くなっている。 Packaging bags used in food packaging applications are required to display the contents and decorate by printing, and for the purpose of obtaining high food hygiene, the printed layer may be in direct contact with food or human fingers. A composite laminate film in which a heat seal layer covering the printing layer is laminated is used so that there is no such problem. In addition, there are many cases where such a composite laminate film is provided with a function capable of performing hot water treatment to produce a packaging bag that can easily cook the contents of the entire bag.
熱水処理は、殺菌効果が高く、包装袋が完全密封されている事から、内容物の腐敗を起こしにくいという点で、長期保存に有効な手段である。しかし、ガスバリア性が充分でないと、保存の間に酸素が包装袋の中に入り込み、内容物の変質・劣化が起こる。従って、熱水処理用包装袋において、いかに酸素等の透過を抑えられるかが、包装袋の価値を決める大きな要因となる。 The hot water treatment is an effective means for long-term storage in that the sterilization effect is high and the packaging bag is completely sealed, so that the contents are not easily spoiled. However, if the gas barrier property is not sufficient, oxygen enters the packaging bag during storage, and the contents are deteriorated and deteriorated. Therefore, how to suppress permeation of oxygen or the like in the hot water treatment packaging bag is a major factor that determines the value of the packaging bag.
従来、食品、医療等の包装用途に使用される包装袋では、酸素や水蒸気等のガスを遮断するために、種々のガスバリア層を設ける方法が考えられている。とりわけ、高いガスバリア性を有する材料として利用されてきたのは、印刷基材フィルム等に蒸着方式により積層される金属（例えば、特許文献１参照）や金属酸化物（例えば、特許文献２参照）である。そして、上記の熱水処理用包装袋においても、長期保存用には、アルミニウム蒸着フィルムやアルミ自体の箔をラミネートした熱水処理用包装袋が主流になっている。しかしながら、これらの材料を利用した複合ラミネートフィルムは総じて高価である。また、透明性が要求される分野で利用できないという問題を有している。 2. Description of the Related Art Conventionally, in packaging bags used for packaging applications such as food and medicine, various gas barrier layers have been considered in order to block gases such as oxygen and water vapor. In particular, metals that have been used as materials having a high gas barrier property are metals (for example, see Patent Document 1) and metal oxides (for example, see Patent Document 2) that are laminated on a printing substrate film or the like by a vapor deposition method. is there. And also in the said hot water treatment packaging bag, the hot water treatment packaging bag which laminated | stacked the aluminum vapor deposition film and the foil of aluminum itself has become the mainstream for long-term preservation | save. However, the composite laminate film using these materials is generally expensive. In addition, there is a problem that it cannot be used in fields where transparency is required.
そこで、最近開発されている、例えば、ベースフィルム層とヒートシール材層の間に高水素結合樹脂（好ましいものとしては、ポリビニルアルコール）、無機層状化合物（好ましくは粘土鉱物）、水素結合性基用架橋剤（好ましくは、ジルコニア化合物）を含むガスバリア層を設けたレトルト用包装袋（例えば、特許文献３参照）の利用が検討されている。しかし、このようなガスバリア層を有するレトルト用包装袋は、乾燥状態において極めて優れたバリア性を有するが、吸湿性が高いため、高湿度下では結晶性が崩れてバリア性が低下するので、熱水処理時においてもバリア性が低下し、熱水処理後の適性が低下する問題を有している。 Therefore, recently developed, for example, between a base film layer and a heat seal material layer, a high hydrogen bond resin (preferably, polyvinyl alcohol), an inorganic layered compound (preferably clay mineral), for a hydrogen bondable group Use of a retort packaging bag (see, for example, Patent Document 3) provided with a gas barrier layer containing a crosslinking agent (preferably, a zirconia compound) has been studied. However, the retort packaging bag having such a gas barrier layer has an extremely excellent barrier property in a dry state, but has a high hygroscopic property, so that the crystallinity is lost and the barrier property is lowered under high humidity. Even during water treatment, the barrier property is lowered, and the suitability after hot water treatment is lowered.
また、例えば、ベースフィルム層、高水素結合樹脂（好ましいものとしては、ポリビニルアルコール、エチレン−ビニルアルコール共重合体等）、無機層状化合物（好ましくは粘土鉱物）、水素結合性基用架橋剤（好ましくは、有機チタン化合物）を含むガスバリア層、延伸フィルム層、ヒートシール材層がこの順に積層したレトルト用包装用フィルム積層体（例えば、特許文献４参照）の利用が検討されている。しかし、このようなガスバリア層を有するレトルト用袋は、熱水処理後のラミネート強度が低下する問題を有している。
そこで、本発明の課題は、熱水処理しても、バリア性が良好で、且つラミネート強度の低下が少ないラミネート用バリア性コーティング組成物及びその組成物から得られるバリア層を有するラミネート用バリア性複合フィルムを提供することである。 Accordingly, an object of the present invention is to provide a barrier coating composition for a laminate that has good barrier properties and little decrease in laminate strength even after hot water treatment, and a barrier property for laminates having a barrier layer obtained from the composition. It is to provide a composite film.
本発明者らは、研究を重ねた結果、少なくともベースフィルム層、バリア層、ヒートシール材層をこの順に設けたラミネート用バリア性複合フィルムにおいて、バリア層を、無機層状化合物とエチレン−ビニルアルコール系共重合体（エチレン−酢酸ビニル系共重合体をケン化して得られるエチレン−ビニルアルコール系共重合体を過酸化物で処理した水酸基及び／又はカルボキシル基を有するもの）とを特定質量比率となるように含有させ、且つ架橋剤として水溶性ジルコニウム化合物を特定量含有させたラミネート用バリア性コーティング組成物により設けることにより上記の課題を解決できることを見出し、本発明を完成させたものである。 As a result of repeated research, the inventors of the present invention have found that, in a barrier composite film for lamination in which at least a base film layer, a barrier layer, and a heat seal material layer are provided in this order, A specific mass ratio of a copolymer (having a hydroxyl group and / or a carboxyl group obtained by treating an ethylene-vinyl alcohol copolymer obtained by saponifying an ethylene-vinyl acetate copolymer with a peroxide). Thus, the present invention has been completed by finding that the above problems can be solved by providing a barrier coating composition for a laminate containing a specific amount of a water-soluble zirconium compound as a crosslinking agent.
即ち、本発明は、（１）（Ａ）エチレン−酢酸ビニル系共重合体をケン化し、更に過酸化物で処理したエチレン−ビニルアルコール系共重合体、（Ｂ）無機層状化合物、及び、（Ｃ）溶媒を含有するラミネート用バリア性コーティング組成物において、更に、（Ｄ）水溶性ジルコニウム化合物を含有し、以下の式１及び式２を満足するラミネート用バリア性コーティング組成物に関する。
（式１） ＷＢ／ＷＡ＝１０／９０〜３５／６５
（式１中、ＷＡはラミネート用バリア性コーティング組成物中の（Ａ）成分の含有量（質量）、ＷＢはラミネート用バリア性コーティング組成物中の（Ｂ）成分の含有量（質量）を表す。）
（式２） ｛ＷＤ／（ＷＡ＋ＷＢ＋ＷＤ）｝×１００＝０．１〜１０
（式２中、ＷＡ、ＷＢは上記と同じ定義、ＷＤはラミネート用バリア性コーティング組成物中の（Ｄ）成分の含有量（質量）を表す。）
また、本発明は、（２）上記ラミネート用バリア性コーティング組成物において、上記式１による（Ａ）成分と（Ｂ）成分との質量比率（ＷＢ／ＷＡ）が１５／８５〜３０／７０である上記（１）項に記載のラミネート用バリア性コーティング組成物に関する。
また、本発明は、（３）上記（Ｂ）成分の無機層状化合物が、モンモリロナイトである上記（１）項又は（２）項記載のラミネート用バリア性コーティング組成物に関する。
また、本発明は、（４）上記（Ｄ）成分の水溶性ジルコニウム化合物が、塩酸化ジルコニウムである上記（１）〜（３）項のいずれかに記載のラミネート用バリア性コーティング組成物に関する。
また、本発明は、（５）少なくともベースフィルム層、バリア層、ヒートシール材層から構成され、更に上記各層をこの順に設けたラミネート用バリア性複合フィルムにおいて、該バリア層が、上記（１）〜（４）項のいずれかに記載のラミネート用バリア性コーティング組成物から得られるものであるラミネート用バリア性複合フィルムに関する。
また、本発明は、（６）更に、上記ベースフィルム層と上記ヒートシール材層との間に印刷層が積層された上記（５）項記載のラミネート用バリア性複合フィルムに関する。
That is, the present invention includes (1) (A) an ethylene-vinyl alcohol copolymer obtained by saponifying an ethylene-vinyl acetate copolymer and further treated with a peroxide, (B) an inorganic layered compound, and ( C) A barrier coating composition for a laminate containing a solvent, further comprising (D) a water-soluble zirconium compound and satisfying the following formulas 1 and 2:
(Equation 1) W B / W A = 10 / 90~35 / 65
(In the formula 1, the content of W A component (A) of the barrier coating composition laminate (mass), W B is the content of the component (B) of the barrier coating composition laminate (mass) Represents.)
(Formula 2) {W D / (W A + W B + W D )} × 100 = 0.1-10
(In the formula 2, W A, W B is the same definition as above, W D represents the content of component (D) of the barrier coating composition for laminating the (mass).)
Further, the present invention provides (2) the barrier coating composition for laminate, wherein the mass ratio (W B / W A ) between the component (A) and the component (B) according to the above formula 1 is 15 / 85-30 / The laminate barrier coating composition according to item (1), which is 70.
The present invention also relates to (3) the barrier coating composition for laminate according to the above item (1) or (2), wherein the inorganic layered compound of the component (B) is montmorillonite.
The present invention also relates to (4) the barrier coating composition for laminate according to any one of the above (1) to (3), wherein the water-soluble zirconium compound as the component (D) is zirconium hydrochloride.
The present invention also provides (5) a barrier composite film for laminating comprising at least a base film layer, a barrier layer, and a heat seal material layer, and further provided with the above layers in this order. The present invention relates to a barrier composite film for laminate, which is obtained from the barrier coating composition for laminate according to any one of items (4) to (4).
The present invention also relates to (6) the barrier composite film for lamination according to the above item (5), wherein a printed layer is further laminated between the base film layer and the heat seal material layer.
以下、本発明のラミネート用バリア性コーティング組成物及びその組成物から得られるバリア層を有するラミネート用バリア性複合フィルムについて詳細に説明する。 The laminate barrier coating composition of the present invention and the laminate barrier composite film having a barrier layer obtained from the composition will be described in detail below.
〔ラミネート用バリア性コーティング組成物〕
先ず、本発明のラミネート用バリア性コーティング組成物について説明する。
本発明のラミネート用バリア性コーティング組成物を構成する（Ａ）成分であるエチレン−ビニルアルコール系共重合体としては、エチレン−酢酸ビニル系共重合体をケン化し、更に過酸化物で処理して得られるものが使用できる。
[Barrier coating composition for laminate]
First, the barrier coating composition for laminate of the present invention will be described.
As the ethylene-vinyl alcohol copolymer that is the component (A) constituting the barrier coating composition for laminate of the present invention, the ethylene-vinyl acetate copolymer is saponified and further treated with a peroxide. What is obtained can be used.
