JP5088921B2 - Method for producing gas barrier film - Google Patents
Method for producing gas barrier film Download PDFInfo
- Publication number
- JP5088921B2 JP5088921B2 JP2006166721A JP2006166721A JP5088921B2 JP 5088921 B2 JP5088921 B2 JP 5088921B2 JP 2006166721 A JP2006166721 A JP 2006166721A JP 2006166721 A JP2006166721 A JP 2006166721A JP 5088921 B2 JP5088921 B2 JP 5088921B2
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- film
- gas barrier
- unsaturated carboxylic
- polyvalent metal
- 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.)
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- -1 carboxylic acid compound Chemical class 0.000 claims description 83
- 229910052751 metal Inorganic materials 0.000 claims description 57
- 239000002184 metal Substances 0.000 claims description 57
- 150000003839 salts Chemical class 0.000 claims description 51
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- 239000000243 solution Substances 0.000 claims description 24
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- 239000000126 substance Substances 0.000 claims description 13
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
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- 229940126062 Compound A Drugs 0.000 claims 1
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- 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
- 239000012528 membrane Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 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
- 235000021317 phosphate Nutrition 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment 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
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 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
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 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
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-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
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000008707 rearrangement Effects 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
- 239000012748 slip agent Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 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
- 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
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 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
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 230000002087 whitening effect Effects 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Wrappers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Description
本発明は、透明性を有し、酸素、水蒸気等のガスバリア性、特に高湿度下でのガスバリ
ア性に優れた包装材料に好適なガスバリア性膜の製造方法に関する。
The present invention relates to a method for producing a gas barrier film suitable for a packaging material having transparency and excellent gas barrier properties such as oxygen and water vapor, particularly gas barrier properties under 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る。
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。そして、これら
は酸素ガスバリア性は発現するものの防湿性については十分とはいえない状況である。
In recent years, as a barrier material against oxygen or water vapor, inorganic oxides such as silicon oxide and aluminum oxide have been formed on film substrates by vacuum deposition, sputtering, ion plating, chemical vapor deposition, etc. A transparent gas barrier film is attracting 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 be cracked by rubbing or stretching during post-processing printing or laminating or filling the contents, and the gas barrier property may be lowered.
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 reduced oxygen barrier property under high humidity, and the composition of polyvinyl alcohol and poly (meth) acrylic acid has sufficiently advanced esterification, In order to improve the gas barrier properties of the film, heating at a high temperature for a long time is required. These are oxygen gas barrier properties but are not sufficient in terms of moisture resistance.
そこで本発明は、透明性、ガスバリア性のみならず、防湿性にも優れた膜を提供するこ
とを目的とするものである。
Accordingly, an object of the present invention is to provide a film having not only transparency and gas barrier properties but also excellent moisture resistance.
本発明は、基材層に重合度が２０未満の不飽和カルボン酸化合物の多価金属塩溶液を塗
工した後、不飽和カルボン酸化合物の多価金属塩を重合することにより得られる膜を熱処
理することを特徴とするガスバリア性膜の製造方法に関する。
The present invention provides a film obtained by polymerizing a polyvalent metal salt of an unsaturated carboxylic acid compound after coating the base layer with a polyvalent metal salt solution of an unsaturated carboxylic acid compound having a degree of polymerization of less than 20. The present invention relates to a method for manufacturing a gas barrier film characterized by performing a heat treatment.
また、本発明は、基材層に重合度が２０未満の不飽和カルボン酸化合物と多価金属化合
物とを含む溶液を塗工し、不飽和カルボン酸化合物の多価金属塩を形成させた後、不飽和
カルボン酸化合物の多価金属塩を重合することにより得られる膜を熱処理することを特徴
とするガスバリア性膜の製造方法に関する。
In the present invention, the base layer is coated with a solution containing an unsaturated carboxylic acid compound having a polymerization degree of less than 20 and a polyvalent metal compound to form a polyvalent metal salt of the unsaturated carboxylic acid compound. The present invention also relates to a method for producing a gas barrier film characterized by heat-treating a film obtained by polymerizing a polyvalent metal salt of an unsaturated carboxylic acid compound.
重合度が２０未満の不飽和カルボン酸化合物多価金属塩を重合して得られた膜に熱処理
をすることにより、透明性に優れ、且つガスバリア性に優れたガスバリア性膜を製造する
ことができる。
By heat-treating a film obtained by polymerizing an unsaturated carboxylic acid compound polyvalent metal salt having a degree of polymerization of less than 20, a gas barrier film having excellent transparency and gas barrier properties can be produced. .
不飽和カルボン酸化合物
本発明に係わる不飽和カルボン酸化合物は、アクリル酸、メタクリル酸、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）は、後述の多価金属化合物との塩を重合して得られる膜は、高湿度
下でのガスバリア性が改良されない虞がある。
これら不飽和カルボン酸化合物の中でも単量体が多価金属化合物で完全に中和された塩
が形成し易く、当該塩を重合して得られる膜のガスバリア性に優れるので好ましい。
Unsaturated carboxylic acid compound The unsaturated carboxylic acid compound according to the present invention includes acrylic acid, methacrylic acid, maleic acid,
It is a carboxylic acid compound having an α, β-ethylenically unsaturated group such as itaconic acid, and a degree of polymerization is less than 20, preferably a monomer or a polymer having 10 or less. A polymer obtained by polymerizing a polymer (polymer compound) having a degree of polymerization exceeding 20 with a polyvalent metal compound described later may not have improved gas barrier properties under high humidity.
Among these unsaturated carboxylic acid compounds, a salt in which a monomer is completely neutralized with a polyvalent metal compound is easy to form, and a film obtained by polymerizing the salt is excellent in gas barrier properties, which is preferable.
多価金属化合物
本発明に係わる多価金属化合物は、具体的には、マグネシウム（Ｍｇ）、カルシウム（
Ｃａ）、バリウム（Ｂａ）、亜鉛（Ｚｎ）、銅（Ｃｕ）、コバルト（Ｃｏ）、ニッケル（
Ｎｉ）、アルミニウム（Ａｌ）、鉄（Ｆｅ）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。これらは、少なくとも１種が使用され、１種のみの使用であっ
ても、２種以上を併用してもよい。
Polyvalent metal compound Specifically, the polyvalent metal compound according to the present invention includes magnesium (Mg), calcium (
Ca), barium (Ba), zinc (Zn), copper (Cu), cobalt (Co), nickel (
Ni), aluminum (Al), bivalent or higher metals such as iron (Fe), oxides of these metals,
Examples thereof include hydroxides, halides, carbonates, phosphates, phosphites, hypophosphites, sulfates and sulfites. 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 is particularly excellent. At least 1 type is used for these, and even 1 type may be used or 2 or more types may be used together.
