JP4851045B2 - Hydroxyl group-containing acrylic polymer, thermoplastic resin composition, thermoplastic resin film, laminate, building material - Google Patents

Description

【０１１５】

【０１１６】
（ハ）
脱イオン水 １０部
ソジウムホルムアルデヒドスルホキシレート ０．１５部。
【０１１７】
（ニ）
ＭＭＡ ５７．０部
ＭＡ ３．０部
ｎＯＭ ０．２部
ｔＢＨ ０．１部。
【０１１８】
上記の様にして得たゴム含有重合体（Ａ−１）５６部と、熱可塑性重合体（Ａ−２）であるＭＭＡ／ＭＡ共重合体（ＭＭＡ／ＭＡ＝９９／１、還元粘度０．０６Ｌ／ｇ）４４部とを混合して、アクリル樹脂組成物（Ａ）を得た。
【０１１９】
＜製造例２＞アクリル樹脂組成物（Ｂ）
冷却器付き重合容器内にイオン交換水２５０部、スルホコハク酸のエステルソーダ塩２部、ソジウムホルムアルデヒドスルホキシレート０．０５部を仕込み、窒素下で撹拌後、ＭＭＡ１．６部、ＢＡ８部、１，３ＢＤ０．４部、ＡＭＡ０．１部およびクメンハイドロパーオキサイド０．０４部からなる混合物を仕込んだ。７０℃に昇温後、６０分間反応を継続させ最内層重合体（Ｂ−ａ）の重合を完結した。その後、架橋弾性重合体（Ｂ−ｂ）を形成する為のＭＭＡ１．５部、ＢＡ２２．５部、１，３ＢＤ１．０部、ＡＭＡ０．２５部およびクメンハイドロパーオキサイド０．０５部からなる混合物を６０分間で添加し、重合して、最内層重合体（Ｂ−ａ）と架橋弾性重合体（Ｂ−ｂ）からなる２層架橋ゴム弾性体を得た。
【０１２０】
続いて、この２層架橋ゴム弾性体の存在下に、ＭＭＡ５部、ＢＡ５部およびＡＭＡ０．１部の混合物を反応させて、中間層（Ｂ−ｄ）を形成し、最後に、ＭＭＡ５２．２５部とＢＡ２．７５部からなる混合物を反応させて最外層重合体（Ｂ−ｃ）を形成し、多層構造重合体のラテックスを得た。
【０１２１】
この多層構造重合体の粒子径は０．１２μｍであった。得られた重合体ラテックスを、目開き７５μｍのフィルターで濾過した後、重合体１００部に対して５部の酢酸カルシウムを用いて塩析し、洗浄し、乾燥してアクリル樹脂組成物（Ｂ）を得た。
【０１２２】
＜製造例３＞熱可塑性重合体（Ｃ）
反応容器に窒素置換したイオン交換水２００部を仕込み、乳化剤オレイン酸カリウム１部、過硫酸カリウム０．３部を仕込んだ。続いてＭＭＡ４０部、ＢＡ１０部、ｎＯＭ０．００５部を仕込み、窒素雰囲気下６５℃にて３時間撹拌し、重合を完結させた。引き続いて、ＭＭＡ４８部およびＢＡ２部からなる単量体混合物を２時間にわたり滴下し、滴下終了後２時間保持し、重合を完結させた。得られたラテックスを０．２５％硫酸水溶液に添加し、重合体を酸凝析し、その後脱水、水洗、乾燥し、粉体状で重合体を回収した。得られた共重合体の還元粘度η_sp／ｃは０．３８Ｌ／ｇであった。
【０１２３】
＜実施例１＞水酸基含有アクリル系重合体（ＩＩ−１）、熱可塑性樹脂組成物（ＩＩＩａ−１）
撹拌機、還流冷却器、窒素ガス導入口等の付いた反応容器に、次の混合物を仕込んだ。
【０１２４】

【０１２５】
容器内を十分に窒素ガスで置換し、その後撹拌しながら７５℃まで加熱し、窒素ガス気流中で重合を進めた。２時間後に９０℃に昇温して更に４５分保持して重合を完了した。得られた重合体ビーズを、脱水、乾燥して水酸基含有アクリル系重合体（ＩＩ−１）を得た。この水酸基含有アクリル系重合体（ＩＩ−１）の固有粘度は、０．０７６Ｌ／ｇであった。また、ガラス転移温度は９３℃であった。
【０１２６】
次に、アクリル樹脂組成物（Ａ）１００部に対し水酸基含有アクリル系重合体（ＩＩ−１）１０部を加え、さらに熱可塑性重合体（Ｃ）１部、紫外線吸収剤であるチヌビン１５７７（チバガイギー社製）１部を加えたものをヘンシェルミキサーを用いて混合した。次いで、４０ｍｍφのスクリュー型２軸押出機（Ｌ／Ｄ＝２６）を用いて、シリンダー温度２００℃〜２６０℃、ダイ温度２５０℃の条件下で溶融混練しペレット化して、熱可塑性樹脂組成物（ＩＩＩａ−１）のペレットを得た。
【０１２７】
このペレットを８０℃で一昼夜乾燥し、３００ｍｍＴダイを取り付け、４００メッシュのスクリーンメッシュを設けた４０ｍｍφのノンベントスクリュー型押出機（Ｌ／Ｄ＝２６）を用いて、シリンダー温度２００℃〜２４０℃、Ｔダイ温度２５０℃の条件下で、Ｔダイを介して溶融押出を行った。押出した樹脂は、７５℃に温調した冷却用の鏡面ロール（クロムメッキ加工した表面粗度が０．２Ｓのロール）を用いて、厚さ５０μｍのアクリル樹脂フィルムを製膜した。
【０１２８】
次いで、２４０℃でＡＢＳ樹脂（三菱レイヨン製ダイヤペットＡＢＳ３００１Ｍ）を押し出し成形して２ｍｍシート状に成形する際に、溶融ＡＢＳ樹脂と冷却ロールの間に前出のアクリル樹脂フィルムを導入することにより押し出しラミネーションして積層体を作製し評価した。
【０１２９】
＜実施例２＞熱可塑性樹脂組成物（ＩＩＩｂ−１）
アクリル樹脂組成物（Ａ）１００部の代わりに、アクリル樹脂組成物（Ｂ）１００部を用いたこと以外は、熱可塑性樹脂組成物（ＩＩＩａ−１）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−１）を作製し評価した。
【０１３０】
＜実施例３＞水酸基含有アクリル系重合体（ＩＩ−２）、熱可塑性樹脂組成物（ＩＩＩｂ−２）
モノマー組成をＭＭＡ／ＭＡ／ＨＥＭＡ＝７９／１／２０の代わりに、ＭＭＡ／ＭＡ／ＨＥＭＡ＝８９／１／１０に変更し、更にｎ−オクチルメルカプタン量を０．１１部に変更した以外は、水酸基含有アクリル系重合体（ＩＩ−１）と同様にして、水酸基含有アクリル系重合体（ＩＩ−２）を作製した。固有粘度は０．０９Ｌ／ｇであり、ガラス転移温度は９８℃であった。この水酸基含有アクリル系重合体（ＩＩ−２）を用いた以外は、熱可塑性樹脂組成物（ＩＩＩｂ−１）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−２）を作製し評価した。
【０１３１】
＜比較例１＞水酸基含有アクリル系重合体（ＩＩ−３）、熱可塑性樹脂組成物（ＩＩＩｂ−３）
モノマー組成をＭＭＡ／ＭＡ／ＨＥＭＡ＝７９／１／２０の代わりに、ＭＭＡ／ＭＡ／ＨＥＭＡ＝６９／１／３０に変更し、更にｎ−オクチルメルカプタン量を０．１５部に変更した以外は、水酸基含有アクリル系重合体（ＩＩ−１）と同様にして、水酸基含有アクリル系重合体（ＩＩ−３）を作製した。固有粘度は０．０７２Ｌ／ｇであり、ガラス転移温度は８７℃であった。この水酸基含有アクリル系重合体（ＩＩ−３）を用いた以外は、熱可塑性樹脂組成物（ＩＩＩｂ−１）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−３）を作製し評価した。
【０１３２】
＜実施例４＞水酸基含有アクリル系重合体（ＩＩ−４）、熱可塑性樹脂組成物（ＩＩＩｂ−４）
モノマー組成をＭＭＡ／ＭＡ／ＨＥＭＡ＝７９／１／２０の代わりに、ＭＭＡ／ＭＡ／ＨＥＭＡ＝９４／１／５に変更し、更にｎ−オクチルメルカプタン量を０．１１部に変更した以外は、水酸基含有アクリル系重合体（ＩＩ−１）と同様にして、水酸基含有アクリル系重合体（ＩＩ−４）を作製した。固有粘度は０．０８９Ｌ／ｇであり、ガラス転移温度は１０１℃であった。この水酸基含有アクリル系重合体（ＩＩ−４）を用いた以外は、熱可塑性樹脂組成物（ＩＩＩｂ−１）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−４）を作製し評価した。
【０１３３】
＜比較例２＞水酸基含有アクリル系重合体（ＩＩ−５）、熱可塑性樹脂組成物（ＩＩＩｂ−５）
モノマー組成をＭＭＡ／ＭＡ／ＨＥＭＡ＝７９／１／２０の代わりに、ＭＭＡ／ＭＡ／ＨＥＭＡ＝７５／５／２０に変更した以外は、水酸基含有アクリル系重合体（ＩＩ−１）と同様にして、水酸基含有アクリル系重合体（ＩＩ−５）を作製した。固有粘度は０．０７５Ｌ／ｇであり、ガラス転移温度は８８℃であった。この水酸基含有アクリル系重合体（ＩＩ−５）を用いた以外は、熱可塑性樹脂組成物（ＩＩＩｂ−１）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−５）を作製し評価した。
【０１３４】
＜比較例３＞水酸基含有アクリル系重合体（ＩＩ−６）、熱可塑性樹脂組成物（ＩＩＩｂ−６）
モノマー組成をＭＭＡ／ＭＡ／ＨＥＭＡ＝７９／１／２０の代わりに、ＭＭＡ／ＭＡ／ＨＥＭＡ＝７０／１０／２０に変更した以外は、水酸基含有アクリル系重合体（ＩＩ−１）と同様にして、水酸基含有アクリル系重合体（ＩＩ−６）を作製した。固有粘度は０．０７３Ｌ／ｇであり、ガラス転移温度は８２℃であった。この水酸基含有アクリル系重合体（ＩＩ−６）を用いた以外は、熱可塑性樹脂組成物（ＩＩＩｂ−１）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−６）を作製し評価した。
【０１３５】
＜実施例５＞熱可塑性樹脂組成物（ＩＩＩｂ−７）
アクリル樹脂組成物（Ｂ）１００部に対して、水酸基含有アクリル系重合体（ＩＩ−２）の添加量を２０部に変更する以外は、熱可塑性樹脂組成物（ＩＩＩｂ−２）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−７）を作製し評価した。
【０１３６】
