JP6106460B2 - Gas barrier film, gas barrier laminate, and method for producing the same - Google Patents
Gas barrier film, gas barrier laminate, and method for producing the same Download PDFInfo
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- JP6106460B2 JP6106460B2 JP2013036749A JP2013036749A JP6106460B2 JP 6106460 B2 JP6106460 B2 JP 6106460B2 JP 2013036749 A JP2013036749 A JP 2013036749A JP 2013036749 A JP2013036749 A JP 2013036749A JP 6106460 B2 JP6106460 B2 JP 6106460B2
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- acrylate
- gas barrier
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- meth
- solution
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 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
- 230000020169 heat generation Effects 0.000 description 1
- 239000012793 heat-sealing layer Substances 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical class C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 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
- 238000007750 plasma spraying Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002401 polyacrylamide 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
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005630 polypropylene random copolymer 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
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 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
- 230000001681 protective effect Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Description
本発明は、透明性を有し、低湿度下及び高湿度下での水蒸気等のガスバリア性に優れるガスバリア性膜、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, a gas barrier laminate, and a method for producing the same, which are transparent and have excellent gas barrier properties such as water vapor under low and high humidity.
近年、酸素あるいは水蒸気等に対するバリア性材料として、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蒸着して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。
In recent years, inorganic oxides such as silicon oxide and aluminum oxide have been deposited on film substrates as a barrier material against oxygen or water vapor by vacuum deposition, sputtering, ion plating, chemical vapor deposition, etc. A transparent gas barrier film formed is drawing attention.
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, the inorganic oxide may crack due to rubbing or elongation during post-processing printing or laminating or filling the contents, and the gas barrier property may be lowered. However, there is a problem that sufficient gas barrier properties cannot be obtained.
一方、ガスバリア性を有する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を二軸延伸フィルム基材に積層する方法（例えば、特許文献１）、あるいはポリビニルアルコールとポリ（メタ）アクリル酸との組成物を二軸延伸フィルム基材に被覆する方法（例えば、特許文献２）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酸素バリア性が低下し、ポリビニルアルコールとポリ（メタ）アクリル酸との組成物は、エステル化を十分に進行させてフィルムのガスバリア性を高めるためには高温で長時間の加熱が必要であるため生産性に問題があり、また、高湿度下でのガスバリア性は不十分であった。また、高温で長時間反応させることによりフィルムが着色し、外観を損ねるため食品包装用には改善が必要である。 On the other hand, a method of laminating a polyvinyl alcohol having a gas barrier property and an ethylene / vinyl alcohol copolymer on a biaxially stretched film substrate (for example, Patent Document 1), or a composition of polyvinyl alcohol and poly (meth) acrylic acid A method of coating a biaxially stretched film substrate (for example, Patent Document 2) has been proposed. However, the gas barrier film formed by laminating polyvinyl alcohol has a low oxygen barrier property under high humidity, and the composition of polyvinyl alcohol and poly (meth) acrylic acid is sufficiently esterified to advance the film. In order to improve the gas barrier property, heating at a high temperature for a long time is necessary, so there is a problem in productivity, and the gas barrier property under high humidity is insufficient. Further, since the film is colored by reacting at high temperature for a long time and the appearance is impaired, improvement for food packaging is necessary.
高湿度下でのガスバリア性を解決する方法として、アクリル酸亜鉛などの不飽和カルボン酸多価金属塩を重合してなるガスバリア性膜（例えば、特許文献３）が提案されている。当該特許文献３には、アクリル酸亜鉛などの不飽和カルボン酸多価金属塩と５０モル％以下のアクリル酸リチウムなどの不飽和カルボン酸一価金属塩との混合物を重合してなるガスバリア性膜も提案されている。
アクリル酸亜鉛などの不飽和カルボン酸多価金属塩を重合してなるガスバリア性膜は、低湿度下及び高湿度下での水蒸気等のガスバリア性に優れるものの、用途によっては更なるガスバリア性の改善が求められている。
As a method for solving the gas barrier property under high humidity, a gas barrier film (for example, Patent Document 3) formed by polymerizing an unsaturated carboxylic acid polyvalent metal salt such as zinc acrylate has been proposed. Patent Document 3 discloses a gas barrier film formed by polymerizing a mixture of an unsaturated carboxylic acid polyvalent metal salt such as zinc acrylate and an unsaturated carboxylic acid monovalent metal salt such as 50 mol% or less of lithium acrylate. Has also been proposed.
Gas barrier film made by polymerizing unsaturated carboxylic acid polyvalent metal salt such as zinc acrylate is excellent in gas barrier properties such as water vapor under low and high humidity, but further improvement of gas barrier properties depending on the application. Is required.
本発明は、透明性を有し、高湿度下での水蒸気等のガスバリア性に優れるガスバリア性膜を得ることを目的とする。 An object of the present invention is to obtain a gas barrier film having transparency and excellent gas barrier properties such as water vapor under high humidity.
本発明は、アクリル酸亜鉛から導かれる単位を４〜９８質量％、アクリル酸マグネシウムから導かれる単位を１〜４８質量％、及びアクリル酸リチウムから導かれる単位を１〜４８質量％含む〔但し、ａ＋ｂ＋ｃ＝１００質量％とする。〕アクリル酸多価金属塩の重合体からなるガスバリア性膜、当該ガスバリア性膜を有するガスバリア性積層体、及びその製造方法を提供するものである。 The present invention comprises 4 to 98% by mass of units derived from zinc acrylate, 1 to 48% by mass of units derived from magnesium acrylate, and 1 to 48% by mass of units derived from lithium acrylate [provided that a + b + c = 100 mass%. The present invention provides a gas barrier film comprising a polymer of a polyvalent metal salt of acrylic acid, a gas barrier laminate having the gas barrier film, and a method for producing the same.
本発明のガスバリア性膜は、高温高湿下でも優れバリア性を持ち、なおかつ経時安定なバリア性も有する。 The gas barrier film of the present invention has excellent barrier properties even at high temperatures and high humidity, and also has stable barrier properties over time.
（ガスバリア性膜）
本発明のガスバリア性膜は、アクリル酸亜鉛から導かれる単位（ａ）を４〜９８質量％、好ましくは５０〜９４質量％、さらに好ましくは７０〜９０質量％、アクリル酸マグネシウムから導かれる単位（ｂ）を１〜４８質量％、好ましくは１〜３５質量％、さらに好ましくは２〜２５質量％及びアクリル酸リチウムから導かれる単位（ｃ）を１〜４８質量％、好ましくは１〜３５質量％、さらに好ましくは４〜２５質量％の範囲で含む〔但し、ａ＋ｂ＋ｃ＝１００質量％とする。〕アクリル酸多価金属塩の重合体からなる。
(Gas barrier film)
In the gas barrier film of the present invention, the unit (a) derived from zinc acrylate is 4 to 98% by mass, preferably 50 to 94% by mass, more preferably 70 to 90% by mass, and units derived from magnesium acrylate ( 1) to 48% by weight of b), preferably 1 to 35% by weight, more preferably 2 to 25% by weight, and 1 to 48% by weight of unit (c) derived from lithium acrylate, preferably 1 to 35% by weight. More preferably, it is contained in the range of 4 to 25% by mass [provided that a + b + c = 100% by mass. It consists of a polymer of polyvalent metal salt of acrylic acid.
