JP4732022B2 - Method for producing gas barrier film - Google Patents
Method for producing gas barrier film Download PDFInfo
- Publication number
- JP4732022B2 JP4732022B2 JP2005173619A JP2005173619A JP4732022B2 JP 4732022 B2 JP4732022 B2 JP 4732022B2 JP 2005173619 A JP2005173619 A JP 2005173619A JP 2005173619 A JP2005173619 A JP 2005173619A JP 4732022 B2 JP4732022 B2 JP 4732022B2
- Authority
- JP
- Japan
- Prior art keywords
- gas barrier
- carboxylic acid
- film
- polyvalent metal
- unsaturated carboxylic
- 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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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 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
- 229920003169 water-soluble polymer Polymers 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
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (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り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。
他方、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に高温で長時間の反応が必要なことから、ポリアクリル酸にイソシアネート化合物等の架橋剤成分を添加する方法（例えば、特許文献３）、更には金属イオンと反応させる方法（例えば、特許文献４）等が提案されているが、かかる方法においても、ポリアクリル酸を架橋剤成分で架橋するには、実施例に記載されているように、１８０〜２００℃で５分間と高温での処理を必要とする。
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 property of the film, heating at a high temperature for a long time is required, which causes 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.
On the other hand, since a composition of polyvinyl alcohol and poly (meth) acrylic acid requires a long reaction at a high temperature for esterification, a method of adding a crosslinking agent component such as an isocyanate compound to polyacrylic acid (for example, a patent) Document 3) and a method of reacting with a metal ion (for example, Patent Document 4) have been proposed. In this method, polyacrylic acid is crosslinked with a crosslinking agent component as described in Examples. As shown, it requires treatment at 180 to 200 ° C. for 5 minutes and at a high temperature.
そこで本発明は、不飽和カルボン酸化合物を１８０〜２００℃の高温での熱処理による架橋を行わずに、透明性に優れ、且つ高湿度下でのガスバリア性に優れたガスバリア性膜を安定して得る方法を開発することを目的とした。 Therefore, the present invention stably stabilizes a gas barrier film excellent in transparency and gas barrier properties under high humidity without crosslinking the unsaturated carboxylic acid compound by heat treatment at a high temperature of 180 to 200 ° C. The purpose was to develop a method to obtain.
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溶媒の存在下で予備重合し、次いで本重合、好ましくは塗工液を一部乾燥後、本重合することを特徴とするガスバリア性膜の製造方法を提供するものである。 In the present invention, the base layer is coated with a polyvalent metal salt solution of an unsaturated carboxylic acid compound having a degree of polymerization of less than 20, and then the polyvalent metal salt of the unsaturated carboxylic acid compound is prepolymerized in the presence of a solvent. Then, the present invention provides a method for producing a gas barrier film, characterized in that the main polymerization, preferably a partial drying of the coating solution, followed by the main polymerization.
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、溶媒の存在下で予備重合し、次いで本重合、好ましくは塗工液を一部乾燥後本重合することを特徴とするガスバリア性膜の製造方法を提供するものである。 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 provides a method for producing a gas barrier film, characterized by pre-polymerization in the presence of a solvent, followed by main polymerization, preferably main polymerization after partially drying the coating solution.
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する際に、当該不飽和カルボン酸化合物多価金属塩の溶液を溶媒の存在下で予備重合した後、本重合することにより、透明性に優れ、且つ高湿度下でのガスバリア性に優れたガスバリア性膜を安定して製造し得る。 When polymerizing an unsaturated carboxylic acid compound polyvalent metal salt having a degree of polymerization of less than 20, the solution of the unsaturated carboxylic acid compound polyvalent metal salt is prepolymerized in the presence of a solvent, followed by main polymerization, A gas barrier film having excellent transparency and excellent gas barrier properties under high humidity can be stably 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 is a carboxylic acid compound having an α, β-ethylenically unsaturated group such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, and the like. Less than, preferably a monomer or 10 or less polymer. 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、ニ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 The polyvalent metal compound according to the present invention specifically includes magnesium (Mg), calcium (Ca), barium (Ba), zinc (Zn), copper (Cu), cobalt (Co), nickel (Ni), aluminum (Al), iron (Fe) and other divalent or higher metals, oxides, hydroxides, halides, carbonates, phosphates, phosphites, hypophosphorous acid of these metals Salt, sulfate or sulfite. 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。
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 / vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, fluororesin Or the mixture etc. can be illustrated. 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.
ガスバリア性膜の製造方法
本発明のガスバリア性膜の製造方法は、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溶媒の存在下で予備重合し、次いで本重合、好ましくは塗工液を一部乾燥後本重合することを特徴とするガスバリア性膜の製造方法である。
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。
Method for Producing Gas Barrier Film In the method for producing a gas barrier film of the present invention, after applying a polyvalent metal salt solution of an unsaturated carboxylic acid compound having a degree of polymerization of less than 20 to a base material layer, A method for producing a gas barrier film, characterized in that a polyvalent metal salt is prepolymerized in the presence of a solvent, followed by main polymerization, preferably by partly drying and then main polymerization.
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.
In addition, when a mixed solution of an unsaturated carboxylic acid compound and a polyvalent metal compound is used, the unsaturated carboxylic acid compound is usually added while the unsaturated carboxylic acid compound and the polyvalent metal compound are dissolved in a solvent. Although a valent metal salt is formed, it is preferable to mix for 1 minute or more in order to ensure the formation of the polyvalent metal salt.
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. 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, bar coater, bar reverse coater, die coater, etc. What is necessary is just to apply | coat so that it may become 0.05-10 g / m < 2 > in the quantity (solid content) in the solution (solid content) of a saturated carboxylic acid compound polyvalent metal salt, Preferably it is 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 ( Acrylic acid divalent esters of glycols such as (meth) acrylate, PEG # 600 • di (meth) acrylate, neopentyl glycol • di (meth) acrylate, 1,4-butanediol • di (meth) acrylate, and other Vinyl esthetics such as saturated carboxylic acid (di) ester compounds and vinyl acetate Monomers such as compounds or low molecular weight compounds, polyvinyl alcohol, ethylene / vinyl alcohol copolymers, polyvinyl pyrrolidone, polyvinyl ethyl ether, polyacrylamide, polyethyleneimine, starch, gum arabic, methylcellulose and other water-soluble polymers, acrylic High molecular weight compounds such as acid ester polymers, ethylene / acrylic acid copolymers, polyvinyl acetate, ethylene / vinyl acetate copolymers, polyesters and polyurethanes 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.
