JP2004168896A - Composition and utilization thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive capable of improving resistance to surface stain of a cured product by being compounded with a curable composition containing (A) an organic polymer having at least one silicon group hydrolyzable and crosslinkable by the hydrolysis in the molecule. <P>SOLUTION: The composition contains (B) a fluorine-containing polymer containing a polymerization unit having a photocurable functional group, and (C) a compound having a nitroso group, a hydroxyamino group or a salt thereof. <P>COPYRIGHT: (C)2004,JPO

Description

【００２０】
Ｒ^ｆ１、Ｒ^ｆ２はポリフルオロ炭化水素基。
なお、Ｒ^ｆ１は、連結基を含むポリフルオロ炭化水素基であることが好ましく、Ｒ^ｆ２は、連結基を含まないポリフルオロ炭化水素基であることが好ましい。
【００２１】
含フッ素重合体（Ｂ１）はポリフルオロ炭化水素基を有する重合単位（ｐ）を全重合単位に対して２０〜９５モル％、特に３０〜９０モル％含有する重合体であることが好ましい。２０モル％よりも少ないと、充分な表面耐汚染性が発揮されず、長期使用において汚れなどが著しくなることがある。
【００２２】
［重合性モノマー（ｂ）／（ｃ）］
光硬化性官能基を有する重合単位（ｑ）は、光硬化性官能基を有する重合性モノマー（ｂ）に基づく重合単位であるか、または、光硬化性官能基を導入しうる官能基を有する重合性モノマー（ｃ）を重合性モノマー（ａ）などと共重合して共重合体を製造した後に、光硬化性官能基を導入することにより生成される、重合性モノマー（ｃ）に基づく重合単位であって、かつ光硬化性官能基が導入された重合単位であることが好ましい。
【００２３】
前者の場合、光硬化性官能基としては、上記例示した基のうち熱重合性を有しない官能基に制限される。具体的にはシンナモイル基が好ましい。重合性モノマー（ｂ）としては具体的にはたとえばアリルシンナメート、アリルアルコール−アルキレンオキシド付加物のケイ皮酸エステル、アクリル酸（２−ヒドロキシエチル）エステルのケイ皮酸エステルなどがある。
【００２４】
また、後者の重合性モノマー（ｃ）は、重合性部位を有しかつ官能基を有する重合性モノマーであり、重合後、該官能基と反応性を有する基と光硬化性官能基とを併有する化合物、を反応させて光硬化性官能基を導入できる。該官能基としては水酸基が好ましい。
【００２５】
水酸基含有重合性モノマーとしては、アリルアルコール、ヒドロキシアルキルビニルエーテル、ヒドロキシアルキルアリルエーテル、（メタ）アクリル酸（ヒドロキシアルキル）エステルや、これらのアルキレンオキシド付加物等が挙げられる。また、アクリル酸、メタクリル酸、アリルグリシジルエーテル等、の水酸基と反応しうる官能基を有する重合性モノマーとジオールを反応させて得られるモノマーも使用しうる。なお、本発明においてたとえばアクリル酸とメタクリル酸を便宜上（メタ）アクリル酸と記載することもある。
【００２６】
また、水酸基と反応性を有する基と光硬化性官能基とを併有する化合物としては、（メタ）アクリル酸、（メタ）アクリル酸クロリド、（メタ）アクリル酸（２−イソシアネートエチル）エステル、（メタ）アクリル酸とイソシアネートホロンジイソシアネートなどジイソシアネートとの反応物等の（メタ）アクリル酸誘導体、およびシンナモイルクロリド等が挙げられる。
【００２７】
水酸基含有重合性モノマーなどの重合性モノマー（ｃ）と重合性モノマー（ａ）などとを共重合して共重合体（Ｄ）を得た後、（Ｄ）における水酸基などの官能基に、直接、水酸基などの官能基と反応性を有する基と光硬化性官能基とを併有する化合物を反応させてもよく、また、共重合体における水酸基などの官能基に、直結してポリエーテル鎖、ポリウレタン鎖、ポリアミド鎖およびポリエステル鎖から選ばれるスペーサを生成させ、ついで光硬化性官能基を導入してもよい。特に炭素数２〜１０程度、特に炭素数２〜６のアルキレンオキシドを開環重合して得られるポリエーテル鎖やカプロラクトン等の環状エステルを開環重合して得られるポリエステル鎖が好ましい。なお、共重合体（Ｄ）に該光硬化性官能基を導入する際、光硬化性官能基を導入しうる基が残っていてもよい。
【００２８】
含フッ素重合体（Ｂ１）は光硬化性官能基を有する重合単位（ｑ）を全重合単位に対して５〜８０モル％含有することが好ましい。光硬化性官能基を有する重合単位（ｑ）が５モル％よりも少ないと、充分な光硬化皮膜が形成されず、長期使用において汚れなどが著しくなることがある。全重合単位に対して１０〜７０モル％、特に１０〜５０モル％含有することが好ましい。
【００２９】
［重合性モノマー（ｄ）］
含フッ素重合体（Ｂ１）は重合単位（ｐ）、重合単位（ｑ）以外の重合単位（ｒ）を有していてもよい。重合単位（ｒ）は（ａ）、（ｂ）以外の重合性モノマー（ｄ）が重合することにより生成する重合単位であることが好ましい。また、重合性モノマー（ｃ）が重合することにより生成する重合単位であって、光硬化性官能基が導入されなかった重合単位であってもよい。
【００３０】
重合単位（ｒ）は全重合単位に対して０〜７５モル％の割合であることが好ましい。すなわち、重合単位（ｐ）と重合単位（ｑ）の合計が、全重合単位に対して２５モル％以上の割合で含まれることが好ましい。
【００３１】
重合性モノマー（ｄ）としては、ビニル基、アリル基、アクリロイル基、メタクリロイル基、イソプロペニル基などの重合性部位を有する重合性モノマーが挙げられる。
【００３２】
具体的にはビニルエーテル類、オレフィン類、アリルエーテル類、ビニルエステル類、アリルエステル類、アクリル酸エステル類、メタクリル酸エステル類、イソプロペニルエーテル類、イソプロペニルエステル類、クロトン酸エステル類およびその他の重合性モノマー、が例示できる。なかでも炭素数１〜１５程度の直鎖状、分岐状または脂環状のアルキル基を有する化合物が好ましい。より具体的な化合物としては、下記のものが挙げられる。
【００３３】
メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル、イソブチルビニルエーテル、シクロヘキシルビニルエーテル、クロロエチルビニルエーテル、などのビニルエーテル類；エチレン、プロピレン、１−ブテン、イソブチレン、シクロヘキセン、スチレン、α−メチルスチレンなどのオレフィン類；メチルアリルエーテル、エチルアリルエーテル、ブチルアリルエーテル、シクロヘキシルアリルエーテル、などのアリルエーテル類；酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、イソ酪酸ビニル、吉草酸ビニル、カプロン酸ビニル、カプリル酸ビニル、ベオバ９およびベオバ１０（シェル化学社製、炭素数９または炭素数１０の分岐脂肪酸のビニルエステルの商品名）、バーサティック酸ビニルなどの脂肪酸ビニルエステル類；酢酸アリルなどのアリルエステル類；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸シクロヘキシルなどの（メタ）アクリル酸エステル類；クロトン酸エチル、クロトン酸ブチル、クロトン酸シクロヘキシルなどのクロトン酸エステル類；（メタ）アクリル酸アミドなどの（メタ）アクリル系アミド類；アクリロニトリル、２，４−ジシアノブテン−１などのシアノ基含有モノマー類；イソプレン、ブタジエンなどのジエン類；塩化ビニル、塩化ビニリデン、などのハロゲン化オレフィン類などがある。
【００３４】
分子量１００〜３０００程度のポリオキシアルキレン鎖を有する重合性モノマー、たとえば分子量１００〜３０００のポリオキシプロピレングリコールモノアルキルエーテルモノ（メタ）アクリレートなどが挙げられる。また式１で表される加水分解性ケイ素基を有する重合性モノマーや後述のフルオロオレフィン（ｅ）も使用できる。
【００３５】
重合方法は溶液重合、乳化重合、懸濁重合、バルク重合のいずれの方法によってもよく、所定量の重合性モノマーに重合開始剤、電離性放射線などの重合開始源を作用させることにより重合が行われる。また適当な連鎖移動剤を存在させて、分子量を調節してもよい。さらに、後述する加水分解性ケイ素基を有する有機重合体の存在下で重合を行ってもよい。
【００３６】
含フッ素重合体（Ｂ１）の数平均分子量は１０００〜５０００００であることが好ましい。数平均分子量が５０００００超では硬化体の表面に移行しにくく不都合である。数平均分子量が１０００未満では耐候性などの物性が劣る。好ましくは、３０００〜５００００、特には３０００〜１５０００である。
【００３７】
［含フッ素重合体（Ｂ２）］
