JP2007131712A - Gas barrier film, gas barrier laminate and method for preparation of the same - Google Patents
Gas barrier film, gas barrier laminate and method for preparation of the same Download PDFInfo
- Publication number
- JP2007131712A JP2007131712A JP2005325418A JP2005325418A JP2007131712A JP 2007131712 A JP2007131712 A JP 2007131712A JP 2005325418 A JP2005325418 A JP 2005325418A JP 2005325418 A JP2005325418 A JP 2005325418A JP 2007131712 A JP2007131712 A JP 2007131712A
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- unsaturated carboxylic
- gas barrier
- acid compound
- metal salt
- 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 109
- 238000000034 method Methods 0.000 title description 34
- 238000002360 preparation method Methods 0.000 title description 5
- -1 carboxylic acid compound Chemical class 0.000 claims abstract description 152
- 229910052751 metal Inorganic materials 0.000 claims abstract description 124
- 239000002184 metal Substances 0.000 claims abstract description 124
- 150000003839 salts Chemical class 0.000 claims abstract description 113
- 229920001577 copolymer Polymers 0.000 claims abstract description 39
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 239000011833 salt mixture Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 27
- 238000002835 absorbance Methods 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000862 absorption spectrum Methods 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 230000005865 ionizing radiation Effects 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 239000012528 membrane Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 84
- 239000011259 mixed solution Substances 0.000 abstract description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 7
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
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- 238000010438 heat treatment Methods 0.000 abstract description 3
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
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- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
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- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 5
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 4
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical group CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
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- 229910003002 lithium salt Inorganic materials 0.000 description 3
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 description 3
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- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical class C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 2
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical class CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 2
- 244000215068 Acacia senegal Species 0.000 description 2
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- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012793 heat-sealing layer Substances 0.000 description 1
- ILVUABTVETXVMV-UHFFFAOYSA-N hydron;bromide;iodide Chemical compound Br.I ILVUABTVETXVMV-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- PGAPATLGJSQQBU-UHFFFAOYSA-M thallium(i) bromide Chemical compound [Tl]Br PGAPATLGJSQQBU-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
本発明は、透明性を有し、ガスバリア性、特に高湿度下での酸素ガスバリア性に優れた包装材料に好適なガスバリア性膜、ガスバリア性積層体及びその製造方法に関する。 The present invention relates to a gas barrier film suitable for a packaging material having transparency and excellent gas barrier properties, particularly oxygen gas barrier properties under high humidity, a gas barrier laminate, and a method for producing the same.
従来、酸素あるいは水蒸気等に対するバリア性材料として、アルミ等の金属箔をガスバリア層として用いた包装材料が一般的に用いられているが、包装材料を透視して内容物を確認することができない等の問題ある。そのため近年では、フィルム基材に酸化ケイ素、酸化アルミニウム等の無機酸化物を、真空蒸着法、スパッタリング法、イオンプレーティング法、化学気相成長法等で形成してなる透明ガスバリア性フィルムが注目されている。そして、かかる透明ガスバリア性フィルムは、一般には透明性、剛性に優れる二軸延伸ポリエステルフィルムからなる基材面に無機酸化物を蒸着したフィルムであるので、そのままでは蒸着層が使用時の摩擦等に弱く、包装用フィルムとして使用する場合、後加工の印刷やラミネート時、又、内容物の充填時に、擦れや伸びにより無機酸化物にクラックが入りガスバリア性が低下することがあり、無機酸化物蒸着だけでは十分なガスバリア性が得られないといった問題がある。
かかる欠点を改良する方法として、ガスバリア性を有するポリビニルアルコールを金属酸化物薄膜上に積層する方法（例えば、特許文献１）、無機化合物からなる蒸着層面に水溶性高分子と、（ａ）１種以上のアルコキシドまたは／およびその加水分解物または（ｂ）塩化錫の少なくともいずれか１つを含む水溶液、或いは水／アルコール混合溶液を主剤とするコーティング剤を塗布した積層フィルム（特許文献２）、特定のオルガノシラン、シリル基含有フッ素系重合体及びオルガノポリシロキサンからなるコーティング組成物を塗布してなる積層フィルム（特許文献３）、あるいはポリビニルアルコール系樹脂と金属アルコレート類からなるコーティング剤を塗布してなるガスバリアコーティングフィルム（特許文献４）等が提案されている。しかしながら、ポリビニルアルコールを積層してなるガスバリア性フィルムは、高湿度下でのガスバリア性が低下する場合あり、エチレン・ビニルアルコール共重合体とポリ（メタ）アクリル酸との組成物では、高湿度下でのガスバリア性を持たせるために、１８０〜２００℃で５分間と高温での処理を必要とする。
Conventionally, as a barrier material against oxygen or water vapor, a packaging material using a metal foil such as aluminum as a gas barrier layer is generally used, but the contents cannot be confirmed through the packaging material, etc. There is a problem. Therefore, in recent years, a transparent gas barrier film in which an inorganic oxide such as silicon oxide or aluminum oxide is formed on a film substrate by vacuum deposition, sputtering, ion plating, chemical vapor deposition, or the like has attracted attention. ing. Such a transparent gas barrier film is a film obtained by depositing an inorganic oxide on a base material surface made of a biaxially stretched polyester film that is generally excellent in transparency and rigidity. When used as a packaging film, it may cause cracks in the inorganic oxide due to rubbing or elongation during post-processing printing or laminating or filling the contents, and the gas barrier property may be reduced. However, there is a problem that sufficient gas barrier properties cannot be obtained.
As a method for improving such a defect, a method of laminating a polyvinyl alcohol having gas barrier properties on a metal oxide thin film (for example, Patent Document 1), a water-soluble polymer on a vapor deposition layer surface made of an inorganic compound, and (a) one kind A laminated film coated with an aqueous solution containing at least one of the above alkoxides and / or their hydrolysates or (b) tin chloride, or a water / alcohol mixed solution (Patent Document 2), specific A laminated film (Patent Document 3) obtained by applying a coating composition comprising an organosilane, a silyl group-containing fluoropolymer and an organopolysiloxane, or a coating agent comprising a polyvinyl alcohol resin and a metal alcoholate. Gas barrier coating film (Patent Document 4) etc. That. However, the gas barrier film formed by laminating polyvinyl alcohol may have a reduced gas barrier property under high humidity. In the composition of ethylene / vinyl alcohol copolymer and poly (meth) acrylic acid, In order to give the gas barrier property in the above, treatment at a high temperature of 180 to 200 ° C. for 5 minutes is required.
そこで本発明は、高温での熱処理を必要とせず、しかも、酸素バリア性が高く帯電防止性を有するガスバリア性膜及びガスバリア積層体を得ることを目的とする。 Accordingly, an object of the present invention is to obtain a gas barrier film and a gas barrier laminate that do not require heat treatment at a high temperature and that have high oxygen barrier properties and antistatic properties.
本発明は、５０モル％を超える割合の不飽和カルボン酸化合物一価金属塩を含む不飽和カルボン酸化合物多価金属塩共重合体が形成されてなることを特徴とするガスバリア性膜、及び基材層の少なくとも片面にかかるガスバリア性膜が積層されてなるガスバリア性積層体を提供するものである。 The present invention relates to a gas barrier film characterized in that an unsaturated carboxylic acid compound polyvalent metal salt copolymer containing an unsaturated carboxylic acid compound monovalent metal salt in a proportion exceeding 50 mol% is formed. The present invention provides a gas barrier laminate comprising a gas barrier film laminated on at least one surface of a material layer.
本発明は、基材層の少なくとも片面に、５０モル％を超える割合の重合度が２０未満の不飽和カルボン酸化合物の一価金属塩と５０モル％未満の重合度が２０未満の不飽和カルボン酸化合物の多価金属塩との混合物の溶液、好ましくは水溶液を塗布した後、該金属塩混合物を、好ましくは水分の存在下に重合することにより不飽和カルボン酸化合物金属塩の共重合体層を形成させることを特徴とするガスバリア性積層体の製造方法に関する。 The present invention relates to a monovalent metal salt of an unsaturated carboxylic acid compound having a degree of polymerization of less than 20 and a unsaturated carboxylic acid having a degree of polymerization of less than 20 of less than 50 mol% on at least one side of the substrate layer. After applying a solution of a mixture of a polyvalent metal salt of an acid compound, preferably an aqueous solution, and then polymerizing the metal salt mixture, preferably in the presence of moisture, a copolymer layer of an unsaturated carboxylic acid compound metal salt It is related with the manufacturing method of the gas-barrier laminated body characterized by forming.
本発明の５０モル％を超える割合の不飽和カルボン酸化合物一価金属塩を含む不飽和カルボン酸化合物多価金属塩共重合体からなるガスバリア性膜が基材層に積層されてなるガスバリア性積層体は、遊離のカルボン酸が少ないので、高湿度下でのガスバリア性に優れている。
本発明のガスバリア性積層体の製造方法は、５０モル％を超える割合の重合度が２０未満の不飽和カルボン酸化合物の一価金属塩と５０モル％未満の重合度が２０未満の不飽和カルボン酸化合物の多価金属塩との混合物（不飽和カルボン酸化合物の一価金属塩と不飽和カルボン酸化合物の多価金属塩との合計量が１００モル％）の水溶液を用いることにより、該金属塩混合物が重合時に適度に水分を保持することができるので、基材層の形状がフィルム状に限らず、あらゆる形状の基材に塗布することが容易であり、しかも、中和度が高い、即ち、ガスバリア性に優れる不飽和カルボン酸多価金属化合物共重合体からなる膜を容易に製造し得る。
A gas barrier laminate in which a gas barrier film comprising an unsaturated carboxylic acid compound polyvalent metal salt copolymer containing an unsaturated carboxylic acid compound monovalent metal salt in a proportion exceeding 50 mol% of the present invention is laminated on a base material layer Since the body has a small amount of free carboxylic acid, it has excellent gas barrier properties under high humidity.
