JP3794444B2 - Aqueous resin composition with improved durability, antifouling coating agent and releasable coating agent - Google Patents

Description

【００５０】
（ただし、式中のｎは１〜１５０なる範囲内の整数であるものとする。）
【００５１】
Ｓ−２：
【００５２】
【化２】

【００５３】
（ただし、式中のｎは１〜１５０なる範囲内の整数であるものとする。）
【００５４】
Ｓ−３：
【００５５】
【化３】

【００５６】
（ただし、式中のｎは１〜１５０なる範囲内の整数であるものとする。）
【００５７】
Ｓ−４：
【００５８】
【化４】

【００５９】
（ただし、式中のｎは１〜１５０なる範囲内の整数であるものとする。）
【００６０】
Ｓ−５：
【００６１】
【化５】

【００６２】
（ただし、式中のｎは１〜１５０なる範囲内の整数であるものとする。）
【００６３】
Ｓ−６：
【００６４】
【化６】

【００６５】
（ただし、式中のｎは１〜１５０なる範囲内の整数であるものとする。）
【００６６】
本発明に係る、それぞれ、水性樹脂組成物ならびに防汚性コート剤および離型性コート剤を調製するに当たって用いられる、前記した水分散性ウレタン樹脂は、上掲したような各原料類を用いて、公知慣用の方法によって調製されるものである。
【００６７】
具体的なる調製の方法として特に代表的なもののみを例示するにとどめれば、次のようなものである。すなわち、前掲したような、ポリイソシアネートと、活性水素含有化合物（親水性基含有化合物をも含む。）とを、イソシアネート基／活性水素基なる当量比で以て、０．８／１〜１．２／１の比率で、好ましくは、０．９／１〜１．１／１の比率で、温度が２０〜１２０℃の条件、好ましくは、３０〜１００℃の条件で以て反応せしめるというようにすればよい。
【００６８】
これらの反応は、有機溶剤中で以て行うことができる。そして、当該有機溶剤としては、特に限定されるものではなく、公知慣用の種々のの有機溶剤が使用できるが、これらのうちでも特にメチルエチルケトンの使用が望ましい。
【００６９】
次いで、本発明に係る、それぞれ、水性樹脂組成物ならびに防汚性コート剤および離型性コート剤の調製に際し、前記したビニル系重合体を調製するに当たって用いられる、前記したパーフルオロアルキル基含有エチレン性不飽和単量体としては、特に限定されるものではなく、公知慣用の種々の化合物が、いずれも、使用可能である。
【００７０】
当該パーフルオロアルキル基含有エチレン性不飽和単量体として特に代表的なもののみを例示するにとどめれば、次の一般式
【００７１】
【化７】

【００７２】
［ただし、式中のＲｆは炭素原子数が４〜２０なるパーフルオロアルキル基を、Ｒ₁ は水素原子あるいはメチル基を、Ａは−Ｑ−、−ＣＯＮ（Ｒ₂ ）−Ｑ−または−ＳＯ₂ Ｎ（Ｒ₂ ）−Ｑ−（ただし、−Ｑ−は炭素原子数が１〜１０なるアルキレン基を、Ｒ₂ は炭素原子数が１〜４なるアルキル基を表わすものとする。）を表わすものとする。］
【００７３】
で示されるような、いわゆるパーフルオロアルキル基含有（メタ）アクリレートなどである。
【００７４】
ここにおいて、上記パーフルオロアルキル基含有（メタ）アクリレートとしては、具体的には、次のような化合物などが挙げられる。
【００７５】
すなわち
【００７６】
Ｂ−１：
【００７７】
【化８】
ＣＦ₃（ＣＦ₂）_nＣＨ₂ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂
【００７８】
（ただし、式中のｎは５〜１１なる範囲内の整数であるものとし、しかも、その平均は９であるものとする。）
【００７９】
Ｂ−２：
【００８０】
【化９】
ＣＦ₃（ＣＦ₂）₇ＣＨ₂ＣＨ₂ＯＣＯＣ（ＣＨ₃）＝ＣＨ₂
【００８１】
Ｂ−３：
【００８２】
【化１０】
ＣＦ₃（ＣＦ₂）₅ＣＨ₂ＣＨ₂ＯＣＯＣ（ＣＨ₃）＝ＣＨ₂
【００８３】
Ｂ−４：
【００８４】
【化１１】
（ＣＦ₃）₂ＣＦ（ＣＦ₂）₆（ＣＨ₂）₃ＯＣＯＣＨ＝ＣＨ₂
【００８５】
Ｂ−５：
【００８６】
【化１２】
（ＣＦ₃）₂ＣＦ（ＣＦ₂）₁₀（ＣＨ₂）₃ＯＣＯＣＨ＝ＣＨ₂
【００８７】
Ｂ−６：
【００８８】
【化１３】
ＣＦ₃（ＣＦ₂）₇ＳＯ₂Ｎ（Ｃ₃Ｈ₇）ＣＨ₂ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂
【００８９】
Ｂ−７：
【００９０】
【化１４】
ＣＦ₃（ＣＦ₂）₇ＳＯ₂Ｎ（ＣＨ₃）ＣＨ₂ＣＨ₂ＯＣＯＣ（ＣＨ₃）＝ＣＨ₂
【００９１】
Ｂ−８：
【００９２】
【化１５】
ＣＦ₃（ＣＦ₂）₇ＳＯ₂Ｎ（ＣＨ₃）ＣＨ₂ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂
【００９３】
Ｂ−９：
【００９４】
【化１６】
ＣＦ₃（ＣＦ₂）₇（ＣＨ₂）₄ＯＣＯＣＨ＝ＣＨ₂
【００９５】
Ｂ−１０：
【００９６】
【化１７】
ＣＦ₃（ＣＦ₂）₆ＣＯＯＣＨ＝ＣＨ₂
【００９７】
Ｂ−１１：
【００９８】
【化１８】
ＣＦ₃（ＣＦ₂）₇ＳＯ₂Ｎ（Ｃ₄Ｈ₉）（ＣＨ₂）₄ＯＣＯＣＨ＝ＣＨ₂
【００９９】
Ｂ−１２：
【０１００】
【化１９】
ＣＦ₃（ＣＦ₂）₇ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂
【０１０１】
Ｂ−１３：
【０１０２】
【化２０】
ＣＦ₃（ＣＦ₂）₅ＣＯＮ（Ｃ₃Ｈ₇）ＣＨ₂ＣＨ₂ＯＣＯＣ（ＣＨ₃）＝ＣＨ₂
【０１０３】
またはＢ−１４：
【０１０４】
【化２１】
ＣＦ₃（ＣＦ₂）₇ＣＯＮ（Ｃ₂Ｈ₅）ＣＨ₂ＣＨ₂ＯＣＯＣＨ＝ＣＨ₂
【０１０５】
などのような化合物が特に代表的なものとして例示される。
【０１０６】
ポリジメチルシロキサン基含有エチレン性不飽和単量体としては、分子中に、該ポリジメチルシロキサン基とエチレン性不飽和二重結合を併せ有するというようなものであれば、どのような化合物であっても構わないが、それらのうちでも特に代表的なもののみを例示するにとどめれば、次のような一般式
【０１０７】
【化２２】

【０１０８】
（ただし、式中のｎは１〜１５０なる範囲内の整数であるものとする。）
【０１０９】
で示される部類の、いわゆるマクロモノマーなどである。
【０１１０】
これらの両単量体類（モノマー類）としての、それぞれ、パーフルオロアルキル基含有エチレン性不飽和単量体および／またはポリジメチルシロキサン基含有エチレン性不飽和単量体と共重合可能なる其の他のエチレン性単量体として特に代表的なもののみを例示するにとどめれば、
【０１１１】
エチレン、プロピレン、塩化ビニル、塩化ビニリデン、スチレン、α−メチルスチレン、酢酸ビニル、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソ（ｉｓｏ）−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ｉｓｏ−ステアリル（メタ）アクリレートなどをはじめ、
【０１１２】
さらには、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボロニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、メチルビニルエーテル、プロピルビニルエーテル、オクチルビニルエーテル、ブタジエン、イソプレン、クロロプレン、２−ヒドロキシエチル（メタ）アクリレート、（メタ）アクリル酸、（メタ）アクリルアミドまたは３−クロロ−２−ヒドロキシ（メタ）アクリレートなどである。
【０１１３】
さらに、その他のエチレン性不飽和単量体として、架橋性のエチレン性不飽和単量体を使用することができるが、そうした架橋性のエチレン性不飽和単量体として特に代表的なもののみを例示するにとどめれば、Ｎ−メチロール（メタ）アクリルアミド、グリシジル（メタ）アクリレート、ジアセトンアクリルアミド、アセトアセトキシエチルアクリレート、アセトアセトキシエチルメタクリレート、アセトアセトキシエチルクロトナート、アセトアセトキシプロピルアクリレート、アセトアセトキシプロピルメタクリレート、アセトアセトキシプロピルクロトナート、２−シアノアセトアセトキシエチルメタクリレート、Ｎ−（２−アセトアセトキシエチル）アクリルアミドまたはＮ−（２−アセトアセトキシエチル）メタクリルアミドなどをはじめ、さらには、アセト酢酸アリルまたはアセト酢酸ビニルなどで代表されるような種々のアセトアセチル基含有エチレン性不飽和単量体などである。
【０１１４】
また、多官能性エチレン性不飽和単量体として特に代表的なるもののみを例示するにとどめれば、エチレンジ（メタ）アクリレート、ポリオキシアルキレンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ビスフェノールＡエチレンオキシド付加物ジ（メタ）アクリレートなどで代表されるような種々の多価アルコールとアクリル酸ないしはメタクリル酸とのエステル類などをはじめ、
【０１１５】
さらには、ウレタン樹脂骨格と不飽和基とを有するウレタン樹脂ジ（メタ）アクリレート類、エポキシ樹脂を骨格とするエポキシジ（メタ）アクリレート類あるいはポリエステル樹脂骨格の多官能性オリゴエステル（メタ）アクリレート類などである。
【０１１６】
そして、パーフルオロアルキル基含有エチレン性不飽和単量体の使用量は特に制限されないが、エチレン性不飽和単量体の総重量１００重量部に対し、つまり、エチレン性不飽和単量体の総重量１００重量部を基準として、４０〜９５重量部であることが望ましい。
【０１１７】
当該パーフルオロアルキル基含有エチレン性不飽和単量体が、４０重量部未満である場合には、どうしても、とりわけ、防汚性、撥水性、撥油性、離型性、剥離性ならびに潤滑性などのような、いわゆるフッ素樹脂の特性が充分に得られ難くなるし、一方、９５重量部よりも多くなったような場合には、それ以上のフッ素樹脂に基づく機能は得られ難くなるし、製造コストの面からは好ましくない。
【０１１８】
ポリジメチルシロキサン基含有エチレン性不飽和単量体の使用量も亦、特に制限されないが、エチレン性不飽和単量体の総重量１００重量部に対し、つまり、エチレン性不飽和単量体の総重量１００重量部を基準として、３０重量部以下であることが望ましい。
【０１１９】
当該ポリジメチルシロキサン基含有エチレン性不飽和単量体が３０重量部より多い場合は、どうしても、安定なる水分散体を得ることが困難になるために好ましくない。
【０１２０】
また、パーフルオロアルキル基含有エチレン性不飽和単量体およびポリジメチルシロキサン基含有エチレン性不飽和単量体を併用する場合には、これらの両単量体の使用量は、特に制限されないが、パーフルオロアルキル基含有エチレン性不飽和単量体が、エチレン性不飽和単量体の総量１００重量部に対し、５〜７０重量部であり、かつポリジメチルシロキサン基含有エチレン性不飽和単量体が、エチレン性不飽和単量体の総重量１００重量部に対し、３０重量部以下であることが望ましい。
【０１２１】
こうした、パーフルオロアルキル基含有エチレン性不飽和単量体と、ポリジメチルシロキサン基含有エチレン性不飽和単量体との併用によれば、本発明の効果を維持しつつ、両者の使用量を減少させることが可能になり、製造コストの面からも亦、有利である。
【０１２２】
この際に、パーフルオロアルキル基含有エチレン性不飽和単量体が５重量部未満の場合には、フッ素樹脂による離型・剥離機能が充分得られ難くなるし、一方、７０重量部より多くしても、それ以上のフッ素による機能は得られずに、製造コストの面からは好ましくない。
【０１２３】
ポリジメチルシロキサン基含有エチレン性不飽和単量体が３０重量部よりも多いような場合には、単独で以て用いた場合と同様に、安定なるエマルジョンは得られ難くなるし、製造コストの面からも好ましくない。
【０１２４】
本発明において、水分散性ウレタン樹脂と、パーフルオロアルキル基含有エチレン性不飽和単量体および／またはジメチルポリシロキサン基含有エチレン性不飽和単量体と、さらには、これらの両単量体と共重合可能なる其の他のエチレン性不飽和単量体とを反応させて得られる共重合体との割合は、前者水分散性ウレタン樹脂／後者共重合体なる重量比で以て、９／１〜１／９であることが、ビニル系共重合体の特性とウレタン樹脂の特性とを併せ有するという形の水分散体が得られることからも好ましく、耐久性のある樹脂特性を得るためには、上記重量比で以て、３／７〜７／３であることが特に好ましい。
【０１２５】
本発明に係る、それぞれ、水性樹脂組成物ならびに防汚性コート剤および離型性コート剤を調製するに当たって用いられる、前記した、ポリカルボジミド系樹脂としては、公知慣用の種々の化合物が使用可能であり、特に限定される物ではないが、それらのうちでも特に代表的なもののみを例示するにとどめれば、
【０１２６】
次の一般式
【０１２７】
【化２３】