アクリル酸マグネシウムから導かれる単位（ｂ）の量が１質量％未満のアクリル酸多価金属塩の重合体からなるガスバリア性膜は６０℃、９０％湿度下の水蒸気バリア性が改良されない虞があり、一方、（ｂ）の量が４８質量％を超えるアクリル酸多価金属塩の重合体からなるガスバリア性膜は、６０℃、９０％湿度下の水蒸気バリア性が改良されない虞がある。
アクリル酸リチウムから導かれる単位（ｃ）の量が１質量％未満のアクリル酸多価金属塩の重合体からなるガスバリア性膜は、６０℃、９０％湿度下の水蒸気バリア性が改良されない虞があり、一方、（ｃ）の量が４８質量％を超えるアクリル酸多価金属塩の重合体からなるガスバリア性膜は、６０℃、９０％湿度下の水蒸気バリア性が改良されない虞がある。
本発明のアクリル酸多価金属塩の重合体からなるガスバリア性膜（以下、単に「ガスバリア性膜」と記載する場合がある。）は、その表面に無機化合物層が形成されていてもよい。
A gas barrier film made of a polymer of a polyvalent metal salt of acrylic acid whose amount of the unit (b) derived from magnesium acrylate is less than 1% by mass may not improve the water vapor barrier property at 60 ° C. and 90% humidity. On the other hand, a gas barrier film made of a polymer of polyvalent metal acrylate with an amount of (b) exceeding 48% by mass may not improve the water vapor barrier property at 60 ° C. and 90% humidity.
A gas barrier film made of a polymer of polyvalent metal acrylate having a unit (c) derived from lithium acrylate of less than 1% by mass may not improve the water vapor barrier property at 60 ° C. and 90% humidity. On the other hand, a gas barrier film made of a polymer of polyvalent metal acrylate with an amount of (c) exceeding 48% by mass may not improve the water vapor barrier property at 60 ° C. and 90% humidity.
The gas barrier film (hereinafter sometimes simply referred to as “gas barrier film”) made of a polymer of polyvalent metal acrylate of the present invention may have an inorganic compound layer formed on the surface thereof.
（無機化合物層）
本発明に係る無機化合物層を形成する無機化合物は蒸着できる無機化合物であれば、特に限定はされないが、具体的には、例えば、クロム（Ｃｒ）、亜鉛（Ｚｎ）、コバルト（Ｃｏ）、アルミニウム（Ａｌ）、錫（Ｓｎ）及び珪素（Ｓｉ）等の金属あるいはこれら金属の酸化物、窒化物、窒酸化物、硫化物、リン化物等が挙げられる。これら無機化合物の中でも、酸化物、特に酸化アルミニウム、シリカ（酸化珪素）等の酸化物、珪素窒酸化物が透明性に優れるので好ましい。
これら無機化合物層をガスバリア性膜の表面に形成させる方法としては、触媒ＣＶＤ（ＣＡＴ−ＣＶＤ）、化学蒸着（ＣＶＤ）、低圧ＣＶＤ及びプラズマＣＶＤ等の化学蒸着法、真空蒸着（反応性真空蒸着）、スパッタリング（反応性スパッタリング）及びイオンプレーティング（反応性イオンプレーティング）等の物理蒸着法（ＰＶＤ）、低圧プラズマスプレイ及びプラズマスプレイ等のプラズマスプレイ法が例示できる。
形成される無機化合物層の厚さは、通常１５〜５０００Å、好ましくは１５〜１０００Å、より好ましくは２０〜４５０Åの範囲である。５０００Åを越えると耐屈曲性が低下するとなる虞があり、一方、１５Å未満では充分な耐ガスバリア性が得られない虞がある。
(Inorganic compound layer)
The inorganic compound that forms the inorganic compound layer according to the present invention is not particularly limited as long as it is an inorganic compound that can be deposited. Specifically, for example, chromium (Cr), zinc (Zn), cobalt (Co), aluminum Examples thereof include metals such as (Al), tin (Sn), and silicon (Si), and oxides, nitrides, nitride oxides, sulfides, and phosphides of these metals. Among these inorganic compounds, oxides, particularly oxides such as aluminum oxide and silica (silicon oxide), and silicon nitride oxide are preferable because of excellent transparency.
Methods for forming these inorganic compound layers on the surface of the gas barrier film include chemical vapor deposition methods such as catalytic CVD (CAT-CVD), chemical vapor deposition (CVD), low pressure CVD and plasma CVD, and vacuum vapor deposition (reactive vacuum vapor deposition). Examples thereof include physical vapor deposition (PVD) such as sputtering (reactive sputtering) and ion plating (reactive ion plating), and plasma spraying such as low-pressure plasma spray and plasma spray.
The thickness of the inorganic compound layer to be formed is usually in the range of 15 to 5000 mm, preferably 15 to 1000 mm, more preferably 20 to 450 mm. If it exceeds 5000 mm, the bending resistance may be lowered. On the other hand, if it is less than 15 mm, sufficient gas barrier resistance may not be obtained.
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、前記本発明のガスバリア性膜が形成されてなる積層体である。
（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、中空体、カップ、トレー等の種々公知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。
(Gas barrier laminate)
The gas barrier laminate of the present invention is a laminate in which the gas barrier film of the present invention is formed on at least one surface of a base material layer.
(Base material layer)
The base material layer forming the gas barrier laminate of the present invention has various known shapes such as a sheet or film made of a thermosetting resin or a thermoplastic resin, a hollow body, a cup, a tray, paper, aluminum foil, etc. Consists of.
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.
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。
また、本発明に係る基材層は、少なくとも片面に、前記無機化合物層が形成されていてもよい。
かかる基材層の表面あるいはガスバリア性膜の表面に蒸着される無機化合物としては、蒸着できる無機化合物であればとくに限定はされないが、具体的には、例えば、クロム（Ｃｒ）、亜鉛（Ｚｎ）、コバルト（Ｃｏ）、アルミニウム（Ａｌ）、錫（Ｓｎ）及び珪素（Ｓｉ）等の金属あるいはこれら金属の酸化物、窒化物、硫化物、リン化物等が挙げられる。これら無機化合物の中でも、酸化物、とくに酸化アルミニウム、酸化亜鉛、シリカ（酸化珪素）等の酸化物が透明性に優れるので好ましい。
これら無機化合物の蒸着層（Ｄ）を基材層（Ｃ）表面あるいはガスバリア性膜の表面に形成させる方法としては、化学蒸着（ＣＶＤ）、低圧ＣＶＤ及びプラズマＣＶＤ等の化学蒸着法、真空蒸着法（反応性真空蒸着）、スパッタリング（反応性スパッタリング）及びイオンプレーティング（反応しイオンプレーティング）等の物理蒸着法（ＰＶＤ）、低圧プラズマスプレイ及びプラズマスプレイ等のプラズマスプレイ法が例示出来る。
In order to improve the adhesion with the gas barrier film, these substrate layers are subjected to surface activation treatment such as corona treatment, flame treatment, plasma treatment, undercoat treatment, primer coat treatment, flame treatment, etc. You may keep going.
In the base material layer according to the present invention, the inorganic compound layer may be formed on at least one surface.
The inorganic compound deposited on the surface of the base material layer or the gas barrier film is not particularly limited as long as it is an inorganic compound that can be deposited. Specifically, for example, chromium (Cr), zinc (Zn) And metals such as cobalt (Co), aluminum (Al), tin (Sn), and silicon (Si), and oxides, nitrides, sulfides, phosphides, and the like of these metals. Among these inorganic compounds, oxides, particularly oxides such as aluminum oxide, zinc oxide, and silica (silicon oxide) are preferable because of excellent transparency.
As a method of forming the vapor deposition layer (D) of these inorganic compounds on the surface of the base material layer (C) or the surface of the gas barrier film, chemical vapor deposition such as chemical vapor deposition (CVD), low pressure CVD and plasma CVD, or vacuum vapor deposition Examples thereof include physical vapor deposition methods (PVD) such as (reactive vacuum deposition), sputtering (reactive sputtering) and ion plating (reacted ion plating), and plasma spray methods such as low-pressure plasma spray and plasma spray.
