JP2006167490A - Coating film formed from new silicone-containing fluorine based copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve characteristic of a coating film, particularly water-repellency/oil-repellency formed from a coating composition based on a fluorine-containing copolymer containing fluoroolefin and reactive silicone as indispensable components. <P>SOLUTION: The coating film is formed on a substrate via a curing reaction using the silicone-containing fluorine based copolymer containing the fluoroolefin and the reactive silicone as the indispensable components or the composition containing it. In the coating film with excellent contamination-proof property, water-repellency/oil-repellency, chemical-resistance and weather-resistance, the atom number of Si atom existing in the coating film surface is 2-30 atomic% or the F atom is 2-32 atomic% in addition to the existing Si atom when measured by X-ray photoelectron spectroscopy. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

（ここで、Ｒ¹は、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯ（ＣＨ₂）_r1−、ＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂）_r1−、又はＣＨ₂＝ＣＨ−を示す。Ｒ²は、炭素数１〜１２のアルキル基、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯ（ＣＨ₂）_r2−、ＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂）_r2−、又はＣＨ₂＝ＣＨ−を示す。ｎは２０〜１５０の整数、ｒ₁は１〜６の整数、ｒ₂は１〜６の整数を示す。）
Ｒ²−Ｓｉ［ＯＳｉ（ＣＨ₃）₃］₃ （２）
ＣＨ₂＝Ｃ（Ｒ³）Ｓｉ（Ｒ⁴）（Ｒ⁵）（Ｒ⁶） （３）
ここで、Ｒ³は水素原子、又はメチル基を表す。Ｒ⁴、Ｒ⁵、及びＲ⁶は、それぞれ水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ｓｅｃ−ブチル基、フェニル基、置換フェニル基、−ＣＦ₃、−Ｃ₂Ｈ₄ＣＦ₃、又は−ＯＳｉ（ＣＨ₃）₃を示す。Ｒ⁴、Ｒ⁵、Ｒ⁶は、それぞれ同一又は異なっていてもよい。）
さらに上記課題は、
重合単位として（ａ）フルオロオレフィンを１５〜８５モル％；（ｂ）式（１）、（２）及び（３）から選択される１種以上の反応性シリコーンを０．００１〜３０モル％；及び（ｃ）水酸基含有不飽和単量体を１〜５０モル％；より構成される、水酸基を含有した反応性シリコーン含有フッ素系共重合体（Ｃ）；と
不飽和イソシアネート（ｄ）
との反応により生成されたシリコーン含有フッ素系共重合体（Ｄ）を用いて形成された本発明の塗膜により解決する。
【００１３】
さらに上記課題は、シリコーン含有フッ素系共重合体（Ａ）、（Ａ’）、及び（Ｄ）からなる群より選択される１種以上のフッ素系共重合体と；アクリル系樹脂（Ｂ）、反応性希釈剤（Ｅ）、及び光硬化性（メタ）アクリレート樹脂（Ｆ）からなる群より選択される１種以上の成分と；を含む樹脂組成物を用いて形成された本発明の塗膜により解決する。
【００１４】
さらに、本発明の塗膜は：シリコーン含有フッ素系共重合体（Ａ）、（Ａ’）、及び（Ｄ）からなる群より選択される１種以上の共重合体を含む組成物を塗布し；該組成物を硬化させ；Ｘ線光電子分光法により測定された塗膜表面に存在するＳｉ原子の割合を２〜３０ａｔｏｍｉｃ％とし、Ｆ原子の割合を２〜３２ａｔｏｍｉｃ％とする；製造方法により製造される。
【００１５】
そして本願発明の優れた塗膜特性は、塗膜表面に存在するＳｉ原子の原子数とＦ原子の原子数とに起因していることを、ＸＰＳによる測定で突き止めることができた。即ち、上記のシリコーン含有フッ素系共重合体は、塗膜化した際、Ｓｉ原子が塗膜表面に選択的に局在するものであることがわかった。
【００１６】
【発明の実施の形態】
以下、本発明をより詳細に説明する。
本発明における塗膜表面組成は、ＸＰＳにより測定される。本願における組成は、実施例１記載の装置、条件により測定した値を使用した。
【００１７】
油性マジックはじき性、油性マジック繰り返し除去性、撥水性も、実施例１記載の方法、条件で測定した値を用いた。
塗膜表面のＳｉ原子の原子数は、２ａｔｏｍｉｃ％以上、特には３ａｔｏｍｉｃ％以上を占めることが好ましい。また、その上限は５０ａｔｏｍｉｃ％、好ましくは３０ａｔｏｍｉｃ％、さらに好ましくは２０ａｔｏｍｉｃ％である。上記範囲未満では油性マジックの除去性やはじき性が悪く、撥水性も劣る。また上記範囲より大では反応性シリコーンの分子量が大きくなり、製造上の取扱いが難しくなる。
【００１８】
塗膜表面のＦ原子は１ａｔｏｍｉｃ％以上、好ましくは２ａｔｏｍｉｃ％以上を占める。また、５０ａｔｏｍｉｃ％以下、好ましくは３２ａｔｏｍｉｃ％以下、さらに好ましくは２５ａｔｏｍｉｃ％以下である。上記範囲未満ではフッ素樹脂としての特性が発揮されず、上記範囲より大では繰り返し油性マジック除去性やはじき性が悪くなる。
【００１９】
Ｓｉ原子又はＦ原子の表面組成の何れか一方のみが上記の範囲にあってもよいが、両者が上記の範囲にあることが好ましい。
Ｓｉ原子の原子数とＦ原子の原子数との比（Ｓｉ／Ｆ値）としては、０．０６２５〜１５．０、特に０．０６２５〜１０．０が好ましい。Ｓｉ原子、Ｆ原子の表面組成が上記範囲にある場合において、さらにＳｉ／Ｆ値が０．０６２５〜１５．０、好ましくは０．０６２５〜１０．０、より好ましくは０．１２〜１０．０、さらに好ましくは０．１４〜１０．０であることが望ましい。
【００２０】
塗膜の撥水性の点から、水との接触角は９８〜１２０度であり、好ましくは９８〜１１０度である。
塗膜の厚みは０．００００５ｍｍ以上、好ましくは０．０００１ｍｍ以上、さらに好ましくは０．０００２ｍｍ以上である。また、２ｍｍ以下、好ましくは０．５ｍｍ以下、さらに好ましくは０．３ｍｍ以下である。塗膜が薄すぎると完全に被覆できない領域が生じ、厚すぎても効果に大きな差異が生じず、経済的でない。
【００２１】
本発明の塗膜に用いられる基材に特に制限はなく、有機材料も無機材料も用いることができる。例えば、使用できる基材の材料として、木材、プラスチック（アクリル材、ＰＥＴ等）、金属、グラファイト、紙、コンクリート、不燃材（石膏ボード、珪酸カルシウム板、フレキシブルボードなどのセラミックス材等）、ガラス等が挙げられる。透明な材質としては、アクリル材又はＰＥＴが好ましい。
【００２２】
基材の形状に特に制限はなく、平面状であっても凹凸があってもよい。本発明の塗膜を有する物品は、各種の内装用途、屋外用途に用いることができる。
該シリコーン含有フッ素系共重合体の重合単位である（ａ）フルオロオレフィンに特に制限はないが、ＣＨ₂＝ＣＨＦ、ＣＨ₂＝ＣＦ₂、ＣＨＦ＝ＣＨＦ、ＣＨＦ＝ＣＦ₂、ＣＦ₂＝ＣＦ₂、ＣＦ₂＝ＣＦＣｌ、及びＣＦ₂＝ＣＦ（ＣＦ₃）を好ましく用いることができ、ＣＦ₂＝ＣＦ₂、及び／又はＣＨ₂＝ＣＦ₂が特に好ましい。複数のフルオロオレフィンの混合物を使用することもできる。
【００２３】
（ｂ）反応性シリコーンとしては、

（ここで、Ｒ¹はＲ²¹（ＣＨ₂）_r1−（Ｒ²¹は不飽和カルボキシル基を表す）又はアルケニル基、好ましくはＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂）_r1−、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯ（ＣＨ₂）_r1−、又はＣＨ₂＝ＣＨ−を示す。ｒ₁は１〜６の整数を表し、好ましくはｒ₁＝３である。Ｒ²は、炭素数１〜１２のアルキル基、炭素数１〜１２のアルケニル基、又はＲ²¹（ＣＨ₂）_r1−（Ｒ²¹は不飽和カルボキシル基を表す）を表し、好ましくは炭素数１〜１２のアルキル基、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯ（ＣＨ₂）_r2−、ＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂）_r2−、又はＣＨ₂＝ＣＨ−を示す。ｒ₂は１〜６の整数を表し、好ましくはｒ₂＝３である。ｎは２０〜１５０の整数を示す。）
Ｒ²−Ｓｉ［ＯＳｉ（ＣＨ₃）₃］₃ （２）
ＣＨ₂＝Ｃ（Ｒ³）Ｓｉ（Ｒ⁴）（Ｒ⁵）（Ｒ⁶） （３）
（ここで、Ｒ³は水素原子、Ｃ₁−Ｃ₄のアルキル基を表し、好ましくは水素原子、メチル基を表す。Ｒ⁴、Ｒ⁵、及びＲ⁶は、それぞれＣ₁−Ｃ₆のアルキル基、Ｃ₁−Ｃ₆のアルケニル基、アリール基、置換アリール基、複素環基、フルオロアルキル基、トリアルキルシロキシ基を表し、好ましくは、水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基、ｓｅｃ−ブチル基、フェニル基、置換フェニル基、−ＣＦ₃、−Ｃ₂Ｈ₄ＣＦ₃、−ＯＳｉ（ＣＨ₃）₃を示す。Ｒ⁴、Ｒ⁵、Ｒ⁶は、それぞれ同一又は異なっていてもよい。）
