JP4917299B2 - Stretched molded body and method for producing the same - Google Patents
Stretched molded body and method for producing the same Download PDFInfo
- Publication number
- JP4917299B2 JP4917299B2 JP2005325482A JP2005325482A JP4917299B2 JP 4917299 B2 JP4917299 B2 JP 4917299B2 JP 2005325482 A JP2005325482 A JP 2005325482A JP 2005325482 A JP2005325482 A JP 2005325482A JP 4917299 B2 JP4917299 B2 JP 4917299B2
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- JP
- Japan
- Prior art keywords
- carboxylic acid
- unsaturated carboxylic
- polyvalent metal
- layer
- acid compound
- 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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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 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
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- 238000009832 plasma treatment Methods 0.000 description 1
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- 238000012805 post-processing Methods 0.000 description 1
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- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
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- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
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- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
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- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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延伸フィルムなどの延伸成形体及びその製造方法に関する。 The present invention relates to a stretched molded article such as a stretched film having transparency and excellent gas barrier properties such as oxygen and water vapor, particularly gas barrier properties under high humidity, and a method for producing the same.
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、透明性を有し、酸素、炭酸ガス等のガスバリア性、特に高湿度下でのガスバリア性に優れた延伸フィルムなどの延伸成形体を得ることを目的とした。 Therefore, an object of the present invention is to obtain a stretched molded body such as a stretched film having transparency and excellent gas barrier properties such as oxygen and carbon dioxide, particularly gas barrier properties under high humidity.
本発明は、少なくとも一方向に延伸された基材層（Ｘ）の少なくとも片面に、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未満である不飽和カルボン酸化合物多価金属塩の重合体（ａ）を含有する層（Ｙ）が形成されてなることを特徴とする延伸成形体に関する。 In the present invention, at least one surface of the base material layer (X) stretched in at least one direction has an absorbance A 0 based on νC═O of a carboxylic acid group near 1700 cm −1 in the infrared absorption spectrum and a carboxy near 1520 cm −1. Formation of a layer (Y) containing a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt having a ratio (A 0 / A) to an absorbance A based on νC═O of rate ions of less than 0.25 It is related with the extending | stretching molded object characterized by being made.
本発明は、少なくとも一軸方向に延伸された基材層（Ｘ）の少なくとも片面に、重合度が２０未満の不飽和カルボン酸化合物多価金属塩を含有する溶液（ｓ）を塗工した後、不飽和カルボン酸化合物多価金属塩を重合し、不飽和カルボン酸化合物多価金属塩の重合体（ａ）を含有する層（Ｙ）を形成することを特徴とする延伸成形体の製造方法に関する。
また本発明は、未延伸の基材層（Ｘ）の少なくとも片面に、重合度が２０未満の不飽和カルボン酸化合物多価金属塩を含有する溶液（ｓ）を塗工し、延伸処理と同時及び／または延伸処理の後に、不飽和カルボン酸化合物多価金属塩の重合物（ａ）を含有する層（Ｙ）を形成させることを特徴とする延伸成形体の製造方法に関する。
In the present invention, after applying a solution (s) containing an unsaturated carboxylic acid compound polyvalent metal salt having a polymerization degree of less than 20 on at least one surface of the base material layer (X) stretched in at least uniaxial direction, The present invention relates to a method for producing a stretched molded article, characterized by polymerizing an unsaturated carboxylic acid compound polyvalent metal salt to form a layer (Y) containing the polymer (a) of the unsaturated carboxylic acid compound polyvalent metal salt. .
In the present invention, at least one surface of the unstretched substrate layer (X) is coated with a solution (s) containing an unsaturated carboxylic acid compound polyvalent metal salt having a polymerization degree of less than 20, and simultaneously with the stretching treatment. And / or, after the stretching treatment, a layer (Y) containing a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt is formed.
本発明の不飽和カルボン酸化合物多価金属塩の重合体（ａ）を含有する層（Ｙ）が形成された延伸フィルムなどの延伸成形体は高湿度下でのガスバリア性に優れている。
本発明の製造方法は、重合度が２０未満の不飽和カルボン酸化合物を用いることにより、基材層の片面あるいは両面に塗工することが容易であり、しかも、中和度が高い、即ち、ガスバリア性に優れる不飽和カルボン酸多価金属化合物の重合体（ａ）を含有する層（Ｙ）を有する延伸成形体を容易に製造することができる。
The stretched molded article such as a stretched film on which the layer (Y) containing the polymer (a) of the unsaturated carboxylic acid compound polyvalent metal salt of the present invention is formed has excellent gas barrier properties under high humidity.
The production method of the present invention can be easily applied to one or both sides of the base material layer by using an unsaturated carboxylic acid compound having a polymerization degree of less than 20, and has a high degree of neutralization. It is possible to easily produce a stretched molded article having a layer (Y) containing a polymer (a) of an unsaturated carboxylic acid polyvalent metal compound having excellent gas barrier properties.
延伸成形体
本発明の延伸形成体は、フィルム、シート、テープ、繊維などの成形体として特に限定することなく用いることができる。
本発明の延伸フィルム等の延伸成形体は、少なくとも一軸方向に延伸された基材層（Ｘ）の少なくとも片面に前記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未満である不飽和カルボン酸化合物多価金属塩の重合体（ａ）を含有する層（Ｙ）が形成されている。重合体（ａ）を含有する層（Ｙ）は延伸フィルムの片面に形成さていても、両面に形成されていてもよい。
延伸フィルム
本発明の延伸フィルムの厚さは用途に応じて種々決定され得るが、通常は、基材層の厚さが５〜５００μｍ、好ましくは５〜１００μｍ、より好ましくは９〜３０μｍ、不飽和カルボン酸化合物多金属塩の共重合体層の厚さが０．０１〜１００μｍ、好ましくは０．０５〜５０μｍ、より好ましくは０．１〜１０μｍ、ガスバリア性積層体の全体の厚さが２０〜７５０μｍ、より好ましくは２５〜４３０μｍの範囲にある。
Stretched molded body The stretched molded body of the present invention can be used without any particular limitation as a molded body of a film, sheet, tape, fiber or the like.
The stretched molded product such as the stretched film of the present invention has an absorbance A based on νC═O of a carboxylic acid group near 1700 cm −1 in the infrared absorption spectrum on at least one surface of the base material layer (X) stretched at least in a uniaxial direction. 0 and 1520cm ratio between the absorbance a, based on the νC = O -1 vicinity of carboxylate ion (a 0 / a) is less than 0.25 unsaturated carboxylic acid compound polyvalent polymer metal salt (a) The containing layer (Y) is formed. The layer (Y) containing the polymer (a) may be formed on one side of the stretched film or may be formed on both sides.
Stretched film Although the thickness of the stretched film of the present invention can be variously determined depending on the application, the thickness of the base layer is usually 5 to 500 μm, preferably 5 to 100 μm, more preferably 9 to 30 μm, and unsaturated. The thickness of the copolymer layer of the carboxylic acid compound polymetal salt is 0.01 to 100 μm, preferably 0.05 to 50 μm, more preferably 0.1 to 10 μm, and the total thickness of the gas barrier laminate is 20 to 20 μm. It exists in the range of 750 micrometers, More preferably, 25-430 micrometers.
基材層（Ｘ）
本発明の延伸形成体を構成する基材層（Ｘ）は、熱可塑性樹脂からなるフィルム、シート、テープ、繊維など特に限定することなく用いることができる。
熱可塑性樹脂としては、種々公知の熱可塑性樹脂、例えば、ポリオレフィン（ポリエチレン、ポリプロピレン、ポリ４−メチル・１−ペンテン、ポリブテン等）、ポリエステル（ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等）、ポリアミド（ナイロン−６、ナイロン−６６、ポリメタキシレンアジパミド等）、ポリ塩化ビニル、ポリイミド、エチレン・酢酸ビニル共重合体もしくはその鹸化物、ポリビニルアルコール、ポリアクリロニトリル、ポリカーボネート、ポリスチレン、アイオノマー、あるいはこれらの混合物等を例示することができる。これらのうちでは、ポリプロピレン、ポリエステル、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く、とくにポリエチレンテレフタレート及びポリエチレンナフタレート等のポリエステルがバリア性、耐熱性等に優れているので好ましい。
基材層（Ｘ）は、少なくとも一軸方向に延伸された基材層であり、延伸された基材層は、耐熱性、剛性、透明性及びガスバリア性に優れている。
また、これら基材層（Ｘ）は、ガスバリア性に優れた層（Ｙ）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。
重合体（ａ）を含有する層（Ｙ）
基材層（Ｘ）の片面または両面には、不飽和カルボン酸化合物多価金属塩の重合体（ａ）を含有する層（Ｙ）が形成される。
Base material layer (X)
The base material layer (X) constituting the stretch-formed product of the present invention can be used without any particular limitation, such as a film, sheet, tape, fiber, etc. made of a thermoplastic resin.
As the thermoplastic resin, various known thermoplastic resins such as polyolefin (polyethylene, polypropylene, poly-4-methyl / 1-pentene, polybutene, etc.), polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide (Nylon-6, nylon-66, polymetaxylene adipamide, etc.), polyvinyl chloride, polyimide, ethylene / vinyl acetate copolymer or saponified product thereof, polyvinyl alcohol, polyacrylonitrile, polycarbonate, polystyrene, ionomer, or these And the like. Of these, polypropylene, polyester, polyamide and the like are preferable thermoplastic resins having good stretchability and transparency, and polyesters such as polyethylene terephthalate and polyethylene naphthalate are particularly preferable because of excellent barrier properties and heat resistance.
The base material layer (X) is a base material layer stretched at least in a uniaxial direction, and the stretched base material layer is excellent in heat resistance, rigidity, transparency, and gas barrier properties.
Moreover, in order to improve adhesiveness with the layer (Y) excellent in gas barrier property, these base material layers (X), for example, corona treatment, flame treatment, plasma treatment, undercoat treatment, primer A surface activation process such as a coating process or a frame process may be performed.
Layer (Y) containing polymer (a)
A layer (Y) containing a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt is formed on one surface or both surfaces of the base material layer (X).