基材層の少なくとも片面に無機化合物層を形成させる場合は、基材層の表面にアンダーコート層を設けることが望ましい。アンダーコート層としては、分子内にビニル基を少なくとも１つ以上有する重合性モノマー、オリゴマーをコートして、紫外線や電子線等による架橋反応によりコート層を形成させるものが好適である。重合性モノマーとしては、エポキシ（メタ）アクリレート系、ウレタン（メタ）アクリレート系、ポリエステル（メタ）アクリレート系、ポリエーテル（メタ）アクリレート系、ビニル系、不飽和ポリエステル系のオリゴマーや各種単官能、多官能のアクリレート、メタクリレート、ビニルエステル等のモノマーが挙げられる。中もで、エポキシ（メタ）アクリレート系、ウレタン（メタ）アクリレート系、特にウレタン（メタ）アクリレート系のアンダーコート層を設けることが望ましい。 When an inorganic compound layer is formed on at least one surface of the base material layer, it is desirable to provide an undercoat layer on the surface of the base material layer. As the undercoat layer, a layer in which a polymerizable monomer or oligomer having at least one vinyl group in the molecule is coated and a coat layer is formed by a crosslinking reaction by ultraviolet rays or electron beams is suitable. Polymerizable monomers include epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates, vinyls, unsaturated polyesters, various monofunctional, Examples include monomers such as functional acrylates, methacrylates, and vinyl esters. Among them, it is desirable to provide an epoxy (meth) acrylate-based, urethane (meth) acrylate-based, particularly urethane (meth) acrylate-based undercoat layer.
エポキシ（メタ）アクリレート系化合物としては、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、ビスフェノールＳ型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールノボラク型エポキシ化合物、脂肪族エポキシ化合物等のエポキシ化合物とアクリル酸またはメタクリル酸を反応させて得られる化合物、更にはこれらの化合物をカルボン酸またはその無水物と反応させて得られる酸変性エポキシ（メタ）アクリレートが例示される。これらのエポキシ（メタ）アクリレート系の化合物は、光重合開始剤及び必要に応じて他の光重合あるいは熱反応性モノマーからなる希釈剤と共に、基材層の表面に塗布され、その後紫外線等を照射して架橋反応によりアンダーコート層が形成される。 Epoxy (meth) acrylate compounds include epoxy compounds such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, aliphatic epoxy compounds and the like. Examples include compounds obtained by reacting acrylic acid or methacrylic acid, and acid-modified epoxy (meth) acrylates obtained by reacting these compounds with carboxylic acids or anhydrides thereof. These epoxy (meth) acrylate compounds are applied to the surface of the base material layer together with a photopolymerization initiator and, if necessary, other photopolymerization or heat-reactive monomer diluent, and then irradiated with ultraviolet rays. Thus, an undercoat layer is formed by a crosslinking reaction.
ウレタン（メタ）アクリレート系化合物は、ポリオール化合物とジイソシアネート化合物からなるオリゴマーをアクリレート化したものから構成される。
ポリウレタン系オリゴマーは、ポリイソシアネートとポリオールとの縮合生成物から得ることができる。具体的なポリイソシアネートとしては、メチレン・ビス（ｐ−フェニレンジイソシアネート）、ヘキサメチレンジイソシアネート・ヘキサントリオールの付加体、ヘキサメチレンジイソシアネート、トリレンジイソシアネート、トリレンジイソシアネートトリメチロールプロパンのアダクト体、１，５−ナフチレンジイソシアネート、チオプロピルジイソシアネート、エチルベンゼン−２，４−ジイソシアネート、２，４−トリレンジイソシアネート二量体、水添キシリレンジイソシアネート、トリス（４−フェニルイソシアネート）チオフォスフェートなどが例示でき、また、具体的なポリオールとしては、ポリオキシテトラメチレングリコールなどのポリエーテル系ポリオール、ポリアジペートポリオール、ポリカーボネートポリオールなどのポリエステル系ポリオール、アクリル酸エステル類とヒドロキシエチルメタアクリレートとのコポリマーなどがある。アクリレートを構成する単量体としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２エチルヘキシル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、フェニル（メタ）アクリレートなどがある。
これらのエポキシ（メタ）アクリレート系化合物、ウレタン（メタ）アクリレート系化合物は、必要に応じて、併用される。また、これらを重合させる方法としては、公知の種々の方法、具体的には電離性放射線の照射又は加熱などによる方法があげられる。
これらを紫外線で硬化して使用する場合は、アセトフェノン類、ベンゾフェノン類、ミフィラベンゾイルベンゾエート、α−アミロキシムエステルまたはチオキサントン類などを光重合開始剤として、また、ｎ−ブチルアミン、トリエチルアミン、トリｎ−ブチルホスフィンなどを光増感剤として混合して使用するのが好ましい。本発明では、エポキシ（メタ）アクリレート系化合物とウレタン（メタ）アクリレート系化合物は、併用することも行われる。
The urethane (meth) acrylate compound is composed of an acrylated oligomer composed of a polyol compound and a diisocyanate compound.
The polyurethane-based oligomer can be obtained from a condensation product of polyisocyanate and polyol. Specific polyisocyanates include adducts of methylene bis (p-phenylene diisocyanate), hexamethylene diisocyanate / hexane triol, hexamethylene diisocyanate, tolylene diisocyanate, tolylene diisocyanate trimethylolpropane, 1,5- Examples include naphthylene diisocyanate, thiopropyl diisocyanate, ethylbenzene-2,4-diisocyanate, 2,4-tolylene diisocyanate dimer, hydrogenated xylylene diisocyanate, tris (4-phenyl isocyanate) thiophosphate, and the like. Typical polyols include polyether polyols such as polyoxytetramethylene glycol, polyadipate polyols, and polycarbonate polyols. What polyester polyols, and the like copolymers of acrylic acid esters and hydroxyethyl methacrylate. As monomers constituting the acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenyl (Meth) acrylate and the like.
These epoxy (meth) acrylate compounds and urethane (meth) acrylate compounds are used in combination as necessary. Examples of a method for polymerizing these include various known methods, specifically, a method using irradiation with ionizing radiation or heating.
When these are used after being cured with ultraviolet rays, acetophenones, benzophenones, mifilabenzoylbenzoate, α-amyloxime ester or thioxanthone are used as photopolymerization initiators, and n-butylamine, triethylamine, tri-n- It is preferable to use butyl phosphine or the like as a photosensitizer. In the present invention, the epoxy (meth) acrylate compound and the urethane (meth) acrylate compound are also used in combination.
また、これらのエポキシ（メタ）アクリレート系化合物やウレタン（メタ）アクリレート系化合物は、（メタ）アクリル系モノマーで希釈することが行われる。このような（メタ）アクリル系モノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、フェニル（メタ）アクリレート、多官能モノマーとしてトリメチロールプロパントリ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレートなどが例示でされる。 In addition, these epoxy (meth) acrylate compounds and urethane (meth) acrylate compounds are diluted with (meth) acrylic monomers. Examples of such (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, and butoxyethyl (meth). Acrylate, phenyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) as multifunctional monomer Examples include acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. I am in.