不飽和カルボン酸化合物の多価金属塩
本発明に係わる不飽和カルボン酸化合物の多価金属塩は、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ガスバリア性膜の耐熱水性
に優れるので好ましい。
Polyvalent metal salt of unsaturated carboxylic acid compound The polyvalent metal salt of the unsaturated carboxylic acid compound according to the present invention is a salt of an unsaturated carboxylic acid compound having a polymerization degree of less than 20 and the polyvalent metal compound. These unsaturated carboxylic acid compound polyvalent metal salts may be one kind or a mixture of two or more kinds. Among these unsaturated carboxylic acid compound polyvalent metal salts, the gas barrier film from which zinc (meth) acrylate is obtained is particularly excellent in hot water resistance, which is preferable.
基材層
本発明に係わる基材層は、前記不飽和カルボン酸化合物の多価金属塩の溶液を塗工でき
るものであれば、とくに限定はされず、熱硬化性樹脂、熱可塑性樹脂あるいは紙等の有機
質材料、ガラス、陶、セラミック、セメントあるいはアルミニウム、鉄、銅、ステンレス
等の金属等の無機質材料、有機質材料同士あるいは有機質材料と無機質材料との組合せか
らなる多層構造の基材層を例示することができる。
また、基材層の形状も、とくに限定はされず、シートまたはフィルム状物、トレー、カ
ップ、中空体等の形状を有するものを例示することができる。
これら基材層の材料として、熱硬化性樹脂、熱可塑性樹脂あるいは紙等の有機質材料を
用いる場合は、不飽和カルボン酸化合物の多価金属塩の重合体からなるガスバリア性膜を
備えた積層体として用いることができる。
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、フッ素樹脂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。これら熱可塑
性樹脂からなる基材層はガスバリア性膜の用途に応じて、単層であっても、二種以上の熱
可塑性樹脂からなる積層体であってもよい。
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し、ポリ塩化ビニリデン、ポリビニルアルコール、エ
チレン・ビニアルコール共重合体、アクリル樹脂、ウレタン系樹脂等がコーティングされ
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。
なお、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る等、その他の無機薄膜層を設ける場合、珪素、アルミニウム、チ
タン、ジルコニウム、錫、マグネシウム、インジウムなどの酸化物、窒化物、弗化物の単
体、或いはそれらの複合物等が用いられる。特に酸化アルミニウムは、無色透明であり、
ボイル・レトルト耐性等の特性にも優れており、広範囲の用途に用いることができる。
Base Material Layer The base material layer according to the present invention is not particularly limited as long as it can be applied with a solution of the polyvalent metal salt of the unsaturated carboxylic acid compound, and is not limited to thermosetting resin, thermoplastic resin or paper. Examples of organic materials such as glass, porcelain, ceramics, cement or inorganic materials such as metals such as aluminum, iron, copper, and stainless steel, and base materials with a multilayer structure composed of organic materials or combinations of organic materials and inorganic materials can do.
Further, the shape of the base material layer is not particularly limited, and examples thereof include a sheet or film-like material, a tray, a cup, and a hollow body.
When an organic material such as a thermosetting resin, a thermoplastic resin, or paper is used as a material for these base material layers, a laminate having a gas barrier film made of a polyvalent metal salt polymer of an unsaturated carboxylic acid compound Can be used as
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
Examples thereof include a vinyl acetate copolymer or a saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, fluororesin or a mixture thereof. Of these, thermoplastic resins having good stretchability and transparency, such as polypropylene, polyethylene terephthalate, and polyamide, are preferable. The base material layer made of these thermoplastic resins may be a single layer or a laminate made of two or more kinds of thermoplastic resins depending on the use of the gas barrier film.
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, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl alcohol copolymer, acrylic resin, A urethane-based resin or the like may be coated.
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.
In addition, when providing other inorganic thin film layers such as an inorganic compound such as aluminum, zinc or silica or oxides thereof deposited on the surface of the base material layer, silicon, aluminum, titanium, zirconium, tin, magnesium, An oxide such as indium, nitride, fluoride alone, or a composite thereof is used. In particular, aluminum oxide is colorless and transparent,
It has excellent characteristics such as boil and retort resistance and can be used in a wide range of applications.
無機薄膜層を形成する方法としては特に限定されず、公知の方法を利用することができ
る。例えば、スパッタやＣＶＤ法により成膜を行う方法がある。これらの無機薄膜層は、
透明樹脂層（Ｂ）上に形成することが望ましい。
また、表面平滑性に優れた形状の膜を得るためには、透明樹脂層（Ｂ）の表面と、透明
無機薄膜の形成における無機原子や化合物の結合反応が速やかに行われることが好ましい
。
これらの結合反応を迅速に行うには、その無機原子や化合物が化学的に活性な分子種も
しくは原子種であることが望ましい。
It does not specifically limit as a method to form an inorganic thin film layer, A well-known method can be utilized. For example, there is a method of forming a film by sputtering or CVD. These inorganic thin film layers are
It is desirable to form on a transparent resin layer (B).
In addition, in order to obtain a film having a shape excellent in surface smoothness, it is preferable that the bonding reaction between the surface of the transparent resin layer (B) and inorganic atoms or compounds in the formation of the transparent inorganic thin film is rapidly performed.
In order to perform these bonding reactions quickly, it is desirable that the inorganic atom or compound is a chemically active molecular species or atomic species.
よって成膜法としては化学的気相蒸着法（ＣＶＤ法）が望ましい。これにより、透明樹
脂層（Ｂ）の表面と、窒化珪素や酸化窒化珪素などの珪素を含有する化学的に活性な分子
種が速やかに反応することにより、無機薄膜層の表面の平滑性が改良され、孔を少なくす
ることができるものと予想される。
Therefore, the chemical vapor deposition method (CVD method) is desirable as the film forming method. As a result, the surface of the transparent resin layer (B) and the chemically active molecular species containing silicon such as silicon nitride and silicon oxynitride react quickly, thereby improving the smoothness of the surface of the inorganic thin film layer. It is expected that the number of holes can be reduced.