不飽和カルボン酸化合物多価金属塩の重合体（ａ）
不飽和カルボン酸化合物多価金属塩の重合体（ａ）は、不飽和カルボン酸多価金属塩を重合することによって得ることができる。
不飽和カルボン酸化合物
重合体（ａ）に用いられる不飽和カルボン酸化合物多価金属塩を形成する不飽和カルボン酸化合物は、アクリル酸、メタアクリル酸、マレイン酸、イタコン酸等のα、β−エチレン性不飽和基を有するカルボン酸化合物であり、重合度が２０未満、好ましくは単量体若しくは重合度１０以下の重合体である。重合度が２０を越える重合体（高分子化合物）を用いた場合は、後述の多価金属化合物との塩が完全には形成されない虞があり、その結果、当該金属塩を重合して得られる層は高湿度下でのガスバリア性が劣る虞がある。これら不飽和カルボン酸化合物は、一種でも二種以上の混合物であってもよい。
これら不飽和カルボン酸化合物の中でも単量体が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重合体層を基材層の少なくとも片面に積層してなるガスバリア性積層体は高湿度下でのガスバリア性に特に優れるので好ましい。
Polymer (a) of unsaturated carboxylic acid compound polyvalent metal salt
The polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt can be obtained by polymerizing an unsaturated carboxylic acid polyvalent metal salt.
The unsaturated carboxylic acid compound forming the unsaturated carboxylic acid compound polyvalent metal salt used in the unsaturated carboxylic acid compound polymer (a) is α, β-, such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid. It is a carboxylic acid compound having an ethylenically unsaturated group, and has a polymerization degree of less than 20, preferably a monomer or a polymer having a polymerization degree of 10 or less. When a polymer (polymer compound) having a degree of polymerization exceeding 20 is used, a salt with a polyvalent metal compound described later may not be completely formed. As a result, it is obtained by polymerizing the metal salt. The layer may have poor gas barrier properties under high humidity. These unsaturated carboxylic acid compounds may be one kind or a mixture of two or more kinds.
Among these unsaturated carboxylic acid compounds, it is easy to form a salt in which the monomer is completely neutralized with a polyvalent metal compound, and a polymer layer obtained by polymerizing the salt is laminated on at least one side of the base material layer. The gas barrier laminate thus obtained is preferable because it is particularly excellent in gas barrier properties under high humidity.
多価金属化合物
本発明に係わる不飽和カルボン酸化合物多価金属塩を形成する成分である多価金属化合物は、周期表の２Ａ〜７Ａ族、１Ｂ〜３Ｂ族及び８族に属する金属及び金属化合物であり、具体的には、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、バリウム（Ｂａ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、銅（Ｃｕ）、亜鉛（Ｚｎ）、アルミニウム（Ａｌ）等の二価以上の金属、これら金属の酸化物、水酸化物、ハロゲン化物、炭酸塩、リン酸塩、亜リン酸塩、次亜リン酸塩、硫酸塩若しくは亜硫酸塩等である。これら金属化合物の中でも、二価の金属化合物が好ましく、特には酸化マグネシウム、酸化カルシウム、酸化バリウム、酸化亜鉛、水酸化マグネシウム、水酸化カルシウム、水酸化バリウム、水酸化亜鉛等が好ましい。これら二価の金属化合物を用いた場合は、前記不飽和カルボン酸化合物との塩を重合して得られる層（Ｙ）の高湿度下でのガスバリア性が特に優れている。これら多価金属化合物は、少なくとも一種が使用され、一種のみの使用であっても、二種以上を併用してもよい。これら多価金属化合物の中でもＭｇ、Ｃａ、Ｚｎ、ＢａおよびＡｌ、特にＺｎが好ましい。
Polyvalent metal compound The polyvalent metal compound which is a component forming the unsaturated carboxylic acid compound polyvalent metal salt according to the present invention is a metal or metal compound belonging to groups 2A to 7A, 1B to 3B and 8 of the periodic table. Specifically, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc ( Zn), bivalent or higher metals such as aluminum (Al), oxides, hydroxides, halides, carbonates, phosphates, phosphites, hypophosphites, sulfates or sulfites of these metals Such as salt. 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 layer (Y) obtained by polymerizing a salt with the unsaturated carboxylic acid compound is particularly excellent. At least one kind of these polyvalent metal compounds is used, and only one kind may be used or two or more kinds may be used in combination. Among these polyvalent metal compounds, Mg, Ca, Zn, Ba and Al, and particularly Zn are preferable.
不飽和カルボン酸化合物多価金属塩
本発明に用いられる不飽和カルボン酸化合物多価金属塩の重合体（ａ）を構成する成分である不飽和カルボン酸化合物多価金属塩は、前記重合度が２０未満の不飽和カルボン酸化合物と前記多価金属化合物との塩である。これら不飽和カルボン酸化合物多価金属塩は一種でも二種以上の混合物であってもよい。かかる不飽和カルボン酸化合物多価金属塩の中でも、特に（メタ）アクリル酸亜鉛が得られる重合体層の耐熱水性に優れるので好ましい。
Unsaturated carboxylic acid compound polyvalent metal salt The unsaturated carboxylic acid compound polyvalent metal salt, which is a component constituting the polymer (a) of the unsaturated carboxylic acid compound polyvalent metal salt used in the present invention, has the above-mentioned degree of polymerization. It is a salt of an unsaturated carboxylic acid compound 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 such unsaturated carboxylic acid compound polyvalent metal salts, the polymer layer from which zinc (meth) acrylate is obtained is particularly excellent in the hot water resistance, which is preferable.
本発明における重合体（ａ）を含有する層（Ｙ）は、本発明の目的を損なわない範囲で、ポリビニルアルコール、エチレン・ビニルアルコール共重合体、ポリビニルピロリドン、ポリビニルエチルエーテル、ポリアクリルアミド、ポリエチレンイミン、澱粉、アラビアガム、メチルセルロース等の水溶性重合体、アクリル酸エステル重合体、エチレン・アクリル酸共重合体、ポリ酢酸ビニル、エチレン・酢酸ビニル共重合体、ポリエステル、ポリウレタン等の高分子量の化合物等、滑剤、スリップ剤、アンチ・ブロッキング剤、帯電防止剤、防曇剤、顔料、染料、無機また有機の充填剤等の各種添加剤が含まれていてもよいし、後述の基材との濡れ性、密着性等を改良するために、各種界面活性剤等が含まれていてもよい。これらの他の成分の割合は、必要に応じて変えることができる。 The layer (Y) containing the polymer (a) in the present invention is within the range not impairing the object of the present invention, and polyvinyl alcohol, ethylene / vinyl alcohol copolymer, polyvinyl pyrrolidone, polyvinyl ethyl ether, polyacrylamide, polyethyleneimine Water-soluble polymers such as starch, gum arabic and methylcellulose, acrylic acid ester polymers, ethylene / acrylic acid copolymers, polyvinyl acetate, ethylene / vinyl acetate copolymers, polyesters, polyurethanes and other high molecular weight compounds Various additives such as lubricants, slip agents, anti-blocking agents, antistatic agents, antifogging agents, pigments, dyes, inorganic or organic fillers may be included, and wetting with the substrate described below Various surfactants and the like may be included in order to improve the properties and adhesion. The proportions of these other components can be varied as required.
これらの中でも、ビニルアルコール系重合体（ｂ）は、基材層（Ｘ）にコーティングしやすく、ガスバリア性にも優れているので、併用することが望ましい。
即ち、本発明の重合体（ａ）を含有する層（Ｙ）は、不飽和カルボン酸化合物多価金属塩の重合体（ａ）およびビニルアルコール系重合体（ｂ）からなること好適である。
ビニルアルコール重合体（ｂ）
ビニルアルコール系重合体としては、ポリビニルアルコール、エチレン−ビニルアルコール共重合体、変性ビニルアルコール系重合体などがある。ポリビニルアルコールは混合可能であれば特に問題ないが、好ましくは重合度が１００〜３０００、更には２００〜２５００、最も好ましくは３００〜２０００の範囲にある。この範囲にあると、水溶液にして基材層にコーティングし易く延伸性、ガスバリア性も良い。また、ケン化度は９０％以上、好ましくは９５％以上であり、この範囲であればガスバリア性が良い。また、耐水性や延伸性からオレフィン含有ポリビニルアルコールを使用してもよい。オレフィン含有量が０〜２５モル％、好ましくは１〜２０モル％、更には２〜１６モル％、オレフィンとしては、炭素数４以下のものが好ましく、エチレン、プロピレン、ｎ−ブテン、イソブテン等が挙げられるが、耐水性の点でエチレンが最も好ましい。
また、ビニルアルコール系重合体の好適な例として、変性ビニルアルコール系重合体がある。
変性ビニルアルコール系重合体としては、ビニルアルコール系重合体に、種々の公知の反応性を有する基（反応性基）を付加、置換、あるいはエステル化等により反応性基を結合して変性したもの、酢酸ビニル等のビニルエステルと反応性基を有する不飽和化合物とを共重合して得た共重合体を鹸化したもの等を挙げることができる。これら反応性重合基としては、（メタ）アクリレート基、（メタ）アクリロイル基、（メタ）アクリルアミド基、ビニル基、アリル基、スチリル基、チオール基、シリル基、アセトアセチル基、エポキシ基などが挙げられる。反応性基の量は、適宜決めることができるが、基体となるビニルアルコール系重合体のＯＨ基の量が少なくなるとビニルアルコール系重合体が本来有するガスバリア性が損なわれる虞があるので、通常、反応性基の量は、０．００１〜５０モル％の範囲にある（反応性基とＯＨ基の合計で１００モル％とする）。また、これら変性ビニルアルコール系重合体は、好ましくは水、低級アルコール、有機溶媒に溶解性であるものであり、特に水−低級アルコール系混合溶媒に溶解するものが好ましい。
Among these, since the vinyl alcohol polymer (b) is easy to coat the base material layer (X) and has excellent gas barrier properties, it is desirable to use it together.
That is, the layer (Y) containing the polymer (a) of the present invention is preferably composed of a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt and a vinyl alcohol polymer (b).
Vinyl alcohol polymer (b)
Examples of the vinyl alcohol polymer include polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, and a modified vinyl alcohol polymer. Polyvinyl alcohol has no particular problem as long as it can be mixed, but preferably has a degree of polymerization of 100 to 3000, more preferably 200 to 2500, and most preferably 300 to 2000. Within this range, the base layer is easily coated with an aqueous solution and has good stretchability and gas barrier properties. Further, the saponification degree is 90% or more, preferably 95% or more. If it is within this range, the gas barrier property is good. Moreover, you may use olefin containing polyvinyl alcohol from water resistance or extending | stretching property. The olefin content is 0 to 25 mol%, preferably 1 to 20 mol%, more preferably 2 to 16 mol%, and the olefin is preferably those having 4 or less carbon atoms, such as ethylene, propylene, n-butene, isobutene and the like. Among them, ethylene is most preferable from the viewpoint of water resistance.
A suitable example of the vinyl alcohol polymer is a modified vinyl alcohol polymer.
