JP3724597B2 - Liquid curable resin composition - Google Patents

Description

【０１３７】
〔ただし、Ｒは１価の有機基を表わすものとし、しかも、３個の酸素原子は、それぞれ、珪素原子に結合しているものとする。〕
【０１３８】
上掲の一般式［Ｉ］において、１価の有機基である「Ｒ」として特に代表的なもののみを例示するにとどめれば、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基もしくはｎ−オクチル基の如き、Ｃ₁ 〜Ｃ₈ なる種々のアルキル基；
【０１３９】
フェニル基もしくはｐ−トリル基の如き、各種のアリール基；または１−フェネチル基もしくは２−フェネチル基の如き、各種のアラルキル基などのような、種々のアリール基を有する基；
【０１４０】
あるいはビニル基または３−メタアクリロイルオキシ基の如き、各種の重合性二重結合を有する基などをはじめ、さらには、３−グリシドキシプロピル基もしくは２−（３，４−エポキシシクロヘキシル）エチル基の如き、各種のエポキシ基を有する基などである。
【０１４１】
なお、ここにおいて、アリール基を有する基（アリール基含有基）とは、上述したようなアリール基と、さらに、アルキル基にアリール基が付いた形の、いわゆるアラルキル基などをも、総括して指称するものである。
【０１４２】
当該ポリシロキサン（ＰＳ−１）中に含まれる加水分解性基とは、珪素原子に結合した、、それぞれ、アルコキシ基、ハロゲン、フェノキシ基、イソプロペニルオキシ基、アセトキシ基またはイミノオキシ基の如き、珪素原子との結合部分で以て、容易に加水分解されて、
【０１４３】
それぞれ、アルコール、ハロゲン化水素、フェノール、アセトン、酢酸またはオキシム化合物として脱離して、珪素原子に結合した、水酸基を生じさせるような官能基を指称するものである。
【０１４４】
そして、当該ポリシロキサン（ＰＳ−１）中に含まれる、これらの珪素原子に結合した、水酸基および／または加水分解性基の数としては、一分子平均で、０．６個未満が、好ましくは、０．４個未満が適切であるし、さらに一層好ましくは、０．２個未満が適切である。
【０１４５】
さらに、これらの珪素原子に結合した、水酸基および／または加水分解性基の含有量としては、当該ポリシロキサン（ＰＳ−１）の固形分の１，０００グラム当たり、０．３モル未満が、好ましくは、０．２モル未満が適切であるし、さらに一層好ましくは、０．１モル未満が適切である。
【０１４６】
これらの珪素原子に結合した、水酸基および／または加水分解性基の数が、一分子平均で、０．６個を超えるようになったり、該基の含有量が、当該ポリシロキサン（ＰＳ−１）の固形分の１，０００ｇ当たり、０．３モルを超えるようになったりする場合には、本発明の組成物を、一液型組成物として使用する場合において、とりわけ、貯蔵安定性が低下するようになり易く、また、硬化塗膜の、とりわけ、耐アルカリ性などが低下するようになり易くなるので、いずれの場合も好ましくない。
【０１４７】
このようなポリシロキサン（ＰＳ−１）は、たとえば、必須の原料成分として、トリアルコキシシラン化合物もしくはトリクロロシラン化合物の如き、各種の三官能性のシラン化合物と、エポキシ基含有アルコキシシラン化合物の如き、各種のエポキシ基含有シラン化合物とを使用し、
【０１４８】
さらには、必要により、ジアルコキシシラン化合物もしくはジクロロシラン化合物の如き、各種の二官能性のシラン化合物や、テトラアルコキシシランもしくはテトラクロロシランの如き、各種の四官能性のシラン化合物などをも使用して、調製することが出来る。
【０１４９】
当該ポリシロキサン（ＰＳ−１）を調製する際に用いられる、上記した三官能性のシラン化合物として特に代表的なもののみを例示するにとどめれば、メチルトリメトキシシラン、エチルトリメトキシシラン、ｎ−プロピルトリメトキシシラン、フェニルトリメトキシシラン、ビニルトリメトキシシラン、
【０１５０】
メチルトリエトキシシラン、エチルトリエトキシシラン、ｎ−プロピルトリエトキシシラン、フェニルトリエトキシシランもしくはビニルトリエトキシシランの如き、各種のトリアルコキシシラン化合物；
【０１５１】
またはメチルトリクロロシラン、エチルトリクロロシラン、ｎ−プロピルトリクロロシランもしくはフェニルトリクロロシランもしくはビニルトリクロロシランの如き、各種のトリクロロシラン化合物；
【０１５２】
あるいはメチルトリアセトキシシラン、エチルトリアセトキシシランもしくはフェニルトリアセトキシシランの如き、各種のトリアセトキシシラン化合物などである。
【０１５３】
また、後掲する如きエポキシ基含有シラン化合物のうち、三官能性のシラン化合物も、ここで言う三官能性のシラン化合物の一つとして使用することが出来ることは、勿論である。
【０１５４】
そして、前記エポキシ基含有シラン化合物として特に代表的なもののみを例示するにとどめれば、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルトリイソプロペニルオキシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリエトキシシランの如き、各種の三官能性のシラン化合物；
【０１５５】
または３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルメチルジイソプロペニルオキシラン、２−（３，４−エポキシシクロヘキシル）エチルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルエチルジエトキシシランの如き、各種の二官能性のシラン化合物；
【０１５６】
あるいは３−グリシドキシプロピルジメチルメトキシシラン、３−グリシドキシプロピルジメチルエトキシシラン、３−グリシドキシプロピルジメチルイソプロペニルオキシラン、２−（３，４−エポキシシクロヘキシル）エチルジメチルメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルジメチルエトキシシランの如き、各種の一官能性のシラン化合物などである。
【０１５７】
前記した二官能性のシラン化合物として特に代表的なもののみを例示するにとどめれば、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、
【０１５８】
ジ−ｎ−プロピルジメトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、メチルフェニルジメトキシシランもしくはメチルフェニルジエトキシシランの如き、各種のジアルコキシシラン化合物；
【０１５９】
またはジメチルジクロロシラン、ジエチルジクロロシラン、ジフェニルジクロロシラン、メチルフェニルジクロロシランもしくはジ−ｎ−プロピルジクロロシランの如き、各種のジクロロシラン化合物；
【０１６０】
あるいはジメチルジアセトキシシラン、ジエチルジアセトキシシラン、ジ−ｎ−プロピルジアセトキシシランもしくはジフェニルジアセトキシシランの如き、各種のジアセトキシシラン化合物；
【０１６１】
さらには、ヘキサメチルトリシクロシロキサンもしくはオクタメチルテトラシクロシロキサンの如き、環状の各種のポリシロキサン類などである。
【０１６２】
前記した四官能性のシラン化合物として特に代表的なもののみを例示するにとどめれば、テトラメトキシシラン、テトラエトキシシランもしくはテトラ−ｎ−ブトキシシランの如き、各種のテトラアルコキシシラン化合物；またはテトラクロロシランもしくはテトラブロモシランの如き、各種のテトラハロゲノシラン化合物などである。
【０１６３】
前掲したような、各種のシラン化合物を使用して、当該ポリシロキサン（ＰＳ−１）を調製するには、公知慣用の種々の方法を適用することが出来るが、たとえば、 （ｘｉ） 三官能性のシラン化合物と、エポキシ基含有シラン化合物との混合物を加水分解縮合せしめるという方法であるとか、
【０１６４】
（ｘｉｉ） 三官能性のシラン化合物を加水分解縮合させて、分岐構造（分枝状構造）を有する、末端官能性のシラン化合物を調製したのちに、エポキシ基含有シラン化合物を反応せしめるという方法であるとか、あるいは
【０１６５】
（ｘｉｉｉ） 三官能性のシラン化合物と、二官能性シラン化合物との混合物を加水分解縮合させて、分岐構造（分枝状構造）を有する末端官能性のシラン化合物を調製したのちに、エポキシ基含有シラン化合物を反応せしめるという方法などの、種々の方法を適用することが出来る。
【０１６６】
このようにして、当該ポリシロキサン（ＰＳ−１）を調製する際に、必要により、一官能性のシラン化合物を併用して、珪素原子に結合した、水酸基を、あるいは前掲したような、各種の加水分解性基を、効率的に、低減化せしめることが出来る。
【０１６７】
かかる一官能性のシラン化合物として特に代表的なもののみを例示するにとどめれば、トリメチルクロロシラン、トリエチルクロロシラン、トリ−ｎ−プロピルクロロシランもしくはトリフェニルクロロシランの如き、各種のモノクロロシラン類；
【０１６８】
またはトリメチルメトキシシラン、トリメチルエトキシシラン、トリエチルメトキシシラン、トリエチルエトキシシラン、トリフェニルメトキシシランもしくはトリフェニルエトキシシランの如き、各種のモノアルコキシシラン化合物；
【０１６９】
あるいはトリメチルシリルアセテートもしくはトリエチルシリアセテートの如き、各種のモノアセテート化合物；またはトリメチルシランもしくはトリエチルシランの如き、各種のヒドロシラン化合物などである。
【０１７０】
このようにして調製される、当該ポリシロキサン（ＰＳ−１）のエポキシ当量としては、１５０〜６，０００なる範囲内が、好ましくは、２００〜４，０００なる範囲内が適切であるし、さらに一層好ましくは、２５０〜２，５００なる範囲内が適切である。
【０１７１】
エポキシ当量が１５０未満である場合には、どうしても、とりわけ、耐候性などの特徴が出にくいというようになり易いし、一方、６，０００を超えて余りに大きくなる場合には、どうしても、とりわけ、硬化性などが低下するようになり易くなるので、いずれの場合も好ましくない。
【０１７２】
また、当該ポリシロキサン（ＰＳ−１）は、珪素原子上に、架橋用の官能基としてのエポキシ基を有する１価の有機基と共に、アリール基やアラルキル基などのような、種々のアリール基含有基、アルキル基、置換アルキル基またはビニル基の如き、エポキシ基を有しない、１価の有機基をも有するような形の化合物ではあるけれども、
【０１７３】
本発明の目的に合致せしめると共に、本発明の効果を発現化せしめるためには、前述した重合体（Ａ）、（Ｄ）あるいは（Ｅ）との相溶性、すなわち、クリヤー組成物から得られる硬化物の透明性などの面からも、あるいは下塗り塗膜との層間付着性やリコート性などの面からも、当該ポリシロキサン（ＰＳ−１）としては、特に、下掲するような形の化合物の使用が、特に望ましい。
【０１７４】
（１） 珪素原子上の、エポキシ基含有基を除く、１価の有機基（ｓ）として、アリール基含有基（ｓ−１）とアリール基不含の基（ｓ−２）とを併有し、しかも、アリール基含有基（ｓ−１）／アリール基不含の基（ｓ−２）なる比率が、モル比で以て、約１／９以上となるようなものであること、
【０１７５】
（２） 珪素原子上の、エポキシ基含有基を除く、１価の有機基（ｓ）として、アリール基含有基（ｓ−１）のみを有するというようなものであること、
【０１７６】
（３） 珪素原子上の、エポキシ基含有基を除く、１価の有機基（ｓ）として、アリール基含有基（ｓ−１）とアリール基不含の基（ｓ−２）とを併有し、しかも、アリール基含有基（ｓ−１）／アリール基不含の基（ｓ−２）なる比率が、モル比で以て、１／９未満であり、かつ、２００〜５００なるエポキシ当量を有するというようなものであること、
【０１７７】
あるいは
【０１７８】
（４） 珪素原子上の、エポキシ基含有基を除く、１価の有機基（ｓ）として、アリール基不含の基（ｓ−２）を有するものであって、しかも、２００〜５００なる範囲内のエポキシ当量を有するというようなものであること。
【０１７９】
上掲した、それぞれ、（１）〜（４）のような形の当該ポリシロキサン（ＰＳ−１）のうちでも、アリール基含有基（ｓ−１）およびアリール基不含の基（ｓ−２）としては、工業的な見地からも、それぞれ、フェニル基および炭素数が１〜４なるアルキル基の利用が、特に望ましい。
【０１８０】
このようなエポキシ基含有ポリシロキサンとして特に代表的なもののみを例示するにとどめれば、「Ｄ１０−０」、「Ｄ７−３」、「Ｄ４−６」、「Ｄ１−９」もしくは「Ｔ７−３」［東レ・ダウコーニング・シリコーン（株）製の商品名］や、「ＸＣ９６−Ａ４４６２」［東芝シリコーン（株）製の商品名］などのようなものである。
【０１８１】
次いで、前記した末端および／または側鎖にエポキシ基を有する、線状のポリシロキサン（ＰＳ−２）中に含まれる、珪素原子に結合した、水酸基および／または加水分解性基の数としては、一分子平均で、０．６個未満が、好ましくは、０．４個未満が適切であるし、一層好ましくは、０．２個未満が適切である。
【０１８２】
これらの珪素原子に結合した、水酸基および／または加水分解性基数が、一分子平均で、０．６個を超えて余りにるようになると、硬化塗膜の、とりわけ、耐アルカリ性などが低下するようになり易くなるので、好ましくない。
【０１８３】
かかるポリシロキサン（ＰＳ−２）の最も好ましいものの、より具体的なものとしては、下掲の組成式［ＩＩ］、［ＩＩＩ］、［ＩＶ］または［Ｖ］で以て示されるような、珪素原子に結合した、水酸基および／または加水分解性基を、一切、有しない形の化合物などが挙げられる。
【０１８４】
【化３】

【０１８５】
〔ただし、式中のＲ¹ 、Ｒ² 、Ｒ³ およびＲ⁴ は、それぞれ、同一であっても異なっていてもよい、アリール基、アラルキル基または炭素数が１〜４なるアルキル基を、Ｘはエポキシ基を有する１価の有機基を表わすものとし、また、ａは２〜４０なる整数であるものとする。〕
【０１８６】
【化４】

【０１８７】
〔ただし、式中のＲ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ およびＲ⁵ は、それぞれ、同一であっても異なっていてもよい、アリール基、アラルキル基または炭素数が１〜４なるアルキル基を、Ｘはエポキシ基を有する１価の有機基を表わすものとし、また、ｂは１〜３９なる整数であり、ｃは１〜２０なる整数であって、しかも、ｂとｃとの総和は２〜４０なる整数の範囲内にあるものとする。〕
【０１８８】
【化５】

【０１８９】
〔ただし、式中のＲ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ およびＹは、それぞれ、同一であっても異なっていてもよい、アリール基、アラルキル基または炭素数が１〜４なるアルキル基を、Ｘはエポキシ基を有する１価の有機基を表わすものとし、また、ｄは１〜３８なる整数であり、ｅは２〜２０なる整数であって、しかも、ｄとｅとの総和は３〜４０なる整数の範囲内にあるものとする。〕
【０１９０】
【化６】

【０１９１】
〔ただし、式中のＲ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ およびＹは、それぞれ、同一であっても異なっていてもよい、アリール基、アラルキル基または炭素数が１〜４なるアルキル基を、Ｘはエポキシ基を有する１価の有機基を表わすものとし、また、ｆは１〜３９なる整数であり、ｇは１〜２０なる整数であって、しかも、ｆとｇとの総和は２〜４０なる整数の範囲内にあるものとする。〕
【０１９２】
前掲した組成式［ＩＩ］で以て示されるようなポリシロキサンの中でも、とりわけ、リコート性などの面からすれば、エポキシ当量が２０２〜４００なる範囲内のもの、あるいは、エポキシ当量が４００〜１，５００程度であって、しかも、珪素原子に結合している有機基である、それぞれ、Ｒ¹ 、Ｒ² 、Ｒ³ およびＲ⁴ の合計量に占める、アリール基もしくはアラルキル基の如き、各種のアリール基含有基の割合が約１０モル％以上なる形のものであることが、特に望ましい。
【０１９３】
また、前掲した組成式［ＩＩＩ］で示されるポリシロキサンの中でも、とりわけ、リコート性などの面からすれば、エポキシ当量が１６０〜４００なる範囲内のもの、あるいは、エポキシ当量が４００〜１，５００程度であって、しかも、珪素原子に結合している有機基である、それぞれ、Ｒ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ およびＲ⁵ の合計量に占める、アリール基もしくはアラルキル基の如き、各種のアリール基含有基の割合が１０モル％以上なる形のものであることが、特に望ましい。
【０１９４】
さらに、前掲した組成式［ＩＶ］で示されるポリシロキサンの中でも、とりわけ、リコート性などの面からするならば、エポキシ当量が１６０〜４００なる範囲内のもの、あるいはエポキシ当量が４００〜１，５００程度であって、しかも、珪素原子に結合している有機基である、それぞれ、Ｒ¹ 、Ｒ² 、Ｒ³、Ｒ⁴ およびＲ⁵ の合計量に占める、アリール基もしくはアラルキル基の如き、各種のアリール基含有基の割合が約１０モル％以上なる形のものであることが、特に望ましい。
【０１９５】
さらにまた、前掲した組成式［Ｖ］で示されるポリシロキサンの中でも、とりわけ、リコート性などの面からすれば、エポキシ当量が１６０〜４００のもの、あるいはエポキシ当量が４００〜１，５００程度であって、しかも、珪素原子に結合している有機基である、それぞれ、Ｒ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ およびＲ⁵ の合計量に占める、アリール基もしくはアラルキル基の如き、各種のアリール基含有基の割合が１０モル％以上なる形のものであるということが、特に望ましい。
【０１９６】
次いで、前記した、一分子当たり、２個以上のエポキシ基を有する、環状構造のポリシロキサン（ＰＳ−３）中に含まれる、珪素原子に結合した、水酸基および／または加水分解性基の数としては、通常、一分子平均で、０．６個未満が適切であり、好ましくは、０．４個未満が適切であるし、さらに一層好ましくは、０．２個未満が適切である。
【０１９７】
これらの珪素原子に結合した、加水分解性基および／または珪素原子に結合した、水酸基数が、一分子平均、０．６個を超えて余りに多くなるようになると、どうしても、硬化塗膜の、とりわけ、耐アルカリ性などが低下するようになり易くなるので、あまり好ましくない。
【０１９８】
かかるポリシロキサン（ＰＳ−３）の最も好ましいものの、より具体的なものとしては、下掲の組成式［ＶＩ］で以て示されるような、珪素原子に結合した、加水分解性基および／または珪素原子に結合した、水酸基を、一切、有しない形の化合物が挙げられる。
【０１９９】
【化７】

