JP4565608B2 - Surface treatment agent for synthetic polymer film, surface treatment method for synthetic polymer film, and surface-treated synthetic polymer film - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、合成高分子フィルム用表面処理剤（以下、単に表面処理剤という）、合成高分子フィルムの表面処理方法（以下、単に表面処理方法という）及び表面処理合成高分子フィルムに関する。合成高分子フィルムには、該合成高分子フィルムに帯電防止性や防曇性を付与するため、その表面に表面処理剤が塗布される。かかる表面処理剤には、合成高分子フィルム本来の物性、例えば透明性を損なうことなく、該合成高分子フィルムに所望の帯電防止性や防曇性を付与できるものであることが要求されるのはいうまでもないが、合成高分子フィルムの成形や印刷等の工程における高速化が図られる近年においては、同時に優れた滑り性を付与できるものであることが要求される。本発明はかかる要求に応える表面処理剤及び表面処理方法並びに表面処理合成高分子フィルムに関する。
【０００２】
【従来の技術】
従来、合成高分子フィルムに帯電防止性や防曇性を付与する表面処理剤として各種の有機化合物が知られている。かかる有機化合物のなかには、側鎖に含窒素有機基を有する重合体として、Ｎ−ビニルピロリドンを必須成分とする単量体組成の共重合体のカチオン化物や両性化物が知られており（特許文献１参照）、またジアルキルアミノアルキル（メタ）アクリレート及び炭素数１６以上のアルキル基を有する（メタ）アクリル酸アルキルを必須成分とする単量体組成の共重合体のモノハロゲン化酢酸塩による両性化物が知られている（特許文献２参照）。ところが、これら従来の表面処理剤には、合成高分子フィルムに相応の帯電防止性や防曇性を付与することができるものの、該合成高分子フィルムの滑り性を著しく損なうという問題があり、なかには該合成高分子フィルム本来の物性、例えば透明性を損なうものもあるという問題がある。
【０００３】
【特許文献１】
特公昭５７−４６７５号公報
【特許文献２】
特公昭５９−２７７６９号公報
【０００４】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、合成高分子フィルムそれ自体の物性を損なうことなく、該合成高分子フィルムに優れた帯電防止性及び防曇性を付与すると同時に優れた滑り性をも付与することができる表面処理剤及び表面処理方法並びにこれらの特性を付与した表面処理合成高分子フィルムを提供する処にある。
【０００５】
【課題を解決するための手段】
しかして本発明者らは、上記の課題を解決するべく研究した結果、表面処理剤として、特定のビニル共重合体と滑剤とから成り、且つこれらを所定割合で含有して成るものを用いるのが正しく好適であることを見出した。
【０００６】
すなわち本発明は、下記のビニル共重合体と下記の滑剤とから成り、且つ該ビニル共重合体／該滑剤＝５０／５０〜８０／２０（重量比）の割合で含有して成ることを特徴とする表面処理剤に係る。
【０００７】
ビニル共重合体：下記の式１で示されるビニル単量体から形成された構成単位を１０〜６０重量％、下記の式２で示されるビニル単量体から形成された構成単位を１０〜４０重量％及び下記の式３で示されるビニル単量体から形成された構成単位を１０〜７０重量％（合計１００重量％）の割合で有する数平均分子量２００００〜９００００のビニル共重合体
【０００８】
【式１】
【式２】
【式３】
式１，式２，式３において、
Ｒ１，Ｒ５，Ｒ７：水素原子又はメチル基
Ｒ２：炭素数１〜４のアルキレン基
Ｒ３，Ｒ４：炭素数１〜６のアルキル基
Ｒ６：炭素数１〜４のモノヒドロキシアルキル基又は炭素数２〜４のジヒドロキシアルキル基
Ｒ８：メチル基又はエチル基
【００１２】
滑剤：炭素数１６〜１８の脂肪族カルボン酸アルカリ金属塩、炭素数１６〜１８の脂肪族カルボン酸アルカリ土類金属塩及び粒子径が０．１〜５０μｍの範囲内にあり且つ平均粒子径が１０μｍ以下の球状粒子であるシリカ粒子から選ばれる一つ又は二つ以上
【００１３】
また本発明は、前記のような本発明の表面処理剤を水性液となし、該水性液を合成高分子フィルム１ｍ２当たり該表面処理剤として０．０１〜３ｇの割合となるよう塗布することを特徴とする表面処理方法に係る。
【００１４】
更に本発明は、前記のような本発明の表面処理方法により得られる表面処理合成高分子フィルムに係る。
【００１５】
まず本発明の表面処理剤について説明する。本発明の表面処理剤はビニル共重合体と滑剤とから成っている。本発明の表面処理剤に供するビニル共重合体は、式１で示されるビニル単量体から形成された構成単位と、式２で示されるビニル単量体から形成された構成単位と、式３で示されるビニル単量体から形成された構成単位とで構成されている。式１で示されるビニル単量体において、式１中のＲ１は水素原子又はメチル基である。Ｒ２はメチレン基、エチレン基、トリメチレン基、テトラメチレン基等の炭素数１〜４のアルキルレン基である。Ｒ３とＲ４とはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、イソペンチル基、ヘキシル基等の炭素数１〜６のアルキル基である。かかるビニル単量体としては、式１中のＲ１が水素原子又はメチル基、Ｒ２がエチレン基、Ｒ３とＲ４とがメチル基又はエチル基である場合のものが好ましい。
【００１６】
式２で示されるビニル単量体において、式２中のＲ５は水素原子又はメチル基である。Ｒ６は、１）ヒドロキシメチル基、２−ヒドロキシエチル基、３−ヒドロキシプロピル基、４−ヒドロキシブチル基等の炭素数１〜４のモノヒドロキシアルキル基、又は２）２，２−ジヒドロキシエチル基、２，３−ジヒドロキシプロピル基、４，４−ジヒドロキシブチル基等の炭素数２〜４のジヒドロキシアルキル基であるが、Ｒ６としては２−ヒドロキシエチル基が好ましい。式２で示されるビニル単量体の具体例としては、ヒドロキシメチルアクリレート、２−ヒドロキシエチルアクリレート、３−ヒドロキシプロピルアクリレート、４−ヒドロキシブチルアクリレート、ヒドロキシメチルメタクリレート、２−ヒドロキシエチルメタクリレート、３−ヒドロキシプロピルメタクリレート、４−ヒドロキシブチルメタクリレート、２，２−ジヒドロキシエチルアクリレート、２，３−ジヒドロキシプロピルアクリレート、４，４−ジヒドロキシブチルアクリレート、２，２−ジヒドロキシエチルメタクリレート、２，３−ジヒドロキシプロピルメタクリレート、４，４−ジヒドロキシブチルメタクリレート等が挙げられるが、なかでも２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレートが好ましい。
【００１７】
式３で示されるビニル単量体において、式３中のＲ７は水素原子又はメチル基であり、Ｒ８はメチル基又はエチル基である。式３で示されるビニル単量体の具体例としては、メチルアクリレート、エチルアクリレート、メチルメタクリレート及びエチルメタクリレートが挙げられるが、なかでもエチルアクリレート、メチルメタクリレートが好ましい。
【００１８】
本発明の表面処理剤に供するビニル共重合体は、以上説明した式１で示されるビニル単量体から形成された構成単位と、式２で示されるビニル単量体から形成された構成単位と、式３で示されるビニル単量体から形成された構成単位とから成るものであり、式１で示されるビニル単量体から形成された構成単位を１０〜６０重量％、式２で示されるビニル単量体から形成された構成単位を１０〜４０重量％及び式３で示されるビニル単量体から形成された構成単位を１０〜７０重量％（合計１００重量％）の割合で有するものであって、且つ数平均分子量が２００００〜９００００のものである。
【００１９】
以上説明した本発明の表面処理剤に供するビニル共重合体は、公知の方法により合成できる。例えば、式１で示されるビニル単量体と式２で示されるビニル単量体と式３で示されるビニル単量体とをメタノール等の溶媒に溶解し、ラジカル重合開始剤、ラジカル連鎖移動剤を適宜添加した後、窒素雰囲気下に、ラジカル重合温度にてラジカル重合反応を行なうことにより合成できる。