＜実施例６＞熱可塑性樹脂組成物（ＩＩＩｂ−８）
アクリル樹脂組成物（Ｂ）１００部に対して、水酸基含有アクリル系重合体（ＩＩ−２）の添加量を３０部に変更する以外は、熱可塑性樹脂組成物（ＩＩＩｂ−２）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−８）を作製し評価した。
【０１３７】
＜実施例７＞水酸基含有アクリル系重合体（ＩＩ−７）、熱可塑性樹脂組成物（ＩＩＩｂ−９）
ｎ−オクチルメルカプタン量を０．０９部に変更した以外は、水酸基含有アクリル系重合体（ＩＩ−１）と同様にして水酸基含有アクリル系重合体（ＩＩ−７）調製した。固有粘度は０．１１Ｌ／ｇであり、ガラス転移温度は９３℃であった。この水酸基含有アクリル系重合体（ＩＩ−７）を用いた以外は、熱可塑性樹脂組成物（ＩＩＩｂ−１）の場合と同様に熱可塑性樹脂組成物（ＩＩＩｂ−９）を作製し評価した。
【０１３８】
＜実施例８＞熱可塑性樹脂組成物（ＩＩＩ−１０）
ポリカーボネート樹脂（商品名：レキサンＭＬ５５００、ゼネラルエレクトリック社製）１００質量部に、水酸基含有アクリル系重合体（ＩＩ−１）１０質量部をヘンシェルミキサーで混合する以外は、熱可塑性樹脂組成物（ＩＩＩａ−１）と同様に熱可塑性樹脂組成物（ＩＩＩ−１０）を作製し評価した。
【０１３９】
＜実施例９＞熱可塑性樹脂組成物（ＩＩＩ−１１）
塩化ビニル樹脂（Ｐ＝１１００）７０質量部、安定剤（ジブチルスズマレエート）２質量部、耐衝撃助剤（三菱レイヨン社製、商品名：メタブレンＣ−１０２）２５質量部、加工助剤（三菱レイヨン社製、商品名：メタブレンＰ−５５１）１質量部、滑材（ブチルステアリレート）１質量部、カーボンブラック０．５質量部、水酸基含有アクリル系重合体（ＩＩ−１）１０質量部をヘンシェルミキサーで混合する以外は、熱可塑性樹脂組成物（ＩＩＩａ−１）と同様に熱可塑性樹脂組成物（ＩＩＩ−１１）を作製し、１６０℃の条件下で製膜する以外は熱可塑性樹脂組成物（ＩＩＩａ−１）と同様に評価した。
【０１４０】
＜実施例１０＞熱可塑性樹脂組成物（ＩＩＩ−１２）
ＡＳＡ樹脂（三菱レイヨン社製、商品名：ダイヤラックＥ６１０黒着色品）１００質量部に対し、水酸基含有アクリル系重合体（ＩＩ−１）１０質量部をヘンシェルミキサーで混合する以外は、熱可塑性樹脂組成物（ＩＩＩａ−１）と同様に熱可塑性樹脂組成物（ＩＩＩ−１２）を作製し評価した。
【０１４１】
＜比較例４＞水酸基含有アクリル系重合体（ＩＩ−８）、熱可塑性樹脂組成物（ＩＩＩｂ−１３）
モノマー組成をＭＭＡ／ＭＡ／ＨＥＭＡ＝８９／１／１０の代わりに、ＭＭＡ／ＭＡ／ＨＥＭＡ＝９８．５／１／０．５に変更した以外は、水酸基含有アクリル系重合体（ＩＩ−２）と同様にして、水酸基含有アクリル系重合体（ＩＩ−８）を作製した。固有粘度は０．０９１Ｌ／ｇであり、ガラス転移温度は１０３℃であった。この水酸基含有アクリル系重合体（ＩＩ−８）を用いた以外は、熱可塑性樹脂組成物（ＩＩＩｂ−２）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−１３）を作製し評価した。
【０１４２】
＜比較例５＞水酸基含有アクリル系重合体（ＩＩ−９）、熱可塑性樹脂組成物（ＩＩＩｂ−１４）
モノマー組成をＭＭＡ／ＭＡ／ＨＥＭＡ＝７９／１／２０の代わりに、ＭＭＡ／ＭＡ／ＨＥＭＡ＝４９／１／５０に変更し、更にｎ−オクチルメルカプタン量を０．１９部に変更した以外は、水酸基含有アクリル系重合体（ＩＩ−１）と同様にして、水酸基含有アクリル系重合体（ＩＩ−９）を作製した。固有粘度は０．０６Ｌ／ｇであり、ガラス転移温度は７７℃であった。この水酸基含有アクリル系重合体（ＩＩ−９）を用いた以外は、熱可塑性樹脂組成物（ＩＩＩｂ−１）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−１４）を作製し評価した。
【０１４３】
＜比較例６＞水酸基含有アクリル系重合体（ＩＩ−１０）、熱可塑性樹脂組成物（ＩＩＩｂ−１５）
モノマー組成をＭＭＡ／ＭＡ／ＨＥＭＡ＝７９／１／２０の代わりに、ＭＭＡ／ＭＡ／ＨＥＭＡ＝６０／２０／２０に変更し、更にｎ−オクチルメルカプタン量を０．０８部に変更した以外は、水酸基含有アクリル系重合体（ＩＩ−１）と同様にして、水酸基含有アクリル系重合体（ＩＩ−１０）を作製した。固有粘度は０．１１Ｌ／ｇであり、ガラス転移温度は７１℃であった。この水酸基含有アクリル系重合体（ＩＩ−１０）を用いた以外は、熱可塑性樹脂組成物（ＩＩＩｂ−１）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−１５）を作製し評価した。
【０１４４】
＜比較例７＞水酸基含有アクリル系重合体（ＩＩ−１１）、熱可塑性樹脂組成物（ＩＩＩａ−１６）
モノマー組成をＭＭＡ／ＭＡ／ＨＥＭＡ＝７９／１／２０の代わりに、ＭＭＡ／ＭＡ／ＨＥＭＡ＝６０／１０／３０に変更し、更にｎ−オクチルメルカプタン量を０．１５部に変更した以外は、水酸基含有アクリル系重合体（ＩＩ−１）と同様にして、水酸基含有アクリル系重合体（ＩＩ−１１）を作製した。固有粘度は０．０６９Ｌ／ｇであり、ガラス転移温度は７７℃であった。この水酸基含有アクリル系重合体（ＩＩ−１１）を用いた以外は、熱可塑性樹脂組成物（ＩＩＩａ−１）と同様にして熱可塑性樹脂組成物（ＩＩＩａ−１６）を作製し評価した。
【０１４５】
＜比較例８＞熱可塑性樹脂組成物（ＩＩＩｂ−１６）
アクリル樹脂組成物（Ａ）１００部の代わりに、アクリル樹脂組成物（Ｂ）１００部を用いたこと以外は、熱可塑性樹脂組成物（ＩＩＩａ−１６）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−１６）を作製し評価した。
【０１４６】
＜参考例１＞熱可塑性樹脂組成物（ＩＩＩｂ−１７）
アクリル樹脂組成物（Ｂ）１００部に対して、水酸基含有アクリル系重合体（ＩＩ−１）の添加量を０．５部に変更する以外は、熱可塑性樹脂組成物（ＩＩＩｂ−１）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−１７）を作製し評価した。
【０１４７】
＜参考例２＞熱可塑性樹脂組成物（ＩＩＩｂ−１８）
アクリル樹脂組成物（Ｂ）１００部に対して、水酸基含有アクリル系重合体（ＩＩ−１）の添加量を５０部に変更する以外は、熱可塑性樹脂組成物（ＩＩＩｂ−１）と同様にして熱可塑性樹脂組成物（ＩＩＩｂ−１８）を作製し評価した。
【０１４８】
＜比較例９＞熱可塑性樹脂組成物（ＩＩＩ−１９）
水酸基含有アクリル系重合体（ＩＩ−１）の代わりに水酸基含有アクリル系重合体（ＩＩ−１０）を用いる以外は、熱可塑性樹脂組成物（ＩＩＩ−１０）と同様に熱可塑性樹脂組成物（ＩＩＩ−１９）を作製し評価した。
【０１４９】
＜比較例１０＞熱可塑性樹脂組成物（ＩＩＩ−２０）
水酸基含有アクリル系重合体（ＩＩ−１）の代わりに水酸基含有アクリル系重合体（ＩＩ−１０）を用いる以外は、熱可塑性樹脂組成物（ＩＩＩ−１１）と同様に熱可塑性樹脂組成物（ＩＩＩ−２０）を作製し評価した。
【０１５０】
＜比較例１１＞熱可塑性樹脂組成物（ＩＩＩ−２１）
水酸基含有アクリル系重合体（ＩＩ−１）の代わりに水酸基含有アクリル系重合体（ＩＩ−１０）を用いる以外は、熱可塑性樹脂組成物（ＩＩＩ−１２）と同様に熱可塑性樹脂組成物（ＩＩＩ−２１）を作製し評価した。
【０１５１】
以上の組成を表１にまとめた。
【０１５２】
【表１】

【０１５３】
評価結果を表２にまとめた。
【０１５４】
【表２】

【０１５５】
但し、表２において、熱可塑性樹脂組成物（ＩＩＩ−１１）、（ＩＩＩ−１２）、（ＩＩＩ−２０）及び（ＩＩＩ−２１）の耐水白化性に関する評価は、グレースケールによるものである。
【０１５６】
以上より、本発明の水酸基含有アクリル系重合体を艶消し剤として使用することにより、十分な耐水白化性を有する優れた艶消し外観を実現できることが分かった。
【０１５７】
【発明の効果】
以上説明したように、炭素数１〜８のアルキル基を有する（メタ）アクリル酸ヒドロキシアルキルエステル１〜２０質量部、炭素数１〜１３のアルキル基を有するメタクリル酸アルキルエステル７９〜９９質量部およびアクリル酸アルキルエステル１０質量部未満を含む合計１００質量部の単量体組成物を重合して得られ、ガラス転移温度が９３〜１２０℃である水酸基含有アクリル系重合体を、艶消し剤として熱可塑性樹脂に添加すれば、良好な艶消し外観を有し、かつ屋外用途に適用可能な耐水白化性を有する熱可塑性樹脂組成物を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a matting agent, and relates to a thermoplastic resin composition and a thermoplastic resin film excellent in water whitening resistance that are useful for decorating the surface of a substrate and have a good matte appearance, and in particular, an acrylic resin film and the film. It is related with the laminated body which has on the surface.