The modified vinyl alcohol polymer is modified by adding a reactive group to the vinyl alcohol polymer by adding, replacing, or esterifying various known reactive groups (reactive groups). And a saponified copolymer obtained by copolymerizing a vinyl ester such as vinyl acetate and an unsaturated compound having a reactive group. Examples of these reactive polymerizable groups include (meth) acrylate groups, (meth) acryloyl groups, (meth) acrylamide groups, vinyl groups, allyl groups, styryl groups, thiol groups, silyl groups, acetoacetyl groups, and epoxy groups. It is done. The amount of the reactive group can be appropriately determined, but since the gas barrier property inherent to the vinyl alcohol polymer may be impaired when the amount of the OH group of the vinyl alcohol polymer serving as the substrate is decreased, usually, The amount of reactive groups is in the range of 0.001 to 50 mol% (the total of reactive groups and OH groups is 100 mol%). These modified vinyl alcohol polymers are preferably soluble in water, lower alcohols, and organic solvents, and those that are particularly soluble in water-lower alcohol mixed solvents are preferred.
ビニルアルコール系重合体の水溶液には、水以外の溶媒、例えばメタノール、エタノール、イソプロパノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、或いはその他ジエチルエーテル、テトラヒドロフラン等を必要に応じて、１種または２種以上を組み合わせて加えることも可能である。又、ポリビニルアルコール系重合体には、本発明の特徴を阻害しない範囲で濡れ性向上剤、帯電防止剤、その他各種添加剤を加えることが可能である。
これらビニルアルコール系重合体（ｂ）を併用する場合、本発明の重合体（ａ）を含有する層（Ｙ）は、一般に、不飽和カルボン酸化合物多価金属塩の重合体（ａ）が１〜９９重量％、ビニルアルコール系重合体（ｂ）が１〜９９重量％から構成されることが通常である。
重合体（ａ）を含有する層（Ｙ）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（ａ）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（ａ）を含有する層（Ｙ）は、ガスバリア性に優れており、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、重合体（ａ）を含有する層（Ｙ）の（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を越える膜からなる層は、遊離のカルボン酸基の含有量が多く、高湿度下での耐ガスバリア性が改良されない虞がある。
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、延伸フィルム（ガスバリア性に優れた積層体）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（ａ）を含有する層（Ｙ））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。
In the aqueous solution of the vinyl alcohol polymer, a solvent other than water, for example, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, or other diethyl ether, tetrahydrofuran and the like, if necessary, It is also possible to add two or more types in combination. In addition, a wettability improver, an antistatic agent, and other various additives can be added to the polyvinyl alcohol polymer as long as the characteristics of the present invention are not impaired.
When these vinyl alcohol polymers (b) are used in combination, the layer (Y) containing the polymer (a) of the present invention generally has a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt of 1 (1). It is usually composed of ˜99% by weight and the vinyl alcohol polymer (b) from 1 to 99% by weight.
The layer (Y) containing the polymer (a) usually has an absorbance A 0 based on νC═O of carboxylic acid groups near 1700 cm −1 in the infrared absorption spectrum and νC═O of carboxylate ions near 1520 cm −1. A polymer (a) of a polyvalent metal salt of an unsaturated carboxylic acid compound having a ratio (A 0 / A) with an absorbance A based on the formula (A 0 / A) of less than 0.25, preferably less than 0.20.
The layer (Y) containing a polymer (a) of a polyvalent metal salt of an unsaturated carboxylic acid compound has excellent gas barrier properties, and is free from carboxylate ions formed by ionic crosslinking of a carboxylic acid group and a polyvalent metal. In the infrared spectrum, the absorption based on νC═O of the free carboxylic acid group is around 1700 cm −1 , and the absorption based on νC═O of the carboxylate ion is around 1520 cm −1 , respectively. is there.
Therefore, the fact that the (A 0 / A) of the layer (Y) containing the polymer (a) is less than 0.25 indicates that there are no or few free carboxylic acid groups. A layer composed of 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) Cut out a sample for measurement of 1 cm × 3 cm from a stretched film (a laminate having excellent gas barrier properties), and its surface (layer (Y) containing an unsaturated carboxylic acid compound polyvalent metal salt polymer (a)). An infrared absorption spectrum was obtained by infrared total reflection measurement (ATR method), and absorbance A 0 and absorbance A were first determined by the following procedure.
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。
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.
延伸フィルムの製造方法（１）
本発明の延伸フィルムの製造する方法としては、延伸された基材層の少なくとも片面に、重合度が２０未満の不飽和カルボン酸化合物多価金属塩を含有する溶液（ｓ）を塗工した後、不飽和カルボン酸化合物多価金属塩を重合し、不飽和カルボン酸化合物多価金属塩の重合体（ａ）を含有する層（Ｙ）を形成させる方法がある。
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含有する溶液（ｓ）を作成する方法としては、予め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、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。
本発明の延伸フィルムの製造方法として、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有する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化学当量比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化学当量比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重合体層となり、結果として、ガスバリア性が低い延伸フィルムとなる虞がある。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化学当量比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化学当量比以下、好ましくは２化学当量比以下で十分である。
なお、本発明における化学当量比は、不飽和カルボン酸化合物に対する多価金属化合物の化学当量比を示し、以下の式により算出される値である。
化学当量比＝（多価金属化合物のモル数）×（多価金属化合物の価数）／不飽和カルボン酸化合物に含まれるカルボキシル基のモル数
例えば、多価金属化合物として水酸化カルシウム（分子量７４ｇ／モル）を３７ｇ、不飽和カルボン酸化合物としてアクリル酸単量体（分子量７２ｇ／モル）７２ｇを混合した場合の化学当量比は１となる。
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多価金属塩の溶液に用いる溶媒は、水、メチルアルコール、エチルアルコール、イソプロピルアルコール等の低級アルコール若しくはアセトン、メチルエチルケトン等の有機溶媒あるいはそれらの混合溶媒が挙げられるが、水が最も好ましい。
Manufacturing method of stretched film (1)
As a method for producing the stretched film of the present invention, after applying a solution (s) containing an unsaturated carboxylic acid compound polyvalent metal salt having a degree of polymerization of less than 20 on at least one side of the stretched substrate layer There is a method of polymerizing an unsaturated carboxylic acid compound polyvalent metal salt to form a layer (Y) containing a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt.
As a method for preparing a solution (s) containing an unsaturated carboxylic acid compound polyvalent metal salt having a degree of polymerization of less than 20, the unsaturated carboxylic acid compound and the polyvalent metal compound are reacted in advance and unsaturated. The polyvalent metal salt of the carboxylic acid compound may be used as 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.
As a method for producing a stretched 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 equivalent ratio with respect to the unsaturated carboxylic acid compound. When a mixed solution having a polyvalent metal compound addition amount of 0.3 chemical equivalent ratio or less is used, a polymer layer having a large content of free carboxylic acid groups is obtained, and as a result, a stretched film having a low gas barrier property is obtained. There is a fear. In addition, the upper limit of the amount of polyvalent metal compound added is not particularly limited, but when the amount of polyvalent metal compound added exceeds 1 chemical equivalent ratio, unreacted polyvalent metal compound increases. The ratio is preferably less than the ratio, preferably less than the 2 chemical equivalent ratio.
In addition, the chemical equivalent ratio in this invention shows the chemical equivalent ratio of the polyvalent metal compound with respect to an unsaturated carboxylic acid compound, and is a value calculated by the following formula | equation.
Chemical equivalent ratio = (number of moles of polyvalent metal compound) × (valence of polyvalent metal compound) / number of moles of carboxyl group contained in unsaturated carboxylic acid compound For example, calcium hydroxide (molecular weight 74 g) as the polyvalent metal compound The chemical equivalent ratio is 1 when 37 g of acrylic acid monomer (molecular weight 72 g / mol) is mixed as an unsaturated carboxylic acid compound.
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 the solution of the unsaturated carboxylic acid compound polyvalent metal salt include water, lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, organic solvents such as acetone and methyl ethyl ketone, and mixed solvents thereof. Most preferred.
基材層（Ｘ）に不飽和カルボン酸化合物の多価金属塩を含有する溶液（ｓ）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（Ｘ）に不飽和カルボン酸化合物の多価金属塩を含有する溶液（ｓ）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（ｓ）中（固形分）の量で０．０５〜１００ｇ／ｍ２、好ましくは０．１〜５０ｇ／ｍ２となるよう塗布すればよい。基材層（Ｘ）の表面に不飽和カルボン酸化合物多価金属塩の溶液（ｓ）を塗工する方法としては、種々公知の方法、例えば、刷毛等により塗布する方法、当該溶液（ｓ）に基材層（Ｘ）を浸漬する方法、当該溶液（ｓ）を基材層（Ｘ）の表面に噴霧する方法等を採り得る。
As a method of applying the solution (s) containing the polyvalent metal salt of an unsaturated carboxylic acid compound to the base material layer (X), a method of applying the solution to the surface of the base material layer, a base material layer on the solution Various known coating methods such as a method of immersing the solution and a method of spraying the solution on the surface of the base material layer can be employed.
Examples of the method for applying the solution (s) containing the polyvalent metal salt of the unsaturated carboxylic acid compound to the base material layer (X) include an air knife coater, a direct gravure coater, a gravure offset, an arc gravure coater, and a gravure reverse. And various other known types such as a gravure coater such as a jet nozzle method, a reverse roll coater such as a top feed reverse coater, a bottom feed reverse coater and a nozzle feed reverse coater, a 5-roll coater, a lip coater, a bar coater, a bar reverse coater, and a die coater. Using a coating machine, the amount in the solution (s) of the unsaturated carboxylic acid compound polyvalent metal salt (solid content) is 0.05 to 100 g / m 2 , preferably 0.1 to 50 g / m 2. It may be applied as follows. As a method of applying the solution (s) of the unsaturated carboxylic acid compound polyvalent metal salt to the surface of the base material layer (X), various known methods, for example, a method of applying with a brush or the like, the solution (s) For example, a method of immersing the base material layer (X), a method of spraying the solution (s) on the surface of the base material layer (X) and the like can be employed.
不飽和カルボン酸化合物多価金属塩を溶解させる際には、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）アクリル酸エチルなどの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、滑剤、スリップ剤、アンチ・ブロッキング剤、帯電防止剤、防曇剤、顔料、染料、無機また有機の充填剤等の各種添加剤を添加しておいてもよいし、基材層との濡れ性を改良するために、各種界面活性剤等を添加しておいてもよい。 When the unsaturated carboxylic acid compound polyvalent metal salt is dissolved, other unsaturated carboxylic acids (di) such as methyl (meth) acrylate and ethyl (meth) acrylate, as long as the object of the present invention is not impaired. Monomers such as ester compounds, vinyl ester compounds such as vinyl acetate, or low molecular weight compounds, lubricants, slip agents, anti-blocking agents, antistatic agents, antifogging agents, pigments, dyes, inorganic or organic fillers, etc. In order to improve the wettability with the base material layer, various surfactants and the like may be added.
