JP2004210975A - Coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition most suitable for various types of outdoor coating which has excellent contamination-controlling performance, especially an excellent capability of decontaminating oil dirt, permits easy wiping up of any scribble and is also excellent in weather resistance and adhesion. <P>SOLUTION: The composition comprises (A) one or more of fluoroolefin resins having functional groups and nonfluorinated acrylic resins having functional groups, (B) one or more silicon-containing fluorine compounds selected from (B1) silicon-containing fluorinated low molecular compounds of the formula: RfSi(OR<SP>1</SP>)<SB>n</SB>(R<SP>2</SP>)<SB>3-n</SB>(wherein Rf is a low molecular weight fluorine-containing group) and (B2) silicon-containing fluorinated compounds of the formula: YSi(OR<SP>1</SP>)<SB>n</SB>(R<SP>2</SP>)<SB>3-n</SB>(wherein Y is a high molecular weight fluorinated radical) and, if necessary, (C) a curing agent. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００９０】
［式中、Ｒ^１６は水素原子またはヒドロキシアルキル基を示す。］
【００９１】
【化２】

【００９２】
［式中、Ｒ^１６は前記に同じ。］
【００９３】
【化３】

【００９４】
［式中、Ｚは水素原子またはメチル基を示し、ｍは２〜８の整数、ｐは２〜１８の整数、ｑは０〜７の整数を示す。］
【００９５】
【化４】

【００９６】
［式中、Ｚは前記に同じ、Ｔ_１およびＴ_２は、同一もしくは異なって、炭素数１〜２０の２価の炭化水素基を示す。ｓおよびｖはそれぞれ０〜１０の整数を示す。ただし、ｓとｖの和は、１〜１０である。］
【００９７】
式（８）および（９）における、ヒドロキシアルキル基は、アルキル部分の炭素数が１〜６のヒドロキシアルキル基である。具体的には、−Ｃ_２Ｈ_４ＯＨ、−Ｃ_３Ｈ_６ＯＨ、−Ｃ_４Ｈ_８ＯＨなどをあげることができる。
【００９８】
式（１１）における炭素数１〜２０の２価の炭化水素基としては、たとえば
【００９９】
【化５】

【０１００】
などをあげることができる。
【０１０１】
式（８）の単量体成分としては、たとえば
ＣＨ_２＝ＣＨＯＨ、
ＣＨ_２＝ＣＨＯ（ＣＨ_２）_４ＯＨ
などをあげることができる。
【０１０２】
式（９）の単量体成分としては、たとえば
【０１０３】
【化６】

【０１０４】
などをあげることができる。
【０１０５】
式（１０）の単量体成分としては、たとえば
【０１０６】
【化７】

【０１０７】
などをあげることができる。
【０１０８】
式（１１）の単量体成分としては、たとえば
【０１０９】
【化８】

【０１１０】
などをあげることができる。
【０１１１】
さらに、前記以外にも前記式（８）〜（１１）で表わされる水酸基含有不飽和単量体とε−カプロラクトン、γ−バレロラクトンなどのラクトン類との付加物などが使用できる。
【０１１２】
その他の重合性不飽和単量体（ｂ）としては、下記（ｂ−１）〜（ｂ−９）のものをあげることができる。
【０１１３】
（ｂ−１）オレフィン系化合物：たとえばエチレン、プロピレン、ブチレン、イソプレン、クロロプレンなど。
【０１１４】
（ｂ−２）ビニルエーテルおよびアリルエーテル：たと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など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など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類など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などのアラルキルビニルエーテル類など。
【０１１５】
（ｂ−３）ビニルエステルおよびプロペニルエステル；たとえば酢酸ビニル、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、ピバリック酸ビニル、カプリン酸ビニルなどのビニルエステル類および酢酸イソプロペニル、プロピオン酸イソプロペニルなどのプロペニルエステルなど。
【０１１６】
（ｂ−４）：アクリル酸またはメタクリル酸のエステル：たとえばアクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸イソプロピル、アクリル酸ブチル、アクリル酸ヘキシル、アクリル酸オクチル、アクリル酸ラウリル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸イソプロピル、メタクリル酸ブチル、メタクリル酸ヘキシル、メタクリル酸オクチル、メタクリル酸ラウリルなどのアクリル酸またはメタクリル酸の炭素数１〜１８のアルキルエステル；アクリル酸メトキシブチル、メタクリル酸メトキシブチル、アクリル酸メトキシエチル、メタクリル酸メトキシエチル、アクリル酸エトキシブチル、メタクリル酸エトキシブチルなどのアクリル酸またはメタクリル酸の炭素数２〜１８のアルコキシアルキルエステル類など。
【０１１７】
（ｂ−５）ビニル芳香族化合物：たとえばスチレン、α−メチルスチレン、ビニルトルエン、ｐ−クロルスチレンなど。
【０１１８】
（ｂ−６）その他：アクリロニトリル、メタクリルロニトリルなど。
【０１１９】
（ｂ−７）カルボキシル基含有単量体：式（１２）：
【０１２０】
【化９】

【０１２１】
（式中、Ｒ^１７、Ｒ^１８およびＲ^１９は同じかまたは異なり、いずれも水素原子、アルキル基、フェニル基、カルボキシル基またはエステル基であり、ｎは０または１である）または式（１３）：
【０１２２】
【化１０】

【０１２３】
（式中、Ｒ^２０およびＲ^２１は同じかまたは異なり、いずれも飽和または不飽和の直鎖または環状アルキル基、ｎは０または１、ｍは０または１である）で表わされるカルボキシル基含有ビニル単量体があげられる。具体例としては、たとえばアクリル酸、メタクリル酸、ビニル酢酸、クロトン酸、桂皮酸、３−アリルオキシプロピオン酸、イタコン酸、イタコン酸モノエステル、マレイン酸、マレイン酸モノエステル、マレイン酸無水物、フマル酸、フマル酸モノエステル、フタル酸ビニル、ピロメリット酸ビニルなどがあげられる。
【０１２４】
（ｂ−８）エポキシ基含有単量体：
【０１２５】
【化１１】

【０１２６】
（ｂ−９）アミノ含有単量体：
【０１２７】
【化１２】

【０１２８】
前記アクリルポリオール樹脂としては、水酸基、カルボキシル基、エポキシ基、アミノ基を有していてもよいが、水酸基が特に好ましい。
【０１２９】
前記アクリルポリオール樹脂の水酸基価としては０〜２００（ｍｇＫＯＨ／ｇ）であり、０〜１００（ｍｇＫＯＨ／ｇ）であることが好ましい。前記水酸基価が少なくなると硬化不良になりやすい傾向があり、２００（ｍｇＫＯＨ／ｇ）を超えると塗膜の可撓性に問題が生じる傾向がある。
【０１３０】
前記アクリルポリオール樹脂としては、たとえば三菱レーヨン（株）製ダイヤナール、大日本インキ化学工業（株）製アクリディック、日立化成工業（株）製ヒタロイド、三井東圧化学（株）製オレスターなどの市販品を用いることができる。
【０１３１】
アクリルシリコン樹脂としては、たとえばつぎにあげるようなアクリルシリコンモノマーを式（８）〜（１１）の化合物および／またはその他重合性不飽和単量体（ｂ）と共に重合したものであればよい。
【０１３２】
該アクリルシリコンモノマーは、１分子中に、少なくとも１個のシラン基と、ラジカル重合性不飽和基とを有する化合物である。ラジカル重合性不飽和基としては、たとえば
【０１３３】
【化１３】

【０１３４】
［式中、Ｒ^２２は水素原子またはメチル基である］
などをあげることができる。
【０１３５】
ラジカル重合性不飽和基が
【０１３６】
【化１４】

【０１３７】
のシラン基含有重合性不飽和単量体としては、たとえば下記式（１４）で表わされる化合物をあげることができる：
【０１３８】
【化１５】

【０１３９】
［式中、Ｒ^２２は上記と同じ、Ｒ^２３は炭素数１〜２０の炭化水素基を示し、Ｗは同一または異なって、水素原子、水酸基、加水分解性基、炭素数１〜８のアルキル基、アリール基またはアラルキル基を示す。ただし、Ｗの少なくとも１個は加水分解性基である］。
【０１４０】
式（１４）で表わされる化合物の具体例としては、たとえばγ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルトリプロポキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジプロポキシシラン、γ−（メタ）アクリロキシブチルフェニルジメトキシシラン、γ−（メタ）アクリロキシブチルフェニルジエトキシシラン、γ−（メタ）アクリロキシブチルフェニルジプロポキシシラン、γ−（メタ）アクリロキシプロピルジメチルメトキシシラン、γ−（メタ）アクリロキシプロピルジメチルエトキシシラン、γ−（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、γ−（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、γ−（メタ）アクリロキシプロピルトリシラノール、γ−（メタ）アクリロキシプロピルメチルジヒドロキシシラン、γ−（メタ）アクリロキシブチルフェニルジヒドロキシシラン、γ−（メタ）アクリロキシプロピルジメチルヒドロキシシラン、γ−（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などがあげられる。
【０１４１】
前記アクリルシリコン樹脂はさらに水酸基、エポキシ基を有してもよい。
【０１４２】
前記アクリルシリコン樹脂としては、たとえば鐘淵化学工業（株）製ゼムラック、三洋化成工業（株）製クリヤマーなどの市販品を用いることができる。
【０１４３】
樹脂（Ａ）としては、耐候性により優れる点から官能基含有フルオロオレフィン樹脂（Ａ１）の方が好ましい。
【０１４４】
本発明の塗料組成物は、かかる樹脂（Ａ）とケイ素含有含フッ素化合物（Ｂ）とを本質的に含むものであるが、要すれば硬化剤（Ｃ）を配合してもよい。
【０１４５】
樹脂（Ａ）１００重量部に対するケイ素含有含フッ素化合物（Ｂ）の配合量は、１０，０００〜０．５重量部であり、好ましい下限は１重量部、さらには５重量部である。好ましい上限は９，０００重量部、さらには８，０００重量部である。ケイ素含有含フッ素化合物（Ｂ）が多くなりすぎると成膜性がわるくなり、また耐候性も低下し、少なすぎると撥水撥油性がわるくなる傾向にある。硬化剤（Ｃ）の配合量は、硬化剤の種類によって適宜選択すればよいが、通常、樹脂（Ａ）とケイ素含有含フッ素化合物（Ｂ）の合計１００重量部に対して０〜２００重量部である。好ましい上限は１００重量部、さらには８０重量部であり、好ましい下限は５重量部、さらには１０重量部である。
【０１４６】
樹脂（Ａ）が前記加水分解性シリケート基を有する場合は、硬化剤（Ｃ）を特に配合しなくても、ケイ素含有含フッ素化合物（Ｂ）中の加水分解性アルキルシリケート残基との充分な効果反応が達成できる。
【０１４７】
樹脂（Ａ）が有する官能基がたとえば水酸基である場合は、硬化剤（Ｃ）を配合することが好ましい。
【０１４８】
好ましい硬化剤（Ｃ）としては、イソシアネート化合物および／またはＳｉ（ＯＲ^９）_４（Ｒ^９は炭素数１〜１０の非フッ素アルキル基）、Ｒ^１０Ｓｉ（ＯＲ^１１）_３（Ｒ^１０およびＲ^１１は同じかまたは異なり、炭素数１〜１０の非フッ素アルキル基）、これらの単独縮合オリゴマーおよびこれらの共縮合コオリゴマーよりなる群から選ばれた少なくとも１種があげられる。
【０１４９】
イソシアネート化合物にはブロックイソシアネート化合物も含まれ、具体例としては、たとえば２，４−トリレンジイソシアネート、ジフェニルメタン−４，４´−ジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、リジンメチルエステルジイソシアネート、メチルシクロヘキシルジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ｎ−ペンタン−１，４−ジイソシアネート、これらの三量体、これらのアダクト体やビュウレット体、これらの重合体で２個以上のイソシアネート基を有するもの、さらにブロック化されたイソシアネート類などがあげられるが、これらに限定されるものではない。
【０１５０】
また、加水分解性アルキルシリケート残基を有するイソシアネート化合物も好ましく使用できる。
【０１５１】
加水分解性アルキルシリケート残基としては、−ＳｉＲ^６ _３−ｍ（ＯＲ^７）_ｍ（式中、Ｒ^６は炭素数１〜１８のフッ素原子を含んでいてもよい非加水分解性の炭化水素基；Ｒ^７は炭素数１〜１８の炭化水素基；ｍは１〜３の整数）で示されるケイ素含有官能基が好ましい。かかるケイ素含有官能基については、樹脂（Ａ）において説明したものが好ましくあげられる。
【０１５２】
加水分解性アルキルシリケート残基を有するイソシアネート化合物の具体例としては、たとえばＯＣＮＣ_３Ｈ_６Ｓｉ（ＯＣＨ_３）_３、ＯＣＮＣ_３Ｈ_６Ｓｉ（ＯＣ_２Ｈ_５）_３、ＯＣＮＣ_３Ｈ_６Ｓｉ（ＯＣＯＣＨ_３）_３、ＯＣＮＣ_３Ｈ_６Ｓｉ（ＣＨ_３）（ＯＣＨ_３）_２などがあげられる。
【０１５３】
イソシアネート化合物と樹脂（Ａ）との混合割合はＮＣＯ／ＯＨ（モル比）で０．５〜５．０が好ましく、さらに０．８〜１．２がより好ましい。また、イソシアネートが湿気硬化タイプの場合は１．１〜１．５が好ましい。
【０１５４】
硬化剤（Ｃ）としては、イソシアネート化合物に代えて、または加えて、Ｓｉ（ＯＲ^９）_４（Ｒ^９は炭素数１〜１０の非フッ素アルキル基）、Ｒ^１０Ｓｉ（ＯＲ^１１）_３（Ｒ^１０およびＲ^１１は同じかまたは異なり、炭素数１〜１０の非フッ素アルキル基）、これらの単独縮合オリゴマーおよびこれらの共縮合コオリゴマーよりなる群から選ばれた少なくとも１種を使用することもできる。
【０１５５】
これらの４官能または３官能の非フッ素アルキルシリケートとしては、たとえば米国特許第５，６３５，５７２号明細書などに記載されたものが使用できる。
【０１５６】
具体的には、たとえばテトラアルコキシシランまたはこの縮合物、アルキルトリアルコキシシランまたはこの縮合物、ポリシルセスキオキサン、コロイダルシリカなどがあげられる。
【０１５７】
テトラアルコキシシランとしては、テトラメトキシシラン、テトラエトキシシラン、テトラブトキシシランまたはこれらの縮合物などが例示され、市販品としては、三菱化学（株）製のＭＳ５１、ＭＳ５６、ＭＳ５７など、コルコート社製のエチルシリケート２８、エチルシリケート４０、エチルシリケート４８などが使用できる。
【０１５８】
ポリシルセスキオキサンとしては、ポリフェニルシルセスキオキサン、ポリメチルシルセスキオキサン、ポリハイドロジェンシルセスキオキサンなどがあげられる。
【０１５９】
コロイダルシリカとしてはたとえば日産化学（株）製のスノーテックスなどが使用できる。
【０１６０】
これらのうち架橋密度が高く強固な被膜が形成できる点から、テトラアルコキシシランの縮合物が好ましい。
【０１６１】
かかるシリケート系硬化剤の配合量は、硬化剤の種類によって適宜選択すればよいが、通常、樹脂（Ａ）とケイ素含有含フッ素化合物（Ｂ）の合計１００重量部に対して０〜１００重量部である。好ましい上限は５０重量部であり、好ましい下限は１０重量部である。
【０１６２】
本発明においては、硬化剤に加えて硬化触媒を添加してもよい。
【０１６３】
硬化触媒としては、たとえば有機スズ化合物、有機酸性リン酸エステル、有機チタネート化合物、酸性リン酸エステルとアミンとの反応物、飽和または不飽和の多価カルボン酸またはその酸無水物、有機スルホン酸、アミン系化合物、アルミニウムキレート化合物、チタニウムキレート化合物、ジルコニウムキレート化合物などがあげられる。
【０１６４】
前記有機スズ化合物の具体例としては、ジブチルスズジラウレート、ジブチルスズマレエート、ジオクチルスズマレエート、ジブチルスズジアセテートなどがあげられる。
【０１６５】
前記有機酸性リン酸エステルの具体例としては、
【０１６６】
【化１６】