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した後に、かかる不飽和カルボン酸化合物の多価金属塩を予備重合及び本重合するには、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。
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、電子線等が上げられる。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の多価金属塩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、ダロキュアー１１７３（チバ・スペシャリティ・ケミカルズ社製）、イルガキュアー１８４（チバ・スペシャリティ・ケミカルズ社製）、エサキュアーＫＴ５５（ランベルティー社製）等の商品名で製造・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−モルフォリンが挙げられる。
In order to pre-polymerize and main-polymerize the polyvalent metal salt of the unsaturated carboxylic acid compound after applying the polyvalent metal salt solution of the unsaturated carboxylic acid compound to the base material layer, various known methods, specifically, For example, there is a method by irradiation with ionizing radiation or heating.
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 polyvalent metal salt of the unsaturated carboxylic acid compound. As the photopolymerization initiator, known ones can be used. For example, Darocur 1173 (manufactured by Ciba Specialty Chemicals), Irgacure 184 (manufactured by Ciba Specialty Chemicals), Esacure KT55 (Lamberti) And a radical polymerization initiator manufactured and sold under a trade name such as 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の多価金属塩の溶液を予備重合する際は、不飽和カルボン酸化合物多価金属塩を溶媒の存在下で予備重合する必要がある。予備重合する際の不飽和カルボン酸化合物多価金属塩の溶液の濃度は、不飽和カルボン酸化合物多価金属塩の結晶が析出しない限り、とくに限定はされないが、通常、７０重量％以下、とくに６０〜２０重量％の範囲、換言すれば、溶媒（水）の含有量を３０重量％以上、とくに４０〜８０重量％の範囲にしておくことが好ましい。
また、不飽和カルボン酸化合物多価金属塩を溶媒の存在下で予備重合する際の温度は、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。予備重合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、本重合後に溶媒を乾燥する時間が長くなり、ガスバリア性膜の製造ライン等を長くする必要がある。
不飽和カルボン酸化合物多価金属塩の溶液を予備重合する際には、不飽和カルボン酸化合物多価金属塩の重合率を７０％以下、とくに３０〜６０％の範囲に留めておくことが好ましい。予備重合する際に、重合率を７０％以下に留めておくと、不飽和カルボン酸化合物多価金属塩の溶液中の水分量が３０重量％以下と低くても、本重合して得られるガスバリア性膜の外観及びガスバリア性が優れる。
本発明における不飽和カルボン酸化合物多価金属塩の重合率（予備重合及び本重合後）は、以下の測定方法により求めた。
重合率（％）：〔（Ｂ１／Ｂ）ＵＶ後／（Ｂ１／Ｂ）モノマー〕×１００
＊（Ｂ１／Ｂ）ＵＶ後：紫外線照射（重合後）後の（Ｂ１／Ｂ）
＊（Ｂ１／Ｂ）モノマー：モノマー（重合前）の（Ｂ１／Ｂ）
（Ｂ１／Ｂ）については下記に記載のとおり規定した。
８３０ｃｍ−１付近のビニル基に結合する水素のδＣ−Ｈに基づく吸光度Ｂ１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Ｂとの比（Ｂ１／Ｂ）は、（予備）重合させた膜から１ｃｍ×３ｃｍの測定用サンプルを切り出し、その表面（重合体（Ａ）層）の赤外線吸収スペクトルを赤外線全反射測定（ＡＴＲ法）により得、以下の手順で、先ず、吸光度Ｂ１及び吸光度Ｂを求める。
８３０ｃｍ−１付近のビニル基に結合する水素のδＣ−Ｈに基づく吸光度Ｂ１：赤外線吸収スペクトルの８００ｃｍ−１と８５０ｃｍ−１の吸光度とを直線（Ｐ）で結び、８００〜８５０ｃｍ−１間の最大吸光度（８３０ｃｍ−１付近）から垂直に直線（Ｑ）を下ろし、当該直線（Ｑ）と直線（Ｐ）との交点と最大吸光度との吸光度の距離（長さ）を吸光度Ｂ１とする。
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Ｂ：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Ｂ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付近である。
次いで、上記方法で求めた吸光度Ｂ１及び吸光度Ｂから比（Ｂ１／Ｂ）を求める。また重合率は上記計算式のように、モノマーの吸光度比（Ｂ１／Ｂ）モノマーとＵＶ照射（重合後）後の（Ｂ１／Ｂ）ＵＶ後を測定し求める。
なお、本発明のおける赤外線スペクトルの測定（赤外線全反射測定：ＡＴＲ法）は、日本分光社製ＦＴ−ＩＲ３５０装置を用い、ＫＲＳ−５（Ｔｈａｌｌｉｕｍ Ｂｒｏｍｉｄｅ−Ｉｏｄｉｄｅ）結晶を装着して、入射角４５度、室温、分解能４ｃｍ−１、積算回数１５０回の条件で行う。
When prepolymerizing a solution of an unsaturated carboxylic acid compound polyvalent metal salt, it is necessary to prepolymerize the unsaturated carboxylic acid compound polyvalent metal salt in the presence of a solvent. The concentration of the unsaturated carboxylic acid compound polyvalent metal salt solution at the time of prepolymerization is not particularly limited as long as the unsaturated carboxylic acid compound polyvalent metal salt crystals do not precipitate, but is usually 70% by weight or less, particularly The range of 60 to 20% by weight, in other words, the content of the solvent (water) is preferably 30% by weight or more, particularly 40 to 80% by weight.
The temperature at which the unsaturated carboxylic acid compound polyvalent metal salt is prepolymerized in the presence of a solvent is not particularly limited as long as it is not the temperature at which the solvent boils, but is usually 60 ° C. or less, particularly from room temperature to 50 ° C. It is preferable to carry out within a range. If the temperature at the prepolymerization is too high, the solvent evaporates faster and crystals of the unsaturated carboxylic acid compound polyvalent metal salt are likely to precipitate, whereas if the temperature is too low, the solvent is removed after the main polymerization. It is necessary to lengthen the drying time and lengthen the production line of the gas barrier film.