上記エチレン−酢酸ビニル系共重合体をケン化し、更に過酸化物で処理して得られるエチレン−ビニルアルコール系共重合体の具体例としては、エチレン及び酢酸ビニルを共重合して得られるエチレン−酢酸ビニル共重合体をケン化し、更に過酸化物で処理して得られるもの、並びに、エチレン及び酢酸ビニルとともに、その他の単量体を共重合して得られるエチレン−酢酸ビニル系共重合体をケン化し、更に過酸化物で処理して得られるものが挙げられる。 Specific examples of the ethylene-vinyl alcohol copolymer obtained by saponifying the ethylene-vinyl acetate copolymer and further treating with a peroxide include ethylene-vinyl acetate copolymer obtained by copolymerizing ethylene and vinyl acetate. What is obtained by saponifying a vinyl acetate copolymer and further treating with a peroxide, and ethylene-vinyl acetate copolymer obtained by copolymerizing other monomers together with ethylene and vinyl acetate. Examples thereof include those obtained by saponification and further treatment with a peroxide.
バリア層を設けるための材料としては、エチレン−酢酸ビニル系共重合体の共重合前の単量体におけるエチレン比率が２０〜６０モル％であることが好ましい。エチレン比率が２０モル％未満であると、高湿度下におけるバリア性が低下し、一方、エチレン比率が６０モル％を超えると、全般に渡ってのバリア性が低下する傾向がある。
上記エチレン−酢酸ビニル系共重合体は、酢酸ビニル成分のケン化度が９５モル％以上のものが好ましく、９５モル％未満ではバリア性や耐油性が不充分になる傾向がある。
As a material for providing the barrier layer, the ethylene ratio in the monomer before copolymerization of the ethylene-vinyl acetate copolymer is preferably 20 to 60 mol%. When the ethylene ratio is less than 20 mol%, the barrier property under high humidity is lowered. On the other hand, when the ethylene ratio exceeds 60 mol%, the barrier property tends to be lowered over the whole.
The ethylene-vinyl acetate copolymer preferably has a vinyl acetate component having a saponification degree of 95 mol% or more. If it is less than 95 mol%, the barrier property and oil resistance tend to be insufficient.
上記過酸化物としては、以下の（１）〜（７）ようなものが挙げられる。
（１）Ｈ２Ｏ２
（２）Ｍ２Ｏ２型（Ｍ：Ｎａ、Ｋ、ＮＨ４、Ｒｂ、Ｃｓ、Ａｇ、Ｌｉ等）
（３）Ｍ’Ｏ２型（Ｍ’：Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｃｓ、Ｈｇ等）
（４）Ｒ−Ｏ−Ｏ−Ｒ型（Ｒはアルキル基を表す。以下同様：過酸化ジエチル等の過酸化ジアルキル類
（５）Ｒ−ＣＯ−Ｏ−Ｏ−ＣＯ−Ｒ型：過酸化ジアセチル、過酸化ジアミル、過酸化時ベンゾイル等の過酸化アシル等
（６）過酸化酸型
ａ）−Ｏ−Ｏ−結合を持つ酸：過硫酸（Ｈ２ＳＯ５）、過リン酸（Ｈ３ＰＯ５）等
ｂ）Ｒ−ＣＯ−Ｏ−ＯＨ：過ギ酸、過酢酸、過安息香酸、過フタル酸等
（７）過酸化水素包含物：（ＮａＯＯＨ）２／Ｈ２Ｏ２、（ＫＯＯＨ）２／３Ｈ２Ｏ２等
このなかでも特に過酸化水素は、後から還元剤、還元性酵素や触媒を用いて、容易に分解処理することが可能であるために好適である。
Examples of the peroxide include the following (1) to (7).
(1) H 2 O 2
(2) M 2 O 2 type (M: Na, K, NH 4 , Rb, Cs, Ag, Li, etc.)
(3) M′O 2 type (M ′: Mg, Ca, Sr, Ba, Zn, Cs, Hg, etc.)
(4) R—O—O—R type (R represents an alkyl group; hereinafter the same: dialkyl peroxides such as diethyl peroxide) (5) R—CO—O—O—CO—R type: diacetyl peroxide , Diamyl peroxide, acyl peroxide such as benzoyl at the time of peroxide, etc. (6) Peroxy acid type a) Acid having —O—O— bond: persulfuric acid (H 2 SO 5 ), perphosphoric acid (H 3 PO 5 ) etc. b) R—CO—O—OH: performic acid, peracetic acid, perbenzoic acid, perphthalic acid, etc. (7) Hydrogen peroxide inclusions: (NaOOH) 2 / H 2 O 2 , (KOOH) 2 / 3H 2 O 2, etc., especially hydrogen peroxide among this, the reducing agent later, by using a reducing enzymes and catalysts are suitable for it is possible to easily decomposed.
上記エチレン−酢酸ビニル系共重合体をケン化して得られた重合体を過酸化物で処理する方法としては特に限定されず、公知の処理方法を用いることができ、具体的には以下の方法を挙げることができる。
（１）上記溶媒に、ケン化して得られた重合体を溶解した溶液に、上記過酸化物、分子鎖切断を行うための触媒、例えば硫酸鉄等を添加し、攪拌下で４０〜９０℃で加熱する方法
The method for treating the polymer obtained by saponifying the ethylene-vinyl acetate copolymer with a peroxide is not particularly limited, and a known treatment method can be used. Can be mentioned.
(1) To the solution in which the polymer obtained by saponification is dissolved in the solvent, the peroxide, a catalyst for performing molecular chain cleavage, such as iron sulfate, is added and stirred at 40 to 90 ° C. How to heat with
また、処理後において、残存過酸化物が残存していると、バリア性が低下する傾向にあるので、本発明の効果を阻害しない限り従来公知の除去方法で残存過酸化物を除去する方が望ましい。好ましい、具体例としては、カタラーゼ等の酵素を添加して残存過酸化物を分解除去する方法を挙げることができる。 In addition, if the residual peroxide remains after the treatment, the barrier property tends to decrease. Therefore, it is better to remove the residual peroxide by a conventionally known removal method unless the effect of the present invention is impaired. desirable. Preferable specific examples include a method in which an enzyme such as catalase is added to decompose and remove the remaining peroxide.
また、本発明のラミネート用バリア性コーティング組成物を構成する（Ｃ）成分である溶媒（溶剤）としては、（Ａ）成分のエチレン−ビニルアルコール系共重合体を溶解し得る、水性及び非水性のどちらの溶剤でも使用できる。 Further, as the solvent (solvent) which is the component (C) constituting the barrier coating composition for laminate of the present invention, an aqueous and non-aqueous solution capable of dissolving the ethylene-vinyl alcohol copolymer of the component (A) Either of these solvents can be used.
本発明におけるエチレン−ビニルアルコール系共重合体では、過酸化物等で処理することにより低分子量化したエチレン−ビニルアルコール系共重合体と、水と低級アルコールとの混合溶剤を利用して、ラミネート用バリア性コーティング組成物を構成することが好ましい。具体的には、水と、エチルアルコール、ｎ−プロピルアルコール、ｉｓｏ−プロピルアルコール、ｎ−ブチルアルコール、ｉｓｏ−ブチルアルコール、ｓｅｃ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール等の炭素数２〜４の低級アルコールの少なくとも１種を１５〜７０質量％含む混合溶剤を使用すると、エチレン−ビニルアルコール系共重合体の溶解性が良好となり、適度な固形分を維持するためにも好適である。混合溶剤中の低級アルコールの含有量が７０質量％を超えると、後述する無機層状化合物を分散した場合、へき開が不充分になる。一方、混合溶剤中の低級アルコールが１５質量％未満であると、ラミネート用バリア性コーティング組成物の塗布適性が低下する傾向がある。 The ethylene-vinyl alcohol copolymer in the present invention is laminated using a mixed solvent of an ethylene-vinyl alcohol copolymer that has been reduced in molecular weight by treatment with a peroxide or the like, and water and a lower alcohol. It is preferable to constitute a barrier coating composition for use. Specifically, water and lower alcohols having 2 to 4 carbon atoms such as ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, etc. When a mixed solvent containing 15 to 70% by mass of at least one of the above is used, the solubility of the ethylene-vinyl alcohol copolymer is improved, and it is also suitable for maintaining an appropriate solid content. If the content of the lower alcohol in the mixed solvent exceeds 70% by mass, cleavage will be insufficient when an inorganic layered compound described later is dispersed. On the other hand, when the lower alcohol in the mixed solvent is less than 15% by mass, the applicability of the laminate barrier coating composition tends to be lowered.
また、本発明のラミネート用バリア性コーティング組成物を構成する（Ｂ）成分である無機層状化合物としては、分散媒に膨潤・へき開する無機層状化合物が好ましく用いられ、フィロケイ酸塩の１：１構造をもつカオリナイト族、ジャモン石群に属するアンチゴライト族、層間カチオンの数によってスメクタイト族、含水ケイ酸塩鉱物であるバーミキュライト族、マイカ族等を挙げることができる。 In addition, as the inorganic layered compound that is the component (B) constituting the barrier coating composition for laminate of the present invention, an inorganic layered compound that swells and cleaves in the dispersion medium is preferably used, and the 1: 1 structure of the phyllosilicate is used. The kaolinite group having the above, the antigolite group belonging to the jamonite group, the smectite group, the hydrated silicate mineral vermiculite group, the mica group, and the like can be exemplified.
上記無機層状化合物としては、具体的には、カオリナイト、ナクライト、ディッカイト、ハロイサイト、加水ハロイサイト、アンチゴライト、クリソタイル、パイロフィライト、モンモリロナイト、バイデライト、サポナイト、ヘクトライト、ソーコナイト、スチーブンサイト、テトラシリリックマイカ、ナトリウムテニオライト、白雲母、マーガライト、タルク、バーミキュライト、金雲母、ザンソフィライト、緑泥石等を挙げることができる。また鱗片状シリカ等も使用できる。これらは単独で用いてもよく、２種以上を併用してもよい。これらの無機層状化合物でも、無機層状化合物中に酸化還元性を有する金属イオン、特に鉄イオンが存在するものが有効である。
更に、これらの中でも、ラミネート用バリア性コーティング組成物に使用した場合の基材に対するブリード性、印刷適性からモンモリロナイトの使用が好ましい。
Specific examples of the inorganic layered compound include kaolinite, nacrite, dickite, halloysite, hydrous halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, saponite, hectorite, soconite, stevensite, tetracite. Examples include lyric mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite. Also, scaly silica can be used. These may be used alone or in combination of two or more. Of these inorganic layered compounds, those in which a metal ion having redox properties, particularly iron ions, are present in the inorganic layered compound are effective.
Furthermore, among these, use of montmorillonite is preferable from the viewpoint of bleeding property and printability with respect to a substrate when used in a barrier coating composition for laminate.
上記モンモリロナイトとしては、従来からガスバリヤ剤に使用されている公知のものが使用できる。
例えば、一般式：（Ｘ，Ｙ）２〜３Ｚ４Ｏ１０（ＯＨ）２・ｍＨ２Ｏ・（Ｗω）（式中、Ｘは、Ａｌ、ＦｅＩＩＩ、ＣｒＩＩＩを表す。Ｙは、Ｍｇ、ＦｅＩＩ、ＭｎＩＩ、Ｎｉ、Ｚｎ、Ｌｉを表す。Ｚは、Ｓｉ、Ａｌを表す。Ｗは、Ｋ、Ｎａ、Ｃａを表す。Ｈ２Ｏは、層間水を表す。）で示されるモンモリロン石群鉱物を使用することができる。これらのなかでも、ＷはＮａであるものが水性媒体中でへき開する点から好ましい。
As said montmorillonite, the well-known thing conventionally used for the gas barrier agent can be used.