The method for producing a gas barrier laminate of the present invention comprises a monovalent metal salt of an unsaturated carboxylic acid compound having a degree of polymerization of less than 20 and a unsaturated carboxylic acid having a degree of polymerization of less than 20 of less than 50 mol%. By using an aqueous solution of a mixture of a polyvalent metal salt of an acid compound (a total amount of a monovalent metal salt of an unsaturated carboxylic acid compound and a polyvalent metal salt of an unsaturated carboxylic acid compound is 100 mol%), the metal Since the salt mixture can appropriately retain moisture during polymerization, the shape of the base material layer is not limited to a film shape, it is easy to apply to a base material of any shape, and the degree of neutralization is high. That is, a film made of an unsaturated carboxylic acid polyvalent metal compound copolymer having excellent gas barrier properties can be easily produced.
不飽和カルボン酸化合物
本発明のガスバリア性膜である５０モル％を超える割合の不飽和カルボン酸化合物一価金属塩を含む不飽和カルボン酸化合物多価金属塩共重合体（以下、「共重合体」と略称する場合がある。）を形成する成分である不飽和カルボン酸化合物は、アクリル酸、メタアクリル酸、マレイン酸、イタコン酸等のα、β―エチレン性不飽和基を有するカルボン酸化合物であり、重合度が２０未満、好ましくは単量体若しくは１０以下の重合体である。重合度が２０を越える重合体（高分子化合物）を用いた場合は、後述の多価金属化合物及び／又は一価金属化合物との塩が完全には形成されない虞があり、その結果、当該金属塩を共重合して得られる層は高湿度下でのガスバリア性が劣る虞がある。これら不飽和カルボン酸化合物は、一種でも二種以上の混合物であってもよい。
これら不飽和カルボン酸化合物の中でも単量体が一価金属化合物及び多価金属化合物で完全に中和された塩が形成し易く、当該塩を共重合して得られる共重合体層を基材層の少なくとも片面に積層してなるガスバリア性積層体は高湿度下でのガスバリア性に特に優れるので好ましい。
Unsaturated carboxylic acid compound Unsaturated carboxylic acid compound polyvalent metal salt copolymer (hereinafter referred to as "copolymer") containing the unsaturated carboxylic acid compound monovalent metal salt in a proportion exceeding 50 mol%, which is the gas barrier film of the present invention. The unsaturated carboxylic acid compound that is a component that forms a) is a carboxylic acid compound having an α, β-ethylenically unsaturated group such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid. The degree of polymerization is less than 20, preferably a monomer or 10 or less polymer. When a polymer (polymer compound) having a degree of polymerization exceeding 20 is used, there is a possibility that a salt with a polyvalent metal compound and / or a monovalent metal compound described later may not be formed completely. The layer obtained by copolymerizing the salt may be inferior in gas barrier properties under high humidity. These unsaturated carboxylic acid compounds may be one kind or a mixture of two or more kinds.
Among these unsaturated carboxylic acid compounds, a monomer is easily formed as a salt completely neutralized with a monovalent metal compound and a polyvalent metal compound, and a copolymer layer obtained by copolymerizing the salt is used as a base material. A gas barrier laminate obtained by laminating at least one side of the layer is preferable because it is particularly excellent in gas barrier properties under high humidity.
多価金属化合物
本発明に係わる共重合体を形成する成分の一つである多価金属化合物は、周期表の２Ａ〜７Ａ族、１Ｂ〜３Ｂ族及び８族に属する金属及び金属化合物であり、具体的には、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、バリウム（Ｂａ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、アルミニウム（Ａｌ）等の二価以上の金属、これら金属の酸化物、水酸化物、ハロゲン化物、炭酸塩、リン酸塩、亜リン酸塩、次亜リン酸塩、硫酸塩若しくは亜硫酸塩等である。これら金属化合物の中でも、二価の金属化合物が好ましく、特には酸化マグネシウム、酸化カルシウム、酸化バリウム、酸化亜鉛、水酸化マグネシウム、水酸化カルシウム、水酸化バリウム、水酸化亜鉛等が好ましい。これら二価の金属化合物を用いた場合は、前記不飽和カルボン酸化合物との塩を重合して得られる膜の高湿度下でのガスバリア性が特に優れている。これら多価金属化合物は、少なくとも一種が使用され、一種のみの使用であっても、二種以上を併用してもよい。これら多価金属化合物の中でもＭｇ、Ｃａ、Ｚｎ、ＢａおよびＡｌが好ましく、中でも、特にＺｎが好ましい。
The polyvalent metal compound which is one of the components forming the copolymer according to the present invention is a metal and a metal compound belonging to groups 2A to 7A, 1B to 3B and 8 of the periodic table, Specifically, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), Bivalent or higher metals such as aluminum (Al), oxides, hydroxides, halides, carbonates, phosphates, phosphites, hypophosphites, sulfates or sulfites of these metals is there. Among these metal compounds, divalent metal compounds are preferable, and magnesium oxide, calcium oxide, barium oxide, zinc oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and the like are particularly preferable. When these divalent metal compounds are used, the gas barrier property under high humidity of the film obtained by polymerizing the salt with the unsaturated carboxylic acid compound is particularly excellent. At least one kind of these polyvalent metal compounds is used, and only one kind may be used or two or more kinds may be used in combination. Among these polyvalent metal compounds, Mg, Ca, Zn, Ba and Al are preferable, and among them, Zn is particularly preferable.
一価金属化合物
本発明に係わる共重合体を形成する成分の一つである一価金属化合物は、周期表の１Ａ族、即ち、アルカリ金属及びその金属化合物であり、具体的には、リチウム（Ｌｉ）、ナトリウム（Ｎａ）、カリウム（Ｋ）等の一価金属、これら金属の酸化物、水酸化物、ハロゲン化物、炭酸塩、リン酸塩、亜リン酸塩、次亜リン酸塩、硫酸塩若しくは亜硫酸塩等であり、具体的には酸化ナトリウム、酸化カリウム、水酸化ナトリウム、水酸化カリウム等を挙げることができる。これら一価の金属化合物を用いた場合は、前記不飽和カルボン酸化合物多価金属塩と共重合して得られる膜の高湿度下でのガスバリア性が特に優れている。これら一価金属化合物は、少なくとも一種が使用され、一種のみの使用であっても、二種以上を併用してもよい。これら多価金属化合物の中でもＮａ（ナトリウム）およびＫ（カリウム）が好ましい。
Monovalent metal compound The monovalent metal compound which is one of the components forming the copolymer according to the present invention is a group 1A of the periodic table, that is, an alkali metal and its metal compound. Specifically, lithium ( Li), monovalent metals such as sodium (Na), potassium (K), oxides, hydroxides, halides, carbonates, phosphates, phosphites, hypophosphites, sulfuric acids of these metals Salt or sulfite, and specific examples include sodium oxide, potassium oxide, sodium hydroxide, potassium hydroxide, and the like. When these monovalent metal compounds are used, the gas barrier property under high humidity of the film obtained by copolymerization with the unsaturated carboxylic acid compound polyvalent metal salt is particularly excellent. At least one kind of these monovalent metal compounds is used, and only one kind may be used or two or more kinds may be used in combination. Among these polyvalent metal compounds, Na (sodium) and K (potassium) are preferable.
不飽和カルボン酸化合物多価金属塩
本発明に係る共重合体の基となる不飽和カルボン酸化合物多価金属塩は、前記重合度が２０未満の不飽和カルボン酸化合物と前記多価金属化合物との塩である。これら不飽和カルボン酸化合物多価金属塩は一種でも二種以上の混合物であってもよい。かかる不飽和カルボン酸化合物多価金属塩の中でも、特に（メタ）アクリル酸亜鉛が得られる共重合体層の耐熱水性に優れるので好ましい。
Unsaturated carboxylic acid compound polyvalent metal salt Unsaturated carboxylic acid compound polyvalent metal salt which is the group of the copolymer according to the present invention comprises an unsaturated carboxylic acid compound having a degree of polymerization of less than 20 and the polyvalent metal compound. Of salt. These unsaturated carboxylic acid compound polyvalent metal salts may be one kind or a mixture of two or more kinds. Among such unsaturated carboxylic acid compound polyvalent metal salts, the copolymer layer from which zinc (meth) acrylate is obtained is particularly excellent in the hot water resistance, and therefore preferred.
不飽和カルボン酸化合物一価金属塩
本発明に係る不飽和カルボン酸化合物金属塩共重合体の基となる不飽和カルボン酸化合物一価金属塩は、前記重合度が２０未満の不飽和カルボン酸化合物と前記一価金属化合物との塩である。これら不飽和カルボン酸化合物一価金属塩は一種でも二種以上の混合物であってもよい。
かかる不飽和カルボン酸化合物一価金属塩を用いた場合、得られる共重合体層の帯電防止性に優れるという特徴がある。また、一価金属塩の添加量が多いほど帯電防止性は向上する。
Unsaturated carboxylic acid compound monovalent metal salt Unsaturated carboxylic acid compound monovalent metal salt which is the group of the unsaturated carboxylic acid compound metal salt copolymer according to the present invention is an unsaturated carboxylic acid compound having a degree of polymerization of less than 20. And a salt of the monovalent metal compound. These unsaturated carboxylic acid compound monovalent metal salts may be one kind or a mixture of two or more kinds.
When such an unsaturated carboxylic acid compound monovalent metal salt is used, the resulting copolymer layer is characterized by excellent antistatic properties. In addition, the antistatic property improves as the amount of the monovalent metal salt added increases.