【００２０】
本発明の表面処理剤に供する滑剤は、脂肪族カルボン酸塩及びシリカ粒子から選ばれる一つ又は二つ以上である。
【００２１】
滑剤としての脂肪族カルボン酸塩は、１）パルミチン酸アルカリ金属塩、パルミトレイン酸アルカリ金属塩、オレイン酸アルカリ金属塩、ステアリン酸アルカリ金属塩、イソステアリン酸アルカリ金属塩等の炭素数１６〜１８の脂肪族カルボン酸アルカリ金属塩、２）パルミチン酸アルカリ土類金属塩、パルミトレイン酸アルカリ土類金属塩、オレイン酸アルカリ土類金属塩、ステアリン酸アルカリ土類金属塩、イソステアリン酸アルカリ土類金属塩等の炭素数１６〜１８の脂肪族カルボン酸アルカリ土類金属塩である。
【００２２】
また滑剤としてのシリカ粒子は、スプレードライヤー法等のそれ自体は公知の方法によって製造されるＳｉＯ２を主成分とする粒子であるが、粒子径が０．１〜５０μｍの範囲内にあり且つ平均粒子径が１０μｍ以下のものである。なかでも粒子径が１〜５μｍの範囲内にある粒子を５０重量％以上含有しており且つ平均粒子径が５μｍ以下のものが好ましい。また滑剤としてのシリカ粒子としては、粒子の長径／短径の比が１．０〜１．２の範囲内にある球状粒子を用いるが、真球状の球状粒子が好ましい。
【００２３】
本発明の表面処理剤は、以上説明したビニル共重合体と滑剤とから成るものであり、且つビニル共重合体／滑剤＝５０／５０〜８０／２０（重量比）の割合で含有して成るものである。
【００２４】
次に本発明の表面処理方法を説明する。本発明の表面処理方は、以上説明した本発明の表面処理剤を水性液となし、該水性液を合成高分子フィルム１ｍ２当たり表面処理剤として０．０１〜３ｇの割合、好ましくは０．０２〜１ｇの割合となるよう塗布する方法である。
【００２５】
合成高分子フィルムに表面処理剤の水性液を塗布する方法としては、スプレーコート法、ロールコート法、グラビアコート法、エアナイフコート法、バーコート法、キスコート法、フローコート法、ディップコート法等が挙げられる。
【００２６】
本発明の表面処理方法を適用する合成高分子フィルムとしては、ポリオレフィン、ポリエステル、ポリスチレン、ポリメチルメタクリレート、ポリアミド、ポリカーボネート等が挙げられるが、なかでもポリオレフィン、ポリエステルに適用する場合に効果の発現が高い。
【００２７】
最後に、本発明の表面処理合成高分子フィルムについて説明する。本発明の表面処理合成高分子フィルムは、以上説明した本発明の表面処理方法により得られるものである。かかる表面処理合成高分子フィルムは、合成高分子フィルム本来の物性を損なうことなく、優れた帯電防止性及び防曇性を有し、同時に優れた滑り性をも有する。したがって本発明の表面処理合成高分子フィルムは、包装用フィルム、包装用容器、農業用フィルムとして好適である。
【００２８】
【発明の実施の形態】
本発明の表面処理剤の実施形態としては、次の１）〜４）が挙げられる。
１）下記のビニル共重合体（Ａ−１）と下記の滑剤（Ｋ−１）とから成り、且つビニル共重合体（Ａ−１）／滑剤（Ｋ−１）＝５０／５０（重量比）の割合で含有して成る表面処理剤。
ビニル共重合体（Ａ−１）：式１中のＲ１がメチル基、Ｒ２がエチレン基、Ｒ３がメチル基、Ｒ４がメチル基である場合の式１で示されるビニル単量体（Ｍ−１）から形成された構成単位を４０重量％、式２中のＲ５がメチル基、Ｒ６がヒドロキシエチル基である場合の式２で示されるビニル単量体（Ｓ−１）から形成された構成単位を２０重量％、式３中のＲ７がメチル基、Ｒ８がメチル基である場合の式３で示されるビニル単量体（Ｔ−１）から形成された構成単位を４０重量％（合計１００重量％）有する数平均分子量５５０００のビニル共重合体
滑剤（Ｋ−１）：オレイン酸ナトリウム
【００２９】
２）下記のビニル共重合体（Ａ−４）と前記の滑剤（Ｋ−１）とから成り、且つビニル共重合体（Ａ−４）／滑剤（Ｋ−１）＝６５／３５（重量比）の割合で含有して成る表面処理剤。
ビニル共重合体（Ａ−４）：式１中のＲ１がメチル基、Ｒ２がエチレン基、Ｒ３がエチル基、Ｒ４がエチル基である場合の式１で示されるビニル単量体（Ｍ−２）から形成された構成単位を４０重量％、前記のビニル単量体（Ｓ−１）から形成された構成単位を２０重量％、前記のビニル単量体（Ｔ−１）から形成された構成単位を４０重量％（合計１００重量％）有する数平均分子量５００００のビニル共重合体（Ａ−４）
【００３０】
３）下記のビニル共重合体（Ａ−６）と下記の滑剤（Ｋ−２）とから成り、且つビニル共重合体（Ａ−６）／滑剤（Ｋ−２）＝７５／２５（重量比）の割合で含有して成る表面処理剤。
ビニル共重合体（Ａ−６）：式１中のＲ１が水素原子、Ｒ２がエチレン基、Ｒ３がエチル基、Ｒ４がエチル基である場合の式１で示されるビニル単量体（Ｍ−３）から形成された構成単位を４０重量％、前記のビニル単量体（Ｓ−１）から形成された構成単位を２０重量％、式３中のＲ７が水素原子、Ｒ８がエチル基である場合の式３で示されるビニル単量体（Ｔ−２）から形成された構成単位を４０重量％（合計１００重量％）有する数平均分子量５００００のビニル共重合体（Ａ−６）
滑剤（Ｋ−２）：イソステアリン酸カリウム
【００３１】
４）下記のビニル共重合体（Ａ−２）と下記の滑剤（Ｋ−３）とから成り、且つビニル共重合体（Ａ−２）／滑剤（Ｋ−３）＝６０／４０（重量比）の割合で含有して成る表面処理剤。
ビニル共重合体（Ａ−２）：前記のビニル単量体（Ｍ−１）から形成された構成単位を５５重量％、前記のビニル単量体（Ｓ−１）から形成された構成単位を１５重量％、前記のビニル単量体（Ｔ−１）から形成された構成単位を３０重量％（合計１００重量％）有する数平均分子量２５０００のビニル共重合体
滑剤（Ｋ−３）：粒子径が０．１〜５０μｍの範囲内にあり且つ平均粒子径が２μｍの球状シリカ粒子
【００３２】
本発明の表面処理方法及び表面処理合成高分子フィルムの実施形態としては、次の５）〜１０）が挙げられる。
５）前記１）〜４）のうちでいずれかの表面処理剤を水性液となし、該水性液を延伸ポリプロピレンフィルム１ｍ２当たり該表面処理剤として０．０５〜０．５ｇの割合となるよう塗布する表面処理方法、及び該表面処理方法により得られる表面処理ポリプロピレンフィルム。
【００３３】
６）前記１）〜４）のうちでいずれかの表面処理剤を水性液となし、該水性液を二軸延伸ポリエチレンテレフタレートフィルム１ｍ２当たり該表面処理剤として０．０５〜０．５ｇの割合となるよう塗布する表面処理方法、及び該表面処理方法により得られる表面処理ポリエチレンテレフタレートフィルム。
【００３４】
７）前記１）〜４）のうちでいずれかの表面処理剤を水性液となし、該水性液をポリスチレンフィルム１ｍ２当たり該表面処理剤として０．０５〜０．５ｇの割合となるよう塗布する表面処理方法、及び該表面処理方法により得られる表面処理ポリスチレンフィルム。
【００３５】
８）前記１）〜４）のうちでいずれかの表面処理剤を水性液となし、該水性液をポリメチルメタクリレートフィルム１ｍ２当たり該表面処理剤として０．０５〜０．５ｇの割合となるよう塗布する表面処理方法、及び該表面処理方法により得られる表面処理ポリメチルメタクリレートフィルム。
【００３６】
９）前記１）〜４）のうちでいずれかの表面処理剤を水性液となし、該水性液を延伸ポリアミドフィルム１ｍ２当たり該表面処理剤として０．０５〜０．５ｇの割合となるよう塗布する表面処理方法、及び該表面処理方法により得られる表面処理ポリアミドフィルム。
【００３７】
１０）前記１）〜４）のうちでいずれかの表面処理剤を水性液となし、該水性液をポリカーボネートフィルム１ｍ２当たり該表面処理剤として０．０５〜０．５ｇの割合となるよう塗布する表面処理方法、及び該表面処理方法により得られる表面処理ポリカーボネートフィルム。
【００３８】
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例及び比較例において、％は重量％を意味する。
【００３９】
【実施例】
試験区分１（ビニル共重合体の合成）