膜の製造方法
本発明においては、予め基材層に成形された膜を熱処理してガスバリア性膜が製造され
る。熱処理に供される膜は、基材層に重合度が２０未満の不飽和カルボン酸化合物の多価
金属塩溶液を塗工した後、不飽和カルボン酸化合物の多価金属塩を重合することにより得
られる。
また、熱処理に供される膜は、基材層に重合度が２０未満の不飽和カルボン酸化合物と
多価金属化合物とを含む溶液を塗工し、不飽和カルボン酸化合物の多価金属塩を形成させ
た後、不飽和カルボン酸化合物の多価金属塩を重合することによっても得られる。
不飽和カルボン酸化合物多価金属塩の溶液を調整する方法としては、予め前記不飽和カ
ルボン酸と前記多価金属化合物とを反応させて、不飽和カルボン酸化合物の多価金属塩と
した後、当該不飽和カルボン酸化合物多価金属塩を水等の溶媒に溶かして溶液としてもよ
いし、直接溶媒に前記不飽和カルボン酸化合物と前記多価金属化合物を溶かして多価金属
塩の溶液としてもよい。
本発明のガスバリア性膜の製造方法として、直接溶媒に前記不飽和カルボン酸化合物と
前記多価金属化合物を溶かす場合、即ち、前記不飽和カルボン酸化合物と前記多価金属化
合物とを含む溶液を用いる場合は、前記不飽和カルボン酸化合物に対して、０．３化学当
量を越える量の前記多価金属化合物を添加することが好ましい。多価金属化合物の添加量
が０．３化学当量以下の混合溶液を用いた場合は、遊離のカルボン酸基の含有量が多いガ
スバリア性膜となり、結果として、ガスバリア性が低い膜となる虞がある。また、多価金
属化合物の添加量の上限はとくに限定はされないが、多価金属化合物の添加量が１化学当
量を越えると未反応の多価金属化合物が多くなるので、通常、５化学当量以下、好ましく
は２化学当量以下で十分である。
また、不飽和カルボン酸化合物と多価金属化合物との混合溶液を用いる場合は、通常、
不飽和カルボン酸化合物と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
酸化合物の多価金属塩が形成されるが、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。
不飽和カルボン酸化合物の多価金属塩の溶液を調整するために用いる溶媒は、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。
基材層に不飽和カルボン酸化合物の多価金属塩の溶液を塗工する方法としては、当該溶
液を基材層表面に塗布する方法、当該溶液に基材層を浸漬する方法、当該溶液を基材層表
面に噴霧する方法等種々公知の塗工方法を採り得る。
基材層に不飽和カルボン酸化合物の多価金属塩の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。
In the present invention, a gas barrier film is produced by heat-treating a film previously formed on the base material layer. The film to be subjected to the heat treatment is obtained by coating the base layer with a polyvalent metal salt solution of an unsaturated carboxylic acid compound having a degree of polymerization of less than 20, and then polymerizing the polyvalent metal salt of the unsaturated carboxylic acid compound. can get.
In addition, the film to be subjected to the heat treatment is prepared by applying a solution containing an unsaturated carboxylic acid compound having a polymerization degree of less than 20 and a polyvalent metal compound to the base material layer, and applying a polyvalent metal salt of the unsaturated carboxylic acid compound. After forming, it can also be obtained by polymerizing a polyvalent metal salt of an unsaturated carboxylic acid compound.
As a method for preparing a solution of an unsaturated carboxylic acid compound polyvalent metal salt, after previously reacting the unsaturated carboxylic acid and the polyvalent metal compound to obtain a polyvalent metal salt of an unsaturated carboxylic acid compound, The unsaturated carboxylic acid compound polyvalent metal salt may be dissolved in a solvent such as water to form a solution, or the unsaturated carboxylic acid compound and the polyvalent metal compound may be directly dissolved in a solvent to form a polyvalent metal salt solution. Good.
As a method for producing a gas barrier film of the present invention, when the unsaturated carboxylic acid compound and the polyvalent metal compound are directly dissolved in a solvent, that is, a solution containing the unsaturated carboxylic acid compound and the polyvalent metal compound is used. In this case, it is preferable to add the polyvalent metal compound in an amount exceeding 0.3 chemical equivalents relative to the unsaturated carboxylic acid compound. When a mixed solution having a polyvalent metal compound addition amount of 0.3 chemical equivalent or less is used, a gas barrier film having a large content of free carboxylic acid groups may be formed, resulting in a film having a low gas barrier property. is there. The upper limit of the amount of polyvalent metal compound is not particularly limited, but when the amount of polyvalent metal compound exceeds 1 chemical equivalent, the amount of unreacted polyvalent metal compound increases. Preferably, 2 chemical equivalents or less are sufficient.
When using a mixed solution of an unsaturated carboxylic acid compound and a polyvalent metal compound,
While the unsaturated carboxylic acid compound and the polyvalent metal compound are dissolved in the solvent, the polyvalent metal salt of the unsaturated carboxylic acid compound is formed. In order to ensure the formation of the polyvalent metal salt, 1 It is preferable to mix for at least minutes.
Examples of the solvent used for preparing the solution of the polyvalent metal salt of the unsaturated carboxylic acid compound include water, lower alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, organic solvents such as acetone and methyl ethyl ketone, or a mixed solvent thereof. But
Water is most preferred.
As a method of applying a solution of an unsaturated carboxylic acid compound polyvalent metal salt to the base material layer, a method of applying the solution to the surface of the base material layer, a method of immersing the base material layer in the solution, Various known coating methods such as a method of spraying on the surface of the base material layer can be adopted.
Examples of a method for applying a polyvalent metal salt solution of an unsaturated carboxylic acid compound to the base material layer include gravure coaters such as an air knife coater, direct gravure coater, gravure offset, arc gravure coater, gravure reverse and jet nozzle method. , Reverse roll coaters such as top feed reverse coater, bottom feed reverse coater and nozzle feed reverse coater, 5-roll coater, lip coater,
Using various known coating machines such as a bar coater, a bar reverse coater and a die coater, 0.05 to 10 g / m 2 , preferably in an amount of the unsaturated carboxylic acid compound polyvalent metal salt (solid content), preferably What is necessary is just to apply | coat so that it may become 0.1-5 g / m < 2 >.
不飽和カルボン酸化合物の多価金属塩を溶解する際若しくは不飽和カルボン酸化合物と
多価金属化合物とを溶解する際には、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、エチレングリコール・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、トリエチレングリコール・ジ（メタ
）アクリレート、ＰＥＧ＃２００・ジ（メタ）アクリレート、ＰＥＧ＃４００・ジ（メタ
）アクリレート、ＰＥＧ＃６００・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、１，４−ブタンジオール・ジ（メタ）アクリレートなどのグリ
コール類のアクリル酸二価エステル、その他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多価金属塩を溶解する際若しくは不飽和カルボン酸化合
物と多価金属化合物とを溶解する際には、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 dissolving the polyvalent metal salt of the unsaturated carboxylic acid compound or when dissolving the unsaturated carboxylic acid compound and the polyvalent metal compound, methyl (meth) acrylate, as long as the object of the present invention is not impaired, Ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, PEG # 200 • di (meth) acrylate, PEG # 400 • di ( (Meth) acrylate, PEG # 600 / di (meth) acrylate, neopentyl glycol /
Di (meth) acrylate, 1,4-butanediol di (meth) acrylate and other glycol diacrylates, other unsaturated carboxylic acid (di) ester compounds,
Monomers such as vinyl ester compounds such as vinyl acetate or low molecular weight compounds, polyvinyl alcohol, ethylene / vinyl alcohol copolymers, polyvinyl pyrrolidone, polyvinyl ethyl ether, polyacrylamide, polyethylene imine, starch, gum arabic, methyl cellulose, etc. Water-soluble polymers, acrylic acid ester polymers, ethylene / acrylic acid copolymers, polyvinyl acetate, ethylene / vinyl acetate copolymers, polyesters, polyurethanes and other high molecular weight compounds may be added.