【０１６７】
などがあげられる。
【０１６８】
前記有機チタネート化合物としては、たとえばテトラブチルチタネート、テトライソプロピルチタネート、トリエタノールアミンチタネートなどのチタン酸エステルがあげられる。
【０１６９】
さらに前記アミン系化合物の具体例としては、たとえばブチルアミン、オクチルアミン、ジブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジエチレントリアミン、トリエチレンテトラミン、オレイルアミン、シクロヘキシルアミン、ベンジルアミン、ジエチルアミノプロピルアミン、キシリレンジアミン、トリエチレンジアミン、グアニジン、ジフェニルグアニジン、２，４，６−トリス（ジメチルアミノメチル）フェノール、モルホリン、Ｎ−メチルモルホリン、１，８−ジアザビシクロ（５．４．０）ウンデセン−７（ＤＢＵ）などのアミン系化合物、さらにはそれらのカルボン酸などの塩、過剰のポリアミンと多塩基酸よりえられる低分子量ポリアミド樹脂、過剰のポリアミンとエポキシ化合物の反応生成物などがあげられる。
【０１７０】
前記キレート化合物の具体例としてはアルミニウムトリス（エチルアセトアセテート）、アルミニウムトリス（アセチルアセトナート）、ジルコニウムテトラキス（アセチルアセトナート）、ジイソプロポキシ・ビス（エチルアセトアセテート）チタネートなどがあげられる。
【０１７１】
硬化触媒は１種を用いてもよく、２種以上を併用してもよい。好ましい硬化触媒としては、有機スズ化合物、アルミニウムキレート化合物があげられる。硬化触媒の配合量は、樹脂（Ａ）とケイ素含有含フッ素化合物（Ｂ）と硬化剤（Ｃ）の合計１００重量部に対して０〜１０重量部、好ましくは０．００１〜５重量部である。
【０１７２】
本発明においては、前記塗料組成物に有機溶剤を配合することができる。
【０１７３】
有機溶剤としては、たとえばキシレン、トルエン、ソルベッソ１００、ソルベッソ１５０、ヘキサンなどの炭化水素系溶剤、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸エチレングリコールモノメチルエーテル、酢酸エチレングリコールモノエチルエーテル、酢酸エチレングリコールモノブチルエーテル、酢酸ジエチレングリコールモノメチルエーテル、酢酸ジエチレングリコールモノエチルエーテル、酢酸ジエチレングリコールモノブチルエーテル、酢酸エチレングリコール、酢酸ジエチレングリコールなどのエステル系溶剤、ジメチルエーテル、ジエチルエーテル、ジブチルエーテル、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ブチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、テトラヒドロフランなどのエーテル系溶剤、メチルエチルケトン、メチルイソブチルケトン、アセトンなどのケトン系溶剤、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルアセトアミド、アセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ−メチルホルムアミドなどのアミド系溶剤、ジメチルスルホキシドなどのスルホン酸エステル系溶剤、メタノール、エタノール、イソプロパノール、ブタノール、エチレングリコール、ジエチレングリコール、ポリエチレングリコール（重合度３〜１００）、ＣＦ_３ＣＨ_２ＯＨ、Ｆ（ＣＦ_２）_２ＣＨ_２ＯＨ、（ＣＦ_３）_２ＣＨＯＨ、Ｆ（ＣＦ_２）_３ＣＨ_２ＯＨ、Ｆ（ＣＦ_２）_４Ｃ_２Ｈ_５ＯＨ、Ｈ（ＣＦ_２）_２ＣＨ_２ＯＨ、Ｈ（ＣＦ_２）_３ＣＨ_２ＯＨ、Ｈ（ＣＦ_２）_４ＣＨ_２ＯＨなどのアルコール系溶剤などがあげられるが、相溶性、塗膜外観、貯蔵安定性の点から低級アルコール、低級フッ素アルコールなどのアルコール系溶剤が好ましい。
【０１７４】
前記樹脂（Ａ）とアルコール系溶剤との配合割合については、樹脂（Ａ）１００重量部に対してアルコールが１〜５０重量部であり、硬化性、塗膜外観の点から１〜２５重量部であることがさらに好ましい。
【０１７５】
また、硬化剤が常温硬化型のイソシアネートなどのようにアルコールと反応性の高い場合には、さらにアルコールは１〜１５重量部であるのが好ましく、アルコールの種類も２級または３級アルコールが好ましい。
【０１７６】
本発明の塗料組成物は、溶剤溶解性に優れ、形成された塗膜は高度の耐候性を有し、防汚染付着性、特に油性汚れの除去（落書きの除去）性や耐薬品性、光学的性質、機械的性質、基材への密着性、耐熱黄変性などに優れたものである。また、該組成物は、通常の硬化用組成物と同じく建材、内装材などの屋内用あるいは建材、自動車、航空機、船舶、電車などの屋外用の塗料として金属、コンクリート、プラスチックなどに直接、あるいはウォッシュプライマー、錆止め塗料、エポキシ樹脂、アクリル樹脂塗料、ポリエステル樹脂塗料などの下塗り塗料の上に重ねて塗装することができる。さらにシーリング剤やフィルム形成剤としても使用できる。
【０１７７】
また塗料組成は、クリヤー、ソリッド、充填剤（フィラー）配合など種々の形態を採用できる。
【０１７８】
塗装方法については、スプレー、ハケ、ローラ、カーテンフロー、ロール、ディップなど種々の方法が用いられる。
【０１７９】
本発明の塗料組成物には、たとえば顔料、顔料分散剤、増粘剤、レベリング剤、消泡剤、造膜助剤、紫外線吸収剤、ＨＡＬＳ、艶消し剤、フィラー、コロイダルシリカ、防カビ剤、シランカップリング剤、皮張り防止剤、酸化防止剤、難燃剤、垂れ防止剤、帯電防止剤、防錆剤、水溶性樹脂（ポリビニルアルコール、ポリエチレンオキサイドなど）などの塗料用添加剤を配合することもできる。
【０１８０】
前記顔料としては、たとえば酸化チタン、酸化鉄、アルミメタリック顔料、カーボンブラック、焼成顔料、フタロシアニン系顔料、有機顔料、体質顔料などがあげられる。
【０１８１】
前記酸化チタンとしては、たとえば石原産業（株）製タイペークＣＲ−９０、ＣＲ−９３、ＣＲ−９５、ＣＲ−９７などがあげられる。
【０１８２】
前記酸化鉄としては、たとえば戸田工業（株）製トダカラー１２０ＥＤ、１４０ＥＤ、１６０ＥＤ、ＫＮ−Ｒ、ＫＮ−Ｖ、チタン工業（株）製ＴＡＲＯＸのＬＬ−ＸＬＯ、ＨＹ−１００、ＨＹ−２００、ＢＬ−１００、ＢＬ−５００などがあげられる。
【０１８３】
前記アルミメタリック顔料としては、たとえば東洋アルミニウム（株）製アルペースト０１００ＭＡ、０７００Ｍ、０２００Ｍ、０２１５Ｍ、１９５０Ｍ、１９００Ｍ、１１００Ｍ、１１０９Ｍ、１２００Ｍ、８８２０ＹＦ、７０８０Ｎ、ＭＧ６００、１７００Ｎなどがあげられる。
【０１８４】
前記カーボンブラックとしては、たとえば三菱化学（株）製ＭＡ７、ＭＡ１１、ＭＡ１００、ＯＩＬ７Ｂ、ＯＩＬ３０Ｂ、ＯＩＬ３１Ｂなどがあげられる。
【０１８５】
前記焼成顔料としては、たとえば大日精化（株）製ダイピロキサイド＃９５１０、＃９５１２、＃９４１０、＃９３１０などがあげられる。
【０１８６】
前記フタロシアニン系顔料としては、たとえば大日精化（株）製＃５１９５Ｎ、＃５３７０などがあげられる。
【０１８７】
前記体質顔料としては、たとえば、アスベステン、炭酸カルシウム、沈降性炭酸カルシウム、クレー、カオリン、陶土、珪酸アルミニウム、珪藻土、ホワイトカーボン、シリカ白、含水微粉珪酸、ベントナイト、タルク、珪酸マグネシウム、炭酸マグネシウム、バライト粉、硫酸バリウム、沈降性硫酸バリウムなどがあげられる。
【０１８８】
前記顔料分散剤としては、たとえばビックケミー・ジャパン（株）製Ａｎｔｉ−Ｔｅｒｒａ−Ｐ、Ａｎｔｉ−Ｔｅｒｒａ−Ｕ、Ａｎｔｉ−Ｔｅｒｒａ−２０３／２０４、Ｄｉｓｐｅｒｂｙｋ、Ｄｉｓｐｅｒｂｙｋ−１０１、Ｄｉｓｐｅｒｂｙｋ−１１０、Ｄｉｓｐｅｒｂｙｋ１３０、Ｄｉｓｐｅｒｂｙｋ１６１、Ｄｉｓｐｅｒｂｙｋ−１６４、Ｄｉｓｐｅｒｂｙｋ−１７０、Ｂｙｋｕｍｅｎ、ＢＹＫ−Ｐ１０４／Ｐ１０５、ＢＹＫ−１０４Ｓ、ＢＹＫ−２４０Ｓ、Ｌａｃｔｉｍｏｎなどがあげられる。
【０１８９】
前記レベリング剤としては、たとえばビックケミー・ジャパン（株）製ＢＹＫ−３００、ＢＹＫ−３０２、ＢＹＫ−３０６、ＢＹＫ−３０７、ＢＹＫ−３３５、ＢＹＫ−３１０、ＢＹＫ−３２０、ＢＹＫ−３２２、ＢＹＫ−３２３、ＢＹＫ−３２４、ＢＹＫ−３２５、ＢＹＫ−３３０、ＢＹＫ−３３１、ＢＹＫ−３３３、ＢＹＫ−３４４、ＢＹＫ−３７０、ＢＹＫ−３５４、ＢＹＫ−３５５、ＢＹＫ−３５８などがあげられる。
【０１９０】
前記増粘剤としては、たとえば楠本化成（株）製ディスパロン＃６９００−２０Ｘ、＃６９００−１０Ｓ、＃４２００−２０、＃４２００−１０、ＮＬケミカルズ（株）製ベントンＳＤ−１、ＳＤ−２、ＳＤ−３、＃２７、＃３４、＃３８、ＭＰＡ−２０００Ｘなどがあげられる。
【０１９１】
前記消泡剤としては、たとえばビックケミー・ジャパン（株）製ＢＹＫ−０５１、ＢＹＫ−０５２、ＢＹＫ−０５３、ＢＹＫ−０５５、ＢＹＫ−０５７、ＢＹＫ−０６５、ＢＹＫ−０６６、ＢＹＫ−０７０、ＢＹＫ−０７７、ＢＹＫ−０８０、ＢＹＫ−０８８、ＢＹＫ−１４１などがあげられる。
【０１９２】
前記紫外線吸収剤としては、たとえばベンゾフェノン系およびベンゾトリアゾール系のものが好適であり、これらのうちでもベンゾフェノン系では、２，２´−ジヒドロキシ−４，４´−ジメトキシベンゾフェノン、２，２´−ジヒドロキシ−４−メトキシベンゾフェノンおよび２，２´，４，４´−テトラヒドロキシベンゾフェノンが、ベンゾトリアゾール系では２−（２´−ヒドロキシ−５´−メチルフェニル）ベンゾトリアゾール、２−（２´−ヒドロキシ−５´−メチルフェニル）−５，６−ジクロルベンゾトリアゾール）、２−（２´−ヒドロキシ−５´−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール、２−（２´−ヒドロキシ−３´，５´−ジ−ｔｅｒｔ−ブチルフェニル）−５−クロル−ベンゾトリアゾール、２−（２´−ヒドロキシ−５´−フェニルフェニル）−５−クロルベンゾトリアゾール、２−（２´−ヒドロキシ−３´−ｔｅｒｔブチルフェニル）−５−クロロベンゾトリアゾール、２−（２´−ヒドロキシ−３´，５´−ジｔｅｒｔブチルフェニル）ベンゾトリアゾールおよび２−（２´−ヒドロキシ−５´−ｔｅｒｔオクチルフェニル）ベンゾトリアゾールが有効である。
【０１９３】
とくに好適な紫外線吸収剤は、式：
【０１９４】
【化１７】