ガスバリア性膜（共重合体）
本発明のガスバリア性膜は、５０モル％を超える割合、好ましくは５０モル％を超えてから９９．９９９モル％まで、より好ましくは５０モル％を超えてから９０モル％まで、さらに好ましくは５０モル％を超えて８０モル％までの範囲の不飽和カルボン酸化合物一価金属塩と５０モル％未満、好ましくは０．００１ないし５０モル％未満、より好ましくは１０ないし５０モル％未満、さらに好ましくは２０ないし５０モル％未満の前記不飽和カルボン酸化合物多金属塩との共重合体（不飽和カルボン酸化合物の一価金属塩と不飽和カルボン酸化合物の多価金属塩との合計量が１００モル％）である。
本発明のガスバリア性膜（共重合体）は、好ましくは、赤外線吸収スペクトルにおける１７００ｃｍ−１付近のカルボン酸基のνＣ＝Ｏに基づく吸光度Ａ０と１５２０ｃｍ−１付近のカルボキシレートイオンのνＣ＝Ｏに基づく吸光度Ａとの比（Ａ０／Ａ）が０．２５未満、より好ましくは０．２０未満の範囲にある不飽和カルボン酸化合物多価金属塩と不飽和カルボン酸化合物一価金属塩との共重合体からなる。
また、不飽和カルボン酸化合物一価金属塩を共重合した場合は、得られるガスバリア性膜の表面固有抵抗値が低くなり、帯電防止性に優れたガスバリア性膜が得られると言う特徴があり、不飽和カルボン酸化合物一価金属塩の添加量が多いほど帯電防止性が優れる。
本発明の不飽和カルボン酸化合物の一価金属塩と多価金属塩との共重合体からなるガスバリア性膜は、カルボン酸基と多価金属及び一価金属とがそれぞれイオン架橋してなるカルボキシレートイオンと遊離のカルボン酸基が存在し、夫々、赤外線スペクトルで、遊離のカルボン酸基のνＣ＝Ｏに基づく吸収が１７００ｃｍ−１付近にあり、カルボキシレートイオンのνＣ＝Ｏに基づく吸収が１５２０ｃｍ−１付近にある。
本発明に係る共重合体において、（Ａ０／Ａ）が０．２５未満であるということは、遊離のカルボン酸基が存在しないか、少ないことを示しており、０．２５を越える層は、遊離のカルボン酸基の含有量が多く、高湿度下での耐ガスバリア性が改良されない虞があるので、（Ａ０／Ａ）が０．２５未満であることが好ましい。
本発明における１７００ｃｍ−１付近のカルボン酸基のνＣ＝Ｏに基づく吸光度Ａ０と赤外線吸収スペクトルにおける１５２０ｃｍ−１付近のカルボキシレートイオンのνＣ＝Ｏに基づく吸光度Ａとの比（Ａ０／Ａ）は、ガスバリア性積層フィルムから１ｃｍ×３ｃｍの測定用サンプルを切り出し、その表面（不飽和カルボン酸化合物金属塩共重合体層）の赤外線吸収スペクトルを赤外線全反射測定（ＡＴＲ法）によって得、以下の手順で、先ず、吸光度Ａ０及び吸光度Ａを求めた。
１７００ｃｍ−１付近のカルボン酸基のνＣ＝Ｏに基づく吸光度Ａ０：赤外線吸収スペクトルの１６６０ｃｍ−１と１７６０ｃｍ−１の吸光度とを直線（Ｎ）で結び、１６６０〜１７６０ｃｍ−１間の最大吸光度（１７００ｃｍ−１付近）から垂直に直線（Ｏ）を下ろし、当該直線（Ｏ）と直線（Ｎ）との交点と最大吸光度との吸光度の距離（長さ）を吸光度Ａ０とした。
１５２０ｃｍ−１付近のカルボキシレートイオンのνＣ＝Ｏに基づく吸光度Ａ：赤外線吸収スペクトルの１４８０ｃｍ−１と１６３０ｃｍ−１の吸光度とを直線（Ｌ）で結び、１４８０〜１６３０ｃｍ−１間の最大吸光度（１５２０ｃｍ−１付近）から垂直に直線（Ｍ）を下ろし、当該直線（Ｍ）と直線（Ｌ）との交点と最大吸光度との吸光度の距離（長さ）を吸光度Ａとした。尚、最大吸光度（１５２０ｃｍ−１付近）は、対イオンの金属種によりピーク位置が変化することがあり、例えば、カルシウムでは１５２０ｃｍ−１付近、亜鉛では１５２０ｃｍ−１付近、マグネシウムでは１５４０ｃｍ−１付近及びナトリウム（Ｎａ）では１５４０ｃｍ−１付近である。
次いで、上記方法で求めた吸光度Ａ０及び吸光度Ａから比（Ａ０／Ａ）を求めた。
なお、本発明のおける赤外線スペクトルの測定（赤外線全反射測定：ＡＴＲ法）は、日本分光社製ＦＴ−ＩＲ３５０装置を用い、ＫＲＳ−５（Ｔｈａｌｌｉｕｍ Ｂｒｏｍｉｄｅ−Ｉｏｄｉｄｅ）結晶を装着して、入射角４５度、室温、分解能４ｃｍ−１、積算回数１５０回の条件で行った。
Gas barrier film (copolymer)
The gas barrier film of the present invention has a proportion of more than 50 mol%, preferably more than 50 mol% to 99.999 mol%, more preferably more than 50 mol% to 90 mol%, still more preferably 50 mol%. Unsaturated carboxylic acid compound monovalent metal salt in the range of more than mol% to 80 mol% and less than 50 mol%, preferably less than 0.001 to 50 mol%, more preferably less than 10 to 50 mol%, still more preferably Is a copolymer of 20 to less than 50 mol% of the unsaturated carboxylic acid compound polymetal salt (the total amount of the monovalent metal salt of the unsaturated carboxylic acid compound and the polyvalent metal salt of the unsaturated carboxylic acid compound is 100). Mol%).
The gas barrier film (copolymer) of the present invention preferably has an absorbance A 0 based on νC═O of a carboxylic acid group near 1700 cm −1 in the infrared absorption spectrum and νC═O of a carboxylate ion near 1520 cm −1. An unsaturated carboxylic acid compound polyvalent metal salt and an unsaturated carboxylic acid compound monovalent metal salt having a ratio (A 0 / A) to an absorbance A based on the formula (A 0 / A) of less than 0.25, more preferably less than 0.20 It consists of a copolymer.
In addition, when an unsaturated carboxylic acid compound monovalent metal salt is copolymerized, the surface specific resistance value of the obtained gas barrier film is reduced, and a gas barrier film having excellent antistatic properties is obtained, The higher the amount of unsaturated carboxylic acid compound monovalent metal salt added, the better the antistatic properties.
The gas barrier film comprising a copolymer of a monovalent metal salt and a polyvalent metal salt of the unsaturated carboxylic acid compound of the present invention is a carboxy group formed by ionic crosslinking of a carboxylic acid group, a polyvalent metal and a monovalent metal. In the infrared spectrum, the absorption based on νC═O of the free carboxylic acid group is around 1700 cm −1 and the absorption based on νC═O of the carboxylate ion is 1520 cm, respectively. Near -1 .
In the copolymer according to the present invention, (A 0 / A) being less than 0.25 indicates that there are few or no free carboxylic acid groups. Since the content of free carboxylic acid groups is large and the gas barrier resistance under high humidity may not be improved, (A 0 / A) is preferably less than 0.25.
Ratio of absorbance A 0 based on νC═O of a carboxylic acid group near 1700 cm −1 in the present invention to absorbance A based on νC═O of a carboxylate ion near 1520 cm −1 in an infrared absorption spectrum (A 0 / A) Cut out a sample for measurement of 1 cm × 3 cm from the gas barrier laminate film, and obtained the infrared absorption spectrum of the surface (unsaturated carboxylic acid compound metal salt copolymer layer) by infrared total reflection measurement (ATR method), In the procedure, first, absorbance A 0 and absorbance A were determined.
1700cm absorbance based νC = O -1 vicinity of the carboxylic acid groups A 0: a absorbance of the infrared absorption spectrum of 1660 cm -1 and 1760 cm -1 connected by a straight line (N), 1660~1760cm maximum absorbance between -1 ( The straight line (O) was dropped vertically from around 1700 cm −1, and the absorbance distance (length) between the intersection of the straight line (O) and the straight line (N) and the maximum absorbance was defined as absorbance A 0 .
1520 cm -1 vicinity of carboxylate ion of νC = O based upon the absorbance A: connected by a straight line (L) and the absorbance of the infrared absorption spectrum of 1480 cm -1 and 1630 cm -1, the maximum absorbance between 1480~1630cm -1 (1520cm The straight line (M) was dropped vertically from the vicinity of −1 ), and the absorbance distance (length) between the intersection of the straight line (M) and the straight line (L) and the maximum absorbance was defined as absorbance A. The peak position of maximum absorbance (near 1520 cm −1 ) may vary depending on the metal species of the counter ion. For example, calcium is near 1520 cm −1 , zinc is near 1520 cm −1 , magnesium is near 1540 cm −1 , and In sodium (Na), it is around 1540 cm −1 .
Next, the ratio (A 0 / A) was determined from the absorbance A 0 and the absorbance A determined by the above method.
In addition, the measurement of the infrared spectrum (infrared total reflection measurement: ATR method) in the present invention uses an FT-IR350 apparatus manufactured by JASCO Corporation, and a KRS-5 (Thallium Bromide-Iodide) crystal is attached, and the incident angle is 45. Degree, room temperature, resolution of 4 cm −1 , and accumulation of 150 times.
本発明のガスバリア性膜の厚さは種々用途により決め得るが、通常は、０．０１〜１００μｍ、好ましくは０．０５〜５０μｍ、より好ましくは０．１〜１０μｍの範囲にある。 The thickness of the gas barrier film of the present invention can be determined according to various uses, but is usually in the range of 0.01 to 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm.