[0002]
[Prior art]
Laminates in which a thermoplastic resin layer is laminated on the surface of various substrates are used as industrial members having various functions by imparting the features of the thermoplastic resin to be laminated to the surface of the substrate.
[0003]
In particular, acrylic resin films take advantage of excellent weather resistance, transparency, and processability, and can be applied to resin substrates such as vinyl chloride resin, ABS resin, polycarbonate resin, polyester resin, and polyolefin resin, and to the surface of metal, wood, cloth, etc. By bonding, it is applied to the protection of substrates and the provision of design properties.
[0004]
Indoor use of a laminate having an acrylic resin film bonded to the surface includes a housing for home appliances, wallpaper, a decorative board, and an interior material for automobiles. Moreover, there are exterior building materials such as roofs such as carports and verandas, entrance doors, window frames and signboards as outdoor applications.
[0005]
On the other hand, it is possible to give matteness to the thermoplastic resin layer laminated on the base material, and to express a sense of quality, calmness, or decorate the metallic tone, especially for building materials such as wallpaper, entrance doors, window frames, etc. It is required for applications such as vehicle interior parts.
[0006]
In addition, when using a laminate with laminated thermoplastic resin layers for outdoor applications such as entrance doors, resin sashes, window frames, outer wall materials, etc., it is necessary that the appearance change with respect to rain be small, and in particular the surface of the laminate must have water. In the attached state, it is important that less whitening occurs when the temperature of the laminate surface rises due to direct sunlight.
[0007]
The above-mentioned water whitening resistance is particularly affected by the tensile stress remaining in the thermoplastic resin layer on the surface of the laminate or the tensile stress remaining when the laminate is bent or stretched, as well as direct sunlight when adhering to water. Considering the temperature of the rising laminate surface, water whitening resistance when exposed to 100 ° C. water under a tensile stress of 0.02 MPa becomes important.
[0008]
When the whitening change of the thermoplastic resin layer is 25% (LabW) or less when the water whitening test is performed under such a tensile stress, a laminate obtained by laminating the thermoplastic resin layer is, for example, an outer wall material, a resin sash, etc. Can be used for outdoor building materials.
[0009]
On the other hand, as a conventional technique, JP-A-7-238202 discloses a laminate using an acrylic resin composition having excellent matting properties and a film.
[0010]
Japanese Patent Application Laid-Open No. 9-235440 discloses a matte acrylic resin film having improved water whitening resistance and a laminate using the film.
[0011]
Japanese Patent Application Laid-Open No. 11-335511 discloses a matte acrylic resin film excellent in bending whitening, impact resistance, solvent resistance, plasticizer migration, and processability.
[0012]
Japanese Patent Application Laid-Open No. 11-80487 discloses an acrylic resin film having good processability.
[0013]
JP-A-7-316374 and JP-A-7-316389 disclose thermoplastic resin compositions having excellent matting properties.
[0014]
[Problems to be solved by the invention]
However, JP-A-7-316374, JP-A-7-316389, and JP-A-7-238202 do not describe in detail the water whitening resistance of the thermoplastic resin composition and the acrylic resin. Furthermore, in the thermoplastic resin compositions described in these publications, when an acrylic resin was produced in a film shape and subjected to a water whitening test under tensile stress, the difference in whiteness before and after the test was 25% ( Some of them greatly exceeded LabW). In this way, the resin composition inferior in water whitening resistance under tensile stress is used as a covering material for doors, window frame materials, outer wall materials, shutters, and other semi-exterior applications. It was difficult and the industrial utility value was low.
[0015]
Moreover, when the colored thermoplastic resin composition was used, some samples after the test turned white. That is, the colored thermoplastic resin composition is also excellent in matteness, but has insufficient water whitening resistance. For example, exterior materials such as door materials, window frame materials, outer wall materials, shutters, and semi-exterior applications It was difficult to use as a coating material, and the industrial utility value was low.
[0016]
The acrylic resin film disclosed in JP-A-9-235440 is satisfactory in terms of water whitening resistance, but may have insufficient matting properties. That is, such an acrylic resin film has excellent water whitening resistance and can be used as a coating material for exterior and semi-exterior applications, but lacks matte properties when processed into a molded product. Lack of feeling and industrial utility value was low.
[0017]
Japanese Patent Application Laid-Open No. 11-335511 does not describe in detail the water whitening resistance of a matte acrylic resin film. Further, the matte property may be insufficient, and the industrial utility value may be low due to lack of luxury when processed into a molded product.
[0018]
Regarding the acrylic resin film having good processability described in JP-A-11-80487, although matte and water whitening resistance are taken into consideration, a film having excellent water whitening resistance may have poor matte properties. On the contrary, a film having excellent matting properties may have poor water whitening resistance, and it may be difficult to obtain an acrylic resin film in which both performances are highly balanced. As a result, when used for exterior materials such as door materials, window frame materials, outer wall materials, shutters, and coating materials for semi-exterior applications, both water whitening resistance and matte properties after molding cannot be achieved. Value was low.
[0019]
In view of the circumstances as described above, a matting agent capable of realizing a thermoplastic resin composition having a good matte appearance and having water whitening resistance applicable to outdoor use. Hydroxyl group-containing acrylic polymer useful as , Such matting agent Hydroxyl-containing acrylic polymer as A thermoplastic resin composition, a thermoplastic resin film, this the film Is made up of stacked Laminate and Building materials It is an object of the present invention to provide
[0020]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors include, as a matting agent, a hydroxyl group-containing acrylic polymer that is polymerized from a specific type and amount of monomer and has a specific glass transition temperature. The present inventors have found that the thermoplastic resin composition has not only matte properties but also very good water whitening resistance, and has completed the present invention.
[0021]
That is, according to the present invention, 1 to 20 parts by mass of a (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, 79 to 99 parts by mass of a methacrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms. and Acrylic acid alkyl ester Obtained by polymerizing a total of 100 parts by weight of the monomer composition including less than 10 parts by weight, the glass transition temperature is 93 A hydroxyl group-containing acrylic polymer having a temperature of ˜120 ° C. is provided.
[0022]
Also, Acrylic resin, polycarbonate resin, vinyl chloride resin or A SA Made of resin Thermoplastic resin (I) [However, it contains 50 to 100 parts by mass of the following hydroxyl group-containing acrylic polymer (II) and 50 to 100 parts by mass of methyl methacrylate and other vinyl monomers copolymerizable therewith if necessary. A thermoplastic obtained by polymerizing a total of 100 parts by mass of the monomer composition, and having a reduced viscosity of the polymer (0.1 g of the polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) exceeding 0.2 L / g The polymer (C) is excluded. ] 100 parts by mass;
1 to 20 parts by mass of a (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, 79 to 99 parts by mass of an alkyl methacrylate having 1 to 13 carbon atoms and 10 parts by mass of an alkyl alkyl ester 1 to 40 parts by mass of a hydroxyl group-containing acrylic polymer (II) obtained by polymerizing a total of 100 parts by mass of the monomer composition including less than 100 parts and having a glass transition temperature of 93 to 120 ° C.
A thermoplastic resin composition (III) is provided.
It is.
[0023]
This thermoplastic resin composition (III) is suitable for a thermoplastic resin film, and a laminate can be prepared by laminating this thermoplastic resin film, and this laminate is suitable as a building material.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0025]
Examples of the (meth) acrylic acid hydroxyalkyl ester having a C1-C8 alkyl group used for the hydroxyl group-containing acrylic polymer (II) include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and methacrylic acid. Examples include 2,3-dihydroxypropyl, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and the like. Of these, 2-hydroxyethyl methacrylate is preferable.
[0026]
The amount of these (meth) acrylic acid hydroxyalkyl esters used is 1 part by mass or more, preferably 5 parts by mass or more, and more preferably 10 parts by mass or more in order to achieve a sufficient matting effect. On the other hand, in order to realize sufficient water whitening resistance, 20 parts by mass or less Is .
[0027]
As the alkyl methacrylate having an alkyl group having 1 to 13 carbon atoms used for the hydroxyl group-containing acrylic polymer (II), for example, lower methacrylate alkyl esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate are preferable. Of these, methyl methacrylate is most suitable. The amount of these methacrylic acid alkyl esters used is 79 parts by mass or more. And On the other hand, it is 99 parts by mass or less, and 95 parts by mass or less is more preferable.
[0028]
Furthermore, it is preferable to use together the alkyl acrylate ester which has a C1-C8 alkyl group as a monomer of a hydroxyl-containing acrylic polymer (II). Specifically, lower acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate are preferable. By using these alkyl acrylates, the thermal decomposition resistance of the film is improved.
[0029]
The amount of the alkyl acrylate used is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and more preferably 2 parts by mass or less with respect to 100 parts by mass of the monomer composition in order to improve water whitening resistance. Is more preferable. Moreover, 0.1 mass part or more is preferable from a thermal decomposable viewpoint.
[0030]
Furthermore, at least one of the above-mentioned (meth) acrylic acid hydroxyalkyl ester and other vinyl monomer copolymerizable with methacrylic acid alkyl ester is added to the monomer composition of the hydroxyl group-containing acrylic polymer (II). It can also be added.
[0031]
Specifically, aromatic vinyl compounds such as styrene, vinyl cyanide monomers such as acrylonitrile, unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, N-cyclohexylmaleimide and the like Is mentioned. In particular, the use of unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, and N-cyclohexylmaleimide can increase the glass transition temperature of the hydroxyl group-containing acrylic polymer (II). Further, the water whitening resistance is further improved. The amount of these other copolymerizable vinyl monomers used is in the range of 50 parts by mass or less with respect to 100 parts by mass of the monomer composition.
[0032]
The glass transition temperature of the hydroxyl group-containing acrylic polymer (II) is: 93 It must be ˜120 ° C. In particular, from the viewpoint of water whitening resistance, the glass transition temperature is 93 It is necessary that the temperature is not lower than ° C.