【０１９５】
（式中、Ｒ^２４およびＲ^２５は同じかまたは異なり、いずれも水素原子、低級アルキル基、なかでも分岐鎖状の低級アルキル基、またはアリール基、とくにフェニル基を表わし、Ｘは水素原子またはハロゲン原子、とくに塩素原子である）
で示されるものである。
【０１９６】
前記ＨＡＬＳとしては、たとえばチバ・ガイギー（株）製チヌビン−７７０、２９２、６２２１２３、４４０などがあげられる。
【０１９７】
前記艶消し剤としては、たとえばヘキストインダストリー（株）製セリダスト＃３６２０、＃９６１５Ａ、＃９６１２Ａ、＃３７１５、＃３９１０など、ヘキストワックスＰＥ５２０、ホワイトカーボンなどがあげられる。
【０１９８】
前記シランカップリング剤としては、たとえばメチルトリメトキシシラン、エチルトリエトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、ビニルトリメトキシシラン、３−（グリシジルオキシ）プロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−トリメトキシシリルプロピルイソシアネート、３−トリエトキシシリルプロピルイソシアネート、メチルトリス（エチルメチルケトオキシム）シランなどがあげられ、アルキルケトオキシム基またはイソシアネート基を含有するものが好ましい。
【０１９９】
本発明の塗料組成物は、各種基材に塗装することができ、塗装する基材としては、たとえば金属系基材、セメント系基材、プラスチック系基材などがあげられる。
【０２００】
前記金属系基材としては、たとえば鉄およびその化成処理物またはメッキ物、アルミおよびその化成処理物、ステンレス鋼およびその化成処理物などがあげられる。
【０２０１】
前記セメント系基材としては、たとえばセメント類、石灰類、セッコウ類、コンクリート、セメントモルタル、石綿スレート、石膏ボードなどがあげられる。
【０２０２】
前記プラスチック系基材としては、たとえばポリ塩化ビニル類、ポリエステル類、ポリカーボネート類、アクリル類、ポリオレフィン類、ポリスチレン類、ポリウレタン類、ポリアミド類、ナイロン類、天然ゴム類、ウレタンゴム類、ＡＢＳ樹脂類などがあげられる。
【０２０３】
基材が金属系基材の場合は、たとえばつぎのような下塗り塗料、中塗り塗料を塗装したのちに、本発明の塗料組成物を塗装するのが、防食性、相間密着性の点から好ましい。
【０２０４】
この場合、ジンクリッチペイント塗料が下塗り塗料として好ましい。
【０２０５】
有機質系のジンクリッチペイントのビヒクルとしては、たとえばエポキシ樹脂−ポリアミド樹脂の組合せ、塩化ゴム、ポリスチレン樹脂、シリコーン樹脂などがあげられる。また無機質系のジンクリッチペイントのビヒクルとしてはエチルシリケート、ナトリウムシリケート、リチウムシリケート、カリウムシリケート、アンモニウムシリケートなどがあげられる。とくに本発明の目的に対して好ましいビヒクルは、エポキシ樹脂−ポリアミド樹脂の組合せ、エチルシリケート、カリウムシリケート、リチウムシリケートである。
【０２０６】
その他下塗り塗料、中塗り塗料の例としては、好ましくはエポキシ樹脂（タール変性、ウレタン変性を含む）、ビニル系樹脂（タール変性、アクリル樹脂を含む）、塩化ゴム、ポリウレタン樹脂、およびフェノール樹脂から選ばれた少くとも１種の合成樹脂に、通常使用される着色顔料、体質顔料、沈殿防止剤、分散剤、硬化剤、硬化促進剤、希釈剤、溶剤などを混練してえられる塗料である。
【０２０７】
前記エポキシ樹脂は、分子中に２個以上のエポキシ基を有する、通常塗料用に使用される樹脂である。
【０２０８】
前記エポキシ樹脂のうち、たとえばビスフェノール型エポキシ樹脂としては、一般に市販されているシェル化学（株）製の商品名エピコート８２８、８３４、８３６、１００１、１００４、ＤＸ−２５５、チバガイギー（株）製の商品名アラルダイトＧＹ−２６０、ダウ・ケミカル（株）製の商品名ＤＥＲ３３０、３３１、３３７、大日本インキ化学工業（株）製の商品名エピクロン８００などがあげられる。フェノールノボラック型エポキシ樹脂としては一般に市販されているダウ・ケミカル（株）製の商品名ＤＥＮ４３１、４３８、ポリグリコール型エポキシ樹脂としては、市販されているチバガイギー（株）製の商品名アラルダイトＣＴ−５０８、ダウケミカル（株）製の商品名ＤＥＲ−７３２、７３６などがあげられる。また、エステル型エポキシ樹脂としては、たとえば大日本インキ化学工業（株）製の商品名エピクロン２００、４００；線状脂肪族エポキシ樹脂としては、たとえば日本曹達（株）製の商品名ＢＦ−１０００のごときエポキシ化ポリブタジエンなどがあげられる。
【０２０９】
さらにこれらの樹脂から、容易に類推されるエポキシ系化合物、ならびに前記エポキシ樹脂の誘導体も同様に使用可能であり本発明の技術的範囲内に含まれる。
【０２１０】
たとえばポリオール型エポキシ樹脂、脂環式エポキシ樹脂、ハロゲン含有エポキシ樹脂などが含まれる。
【０２１１】
前記エポキシ樹脂には天然アスファルト、アスファルタイト、アスファルト性パイロビチュメン、タール、コールタール、人造アスファルト、ピッチなどの歴青質を混合することができる。
【０２１２】
また、前記エポキシ樹脂の硬化剤としては、アミンアダクト、ポリアミド樹脂など通常塗料用に使用されるものが使用可能である。
【０２１３】
前記硬化剤のうち、たとえばポリアミド樹脂としては一般に市販されている富士化成工業（株）製商品名トーマイドＹ−２５、２４５、２４００、２５００、第一ゼネラル（株）製商品名ゼナミド２０００、バーサミド１１５、１２５、三和化学（株）製商品名サンマイド３２０、３３０、Ｘ２０００、シェル化学（株）製商品名エピキュアー３２５５、４２５５、アミンアダクト樹脂として富士化学工業（株）製商品名トーマイド２３８、フジキュアー２０２、旭電化（株）製商品名アデカハードナーＥＨ−５３１などがあげられる。脂肪族ポリアミンとしては三和化学（株）製商品名サンマイドＴ−１００、Ｄ−１００、Ｐ−１００、複素環状ジアミン誘導体としては味の素（株）製エポメートＢ−００２、Ｃ−００２、Ｓ−００５などがあげられる。
【０２１４】
前記硬化剤のエポキシ樹脂に対する添加量は当量前後、すなわちエポキシ樹脂１当量に対して約０．７〜１．３当量の範囲である。
【０２１５】
また、ポリイソシアネートを前記エポキシ樹脂の硬化剤として使用することもできる。
【０２１６】
本発明に使用されるビニル系樹脂としては、たとえば塩化ビニル、塩化ビニリデン、酢酸ビニル、プロピオン酸ビニル、スチレン、ビニルトルエン、ビニルアルコール、アクリル酸、メタクリル酸、無水マレイン酸、アクリル酸アルキルエステル、メタクリル酸アルキルエステルなどのモノマーの１種もしくは２種以上の共重合体であり、塩化ビニル樹脂、塩化ビニル−酢酸ビニル共重合体樹脂、アクリル樹脂などがあげられる。
【０２１７】
また、本発明に使用される塩化ゴム樹脂は天然ゴムの塩素化物で通常塩素含量６５〜６８％の化合物である。
【０２１８】
塩化ゴムはロジン、クマロン−インデン樹脂、フェノール樹脂、塩化ビニル樹脂、石油樹脂、ニトリルゴム、クロロプレンゴム、アルキド樹脂と混合して使用することができる。
【０２１９】
また、塩化ゴムは塩化パラフィン、塩化ジフェニル、ジオクチルフタレート、トリクレジルフォスフェートなどの可塑剤と混合して使用される。
【０２２０】
さらに、本発明に使用されるポリウレタン樹脂は、分子中に２個以上の活性水素を有する化合物、たとえば多塩基酸と多価アルコールからえられるポリエステルポリオール、ポリエーテルポリオール、ポリオキシアルキレングリコール、アクリルポリオールなどが主剤であり、前述した分子中に２個以上のイソシアネート基を有するポリイソシアネートが硬化剤である組成物である。
【０２２１】
基材がセメント系基材の場合は、たとえばつぎのような下塗り塗料、中塗り塗料を塗装したのちに、本発明の塗料用組成物を塗装するのが好ましい。
【０２２２】
下塗り塗料としては、未硬化型合成樹脂エマルジョン系複層仕上げ塗料、反応硬化型水溶性エポキシ樹脂複層模様仕上げ塗料および反応硬化型溶剤系エポキシ樹脂複層仕上げ塗料などの複層仕上げ塗料を用いることがとくに好ましい。前記未硬化型合成樹脂エマルジョンの樹脂成分としては、たとえばアクリル系樹脂、酢酸ビニル系樹脂およびこれらの変性樹脂などが包含される。また、前記反応硬化型水性または溶剤系のエポキシ樹脂の硬化系としては、たとえばエポキシ−ポリアミン系、エポキシ−ポリアミド系、エポキシ−ポリアミンポリアミド系などが包含される。
【０２２３】
下塗り塗料をセメント系基材に塗装する方法は、たとえば吹付け塗装、ローラー塗装などにより行うことができる。塗布量は通常０．５〜２．０ｋｇ／ｍ^２で充分と思われる。また、乾燥は通常１〜３日行われるのが一般的である。
【０２２４】
前記下塗り塗料をセメント系基材に塗装する前に、一般的に建築用下地処理に使用されている従来から公知のプライマー、サーフェサーシーラーなどを塗装しておくことができる。また、前記下塗り塗料以外にも溶剤型エポキシ樹脂系などのシーラーに直接もしくは該シーラーを塗布し、つぎにイソシアネート硬化型樹脂塗料などで平滑仕上げを行なったものも包含される。
【０２２５】
本発明の塗料組成物を下塗り塗膜に塗装する方法は、たとえばローラー塗装、刷毛塗装、吹付け塗装などにより行うことができる。塗布量は０．０５〜０．５ｋｇ／ｍ^２、好ましくは０．１〜０．３ｋｇ／ｍ^２である。また、乾燥については、常温で１日以上乾燥させることにより硬化塗膜が形成できる。
【０２２６】
改修塗装方法としては、セメント系基材に塗装した建築外装用塗膜の旧上塗り塗膜に必要に応じて下地処理を行なったのち、本発明の塗料組成物を塗装して改修を行なう方法がある。
【０２２７】
前記方法において旧上塗り塗膜としては、とくに限定されないが前記の本発明の塗料組成物に使用されるような硬化型フッ素塗料、硬化型アクリル塗料、アクリルシリコン塗料、カルボニル−ヒドラジド硬化型水性塗料、酢酸ビニル変性アクリル樹脂系塗料などの非架橋溶剤系塗料およびアクリル樹脂系水性塗料などの非架橋水性塗料によって形成された塗膜であることがとくに好ましい。
【０２２８】
また、前記カルボニル−ヒドラジド硬化系水性塗料としては、カルボニル基含有共重合体水分散液にジヒドラジド架橋剤およびヒドラジン残基を有する水性ポリウレタン樹脂を配合してなる塗料（たとえば特願平４−１７１６８３号公報）があげられる。前記旧上塗り塗膜とセメント系基材とのあいだにはプライマー、サーフェサーが塗装されていてもよく、また、さらにプライマー、サーフェサーの上に複層塗材が塗装されていてもよい。
【０２２９】
旧上塗り塗膜に必要に応じて行なう下地処理は、たとえば下記の下地処理剤を塗布することによって実施できる。該下地処理剤としては、たとえばセメント系（たとえばセメント／合成樹脂エマルジョン系など）のフィラーまたはサーフェサー、反応硬化樹脂系（たとえばエポキシポリアミン系、エポキシポリアミド系など）の浸透型シーラーなどが好ましい例としてあげられる。
【０２３０】
下地処理方法は前記下地処理剤をたとえばローラー、刷毛などで塗装することによって実施できる。また、下地処理剤の塗布量は、たとえばフィラーのものでは０．３〜２．０ｋｇ／ｍ^２、サーフェサーでは０．１〜１．０ｋｇ／ｍ^２、浸透型シーラーでは０．０１〜０．５ｋｇ／ｍ^２で充分と考える。
【０２３１】
また、これらの下地処理剤を塗装したのち、さらにポリイソシアネート硬化型溶剤系塗料を塗装することができる。この塗料の塗装は、たとえばローラー、刷毛、吹付けによって行なうことができる。また、塗布量は０．０５〜０．５ｋｇ／ｍ^２で充分と考える。前記下地処理剤およびポリイソシアネート硬化型溶剤系塗料の乾燥は通常１〜３回行なわれる。また、本発明の塗料組成物の塗装、乾燥は前記した本発明の塗料組成物の場合と同様の方法で行なうことができる。
【０２３２】
基材がプラスチック系基材である場合も前記金属系基材、セメント系基材に使用される下塗り塗料、中塗り塗料を塗装したのちに、本発明の塗料組成物を塗装することもできる。
【０２３３】
基材がプラスチック系基材のうちでもフィルム、シートである場合の塗装方法としては、たとえばグラビアコーティング法、ドクターブレード法、ロールコート法、リバースロール法、エヤーナイフコート法などがあげられる。これらの塗装方法の場合、塗装膜厚としては塗膜外観、塗装性の点から１〜２０μｍ、好ましくは１〜１０μｍが適当である。
【０２３４】
本発明の塗料組成物が塗装された物品の用途としては、たとえば建築用防水シート、トンネル用防水シート、農業用ビニールシート、農業用ビニールフィルム、養生シート、建築用保護シート、車両用保護シート、メッシュシート、メッシュスクリーン、ポリカーボネート屋根、アクリルボード壁、ポリカーボネート壁、ガードレール、信号機、トンネル内壁、トンネル内装板、道路標識、案内板、高速道路側壁、高速道路防音壁、道路灯、橋梁、橋桁、橋脚、煙突、壁紙、畳、マット、テーブルクロス、換気扇、マーキングフィルム、ジオメンブレン、広告板、郵便ポスト、電柱、テント、自動車、航空機、船舶、電車などがあげられる。
【０２３５】
【実施例】
つぎに、本発明を実施例にもとづいてさらに具体的に説明するが、本発明はこれらのみに限定されるものではない。実施例および製造例中の「部」は重量部である。
【０２３６】
実施例１
ゼッフルＧＫ−５１０（水酸基含有テトラフルオロエチレン共重合体。水酸基価６０ｍｇＫＯＨ／ｇ、酸価９ｍｇＫＯＨ／ｇ、数平均分子量１２０００、酢酸ブチル溶液、固形分５０％）の１００部に、硬化剤としてＯＣＮ−Ｃ_３Ｈ_６−Ｓｉ（ＯＣＨ_３）_３の５部およびコロネートＨＸ（日本ポリウレタン（株）製のイソシアネート系硬化剤）の５部を加え、さらにＣ_８Ｆ_１７ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３の５部と酢酸ブチル５０部を加え、よく撹拌して本発明の塗料組成物を得た。
【０２３７】
この塗料組成物をスプレー塗装によりスレート製のフレキシブルボード（７×１５×０．３ｃｍ。日本テストパネル（株）製）に２００ｇ／ｍ^２の塗装量で塗装し、室温で１週間かけて乾燥して塗板を得た。
【０２３８】
この塗板について、以下の試験を行なった。結果を表１に示す。
【０２３９】
油性インク汚染試験：
塗板にマジック（株）製の油性インク（マジックインキ。（株）内田洋行の登録商標。）の赤色を塗り、２４時間放置したのち、エチルアルコールを含浸した紙タオルで拭き取り、拭き取れなかった領域の残存率をつぎの基準で評価する。
Ａ：５％未満
Ｂ：５〜１５％
Ｃ：１５％超で３０％以下
Ｄ：３０％超
【０２４０】
自動車オイル汚染試験：
塗板に自動車の廃ミッションオイルを塗り、２４時間放置したのち、乾燥した紙タオルで拭き取り、拭き取れなかった領域の残存率をつぎの基準で評価する。
Ａ：５％未満
Ｂ：５〜１５％
Ｃ：１５％超で３０％以下
Ｄ：３０％超
【０２４１】
ラッカー汚染試験：
塗板に関西ペイント（株）製のラッカースプレーの赤色をスプレー塗装し、２４時間放置したのち、メチルエチルケトンを含浸させた紙タオルで拭き取り、拭き取れなかった領域の残存率をつぎの基準で評価する。
Ａ：５％未満
Ｂ：５〜１５％
Ｃ：１５％超で３０％以下
Ｄ：３０％超
【０２４２】
耐候性試験：
ＪＩＳ Ｋ５４００に準じ、サンシャインウェザオメータ（スガ試験機（株）製）を用い、５００時間の促進耐候性試験を行なったのち、前記の油性インク汚染試験を行なう。
【０２４３】
密着性試験：
ＪＩＳ Ｋ５４００に準じて碁盤目試験を行なう。フレキシブルボードでは４ｍｍ幅の碁盤目、他の塗板については１ｍｍ幅の碁盤目で行なう。
【０２４４】
碁盤目試験は、塗装後（初期）および、塗板を１００℃の沸騰水に２時間浸漬し、引き上げた後冷却したもの（耐沸騰水試験後）について行なう。
【０２４５】
なお、密着性試験については、被塗物としてフレキシブルボードに加えてガラス板、天然御影石（中国産。ニッタイ工業より入手）およびアルミニウム板（日本テストパネル（株）製のＡ１０５０Ｐ（ＡＭ７１２処理））を用い、これらに塗料組成物をスプレー塗装により２００ｇ／ｍ^２の塗装量で塗装し、室温で１週間かけて乾燥した塗板についても試験をした。
【０２４６】
製造例１（樹脂（Ａ１）の製造）
１０００ｍｌのステンレススチール製オートクレーブに酢酸ブチル２００ｇ、ビニルトリメトキシシラン（ＴＭＶＳ）２９．５ｇ、ｎ−ブチルビニルエーテル（ｎＢＶＥ）２０．０ｇ、２，２‘−アゾビス（２，４−ジメチルバレロニトリル）５．０ｇを仕込み、０℃に氷冷したのち、減圧下に脱気した。これにイソブチレン（ＩＢ）３３．５ｇとテトラフルオロエチレン（ＴＦＥ）１００ｇを仕込み、攪拌下に５０℃に加熱し、２８時間反応させ、反応器内圧力が１．４ＭＰａＧから１ＭＰａＧに下がった時点で反応を停止した（収率２４．６％）。得られた加水分解性アルキルシリケート基含有含フッ素共重合体は、^１９Ｆ−ＭＮＲ、^１Ｈ−ＭＮＲおよび元素分析での分析の結果、ＴＦＥ／ＩＢ／ｎＢＶＥ／ＴＭＶＳ＝４５／４０／８／７モル％であり、ＧＰＣにより測定した数平均分子量は３９００、ＤＳＣにより測定したガラス転移温度は−２１℃であった。
【０２４７】
製造例２（ケイ素含有含フッ素高分子量化合物（Ｂ２）の製造）
攪拌器、不活性ガス導入口、還流冷却器および温度計を備えた５００ｍｌの四ツ口フラスコに、ＣＦ_３ＣＦ_２（ＣＦ_２ＣＦ_２）_ｎＣＨ_２ＣＨ_２ＯＣＯＣＨ＝ＣＨ_２（ｎが３と４の８６／１４重量比の混合物）２６．０ｇ、ステアリルアクリレート１３．０ｇ、γ−メタクリロキシプロピルトリメトキシシラン１．０ｇおよび酢酸ブチル１２０ｇを入れ、７０℃に昇温後、アゾビスイソブチロニトリル０．３ｇを加えて７０℃にて１２時間攪拌下に重合を行なった。ガスクロマトグラフィーにより測定した重合転化率は９７％以上であった。
【０２４８】
得られたケイ素含有含フッ素高分子量化合物は、ＧＰＣにより測定した数平均分子量が１０，０００のものであった。
【０２４９】
この重合反応液に酢酸ブチルを加えて固形分濃度を２５重量％に調整した。
【０２５０】
実施例２
ゼッフルＧＫ−５１０の１００部に、硬化剤としてコロネートＨＸの１２部を加え、さらに製造例２で得られたケイ素含有含フッ素高分子量化合物の１００部と酢酸ブチル５０部を加え、よく撹拌して本発明の塗料組成物を得た。
【０２５１】
この塗料組成物をスプレー塗装によりフレキシブルボード（７×１５×０．３ｃｍ）に２００ｇ／ｍ^２の塗装量で塗装し、室温で１週間かけて乾燥して塗板を得た。
【０２５２】
この塗板について、実施例１と同様な試験を行なった。結果を表１に示す。
【０２５３】
なお、密着性試験については、被塗物としてガラス板、天然御影石、アルミニウム板に塗料組成物をスプレー塗装により２００ｇ／ｍ^２の塗装量で塗装し、室温で１週間かけて乾燥した塗板についても試験をした。
【０２５４】
実施例３
ゼッフルＧＫ−５１０の１００部に、硬化剤としてＯＣＮ−Ｃ_３Ｈ_６−Ｓｉ（ＯＣＨ_３）_３の１０部を加え、さらに製造例２で得られたケイ素含有含フッ素高分子量化合物の５部と酢酸ブチル５０部を加え、よく撹拌して本発明の塗料組成物を得た。
【０２５５】
この塗料組成物をスプレー塗装によりフレキシブルボード（７×１５×０．３ｃｍ）に２００ｇ／ｍ^２の塗装量で塗装し、室温で１週間かけて乾燥して塗板を得た。
【０２５６】
この塗板について、実施例１と同様な試験を行なった。結果を表１に示す。
【０２５７】
なお、密着性試験については、被塗物としてガラス板、天然御影石、アルミニウム板に塗料組成物をスプレー塗装により２００ｇ／ｍ^２の塗装量で塗装し、室温で１週間かけて乾燥した塗板についても試験をした。
【０２５８】
実施例４
製造例１で得た樹脂（Ａ１）の１００部に、製造例２で得られたケイ素含有含フッ素高分子量化合物の１００部、硬化促進剤としてジブチル錫ジラウレート０．１部および酢酸ブチル５０部を加え、よく撹拌して本発明の塗料組成物を得た。
【０２５９】
この塗料組成物をスプレー塗装によりフレキシブルボード（７×１５×０．３ｃｍ）に２００ｇ／ｍ^２の塗装量で塗装し、室温で１週間かけて乾燥して塗板を得た。
【０２６０】
この塗板について、実施例１と同様な試験を行なった。結果を表１に示す。
【０２６１】
なお、密着性試験については、被塗物としてガラス板、天然御影石、アルミニウム板に塗料組成物をスプレー塗装により２００ｇ／ｍ^２の塗装量で塗装し、室温で１週間かけて乾燥した塗板についても試験をした。
【０２６２】
比較例１
ゼッフルＧＫ−５１０の１００部に、硬化剤としてコロネートＨＸの１２部を加え、よく撹拌して比較用の塗料組成物を得た。
【０２６３】
この塗料組成物をスプレー塗装によりフレキシブルボード（７×１５×０．３ｃｍ）に２００ｇ／ｍ^２の塗装量で塗装し、室温で１週間かけて乾燥して塗板を得た。
【０２６４】
この塗板について、実施例１と同様な試験を行なった。結果を表１に示す。
【０２６５】
なお、密着性試験については、被塗物としてガラス板、天然御影石、アルミニウム板に塗料組成物をスプレー塗装により２００ｇ／ｍ^２の塗装量で塗装し、室温で１週間かけて乾燥した塗板についても試験をした。
【０２６６】
比較例２
Ｃ_８Ｆ_１７ＣＨ_２ＣＨ_２Ｓｉ（ＯＣＨ_３）_３の１０部と酢酸ブチル９０部を混合し、さらにジブチル錫ジラウレート０．１部を加え、攪拌して、比較用の塗料組成物を得た。
【０２６７】
この塗料組成物をスプレー塗装によりフレキシブルボード（７×１５×０．３ｃｍ）に２００ｇ／ｍ^２の塗装量で塗装し、室温で１週間かけて乾燥して塗板を得た。
【０２６８】
この塗板について、実施例１と同様な試験を行なった。結果を表１に示す。
【０２６９】
なお、密着性試験については、被塗物としてガラス板、天然御影石、アルミニウム板に塗料組成物をスプレー塗装により２００ｇ／ｍ^２の塗装量で塗装し、室温で１週間かけて乾燥した塗板についても試験をした。
【０２７０】
【表１】