【０１２８】
で示されるような、いわゆるイソシアネート基含有のカルボジミド化合物（Ａ）
【０１２９】
（ただし、式中のＲは芳香族または脂肪族の２価連結基を表わすものとする。）
【０１３０】
あるいは此等の化合物（Ａ）より誘導される、いわゆるイソシアネート基不含の、次の一般式
【０１３１】
【化２４】

【０１３２】
（ただし、式中のＲは芳香族または脂肪族の２価連結基を、また、Ｒ’はアルキル基、アラルキル基またはオキシアルキレン基を表わすものとする。）
【０１３３】
で示されるような、親水性基不含または親水性基含有カルボジミド化合物（Ｂ）
【０１３４】
などのポリカルボジミド系樹脂である。
【０１３５】
これらは、必要に応じて、水分散体として使用することができるが、当該カルボジミド化合物としては、分子中に親水性基を有し、それ自身が水溶解性ないしは水分散性を有するものであるということが望ましく、さらに、一層の高架橋効果を得るためには、このカルボジミド基に連結した官能基として、脂肪族アルキレン基、脂環族アルキレン基、脂肪族アルキル基または脂環族アルキル基を有するものである化合物の使用が望ましい。
【０１３６】
本発明に係る、それぞれ、水性樹脂組成物ならびに防汚性コート剤および離型性コート剤を調製するに当たって用いられる、前述したビニル系重合体と、前述した水分散性ウレタン樹脂とから構成される、前記した水分散体の調整方法としては、特に制限されないが、それらのうちでも特に代表的なもののみを例示するにとどめれば、
【０１３７】
▲１▼ エチレン性不飽和単量体混合物の全量または一部を、予め水分散化せしめた親水性基含有水分散性ウレタン樹脂の存在する水性媒体中へ滴下して、重合開始源により重合せしめるというような方法であるとか、
【０１３８】
▲２▼ 予め水分散化した親水性基含有水分散性ウレタン樹脂の存在下に、エチレン性不飽和単量体混合物を、たとえば、ドイツ国ゴーリン社製のホモジナイザーまたはマイクロフルイダイザーあるいはナノマイザーなどのような、いわゆる高剪断力を有する攪拌機や混合機などにより、水に分散せしめ、重合開始源により重合せしめるというような方法であるとか、
【０１３９】
▲３▼ 予め有機溶媒中で重合せしめて得られるエチレン性不飽和単量体の重合物と、親水性基含有水分散性ウレタン樹脂とを有機溶剤中で混合して、ウレタン樹脂の親水性基を中和せしめたのち、転相乳化により、水分散化せしめるというような方法であるとか、
【０１４０】
▲４▼ 親水性基含有水分散性ウレタン樹脂の存在下に、エチレン性不飽和単量体を有機溶剤中で重合せしめることにより、親水性基含有水分散性ウレタン樹脂とエチレン性不飽和単量体の重合物との混合溶液を調製し、次いで、ウレタン樹脂中の親水性基を中和せしめたのち、転相乳化により、水分散化せしめるというような方法であるとか、
【０１４１】
▲５▼ エチレン性不飽和単量体混合物と、親水性基含有水分散性ウレタン樹脂とを有機溶剤中で混合せしめ、次いで、ウレタン樹脂の親水性基を中和せしめたのち、転相乳化により、水分散化せしめ、しかるのち、重合開始原の存在下に、重合せしめるというような方法などである。
【０１４２】
これらの方法のうちでも、安定なる水分散体を得るためには、エチレン性不飽和単量体混合物と、親水基含有水分散性ウレタン樹脂とを有機溶剤中で混合せしめ、次いで、ウレタン樹脂の親水性基を中和せしめ、転相乳化により、水分散化せしめ、しかるのち、重合開始原の存在下に重合せしめるという形の、上記▲５▼なる方法によるのが、特に望ましい。
【０１４３】
親水性基含有の水分散性ウレタン樹脂中のの親水性基の中和剤として特に代表的なもののみを例示するにとどめれば、アンモニアなどのような種々の揮発性塩基などをはじめ、さらには、トリメチルアミン、トリエチルアミン、ジメチルエタノールアミン、メチルジエタノールアミンまたはトリエタノールアミンなどのような種々の三級アミン類；あるいは水酸化ナトリウムまたは水酸化カリウムなどのような種々の不揮発性塩基などであるが、就中、揮発性が高いアンモニアの使用が特に望ましい。
【０１４４】
ウレタン樹脂／単量体混合物の水分散体を形成させる前に、ウレタン樹脂を水性分散性にするに充分なる量、すなわち、従来型技術により良く知られているように、親水性基を実質的に中和する量の中和剤を混合物に加えるということが、微粒子分散体を得るためにも望ましい。
【０１４５】
つまり、当該中和剤を、親水性基の１当量当たり、６５〜１１０％の範囲内の当量で以て添加せしめるということが望ましく、親水性基の８０％以上を中和するまで、中和剤を添加するということが特に望ましい。
【０１４６】
ウレタン樹脂／単量体混合物は、転相乳化法により、水中に分散させることができる。転相乳化は、これまでにも良く知られているような方法で以て行なうことが可能であり、ウレタン樹脂／単量体混合物に、攪拌下、水を滴下せしめる方法や、分割添加せしめる方法の、いずれも可能である。こうした種々の方法のうちでも、高度な安定性を有する水分散体を得るためには、分割添加によるのが望ましい。
【０１４７】
このとき、１回に添加する水の量は、ウレタン樹脂／単量体混合物全量に対し、１／３０〜１／５の範囲内が適切であり、添加した水が、ウレタン樹脂／単量体混合物と均一に混合された時点で、次の水を添加せしめるというようにすることが望ましい。
【０１４８】
また、前記した重合開始源としては、特に制限されないが、それらのうちでも特に代表的なもののみを例示するにとどめれば、アゾ化合物や、有機過酸化物などのような各種の重合開始剤などをはじめ、さらには、紫外線あるいはγ−線などのような各種の電離性放射線などであり、これらの種々の重合開始源が採用され得る。
【０１４９】
ウレタン樹脂／単量体混合物の重合反応は、重合開始源が活性種を解離するのに充分な温度で行なわれ、使用する重合開始剤の活性度ならびに反応媒体により、適宜、選択し得るというものである。メチルエチルケトンを反応溶剤として使用する場合の好適なる温度範囲は、５０℃〜８０℃程度であり、就中、６０℃〜７５℃が、より望ましい。
【０１５０】
本発明における、ビニル系重合体と親水性基含有の水分散性ウレタン樹脂とから構成される水分散体と、ポリカルボジミド系樹脂との使用比率は、前者水分散体／後者ポリカルボジミド系樹脂なる重量比で以て、１００／１〜１００／２０であることが、とりわけ、耐久性などが得られるという面で望ましい。
【０１５１】
以上のようにして得られる、本発明の水性樹脂組成物は、主として、よりわけ、防汚性、撥水性、撥油性、離型性、剥離性ならびに潤滑性などの、いわゆる表面諸特性を付与するコート剤として利用することができる。
【０１５２】
本発明に係る水性樹脂組成物を、こうした、いわゆる塗工剤として使用するに際して用いられる被塗物基材として特に代表的なるもののみを例示するにとどめるならば、
【０１５３】
ポリエチレンテレフタレート・フィルム、ポリプロピレン・フィルム、ポリスチレン・フィルムまたはポリ塩化ビニル・フィルムなどで代表されるような種々の合成フィルム類；
【０１５４】
情報記録紙、包装紙、段ボール紙、板紙または耐水耐油紙などで代表されるような種々の紙類；
【０１５５】
ポリエステル、ナイロンもしくはアクリルの如き、各種の合成繊維類、綿、絹、麻もしくは羊毛の如き、各種の天然繊維類または合成皮革、人工皮革もしくは天然皮革の如き、各種の革製品類などで代表されるような種々の布類；
【０１５６】
鉄またはアルミニウムなどで代表されるような種々の金属類；あるいはセラミックまたはコンクリートなどで代表されるような種々の無機質基材類などである。
【０１５７】
また、本発明に係る水性樹脂組成物を処理する方法としては、基材の種類に応じて、任意の方法が適用可能であるが、そうした処理法として特に代表的なもののみを例示するにとどめれば、浸漬塗布法、ロールコータ、グラビアコータまたは刷毛塗りなどである。
【０１５８】
本発明に係る水性樹脂組成物が処理された基材は、通常の場合、当該水性樹脂組成物を硬化させて皮膜を形成せしめることによって、容易に得られる。こうした硬化の条件は、基材の耐熱性やパーフルオロアルキル基含有エチレン性不飽和単量体および／またはポリジメチルシロキサン基含有エチレン性不飽和単量体と、これらの両単量体類と共重合可能なる其の他のエチレン性不飽和単量体との共重合体であるビニル系重合体と、親水性基含有の水分散性ウレタン樹脂とから構成される水分散体の皮膜形成温度に応じて、適宜、変更され得る。
【０１５９】
通常の場合、パーフルオロアルキル基含有エチレン性不飽和単量体および／またはポリジメチルシロキサン基含有エチレン性不飽和単量体と、これらの両単量体類と共重合可能なる其の他のエチレン性不飽和単量体との共重合体であるビニル系重合体と、親水性基含有の水分散性ウレタン樹脂とから構成される水分散体の皮膜形成温度から、基材の耐熱温度までの範囲内で、硬化を実施するというようにするのが望ましい。具体的には、室温より１８０℃程度の温度が適切であり、１００〜１８０℃なる範囲内であり、また、硬化時間の方は、皮膜の膜厚に応じて変更され得るが、具体的には、１分間から１時間程度が適切である。
【０１６０】
【実施例】
次に、本発明を、実施例および比較例により、具体的に説明することにするが、本発明は、決して、これらの例示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、特に断わりの無い限りは、すべて、重量基準であるものとする。また、用いた単量体は、上述して来たような、発明の詳細な説明の欄において示した呼称を、そのまま使用した。
【０１６１】
合成例１
温度計、撹拌装置および還流冷却管を備えた４ツ口フラスコに、先ず、エチレングリコール／ネオペンチルグリコール／テレフタール酸／イソフタール酸／アジピン酸を反応させて得られたポリエステル（ＯＨ価＝９１）の１６０部を、３５０部のメチルエチルケトンに加えて、充分に攪拌した。
【０１６２】
次いで、４３部のヘキサメチレンジイソシアネートを加え、７５℃に加温し、この温度で、３時間のあいだ反応させた。しかるのち、この溶液を５５℃以下に冷却してから、１３部のジメチロールプロピオン酸を投入して、１５時間のあいだ反応させるということによって、水分散性を有するポリウレタン溶液が得られた。
【０１６３】
パーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ−１）の１９４部、メチルメタクリレートの１１部、２−ヒドロキシエチルメタクリレートの６．５部およびＮ−メチロールアクリルアマイドの４．３部よりなる単量体混合物と、ラウリルメルカプタンの２．２部とを、１００部のメチルエチルケトンに溶解させ、ポリウレタン溶液に添加して溶解させた。
【０１６４】
５％アンモニア水溶液の３３部を添加し、０．５時間のあいだ、５５℃に保ったのち、１，３００部の水を２０部ずつ分割して、１時間かけて添加し、均一なる水分散体を得た。此の水分散体を、７０℃にまで昇温して、攪拌しながら、１．１部の過硫酸アンモニウムを加えて、６時間のあいだ重合反応を行なった。
【０１６５】
かくして得られた水分散体をナスフラスコに移し、ロータリエバポレータを用いて、５５℃、３６０ｍｍＨｇの条件で以て脱溶剤せしめることによって、固形分が２５％の安定なる水分散体（Ｉ）を、１，７２０部という収率で以て得た。
【０１６６】
合成例２
温度計、撹拌装置および還流冷却管を備えた４ツ口フラスコに、先ず、エチレングリコール／ネオペンチルグリコール／テレフタール酸／イソフタール酸／アジピン酸を反応させて得られたポリエステル（ＯＨ価＝９１）の１６０部を、３５０部のメチルエチルケトンに加えて、充分に攪拌した。
【０１６７】
次いで、４３部のヘキサメチレンジイソシアネートを加え、７５℃に加温し、この温度で、３時間のあいだ反応させた。しかるのち、この溶液を５５℃以下に冷却してから、１３部のジメチロールプロピオン酸を投入して、１５時間のあいだ反応させるということによって、水分散性を有するポリウレタン溶液が得られた。
【０１６８】
パーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ−１）の１９４部、メチルメタクリレートの１１３部、２−ヒドロキシエチルメタクリレートの９．７部およびＮ−メチロールアクリルアマイドの６．５部よりなる単量体混合物と、ラウリルメルカプタン の３．２部とを、１００部のメチルエチルケトンに溶解させ、ポリウレタン溶液に添加して溶解させた。
【０１６９】
５％アンモニア水溶液の３３部を添加し、０．５時間のあいだ、５５℃に保ったのち、１，５９０部の水を２０部ずつ分割して、１時間かけて添加し、均一なる水分散体を得た。此の水分散体を、７０℃にまで昇温して、攪拌しながら、１．６部の過硫酸アンモニウムを加えて、６時間のあいだ重合反応を行なった。
【０１７０】
かくして得られた水分散体をナスフラスコに移したのち、ロータリエバポレータを用いて、５５℃、３６０ｍｍＨｇの条件で以て脱溶剤せしめることによって、固形分が２５％の安定なる水分散体（ＩＩ）を、２，１６０部という収率で以て得た。
【０１７１】
合成例３
温度計、撹拌装置および還流冷却管を備えた４ツ口フラスコに、先ず、エチレングリコール／ネオペンチルグリコール／テレフタール酸／イソフタール酸／アジピン酸を反応させて得られたポリエステル（ＯＨ価＝９１）の１６０部を、３５０部のメチルエチルケトンに加えて、充分に攪拌した。
【０１７２】
次いで、４３部のヘキサメチレンジイソシアネートを加え、７５℃に加温し、この温度で、３時間のあいだ反応させた。しかるのち、この溶液を５５℃以下に冷却してから、１３部のジメチロールプロピオン酸を投入して、１５時間のあいだ反応させるということによって、水分散性を有するポリウレタン溶液が得られた。
【０１７３】
パーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ−１）の８４部、メチルメタクリレートの４．６部、２−ヒドロキシエチルメタクリレートの２．８部およびＮ−メチロールアクリルアマイドの１．９部よりなる単量体混合物と、ラウリルメルカプタン の０．９部とを、５０部のメチルエチルケトンに溶解させ、ポリウレタン溶液に添加して溶解させた。
【０１７４】
５％アンモニア水溶液の３３部を添加し、０．５時間のあいだ、５５℃に保ったのち、９００部の水を２０部ずつ分割して、１時間かけて添加し、均一なる水分散体を得た。此の水分散体を、７０℃にまで昇温して、攪拌しながら、過硫酸アンモニウム（０．５部）を加えて、６時間のあいだ重合反応を行なった。かくしてかくして得られた水分散体をナスフラスコに移し、ロータリエバポレータを用いて、５５℃、３６０ｍｍＨｇの条件で以て脱溶剤せしめることによって、固形分が２５％の安定なる水分散体（ＩＩＩ）を、１，２３０部という収率で以て得た。
【０１７５】
合成例４
温度計、撹拌装置および還流冷却管を備えた４ツ口フラスコに、先ず、エチレングリコール／ネオペンチルグリコール／テレフタール酸／イソフタール酸／アジピン酸を反応して得られたポリエステル（ＯＨ価＝９１）の１６０部と、「エポキシエステル３００２Ｍ」［共栄社化学（株）製の、ビスフェノールＡプロピレンオキシド２モル付加物ジグリシジルエーテルのメタアクリル酸付加物の商品名］の１２部とを、１５０部のメチルエチルケトンに加えて、充分に攪拌した。
【０１７６】
次いで、４９部のヘキサメチレンジイソシアネートを加え、７５℃に加温し、この温度で、３時間のあいだ反応させた。しかるのち、この溶液を５５℃以下に冷却してから、１４部のジメチロールプロピオン酸を投入して、１５時間のあいだ反応させるということによって、水分散性を有するポリウレタン溶液が得られた。
【０１７７】
パーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ−１）の２１１部、メチルメタクリレートの１２部、２−ヒドロキシエチルメタクリレートの７．１部およびＮ−メチロールアクリルアマイドの４．７部よりなる単量体混合物と、ラウリルメルカプタンの２．３部とを、１２０部のメチルエチルケトンに溶解させ、ポリウレタン溶液に添加して溶解させた。
【０１７８】
５％アンモニア水溶液の３８部を添加し、０．５時間のあいだ、５５℃に保ったのち、１，３７０部の水を２０部ずつ分割して、１時間かけて添加し、均一なる水分散体を得た。此の水分散体を、７０℃にまで昇温して、攪拌しながら、１．２部の過硫酸アンモニウムを加えて、６時間のあいだ重合反応を行なった。
【０１７９】
かくして得られた水分散体をナスフラスコに移し、ロータリエバポレータを用いて、５５℃、３６０ｍｍＨｇの条件で以て脱溶剤せしめることによって、固形分が２５％の安定なる水分散体（ＩＶ）が、１，８８０部という収率で以て得られた。
【０１８０】
合成例５
温度計、撹拌装置および還流冷却管を備えた４ツ口フラスコに、先ず、エチレングリコール／ネオペンチルグリコール／テレフタール酸／イソフタール酸／アジピン酸を反応させて得られたポリエステル（ＯＨ価＝９１）の１６０部と、ビスフェノールＡプロピレンオキサイド（ＰＯ）２モル付加物ジグリシジルエーテルのメタクリル酸付加物の１２部を、１５０部のメチルエチルケトンに加えて、充分に攪拌した。
【０１８１】
次いで、４９部のヘキサメチレンジイソシアネートを加え、７５℃に加温し、この温度で、３時間のあいだ反応させた。しかるのち、この溶液を５５℃以下に冷却してから、１４部のジメチロールプロピオン酸を投入して、１５時間のあいだ反応させるということによって、水分散性を有するポリウレタン溶液が得られた。
【０１８２】
パーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ−１）の１７６部、「ＵＡ−３０６Ｈ」［共栄社化学（株）製の、ペンタエリストロールトリアクリレートヘキサメチレンジイソシアネートウレタンプレポリマーなる多官能アクリレートの商品名］の２３．５部、メチルメタクリレートの３６部、２−ヒドロキシエチルメタクリレートの７．１部およびＮ−メチロールアクリルアマイドの４．７部よりなる単量体混合物と、ラウリルメルカプタンの２．３部とを、１２０部のメチルエチルケトンに溶解させ、ポリウレタン溶液に添加して溶解させた。
【０１８３】
５％アンモニア水溶液の３８部を添加し、０．５時間のあいだ、５５℃に保ったのち、１，３７０部の水を２０部ずつ分割して、１時間かけて添加し、均一なる水分散体を得た。此の水分散体を、７０℃にまで昇温して、攪拌しながら、１．２部の過硫酸アンモニウムを加えて、６時間のあいだ重合反応を行なった。
【０１８４】
かくして得られた水分散体をナスフラスコに移し、ロータリエバポレータを用いて、５５℃、３６０ｍｍＨｇの条件で以て脱溶剤せしめることによって、固形分が２５％の安定なる水分散体（Ｖ）を、１，８８０部という収率で以て得た。
【０１８５】
合成例６
温度計、撹拌装置および還流冷却管を備えた４ツ口フラスコに、先ず、エチレングリコール／ネオペンチルグリコール／テレフタール酸／イソフタール酸／アジピン酸を反応させて得られたポリエステル（ＯＨ価＝９１）の１６０部と、シリコーン（Ｓ−１）の２６部とを、１７０部のメチルエチルケトンに加えて、充分に攪拌した。
【０１８６】
次いで、５４部のヘキサメチレンジイソシアネートを加え、７５℃に加温し、この温度で、３時間のあいだ反応させた。しかるのち、この溶液を５５℃以下に冷却してから、１６部のジメチロールプロピオン酸を投入して、１５時間のあいだ反応させるということによって、水分散性を有するポリウレタン溶液が得られた。
【０１８７】
パーフルオロアルキル基含有エチレン性不飽和単量体（Ｂ−１）の１８３部、メチルメタクリレートの３９部、２−ヒドロキシエチルメタクリレートの７．９部、ポリジメチルシロキサン基含有エチレン性不飽和単量体（Ｓ−５）の２６部およびＮ−メチロールアクリルアマイドの８．７部よりなる単量体混合物と、ラウリルメルカプタンの２．６部とを、１３０部のメチルエチルケトンに溶解させ、ポリウレタン溶液に添加して溶解させた。
【０１８８】
５％アンモニア水溶液の４０部を添加し、０．５時間のあいだ、５５℃に保ったのち、１，５００部の水を２０部ずつ分割して、１時間かけて添加し、均一なる水分散体を得た。此の水分散体を、７０℃にまで昇温して、攪拌しながら、１．５部の過硫酸アンモニウムを加えて、６時間のあいだ重合反応を行なった。
【０１８９】
かくして得られた水分散体をナスフラスコに移し、ロータリエバポレータを用いて、５５℃、３６０ｍｍＨｇの条件で以て脱溶剤せしめることによって、固形分が２５％の安定なる水分散体（ＶＩ）を、２，１２０部という収率で以て得た。
【０１９０】
実施例１
合成例１で得られた水分散体（Ｉ）の１００部に対して、８部の「カルボジライトＶ−０２」［日清紡（株）製の、水添ＭＤＩ系水溶性性ポリカルボジミド系樹脂であって、有効成分が４０重量％なる、淡黄色の透明液体であり、しかも、ノニオン性で、カルボジミド当量（樹脂分）が５９０なる樹脂の商品名］を配合せしめることによって、目的とする水性樹脂組成物を調製した。
【０１９１】
次いで、この水性樹脂組成物を、膜厚が２００マイクロメータないしはミクロン（μｍ）となるようにキャスティングせしめて、室温で、４８時間のあいだ乾燥せしめたのち、１２０℃で、５分間のあいだ熱処理を行なった。しかるのち、かくして得られたキャスティング皮膜を、３ｃｍ×３ｃｍのサイズにカットせしめて、耐溶剤性の評価判定試験を行なった。
【０１９２】
すなわち、５０ｇのメチルエチルケトン（以下、ＭＥＫと略記する。）中に、４８時間のあいだ浸漬せしめて放置した際の、それぞれ、面積膨潤率ならびに溶出率の測定を行なった。それらの結果を、まとめて、第１表に示す。
【０１９３】
実施例２および３合成例４または５で得られた水分散体（ＩＶ）または（Ｖ）と、「カルボジライトＶ−０４」［日清紡（株）製の、ＴＭＸＤＩ（テトラメチルキシリレンジイソシアネート）系水溶性ポリカルボジミド系樹脂であって、有効成分が４０重量％なる、淡黄褐色の透明液体であり、しかも、ノニオン性で、カルボジミド当量（樹脂分）が３３８なる樹脂の商品名］と、「カルボジライトＶ−０６」（同上社製の、ＴＤＩ（トリレンジイソシアネート）系水溶性ポリカルボジミド系樹脂であって、有効成分が４０重量％なる、黄色の透明液体であり、ノニオン性で、しかも、カルボジミド当量（樹脂分）が２５７なる樹脂の商品名）とを、各別に、第１表に示すような割合で配合せしめ、以後は、実施例１と同様にして、耐溶剤性の評価判定試験を行なった。それらの結果を、まとめて、第１表に示す。
【０１９４】
【表１】