本発明のガスバリア性膜は、本発明の目的を損なわない範囲で、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、１，４−ブタンジオール・ジアクリレート、ジエチレングリコール・ジアクリレート、テトラエチレングリコール・ジアクリレート、ポリエチレングリコール・ジアクリレート、ヘキサンジオール・ジアクリレート、トリプロピレングリコール・ジアクリレート、ネオペンチルグリコールジアクリレート、などの不飽和カルボン酸（ジ）エステル化合物、酢酸ビニルなどのビニルエステル化合物等の単量体あるいは低分子量の化合物が共重合されていてもよい。
また、本発明のガスバリア性膜は、本発明の目的を損なわない範囲で、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、ポリビニルピロリドン、ポリビニルエチルエーテル、ポリアクリルアミド、ポリエチレンイミン、澱粉、アラビアガム、メチルセルロース等の水溶性重合体、アクリル酸エステル重合体、エチレン・アクリル酸共重合体、ポリ酢酸ビニル、エチレン・酢酸ビニル共重合体、ポリエステル、ポリウレタン等の高分子量の化合物等、滑剤、スリップ剤、アンチ・ブロッキング剤、帯電防止剤、防曇剤、顔料、染料、無機また有機の充填剤等の各種添加剤が含まれていてもよいし、後述の基材との濡れ性、密着性等を改良するために、各種界面活性剤等が含まれていてもよい。
The gas barrier film of the present invention is a methyl (meth) acrylate, ethyl (meth) acrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, tetraethylene glycol as long as the object of the present invention is not impaired.・ Unsaturated carboxylic acid (di) ester compounds such as diacrylate, polyethylene glycol diacrylate, hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, vinyl ester compounds such as vinyl acetate, etc. Monomers or low molecular weight compounds may be copolymerized.
In addition, the gas barrier film of the present invention is within the range not impairing the object of the present invention, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl pyrrolidone, polyvinyl ethyl ether, polyacrylamide, polyethyleneimine, starch, gum arabic, methylcellulose Water-soluble polymers such as acrylic acid ester polymers, ethylene / acrylic acid copolymers, polyvinyl acetate, ethylene / vinyl acetate copolymers, polyesters, polyurethanes and other high molecular weight compounds, lubricants, slip agents, anti -Various additives such as blocking agents, antistatic agents, antifogging agents, pigments, dyes, inorganic or organic fillers may be included, and wettability, adhesion, etc. with the substrate described later are improved. In order to do so, various surfactants and the like may be included.
ガスバリア性積層体
本発明のガスバリア性積層体は、基材層の少なくとも片面に前記、５０モル％を超える割合、好ましくは５０モル％を超えてから９９．９９９モル％まで、より好ましくは５０モル％を超えてから９０モル％まで、さらに好ましくは５０モル％を超えて８０モル％までの範囲の不飽和カルボン酸化合物一価金属塩を含む不飽和カルボン酸化合物多価金属塩との共重合体層からなるガスバリア性膜が形成されてなる。
本発明のガスバリア性積層体は、後述の基材層の形状により、また用途に応じ、積層フィルム、中空容器、トレー等の種々公知の形状を有する積層体とすることができる。
本発明のガスバリア性積層体の厚さは用途の応じて種々決定され得るが、通常は、基材層の厚さが５〜５００μｍ、好ましくは５〜１００μｍ、より好ましくは９〜３０μｍ、不飽和カルボン酸化合物多金属塩の共重合体層の厚さが０．０１〜１００μｍ、好ましくは０．０５〜５０μｍ、より好ましくは０．１〜１０μｍ、ガスバリア性積層体の全体の厚さが２０〜７５０μｍ、より好ましくは２５〜４３０μｍの範囲にある。
Gas barrier laminate The gas barrier laminate of the present invention has a ratio of more than 50 mol%, preferably more than 50 mol% to 99.999 mol%, more preferably 50 mol, on at least one side of the base material layer. % Of unsaturated carboxylic acid compound polyvalent metal salt including unsaturated carboxylic acid compound monovalent metal salt in the range of greater than 50% to 90 mole%, more preferably greater than 50 mole% to 80 mole% A gas barrier film made of a combined layer is formed.
The gas barrier laminate of the present invention can be made into a laminate having various known shapes such as a laminate film, a hollow container, a tray and the like depending on the shape of the base material layer described later and depending on the application.
The thickness of the gas barrier laminate of the present invention can be variously determined depending on the application, but usually the thickness of the base material layer is 5 to 500 μm, preferably 5 to 100 μm, more preferably 9 to 30 μm, and unsaturated. The thickness of the copolymer layer of the carboxylic acid compound polymetal salt is 0.01 to 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm, and the total thickness of the gas barrier laminate is 20 to 20 μm. It exists in the range of 750 micrometers, More preferably, 25-430 micrometers.
基材層
本発明のガスバリア性積層体を形成する基材層は、熱硬化性樹脂あるいは熱可塑性樹脂からなるシートまたはフィルム、トレー、中空体等の形状を有するもの、紙、アルミニウム箔等からなる。
熱硬化性樹脂としては、種々公知の熱硬化性樹脂、例えば、エポキシ樹脂、不飽和ポリエステル樹脂、フェノール樹脂、ユリア・メラミン樹脂、ポリウレタン樹脂、シリコーン樹脂、ポリイミド等を例示することができる。
熱可塑性樹脂としては、種々公知の熱可塑性樹脂、例えば、ポリオレフィン（ポリエチレン、ポリプロピレン、ポリ４−メチル・１−ペンテン、ポリブテン等）、ポリエステル（ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等）、ポリアミド（ナイロン−６、ナイロン−６６、ポリメタキシレンアジパミド等）、ポリ塩化ビニル、ポリイミド、エチレン・酢酸ビニル共重合体もしくはその鹸化物、ポリビニルアルコール、ポリアクリロニトリル、ポリカーボネート、ポリスチレン、アイオノマー、あるいはこれらの混合物等を例示することができる。これらのうちでは、ポリプロピレン、ポリエチレンテレフタレート、ポリアミド等、延伸性、透明性が良好な熱可塑性樹脂が好ましい。
また、基材層の表面に、アルミニウム、亜鉛若しくはシリカ等の無機化合物あるいはその酸化物等が蒸着されていてもよい。
また、これら基材層は、ガスバリア性膜との接着性を改良するために、その表面を、例えば、コロナ処理、火炎処理、プラズマ処理、アンダーコート処理、プライマーコート処理、フレーム処理等の表面活性化処理を行っておいてもよい。
本発明のガスバリア性積層体は、種々用途に応じ、ガスバリア性膜の表面に更に基材層に用いる各種フィルムを積層してもよいし、アルミニウム、亜鉛若しくはシリカ等の無機化合物あるいはその酸化物等が蒸着されていてもよい。
Base material layer The base material layer forming the gas barrier laminate of the present invention comprises a sheet or film made of a thermosetting resin or a thermoplastic resin, a tray, a hollow body, or the like, paper, aluminum foil or the like. .
Examples of the thermosetting resin include various known thermosetting resins such as epoxy resins, unsaturated polyester resins, phenol resins, urea / melamine resins, polyurethane resins, silicone resins, and polyimides.
As the thermoplastic resin, various known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (Nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, or these And the like. Of these, thermoplastic resins having good stretchability and transparency, such as polypropylene, polyethylene terephthalate, and polyamide, are preferable.
In addition, an inorganic compound such as aluminum, zinc, or silica or an oxide thereof may be deposited on the surface of the base material layer.
In addition, in order to improve the adhesion with the gas barrier film, these base material layers have surface activity such as corona treatment, flame treatment, plasma treatment, undercoat treatment, primer coat treatment, flame treatment, etc. It is also possible to carry out the conversion process.
The gas barrier laminate of the present invention may be laminated with various films used for the base material layer on the surface of the gas barrier film according to various uses, or an inorganic compound such as aluminum, zinc or silica or an oxide thereof. May be deposited.
ガスバリア性積層フィルムの製造方法
本発明のガスバリア性積層体の製造方法は、前記基材層の少なくとも片面に、５０モル％を超える割合、好ましくは５０を超え９９．９９９モル％まで、より好ましくは５０を超え９０モル％、さらに好ましくは５０を超え８０モル％までの範囲の前記重合度が２０未満の不飽和カルボン酸化合物の一価金属塩と５０モル％未満、好ましくは０．００１〜５０モル％未満、より好ましくは１０〜５０モル％未満、さらに好ましくは２０〜５０モル％未満の前記不飽和カルボン酸化合物多金属塩との混合物（不飽和カルボン酸化合物の一価金属塩と不飽和カルボン酸化合物の多価金属塩との合計量が１００モル％）を重合することにより不飽和カルボン酸化合物金属塩の共重合体の層（ガスバリア性膜）を形成させることを特徴とする。
基材層の少なくとも片面に、ガスバリア性膜を形成させる方法としては、例えば、不飽和カルボン酸化合物一価金属塩が５０モル％を超え、不飽和カルボン酸化合物多価金属塩が５０モル％以下となるように水等の溶媒に溶解した後、当該混合物の溶液を塗布する方法、個別に不飽和カルボン酸化合物一価金属塩の溶液及び不飽和カルボン酸化合物多価金属塩の溶液を作成した後、不飽和カルボン酸化合物一価金属塩の濃度が５０モル％を超えるように混合した溶液を塗布する方法、あるいは重合度が２０未満の不飽和カルボン酸化合物若しくはその溶液に前記一価金属化合物と多価金属化合物とを一価金属塩の濃度が５０モル％を超えるような比率で添加して不飽和カルボン酸化合物一価金属塩と不飽和カルボン酸化合物多価金属塩とを形成させた溶液を塗布する方法等を例示できるが、かかる方法には限定されず、要は基材層に塗布されるものとして、重合度が２０未満の不飽和カルボン酸化合物から形成された前記不飽和カルボン酸化合物一価金属塩を５０モル％を超えて含んだ、前記不飽和カルボン酸化合物多価金属塩との混合物が形成されておればよい。
又、基材層の形状により、塗布する方法に限らず、当該混合物の溶液に基材層を浸漬する方法、当該混合物の溶液を基材層表面に噴霧する方法等種々公知の塗工方法を採り得る。
Method for Producing Gas Barrier Laminate Film In the method for producing a gas barrier laminate of the present invention, a ratio exceeding 50 mol%, preferably exceeding 50 and 99.999 mol%, more preferably, on at least one side of the base material layer. The monovalent metal salt of an unsaturated carboxylic acid compound having a degree of polymerization of less than 20 and less than 50 mol%, preferably less than 50 mol%, preferably 0.001-50, more than 50 and 90 mol%, more preferably more than 50 and up to 80 mol%. Less than mol%, more preferably less than 10 to 50 mol%, still more preferably less than 20 to 50 mol% of a mixture with the unsaturated carboxylic acid compound polymetal salt (unsaturated carboxylic acid compound monovalent metal salt and unsaturated The copolymer layer of the unsaturated carboxylic acid compound metal salt (gas barrier film) is polymerized by polymerizing 100 mol% of the total amount of the carboxylic acid compound and the polyvalent metal salt. And characterized in that made.
