JP3844212B2 - COATING COMPOSITION AND COATED ARTICLE USING THE COATING COMPOSITION - Google Patents

Description

（但し、式中Ｒ^１は水素原子または炭素原子数１〜１０の炭化水素基、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は互いに同一でも異なっていてもよい水素原子または炭素原子数１〜１０の炭化水素基、ｎは２以上の整数である。）
で示される片末端ラジカル重合性ポリシロキサン及び／または下記一般式（２）
【化６】

（但し、式中Ｒ^７は水素原子または炭素原子数１〜１０の炭化水素基、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２は互いに同一でも異なっていてもよい水素原子または炭素原子数１〜１０の炭化水素基、ｐは０〜１０の整数、ｑは２以上の整数である。）
で示される片末端ラジカル重合性ポリシロキサン５〜４０重量％、
（Ｃ） アルコキシシリル基を有する単量体 ５〜５５重量％、
（Ｄ） 水酸基を有する単量体 １５〜５０重量％、
（Ｅ） 成分（Ａ）〜（Ｄ）とラジカル重合以外に反応しない官能基を有する単量体０〜７３重量％、
（但し、（Ａ）〜（Ｅ）はそれらの総和が１００重量％となる値をとる）を共重合してなる基体樹脂（ａ）及び該基体樹脂（ａ）と架橋反応することが可能である硬化剤（ｂ）を含有してなる被覆組成物を用いる本発明によって解決することが可能である。
上記雪や氷の付着を防ぎ、又は貼り紙が自然にはがれるようにすることについての課題は、
（Ａ） ウレタン結合を介してラジカル重合性不飽和結合を有するフッ素樹脂２〜７０重量％、
（Ｂ）下記一般式（１）
【化７】

（但し、式中Ｒ^１は水素原子または炭素原子数１〜１０の炭化水素基、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は互いに同一でも異なっていてもよい水素原子または炭素原子数１〜１０の炭化水素基、ｎは２以上の整数である。）
で示される片末端ラジカル重合性ポリシロキサン及び／または下記一般式（２）
【化８】

（但し、式中Ｒ^７は水素原子または炭素原子数１〜１０の炭化水素基、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２は互いに同一でも異なっていてもよい水素原子または炭素原子数１〜１０の炭化水素基、ｐは０〜１０の整数、ｑは２以上の整数である。）
で示される片末端ラジカル重合性ポリシロキサン ５〜４０重量％、
（Ｃ） アルコキシシリル基を有する単量体 ５〜５５重量％、
（Ｄ） 水酸基を有する単量体 ３〜３０重量％、
（Ｅ） 成分（Ａ）〜（Ｄ）とラジカル重合以外に反応しない官能基を有する単量体 ０〜８５重量％、
（但し、（Ａ）〜（Ｅ）はそれらの総和が１００重量％となる値をとる）を共重合してなる基体樹脂（ａ）及び該基体樹脂（ａ）と架橋反応することが可能である硬化剤（ｂ）を必須構成成分として構成される被覆組成物を用いるという本発明によって解決することが可能である。
【００１２】
また、本発明は上記被覆組成物を用いた被覆物品に関する。
【００１３】
【発明の実施の形態】
以下、本発明の被覆組成物及び該被覆組成物を用いた被覆物品について詳細に説明する。本発明に用いられるウレタン結合を介してラジカル重合性を有する有機溶剤可溶性フッ素樹脂（Ａ）は、水酸基を有するフッ素樹脂（Ａ−１）とイソシアネート基を有するラジカル重合性単量体（Ａ−２）を反応させることによって得られる。イソシアネート基を有するラジカル重合性単量体（Ａ−２）はジイソシアネート（Ａ−２−１）と水酸基を有するラジカル重合性単量体（Ａ−２−２）の反応物、メタクリロイルイソシアネート、２−イソシアナトエチルメタクリレート、ｍ−またはｐ−イソプロペニル−α，α−ジメチルベンジルイソシアネートから１種または２種以上を選択して用いられ、好ましくはメタクリロイルイソシアネート、２−イソシアナトエチルメタクリレート、ｍ−またはｐ−イソプロペニル−α，α−ジメチルベンジルイソシアネートの１種または２種以上が用いられる。
【００１４】
前記ジイソシアネート（Ａ−２−１）は、例えば、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、１，３−ビス（ジイソシアナトメチル）シクロヘキサン、１，３−ビス（α，α−ジメチルイソシアナトメチル）ベンゼン、４，４’−ジフェニルメタンジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネート等が挙げられ、単独又は２種類以上を混合して用いることができる。また、前記水酸基を有するラジカル重合性単量体（Ａ−２−２）は、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ｐ−ヒドロキシスチレン、ｐ−ヒドロキシメチルスチレン等が挙げられ、同様に単独又は２種類以上を混合して用いることができる。
【００１５】
ジイソシアネート（Ａ−２−１）と水酸基を有するラジカル重合性単量体（Ａ−２−２）の反応は公知の方法によりモル比１／１にて実施することができる。
【００１６】
前記水酸基を有するフッ素樹脂（Ａ−１）の水酸基価は５〜２５０とすることが好ましく、１０〜２００とすることがより好ましく、２０〜１５０とすることが更に好ましい。水酸基価が５未満であると、イソシアネート基を有するラジカル重合性単量体（Ａ−２）の導入量が著しく少なくなるためにグラフト化が十分に進行せず反応混合物が濁る傾向にある。また、結果的に基体樹脂（ａ）の水酸基価が小さくなるために落書き除去機能が低下する。一方、水酸基価が２５０を越えると後述の片末端ラジカル重合性ポリシロキサン（Ｂ）との相溶性が悪化して相分離を起こし、グラフト共重合自体が進行しなくなる場合がある。
また、後述する硬化剤（ｂ）の添加量が必然的に増えるため被覆物の親水部（ウレタン結合による架橋部）が増加して表面エネルギーが大きくなり、結果的に着氷雪防止機能及び貼り紙防止機能が低下するため好ましくない。
【００１７】
このような水酸基を有するフッ素樹脂（Ａ−１）は公知の方法で調製することができるが、市販品を用いることもできる。市販品としては、ルミフロン(登録商標）ＬＦ−１００、ＬＦ−２００、ＬＦ−３０２、ＬＦ−４００、ＬＦ−５５４、ＬＦ−６００、ＬＦ−９８６Ｎ（旭硝子社製）、セフラルコート(登録商標）ＰＸ−４０、Ａ６０６Ｘ、Ａ２０２Ｂ、ＣＦ−８０３（セントラル硝子社製）、ザフロン(登録商標）ＦＣ−１１０、ＦＣ−２２０、ＦＣ−２５０、ＦＣ−２７５、ＦＣ−３１０、ＦＣ−５７５、ＸＦＣ−９７３（東亞合成社製）、ゼッフル(登録商標）ＧＫ−５１０（ダイキン工業社製）、フルオネート(登録商標）Ｋ−７００、Ｋ−７０２、Ｋ−７０３、Ｋ−７０４、Ｋ−７０５（大日本インキ化学工業社製）等が挙げられる。
【００１８】
これらの水酸基を有するフッ素樹脂（Ａ−１）は、単独で使用してもよく、又は２種類以上混合して使用しても良い。
【００１９】
イソシアネート基を有するラジカル重合性単量体（Ａ−２）は、水酸基を有するフッ素樹脂（Ａ−１）の水酸基１当量あたり０．００１モル以上０．１モル未満の量を反応させる。好ましくは水酸基を有するフッ素樹脂（Ａ−１）の水酸基１当量あたり０．０１モル以上０．０８モル未満である。このイソシアネート基を有するラジカル重合性単量体（Ａ−２）が０．００１モル未満であるとグラフト共重合が困難となり、反応混合物が濁るおそれがある。また、０．１モル以上であるとグラフト共重合の際にゲル化が起こりやすくなり好ましくない。
【００２０】
また、水酸基を有するフッ素樹脂（Ａ−１）とイソシアネート基を有するラジカル重合性単量体（Ａ−２）の反応は、無触媒下あるいは触媒存在下で、室温〜８０℃で行えばよい。
【００２１】
本発明に用いられる片末端ラジカル重合性ポリシロキサン（Ｂ）は一般式（１）
【化９】

〔式中のＲ^１は水素原子または炭素原子数１〜１０の炭化水素基であり、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、フェニル基、シクロヘキシル基が挙げられ、好ましくは水素原子、メチル基である。また式中のＲ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は互いに同一でも異なっていてもよい水素原子または炭素原子数１〜１０の炭化水素基であり、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、フェニル基、シクロヘキシル基が挙げられ、好ましくはＲ^２、Ｒ^３、Ｒ^４、Ｒ^５についてはメチル基、フェニル基、Ｒ^６についてはメチル基、ブチル基、フェニル基である。また式中のｎは２以上の整数であり、好ましくは１０以上の整数、より好ましくは３０以上の整数である。〕
で、及び／または、一般式（２）
【化１０】