【０２００】
〔ただし、式中のＲ¹ 、Ｒ² およびＲ³ は、それぞれ、同一であっても異なっていてもよい、アリール基、アラルキル基または炭素数が１〜４なるアルキル基を、Ｘはエポキシ基を有する１価の有機基を表わすものとし、また、ｈは０あるいは１〜４なる整数であり、ｉは２〜６なる整数であって、しかも、ｈとｉとの総和は３〜６なる整数の範囲内にあるものとする。〕
【０２０１】
前掲した組成式［ＩＩ］〜［ＶＩ］において、アリール基として特に代表的なもののみを例示するにとどめれば、フェニル基もしくはｐ−トリル基などのようなものであるし、
【０２０２】
また、アラルキル基として特に代表的なもののみを例示するにとどめれば、２−フェニルエチル基もしくは１−フェニルエチル基などのようなものであるし、
【０２０３】
あるいはエポキシ基を有する１価の有機基として特に代表的なもののみを例示するにとどめれば、３−グリシドキシプロピル基もしくは２−（３，４−エポキシシクロヘキシル）エチル基などのようなものである。
【０２０４】
以上に掲げたような、各種のエポキシ基を有するポリシロキサン（ＰＳ−１）、（ＰＳ−２）または（ＰＳ−３）のうちでも、硬化塗膜の、とりわけ、耐候性などの面からすれば、ポリシロキサン（ＰＳ−１）の使用が、特に望ましい。
【０２０５】
前述したような、各種のカルボキシル基含有重合体（Ａ）、アミノ基含有重合体（Ｄ）あるいはカルボキシル基・アミノ基併有重合体（Ｅ）と、当該ポリシロキサン（Ｂ）と、化合物（Ｃ）から、本発明の硬化性樹脂組成物を調製する場合の重量配合比率としては、
【０２０６】
成分（Ｃ）がアミノ樹脂以外の場合には、それぞれ、成分（Ａ）と成分（Ｂ）との固形分合計量の１００重量部に対して；成分（Ｄ）と成分（Ｂ）との固形分合計量の１００重量部に対して；あるいは成分（Ｅ）と成分（Ｂ）との固形分合計量の１００重量部に対して、
【０２０７】
成分（Ｃ）の固形分合計量が１〜２５０重量部となるように、好ましくは、２〜２００重量部となるように、特に好ましくは、３〜１５０重量部となるように、各成分を混合せしめるというようにすればよい。
【０２０８】
成分（Ｃ）として、前述したアミノ樹脂を使用するという場合には、それぞれ、成分（Ａ）と成分（Ｂ）との固形分合計量の１００重量部；成分（Ｄ）と成分（Ｂ）との固形分合計量の１００重量部に対して、
【０２０９】
あるいは成分（Ｅ）と成分（Ｂ）との固形分合計量の１００重量部に対して、アミノ樹脂の固形分量が、１〜７０重量部となるように、好ましくは、２〜５０重量部となるように、アミノ樹脂を配合せしめるというようにすればよい。
【０２１０】
成分（Ｃ）として、エポキシ基もしくはシクロカーボネート基などのような、カルボキシル基もしくはアミノ基との反応性に優れる官能基を有する化合物を使用するというような場合における当量配合比率としては、それぞれ、成分（Ａ）、成分（Ｄ）または成分（Ｅ）中に含まれるカルボキシル基および／またはアミノ基の１当量に対して、
【０２１１】
それぞれ、成分（Ｂ）および成分（Ｃ）中のカルボキシル基もしくはアミノ基と反応する官能基の合計量が、０．２〜５当量なる範囲内となるように、好ましくは、０．５〜２．０当量なる範囲内となるように、一層好ましくは、０．７〜１．５当量なる範囲内となるように、此の成分（Ｃ）を配合せしめるというようにすればよい。
【０２１２】
当該化合物（Ｃ）として、イソシアネート基もしくはブロックされたイソシアネート基などのような、水酸基との反応性に優れる官能基を有する化合物を使用する場合における当量配合比率としては、成分（Ａ）、成分（Ｄ）または成分（Ｅ）中に含まれる水酸基および／またはカルボキシル基をまとめての１当量に対して、
【０２１３】
此の成分（Ｃ）中の水酸基と反応する官能基が、０．２〜５当量なる範囲内となるように、好ましくは、０．５〜２．０当量なる範囲内となるように、一層好ましくは、０．７〜１．５当量なる範囲内となるように、成分（Ｃ）を配合せしめるというようにすればよい。
【０２１４】
そして、とりわけ、耐候性やリコート性などの面からは、本発明の組成物の合計固形分量に占める（Ｂ）の割合を、５〜９５重量％なる範囲内に、好ましくは、１０〜９０重量％なる範囲内に、一層好ましくは、１５〜８５重量％なる範囲内に、適宜、調整せしめるということが適切である。
【０２１５】
本発明の液状硬化性樹脂組成物は、また、その応用用途に応じて、有機溶剤溶液型、有機溶剤分散型あるいは無溶剤液状型などのような、いずれの形態としてでも、用いることが出来る。
【０２１６】
本発明の液状硬化性樹脂組成物は、そのままで、クリヤー組成物として使用することも出来るし、さらに、顔料が配合された形で以て、いわゆる着色組成物として使用することも出来る。
【０２１７】
さらには、本発明組成物には、必要に応じて、硬化触媒、レベリング剤、紫外線吸収剤、酸化防止剤または顔料分散剤などのような、公知慣用の各種の添加剤類などをも配合せしめることが出来る。
【０２１８】
かかる添加剤類のうち、硬化触媒として特に代表的なもののみを例示するにとどめれば、トリメチルホスフィン、トリエチルホスフィンもしくはトリフェニルホスフィンの如き、各種の有機ホスフィン類；ジブチル錫ジアセテート、ジブチル錫ジオクトエート、ジブチル錫ジラウレート、オクチル酸錫、ナフテン酸亜鉛もしくはオクチル酸亜鉛の如き、各種の金属カルボキシレート類；
【０２１９】
１，８−ジアザビシクロ［５．４．０］ウンデセン−７（ＤＢＵ）、１，５−ジアザビシクロ［４．３．０］ノネン−５（ＤＢＮ）もしくは１，４−ジアザビシクロ［２．２．２］オクタン（ＤＡＢＣＯ）；
【０２２０】
トリ−ｎ−ブチルアミンもしくはジメチルベンジルアミンの如き、各種の３級アミン類；テトラメチルアンモニウム塩、テトラブチルアンモニウム塩、トリメチル（２−ヒドロキシプロピル）アンモニウム塩、シクロヘキシルトリメチルアンモニウム塩、テトラキス（ヒドロキシメチル）アンモニウム塩もしくはｏ−トリフルオロメチルフェニルトリメチルアンモニウム塩の如き、各種の４級アンモニウム塩類；
【０２２１】
イミダゾール、１−メチルイミダゾール、２，４−ジメチルイミダゾールもしくは１，４−ジエチルイミダゾールの如き、各種のイミダゾール類；またはトリイソプロピルアルミネート（アルミニウム・トリイソプロポキサイド）もしくはテトライソプロピルチタネートの如き、各種の金属アルコラート類；
【０２２２】
あるいはテトラメチルホスホニウム塩、テトラエチルホスホニウム塩、テトラプロピルホスホニウム塩、テトラブチルホスホニウム塩、トリメチル（２−ヒドロキシプロピル）ホスホニウム塩、テトラフェニルホスホニウム塩もしくはベンジルトリフェニルホスホニウム塩の如き、各種の４級ホスホニウム塩類などである。
【０２２３】
なお、前掲した４級アンモニウム塩類および４級ホスホニウム塩類における、いわゆる対アニオンとして特に代表的なもののみを例示するにとどめれば、クロライド、ブロマイド、カルボキシレートまたはハイドロキサイドなどのような、種々のアニオンなどである。
【０２２４】
かかる硬化触媒類の添加は、（Ａ）成分と、（Ｂ）成分と、（Ｃ）成分とからなる組成物に対して、とりわけ、低温硬化性ないしは常温硬化性などを付与せしめるというために、特に有効であると言える。
【０２２５】
（Ａ）成分と、（Ｂ）成分と、（Ｃ）成分とからなる、此の形の組成物に硬化触媒類を添加するという場合には、これらの三成分の固形分合計量の１，０００グラムに対して、触媒効果を有する基ないしは原子団の量が、５〜１，０００ミリモルとなるような範囲が、好ましくは、１０〜５００ミリモルとなるような範囲が適切である。
【０２２６】
また、前掲したような代表的な諸硬化触媒に加えて、前述したような触媒効果を発現する原子団や基などを有する、各種の重合体類などもまた、有効なる触媒として使用することが出来る。
【０２２７】
かくして得られる、本発明の液状硬化性樹脂組成物は、（Ａ）成分と、（Ｂ）成分と、（Ｃ）成分とを組み合わせた場合には、１００℃〜２５０℃程度の温度範囲で以て、３０秒間〜１時間程度の焼き付けを行なうことによって、極めて耐久性などに優れる硬化物を得ることが出来る。
【０２２８】
これとは別に、（Ｂ）成分と（Ｃ）成分に、（Ｄ）成分あるいは（Ｅ）成分を組み合わせた場合には、アミノ基の含有量に応じて、常温硬化から焼き付け硬化に到るまでの、幅広い硬化条件の設定が可能である。
【０２２９】
また、（Ａ）成分と、（Ｂ）成分と、（Ｃ）成分を組み合わせた場合であっても、前掲したような硬化触媒の種類を、適宜、適切に選択して、その最適量で以て添加し配合せしめることによって、常温での硬化も可能となる。
【０２３０】
以上のようにして得られる、本発明の液状硬化性樹脂組成物は、鉄、ステンレス・スチール、アルミニウムもしくは真鍮などのような種々の金属類または其れらの諸製品；
【０２３１】
コンクリート、スレート、モルタルもしくはガラスなどのような種々の無機系素材類または其れらの諸製品；ポリプロピレン、ポリスチレン、ＡＢＳ樹脂もしくはポリメチルメタクリレートなどのような種々のプラスチック素材類または其れらの諸製品をはじめとする、
【０２３２】
各種の対象物への塗料用として利用し、適用することが出来るし、さらには、それぞれ、接着剤としても、あるいはシーリング剤としても、利用し、適用することが出来る。
【０２３３】
【実施例】
次に、本発明を、参考例、実施例および比較例により、一層、具体的に説明することにするが、本発明は、決して、これらの例のみに限定されるものではない。以下において、部および％は、特に断りの無い限り、すべて、重量基準であるものとする。
【０２３４】
参考例１〔カルボキシル基含有重合体（Ａ）の調製例〕
温度計、還流冷却器、攪拌機、滴下漏斗および窒素ガス導入管を備えた反応容器に、キシレンの５００部およびｎ−ブタノールの３００部を仕込んで、窒素ガスの通気下に、１１０℃にまで昇温した。
【０２３５】
次いで、同温度で、メチルメタクリレート（ＭＭＡ）の３００部、ｎ−ブチルメタクリレート（ＢＭＡ）の３７２部、ｎ−ブチルアクリレート（ＢＡ）の１７８部およびアクリル酸（ＡＡ）の１５０部と、キシレンの２００部と、ｔｅｒｔ−ブチルパーオキシオクトエート（ＴＢＯ）の２０部およびｔｅｒｔ−ブチルパーオキシベンゾエート（ＴＢＺ）の１０部とからなる混合物を、４時間に亘って滴下した。
【０２３６】
その後も、同温度に、１５時間のあいだ保持して、不揮発分（Ｎ．Ｖ．）が５０％で、かつ、数平均分子量（Ｍｎ）が６，９００なる、カルボキシル基含有アクリル系重合体の溶液を得た。以下、これを重合体（Ａ−１）と略記する。
【０２３７】
参考例２（同上）
単量体として、スチレン（ＳＴ）の１００部、ＭＭＡの２００部、２−エチルヘキシルメタクリレート（ＥＨＭＡ）の５５０部およびメタクリル酸（ＭＡＡ）の１５０部からなる混合物を使用するように変更した以外は、参考例１と同様にして重合を行なって、Ｎ．Ｖ．が５０％で、かつ、Ｍｎが６，５００なる、カルボキシル基含有アクリル系重合体の溶液を得た。以下、これを重合体（Ａ−２）と略記する。
【０２３８】
参考例３（同上）
単量体として、シクロヘキシルメタクリレート（ＣＨＭＡ）の６７３部、ＢＡの２７７部およびＡＡの５０部からなる混合物を使用するように変更した以外は、参考例１と同様にして重合を行ない、Ｎ．Ｖ．が５０％で、かつ、Ｍｎが５，５００なるカルボキシル基を有するアクリル系重合体の溶液を得た。以下、これを重合体（Ａ−３）と略記する。
【０２３９】
参考例４（同上）
単量体として、ＣＨＭＡの６２３部、ＢＡの２７７部、２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）の５０部およびＡＡの５０部よりなる混合物を使用するように変更した以外は、参考例１と同様にして重合を行なって、Ｎ．Ｖ．が５０％で、かつ、Ｍｎが５，７００なるカルボキシル基を有するアクリル系重合体の溶液を得た。以下、これを重合体（Ａ−４）と略記する。
【０２４０】
参考例５（同上）
２リットルのステンレス製オートクレーブを、窒素ガスで置換してから、此のオートクレーブに、アジピン酸モノビニルエステル（ＭＶＡ）の２００部、「ベオバ−９」〔オランダ国シェル社製の、分岐状（分枝状）カルボン酸のビニルエステルの商品名〕の２００部およびエチルビニルエーテル（ＥＶＥ）の２００部と、メチルイソブチルケトン（ＭＩＢＫ）の６６７部と、２，２’−アゾビス（２，４−ジメチルバレロニトリル）の２０部とを仕込んだ。
【０２４１】
次いで、液化採取したクロロトリフルオロエチレン（ＣＴＦＥ）の４８０部を圧入してから密閉して、攪拌下に、６０℃にまで昇温した。しかるのち、同温度で、２０時間に亘る重合反応を行なって、Ｎ．Ｖ．が５８．０％で、かつ、数平均分子量が２１，０００なる、カルボキシル基含有フルオロオレフィン系重合体の溶液を得た。以下、これを重合体（Ａ−５）と略記する。
【０２４２】
参考例６（同上）
温度計、脱水トラップ付き還流冷却器、攪拌機および窒素ガス導入管を備えた反応容器に、トリメチロールプロパンの１３２部およびネオペンチルグリコールの１９０部を仕込んで、窒素ガスの通気下で、１５０℃にまで昇温した。
【０２４３】
次いで、ヘキサヒドロフタル酸の１３４部、イソフタル酸の２８８部、アジピン酸の２５３部および「カージュラ Ｅ」〔シェル社製の、分岐状（分枝状）モノカルボン酸のグリシジルエステルの商品名〕の１０５部と、水酸化リチウムの０．８５部とを加えて、２２０℃にまで昇温し、さらに、同温度で、酸価が１００となるまで、脱水縮合反応を行なった。
【０２４４】
その後は、冷却をして、キシレンの５３９部を加えることによって、Ｎ．Ｖ．が６５％で、かつ、固形分の酸価が１００なる、カルボキシル基を有するポリエステル樹脂の溶液を得た。以下、これを重合体（Ａ−６）と略記する。
【０２４５】
参考例７（同上）
参考例６と同様の反応器に、やし油の３００部と、水酸化ナトリウムの０．１５部と、トリメチロールプロパンの１３２部とを仕込んで、窒素ガスの通気下で、２５０℃にまで昇温し、同温度に、１時間のあいだ保持することによって、エステル交換反応を行なった。
【０２４６】
次いで、１５０℃に降温して、トリメチロールプロパンの７７部、ペンタエリスリトールの９４部、ヘキサヒドロ無水フタル酸の３５１部および無水フタル酸の４４部と、ｐ−ｔｅｒｔ−ブチル安息香酸の４９部と、キシレンの４０部とを加えて、１６０〜１８０℃に、３時間のあいだ保持してから、２２０℃にまで、２時間をかけて、徐々に昇温して、さらに、固形分の酸価が５．０となるまで、同温度で、２時間のあいだ、脱水縮合反応を行なった。
【０２４７】
しかるのち、１７０℃に降温して、無水コハク酸の２１４部を加え、同温度に、３時間のあいだ保持してから冷却して、キシレンの２７０部と、メチルイソブチルケトンの２７０部とを加えて、Ｎ．Ｖ．が６０％で、かつ、固形分の酸価が１００なる、カルボキシル基を有するポリエステル樹脂の溶液を得た。以下、これを重合体（Ａ−７）と略記する。
【０２４８】
参考例８〔アミノ基含有重合体（Ｄ）の調製例〕
参考例１と同様の反応器に、トルエンの３９２部およびイソブタノールの４０８部を仕込んで、窒素ガスの通気下で、８０℃にまで昇温した。
【０２４９】
次いで、同温度で、ＳＴの２００部、ＭＭＡの３００部、ＢＭＡの２００部、ＢＡの２００部および２−（Ｎ，Ｎ−ジメチルアミノ）エチルメタクリレート（ＤＭＭＡ）の１００部と、アゾビスイソブチロニトリル（ＡＩＢＮ）の５部およびＴＢＯの５部と、トルエンの２００部とからなる混合物を、３時間かけて滴下した。
【０２５０】
滴下終了後も、同温度に、２時間のあいだ保持してから、さらに、ＡＩＢＮの５部と、トルエンの４４８部およびイソブタノールの３７部とからなる混合物を、１時間を要して滴下した。
【０２５１】
さらに、同温度に、１２時間のあいだ保持して、Ｎ．Ｖ．が４０％で、かつ、Ｍｎが１１，０００なる、３級アミノ基含有アクリル系重合体を得た。以下、これを重合体（Ｄ−１）と略記する。
【０２５２】
参考例９（同上）
単量体として、ＳＴの２００部、ＭＭＡの２００部、ＣＨＭＡの３００部、ＥＨＭＡの２００部およびＮ−（３−ジメチルアミノ）プロピルメタクリルアミドの１００部を使用するように変更した以外は、参考例８と同様にして重合を行なって、Ｎ．Ｖ．が４０％で、かつ、Ｍｎが１２，０００なる、３級アミノ基含有アクリル系重合体の溶液を得た。以下、これを重合体（Ｄ−２）と略記する。
【０２５３】
参考例１０（同上）
参考例１と同様の反応器に、トルエンの３９２部および酢酸ｎ−ブチルの４０８部を仕込んで、窒素ガスの通気下で、８０℃にまで昇温した。
【０２５４】
次いで、同温度で、ＳＴの２００部、ＭＭＡの２５０部、ＢＭＡの２００部、ＢＡの２００部、ＨＥＭＡの５０部およびＤＭＭＡの１００部と、ＡＩＢＮの５部およびＴＢＯの５部と、トルエンの２００部とからなる混合物を、３時間かけて滴下した。
【０２５５】
滴下終了後も、同温度に、２時間のあいだ保持してから、さらに、ＡＩＢＮの５部と、トルエンの４４８部および酢酸ｎ−ブチルの３７部とからなる混合物を、１時間を要して滴下した。
【０２５６】
さらに、同温度に、１２時間のあいだ保持して、Ｎ．Ｖ．が４０％で、かつ、Ｍｎが１２，０００なる、３級アミノ基含有アクリル系重合体を得た。以下、これを重合体（Ｄ−３）と略記する。
【０２５７】
参考例１１（同上）
参考例５と同様の反応器内を、窒素ガスで置換してから、此の反応容器に、２−（Ｎ，Ｎ−ジメチルアミノ）エチルビニルエーテル（ＤＡＥＶＥ）の１００部、ＥＶＥの１００部および「ベオバ−９」の４００部と、ｔｅｒｔ−ブチルパーオキシピバレート（ＴＢＰＶ）の１０部と、ＭＩＢＫの４２９部とを仕込んだ。
【０２５８】
次いで、液化採取したヘキサフルオロプロピレンの４００部を圧入し密閉してから、攪拌下に６０℃にまで昇温し、同温度で、１７時間に亘る重合反応を行なうことによって、Ｎ．Ｖ．が６８％で、かつ、Ｍｎが１５，０００なる、３級アミノ基含有フルオロオレフィン系重合体の溶液を得た。以下、これを重合体（Ｄ−４）と略記する。
【０２５９】
参考例１２〔カルボキシル基・アミノ基併有重合体（Ｅ）の調製例〕
単量体として、ＳＴの２００部、ＭＭＡの３００部、ＢＭＡの２００部、ＢＡの１００部、２−（Ｎ，Ｎ−ジメチルアミノ）エチルアクリレートの１５０部およびＡＡの５０部を用いるように変更した以外は、参考例８と同様にして重合を行なって、Ｎ．Ｖ．が４０％で、かつ、Ｍｎが１１，０００なる、カルボキシル基と３級アミノ基とを併有するアクリル系重合体の溶液を得た。以下、これを重合体（Ｅ−１）と略記する。
【０２６０】
参考例１３（同上）
参考例１と同様の反応器に、トルエンの３９２部および酢酸ｎ−ブチルの４０８部を仕込んで、窒素ガスの通気下で、８０℃にまで昇温した。
【０２６１】
次いで、同温度で、ＳＴの２００部、ＭＭＡの３００部、ＥＨＭＡの３５０部、ＨＥＭＡの７０部、ＡＡの３０部およびＤＭＭＡの５０部と、ＡＩＢＮの５部およびＴＢＯの５部と、トルエンの２００部とからなる混合物を、３時間かけて滴下した。
【０２６２】
滴下終了後も、同温度に、２時間のあいだ保持してから、さらに、ＡＩＢＮの５部と、トルエンの４４８部および酢酸ｎ−ブチルの３７部とからなる混合物を、１時間を要して滴下した。
【０２６３】
さらに、同温度に、１２時間のあいだ保持することによって、Ｎ．Ｖ．が４０％で、かつ、Ｍｎが１２，０００なる、３級アミノ基含有アクリル系重合体を得た。以下、これを重合体（Ｅ−２）と略記する。
【０２６４】
参考例１４（同上）
ＣＴＦＥ以外の単量体成分として、それぞれ、ＭＶＡの２００部、「ベオバ−９」の２００部、ＥＶＥの１５０部およびＤＡＥＶＥの５０部を使用するように変更した以外は、参考例５と同様にして重合を行ない、Ｎ．Ｖ．が５８％で、かつ、Ｍｎが２０，０００なる、カルボキシル基・アミノ基併有フルオロオレフィン系重合体の溶液を得た。以下、これを重合体（Ｅ−３）と略記する。
【０２６５】
参考例１５〔活性水素を有する基と反応する官能基を含有する化合物（Ｃ）の調製例〕
【０２６６】
参考例１と同様の反応容器に、キシレンの１，４００部を仕込んで、窒素ガスの通気下に、１１０℃にまで昇温した。
【０２６７】
次いで、同温度で、ＭＭＡの１００部、ＢＭＡの２１０部、ＢＡの１８４部およびＧＭＡの５０６部と、ＴＢＯの６０部およびＴＢＺの１２部と、キシレンの１００部とからなる混合物を、５時間に亘って滴下した。
【０２６８】
滴下終了後も、同温度に、１５時間のあいだ保持することによって、Ｎ．Ｖ．が４０％で、かつ、数平均分子量が２，９００なる、エポキシ基を有するアクリル系重合体の溶液を得た。以下、これを化合物（Ｃ−１）と略記する。
【０２６９】
参考例１６（同上）
参考例１と同様の反応容器に、キシレンの５００部およびｎ−ブタノールの３００部を仕込んで、窒素ガスの通気下に、１２０℃にまで昇温した。
【０２７０】
次いで、同温度で、ＭＭＡの２００部、ＳＴの２００部、ＢＭＡの３００部、２−オキソ−１，３−ジオキソラン−４−イルメチルメタクリレートの３００部、ＡＩＢＮの１０部と、ＴＢＯの２０部およびＴＢＺの１０部と、キシレンの２００部とからなる混合物を、５時間に亘って滴下した。
【０２７１】
滴下終了後も、同温度に、１５時間のあいだ保持することによって、Ｎ．Ｖ．が５０％で、かつ、数平均分子量が１０，０００なる、シクロカーボネート基を有するアクリル系重合体の溶液を得た。以下、これを化合物（Ｃ−２）と略記する。
【０２７２】
以下に掲げる諸実施例において使用する、前記（Ｂ）成分であるエポキシ基含有ポリシロキサンの性状値ないしは特性値を、まとめて、第１表に示す。
【０２７３】
【表１】