［重合性モノマー（ｅ）］
本発明における含フッ素重合体（Ｂ２）は、フルオロオレフィン（ｅ）に基づく重合単位（ｓ）を全重合単位に対して２０〜７０モル％、特に３０〜６０モル％含有することが好ましい。フルオロオレフィンに基づく重合単位（ｓ）とはフルオロオレフィン（ｅ）を重合することにより得られる重合単位である。
【００３８】
フルオロオレフィン（ｅ）とはエチレン性不飽和基を有する化合物であって、該エチレン性不飽和基を形成する炭素原子に直結する水素原子の１個以上がフッ素原子に置換されている化合物をいう。炭素数２〜６の化合物が好ましく、炭素数２〜４の化合物が特に好ましい。フルオロオレフィン（ｅ）としてはフッ素原子以外のハロゲン原子を含む化合物であってもよい。エチレン性不飽和基を形成する炭素原子に直結する水素原子が完全にハロゲン原子に置換されているパーハロオレフィンが特に好ましい。
【００３９】
フルオロオレフィン（ｅ）の具体例としては、テトラフルオロエチレン、クロロトリフルオロエチレン、トリフルオロエチレン、フッ化ビニリデン、フッ化ビニル、ヘキサフルオロプロピレンなどが挙げられる。
【００４０】
光硬化性官能基を有する重合単位（ｔ）は、重合体（Ｂ１）で説明した重合単位（ｑ）と同様の重合単位であり、上記の重合性モノマー（ｂ）を重合して得られる重合単位または重合性モノマー（ｃ）を重合した後光硬化性官能基を導入して得られる重合単位が好ましい。
【００４１】
また、この光硬化性官能基を有する重合単位（ｔ）は、全重合単位に対して５〜８０モル％の割合で含まれ、全重合単位に対して５〜４０モル％の割合で含まれることが特に好ましい。
【００４２】
本発明の含フッ素重合体は、重合単位（ｓ）と重合単位（ｔ）とのみからなっていてもよく、（ｓ）、（ｔ）以外の重合単位（ｕ）、すなわち（ｅ）、（ｇ）以外のモノマー（ｊ）に基づく重合単位（ｕ）を有していてもよい。この場合、重合単位（ｕ）は全重合単位に対して０〜７０モル％の割合が好ましい。すなわち、重合単位（ｓ）と重合単位（ｔ）の合計が、全重合単位に対して３０モル％以上が好ましい。
【００４３】
重合性モノマー（ｊ）は、エチレン性不飽和基を形成する炭素原子に直結する水素原子がフッ素原子に置換されてなく、また、光硬化性官能基を有しない。上記した重合性モノマー（ｄ）で例示したものが使用できる。また、重合性モノマー（ａ）も使用できる。
重合方法は重合体（Ｂ１）で例示した方法と同様の方法が採用できる。
含フッ素重合体（Ｂ２）の数平均分子量は１０００〜５０００００であることが好ましい。数平均分子量が５０００００超では硬化体の表面に移行しにくく不都合である。数平均分子量が１０００未満では耐候性などの物性が劣る。好ましくは、３０００〜５００００、特には３０００〜１５０００である。
【００４４】
［化合物（Ｃ）］
本発明において、ニトロソ基またはヒドロキシアミノ基もしくはその塩を有する化合物（Ｃ）を使用する。化合物（Ｃ）は、重合禁止剤または重合抑制剤として機能すると考えられる。具体的には、Ｎ−メチル−Ｎ−ニトロソアニリン、Ｎ−ニトロソフェニルヒドロキシルアミンまたはその塩類等が挙げられ、Ｎ−ニトロソフェニルヒドロキシルアミン塩類が好ましい。
【００４５】
Ｎ−ニトロソフェニルヒドロキシルアミン塩類としては、Ｎ−ニトロソフェニルヒドロキシアミンアンモニウム塩やＮ−ニトロソフェニルヒドロキシアミンアルミニウム塩が好ましい。
【００４６】
これらは、単独または混合し使用することができる。また、他の重合禁止剤もしくは重合抑制剤と併用してもよい。また、他の重合禁止剤もしくは重合抑制剤を併用してもよい。具体的には、ヒドロキノン、ｐ−メトキシフェノール、４−ｔ−ブチルカテコール、２−ｔ−ブチルヒドロキノン、２，６−ジ−ｔ−ブチル−４−メチルフェノールなどのフェノール系の化合物、フェノチアジン等が挙げられる。
【００４７】
化合物（Ｃ）の使用量は、光硬化性官能基を有する重合単位を有する含フッ素重合体（Ｂ）１００質量部に対して、０．００１質量部〜１０質量部の範囲が好ましい。
【００４８】
０．００１質量部未満では貯蔵安定性効果や硬化性組成物施工後における表面移行前の内部での硬化の防止効果が充分に発揮されない。また、１０質量部を超えると硬化性組成物施工後における表面移行後の光硬化性をも阻害し、硬化性組成物の耐表面汚染効果が充分に発揮されない。より好ましい割合は、０．００１質量部〜１０質量部の範囲であり、特に好ましくは、０．０１質量部〜５質量部の範囲である。
【００４９】
化合物（Ｃ）は、含フッ素重合体（Ｂ）の製造直後または製造の途中で含フッ素重合体（Ｂ）に添加することが好ましい。有機溶媒中で含フッ素重合体（Ｂ）を製造する場合には、溶媒を留去する前にまたは溶媒を留去した直後に添加できる。また、あらかじめ光硬化性官能基を導入しうる官能基を有する含フッ素重合体を製造した後光硬化性官能基を導入する場合、反応を阻害しない限り光硬化性官能基を導入する前に化合物（Ｃ）を添加できる。
【００５０】
［有機重合体（Ａ）］
本発明における加水分解により架橋可能な加水分解性ケイ素基（以下単に加水分解性ケイ素基ともいう）を分子内に１つ以上有する有機重合体（Ａ）としては、ポリエーテル、ポリエステルおよびポリカーボネートから選ばれる有機重合体から誘導される有機重合体が挙げられる。またエチレン、プロピレン、イソブチレンなどのオレフィン類、（メタ）アクリル酸エステル類、ビニルアルキルエーテル類、ブタジエンやクロロプレンなどのジエン類、クロロトリフルオロエチレンやテトラフルオロエチレンなどのハロゲン化オレフィン類、などの重合性モノマーと加水分解性ケイ素基含有重合性モノマーを共重合して得られる加水分解性ケイ素基含有ビニル系重合体などが挙げられる。
【００５１】
特にポリエーテル、ポリエステルおよびポリカーボネートから選ばれる有機重合体から誘導される有機重合体であることが好ましい。なかでもポリエーテルから誘導される加水分解性ケイ素基含有ポリエーテルが特に好ましい。
【００５２】
加水分解性ケイ素基含有ポリエーテルは、触媒の存在下、活性水素を含有する開始剤にプロピレンオキシドなどの環状エーテルを開環重合反応させて得られる水酸基含有ポリエーテルから誘導されることが特に好ましい。
【００５３】
開始剤としては、多価アルコール、多価カルボン酸、多価アミンなどの多価活性水素化合物、末端不飽和基含有モノオールが、触媒としてはナトリウム、カリウム、セシウムなどのアルカリ金属やそれらアルカリ金属の水酸化物などのアルカリ金属化合物、複合金属シアン化物錯体、金属ポルフィリン錯体などが、挙げられる。
【００５４】
本発明において加水分解性ケイ素基とは、シラノール基やアルコキシシリル基のように、湿分や硬化触媒などにより縮合反応を起こし有機重合体の架橋によって高分子量化を促進しうるものであり、好ましくは式１で表される基である。
【００５５】
【化３】

【００５６】
式中、Ｒ^１は炭素数１〜２０の置換または非置換の１価の炭化水素基、Ｘは水酸基または１価の加水分解性基、ａは１〜３の整数である。
【００５７】
加水分解性ケイ素基含有ポリエーテルは、水酸基含有ポリエーテルから誘導される場合、通常、有機基を介して式１で表される加水分解性ケイ素基が導入される。よって、本発明における有機重合体（Ａ）は式７で表される基を有することが好ましい。
【００５８】
【化４】

【００５９】
式中、Ｒ^０は炭素数１〜１０の置換または非置換の２価の炭化水素基、Ｒ^１、Ｘ、ａは上記に同じ。
【００６０】
ここで、式７中のＲ^０としては、炭素数８以下の２価の炭化水素基が好ましい。式１、式７中のＲ^１としては、炭素数８以下のアルキル基、フェニル基またはフルオロアルキル基が好ましく、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、シクロヘキシル基またはフェニル基が特に好ましい。
【００６１】
式１、式７中のＸは水酸基または１価の加水分解性基であり、加水分解性基としてはたとえばハロゲン原子、アルコキシ基、アシルオキシ基、アミド基、アミノ基、アミノオキシ基、またはケトキシメート基が好ましい。これらのうち炭素原子を有する加水分解性基の炭素数は６以下、特には４以下が好ましい。好ましいＸは炭素数４以下のアルコキシ基、特にはメトキシ基、エトキシ基またはプロポキシ基である。式１、式７中のａは２または３が好ましい。
【００６２】
本発明における有機重合体（Ａ）は公知の方法で製造できる。
【００６３】
有機重合体（Ａ）の分子量は１０００〜５００００が好ましい。有機重合体（Ａ）として加水分解性ケイ素基含有ポリエーテルを使用する場合には、分子量が８０００〜５００００のものを使用することが好ましい。分子量が８０００未満のときは硬化体が硬くなり、かつ伸びが低くなるので好ましくない。分子量が５００００を超えると硬化体の柔軟性および伸びは問題ないが、粘度が著しく大きくなり、実用性が低くなる。分子量は１００００〜３００００が特に好ましい。
【００６４】
［組成物および硬化性組成物］
本発明は、光硬化性官能基を有する重合単位を有する含フッ素重合体（Ｂ）と化合物（Ｃ）とを含有する組成物である。光硬化性官能基を有する重合単位を有する含フッ素重合体（Ｂ）に対して、特定の化合物（Ｃ）を、重合禁止剤または重合抑制剤として添加することにより、重合体（Ｂ）の貯蔵安定性、熱安定性を向上できる。
【００６５】