For example, the general formula: (X, Y) 2~3 Z 4 O 10 (OH) 2 · mH 2 O · (Wω) ( In the formula, X, .Y representing Al, Fe III, a Cr III is, Mg , Fe II , Mn II , Ni, Zn, Li. Z represents Si, Al. W represents K, Na, Ca. H 2 O represents interlayer water.) Stone group minerals can be used. Among these, W is preferably Na because it is cleaved in an aqueous medium.
本発明のラミネート用バリア性コーティング組成物において、（Ａ）成分：エチレン−ビニルアルコール系共重合体と、（Ｂ）成分：無機層状化合物との質量比率は、（式１）を満足する範囲で、好ましくは（式１−１）を満足する範囲で使用される。
（式１） ＷＢ／ＷＡ＝１０／９０〜３５／６５
（式１−１） ＷＢ／ＷＡ＝１５／８５〜３０／７０
（式１、式１−１中、ＷＡはラミネート用バリア性コーティング組成物中の（Ａ）成分の含有量（質量）、ＷＢはラミネート用バリア性コーティング組成物中の（Ｂ）成分の含有量（質量）を表す。）
上記（Ｂ）成分：無機層状化合物の質量比率が少なくなると、接着性は高くなるがバリア性が低下し、一方、多くなりすぎるとバリア性は高くなるがラミネート強度が低下し熱水処理適性が低下する傾向にある。
In the barrier coating composition for a laminate of the present invention, the mass ratio of (A) component: ethylene-vinyl alcohol copolymer and (B) component: inorganic layered compound is within a range satisfying (Formula 1). Preferably, it is used in a range satisfying (Formula 1-1).
(Equation 1) W B / W A = 10 / 90~35 / 65
(Equation 1-1) W B / W A = 15 / 85~30 / 70
(Formula 1, in Formula 1-1, W A is the content of the component (A) in the laminating barrier coating composition (mass), W B is the barrier coating composition laminate component (B) Represents content (mass).)
When the mass ratio of the component (B): inorganic layered compound is decreased, the adhesion is increased but the barrier property is decreased. On the other hand, when the amount is too large, the barrier property is increased, but the laminate strength is decreased and the hydrothermal treatment suitability is improved. It tends to decrease.
上記ラミネート用バリア性コーティング組成物において、エチレン−ビニルアルコール系樹脂（ＷＡ）と無機層状化合物（ＷＢ）との合計の含有量（ＷＡ＋ＷＢ）は、ラミネート用バリア性コーティング組成物１００質量％中に１〜３０質量％含有されていることが好ましい。上記含有量が１質量％より少なくなると、適度の膜厚を有するバリア層を形成するために複数回の塗工が必要になる等の不利が生じることがあり、一方、３０質量％より多くなると、流動性が低下して、塗工が困難になる等の不利が生じる。 In the barrier coating composition for laminating, the total content (W A + W B ) of the ethylene-vinyl alcohol-based resin (W A ) and the inorganic layered compound (W B ) is the barrier coating composition for laminating 100. It is preferable that 1-30 mass% is contained in the mass%. When the content is less than 1% by mass, disadvantages such as the need for multiple coatings to form a barrier layer having an appropriate film thickness may occur, while on the other hand, when the content exceeds 30% by mass. However, there are disadvantages such as poor fluidity and difficult coating.
また、本発明のラミネート用バリア性コーティング組成物を構成する（Ｄ）成分である水溶性ジルコニウム化合物は、水溶性を有するジルコニウム含有化合物である。本発明において水溶性ジルコニウム化合物は架橋剤として機能するものであり、上記エチレン−ビニルアルコール系共重合体及び無機層状化合物とともに使用することにより、熱水処理をしても、良好なバリア性を有し、ラミネート強度の低下が少ないラミネート用バリア性複合フィルムを得ることができる。 Moreover, the water-soluble zirconium compound which is the component (D) constituting the barrier coating composition for laminate of the present invention is a zirconium-containing compound having water solubility. In the present invention, the water-soluble zirconium compound functions as a crosslinking agent. By using it together with the ethylene-vinyl alcohol copolymer and the inorganic layered compound, the water-soluble zirconium compound has a good barrier property even when subjected to hydrothermal treatment. In addition, it is possible to obtain a barrier composite film for laminating with little decrease in laminating strength.
上記水溶性ジルコニウム化合物としては、塩酸化ジルコニウム、ヒドロキシ塩化ジルコニウム、塩基性硫酸ジルコニウム、硝酸ジルコニウム、炭酸ジルコニウムアンモニウム、硫酸ジルコニウムナトリウム、クエン酸ジルコニウムナトリウム、乳酸ジルコニウム、酢酸ジルコニウム、硫酸ジルコニウム、オキシ硫酸ジルコニウム、オキシ硝酸ジルコニウム、塩基性炭酸ジルコニウム、水酸化ジルコニウム、炭酸ジルコニウムカリウム、塩化ジルコニウム、塩化ジルコニウム八水和物、オキシ塩化ジルコニウム等が例示でき、塗布凝集力の向上による熱水処理後の熱水処理適性及びラミネート用バリア性コーティング組成物の安定性の点から、塩酸化ジルコニウム、ヒドロキシ塩化ジルコニウムが好ましく、特に塩酸化ジルコニウムが好ましい。これらは、単独で用いてもよく、２種以上を併用してもよい。 Examples of the water-soluble zirconium compound include zirconium chloride, hydroxy zirconium chloride, basic zirconium sulfate, zirconium nitrate, ammonium zirconium carbonate, sodium zirconium sulfate, sodium zirconium citrate, zirconium lactate, zirconium acetate, zirconium sulfate, zirconium oxysulfate, Examples include zirconium oxynitrate, basic zirconium carbonate, zirconium hydroxide, potassium zirconium carbonate, zirconium chloride, zirconium chloride octahydrate, zirconium oxychloride, etc. From the viewpoint of the stability of the barrier coating composition for laminating, zirconium hydrochloride and hydroxy zirconium chloride are preferred, and zirconium hydroxide is particularly preferred.These may be used alone or in combination of two or more.
本発明のラミネート用バリア性コーティング組成物において、（Ｄ）成分：水溶性ジルコニウム化合物の合計使用量（固形中の含有量）は、（式２）を満足する範囲で使用される。
（式２） ｛ＷＤ／（ＷＡ＋ＷＢ＋ＷＤ）｝×１００＝０．１〜１０（質量％）
（式２中、ＷＡ、ＷＢは上記と同じ定義、ＷＤはラミネート用バリア性コーティング組成物中の（Ｄ）成分の含有量（質量）を表す。）
上記水溶性ジルコニウム化合物の使用量が０．１質量％より少なくなると、熱水処理後のラミネート強度低下等の熱水処理適性が低下し、一方使用量が１０質量％より多くなると、バリア性が低下する問題を有する。
上記ラミネート用バリア性コーティング組成物は、更に他の成分として、必要に応じて、紫外線吸収剤、帯電防止剤、レベリング剤、消泡剤等を１種又は２種以上加えることができる。
In the barrier coating composition for a laminate of the present invention, the total amount of component (D): water-soluble zirconium compound (content in solid) is used in a range satisfying (Formula 2).
(Formula 2) {W D / (W A + W B + W D )} × 100 = 0.1 to 10 (mass%)
(In the formula 2, W A, W B is the same definition as above, W D represents the content of component (D) of the barrier coating composition for laminating the (mass).)
When the amount of the water-soluble zirconium compound used is less than 0.1% by mass, the suitability for hot water treatment such as reduction in laminate strength after the hot water treatment is reduced. On the other hand, when the amount used is more than 10% by mass, the barrier property is reduced. Has the problem of lowering.
The barrier coating composition for laminate may further contain one or more ultraviolet absorbers, antistatic agents, leveling agents, antifoaming agents and the like as other components as required.
〔ラミネート用バリア性コーティング組成物の製造方法〕
上記構成材料を使用してラミネート用バリア性コーティング組成物を製造する方法としては、例えば、（１）溶媒にエチレン−ビニルアルコール系樹脂を溶解した溶液に、過酸化物を添加して加温・反応させ分子鎖切断を行い、その後、残存過酸化物を除去しエチレン−ビニルアルコール系樹脂の樹脂溶液を得る。次いで、無機層状化合物（水等の分散媒に予め膨潤・へき開させておいてもよい）、水溶性ジルコニウム化合物を添加混合し、攪拌装置や分散装置を利用して無機層状化合物を分散させる方法、（２）無機層状化合物を、水等の分散媒に膨潤・へき開させた後、攪拌装置や分散装置を利用し、更に、無機層状化合物をへき開、分散した分散液（分散溶液）に、予め溶媒にエチレン−ビニルアルコール系樹脂を溶解させた溶液に過酸化物を添加して加温・反応させ分子鎖切断を行い、その後、残存過酸化物を除去したエチレン−ビニルアルコール系樹脂の樹脂溶液、水溶性ジルコニウム化合物を添加混合する方法等を挙げることができる。
[Method for Producing Laminate Barrier Coating Composition]
Examples of a method for producing a barrier coating composition for a laminate using the above constituent materials include (1) adding a peroxide to a solution in which an ethylene-vinyl alcohol resin is dissolved in a solvent, The reaction is performed to cleave the molecular chain, and then the remaining peroxide is removed to obtain a resin solution of ethylene-vinyl alcohol resin. Next, an inorganic layered compound (which may be previously swollen and cleaved in a dispersion medium such as water), a water-soluble zirconium compound is added and mixed, and the inorganic layered compound is dispersed using a stirrer or a dispersing device, (2) After the inorganic layered compound is swollen and cleaved in a dispersion medium such as water, a stirrer or a dispersing device is used, and the inorganic layered compound is further cleaved and dispersed in a dispersion (dispersion solution) in advance. A solution of an ethylene-vinyl alcohol resin in which an ethylene-vinyl alcohol resin is dissolved, and a peroxide is added to the solution to heat and react to cause molecular chain scission, and then the remaining peroxide is removed. Examples thereof include a method of adding and mixing a water-soluble zirconium compound.
上記攪拌装置や分散装置としては、通常の撹拌装置や分散装置であれば特に限定されず、これらを用いて分散液中で無機層状化合物を均一に分散することができるが、透明で安定なラミネート用バリア性コーティング組成物が得られる点から、高圧分散機、超音波分散機等を使用することが好ましい。高圧分散機としては、例えば、ナノマイザー（商品名、ナノマイザー社製）、マイクロフルイタイザー（商品名、マイクロフライデックス社製）、アルチマイザー（商品名、スギノマシン社製）、ＤｅＢｅｅ（商品名、Ｂｅｅ社製）、ニロ・ソアビホモジナイザー（商品名、ニロ・ソアビ社）等が挙げられ、これら高圧分散機の圧力条件として１００ＭＰａ以下で分散処理を行うことが好ましい。圧力条件が１００ＭＰａを超えると、無機層状化合物の破砕が起こり易くなり、目的であるバリア性が低下する場合がある。 The stirring device and the dispersion device are not particularly limited as long as they are ordinary stirring devices and dispersion devices, and these can be used to uniformly disperse the inorganic layered compound in the dispersion liquid. It is preferable to use a high-pressure disperser, an ultrasonic disperser, or the like from the viewpoint that a barrier coating composition for use can be obtained. Examples of the high-pressure disperser include a nanomizer (trade name, manufactured by Nanomizer), a microfluidizer (trade name, manufactured by Microfridex), an optimizer (trade name, manufactured by Sugino Machine), and DeBee (trade name, Bee). And Niro Soabi homogenizer (trade name, Niro Soabi) and the like. It is preferable to carry out the dispersion treatment at 100 MPa or less as the pressure condition of these high-pressure dispersers. When the pressure condition exceeds 100 MPa, the inorganic layered compound tends to be crushed, and the target barrier property may be lowered.