【０２７１】
【発明の効果】
本発明の塗料組成物によれば、汚染防止、特に油性汚れの除去性に優れるので、落書きをされても容易に拭き取り除去でき、しかも耐候性、密着性にも優れるので、屋外の各種の塗装に最適である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a coating composition having good adhesion to a substrate and providing a coating film having particularly excellent stain removal properties.
[0002]
[Prior art]
It is common practice to form a water-repellent antifouling coating on the surface of various substrates, for example, stone, concrete, metal, plastic, wood, etc., to prevent the adhesion of dirt or to facilitate the removal. . Such antifouling paints are roughly classified into (1) an inorganic paint composition mainly composed of a silicone compound (for example, Patent Document 1) and (2) a curable resin made of a fluororesin or an acrylic resin. A coating composition (for example, Patent Literature 2, Patent Literature 3, Patent Literature 4, Patent Literature 5 and the like) and a coating composition (3) in which a film-forming resin is mixed with an antifouling silicon-containing low molecular weight compound. Literature 6, Patent Literature 7, Patent Literature 8, Patent Literature 9, Patent Literature 10, Patent Literature 11, Patent Literature 12, etc.) are known.
[0003]
When the inorganic coating of the above (1) is formed on the surface of the substrate, it is difficult to coat the substrate uniformly and continuously, and a long-term antifouling effect cannot be expected.
[0004]
In the method (2) of coating with a water- and oil-repellent resin, the strength of the coating film itself can be obtained, but the antifouling effect is insufficient.
[0005]
The coating composition in which the film-forming resin of (3) is blended with an antifouling silicon-containing low molecular weight compound is intended to compensate for the problems of (1) and (2). It is difficult to uniformly disperse the compound in the film-forming resin, and further to concentrate the silicon-containing low-molecular-weight compound on the surface, and in particular, it is difficult to keep the silicon-containing low-molecular-weight compound on the surface for a long time, and it is still No paint composition has been found which gives a coating film capable of maintaining an antifouling effect over a long period of time.
[0006]
By the way, attempts have been made to achieve an antifouling effect by making the surface hydrophilic rather than water and oil repellent. For example, Patent Document 13 discloses a coating composition in which a fluorine resin or the like is used as a coating film forming component, and a tri- or tetra-functional (having 3 to 4 hydrolyzable groups) fluorine-containing silicate compound is blended as an antifouling agent. I have. However, this coating composition achieves an antifouling effect by hydrolyzing the fluorinated silicate concentrated on the coating film surface and hydrophilizing the surface with the hydrolyzed hydrophilic group, and The group having fluorine is a hydrolyzable group and is hydrolyzed to be separated and no longer exists on the surface of the coating film.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a coating composition which makes the surface of a coating film water-repellent and oil-repellent, and which can maintain an antifouling effect, in particular, a stain-removing property and a wiping property even outdoors for a long period of time.
[0008]
[Patent Document 1]
JP-A-64-45411
[Patent Document 2]
Japanese Patent Publication No. 60-21686
[Patent Document 3]
JP-A-57-23662
[Patent Document 4]
JP-A-63-264675
[Patent Document 5]
JP-A-5-25422
[Patent Document 6]
JP-A-1-51477
[Patent Document 7]
JP-A-9-78029
[Patent Document 8]
WO98 / 22530 pamphlet
[Patent Document 9]
JP-A-5-339538
[Patent Document 10]
JP-A-11-29722
[Patent Document 11]
JP-A-2-75649
[Patent Document 12]
JP-A-10-88065
[Patent Document 13]
WO97 / 11130 pamphlet
[0009]
[Means for Solving the Problems]
The present invention
(A) a functional group-containing fluoroolefin resin and / or a functional group-containing non-fluorinated acrylic resin, and
(B) (B1) Equation (1):
RfSi (OR¹)_n(R²)_3-n            (1)
(In the formula, Rf is a linear or branched non-hydrolyzable fluoroalkyl group having 3 to 20 carbon atoms, which may contain a functional group, and an oxygen atom and / or a nitrogen atom in the middle. May contain atoms; R¹Is a non-fluorinated alkyl group having 1 to 10 carbon atoms, -N = CR³R⁴Or -C (= O) R⁵(R³, R⁴And R⁵Are the same or different, and each is a non-fluorinated alkyl group having 1 to 10 carbon atoms);²Is a hydrogen atom, a non-fluorinated alkyl group having 1 to 10 carbon atoms or Rf; n is an integer of 1 to 3), and a fluorine-containing silicon-containing low molecular weight compound represented by the formula (B2):
YSi (OR¹)_n(R²)_3-n            (2)
(Wherein, Y is a non-hydrolyzable and non-functional fluoroolefin copolymer radical having 21 or more carbon atoms, a fluorine-containing acryl having 21 or more carbon atoms and optionally containing a functional group) Copolymer radical, fluorinated polyether radical having 21 or more carbon atoms and optionally containing a functional group, fluorinated polyester radical having 21 or more carbon atoms and optionally containing a functional group or 21 or more carbon atoms A fluorine-containing polyurethane radical optionally containing a functional group;¹, R²And n is the same as defined above), at least one silicon-containing fluorine-containing compound selected from the group consisting of silicon-containing fluorine-containing high molecular weight compounds
And a coating composition comprising:
[0010]
As the functional group of the resin (A), a hydroxyl group or a hydrolyzable alkyl silicate residue, preferably -SiR⁶ _3-m(OR⁷)_m(Where R⁶Is a non-hydrolyzable hydrocarbon group which may contain a fluorine atom having 1 to 18 carbon atoms; R⁷Is a hydrocarbon group having 1 to 18 carbon atoms; m is an integer of 1 to 3).
[0011]
The coating composition may further contain (C) a curing agent.
[0012]
However, the resin (A) may be a fluoroolefin resin having a hydrolyzable alkyl silicate residue, and in that case, it may not include a curing agent.
[0013]
As the curing agent (C), an isocyanate compound and / or Si (OR⁹)₄(R⁹Is a non-fluorinated alkyl group having 1 to 10 carbon atoms), R¹⁰Si (OR¹¹)₃(R¹⁰And R¹¹Are the same or different, and preferably include at least one selected from the group consisting of a non-fluorinated alkyl group having 1 to 10 carbon atoms), a homocondensed oligomer thereof and a co-condensed co-oligomer thereof.
[0014]
When the curing agent (C) is an isocyanate compound, the isocyanate compound having the hydrolyzable alkyl silicate residue is preferably exemplified.
[0015]
Suitable combinations include, but are not limited to, a combination in which the resin (A) is a hydroxyl group-containing fluoroolefin resin and the curing agent (C) is an isocyanate compound having the hydrolyzable alkyl silicate residue. can give.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
In the composition of the present invention, the silicon-containing fluorine-containing compound as the component (B) is condensed with the hydrolyzable group and the functional group in the resin as the component (A) via the curing agent (C) or directly. By chemically bonding to the resin (A) to obtain a non-hydrolyzable fluoroalkyl group of the silicon-containing fluorine-containing compound at a high concentration near the surface of the coating film, excellent antifouling properties can be obtained. It is thought to be applied to the film surface.
[0017]
First, the silicon-containing fluorine-containing compound as the component (B) will be described. As the component (B), a silicon-containing fluorine-containing low molecular weight compound (B1) and a silicon-containing fluorine-containing high molecular weight compound (B2) can be used.
[0018]
The silicon-containing fluorine-containing low molecular weight compound (B1) is represented by the formula (1):
RfSi (OR¹)_n(R²)_3-n            (1)
(In the formula, Rf is a linear or branched non-hydrolyzable fluoroalkyl group having 3 to 20 carbon atoms, which may contain a functional group, and an oxygen atom and / or a nitrogen atom in the middle. May contain atoms; R¹Is a non-fluorinated alkyl group having 1 to 10 carbon atoms, -N = CR³R⁴Or -C (= O) R⁵(R³, R⁴And R⁵Are the same or different, and each is a non-fluorinated alkyl group having 1 to 10 carbon atoms);²Is a hydrogen atom, a non-fluoroalkyl group having 1 to 10 carbon atoms or Rf; n is an integer of 1 to 3).
[0019]
Rf is a linear or branched fluoroalkyl group having 3 to 20 carbon atoms, and needs to be non-hydrolyzable. The Rf group imparts water and oil repellency to the coating film surface. Furthermore, since it contains fluorine, when forming a coating film, it gathers on the surface of the coating film and has an effect of increasing the surface concentration. When the number of carbon atoms is 2 or less, oil repellency decreases, which is not preferable. If it exceeds 20, it is classified as a high molecular weight compound described later. A preferred lower limit is 4 and even 5. The preferred upper limit for the low molecular weight compound is 15, more preferably 12.
[0020]
The Rf group may or may not have a functional group. Examples of the functional group include a hydroxyl group, a carboxyl group, a glycidyl group, an amino group and the like.
[0021]
Further, the Rf group may have an oxygen atom and / or a nitrogen atom in its chain (not at the terminal). When it contains an oxygen atom in the middle, it is a fluoroether group.
[0022]
The following are specific examples of the Rf group.
[0023]
(1) Fluoroalkyl group having no functional group
C₄F₉C₂H₄-, C₈F₁₇C₂H₄-, C₉F₁₉C₂H₄-, C₄F₉SO₂N (CH₃) C₂H₄-, C₄F₉C₂H₄N (CH₃) C₃H₉-Etc.
[0024]
(2) Fluoroalkyl group having functional group
OHC₂H₄CF₂CF₂CF₂CF₂C₂H₄−,
HOOCCF₂CF₂CF₂CF₂C₂H₄-Etc.
[0025]
(3) Fluoroether group having no functional group
CF₃OCF₂CF₂OC₂H₄−,
CF₃(CF₂CF₂O)₂-C₂H₄−,
CF₃O (CF₂O)₂(CF₂CF₂O)₂−,
X- (C₃F₆O)_l− (C₂F₄O)_m− (CF₂O)_n− (C₂F₄)_p− (Y¹)_r-(X is F or C_qF_2qO- (q = 1 to 5); Y¹Is -OCONH (CH₂)₃-Or -OCONH (CH₂)₂OCOC (CH₃)-; L, m, n, p and r are the same or different integers of 0 or more. However, the total number of carbon atoms in Rf is 1 to 20)
[0026]
(4) a fluoroether group having a functional group
HOCH₂CF₂O (CF₂CF₂O)₃-C₂H₄-, HOOCCF₂O (CF₂CF₂O)₃-C₂H₄−,
X- (C₃F₆O)_l− (C₂F₄O)_m− (CF₂O)_n− (C₂F₄)_p− (Y¹)_r-(X is -OH, -SH, -NHR, -COR, -COOR, -CN, -NCO, -OCOCR = CH₂, -OCR = CH₂(R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), -OCF = CF₂, Epoxy group; Y¹Is -OCONH (CH₂)₃-Or -OCONH (CH₂)₂OCOC (CH₃)-; L, m, n, p and r are the same or different integers of 0 or more. However, the total number of carbon atoms in Rf is 1 to 20)
Of these, a fluoroalkyl group and a fluoroether group having no functional group are preferable because of excellent water and oil repellency.
[0027]
R¹Is a group which is eliminated by hydrolysis, each of which is a non-fluorinated alkyl group having 1 to 10 carbon atoms, -N = CR³R⁴Or -C (= O) R⁵(R³, R⁴And R⁵Are the same or different, and each is a non-fluorinated alkyl group having 1 to 10 carbon atoms). R²Is a hydrogen atom, a non-fluorinated alkyl group having 1 to 10 carbon atoms or Rf, and is a non-hydrolyzable group. The SiO radical generated by the hydrolysis reacts with the functional group of the resin (A) to chemically fix Rf to the resin (A).
[0028]
Examples of the non-fluorinated alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl and the like, and methyl and ethyl are particularly preferable in terms of good hydrolyzability.
[0029]
-N = CR³R⁴Is, for example, -N (CH₃) C₂H₅, -N = C (CH₃) C₂H₅And so on.
[0030]
-C (= O) R⁵Is, for example, -C (= O) CH₃, -C (= O) C₂H₅And so on.
[0031]
n is an integer of 1 to 3, and when n = 4, all groups become hydrolyzable, and the desired water / oil repellency cannot be obtained.
[0032]
Specific examples of the silicon-containing fluorine-containing low molecular weight compound (B1) include the following, but are not limited thereto.
C₄F₉C₂H₄Si (OCH₃)₃,
C₄F₉C₂H₄Si (ON = C (CH₃) C₂H₅)₃,
C₈F₁₇C₂H₄Si (OCH₃)₃,
C₈F₁₇C₂H₄Si (ON = C (CH₃) C₂H₅)₃,
C₉F₁₉C₂H₄Si (OCH₃)₃,
C₉F₁₉C₂H₄Si (ON = C (CH₃) C₂H₅)₃,
CF₃CF₂CF₂OCF (CF₃) CF₂OCF (CF₃) CONHCH₂CH₂CH₂Si (OCH₃)₃,
CF₃CF₂CF₂OCF (CF₃) CF₂OCF (CF₃) CONHCH₂CH₂CH₂Si (ON = C (CH₃) C₂H₅)₃,
CF₃CF₂CF₂OCF (CF₃) CF₂OCF (CF₃) CONHCH₂CH₂CH₂Si (OCOCH₃)₃,
F (CF₂CF₂CF₂O)₃CF₂CF₂OCONH (CH₂)₃Si (OCH₃)₃, C₉F₁₉C₂H₄Si (OCH₃)₂CH₃,
(C₉F₁₉C₂H₄)₂Si (OCH₃)₂,
CF₃CF₂CF₂OCF (CF₃) CF₂OCF (CF₃) CONHCH₂CH₂CH₂Si (OCOCH₃)₂CH₃,
[CF₃CF₂CF₂OCF (CF₃) CF₂OCF (CF₃) CONHCH₂CH₂CH₂]₂Si (OCH₃)₂,
CF₃CF₂CF₂OCF (CF₃) CF₂OCF (CF₃) CONHCH₂CH₂CH₂Si (OCH₃) (CH₃)₂
[0033]
Among these, a fluoroalkyl group in which Rf has no functional group is preferable from the viewpoint of easy synthesis.
[0034]
Next, the silicon-containing fluorine-containing high molecular weight compound (B2) will be described.
[0035]
The silicon-containing fluorine-containing high molecular weight compound (B2) has the formula (2):
YSi (OR¹)_n(R²)_3-n            (2)
(Wherein, Y is a non-hydrolyzable and non-functional fluoroolefin copolymer radical having 21 or more carbon atoms, a fluorine-containing acryl having 21 or more carbon atoms and optionally containing a functional group) Copolymer radical, fluorinated polyether radical having 21 or more carbon atoms and optionally containing a functional group, fluorinated polyester radical having 21 or more carbon atoms and optionally containing a functional group or 21 or more carbon atoms A fluorine-containing polyurethane radical optionally containing a functional group;¹, R²And n are the same as those described above).
[0036]
That is, a hydrolyzable silicon group -Si (OR¹)_n(R²)_3-nAre linked. The hydrolyzable silicon group may be directly bonded to the main chain of the fluorine-containing polymer chain Y or may be bonded to a side chain. However, it is preferably bonded to a side chain from the viewpoint that a hydrolyzable silicon group can be efficiently introduced.
[0037]
Examples of the fluorine-containing polymer chain Y include radicals of non-hydrolyzable high molecular weight compounds, and specifically, a fluoroolefin copolymer radical having no functional group and having 21 or more carbon atoms, and a radical having 21 or more carbon atoms. A fluorine-containing acrylic copolymer radical which may contain a functional group, a fluorine-containing polyether radical having 21 or more carbon atoms and which may contain a functional group, a fluorine-containing polyether radical which has 21 or more carbon atoms and contains a functional group And a fluorine-containing polyester radical which may have a carbon number of 21 or more and may contain a functional group.
[0038]
Examples of the fluoroolefin copolymer radical having no functional group and having 21 or more carbon atoms include a copolymer of a fluoroolefin and a copolymer of a fluoroolefin and another monomer, and have a molecular weight of 500 or more, preferably It is 1000 or more, and the upper limit is 1,000,000 or less, preferably 100,000 or less.
[0039]
Examples of the fluoroolefin include perfluoroolefins such as tetrafluoroethylene, hexafluoropropylene, and perfluoro (alkyl vinyl ether); chlorotrifluoroethylene; trifluoroethylene, vinylidene fluoride, and vinyl fluoride.
[0040]