As a method for forming a gas barrier film on at least one surface of the base material layer, for example, the unsaturated carboxylic acid compound monovalent metal salt exceeds 50 mol%, and the unsaturated carboxylic acid compound polyvalent metal salt is 50 mol% or less. After dissolving in a solvent such as water, a method of applying the solution of the mixture, individually prepared a solution of unsaturated carboxylic acid compound monovalent metal salt and a solution of unsaturated carboxylic acid compound polyvalent metal salt Thereafter, a method of applying a mixed solution such that the concentration of the unsaturated carboxylic acid compound monovalent metal salt exceeds 50 mol%, or the unsaturated carboxylic acid compound having a polymerization degree of less than 20 or the monovalent metal compound in the solution. And a polyvalent metal compound are added at a ratio such that the concentration of the monovalent metal salt exceeds 50 mol% to form an unsaturated carboxylic acid compound monovalent metal salt and an unsaturated carboxylic acid compound polyvalent metal salt. However, the method is not limited to such a method, and the main point is that the solution formed from an unsaturated carboxylic acid compound having a degree of polymerization of less than 20 is applied to the base material layer. A mixture with the unsaturated carboxylic acid compound polyvalent metal salt containing the saturated carboxylic acid compound monovalent metal salt in excess of 50 mol% may be formed.
Further, depending on the shape of the base material layer, not only the method of coating, but also various known coating methods such as a method of immersing the base material layer in the solution of the mixture, a method of spraying the solution of the mixture on the surface of the base material layer, etc. It can be taken.
重合度が２０未満の不飽和カルボン酸化合物と一価金属化合物及び多価金属化合物とを混合した溶液を用いる場合は、不飽和カルボン酸化合物に対して、不飽和カルボン酸一価金属塩と不飽和カルボン酸化合物多価金属塩が上記の範囲で形成されるように、多価金属化合物と一価金属化合物を添加すれば良いが、一価金属化合物と多価金属化合物との添加量が不飽和カルボン酸に対して少ない場合は、遊離のカルボン酸基の含有量が多い積層体となり、結果として、ガスバリア性が低い積層体となる虞がある。また、一価金属化合物と多価金属化合物の添加量が不飽和カルボン酸化合物のカルボキシル基に対して１化学当量を超える場合は、未反応の金属化合物が存在する事になり、形成される不飽和カルボン酸化合物一価金属塩と不飽和カルボン酸化合物多価金属塩との割合が制御できない虞がある。従って、一価金属化合物と多価金属化合物との添加量は、不飽和カルボン酸のカルボキシル基に対して１化学当量であることが好ましい。
また、不飽和カルボン酸化合物と一価金属化合物及び多価金属化合物とを混合した溶液を用いる場合は、通常、不飽和カルボン酸化合物と一価金属化合物及び多価金属化合物とを溶媒に溶かしている間に、不飽和カルボン酸化合物の一価金属塩と多価金属塩が形成されるが、一価金属塩と多価金属塩の形成を確実にするために、１分以上混合しておくことが好ましい。
When using a solution in which an unsaturated carboxylic acid compound having a polymerization degree of less than 20 is mixed with a monovalent metal compound and a polyvalent metal compound, the unsaturated carboxylic acid monovalent metal salt and the unsaturated carboxylic acid compound are mixed with the unsaturated carboxylic acid compound. The polyvalent metal compound and the monovalent metal compound may be added so that the saturated carboxylic acid compound polyvalent metal salt is formed within the above range, but the addition amount of the monovalent metal compound and the polyvalent metal compound is not sufficient. When the amount is less than that of the saturated carboxylic acid, a laminate having a large content of free carboxylic acid groups may be formed, resulting in a laminate having a low gas barrier property. In addition, when the addition amount of the monovalent metal compound and the polyvalent metal compound exceeds one chemical equivalent with respect to the carboxyl group of the unsaturated carboxylic acid compound, an unreacted metal compound is present and the formed unreacted metal compound. There is a possibility that the ratio between the saturated carboxylic acid compound monovalent metal salt and the unsaturated carboxylic acid compound polyvalent metal salt cannot be controlled. Therefore, the addition amount of the monovalent metal compound and the polyvalent metal compound is preferably 1 chemical equivalent with respect to the carboxyl group of the unsaturated carboxylic acid.
In addition, when using a solution in which an unsaturated carboxylic acid compound is mixed with a monovalent metal compound and a polyvalent metal compound, the unsaturated carboxylic acid compound, the monovalent metal compound and the polyvalent metal compound are usually dissolved in a solvent. The monovalent metal salt and polyvalent metal salt of the unsaturated carboxylic acid compound are formed during the process, but in order to ensure the formation of the monovalent metal salt and the polyvalent metal salt, they are mixed for 1 minute or more. It is preferable.
これら方法の中でも、予め、不飽和カルボン酸化合物一価金属塩及び不飽和カルボン酸化合物多価金属塩を用いる方法が、不飽和カルボン酸化合物一価金属塩の添加量を５０モル％を超える範囲で任意に調整できるので好ましい。 Among these methods, the method using an unsaturated carboxylic acid compound monovalent metal salt and an unsaturated carboxylic acid compound polyvalent metal salt in advance is within a range where the addition amount of the unsaturated carboxylic acid compound monovalent metal salt exceeds 50 mol%. It is preferable because it can be arbitrarily adjusted.
重合度が２０未満の不飽和カルボン酸化合物一価金属塩と多価金属塩との混合溶液に用いる溶媒は、水、メチルアルコール、エチルアルコール、イソプロピルアルコール等の低級アルコール若しくはアセトン、メチルエチルケトン等の有機溶媒あるいはそれらの混合溶媒が挙げられるが、水が最も好ましい。
基材層の少なくとも片面に重合度が２０未満の不飽和カルボン酸化合物一価金属塩と多価金属塩との混合溶液を塗布する方法としては、例えば、エアーナイフコーター、ダイレクトグラビアコーター、グラビアオフセット、アークグラビアコーター、グラビアリバースおよびジェットノズル方式等のグラビアコーター、トップフィードリバースコーター、ボトムフィードリバースコーターおよびノズルフィードリバースコーター等のリバースロールコーター、５本ロールコーター、リップコーター、バーコーター、バーリバースコーター、ダイコーター、スピンコーター、ディップコーター等種々公知の塗工機を用いて、重合度が２０未満の不飽和カルボン酸化合物一価金属塩と多価金属塩との混合溶液を乾燥、重合させた後の厚みで０．０１〜１００μｍ、好ましくは０．０５〜５０μｍ、より好ましくは０．１〜１０μｍとなるように、共重合体層の比重に応じて、適宜塗布すればよい。
The solvent used in the mixed solution of the unsaturated carboxylic acid compound monovalent metal salt and polyvalent metal salt having a polymerization degree of less than 20 is water, lower alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol or the like, or organic such as acetone, methyl ethyl ketone, etc. Although a solvent or those mixed solvents are mentioned, water is the most preferable.
Examples of a method for applying a mixed solution of an unsaturated carboxylic acid compound monovalent metal salt and a polyvalent metal salt having a polymerization degree of less than 20 on at least one surface of the base material layer include, for example, an air knife coater, a direct gravure coater, and a gravure offset. , Arc gravure coaters, gravure reverse and jet nozzle type gravure coaters, top feed reverse coaters, bottom feed reverse coaters and reverse feed roll coaters such as nozzle feed reverse coaters, 5-roll coaters, lip coaters, bar coaters, bar reverse coaters The mixed solution of unsaturated carboxylic acid compound monovalent metal salt and polyvalent metal salt having a polymerization degree of less than 20 was dried and polymerized using various known coating machines such as a die coater, spin coater, dip coater, etc. 0.0 after the thickness ～100Myuemu, preferably 0.05 to 50, as more preferably a 0.1 to 10 [mu] m, depending on the specific gravity of the copolymer layer may be appropriately applied.
不飽和カルボン酸化合物一価金属塩及び／または不飽和カルボン酸化合物多価金属塩を溶解させる際若しくは不飽和カルボン酸化合物と一価金属化合物及び多価金属化合物とを溶解させる際には、前述した如く、本発明の目的を損なわない範囲で、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、１，４−ブタンジオール・ジアクリレート、ジエチレングリコール・ジアクリレート、テトラエチレングリコール・ジアクリレート、ポリエチレングリコール・ジアクリレート、ヘキサンジオール・ジアクリレート、トリプロピレングリコール・ジアクリレート、ネオペンチルグリコールジアクリレート、などの不飽和カルボン酸（ジ）エステル化合物、酢酸ビニルなどのビニルエステル化合物等の単量体あるいは低分子量の化合物、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、ポリビニルピロリドン、ポリビニルエチルエーテル、ポリアクリルアミド、ポリエチレンイミン、澱粉、アラビアガム、メチルセルロース等の水溶性重合体、アクリル酸エステル重合体、エチレン・アクリル酸共重合体、ポリ酢酸ビニル、エチレン・酢酸ビニル共重合体、ポリエステル、ポリウレタン等の高分子量の化合物等を添加してもよい。
また、不飽和カルボン酸化合物一価金属塩及び／または不飽和カルボン酸化合物多価金属塩を溶解させる際若しくは不飽和カルボン酸化合物と一価金属化合物及び多価金属化合物とを溶解させる際には、本発明の目的を損なわない範囲で、滑剤、スリップ剤、アンチ・ブロッキング剤、帯電防止剤、防曇剤、顔料、染料、無機また有機の充填剤等の各種添加剤を添加しておいてもよいし、基材層との濡れ性を改良するために、各種界面活性剤等を添加しておいてもよい。
When the unsaturated carboxylic acid compound monovalent metal salt and / or the unsaturated carboxylic acid compound polyvalent metal salt is dissolved, or when the unsaturated carboxylic acid compound, the monovalent metal compound and the polyvalent metal compound are dissolved, As described above, methyl (meth) acrylate, ethyl (meth) acrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene are within the range not impairing the object of the present invention. Monomers such as glycol diacrylate, hexanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, and other unsaturated carboxylic acid (di) ester compounds, vinyl ester compounds such as vinyl acetate, etc. Molecular weight compounds Water-soluble polymers such as vinyl alcohol, ethylene / vinyl alcohol copolymer, polyvinyl pyrrolidone, polyvinyl ethyl ether, polyacrylamide, polyethyleneimine, starch, gum arabic, and methyl cellulose, acrylate polymer, ethylene / acrylic acid copolymer High molecular weight compounds such as polyvinyl acetate, ethylene / vinyl acetate copolymer, polyester, and polyurethane may be added.