When prepolymerizing the solution of the unsaturated carboxylic acid compound polyvalent metal salt, the polymerization rate of the unsaturated carboxylic acid compound polyvalent metal salt is preferably 70% or less, particularly preferably in the range of 30 to 60%. . When the prepolymerization is carried out, if the polymerization rate is kept at 70% or less, the gas barrier obtained by the main polymerization can be obtained even if the water content in the unsaturated carboxylic acid compound polyvalent metal salt solution is as low as 30% by weight or less. The appearance and gas barrier properties of the conductive film are excellent.
The polymerization rate (after prepolymerization and main polymerization) of the unsaturated carboxylic acid compound polyvalent metal salt in the present invention was determined by the following measurement method.
Polymerization rate (%): [(B 1 / B) after UV / (B 1 / B) monomer ] × 100
* (B 1 / B) after UV: ultraviolet irradiation (after polymerization) after (B 1 / B)
* (B 1 / B) Monomer: Monomer (before polymerization) of (B 1 / B)
(B 1 / B) was defined as described below.
Ratio of absorbance B 1 based on δC—H of hydrogen bonded to a vinyl group near 830 cm −1 to absorbance B based on νC═O of carboxylate ions near 1520 cm −1 in the infrared absorption spectrum (B 1 / B) Cut out a measurement sample of 1 cm × 3 cm from the (preliminary) polymerized film, and obtained the infrared absorption spectrum of the surface (polymer (A) layer) by infrared total reflection measurement (ATR method). First, absorbance B 1 and absorbance B are determined.
830 cm -1 vicinity absorbance based .delta.C-H of hydrogen binding to vinyl groups B 1: bear and the absorbance of the infrared absorption spectrum of 800 cm -1 and 850 cm -1 in a straight line (P), between 800～850Cm -1 A straight line (Q) is dropped vertically from the maximum absorbance (near 830 cm −1 ), and the distance (length) of the absorbance between the intersection of the straight line (Q) and the straight line (P) and the maximum absorbance is defined as absorbance B 1 .
1520 cm -1 absorbance based νC = O of carboxylate ions in the vicinity of B: the absorbance of the infrared absorption spectrum of 1480 cm -1 and 1630 cm -1 connected by a straight line (L), 1480~1630cm maximum absorbance between -1 (1520 cm The straight line (M) was dropped vertically from the vicinity of −1 ), and the absorbance distance (length) between the intersection of the straight line (M) and the straight line (L) and the maximum absorbance was defined as absorbance B. 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 , and magnesium is near 1540 cm −1 . is there.
Next, the ratio (B 1 / B) is determined from the absorbance B 1 and absorbance B determined by the above method. The rate of polymerization as described above formulas, the absorbance ratio of the monomer (B 1 / B) monomer and UV irradiation (after polymerization) after (B 1 / B) obtaining measured after UV.
In addition, the measurement of the infrared spectrum (infrared total reflection measurement: ATR method) in the present invention uses an FT-IR350 apparatus manufactured by JASCO Corporation, and a KRS-5 (Thallium Bromide-Iodide) crystal is attached, and the incident angle is 45. Degree, room temperature, resolution of 4 cm −1 , and 150 times of integration.
不飽和カルボン酸化合物多価金属塩の溶液を電離性放射線を照射して予備重合する場合は、通常、電離性放射線の照射量を１〜５０ｍＪ、とくに３〜１５ｍＪの範囲にすることが好ましい。照射量が５０ｍＪを超えると予備重合時の重合率が高くなり、本重合して得られるガスバリア性膜の外観、特に透明性が低下する虞がある。 When prepolymerizing a solution of an unsaturated carboxylic acid compound polyvalent metal salt by irradiating with ionizing radiation, it is usually preferable to set the irradiation amount of ionizing radiation to a range of 1 to 50 mJ, particularly 3 to 15 mJ. When the irradiation amount exceeds 50 mJ, the polymerization rate at the time of prepolymerization increases, and the appearance, particularly transparency, of the gas barrier film obtained by the main polymerization may be reduced.
予備重合した後引き続き本重合を行うが、本重合する際には、塗工液を一部乾燥後に行うことが好ましい。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３〜６０重量％の範囲で溶媒を含む状態で本重合することが好ましい。塗工液に含まれる溶媒がない場合は、本重合して得られるガスバリア性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多すぎる場合は、本重合して得られるガスバリア性膜の外観、特に透明性が低下する虞がある。
予備重合後の本重合を電離性放射線を照射して行う場合は、通常、電離性放射線の照射量を５０〜３００ｍＪ、とくに１００〜２００ｍＪの範囲にすることが好ましい。照射量をかかる範囲にすることにより、重合率が８０％以上、好ましくは９０％のガスバリア性膜が安定して得られる。
Subsequent to the prepolymerization, the main polymerization is continued. In the main polymerization, it is preferable that the coating liquid is partially dried. In addition, the drying of the coating liquid does not completely remove the solvent, but a suitable solvent (water if an aqueous solution is used) in the coating liquid, preferably in a state containing the solvent in the range of 3 to 60% by weight. The main polymerization is preferable. When there is no solvent contained in the coating liquid, there is a risk that the oxygen barrier property of the gas barrier film obtained by the main polymerization may be reduced. When too much solvent is contained in the coating liquid, the main liquid is obtained by polymerization. There is a possibility that the appearance, particularly transparency, of the gas barrier film is reduced.
When the main polymerization after the prepolymerization is performed by irradiating with ionizing radiation, it is usually preferable to set the irradiation amount of the ionizing radiation in the range of 50 to 300 mJ, particularly 100 to 200 mJ. By setting the irradiation amount in such a range, a gas barrier film having a polymerization rate of 80% or more, preferably 90% can be stably obtained.
ガスバリア性膜
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。
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、高湿度下での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 Ｂｒｏｍｉｄｅ−Ｉｏｄｉｄｅ）結晶を装着して、入射角４５度、室温、分解能４ｃｍ-1、積算回数１５０回の条件で行った。
Gas barrier film 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 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 on ═O 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 .