式（１）〜（３）からなる群より選択される反応性シリコーンとしては、片末端がメタクリル変性、アクリル変性、又はビニル変性されたポリジメチルシロキサン、両末端がアクリル変性、アクリル変性、又はビニル変性されたポリジメチルシロキサン等が好適である。好ましくは、該反応性シリコーンは下記の式（４）〜（８）のいずれかで表される。
【００２４】
ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣ₃Ｈ₆−Ｓｉ（ＣＨ₃）₂−Ｏ−［Ｓｉ（ＣＨ₃）₂−Ｏ］_p−Ｓｉ（ＣＨ₃）₂−Ｒ⁷ （４）
（ここで、Ｒ⁷は炭素数１〜１２のアルキル基又はＣＨ₂＝ＣＨ−を示す。ｐは２５〜１５０の整数を示す。）
ＣＨ₂＝ＣＨＣＯＯＣ₃Ｈ₆−Ｓｉ（ＣＨ₃）₂−Ｏ−［Ｓｉ（ＣＨ₃）₂−Ｏ］_s−Ｓｉ（ＣＨ₃）₂−Ｒ⁸ （５）
（ここで、Ｒ⁸は炭素数１〜１２のアルキル基又はＣＨ₂＝ＣＨ−を示す。ｓは２５〜１５０の整数を示す。）

（ここでＲ⁹は、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯ（ＣＨ₂）₃−又はＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂）₃−を示す。ｑは２０〜１５０の整数を示す。）
ＣＨ₂＝ＣＨ−Ｓｉ（ＣＨ₃）₂−Ｏ−［Ｓｉ（ＣＨ₃）₂−Ｏ］_y−Ｓｉ（ＣＨ₃）₂−Ｒ¹⁰ （７）
（ここで、Ｒ¹⁰は炭素数１〜１２のアルキル基又はＣＨ₂＝ＣＨ−を示す。ｙは２５〜１５０の整数を示す。）
ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣ₃Ｈ₆−Ｓｉ［ＯＳｉ（ＣＨ₃）₃］₃ （８）
これらの反応性シリコーンはそれぞれ単独で用いてもよいし、２種以上を組み合わせてもよい。これらの反応性シリコーンの数平均分子量は、２００〜３０，０００が好ましい。
【００２５】
塗膜表面における上記のＳｉ原子及び／又はＦ原子の割合を充足するため、反応性シリコーンの量は、０．００１モル％以上、好ましくは０．００２モル％以上、より好ましくは０．０１モル％以上であり、５０モル％以下、好ましくは３０モル％以下、より好ましくは２０モル％、さらに好ましくは１０モル％以下である。
【００２６】
（ｃ）水酸基含有不飽和単量体としては、式（９）の単量体が挙げられる。
ＣＲ¹¹Ｒ¹²＝ＣＨＲ¹³ （９）
（Ｒ¹¹、Ｒ¹²及びＲ¹³は同一であっても異なってもよいが、少なくとも１つが水酸基を含有する。具体的には：水素原子、水酸基、Ｃ₁−Ｃ₆のアルキル基、Ｃ₁−Ｃ₆のアルケニル基、Ｃ₁−Ｃ₆のヒドロキシアルキル基、Ｃ₁−Ｃ₆のヒドロキシアルケニル基、Ｃ₁−Ｃ₆のアルコキシル基、アリール基及び置換アリール基からなる群より選択することができる。）
例えば、ヒドロキシブチルビニル、ヒドロキシブチルビニルエーテル、ヒドロキシプロピルビニル、ヒドロキシプロピルビニルエーテル、メタクリル酸２−ヒドロキシエチル、メタクリル酸２−ヒドロキシプロピル、メタクリル酸２−ヒドロキシブチル、アクリル酸２−ヒドロキシエチル、アクリル酸２−ヒドロキシプロピル、アクリル酸２−ヒドロキシブチルを用いることもできる。それらの中でも、ヒドロキシブチルビニルエーテルが好ましい。複数の水酸基含有不飽和単量体の混合物を用いることもできる。
【００２７】
水酸基含有含フッ素共重合体（Ｃ）中の（ｃ）水酸基含有不飽和単量体の量は、１モル％以上、好ましくは５モル％以上であり、５０モル％以下、好ましくは３０モル％以下、さらに好ましくは２５モル％以下である。（ｃ）水酸基含有不飽和単量体が少なすぎると常温又は加熱硬化が起こりにくくなり、多すぎると塗膜中のＦ量が減り、フッ素樹脂としての効果が得られにくい。
【００２８】
該シリコーン含有フッ素系共重合体は、上記の（ａ）、（ｂ）、及び（ｃ）以外の単量体を含むこともできる。例えば、式（１０）においてＲ¹¹、Ｒ¹²及びＲ¹³が何れも水酸基を含有しない単量体を用いることができる。（ｃ）をヒドロキシブチルビニルエーテルとする場合には、ブチルビニルエーテル等を用いることもできる。
【００２９】
本発明の塗膜の製造には、既知の硬化方法の何れを用いてもよい。硬化方法としては、常温硬化、加熱硬化、紫外線硬化、電子線硬化が挙げられる。
本発明の塗膜に含まれるシリコーン含有フッ素系共重合体（Ａ、Ａ’、Ｃ及びＤ）は、不飽和二重結合を有してもよい。不飽和二重結合を有すると、硬化剤を用いなくても架橋反応を起こせるという利点がある。また他の成分が共存する場合には、その成分との反応が起こりやすいという利点がある。
【００３０】
上記シリコーン含有フッ素系共重合体（Ａ、Ａ’、Ｃ及びＤ）を常温硬化させる場合は、多価イソシアネート類を用いて効率よく常温で硬化させることができる。該多価イソシアネート類としては、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などの無黄変性ジイソシアネートやその付加物、イソシアヌレート類を有する多価イソシアネートが好ましく挙げられるが、これらの中でイソシアヌレート類を有する多価イソシアネートが特に有効である。イソシアネート類を用いて常温硬化を行わせる場合には、ジブチル錫ジラウレート等の公知触媒の添加によって硬化を促進させることができる。
【００３１】
上記シリコーン含有フッ素系共重合体（Ａ、Ａ’、Ｃ及びＤ）を、加熱硬化させることもできる。硬化剤としては、メラミン硬化剤、尿素樹脂硬化剤、多塩基酸硬化剤などが挙げられる。該メラミン硬化剤としては、例えばブチル化メラミン、メチル化メラミン、エポキシ変性メラミン等が挙げられ、用途に応じて各種変性度のものが適宜用いられ、また自己縮合度も適宜選ぶことができる。尿素樹脂硬化剤としては、例えばメチル化尿素樹脂やブチル化尿素樹脂等が挙げられ、多塩基酸硬化剤としては、例えば長鎖脂肪族ジカルボン酸、芳香族多価カルボン酸類及びこれらの酸無水物等が挙げられる。
【００３２】
さらに、ブロック化多価イソシアネート類も硬化剤として好適に用いる事ができる。またメラミン硬化剤又は尿素樹脂硬化剤の使用に際しては、酸性触媒の添加によって硬化を促進させることができる。
【００３３】
熱重合開始剤としては、ベンゾイルパーオキサイド、アゾビスイソブチロニトリル、ｔ−ブチルパーオキシ−２−エチルヘキサネート、ｔ−ブチルパーオキシイソプロピルモノカーボネート等が用いられる。
【００３４】
上記シリコーン含有フッ素系共重合体（Ａ、Ａ’、Ｃ及びＤ）を、紫外線硬化させることもできる。紫外線硬化の場合に使用する光重合開始剤としては、ベンゾインエーテル、ベンゾフェノン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、２−メチル−１−[４−（メチルチオ）フェニル]−２−モンフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフェリノフェニル）−ブタノン−１、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン等が用いられる。
【００３５】
紫外線硬化は、従来公知の方法により行うことができる。例えば、高圧水銀ランプを使用するときは、１００〜１０００ｍＪ／ｃｍ²の条件等で硬化可能である。
【００３６】
上記シリコーン含有フッ素系共重合体（Ａ、Ａ’、Ｃ及びＤ）を、電子線硬化させることもできる。電子線硬化の場合には、重合開始剤を混合しなくとも硬化させることができる。硬化条件としては、例えば１１０ｋＶで３０ｋＧｙ又は２００ｋＶで３０ｋＧｙの条件等が挙げられる。
【００３７】
上記シリコーン含有フッ素系共重合体とその他の成分とを含む組成物も、本発明の塗膜に用いることができる。該組成物を、前述の方法により硬化させることもできる。
【００３８】
上記組成物中のシリコーン含有フッ素系共重合体以外の成分として、アクリル系樹脂（Ｂ）、反応性希釈剤（Ｅ）、光硬化性（メタ）アクリレート樹脂（Ｆ）等が挙げられる。シリコーン含有フッ素系共重合体以外の上記成分の何れか１種を使用することもでき、組み合わせて使用することもできる。該フッ素共重合体として１種のみを用いてもよく、複数を組み合わせて用いてもよい。例えば、シリコーン含有フッ素系共重合体（Ａ）、（Ａ’）、（Ｃ）及び（Ｄ）から選択される少なくとも１種のシリコーン含有フッ素系共重合体とアクリル樹脂（Ｂ）とからなる組成物を用いることもできる。また、シリコーン含有フッ素系共重合体（Ａ）、（Ａ’）、（Ｃ）及び（Ｄ）から選択される少なくとも１種のシリコーン含有フッ素系共重合体と；反応性希釈剤（Ｅ）及び／又は光硬化性（メタ）アクリレート樹脂（Ｆ）と；からなる組成物を用いることもできる。硬化方法に応じて、上記組成物に硬化剤、光重合開始剤、熱重合開始剤等を添加することもできる。
【００３９】
アクリル系樹脂（Ｂ）の具体例としては、一般的にアクリル樹脂と称されているメチル（メタ）アクリレート共重合体、エチル（メタ）アクリレート共重合体、ブチル（メタ）アクリレート共重合体、スチレンを含有する（メタ）アクリレート共重合体、ヒドロキシエチル（メタ）アクリレート共重合体、などが挙げられる。これらアクリル系樹脂は、それぞれ単独で用いてもよいし、２種以上を組み合せてもよい。
【００４０】
市販されているアクリル系樹脂としては、アクリディックＡ−８１４、アクリディックＡ−８１０−４５（大日本インキ工業（株）製）、テストロイド４２１１−４６、テストロイド４２１２−４６（日立化成ポリマー（株）製）、ダイヤナールＬＲ−６２０、ダイヤナールＬＲ−１９９、ダイヤナールＬＲ−２５１６、ダイヤナールＳＳ−７９２（三菱レイヨン（株）製）、ヒタロイド３０４６Ｃ、ヒタロイド３０１８（日立化成工業（株）製）などがあり、それぞれ単独で用いてもよいし、２種以上を組み合せてもよい。
【００４１】
樹脂組成物中にアクリル樹脂（Ｂ）が用いられる場合、シリコーン含有フッ素系共重合体は樹脂組成物の５〜９５重量％、好ましくは２０〜８０重量％、さらに好ましくは４０〜６０重量％を占める。アクリル樹脂（Ｂ）は、９５〜５重量％、好ましくは８０〜２０重量％、さらに好ましくは６０〜４０重量％を占める。アクリル系樹脂を使用することにより、塗膜の寿命や硬度等が改善される場合がある。