基材層（Ｘ）の少なくとも片面に形成した（塗工した）不飽和カルボン酸化合物多価金属塩の溶液（塗工層）を重合させるには、種々公知の方法、具体的には例えば、電離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、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 (coating layer) of the unsaturated carboxylic acid compound polyvalent metal salt formed (coated) on at least one surface of the base material layer (X), various known methods, specifically, for example, Examples thereof include irradiation with ionizing radiation and 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 unsaturated carboxylic acid compound polyvalent metal salt. As the photopolymerization initiator, known ones can be used. For example, 2-hydroxy-2methyl-1-phenyl-propan-1-one (trade name; Darocur 1173, manufactured by Ciba Specialty Chemicals), 1-Hydroxy-cyclohexyl ruphenyl ketone (Ciba Specialty Chemicals product name; Irgacure 184), Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba Specialty Chemicals product name) Irgacure 819), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name; Irgacure 2959, manufactured by Ciba Specialty Chemicals) ), Α-hydroxyketone, acylphosphine oxy A mixture of id, 4-methylbenzophenone and 2,4,6-trimethylbenzophenone (Lamberty Chemical Specialty, trade name; Essaure KT046), Esacure KT55 (Lamberti Chemical Specialty), 2,4,6- A radical polymerization initiator manufactured and sold under the trade name of trimethylbenzoyldiphenylphosphine oxide (trade name; Speed Cure TPO manufactured by Ramson Fire Chemical Co., Ltd.) can be mentioned. Furthermore, a polymerization accelerator can be added to improve the polymerization degree or polymerization rate, and examples thereof include N, N-dimethylamino-ethyl- (meth) acrylate and N- (meth) acryloyl-morpholine. .
不飽和カルボン酸化合物多価金属塩を重合させる際は、溶液（ｓ）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（ｓ）を塗工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重合体層の形成が不十分になり、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、塗工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。 When the unsaturated carboxylic acid compound polyvalent metal salt is polymerized, the solution (s) may be polymerized in a state containing a solvent such as water, or may be polymerized after being partially dried. When (s) is polymerized immediately after coating, the resulting polymer layer may be whitened because of the large evaporation of the solvent when the metal salt is polymerized. On the other hand, the solvent (moisture) decreases, and the unsaturated carboxylic acid compound polyvalent metal salt may precipitate as crystals. When polymerization is performed in such a state, formation of the resulting polymer layer becomes insufficient, resulting in heavy polymerization. There is a possibility that the gas barrier property may not be stable due to whitening of the combined layer. Therefore, when the coated unsaturated carboxylic acid compound polyvalent metal salt is polymerized, it is preferably polymerized in a state containing appropriate moisture.
延伸フィルムの製造方法（２）
本発明の延伸フィルムの他の製造方法として、未延伸の基材層（Ｘ）の少なくとも片面に、重合度が２０未満の不飽和カルボン酸化合物多価金属塩を含有する溶液（ｓ）を塗工し、延伸処理と同時 及び／または 延伸処理の後に、不飽和カルボン酸化合物多価金属塩の重合物（ａ）を含有する層（Ｙ）を形成させることを特徴とする延伸フィルムの製造方法がある。
このような製造方法の具体例の１つとして、未延伸の基材層（Ｘ）の少なくとも片面に、重合度が２０未満の不飽和カルボン酸化合物多価金属塩を含有する溶液（ｓ）を塗工し、不飽和カルボン酸化合物多価金属塩を予備重合させ、予備重合体（ａ’）を含有する層（Ｙ）を形成させ、次いで、当該予備重合体（ａ’）を含有する層（Ｙ）と未延伸の基材層（Ｘ）を共に延伸し、その延伸の際、あるいはその後、当該予備重合物（ａ’）の重合をさらに進め、不飽和カルボン酸化合物多価金属塩の重合体（ａ）を含有する層（Ｙ）を形成することによって延伸フィルムを製造する方法（２−１）がある。
Manufacturing method of stretched film (2)
As another production method of the stretched film of the present invention, a solution (s) containing an unsaturated carboxylic acid compound polyvalent metal salt having a degree of polymerization of less than 20 is applied to at least one surface of the unstretched substrate layer (X). And a layer (Y) containing a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt is formed at the same time and / or after the stretching treatment. There is.
As one specific example of such a production method, a solution (s) containing an unsaturated carboxylic acid compound polyvalent metal salt having a degree of polymerization of less than 20 on at least one surface of the unstretched base material layer (X). Coating, prepolymerizing an unsaturated carboxylic acid compound polyvalent metal salt to form a layer (Y) containing a prepolymer (a ′), and then a layer containing the prepolymer (a ′) (Y) and the unstretched base material layer (X) are stretched together, and at the time of stretching, or thereafter, the prepolymerized product (a ′) is further polymerized, and the unsaturated carboxylic acid compound polyvalent metal salt There is a method (2-1) for producing a stretched film by forming a layer (Y) containing a polymer (a).
延伸フィルムの製造方法（２−１）
この製造方法（２−１）では、未延伸の基材層（Ｘ）の少なくとも片面に、重合度が２０未満の不飽和カルボン酸化合物多価金属塩を含有する溶液（ｓ）を塗工した後に、不飽和カルボン酸化合物多価金属塩を予備重合させて、予備重合体（ａ’）を含有する層（Ｙ）を形成させることを特徴とする。
ここまでの段階で、層（Ｙ）は、予備重合体（ａ’）の状態で、フィルムの形態を保持し始めている。この段階で、当該予備重合体（ａ’）を含有する層（Ｙ）と未延伸の基材層（Ｘ）を共に延伸処理する。
これによって、延伸フィルムが成形される。
Manufacturing method of stretched film (2-1)
In this production method (2-1), a solution (s) containing an unsaturated carboxylic acid compound polyvalent metal salt having a degree of polymerization of less than 20 was applied to at least one surface of the unstretched base material layer (X). Then, the unsaturated carboxylic acid compound polyvalent metal salt is prepolymerized to form a layer (Y) containing the prepolymer (a ′).
At this stage, the layer (Y) is starting to retain the film form in the state of the prepolymer (a ′). At this stage, the layer (Y) containing the prepolymer (a ′) and the unstretched base material layer (X) are both stretched.
Thereby, a stretched film is formed.
予備重合
予備重合は、重合率が高くなり過ぎると予備重合体（ａ’）と未延伸の基材層（Ｘ）を延伸する際に、不飽和カルボン酸化合物多価金属塩の重合体層に亀裂が入る場合があるので、通常、予備重合の重合率（重合率の求め方は下記に示す）を１〜７０％、好ましくは３〜６０％、より好ましくは５〜５０％の範囲にすることが好ましい。
不飽和カルボン酸化合物の多価金属塩の溶液（ｓ）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、ガスバリア性に優れた層（Ｙ）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は、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層（Ｙ）の外観及びガスバリア性が優れる。
In the prepolymerization prepolymerization, when the polymerization rate becomes too high, when the prepolymer (a ′) and the unstretched base material layer (X) are stretched, the polymer layer of the unsaturated carboxylic acid compound polyvalent metal salt is formed. Since cracks may occur, the polymerization rate of pre-polymerization (how to obtain the polymerization rate is shown below) is usually in the range of 1 to 70%, preferably 3 to 60%, more preferably 5 to 50%. It is preferable.
When prepolymerizing the solution (s) of the polyvalent metal salt of the unsaturated carboxylic acid compound, 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 layer (Y) excellent in gas barrier properties.
In the prepolymerization of the unsaturated carboxylic acid compound polyvalent metal salt solution, if the polymerization rate is kept at 70% or less, the water content in the unsaturated carboxylic acid compound polyvalent metal salt solution is as low as 30% by weight or less. However, the appearance and gas barrier properties of the layer (Y) obtained by the main polymerization are excellent.
不飽和カルボン酸化合物多価金属塩の溶液（ｓ）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／ｃｍ２、とくに３〜１５ｍＪ／ｃｍ２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に優れた層（Ｙ）の外観、特に透明性が低下する虞がある。 When the unsaturated carboxylic acid compound polyvalent metal salt solution (s) is preliminarily polymerized by irradiation with ionizing radiation, the irradiation dose of ionizing radiation is usually 1 to 50 mJ / cm 2 , particularly 3 to 15 mJ / cm. A range of 2 is preferable. When the irradiation amount exceeds 50 mJ, the polymerization rate at the time of preliminary polymerization increases, and the appearance of the layer (Y) excellent in gas barrier properties obtained by the main polymerization, particularly transparency, may be deteriorated.
延伸処理および本重合
予備重合の後に、予備重合体（ａ’）と未延伸の基材層（Ｘ）を共に延伸する。
延伸は、一軸または２軸方向に通常１．２〜５０倍程度である。延伸温度は基材層の種類に応じて適宜調整することができる。延伸処理は、少なくとも一軸方向に、１．２〜１０倍程度が通常であり、特に１．２〜５倍が好ましい。延伸温度は、基材層（Ｘ）の素材により適宜調節することができるが、通常は５０℃から２５０℃である。
この製造方法においては、延伸処理の後に、予備重合体（ａ’）を本重合させてもよく、また延伸処理と並行して、予備重合体（ａ’）を本重合させてもよい。
予備重合体（ａ’）は本重合により、不飽和カルボン酸化合物多価金属塩の重合体（ａ）を形成する。
なお、本重合は、予備重合体（ａ’）中の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層（Ｙ）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層（Ｙ）の外観、特に透明性が低下する虞がある。
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５０〜１０００ｍＪ／ｃｍ２、とくに１００〜５００ｍＪ／ｃｍ２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％のガスバリア性に優れた層（Ｙ）が安定して得られる。
After the stretching treatment and main polymerization prepolymerization, the prepolymer (a ′) and the unstretched base material layer (X) are stretched together.
Stretching is usually about 1.2 to 50 times in a uniaxial or biaxial direction. The stretching temperature can be appropriately adjusted according to the type of the base material layer. The stretching treatment is usually about 1.2 to 10 times, particularly preferably 1.2 to 5 times, at least in the uniaxial direction. The stretching temperature can be appropriately adjusted depending on the material of the base material layer (X), but is usually 50 ° C to 250 ° C.
In this production method, the prepolymer (a ′) may be main-polymerized after the stretching treatment, or the prepolymer (a ′) may be main-polymerized in parallel with the stretching treatment.
The prepolymer (a ′) forms a polymer (a) of an unsaturated carboxylic acid compound polyvalent metal salt by main polymerization.
The main polymerization is preferably performed after partially drying the coating solution in the prepolymer (a ′). 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 layer (Y) obtained by the main polymerization may be reduced, and when too much solvent is contained in the coating liquid, the main polymerization is performed. There is a possibility that the appearance of the layer (Y) to be obtained, particularly the transparency, may be lowered.