【０１９５】
《第１表の脚注》
面積膨潤率＝（ＭＥＫ浸漬後の面積／ＭＥＫ浸漬前の面積）×１００
溶出率 ＝（１−ＭＥＫ浸漬後の重量／ＭＥＫ浸漬前の重量）×１００
【０１９６】
実施例４
合成例１で得られた水分散体（Ｉ）の１００部に対して、「カルボジライトＶ−０２」の８部を配合せしめることによって、目的とする防汚性コート剤を調製した。さらに、「ボンコートＨＶ」［大日本インキ化学工業（株）製の、ポリアクリル酸型増粘剤の商品名］と、アンモニア水溶液とを、第２表に示すような割合で配合せしめてから、回転数が３００ｒｐｍという条件下で攪拌分散せしめた処、２５℃における粘度が１，１００ｍＰａ・ｓなる配合液が得られた。
【０１９７】
次いで、この配合液を、ＳＵＳ板上に、バーコーターＮｏ．１４を用いて塗布せしめ、１２０℃で、５分間のあいだ熱処理を行なった。しかるのち、かくして得られた塗工膜について、耐ＭＥＫラビングテストならびに各種の汚れ物質に対する防汚テストを実施した。それらの結果を、まとめて、第２表に示す。
【０１９８】
実施例５
合成例１で得られた水分散体（Ｉ）の１００部に対して、「カルボジライトＶ−０４」の５部を配合せしめることによって、目的とする防汚性コート剤を調製し、さらに、「ボンコートＨＶ」と、アンモニア水溶液とを、第２表に示すような割合で以て配合せしめ、回転数が３００ｒｐｍという条件下で攪拌分散せしめた処、２５℃における粘度が１，１００ｍＰａ・ｓなる配合液が得られた。
【０１９９】
次いで、この配合液を、ＳＵＳ板上に、バーコーターＮｏ．１４を用いて塗布せしめて、１２０℃で、５分間のあいだ熱処理を行なった。しかるのち、かくして得られた塗工膜について、耐ＭＥＫラビングテストならびに各種の防汚テストを実施した。それらの結果を、まとめて、第２表に示す。
【０２００】
【表２】