〔ラミネート用バリア性複合フィルム〕
次に、ラミネート用バリア性コーティング組成物及びその組成物から得られるバリア層を有するラミネート用バリア性複合フィルムについて説明する。
本発明のラミネート用バリア性複合フィルムは、少なくともベースフィルム層、バリア層、ヒートシール材層をこの順に設けたものである。
[Barrier composite film for laminating]
Next, the barrier barrier composite composition for laminate and the barrier composite film for laminate having a barrier layer obtained from the composition will be described.
The barrier composite film for laminating of the present invention comprises at least a base film layer, a barrier layer, and a heat seal material layer in this order.
本発明のラミネート用バリア性複合フィルムを構成するベースフィルム層としては、例えば、従来から軟包装で使用されているポリオレフィン、変性ポリオレフィン、ポリエステル、ナイロン、ポリスチレン等からなる各種プラスチックフィルム、及びこれらの２種以上からなる複合フィルムを挙げることができ、これらのフィルムは、コロナ放電処理又は表面コート処理されていることが好ましい。また、ガスバリア性の面からはポリオレフィン系フィルムが好ましい。 Examples of the base film layer constituting the barrier composite film for laminate of the present invention include various plastic films made of polyolefin, modified polyolefin, polyester, nylon, polystyrene, etc., which have been conventionally used in flexible packaging, and these 2 The composite film which consists of a seed | species or more can be mentioned, It is preferable that these films are corona-discharge-treated or surface-coated. From the viewpoint of gas barrier properties, polyolefin films are preferred.
本発明のラミネート用バリア性複合フィルムを構成するバリア層としては、上記に記載したラミネート用バリア性コーティング組成物を、各種塗工手段を用いて形成することができる。上述した成分を含むラミネート用バリア性コーティング組成物を使用することにより、熱水処理をしても、良好なバリア性を有し、ラミネート強度の低下が少ないフィルムを得ることができる。 As the barrier layer constituting the barrier composite film for laminate of the present invention, the barrier coating composition for laminate described above can be formed using various coating means. By using the barrier coating composition for a laminate containing the above-described components, a film having good barrier properties and little decrease in laminate strength can be obtained even when subjected to hot water treatment.
本発明のラミネート用バリア性複合フィルムを構成するヒートシール材層としては、従来から軟包装で使用されている熱融着性のシート材料であり、例えば、ポリエチレンフィルム、ポリプロピレンフィルム等が挙げられる。上記ヒートシール材層は、また、低密度ポリエチレン、エチレン−酢酸ビニル共重合体、ポリプロピレンポリマー等の熱溶融ポリマーを溶融状態で積層して、冷却によりフィルム状に成形したものであってもよい。この場合、ヒートシール材層に接着層を先に設けることができないため、バリア層側に接着層を設けた後、接着層に溶融状態で上記熱溶融ポリマーを積層する方法が用いられる。 The heat sealing material layer constituting the barrier composite film for laminating of the present invention is a heat-fusible sheet material conventionally used in soft packaging, and examples thereof include a polyethylene film and a polypropylene film. The heat sealing material layer may be formed by laminating a hot-melt polymer such as low-density polyethylene, an ethylene-vinyl acetate copolymer, and a polypropylene polymer in a molten state, and forming the film by cooling. In this case, since the adhesive layer cannot be provided on the heat seal material layer first, after the adhesive layer is provided on the barrier layer side, the above-described hot-melt polymer is laminated on the adhesive layer in a molten state.
更に、ラミネート用バリア性複合フィルムには、ベースフィルム層とバリア層の間に接着層を、バリア層とヒートシール材層の間に接着層を、ベースフィルム層とヒートシール材層との間に印刷層を設けることもできる。 Further, in the barrier composite film for laminating, an adhesive layer is provided between the base film layer and the barrier layer, an adhesive layer is provided between the barrier layer and the heat seal material layer, and between the base film layer and the heat seal material layer. A printing layer can also be provided.
ベースフィルム層とバリア層との間に設ける接着層、バリア層とヒートシール材層の間の接着層としては、従来から包装用複合ラミネートフィルムの製造に用いられているラミネート用接着剤組成物を適宜選択し、各種塗工手段を用いて形成することができる。ラミネート用接着剤組成物としては、例えばウレタン系、ポリエステル系、アクリル系等の各種ラミネート用接着剤、チタン系、イソシアネート系、イミン系、ポリブタジエン系等の各種ラミネート用アンカーコート剤等を挙げることができる。 As an adhesive layer provided between the base film layer and the barrier layer, and an adhesive layer between the barrier layer and the heat seal material layer, an adhesive composition for laminating that has been conventionally used in the manufacture of composite laminate films for packaging is used. It can select suitably and can form using various coating means. Examples of the laminating adhesive composition include various laminating adhesives such as urethane, polyester, and acrylic, and anchor coating agents for laminating such as titanium, isocyanate, imine, and polybutadiene. it can.
また、ラミネート用接着剤組成物としては、アミノ基、水酸基及びカルボキシル基の少なくとも１つの官能基を有するポリウレタン樹脂を主成分とする主剤とエポキシ系硬化剤及びイソシアネート系硬化剤とからなる硬化剤とを用い、これらの材料を溶媒中に含有させた接着剤組成物も使用できる。 The laminating adhesive composition includes a main agent mainly composed of a polyurethane resin having at least one functional group of an amino group, a hydroxyl group and a carboxyl group, and a curing agent comprising an epoxy curing agent and an isocyanate curing agent. An adhesive composition containing these materials in a solvent can also be used.
上記ポリウレタン樹脂としては、例えば、高分子ポリオールと有機ジイソシアネートとを反応させて得られる、分子末端にイソシアネート基を有するウレタンプレポリマーを、更に鎖伸長剤で鎖伸長した後、必要に応じて反応停止剤を用いて反応させる方法を用いて得られる、分子内に水酸基、アミノ基及びカルボキシル基からなる群より選択される少なくとも１つの官能基を有するポリウレタン樹脂を挙げることができる。 As the polyurethane resin, for example, a urethane prepolymer having an isocyanate group at the molecular end obtained by reacting a polymer polyol and an organic diisocyanate is further chain-extended with a chain extender, and the reaction is stopped if necessary. Examples thereof include a polyurethane resin having at least one functional group selected from the group consisting of a hydroxyl group, an amino group and a carboxyl group in the molecule, obtained by a method of reacting with an agent.
上記有機ジイソシアネート化合物、高分子ポリオール化合物、鎖伸長剤、反応停止剤等としては、従来公知のものを用いることができ、例えば、特開平０６−１３６３１３号公報、特開平０６−２４８０５１号公報、特開平０７−２５８３５７号公報及び特開平０７−３２４１７９号公報等に記載された各化合物を使用することができる。 As the organic diisocyanate compound, polymer polyol compound, chain extender, reaction terminator, and the like, conventionally known compounds can be used. For example, JP-A-06-136313, JP-A-06-248051, Each compound described in Kaihei 07-258357 and JP-A-07-324179 can be used.
上記イソシアネート系硬化剤、エポキシ系硬化剤としては、包装用複合ラミネートフィルムの製造に用いられている、従来公知の二液接着剤の成分であるポリイソシアネート系硬化剤、エポキシ系硬化剤を使用することができる。 As the isocyanate curing agent and epoxy curing agent, a polyisocyanate curing agent and an epoxy curing agent, which are components of a conventionally known two-component adhesive, used in the manufacture of a composite laminate film for packaging are used. be able to.
上記主剤及び硬化剤の材料を溶解又は分散させる溶媒（溶剤）としては、例えば、ベンゼン、トルエン等の芳香族系溶剤；メタノール、エタノール等のアルコール系溶剤；アセトン、メチルエチルケトン等のケトン系溶剤；酢酸エチル、酢酸ブチル等のエステル系溶剤；エチレングリコールモノメチルエーテル等の多価アルコール誘導体等が挙げられる。 Examples of the solvent (solvent) for dissolving or dispersing the materials of the main agent and the curing agent include aromatic solvents such as benzene and toluene; alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; Examples include ester solvents such as ethyl and butyl acetate; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether, and the like.
上記印刷層（内容物表示や装飾機能のための印刷層）としては、従来から軟包装で使用されている有機溶剤型印刷インキ組成物、水性印刷インキ組成物等を、通常、グラビア印刷方式やフレキソ印刷方式にて印刷することにより形成することができる。 As the above-mentioned printing layer (printing layer for contents display and decoration function), organic solvent type printing ink composition, water-based printing ink composition and the like conventionally used in soft packaging, usually gravure printing method and It can be formed by printing with a flexographic printing method.
上記有機溶剤型印刷インキ組成物としては、例えば、顔料とポリウレタン樹脂とを含む芳香族・非芳香族混合系有機溶剤性印刷インキ組成物の他、特開平０１−２６１４７６号公報（顔料、ポリウレタン樹脂、塩素化ポリプロピレンを含む芳香族・非芳香族混合系有機溶剤性印刷インキ組成物）、特公平０７−１１３０９８号公報（顔料、ポリウレタン樹脂を含む非芳香族系有機溶剤性印刷インキ組成物）、特開平０７−３２４１７９号公報（顔料、ポリウレタン樹脂、非芳香族系・非ケトン系有機溶剤性印刷インキ組成物）等で開示された有機溶剤性印刷インキ組成物等が挙げられる。 Examples of the organic solvent-type printing ink composition include, for example, an aromatic / non-aromatic mixed organic solvent-based printing ink composition containing a pigment and a polyurethane resin, as well as JP-A-01-261476 (pigment, polyurethane resin). , Aromatic / non-aromatic mixed organic solvent-based printing ink composition containing chlorinated polypropylene), JP 07-113098 (non-aromatic organic solvent-based printing ink composition containing pigment and polyurethane resin), Examples thereof include organic solvent-based printing ink compositions disclosed in JP-A-07-324179 (pigments, polyurethane resins, non-aromatic / non-ketone organic solvent-based printing ink compositions), and the like.
また、上記水性印刷インキ組成物としては、例えば、特開平０６−１５５６９４号公報（顔料、アクリル系バインダー樹脂、ヒドラジン系架橋剤を含む水性印刷インキ組成物）、特開平０６−２０６９７２号公報（顔料、水、ポリウレタン系バインダー樹脂を含む水性印刷インキ組成物）等で開示された水性印刷インキ組成物等が挙げられる。 Examples of the water-based printing ink composition include, for example, Japanese Patent Laid-Open No. 06-155694 (water-based printing ink composition containing a pigment, an acrylic binder resin, and a hydrazine-based crosslinking agent), and Japanese Patent Laid-Open No. 06-206972 (pigment). Water, a water-based printing ink composition including a polyurethane-based binder resin) and the like.
尚、最近では、環境対応インキとして、水性タイプの印刷インキ組成物や、有機溶剤系印刷インキ組成物であっても芳香族及びケトン系有機溶剤を極力使用しないタイプのものが使用されており、本発明でも、これらを好適に用いることができる。
更に、本発明のラミネート用バリア性複合フィルムにおいては、他の機能層、例えば、紫外線遮蔽層、抗菌層、バリア層以外の層同士を接着するための接着層等を有していてもよい。
In recent years, as environmentally friendly inks, water-based printing ink compositions and organic solvent-based printing ink compositions have been used that do not use aromatic and ketone-based organic solvents as much as possible. In the present invention, these can be preferably used.