Other monomers include, for example, alkyl vinyl ethers, alkyl vinyl esters, non-fluorinated olefins, (meth) acrylates, styrenes and the like.
[0041]
As a method of introducing a hydrolyzable silicon-containing group into the fluorine-containing polymer chain Y, a copolymerization method using a monomer having a hydrolyzable silicon-containing group as a copolymerization component; After copolymerization into a functional group-containing fluorine-containing copolymer, there is a polymer reaction method in which a functional group is reacted with a hydrolyzable silicon compound. Either method may be used, but a copolymerization method is preferred from the viewpoint of ease of synthesis.
[0042]
As the fluoroolefin copolymer radical having no functional group, specifically, those described in JP-A-4-279612 can be preferably used.
[0043]
As the fluorine-containing acrylic copolymer radical having at least 21 carbon atoms and optionally containing a functional group, a homopolymer of a fluorine-containing acrylic monomer or a copolymerizable monomer with a fluorine-containing acrylic monomer may be used. And a radical of a copolymer with a monomer.
[0044]
As the silicon-containing fluorine-containing high molecular weight compound (B2) having the fluorine-containing acrylic copolymer radical as the fluorine-containing polymer chain Y, specifically, a fluorine-containing ester of acrylic acid or a fluorine-containing ester of methacrylic acid (fluoro) Acrylates), copolymers of silicone-based vinyl monomers and, if necessary, any other monomers are preferred.
[0045]
Specific examples of the fluoroacrylate include, for example, monomers represented by the following formulas (3) to (7).
(3) Rf¹SO₂NR¹²R^ThirteenOCOCR¹⁴= CH₂,
(4) Rf¹− (CH₂)_nOCOCR¹⁴= CH₂,
(5) Rf¹CONR¹²R^ThirteenOCOCR¹⁴= CH₂,
(6) Rf¹CH₂CH (OH) CH₂OCOCR¹⁴= CH₂,
(7) Rf¹CH₂CH (OCOR^Fifteen) CH₂OCOCR¹⁴= CH₂
(Where Rf¹Is a perfluoroalkyl group having 3 to 21 carbon atoms;¹²Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;^ThirteenIs an alkylene group having 1 to 10 carbon atoms; R¹⁴Is a hydrogen atom or a methyl group; R^FifteenIs an alkyl group having 1 to 10 carbon atoms; n is an integer of 1 to 10).
[0046]
Specifically, for example
CF₃(CF₂)₇(CH₂)₁₁OCOCH = CH₂,
CF (CF₃)₂(CF₂)₆(CH₂)₃OCOCH = CH₂,
CF (CF₃)₂(CF₂)₁₀(CH₂)₂OCOCH = CH₂,
CF₃(CF₂)₇SO₂N (C₃H₇) (CH₂)₈OCOCH = CH₂,
CF (CF₃)₂(CF₂)₆CH₂CH (OH) CH₂OCOCH = CH₂,
H (CF₂) CH₂OCOCH = CH₂,
CF (CF₃) (CCIF₂) (CF₂)₇CONHCOOCH = CH₂,
CF₃(CF₂)₄(CH₂) OCOCH = CH₂,
CF (CF₃)₂(CF₂)₆(CH₂)₂OCOCH = CH₂,
CF₃(CF₂)₇SO₂N (CH₃) (CH₂)₂OCOCH = CH₂,
CF (CF₃)₂(CF₂)₆CH₂CH (OCOCH₃) OCOCH = CH₂,
CCIF₂(CF₂)₁₀CH₂OCOCH = CH₂,
C₃F₇O [CF (CF₃) CF₂O]_nCF (CF₃) CH₂CH₂OCOCH = CH₂,
C₃F₇O [CF (CF₃) CF₂O]_nCF₂CF₂CH₂CH₂OCOCH = CH₂,
C₈F₁₇-Ph-CH₂OCOCH = CH₂
(N is an integer of 1 to 500, Ph is divalent phenyl)
Acrylates such as;
CF₃(CF₂)₄(CH₂) OCOC (CH₃) = CH₂,
CF (CF₃)₂(CF₂)₆(CH₂)₂OCOC (CH₃) = CH₂,
CF₃(CF₂)₇SO₂N (CH₃) (CH₂)₂OCOC (CH₃) = CH₂,
CF (CF₃)₂(CF₂)₆CH₂CH (OCOCH₃) OCOC (CH₃) = CH₂,
CCIF₂(CF₂)₁₀CH₂OCOC (CH₃) = CH₂,
CF₃(CF₂)₇(CH₂)₁₁OCOC (CH₃) = CH₂,
CF (CF₃)₂(CF₂)₆(CH₂)₃OCOC (CH₃) = CH₂,
CF (CF₃)₂(CF₂)₁₀(CH₂)₂OCOC (CH₃) = CH₂,
CF₃(CF₂)₇SO₂N (C₃H₇) (CH₂)₈OCOC (CH₃) = CH₂,
CF (CF₃)₂(CF₂)₆CH₂CH (OH) CH₂OCOC (CH₃) = CH₂,
H (CF₂) CH₂OCOC (CH₃) = CH₂,
CF (CF₃) (CCIF₂) (CF₂)₇CONHCOOC (CH₃) = CH₂,
C₃F₇O [CF (CF₃) CF₂O]_nCF (CF₃) CH₂OCOC (CH₃) = CH₂,
C₈F₁₇-Ph-CH₂OCOC (CH₃) = CH₂,
C₈F₁₇-Ph-COOCH₂CH (OH) CH₂OCOC (CH₃) = CH₂
(N is an integer of 1 to 500, Ph is divalent phenyl)
And the like.
[0047]
Of these, (meth) acrylates are preferred from the viewpoint of easy synthesis.
[0048]
Examples of the silicone-based vinyl monomer include the following monomers.
CH₂= CHCO₂(CH₂)₃Si (OCH₃)₃, CH₂= CHCO₂(CH₂)₃Si (OC₂H₅)₃, CH₂= C (CH₃) CO₂(CH₂)₃Si (OCH₃)₃, CH₂= C (CH₃) CO₂(CH₂)₃Si (OC₂H₅)₃, CH₂= CHCO₂(CH₂)₃SiCH₃(OC₂H₅)₂, CH₂= C (CH₃) CO₂(CH₂)₃SiC₂H₅(OCH₃)₂, CH₂= C (CH₃) CO₂(CH₂)₃Si (CH₃)₂(OC₂H₅), CH₂= C (CH₃) CO₂(CH₂)₃Si (CH₃)₂OH, CH₂= CH (CH₂)₃Si (OCOCH₃)₃, CH₂= C (CH₃) CO₂(CH₂)₃SiC₂H₅(OCOCH₃)₂, CH₂= C (CH₃) CO₂(CH₂)₃SiCH₃(N (CH₃) COCH₃)₂, CH₂= CHCO₂(CH₂)₃SiCH₃[ON (CH₃) C₂H₅]₂, CH₂= C (CH₃) CO₂(CH₂)₃SiC₆H₅[ON (CH₃) C₂H₅]₂(Meth) acrylates such as CH; CH₂= CHSi [ON = C (CH₃) (C₂H₅)]₃, CH₂= CHSi (OCH₃)₃, CH₂= CHSi (OC₂H₅)₃, CH₂= CHSiCH₃(OCH₃)₂, CH₂= CHSi (OCOCH₃)₃, CH₂= CHSi (CH₃)₂(OC₂H₅), CH₂= CHSi (CH₃)₂SiCH₃(OCH₃)₂, CH₂= CHSiC₂H₅(OCOCH₃)₂, CH₂= CHSiCH₃[ON (CH₃) C₂H₅]₂, Vinyltrichlorosilane or vinylsilanes such as partial hydrolysates thereof; trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylbutyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl Examples thereof include vinyl ethers such as vinyl ether.
[0049]
Among these, vinylsilanes and (meth) acrylates are preferable, and (meth) acrylates are particularly preferable, since a hydrolyzable silicate group can be efficiently introduced into the copolymer.
[0050]
The other monomer may be a monomer copolymerizable with the fluoroacrylate and the silicone vinyl monomer.
[0051]
For example, the following can be exemplified, but the present invention is not limited to these.
(1) Acrylic acid or methacrylic acid
(2) Esters of acrylic acid or methacrylic acid
Methyl ester, ethyl ester, propyl ester, butyl ester, isobutyl ester, t-butyl ester, hexyl ester, 2-ethylhexyl ester, decyl ester, lauryl ester, stearyl ester, isobornyl ester, β-hydroxyethyl ester, glycidyl ester , Phenyl esters, benzyl esters, 4-cyanophenyl esters, RO (CH₂CH₂O)_mAn alcohol ester represented by H (R is an alkyl group, m is an integer of 1 or more).
(3) Fatty acid vinyl esters
Vinyl esters such as acetic acid, propionic acid, caprylic acid, lauric acid and stearic acid.
(4) Styrene monomers
Styrene, α-methylstyrene, p-methylstyrene.
(5) Allyl esters of fatty acids
Allyl heptanoate, allyl caprylate, allyl caproate.
(6) Vinyl alkyl ketones
Vinyl methyl ketone, vinyl ethyl ketone.
(7) Acrylamides
N-methylacrylamide, H-methylol methacrylamide.
(8) Dienes
2,3-dichloro-1,3-butadiene, isoprene.
(9) Alkylene glycol esters such as ethylene dimethacrylate and acrylic acid or methacrylic acid esters of polyalkylene glycol.
[0052]
The content of the fluoroacrylate is preferably 50.0 to 98.0% by weight, more preferably 60.0 to 80.0% by weight. If the amount is too small, the water / oil repellency decreases, and if the amount is too large, the solvent solubility of the obtained polymer becomes poor, and as a result, the oil repellency decreases.
[0053]
The content of the silicone-based vinyl monomer is preferably 2.0 to 6.0% by weight, and more preferably 2.0 to 3.0% by weight. If the amount is too small, the adhesion decreases, and if it is too large, the oil repellency decreases.
[0054]
The other copolymerizable monomer is the balance, preferably 48% by weight or less, more preferably 40% by weight or less.
[0055]
The molecular weight is between 500 and 1,000,000, preferably between 5,000 and 100,000.
[0056]
The silicon-containing fluorine-containing high molecular weight compound (B2) containing a fluorine-containing polyether radical having 21 or more carbon atoms and optionally containing a functional group is described in, for example, US Pat. No. 5,279,820. What is being done. Functional groups may or may not be present.
[0057]
As a specific radical, for example,
X- (C₃F₆O)_l− (C₂F₄O)_m− (CF₂O)_n− (C₂F₄)_p− (Y²)_r-(X is F, Cl, H, an alkyl group having 1 to 8 carbon atoms or C_qF_2qO- (q = 1 to 15); Y²Is an alkylene group having 1 to 20 carbon atoms, -SO₂OCONH (CH₂)₃-, -OCONH (CH₂)₃-, -OCOOCH₂CH (OH) CH₂O (CH₂)₃-Or -CONH (CH₂)₃-; L, m, n, p and r are the same or different and are integers from 0 to 200. However, the total number of carbon atoms of the radical is 21 or more).
[0058]
For the introduction of the hydrolyzable silicate group, a method of copolymerizing the above-mentioned silicone vinyl monomer is preferable.
[0059]
Hydrolyzable silicate group -Si (OR¹)_n(R²)_3-nIs preferably 2.0 to 6.0% by weight, more preferably 2.0 to 3.0% by weight. If the amount is too small, the adhesion decreases, and if it is too large, the oil repellency decreases.
[0060]
The molecular weight is between 500 and 1,000,000, preferably between 5,000 and 100,000.
[0061]
Examples of the silicon-containing fluorine-containing high molecular weight compound (B2) having a fluorine-containing polyester radical having 21 or more carbon atoms and optionally containing a functional group include those described in JP-A-8-73836. can give.
[0062]
Functional groups may or may not be present. Suitable functional groups include, for example, a hydroxyl group, a carboxyl group, an amino group, a glycidyl group and the like.
[0063]
As a specific radical, for example,
H₂C = C (COO-A-Rf²)₂,
Rf²-A-OOC-CH = CH-COO-A-Rf²
(Rf²Is a fluoroalkyl group, A is an alkylene group having 1 to 4 carbon atoms)
And a radical of a homopolymer of such a monomer or a copolymer with another monomer.
[0064]
For the introduction of the hydrolyzable silicate group, a method of copolymerizing the above-mentioned silicone vinyl monomer is preferable.
[0065]
Hydrolyzable silicate group -Si (OR¹)_n(R²)_3-nIs preferably 2.0 to 6.0% by weight, more preferably 2.0 to 3.0% by weight. If the amount is too small, the adhesion decreases, and if it is too large, the oil repellency decreases.
[0066]
The molecular weight is between 500 and 1,000,000, preferably between 5,000 and 100,000.
[0067]
In addition, a silicon-containing fluorine-containing high molecular weight compound containing a fluorine-containing polyurethane radical having 21 or more carbon atoms and optionally containing a functional group can also be used.
[0068]
Hydrolyzable silicate group -Si (OR¹)_n(R²)_3-nIs preferably 2.0 to 6.0% by weight, more preferably 2.0 to 3.0% by weight. If the amount is too small, the adhesion decreases, and if it is too large, the oil repellency decreases.
[0069]
The molecular weight is between 500 and 1,000,000, preferably between 5,000 and 100,000.
[0070]
Among these high molecular weight radicals, a fluoroolefin copolymer radical having no functional group, a fluoroacrylate radical, and a fluoroether radical are preferable from the viewpoint of excellent water and oil repellency, and a fluoroacrylate radical is particularly preferable.
[0071]
The coating composition of the present invention contains the silicon-containing fluorine-containing compound (B) and the functional group-containing fluoroolefin resin (A1) and / or the functional group-containing non-fluorine acrylic resin (A2) as the component (A).
[0072]
Examples of the functional group contained in the resin of the component (A) include a hydroxyl group, a hydrolyzable alkyl silicate residue, a carboxyl group, an amino group, and the like, but are excellent in reactivity with the silicon-containing fluorine-containing compound (B). A hydroxyl group and a hydrolyzable alkyl silicate residue are preferred from the viewpoints of good reactivity with an isocyanate compound as a curing agent and further improvement in adhesion.
[0073]
Examples of the hydrolyzable alkyl silicate residue include -SiR⁶ _3-m(OR⁷)_m(Where R⁶Is a non-hydrolyzable hydrocarbon group which may contain a fluorine atom having 1 to 18 carbon atoms; R⁷Is a hydrocarbon group having 1 to 18 carbon atoms; m is an integer of 1 to 3).
[0074]
R⁶Examples include methyl, ethyl, propyl and the like.
[0075]
R⁷Examples thereof include methyl, ethyl, propyl and the like, and particularly preferred is methyl from the viewpoint of excellent reactivity (hydrolysis).
[0076]
m is an integer of 1 to 3, and is preferably 3 from the viewpoint of excellent hydrolyzability.
[0077]
Among the functional group-containing fluoroolefin resins (A1), examples of the fluoroolefin resin having a hydroxyl group or a carboxyl group as a functional group include tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoro (alkyl vinyl ether), and trifluoroethylene. And a copolymer of a fluoroolefin such as vinylidene fluoride and vinyl fluoride, and a functional group-containing monomer, and if necessary, a monomer copolymerizable with these monomers. A typical example of the hydroxyl group-containing monomer is hydroxybutyl vinyl ether, and a typical example of the carboxyl group-containing monomer is maleic acid. Other comonomers include alkyl vinyl esters, alkyl vinyl ethers, olefins such as ethylene, propylene, isobutene, (meth) acrylates, and styrene.
[0078]
More specifically, as described in JP-B-60-21686, JP-A-3-121107, JP-A-4-279612, JP-A-4-28707, JP-A-2-232221, and the like. Are given. The number average molecular weight (by GPC) of the copolymer is from 1,000 to 100,000, preferably from 1500 to 30,000. If the molecular weight is less than 1,000, curability and weather resistance tend to be insufficient, and if it exceeds 100,000, problems tend to occur in workability and coatability.
[0079]
More specifically, tetrafluoroethylene / alkyl vinyl ether / hydroxybutyl vinyl ether copolymer, chlorotrifluoroethylene / alkyl vinyl ether / hydroxybutyl vinyl ether copolymer, tetrafluoroethylene / alkyl vinyl ether / maleic acid copolymer And copolymers such as chlorotrifluoroethylene / alkyl vinyl ether / maleic acid copolymers, but are not limited thereto.
[0080]
The hydroxyl value of the copolymer is from 0 to 200 (mgKOH / g), and preferably from 0 to 150 (mgKOH / g). When the number of hydroxyl groups is small, curing tends to be poor, and when it exceeds 200 (mgKOH / g), a problem tends to occur in the flexibility of the coating film.
[0081]
The acid value of the copolymer is from 0 to 200 (mgKOH / g), and more preferably from 0 to 100 (mgKOH / g). When the acid value is low, curing tends to be poor, and when it exceeds 200 (mgKOH / g), a problem tends to occur in the flexibility of the coating film.
[0082]
Commercially available copolymers include, for example, Zeffle manufactured by Daikin Industries, Ltd .; Lumiflon manufactured by Asahi Glass Co., Ltd .; Zaflon and the like.
[0083]
Among the functional group-containing fluoroolefin resins (A1), examples of the fluoroolefin resin having a hydrolyzable alkyl silicate residue as a functional group include those described in JP-A-4-4246. . The number average molecular weight (by GPC) of the copolymer is from 1,000 to 100,000, preferably from 1500 to 30,000. If the molecular weight is less than 1,000, curability and weather resistance tend to be insufficient, and if it exceeds 100,000, problems tend to occur in workability and coatability.
[0084]
Specific examples include copolymers such as a copolymer containing tetrafluoroethylene / vinylmethoxysilane and a copolymer containing tetrafluoroethylene / trimethoxysilylethyl vinyl ether.
[0085]
The content of the hydrolyzable alkyl silicate residue in the copolymer is 1 to 50 mol%, preferably 5 to 40 mol%. When the amount of the hydrolyzable alkyl silicate residue is small, curing tends to be poor, and when too large, the flexibility of the coating film tends to cause a problem.
[0086]
As the functional group-containing non-fluorine acrylic resin (A2), the following acrylic polyol resin or acrylic silicone resin is preferable.
[0087]
The acrylic polyol resin may be a polymer containing, for example, the following hydroxyl-containing polymerizable unsaturated monomer (a) and, if necessary, another polymerizable unsaturated monomer (b) as a monomer component. .
[0088]
Examples of the monomer (a) include compounds represented by the following formulas (8) to (11).
[0089]
Embedded image

