JP2004263145A - Water-dispersed powder slurry coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a powder slurry coating material produced by using a surfactant and giving a coating film having excellent water-resistance and coating film strength. <P>SOLUTION: The water-dispersed powder slurry coating material contains (A) fine particles of a resin (a1) having active hydrogen and (B) a reactive surfactant having a (blocked) isocyanate group and/or epoxy group in an aqueous medium. The reactive surfactant (B) contains a hydrophobic part having a 6-100C hydrocarbon group having aromatic ring and a (blocked) isocyanate group and/or epoxy group and a hydrophilic part composed of at least one kind of unit selected from oxyethylene unit, an anionic group, a cationic group and an amphoteric ion group. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００４０】
式中、Ｑは、１価フェノール又は１価の芳香族アルコール（ｂ１）とブロック化されていてもよいイソシアネート基を有するビニルモノマー（ｂ２）及び／又はエポキシ基を有するビニルモノマー（ｂ２’）との付加物もしくはそのポリオキシアルキレンエーテル（ｂ３）の残基を、Ｇは、ウレア結合を有していてもよい有機ジイソシアネート（ｂ４）の残基を、Ｘは、Ｏ又はＮＨを、Ｊは、ポリオキシエチレン単位を含有するポリオキシアルキレン鎖を有するジオール及び／又はジアミン（ｂ５）の残基を、Ｚは、水素、−ＣＯＯ−Ｑで表される基、または、−ＣＯ−Ｙ（Ｙは、−ＯＲ^１（Ｒ^１：炭素数１〜１８の１価アルコールの残基）又は−ＮＲ^２Ｒ^３（Ｒ^２：炭素数１〜１８の炭化水素基又は炭素数１〜１６のヒドロキシアルキル基、Ｒ^３：水素、炭素数１〜１８の炭化水素基又は炭素数１〜１６のヒドロキシアルキル基）である）を、それぞれ表す。ｍは、１〜５００の整数である。
【００４１】
本発明において、上記ウレタン樹脂（Ｌ）の製法は特に限定されず、通常のポリウレタン樹脂を製造する方法（ワンショット法または多段法）で、上記付加物もしくはそのポリオキシアルキレンエーテル（ｂ３）〜ジオール及び／又はジアミン（ｂ５）、必要に応じて上記伸長剤（ｂ１０）、および停止剤（ｂ１１）をウレタン化反応させることにより得られる。ウレタン化の反応温度は好ましくは３０〜２００℃、より好ましくは５０〜１８０℃である。反応時間は好ましくは０．１〜３０時間、より好ましくは０．１〜８時間である。
該ウレタン化反応は無溶剤系又はイソシアネートに不活性な有機溶剤中で行なうことが好ましい。該有機溶剤としては、例えば、アセトン、テトラヒドロフラン、ジメチルホルムアミド、ジメチルスルホキサイド、トルエン、ジオキサン等が挙げられる。該有機溶剤はウレタン樹脂（Ｌ）を生成させたのち、蒸留法等により除去されるのが好ましい。
【００４２】
上記ウレタン化反応において、ヒドロキシル（ＯＨ）基及びアミノ基（ＮＨ_２）と、上記有機ジイソシアネート（ｂ４）のイソシアネート（ＮＣＯ）基の当量比［（ＯＨ＋ＮＨ_２）／ＮＣＯ比］は、好ましくは１：（０．８〜１．５）、さらに好ましくは１：（０．９〜１．３）である。ＮＣＯ基の当量比が０．８〜１．５であると、得られるポリウレタン樹脂が適度の分子量となり、得られる樹脂水性分散体からの皮膜の耐水性が良好となる。
【００４３】
アニオン、カチオン、もしくは両性イオンを有する、本発明における反応性界面活性剤（Ｂ２）において、親水基としては、特に限定されず、例えば、アニオン基であればカルボン酸塩の基（−ＣＯＯ⁻Ｘ^＋）、スルホン酸塩の基（−ＳＯ_３ ⁻Ｘ^＋）、硫酸エステル塩の基（−ＯＳＯ_３ ⁻Ｘ^＋）、リン酸エステル塩の基（−ＯＰＯ_３Ｈ⁻Ｘ^＋，−ＯＰＯ_３ ^２−・２Ｘ^＋）等が（Ｘは、例えば、ナトリウム、カリウム、アンモニウム、アルカノールアミン塩等）、カチオン基であれば第１級アミンの塩の基、第２級アミンの塩の基、第３級アミンの塩の基、第４級アンモニウム塩の基等が、両性イオン基ではベタイン基等の親水基が挙げられる。
【００４４】
親水基の含量は、上記反応性界面活性剤（Ｂ２）の重量に対して好ましくは０．１重量％以上、さらに好ましくは１重量％以上、特に好ましくは５重量％以上であり、好ましくは５０重量％以下、さらに好ましくは２０重量％以下、特に好ましくは１０重量％以下含有する。該親水基の含有量が０．１重量％以上５０重量％以下であると、乳化力が強く、安定なスラリー塗料を得ることができる。
【００４５】
上記反応性界面活性剤（Ｂ２）の重量平均分子量は好ましくは３００〜１００，０００、さらに好ましくは８００〜５０，０００、特に好ましくは１，０００〜８，０００である。重量平均分子量は、十分な界面活性能力が得られる点で、３００以上が好ましく、低粘度で安定な樹脂水性分散体が得られる点で１００，０００以下が好ましい。
【００４６】
本発明における反応性界面活性剤（Ｂ２）は、好ましくは、例えば、１価フェノール又は１価の芳香族アルコール（ｂ１）とブロック化されていてもよいイソシアネート基を有するビニルモノマー（ｂ２）及び／又はエポキシ基を有するビニルモノマー（ｂ２’）とからなる付加反応物の残基又はそのアルキレンオキサイド付加物の残基（ｂ３’）と、アニオン基、カチオン基、及び両性イオン基の群から選ばれる少なくとも１種のイオン基を主要構成要素としてなる。
【００４７】
アニオン基、カチオン基、及び両性イオン基の群から選ばれる少なくとも１種のイオン基は、残基（ｂ３’）中のいずれの部位に付加されていてもよく、例えば、芳香環、上記１価フェノール又は１価の芳香族アルコール（ｂ１）により導入された水酸基、又は、この水酸基にアルキレンオキサイドが付加されたことにより導入された水酸基等に付加され得る。
【００４８】
本発明において、上記反応性界面活性剤（Ｂ２）の製法は特に限定されず、たとえば、上述した付加物もしくはそのポリオキシアルキレンエーテル（ｂ３）の末端ヒドロキシル基を、アニオン化（Ｂ２−１）、カチオン化（Ｂ２−２）、両性イオン化（Ｂ２−３）することで得られる。
【００４９】
上記アニオン化（Ｂ２−１）の方法としては、例えば、上述の付加物もしくはそのポリオキシアルキレンエーテル（ｂ３）の末端ヒドロキシル基の、無水硫酸、クロルスルホン酸等による硫酸エステル化、無水リン酸などによるリン酸エステル化などが挙げられる。反応温度は好ましくは２０℃〜２００℃、より好ましくは２０℃〜１００℃である。反応時間は好ましくは０．１〜３０時間、より好ましくは０．１〜１０時間である。
【００５０】
上記カチオン化（Ｂ２−２）の方法としては、例えば、アミノ化された上記付加物もしくはそのポリオキシアルキレンエーテル（ｂ３）末端の、酸による中和、アルキル化剤による第４級化などが挙げられる。中和に用いる酸は特に限定されず、例えば、塩酸、酢酸などが挙げられる。また、第４級化に用いるアルキル化剤は、例えば、メチルクロライド、メチルブロマイド、ベンジルクロライド、長鎖アルキルクロライド、エピクロルヒドリン、ジメチル硫酸、エチレンオキサイド等が挙げられる。末端をアミノ化する方法としては、例えば上述の付加物もしくはそのポリオキシアルキレンエーテル（ｂ３）のヒドロキシル基に、水酸化カリウム等のアルカリ触媒存在下、アクリロニトリルを１０〜８０℃で滴下して付加させた後、用いたアルカリ触媒を除去して、メタノール等の溶媒中で高圧下（例えば３０〜１００ｋｇ／ｃｍ^２）、ニッケルやコバルト等の触媒を用いて水素添加する方法等が挙げられる。
中和反応の反応温度は、好ましくは２０〜１５０℃、より好ましくは２０〜１００℃である。反応時間は好ましくは０．１〜２０時間、より好ましくは０．１〜６時間である。
アルキル化剤による反応温度は、好ましくは５０〜３００℃、より好ましくは８０〜１５０℃である。反応時間は好ましくは０．１〜２０時間、より好ましくは０．１〜１２時間である。
【００５１】
上記両性イオン化（Ｂ２−３）の方法としては、例えば、上記付加物もしくはそのポリオキシアルキレンエーテル（ｂ３）の末端のアミノ基を上記アルキル化剤で第３級化した後、モノクロル酢酸ナトリウムの水溶液と反応させる方法、ビニル基含有エステルもしくはビニル基含有ニトリルを付加させた後、アルカリでケン化する方法などが挙げられる。ビニル基含有エステルとしては、アクリル酸メチル、アクリロニトリル等が挙げられる。
【００５２】
また、末端ＯＨのノニオン性の反応性界面活性剤（Ｂ１）を反応させ、アニオン基、カチオン基、及び両性イオン基の群から選ばれる少なくとも１種の基を有するものは上述した本発明における反応性界面活性剤（Ｂ３）となる。その製造は、上述の反応性界面活性剤（Ｂ２）の製法に準じて行うことができる。
【００５３】
本発明における反応性界面活性剤（Ｂ３）において、アニオン基、カチオン基、又は両性イオン基の含量は、上記反応性界面活性剤（Ｂ３）の重量に対して好ましくは０．１重量％以上、さらに好ましくは１重量％以上、特に好ましくは５重量％以上であり、好ましくは５０重量％以下、さらに好ましくは２０重量％以下、特に好ましくは１０重量％以下含有する。該親水基の含有量が０．１重量％以上５０重量％以下であると、乳化力が強く、安定なスラリー塗料を得ることができる。
【００５４】
上記反応性界面活性剤（Ｂ３）の重量平均分子量は好ましくは１，０００〜１００，０００、さらに好ましくは２，０００〜５０，０００、特に好ましくは４，０００〜２０，０００である。重量平均分子量は、十分な界面活性能力が得られる点で、１，０００以上が好ましく、低粘度で安定な樹脂水性分散体が得られる点で１００，０００以下が好ましい。
【００５５】
本発明において、反応性界面活性剤（Ｂ）のＨＬＢは、エチレン性不飽和単量体を乳化する力および樹脂微粒子を分散させて安定な水性分散体又は水性エマルジョンとする観点から、５〜４０が好ましく、５〜２０がさらに好ましい。上記反応性界面活性剤（Ｂ）のＨＬＢの調整は、たとえば上記反応性界面活性剤（Ｂ）中の疎水基の種類とその含有量の調整および親水基の種類とその含有量の調整により行うことができる。該ＨＬＢは、例えば、藤本武彦著「全訂版新・界面活性剤入門」三洋化成工業株式会社、１９９２年発行の１９７頁に記載の小田の方法により求めることができる。すなわち、各官能基の無機性（親水性）又は有機性（疎水性）の数値を炭素原子数に基づいて評価した有機性と無機性の数値（この数値は、例えば、上記文献の第３・３・１１表に掲載されている）を用いて、上記反応性界面活性剤（Ｂ）中の疎水基の種類とその含有量及び親水基の種類とその含有量から、その有機性の値と無機性の値を求め、以下の式によりＨＬＢを計算する。
ＨＬＢ＝１０×（無機性／有機性）
【００５６】
本発明のスラリー塗料において、微粒子（Ａ）は、活性水素を含有する樹脂（ａ１）からなり、さらに硬化剤（ａ２）を含有することが好ましい。樹脂（ａ１）と硬化剤（ａ２）とは、例えば、有機系溶剤に溶解させるか、溶融混練させることで混合されることが好ましい。
微粒子（Ａ）は、例えば、上記樹脂（ａ１）、及び好ましくは硬化剤（ａ２）、の溶剤溶液を水中に分散し、該溶剤を脱溶剤する方法、又は、上記樹脂（ａ１）と好ましくはさらに硬化剤（ａ２）とを溶融混練したものを粉砕する方法によって得られる。また、後述するように、反応性界面活性剤（Ｂ）を含む水性媒体中に、樹脂（ａ１）および好ましくは硬化剤（ａ２）を溶剤に溶解したものを、分散させ、該溶剤を脱溶剤することにより、スラリー塗料の製造時において製造することもできる。
本発明のスラリー塗料において、微粒子（Ａ）の粒子形状は不定形であっても球状であっても良いが、塗膜の平滑性、均一性の点で球状の方が好ましい。ここで球状というのは粒子の長径／短径の比率が１．０〜１．５の範囲にあるものを指す。
また、該微粒子（Ａ）の平均粒径は、本発明のスラリー塗料中、好ましくは０．１〜５０μｍ、より好ましくは０．５〜２０μｍ、さらに好ましくは１．０〜１０μｍである。粒径の測定法は電子顕微鏡測定、沈降法、エレクトロゾーン法、動的光散乱法等があるが、測定粒度範囲の適合性より、動的光散乱法での測定が好ましい。
【００５７】
微粒子（Ａ）は、平均の長径／短径比率が１．０〜１．５の球形であり、好ましくは１．０〜１．２である。長径／短径比率は光学顕微鏡を用いて粒子を観察し、Ｈｅｙｗｏｏｄの定義により、粒子の平面図について輪郭に接する二つの平行線の最短距離を短径、それに直角方向の平行線の最大距離を長径とし、測定される値の長径と短径の比率を計算して求める。
【００５８】
活性水素を含有する樹脂（ａ１）を溶解させる有機系溶剤としては、たとえば、芳香族炭化水素系溶剤、脂肪族または脂環式炭化水素系溶剤、ハロゲン系溶剤、エステル系またはエステルエーテル系溶剤、エーテル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、スルホキシド系溶剤、複素環式化合物系溶剤、ならびにこれらの２種以上の混合溶剤が挙げられる。これらのうち好ましいのはエーテル系溶剤またはエステルエーテル系溶剤または芳香族炭化水素系溶剤である。
【００５９】
芳香族炭化水素系溶剤としては、例えば、トルエン、キシレン、エチルベンゼン、テトラリンなどが挙げられる。
脂肪族または脂環式炭化水素系溶剤としては、例えば、ｎ−ヘキサン、ｎ−ヘプタン、ミネラルスピリット、シクロヘキサンなどが挙げられる。
ハロゲン系溶剤としては、例えば、塩化メチル、臭化メチル、ヨウ化メチル、メチレンジクロライド、四塩化炭素、トリクロロエチレン、パークロロエチレンなどが挙げられる。
エステル系溶剤としては、例えば、酢酸エチル、酢酸ブチルなどが挙げられる。
エステルエーテル系溶剤としては、例えば、メトキシブチルアセテート、メチルセロソルブアセテート、エチルセロソルブアセテートなどが挙げられる。