Therefore, in the gas barrier film obtained by the production method of the present invention, (A 0 / A) being less than 0.25 indicates that there are no or few free carboxylic acid groups. A film exceeding .25 has a large content of free carboxylic acid groups, and there is a possibility that the gas barrier resistance under high humidity may not be improved.
Ratio of absorbance A 0 based on νC═O of a carboxylic acid group near 1700 cm −1 in the present invention to absorbance A based on νC═O of a carboxylate ion near 1520 cm −1 in an infrared absorption spectrum (A 0 / A) Cuts out a measurement sample of 1 cm × 3 cm from a gas barrier film (gas barrier laminate), and measures the infrared absorption spectrum of the surface (unsaturated carboxylic acid compound polyvalent metal salt polymer layer) by infrared total reflection measurement (ATR method). First, the absorbance A 0 and absorbance A were determined by the following procedure.
1700cm absorbance based νC = O -1 vicinity of the carboxylic acid groups A 0: a absorbance of the infrared absorption spectrum of 1660 cm -1 and 1760 cm -1 connected by a straight line (N), 1660~1760cm maximum absorbance between -1 ( The straight line (O) was dropped vertically from around 1700 cm −1, and the absorbance distance (length) between the intersection of the straight line (O) and the straight line (N) and the maximum absorbance was defined as absorbance A 0 .
1520 cm -1 vicinity of carboxylate ion of νC = O based upon the absorbance A: connected by a straight line (L) and the absorbance of the infrared absorption spectrum of 1480 cm -1 and 1630 cm -1, the maximum absorbance between 1480~1630cm -1 (1520cm The straight line (M) was dropped vertically from the vicinity of −1 ), and the absorbance distance (length) between the intersection of the straight line (M) and the straight line (L) and the maximum absorbance was defined as absorbance A. The peak position of maximum absorbance (near 1520 cm −1 ) may vary depending on the metal species of the counter ion. For example, calcium is near 1520 cm −1 , zinc is near 1520 cm −1 , magnesium is near 1540 cm −1 , and In sodium (Na), it is around 1540 cm −1 .
Next, the ratio (A 0 / A) was determined from the absorbance A 0 and the absorbance A determined by the above method.
In addition, the measurement of the infrared spectrum in the present invention (infrared total reflection measurement: ATR method)
Using a FT-IR350 apparatus manufactured by JASCO Corporation, a KRS-5 (Thallium Bromide-Iodide) crystal was mounted, and the measurement was performed under the conditions of an incident angle of 45 degrees, room temperature, resolution of 4 cm −1 , and number of integrations of 150 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 Polypropylene random copolymer, ethylene / butene-1 random copolymer, polyolefin such as propylene / butene-1 random copolymer, or a composition of two or more, ethylene / vinyl acetate copolymer (EVA), ethylene・ (Meth) acrylic acid copolymer or metal salt thereof, EVA and polyolefin A layer obtained from the object or the like.
Among these, a heat-sealing layer obtained from an ethylene-based polymer such as high-pressure method low-density polyethylene, linear low-density polyethylene (so-called LLDPE), or high-density polyethylene is preferable because it has excellent low-temperature heat sealability and heat seal strength.
次に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。
＜評価方法＞
（１）重合率［％］：上記記載の方法で測定した。
（２）酸素透過度［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］：積層フィルムを、モコン社製 ＯＸ−ＴＲＡＮ２／２１ ＭＬを用いて、ＪＩＳ Ｋ ７１２６に準じ、温度；２０℃、湿度；９０％ＲＨの条件で測定した。
（３）吸光度比（Ａ０／Ａ）：上記記載の方法で測定した。
（４）ヘイズ［％］：ＪＩＳ Ｋ ７１３６に準拠し、フィルム１枚のヘイズ（％）を測定した。測定装置にはＨａｚｅ Ｍｅｔｅｒ（日本電色工業社製 ＮＤＨ−２０００）を使用した。
（５）塗工液（塗工膜）の水分量［重量％］：不飽和カルボン酸化合物多価金属塩溶液を塗工した積層フィルムあるいは重合後の積層フィルムから１２０×２９７ｍｍの測定用サンプルを切り出しその重量（Ｗｇ）を測定した後、温度；１３０℃の熱風乾燥器で１０分間乾燥してその重量（Ｗ乾ｇ）を測定する。それとは別に基材フィルム（不飽和カルボン酸化合物多価金属塩溶液を塗工するフィルム）から１２０×２９７ｍｍの測定用サンプルを切り出しその重量（Ｗ基材ｇ）を測定する。そして、前記各フィルムの重量を用い、以下の式で塗工膜中の水分量を求めた。
水分量（重量％）＝〔｛（Ｗ−Ｗ基材）−（Ｗ乾−Ｗ基材）｝／（Ｗ−Ｗ基材）〕×１００
The physical property values and the like in Examples and Comparative Examples were obtained by the following evaluation methods.
<Evaluation method>
(1) Polymerization rate [%]: Measured by the method described above.
(2) Oxygen permeability [ml / (m 2 · day · MPa)]: Using OX-TRAN 2/21 ML manufactured by Mocon Co., Ltd., according to JIS K 7126, temperature: 20 ° C., humidity: 90 It was measured under the condition of% RH.
(3) Absorbance ratio (A 0 / A): measured by the method described above.
(4) Haze [%]: Based on JIS K7136, the haze (%) of one film was measured. A Haze Meter (NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd.) was used as a measuring device.
(5) Water content [% by weight] of coating solution (coating film): 120 × 297 mm measurement sample from laminated film coated with unsaturated carboxylic acid compound polyvalent metal salt solution or laminated film after polymerization After cutting and measuring its weight (Wg), it is dried for 10 minutes in a hot air drier at a temperature of 130 ° C. and its weight (W dry g) is measured. Separately, a sample for measurement of 120 × 297 mm is cut out from a substrate film (film to which an unsaturated carboxylic acid compound polyvalent metal salt solution is applied), and the weight (W substrate g) is measured. And the moisture content in a coating film was calculated | required with the following formula | equation using the weight of each said film.