[0090]
[Wherein, R¹⁶Represents a hydrogen atom or a hydroxyalkyl group. ]
[0091]
Embedded image

[0092]
[Wherein, R¹⁶Is the same as above. ]
[0093]
Embedded image

[0094]
[In the formula, Z represents a hydrogen atom or a methyl group, m represents an integer of 2 to 8, p represents an integer of 2 to 18, and q represents an integer of 0 to 7. ]
[0095]
Embedded image

[0096]
Wherein Z is the same as above,₁And T₂Represents the same or different and is a divalent hydrocarbon group having 1 to 20 carbon atoms. s and v each represent an integer of 0 to 10. Here, the sum of s and v is 1 to 10. ]
[0097]
In formulas (8) and (9), the hydroxyalkyl group is a hydroxyalkyl group having 1 to 6 carbon atoms in the alkyl portion. Specifically, -C₂H₄OH, -C₃H₆OH, -C₄H₈OH and the like.
[0098]
Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in the formula (11) include, for example,
[0099]
Embedded image

[0100]
And so on.
[0101]
As the monomer component of the formula (8), for example,
CH₂= CHOH,
CH₂= CHO (CH₂)₄OH
And so on.
[0102]
As the monomer component of the formula (9), for example,
[0103]
Embedded image

[0104]
And so on.
[0105]
As the monomer component of the formula (10), for example,
[0106]
Embedded image

[0107]
And so on.
[0108]
As the monomer component of the formula (11), for example,
[0109]
Embedded image

[0110]
And so on.
[0111]
Further, in addition to the above, adducts of the hydroxyl group-containing unsaturated monomers represented by the above formulas (8) to (11) with lactones such as ε-caprolactone and γ-valerolactone can be used.
[0112]
As other polymerizable unsaturated monomers (b), the following (b-1) to (b-9) can be exemplified.
[0113]
(B-1) Olefin-based compounds: for example, ethylene, propylene, butylene, isoprene, chloroprene and the like.
[0114]
(B-2) Vinyl ether and allyl ether: for example, 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, 4-methyl-1-pentyl vinyl ether, etc. Chain alkyl vinyl ethers, cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, o-, m-, p-trivinyl ether; aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether; .
[0115]
(B-3) vinyl esters and propenyl esters; for example, vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl isocaproate, vinyl pivalate, vinyl caprate and isopropenyl acetate; Propenyl esters such as isopropenyl propionate;
[0116]
(B-4): Ester of acrylic acid or methacrylic acid: For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate C1-C18 alkyl esters of acrylic acid or methacrylic acid such as ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate; methoxybutyl acrylate; C2 to C2 of acrylic acid or methacrylic acid such as methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc. Including 8 alkoxyalkyl esters.
[0117]
(B-5) Vinyl aromatic compound: for example, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene and the like.
[0118]
(B-6) Others: acrylonitrile, methacrylonitrile, and the like.
[0119]
(B-7) Carboxyl group-containing monomer: Formula (12):
[0120]
Embedded image

[0121]
(Where R¹⁷, R¹⁸And R¹⁹Are the same or different, and each is a hydrogen atom, an alkyl group, a phenyl group, a carboxyl group or an ester group, and n is 0 or 1) or a formula (13):
[0122]
Embedded image

[0123]
(Where R²⁰And R²¹Are the same or different, each of which is a saturated or unsaturated linear or cyclic alkyl group, n is 0 or 1, and m is 0 or 1). Specific examples include, for example, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid Acids, monoesters of fumaric acid, vinyl phthalate, vinyl pyromellitate and the like can be mentioned.
[0124]
(B-8) Epoxy group-containing monomer:
[0125]
Embedded image

[0126]
(B-9) Amino-containing monomer:
[0127]
Embedded image

[0128]
The acrylic polyol resin may have a hydroxyl group, a carboxyl group, an epoxy group, or an amino group, but a hydroxyl group is particularly preferable.
[0129]
The hydroxyl value of the acrylic polyol resin is 0 to 200 (mgKOH / g), and preferably 0 to 100 (mgKOH / g). If the hydroxyl value is low, curing tends to be poor, and if it exceeds 200 (mgKOH / g), a problem tends to occur in the flexibility of the coating film.
[0130]
Examples of the acrylic polyol resin include Dianal manufactured by Mitsubishi Rayon Co., Ltd., Acridic manufactured by Dainippon Ink and Chemicals, Hitachi Chemical Co., Ltd., Hitaloid manufactured by Mitsui Toatsu Chemicals, Inc. Commercial products can be used.
[0131]
As the acrylic silicone resin, for example, a resin obtained by polymerizing the following acrylic silicone monomers together with the compounds of the formulas (8) to (11) and / or other polymerizable unsaturated monomers (b) may be used.
[0132]
The acrylic silicon monomer is a compound having at least one silane group and a radically polymerizable unsaturated group in one molecule. As the radical polymerizable unsaturated group, for example,
[0133]
Embedded image

[0134]
[Wherein, R²²Is a hydrogen atom or a methyl group]
And so on.
[0135]
Radical polymerizable unsaturated groups
[0136]
Embedded image

[0137]
Examples of the silane group-containing polymerizable unsaturated monomer include compounds represented by the following formula (14):
[0138]
Embedded image

[0139]
[Wherein, R²²Is the same as above, R²³Represents a hydrocarbon group having 1 to 20 carbon atoms, and W represents the same or different and represents a hydrogen atom, a hydroxyl group, a hydrolyzable group, an alkyl group having 1 to 8 carbon atoms, an aryl group or an aralkyl group. Provided that at least one of W is a hydrolyzable group].
[0140]
Specific examples of the compound represented by the formula (14) include, for example, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane Γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane Γ- (meth) acryloxybutylphenyldiethoxysilane, γ- (meth) acryloxybutylphenyldipropoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane , Γ- (meta Acryloxypropylphenylmethylmethoxysilane, γ- (meth) acryloxypropylphenylmethylethoxysilane, γ- (meth) acryloxypropyltrisilanol, γ- (meth) acryloxypropylmethyldihydroxysilane, γ- (meth) acryl Roxybutylphenyldihydroxysilane, γ- (meth) acryloxypropyldimethylhydroxysilane, γ- (meth) acryloxypropylphenylmethylhydroxysilane and the like can be mentioned.
[0141]
The acrylic silicone resin may further have a hydroxyl group or an epoxy group.
[0142]
As the acrylic silicone resin, for example, commercially available products such as Zemrak manufactured by Kanegafuchi Chemical Industry Co., Ltd. and Cryamar manufactured by Sanyo Chemical Industry Co., Ltd. can be used.
[0143]
As the resin (A), the functional group-containing fluoroolefin resin (A1) is more preferable in terms of better weather resistance.
[0144]
The coating composition of the present invention essentially contains the resin (A) and the silicon-containing fluorine-containing compound (B), but may contain a curing agent (C) if necessary.
[0145]
The blending amount of the silicon-containing fluorine-containing compound (B) with respect to 100 parts by weight of the resin (A) is from 10,000 to 0.5 part by weight, and a preferable lower limit is 1 part by weight, further preferably 5 parts by weight. A preferred upper limit is 9,000 parts by weight, more preferably 8,000 parts by weight. If the amount of the silicon-containing fluorine-containing compound (B) is too large, the film-forming properties are deteriorated, and the weather resistance is also reduced. If the amount is too small, the water / oil repellency tends to be poor. The blending amount of the curing agent (C) may be appropriately selected depending on the type of the curing agent, but is usually 0 to 200 parts by weight based on 100 parts by weight of the total of the resin (A) and the silicon-containing fluorine-containing compound (B). It is. A preferred upper limit is 100 parts by weight, more preferably 80 parts by weight, and a preferred lower limit is 5 parts by weight, more preferably 10 parts by weight.
[0146]
When the resin (A) has the hydrolyzable silicate group, the resin (A) can be sufficiently mixed with the hydrolyzable alkyl silicate residue in the silicon-containing fluorine-containing compound (B) even if the curing agent (C) is not particularly blended. An effect response can be achieved.
[0147]
When the functional group of the resin (A) is, for example, a hydroxyl group, it is preferable to incorporate a curing agent (C).
[0148]
Preferred curing agents (C) include isocyanate compounds and / or Si (OR⁹)₄(R⁹Is a non-fluorinated alkyl group having 1 to 10 carbon atoms), R¹⁰Si (OR¹¹)₃(R¹⁰And R¹¹Are the same or different, and include at least one selected from the group consisting of non-fluorinated alkyl groups having 1 to 10 carbon atoms), homo-condensed oligomers thereof, and co-condensed co-oligomers thereof.
[0149]
The isocyanate compound also includes a blocked isocyanate compound, and specific examples thereof include, for example, 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, Trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, trimers thereof, adducts and burettes thereof, polymers having two or more isocyanate groups, and further blocks But is not limited thereto.
[0150]
Also, an isocyanate compound having a hydrolyzable alkyl silicate residue can be preferably used.
[0151]
Examples of the hydrolyzable alkyl silicate residue include -SiR⁶ _3-m(OR⁷)_m(Where R⁶Is a non-hydrolyzable hydrocarbon group which may contain a fluorine atom having 1 to 18 carbon atoms; R⁷Is a hydrocarbon group having 1 to 18 carbon atoms; m is an integer of 1 to 3). As the silicon-containing functional group, those described for the resin (A) are preferable.
[0152]
Specific examples of isocyanate compounds having a hydrolyzable alkyl silicate residue include, for example, OCNC₃H₆Si (OCH₃)₃, OCNC₃H₆Si (OC₂H₅)₃, OCNC₃H₆Si (OCOCH₃)₃, OCNC₃H₆Si (CH₃) (OCH₃)₂And so on.
[0153]
The mixing ratio of the isocyanate compound and the resin (A) is preferably 0.5 to 5.0, more preferably 0.8 to 1.2, in NCO / OH (molar ratio). When the isocyanate is a moisture-curable type, the ratio is preferably 1.1 to 1.5.
[0154]
As the curing agent (C), instead of or in addition to the isocyanate compound, Si (OR⁹)₄(R⁹Is a non-fluorinated alkyl group having 1 to 10 carbon atoms), R¹⁰Si (OR¹¹)₃(R¹⁰And R¹¹May be the same or different, and at least one selected from the group consisting of a non-fluorinated alkyl group having 1 to 10 carbon atoms), a homocondensed oligomer thereof, and a co-condensed co-oligomer thereof may also be used.
[0155]
As these tetrafunctional or trifunctional non-fluorinated alkyl silicates, those described in, for example, US Pat. No. 5,635,572 can be used.
[0156]
Specific examples include tetraalkoxysilane or a condensate thereof, alkyltrialkoxysilane or a condensate thereof, polysilsesquioxane, colloidal silica, and the like.
[0157]
Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane and condensates thereof, and commercially available products such as MS51, MS56, and MS57 manufactured by Mitsubishi Chemical Co., Ltd. Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 and the like can be used.
[0158]
Examples of the polysilsesquioxane include polyphenylsilsesquioxane, polymethylsilsesquioxane, polyhydrogensilsesquioxane, and the like.
[0159]
As the colloidal silica, for example, Snowtex manufactured by Nissan Chemical Co., Ltd. can be used.
[0160]
Among these, a condensate of tetraalkoxysilane is preferable because a strong coating having a high crosslinking density can be formed.
[0161]
The amount of the silicate-based curing agent may be appropriately selected depending on the type of the curing agent, but is usually 0 to 100 parts by weight based on the total of 100 parts by weight of the resin (A) and the silicon-containing fluorine-containing compound (B). It is. A preferred upper limit is 50 parts by weight, and a preferred lower limit is 10 parts by weight.
[0162]
In the present invention, a curing catalyst may be added in addition to the curing agent.
[0163]
As the curing catalyst, for example, an organotin compound, an organic acid phosphate, an organic titanate compound, a reaction product of an acid phosphate and an amine, a saturated or unsaturated polyvalent carboxylic acid or an acid anhydride thereof, an organic sulfonic acid, Examples include amine compounds, aluminum chelates, titanium chelates, and zirconium chelates.
[0164]
Specific examples of the organotin compound include dibutyltin dilaurate, dibutyltin maleate, dioctyltin maleate, dibutyltin diacetate, and the like.
[0165]
As specific examples of the organic acid phosphate,
[0166]
Embedded image