エーテル系溶剤としては、例えば、ジエチルエーテル、テトラヒドロフラン、ジオキサン、エチルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテルなどが挙げられる。
ケトン系溶剤としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジ−ｎ−ブチルケトン、シクロヘキサノンなどが挙げられる。
アルコール系溶剤としては、例えば、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｔ−ブタノール、２−エチルヘキシルアルコール、ベンジルアルコールなどが挙げられる。
アミド系溶剤としては、例えば、ジメチルホルムアミド、ジメチルアセトアミドなどが挙げられる。
スルホキシド系溶剤としては、例えば、ジメチルスルホキシドなどが挙げられる。
複素環式化合物系溶剤としては、例えば、Ｎ−メチルピロリドンなどが挙げられる。
【００６０】
本発明において、活性水素［アルコール性水酸基、フェノール性水酸基、アミノ基、カルボン酸基、リン酸基、チオール基など］を含有する樹脂（ａ１）は、例えば、アクリル樹脂（ａ１▲１▼）、ポリエステル樹脂（ａ１▲２▼）、ポリウレタン樹脂（ａ１▲３▼）、エポキシ樹脂（ａ１▲４▼）等で、活性水素基を含有したものが挙げられる。
反応性界面活性剤（Ｂ）がブロック化されていてもよいイソシアネート基を有する場合は、上記いずれの活性水素を有する樹脂に対しても反応性界面活性剤（Ｂ）は好ましく用いられるが、特にアクリル樹脂（ａ１▲１▼）が好ましい。
反応性界面活性剤（Ｂ）がエポキシ基を有する場合は、アルコール性水酸基、カルボン酸基、アミノ基、チオール基の活性水素を有する樹脂に対して反応性界面活性剤（Ｂ）は好ましく用いられ、特にアルコール性水酸基、カルボン酸基の活性水素を有するアクリル樹脂（ａ１▲１▼）が好ましい。
上記樹脂（ａ１）の活性水素当量は、好ましくは５０〜５０，０００、より好ましくは１００〜１０，０００、さらに好ましくは２００〜５，０００である。
【００６１】
上記アクリル樹脂（ａ１▲１▼）を構成するモノマーとしては、（ｉ）［（メタ）アクリル酸又は水酸基を有する（メタ）アクリル酸エステル］（ａ１▲１▼１）、及び（ｉｉ）［水酸基を有しない（メタ）アクリル酸エステル、アクリルアミド、アクリロニトリル］（ａ１▲１▼２）、（ｉｉｉ）必要により他のモノマー（ａ１▲１▼３）が挙げられる。
アクリル系樹脂（ａ１▲１▼）におけるモノマー（ａ１▲１▼１）、モノマー（ａ１▲１▼２）及びモノマー（ａ１▲１▼３）の重量％比は、好ましくは（１〜１００）／（０〜８０）／（０〜５０）であり、より好ましくは（１〜５０）／（１〜５０）／（０〜２０）である。
上記アクリル樹脂（ａ１▲１▼）は溶液重合、塊状重合、懸濁重合などの公知の重合法により製造され、重量平均分子量は、好ましくは１，０００〜２００，０００、より好ましくは２，０００〜１００，０００、さらに好ましくは３，０００〜５０，０００である。
上記モノマー（ａ１▲１▼１）としては、例えば、アクリル酸、メタクリル酸、ヒドロキシアルキル（炭素数２〜４）（メタ）アクリレート、たとえば２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレートなどが挙げられる。
これらのうち好ましいものは２−ヒドロキシエチル（メタ）アクリレートである。
上記モノマー（ａ１▲１▼２）としては、例えば、アクリルアミド、アクリロニトリル、（メタ）アクリレート（シクロ）アルキルエステル［（メタ）アクリレートと炭素数１〜２５のアルコール類（メチルアルコール、エチルアルコール、ブチルアクコール、ステアリルアルコール、エチレングリコール、１，４ブタンジオール、シクロヘキサノール、イソボルネオールなど）とのエステル］などが挙げられる。
これらのうち好ましいものはメチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリルレートである。
上記モノマー（ａ１▲１▼３）としては、例えば、スチレンなどが挙げられ、これらのうち好ましいものは、スチレンである。
【００６２】
ポリエステル樹脂（ａ１▲２▼）としては、例えば、低分子ポリオールおよび／または重量平均分子量５，０００以下のポリアルキレンエーテルジオールとポリカルボン酸とを反応させて得られる縮合ポリエステルポリオール、ラクトンの開環重合により得られるポリラクトンジオール、低分子ジオールと低級アルコール（メタノールなど）の炭酸ジエステルとを反応させて得られるポリカーボネートジオールなどが含まれる。
【００６３】
上記低分子ポリオールとしては、上記ポリエーテルジオール（ｂ５−１）の低分子ジオールとして記載したものが挙げられる。
また、重量平均分子量５，０００以下のポリアルキレンエーテルジオールとしては、例えば、ポリテトラメチレンエーテルグリコール、ポリプロピレングリコール、ポリエチレングリコール、およびこれらの２種以上の混合物が挙げられる。
【００６４】
また、ポリカルボン酸としては、例えば、脂肪族ジカルボン酸（コハク酸、アジピン酸、アゼライン酸、セバチン酸など）、芳香族ジカルボン酸（テレフタル酸、イソフタル酸、フタル酸など）、これらのジカルボン酸のエステル形成性誘導体［酸無水物、低級アルキル（炭素数１〜４）エステルなど］およびこれらの２種以上の混合物が挙げられ；ラクトンとしてはε−カプロラクトン、γ−ブチロラクトン、γ−バレロラクトン、およびこれらの２種以上の混合物が挙げられる。
【００６５】
ポリエステル化は、通常の方法、たとえば低分子ポリオールおよび／または重量平均分子量５，０００以下のポリエーテルポリオールを、ポリカルボン酸もしくはそのエステル形成性誘導体［たとえば無水物（無水マレイン酸、無水フタル酸など）、低級エステル（アジピン酸ジメチル、テレフタル酸ジメチルなど）、ハライド等］と、またはその無水物およびアルキレンオキサイド（たとえばエチレンオキサイドおよび／またはプロピレンオキサイド）とを反応（縮合）させ、一方の構成成分であるポリオールを過剰に用いることで活性水素基を末端に残存させる方法、あるいは開始剤（低分子ジオールおよび／または重量平均分子量５，０００以下のポリエーテルジオール）にラクトンを付加させる方法により製造することができる。
【００６６】
上記ポリエステル樹脂（ａ１▲２▼）の具体例としては、例えば、ポリエチレンアジペートジオール、ポリブチレンアジペートジオール、ポリヘキサメチレンアジペートジオール、ポリネオペンチルアジペートジオール、ポリエチレンプロピレンアジペートジオール、ポリエチレンブチレンアジペートジオール、ポリブチレンヘキサメチレンアジペートジオール、ポリジエチレンアジペートジオール、ポリ（ポリテトラメチレンエーテル）アジペートジオール、ポリエチレンアゼレートジオール、ポリエチレンセバケートジオール、ポリブチレンアゼレートジオール、ポリブチレンセバケートジオール、ポリカプロラクトンジオールまたはトリオール、ポリヘキサメチレンカーボネートジオールなどが挙げられる。
【００６７】
水酸基含有ポリエステルの構成成分の比率は、ポリオールとポリカルボン酸の比率が、水酸基［ＯＨ］とカルボキシル基［ＣＯＯＨ］のモル比［ＯＨ］／［ＣＯＯＨ］として、好ましくは２／１〜１／１、より好ましくは１．５／１〜１／１、さらに好ましくは１．３／１〜１．０２／１である。他の構成成分の場合も、構成成分が変わるだけで比率は同様である。重量平均分子量は、好ましくは１，０００〜５０，０００、より好ましくは２，０００〜２０，０００、さらに好ましくは３，０００〜１５，０００である。
【００６８】
ポリエステル樹脂（ａ１▲２▼）の活性水素基としては例えば、アルコールとカルボン酸の重縮合末端のアルコール性水酸基やカルボン酸基が挙げられる。
【００６９】
ポリウレタン樹脂（ａ１▲３▼）としては、例えば、ポリオールとジイソシアネートの重付加物などが挙げられる。
ジイソシアネートの具体例としては、上記に例示のものが挙げられる。ポリオールの具体例としては、例えば、活性水素原子含有多官能化合物にアルキレンオキサイド（以下ＡＯと略記）が付加した構造の化合物およびこれらの２種以上の混合物が挙げられる。
【００７０】
活性水素原子含有多官能化合物としては、例えば、多価アルコール（ａ１▲３▼１）、多価フェノール類（ａ１▲３▼２）、アミン類（ａ１▲３▼３）、ポリカルボン酸（ａ１▲３▼４）、リン酸類（ａ１▲３▼５）、ポリチオール（ａ１▲３▼６）などが挙げられる。
【００７１】
多価アルコール（ａ１▲３▼１）としては、例えば、エチレングリコール、プロピレングリコール、１，３−ブチレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、ジエチレングリコール、ネオペンチルグリコール、ビス（ヒドロキシメチル）シクロヘキサン、ビス（ヒドロキシエチル）ベンゼンなどの２価アルコール；グリセリン、トリメチロールプロパン、ペンタエリスリトール、ジグリセリン、α−メチルグルコシド、ソルビトール、キシリット、マンニット、ジペンタエリスリトール、グルコース、フルクトース、ショ糖などの３〜８価の多価アルコールなどが挙げられる。
【００７２】
多価フェノール類（ａ１▲３▼２）としては、例えば、ピロガロール、カテコール、ヒドロキノンなどの多価フェノールのほかビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳなどのビスフェノール類などが挙げられる。
【００７３】
アミン類（ａ１▲３▼３）としては、例えば、アンモニア、炭素数１〜２０のアルキルアミン類（ブチルアミンなど）、アニリンなどのモノアミン類；エチレンジアミン，トリメチレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミンなどの脂肪族ポリアミン；ピペラジン、Ｎ−アミノエチルピペラジンおよびその他特公昭５５−２１０４４号公報記載の複素環式ポリアミン類；ジシクロヘキシルメタンジアミン、イソホロンジアミンなどの脂環式ポリアミン；フェニレンジアミン、トリレンジアミン、ジエチルトリレンジアミン、キシリレンジアミン、ジフェニルメタンジアミン、ジフェニルエーテルジアミン、ポリフェニルメタンポリアミンなどの芳香族ポリアミン；およびモノエタノールアミン、ジエタノールアミン、トリエタノールアミン、トリイソプロパノールアミンなどのアルカノールアミン類などが挙げられる。
【００７４】
ポリカルボン酸（ａ１▲３▼４）としては例えば、コハク酸、アジピン酸などの脂肪族ポリカルボン酸、フタル酸、テレフタル酸、トリメリット酸などの芳香族ポリカルボン酸があげられる。
【００７５】
リン酸類（ａ１▲３▼５）としては例えば、燐酸、亜燐酸、ホスホン酸などが挙げられる。また、ポリチオール（ａ１▲３▼６）としてはグリシジル基含有化合物と硫化水素との反応で得られる多価ポリチオール化合物などが挙げられる。
【００７６】
上述した活性水素原子含有化合物は２種以上使用することもできる。
【００７７】
上述の活性水素原子含有化合物に付加するＡＯとしては、例えば、エチレンオキサイド（ＥＯ）、プロピレンオキサイド（ＰＯ）、１，２−、２，３−もしくは１，３−ブチレンオキサイド、テトラヒドロフラン（ＴＨＦ）、スチレンオキサイド、α−オレフィンオキサイド、エピクロルヒドリンなどがあげられる。
【００７８】
ＡＯは単独でも２種以上併用してもよく、後者の場合はブロック付加（チップ型、バランス型、活性セカンダリー型など）でもランダム付加でも両者の混合系〔ランダム付加後にチップしたもの：分子中に任意に分布されたエチレンオキシド鎖を０〜５０重量％（好ましくは５〜４０重量％）有し、０〜３０重量％（好ましくは５〜２５重量％）のＥＯ鎖が分子末端にチップされたもの〕でもよい。これらのＡＯのうちで好ましいものはＥＯ単独、ＰＯ単独、ＴＨＦ単独、ＰＯおよびＥＯの併用、ＰＯおよび／またはＥＯとＴＨＦの併用（併用の場合、ランダム、ブロックおよび両者の混合系）である。
【００７９】
活性水素原子含有化合物へのＡＯの付加は、通常の方法で行うことができ、無触媒でまたは触媒（アルカリ触媒、アミン系触媒、酸性触媒）の存在下（とくにＡＯ付加の後半の段階で）に常圧または加圧下に１段階または多段階で行なわれる。
【００８０】
ポリオールの不飽和度は少ない方が好ましく、好ましくは０．１ｍｅｑ／ｇ以下、より好ましくは０．０５ｍｅｑ／ｇ以下、さらに好ましくは０．０２ｍｅｑ／ｇ以下である。
【００８１】
ポリオールとジイソシアネートの比率は、水酸基［ＯＨ］とイソシアネート基［ＮＣＯ］のモル比［ＯＨ］／［ＮＣＯ］として、好ましくは２／１〜１／１、より好ましくは１．５／１〜１／１、さらに好ましくは１．３／１〜１．０２／１である。他の構成成分の場合も、構成成分が変わるだけで比率は同様である。重量平均分子量は好ましくは１，０００〜５０，０００、より好ましくは２，０００〜２０，０００、さらに好ましくは３，０００〜１５，０００である。
【００８２】
ポリウレタン樹脂（ａ１▲３▼）の活性水素基としては例えば、活性水素原子含有化合物由来のウレタン化されていない活性水素基や、ウレタン結合中の水素が挙げられる。
【００８３】
エポキシ樹脂（ａ１▲４▼）としては、例えば、ポリエポキシド（ａ１▲４▼１）とポリカルボン酸（ａ１▲４▼２）との付加縮合物などが挙げられる。この付加重合の際、活性水素基を含有する水酸基が発生する。
エポキシ樹脂（ａ１▲４▼）の活性水素基としては例えば、エポキシ化により生成するアルコール性活性水素基が挙げられる。
【００８４】
ポリカルボン酸（ａ１▲４▼２）としては、上記に例示のものが挙げられる。また、ポリエポキシド（ａ１▲４▼１）は、脂肪族系、脂環族系、複素環系あるいは芳香族系のいずれであってよい。
【００８５】
芳香族系のポリエポキシド（ａ１▲４▼１）としては、例えば、多価フェノールのグリシジルエーテル体が挙げられ、例えば、ビスフェノールＦジグリシジルエーテル、ビスフェノールＡジグリシジルエーテル、ビスフェノールＢジグリシジルエーテル、ビスフェノールＡＤジグリシジルエーテル、ビスフェノールＳジグリシジルエーテル、ハロゲン化ビスフェノールＡジグリシジル、テトラクロロビスフェノールＡジグリシジルエーテル、カテキンジグリシジルエーテル、レゾルシノールジグリシジルエーテル、ハイドロキノンジグリシジルエーテル、ピロガロールトリグリシジルエーテル、１，５−ジヒドロキシナフタリンジグリシジルエーテル、ジヒドロキシビフェニルジグリシジルエーテル、オクタクロロ−４，４’−ジヒドロキシビフェニルジグリシジルエーテル、フェノールまたはクレゾールノボラック樹脂のグリシジルエーテル体、ビスフェノールＡ２モルとエピクロロヒドリン３モルの反応から得られるジグリシジルエーテル体、フェノールとグリオキザール、グルタールアルデヒド、またはホルムアルデヒドの縮合反応によって得られるポリフェノールのポリグリシジルエーテル体、およびレゾルシンとアセトンの縮合反応によって得られるポリフェノールのポリグリシジルエーテル体が挙げられる。