Water content (% by weight) = [{(W-W substrate )-(W dry- W substrate )} / (WW substrate )] × 100
＜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 A surfactant (trade name; Emulgen 120, manufactured by Kao Corporation) was mixed so that the molar fractions were 98.5%, 1.2%, and 0.3%, respectively, and consisted of a Zn acrylate solution (X). An unsaturated carboxylic acid compound polyvalent metal salt solution was prepared.
実施例１（参考例とする）
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２０ｍＷ/ｃｍ2、積算光量３ｍＪ/ｃｍ２の条件で紫外線を照射して予備重合を行った。得られた予備重合膜の重合率を上記記載の方法で測定した結果、予備重合膜の重合率は５７．４％で、水分量は７０重量％であった。
次いで、得られた予備重合膜を乾燥せずに、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１８９ｍＷ/ｃｍ2、積算光量１９０ｍＪ/ｃｍ２の条件で紫外線を照射して、本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の重合率［％］、酸素透過度（９０％ＲＨ）［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］、吸光度比（Ａ０／Ａ）及びヘイズ［％］を表１に示す。
Example 1 (referred to as a reference example)
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 , fasten the coated surface to a stainless steel plate, and immediately use a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic Co., Ltd.), UV intensity 20 mW / cm 2 Preliminary polymerization was performed by irradiating ultraviolet rays under the condition of an integrated light amount of 3 mJ / cm 2 . As a result of measuring the polymerization rate of the obtained prepolymerized film by the method described above, the polymerization rate of the prepolymerized film was 57.4% and the water content was 70% by weight.
Next, without drying the obtained prepolymerized film, a UV irradiation apparatus (EYE GRANDAGE model ECS manufactured by Eye Graphic Co., Ltd.)
301G1) was used to irradiate ultraviolet rays under the conditions of a UV intensity of 189 mW / cm 2 and an integrated light amount of 190 mJ / cm 2 to obtain a gas barrier laminated film in which main polymerization was performed and a gas barrier film was laminated.
The polymerization rate [%], oxygen permeability (90% RH) [ml / (m 2 · day · MPa)], absorbance ratio (A 0 / A) and haze [%] of the obtained gas barrier laminate film are shown. It is shown in 1.
実施例２
実施例１で得た予備重合膜を、熱風乾燥器を使用して温度；６０℃、時間；８秒の条件で乾燥し、予備重合膜中の水分量を４５重量％にした後、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１８９ｍＷ/ｃｍ2、積算光量１９０ｍＪ/ｃｍ２の条件で紫外線を照射して、本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の重合率［％］、酸素透過度（９０％ＲＨ）［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］、吸光度比（Ａ０／Ａ）及びヘイズ［％］を表１に示す。
Example 2
The prepolymerized film obtained in Example 1 was dried using a hot air dryer under the conditions of temperature: 60 ° C., time: 8 seconds, and the water content in the prepolymerized film was adjusted to 45% by weight, followed by UV irradiation. device using a (eye graphics Co. eYE GRANDAGE model ECS 301G1), UV intensity 189mW / cm 2, was irradiated with ultraviolet light under conditions of integrated quantity of light 190 mJ / cm 2, the polymerization gas-barrier laminate obtained by laminating the gas barrier film A film was obtained.
The polymerization rate [%], oxygen permeability (90% RH) [ml / (m 2 · day · MPa)], absorbance ratio (A 0 / A) and haze [%] of the obtained gas barrier laminate film are shown. It is shown in 1.
実施例３
実施例１で得た予備重合膜を、熱風乾燥器を使用して温度；６０℃、時間；１６秒の条件で乾燥し、予備重合膜中の水分量を３０重量％にした後、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１８９ｍＷ/ｃｍ2、積算光量１９０ｍＪ/ｃｍ２の条件で紫外線を照射して、本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の重合率［％］、酸素透過度（９０％ＲＨ）［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］、吸光度比（Ａ０／Ａ）及びヘイズ［％］を表１に示す。
Example 3
The prepolymerized film obtained in Example 1 was dried using a hot air dryer under the conditions of temperature: 60 ° C., time: 16 seconds, the water content in the prepolymerized film was adjusted to 30% by weight, and then UV irradiation was performed. device using a (eye graphics Co. eYE GRANDAGE model ECS 301G1), UV intensity 189mW / cm 2, was irradiated with ultraviolet light under conditions of integrated quantity of light 190 mJ / cm 2, the polymerization gas-barrier laminate obtained by laminating the gas barrier film A film was obtained.
The polymerization rate [%], oxygen permeability (90% RH) [ml / (m 2 · day · MPa)], absorbance ratio (A 0 / A) and haze [%] of the obtained gas barrier laminate film are shown. It is shown in 1.
実施例４
実施例１で得た予備重合膜を、熱風乾燥器を使用して温度；６０℃、時間；３０秒の条件で乾燥し、予備重合膜中の水分量を１９重量％にした後、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１８９ｍＷ/ｃｍ2、積算光量１９０ｍＪ/ｃｍ２の条件で紫外線を照射して、本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の重合率［％］、酸素透過度（９０％ＲＨ）［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］、吸光度比（Ａ０／Ａ）及びヘイズ［％］を表１に示す。
Example 4
The prepolymerized film obtained in Example 1 was dried using a hot air dryer under the conditions of temperature: 60 ° C., time: 30 seconds, the water content in the prepolymerized film was adjusted to 19% by weight, and then UV irradiation was performed. device using a (eye graphics Co. eYE GRANDAGE model ECS 301G1), UV intensity 189mW / cm 2, was irradiated with ultraviolet light under conditions of integrated quantity of light 190 mJ / cm 2, the polymerization gas-barrier laminate obtained by laminating the gas barrier film A film was obtained.
The polymerization rate [%], oxygen permeability (90% RH) [ml / (m 2 · day · MPa)], absorbance ratio (A 0 / A) and haze [%] of the obtained gas barrier laminate film are shown. It is shown in 1.