【０２７４】
【表２】

【０２７５】
【表３】

【０２７６】
実施例１〜５ならびに比較例１および２
第２表に示すような使用比率で以て、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、硬化触媒および添加剤を混合せしめて得られる、それぞれのクリヤー組成物を、「ソルベッソ １００」（米国エクソン社製の、芳香族炭化水素混合物の商品名）／ｎ−ブタノール＝７０／３０（重量部比）なる混合溶剤で以て、フォード・カップ＃４による粘度が２０秒となるように希釈せしめることによって、各種のクリヤー塗料を調製した。
【０２７７】
次いで、予め、ポリエステル−メラミン系の塗料が塗装され、焼き付けされた鋼板上に、上述のようにして調製した、それぞれのクリヤー塗料を、乾燥膜厚が約３０ミクロン（μｍ）となるように、エアースプレー塗装した。
【０２７８】
しかるのち、第２表に示す通りの条件で以て、焼き付けを行なうことによって、各種の硬化塗膜を得た。
【０２７９】
それぞれの塗膜について、諸性能の評価検討を行なった。それらの結果は、まとめて、同表に示す。
【０２８０】
【表４】

【０２８１】
《第２表の脚注》
表中の各成分の配合割合は、いずれも、重量部で以て示されている。
【０２８２】
「Ｌ−１１７−６０」………「スーパーベッカミン Ｌ−１１７−６０」の略記であって、大日本インキ化学工業（株）製の、ｎ−ブチルエーテル化メラミン・ホルムアルデヒド樹脂溶液の商品名であり、不揮発分が６０％なるものである。
【０２８３】
「Ｂ７−８８７」……………「バーノック Ｂ７−８８７−６０」の略記であって、大日本インキ化学工業（株）製の、無黄変タイプのブロック・ポリイソシアネート化合物の溶液の商品名であり、不揮発分が６０％で、かつ、ブロックされたイソシアネート基含有率が７．９％なるものである。
【０２８４】
【表５】

【０２８５】
《第２表の脚注》
【０２８６】
「１−ＭＩｍ」………１−メチルイミダゾールの略記
【０２８７】
「ＴＢＡＡｃ」…………………………テトラブチルアンモニウムアセテートの略記
【０２８８】
「チヌビン ９００」…………………スイス国チバ・ガイギー社製の、ベンゾトリアゾール系の紫外線吸収剤の商品名である。
【０２８９】
「ＬＳ−７６５」………………………「サノール ＬＳ−７６５」の略記であって、三共（株）製の、ヒンダード・アミン系の酸化防止剤の商品名である。
【０２９０】
表中の「硬化条件」における“Ｉ”は、「１４０℃で３０分間の焼き付け」を表わし、もう一方の“ＩＩ”の方は、「１６０℃で３０分間の焼き付け」を表わしている。
【０２９１】
表中の「促進耐候性」は、スガ試験機（株）製のデューパネル光コントロール・ウェザーメーターを使用して、１，５００時間に及ぶ曝露を行なったのちの、６０度鏡面反射率（％）なる光沢値を、未曝露時における塗膜の、同上の光沢値で以て除して、１００倍した値（光沢保持率：％）で以て評価判定をし、その値を以て表示したものである。
【０２９２】
ただし、デューパネル光コントロール・ウェザーメーターでの曝露は、下記の条件を以て１サイクルとし、それを繰り返し行ったというものである。
【０２９３】
紫外線照射：７０℃に８時間
【０２９４】
加 湿：４０℃に４時間
【０２９５】
表中の「初期撥水性」は、協和界面化学（株）製のＣＡ−Ｚ型自動接触角測定装置を使用して、それぞれの硬化塗膜上に載せた水滴と、該硬化塗膜との接触角を測定して、その接触角度で以て表示したものであり、水との接触角度で以て表示しているものである。
【０２９６】
表中の「耐候性試験後の撥水性」は、スガ試験機（株）製のデューパネル光コントロール・ウェザーメーターを使用して、「促進耐候性」の場合と同様の条件で、１，５００時間に及ぶ曝露を行なったのちの、硬化塗膜についての、水との接触角度を、上述した「初期撥水性」の場合と同様にして測定をし、その接触角度で以て表示したものである。
【０２９７】
表中の「耐洗車傷性」は、その代用試験としての、太平理化工業（株）製のラビング・テスターを使用して、クレンザーの水分散液（重量濃度＝５％）を滲み込ませたフェルトで以て、５００グラムなる重りの荷重下に、塗膜を、各別に、往復６０回、ラビングしたのちの、２０度鏡面反射率（％）なる光沢値を、未試験塗膜の同上の光沢値で以て除して、１００倍した値（光沢保持率：％）で以て表示したものである。
【０２９８】
【表６】

【０２９９】
《第２表の脚注》
「ＸＣ９６」……………………………「ＸＣ９６−Ａ４４６２」の略記である。
【０３００】
「ＥＸ−６１２」………………………「デナコール ＥＸ−６１２」の略記であって、長瀬化成工業（株）製の、ソルビトール・ポリグリシジルエーテルであり、エポキシ当量が１７０なるものである。
【０３０１】
【表７】

【０３０２】
同表に示すような結果からも、すでに、明かなように、本発明の組成物から得られる硬化塗膜は、比較例１および２の場合の硬化塗膜に比して、耐候性、耐候性試験後の撥水性ならびに耐洗車傷性に優れているということが、無理なく、知り得よう。
【０３０３】
実施例６〜８ならびに比較例３および４
まず、第３表に示すような使用比率で以て、（Ａ）成分と、顔料との混合物を、サンドミルを使用して、分散化せしめることによって、各種の、白色のベースを調製した。
【０３０４】
次いで、それぞれの白色ベースに、（Ｂ）成分と、（Ｃ）成分と、硬化触媒とを配合せしめることによって、あるいは「デナコール ＥＸ−６１２」と、硬化触媒とを配合せしめることによって、各種の白色組成物を調製した。
【０３０５】
さらに、それぞれの白色組成物を、「ソルベッソ １００」／ｎ−ブタノール＝７０／３０（重量部比）なる混合溶剤で以て、フォード・カップ＃４による粘度が２５秒となるように希釈せしめることによって、顔料重量濃度（ＰＷＣ）が４０％なる、各種の白色塗料を調製した。
【０３０６】
かくして得られた、それぞれの塗料を、予め、ポリエステル−メラミン系の塗料が塗装され、焼き付けされた鋼板上に、乾燥膜厚が約３０μｍとなるように、エアースプレー塗装し、第３表に示すような条件で以て、焼き付けを行なって、各種の硬化塗膜を得た。
【０３０７】
それぞれの塗膜について、諸性能を評価した結果を、まとめて、同表に示す。
【０３０８】
【表８】

【０３０９】
《第３表の脚註》
表中の各成分の配合割合は、いずれも、重量部で以て示されている。
【０３１０】
「ＣＲ−９３」………「タイペーク ＣＲ−９３」の略記であって、石原産業（株）製の、ルチル型酸化チタンの商品名である。
【０３１１】
【表９】

【０３１２】
【表１０】

【０３１３】
【表１１】

【０３１４】
《第３表の脚注》
表中の「促進耐候性」は、サンシャイン・ウエザオメーターによる２，０００時間に及ぶ曝露を行なったのちの、６０度鏡面反射率（％）なる光沢値を、未曝露時における塗膜の、同上の光沢値で以て除して、１００倍した値（光沢保持率：％）で以て評価判定をし、その値を以て表示したものである。
【０３１５】
表中の「初期撥水性」および「耐洗車傷性」の評価判定は、実施例１〜５ならびに比較例１および２の場合におけると同様の要領に従った。
【０３１６】
表中の「耐候性試験後の撥水性」は、サンシャイン・ウエザオメーターを使用して、１，５００時間に及ぶ曝露を行なったのちの、硬化塗膜についての、水との接触角度を、上述した「初期撥水性」の場合と同様にして測定し、その接触角度で以て表示したものである。
【０３１７】
同表に示す結果からも、すでに、明らかなように、本発明の組成物を用いて得られる硬化塗膜は、いずれも、「デナコール ＥＸ−６１２」から調製された、それぞれ、比較例３および４の場合の硬化塗膜に比して、とりわけ、耐候性、耐候性試験後の撥水性ならびに耐洗車傷性などに優れるというものであることが、無理なく、知り得よう。
【０３１８】
実施例９〜１５ならびに比較例５および６
まず、第４表に示すような使用比率で以て、（Ｄ）成分または（Ｅ）成分と、顔料との混合物を、サンドミルによって分散せしめ、各種の、白色のベースを調製した。
【０３１９】
次いで、こうした、それぞれの白色ベースに、（Ｂ）成分と、（Ｃ）成分とを配合せしめることによって、あるいは「デナコール ＥＸ−６１２」を配合せしめることによって、白色組成物を調製した。
【０３２０】
さらに、実施例１１および１４の白色組成物については、キシレン／トルエン／酢酸ｎ−ブチル／酢酸エチル／２−エトキシエチルアセテート＝４０／３０／２０／１０（重量部比）なる混合溶剤で以て、そして、実施例１１および１４以外の白色組成物については、キシレン／トルエン／ｎ−ブタノール／酢酸エチル／２−エトキシエチルアセテート＝４０／３０／２０／１０（重量部比）なる混合溶剤で以て、フォード・カップ＃４による粘度が１７秒となるように希釈せしめることによって、ＰＷＣが３５％なる、各種の白色塗料を調製した。
【０３２１】
かくして得られた、それぞれの塗料を、予め、ポリエステル−メラミン系の塗料が塗装され、焼き付けされた鋼板上に、乾燥膜厚が約３０μｍとなるように、エアースプレー塗装し、室温に、１０日間のあいだ放置してから、各種の硬化塗膜を得た。
【０３２２】
それぞれの塗膜について、諸性能を評価検討した結果を、まとめて、同表に示す。
【０３２３】
【表１２】