さらに、本発明において前記芳香族系のポリエポキシドとして、例えば、トリレンジイソシアネートまたはジフェニルメタンジイソシアネートとグリシドールの付加反応によって得られるジグリシジルウレタン化合物、前記２反応物にポリオールも反応させて得られるグリシジル基含有ポリウレタン（プレ）ポリマーおよびビスフェノールＡのアルキレンオキシド（エチレンオキシドまたはプロピレンオキシド）付加物のジグリシジルエーテル体も含む。
【００８６】
複素環系のポリエポキシド（ａ１▲４▼１）としては、例えば、トリスグリシジルメラミンが挙げられる。
【００８７】
脂環族系のポリエポキシド（ａ１▲４▼１）としては、例えば、ビニルシクロヘキセンジオキシド、リモネンジオキシド、ジシクロペンタジエンジオキシド、ビス（２，３−エポキシシクロペンチル）エーテル、エチレングリコールビスエポキシジシクロペンチルエール、３，４−エポキシ−６−メチルシクロヘキシルメチル−３’，４’−エポキシ−６’−メチルシクロヘキサンカルボキシレート、ビス（３，４−エポキシ−６−メチルシクロヘキシルメチル）アジペート、およびビス（３，４−エポキシ−６−メチルシクロヘキシルメチル）ブチルアミンが挙げられる。また、脂環族系としては、前記芳香族系ポリエポキシド化合物の核水添化物も含む。
【００８８】
脂肪族系のポリエポキシド（ａ１▲４▼１）としては、例えば、多価脂肪族アルコールのポリグリシジルエーテル体、多価脂肪酸のポリグリシジルエステル体、およびグリシジル脂肪族アミンが挙げられる。
多価脂肪族アルコールのポリグリシジルエーテル体としては、例えば、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、テトラメチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、およびソルビトールポリグリシジルエーテルが挙げられる。
多価脂肪酸のポリグリシジルエステル体としては、例えば、ジグリシジルアジペートが挙げられる。
グリシジル脂肪族アミンとしては、例えば、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジルヘキサメチレンジアミンが挙げられる。
また、本発明において脂肪族系としては、グリシジル（メタ）アクリレートの（共）重合体も含む。
【００８９】
これらのうち、好ましいのはビスフェノールＡジグリシジルエーテルとアジピン酸との縮合物である。
付加縮合の際、活性水素基を含有する基が発生するため、活性水素を有する樹脂（ａ１）の活性水素当量は５０〜５０，０００となることにより、重量平均分子量は、好ましくは１，０００〜２００，０００、より好ましくは２，０００〜１００，０００、さらに好ましくは３，０００〜５０，０００である。
【００９０】
反応性界面活性剤（Ｂ）がブロック化されていてもよいイソシアネート基を有する場合は、硬化剤（ａ２）としては、活性水素と反応し得る官能基が１分子中に２個以上含有された化合物であれば特に限定されず、例えば、ブロック化されていても良いイソシアネート基含有化合物、エポキシ基含有化合物、メラミン樹脂、シリルエーテル基含有化合物、（ヘミ）アセタール基含有化合物等が挙げられる。
これらのうちで好ましいのは、ブロック化されていても良いイソシアネート基含有化合物である。
【００９１】
ブロック化されていても良いイソシアネート基含有化合物としては、例えば、上記に例示の有機ジイソシアネート、並びに、これらの変性物（ウレタン基、カルボジイミド基、アロファネート基、ウレア基、ビューレット基、イソシアヌレート基またはオキサゾリドン基含有変性物など）、ＨＤＩイソシアヌレート、ＨＤＩビューレット、ＩＰＤＩイソシアヌレート、ＩＰＤＩビューレット、粗製ＭＤＩ［粗製ジアミノジフェニルメタン｛ホルムアルデヒドと芳香族アミン（アニリン）またはその混合物との縮合生成物：ジアミノジフェニルメタンと少量（たとえば５〜２０質量％）の３官能以上のポリアミンとの混合物｝のホスゲン化物］、ポリアリルポリイソシアネート（ＰＡＰＩ）、およびこれらのブロックイソシアネート化合物が挙げられる。
これらのうちで好ましいものはＨＤＩイソシアヌレートおよびＩＰＤＩイソシアヌレートである。
ブロック化剤としては、上記に例示のブロック化剤、およびこれらの２種以上の併用が挙げられる。
活性水素を含有する樹脂（ａ１）とブロック化されていてもよいイソシアネート基を有する硬化剤（ａ２）の比率は、樹脂（ａ１）の活性水素基と硬化剤（ａ２）のイソシアネート基のモル比として、好ましくは１／１以上２／１以下、より好ましくは１．２／１以上１．８／１以下、さらに好ましくは１．３／１以上１．６／１以下である。
【００９２】
エポキシ基含有化合物としては、例えば、脂肪族系、脂環族系、複素環系あるいは芳香族系のポリエポキシド化合物が挙げられ、上記に挙げたポリエポキシドが挙げられる。
【００９３】
これらのうち、好ましいのは多価脂肪族アルコールのポリグリシジルエーテル体および多価フェノールのグリシジルエーテル体である。
活性水素を含有する樹脂（ａ１）とエポキシ基を有する硬化剤（ａ２）の比率は、（ａ１）の活性水素基と（ａ２）のエポキシ基のモル比として、好ましくは１／１以上２／１以下、より好ましくは１．２／１以上１．８／１以下、さらに好ましくは１．３／１以上１．６／１以下である。
【００９４】
反応性界面活性剤（Ｂ）がエポキシ基を有する場合は、硬化剤（ａ２）としては、活性水素と反応し得る官能基が１分子中に２個以上含有された化合物であれば特に限定されず、例えば、上記に例示の化合物等が挙げられる。
これらのうちで好ましいのは、エポキシ基含有化合物またはブロック化されていても良いイソシアネート基含有化合物である。
【００９５】
本発明のスラリー塗料において、反応性界面活性剤（Ｂ）の含有量は、微粒子（Ａ）および上記反応性界面活性剤（Ｂ）の合計重量に対して好ましくは０．１〜１０重量％、さらに好ましくは０．５〜８重量％、最も好ましくは１〜５重量％である。
【００９６】
本発明のスラリー塗料中の樹脂分は、好ましくは２０〜７５重量％、さらに好ましくは２０〜６０重量％であり、該分散体の２５℃における粘度は好ましくは１０〜１００，０００ｍＰａ・ｓ、さらに好ましくは５０〜５，０００ｍＰａ・ｓである。また、該スラリー塗料中の樹脂粒子径は、０．１〜５０μｍである。
樹脂分が２０〜７５重量％であるとき、微粒子（Ａ）の水中での分散性は良好となり、分散体粘度が１０〜１００，０００ｍＰａ・ｓであるとき、塗料としての取り扱いが容易となる。また、微粒子（Ａ）の平均粒径が０．１〜５０μｍであるとき、水中での粒子の沈降は無く、焼付け時の水分揮発および粘度調整が容易となる。
【００９７】
なお、本発明の効果を阻害しない範囲において、反応性界面活性剤（Ｂ）とともに必要により公知のその他の乳化剤または界面活性剤（ノニオン性乳化剤および界面活性剤、アニオン乳化剤および界面活性剤、カチオン乳化剤および界面活性剤、各種反応性乳化剤および界面活性剤）等を併用することができる。併用する場合の該他の乳化剤および界面活性剤の使用量は、乳化剤または界面活性剤の全量に対して好ましくは４４重量％以下、より好ましくは３７重量％以下である。
【００９８】
本発明の方法で得られるスラリー塗料には、目的とする用途に応じて必要により公知の添加剤（Ｃ）（たとえば粘弾性調整剤、反応促進剤、動的表面張力調整剤、充填剤、増粘剤、耐熱もしくは耐候安定剤、レベリング剤、消泡剤、防腐剤、着色料など）を任意に含有させることができる。
【００９９】
粘弾性調整剤としては、たとえばポリカルボン酸系、ポリスルホン酸系、ポリエーテル変性カルボン酸系、ポリエーテル系等の高分子型粘弾性調整剤、ウレタン変性ポリエーテル系等の会合型粘弾性調整剤が挙げられる。また、反応性界面活性剤（Ｂ）を粘弾性調整剤として使用することもできる。配合量はスラリー塗料に対して好ましくは０．０５％以上１０．０％以下、より好ましくは０．１以上５％以下である。
【０１００】
反応促進剤としては、たとえばジアザビシクロオクタン、１，８−ジアザビシクロ（５，４，０）−ウンデセン−７などのアミン化合物、ジブチル錫ジラウレート、オクチル酸ジルコニウムなどの金属含有化合物が挙げられる。配合量はスラリー塗料に対して好ましくは０．０５％以上５．００％以下、より好ましくは０．１％以上３％以下である。
【０１０１】
動的表面張力調整剤としては、たとえばアセチレングリコール系動的表面張力調整剤、フッ素系動的表面張力調整剤やシリコーン系動的表面張力調整剤等が挙げられる。配合量はスラリー塗料に対して好ましくは０．０５％以上２０．０％以下、より好ましくは０．１以上１０％以下である。
【０１０２】
耐候安定剤としては、たとえばフェニルサリシレート、ｐ−ｔｅｒｔ−ブチルフェニルサリシレート等のサリチル酸系紫外線吸収剤、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン等のベンゾフェノン系紫外線吸収剤、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール等のベンゾトリアゾール系紫外線吸収剤、２−エチルヘキシル−２−シアノ−３，３’−ジフェニルアクリレート等のシアノアクリレート系紫外線吸収剤、オクチル化ジフェニルアミン、イソオクチル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェノール）プロピオネート等のヒンダードアミン系光安定剤が挙げられる。配合量はスラリー塗料に対して好ましくは０．０５％以上１０％以下、より好ましくは０．５％以上３％以下である。
【０１０３】
レベリング剤としては特に限定されないが、たとえば低分子ポリエチレン、低分子ポリプロピレンなどのオレフィン系樹脂、エチレン−アクリル共重合体、エチレン−メタクリル共重合体などのオレフィン共重合体、（メタ）アクリル共重合体、ポリビニルピロリドンなどが挙げられる。配合量はスラリー塗料に対して好ましくは０．２％以上６％以下、より好ましくは０．５％以上３％以下である。
【０１０４】
必要により用いる着色料としては特に限定されないが、たとえば無機顔料、有機顔料、染料などが挙げられる。無機顔料としてはたとえば、酸化チタン、カーボンブラック、酸化クロム、フェライト等が挙げられる。有機顔料としてはアゾレーキ系、モノアゾ系、ジスアゾ系、キレートアゾ系等のアゾ顔料、ベンズイミダゾロン系、フタロシアニン系、キナクリドン系、ジオキサジン系、イソインドリノン系、チオインジゴ系、ペリレン系、キノフタロン系、アンスラキノン系等の多環式顔料が挙げられる。染料としてはニグロシン系、アニリン系が挙げられる。配合量としては着色料の種類によって異なるが、スラリー塗料に対して好ましくは０．５％以上３０％以下、より好ましくは１．０％以上１０％以下である。
【０１０５】
本発明のスラリー塗料を製造する方法としては、下記の方法が例示できるが、これらに限定されない。
▲１▼脱溶剤法［反応性界面活性剤（Ｂ）を含む水性媒体中（水、またはメタノール、イソプロパノール等のアルコールやアセトン等のケトン溶剤の水混和性溶媒と水との混合溶媒）に、樹脂（ａ１）および必要により硬化剤（ａ２）を上記記載の有機系溶剤に溶解させたものを、ホモミキサー等で反応容器に分散させ、必要により最高１００℃まで加熱しながら、０．１〜１５Ｔｏｒｒまで減圧して、水を残存させるよう、上記の水混和性溶媒及び有機系溶剤だけを脱溶剤し、平均粒径０．１μｍ〜５０μｍとした樹脂粒子を水中に分散させる方法］；
▲２▼粉砕粒子分散法［樹脂（ａ１）、および必要により硬化剤（ａ２）を溶融混練し、冷却、粉砕し、平均粒径０．１〜５０μｍとした樹脂粒子を、反応性界面活性剤（Ｂ）を含む水性媒体と、ディスパーサー等で反応容器に分散させる方法］。
上記▲１▼による製造における樹脂（ａ１）、および必要により硬化剤（ａ２）の、有機系溶剤中での濃度は、好ましくは２０〜７５重量％、より好ましくは４０〜６０重量％である。
また、上記▲１▼および▲２▼の製造法による樹脂（ａ１）、および必要により硬化剤（ａ２）の、分散体中での濃度は、好ましくは５〜７０重量％、より好ましくは３０〜６０重量％である。また、分散体の２５℃粘度は、好ましくは５０〜３００，０００ｍＰａ・ｓ、より好ましくは１００〜１０，０００ｍＰａ・ｓ、さらに好ましくは１，０００〜８，０００ｍＰａ・ｓである。
また、上記製造法▲１▼における系内温度は好ましくは−５〜１００℃、より好ましくは３０〜８０℃、脱溶剤は好ましくは０．１〜５０時間、より好ましくは２〜１０時間である。
【０１０６】
上記の製造方法で用いる分散機としては、例えば、ホモミキサー、高圧ホモミキサー、ディスパーサー、高圧ホモジナイザー、スタティックミキサー、膜乳化機、フィルミックス、超音波分散機等が挙げられる。このうち好ましいのはホモミキサーである。
【０１０７】
本発明において、反応性界面活性剤（Ｂ）は、良好な界面活性能と分散安定性を示す。それとともに、分散体を塗布後、焼き付けを行うことによって、該界面活性剤が被分散体と化学結合を起こし、皮膜中に取り込まれ、優れた耐水性と強度を示す。
【０１０８】
本発明の水分散粉体スラリー塗料は、従来の水性塗料用塗装設備、または溶剤塗料用塗装設備である、スプレー塗装機を使用して塗装することができ、新規の設備を必要としない。
塗膜形成方法は、被塗装物に対して、該スラリー塗料を、ウェット膜厚、好ましくは１０以上２００μｍ以下、より好ましくは１０μｍ以上１００μｍ以下となるようにスプレー塗布する。塗料がスプレーノズルから被塗装物まで浮遊する間に、塗料中の水分が揮発して樹脂分が増加する。被塗装物に塗着時の塗料樹脂分（重量％）は、塗着塗料量と加熱後の塗膜重量との差を塗着塗料量で除した値と１００との差で表すことができ、好ましくは５０重量％以上９５重量％以下、さらに好ましくは６０重量％以上９０重量％以下であり、塗着した塗料中の樹脂分が５０重量％以上であると、塗料のタレが発生せず、平滑な塗膜が作成できる。
塗装された被塗装物を、好ましくは１００℃以上２００℃以下、より好ましくは１２０℃以上１８０℃以下の温度で、好ましくは５分以上６０分以下、より好ましくは５分以上３０分以下、さらに好ましくは５分以上２０分以下の時間加熱することで塗膜を形成することができる。
本発明の塗料を塗布し、焼き付けることによって得られる塗膜の被塗装物の膜厚は、好ましくは１０μｍ以上１５０μｍ以下、より好ましくは１５μｍ以上５０μｍ以下である。
【０１０９】