・ビニル共重合体（Ａ−１）の合成
反応容器にイソプロパノール３００ｇ、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート６５．９ｇ（０．４２モル）、ヒドロキシエチルメタクリレート４５．１ｇ（０．３５モル）、メチルメタクリレート９０．３ｇ（０．９０モル）及びアゾビスイソブチロニトリル１．２ｇを仕込み、混合し、窒素ガス雰囲気下に、８０℃で３時間ラジカル重合反応を行なった。次にモノクロル酢酸ナトリウム４８．７ｇ（０．４２モル）と水６２９ｇとからなる水溶液を、１０分かけて滴下した後、９０℃まで昇温してイソプロパノール１８０ｇを留去した。最終的に反応固形分２５％の水性液を得た。反応固形分の一部を精製して分析した結果、式１中のＲ１がメチル基、Ｒ２がエチレン基、Ｒ３がメチル基、Ｒ４がメチル基である場合の式１で示されるビニル単量体（Ｍ−１）から形成された構成単位を４０重量％、式２中のＲ５がメチル基、Ｒ６がヒドロキシエチル基である場合の式２で示されるビニル単量体（Ｓ−１）から形成された構成単位を２０重量％、式３中のＲ７がメチル基、Ｒ８がメチル基である場合の式３で示されるビニル単量体（Ｔ−１）から形成された構成単位を４０重量％（合計１００重量％）有する数平均分子量５５０００のビニル共重合体（Ａ−１）であった。
【００４０】
・ビニル共重合体（Ａ−２）〜（Ａ−９）及び（ａ−１）〜（ａ−４）の合成
ビニル共重合体（Ａ−１）と同様にして、ビニル共重合体（Ａ−２）〜（Ａ−９）及び（ａ−１）〜（ａ−４）を合成した。ビニル共重合体（Ａ−１）も含め、これらの内容を表１にまとめて示した。
【００４１】
【表１】
表１において、
Ｍ−１：式１中のＲ１がメチル基、Ｒ２がエチレン基、Ｒ３がメチル基、Ｒ４がメチル基である場合の式１で示されるビニル単量体から形成された構成単位
Ｍ−２：式１中のＲ１がメチル基、Ｒ２がエチレン基、Ｒ３がエチル基、Ｒ４がエチル基である場合の式１で示されるビニル単量体から形成された構成単位
Ｍ−３：式１中のＲ１が水素原子、Ｒ２がエチレン基、Ｒ３がエチル基、Ｒ４がエチル基である場合の式１で示されるビニル単量体から形成された構成単位
Ｓ−１：式２中のＲ５がメチル基、Ｒ６がヒドロキシエチル基である場合の式２で示されるビニル単量体から形成された構成単位
Ｓ−２：式２中のＲ５が水素原子、Ｒ６がヒドロキシエチル基である場合の式２で示されるビニル単量体から形成された構成単位
Ｔ−１：式３中のＲ７がメチル基、Ｒ８がメチル基である場合の式３で示されるビニル単量体から形成された構成単位
Ｔ−２：式３中のＲ７が水素原子、Ｒ８がエチル基である場合の式３で示されるビニル単量体から形成された構成単位
Ｔ−３：式３中のＲ７が水素原子、Ｒ８がブチル基である場合の式３で示されるビニル単量体から形成された構成単位
Ｕ−１：下記の式４中のＲ９が水素原子、Ｒ１０がメチル基、Ｒ１１がメチル基である場合の式４で示されるビニル単量体から形成された構成単位
【００４３】
【式４】
試験区分２（表面処理剤の調製）
・実施例１｛表面処理剤（Ｐ−１）の調製｝
試験区分１で合成したビニル共重合体（Ａ−１）の２５％水性液２４ｇと、オレイン酸ナトリウム４ｇと、水７２ｇとを混合して均一な水性液とした。これを実施例１の表面処理剤（Ｐ−１）の水性液とした。
【００４５】
・実施例２〜４、参考例５〜１１及び比較例１〜６｛表面処理剤（Ｐ−２）〜（Ｐ−１１）及び（Ｒ−１）〜（Ｒ−６）の調製｝
表面処理剤（Ｐ−１）と同様にして、表面処理剤（Ｐ−２）〜（Ｐ−１１）及び（Ｒ−１）〜（Ｒ−６）を調製した。これらをそれぞれ、実施例２〜４の表面処理剤（Ｐ−２）〜（Ｐ−４）、参考例５〜１１の表面処理剤（Ｐ−５）〜（Ｐ−１１）及び比較例１〜６の表面処理剤（Ｒ−１）〜（Ｒ−６）の水性液とした。実施例１の表面処理剤（Ｐ−１）も含め、これらの内容を表２にまとめて示した。
【００４６】
【表２】
表２において、
Ｋ−１：オレイン酸ナトリウム
Ｋ−２：イソステアリン酸カリウム
Ｋ−３：粒子径が０．１〜５０μｍの範囲内にあり且つ平均粒子径が２μｍの球状シリカ粒子
Ｋ−４：ステアリン酸アミド
Ｋ−５：ラウリン酸
Ｋ−６：ソルビタントリステアラート
Ｋ−７：数平均分子量５０００の酸化ポリエチレンワックス
Ｋ−８：アミノ当量１０００のアミノ変性ジメチルポリシロキサン
Ｋ−９：粒子径が０．１〜５０μｍの範囲内にあり且つ平均粒子径が２μｍの球状ポリメチルシルセスキオキサン粒子
Ｋ−１０：平均粒子径が５μｍのタルク粉末
【００４８】
試験区分３（合成高分子フィルムの表面処理及び表面処理合成高分子フィルムの調製）
・実施例１２
試験区分２で調製した表面処理剤（Ｐ−１）の水性液を更に水希釈して表面処理剤（Ｐ−１）の１％水性液とし、この水性液をバーコーターにより膜厚１００μｍの延伸ポリプロピレンフィルムに塗布した後、７０℃で３分間熱風乾燥して、表面処理ポリプロピレンフィルムを得た。
【００４９】
・実施例１３〜１５、参考例１６〜２２及び比較例７〜１２
実施例１２の表面処理ポリプロピレンフィルムと同様にして、実施例１３〜１５、参考例１６〜２２及び比較例７〜１２の表面処理ポリプロピレンフィルムを得た。実施例１２の表面処理ポリプロピレンフィルムも含め、これらの内容を表３にまとめて示した。
【００５０】
・実施例２３
試験区分２で調製した表面処理剤（Ｐ−１）の水性液を更に水希釈して表面処理剤（Ｐ−１）の１％水性液とし、この水性液をバーコーターにより膜厚１００μｍの二軸延伸ポリエチレンテレフタレートフィルムに塗布した後、７０℃で３分間熱風乾燥して、表面処理ポリエチレンテレフタレートフィルムを得た。
【００５１】
・実施例２４〜２６、参考例２７〜３３及び比較例１３〜１８
実施例２３の表面処理ポリエチレンテレフタレートフィルムと同様にして、実施例２４〜２６、参考例２７〜３３及び比較例１３〜１８の表面処理ポリエチレンテレフタレートフィルムを得た。実施例２３の表面処理ポリエチレンテレフタレートフィルムも含め、これらの内容を表４にまとめて示した。
【００５２】
・実施例３４
試験区分２で調製した表面処理剤（Ｐ−１）の水性液を更に水希釈して表面処理剤（Ｐ−１）の１％水性液とし、この水性液をバーコーターにより膜厚１００μｍのポリスチレンフィルムに塗布した後、７０℃で３分間熱風乾燥して、表面処理ポリスチレンフィルムを得た。
【００５３】
・実施例３５〜３７、参考例３８〜４４及び比較例１９〜２４
実施例３４の表面処理ポリスチレンフィルムと同様にして、実施例３５〜３７、参考例３８〜４４及び比較例１９〜２４の表面処理ポリスチレンフィルムを得た。実施例３４の表面処理ポリスチレンフィルムも含め、これらの内容を表５にまとめて示した。
【００５４】
・実施例４５
試験区分２で調製した表面処理剤（Ｐ−１）の水性液を更に水希釈して表面処理剤（Ｐ−１）の１％水性液とし、この水性液をバーコーターにより膜厚１００μｍのポリメチルメタクリレートフィルムに塗布した後、７０℃で３分間熱風乾燥して、表面処理ポリメチルメタクリレートフィルムを得た。
【００５５】
・実施例４６〜４８、参考例４９〜５５及び比較例２５〜３０
実施例４５の表面処理ポリメチルメタクリレートフィルムと同様にして、実施例４６〜４８、参考例４９〜５５及び比較例２５〜３０の表面処理ポリメチルメタクリレートフィルムを得た。実施例４５の表面処理ポリメチルメタクリレートフィルムも含め、これらの内容を表６にまとめて示した。
【００５６】
・実施例５６
試験区分２で調製した表面処理剤（Ｐ−１）の水性液を更に水希釈して表面処理剤（Ｐ−１）の１％水性液とし、この水性液をバーコーターにより膜厚１００μｍの延伸ポリアミドフィルムに塗布した後、７０℃で３分間熱風乾燥して、表面処理ポリアミドフィルムを得た。
【００５７】
・実施例５７〜５９、参考例６０〜６６及び比較例３１〜３６
実施例５６の表面処理ポリアミドフィルムと同様にして、実施例５７〜５９、参考例６０〜６６及び比較例３１〜３６の表面処理ポリアミドフィルムを得た。実施例５６の表面処理ポリアミドフィルムも含め、これらの内容を表７にまとめて示した。
【００５８】
・実施例６７