〔式中のＲ^７は水素原子または炭素原子数１〜１０の炭化水素基であり、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、フェニル基、シクロヘキシル基が挙げられ、好ましくは水素原子、メチル基である。また式中のＲ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２は互いに同一でも異なっていてもよい水素原子または炭素原子数１〜１０の炭化水素基であり、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、フェニル基、シクロヘキシル基が挙げられ、好ましくはＲ^８、Ｒ^９、Ｒ^１０、Ｒ^１１についてはメチル基、フェニル基、Ｒ^１２についてはメチル基、ブチル基、フェニル基である。また式中のｐは０〜１０の整数であり、好ましくは３である。また、式中のｑは２以上の整数であり、好ましくは１０以上の整数、より好ましくは３０以上の整数である。〕で示される。
【００２２】
このような片末端ラジカル重合性ポリシロキサン（Ｂ）は公知の方法にて調製することができるが、市販品を用いることもでき、市販品の例としては、サイラプレーン(登録商標）ＦＭ−０７１１（数平均分子量１，０００；チッソ社製）、サイラプレーン(登録商標）ＦＭ−０７２１（数平均分子量５，０００；チッソ社製）、サイラプレーン(登録商標）ＦＭ−０７２５（数平均分子量１０，０００；チッソ社製）、Ｘ−２２−１７４ＤＸ（数平均分子量４，６００；信越化学工業社製）等が挙げられる。
【００２３】
これらの片末端ラジカル重合性ポリシロキサン（Ｂ）は、単独でも又は２種類以上混合して使用しても良い。
【００２４】
これらの片末端ラジカル重合性ポリシロキサン（Ｂ）は基体樹脂全量に対して５〜４０重量％の範囲で用いられ、好ましくは１０〜３０重量％の範囲である。５重量％未満とすると、初期の落書き除去機能が不十分及び／又は落書き除去機能の維持性が悪化し、初期の着氷雪防止機能が不十分及び／又は着氷雪防止機能の維持性が悪化し、又は初期の貼り紙防止機能が不十分及び／又は貼り紙防止機能の維持性が悪化し、４０重量％を越えると被覆組成物の単位体積あたりの架橋密度が低下するためにラッカースプレー、フェルトペン等のラッカーやインキのしみ込みが起こりやすくなり、結果的に初期の落書き除去機能が不十分となり、また被覆の強度が低下して着氷雪防止機能の維持性が不十分となり、また貼り紙防止機能の維持性が不十分となる。
【００２５】
本発明に用いられるアルコキシシリル基を有する単量体（Ｃ）はジアルコキシアルキル基又はトリアルコキシシリル基とラジカル重合性二重結合を有するものであれば特に制限なく用いられ、例えば、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、グリシジル（メタ）アクリレートや３，４−エポキシシクロヘキシルメチル（メタ）アクリレートとγ−アミノプロピルトリメトキシシランやγ−アミノプロピルトリエトキシシランのモル比１／１反応物、グリシジル（メタ）アクリレートや３，４−エポキシシクロヘキシルメチル（メタ）アクリレートとγ−メルカプトプロピルトリメトキシシランやγ−メルカプトプロピルトリエトキシシランのモル比１／１反応物、２−ヒドロキシエチル（メタ）アクリレートや２−ヒドロキシプロピル（メタ）アクリレートとγ−イソシアナトプロピルトリメトキシシランのモル比１／１反応物等が挙げられる。中でも、共重合性の観点から、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシランが好ましく、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシランが特に好ましい。
【００２６】
これらのアルコキシシリル基を有する単量体（Ｃ）は、単独で使用しても又は２種類以上混合して使用しても良い。
【００２７】
これらのアルコキシシリル基を有する単量体（Ｃ）は、基体樹脂（ａ）全量に対して５〜５５重量％の範囲で用いられ、好ましくは１０〜５０重量％、更に好ましくは１５〜４０重量％である。５重量％未満とすると被覆組成物の架橋密度が上がらなくなるため、初期の落書き除去機能が低下し、又は被覆の強度に問題が生じ結果的に着氷雪防止機能と貼り紙防止機能の維持性が低下する。また、５５重量％を越えると架橋密度が上がりすぎ被覆が脆くなったり、後述する成分（Ｅ）の導入量が少なくなるため基体樹脂（ａ）のガラス転移温度（Ｔｇ）調整が困難となり結果的に落書き除去機能が低下することがある。
【００２８】
本発明に用いられる水酸基を有する単量体（Ｄ）は水酸基とラジカル重合性二重結合を有するものであれば特に制限なく用いられ、例えば、ｐ−ヒドロキシスチレン、ｐ−ヒドロキシメチルスチレン、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ジ−２−ヒドロキシエチルフマレートをはじめ、ポリエチレングリコールまたはポリプロピレングリコールモノ（メタ）アクリレート、またはこれらのε−カプロラクトン付加物、プラクセル(登録商標）ＦＭ乃至はＦＡシリーズ（ダイセル化学社製；カプロラクトン付加単量体）のごとき各種のα，β−エチレン性不飽和カルボン酸のヒドロキシアルキルエステル類、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸のごときα，β−エチレン性不飽和カルボン酸とε−カプロラクトンとの付加物、またはこれらのα，β−エチレン性不飽和カルボン酸とブチルグリシジルエーテル、フェニルグリシジルエーテル、カージュラ(登録商標）E（シェル化学社製）のごときエポキシ化合物との付加物等が挙げられる。中でも、主として重合体のＴｇ調整という観点から２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートが好ましく用いられる。
【００２９】
これらの水酸基を有する単量体（Ｄ）は、単独で使用しても又は２種類以上混合して使用しても良い。
【００３０】
落書き除去機能に関しては、この水酸基を有する単量体（Ｄ）は基体樹脂（ａ）全量に対して１５〜５０重量％の範囲で用いられ、好ましくは２０〜３０重量％の範囲である。
着氷雪防止機能と貼り紙防止機能に関しては、この水酸基を有する単量体（Ｄ）は基体樹脂（ａ）全量に対して３〜３０重量％の範囲で用いられ、好ましくは５〜１５重量％の範囲である。
水酸基を有する単量体（Ｄ）を３％未満とすると被覆組成物の架橋密度が上がらず被覆の強度や耐溶剤性が低下する。落書き除去機能には、１５％未満でも被覆組成物の架橋密度が不十分なため初期の落書き除去機能が低下する。
一方３０重量％を越えると、後述する硬化剤（ｂ）の添加量が必然的に増えるため被覆単位体積あたりの親水部（ウレタン結合による架橋部）が増加し、着氷雪防止機能又は貼り紙防止機能が低下するため好ましくない。また、５０重量％を越えると架橋密度が上がりすぎ被覆が脆くなったり、基体樹脂（ａ）が分子ミセルを形成して濁ってしまい、被覆外観が低下することがある。
【００３１】
本発明における成分（Ａ）〜（Ｄ）とラジカル重合以外に反応しない官能基を有する単量体（Ｅ）は、ラジカル重合するときの反応温度、反応条件において成分（Ａ）〜（Ｄ）と反応しないものが選ばれ、例えば、スチレン、ｐ−メチルスチレン、ｐ−クロロメチルスチレン、ビニルトルエン等のスチレン類、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｉ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート等の炭化水素基をもつ（メタ）アクリレート類、これらの水素原子をフッ素、塩素、臭素原子等で置換した（メタ）アクリレート類、酢酸ビニル、安息香酸ビニル、ベオバ(登録商標）（シェル化学社製；分岐状モノカルボン酸のビニルエステル）等のビニルエステル類、アクリロニトリル、メタクリロニトリル等のアクリロニトリル類、エチルビニルエーテル、ｎ−ブチルビニルエーテル、ｉ−ブチルビニルエーテル、シクロヘキシルビニルエーテル等のビニルエーテル類、これらの水素原子をフッ素、塩素、臭素原子等で置換したビニルエーテル類、（メタ）アクリルアミド、ジメチル（メタ）アクリルアミド、ジアセトンアクリルアミド等のアクリルアミド類、これらの水素原子をフッ素、塩素、臭素原子等で置換したアクリルアミド類、グリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチル（メタ）アクリレート、３，４−エポキシビニルシクロヘキサン等のエポキシ基含有ビニル化合物類、エチレン、プロピレン等のオレフィン類、塩化ビニル、塩化ビニリデン、臭化ビニル、フッ化ビニル、テトラフルオロエチレン、クロロトリフルオロエチレン等のハロゲン化オレフィン類、その他マレイミド、ビニルスルホン等が挙げられ、これらは適宜組み合わせて複数が用いられるが、主として共重合性の観点から（メタ）アクリレート類が好ましく用いられる。
【００３２】
一方、成分（Ｅ）として好ましくないものとしては、ビニルピリジン、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、４−（Ｎ，Ｎ−ジメチルアミノ）スチレン、Ｎ−｛２−（メタ）アクリロイルオキシエチル｝ピペリジン等の塩基性窒素含有ビニル化合物類、（メタ）アクリル酸、アンゲリカ酸、クロトン酸、マレイン酸、４−ビニル安息香酸、ｐ−ビニルベンゼンスルホン酸、２−（メタ）アクリロイルオキシエタンスルホン酸、モノ｛２−（メタ）アクリロイルオキシエチル｝アシッドホスフェート等の酸性ビニル化合物類が挙げられる。上記塩基性窒素含有ビニル化合物類及び酸性ビニル化合物類はアルコキシシリル基を有する単量体（Ｃ）のアルコキシシリル基を解離、縮合させる触媒の働きをなすので、重合中あるいは基体樹脂（ａ）を長期保存するときに増粘、ゲル化する場合がある。
【００３３】
落書き除去機能に関しては、上記成分（Ｅ）は、最終的な基体樹脂（ａ）のＴｇが４０℃以上となるように組み合わせて用いるのが好ましい。最終的な基体樹脂（ａ）のＴｇが４０℃未満の場合には該被覆組成物が硬化した後の被覆のＴｇがあまり上がらないため、特に夏季、被覆物が直射日光等によって高温にさらされた場合の落書き除去機能が低下する場合がある。落書き除去機能に関しては、これら成分（Ｅ）は、全量に対し０〜７３重量％の範囲で用いられる。７３重量％を越えると他の成分、特に架橋密度を上げるための成分（Ｃ）、（Ｄ）の導入量が低下するため落書き除去機能あるいはその維持性が不十分となる。
着氷雪防止機能又は貼り紙防止機能に関しては、上記成分（Ｅ）は、全量に対し０〜８５重量％の範囲で用いられる。８５重量％を越えると他の成分（Ｂ）〜（Ｄ）の導入量が低下することになる。成分（Ｂ）の導入量が低下した場合にはそれらの機能あるいはその維持性が不十分となり、成分（Ｃ）及び／又は（Ｄ）の導入量が低下した場合には被覆物の強度が低下する。
ここで、０重量％とは、成分（Ｅ）が存在しないことを意味する。
【００３４】
本発明における成分（Ａ）と（Ｂ）〜（Ｄ）の比率［（Ａ）／（（Ｂ）＋（Ｃ）＋（Ｄ））；以下ベースグラフト比と略］は７０／３０〜２／９８の範囲が選ばれる。ベースグラフト比が７０／３０を越えて成分（Ａ）の比率が多い場合は成分（Ｂ）〜（Ｄ）の導入量が少なくなるため、被覆の光沢が低下し、また、落書き除去機能、着氷雪防止機能、及び貼り紙防止機能が低下する。また、ベースグラフト比が２／９８より小さく成分（Ｂ）＋（Ｃ）＋（Ｄ）の比率が多い場合には被覆の耐候性及び接触角維持性が低下し、また、落書き除去機能、着氷雪防止機能及び貼り紙防止機能の維持性が低下する。
【００３５】
以上に挙げられたような単量体類を用いて基体樹脂（ａ）を調製するには公知慣用の重合方法のうち、溶液ラジカル重合法または非水分散ラジカル重合法によるのが最も簡便であり、特に推奨される。
【００３６】