本発明の方法で得られる水分散粉体スラリー塗料は、特に自動車用トップコートとして、あるいは建築物や家電製品等、種々の製品の塗装に用いることができる。
【０１１０】
【実施例】
以下、実施例により本発明を更に詳細に説明するが、本発明はこれに限定されるものではない。以下において「部」は重量部、「％」は重量％を示す。
なお、以下の実施例において、反応性界面活性剤（Ｂ）、活性水素を有する樹脂（ａ１）及び付加物（ｂ３）の分子量は、ＧＰＣにより測定を行った。
【０１１１】
製造例１
攪拌機、滴下ロート、窒素ガス導入管、温度計、還流冷却器を備えた反応容器に４−α−クミルフェノール５３部およびルイス酸触媒（水澤化学工業社製、ＧａｌｌｅｏｎＥａｒｔｈ）２３部を仕込み、攪拌下、系内を窒素ガスで置換し、９０℃に昇温した。同温度にて３−イソプロペニル−α、α−ジメチルベンジルイソシアネートのエタノールブロック物４１０部を３時間かけて滴下し、さらに同温度にて５時間反応させた。これを３０℃に冷却後、触媒を濾別することにより、３−イソプロペニル−α，α−ジメチルベンジルイソシアネートエタノールブロック物７モルを４−α−クミルフェノール１モルに付加したもの（数平均分子量１，９００）（Ｂ０−１）を４６３部を得た。（Ｂ０−１）にＥＯを付加したもの（ＥＯ含量４５％）３１．１部、ポリエチレングリコール（数平均分子量６，０００）６６．２部およびヘキサメチレンジイソシアネート（以下ＨＤＩと略記）２．６部を８０℃で３時間反応させ、オキシエチレン単位含量６６重量％、重量平均分子量２７，０００の反応性界面活性剤［Ｂ−１］１００部を得た。
【０１１２】
製造例２
製造例１と同様のフリーデルクラフツ反応にて得られた、ヒドロキシル基含有炭化水素［スチレン２モルと、３−イソプロペニル−α，α−ジメチルベンジルイソシアネートのエタノールブロック物５モルを４−α−クミルフェノール１モルに付加したものにＥＯを付加したもの（ＥＯ含量１０％）；数平均分子量１，８００］１６．５部、ポリエチレングリコール（数平均分子量９，０００）８１．４部およびＴＤＩ２．２部を８０℃で３時間反応させ、オキシエチレン単位含量８０重量％、重量平均分子量３３，０００の反応性界面活性剤［Ｂ−２］１００部を得た。
【０１１３】
製造例３
製造例１と同様のフリーデルクラフツ反応にて得られた、ヒドロキシル基含有炭化水素［スチレン７モルと、３−イソプロペニル−α，α−ジメチルベンジルイソシアネートのエタノールブロック物２モルを４−α−クミルフェノール１モルに付加したものにＥＯを付加したもの（ＥＯ含量１０％）；数平均分子量２，０００］３２．１部、ポリエチレングリコール（数平均分子量３，０００）６１．６部およびＩＰＤＩ６．８部を８０℃で３時間反応させ、オキシエチレン単位含量６０重量％、重量平均分子量１５，０００の反応性界面活性剤［Ｂ−３］１００部を得た。
【０１１４】
製造例４
製造例１と同様のフリーデルクラフツ反応にて得られた、ヒドロキシル基含有炭化水素［スチレン５モルと、スチレン−ｐ−グリシジルエーテル１モルをフェノール１モルに付加したものにＥＯを付加したもの（ＥＯ含量４０％）；数平均分子量１，０００］１０．５部、ポリエチレングリコール（数平均分子量９，０００）８７．１部およびＨＤＩ２．３部を８０℃で３時間反応させ、オキシエチレン単位含量８０重量％、重量平均分子量３１，０００の反応性界面活性剤［Ｂ−４］１００部を得た。
【０１１５】
製造例５
製造例１と同様のフリーデルクラフツ反応にて得られた、ヒドロキシル基含有炭化水素［スチレン３モルと、３−イソプロペニル−α，α−ジメチルベンジルイソシアネート３モル、及び２，３−ジグリシジルオキシスチレンを４−α−クミルフェノール１モルに付加したものにＥＯを付加したもの（ＥＯ含量５％）；数平均分子量１，３００］２９．４部、ポリエチレングリコール（数平均分子量３，０００）６５．１部およびＨＤＩ５．５部を８０℃で３時間反応させ、オキシエチレン単位含量２６重量％、重量平均分子量１２，０００の反応性界面活性剤［Ｂ−５］１００部を得た。
【０１１６】
製造例６
製造例１と同様のフリーデルクラフツ反応にて得られた、ヒドロキシル基含有炭化水素［スチレン５モルと３−イソプロペニル−α，α−ジメチルベンジルイソシアネートのエタノールブロック物２モルを４−α−クミルフェノール１モルに付加したものにＰＯを付加したもの（ＰＯ含量１５％）；数平均分子量３，２００］８６．４部に無水硫酸１３．６部を発熱が無いように少量ずつ添加し、８０℃で３時間反応させた後、水酸化ナトリウムで中和して、親水基含量１６重量％、重量平均分子量８，０００の反応性界面活性剤［Ｂ−６］１００部を得た。
【０１１７】
製造例７
製造例１と同様のフリーデルクラフツ反応にて得られた、ヒドロキシル基含有炭化水素［３−イソプロペニル−α，α−ジメチルベンジルイソシアネートのメチルエチルケトンオキシムブロック物７モルをフェノール１モルに付加したものにＥＯを付加したもの（ＥＯ含量１０％）；数平均分子量１，８００］５２．６部に氷酢酸６５部、重クロム酸ナトリウム２水和物５２．６部を１５℃で５時間反応させてカルボン酸とし、アミノエチルエタノールアミン４４部と２３０℃で１２時間反応させ、親水基含量２７重量％、重量平均分子量５，８００の反応性界面活性剤［Ｂ−７］１００部を得た。
【０１１８】
製造例８
製造例１と同様のフリーデルクラフツ反応にて得られた、ヒドロキシル基含有炭化水素［スチレン５モルと３−イソプロペニル−α，α−ジメチルベンジルイソシアネートのエタノールブロック物２モルをフェノール１モルに付加したものにＰＯを付加したもの（ＰＯ含量１５％）；数平均分子量７，２００］５１．４部に、水酸化カリウム０．５部存在下、アクリロニトリル１５．２部を６０℃で１時間滴下後、メタノール３００部中、８０℃でコバルト０．２部、水素ガスを用いて６時間反応させ、アミノ基含有炭化水素（Ｂ０−６）６６．４部を得た。（Ｂ０−６）と水酸化ナトリウム１０．６部、メチルクロライド２４．５部を１５０℃で６時間反応させ３級アンモニウム化した後、モノクロル酢酸ナトリウムの３０％水溶液７３．６部を７０℃で５時間反応させ、親水基含量２１重量％、重量平均分子量８，０００の反応性界面活性剤［Ｂ−８］１００部を得た。
【０１１９】
比較製造例１
ポリオキシアルキレンモノオール［スチレン７モル付加４−α−クミルフェノールにエチレンオキサイドを付加したもの（ＥＯ含量６０％）；数平均分子量１，５００］１９．３部、ポリエチレングリコール（数平均分子量６，０００）７７．４部およびＨＤＩ３．３部を８０℃で３時間反応させ、親水基含量７７重量％、重量平均分子量１８，０００の界面活性剤［Ｂ’−９］１００部を得た。
【０１２０】
アクリル系ヒドロキシ官能性樹脂の調製
キシレンの２５０部を反応器に入れ、加熱して１００℃とし、ついで、次に示されるような割合の混合物を約３時間滴下した。その間の反応は、窒素雰囲気下にて行った。この滴下終了後、２時間のあいだ、１００℃に保持して、反応を続行した。
（１） スチレン ２３ 部
（２） メチルメタクリレート ２３ 部
（３） アクリル酸ブチル ２０ 部
（４） アクリル酸ヒドロキシエチル ３３ 部
（５） パーオキシＤ（日本油脂製、過酸化物） １ 部
反応終了後、減圧蒸留によって有機溶剤および残存モノマーを除去し、その後、真空乾燥させることにより、水酸基当量４２０、重量平均分子量３０，０００のアクリル系ヒドロキシ官能性樹脂［アクリル樹脂１］を得た。
上記で得られた［アクリル樹脂１］５９部とＭＥＫオキシムブロックされたＨＤＩイソシアヌレート（旭化成製、ジュラネート）４１部を１００℃で加熱ニーダーを用いて混練後、５μｍ程度に粉砕し、平均粒径７μｍ、長径／短径比１．２の［アクリル樹脂２］を得た。
【０１２１】
ポリエステル系樹脂の調製
反応器にネオペンチルグリコール２００部、エチレングリコール９３部、テレフタル酸３５５部を投入し、２３０℃に加熱し生成する水を留去しながら２時間反応を進めた。その後０．２部のジブチルチンオキサイドを添加し、酸価が０．５以下になるまで反応を続けることで、本発明の塗膜に用いる、両末端に水酸基を有する、重量平均分子量１４，０００、水酸基価１６．５ｍｇＫＯＨ／ｇのポリエステル樹脂［ポリエステル樹脂１］を得た。
上記で得られた［ポリエステル樹脂１］９３部とＭＥＫオキシムブロックされたＨＤＩイソシアヌレート（旭化成製、ジュラネート）７部を１００℃で加熱ニーダーを用いて混練後、５μｍ程度に粉砕し、平均粒径７μｍ、長径／短径比１．２の［ポリエステル樹脂２］を得た。
【０１２２】
分散液の調製例
製造例１〜８により得られた反応性界面活性剤［Ｂ−１］〜［Ｂ−８］、および比較製造例１で得られた界面活性剤［Ｂ’−９］、低分子量界面活性剤［Ｂ’−１０］（オクチルフェノールのＥＯ付加物、数平均分子量１，０００）、ＰＶＡ［Ｂ’−１１］（部分ケン化ポリビニルアルコール、重合度１，７００、ケン化度８８％）のそれぞれ３部を水１００部に分散し、分散液を得た。これを［分散液１］〜［分散液１１］とする。
【０１２３】
実施例１〜８、比較例１〜３
ビーカー内に、［アクリル樹脂１］５９部、ＭＥＫオキシムブロックされたＨＤＩイソシアヌレート（旭化成製、ジュラネート）４１部、およびテトラヒドロフラン１００部を混合しておき、これを［分散液１］〜［分散液１１］１００部に添加した後、ウルトラディスパーサー（ヤマト科学製）を使用して、回転数９，０００ｒｐｍで１分間混合し、平均粒径を５μｍとした。混合後、攪拌棒および温度計をセットした４つ口フラスコにこの混合液を投入し、２５℃、減圧下で１０時間脱溶剤した。次いでウレタン化触媒（「ＴＥＤＡ」、東ソー製）０．１部、耐光安定剤（「ＤＩＣ−ＴＢＳ」、大日本インキ化学工業製）０．１部、粘弾性付与剤（「ＳＮシックナー−６５１」、サンノプコ社製）３．０部を加え、表１に示すような分散粒子の平均粒径、長径／短径比及び粘度を有するスラリー塗料を得た。
【０１２４】
実施例９〜１６、比較例４〜６
分散液の調製例により得られた［分散液１］〜［分散液１１］１００部中に、上記で得られた、アクリル系ヒドロキシ官能性樹脂微粉の［アクリル樹脂２］１００部を加え、ウルトラディスパーサー（ヤマト科学製）を使用し、回転数９，０００ｒｐｍで１分間混合した。次いでウレタン化触媒（「ＴＥＤＡ」、東ソー製）０．１部、耐光安定剤（「ＤＩＣ−ＴＢＳ」、大日本インキ化学工業製）０．１部を加え、表２に示すような分散粒子の平均粒径、長径／短径比及び粘度を有するスラリー塗料を得た。
【０１２５】
実施例１７〜２４、比較例７〜９
ビーカー内に、［ポリエステル樹脂１］９３部、ＭＥＫオキシムブロックされたＨＤＩイソシアヌレート（旭化成製、ジュラネート）７部、およびテトラヒドロフラン１００部を混合しておき、これを［分散液１］〜［分散液１１］１００部に添加した後、ウルトラディスパーサー（ヤマト科学製）を使用して、回転数９，０００ｒｐｍで１分間混合し、平均粒径を５μｍとした。混合後、攪拌棒および温度計をセットした４つ口フラスコにこの混合液を投入し、２５℃、減圧下で１０時間脱溶剤した。次いでウレタン化触媒（「ＴＥＤＡ」、東ソー製）０．１部、耐光安定剤（「ＤＩＣ−ＴＢＳ」、大日本インキ化学工業製）０．１部、粘弾性付与剤（「ＳＮシックナー−６５１」、サンノプコ社製）３．０部を加え、表３に示すような分散粒子の平均粒径、長径／短径比及び粘度を有するスラリー塗料を得た。
【０１２６】
実施例２５〜３２、比較例１０〜１２
分散液の調製例により得られた［分散液１］〜［分散液１１］１００部中に、上記で得られた、ポリエステル系ヒドロキシ官能性樹脂微粉の［ポリエステル樹脂２］１００部を加え、ウルトラディスパーサー（ヤマト科学製）を使用し、回転数９，０００ｒｐｍで１分間混合した。次いでウレタン化触媒（「ＴＥＤＡ」、東ソー製）０．１部、耐光安定剤（「ＤＩＣ−ＴＢＳ」、大日本インキ化学工業製）０．１部を加え、表４に示すような分散粒子の平均粒径、長径／短径比及び粘度を有するスラリー塗料を得た。
【０１２７】
上記方法で得られた各スラリー塗料について、下記試験方法により評価を行った。その結果を表１、表２、表３および表４に示す。
【０１２８】
（試験片の作成）
得られたスラリー塗料をリン酸亜鉛処理鋼板にスプレー塗布し、６０℃で１０分間前焼付けした後、１６０℃で１０分間焼付け乾燥して、膜厚０．０３ｍｍの塗膜を得た。
（試験方法）
耐水性評価：上記で得られた塗膜を水に８０℃で１２０時間浸漬後、２０℃で３時間徐冷し、表面を布で拭き取った後、外観を観察した。
○：浸漬前外観との変化なし
×：しわ、割れ、ふくれ、はがれ等の外観不良が発生
溶出率の測定：上記で得られた塗膜を水に２５℃で１時間浸漬し、水浸後のフィルムを６０℃で１時間乾燥し、漬浸前のフィルムの重量と比較して、重量減少率を測定し溶出率とした。
塗膜強度の測定：上記で得られた塗膜を、フィッシャー硬度計（フィッシュアー・インストルメンツ製フィッシャースコープＨ１００Ｖ）で表面硬さを測定した。（加重０．４〜１００ｍＮ、押し込み深さ５μｍ）この試験方法は塗料の皮膜硬さを高精度で数値化できるうえ、一回の試験で押し込み硬さ、ヤング率等、多くの塗膜強度の要素を評価できるものである。この表面硬さを測定することにより塗膜強度を評価することができる。
分散性の評価：得られたスラリー塗料を遠心分離器にて、６，０００ｒｐｍで１５分間遠心分離し、分散樹脂の沈降状態を目視判定した。
○：遠心分離前後で、分散体外観がほぼ同じである
△：遠心分離により、一部の分散体が沈降
×：遠心分離により、分散体が完全に沈降
【０１２９】
【表１】

【０１３０】
【表２】

【０１３１】
【表３】

【０１３２】
【表４】

【０１３３】
【発明の効果】
本発明の水分散粉体スラリー塗料は、分子内にイソシアネート基、ブロック化されたイソシアネート基及びエポキシ基からなる群より選ばれる少なくとも１種の基を含有しているため、活性水素基を含有する樹脂を分散している場合、優れた塗膜強度を示すと共に、硬化された塗膜の耐水性等の塗膜物性に優れている。また、塗料保存時には、樹脂の分散安定性が優れている。
上記効果を奏することから本発明の水分散粉体スラリー塗料は、例えば、自動車、建築物、産業機械等の塗料用にきわめて有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a powder slurry coating composition. More specifically, the present invention relates to a powder slurry coating composition excellent in dispersibility of a resin dispersed in water and strength of a cured coating film after baking.