[0033]
Further, the intrinsic viscosity as an index of the molecular weight of the hydroxyl group-containing acrylic polymer (II) is preferably 0.05 L / g or more, more preferably 0.06 L / g or more from the viewpoint of matte appearance and appearance. 0.3 L / g or less is preferable, and 0.15 L / g or less is more preferable.
[0034]
In order to adjust the molecular weight, it is preferable to use a polymerization regulator such as mercaptan. As the mercaptan, for example, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and the like can be used. However, it is not limited to these, and various conventionally known mercaptans can be used.
[0035]
Although the manufacturing method of hydroxyl-containing acrylic polymer (II) is not specifically limited, Suspension polymerization, emulsion polymerization, etc. are preferable. As the initiator for suspension polymerization, various conventionally known initiators can be used, and specific examples include organic peroxides and azo compounds. In addition, various conventionally known suspension stabilizers can be used. Specifically, the organic colloidal polymer substance, the inorganic colloidal polymer substance, the inorganic fine particles, and the surfactant and the surfactant are used. A combination etc. are mentioned. Suspension polymerization is usually carried out by suspending monomers with an initiator in the presence of a suspension stabilizer. In addition, suspension polymerization can be performed by using a polymer soluble in the monomer dissolved in the monomer.
[0036]
The hydroxyl group-containing acrylic polymer (II) produced as described above is suitable as a matting agent for thermoplastic resins, especially acrylic resins, and has a good matte appearance and water whitening resistance applicable to outdoor use. A particularly good acrylic resin film can be realized.
[0037]
When mix | blending a thermoplastic polymer (I) with a hydroxyl-containing acrylic polymer (II) as a matting agent, the compounding quantity with respect to 100 mass parts of thermoplastic resins (I) is 1-40 mass parts. A sufficient matting effect is exhibited with an addition amount of 1 part by mass or more. Furthermore, it is preferable to add 5 parts by mass or more in order to obtain good matting properties. Further, in order to obtain good water whitening resistance, it is necessary to use 40 parts by mass or less, preferably 20 parts by mass, more preferably 10 parts by mass or less.
[0038]
As thermoplastic resin (I), acrylic resin, polycarbonate resin, vinyl chloride resin Or ASA tree Fat Use . Of these, acrylic resins are preferred for industrially utilizing a good matte appearance and water whitening resistance.
[0039]
Various acrylic resins can be used as the acrylic resin. However, from the viewpoint of film forming property, it is preferable to use the acrylic resin composition (A) described below or the acrylic resin composition (B) containing the multilayer structure polymer described below.
[0040]
First, the acrylic resin composition (A) will be described. The acrylic resin composition (A) is a thermoplastic polymer (A-2) 0. 5 parts by weight containing 5.5 to 99.9 parts by mass of a rubber-containing polymer (A-1) and a methacrylic acid alkyl ester. It is a resin composition containing 1-94.5 mass parts and [total 100 mass parts of a component (A-1) and a component (A-2)].
[0041]
The rubber-containing polymer (A-1) used for the acrylic resin composition (A) is an elastic copolymer (a- as an inner layer having a structure of one layer or two layers or more obtained from an alkyl acrylate ester as a main component. In the presence of 1), a monomer having an alkyl methacrylate as a main component is graft-polymerized to form a hard polymer (a-2) as an outer layer having a structure of one layer or two or more layers. A rubber-containing polymer having a multilayer structure of two or more layers.
[0042]
Examples of the alkyl acrylate ester used for the elastic copolymer (a-1) include conventionally known various alkyl acrylate esters. In particular, butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable. This alkyl acrylate is used as a main component of the monomers constituting the elastic copolymer (a-1). Specifically, the usage amount of the acrylic acid alkyl ester is preferably 35 to 99.9% by mass in all monomers. If this usage-amount is 35 mass% or more, the moldability of a film will become favorable. A more preferable usage amount is 50% by mass or more. Each range of these usage-amounts shows the usage-amount of the alkyl acrylate ester as a whole of an elastic copolymer (a-1), when an elastic copolymer (a-1) has a structure of two or more layers. Is. For example, when making an elastic copolymer (a-1) into a hard core structure, the usage-amount of the acrylic acid alkylester of the 1st layer (core part) can also be made into less than 35 mass%.
[0043]
As the monomer constituting the elastic copolymer (a-1), together with the alkyl acrylate ester, other vinyl monomers copolymerizable therewith can also be used. When other vinyl monomers are used, the amount used is preferably 64.9% by mass or less based on the total monomers. As other vinyl monomers, for example, methacrylic acid alkyl esters such as methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, styrene, acrylonitrile and the like are preferable. These can be used individually by 1 type or in combination of 2 or more types.
[0044]
A crosslinkable monomer is preferably used as a part of the monomer constituting the elastic copolymer (a-1). Examples of the crosslinkable monomer include ethylene glycol dimethacrylate, butanediol dimethacrylate, allyl acrylate, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl maleate , Trimethylolpropane triacrylate, and allyl cinnamate. These can be used individually by 1 type or in combination of 2 or more types. The amount of the crosslinkable monomer used is preferably 0.1 to 10% by mass in the total monomers.
[0045]
The rubber-containing polymer (A-1) is obtained by graft polymerization of a monomer mainly composed of an alkyl methacrylate in the presence of the elastic copolymer (a-1) described above. -2) is a rubber-containing polymer having a multilayer structure of two or more layers. That is, the elastic copolymer (a-1) constitutes the inner layer, and the hard polymer (a-2) constitutes the outer layer.
[0046]
In the graft polymerization for obtaining the hard polymer (a-2), methacrylic acid alkyl ester is used as a main component. Specifically, the amount of methacrylic acid alkyl ester used is preferably 50% by mass or more based on the total amount of monomers used for graft polymerization. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like.
[0047]
As a monomer used for graft polymerization for obtaining the hard polymer (a-2), other vinyl monomers copolymerizable therewith can be used together with the alkyl methacrylate. When other vinyl monomers are used, the amount used is preferably 50% by mass or less based on the total monomers. As other vinyl monomers, for example, acrylic acid alkyl esters such as methyl acrylate, butyl acrylate, cyclohexyl acrylate, styrene, acrylonitrile and the like are preferable. These can be used individually by 1 type or in combination of 2 or more types.
[0048]
These monomers are graft polymerized in one or more stages in the presence of the elastic copolymer (a-1) to form a hard polymer (a-2) as an outer layer, and a rubber-containing polymer. (A-1) is obtained. The amount of the hard polymer (a-2) in the rubber-containing polymer (A-1) is preferably 10 parts by mass or more, and 20 parts by mass or more with respect to 100 parts by mass of the elastic copolymer (a-1). On the other hand, 400 parts by mass or less is preferable, and 200 parts by mass or less is more preferable.
[0049]
The particle diameter of the rubber-containing polymer (A-1) is preferably 0.01 μm or more, more preferably 0.08 μm or more, and on the other hand, 0.5 μm or less is preferable, and 0.3 μm or less is more preferable. In particular, from the viewpoint of film formability, the particle diameter is preferably 0.08 μm or more.
[0050]
As a production method of the rubber-containing polymer (A-1), that is, a polymerization method for forming the elastic copolymer (a-1) and a polymerization method for forming the hard polymer (a-2), For example, a conventionally known emulsion polymerization method can be used. Although the optimum value of the polymerization temperature varies depending on the type and amount of the polymerization initiator used, it is usually preferably 40 ° C or higher, more preferably 60 ° C or higher, on the other hand, 95 ° C or lower, more preferably 120 ° C or lower.
[0051]
Various conventionally known polymerization initiators can be used. The polymerization initiator may be added to one or both of the aqueous phase and the monomer phase.
[0052]
Examples of the emulsifier used in the emulsion polymerization include anionic, cationic and nonionic surfactants, and anionic surfactants are particularly preferable. Anionic surfactants include, for example, carboxylate surfactants such as potassium oleate, sodium stearate, sodium myristate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate; sulfuric acid such as sodium lauryl sulfate Ester salt surfactants; sulfonate surfactants such as sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate; phosphate ester-based interfaces such as sodium polyoxyethylene alkylphenyl ether phosphate An active agent etc. are mentioned.
[0053]
The polymer latex obtained by emulsion polymerization may be filtered through a filter having an opening of 100 μm or less, and then coagulated by a known coagulation method such as an acid coagulation method, a salt coagulation method, a freeze coagulation method, or a spray drying method. . In the acid coagulation method, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. In the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate and calcium chloride, and organic salts such as calcium acetate and magnesium acetate can be used. The rubber-containing polymer (A-1) is obtained by further washing, dehydrating and drying the solidified polymer.
[0054]
The thermoplastic polymer (A-2) used for the acrylic resin composition (A) is a polymer obtained using a methacrylic acid alkyl ester as a main component, and various conventionally known ones can be used.
[0055]
As a thermoplastic polymer (A-2), 50-99.9 mass parts of methacrylic acid alkyl ester which has a C1-C4 alkyl group, 0.1-50 mass parts of acrylic acid alkyl esters, and these If necessary, a total of 100 parts by mass of 49.9 parts by mass or less of other vinyl monomers copolymerizable with the polymer was obtained, and reduced viscosity (0.1 g of polymer was added to 100 mL of chloroform). It is preferable from the viewpoint of film forming property that the polymer is dissolved and measured at 25 ° C.) of 0.1 L / g or less.
[0056]
More specifically, it is preferable that the reduced viscosity is 0.1 L / g or less because appropriate elongation occurs when the film raw material resin is melted and the film forming property is improved. Moreover, since the reduced viscosity is 0.05 L / g or more, since a film does not become weak, it is preferable at the point which becomes difficult to raise | generate a film break at the time of film forming and printing.
[0057]
As the alkyl methacrylate used for obtaining the thermoplastic polymer (A-2), for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like are preferable, and methyl methacrylate is particularly preferable.
[0058]
Further, as the alkyl acrylate ester, for example, methyl acrylate, ethyl acrylate, butyl acrylate and the like are preferable, and methyl acrylate is particularly preferable.
[0059]
Further, other vinyl monomers include aromatic vinyl compounds such as styrene, vinyl cyanide monomers such as acrylonitrile, unsaturated dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide N-cyclohexylmaleimide and the like.