Further, when the unsaturated carboxylic acid compound polyvalent metal salt is dissolved, or when the unsaturated carboxylic acid compound and the polyvalent metal compound are dissolved, the lubricant, slip agent, -Various additives such as blocking agents, antistatic agents, antifogging agents, pigments, dyes, inorganic or organic fillers may be added, and in order to improve the wettability with the base material layer, Various surfactants and the like may be added.
不飽和カルボン酸化合物多価金属塩の溶液を重合するには、種々の公知の方法、具体的
には電離性放射線の照射または加熱などによる方法があげられる。
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０．０
１〜０．００２ｎｍ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多価
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。
In order to polymerize the solution of the unsaturated carboxylic acid compound polyvalent metal salt, there are various known methods, specifically, methods such as irradiation with ionizing radiation or heating.
When ionizing radiation is used, there is no particular limitation 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
Line, visible light, ultraviolet light, electron beam, etc. 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 0.0
An electron beam in the range of 1 to 0.002 nm is preferable because it is easy to handle and devices are widespread.
When using visible light and ultraviolet rays as ionizing radiation, it is necessary to add a photopolymerization initiator to a mixed solution of unsaturated carboxylic acid compound polyvalent metal salt and 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, manufactured by Ciba Specialty Chemicals;
DAROCURE 1173), 1-hydroxy-cyclohexyl phenyl ketone (Ciba
Specialty Chemicals product name; Irgacure 184), screw (2, 4,
6-trimethylbenzoyl) -phenylphosphine oxide (trade name; Irgacure 819 manufactured by Ciba Specialty Chemicals), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1 -Propan-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals), α-hydroxyketone, acylphosphine oxide, 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (Lamberti Product name; Esacure KT046), Esacure KT55 (Lamberti Chemical
Specialty), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name; manufactured by Ramson Fire Chemical Co., Ltd .; trade name of Speedcure TPO) includes a radical polymerization initiator manufactured and sold. 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多価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。
また、塗工液の乾燥は溶媒を完全に除去するのではなく、塗工液中に適度の溶媒（水溶液を用いる場合は水分）、好ましくは２０〜６０重量％の範囲で溶媒を含む状態で電子線を照射することが好ましい。塗工液に含まれる溶媒が２０重量％未満の場合は得られる膜の酸素バリア性が低下する虞があり、塗工液に含まれる溶媒が６０重量％以上の場合は得られる膜の酸素バリア性や外観、特に透明性が低下する虞がある。
また、不飽和カルボン酸化合物多価金属塩を溶媒の存在下で電離放射線を照射する際の温度は、溶媒が沸騰する温度でない限りとくに限定はされないが、通常、６０℃以下、とくに常温〜５０℃の範囲で行うことが好ましい。電離放射線を照射する際の温度を高くし過ぎると、溶媒の蒸発が速くなり、不飽和カルボン酸化合物多価金属塩の結晶が析出し易くなり、一方、温度が低すぎる場合は、不飽和カルボン酸化合物多価金属塩を重合させた後に溶媒を乾燥する時間が長くなり、膜の製造ライン等を長くする必要がある。
When polymerizing the unsaturated carboxylic acid compound polyvalent metal salt, the solution may be polymerized in a state of containing a solvent such as water, or may be polymerized after partially drying, but after applying the solution When the polymerization is performed immediately, 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, as the solvent (moisture) decreases, the unsaturated carboxylic acid compound polyvalent metal salt may precipitate as crystals, and when the polymerization is carried out in such a state, the formation of the copolymer layer obtained becomes insufficient, There is a possibility that the gas barrier property may not be stabilized due to whitening of the copolymer 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 addition, the drying of the coating liquid does not completely remove the solvent, but an appropriate solvent (water if an aqueous solution is used) in the coating liquid, preferably in a state containing the solvent in the range of 20 to 60% by weight. It is preferable to irradiate an electron beam. When the solvent contained in the coating liquid is less than 20% by weight, the oxygen barrier property of the resulting film may be reduced. When the solvent contained in the coating liquid is 60% by weight or more, the obtained film has an oxygen barrier. There is a risk that the property and appearance, particularly transparency, may be reduced.
The temperature at the time of irradiating ionizing radiation unsaturated carboxylic acid compound polyvalent metal salt in the presence of a solvent is not particularly limited is as long as the solvent is not the temperature at which boiling is usually, 60 ° C. or less, in particular room temperature to 50 It is preferable to carry out in the range of ° C. If the temperature at the time of irradiation with ionizing radiation is too high, the solvent evaporates faster and crystals of the unsaturated carboxylic acid compound polyvalent metal salt tend to precipitate, whereas if the temperature is too low, the unsaturated carboxylic acid The time for drying the solvent after polymerizing the acid compound polyvalent metal salt becomes longer, and it is necessary to lengthen the film production line and the like.
ガスバリア性膜
上記の重合によって得られた膜を熱処理することによって本発明のガスバリア性膜が得られる。
熱処理は、膜を通常６０〜３５０℃、好ましくは１００〜３００℃、さらに好ましくは１５０〜２５０℃の温度範囲で行うことが望ましく、不活性ガス雰囲気下とすることが望ましい。また、圧力は特に限定されず、加圧下、減圧下、常圧下のいずれでもよい。加熱処理時間は、通常３０秒から９０分程度であり、中でも１分から７０分が好適であり、特に５分から６０分が好適である。
熱処理に供される膜は、通常基材層に塗布されたまま熱処理されるが、必要に応じて基材層から剥離して熱処理してもよい。
本発明においては、重合された膜を引き続き連続的に熱処理してもよく、また膜を一旦常温にもどした後に、熱処理に供してもよい。通常は重合により膜を形成する工程と熱処理の工程を連続させることが製造効率上望ましい。
熱処理に供される膜は、重合により膜の構造が確定しているものと推定される。これを更に熱処理することにより、脱水および膜構造が部分的な再配置によってより安定化された膜となり、ガスバリア性がより安定するものと推定される。
本発明の製造方法で得られるガスバリア性膜は、通常、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、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の多価金属塩の重合体からなる。
不飽和カルボン酸化合物の多価金属塩の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が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。
Gas barrier film The gas barrier film of the present invention can be obtained by heat-treating the film obtained by the above polymerization.
The heat treatment is usually performed in a temperature range of 60 to 350 ° C. , preferably 100 to 300 ° C. , more preferably 150 to 250 ° C. , and preferably in an inert gas atmosphere. The pressure is not particularly limited, and may be any of under pressure, under reduced pressure, and normal pressure. The heat treatment time is usually about 30 seconds to 90 minutes, with 1 minute to 70 minutes being preferred, and 5 minutes to 60 minutes being particularly preferred.