実施例５
実施例１で得た予備重合膜を、熱風乾燥器を使用して温度；６０℃、時間；６０秒の条件で乾燥し、予備重合膜中の水分量を６重量％にして、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１８９ｍＷ/ｃｍ2、積算光量１９０ｍＪ/ｃｍ２の条件で紫外線を照射して、本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の重合率［％］、酸素透過度（９０％ＲＨ）［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］、吸光度比（Ａ０／Ａ）及びヘイズ［％］を表１に示す。
Example 5
The prepolymerized film obtained in Example 1 was dried using a hot air dryer under the conditions of temperature: 60 ° C., time: 60 seconds, the water content in the prepolymerized film was 6% by weight, and UV irradiation apparatus using (eye graphics Co. eYE GRANDAGE model ECS 301G1), UV intensity 189mW / cm 2, was irradiated with ultraviolet light under conditions of integrated quantity of light 190 mJ / cm 2, the polymerized gas-barrier laminated gas-barrier film laminate film Got.
The polymerization rate [%], oxygen permeability (90% RH) [ml / (m 2 · day · MPa)], absorbance ratio (A 0 / A) and haze [%] of the obtained gas barrier laminate film are shown. It is shown in 1.
実施例６
上記アクリル酸Ｚｎ塩溶液（Ｘ）を厚さ２０μｍの二軸延伸ポリプロピレンフィルム（東セロ社製 商品名；ＯＰ ＨＥ−１）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２０ｍＷ/ｃｍ2、積算光量３ｍＪ/ｃｍ２の条件で紫外線を照射して予備重合を行った。得られた予備重合膜の重合率を上記記載の方法で測定した結果、予備重合膜の重合率は５７．４％で、水分量は７０重量％であった。
次いで、得られた予備重合膜を、熱風乾燥器を使用して温度；６０℃、時間；８秒の条件で乾燥し、予備重合膜中の水分量を４５重量％にした後、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１８９ｍＷ/ｃｍ2、積算光量１９０ｍＪ/ｃｍ２の条件で紫外線を照射して、本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の重合率［％］、酸素透過度（９０％ＲＨ）［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］、吸光度比（Ａ０／Ａ）及びヘイズ［％］を表１に示す。
Example 6
The coating amount of the above-described Zn acrylate solution (X) is a solid content on a corona-treated surface of a base film made of a biaxially stretched polypropylene film (trade name; OP HE-1 manufactured by Tosero Co., Ltd.) having a thickness of 20 μm. To 3.5 g / m 2 , fixed to a stainless steel plate with the coating surface up, and using a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic), UV intensity 20 mW / cm 2 Preliminary polymerization was performed by irradiating ultraviolet rays under the condition of an integrated light amount of 3 mJ / cm 2 . As a result of measuring the polymerization rate of the obtained prepolymerized film by the method described above, the polymerization rate of the prepolymerized film was 57.4% and the water content was 70% by weight.
Next, the obtained prepolymerized film was dried using a hot air dryer under conditions of temperature: 60 ° C., time: 8 seconds, and the water content in the prepolymerized film was adjusted to 45% by weight. using (eye graphics Co. eYE GRANDAGE model ECS 301G1), UV intensity 189mW / cm 2, was irradiated with ultraviolet light under conditions of integrated quantity of light 190 mJ / cm 2, the polymerized gas-barrier laminated gas-barrier film laminate film Got.
The polymerization rate [%], oxygen permeability (90% RH) [ml / (m 2 · day · MPa)], absorbance ratio (A 0 / A) and haze [%] of the obtained gas barrier laminate film are shown. It is shown in 1.
実施例７
上記アクリル酸Ｚｎ塩溶液（Ｘ）を厚さ１５μｍの二軸延伸ポリアミドフィルム（ユニチカ社製 商品名；エンブレムＯＮ１５、）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２０ｍＷ/ｃｍ2、積算光量３ｍＪ/ｃｍ２の条件で紫外線を照射して予備重合を行った。得られた予備重合膜の重合率を上記記載の方法で測定した結果、予備重合膜の重合率は５７．４％で、水分量は７０重量％であった。
次いで、得られた予備重合膜を、熱風乾燥器を使用して温度；６０℃、時間；８秒の条件で乾燥し、予備重合膜中の水分量を４５重量％にして、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１８９ｍＷ/ｃｍ2、積算光量１９０ｍＪ/ｃｍ２の条件で紫外線を照射して、本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の重合率［％］、酸素透過度（９０％ＲＨ）［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］、吸光度比（Ａ０／Ａ）及びヘイズ［％］を表１に示す。
Example 7
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 polyamide film having a thickness of 15 μm (trade name; Emblem ON15, manufactured by Unitika Ltd.) with a Mayer bar. It is applied to 3.5 g / m 2 , fixed on a stainless steel plate with the application surface facing up, and using a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic Co., Ltd.), a UV intensity of 20 mW / cm 2 , Preliminary polymerization was performed by irradiating with ultraviolet rays under the condition of an integrated light quantity of 3 mJ / cm 2 . As a result of measuring the polymerization rate of the obtained prepolymerized film by the method described above, the polymerization rate of the prepolymerized film was 57.4% and the water content was 70% by weight.
Next, the obtained prepolymerized film was dried using a hot air dryer under conditions of temperature: 60 ° C., time: 8 seconds, the moisture content in the prepolymerized film was changed to 45% by weight, and a UV irradiation device ( EYE GRANDAGE Model ECS 301G1) manufactured by Eye Graphic Co., Ltd. is used to irradiate ultraviolet rays under the conditions of UV intensity of 189 mW / cm 2 and integrated light quantity of 190 mJ / cm 2 , and polymerize the gas barrier laminated film on which a gas barrier film is laminated. Obtained.
The polymerization rate [%], oxygen permeability (90% RH) [ml / (m 2 · day · MPa)], absorbance ratio (A 0 / A) and haze [%] of the obtained gas barrier laminate film are shown. It is shown in 1.
参考例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（商品名；エンブレットＰＥＴ１２、ユニチカ社製）からなる基材フィルムのコロナ処理面に、メイヤーバーで塗布量が固形分で３．５ｇ／ｍ２になるように塗布した後、塗工液中の水分量が７０重量％の状態で、直ちに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１８９ｍＷ/ｃｍ2、積算光量１９０ｍＪ/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の重合率［％］、酸素透過度（９０％ＲＨ）［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］、吸光度比（Ａ０／Ａ）及びヘイズ［％］を表２に示す。
Reference example 1
The coating amount of the above-described Zn acrylate solution (X) is a solid content on the corona-treated surface of a base film made of a biaxially stretched polyester film (trade name; Emblet PET12, manufactured by Unitika) with a thickness of 12 μm. in after coating to be 3.5 g / m 2, with moisture content of 70% by weight state in the coating liquid, using a UV irradiation apparatus (eye graphic Co. eYE GRANDAGE model ECS 301G1) immediately, UV A gas barrier laminate film was obtained by polymerizing by irradiation with ultraviolet rays under the conditions of an intensity of 189 mW / cm 2 and an integrated light amount of 190 mJ / cm 2 .