重合の際に用いられる溶剤としては例えば、トルエン、キシレン、ソルベッソ(登録商標)１００（エッソ石油社製）等の芳香族炭化水素類、ｎ−ヘキサン、シクロヘキサン、オクタン、ミネラルスピリット、ケロシン等の脂肪族、脂環族炭化水素類、酢酸エチル、酢酸ｎ−ブチル、酢酸ｉ−ブチル，ブチルセロソルブアセテート等のエステル類、メタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール、ｎ−ブタノール、ｉ−ブタノール等のアルコール類、エチレングリコール、プロピレングリコール、エチルセロソルブ、ブチルセロソルブ等のグリコールまたはグリコールエーテル類が挙げられ、単独または２種類以上を併用して用いることができる。
【００３７】
重合はアゾ系または過酸化物のような公知慣用の種々のラジカル重合開始剤を用いて常法により実施できる。
【００３８】
重合時間は特に制限されないが、通常工業的には１〜４８時間の範囲が選ばれる。また、重合温度は通常３０〜１５０℃、好ましくは６０〜１２０℃である。
【００３９】
重合時、更に必要に応じて副反応を起こさなければ、公知慣用の連鎖移動剤、例えばブチルメルカプタン、ドデシルメルカプタン、α−メチルスチレンダイマー等を添加することもできる。
【００４０】
本発明における基体樹脂（ａ）は、概ね重量平均分子量がポリスチレン換算のＧＰＣ（ゲルパーミエーションクロマトグラフィー）により５，０００〜２，０００，０００なる範囲が適切である。５，０００未満とすると造膜性、被覆物の耐候性、及び耐薬品性が悪化するために結果的に落書き除去機能の維持性、着氷雪防止機能の維持性又は貼り紙防止機能の維持性が低下し、２，０００，０００を越えると重合時ゲル化の危険があり好ましくない。
【００４１】
本発明の基体樹脂（ａ）と架橋反応することができる硬化剤（ｂ）は基体樹脂（ａ）の水酸基と反応できる硬化剤が適宜選ばれ、一般にアクリル硬化型塗料の硬化剤として知られているものを使用することができる。このような硬化剤としては、例えば、アニリンアルデヒド樹脂、尿素樹脂、メラミン樹脂、ポリイソシアネート、ブロック化ポリイソシアネート等が挙げられる。
被塗物が鋼板、れんが、ブロック、看板、交通標識、パラボラアンテナ（小型）等のプレコートが可能であるものであれば任意のものが使用可能であるが、一般に、アフターコートとして既設の建築物外壁、電柱、橋脚、看板、電話ボックス等の構造物に被覆する場合が多いため、このような場合には常温で硬化が可能であるポリイソシアネートが選ばれる。このように、常温で硬化する場合には、イソシアネート基を基体樹脂の水酸基価の０．５〜１．５当量用い、好ましくは落書き除去機能に関しては１〜１．４当量、着氷雪防止機能又は貼り紙防止機能に関しては０．８〜１．２当量用いる。
【００４２】
また、本発明の被覆組成物は任意公知の塗装方法が適用でき、その不揮発分は特に制限されるものではなく、適宜選択されるが、通常１０〜５０重量％とすることが好ましい。
【００４３】
更に、本発明の被覆組成物は必要に応じて本発明の趣旨を損なわない範囲で他の樹脂、例えば、フッ素樹脂、アクリル樹脂、ポリエステル樹脂、アルキッド樹脂、シリコーン樹脂等を添加することもできる。
本発明の被覆組成物は必要に応じて本発明の趣旨を損なわない範囲で各種添加剤、例えば界面活性剤、増量剤、着色顔料、防錆顔料、フッ素樹脂粉末、シリコーン樹脂粉末、防錆剤、染料、ワックス等を添加することもできる。落書き除去機能に関しては、一般に、上記添加剤は被覆単位体積あたりの架橋密度を低下させ、ラッカースプレー、フェルトペン等のラッカーやインキがしみ込みやすくなるので、必要最小限の量に留めるべきである。
【００４４】
また、本発明の「被覆物品」とは本発明の被覆組成物を被覆したものであり、落書き除去機能が必要とされる物、着氷雪防止機能が必要とされる物、又は貼り紙防止機能が必要とされる物であれば特に制限されないが、建築物外壁及び屋根、門扉、電柱、橋脚、電線、送電鉄塔、看板、交通標識、航空機、鉄道車輌、船舶、電話ボックス等の屋外構造物等も含むものとし、一般には、そのような屋外構造物に適用される場合も多いと考えられる。
【００４５】
【実施例】
以下本発明を参考例、製造例、実施例により説明するが、本発明は以下に示される例示例に何ら限定されるものではない。以下の例示例において特に記載のない限り“部”は重量部を表すものとする。
【００４６】
以下の例示例において用いられた材料の市販品名を次に示す。
水酸基を有するフッ素樹脂（Ａ−１）
・セフラルコート（商標）ＣＦ−８０３ （セントラル硝子社製，水酸基価；６０，数平均分子量；１５，０００）
片末端ラジカル重合性ポリシロキサン（Ｂ）
・サイラプレーン（登録商標）ＦＭ−０７２１ （チッソ社製，数平均分子量５，０００）
ラジカル重合開始剤
・パーブチル（登録商標)Ｏ （ｔ−ブチルパーオキシ−２−エチルヘキサノエート；日本油脂社製）
硬化剤；成分（ｂ）
・コロネート（登録商標)ＨＸ （ヘキサメチレンジイソシアネートのイソシアヌレート型ポリイソシアネート；日本ポリウレタン社製）
【００４７】
また、実施例における試験項目を以下に示す。
被覆組成物硬化物の皮膜の外観
皮膜の異常を目視にて確認した。
落書き除去性（初期）
被覆組成物硬化物の皮膜表面上に黒色のマジックインキ(株式会社内田洋行の登録商標、寺西化学工業株式会社製フェルトペン）で線を引き、室温で２４時間乾燥後、布で乾拭きし、マジックインキ(登録商標）の跡が全く残らないものを○、僅かに跡が残るものを△、はっきりと跡が残るものを×で表した。
撥水性（初期、曝露後）
機器として協和界面科学社製ＣＡ−Ｗ型自動接触角計を用い、被覆組成物を被覆した被覆板上に約５μｌの脱イオン水を載せ、このときの接触角を測定した。載せる位置を変えて６点測定し、最も小さい値と最も大きい値を除いた４点で平均値を計算して四捨五入によって整数値に丸めた。結果を図１と図２に示す。また、ＡＴＬＡＳ社製Ｃｉ４０００サンシャインウェザオメーターを用い、キセノンを光源としてＩＳＯ１１３４１；ｍｅｔｈｏｄ１屋外（塗料、ワニスの促進耐候性試験法）に従って被覆板を曝露した。最大６００時間まで、１００時間経過する毎に被覆板をとりだし、十分水分を取り除いた後、上記同様に接触角測定を行った。結果を図１と図２に併せて示す。
落書き除去性（曝露後）
上記曝露条件で６００時間曝露した被覆組成物硬化物の表面に、マジックインキ(登録商標）黒で線を引いてマジックインキ(登録商標）の溶剤が十分乾燥した（約２時間）後、その表面を前記同様に乾拭きして評価した。
耐溶剤性
被覆板上にキシレンを一滴のせてキシレンが揮発するまで常温で放置し、塗膜の状態を目視で観察した。
着氷防止性
被覆板を−２０℃の冷凍庫中に入れ、一晩放置した。この被覆板上にスポイトで５０μｌの水道水を、水滴がそれぞれ一滴となるように３個載せ、更に２時間−２０℃に保って氷結させた。被覆板を水平に保ったまま、被覆板を手で軽くたたくだけで氷が落ちた場合を○、氷に手で触れることによって落ちた場合を△、氷が除去できないもの、あるいは氷が破壊して表面に氷の一部が残存するものを×として評価した。測定は上記サンシャインウェザオメーター１００時間曝露する毎に行った。結果を表４に示す。
貼り紙防止性１
被覆板を２３℃、相対湿度５０％の恒温室中に入れ、一晩放置し状態調節した。この被覆板に、裏面に水性糊（トンボ鉛筆社製；アクアピット（登録商標））を全面に塗布した紙（３０×５０ｍｍ）を貼り付け、被覆板を垂直に保った。糊の乾燥につれて自動的にはがれたものを○、はがれなかったものを×で評価した。評価は、上記サンシャインウェザオメーター０時間（照射前）と６００時間経過したものについて行った。結果を表５に示す。
貼り紙防止性２
上記同様に状態調節した被覆板に、布ガムテープ（積水化学工業社製；布テープＮｏ．６００）を貼り付けて手ではがし、はがれたものを○、被覆表面に糊が残ったり、被覆が破損した場合を×で評価した。評価は、上記サンシャインウェザオメーター０時間（照射前）と６００時間経過したものについて行った。結果を表５に示す。
【００４８】
【参考例１】
ウレタン結合を介してラジカル重合性を有するフッ素樹脂（Ａ）の合成例
機械式撹拌装置、温度計、コンデンサー、乾燥窒素ガス導入口を備えたガラス製反応器に、セフラルコートＣＦ−８０３ １，５５４部、キシレン ２３３部、２−イソシアナトエチルメタクリレート ６．３部を入れ、乾燥窒素雰囲気下８０℃に加熱した。８０℃で２時間反応し、サンプリング物の赤外吸収スペクトルによりイソシアネートの吸収が消失したことを確認した後、反応混合物を取り出し、不揮発分５０％の成分（Ａ）を得た。
【００４９】
【製造例＜表１＞１】
落書き防止被覆組成物用基体樹脂（ａ）の合成例＜表１＞１
機械式撹拌装置、温度計、コンデンサー、乾燥窒素ガス導入口を備えたガラス製反応器に、参考例１で合成した成分（Ａ） ４０部、酢酸ｎ−ブチル ８０部を入れ、窒素雰囲気中で９０℃まで加熱した後、予め混合したメチルメタクリレート ２０部、２−エチルヘキシルメタクリレート ７部、２−ヒドロキシエチルメタクリレート ２３部、ＦＭ−０７２１ １０部，γ−メタクリロキシプロピルトリメトキシシラン ２０部、パーブチルＯ ２部、キシレン ２２部の混合物を同温度で２時間かけて滴下した。２時間同温度で保持した後パーブチルＯ１部を追加し、更に９０℃で５時間保持することによって、不揮発分が４５％、重量平均分子量が５８，０００である目的とする基体樹脂（ａ）の溶液を得た。
【製造例＜表２＞１】
着氷雪防止被覆組成物及び貼紙防止被覆組成物用基体樹脂（ａ）の合成例＜表２＞１
機械式撹拌装置、温度計、コンデンサー、乾燥窒素ガス導入口を備えたガラス製反応器に、参考例１で合成した成分（Ａ） ６０部、酢酸ｎ−ブチル ９０部を入れ、窒素雰囲気中で９０℃まで加熱した後、予め混合したメチルメタクリレート １５部、２−エチルヘキシルメタクリレート １０部、２−ヒドロキシエチルメタクリレート １０部、ＦＭ−０７２１ １５部，γ−メタクリロキシプロピルトリメトキシシラン ２０部、パーブチルＯ ２部、キシレン ３０部の混合物を同温度で２時間かけて滴下した。２時間同温度で保持した後パーブチルＯ １部を追加し、更に９０℃で５時間保持することによって、不揮発分が４０％、重量平均分子量が９６，０００である目的とする基体樹脂（ａ）の溶液を得た。
【００５０】
【製造例＜表１＞２〜１０】
落書き防止被覆組成物用基体樹脂（ａ）又はその比較用基体樹脂の合成例＜表１＞２〜１０
各成分の仕込量を表１に示したように変更した以外は、製造例＜表１＞１と同様に操作して表１の基体樹脂（ａ）又はその比較用基体樹脂の溶液を得た。これらのうち、製造例＜表１＞２及び＜表１＞３は本発明の請求項の基体樹脂（ａ）に合致した例である。また、製造例４は成分（Ａ）が入っていない場合、製造例＜表１＞５及び＜表１＞６は成分（Ｂ）が基体樹脂全体のそれぞれ３重量％、４５重量％の場合、製造例＜表１＞７及び＜表１＞８は成分（Ｃ）が基体樹脂全体のそれぞれ３重量％、６０重量％の場合、製造例＜表１＞９及び＜表１＞１０は成分（Ｄ）が基体樹脂全体のそれぞれ１０重量％、５５重量％の例であって、いずれも本発明の請求項で定義される基体樹脂（ａ）には該当しない例である。
【製造例＜表２＞２〜１０】
着氷雪防止被覆組成物及び貼紙防止被覆組成物用基体樹脂（ａ）又はその比較用基体樹脂の合成例＜表２＞２〜１０
各成分の仕込量を表２に示したように変更した以外は、製造例＜表２＞１と同様に操作して表２の基体樹脂（ａ）又はその比較用基体樹脂の溶液を得た。これらのうち、製造例＜表２＞２及び＜表２＞３は本発明の請求項の基体樹脂（ａ）に合致した例である。また、製造例＜表２＞４は成分（Ａ）が入っていない場合、製造例＜表２＞５及び＜表２＞６は成分（Ｂ）が基体樹脂（ａ）全体のそれぞれ３重量％、５５重量％の場合、製造例＜表２＞７及び＜表２＞８は成分（Ｄ）が基体樹脂（ａ）全体のそれぞれ０重量％、４０重量％の場合、製造例＜表２＞９及び＜表２＞１０は成分（Ｃ）が基体樹脂（ａ）全体のそれぞれ３重量％、６０重量％の例であって、いずれも本発明の請求項で定義される基体樹脂（ａ）には該当しない例である。
【００５１】
【表１】