[0060]
The manufacturing method of a thermoplastic polymer (A-2) is not specifically limited, For example, various polymerization methods, such as suspension polymerization, emulsion polymerization, and block polymerization, can be used. During the polymerization, a chain transfer agent, other polymerization aids, and the like may be used. Various chain transfer agents can be used, and mercaptans are particularly preferred.
[0061]
Next, the acrylic resin composition (B) will be described. The acrylic resin composition (B) has a basic structure of an innermost layer polymer (Ba) shown below, a crosslinked elastic polymer (Bb) shown below, and an outermost layer polymer (Bc) shown below. Furthermore, it has at least one intermediate layer (Bd) shown below between the layer made of the crosslinked elastic polymer (Bb) and the layer made of the outermost layer polymer (Bc). A multilayer structure polymer in which the content ratio of the acrylic acid alkyl ester monotonously decreases in the order of the cross-linked elastic polymer (Bb), the intermediate layer (Bd), and the outermost layer polymer (Bc). It is a resin composition as a main component.
[0062]
The innermost layer polymer (Ba) used in the acrylic resin composition (B) is an acrylic acid alkyl ester having a C 1-8 alkyl group or a methacrylic acid alkyl ester having a C 1-4 alkyl group ( B-a1) 80 to 100 parts by mass, another monomer (B-a2) having a copolymerizable double bond, if necessary, 20 parts by mass or less, and a polyfunctional monomer (B- It is a polymer obtained by polymerizing a monomer composition in which 0.1 to 5 parts by mass of a graft crossing agent is added to 100 parts by mass of a3) as necessary, including 10 parts by mass or less.
[0063]
Among the (meth) acrylic acid alkyl ester (B-a1) used for the innermost layer polymer (Ba), examples of the acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms include methyl acrylate and acrylic Ethyl acid, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and the like are preferable, and an alkyl acrylate having a low Tg is particularly preferable. These can be used individually by 1 type or in combination of 2 or more types.
[0064]
Among the (meth) acrylic acid alkyl ester (B-a1), examples of the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. . These can be used individually by 1 type or in combination of 2 or more types.
[0065]
The (meth) acrylic acid alkyl ester (B-a1) is most preferably used in a multistage manner thereafter, but depending on the purpose of the final product to be obtained, two or more types of monomers may be mixed. Alternatively, other types of (meth) acrylic acid alkyl esters can also be used.
[0066]
Examples of other monomer (B-a2) having a copolymerizable double bond include acrylic acid higher alkyl ester, acrylic acid lower alkoxy ester, acrylic acid cyanoethyl ester, acrylamide, acrylic acid, and methacrylic acid. Acrylic monomers are preferred. Styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, and the like can also be used.
[0067]
Examples of the polyfunctional monomer (B-a3) include diglycolic acid ethylene glycol, dimethacrylic acid 1,3-butylene glycol, dimethacrylic acid 1,4-butylene glycol, dimethacrylic acid propylene glycol and the like. Methacrylic acid alkylene glycol esters are preferred. Further, polyvinylbenzene such as divinylbenzene and trivinylbenzene, alkylene glycol diacrylate, and the like can also be used. These monomers usually work effectively to bridge the layer in which they are contained, and do not act on bonding between layers with other layers. Moreover, even if no polyfunctional monomer (B-a3) is used, a fairly stable multilayer structure can be obtained as long as the grafting agent is present. For example, when the hot strength or the like is strictly required, a polyfunctional monomer (B-a3) may be arbitrarily used depending on the purpose.
[0068]
Examples of the graft crossing agent described above include allyl, methallyl, or crotyl esters of copolymerizable α, β-unsaturated carboxylic acid or dicarboxylic acid. Of these, allyl esters such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid are preferred, and allyl methacrylate is particularly effective. Further, triallyl cyanurate, triallyl isocyanurate and the like can be used. In such graft crossing agents, the conjugated unsaturated bond of the ester mainly reacts and bonds much faster than the allyl group, methallyl group or crotyl group. A substantially significant portion of the allyl, methallyl, or crotyl group that reacts slowly acts effectively during the polymerization of the next layer polymer to provide a graft bond between adjacent two layers.
[0069]
The amount of the grafting agent used is extremely important, and is added within the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of components (B-a1) to (B-a3). If this addition amount is 0.1 parts by mass or more, the effective amount of graft bonding increases. Further, if it is 5 parts by mass or less, the amount of reaction with the crosslinked elastic polymer (Bb) polymerized and formed in the second stage is moderately suppressed, and the two-layer crosslinked rubber elastic body having a two-layer elastic structure is formed. Elasticity reduction can be prevented. The amount added is preferably 0.5 parts by mass or more, and more preferably 2 parts by mass or less.
[0070]
The content of the innermost layer polymer (Ba) in the acrylic resin composition (B) is preferably 5% by mass or more, on the other hand, preferably 35% by mass or less, and more preferably 15% by mass or less. Moreover, it is preferable that it is lower than content of a cross-linked elastic polymer (Bb).
[0071]
The cross-linked elastic polymer (Bb) used in the acrylic resin composition (B) is a main component that gives rubber elasticity to the multilayer structure polymer, and is an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms ( B-b1) 20 to 100 parts by mass of another monomer (B-b2) having a copolymerizable double bond and 80 to 100 parts by mass as necessary, and a polyfunctional monomer (B- A polymer (B-) obtained by polymerizing a monomer composition in which 0.1 to 5 parts by mass of a graft crossing agent is added to 100 parts by mass of b3) as necessary and 10 parts by mass or less. b).
[0072]
Specific examples of the components (B-b1) to (B-b3) and the graft crossing agent used for the crosslinked elastic body (B-b) include the components described in the innermost layer polymer (Ba) ( The same as B-a1) to (B-a3) and the graft crossing agent can be used.
[0073]
As for content of the crosslinked elastic polymer (Bb) in an acrylic resin composition (B), 10-45 mass% is preferable. Moreover, it is preferable that it is higher than content of an innermost layer polymer (Ba).
[0074]
The outermost layer polymer (Bc) used in the acrylic resin composition (B) is an effective component for distributing the film-forming property and moldability to the acrylic resin, and has 1 to 4 carbon alkyl ester. (B-c1) A monomer containing 51 to 100 parts by mass and another monomer (B-c2) having a copolymerizable double bond as needed is polymerized to 49 parts by mass or less. The glass transition temperature is preferably 60 ° C. or higher.
[0075]
As the methacrylic acid alkyl ester (Bc1) and other monomer (Bc2) used for the outermost layer polymer (Bc), the methacrylic acid alkyl ester (B-a) used for the innermost layer polymer (Ba) ( The thing equivalent to what was mentioned as an example of B-a1) and another monomer (B-a2) can be used.
[0076]
As for content of the outermost layer polymer (Bc) in an acrylic resin composition (B), 10-80 mass% is preferable.
[0077]
The intermediate layer (Bd) used for the acrylic resin composition (B) has 10 to 90 parts by mass of an alkyl acrylate ester (Bd1) having an alkyl group having 1 to 8 carbon atoms, and 1 to 4 carbon atoms. 90 to 10 parts by mass of an alkyl methacrylate having an alkyl group (B-d2) and a monomer having a copolymerizable double bond (B-d3), if necessary, 20 parts by mass or less, polyfunctional A monomer composition in which 0.1 to 5 parts by mass of a graft crossing agent is added to 100 parts by mass of the polymerizable monomer (B-d4) as necessary, including 10 parts by mass or less. In this layer, the amount of alkyl acrylate ester monotonously decreases from the cross-linked elastic polymer (Bb) toward the outermost layer (Bc).
[0078]
The components (Bd1) to (Bd4) used for the intermediate layer (Bd) and the graft crossing agent include the components (Ba1) to (B) used for the innermost layer polymer (Ba). -A3) and those equivalent to the examples of the grafting agent can be mentioned. Moreover, the content ratio (monomer composition ratio) of the acrylic acid alkyl ester in the intermediate layer (Bd) is set lower than the content ratio of the acrylic acid alkyl ester of the crosslinked elastic polymer (Bb), and the outermost layer ( It is set higher than the content ratio of the acrylic acid alkyl ester of Bc).
[0079]
As for content of the intermediate | middle layer (Bd) in an acrylic resin composition (B), 5-35 mass% is preferable. If this content is 5% by mass or more, the function as an intermediate layer is effectively expressed, and if it is 35% by mass or less, the balance of the final polymer becomes good.
[0080]
The acrylic resin composition (B) comprises the innermost layer polymer (Ba), the cross-linked elastic polymer (Bb), the intermediate layer (Bd) and the outermost layer polymer (Bc) described above. The main component is a multilayer structure polymer composed of each of the above layers. In order to produce this multilayer structure polymer, multistage polymerization for obtaining the above-mentioned four kinds of polymers (Ba) to (Bc) may be carried out sequentially in the same system. However, in that case, in addition to the multilayer polymer composed of the four types of polymers (Ba) to (Bc), homopolymer particles and polymer particles having a two- to three-layer structure tend to be generated. It is in. That is, the acrylic resin composition (B) referred to in the present invention is a case where other than the multilayer structure polymer composed of such four kinds of polymers (Ba) to (Bc) are mixed. Is also included.
[0081]
As the method for producing the acrylic resin composition (B), a sequential multi-stage polymerization method by an emulsion polymerization method is most suitable. However, it is not particularly limited to this, and for example, it can be produced by emulsion suspension polymerization in which the outermost layer polymer (Bc) after emulsion polymerization is converted to a suspension polymerization system.
[0082]
The polymer latex obtained by emulsion polymerization or the like can be filtered, for example, through a filter having an opening of 100 μm or less, and then coagulated by a known coagulation method such as an acid coagulation method, a salt coagulation method, a freeze coagulation method, or a spray drying method. Good. In the acid coagulation method, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. In the salt coagulation method, inorganic salts such as sodium sulfate, magnesium sulfate, aluminum sulfate and calcium chloride, and organic salts such as calcium acetate and magnesium acetate can be used. The solidified polymer may be further washed, dehydrated and dried.
[0083]
Furthermore, it is preferable to blend 0.1-20 parts by mass of the thermoplastic polymer (C) shown below with respect to 100 parts by mass of the acrylic resin composition (A) or acrylic resin composition (B) described above. .
[0084]
The thermoplastic polymer (C) polymerizes a total of 100 parts by weight including 50 to 100 parts by weight of methyl methacrylate and 50 parts by weight or less of other vinyl monomers copolymerizable therewith as necessary. A thermoplastic polymer having a reduced viscosity (0.1 g of polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) exceeding 0.2 L / g is obtained.