Furthermore, the barrier composite film for laminate of the present invention may have other functional layers, for example, an ultraviolet shielding layer, an antibacterial layer, an adhesive layer for bonding layers other than the barrier layer, and the like.
〔ラミネート用バリア性複合フィルムの製造方法〕
本発明のラミネート用バリア性複合フィルムを製造する方法としては、結果的に高いバリア性、熱水処理性、ラミネート適性、及び必要に応じて印刷により付加される装飾や表示機能を有するものであれば、どの方法であっても良いが、好ましくは、例えば以下の（Ａ）〜（Ｄ）の方法等が挙げられる。
最も基本的な構成として、
（Ａ）ベースフィルム（ベースフィルムには複合フィルムも含まれる）に、上記ラミネート用バリア性コーティング組成物、接着剤組成物を順次塗工した後、ヒートシール材層を積層することによりラミネート用バリア性複合フィルムを得る方法、
（Ｂ）ベースフィルム（ベースフィルムには複合フィルムも含まれる）に、上記接着剤組成物、ラミネート用バリア性コーティング組成物、接着剤組成物を順次塗工した後、ヒートシール材層を積層することによりラミネート用バリア性複合フィルムを得る方法、
（Ｃ）ベースフィルム（ベースフィルムには複合フィルムも含まれる）に、先にインキ組成物を印刷して印刷層を形成した後、上記接着剤組成物、ラミネート用バリア性コーティング組成物、接着剤組成物を順次塗工した後、ヒートシール材層を積層することによりラミネート用バリア性複合フィルムを得る方法、
（Ｄ）ベースフィルム（ベースフィルムには複合フィルムも含まれる）に、上記接着剤組成物、ラミネート用バリア性コーティング組成物、接着剤組成物を順次塗工した後、インキ組成物を印刷して印刷層を形成し、更にヒートシール材層を積層することによりラミネート用バリア性複合フィルムを得る方法、等である。
[Method for producing barrier composite film for laminating]
As a method for producing the barrier composite film for laminate of the present invention, as a result, it has a high barrier property, hydrothermal treatment property, suitability for lamination, and, if necessary, a decoration or display function added by printing. Any method may be used, but preferably, the following methods (A) to (D) are exemplified.
As the most basic configuration,
(A) A barrier film for laminating is performed by sequentially applying the barrier coating composition for laminating and the adhesive composition to a base film (including a composite film), and then laminating a heat seal material layer. A method for obtaining a conductive composite film,
(B) The above adhesive composition, laminating barrier coating composition, and adhesive composition are sequentially applied to a base film (including a composite film), and then a heat seal material layer is laminated. A method for obtaining a barrier composite film for lamination,
(C) After the ink composition is first printed on a base film (including a composite film), a printed layer is formed, and then the above adhesive composition, laminating barrier coating composition, and adhesive A method of obtaining a barrier composite film for laminating by laminating a heat sealing material layer after sequentially applying the composition,
(D) After coating the adhesive composition, the barrier barrier coating composition for laminating, and the adhesive composition on the base film (including the composite film), the ink composition is printed. And a method of obtaining a barrier composite film for laminating by forming a printed layer and further laminating a heat seal material layer.
尚、上記接着剤組成物及びラミネート用バリア性コーティング組成物の塗工方法については、通常のグラビアシリンダー等を用いたロールコーティング法、ドクターナイフ法やエアーナイフ・ノズルコーティング法、バーコーティング法、スプレーコーティング法、ディップコーティング法及びこれらの方法を組合わせたコーティング法等を用いることができる。
また、印刷層を形成するには、通常、グラビア印刷方式やフレキソ印刷方式が使用できる。
In addition, about the coating method of the said adhesive composition and the barrier coating composition for a laminate, the roll coating method using a normal gravure cylinder etc., a doctor knife method, an air knife nozzle coating method, a bar coating method, a spray A coating method, a dip coating method, a coating method combining these methods, and the like can be used.
In order to form a printing layer, a gravure printing method or a flexographic printing method can be usually used.
以上の方法から得られるラミネート用バリア性複合フィルムにおいて、接着層の膜厚（乾燥後）は、好ましくは２〜３μｍ、また、バリア層の膜厚（乾燥後）は、好ましくは０．１〜５μｍである。 In the barrier composite film for laminate obtained from the above method, the thickness of the adhesive layer (after drying) is preferably 2 to 3 μm, and the thickness of the barrier layer (after drying) is preferably 0.1 to 5 μm.
接着層の膜厚が２μｍより薄くなると、バリア層と他層との接着性が低下するおそれがあり、一方、３μｍより厚くなると、膜厚の増加に見合った接着性の増加が見られず、また、ラミネート用バリア性複合フィルムを包装袋として用いたときに、良好な取扱い性を得ることができないおそれがある。また、バリア層が０．１μｍより薄くなると、高いバリア性を得ることが困難となり、一方、５μｍを超えても顕著なバリア性の向上がみられす、バリア層中の無機層状化合物が多い場合に透明な塗膜を得ることが困難となる。
尚、１回の塗工により上記範囲内の膜厚を有する塗膜が得られない場合は、多数回の塗工を行うことも可能である。
If the thickness of the adhesive layer is less than 2 μm, the adhesion between the barrier layer and the other layer may be reduced. Moreover, when the barrier composite film for laminate is used as a packaging bag, there is a possibility that good handleability cannot be obtained. In addition, when the barrier layer is thinner than 0.1 μm, it is difficult to obtain high barrier properties. On the other hand, when the barrier layer exceeds 5 μm, significant improvement in barrier properties is observed, and there are many inorganic layered compounds in the barrier layer. It becomes difficult to obtain a transparent coating film.
In addition, when the coating film which has the film thickness in the said range is not obtained by one time of application | coating, it is also possible to perform many times of application.
他の機能層を設ける場合も、それぞれの機能層を設けるための良好な手段と、上記（Ａ）〜（Ｄ）の方法を組み合わせて、目的にあったラミネート用バリア性複合フィルムを製造することができる。 When providing other functional layers, a good means for providing each functional layer is combined with the above methods (A) to (D) to produce a barrier composite film for laminating purposes. Can do.
以上の製造方法から得られたラミネート用バリア性複合フィルムは、ヒートシーラー等を用いて、中折りして２辺を溶封するか又は２枚のラミネート用バリア性複合フィルムを重ねて三辺を溶封して先に袋状とした後、内容物を詰め、残りの一辺を溶封して、密封された包装袋として利用することができる。そして、得られた包装袋は、食品や医療品の包装袋として利用できる。 The barrier composite film for lamination obtained from the above production method is folded in two with a heat sealer or the like, or two sides are sealed, or two layers of the barrier composite film for lamination are overlapped to form three sides. After sealing and making it into a bag shape, the contents can be packed and the remaining side can be sealed and used as a sealed packaging bag. The obtained packaging bag can be used as a packaging bag for foods and medical products.
本発明のラミネート用バリア性コーティング組成物は、上述した構成からなるので、熱水処理しても、バリア性が良好で、且つラミネート強度の低下が少ないラミネート用バリア性複合フィルムを得ることができる。 Since the barrier coating composition for laminate according to the present invention has the above-described configuration, a barrier composite film for laminate having a good barrier property and little decrease in laminate strength can be obtained even by hot water treatment. .
以下に実施例をあげて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「％」は「質量％」を意味し、「部」は「質量部」を意味する。 The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. Unless otherwise specified, “%” means “% by mass”, and “part” means “part by mass”.
（バリア層を形成するためのラミネート用バリア性コーティング組成物）
＜エチレン−ビニルアルコール系共重合体溶液の調製＞
精製水２９．４９６質量部とｎ−プロピルアルコール（ＮＰＡ）４２．５質量部の混合溶媒に、エチレン−ビニルアルコール共重合体（商品名：ＳＧ−５２５、日本合成化学社製、エチレン−酢酸ビニル共重合体をケン化して得られた重合体、エチレン比率２６モル％、酢酸ビニル成分のケン化度約１００％、以下、ＥＶＯＨと略記することがある。）１５質量部を加え、更に濃度が３０％の過酸化水素水１３質量部とＦｅＳＯ４の０．００４質量部を添加して攪拌下で８０℃に加温し、約２時間反応させた。その後冷却して カタラーゼを３０００ｐｐｍになるように添加し、残存過酸化水素を除去し、これにより固形分１５％のほぼ透明なエチレン−ビニルアルコール共重合体溶液（ＥＶＯＨ溶液）を得た。
(Barrier coating composition for laminating to form a barrier layer)
<Preparation of ethylene-vinyl alcohol copolymer solution>
In a mixed solvent of 29.496 parts by mass of purified water and 42.5 parts by mass of n-propyl alcohol (NPA), an ethylene-vinyl alcohol copolymer (trade name: SG-525, manufactured by Nippon Synthetic Chemical Co., Ltd., ethylene-vinyl acetate) A polymer obtained by saponifying a copolymer, an ethylene ratio of 26 mol%, a saponification degree of a vinyl acetate component of about 100%, hereinafter abbreviated as EVOH.) 15 parts by mass is added, and the concentration is further increased. 13 parts by mass of 30% hydrogen peroxide and 0.004 part by mass of FeSO 4 were added, heated to 80 ° C. with stirring, and reacted for about 2 hours. Thereafter, the mixture was cooled and catalase was added to 3000 ppm to remove residual hydrogen peroxide, whereby an almost transparent ethylene-vinyl alcohol copolymer solution (EVOH solution) having a solid content of 15% was obtained.
＜ポリビニルアルコール樹脂溶液の調製＞
精製水５０％、ｎ−プロピルアルコール（ＮＰＡ）５０％を含む混合溶剤７０質量部に、完全けん化ポリビニルアルコール樹脂（商品名：ゴーセノールＮＬ−０５、日本合成化学社製、けん化度９９．５％以上）３０質量部を加え、溶解させ、これにより固形分３０％の透明なポリビニルアルコール溶液を得た。
<Preparation of polyvinyl alcohol resin solution>
To 70 parts by mass of a mixed solvent containing 50% purified water and 50% n-propyl alcohol (NPA), a completely saponified polyvinyl alcohol resin (trade name: Gohsenol NL-05, manufactured by Nippon Synthetic Chemical Co., Ltd., saponification degree: 99.5% or more ) 30 parts by mass was added and dissolved, thereby obtaining a transparent polyvinyl alcohol solution having a solid content of 30%.
＜無機層状化合物分散液の調製＞
無機層状化合物であるモンモリロナイト（商品名：クニピアＦ、クニミネ工業社製）４質量部を精製水９６質量部中に攪拌しながら添加し、高圧分散装置にて圧力５０ＭＰａの設定にて充分に分散した。その後、４０℃にて１日間保温し固形分４％の無機層状化合物分散液を得た。
<Preparation of inorganic layered compound dispersion>
4 parts by mass of montmorillonite (trade name: Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.), which is an inorganic layered compound, was added to 96 parts by mass of purified water while stirring, and was sufficiently dispersed at a pressure of 50 MPa with a high-pressure dispersing apparatus. . Thereafter, the mixture was kept at 40 ° C. for 1 day to obtain an inorganic layered compound dispersion having a solid content of 4%.