The film to be subjected to the heat treatment is usually heat-treated while being applied to the base material layer, but may be peeled off from the base material layer and heat-treated if necessary.
In the present invention, the polymerized film may be continuously heat-treated, or may be subjected to heat treatment after the film is once returned to room temperature. Usually, it is desirable in terms of production efficiency that the process of forming a film by polymerization and the process of heat treatment are continued.
It is presumed that the film subjected to the heat treatment has a film structure determined by polymerization. By further heat-treating this, it is presumed that the dehydration and the film structure become a more stabilized film by partial rearrangement, and the gas barrier property is more stable.
The gas barrier film obtained by the production method of the present invention usually has an absorbance A 0 based on νC═O of a carboxylic acid group near 1700 cm −1 in an infrared absorption spectrum and νC═O of a carboxylate ion near 1520 cm −1. It consists of a polymer of a polyvalent metal salt of an unsaturated carboxylic acid compound in which the ratio (A 0 / A) to the absorbance A based is less than 0.25, preferably less than 0.20.
A gas barrier film made of a polymer of a polyvalent metal salt of an unsaturated carboxylic acid compound has a carboxylate ion formed by ionic crosslinking of a carboxylic acid group and a polyvalent metal, and a free carboxylic acid group. Thus, 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 around 1520 cm −1 .
したがって、本発明の製造方法で得られるガスバリア性膜において、（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を越える膜は、遊離のカルボン酸基の含有量が多く、耐ガスバリア性が
改良されない虞がある。
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、ガスバリア性膜（ガスバリア性積層体）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多価金
属塩重合体層）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 Ｂｒｏｍｉｄ
ｅ−Ｉｏｄｉｄｅ）結晶を装着して、入射角４５度、室温、分解能４ｃｍ-1、積算回数１
５０回の条件で行った。
Therefore, in the gas barrier film obtained by the production method of the present invention, (A 0 / A) is 0.
. A value of less than 25 indicates that there are no or few free carboxylic acid groups, and a film exceeding 0.25 has a high content of free carboxylic acid groups, and the gas barrier resistance is not improved. There is a fear.
Absorbance A 0 based on νC═O of a carboxylic acid group near 1700 cm −1 in the present invention and νC of a carboxylate ion near 1520 cm −1 in an infrared absorption spectrum in the present invention.
The ratio of the absorbance A based on O (A 0 / A) was determined by cutting out a measurement sample of 1 cm × 3 cm from a gas barrier film (gas barrier laminate), and its surface (unsaturated carboxylic acid compound polyvalent metal salt polymer). obtain an infrared absorption spectrum of the layer) to the infrared total reflection (ATR method), the following procedure was first determined absorbance a 0 and absorbance a.
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
The straight line (O) is lowered vertically from the maximum absorbance between ˜1760 cm −1 (near 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 is calculated. and the absorbance a 0.
1520 cm -1 vicinity of carboxylate ion of νC = O based upon the absorbance A: bear and the absorbance of the infrared absorption spectrum of 1480 cm -1 and 1630 cm -1 in a straight line (L),
From a maximum absorbance between 1480 and 1630 cm −1 (near 1520 cm −1 ), a straight line (
M) was lowered, 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 this invention uses FT-IR350 apparatus by JASCO Corporation, and KRS-5 (Thallium Bromid).
e-Iodide) crystal attached, incident angle 45 degrees, room temperature, resolution 4 cm -1 , number of integration 1
The test was performed 50 times.
本発明の製造方法により得られるガスバリア性膜は、基材層から剥離してガスバリア性
膜単層としても用い得るが、通常は、基材層にガスバリア性膜を積層した積層体として用
いる。かかるガスバリア性積層体は、基材層の形状により、また用途に応じ、積層フィル
ム、積層シート、トレー、カップ、中空体（ボトル）等の種々の形状を取り得る。
The gas barrier film obtained by the production method of the present invention can be peeled from the base material layer and used as a gas barrier film single layer, but is usually used as a laminate in which the gas barrier film is laminated on the base material layer. Such a gas barrier laminate can take various shapes such as a laminate film, a laminate sheet, a tray, a cup, and a hollow body (bottle) depending on the shape of the base material layer and the use.
本発明の製造方法により得られる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。
If the laminated body is a laminated film, the gas barrier laminate obtained by the production method of the present invention is a laminated film suitable as a packaging film that can be heat-sealed by laminating a heat fusion layer on at least one side thereof. Is obtained. 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 Propylene 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 the like It is a layer obtained from a metal salt, a composition of EVA and polyolefin 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.
次に実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を越えない限り
これらの実施例に制約されるものではない。
EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist.
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。 The physical property values and the like in Examples and Comparative Examples were obtained by the following evaluation methods.
＜評価方法＞
（１） 水蒸気透過度［ｇ／（ｍ２・ｄａｙ）］：
多層フィルムを折り返し、２方をヒートシールして（線状低密度ポリエチレンフィルム面）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、これを４０℃、９０％Ｒ．Ｈ．の条件で３日間放置し、その重量差で水蒸気透過度を測定した。
尚、実施例８から２５および参考例１から１０においては、３日後と１０日後の重量差で水蒸気透過度を測定した。
<Evaluation method>
(1) Water vapor permeability [g / (m 2 · day)]:
Fold the multilayer film and heat-seal the two sides (linear low-density polyethylene film surface) to form a bag, then add calcium chloride as the contents, and heat-seal the other to a surface area of 0.01 m 2 A bag was prepared so as to be 40 ° C. , 90% R.D. H. The water vapor permeability was measured by the difference in weight.
In Examples 8 to 25 and Reference Examples 1 to 10, the water vapor permeability was measured by the difference in weight after 3 days and after 10 days.
＜溶液（Ｘ）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％）〕と、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）をモル分率でそれぞれ９８．５％、１．２％、０．３％となるように混合し、
アクリル酸Ｚｎ塩溶液（Ｘ）からなる不飽和カルボン酸化合物多価金属塩溶液を作製した
。
<Preparation of solution (X)>
Zinc acrylate (Zn salt of acrylic acid) aqueous solution (manufactured by Asada Chemical Co., Ltd., concentration 30 wt% (acrylic acid component: 20 wt%, Zn component 10 wt%)) and photopolymerization 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 mixed so that the molar fraction was 98.5%, 1.2%, and 0.3%,
An unsaturated carboxylic acid compound polyvalent metal salt solution composed of the Zn acrylate solution (X) was prepared.