中でもアンダーコート層としてウレタン（メタ）アクリレート系化合物を用いた場合は、得られるガスバリア性フィルムの酸素ガスバリア性の改良に寄与する。
これらのアンダーコート層は、通常０．０５〜５．０ｇ／ｍ２が通常であり、中でも０．１〜３．０ｇ／ｍ２が好適である。
また、無機化合物層の表面は、本発明のガスバリア性膜を設ける前に、コロナ処理、グロー放電処理、大気圧プラズマ処理、真空プラズマ放電処理などの前処理をすることが望ましい。中でもコロナ処理が好適である。コロナ処理の条件は、特に限定されないが、例えば放電周波数は、５〜４０ｋＨｚ、中でも１０〜３０ｋＨｚ程度を用いることもでき、波形として例えば交流正弦波がある。電極と誘電体ロールとのギャップのクリアランスを０．１〜１０ミリメートル、中でも１．０〜２．０ミリメートル程度とし、処理量として０．３〜０．４ＫＶ・Ａ・分／ｍ２程度とすることもできる。空気中常圧で処理できる点で好適である。
In particular, when a urethane (meth) acrylate compound is used as the undercoat layer, it contributes to the improvement of the oxygen gas barrier property of the obtained gas barrier film.
These undercoat layers are usually 0.05 to 5.0 g / m 2 , and 0.1 to 3.0 g / m 2 is particularly preferable.
The surface of the inorganic compound layer is preferably subjected to pretreatment such as corona treatment, glow discharge treatment, atmospheric pressure plasma treatment, and vacuum plasma discharge treatment before providing the gas barrier film of the present invention. Of these, corona treatment is preferred. The conditions for the corona treatment are not particularly limited, but for example, the discharge frequency may be 5 to 40 kHz, especially about 10 to 30 kHz, and the waveform includes, for example, an AC sine wave. The clearance of the gap between the electrode and the dielectric roll is set to 0.1 to 10 mm, particularly about 1.0 to 2.0 mm, and the processing amount is set to about 0.3 to 0.4 KV · A · min / m 2 . You can also It is preferable in that it can be processed at normal pressure in air.
（熱融着層）
本発明のガスバリア性積層体は、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。
(Heat-fusion layer)
In the gas barrier laminate of the present invention, 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 Polyolefin such as propylene random copolymer alone or two or more compositions, ethylene / vinyl acetate copolymer (EVA), ethylene / (meth) acrylic acid copolymer or metal salt thereof, composition of EVA and polyolefin It is a layer obtained from things.
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.
＜ガスバリア性膜及びガスバリア性積層体の製造方法＞
本発明のガスバリア性膜及びガスバリア性積層体の製造方法（以下、ガスバリア層膜等の製造方法ともいう）は、基材層の少なくとも片面にアクリル酸亜鉛（ａ′）４〜９８質量％、好ましくは５０〜９４質量％、さらに好ましくは７０〜９０質量％、アクリル酸マグネシウム（ｂ′）１〜４８質量％、好ましくは１〜３５質量％、さらに好ましくは２〜２５質量％、及びアクリル酸リチウム（ｃ′）１〜４８質量％、好ましくは１〜３５質量％、さらに好ましくは４〜２５質量％の範囲で含むアクリル酸多価金属塩混合物〔但し、ａ′＋ｂ′＋ｃ′＝１００質量％とする。〕の溶液を塗布した後、不飽和カルボン酸化合物多価金属塩混合物を重合することを特徴とするガスバリア性積層体の製造方法である。
本発明のガスバリア性膜等の製造方法に於いて、基材として前記基材層を用いれば、本発明のガスバリア性積層体が得られる。また、基材として前記基材層、若しくは、ガラス、セラミック、金属等の無機物等あるいはその他の材料を用い、不飽和カルボン酸化合物多価金属塩混合物を重合して得られる重合体を基材から剥離すれば単層の本発明のガスバリア性膜が得られる。
不飽和カルボン酸化合物多価金属塩混合物の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。
<Method for producing gas barrier film and gas barrier laminate>
The method for producing a gas barrier film and a gas barrier laminate of the present invention (hereinafter also referred to as a method for producing a gas barrier layer film or the like) is preferably 4 to 98% by mass of zinc acrylate (a ′) on at least one side of the substrate layer. Is 50 to 94 mass%, more preferably 70 to 90 mass%, magnesium acrylate (b ') 1 to 48 mass%, preferably 1 to 35 mass%, more preferably 2 to 25 mass%, and lithium acrylate (C ') Acrylic acid polyvalent metal salt mixture containing 1 to 48% by mass, preferably 1 to 35% by mass, more preferably 4 to 25% by mass [provided that a' + b '+ c' = 100% by mass And And then polymerizing the unsaturated carboxylic acid compound polyvalent metal salt mixture, the method for producing a gas barrier laminate.
In the method for producing a gas barrier film or the like of the present invention, when the substrate layer is used as a substrate, the gas barrier laminate of the present invention is obtained. In addition, a polymer obtained by polymerizing an unsaturated carboxylic acid compound polyvalent metal salt mixture from the base material layer, or an inorganic material such as glass, ceramic, metal, or other materials as a base material is used. When peeled, a single-layer gas barrier film of the present invention can be obtained.
Examples of the solvent used for the solution of the unsaturated carboxylic acid compound polyvalent metal salt mixture include water, lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, organic solvents such as acetone and methyl ethyl ketone, and mixed solvents thereof. Is most preferred.
基材層等の少なくとも片面に不飽和カルボン酸化合物多価金属塩混合物の溶液を塗布する方法としては、とくに限定はされず、種々公知の方法を採り得る。具体的には、当該溶液に基材層等を浸漬する方法、当該溶液を基材層等の表面に噴霧する方法に加え、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、ダイコーター等種々公知の塗工機を用いて、不飽和カルボン酸化合物多価金属塩混合物の溶液中（固形分）の量で０．０５〜１０ｇ／ｍ２、好ましくは０．１〜５ｇ／ｍ２となるよう塗布すればよい。
なお、不飽和カルボン酸化合物多価金属塩混合物を溶解させる際に、不飽和カルボン酸化合物多価金属塩混合物の他に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）アクリル酸エチルなどの不飽和カルボン酸エステル化合物、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、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（重合体）等を添加してもよい。
The method for applying the solution of the unsaturated carboxylic acid compound polyvalent metal salt mixture to at least one surface of the substrate layer or the like is not particularly limited, and various known methods can be adopted. Specifically, in addition to a method of immersing a base material layer or the like in the solution, a method of spraying the solution onto the surface of the base material layer or the like, for example, an air knife coater, a direct gravure coater, a gravure offset, an arc gravure coater, 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, die coaters, etc. Using a known coating machine, the amount of the unsaturated carboxylic acid compound polyvalent metal salt mixture in the solution (solid content) is 0.05 to 10 g / m 2 , preferably 0.1 to 5 g / m 2. It may be applied as follows.
In addition, when dissolving the unsaturated carboxylic acid compound polyvalent metal salt mixture, in addition to the unsaturated carboxylic acid compound polyvalent metal salt mixture, methyl (meth) acrylate, (meta ) Monomers or low molecular weight compounds such as unsaturated carboxylic acid ester compounds such as ethyl acrylate, vinyl ester compounds such as vinyl acetate, acrylic acid ester polymers, ethylene / acrylic acid copolymers, polyvinyl acetate, ethylene -A high molecular weight compound (polymer) such as a vinyl acetate copolymer, polyester, or polyurethane may be added.
また、不飽和カルボン酸化合物多価金属塩混合物を溶解させる際には、本発明の目的を損わない範囲で、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。
基材層等に塗布した不飽和カルボン酸化合物多価金属塩混合物を重合させて重合体とする方法としては、種々公知の方法、具体的には例えば、電離性放射線の照射また加熱等による方法が挙げられる。
In addition, when dissolving the unsaturated carboxylic acid compound polyvalent metal salt mixture, the lubricant, slip agent, anti-blocking agent, antistatic agent, antifogging agent, pigment, as long as the object of the present invention is not impaired. Various additives such as dyes, inorganic or organic fillers may be added, and various surfactants may be added in order to improve wettability with the base material layer.