[0002]
[Prior art]
Powder slurry paints have a form in which resin microparticles are dispersed in water.When used, surface active agents are used to suppress coalescence and sedimentation of particles and to stably disperse resin microparticles in water. An agent is used (for example, see Patent Document 1).
[0003]
[Patent Document 1]
JP 2001-220544 A
[0004]
[Problems to be solved by the invention]
However, when the powder slurry is actually used as a coating material using a surfactant, the surfactant remaining after evaporating and drying the aqueous medium deteriorates the water resistance of the coating film. In addition, these surfactants exert a plasticizing effect and deteriorate the strength of the coating film. An object of the present invention is to provide a powder slurry coating which has the above-mentioned problems and is excellent in water resistance and coating strength.
[0005]
[Means for Solving the Problems]
The present inventors have intensively studied to solve the above problems, and as a result, have reached the present invention. That is, the present invention provides, in an aqueous medium, fine particles (A) composed of a resin (a1) having active hydrogen and a reactive surfactant (B) having an isocyanate group and / or an epoxy group which may be blocked. ) Is a water-dispersed powder slurry paint.
The present invention is also a coating film obtained by applying and baking the above water-dispersed powder slurry coating.
Hereinafter, the present invention will be described in detail.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
The reactive surfactant (B) in the present invention comprises a hydrophobic part and a hydrophilic part, and preferably has an isocyanate group and / or an epoxy group which may be blocked in the hydrophobic part. As the hydrophobic part, those having an aromatic ring-containing hydrocarbon group having 6 to 100 carbon atoms and an optionally blocked isocyanate group and / or epoxy group are preferable. The hydrophilic part is preferably at least one group selected from the group consisting of an oxyethylene unit, an anionic group, a cationic group, and a zwitterionic group.
Hereinafter, a reactive surfactant (B) having an oxyethylene unit as the hydrophilic part is selected from the reactive surfactant (B1) in the present invention, and an anionic group, a cationic group, and a zwitterionic group as the hydrophilic part. (B) having at least one group selected from the group consisting of a reactive surfactant (B2), an anionic group, a cationic group, and (B1) having at least one group selected from the group of zwitterionic groups in the present invention. This is referred to as the reactive surfactant (B3) in the present invention.
[0007]
The reactive surfactant (B) converts the optionally blocked isocyanate group and / or epoxy group into a reactive interface from the viewpoint of the water resistance of the film obtained from the aqueous dispersion obtained by using the reactive surfactant. Activator (B) contains preferably 1 to 20, more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 5, molecules per molecule.
[0008]
The hydrophilic part of the reactive surfactant (B) contains one or more hydrophilic groups of an oxyethylene unit [polyoxyethylene group or the like], an anionic group, a cationic group, and a zwitterionic group. Is preferred.
[0009]
When the hydrophilic group is particularly an oxyethylene unit, the oxyethylene unit is preferably at least 20% by weight, more preferably at least 30% by weight, particularly preferably at least 50% by weight, based on the weight of the reactive surfactant (B). % By weight, preferably 90% by weight or less, more preferably 85% by weight or less, particularly preferably 80% by weight or less. When the oxyethylene unit is at least 20% by weight and at most 90% by weight, a stable slurry coating can be obtained with strong emulsifying power.
[0010]
The reactive surfactant (B) in the present invention contains one or more kinds of hydrophobic parts. As the hydrophobic portion, for example, a hydrocarbon group having 6 to 100 or more carbon atoms, preferably 8 to 80 carbon atoms and having an aromatic ring, in the molecule, an isocyanate group which may be blocked and / or epoxy And those containing a group. Examples of the hydrocarbon group having an aromatic ring include styrenated phenyl groups, residues of bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.) excluding the hydroxyl group, and those obtained by adding a vinyl monomer to these compounds. And the like.
The hydrophobic portion may also be a hydrophobic oxyalkylene unit other than the oxyethylene unit, for example, an oxypropylene unit, an oxytetramethylene unit, or the like.
[0011]
The method for introducing these optionally blocked isocyanate groups and / or epoxy groups contained in the hydrophobic portion is not particularly limited, but, for example, an optionally blocked isocyanate monomer having a double bond There is a method of subjecting (b2) and / or a vinyl monomer having an epoxy group (b2 ′) to addition polymerization with another unsaturated monomer.
[0012]
Specific examples of the isocyanate compound having a double bond include, for example, isocyanate ethyl (meth) acrylate, isocyanate propyl (meth) acrylate, isocyanate butyl (meth) acrylate, isocyanate hexyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 3-ethylenyl-α, α-dimethylbenzyl isocyanate, and mixtures of two or more of the above.
Of these, preferred are 3-isopropenyl-α, α-dimethylbenzyl isocyanate and 3-ethylenyl-α, α-dimethylbenzyl isocyanate.
[0013]
Examples of the isocyanate group blocking agent include lactams (such as ε-caprolactam, δ-valerolactam, and γ-butyrolactam), phenols (such as phenol, cresol, ethylphenol, butylphenol, nonylphenol, and dinonylphenol), and oximes. (Methyl ethyl ketone oxime, acetophenone oxime, benzophenone oxime, etc.), alcohols (methanol, ethanol, butanol cyclohexanol, etc.), diketones (dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc.), mercaptans (Butyl mercaptan, dodecyl mercaptan, etc.), uretdiones (isophorone diisocyanate dimer, hexamethylene diisocyanate dimer, etc.), Bromide compound (acetanilide, acetamide, etc.), imides (succinimide, maleimide, etc.) and sulfites (sodium bisulfite, etc.), and mixtures of two or more of the above.
Of these, alcohols, lactams, oximes, and phenols are preferred, and methanol, ethanol, and methyl ethyl ketone oxime are particularly preferred.
[0014]
The above-mentioned vinyl monomer having an epoxy group (b2 ′) is not particularly limited as long as it is various known compounds containing an epoxy group and a polymerizable vinyl group in a molecule. For example, unsaturated carboxylic acid glycidyl ester ((meth) ) Glycidyl acrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4 , 5-epoxypentyl, 6,7-epoxyheptyl (meth) acrylate, 6,7-epoxyheptyl α-ethylacrylate, methyl glycidyl (meth) acrylate, and the like, and unsaturated glycidyl ether (styrene- p-glycidyl ether, 2,3-diglycidyloxystyrene, 4-vinyl-1-cyclohexane Sen-1,2-epoxide, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 2,3-dihydroxymethyl Styrene diglycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether, 2 1,3,4-trihydroxymethylstyrene triglycidyl ether, 1,3,5-trihydroxymethylstyrene triglycidyl ether, 5-vinylpyrogallol triglycidyl ether, 4-vinylpyrogallol triglycidyl ether And vinyl phlorogrisinol triglycidyl ether).
[0015]
The other unsaturated monomer is not particularly limited, and an aliphatic vinyl-based hydrocarbon, an alicyclic vinyl-based hydrocarbon, and an aromatic vinyl-based hydrocarbon can be used.
Examples of the aliphatic vinyl hydrocarbon include ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 7-octadiene, α-olefins other than the above, and the like; alicyclic vinyl hydrocarbons such as cyclohexene, (di) cyclopentadiene, pinene, limonene, indene, vinylcyclohexene, ethylidene bicycloheptene; Examples of aromatic vinyl hydrocarbons include styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, and chlorostyrene. Examples include butylbenzene, vinylnaphthalene, divinylbenzene, divinyltoluene, divinylxylene, divinylketone, and trivinylbenzene.
[0016]
The nonionic reactive surfactant (B1) in the present invention preferably comprises, for example, a urethane resin (L) having an isocyanate group and / or an epoxy group which may be blocked. The urethane resin (L) is a vinyl monomer (b2) having an isocyanate group which may be blocked with a monohydric phenol or a monovalent aromatic alcohol (b1) and / or a vinyl monomer having an epoxy group (b2 ′). Or an alkylene oxide adduct thereof (b3), an organic diisocyanate (b4), and a diol and / or diamine (b5) having a polyoxyalkylene chain containing a polyoxyethylene unit. However, if necessary, an elongation agent (b10) and a terminator (b11) may be used.
[0017]
The weight average molecular weight of the reactive surfactant (B1) is preferably from 1,000 to 150,000, more preferably from 5,000 to 100,000, and particularly preferably from 10,000 to 25,000. The weight average molecular weight is preferably 1,000 or more from the viewpoint of obtaining sufficient surface activity, and is preferably 150,000 or less from the viewpoint of obtaining a low-viscosity and stable aqueous resin dispersion. The weight average molecular weight can be measured by a gel permeation chromatography (GPC) method. That is, a polymer solution is passed through a column filled with polystyrene gel or the like, and the polymer concentration and molecular weight of the eluate are detected as a function of the amount of elution.
[0018]
In the addition reaction with the monohydric phenol or the monohydric aromatic alcohol (b1), the vinyl monomer (b2) and / or the vinyl monomer having an epoxy group (b2 ′) and, if necessary, an isocyanate group and You may use the vinyl monomer (b9) which does not have both epoxy groups.
[0019]
The above-mentioned monohydric phenol or monovalent aromatic alcohol (b1) is not particularly restricted but includes, for example, phenol, alkyl (1 to 18 carbon atoms) phenol (for example, nonylphenol, dodecylphenol, octylphenol and the like), arylalkylated phenol ( For example, cumyl phenol, etc.), alkyl (C1-18) ethers of bisphenols (for example, monomethyl ether of bisphenol A, monobutyl ether of bisphenol A, monobutyl ether of bisphenol S, etc.), and a mixture of two or more of the above And the like.
Of these, phenol and cumylphenol are preferred.
Examples of the monovalent aromatic alcohol include benzyl alcohol, 2-biphenylethanol, and 4-biphenylethanol.
Of these, preferred is benzyl alcohol.
[0020]
Examples of the vinyl monomer (b2) include the isocyanate compounds having a double bond described above.
Of these, preferred are 3-isopropenyl-α, α-dimethylbenzyl isocyanate and 3-ethylenyl-α, α-dimethylbenzyl isocyanate.
[0021]
The vinyl monomer having an epoxy group (b2 ′) is not particularly limited as long as it is various known compounds containing an epoxy group and a polymerizable vinyl group in a molecule, and includes the above-described vinyl monomer having an epoxy group. Can be.
Of these, preferred are styrene-p-glycidyl ether and 2,3-diglycidyloxystyrene.
[0022]
The vinyl monomer (b9) having neither an isocyanate group nor an epoxy group used as required is not particularly limited, and examples thereof include the unsaturated monomers described above.
Of these, styrene is preferred.
[0023]
In the addition reaction product or the alkylene oxide adduct thereof (b3), the monohydric phenol or the monovalent aromatic alcohol (b1), the vinyl monomer (b2) and / or the vinyl monomer having an epoxy group (b2 ′), If necessary, the method of adding the vinyl monomer (b9) having neither the isocyanate group nor the epoxy group is not particularly limited, but the Friedel-Crafts reaction is preferred.
As a method of the Friedel-Crafts reaction, a known method can be used. For example, a vinyl monomer (b2) having an isocyanate group which may be blocked with a monohydric phenol or a monovalent aromatic alcohol (b1) and And / or a method of polyadding a vinyl monomer (b2 ′) having an epoxy group and, if necessary, a vinyl monomer (b9) using a known Lewis acid catalyst (eg, iron chloride, aluminum chloride, etc.). Can be
[0024]
In the present invention, the addition reaction product or the alkylene oxide adduct thereof (b3) may also include the above-mentioned monohydric phenol or monovalent aromatic alcohol (b1), the above-mentioned vinyl monomer (b2) and / or the above-mentioned vinyl having an epoxy group. The alkylene oxide may be further added to the addition reaction product obtained by adding the monomer (b2 ′) and, if necessary, the vinyl monomer (b9).