【００４２】
反応性希釈剤（Ｅ）は、単官能性のもの、二官能性のもの及び多官能性のものがある。分子中に不飽和二重結合等を含有していることが好ましい。例えば、単官能アクリレート又はメタアクリレート（（メタ）アクリレートと表記することがある）、二官能（メタ）アクリレート、３官能（メタ）アクリレート、４官能以上の（メタ）アクリレートを用いることができる。これらの分子はそれ自体が架橋反応をすることができるため、架橋により塗膜成分となる。また同時に、シリコーン含有フッ素系共重合体を溶液の状態にすることもでき、溶媒と同様の働きをすることができる。従って、溶媒に代えて反応性希釈剤を用いることもできる。この様な使用態様により、有機溶媒を使用する場合に比べ大気中に排出される有機溶媒量を減量させることが出来るという利点がある。さらに、反応性希釈剤（Ｅ）は低粘度であるため、シリコーン含有フッ素系共重合体組成物の粘度を下げることが可能であり、作業性も改善することが出来る。この様な特性により、反応性希釈剤（Ｅ）は何れの硬化方法においても使用することができる。
【００４３】
この様な反応性希釈剤としては、具体的には、次のようなアクリレート化合物、メタクリレート化合物及びエーテル類からなる群より選択される１種以上のものが挙げられる。
【００４４】
単官能性アクリレートとしては、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ラウリル（メタ）アクリレート、セチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、３−メトキシブチル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、２−エチルヘキシルカルビトール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、メトキシトリプロピレングリコール（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−アクリロイルオキシエチル−２−ヒドロキシプロピルフタレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、２−アクリロイルオキシエチルハイドロゲンフタレート、２−アクリロイルオキシプロピルハイドロゲンフタレート、ジメチルアミノエチル（メタ）アクリレート、β−カルボキシエチル（メタ）アクリレート、イソボニル（メタ）アクリレート、オキシエチル化フェノールアクリレート、フェノールＥＯ変性（メタ）アクリレート、パラクミルフェノールＥＯ変性（メタ）アクリレート、ノニルフェノールＥＯ変性（メタ）アクリレート等が挙げられる。
【００４５】
また、二官能性アクリレートとしては、１，６−ヘキサンジオールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジプロピレングルコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ビスフェノールＡ ＥＯ変性ジ（メタ）アクリレート、イソシアヌル酸ＥＯ変性ジ（メタ）アクリレート等が挙げられる。
【００４６】
三官能（メタ）アクリレートモノマーの具体例としては、ペンタエリスルトールトリアクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンエトキシトリアクリレート、トリメチロールプロパンＥＯ変性トリアクリレート、トリメチロールプロパンＰＯ変性トリアクリレート、イソシアヌル酸ＥＯ変性トリアクリレート等が挙げられる。
【００４７】
四官能以上の（メタ）アクリレートの具体例としては、ジトリメチロールプロパンテトラアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスルトールヘキサアクリレート等が挙げられる。
【００４８】
光硬化性（メタ）アクリレート樹脂（Ｆ）は、紫外線硬化等の光硬化を行う場合に好ましい。例えば、従来より公知の脂肪族／芳香族ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、ポリエーテル（メタ）アクリレート等が挙げられる。
【００４９】
具体例として、Ｅｂｅｃｒｙｌ ２１０、Ｅｂｅｃｒｙｌ ８４０２、Ｅｂｅｃｒｙｌ １２９０Ｋ（３品種ともダイセル・ユーシービー製）等の芳香族及び脂肪族ウレタンアクリレート、ＫＡＹＡＲＡＤ ＥＡＭ−２３００、ＫＡＹＡＲＡＤ Ｒ−１９０（２品種とも日本化薬製）、Ｅｂｅｃｒｙｌ ６００（ダイセル・ユーシービー製）等のエポキシアクリレート、Ｅｂｅｃｒｙｌ ８０、Ｅｂｅｃｒｙｌ ８００、Ｅｂｅｃｒｙｌ ８１０（３品種ともダイセル・ユーシービー製）アロニックスＭ−７１００（東亜合成製）等のポリエステルアクリレートが挙げられる。これらの光架橋性（メタ）アクリレート樹脂は、それぞれ単独で用いてもよいし、２種以上を組み合せてもよい。
【００５０】
上記（メタ）アクリレートモノマー、芳香族又は脂肪族ウレタンアクリレート、エポキシアクリレート、及びポリエステルアクリレートのモノマー若しくはオリゴマーは、それぞれ単独で用いてもよいし、２種以上を組み合せてもよい。しかしながら、これらを選択するときには、取り扱い上、皮膚刺激性（Ｐ．Ｐ．Ｉ．値）が低い化合物が好ましい。
【００５１】
本発明のシリコーン含有フッ素系共重合体の少なくとも１種と、アクリル系樹脂（Ｂ）、反応性希釈剤（Ｅ）、及び光硬化性（メタ）アクリレート樹脂（Ｆ）からなる群より選択される少なくとも１種との混合は、ボールミル、ペイントシェーカー、サンドミル、三本ロールミル、ニーダーなどの通常の塗料化に用いられる種々の機器を用いて行うことが出来る。この際、必要に応じて顔料、分散安定剤、粘度調節剤、レベリング剤等を添加して混合することもできる。
【００５２】
本発明のシリコーン含有フッ素系共重合体を主成分とする硬化性フッ素樹脂塗料を製造する場合には、種々の溶媒が使用可能であり、例えば、キシレン、トルエン等の芳香族炭化水素類、酢酸エチル、酢酸ブチル等の酢酸エステル類、メチルエチルケトン、メチルイソブチルケトン等のケトン類、エチルセロソルブ等のグリコールエーテル類、ブタノール等のアルコール類、市販の各種シンナー類等が挙げられるが、特に好ましい溶媒としては、酢酸ブチル、酢酸エチル、トルエン、キシレン、芳香族炭化水素混合物、メチルエチルケトン、メチルイソブチルケトン、メタノール、ブタノール、イソプロピルアルコール、エタノール及びソルベッソ（登録商標）が挙げられる。これらの溶媒は、単独で、又は２種以上の組み合わせで使用できる。
【００５３】
【実施例】
次に、本発明を実施例により及び比較実施例との対比によって更に詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
【００５４】
〔実施例１〕
内容積１Ｌのステンレス製攪拌機付きオートクレーブ（耐圧１０ＭＰａ）に、脱気した後、フッ化ビニリデン／テトラフルオロエチレン／ヒドロキシブチルビニルエーテル／ブチルビニルエーテル／反応性シリコーンオイルＩ（Ｍｗ＝約４７００）を３０／４０／１５／１４．９７／０．０３モル％の組成比で仕込み、重合溶媒に酢酸ブチル、重合開始剤にｔ−ブチルパーオキシピバレートを使用し、これらを同オートクレーブに仕込み、攪拌しながら内温度を６０℃に昇温した。その後、攪拌しながら反応を続け、２０時間後反応を終了し、シリコーン含有フッ素系重合体を製造した。該共重合体の硬化塗膜を作成し、塗膜特性を次の方法で調べた。結果を表１に示す。
反応性シリコーンオイルＩ：ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣ₃Ｈ₆−Ｓｉ（ＣＨ₃）₂−Ｏ−［Ｓｉ（ＣＨ₃）₂−Ｏ］₆₄−Ｓｉ（ＣＨ₃）₂−Ｃ₄Ｈ₉
【００５５】
【表１】

【００５６】
〔硬化塗膜作成条件〕 該シリコーン含有フッ素系重合体の水酸基／ＮＣＯ基比が１／１となるようにコロネートＨＸ〔日本ポリウレタン工業（株）製〕を加え、コロナ放電処理済みのＰＥＴフィルムに＃１０バーコーターを用いて塗布し、８０℃で２４時間加熱処理した。
【００５７】
〔塗膜表面組成測定〕 使用したＸＰＳ装置は、Ｋｒａｔｏｓ Ａｎａｌｙｔｉｃａｌ Ｉｎｃ．（英国）製の島津／ＫＲＡＴＯＳ ＡＸＩＳ−ＨＳであった。
［測定条件］ 測定Ｘ線源：単色化ＡｌＫα線（６０Ｗ）、分析面積：２×４ｍｍ、測定元素：Ｓｉ，Ｆ，Ｃ，Ｏ、
［サーベイスキャン測定（定性分析）］ 測定エネルギー範囲：０〜１１００ｅＶ、Ｐａｓｓ Ｅｎｅｒｇｙ：１６０ｅＶ、ｓｔｅｐ：１．０ｅＶ、Ｄｗｅｌｌ：３００ｍｓ、帯電中和装置フィラメント：電流２Ａ、電位−１．０Ｖ、バイアス電圧−２．７Ｖ、ｔａｋｅ ｏｆｆ ａｎｇｌｅ（取り出し角）９０°
［マルチスキャン測定（定量・状態分析）］ 各元素の測定エネルギー範囲：Ｓｉ２_p ８７〜１０７ｅＶ、Ｆ１_s ６７８〜６９８ｅＶ、Ｃ１_s ２７８〜２９８ｅＶ、Ｏ１_s ５２１〜５４１ｅＶ、Ｐａｓｓ ｅｎｅｒｇｙ：４０ｅＶ、ｓｔｅｐ：０．１ｅＶ、Ｄｗｅｌｌ：２９８ｍｓ、帯電中和装置フィラメント：電流２Ａ、電位−１．０Ｖ、バイアス電圧−２．７Ｖ、ｔａｋｅ ｏｆｆ ａｎｇｌｅ（取り出し角）９０°
原子組成比（ａｔｏｍｉｃ％）は、上記装置のシステムにより求められる。
【００５８】
Ｓｉ（ａｔｏｍｉｃ％）＝Ｓｉ／（Ｓｉ＋Ｆ＋Ｃ＋Ｏ） × １００
Ｆ（ａｔｏｍｉｃ％） ＝Ｆ／（Ｓｉ＋Ｆ＋Ｃ＋Ｏ） × １００
によってそれぞれ計算した。
【００５９】
表２に、上記組成式に基づいて計算したシリコーン含有フッ素系共重合体塗膜の平均Ｓｉ量、ＸＰＳによる塗膜表面上Ｓｉ量の実測値、及びＸＰＳによる塗膜表面上Ｆ量の実測値を示す。バルクの平均Ｓｉ量と比較して表面の実測値は高く、表面付近にＳｉ部位が局在していることがわかる。
【００６０】
【表２】

【００６１】
〔油性マジックはじき性〕 油性マジック（黒・赤マジックインキ：登録商標）により塗膜表面を塗りつぶし、はじき性を評価する（初期）。更にこの塗膜を室温で１時間放置後、乾拭きにより除去する。この操作を２０回繰り返した後の塗膜表面のはじき性を５段階評価する。