As a method of polymerizing the unsaturated carboxylic acid compound polyvalent metal salt mixture applied to the base material layer to form a polymer, various known methods, specifically, for example, a method by irradiation with ionizing radiation or heating, etc. Is mentioned.
電離性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、電子線等が挙げられる。これらの電離性放射線の中でも、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。
電離性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多価金属塩混合物の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−シクロヘキシル−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・スペシャルティ社製）、 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ＴＰ０）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。
When ionizing radiation is used, 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, and visible rays. , Ultraviolet rays, electron beams and the like. 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 the ionizing radiation, it is necessary to add a photopolymerization initiator to the solution of the unsaturated carboxylic acid compound polyvalent metal salt mixture. As the photopolymerization initiator, known ones can be used, for example, 2-hydroxy-2methyl-1-phenyl-propan-1-one (trade name, manufactured by Ciba Specialty Chemicals; Darocur 1173), 1-Hydroxy-cyclohexyl-phenyl ketone (trade name; manufactured by Ciba Specialty Chemicals; Irgacure 184), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name, manufactured by Ciba Specialty Chemicals) Irgacure 819), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name, manufactured by Ciba Specialty Chemicals); Irgacure 2959 ), Α-hydroxyketone, acylphosphine oxa , 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (Lamberty Chemical Specialty, trade name; Essaure KT046), Esacure KT55 (Lamberti Chemical Specialty, Inc.), 2, 4, A radical polymerization initiator manufactured and sold under the trade name of 6-trimethylbenzoyldiphenylphosphine oxide (trade name; speed cure TP0 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多価金属塩混合物を重合させる際は、溶液が水等の溶媒を含んだ状態で重合させてもよいし、一部乾燥後に重合させてもよいが、塗布した溶液が水等の溶媒を多量に含む場合は、溶液を塗布後直ぐに重合させた際に、得られるガスバリア性膜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多価金属塩が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ガスバリア性膜の形成が不十分になり、外観が白化したり、得られる膜の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混合物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。
また、不飽和カルボン酸化合物多価金属塩混合物を重合させる際には、一段階で重合させてもよいし、二段階以上に分けて、即ち、予備重合させた後、本重合させてもよい。
When the unsaturated carboxylic acid compound polyvalent metal salt mixture is polymerized, the solution may be polymerized in a state of containing a solvent such as water, or may be polymerized partially after drying. In the case where a large amount of such a solvent is contained, the resulting gas barrier film may be whitened when the solution is polymerized immediately after coating. On the other hand, the solvent (moisture) decreases, and an unsaturated carboxylic acid compound polyvalent metal salt may precipitate. When polymerization is performed in such a state, formation of a gas barrier film is insufficient, and the appearance is white. Or the gas barrier property of the resulting film may not be stable. Therefore, when polymerizing the coated unsaturated carboxylic acid compound polyvalent metal salt mixture, it is preferable to polymerize in a state containing appropriate moisture.
In addition, when the unsaturated carboxylic acid compound polyvalent metal salt mixture is polymerized, it may be polymerized in one stage, or may be divided into two or more stages, that is, it may be prepolymerized and then main polymerized. .
（オーバーコート層）
本発明のガスバリア性積層体を構成する不飽和カルボン酸化合物多価金属塩の重合体層上にはオーバーコート層を積層してもよい。オーバーコート層を積層することで、不飽和カルボン酸化合物多価金属塩の重合体の膜割れを防ぐ効果がある。オーバーコート層は、分子内にビニル基を少なくとも１つ以上有する重合性モノマー、オリゴマーをコートして、紫外線や電子線等による架橋反応によりコート層を形成させるものが好適である。重合性モノマーとしては、エポキシ（メタ）アクリレート系、ウレタン（メタ）アクリレート系、ポリエステル（メタ）アクリレート系、ポリエーテル（メタ）アクリレート系、ビニル系、不飽和ポリエステル系のオリゴマーや各種単官能、多官能のアクリレート、メタクリレート、ビニルエステル等のモノマーが挙げられる。中もで、エポキシ（メタ）アクリレート系、ウレタン（メタ）アクリレート系、特にウレタン（メタ）アクリレート系のアンダーコート層を設けることが望ましい。これらのエポキシ（メタ）アクリレート系化合物、ウレタン（メタ）アクリレート系化合物は、必要に応じて、併用される。また、これらを重合させる方法としては、公知の種々の方法、具体的には電離性放射線の照射又は加熱などによる方法があげられる。
これらを紫外線で硬化して使用する場合は、アセトフェノン類、ベンゾフェノン類、ミフィラベンゾイルベンゾエート、α−アミロキシムエステルまたはチオキサントン類などを光重合開始剤として、また、ｎ−ブチルアミン、トリエチルアミン、トリｎ−ブチルホスフィンなどを光増感剤として混合して使用するのが好ましい。
(Overcoat layer)
An overcoat layer may be laminated on the polymer layer of the unsaturated carboxylic acid compound polyvalent metal salt constituting the gas barrier laminate of the present invention. By laminating the overcoat layer, there is an effect of preventing film cracking of the polymer of the unsaturated carboxylic acid compound polyvalent metal salt. The overcoat layer is preferably one in which a polymerizable monomer or oligomer having at least one vinyl group in the molecule is coated, and a coat layer is formed by a crosslinking reaction by ultraviolet rays or electron beams. Polymerizable monomers include epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates, vinyls, unsaturated polyesters, various monofunctional, Examples include monomers such as functional acrylates, methacrylates, and vinyl esters. Among them, it is desirable to provide an epoxy (meth) acrylate-based, urethane (meth) acrylate-based, particularly urethane (meth) acrylate-based undercoat layer. These epoxy (meth) acrylate compounds and urethane (meth) acrylate compounds are used in combination as necessary. Examples of a method for polymerizing these include various known methods, specifically, a method using irradiation with ionizing radiation or heating.
When these are used after being cured with ultraviolet rays, acetophenones, benzophenones, mifilabenzoylbenzoate, α-amyloxime ester or thioxanthone are used as photopolymerization initiators, and n-butylamine, triethylamine, tri-n- It is preferable to use butyl phosphine or the like as a photosensitizer.
本発明のガスバリア性積層体は、熱処理をすることが望ましい。熱処理によって重合体層の水蒸気ガスバリア性を更に向上させることができる。熱処理としては、対流伝熱によるもの（例えばドライヤー、オーブン）、伝導伝熱によるもの（例えば加熱ロール）、輻射伝熱によるもの（例えば赤外線、遠赤外線のヒータ等の電磁波を用いるもの）、内部発熱によるもの（例えばマイクロ波）があげられる。オーブンによる熱処理の場合、フィルム基材の種類にもよるが、通常６０℃〜３５０℃程度で、１分〜５時間程度が通常であり、特に１００℃〜２００℃、５分〜２時間が望ましい。長尺のガスバリア積層フィルムを連続で加熱する場合は、加熱ロール及び遠赤外線炉による処理が、処理速度が速く有効である。また、これらの熱処理は、減圧下で行ってもよい。 The gas barrier laminate of the present invention is preferably heat treated. The water vapor gas barrier property of the polymer layer can be further improved by the heat treatment. Heat treatment includes convection heat transfer (eg, dryer, oven), conduction heat transfer (eg, heating roll), radiant heat transfer (eg, use of electromagnetic waves such as infrared and far infrared heaters), internal heat generation (For example, microwaves). In the case of heat treatment in an oven, although it depends on the type of film substrate, it is usually about 60 ° C. to 350 ° C., usually about 1 minute to 5 hours, and particularly preferably 100 ° C. to 200 ° C., 5 minutes to 2 hours. . When a long gas barrier laminated film is continuously heated, treatment with a heating roll and a far-infrared furnace is effective because of its high treatment speed. These heat treatments may be performed under reduced pressure.