The alkylene oxide (hereinafter abbreviated as AO, having 1 to 30 carbon atoms) to be used is not particularly limited. Examples thereof include ethylene oxide (hereinafter, abbreviated as EO), propylene oxide (hereinafter, abbreviated as PO), and 1,2. -, 1,3- or 2,3-butylene oxide, tetrahydrofuran, α-olefin (C4-30) oxide, epichlorohydrin, styrene oxide, and a mixture of two or more of the above. Of these, EO is preferred. The mode of addition is preferably random and / or block.
The addition mole number of the alkylene oxide is preferably 1 to 30 mol, more preferably 1 to 10 mol, and still more preferably 1 to 5 mol.
[0025]
In the above-mentioned addition reaction product or its alkylene oxide adduct (b3), the above-mentioned monohydric phenol or monovalent aromatic alcohol (b1) which is a constitutional unit, the above-mentioned vinyl monomer (b2) and / or the above-mentioned vinyl monomer having an epoxy group The weight ratio of (b2 ′), the vinyl monomer (b9), and the added AO is preferably (1 to 5) / (1 to 20) / (0 to 20) / (0 to 50). Preferably it is (1-3) / (1-10) / (1-10) / (1-25).
[0026]
The organic diisocyanate (b4) is not particularly limited.
{Circle around (1)} Aliphatic diisocyanates having 2 to 18 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter) [for example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4 -Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6- Diisocyanatohexanoate, etc.];
(2) alicyclic diisocyanate having 4 to 15 carbon atoms [for example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) , Bis (2-isocyanatoethyl) -4-cyclohexene and the like];
(3) Aromatic diisocyanate having 6 to 14 carbon atoms [for example, 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4 ′ -Or 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4 '-Diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, etc.];
(4) C8-15 araliphatic diisocyanates [e.g., m- or p-xylylene diisocyanate (XDI), [alpha], [alpha], [alpha] ', [alpha]'-tetramethylxylylene diisocyanate (TMXDI), and the like];
(5) Modified products of these diisocyanates [eg, modified diisocyanates having a carbodiimide group, a uretdione group, a uretoimine group, a urea group, etc.];
(6) and mixtures of two or more of (1) to (5).
Preferred among these are HDI, TDI and IPDI.
[0027]
The diol and / or diamine (b5) having a polyoxyalkylene chain has a polyoxyethylene unit based on the weight of the diol and / or diamine (b5) from the viewpoint of the emulsifying power of the reactive surfactant (B). The content is preferably 20 to 100% by weight, more preferably 50 to 100% by weight, and particularly preferably 70 to 100% by weight.
Examples of the diol and / or diamine (b5) include polyether diols (b5-1) having terminal hydroxyl groups, polyester diols (b5-2) having terminal hydroxyl groups, and polyether diamines (b5-3) having terminal amino groups. And only a diol component, only a diamine component, or both a diol component and a diamine component can be used.
[0028]
As the polyether diol (b5-1), for example, a compound having a structure in which AO is added to a low molecular diol or a dihydric phenol, a mixture of two or more of these, and the like can be used.
[0029]
The low-molecular diol is not particularly limited. For example, ethylene glycol (hereinafter abbreviated as EG), diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol (hereinafter abbreviated as 14BG), 1,3-butanediol , Neopentyl glycol, 1,6-hexanediol; low molecular weight diols having a cyclic group [for example, those described in JP-B-45-1474, bis (hydroxymethyl) cyclohexane, bis (hydroxyethyl) benzene, bisphenol A Of ethylene oxide and the like, and mixtures of two or more of these.
[0030]
The dihydric phenol to which AO is to be added is not particularly limited, and for example, a dihydric phenol having 6 to 30 carbon atoms can be used. Specifically, monocyclic divalent, for example, catechol, resorcinol, hydroquinone and the like; condensed ring divalent, for example, dihydroxynaphthalene and the like; bisphenol, for example, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxydiphenylthioether and the like; And binaphthol; and alkyl (C 1-10) or halogen (chlorine, bromine, etc.) substituted products thereof (for example, brominated bisphenol A).
[0031]
Examples of the polyester diol (b5-2) include, among the condensed polyester diols obtained by reacting the polyether diol (b5-1) having a number average molecular weight of 1,000 or less with a dicarboxylic acid and / or a low molecular diol, Examples include those containing a polyoxyethylene unit as described above.
[0032]
Examples of the low molecular diol include those described above.
Examples of the dicarboxylic acids include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), and ester-forming properties of these dicarboxylic acids. Derivatives [acid anhydrides, lower alkyl (C1-4) esters, etc.], and mixtures of two or more of these.
[0033]
As the polyether diamine (b5-3), those obtained by further modifying the terminal hydroxyl group of the polyether diol (b5-1) to an amino group can be used.
A known method can be used to modify the terminal hydroxyl group to an amino group. For example, the terminal cyanoalkyl group obtained by cyanoalkylating the terminal hydroxyl group of the polyether diol (b5-1) can be reduced to obtain an amino group. A method of alkylating (for example, a method of reacting the above-mentioned polyether diol (b5-1) having a terminal hydroxyl group with acrylonitrile or nonennitrile and hydrogenating the resulting cyanoethylated product) is exemplified.
Among these, a preferred method is a method of reducing the terminal cyanoalkyl group obtained by cyanoalkylating the terminal hydroxyl group of the polyether diol (b5-1) and aminoalkylating the same.
[0034]
The number average molecular weight per hydroxyl group and / or amino group of the diol and / or diamine (b5) is preferably from 100 to 10,000 or more, more preferably from 400 to 4,000.
[0035]
Examples of the elongating agent (b10) used as needed include water; the low-molecular diol described above; diamines [aliphatic diamines having 2 to 6 carbon atoms (eg, ethylenediamine, 1,2-propylenediamine, etc.) ), An alicyclic diamine having 6 to 15 carbon atoms (eg, isophoronediamine, 4,4′-diaminodicyclohexylmethane, etc.), an aromatic diamine having 6 to 15 carbon atoms (eg, 4,4′-diaminodiphenylmethane, etc.)] Monoalkanolamine (eg, monoethanolamine), hydrazine or a derivative thereof (eg, adipic acid dihydrazide), and a mixture of two or more thereof. Of these, preferred are low molecular weight diols, and particularly preferred are EG and 14BG.
[0036]
The terminator (b11) is not particularly limited, and includes, for example, monohydric aliphatic alcohol (b11-1), aliphatic monoamine (b11-2) and the like.
Examples of the alcohol (b11-1) include saturated aliphatic monohydric alcohols having 1 to 18 carbon atoms (ethyl alcohol, propyl alcohol, butyl alcohol, octyl alcohol, lauryl alcohol, 2-octyl alcohol, 2-ethylhexyl alcohol, and the like). ) And unsaturated monohydric aliphatic alcohols having 1 to 18 carbon atoms (such as oleyl alcohol).
[0037]
Examples of the monoamine (b11-2) include aliphatic monoamines having 1 to 18 carbon atoms [octylamine, 2-ethylhexylamine, dodecylamine, dibutylamine, dioctylamine, di (2-ethylhexyl) amine, etc.], carbon Examples thereof include an unsaturated aliphatic monoamine having 1 to 18 carbon atoms (eg, oleylamine) and a hydroxyalkyl group-containing monoamine having 1 to 16 carbon atoms (eg, monoethanolamine and diethanolamine).
Of these, preferred are monohydric aliphatic alcohols and aliphatic monoamines, and particularly preferred are monohydric aliphatic alcohols.
[0038]
In the present invention, as the urethane resin (L), a compound represented by the following general formula (1) is preferable.
[0039]
Embedded image

[0040]
In the formula, Q is a monovalent phenol or a monovalent aromatic alcohol (b1) and a vinyl monomer (b2) having an optionally blocked isocyanate group and / or a vinyl monomer (b2 ′) having an epoxy group. G is a residue of the polyoxyalkylene ether (b3), G is a residue of an organic diisocyanate (b4) optionally having a urea bond, X is O or NH, and J is Z represents hydrogen, a group represented by -COO-Q, or -CO-Y (Y represents a residue of a diol and / or a diamine (b5) having a polyoxyalkylene chain containing a polyoxyethylene unit. , -OR¹(R¹: A residue of a monohydric alcohol having 1 to 18 carbon atoms) or -NR²R³(R²: A hydrocarbon group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 16 carbon atoms, R³: Hydrogen, a hydrocarbon group having 1 to 18 carbon atoms or a hydroxyalkyl group having 1 to 16 carbon atoms). m is an integer of 1 to 500.
[0041]
In the present invention, the method for producing the urethane resin (L) is not particularly limited, and the adduct or its polyoxyalkylene ether (b3) to diol may be produced by a usual method for producing a polyurethane resin (one-shot method or multi-stage method). And / or a diamine (b5), and if necessary, the elongating agent (b10) and the terminating agent (b11) by a urethanization reaction. The reaction temperature for urethanization is preferably 30 to 200 ° C, more preferably 50 to 180 ° C. The reaction time is preferably 0.1 to 30 hours, more preferably 0.1 to 8 hours.
The urethanization reaction is preferably carried out in a solventless system or an organic solvent inert to isocyanate. Examples of the organic solvent include acetone, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, toluene, dioxane and the like. The organic solvent is preferably removed by a distillation method or the like after forming the urethane resin (L).
[0042]
In the urethanization reaction, a hydroxyl (OH) group and an amino group (NH₂) And the equivalent ratio of isocyanate (NCO) groups of the organic diisocyanate (b4) [(OH + NH₂) / NCO ratio] is preferably 1: (0.8 to 1.5), more preferably 1: (0.9 to 1.3). When the equivalent ratio of the NCO groups is 0.8 to 1.5, the obtained polyurethane resin has an appropriate molecular weight, and the water resistance of the film formed from the obtained aqueous resin dispersion is improved.
[0043]
In the reactive surfactant (B2) of the present invention having an anion, a cation, or an amphoteric ion, the hydrophilic group is not particularly limited. For example, a carboxylate group (—COO) as long as it is an anionic group⁻X⁺), Sulfonate groups (—SO₃ ⁻X⁺), Groups of sulfate salts (-OSO₃ ⁻X⁺), A group of a phosphate salt (—OPO)₃H⁻X⁺, -OPO₃ ^2-・ 2X⁺), Etc. (X is, for example, a sodium, potassium, ammonium, alkanolamine salt, etc.), and if it is a cationic group, a primary amine salt group, a secondary amine salt group, a tertiary amine salt And a group of a quaternary ammonium salt, and a zwitterionic group include a hydrophilic group such as a betaine group.
[0044]
The content of the hydrophilic group is preferably at least 0.1% by weight, more preferably at least 1% by weight, particularly preferably at least 5% by weight, and preferably at least 50% by weight, based on the weight of the reactive surfactant (B2). % By weight, more preferably 20% by weight or less, particularly preferably 10% by weight or less. When the content of the hydrophilic group is 0.1% by weight or more and 50% by weight or less, emulsifying power is strong and a stable slurry coating can be obtained.
[0045]
The reactive surfactant (B2) preferably has a weight average molecular weight of 300 to 100,000, more preferably 800 to 50,000, and particularly preferably 1,000 to 8,000. The weight average molecular weight is preferably 300 or more from the viewpoint of obtaining sufficient surface activity, and is preferably 100,000 or less from the viewpoint of obtaining a low-viscosity and stable aqueous resin dispersion.
[0046]
The reactive surfactant (B2) in the present invention is preferably, for example, a monovalent phenol or a monovalent aromatic alcohol (b1) and a vinyl monomer (b2) having an isocyanate group which may be blocked, and / or Or a residue of an addition reaction product comprising a vinyl monomer having an epoxy group (b2 ′) or a residue (b3 ′) of an alkylene oxide adduct thereof, and an anion group, a cationic group, and a zwitterionic group. At least one type of ionic group is a main component.
[0047]
At least one ionic group selected from the group consisting of an anionic group, a cationic group, and a zwitterionic group may be added to any site in the residue (b3 ′). It can be added to a hydroxyl group introduced by phenol or a monovalent aromatic alcohol (b1), or to a hydroxyl group introduced by adding an alkylene oxide to this hydroxyl group.
[0048]
In the present invention, the method for producing the reactive surfactant (B2) is not particularly limited. For example, the above-mentioned adduct or the terminal hydroxyl group of the polyoxyalkylene ether (b3) is anionized (B2-1), It is obtained by cationization (B2-2) and amphoteric ionization (B2-3).
[0049]
Examples of the method of the anionization (B2-1) include, for example, the esterification of the above-mentioned adduct or the terminal hydroxyl group of the polyoxyalkylene ether (b3) with sulfuric anhydride, chlorosulfonic acid, etc., phosphoric anhydride, etc. And the like. The reaction temperature is preferably from 20C to 200C, more preferably from 20C to 100C. The reaction time is preferably 0.1 to 30 hours, more preferably 0.1 to 10 hours.
[0050]
Examples of the method of cationization (B2-2) include neutralization of the aminated adduct or the polyoxyalkylene ether (b3) terminal thereof with an acid, quaternization with an alkylating agent, and the like. Can be The acid used for the neutralization is not particularly limited, and examples thereof include hydrochloric acid and acetic acid. Examples of the alkylating agent used for quaternization include methyl chloride, methyl bromide, benzyl chloride, long-chain alkyl chloride, epichlorohydrin, dimethyl sulfate, and ethylene oxide. As a method for aminating the terminal, for example, acrylonitrile is added dropwise to the hydroxyl group of the above-mentioned adduct or its polyoxyalkylene ether (b3) at 10 to 80 ° C. in the presence of an alkali catalyst such as potassium hydroxide. After that, the used alkali catalyst is removed, and the solvent is removed under a high pressure (for example, 30 to 100 kg / cm) in a solvent such as methanol.²), Hydrogenation using a catalyst such as nickel or cobalt, and the like.
The reaction temperature of the neutralization reaction is preferably 20 to 150C, more preferably 20 to 100C. The reaction time is preferably 0.1 to 20 hours, more preferably 0.1 to 6 hours.
The reaction temperature with the alkylating agent is preferably 50 to 300 ° C, more preferably 80 to 150 ° C. The reaction time is preferably 0.1 to 20 hours, more preferably 0.1 to 12 hours.
[0051]
Examples of the method of the amphoteric ionization (B2-3) include, for example, after the terminal amino group of the adduct or its polyoxyalkylene ether (b3) is tertiary-terminated with the alkylating agent, and then an aqueous solution of sodium monochloroacetate is used. And a method of adding a vinyl group-containing ester or a vinyl group-containing nitrile, followed by saponification with an alkali. Examples of the vinyl group-containing ester include methyl acrylate and acrylonitrile.