【０２０１】
《第２表の脚注》
（１）原則として、２４時間後の拭き取り
（２）２４時間後のシンナーによる拭き取り
【０２０２】
◎：汚れの残存ならびに塗膜破壊、共になし
△：汚れ残存あるも、塗膜破壊なし
×：汚れの残存ならびに塗膜破壊、共にあり
【０２０３】
実施例６〜９
合成例２〜５で得られた水分散体（ＩＩ）〜（Ｖ）の１００部に対して、第２表に示すような各種のカルボジライトを、各別に、配合せしめることによって、目的とする防汚コート剤を調製し、さらに、「ボンコートＨＶ」と、アンモニア水溶液とを、第２表に示すような割合で以て配合せしめた。
【０２０４】
実施例４と同様にして、ＳＵＳ板上に塗工せしめてから、耐ＭＥＫラビングテストならびに各種の防汚テストを実施した。それらの結果を、まとめて、第２表に示す。
【０２０５】
【表３】

【０２０６】
実施例１０
合成例６で得られた水分散体（ＶＩ）の８部に対して、０．６部の「カルボジライトＶ−０２」を配合せしめることによって、目的とする離型性コート剤を調製し、さらに、この配合液を、２０％イソプロピルアルコール（以下、ＩＰＡと略記する。）水溶液の９２部で以て希釈せしめ、次いで、かくして得られた希釈液を、バーコーターＮｏ．８を用いて、二軸延伸ポリプロピレン（以下、ＯＰＰと略記する。）フィルムのコロナ放電処理面に塗布せしめて、１１０℃で、２分間のあいだ乾燥した。
【０２０７】
しかるのち、次に示すような要領に従って、剥離性能の評価判定試験を行なった。それらの結果を、まとめて、第３表に示す。
【０２０８】
［剥離性能試験法］
【０２０９】
本発明に係る離型性コート剤塗布面に、ゴム系粘着テープ［日東電工（株）製のＮＯ．３１Ｅを使用した。］を、自重が２ｋｇなるローラーで以て圧着せしめた。
【０２１０】
先ず、剥離性能の方は、以上のようにして得られたテープ試験片を、２５℃に、２４時間のあいだ保存したのちの剥離力（常態剥離力）と、７０℃、９５％ＲＨという条件下に、２日間のあいだ保存したのちの剥離力（エージング後剥離力）と、２５℃に、２４時間のあいだ保存したのちの、テープの残留接着力（常態残留接着力）と、７０℃で、９５％ＲＨという条件下に、２日間のあいだ保存したのちの残留接着力（エージング後残留接着力）とを測定するということによって評価判定したものである。
【０２１１】
次いで、剥離力の方は、剥離速度が３００ｍｍ／ｍｉｎなる条件下で、１８０度剥離時の抵抗として測定したものであるし、他方、残留接着力の方は、以上のようにして得られたテープ試験片を、ステンレスパネルに貼着せしめてから、剥離速度が３００ｍｍ／ｍｉｎなる条件下で、１８０度剥離時の抵抗として測定したものである。
【０２１２】
【表４】

【０２１３】
比較例１
実施例１と同様にして、合成例１で得られた水分散体（Ｉ）を、膜厚が２００μｍとなるように、キャスティングせしめてから、室温で、４８時間のあいだ乾燥せしめたのち、１２０℃、５分間という条件下で熱処理を行なった。
【０２１４】
次いで、かくして得られたキャスティング皮膜を、３ｃｍ×３ｃｍのサイズにカットせしめて、耐溶剤性の評価判定試験を行なった。すばわち、５０ｇのＭＥＫ中に、４８時間のあいだ浸漬せしめて放置した際の、それぞれ、面積膨潤率ならびに溶出率の測定を行なった。それらの結果を、まとめて、第１表に示す。
【０２１５】
比較例２
合成例１で得られた水分散体（Ｉ）の１００部に対して、「ボンコートＨＶ」と、アンモニア水溶液とを、第２表に示すような割合で配合せしめ、回転数が３００ｒｐｍという条件下で攪拌分散させた処、２５℃における粘度が２，１００ｍＰａ・ｓなる配合液が得られた。
【０２１６】
次いで、この配合液を、ＳＵＳ板上に、バーコーターＮｏ．１４を用いて塗布せしめてから、１２０℃で、５分間のあいだ熱処理を行なった。かくして得られた塗工膜についで、耐ＭＥＫラビングテストならびに各種の防汚テストを実施した。それらの結果を、まとめて、第２表に示す。
【０２１７】
比較例３
合成例６で得られた水分散体（ＶＩ）の８部を、９２部の２０％ＩＰＡ水溶液で以て希釈せしめた。次いで、かくして得られた希釈液を、バーコーターＮｏ．８を用いて、コロナ処理をしたＯＰＰ表面に塗布せしめ、しかるのち、剥離性能の評価判定試験を行なった。それらの結果を、まとめて、第３表に示す。
【０２１８】
【表５】

【０２１９】
《第３表の脚注》
ブランク ： 未塗工ＯＰＰフィルムならびにＳＵＳ板を用いたときの試験結果
【０２２０】
常 態：（条件）２５℃、６５％という条件下で、２４時間後
エージング：（条件）７０℃、９５％という条件下で、４８時間後
【０２２１】
なお、「剥離力」における、それぞれ、「常態剥離力」および「エージング後剥離力」ならびに「残留接着力」における、それぞれ、「常態残留接着力」および「エージング後残留接着力」の単位は、いずれも、“ｇｆ／ｃｍ²”である。
【０２２２】
【発明の効果】
本発明に係る水性樹脂組成物は、とりわけ、耐溶剤性ならびに耐湿熱性などに優れるものであり、主として、フッ素あるいはシリコーン塗工膜を形成することが可能であるし、加えて、とりわけ、防汚性などにも優れるし、しかも、移行性が少なく、剥離性にも優れるという、極めて実用性の高い離型性塗工膜を形成し得るというものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel and useful aqueous resin composition, and an antifouling coating agent and a releasable coating agent, respectively. More particularly, the present invention provides:Perfluoroalkyl group-containing ethylenically unsaturated monomers and / or polydimethylsiloxane group-containing ethylenically unsaturated monomers, and other ethylenically unsaturated monomers copolymerizable with both of these monomers. Vinyl polymer that is a copolymer with polymerAnd an aqueous dispersion composed of a hydrophilic group-containing water-dispersible urethane resin,Polycarbodiimide resinIn addition, the present invention relates to an aqueous resin composition having improved durability, an antifouling coating agent, and a releasable coating agent.
[0002]
Each of the aqueous resin composition and the antifouling coating agent and the releasable coating agent according to the present invention mainly has functionality on various substrate surfaces such as various synthetic films, cellophane, paper or cloth. The composition to be applied or the coating agent is provided.
[0003]
[Prior art]
Until now, a fluorinated vinyl polymer comprising a perfluoroalkyl group-containing ethylenically unsaturated monomer as a main constituent unit has been obtained by emulsion polymerization in the presence of a surfactant. It has been known that an aqueous dispersion liquid can be obtained, and has been used as a water / oil repellent agent, an antifouling agent or a surface modifier.
[0004]
Furthermore, polyurethane-fluorinated vinyl polymer aqueous dispersions utilizing the dispersibility of water-dispersible urethane resins are also known (Japanese Patent Laid-Open No. 4-227614 or Japanese Patent Laid-Open No. 8120034). The use as is proposed.
[0005]
On the other hand, silicone release agents and release agents are often used as release agents for pressure-sensitive adhesives and back release agents for tapes. A curable type or a thermosetting type is known, and as an aqueous dispersion, a polymerizable organopolysiloxane and other vinyl monomers are emulsion-polymerized in an aqueous medium in the presence of an emulsifier. It is an aqueous dispersion that can be obtained (Japanese Patent Laid-Open No. 51-146525),
[0006]
It is a block copolymer obtained by reacting an organopolysiloxane having an alkoxy group, a hydrophilic polyol, and a diisocyanate (Japanese Patent Laid-Open No. 61-28527), polysiloxane diol, acid diol, and It is an aqueous urethane resin comprising other polyol and polyisocyanate as constituents (Japanese Patent Laid-Open No. 5-25239),
[0007]
Furthermore, in the presence of a terminal hydroxyl group-containing polysiloxane, a form obtained using a polymerizable silane compound, an unsaturated organic acid and other monomers copolymerizable therewith, respectively. Polymers (JP-A-3-255183) have been reported.
[0008]
[Problems to be solved by the invention]
However, the fluorine-based vinyl polymers as listed above are not likely to be coating agents because they usually lack film-forming properties, and an aqueous dispersion of the polyurethane-fluorinated vinyl polymer as listed above. Although the body provides a coating film with excellent film formability, it has a problem in durability, such as insufficient resistance to solvents and deterioration at high temperatures and high humidity.
[0009]
In addition, in applications such as release agents and release agents that use a silicone resin release film such as those listed above, surfaces that come into contact with the surface of these films, for example, the adhesive tape surface of the adhesive tape The decrease in the adhesive strength due to the migration of the silicone resin is an important problem, and in particular, the aqueous dispersion having the shape as described above is insufficient. Further, the self-dispersing water dispersion has insufficient stability, and the emulsion using an emulsifier has a problem of a decrease in adhesiveness due to transfer of the emulsifier.
[0010]
Thus, as long as the conventional technology is followed, the stability and resistance to solvents are inevitably excellent, and a coating film excellent in film formability is provided, and also so-called durability is excellent. It has been difficult to obtain such an aqueous antifouling coating agent or releasable coating agent as well as a highly practical aqueous resin composition.
[0011]
However, the present inventors have eagerly and researched, in particular, for an aqueous resin composition and an antifouling coating agent and a releasable coating agent, respectively, which have improved durability and the like and are useful. Started.
[0012]
Therefore, the problem to be solved by the present invention is, in one aspect, an aqueous resin composition and an antifouling coating agent and a releasable coating, respectively, which have improved durability, among others, and are useful. To try to provide the agent.
[0013]
[Means for Solving the Problems]
Therefore, in view of the actual situation as described above, the present inventors focused on the problem to be solved by the invention as described above, and as a result of earnestly examining it,Perfluoroalkyl group-containing ethylenically unsaturated monomers and / or polydimethylsiloxane group-containing ethylenically unsaturated monomers, and other ethylenically unsaturated monomers copolymerizable with both of these monomers. Vinyl polymer that is a copolymer with polymerAnd an aqueous dispersion composed of a hydrophilic group-containing water-dispersible urethane resin,Polycarbodiimide resinIn order to find out that the water-based resin composition comprising the above is excellent in durability and the like, the present study was completed here.
[0014]
That is, the present invention basically includesPerfluoroalkyl group-containing ethylenically unsaturated monomers and / or polydimethylsiloxane group-containing ethylenically unsaturated monomers, and other ethylenically unsaturated monomers copolymerizable with both of these monomers. Vinyl polymer that is a copolymer with polymerAnd an aqueous dispersion composed of a hydrophilic group-containing water-dispersible urethane resin,Polycarbodiimide resinAn aqueous resin composition with improved durability, and an antifouling coating agent and a releasable coating agent comprising:
[0015]
Preferably, a perfluoroalkyl group-containing ethylenically unsaturated monomer and / or a polydimethylsiloxane group-containing ethylenically unsaturated monomer and other ethylenically unsaturated monomers copolymerizable with both of these monomers. An aqueous dispersion composed of a copolymer obtained from a saturated monomer and a water-dispersible urethane resin whose hydrophilic group is a carboxyl group or a carboxylate group;Polycarbodiimide resinIt is an object of the present invention to provide an aqueous resin composition with improved durability and an antifouling coating agent and a releasable coating agent.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
Thus, this applicationPerfluoroalkyl group-containing ethylenically unsaturated monomers and / or polydimethylsiloxane group-containing ethylenically unsaturated monomers, and other ethylenically unsaturated monomers copolymerizable with both of these monomers. Vinyl polymer that is a copolymer with polymerAnd an aqueous dispersion composed of a hydrophilic group-containing water-dispersible urethane resin,Polycarbodiimide resinA water-based resin composition with improved durability, an antifouling coating agent and a release coating agent comprising:
[0017]
In particular, as the above-mentioned vinyl polymer, the above-mentioned perfluoroalkyl group-containing ethylenically unsaturated monomer and / or polydimethylsiloxane group-containing ethylenically unsaturated monomer, and a copolymer of both of these monomers Water-based resin composition with improved durability and antifouling coating agent and releasable coating agent comprising using a copolymer in a form obtained from other possible ethylenically unsaturated monomers And is charging
[0018]
Further, the present application relates to the above-mentioned vinyl polymer as the perfluoroalkyl group-containing ethylenically unsaturated monomer, with respect to 100 parts by weight of the total ethylenically unsaturated monomer, that is, the ethylene polymer. Based on a total weight of 100 parts by weight of the unsaturated unsaturated monomer,40 to 95 parts by weightClaiming an aqueous resin composition with improved durability, and an antifouling coating agent and a releasable coating agent comprising using a copolymer in the form obtained within the scope of ,
[0020]
Furthermore, the above-mentioned vinyl polymer is the above-mentioned perfluoroalkyl group-containing ethylenically unsaturated monomer, with respect to 100 parts by weight of the total ethylenically unsaturated monomer, that is, the ethylene polymer. Based on a total weight of 100 parts by weight of the unsaturated unsaturated monomer,5 to 70 parts by weightIn addition, as the above-mentioned polydimethylsiloxane group-containing ethylenically unsaturated monomer, the total weight of the ethylenically unsaturated monomer is 100 parts by weight, that is, the ethylenically unsaturated monomer. Based on the total body weight of 100 parts by weight,30 parts by weight or lessClaiming an aqueous resin composition with improved durability, an antifouling coating agent and a release coating agent comprising using a copolymer in the form obtained in
[0021]
Alternatively, in the present application, the above-described hydrophilic group-containing water-dispersible urethane resin is improved in durability, particularly comprising using a form having a carboxyl group or a carboxylate group as the hydrophilic group. Claiming an aqueous resin composition and an antifouling coating agent and a releasable coating agent,
[0022]
The present application also relates to an aqueous resin composition having improved durability, and an antifouling method, comprising using a hydrophilic group-containing water-dispersible urethane resin having a polydimethylsiloxane group. Claiming an adhesive coating agent and a releasable coating agent,
[0023]
Above,Polycarbodiimide resinClaiming an aqueous resin composition with improved durability, an antifouling coating agent and a releasable coating agent, comprising the specific property of being water-soluble or water-dispersible. And
[0024]
In addition,Polycarbodiimide resinBut thatCarbodiimide groupIn particular, the functional group bonded to is an aliphatic alkylene group, an aliphatic alkyl group, an alicyclic alkylene group or an alicyclic alkyl group, and has a nonionic hydrophilic property in the molecule of the compound. Claiming an aqueous resin composition with improved durability, an antifouling coating agent and a releasable coating agent consisting of a specific group having a group,
[0025]
In the present application, the ratio of the above-described vinyl polymer to the above-described hydrophilic group-containing water-dispersible urethane resin is expressed by a weight ratio.7/3 to 3/7Claiming a specific, improved durability aqueous resin composition as well as an antifouling and releasable coating agent,
[0026]
And, the present application is an aqueous dispersion composed of the above-described vinyl polymer and a hydrophilic group-containing water-dispersible urethane resin.Polycarbodiimide resinAnd the ratio by weight,100/10 to 100/20Claiming a water-based resin composition with improved durability and an antifouling and releasable coating agent comprising a specific composition of the form
[0027]
Hereinafter, the contents of the present invention will be described in more detail.
[0028]
Here, as the above-described water-dispersible urethane resin containing a hydrophilic group constituting an aqueous resin composition and an antifouling coating agent and a releasable coating agent, respectively, according to the present invention, In addition, as long as it is a urethane resin having a so-called hydrophilic group, any of various known types can be used.
[0029]
Such a water-dispersible urethane resin can be obtained, for example, by reacting an active hydrogen-containing compound, a hydrophilic group-containing compound, and a polyisocyanate.
[0030]
First, only typical examples of the above-mentioned polyisocyanate are exemplified. 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4, 4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-bifu Anyylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene Isocyanate, dodecamethylene diisocyanate,
[0031]
Trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane Although it is diisocyanate or 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate, these may of course be used alone or in combination of two or more.
[0032]
Next, only typical examples of the active hydrogen-containing compounds described above are exemplified, and examples thereof include polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols, polyester amide polyols, and polythioether polyols. The so-called high molecular weight polyols and the molecular weight300 or lessSo-called low molecular weight compounds,Unsaturated group-containing compoundsGenerally, it is divided in this way.
[0033]
Of the active hydrogen-containing compounds, only typical polyester polyols are exemplified. Ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentane Diol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight =300-6,000), Dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone or their alkylene oxide adducts, etc. As represented by so-called glycol components,
[0034]
Succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1 , 4-Naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid or the like Dicarboxylic acid anhydrides or ester-forming derivatives; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, or ester-forming derivatives of these hydryloxycarboxylic acids, etc. Polyester in the form of being obtained by dehydration condensation reaction with an acid component And the like.
[0035]
In addition, polyesters obtained by a ring-opening polymerization reaction of so-called cyclic ester compounds, such as ε-caprolactone, or copolyesters thereof can also be used.
[0036]
Examples of the polyethers among the active hydrogen-containing compounds are only typical ones, and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1, 4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, aconite sugar, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine , Having at least two active hydrogen atoms in the molecule, as typified by pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid or 1,2,3-propanetrithiol One or more compounds are used, and one or two of various monomers represented by ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene and the like are used as initiators. Using the above, it is in the form of addition-polymerized by a conventional method.
[0037]
Of these active hydrogen-containing compounds, only a typical polycarbonate polyol is exemplified, and various glycols represented by 1,4-butanediol, 1,6-hexanediol, diethylene glycol and the like are exemplified. And compounds obtained by reaction with diphenyl carbonate or phosgene.
[0038]
Further, only typical examples of the low molecular weight compounds described above are exemplified. As the raw materials for the polyester polyol, various glycol components as already listed above: glycerin, trimethylolethane, trimethylolpropane, A so-called polyhydroxy compound represented by sorbitol or pentaerythritol; or ethylenediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, 3 , 3-dimethyl-4,4-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 1,2-propanediamine, hydrazine, diethylenetriamine or triethylenetriamine So-called amine compounds.
[0039]
Furthermore, only typical examples of the unsaturated group-containing compound described above are exemplified. (Meth) acrylic acid adduct of propylene glycol diglycidyl ether, (meth) acrylic of polyoxyalkylene glycol diglycidyl ether (Meth) acrylic acid adducts of so-called diepoxy compounds represented by acid addition products, bisphenol A or (meth) acrylic acid addition products of diglycidyl ethers of propylene oxide adducts thereof, or glycerin mono (meta ) Acrylate or dihydroxy (meth) acrylate such as trimethylolpropane mono (meth) acrylate.
[0040]
Furthermore, examples of the aforementioned hydrophilic group-containing compound include compounds having one or more active hydrogen atoms and a hydrophilic group in the molecule.
[0041]
Here, examples of the hydrophilic group include various nonionic groups such as a polyoxyalkylene group, and also a carboxylic acid group, a sulfonic acid group, or a carboxy group that is a salt thereof. A rate group or a sulfonate group is exemplified, and among these, a carboxylic acid group and a carboxylate group are preferable.
[0042]
Specific examples of the hydrophilic group-containing compound include 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine, and the like. So-called sulfonic acid-containing compounds such as 4,6-disulfonic acid, 2,4-diaminotoluene-5-sulfonic acid, taurine or 2-aminoethyl-2-aminoethanesulfonic acid, or the like Including polyester polyols obtained by copolymerizing derivatives or these,
[0043]
Furthermore, representatives are 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3,4-diaminobenzoic acid, and the like. The so-called carboxylic acid-containing compounds or their derivatives, or polyester polyols obtained by copolymerizing these, may be used, but these may be used alone or in combination of two or more. Of course.
[0044]
As the content of such hydrophilic groups, per 100 parts by weight of the finally obtained water-dispersible urethane resin,0.5-5%If it is less than this range, it will be difficult to obtain a stable aqueous dispersion.On the other hand, if it exceeds this range, the viscosity of the aqueous dispersion will be extremely high. In either case, it becomes too large, and it becomes impossible to handle itself.
[0045]
The above-described water-dispersible urethane resin containing a polydimethylsiloxane group, which is used in preparing an aqueous resin composition and an antifouling coating agent and a releasable coating agent, respectively, according to the present invention, It is not particularly limited as long as it is a urethane resin having both a polydimethylsiloxane group and a hydrophilic group. For example, it has one or more active hydrogen capable of reacting with an isocyanate group in the molecule. It can be easily obtained by using polysiloxane.
[0046]
If only typical examples of such polysiloxanes having one or more active hydrogens in the molecule are exemplified, the following compounds may be mentioned.
[0047]
That is,
[0048]
S-1:
[0049]
[Chemical 1]

