JP2004250517A - Coating composition and coated material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition which has stable coatability over a long period and gives coating films having water-repelling and oil-repelling performances in excellent durability. <P>SOLUTION: This coating composition is characterized by comprising (A) a copolymer comprising (a) 20 to 60 wt. % of constituent units originated from a fluoroalkyl group-having (meth)acrylate, (b) 8 to 36 wt. % of constituent units originated from an epoxy group-having (meth)acrylate, (c) 7 to 24 wt. % of constituent units originated from a hydrolyzable silicon-containing group-having (meth)acrylate, and (d) 12 to 65 wt. % of constituent units originated from a cross-linking reactive group-free ethylenic unsaturated compound in a solid concentration of 0.1 to 11 wt. %, (B) a cross-linking agent for the epoxy group, and (C) a solvent. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００１４】
［式中Ｒ^１は水素原子またはメチル基、Ａ^１は−（ＣＨ_２）_ｋ−、−ＳＯ_２Ｎ（Ｒ^２）−（ＣＨ_２）_ｋ−、―ＣＯＮＲ^２−（ＣＨ_２）_ｋ−ＣＨ_２ＣＨ（ＯＣＯＲ^１）ＣＨ_２−、−Ｏ−Ａｒ−ＣＨ_２−、（Ｒ^２は水素原子または炭素数１〜１０の直鎖状または分岐状のアルキル基、Ａｒはアリール基を示し、ｋは１〜１０の整数である。）、Ｒ_ｆは炭素数３〜２０の直鎖状または分岐状のフルオロアルキル基を示す。］
で表される化合物が挙げられる。
【００１５】
このような単量体の具体例としては、以下のものが挙げられるがこれらに限定されるものではない。
ＣＦ_３（ＣＦ_２）_３（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_４ＣＨ_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_５ＣＨ_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_５（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_６（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_９（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_１１（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_２（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_４（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_６（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_６（ＣＨ_２）_３ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_３（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_３ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_４ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_５ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_５（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_６（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_７（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_９（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_１１（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_２（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_４（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_６（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２
（ＣＦ_３）_２ＣＦ（ＣＦ_２）_６（ＣＨ_２）_３ＯＣＯＣＨ＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_７ＳＯ_２Ｎ（ＣＨ_３）（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_７ＳＯ_２Ｎ（Ｃ_２Ｈ_５）（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_７ＳＯ_２Ｎ（ＣＨ_３）（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_７ＳＯ_２Ｎ（Ｃ_２Ｈ_５）（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_４ＣＯＮＨ（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_８ＣＯＮＨ（ＣＨ_２）_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_７ＣＯＮＨ（ＣＨ_２）_２ＯＣＯＣＨ＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_４Ｏ−Ｃ_６Ｈ_４−ＣＨ_２ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_８Ｏ−Ｃ_６Ｈ_４−Ｃ_３Ｈ_６ＯＣＯＣ（ＣＨ_３）＝ＣＨ_２
ＣＦ_３（ＣＦ_２）_７Ｏ−Ｃ_６Ｈ_４−ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２
上記一般式（Ｉ）において、Ｒ_ｆで示されるフルオロアルキル基はパーフルオロアルキル基であることが好ましく、パーフルオロアルキル基の炭素数は６〜１２であることが好ましい。炭素数が６よりも小さいと撥水性が低下するため好ましくなく、また１２よりも大きいと溶解性、経済性が低下することから好ましくない。本発明においては、フルオロアルキル基を含有する（メタ）アクリレートは、１種用いてもよいし、２種以上を組み合わせて用いてもよく、２種以上を用いる場合には、フルオロアルキル基の炭素数が異なるフルオロアルキル基を有する（メタ）アクリレートを用いることが好ましい。
【００１６】
また、（ｂ）構成単位を形成する単量体のエポキシ基を有する（メタ）アクリル酸エステルとしては、例えば一般式（ＩＩ）
【化２】

【００１７】
（式中、Ｒ^２およびＲ^３は、それぞれ水素原子またはメチル基を示し、それらはたがいに同一でも異なっていてもよく、Ａ^２は直接結合またはエーテル結合を有していてもよい炭素数１〜１０のアルキレン基、Ｒ^４は水素原子または炭素数１〜１０のアルキル基を示す。）
で表される化合物を用いることができる。
【００１８】
前記一般式（ＩＩ）において、Ａ^２のうちの炭素数１〜１０のアルキレン基は、直鎖状、分岐状のいずれであってもよく、その例としては、メチレン基、エチレン基、メチルエチレン基、トリメチレン基、各種ブチレン基、各種ペンチレン基、各種ヘキシレン基などが挙げられる。このアルキレン基はエーテル結合を有していてもよい。また、Ｒ^４のうちの炭素数１〜１０のアルキル基は、直鎖状、分岐状のいずれであってもよく、その例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、各種ブチル基、各種ペンチル基、各種ヘキシル基、各種オクチル基などが挙げられる。
【００１９】
前記一般式（ＩＩ）で表される化合物としては、例えば以下のようなものが挙げられるが、これらに限定されるものではない。
【化３】

【００２０】
本発明においては、前記エポキシ基を有する（メタ）アクリル酸エステルは、１種を用いてもよく、２種以上を組み合わせて用いてもよい。
【００２１】
次に、（ｃ）構成単位を形成する単量体の加水分解性ケイ素含有基を有する（メタ）アクリル酸エステルとしては、例えば前記一般式（ＩＩＩ）
【化４】

【００２２】
（式中、Ｒ^５は水素原子又はメチル基、Ｒ^６は水素原子、水酸基または加水分解性基、Ｒ^７は非加水分解性基、Ａ^３は炭素数１〜４のアルキレン基、ｎは１〜３の整数を示し、Ｒ^６が複数ある場合、複数のＲ^６はたがいに同一であっても異なっていてもよく、Ｒ^７が複数ある場合、複数のＲ^７はたがいに同一であっても異なっていてもよい。）
で表される化合物を用いることができる。
【００２３】
前記一般式（ＩＩＩ）において、Ｒ^６のうちの加水分解性基としては、例えば、低級アルコキシル基、イソシアネート基、塩素原子などのハロゲン原子、アセチルアセトネート基、アルコキシカルボニル基などが挙げられるが、これらの中で低級アルコキシル基が好ましい。一方、Ｒ^７で示される非加水分解性基としては、例えば炭素数１〜８のアルキル基、炭素数６〜１０のアリール基または炭素数７〜１０のアラルキル基などが挙げられる。また、Ａ^３で示される炭素数１〜４のアルキレン基は、直鎖状、分岐状のいずれであってもよく、その例としては、メチレン基、エチレン基、メチルエチレン基、トリメチレン基、テトラメチレン基などを挙げることができる。
【００２４】
この一般式（ＩＩＩ）で表される化合物としては、例えば３−（メタ）アクリロキシプロピルトリメトキシシラン、３−（メタ）アクリロキシプロピルトリエトキシシラン、３−（メタ）アクリロキシプロピルトリプロポキシシラン、３−（メタ）アクリロキシプロピルメチルジメトキシシラン、３−（メタ）アクリロキシプロピルメチルジエトキシシラン、３−（メタ）アクリロキシプロピルメチルジプロポキシシラン、４−（メタ）アクリロキシブチルフェニルジメトキシシラン、４−（メタ）アクリロキシブチルフェニルジエトキシシラン、４−（メタ）アクリロキシブチルフェニルジプロポキシシラン、３−（メタ）アクリロキシプロピルジメチルメトキシシラン、３−（メタ）アクリロキシプロピルジメチルエトキシシラン、３−（メタ）アクリロキシプロピルフェニルメチルメトキシシラン、３−（メタ）アクリロキシプロピルフェニルメチルエトキシシラン、３−（メタ）アクリロキシプロピルトリヒドロキシシラン、３−（メタ）アクリロキシプロピルメチルジヒドロキシシラン、４−（メタ）アクリロキシブチルフェニルジヒドロキシシラン、３−（メタ）アクリロキシプロピルジメチルヒドロキシシラン、３−（メタ）アクリロキシプロピルフェニルメチルヒドロキシシラン、
【００２５】
【化５】