【表２】

【００５２】
【実施例＜表３＞１】
予め紙ヤスリで研磨した冷間圧延鋼板（５０×１５０ｍｍ）上に、２液型フッ素樹脂塗料である大日本塗料社製Ｖフロン（登録商標)＃１００（白色）を、バーコーター＃７５を用いて、乾燥膜厚約５０μｍとなるよう塗装し、２４時間養生し白色塗膜を形成した。製造例＜表１＞１で得られた基体樹脂（ａ）に該樹脂の水酸基当量に対して１．２倍当量のコロネート（登録商標)ＨＸを加え、更に塗料中の不揮発分が３５重量％になるように酢酸ｎ−ブチルで希釈して、被覆組成物を調製し、上記白色塗膜上に塗装した。これを２３℃、相対湿度５０％下で７日間養生して被覆板を得た。前述の各種試験を行い、結果を表３及び図１に示す。この被覆の落書き除去性は○、接触角は１０２°と良好で、かつ曝露後の落書き除去性、接触角の維持性も良好な結果を示した。
【実施例＜表４＞１】
予め紙ヤスリで研磨した冷間圧延鋼板（５０×１５０ｍｍ）上に、２液型フッ素樹脂塗料である大日本塗料社製Ｖフロン（登録商標）＃１００（白色）を、バーコーター＃７５を用いて、乾燥膜厚約５０μｍとなるよう塗装し、２４時間養生し白色塗膜を形成した。製造例＜表２＞１で得られた基体樹脂（ａ）に該樹脂の水酸基当量に対して１．０当量のコロネート（登録商標）ＨＸを加え、更に塗料中の不揮発分が３５重量％になるように酢酸ｎ−ブチルで希釈して、被覆組成物を調製し、上記白色塗膜上に塗装した。これを２３℃、相対湿度５０％下で７日間養生して被覆板を得た。前述の各種試験を行い、結果を表４及び図２に示す。この被覆は全ての試験項目において良好な結果を示した。
【実施例＜表５＞１】
予め紙ヤスリで研磨した冷間圧延鋼板（５０×１５０ｍｍ）上に、２液型フッ素樹脂塗料である大日本塗料社製Ｖフロン（登録商標）＃１００（白色）を、バーコーター＃７５を用いて、乾燥膜厚約５０μｍとなるよう塗装し、２４時間養生し白色塗膜を形成した。製造例＜表２＞１で得られた基体樹脂（ａ）に該樹脂の水酸基当量に対して１．０当量のコロネート（登録商標）ＨＸを加え、更に塗料中の不揮発分が３５重量％になるように酢酸ｎ−ブチルで希釈して、被覆組成物を調製し、上記白色塗膜上に塗装した。これを２３℃、相対湿度５０％下で７日間養生して被覆板を得た。前述の各種試験を行い、結果を表５及び図２に示す。この被覆は全ての試験項目において良好な結果を示した。
【００５３】
【実施例＜表３＞２、＜表３＞３、比較例＜表３＞１〜＜表３＞７】
実施例＜表３＞１で用いた基体樹脂（ａ）に代えて製造例＜表１＞２〜＜表１＞１０で得られた基体樹脂（ａ）又は比較用基体樹脂を用い、実施例＜表３＞１と同様にして被覆板を作製した。結果を表３に示す。実施例＜表３＞２および＜表３＞３においては全ての評価項目において良好なる結果を示した。しかし、比較例＜表３＞１、＜表３＞２においては初期の落書き除去性は良好なるものの、曝露後の落書き除去性維持性に難点がみられた。また、接触角も曝露によって大きく低下した。比較例３において被覆表面に未反応残存モノマーのブリードがみられ、べたつく上に、被覆の単位体積あたりの架橋密度が低下するため初期より落書きのしみ込みがみられた。同様に比較例＜表３＞４、＜表３＞６でも初期より落書きのしみ込みがみられた。比較例＜表３＞５、＜表３＞７では基体樹脂（ａ）がミセルを形成して濁ってしまい、このため被覆外観も濁り外観不良を呈した。
なお、図１に実施例＜表３＞１、実施例＜表３＞２、実施例＜表３＞３、比較例＜表３＞１、比較例＜表３＞２（図中では単に実施例１、実施例２、実施例３、比較例１、比較例２と記載）の被覆組成物硬化物表面の前記「撥水性（初期、曝露後）」試験結果を示す。
【００５４】
【表３】

【実施例＜表４＞２、＜表４＞３、比較例＜表４＞１〜＜表４＞７】
実施例＜表４＞１で用いた基体樹脂（ａ）に代えて製造例＜表２＞２〜＜表２＞１０で得られた基体樹脂（ａ）又は比較用基体樹脂を用い、実施例＜表４＞１と同様にして被覆板を作製した。結果を表４に示す。実施例＜表４＞２および＜表４＞３においては全ての評価項目において良好なる結果を示した。しかし、比較例＜表４＞１、＜表４＞２においては着氷防止性は良好なるものの、曝露後の着氷防止性に難点がみられた。また、接触角も曝露によって大きく低下した。比較例＜表４＞３において被覆表面に未反応残存モノマーのブリードがみられ、べたついていた。比較例＜表４＞４、＜表４＞６は被覆の耐溶剤性に難点があった。比較例＜表４＞５、＜表４＞７では基体樹脂（ａ）がミセルを形成して濁ってしまい、このため被覆外観も濁り外観不良を呈した。
なお、図２に実施例＜表４＞１、実施例＜表４＞２、実施例＜表４＞３、比較例＜表４＞１、比較例＜表４＞２（図中では単に実施例１、実施例２、実施例３、比較例１、比較例２と記載）の被覆組成物硬化物表面の前記「撥水性（初期、曝露後）」試験結果を示す。
【００５５】
【表４】

【実施例＜表５＞２、＜表５＞３、比較例＜表５＞１〜＜表５＞７】
実施例＜表４＞１で用いた基体樹脂（ａ）に代えて製造例＜表２＞２〜＜表２＞１０で得られた基体樹脂（ａ）又は比較用基体樹脂を用い、実施例＜表４＞１と同様にして被覆板を作製し、更に貼紙防止性の試験をした。結果を表５に示す（外観と耐溶剤性は表４と重複）。実施例＜表５＞２および＜表５＞３においては全ての評価項目において良好なる結果を示した。しかし、比較例＜表５＞１、＜表５＞２においては初期の貼り紙防止性１，２とも良好であったが、曝露後の貼り紙防止性に難点がみられた。また、接触角も曝露によって大きく低下した。比較例＜表５＞３において被覆表面に未反応残存モノマーのブリードがみられ、初期の貼り紙防止性２で被覆が破損した。比較例＜表５＞４、＜表５＞６は被覆の耐溶剤性に難点があり、また、初期の貼り紙防止性２で被覆が破損した。比較例＜表５＞５、＜表５＞７では、基体樹脂（ａ）がミセルを形成して濁ってしまい、このため被覆外観も濁り外観不良を呈し、また、曝露後の貼り紙防止性１，２とも良好でなかった。
【表５】

【００５６】
表６は図１の接触角の値を参考までに表にしたものである。表７は図２の接触角の値を参考までに表にしたものである。
【表６】

【表７】

【００５７】
以上のデータより、本発明の被覆組成物を用いることによって得られる被覆物品は、表面に優れた落書き除去性、接触角維持性を与えることが可能であり、表面に優れた着氷雪防止性を与えることが可能であり、また表面に優れた貼り紙防止性を与えることが可能であるのは明らかである。
【００５８】
【発明の効果】
本発明の被覆用の組成物及び該組成物を用いた被覆物品は、被覆したときに落書き除去機能を付与でき、その機能の維持性が良好であることから、各種基材の表面処理に適用することができる。具体的には、自動車、鉄道車輌、その他の車輌、建築物（住宅、ビル）等屋外構造物の外板及び外壁、門扉、橋脚、あるいは洗濯機、冷蔵庫等電気機器の外板、また道路標識、カーブミラー等に適用され、耐汚染性、落書き除去に有効である。
本発明の被覆組成物及び該組成物を用いた被覆物品は、被覆したときに着氷雪防止機能を付与でき、その機能の維持性が良好であることから、各種基材の表面処理に適用することができる。具体的には、自動車、鉄道車輌、船舶、その他の車輌、建築物（住宅、ビル、鉄塔、門扉）等屋外構造物の外板、外壁及び屋根、熱交換器、エアコンディショナーの放熱フィン、道路標識、看板、案内板、カーブミラー、パラボラアンテナ等に適用され、着氷雪防止に有効である。
本発明の被覆組成物及び該組成物を用いた被覆物品は、被覆したときに貼り紙防止機能を付与でき、その機能の維持性が良好であることから、各種基材の表面処理に適用することができる。具体的には、建築物外壁、電柱、橋脚、看板、電話ボックス等に適用され、貼り紙防止に有効である。
【図面の簡単な説明】
【図１】 図１は、脱イオン水の接触角により示される本発明の実施例＜表３＞１被覆組成物硬化物の表面の撥水性の、耐候試験条件下における経時的変化を、比較例の硬化物表面と比較したグラフである。
【図２】 図２は、脱イオン水の接触角により示される本発明の実施例＜表４＞１又は実施例＜表５＞１被覆組成物硬化物の表面の撥水性の、耐候試験条件下における経時的変化を、比較例の硬化物表面と比較したグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a coating composition that makes it difficult for deposits to adhere to the coating surface, or to easily remove deposits stuck to the coating surface.
That is, the present invention is a coating composition for applying to a structure such as an outer wall of a building, a utility pole, and a pier and removing graffiti by a lacquer spray, a felt pen, etc. by a simple method such as wiping. A coated article formed by coating the coating composition is provided.
In addition, the present invention can be applied to building exterior walls, roofs, utility poles, electric wires, power transmission towers, signboards, traffic signs, aircraft, railway vehicles, ships, etc. to prevent or easily remove snow and ice. Or a coating composition for facilitating snow falling on an inclined surface and a coated article coated with the coating composition.
In addition, the present invention can be applied to structures such as building outer walls, utility poles, bridge piers, signboards, telephone boxes, etc., and posters, advertising leaflets, etc. stuck on the surface of the walls are naturally peeled off or easily removed. And a coated article formed by coating the coating composition.
[0002]
[Prior art]
A coating composition applied to a structure such as a building outer wall, a gate, a utility pole, and a bridge pier can impart beauty of the appearance and corrosion resistance to the structure. In recent years, however, scribbling with lacquer sprays, felt-tip pens, etc. frequently occurs especially in urban areas, and the beauty of the structure is significantly impaired. In order to remove such graffiti, it is necessary to remove it by using solvent or forcibly scraping it off, or peeling off the existing paint film and repainting it, which is very laborious. . Therefore, the coating composition is required to have not only beauty and anticorrosive properties but also a function that can easily remove graffiti.
In particular, in cold regions, parabolic antennas that cause physical and human damage to structures such as building outer walls, roofs, utility poles, power transmission towers, signboards, etc. due to snow and ice falling on them. There are problems such as communication failure caused by snowfall, disconnection caused by snowfall on electric wires, and snow accumulated on an inclined roof is difficult to slide down and requires snow to be removed from the roof. In addition, problems such as falling ice and increased fuel consumption caused by icing have occurred in aircraft, railway vehicles, ships, and the like. Therefore, the coating composition is required not only to have beauty and anticorrosion properties but also to prevent icing snow.
In addition, posters, advertising flyers, and other stickers are frequently generated on building outer walls, utility poles, bridge piers, signboards, telephone boxes, etc., especially in urban areas, and the beauty of the structure is significantly impaired. In order to remove such a sticker, it is necessary to remove not only the paper portion but also the adhesive portion by human power, which is very troublesome. Therefore, the coating composition is required not only to have beauty and anticorrosive properties but also to have a function of easily removing the sticker.
[0003]
Therefore, in relation to facilitating graffiti removal and sticker removal, graffiti or sticker is easily removed using a coating composition in which a lubricating material such as silicone oil, polyethylene wax, or liquid paraffin is added to the coating composition. A method has been proposed.
However, in the coating composition to which the silicone oil, polyethylene wax, liquid paraffin, etc. are added, the additive bleeds out over time, so it is difficult to maintain the graffiti removal function and the sticker removal function is difficult to maintain. . In many cases, the compatibility between the coating composition and the above additives is poor, the transparency of the coating film is lowered, the beauty is impaired, and the surface is sticky.
Also, with respect to preventing the attachment of snow and ice, polytetrafluoroethylene, polyvinylidene fluoride, poly (perfluoroalkyl acrylate), tetrafluoroethylene or chlorotrifluoroethylene / Coating with a fluorine-containing compound such as an alkyl vinyl ether copolymer or a polyalkylsiloxane-containing compound is performed. However, it has been found that, when the fluorine-containing compound is used for coating, the adhesive strength with ice is large although the contact angle is relatively high (for example, Journal of the Japan Adhesive Society, Vol. 30, No. 30). 9 (1994)). In order to further increase the contact angle with respect to prevention of snow accretion, a paint of a type in which fluororesin fine particles are added to the coating composition as in JP-A-10-36707 is commercially available. However, in this type of paint, since the surface energy of the binder resin itself is small, the particles are not sufficiently fixed in the binder, and the particles are detached from the coating due to rubbing on the surface or collision of wind and rain or sand particles. There was a problem that the ice / snow prevention function deteriorated. On the other hand, many investigations have been made on coating compositions containing polyalkylsiloxane-containing compounds as constituent components. For example, there has been proposed a method for preventing adhesion of ice and snow by using a coating composition obtained by adding a lubricating material such as silicone oil, polyethylene wax, liquid paraffin to a binder resin typified by a silicone resin. .
As described above, in the coating composition to which the above silicone oil, polyethylene wax, liquid paraffin, etc. are added, the above additive bleeds out over time, so it is difficult to maintain the icing and snowing function. In addition, the compatibility of the above additives is poor, the transparency of the coating film is lowered and the beauty is impaired, or the surface is sticky, and the dirt component adheres to the beauty.
[0004]
Therefore, it has been considered that a silicone component is contained in the base resin in the coating composition by using a reactive silicone oil. For example, a technique represented by JP-A-10-140075 describes a base resin in which a polydimethylsiloxane oil having radical polymerizability and a (meth) acrylic acid ester are copolymerized and the polydimethylsiloxane is arranged in a graft type. ing. [Note: “(meth) acryl” in (meth) acrylic acid, (meth) acrylate, (meth) acrylamide notation in this specification means to describe both “acryl” and “methacryl” It shall be. ]
[0005]
However, when the base resin is used, the graffiti removing function, the icing and snow preventing function, and the sticker removing function are maintained more than expected, but more than expected. In other words, you can remove graffiti with lacquer spray, felt-tip pen, etc. with a simple operation such as dry wiping as soon as you paint, snow and ice can easily fall without removing any hand, or sticker can be removed easily However, due to the external environment such as sunlight, rainfall, etc., the performance may be reduced due to the deterioration of the coating film presumably due to the dropping of the polydimethylsiloxane part and / or the cutting of the crosslinked part. In the end, a great deal of labor was required, such as removing graffiti by forcibly rubbing, and there was a problem from the viewpoint of maintaining the above functions.
[0006]
Japanese Patent Laid-Open No. 9-100445 copolymerizes (meth) acrylic acid ester using a polydimethylsiloxane compound capable of generating radicals such as an azo group and a peroxy group, and arranges polydimethylsiloxane in a block type in the molecular chain. A base resin is described.
[0007]
However, since the polydimethylsiloxane compound capable of generating radicals such as the azo group and peroxy group is very expensive, the resin itself is very expensive. If the amount of the polydimethylsiloxane capable of generating radicals is reduced to make it cheaper, the graffiti removal function, the icing and snow prevention function, and the sticker removal function are degraded. In addition, from the viewpoint of maintaining the graffiti removal function, the icing and snow prevention function, and the sticker removal function for a long period of time, it is unexpected that polydimethylsiloxane will not fall off, but unexpectedly, the function maintainability There was also a problem that was not good.
In JP-A-11-349893, JP-A-2000-7995, etc., in addition to increasing the water repellency of a conventional ice / snow prevention function equal base resin, even if the contact angle is not large, water droplets can be slid down. Describes a technique for producing an ice / snow prevention function. In the above technique, a siloxane / sulfonic acid adduct is added, and this is made to function as a kind of surfactant, thereby causing slipping of water droplets. This additive is added in a relatively large amount. In addition, the strength of the coating is inferior, and further, if the additive is washed away, the effect is lost. Also, based on the same concept, Japanese Patent Application Laid-Open No. 2000-160132 describes a technique for obtaining a grafted product by directly reacting a fluororesin and polysiloxane. However, this type of grafted product also has problems in the mechanical strength of the coating and the maintenance of the function.
[0008]
As means for solving the above-mentioned problems, the present inventors disclosed in Japanese Patent Application Laid-Open No. 2000-119354, polydimethylsiloxane and other monomers having radical polymerization in the presence of a fluororesin having a radical polymerizable unsaturated bond. A base resin was proposed in which polydimethylsiloxane was disposed on the “leaf” portion of the “trunk-branch-leaf”.
[0009]
However, although the base resin has good maintainability of the contact angle of water and oil, it is still insufficient from the viewpoint of maintaining the graffiti removal function, the icing snow prevention function, and the sticker removal function for a long time. It was.
[0010]
[Problems to be solved by the invention]
Under the circumstances as described above, one of the problems of the present invention is to apply to structures such as building outer walls, utility poles, piers, etc., and remove graffiti by lacquer spray, felt pens, etc. by a simple method such as wiping. An object of the present invention is to provide a coating composition and a coated article formed by coating the coating composition for maintaining the graffiti removal function for a long period of time.
Another object of the present invention is to prevent or adhere to the adhesion of snow and ice by applying to building outer walls, roofs, power poles, electric wires, power transmission towers, signboards, traffic signs, airplanes, railway vehicles, ships, etc. To provide a coating composition that makes it possible to easily remove snow and ice, or to make it easier for snow on an inclined roof or the like to slide down, and a coated article formed by coating the coating composition. is there.
Still another problem of the present invention is that posters, advertising leaflets and the like applied to structures such as building outer walls, utility poles, bridge piers, signboards, telephone boxes, etc. are naturally peeled off. An object of the present invention is to provide a coating composition and a coated article formed by coating the coating composition, which can be easily removed.
[0011]
[Means for Solving the Problems]
The challenge to the above feature to remove graffiti is
(A) 2 to 70% by weight of a fluororesin having a radically polymerizable unsaturated bond via a urethane bond,
(B) The following general formula (1)
[Chemical formula 5]