[0050]
(However, n in the formula is an integer in the range of 1 to 150.)
[0051]
S-2:
[0052]
[Chemical formula 2]

[0053]
(However, n in the formula is an integer in the range of 1 to 150.)
[0054]
S-3:
[0055]
[Chemical Formula 3]

[0056]
(However, n in the formula is an integer in the range of 1 to 150.)
[0057]
S-4:
[0058]
[Formula 4]

[0059]
(However, n in the formula is an integer in the range of 1 to 150.)
[0060]
S-5:
[0061]
[Chemical formula 5]

[0062]
(However, n in the formula is an integer in the range of 1 to 150.)
[0063]
S-6:
[0064]
[Chemical 6]

[0065]
(However, n in the formula is an integer in the range of 1 to 150.)
[0066]
The above-mentioned water-dispersible urethane resin used in preparing the aqueous resin composition and the antifouling coating agent and the releasable coating agent, respectively, according to the present invention, is prepared using the raw materials as listed above. It is prepared by a known and commonly used method.
[0067]
As a specific preparation method, only typical ones will be exemplified as follows. That is, as described above, the polyisocyanate and the active hydrogen-containing compound (including the hydrophilic group-containing compound) are used in an equivalent ratio of isocyanate group / active hydrogen group,0.8 / 1-1.2 / 1The reaction is preferably performed at a ratio of 0.9 / 1 to 1.1 / 1 and a temperature of 20 to 120 ° C., preferably 30 to 100 ° C. Good.
[0068]
These reactions can be performed in an organic solvent. The organic solvent is not particularly limited, and various known and commonly used organic solvents can be used. Among these, methyl ethyl ketone is particularly preferable.
[0069]
Next, the above-mentioned perfluoroalkyl group-containing ethylene used in preparing the above-described vinyl polymer in the preparation of the aqueous resin composition and the antifouling coating agent and the release coating agent, respectively, according to the present invention. The unsaturated unsaturated monomer is not particularly limited, and any of various known and commonly used compounds can be used.
[0070]
If only typical ones are exemplified as the perfluoroalkyl group-containing ethylenically unsaturated monomers, the following general formula
[0071]
[Chemical 7]

[0072]
[In the formula, Rf represents a perfluoroalkyl group having 4 to 20 carbon atoms, R₁ Is a hydrogen atom or a methyl group, A is -Q-, -CON (R₂ ) -Q- or -SO₂ N (R₂) -Q- (wherein -Q- represents an alkylene group having 1 to 10 carbon atoms, R₂ Represents an alkyl group having 1 to 4 carbon atoms. ). ]
[0073]
And so-called perfluoroalkyl group-containing (meth) acrylates.
[0074]
Here, specific examples of the perfluoroalkyl group-containing (meth) acrylate include the following compounds.
[0075]
Ie
[0076]
B-1:
[0077]
[Chemical 8]
CF_Three(CF₂)_nCH₂CH₂OCOCH = CH₂
[0078]
(However, n in the formula is an integer in the range of 5 to 11, and the average is 9.)
[0079]
B-2:
[0080]
[Chemical 9]
CF_Three(CF₂)₇CH₂CH₂OCOC (CH_Three) = CH₂
[0081]
B-3:
[0082]
[Chemical Formula 10]
CF_Three(CF₂)_FiveCH₂CH₂OCOC (CH_Three) = CH₂
[0083]
B-4:
[0084]
Embedded image
(CF_Three)₂CF (CF₂)₆(CH₂)_ThreeOCOCH = CH₂
[0085]
B-5:
[0086]
Embedded image
(CF_Three)₂CF (CF₂)_Ten(CH₂)_ThreeOCOCH = CH₂
[0087]
B-6:
[0088]
Embedded image
CF_Three(CF₂)₇SO₂N (C_ThreeH₇) CH₂CH₂OCOCH = CH₂
[0089]
B-7:
[0090]
Embedded image
CF_Three(CF₂)₇SO₂N (CH_Three) CH₂CH₂OCOC (CH_Three) = CH₂
[0091]
B-8:
[0092]
Embedded image
CF_Three(CF₂)₇SO₂N (CH_Three) CH₂CH₂OCOCH = CH₂
[0093]
B-9:
[0094]
Embedded image
CF_Three(CF₂)₇(CH₂)_FourOCOCH = CH₂
[0095]
B-10:
[0096]
Embedded image
CF_Three(CF₂)₆COOCH = CH₂
[0097]
B-11:
[0098]
Embedded image
CF_Three(CF₂)₇SO₂N (C_FourH₉) (CH₂)_FourOCOCH = CH₂
[0099]
B-12:
[0100]
Embedded image
CF_Three(CF₂)₇CH₂CH (OH) CH₂OCOCH = CH₂
[0101]
B-13:
[0102]
Embedded image
CF_Three(CF₂)_FiveCON (C_ThreeH₇) CH₂CH₂OCOC (CH_Three) = CH₂
[0103]
Or B-14:
[0104]
Embedded image
CF_Three(CF₂)₇CON (C₂H_Five) CH₂CH₂OCOCH = CH₂
[0105]
Examples of such compounds are particularly representative.
[0106]
The polydimethylsiloxane group-containing ethylenically unsaturated monomer is any compound as long as it has both the polydimethylsiloxane group and the ethylenically unsaturated double bond in the molecule. However, if only a representative one of them is exemplified, the following general formula
[0107]
Embedded image