【００２６】
などを挙げることができるが、これらに限定されるものではない。
本発明においては、前記加水分解性ケイ素含有基を有する（メタ）アクリル酸エステルは、１種を用いてもよく、２種以上を組み合わせて用いてもよい。
さらに、（ｄ）構成単位を形成する単量体の架橋性反応基を有しないエチレン性不飽和化合物としては、例えばオレフィン系化合物、ビニルエーテルおよびアリルエーテル、ビニルエステルおよびプロペニルエステル、（メタ）アクリル酸エステル、ビニル芳香族化合物などを挙げることができるがこれらに限定されるものではない。
【００２７】
さらに具体的には、オレフィン化合物としては、例えばエチレン、プロピレン、ブチレン、イソプレン、クロロプレン等を挙げることができる。
ビニルエーテルおよびアリルエーテルとしては、例えばエチルビニルエーテル、プロピルビニルエーテル、イソプロピルビニルエーテル、ブチルビニルエーテル、ｔｅｒｔ−ブチルビニルエーテル、ペンチルビニルエーテル、ヘキシルビニルエーテル、イソヘキシルビニルエーテル、オクチルビニルエーテル、４−メチル−１−ペンチルビニルエーテル等の鎖状アルキルビニルエーテル類、シクロペン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シクロアルキルビニルエーテル類、フェニルビニルエーテル、ｏ−，ｍ−，ｐ−トリビニルエーテル等のアリールビニルエーテル類、ベンジルビニルエーテル、フェネチルビニルエーテル等のアラルキルビニルエーテル類等を挙げることができる。
【００２８】
ビニルエステルおよびプロペニルエステルとしては、例えば酢酸ビニル、乳酸ビニル、酪酸ビニル、イソ酪酸ビニル、カプロン酸ビニル、イソカプロン酸ビニル、ピバリン酸ビニル、カプリン酸ビニル等のビニルエステル、及び酢酸イソプロペニル、プロピオン酸イソプロペニル等のプロペニルエステル等を挙げることができる。
（メタ）アクリル酸エステルとしては、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸ラウリルなどの（メタ）アクリル酸の炭素数１〜１８のアルキルエステルを挙げることができる。
ビニル系芳香族化合物としては、例えばスチレン、α−メチルスチレン、ビニルトルエン、ｐ−クロルスチレン等を挙げることができる。
その他、アクリロニトリル、メタクリロニトリルを使用することもできる。
【００２９】
本発明においては、前記架橋性反応基を有しないエチレン性不飽和化合物は、１種を用いてもよく、２種以上を組み合わせて用いてもよい。
本発明においては、前記の各単量体を、従来公知のラジカル重合開始剤の存在下に、ラジカル重合させることにより、（Ａ）成分の共重合体が得られる。
このようにして得られた共重合体中の各構成単位の含有割合は、（ａ）構成単位が２０〜６０重量％、（ｂ）構成単位が８〜３６重量％、（ｃ）構成単位が７〜２４重量％および（ｄ）構成単位１２〜６５重量％の範囲で選定される。
【００３０】
（ａ）構成単位の含有量が２０重量％未満では硬化被膜の撥水性が低下し、６０重量％を超えると、該硬化被膜の耐久性が低下すると共に、経済性に劣る。（ｂ）構成単位の含有量が８重量％未満では硬化被膜の耐久性が劣り、３６重量％を超えると組成物の安定性が低下する。この（ｂ）構成単位の好ましい含有量は８〜２０重量％である。（ｂ）構成単位の含有量がこの範囲にあれば、後述する（Ｂ）成分のエポキシ基用架橋剤の好ましい量およびコーティング組成物の固形分含有量の範囲において、優れた組成物の安定性および硬化被膜の耐久性を示すが、２０重量％を超えると組成物の安定性が若干低下するおそれがあるので、この場合は、エポキシ基用架橋剤量や組成物中の固形分含有量を少なくすることが有利である。（ｃ）構成単位の含有量が７重量％未満であったり、２４重量％を超えると硬化被膜の耐久性が低下する。（ｄ）構成単位の含有量が１２重量％未満では組成物の安定性が低下すると共に、経済性に劣り、６５重量％を超えると撥水性が低下する。
【００３１】
組成物の安定性、硬化被膜の撥水性や耐久性及び経済性などを考慮すると、各構成単位の好ましい含有量は、（ａ）構成単位が３０〜５５重量％、（ｂ）構成単位が８〜２０重量％、（ｃ）構成単位が１０〜２０重量％および（ｄ）構成単位が１２〜５２重量％の範囲で選定される。
本発明のコーティング組成物においては、前記（Ａ）成分の共重合体は、固形分として０．１〜１１重量％の濃度で含まれる。この濃度が０．１重量％未満では基材に対する被覆が不十分となり、撥水性が低下して本発明の目的が達せられない。一方、１１重量％を超えると組成物の安定性が低下する。前記共重合体の好ましい濃度は、固形分として０．５〜１１重量％であり、特に１〜１１重量％の範囲が好適である。
【００３２】
本発明のコーティング組成物において、（Ｂ）成分として用いられるエポキシ基用架橋剤としては、エポキシ基を架橋し得るものであればよく、特に制限されず、従来エポキシ基樹脂の硬化剤として知られている公知架橋剤の中から適宜選択することができる。このようなエポキシ基用架橋剤としては、各種アミン類や酸無水物などがあるが、アミン類が好ましい。アミン類としては、１分子中に少なくとも２個の一級若しくは二級アミノ基を有する化合物が好ましい。このようなアミン類としては、脂肪族・脂環式ポリアミン、ポリアミド・アミン、芳香族ポリアミンなどがあるが、これらの中で常温硬化型の脂肪族・脂環式ポリアミンおよびポリアミド・アミンが特に好適である。
【００３３】
上記脂肪族・脂環式ポリアミンとしては、例えばエチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、イミノビスプロピルアミン、ビス（ヘキサメチレン）トリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、１，３，６−トリス（アミノメチル）ヘキサン、Ｎ−ベンジルエチレンジアミン、トリメチルヘキサメチレンジアミン、ジメチルアミノプロピルアミン、アミノエチルエタノールアミン、ジエチレングリコール・ビスプロピレンジアミン、ポリプロピレングリコールの両末端水酸基をアミノ基に変換したジアミン、メンチンジアミン、イソホロンジアミン、Ｎ−アミノエチルピペラジン、１，３−ビス（アミノメチル）シクロヘキサン、パラメンタンジアミン、メツホロンジアミン、ビス−（４−アミノ−３−メチルシクロヘキシル）メタンなどが挙げられる。また、ポリアミド・アミンとしては、各種市販品のものを用いることができる。
芳香族ポリアミンとしては、例えばｍ−フェニレンジアミン、４−４’−ジアミンジフェニルメタン、４−４’−ジアミノジフェニルスルホン、ジアミノジフェニルエーテルなどが挙げられる。
【００３４】
本発明においては、この（Ｂ）成分のエポキシ基用架橋剤は１種用いてもよく、２種以上を組み合わせて用いてもよい。
このエポキシ基用架橋剤の含有量は、（Ａ）成分共重合体中の（Ｂ）成分由来の構成単位におけるエポキシ基に対し、好ましくは０．５〜１０倍当量の範囲で、かつ後述の（Ｃ）成分の溶剤１００重量部に対し、好ましくは５重量部以下の範囲で選定される。この架橋剤の量が、エポキシ基に対し、０．５倍当量未満では硬化反応が進行しにくく、硬化被膜の耐久性が不十分となるおそれがあり、一方１０倍当量を超えると組成物の安定性が低下する原因となる。また、溶剤１００重量部に対し、５重量部を超えると硬化被膜の透明性が低下するため好ましくない。
【００３５】
本発明のコーティング組成物においては、所望により、架橋促進剤として、従来エポキシ樹脂の硬化促進剤として知られている公知の化合物、例えば第三級アミン類、イミダゾール類、有機金属化合物、第四級アンモニウム化合物、有機リン系化合物、ホウ素系化合物、金属ハロゲン化物などの中から、適宜１種以上選び含有させることができる。
