JP7384761B2 - 製造工程で被覆する二軸配向ポリエチレン薄膜とその製法 - Google Patents
製造工程で被覆する二軸配向ポリエチレン薄膜とその製法 Download PDFInfo
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- JP7384761B2 JP7384761B2 JP2020122541A JP2020122541A JP7384761B2 JP 7384761 B2 JP7384761 B2 JP 7384761B2 JP 2020122541 A JP2020122541 A JP 2020122541A JP 2020122541 A JP2020122541 A JP 2020122541A JP 7384761 B2 JP7384761 B2 JP 7384761B2
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Description
本発明の薄膜は、ポリウレタン層の層(A)を含むことを特徴とする。ポリウレタン層(A)は、全薄膜の酸素不透過特性と水蒸気不透過特性とを明らかに改善する強い拡散抑制作用を有する。また、層(A)により、特に金属及び金属酸化物を備える本発明の薄膜の耐久性のある被覆が可能になる。
ポリウレタンと共有結合を形成する官能基を有する重合体を含む層(B)(接着層)により、ポリウレタン層(A)薄膜への結合力を改善することができる。好適な重合体は、ポリエチレンである。他の重合体を使用する層(B)は、別途ポリエチレンを配合しなければならない。層(B)は、層(B)の全質量に対し、好ましくは少なくとも50重量%、特に好ましくは少なくとも70重量%、最適には少なくとも90重量%ポリエチレンを含有する。層(B)内のポリエチレンの官能基は、接着剤となる。層(B)の官能基がなく又は不十分量のとき、層(A)は、層(B)から剥離し易く、多層の薄膜構造は、不安定になる。層(B)内のポリエチレンは、層(B)が含有する官能基を有する単一の重合体が好ましい。層(B)中にポリエチレンを配合すると、層(B)、層(C)及び層(D)の処理に類似の特性を生ずる。ポリエチレンは、高密度ポリエチレン、低密度ポリエチレン、線状低密度ポリエチレン並びにそれらの共重合体及びブロック共重合体からなる群から選択される重合体であるが、前記の通り、ポリプロピレン(PP)とポリフェニレンエーテル(PPE)で構成される共重合体を採用できよう。これらの中で、線状低密度ポリエチレンが最も好ましい。
層(C)は、特に本発明の薄膜の機械的特性に決定的に重要な主層(基層又は支持層とも称する)である。層(C)の二軸配向性と層厚は、層(C)の不透過特性と光学特性に顕著に寄与する。
層(A)を有する薄膜の底面に、有効な表面性質、特に十分な表面粗度を与える層(D)は、本発明の薄膜をロールで搬送し、ロールから高速で繰り出すのに役立つ。層(D)は、ポリエチレン薄膜の通常の「表面薄層」を形成する。好適な層(D)は、ポリエチレン同種重合体を含有するが、ポリエチレン共重合体も含有してもよい。
・前記組成の層(B)~層(D)を備えかつ層(B)と層(D)を外側層とする薄膜を縦方向に一軸で伸張する工程と、
・延伸した薄膜の層(B)上に、ポリウレタンとナノ粒子を含有する流体分散系塗料を塗布する工程と、
・流体分散系塗料を乾燥して、層(A)を形成する工程と、
・薄膜を横方向に延伸して、二軸配向薄膜を製造する工程。
・前記組成を有しかつ全成分を備える少なくとも層(B)、層(C)及び層(D)用の重合体を準備する工程と、
・各重合体を溶融する工程と、
・層(B)と層(D)を薄膜の外側層として、溶融した重合体を金型スリットから押し出して、層(B)、層(C)及び層(D)に対応する少なくとも3層を備える薄膜を形成する工程と、
・得られた薄膜を冷却ロール上で冷却して、層(B)、層(C)及び層(D)を備える薄膜を形成する工程と、
・形成した薄膜を縦方向に延伸する工程と、
・少なくともポリウレタンとナノ粒子を含む流体分散系塗料を層(B)上に塗布して、層(B)上に均一な層を形成する工程と、
・層(B)上の流体分散系塗料を加熱により乾燥して、層(A)を形成する工程と、
・層(A)を形成した薄膜を横方向に延伸して、二軸配向薄膜を製造する工程。
・層(B)と層(D)とを薄膜の外側層として、前記組成物を備える非配向の層(B)~層(D)(主薄膜)で構成される薄膜を準備する工程と、
・ポリウレタンとナノ粒子とを含む流体分散系塗料を層(B)上に塗布する工程と、
・流体分散系塗料を加熱により乾燥させて層(A)を形成する工程と、
・縦方向と横方向とに同時に薄膜を延伸して、二軸配向薄膜を製造する工程。
・全成分を備える少なくとも層(B)、層(C)及び層(D)用の重合体を準備する工程と、
・各重合体を溶融する工程と、
・層(B)と層(D)を外側層として、金型スリットから溶融した重合体を押出して、層(B)、層(C)及び層(D)に対応する少なくとも3層を備える薄膜を形成する工程と、
・得られた薄膜を冷却ロール上で冷却して、層(B)、層(C)及び層(D)を備える冷却された薄膜を形成する工程と、
・少なくともポリウレタンとナノ粒子とを含有する流体分散系塗料を層(B)上に塗布する工程と、
・層(B)上の流体分散系塗料を加熱により乾燥して層(A)を形成する工程と、
・得られた層(A)を有する薄膜を縦方向と横方向とに同時に延伸して、二軸配向薄膜を製造する工程。
