JP3733300B2 - Gas barrier laminate film and method for producing gas barrier laminate film - Google Patents

Description

【０１７１】
前記表１から明らかなように実施例１のガスバリア性積層フィルムは、厚さ１μｍ、２μｍの薄いガスバリア層を有する状態で参照例４の厚さ３０μｍのＰＶＤＣフィルムと同等またはそれ以上優れた酸素遮断性を有することがわかる。また、ガスバリア層の厚さが２μｍである実施例１および比較例１のガスバリア性積層フィルムを対比すれば明らかなように実施例１の積層フィルムは比較例１の積層フィルムに比べて優れた酸素遮断性および水蒸気遮断性を有することがわかる。
【０１７２】
また、実施例１のガスバリア性積層フィルムは基材フィルムであるＯＰＰと同等の透明性を有していた。
【０１７３】
なお、酸化ケイ素の蒸着フィルムである比較例３のガスバリア性積層フィルムは屈曲を繰り返すと酸化ケイ素蒸着膜にピンホールやクラックが発生してその酸素および水蒸気遮断性が極端に低下する。これに対し、実施例１のガスバリア性積層フィルムは屈曲を繰り返しても前記表１の優れた酸素遮断性および水蒸気遮断性が維持された。
【０１７４】
また、ＥＶＯＨ，ＰＶＡの単独フィルムは乾燥雰囲気中での酸素遮断性が優れているものの、湿潤雰囲気に曝されるとその酸素遮断性が極端に低下する。
【０１７５】
（実施例２）
実施例１で調製したガスバリアコート剤を厚さ１２μｍのＰＥＴフィルムに厚さが１μｍおよび２μｍになるようにロールコータ法によりそれぞれ塗布し、乾燥して前記ＰＥＴフィルムにガスバリア層を形成することにより２種のガスバリア性積層フィルムを製造した。
【０１７６】
（比較例４）
２５重量％濃度のポリ塩化ビニリデン（ＰＶＤＣ）のＩＰＡ溶液（ガスバリアコート剤）を厚さ１２μｍのＰＥＴフィルムに厚さが２．０μｍになるようにロールコータ法により塗布し、乾燥することによりガスバリア性積層フィルムを製造した。
【０１７７】
得られた実施例２および比較例４の積層フィルムについて、実施例１と同様な方法により酸素透過量および水蒸気透過量を測定した。その結果を下記表２に示す。なお、下記表２には参照例５として、厚さ１２μｍのＰＥＴフィルムの酸素透過量および水蒸気透過量を併記した。
【０１７８】
【表２】

【０１７９】
なお、実施例２のガスバリア性積層フィルムは基材フィルムであるＰＥＴと同等の透明性を有していた。
【０１８０】
また、実施例２のガスバリア性積層フィルムは屈曲を繰り返しても前記表２の優れた酸素遮断性および水蒸気遮断性が維持された。
【０１８１】
（実施例３）
水とイソプロピルアルコール（ＩＰＡ）とを５０：５０の重量比で混合した溶剤にエチレンビニルアルコール共重合体（ＥＶＯＨ）を２５重量％添加し、８０℃の温度下で前記樹脂を溶解した後、この溶液に酸化ケイ素粉末の凝集物（一次粒子の平均粒径；７ｎｍ）および酸化チタン粉末の凝集物（一次粒子の平均粒 径；２０ｎｍ）を前記ＥＶＯＨに対してそれぞれ２０重量％、１０重量％添加して液状混合物を調製した。つづいて、この液状混合物を８０℃の温度維持しながら、前述した図３に示す衝突破砕装置を用い、下記に示す条件で衝突破砕を５回繰り返した。この工程により前記各凝集物が解粉され、同時に前記ＥＶＯＨと均一に分散接合または結合がなされ、平均粒径７ｎｍのＳｉＯ₂超微粉末および平均粒径２０ｎｍのＴｉＯ₂超微粉末と前記ＥＶＯＨとが溶剤の存在下で均一に分散接合された多数の複合超微粒子を含むガスバリアコート剤が調製された。
【０１８２】
＜衝突破砕条件＞
・液状混合物の加圧力；約１８００Ｋｇ／ｃｍ^2
・ノズル部を通過する液状混合物の加速度；約２５０ｍ／ｓｅｃ
得られたガスバリアコート剤は、常温ないしそれ以下の温度で酸化ケイ素のような無機化合物の超微粉末が析出したり、繊維状に成長したりすることなく、安定した性状を有するものであった。また、前記ガスバリアコート剤中の前記複合超微粒子は平均粒径が０．１μｍであった。
【０１８３】
次いで、前記ガスバリアコート剤を厚さ１６μｍのナイロンフィルムに厚さが１μｍおよび２μｍになるようにロールコータ法によりそれぞれ塗布し、乾燥して前記ナイロンフィルムにガスバリア層を形成することによって２種のガスバリア性積層フィルムを製造した。
【０１８４】
前記ガスバリア層を電子顕微鏡で観察した。その結果、ＥＶＯＨに平均粒径７ｎｍの酸化ケイ素超微粉末および平均粒径２０ｎｍの酸化チタン超微粉末が均一に分散されていることが確認された。
【０１８５】
（比較例５）
２５重量％濃度のポリ塩化ビニリデン（ＰＶＤＣ）のＩＰＡ溶液（ガスバリアコート剤）を厚さ１６μｍのナイロンフィルムに厚さが２．０μｍになるようにロールコータ法により塗布し、乾燥することによりガスバリア性積層フィルムを製造した。
【０１８６】
得られた実施例３および比較例５の積層フィルムについて、実施例１と同様な方法により酸素透過量および水蒸気透過量を測定した。その結果を下記表３に示す。なお、下記表３には参照例６として、厚さ１６μｍのナイロンフィルムの酸素透過量および水蒸気透過量を併記した。
【０１８７】
【表３】

【０１８８】
なお、実施例３のガスバリア性積層フィルムは基材フィルムであるナイロンと同等の透明性を有していた。
【０１８９】
また、実施例３のガスバリア性積層フィルムは屈曲を繰り返しても前記表３の優れた酸素遮断性および水蒸気遮断性が維持された。
【０１９０】
（実施例４）
実施例３で調製したガスバリアコート剤を厚さ３０μｍのＰＥフィルムに厚さが１μｍおよび２μｍになるようにロールコータ法によりそれぞれ塗布し、乾燥して前記ＰＥフィルムにガスバリア層を形成することにより２種のガスバリア性積層フィルムを製造した。
【０１９１】
得られた実施例４の積層フィルムについて、実施例１と同様な方法により酸素透過量および水蒸気透過量を測定した。その結果を下記表４に示す。なお、下記表４には参照例７として、厚さ３０μｍのＰＥフィルムの酸素透過量および水蒸気透過量を併記した。
【０１９２】
【表４】

【０１９３】
なお、実施例４のガスバリア性積層フィルムは基材フィルムであるＰＥと同等の透明性を有していた。
【０１９４】
また、実施例４のガスバリア性積層フィルムは屈曲を繰り返しても前記表４の優れた酸素遮断性および水蒸気遮断性が維持された。
【０１９５】
（実施例５）
水とイソプロピルアルコール（ＩＰＡ）とを５０：５０の重量比で混合した溶剤にポリビニルアルコール（ＰＶＡ）を２５重量％添加し、９５℃の温度下で前記樹脂を溶解した後、この溶液に酸化ケイ素粉末の凝集物（一次粒子の平均粒 径；７ｎｍ）および酸化チタン粉末の凝集物（一次粒子の平均粒径；２０ｎｍ）を前記ＰＶＡに対してそれぞれ２５重量％、５重量％添加して液状混合物を調製した。つづいて、この液状混合物を９５℃の温度維持しながら、前述した図３に示す衝突破砕装置を用い、下記に示す条件で衝突破砕を４回繰り返した。この工程により前記各凝集物が解粉され、同時に前記ＰＶＡと均一に分散接合または結合がなされ、平均粒径７ｎｍのＳｉＯ₂超微粉末および平均粒径２０ｎｍのＴｉ Ｏ₂超微粉末と前記ＰＶＡとが溶剤の存在下で均一に分散接合された多数の複合超 微粒子を含むガスバリアコート剤が調製された。
【０１９６】
＜衝突破砕条件＞
・液状混合物の加圧力；約２０００Ｋｇ／ｃｍ^2
・ノズル部を通過する液状混合物の加速度；約３００ｍ／ｓｅｃ
得られたガスバリアコート剤は、常温ないしそれ以下の温度で酸化ケイ素のような無機化合物の超微粉末が析出したり、繊維状に成長したりすることなく、安定した性状を有するものであった。また、前記ガスバリアコート剤中の前記複合超微粒子は平均粒径が０．１μｍであった。
【０１９７】
次いで、前記ガスバリアコート剤を厚さ３０μｍの無延伸ポリプロピレン（ＣＰＰ）フィルムに厚さが１μｍおよび２μｍになるようにロールコータ法によりそれぞれ塗布し、乾燥して前記ナイロンフィルムにガスバリア層を形成することによって２種の積層フィルムを製造した。
【０１９８】
前記ガスバリア層を電子顕微鏡で観察した。その結果、ＰＶＡに平均粒径７ｎｍの酸化ケイ素超微粉末および平均粒径２０ｎｍの酸化チタン超微粉末が均一に分散されていることが確認された。
【０１９９】
得られた実施例５の積層フィルムについて、実施例１と同様な方法により酸素透過量および水蒸気透過量を測定した。その結果を下記表５に示す。なお、下記表５には参照例８として、厚さ３０μｍのＣＰＰフィルムの酸素透過量および水蒸気透過量を併記した。
【０２００】
【表５】