本発明は、また、加水分解により架橋可能な加水分解性ケイ素基を分子内に１つ以上有する有機重合体（Ａ）、光硬化性官能基を有する重合単位を有する含フッ素重合体（Ｂ）および化合物（Ｃ）を含有する硬化性組成物、である。
【００６６】
化合物（Ｃ）を含まず、光硬化性官能基を有する重合単位を有する重合体（Ｂ）および、加水分解により架橋可能な加水分解性ケイ素基を分子内に１つ以上有する有機重合体（Ａ）を含有する硬化性組成物は公知である。
【００６７】
しかし、本発明のように、光硬化性官能基を有する含フッ素重合体（Ｂ）とともに化合物（Ｃ）を、加水分解性ケイ素基含有有機重合体（Ａ）を硬化成分とする硬化性組成物に配合した場合、重合体（Ｂ）のみを配合した場合に見られた硬化性組成物の製造過程でのゲル化や増粘は起きにくいことがわかった。また重合体（Ｂ）と化合物（Ｃ）が配合された状態においても硬化性組成物の貯蔵安定性および物性が損なわれることもなく、かつ硬化性組成物が硬化して得られる硬化体の表面耐汚染性に優れることが見出された。
【００６８】
表面耐汚染性に優れる理由は、明らかではないが次のように考えられる。本発明における含フッ素重合体（Ｂ）は、有機重合体（Ａ）の硬化触媒として用いられる有機錫触媒などの作用によって、高分子量化しゲル化する性質がある。しかし化合物（Ｃ）が存在することにより反応性が抑えられるので、含フッ素重合体（Ｂ）が表面移行する前に、硬化性組成物内部で反応し硬化・ゲル化することを防止できると考えられる。
【００６９】
含フッ素重合体（Ｂ）は、有機重合体（Ａ）１００質量部に対し、０．１〜４０質量部、特に０．５〜２０質量部使用することが好ましい。
【００７０】
［その他］
本発明の、有機重合体（Ａ）、光硬化性官能基を有する重合単位を有する含フッ素重合体（Ｂ）、および、化合物（Ｃ）を含有する硬化性組成物には、必要により、光重合開始剤、充填剤、可塑剤、硬化触媒、その他の添加剤などを配合してもよい。
【００７１】
光重合開始剤としては、ベンゾフェノン、アセトフェノン、ベンゾイン、２−クロロチオキサントン、ベンジル、２−エチルアントラキノン、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オンなどを例示できる。
【００７２】
充填剤としては、炭酸カルシウム、フュームシリカ、沈降性シリカ、無水ケイ酸、含水ケイ酸およびカーボンブラック、炭酸マグネシウム、ケイソウ土、焼成クレー、クレー、タルク、酸化チタン、ベントナイト、有機ベントナイト、酸化第二鉄、酸化亜鉛、活性亜鉛華、シラスバルーン、木粉、パルプ、木綿チップ、マイカ、くるみ穀粉、もみ穀粉、グラファイト、アルミニウム微粉末、フリント粉末などの粉体状充填剤、ガラス繊維、ガラスフィラメント、炭素繊維、ケブラー繊維、ポリエチレンファイバーなどの繊維状充填剤が例示できる。
【００７３】
可塑剤としては、フタル酸ジオクチル、フタル酸ジブチル、フタル酸ブチルベンジルなどのフタル酸エステル類、脂肪族カルボン酸エステル、アルコールエステル類、リン酸エステル類、エポキシ可塑剤、ポリエステル系可塑剤、ポリエーテル類、各種オリゴマー類などの高分子可塑剤が例示される。
【００７４】
硬化促進触媒としては、２−エチルヘキサン酸錫、ジブチル錫ジラウレート、ジオクチル錫ジラウレートおよびカルボン酸型有機錫化合物およびこれらのカルボン酸型有機錫化合物と上記のアミン類との混合物、アルキルチタン酸塩等の金属塩、リン酸等の酸性化合物、脂肪族ジアミン、脂肪族ポリアミン類、複素環式アミン類、芳香族アミン類、エタノールアミン類、トリエチルアミン、エポキシ樹脂の硬化剤として用いられる各種変性アミンなどのアミン化合物。含硫黄型有機錫化合物、有機錫オキシド、および有機錫オキシドとフタル酸ジオクチルなどのエステル化合物との反応生成物、キレート錫化合物およびこれらの錫化合物とアルコキシシランとの反応生成物等の錫化合物が挙げられる。
【００７５】
その他添加剤としては、接着性を改良する目的で用いられる接着性付与剤等が挙げられる。これらの接着性付与剤としては（メタ）アクリロイルオキシ基含有シラン類、アミノ基含有シラン類、メルカプト基含有シラン類、エポキシ基含有シラン類、カルボキシル基含有シラン類などがある。
【００７６】
また２種以上のシランカップリング剤を反応させて得られる反応物を用いてもよい。反応物の例としてはアミノ基含有シラン類とエポキシ基含有シラン類との反応物、アミノ基含有シラン類と（メタ）アクリロイルオキシ基含有シラン類との反応物、エポキシ基含有シラン類とメルカプト基含有シラン類の反応物、メルカプト基含有シラン類どうしの反応物などが挙げられる。これらの反応物は該シランカップリング剤を混合し室温〜１５０℃の温度範囲で１〜８時間撹拌することによって容易に得られる。
その他にも各種溶剤、脱水剤、チキソ性付与剤、老化防止剤などを配合することができる。
【００７７】
上記の光重合開始剤、充填剤、可塑剤、硬化促進触媒、その他の添加剤等は単独で使用してもよく、２種類以上併用してもよい。
【００７８】
［用途］
本発明の組成物は、建築用のまたはそれ以外の用途の、シーリング材、接着剤、コーティング材、防水剤などの用途に使用できる硬化性組成物の添加剤として使用できる。特に加水分解性ケイ素基を有する有機重合体を硬化成分とする硬化性組成物の添加剤として使用できる。
【００７９】
また、本発明の硬化性組成物は、建築用のまたはそれ以外の用途の、シーリング材、接着剤、コーティング材、防水剤などの用途に使用できる。特に硬化体の表面耐汚染性が要求される用途に好適である。
【００８０】
【実施例】
以下に本発明の実施例を挙げるが、本発明はこれらに限定されない。なお、実施例で使用した化合物Ｘ１〜Ｘ３は下記の化合物である。
【００８１】
Ｘ１：２，６−ジ−ｔ−ブチル−４−メチルフェノール、
Ｘ２：ニトロソフェニルヒドロキシアミンアンモニウム塩、
Ｘ３：ニトロソフェニルヒドロキシアミンアルミニウム塩。
【００８２】
（例１）「含フッ素重合体の合成」
Ｃ_ｔＦ_２ｔ＋１ＣＨ_２ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２（ｔの平均値９）２３．９ｇ、アクリル酸（２−ヒドロキシエチル）エステル５．４ｇ、メチルイソブチルケトン３０．０ｇおよびアゾイソブチロニトリル１．５ｇを１００ｍＬフラスコに投入し、窒素雰囲気下、７０℃にて１０時間加熱し重合させた。その後、化合物Ｘ１の０．３ｇ、メタクリル酸（２−イソシアネートエチル）エステル３．１ｇ、触媒量の２−エチルヘキサン酸錫を入れ、５０℃にて２０時間加熱し反応させた。ついで、溶媒および未反応モノマーを留去し、アクリロイル基含量２０モル％、重量平均分子量７０００の含フッ素重合体組成物Ｂ１−１を得た。なお、組成物Ｂ１−１は、少量のＸ１を含む。
【００８３】
含フッ素重合体組成物Ｂ１−１を７０℃のオーブンに保管し、貯蔵安定性試験を行った。結果を表１に示す。貯蔵安定性試験の評価基準は次の判定基準による。なお、「ゲル化」とは、加水分解性ケイ素基含有有機重合体を含有する硬化性組成物に配合できない状態に固化した状態をいう。
○：２４時間以上ゲル化しない、
×：２４時間以内にゲル化する。
【００８４】
（例２〜例６）
例１において、溶媒と未反応モノマーを留去する前に、含フッ素重合体Ｂ１−１の１００ｇに対して、表１に示した化合物（Ｘ１〜Ｘ３）を表１に示すｇ数、さらに添加したこと以外は、例１と同様に行い、含フッ素重合体組成物Ｂ１−２〜Ｂ１−６を得た。例１と同様に貯蔵安定性試験を行った。結果を表１に示す。
【００８５】
（例７）「含フッ素重合体の合成」
内容積５５０ｍＬのステンレス製撹拌機付耐圧反応器に、キシレン２５２ｇ、エタノール７１ｇ、炭酸カリウム１．４ｇ、アゾイソブチロニトリル４．４ｇ、エチルビニルエーテル４０．０ｇおよびヒドロキシブチルビニルエーテル１６．１ｇを入れた後、液体窒素により溶残空気を除去し、次いでテトラフルオロエチレン６９．５ｇを導入し、６５℃にて１０時間加熱し重合させた後、反応溶液を濾過し、溶媒を留去した。１Ｌフラスコに移しとり、アセトン１００ｇ、トリエチルアミン１６．４ｇおよびヒドロキノンモノメチルエーテル１５ｍｇを加え、窒素気流下４０℃で１０分間撹拌した。
【００８６】
次いで、シンナモイルクロリド２４．６ｇを１００ｇのアセトンに溶かした溶液を３０分にわたり滴下し、５７℃で１時間３０分反応させた。その後、アンモニウム塩を濾別し、濾液を再沈澱させ、シンナモイル基含有量１０モル％、重量平均分子量７０００の含フッ素重合体組成物Ｂ２−１を得た。例１と同様に貯蔵安定性試験を行った。結果を表１に示す。
【００８７】
（例８）
５００ｍＬフラスコに、例７において得られた含フッ素重合体組成物Ｂ２−１を１００ｇ、メチルイソブチルケトンを１００ｇ、化合物Ｘ３を表１に示したｇ数加え、均一に分散させた後、溶媒を留去し、含フッ素重合体組成物Ｂ２−２を得た。例１と同様に貯蔵安定性試験を行った結果を表１に示す。
【００８８】
【表１】

【００８９】
例１〜２および例７（比較例）、ならびに、例３〜６および例８（実施例）を比較することにより、本発明における特定の重合禁止剤または重合抑制剤配合した含フッ素重合体組成物は、熱安定性に優れることが分かる。
【００９０】
（例９〜１１）「硬化性組成物の製造例」