(However, R in the formula¹Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R², R³, R⁴, R⁵, R⁶Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and n is an integer of 2 or more. )
A one-end radical-polymerizable polysiloxane represented by the following general formula (2):
[Chemical 6]

(However, R in the formula⁷Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R⁸, R⁹, R¹⁰, R¹¹, R¹²Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, p is an integer of 0 to 10, and q is an integer of 2 or more. )
5 to 40% by weight of one-end radical polymerizable polysiloxane represented by
(C) a monomer having an alkoxysilyl group 5 to 55% by weight,
(D) 15 to 50% by weight of a monomer having a hydroxyl group,
(E) 0 to 73% by weight of a monomer having a functional group that does not react with components (A) to (D) other than radical polymerization,
(However, (A) to (E) take a value such that the sum of them is 100% by weight) The base resin (a) obtained by copolymerization and the base resin (a) can be crosslinked. This can be solved by the present invention using a coating composition containing a certain curing agent (b).
The problem about preventing the adhesion of snow and ice, or allowing the sticker to peel off naturally,
(A) 2 to 70% by weight of a fluororesin having a radically polymerizable unsaturated bond via a urethane bond,
(B) The following general formula (1)
[Chemical 7]

(However, R in the formula¹Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R², R³, R⁴, R⁵, R⁶Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and n is an integer of 2 or more. )
A one-end radical-polymerizable polysiloxane represented by the following general formula (2):
[Chemical 8]

(However, R in the formula⁷Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R⁸, R⁹, R¹⁰, R¹¹, R¹²Are the same or different hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, p is an integer of 0 to 10, and q is an integer of 2 or more. )
5 to 40% by weight of a single-end radical polymerizable polysiloxane represented by
(C) a monomer having an alkoxysilyl group 5 to 55% by weight,
(D) 3 to 30% by weight of a monomer having a hydroxyl group,
(E) 0 to 85% by weight of a monomer having a functional group that does not react other than the components (A) to (D) and radical polymerization
(However, (A) to (E) take a value such that the sum of them is 100% by weight) The base resin (a) obtained by copolymerization and the base resin (a) can be crosslinked. It can be solved by the present invention that a coating composition comprising a certain curing agent (b) as an essential constituent is used.
[0012]
The present invention also relates to a coated article using the above coating composition.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the coating composition of the present invention and the coated article using the coating composition will be described in detail. The organic solvent-soluble fluororesin (A) having radical polymerizability through the urethane bond used in the present invention is composed of a fluororesin (A-1) having a hydroxyl group and a radical polymerizable monomer having an isocyanate group (A-2). ) Is reacted. The radical polymerizable monomer (A-2) having an isocyanate group is a reaction product of a diisocyanate (A-2-1) and a radical polymerizable monomer (A-2-2) having a hydroxyl group, methacryloyl isocyanate, 2- One or more selected from isocyanatoethyl methacrylate, m- or p-isopropenyl-α, α-dimethylbenzyl isocyanate, and preferably methacryloyl isocyanate, 2-isocyanatoethyl methacrylate, m- or p One or more of isopropenyl-α, α-dimethylbenzyl isocyanate is used.
[0014]
Examples of the diisocyanate (A-2-1) include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 1,3-bis (diisocyanatomethyl) cyclohexane, 1,3-bis (α, α -Dimethylisocyanatomethyl) benzene, 4,4'-diphenylmethane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate and the like can be mentioned, and these can be used alone or in admixture of two or more. The radical polymerizable monomer (A-2-2) having a hydroxyl group is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, Examples thereof include 4-hydroxybutyl (meth) acrylate, p-hydroxystyrene, p-hydroxymethylstyrene, and the like, and can be used alone or in admixture of two or more.
[0015]
The reaction of the diisocyanate (A-2-1) and the radically polymerizable monomer (A-2-2) having a hydroxyl group can be carried out at a molar ratio of 1/1 by a known method.
[0016]
The hydroxyl value of the fluororesin (A-1) having a hydroxyl group is preferably 5 to 250, more preferably 10 to 200, and still more preferably 20 to 150. If the hydroxyl value is less than 5, the amount of the radically polymerizable monomer (A-2) having an isocyanate group is remarkably reduced, so that grafting does not proceed sufficiently and the reaction mixture tends to become cloudy. Moreover, since the hydroxyl value of base resin (a) becomes small as a result, a graffiti removal function falls. On the other hand, when the hydroxyl value exceeds 250, the compatibility with the below-mentioned one-end radical polymerizable polysiloxane (B) is deteriorated and phase separation may occur, and the graft copolymerization itself may not proceed.
In addition, since the amount of the curing agent (b) to be described later increases inevitably, the hydrophilic portion of the coating (crosslinked portion by urethane bond) increases and the surface energy increases, resulting in the function of preventing icing and snow and preventing sticking. It is not preferable because the function is lowered.
[0017]
The fluororesin (A-1) having such a hydroxyl group can be prepared by a known method, but a commercially available product can also be used. Commercially available products include Lumiflon (registered trademark) LF-100, LF-200, LF-302, LF-400, LF-554, LF-600, LF-986N (manufactured by Asahi Glass Co., Ltd.), Cefalcoat (registered trademark) PX- 40, A606X, A202B, CF-803 (manufactured by Central Glass Co., Ltd.), ZAFLON (registered trademark) FC-110, FC-220, FC-250, FC-275, FC-310, FC-575, XFC-973 (Dongguan) Synthetic Co., Ltd.), Zeffle (registered trademark) GK-510 (manufactured by Daikin Industries), Fluonate (registered trademark) K-700, K-702, K-703, K-704, K-705 (Dainippon Ink and Chemicals, Inc.) Etc.).
[0018]
These fluororesins (A-1) having a hydroxyl group may be used alone or in combination of two or more.
[0019]
The radical polymerizable monomer (A-2) having an isocyanate group reacts in an amount of 0.001 mol or more and less than 0.1 mol per equivalent of hydroxyl group of the fluororesin (A-1) having a hydroxyl group. Preferably it is 0.01 mol or more and less than 0.08 mol per equivalent of hydroxyl group of the fluororesin (A-1) having a hydroxyl group. If the radical polymerizable monomer (A-2) having an isocyanate group is less than 0.001 mol, graft copolymerization becomes difficult and the reaction mixture may become cloudy. Moreover, when it is 0.1 mol or more, gelation tends to occur during graft copolymerization, which is not preferable.
[0020]
The reaction between the fluororesin having a hydroxyl group (A-1) and the radical polymerizable monomer having an isocyanate group (A-2) may be performed at room temperature to 80 ° C. in the absence of a catalyst or in the presence of a catalyst.
[0021]
The one-end radical polymerizable polysiloxane (B) used in the present invention has the general formula (1)
[Chemical 9]