【０２０１】
なお、実施例５のガスバリア性積層フィルムは基材フィルムであるＣＰＰと同等の透明性を有していた。
【０２０２】
また、実施例５のガスバリア性積層フィルムは屈曲を繰り返しても前記表５の優れた酸素遮断性および水蒸気遮断性が維持された。
【０２０３】
（実施例６）
水とイソプロピルアルコール（ＩＰＡ）とを５０：５０の重量比で混合した溶剤にポリビニルアルコール（ＰＶＡ）を添加し、１００℃の温度下で前記ＰＶＡを溶解した後、この溶液に疎水化処理した酸化ケイ素粉末の凝集物（一次粒子の平均粒径；７ｎｍ）［日本アエロジル社製商品名；Ｒ−８１２］を添加して液状混合物を調製した。なお、前記ＰＶＡおよび前記疎水化処理酸化ケイ素（Ｒ−８１２）は前記溶剤に対してそれぞれ７０重量％、３０重量％となるように添加した。
【０２０４】
次いで、前記液状混合物を８０℃の温度維持しながら、前述した図３に示す衝突破砕装置を用い、下記に示す条件で衝突破砕を８回繰り返した。この工程により前記凝集物が解粉され、同時に前記混合樹脂と均一に分散接合または結合がなされ、平均粒径７ｎｍの疎水化処理酸化ケイ素（Ｒ−８１２）の超微粉末と前記ＰＶＡとが溶剤の存在下で 均一に分散接合された多数の複合超微粒子を含むガスバリアコート剤が調製された。
【０２０５】
＜衝突破砕条件＞
・液状混合物の加圧力；約２０００Ｋｇ／ｃｍ^2
・ノズル部を通過する液状混合物の加速度；約２００ｍ／ｓｅｃ
得られたガスバリアコート剤は、常温ないしそれ以下の温度で疎水化処理酸化ケイ素（Ｒ−８１２）の超微粉末が析出したり、繊維状に成長したりすることなく、安定した性状を有するものであった。また、前記ガスバリアコート剤中の前記複合超微粒子は平均粒径が０．１μｍであった
次いで、前記ガスバリアコート剤を厚さ３０μｍの延伸ポリプロピレン（ＯＰＰ）フィルムに厚さが２μｍになるようにロールコータ法により塗布し、乾燥して前記ＯＰＰフィルムにガスバリア層を形成することによりガスバリア性積層フィルムを製造した。
【０２０６】
前記ガスバリア層を電子顕微鏡で観察した。その結果、このガスバリア層はＰＶＡに平均粒径７ｎｍの疎水化処理酸化ケイ素超微粉末（Ｒ−８１２の超微粉末）が均一に分散されていることが確認された。
【０２０７】
また、前記ガスバリア層は前記ＯＰＰフィルム表面に実質的に平行な面１ｍ²当たりに存在する多数の疎水化処理酸化ケイ素超微粉末（Ｒ−８１２の超微粉末）における比表面積の合計が１００ｍ²であった。
【０２０８】
（実施例７）
水とイソプロピルアルコール（ＩＰＡ）とを５０：５０の重量比で混合した溶剤にポリビニルアルコール（ＰＶＡ）を添加し、１００℃の温度下で前記ＰＶＡを溶解した後、この溶液に親水化処理した酸化ケイ素粉末の凝集物（一次粒子の平均粒径；７ｎｍ）［日本アエロジル社製商品名；３８０］を添加して液状混合物を調製した。なお、前記ＰＶＡおよび前記親水化処理酸化ケイ素（３８０）は前記溶剤に対してそれぞれ７０重量％、３０重量％となるように添加した。
【０２０９】
次いで、前記液状混合物を８０℃の温度維持しながら、前述した図３に示す衝突破砕装置を用い、実施例６と同様な条件で衝突破砕を８回繰り返した。この工程により前記凝集物が解粉され、同時に前記ＰＶＡと均一に分散接合または結合がなされ、平均粒径７ｎｍの親水化処理酸化ケイ素（３８０）の超微粉末と前記ＰＶＡとが溶剤の存在下で均一に分散接合された多数の複合超微粒子を含むガスバリアコート剤が調製された。
【０２１０】
得られたガスバリアコート剤は、常温ないしそれ以下の温度で親水化処理酸化ケイ素（３８０）の超微粉末が析出したり、繊維状に成長したりすることなく、安定した性状を有するものであった。また、前記ガスバリアコート剤中の前記複合超微粒子は平均粒径が０．１μｍであった。
【０２１１】
次いで、前記ガスバリアコート剤を厚さ３０μｍの延伸ポリプロピレン（ＯＰＰ）フィルムに厚さが２μｍおよび４μｍになるようにロールコータ法によりそれぞれ塗布し、乾燥して前記ＯＰＰフィルムにガスバリア層を形成することにより２種のガスバリア性積層フィルムを製造した。
【０２１２】
前記各ガスバリア層を電子顕微鏡で観察した。その結果、このガスバリア層はＰＶＡに平均粒径７ｎｍの親水性酸化ケイ素超微粉末（３８０の超微粉末）が均一に分散されていることが確認された。
【０２１３】
また、前記各ガスバリア層は前記ＯＰＰフィルム表面に実質的に平行な面１ｍ²当たりに存在するする多数の親水化処理酸化ケイ素超微粉末（３８０の超微粉末）における比表面積の合計が１４０ｍ²であった。
【０２１４】
（実施例８）
水とイソプロピルアルコール（ＩＰＡ）とを５０：５０の重量比で混合した溶剤にポリビニルアルコール（ＰＶＡ）とエチレンビニルアルコール共重合体（ＥＶＯＨ）との混合物（ＰＶＡ：ＥＶＯＨ＝７０：３０）を添加し、１００℃の温度下で前記各樹脂を溶解した後、この溶液に親水化処理した酸化ケイ素粉末の凝集物（一次粒子の平均粒径；７ｎｍ）［日本アエロジル社製商品名；３８０］を添加して液状混合物を調製した。なお、前記混合樹脂および前記親水化処理酸化ケイ素（３８０）は前記溶剤に対してそれぞれ７０重量％、３０重量％となるように添加した。
【０２１５】
次いで、前記液状混合物を８０℃の温度維持しながら、前述した図３に示す衝突破砕装置を用い、実施例６と同様な条件で衝突破砕を８回繰り返した。この工程により前記凝集物が解粉され、同時に前記ＰＶＡ−ＥＶＯＨの混合樹脂と均一に分散接合または結合がなされ、平均粒径７ｎｍの親水化処理酸化ケイ素（３８０）の超微粉末と前記ＰＶＡ−ＥＶＯＨの混合樹脂とが溶剤の存在下で均一に分散接合された多数の複合超微粒子を含むガスバリアコート剤が調製された。
【０２１６】
得られたガスバリアコート剤は、常温ないしそれ以下の温度で親水化処理酸化ケイ素（３８０）の超微粉末が析出したり、繊維状に成長したりすることなく、安定した性状を有するものであった。また、前記ガスバリアコート剤中の前記複合超微粒子は平均粒径が０．１μｍであった。
【０２１７】
次いで、前記ガスバリアコート剤を厚さ３０μｍの延伸ポリプロピレン（ＯＰＰ）フィルムに厚さが２μｍになるようにロールコータ法によりそれぞれ塗布 し、乾燥して前記ＯＰＰフィルムにガスバリア層を形成することによりバリア性積層フィルムを製造した。
【０２１８】
前記ガスバリア層を電子顕微鏡で観察した。その結果、このガスバリア層はＰＶＡ−ＥＶＯＨの混合樹脂に平均粒径７ｎｍの親水性酸化ケイ素超微粉末（３８０の超微粉末）が均一に分散されていることが確認された。
【０２１９】
また、前記ガスバリア層は前記ＯＰＰフィルム表面に実質的に平行な面１ｍ²当たりに存在する多数の親水化処理酸化ケイ素超微粉末（３８０の超微粉末）における比表面積の合計が１４０ｍ²であった。
【０２２０】
（実施例９）
水とイソプロピルアルコール（ＩＰＡ）とを５０：５０の重量比で混合した溶剤にポリビニルアルコール（ＰＶＡ）を添加し、１００℃の温度下で前記ＰＶＡを溶解した後、この溶液に親水化処理した酸化ケイ素粉末の凝集物（一次粒子の平均粒径；７ｎｍ）［日本アエロジル社製商品名；３８０］を添加して液状混合物を調製した。なお、前記ＰＶＡおよび前記親水化処理酸化ケイ素（３８０）は前記溶剤に対してそれぞれ７０重量％、３０重量％となるように添加した。
【０２２１】
次いで、前記液状混合物を８０℃の温度維持しながら、前述した図３に示す衝突破砕装置を用い、実施例６と同様な条件で衝突破砕を８回繰り返した。この工程により前記凝集物が解粉され、同時に前記ＰＶＡと均一に分散接合または結合がなされ、平均粒径７ｎｍの親水化処理酸化ケイ素（３８０）の超微粉末と前記ＰＶＡとが溶剤の存在下で均一に分散接合された多数の複合超微粒子を含む溶液が調製された。この溶液は、常温ないしそれ以下の温度で親水化処理酸化ケイ素（３８０）の超微粉末が析出したり、繊維状に成長したりすることなく、安定した性状を有するものであった。また、前記溶液中の前記複合超微粒子は平均粒径が０．１μｍであった。
【０２２２】
次いで、前記溶液にシランカップング剤（東レ・ダウコーニング社製商品名ＳＨ−６０４０）を前記親水化処理酸化ケイ素に対して１０重量％添加し、攪拌混合することによりバリアコート剤を調製した。このガスバリアコート剤を厚さ３０μｍの延伸ポリプロピレン（ＯＰＰ）フィルムに厚さが２μｍになるようにロールコータ法により塗布し、乾燥して前記ＯＰＰフィルムにガスバリア層を形成することによりガスバリア性積層フィルムを製造した。
【０２２３】
前記ガスバリア層を電子顕微鏡で観察した。その結果、このガスバリア層はＰＶＡに平均粒径７ｎｍの親水性酸化ケイ素超微粉末（３８０の超微粉末）が均一に分散されているとともに、それらＰＶＡと親水性酸化ケイ素超微粉末とがシランカップリング剤により結合、架橋されていることが確認された。
【０２２４】
また、前記ガスバリア層は前記ＯＰＰフィルム表面に実質的に平行な面１ｍ²当たりに存在する多数の親水化処理酸化ケイ素超微粉末（３８０の超微粉末）における比表面積の合計が１１０ｍ²であった。
【０２２５】
（実施例１０）
水とイソプロピルアルコール（ＩＰＡ）とを５０：５０の重量比で混合した溶剤にポリビニルアルコール（ＰＶＡ）を添加し、１００℃の温度下で前記ＰＶＡを溶解した後、この溶液に親水化処理した酸化ケイ素粉末の凝集物（一次粒子の平均粒径；７ｎｍ）［日本アエロジル社製商品名；３８０］および疎水化処理した酸化ケイ素粉末の凝集物（一次粒子の平均粒径；７ｎｍ）［日本アエロジル社製商品名；Ｒ−８１２］をそれぞれ添加して液状混合物を調製した。なお、前記ＰＶＡ、前記親水化処理酸化ケイ素粉末（３８０）および疎水化処理酸化ケイ素粉末（Ｒ−８１２）は前記溶剤に対してそれぞれ６０重量％、３０重量％および１０重量％となるように添加した。
【０２２６】
次いで、前記液状混合物を８０℃の温度維持しながら、前述した図３に示す衝突破砕装置を用い、実施例６と同様な条件で衝突破砕を８回繰り返した。この工程により前記各凝集物が解粉され、同時に前記ＰＶＡと均一に分散接合または結合がなされ、平均粒径７ｎｍの親水化処理酸化ケイ素（３８０）の超微粉末と平均粒径７ｎｍの疎水化処理酸化ケイ素粉末（Ｒ−８１２）の超微粉末と前記ＰＶＡとが溶剤の存在下で均一に分散接合された多数の複合超微粒子を含むガスバリアコート剤が調製された。
【０２２７】
得られたガスバリアコート剤は、常温ないしそれ以下の温度で親水化処理酸化ケイ素（３８０）の超微粉末および疎水化処理酸化ケイ素粉末（Ｒ−８１２）の超微粉末が析出したり、繊維状に成長したりすることなく、安定した性状を有するものであった。また、前記ガスバリアコート剤中の前記複合超微粒子は平均粒径が０．１μｍであった。
【０２２８】
次いで、前記ガスバリアコート剤を厚さ３０μｍの延伸ポリプロピレン（ＯＰＰ）フィルムに厚さが２μｍになるようにロールコータ法により塗布し、乾燥して前記ＯＰＰフィルムにガスバリア層を形成することによりガスバリア性積層フィルムを製造した。
【０２２９】
前記ガスバリア層を電子顕微鏡で観察した。その結果、このガスバリア層はＰＶＡに平均粒径７ｎｍの親水性酸化ケイ素超微粉末（３８０の超微粉末）および平均粒径７ｎｍの疎水化処理酸化ケイ素超微粉末（Ｒ−８１２の超微粉末）が均一に分散されていることが確認された。
【０２３０】
また、前記ガスバリア層は前記ＯＰＰフィルム表面に実質的に平行な面１ｍ²当たりに存在する多数の親水化処理酸化ケイ素超微粉末（３８０の超微粉末）および疎水化処理酸化ケイ素超微粉末（Ｒ−８１２の超微粉末）における比表面積の合計が２５０ｍ²であった。
【０２３１】
（実施例１１）
水とイソプロピルアルコール（ＩＰＡ）とを５０：５０の重量比で混合した溶剤にポリビニルアルコール（ＰＶＡ）を添加し、１００℃の温度下で前記ＰＶＡを溶解した後、この溶液に超疎水化処理した酸化ケイ素粉末の凝集物（一次粒子の平均粒径；７ｎｍ）［日本アエロジル社製商品名；ＲＹ−３００］を添加して液状混合物を調製した。なお、前記ＰＶＡおよび超疎水化処理酸化ケイ素粉末（ＲＹ−３００）は前記溶剤に対してそれぞれ７０重量％および３０重量％となるように添加した。
【０２３２】
次いで、前記液状混合物を８０℃の温度維持しながら、前述した図３に示す衝突破砕装置を用い、実施例６と同様な条件で衝突破砕を８回繰り返した。この工程により前記凝集物が解粉され、同時に前記ＰＶＡと均一に分散接合または結合がなされ、平均粒径７ｎｍの超疎水化処理酸化ケイ素（ＲＹ−３００）の超微粉末と前記ＰＶＡとが溶剤の存在下で均一に分散接合された多数の複合超微粒子を含むガスバリアコート剤が調製された。
【０２３３】
得られたガスバリアコート剤は、常温ないしそれ以下の温度で超疎水化処理酸化ケイ素（ＲＹ−３００）の超微粉末が析出したり、繊維状に成長したりすることなく、安定した性状を有するものであった。また、前記ガスバリアコート剤中の前記複合超微粒子は平均粒径が０．１μｍであった
次いで、厚さ３０μｍの延伸ポリプロピレン（ＯＰＰ）フィルムに実施例７と同様なガスバリアコート剤［ＰＶＡおよび前記親水化処理酸化ケイ素（３８０）の超微粉末からなる複合超微粒子含有］を厚さが２μｍになるようにロールコータ法により塗布し、乾燥して前記ＯＰＰフィルムに第１ガスバリア層（下層ガスバリア層）を形成した。つづいて、この下層ガスバリア層に前記ガスバリアコート剤を厚さが２μｍになるようにロールコータ法により塗布し、乾燥して前記下層ガスバリア層に第２ガスバリア層（上層ガスバリア層）を形成することによりガスバリア性積層フィルムを製造した。
【０２３４】
前記下層ガスバリア層および上層ガスバリア層を電子顕微鏡で観察した。その結果、下層ガスバリア層はＰＶＡに平均粒径７ｎｍの親水性酸化ケイ素超微粉末（３８０の超微粉末）が均一に分散されていることが確認された。上層ガスバリア層は、ＰＶＡに平均粒径７ｎｍの超疎水化処理酸化ケイ素超微粉末（ＲＹ−３００の超微粉末）が均一に分散されていることが確認された。
【０２３５】
また、前記下層ガスバリア層は前記ＯＰＰフィルム表面に実質的に平行な面１ｍ²当たりに存在する多数の親水化処理酸化ケイ素超微粉末（３８０の超微粉末）における比表面積の合計が１４０ｍ²であった。前記上層ガスバリア層は前記ＯＰＰフィルム表面に実質的に平行な面１ｍ²当たりに存在する多数の超疎水化処理酸化ケイ素超微粉末（ＲＹ−３００の超微粉末）における比表面積の合計が１００ｍ²であった。
【０２３６】
得られた実施例６〜１１のガスバリア性積層フィルムについて、実施例１と同様な方法により酸素透過量および水蒸気透過量を測定した。その結果を下記表６に示す。
【０２３７】
なお、下記表６には前記参照例１（厚さ３０μｍのＯＰＰフィルム）の酸素透過量および水蒸気透過量を併記した。
【０２３８】
【表６】

【０２３９】
前記表６から明らかなように実施例６〜１１のガスバリア性積層フィルムはＯＰＰ単体フィルムに比べて優れた酸素遮断性および水蒸気遮断性を有することがわかる。
【０２４０】
特に、実施例６のようなＰＶＡと疎水化処理酸化ケイ素（Ｒ−８１２）の超微粉末からなる複合超微粒子を含むガスバリアコート剤を用いて製造されたガスバリア性積層フィルムと、実施例７のようなＰＶＡと親水化処理酸化ケイ素（３８０）の超微粉末からなる複合超微粒子を含むガスバリアコート剤を用いて製造されたガスバリア性積層フィルムとを対比すると、ガスバリア層が同厚さ（２μｍ）の場合、実施例６の積層フィルムが実施例７の積層フィルムに比べて酸素遮断性および水蒸気遮断性が優れることがわかる。ただし、実施例６の積層フィルムにおいてそのガスバリア層の厚さを４μｍにすると、酸素遮断性および水蒸気遮断性が格段に向上されることがわかる。
【０２４１】
また、実施例８のようなＰＶＡ，ＥＶＯＨの混合樹脂と親水化処理酸化ケイ素（３８０）の超微粉末からなる複合超微粒子を含むガスバリアコート剤を用いて製造されたガスバリア性積層フィルムは、ガスバリア層が２μｍの場合において疎水化処理酸化ケイ素（Ｒ−８１２）の超微粉末を含むガスバリア層を有する実施例７の積層フィルムと同等の酸素遮断性および水蒸気遮断性を有することがわかる。
【０２４２】
さらに、実施例９のようなＰＶＡと親水化処理酸化ケイ素（３８０）の超微粉末からなる複合超微粒子にシランカップリング剤を配合したガスバリアコート剤を用いて製造されたガスバリア性積層フィルムや実施例１０のようなＰＶＡと親水化処理酸化ケイ素（３８０）の超微粉末と疎水化処理酸化ケイ素（Ｒ−８１２）の超微粉末からなる複合超微粒子を含むガスバリアコート剤を用いて製造されたガスバリア性積層フィルムは、実施例６の積層フィルム（ガスバリア層が同厚さ；２μｍ）に比べて酸素遮断性および水蒸気遮断性が著しく向上されることがわかる。
【０２４３】
さらに、実施例１１のようなＰＶＡおよび親水化処理酸化ケイ素（３８０）の超微粉末からなる下層ガスバリア層と、ＰＶＡおよび超疎水化処理酸化ケイ素（ＲＹ−３００）の超微粉末からなる上層ガスバリア層を有するガスバリア性積層フィルムはガスバリア層の厚さを４μｍとした実施例７のガスバリア性積層フィルムに比べて酸素遮断性が若干低いものの、より優れた水蒸気遮断性を有することがわかる。
【０２４４】
なお、実施例６〜１１のガスバリア性積層フィルムは基材フィルムであるＯＰＰと同等の透明性を有していた。
【０２４５】
実施例６〜１１のガスバリア性積層フィルムは屈曲を繰り返しても前記表６の優れた酸素遮断性および水蒸気遮断性が維持された。
【０２４６】
（実施例１２）
厚さ１２μｍのＰＥＴフィルムに実施例６で調製したガスバリアコート剤を厚さが２μｍになるようにロールコータ法により塗布し、乾燥して前記ＰＥＴフィルムにガスバリア層を形成することによりガスバリア性積層フィルムを製造した。
【０２４７】
前記ガスバリア層を電子顕微鏡で観察した。その結果、このガスバリア層ＰＶＡに平均粒径７ｎｍの疎水化処理酸化ケイ素超微粉末（Ｒ−８１２の超微粉末）が均一に分散されていることが確認された。
【０２４８】
また、前記ガスバリア層は前記ＰＥＴフィルム表面に実質的に平行な面１ｍ²当たりに存在する多数の疎水化処理酸化ケイ素超微粉末（Ｒ−８１２の超微粉末）における比表面積の合計が１００ｍ²であった。
【０２４９】
（実施例１３）
厚さ１２μｍのＰＥＴフィルムに実施例７で調製したガスバリアコート剤を厚さが２μｍになるようにロールコータ法により塗布し、乾燥して前記ＰＥＴフィルムにガスバリア層を形成することによりガスバリア性積層フィルムを製造した。
【０２５０】
前記ガスバリア層を電子顕微鏡で観察した。その結果、このガスバリア層はＰＶＡに平均粒径７ｎｍの親水化処理酸化ケイ素超微粉末（３８０の超微粉末）が均一に分散されていることが確認された。
【０２５１】
また、前記ガスバリア層は前記ＰＥＴフィルム表面に実質的に平行な面１ｍ²当たりに存在する多数の親水化処理酸化ケイ素超微粉末（３８０の超微粉末）における比表面積の合計が１４０ｍ²であった。
【０２５２】
（実施例１４）
竜王コート紙に実施例６で調製したガスバリアコート剤を厚さが２μｍになるようにロールコータ法により塗布し、乾燥して前記竜王コート紙にガスバリア層を形成することによりガスバリア性積層フィルムを製造した。
【０２５３】
前記ガスバリア層を電子顕微鏡で観察した。その結果、このガスバリア層はＰＶＡに平均粒径７ｎｍの疎水化処理酸化ケイ素超微粉末（Ｒ−８１２の超微粉末）が均一に分散されていることが確認された。
【０２５４】
また、前記ガスバリア層は前記竜王コート紙表面に実質的に平行な面１ｍ²当たりに存在する多数の疎水化処理酸化ケイ素超微粉末（Ｒ−８１２の超微粉末）における比表面積の合計が１００ｍ²であった。
【０２５５】
（実施例１５）
竜王コート紙に実施例７で調製したガスバリアコート剤を厚さが２μｍになるようにロールコータ法により塗布し、乾燥して前記竜王コート紙にガスバリア層を形成することによりガスバリア性積層フィルムを製造した。
【０２５６】
前記ガスバリア層を電子顕微鏡で観察した。その結果、このガスバリア層はＰＶＡに平均粒径７ｎｍの親水化処理酸化ケイ素超微粉末（３８０の超微粉末）が均一に分散されていることが確認された。
【０２５７】
また、前記ガスバリア層は前記竜王コート紙表面に実質的に平行な面１ｍ²当たりに存在する多数の親水化処理酸化ケイ素超微粉末（３８０の超微粉末）における比表面積の合計が１４ｍ²であった。
【０２５８】
得られた実施例１２〜１５のガスバリア性積層フィルムについて、実施例１と同様な方法により酸素透過量および水蒸気透過量を測定した。その結果を下記表７に示す。
【０２５９】
なお、下記表７には前記参照例５（厚さ１２μｍのＰＥＴフィルム）および参照例９（竜王コート紙単体）の酸素透過量および水蒸気透過量を併記した。
【０２６０】
【表７】