【００６２】
５（良くはじく）〜１（全くはじかない）。
〔油性マジック繰り返し除去性〕 油性マジック（黒・赤マジックインキ：登録商標）により塗膜表面を塗りつぶし、室温で１時間放置後乾拭きにより除去し、その除去性を評価する（初期）。更にこれを２０回繰り返した後の塗膜表面の除去性を、５段階評価する。
【００６３】
５（完全に除去できる）〜１（全く除去できない）。
〔撥水性〕 水の接触角（単位：度）で評価した。
〔実施例２〜４〕
実施例１で使用の反応性シリコーンオイルＩの量を０．１モル％、０．２モル％、０．４モル％に変え、実施例１の操作に準拠して重合体を製造し、それらの重合体を用いて得た塗膜の特性を同様に調べた。結果を表１に示す。
【００６４】
〔実施例５〕
実施例１で使用の反応性シリコーンオイルＩを、Ｍｗ＝約２１００の反応性シリコーンオイルＩＩ（０．０３モル％）に変え、実施例１の操作に準拠して重合体を製造し、その重合体を用いて得た塗膜の特性を同様に調べた。結果を表１に示す。
反応性シリコーンオイルＩＩ：ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣ₃Ｈ₆−Ｓｉ（ＣＨ₃）₂−Ｏ−［Ｓｉ（ＣＨ₃）₂−Ｏ］₂₅−Ｓｉ（ＣＨ₃）₃
〔実施例６〜８〕
実施例５で使用の反応性シリコーンオイルＩＩの量を０．００１モル％、０．００２モル％、０．０１モル％に変え、実施例５と同様に重合体を製造し、それらの重合体を用いて得た塗膜の特性を同様に調べた。結果を表１に示す。
【００６５】
〔実施例９〕
実施例３で使用の反応性シリコーンオイルＩを、Ｍｗ＝約１１４００の反応性シリコーンオイルＩＩＩ（０．２モル％）に変え、実施例３と同様に重合体を製造し、その重合体を用いて得た塗膜の特性を同様に調べた。結果を表１に示す。反応性シリコーンオイルＩＩＩ：ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣ₃Ｈ₆−Ｓｉ（ＣＨ₃）₂−Ｏ−［Ｓｉ（ＣＨ₃）₂−Ｏ］₁₄₀−Ｓｉ（ＣＨ₃）₂−Ｃ₄Ｈ₉
〔実施例１０〕
実施例１で得られたシリコーン含有フッ素系共重合体とダイヤナールＬＲ−１９９（三菱レーヨン（株）製）を固形分換算で５／５となるように混合し、シリコーン含有フッ素系共重合体組成物を作成した。これらの特性を同様に調べた。結果を表１に示す。
【００６６】
〔実施例１１〕
内容積１Ｌのステンレス製攪拌機付きオートクレーブ（耐圧１０ＭＰａ）に、脱気した後、フッ化ビニリデン／テトラフルオロエチレン／ヒドロキシブチルビニルエーテル／ブチルビニルエーテル／反応性シリコーンオイルＩ（Ｍｗ＝約４７００）を３０／４０／１５／１４．９７／０．０３モル％の組成比で仕込み、重合溶媒に酢酸ブチル、重合開始剤にｔ−ブチルパーオキシピバレートを使用し、これらを同オートクレーブに仕込み、攪拌しながら内温度を６０℃に昇温した。その後、攪拌しながら反応を続け、２０時間後反応を終了し、水酸基含有共重合体を製造した。続いて、該水酸基含有共重合体の水酸基と２−イソシアネートエチルメタクリレートのイソシアネート基が当量になるように加え反応を行い、不飽和二重結合を含むシリコーン含有フッ素系共重合体を製造した。該重合体の硬化塗膜を下記の条件で作成し、塗膜特性を実施例１と同様に調べた。結果を表１に示す。
【００６７】
〔硬化塗膜作成条件〕 上記重合体の５０％酢酸ブチル溶液をコロナ放電処理済みのＰＥＴフィルムに＃１０バーコーターを用いて塗布し、８０℃で１分間乾燥した後、酸素濃度２００ｐｐｍの雰囲気下で岩崎電気製電子線照射装置ＥＣ２５０／１５／１８０Ｌにて加速電圧２００ｋV、線量３０ｋＧｙの条件にて電子線を照射した。
【００６８】
〔実施例１２〕
実施例１１で得られた不飽和二重結合を含むシリコーン含有フッ素系共重合体の上記５０％酢酸ブチル溶液１００ｇと、Ｅｂｅｃｒｙｌ ８０（ダイセル・ユーシービー製ポリエステルアクリレート）３０ｇと、１，６−ヘキサンジオールジアクリレート２０ｇと、２−メチル−１−〔４−（メチルチオ）フェニル〕−２−モンフォリノプロパノン−１−オン（チバガイギー（株）製）５ｇとを混合してシリコーン含有フッ素系共重合体組成物を作成した。該組成物の硬化塗膜を下記の条件で作成し、塗膜特性を実施例１と同様に調べた。結果を表１に示す。
【００６９】
〔硬化塗膜作成条件〕 上記共重合体組成物酢酸ブチル溶液をコロナ放電処理済みのＰＥＴフィルムに＃１０バーコーターを用いて塗布し、８０℃で１分間乾燥した後、空気中で２５０ｍＪ／ｃｍ²の紫外線を照射した。
【００７０】
〔比較実施例１〕
実施例１の仕込み組成の反応性シリコーンオイルＩを除いた仕込み組成で、実施例１と同様に重合体の製造を行い、その塗膜特性を同様に調べた。結果を表１に示す。
【００７１】
〔比較実施例２〕
実施例１１の仕込み組成の反応性シリコーンオイルＩを除いた仕込み組成で、実施例１１と同様に重合体の製造を行い、その塗膜特性を実施例１１と同様に調べた。結果を表１に示す。
【００７２】
〔比較実施例３〕
実施例５で使用の反応性シリコーンオイルＩＩを０．０００８モル％に変え、実施例５と同様に重合体の製造を行い、その塗膜特性を同様に調べた。結果を表１に示す。
【００７３】
【発明の効果】
本発明は、防汚性、撥水撥油性、耐薬品性、耐候性等に優れ、且つＸＰＳで測定された塗膜表面に存在するＳｉ原子の原子数が２〜３０ａｔｏｍｉｃ％を占める塗膜、特に、塗膜表面に存在するＳｉ原子の原子数が２〜３０ａｔｏｍｉｃ％、Ｆ原子の原子数が２〜３２ａｔｏｍｉｃ％を占めることを特徴とする塗膜に関するものであり、その塗膜表面にＳｉユニットが偏在するため（すなわち、シリコーン含有フッ素系共重合体中のＳｉ部位が塗膜表面方向へ偏在した状態となるため）、少量の反応性シリコーンオイルの使用で優れた特性を示す塗膜表面を得ることができる。また他樹脂、他モノマーと混合する場合にも本発明の該シリコーン含有フッ素系共重合体中の Ｓｉユニットが表面付近に高濃度で局在するため、少量の該共重合体の混合で優れた塗膜表面を得ることができる。
【００７４】
本発明のシリコーン含有フッ素系共重合体及び組成物の硬化塗膜は、優れた特性（防汚性、撥水撥油性、耐薬品性、耐候性等）を有するため、内装用途（壁、床、家具等）のような防汚性の要求される分野、離型フィルム用途、屋外用途（外壁、フィルム等）のような耐候性の要求される分野、落書き防止用途等に好適である。また大型建造物、運輸車両、船舶等の内外塗装用に有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention is excellent in antifouling property, water / oil repellency, chemical resistance, weather resistance and the like, and has a coating film surface measured by X-ray photoelectron spectroscopy (hereinafter sometimes abbreviated as “XPS”). A coating film in which the number of Si atoms present in the film occupies 2 to 30 atomic%, in particular, the number of F atoms present in the coating film surface is 2 to 32 atomic%, and the number of Si atoms in the film occupies 2 to 30 atomic%. It is related with the coating film characterized by this. The present invention also relates to a method for producing the coating film.
[0002]
[Prior art]
As solvent-soluble fluororesins for paints, those obtained by copolymerizing a hydrocarbon monomer such as hydroxyalkyl vinyl ether and a fluoroolefin are generally used. Such a paint based on a fluorinated copolymer contains about 50% of a hydrocarbon monomer in order to obtain solubility in an organic solvent. However, the fluorine content in the fluorine-containing copolymer is reduced, and the coating film properties such as water / oil repellency and stain resistance required for the fluororesin are hardly exhibited. On the other hand, water and oil repellency can be improved by adding a small amount of an organosilicon compound such as silicone oil to these fluorine-containing copolymers, but it is difficult to maintain water and oil repellency over a long period of time. Moreover, since silicone oil will bleed out from the coating-film surface depending on a use, silicone oil may be unable to be used.