実施例１
上記アクリル酸Ｚｎ塩溶液（Ｘ）を厚さ１２μｍの二軸延伸ポリエステルフィルム（ユニチカ社製 商品名；エンブレットＰＥＴ１２）からなる基材フィルムのコロナ処理面に、メイヤーバーで塗布量が固形分で３．５ｇ／ｍ２になるように塗布し、塗工面を上にしてステンレス板に固定し、直ちに紫外線照射装置（アイグラフィック社製
ＥＹＥ ＧＲＡＮＤＡＧＥ 型式ＥＣＳ
３０１Ｇ１）を用いて、照度：１８０ｍＷ/ｃｍ2、積算光量：１８０ｍＪ/ｃｍ２の条件で紫外線を照射して重合し、ガスバリア性膜を積層した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オーブン中で２００℃、６０分間熱処理した。
次に、厚さ５０μｍの線状低密度ポリエチレンフィルム（東セロ社製 商品名：Ｔ．Ｕ．Ｘ． ＦＣＳ）の片面に、ウレタン系接着剤（ポリウレタン系接着剤（三井武田ケミカル社製 商品名：タケラックＡ３１０）：１２重量部、イソシアネート系硬化剤（三井武田ケミカル社製
商品名：タケネートＡ３）：１重量部及び酢酸エチル（関東化学社製）：７重量部）を塗布・乾燥後、得られたガスバリア性積層フィルムのアクリル酸多価金属塩重合体層（不飽和カルボン酸化合物多価金属塩重合体層）面を貼り合わせ（ドライラミネート）し、多層フィルムを得た。
得られたガスバリア性積層フィルムの防湿性を表１に示す。
Example 1
The coating amount of the acrylic acid Zn salt solution (X) is a solid content on a corona-treated surface of a base film made of a biaxially stretched polyester film having a thickness of 12 μm (trade name; Emblet PET12, manufactured by Unitika). Apply to 3.5 g / m 2 and fix to stainless steel plate with the coated surface facing up. Immediately UV irradiation device (EYE GRANDAGE model ECS manufactured by Eye Graphic)
301G1) was used to polymerize by irradiating with ultraviolet rays under the conditions of illuminance: 180 mW / cm 2 and integrated light quantity: 180 mJ / cm 2 to obtain a gas barrier laminated film in which a gas barrier film was laminated. The obtained gas barrier laminate film was heat-treated at 200 ° C. for 60 minutes in an oven.
Next, a urethane adhesive (polyurethane adhesive (manufactured by Takeshi Mitsui Chemicals, Inc.) is applied to one side of a 50 μm-thick linear low density polyethylene film (trade name: TUX FCS manufactured by Tosero). Takelac A310): 12 parts by weight, isocyanate-based curing agent (trade name: Takenate A3 manufactured by Mitsui Takeda Chemical Co., Ltd .: 1 part by weight and ethyl acetate (manufactured by Kanto Chemical Co., Ltd.): 7 parts by weight) are obtained after coating and drying. The multi-layer film was obtained by laminating (dry-laminating) the acrylic polyvalent metal salt polymer layer (unsaturated carboxylic acid compound polyvalent metal salt polymer layer) surface of the gas barrier laminate film.
Table 1 shows the moisture resistance of the obtained gas barrier laminate film.
実施例２
熱処理条件を１５０℃、６０分間とした以外は、実施例１と同様にして、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防湿性を表１に示す。
Example 2
A gas barrier laminate film was obtained in the same manner as in Example 1 except that the heat treatment conditions were 150 ° C. and 60 minutes.
Table 1 shows the moisture resistance of the obtained gas barrier laminate film.
実施例３
熱処理条件を１００℃、６０分間とした以外は、実施例１と同様にして、多層フィルムを得た。
得られた多層フィルムの防湿性を表１に示す。
Example 3
A multilayer film was obtained in the same manner as in Example 1 except that the heat treatment conditions were 100 ° C. and 60 minutes.
The moisture resistance of the obtained multilayer film is shown in Table 1.
実施例４
熱処理条件を１５０℃、３０分間とした以外は、実施例１と同様にして、多層フィルムを得た。
得られた多層フィルムの防湿性を表１に示す。
Example 4
A multilayer film was obtained in the same manner as in Example 1 except that the heat treatment conditions were 150 ° C. and 30 minutes.
The moisture resistance of the obtained multilayer film is shown in Table 1.
実施例５
紫外線照射装置に（フージョン社製 型式：ＣＶ−１１０Ｑ−Ｇ、種類
Ｆ６００Ｖ−１０）を用いて、照度：１７６０ｍＷ／ｃｍ ２ 及び光量：５６０ｍＪ／ｃｍ ２ の紫外線を照射して重合し、ガスバリア性膜を積層したガスバリア性積層フィルムを得た以外は、実施例１と同様にして、多層フィルムを得た。
得られたガスバリア性積層フィルムの防湿性を表１に示す。
Example 5
Using a UV irradiation device (model: CV-110Q-G, type F600V-10, manufactured by Fusion Co., Ltd.), polymerizing by irradiating with ultraviolet rays of illuminance: 1760 mW / cm 2 and light amount: 560 mJ / cm 2 , gas barrier film A multilayer film was obtained in the same manner as in Example 1 except that a gas barrier laminate film obtained by laminating was obtained.
Table 1 shows the moisture resistance of the obtained gas barrier laminate film.
実施例６
熱処理条件を１５０℃、６０分間とした以外は、実施例５と同様にして、多層フィルムを得た。
得られたガスバリア性積層フィルムの防湿性を表１に示す。
Example 6
A multilayer film was obtained in the same manner as in Example 5 except that the heat treatment conditions were 150 ° C. and 60 minutes.
Table 1 shows the moisture resistance of the obtained gas barrier laminate film.
実施例７
熱処理条件を１００℃、６０分間とした以外は、実施例5と同様にして、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防湿性を表１に示す。
Example 7
A gas barrier laminate film was obtained in the same manner as in Example 5 except that the heat treatment conditions were 100 ° C. and 60 minutes.
Table 1 shows the moisture resistance of the obtained gas barrier laminate film.
Ｓ ３０１Ｇ１）を用いて、紫外線を照射して重合した。
＊注２ 紫外線照射装置に（フージョン社製 型式：ＣＶ−１１０Ｑ−Ｇ、種類 Ｆ６０
０Ｖ−１０）を用いて、紫外線を照射して重合した。
S 301G1) was used for polymerization by irradiation with ultraviolet rays.
* Note 2 To UV irradiation equipment (Fusion model: CV-110Q-G, type F60
0V-10) was used for polymerization by irradiation with ultraviolet rays.