【０２６１】
また、実施例１２、１３のガスバリア性積層フィルムは基材フィルムであるＰＥＴと同等の透明性を有していた。
【０２６２】
さらに、実施例１２〜１５のガスバリア性積層フィルムは屈曲を繰り返しても前記表７の優れた酸素遮断性および水蒸気遮断性が維持された。
【０２６３】
【発明の効果】
以上詳述したように、本発明によれば屈曲させてもピンホールやクラックが発生せず、かつ無機化合物や金属の膜状態と同等もしくはそれ以上の優れたガスバリア性を有するガスバリア層を備え、食品、医薬等の各種の物品の包装材料に好適なガスバリア性積層フィルムを提供できる。
【０２６４】
本発明は、屈曲させてもピンホールやクラックが発生せず、優れたガスバリア性を有するガスバリア層を備え、かつ基材である有機樹脂フィルムと同等の透明性を有するガスバリア性積層フィルムを提供できる。
【０２６５】
本発明は、真空蒸着のような大掛かりな装置を使用せずに塗布手段により前述の優れたガスバリア性を有するガスバリア層を形成することが可能なガスバリア性積層フィルムの製造方法を提供できる。
【０２６６】
本発明は、優れた前記特性を有するガスバリア性積層フィルムを得ることが可能なガスバリアコート剤を提供できる。
【図面の簡単な説明】
【図１】本発明に係わるガスバリア性積層フィルムを示す断面図。
【図２】図１のフィルムの要部拡大断面図。
【図３】本発明の製造方法に用いられるガスバリアコート剤を調製するための衝突破砕装置を示す断面図。
【符号の説明】
１…ガスバリア性積層フィルム、
２…有機高分子フィルム、
３…ガスバリア層、
４…ガスバリア性有機高分子、
５…超微粉末、
１１…本体、
１４…空洞部、
１６ａ，１６ｂ…加速流路、
１７ａ，１７ｂ…ノズル部、
１９…上部ブロック、
２４…下部ブロック。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a gas barrier laminated film used for packaging materials for various articles such as food and medicine, a method for producing the gas barrier laminated film, and a gas barrier coating agent for forming a gas barrier layer on a substrate film.
[0002]
[Prior art]
Foods such as snacks, pharmaceuticals, and articles that do not want to be exposed to oxygen or water vapor are packaged with a film having a barrier property against gas such as oxygen or water vapor and protected from the outside for a long time. .
[0003]
Conventionally known as the gas barrier film are polyvinylidene chloride (PVDC) and ethylene / vinyl alcohol copolymer (EV OH resin), which have less gas diffusion and penetration. However, the PVDC film has a problem that harmful chlorine gas is generated at the time of incineration at the time of disposal. In addition, when the EVOH resin film is exposed to a humid atmosphere (humid atmosphere), there is a problem that the oxygen barrier property is remarkably lowered.
[0004]
For these reasons, laminated films having a gas barrier layer have been developed and put into practical use. Specifically, a gas barrier laminate film in which a gas barrier layer made of aluminum (Al) is vapor-deposited on a polyethylene terephthalate (PET) film, and a gas barrier property in which a gas barrier layer of an inorganic compound such as silicon oxide is coated on the PET film by vacuum vapor deposition or the like. There is a laminated film.
[0005]
However, the laminated film having the gas barrier layer has a gas barrier layer made of Al or an inorganic compound on the lower surface of a long PET film which is movably disposed in an upper portion of the chamber by evaporating Al or an inorganic compound in a vacuum chamber. Since it is manufactured by forming, not only a large-scale apparatus is required, but also the manufacturing efficiency of the laminated film per hour is naturally limited.
[0006]
Moreover, the laminated film which has a gas barrier layer which consists of an insulating inorganic compound like a silicon oxide has the characteristics that it can be used for a microwave oven like a resin film. However, since this laminated film is formed by vapor deposition of a hard inorganic compound such as silicon oxide, the gas barrier layer generates pinholes and cracks in the gas barrier layer, and the barrier property against oxygen and water vapor is remarkably deteriorated. There was a problem.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a gas barrier laminate film having a gas barrier layer that does not cause pinholes or cracks even when bent and has an excellent gas barrier property equal to or higher than that of an inorganic compound or metal film. To do.
[0008]
The present invention provides a gas barrier laminated film having a gas barrier layer having excellent gas barrier properties that does not generate pinholes and cracks even when bent, and having transparency equivalent to an organic polymer film as a substrate. It is something to try.
[0009]
The present invention intends to provide a method for producing a gas barrier laminated film capable of forming the gas barrier layer having the above-described excellent gas barrier property by a coating means without using a large-scale apparatus such as vacuum deposition. It is.
[0011]
[Means for Solving the Problems]
  Gas barrier laminate film according to the present invention,Base film;
  A first gas barrier layer comprising a large number of ultrafine powders having an average particle size of 100 nm or less, comprising a gas barrier organic polymer and a hydrophilic inorganic compound dispersed in the polymer, laminated on the base film;
  A second gas barrier layer, which is laminated on the first gas barrier layer, and includes a number of ultrafine powders having an average particle size of 100 nm or less made of a gas barrier organic polymer and a hydrophobic inorganic compound dispersed in the polymer;
Comprising
  The first gas barrier layer has a surface 1 m in which individual ultrafine powders are in close contact with each other over the entire surface direction and thickness direction of the base film and are substantially parallel to the surface of the base film. ² The total specific surface area of a large number of ultrafine powders per unit is 100 to 600 m ² And
  The second gas barrier layer is a surface in which individual ultrafine powders are in close contact with each other over the entire surface direction and thickness direction of the first gas barrier layer and are substantially parallel to the surface of the base film. 1m ² The total specific surface area of a large number of ultrafine powders per unit is 50 to 200 m ² IsIt is characterized by this.
[0018]
  The gas barrier laminate film according to the present invention is a base film;
  Gas barrier organic polymer and hydrophobic inorganic compound dispersed in the polymer laminated on the base filmA large number of particles having an average particle size of 100 nm or lessContains ultra fine powderA first gas barrier layer; and
  A second gas barrier layer, which is laminated on the first gas barrier layer, and includes a number of ultrafine powders having an average particle diameter of 100 nm or less made of a gas barrier organic polymer and a hydrophilic inorganic compound dispersed in the polymer;
Comprising
The first gas barrier layer has a surface 1 m in which individual ultrafine powders are in close contact with each other over the entire surface direction and thickness direction of the base film and are substantially parallel to the surface of the base film. ² The total specific surface area of a large number of ultrafine powders per unit is 50 to 200 m ² And
  The second gas barrier layer is a surface in which individual ultrafine powders are in close contact with each other over the entire surface direction and thickness direction of the first gas barrier layer and are substantially parallel to the surface of the base film. 1m ² The total specific surface area of a large number of ultrafine powders per unit is 100 to 600 m ² IsIt is characterized by this.
[0022]
  The method for producing a gas barrier laminate film according to the present invention comprises a hydrophilic inorganic compound.A large number of particles having an average particle size of 100 nm or lessUltra fine powder and hydrophobic inorganic compoundA large number of particles having an average particle size of 100 nm or lessSuper fine powderMixedPreparing a gas barrier coating agent containing a large number of composite ultrafine particles in which a mixed ultrafine powder and a gas barrier organic polymer are dispersed and bonded or bonded in the presence of a solvent; and
  A surface 1 m substantially parallel to the surface of the base film by applying the barrier coating agent to the base film and drying it.²The total specific surface area of a large number of ultrafine powders per unit is 150 to 600 m²Forming a gas barrier layer which is
It is characterized by comprising.
[0023]
  The method for producing a gas barrier laminate film according to the present invention comprises a hydrophobic inorganic compoundA large number of particles having an average particle size of 100 nm or lessPreparing a first gas barrier coating agent containing a large number of composite ultrafine particles in which an ultrafine powder and a gas barrier organic polymer are dispersed or bonded in the presence of a solvent;
  Hydrophilic inorganic compoundA large number of particles having an average particle size of 100 nm or lessPreparing a second gas barrier coating agent containing a large number of composite ultrafine particles in which an ultrafine powder and a gas barrier organic polymer are dispersed and bonded or bonded in the presence of a solvent; and
  A surface 1 m substantially parallel to the surface of the base film by applying to the base film using the first and second barrier coating agents and drying.²The total specific surface area of a large number of hydrophobic inorganic compound ultrafine powders present per unit is 50 to 200 m²The first gas barrier layer and the surface substantially parallel to the surface of the base film 1m²The total specific surface area of a large number of hydrophilic inorganic compound ultrafine powders per unit is 100 to 600 m²Forming a second gas barrier layer which is
It is characterized by comprising.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the gas barrier laminate film according to the present invention will be described in detail with reference to FIGS.
[0026]
The gas barrier laminated film 1 includes an organic polymer film 2 and a gas barrier layer 3 laminated on one side of the film 2. The gas barrier layer 3 contains a gas barrier organic polymer 4 and a number of ultrafine powders 5 dispersed in the polymer 4 and made of at least one material selected from inorganic compounds and metals and having an average particle size of 100 nm or less. To do.
[0027]
As the organic polymer film, various organic resin films applied to packaging materials can be used. For example, polyethylene terephthalate (PET) film, nylon film, oriented polypropylene film, non-oriented polyethylene film, ethyl vinyl An acetate copolymer (EVA) film, a polypropylene film, etc. can be used. These films can be used in the form of one layer or two or more layers.
[0028]
The ultrafine powder is made of an inorganic compound such as silicon oxide, zirconium oxide, titanium oxide, alumina, magnesium oxide or tin oxide, or a metal such as aluminum, tin or zinc. The ultrafine powder can be used in the form of one or a mixture of two or more selected from the inorganic compounds and metals. By using an insulating inorganic compound such as silicon oxide as the ultrafine powder, the entire laminated film can be made insulating. The ultrafine powder is particularly preferably silicon oxide that can be easily made into ultrafine powder.
[0029]
The ultrafine powder having the average particle diameter can impart excellent oxygen barrier properties and water vapor barrier properties to the gas barrier layer. When the average particle diameter of the ultrafine powder exceeds 100 nm, it becomes difficult to increase the amount of dispersion of the ultrafine powder per volume in the gas barrier layer. A more preferable average particle size of the ultrafine powder is 50 nm or less.
[0030]
The gas barrier organic polymer has oxygen and water vapor transmission rates of 10 cc / m, respectively.²・ 24hr or less, 10g / m²-It is preferable that it is 24 hours or less, for example, an ethylene vinyl alcohol copolymer, polyvinyl alcohol, etc. can be mentioned, These can be used with the form of 1 type, or 2 or more types of mixtures.
[0031]
The gas barrier layer preferably has a thickness of 1 μm or more. When the thickness of the gas barrier layer is less than 1 μm, it becomes difficult to impart high gas barrier properties to the laminated film. The thickness of the gas barrier layer is more preferably 2 to 5 μm, still more preferably 2 to 3 μm.
[0032]
It should be noted that the same or different organic polymer film as the organic polymer film, or paper, non-woven fabric or the like may be laminated on the surface of the gas barrier layer opposite to the organic polymer film with an adhesive.
[0033]
The gas barrier laminate film of the present invention described above is an organic polymer film, and is laminated on the organic polymer film, dispersed in the gas barrier organic polymer and the polymer, and at least one selected from inorganic compounds and metals. And a gas barrier layer including a number of ultrafine powders having an average particle diameter of 100 nm or less made of a material.
[0034]
Such a laminated film has a gas barrier layer having a gas barrier organic polymer as a base material, and thus has an action of blocking oxygen and water vapor. Further, since a large number of ultrafine powders having an average particle diameter of 100 nm or less made of at least one material selected from inorganic compounds and metals having high gas barrier properties are dispersed in the gas barrier layer itself, the gas barrier organic It has superior oxygen barrier properties and water vapor barrier properties compared to a layer consisting of a polymer alone.
[0035]
That is, as shown in FIG. 1 and FIG. 2 described above, the presence of a large number of ultrafine powders 5 having an average particle size of 100 nm or less dispersed in the gas barrier organic polymer 4 causes the gas barrier layer 3 to bend with respect to gases such as oxygen and water vapor. Since a so-called tortuous path is formed, a gas barrier laminated film exhibiting excellent oxygen barrier properties and water vapor barrier properties can be obtained.
[0036]
Furthermore, since the gas barrier layer contains a large number of ultrafine powders and organic polymers, it has an appropriate flexibility and can prevent occurrence of pinholes and cracks even when bent.
[0037]
Therefore, according to the present invention, pinholes and cracks do not occur even when bent, and excellent oxygen barrier properties (for example, 10 g / m 2) equivalent to or better than those of inorganic compounds and metal films.²・ 24 hr or less), water vapor barrier (for example, 10 cc / m)²A gas barrier laminate film suitable for packaging materials for various articles such as foods and medicines having a gas barrier layer having a gas barrier property such as 24 hr or less) can be provided.
[0038]
Furthermore, by using at least one resin selected from ethylene vinyl alcohol copolymer and polyvinyl alcohol as a gas barrier organic polymer constituting the gas barrier layer, and using silicon oxide as ultrafine particles, excellent oxygen barrier properties, A gas barrier laminate film having gas barrier properties such as water vapor barrier properties and high transparency equivalent to an organic polymer film as a substrate can be provided.
[0039]
In particular, if the thickness of the gas barrier layer is 1 μm or more compared to a conventional deposited film of Al or ceramic, a laminated film including a gas barrier layer having further superior oxygen barrier properties and water vapor barrier properties can be realized.
[0040]
Furthermore, by using at least one resin selected from ethylene vinyl alcohol copolymer and polyvinyl alcohol as a gas barrier organic polymer constituting the gas barrier layer, and using silicon oxide as ultrafine particles, excellent oxygen barrier properties, A gas barrier laminate film having gas barrier properties such as water vapor barrier properties and high transparency equivalent to an organic polymer film as a substrate can be provided.
[0041]
Furthermore, at least one selected from ethylene vinyl alcohol copolymer and polyvinyl alcohol is used as a gas barrier organic polymer constituting the gas barrier layer using a film or paper of organic polymer not containing chlorine such as PET and OPP as a substrate. By using one resin, the gas barrier layer can be easily removed from the substrate by treating the waste product with, for example, a mixed solvent of alcohol and water. As a result, it is easy to collect and reuse the base material, and even when incinerated waste products do not discharge chlorine-based compounds harmful to the human body, so it is possible to provide an environmentally friendly gas barrier laminated film .
[0042]
Next, the gas barrier coating agent according to the present invention will be described.
[0043]
This gas barrier coating agent has an average particle diameter in which an ultrafine powder having an average particle diameter of 100 nm or less made of at least one material selected from inorganic compounds and metals and a gas barrier organic polymer are dispersed and bonded or bonded in the presence of a solvent. Contains a large number of composite ultrafine particles of 1 μm or less.
[0044]
The gas barrier coating agent is an emulsified form composed of a large number of the composite ultrafine particles, or when the amount of the solvent is large, a form in which a large number of the composite ultrafine particles are individually dispersed or aggregated and suspended in the solvent, Have
[0045]
As the inorganic compound, metal, and gas barrier organic polymer, the same materials as those described in the invention of the gas barrier laminated film are used.
[0046]
When the average particle diameter of the ultrafine powder exceeds 100 nm, it becomes difficult to increase the amount of dispersion of the ultrafine powder per volume in the barrier layer. A more preferable average particle size of the ultrafine powder is 50 nm or less.
[0047]
Examples of the solvent include alcohols such as ethyl alcohol, isopropyl alcohol and isobutyl alcohol, ketones such as methyl ethyl ketone, organic solvents such as toluene and xylene, or water, and these solvents may be used alone or in a mixed solution. Can be used.
[0048]
The composite ultrafine particles have a form having an average particle diameter of 1.0 μm or less in which a plurality of the ultrafine powders and the organic polymer are dispersed or bonded, for example, at a molecular level. The average particle size of the composite ultrafine particles is desirably 0.1 μm or less, more preferably 0.01 μm or less.
[0049]
The gas barrier coating agent is prepared, for example, by the following method.
[0050]
First, a gas barrier organic polymer is dissolved in a solvent to form a liquid, and fine particles of at least one material selected from an inorganic compound and a metal are mixed therewith. Subsequently, after pressurizing the liquid mixture, a gas barrier coating agent is prepared by repeating the operation of crushing and crushing the liquid mixture at a high speed a plurality of times.
[0051]
Specifically, a gas barrier coating agent is prepared by a collision crushing apparatus shown in FIG.
[0052]
In FIG. 3, the body 11 has rectangular holes 12, 13 into which upper and lower blocks, which will be described later, are inserted and fixed, respectively. The main body 11 located between the rectangular holes 12 and 13 is formed with a trapezoidal cavity 14 where the accelerated flow of the raw material collides with each other. In addition, the upper and lower opening diameters of the cavity portion 14 having the trapezoidal shape are smaller than the upper and lower rectangular holes 12 and 13. A pair of protrusions 15 a and 15 b inclined downward at a desired angle are formed on the main body 11 so as to face each other on the intermediate inner surface of the cavity portion 14.
[0053]
The pair of acceleration channels 16a and 16b has one end opened on the opposing inner surface of the upper rectangular hole 12, and the other end opened on the tip surface of the protrusions 15a and 15b. Is formed. The nozzle portions 17a and 17b are interposed in the acceleration flow paths 16a and 16b located at the bases of the protrusions 15a and 15b, respectively.
[0054]
A rectangular upper block 19 provided with a threaded hole 18 is inserted and fixed in the upper rectangular hole 12 of the main body 11. The pair of branch flow paths 20 a and 20 b are communicated with the hole 18 through an inverted conical through hole 21. Each of the branch channels 20a and 20b is opened on the outer surface facing the upper block 12 so as to communicate with the acceleration channels 16a and 16b. A raw material supply pipe (not shown) is screwed and connected to the threaded hole 18 of the upper block 12. Further, O-rings 22a and 22b are interposed in communication portions between the acceleration channels 16a and 16b of the main body 11 and the branch channels 20a and 20b of the upper block 19, respectively.
[0055]
A rectangular lower block 24 in which a threaded hole 23 is formed is inserted and fixed in the lower rectangular hole 13 of the main body 11. The hole 23 communicates with the cavity portion 14 of the main body 11 through a cylindrical hole 25. A processing liquid discharge pipe (not shown) is screwed and connected to the threaded hole 23 of the lower block 24.
[0056]
The preparation of the gas barrier coating agent using the apparatus shown in FIG. 3 will be described. First, the liquid mixture obtained by the above-described method is pressurized from a raw material supply pipe (not shown) and supplied into the upper block 19. When the pressurized liquid mixture is supplied into the upper block 19, the liquid mixture is separated into the branch flow paths 20a and 20b through the reverse conical through holes 21, and is further supplied to the acceleration flow paths 16a and 16b. . The liquid mixture that has flowed into the acceleration channels 16a and 16b is further accelerated in the process of passing through the nozzle portions 17a and 17b, and is injected into the cavity portion 14 of the main body 11 from the openings of the protrusion portions 15a and 15b. At this time, since the protrusions 15a and 15b are inclined downward and face each other, the liquid mixture ejected from the openings of the protrusions 15a and 15b collides with each other near the center of the cavity 14. The mixture is then crushed. The liquid mixture subjected to the crushing process is discharged from the hollow part 14 through the cylindrical hole 25 of the lower block part 24 and the threaded hole 23 to the processing discharge pipe.
[0057]
By repeating the collision crushing step of the liquid mixture using such a collision crushing apparatus a plurality of times, the gas barrier organic polymer and the fine particles made of at least one material selected from the inorganic compound and metal are crushed uniformly. To be dispersed joined or bonded. Therefore, a gas barrier coating agent containing a large number of composite ultrafine particles in which a gas barrier organic polymer and an ultrafine powder having an average particle size of 100 nm or less are bonded or bonded is prepared.
[0058]
The fine particles of at least one material selected from the inorganic compound and metal preferably have an average particle size of 1000 nm or less from the viewpoint of shortening the generation time of the composite fine particles. Moreover, you may use the aggregate of the ultrafine powder (100 nm or less) which has a final particle diameter.
[0059]
The fine powder of at least one material selected from the organic polymer, the inorganic compound and the metal in the liquid mixture is preferably 20% by weight or more, preferably 25 to 40% by weight with respect to the solvent.
[0060]
The fine powder of at least one material selected from the inorganic compound and metal is preferably added in a proportion of 20 to 60% by weight with respect to the organic polymer. When the addition amount of the fine powder is less than 20% by weight, it becomes difficult to impart sufficiently high oxygen barrier properties and water vapor barrier properties to the gas barrier layer formed by applying and drying the gas barrier coating agent. On the other hand, when the addition amount of the fine powder exceeds 60% by weight, the flexibility of the gas barrier layer formed by applying and drying the gas barrier coating agent is lowered, resulting in the flexibility of the laminated film itself. There is a risk that the sex and the like will decrease. Further, since the amount of the organic polymer in the gas barrier layer formed by applying and drying the gas barrier coating agent is relatively reduced, the adhesive strength of the gas barrier layer to the organic polymer film may be reduced. The addition amount of the fine powder with respect to the organic polymer is more preferably 30 to 50% by weight.
[0061]
The pressure applied to the liquid mixture is 1000 kg / cm.²It is preferable to set the pressure above.
[0062]
The speed at the time of colliding and crushing the liquid mixture is preferably 100 m / sec or more. By gasifying and crushing the liquid mixture at such a high speed, it becomes possible to prepare a gas barrier coating agent containing a large number of composite ultrafine particles having a desired average particle size in a short time.
[0063]
The liquid mixture is heated to a temperature lower than the decomposition temperature of the organic polymer, preferably to a temperature of 30 to 100 ° C. in the step of dissolving the organic polymer in a solvent and the step of colliding and crushing each other at the time of preparation. Allow.
[0064]
Next, the manufacturing method of the gas barrier laminated film concerning this invention is demonstrated.
[0065]
A gas barrier laminate film is produced by applying the gas barrier coating agent described above to an organic polymer film and drying to form a gas barrier layer.
[0066]
As the coating means, for example, the gas barrier coating agent is accommodated in a container, and a gas barrier is applied to the lower surface of the film through a long organic polymer film between a lower roll and an upper roll partially immersed in the gas barrier coating agent. The roll coater method etc. which apply | coat a coating agent are employable.
[0067]
The thickness of the gas barrier layer is preferably 1 μm or more. When the thickness of the gas barrier layer is less than 1 μm, it is difficult to impart high gas barrier properties to the obtained gas barrier laminate film. The thickness of the gas barrier layer is more preferably 2 to 5 μm, still more preferably 2 to 4 μm.
[0068]
In addition, the said base material accept | permits using paper other than an organic polymer film.
[0069]
The gas barrier coating agent according to the present invention described above is obtained by dispersing or bonding an ultrafine powder having an average particle size of 100 nm or less made of at least one material selected from inorganic compounds and metals and a gas barrier organic polymer in the presence of a solvent. It contains a large number of combined ultrafine particles having an average particle size of 1 μm or less, and even when left for a long period of time, the composite ultrafine particles do not aggregate and can maintain a stable emulsion or floating form.
[0070]
By applying such a gas barrier coating agent to a substrate such as an organic polymer film and drying to form a gas barrier layer, no pinholes or cracks occur even when bent as described above, and an inorganic compound or metal A gas barrier laminate film having a gas barrier layer having gas barrier properties such as oxygen barrier properties and water vapor barrier properties equivalent to or better than the above film state can be produced.
[0071]
The gas barrier layer can be formed by applying the gas barrier coating agent to one side of a substrate such as an organic polymer film. For this reason, a gas barrier laminate film can be easily and mass-produced without using a large-scale apparatus like the conventional method of forming a gas barrier layer of aluminum or an inorganic compound by vacuum deposition.
[0072]
In particular, by using a gas barrier coating agent comprising 20 to 60% by weight of an ultrafine powder made of at least one material selected from the above inorganic compounds and metals and 40 to 80% by weight of the gas barrier organic polymer, the gas barrier coating is used. After coating and drying of the agent, the ultrafine powder is substantially in the form of a film, and the gas barrier layer having excellent oxygen barrier property and water vapor barrier property with excellent tortuous pass effect can be formed in good contact with the organic polymer film. . As a result, the gas barrier property can be further improved, and a gas barrier laminate film having excellent adhesion strength between the gas barrier layer and the organic polymer film can be produced.
[0073]
In addition, when a gas barrier coating agent is applied to the organic polymer film and dried to form a gas barrier layer, if the thickness of the gas barrier layer is 1 μm or more compared to a conventional deposited film of Al or ceramic, A laminated film having a gas barrier layer having excellent oxygen barrier properties and water vapor barrier properties can be produced.
[0074]
Next, another gas barrier laminate film according to the present invention will be described.
[0075]
The gas barrier laminate film is laminated on a base film, and includes a gas barrier organic polymer and a number of ultrafine powders composed of at least one material selected from inorganic compounds and metals dispersed in the polymer, Surface substantially parallel to the surface of the base film 1m²The total specific surface area of a large number of ultrafine powders per unit is 50 to 600 m²It has the structure which laminated | stacked the gas barrier layer which is.
[0076]
The base film is made of the above-described organic polymer or paper.
[0077]
As the inorganic compound, metal, and gas barrier organic polymer, the same ones as described above are used.
[0078]
The ultrafine powder preferably has an average particle size of 100 nm or less, more preferably an average particle size of 50 nm or less.
[0079]
In the gas barrier layer, “a surface substantially parallel to the surface of the base film” means all surfaces substantially parallel to the surface of the base film. “Sum of specific surface areas of a number of ultrafine powders” means the surface of the gas barrier layer substantially parallel to the surface of the base film 1 m²It means a value obtained by adding all the outer peripheral areas of the ultra-fine powder present at the center. For this reason, the surface 1 m of the gas barrier layer substantially parallel to the surface of the base film²Even if the number and particle size of a large number of ultrafine powders per unit are the same, if the surface properties of the ultrafine powder are different, for example, if there are wrinkles on the surface, The total specific surface area is increased compared to the case without it.
[0080]
In the gas barrier layer, a surface substantially parallel to the surface of the base film 1 m²The total specific surface area of a large number of ultrafine powders per unit is 50 to 600 m²The reason is as follows. The total specific surface area is 50 m²If it is less, it becomes difficult to form a gas barrier layer having sufficiently high oxygen barrier properties and water vapor barrier properties. Meanwhile, the total specific surface area is 600 m.²If it exceeds 1, the flexibility of the gas barrier layer is lowered, and as a result, the flexibility of the laminated film itself may be lowered. In addition, the amount of the gas barrier organic polymer in the gas barrier layer may be relatively decreased, and the adhesion strength of the gas barrier layer to the base material film may be decreased. More preferable surface 1 m substantially parallel to the surface of the base film²The sum of the specific surface areas of a large number of ultrafine powders per unit is 50 to 400 m²It is.
[0081]
Such a gas barrier laminate film has a surface 1 m substantially parallel to the surface of the base film.²The total specific surface area of a large number of ultrafine powders per unit is 50 to 600 m²Thus, the gas barrier layer having the above-described tortuous pass effect is provided. For this reason, pinholes and cracks do not occur even when bent, and gas barrier properties such as oxygen barrier properties and water vapor barrier properties equivalent to or better than those of inorganic compounds and metals are exhibited.
[0082]
Next, another gas barrier coating agent, a gas barrier laminate film and a method for producing a gas barrier laminate film according to the present invention will be described.
[0083]
(1-1) Gas barrier coating agent
This gas barrier coating agent contains a large number of composite ultrafine particles in which at least one ultrafine powder selected from a hydrophobic inorganic compound and a hydrophilic inorganic compound and a gas barrier organic polymer are dispersed and bonded or bonded in the presence of a solvent. To do.
[0084]
Examples of the hydrophobic inorganic compound include trade names manufactured by Nippon Aerosil Co., Ltd., which are silicon oxide fine powders; R-812, RY-300, and the like.
[0085]
Examples of the hydrophilic inorganic compound include trade name: 380 manufactured by Nippon Aerosil Co., Ltd., which is silicon oxide fine powder.
[0086]
The ultrafine powder desirably has an average particle size of 100 nm or less, more preferably 50 nm or less.
[0087]
The gas barrier organic polymer has oxygen and water vapor transmission rates of 10 cc / m, respectively.²・ 24hr or less, 10g / m²-It is preferable that it is 24 hours or less. As such a gas barrier organic polymer, for example, at least one water-soluble organic polymer selected from polyvinyl alcohol and ethylene vinyl alcohol copolymer can be used. In particular, the former polyvinyl alcohol is preferable because it is less expensive than the latter ethylene vinyl alcohol copolymer.
[0088]
Examples of the solvent include alcohols such as ethyl alcohol, isopropyl alcohol, and isobutyl alcohol, ketones such as methyl ethyl ketone, organic solvents such as toluene and xylene, and water. These solvents may be used alone or in the form of a mixed solution. Can be used.
[0089]
In particular, the solvent is preferably a mixed solution of alcohol and water. It is preferable that the said liquid mixture consists of 30-50 volume% of alcohol and 50-70 volume% of water. The gas barrier coating agent containing such a mixed solution as a solvent can further stabilize the emulsion form and floating form of the composite ultrafine particles over a long period of time, and can also be used for drying treatment when forming a gas barrier layer described later. It becomes possible to speed up.
[0090]