[0052]
A nonionic reactive surfactant (B1) having a terminal OH and having at least one group selected from the group consisting of an anionic group, a cationic group, and a zwitterionic group can be used as the above-mentioned reaction in the present invention. It becomes a surfactant (B3). The production can be carried out according to the method for producing the above-mentioned reactive surfactant (B2).
[0053]
In the reactive surfactant (B3) of the present invention, the content of the anionic group, the cationic group, or the zwitterionic group is preferably 0.1% by weight or more based on the weight of the reactive surfactant (B3). It is more preferably at least 1% by weight, particularly preferably at least 5% by weight, preferably at most 50% by weight, more preferably at most 20% by weight, particularly preferably at most 10% by weight. When the content of the hydrophilic group is 0.1% by weight or more and 50% by weight or less, emulsifying power is strong and a stable slurry coating can be obtained.
[0054]
The reactive surfactant (B3) preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 4,000 to 20,000. The weight average molecular weight is preferably 1,000 or more from the viewpoint of obtaining sufficient surface activity, and is preferably 100,000 or less from the viewpoint of obtaining a low-viscosity and stable aqueous resin dispersion.
[0055]
In the present invention, the HLB of the reactive surfactant (B) is 5 to 40 from the viewpoint of emulsifying the ethylenically unsaturated monomer and dispersing the resin fine particles into a stable aqueous dispersion or aqueous emulsion. Is preferable, and 5-20 are more preferable. The HLB of the reactive surfactant (B) is adjusted, for example, by adjusting the type and content of the hydrophobic group and adjusting the type and content of the hydrophilic group in the reactive surfactant (B). be able to. The HLB can be determined, for example, by the method of Oda described in Takehiko Fujimoto, “Introduction to a New Edition of Surfactants,” Sanyo Chemical Industries, Ltd., p.197, 1992. That is, the numerical values of the inorganic (hydrophilic) or organic (hydrophobic) of each functional group are evaluated based on the number of carbon atoms, and the numerical values of the organic and inorganic properties (for example, the numerical values of the third and the fourth literatures in the above document) Using the type of hydrophobic group and its content and the type and content of hydrophilic group in the reactive surfactant (B), the organic value and The inorganic value is determined, and the HLB is calculated by the following equation.
HLB = 10 × (inorganic / organic)
[0056]
In the slurry coating of the present invention, the fine particles (A) are preferably made of a resin (a1) containing active hydrogen, and preferably further contain a curing agent (a2). It is preferable that the resin (a1) and the curing agent (a2) are mixed, for example, by being dissolved in an organic solvent or melt-kneaded.
The fine particles (A) are prepared, for example, by dispersing a solvent solution of the resin (a1), and preferably the curing agent (a2) in water, and removing the solvent, or by mixing the resin (a1) with the resin (a1). Further, it is obtained by a method of pulverizing a material obtained by melt-kneading the curing agent (a2). As will be described later, a resin (a1) and preferably a curing agent (a2) dissolved in a solvent are dispersed in an aqueous medium containing the reactive surfactant (B), and the solvent is removed. By doing so, it can be manufactured at the time of manufacturing the slurry paint.
In the slurry coating of the present invention, the particle shape of the fine particles (A) may be irregular or spherical, but the spherical shape is preferable in terms of the smoothness and uniformity of the coating film. Here, the term “spherical” refers to particles having a ratio of the major axis / minor axis of the particles in the range of 1.0 to 1.5.
The average particle size of the fine particles (A) in the slurry coating of the present invention is preferably 0.1 to 50 μm, more preferably 0.5 to 20 μm, and still more preferably 1.0 to 10 μm. The particle size may be measured by an electron microscope, a sedimentation method, an electrozone method, a dynamic light scattering method, or the like, but the measurement by the dynamic light scattering method is preferred from the viewpoint of suitability of the measured particle size range.
[0057]
The fine particles (A) are spherical with an average ratio of major axis / minor axis of 1.0 to 1.5, preferably 1.0 to 1.2. The major axis / minor axis ratio is determined by observing the particles using an optical microscope, and defining the shortest distance between two parallel lines that are in contact with the contour in the plane view of the particles according to the definition of Heywood as the minor axis, and the maximum distance between the parallel lines perpendicular to the outline. The length is defined as the major axis, and the ratio of the major axis to the minor axis measured is calculated and obtained.
[0058]
Examples of the organic solvent that dissolves the resin (a1) containing active hydrogen include an aromatic hydrocarbon solvent, an aliphatic or alicyclic hydrocarbon solvent, a halogen solvent, an ester or ester ether solvent, Examples include ether solvents, ketone solvents, alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic compound solvents, and mixed solvents of two or more of these. Of these, ether solvents, ester ether solvents and aromatic hydrocarbon solvents are preferred.
[0059]
Examples of the aromatic hydrocarbon solvent include toluene, xylene, ethylbenzene, tetralin and the like.
Examples of the aliphatic or alicyclic hydrocarbon solvent include n-hexane, n-heptane, mineral spirit, cyclohexane and the like.
Examples of the halogen-based solvent include methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, and the like.
Examples of the ester solvent include ethyl acetate, butyl acetate and the like.
Examples of the ester ether solvent include methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and the like.
Examples of the ether-based solvent include diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone.
Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, and benzyl alcohol.
Examples of the amide solvent include dimethylformamide, dimethylacetamide and the like.
Examples of the sulfoxide-based solvent include dimethyl sulfoxide.
Examples of the heterocyclic compound-based solvent include N-methylpyrrolidone.
[0060]
In the present invention, the resin (a1) containing active hydrogen [alcoholic hydroxyl group, phenolic hydroxyl group, amino group, carboxylic acid group, phosphoric acid group, thiol group, etc.] is, for example, an acrylic resin (a1１1); Examples thereof include polyester resins (a1-2), polyurethane resins (a1-3), and epoxy resins (a1-4), which contain active hydrogen groups.
When the reactive surfactant (B) has an isocyanate group which may be blocked, the reactive surfactant (B) is preferably used for any of the above resins having active hydrogen. Acrylic resin (a1) is preferred.
When the reactive surfactant (B) has an epoxy group, the reactive surfactant (B) is preferably used for a resin having an active hydrogen of an alcoholic hydroxyl group, a carboxylic acid group, an amino group, and a thiol group. Particularly, an acrylic resin (a1-1) having an active hydrogen of an alcoholic hydroxyl group or a carboxylic acid group is preferable.
The active hydrogen equivalent of the resin (a1) is preferably 50 to 50,000, more preferably 100 to 10,000, and still more preferably 200 to 5,000.
[0061]
The monomers constituting the acrylic resin (a1-1) include (i) [(meth) acrylic acid or (meth) acrylate having a hydroxyl group] (a1-1) 1), and (ii) [hydroxyl group]. (Meth) acrylic acid ester, acrylamide, acrylonitrile) having no (a1-1) 2), and (iii) other monomer (a1-1-3) if necessary.
The weight percent ratio of the monomer (a1-1), the monomer (a1-2) and the monomer (a1-3) in the acrylic resin (a1-1) is preferably (1-100) / (0-80) / (0-50), and more preferably (1-50) / (1-50) / (0-20).
The acrylic resin (a1) is produced by a known polymerization method such as solution polymerization, bulk polymerization, or suspension polymerization, and has a weight average molecular weight of preferably 1,000 to 200,000, more preferably 2,000. １００100,000, more preferably 3,000-50,000.
Examples of the monomer (a1-1) include acrylic acid, methacrylic acid, hydroxyalkyl (2-4 carbon atoms) (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) A) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
Of these, preferred is 2-hydroxyethyl (meth) acrylate.
Examples of the monomer (a1 （2) include acrylamide, acrylonitrile, (meth) acrylate (cyclo) alkyl ester [(meth) acrylate and alcohols having 1 to 25 carbon atoms (methyl alcohol, ethyl alcohol, butyl alcohol). And esters of alcohols such as coal, stearyl alcohol, ethylene glycol, 1,4-butanediol, cyclohexanol, and isoborneol].
Of these, preferred are methyl (meth) acrylate and n-butyl (meth) acrylate.
Examples of the monomer (a1 ▲ 3) include styrene, and among them, styrene is preferred.
[0062]
Examples of the polyester resin (a1-2) include low-molecular-weight polyols and / or condensed polyester polyols obtained by reacting a polyalkylene ether diol having a weight-average molecular weight of 5,000 or less with a polycarboxylic acid, and ring-opening of lactones. Polylactone diols obtained by polymerization, polycarbonate diols obtained by reacting low molecular diols with carbonic acid diesters of lower alcohols (such as methanol) and the like are included.
[0063]
Examples of the low molecular polyol include those described as the low molecular diol of the polyether diol (b5-1).
Examples of the polyalkylene ether diol having a weight average molecular weight of 5,000 or less include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, and a mixture of two or more of these.
[0064]
Examples of the polycarboxylic acid include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), and dicarboxylic acids of these dicarboxylic acids. Ester-forming derivatives [such as acid anhydrides, lower alkyl (C 1-4) esters] and mixtures of two or more thereof; lactones include ε-caprolactone, γ-butyrolactone, γ-valerolactone, and A mixture of two or more of these may be mentioned.
[0065]
Polyesterification is carried out by a conventional method, for example, by converting a low-molecular-weight polyol and / or a polyether polyol having a weight-average molecular weight of 5,000 or less to a polycarboxylic acid or an ester-forming derivative thereof (eg, an anhydride (eg, maleic anhydride, phthalic anhydride, etc.) ), Lower esters (dimethyl adipate, dimethyl terephthalate, etc.), halides and the like) or an anhydride thereof and an alkylene oxide (eg, ethylene oxide and / or propylene oxide) (condensation). Production by a method in which an active hydrogen group is left at a terminal by using a certain polyol in excess, or a method in which a lactone is added to an initiator (a low molecular weight diol and / or a polyether diol having a weight average molecular weight of 5,000 or less). Can be.
[0066]
Specific examples of the polyester resin (a1-2) include, for example, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butyl adipate diol, polybutylene Hexamethylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol, polycaprolactone diol or triol, polyhexa Examples include methylene carbonate diol.
[0067]
As for the ratio of the constituent components of the hydroxyl group-containing polyester, the ratio of the polyol to the polycarboxylic acid is preferably 2/1 to 1/1 as the molar ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. , More preferably 1.5 / 1 to 1/1, and still more preferably 1.3 / 1 to 1.02 / 1. In the case of other components, the ratio is the same except that the components are changed. The weight average molecular weight is preferably from 1,000 to 50,000, more preferably from 2,000 to 20,000, and still more preferably from 3,000 to 15,000.
[0068]
Examples of the active hydrogen group of the polyester resin (a1-2) include an alcoholic hydroxyl group and a carboxylic acid group at the polycondensation terminal of an alcohol and a carboxylic acid.
[0069]
Examples of the polyurethane resin (a1 ▲ 3) include a polyadduct of a polyol and a diisocyanate.
Specific examples of the diisocyanate include those described above. Specific examples of the polyol include, for example, compounds having a structure in which an alkylene oxide (hereinafter abbreviated as AO) is added to an active hydrogen atom-containing polyfunctional compound, and a mixture of two or more thereof.
[0070]
Examples of the active hydrogen atom-containing polyfunctional compound include polyhydric alcohol (a1-3) 1, polyhydric phenols (a1-3) 2, amines (a1-3) 3, and polycarboxylic acid (a1). (3) 4), phosphoric acids (a1 3 5), polythiol (a1 3 6) and the like.
[0071]
Examples of the polyhydric alcohol (a1 ▲ 3) 1 include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and bis ( Dihydric alcohols such as (hydroxymethyl) cyclohexane and bis (hydroxyethyl) benzene; glycerin, trimethylolpropane, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sho Examples thereof include polyhydric alcohols having 3 to 8 valences such as sugar.
[0072]
Examples of the polyhydric phenols (a1 ▲ 3 ▼ 2) include polyphenols such as pyrogallol, catechol and hydroquinone, as well as bisphenols such as bisphenol A, bisphenol F and bisphenol S.
[0073]
Examples of the amines (a1 ▲ 3) include ammonia, monoamines such as alkylamines having 1 to 20 carbon atoms (such as butylamine) and aniline; and fats such as ethylenediamine, trimethylenediamine, hexamethylenediamine, and diethylenetriamine. Group polyamines; piperazine, N-aminoethylpiperazine and other heterocyclic polyamines described in JP-B-55-21044; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, diethyltolylenediamine Aromatic polyamines such as amines, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine; and monoethanolamine, diethanolamine, triethanolamine Ethanolamine, and the like alkanolamines such as triisopropanolamine.
[0074]
Examples of the polycarboxylic acid (a1 ▲ 3 ▼ 4) include aliphatic polycarboxylic acids such as succinic acid and adipic acid, and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid.
[0075]
Examples of the phosphoric acids (a1 ▲ 3 ▼ 5) include phosphoric acid, phosphorous acid, phosphonic acid and the like. Examples of the polythiol (a1 ▲ 3 ▼ 6) include polyvalent polythiol compounds obtained by reacting a glycidyl group-containing compound with hydrogen sulfide.
[0076]
The active hydrogen atom-containing compounds described above may be used in combination of two or more.
[0077]
Examples of AO to be added to the above active hydrogen atom-containing compound include ethylene oxide (EO), propylene oxide (PO), 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran (THF), Styrene oxide, α-olefin oxide, epichlorohydrin and the like can be mentioned.
[0078]
AO may be used alone or in combination of two or more types. In the latter case, a block addition (chip type, balance type, active secondary type, etc.) or a random addition or a mixed system of both (a chip added after random addition: in the molecule) Having 0 to 50% by weight (preferably 5 to 40% by weight) of ethylene oxide chains arbitrarily distributed, and having EO chains of 0 to 30% by weight (preferably 5 to 25% by weight) chipped at molecular terminals ]. Among these AOs, preferred are EO alone, PO alone, THF alone, a combination of PO and EO, and a combination of PO and / or EO with THF (in the case of a combination, random, block and a mixed system of both).
[0079]
The addition of AO to an active hydrogen atom-containing compound can be carried out in a usual manner, without a catalyst or in the presence of a catalyst (alkali catalyst, amine catalyst, acidic catalyst) (particularly in the latter stage of AO addition). The reaction is carried out in one or more stages under normal pressure or pressure.
[0080]
The degree of unsaturation of the polyol is preferably as small as possible, preferably 0.1 meq / g or less, more preferably 0.05 meq / g or less, and still more preferably 0.02 meq / g or less.
[0081]
The ratio of the polyol to the diisocyanate is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, as the molar ratio [OH] / [NCO] of the hydroxyl group [OH] and the isocyanate group [NCO]. 1, more preferably 1.3 / 1 to 1.02 / 1. In the case of other components, the ratio is the same except that the components are changed. The weight average molecular weight is preferably from 1,000 to 50,000, more preferably from 2,000 to 20,000, even more preferably from 3,000 to 15,000.