試験区分２で調製した表面処理剤（Ｐ−１）の水性液を更に水希釈して表面処理剤（Ｐ−１）の１％水性液とし、この水性液をバーコーターにより膜厚１００μｍのポリカーボネートフィルムに塗布した後、７０℃で３分間熱風乾燥して、表面処理ポリカーボネートフィルムを得た。
【００５９】
・実施例６８〜７０、参考例７１〜７７及び比較例３７〜４２
実施例６７の表面処理ポリカーボネートフィルムと同様にして、実施例６８〜７０、参考例７１〜７７及び比較例３７〜４２の表面処理ポリカーボネートフィルムを得た。実施例６７の表面処理ポリカーボネートフィルムも含め、これらの内容を表８にまとめて示した。
【００６０】
試験区分４（表面処理合成高分子フィルムの評価）
試験区分３で調製した合計６種の表面処理合成高分子フィルムについて、帯電防止性、防曇性、滑り性及び透明性を以下のように評価した。結果を表３〜表８にまとめて示した。
・帯電防止性の評価
表面処理合成高分子フィルムを、２０℃で相対湿度６５％の条件下に２４時間調湿した後、同条件で表面比抵抗（Ω）を表面抵抗値測定装置（シシド電気社製、商品名メガレスタＨＴ−３０１）を用いて測定し、下記の基準で評価した。
評価基準
◎：表面比抵抗が１×１０１０Ω未満
○：表面比抵抗が１×１０１０Ω以上１×１０１１未満
△：表面比抵抗が１×１０１１Ω以上１×１０１２未満
×：表面比抵抗が１×１０１２Ω以上
【００６１】
・防曇性の評価
防曇性評価用プラスチック容器に２０℃の水を張り、この容器に表面処理合成高分子フィルムをその処理面を下にして張り付け、５℃の冷蔵庫に１時間放置した。その後、表面処理合成高分子フィルムの曇りを肉眼観察し、下記の基準で評価した。
評価基準
◎：全く曇りが見られない
○：曇りは見られないが、大粒の水滴が見られる
△：処理面積の２割未満が微小水滴で曇り、不透明状態を呈する
×：処理面積の２割以上が微小水滴で曇り、不透明状態を呈する
【００６２】
・滑り性の評価
ＪＩＳ−Ｋ７１２５に準拠して、表面処理合成高分子フィルムの動摩擦係数を測定し、下記の基準で評価した。
評価基準
◎：動摩擦係数が０．２５未満
○：動摩擦係数が０．２５以上０．３０未満
△：動摩擦係数が０．３０以上０．３５未満
×：動摩擦係数が０．３５以上
【００６３】
・透明性の評価
表面処理合成高分子フィルムを未処理合成高分子フィルムと比較して肉眼観察し、下記の基準で評価した。
評価基準
◎：未処理合成高分子フィルムと同程度の透明性を有する
○：未処理合成高分子フィルムより僅かに濁りがある
△：未処理合成高分子フィルムより明らかに濁りがある
×：未処理合成高分子フィルムより著しく濁りがある
【００６４】
【表３】
【表４】
【表５】
【表６】
【表７】
【表８】
【発明の効果】
既に明らかなように、以上説明した本発明には、合成高分子フィルム本来の物性を損なうことなく、該合成高分子フィルムに優れた帯電防止性及び防曇性を付与し、同時に優れた滑り性をも付与することができるという効果がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a surface treatment agent for a synthetic polymer film (hereinafter simply referred to as a surface treatment agent), a surface treatment method for a synthetic polymer film (hereinafter simply referred to as a surface treatment method), and a surface-treated synthetic polymer film. A surface treatment agent is applied to the surface of the synthetic polymer film in order to impart antistatic properties and antifogging properties to the synthetic polymer film. Such a surface treatment agent is required to be able to impart desired antistatic properties and antifogging properties to the synthetic polymer film without impairing the original physical properties of the synthetic polymer film, for example, transparency. Needless to say, in recent years when high speed is achieved in processes such as molding and printing of synthetic polymer films, it is required to be able to impart excellent slipperiness at the same time. The present invention relates to a surface treatment agent, a surface treatment method, and a surface-treated synthetic polymer film that meet such requirements.
[0002]
[Prior art]
Conventionally, various organic compounds are known as surface treatment agents that impart antistatic properties and antifogging properties to synthetic polymer films. Among such organic compounds, as a polymer having a nitrogen-containing organic group in the side chain, a cationized product and an amphoteric product of a copolymer having a monomer composition containing N-vinylpyrrolidone as an essential component are known (Patent Documents). 1), and an amphoteric product of a monohalogenated acetate of a copolymer having a monomer composition containing a dialkylaminoalkyl (meth) acrylate and an alkyl (meth) acrylate having an alkyl group having 16 or more carbon atoms as an essential component Is known (see Patent Document 2). However, these conventional surface treatment agents can give the antistatic property and antifogging property corresponding to the synthetic polymer film, but there is a problem that the slipperiness of the synthetic polymer film is remarkably impaired. There is a problem in that some of the original physical properties of the synthetic polymer film, such as transparency, are impaired.