The composite ultrafine particles have a form in which a plurality of the ultrafine powders and the organic polymer are dispersedly bonded or bonded at a molecular level, for example. The composite ultrafine particles desirably have an average particle size of 1.0 μm or less, more preferably 0.1 μm or less, and still more preferably 0.01 μm or less.
[0091]
The composite ultrafine particles are preferably composed of 45 to 85% by weight of a liquid gas barrier organic polymer and 15 to 55% by weight of the ultrafine particles. When the blending amount of the ultrafine powder is less than 15% by weight, it becomes difficult to impart sufficiently high oxygen barrier properties and water vapor barrier properties to the gas barrier layer formed by applying and drying the gas barrier coating agent. . On the other hand, when the blending amount of the ultrafine powder exceeds 55% by weight, the flexibility of the gas barrier layer formed by applying and drying the gas barrier coating agent decreases, and as a result, the laminated film itself can be used. Flexibility or the like may be reduced. Moreover, since the amount of the organic polymer in the gas barrier layer formed by applying and drying the gas barrier coating agent on the base film is relatively reduced, the adhesive strength of the gas barrier layer to the base film is reduced. There is a fear. More preferably, the liquid gas barrier organic polymer and the ultrafine particles are 50 to 80% by weight and 20 to 50% by weight, respectively.
[0092]
The gas barrier coating agent is prepared, for example, by the following method.
[0093]
First, a gas barrier organic polymer is dissolved in a solvent to form a liquid, and at least one fine particle selected from a hydrophobic inorganic compound and a hydrophilic inorganic compound is mixed therewith. Subsequently, after pressurizing this liquid mixture using the above-described collision crushing apparatus shown in FIG. 3, a gas barrier coating agent is prepared by repeating the operation of crushing and crushing the liquid mixture at a high speed a plurality of times.
[0094]
The fine particles preferably have an average particle size of 1000 nm or less from the viewpoint of shortening the production time of the composite fine particles. Moreover, you may use the aggregate of the ultrafine powder (100 nm or less) which has a final particle diameter.
[0095]
  As the fine particles of the hydrophobic inorganic compound, for example, trade names manufactured by Nippon Aerosil Co., Ltd., which are fine silicon oxide powders; R-812 and RY-300 are suitable. As the fine powder of the hydrophilic inorganic compound, for example, trade name manufactured by Nippon Aerosil Co., Ltd., which is a fine powder of silicon oxide;380Is preferred.
[0096]
(1-2A) Gas barrier laminated film
The gas barrier laminate film includes a base film containing a gas barrier organic polymer and an ultrafine powder composed of a hydrophobic inorganic compound dispersed in the polymer, and a surface 1 m substantially parallel to the base film surface.²The total specific surface area of a large number of ultrafine powders per unit is 50 to 200 m²It has the structure which laminated | stacked the gas barrier layer which is. Such a gas barrier laminate film has a structure similar to that shown in FIGS.
[0097]
(1-2B) Gas barrier laminated film
The gas barrier laminate film includes a base film containing a gas barrier organic polymer and an ultrafine powder composed of a hydrophilic inorganic compound dispersed in the polymer, and a surface substantially parallel to the surface of the base film.²The total specific surface area of a large number of ultrafine powders per unit is 100 to 600 m²It has the structure which laminated | stacked the gas barrier layer which is. Such a gas barrier laminate film has a structure similar to that shown in FIGS.
[0098]
(1-2C) Gas barrier laminated film
This gas barrier laminated film includes a base film containing a gas barrier organic polymer and a mixed ultrafine powder composed of a superfine powder of a hydrophilic inorganic compound and a superfine powder of a hydrophobic inorganic compound dispersed in the polymer. 1m surface substantially parallel to the surface of the base film²The total specific surface area of a large number of ultrafine powders per unit is 150 to 600 m²It has the structure which laminated | stacked the gas barrier layer which is.
[0099]
(1-2D) Gas barrier laminated film
This gas barrier laminate film includes a gas barrier organic polymer in a base film and an ultrafine powder of a hydrophilic inorganic compound dispersed in the polymer, and has a surface substantially parallel to the surface of the base film.²The total specific surface area of a large number of hydrophilic inorganic compound ultrafine powders per unit is 100 to 600 m²A gas barrier organic polymer and an ultrafine powder of a hydrophobic inorganic compound dispersed in the polymer, the gas barrier layer being substantially parallel to the surface of the base film. 1m surface²The total specific surface area of a large number of hydrophobic inorganic compound ultrafine powders present per unit is 50 to 200 m²The second gas barrier layer is laminated. In the gas barrier laminate film, the first and second gas barrier layers may be reversed.
[0100]
The base film is made of, for example, an organic polymer or paper.
[0101]
As the organic polymer film, various organic resin films applied to packaging materials can be used. For example, polyethylene terephthalate (PET) film, nylon film, oriented polypropylene film, non-oriented polyethylene film, ethyl vinyl An acetate copolymer (EVA) film, a polypropylene film, etc. can be used. These films can be used in the form of one layer or two or more layers. The organic polymer film allows an anchor coat treatment to be performed on a surface to which the gas barrier layer is applied.
[0102]
Various wrapping papers can be used as the paper. The paper allows a seal coat treatment to be applied to the surface to which the gas barrier layer is applied.
[0103]
As the hydrophobic inorganic compound and the hydrophilic inorganic compound, those similar to those described in (1-1) are used.
[0104]
The ultrafine powder desirably has an average particle size of 100 nm or less, more preferably 50 nm or less.
[0105]
As the gas barrier organic polymer, at least one water-soluble organic polymer selected from polyvinyl alcohol and ethylene vinyl alcohol copolymer similar to those described in (1-1) can be used. In particular, the former polyvinyl alcohol is preferable because it is less expensive than the latter ethylene vinyl alcohol copolymer.
[0106]
The gas barrier layer preferably has a composition comprising 40 to 80% by weight of the gas barrier organic polymer and 20 to 60% by weight of the ultrafine particles. When the blending amount of the ultrafine powder is less than 20% by weight, it becomes difficult to impart sufficiently high oxygen barrier properties and water vapor barrier properties to the gas barrier layer formed by applying and drying the gas barrier coating agent. . On the other hand, when the blending amount of the ultrafine powder exceeds 60% by weight, the flexibility of the gas barrier layer formed by applying and drying the gas barrier coating agent decreases, and as a result, the laminated film itself can be used. Flexibility or the like may be reduced. In addition, since the amount of the organic polymer in the gas barrier layer formed by applying and drying the gas barrier coating agent is relatively reduced, the adhesive strength of the gas barrier layer to the base film may be reduced. More preferably, the weight of the gas barrier organic polymer and the blending amount of the ultrafine particles are 50 to 70% by weight and 30 to 50% by weight, respectively.
[0107]
In the gas barrier layer of the gas barrier laminate film of (1-2A), a surface 1 m substantially parallel to the substrate film surface²The total specific surface area of a large number of hydrophobic inorganic compound ultrafine powders per unit area is 50 to 200 m.²The reason for this is as follows. The total specific surface area is 50 m²If it is less than this, it becomes difficult to form a gas barrier layer having sufficiently high oxygen barrier properties and water vapor barrier properties (particularly water vapor barrier properties). Meanwhile, the total specific surface area is 200 m.²If it exceeds 1, the flexibility of the gas barrier layer is lowered, and as a result, the flexibility of the laminated film itself may be lowered. In addition, the amount of the gas barrier organic polymer in the gas barrier layer may be relatively decreased, and the adhesion strength of the gas barrier layer to the base material film may be decreased. More preferable surface 1 m substantially parallel to the surface of the base film²The sum of specific surface areas of a large number of ultrafine powders per unit is 50 to 150 m.²It is.
[0108]
In the gas barrier layer of the gas barrier laminate film of (1-2B), a surface 1 m substantially parallel to the substrate film surface²The total specific surface area of a large number of hydrophilic inorganic compound ultrafine powders per unit is 100 to 600 m.²The reason for this is as follows. The total specific surface area is 200 m²If it is less than this, it becomes difficult to form a gas barrier layer having sufficiently high oxygen barrier properties and water vapor barrier properties (particularly oxygen barrier properties). Meanwhile, the total specific surface area is 600 m.²If it exceeds 1, the flexibility of the gas barrier layer is lowered, and as a result, the flexibility of the laminated film itself may be lowered. In addition, the amount of the gas barrier organic polymer in the gas barrier layer may be relatively decreased, and the adhesion strength of the gas barrier layer to the base material film may be decreased. More preferable surface 1 m substantially parallel to the surface of the base film²The sum of the specific surface areas of a large number of ultrafine powders per unit is 250 to 300 m.²It is.
[0109]
In the gas barrier layer of the gas barrier laminate film of (1-2C), a surface 1 m substantially parallel to the substrate film surface²The total specific surface area of a large number of ultrafine powders per unit is 150 to 600 m²The reason for this is as follows. The total specific surface area is 150 m²If it is less, it becomes difficult to form a gas barrier layer having sufficiently high oxygen barrier properties and water vapor barrier properties. Meanwhile, the total specific surface area is 600 m.²If it exceeds 1, the flexibility of the gas barrier layer is lowered, and as a result, the flexibility of the laminated film itself may be lowered. In addition, the amount of the gas barrier organic polymer in the gas barrier layer may be relatively decreased, and the adhesion strength of the gas barrier layer to the base material film may be decreased. More preferable surface 1 m substantially parallel to the surface of the base film²The sum of the specific surface areas of a large number of ultrafine powders per unit is 200 to 400 m²It is.
[0110]
In the gas barrier laminate film of (1-2C), the ultrafine powder (mixed ultrafine powder) dispersed in the gas barrier layer is 50 to 70% by weight of the ultrafine powder of the hydrophilic inorganic compound and the hydrophobic inorganic compound. This is preferably 30 to 50% by weight of ultrafine powder. A gas barrier laminate film having such a gas barrier layer is imparted with a good balance between oxygen barrier properties and water vapor barrier properties.
[0111]
In the gas barrier laminate film of (1-2D), the first gas barrier layer is a surface 1 m substantially parallel to the surface of the base film.²The total specific surface area of a large number of hydrophilic inorganic compound ultrafine powders per unit is 100 to 600 m.²And the second gas barrier layer is a surface 1 m substantially parallel to the surface of the base film.²The total specific surface area of a large number of hydrophobic inorganic compound ultrafine powders per unit area is 50 to 200 m.²The reason specified in (1) is the same as described in (1-2B) and (1-2A) above.
[0112]
The gas barrier layer preferably has a thickness of 1 μm or more. When the thickness of the gas barrier layer is less than 1 μm, it becomes difficult to impart high gas barrier properties to the gas barrier laminate film. The thickness of the gas barrier layer is more preferably 2 to 6 μm, still more preferably 2 to 4 μm.
[0113]
In addition, the same or different organic polymer film (top coat) as the organic polymer film (top coat) or paper, non-woven fabric or the like is laminated on the surface of the gas barrier layer opposite to the organic polymer film with an adhesive Allow.
[0114]
(1-3A) Method for producing gas barrier laminate film
A gas barrier coating agent (ultrafine powder is a hydrophobic inorganic compound) described in (1-1) above is applied to a base film, dried, and a surface 1 m substantially parallel to the base film surface²The total specific surface area of a large number of ultrafine powders per unit is 50 to 200 m²A gas barrier layered film is produced by forming a gas barrier layer.
[0115]
(1-3B) Method for producing gas barrier laminate film
A surface 1 m substantially parallel to the surface of the base film after applying the gas barrier coating agent (ultrafine powder is a hydrophilic inorganic compound) described in (1-1) to the base film and drying it.²The total specific surface area of a large number of ultrafine powders per unit is 100 to 600 m²A gas barrier layered film is produced by forming a gas barrier layer.
[0116]
(1-3C) Method for producing gas barrier laminate film
The gas barrier coating agent (ultrafine powder is a mixed ultrafine powder of a hydrophilic inorganic compound and a hydrophobic inorganic compound) described in (1-1) above is applied to a substrate film and dried to substantially form the surface of the substrate film. Parallel plane 1m²The total specific surface area of a large number of ultrafine powders per unit is 150 to 600 m²A gas barrier layered film is produced by forming a gas barrier layer.
[0117]
(1-3D) Method for producing gas barrier laminate film
A surface 1 m substantially parallel to the surface of the base film after applying the gas barrier coating agent (ultrafine powder is a hydrophilic inorganic compound) described in (1-1) to the base film and drying it.²The total specific surface area of a large number of hydrophilic inorganic compound ultrafine powders per unit is 100 to 600 m²A first gas barrier layer is formed. Subsequently, the gas barrier coating agent (ultrafine powder is a hydrophobic inorganic compound) described in (1-1) above is applied onto the gas barrier layer, dried, and substantially parallel to the substrate film surface. 1m²The total specific surface area of a large number of hydrophobic inorganic compound ultrafine powders present per unit is 50 to 200 m²A gas barrier laminate film is produced by forming the second gas barrier layer. In this case, the first and second gas barrier layers may be inverted.
[0118]
As the coating means, for example, the gas barrier coating agent is accommodated in a container, and a gas barrier is applied to the lower surface of the film through a long organic polymer film between a lower roll and an upper roll partially immersed in the gas barrier coating agent. The roll coater method etc. which apply | coat a coating agent are employable.
[0119]
The gas barrier coating agent described above includes a large number of composite ultrafine particles in which at least one ultrafine powder selected from a hydrophobic inorganic compound and a hydrophilic inorganic compound and a gas barrier organic polymer are dispersed and bonded or bonded in the presence of a solvent. Even when left for a long period of time, the composite ultrafine particles do not aggregate and can stably maintain a milky or floating form.
[0120]
The gas barrier laminate film of (1-2A) obtained by applying such a gas barrier coating agent (ultrafine powder is a hydrophobic inorganic compound) to a base film and drying is as follows. Play.
[0121]
(A) Since the gas barrier layer having a gas barrier organic polymer as a base material is provided, an action of blocking oxygen and water vapor is imparted.
[0122]
(B) In the gas barrier layer, a number of inorganic compound ultrafine powders having high gas barrier properties and hydrophobic properties (moisture resistance) are dispersed. Further, the gas barrier layer has a surface 1 m substantially parallel to the surface of the base film.²The total specific surface area of a large number of ultrafine powders per unit is 50 to 200 m²It has become. For this reason, it has superior oxygen barrier properties and water vapor barrier properties as compared with a layer composed only of a gas barrier organic polymer.
[0123]
In other words, the presence of a large number of ultrafine powders dispersed in a gas barrier organic polymer with a specific specific surface area allows the gas barrier layer to exhibit a tortuous pass effect for gases such as oxygen and water vapor and a moisture prevention effect of the ultrafine powder itself. Therefore, it is possible to obtain a gas barrier laminate film that exhibits excellent oxygen barrier properties and water vapor barrier properties. In particular, when the average particle size of the ultrafine powder is 100 nm or less, the tortuous pass effect can be more effectively exhibited.
[0124]
(C) Since the gas barrier layer contains a large number of ultrafine powders and an organic polymer, the gas barrier layer has moderate flexibility and can prevent pinholes and cracks even when bent.
[0125]
Therefore, pinholes and cracks do not occur even when bent by the actions (a) to (c) described above, and the oxygen barrier property, water vapor barrier property, etc. are equal to or better than the film state of the inorganic compound. A gas barrier laminate film suitable for packaging materials for various articles such as foods and medicines having a gas barrier layer having gas barrier properties (particularly high water vapor barrier properties) can be provided.
[0126]
(D) If the thickness of the gas barrier layer is 1 μm or more compared to a conventional deposited film of Al or ceramic, a laminated film having a gas barrier layer having further superior oxygen barrier properties and water vapor barrier properties can be realized. .
[0127]
(E) As a base material, an organic polymer film or paper containing no chlorine such as PET and OPP is used, and the gas barrier organic polymer constituting the gas barrier layer is selected from ethylene vinyl alcohol copolymer and polyvinyl alcohol. By using at least one resin, the gas barrier layer can be easily removed from the substrate by treating the waste-treated product with, for example, a mixed solvent of alcohol and water. As a result, it is easy to collect and reuse the base material, and even when incinerated waste products do not discharge chlorine-based compounds harmful to the human body, so it is possible to provide an environmentally friendly gas barrier laminated film .
[0128]
The gas barrier laminate film of (1-2B) obtained by applying the gas barrier coating agent (ultrafine powder is a hydrophilic inorganic compound) to a base film and drying is described above (a) to (e ) Have the excellent properties listed.
[0129]
In particular, a surface 1 m substantially parallel to the surface of the base film²The total specific surface area of a large number of ultrafine powders per unit is 100 to 600 m²In other words, by having a gas barrier layer containing ultrafine powder in the form of a lot of soot, it is possible to develop a high tough path effect for gases such as oxygen and water vapor, so that excellent oxygen barrier properties and water vapor barrier properties (especially oxygen barrier properties) A gas barrier laminate film exhibiting a barrier property can be obtained. In addition, by making the average particle size of the ultrafine powder 100 nm or less, the tortuous pass effect can be more effectively exhibited.
[0130]
The gas barrier laminate film of the above (1-2C) obtained by applying the gas barrier coating agent (both ultrafine powders of both a hydrophilic inorganic compound and a hydrophobic inorganic compound) to a base film and drying is described above. (A) to (e) have excellent characteristics listed.
[0131]
In particular, a surface 1 m substantially parallel to the surface of the base film²The total specific surface area in the ultrafine powder of both the hydrophilic inorganic compound and the hydrophobic inorganic compound present per unit is 150 to 600 m²By having such a gas barrier layer, it is possible to achieve a balanced high toughness pass effect and moisture proof effect against gases such as oxygen and water vapor. For this reason, the gas-barrier laminated | multilayer film which shows the outstanding oxygen barrier property and water vapor barrier property can be obtained. Moreover, the tortuous pass effect can be more effectively exhibited by setting the average particle size of the ultrafine powder to 100 nm or less.
[0132]
The gas barrier laminate films having the two gas barrier layers (1-2D) obtained by applying the gas barrier coating agent to a base film and drying are listed in (a) to (e) above. It has excellent characteristics.
[0133]
In particular, a surface 1 m substantially parallel to the surface of the base film²The total specific surface area of a large number of hydrophilic inorganic compound ultrafine powders per unit is 100 to 600 m²Excellent tortuous pass effect by the first gas barrier layer and a surface substantially parallel to the surface of the base film 1m²The total specific surface area of a large number of hydrophobic inorganic compound ultrafine powders present per unit is 50 to 200 m²Due to the excellent moisture-proof effect of the second gas barrier layer, a gas barrier laminate film exhibiting excellent oxygen barrier properties and water vapor barrier properties can be obtained. Moreover, the tortuous pass effect can be more effectively exhibited by setting the average particle size of the ultrafine powder to 100 nm or less.
[0134]
Moreover, according to the manufacturing method mentioned above, the said gas barrier coating agent can be apply | coated to the single side | surface of a base film, and the said gas barrier layer can be formed. For this reason, a gas barrier laminate film can be easily and mass-produced without using a large-scale apparatus like the conventional method of forming a gas barrier layer of aluminum or an inorganic compound by vacuum deposition.
[0135]
(2-1) Gas barrier coating agent
This gas barrier coating agent comprises (a) a number of composite ultrafine particles in which ultrafine particles comprising silicon oxide and a gas barrier organic polymer are dispersed and bonded or bonded in the presence of a solvent, and (b) a silane coupling agent. contains.
[0136]
The silicon oxide is allowed to be subjected to a hydrophilic treatment or a hydrophobic treatment.
[0137]
The ultrafine powder desirably has an average particle size of 100 nm or less, more preferably 50 nm or less.
[0138]
As the gas barrier organic polymer, at least one water-soluble organic polymer selected from polyvinyl alcohol and ethylene vinyl alcohol copolymer can be used in the same manner as described in (1-1). In particular, the former polyvinyl alcohol is preferable because it is less expensive than the latter ethylene vinyl alcohol copolymer.
[0139]
As the solvent, the same solvent as described in (1-1) is used. In particular, the solvent is preferably a mixed solution of alcohol and water. It is preferable that the said liquid mixture consists of 30-50 volume% of alcohol and 50-70 volume% of water. The gas barrier coating agent containing such a mixed solution as a solvent can further stabilize the emulsion form and floating form of the composite ultrafine particles over a long period of time, and can also be used for the drying treatment during the formation of the gas barrier layer described later. It becomes possible to speed up.
[0140]
The composite ultrafine particles desirably have an average particle size of 1.0 μm or less, more preferably 0.1 μm or less, and still more preferably 0.01 μm or less.
[0141]
The composite ultrafine particles are preferably composed of 40 to 80% by weight of a liquid gas barrier organic polymer and 20 to 60% by weight of the ultrafine particles for the same reason as described in (1-1).
[0142]
Examples of the silane coupling agent include trade name SH-6040 manufactured by Toray Dow Corning.
[0143]
The silane coupling agent (b) is preferably blended in an amount of 5 to 15% by weight with respect to the composite ultrafine particles (a). When the addition amount of the silane coupling agent is less than 5% by weight, the chemical bonding between the organic polymer and the ultrafine powder is not sufficiently performed, and it is difficult to exert a gas blocking effect such as oxygen and water vapor. Become. On the other hand, when the addition amount of the silane coupling agent exceeds 15% by weight, the chemical bond between the organic polymer and the ultrafine powder becomes non-uniform, and the gas barrier property may be lowered.
[0144]
The gas barrier coating agent is prepared, for example, by the following method.
[0145]
First, a gas barrier organic polymer is dissolved in a solvent to form a liquid, and fine particles made of silicon oxide are mixed therewith. Subsequently, after pressurizing the liquid mixture using the collision crushing apparatus shown in FIG. 3 described above, the operation of crushing and crushing the liquid mixture at a high speed is repeated a plurality of times, whereby ultrafine particles are suspended or suspended. Make a solution. Finally, a gas barrier coating agent is prepared by adding a silane coupling agent to this solution and stirring and mixing.
[0146]
The fine particles preferably have an average particle size of 1000 nm or less from the viewpoint of shortening the production time of the composite fine particles. Moreover, you may use the aggregate of the ultrafine powder (100 nm or less) which has a final particle diameter.
[0147]
(2-2) Gas barrier laminate film
In this gas barrier laminate film, a gas barrier organic polymer and (a) ultrafine powder composed of silicon oxide and gas barrier organic polymer dispersed in the polymer are dispersed and bonded in the presence of a solvent. It has a structure in which a gas barrier layer containing a large number of combined ultrafine particles and (b) a silane coupling agent is laminated.
[0148]
The base film is made of, for example, the same organic polymer or paper as described in (1-2A) above.
[0149]
The ultrafine powder made of silicon oxide desirably has an average particle size of 100 nm or less, more preferably 50 nm or less.
[0150]
As the gas barrier organic polymer, at least one water-soluble organic polymer selected from, for example, polyvinyl alcohol and ethylene vinyl alcohol copolymer can be used as described in (1-2A) above.
[0151]
The gas barrier layer has a surface 1 m substantially parallel to the surface of the base film.²The total specific surface area of a large number of ultrafine powders per unit is 50 to 600 m²It is preferable that
[0152]
The gas barrier layer preferably has a thickness of 1 μm or more for the same reason as described in (1-2A) above.
[0153]
In addition, the same or different organic polymer film (top coat) as the organic polymer film (top coat) or paper, non-woven fabric or the like is laminated on the surface of the gas barrier layer opposite to the organic polymer film with an adhesive Allow.
[0154]
(2-3) Method for producing gas barrier film
A gas barrier laminate film is produced by applying the gas barrier coating agent described in (2-1) above to a base film and drying to form a gas barrier layer.
[0155]
As the coating means, for example, the same roll coater method as described in the above (1-3A) can be adopted.
[0156]
The gas barrier coating agent described above contains a large number of composite ultrafine particles in which ultrafine powder made of silicon oxide and a gas barrier organic polymer are dispersed and bonded or bonded in the presence of a solvent, and a silane coupling agent. Even if it is allowed to stand, the composite ultrafine particles do not aggregate and can maintain a stable emulsion or floating form.
[0157]
A gas barrier laminate film can be obtained by applying such a gas barrier coating agent to a base film and drying to form a gas barrier layer. This gas barrier laminate film has the excellent properties listed in (a) to (e) above.
[0158]
In particular, a gas barrier layer containing a large number of composite ultrafine particles in which ultrafine powders of silicon oxide and a gas barrier organic polymer are dispersedly bonded or bonded in the presence of a solvent and a silane coupling agent is dispersed in silicon oxide. Since the ultrafine powder and gas barrier organic polymer are chemically bonded by the silane coupling agent, in addition to the above-mentioned tough path effect, the interaction force between ultrafine powders, the ultrafine powder interface against gas permeation High excretion at work. As a result, it is possible to obtain a gas barrier laminate film that exhibits oxygen barrier properties and water vapor barrier properties that are significantly superior to those of gas barrier laminate films having a gas barrier layer that does not contain a silane coupling agent.
[0159]
Further, a surface 1 m substantially parallel to the surface of the base film²The total specific surface area of a large number of ultrafine powders per unit is 50 to 600 m²By laminating the gas barrier layer on the base film, the tortuous pass effect is further enhanced, so that a gas barrier laminated film having water vapor barrier properties and further excellent oxygen barrier properties can be obtained.
[0160]
Furthermore, according to the manufacturing method described in the above (2-3), the gas barrier coating agent can be applied to one side of a base film to form the gas barrier layer. Therefore, a gas barrier layer of aluminum or an inorganic compound can be formed by conventional vacuum deposition. A gas barrier laminate film can be easily and mass-produced without using a large-scale apparatus as in the method of forming the film.
[0161]
【Example】
Hereinafter, preferred embodiments of the present invention will be described.
[0162]
Example 1
25 weight of a mixture of ethylene vinyl alcohol copolymer (EVOH) and polyvinyl alcohol (PVA) (EVOH: PVA = 60: 40) in a solvent in which water and isopropyl alcohol (IPA) are mixed at a weight ratio of 50:50 %, And each resin was dissolved at a temperature of 100 ° C., and then aggregates of silicon oxide powder (average particle size of primary particles; 7 nm) and aggregates of titanium oxide powder (average particle size of primary particles) were added to this solution. A liquid mixture was prepared by adding 30% by weight and 20% by weight, respectively, to the mixed resin. Subsequently, while maintaining the temperature of the liquid mixture at 100 ° C., the collision crushing apparatus shown in FIG. 3 described above was used, and the collision crushing was repeated 8 times under the following conditions. Through this process, each of the agglomerates is pulverized, and at the same time, dispersed and bonded or bonded to the mixed resin is uniformly formed.₂Ultra fine powder and TiO with an average particle size of 20 nm₂A gas barrier coating agent containing a large number of composite ultrafine particles in which ultrafine powder and the mixed resin were uniformly dispersed and bonded in the presence of a solvent was prepared.
[0163]
<Collision crushing conditions>
Applied pressure of liquid mixture: about 1500 kg / cm²
Acceleration of the liquid mixture passing through the nozzle part; approx. 200 m / sec
The obtained gas barrier coating agent had stable properties without precipitation of ultrafine powder of an inorganic compound such as silicon oxide or growth into a fiber at room temperature or lower. . The composite ultrafine particles in the gas barrier coating agent had an average particle size of 0.1 μm.
Next, the gas barrier coating agent is applied to a stretched polypropylene (OPP) film having a thickness of 30 μm by a roll coater method so as to have a thickness of 1 μm and 2 μm, and dried to form a gas barrier layer on the OPP film. Two types of gas barrier laminate films were produced.
[0164]
The gas barrier layer was observed with an electron microscope. As a result, it was confirmed that the silicon oxide ultrafine powder having an average particle diameter of 7 nm and the titanium oxide ultrafine powder having an average particle diameter of 20 nm were uniformly dispersed in EVOH and PVA.
[0165]
(Comparative Example 1)
A polyvinylidene chloride (PVDC) solution (gas barrier coating agent) was applied to a 30 μm thick OPP film by a roll coater method so as to have a thickness of 2.0 μm, and dried to produce a gas barrier laminated film.
[0166]
(Comparative Example 2)
A gas barrier laminate film was manufactured by vacuum-depositing an aluminum thin film having a thickness of 50 nm on a PET film having a thickness of 12 μm.
[0167]
(Comparative Example 3)
A gas barrier laminate film was produced by vacuum-depositing a 50 nm thick silicon oxide thin film on a 60 μm thick CPP film.
[0168]
About the obtained gas-barrier laminated film of Example 1 and Comparative Example 1-3, the oxygen transmission rate and the water vapor transmission rate were measured. The oxygen permeation amount is a product name manufactured by JASCO Corporation; a sample having a diameter of 10 cm cut out from the laminated film using gas palm is oxygen concentration 100%, 25 ° C., 65% 5kg / cm for H²The measurement was performed under the condition of pressurizing to the above. In addition, the water vapor transmission rate is Swiss Dr. A product name of Lyssy, Inc .; a sample having a diameter of 10 cm cut out from the laminated film using L80-4000 type was 40 ° C. and 90% R.D. according to JIS K7129A. Measured under H conditions. The results are shown in Table 1 below.
[0169]
In Table 1 below, as Reference Example 1-4, the oxygen transmission rate and water vapor transmission rate of a 30 μm thick OPP film, a 20 μm thick PVA film, a 15 μm EVOH film, and a 30 μm thick PVDC film are shown. Also written.
[0170]
[Table 1]