[0108]
(However, n in the formula is an integer in the range of 1 to 150.)
[0109]
And so-called macromonomers.
[0110]
Both of these monomers (monomers) can be copolymerized with a perfluoroalkyl group-containing ethylenically unsaturated monomer and / or a polydimethylsiloxane group-containing ethylenically unsaturated monomer, respectively. If only the typical ones are exemplified as other ethylenic monomers,
[0111]
Ethylene, propylene, vinyl chloride, vinylidene chloride, styrene, α-methylstyrene, vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso (iso) -butyl (meth) acrylate , Tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl Including (meth) acrylate, iso-stearyl (meth) acrylate, etc.
[0112]
Furthermore, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl vinyl ether, propyl vinyl ether, octyl vinyl ether, butadiene, isoprene Chloroprene, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, (meth) acrylamide or 3-chloro-2-hydroxy (meth) acrylate.
[0113]
Further, as other ethylenically unsaturated monomers, crosslinkable ethylenically unsaturated monomers can be used, but only typical ones as such crosslinkable ethylenically unsaturated monomers are used. To illustrate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, diacetone acrylamide, acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxyethyl crotonate, acetoacetoxypropyl acrylate, acetoacetoxypropyl methacrylate Acetoacetoxypropyl crotonate, 2-cyanoacetoacetoxyethyl methacrylate, N- (2-acetoacetoxyethyl) acrylamide or N- (2-acetoacetoxyethyl) methacrylamide. Including news, and the like various acetoacetyl group containing ethylenically unsaturated monomer as typified by allyl acetoacetate or acetoacetate vinyl acetate.
[0114]
In addition, only typical examples of the polyfunctional ethylenically unsaturated monomer are exemplified. Ethylene di (meth) acrylate, polyoxyalkylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Esters of various polyhydric alcohols such as bisphenol A ethylene oxide adduct di (meth) acrylate and acrylic acid or methacrylic acid,
[0115]
Furthermore, urethane resin di (meth) acrylates having a urethane resin skeleton and unsaturated groups, epoxy di (meth) acrylates having an epoxy resin skeleton, or polyfunctional oligoester (meth) acrylates having a polyester resin skeleton, etc. It is.
[0116]
The amount of the perfluoroalkyl group-containing ethylenically unsaturated monomer is not particularly limited, but the total weight of the ethylenically unsaturated monomer is 100 parts by weight, that is, the total amount of the ethylenically unsaturated monomer. Based on 100 parts by weight40 to 95 parts by weightIt is desirable that
[0117]
The perfluoroalkyl group-containing ethylenically unsaturated monomer isLess than 40 parts by weightIn this case, the properties of the so-called fluororesin such as antifouling property, water repellency, oil repellency, mold release property, releasability and lubricity are hardly obtained.95 parts by weightIn the case where the amount is larger than the above, it is difficult to obtain a function based on more fluororesin, which is not preferable from the viewpoint of manufacturing cost.
[0118]
The amount of the polydimethylsiloxane group-containing ethylenically unsaturated monomer is not particularly limited, but is 100 parts by weight of the ethylenically unsaturated monomer, that is, the total amount of ethylenically unsaturated monomer. Based on 100 parts by weight30 parts by weight or lessIt is desirable that
[0119]
The polydimethylsiloxane group-containing ethylenically unsaturated monomer is30 parts by weightWhen the amount is larger, it is inevitably difficult to obtain a stable aqueous dispersion.
[0120]
In addition, when the perfluoroalkyl group-containing ethylenically unsaturated monomer and the polydimethylsiloxane group-containing ethylenically unsaturated monomer are used in combination, the amount used of these both monomers is not particularly limited, Contains perfluoroalkyl groupEthylenic unsaturationThe monomer is 100 parts by weight of the total amount of the ethylenically unsaturated monomer,5 to 70 parts by weightAnd the polydimethylsiloxane group-containing ethylenically unsaturated monomer is 100 parts by weight based on the total weight of the ethylenically unsaturated monomer,30 parts by weight or lessIt is desirable that
[0121]
According to the combined use of the perfluoroalkyl group-containing ethylenically unsaturated monomer and the polydimethylsiloxane group-containing ethylenically unsaturated monomer, the amount of the both is reduced while maintaining the effect of the present invention. This is also advantageous in terms of manufacturing cost.
[0122]
At this time, the perfluoroalkyl group-containing ethylenically unsaturated monomer isLess than 5 parts by weightIn this case, it is difficult to obtain a release / peeling function with a fluororesin. On the other hand, even if the amount exceeds 70 parts by weight, no further function with fluorine can be obtained. It is not preferable.
[0123]
Polydimethylsiloxane group-containing ethylenically unsaturated monomer30 parts by weightIn the case where the amount is larger than that, it is difficult to obtain a stable emulsion as in the case of using alone, and it is not preferable from the viewpoint of production cost.
[0124]
In the present invention, water dispersible urethane resinWhen,Perfluoroalkyl group-containing ethylenically unsaturated monomers and / or dimethylpolysiloxane group-containing ethylenically unsaturated monomers, and other ethylenically unsaturated monomers copolymerizable with both of these monomers. The ratio of the copolymer obtained by reacting with the saturated monomer is the weight ratio of the former water-dispersible urethane resin / the latter copolymer,9/1-1/9It is preferable from the fact that an aqueous dispersion having the characteristics of a vinyl copolymer and the characteristics of a urethane resin is obtained, and in order to obtain durable resin characteristics, the weight ratio is So,3/7-7/3It is particularly preferred that
[0125]
Each of the water-based resin composition and the antifouling coating agent and the releasable coating agent according to the present invention, respectively, used in preparing the above-described,Polycarbodiimide resinAs, various known and commonly used compounds can be used, and are not particularly limited, but only typical ones among them are exemplified.
[0126]
The following general formula
[0127]
Embedded image

[0128]
A carbodiimide compound containing an isocyanate group (A)
[0129]
(In the formula, R represents an aromatic or aliphatic divalent linking group.)
[0130]
Alternatively, the following general formula derived from these compounds (A) and containing no so-called isocyanate group:
[0131]
Embedded image