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。
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。
EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples.
The physical property values and the like in Examples and Comparative Examples were obtained by the following evaluation methods.
＜アクリル酸亜鉛（ａ′）溶液の作製＞
アクリル酸亜鉛（アクリル酸のＺｎ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％、Ｚｎ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、アクリル酸Ｚｎ（ａ′）溶液を作製した。
<Preparation of zinc acrylate (a ') solution>
Photopolymerization diluted to 25 wt% with methyl alcohol in an aqueous solution of zinc acrylate (Zn salt of acrylic acid) (Asada Chemical Co., Ltd., concentration 30 wt% (acrylic acid component: 20 wt%, Zn component 10 wt%)). Initiator [1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name, manufactured by Ciba Specialty Chemicals; Irgacure 2959)] and Surfactant (trade name; Emulgen 120, manufactured by Kao Corporation) was added to acrylic acid at a solid content ratio of 2% and 0.4%, respectively, to prepare a Zn (a ′) acrylate solution.
＜アクリル酸マグネシウム（ｂ′）溶液の作製＞
アクリル酸マグネシウム（アクリル酸のＭｇ塩）水溶液（浅田化学社製、濃度３０重量％（アクリル酸成分：２６重量％、Ｍｇ成分４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、アクリル酸Ｍｇ（ｂ′）溶液を作製した
<Preparation of Magnesium Acrylate (b ') Solution>
Photopolymerization of magnesium acrylate (Mg salt of acrylic acid) aqueous solution (manufactured by Asada Chemical Co., Ltd., concentration 30 wt% (acrylic acid component: 26 wt%, Mg component 4 wt%)) diluted to 25 wt% with methyl alcohol. 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 at a solid content ratio of 2% and 0.4%, respectively, to prepare an Mg (b ′) acrylate solution.
＜アクリル酸リチウム（ｃ′）溶液の作製＞
アクリル酸（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等モルの水酸化リチウム一水和物（関東化学社製）を添加して、アクリル酸リチウム（アクリル酸のＬｉ塩）水溶液を作製した。
次に、作製したアクリル酸リチウム水溶液に、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、アクリル酸Ｌｉ（ｃ′）溶液を作製した。
<Preparation of Lithium Acrylate (c ') Solution>
Acrylic acid (manufactured by Kyoeisha Chemical Co., Ltd.) was diluted with water to prepare a 25% aqueous solution. An equimolar amount of lithium hydroxide monohydrate (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 lithium acrylate (Li salt of acrylic acid).
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 aqueous lithium acrylate solution. Propan-1-one (trade name, manufactured by Ciba Specialty Chemicals; Irgacure 2959)] and a surfactant (trade name, manufactured by Kao Corporation; Emulgen 120) were 2% and 0% in terms of solid content with respect to acrylic acid, respectively. .4% was added to prepare a Li (c ′) acrylate solution.
＜オーバーコート塗剤（ｄ）溶液の作製＞
アクリル系ＵＶ硬化塗材（三井化学社製 商品名 ＲＡ３０５０）を酢酸エチルで希釈し、固形３０重量％酢酸エチル溶液にしたのち、酢酸エチルで３０重量％に希釈した光重合開始剤〔2,2-ジメトキシ-1,2-ジフェニルエタン-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 ６５１）〕をアクリル系ＵＶ硬化塗材に対して固形分比率４％添加し、オーバーコート塗剤（ｄ）を作製した。
<Preparation of overcoat coating solution (d)>
A photopolymerization initiator [2,2] obtained by diluting an acrylic UV curable coating material (trade name RA3050, manufactured by Mitsui Chemicals, Inc.) with ethyl acetate to form a solid 30% by weight ethyl acetate solution and then diluted to 30% by weight with ethyl acetate. -Dimethoxy-1,2-diphenylethane-1-one (product name; Irgacure 651) manufactured by Ciba Specialty Chemicals Co., Ltd.] was added to the acrylic UV curable coating material at a solid content ratio of 4%, and overcoat coating was applied. Agent (d) was prepared.
＜積層バリアフィルムの作製＞
厚さ５０μｍの無延伸ポリプロピレンフィルム（三井化学東セロ社製 商品名：Ｔ.Ｕ.Ｘ. ＦＣＳ）の片面に、エステル系接着剤（ポリエステル系接着剤（三井化学ポリウレタン社製 商品名：タケラックＡ３１０）：１２重量部、イソシアネート系硬化剤（三井化学ポリウレタン社製 商品名：タケネートＡ３）：１重量部及び酢酸エチル：７重量部）を塗布し乾燥後、実施例、比較例で得られたガスバリア性積層フィルムのバリア面と貼り合わせ（ドライラミネート）、多層フィルムを得た。
<Production of laminated barrier film>
On one side of a 50 μm-thick unstretched polypropylene film (trade name: T.U.X. FCS, manufactured by Mitsui Chemicals, Inc.), an ester adhesive (polyester adhesive (trade name: Takelac A310, manufactured by Mitsui Chemicals Polyurethanes)) : 12 parts by weight, an isocyanate-based curing agent (trade name: Takenate A3 manufactured by Mitsui Chemicals Polyurethanes Co., Ltd .: 1 part by weight and 7 parts by weight of ethyl acetate) and drying, gas barrier properties obtained in Examples and Comparative Examples The laminated film was bonded to the barrier surface (dry lamination) to obtain a multilayer film.
＜評価方法＞
水蒸気透過度［ｇ／（ｍ２・ｄａｙ）］：上記多層フィルムを無延伸ポリプロピレンフィルムが内面になるように重ねて３方をヒートシールし、袋状にした後、内容物として塩化カルシウムを入れ、もう１方をヒートシールにより、表面積が０．０１ｍ２になるように袋を作成し、６０℃９０％Ｒ．Ｈ．の条件で６３時間（初期値）、５７０時間放置し、その重量差で水蒸気透過度を測定した。
<Evaluation method>
Water vapor permeability [g / (m 2 · day)]: The above multilayer film is overlapped so that the unstretched polypropylene film becomes the inner surface, and heat-sealed in three directions to form a bag, and then calcium chloride is added as the contents. The other side is heat-sealed to make a bag with a surface area of 0.01 m 2 , and 60 ° C. 90% R.D. H. The sample was allowed to stand for 63 hours (initial value) and 570 hours under the following conditions, and the water vapor permeability was measured by the weight difference.
〔実施例１〕
アクリル酸Ｚｎ（ａ′）溶液、アクリル酸Ｍｇ（ｂ′）溶液、及びアクリル酸Ｌｉ（ｃ′）溶液を用い、アクリル酸Ｚｎ（ａ′）が７９質量％、アクリル酸Ｍｇ（ｂ′）が９質量％、及びアクリル酸Ｌｉ（ｃ′）が１２質量％になるように混合して、アクリル酸多価金属塩混合物の溶液を得た後、厚さ５０μｍの二軸延伸ポリエステルフィルム（商品名；エンブレットＰＥＴ５０、ユニチカ社製）からなる基材フィルムのコロナ処理面に、メイヤーバーを用いて、２．５ｇ／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った後、得られたガスバリア性積層フィルムを熱板の上に載置して加熱処理した。加熱処理の条件は、熱板の温度２００℃、保持時間６０分である。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。
結果を表１に示す。
[Example 1]
Using Zn (a ′) acrylate solution, Mg (b ′) acrylate solution, and Li (c ′) acrylate solution, Zn (a ′) acrylate was 79% by mass, and Mg (b ′) acrylate was After mixing 9% by mass and 12% by mass of acrylic acid Li (c ′) to obtain a solution of an acrylic acid polyvalent metal salt mixture, a biaxially stretched polyester film having a thickness of 50 μm (trade name) Applied to a corona-treated surface of a base film made of Emblet PET50 (manufactured by Unitika) using a Mayer bar so as to be 2.5 g / m 2 , and a temperature using a hot air dryer; 60 ° C. , Time; dried for 30 seconds. Immediately after this, the coated surface is fastened and fixed to the stainless steel plate, and using a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic Co., Ltd.), the UV intensity is 190 mW / cm 2 and the integrated light quantity is 250 mJ / cm 2 . After carrying out the polymerization by irradiating with ultraviolet rays under the conditions, the obtained gas barrier laminate film was placed on a hot plate and heat-treated. The conditions for the heat treatment are a hot plate temperature of 200 ° C. and a holding time of 60 minutes. The obtained gas barrier laminate film was evaluated by the method described above.