【００３６】
本発明のコーティング組成物において、（Ｃ）成分の溶剤としては、（Ａ）成分である共重合体の溶解性などの点から、ケトン類、芳香族炭化水素類、エーテル類、エステル類およびアルコール類の中から選ばれる少なくとも１種が用いられる。ここで、ケトン類としては、例えばアセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどが挙げられ、芳香族炭化水素類としては、例えばベンゼン、トルエン、キシレン、エチルベンゼン、ジエチルベンゼン、プソイドキュメンなどが挙げられる。また、エーテル類としては、例えばテトラヒドロフラン、ジオキサン、さらにはエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテルなどのセロソルブ系溶剤などが挙げられ、エステル類としては、例えば、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸プロピル、酪酸メチル、酪酸エチルなどが挙げられる。アルコール類としては、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、オクタノール、シクロヘキサノール、ベンジルアルコールなどが挙げられる。これらの溶剤は１種を単独で用いてもよく、２種以上を混合して用いてもよい。
【００３７】
本発明のコーティング組成物には、本発明の目的が損なわれない範囲で、必要に応じ、各種添加剤、例えばレベリング剤、カップリング剤、増粘剤、タレ防止剤、充填剤、可塑剤、酸化防止剤、紫外線吸収剤、光安定剤、帯電防止剤、凍結防止剤などを含有されることができる。
本発明のコーティング組成物は、長時間にわたり安定した塗工性を有すると共に、撥水撥油性能の持続性に優れた硬化被膜を形成することができる。
【００３８】
次に、本発明の被コーティング材は、基材表面に、前述の本発明のコーティング組成物を用いて形成された撥水性硬化被膜を有するものである。
前記基材の材質としては、金属、セラミックス、ガラス、プラスチック、木、石、セメント、コンクリート、繊維、布帛、紙、それらの組合わせ、それらの積層体、それらの塗装体等が挙げられる。本発明の組成物が適用可能な部材は、表面の防滴性、防錆性、水切れ性、水系汚れ付着防止性、流水洗浄性、着氷雪防止性等が要求されるあらゆる部材に適用できる。
【００３９】
具体的には、外壁や屋根のような建築外装；窓枠；自動車、鉄道車両、航空機、船舶、自転車、オートバイのような乗物の外装及び塗装；防音壁、ビニールハウス、碍子、乗物用カバー、テント材、反射板、雨戸、網戸、太陽電池用カバー、太陽熱温水器等の集熱器用カバー、街灯、舗道、屋外照明、人工滝、人工噴水用石材、タイル、橋、温室、外壁材、壁間や碍子間のシーラー、ガードレール、ベランダ、自動販売機、エアコン室外機、屋外ベンチ、各種表示装置、シャッター、料金所、料金ボックス、防塵カバー及び塗装、機械装置や物品の塗装、広告塔の外装及び塗装、構造部材及びそれら物品に粘着可能なフィルム、ワッペン等である。
【００４０】
本発明のコーティング組成物を塗布した硬化被膜に密着性が要求される場合においては、加水分解性ケイ素含有基、エポキシ基と結合する反応基が基材表面に被覆されていることが好ましい。
密着性をより向上させるために、基材に本発明のコーティング組成物を塗布したり、吹き付けたりしてコーティングする前に、中間層を少なくとも１層コーティングしたり、コロナ放電処理を施す等基材に前処理を施してもよい。
【００４１】
基材表面に、本発明のコーティング組成物を塗布する方法としては特に制限はなく、状況に応じて、従来公知の方法、例えばスピンコーティング法、ディップコーティング法、フローコーティング法、スプレーコーティング法、ロールコーティング法、スクリーン印刷法、バーコーター法、刷毛塗り、スポンジ塗りなどの中から適宜選択することができる。
このようにして、基材表面に形成された塗膜は、室温でも充分に硬化を促進させたり、基材との密着性をより向上させたり、平面平滑性を向上させる目的で、４０〜１５０℃の温度で５分〜１週間程度保持し、硬化させてもよい。
このようにして形成された撥水性硬化被膜の厚さは、２５０〜１５００ｎｍの範囲にあることが好ましい。この厚さが２５０ｎｍ未満では硬化被膜の耐久性が不十分となるおそれがあり、１５００ｎｍを超えると透明性が低下する原因となると共に、経済性の面からも好ましくない。この硬化被膜のより好ましい厚さは、３００〜１０００ｎｍの範囲である。
【００４２】
【実施例】
次に、本発明を実施例により、さら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。
なお、コーティング組成物のポットライフ、および被覆物試験板の物性は、以下に示す方法に従って求めた。
（１）コーティング組成物のポットライフ
コーティング組成物について、オストワルド粘度計にて比粘度を測定することで評価した。２５℃１０時間後の比粘度が、２５℃３０分後の比粘度と比較してその増加率を求めた。目安として、増加率が２５％未満の場合合格、２５％以上の場合不合格である。
（２）被覆物試験板の物性
（イ）膜厚
被覆物試験板の断面を走査型電子顕微鏡（日立製作所社製「Ｓ−４１００」）にて観察することで被覆物試験板の膜厚を測定した。
（ロ）撥水性
被覆物試験板を接触角計（協和界面科学社製「ＣＡ−Ｘ１５０型」）を用い、約１μＬの水滴を被覆物試験板上にのせ、水接触角を測定した。目安として、水接触角が１１０°以上の場合合格、１１０°未満の場合不合格である。
（ハ）透明性
ＪＩＳＫ７１０５に準じて、被覆物試験板のヘイズ値を測定した。目安として、ヘイズ値が２％未満の場合合格、２％以上の場合不合格である。
（ニ）耐摺動性
被覆物試験板を、摺動試験機（東洋精機製作所社製「ウォッシャビリティーテスター」）を用い、ベンコット（旭化成工業社製「Ｍ−３」）で荷重１２２．６ｍＮ／ｃｍ^２の負荷を加え、１分間に３５回のストロークで１０００回摺動させた。１０００回摺動後の水接触角を測定した。目安として、水接触角が１００°以上の場合合格、１００°未満の場合不合格である。
【００４３】
製造例１
メチルイソブチルケトン（和光純薬工業社製）３４０重量部に、メタクリル酸メチル（ＭＭＡ、和光純薬工業社製）２６．３重量部、メタクリル酸グリシジル（ＧＭＡ、和光純薬工業社製）１８．７重量部、３−メタクリルオキシプロピルトリメトキシシラン（ＭＰＴＭＳ、信越化学工業社製「ＬＳ−３３８０」）１３．０重量部、２−（パーフルオロオクチル）エチルメタクリレート（ＦＭＡ、ダイキンファインケミカル研究所社製「Ｍ−１８２０」）４２．０重量部を加え、よく攪拌した後、これにメチルイソブチルケトン９６重量部に２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．１重量部を溶かした溶液に加え、５６℃において１時間加熱攪拌させ共重合体分散液を作製した。作製した共重合体分散液を常温になるまで冷却した後、メタノール（和光純薬工業社製）１２３０重量部に流し込み、共重合体を沈澱させ、得られた沈殿物を減圧乾燥することで共重合体（Ｉ）を得た。
【００４４】
製造例２
製造例１において、ＭＭＡ、ＧＭＡ、ＭＰＴＭＳおよびＦＭＡの使用割合を表１に示すように変えた以外は、製造例１と同様にして共重合体（ＩＩ）を得た。
比較製造例１〜５
製造例１において、ＭＭＡ、ＧＭＡ、ＭＰＴＭＳおよびＦＭＡの使用割合を表１に示すように変えた以外は、製造例１と同様にして共重合体（ＩＩＩ）〜（ＶＩＩ）を得た。
【００４５】
【表１】