[0003]
The present inventors have reported that a fluorine-containing copolymer containing a specific organosilicon compound or reactive silicone provides a coating film excellent in water and oil repellency, chemical resistance and weather resistance (for example, Patent Literatures 1 to 3). However, it has not been clarified why such a coating film made of a fluorine-containing copolymer containing an organosilicon compound or reactive silicone has such excellent characteristics.
[0004]
In addition, it has been found that when the amount of the organosilicon compound in the fluorine-containing copolymer reaches a specific ratio, a coating film showing further excellent water and oil repellency is formed. It was also unclear as to what kind of features above. Then, it has been demanded to elucidate these phenomena, further improve the characteristics, and realize a coating film more suitable for outdoor use requiring weather resistance, interior use requiring antifouling property and the like.
[0005]
In addition, an example in which a release film surface having good wettability with respect to water obtained by reacting an alkyd resin, an amino resin and a modified silicone resin was measured using an X-ray photoelectron spectrometer has been reported (for example, a patent Reference 4).
[0006]
[Patent Document 1]
JP 2000-313725 A
[Patent Document 2]
JP 2001-247622 A
[Patent Document 3]
JP 2001-288216 A
[Patent Document 4]
Japanese Patent No. 3150605
[0007]
[Problems to be solved by the invention]
An object of the present invention is to form a fluorine-containing copolymer excellent in antifouling properties, water and oil repellency, repeated decontamination, chemical resistance, and weather resistance, and a composition thereof that solves the above-described problems. And a method for producing such a coating.
[0008]
[Means for Solving the Problems]
As a result of intensive studies, the inventors of the present invention are coating films comprising a silicone-containing fluorine-based copolymer or a composition containing the same, and the number of Si atoms and F atoms present on the coating surface measured by XPS It has been found that a coating film in which a certain number of atoms occupy a certain ratio exhibits a very excellent water and oil repellency effect, and the present invention has been completed.
[0009]
That is, the above-described problem is a coating film formed from a composition containing a silicone-fluorine copolymer applied on a substrate, and Si atoms present on the coating film surface measured by X-ray photoelectron spectroscopy. This is solved by the coating film of the present invention characterized in that the number of atoms occupies 2 to 30 atomic%. In the coating film, the number of F atoms present on the coating film surface measured by X-ray photoelectron spectroscopy may occupy 2 to 32 atomic%.
[0010]
Said subject is the coating film formed from the composition containing the silicone containing fluorine-type copolymer apply | coated on the base-material surface, Comprising: Si which exists in the coating-film surface measured by X-ray photoelectron spectroscopy The problem is solved by the coating film of the present invention, wherein the ratio of the number of atoms to the number of atoms of F (Si / F value) is 0.0625 to 10.0.
[0011]
In particular, 0.1 to 85 mol% of fluoroolefin as polymerized units; and (b) one or more reactive silicones selected from the group consisting of formulas (1), (2) and (3) A reactive silicone-containing fluorocopolymer (A) characterized by containing 001-30 mol%; acrylic, wood, plastic, metal, graphite, paper, concrete, incombustible material (gypsum board, calcium silicate board) , Ceramic materials such as flexible boards, etc.), coated on a substrate such as glass and cured by heat or light, etc., anti-fouling, water and oil repellency, repeated decontamination, repeated contamination The present inventors have found that the coating film characteristics such as repellency, weather resistance and erosion resistance against alkalis and acids are very excellent. Moreover, it is excellent also as a coating film for topcoats after applying another coating agent on these substrates.
[0012]

(Where R¹Is CH₂= C (CH_Three) COO (CH₂)_r1-, CH₂= CHCOO (CH₂)_r1-Or CH₂= CH-. R²Is an alkyl group having 1 to 12 carbon atoms, CH₂= C (CH_Three) COO (CH₂)_r2-, CH₂= CHCOO (CH₂)_r2-Or CH₂= CH-. n is an integer of 20 to 150, r₁Is an integer from 1 to 6, r₂Represents an integer of 1-6. )
R²-Si [OSi (CH_Three)_Three]_Three                          (2)
CH₂= C (R^Three) Si (R^Four) (R^Five) (R⁶(3)
Where R^ThreeRepresents a hydrogen atom or a methyl group. R^Four, R^FiveAnd R⁶Are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, sec-butyl group, phenyl group, substituted phenyl group, and -CF, respectively._Three, -C₂H_FourCF_ThreeOr -OSi (CH_Three)_ThreeIndicates. R^Four, R^Five, R⁶May be the same or different. )
Furthermore, the above issues
(A) 15 to 85 mol% of a fluoroolefin as polymerized units; (b) 0.001 to 30 mol% of one or more reactive silicones selected from formulas (1), (2) and (3); And (c) a hydroxyl group-containing reactive silicone-containing fluorocopolymer (C) comprising 1 to 50 mol% of a hydroxyl group-containing unsaturated monomer; and
Unsaturated isocyanate (d)
It solves with the coating film of this invention formed using the silicone containing fluorine-type copolymer (D) produced | generated by reaction with this.
[0013]
Furthermore, the above-described problem is one or more fluorine-based copolymers selected from the group consisting of silicone-containing fluorine-based copolymers (A), (A ′), and (D); and acrylic resins (B), The coating film of the present invention formed using a resin composition comprising: a reactive diluent (E) and one or more components selected from the group consisting of a photocurable (meth) acrylate resin (F) To solve.
[0014]
Furthermore, the coating film of the present invention is coated with a composition containing at least one copolymer selected from the group consisting of: a silicone-containing fluorocopolymer (A), (A ′), and (D). Curing the composition; setting the proportion of Si atoms present on the coating surface measured by X-ray photoelectron spectroscopy to 2 to 30 atomic%, and the proportion of F atoms to 2 to 32 atomic%; Is done.
[0015]
And it was able to ascertain by the measurement by XPS that the outstanding coating-film characteristic of this invention originates in the number of atoms of Si atom which exists in the coating-film surface, and the number of atoms of F atom. That is, it was found that when the silicone-containing fluorine-based copolymer was formed into a coating film, Si atoms were selectively localized on the coating film surface.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
The coating film surface composition in the present invention is measured by XPS. As the composition in the present application, values measured according to the apparatus and conditions described in Example 1 were used.
[0017]
The values measured by the method and conditions described in Example 1 were used for oil-based magic repellent properties, oil-based magic removability, and water repellency.
It is preferable that the number of Si atoms on the surface of the coating film occupies 2 atomic% or more, particularly 3 atomic% or more. The upper limit is 50 atomic%, preferably 30 atomic%, and more preferably 20 atomic%. If it is less than the above range, the oily magic removability and repellency are poor and the water repellency is also poor. On the other hand, if it is larger than the above range, the molecular weight of the reactive silicone becomes large and handling in production becomes difficult.
[0018]
F atoms on the surface of the coating occupy 1 atomic% or more, preferably 2 atomic% or more. Also, it is 50 atomic% or less, preferably 32 atomic% or less, and more preferably 25 atomic% or less. If it is less than the above range, the characteristics as a fluororesin will not be exhibited, and if it is greater than the above range, the oily magic removability and repelling property will deteriorate.
[0019]
Only one of the surface composition of Si atom or F atom may be in the above range, but it is preferable that both are in the above range.
The ratio of the number of Si atoms to the number of F atoms (Si / F value) is preferably 0.0625 to 15.0, particularly preferably 0.0625 to 10.0. In the case where the surface composition of Si atoms and F atoms is in the above range, the Si / F value is 0.0625 to 15.0, preferably 0.0625 to 10.0, and more preferably 0.12 to 10.0. More preferably, it is desirable to be 0.14 to 10.0.
[0020]
From the viewpoint of the water repellency of the coating film, the contact angle with water is 98 to 120 degrees, preferably 98 to 110 degrees.
The thickness of the coating film is 0.00005 mm or more, preferably 0.0001 mm or more, more preferably 0.0002 mm or more. Moreover, it is 2 mm or less, Preferably it is 0.5 mm or less, More preferably, it is 0.3 mm or less. If the coating film is too thin, a region that cannot be completely coated is generated.
[0021]
There is no restriction | limiting in particular in the base material used for the coating film of this invention, An organic material and an inorganic material can be used. Examples of usable base materials include wood, plastics (acrylic materials, PET, etc.), metals, graphite, paper, concrete, noncombustible materials (ceramic materials such as gypsum board, calcium silicate plate, flexible board, etc.), glass, etc. Is mentioned. As the transparent material, an acrylic material or PET is preferable.
[0022]
There is no restriction | limiting in particular in the shape of a base material, It may be planar or uneven. The article having the coating film of the present invention can be used for various interior applications and outdoor applications.
There is no particular limitation on the (a) fluoroolefin which is a polymerization unit of the silicone-containing fluorocopolymer, but CH₂= CHF, CH₂= CF₂, CHF = CHF, CHF = CF₂, CF₂= CF₂, CF₂= CFCl and CF₂= CF (CF_Three) Can be preferably used, and CF₂= CF₂And / or CH₂= CF₂Is particularly preferred. Mixtures of multiple fluoroolefins can also be used.