表１から分かるように、基材層に塗工した不飽和カルボン酸化合物の多価金属塩溶液を
重合して得られる膜を熱処理したガスバリア性積層フィルム（実施例１〜７）は、酸素バ
リア性に優れていることが分かる。
実施例 ８〜２５および参考例１〜５
〈基材の調製〉
基材１ 厚さ１２μｍの二軸延伸ポリエチレンテレフタレートからなる基材のコロナ処理面に蒸着装置により、酸化ケイ素を蒸着し、反応ガスとして酸素を導入し、２０ナノメートルの薄膜を積層（ＳｉＯ膜）した基材
基材２ 厚さ１２μｍの二軸延伸ポリエチレンテレフタレートからなる基材のコロナ処理面に蒸着装置により、アルミを蒸着し、反応ガスとして酸素を導入し、１０ナノメートルの薄膜を積層（ＡｌＯ膜）した基材
基材３ 厚さ５０μｍの二軸延伸ポリエチレンテレフタレート（ユニチカ社製 商品名
；エンブレットＳ−５０）からなる基材のコロナ処理面にＲＦマグネトロンスパッタリング装置により、Ｓｉターゲットを使用し、反応ガスとして窒素を導入し、３０ナノメートルの薄膜を積層（ＳｉＮ膜）した基材
基材４ 基材３の調製において、導入する窒素ガスを酸素ガスとして、ＳｉＯ膜とする以外は同様にして調製した。
基材５ 厚さ５０μｍの二軸延伸ポリエチレンテレフタレート（ユニチカ社製 商品名
；エンブレットＳ−５０）からなる基材のコロナ処理面にＤＣマグネトロンスパッタリング装置により、ＩＴＯターゲットを使用し、反応ガスとして酸素を導入し、３０ナノメートルの薄膜を積層（ＩＴＯ膜）した基材
基材６ 厚さ５０μｍの二軸延伸ポリエチレンテレフタレート（ユニチカ社製 商品名
；エンブレットＳ−５０）からなる基材のコロナ処理面に、エポキシアクリレート系ＵＶ
硬化塗材（日本化工塗料社製 商品名；ＦＡ−１８）を酢酸エチルで希釈し、メイヤーバ
ーを用いて１．２ｇ／ｍ２（固形分）になるようにコートし、１００℃、１５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 ＧＲＡＮＤＡＧ
Ｅ 型式ＥＣＳ ３０１Ｇ１）を用いて、ＵＶ強度：２５０ｍＷ／ｃｍ２、積算光量：１
１７ｍＪ／ｃｍ２の条件で紫外線を照射してコート膜の重合を行いコートフィルムを得た
。
さらに、コートフィルムのコート面に、ＤＣマグネトロンスパッタリング装置により、
ＩＴＯターゲットを使用し、反応ガスとして酸素を導入し、３０ナノメートルの薄膜を積
層（ＩＴＯ膜）した基材
基材７ ポリエチレンナフタレートのフィルム（厚さ１００ミクロン、帝人社製 Ｑ６
５）からなる基材の平滑面に、ＤＣマグネトロンスパッタリング装置により、ＩＴＯターゲットを使用し、反応ガスとして酸素を導入し、３０ナノメートルの薄膜を積層（ＩＴＯ膜）した基材
基材８ ポリエチレンナフタレートのフィルム（厚さ１００ミクロン、帝人社製 Ｑ６
５）からなる平滑面に、ＲＦマグネトロンスパッタリング装置により、Ｓｉターゲットを使用し、反応ガスとして窒素を導入し、３０ナノメートルの薄膜を積層（ＳｉＮ膜）した基材
基材９ ポリエチレンナフタレートのフィルム（厚さ１００ミクロン、帝人社製 Ｑ６
５）からなる平滑面に、ＣａｔＣＶＤ法により厚さ５０ｎｍのＳｉＮ膜を形成させた基材。
〈塗工液の作製〉
溶液（イ）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％）と、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）をモル分率でそれぞれ９８．５％、１．２％、０．３％となるように混合し、ア
クリル酸Ｚｎ塩溶液を作製した。
溶液（ロ）の作製
溶液（イ）に、シリル変性ＰＶＡ（クラレ社製 商品名：Ｒ１１３０）の１０％水溶液
を、アクリル酸亜鉛とシリル変性ＰＶＡの固形分比率が８７．５％、１２．５％になるよ
うに混合し、溶液（ロ）を作製した。
〈実施例８のガスバリア性積層フィルムの調製〉
上記の基材の無機膜形成面に、溶液（イ）をメイヤーバーで塗布量が固形分で２．５ｇ
／ｍ２になるように塗布し、塗工面を上にしてステンレス板に固定し、直ちに紫外線照射
装置（アイグラフィック社製 ＥＹＥ ＧＲＡＮＤＡＧＥ 型式ＥＣＳ ３０１Ｇ１）を
用いて、照度：１８０ｍＷ/ｃｍ2、積算光量：１８０ｍＪ/ｃｍ２の条件で紫外線を照射
して重合し、ガスバリア性膜を積層した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オーブン中で２００℃、６０分間熱処理した。
次に、厚さ５０μｍの線状低密度ポリエチレンフィルム（東セロ社製 商品名：Ｔ．Ｕ
．Ｘ． ＦＣＳ）の片面に、ウレタン系接着剤（ポリウレタン系接着剤（三井武田ケミカ
ル社製 商品名：タケラックＡ３１０）：１２重量部、イソシアネート系硬化剤（三井武
田ケミカル社製 商品名：タケネートＡ３）：１重量部及び酢酸エチル（関東化学社製）
：７重量部）を塗布・乾燥後、得られたガスバリア性積層フィルムのアクリル酸多価金属
塩重合体層（不飽和カルボン酸化合物多価金属塩重合体層）面を貼り合わせ（ドライラミ
ネート）、多層フィルムを得た。
得られたガスバリア性積層フィルムの防湿性を表２に示す。
〈実施例 ９ないし２５、参考例１ないし５のガスバリア性積層フィルムの調製〉
実施例８において、基材、塗工液、塗布量、熱処理の条件を表２に示す条件とする以外
は同様に基材を調製した。
評価結果を表２に示す。なお、表２中の表示は以下による。
Examples 8-25 and Reference Examples 1-5
<Preparation of substrate>
Base material 1 Silicon oxide is deposited on the corona-treated surface of a base material made of biaxially stretched polyethylene terephthalate with a thickness of 12 μm by a vapor deposition device, oxygen is introduced as a reaction gas, and a 20 nanometer thin film is laminated (SiO film) Base material
Base material 2 Aluminum was deposited on a corona-treated surface of a base material made of biaxially stretched polyethylene terephthalate having a thickness of 12 μm by a vapor deposition apparatus, oxygen was introduced as a reaction gas, and a 10 nanometer thin film was laminated (AlO film). Base material
Substrate 3 50 μm thick biaxially stretched polyethylene terephthalate (trade name; manufactured by Unitika Ltd .; Emblet S-50), a corona-treated surface of the substrate using an RF magnetron sputtering apparatus, an Si target, and nitrogen as a reaction gas , And a substrate with a 30 nanometer thin film (SiN film)
Base material 4 The base material 3 was prepared in the same manner as the base material 3, except that the nitrogen gas to be introduced was oxygen gas and the SiO film was used.
Substrate 5 A 50 m-thick biaxially stretched polyethylene terephthalate (trade name; manufactured by Unitika Ltd .; Emblet S-50) is a corona-treated surface using a DC magnetron sputtering apparatus, an ITO target, and oxygen as a reaction gas. , And a substrate with a 30 nanometer thin film (ITO film)
Substrate 6 Epoxy acrylate UV is applied to the corona-treated surface of the substrate made of biaxially stretched polyethylene terephthalate (product name: Emblet S-50, manufactured by Unitika Ltd.) with a thickness of 50 μm.