The polymerization rate [%], oxygen permeability (90% RH) [ml / (m 2 · day · MPa)], absorbance ratio (A 0 / A) and haze [%] of the obtained gas barrier laminate film are shown. It is shown in 2.
参考例２
参考例１と同様にして上記アクリル酸Ｚｎ塩溶液（Ｘ）を二軸延伸ポリエステルフィルムからなる基材フィルムに塗布した後、熱風乾燥器を使用して温度；６０℃、時間；８秒の条件で乾燥し、重合前の塗工液の水分量を４５重量％にした後、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１８９ｍＷ/ｃｍ2、積算光量１９０ｍＪ/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の重合率［％］、酸素透過度（９０％ＲＨ）［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］、吸光度比（Ａ０／Ａ）及びヘイズ［％］を表２に示す。
Reference example 2
In the same manner as in Reference Example 1, the above-described Zn acrylate solution (X) was applied to a base film made of a biaxially stretched polyester film, and then the temperature; 60 ° C., time; 8 seconds using a hot air dryer Then, the water content of the coating liquid before polymerization is adjusted to 45% by weight, and using a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic Co., Ltd.), the UV intensity is 189 mW / cm 2 , the integrated light quantity is 190 mJ / A gas barrier laminated film was obtained by polymerizing by irradiating ultraviolet rays under the condition of cm 2 and laminating the gas barrier film.
The polymerization rate [%], oxygen permeability (90% RH) [ml / (m 2 · day · MPa)], absorbance ratio (A 0 / A) and haze [%] of the obtained gas barrier laminate film are shown. It is shown in 2.
参考例３
参考例１と同様にして上記アクリル酸Ｚｎ塩溶液（Ｘ）を二軸延伸ポリエステルフィルムからなる基材フィルムに塗布した後、熱風乾燥器を使用して温度；６０℃、時間；１６秒の条件で乾燥し、重合前の塗工液の水分量を３０重量％にした後、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１８９ｍＷ/ｃｍ2、積算光量１９０ｍＪ/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の重合率［％］、酸素透過度（９０％ＲＨ）［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］、吸光度比（Ａ０／Ａ）及びヘイズ［％］を表２に示す。
Reference example 3
In the same manner as in Reference Example 1, the above-described Zn acrylate solution (X) was applied to a base film composed of a biaxially stretched polyester film, and then the temperature; 60 ° C., time; 16 seconds using a hot air dryer Then, the water content of the coating liquid before polymerization is adjusted to 30% by weight, and using a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic Co., Ltd.), the UV intensity is 189 mW / cm 2 , the integrated light quantity is 190 mJ / Ultraviolet rays were irradiated under the condition of cm 2 to obtain a gas barrier laminated film in which a gas barrier film was laminated by polymerization.
The polymerization rate [%], oxygen permeability (90% RH) [ml / (m 2 · day · MPa)], absorbance ratio (A 0 / A) and haze [%] of the obtained gas barrier laminate film are shown. It is shown in 2.
参考例４
参考例１と同様にして上記アクリル酸Ｚｎ塩溶液（Ｘ）を二軸延伸ポリエステルフィルムからなる基材フィルムに塗布した後、熱風乾燥器を使用して温度；６０℃、時間；３０秒の条件で乾燥し、重合前の塗工液の水分量を１９重量％にした後、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１８９ｍＷ/ｃｍ2、積算光量１９０ｍＪ/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の重合率［％］、酸素透過度（９０％ＲＨ）［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］、吸光度比（Ａ０／Ａ）及びヘイズ［％］を表２に示す。
Reference example 4
In the same manner as in Reference Example 1, the above-mentioned Zn acrylate solution (X) was applied to a base film composed of a biaxially stretched polyester film, and then the temperature; 60 ° C., time; 30 seconds using a hot air dryer Then, the water content of the coating liquid before polymerization is set to 19% by weight, and using a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic Co., Ltd.), the UV intensity is 189 mW / cm 2 , the integrated light quantity is 190 mJ / A gas barrier laminated film was obtained by polymerizing by irradiating ultraviolet rays under the condition of cm 2 and laminating the gas barrier film.
The polymerization rate [%], oxygen permeability (90% RH) [ml / (m 2 · day · MPa)], absorbance ratio (A 0 / A) and haze [%] of the obtained gas barrier laminate film are shown. It is shown in 2.
参考例５
参考例１と同様にして上記アクリル酸Ｚｎ塩溶液（Ｘ）を二軸延伸ポリエステルフィルムからなる基材フィルムに塗布した後、熱風乾燥器を使用して温度；６０℃、時間；６０秒の条件で乾燥し、重合前の塗工液の水分量を６重量％にした後、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１８９ｍＷ/ｃｍ2、積算光量１９０ｍＪ/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の重合率［％］、酸素透過度（９０％ＲＨ）［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］、吸光度比（Ａ０／Ａ）及びヘイズ［％］を表２に示す。
Reference Example 5
In the same manner as in Reference Example 1, the above-described Zn acrylate solution (X) was applied to a base film composed of a biaxially stretched polyester film, and then the temperature; 60 ° C., time; 60 seconds using a hot air dryer Then, the water content of the coating liquid before polymerization is adjusted to 6% by weight. Then, using a UV irradiation device (EYE GRANDAGE model ECS 301G1 manufactured by Eye Graphic Co., Ltd.), the UV intensity is 189 mW / cm 2 , the integrated light quantity is 190 mJ / A gas barrier laminated film was obtained by polymerizing by irradiating ultraviolet rays under the condition of cm 2 and laminating the gas barrier film.
The polymerization rate [%], oxygen permeability (90% RH) [ml / (m 2 · day · MPa)], absorbance ratio (A 0 / A) and haze [%] of the obtained gas barrier laminate film are shown. It is shown in 2.