Further, when the unsaturated carboxylic acid compound monovalent metal salt and / or the unsaturated carboxylic acid compound polyvalent metal salt is dissolved, or when the unsaturated carboxylic acid compound, the monovalent metal compound and the polyvalent metal compound are dissolved. Addition of various additives such as lubricants, slip agents, anti-blocking agents, antistatic agents, antifogging agents, pigments, dyes, inorganic or organic fillers, etc. within the range not impairing the object of the present invention. Alternatively, various surfactants and the like may be added in order to improve the wettability with the base material layer.
基材層の少なくとも片面に形成した（塗布した）５０モル％を超える不飽和カルボン酸化合物一価金属塩と５０モル％以下の不飽和カルボン酸化合物多価金属塩とを含む溶液（塗布層）を重合させるには、種々公知の方法、具体的には例えば、電離放射線の照射また加熱等による方法が挙げられる。
電離放射線を使用する場合は、波長領域が０．０００１〜８００ｎｍの範囲のエネルギー線であれば特に限定されないが、かかるエネルギー線としては、α線、β線、γ線、Ｘ線、可視光線、紫外線、電子線等が上げられる。これらの電離放射線の中でも、波長領域が４００〜８００ｎｍの範囲の可視光線、５０〜４００ｎｍの範囲の紫外線および０．０１〜０．００２ｎｍの範囲の電子線が、取り扱いが容易で、装置も普及しているので好ましい。
電離放射線として可視光線および紫外線を用いる場合は、不飽和カルボン酸化合物一価金属塩と多価金属塩の混合溶液に光重合開始剤を添加することが必要となる。光重合開始剤としては、公知のものを使用することができ、例えば、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン（チバ・スペシャリティ・ケミカルズ社製 商品名；ダロキュアー １１７３）、１−ヒドロキシーシクロヘキシルーフェニルケトン（チバ・スペシャリティ・ケミカルズ社製 商品名；イルガキュアー １８４）、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド（チバ・スペシャリティ・ケミカルズ社製 商品名；イルガキュアー８１９）、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン（チバ・スペシャリティ・ケミカルズ社製 商品名；イルガキュアー ２９５９）、α―ヒドロキシケトン、アシルホスフィンオキサイド、４−メチルベンゾフェノン及び２，４，６−トリメチルベンゾフェノンの混合物（ランベルティ・ケミカル・スペシャルティ社製 商品名；エサキュアー ＫＴ０４６）、エサキュアー ＫＴ５５（ランベルティー・ケミカル・スペシャルティ）、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド（ラムソン・ファイア・ケミカル社製 商品名；スピードキュアＴＰＯ）の商品名で製造・販売されているラジカル重合開始剤を挙げることができる。さらに、重合度または重合速度を向上させるため重合促進剤を添加することができ、例えば、Ｎ、Ｎ-ジメチルアミノ-エチル-（メタ）アクリレート、Ｎ-（メタ）アクリロイル-モルフォリン等が挙げられる。
A solution (coating layer) comprising an unsaturated carboxylic acid compound monovalent metal salt exceeding 50 mol% and an unsaturated carboxylic acid compound polyvalent metal salt of 50 mol% or less formed (coated) on at least one surface of the base material layer In order to polymerize, there are various known methods, specifically, for example, a method by irradiation with ionizing radiation or heating.
When using ionizing radiation, it is not particularly limited as long as the wavelength region is an energy ray in the range of 0.0001 to 800 nm. Examples of such energy rays include α rays, β rays, γ rays, X rays, visible rays, Ultraviolet rays, electron beams, etc. are raised. Among these ionizing radiations, visible light in the wavelength range of 400 to 800 nm, ultraviolet light in the range of 50 to 400 nm, and electron beam in the range of 0.01 to 0.002 nm are easy to handle and the devices are widespread. Therefore, it is preferable.
When visible light and ultraviolet light are used as ionizing radiation, it is necessary to add a photopolymerization initiator to a mixed solution of an unsaturated carboxylic acid compound monovalent metal salt and a polyvalent metal salt. As the photopolymerization initiator, known ones can be used. For example, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name; Darocur 1173, manufactured by Ciba Specialty Chemicals) , 1-hydroxy-cyclohexyl ruphenyl ketone (Ciba Specialty Chemicals product name; Irgacure 184), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Chemicals product) Name; Irgacure 819), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals) 2959), α-hydroxyketone, acylphosphine. Side, 4-methylbenzophenone and 2,4,6-trimethylbenzophenone mixture (Lamberty Chemical Specialty, trade name; Esacure KT046), Esacure KT55 (Lamberty Chemical Specialty), 2,4,6- A radical polymerization initiator manufactured and sold under the trade name of trimethylbenzoyldiphenylphosphine oxide (trade name; Speed Cure TPO manufactured by Ramson Fire Chemical Co., Ltd.) can be mentioned. Furthermore, a polymerization accelerator can be added to improve the polymerization degree or polymerization rate, and examples thereof include N, N-dimethylamino-ethyl- (meth) acrylate and N- (meth) acryloyl-morpholine. .
不飽和カルボン酸化合物一価金属塩と多価金属塩とを重合させる際は、溶液が水等の溶媒を含んだ状態で重合させてもよいし、一部乾燥させた後に重合させてもよいが、溶液を塗布後直ぐに重合させた場合は、金属塩が重合する際に溶媒の蒸発が多いためか、得られる共重合体層が白化する場合がある。一方、溶媒（水分）が少なくなるとともに、不飽和カルボン酸化合物金属塩が結晶として析出する場合があり、かかる状態で重合を行うと得られる共重合体層の形成が不十分になり、共重合体層が白化を起こしたりしてガスバリア性が安定しない虞がある。したがって、塗布した不飽和カルボン酸化合物多価金属塩を重合させる際には、適度な水分を含んだ状態で重合することが好ましい。
本発明においては、不飽和カルボン酸化合物多価金属塩に５０モル％を超える不飽和カルボン酸化合物一価金属塩を含ませることにより、理由は定かではないが、混合溶液から金属塩が析出する時間が伸び、結果として、塗布した混合溶液が適度な水分を含んだ状態を長くすることができるので、安定して不飽和カルボン酸化合物一価金属塩と多価金属塩とを重合させることができる。一方、不飽和カルボン酸化合物一価金属塩を添加しない場合は、塗布した不飽和カルボン酸化合物多価金属塩溶液を重合させる際に溶液中の水分の調整に注意をする必要があるだけで、得られる共重合体層への影響は全くない。
When the unsaturated carboxylic acid compound monovalent metal salt and the polyvalent metal salt are polymerized, the solution may be polymerized in a state containing a solvent such as water, or may be polymerized after being partially dried. However, when the solution is polymerized immediately after coating, the resulting copolymer layer may be whitened because of the large evaporation of the solvent when the metal salt is polymerized. On the other hand, the solvent (moisture) decreases, and the unsaturated carboxylic acid compound metal salt may precipitate as crystals. When polymerization is performed in such a state, formation of the resulting copolymer layer becomes insufficient, There is a possibility that the gas barrier property may not be stable due to whitening of the combined layer. Accordingly, when the applied unsaturated carboxylic acid compound polyvalent metal salt is polymerized, it is preferably polymerized in a state containing appropriate moisture.
In the present invention, when the unsaturated carboxylic acid compound polyvalent metal salt contains 50 mol% or more of the unsaturated carboxylic acid compound monovalent metal salt, the reason is not clear, but the metal salt is precipitated from the mixed solution. Since the time is extended and, as a result, the applied mixed solution can be kept in a state containing appropriate moisture, the unsaturated carboxylic acid compound monovalent metal salt and polyvalent metal salt can be polymerized stably. it can. On the other hand, when the unsaturated carboxylic acid compound monovalent metal salt is not added, it is only necessary to pay attention to the adjustment of moisture in the solution when polymerizing the applied unsaturated carboxylic acid compound polyvalent metal salt solution. There is no influence on the resulting copolymer layer.
本発明のガスバリア性積層体は、積層体が積層フィルムであれば、その少なくとも片面に、熱融着層を積層することにより、ヒートシール可能な包装用フィルムとして好適な積層フィルムが得られる。かかる熱融着層としては、通常熱融着層として公知のエチレン、プロピレン、ブテン−１、ヘキセン−１、４−メチル・ペンテン−１、オクテン−１等のα−オレフィンの単独若しくは共重合体、高圧法低密度ポリエチレン、線状低密度ポリエチレン（所謂ＬＬＤＰＥ）、高密度ポリエチレン、ポリプロピレン、ポリプロピレンランダム共重合体、ポリブテン、ポリ４−メチル・ペンテン−１、低結晶性あるいは非晶性のエチレン・プロピレンランダム共重合体、エチレン・ブテン−１ランダム共重合体、プロピレン・ブテン−１ランダム共重合体等のポリオレフィンを単独若しくは２種以上の組成物、エチレン・酢酸ビニル共重合体（ＥＶＡ）、エチレン・（メタ）アクリル酸共重合体あるいはその金属塩、ＥＶＡとポリオレフィンとの組成物等から得られる層である。
中でも、高圧法低密度ポリエチレン、線状低密度ポリエチレン（所謂ＬＬＤＰＥ）、高密度ポリエチレン等のエチレン系重合体から得られる熱融着層が低温ヒートシール性、ヒートシール強度に優れるので好ましい。
In the gas barrier laminate of the present invention, if the laminate is a laminate film, a laminate film suitable as a heat-sealable packaging film can be obtained by laminating a heat fusion layer on at least one surface thereof. As such a heat-fusible layer, a homo- or copolymer of α-olefin such as ethylene, propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1, etc., which are generally known as heat-fusible layers , High pressure method low density polyethylene, linear low density polyethylene (so-called LLDPE), high density polyethylene, polypropylene, polypropylene random copolymer, polybutene, poly-4-methyl pentene-1, low crystalline or amorphous ethylene Polypropylene random copolymer, ethylene / butene-1 random copolymer, polyolefin such as propylene / butene-1 random copolymer, or a composition of two or more, ethylene / vinyl acetate copolymer (EVA), ethylene・ (Meth) acrylic acid copolymer or metal salt thereof, EVA and polyolefin A layer obtained from the object or the like.