[0171]
As is apparent from Table 1, the gas barrier laminate film of Example 1 has an oxygen barrier which is equal to or better than the PVDC film of Reference Example 4 having a thin gas barrier layer having a thickness of 1 μm and 2 μm. It turns out that it has sex. Further, as is clear from the comparison of the gas barrier laminated film of Example 1 and Comparative Example 1 in which the thickness of the gas barrier layer is 2 μm, the laminated film of Example 1 is superior in oxygen to the laminated film of Comparative Example 1. It turns out that it has barrier property and water vapor barrier property.
[0172]
Further, the gas barrier laminate film of Example 1 had transparency equivalent to OPP which is a base film.
[0173]
In addition, if the gas barrier laminated film of Comparative Example 3 which is a silicon oxide vapor-deposited film is repeatedly bent, pinholes and cracks are generated in the silicon oxide vapor-deposited film, and its oxygen and water vapor barrier properties are extremely lowered. In contrast, the gas barrier laminate film of Example 1 maintained the excellent oxygen barrier properties and water vapor barrier properties shown in Table 1 even when it was repeatedly bent.
[0174]
Moreover, although the single film of EVOH and PVA has excellent oxygen barrier properties in a dry atmosphere, the oxygen barrier properties are extremely lowered when exposed to a wet atmosphere.
[0175]
(Example 2)
The gas barrier coating agent prepared in Example 1 was applied to a PET film having a thickness of 12 μm by a roll coater method so as to have a thickness of 1 μm and 2 μm, and dried to form a gas barrier layer on the PET film. A seed gas barrier laminate film was produced.
[0176]
(Comparative Example 4)
A 25 wt% concentration of polyvinylidene chloride (PVDC) IPA solution (gas barrier coating agent) is applied to a PET film having a thickness of 12 μm by a roll coater method so as to have a thickness of 2.0 μm, and dried to provide a gas barrier property. A laminated film was produced.
[0177]
About the obtained laminated film of Example 2 and Comparative Example 4, the oxygen transmission rate and the water vapor transmission rate were measured by the same method as in Example 1. The results are shown in Table 2 below. In Table 2 below, as Reference Example 5, the oxygen permeation amount and water vapor permeation amount of a 12 μm thick PET film are also shown.
[0178]
[Table 2]