【００４６】
実施例１
メチルイソブチルケトン（ＭＩＢＫ）８７．６重量部に、製造例１で得られた共重合体（Ｉ）９．９重量部を添加、攪拌したのち、さらにジアミン（サンテクノケミカル社製「ジェファーミンＤ−２３０」、活性水素当量約６０ｇ／ｅｑ）２．５重量部添加し、１５分間攪拌して、撥水性コーティング組成物Ａ１を調製した。
実施例２〜４
実施例１において、共重合体として、表２に示す種類のものを用い、かつＭＩＢＫ、共重合体およびジアミンの使用割合を、表２に示すように変えた以外は、実施例１と同様にして、撥水性コーティング組成物Ａ２〜Ａ４を調製した。
比較例１〜６
実施例１において、共重合体として、表２に示す種類のものを用い、かつＭＩＢＫ、共重合体およびジアミンの使用割合を、表２に示すように変えた以外は、実施例１と同様にして、撥水性コーティング組成物Ａ５〜Ａ１０を調製した。
【００４７】
【表２】

【００４８】
実施例５
１，３−ビス（トリフルオロメチル）ベンゼン９２．６重量部に、製造例１で得られた共重合体（Ｉ）５．９重量部を添加、攪拌したのち、さらにジアミン（サンテクノケミカル社製「ジェファーミンＤ−２３０」、活性水素当量約６０ｇ／ｅｑ）１．５重量部添加し、１５分間攪拌して、撥水性コーティング組成物Ａ１１を調製した。
【００４９】
実施例６
９０×９０ｍｍに切断したポリエチレンテレフタレートフィルム（東レ・デュポン社製「ルミラーＵ９４」、膜厚１００μｍ、以下ＰＥＴフィルムと称す。）にコロナ処理（春日電機社製「ＡＧＦ−０１０」、０．１ｋＷ）を施したのち、実施例１で得られた撥水性コーティング組成物Ａ１を２ｍＬ滴下し、スピンコーター（エイブル社製「ＡＳＳ３０１」）にて１５００ｒｐｍで２０秒間スピンコートした後、１２０℃で１２時間乾燥することによりコーティング組成物Ａ１の被覆物試験板を得た。
コーティング組成物のポットライフおよび被覆物試験板の物性を表３に示す。
【００５０】
実施例７〜１０及び比較例７〜１２
実施例６において、撥水性コーティング組成物として、表３に示す種類のものを用いた以外は、実施例６と同様にして被覆物試験板を作製した。
各コーティング組成物のポットライフおよび各被覆物試験板の物性を表３に示す。
【００５１】
【表３】

【００５２】
表３から明らかなように、実施例１〜３は、ポットライフおよび試験板の全ての物性が良好である。また、実施例４は共重合体に対して架橋剤の量が多くて、ポットライフが不十分であり、実施例５は、使用した溶剤の影響で、試験板の透明性に劣る。一方、比較例７〜１１は、重要な物性である撥水性あるいは耐摺動性（耐久性）が悪く、また、比較例１２は、コーティング組成物中の共重合体の量が多く、ポットライフが短い。
【００５３】
実施例１１
ＰＥＴフィルムに実施例１で得られた撥水性コーティング組成物Ａ１をマイクログラビアコーター（康井精機社製斜線型グラビア、グラビアメッシュ＃７０、コーティング速度１０ｍ／分）にてコートした後１２０℃で１２時間乾燥することにより、コーティング組成物Ａ１の被覆物試験板を得た。
被覆物試験板の膜厚および物性を表４に示す。
【００５４】
実施例１２〜１４
実施例１１において、マイクログラビアコーターのグラビアメッシュ、コーティング速度を表４に示すグラビアメッシュ、コーティング速度に変えた以外は、実施例１１と同様にして、コーティング組成物Ａ１の被覆物試験板を作製した。
各被覆物試験板の膜厚および物性を表４に示す。
【００５５】
【表４】