When performing the polymerization by irradiation with ionizing radiation, usually, 50~1000mJ / cm 2 irradiation amount of ionizing radiation, particularly it is preferably in the range of 100 to 500 mJ / cm 2. By setting the irradiation amount in such a range, a layer (Y) excellent in gas barrier properties having a polymerization rate of 80% or more, preferably 90%, can be stably obtained.
延伸フィルムの製造方法（２−２）
本発明の延伸フィルムの他の製造方法として、未延伸の基材層（Ｘ）の少なくとも片面に、重合度が２０未満の不飽和カルボン酸化合物多価金属塩を含有する溶液（ｓ）を塗工し、未延伸の基材層（Ｘ）と当該重合体（ａ）を含有する層（Ｙ）を共に延伸処理した後、当該不飽和カルボン酸化合物多価金属塩を重合することにより、不飽和カルボン酸化合物多価金属塩の重合体（ａ）を含有する層（Ｙ）を形成することを特徴とする請求項７に記載の延伸成形体の製造方法がある。
Manufacturing method of stretched film (2-2)
As another production method of the stretched film of the present invention, a solution (s) containing an unsaturated carboxylic acid compound polyvalent metal salt having a degree of polymerization of less than 20 is applied to at least one surface of the unstretched substrate layer (X). After the unstretched base material layer (X) and the layer (Y) containing the polymer (a) are stretched together, the unsaturated carboxylic acid compound polyvalent metal salt is polymerized, thereby The layer (Y) containing a polymer (a) of a saturated carboxylic acid compound polyvalent metal salt is formed, and there is a method for producing a stretched molded product according to claim 7.
この製造方法は、製造方法（２−１）とは、予備重合を行うことなく、延伸処理の後に重合を行う点が相違する。なお、延伸倍率、延伸温度は、製造方法（２−１）の場合と同様である。 This manufacturing method is different from the manufacturing method (2-1) in that polymerization is performed after the stretching treatment without performing preliminary polymerization. In addition, a draw ratio and a drawing temperature are the same as in the case of the production method (2-1).
接着性樹脂（ｃ）からなる層（Ｚ）
基材層（Ｘ）と、重合体（ａ）を含有する層（Ｙ）の間には、接着性を高めるために接着性樹脂（ｃ）からなる層（Ｚ）を設けることが望ましい。
接着性樹脂（ｃ）からなる層（Ｚ）として、エポキシ系、ウレタン系、アクリル系などのプライマーをアンダーコートした層が例示される。また、他の好適に用いられる接着性を改良する層（Ｚ）として、接着性樹脂（ｃ）からなる層（Ｚ）がある。
Layer (Z) made of adhesive resin (c)
Between the base material layer (X) and the layer (Y) containing the polymer (a), it is desirable to provide a layer (Z) made of an adhesive resin (c) in order to enhance the adhesiveness.
Examples of the layer (Z) made of the adhesive resin (c) include a layer under-coated with an epoxy-based, urethane-based, acrylic-based primer or the like. Moreover, there exists a layer (Z) which consists of adhesive resin (c) as another layer (Z) which improves the adhesiveness used suitably.
接着性樹脂（ｃ）
接着性樹脂（ｃ）としては、種々公知の接着性樹脂を用いることができ、特に変性ポリオレフィンやアイオノマー樹脂が好ましい。
変性ポリオレフィン
本発明で用いられる変性ポリオレフィンには、ポリオレフィンの一部もしくは全部が不飽和カルボン酸もしくはその誘導体（グラフトモノマー）でグラフト変性したものである。
ポリオレフィンとしては、例えばポリエチレン、エチレン−α−オレフィン共重合体、ポリプロピレンなどがある。中でもプロピレン系重合体には、プロピレン単独重合体又はプロピレンとそれ以外のα−オレフィンの合計モル数に基づいてプロピレン以外の該α−オレフィンが１０モル％以下、好ましくは７％以下を占める、プロピレンとそれ以外のα−オレフィンとのランダム共重合体が例示される。
プロピレン以外のα−オレフィンとしては、通常炭素数２０以下のα−オレフィン、具体的にはエチレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン、１−デセン、１−テトラデセン、１−オクタデセンなどが用いられ、それぞれ単独あるいは二種以上の混合して用いられる。
プロピレン系重合体のＭＦＲ（２３０℃、２．１６ｋｇ荷重）は、０．１〜５０ｇ／１０分が好ましく、５．０〜３０ｇ／１０分がより好ましい。
また密度は０．８８０〜０．９１０ｇ／ｃｍ３ が好ましく、０．８８０〜０．９００ｇ／ｃｍ３がより好ましい。
ポリオレフィンへの不飽和カルボン酸もしくはその誘導体（グラフトモノマー）のグラフト量は、通常０．０１〜１０重量％、好ましくは０．１〜５重量％である。 このようなグラフト量の場合、基材層（Ｘ）と重合体（ａ）を含有する層（Ｙ）との間の接着性が良好であり好ましい。
Adhesive resin (c)
As the adhesive resin (c), various known adhesive resins can be used, and modified polyolefins and ionomer resins are particularly preferable.
Modified polyolefin The modified polyolefin used in the present invention is one in which a part or all of the polyolefin is graft-modified with an unsaturated carboxylic acid or a derivative thereof (graft monomer).
Examples of the polyolefin include polyethylene, ethylene-α-olefin copolymer, and polypropylene. Among them, the propylene-based polymer includes propylene homopolymer or propylene, and the α-olefin other than propylene accounts for 10 mol% or less, preferably 7% or less based on the total number of moles of propylene and the other α-olefin. And random copolymers of other α-olefins.
As the α-olefin other than propylene, usually an α-olefin having 20 or less carbon atoms, specifically ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1 -Tetradedecene, 1-octadecene, etc. are used, and each is used individually or in mixture of 2 or more types.
The MFR (230 ° C., 2.16 kg load) of the propylene-based polymer is preferably 0.1 to 50 g / 10 minutes, and more preferably 5.0 to 30 g / 10 minutes.
The density is preferably 0.880~0.910g / cm 3, 0.880~0.900g / cm 3 is more preferable.
The amount of unsaturated carboxylic acid or its derivative (graft monomer) grafted onto the polyolefin is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight. In the case of such a graft amount, the adhesiveness between the base material layer (X) and the layer (Y) containing the polymer (a) is good and preferable.
不飽和カルボン酸としては、例えばアクリル酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸等をあげることができる。また不飽和カルボン酸の誘導体とは酸無水物、エステル、アミド、イミド、金属塩などで、例えば無水マレイン酸、無水シトラコン酸、無水イタコン酸、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸ブチル、メタクリル酸ブチル、アクリル酸グリシジル、メタクリル酸グリシジル、マレイン酸モノエチルエステル、マレイン酸ジエチルエステル、フマル酸モノメチルエステル、フマル酸ジメチルエステル、イタコン酸モノメチルエステル、イタコン酸ジエチルエステル、アクリルアミド、メタクリルアミド、マレイン酸モノアミド、マレイン酸ジアミド、マレイン酸−Ｎ−モノエチルアミド、マレイン酸−Ｎ,Ｎ−ジエチルアミド、マレイン酸−Ｎ−モノブチルアミド、マレイン酸−Ｎ,Ｎ−ジブチルアミド、フマル酸モノアミド、フマル酸ジアミド、フマル酸−Ｎ−モノエチルアミド、フマル酸−Ｎ−モノブチルアミド、フマル酸−Ｎ,Ｎ−ジブチチルアミド、マレイミド、Ｎ−フェニルマレイミド、アクリル酸ナトリウム、メタクリル酸ナトリウム、アクリル酸カリウム、メタクリル酸カリウム等を挙げることができる。 Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and the like. Unsaturated carboxylic acid derivatives are acid anhydrides, esters, amides, imides, metal salts, etc., such as maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid. Ethyl acetate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid diethyl ester, Acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N- Butyramide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N-monobutyramide, fumaric acid-N, N-dibutyrylamide, maleimide, N-phenylmaleimide, sodium acrylate, Examples include sodium methacrylate, potassium acrylate, and potassium methacrylate.
さらに、エポキシ基含有誘導体としては、グリシジルアクリレート、グリシジルメタクリレートなど、マレイン酸のモノおよびジグリシジルエステル、フマル酸のモノおよびジグリシジルエステル、クロトン酸のモノおよびジグリシジルエステル、テトラヒドロフタル酸のモノおよびジグリシジルエステル、イタコン酸のモノおよびグリシジルエステル、ブテントリカルボン酸のモノおよびジグリシジルエステル、シトラコン酸のモノおよびジグリシジルエステル、エンド-シス-ビシクロ［2.2.1］ヘプト−5−エン−2,3-ジカルボン酸（ナジック酸TM）のモノおよびジグリシジルエステル、エンド-シス−ビシクロ［2.2.1］ヘプト−5−エン−2−メチル−2,3−ジカルボン酸（メチルナジック酸TM）のモノおよびジグリシジルエステル、アリルコハク酸のモノおよびグリシジルエステルなどのジカルボン酸モノおよびアルキルグリシジルエステル（モノグリシジルエステルの場合のアルキル基の炭素数１〜１２）、p−スチレンカルボン酸のアルキルグリシジルエステル、アリルグリシジルエーテル、2−メチルアリルグリシジルエーテル、スチレン−p−グリシジルエーテル、3,4−エポキシ−1−ブテン、3,4−エポキシ−3−メチル−1−ブテン、3,4−エポキシ−1−ペンテン、3,4−エポキシ−3−メチル−1−ペンテン、5,6−エポキシ−1−ヘキセン、ビニルシクロヘキセンモノオキシドなどを例示することができる。水酸基含有誘導体としては、ヒドロキシエチル（メタ）アクリレート、2−ヒドロキシプロピル（メタ）アクリレート、3−ヒドロキシプロピル（メタ）アクリレート、2−ヒドロキシ−3−フェノキシ−プロピル（メタ）アクリレート、3−クロロ−2−ヒドロキシプロピル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、ペンタエリスリトールモノ（メタ）アクリレート、トリメチロールプロパンモノ（メタ）アクリレート、テトラメチロールエタンモノ（メタ）アクリレート、ブタンジオールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、2-（6-ヒドロキシヘキサノイルオキシ）エチルアクリレートなどの（メタ）アクリル酸エステル；10-ウンデセン-1-オール、1-オクテン-3-オール、2-メタノールノルボルネン、ヒドロキシスチレン、ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル、N-メチロールアクリルアミド、2-（メタ）アクロイルオキシエチルアシッドフォスフェート、グリセリンモノアリルエーテル、アリルアルコール、アリロキシエタノール、2-ブテン-1,4-ジオール、グリセリンモノアルコールなどが挙げられる。 Further, epoxy group-containing derivatives include mono- and diglycidyl esters of maleic acid, mono- and diglycidyl esters of fumaric acid, mono- and diglycidyl esters of crotonic acid, mono- and di-glycols of tetrahydrophthalic acid, such as glycidyl acrylate and glycidyl methacrylate Glycidyl esters, mono and glycidyl esters of itaconic acid, mono and diglycidyl esters of butenetricarboxylic acid, mono and diglycidyl esters of citraconic acid, endo-cis-bicyclo [2.2.1] hept-5-ene-2,3- Mono- and diglycidyl esters of dicarboxylic acids (Nadic acid TM), mono- and di-glycosyl esters of endo-cis-bicyclo [2.2.1] hept-5-ene-2-methyl-2,3-dicarboxylic acid (Methyl nadic acid TM) Glycidyl ester, allyl succinic acid Mono- and glycidyl esters of dicarboxylic acids such as mono- and glycidyl esters (C1-C12 of alkyl groups in the case of mono-glycidyl esters), alkyl glycidyl esters of p-styrene carboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether , Styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3- Examples thereof include methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide and the like. Hydroxyl-containing derivatives include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-propyl (meth) acrylate, 3-chloro-2 -Hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene (Meth) acrylic acid esters such as glycol mono (meth) acrylate and 2- (6-hydroxyhexanoyloxy) ethyl acrylate; 10-undecen-1-ol, 1-octen-3-ol, 2-methanol Norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerol monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4 -Diol, glycerin monoalcohol and the like.