【０３２４】
《第４表の脚註》
表中の各成分の配合割合は、いずれも、重量部で以て示されている。
【０３２５】
「ＤＮ−９９０Ｓ」………「バーノック ＤＮ−９９０Ｓ」の略記であって、大日本インキ化学工業（株）製の、無黄変型ポリイソシアネート樹脂の商品名であり、不揮発分が１００％で、かつ、イソシアネート基含有率が１７．３％なるものである。
【０３２６】
表中の「促進耐候性」、「初期撥水性」、「耐候性試験後の撥水性」および「耐洗車傷性」は、第３表における場合の評価と同様にして行った。
【０３２７】
【表１３】

【０３２８】
【表１４】

【０３２９】
【表１５】

【０３３０】
【表１６】

【０３３１】
【表１７】

【０３３２】
同表に示す結果からも、すでに、明らかなように、本発明の組成物から得られる硬化塗膜は、いずれも、「デナコール ＥＸ−６１２」から調製された、それぞれ、比較例５および６の場合の硬化塗膜に比して、とりわけ、耐候性、耐候性試験後の撥水性ならびに耐洗車傷性などに優れるということが、無理なく、知り得よう。
【０３３３】
【発明の効果】
本発明の液状硬化性樹脂組成物は、とりわけ、耐洗車傷性などにも優れるし、加えて、曝露時の光沢保持性（耐候性）ならびに撥水性保持性などといった、いわゆる耐久性などにも優れるというものであり、特徴的には、非常に高度の耐久性を有するという、極めて実用性の高いものである。[0001]
[Industrial application fields]
The present invention relates to a novel and useful liquid curable resin composition. More specifically, the present invention relates to a polymer having a specific group, a carboxyl group or an amino group, a polysiloxane having a specific epoxy group, and a compound having a functional group that reacts with a group having active hydrogen. The present invention relates to a liquid curable resin composition, which is contained as an essential film-forming component, and particularly forms a cured product having excellent durability.
[0002]
The curable resin composition of the present invention is used and applied in various fields, particularly for paints or as an adhesive or a sealing agent.
[0003]
[Prior art]
So far, as a curable resin composition that forms a cured product having excellent durability, an acrylic polymer having a so-called functional group such as a hydroxyl group, a carboxyl group, or an amino group mainly in the paint field, A base polymer component such as a polyester resin or an alkyd resin in which a so-called curing agent such as an amino resin, a polyisocyanate resin or an epoxy resin is blended has been widely used.
[0004]
However, cured products obtained from such formulations are inferior in so-called durability, such as gloss retention during exposure and water repellency retention, and are used for applications that require high durability. There is a problem that it cannot be used substantially.
[0005]
In addition, for automobile topcoats, high car wash resistance is also required, but there is still no satisfactory one yet.
[0006]
[Problems to be solved by the invention]
As described above, as long as the conventional technology is followed, it is impossible to obtain a highly practical curable resin composition having high durability, and particularly, gloss retention at the time of exposure, water repellency. The emergence of a novel and extremely practical curable resin composition that imparts a high degree of durability, etc., in terms of retention or car wash scuff resistance is urgently desired.
[0007]
For this reason, the present inventors have sought a curable resin composition that can form a cured product having such a high degree of durability, and in particular, a liquid curable resin composition, We have earnestly started research.
[0008]
Therefore, the problem to be solved by the present invention is, inter alia, a highly practical curable resin composition capable of forming a cured product having a high degree of durability, in particular, extremely practical. It is in providing a liquid curable resin composition with high.
[0009]
[Means for Solving the Problems]
Therefore, in view of the present situation, the present inventors have made intensive studies and focused on the problems to be solved by the invention as described above. As a result, the inventors have found that a compound having a carboxyl group and / or an amino group is present. A liquid curable resin composition comprising a combination, a specific polysiloxane having an epoxy group, and a compound having a functional group that reacts with a group having active hydrogen has gloss retention, water repellency retention, and car wash resistance. The present invention is completed here in order to find that a cured product having excellent durability and so-called durability can be obtained, and to be convinced that the above-mentioned problems can be solved brilliantly. It reached.
[0010]
〔Constitution〕
[0011]
That is, the present invention basically has a polymer (A) having a carboxyl group as an essential functional group in the molecule, a structural unit represented by the general formula [I], and in one molecule. The number of hydroxyl groups and / or hydrolyzable groups bonded to a silicon atom contained in the group is less than 0.6 on average and less than 0.3 mol per 1000 grams of the solid content, and at least two in one molecule A branched polysiloxane (B) having an epoxy group and a compound having a functional group that reacts with a group having active hydrogen, and a compound (C) excluding this polysiloxane (B) And at least one functional group that reacts with the group having active hydrogen is selected from the group consisting of an epoxy group, a cyclocarbonate group, an isocyanate group, a blocked isocyanate group, a hydroxymethylamino group, and an alkoxymethylamino group. belongs to It is intended to provide a highly practical curable resin composition that can give a cured product excellent in durability, among others,
[0012]
In addition, a polymer (D) having an amino group as an essential functional group in the molecule and a structural unit represented by the general formula [I], and bonded to a silicon atom contained in one molecule A branched chain having at least two epoxy groups in one molecule, having an average of less than 0.6 hydroxyl groups and / or hydrolyzable groups and less than 0.3 moles per 1000 grams of solid content Containing a polysiloxane (B) and a compound having a group that reacts with a group having active hydrogen and excluding the polysiloxane (B) And at least one functional group that reacts with the group having active hydrogen is selected from the group consisting of an epoxy group, a cyclocarbonate group, an isocyanate group, a blocked isocyanate group, a hydroxymethylamino group, and an alkoxymethylamino group. belongs to An object of the present invention is to provide a curable resin composition.
[0013]
Furthermore, the present invention includes, in one molecule, a polymer (E) having both a carboxyl group and an amino group as essential functional groups, and a structural unit represented by the general formula [I], In one molecule, the number of hydroxyl groups and / or hydrolyzable groups bonded to silicon atoms contained in one molecule is less than 0.6 on average and less than 0.3 mol per 1000 grams of solid content. A compound containing a branched polysiloxane (B) having at least two epoxy groups, and a compound having a group that reacts with a group having active hydrogen, excluding the polysiloxane (B) ( C) and And at least one functional group that reacts with the group having active hydrogen is selected from the group consisting of an epoxy group, a cyclocarbonate group, an isocyanate group, a blocked isocyanate group, a hydroxymethylamino group, and an alkoxymethylamino group. belongs to Another object of the present invention is to provide a curable resin composition.
[0014]
Here, first, the polymer (A) having a carboxyl group used in the present invention refers to a polymer having at least two carboxyl groups per molecule as an essential functional group. Is.
[0015]
As examples of such a polymer (A), only typical ones are exemplified. Various vinyls such as acrylic polymers, fluoroolefin polymers, vinyl ester polymers or aromatic vinyl polymers are used. Or a polyester resin, an alkyd resin, a polyurethane resin, or the like.
[0016]
Among these, acrylic polymers, fluoroolefin polymers, polyester resins or alkyd resins are particularly preferable.
[0017]
In order to prepare a carboxyl group-containing vinyl polymer of the carboxyl group-containing polymer (A), for example, (i) a vinyl monomer having a carboxyl group is homopolymerized, or the carboxyl group A method of copolymerizing the vinyl-containing monomer and other vinyl monomers copolymerizable with these monomers,
[0018]
(Ii) Various known and commonly used methods such as a method of adding a polyvalent carboxylic acid anhydride to a vinyl polymer having a hydroxyl group as an essential functional group prepared in advance. Although it can be applied, the method (i) is the simplest.
[0019]
Examples of carboxyl group-containing vinyl monomers that can be used in preparation according to the above method (i) are only typical, and (meth) acrylic acid, crotonic acid, itaconic acid, Various unsaturated carboxylic acids, such as maleic acid or fumaric acid;
[0020]
Monoesters (half-esters) of unsaturated dicarboxylic acids such as monomethyl itaconate, monobutyl itaconate, monomethyl maleate, monobutyl maleate, monomethyl fumarate, monobutyl fumarate and saturated monohydric alcohols;
[0021]
Various monovinyl esters from various saturated dicarboxylic acids such as monovinyl adipate or monovinyl succinate; or various saturated polycarboxylic acids such as succinic anhydride, glutaric anhydride, phthalic anhydride or trimellitic anhydride And an addition reaction product of various hydroxyl group-containing vinyl monomers as described later.
[0022]
Examples of other vinyl monomers that can be copolymerized with the carboxyl group-containing vinyl monomers as described above are only typical, and methyl (meth) acrylate and ethyl (meth) acrylate , N-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or lauryl (meth) acrylate, C ₁ ~ C _{twenty two} Various alkyl (meth) acrylates having an alkyl group;
[0023]
Various alicyclic alkyl (meth) acrylates such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate or isobornyl (meth) acrylate; various aralkyls such as benzyl (meth) acrylate or phenethyl (meth) acrylate ( (Meth) acrylates;
[0024]
Various alkyl esters of crotonic acid such as methyl crotonate or ethyl crotonate; various unsaturated dicarboxylic acids such as dimethyl malate, dibutyl malate, dimethyl fumarate, dibutyl fumarate, dimethyl itaconate or dibutyl itaconate Dialkyl esters of acids;
[0025]
Various aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene or vinyltoluene; such as N, N-dimethyl (meth) acrylamide or N, N-diethyl (meth) acrylamide Various N, N-disubstituted (meth) acrylamides; various cyano group-containing monomers such as (meth) acrylonitrile or crotononitrile;
[0026]
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether or 2-hydroxyethyl allyl Hydroxyl-containing monomers such as ethers;
[0027]
Various haloolefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, vinyl chloride or vinylidene chloride; various α such as ethylene, propylene, isobutylene or 1-butene -Olefins;
[0028]
Or vinyl acetate, vinyl propionate, vinyl pivalate or C ₈ ~ C _Ten And various carboxylic acid vinyl esters such as vinyl versatate having a branched alkyl group, and various alkyl- or cycloesters such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether or cyclohexyl vinyl ether. And alkyl vinyl ethers.
[0029]
In order to prepare the carboxyl group-containing vinyl (co) polymer (A) using various monomers as listed above, a solution polymerization method, a non-aqueous dispersion polymerization method or a bulk polymerization method is used. Various known polymerization methods such as the above can be applied. Among them, the solution radical polymerization method or the non-aqueous dispersion radical polymerization method in an organic solvent is particularly convenient.
[0030]
As the polymerization initiator used when applying the solution radical polymerization method, various known and commonly used compounds can be used, but only typical ones among them are exemplified. Various azo compounds such as 2,2′-azobis (isobutyronitrile) or 2,2′-azobis (2,4-dimethylvaleronitrile);
[0031]
tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, di-tert-butyl peroxide, dicumyl Various peroxides such as peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide or diisopropyl peroxycarbonate.
[0032]
As the organic solvent, various known and commonly used compounds can be used, but only typical ones among them can be exemplified as methanol, ethanol, n-propanol, i-propanol. Various alcohols such as n-butanol, i-butanol, tert-butanol, amyl alcohol, i-amyl alcohol or tert-amyl alcohol;
[0033]
Glycol ethers such as ethyl cellosolve or butyl cellosolve; various esters such as methyl acetate, ethyl acetate, n-butyl acetate or i-butyl acetate; various ether esters such as ethyl cellosolve acetate or butyl cellosolve acetate;
[0034]
Various aromatic hydrocarbons such as benzene, toluene or xylene; such as n-hexane, n-heptane, n-octane, isooctane, n-decane, cyclohexane, methylcyclohexane or 1,3,5-trimethylcyclohexane; Various aliphatic or alicyclic hydrocarbons;
[0035]
Furthermore, there are various ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone, and it goes without saying that these solvents may be used alone or in combination of two or more.
[0036]
By applying a known and commonly used solution radical polymerization method using monomers, a polymerization initiator, and an organic solvent, respectively, the target carboxyl group-containing vinyl polymer (A ) Can be prepared.
[0037]
Further, in order to prepare this carboxyl group-containing vinyl polymer (A) according to the non-aqueous dispersion radical polymerization method, among the various solvents as described above, aliphatic or alicyclic hydrocarbons are used. Is used as an essential solvent component, and is dissolved in such aliphatic or alicyclic hydrocarbons, in the presence of various polymers for the known and usual dispersion stabilization, as described above. Various monomers may be radically polymerized.
[0038]
The amount of the carboxyl group to be introduced into the carboxyl group-containing vinyl polymer (A) thus obtained is 0.1 to 0.1 g per 1,000 g of the solid content of the vinyl polymer (A). The range of 7 mol is appropriate, preferably the range of 0.2 to 6 mol is appropriate, and still more preferably the range of 0.3 to 4 mol is appropriate.
[0039]
When the amount is less than 0.1 mol, the curability is inevitably inferior, and as a result, the durability of the resulting cured product also decreases. On the other hand, when it exceeds 7 mol, the amount is excessively increased. In any case, the compatibility with the polysiloxane having an epoxy group is lowered, and the water resistance and chemical resistance of the cured product are lowered.
[0040]
The vinyl polymer (A) has a number average molecular weight in the range of 300 to 100,000, preferably in the range of 600 to 50,000, and more preferably 600. A range of ˜30,000 is appropriate.
[0041]
If it is less than 300, the curability and the mechanical strength of the cured product are inevitably inferior. On the other hand, if it exceeds 100,000, it is inevitably non-volatile. In this case, it is not preferable because the content is remarkably reduced and the coating workability is deteriorated.
[0042]
Next, in order to prepare the above-mentioned polyester resin (A) having a carboxyl group used in the present invention, various known and commonly used polyvalent carboxylic acid components and polyhydric alcohol components are used. If necessary, a monovalent carboxylic acid component other than fatty acid may be used in accordance with various known and commonly used methods.
[0043]
In order to prepare the alkyd resin (A) having a carboxyl group used in the present invention, in addition to various known and commonly used polyvalent carboxylic acid components and polyhydric alcohol components, fatty acids or fats and oils What is necessary is just to carry out in accordance with a well-known and usual method using what is called oil components like these, and also using monovalent carboxylic acid components other than a fatty acid if necessary.
[0044]
Examples of such polyvalent carboxylic acid components used in preparing the carboxyl group-containing polyester resin or alkyd resin are only phthalic acid, isophthalic acid, terephthalic acid, succinic acid. , Adipic acid, sebacic acid, trimellitic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid, but also various reactivity such as these acid anhydrides or methyl esters. Derivatives can also be used.
[0045]
Examples of monovalent carboxylic acids other than fatty acids are various compounds such as benzoic acid or p-tert-butylbenzoic acid.
[0046]
Further, only typical examples of the polyhydric alcohol component are exemplified: ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, trimethylolethane. , Pentaerythritol or diglycerin,
[0047]
Furthermore, various epoxy compounds such as ethylene oxide, propylene oxide, versatic acid monoglycidyl ester or bisphenol glycidyl ether type epoxy resin can also be used as reactive derivatives of polyhydric alcohols.
[0048]
Furthermore, only typical oil components used in preparing the alkyd resin are exemplified, such as safflower oil, linseed oil, tung oil, soybean oil, cottonseed oil, castor oil or tall oil. Various oils, in addition to these oils,
[0049]
Various fatty acids such as stearic acid, oleic acid, linoleic acid, linolenic acid, linolenic acid, eleostearic acid, ricinoleic acid or palmitic acid derived from such oils can also be used.
[0050]
To prepare a polyester resin or alkyd resin having a carboxyl group as an essential functional group from various raw materials as described above, a condensation method in the absence of a solvent, a dehydration condensation method in the presence of a solvent, etc. Various known and conventional methods can be applied.
[0051]
The number average molecular weight of the polymer (A) other than the vinyl polymer such as a polyester resin, an alkyd resin, or a polyurethane resin that is prepared in this manner is 300 to 30,000. The range is preferably within the range of 500 to 20,000, and more preferably within the range of 500 to 10,000.
[0052]
If it is less than 300, the mechanical strength of the cured product is inevitably deteriorated. On the other hand, if it exceeds 30,000, the content of carboxyl groups in the polymer is inevitably high. Since it becomes low, sclerosis | hardenability etc. become remarkably low, and also it becomes inferior to coating workability | operativity etc. as a result, in any case, it is unpreferable.
[0053]
The polymer (D) having an amino group as an essential functional group used in the present invention is selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group, at least This refers to a polymer having at least two amino groups per molecule.
[0054]
Examples of the amino group-containing polymer (D) include only typical ones, such as acrylic polymers, fluoroolefin polymers, vinyl ester polymers or aromatic vinyl polymers. Examples include various vinyl polymers, polyester resins, alkyd resins, and polyurethane resins.
[0055]
Among these, acrylic polymers, fluoroolefin polymers, polyester resins or alkyd resins are particularly preferable.
[0056]
In order to prepare a vinyl polymer having a primary amino group or a secondary amino group in the polymer (D), (iii) an epoxy group-containing vinyl polymer prepared in advance to ammonia or methylamine, A method of reacting various primary amines such as ethylamine or n-propylamine,
[0057]
(Iv) A carboxyl group-containing vinyl polymer prepared in advance to various alkylene imines such as ethyleneimine or propyleneimine; or various N-substituted alkylenes such as N-methylethyleneimine or N-methylpropyleneimine. What is necessary is just to follow the well-known and usual various methods, such as the method of adding imines etc.
[0058]
In accordance with the method (iii) above, the epoxy group-containing vinyl polymer used when preparing a vinyl polymer having a primary amino group or a secondary amino group as an essential functional group is, for example, glycidyl ( Or homopolymerizing various epoxy group-containing vinyl monomers such as (meth) acrylate, glycidyl vinyl ether or allyl glycidyl ether,
[0059]
Or what is necessary is just to make it copolymerize with the other monomers which can be copolymerized used when preparing the carboxyl group-containing vinyl polymer mentioned above. In order to prepare a vinyl polymer having a primary amino group or a secondary amino group by reacting the epoxy group-containing vinyl polymer thus obtained with ammonia or primary amines, for example, US Pat. Nos. 4,545,521 and U.S. Pat. No. 4,785,054 may be used.
[0060]
In order to prepare a vinyl polymer having a primary amino group or a secondary amino group in accordance with the method (iv), the carboxyl group-containing vinyl polymer prepared as described above is prepared by, for example, The alkyleneimine or the N-substituted alkyleneimine may be added in accordance with a method as disclosed in JP-A-277574.
[0061]
To prepare a vinyl polymer having a tertiary amino group as an essential functional group among the amino group-containing polymer (D), (v) an epoxy group-containing vinyl prepared in advance as described above. It is a method in which various secondary amines such as dimethylamine, diethylamine or di-n-propylamine are reacted with the polymer,
[0062]
(Vi) A method in which a vinyl monomer having a tertiary amino group is homopolymerized or copolymerized with another vinyl monomer capable of copolymerization, or (vii) prepared in advance. Such as a method of reacting a compound having both an active hydrogen group and a tertiary amino group with a carboxylic acid anhydride-containing vinyl polymer,
[0063]
Various known and commonly used methods can be applied. Among these, the method (vi) or (vii) is convenient, and a tertiary amino group is obtained by the method (vii). In order to prepare the vinyl-containing polymer (D), for example, a method as disclosed in JP-A-60-188407 may be followed.
[0064]
Only typical examples of the tertiary amino group-containing vinyl monomer used in preparing the tertiary amino group-containing vinyl polymer (D) according to the method (vi) are exemplified. 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylamino Various tertiary amino group-containing (meth) acrylic esters such as butyl (meth) acrylate or N- [2- (meth) acryloyloxy] ethylmorpholine;