【００５６】
表４から分かるように、実施例１１〜１３は、被覆物試験板の全ての物性において良好であるが、実施例１４は、膜厚が薄すぎるため、耐摺動性（耐久性）に劣る。
【００５７】
【発明の効果】
本発明によれば、長時間にわたり安定した塗工性を有すると共に、撥水撥油性能の持続性に優れる硬化被膜を与えるコーティング組成物、および基材上に該組成物を用いて形成された上記特性を備えた硬化被膜を有する被コーティング材を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a coating composition and a material to be coated. More specifically, the present invention provides a coating composition having a stable coating property over a long period of time and a cured film having excellent durability of water and oil repellency, and a coating composition formed on a substrate using the composition. The present invention relates to a material to be coated having a cured film having the above characteristics.
[0002]
[Prior art]
It is well known that, when a compound containing a fluoroalkyl group is coated on the surface, the surface energy is remarkably reduced to exhibit water and oil repellency.
For example, it is disclosed that water- and oil-repellency is exhibited by applying a copolymer of a perfluoroalkyl group-containing polymerizable monomer to an object to be coated (for example, see Patent Document 1).
Further, for example, a copolymer of a fluorine-based monomer and a long-chain alkyl group-containing (meth) acrylate such as stearyl (meth) acrylate has better water and oil repellency than a polymer of a fluorine-based monomer alone. (For example, see Patent Document 2).
[0003]
Further, for example, a perfluoroalkyl group-containing α, β-unsaturated monomer (I) having 3 to 20 carbon atoms, a polysiloxane chain-containing α, β-unsaturated monomer (II), and a perfluoroalkyl group The isocyanate group (a) and the acryloyl or methacryloyl group are added to the hydroxyl group of a polymer obtained by reacting a hydroxyl group-containing α, β-unsaturated monomer (III) containing no polysiloxane chain and having no polysiloxane chain as an essential component. (B) a copolymer (A) having an acryloyl group or a methacryloyl group having a structure obtained by addition reaction of an isocyanate group (c) of a containing monomer, and any one of an acryloyl group, a methacryloyl group, and a vinyl group in a molecule; A coating agent containing a hydrocarbon monomer containing one or more groups has been disclosed (for example, see Patent Document 3). It is exemplified as a film forming agent which forms a film excellent in surface smoothness, friction reducing property, scratch resistance, water repellency, oil repellency and the like.
[0004]
It is also well known to introduce a crosslinkable functional group in order to maintain the water / oil repellency of the surface coated with a compound containing a fluoroalkyl group.
For example, it is disclosed that durability is improved by blending and copolymerizing polyoxyalkylene glycol di (meth) acrylate (for example, see Patent Document 4).
Further, for example, it is disclosed that a monomer forming an epoxy group-containing (meth) acrylate ester is blended and copolymerized to improve durability (for example, see Patent Document 5).
[0005]
Further, for example, it is disclosed that the durability is improved by blending and copolymerizing a polymerizable functional compound having a group that can be converted into an -NCO group at a temperature of 100 ° C. or higher (for example, Patent Reference 6).
Further, for example, it has been disclosed that by incorporating a compound having a blocked isocyanate group, the resistance to washing and dry cleaning is improved (for example, see Patent Document 7).
Further, for example, it is disclosed that a water / oil repellent having excellent durability can be provided by blending and copolymerizing an oxazoline residue-containing monomer (for example, see Patent Document 8).
[0006]
It is also well known to introduce a reactive group that chemically bonds to the substrate in order to improve the adhesion to the substrate.
For example, it is disclosed that a silane coupling agent is applied on a silicone resin film and then a film made of a fluoroalkyl acrylate polymer is formed (for example, see Patent Document 9).
Further, for example, it is disclosed that the adhesion to a substrate is improved by blending and copolymerizing a vinyl compound having an alkoxysilyl group or an acyloxysilyl group (for example, see Patent Document 10).
Further, for example, a copolymer containing a polymerizable silane compound as a part of a main component is disclosed (for example, see Patent Document 11).
Further, for example, it is disclosed that durability can be improved by having a group selected from the group consisting of a chlorine atom, a urethane group, an amide group, and an ester group as a group that adheres to an object to be processed (for example, see Patent Reference 12).
[0007]
When a coating composition containing a compound having a fluoroalkyl group and a crosslinkable functional group or a reactive group as an active ingredient is applied to develop water- and oil-repellency on the surface of the base material, coatability, design, From the viewpoints of workability, economy, stability and the like, the coating composition is required to be stable in terms of viscosity, turbidity and composition during coating. However, there has been a problem that it is difficult to obtain a coating composition that satisfies such characteristics and that maintains a high water-repellent and oil-repellent performance over a long period of time. The material to be coated with the coating composition is required to dry and cure promptly after coating, but the coating composition satisfies this property and exhibits stable coating properties for a long time. Was difficult to obtain.
[0008]
[Patent Document 1]
U.S. Pat. No. 3,102,103
[Patent Document 2]
JP-A-55-9619
[Patent Document 3]
JP-A-8-176504
[Patent Document 4]
JP-A-53-134787
[Patent Document 5]
JP-A-64-56711
[Patent Document 6]
JP-A-54-131579
[Patent Document 7]
JP-A-2-92985
[Patent Document 8]
JP-A-7-216346
[Patent Document 9]
JP-A-2-107380
[Patent Document 10]
JP-A-64-45411
[Patent Document 11]
JP-A-10-7986
[Patent Document 12]
JP-A-10-316719
[0009]
[Problems to be solved by the invention]
Under such circumstances, the present invention provides a coating composition which has a stable coating property over a long period of time, and provides a cured film having excellent durability of water and oil repellency, and the composition on a substrate. It is an object of the present invention to provide an inexpensive and simple material to be coated having a cured film having the above characteristics formed by using an object.
[0010]
[Means for Solving the Problems]
The present inventor has conducted extensive studies to achieve the above object, and as a result, a coating composition containing a copolymer having a specific plurality of structural units at a predetermined ratio at a certain concentration, and containing a crosslinking agent and a solvent. As a result, the present inventors have found that the object can be achieved, and have completed the present invention based on this finding.
[0011]
That is, the present invention
(1) (A) (a) 20 to 60% by weight of a structural unit derived from a (meth) acrylic acid ester having a fluoroalkyl group, and (b) structural unit 8 to a structural unit derived from a (meth) acrylic acid ester having an epoxy group. 36% by weight, (c) 7 to 24% by weight of a structural unit derived from a (meth) acrylate ester having a hydrolyzable silicon-containing group, and (d) derived from an ethylenically unsaturated compound having no crosslinkable reactive group. A copolymer composed of 12 to 65% by weight of a structural unit is contained in a concentration of 0.1 to 11% by weight as a solid content, and (B) a crosslinking agent for an epoxy group and (C) a solvent are contained. A coating composition,
(2) The coating composition according to the above (1), wherein the crosslinking agent for an epoxy group of the component (B) is a compound having at least two primary or secondary amino groups in one molecule.
(3) The solvent according to the above (1) or (2), wherein the solvent of the component (C) is at least one selected from ketones, aromatic hydrocarbons, ethers, esters and alcohols. Coating composition,
(4) A material to be coated, characterized by having a water-repellent cured film formed on the surface of the substrate using the coating composition according to the above (1), (2) or (3), and
(5) The coating material according to the above (4), wherein the water-repellent cured film has a thickness of 250 to 1500 nm.
Is provided.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
In the coating composition of the present invention, the copolymer used as the component (A) is (a) a structural unit derived from a (meth) acrylic ester having a fluoroalkyl group, and (b) a (meth) having an epoxy group. A constitutional unit derived from an acrylate ester, (c) a constitutional unit derived from a (meth) acrylate ester having a hydrolyzable silicon-containing group, and (d) a constitution derived from an ethylenically unsaturated compound having no crosslinkable reactive group. It is made up of units. Here, the (meth) acrylate refers to an acrylate or a methacrylate.
[0013]
In the copolymer, (a) the (meth) acrylate having a fluoroalkyl group of a monomer forming a structural unit may be, for example, a compound represented by the general formula (I):
Embedded image

[0014]
[Where R¹Is a hydrogen atom or a methyl group, A¹Is-(CH₂)_k-, -SO₂N (R²)-(CH₂)_k-, -CONR²− (CH₂)_k-CH₂CH (OCOR¹) CH₂-, -O-Ar-CH₂−, (R²Represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, Ar represents an aryl group, and k is an integer of 1 to 10. ), R_fRepresents a linear or branched fluoroalkyl group having 3 to 20 carbon atoms. ]
The compound represented by is mentioned.
[0015]
Specific examples of such monomers include, but are not limited to, the following.
CF₃(CF₂)₃(CH₂)₂OCOC (CH₃) = CH₂
CF₃(CF₂)₃CH₂OCOC (CH₃) = CH₂
CF₃(CF₂)₄CH₂OCOC (CH₃) = CH₂
CF₃(CF₂)₅CH₂OCOC (CH₃) = CH₂
CF₃(CF₂)₅(CH₂)₂OCOC (CH₃) = CH₂
CF₃(CF₂)₆(CH₂)₂OCOC (CH₃) = CH₂
CF₃(CF₂)₇(CH₂)₂OCOC (CH₃) = CH₂
CF₃(CF₂)₉(CH₂)₂OCOC (CH₃) = CH₂
CF₃(CF₂)₁₁(CH₂)₂OCOC (CH₃) = CH₂
(CF₃)₂CF (CF₂)₂(CH₂)₂OCOC (CH₃) = CH₂
(CF₃)₂CF (CF₂)₄(CH₂)₂OCOC (CH₃) = CH₂
(CF₃)₂CF (CF₂)₆(CH₂)₂OCOC (CH₃) = CH₂
(CF₃)₂CF (CF₂)₆(CH₂)₃OCOC (CH₃) = CH₂
CF₃(CF₂)₃(CH₂)₂OCOCH = CH₂
CF₃(CF₂)₃CH₂OCOCH = CH₂
CF₃(CF₂)₄CH₂OCOCH = CH₂
CF₃(CF₂)₅CH₂OCOCH = CH₂
CF₃(CF₂)₅(CH₂)₂OCOCH = CH₂
CF₃(CF₂)₆(CH₂)₂OCOCH = CH₂
CF₃(CF₂)₇(CH₂)₂OCOCH = CH₂
CF₃(CF₂)₉(CH₂)₂OCOCH = CH₂
CF₃(CF₂)₁₁(CH₂)₂OCOCH = CH₂
(CF₃)₂CF (CF₂)₂(CH₂)₂OCOCH = CH₂
(CF₃)₂CF (CF₂)₄(CH₂)₂OCOCH = CH₂
(CF₃)₂CF (CF₂)₆(CH₂)₂OCOCH = CH₂
(CF₃)₂CF (CF₂)₆(CH₂)₃OCOCH = CH₂
CF₃(CF₂)₇SO₂N (CH₃) (CH₂)₂OCOC (CH₃) = CH₂
CF₃(CF₂)₇SO₂N (C₂H₅) (CH₂)₂OCOC (CH₃) = CH₂
CF₃(CF₂)₇SO₂N (CH₃) (CH₂)₂OCOCH = CH₂
CF₃(CF₂)₇SO₂N (C₂H₅) (CH₂)₂OCOCH = CH₂
CF₃(CF₂)₄CONH (CH₂)₂OCOC (CH₃) = CH₂
CF₃(CF₂)₈CONH (CH₂)₂OCOC (CH₃) = CH₂
CF₃(CF₂)₇CONH (CH₂)₂OCOCH = CH₂
CF₃(CF₂)₄OC₆H₄-CH₂OCOC (CH₃) = CH₂
CF₃(CF₂)₈OC₆H₄-C₃H₆OCOC (CH₃) = CH₂
CF₃(CF₂)₇OC₆H₄-CH₂OCOCH = CH₂
In the above general formula (I), R_fIs preferably a perfluoroalkyl group, and the perfluoroalkyl group preferably has 6 to 12 carbon atoms. If the number of carbon atoms is less than 6, the water repellency is lowered, which is not preferable. In the present invention, the (meth) acrylate containing a fluoroalkyl group may be used singly, or two or more kinds may be used in combination. It is preferable to use (meth) acrylates having different numbers of fluoroalkyl groups.
[0016]
Further, (b) (meth) acrylic acid ester having an epoxy group of a monomer forming a structural unit includes, for example, a compound represented by the general formula (II):
Embedded image