[0179]
In addition, the gas-barrier laminated film of Example 2 had transparency equivalent to PET which is a base film.
[0180]
Further, the gas barrier laminate film of Example 2 maintained the excellent oxygen barrier properties and water vapor barrier properties shown in Table 2 even when it was repeatedly bent.
[0181]
(Example 3)
After adding 25% by weight of ethylene vinyl alcohol copolymer (EVOH) to a solvent in which water and isopropyl alcohol (IPA) are mixed at a weight ratio of 50:50, the resin is dissolved at a temperature of 80 ° C. Aggregates of silicon oxide powder (average particle size of primary particles; 7 nm) and agglomerates of titanium oxide powder (average particle size of primary particles; 20 nm) were added to the solution by 20 wt% and 10 wt%, respectively, with respect to the EVOH. Thus, a liquid mixture was prepared. Subsequently, while maintaining the temperature of the liquid mixture at 80 ° C., the collision crushing apparatus shown in FIG. 3 described above was used, and the collision crushing was repeated 5 times under the following conditions. Through this process, the agglomerates are pulverized, and at the same time, dispersedly bonded or bonded to the EVOH are uniformly formed.₂Ultra fine powder and TiO with an average particle size of 20 nm₂A gas barrier coating agent containing a large number of composite ultrafine particles in which ultrafine powder and the EVOH were uniformly dispersed and bonded in the presence of a solvent was prepared.
[0182]
<Collision crushing conditions>
・ Pressure force of liquid mixture; about 1800 Kg / cm^2
・Acceleration of liquid mixture passing through nozzle part; approx. 250 m / sec
The obtained gas barrier coating agent had stable properties without precipitation of ultrafine powder of an inorganic compound such as silicon oxide or growth into a fiber at room temperature or lower. . The composite ultrafine particles in the gas barrier coating agent had an average particle size of 0.1 μm.
[0183]
Next, the gas barrier coating agent is applied to a nylon film having a thickness of 16 μm by a roll coater method so as to have a thickness of 1 μm and 2 μm, and dried to form a gas barrier layer on the nylon film. The laminated film was manufactured.
[0184]
The gas barrier layer was observed with an electron microscope. As a result, it was confirmed that the silicon oxide ultrafine powder having an average particle diameter of 7 nm and the titanium oxide ultrafine powder having an average particle diameter of 20 nm were uniformly dispersed in EVOH.
[0185]
(Comparative Example 5)
A 25 wt% concentration of polyvinylidene chloride (PVDC) IPA solution (gas barrier coating agent) is applied to a nylon film having a thickness of 16 μm by a roll coater method so as to have a thickness of 2.0 μm, and dried to provide a gas barrier property. A laminated film was produced.
[0186]
About the obtained laminated film of Example 3 and Comparative Example 5, the oxygen transmission rate and the water vapor transmission rate were measured in the same manner as in Example 1. The results are shown in Table 3 below. In Table 3 below, as Reference Example 6, the oxygen permeation amount and water vapor permeation amount of a 16 μm thick nylon film are also shown.
[0187]
[Table 3]