[0023]
(B) As reactive silicone,

(Where R¹Is R^{twenty one}(CH₂)_r1-(R^{twenty one}Represents an unsaturated carboxyl group) or an alkenyl group, preferably CH₂= CHCOO (CH₂)_r1-, CH₂= C (CH_Three) COO (CH₂)_r1-Or CH₂= CH-. r₁Represents an integer of 1 to 6, preferably r₁= 3. R²Is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, or R^{twenty one}(CH₂)_r1-(R^{twenty one}Represents an unsaturated carboxyl group), preferably an alkyl group having 1 to 12 carbon atoms, CH₂= C (CH_Three) COO (CH₂)_r2-, CH₂= CHCOO (CH₂)_r2-Or CH₂= CH-. r₂Represents an integer of 1 to 6, preferably r₂= 3. n represents an integer of 20 to 150. )
R²-Si [OSi (CH_Three)_Three]_Three                          (2)
CH₂= C (R^Three) Si (R^Four) (R^Five) (R⁶(3)
(Where R^ThreeIs a hydrogen atom, C₁-C_FourAnd preferably represents a hydrogen atom or a methyl group. R^Four, R^FiveAnd R⁶Are respectively C₁-C₆Alkyl group of₁-C₆Represents an alkenyl group, an aryl group, a substituted aryl group, a heterocyclic group, a fluoroalkyl group, or a trialkylsiloxy group, preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group. , T-butyl group, sec-butyl group, phenyl group, substituted phenyl group, -CF_Three, -C₂H_FourCF_Three, -OSi (CH_Three)_ThreeIndicates. R^Four, R^Five, R⁶May be the same or different. )
The reactive silicone selected from the group consisting of formulas (1) to (3) includes polydimethylsiloxane having one end that is methacryl-modified, acrylic-modified, or vinyl-modified, and both ends that are acrylic-modified, acrylic-modified, or vinyl. Modified polydimethylsiloxane and the like are preferred. Preferably, the reactive silicone is represented by any of the following formulas (4) to (8).
[0024]
CH₂= C (CH_ThreeCOOC_ThreeH₆-Si (CH_Three)₂-O- [Si (CH_Three)₂-O]_p-Si (CH_Three)₂-R⁷                      (4)
(Where R⁷Is an alkyl group having 1 to 12 carbon atoms or CH₂= CH-. p shows the integer of 25-150. )
CH₂= CHCOOC_ThreeH₆-Si (CH_Three)₂-O- [Si (CH_Three)₂-O]_s-Si (CH_Three)₂-R⁸                              (5)
(Where R⁸Is an alkyl group having 1 to 12 carbon atoms or CH₂= CH-. s shows the integer of 25-150. )

(Where R⁹Is CH₂= C (CH_Three) COO (CH₂)_Three-Or CH₂= CHCOO (CH₂)_Three-Is shown. q represents an integer of 20 to 150. )
CH₂= CH-Si (CH_Three)₂-O- [Si (CH_Three)₂-O]_y-Si (CH_Three)₂-R^Ten                                                    (7)
(Where R^TenIs an alkyl group having 1 to 12 carbon atoms or CH₂= CH-. y shows the integer of 25-150. )
CH₂= C (CH_ThreeCOOC_ThreeH₆-Si [OSi (CH_Three)_Three]_Three  (8)
These reactive silicones may be used alone or in combination of two or more. The number average molecular weight of these reactive silicones is preferably 200 to 30,000.
[0025]
In order to satisfy the above-mentioned proportion of Si atoms and / or F atoms on the surface of the coating film, the amount of reactive silicone is 0.001 mol% or more, preferably 0.002 mol% or more, more preferably 0.01 mol. % Or more, 50 mol% or less, preferably 30 mol% or less, more preferably 20 mol%, still more preferably 10 mol% or less.
[0026]
(C) As a hydroxyl-containing unsaturated monomer, the monomer of Formula (9) is mentioned.
CR¹¹R¹²= CHR¹³              (9)
(R¹¹, R¹²And R¹³May be the same or different, but at least one of them contains a hydroxyl group. Specifically: hydrogen atom, hydroxyl group, C₁-C₆Alkyl group of₁-C₆An alkenyl group of C₁-C₆A hydroxyalkyl group, C₁-C₆A hydroxyalkenyl group of C₁-C₆Selected from the group consisting of an alkoxyl group, an aryl group and a substituted aryl group. )
For example, hydroxybutyl vinyl, hydroxybutyl vinyl ether, hydroxypropyl vinyl, hydroxypropyl vinyl ether, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 2-hydroxyethyl acrylate, 2-acrylate Hydroxypropyl and 2-hydroxybutyl acrylate can also be used. Of these, hydroxybutyl vinyl ether is preferred. A mixture of a plurality of hydroxyl group-containing unsaturated monomers can also be used.
[0027]
The amount of the (c) hydroxyl group-containing unsaturated monomer in the hydroxyl group-containing fluorine-containing copolymer (C) is 1 mol% or more, preferably 5 mol% or more, and 50 mol% or less, preferably 30 mol%. Hereinafter, it is more preferably 25 mol% or less. (C) When there are too few hydroxyl-containing unsaturated monomers, it will become difficult to perform normal temperature or heat-curing, and when too large, the amount of F in a coating film will reduce and it will be difficult to obtain the effect as a fluororesin.
[0028]
The silicone-containing fluorine-based copolymer can also contain monomers other than the above (a), (b), and (c). For example, in formula (10), R¹¹, R¹²And R¹³However, any of these monomers can be used that do not contain a hydroxyl group. When (c) is hydroxybutyl vinyl ether, butyl vinyl ether or the like can also be used.
[0029]
Any known curing method may be used for producing the coating film of the present invention. Examples of the curing method include room temperature curing, heat curing, ultraviolet curing, and electron beam curing.
The silicone-containing fluorine-based copolymer (A, A ′, C and D) contained in the coating film of the present invention may have an unsaturated double bond. Having an unsaturated double bond has an advantage that a crosslinking reaction can be caused without using a curing agent. Moreover, when other components coexist, there exists an advantage that reaction with the component occurs easily.
[0030]
When the silicone-containing fluorine-based copolymer (A, A ′, C and D) is cured at room temperature, it can be efficiently cured at room temperature using polyvalent isocyanates. Preferred examples of the polyisocyanates include non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, adducts thereof, and polyisocyanates having isocyanurates. Among these, polyisocyanates having isocyanurates are preferable. Divalent isocyanates are particularly effective. When normal temperature curing is performed using isocyanates, curing can be promoted by the addition of a known catalyst such as dibutyltin dilaurate.
[0031]
The silicone-containing fluorine-based copolymer (A, A ′, C, and D) can be cured by heating. Examples of the curing agent include melamine curing agent, urea resin curing agent, polybasic acid curing agent and the like. Examples of the melamine curing agent include butylated melamine, methylated melamine, epoxy-modified melamine and the like, and those having various degrees of modification can be appropriately used depending on the use, and the degree of self-condensation can also be appropriately selected. Examples of urea resin curing agents include methylated urea resins and butylated urea resins, and examples of polybasic acid curing agents include long-chain aliphatic dicarboxylic acids, aromatic polyvalent carboxylic acids, and acid anhydrides thereof. Etc.
[0032]
Furthermore, blocked polyvalent isocyanates can also be suitably used as curing agents. Further, when using a melamine curing agent or urea resin curing agent, curing can be promoted by adding an acidic catalyst.
[0033]
As the thermal polymerization initiator, benzoyl peroxide, azobisisobutyronitrile, t-butylperoxy-2-ethylhexanate, t-butylperoxyisopropyl monocarbonate, or the like is used.
[0034]
The silicone-containing fluorocopolymers (A, A ′, C, and D) can be UV-cured. Examples of the photopolymerization initiator used in the case of UV curing include benzoin ether, benzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-monforinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl -Phenyl-ketone and the like are used.
[0035]
UV curing can be performed by a conventionally known method. For example, when using a high-pressure mercury lamp, 100 to 1000 mJ / cm²It can be cured under the above conditions.
[0036]
The silicone-containing fluorocopolymers (A, A ′, C and D) can also be electron beam cured. In the case of electron beam curing, curing can be performed without mixing a polymerization initiator. Examples of the curing conditions include a condition of 110 kV at 30 kGy or 200 kV at 30 kGy.
[0037]
A composition containing the silicone-containing fluorine-based copolymer and other components can also be used for the coating film of the present invention. The composition can also be cured by the method described above.
[0038]
Examples of components other than the silicone-containing fluorine-based copolymer in the composition include an acrylic resin (B), a reactive diluent (E), and a photocurable (meth) acrylate resin (F). Any one of the above components other than the silicone-containing fluorine-based copolymer can be used, or can be used in combination. As the fluorine copolymer, only one kind may be used, or a plurality may be used in combination. For example, a composition comprising at least one silicone-containing fluorocopolymer selected from silicone-containing fluorocopolymers (A), (A ′), (C) and (D) and an acrylic resin (B) Things can also be used. And at least one silicone-containing fluorocopolymer selected from silicone-containing fluorocopolymers (A), (A ′), (C) and (D); a reactive diluent (E) and A composition comprising: a photocurable (meth) acrylate resin (F); Depending on the curing method, a curing agent, a photopolymerization initiator, a thermal polymerization initiator, or the like may be added to the composition.
[0039]
Specific examples of the acrylic resin (B) include methyl (meth) acrylate copolymer, ethyl (meth) acrylate copolymer, butyl (meth) acrylate copolymer, and styrene, which are generally called acrylic resins. (Meth) acrylate copolymer, hydroxyethyl (meth) acrylate copolymer, and the like. These acrylic resins may be used alone or in combination of two or more.
[0040]
Examples of commercially available acrylic resins include Acrydic A-814, Acrydic A-810-45 (manufactured by Dainippon Ink & Chemicals), Testroid 4211-46, Testroid 4212-46 (Hitachi Chemical Polymer ( ), Dianal LR-620, Dianar LR-199, Dianar LR-2516, Dianar SS-792 (Mitsubishi Rayon Co., Ltd.), Hitaroid 3046C, Hitaroid 3018 (Hitachi Chemical Co., Ltd.) ), Etc., and may be used alone or in combination of two or more.
[0041]
When the acrylic resin (B) is used in the resin composition, the silicone-containing fluorocopolymer is 5 to 95% by weight, preferably 20 to 80% by weight, more preferably 40 to 60% by weight of the resin composition. Occupy. The acrylic resin (B) accounts for 95 to 5% by weight, preferably 80 to 20% by weight, and more preferably 60 to 40% by weight. By using an acrylic resin, the life and hardness of the coating film may be improved.