[0132]
(In the formula, R represents an aromatic or aliphatic divalent linking group, and R 'represents an alkyl group, an aralkyl group, or an oxyalkylene group.)
[0133]
A hydrophilic group-free or hydrophilic group-containing carbodiimide compound (B) as shown by
[0134]
SuchPolycarbodiimide resinIt is.
[0135]
These can be used as a water dispersion as required, but the carbodiimide compound has a hydrophilic group in the molecule and itself has water solubility or water dispersibility. In order to obtain a further high crosslinking effect, it has an aliphatic alkylene group, an alicyclic alkylene group, an aliphatic alkyl group or an alicyclic alkyl group as a functional group linked to the carbodiimide group. It is desirable to use compounds that are.
[0136]
Each of the water-based resin composition, the antifouling coating agent, and the release coating agent according to the present invention is used to prepare the vinyl polymer and the water-dispersible urethane resin. Of the aqueous dispersion described aboveAdjustment methodIs not particularly limited, but only a representative one of them will be exemplified.
[0137]
(1) The whole or part of the ethylenically unsaturated monomer mixture is dropped into an aqueous medium containing a hydrophilic group-containing water-dispersible urethane resin that has been previously water-dispersed and polymerized by a polymerization initiation source. Or a method like this
[0138]
(2) An ethylenically unsaturated monomer mixture in the presence of a hydrophilic group-containing water-dispersible urethane resin that has been previously water-dispersed, such as a homogenizer, microfluidizer, or nanomizer manufactured by Gorin, Germany. It is a method of dispersing in water with a stirrer or mixer having so-called high shearing force, and polymerizing with a polymerization initiation source,
[0139]
(3) A polymer of an ethylenically unsaturated monomer obtained by prepolymerization in an organic solvent and a hydrophilic group-containing water-dispersible urethane resin are mixed in an organic solvent to obtain a hydrophilic group of the urethane resin. After neutralizing the water, it is a method to disperse in water by phase inversion emulsification,
[0140]
(4) By polymerizing an ethylenically unsaturated monomer in an organic solvent in the presence of a hydrophilic group-containing water-dispersible urethane resin, the hydrophilic group-containing water-dispersible urethane resin and the ethylenically unsaturated monomer Preparing a mixed solution with the polymer of the body, and then neutralizing the hydrophilic group in the urethane resin and then dispersing in water by phase inversion emulsification,
[0141]
(5) Mixing an ethylenically unsaturated monomer mixture with a hydrophilic group-containing water-dispersible urethane resin in an organic solvent, and then neutralizing the hydrophilic group of the urethane resin, followed by phase inversion emulsification. And a method of dispersing in water and then polymerizing in the presence of a polymerization initiator.
[0142]
Among these methods, in order to obtain a stable aqueous dispersion, an ethylenically unsaturated monomer mixture and a hydrophilic group-containing water-dispersible urethane resin are mixed in an organic solvent, and then the urethane resin is mixed. It is particularly desirable to use the method (5) above in which the hydrophilic group is neutralized and dispersed in water by phase inversion emulsification, and then polymerized in the presence of a polymerization initiator.
[0143]
Examples of neutralizing agents for hydrophilic groups in hydrophilic group-containing water-dispersible urethane resins include only typical ones, including various volatile bases such as ammonia, Are various tertiary amines such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine or triethanolamine; or various non-volatile bases such as sodium hydroxide or potassium hydroxide. Of these, use of ammonia having high volatility is particularly desirable.
[0144]
Before forming an aqueous dispersion of the urethane resin / monomer mixture, an amount sufficient to render the urethane resin water-dispersible, i.e., as is well known in the prior art, the hydrophilic groups are substantially In order to obtain a fine particle dispersion, it is desirable to add an amount of neutralizing agent to the mixture.
[0145]
That is, the neutralizing agent is added per equivalent of the hydrophilic group,65-110%It is desirable to add with an equivalent amount within the range of80% or moreIt is particularly desirable to add a neutralizing agent until it is neutralized.
[0146]
The urethane resin / monomer mixture can be dispersed in water by a phase inversion emulsification method. Phase inversion emulsification can be carried out by methods well known to date, such as a method in which water is added dropwise to a urethane resin / monomer mixture with stirring, or a method in which addition is carried out in portions. Both are possible. Among these various methods, in order to obtain an aqueous dispersion having a high degree of stability, it is desirable to use divided addition.
[0147]
At this time, the amount of water added at one time is based on the total amount of the urethane resin / monomer mixture.1/30-1/5It is desirable to add the next water when the added water is uniformly mixed with the urethane resin / monomer mixture.
[0148]
Further, the above-mentioned polymerization initiator is not particularly limited, but various polymerization initiators such as azo compounds and organic peroxides can be used as long as only typical ones are exemplified. And various ionizing radiations such as ultraviolet rays and γ-rays, and these various polymerization initiation sources can be employed.
[0149]
The polymerization reaction of the urethane resin / monomer mixture is performed at a temperature sufficient for the polymerization initiator to dissociate the active species, and can be appropriately selected depending on the activity of the polymerization initiator used and the reaction medium. It is. A suitable temperature range when using methyl ethyl ketone as a reaction solvent is about 50 ° C. to 80 ° C., among which 60 ° C. to 75 ° C. is more desirable.
[0150]
In the present invention, an aqueous dispersion composed of a vinyl polymer and a hydrophilic group-containing water-dispersible urethane resin,Polycarbodiimide resinThe ratio of use to the former water dispersion / the latterPolycarbodiimide resinWith a weight ratio of100/1 to 100/20In particular, it is desirable in terms of obtaining durability and the like.
[0151]
The aqueous resin composition of the present invention obtained as described above mainly imparts so-called surface characteristics such as antifouling property, water repellency, oil repellency, releasability, releasability and lubricity. It can be used as a coating agent.
[0152]
If the water-based resin composition according to the present invention is only exemplified as a typical substrate material to be used when used as a so-called coating agent,
[0153]
Various synthetic films such as polyethylene terephthalate film, polypropylene film, polystyrene film or polyvinyl chloride film;
[0154]
Various papers such as information recording paper, wrapping paper, corrugated paper, paperboard or water / oil resistant paper;
[0155]
Various synthetic fibers such as polyester, nylon or acrylic, various types such as cotton, silk, hemp or woolNaturalVarious fabrics as represented by various leather products, such as fibers or synthetic leather, artificial leather or natural leather;
[0156]
There are various metals such as iron or aluminum; or various inorganic substrates such as ceramic or concrete.
[0157]
In addition, as a method of treating the aqueous resin composition according to the present invention, any method can be applied depending on the type of the base material.As a processing methodIn particular, only typical ones are exemplified by a dip coating method, a roll coater, a gravure coater, or a brush coating.
[0158]
In general, the base material treated with the aqueous resin composition according to the present invention is easily obtained by curing the aqueous resin composition to form a film. Such curing conditions include the heat resistance of the substrate andPerfluoroalkyl group-containing ethylenically unsaturated monomers and / or polydimethylsiloxane group-containing ethylenically unsaturated monomers, and other ethylenically unsaturated monomers copolymerizable with both of these monomers. Vinyl polymer that is a copolymer with polymerAnd a film forming temperature of an aqueous dispersion composed of a hydrophilic group-containing water-dispersible urethane resin can be appropriately changed.
[0159]
Usually,Perfluoroalkyl group-containing ethylenically unsaturated monomers and / or polydimethylsiloxane group-containing ethylenically unsaturated monomers, and other ethylenically unsaturated monomers copolymerizable with both of these monomers. Vinyl polymer that is a copolymer with polymerIt is desirable to carry out the curing within the range from the film forming temperature of the aqueous dispersion composed of the hydrophilic group-containing water-dispersible urethane resin to the heat-resistant temperature of the substrate. Specifically, a temperature of about 180 ° C. from room temperature is appropriate and is in the range of 100 to 180 ° C., and the curing time can be changed according to the film thickness of the film. 1 minute to 1 hour is appropriate.
[0160]
【Example】
EXAMPLES Next, although an Example and a comparative example demonstrate this invention concretely, this invention is in no way limited only to these illustration examples. In the following, all parts and% are based on weight unless otherwise specified. Further, as the monomers used, the names shown in the detailed description of the invention as described above were used as they were.
[0161]
Synthesis example 1
First, a polyester (OH value = 91) obtained by reacting ethylene glycol / neopentyl glycol / terephthalic acid / isophthalic acid / adipic acid with a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. 160 parts were added to 350 parts of methyl ethyl ketone and stirred thoroughly.
[0162]
Subsequently, 43 parts of hexamethylene diisocyanate was added, and the mixture was heated to 75 ° C. and reacted at this temperature for 3 hours. Thereafter, this solution was cooled to 55 ° C. or lower, and 13 parts of dimethylolpropionic acid was added to react for 15 hours, thereby obtaining a polyurethane solution having water dispersibility.
[0163]
194 parts of perfluoroalkyl group-containing ethylenically unsaturated monomer (B-1), 11 parts of methyl methacrylate, 6.5 parts of 2-hydroxyethyl methacrylate and 4.3 parts of N-methylol acrylamide The monomer mixture and 2.2 parts of lauryl mercaptan were dissolved in 100 parts of methyl ethyl ketone and added to the polyurethane solution to dissolve.
[0164]
Add 33 parts of 5% aqueous ammonia and maintain at 55 ° C for 0.5 hour, then divide 1,300 parts of water into 20 parts and add over 1 hour to achieve uniform water dispersion Got the body. The aqueous dispersion was heated to 70 ° C., and 1.1 parts of ammonium persulfate was added with stirring to carry out a polymerization reaction for 6 hours.
[0165]
The aqueous dispersion thus obtained was transferred to an eggplant flask and desolvated using a rotary evaporator under the conditions of 55 ° C. and 360 mmHg, whereby a stable aqueous dispersion (I) having a solid content of 25% was obtained. A yield of 1,720 parts was obtained.
[0166]
Synthesis example 2
First, a polyester (OH value = 91) obtained by reacting ethylene glycol / neopentyl glycol / terephthalic acid / isophthalic acid / adipic acid with a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. 160 parts were added to 350 parts of methyl ethyl ketone and stirred thoroughly.
[0167]
Subsequently, 43 parts of hexamethylene diisocyanate was added, and the mixture was heated to 75 ° C. and reacted at this temperature for 3 hours. Thereafter, this solution was cooled to 55 ° C. or lower, and 13 parts of dimethylolpropionic acid was added to react for 15 hours, thereby obtaining a polyurethane solution having water dispersibility.
[0168]
194 parts of perfluoroalkyl group-containing ethylenically unsaturated monomer (B-1), 113 parts of methyl methacrylate, 9.7 parts of 2-hydroxyethyl methacrylate, and 6.5 parts of N-methylol acrylamide The monomer mixture and 3.2 parts of lauryl mercaptan were dissolved in 100 parts of methyl ethyl ketone and added to the polyurethane solution to dissolve.
[0169]
Add 33 parts of 5% aqueous ammonia and maintain at 55 ° C. for 0.5 hours, then divide 1,590 parts of water into 20 parts and add over 1 hour to achieve uniform water dispersion Got the body. The aqueous dispersion was heated to 70 ° C., and 1.6 parts of ammonium persulfate was added with stirring to carry out a polymerization reaction for 6 hours.
[0170]
After the aqueous dispersion thus obtained was transferred to an eggplant flask, it was desolvated using a rotary evaporator under the conditions of 55 ° C. and 360 mmHg, thereby stabilizing the aqueous dispersion (II) with a solid content of 25%. Was obtained with a yield of 2,160 parts.
[0171]
Synthesis example 3
First, a polyester (OH value = 91) obtained by reacting ethylene glycol / neopentyl glycol / terephthalic acid / isophthalic acid / adipic acid with a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. 160 parts were added to 350 parts of methyl ethyl ketone and stirred thoroughly.
[0172]
Subsequently, 43 parts of hexamethylene diisocyanate was added, and the mixture was heated to 75 ° C. and reacted at this temperature for 3 hours. Thereafter, this solution was cooled to 55 ° C. or lower, and 13 parts of dimethylolpropionic acid was added to react for 15 hours, thereby obtaining a polyurethane solution having water dispersibility.
[0173]
84 parts of perfluoroalkyl group-containing ethylenically unsaturated monomer (B-1), 4.6 parts of methyl methacrylate, 2.8 parts of 2-hydroxyethyl methacrylate and 1.9 parts of N-methylol acrylamide A monomer mixture consisting of 0.9 part of lauryl mercaptan was dissolved in 50 parts of methyl ethyl ketone and added to the polyurethane solution to dissolve.
[0174]
After adding 33 parts of 5% aqueous ammonia and maintaining at 55 ° C. for 0.5 hour, 900 parts of water was divided into 20 parts and added over 1 hour to obtain a uniform aqueous dispersion. Obtained. The aqueous dispersion was heated to 70 ° C., and ammonium persulfate (0.5 part) was added with stirring to carry out a polymerization reaction for 6 hours. The aqueous dispersion thus obtained was transferred to an eggplant flask and desolvated using a rotary evaporator at 55 ° C. and 360 mmHg to obtain a stable aqueous dispersion (III) having a solid content of 25%. The yield was 1,230 parts.
[0175]
Synthesis example 4
First, a polyester (OH value = 91) obtained by reacting ethylene glycol / neopentyl glycol / terephthalic acid / isophthalic acid / adipic acid with a four-necked flask equipped with a thermometer, a stirring device and a reflux condenser. 160 parts of "Epoxy ester 3002M" [trade name of bisphenol A propylene oxide 2-mole adduct diglycidyl ether methacrylic acid adduct made by Kyoeisha Chemical Co., Ltd.] into 150 parts of methyl ethyl ketone In addition, it was thoroughly stirred.
[0176]
Subsequently, 49 parts of hexamethylene diisocyanate was added, and the mixture was heated to 75 ° C. and reacted at this temperature for 3 hours. Thereafter, this solution was cooled to 55 ° C. or lower, and then 14 parts of dimethylolpropionic acid was added and allowed to react for 15 hours, thereby obtaining a polyurethane solution having water dispersibility.
[0177]
It consists of 211 parts of perfluoroalkyl group-containing ethylenically unsaturated monomer (B-1), 12 parts of methyl methacrylate, 7.1 parts of 2-hydroxyethyl methacrylate and 4.7 parts of N-methylol acrylamide. The monomer mixture and 2.3 parts of lauryl mercaptan were dissolved in 120 parts of methyl ethyl ketone and added to the polyurethane solution to dissolve.
[0178]
38 parts of 5% aqueous ammonia solution was added and maintained at 55 ° C. for 0.5 hour, then 1,370 parts of water was divided into 20 parts and added over 1 hour to achieve uniform water dispersion Got the body. The aqueous dispersion was heated to 70 ° C., and 1.2 parts of ammonium persulfate was added while stirring to carry out a polymerization reaction for 6 hours.
[0179]
The aqueous dispersion thus obtained was transferred to an eggplant flask and desolvated using a rotary evaporator under the conditions of 55 ° C. and 360 mmHg, whereby a stable aqueous dispersion (IV) having a solid content of 25% was obtained. A yield of 1,880 parts was obtained.
[0180]
Synthesis example 5
First, a polyester (OH value = 91) obtained by reacting ethylene glycol / neopentyl glycol / terephthalic acid / isophthalic acid / adipic acid with a four-necked flask equipped with a thermometer, a stirring device and a reflux condenser. 160 parts and 12 parts of bisphenol A propylene oxide (PO) 2-mole adduct diglycidyl ether methacrylic acid adduct were added to 150 parts of methyl ethyl ketone and stirred thoroughly.
[0181]
Subsequently, 49 parts of hexamethylene diisocyanate was added, and the mixture was heated to 75 ° C. and reacted at this temperature for 3 hours. Thereafter, this solution was cooled to 55 ° C. or lower, and then 14 parts of dimethylolpropionic acid was added and allowed to react for 15 hours, thereby obtaining a polyurethane solution having water dispersibility.
[0182]
176 parts of perfluoroalkyl group-containing ethylenically unsaturated monomer (B-1), "UA-306H" [Kyoeisha Chemical Co., Ltd., polyfunctional acrylate made of pentaerythrol triacrylate hexamethylene diisocyanate urethane prepolymer Product name] 23.5 parts, methyl methacrylate 36 parts, 2-hydroxyethyl methacrylate 7.1 parts and N-methylol acrylamide 4.7 parts, and lauryl mercaptan 2. 3 parts were dissolved in 120 parts of methyl ethyl ketone and added to the polyurethane solution to dissolve.
[0183]
38 parts of 5% aqueous ammonia solution was added and maintained at 55 ° C. for 0.5 hour, then 1,370 parts of water was divided into 20 parts and added over 1 hour to achieve uniform water dispersion Got the body. The aqueous dispersion was heated to 70 ° C., and 1.2 parts of ammonium persulfate was added while stirring to carry out a polymerization reaction for 6 hours.
[0184]
The aqueous dispersion thus obtained was transferred to an eggplant flask and desolvated using a rotary evaporator under the conditions of 55 ° C. and 360 mmHg, whereby a stable aqueous dispersion (V) having a solid content of 25% was obtained. A yield of 1,880 parts was obtained.
[0185]
Synthesis Example 6
First, a polyester (OH value = 91) obtained by reacting ethylene glycol / neopentyl glycol / terephthalic acid / isophthalic acid / adipic acid with a four-necked flask equipped with a thermometer, a stirring device and a reflux condenser. 160 parts and 26 parts of silicone (S-1) were added to 170 parts of methyl ethyl ketone and sufficiently stirred.
[0186]
Subsequently, 54 parts of hexamethylene diisocyanate was added, and the mixture was heated to 75 ° C. and reacted at this temperature for 3 hours. Thereafter, this solution was cooled to 55 ° C. or lower, and then 16 parts of dimethylolpropionic acid was added to react for 15 hours, thereby obtaining a polyurethane solution having water dispersibility.
[0187]
183 parts of perfluoroalkyl group-containing ethylenically unsaturated monomer (B-1), 39 parts of methyl methacrylate, 7.9 parts of 2-hydroxyethyl methacrylate, polydimethylsiloxane group-containing ethylenically unsaturated monomer A monomer mixture consisting of 26 parts of (S-5) and 8.7 parts of N-methylol acrylamide and 2.6 parts of lauryl mercaptan are dissolved in 130 parts of methyl ethyl ketone and added to the polyurethane solution. And dissolved.
[0188]
Add 40 parts of 5% aqueous ammonia and maintain at 55 ° C. for 0.5 hours, then divide 1,500 parts of water into 20 parts and add over 1 hour to achieve uniform water dispersion Got the body. The aqueous dispersion was heated to 70 ° C. and 1.5 parts of ammonium persulfate was added with stirring to carry out a polymerization reaction for 6 hours.
[0189]
The aqueous dispersion thus obtained was transferred to an eggplant flask and desolvated using a rotary evaporator under the conditions of 55 ° C. and 360 mmHg, whereby a stable aqueous dispersion (VI) having a solid content of 25% was obtained. The yield was 2,120 parts.
[0190]
Example 1
8 parts of “Carbodilite V-02” [manufactured by Nisshinbo Co., Ltd., a hydrogenated MDI-based water-soluble polycarbodiimide-based resin with respect to 100 parts of the aqueous dispersion (I) obtained in Synthesis Example 1. , A light yellow transparent liquid having an active ingredient content of 40% by weight, and a non-ionic resin product name having a carbodiimide equivalent (resin content) of 590. Was prepared.
[0191]
Next, this aqueous resin composition was cast so as to have a film thickness of 200 micrometers or micron (μm), dried at room temperature for 48 hours, and then subjected to heat treatment at 120 ° C. for 5 minutes. I did it. Thereafter, the casting film thus obtained was cut into a size of 3 cm × 3 cm, and a solvent resistance evaluation judgment test was performed.
[0192]
That is, the area swelling rate and the elution rate were measured when immersed in 50 g of methyl ethyl ketone (hereinafter abbreviated as MEK) for 48 hours and left standing. The results are summarized in Table 1.
[0193]
Examples 2 and 3 The aqueous dispersion (IV) or (V) obtained in Synthesis Example 4 or 5 and “Carbodilite V-04” [manufactured by Nisshinbo Co., Ltd.]TMXDI (tetramethylxylylene diisocyanate)A water-soluble polycarbodiimide-based resin, which is a light tan transparent liquid with an active ingredient of 40% by weight, and is a nonionic resin having a carbodiimide equivalent (resin content) of 338. Carbodilite V-06 "(TDI (tolylene diisocyanate) -based water-soluble polycarbodiimide resin manufactured by the same company, which is a yellow transparent liquid with an active ingredient of 40% by weight, nonionic and carbodiimide equivalent) (Product name of resin having a resin content of 257) was added separately in the proportions shown in Table 1, and thereafter, a solvent resistance evaluation judgment test was conducted in the same manner as in Example 1. It was. The results are summarized in Table 1.
[0194]
[Table 1]