Among these, a heat-sealing layer obtained from an ethylene-based polymer such as high-pressure method low-density polyethylene, linear low-density polyethylene (so-called LLDPE), or high-density polyethylene is preferable because it has excellent low-temperature heat sealability and heat seal strength.
次に、本発明を実施例によりさらに具体的に説明するが、本発明はこれら実施例により何等限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples.
実施例及び比較例における物性値等は、以下の評価方法により求めた。
＜評価方法＞
（１）酸素透過度［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］：多層フィルムを、モコン社製 ＯＸ−ＴＲＡＮ２／２１を用いて、ＪＩＳ Ｋ ７１２６に準じ、温度２０℃、湿度５０％Ｒ．Ｈ．の条件で測定した。
（２）吸光度比（Ａ０／Ａ）：上記記載の方法で測定した。
（３）表面固有抵抗：２３℃、５０％Ｒ．Ｈ．の恒温恒湿室に２４時間多層フィルムを放置させた後、２３℃、５０％Ｒ．Ｈ．の条件でデジタル超高抵抗／微少電流計（ＡＤＶＡＮＴＥＳＴ Ｒ８３４０Ａ）により共重合体層面の表面固有抵抗値を測定した。
（４）ブロッキング：作成した積層フィルムを数枚重ね２３℃３５％ＲＨの環境に放置しコート面がポリエステルフィルム面に張り付くかどうか確認した。○はフィルムを剥がすと剥がれる。×は剥がれにくくブロッキングしている。
The physical property values and the like in Examples and Comparative Examples were obtained by the following evaluation methods.
<Evaluation method>
(1) Oxygen permeability [ml / (m 2 · day · MPa)]: A multilayer film was manufactured using Moxon OX-TRAN 2/21 according to JIS K 7126, temperature 20 ° C., humidity 50% R.D. H. It measured on condition of this.
(2) Absorbance ratio (A0 / A): measured by the method described above.
(3) Surface resistivity: 23 ° C., 50% R.D. H. The multilayer film was allowed to stand in a constant temperature and humidity chamber for 24 hours, and then 23 ° C., 50% R.D. H. The surface specific resistance value of the copolymer layer surface was measured with a digital ultrahigh resistance / microammeter (ADVANTEST R8340A) under the following conditions.
(4) Blocking: Several layers of the prepared laminated film were stacked and allowed to stand in an environment of 23 ° C. and 35% RH, and it was confirmed whether the coated surface stuck to the polyester film surface. ○ is peeled off when the film is peeled off. X is blocking easily.
＜溶液（Ｘ）の作製＞
アクリル酸亜鉛（アクリル酸の亜鉛塩）水溶液（浅田化学社製、濃度３０重量％（アクリル酸成分：２０重量％、亜鉛成分１０重量％））に、メチルアルコールで２５重量％に希釈した光重合開始剤〔１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン（チバ・スペシャリティ・ケミカルズ社製 商品名；イルガキュアー ２９５９）〕及び界面活性剤（花王社製 商品名；エマルゲン１２０）をアクリル酸に対して固形分比率でそれぞれ２％及び０．４％添加し、不飽和カルボン酸化合物亜鉛塩溶液（Ｘ）を作製した。
<Preparation of solution (X)>
Photopolymerization diluted to 25 wt% with methyl alcohol in an aqueous solution of zinc acrylate (zinc salt of acrylic acid) (Asada Chemical Co., Ltd., concentration 30 wt% (acrylic acid component: 20 wt%, zinc component 10 wt%)). Initiator [1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals)] and Surfactant (trade name; manufactured by Kao Corporation; Emulgen 120) was added to acrylic acid in a solid content ratio of 2% and 0.4%, respectively, to prepare an unsaturated carboxylic acid compound zinc salt solution (X).
＜溶液（Ｙ）の作製＞
アクリル酸（単量体）（共栄社化学社製）を水で希釈して２５％水溶液を作成した。この水溶液中のアクリル酸のカルボキシル基に対して１化学当量の水酸化ナトリウム（関東化学社製）を添加して、アクリル酸ナトリウム（アクリル酸のナトリウム塩）水溶液を作製した。
次に、作製したアクリル酸ナトリウム水溶液に、メチルアルコールで２５重量％に希釈した光重合開始剤〔１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン（チバ・スペシャリティ・ケミカルズ社製 商品名；イルガキュアー ２９５９）〕及び界面活性剤（花王社製 商品名；エマルゲン１２０）をアクリル酸に対して固形分比率でそれぞれ２％及び０．４％添加し、不飽和カルボン酸化合物ナトリウム塩溶液（Ｙ）を作製した。
<Preparation of solution (Y)>
Acrylic acid (monomer) (manufactured by Kyoeisha Chemical Co., Ltd.) was diluted with water to prepare a 25% aqueous solution. One chemical equivalent of sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added to the carboxyl group of acrylic acid in the aqueous solution to prepare an aqueous solution of sodium acrylate (a sodium salt of acrylic acid).
Next, a photopolymerization initiator [1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-diluted to 25% by weight with methyl alcohol was added to the prepared aqueous sodium acrylate solution. Propane-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals) and surfactant (trade name: Emulgen 120, manufactured by Kao Corporation) were 2% and 0% in terms of solid content with respect to acrylic acid, respectively. .4% was added to prepare an unsaturated carboxylic acid compound sodium salt solution (Y).
＜溶液（Ｚ）の作製＞
アクリル酸（単量体）（共栄社化学社製）を水で希釈して２５％水溶液を作成した。この水溶液中のアクリル酸のカルボキシル基に対して１化学当量の水酸化カリウム（関東化学社製）を添加して、アクリル酸カリウム（アクリル酸のカリウム塩）水溶液を作製した。
次に、作製したアクリル酸カリウム水溶液に、メチルアルコールで２５重量％に希釈した光重合開始剤〔１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン（チバ・スペシャリティ・ケミカルズ社製 商品名；イルガキュアー ２９５９）〕及び界面活性剤（花王社製 商品名；エマルゲン１２０）をアクリル酸に対して固形分比率でそれぞれ２％及び０．４％添加し、不飽和カルボン酸化合物カリウム溶液（Ｚ）を作製した。
<Preparation of solution (Z)>
Acrylic acid (monomer) (manufactured by Kyoeisha Chemical Co., Ltd.) was diluted with water to prepare a 25% aqueous solution. One chemical equivalent of potassium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added to the carboxyl group of acrylic acid in the aqueous solution to prepare a potassium acrylate (potassium salt of acrylic acid) aqueous solution.
Next, a photopolymerization initiator [1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-diluted to 25 wt% with methyl alcohol was added to the prepared potassium acrylate aqueous solution. Propane-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals) and surfactant (trade name: Emulgen 120, manufactured by Kao Corporation) were 2% and 0% in terms of solid content with respect to acrylic acid, respectively. .4% was added to prepare an unsaturated carboxylic acid compound potassium solution (Z).
＜溶液（Ｗ）の作製＞
アクリル酸（単量体）（共栄社化学社製）を水で希釈して２５％水溶液を作成した。この水溶液中のアクリル酸のカルボキシル基に対して１化学当量の水酸化リチウム（関東化学社製）を添加して、アクリル酸リチウム（アクリル酸リチウム塩）水溶液を作製した。
次に、作製したアクリル酸カリウム水溶液に、メチルアルコールで２５重量％に希釈した光重合開始剤〔１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン（チバ・スペシャリティ・ケミカルズ社製 商品名；イルガキュアー ２９５９）〕及び界面活性剤（花王社製 商品名；エマルゲン１２０）をアクリル酸に対して固形分比率でそれぞれ２％及び０．４％添加し、不飽和カルボン酸化合物リチウム溶液（Ｗ）を作製した。
<Preparation of solution (W)>
Acrylic acid (monomer) (manufactured by Kyoeisha Chemical Co., Ltd.) was diluted with water to prepare a 25% aqueous solution. One chemical equivalent of lithium hydroxide (manufactured by Kanto Chemical Co., Inc.) was added to the carboxyl group of acrylic acid in this aqueous solution to prepare a lithium acrylate (lithium acrylate salt) aqueous solution.
Next, a photopolymerization initiator [1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-diluted to 25 wt% with methyl alcohol was added to the prepared potassium acrylate aqueous solution. Propane-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals) and surfactant (trade name: Emulgen 120, manufactured by Kao Corporation) were 2% and 0% in terms of solid content with respect to acrylic acid, respectively. .4% was added to prepare an unsaturated carboxylic acid compound lithium solution (W).