これらの中では、不飽和カルボン酸またはその酸無水物、中でもジカルボン酸またはその酸無水物が好適であり、マレイン酸、ナジック酸またはこれらの酸無水物、無水マレイン酸、ヒドロキシエチル（メタ）アクリレート、グリシジルメタクリレート、メタクリル酸アミノプロピル、グリシジルマレエート、ヒドロキシエチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、グリシジル（メタ）アクリレート、メタクリル酸アミノエチルおよびメタクリル酸アミノプロピルなどを好適例として挙げることができる。 Among these, unsaturated carboxylic acids or acid anhydrides thereof, particularly dicarboxylic acids or acid anhydrides thereof are preferred, and maleic acid, nadic acid or acid anhydrides thereof, maleic anhydride, hydroxyethyl (meth) acrylate Suitable examples include glycidyl methacrylate, aminopropyl methacrylate, glycidyl maleate, hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate, and aminopropyl methacrylate. it can.
これらの不飽和エチレン性単量体をプロピレン系重合体他のポリオレフィンにグラフト共重合してグラフト変性プロピレン重合体他の変性ポリオレフィンを製造するには、従来公知の種々の方法を採用することができる。
たとえば、プロピレン系重合体を溶融させグラフトモノマーを添加してグラフト共重合させる方法あるいは溶媒に溶解させグラフトモノマーを添加してグラフト共重合させる方法がある。いずれの場合にも、前記グラフトモノマーを効率よくグラフト共重合させるためには、ラジカル開始剤の存在下に反応を実施することが好ましい。グラフト反応は、通常６０〜３５０℃の温度で行われる。ラジカル開始剤の使用割合は、ポリオレフィン１００重量部に対して通常０．００１〜１重量部の範囲である。
In order to produce a graft-modified propylene polymer or other modified polyolefin by graft copolymerization of these unsaturated ethylenic monomers with a propylene-based polymer or other polyolefin, various conventionally known methods can be employed. .
For example, there are a method in which a propylene-based polymer is melted and a graft monomer is added to carry out graft copolymerization, or a method in which it is dissolved in a solvent and a graft monomer is added to carry out graft copolymerization. In any case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator. The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The use ratio of the radical initiator is usually in the range of 0.001 to 1 part by weight with respect to 100 parts by weight of the polyolefin.
ラジカル開始剤としては、有機ペルオキシド、有機ペルエステル、たとえばジクミルペルオキシド、ジ−ｔｅｒｔ−ブチルペルオキシド、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキシン−３、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキサン、１，４−ビス（ｔｅｒｔ−ブチルペルオキシイソプロピル）ベンゼンなどのジアルキルペルオキシドが好適である。
変性ポリオレフィンからなる層（Ｚ）の厚さは、通常０．０１〜５．０μｍ、好ましくは０．０１〜３．０μｍ、より好ましくは０．０１〜２．０μｍであり、この範囲であれば接着性がより優れる。
As radical initiators, organic peroxides, organic peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5- Dialkyl peroxides such as dimethyl-2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.
The thickness of the layer (Z) made of the modified polyolefin is usually 0.01 to 5.0 μm, preferably 0.01 to 3.0 μm, more preferably 0.01 to 2.0 μm. More excellent adhesion.
アイオノマー樹脂
本発明用いられるアイオノマー樹脂は、エチレンによって代表されるオレフィンとα,β−エチレン性不飽和カルボン酸またはその誘導体との共重合体、またはオレフィン重合体の不飽和カルボン酸またはその誘導体のグラフト共重合体であり、共重合体中の遊離カルボキシル基は完全にまたは部分的にナトリウム、カリウムなどのアルカリ金属または亜鉛等のアルカリ土類金属で中和されている。これら、カルボキシル基の全部または一部がナトリウム、亜鉛などの金属で中和された樹脂である。アイオノマー樹脂は、イオン基を有するため、ホモミキサー等の装置を用いて溶融物を熱水中で高速攪拌混合した場合、水に対して自己分散する性質を有し、それ自体で水性分散液を形成し易い。
Ionomer resin The ionomer resin used in the present invention is a copolymer of an olefin represented by ethylene and an α, β-ethylenically unsaturated carboxylic acid or a derivative thereof, or a graft of an unsaturated carboxylic acid of an olefin polymer or a derivative thereof. A free carboxyl group in the copolymer is completely or partially neutralized with an alkali metal such as sodium or potassium or an alkaline earth metal such as zinc. These are resins in which all or part of the carboxyl groups are neutralized with a metal such as sodium or zinc. Since the ionomer resin has an ionic group, it has the property of self-dispersing in water when the melt is stirred and mixed in hot water using a device such as a homomixer. Easy to form.
かかるアイオノマー樹脂を接着性樹脂（ｃ）からなる層（Ｚ）として用いる場合、アイオノマー樹脂とポリビニルアルコール系重合体との混合物としてもよい。この場合、アイオノマー樹脂とポリビニルアルコール系重合体との比は１００：０〜２０：８０、好ましくは１００：０〜３０：７０、さらに好ましくは、１００：０〜４０：６０であることが望ましく、この範囲であれば基材層（Ｘ）と重合体（ａ）を含有する層（Ｙ）との接着性がより優れる。 When using this ionomer resin as a layer (Z) which consists of adhesive resin (c), it is good also as a mixture of an ionomer resin and a polyvinyl alcohol-type polymer. In this case, the ratio of the ionomer resin to the polyvinyl alcohol polymer is 100: 0 to 20:80, preferably 100: 0 to 30:70, and more preferably 100: 0 to 40:60, If it is this range, the adhesiveness of the base material layer (X) and the layer (Y) containing a polymer (a) will be more excellent.
上記アイオノマー樹脂とポリビニルアルコール系重合体との混合物はアイオノマー樹脂の水分散液とポリビニルアルコール系重合体水溶液との混合液であってもよい。
本発明において、アイオノマー樹脂水分散液またはアイオノマー樹脂の水分散液とポリビニルアルコール系重合体水溶液との混合液においては、水以外の溶媒、例えばメタノール、エタノール、イソプロパノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、或いはその他ジエチルエーテル、テトラヒドロフラン等を必要に応じて、１種または２種以上を組み合わせて加えることも可能である。
The mixture of the ionomer resin and the polyvinyl alcohol polymer may be a mixture of an ionomer resin aqueous dispersion and a polyvinyl alcohol polymer aqueous solution.
In the present invention, an ionomer resin aqueous dispersion or a mixture of an ionomer resin aqueous dispersion and an aqueous polyvinyl alcohol polymer solution is a solvent other than water, for example, alcohols such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, etc. These ketones, or other diethyl ether, tetrahydrofuran and the like can be added alone or in combination of two or more as required.
アイオノマー樹脂またはアイオノマー樹脂とポリビニルアルコール系重合体との混合物を接着性樹脂として用いる場合、接着性樹脂（ｃ）からなる層（Ｚ）の厚さは、通常０．０１〜５．０μｍ、好ましくは０．０１〜３．０μｍ、より好ましくは０．０１〜２．０μｍであり、この範囲であれば接着性がより優れる。 When an ionomer resin or a mixture of an ionomer resin and a polyvinyl alcohol polymer is used as an adhesive resin, the thickness of the layer (Z) made of the adhesive resin (c) is usually 0.01 to 5.0 μm, preferably It is 0.01-3.0 micrometers, More preferably, it is 0.01-2.0 micrometers, and if it is this range, adhesiveness will be more excellent.
保護層
本発明の延伸フィルム等の延伸成形体には、重合体（ａ）を含有する層（Ｙ）の上に、さらに保護層が積層されていてもよい。
かかる保護層としては、重合体（ａ）を含有する層（Ｙ）を保護し得る層であればとくに限定はされず、種々公知の保護層、例えば、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、アミノ樹脂、ポリイミド等の熱硬化性樹脂、ポリオレフィン（ポリエチレン、ポリプロピレン、ポリ４−メチル・１−ペンテン、ポリブテン等）、ポリエステル（ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等）、ポリアミド（ナイロン−６、ナイロン−６６、ポリメタキシレンアジパミド等）、ポリ塩化ビニル、ポリイミド、エチレン・酢酸ビニル共重合体もしくはその鹸化物、ポリビニルアルコール、ポリアクリロニトリル、ポリカーボネート、ポリスチレン、アイオノマー、あるいはこれらの混合物等の熱可塑性樹脂等が挙げられる。
Protective layer In the stretched molded product such as the stretched film of the present invention, a protective layer may be further laminated on the layer (Y) containing the polymer (a).
The protective layer is not particularly limited as long as it can protect the layer (Y) containing the polymer (a), and various known protective layers such as a poxy resin, an unsaturated polyester resin, and a phenol resin. , Thermosetting resins such as urea / melamine resin, polyurethane resin, silicone resin, amino resin, polyimide, 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 DOO, polystyrene, ionomer or thermoplastic resins such as these mixtures, and the like.
本発明の延伸フィルムは通常は、基材層（Ｘ）にガスバリア性に優れた層（Ｙ）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（Ｘ）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 stretched film of the present invention is usually used as a laminate in which a layer (Y) excellent in gas barrier properties is laminated on a base material layer (X). 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 (X) and depending on the application.