エチレングリコールを開始剤として、亜鉛ヘキサシアノコバルテート錯体触媒を用いて製造した、数平均分子量１７０００のポリオキシプロピレンポリオールの末端水酸基をアリルオキシ基に変換後、さらにメチルジメトキシシリルプロピルオキシ基（全末端の７５％）に変換してケイ素基含有重合体を得た。
【００９１】
該重合体１００部に対し、上記含フッ素重合体組成物Ｂ１−１（例９）またはＢ１−６（例１０）を５部、表面処理膠質炭酸カルシウム（白石工業社製、白艶化ＣＣＲ）１２０部、重質炭酸カルシウム（白石工業社製ホワイトンＳＢ）２０部、酸化チタン（イシハラ産業社製Ｒ８２０）１０部、フタル酸ジオクチル３０部、チキソ性付与剤（楠本化成社製ディスパロン３０５）３部、エポキシ化可塑剤（新日本理化社製サンソサイザーＥＰＳ）２０部、トリメチロールプロパントリスアクリレート（東亞合成社製アロニクスＭ３０９）３部、紫外線吸収剤（チバ・ガイギー社製、チヌビン３２７）１部、酸化防止剤（チバ・ガイギー社製、イルガノックス１０１０）１部、をプラスチック製容器内で混ぜ三本ロールにて混練し、これを主剤とした。
【００９２】
また、硬化剤として２−エチルヘキサン酸錫３部、ラウリルアミン１部、フタル酸ジオクチル６部、重質炭酸カルシウム（白石工業社製ホワイトンＳＢ）１５部、カオリン（ＥＮＧＥＬＨＡＲＤ社製カオリンＡＳＰ−１７０）５０部を混合したものを用いた。上記主剤１００部に対し硬化剤３部加え、十分に混練した。
【００９３】
この混練物を縦１００ｍｍ、横２５ｍｍ、厚さ５ｍｍの型に入れ、シート状とし２０℃、６５％湿度の恒温恒湿槽に７日間入れ、硬化体シートを得た。また、また、同様に、含フッ素重合体組成物を含まない硬化体シートを作成した（例１１）。
【００９４】
この硬化体シートを茨城県鹿島郡にある旭硝子株式会社鹿島工場内に４５度の角度に放置し、半年後の天曝耐汚染性を目視にて観察した。耐汚染性の状態は、例１０が最も優良であり、次いで例９が優良であったが、これらに比べると例１１は甚だ汚れがひどく付着していた。
【００９５】
【表２】

【００９６】
【発明の効果】
本発明における特定の重合禁止剤または重合抑制剤を添加した含フッ素重合体組成物からなる組成物は熱安定性が良好で貯蔵安定性に優れる効果を有する。その結果、加水分解性ケイ素基含有有機重合体を含有する硬化性組成物に配合する過程でもゲル化や増粘を起こさず、硬化性組成物に配合された状態においても貯蔵安定性がよい。硬化性組成物の硬化体の基本物性に悪影響を与えることなく、硬化性組成物の硬化体の耐候性、表面耐汚染性を向上させることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention improves the weather resistance and surface contamination resistance of a cured product of a curable composition by adding it to a curable composition containing an organic polymer having one or more hydrolyzable silicon groups in the molecule as a curing component. The present invention relates to compositions that can be improved and that themselves have thermal stability, as well as their use.
[0002]
[Prior art]
A curable composition in which various compounding agents are blended with a polymer having one or more hydrolyzable silicon groups in the molecule is widely used for sealing materials, waterproofing materials, coating materials, adhesives and the like.
[0003]
However, for example, when this curable composition is used for a building sealing material, there is a problem with the long-term weather resistance of the cured body depending on the composition and construction conditions, and after the long-term outdoor exposure, stickiness and cracks occur on the surface. Or dirt such as dust adheres to it, which causes the appearance to be damaged.
[0004]
For the purpose of solving this problem, by adding a photocurable substance that can be cured by light energy to a curable composition containing an organic polymer having a hydrolyzable silicon group, the weather resistance and surface of the cured product are improved. Proposals have been made to improve stain resistance. This proposal is based on the idea of improving the weather resistance and surface contamination resistance of a cured body by forming a cured film of a photocurable material on the surface of the cured body after applying the curable composition (for example, patents) Literatures 1-3).
[0005]
It has also been proposed that by blending a fluorine-containing polymer having a polymer unit having a photocurable functional group with an organic polymer having a hydrolyzable silicon group, it exhibits better weather resistance and surface contamination resistance. (Patent Documents 4 to 5).
[0006]
[Patent Document 1]
Japanese Examined Patent Publication No. 62-26349
[Patent Document 2]
JP-A-57-190044
[Patent Document 3]
JP-A-3-294361
[Patent Document 4]
JP-A-9-291184
[Patent Document 5]
Japanese Patent Laid-Open No. 9-208782
[0007]
[Problems to be solved by the invention]
However, a photo-curable substance that can be cured by light energy is gradually cured by energy other than light. Therefore, during long-term storage or during the manufacture of a sealing material, the photo-curable substance is heated by heating. There was a problem of loss of original performance due to thickening, gelation and solidification.
[0008]
In addition, after construction of the curable composition, before the cured film is formed by the curing of the photocurable material on the cured body surface by natural light, it is also cured inside the cured body by the heat of natural light, etc. There was a problem that the effect was not fully exhibited.