[0042]
The reactive diluent (E) includes a monofunctional one, a bifunctional one and a polyfunctional one. The molecule preferably contains an unsaturated double bond or the like. For example, monofunctional acrylate or methacrylate (may be referred to as (meth) acrylate), bifunctional (meth) acrylate, trifunctional (meth) acrylate, tetrafunctional or higher (meth) acrylate can be used. Since these molecules themselves can undergo a crosslinking reaction, they become coating film components by crosslinking. At the same time, the silicone-containing fluorine-based copolymer can be made into a solution and can function in the same manner as a solvent. Therefore, a reactive diluent can be used in place of the solvent. Such a use mode has an advantage that the amount of the organic solvent discharged into the atmosphere can be reduced as compared with the case of using the organic solvent. Furthermore, since the reactive diluent (E) has a low viscosity, the viscosity of the silicone-containing fluorine-based copolymer composition can be lowered, and workability can be improved. Due to such characteristics, the reactive diluent (E) can be used in any curing method.
[0043]
Specific examples of such a reactive diluent include one or more selected from the group consisting of the following acrylate compounds, methacrylate compounds and ethers.
[0044]
Monofunctional acrylates include isobutyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-acrylo Ruoxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, β-carboxyethyl ( Examples include meth) acrylate, isobornyl (meth) acrylate, oxyethylated phenol acrylate, phenol EO-modified (meth) acrylate, paracumylphenol EO-modified (meth) acrylate, and nonylphenol EO-modified (meth) acrylate.
[0045]
Examples of the bifunctional acrylate include 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, bisphenol A EO modified di (meth) acrylate, And isocyanuric acid EO-modified di (meth) acrylate.
[0046]
Specific examples of trifunctional (meth) acrylate monomers include pentaerythritol triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytriacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane PO-modified tri Examples thereof include acrylate and isocyanuric acid EO-modified triacrylate.
[0047]
Specific examples of tetrafunctional or higher functional (meth) acrylates include ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like.
[0048]
The photocurable (meth) acrylate resin (F) is preferable when performing photocuring such as ultraviolet curing. Examples thereof include conventionally known aliphatic / aromatic urethane (meth) acrylates, epoxy (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates, and the like.
[0049]
Specific examples include aromatic and aliphatic urethane acrylates such as Ebecryl 210, Ebecryl 8402, and Ebecryl 1290K (all three types are manufactured by Daicel UCB), KAYARAD EAM-2300, and KAYARAD R-190 (both types are manufactured by Nippon Kayaku). And epoxy acrylates such as Ebecryl 600 (manufactured by Daicel UCB), and polyester acrylates such as Ebecryl 80, Ebecryl 800, Ebecryl 810 (all three types manufactured by Daicel UCB) and Aronix M-7100 (manufactured by Toagosei Co., Ltd.). These photocrosslinkable (meth) acrylate resins may be used alone or in combination of two or more.
[0050]
The above (meth) acrylate monomers, aromatic or aliphatic urethane acrylates, epoxy acrylates, and polyester acrylate monomers or oligomers may be used alone or in combinations of two or more. However, when these are selected, a compound having low skin irritation (PPI value) is preferable in handling.
[0051]
Selected from the group consisting of at least one silicone-containing fluorocopolymer of the present invention, an acrylic resin (B), a reactive diluent (E), and a photocurable (meth) acrylate resin (F). Mixing with at least one kind can be carried out using various equipments used for ordinary coating, such as a ball mill, a paint shaker, a sand mill, a three-roll mill, and a kneader. At this time, a pigment, a dispersion stabilizer, a viscosity modifier, a leveling agent, and the like can be added and mixed as necessary.
[0052]
When producing a curable fluororesin coating mainly composed of the silicone-containing fluorocopolymer of the present invention, various solvents can be used, for example, aromatic hydrocarbons such as xylene and toluene, acetic acid Acetic esters such as ethyl and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, glycol ethers such as ethyl cellosolve, alcohols such as butanol, various commercially available thinners, and the like are particularly preferable solvents. , Butyl acetate, ethyl acetate, toluene, xylene, aromatic hydrocarbon mixtures, methyl ethyl ketone, methyl isobutyl ketone, methanol, butanol, isopropyl alcohol, ethanol and Solvesso (registered trademark). These solvents can be used alone or in combination of two or more.
[0053]
【Example】
Next, the present invention will be described in more detail with reference to examples and comparison with comparative examples, but the present invention is not limited to these examples.
[0054]
[Example 1]
After degassing into an autoclave (withstand pressure of 10 MPa) with a stainless steel stirrer having an internal volume of 1 L, 30/40 of vinylidene fluoride / tetrafluoroethylene / hydroxybutyl vinyl ether / butyl vinyl ether / reactive silicone oil I (Mw = about 4700) /15/14.97/0.03 mol% composition ratio, using butyl acetate as a polymerization solvent and t-butyl peroxypivalate as a polymerization initiator, charging them into the autoclave and stirring The temperature was raised to 60 ° C. Thereafter, the reaction was continued with stirring, and after 20 hours, the reaction was terminated to produce a silicone-containing fluoropolymer. A cured coating film of the copolymer was prepared, and the coating film characteristics were examined by the following method. The results are shown in Table 1.
Reactive silicone oil I: CH₂= C (CH_ThreeCOOC_ThreeH₆-Si (CH_Three)₂-O- [Si (CH_Three)₂-O]₆₄-Si (CH_Three)₂-C_FourH₉
[0055]
[Table 1]

[0056]
[Conditions for making cured coating film] Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) was added so that the hydroxyl group / NCO group ratio of the silicone-containing fluoropolymer was 1/1, and the corona discharge treated PET film was added. It was applied using a # 10 bar coater and heat-treated at 80 ° C. for 24 hours.
[0057]
[Measurement of coating surface composition] The XPS apparatus used was manufactured by Kratos Analytical Inc. (UK) Shimadzu / KRATOS AXIS-HS.
[Measurement Conditions] Measurement X-ray source: monochromatic AlKα ray (60 W), analysis area: 2 × 4 mm, measurement elements: Si, F, C, O,
[Survey scan measurement (qualitative analysis)] Measurement energy range: 0 to 1100 eV, Pass Energy: 160 eV, step: 1.0 eV, Dwell: 300 ms, charging neutralizer filament: current 2 A, potential -1.0 V, bias voltage- 2.7V, take off angle (removal angle) 90 °
[Multi-scan measurement (quantitative / state analysis)] Measurement energy range of each element: Si2_p  87-107eV, F1_s  678-698 eV, C1_s  278-298 eV, O1_s  521 to 541 eV, Pass energy: 40 eV, step: 0.1 eV, Dwell: 298 ms, charging neutralizer filament: current 2 A, potential -1.0 V, bias voltage -2.7 V, take off angle (take-off angle) 90 °
The atomic composition ratio (atomic%) is determined by the system of the apparatus.
[0058]
Si (atomic%) = Si / (Si + F + C + O) × 100
F (atomic%) = F / (Si + F + C + O) × 100
Respectively.
[0059]
Table 2 shows the average Si amount of the silicone-containing fluorocopolymer coating film calculated based on the above composition formula, the actual measurement value of the Si amount on the coating film surface by XPS, and the actual measurement value of the F amount on the coating film surface by XPS. Indicates. The measured value of the surface is higher than the average amount of Si in the bulk, and it can be seen that the Si site is localized near the surface.
[0060]
[Table 2]

[0061]
[Oil-based magic repellency] The surface of the coating film is painted with oil-based magic (black / red magic ink: registered trademark) to evaluate the repellency (initial stage). Furthermore, this coating film is left at room temperature for 1 hour and then removed by dry wiping. The repellency of the coating film surface after repeating this operation 20 times is evaluated in five stages.
[0062]
5 (repells well) to 1 (does not repel at all).
[Repeatable removal of oil-based magic] The surface of the coating film is painted with oil-based magic (black / red magic ink: registered trademark), left at room temperature for 1 hour, then removed by dry wiping, and the removal property is evaluated (initial). Furthermore, the removal property of the coating film surface after repeating this 20 times is evaluated in five stages.
[0063]
5 (can be completely removed) to 1 (cannot be removed at all).
[Water Repellency] The water contact angle (unit: degree) was evaluated.
[Examples 2 to 4]
The amount of the reactive silicone oil I used in Example 1 was changed to 0.1 mol%, 0.2 mol%, and 0.4 mol%, and a polymer was produced according to the operation of Example 1, The characteristics of the coating film obtained using the polymer were similarly examined. The results are shown in Table 1.
[0064]
Example 5
The reactive silicone oil I used in Example 1 was changed to a reactive silicone oil II (0.03 mol%) of Mw = about 2100, and a polymer was produced according to the procedure of Example 1, and its weight was The characteristics of the coating film obtained using the coalescence were similarly examined. The results are shown in Table 1.
Reactive silicone oil II: CH₂= C (CH_ThreeCOOC_ThreeH₆-Si (CH_Three)₂-O- [Si (CH_Three)₂-O]_{twenty five}-Si (CH_Three)_Three
[Examples 6 to 8]
The amount of the reactive silicone oil II used in Example 5 was changed to 0.001 mol%, 0.002 mol%, and 0.01 mol%, and polymers were produced in the same manner as in Example 5. The characteristics of the coating film obtained using this were similarly examined. The results are shown in Table 1.
[0065]
Example 9
The reactive silicone oil I used in Example 3 was changed to reactive silicone oil III (0.2 mol%) having Mw = about 11400, and a polymer was produced in the same manner as in Example 3, and the polymer was used. The properties of the coating film obtained in this manner were examined in the same manner. The results are shown in Table 1. Reactive silicone oil III: CH₂= C (CH_ThreeCOOC_ThreeH₆-Si (CH_Three)₂-O- [Si (CH_Three)₂-O]₁₄₀-Si (CH_Three)₂-C_FourH₉
Example 10
The silicone-containing fluorine-based copolymer obtained in Example 1 and Dynal LR-199 (manufactured by Mitsubishi Rayon Co., Ltd.) are mixed so that the solid content is 5/5, and the silicone-containing fluorine-based copolymer is mixed. A composition was prepared. These characteristics were examined similarly. The results are shown in Table 1.