[0085]
By using such a thermoplastic polymer (C), the film-forming property is improved, which is particularly effective when a high level of thickness accuracy and film-forming speed are required. Moreover, since the reduced viscosity of a thermoplastic polymer (C) exceeds 0.2 L / g, it becomes a film with favorable thickness accuracy. In addition, as an upper limit of reduced viscosity, 2 L / g or less is preferable and 1.2 L / g or less is more preferable.
[0086]
Examples of other vinyl monomers copolymerizable with methyl methacrylate in the thermoplastic polymer (C) include alkyl acrylates, alkyl methacrylates other than methyl methacrylate, aromatic vinyl compounds, and vinyl cyanide. Compounds and the like.
[0087]
As a polymerization method for producing the thermoplastic polymer (C), an emulsion polymerization method is preferred. In the method for producing the thermoplastic polymer (C), for example, the polymer latex produced by the emulsion polymerization method is separated and collected by various coagulants, or the solid content is separated and collected by spray drying. obtain.
[0088]
As a preferable usage-amount of a thermoplastic polymer (C), it is 0.1-20 mass parts with respect to 100 mass parts of an acrylic resin composition (A) or an acrylic resin composition (B). When the amount used is 0.1 parts by mass or more, the effect of improving the film forming property is exhibited. On the other hand, when the amount is 20 parts by mass or less, the viscosity of the resin composition becomes moderate and good film-forming properties are obtained. It is done.
[0089]
As the thermoplastic resin film obtained by using the thermoplastic resin composition (III) as described above, one having a 60 ° surface glossiness of 50% or less is preferable. If the surface glossiness is 50% or less, the film surface is less glossy and can have a high-grade feeling when processed into a product, which has a high industrial utility value. More preferably, the surface gloss is 25% or less.
[0090]
In general, when the film is secondarily processed, heat is often received. At this time, the matte film may be delustered. However, if the surface glossiness at the initial stage of the film is preferably 50% or less, more preferably 25% or less, sufficient matteness can be maintained after the secondary processing even if this delustering occurs.
[0091]
The water whitening resistance of the thermoplastic resin film and the acrylic resin film is determined by observing the difference in whiteness after the test after being immersed in water at 100 ° C. for 2 hours under the condition of tensile stress of 0.02 MPa and then left at room temperature for 24 hours ( LabW) is preferably 25% or less, more preferably 20% or less, and even more preferably 10% or less compared to before the test. When the whiteness difference is 20% or less, the design change of the film and the laminate laminated with the rain exposure is small, and when the whiteness difference is 10% or less, the film and the rain exposure film are laminated. There is almost no change in the design of the laminate, and such thermoplastic resin composition molded products and acrylic resin films can withstand use in outdoor applications where water whitening resistance is particularly required. Will increase.
[0092]
In the case of a colored thermoplastic resin film and an acrylic resin film, the water whitening resistance is determined by immersing in water at 100 ° C. for 2 hours under the condition that the stress applied to the film is 0.02 MPa, and then leaving it at room temperature for 24 hours. Later, No. 4 or more is preferable in the evaluation using the gray scale for color fading. If the water whitening resistance is No. 4 or more, the appearance of the pre-test film and the post-test film is the same in the visual range. Such a thermoplastic resin film and an acrylic resin film can withstand use in outdoor applications particularly requiring water whitening resistance, and thus increase the industrial utility value.
[0093]
The thermoplastic resin composition, thermoplastic resin film, and acrylic resin film described above can be added to general compounding agents, for example, stabilizers, lubricants, processing aids, plasticizers, impact aids, foams, as necessary. Agents, fillers, colorants, UV absorbers and the like can be included.
[0094]
In particular, in terms of protecting the substrate, it is preferable to add an ultraviolet absorber in order to impart weather resistance. The molecular weight of the ultraviolet absorber is preferably 300 or more, and more preferably 400 or more. If this molecular weight is 300 or more, it is difficult to volatilize when vacuum forming or pressure forming is performed in an injection mold, and mold contamination is difficult to occur. The type of the UV absorber is not particularly limited, but a benzotriazole UV absorber having a molecular weight of 400 or more and a triazine UV absorber having a molecular weight of 400 or more are particularly preferable. Examples of the former commercial product include Ciba Geigy's trade name Tinuvin 234, Asahi Denka Kogyo Co., Ltd., trade name Adeka Stub LA-31. Examples of the latter commercial product include Ciba Geigy's trade name Tinuvin 1577.
[0095]
Although the thickness of a thermoplastic resin film and an acrylic resin film is not specifically limited, It is preferable that it is 300 micrometers or less. When the thickness is 300 μm or less, it has appropriate rigidity, so that the laminating property, the secondary workability and the like are improved. In addition, it is economically advantageous in terms of mass per unit area. Furthermore, the film forming property is stable and the production of the film becomes easy.
[0096]
As a base material which laminates a thermoplastic resin composition, a thermoplastic resin film, and an acrylic resin film, a resin molded product is mentioned, for example. The resin constituting the molded article may be any resin that can be melt-bonded to a thermoplastic resin film or an acrylic resin film. For example, ABS resin, ASA resin, polystyrene resin, polycarbonate resin, vinyl chloride resin, acrylic resin, Examples thereof include polyester resins and resins containing these as main components. Among these, ABS resin, ASA resin, polycarbonate resin, vinyl chloride resin, or a resin containing these as a main component is preferable from the viewpoint of adhesiveness. In particular, ABS resin, polycarbonate resin, or a resin containing these as a main component is more preferable. preferable. However, even if the base resin is not heat-sealed, such as polyolefin resin, it is possible to laminate the acrylic resin film and the base material by interposing an adhesive layer.
[0097]
A film forming method and a laminating method are not particularly limited and a conventionally known method can be used. For example, there is a method of heating a film using a roll or the like and laminating it on a substrate. Moreover, when laminating | stacking on a base material by an in-mold and insert molding method, a film is vacuum-formed first.
[0098]
Moreover, it can also laminate | stack by well-known methods, such as a co-extrusion method, as a method of laminating | stacking a thermoplastic resin composition on a base material.
[0099]
When the thermoplastic resin film and acrylic resin film of the present invention are laminated on a two-dimensional base material, a known method such as thermal lamination can be used for the base material that can be heat-sealed. Moreover, it is also possible to stick together through the adhesive agent with respect to the base material which is not heat-seal | fused. In the case of performing lamination molding on a three-dimensional base material, a known molding method such as an insert molding method or an in-mold molding method can be used. Among these, the in-mold molding method is particularly preferable from the viewpoint of productivity.
[0100]
Although it does not specifically limit as a use of this laminated molded article, It is suitable to use as a building material of the outdoor use for which water whitening resistance is required. Specifically, it is a roof such as a carport or a veranda, an exterior building material such as a front door, a window frame, an outer wall, or a signboard.
[0101]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not restrict | limited by these Examples. Unless otherwise specified, “part” represents “part by mass”, “%” represents “% by mass”, and a commercially available high-purity product was used.
[0102]
Abbreviations are as follows:
Methyl methacrylate MMA
Methyl acrylate MA
Butyl acrylate BA
Styrene St
α-Methylstyrene αM-ST
Cyclohexyl maleimide CHMI
Hydroxyethyl methacrylate HEMA
Allyl methacrylate AMA
1,3-butylene glycol dimethacrylate 1,3BD
t-Butyl hydroperoxide tBH
t-Hexyl hydroperoxide tHH
Lauryl peroxide LPO
n-octyl mercaptan nOM.
[0103]
The various physical properties in the examples were measured according to the following methods.
[0104]
<Reduced viscosity and intrinsic viscosity>
The reduced viscosity of the thermoplastic polymers (A-2) and (C) and the intrinsic viscosity of the hydroxyl group-containing acrylic polymer (II) are measured using an AVL-2C automatic viscometer manufactured by Sun Electronics Co., Ltd. Measurement was performed at 25 ° C. using chloroform. In the measurement of the reduced viscosity, a sample prepared by dissolving 0.1 g of a sample in 100 mL of chloroform was used.
[0105]
<Particle size>
Regarding the particle diameters of the rubber-containing polymer (A-1) and the multilayer structure polymer [acrylic resin composition (B)], the final particle diameter of the polymer latex of those polymers obtained by emulsion polymerization was determined as Otsuka Electronics Co., Ltd. ) Using a light scattering photometer DLS-700 manufactured by KK).
[0106]
<Glass transition temperature of hydroxyl group-containing acrylic polymer (II)>
The glass transition temperature (Tg) was determined according to the following empirical formula by Fox et al.
1 / Tg = Σ (1 / Tg _i )
Where Tg _i Is the glass transition temperature of the homopolymer obtained by polymerizing the i-th monomer, and Σ means the sum of i.
[0107]
<60 ° surface gloss of film and laminate>
60 degree surface glossiness measured the film surface which was not touching the cooling roll using the gloss meter (Murakami Color Research Laboratory make, GM-26D type).
[0108]
<Water whitening resistance>
As a water whitening resistance, a 50 μm film was prepared, a sample before the test, and a sample after the test that was immersed in water at 100 ° C. for 2 hours under the condition of a tensile stress of 0.02 MPa and then left at room temperature for 24 hours. In addition, whiteness (LabW) was measured based on JIS L 1015 using SM-4 manufactured by Suga Test Instruments Co., Ltd.
[0109]
Moreover, about the colored film, it evaluated using the gray scale for discoloration according to JISL0804 after a test.
[0110]
<Surface appearance>
The surface condition (roughness, uniformity) as a guideline for evaluation of dispersibility was visually evaluated according to the following criteria;
○: very good,
Δ: Good,
X: Defect.
[0111]
<Production Example 1> Acrylic resin composition (A)
The following (a) is charged into a reaction vessel, and the following raw materials (b) shown below are continuously added over 200 minutes at 80 ° C. in a nitrogen atmosphere while stirring, followed by further polymerization for 120 minutes, A latex of coalescence (a-1) was obtained.
[0112]
Subsequently, the following (c) shown below is added to the latex of the elastic copolymer (a-1), and the following raw materials (d) are continuously added for 100 minutes at 80 ° C. in a nitrogen atmosphere while stirring. And then polymerizing continuously at 80 ° C. for 60 minutes to form a hard polymer (a-2) to obtain a latex of a rubber-containing polymer (A-1). The rubber-containing polymer (A-1) had an average particle size of 0.12 μm.