＜塩酸化ジルコニウム＞
商品名：Ｚｃ−２０、第一稀元素化学社製、固形分２０％）
＜他の架橋剤＞
カルボジイミド化合物（商品名：Ｖ−０２、日清紡社製、固形分４０％）
シランカップリング剤（商品名：ＫＢＥ−４０３、信越化学社製、固形分１００％）
<Zirconium chloride>
(Product name: Zc-20, manufactured by Daiichi Rare Element Chemical Co., Ltd., solid content 20%)
<Other cross-linking agents>
Carbodiimide compound (trade name: V-02, Nisshinbo Co., Ltd., solid content 40%)
Silane coupling agent (trade name: KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%)
＜実施例１のラミネート用バリア性コーティング組成物＞
無機層状化合物／ＥＶＯＨ＝２５／７５（固形分質量比）、塩酸化ジルコニウム３質量％）
精製水４４．２％、ＮＰＡ５５．８％の混合溶剤４３．７質量部に、ＥＶＯＨ溶液を２５質量部添加し、充分に攪拌混合した。更にこの溶液に、高速攪拌を行いながら無機層状化合物分散液３１．３質量部を添加した。この混合溶液１００部に対して、３部の陽イオン交換樹脂を添加しイオン交換樹脂の破砕が起きない程度の攪拌速度で１時間攪拌して、陽イオンの除去を行った後、陽イオン交換樹脂のみをストレーナで濾別した。
以上の操作から得られた混合溶液を、更に高圧分散装置にて圧力５０ＭＰａの設定で分散処理した後、分散処理した混合液９７質量部に対して塩酸化ジルコニウム（商品名：Ｚｃ−２０）の０．７５質量部、精製水４４．２％、ＮＰＡ５５．８％の混合溶剤２．２５質量部とを添加し混合攪拌を行い、それを２５５メッシュのフィルターにて濾過し固形分５％の実施例１のラミネート用バリア性コーティング組成物を得た。
<Barrier Coating Composition for Laminate of Example 1>
Inorganic layered compound / EVOH = 25/75 (mass ratio of solid content), zirconium hydrochloride 3% by mass)
25 parts by mass of the EVOH solution was added to 43.7 parts by mass of a mixed solvent of 44.2% purified water and 55.8% NPA, and the mixture was sufficiently stirred and mixed. Further, 31.3 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After removing cations after adding 3 parts of cation exchange resin to 100 parts of this mixed solution and stirring for 1 hour at a stirring speed at which crushing of the ion exchange resin does not occur, cation exchange is performed. Only the resin was filtered off with a strainer.
The mixed solution obtained from the above operation was further dispersed in a high-pressure dispersion apparatus at a pressure of 50 MPa, and then zirconium chloride (trade name: Zc-20) was added to 97 parts by mass of the dispersed mixture. 0.75 parts by mass, purified water 44.2%, NPA 55.8% mixed solvent 2.25 parts by mass was added and mixed and stirred, and it was filtered through a 255 mesh filter to achieve a solid content of 5%. The barrier coating composition for laminate of Example 1 was obtained.
＜実施例２のラミネート用バリア性コーティング組成物＞
無機層状化合物／ＥＶＯＨ＝２５／７５（固形分質量比）、塩酸化ジルコニウム０．５質量％
精製水４４．２％、ＮＰＡ５５．８％の混合溶剤４３．７質量部に、ＥＶＯＨ溶液を２５質量部添加し、充分に攪拌混合した。更にこの溶液に、高速攪拌を行いながら無機層状化合物分散液３１．３質量部を添加した。この混合溶液１００部に対して、３部の陽イオン交換樹脂を添加しイオン交換樹脂の破砕が起きない程度の攪拌速度で１時間攪拌して、陽イオンの除去を行った後、陽イオン交換樹脂のみをストレーナで濾別した。
以上の操作から得られた混合溶液を、更に高圧分散装置にて圧力５０ＭＰａの設定で分散処理した後、分散処理した混合液９９．５質量部に対して塩酸化ジルコニウム（商品名：Ｚｃ−２０）の０．１２５質量部、精製水４４．２％、ＮＰＡ５５．８％の混合溶剤０．３７５質量部とを添加し混合攪拌を行い、それを２５５メッシュのフィルターにて濾過し固形分５％の実施例２のラミネート用バリア性コーティング組成物を得た。
<Barrier Coating Composition for Laminate of Example 2>
Inorganic layered compound / EVOH = 25/75 (solid content mass ratio), zirconium hydrochloride 0.5% by mass
25 parts by mass of the EVOH solution was added to 43.7 parts by mass of a mixed solvent of 44.2% purified water and 55.8% NPA, and the mixture was sufficiently stirred and mixed. Further, 31.3 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After removing cations after adding 3 parts of cation exchange resin to 100 parts of this mixed solution and stirring for 1 hour at a stirring speed at which crushing of the ion exchange resin does not occur, cation exchange is performed. Only the resin was filtered off with a strainer.
The mixed solution obtained from the above operation was further subjected to a dispersion treatment with a high-pressure dispersion apparatus at a pressure of 50 MPa, and zirconium hydroxide (trade name: Zc-20 was added to 99.5 parts by weight of the dispersion treatment mixture. ) 0.125 parts by mass, purified water 44.2%, NPA 55.8% mixed solvent 0.375 parts by mass, mixed and stirred, filtered through a 255 mesh filter, and 5% solids The barrier coating composition for laminating of Example 2 was obtained.
＜実施例３のラミネート用バリア性コーティング組成物＞
無機層状化合物／ＥＶＯＨ＝２５／７５（固形分質量比）、塩酸化ジルコニウム５質量％
精製水４４．２％、ＮＰＡ５５．８％の混合溶剤４３．７質量部に、ＥＶＯＨ溶液を２５質量部添加し、充分に攪拌混合した。更にこの溶液に、高速攪拌を行いながら無機層状化合物分散液３１．３質量部を添加した。この混合溶液１００部に対して、３部の陽イオン交換樹脂を添加しイオン交換樹脂の破砕が起きない程度の攪拌速度で１時間攪拌して、陽イオンの除去を行った後、陽イオン交換樹脂のみをストレーナで濾別した。
以上の操作から得られた混合溶液を、更に高圧分散装置にて圧力５０ＭＰａの設定で分散処理した後、分散処理した混合液９５質量部に対して塩酸化ジルコニウム（商品名：Ｚｃ−２０）の１．２５質量部、精製水４４．２％、ＮＰＡ５５．８％の混合溶剤３．７５質量部とを添加し混合攪拌を行い、それを２５５メッシュのフィルターにて濾過し固形分５％の実施例３のラミネート用バリア性コーティング組成物を得た。
<Barrier Coating Composition for Laminate of Example 3>
Inorganic layered compound / EVOH = 25/75 (solid content mass ratio), zirconium hydrochloride 5 mass%
25 parts by mass of the EVOH solution was added to 43.7 parts by mass of a mixed solvent of 44.2% purified water and 55.8% NPA, and the mixture was sufficiently stirred and mixed. Further, 31.3 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After removing cations after adding 3 parts of cation exchange resin to 100 parts of this mixed solution and stirring for 1 hour at a stirring speed at which crushing of the ion exchange resin does not occur, cation exchange is performed. Only the resin was filtered off with a strainer.
The mixed solution obtained from the above operation was further subjected to a dispersion treatment with a high-pressure dispersion device at a pressure of 50 MPa, and then zirconium chloride (trade name: Zc-20) was added to 95 parts by mass of the dispersion treatment. Add 1.25 parts by mass, purified water 44.2%, NPA 55.8% mixed solvent 3.75 parts by mass, mix and stir, filter with a 255 mesh filter, and implement solid content 5% The barrier coating composition for laminate of Example 3 was obtained.
＜実施例４のラミネート用バリア性コーティング組成物＞
無機層状化合物／ＥＶＯＨ＝１５／８５（固形分質量比）、塩酸化ジルコニウム３質量％
精製水４４．２％、ＮＰＡ５５．８％の混合溶剤５２．９質量部に、ＥＶＯＨ溶液を２８．３質量部添加し、充分に攪拌混合した。更にこの溶液に、高速攪拌を行いながら無機層状化合物分散液１８．８質量部を添加した。この混合溶液１００部に対して、３部の陽イオン交換樹脂を添加しイオン交換樹脂の破砕が起きない程度の攪拌速度で１時間攪拌して、陽イオンの除去を行った後、陽イオン交換樹脂のみをストレーナで濾別した。
以上の操作から得られた混合溶液を、更に高圧分散装置にて圧力５０ＭＰａの設定で分散処理した後、分散処理した混合液９７質量部に対して塩酸化ジルコニウム（商品名：Ｚｃ−２０）の０．７５質量部、精製水４４．２％、ＮＰＡ５５．８％の混合溶剤２．２５質量部とを添加し混合攪拌を行い、それを２５５メッシュのフィルターにて濾過し固形分５％の実施例４のラミネート用バリア性コーティング組成物を得た。
<Barrier Coating Composition for Laminate of Example 4>
Inorganic layered compound / EVOH = 15/85 (mass ratio of solid content), 3% by mass of zirconium hydrochloride
28.3 parts by mass of the EVOH solution was added to 52.9 parts by mass of a mixed solvent of 44.2% purified water and 55.8% NPA, and the mixture was sufficiently stirred and mixed. Further, 18.8 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After removing cations after adding 3 parts of cation exchange resin to 100 parts of this mixed solution and stirring for 1 hour at a stirring speed at which crushing of the ion exchange resin does not occur, cation exchange is performed. Only the resin was filtered off with a strainer.
The mixed solution obtained from the above operation was further dispersed in a high-pressure dispersion apparatus at a pressure of 50 MPa, and then zirconium chloride (trade name: Zc-20) was added to 97 parts by mass of the dispersed mixture. 0.75 parts by mass, purified water 44.2%, NPA 55.8% mixed solvent 2.25 parts by mass was added and mixed and stirred, and it was filtered through a 255 mesh filter to achieve a solid content of 5%. The barrier coating composition for laminate of Example 4 was obtained.
＜実施例５のラミネート用バリア性コーティング組成物＞
無機層状化合物／ＥＶＯＨ＝３０／７０（固形分質量比）、塩酸化ジルコニウム３質量％
精製水４４．２％、ＮＰＡ５５．８％の混合溶剤３９．２質量部に、ＥＶＯＨ溶液を２３．３質量部添加し、充分に攪拌混合した。更にこの溶液に、高速攪拌を行いながら無機層状化合物分散液３７．５質量部を添加した。この混合溶液１００部に対して、３部の陽イオン交換樹脂を添加しイオン交換樹脂の破砕が起きない程度の攪拌速度で１時間攪拌して、陽イオンの除去を行った後、陽イオン交換樹脂のみをストレーナで濾別した。
以上の操作から得られた混合溶液を、更に高圧分散装置にて圧力５０ＭＰａの設定で分散処理した後、分散処理した混合液９７質量部に対して塩酸化ジルコニウム（商品名：Ｚｃ−２０）の０．７５質量部、精製水４４．２％、ＮＰＡ５５．８％の混合溶剤２．２５質量部とを添加し混合攪拌を行い、それを２５５メッシュのフィルターにて濾過し固形分５％の実施例５のラミネート用バリア性コーティング組成物を得た。
<Barrier Coating Composition for Laminate of Example 5>
Inorganic layered compound / EVOH = 30/70 (solid content mass ratio), zirconium hydrochloride 3% by mass
23.3 parts by mass of the EVOH solution was added to 39.2 parts by mass of a mixed solvent of 44.2% purified water and 55.8% NPA, followed by thorough mixing. Further, 37.5 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After removing cations after adding 3 parts of cation exchange resin to 100 parts of this mixed solution and stirring for 1 hour at a stirring speed at which crushing of the ion exchange resin does not occur, cation exchange is performed. Only the resin was filtered off with a strainer.