[0003]
[Patent Document 1]
Japanese Patent Publication No.57-4675
[Patent Document 2]
Japanese Patent Publication No.59-27769
[0004]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to impart excellent antistatic properties and antifogging properties to the synthetic polymer film without impairing the physical properties of the synthetic polymer film itself. The present invention provides a surface treatment agent and a surface treatment method that can be used, and a surface-treated synthetic polymer film imparted with these characteristics.
[0005]
[Means for Solving the Problems]
Therefore, as a result of researches to solve the above problems, the present inventors use a surface treatment agent comprising a specific vinyl copolymer and a lubricant, and containing these in a predetermined ratio. Has been found to be correct and suitable.
[0006]
That is, the present invention comprises the following vinyl copolymer and the following lubricant, and is contained at a ratio of the vinyl copolymer / the lubricant = 50/50 to 80/20 (weight ratio). This relates to the surface treatment agent.
[0007]
Vinyl copolymer: 10 to 60% by weight of a structural unit formed from a vinyl monomer represented by the following formula 1, and 10 to 40 structural units formed from a vinyl monomer represented by the following formula 2. Number average molecular weight having 10% to 70% by weight (total 100% by weight) of structural units formed from vinyl monomers represented by weight% and the following formula 3 20000 ~ 90,000 vinyl copolymer
[0008]
[Formula 1]
[Formula 2]
[Formula 3]
In Equation 1, Equation 2, and Equation 3,
R 1 , R 5 , R 7 : Hydrogen atom or methyl group
R 2 : C1-C4 alkylene group
R 3 , R 4 : C1-C6 alkyl group
R 6 : C1-C4 monohydroxyalkyl group or C2-C4 dihydroxyalkyl group
R 8 : Methyl group or ethyl group
[0012]
Lubricant: Alkaline metal salt of aliphatic carboxylic acid having 16 to 18 carbon atoms, Alkaline metal salt of aliphatic carboxylic acid having 16 to 18 carbon atoms and particle diameter in the range of 0.1 to 50 μm and average particle diameter One or more selected from silica particles that are spherical particles of 10 μm or less
[0013]
In the present invention, the surface treatment agent of the present invention as described above is an aqueous liquid, and the aqueous liquid is used as a synthetic polymer film 1 m. 2 The surface treatment method is characterized in that the surface treatment agent is applied at a ratio of 0.01 to 3 g.
[0014]
Furthermore, the present invention relates to a surface-treated synthetic polymer film obtained by the surface treatment method of the present invention as described above.
[0015]
First, the surface treatment agent of the present invention will be described. The surface treating agent of the present invention comprises a vinyl copolymer and a lubricant. The vinyl copolymer used for the surface treatment agent of the present invention includes a structural unit formed from a vinyl monomer represented by Formula 1, a structural unit formed from a vinyl monomer represented by Formula 2, and a formula 3 It is comprised with the structural unit formed from the vinyl monomer shown by. In the vinyl monomer represented by formula 1, R in formula 1 1 Is a hydrogen atom or a methyl group. R 2 Is an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a trimethylene group or a tetramethylene group. R 3 And R 4 Is an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, and hexyl group. Such vinyl monomers include R in Formula 1 1 Is a hydrogen atom or a methyl group, R 2 Is ethylene group, R 3 And R 4 Those in which and are a methyl group or an ethyl group are preferred.
[0016]
In the vinyl monomer represented by formula 2, R in formula 2 5 Is a hydrogen atom or a methyl group. R 6 1) a monohydroxyalkyl group having 1 to 4 carbon atoms such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, or 2) 2,2-dihydroxyethyl group, 2 , 3-dihydroxypropyl group, 4,4-dihydroxybutyl group and the like, which are dihydroxyalkyl groups having 2 to 4 carbon atoms such as R 6 Is preferably a 2-hydroxyethyl group. Specific examples of the vinyl monomer represented by Formula 2 include hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxy Propyl methacrylate, 4-hydroxybutyl methacrylate, 2,2-dihydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, 4,4-dihydroxybutyl acrylate, 2,2-dihydroxyethyl methacrylate, 2,3-dihydroxypropyl methacrylate, 4 , 4-dihydroxybutyl methacrylate, etc., among which 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred. Arbitrariness.
[0017]
In the vinyl monomer represented by formula 3, R in formula 3 7 Is a hydrogen atom or a methyl group, R 8 Is a methyl group or an ethyl group. Specific examples of the vinyl monomer represented by Formula 3 include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Among them, ethyl acrylate and methyl methacrylate are preferable.
[0018]
The vinyl copolymer to be used for the surface treatment agent of the present invention includes a structural unit formed from the vinyl monomer represented by the formula 1 described above, and a structural unit formed from the vinyl monomer represented by the formula 2. And a structural unit formed from a vinyl monomer represented by the formula 3, wherein 10 to 60% by weight of a structural unit formed from the vinyl monomer represented by the formula 1 is represented by the formula 2. 10 to 40% by weight of structural units formed from vinyl monomers and 10 to 70% by weight (total 100% by weight) of structural units formed from vinyl monomers represented by Formula 3 And the number average molecular weight is 20000-90000.
[0019]
The vinyl copolymer used for the surface treating agent of the present invention described above can be synthesized by a known method. For example, a vinyl monomer represented by formula 1, a vinyl monomer represented by formula 2 and a vinyl monomer represented by formula 3 are dissolved in a solvent such as methanol, and a radical polymerization initiator, radical chain transfer agent Can be synthesized by performing a radical polymerization reaction at a radical polymerization temperature in a nitrogen atmosphere.
[0020]
The lubricant used for the surface treatment agent of the present invention is one or more selected from aliphatic carboxylates and silica particles.
[0021]
Aliphatic carboxylates as lubricants are: 1) Fatty acids having 16 to 18 carbon atoms such as alkali metal palmitate, alkali metal palmitoleate, alkali metal oleate, alkali metal stearate, alkali metal isostearate, etc. Carboxylic acid alkali metal salts, 2) palmitic acid alkaline earth metal salts, palmitoleic acid alkaline earth metal salts, oleic acid alkaline earth metal salts, stearic acid alkaline earth metal salts, isostearic acid alkaline earth metal salts, etc. It is a C16-18 aliphatic carboxylic acid alkaline earth metal salt.
[0022]
Silica particles as a lubricant are produced by a method known per se such as a spray dryer method. 2 In which the particle diameter is in the range of 0.1 to 50 μm and the average particle diameter is 10 μm or less. Among them, particles containing 50% by weight or more of particles having a particle size in the range of 1 to 5 μm and an average particle size of 5 μm or less are preferable. Further, as the silica particles as the lubricant, spherical particles having a major axis / minor axis ratio in the range of 1.0 to 1.2 are used, but true spherical particles are preferable.
[0023]
The surface treatment agent of the present invention comprises the vinyl copolymer and lubricant described above, and is contained in a ratio of vinyl copolymer / lubricant = 50/50 to 80/20 (weight ratio). Is.
[0024]
Next, the surface treatment method of the present invention will be described. In the surface treatment method of the present invention, the surface treatment agent of the present invention described above is an aqueous liquid, and the aqueous liquid is used as a synthetic polymer film 1 m. 2 It is the method of apply | coating so that it may become a ratio of 0.01-3g, and preferably 0.02-1g as a surface treatment agent.
[0025]
Examples of methods for applying an aqueous surface treatment agent to a synthetic polymer film include spray coating, roll coating, gravure coating, air knife coating, bar coating, kiss coating, flow coating, and dip coating. Can be mentioned.
[0026]
Examples of the synthetic polymer film to which the surface treatment method of the present invention is applied include polyolefins, polyesters, polystyrenes, polymethyl methacrylates, polyamides, polycarbonates, and the like, and the effects are particularly high when applied to polyolefins and polyesters. .