[0009]
[Means for Solving the Problems]
As a result of intensive studies aimed at solving the above-mentioned problems, the inventors of the present invention have a composition containing a fluoropolymer having a polymer unit having a photocurable functional group, which contains a specific compound. Has a good storage stability in itself and does not cause gelation or thickening even in the process of blending with a curable composition containing an organic polymer having a hydrolyzable silicon group. Even if it is blended in a product, the storage stability and physical properties of the curable composition are not impaired, and the surface of the curable composition is sufficiently photocured after application of the curable composition to improve the surface contamination resistance of the curable composition. As a result, the inventors have found out that the present invention can be achieved. The present invention is the following invention.
[0010]
A composition comprising a fluorine-containing polymer (B) having a polymer unit having a photocurable functional group, and a compound (C) having a nitroso group, a hydroxyamino group or a salt thereof. An organic polymer having one or more hydrolyzable silicon groups crosslinkable by hydrolysis (A) a fluoropolymer (B) having a polymer unit having a photocurable functional group, and a nitroso group or hydroxy A curable composition containing a compound (C) having an amino group or a salt thereof.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
[Fluoropolymer (B) having a polymerization unit having a photocurable functional group]
The fluorine-containing polymer (B) having a polymer unit having a photocurable functional group in the present invention has a polymer unit having a photocurable functional group selected from an acryloyl group, a methacryloyl group, a cinnamoyl group and an azide group.
[0012]
The fluorine-containing polymer (B) having a polymer unit having a photocurable functional group has a polymer unit (p) having a polyfluorohydrocarbon group in an amount of 20 to 95 mol% based on the total polymer units, and a photocurable functional group. A polymer (B1) containing 5 to 80 mol% of the polymerized units (q) having a total amount of 5 to 80 mol% and optionally 0 to 75 mol% of the other polymerized units (r) based on the total polymerized units. Or 20 to 70 mol% of the polymerized units (s) based on fluoroolefin with respect to all polymerized units, and 1 to 80 mol% of polymerized units (t) having a photocurable functional group with respect to all polymerized units. And it is preferably a polymer (B2) having 0 to 70 mol% of other polymerized units (u) relative to the total polymerized units.
[0013]
[Fluoropolymer (B1)]
[Polymerizable monomer (a)]
The fluoropolymer (B1) in the present invention has a polymer unit (p) having a polyfluorohydrocarbon group. The polymerized unit (p) having a polyfluorohydrocarbon group is preferably a polymerized unit produced by polymerizing the polymerizable monomer (a) having a polyfluorohydrocarbon group. Examples of the polymerizable unsaturated group in the polymerizable monomer (a) include a vinyl group, an allyl group, a (meth) acryloyl group, and an isopropenyl group.
[0014]
The polyfluorohydrocarbon group means a group in which two or more hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms, and a group in which substantially all of the hydrogen atoms are substituted with fluorine atoms is preferable. The number of carbon atoms of the polyfluorohydrocarbon group is preferably 2 to 40, particularly 2 to 22, and more preferably 4 to 18. Most preferably, it is 6-14.
[0015]
The polyfluorohydrocarbon group in the present invention may contain a linking group. A moiety that is a linking moiety in which a polyfluorohydrocarbon group is bonded to another group and is an organic group that does not contain a fluorine atom is referred to as a linking group. With respect to the number of fluorine atoms in the polyfluorohydrocarbon group excluding the linking group, the ratio of the number of substituted fluorine atoms to the number of hydrogen atoms in the unsubstituted hydrocarbon group is preferably 50% or more, particularly preferably 80% or more. The case of 100% is most preferable. Furthermore, some or all of the hydrogen atoms that are not substituted may be substituted with chlorine atoms. The tip portion of the polyfluorohydrocarbon group is preferably a perfluorohydrocarbon group portion.
[0016]
The structure of the polyfluorohydrocarbon group may be linear or branched, and is preferably linear. The polyfluorohydrocarbon group is preferably monovalent to trivalent, particularly preferably monovalent or divalent.
[0017]
In the polyfluorohydrocarbon group, an etheric oxygen atom or a thioetheric sulfur atom may be inserted between carbon-carbon bonds. Moreover, you may have unsaturated groups, such as a carbon-carbon unsaturated double bond.
[0018]
Examples of the polymerizable monomer (a) include the following.
C ₈ F ₁₇ CH = CH ₂ Such as polyfluoroolefin compounds.
A polyfluoroalkyl ester of acrylic acid represented by Formula 2.
A polyfluoroalkyl ester of methacrylic acid represented by Formula 3.
Vinyl (polyfluoroalkyl) ether represented by Formula 4.
Allyl (polyfluoroalkyl) ether represented by the formula 5:
Polyfluoroalkylcarboxylic acid vinyl ester represented by Formula 6.
F (CF ₂ ) _m CH ₂ NHCOCH = CH ₂ Such as acrylic amide.
F (CF ₂ ) _m CH ₂ NHCOC (CH ₃ ) = CH ₂ Such as methacrylamide.
[0019]
[Chemical formula 2]

[0020]
R ^f1 , R ^f2 Is a polyfluorohydrocarbon group.
R ^f1 Is preferably a polyfluorohydrocarbon group containing a linking group, and R ^f2 Is preferably a polyfluorohydrocarbon group containing no linking group.
[0021]
The fluorine-containing polymer (B1) is preferably a polymer containing 20 to 95 mol%, particularly 30 to 90 mol% of the polymer units (p) having a polyfluorohydrocarbon group with respect to all the polymerized units. When the amount is less than 20 mol%, sufficient surface contamination resistance is not exhibited, and stains and the like may become remarkable in long-term use.
[0022]
[Polymerizable monomer (b) / (c)]
The polymerized unit (q) having a photocurable functional group is a polymerized unit based on the polymerizable monomer (b) having a photocurable functional group, or has a functional group capable of introducing a photocurable functional group. Polymerization based on the polymerizable monomer (c) produced by introducing a photocurable functional group after copolymerizing the polymerizable monomer (c) with the polymerizable monomer (a) to produce a copolymer. It is preferably a unit and a polymerized unit having a photocurable functional group introduced therein.
[0023]
In the former case, the photocurable functional group is limited to a functional group having no thermal polymerizability among the groups exemplified above. Specifically, a cinnamoyl group is preferable. Specific examples of the polymerizable monomer (b) include allyl cinnamate, cinnamate esters of allyl alcohol-alkylene oxide adducts, and cinnamic acid esters of acrylic acid (2-hydroxyethyl) ester.
[0024]
The latter polymerizable monomer (c) is a polymerizable monomer having a polymerizable moiety and having a functional group. After polymerization, the functional group and a reactive group are combined with a photocurable functional group. The photocurable functional group can be introduced by reacting the compound having the same. The functional group is preferably a hydroxyl group.
[0025]
Examples of the hydroxyl group-containing polymerizable monomer include allyl alcohol, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, (meth) acrylic acid (hydroxyalkyl) ester, and alkylene oxide adducts thereof. In addition, monomers obtained by reacting a diol with a polymerizable monomer having a functional group capable of reacting with a hydroxyl group such as acrylic acid, methacrylic acid, and allyl glycidyl ether may also be used. In the present invention, for example, acrylic acid and methacrylic acid are sometimes referred to as (meth) acrylic acid for convenience.
[0026]
Examples of the compound having both a hydroxyl group-reactive group and a photocurable functional group include (meth) acrylic acid, (meth) acrylic acid chloride, (meth) acrylic acid (2-isocyanatoethyl) ester, ( Examples include (meth) acrylic acid derivatives such as a reaction product of (meth) acrylic acid and diisocyanate such as isocyanatephorone diisocyanate, and cinnamoyl chloride.
[0027]
A copolymerizable monomer (c) such as a hydroxyl group-containing polymerizable monomer and a polymerizable monomer (a) are copolymerized to obtain a copolymer (D), and then directly onto a functional group such as a hydroxyl group in (D). In addition, a compound having both a functional group such as a hydroxyl group and a reactive group and a photocurable functional group may be reacted, and a polyether chain directly bonded to a functional group such as a hydroxyl group in the copolymer; A spacer selected from a polyurethane chain, a polyamide chain, and a polyester chain may be generated, and then a photocurable functional group may be introduced. In particular, a polyester chain obtained by ring-opening polymerization of a polyether ester or a cyclic ester such as caprolactone, which is obtained by ring-opening polymerization of an alkylene oxide having about 2 to 10 carbon atoms, particularly 2 to 6 carbon atoms, is preferable. In addition, when introduce | transducing this photocurable functional group into a copolymer (D), the group which can introduce | transduce a photocurable functional group may remain | survive.
[0028]
The fluorine-containing polymer (B1) preferably contains 5 to 80 mol% of a polymer unit (q) having a photocurable functional group with respect to all polymer units. If the number of polymerized units (q) having a photocurable functional group is less than 5 mol%, a sufficient photocured film may not be formed, and stains and the like may become prominent during long-term use. It is preferable to contain 10 to 70 mol%, particularly 10 to 50 mol%, based on all polymerized units.