[0167]
And so on.
[0168]
Examples of the organic titanate compound include titanates such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate.
[0169]
Further, specific examples of the amine compound include, for example, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine. Amine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,8-diazabicyclo (5.4.0) undecene-7 (DBU), etc. Amine compounds, furthermore salts thereof such as carboxylic acids, low molecular weight polyamide resin obtained from excess polyamine and polybasic acid, excess polyamine and epoxy compound Such as the reaction product, and the like.
[0170]
Specific examples of the chelate compound include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), zirconium tetrakis (acetyl acetonate), diisopropoxy bis (ethyl acetoacetate) titanate, and the like.
[0171]
One curing catalyst may be used, or two or more curing catalysts may be used in combination. Preferred curing catalysts include organotin compounds and aluminum chelate compounds. The amount of the curing catalyst is from 0 to 10 parts by weight, preferably from 0.001 to 5 parts by weight, based on 100 parts by weight of the resin (A), the silicon-containing fluorine-containing compound (B) and the curing agent (C) in total. is there.
[0172]
In the present invention, an organic solvent can be added to the coating composition.
[0173]
Examples of the organic solvent include hydrocarbon solvents such as xylene, toluene, Solvesso 100, Solvesso 150, and hexane; methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monoacetate. Ethyl solvents such as butyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol acetate, diethylene glycol acetate, dimethyl ether, diethyl ether, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monobutyl ether, ethylene glycol dye Ether solvents such as ethylene ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetrahydrofuran, etc., methyl ethyl ketone, methyl isobutyl ketone, acetone Amide solvents such as ketone solvents such as N, N-dimethylacetamide, N-methylacetamide, acetamide, N, N-dimethylformamide, N, N-diethylformamide and N-methylformamide, and sulfonic acids such as dimethylsulfoxide Ester solvents, methanol, Ethanol, isopropanol, butanol, ethylene glycol, diethylene glycol, polyethylene glycol (polymerization degree of 3 to 100), CF₃CH₂OH, F (CF₂)₂CH₂OH, (CF₃)₂CHOH, F (CF₂)₃CH₂OH, F (CF₂)₄C₂H₅OH, H (CF₂)₂CH₂OH, H (CF₂)₃CH₂OH, H (CF₂)₄CH₂Examples thereof include alcoholic solvents such as OH, and alcoholic solvents such as lower alcohols and lower fluorine alcohols are preferable from the viewpoint of compatibility, appearance of the coating film, and storage stability.
[0174]
Regarding the mixing ratio of the resin (A) and the alcohol-based solvent, the alcohol is 1 to 50 parts by weight with respect to 100 parts by weight of the resin (A), and 1 to 25 parts by weight in terms of curability and coating film appearance. Is more preferable.
[0175]
When the curing agent is highly reactive with alcohol, such as a room temperature-curable isocyanate, the alcohol is preferably 1 to 15 parts by weight, and the type of alcohol is preferably a secondary or tertiary alcohol. .
[0176]
The coating composition of the present invention has excellent solvent solubility, and the formed coating film has a high degree of weather resistance, and has anti-staining and adhesion properties, especially oil-based stain removal (removal of graffiti), chemical resistance, and optical properties. It has excellent mechanical properties, mechanical properties, adhesion to a substrate, heat-resistant yellowing, and the like. In addition, the composition may be used as a general hardening composition for building materials, interior materials such as interior or building materials, automobiles, aircraft, ships, trains, and other outdoor paints such as metals, concrete, plastics, and the like, or directly. It can be applied over the undercoat such as wash primer, rust preventive paint, epoxy resin, acrylic resin paint and polyester resin paint. Further, it can be used as a sealing agent or a film forming agent.
[0177]
The coating composition may take various forms such as clear, solid, and compounding of a filler.
[0178]
Regarding the coating method, various methods such as spraying, brushing, roller, curtain flow, roll, and dipping are used.
[0179]
The coating composition of the present invention includes, for example, a pigment, a pigment dispersant, a thickener, a leveling agent, a defoaming agent, a film forming aid, an ultraviolet absorber, a HALS, a matting agent, a filler, a colloidal silica, and a fungicide. , Coating additives such as silane coupling agent, anti-skinning agent, antioxidant, flame retardant, anti-sagging agent, antistatic agent, rust inhibitor, water-soluble resin (polyvinyl alcohol, polyethylene oxide, etc.) You can also.
[0180]
Examples of the pigment include titanium oxide, iron oxide, aluminum metallic pigment, carbon black, calcined pigment, phthalocyanine pigment, organic pigment, extender pigment and the like.
[0181]
Examples of the titanium oxide include Taipaque CR-90, CR-93, CR-95, and CR-97 manufactured by Ishihara Sangyo Co., Ltd.
[0182]
Examples of the iron oxide include Todacolor 120ED, 140ED, 160ED, KN-R, and KN-V manufactured by Toda Kogyo Co., Ltd., and LL-XLO, HY-100, HY-200, and BL-TAROX manufactured by Titanium Industry Co., Ltd. 100, BL-500 and the like.
[0183]
Examples of the aluminum metallic pigment include Alpaste 0100MA, 0700M, 0200M, 0215M, 1950M, 1900M, 1100M, 1109M, 1200M, 8820YF, 7080N, MG600, and 1700N manufactured by Toyo Aluminum Co., Ltd.
[0184]
Examples of the carbon black include MA7, MA11, MA100, OIL7B, OIL30B, and OIL31B manufactured by Mitsubishi Chemical Corporation.
[0185]
Examples of the calcined pigment include Dipiroxide # 9510, # 9512, # 9410, # 9310 manufactured by Dainichi Seika Co., Ltd.
[0186]
Examples of the phthalocyanine pigment include # 5195N and # 5370 manufactured by Dainichi Seika Co., Ltd.
[0187]
Examples of the extender pigments include asbestos, calcium carbonate, precipitated calcium carbonate, clay, kaolin, porcelain earth, aluminum silicate, diatomaceous earth, white carbon, silica white, hydrated fine silica, bentonite, talc, magnesium silicate, magnesium carbonate, barite Powder, barium sulfate, precipitated barium sulfate, and the like.
[0188]
As the pigment dispersant, for example, Anti-Terra-P, Anti-Terra-U, Anti-Terra-203 / 204, Disperbyk, Disperbyk-101, Disperbyk-110, Disperbyk130, Disperbyk161 -164, Disperbyk-170, Bykumen, BYK-P104 / P105, BYK-104S, BYK-240S, Lactimon and the like.
[0189]
Examples of the leveling agent include BYK-300, BYK-302, BYK-306, BYK-307, BYK-335, BYK-310, BYK-320, BYK-322, and BYK-323 manufactured by BYK Japan KK. BYK-324, BYK-325, BYK-330, BYK-331, BYK-333, BYK-344, BYK-370, BYK-354, BYK-355, BYK-358 and the like.
[0190]
Examples of the thickener include Disparon # 6900-20X, # 6900-10S, # 4200-20, # 4200-10 manufactured by Kusumoto Kasei Co., Ltd., Benton SD-1 and SD-2 manufactured by NL Chemicals Co., Ltd. SD-3, # 27, # 34, # 38, MPA-2000X and the like.
[0191]
Examples of the defoaming agent include BYK-051, BYK-052, BYK-053, BYK-055, BYK-057, BYK-065, BYK-066, BYK-070, and BYK-077 manufactured by BYK Japan KK. , BYK-080, BYK-088, BYK-141 and the like.
[0192]
As the ultraviolet absorber, for example, benzophenone-based and benzotriazole-based ones are preferable. Among these, benzophenone-based ones are 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and 2,2'-dihydroxy. 4-methoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone are 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy- 5'-methylphenyl) -5,6-dichlorobenzotriazole), 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'- Di-tert-butylphenyl) -5-chloro-benzotriazole, 2- (2′-hydroxy -5'-phenylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tertbutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'- Ditertbutylphenyl) benzotriazole and 2- (2'-hydroxy-5'-tertoctylphenyl) benzotriazole are effective.
[0193]
Particularly suitable UV absorbers have the formula:
[0194]
Embedded image