[0027]
Finally, the surface-treated synthetic polymer film of the present invention will be described. The surface-treated synthetic polymer film of the present invention is obtained by the surface treatment method of the present invention described above. Such a surface-treated synthetic polymer film has excellent antistatic properties and antifogging properties without impairing the original physical properties of the synthetic polymer film, and at the same time has excellent slipperiness. Therefore, the surface-treated synthetic polymer film of the present invention is suitable as a packaging film, a packaging container, and an agricultural film.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the surface treatment agent of the present invention include the following 1) to 4).
1) Consisting of the following vinyl copolymer (A-1) and the following lubricant (K-1), and vinyl copolymer (A-1) / lubricant (K-1) = 50/50 (weight ratio) ) And a surface treatment agent.
Vinyl copolymer (A-1): R in formula 1 1 Is a methyl group, R 2 Is ethylene group, R 3 Is a methyl group, R 4 40% by weight of the structural unit formed from the vinyl monomer (M-1) represented by the formula 1 when R is a methyl group, R in the formula 2 5 Is a methyl group, R 6 20% by weight of a structural unit formed from the vinyl monomer (S-1) represented by the formula 2 when R is a hydroxyethyl group, R in the formula 3 7 Is a methyl group, R 8 Vinyl copolymer having a number average molecular weight of 55000 and having 40% by weight (100% by weight in total) of the structural units formed from the vinyl monomer (T-1) represented by formula 3 when is a methyl group
Lubricant (K-1): Sodium oleate
[0029]
2) Consisting of the following vinyl copolymer (A-4) and the lubricant (K-1), and vinyl copolymer (A-4) / lubricant (K-1) = 65/35 (weight ratio) ) And a surface treatment agent.
Vinyl copolymer (A-4): R in formula 1 1 Is a methyl group, R 2 Is ethylene group, R 3 Is an ethyl group, R 4 40% by weight of the structural unit formed from the vinyl monomer (M-2) represented by the formula 1 when is an ethyl group, and the structural unit formed from the vinyl monomer (S-1). A vinyl copolymer (A-4) having a number average molecular weight of 50,000 having 20% by weight and 40% by weight (100% by weight in total) of the structural units formed from the vinyl monomer (T-1).
[0030]
3) Consists of the following vinyl copolymer (A-6) and the following lubricant (K-2), and vinyl copolymer (A-6) / lubricant (K-2) = 75/25 (weight ratio) ) And a surface treatment agent.
Vinyl copolymer (A-6): R in formula 1 1 Is a hydrogen atom, R 2 Is ethylene group, R 3 Is an ethyl group, R 4 40% by weight of the structural unit formed from the vinyl monomer (M-3) represented by Formula 1 when is an ethyl group, and the structural unit formed from the vinyl monomer (S-1). 20% by weight, R in formula 3 7 Is a hydrogen atom, R 8 A vinyl copolymer having a number average molecular weight of 50,000 (A-) having 40% by weight (total 100% by weight) of structural units formed from the vinyl monomer (T-2) represented by the formula 3 when is an ethyl group 6)
Lubricant (K-2): potassium isostearate
[0031]
4) Consisting of the following vinyl copolymer (A-2) and the following lubricant (K-3), and vinyl copolymer (A-2) / lubricant (K-3) = 60/40 (weight ratio) ) And a surface treatment agent.
Vinyl copolymer (A-2): 55% by weight of the structural unit formed from the vinyl monomer (M-1) and the structural unit formed from the vinyl monomer (S-1). A vinyl copolymer having a number average molecular weight of 25,000, having 15% by weight and 30% by weight (100% by weight in total) of structural units formed from the vinyl monomer (T-1).
Lubricant (K-3): spherical silica particles having a particle diameter in the range of 0.1 to 50 μm and an average particle diameter of 2 μm
[0032]
Examples of the surface treatment method and the surface treatment synthetic polymer film of the present invention include the following 5) to 10).
5) Any one of the surface treatment agents in the above 1) to 4) is made into an aqueous liquid, and the aqueous liquid is made into a stretched polypropylene film 1 m. 2 The surface treatment method which apply | coats so that it may become a ratio of 0.05-0.5g as this surface treatment agent per surface, and the surface treatment polypropylene film obtained by this surface treatment method.
[0033]
6) The surface treatment agent of any one of 1) to 4) is an aqueous liquid, and the aqueous liquid is used as a biaxially stretched polyethylene terephthalate film 1m. 2 A surface treatment method for applying a surface treatment agent of 0.05 to 0.5 g per surface, and a surface-treated polyethylene terephthalate film obtained by the surface treatment method.
[0034]
7) Any one of the surface treatment agents 1) to 4) is an aqueous liquid, and the aqueous liquid is converted to a polystyrene film 1m. 2 The surface treatment method which apply | coats so that it may become a ratio of 0.05-0.5g as this surface treatment agent per surface, and the surface treatment polystyrene film obtained by this surface treatment method.
[0035]
8) Any one of the above-mentioned 1) to 4) is used as an aqueous liquid, and the aqueous liquid is used as a polymethyl methacrylate film 1m. 2 A surface treatment method for applying a surface treatment agent of 0.05 to 0.5 g per surface, and a surface-treated polymethylmethacrylate film obtained by the surface treatment method.
[0036]
9) The surface treatment agent of any one of 1) to 4) is an aqueous liquid, and the aqueous liquid is used as a stretched polyamide film 1m. 2 A surface treatment method for applying a surface treatment agent at a ratio of 0.05 to 0.5 g per surface, and a surface-treated polyamide film obtained by the surface treatment method.
[0037]
10) Any one of the above-mentioned 1) to 4) is used as an aqueous liquid, and the aqueous liquid is converted into a polycarbonate film 1m. 2 A surface treatment method for applying the surface treatment agent at a ratio of 0.05 to 0.5 g per surface, and a surface-treated polycarbonate film obtained by the surface treatment method.
[0038]
Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following examples and comparative examples,% means% by weight.
[0039]
【Example】
Test Category 1 (Synthesis of vinyl copolymer)
・ Synthesis of vinyl copolymer (A-1)
In a reaction vessel, 300 g of isopropanol, 65.9 g (0.42 mol) of N, N-dimethylaminoethyl methacrylate, 45.1 g (0.35 mol) of hydroxyethyl methacrylate, 90.3 g (0.90 mol) of methyl methacrylate and azo 1.2 g of bisisobutyronitrile was charged, mixed, and subjected to radical polymerization reaction at 80 ° C. for 3 hours in a nitrogen gas atmosphere. Next, an aqueous solution composed of 48.7 g (0.42 mol) of sodium monochloroacetate and 629 g of water was dropped over 10 minutes, and then the temperature was raised to 90 ° C. to distill off 180 g of isopropanol. Finally, an aqueous liquid having a reaction solid content of 25% was obtained. As a result of purifying and analyzing a part of the reaction solid, R in Formula 1 1 Is a methyl group, R 2 Is ethylene group, R 3 Is a methyl group, R 4 40% by weight of the structural unit formed from the vinyl monomer (M-1) represented by the formula 1 when R is a methyl group, R in the formula 2 5 Is a methyl group, R 6 20% by weight of a structural unit formed from the vinyl monomer (S-1) represented by the formula 2 when R is a hydroxyethyl group, R in the formula 3 7 Is a methyl group, R 8 A vinyl copolymer having a number average molecular weight of 55000 (A-) having 40% by weight (100% by weight in total) of the structural units formed from the vinyl monomer (T-1) represented by the formula 3 when is a methyl group 1).
[0040]
Synthesis of vinyl copolymers (A-2) to (A-9) and (a-1) to (a-4)
In the same manner as the vinyl copolymer (A-1), vinyl copolymers (A-2) to (A-9) and (a-1) to (a-4) were synthesized. These contents including the vinyl copolymer (A-1) are summarized in Table 1.