[0029]
[Polymerizable monomer (d)]
The fluoropolymer (B1) may have a polymerization unit (r) other than the polymerization unit (p) and the polymerization unit (q). The polymerized unit (r) is preferably a polymerized unit formed by polymerizing a polymerizable monomer (d) other than (a) and (b). Moreover, it is a polymerization unit produced | generated when a polymerizable monomer (c) superpose | polymerizes, Comprising: The polymerization unit in which the photocurable functional group was not introduce | transduced may be sufficient.
[0030]
It is preferable that a polymerization unit (r) is the ratio of 0-75 mol% with respect to all the polymerization units. That is, the total of the polymerized units (p) and the polymerized units (q) is preferably contained at a ratio of 25 mol% or more with respect to the total polymerized units.
[0031]
Examples of the polymerizable monomer (d) include polymerizable monomers having a polymerizable site such as vinyl group, allyl group, acryloyl group, methacryloyl group, and isopropenyl group.
[0032]
Specifically, vinyl ethers, olefins, allyl ethers, vinyl esters, allyl esters, acrylic acid esters, methacrylic acid esters, isopropenyl ethers, isopropenyl esters, crotonic acid esters and other polymerizations Can be exemplified. Of these, compounds having a linear, branched or alicyclic alkyl group having about 1 to 15 carbon atoms are preferred. More specific compounds include the following.
[0033]
Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, chloroethyl vinyl ether; olefins such as ethylene, propylene, 1-butene, isobutylene, cyclohexene, styrene, α-methylstyrene; methyl allyl ether , Allyl ethers such as ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl caproate, vinyl caprylate, Veova 9 and Veova 10 (Trade name of vinyl ester of branched fatty acid having 9 or 10 carbon atoms, manufactured by Shell Chemical Co., Ltd.), fatty acid vinyl ester such as vinyl versatate Allyl esters such as allyl acetate; (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate; crotonic acid Crotonic esters such as ethyl, butyl crotonate and cyclohexyl crotonate; (meth) acrylic amides such as (meth) acrylic amide; cyano group-containing monomers such as acrylonitrile and 2,4-dicyanobutene-1; isoprene And dienes such as butadiene; halogenated olefins such as vinyl chloride and vinylidene chloride.
[0034]
Examples thereof include a polymerizable monomer having a polyoxyalkylene chain having a molecular weight of about 100 to 3,000, such as a polyoxypropylene glycol monoalkyl ether mono (meth) acrylate having a molecular weight of 100 to 3,000. Moreover, the polymerizable monomer which has a hydrolyzable silicon group represented by Formula 1, and the below-mentioned fluoroolefin (e) can also be used.
[0035]
The polymerization method may be any of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. Polymerization is performed by causing a predetermined amount of polymerizable monomer to act on a polymerization initiator such as a polymerization initiator or ionizing radiation. Is called. In addition, the molecular weight may be adjusted by the presence of a suitable chain transfer agent. Furthermore, you may superpose | polymerize in presence of the organic polymer which has a hydrolysable silicon group mentioned later.
[0036]
The number average molecular weight of the fluoropolymer (B1) is preferably 1,000 to 500,000. If the number average molecular weight exceeds 500,000, it is difficult to transfer to the surface of the cured product. When the number average molecular weight is less than 1000, physical properties such as weather resistance are inferior. Preferably, it is 3000-50000, especially 3000-15000.
[0037]
[Fluoropolymer (B2)]
[Polymerizable monomer (e)]
The fluoropolymer (B2) in the present invention preferably contains 20 to 70 mol%, particularly 30 to 60 mol%, of the polymerized units (s) based on the fluoroolefin (e) with respect to the total polymerized units. The polymerized unit (s) based on the fluoroolefin is a polymerized unit obtained by polymerizing the fluoroolefin (e).
[0038]
The fluoroolefin (e) is a compound having an ethylenically unsaturated group, and is a compound in which one or more hydrogen atoms directly bonded to carbon atoms forming the ethylenically unsaturated group are substituted with fluorine atoms. . A compound having 2 to 6 carbon atoms is preferable, and a compound having 2 to 4 carbon atoms is particularly preferable. The fluoroolefin (e) may be a compound containing a halogen atom other than a fluorine atom. Particularly preferred are perhaloolefins in which the hydrogen atom directly connected to the carbon atom forming the ethylenically unsaturated group is completely substituted with a halogen atom.
[0039]
Specific examples of the fluoroolefin (e) include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene and the like.
[0040]
The polymer unit (t) having a photocurable functional group is a polymer unit similar to the polymer unit (q) described in the polymer (B1), and is obtained by polymerizing the polymerizable monomer (b). Polymerized units obtained by polymerizing the unit or polymerizable monomer (c) and then introducing a photocurable functional group are preferred.
[0041]
The polymerized unit (t) having a photocurable functional group is contained in a proportion of 5 to 80 mol% with respect to the total polymerized units, and contained in a proportion of 5 to 40 mol% with respect to the total polymerized units. It is particularly preferred.
[0042]
The fluorine-containing polymer of the present invention may be composed only of the polymerization unit (s) and the polymerization unit (t), and the polymerization unit (u) other than (s) and (t), that is, (e), ( It may have a polymerized unit (u) based on the monomer (j) other than g). In this case, the polymerization unit (u) is preferably in a proportion of 0 to 70 mol% with respect to all the polymerization units. That is, the total of the polymerization units (s) and the polymerization units (t) is preferably 30 mol% or more with respect to all the polymerization units.
[0043]
In the polymerizable monomer (j), the hydrogen atom directly bonded to the carbon atom forming the ethylenically unsaturated group is not substituted with a fluorine atom and does not have a photocurable functional group. What was illustrated by the above-mentioned polymerizable monomer (d) can be used. A polymerizable monomer (a) can also be used.
As the polymerization method, a method similar to the method exemplified for the polymer (B1) can be adopted.
The number average molecular weight of the fluoropolymer (B2) is preferably 1,000 to 500,000. If the number average molecular weight exceeds 500,000, it is difficult to transfer to the surface of the cured product. When the number average molecular weight is less than 1000, physical properties such as weather resistance are inferior. Preferably, it is 3000-50000, especially 3000-15000.
[0044]
[Compound (C)]
In the present invention, the compound (C) having a nitroso group or a hydroxyamino group or a salt thereof is used. The compound (C) is considered to function as a polymerization inhibitor or a polymerization inhibitor. Specific examples include N-methyl-N-nitrosoaniline, N-nitrosophenylhydroxylamine or salts thereof, and N-nitrosophenylhydroxylamine salts are preferred.
[0045]
As N-nitrosophenylhydroxylamine salts, N-nitrosophenylhydroxyamine ammonium salts and N-nitrosophenylhydroxyamine aluminum salts are preferable.
[0046]
These can be used alone or in combination. Moreover, you may use together with another polymerization inhibitor or a polymerization inhibitor. Further, other polymerization inhibitors or polymerization inhibitors may be used in combination. Specifically, phenol compounds such as hydroquinone, p-methoxyphenol, 4-t-butylcatechol, 2-t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol, phenothiazine, etc. Can be mentioned.
[0047]
The amount of the compound (C) used is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the fluoropolymer (B) having a polymer unit having a photocurable functional group.
[0048]
When the amount is less than 0.001 part by mass, the storage stability effect and the effect of preventing the internal curing before the surface transition after the curable composition construction is not sufficiently exhibited. Moreover, when it exceeds 10 mass parts, the photocurability after the surface transfer after construction of a curable composition will also be inhibited, and the surface contamination-resistant effect of a curable composition will not fully be exhibited. A more desirable ratio is in the range of 0.001 to 10 parts by mass, and particularly preferably in the range of 0.01 to 5 parts by mass.
[0049]
The compound (C) is preferably added to the fluoropolymer (B) immediately after the production of the fluoropolymer (B) or during the production. When the fluoropolymer (B) is produced in an organic solvent, it can be added before or after the solvent is distilled off. In addition, in the case of introducing a photocurable functional group after producing a fluoropolymer having a functional group capable of introducing a photocurable functional group in advance, the compound before introducing the photocurable functional group unless the reaction is inhibited (C) can be added.
[0050]
[Organic polymer (A)]
The organic polymer (A) having one or more hydrolyzable silicon groups (hereinafter also simply referred to as hydrolyzable silicon groups) crosslinkable by hydrolysis in the present invention is selected from polyethers, polyesters and polycarbonates. And an organic polymer derived from the organic polymer. Polymerization of olefins such as ethylene, propylene and isobutylene, (meth) acrylic acid esters, vinyl alkyl ethers, dienes such as butadiene and chloroprene, and halogenated olefins such as chlorotrifluoroethylene and tetrafluoroethylene And a hydrolyzable silicon group-containing vinyl polymer obtained by copolymerizing a polymerizable monomer and a hydrolyzable silicon group-containing polymerizable monomer.