[0017]
(Where R²And R³Represents a hydrogen atom or a methyl group, each of which may be the same or different;²Is an alkylene group having 1 to 10 carbon atoms which may have a direct bond or an ether bond;⁴Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. )
Can be used.
[0018]
In the general formula (II), A²Among them, the alkylene group having 1 to 10 carbon atoms may be linear or branched, and examples thereof include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, various butylene groups, and various Examples include a pentylene group and various hexylene groups. This alkylene group may have an ether bond. Also, R⁴Among them, the alkyl group having 1 to 10 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, Examples include various pentyl groups, various hexyl groups, various octyl groups, and the like.
[0019]
Examples of the compound represented by the general formula (II) include the following, but are not limited thereto.
Embedded image

[0020]
In the present invention, the (meth) acrylic ester having an epoxy group may be used alone or in combination of two or more.
[0021]
Next, (c) the (meth) acrylic acid ester having a hydrolyzable silicon-containing group of the monomer forming the structural unit includes, for example, the compound represented by the general formula (III)
Embedded image

[0022]
(Where R⁵Is a hydrogen atom or a methyl group, R⁶Is a hydrogen atom, a hydroxyl group or a hydrolyzable group, R⁷Is a non-hydrolyzable group, A³Is an alkylene group having 1 to 4 carbon atoms, n is an integer of 1 to 3,⁶When there are a plurality of⁶Each may be the same or different, and R⁷When there are a plurality of⁷They may be the same or different. )
Can be used.
[0023]
In the general formula (III), R⁶Examples of the hydrolyzable group include a lower alkoxyl group, an isocyanate group, a halogen atom such as a chlorine atom, an acetylacetonate group, and an alkoxycarbonyl group. Of these, a lower alkoxyl group is preferable. On the other hand, R⁷Examples of the non-hydrolysable group represented by include an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Also, A³The alkylene group having 1 to 4 carbon atoms represented by may be linear or branched, and examples thereof include a methylene group, an ethylene group, a methylethylene group, a trimethylene group, and a tetramethylene group. Can be mentioned.
[0024]
Examples of the compound represented by the general formula (III) include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and 3- (meth) acryloxypropyltripropoxysilane 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropylmethyldipropoxysilane, 4- (meth) acryloxybutylphenyldimethoxysilane 4- (meth) acryloxybutylphenyldiethoxysilane, 4- (meth) acryloxybutylphenyldipropoxysilane, 3- (meth) acryloxypropyldimethylmethoxysilane, 3- (meth) acryloxypropyldimethylethoxysilane , 3- (Meth) acryloxypropylphenylmethylmethoxysilane, 3- (meth) acryloxypropylphenylmethylethoxysilane, 3- (meth) acryloxypropyltrihydroxysilane, 3- (meth) acryloxypropylmethyldihydroxysilane, 4- ( (Meth) acryloxybutylphenyldihydroxysilane, 3- (meth) acryloxypropyldimethylhydroxysilane, 3- (meth) acryloxypropylphenylmethylhydroxysilane,
[0025]
Embedded image