[R in the formula¹Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, and a cyclohexyl group, preferably a hydrogen atom, It is a methyl group. R in the formula², R³, R⁴, R⁵, R⁶Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be the same as or different from each other, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group and a cyclohexyl group. Preferably R², R³, R⁴, R⁵For methyl, phenyl, R⁶Is a methyl group, a butyl group or a phenyl group. N in the formula is an integer of 2 or more, preferably an integer of 10 or more, more preferably an integer of 30 or more. ]
And / or general formula (2)
[Chemical Formula 10]

[R in the formula⁷Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, and a cyclohexyl group, preferably a hydrogen atom, It is a methyl group. R in the formula⁸, R⁹, R¹⁰, R¹¹, R¹²Is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be the same as or different from each other, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group and a cyclohexyl group. Preferably R⁸, R⁹, R¹⁰, R¹¹For methyl, phenyl, R¹²Is a methyl group, a butyl group or a phenyl group. Moreover, p in a formula is an integer of 0-10, Preferably it is 3. Moreover, q in a formula is an integer greater than or equal to 2, Preferably it is an integer greater than or equal to 10, More preferably, it is an integer greater than or equal to 30. ] Is shown.
[0022]
Such a one-terminal radically polymerizable polysiloxane (B) can be prepared by a known method, but a commercially available product can also be used, and an example of a commercially available product is Silaplane (registered trademark) FM-0711. (Number average molecular weight 1,000; manufactured by Chisso), Silaplane (registered trademark) FM-0721 (number average molecular weight 5,000; manufactured by Chisso), Silaplane (registered trademark) FM-0725 (number average molecular weight 10, 000; manufactured by Chisso Corporation), X-22-174DX (number average molecular weight 4,600; manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
[0023]
These single-terminal radically polymerizable polysiloxanes (B) may be used alone or in combination of two or more.
[0024]
These one-terminal radically polymerizable polysiloxane (B) is used in the range of 5 to 40% by weight, preferably in the range of 10 to 30% by weight, based on the total amount of the base resin. If it is less than 5% by weight, the initial graffiti removal function is insufficient and / or the maintainability of the graffiti removal function is deteriorated, and the initial anti-icing snow prevention function is insufficient and / or the maintainability of the anti-icing snow prevention function is deteriorated. Or, the initial anti-sticking function is inadequate and / or the maintainability of the anti-sticking function is deteriorated, and if it exceeds 40% by weight, the crosslinking density per unit volume of the coating composition is lowered, so that lacquer spray, felt pen, etc. Lacquer and ink are more likely to penetrate, resulting in insufficient initial graffiti removal function, insufficient strength of the coating and insufficient maintenance of the icing and snow prevention function, Sustainability is insufficient.
[0025]
The monomer (C) having an alkoxysilyl group used in the present invention is not particularly limited as long as it has a dialkoxyalkyl group or a trialkoxysilyl group and a radical polymerizable double bond. Roxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, glycidyl (meth) acrylate and 3 , 4-epoxycyclohexylmethyl (meth) acrylate and γ-aminopropyltrimethoxysilane or γ-aminopropyltriethoxysilane molar ratio 1/1 reaction product, glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl Mole ratio 1/1 of (meth) acrylate and γ-mercaptopropyltrimethoxysilane or γ-mercaptopropyltriethoxysilane, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and γ-isocyanate Examples include a reactant having a molar ratio of natopropyltrimethoxysilane of 1/1. Among them, from the viewpoint of copolymerization, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane are preferable, and γ- Particularly preferred are methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane.
[0026]
These monomers (C) having an alkoxysilyl group may be used alone or in combination of two or more.
[0027]
These alkoxysilyl group-containing monomers (C) are used in an amount of 5 to 55% by weight, preferably 10 to 50% by weight, more preferably 15 to 40% by weight, based on the total amount of the base resin (a). %. If it is less than 5% by weight, the crosslinking density of the coating composition will not increase, so the initial graffiti removal function will decrease, or there will be a problem with the strength of the coating, resulting in a decrease in maintainability of the anti-icing and snow preventing function and the paper sticking preventing function. To do. On the other hand, if it exceeds 55% by weight, the crosslink density becomes too high and the coating becomes brittle, or the amount of component (E) to be described later is reduced, so that it becomes difficult to adjust the glass transition temperature (Tg) of the base resin (a). The graffiti removal function may deteriorate.
[0028]
The monomer (D) having a hydroxyl group used in the present invention is not particularly limited as long as it has a hydroxyl group and a radical polymerizable double bond, and examples thereof include p-hydroxystyrene, p-hydroxymethylstyrene, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, di-2-hydroxyethyl fuma Various kinds of products such as rate, polyethylene glycol or polypropylene glycol mono (meth) acrylate, or their ε-caprolactone adduct, Plaxel (registered trademark) FM or FA series (manufactured by Daicel Chemical Industries, Ltd .; caprolactone adduct monomer) α, β-D Hydroxyalkyl esters of tyrenically unsaturated carboxylic acids, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, α, β-ethylenically unsaturated carboxylic acids and ε-caprolactone Examples include adducts or adducts of these α, β-ethylenically unsaturated carboxylic acids with epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and Cardura (registered trademark) E (manufactured by Shell Chemical Co., Ltd.). Among them, mainly from the viewpoint of adjusting Tg of the polymer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate is preferably used.
[0029]
These monomers (D) having a hydroxyl group may be used alone or in combination of two or more.
[0030]
Regarding the graffiti removal function, the hydroxyl group-containing monomer (D) is used in a range of 15 to 50% by weight, preferably in a range of 20 to 30% by weight, based on the total amount of the base resin (a).
With regard to the function of preventing icing and snowing and preventing paper sticking, the monomer (D) having a hydroxyl group is used in the range of 3 to 30% by weight, preferably 5 to 15% by weight, based on the total amount of the base resin (a). It is a range.
If the monomer (D) having a hydroxyl group is less than 3%, the crosslinking density of the coating composition does not increase, and the strength and solvent resistance of the coating decrease. Even if the graffiti removal function is less than 15%, the initial graffiti removal function deteriorates because the crosslinking density of the coating composition is insufficient.
On the other hand, if it exceeds 30% by weight, the amount of the curing agent (b) to be described later will inevitably increase, so the hydrophilic part (crosslinked part due to urethane bond) per unit volume of coating will increase, and the function of preventing icing and snowing or preventing sticking to paper Is unfavorable because of lowering. On the other hand, if it exceeds 50% by weight, the crosslink density is too high and the coating becomes brittle, or the base resin (a) becomes turbid due to the formation of molecular micelles.
[0031]
The monomer (E) having a functional group that does not react other than radical polymerization with the components (A) to (D) in the present invention is different from the components (A) to (D) at the reaction temperature and reaction conditions at the time of radical polymerization. Those that do not react are selected, for example, styrenes such as styrene, p-methylstyrene, p-chloromethylstyrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i -Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Rate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylates having a hydrocarbon group such as benzyl (meth) acrylate, these hydrogen atoms as fluorine, chlorine, bromine atoms, etc. Substituted (meth) acrylates, vinyl acetate, vinyl benzoate, Veova (registered trademark) (manufactured by Shell Chemical Co., Ltd .; vinyl ester of branched monocarboxylic acid), etc., acrylonitrile such as acrylonitrile, methacrylonitrile, etc. , Vinyl ethers such as ethyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, cyclohexyl vinyl ether, vinyl ethers in which these hydrogen atoms are substituted with fluorine, chlorine, bromine atoms, etc., (meth) acrylamide, dimethyl ( ) Acrylamides such as acrylamide and diacetone acrylamide, acrylamides in which these hydrogen atoms are substituted with fluorine, chlorine, bromine atoms, etc., glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3, Epoxy group-containing vinyl compounds such as 4-epoxyvinylcyclohexane, olefins such as ethylene and propylene, halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, tetrafluoroethylene and chlorotrifluoroethylene In addition, maleimide, vinyl sulfone and the like can be mentioned, and a plurality of these can be used in appropriate combination, and (meth) acrylates are preferably used mainly from the viewpoint of copolymerization.
[0032]
On the other hand, as an unfavorable component (E), vinyl pyridine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, 4 -Basic nitrogen-containing vinyl compounds such as (N, N-dimethylamino) styrene and N- {2- (meth) acryloyloxyethyl} piperidine, (meth) acrylic acid, angelic acid, crotonic acid, maleic acid, 4 Examples include acidic vinyl compounds such as vinyl benzoic acid, p-vinylbenzenesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, and mono {2- (meth) acryloyloxyethyl} acid phosphate. The basic nitrogen-containing vinyl compounds and acidic vinyl compounds function as a catalyst for dissociating and condensing the alkoxysilyl group of the monomer (C) having an alkoxysilyl group. When stored for a long time, it may thicken and gel.
[0033]
Regarding the graffiti removal function, the component (E) is preferably used in combination so that the final base resin (a) has a Tg of 40 ° C. or higher. If the Tg of the final substrate resin (a) is less than 40 ° C., the Tg of the coating after the coating composition is cured will not increase so much, especially in the summer, the coating is exposed to high temperatures by direct sunlight, etc. The graffiti removal function may decrease. Regarding the graffiti removal function, these components (E) are used in the range of 0 to 73% by weight based on the total amount. If it exceeds 73% by weight, the amount of introduction of other components, particularly components (C) and (D) for increasing the crosslinking density is lowered, so that the graffiti removing function or its maintainability becomes insufficient.
With regard to the function of preventing icing and snowing or preventing paper sticking, the component (E) is used in the range of 0 to 85% by weight based on the total amount. If it exceeds 85% by weight, the amount of other components (B) to (D) introduced will be reduced. When the introduction amount of the component (B) is lowered, the function or the maintenance thereof is insufficient, and when the introduction amount of the component (C) and / or (D) is lowered, the strength of the coating is lowered. To do.
Here, 0% by weight means that the component (E) is not present.
[0034]
The ratio of the components (A) and (B) to (D) in the present invention [(A) / ((B) + (C) + (D)); hereinafter, the base graft ratio is abbreviated] is 70/30 to 2 / A range of 98 is selected. When the base graft ratio exceeds 70/30 and the ratio of component (A) is large, the amount of introduction of components (B) to (D) decreases, so that the gloss of the coating is reduced, and the graffiti removal function, wearing Ice / snow prevention function and sticker prevention function deteriorate. In addition, when the base graft ratio is less than 2/98 and the ratio of components (B) + (C) + (D) is large, the weather resistance and contact angle maintenance of the coating are lowered, and the graffiti removal function, wearing Maintainability of the ice / snow prevention function and the sticker prevention function is deteriorated.
[0035]
For preparing the base resin (a) using the monomers as mentioned above, it is most convenient to use a solution radical polymerization method or a non-aqueous dispersion radical polymerization method among known polymerization methods. Especially recommended.
[0036]
Examples of the solvent used in the polymerization include aromatic hydrocarbons such as toluene, xylene, Solvesso (registered trademark) 100 (manufactured by Esso Petroleum), fats such as n-hexane, cyclohexane, octane, mineral spirit, and kerosene. , Alicyclic hydrocarbons, esters such as ethyl acetate, n-butyl acetate, i-butyl acetate, butyl cellosolve acetate, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, etc. Examples include alcohols, glycols such as ethylene glycol, propylene glycol, ethyl cellosolve, and butyl cellosolve, or glycol ethers. These may be used alone or in combination of two or more.
[0037]
The polymerization can be carried out by a conventional method using various known and conventional radical polymerization initiators such as azo compounds or peroxides.