[0051]
In particular, an organic polymer derived from an organic polymer selected from polyether, polyester and polycarbonate is preferable. Of these, hydrolyzable silicon group-containing polyethers derived from polyethers are particularly preferred.
[0052]
The hydrolyzable silicon group-containing polyether is particularly preferably derived from a hydroxyl group-containing polyether obtained by ring-opening polymerization reaction of a cyclic ether such as propylene oxide with an initiator containing active hydrogen in the presence of a catalyst. .
[0053]
Initiators include polyhydric active hydrogen compounds such as polyhydric alcohols, polycarboxylic acids, and polyamines, and terminally unsaturated group-containing monools, and catalysts include alkali metals such as sodium, potassium, cesium, and the like. And alkali metal compounds such as hydroxides, double metal cyanide complexes, metal porphyrin complexes, and the like.
[0054]
In the present invention, the hydrolyzable silicon group is a group capable of causing a condensation reaction by moisture, a curing catalyst, or the like, such as a silanol group or an alkoxysilyl group, and promoting high molecular weight by crosslinking of the organic polymer. Is a group represented by Formula 1.
[0055]
[Chemical Formula 3]

[0056]
Where R ¹ Is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a hydroxyl group or a monovalent hydrolyzable group, and a is an integer of 1 to 3.
[0057]
When the hydrolyzable silicon group-containing polyether is derived from a hydroxyl group-containing polyether, the hydrolyzable silicon group represented by the formula 1 is usually introduced via an organic group. Therefore, the organic polymer (A) in the present invention preferably has a group represented by Formula 7.
[0058]
[Formula 4]

[0059]
Where R ⁰ Is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ , X and a are the same as above.
[0060]
Where R in Equation 7 ⁰ Is preferably a divalent hydrocarbon group having 8 or less carbon atoms. R in Formula 1 and Formula 7 ¹ Is preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group, particularly preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group or a phenyl group.
[0061]
X in Formula 1 and Formula 7 is a hydroxyl group or a monovalent hydrolyzable group. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, or a ketoximate group. Is preferred. Among these, the number of carbon atoms of the hydrolyzable group having a carbon atom is preferably 6 or less, particularly 4 or less. Preferred X is an alkoxy group having 4 or less carbon atoms, particularly a methoxy group, an ethoxy group or a propoxy group. A in Formula 1 and Formula 7 is preferably 2 or 3.
[0062]
The organic polymer (A) in the present invention can be produced by a known method.
[0063]
The molecular weight of the organic polymer (A) is preferably 1000 to 50000. When a hydrolyzable silicon group-containing polyether is used as the organic polymer (A), it is preferable to use one having a molecular weight of 8000 to 50,000. When the molecular weight is less than 8000, the cured product becomes hard and the elongation becomes low. When the molecular weight exceeds 50,000, there is no problem in the flexibility and elongation of the cured product, but the viscosity is remarkably increased and the practicality is lowered. The molecular weight is particularly preferably 10,000 to 30,000.
[0064]
[Composition and curable composition]
The present invention is a composition containing a fluoropolymer (B) having a polymer unit having a photocurable functional group and a compound (C). Storage of the polymer (B) by adding a specific compound (C) as a polymerization inhibitor or polymerization inhibitor to the fluoropolymer (B) having a polymer unit having a photocurable functional group Stability and thermal stability can be improved.
[0065]
The present invention also provides an organic polymer (A) having one or more hydrolyzable silicon groups in the molecule that can be crosslinked by hydrolysis, and a fluorinated polymer (B) having a polymer unit having a photocurable functional group. And a curable composition containing the compound (C).
[0066]
A polymer (B) having no polymer (C) and having a polymer unit having a photocurable functional group, and an organic polymer (A) having at least one hydrolyzable silicon group crosslinkable by hydrolysis in the molecule ) -Containing curable compositions are known.
[0067]
However, as in the present invention, a curable composition comprising a compound (C) together with a fluoropolymer (B) having a photocurable functional group and a hydrolyzable silicon group-containing organic polymer (A) as a curing component. It was found that gelation and thickening in the production process of the curable composition observed when only the polymer (B) was blended did not occur. The surface of the cured product obtained by curing the curable composition without impairing the storage stability and physical properties of the curable composition even when the polymer (B) and the compound (C) are blended. It has been found to be excellent in stain resistance.
[0068]
The reason for excellent surface contamination resistance is not clear, but is considered as follows. The fluoropolymer (B) in the present invention has the property of becoming high molecular weight and gelled by the action of an organic tin catalyst used as a curing catalyst for the organic polymer (A). However, since the reactivity is suppressed by the presence of the compound (C), it is considered that the reaction can be prevented from curing and gelling by reacting inside the curable composition before the fluoropolymer (B) migrates to the surface. It is done.
[0069]
The fluoropolymer (B) is preferably used in an amount of 0.1 to 40 parts by weight, particularly 0.5 to 20 parts by weight, based on 100 parts by weight of the organic polymer (A).
[0070]
[Others]
In the curable composition containing the organic polymer (A), the fluorinated polymer (B) having a polymer unit having a photocurable functional group, and the compound (C) according to the present invention, if necessary, You may mix | blend a polymerization initiator, a filler, a plasticizer, a curing catalyst, another additive, etc.
[0071]
Examples of photopolymerization initiators include benzophenone, acetophenone, benzoin, 2-chlorothioxanthone, benzyl, 2-ethylanthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and the like. It can be illustrated.
[0072]
Fillers include calcium carbonate, fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, second oxide Powdered fillers such as iron, zinc oxide, activated zinc white, white balloon, wood flour, pulp, cotton chips, mica, walnut flour, rice flour, graphite, aluminum fine powder, flint powder, glass fiber, glass filament, Examples thereof include fibrous fillers such as carbon fiber, Kevlar fiber, and polyethylene fiber.
[0073]
Plasticizers include phthalates such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, aliphatic carboxylic esters, alcohol esters, phosphate esters, epoxy plasticizers, polyester plasticizers, polyethers And polymer plasticizers such as various oligomers.
[0074]
Examples of the curing accelerating catalyst include 2-ethylhexanoic acid tin, dibutyltin dilaurate, dioctyltin dilaurate, carboxylic acid type organic tin compounds, mixtures of these carboxylic acid type organic tin compounds and the above amines, alkyl titanates, etc. Metal salts, acid compounds such as phosphoric acid, aliphatic diamines, aliphatic polyamines, heterocyclic amines, aromatic amines, ethanolamines, triethylamine, various modified amines used as curing agents for epoxy resins, etc. Amine compounds. Tin compounds such as sulfur-containing organotin compounds, organotin oxides, reaction products of organotin oxides with ester compounds such as dioctyl phthalate, chelate tin compounds, and reaction products of these tin compounds with alkoxysilanes Can be mentioned.
[0075]
Examples of other additives include an adhesion-imparting agent used for the purpose of improving adhesion. Examples of these adhesion imparting agents include (meth) acryloyloxy group-containing silanes, amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, and carboxyl group-containing silanes.
[0076]
Moreover, you may use the reaction material obtained by making 2 or more types of silane coupling agents react. Examples of reactants include reactants of amino group-containing silanes and epoxy group-containing silanes, reactants of amino group-containing silanes and (meth) acryloyloxy group-containing silanes, epoxy group-containing silanes and mercapto groups Reaction products of silanes containing silanes, reaction products of silanes containing mercapto groups, and the like. These reactants can be easily obtained by mixing the silane coupling agent and stirring in the temperature range of room temperature to 150 ° C. for 1 to 8 hours.
In addition, various solvents, dehydrating agents, thixotropic agents, anti-aging agents, and the like can be blended.
[0077]
The above photopolymerization initiators, fillers, plasticizers, curing acceleration catalysts, other additives, and the like may be used alone or in combination of two or more.
[0078]
[Usage]
The composition of the present invention can be used as an additive for a curable composition that can be used for applications such as sealing materials, adhesives, coating materials, waterproofing agents, for architectural or other purposes. In particular, it can be used as an additive for a curable composition containing a hydrolyzable silicon group-containing organic polymer as a curing component.
[0079]
Moreover, the curable composition of this invention can be used for uses, such as a sealing material, an adhesive agent, a coating material, and a waterproofing agent, for construction or other uses. It is particularly suitable for applications that require surface contamination resistance of the cured product.
[0080]
【Example】
Examples of the present invention will be given below, but the present invention is not limited thereto. In addition, the compounds X1-X3 used in the Example are the following compounds.
[0081]
X1: 2,6-di-tert-butyl-4-methylphenol,
X2: nitrosophenylhydroxyamine ammonium salt,
X3: nitrosophenylhydroxyamine aluminum salt.