表１及び表２から明らかなように、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に紫外線等の電離性放射線を照射して不飽和カルボン酸化合物の多価金属塩を重合させる際には水等の溶媒の存在が重要である。
しかも、参考例１〜５に示すように、不飽和カルボン酸化合物の多価金属塩溶液に含まれる水分量を変化させた場合、溶液に含まれる水分量を４５重量％に調整して重合させた場合（参考例２）は酸素バリア性及び透明性がともに優れたガスバリア性積層フィルムが得られるが、溶液に含まれる水分量が７０重量％（参考例１）と多い状態、あるいは３０重量％以下にした状態（参考例３〜５）で、不飽和カルボン酸化合物の多価金属塩を重合させた場合は酸素バリア性及び透明性がともに優れたガスバリア性積層フィルムが得られない虞があり、重合時の水分量を厳しく調整する必要があることが分かる。
それに対し、基材層に不飽和カルボン酸化合物の多価金属塩溶液を塗工し、溶液に含まれる水分量を乾燥せずに７０重量％の水分を含む状態で、不飽和カルボン酸化合物の多価金属塩を予備重合し、引き続き本重合して得た場合（実施例１）は、得られるガスバリア性積層フィルムは参考例１で得られるガスバリア性積層フィルムに比べ、幾分酸素バリア性及び透明性に優れる。とくに、溶液に含まれる水分量を乾燥せずに７０重量％の水分を含む状態で不飽和カルボン酸化合物の多価金属塩を予備重合し、次いで、本重合する前に、予備重合膜を乾燥し含まれる水分量を３０重量％〜６重量％（実施例３〜５）と低くしても、酸素バリア性及び透明性に優れたガスバリア性積層フィルムが得られること、即ち、予備重合することにより、本重合前の水分量を厳しく調整する必要がなくなることが明らかであり、ガスバリア性積層フィルムの製造条件に余裕ができる。
As is clear from Tables 1 and 2, the polyvalent metal salt of the unsaturated carboxylic acid compound is obtained by irradiating the polyvalent metal salt solution of the unsaturated carboxylic acid compound coated on the base material layer with ionizing radiation such as ultraviolet rays. In the polymerization, the presence of a solvent such as water is important.
Moreover, as shown in Reference Examples 1 to 5, when the amount of water contained in the polyvalent metal salt solution of the unsaturated carboxylic acid compound was changed, the amount of water contained in the solution was adjusted to 45% by weight for polymerization. In the case of (Reference Example 2), a gas barrier laminate film excellent in both oxygen barrier properties and transparency can be obtained, but the amount of water contained in the solution is as high as 70% by weight (Reference Example 1), or 30% by weight. In the state described below (Reference Examples 3 to 5), when a polyvalent metal salt of an unsaturated carboxylic acid compound is polymerized, there is a possibility that a gas barrier laminate film excellent in both oxygen barrier properties and transparency may not be obtained. It can be seen that it is necessary to strictly adjust the water content during polymerization.
On the other hand, a polyvalent metal salt solution of an unsaturated carboxylic acid compound is applied to the base material layer, and the moisture content of the unsaturated carboxylic acid compound is not dried and contains 70% by weight of water. In the case where the polyvalent metal salt was prepolymerized and then obtained by subsequent main polymerization (Example 1), the obtained gas barrier laminate film was somewhat more oxygen barrier and less than the gas barrier laminate film obtained in Reference Example 1. Excellent transparency. In particular, the polyvalent metal salt of an unsaturated carboxylic acid compound is prepolymerized in a state containing 70% by weight of water without drying the amount of water contained in the solution, and then the prepolymerized film is dried before main polymerization. Even when the water content is as low as 30 wt% to 6 wt% (Examples 3 to 5), a gas barrier laminate film excellent in oxygen barrier properties and transparency can be obtained, that is, prepolymerized. Thus, it is clear that there is no need to strictly adjust the amount of water before the main polymerization, and the production conditions for the gas barrier laminate film can be afforded.
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、高湿度下での耐酸素透過性（ガスバリア性）に優れているので、かかる特徴を活かして、包装材料、特に高いガスバリア性が要求される内容物の食品包装材料を始め、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。 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 gas barrier properties are excellent in oxygen permeation resistance (gas barrier properties) under high humidity. Therefore, taking advantage of such characteristics, it can be suitably used as packaging materials, particularly food packaging materials having contents that require high gas barrier properties, as well as various packaging materials such as medical uses and industrial uses.
Claims (5)
Polyhydric prepolymerization metal salt The process of claim 1 Symbol placement of the gas barrier film performing polymerization rate of polyvalent metal salt of an unsaturated carboxylic acid compound in 70% or less of an unsaturated carboxylic acid compound.
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| KR101696497B1 (en) * | 2009-04-15 | 2017-01-13 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Process and apparatus for coating with reduced defects |
| JP5619051B2 (en) * | 2012-02-29 | 2014-11-05 | 富士フイルム株式会社 | Method for producing a film with a coating film |
| JP5244248B2 (en) * | 2012-03-07 | 2013-07-24 | 三井化学東セロ株式会社 | Method for producing gas barrier laminated film |
| KR102154108B1 (en) | 2013-03-26 | 2020-09-09 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Active-energy-ray-curable resin, and gas barrier laminate comprising cured product of said resin |
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| JPS51141808A (en) * | 1975-05-29 | 1976-12-07 | Asada Kagaku Kogyo Kk | Process for preparation of reactive carboxylic acid divalent metal com plexes |
| JP2003286349A (en) * | 2001-01-29 | 2003-10-10 | Nippon Kayaku Co Ltd | Molded articles |
| WO2003091317A1 (en) * | 2002-04-23 | 2003-11-06 | Kureha Chemical Industry Company, Limited | Film and process for producing the same |
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| JPS51141808A (en) * | 1975-05-29 | 1976-12-07 | Asada Kagaku Kogyo Kk | Process for preparation of reactive carboxylic acid divalent metal com plexes |
| JP2003286349A (en) * | 2001-01-29 | 2003-10-10 | Nippon Kayaku Co Ltd | Molded articles |
| WO2003091317A1 (en) * | 2002-04-23 | 2003-11-06 | Kureha Chemical Industry Company, Limited | Film and process for producing the same |
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