The results are shown in Table 1.
〔実施例２〕
アクリル酸Ｚｎ（ａ′）溶液、アクリル酸Ｍｇ（ｂ′）溶液、及びアクリル酸Ｌｉ（ｃ′）溶液を用い、アクリル酸Ｚｎ（ａ′）が７９質量％、アクリル酸Ｍｇ（ｂ′）が９質量％、及びアクリル酸Ｌｉ（ｃ′）が１２質量％になるように混合して、アクリル酸多価金属塩混合物の溶液を得た後、厚さ５０μｍの二軸延伸ポリエステルフィルム（商品名；エンブレットＰＥＴ５０、ユニチカ社製）からなる基材フィルムのコロナ処理面に、メイヤーバーを用いて、２．５ｇ／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った。形成したガスバリア重合膜層の上に、オーバーコート塗剤（ｄ）をメイヤーバーで３ｇ／ｍ２（固形分）になるように塗布し、６０℃、３０秒間乾燥した。続いて、コート面に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オーバーコート層の重合を行った。得られたガスバリア性積層フィルムを熱板の上に載置して加熱処理した。加熱処理の条件は、熱板の温度２００℃、保持時間６０分である。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。 結果を表１に示す。
[Example 2]
Using Zn (a ′) acrylate solution, Mg (b ′) acrylate solution, and Li (c ′) acrylate solution, Zn (a ′) acrylate was 79% by mass, and Mg (b ′) acrylate was After mixing 9% by mass and 12% by mass of acrylic acid Li (c ′) to obtain a solution of an acrylic acid polyvalent metal salt mixture, a biaxially stretched polyester film having a thickness of 50 μm (trade name) Applied to a corona-treated surface of a base film made of Emblet PET50 (manufactured by Unitika) using a Mayer bar so as to be 2.5 g / m 2 , and a temperature using a hot air dryer; 60 ° C. , Time; dried for 30 seconds. Immediately after this, the coated surface is fastened and fixed to the stainless steel plate, and using a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic Co., Ltd.), the UV intensity is 190 mW / cm 2 and the integrated light quantity is 250 mJ / cm 2 . Polymerization was performed by irradiating ultraviolet rays under the conditions. On the formed gas barrier polymer film layer, the overcoat coating agent (d) was applied with a Mayer bar so as to be 3 g / m 2 (solid content), and dried at 60 ° C. for 30 seconds. Subsequently, the coat surface is irradiated with ultraviolet rays under the conditions of UV intensity: 190 mW / cm 2 and integrated light quantity: 250 mJ / cm 2 using an UV irradiation apparatus (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic). Was polymerized. The obtained gas barrier laminate film was placed on a hot plate and heat-treated. The conditions for the heat treatment are a hot plate temperature of 200 ° C. and a holding time of 60 minutes. The obtained gas barrier laminate film was evaluated by the method described above. The results are shown in Table 1.
〔実施例３〕
実施例２で用いたアクリル酸多価金属混合物の溶液に替えて、アクリル酸Ｚｎ（ａ′）溶液、アクリル酸Ｍｇ（ｂ′）溶液、及びアクリル酸Ｌｉ（ｃ′）溶液を用い、アクリル酸Ｚｎ（ａ′）が８４質量％、アクリル酸Ｍｇ（ｂ′）が４質量％、及びアクリル酸Ｌｉ（ｃ′）が１２質量％になるように混合して、アクリル酸多価金属塩混合物の溶液を用いる以外は実施例２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の評価結果を表１に示す
Example 3
Instead of the solution of the polyvalent metal acrylate mixture used in Example 2, a Zn (a ′) acrylate solution, a Mg (b ′) acrylate solution, and a Li (c ′) acrylate solution were used. A mixture of 84% by mass of Zn (a ′), 4% by mass of Mg (b ′) acrylate, and 12% by mass of Li (c ′) acrylate, A gas barrier laminate film was obtained in the same manner as in Example 2 except that the solution was used.
The evaluation results of the obtained gas barrier laminate film are shown in Table 1.
〔実施例４〕
実施例２で用いたアクリル酸多価金属混合物の溶液に替えて、アクリル酸Ｚｎ（ａ′）溶液、アクリル酸Ｍｇ（ｂ′）溶液、及びアクリル酸Ｌｉ（ｃ′）溶液を用い、アクリル酸Ｚｎ（ａ′）が８７質量％、アクリル酸Ｍｇ（ｂ′）が９質量％、及びアクリル酸Ｌｉ（ｃ′）が４質量％になるように混合して、アクリル酸多価金属塩混合物の溶液を用いる以外は実施例２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の評価結果を表１に示す
Example 4
Instead of the solution of the polyvalent metal acrylate mixture used in Example 2, a Zn (a ′) acrylate solution, a Mg (b ′) acrylate solution, and a Li (c ′) acrylate solution were used. Mixing so that Zn (a ′) is 87 mass%, acrylic acid Mg (b ′) is 9 mass%, and acrylic acid Li (c ′) is 4 mass%. A gas barrier laminate film was obtained in the same manner as in Example 2 except that the solution was used.
The evaluation results of the obtained gas barrier laminate film are shown in Table 1.
〔実施例５〕
実施例２で用いたアクリル酸多価金属混合物の溶液に替えて、アクリル酸Ｚｎ（ａ′）溶液、アクリル酸Ｍｇ（ｂ′）溶液、及びアクリル酸Ｌｉ（ｃ′）溶液を用い、アクリル酸Ｚｎ（ａ′）が７１質量％、アクリル酸Ｍｇ（ｂ′）が２５質量％、及びアクリル酸Ｌｉ（ｃ′）が４質量％になるように混合して、アクリル酸多価金属塩混合物の溶液を用いる以外は実施例２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の評価結果を表１に示す
Example 5
Instead of the solution of the polyvalent metal acrylate mixture used in Example 2, a Zn (a ′) acrylate solution, a Mg (b ′) acrylate solution, and a Li (c ′) acrylate solution were used. Mixing so that Zn (a ′) is 71 mass%, acrylic acid Mg (b ′) is 25 mass%, and acrylic acid Li (c ′) is 4 mass%. A gas barrier laminate film was obtained in the same manner as in Example 2 except that the solution was used.
The evaluation results of the obtained gas barrier laminate film are shown in Table 1.
〔比較例１〕
実施例２で用いたアクリル酸多価金属塩混合物の溶液に替えて、アクリル酸Ｚｎ（ａ′）溶液を単独で用いる以外は実施例２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の評価結果を表１に示す。
[Comparative Example 1]
A gas barrier laminate film was obtained in the same manner as in Example 2 except that the Zn (a ′) acrylate solution was used alone in place of the solution of polyvalent metal acrylate mixture used in Example 2.