[0026]
And the like, but are not limited to these.
In the present invention, the (meth) acrylic acid ester having a hydrolyzable silicon-containing group may be used alone or in combination of two or more.
Further, (d) the ethylenically unsaturated compound having no crosslinkable reactive group of the monomer forming the structural unit includes, for example, olefinic compounds, vinyl ethers and allyl ethers, vinyl esters and propenyl esters, (meth) acrylic acid Examples thereof include esters and vinyl aromatic compounds, but are not limited thereto.
[0027]
More specifically, examples of the olefin compound include ethylene, propylene, butylene, isoprene, chloroprene and the like.
Examples of vinyl ethers and allyl ethers include chains such as ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, and 4-methyl-1-pentyl vinyl ether. Examples thereof include cycloalkyl vinyl ethers such as alkyl vinyl ethers, cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, o-, m- and p-trivinyl ether, and aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether. it can.
[0028]
Examples of vinyl esters and propenyl esters include vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl pivalate, and vinyl caprate; and isopropenyl acetate and isopropionate. And propenyl esters such as propenyl.
Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid. Examples thereof include alkyl esters of (meth) acrylic acid having 1 to 18 carbon atoms, such as hexyl, octyl (meth) acrylate, and lauryl (meth) acrylate.
Examples of the vinyl aromatic compound include styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene and the like.
In addition, acrylonitrile and methacrylonitrile can also be used.
[0029]
In the present invention, one kind of the ethylenically unsaturated compound having no crosslinkable reactive group may be used, or two or more kinds thereof may be used in combination.
In the present invention, a copolymer of the component (A) is obtained by subjecting each of the above monomers to radical polymerization in the presence of a conventionally known radical polymerization initiator.
The content ratio of each structural unit in the copolymer thus obtained is as follows: (a) the structural unit is 20 to 60% by weight, (b) the structural unit is 8 to 36% by weight, and (c) the structural unit is It is selected in the range of 7 to 24% by weight and (d) the constituent unit of 12 to 65% by weight.
[0030]
(A) If the content of the constituent units is less than 20% by weight, the water repellency of the cured film is reduced, and if it exceeds 60% by weight, the durability of the cured film is reduced and the economical efficiency is poor. (B) If the content of the constituent units is less than 8% by weight, the durability of the cured film is poor, and if it exceeds 36% by weight, the stability of the composition is reduced. The preferred content of the structural unit (b) is 8 to 20% by weight. If the content of the structural unit (b) is within this range, excellent stability of the composition within the range of the preferred amount of the epoxy group crosslinking agent of the component (B) described later and the solid content of the coating composition. And shows the durability of the cured film. However, if it exceeds 20% by weight, the stability of the composition may be slightly reduced. In this case, the amount of the epoxy group crosslinking agent and the solid content in the composition are reduced. It is advantageous to reduce it. (C) If the content of the structural unit is less than 7% by weight or more than 24% by weight, the durability of the cured film is reduced. (D) If the content of the structural unit is less than 12% by weight, the stability of the composition is reduced, and the economical efficiency is poor. If it exceeds 65% by weight, the water repellency is reduced.
[0031]
In consideration of the stability of the composition, the water repellency, durability and economy of the cured film, the preferred content of each structural unit is (a) 30 to 55% by weight of the structural unit and (b) 8% of the structural unit. -20% by weight, (c) 10-20% by weight of the structural unit, and (d) 12-52% by weight of the structural unit.
In the coating composition of the present invention, the copolymer of the component (A) is contained at a concentration of 0.1 to 11% by weight as a solid content. If the concentration is less than 0.1% by weight, the coating on the substrate becomes insufficient, and the water repellency is reduced, so that the object of the present invention cannot be achieved. On the other hand, when the content exceeds 11% by weight, the stability of the composition decreases. A preferable concentration of the copolymer is 0.5 to 11% by weight as a solid content, and a range of 1 to 11% by weight is particularly preferable.
[0032]
In the coating composition of the present invention, the crosslinking agent for an epoxy group used as the component (B) is not particularly limited as long as it can crosslink an epoxy group, and is conventionally known as a curing agent for an epoxy group resin. It can be appropriately selected from known crosslinking agents. Examples of such a crosslinking agent for an epoxy group include various amines and acid anhydrides, and amines are preferable. As the amines, compounds having at least two primary or secondary amino groups in one molecule are preferable. Examples of such amines include aliphatic / alicyclic polyamines, polyamide amines, and aromatic polyamines, and among them, room temperature-curable aliphatic / alicyclic polyamines and polyamide amines are particularly preferable. It is.
[0033]
Examples of the aliphatic / alicyclic polyamine include ethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, The hydroxyl groups at both ends of 3,3,6-tris (aminomethyl) hexane, N-benzylethylenediamine, trimethylhexamethylenediamine, dimethylaminopropylamine, aminoethylethanolamine, diethylene glycol / bispropylenediamine, and polypropylene glycol were converted to amino groups. Diamine, mentin diamine, isophorone diamine, N-aminoethylpiperazine, 1,3-bis (aminomethyl) cyclohexane, Tanjiamin, Metsu isophoronediamine, bis - (4-amino-3-methylcyclohexyl) methane, and the like. As the polyamide amine, various commercially available products can be used.
Examples of the aromatic polyamine include m-phenylenediamine, 4-4'-diaminediphenylmethane, 4-4'-diaminodiphenylsulfone, and diaminodiphenyl ether.
[0034]
In the present invention, one kind of the epoxy group crosslinking agent (B) may be used alone, or two or more kinds may be used in combination.
The content of the crosslinking agent for an epoxy group is preferably in the range of 0.5 to 10 equivalents to the epoxy group in the structural unit derived from the component (B) in the component (A) copolymer, and It is preferably selected within a range of 5 parts by weight or less based on 100 parts by weight of the solvent as the component (C). If the amount of the crosslinking agent is less than 0.5 equivalents to the epoxy group, the curing reaction does not easily proceed, and the durability of the cured film may be insufficient. This causes a decrease in stability. On the other hand, if the amount exceeds 5 parts by weight with respect to 100 parts by weight of the solvent, the transparency of the cured film is undesirably reduced.
[0035]
In the coating composition of the present invention, if desired, as a crosslinking accelerator, a known compound conventionally known as a curing accelerator for an epoxy resin, for example, tertiary amines, imidazoles, organometallic compounds, and quaternary compounds One or more of ammonium compounds, organic phosphorus compounds, boron compounds, metal halides and the like can be appropriately selected and contained.
[0036]
In the coating composition of the present invention, as the solvent of the component (C), ketones, aromatic hydrocarbons, ethers, esters and alcohols from the viewpoint of the solubility of the copolymer as the component (A). At least one selected from the group is used. Here, ketones include, for example, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like, and aromatic hydrocarbons include, for example, benzene, toluene, xylene, ethylbenzene, diethylbenzene, pseudocumene, and the like. . Examples of ethers include, for example, tetrahydrofuran, dioxane, and cellosolve solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether.Examples of esters include: Examples include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, and the like. Examples of alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, cyclohexanol, benzyl alcohol and the like. These solvents may be used alone or as a mixture of two or more.
[0037]
In the coating composition of the present invention, as long as the object of the present invention is not impaired, if necessary, various additives, for example, a leveling agent, a coupling agent, a thickener, an anti-sagging agent, a filler, a plasticizer, It may contain an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antifreezing agent, and the like.
ADVANTAGE OF THE INVENTION The coating composition of this invention has stable coating property over a long period of time, and can form the cured film excellent in persistence of water-repellent and oil-repellent performance.
[0038]
Next, the material to be coated of the present invention has a water-repellent cured film formed on the surface of the substrate by using the above-described coating composition of the present invention.
Examples of the material of the substrate include metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, fabric, paper, combinations thereof, laminates thereof, and painted bodies thereof. The member to which the composition of the present invention can be applied can be applied to any member requiring surface drip-proof, rust-proof, water-repellent, water-based dirt adhesion-preventing properties, running-water washing properties, icing and snow-preventing properties, and the like.
[0039]
Specifically, architectural exteriors such as exterior walls and roofs; window frames; exteriors and coatings of vehicles such as automobiles, railway vehicles, aircraft, ships, bicycles, and motorcycles; soundproof walls, greenhouses, insulators, and vehicle covers; Tent materials, reflectors, shutters, screen doors, covers for solar cells, covers for heat collectors such as solar water heaters, street lights, pavements, outdoor lighting, artificial waterfalls, stones for artificial fountains, tiles, bridges, greenhouses, exterior wall materials, walls Seals, guardrails, verandas, vending machines, air conditioner outdoor units, outdoor benches, various display devices, shutters, toll booths, toll booths, toll boxes, dust proof covers and painting, painting of machinery and articles, exterior of advertising towers, etc. And coatings, structural members, and films, patches, and the like that can be adhered to these articles.
[0040]
When the cured film coated with the coating composition of the present invention requires adhesion, it is preferable that the surface of the base material is coated with a reactive group that binds to a hydrolyzable silicon-containing group or an epoxy group.
In order to further improve the adhesion, the substrate is coated with the coating composition of the present invention, or before coating by spraying, the substrate is coated with at least one intermediate layer or subjected to corona discharge treatment. May be subjected to a pretreatment.
[0041]
The method for applying the coating composition of the present invention to the surface of a substrate is not particularly limited, and depending on the situation, a conventionally known method, for example, a spin coating method, a dip coating method, a flow coating method, a spray coating method, or a roll It can be appropriately selected from a coating method, a screen printing method, a bar coater method, a brush coating, a sponge coating and the like.
In this way, the coating film formed on the surface of the base material can sufficiently promote curing even at room temperature, further improve the adhesion to the base material, or improve the flatness of the surface by 40 to 150. You may hold | maintain at the temperature of 5 degreeC for about 5 minutes to 1 week, and may make it harden.
The thickness of the water-repellent cured film thus formed is preferably in the range of 250 to 1500 nm. If the thickness is less than 250 nm, the durability of the cured film may be insufficient. If the thickness exceeds 1500 nm, the transparency may be reduced, and it is not preferable in terms of economy. A more preferred thickness of this cured coating is in the range of 300-1000 nm.
[0042]
【Example】
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The pot life of the coating composition and the physical properties of the coated test plate were determined according to the following methods.
(1) Pot life of coating composition
The coating composition was evaluated by measuring the specific viscosity with an Ostwald viscometer. The specific viscosity at 25 ° C. for 10 hours was compared with the specific viscosity at 25 ° C. for 30 minutes to determine the rate of increase. As a guide, if the rate of increase is less than 25%, it passes, and if it is 25% or more, it fails.
(2) Physical properties of coated test plate
(B) Film thickness
The film thickness of the coated test plate was measured by observing the cross section of the coated test plate with a scanning electron microscope (“S-4100” manufactured by Hitachi, Ltd.).
(B) Water repellency
Using a contact angle meter (“CA-X150 type” manufactured by Kyowa Interface Science Co., Ltd.), about 1 μL of water droplets were placed on the coated test plate, and the water contact angle was measured. As a guide, if the water contact angle is 110 ° or more, it passes, and if it is less than 110 °, it fails.
(C) Transparency
The haze value of the coated test plate was measured according to JIS K7105. As a guide, if the haze value is less than 2%, the test is acceptable and if it is 2% or more, the test is rejected.
(D) Sliding resistance
Using a sliding tester ("Washability Tester" manufactured by Toyo Seiki Seisaku-Sho, Ltd.), the coated test plate was tested with Bencott ("M-3" manufactured by Asahi Kasei Kogyo Co., Ltd.) with a load of 122.6 mN / cm.², And slid 1000 times with 35 strokes per minute. The water contact angle after 1000 slides was measured. As a guide, if the water contact angle is 100 ° or more, it passes, and if it is less than 100 °, it fails.
[0043]
Production Example 1
17. 340 parts by weight of methyl isobutyl ketone (manufactured by Wako Pure Chemical Industries), 26.3 parts by weight of methyl methacrylate (MMA, manufactured by Wako Pure Chemical Industries), and glycidyl methacrylate (GMA; manufactured by Wako Pure Chemical Industries) 7 parts by weight, 13.0 parts by weight of 3-methacryloxypropyltrimethoxysilane (MPTMS, "LS-3380" manufactured by Shin-Etsu Chemical Co., Ltd.), 2- (perfluorooctyl) ethyl methacrylate (FMA, manufactured by Daikin Fine Chemical Laboratory) After adding 42.0 parts by weight of "M-1820") and stirring well, 2.1 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 96 parts by weight of methyl isobutyl ketone. The mixture was heated and stirred at 56 ° C. for 1 hour to prepare a copolymer dispersion. After cooling the prepared copolymer dispersion to room temperature, it is poured into 1230 parts by weight of methanol (manufactured by Wako Pure Chemical Industries, Ltd.) to precipitate the copolymer, and the obtained precipitate is dried under reduced pressure to be copolymerized. Polymer (I) was obtained.
[0044]
Production Example 2
In Production Example 1, a copolymer (II) was obtained in the same manner as in Production Example 1, except that the proportions of MMA, GMA, MPTMS and FMA were changed as shown in Table 1.
Comparative Production Examples 1 to 5
In Production Example 1, copolymers (III) to (VII) were obtained in the same manner as in Production Example 1, except that the use ratios of MMA, GMA, MPTMS and FMA were changed as shown in Table 1.
[0045]
[Table 1]