本発明の製造方法により得られるガスバリア性のある延伸フィルムは、その少なくとも片面に、熱融着層を積層することにより、ヒートシール可能な包装用フィルムとして好適な積層フィルムが得られる。かかる熱融着層としては、通常熱融着層として公知のエチレン、プロピレン、ブテン−１、ヘキセン−１、４−メチル・ペンテン−１、オクテン−１等のα−オレフィンの単独若しくは共重合体、高圧法低密度ポリエチレン、線状低密度ポリエチレン（所謂ＬＬＤＰＥ）、高密度ポリエチレン、ポリプロピレン、ポリプロピレンランダム共重合体、ポリブテン、ポリ４−メチル・ペンテン−１、低結晶性あるいは非晶性のエチレン・プロピレンランダム共重合体、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。
A stretched film having a gas barrier property obtained by the production method of the present invention is laminated on at least one surface thereof to obtain a laminated film suitable as a heat-sealable packaging film. 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.
また、延伸フィルムの重合体（ａ）を含有する層（Ｙ）側には、その表面に従来公知の種々の方法により保護層を形成させることも行われる。
例えば、熱硬化性樹脂からなる保護層を形成させる場合は、モノマーあるいはプレポリマーを重合体（ａ）を含有する層（Ｙ）上に塗工した後、硬化させる方法、熱可塑性樹脂からなる保護層を形成させる場合は、熱可塑性樹脂の溶液あるいはエマルションを塗工した後、乾燥させる方法等を採り得る。
Further, a protective layer may be formed on the surface of the stretched film containing the polymer (a) by a variety of conventionally known methods on the surface thereof.
For example, when forming a protective layer made of a thermosetting resin, a method in which a monomer or prepolymer is coated on the layer (Y) containing the polymer (a) and then cured, and a protective material made of a thermoplastic resin In the case of forming a layer, a method of drying after applying a solution or emulsion of a thermoplastic resin may be employed.
次に、本発明を実施例によりさらに具体的に説明するが、本発明はこれら実施例により何等限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples.
実施例及び比較例における物性値等は、以下の評価方法により求める。
＜評価方法＞
（１）酸素透過度［ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）］：延伸フィルムを、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％Ｒ．Ｈ．の条件で測定する。
（２）吸光度比（Ａ０／Ａ）：前記記載の方法で測定する。
（３）重合率：〔１−（Ａ１／Ａ）ＵＶ後／（Ａ１／Ａ）モノマー〕×１００
＊（Ａ１／Ａ）ＵＶ後：紫外線照射（重合後）後の（Ａ１／Ａ）
＊（Ａ１／Ａ）モノマー：モノマー（重合前）の（Ａ１／Ａ）
（Ａ１／Ａ）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Ａ１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（Ａ１／Ａ）は、延伸フィルムから１ｃｍ×３ｃｍの測定用サンプルを切り出し、その表面（重合体（ａ）を含有する層（Ｙ））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Ａ１及び吸光度Ａを求める。
The physical property values and the like in Examples and Comparative Examples are obtained by the following evaluation methods.
<Evaluation method>
(1) Oxygen permeability [ml / (m 2 · day · MPa)]: The stretched film is OX-TRAN 2/21 ML manufactured by Mocon, according to JIS K 7126, temperature 20 ° C., humidity 90% R . H. Measure under the following conditions.
(2) Absorbance ratio (A 0 / A): measured by the method described above.
(3) Polymerization rate: [1- (A 1 / A) after UV / (A 1 / A) monomer ] × 100
* (A 1 / A) after UV: ultraviolet irradiation (after polymerization) after (A 1 / A)
* (A 1 / A) monomer: monomer (before polymerization) of (A 1 / A)
(A 1 / A) was defined as described below.
Ratio of absorbance A 1 based on δC—H of hydrogen bonded to a vinyl group near 830 cm −1 to absorbance A based on νC═O of carboxylate ions near 1520 cm −1 in the infrared absorption spectrum (A 1 / A) Cut out a sample for measurement of 1 cm × 3 cm from the stretched film, and obtained an infrared absorption spectrum of the surface (layer (Y) containing the polymer (a)) by infrared total reflection measurement (ATR method). First, the absorbance A 1 and the absorbance A are obtained.
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Ａ１：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Ａ１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付近である。
次いで、上記方法で求めた吸光度Ａ１及び吸光度Ａから比（Ａ１／Ａ）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（Ａ１／Ａ）モノマーとＵＶ照射（重合後）後の（Ａ１／Ａ）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。
830cm absorbance based .delta.C-H of hydrogen binding to vinyl groups in the vicinity of -1 A 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 absorbance between the intersection of the straight line (Q) and the straight line (P) and the maximum absorbance is defined as absorbance A 1 .
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 , and magnesium is near 1540 cm −1 . is there.
Next, the ratio (A 1 / A) is determined from the absorbance A 1 and the absorbance A determined by the above method. Further, the polymerization rate is determined by measuring the monomer absorbance ratio (A 1 / A) monomer and the UV irradiation (after polymerization) (A 1 / A) 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.
＜溶液（ｓ１）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：１５重量％（アクリル酸成分：１０重量％、Ｚｎ成分：５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、不飽和カルボン酸化合物Ｚｎ塩溶液（ｓ１）を作製する。
<Preparation of solution (s1)>
Aqueous solution of zinc acrylate (Zn salt of acrylic acid) [Asada Chemical Co., Ltd., concentration: 15 wt% (acrylic acid component: 10 wt%, Zn component: 5 wt%)] and methyl alcohol diluted to 25 wt% Photopolymerization 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) are mixed so that the molar fractions are 98.5%, 1.2%, and 0.3%, respectively, and the unsaturated carboxylic acid compound Zn salt solution is mixed. (S1) is produced.
＜溶液（ｓ２）の作製＞
重合度１０００でエチレン含有量が８．６ｍｏｌ％、ケン化度が９５％以上のポリビニルアルコール系重合体の１５％水溶液を作製する。
<Preparation of solution (s2)>
A 15% aqueous solution of a polyvinyl alcohol polymer having a polymerization degree of 1000, an ethylene content of 8.6 mol%, and a saponification degree of 95% or more is prepared.
＜溶液（ｓ３）の作製＞
シリル変性ポリビニルアルコール樹脂、Ｒ１１３０（クラレ社製）の１５％水溶液を作製する。
<Preparation of solution (s3)>
A 15% aqueous solution of silyl-modified polyvinyl alcohol resin, R1130 (manufactured by Kuraray Co., Ltd.) is prepared.
実施例１
ポリエチレンテレフタレートからなる未延伸フィルムの表面に不飽和カルボン酸化合物Ｚｎ塩溶液（ｓ１）をメイヤバーを用いて乾燥後の塗布量が１０ｇ／ｍ２となるよう塗工する。次いで、未延伸フィルム全体をオーブン中で６０℃、１分の条件で乾燥後、紫外線照射装置を用い照射光量５ｍＪ／ｃｍ２になるように未延伸フィルム全体に照射し予備重合させた。このとき塗工した重合体層の重合率は３５％であった。次いで、延伸フィルムを二軸延伸（延伸倍率１．５倍×１．５倍）した後、さらに紫外線を照射光量２００ｍＪ／ｃｍ２になるよう照射し、重合率を９０％として、重合体層が形成された延伸フィルムを得た。吸光度比（Ａ０／Ａ）が０．１であった。また、延伸フィルムから９０ｍｍ×９０ｍｍの大きさでサンプルを切り出しその酸素透過度を測定すると、１ｍｌ／ｍ２・ｄａｙ・ＭＰａであった。
Example 1
An unsaturated carboxylic acid compound Zn salt solution (s1) is applied to the surface of an unstretched film made of polyethylene terephthalate using a Mayer bar so that the coating amount after drying is 10 g / m 2 . Next, the whole unstretched film was dried in an oven at 60 ° C. for 1 minute, and then irradiated to the whole unstretched film so as to have an irradiation light amount of 5 mJ / cm 2 by using an ultraviolet irradiation device, and prepolymerized. The polymerization rate of the polymer layer applied at this time was 35%. Next, the stretched film was biaxially stretched (stretching ratio: 1.5 × 1.5 times), and further irradiated with ultraviolet rays so as to have an irradiation light amount of 200 mJ / cm 2. A formed stretched film was obtained. The absorbance ratio (A 0 / A) was 0.1. Further, when a sample was cut out from the stretched film with a size of 90 mm × 90 mm and its oxygen permeability was measured, it was 1 ml / m 2 · day · MPa.
実施例２
メルトフローレート２．０ｇ／１０分のポリプロピレンを押出し機内で溶融し、Ｔダイよりシート状に押出し、未延伸のシートを得た。この未延伸シートを周速の異なる加熱ロール群からなる縦延伸機で５倍に延伸し、つづいてこの縦延伸シートの片面に、コロナ放電処理を施した。次に溶液ｓ１と溶液ｓ２とを固形分比率（ｗｔ％）で５（ｓ１）：９５（ｓ２）となるように混合し、この混合液を縦延伸シートのコロナ面上に乾燥後の塗膜が２０ｇ／ｍ２となるように塗工し乾燥した後、テンター横延伸機に連続的に導入し延伸倍率１０倍で横延伸し、その後さらに紫外線を照射光量２００ｍＪ／ｃｍ２になるよう照射し積層フィルムを得た。その吸光度比（Ａ０／Ａ）は０．１であり、酸素透過度を測定すると、１００ｍｌ／ｍ２・ｄａｙ・ＭＰａであった。
Example 2
Polypropylene having a melt flow rate of 2.0 g / 10 min was melted in an extruder and extruded from a T-die into a sheet to obtain an unstretched sheet. This unstretched sheet was stretched 5 times by a longitudinal stretching machine composed of heating roll groups having different peripheral speeds, and then one side of the longitudinally stretched sheet was subjected to corona discharge treatment. Next, the solution s1 and the solution s2 are mixed so that the solid content ratio (wt%) is 5 (s1): 95 (s2), and this mixed solution is dried on the corona surface of the longitudinally stretched sheet. After coating and drying so as to be 20 g / m 2 , it is continuously introduced into a tenter transverse stretching machine and stretched transversely at a stretching ratio of 10 times, and then further irradiated with ultraviolet rays so that the irradiation light quantity becomes 200 mJ / cm 2. A laminated film was obtained. The absorbance ratio (A 0 / A) was 0.1, and the oxygen permeability measured was 100 ml / m 2 · day · MPa.