[0065]
N- (2-dimethylamino) ethyl (meth) acrylamide, N- (2-diethylamino) ethyl (meth) acrylamide, N- (2-di-n-propylamino) ethyl (meth) acrylamide, N- (3- Tertiary amino group-containing (meth) acrylamides such as dimethylamino) propyl (meth) acrylamide, N- (4-dimethylamino) butyl (meth) acrylamide or N- [2- (meth) acrylamide] ethylmorpholine;
[0066]
N- (2-dimethylamino) ethylcrotonic acid amide, N- (2-diethylamino) ethylcrotonic acid amide, N- (2-di-n-propylamino) ethylcrotonic acid amide, N- (3-dimethylamino) Various tertiary amino group-containing crotonic acid amides such as propyl crotonic acid amide or N- (4-dimethylamino) butyl crotonic acid amide;
[0067]
And various tertiary amino group-containing vinyl ethers such as 2-dimethylaminoethyl vinyl ether, 2-diethylaminoethyl vinyl ether, 3-dimethylaminopropyl vinyl ether and 4-dimethylaminobutyl vinyl ether.
[0068]
In order to prepare a tertiary amino group-containing vinyl polymer using such a tertiary amino group-containing vinyl monomer, the same method as that for preparing a carboxyl group-containing vinyl polymer as described above is used. Thus, one or a mixture of these various vinyl monomers can be radically polymerized, or these various monomers can be copolymerized with these other monomers. The mixture with the above may be radically copolymerized.
[0069]
The other vinyl monomers that can be copolymerized used at that time include various kinds of vinyl monomers that are used in preparing the carboxyl group-containing vinyl polymer (A) as described above. A compound can be mentioned.
[0070]
The amount of amino groups to be introduced into the amino group-containing vinyl polymer (D) thus obtained is 0.1 to 7 per 1,000 grams of the solid content of the vinyl polymer (D). The range of mol is preferably within the range of 0.2 to 6 mol, and more preferably within the range of 0.3 to 4 mol.
[0071]
When the amount is less than 0.1 mol, the curability is inevitably inferior, and as a result, the durability of the resulting cured product is also reduced. On the other hand, when it exceeds 7 mol, the amount is excessively increased. In any case, the compatibility with the epoxy group-containing polysiloxane is lowered, and as a result, the water resistance and chemical resistance of the cured product are lowered.
[0072]
Further, the number average molecular weight of the vinyl polymer (D) is preferably in the range of 300 to 100,000, preferably in the range of 600 to 50,000, and more preferably 600 to 50,000. A range of 30,000 is appropriate.
[0073]
If it is less than 300, the curability and the mechanical strength of the cured product are inevitably deteriorated. On the other hand, if it is too high exceeding 100,000, the nonvolatile content of the resulting composition is inevitably increased. Is extremely low and is inferior in coating workability and the like.
[0074]
As the type of amino group to be introduced into the vinyl polymer (D), it is particularly preferable to use a tertiary amino group from the viewpoints of weather resistance and yellowing by ultraviolet rays.
[0075]
In order to prepare a polyester resin or alkyd resin having a primary or secondary amino group in the amino group-containing polymer (D), (viii) a carboxyl group-containing polymer prepared as described above is used. A method of reacting a polyester resin or alkyd resin with an alkyleneimine or N-substituted alkyleneimine used in preparing the amino group-containing vinyl polymer as described above may be used. .
[0076]
Furthermore, in order to prepare a polyester resin or an alkyd resin having a tertiary amino group in the amino group-containing polymer (D), for example, (ix) using various raw materials as described above, it is known that In a polyester resin or alkyd resin having a hydroxyl group in a form prepared by various methods of
[0077]
This is a method of reacting a diisocyanate compound with an excess of an isocyanate group and then reacting a compound having both an active hydrogen group that reacts with the isocyanate group and a tertiary amino group. Or
[0078]
(X) an adduct of a diisocyanate compound prepared in advance with respect to a polyester resin or alkyd resin having a hydroxyl group and a compound having both an active hydrogen group that reacts with an isocyanate group and a tertiary amino group; Various known and conventional methods such as a method of reacting an isocyanate group-containing compound can be applied.
[0079]
As typical examples of the diisocyanate compound used in applying the method (ix), only hexamethylene diisocyanate, isophorone diisocyanate, toluene-2,4-diisocyanate, toluene-2,6 are used. -Diisocyanates,
[0080]
Diphenylmethane-4,4′-diisocyanate, hydrogenated diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate or hydrogenated xylylene diisocyanate, each of which is an aliphatic, aromatic or alicyclic compound. is there.
[0081]
If only a particularly representative compound is used as a compound having both an active hydrogen group that reacts with an isocyanate group and a tertiary amino group, which is used when the method (ix) is applied, 2-dimethyl Various hydroxyl group-containing tertiary amines such as aminoethanol, 3-dimethylaminopropanol or 2-hydroxypropyldimethylamine,
[0082]
These include various primary amino group-containing tertiary amines such as N, N-dimethylethylenediamine, 3-dimethylaminopropylamine or N- (2-aminoethyl) morpholine.
[0083]
The number average molecular weight of the polymer (D) other than the vinyl polymer such as polyester resin, alkyd resin or polyurethane resin having an amino group thus prepared is 300 to 30,000. The range is preferably within the range of 500 to 20,000, and more preferably within the range of 500 to 10,000.
[0084]
If it is less than 300, the mechanical strength of the cured product is inevitably deteriorated. On the other hand, if it exceeds 30,000, the content of amino groups in the polymer is inevitably high. Since it becomes low, sclerosis | hardenability etc. will fall remarkably and by extension will also become inferior to coating workability | operativity etc., it is not preferable in any case.
[0085]
As the type of amino group to be introduced into the polymer (D) other than the vinyl polymer, particularly from the viewpoint of weather resistance and yellowing due to ultraviolet rays, the use of a tertiary amino group is particularly important. desirable.
[0086]
Next, the above-mentioned polymer (E) having both a carboxyl group and an amino group as essential functional groups used in the present invention is a primary amino group, a secondary amino group, and a tertiary. A form that has at least one amino group and a carboxyl group selected from the group consisting of amino groups, and that the amino group and the carboxyl group together have at least two per molecule. This polymer is referred to.
[0087]
As examples of such a polymer (E), only typical ones are exemplified. Various vinyls such as an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer, or an aromatic vinyl polymer are used. In addition to polymer-based polymers, polyester resins, alkyd resins, polyurethane-based resins and the like are also included.
[0088]
Among these, acrylic polymers, fluoroolefin polymers, polyester resins or alkyd resins are particularly preferable.
[0089]
In order to prepare a vinyl polymer having both a primary amino group or a secondary amino group and a carboxyl group in the polymer (E), for example, in the method (iv) described above, a carboxyl group-containing vinyl system is prepared. An alkyleneimine or N-substituted alkyleneimine as described above may be added to the polymer at such a ratio that the carboxyl group becomes excessive.
[0090]
In order to prepare a vinyl polymer having both a tertiary amino group and a carboxyl group in the polymer (E), a carboxyl group-containing vinyl monomer as described above and a tertiary amino group-containing vinyl are used. A mixture with a monomer,
[0091]
Alternatively, a mixture of other vinyl monomers that can be copolymerized, a carboxyl group-containing vinyl monomer, and a tertiary amino group-containing vinyl monomer as described above, The copolymer may be copolymerized by a method.
[0092]
The total amount of the carboxyl group and amino group to be introduced into the vinyl polymer (E) having both a carboxyl group and an amino group thus obtained is the solid content of the vinyl polymer (E). Within a range of 0.1 to 7 mol per 1,000 gram, preferably within a range of 0.2 to 6 mol, and even more preferably within a range of 0.3 to 4 mol. Is appropriate.
[0093]
When the amount is less than 0.1 mol, the curability and the like are inevitably inferior, and as a result, the durability of the resulting cured product also decreases. On the other hand, the amount exceeds about 7 mol and becomes too much. In some cases, the compatibility with the epoxy group-containing polysiloxane is inevitably lowered, and further, the water resistance and chemical resistance of the cured product are lowered.
[0094]
The molar ratio of these two functional groups to be introduced into the vinyl polymer (E) is such that the ratio of carboxyl group: amino group is 0.1: 99.9 to 99.9: 0. Is within the range of 0.2: 99.8 to 99.8: 0.2, more preferably within the range of 0.3: 99.7 to 99.7: A range of 0.3 is appropriate.
[0095]
Further, the number average molecular weight of the vinyl polymer (E) is preferably in the range of 300 to 100,000, preferably in the range of 600 to 50,000, and still more preferably 600. A range of ˜30,000 is appropriate.
[0096]
If it is less than 300, the curability and the mechanical strength of the cured product are inevitably deteriorated. On the other hand, if it exceeds 100,000 and the nonvolatile content of the composition obtained is too high. In both cases, it is remarkably lowered, and as a result, it becomes inferior in coating workability and the like.
[0097]
As the type of amino group to be introduced into the vinyl polymer (E), the use of a tertiary amino group is particularly desirable from the viewpoints of weather resistance and yellowing by ultraviolet rays.
[0098]
In order to prepare a polyester resin or alkyd resin having both a primary amino group or a secondary amino group and a carboxyl group in the polymer (E), the polyester resin or alkyd resin is prepared by the method (viii) described above. The alkylene imines or N-substituted alkylene imines may be reacted at a ratio such that a part of the carboxyl groups introduced into the resin remains unreacted.
[0099]
In order to prepare a polyester resin or an alkyd resin having both a tertiary amino group and a carboxyl group in the polymer (E), for example, in the method (ix) or (x) described above, the polyester resin or As the alkyd resin, a resin having a carboxyl group may be used.
[0100]
The number average molecular weight of the polymer (E) other than the vinyl polymer such as polyester resin, alkyd resin or polyurethane resin having both carboxyl group and amino group thus prepared is 300 The range of ˜30,000 is preferable, and the range of 500 to 20,000 is preferable, and the range of 500 to 10,000 is more preferable.
[0101]
When it is less than 300, the mechanical strength of the cured product is inevitably deteriorated. On the other hand, when it exceeds 30,000, the content of amino groups and carboxyl groups in the polymer is excessive. Since the amount is low, curability and the like are remarkably lowered, and as a result, the coating workability is also inferior, which is not preferable in either case.
[0102]
Further, the total amount of carboxyl groups and amino groups to be introduced into the polymer (E) having both a carboxyl group and an amino group other than the vinyl polymer is at least two per molecule. And
[0103]
Moreover, the molar ratio of these two functional groups is such that the ratio of carboxyl group: amino group is within the range of 0.1: 99.9 to about 99.9: 0.1, preferably 0.2: The range of 99.8 to 99.8: 0.2 is appropriate, and the range of 0.3: 99.7 to 99.7: 0.3 is more preferable.
[0104]
In addition to the vinyl polymer, the type of amino group to be introduced into the carboxyl group / amino group combined polymer (E) is, in particular, from the viewpoint of weather resistance and yellowing due to ultraviolet rays. Use of a tertiary amino group is desirable.
[0105]
Furthermore, it has a polymerizable unsaturated double bond (polymerizable double bond) as a carboxyl group-containing polymer (A), an amino group-containing polymer (D), or a carboxyl group-amino group combined polymer (E). In the presence of a polymer other than a vinyl polymer, such as a polyester resin or an alkyd resin,
[0106]
Carboxyl group and / or tertiary obtained by radical polymerization of various vinyl monomers containing a carboxyl group-containing vinyl monomer and / or tertiary amino group-containing vinyl monomer as essential components A polyester resin or an alkyd resin in which a vinyl polymer segment having an amino group is grafted can also be used.
[0107]
In the polymer (A), polymer (D) or polymer (E) prepared as described above, and further, a hydroxyl group is also introduced into each polymer, as the component (C), The composition of the present invention, which is obtained by blending various compounds such as a polyisocyanate compound, a block polyisocyanate compound or an amino resin as described later, has a higher degree of car wash scratch resistance. A coating film can be obtained.
[0108]
The compound having a functional group that reacts with a group having active hydrogen used in the present invention and excluding the polysiloxane (B) component is a compound such as a carboxyl group, a hydroxyl group or an amino group. Each of the functional groups that react with various active hydrogen-containing groups is at least one selected from an epoxy group, a cyclocarbonate group, a hydroxymethylamino group, an alkoxymethylamino group, an isocyanate group, or a blocked isocyanate group. A compound having at least two functional groups per molecule is designated.
[0110]
Examples of compounds having an epoxy group, in particular, typical examples of polyepoxy compounds are ethylene glycol, hexanediol, neopentyl glycol, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol. Polyglycidyl ethers such as aliphatic or cycloaliphatic polyols such as sorbitol or hydrogenated bisphenol A;
[0111]
Diglycidyl ethers such as polyether polyols such as polyethylene glycol, polypropylene glycol or polytetraethylene glycol; polyglycidyl ethers of tris (2-hydroxyethyl) isocyanurate; adipic acid, butanetetracarboxylic acid, propanetricarboxylic acid, Polyglycidyl esters such as aliphatic or aromatic polycarboxylic acids such as phthalic acid, terephthalic acid or trimellitic acid;
[0112]
Various alicyclic polyepoxy compounds such as bis (3,4-epoxycyclohexylmethyl) adipate or 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate; or glycidyl (meth) acrylate, 3, Homopolymers of various epoxy group-containing vinyl monomers, such as 4-epoxycyclohexylmethyl (meth) acrylate, vinylcyclohexene oxide or glycidyl vinyl ether;
[0113]
Alternatively, various epoxy group-containing vinyl monomers such as those listed above can be copolymerized with these, (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl units, respectively. Various vinyl copolymers such as an epoxy group-containing acrylic copolymer, vinyl ester copolymer or fluoroolefin copolymer obtained by copolymerization with a monomer or the like.
[0114]
Of these compounds (C), various representative examples of amino resins having hydroxymethylamino groups or alkoxymethylamino groups are given below.
[0115]
N-hydroxymethylamide group or N-alkoxymethylamide group such as N-methylol (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, N-methylolcrotonamide or N-alkoxymethylcrotonamide, Homopolymers of various vinyl monomers;
[0116]
Alternatively, vinyl monomers having various N-hydroxymethylamide groups or N-alkoxymethylamide groups as listed above can be copolymerized with these, (meth) acrylic, vinylester, vinylether, respectively. , Aromatic vinyl or fluoroolefin vinyl monomers
[0117]
Various vinyls such as acrylic copolymers, vinyl ester copolymers or fluoroolefin copolymers having N-hydroxymethylamide groups or N-alkoxymethylamide groups obtained by copolymerization. Copolymer.
[0118]
Next, only the typical examples of the amino resin described above are exemplified, and various amino group-containing compounds such as melamine, benzoguanamine, acetoguanamine, urea or glycouril are converted into various kinds such as formaldehyde or acetaldehyde. Alkylolates obtained by reacting with aldehyde compounds;
[0119]
Alternatively, it is a partially or completely etherified product obtained by reacting such an alkylolated product with various lower alcohols such as methanol, ethanol, n-butanol or i-butanol.
[0120]
Of these compounds (C) having a particularly preferred functional group, compounds having a cyclocarbonate group, and in particular, only typical ones as polycyclocarbonate compounds are exemplified. Various polyepoxy compounds, for example, polycyclocarbonate compounds having an ethylene carbonate ring obtained by converting an epoxy group into an ethylene carbonate group by reacting with carbon dioxide in the presence of a catalyst;
[0121]
Or a homopolymer of a vinyl monomer containing a cyclocarbonate group, such as 2-oxo-1,3-dioxolan-4-ylmethyl (meth) acrylate or 2-oxo-1,3-dioxolan-4-ylmethyl vinyl ether, Alternatively, these cyclocarbonate group-containing vinyl monomers can be copolymerized with these,
[0122]
Ethylene carbonate group-containing acrylic copolymer and vinyl ester copolymer obtained by copolymerization with (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers And various vinyl copolymers such as a polymer or a fluoroolefin copolymer.
[0123]
Of these compounds (C), only compounds having an isocyanate group, especially polyisocyanate compounds, which are particularly representative are exemplified. Hexamethylene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, α, α, α ′, α′-tetramethyl-m-xylylene diisocyanate, 1,3-bisisocyanatomethylcyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5- Various diisocyanates such as diisocyanate cyclohexane or lysine diisocyanate;
[0124]
A polyisocyanate resin in a form obtained by reacting various diisocyanates as described above with various polyols; a biuret structure obtained by reacting the polyisocyanates as described above with water. Or polyisocyanates having a so-called isocyanurate structure obtained by cyclization and trimerization of various diisocyanates as described above;
[0125]
Furthermore, homopolymers of vinyl monomers having an isocyanate group, such as 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate or (meth) acryloyl isocyanate, or the like Isocyanate group-containing vinyl monomer is obtained by copolymerizing with (meth) acrylic, vinyl ester, vinyl ether, aromatic vinyl or fluoroolefin vinyl monomers that can be copolymerized with these, These include various vinyl copolymers such as acrylic copolymers, vinyl ester copolymers or fluoroolefin copolymers containing isocyanate groups.
[0126]
Among such polyisocyanates, in particular, from the viewpoint of weather resistance, aliphatic or alicyclic diisocyanate compounds, various prepolymers or vinyl polymers having an isocyanate group, such as those derived therefrom, are used. Use is particularly desirable.
[0127]
Among the compounds (C), the compound having a blocked isocyanate group, in particular, the blocked polyisocyanate compound is obtained by reacting various polyisocyanate compounds as described above with various known and commonly used blocking agents. In addition to the form as prepared, compounds in a blocked form can be used as the uretdione structure by cyclizing and dimerizing the isocyanate groups.
[0128]
Various oxime compounds, such as acetone oxime or methyl ethyl ketoxime, will be exemplified only when the typical blocking agents used in preparing the block polyisocyanate are exemplified.
[0129]
Various amide compounds such as 2-pyrrolidone, ε-caprolactam or acetanilide; various active methylene compounds such as methyl acetoacetate, ethyl acetoacetate or acetylacetone;
[0130]
Various phenolic hydroxyl group-containing compounds such as phenol or salicylic acid ester; or various carbinol group-containing compounds such as methanol or lactic acid ester.
[0131]
Of course, the various compounds (C) as described above may be used alone or in combination of two or more.
[0132]
In the present invention, the carboxyl group-containing polymer (A) and the amino group-containing polymer (D) or the carboxyl group / amino group combined polymer (E) are used in combination, respectively, As the polysiloxane (B), various known and conventional compounds can be used.
[0133]
From the standpoint of alkali resistance of the cured coating film, etc .: (1) Content of a hydroxyl group and / or hydrolyzable group bonded to a silicon atom, which is a polysiloxane having a branched structure (branched structure) Of less than a specific amount [hereinafter also referred to as polysiloxane (PS-1). Or (2) a linear polysiloxane having an epoxy group at the terminal and / or side chain, and the content of hydroxyl groups and / or hydrolyzable groups bonded to silicon atoms is a specific amount. Less than [hereinafter also referred to as polysiloxane (PS-2). ],
[0134]
Or (3) a polysiloxane having a cyclic structure and having a hydroxyl group and / or hydrolyzable group content less than a specific amount bonded to a silicon atom [hereinafter also referred to as polysiloxane (PS-3) . ] Is particularly desirable.
[0135]
Among these, first, as a more specific one of the above-described polysiloxane (PS-1), in each molecule, a structural unit represented by the following general formula [I] and at least two In addition, it has a specific structure in which the number of hydroxyl groups and / or hydrolyzable groups bonded to silicon atoms contained in one molecule is less than 0.6 on average. Branched (branched) polysiloxanes are particularly representative compounds.
[0136]
[Chemical formula 2]