[0041]
[Table 1]
In Table 1,
M-1: R in Formula 1 1 Is a methyl group, R 2 Is ethylene group, R 3 Is a methyl group, R 4 A structural unit formed from a vinyl monomer represented by formula 1 when is a methyl group
M-2: R in Formula 1 1 Is a methyl group, R 2 Is ethylene group, R 3 Is an ethyl group, R 4 A structural unit formed from a vinyl monomer represented by formula 1 when is an ethyl group
M-3: R in Formula 1 1 Is a hydrogen atom, R 2 Is ethylene group, R 3 Is an ethyl group, R 4 A structural unit formed from a vinyl monomer represented by formula 1 when is an ethyl group
S-1: R in Formula 2 5 Is a methyl group, R 6 A structural unit formed from a vinyl monomer represented by formula 2 when is a hydroxyethyl group
S-2: R in Formula 2 5 Is a hydrogen atom, R 6 A structural unit formed from a vinyl monomer represented by formula 2 when is a hydroxyethyl group
T-1: R in Formula 3 7 Is a methyl group, R 8 A structural unit formed from a vinyl monomer represented by formula 3 when is a methyl group
T-2: R in Formula 3 7 Is a hydrogen atom, R 8 A structural unit formed from a vinyl monomer represented by formula 3 when is an ethyl group
T-3: R in Formula 3 7 Is a hydrogen atom, R 8 A structural unit formed from a vinyl monomer represented by formula 3 when is a butyl group
U-1: R in Formula 4 below 9 Is a hydrogen atom, R 10 Is a methyl group, R 11 A structural unit formed from a vinyl monomer represented by formula 4 when is a methyl group
[0043]
[Formula 4]
Test Category 2 (Preparation of surface treatment agent)
Example 1 {Preparation of surface treatment agent (P-1)}
24 g of a 25% aqueous solution of vinyl copolymer (A-1) synthesized in Test Category 1, 4 g of sodium oleate, and 72 g of water were mixed to obtain a uniform aqueous solution. This was used as the aqueous liquid of the surface treating agent (P-1) of Example 1.
[0045]
Examples 2 to 4, Reference Examples 5 to 11 and Comparative Examples 1 to 6 {Preparation of surface treatment agents (P-2) to (P-11) and (R-1) to (R-6)}
Surface treatment agents (P-2) to (P-11) and (R-1) to (R-6) were prepared in the same manner as the surface treatment agent (P-1). These were treated with surface treatment agents (P-2) to (P-4) of Examples 2 to 4, surface treatment agents (P-5) to (P-11) of Reference Examples 5 to 11, and Comparative Examples 1 to 4, respectively. No. 6 surface treatment agents (R-1) to (R-6) were used as aqueous solutions. These contents including the surface treating agent (P-1) of Example 1 are summarized in Table 2.
[0046]
[Table 2]
In Table 2,
K-1: Sodium oleate
K-2: Potassium isostearate
K-3: spherical silica particles having a particle diameter in the range of 0.1 to 50 μm and an average particle diameter of 2 μm
K-4: Stearic acid amide
K-5: Lauric acid
K-6: Sorbitan Tristearate
K-7: Oxidized polyethylene wax having a number average molecular weight of 5000
K-8: amino-modified dimethylpolysiloxane having an amino equivalent of 1000
K-9: spherical polymethylsilsesquioxane particles having a particle diameter in the range of 0.1 to 50 μm and an average particle diameter of 2 μm
K-10: Talc powder with an average particle size of 5 μm
[0048]
Test category 3 (surface treatment of synthetic polymer film and preparation of surface-treated synthetic polymer film)
Example 12
The aqueous solution of the surface treatment agent (P-1) prepared in Test Category 2 was further diluted with water to make a 1% aqueous solution of the surface treatment agent (P-1), and this aqueous solution was stretched to a thickness of 100 μm with a bar coater. After apply | coating to a polypropylene film, it dried with hot air at 70 degreeC for 3 minute (s), and obtained the surface treatment polypropylene film.
[0049]
Examples 13 to 15, Reference Examples 16 to 22 and Comparative Examples 7 to 12
In the same manner as the surface-treated polypropylene film of Example 12, the surface-treated polypropylene films of Examples 13 to 15, Reference Examples 16 to 22 and Comparative Examples 7 to 12 were obtained. These contents including the surface-treated polypropylene film of Example 12 are summarized in Table 3.
[0050]
Example 23
The aqueous solution of the surface treatment agent (P-1) prepared in Test Category 2 was further diluted with water to obtain a 1% aqueous solution of the surface treatment agent (P-1). After coating on an axially stretched polyethylene terephthalate film, it was dried with hot air at 70 ° C. for 3 minutes to obtain a surface-treated polyethylene terephthalate film.
[0051]
Examples 24 to 26, Reference Examples 27 to 33, and Comparative Examples 13 to 18
In the same manner as the surface-treated polyethylene terephthalate film of Example 23, surface-treated polyethylene terephthalate films of Examples 24-26, Reference Examples 27-33, and Comparative Examples 13-18 were obtained. These contents including the surface-treated polyethylene terephthalate film of Example 23 are summarized in Table 4.
[0052]
Example 34
The aqueous solution of the surface treatment agent (P-1) prepared in Test Category 2 was further diluted with water to make a 1% aqueous solution of the surface treatment agent (P-1), and this aqueous solution was polystyrene having a film thickness of 100 μm using a bar coater. After coating on the film, it was dried with hot air at 70 ° C. for 3 minutes to obtain a surface-treated polystyrene film.
[0053]
Examples 35-37, Reference Examples 38-44 and Comparative Examples 19-24
In the same manner as the surface-treated polystyrene film of Example 34, surface-treated polystyrene films of Examples 35 to 37, Reference Examples 38 to 44, and Comparative Examples 19 to 24 were obtained. These contents including the surface-treated polystyrene film of Example 34 are summarized in Table 5.
[0054]
Example 45
The aqueous solution of the surface treatment agent (P-1) prepared in Test Category 2 was further diluted with water to make a 1% aqueous solution of the surface treatment agent (P-1). After apply | coating to a methylmethacrylate film, it dried with hot air at 70 degreeC for 3 minute (s), and obtained the surface treatment polymethylmethacrylate film.
[0055]
Examples 46 to 48, Reference Examples 49 to 55, and Comparative Examples 25 to 30
In the same manner as the surface-treated polymethyl methacrylate film of Example 45, the surface-treated polymethyl methacrylate films of Examples 46 to 48, Reference Examples 49 to 55, and Comparative Examples 25 to 30 were obtained. These contents including the surface-treated polymethylmethacrylate film of Example 45 are summarized in Table 6.
[0056]
Example 56
The aqueous solution of the surface treatment agent (P-1) prepared in Test Category 2 was further diluted with water to make a 1% aqueous solution of the surface treatment agent (P-1), and this aqueous solution was stretched to a thickness of 100 μm with a bar coater. After apply | coating to a polyamide film, it dried with hot air at 70 degreeC for 3 minute (s), and obtained the surface treatment polyamide film.
[0057]
Examples 57 to 59, Reference Examples 60 to 66, and Comparative Examples 31 to 36
In the same manner as the surface-treated polyamide film of Example 56, surface-treated polyamide films of Examples 57 to 59, Reference Examples 60 to 66, and Comparative Examples 31 to 36 were obtained. These contents including the surface-treated polyamide film of Example 56 are summarized in Table 7.
[0058]
Example 67
The aqueous solution of the surface treatment agent (P-1) prepared in Test Category 2 was further diluted with water to give a 1% aqueous solution of the surface treatment agent (P-1). After coating on the film, it was dried with hot air at 70 ° C. for 3 minutes to obtain a surface-treated polycarbonate film.
[0059]
Examples 68 to 70, Reference Examples 71 to 77, and Comparative Examples 37 to 42
In the same manner as the surface-treated polycarbonate film of Example 67, surface-treated polycarbonate films of Examples 68 to 70, Reference Examples 71 to 77, and Comparative Examples 37 to 42 were obtained. These contents including the surface-treated polycarbonate film of Example 67 are summarized in Table 8.