[0038]
The polymerization time is not particularly limited, but usually a range of 1 to 48 hours is selected industrially. Moreover, superposition | polymerization temperature is 30-150 degreeC normally, Preferably it is 60-120 degreeC.
[0039]
In the polymerization, if a side reaction does not occur as required, a known and commonly used chain transfer agent such as butyl mercaptan, dodecyl mercaptan, α-methylstyrene dimer or the like can be added.
[0040]
In the present invention, the base resin (a) has a weight average molecular weight of about 5,000 to 2,000,000 by GPC (gel permeation chromatography) in terms of polystyrene. If it is less than 5,000, the film-forming property, the weather resistance of the coating, and the chemical resistance deteriorate, resulting in the maintainability of the graffiti removal function, the icing / snow prevention function, or the sticker prevention function. If it decreases and exceeds 2,000,000, there is a risk of gelation during polymerization, which is not preferred.
[0041]
As the curing agent (b) capable of cross-linking with the base resin (a) of the present invention, a curing agent capable of reacting with the hydroxyl group of the base resin (a) is appropriately selected, and is generally known as a curing agent for acrylic curable paints. You can use what you have. Examples of such a curing agent include aniline aldehyde resin, urea resin, melamine resin, polyisocyanate, and blocked polyisocyanate.
Any object can be used as long as it can be precoated such as steel plate, brick, block, signboard, traffic sign, parabolic antenna (small size), etc., but generally existing buildings as aftercoat In many cases, a polyisocyanate that can be cured at room temperature is selected because it covers a structure such as an outer wall, a utility pole, a bridge pier, a signboard, or a telephone box. Thus, when curing at room temperature, the isocyanate group is used in an amount of 0.5 to 1.5 equivalents of the hydroxyl value of the base resin, preferably 1 to 1.4 equivalents for the graffiti removal function, 0.8 to 1.2 equivalents are used for the function to prevent sticking.
[0042]
In addition, any known coating method can be applied to the coating composition of the present invention, and its non-volatile content is not particularly limited and is appropriately selected, but it is usually preferably 10 to 50% by weight.
[0043]
Furthermore, the coating composition of the present invention can be added with other resins, for example, a fluororesin, an acrylic resin, a polyester resin, an alkyd resin, a silicone resin and the like as long as they do not impair the spirit of the present invention.
The coating composition of the present invention is various additives as long as it does not impair the spirit of the present invention, for example, surfactant, extender, color pigment, rust preventive pigment, fluororesin powder, silicone resin powder, rust preventive agent. Dyes, waxes and the like can also be added. As for the graffiti removal function, the above additives generally reduce the crosslink density per unit volume of coating, and lacquers and felt pens such as lacquer sprays and felt pens tend to penetrate, so they should be kept to the minimum necessary amount. .
[0044]
In addition, the “coated article” of the present invention is a product coated with the coating composition of the present invention, which has a graffiti removal function, an object that requires an icing and snow prevention function, or a paper sticking prevention function. Although it is not particularly limited as long as it is necessary, outdoor structures such as building outer walls and roofs, gates, utility poles, bridge piers, electric wires, power transmission towers, signs, traffic signs, aircraft, railway vehicles, ships, telephone boxes, etc. In general, it may be applied to such outdoor structures in many cases.
[0045]
【Example】
Hereinafter, the present invention will be described with reference to reference examples, production examples, and examples, but the present invention is not limited to the following examples. In the following examples, “parts” represents parts by weight unless otherwise specified.
[0046]
The commercial names of the materials used in the following illustrative examples are shown below.
Fluororesin having a hydroxyl group (A-1)
-Cefalcoat (trademark) CF-803 (Central Glass Co., Ltd., hydroxyl value: 60, number average molecular weight: 15,000)
One-end radical polymerizable polysiloxane (B)
Silaplane (registered trademark) FM-0721 (manufactured by Chisso Corporation, number average molecular weight 5,000)
Radical polymerization initiator
Perbutyl (registered trademark) O (t-butylperoxy-2-ethylhexanoate; manufactured by NOF Corporation)
Curing agent; component (b)
Coronate (registered trademark) HX (Hexamethylene diisocyanate isocyanurate type polyisocyanate; manufactured by Nippon Polyurethane)
[0047]
In addition, test items in the examples are shown below.
Appearance of the coating composition cured film
Abnormality of the film was confirmed visually.
Graffiti removal (initial)
Draw a line with black magic ink (registered trademark of Yoko Uchida, felt pen made by Teranishi Chemical Co., Ltd.) on the coating surface of the cured coating composition, dry at room temperature for 24 hours, and then wipe with a cloth. Ink (registered trademark) where no trace remains is indicated by ◯, a slight trace remains △, and a clear trace is indicated by X.
Water repellency (initial, after exposure)
Using a CA-W type automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd. as an instrument, about 5 μl of deionized water was placed on the coated plate coated with the coating composition, and the contact angle at this time was measured. 6 points were measured by changing the mounting position, the average value was calculated at 4 points excluding the smallest value and the largest value, and rounded to an integer value by rounding off. The results are shown in FIG. 1 and FIG. Further, using a Ci4000 sunshine weatherometer manufactured by ATLAS, the coated plate was exposed according to ISO11341; method 1 outdoors (coating, varnish accelerated weathering test method) using xenon as a light source. The coating plate was taken out every 100 hours up to 600 hours, and after sufficiently removing moisture, contact angle measurement was performed in the same manner as described above. A result is combined with FIG. 1 and FIG.
Graffiti removal (after exposure)
The surface of the cured coating composition exposed for 600 hours under the above-mentioned exposure conditions was drawn with Magic Ink (registered trademark) black to sufficiently dry the Magic Ink (registered trademark) solvent (about 2 hours), and then the surface Was evaluated by wiping and drying in the same manner as described above.
Solvent resistance
A drop of xylene was placed on the coated plate and allowed to stand at room temperature until the xylene volatilized, and the state of the coating film was visually observed.
Anti-icing property
The coated plate was placed in a freezer at −20 ° C. and left overnight. Three pieces of tap water (50 μl) were placed on the cover plate with a dropper so that each drop would be one drop, and further kept at −20 ° C. for 2 hours to freeze. ○ If the ice has fallen by simply tapping the cover plate with your hand while keeping the cover plate horizontal, △ if the ice has fallen by touching the ice by hand, or if the ice cannot be removed or the ice has been destroyed. A piece of ice remaining on the surface was evaluated as x. The measurement was performed every time the sunshine weatherometer was exposed for 100 hours. The results are shown in Table 4.
Adhesion prevention 1
The coated plate was placed in a thermostatic chamber at 23 ° C. and a relative humidity of 50% and left to stand for conditioning. A paper sheet (30 × 50 mm) coated with an aqueous paste (manufactured by Dragonfly Pencil Co., Ltd .; Aqua Pit (registered trademark)) on the entire surface was attached to the cover plate, and the cover plate was kept vertical. Those that were automatically peeled off as the paste dried were evaluated as ◯, and those that did not peel off were evaluated as ×. The evaluation was performed on the sunshine weatherometer 0 hours (before irradiation) and 600 hours elapsed. The results are shown in Table 5.
Adhesion prevention 2
A cloth gummed tape (manufactured by Sekisui Chemical Co., Ltd .; cloth tape No. 600) is affixed to the coated plate that has been conditioned in the same manner as above, and peeled off by hand. The case where it broke was evaluated by x. The evaluation was performed on the sunshine weatherometer 0 hours (before irradiation) and 600 hours elapsed. The results are shown in Table 5.
[0048]
[Reference Example 1]
Synthesis example of fluororesin (A) having radical polymerizability via urethane bond
In a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser, and a dry nitrogen gas inlet, 1,554 parts of cefal coated CF-803, 233 parts of xylene, 6.3 parts of 2-isocyanatoethyl methacrylate, Heated to 80 ° C. in a dry nitrogen atmosphere. After reacting at 80 ° C. for 2 hours and confirming that the absorption of isocyanate disappeared by the infrared absorption spectrum of the sample, the reaction mixture was taken out to obtain component (A) having a nonvolatile content of 50%.
[0049]
[Production example <Table 1> 1]
Synthesis Example of Base Resin (a) for Graffiti Prevention Coating Composition <Table 1> 1
Into a glass reactor equipped with a mechanical stirrer, a thermometer, a condenser, and a dry nitrogen gas inlet, 40 parts of the component (A) synthesized in Reference Example 1 and 80 parts of n-butyl acetate were placed in a nitrogen atmosphere. After heating to 90 ° C., 20 parts of premixed methyl methacrylate, 7 parts of 2-ethylhexyl methacrylate, 23 parts of 2-hydroxyethyl methacrylate, 10 parts of FM-0721, 20 parts of γ-methacryloxypropyltrimethoxysilane, perbutyl O 2 A mixture of 22 parts of xylene and 22 parts of xylene was added dropwise at the same temperature over 2 hours. After maintaining at the same temperature for 2 hours, 1 part of perbutyl O is added, and further maintained at 90 ° C. for 5 hours, whereby the desired base resin (a) having a nonvolatile content of 45% and a weight average molecular weight of 58,000 is obtained. A solution was obtained.
[Production example <Table 2> 1]
Synthesis example of base resin (a) for anti-icing / snow-preventing coating composition and paper paste-preventing coating composition <Table 2> 1
60 parts of component (A) synthesized in Reference Example 1 and 90 parts of n-butyl acetate were placed in a glass reactor equipped with a mechanical stirrer, thermometer, condenser, and dry nitrogen gas inlet, and in a nitrogen atmosphere. After heating to 90 ° C., premixed methyl methacrylate 15 parts, 2-ethylhexyl methacrylate 10 parts, 2-hydroxyethyl methacrylate 10 parts, FM-0721 15 parts, γ-methacryloxypropyltrimethoxysilane 20 parts, perbutyl O 2 A mixture of 30 parts of xylene and 30 parts of xylene was added dropwise at the same temperature over 2 hours. After maintaining at the same temperature for 2 hours, 1 part of perbutyl O was added, and further maintained at 90 ° C. for 5 hours, whereby a desired base resin (a) having a nonvolatile content of 40% and a weight average molecular weight of 96,000 Solution was obtained.
[0050]
[Production Examples <Table 1> 2 to 10]
Synthesis Examples of Base Resin for Graffiti Prevention Coating Composition (a) or Comparative Base Resin <Table 1> 2 to 10
A base resin (a) in Table 1 or a comparative base resin solution was obtained in the same manner as in Production Example <Table 1> 1 except that the amount of each component was changed as shown in Table 1. . Among these, Production Examples <Table 1> 2 and <Table 1> 3 are examples consistent with the base resin (a) in the claims of the present invention. In addition, when Production Example 4 does not contain the component (A), Production Example <Table 1> 5 and <Table 1> 6 show that the component (B) is 3% by weight and 45% by weight of the whole base resin, Production Examples <Table 1> 7 and <Table 1> 8 are components (C) of 3% by weight and 60% by weight of the whole base resin, respectively, and Production Examples <Table 1> 9 and <Table 1> 10 are components ( D) is an example of 10% by weight and 55% by weight of the whole base resin, respectively, and neither is an example corresponding to the base resin (a) defined in the claims of the present invention.
[Production Examples <Table 2> 2 to 10]
Synthesis examples of base resin (a) for anti-icing and snow-preventing coating composition and anti-sticking coating composition or comparative base resin <Table 2> 2 to 10
A base resin (a) in Table 2 or a comparative base resin solution was obtained in the same manner as in Production Example <Table 2> 1 except that the amount of each component was changed as shown in Table 2. . Among these, the production examples <Table 2> 2 and <Table 2> 3 are examples consistent with the base resin (a) in the claims of the present invention. In addition, in the production example <Table 2> 4, when the component (A) is not contained, in the production examples <Table 2> 5 and <Table 2> 6, the component (B) is 3% by weight of the whole base resin (a). , 55% by weight, Production Examples <Table 2> 7 and <Table 2> 8 show Production Examples <Table 2> when Component (D) is 0% by weight and 40% by weight of the entire base resin (a), respectively. 9 and Table 2 are examples in which the component (C) is 3% by weight and 60% by weight, respectively, of the whole base resin (a), both of which are defined in the claims of the present invention. This is not an example.
[0051]
[Table 1]

[Table 2]