The mixed solution obtained from the above operation was further dispersed in a high-pressure dispersion apparatus at a pressure of 50 MPa, and then zirconium chloride (trade name: Zc-20) was added to 97 parts by mass of the dispersed mixture. 0.75 parts by mass, purified water 44.2%, NPA 55.8% mixed solvent 2.25 parts by mass was added and mixed and stirred, and it was filtered through a 255 mesh filter to achieve a solid content of 5%. The barrier coating composition for laminate of Example 5 was obtained.
＜比較例１のラミネート用バリア性コーティング組成物＞
無機層状化合物／ＥＶＯＨ＝２５／７５（固形分質量比）、塩酸化ジルコニウム０．０５質量％）
精製水４４．２％、ＮＰＡ５５．８％の混合溶剤４３．７質量部に、ＥＶＯＨ溶液を２５質量部添加し、充分に攪拌混合した。更にこの溶液に、高速攪拌を行いながら無機層状化合物分散液３１．３質量部を添加した。この混合溶液１００部に対して、３部の陽イオン交換樹脂を添加しイオン交換樹脂の破砕が起きない程度の攪拌速度で１時間攪拌して、陽イオンの除去を行った後、陽イオン交換樹脂のみをストレーナで濾別した。
以上の操作から得られた混合溶液を、更に高圧分散装置にて圧力５０ＭＰａの設定で分散処理した後、分散処理した混合液９９．９５質量部に対して塩酸化ジルコニウム（商品名：Ｚｃ−２０）の０．０１３質量部、精製水４４．２％、ＮＰＡ５５．８％の混合溶剤０．０３７質量部とを添加し混合攪拌を行い、それを２５５メッシュのフィルターにて濾過し固形分５％の比較例１のラミネート用バリア性コーティング組成物を得た。
<Barrier coating composition for laminate of Comparative Example 1>
Inorganic layered compound / EVOH = 25/75 (solid content mass ratio), zirconium hydrochloride 0.05 mass%)
25 parts by mass of the EVOH solution was added to 43.7 parts by mass of a mixed solvent of 44.2% purified water and 55.8% NPA, and the mixture was sufficiently stirred and mixed. Further, 31.3 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After removing cations after adding 3 parts of cation exchange resin to 100 parts of this mixed solution and stirring for 1 hour at a stirring speed at which crushing of the ion exchange resin does not occur, cation exchange is performed. Only the resin was filtered off with a strainer.
The mixed solution obtained from the above operation was further subjected to a dispersion treatment with a high-pressure dispersion apparatus at a pressure of 50 MPa, and thereafter, zirconium hydroxide (trade name: Zc-20) was added to 99.95 parts by mass of the dispersion mixture. ), 0.013 parts by weight of purified water, 44.2% purified water, and 0.037 parts by weight of a mixed solvent of 55.8% NPA are mixed and stirred. The mixture is filtered through a 255 mesh filter, and the solid content is 5%. The barrier coating composition for laminate of Comparative Example 1 was obtained.
＜比較例２のラミネート用バリア性コーティング組成物＞
無機層状化合物／ＥＶＯＨ＝２５／７５（固形分質量比）、塩酸化ジルコニウム１１質量％）
精製水４４．２％、ＮＰＡ５５．８％の混合溶剤４３．７質量部に、ＥＶＯＨ溶液を２５質量部添加し、充分に攪拌混合した。更にこの溶液に、高速攪拌を行いながら無機層状化合物分散液３１．３質量部を添加した。この混合溶液１００部に対して、３部の陽イオン交換樹脂を添加しイオン交換樹脂の破砕が起きない程度の攪拌速度で１時間攪拌して、陽イオンの除去を行った後、陽イオン交換樹脂のみをストレーナで濾別した。
以上の操作から得られた混合溶液を、更に高圧分散装置にて圧力５０ＭＰａの設定で分散処理した後、分散処理した混合液８９質量部に対して塩酸化ジルコニウム（商品名：Ｚｃ−２０）の２．７５質量部、精製水４４．２％、ＮＰＡ５５．８％の混合溶剤８．２５質量部とを添加し混合攪拌を行い、それを２５５メッシュのフィルターにて濾過し固形分５％の比較例２のラミネート用バリア性コーティング組成物を得た。
<Barrier coating composition for laminate of Comparative Example 2>
Inorganic layered compound / EVOH = 25/75 (solid content mass ratio), zirconium hydrochloride 11 mass%)
25 parts by mass of the EVOH solution was added to 43.7 parts by mass of a mixed solvent of 44.2% purified water and 55.8% NPA, and the mixture was sufficiently stirred and mixed. Further, 31.3 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After removing cations after adding 3 parts of cation exchange resin to 100 parts of this mixed solution and stirring for 1 hour at a stirring speed at which crushing of the ion exchange resin does not occur, cation exchange is performed. Only the resin was filtered off with a strainer.
The mixed solution obtained from the above operation was further dispersed in a high-pressure dispersion apparatus at a pressure of 50 MPa, and then zirconium chloride (trade name: Zc-20) was added to 89 parts by mass of the dispersed solution. 2.75 parts by mass, 44.2% purified water, 8.25 parts by mass of NPA 55.8% mixed solvent were added and mixed and stirred, then filtered through a 255 mesh filter and compared for 5% solids The barrier coating composition for laminate of Example 2 was obtained.
＜比較例３のラミネート用バリア性コーティング組成物＞
無機層状化合物／ＥＶＯＨ＝２５／７５（固形分質量比）、シランカップリング剤３質量％）
精製水４４．２％、ＮＰＡ５５．８％の混合溶剤４３．７質量部に、ＥＶＯＨ溶液を２５質量部添加し、充分に攪拌混合した。更にこの溶液に、高速攪拌を行いながら無機層状化合物分散液３１．３質量部を添加した。この混合溶液１００部に対して、３部の陽イオン交換樹脂を添加しイオン交換樹脂の破砕が起きない程度の攪拌速度で１時間攪拌して、陽イオンの除去を行った後、陽イオン交換樹脂のみをストレーナで濾別した。
以上の操作から得られた混合溶液を、更に高圧分散装置にて圧力５０ＭＰａの設定で分散処理した後、分散処理した混合液９７質量部に対してシランカップリング剤（商品名：ＫＢＥ−４０３）の０．１５質量部、精製水４４．２％、ＮＰＡ５５．８％の混合溶剤２．８５質量部とを添加し混合攪拌を行い、それを２５５メッシュのフィルターにて濾過し固形分５％の比較例３のラミネート用バリア性コーティング組成物を得た。
<Barrier Coating Composition for Laminate of Comparative Example 3>
Inorganic layered compound / EVOH = 25/75 (solid content mass ratio), silane coupling agent 3% by mass)
25 parts by mass of the EVOH solution was added to 43.7 parts by mass of a mixed solvent of 44.2% purified water and 55.8% NPA, and the mixture was sufficiently stirred and mixed. Further, 31.3 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After removing cations after adding 3 parts of cation exchange resin to 100 parts of this mixed solution and stirring for 1 hour at a stirring speed at which crushing of the ion exchange resin does not occur, cation exchange is performed. Only the resin was filtered off with a strainer.
The mixed solution obtained from the above operation was further subjected to a dispersion treatment with a high-pressure dispersion apparatus at a pressure of 50 MPa, and then a silane coupling agent (trade name: KBE-403) with respect to 97 parts by mass of the dispersion treatment mixture. 0.15 parts by mass of purified water, 44.2% purified water, and 2.85 parts by mass of a mixed solvent of 55.8% NPA were mixed and stirred. The mixture was filtered through a 255 mesh filter and the solid content was 5%. The barrier coating composition for laminate of Comparative Example 3 was obtained.
＜比較例４のラミネート用バリア性コーティング組成物＞
無機層状化合物／ＥＶＯＨ＝５／９５（固形分質量比）、塩酸化ジルコニウム３質量％）
精製水４４．２％、ＮＰＡ５５．８％の混合溶剤６２．０８質量部に、ＥＶＯＨ溶液を３１．６７質量部添加し、充分に攪拌混合した。更にこの溶液に、高速攪拌を行いながら無機層状化合物分散液６．２５質量部を添加した。この混合溶液１００部に対して、３部の陽イオン交換樹脂を添加しイオン交換樹脂の破砕が起きない程度の攪拌速度で１時間攪拌して、陽イオンの除去を行った後、陽イオン交換樹脂のみをストレーナで濾別した。
以上の操作から得られた混合溶液を、更に高圧分散装置にて圧力５０ＭＰａの設定で分散処理した後、分散処理した混合液９７質量部に対して塩酸化ジルコニウム（商品名：Ｚｃ−２０）の０．７５質量部、精製水４４．２％、ＮＰＡ５５．８％の混合溶剤２．２５質量部とを添加し混合攪拌を行い、それを２５５メッシュのフィルターにて濾過し固形分５％の比較例４のラミネート用バリア性コーティング組成物を得た。
<Barrier Coating Composition for Laminate of Comparative Example 4>
Inorganic layered compound / EVOH = 5/95 (solid content mass ratio), zirconium hydrochloride 3 mass%)
31.67 parts by mass of the EVOH solution was added to 62.08 parts by mass of a mixed solvent of 44.2% purified water and 55.8% NPA, and the mixture was sufficiently stirred and mixed. Further, 6.25 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After removing cations after adding 3 parts of cation exchange resin to 100 parts of this mixed solution and stirring for 1 hour at a stirring speed at which crushing of the ion exchange resin does not occur, cation exchange is performed. Only the resin was filtered off with a strainer.
The mixed solution obtained from the above operation was further dispersed in a high-pressure dispersion apparatus at a pressure of 50 MPa, and then zirconium chloride (trade name: Zc-20) was added to 97 parts by mass of the dispersed mixture. Add 0.75 parts by mass, purified water 44.2%, NPA 55.8% mixed solvent 2.25 parts by mass, mix and stir, filter through a 255 mesh filter and compare 5% solids The barrier coating composition for laminate of Example 4 was obtained.
＜比較例５のラミネート用バリア性コーティング組成物＞
無機層状化合物／ＥＶＯＨ＝５０／５０（固形分質量比）、塩酸化ジルコニウム３質量％）
精製水４４．２％、ＮＰＡ５５．８％の混合溶剤２０．８質量部に、ＥＶＯＨ溶液を１６．７質量部添加し、充分に攪拌混合した。更にこの溶液に、高速攪拌を行いながら無機層状化合物分散液６２．５質量部を添加した。この混合溶液１００部に対して、３部の陽イオン交換樹脂を添加しイオン交換樹脂の破砕が起きない程度の攪拌速度で１時間攪拌して、陽イオンの除去を行った後、陽イオン交換樹脂のみをストレーナで濾別した。
以上の操作から得られた混合溶液を、更に高圧分散装置にて圧力５０ＭＰａの設定で分散処理した後、分散処理した混合液９７質量部に対して塩酸化ジルコニウム（商品名：Ｚｃ−２０）の０．７５質量部、精製水４４．２％、ＮＰＡ５５．８％の混合溶剤２．２５質量部とを添加し混合攪拌を行い、それを２５５メッシュのフィルターにて濾過し固形分５％の比較例５のラミネート用バリア性コーティング組成物を得た。
<Barrier Coating Composition for Laminate of Comparative Example 5>
Inorganic layered compound / EVOH = 50/50 (solid mass ratio), zirconium hydrochloride 3 mass%)
16.7 parts by mass of the EVOH solution was added to 20.8 parts by mass of a mixed solvent of 44.2% purified water and 55.8% NPA, and the mixture was sufficiently stirred and mixed. Further, 62.5 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After removing cations after adding 3 parts of cation exchange resin to 100 parts of this mixed solution and stirring for 1 hour at a stirring speed at which crushing of the ion exchange resin does not occur, cation exchange is performed. Only the resin was filtered off with a strainer.