[0188]
In addition, the gas-barrier laminated film of Example 3 had transparency equivalent to nylon which is a base film.
[0189]
Further, the gas barrier laminate film of Example 3 maintained the excellent oxygen barrier properties and water vapor barrier properties shown in Table 3 even when it was repeatedly bent.
[0190]
Example 4
The gas barrier coating agent prepared in Example 3 was applied to a PE film having a thickness of 30 μm by a roll coater method so as to have a thickness of 1 μm and 2 μm, and dried to form a gas barrier layer on the PE film. A seed gas barrier laminate film was produced.
[0191]
For the obtained laminated film of Example 4, the oxygen transmission rate and water vapor transmission rate were measured in the same manner as in Example 1. The results are shown in Table 4 below. In Table 4 below, as Reference Example 7, the oxygen transmission rate and water vapor transmission rate of a 30 μm thick PE film are also shown.
[0192]
[Table 4]

[0193]
In addition, the gas-barrier laminated film of Example 4 had transparency equivalent to PE which is a base film.
[0194]
Moreover, even if the gas barrier laminated film of Example 4 was repeatedly bent, the excellent oxygen barrier property and water vapor barrier property of Table 4 were maintained.
[0195]
(Example 5)
After adding 25% by weight of polyvinyl alcohol (PVA) to a solvent in which water and isopropyl alcohol (IPA) are mixed at a weight ratio of 50:50 and dissolving the resin at a temperature of 95 ° C., silicon oxide is added to the solution. A powder mixture (average particle size of primary particles; 7 nm) and agglomerate of titanium oxide powder (average particle size of primary particles; 20 nm) were added to the PVA in an amount of 25% by weight and 5% by weight, respectively. Was prepared. Subsequently, while maintaining the temperature of the liquid mixture at 95 ° C., the collision crushing was repeated four times under the conditions shown below using the collision crushing apparatus shown in FIG. Through this process, the agglomerates are pulverized, and at the same time, the PVA is uniformly dispersed and bonded or bonded together.₂Ultra fine powder and TiO 2 having an average particle diameter of 20 nm₂A gas barrier coating agent containing a large number of composite ultrafine particles in which ultrafine powder and the PVA were uniformly dispersed and bonded in the presence of a solvent was prepared.
[0196]
<Collision crushing conditions>
・ Pressure force of the liquid mixture: about 2000 kg / cm^2
・Acceleration of liquid mixture passing through nozzle part; approx. 300m / sec
The obtained gas barrier coating agent had stable properties without precipitation of ultrafine powder of an inorganic compound such as silicon oxide or growth into a fiber at room temperature or lower. . The composite ultrafine particles in the gas barrier coating agent had an average particle size of 0.1 μm.
[0197]
Next, the gas barrier coating agent is applied to an unstretched polypropylene (CPP) film having a thickness of 30 μm by a roll coater method so as to have a thickness of 1 μm and 2 μm, and dried to form a gas barrier layer on the nylon film. Two types of laminated films were produced by
[0198]
The gas barrier layer was observed with an electron microscope. As a result, it was confirmed that silicon oxide ultrafine powder having an average particle diameter of 7 nm and titanium oxide ultrafine powder having an average particle diameter of 20 nm were uniformly dispersed in PVA.
[0199]
About the obtained laminated film of Example 5, the oxygen permeation amount and the water vapor permeation amount were measured by the same method as in Example 1. The results are shown in Table 5 below. In Table 5 below, as Reference Example 8, the oxygen transmission rate and water vapor transmission rate of a 30 μm thick CPP film are also shown.
[0200]
[Table 5]

[0201]
In addition, the gas-barrier laminated film of Example 5 had transparency equivalent to CPP which is a base film.
[0202]
Moreover, even if the gas barrier laminated film of Example 5 was repeatedly bent, the excellent oxygen barrier property and water vapor barrier property of Table 5 were maintained.
[0203]
(Example 6)
Polyvinyl alcohol (PVA) was added to a solvent in which water and isopropyl alcohol (IPA) were mixed at a weight ratio of 50:50, the PVA was dissolved at a temperature of 100 ° C., and the solution was subjected to a hydrophobic treatment. Silicon powder agglomerates (average particle size of primary particles; 7 nm) [trade name; R-812, manufactured by Nippon Aerosil Co., Ltd.] were added to prepare a liquid mixture. The PVA and the hydrophobized silicon oxide (R-812) were added so as to be 70% by weight and 30% by weight, respectively, with respect to the solvent.
[0204]
Next, while maintaining the temperature of the liquid mixture at 80 ° C., collision crushing was repeated 8 times under the following conditions using the collision crushing apparatus shown in FIG. In this step, the agglomerates are pulverized, and at the same time, dispersed and joined or bonded uniformly with the mixed resin. Hydrophobized silicon oxide (R-812) having an average particle diameter of 7 nm and the PVA are solvent. A gas barrier coating agent containing a large number of composite ultrafine particles uniformly dispersed and bonded in the presence of was prepared.
[0205]
<Collision crushing conditions>
・ Pressure force of the liquid mixture: about 2000 kg / cm^2
・Acceleration of the liquid mixture passing through the nozzle part; approx. 200 m / sec
The obtained gas barrier coating agent has stable properties without precipitation of ultrafine powder of hydrophobized silicon oxide (R-812) or growth into a fiber at room temperature or lower. Met. The composite ultrafine particles in the gas barrier coating agent had an average particle size of 0.1 μm.
Next, the gas barrier coating agent is applied to a stretched polypropylene (OPP) film having a thickness of 30 μm by a roll coater method so as to have a thickness of 2 μm, and dried to form a gas barrier layer on the OPP film. A film was produced.
[0206]
The gas barrier layer was observed with an electron microscope. As a result, it was confirmed that in this gas barrier layer, hydrophobized silicon oxide ultrafine powder (R-812 ultrafine powder) having an average particle diameter of 7 nm was uniformly dispersed in PVA.
[0207]
Further, the gas barrier layer has a surface 1 m substantially parallel to the surface of the OPP film.²The total specific surface area of a large number of hydrophobized silicon oxide ultrafine powders (R-812 ultrafine powder) present per unit is 100 m²Met.
[0208]
(Example 7)
Polyvinyl alcohol (PVA) was added to a solvent in which water and isopropyl alcohol (IPA) were mixed at a weight ratio of 50:50, and the PVA was dissolved at a temperature of 100 ° C. Then, the solution was hydrophilized. A liquid mixture was prepared by adding agglomerates of silicon powder (average particle diameter of primary particles; 7 nm) [trade name of Nippon Aerosil Co., Ltd .; 380]. The PVA and the hydrophilized silicon oxide (380) were added to 70 wt% and 30 wt%, respectively, with respect to the solvent.
[0209]
Next, while maintaining the temperature of the liquid mixture at 80 ° C., collision crushing was repeated 8 times under the same conditions as in Example 6 using the collision crushing apparatus shown in FIG. 3 described above. In this step, the agglomerates are disintegrated and simultaneously dispersed and bonded or bonded to the PVA. The ultrafine powder of hydrophilized silicon oxide (380) having an average particle diameter of 7 nm and the PVA are present in the presence of a solvent. A gas barrier coating agent containing a large number of composite ultrafine particles uniformly dispersed and bonded together was prepared.
[0210]
The obtained gas barrier coating agent has stable properties without precipitation of ultrafine powder of hydrophilized silicon oxide (380) or growth into a fiber at room temperature or lower. It was. The composite ultrafine particles in the gas barrier coating agent had an average particle size of 0.1 μm.
[0211]
Next, the gas barrier coating agent is applied to a stretched polypropylene (OPP) film having a thickness of 30 μm by a roll coater method so as to have a thickness of 2 μm and 4 μm, and dried to form a gas barrier layer on the OPP film. Two types of gas barrier laminate films were produced.
[0212]
Each gas barrier layer was observed with an electron microscope. As a result, it was confirmed that in this gas barrier layer, hydrophilic silicon oxide ultrafine powder having an average particle diameter of 7 nm (superfine powder of 380) was uniformly dispersed in PVA.
[0213]
Each gas barrier layer has a surface 1 m substantially parallel to the surface of the OPP film.²The total specific surface area of a large number of hydrophilized silicon oxide ultrafine powders (380 ultrafine powders) present in the vicinity is 140 m²Met.
[0214]
(Example 8)
A mixture (PVA: EVOH = 70: 30) of polyvinyl alcohol (PVA) and ethylene vinyl alcohol copolymer (EVOH) was added to a solvent in which water and isopropyl alcohol (IPA) were mixed at a weight ratio of 50:50. Then, after each resin was dissolved at a temperature of 100 ° C., agglomerates of silicon oxide powder (average particle size of primary particles; 7 nm) [trade name made by Nippon Aerosil Co., Ltd .; Thus, a liquid mixture was prepared. The mixed resin and the hydrophilized silicon oxide (380) were added so as to be 70% by weight and 30% by weight, respectively, with respect to the solvent.
[0215]
Next, while maintaining the temperature of the liquid mixture at 80 ° C., collision crushing was repeated 8 times under the same conditions as in Example 6 using the collision crushing apparatus shown in FIG. 3 described above. In this step, the agglomerates are pulverized, and at the same time, uniformly bonded or bonded to the mixed resin of PVA-EVOH, and the ultrafine powder of hydrophilized silicon oxide (380) having an average particle diameter of 7 nm and the PVA- A gas barrier coating agent containing a large number of composite ultrafine particles in which EVOH mixed resin was uniformly dispersed and bonded in the presence of a solvent was prepared.
[0216]
The obtained gas barrier coating agent has stable properties without precipitation of ultrafine powder of hydrophilized silicon oxide (380) or growth into a fiber at room temperature or lower. It was. The composite ultrafine particles in the gas barrier coating agent had an average particle size of 0.1 μm.
[0217]
Next, the gas barrier coating agent is applied to a stretched polypropylene (OPP) film having a thickness of 30 μm by a roll coater method so as to have a thickness of 2 μm, and dried to form a gas barrier layer on the OPP film. A laminated film was produced.
[0218]
The gas barrier layer was observed with an electron microscope. As a result, it was confirmed that in this gas barrier layer, hydrophilic silicon oxide ultrafine powder (380 ultrafine powder) having an average particle diameter of 7 nm was uniformly dispersed in a mixed resin of PVA-EVOH.
[0219]
Further, the gas barrier layer has a surface 1 m substantially parallel to the surface of the OPP film.²The total specific surface area of a large number of hydrophilized silicon oxide ultrafine powders (380 ultrafine powders) existing around is 140 m.²Met.
[0220]
Example 9
Polyvinyl alcohol (PVA) was added to a solvent in which water and isopropyl alcohol (IPA) were mixed at a weight ratio of 50:50, and the PVA was dissolved at a temperature of 100 ° C. Then, the solution was hydrophilized. A liquid mixture was prepared by adding agglomerates of silicon powder (average particle diameter of primary particles; 7 nm) [trade name of Nippon Aerosil Co., Ltd .; 380]. The PVA and the hydrophilized silicon oxide (380) were added to 70 wt% and 30 wt%, respectively, with respect to the solvent.
[0221]
Next, while maintaining the temperature of the liquid mixture at 80 ° C., collision crushing was repeated 8 times under the same conditions as in Example 6 using the collision crushing apparatus shown in FIG. 3 described above. In this step, the agglomerates are disintegrated and simultaneously dispersed and bonded or bonded to the PVA. The ultrafine powder of hydrophilized silicon oxide (380) having an average particle diameter of 7 nm and the PVA are present in the presence of a solvent. A solution containing a large number of composite ultrafine particles uniformly dispersed and joined with each other was prepared. This solution had stable properties without precipitation of ultrafine powder of hydrophilized silicon oxide (380) or growth into a fiber at room temperature or lower. The composite ultrafine particles in the solution had an average particle size of 0.1 μm.
[0222]
Next, a silane coupling agent (trade name SH-6040 manufactured by Toray Dow Corning Co., Ltd.) was added to the solution in an amount of 10% by weight based on the hydrophilized silicon oxide, and the mixture was stirred and mixed to prepare a barrier coating agent. The gas barrier coating agent is applied to a stretched polypropylene (OPP) film having a thickness of 30 μm by a roll coater method so as to have a thickness of 2 μm, and dried to form a gas barrier layer on the OPP film. Manufactured.
[0223]
The gas barrier layer was observed with an electron microscope. As a result, in this gas barrier layer, hydrophilic silicon oxide ultrafine powder having an average particle diameter of 7 nm (superfine powder of 380) is uniformly dispersed in PVA, and these PVA and hydrophilic silicon oxide ultrafine powder are mixed with silane. It was confirmed that they were bonded and cross-linked by a coupling agent.
[0224]
Further, the gas barrier layer has a surface 1 m substantially parallel to the surface of the OPP film.²The total specific surface area of a large number of hydrophilized silicon oxide ultrafine powders (380 ultrafine powders) present at the periphery is 110 m.²Met.
[0225]
(Example 10)
Polyvinyl alcohol (PVA) was added to a solvent in which water and isopropyl alcohol (IPA) were mixed at a weight ratio of 50:50, and the PVA was dissolved at a temperature of 100 ° C. Then, the solution was hydrophilized. Aggregates of silicon powder (average particle size of primary particles: 7 nm) [trade name manufactured by Nippon Aerosil Co., Ltd .; 380] and aggregates of hydrophobized silicon oxide powder (average particle size of primary particles: 7 nm) [Nippon Aerosil Co., Ltd. Product name; R-812] was added to prepare a liquid mixture. The PVA, the hydrophilized silicon oxide powder (380), and the hydrophobized silicon oxide powder (R-812) were added to 60 wt%, 30 wt%, and 10 wt%, respectively, with respect to the solvent. did.
[0226]
Next, while maintaining the temperature of the liquid mixture at 80 ° C., collision crushing was repeated 8 times under the same conditions as in Example 6 using the collision crushing apparatus shown in FIG. 3 described above. In this step, each of the agglomerates is disintegrated, and at the same time, uniformly dispersed or bonded to the PVA, and the hydrophilized silicon oxide (380) having an average particle size of 7 nm and the hydrophobized particle having an average particle size of 7 nm. A gas barrier coating agent containing a large number of composite ultrafine particles in which an ultrafine powder of treated silicon oxide powder (R-812) and the PVA were uniformly dispersed and bonded in the presence of a solvent was prepared.
[0227]
The obtained gas barrier coating agent was precipitated at a room temperature or lower temperature, in which ultrafine powder of hydrophilized silicon oxide (380) and ultrafine powder of hydrophobized silicon oxide powder (R-812) were precipitated or fibrous. It has a stable property without growing. The composite ultrafine particles in the gas barrier coating agent had an average particle size of 0.1 μm.
[0228]
Next, the gas barrier coating agent is applied to a stretched polypropylene (OPP) film having a thickness of 30 μm by a roll coater method so as to have a thickness of 2 μm, and dried to form a gas barrier layer on the OPP film. A film was produced.
[0229]
The gas barrier layer was observed with an electron microscope. As a result, this gas barrier layer was made of PVA with a hydrophilic silicon oxide ultrafine powder (380 ultrafine powder) having an average particle size of 7 nm and a hydrophobized silicon oxide ultrafine powder (R-812 ultrafine powder) having an average particle size of 7 nm. ) Was confirmed to be uniformly dispersed.
[0230]
Further, the gas barrier layer has a surface 1 m substantially parallel to the surface of the OPP film.²The total specific surface area of a large number of hydrophilized silicon oxide ultrafine powders (380 ultrafine powders) and hydrophobized silicon oxide ultrafine powders (R-812 ultrafine powders) present in the vicinity is 250 m.²Met.
[0231]
(Example 11)
Polyvinyl alcohol (PVA) was added to a solvent in which water and isopropyl alcohol (IPA) were mixed at a weight ratio of 50:50, and the PVA was dissolved at a temperature of 100 ° C. Then, this solution was superhydrophobized. A liquid mixture was prepared by adding agglomerates of silicon oxide powder (average particle diameter of primary particles; 7 nm) [trade name: RY-300, manufactured by Nippon Aerosil Co., Ltd.]. The PVA and the superhydrophobized silicon oxide powder (RY-300) were added to 70 wt% and 30 wt%, respectively, with respect to the solvent.
[0232]
Next, while maintaining the temperature of the liquid mixture at 80 ° C., collision crushing was repeated 8 times under the same conditions as in Example 6 using the collision crushing apparatus shown in FIG. 3 described above. In this step, the agglomerates are pulverized, and at the same time, the PVA is uniformly dispersed and bonded or bonded. The ultrafine hydrophobized silicon oxide (RY-300) powder having an average particle size of 7 nm and the PVA are solvent. A gas barrier coating agent containing a large number of composite ultrafine particles uniformly dispersed and bonded in the presence of was prepared.
[0233]
The obtained gas barrier coating agent has stable properties without precipitation of ultra-hydrophobized silicon oxide (RY-300) ultrafine powder or growth into a fiber at room temperature or lower. It was a thing. The composite ultrafine particles in the gas barrier coating agent had an average particle size of 0.1 μm.
Then, a gas barrier coating agent [containing composite ultrafine particles comprising ultrafine powder of PVA and hydrophilized silicon oxide (380)] similar to that in Example 7 was applied to an expanded polypropylene (OPP) film having a thickness of 30 μm in thickness of 2 μm. The first gas barrier layer (lower gas barrier layer) was formed on the OPP film by applying by a roll coater method and drying. Subsequently, the gas barrier coating agent is applied to the lower gas barrier layer by a roll coater method so as to have a thickness of 2 μm, and dried to form a second gas barrier layer (upper gas barrier layer) on the lower gas barrier layer. A gas barrier laminate film was produced.
[0234]
The lower gas barrier layer and the upper gas barrier layer were observed with an electron microscope. As a result, it was confirmed that in the lower gas barrier layer, hydrophilic silicon oxide ultrafine powder (380 ultrafine powder) having an average particle diameter of 7 nm was uniformly dispersed in PVA. In the upper gas barrier layer, it was confirmed that ultrahydrophobized silicon oxide ultrafine powder (RY-300 ultrafine powder) having an average particle diameter of 7 nm was uniformly dispersed in PVA.
[0235]
Further, the lower gas barrier layer has a surface 1 m substantially parallel to the surface of the OPP film.²The total specific surface area of a large number of hydrophilized silicon oxide ultrafine powders (380 ultrafine powders) existing around is 140 m.²Met. The upper gas barrier layer is a surface 1 m substantially parallel to the surface of the OPP film.²The total specific surface area of a large number of ultrahydrophobized silicon oxide ultrafine powders (RY-300 ultrafine powders) present per unit is 100 m²Met.
[0236]
About the obtained gas-barrier laminated film of Examples 6-11, the oxygen permeation amount and the water vapor permeation amount were measured by the same method as in Example 1. The results are shown in Table 6 below.
[0237]
In Table 6, the oxygen permeation amount and the water vapor permeation amount of Reference Example 1 (an OPP film having a thickness of 30 μm) are shown.
[0238]
[Table 6]