[0052]
[Example <Table 3> 1]
On a cold-rolled steel plate (50 x 150 mm) polished in advance with a paper file, V Freon (registered trademark) # 100 (white) made by Dainippon Paint Co., Ltd., which is a two-component fluororesin paint, is used with a bar coater # 75. Then, the coating was applied to a dry film thickness of about 50 μm and cured for 24 hours to form a white coating film. Production Example <Table 1> To the base resin (a) obtained in 1 was added 1.2 times equivalent of Coronate (registered trademark) HX with respect to the hydroxyl equivalent of the resin, and the non-volatile content in the paint was 35% by weight. The coating composition was prepared by diluting with n-butyl acetate so as to be and coated on the white coating film. This was cured at 23 ° C. and 50% relative humidity for 7 days to obtain a coated plate. Various tests described above were performed, and the results are shown in Table 3 and FIG. This coating had good scribble removability and a contact angle of 102 °, and the graffiti removability after exposure and the maintenance of the contact angle were also good.
[Example <Table 4> 1]
On a cold-rolled steel plate (50 x 150 mm) polished in advance with a paper file, V Freon (registered trademark) # 100 (white) made by Dainippon Paint Co., Ltd., which is a two-component fluororesin paint, is used with a bar coater # 75. Then, the coating was applied to a dry film thickness of about 50 μm and cured for 24 hours to form a white coating film. Production Example <Table 2> Coronate (registered trademark) HX of 1.0 equivalent to the hydroxyl equivalent of the resin was added to the base resin (a) obtained in 1, and the non-volatile content in the paint was 35% by weight. The coating composition was prepared by diluting with n-butyl acetate and coated on the white coating film. This was cured at 23 ° C. and 50% relative humidity for 7 days to obtain a coated plate. Various tests described above were performed, and the results are shown in Table 4 and FIG. This coating showed good results in all test items.
[Example <Table 5> 1]
On a cold-rolled steel plate (50 x 150 mm) polished in advance with a paper file, V Freon (registered trademark) # 100 (white) made by Dainippon Paint Co., Ltd., which is a two-component fluororesin paint, is used with a bar coater # 75. Then, the coating was applied to a dry film thickness of about 50 μm and cured for 24 hours to form a white coating film. Production Example <Table 2> Coronate (registered trademark) HX of 1.0 equivalent to the hydroxyl equivalent of the resin was added to the base resin (a) obtained in 1, and the non-volatile content in the paint was 35% by weight. The coating composition was prepared by diluting with n-butyl acetate and coated on the white coating film. This was cured at 23 ° C. and 50% relative humidity for 7 days to obtain a coated plate. Various tests described above were performed, and the results are shown in Table 5 and FIG. This coating showed good results in all test items.
[0053]
Examples <Table 3> 2, <Table 3> 3, Comparative Examples <Table 3> 1 to <Table 3> 7]
Example <Example 3> In place of the base resin (a) used in Example 1, the base resin (a) obtained in Production Examples <Table 1> 2 to <Table 1> 10 or the base resin for comparison was used. <Table 3> A coated plate was produced in the same manner as in 1. The results are shown in Table 3. In Examples <Table 3> 2 and <Table 3> 3, good results were shown in all evaluation items. However, in Comparative Examples <Table 3> 1 and <Table 3> 2, the initial graffiti removability was good, but there were difficulties in maintaining the graffiti removability after exposure. Also, the contact angle was greatly reduced by exposure. In Comparative Example 3, bleeding of unreacted residual monomers was observed on the coating surface, and the coating surface was sticky. Since the crosslinking density per unit volume of the coating decreased, graffiti penetration was observed from the beginning. Similarly, in Comparative Examples <Table 3> 4 and <Table 3> 6, graffiti penetration was observed from the beginning. In Comparative Examples <Table 3> 5 and <Table 3> 7, the base resin (a) formed micelles and became turbid, and thus the coating appearance was also turbid and exhibited poor appearance.
FIG. 1 shows an example <Table 3> 1, an example <Table 3> 2, an example <Table 3> 3, a comparative example <Table 3> 1, and a comparative example <Table 3> 2. The results of the “water repellency (initial, after exposure)” test on the surface of the cured coating composition of Example 1, Example 2, Example 3, Comparative Example 1, and Comparative Example 2) are shown.
[0054]
[Table 3]

Examples <Table 4> 2, <Table 4> 3, Comparative Examples <Table 4> 1 to <Table 4> 7]
Example <Table 4> Instead of the base resin (a) used in 1, an example using the base resin (a) obtained in Production Examples <Table 2> 2 to <Table 2> 10 or a comparative base resin <Table 4> A coated plate was produced in the same manner as in 1. The results are shown in Table 4. In Examples <Table 4> 2 and <Table 4> 3, good results were shown in all evaluation items. However, in Comparative Examples <Table 4> 1 and <Table 4> 2, although the anti-icing property was good, there was a difficulty in the anti-icing property after exposure. Also, the contact angle was greatly reduced by exposure. In Comparative Example <Table 4> 3, bleeding of unreacted residual monomer was observed on the coating surface, and it was sticky. Comparative Examples <Table 4> 4 and <Table 4> 6 had difficulty in solvent resistance of the coating. In Comparative Examples <Table 4> 5 and <Table 4> 7, the base resin (a) formed micelles and became turbid. For this reason, the coating appearance was also turbid and exhibited poor appearance.
In FIG. 2, Example <Table 4> 1, Example <Table 4> 2, Example <Table 4> 3, Comparative Example <Table 4> 1, Comparative Example <Table 4> 2 The results of the “water repellency (initial, after exposure)” test on the surface of the cured coating composition of Example 1, Example 2, Example 3, Comparative Example 1, and Comparative Example 2) are shown.
[0055]
[Table 4]

Examples <Table 5> 2, <Table 5> 3, Comparative Examples <Table 5> 1 to <Table 5> 7]
Example <Table 4> Instead of the base resin (a) used in 1, an example using the base resin (a) obtained in Production Examples <Table 2> 2 to <Table 2> 10 or a comparative base resin <Table 4> A coated plate was prepared in the same manner as in 1, and further tested for preventing paper sticking. The results are shown in Table 5 (appearance and solvent resistance overlap with Table 4). In Examples <Table 5> 2 and <Table 5> 3, good results were shown in all evaluation items. However, in Comparative Examples <Table 5> 1 and <Table 5> 2, both of the initial paper-proofing properties 1 and 2 were good, but there were difficulties in paper-proofing properties after exposure. Also, the contact angle was greatly reduced by exposure. In Comparative Example <Table 5> 3, bleeding of unreacted residual monomer was observed on the coating surface, and the coating was damaged due to the initial anti-sticking property 2. In Comparative Examples <Table 5> 4 and <Table 5> 6, the solvent resistance of the coating was difficult, and the coating was damaged due to the initial anti-sticking property 2. In Comparative Examples <Table 5> 5 and <Table 5> 7, the base resin (a) forms micelles and becomes turbid. For this reason, the coated appearance also becomes turbid and poor in appearance, and the post-exposure prevention property 1 Neither was good.
[Table 5]

[0056]
Table 6 shows the contact angle values in FIG. 1 for reference. Table 7 shows the contact angle values in FIG. 2 for reference.
[Table 6]

[Table 7]

[0057]
From the above data, the coated article obtained by using the coating composition of the present invention can give the surface excellent graffiti removal property and contact angle maintenance property, and the surface has excellent anti-icing snow resistance. Obviously, it is possible to give the surface, and it is possible to give excellent anti-sticking properties to the surface.
[0058]
【The invention's effect】
The composition for coating of the present invention and the coated article using the composition can impart a graffiti removing function when coated and have good maintainability of the function. can do. Specifically, skins and exterior walls of outdoor structures such as automobiles, railway vehicles, other vehicles, buildings (houses, buildings), gates, piers, skins of electrical equipment such as washing machines and refrigerators, and road signs It is applied to curved mirrors, etc., and is effective for contamination resistance and graffiti removal.
The coating composition of the present invention and a coated article using the composition can be applied to the surface treatment of various base materials because they can provide an anti-icing and snow-preventing function when coated and have good maintainability of the function. be able to. Specifically, the outer panels, outer walls and roofs of outdoor structures such as automobiles, railway vehicles, ships, other vehicles, buildings (housing, buildings, steel towers, gates), heat exchangers, heat sink fins, roads Applicable to signs, signboards, guide plates, curved mirrors, parabolic antennas, etc., and effective in preventing icing and snow.
The coating composition of the present invention and the coated article using the composition can be applied to the surface treatment of various base materials because they can provide a function to prevent sticking when coated and have good maintainability of the function. Can do. Specifically, it is applied to building outer walls, utility poles, bridge piers, signboards, telephone boxes, etc., and is effective in preventing sticking.
[Brief description of the drawings]
FIG. 1 is a comparative example of the water repellency of the surface of a cured product of a coating composition according to the present invention indicated by the contact angle of deionized water. It is a graph compared with the hardened | cured material surface of an example.
FIG. 2 is an example of the present invention <Table 4> 1 or Example <Table 5> 1 as shown by the contact angle of deionized water. It is the graph which compared the time-dependent change below with the hardened | cured material surface of a comparative example.

Claims (8)

(A) 2 to 70% by weight of a fluororesin having a radically polymerizable unsaturated bond via a urethane bond,
(B) The following general formula (1)

(In the formula, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ may be the same or different from each other. (Number 1 to 10 hydrocarbon group, n is an integer of 2 or more.)
A one-end radical-polymerizable polysiloxane represented by the following general formula (2):

(In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² may be the same or different from each other. (The hydrocarbon group of number 1-10, p is an integer of 0-10, q is an integer of 2 or more.)
5 to 40% by weight of one-end radical polymerizable polysiloxane represented by
(C) a monomer having an alkoxysilyl group 5 to 55% by weight,
(D) 15 to 50% by weight of a monomer having a hydroxyl group,
(E) 0 to 73% by weight of a monomer having a functional group that does not react with components (A) to (D) other than radical polymerization,
(However, (A) to (E) have a total value of 100% by weight.) The base resin (a) obtained by copolymerization and the base resin (a) can be crosslinked. A coating composition comprising the curing agent (b). The fluoropolymer (A) having radical polymerizability via a urethane bond is a reaction product of a fluoropolymer (A-1) having a hydroxyl group and a radical polymerizable monomer (A-2) having an isocyanate group. The coating composition according to claim 1. The coating composition according to claim 1 or 2, wherein the curing agent (b) capable of undergoing a crosslinking reaction with the base resin (a) is a polyisocyanate. An article obtained by coating with the coating composition according to any one of claims 1 to 3 and curing the composition. (A) 2 to 70% by weight of a fluororesin having a radically polymerizable unsaturated bond via a urethane bond,
(B) The following general formula (1)

(In the formula, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ , R ⁶ may be the same or different from each other. (Number 1 to 10 hydrocarbon group, n is an integer of 2 or more.)
A one-end radical-polymerizable polysiloxane represented by the following general formula (2):

(In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² may be the same or different from each other. (The hydrocarbon group of number 1-10, p is an integer of 0-10, q is an integer of 2 or more.)
5 to 40% by weight of a single-end radical polymerizable polysiloxane represented by
(C) a monomer having an alkoxysilyl group 5 to 55% by weight,
(D) 3 to 30% by weight of a monomer having a hydroxyl group,
(E) Monomers having functional groups that do not react other than radical polymerization with components (A) to (D) 0 to 85% by weight,
(However, (A) to (E) have a total value of 100% by weight.) The base resin (a) obtained by copolymerization and the base resin (a) can be crosslinked. A coating composition comprising the curing agent (b). The fluoropolymer (A) having radical polymerizability via a urethane bond is a reaction product of a fluoropolymer (A-1) having a hydroxyl group and a radical polymerizable monomer (A-2) having an isocyanate group. The coating composition according to claim 5. The coating composition according to claim 5 or 6, wherein the curing agent (b) capable of undergoing a crosslinking reaction with the base resin (a) is a polyisocyanate. An article obtained by coating with the coating composition according to any one of claims 5 to 8 and curing the composition.

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