[0082]
(Example 1) “Synthesis of fluoropolymer”
C _t F _{2t + 1} CH ₂ CH ₂ OCOCH = CH ₂ (Average value of 9) 23.9 g, 5.4 g of acrylic acid (2-hydroxyethyl) ester, 30.0 g of methyl isobutyl ketone and 1.5 g of azoisobutyronitrile were put into a 100 mL flask, under a nitrogen atmosphere, Polymerization was carried out by heating at 70 ° C. for 10 hours. Thereafter, 0.3 g of Compound X1, 3.1 g of methacrylic acid (2-isocyanate ethyl) ester, and a catalytic amount of tin 2-ethylhexanoate were added and heated at 50 ° C. for 20 hours to be reacted. Subsequently, the solvent and the unreacted monomer were distilled off to obtain a fluorinated polymer composition B1-1 having an acryloyl group content of 20 mol% and a weight average molecular weight of 7000. Composition B1-1 contains a small amount of X1.
[0083]
The fluoropolymer composition B1-1 was stored in an oven at 70 ° C., and a storage stability test was performed. The results are shown in Table 1. The evaluation criteria for the storage stability test are based on the following criteria. In addition, "gelation" means the state solidified in the state which cannot be mix | blended with the curable composition containing a hydrolyzable silicon group containing organic polymer.
○: It does not gel for more than 24 hours.
X: Gelled within 24 hours.
[0084]
(Examples 2 to 6)
In Example 1, before distilling off the solvent and unreacted monomers, 100 g of the fluoropolymer B1-1 was added to the compounds (X1 to X3) shown in Table 1 in the number of g shown in Table 1. Except having done, it carried out similarly to Example 1 and obtained fluoropolymer composition B1-2 to B1-6. The storage stability test was conducted in the same manner as in Example 1. The results are shown in Table 1.
[0085]
(Example 7) “Synthesis of fluoropolymer”
In a pressure resistant reactor with a stirrer made of stainless steel having an internal volume of 550 mL, 252 g of xylene, 71 g of ethanol, 1.4 g of potassium carbonate, 4.4 g of azoisobutyronitrile, 40.0 g of ethyl vinyl ether and 16.1 g of hydroxybutyl vinyl ether were placed. Thereafter, dissolved air was removed with liquid nitrogen, and then 69.5 g of tetrafluoroethylene was introduced. After heating and polymerizing at 65 ° C. for 10 hours, the reaction solution was filtered and the solvent was distilled off. The flask was transferred to a 1 L flask, 100 g of acetone, 16.4 g of triethylamine and 15 mg of hydroquinone monomethyl ether were added, and the mixture was stirred at 40 ° C. for 10 minutes in a nitrogen stream.
[0086]
Next, a solution obtained by dissolving 24.6 g of cinnamoyl chloride in 100 g of acetone was added dropwise over 30 minutes and reacted at 57 ° C. for 1 hour and 30 minutes. Thereafter, the ammonium salt was filtered off and the filtrate was reprecipitated to obtain a fluorinated polymer composition B2-1 having a cinnamoyl group content of 10 mol% and a weight average molecular weight of 7000. The storage stability test was conducted in the same manner as in Example 1. The results are shown in Table 1.
[0087]
(Example 8)
In a 500 mL flask, 100 g of the fluoropolymer composition B2-1 obtained in Example 7, 100 g of methyl isobutyl ketone, and g of compound X3 shown in Table 1 were added and dispersed uniformly. To obtain a fluoropolymer composition B2-2. The results of the storage stability test as in Example 1 are shown in Table 1.
[0088]
[Table 1]

[0089]
By comparing Examples 1-2 and 7 (Comparative Example) and Examples 3-6 and 8 (Examples), a fluoropolymer composition containing a specific polymerization inhibitor or polymerization inhibitor in the present invention was used. It can be seen that the product is excellent in thermal stability.
[0090]
(Examples 9 to 11) “Production Examples of Curable Composition”
After the terminal hydroxyl group of a polyoxypropylene polyol having a number average molecular weight of 17,000 produced using ethylene glycol as an initiator and a zinc hexacyanocobaltate complex catalyst was converted to an allyloxy group, methyldimethoxysilylpropyloxy group (75 at all terminals) %) To obtain a silicon group-containing polymer.
[0091]
5 parts of the above fluoropolymer composition B1-1 (Example 9) or B1-6 (Example 10) with respect to 100 parts of the polymer, surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., white gloss CCR) 120 parts, 20 parts of heavy calcium carbonate (Whiteon SB manufactured by Shiraishi Kogyo Co., Ltd.), 10 parts of titanium oxide (R820 manufactured by Ishihara Sangyo Co., Ltd.), 30 parts of dioctyl phthalate, thixotropic agent (Dispalon 305 manufactured by Enomoto Kasei Co., Ltd.) 3 Parts, 20 parts of epoxidized plasticizer (Sansocizer EPS manufactured by Shin Nippon Rika Co., Ltd.), 3 parts of trimethylolpropane trisacrylate (Aronics M309 manufactured by Toagosei Co., Ltd.), 1 part of UV absorber (manufactured by Ciba-Geigy Co., Ltd.) , 1 part of an antioxidant (Ciba Geigy, Irganox 1010) was mixed in a plastic container and kneaded with a three-roll, It was.
[0092]
Further, as a curing agent, 3 parts of tin 2-ethylhexanoate, 1 part of laurylamine, 6 parts of dioctyl phthalate, 15 parts of heavy calcium carbonate (Whiteon SB manufactured by Shiroishi Kogyo Co., Ltd.), Kaolin (Kaolin ASP-170 manufactured by ENGELHARD) ) A mixture of 50 parts was used. 3 parts of a curing agent was added to 100 parts of the main agent and kneaded sufficiently.
[0093]
This kneaded product was put into a mold having a length of 100 mm, a width of 25 mm, and a thickness of 5 mm, and was put into a sheet shape and placed in a constant temperature and humidity chamber at 20 ° C. and 65% humidity for 7 days to obtain a cured sheet. Similarly, a cured product sheet not containing the fluoropolymer composition was prepared (Example 11).
[0094]
This cured sheet was left at an angle of 45 degrees in the Kashima factory of Asahi Glass Co., Ltd. in Kashima-gun, Ibaraki, and the weathering resistance after half a year was visually observed. As for the contamination resistance state, Example 10 was the best, and then Example 9 was excellent, but in comparison with these, Example 11 was heavily soiled.
[0095]
[Table 2]

[0096]
【The invention's effect】
A composition comprising a fluoropolymer composition to which a specific polymerization inhibitor or polymerization inhibitor in the present invention has been added has an effect of good thermal stability and excellent storage stability. As a result, neither gelation nor thickening occurs even in the process of blending into the curable composition containing the hydrolyzable silicon group-containing organic polymer, and the storage stability is good even when blended in the curable composition. The weather resistance and surface contamination resistance of the cured product of the curable composition can be improved without adversely affecting the basic physical properties of the cured product of the curable composition.

Claims (7)

A composition comprising a fluorine-containing polymer (B) having a polymer unit having a photocurable functional group, and a compound (C) having a nitroso group, a hydroxyamino group or a salt thereof. The composition according to claim 1, wherein the photocurable functional group in the fluoropolymer (B) is a group selected from an acryloyl group, a methacryloyl group, a cinnamoyl group and an azide group. The fluoropolymer (B) is a polymer unit (p) having a polyfluorohydrocarbon group in an amount of 20 to 95 mol% based on the total polymer units, and a polymer unit (q) having a photocurable functional group is a total polymer unit. The composition according to claim 1 or 2, which is a polymer containing from 5 to 80 mol%, and optionally from 0 to 75 mol% of other polymerized units (r) based on the total polymerized units. The fluoropolymer (B) is a polymer unit (s) based on fluoroolefin of 20 to 70 mol% based on the total polymer units, and a polymer unit (t) having a photocurable functional group based on the total polymer units. The composition according to claim 1 or 2, which is a polymer containing 1 to 80 mol% and optionally 0 to 70 mol% of other polymerized units (u) based on all polymerized units. Content of a compound (C) is 0.001 mass part-10 mass parts with respect to 100 mass parts of fluoropolymers (B) which have a polymerization unit which has a photocurable functional group, Claims 1-4. A composition according to 1. An organic polymer (A) having one or more hydrolyzable silicon groups in the molecule which can be crosslinked by hydrolysis, a fluorinated polymer (B) having a polymer unit having a photocurable functional group, and a nitroso group or A curable composition containing a compound (C) having a hydroxyamino group or a salt thereof. The curable composition according to claim 6, wherein the hydrolyzable silicon group of the organic polymer (A) is a group represented by Formula 1.

In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a hydroxyl group or a monovalent hydrolyzable group, and a is an integer of 1 to 3.