[0239]
As apparent from Table 6, it can be seen that the gas barrier laminated films of Examples 6 to 11 have superior oxygen barrier properties and water vapor barrier properties as compared to the OPP single film.
[0240]
In particular, a gas barrier laminate film manufactured using a gas barrier coating agent containing composite ultrafine particles composed of PVA and hydrophobized silicon oxide (R-812) ultrafine powder as in Example 6; When the PVA and a gas barrier layered film produced using a gas barrier coating agent containing composite ultrafine particles composed of ultrafine powder of hydrophilized silicon oxide (380) are compared, the gas barrier layer has the same thickness (2 μm) In this case, it can be seen that the laminated film of Example 6 is superior in oxygen barrier property and water vapor barrier property to the laminated film of Example 7. However, it can be seen that when the thickness of the gas barrier layer in the laminated film of Example 6 is 4 μm, the oxygen barrier property and the water vapor barrier property are remarkably improved.
[0241]
Further, a gas barrier laminate film produced using a gas barrier coating agent containing composite ultrafine particles composed of a mixed resin of PVA and EVOH and ultrafine powder of hydrophilized silicon oxide (380) as in Example 8 is a gas barrier. It can be seen that when the layer is 2 μm, it has the same oxygen barrier property and water vapor barrier property as the laminated film of Example 7 having a gas barrier layer containing ultrafine powder of hydrophobized silicon oxide (R-812).
[0242]
Further, a gas barrier laminate film produced by using a gas barrier coating agent prepared by mixing a silane coupling agent with a composite ultrafine particle composed of PVA and hydrophilized silicon oxide (380) ultrafine powder as in Example 9 and implementation. It was manufactured using a gas barrier coating agent containing composite ultrafine particles composed of ultrafine powder of PVA and hydrophilized silicon oxide (380) and ultrafine powder of hydrophobized silicon oxide (R-812) as in Example 10. It can be seen that the gas barrier laminated film has significantly improved oxygen barrier properties and water vapor barrier properties as compared with the laminated film of Example 6 (gas barrier layer has the same thickness; 2 μm).
[0243]
Furthermore, a lower gas barrier layer made of ultra fine powder of PVA and hydrophilized silicon oxide (380) as in Example 11, and an upper gas barrier made of ultra fine powder of PVA and super hydrophobized silicon oxide (RY-300) It can be seen that the gas barrier laminate film having a layer has a superior water vapor barrier property although the oxygen barrier property is slightly lower than that of the gas barrier laminate film of Example 7 in which the thickness of the gas barrier layer is 4 μm.
[0244]
In addition, the gas-barrier laminated | multilayer film of Examples 6-11 had transparency equivalent to OPP which is a base film.
[0245]
The gas barrier laminate films of Examples 6 to 11 maintained the excellent oxygen barrier properties and water vapor barrier properties shown in Table 6 even after repeated bending.
[0246]
Example 12
A gas barrier laminate film is formed by applying the gas barrier coating agent prepared in Example 6 to a PET film having a thickness of 12 μm by a roll coater method so as to have a thickness of 2 μm and drying to form a gas barrier layer on the PET film. Manufactured.
[0247]
The gas barrier layer was observed with an electron microscope. As a result, it was confirmed that the hydrophobized silicon oxide ultrafine powder (R-812 ultrafine powder) having an average particle diameter of 7 nm was uniformly dispersed in the gas barrier layer PVA.
[0248]
Further, the gas barrier layer has a surface 1 m substantially parallel to the surface of the PET film.²The total specific surface area of a large number of hydrophobized silicon oxide ultrafine powders (R-812 ultrafine powder) present per unit is 100 m²Met.
[0249]
(Example 13)
A gas barrier laminate film is formed by applying the gas barrier coating agent prepared in Example 7 to a PET film having a thickness of 12 μm by a roll coater method so as to have a thickness of 2 μm, and drying to form a gas barrier layer on the PET film. Manufactured.
[0250]
The gas barrier layer was observed with an electron microscope. As a result, it was confirmed that in this gas barrier layer, hydrophilized silicon oxide ultrafine powder (380 ultrafine powder) having an average particle diameter of 7 nm was uniformly dispersed in PVA.
[0251]
Further, the gas barrier layer has a surface 1 m substantially parallel to the surface of the PET film.²The total specific surface area of a large number of hydrophilized silicon oxide ultrafine powders (380 ultrafine powders) existing around is 140 m.²Met.
[0252]
(Example 14)
The gas barrier coating agent prepared in Example 6 was applied to Ryuo coated paper by a roll coater method so as to have a thickness of 2 μm, and dried to form a gas barrier layer on the Ryuo coated paper to produce a gas barrier laminated film. did.
[0253]
The gas barrier layer was observed with an electron microscope. As a result, it was confirmed that in this gas barrier layer, hydrophobized silicon oxide ultrafine powder (R-812 ultrafine powder) having an average particle diameter of 7 nm was uniformly dispersed in PVA.
[0254]
Further, the gas barrier layer has a surface 1 m substantially parallel to the surface of the Ryuo coated paper.²The total specific surface area of a large number of hydrophobized silicon oxide ultrafine powders (R-812 ultrafine powder) present per unit is 100 m²Met.
[0255]
(Example 15)
The gas barrier coating agent prepared in Example 7 was applied to Ryuo coated paper by a roll coater method to a thickness of 2 μm, and dried to form a gas barrier layer on the Ryuo coated paper to produce a gas barrier laminated film. did.
[0256]
The gas barrier layer was observed with an electron microscope. As a result, it was confirmed that in this gas barrier layer, hydrophilized silicon oxide ultrafine powder (380 ultrafine powder) having an average particle diameter of 7 nm was uniformly dispersed in PVA.
[0257]
Further, the gas barrier layer has a surface 1 m substantially parallel to the surface of the Ryuo coated paper.²The total specific surface area of a large number of hydrophilized silicon oxide ultrafine powders (380 ultrafine powders) present in the vicinity is 14 m²Met.
[0258]
With respect to the obtained gas barrier laminate films of Examples 12 to 15, the oxygen transmission rate and the water vapor transmission rate were measured by the same method as in Example 1. The results are shown in Table 7 below.
[0259]
In Table 7 below, the oxygen permeation amount and water vapor permeation amount of Reference Example 5 (PET film having a thickness of 12 μm) and Reference Example 9 (Ryuo coated paper alone) are also shown.
[0260]
[Table 7]

[0261]
In addition, the gas barrier laminate films of Examples 12 and 13 had the same transparency as PET as the base film.
[0262]
Furthermore, even if the gas barrier laminated films of Examples 12 to 15 were repeatedly bent, the excellent oxygen barrier properties and water vapor barrier properties shown in Table 7 were maintained.
[0263]
【The invention's effect】
As described in detail above, according to the present invention, even if bent, no pinholes or cracks are generated, and a gas barrier layer having an excellent gas barrier property equal to or higher than the film state of an inorganic compound or metal is provided. A gas barrier laminate film suitable for packaging materials for various articles such as food and medicine can be provided.
[0264]
INDUSTRIAL APPLICABILITY The present invention can provide a gas barrier laminated film that has a gas barrier layer having excellent gas barrier properties and does not generate pinholes or cracks even when bent, and has transparency equivalent to an organic resin film as a substrate .
[0265]
INDUSTRIAL APPLICABILITY The present invention can provide a method for producing a gas barrier laminate film capable of forming the gas barrier layer having the above-described excellent gas barrier property by a coating means without using a large apparatus such as vacuum deposition.
[0266]
The present invention can provide a gas barrier coating agent capable of obtaining a gas barrier laminate film having excellent properties.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a gas barrier laminate film according to the present invention.
2 is an enlarged cross-sectional view of a main part of the film of FIG.
FIG. 3 is a cross-sectional view showing a collision crushing apparatus for preparing a gas barrier coating agent used in the production method of the present invention.
[Explanation of symbols]
1 ... Gas barrier laminate film,
2 ... Organic polymer film,
3 ... gas barrier layer,
4 ... Gas barrier organic polymer,
5 ... Ultra fine powder,
11 ... body,
14 ... cavity,
16a, 16b ... acceleration flow path,
17a, 17b ... nozzle part,
19 ... Upper block,
24 ... Lower block.

Claims (13)

Base film;
A first gas barrier layer comprising a large number of ultrafine powders having an average particle size of 100 nm or less, comprising a gas barrier organic polymer and a hydrophilic inorganic compound dispersed in the polymer, laminated on the base film;
A second gas barrier layer, which is laminated on the first gas barrier layer, and includes a number of ultrafine powders having an average particle size of 100 nm or less made of a gas barrier organic polymer and a hydrophobic inorganic compound dispersed in the polymer;
Comprising
The first gas barrier layer has a surface 1 m in which individual ultrafine powders are in close contact with each other over the entire surface direction and thickness direction of the base film and are substantially parallel to the surface of the base film. ² The total specific surface area of a large number of ultrafine powders per unit is 100 to 600 m ² And
The second gas barrier layer is a surface in which individual ultrafine powders are in close contact with each other over the entire surface direction and thickness direction of the first gas barrier layer and are substantially parallel to the surface of the base film. 1m ² The total specific surface area of a large number of ultrafine powders per unit is 50 to 200 m ² A gas barrier laminate film, characterized in that Base film;
A first gas barrier layer comprising a large number of ultrafine powders having an average particle size of 100 nm or less, which is laminated on the base film and is composed of a gas barrier organic polymer and a hydrophobic inorganic compound dispersed in the polymer; and
A second gas barrier layer, which is laminated on the first gas barrier layer, and includes a number of ultrafine powders having an average particle diameter of 100 nm or less made of a gas barrier organic polymer and a hydrophilic inorganic compound dispersed in the polymer;
Comprising
The first gas barrier layer has a surface 1 m in which individual ultrafine powders are in close contact with each other over the entire surface direction and thickness direction of the base film and are substantially parallel to the surface of the base film. ² The total specific surface area of a large number of ultrafine powders per unit is 50 to 200 m ² And
The second gas barrier layer is a surface in which individual ultrafine powders are in close contact with each other over the entire surface direction and thickness direction of the first gas barrier layer and are substantially parallel to the surface of the base film. 1m ² The total specific surface area of a large number of ultrafine powders per unit is 100 to 600 m ² A gas barrier laminate film, characterized in that The gas barrier laminate film according to claim 1 or 2, wherein the base film is made of an organic polymer or paper. The gas barrier laminate film according to claim 1 or 2, wherein the gas barrier organic polymer is at least one water-soluble organic polymer selected from polyvinyl alcohol and an ethylene vinyl alcohol copolymer. The gas barrier laminate film according to claim 1, wherein the gas barrier layer has a thickness of 1 μm or more. A mixed ultrafine powder obtained by mixing a large number of ultrafine powders having an average particle diameter of 100 nm or less made of a hydrophilic inorganic compound and a large number of ultrafine powders having an average particle diameter of 100 nm or less made of a hydrophobic inorganic compound, and a gas barrier organic polymer, Preparing a gas barrier coating agent containing a plurality of composite ultrafine particles dispersed and bonded or bonded in the presence of a solvent; and
A surface 1 m substantially parallel to the surface of the base film by applying the barrier coating agent to the base film and drying it. ² The total specific surface area of a large number of ultrafine powders per unit is 150 to 600 m ² Forming a gas barrier layer which is
A method for producing a gas barrier laminate film, comprising: The barrier coating agent is prepared by mixing gas barrier organic polymer dissolved in a solvent with fine particles of a hydrophilic inorganic compound and fine particles of a hydrophobic inorganic compound, pressurizing the liquid mixture, and then colliding with each other at high speed. It is prepared by repeating the operation to The method for producing a gas barrier laminate film according to claim 6. A first gas barrier coating agent comprising a plurality of composite ultrafine particles in which a large number of ultrafine powders having an average particle size of 100 nm or less and a gas barrier organic polymer made of a hydrophobic inorganic compound are dispersedly bonded or bonded in the presence of a solvent. Preparing step;
A second gas barrier coating agent comprising a number of composite ultrafine particles in which a number of ultrafine powders having an average particle size of 100 nm or less and a gas barrier organic polymer composed of a hydrophilic inorganic compound are dispersed and bonded or bonded in the presence of a solvent. Preparing; and
A surface 1 m substantially parallel to the surface of the base film by applying to the base film using the first and second barrier coating agents and drying. ² The total specific surface area of a large number of hydrophobic inorganic compound ultrafine powders present per unit is 50 to 200 m ² The first gas barrier layer and the surface substantially parallel to the surface of the base film 1m ² The total specific surface area of a large number of hydrophilic inorganic compound ultrafine powders per unit is 100 to 600 m ² Forming a second gas barrier layer which is
A method for producing a gas barrier laminate film, comprising: The method for producing a gas barrier laminate film according to claim 6 or 8, wherein the base film is made of an organic polymer or paper. The method for producing a gas barrier laminated film according to claim 6 or 8, wherein the gas barrier organic polymer is at least one water-soluble organic polymer selected from polyvinyl alcohol and ethylene vinyl alcohol copolymer. The method for producing a gas barrier laminate film according to claim 6 or 8, wherein the solvent is a mixed solution of alcohol and water. The method for producing a gas barrier laminate film according to claim 6 or 8, wherein the composite ultrafine particles have an average particle size of 1 µm or less. The method for producing a gas barrier laminate film according to claim 6 or 8, wherein the composite ultrafine particles comprise 45 to 85% by weight of a liquid gas barrier organic polymer and 15 to 55% by weight of the ultrafine particles.

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