[0113]
This rubber-containing polymer (A-1) latex is coagulated, agglomerated and solidified with 100 parts of polymer using 5 parts of calcium acetate, filtered, washed with water and dried to give a rubber-containing polymer. (A-1) was obtained.
[0114]

[0115]

[0116]
(C)
10 parts of deionized water
Sodium formaldehyde sulfoxylate 0.15 parts.
[0117]
(D)
MMA 57.0 parts
MA 3.0 parts
nOM 0.2 parts
tBH 0.1 part.
[0118]
56 parts of the rubber-containing polymer (A-1) obtained as described above, and MMA / MA copolymer (MMA / MA = 99/1, reduced viscosity 0. 1) as the thermoplastic polymer (A-2). (06 L / g) was mixed with 44 parts to obtain an acrylic resin composition (A).
[0119]
<Production Example 2> Acrylic resin composition (B)
In a polymerization vessel equipped with a condenser, 250 parts of ion-exchanged water, 2 parts of an ester soda salt of sulfosuccinic acid and 0.05 part of sodium formaldehyde sulfoxylate were charged, stirred under nitrogen, 1.6 parts of MMA, 8 parts of BA, , 3BD 0.4 part, AMA 0.1 part and cumene hydroperoxide 0.04 part. After raising the temperature to 70 ° C., the reaction was continued for 60 minutes to complete the polymerization of the innermost layer polymer (Ba). Thereafter, a mixture consisting of 1.5 parts of MMA, 22.5 parts of BA, 1.0 part of 1,3BD, 0.25 part of AMA and 0.05 part of cumene hydroperoxide to form a crosslinked elastic polymer (B-b). It added in 60 minutes and superposed | polymerized and the two-layer crosslinked rubber elastic body which consists of an innermost layer polymer (Ba) and a crosslinked elastic polymer (BB) was obtained.
[0120]
Subsequently, a mixture of 5 parts of MMA, 5 parts of BA and 0.1 part of AMA is reacted in the presence of this two-layer crosslinked rubber elastic body to form an intermediate layer (Bd), and finally, 52.25 parts of MMA. And a mixture of 2.75 parts of BA were reacted to form an outermost layer polymer (Bc) to obtain a latex of multilayer structure polymer.
[0121]
The particle diameter of this multilayer structure polymer was 0.12 μm. The obtained polymer latex is filtered through a filter having a mesh opening of 75 μm, and then salted out with 5 parts of calcium acetate with respect to 100 parts of the polymer, washed and dried to obtain an acrylic resin composition (B). Got.
[0122]
<Production Example 3> Thermoplastic polymer (C)
A reaction vessel was charged with 200 parts of ion-exchanged water substituted with nitrogen, and 1 part of an emulsifier potassium oleate and 0.3 part of potassium persulfate were charged. Subsequently, 40 parts of MMA, 10 parts of BA, and 0.005 part of nOM were charged and stirred at 65 ° C. for 3 hours in a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture consisting of 48 parts of MMA and 2 parts of BA was added dropwise over 2 hours, and maintained for 2 hours after the completion of the addition to complete the polymerization. The obtained latex was added to a 0.25% aqueous sulfuric acid solution, the polymer was acid coagulated, then dehydrated, washed with water, and dried to recover the polymer in powder form. Reduced viscosity η of the obtained copolymer _sp / C was 0.38 L / g.
[0123]
<Example 1> Hydroxyl group-containing acrylic polymer (II-1), thermoplastic resin composition (IIIa-1)
The following mixture was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, and the like.
[0124]

[0125]
The interior of the container was sufficiently replaced with nitrogen gas, and then heated to 75 ° C. with stirring, and polymerization was advanced in a nitrogen gas stream. After 2 hours, the temperature was raised to 90 ° C. and maintained for an additional 45 minutes to complete the polymerization. The obtained polymer beads were dehydrated and dried to obtain a hydroxyl group-containing acrylic polymer (II-1). The intrinsic viscosity of the hydroxyl group-containing acrylic polymer (II-1) was 0.076 L / g. The glass transition temperature was 93 ° C.
[0126]
Next, 10 parts of a hydroxyl group-containing acrylic polymer (II-1) is added to 100 parts of the acrylic resin composition (A), and further 1 part of a thermoplastic polymer (C), Tinuvin 1577 (Ciba Geigy) as an ultraviolet absorber. 1 part) was added and mixed using a Henschel mixer. Next, using a 40 mmφ screw type twin screw extruder (L / D = 26), the mixture was melt-kneaded and pelletized under conditions of a cylinder temperature of 200 ° C. to 260 ° C. and a die temperature of 250 ° C., and a thermoplastic resin composition ( A pellet of IIIa-1) was obtained.
[0127]
The pellets were dried overnight at 80 ° C., attached to a 300 mm T die, and a 40 mmφ non-vent screw type extruder (L / D = 26) provided with a 400 mesh screen mesh, with a cylinder temperature of 200 ° C. to 240 ° C., Melt extrusion was performed through a T die under a T die temperature of 250 ° C. The extruded resin was formed into an acrylic resin film having a thickness of 50 μm using a cooling mirror surface roll (chromium plated roll with a surface roughness of 0.2S) adjusted to 75 ° C.
[0128]
Next, when the ABS resin (Diapet ABS3001M manufactured by Mitsubishi Rayon) is extruded and molded into a 2 mm sheet at 240 ° C., it is extruded by introducing the above acrylic resin film between the molten ABS resin and the cooling roll. Lamination was performed to produce a laminate.
[0129]
<Example 2> Thermoplastic resin composition (IIIb-1)
The thermoplastic resin composition (IIIb) was the same as the thermoplastic resin composition (IIIa-1) except that 100 parts of the acrylic resin composition (B) was used instead of 100 parts of the acrylic resin composition (A). -1) was prepared and evaluated.
[0130]
<Example 3> Hydroxyl group-containing acrylic polymer (II-2), thermoplastic resin composition (IIIb-2)
Except for changing the monomer composition to MMA / MA / HEMA = 89/1/10 instead of MMA / MA / HEMA = 79/1/20, and further changing the amount of n-octyl mercaptan to 0.11 part, A hydroxyl group-containing acrylic polymer (II-2) was produced in the same manner as the hydroxyl group-containing acrylic polymer (II-1). The intrinsic viscosity was 0.09 L / g and the glass transition temperature was 98 ° C. A thermoplastic resin composition (IIIb-2) was prepared and evaluated in the same manner as the thermoplastic resin composition (IIIb-1) except that this hydroxyl group-containing acrylic polymer (II-2) was used.
[0131]
< Comparative Example 1 > Hydroxyl group-containing acrylic polymer (II-3), thermoplastic resin composition (IIIb-3)
Except for changing the monomer composition to MMA / MA / HEMA = 69/1/30 instead of MMA / MA / HEMA = 79/1/20, and further changing the amount of n-octyl mercaptan to 0.15 parts, A hydroxyl group-containing acrylic polymer (II-3) was produced in the same manner as the hydroxyl group-containing acrylic polymer (II-1). The intrinsic viscosity was 0.072 L / g, and the glass transition temperature was 87 ° C. A thermoplastic resin composition (IIIb-3) was prepared and evaluated in the same manner as the thermoplastic resin composition (IIIb-1) except that this hydroxyl group-containing acrylic polymer (II-3) was used.
[0132]
<Example 4 > Hydroxyl group-containing acrylic polymer (II-4), thermoplastic resin composition (IIIb-4)
Except for changing the monomer composition to MMA / MA / HEMA = 94/1/5 instead of MMA / MA / HEMA = 79/1/20 and further changing the amount of n-octyl mercaptan to 0.11 part, A hydroxyl group-containing acrylic polymer (II-4) was produced in the same manner as the hydroxyl group-containing acrylic polymer (II-1). The intrinsic viscosity was 0.089 L / g and the glass transition temperature was 101 ° C. A thermoplastic resin composition (IIIb-4) was prepared and evaluated in the same manner as the thermoplastic resin composition (IIIb-1) except that this hydroxyl group-containing acrylic polymer (II-4) was used.
[0133]
< Comparative Example 2 > Hydroxyl group-containing acrylic polymer (II-5), thermoplastic resin composition (IIIb-5)
Except for changing the monomer composition to MMA / MA / HEMA = 75/5/20 instead of MMA / MA / HEMA = 79/1/20, the same manner as in the hydroxyl group-containing acrylic polymer (II-1) A hydroxyl group-containing acrylic polymer (II-5) was produced. The intrinsic viscosity was 0.075 L / g and the glass transition temperature was 88 ° C. A thermoplastic resin composition (IIIb-5) was prepared and evaluated in the same manner as the thermoplastic resin composition (IIIb-1) except that this hydroxyl group-containing acrylic polymer (II-5) was used.
[0134]
< Comparative Example 3 > Hydroxyl group-containing acrylic polymer (II-6), thermoplastic resin composition (IIIb-6)
Except for changing the monomer composition to MMA / MA / HEMA = 70/10/20 instead of MMA / MA / HEMA = 79/1/20, the same manner as for the hydroxyl group-containing acrylic polymer (II-1) A hydroxyl group-containing acrylic polymer (II-6) was produced. The intrinsic viscosity was 0.073 L / g and the glass transition temperature was 82 ° C. A thermoplastic resin composition (IIIb-6) was prepared and evaluated in the same manner as the thermoplastic resin composition (IIIb-1) except that this hydroxyl group-containing acrylic polymer (II-6) was used.
[0135]
<Example 5 > Thermoplastic resin composition (IIIb-7)
Except changing the addition amount of a hydroxyl-containing acrylic polymer (II-2) to 20 parts with respect to 100 parts of acrylic resin compositions (B), it is carried out similarly to a thermoplastic resin composition (IIIb-2). A thermoplastic resin composition (IIIb-7) was prepared and evaluated.
[0136]
<Example 6 > Thermoplastic resin composition (IIIb-8)
Except changing the addition amount of a hydroxyl-containing acrylic polymer (II-2) to 30 parts with respect to 100 parts of acrylic resin compositions (B), it is the same as that of a thermoplastic resin composition (IIIb-2). A thermoplastic resin composition (IIIb-8) was prepared and evaluated.
[0137]
<Example 7 > Hydroxyl group-containing acrylic polymer (II-7), thermoplastic resin composition (IIIb-9)
A hydroxyl group-containing acrylic polymer (II-7) was prepared in the same manner as the hydroxyl group-containing acrylic polymer (II-1) except that the amount of n-octyl mercaptan was changed to 0.09 part. The intrinsic viscosity was 0.11 L / g and the glass transition temperature was 93 ° C. A thermoplastic resin composition (IIIb-9) was prepared and evaluated in the same manner as the thermoplastic resin composition (IIIb-1) except that this hydroxyl group-containing acrylic polymer (II-7) was used.