[0137]
[However, R represents a monovalent organic group, and three oxygen atoms are each bonded to a silicon atom. ]
[0138]
In the above-mentioned general formula [I], only typical examples of “R” which is a monovalent organic group are exemplified, and methyl group, ethyl group, n-propyl group, n-butyl group are exemplified. Or C, such as an n-octyl group ₁ ~ C ₈ Various alkyl groups
[0139]
Various aryl groups such as phenyl group or p-tolyl group; or groups having various aryl groups such as various aralkyl groups such as 1-phenethyl group or 2-phenethyl group;
[0140]
Or a group having various polymerizable double bonds such as vinyl group or 3-methacryloyloxy group, and further 3-glycidoxypropyl group or 2- (3,4-epoxycyclohexyl) ethyl group Such as groups having various epoxy groups.
[0141]
Here, the group having an aryl group (aryl group-containing group) includes the aryl group as described above and a so-called aralkyl group in which an aryl group is attached to an alkyl group. It is a designation.
[0142]
The hydrolyzable group contained in the polysiloxane (PS-1) is a silicon atom such as an alkoxy group, a halogen, a phenoxy group, an isopropenyloxy group, an acetoxy group or an iminooxy group bonded to a silicon atom, respectively. It is easily hydrolyzed at the bond with the atom,
[0143]
Each of them refers to a functional group that is eliminated as an alcohol, hydrogen halide, phenol, acetone, acetic acid, or oxime compound to form a hydroxyl group bonded to a silicon atom.
[0144]
The number of hydroxyl groups and / or hydrolyzable groups bonded to these silicon atoms contained in the polysiloxane (PS-1) is preferably less than 0.6 on an average per molecule. , Less than 0.4 is suitable, and even more preferably, less than 0.2 is suitable.
[0145]
Further, the content of hydroxyl groups and / or hydrolyzable groups bonded to these silicon atoms is preferably less than 0.3 mol per 1,000 grams of the solid content of the polysiloxane (PS-1). Is suitably less than 0.2 mole, and even more preferably less than 0.1 mole.
[0146]
The number of hydroxyl groups and / or hydrolyzable groups bonded to these silicon atoms exceeds 0.6 on an average per molecule, or the content of these groups is the polysiloxane (PS-1 When the composition of the present invention is used as a one-part composition, the storage stability is particularly deteriorated. In either case, the cured coating film is liable to be deteriorated, in particular, the alkali resistance and the like are easily lowered.
[0147]
Such polysiloxane (PS-1) includes, for example, various trifunctional silane compounds such as trialkoxysilane compounds or trichlorosilane compounds and epoxy group-containing alkoxysilane compounds as essential raw material components, Using various epoxy group-containing silane compounds,
[0148]
Furthermore, if necessary, various bifunctional silane compounds such as dialkoxysilane compounds or dichlorosilane compounds, and various tetrafunctional silane compounds such as tetraalkoxysilane or tetrachlorosilane are also used. Can be prepared.
[0149]
Examples of the trifunctional silane compounds used in preparing the polysiloxane (PS-1) are only typical, and methyltrimethoxysilane, ethyltrimethoxysilane, n -Propyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane,
[0150]
Various trialkoxysilane compounds such as methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, phenyltriethoxysilane or vinyltriethoxysilane;
[0151]
Or various trichlorosilane compounds such as methyltrichlorosilane, ethyltrichlorosilane, n-propyltrichlorosilane or phenyltrichlorosilane or vinyltrichlorosilane;
[0152]
Alternatively, various triacetoxysilane compounds such as methyltriacetoxysilane, ethyltriacetoxysilane, or phenyltriacetoxysilane.
[0153]
Of course, among the epoxy group-containing silane compounds as will be described later, a trifunctional silane compound can also be used as one of the trifunctional silane compounds referred to herein.
[0154]
Then, only typical examples of the epoxy group-containing silane compound are exemplified. 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltri Various trifunctional silane compounds such as isopropenyloxirane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane;
[0155]
Or 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiisopropenyloxirane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2 -Various bifunctional silane compounds such as (3,4-epoxycyclohexyl) ethylethyldiethoxysilane;
[0156]
Or 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropyldimethylisopropenyloxirane, 2- (3,4-epoxycyclohexyl) ethyldimethylmethoxysilane, 2- ( And various monofunctional silane compounds such as 3,4-epoxycyclohexyl) ethyldimethylethoxysilane.
[0157]
Examples of the bifunctional silane compounds described above are only typical, and dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane,
[0158]
Various dialkoxysilane compounds such as di-n-propyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane or methylphenyldiethoxysilane;
[0159]
Or various dichlorosilane compounds such as dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane or di-n-propyldichlorosilane;
[0160]
Or various diacetoxysilane compounds such as dimethyldiacetoxysilane, diethyldiacetoxysilane, di-n-propyldiacetoxysilane or diphenyldiacetoxysilane;
[0161]
Furthermore, various cyclic polysiloxanes such as hexamethyltricyclosiloxane or octamethyltetracyclosiloxane.
[0162]
Examples of the tetrafunctional silane compounds described above include only typical ones. Various tetraalkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane or tetra-n-butoxysilane; or tetrachlorosilane Alternatively, various tetrahalogenosilane compounds such as tetrabromosilane.
[0163]
In order to prepare the polysiloxane (PS-1) using various silane compounds as described above, various known and conventional methods can be applied. For example, (xi) Trifunctionality It is a method of hydrolytic condensation of a mixture of the silane compound and epoxy group-containing silane compound
[0164]
(Xii) A method of hydrolyzing and condensing a trifunctional silane compound to prepare a terminal-functional silane compound having a branched structure (branched structure) and then reacting with an epoxy group-containing silane compound. Or there is
[0165]
(Xiii) After preparing a terminal functional silane compound having a branched structure (branched structure) by hydrolytic condensation of a mixture of a trifunctional silane compound and a bifunctional silane compound, an epoxy group Various methods such as a method of reacting the contained silane compound can be applied.
[0166]
Thus, when preparing the polysiloxane (PS-1), if necessary, a monofunctional silane compound is used in combination with a hydroxyl group bonded to a silicon atom, or various types as described above. Hydrolyzable groups can be efficiently reduced.
[0167]
Examples of such monofunctional silane compounds are only typical, and various monochlorosilanes such as trimethylchlorosilane, triethylchlorosilane, tri-n-propylchlorosilane, or triphenylchlorosilane;
[0168]
Or various monoalkoxysilane compounds such as trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane or triphenylethoxysilane;
[0169]
Alternatively, various monoacetate compounds such as trimethylsilylacetate or triethylsilylacetate; or various hydrosilane compounds such as trimethylsilane or triethylsilane.
[0170]
The epoxy equivalent of the polysiloxane (PS-1) thus prepared is suitably in the range of 150 to 6,000, preferably in the range of 200 to 4,000. More preferably, the range of 250 to 2,500 is appropriate.
[0171]
When the epoxy equivalent is less than 150, it is apt to be difficult to obtain characteristics such as weather resistance, and in particular, when it exceeds 6,000, it is inevitably cured. In any case, it is not preferable.
[0172]
The polysiloxane (PS-1) contains various aryl groups such as an aryl group and an aralkyl group together with a monovalent organic group having an epoxy group as a functional group for crosslinking on a silicon atom. A compound having a monovalent organic group which does not have an epoxy group, such as a group, an alkyl group, a substituted alkyl group or a vinyl group,
[0173]
In order to meet the object of the present invention and to bring out the effects of the present invention, it is compatible with the aforementioned polymer (A), (D) or (E), that is, a curing obtained from the clear composition. The polysiloxane (PS-1) is a compound having the following form, particularly from the viewpoint of transparency of an object, or from the viewpoint of interlayer adhesion with an undercoat film or recoatability. Use is particularly desirable.
[0174]
(1) An aryl group-containing group (s-1) and an aryl group-free group (s-2) are combined as a monovalent organic group (s) excluding an epoxy group-containing group on a silicon atom. Moreover, the ratio of aryl group-containing group (s-1) / aryl group-free group (s-2) is such that the molar ratio is about 1/9 or more,
[0175]
(2) The monovalent organic group (s) excluding the epoxy group-containing group on the silicon atom has only an aryl group-containing group (s-1),
[0176]
(3) An aryl group-containing group (s-1) and an aryl group-free group (s-2) are combined as a monovalent organic group (s) excluding an epoxy group-containing group on a silicon atom. Moreover, the ratio of aryl group-containing group (s-1) / aryl group-free group (s-2) is less than 1/9 in terms of molar ratio, and an epoxy equivalent of 200 to 500 Having something like
[0177]
Or
[0178]
(4) A group having an aryl group-free group (s-2) as a monovalent organic group (s) excluding an epoxy group-containing group on a silicon atom, and a range of 200 to 500 Having an epoxy equivalent weight within.
[0179]
Among the polysiloxanes (PS-1) of the above-mentioned forms (1) to (4), an aryl group-containing group (s-1) and an aryl group-free group (s-2) From the industrial viewpoint, it is particularly desirable to use a phenyl group and an alkyl group having 1 to 4 carbon atoms.
[0180]
If only typical examples of such epoxy group-containing polysiloxanes are exemplified, "D10-0", "D7-3", "D4-6", "D1-9" or "T7-" 3 ”[trade name manufactured by Toray Dow Corning Silicone Co., Ltd.],“ XC96-A4462 ”[trade name manufactured by Toshiba Silicone Co., Ltd.], and the like.
[0181]
Next, as the number of hydroxyl groups and / or hydrolyzable groups bonded to silicon atoms contained in the linear polysiloxane (PS-2) having an epoxy group at the terminal and / or side chain as described above, An average of less than 0.6 per molecule, preferably less than 0.4, and more preferably less than 0.2 is appropriate.
[0182]
If the number of hydroxyl groups and / or hydrolyzable groups bonded to these silicon atoms exceeds 0.6 on an average per molecule, the cured coating, in particular, the alkali resistance, etc., may decrease. Since it becomes easy to become, it is not preferable.
[0183]
Most preferred, but more specific, of such polysiloxane (PS-2) is silicon as represented by the following compositional formula [II], [III], [IV] or [V]. Examples thereof include compounds having no hydroxyl group and / or hydrolyzable group bonded to an atom.
[0184]
[Chemical 3]

[0185]
[However, R in the formula ¹ , R ² , R ^Three And R ^Four Are each an aryl group, an aralkyl group or an alkyl group having 1 to 4 carbon atoms, which may be the same or different, X represents a monovalent organic group having an epoxy group, and a is an integer of 2 to 40. ]
[0186]
[Formula 4]

[0187]
[However, R in the formula ¹ , R ² , R ^Three , R ^Four And R ^Five Are each an aryl group, an aralkyl group or an alkyl group having 1 to 4 carbon atoms, which may be the same or different, X represents a monovalent organic group having an epoxy group, and b is an integer of 1 to 39, c is an integer of 1 to 20, and the sum of b and c is in the range of an integer of 2 to 40. ]
[0188]
[Chemical formula 5]

[0189]
[However, R in the formula ¹ , R ² , R ^Three , R ^Four , R ^Five And Y represents the same or different aryl group, aralkyl group or alkyl group having 1 to 4 carbon atoms, X represents a monovalent organic group having an epoxy group, Further, d is an integer of 1 to 38, e is an integer of 2 to 20, and the sum of d and e is in the range of an integer of 3 to 40. ]
[0190]
[Chemical 6]