The evaluation results of the obtained gas barrier laminate film are shown in Table 1.
〔比較例２〕
実施例２で用いたアクリル酸多価金属混合物の溶液に替えて、アクリル酸Ｚｎ（ａ′）溶液、アクリル酸Ｍｇ（ｂ′）溶液、及びアクリル酸Ｌｉ（ｃ′）溶液を用い、アクリル酸Ｚｎ（ａ′）が４１質量％、アクリル酸Ｍｇ（ｂ′）が９質量％、及びアクリル酸Ｌｉ（ｃ′）が５０質量％になるように混合して、アクリル酸多価金属塩混合物の溶液を用いる以外は実施例２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の評価結果を表１に示す
[Comparative Example 2]
Instead of the solution of the polyvalent metal acrylate mixture used in Example 2, a Zn (a ′) acrylate solution, a Mg (b ′) acrylate solution, and a Li (c ′) acrylate solution were used. Mixing so that Zn (a ′) is 41% by mass, Mg (b ′) acrylate is 9% by mass, and Li (c ′) acrylate is 50% by mass. A gas barrier laminate film was obtained in the same manner as in Example 2 except that the solution was used.
The evaluation results of the obtained gas barrier laminate film are shown in Table 1.
〔比較例３〕
実施例２で用いたアクリル酸多価金属混合物の溶液に替えて、アクリル酸Ｚｎ（ａ′）溶液、アクリル酸Ｍｇ（ｂ′）溶液、及びアクリル酸Ｌｉ（ｃ′）溶液を用い、アクリル酸Ｚｎ（ａ′）が３８質量％、アクリル酸Ｍｇ（ｂ′）が５０量％、及びアクリル酸Ｌｉ（ｃ′）が１２質量％になるように混合して、アクリル酸多価金属塩混合物の溶液を用いる以外は実施例２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の評価結果を表１に示す
[Comparative Example 3]
Instead of the solution of the polyvalent metal acrylate mixture used in Example 2, a Zn (a ′) acrylate solution, a Mg (b ′) acrylate solution, and a Li (c ′) acrylate solution were used. Mixing so that Zn (a ′) is 38% by mass, Mg (b ′) acrylate is 50% by mass, and Li (c ′) acrylate is 12% by mass, A gas barrier laminate film was obtained in the same manner as in Example 2 except that the solution was used.
The evaluation results of the obtained gas barrier laminate film are shown in Table 1.
〔比較例４〕
実施例２で用いたアクリル酸多価金属混合物の溶液に替えて、アクリル酸Ｚｎ（ａ′）溶液、及びアクリル酸Ｌｉ（ｃ′）溶液を用い、アクリル酸Ｚｎ（ａ′）が８８質量％、及びアクリル酸Ｌｉ（ｃ′）が１２質量％になるように混合して、アクリル酸多価金属塩混合物の溶液を用いる以外は実施例２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の評価結果を表１に示す
[Comparative Example 4]
Instead of the solution of the polyvalent metal acrylate mixture used in Example 2, a Zn (a ′) acrylate solution and a Li (c ′) acrylate solution were used, and the Zn (a ′) acrylate was 88% by mass. , And Li (c ′) acrylate was mixed so as to be 12% by mass, and a gas barrier laminate film was obtained in the same manner as in Example 2 except that a solution of a polyvalent metal salt of acrylate was used.
The evaluation results of the obtained gas barrier laminate film are shown in Table 1.
〔比較例５〕
実施例２で用いたアクリル酸多価金属混合物の溶液に替えて、アクリル酸Ｚｎ（ａ′）溶液、及びアクリル酸Ｌｉ（ｃ′）溶液を用い、アクリル酸Ｚｎ（ａ′）が８０質量％、及びアクリル酸Ｌｉ（ｃ′）が２０質量％になるように混合して、アクリル酸多価金属塩混合物の溶液を用いる以外は実施例２と同様に行い、ガスバリア性積層フィルムを得た。
[Comparative Example 5]
Instead of the solution of the polyvalent metal acrylate mixture used in Example 2, a Zn (a ′) acrylate solution and a Li (c ′) acrylate solution were used, and the Zn (a ′) acrylate was 80% by mass. A gas barrier laminate film was obtained in the same manner as in Example 2 except that the mixture was mixed so that Li (c ′) acrylate was 20% by mass and a solution of a polyvalent metal salt of acrylate was used.
〔比較例６〕
実施例２で用いたアクリル酸多価金属混合物の溶液に替えて、アクリル酸Ｚｎ（ａ′）溶液、及びアクリル酸Ｌｉ（ｃ′）溶液を用い、アクリル酸Ｚｎ（ａ′）が７２．７質量％、及びアクリル酸Ｌｉ（ｃ′）が２７．３質量％になるように混合して、アクリル酸多価金属塩混合物の溶液を用いる以外は実施例２と同様に行い、ガスバリア性積層フィルムを得た。
[Comparative Example 6]
In place of the solution of the polyvalent metal acrylate mixture used in Example 2, a Zn (a ′) acrylate solution and a Li (c ′) acrylate solution were used, and Zn (a ′) acrylate was 72.7. The gas barrier laminate film was prepared in the same manner as in Example 2 except that the mixture was mixed so that the mass% and the acrylic acid Li (c ′) were 27.3 mass% and the solution of the polyvalent metal salt of acrylic acid was used. Got.
〔比較例７〕
実施例２で用いたアクリル酸多価金属混合物の溶液に替えて、アクリル酸Ｚｎ（ａ′）溶液、及びアクリル酸Ｌｉ（ｃ′）溶液を用い、アクリル酸Ｚｎ（ａ）が５６．７質量％、及びアクリル酸Ｌｉ（ｃ′）が４２．３質量％になるように混合して、アクリル酸多価金属塩混合物の溶液を用いる以外は実施例２と同様に行い、ガスバリア性積層フィルムを得た。
[Comparative Example 7]
Instead of the solution of the polyvalent metal acrylate mixture used in Example 2, a Zn (a ′) acrylate solution and a Li (c ′) acrylate solution were used, and Zn (a) acrylate was 56.7 masses. %, And Li (c ′) acrylate is 42.3% by mass, and the same procedure is used as in Example 2 except that a solution of a polyvalent metal salt of acrylate is used. Obtained.
以上のように、本発明により得られたガスバリア性積層フィルムの水蒸気透過度は、高湿下においても初期に小さくかつ長時間経過してもその増加が抑制されていることが分かる。 As described above, it can be seen that the water vapor permeability of the gas barrier laminate film obtained according to the present invention is small in the initial stage even under high humidity and its increase is suppressed even after a long time.
本発明のアクリル酸多価金属塩混合物の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ガスバリア性積層体は、高湿度下及び低湿度下での水蒸気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を始め、医療用途、電子材料、工業用途等さまざまな製品の包装材料、あるいは電子材料、精密部品、医薬品等をはじめ、酸素ガスの透過及び湿気を嫌う材料の保護材としても好適に使用し得る。特に、太陽電池のバックシート、有機ＥＬの封止材など電気、電子材料へ利用することができる。
The gas barrier film made of the polymer of the polyvalent metal salt mixture of acrylic acid according to the present invention and the gas barrier laminate formed by forming such a gas barrier film are excellent in water vapor barrier properties under high humidity and low humidity. Therefore, taking advantage of these features, packaging materials, especially food packaging materials that require high gas barrier properties, as well as packaging materials for various products such as medical applications, electronic materials, industrial applications, electronic materials, precision parts, etc. In addition, it can be suitably used as a protective material for materials such as pharmaceuticals that dislike the permeation and moisture of oxygen gas. In particular, it can be used for electrical and electronic materials such as solar cell backsheets and organic EL sealing materials.
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