実施例１
上記の不飽和カルボン酸化合物亜鉛塩溶液（Ｘ）及び不飽和カルボン酸化合物ナトリウム塩溶液（Ｙ）をアクリル酸亜鉛が８６モル％、アクリル酸ナトリウムが１４モル％含まれるように混合した後、当該混合溶液を厚さ１２μｍの二軸延伸ポリエステルフィルム（商品名；エンブレットＰＥＴ１２、ユニチカ社製）からなる基材フィルムのコロナ処理面に、メイヤーバーでコートし、３．５ｇ／ｍ２になるように塗布し、熱風乾燥器を使用して温度；６０℃、時間；３０秒の条件で乾燥した。この後速やかに塗布面を上にしてステンレス板に固定し、ＵＶ照射装置（アイグラフィック社製 ＥＹＥ ＧＲＡＮＤＡＧＥ 型式ＥＣＳ ３０１Ｇ１）を用いて、ＵＶ強度１９０ｍＷ/ｃｍ２、積算光量２５０ｍＪ/ｃｍ２の条件で紫外線を照射して重合を行い、ガスバリア性積層フィルムを得た。得られたガスバリア性積層フィルムを上記記載の方法で評価した。
その評価結果を表１に示す。
Example 1
After mixing the unsaturated carboxylic acid compound zinc salt solution (X) and the unsaturated carboxylic acid compound sodium salt solution (Y) so as to contain 86 mol% of zinc acrylate and 14 mol% of sodium acrylate, biaxially oriented polyester film of the mixed solution thickness 12μm (trade name; Emblet PET 12, manufactured by Unitika Ltd.) on the corona-treated surface of the base film made of, coated with Meyer bar, so as to be 3.5 g / m 2 And dried using a hot air dryer under conditions of temperature; 60 ° C., time; 30 seconds. Immediately after this, the coated surface is fastened and fixed to a stainless steel plate, and using a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic Co., Ltd.) under the conditions of UV intensity 190 mW / cm 2 and integrated light quantity 250 mJ / cm 2 . Polymerization was performed by irradiating with ultraviolet rays to obtain a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.
実施例２
実施例１で用いた混合溶液に代え、上記不飽和カルボン酸化合物亜鉛塩溶液（Ｘ）と不飽和カルボン酸化合物ナトリウム塩溶液（Ｙ）をアクリル酸亜鉛が３３モル％、アクリル酸ナトリウムが６７モル％含まれるように混合した混合溶液を用いる以外は実施例１と同様に行い、ガスバリア性積層フィルムを得た。得られたガスバリア性積層フィルムを上記記載の方法で評価した。
評価結果を表１に示す。
Example 2
Instead of the mixed solution used in Example 1, the unsaturated carboxylic acid compound zinc salt solution (X) and the unsaturated carboxylic acid compound sodium salt solution (Y) were 33 mol% zinc acrylate and 67 mol sodium acrylate. % Was carried out in the same manner as in Example 1 except that a mixed solution mixed so as to be contained was obtained to obtain a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.
実施例３
実施例１で用いた混合溶液に代え、上記不飽和カルボン酸化合物亜鉛塩溶液（Ｘ）と不飽和カルボン酸化合物カリウム塩溶液（Ｚ）をアクリル酸亜鉛が１４モル％、アクリル酸カリウムが８６モル％含まれるように混合した混合溶液を用いる以外は実施例１と同様に行い、ガスバリア性積層フィルムを得た。得られたガスバリア性積層フィルムを上記記載の方法で評価した。
評価結果を表１に示す。
Example 3
Instead of the mixed solution used in Example 1, the unsaturated carboxylic acid compound zinc salt solution (X) and the unsaturated carboxylic acid compound potassium salt solution (Z) were composed of 14 mol% of zinc acrylate and 86 mol of potassium acrylate. % Was carried out in the same manner as in Example 1 except that a mixed solution mixed so as to be contained was obtained to obtain a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.
実施例４
実施例１で用いた混合溶液に代え、上記不飽和カルボン酸化合物亜鉛塩溶液（Ｘ）と不飽和カルボン酸化合物カリウム塩溶液（Ｙ）をアクリル酸亜鉛が３３モル％、アクリル酸カリウムが６７モル％含まれるように混合した混合溶液を用いる以外は実施例１と同様に行い、ガスバリア性積層フィルムを得た。得られたガスバリア性積層フィルムを上記記載の方法で評価した。
評価結果を表１に示す。
Example 4
Instead of the mixed solution used in Example 1, the unsaturated carboxylic acid compound zinc salt solution (X) and the unsaturated carboxylic acid compound potassium salt solution (Y) were 33 mol% zinc acrylate and 67 mol potassium acrylate. % Was carried out in the same manner as in Example 1 except that a mixed solution mixed so as to be contained was obtained to obtain a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.
実施例５
実施例１で用いた混合溶液に代え、上記不飽和カルボン酸化合物亜鉛塩溶液（Ｘ）と不飽和カルボン酸化合物リチウム塩溶液（Ｗ）を用いて、アクリル酸亜鉛が１４モル％、アクリル酸リチウムが８６モル％含まれるように混合した混合溶液を用いる以外は実施例１と同様に行い、ガスバリア性積層フィルムを得た。得られたガスバリア性積層フィルムを上記記載の方法で評価した。
評価結果を表１に示す。
Example 5
Instead of the mixed solution used in Example 1, the unsaturated carboxylic acid compound zinc salt solution (X) and the unsaturated carboxylic acid compound lithium salt solution (W) were used, and zinc acrylate was 14 mol%, lithium acrylate. Was performed in the same manner as in Example 1 except that a mixed solution mixed so as to contain 86 mol% was obtained, thereby obtaining a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.
実施例６
実施例１で用いた混合溶液に代え、上記不飽和カルボン酸化合物亜鉛塩溶液（Ｘ）と不飽和カルボン酸化合物リチウム塩溶液（Ｗ）を用いて、アクリル酸亜鉛が３３モル％、アクリル酸リチウムが６７モル％含まれるように混合した混合溶液を用いる以外は実施例１と同様に行い、ガスバリア性積層フィルムを得た。得られたガスバリア性積層フィルムを上記記載の方法で評価した。
評価結果を表１に示す。
Example 6
Instead of the mixed solution used in Example 1, the unsaturated carboxylic acid compound zinc salt solution (X) and the unsaturated carboxylic acid compound lithium salt solution (W) were used. Was performed in the same manner as in Example 1 except that a mixed solution mixed so as to contain 67 mol% was obtained to obtain a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.
評価結果を表１に示す。 The evaluation results are shown in Table 1.
比較例１
上記の不飽和カルボン酸化合物ナトリウム塩溶液（Ｙ）を、厚さ１２μｍの二軸延伸ポリエステルフィルム（商品名；エンブレットＰＥＴ１２、ユニチカ社製）からなる基材フィルムのコロナ処理面に、メイヤーバーでコートし、３．５ｇ／ｍ２になるように塗布し、熱風乾燥器を使用して温度；６０℃、時間；３０秒の条件で乾燥した。この後速やかに塗布面を上にしてステンレス板に固定し、ＵＶ照射装置（アイグラフィック社製 ＥＹＥ ＧＲＡＮＤＡＧＥ 型式ＥＣＳ ３０１Ｇ１）を用いて、ＵＶ強度１９０ｍＷ/ｃｍ２、積算光量２５０ｍＪ/ｃｍ２の条件で紫外線を照射して重合を行い、ガスバリア性積層フィルムを得た。得られたガスバリア性積層フィルムを上記記載の方法で評価した。
評価結果を表１に示す。
Comparative Example 1
The above unsaturated carboxylic acid compound sodium salt solution (Y) is applied to a corona-treated surface of a base film made of a biaxially stretched polyester film (trade name; Emblet PET12, manufactured by Unitika) with a thickness of 12 μm using a Meyer bar. It was coated and applied to 3.5 g / m 2, and dried using a hot air drier at a temperature of 60 ° C. for a time of 30 seconds. Immediately after this, the coated surface is fastened and fixed to a stainless steel plate, and using a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic) under the conditions of UV intensity 190 mW / cm 2 and integrated light quantity 250 mJ / cm 2 . Polymerization was performed by irradiating with ultraviolet rays to obtain a gas barrier laminate film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.
比較例２
比較例１の溶液に代え、不飽和カルボン酸化合物カリウム塩溶液（Ｚ）を用いた以外は比較例１と同様に行い、ガスバリア性積層フィルムを得た。得られたガスバリア性積層フィルムを上記記載の方法で評価した。
評価結果を表１に示す。
Comparative Example 2
It replaced with the solution of the comparative example 1, and carried out similarly to the comparative example 1 except having used the unsaturated carboxylic acid compound potassium salt solution (Z), and obtained the gas-barrier laminated film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.
比較例３
比較例１の溶液に代え、不飽和カルボン酸化合物リチウム塩溶液（Ｗ）を用いた以外は比較例１と同様に行い、ガスバリア性積層フィルムを得た。得られたガスバリア性積層フィルムを上記記載の方法で評価した。
評価結果を表１に示す。
Comparative Example 3
It replaced with the solution of the comparative example 1, and carried out similarly to the comparative example 1 except having used the unsaturated carboxylic acid compound lithium salt solution (W), and obtained the gas barrier laminated film. The obtained gas barrier laminate film was evaluated by the method described above.
The evaluation results are shown in Table 1.
本発明の５０モル％を超えて不飽和カルボン酸化合物一価金属塩を含む不飽和カルボン酸化合物多価金属塩共重合体からなるガスバリア性膜及びかかるガスバリア性膜を形成してなる積層体は、高湿度下での耐酸素透過性（ガスバリア性）に優れているので、かかる特徴を活かして、包装材料、特に高いガスバリア性が要求される内容物の食品包装材料、特に粒状、粉体、乾燥物の包装用材料を始め、医療用途、工業用途等さまざまな包装材料としても好適に使用し得る。 A gas barrier film comprising an unsaturated carboxylic acid compound polyvalent metal salt copolymer containing an unsaturated carboxylic acid compound monovalent metal salt exceeding 50 mol% of the present invention, and a laminate formed by forming such a gas barrier film, Because of its excellent oxygen permeation resistance (gas barrier properties) under high humidity, taking advantage of such characteristics, it can be used for packaging materials, especially food packaging materials that require high gas barrier properties, especially granular, powder, It can be suitably used as various packaging materials such as dry material packaging materials, medical applications and industrial applications.
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| JP2010042574A (en) * | 2008-08-11 | 2010-02-25 | Tohcello Co Ltd | Gas barrier laminated film |
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