[0066]
Example 11
After degassing into an autoclave (withstand pressure of 10 MPa) with a stainless steel stirrer having an internal volume of 1 L, 30/40 of vinylidene fluoride / tetrafluoroethylene / hydroxybutyl vinyl ether / butyl vinyl ether / reactive silicone oil I (Mw = about 4700) /15/14.97/0.03 mol% composition ratio, using butyl acetate as a polymerization solvent and t-butyl peroxypivalate as a polymerization initiator, charging them into the autoclave and stirring The temperature was raised to 60 ° C. Thereafter, the reaction was continued with stirring, and after 20 hours, the reaction was terminated to produce a hydroxyl group-containing copolymer. Subsequently, the hydroxyl group of the hydroxyl group-containing copolymer and the isocyanate group of 2-isocyanatoethyl methacrylate were added and reacted to produce a silicone-containing fluorine-containing copolymer containing an unsaturated double bond. A cured coating film of the polymer was prepared under the following conditions, and the coating film characteristics were examined in the same manner as in Example 1. The results are shown in Table 1.
[0067]
[Conditions for making cured coating film] A 50% butyl acetate solution of the above polymer was applied to a PET film subjected to corona discharge treatment using a # 10 bar coater, dried at 80 ° C. for 1 minute, and then in an atmosphere with an oxygen concentration of 200 ppm. Then, an electron beam was irradiated with an electron beam irradiation apparatus EC250 / 15 / 180L manufactured by Iwasaki Electric under the conditions of an acceleration voltage of 200 kV and a dose of 30 kGy.
[0068]
Example 12
100 g of the above-mentioned 50% butyl acetate solution of the silicone-containing fluorocopolymer containing an unsaturated double bond obtained in Example 11, 30 g of Ebecryl 80 (polyester acrylate manufactured by Daicel UCB), and 1,6-hexane 20 g of diol diacrylate and 5 g of 2-methyl-1- [4- (methylthio) phenyl] -2-montforinopropan-1-one (manufactured by Ciba Geigy Co., Ltd.) were mixed to form a silicone-containing fluorine-based copolymer. A polymer composition was prepared. A cured coating film of the composition was prepared under the following conditions, and the coating film characteristics were examined in the same manner as in Example 1. The results are shown in Table 1.
[0069]
[Conditions for making a cured coating film] The copolymer composition butyl acetate solution was applied to a PET film subjected to corona discharge treatment using a # 10 bar coater, dried at 80 ° C for 1 minute, and then 250 mJ / cm in air.²The ultraviolet rays were irradiated.
[0070]
[Comparative Example 1]
A polymer was produced in the same manner as in Example 1 with the charged composition excluding the reactive silicone oil I in the charged composition of Example 1, and the coating film characteristics were similarly examined. The results are shown in Table 1.
[0071]
[Comparative Example 2]
A polymer was produced in the same manner as in Example 11 except that the reactive silicone oil I was removed from the charged composition of Example 11. The coating film characteristics were examined in the same manner as in Example 11. The results are shown in Table 1.
[0072]
[Comparative Example 3]
The reactive silicone oil II used in Example 5 was changed to 0.0008 mol%, a polymer was produced in the same manner as in Example 5, and the coating film characteristics were similarly examined. The results are shown in Table 1.
[0073]
【The invention's effect】
The present invention is excellent in antifouling properties, water and oil repellency, chemical resistance, weather resistance, etc., and a coating film in which the number of Si atoms existing on the coating film surface measured by XPS occupies 2 to 30 atomic%, In particular, the present invention relates to a coating film characterized in that the number of Si atoms existing on the surface of the coating film occupies 2 to 30 atomic% and the number of F atoms occupies 2 to 32 atomic%. Is unevenly distributed (that is, Si sites in the silicone-containing fluorine-based copolymer are unevenly distributed in the direction of the surface of the coating film). Obtainable. Also when mixing with other resins and other monomers, the Si unit in the silicone-containing fluorocopolymer of the present invention is localized at a high concentration in the vicinity of the surface, so mixing with a small amount of the copolymer is excellent. A coating surface can be obtained.
[0074]
The cured coating film of the silicone-containing fluorocopolymer and composition of the present invention has excellent properties (antifouling property, water and oil repellency, chemical resistance, weather resistance, etc.), so it can be used for interior applications (walls, floors). It is suitable for fields requiring antifouling properties such as, furniture, etc., release film applications, fields requiring weather resistance such as outdoor applications (outer walls, films, etc.), graffiti prevention applications, and the like. It is also useful for interior and exterior painting of large buildings, transportation vehicles, ships and the like.

Claims (14)

  A coating film formed from a composition containing a silicone-containing fluorine-based copolymer coated on a substrate, wherein the number of Si atoms present on the coating film surface measured by X-ray photoelectron spectroscopy is 2 to 2. A coating film characterized by occupying 30 atomic%.   2. The coating film according to claim 1, wherein the number of F atoms present on the coating film surface measured by X-ray photoelectron spectroscopy occupies 2 to 32 atomic%.   A coating film formed from a composition containing a silicone-containing fluorine-based copolymer coated on a substrate surface, the number of Si atoms present on the coating film surface measured by X-ray photoelectron spectroscopy and The said coating film characterized by ratio (Si / F value) with the number of atoms of F atom being 0.0625-10.0.   The water-repellent coating film according to any one of claims 1 to 3, wherein a contact angle with water is 98 to 110 degrees.   The thickness of a coating film is 0.0001-0.5 mm, The coating film in any one of Claims 1-4.   The coating film according to any one of claims 1 to 5, wherein the substrate is selected from an acrylic material, wood, plastic, metal, graphite, paper, concrete, noncombustible material, and glass. As a polymerization unit, 0.001% of at least one reactive silicone selected from the group consisting of (a) 15 to 85 mol% of fluoroolefin; and (b) the formulas (1), (2) and (3) The coating film according to any one of claims 1 to 6, formed by using a reactive silicone-containing fluorine-based copolymer (A) characterized by comprising:

(Here, R ¹ represents CH ₂ ═C (CH ₃ ) COO (CH ₂ ) _r1 —, CH ₂ ═CHCOO (CH ₂ ) _r1 —, or CH ₂ ═CH—. R ² represents the number of carbon atoms. 1-12 alkyl _{group, CH 2 = C (CH 3} ) COO (CH 2) r2 -, CH 2 = CHCOO (CH 2) r2 -, or .n showing a CH ₂ = CH- is an integer of 20 to 150 R ₁ represents an integer of ₁ to 6, and r ₂ represents an integer of 1 to 6.)
R ² —Si [OSi (CH ₃ ) ₃ ] ₃ (2)
CH ₂ = C (R ³ ) Si (R ⁴ ) (R ⁵ ) (R ⁶ ) (3)
(Wherein R ³ represents a hydrogen atom or a methyl group. R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, t - butyl group, sec- butyl group, a phenyl group, a substituted phenyl _{group, -CF 3, -C 2 H 4} CF 3, .R 4 showing a _{-OSi (CH 3) 3, R} 5, R 6 are each identical Or it may be different.) As polymerized units, (a) 15 to 85 mol% of fluoroolefin; and (b) 0.001 to 30 mol% of one or more reactive silicones selected from the group consisting of formulas (4) to (8) A coating film according to any one of claims 1 to 6, which is formed using a reactive silicone-containing fluorine-based copolymer (A ').
_{CH 2 = C (CH 3)} COOC 3 H 6 -Si (CH 3) 2 -O- [Si (CH 3) 2 -O] p -Si (CH 3) 2 -R 7 (4)
(Here, R ⁷ represents an alkyl group having 1 to 12 carbon atoms or CH ₂ ═CH—. P represents an integer of 25 to 150.)
_{CH 2 = CHCOOC 3 H 6 -Si} (CH 3) 2 -O- [Si (CH 3) 2 -O] s -Si (CH 3) 2 -R 8 (5)
(Here, R ⁸ represents an alkyl group having 1 to 12 carbon atoms or CH ₂ ═CH—. S represents an integer of 25 to 150.)

(Here, R ⁹ represents CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ — or CH ₂ ═CHCOO (CH ₂ ) ₃ —. Q represents an integer of 20 to 150.)
_{CH 2 = CH-Si (CH} 3) 2 -O- [Si (CH 3) 2 -O] y -Si (CH 3) 2 -R 10 (7)
(Here, R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms or CH ₂ ═CH—. Y represents an integer of 25 to 150.)
_{CH 2 = C (CH 3)} COOC 3 H 6 -Si [OSi (CH 3) 3] 3 (8) (A) 15 to 85 mol% of a fluoroolefin as polymerized units; (b) 0.001 to 30 mol% of one or more reactive silicones selected from formulas (1), (2) and (3); And (c) a hydroxyl group-containing reactive silicone-containing fluorine-based copolymer (C) composed of 1 to 50 mol% of a hydroxyl group-containing unsaturated monomer; and an unsaturated isocyanate (d)
The coating film in any one of Claims 1-6 formed using the silicone containing fluorine-type copolymer (D) produced | generated by reaction with.   One or more fluorocopolymers selected from the group consisting of silicone-containing fluorocopolymers (A), (A ′), and (D); an acrylic resin (B), a reactive diluent ( E) and one or more components selected from the group consisting of a photocurable (meth) acrylate resin (F), and the coating according to any one of claims 1 to 6 formed using a resin composition comprising: film.   The coating film according to claim 10, wherein the resin composition contains 5 to 95% by weight of a silicone-containing fluorine-based copolymer and 95 to 5% by weight of an acrylic resin (B).   The coating film of Claim 10 or 11 in which a resin composition contains at least 1 sort (s) of a reactive diluent (E) and photocurable (meth) acrylate resin (F).   The coating film according to any one of claims 7 to 12, wherein the silicone-containing fluorine-based copolymer contains an unsaturated double bond.   Applying a composition comprising one or more copolymers selected from the group consisting of silicone-containing fluorocopolymers (A), (A ′), and (D); curing the composition; X The ratio of Si atoms present on the coating film surface measured by line photoelectron spectroscopy is 2 to 30 atomic%, and the ratio of F atoms is 2 to 32 atomic%;