[0138]
<Example 8 > Thermoplastic resin composition (III-10)
A thermoplastic resin composition (IIIa-) except that 100 parts by mass of a polycarbonate resin (trade name: Lexan ML5500, manufactured by General Electric Co., Ltd.) and 10 parts by mass of a hydroxyl group-containing acrylic polymer (II-1) are mixed with a Henschel mixer. A thermoplastic resin composition (III-10) was prepared and evaluated in the same manner as in 1).
[0139]
<Example 9 > Thermoplastic resin composition (III-11)
70 parts by weight of a vinyl chloride resin (P = 1100), 2 parts by weight of a stabilizer (dibutyltin maleate), 25 parts by weight of an impact resistance aid (trade name: Metablen C-102, manufactured by Mitsubishi Rayon Co., Ltd.), a processing aid (Mitsubishi) Made by Rayon Co., Ltd., trade name: metabrene P-551) 1 part by mass, lubricant (butyl stearylate) 1 part by mass, carbon black 0.5 part by mass, hydroxyl group-containing acrylic polymer (II-1) 10 parts by mass The thermoplastic resin composition is the same except that the thermoplastic resin composition (III-11) is prepared in the same manner as the thermoplastic resin composition (IIIa-1) except that it is mixed with a Henschel mixer, and the film is formed at 160 ° C. Evaluation was performed in the same manner as the product (IIIa-1).
[0140]
<Example 10 > Thermoplastic resin composition (III-12)
A thermoplastic resin except that 10 parts by mass of a hydroxyl group-containing acrylic polymer (II-1) is mixed with 100 parts by mass of ASA resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Dialac E610 black colored product). A thermoplastic resin composition (III-12) was prepared and evaluated in the same manner as the composition (IIIa-1).
[0141]
<Comparative example 4 > Hydroxyl group-containing acrylic polymer (II-8), thermoplastic resin composition (IIIb-13)
Hydroxyl group-containing acrylic polymer (II-2) except that the monomer composition was changed to MMA / MA / HEMA = 98.5 / 1 / 0.5 instead of MMA / MA / HEMA = 89/1/10 In the same manner as above, a hydroxyl group-containing acrylic polymer (II-8) was produced. The intrinsic viscosity was 0.091 L / g and the glass transition temperature was 103 ° C. A thermoplastic resin composition (IIIb-13) was prepared and evaluated in the same manner as the thermoplastic resin composition (IIIb-2) except that this hydroxyl group-containing acrylic polymer (II-8) was used.
[0142]
<Comparative example 5 > Hydroxyl group-containing acrylic polymer (II-9), thermoplastic resin composition (IIIb-14)
The monomer composition was changed to MMA / MA / HEMA = 49/1/50 instead of MMA / MA / HEMA = 79/1/20, and the n-octyl mercaptan amount was changed to 0.19 part, A hydroxyl group-containing acrylic polymer (II-9) was produced in the same manner as the hydroxyl group-containing acrylic polymer (II-1). The intrinsic viscosity was 0.06 L / g and the glass transition temperature was 77 ° C. A thermoplastic resin composition (IIIb-14) was prepared and evaluated in the same manner as the thermoplastic resin composition (IIIb-1) except that this hydroxyl group-containing acrylic polymer (II-9) was used.
[0143]
<Comparative example 6 > Hydroxyl group-containing acrylic polymer (II-10), thermoplastic resin composition (IIIb-15)
Except for changing the monomer composition to MMA / MA / HEMA = 60/20/20 instead of MMA / MA / HEMA = 79/1/20, and further changing the amount of n-octyl mercaptan to 0.08 parts, A hydroxyl group-containing acrylic polymer (II-10) was produced in the same manner as the hydroxyl group-containing acrylic polymer (II-1). The intrinsic viscosity was 0.11 L / g, and the glass transition temperature was 71 ° C. A thermoplastic resin composition (IIIb-15) was prepared and evaluated in the same manner as the thermoplastic resin composition (IIIb-1) except that this hydroxyl group-containing acrylic polymer (II-10) was used.
[0144]
<Comparative example 7 > Hydroxyl group-containing acrylic polymer (II-11), thermoplastic resin composition (IIIa-16)
Except for changing the monomer composition to MMA / MA / HEMA = 60/10/30 instead of MMA / MA / HEMA = 79/1/20, and further changing the amount of n-octyl mercaptan to 0.15 parts, A hydroxyl group-containing acrylic polymer (II-11) was produced in the same manner as the hydroxyl group-containing acrylic polymer (II-1). The intrinsic viscosity was 0.069 L / g and the glass transition temperature was 77 ° C. A thermoplastic resin composition (IIIa-16) was prepared and evaluated in the same manner as the thermoplastic resin composition (IIIa-1) except that this hydroxyl group-containing acrylic polymer (II-11) was used.
[0145]
<Comparative example 8 > Thermoplastic resin composition (IIIb-16)
The thermoplastic resin composition (IIIb) was the same as the thermoplastic resin composition (IIIa-16) except that 100 parts of the acrylic resin composition (B) was used instead of 100 parts of the acrylic resin composition (A). -16) was prepared and evaluated.
[0146]
< Reference example 1 > Thermoplastic resin composition (IIIb-17)
The same as the thermoplastic resin composition (IIIb-1) except that the addition amount of the hydroxyl group-containing acrylic polymer (II-1) is changed to 0.5 part with respect to 100 parts of the acrylic resin composition (B). Thus, a thermoplastic resin composition (IIIb-17) was produced and evaluated.
[0147]
< Reference example 2 > Thermoplastic resin composition (IIIb-18)
Except changing the addition amount of a hydroxyl-containing acrylic polymer (II-1) to 50 parts with respect to 100 parts of acrylic resin compositions (B), it is the same as that of a thermoplastic resin composition (IIIb-1). A thermoplastic resin composition (IIIb-18) was prepared and evaluated.
[0148]
<Comparative example 9 > Thermoplastic resin composition (III-19)
The thermoplastic resin composition (III) is the same as the thermoplastic resin composition (III-10) except that the hydroxyl group-containing acrylic polymer (II-10) is used instead of the hydroxyl group-containing acrylic polymer (II-1). -19) was prepared and evaluated.
[0149]
<Comparative example 10 > Thermoplastic resin composition (III-20)
The thermoplastic resin composition (III) is the same as the thermoplastic resin composition (III-11) except that the hydroxyl group-containing acrylic polymer (II-10) is used instead of the hydroxyl group-containing acrylic polymer (II-1). −20) was prepared and evaluated.
[0150]
<Comparative example 11 > Thermoplastic resin composition (III-21)
The thermoplastic resin composition (III) is the same as the thermoplastic resin composition (III-12) except that the hydroxyl group-containing acrylic polymer (II-10) is used instead of the hydroxyl group-containing acrylic polymer (II-1). -21) was prepared and evaluated.
[0151]
The above compositions are summarized in Table 1.
[0152]
[Table 1]

[0153]
The evaluation results are summarized in Table 2.
[0154]
[Table 2]

[0155]
However, in Table 2, the evaluation regarding the water whitening resistance of the thermoplastic resin compositions (III-11), (III-12), (III-20) and (III-21) is based on gray scale.
[0156]
From the above, it was found that by using the hydroxyl group-containing acrylic polymer of the present invention as a matting agent, an excellent matte appearance having sufficient water whitening resistance can be realized.
[0157]
【The invention's effect】
As explained above, 1 to 20 parts by mass of a (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, 79 to 99 parts by mass of a methacrylic acid alkyl ester having an alkyl group having 1 to 13 carbon atoms, and Acrylic acid alkyl ester Obtained by polymerizing a total of 100 parts by weight of the monomer composition including less than 10 parts by weight, the glass transition temperature is 93 Addition of a hydroxyl group-containing acrylic polymer having a temperature of ˜120 ° C. to a thermoplastic resin as a matting agent, a thermoplastic resin composition having a good matte appearance and water whitening resistance applicable to outdoor use You can get things.

Claims (6)

  1 to 20 parts by mass of a (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, 79 to 99 parts by mass of an alkyl methacrylate having 1 to 13 carbon atoms and 10 parts by mass of an alkyl alkyl ester A hydroxyl group-containing acrylic polymer obtained by polymerizing a total of 100 parts by mass of a monomer composition containing less than 10 parts, and having a glass transition temperature of 93 to 120 ° C. Thermoplastic resin (I) made of acrylic resin, polycarbonate resin, vinyl chloride resin or ASA resin [However, the following hydroxyl group-containing acrylic polymer (II) and 50 to 100 parts by mass of methyl methacrylate, and copolymerized therewith It can be obtained by polymerizing a total of 100 parts by mass of a monomer composition containing other possible vinyl monomers as needed and 50 parts by mass or less. The thermoplastic polymer (C) dissolved in 100 mL and measured at 25 ° C.) exceeding 0.2 L / g is excluded. ] 100 parts by mass;
1 to 20 parts by mass of a (meth) acrylic acid hydroxyalkyl ester having an alkyl group having 1 to 8 carbon atoms, 79 to 99 parts by mass of an alkyl methacrylate having 1 to 13 carbon atoms and 10 parts by mass of an alkyl alkyl ester A thermoplastic comprising 1 to 40 parts by mass of a hydroxyl group-containing acrylic polymer (II) obtained by polymerizing a total of 100 parts by mass of a monomer composition including less than 100 parts, and having a glass transition temperature of 93 to 120 ° C. Resin composition. For 100 parts by mass of the thermoplastic resin (I)
Obtained by polymerizing a total of 100 parts by weight of a monomer composition containing 50 to 100 parts by weight of methyl methacrylate and 50 parts by weight or less of another vinyl monomer copolymerizable therewith. , reduced viscosity of the polymer (a polymer 0.1g was dissolved in chloroform 100 mL, measured at 25 ° C.) further comprises a thermoplastic polymer (C) 0.1 to 20 parts by mass is more than 0.2 L / g according Item 3. The thermoplastic resin composition according to Item 2 .   A thermoplastic resin film comprising the thermoplastic resin composition according to claim 2.   A laminate formed by laminating the thermoplastic resin film according to claim 4.   A building material in which the thermoplastic resin film according to claim 4 is laminated.