タケラック(Takelac)WPB341と称する三井ケミカル社製水溶性分散系塗料のポリウレタン含有量は、30%である。レバシル(Levasil)CT3 PL(別名:PL Levasil 30/50」)と称するアクゾノーベル(Akzonobel)社製コロイダルシリカの水溶性分散系塗料のコロイダルシリカ含有量は、50重量%(粒径:80nm~100nm、比表面積:35m2/g、BET法比表面積:40m2/g)である。枝状接合型無水マレイン酸基を有するポリエチレン同種重合体のアドマー(Admer)NF-408E溶融流量質量(MFR)は、温度190℃で3g/10分、重量:2.16kg(ASTM D 1238)、密度:0.92g/cm3、ビカット軟化温度:100℃(D1525)、融点:120℃である。低密度ポリエチレンの「コンスタブ(Constab)AB 06001 LD」は、その全重量に対し4重量%の合成シリカを含有する。二酸化ケイ素の粒子粒径は、4μmである。ドイツ、リューテン市所在の「コンスタブ・ポリオレフィン・アディティブズ(CONSTAB Polyolefin Additives)有限会社」からこの製品を入手できる。
Claims (19)
- 層(A)~層(D)の順序で配置され、層(B)~層(D)は、二軸配向ポリエチレンを含む4層(A)~層(D)を備えるポリエチレン薄膜において、
層(A)は、ポリウレタンとナノ粒子とを含み、層厚25nm~300nmを有し、
層(B)は、ポリウレタンと共有結合を形成する官能基を備える重合体を含みかつ層(A)に直接接続され、
層(C)は、全薄膜厚の少なくとも50%の層厚を有し、
層(D)は、薄膜の外側層となり、粘着防止剤を含むことを特徴とするポリエチレン薄膜。 - 層(B)~層(D)の各々は、全層質量に対して、少なくとも70重量%ポリエチレンを含む請求項1に記載のポリエチレン薄膜。
- 層(A)の層厚範囲は、50nm~250nmである請求項1又は2に記載のポリエチレン薄膜。
- 層(A)は、非晶質二酸化ケイ素で構成されるナノ粒子を有する請求項1~3の何れか1項に記載のポリエチレン薄膜。
- 層(A)は、平均粒径範囲20nm~150nmのナノ粒子を有する請求項1~4の何れか1項に記載のポリエチレン薄膜。
- 層(A)は、0.5重量%~20重量%のナノ粒子を含有する請求項1~5の何れか1項に記載のポリエチレン薄膜。
- 層(B)は、無水マレイン酸変性ポリエチレンを含む請求項1~6の何れか1項に記載のポリエチレン薄膜。
- 層(B)は、粘着防止剤を含有しない請求項1~7の何れか1項に記載のポリエチレン薄膜。
- 層(A)の表面に直接接続される金属層又は金属酸化物層を有する請求項1~8の何れか1項に記載のポリエチレン薄膜。
- 層(A)の表面に直接接続される酸化アルミニウム層又は二酸化ケイ素層を有する請求項1~9の何れか1項に記載のポリエチレン薄膜。
- 請求項1~10の何れか1項に記載のポリエチレン薄膜を備えることを特徴とする食料品包装品。
- ポリウレタンと共有結合を形成する官能基を備える重合体を含む層(B)と、全薄膜厚の少なくとも50%の層厚を有する層(C)と、粘着防止剤を含む層(D)とを備え、層(B)~層(D)の各々が、ポリエチレンを含む薄膜を準備する工程と、
層(B)と層(D)を薄膜の外側層として、ポリウレタンとナノ粒子を含有する流体分散系塗料を薄膜の層(B)上に塗布する工程と、
流体分散系塗料を乾燥させて、層厚25nm~300nmの層(A)を薄膜の層(B)上に形成する工程と、
薄膜の層(B)上に乾燥した層(A)が形成される薄膜を縦方向に一軸延伸する工程と、
一軸延伸した薄膜を横方向に延伸して、二軸配向薄膜を製造する工程とを含むことを特徴とするポリエチレン薄膜の製法。 - ポリウレタンと共有結合を形成する官能基を備える重合体を含む層(B)と、全薄膜厚の少なくとも50%の層厚を有する層(C)と、粘着防止剤を含む層(D)を備え、層(B)~層(D)の各々が、ポリエチレンを含む薄膜を準備する工程と、
非配向状態の層(B)と層(D)を薄膜の外側層として、ポリウレタンとナノ粒子とを含有する流体分散系塗料を層(B)上に塗布する工程と、
流体分散系塗料を加熱により乾燥させて、層厚25nm~300nmの層(A)を薄膜の層(B)上に形成する工程と、
縦方向と横方向とに同時に薄膜を延伸して、二軸配向薄膜を製造する工程とを含むことを特徴とするポリエチレン薄膜の製法。 - 流体分散系塗料を塗布する工程前に、コロナ処理の表面処理を層(B)の表面に施す工程を含む請求項12又は13に記載のポリエチレン薄膜の製法。
- 製造工程でのリバースグラビアキス被覆法により、層(B)上に流体分散系塗料を塗布する工程を含む請求項12~14の何れか1項に記載のポリエチレン薄膜の製法。
- 流体分散系塗料により層(B)上に形成される湿式層の質量は、3g/m2~20g/m2である請求項12~15の何れか1項に記載のポリエチレン薄膜の製法。
- 流体分散系塗料は、水溶性分散系である請求項12~16の何れか1項に記載のポリエチレン薄膜の製法。
- 縦方向延伸比範囲は、2~8である請求項12~17の何れか1項に記載のポリエチレン薄膜の製法。
- 横方向延伸比範囲は、4~10である請求項12~18の何れか1項に記載のポリエチレン薄膜の製法。
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