[0191]
[However, R in the formula ¹ , R ² , R ^Three , R ^Four , R ^Five And Y represents the same or different aryl group, aralkyl group or alkyl group having 1 to 4 carbon atoms, X represents a monovalent organic group having an epoxy group, Further, f is an integer of 1 to 39, g is an integer of 1 to 20, and the sum of f and g is in the range of an integer of 2 to 40. ]
[0192]
Among the polysiloxanes represented by the above-mentioned composition formula [II], those having an epoxy equivalent in the range of 202 to 400, or having an epoxy equivalent of 400 to 1 are especially considered from the viewpoint of recoatability. , 500, and organic groups bonded to silicon atoms, R ¹ , R ² , R ^Three And R ^Four It is particularly desirable that the ratio of various aryl group-containing groups such as aryl groups or aralkyl groups in the total amount of is about 10 mol% or more.
[0193]
Among the polysiloxanes represented by the above-mentioned composition formula [III], those having an epoxy equivalent in the range of 160 to 400, or having an epoxy equivalent of 400 to 1,500, especially from the viewpoint of recoatability. Each of which is an organic group bonded to a silicon atom, R ¹ , R ² , R ^Three , R ^Four And R ^Five It is particularly desirable that the ratio of various aryl group-containing groups such as aryl groups or aralkyl groups in the total amount of is 10 mol% or more.
[0194]
Further, among the polysiloxanes represented by the above-mentioned composition formula [IV], those having an epoxy equivalent in the range of 160 to 400, or having an epoxy equivalent of 400 to 1,500, especially from the viewpoint of recoatability. Each of which is an organic group bonded to a silicon atom, R ¹ , R ² , R ^Three , R ^Four And R ^Five It is particularly desirable that the ratio of various aryl group-containing groups such as aryl groups or aralkyl groups in the total amount of is about 10 mol% or more.
[0195]
Furthermore, among the polysiloxanes represented by the above-mentioned composition formula [V], those having an epoxy equivalent of 160 to 400, or an epoxy equivalent of about 400 to 1,500, especially from the viewpoint of recoatability. In addition, each of R is an organic group bonded to a silicon atom. ¹ , R ² , R ^Three , R ^Four And R ^Five It is particularly desirable that the ratio of various aryl group-containing groups such as aryl groups or aralkyl groups in the total amount of is 10 mol% or more.
[0196]
Next, the number of hydroxyl groups and / or hydrolyzable groups bonded to silicon atoms contained in the cyclic polysiloxane (PS-3) having two or more epoxy groups per molecule as described above In general, in terms of a single molecule, less than 0.6 is appropriate, preferably less than 0.4, and even more preferably less than 0.2 is appropriate.
[0197]
If the number of hydroxyl groups bonded to these silicon atoms, hydrolyzable groups and / or silicon atoms exceeds one molecule average, more than 0.6, it is unavoidable that In particular, the alkali resistance tends to be lowered, which is not preferable.
[0198]
Most preferred, but more specific, of such polysiloxane (PS-3) is a hydrolyzable group bonded to a silicon atom and / or represented by the following composition formula [VI] and / or Examples thereof include compounds having no hydroxyl group bonded to a silicon atom.
[0199]
[Chemical 7]

[0200]
[However, R in the formula ¹ , R ² And R ^Three Are each an aryl group, an aralkyl group or an alkyl group having 1 to 4 carbon atoms, which may be the same or different, X represents a monovalent organic group having an epoxy group, and h is an integer of 0 or 1 to 4, i is an integer of 2 to 6, and the sum of h and i is in the range of an integer of 3 to 6. ]
[0201]
In the above-described composition formulas [II] to [VI], only a representative example of the aryl group is exemplified as a phenyl group or a p-tolyl group.
[0202]
Moreover, if only a particularly typical one is exemplified as the aralkyl group, it is a 2-phenylethyl group or a 1-phenylethyl group.
[0203]
Alternatively, only typical examples of monovalent organic groups having an epoxy group are exemplified, such as a 3-glycidoxypropyl group or a 2- (3,4-epoxycyclohexyl) ethyl group. It is.
[0204]
Among the polysiloxanes (PS-1), (PS-2), or (PS-3) having various epoxy groups as listed above, the cured coating film, particularly, in terms of weather resistance, etc. For example, the use of polysiloxane (PS-1) is particularly desirable.
[0205]
As described above, various carboxyl group-containing polymers (A), amino group-containing polymers (D), or carboxyl-amino group combined polymers (E), the polysiloxane (B), and the compound (C ) From the weight blending ratio when preparing the curable resin composition of the present invention,
[0206]
When component (C) is other than an amino resin, the solids of component (D) and component (B) are each 100 parts by weight of the total solid content of component (A) and component (B); For 100 parts by weight of the total amount of the components; or for 100 parts by weight of the total amount of the solids of the component (E) and the component (B),
[0207]
Each component is added so that the total solid content of component (C) is 1 to 250 parts by weight, preferably 2 to 200 parts by weight, and particularly preferably 3 to 150 parts by weight. What is necessary is just to make it mix.
[0208]
When the amino resin described above is used as the component (C), 100 parts by weight of the total solid content of the component (A) and the component (B), respectively; the component (D), the component (B), and For 100 parts by weight of the total solid content of
[0209]
Alternatively, the solid content of the amino resin is preferably 1 to 70 parts by weight, preferably 2 to 50 parts by weight with respect to 100 parts by weight of the total solids of component (E) and component (B). As such, an amino resin may be added.
[0210]
As the component (C), the equivalent compounding ratio in the case of using a compound having a functional group excellent in reactivity with a carboxyl group or an amino group, such as an epoxy group or a cyclocarbonate group, With respect to 1 equivalent of the carboxyl group and / or amino group contained in (A), component (D) or component (E),
[0211]
Preferably, the total amount of functional groups that react with the carboxyl group or amino group in the component (B) and the component (C) is in the range of 0.2 to 5 equivalents, preferably 0.5 to 2 The component (C) may be blended so as to be in the range of 0.7 equivalents, more preferably in the range of 0.7 to 1.5 equivalents.
[0212]
As the compound (C), when using a compound having a functional group excellent in reactivity with a hydroxyl group, such as an isocyanate group or a blocked isocyanate group, as an equivalent blending ratio, the component (A), the component ( D) or 1 equivalent of the total of hydroxyl groups and / or carboxyl groups contained in component (E),
[0213]
In this component (C), the functional group that reacts with the hydroxyl group is in a range of 0.2 to 5 equivalents, preferably in a range of 0.5 to 2.0 equivalents. Preferably, the component (C) may be blended so as to be within a range of 0.7 to 1.5 equivalents.
[0214]
In particular, from the viewpoint of weather resistance and recoatability, the proportion of (B) in the total solid content of the composition of the present invention is within the range of 5 to 95% by weight, preferably 10 to 90% by weight. %, And more preferably within the range of 15 to 85% by weight.
[0215]
The liquid curable resin composition of the present invention can be used in any form such as an organic solvent solution type, an organic solvent dispersion type, or a solventless liquid type, depending on the application application.
[0216]
The liquid curable resin composition of the present invention can be used as it is as a clear composition, or it can be used as a so-called colored composition in a form in which a pigment is blended.
[0217]
Furthermore, the composition of the present invention may be blended with various known and conventional additives such as a curing catalyst, a leveling agent, an ultraviolet absorber, an antioxidant, or a pigment dispersant, if necessary. I can do it.
[0218]
Of these additives, only typical examples of curing catalysts are exemplified. Various organic phosphines such as trimethylphosphine, triethylphosphine or triphenylphosphine; dibutyltin diacetate, dibutyltin dioctoate Various metal carboxylates such as dibutyltin dilaurate, tin octylate, zinc naphthenate or zinc octylate;
[0219]
1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or 1,4-diazabicyclo [2.2.2] Octane (DABCO);
[0220]
Various tertiary amines such as tri-n-butylamine or dimethylbenzylamine; tetramethylammonium salt, tetrabutylammonium salt, trimethyl (2-hydroxypropyl) ammonium salt, cyclohexyltrimethylammonium salt, tetrakis (hydroxymethyl) ammonium Various quaternary ammonium salts such as salts or o-trifluoromethylphenyltrimethylammonium salts;
[0221]
Various imidazoles such as imidazole, 1-methylimidazole, 2,4-dimethylimidazole or 1,4-diethylimidazole; or various types such as triisopropylaluminate (aluminum triisopropoxide) or tetraisopropyl titanate Metal alcoholates;
[0222]
Or various quaternary phosphonium salts such as tetramethylphosphonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, trimethyl (2-hydroxypropyl) phosphonium salt, tetraphenylphosphonium salt or benzyltriphenylphosphonium salt, etc. It is.
[0223]
In addition, in the above-described quaternary ammonium salts and quaternary phosphonium salts, various representative examples such as chloride, bromide, carboxylate, hydroxide, and the like can be given only as representative examples of so-called counter anions. Anions and the like.
[0224]
Addition of such curing catalysts, in particular, imparts low temperature curability or room temperature curability to the composition comprising the component (A), the component (B), and the component (C). It can be said that it is particularly effective.
[0225]
When the curing catalyst is added to the composition of this form comprising the component (A), the component (B), and the component (C), 1 of the total solid content of these three components A range in which the amount of the group or atomic group having a catalytic effect is 5 to 1,000 mmol, preferably 10 to 500 mmol, is appropriate for 000 grams.
[0226]
In addition to the various curing catalysts as described above, various polymers having atomic groups and groups that exhibit the catalytic effect as described above may also be used as effective catalysts. I can do it.
[0227]
The liquid curable resin composition of the present invention thus obtained has a temperature range of about 100 ° C. to 250 ° C. when the component (A), the component (B), and the component (C) are combined. Thus, by performing baking for about 30 seconds to about 1 hour, a cured product having extremely excellent durability and the like can be obtained.
[0228]
Apart from this, when the (D) component or the (E) component is combined with the (B) component and the (C) component, depending on the amino group content, from room temperature curing to baking curing It is possible to set a wide range of curing conditions.
[0229]
Further, even when the component (A), the component (B), and the component (C) are combined, the type of the curing catalyst as described above is appropriately selected as appropriate, and the optimum amount is determined. When added and blended, curing at room temperature becomes possible.
[0230]
The liquid curable resin composition of the present invention obtained as described above includes various metals such as iron, stainless steel, aluminum or brass, or various products thereof;
[0231]
Various inorganic materials such as concrete, slate, mortar or glass or their products; various plastic materials such as polypropylene, polystyrene, ABS resin or polymethyl methacrylate or their various materials Including products,
[0232]
It can be used and applied as a coating for various objects, and can also be used and applied as an adhesive or a sealing agent.
[0233]
【Example】
Next, the present invention will be described more specifically with reference examples, examples and comparative examples, but the present invention is not limited to these examples. In the following, all parts and% are based on weight unless otherwise specified.
[0234]
Reference Example 1 [Preparation example of carboxyl group-containing polymer (A)]
A reaction vessel equipped with a thermometer, reflux condenser, stirrer, dropping funnel and nitrogen gas inlet tube was charged with 500 parts of xylene and 300 parts of n-butanol, and the temperature was raised to 110 ° C. under nitrogen gas flow. Warm up.
[0235]
Then, at the same temperature, 300 parts of methyl methacrylate (MMA), 372 parts of n-butyl methacrylate (BMA), 178 parts of n-butyl acrylate (BA) and 150 parts of acrylic acid (AA), and 200 parts of xylene And a mixture of 20 parts of tert-butyl peroxyoctoate (TBO) and 10 parts of tert-butyl peroxybenzoate (TBZ) was added dropwise over 4 hours.
[0236]
Thereafter, the carboxyl group-containing acrylic polymer having a non-volatile content (NV) of 50% and a number average molecular weight (Mn) of 6,900 is maintained at the same temperature for 15 hours. A solution was obtained. Hereinafter, this is abbreviated as polymer (A-1).
[0237]
Reference example 2 (same as above)
The monomer was changed to use a mixture of 100 parts of styrene (ST), 200 parts of MMA, 550 parts of 2-ethylhexyl methacrylate (EHMA) and 150 parts of methacrylic acid (MAA). Polymerization was carried out in the same manner as in Reference Example 1, and N.I. V. Was 50% and Mn was 6,500 to obtain a carboxyl group-containing acrylic polymer solution. Hereinafter, this is abbreviated as a polymer (A-2).
[0238]
Reference example 3 (same as above)
Polymerization was conducted in the same manner as in Reference Example 1 except that a mixture consisting of 673 parts of cyclohexyl methacrylate (CHMA), 277 parts of BA and 50 parts of AA was used as the monomer. V. Was 50%, and a solution of an acrylic polymer having a carboxyl group with Mn of 5,500 was obtained. Hereinafter, this is abbreviated as a polymer (A-3).
[0239]
Reference example 4 (same as above)
The same procedure as in Reference Example 1, except that a mixture of 623 parts of CHMA, 277 parts of BA, 50 parts of 2-hydroxyethyl methacrylate (HEMA) and 50 parts of AA was used as the monomer. Polymerization is carried out. V. Of the acrylic polymer having a carboxyl group of 50% and Mn of 5,700 was obtained. Hereinafter, this is abbreviated as a polymer (A-4).
[0240]
Reference example 5 (same as above)
A 2-liter stainless steel autoclave was replaced with nitrogen gas, and then 200 parts of adipic acid monovinyl ester (MVA), “Beoba-9” (Branch (branch), manufactured by Shell of the Netherlands) was added to the autoclave. 200 parts of carboxylic acid vinyl ester], 200 parts of ethyl vinyl ether (EVE), 667 parts of methyl isobutyl ketone (MIBK), and 2,2′-azobis (2,4-dimethylvaleronitrile) ) 20 parts.
[0241]
Next, 480 parts of liquefied chlorotrifluoroethylene (CTFE) was press-fitted and sealed, and the temperature was raised to 60 ° C. with stirring. Thereafter, a polymerization reaction is carried out at the same temperature for 20 hours. V. Was a carboxyl group-containing fluoroolefin polymer solution having a 58.0% and a number average molecular weight of 21,000. Hereinafter, this is abbreviated as a polymer (A-5).
[0242]
Reference Example 6 (same as above)
A reaction vessel equipped with a thermometer, a reflux condenser with a dehydration trap, a stirrer, and a nitrogen gas introduction tube was charged with 132 parts of trimethylolpropane and 190 parts of neopentyl glycol, and the temperature was adjusted to 150 ° C. under nitrogen gas flow. The temperature was raised to.
[0243]
Next, 134 parts of hexahydrophthalic acid, 288 parts of isophthalic acid, 253 parts of adipic acid, and “Cardura E” (trade name of glycidyl ester of branched (branched) monocarboxylic acid manufactured by Shell) 105 parts and 0.85 parts of lithium hydroxide were added, the temperature was raised to 220 ° C., and a dehydration condensation reaction was performed until the acid value reached 100 at the same temperature.
[0244]
Thereafter, it was cooled and N.D. was added by adding 539 parts of xylene. V. Was 65%, and a solution of a polyester resin having a carboxyl group with a solid acid value of 100 was obtained. Hereinafter, this is abbreviated as a polymer (A-6).
[0245]
Reference example 7 (same as above)
A reactor similar to Reference Example 6 was charged with 300 parts of palm oil, 0.15 part of sodium hydroxide, and 132 parts of trimethylolpropane, and the temperature was increased to 250 ° C. under aeration of nitrogen gas. The ester exchange reaction was carried out by raising the temperature and maintaining the same temperature for 1 hour.
[0246]
The temperature was then lowered to 150 ° C., 77 parts of trimethylolpropane, 94 parts of pentaerythritol, 351 parts of hexahydrophthalic anhydride and 44 parts of phthalic anhydride, 49 parts of p-tert-butylbenzoic acid, 40 parts of xylene was added and held at 160-180 ° C. for 3 hours, then gradually raised to 220 ° C. over 2 hours, and the acid value of the solid content was further increased. The dehydration condensation reaction was carried out at the same temperature for 2 hours until reaching 5.0.
[0247]
Thereafter, the temperature was lowered to 170 ° C., 214 parts of succinic anhydride was added, held at the same temperature for 3 hours, cooled, and 270 parts of xylene and 270 parts of methyl isobutyl ketone were added. N. V. Was 60%, and a solution of a carboxyl group-containing polyester resin having a solid content acid value of 100 was obtained. Hereinafter, this is abbreviated as polymer (A-7).
[0248]
Reference Example 8 [Preparation Example of Amino Group-Containing Polymer (D)]
A reactor similar to that of Reference Example 1 was charged with 392 parts of toluene and 408 parts of isobutanol, and the temperature was raised to 80 ° C. under a stream of nitrogen gas.
[0249]
Then at the same temperature, 200 parts of ST, 300 parts of MMA, 200 parts of BMA, 200 parts of BA and 100 parts of 2- (N, N-dimethylamino) ethyl methacrylate (DMMA), azobisisobutyrate A mixture of 5 parts of rhonitrile (AIBN), 5 parts of TBO and 200 parts of toluene was added dropwise over 3 hours.
[0250]
After completion of dropping, the mixture was kept at the same temperature for 2 hours, and then a mixture of 5 parts of AIBN, 448 parts of toluene and 37 parts of isobutanol was dropped over 1 hour. .
[0251]
Furthermore, it is kept at the same temperature for 12 hours. V. Was a tertiary amino group-containing acrylic polymer having a Mn of 11,000. Hereinafter, this is abbreviated as a polymer (D-1).
[0252]
Reference Example 9 (same as above)
Reference was made except that 200 parts of ST, 200 parts of MMA, 300 parts of CHMA, 200 parts of EHMA and 100 parts of N- (3-dimethylamino) propylmethacrylamide were used as monomers. Polymerization was carried out in the same manner as in Example 8, and N.I. V. Is a tertiary amino group-containing acrylic polymer solution having a Mn of 12,000. Hereinafter, this is abbreviated as a polymer (D-2).
[0253]
Reference Example 10 (same as above)
A reactor similar to that of Reference Example 1 was charged with 392 parts of toluene and 408 parts of n-butyl acetate, and the temperature was raised to 80 ° C. under a stream of nitrogen gas.
[0254]
Then at the same temperature, 200 parts of ST, 250 parts of MMA, 200 parts of BMA, 200 parts of BA, 50 parts of HEMA and 100 parts of DMMA, 5 parts of AIBN and 5 parts of TBO, and toluene A mixture of 200 parts was added dropwise over 3 hours.
[0255]
After completion of dropping, the mixture was kept at the same temperature for 2 hours, and then a mixture of 5 parts of AIBN, 448 parts of toluene and 37 parts of n-butyl acetate was required for 1 hour. It was dripped.
[0256]
Furthermore, it is kept at the same temperature for 12 hours. V. Was a tertiary amino group-containing acrylic polymer having a Mn of 12,000. Hereinafter, this is abbreviated as a polymer (D-3).
[0257]
Reference Example 11 (same as above)
The inside of the reactor similar to that in Reference Example 5 was replaced with nitrogen gas, and then 100 parts of 2- (N, N-dimethylamino) ethyl vinyl ether (DAEVE), 100 parts of EVE and “ 400 parts of Veova-9 ", 10 parts of tert-butyl peroxypivalate (TBPV) and 429 parts of MIBK were charged.
[0258]
Next, 400 parts of the liquefied collected hexafluoropropylene was press-fitted and sealed, then heated to 60 ° C. with stirring, and a polymerization reaction was carried out at the same temperature for 17 hours. V. Is a tertiary amino group-containing fluoroolefin polymer solution having a Mn of 15,000. Hereinafter, this is abbreviated as a polymer (D-4).
[0259]
Reference Example 12 [Preparation Example of Carboxyl Group / Amino Group Copolymer (E)]
Changed to use 200 parts ST, 300 parts MMA, 200 parts BMA, 100 parts BA, 150 parts 2- (N, N-dimethylamino) ethyl acrylate and 50 parts AA as monomers. Polymerization was carried out in the same manner as in Reference Example 8 except that N. V. Of acrylic polymer having both a carboxyl group and a tertiary amino group having a Mn of 11,000. Hereinafter, this is abbreviated as a polymer (E-1).
[0260]
Reference Example 13 (same as above)
A reactor similar to that of Reference Example 1 was charged with 392 parts of toluene and 408 parts of n-butyl acetate, and the temperature was raised to 80 ° C. under a stream of nitrogen gas.
[0261]
Then at the same temperature, 200 parts of ST, 300 parts of MMA, 350 parts of EHMA, 70 parts of HEMA, 30 parts of AA and 50 parts of DMMA, 5 parts of AIBN and 5 parts of TBO, and toluene A mixture of 200 parts was added dropwise over 3 hours.
[0262]
After completion of dropping, the mixture was kept at the same temperature for 2 hours, and then a mixture of 5 parts of AIBN, 448 parts of toluene and 37 parts of n-butyl acetate was required for 1 hour. It was dripped.
[0263]
Furthermore, by holding at the same temperature for 12 hours, N.P. V. Was a tertiary amino group-containing acrylic polymer having a Mn of 12,000. Hereinafter, this is abbreviated as a polymer (E-2).
[0264]
Reference example 14 (same as above)
As monomer components other than CTFE, 200 parts of MVA, 200 parts of “Beova-9”, 150 parts of EVE and 50 parts of DAEVE were used, respectively, in the same manner as in Reference Example 5. Polymerization is carried out. V. Was 58% and Mn was 20,000, and a solution of a carboxyl group / amino group combined fluoroolefin polymer was obtained. Hereinafter, this is abbreviated as a polymer (E-3).
[0265]
Reference Example 15 [Preparation Example of Compound (C) Containing Functional Group Reacting with Group Having Active Hydrogen]
[0266]
In the same reaction vessel as in Reference Example 1, 1,400 parts of xylene was charged, and the temperature was raised to 110 ° C. under nitrogen gas.
[0267]
A mixture of 100 parts MMA, 210 parts BMA, 184 parts BA, 506 parts GMA, 506 parts GMA, 60 parts TBO and 12 parts TBZ and 100 parts xylene at the same temperature is then added for 5 hours. It was dripped over.
[0268]
Even after completion of the dropwise addition, the mixture was kept at the same temperature for 15 hours, so that N.P. V. Was 40% and a number average molecular weight of 2,900 was obtained as an acrylic polymer solution having an epoxy group. Hereinafter, this is abbreviated as compound (C-1).
[0269]
Reference Example 16 (same as above)
In the same reaction vessel as in Reference Example 1, 500 parts of xylene and 300 parts of n-butanol were charged, and the temperature was raised to 120 ° C. under a stream of nitrogen gas.
[0270]
Then at the same temperature, 200 parts of MMA, 200 parts of ST, 300 parts of BMA, 300 parts of 2-oxo-1,3-dioxolan-4-ylmethyl methacrylate, 10 parts of AIBN, and 20 parts of TBO A mixture of 10 parts of TBZ and 200 parts of xylene was added dropwise over 5 hours.
[0271]
Even after completion of the dropwise addition, the mixture was kept at the same temperature for 15 hours, so that N.P. V. Was 50% and a number average molecular weight of 10,000 was obtained as a solution of an acrylic polymer having a cyclocarbonate group. Hereinafter, this is abbreviated as compound (C-2).
[0272]
Table 1 summarizes the property values or characteristic values of the epoxy group-containing polysiloxane that is the component (B) used in the following examples.
[0273]
[Table 1]