[0195]
<< Footnotes in Table 1 >>
Area swelling ratio = (Area after immersion in MEK / Area before immersion in MEK) × 100
Dissolution rate = (1-weight after MEK immersion / weight before MEK immersion) × 100
[0196]
Example 4
The target antifouling coating agent was prepared by adding 8 parts of “Carbodilite V-02” to 100 parts of the aqueous dispersion (I) obtained in Synthesis Example 1. Furthermore, after blending “Boncoat HV” [trade name of polyacrylic acid type thickener manufactured by Dainippon Ink & Chemicals, Inc.] and an aqueous ammonia solution at a ratio shown in Table 2, After stirring and dispersing under the condition of a rotation speed of 300 rpm, a blended liquid having a viscosity at 25 ° C. of 1,100 mPa · s was obtained.
[0197]
Next, this compounded solution was placed on a SUS plate with a bar coater No. 14 was applied, and heat treatment was performed at 120 ° C. for 5 minutes. Thereafter, the coating film thus obtained was subjected to a MEK rubbing test and an antifouling test against various soil substances. The results are summarized in Table 2.
[0198]
Example 5
By blending 5 parts of “Carbodilite V-04” with 100 parts of the aqueous dispersion (I) obtained in Synthesis Example 1, a target antifouling coating agent was prepared. “Boncoat HV” and an aqueous ammonia solution were blended in the proportions shown in Table 2 and stirred and dispersed under the condition that the rotational speed was 300 rpm, and the viscosity at 25 ° C. was 1,100 mPa · s. A liquid was obtained.
[0199]
Next, this compounded solution was placed on a SUS plate with a bar coater No. 14 was applied, and heat treatment was performed at 120 ° C. for 5 minutes. Thereafter, the coating film thus obtained was subjected to a MEK rubbing test and various antifouling tests. The results are summarized in Table 2.
[0200]
[Table 2]

[0201]
<< Footnotes in Table 2 >>
(1) In principle, wipe off after 24 hours
(2) Wipe with thinner after 24 hours
[0202]
◎: No residual dirt or destruction of coating film
Δ: Dirt remaining but no coating film destruction
×: Residual dirt and film destruction
[0203]
Examples 6-9
By adding various types of carbodilite as shown in Table 2 to 100 parts of the aqueous dispersions (II) to (V) obtained in Synthesis Examples 2 to 5, the intended protection can be obtained. A soil coating agent was prepared, and “Boncoat HV” and an aqueous ammonia solution were further blended in proportions as shown in Table 2.
[0204]
In the same manner as in Example 4, after coating on a SUS plate, an MEK rubbing test and various antifouling tests were performed. The results are summarized in Table 2.
[0205]
[Table 3]

[0206]
Example 10
For 8 parts of the aqueous dispersion (VI) obtained in Synthesis Example 6, 0.6 parts of “carbodilite”V-02”To prepare a target releasable coating agent. Further, this compounded solution was diluted with 92 parts of a 20% isopropyl alcohol (hereinafter abbreviated as IPA) aqueous solution, The diluted solution thus obtained was used as a bar coater no. 8 was applied to the corona discharge treated surface of a biaxially stretched polypropylene (hereinafter abbreviated as OPP) film and dried at 110 ° C. for 2 minutes.
[0207]
Thereafter, according to the following procedure, a peel performance evaluation judgment test was performed. The results are summarized in Table 3.
[0208]
[Peeling performance test method]
[0209]
A rubber-based pressure-sensitive adhesive tape [NO. 31E was used. ] Was pressure-bonded with a roller having its own weight of 2 kg.
[0210]
First, the peel performance is determined by the conditions of the peel strength (normal peel strength) after storing the tape test piece obtained as described above at 25 ° C. for 24 hours, and the conditions of 70 ° C. and 95% RH. Below, peel strength after storage for 2 days (peel strength after aging), and residual adhesive strength of tape after being stored for 24 hours at 25 ° C (normal residual adhesive strength) at 70 ° C , The evaluation was made by measuring the residual adhesive strength (residual adhesive strength after aging) after storage for 2 days under the condition of 95% RH.
[0211]
Next, the peel force was measured as the resistance at the time of 180 degree peeling under the condition that the peel speed was 300 mm / min, and the residual adhesive force was obtained as described above. The tape test piece is measured as the resistance at the time of peeling at 180 degrees under the condition that the peeling speed is 300 mm / min after being stuck on the stainless steel panel.
[0212]
[Table 4]

[0213]
Comparative Example 1
In the same manner as in Example 1, the aqueous dispersion (I) obtained in Synthesis Example 1 was cast so that the film thickness was 200 μm, and then dried at room temperature for 48 hours. Heat treatment was performed at 5 ° C. for 5 minutes.
[0214]
Subsequently, the casting film thus obtained was cut into a size of 3 cm × 3 cm, and a solvent resistance evaluation judgment test was performed. In other words, the area swelling rate and the elution rate were measured when immersed in 50 g of MEK for 48 hours and allowed to stand. The results are summarized in Table 1.
[0215]
Comparative Example 2
With respect to 100 parts of the aqueous dispersion (I) obtained in Synthesis Example 1, “Boncoat HV” and an aqueous ammonia solution were blended in the proportions shown in Table 2, and the rotational speed was 300 rpm. When the mixture was stirred and dispersed, a mixture solution having a viscosity at 25 ° C. of 2,100 mPa · s was obtained.
[0216]
Next, this blended solution was placed on a SUS plate with a bar coater No. 14 was applied, and then heat treatment was performed at 120 ° C. for 5 minutes. The coating film thus obtained was then subjected to a MEK rubbing test and various antifouling tests. The results are summarized in Table 2.
[0217]
Comparative Example 3
Eight parts of the aqueous dispersion (VI) obtained in Synthesis Example 6 were diluted with 92 parts of a 20% IPA aqueous solution. Next, the diluted solution thus obtained was used as a bar coater No. 8 was applied to the surface of the OPP that had been subjected to corona treatment. The results are summarized in Table 3.
[0218]
[Table 5]

[0219]
<< Footnotes in Table 3 >>
Blank: Test results when using uncoated OPP film and SUS plate
[0220]
Normal: (Condition) After 24 hours at 25 ° C and 65%
Aging: (Condition) After 48 hours under conditions of 70 ° C and 95%
[0221]
The units of “normal residual adhesive force” and “residual adhesive force after aging” in “peeling force”, “peeling force after aging” and “residual adhesive force”, respectively, In either case, “gf / cm²".
[0222]
【The invention's effect】
The aqueous resin composition according to the present invention is particularly excellent in solvent resistance and moist heat resistance, and can mainly form a fluorine or silicone coating film. In addition, it is possible to form a releasable coating film having excellent practicality, such as excellent transferability, low migration, and excellent releasability.

Claims (20)

Perfluoroalkyl group-containing ethylenically unsaturated monomers and / or polydimethylsiloxane group-containing ethylenically unsaturated monomers, and other ethylenically unsaturated monomers copolymerizable with both of these monomers. Durability characterized by containing an aqueous dispersion composed of a vinyl polymer which is a copolymer with a monomer, a water-dispersible urethane resin containing a hydrophilic group, and a polycarbodiimide resin . Improved aqueous resin composition. The above-mentioned vinyl polymer is in the range of 40 to 95 parts by weight as the perfluoroalkyl group-containing ethylenically unsaturated monomer, with respect to 100 parts by weight of the total weight of the ethylenically unsaturated monomer. The aqueous resin composition with improved durability according to claim 1 , which is used. The above-mentioned vinyl polymer is used within the range of 5 to 70 parts by weight as the perfluoroalkyl group-containing ethylenically unsaturated monomer, with respect to 100 parts by weight of the total amount of ethylenically unsaturated monomers. In addition, the polydimethylsiloxane group-containing ethylenically unsaturated monomer component is used in an amount of 30 parts by weight or less based on 100 parts by weight of the total weight of the ethylenically unsaturated monomer. The aqueous resin composition with improved durability according to claim 1 . The aqueous resin composition with improved durability according to claim 1, wherein the hydrophilic group-containing water-dispersible urethane resin has a carboxyl group or a carboxylate group as the hydrophilic group. The aqueous resin composition with improved durability according to claim 1, wherein the hydrophilic group-containing water-dispersible urethane resin has a polydimethylsiloxane group. The aqueous resin composition with improved durability according to claim 1, wherein the polycarbodiimide-based resin has water solubility or water dispersibility. The polycarbodiimide-based resin described above has an aliphatic alkylene group, an aliphatic alkyl group, an alicyclic alkylene group, or an alicyclic alkyl group as a functional group bonded to the carbodiimide group. The aqueous resin composition with improved durability according to claim 1 or 6 , which has a nonionic hydrophilic group in the molecule. A vinyl polymer described above, the ratio of the hydrophilic group-containing water-dispersible urethane resin, Te than the weight ratio is 7/3 to 3/7, any one of claims 1 to 7 The aqueous resin composition having improved durability according to Item. The ratio of the water dispersion composed of the vinyl polymer and the water-dispersible urethane resin containing a hydrophilic group to the polycarbodiimide resin described above is 100/1 to 100 / The aqueous resin composition with improved durability according to any one of claims 1 to 8 , which is 20 . A vinyl polymer that is a copolymer of a perfluoroalkyl group-containing ethylenically unsaturated monomer and another ethylenically unsaturated monomer copolymerizable with the monomer, and a hydrophilic group An antifouling coating agent with improved durability, comprising an aqueous dispersion composed of a water-dispersible urethane resin and a polycarbodiimide resin . Perfluoroalkyl group-containing ethylenically unsaturated monomers and / or polydimethylsiloxane group-containing ethylenically unsaturated monomers, and other ethylenically unsaturated monomers copolymerizable with both of these monomers. Durability characterized by containing an aqueous dispersion composed of a vinyl polymer which is a copolymer with a monomer, a water-dispersible urethane resin containing a hydrophilic group, and a polycarbodiimide resin . Improved releasable coating agent. The antifouling coating agent with improved durability according to claim 10, wherein the hydrophilic group-containing water-dispersible urethane resin has a carboxylic acid group or a carboxylate group as the hydrophilic group. . The release coating agent with improved durability according to claim 11, wherein the hydrophilic group-containing water-dispersible urethane resin has a carboxylic acid group or a carboxylate group as the hydrophilic group. . The releasable coating agent according to claim 11 , wherein the hydrophilic group-containing water-dispersible urethane resin has a polydimethylsiloxane group. The polycarbodiimide-based resin described above has an aliphatic alkylene group, an aliphatic alkyl group, an alicyclic alkylene group, or an alicyclic alkyl group as a functional group bonded to the carbodiimide group. The antifouling coating agent with improved durability according to claim 10 or 12 , which has a nonionic hydrophilic group in the molecule . The polycarbodiimide-based resin described above has an aliphatic alkylene group, an aliphatic alkyl group, an alicyclic alkylene group, or an alicyclic alkyl group as a functional group bonded to the carbodiimide group. The releasable coating agent with improved durability according to any one of claims 11, 13 and 14, which has a nonionic hydrophilic group in the molecule. A vinyl polymer described above, the ratio of the hydrophilic group-containing water-dispersible urethane resin, Te than the weight ratio is in the range of 7 / 3-3 / 7, in claim 10 or 12 The antifouling coating agent with improved durability described. The ratio between the vinyl polymer and the hydrophilic group-containing water-dispersible urethane resin is within a range of 7/3 to 3/7 in terms of a weight ratio. 14. A releasable coating agent having improved durability according to any one of 14. When configured aqueous dispersion from the above-mentioned vinyl polymer and a hydrophilic group-containing water-dispersible urethane resin, and the proportion of Porikarubojimido based resin, Te than a weight ratio of 100 / 1-100 / 20 The antifouling coating agent with improved durability according to claim 10 or 12 , which is within the range of . The ratio of the water dispersion composed of the vinyl polymer and the water-dispersible urethane resin containing a hydrophilic group and the polycarbodiimide resin described above is 100/1 to 100/20 in weight ratio. The releasable coating agent with improved durability according to claim 11, which is within the range of