Dilute the cured coating material (trade name; FA-18, manufactured by Nippon Kako Paint Co., Ltd.) with ethyl acetate, coat to 1.2 g / m2 (solid content) using a Mayer bar, and dry at 100 ° C. for 15 seconds. did. Subsequently, UV irradiation device (EYE GRANDAG made by Eye Graphic Co., Ltd.)
E type ECS 301G1), UV intensity: 250 mW / cm 2 , integrated light quantity: 1
The coat film was polymerized by irradiating with ultraviolet rays under the condition of 17 mJ / cm 2 to obtain a coat film.
Furthermore, on the coated surface of the coated film, using a DC magnetron sputtering device,
A substrate using an ITO target, oxygen introduced as a reaction gas, and a 30 nanometer thin film (ITO film)
Base material 7 Polyethylene naphthalate film (thickness 100 microns, Teijin Limited Q6
5) A substrate in which a thin film of 30 nm is laminated (ITO film) on a smooth surface of a substrate made of 5) by using a ITO magnetron sputtering apparatus with a DC magnetron sputtering apparatus and introducing oxygen as a reaction gas.
Base material 8 Polyethylene naphthalate film (thickness 100 microns, Teijin Limited Q6
5) A base material obtained by laminating a thin film of 30 nanometers (SiN film) using a Si target and introducing nitrogen as a reaction gas on a smooth surface comprising 5) by an RF magnetron sputtering apparatus
Base material 9 Polyethylene naphthalate film (thickness 100 microns, Teijin Limited Q6
The base material which formed the SiN film | membrane with a thickness of 50 nm on the smooth surface which consists of 5) by CatCVD method.
<Preparation of coating solution>
Preparation of solution (I)
Zinc acrylate (Zn salt of acrylic acid) aqueous solution (manufactured by Asada Chemical Co., Ltd., concentration 30 wt% (acrylic acid component: 20 wt%, Zn component 10 wt%) and photopolymerization diluted with methyl alcohol to 25 wt% Agent [1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (Ciba Specialty Chemicals)
(Trade name; Irgacure 2959)] and a surfactant (trade name; Emulgen 120 manufactured by Kao Corporation) were mixed so that the molar fractions would be 98.5%, 1.2%, and 0.3%, respectively. An acid Zn salt solution was prepared.
Preparation of solution (b) A 10% aqueous solution of silyl-modified PVA (trade name: R1130, manufactured by Kuraray Co., Ltd.) is added to solution (b), and the solid content ratio of zinc acrylate and silyl-modified PVA is 87.5%, 12.5 % To prepare a solution (b).
<Preparation of gas barrier laminate film of Example 8>
On the inorganic film-forming surface of the above substrate, the solution (ii) is applied in a Mayer bar with a solid content of 2.5 g.
/ M 2 , applied to the stainless steel plate with the coating surface up, and immediately using an ultraviolet irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic), illuminance: 180 mW / cm 2 , integrated light quantity : Polymerized by irradiating with ultraviolet rays under the condition of 180 mJ / cm 2 to obtain a gas barrier laminated film in which a gas barrier film was laminated. The obtained gas barrier laminate film was heat-treated in an oven at 200 ° C. for 60 minutes.
Next, a linear low density polyethylene film having a thickness of 50 μm (trade name: TU manufactured by Tosero Co., Ltd.)
. X. On one side of FCS), urethane adhesive (polyurethane adhesive (trade name: Takelac A310, manufactured by Mitsui Takeda Chemical Co., Ltd.): 12 parts by weight, isocyanate curing agent (trade name: Takenate A3, manufactured by Mitsui Takeda Chemical Co., Ltd.): 1 Part by weight and ethyl acetate (manufactured by Kanto Chemical Co., Inc.)
: 7 parts by weight) After coating and drying, the resulting gas barrier laminate film is bonded to the polyvalent metal salt polymer layer (unsaturated carboxylic acid compound polyvalent metal salt polymer layer) surface of the laminated film (dry lamination) A multilayer film was obtained.
Table 2 shows the moisture resistance of the obtained gas barrier laminate film.
<Preparation of Gas Barrier Laminate Films of Examples 9 to 25 and Reference Examples 1 to 5>
In Example 8, a substrate was prepared in the same manner except that the conditions for the substrate, the coating solution, the coating amount, and the heat treatment were as shown in Table 2.
The evaluation results are shown in Table 2. The display in Table 2 is as follows.
本発明のバリアフィルムを利用することにより、液晶表示素子、有機ＥＬ等の素子、面
状発光体、光ディバイス、太陽電池等を収納し、ヒートシールにより封印することができ
る。
すなわち、ガスバリアフィルムがヒートシール性熱可塑性樹脂層を利用して他のバリア
材にヒートシールされて形成された空間に、ＥＬ等の素子や太陽電池を収納して密封する
ことができる。
他のバリア材は、本発明のヒートシール性熱可塑性樹脂層と熱融着可能な従来公知の材
料がその表面を構成するものであれば、特に限定されない。
また、重ね合わされた２枚のガスバリアフィルム、または折りたたまれたガスバリアフィ
ルムの間に有機ＥＬ等の素子や太陽電池等を収納し、相対するヒートシール性熱可塑性樹
脂層の部分をヒートシールして密封することができる。
By utilizing the barrier film of the present invention, liquid crystal display elements, elements such as organic EL, planar light emitters, optical devices, solar cells and the like can be accommodated and sealed by heat sealing.
That is, an element such as an EL or a solar cell can be accommodated and sealed in a space formed by heat sealing a gas barrier film to another barrier material using a heat-sealable thermoplastic resin layer.
Another barrier material will not be specifically limited if the conventionally well-known material which can be heat-seal | fused with the heat-sealable thermoplastic resin layer of this invention comprises the surface.
Also, elements such as organic EL and solar cells are housed between two gas barrier films that are overlaid or folded, and the portions of the heat-sealable thermoplastic resin layers that face each other are heat-sealed and sealed. can do.
本発明の不飽和カルボン酸化合物多価金属塩の重合体からなるガスバリア性膜及びかか
るガスバリア性を形成してなるガスバリア性積層体は、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。
Since the gas barrier film made of the polymer of the unsaturated carboxylic acid compound polyvalent metal salt of the present invention and the gas barrier laminate formed with such a gas barrier property are excellent in oxygen permeation resistance (gas barrier property), this is required. Taking advantage of the characteristics, it can be suitably used as a packaging material, particularly a food packaging material having a high gas barrier property, as well as various packaging materials such as medical use and industrial use.
Claims (6)
The method for producing a gas barrier film according to claim 1 or 2, wherein the solution is an aqueous solution.
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