[0046]
Example 1
After adding 9.9 parts by weight of the copolymer (I) obtained in Production Example 1 to 87.6 parts by weight of methyl isobutyl ketone (MIBK) and stirring the mixture, the mixture was further stirred with a diamine (“Jeffamine D- manufactured by San Techno Chemical Co., Ltd.”). 230 ", 2.5 parts by weight of an active hydrogen equivalent (about 60 g / eq) and stirred for 15 minutes to prepare a water-repellent coating composition A1.
Examples 2 to 4
Example 1 was repeated in the same manner as in Example 1 except that the copolymers shown in Table 2 were used and the proportions of MIBK, the copolymer and the diamine were changed as shown in Table 2. Thus, water-repellent coating compositions A2 to A4 were prepared.
Comparative Examples 1 to 6
Example 1 was repeated in the same manner as in Example 1 except that the copolymers shown in Table 2 were used and the proportions of MIBK, the copolymer and the diamine were changed as shown in Table 2. Thus, water-repellent coating compositions A5 to A10 were prepared.
[0047]
[Table 2]

[0048]
Example 5
5.9 parts by weight of the copolymer (I) obtained in Production Example 1 was added to 92.6 parts by weight of 1,3-bis (trifluoromethyl) benzene, and the mixture was stirred, and then further mixed with a diamine (manufactured by San Techno Chemical Co., Ltd.). 1.5 parts by weight of “Jeffamine D-230” and an active hydrogen equivalent of about 60 g / eq) were added thereto, followed by stirring for 15 minutes to prepare a water-repellent coating composition A11.
[0049]
Example 6
A polyethylene terephthalate film ("Lumirror U94" manufactured by Du Pont-Toray Co., Ltd., film thickness of 100 m, hereinafter referred to as a PET film) cut into 90 x 90 mm was subjected to corona treatment ("AGF-010" manufactured by Kasuga Electric Co., 0.1 kW). After the application, 2 mL of the water-repellent coating composition A1 obtained in Example 1 was dropped, spin-coated with a spin coater (“ASS301” manufactured by Able Co., Ltd.) at 1500 rpm for 20 seconds, and then dried at 120 ° C. for 12 hours. Thus, a coated test plate of the coating composition A1 was obtained.
Table 3 shows the pot life of the coating composition and the physical properties of the coated test plate.
[0050]
Examples 7 to 10 and Comparative Examples 7 to 12
In Example 6, a coated test plate was prepared in the same manner as in Example 6, except that the type shown in Table 3 was used as the water-repellent coating composition.
Table 3 shows the pot life of each coating composition and the physical properties of each coated test plate.
[0051]
[Table 3]

[0052]
As is clear from Table 3, Examples 1 to 3 have good pot life and all physical properties of the test plate. In Example 4, the pot life was insufficient due to the large amount of the crosslinking agent relative to the copolymer, and in Example 5, the transparency of the test plate was poor due to the effect of the solvent used. On the other hand, Comparative Examples 7 to 11 are inferior in water repellency or sliding resistance (durability), which are important physical properties, and Comparative Example 12 is large in the amount of the copolymer in the coating composition. Is short.
[0053]
Example 11
The water-repellent coating composition A1 obtained in Example 1 was coated on a PET film with a microgravure coater (oblique line type gravure, gravure mesh # 70 manufactured by Yasui Seiki Co., Ltd., coating speed 10 m / min), and then coated at 120 ° C. for 12 hours. After drying for a time, a coated test plate of the coating composition A1 was obtained.
Table 4 shows the film thickness and physical properties of the coated test plate.
[0054]
Examples 12 to 14
In Example 11, a coated test plate of the coating composition A1 was produced in the same manner as in Example 11, except that the gravure mesh of the microgravure coater and the coating speed were changed to the gravure mesh and the coating speed shown in Table 4. .
Table 4 shows the film thickness and physical properties of each coated test plate.
[0055]
[Table 4]

[0056]
As can be seen from Table 4, Examples 11 to 13 are good in all physical properties of the coated test plate, but Example 14 is inferior in sliding resistance (durability) because the film thickness is too thin. .
[0057]
【The invention's effect】
According to the present invention, a coating composition that has a stable coating property for a long time and provides a cured film having excellent durability of water and oil repellency, and a coating composition formed on a substrate using the composition A coating material having a cured film having the above characteristics can be provided.

Claims (5)

(A) (a) 20 to 60% by weight of a structural unit derived from a (meth) acrylate having a fluoroalkyl group, and (b) 8-36% by weight of a structural unit derived from a (meth) acrylate having an epoxy group. (C) 7 to 24% by weight of a structural unit derived from a (meth) acrylate ester having a hydrolyzable silicon-containing group, and (d) a structural unit 12 derived from an ethylenically unsaturated compound having no crosslinkable reactive group. And a copolymer composed of (B) a crosslinking agent for an epoxy group, and (C) a solvent. Coating composition. The coating composition according to claim 1, wherein the epoxy group crosslinking agent (B) is a compound having at least two primary or secondary amino groups in one molecule. The coating composition according to claim 1 or 2, wherein the solvent as the component (C) is at least one selected from ketones, aromatic hydrocarbons, ethers, esters, and alcohols. A material to be coated, comprising a water-repellent cured film formed using the coating composition according to claim 1 on a surface of a substrate. The coated material according to claim 4, wherein the water-repellent cured coating has a thickness of 250 to 1500 nm.