実施例３
実施例２で用いたと同様のポリプロピレン樹脂を押出し機内で溶融し、Ｔダイよりシート状に押出し、未延伸のシートを得た。この未延伸シートを周速の異なる加熱ロール群からなる縦延伸機で５倍に延伸し、つづいてこの縦延伸シートの片面に、コロナ放電処理を施した。次に接着性樹脂層としてアイオノマー樹脂の水分散液（三井化学 ケミパールＳ１００）を乾燥後の塗膜が１μｍの厚さになるように塗布し温風で乾燥し、テンター横延伸機に連続的に導入し延伸倍率１０倍で横延伸しアイオノマー樹脂積層フィルムを得た。次に溶液ｓ１と溶液ｓ３とを固形分比率（ｗｔ％）で８７．５（ｓ１）：１２．５（ｓ３）となるように混合し、この混合液をアイオノマー樹脂積層フィルムのアイオノマー樹脂上に乾燥後の塗膜が３．５ｇ／ｍ２となるように塗工し４０℃１５秒で乾燥した後、さらに紫外線を照射光量２００ｍＪ／ｃｍ２になるよう照射し積層フィルムを得た。その吸光度比（Ａ０／Ａ）は０．１であり、その酸素透過度を測定すると、１．５ｍｌ／ｍ２・ｄａｙ・ＭＰａであった。
Example 3
The same polypropylene resin as used in Example 2 was melted in an extruder and extruded from a T-die into a sheet to obtain an unstretched sheet. This unstretched sheet was stretched 5 times by a longitudinal stretching machine composed of heating roll groups having different peripheral speeds, and then one side of the longitudinally stretched sheet was subjected to corona discharge treatment. Next, an aqueous dispersion of ionomer resin (Mitsui Chemicals Chemipearl S100) was applied as an adhesive resin layer so that the coating film after drying had a thickness of 1 μm, dried with warm air, and continuously in a tenter transverse stretching machine. The film was introduced and transversely stretched at a stretch ratio of 10 to obtain an ionomer resin laminated film. Next, the solution s1 and the solution s3 are mixed so that the solid content ratio (wt%) is 87.5 (s1): 12.5 (s3), and this mixed solution is placed on the ionomer resin of the ionomer resin laminated film. The coated film after drying was applied to 3.5 g / m 2 , dried at 40 ° C. for 15 seconds, and then irradiated with ultraviolet rays to an irradiation light amount of 200 mJ / cm 2 to obtain a laminated film. The absorbance ratio (A 0 / A) was 0.1, and the oxygen permeability measured was 1.5 ml / m 2 · day · MPa.
実施例４
アイオノマー樹脂積層フィルム上に塗布する溶液をｓ１にする以外は実施例３と同様に積層フィルムを得た。その吸光度比（Ａ０／Ａ）は０．１２であり、その酸素透過度を測定すると、１．０ｍｌ／ｍ２・ｄａｙ・ＭＰａであった。
Example 4
A laminated film was obtained in the same manner as in Example 3 except that the solution applied onto the ionomer resin laminated film was changed to s1. The absorbance ratio (A 0 / A) was 0.12, and the oxygen transmission rate was 1.0 ml / m 2 · day · MPa.
実施例５
実施例２で用いたと同様のポリプロピレン樹脂を押出し機内で溶融し、Ｔダイよりシート状に押出し、未延伸のシートを得た。この未延伸シートを周速の異なる加熱ロール群からなる縦延伸機で５倍に延伸し、つづいてこの縦延伸シートの片面に、コロナ放電処理を施した。次に接着性樹脂層としてアイオノマー樹脂の水分散液（三井化学 ケミパールＳ１００）を乾燥後の塗膜が１μｍの厚さになるように塗布し温風で乾燥した。次に溶液ｓ１と溶液ｓ２とを固形分比率（ｗｔ％）で５（ｓ１）：９５（ｓ２）となるように混合し、この混合液をアイオノマー樹脂上に乾燥後の塗膜が２０ｇ／ｍ２となるように塗工し乾燥した後、テンター横延伸機に連続的に導入し延伸倍率１０倍で横延伸し、その後さらに紫外線を照射光量２００ｍＪ／ｃｍ２になるよう照射し積層フィルムを得た。その吸光度比（Ａ０／Ａ）は０．１３であり、その酸素透過度を測定すると、１１０ｍｌ／ｍ２・ｄａｙ・ＭＰａであった。
Example 5
The same polypropylene resin as used in Example 2 was melted in an extruder and extruded from a T-die into a sheet to obtain an unstretched sheet. This unstretched sheet was stretched 5 times by a longitudinal stretching machine composed of heating roll groups having different peripheral speeds, and then one side of the longitudinally stretched sheet was subjected to corona discharge treatment. Next, an aqueous dispersion of ionomer resin (Mitsui Chemicals Chemipearl S100) was applied as an adhesive resin layer so that the dried coating film had a thickness of 1 μm and dried with warm air. Next, the solution s1 and the solution s2 are mixed so that the solid content ratio (wt%) is 5 (s1): 95 (s2), and this mixed solution is dried on an ionomer resin so that the coating film after drying is 20 g / m 2. After coating and drying so as to be 2 , the film was continuously introduced into a tenter transverse stretching machine and transversely stretched at a stretching ratio of 10 times, and further irradiated with ultraviolet rays so as to have an irradiation light amount of 200 mJ / cm 2 to obtain a laminated film. It was. The absorbance ratio (A 0 / A) was 0.13, and the oxygen permeability was measured to be 110 ml / m 2 · day · MPa.
実施例６
実施例２で用いたと同様のポリプロピレン樹脂（Ｘ１）と石油樹脂（軟化点１３５℃）をブレンドした結晶性ポリプロピレン樹脂（ＩＩ値：９８．６％）（Ｘ２）と接着性樹脂層として、無水マレイン酸でグラフト変性した変性ポリプロピレン（三井化学 アドマーＱＦ５００）（Ｘ３）を別々の押出し機で溶融したものを一台のダイ内で層状（Ｘ１）／（Ｘ２）／（Ｘ３）の順）に重ねて押出し、未延伸三層シートを得た。この未延伸シートを周速の異なる加熱ロール群からなる縦延伸機で５倍に延伸し、つづいて、この縦延伸シートの（Ｘ３）面に、コロナ放電処理を施した。次に溶液ｓ１と溶液ｓ２とを固形分比率（ｗｔ％）で５（ｓ１）：９５（ｓ２）となるように混合し、この混合液を縦延伸シートのコロナ面上に乾燥後の塗膜が２０ｇ／ｍ２となるように塗工し乾燥した後、テンター横延伸機に連続的に導入し延伸倍率１０倍で横延伸し、その後さらに紫外線を照射光量２００ｍＪ／ｃｍ２になるよう照射し積層フィルムを得た。その吸光度比（Ａ０／Ａ）は０．１５であり、その酸素透過度を測定すると、９８ｍｌ／ｍ２・ｄａｙ・ＭＰａであった。
Example 6
Crystalline polypropylene resin (II value: 98.6%) (X2) blended with the same polypropylene resin (X1) and petroleum resin (softening point 135 ° C.) as used in Example 2, and anhydrous maleic resin Modified polypropylene grafted with acid (Mitsui Chemicals Admer QF500) (X3) is melted in a separate extruder and layered (in the order of (X1) / (X2) / (X3)) in one die. Extrusion gave an unstretched three-layer sheet. This unstretched sheet was stretched 5 times by a longitudinal stretching machine composed of heating roll groups having different peripheral speeds, and subsequently, the (X3) plane of this longitudinally stretched sheet was subjected to corona discharge treatment. Next, the solution s1 and the solution s2 are mixed so that the solid content ratio (wt%) is 5 (s1): 95 (s2), and this mixed solution is dried on the corona surface of the longitudinally stretched sheet. After coating and drying so as to be 20 g / m 2 , it is continuously introduced into a tenter transverse stretching machine and stretched transversely at a stretching ratio of 10 times, and then further irradiated with ultraviolet rays so that the irradiation light quantity becomes 200 mJ / cm 2. A laminated film was obtained. The absorbance ratio (A 0 / A) was 0.15, and the oxygen permeability was measured to be 98 ml / m 2 · day · MPa.
比較例１
メルトフローレート２．０ｇ／１０分のポリプロピレンを押出し機内で溶融し、Ｔダイよりシート状に押出し、未延伸のシートを得た。この未延伸シートを周速の異なる加熱ロール群からなる縦延伸機で５倍に延伸し、つづいてこの縦延伸シートの片面に、コロナ放電処理を施した。次に溶液ｓ１を縦延伸シートのコロナ面上に乾燥後の塗膜が２０ｇ／ｍ２となるように塗工し４０℃１５秒乾燥した後、さらに紫外線を照射光量２００ｍＪ／ｃｍ２になるよう照射し、テンター横延伸機に連続的に導入し延伸倍率１０倍で横延伸し積層フィルムを得た。、その吸光度比（Ａ０／Ａ）は０．１５であり、その酸素透過度を測定すると、２０００ｍｌ／ｍ２・ｄａｙ・ＭＰａ以上であった。
Comparative Example 1
Polypropylene having a melt flow rate of 2.0 g / 10 min was melted in an extruder and extruded from a T-die into a sheet to obtain an unstretched sheet. This unstretched sheet was stretched 5 times by a longitudinal stretching machine composed of heating roll groups having different peripheral speeds, and then one side of the longitudinally stretched sheet was subjected to corona discharge treatment. Next, the solution s1 is applied onto the corona surface of the longitudinally stretched sheet so that the coating film after drying is 20 g / m 2 , dried at 40 ° C. for 15 seconds, and further irradiated with ultraviolet rays so that the irradiation light quantity becomes 200 mJ / cm 2. Irradiated, continuously introduced into a tenter transverse stretching machine and transversely stretched at a stretch ratio of 10 times to obtain a laminated film. The absorbance ratio (A 0 / A) was 0.15, and the oxygen permeability measured was 2000 ml / m 2 · day · MPa or more.
本発明の不飽和カルボン酸化合物多価金属塩の重合体層が形成された延伸フィルムは高湿度下でのガスバリア性に優れており、かかる特徴を活かして、種々の用途用の延伸フィルムと使用される。
The stretched film on which the polymer layer of the unsaturated carboxylic acid compound polyvalent metal salt of the present invention is formed is excellent in gas barrier properties under high humidity, and by utilizing such characteristics, it is used with stretched films for various applications. Is done.
Claims (10)
及び／または 延伸処理の後に不飽和カルボン酸化合物多価金属塩の重合物（ａ）を含有する層（Ｙ）を形成させることを特徴とする延伸成形体の製造方法。 A solution (s) containing an unsaturated carboxylic acid compound polyvalent metal salt having a polymerization degree of less than 20 is applied to at least one surface of the unstretched base material layer (X), and at the same time and / or stretching process. And a layer (Y) containing the polymer (a) of the unsaturated carboxylic acid compound polyvalent metal salt is formed after the step.
Stretched film obtained al is by the production method according to any one of claims 1 to 9.
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