[0274]
[Table 2]

[0275]
[Table 3]

[0276]
Examples 1-5 and Comparative Examples 1 and 2
Each clear composition obtained by mixing the component (A), the component (B), the component (C), the curing catalyst and the additive at the usage ratio as shown in Table 2 is “Solvesso 100”. (A trade name of aromatic hydrocarbon mixture manufactured by Exxon, USA) / n-butanol = 70/30 (parts by weight) with a mixed solvent so that the viscosity of Ford Cup # 4 is 20 seconds. Various clear paints were prepared by diluting to a low temperature.
[0277]
Next, each clear paint prepared in the above-described manner on a steel plate that has been preliminarily coated with a polyester-melamine-based paint and baked is adjusted to have a dry film thickness of about 30 microns (μm). Air spray painted.
[0278]
Thereafter, various cured coatings were obtained by baking under the conditions shown in Table 2.
[0279]
Each film was evaluated for various performances. The results are summarized in the same table.
[0280]
[Table 4]

[0281]
<< Footnotes in Table 2 >>
The blending ratio of each component in the table is shown in parts by weight.
[0282]
“L-117-60”: An abbreviation of “Super Becamine L-117-60”, which is a trade name of an n-butyl etherified melamine / formaldehyde resin solution manufactured by Dainippon Ink & Chemicals, Inc. Yes, the non-volatile content is 60%.
[0283]
“B7-887”: An abbreviation of “Bernock B7-887-60”, a trade name of a solution of a non-yellowing type block polyisocyanate compound manufactured by Dainippon Ink & Chemicals, Inc. The non-volatile content is 60%, and the blocked isocyanate group content is 7.9%.
[0284]
[Table 5]

[0285]
<< Footnotes in Table 2 >>
[0286]
"1-MIm" ... Abbreviation for 1-methylimidazole
[0287]
“TBAAc” ………………………… Tetrabutylammonium acetate abbreviation
[0288]
“Tinuvin 900” is a trade name of a benzotriazole-based UV absorber manufactured by Ciba-Geigy, Switzerland.
[0289]
“LS-765” is an abbreviation for “Sanol LS-765”, which is a trade name of a hindered amine antioxidant manufactured by Sankyo Corporation.
[0290]
In the table, “I” in “curing conditions” represents “baking at 140 ° C. for 30 minutes”, and the other “II” represents “baking at 160 ° C. for 30 minutes”.
[0291]
“Accelerated weather resistance” in the table is a specular reflectance (%) of 60 ° after exposure for 1,500 hours using a dew panel light control / weather meter manufactured by Suga Test Instruments Co., Ltd. ) Is divided by the gloss value of the paint film when unexposed, and multiplied by 100 (gloss retention:%). It is.
[0292]
However, the exposure with the dew panel light control / weather meter was repeated for one cycle under the following conditions.
[0293]
UV irradiation: 8 hours at 70 ° C
[0294]
Humidification: 4 hours at 40 ° C
[0295]
“Initial water repellency” in the table refers to the water droplets placed on each cured coating film using a CA-Z type automatic contact angle measuring device manufactured by Kyowa Interface Chemical Co., Ltd. The contact angle is measured and displayed by the contact angle, and is displayed by the contact angle with water.
[0296]
“Water repellency after weather resistance test” in the table is 1,500 under the same conditions as in the case of “accelerated weather resistance” using a dew panel light control weather meter manufactured by Suga Test Instruments Co., Ltd. After the exposure over time, the contact angle with water of the cured coating was measured in the same manner as in the case of the above-mentioned “initial water repellency”, and displayed with the contact angle. is there.
[0297]
"Car wash scratch resistance" in the table was impregnated with an aqueous dispersion of cleanser (weight concentration = 5%) using a rubbing tester manufactured by Taihei Rika Kogyo Co., Ltd. as a substitute test. After the rubbing of the coating film 60 times in each case under a load of 500 gram weight with a felt, the gloss value of 20 degree specular reflectance (%) is the same as that of the untested coating film. Divided by the gloss value, it is displayed as a value multiplied by 100 (gloss retention rate:%).
[0298]
[Table 6]

[0299]
<< Footnotes in Table 2 >>
“XC96”: An abbreviation for “XC96-A4462.”
[0300]
“EX-612”: An abbreviation for “Denacol EX-612”, a sorbitol polyglycidyl ether manufactured by Nagase Chemical Industries, Ltd., having an epoxy equivalent of 170. is there.
[0301]
[Table 7]

[0302]
As is clear from the results shown in the table, the cured coating film obtained from the composition of the present invention is more resistant to weathering and weathering than the cured coating films of Comparative Examples 1 and 2. You will be able to know that it is excellent in water repellency and car wash scratch resistance after the property test.
[0303]
Examples 6-8 and Comparative Examples 3 and 4
First, various white bases were prepared by dispersing a mixture of the component (A) and the pigment using a sand mill at a usage ratio as shown in Table 3.
[0304]
Next, by blending each of the white bases with the component (B), the component (C), and a curing catalyst, or by blending “Denacol EX-612” with a curing catalyst, various white bases are prepared. A composition was prepared.
[0305]
Furthermore, each white composition is diluted with a mixed solvent of “Solvesso 100” / n-butanol = 70/30 (parts by weight) so that the viscosity by Ford Cup # 4 is 25 seconds. Various white paints having a pigment weight concentration (PWC) of 40% were prepared.
[0306]
Each paint obtained in this manner was air spray-coated on a steel plate that had previously been coated with a polyester-melamine paint and baked to a dry film thickness of about 30 μm, and is shown in Table 3. Under such conditions, baking was performed to obtain various cured coating films.
[0307]
The results of evaluating various performances of each coating film are shown together in the table.
[0308]
[Table 8]

[0309]
《Legs of Table 3》
The blending ratio of each component in the table is shown in parts by weight.
[0310]
“CR-93”: An abbreviation for “Taipeke CR-93”, a trade name of rutile titanium oxide manufactured by Ishihara Sangyo Co., Ltd.
[0311]
[Table 9]

[0312]
[Table 10]

[0313]
[Table 11]

[0314]
<< Footnotes in Table 3 >>
“Accelerated weather resistance” in the table is a gloss value of 60-degree specular reflectance (%) after exposure for 2,000 hours with a sunshine weatherometer. The value is divided by the gloss value same as above and multiplied by 100 (gloss retention rate:%), and the evaluation is determined, and the value is displayed.
[0315]
Evaluation evaluation of “initial water repellency” and “car wash scratch resistance” in the table was the same as in Examples 1 to 5 and Comparative Examples 1 and 2.
[0316]
“Water repellency after weather resistance test” in the table is the contact angle with water of the cured coating film after exposure for 1,500 hours using a sunshine weatherometer. It is measured in the same manner as in the case of the “initial water repellency” described above, and is indicated by the contact angle.
[0317]
As is apparent from the results shown in the table, the cured coating films obtained using the composition of the present invention were all prepared from “Denacol EX-612”, respectively, Comparative Example 3 and Compared with the cured coating film in the case of No. 4, it can be easily understood that the weather resistance, the water repellency after the weather resistance test and the car wash scratch resistance are excellent.
[0318]
Examples 9-15 and Comparative Examples 5 and 6
First, various white bases were prepared by dispersing a mixture of the component (D) or the component (E) and the pigment with a sand mill at a usage ratio as shown in Table 4.
[0319]
Next, a white composition was prepared by blending each of the white bases with the component (B) and the component (C) or by blending “Denacol EX-612”.
[0320]
Furthermore, for the white compositions of Examples 11 and 14, with a mixed solvent of xylene / toluene / n-butyl acetate / ethyl acetate / 2-ethoxyethyl acetate = 40/30/20/10 (parts by weight). The white compositions other than Examples 11 and 14 were mixed with xylene / toluene / n-butanol / ethyl acetate / 2-ethoxyethyl acetate = 40/30/20/10 (parts by weight). Then, various white paints having a PWC of 35% were prepared by diluting so that the viscosity by Ford Cup # 4 was 17 seconds.
[0321]
Each of the paints thus obtained was pre-coated with a polyester-melamine paint and baked on the steel plate so that the dry film thickness was about 30 μm, and then at room temperature for 10 days. After being allowed to stand, various cured coatings were obtained.
[0322]
The results of evaluating and examining various performances for each coating film are summarized in the same table.
[0323]
[Table 12]

[0324]
《Legs of Table 4》
The blending ratio of each component in the table is shown in parts by weight.
[0325]
“DN-990S” is an abbreviation of “Bernock DN-990S”, which is a trade name of a non-yellowing polyisocyanate resin manufactured by Dainippon Ink and Chemicals, Inc., having a non-volatile content of 100%. And isocyanate group content rate is 17.3%.
[0326]
The “accelerated weather resistance”, “initial water repellency”, “water repellency after weather resistance test” and “car wash scratch resistance” in the table were evaluated in the same manner as in the case of Table 3.
[0327]
[Table 13]

[0328]
[Table 14]

[0329]
[Table 15]

[0330]
[Table 16]

[0331]
[Table 17]

[0332]
As is apparent from the results shown in the table, the cured coating films obtained from the composition of the present invention were both prepared from “Denacol EX-612”, respectively of Comparative Examples 5 and 6, respectively. As compared with the case of the cured coating film, it can be easily understood that, in particular, the weather resistance, the water repellency after the weather resistance test and the car wash scratch resistance are excellent.
[0333]
【The invention's effect】
The liquid curable resin composition of the present invention is particularly excellent in car wash scratch resistance and the like, and in addition to so-called durability such as gloss retention (weather resistance) and water repellency retention during exposure. It is excellent and has a very high practicality, characterized by a very high durability.

Claims (12)

The polymer (A) having a carboxyl group and the structural unit represented by the general formula [I], and further, a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom, contained in one molecule, Branched polysiloxane (B) having at least two epoxy groups in one molecule and an active hydrogen-containing group having an average of less than 0.6 and less than 0.3 mole per 1000 grams of solid content A compound having a functional group that reacts with the compound and containing the compound (C) excluding the polysiloxane (B), and the functional group that reacts with the group having active hydrogen is an epoxy group, a cyclocarbonate group, an isocyanate. group, blocked isocyanate group, a hydroxymethyl group, selected from the group consisting of alkoxymethyl amino group, and characterized in that at least one, Jo curable resin composition.

[However, R represents a monovalent organic group, and three oxygen atoms are each bonded to a silicon atom. ] A polymer (D) having an amino group and a structural unit represented by the general formula [I], and a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom, contained in one molecule, Branched polysiloxane (B) having at least 2 epoxy groups in one molecule and an active hydrogen-containing group having an average of less than 0.6 and less than 0.3 mole per 1000 grams of solid content A compound having a functional group that reacts with the compound and containing the compound (C) excluding the polysiloxane (B), and the functional group that reacts with the group having active hydrogen is an epoxy group, a cyclocarbonate group, an isocyanate. group, blocked isocyanate group, a hydroxymethyl group, selected from the group consisting of alkoxymethyl amino group, and characterized in that at least one, liquid hard RESIN composition.

[However, R represents a monovalent organic group, and three oxygen atoms are each bonded to a silicon atom. ] Each molecule has a polymer (E) having both a carboxyl group and an amino group, and a structural unit represented by the general formula [I], and is bonded to a silicon atom contained in one molecule. A branched chain having at least two epoxy groups in one molecule, having an average of less than 0.6 hydroxyl groups and / or hydrolyzable groups and less than 0.3 moles per 1000 grams of solid content A compound having a polysiloxane (B) and a functional group that reacts with a group having active hydrogen, the compound (C) excluding the polysiloxane (B), and reacts with the group having active hydrogen The functional group is selected from the group consisting of an epoxy group, a cyclocarbonate group, an isocyanate group, a blocked isocyanate group, a hydroxymethylamino group, and an alkoxymethylamino group. Characterized in that also is of one curable liquid resin composition.

[However, R represents a monovalent organic group, and three oxygen atoms are each bonded to a silicon atom. ]  The composition according to claim 1, wherein the polymer (A) having a carboxyl group is a vinyl polymer.  The composition according to claim 2, wherein the polymer (D) having an amino group is a vinyl polymer.  The composition according to claim 3, wherein the polymer (E) having both the carboxyl group and the amino group is a vinyl polymer.  The composition according to any one of claims 4 to 6, wherein the vinyl polymer is an acrylic polymer.  The composition according to any one of claims 4 to 6, wherein the vinyl polymer is a fluoroolefin polymer.  The composition according to any one of claims 1 to 3, wherein the compound (C) is at least one selected from the group consisting of a polyepoxy compound, a polyisocyanate compound, a block polyisocyanate compound, and an amino resin. object.  The composition according to claim 1, wherein the polymer (A) has a hydroxyl group.  The composition according to claim 2, wherein the polymer (D) has a hydroxyl group.  The composition according to claim 3, wherein the polymer (E) has a hydroxyl group.