[0195]
(Where R²⁴And R²⁵Are the same or different, each represents a hydrogen atom, a lower alkyl group, especially a branched lower alkyl group or an aryl group, particularly a phenyl group, and X is a hydrogen atom or a halogen atom, particularly a chlorine atom.
It is shown by.
[0196]
Examples of the HALS include Tinuvin-770, 292, 622123, and 440 manufactured by Ciba-Geigy Corporation.
[0197]
Examples of the matting agent include Hoechst Wax PE520, white carbon, and the like, such as Seridust # 3620, # 9615A, # 9612A, # 3715, and # 3910 manufactured by Hoechst Industry Co., Ltd.
[0198]
Examples of the silane coupling agent include methyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, vinyltrimethoxysilane, 3- (glycidyloxy) propyltrimethoxysilane, N- (2-aminoethyl ) -3-Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylisocyanate, 3-triethoxysilylpropylisocyanate, Methyltris (ethylmethylketoxime) silane and the like are preferable, and those containing an alkylketoxime group or an isocyanate group are preferable.
[0199]
The coating composition of the present invention can be applied to various substrates, and examples of the substrate to be coated include metal-based substrates, cement-based substrates, and plastic-based substrates.
[0200]
Examples of the metal-based substrate include iron and its chemical conversion products or plating products, aluminum and its chemical conversion products, stainless steel and its chemical conversion products, and the like.
[0201]
Examples of the cement-based substrate include cements, limes, gypsum, concrete, cement mortar, asbestos slate, gypsum board and the like.
[0202]
Examples of the plastic base material include polyvinyl chlorides, polyesters, polycarbonates, acrylics, polyolefins, polystyrenes, polyurethanes, polyamides, nylons, natural rubbers, urethane rubbers, ABS resins, and the like. Is raised.
[0203]
When the substrate is a metal-based substrate, it is preferable to apply the coating composition of the present invention after applying, for example, the following undercoat paint or intermediate paint, from the viewpoint of anticorrosion properties and phase adhesion. .
[0204]
In this case, a zinc-rich paint is preferred as the undercoat.
[0205]
Examples of the vehicle of the organic zinc-rich paint include a combination of an epoxy resin and a polyamide resin, a chlorinated rubber, a polystyrene resin, and a silicone resin. Examples of vehicles for inorganic zinc-rich paints include ethyl silicate, sodium silicate, lithium silicate, potassium silicate, and ammonium silicate. Particularly preferred vehicles for the purposes of the present invention are epoxy resin-polyamide resin combinations, ethyl silicate, potassium silicate, lithium silicate.
[0206]
Other examples of the undercoat paint and the intermediate paint are preferably selected from epoxy resins (including tar-modified and urethane-modified), vinyl resins (including tar-modified and acrylic resins), chlorinated rubber, polyurethane resins, and phenol resins. A paint obtained by kneading at least one kind of synthetic resin with a commonly used coloring pigment, extender pigment, suspending agent, dispersant, curing agent, curing accelerator, diluent, solvent and the like.
[0207]
The epoxy resin is a resin having two or more epoxy groups in a molecule and usually used for paint.
[0208]
Among the epoxy resins, for example, bisphenol-type epoxy resins are commercially available under the trade names Epicoat 828, 834, 836, 1001, 1004, DX-255, and Ciba Geigy Co., Ltd. Araldite GY-260, trade names DER330, 331, 337 manufactured by Dow Chemical Co., Ltd., and Epicron 800 trade name, manufactured by Dainippon Ink and Chemicals, Inc. The phenol novolak type epoxy resin is generally commercially available under the trade name DEN431, 438 manufactured by Dow Chemical Co., Ltd. The polyglycol type epoxy resin is commercially available under the trade name Araldite CT-508 manufactured by Ciba Geigy Co., Ltd. And DER-732, 736 (trade name, manufactured by Dow Chemical Co., Ltd.). Examples of the ester-type epoxy resin include, for example, Epicron 200, 400 (trade name) manufactured by Dainippon Ink and Chemicals, Inc .; Examples of the linear aliphatic epoxy resin include, for example, BF-1000 (trade name) manufactured by Nippon Soda Co., Ltd. And epoxidized polybutadiene.
[0209]
Further, epoxy compounds which can be easily inferred from these resins, and derivatives of the epoxy resins, can also be used, and are included in the technical scope of the present invention.
[0210]
For example, a polyol type epoxy resin, an alicyclic epoxy resin, a halogen-containing epoxy resin and the like are included.
[0211]
Bituminous substances such as natural asphalt, asphaltite, asphalt pyrobitumen, tar, coal tar, artificial asphalt, and pitch can be mixed with the epoxy resin.
[0212]
As the curing agent for the epoxy resin, those usually used for coating materials such as an amine adduct and a polyamide resin can be used.
[0213]
Among the above-mentioned curing agents, for example, as a polyamide resin, commercially available tomide Y-25, 245, 2400, 2500 manufactured by Fuji Kasei Kogyo Co., Ltd., trade names Zenamide 2000, Versamide 115 manufactured by Daiichi General Co., Ltd. , 125, trade names Sunmide 320, 330, X2000 manufactured by Sanwa Chemical Co., Ltd., epicures 3255, 4255 manufactured by Shell Chemical Co., Ltd., and tomide 238, Fuji Cure 202, manufactured by Fuji Chemical Industry Co., Ltd. as an amine adduct resin. And Adeka Hardener EH-531 (trade name, manufactured by Asahi Denka Co., Ltd.). As aliphatic polyamines, trade names Sunmide T-100, D-100, P-100 manufactured by Sanwa Chemical Co., Ltd., and as heterocyclic diamine derivatives, Epomate B-002, C-002, S-005 manufactured by Ajinomoto Co., Inc. And so on.
[0214]
The amount of the curing agent added to the epoxy resin is around the equivalent, that is, about 0.7 to 1.3 equivalents per equivalent of the epoxy resin.
[0215]
Further, polyisocyanate can also be used as a curing agent for the epoxy resin.
[0216]
Examples of the vinyl resin used in the present invention include vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, styrene, vinyl toluene, vinyl alcohol, acrylic acid, methacrylic acid, maleic anhydride, alkyl acrylate, and methacrylic acid. It is a copolymer of one or more monomers such as acid alkyl esters, and examples thereof include vinyl chloride resins, vinyl chloride-vinyl acetate copolymer resins, and acrylic resins.
[0217]
The chlorinated rubber resin used in the present invention is a chlorinated product of natural rubber and is usually a compound having a chlorine content of 65 to 68%.
[0218]
The chlorinated rubber can be used as a mixture with rosin, coumarone-indene resin, phenol resin, vinyl chloride resin, petroleum resin, nitrile rubber, chloroprene rubber, and alkyd resin.
[0219]
The chlorinated rubber is used by being mixed with a plasticizer such as paraffin chloride, diphenyl chloride, dioctyl phthalate, and tricresyl phosphate.
[0220]
Further, the polyurethane resin used in the present invention is a compound having two or more active hydrogens in a molecule, for example, a polyester polyol, a polyether polyol, a polyoxyalkylene glycol, an acrylic polyol obtained from a polybasic acid and a polyhydric alcohol. And the like are main agents, and the above-mentioned composition is a curing agent of a polyisocyanate having two or more isocyanate groups in a molecule.
[0221]
When the substrate is a cement-based substrate, it is preferable to apply the coating composition of the present invention after applying, for example, the following undercoat or intermediate coating.
[0222]
As the undercoat paint, use a multi-layer paint such as uncured synthetic resin emulsion-based multi-layer paint, reaction-curable water-soluble epoxy resin multi-layer paint, and a reaction-curable solvent-based epoxy resin multi-layer paint. Is particularly preferred. The resin components of the uncured synthetic resin emulsion include, for example, acrylic resins, vinyl acetate resins, and modified resins thereof. Examples of the reaction-curable aqueous or solvent-based epoxy resin curing system include, for example, an epoxy-polyamine system, an epoxy-polyamide system, and an epoxy-polyamine polyamide system.
[0223]
The method of applying the undercoat paint to the cement base material can be performed by, for example, spray coating, roller coating, or the like. The application amount is usually 0.5 to 2.0 kg / m²Seems to be enough. The drying is generally performed for 1 to 3 days.
[0224]
Before the undercoat paint is applied to the cement-based substrate, a conventionally known primer, surfacer sealer, or the like generally used for architectural foundation treatment can be applied. In addition to the above-mentioned undercoat paints, there are included those obtained by directly or applying the sealer to a sealer such as a solvent-type epoxy resin, and then performing a smooth finish with an isocyanate-curable resin paint.
[0225]
The method of applying the coating composition of the present invention to an undercoat film can be performed by, for example, roller coating, brush coating, spray coating, or the like. The application amount is 0.05-0.5kg / m², Preferably 0.1 to 0.3 kg / m²It is. As for drying, a cured coating film can be formed by drying at room temperature for one day or more.
[0226]
As a renovation coating method, a method of applying a coating composition of the present invention and performing a renovation after performing a base treatment as needed on an old overcoating film of a building exterior coating film applied on a cement base material. is there.
[0227]
In the above method, as the old top coat, a curable fluorine paint, a curable acrylic paint, an acrylic silicone paint, a carbonyl-hydrazide curable water-based paint, such as, but not limited to, those used in the paint composition of the present invention, A coating film formed by a non-crosslinked solvent-based paint such as a vinyl acetate-modified acrylic resin-based paint or a non-crosslinked aqueous paint such as an acrylic resin-based water-based paint is particularly preferred.
[0228]
Examples of the carbonyl-hydrazide-curable aqueous paint include a paint obtained by blending a dihydrazide crosslinking agent and an aqueous polyurethane resin having a hydrazine residue with an aqueous dispersion of a carbonyl group-containing copolymer (for example, Japanese Patent Application No. 4-171683). Gazette). A primer and a surfacer may be coated between the old top coat and the cement-based substrate, and a multilayer coating material may be further coated on the primer and the surfacer.
[0229]
The undercoat treatment performed on the old top coat as required can be carried out, for example, by applying the following undercoat agent. Preferred examples of the base treating agent include cement-based (eg, cement / synthetic resin emulsion-based) fillers or surfacers, and reaction-curable resin-based (eg, epoxy polyamine-based, epoxy polyamide-based) penetrating sealers, and the like. Can be
[0230]
The undercoating method can be carried out by applying the undercoating agent with, for example, a roller or a brush. The amount of the base treatment agent applied is, for example, 0.3 to 2.0 kg / m2 for a filler.², 0.1 ~ 1.0kg / m for surfacer², 0.01-0.5kg / m for penetration type sealer²Think that is enough.
[0231]
In addition, after applying these undercoating agents, a polyisocyanate-curable solvent-based paint can be further applied. The application of the paint can be performed by, for example, a roller, a brush, or spraying. Moreover, the application amount is 0.05 to 0.5 kg / m.²Think that is enough. Drying of the undercoating agent and the polyisocyanate-curable solvent-based paint is usually performed 1 to 3 times. The coating and drying of the coating composition of the present invention can be carried out in the same manner as in the case of the coating composition of the present invention.
[0232]
Even when the substrate is a plastic substrate, the coating composition of the present invention can be applied after applying the undercoat or intermediate coating used for the metal substrate or cement substrate.
[0233]
When the base material is a film or sheet among plastic base materials, examples of the coating method include a gravure coating method, a doctor blade method, a roll coating method, a reverse roll method, and an air knife coating method. In the case of these coating methods, the coating film thickness is suitably from 1 to 20 μm, preferably from 1 to 10 μm, from the viewpoint of coating film appearance and coatability.
[0234]
Examples of uses of the article coated with the coating composition of the present invention include, for example, architectural waterproofing sheet, tunnel waterproofing sheet, agricultural vinyl sheet, agricultural vinyl film, curing sheet, architectural protective sheet, vehicle protective sheet, Mesh sheet, mesh screen, polycarbonate roof, acrylic board wall, polycarbonate wall, guardrail, traffic light, tunnel inner wall, tunnel interior board, road sign, information board, highway side wall, highway noise barrier, road light, bridge, bridge girder, pier , Chimneys, wallpapers, tatami mats, mats, tablecloths, ventilation fans, marking films, geomembranes, billboards, post boxes, telephone poles, tents, automobiles, aircraft, ships, trains and the like.
[0235]
【Example】
Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. “Parts” in Examples and Production Examples are parts by weight.
[0236]
Example 1
To 100 parts of Zeffle GK-510 (hydroxyl-containing tetrafluoroethylene copolymer; hydroxyl value 60 mg KOH / g, acid value 9 mg KOH / g, number average molecular weight 12000, butyl acetate solution, solid content 50%), and OCN- C₃H₆-Si (OCH₃)₃And 5 parts of Coronate HX (an isocyanate-based curing agent manufactured by Nippon Polyurethane Co., Ltd.) were added.₈F₁₇CH₂CH₂Si (OCH₃)₃Of butyl acetate and 50 parts of butyl acetate were added and stirred well to obtain a coating composition of the present invention.
[0237]
This coating composition was spray-coated on a slate flexible board (7 × 15 × 0.3 cm; manufactured by Nippon Test Panel Co., Ltd.) at 200 g / m 2.²And dried at room temperature for one week to obtain a coated plate.
[0238]
The following tests were performed on this coated plate. Table 1 shows the results.
[0239]
Oil-based ink contamination test:
The red color of an oil-based ink (Magic Ink, a registered trademark of Uchida Yoko Co., Ltd.) made by Magic Co., Ltd. was applied to the coated plate, left for 24 hours, and then wiped off with a paper towel impregnated with ethyl alcohol. The residual rate is evaluated according to the following criteria.
A: Less than 5%
B: 5 to 15%
C: more than 15% and less than 30%
D: Over 30%
[0240]
Automotive oil pollution test:
The painted plate is painted with waste mission oil of a car and left for 24 hours, then wiped off with a dry paper towel, and the remaining rate of the area not wiped is evaluated according to the following criteria.
A: Less than 5%
B: 5 to 15%
C: more than 15% and less than 30%
D: Over 30%
[0241]
Lacquer contamination test:
A red lacquer spray manufactured by Kansai Paint Co., Ltd. is spray-painted, left for 24 hours, and then wiped off with a paper towel impregnated with methyl ethyl ketone.
A: Less than 5%
B: 5 to 15%
C: more than 15% and less than 30%
D: Over 30%
[0242]
Weather resistance test:
According to JIS K5400, using a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.), an accelerated weathering test for 500 hours is performed, and then the above oil-based ink contamination test is performed.
[0243]
Adhesion test:
A grid test is performed according to JIS K5400. In the case of a flexible board, the grid is 4 mm wide, and in the case of other coated boards, the grid is 1 mm wide.
[0244]
The cross-cut test is performed after coating (initial stage) and on a coated plate immersed in boiling water at 100 ° C. for 2 hours, pulled up, and cooled (after boiling water test).
[0245]
For the adhesion test, in addition to the flexible board, glass plate, natural granite (produced in China, obtained from Nittai Industry Co., Ltd.) and aluminum plate (A1050P (AM712 treatment, manufactured by Nippon Test Panel Co., Ltd.)) were used as the objects to be coated. The coating composition was spray-coated at 200 g / m.²The test was also performed on a coated plate which was coated at a coating amount of 1 and dried at room temperature for one week.
[0246]
Production Example 1 (Production of resin (A1))
4. 200 g of butyl acetate, 29.5 g of vinyltrimethoxysilane (TMVS), 20.0 g of n-butyl vinyl ether (nBVE), and 2,2'-azobis (2,4-dimethylvaleronitrile) in a 1000 ml stainless steel autoclave. After charging 0 g and cooling with ice at 0 ° C., the mixture was degassed under reduced pressure. To this, 33.5 g of isobutylene (IB) and 100 g of tetrafluoroethylene (TFE) were charged, heated to 50 ° C. with stirring, and reacted for 28 hours. When the pressure in the reactor dropped from 1.4 MPaG to 1 MPaG, the reaction was started. Was stopped (yield 24.6%). The resulting hydrolyzable alkyl silicate group-containing fluorinated copolymer,¹⁹F-MNR,¹As a result of analysis by H-MNR and elemental analysis, TFE / IB / nBVE / TMVS = 45/40/8/7 mol%, the number average molecular weight measured by GPC was 3900, and the glass transition temperature measured by DSC was: -21 ° C.
[0247]
Production Example 2 (Production of silicon-containing fluorine-containing high molecular weight compound (B2))
CF was placed in a 500 ml four-necked flask equipped with a stirrer, an inert gas inlet, a reflux condenser, and a thermometer.₃CF₂(CF₂CF₂)_nCH₂CH₂OCOCH = CH₂(A mixture of 86 and 14 weight ratio of n = 3 and 4) 26.0 g, stearyl acrylate 13.0 g, γ-methacryloxypropyltrimethoxysilane 1.0 g and butyl acetate 120 g were added. 0.3 g of azobisisobutyronitrile was added, and polymerization was carried out at 70 ° C. with stirring for 12 hours. The polymerization conversion measured by gas chromatography was 97% or more.
[0248]
The obtained silicon-containing fluorine-containing high molecular weight compound had a number average molecular weight of 10,000 as measured by GPC.
[0249]
Butyl acetate was added to the polymerization reaction solution to adjust the solid concentration to 25% by weight.
[0250]
Example 2
To 100 parts of Zeffle GK-510, 12 parts of coronate HX was added as a curing agent, 100 parts of the silicon-containing fluorine-containing high molecular weight compound obtained in Production Example 2 and 50 parts of butyl acetate were added, and the mixture was stirred well. A coating composition of the present invention was obtained.
[0251]
This coating composition was spray-coated on a flexible board (7 × 15 × 0.3 cm) at 200 g / m 2.²And dried at room temperature for one week to obtain a coated plate.
[0252]
The same test as in Example 1 was performed on this coated plate. Table 1 shows the results.
[0253]
In the adhesion test, the coating composition was spray-coated on a glass plate, natural granite, or aluminum plate as an object to be coated at 200 g / m 2.²The test was also performed on a coated plate which was coated at a coating amount of 1 and dried at room temperature for one week.
[0254]
Example 3
In 100 parts of Zeffle GK-510, OCN-C is used as a curing agent.₃H₆-Si (OCH₃)₃Was added, and 5 parts of the silicon-containing fluorine-containing high molecular weight compound obtained in Production Example 2 and 50 parts of butyl acetate were added, and the mixture was stirred well to obtain a coating composition of the present invention.
[0255]
This coating composition was spray-coated on a flexible board (7 × 15 × 0.3 cm) at 200 g / m 2.²And dried at room temperature for one week to obtain a coated plate.
[0256]
The same test as in Example 1 was performed on this coated plate. Table 1 shows the results.
[0257]
In the adhesion test, the coating composition was spray-coated on a glass plate, natural granite, or aluminum plate as an object to be coated at 200 g / m 2.²The test was also performed on a coated plate which was coated at a coating amount of 1 and dried at room temperature for one week.
[0258]
Example 4
To 100 parts of the resin (A1) obtained in Production Example 1, 100 parts of the silicon-containing fluorine-containing high molecular weight compound obtained in Production Example 2, 0.1 part of dibutyltin dilaurate as a curing accelerator and 50 parts of butyl acetate were added. In addition, the mixture was stirred well to obtain a coating composition of the present invention.
[0259]
This coating composition was spray-coated on a flexible board (7 × 15 × 0.3 cm) at 200 g / m 2.²And dried at room temperature for one week to obtain a coated plate.
[0260]
The same test as in Example 1 was performed on this coated plate. Table 1 shows the results.
[0261]
In the adhesion test, the coating composition was spray-coated on a glass plate, natural granite, or aluminum plate as an object to be coated at 200 g / m 2.²The test was also performed on a coated plate which was coated at a coating amount of 1 and dried at room temperature for one week.
[0262]
Comparative Example 1
To 100 parts of Zeffle GK-510, 12 parts of Coronate HX was added as a curing agent, and the mixture was stirred well to obtain a paint composition for comparison.
[0263]
This coating composition was spray-coated on a flexible board (7 × 15 × 0.3 cm) at 200 g / m 2.²And dried at room temperature for one week to obtain a coated plate.
[0264]
The same test as in Example 1 was performed on this coated plate. Table 1 shows the results.
[0265]
In the adhesion test, the coating composition was spray-coated on a glass plate, natural granite, or aluminum plate as an object to be coated at 200 g / m 2.²The test was also performed on a coated plate which was coated at a coating amount of 1 and dried at room temperature for one week.
[0266]
Comparative Example 2
C₈F₁₇CH₂CH₂Si (OCH₃)₃Was mixed with 90 parts of butyl acetate, and 0.1 part of dibutyltin dilaurate was further added and stirred to obtain a coating composition for comparison.
[0267]
This coating composition was spray-coated on a flexible board (7 × 15 × 0.3 cm) at 200 g / m 2.²And dried at room temperature for one week to obtain a coated plate.
[0268]
The same test as in Example 1 was performed on this coated plate. Table 1 shows the results.
[0269]
In the adhesion test, the coating composition was spray-coated on a glass plate, natural granite, or aluminum plate as an object to be coated at 200 g / m 2.²The test was also performed on a coated plate which was coated at a coating amount of 1 and dried at room temperature for one week.
[0270]
[Table 1]

[0271]
【The invention's effect】
According to the coating composition of the present invention, since it is excellent in prevention of contamination, particularly excellent in removing oily stains, it can be easily wiped and removed even if graffiti is made, and it is also excellent in weather resistance and adhesion, so that it can be used for various kinds of outdoor coating. Ideal for

Claims (9)

(A) a functional group-containing fluoroolefin resin and / or a functional group-containing non-fluorinated acrylic resin, and (B) (B1) Formula (1):
RfSi (OR ¹ ) _n (R ² ) _3-n (1)
(In the formula, Rf is a linear or branched non-hydrolyzable fluoroalkyl group having 3 to 20 carbon atoms, which may contain a functional group, and an oxygen atom and / or a nitrogen atom in the middle. R ¹ may be a non-fluorinated alkyl group having 1 to 10 carbon atoms, —N ＝ CR ³ R ⁴ or —C (＝ O) R ⁵ (where R ³ , R ⁴ and R ⁵ are the same) or different and each is a non-fluorinated alkyl group having 1 to 10 carbon atoms); ^{R 2} is a hydrogen atom, a non-fluorinated alkyl group or Rf having 1 to 10 carbon atoms; silicon-containing free represented by n is an integer of 1 to 3) Fluorine low molecular weight compound, and (B2) Formula (2):
YSi (OR ¹ ) _n (R ² ) _3-n (2)
(Wherein, Y is a non-hydrolyzable and non-functional fluoroolefin copolymer radical having 21 or more carbon atoms, a fluorine-containing acryl having 21 or more carbon atoms and optionally containing a functional group) Copolymer radical, fluorinated polyether radical having 21 or more carbon atoms and optionally containing a functional group, fluorinated polyester radical having 21 or more carbon atoms and optionally containing a functional group or 21 or more carbon atoms Wherein R ¹ , R ² and n are the same as defined above, and at least one silicon-containing fluorine-containing high molecular weight compound selected from the group consisting of silicon-containing fluorine-containing high molecular weight compounds A coating composition containing a fluorine-containing compound. The coating composition according to claim 1, wherein the functional group of the resin (A) is a hydroxyl group or a hydrolyzable alkyl silicate residue. The coating composition according to claim 2, wherein the resin (A) is a fluoroolefin resin having a hydrolyzable alkyl silicate residue and does not contain a curing agent. The hydrolyzable alkyl silicate _{^{residue, -SiR 6 3-m (OR}} 7) m ( wherein, ^{R 6} is a hydrocarbon group having 1 to 18 fluorine atoms may contain a non-hydrolyzable carbon R ⁷ is a hydrocarbon group having 1 to 18 carbon atoms; m is an integer of 1 to 3). 5. The coating composition according to claim 1, further comprising (C) a curing agent. The curing agent (C) is an isocyanate compound and / or Si (OR ⁹ ) ₄ (R ⁹ is a non-fluorinated alkyl group having 1 to 10 carbon atoms), R ¹⁰ Si (OR ¹¹ ) ₃ (R ¹⁰ and R ¹¹ are The coating composition according to claim 5, which is at least one selected from the group consisting of the same or different, non-fluorinated alkyl groups having 1 to 10 carbon atoms), homo-condensed oligomers thereof, and co-condensed co-oligomers thereof. The coating composition according to claim 5, wherein the curing agent (C) is an isocyanate compound having a hydrolyzable alkyl silicate residue. The coating composition according to claim 5, wherein the resin (A) is a hydroxyl group-containing fluoroolefin resin, and the curing agent (C) is an isocyanate compound having a hydrolyzable alkyl silicate residue. The hydrolyzable alkyl silicate _{^{residue, -SiR 6 3-m (OR}} 7) m ( wherein, ^{R 6} is a hydrocarbon group having 1 to 18 fluorine atoms may contain a non-hydrolyzable carbon ; R ⁷ is a hydrocarbon group having 1 to 18 carbon atoms; m is claim 7 or 8 coating composition wherein the silicon-containing functional group represented by an integer of 1 to 3).