The mixed solution obtained from the above operation was further dispersed in a high-pressure dispersion apparatus at a pressure of 50 MPa, and then zirconium chloride (trade name: Zc-20) was added to 97 parts by mass of the dispersed mixture. Add 0.75 parts by mass, purified water 44.2%, NPA 55.8% mixed solvent 2.25 parts by mass, mix and stir, filter through a 255 mesh filter and compare 5% solids The barrier coating composition for laminate of Example 5 was obtained.
＜比較例６のラミネート用バリア性コーティング組成物＞
無機層状化合物／ポリビニルアルコール樹脂＝２５／７５（固形分質量比）、塩酸化ジルコニウム３質量％）
精製水４４．２％、ＮＰＡ５５．８％の混合溶剤５６．２５質量部に、ポリビニルアルコール樹脂溶液を１２．５質量部添加し、充分に攪拌混合した。更にこの溶液に、高速攪拌を行いながら無機層状化合物分散液３１．２５質量部を添加した。この混合溶液１００部に対して、３部の陽イオン交換樹脂を添加しイオン交換樹脂の破砕が起きない程度の攪拌速度で１時間攪拌して、陽イオンの除去を行った後、陽イオン交換樹脂のみをストレーナで濾別した。
以上の操作から得られた混合溶液を、更に高圧分散装置にて圧力５０ＭＰａの設定で分散処理した後、分散処理した混合液９７質量部に対して塩酸化ジルコニウム（商品名：Ｚｃ−２０）の０．７５質量部、精製水４４．２％、ＮＰＡ５５．８％の混合溶剤２．２５質量部とを添加し混合攪拌を行い、それを２５５メッシュのフィルターにて濾過し固形分５％の比較例６のラミネート用バリア性コーティング組成物を得た。
<Barrier Coating Composition for Laminate of Comparative Example 6>
Inorganic layered compound / polyvinyl alcohol resin = 25/75 (mass ratio of solid content), zirconium chloride 3 mass%)
12.5 parts by mass of a polyvinyl alcohol resin solution was added to 56.25 parts by mass of a mixed solvent of 44.2% purified water and 55.8% NPA, and the mixture was sufficiently stirred and mixed. Further, 31.25 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After removing cations after adding 3 parts of cation exchange resin to 100 parts of this mixed solution and stirring for 1 hour at a stirring speed at which crushing of the ion exchange resin does not occur, cation exchange is performed. Only the resin was filtered off with a strainer.
The mixed solution obtained from the above operation was further dispersed in a high-pressure dispersion apparatus at a pressure of 50 MPa, and then zirconium chloride (trade name: Zc-20) was added to 97 parts by mass of the dispersed mixture. Add 0.75 parts by mass, purified water 44.2%, NPA 55.8% mixed solvent 2.25 parts by mass, mix and stir, filter through a 255 mesh filter and compare 5% solids The barrier coating composition for laminate of Example 6 was obtained.
＜実施例１〜５及び比較例１〜６のラミネート用バリア性複合フィルム−加湿用＞
ポリエステルフィルムにラミネート用接着剤組成物（押出しアンカーコート剤、Ａ３２１０／３０７０、三井化学ポリウレタン社製）に塗布し、乾燥後、実施例１〜５及び比較例１〜６のラミネート用バリア性コーティング組成物を塗工し、乾燥させた。得られたバリア層の上に、ポリエーテル系接着剤組成物（Ａ−９６９、三井化学ポリウレタン社製）を用いてドライラミネート機にて無延伸ポリプロピレンフィルムを積層し、４０℃にて３日間エージングして実施例１〜５及び比較例１〜６のラミネート用バリア性複合フィルムを得た。
なお、バリヤ層の膜厚は０．５μｍ（乾燥皮膜）、接着層の膜厚は３μｍ（乾燥皮膜）であった。
<Barrier composite films for laminates of Examples 1 to 5 and Comparative Examples 1 to 6 for humidification>
The polyester film was applied to an adhesive composition for lamination (extruded anchor coating agent, A3210 / 3070, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), and after drying, the barrier coating compositions for laminates of Examples 1 to 5 and Comparative Examples 1 to 6 were used. The product was applied and dried. On the obtained barrier layer, an unstretched polypropylene film was laminated with a dry laminating machine using a polyether-based adhesive composition (A-969, manufactured by Mitsui Chemicals Polyurethanes), and aged at 40 ° C. for 3 days. Thus, barrier composite composite films for Examples 1 to 5 and Comparative Examples 1 to 6 were obtained.
The film thickness of the barrier layer was 0.5 μm (dry film), and the film thickness of the adhesive layer was 3 μm (dry film).
〔評価〕
（酸素透過度）
実施例１〜５及び比較例１〜６のラミネート用バリア性複合フィルムを２３℃、９０％ＲＨの雰囲気下に２日間放置後、ＪＩＳ Ｋ７１２６ Ｂ法に準じて、酸素透過率測定装置（Ｍｏｃｏｎ社製；ＯＸ−ＴＲＡＮ１００、商品名）を用いて酸素透過度（ＯＴＲ値）を測定した。尚、測定は、２３℃において、９０％ＲＨの雰囲気下で行った。結果を表１に示す。
[Evaluation]
(Oxygen permeability)
The barrier composite films for laminates of Examples 1 to 5 and Comparative Examples 1 to 6 were allowed to stand in an atmosphere of 23 ° C. and 90% RH for 2 days. Oxygen permeability (OTR value) was measured using OX-TRAN100 (trade name). The measurement was performed at 23 ° C. in an atmosphere of 90% RH. The results are shown in Table 1.
（加湿前と加湿後のラミネート強度）
（１）加湿前
実施例１〜５及び比較例１〜６の各ラミネート用バリア性複合フィルムを１５ｍｍ幅に切断し、Ｔ型剥離強度を剥離試験機（安田精機社製）を用いて、剥離速度３００ｍｍ／ｍｉｎにてラミネート強度を測定した。結果を表１に示す。
（２）加湿後
実施例１〜５及び比較例１〜６の各ラミネート用バリア性複合フィルムを１５ｍｍ幅に切断した各試料片を２３℃、９０％ＲＨの雰囲気下に２日間放置後、Ｔ型剥離強度を剥離試験機（安田精機社製）を用いて、剥離速度３００ｍｍ／ｍｉｎにて測定した。結果を表１に示す。
(Lamination strength before and after humidification)
(1) Each of the barrier composite films for lamination in Examples 1 to 5 and Comparative Examples 1 to 6 before humidification was cut to a width of 15 mm, and the T-type peel strength was peeled using a peel tester (manufactured by Yasuda Seiki Co., Ltd.). The laminate strength was measured at a speed of 300 mm / min. The results are shown in Table 1.
(2) After humidification, each sample piece obtained by cutting each of the laminated barrier composite films of Examples 1 to 5 and Comparative Examples 1 to 6 into a width of 15 mm was allowed to stand in an atmosphere of 23 ° C. and 90% RH for 2 days. The mold peel strength was measured at a peel speed of 300 mm / min using a peel tester (manufactured by Yasuda Seiki Co., Ltd.). The results are shown in Table 1.
（ボイル適性）
実施例１〜５及び比較例１〜６のラミネート用バリア性複合フィルムのそれぞれについて、２０ｃｍ×２０ｃｍの大きさのものを２枚用いて、同容積となるように製袋し、水を詰めた後に溶封した。溶封した各製袋を９５℃の熱水中に３０分間浸漬し、ラミ浮きの有無からボイル適性を評価した。結果を表１に示す。
評価基準
Ａ：ラミ浮きのないもの
Ｂ：ラミ浮きがあるもの
(Boil aptitude)
About each of the barrier composite films for laminates of Examples 1 to 5 and Comparative Examples 1 to 6, using two sheets having a size of 20 cm × 20 cm, the bags were made to have the same volume and filled with water. Sealed later. Each sealed bag was immersed in hot water at 95 ° C. for 30 minutes, and the suitability of the boil was evaluated based on the presence or absence of lami floating. The results are shown in Table 1.
Evaluation criteria A: No lami float B: Lami float
実施例のラミネート用バリア性複合フィルムは、高湿度下で放置した後でもバリア性が優れていると同時に、加湿によるラミネート強度の低下も抑制できた。また、ボイル適性にも優れていた。一方、比較例では、これらすべての性能に優れたものは得られなかった。 The barrier composite films for laminates of the examples had excellent barrier properties even after being left under high humidity, and at the same time, could suppress a decrease in laminate strength due to humidification. In addition, the boil aptitude was excellent. On the other hand, in the comparative example, the thing excellent in all these performances was not obtained.
本発明のラミネート用バリア性コーティング組成物及びそれを用いたラミネート用バリア性複合フィルムは、食品包装用途で利用される包装袋（特に熱水処理用包装袋）に好適に適用できる。 The laminate barrier coating composition of the present invention and the laminate barrier composite film using the same can be suitably applied to packaging bags (particularly hot water treatment packaging bags) used in food packaging applications.
Claims (6)
更に、（Ｄ）水溶性ジルコニウム化合物を含有し、
以下の式１及び式２を満足する
ことを特徴とするラミネート用バリア性コーティング組成物。
（式１） ＷＢ／ＷＡ＝１０／９０〜３５／６５
（式１中、ＷＡはラミネート用バリア性コーティング組成物中の（Ａ）成分の含有量（質量）、ＷＢはラミネート用バリア性コーティング組成物中の（Ｂ）成分の含有量（質量）を表す。）
（式２） ｛ＷＤ／（ＷＡ＋ＷＢ＋ＷＤ）｝×１００＝０．１〜１０
（式２中、ＷＡ、ＷＢは前記と同じ定義、ＷＤはラミネート用バリア性コーティング組成物中の（Ｄ）成分の含有量（質量）を表す。） (A) An ethylene-vinyl acetate copolymer saponified and further treated with a peroxide, an ethylene-vinyl alcohol copolymer, (B) an inorganic layered compound, and (C) a barrier for a laminate containing a solvent In the protective coating composition,
And (D) a water-soluble zirconium compound,
A barrier coating composition for laminating, which satisfies the following formulas 1 and 2.
(Equation 1) W B / W A = 10 / 90~35 / 65
(In the formula 1, the content of W A component (A) of the barrier coating composition laminate (mass), W B is the content of the component (B) of the barrier coating composition laminate (mass) Represents.)
(Formula 2) {W D / (W A + W B + W D )} × 100 = 0.1-10
(In the formula 2, W A, W B are as defined above, W D represents the content of component (D) of the barrier coating composition for laminating the (mass).)
該バリア層が、請求項１、２、３又は４記載のラミネート用バリア性コーティング組成物から得られるものである
ことを特徴とするラミネート用バリア性複合フィルム。 Consists of at least a base film layer, a barrier layer, a heat seal material layer, and further in the barrier composite film for laminating provided with the respective layers in this order,
A barrier composite film for laminating, wherein the barrier layer is obtained from the barrier coating composition for laminating according to claim 1, 2, 3 or 4.
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