[0060]
Test Category 4 (Evaluation of surface-treated synthetic polymer film)
The antistatic property, antifogging property, slipperiness and transparency of the total 6 types of surface-treated synthetic polymer films prepared in Test Category 3 were evaluated as follows. The results are summarized in Tables 3 to 8.
・ Evaluation of antistatic properties
The surface-treated synthetic polymer film was conditioned at 20 ° C. under a relative humidity of 65% for 24 hours, and the surface resistivity (Ω) was measured under the same conditions by a surface resistance value measuring device (trade name Megaresta, manufactured by Sicid Electric Co., Ltd.). HT-301) and evaluated according to the following criteria.
Evaluation criteria
A: Surface specific resistance is 1 × 10 10 Less than Ω
○: Surface specific resistance is 1 × 10 10 Ω or more 1 × 10 11 Less than
Δ: Surface specific resistance is 1 × 10 11 Ω or more 1 × 10 12 Less than
×: Surface specific resistance is 1 × 10 12 Ω or more
[0061]
・ Evaluation of anti-fogging property
Water at 20 ° C. was spread on a plastic container for evaluation of anti-fogging property, and a surface-treated synthetic polymer film was stuck on the container with the treated side down, and left in a refrigerator at 5 ° C. for 1 hour. Thereafter, the cloudiness of the surface-treated synthetic polymer film was visually observed and evaluated according to the following criteria.
Evaluation criteria
A: No cloudiness is seen
○: Cloudiness is not seen, but large water droplets are seen
Δ: Less than 20% of the treated area is clouded with fine water droplets and is opaque
×: 20% or more of the treated area is clouded with minute water droplets and is opaque
[0062]
・ Evaluation of slipperiness
Based on JIS-K7125, the dynamic friction coefficient of the surface-treated synthetic polymer film was measured and evaluated according to the following criteria.
Evaluation criteria
A: Dynamic friction coefficient is less than 0.25
○: Dynamic friction coefficient is 0.25 or more and less than 0.30
Δ: Dynamic friction coefficient is 0.30 or more and less than 0.35
X: Dynamic friction coefficient is 0.35 or more
[0063]
・ Transparency evaluation
The surface-treated synthetic polymer film was observed with the naked eye in comparison with the untreated synthetic polymer film, and evaluated according to the following criteria.
Evaluation criteria
A: Same transparency as untreated synthetic polymer film
○: Slightly turbid than untreated synthetic polymer film
Δ: Much more turbid than untreated synthetic polymer film
×: Remarkably turbid than untreated synthetic polymer film
[0064]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
[Table 7]
[Table 8]
【The invention's effect】
As is apparent from the above, the present invention described above provides excellent antistatic properties and antifogging properties to the synthetic polymer film without impairing the original physical properties of the synthetic polymer film, and at the same time excellent slipperiness. Is effective.
Claims (4)
ビニル共重合体：下記の式１で示されるビニル単量体から形成された構成単位を１０〜６０重量％、下記の式２で示されるビニル単量体から形成された構成単位を１０〜４０重量％及び下記の式３で示されるビニル単量体から形成された構成単位を１０〜７０重量％（合計１００重量％）の割合で有する数平均分子量２００００〜９００００のビニル共重合体
【式１】
Ｒ１，Ｒ５，Ｒ７：水素原子又はメチル基
Ｒ２：炭素数１〜４のアルキレン基
Ｒ３，Ｒ４：炭素数１〜６のアルキル基
Ｒ６：炭素数１〜４のモノヒドロキシアルキル基又は炭素数２〜４のジヒドロキシアルキル基
Ｒ８：メチル基又はエチル基）
滑剤：炭素数１６〜１８の脂肪族カルボン酸アルカリ金属塩、炭素数１６〜１８の脂肪族カルボン酸アルカリ土類金属塩及び粒子径が０．１〜５０μｍの範囲内にあり且つ平均粒子径が１０μｍ以下の球状粒子であるシリカ粒子から選ばれる一つ又は二つ以上A synthetic polymer comprising the following vinyl copolymer and the following lubricant, and containing the vinyl copolymer / the lubricant in a ratio of 50/50 to 80/20 (weight ratio) Surface treatment agent for film.
Vinyl copolymer: 10 to 60% by weight of a structural unit formed from a vinyl monomer represented by the following formula 1, and 10 to 40 structural units formed from a vinyl monomer represented by the following formula 2. A vinyl copolymer having a number average molecular weight of 20,000 to 90,000 having 10% to 70% by weight (100% by weight in total) of structural units formed from vinyl monomers represented by weight% and the following formula 3 ]
R 1 , R 5 , R 7 : hydrogen atom or methyl group R 2 : alkylene group having 1 to 4 carbon atoms R 3 and R 4 : alkyl group having 1 to 6 carbon atoms R 6 : monohydroxy having 1 to 4 carbon atoms An alkyl group or a dihydroxyalkyl group having 2 to 4 carbon atoms R 8 : a methyl group or an ethyl group)
Lubricant: Alkaline metal salt of aliphatic carboxylic acid having 16 to 18 carbon atoms, Alkaline metal salt of aliphatic carboxylic acid having 16 to 18 carbon atoms and particle diameter in the range of 0.1 to 50 μm and average particle diameter One or more selected from silica particles that are spherical particles of 10 μm or less
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| JP7358030B2 (en) * | 2018-01-31 | 2023-10-10 | 住友ゴム工業株式会社 | Hydrophilic base material |
| JP6533326B1 (en) | 2018-07-25 | 2019-06-19 | 竹本油脂株式会社 | Modifier for resin sheet for molding into a molded body, resin sheet for a resin molded body and resin molded body |
| CN109786620B (en) * | 2018-12-13 | 2022-03-15 | 武汉中兴创新材料技术有限公司 | Coating film and preparation method and application thereof |
| JP6871653B1 (en) | 2020-03-05 | 2021-05-12 | 竹本油脂株式会社 | Method for manufacturing resin sheet modifiers, surface-modified resin sheets and molded products |
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| JPS5927769B2 (en) * | 1975-03-13 | 1984-07-07 | 三菱油化株式会社 | Anti-dielectric agent |
| JPS574675B2 (en) * | 1974-05-07 | 1982-01-27 | ||
| JPS60112421A (en) * | 1983-11-25 | 1985-06-18 | Mitsubishi Petrochem Co Ltd | Thermoforming method of resin sheet |
| JPS612740A (en) * | 1984-06-15 | 1986-01-08 | Teijin Ltd | Antistatic film |
| GB8432488D0 (en) * | 1984-12-21 | 1985-02-06 | Ici Plc | Antistatic polymeric articles |
| JPH0489874A (en) * | 1990-08-02 | 1992-03-24 | Hitachi Maxell Ltd | Silicone coating composition |
| JPH107822A (en) * | 1996-06-20 | 1998-01-13 | Oji Yuka Synthetic Paper Co Ltd | Thermoplastic resin film having good printability |
| JP3946285B2 (en) * | 1996-07-08 | 2007-07-18 | 株式会社ユポ・コーポレーション | Printing paper for electrophotography |
| JPH10110051A (en) * | 1996-10-04 | 1998-04-28 | Oji Yuka Synthetic Paper Co Ltd | Thermoplastic resin film having good printability |
| JPH10315373A (en) * | 1997-05-22 | 1998-12-02 | Teijin Ltd | Mold release film |
-
2003
- 2003-04-30 JP JP2003124892A patent/JP4565608B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002012858A (en) * | 2000-06-27 | 2002-01-15 | Toyobo Co Ltd | Composition for antistatic agent and biaxially oriented film coated with the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8846167B2 (en) | 2012-11-09 | 2014-09-30 | Fuji Xerox Co., Ltd. | Image transfer sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004244605A (en) | 2004-09-02 |
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