[0082]
Examples of the active hydrogen group of the polyurethane resin (a1 ▲ 3) include an active hydrogen group that is not urethanized and is derived from a compound containing an active hydrogen atom, and hydrogen in a urethane bond.
[0083]
Examples of the epoxy resin (a1-4) include an addition condensate of a polyepoxide (a1-4) with a polycarboxylic acid (a1-4). During this addition polymerization, a hydroxyl group containing an active hydrogen group is generated.
Examples of the active hydrogen groups of the epoxy resin (a1 ▲ 4) include alcoholic active hydrogen groups generated by epoxidation.
[0084]
Examples of the polycarboxylic acid (a1 ▲ 2) include those exemplified above. The polyepoxide (a1ａ4 ▲ 1) may be any of aliphatic, alicyclic, heterocyclic and aromatic.
[0085]
Examples of the aromatic polyepoxide (a1１4 ▼ 1) include glycidyl ethers of polyhydric phenols, such as bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, and bisphenol AD. Diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalene Diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxy Phenyl diglycidyl ether, glycidyl ether of phenol or cresol novolak resin, diglycidyl ether obtained from reaction of 2 mol of bisphenol A with 3 mol of epichlorohydrin, obtained by condensation reaction of phenol and glyoxal, glutaraldehyde, or formaldehyde And polyglycidyl ethers of polyphenols obtained by the condensation reaction of resorcinol and acetone.
Further, in the present invention, as the aromatic polyepoxide, for example, a diglycidyl urethane compound obtained by an addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate with glycidol, a glycidyl group-containing polyurethane obtained by reacting a polyol with the two reactants It also includes a (pre) polymer and a diglycidyl ether of an alkylene oxide (ethylene oxide or propylene oxide) adduct of bisphenol A.
[0086]
Examples of the heterocyclic polyepoxide (a1-4) 1 include trisglycidylmelamine.
[0087]
Examples of the alicyclic polyepoxide (a1１4 ▼ 1) include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, and ethylene glycol bisepoxydicyclopentyl. Ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, and bis (3 , 4-epoxy-6-methylcyclohexylmethyl) butylamine. The alicyclic group also includes a nuclei hydrogenated product of the aromatic polyepoxide compound.
[0088]
Examples of the aliphatic polyepoxide (a1１4 ▼ 1) include polyglycidyl ethers of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids, and glycidyl aliphatic amines.
Examples of polyglycidyl ethers of polyhydric aliphatic alcohols include, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and trimethylolpropane triane. Glycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol polyglycidyl ether.
Examples of the polyglycidyl ester of polyvalent fatty acid include diglycidyl adipate.
The glycidyl aliphatic amine includes, for example, N, N, N ', N'-tetraglycidylhexamethylenediamine.
In the present invention, the aliphatic group also includes a (co) polymer of glycidyl (meth) acrylate.
[0089]
Of these, preferred is a condensate of bisphenol A diglycidyl ether and adipic acid.
At the time of addition condensation, a group containing an active hydrogen group is generated, so that the active hydrogen equivalent of the resin (a1) having active hydrogen is 50 to 50,000, and the weight average molecular weight is preferably 1,000. ~ 200,000, more preferably 2,000 ~ 100,000, even more preferably 3,000 ~ 50,000.
[0090]
When the reactive surfactant (B) has an isocyanate group which may be blocked, the curing agent (a2) contains two or more functional groups capable of reacting with active hydrogen in one molecule. The compound is not particularly limited as long as it is a compound, and examples thereof include an isocyanate group-containing compound which may be blocked, an epoxy group-containing compound, a melamine resin, a silyl ether group-containing compound, and a (hemi) acetal group-containing compound.
Of these, preferred is an isocyanate group-containing compound which may be blocked.
[0091]
Examples of the isocyanate group-containing compound which may be blocked include, for example, the organic diisocyanates exemplified above and modified products thereof (urethane group, carbodiimide group, allophanate group, urea group, buret group, isocyanurate group or Oxazolidone group-containing modified product), HDI isocyanurate, HDI buret, IPDI isocyanurate, IPDI buret, crude MDI [condensation product of crude diaminodiphenylmethane @ formaldehyde and aromatic amine (aniline) or a mixture thereof: diaminodiphenylmethane And a small amount (for example, 5 to 20% by mass) of a polyamine having a trifunctional or higher functionality [2], polyallyl polyisocyanate (PAPI), and blocked isocyanate compounds thereof. It is.
Of these, HDI isocyanurate and IPDI isocyanurate are preferred.
Examples of the blocking agent include the above-mentioned blocking agents and a combination of two or more thereof.
The ratio of the resin (a1) containing active hydrogen to the curing agent (a2) having an isocyanate group which may be blocked is determined by the molar ratio of the active hydrogen group of the resin (a1) to the isocyanate group of the curing agent (a2). Is preferably from 1/1 to 2/1, more preferably from 1.2 / 1 to 1.8 / 1, and still more preferably from 1.3 / 1 to 1.6 / 1.
[0092]
Examples of the epoxy group-containing compound include aliphatic, alicyclic, heterocyclic, and aromatic polyepoxide compounds, and the above-mentioned polyepoxides.
[0093]
Of these, polyglycidyl ethers of polyhydric aliphatic alcohols and glycidyl ethers of polyhydric phenols are preferred.
The ratio of the active hydrogen-containing resin (a1) to the epoxy group-containing curing agent (a2) is preferably from 1/1 to 2 / molar as the molar ratio of the (a1) active hydrogen group to the (a2) epoxy group. 1 or less, more preferably 1.2 / 1 or more and 1.8 / 1 or less, still more preferably 1.3 / 1 or more and 1.6 / 1 or less.
[0094]
When the reactive surfactant (B) has an epoxy group, the curing agent (a2) is not particularly limited as long as it is a compound containing two or more functional groups capable of reacting with active hydrogen in one molecule. Examples include the compounds exemplified above.
Of these, preferred are epoxy group-containing compounds and optionally blocked isocyanate group-containing compounds.
[0095]
In the slurry coating of the present invention, the content of the reactive surfactant (B) is preferably 0.1 to 10% by weight based on the total weight of the fine particles (A) and the reactive surfactant (B). More preferably, it is 0.5 to 8% by weight, most preferably 1 to 5% by weight.
[0096]
The resin content in the slurry coating composition of the present invention is preferably 20 to 75% by weight, more preferably 20 to 60% by weight, and the viscosity of the dispersion at 25 ° C is preferably 10 to 100,000 mPa · s. Preferably it is 50 to 5,000 mPa · s. The resin particle diameter in the slurry coating is 0.1 to 50 μm.
When the resin content is 20 to 75% by weight, the dispersibility of the fine particles (A) in water becomes good, and when the dispersion viscosity is 10 to 100,000 mPa · s, the handling as a coating material becomes easy. When the average particle diameter of the fine particles (A) is from 0.1 to 50 μm, there is no sedimentation of the particles in water, and the evaporation of water and the adjustment of viscosity during baking become easy.
[0097]
As long as the effects of the present invention are not impaired, other known emulsifiers or surfactants (nonionic emulsifiers and surfactants, anionic emulsifiers and surfactants, cationic emulsifiers) may be used together with the reactive surfactant (B). And surfactants, various reactive emulsifiers and surfactants). When used in combination, the amount of the other emulsifier and surfactant is preferably 44% by weight or less, more preferably 37% by weight or less, based on the total amount of the emulsifier or surfactant.
[0098]
The slurry coating obtained by the method of the present invention may contain, if necessary, known additives (C) (for example, a viscoelasticity modifier, a reaction accelerator, a dynamic surface tension modifier, a filler, an Viscosifiers, heat or weather resistance stabilizers, leveling agents, defoamers, preservatives, coloring agents, etc.).
[0099]
Examples of the viscoelasticity adjusting agent include a polymer type viscoelasticity adjusting agent such as a polycarboxylic acid type, a polysulfonic acid type, a polyether-modified carboxylic acid type and a polyether type, and an association type viscoelasticity adjusting agent such as a urethane-modified polyether type. Is mentioned. Further, the reactive surfactant (B) can be used as a viscoelasticity modifier. The amount is preferably 0.05% or more and 10.0% or less, more preferably 0.1 or more and 5% or less, based on the slurry paint.
[0100]
Examples of the reaction accelerator include amine compounds such as diazabicyclooctane and 1,8-diazabicyclo (5,4,0) -undecene-7, and metal-containing compounds such as dibutyltin dilaurate and zirconium octylate. The compounding amount is preferably 0.05% or more and 5.00% or less, more preferably 0.1% or more and 3% or less based on the slurry paint.
[0101]
Examples of the dynamic surface tension adjuster include an acetylene glycol-based dynamic surface tension adjuster, a fluorine-based dynamic surface tension adjuster, and a silicone-based dynamic surface tension adjuster. The compounding amount is preferably 0.05% or more and 20.0% or less, more preferably 0.1 or more and 10% or less based on the slurry paint.
[0102]
Examples of the weather stabilizer include salicylic acid-based ultraviolet absorbers such as phenyl salicylate and p-tert-butylphenyl salicylate; benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; Benzotriazole ultraviolet absorbers such as (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2-ethylhexyl-2-cyano- Examples include cyanoacrylate ultraviolet absorbers such as 3,3'-diphenylacrylate, and hindered amine light stabilizers such as octylated diphenylamine and isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate. It is. The compounding amount is preferably 0.05% or more and 10% or less, more preferably 0.5% or more and 3% or less based on the slurry paint.
[0103]
The leveling agent is not particularly limited. For example, olefin resins such as low molecular polyethylene and low molecular polypropylene, olefin copolymers such as ethylene-acryl copolymer and ethylene-methacryl copolymer, and (meth) acryl copolymer And polyvinylpyrrolidone. The compounding amount is preferably 0.2% or more and 6% or less, more preferably 0.5% or more and 3% or less with respect to the slurry paint.
[0104]
The colorant used as necessary is not particularly limited, and examples thereof include inorganic pigments, organic pigments, and dyes. Examples of the inorganic pigment include titanium oxide, carbon black, chromium oxide, and ferrite. As organic pigments, azo pigments such as azo lake type, monoazo type, disazo type, chelated azo type, benzimidazolone type, phthalocyanine type, quinacridone type, dioxazine type, isoindolinone type, thioindigo type, perylene type, quinophthalone type, anthraquinone And other polycyclic pigments. Dyes include nigrosine and aniline dyes. Although the amount varies depending on the type of the coloring agent, it is preferably 0.5% or more and 30% or less, more preferably 1.0% or more and 10% or less with respect to the slurry paint.
[0105]
Examples of the method for producing the slurry paint of the present invention include, but are not limited to, the following methods.
{Circle around (1)} Solvent removal method [in an aqueous medium containing a reactive surfactant (B) (water or a mixed solvent of water and a water-miscible solvent of an alcohol such as methanol or isopropanol or a ketone solvent such as acetone)] A solution obtained by dissolving the resin (a1) and, if necessary, the curing agent (a2) in the above-mentioned organic solvent is dispersed in a reaction vessel with a homomixer or the like. A method in which only the water-miscible solvent and the organic solvent are removed to reduce the pressure to 15 Torr and water remains, and the resin particles having an average particle size of 0.1 μm to 50 μm are dispersed in water];
{Circle around (2)} Pulverized particle dispersion method [The resin (a1) and, if necessary, the curing agent (a2) are melt-kneaded, cooled and pulverized, and the resin particles having an average particle size of 0.1 to 50 μm are converted into a reactive surfactant. (B) Dispersing Into a Reaction Vessel Using an Aqueous Medium Containing Disperser or the Like]
The concentration of the resin (a1) and, if necessary, the curing agent (a2) in the organic solvent in the production according to (1) is preferably 20 to 75% by weight, more preferably 40 to 60% by weight.
Further, the concentration of the resin (a1) and, if necessary, the curing agent (a2) in the dispersion according to the production methods (1) and (2) above is preferably 5 to 70% by weight, more preferably 30 to 70% by weight. 60% by weight. Further, the 25 ° C. viscosity of the dispersion is preferably 50 to 300,000 mPa · s, more preferably 100 to 10,000 mPa · s, and still more preferably 1,000 to 8,000 mPa · s.
In the above production method (1), the temperature in the system is preferably -5 to 100C, more preferably 30 to 80C, and the solvent removal is preferably 0.1 to 50 hours, more preferably 2 to 10 hours. .
[0106]
Examples of the disperser used in the above production method include a homomixer, a high-pressure homomixer, a disperser, a high-pressure homogenizer, a static mixer, a membrane emulsifier, a fill mix, and an ultrasonic disperser. Of these, a homomixer is preferred.
[0107]
In the present invention, the reactive surfactant (B) exhibits good surfactant activity and dispersion stability. At the same time, by baking after applying the dispersion, the surfactant causes a chemical bond with the object to be dispersed, is taken into the film, and exhibits excellent water resistance and strength.
[0108]
The water-dispersed powder slurry coating of the present invention can be applied using a spray coating machine, which is a conventional coating equipment for water-based coating or a coating equipment for solvent coating, and does not require any new equipment.
In the method for forming a coating film, the slurry paint is spray-coated on an object to be coated so as to have a wet film thickness, preferably from 10 to 200 μm, more preferably from 10 to 100 μm. While the paint floats from the spray nozzle to the object to be coated, the moisture in the paint evaporates and the resin content increases. The paint resin content (% by weight) at the time of application to the object to be coated can be expressed by the difference between the value obtained by dividing the difference between the amount of applied paint and the weight of the coated film after heating by the amount of applied paint and 100. It is preferably 50% by weight or more and 95% by weight or less, more preferably 60% by weight or more and 90% by weight or less. When the resin content in the applied paint is 50% by weight or more, no sagging of the paint occurs. A smooth coating film can be formed.
The coated object is preferably at a temperature of 100 ° C. or more and 200 ° C. or less, more preferably at a temperature of 120 ° C. or more and 180 ° C. or less, preferably 5 minutes or more and 60 minutes or less, more preferably 5 minutes or more and 30 minutes or less, furthermore Preferably, the coating film can be formed by heating for 5 to 20 minutes.
The film thickness of the coated object obtained by applying and baking the coating material of the present invention is preferably 10 μm or more and 150 μm or less, more preferably 15 μm or more and 50 μm or less.
[0109]
The water-dispersed powder slurry coating obtained by the method of the present invention can be used particularly as a top coat for automobiles or for coating various products such as buildings and home electric appliances.
[0110]
【Example】
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In the following, "parts" indicates parts by weight and "%" indicates% by weight.
In the following examples, the molecular weights of the reactive surfactant (B), the resin (a1) having active hydrogen and the adduct (b3) were measured by GPC.
[0111]
Production Example 1
A reaction vessel equipped with a stirrer, a dropping funnel, a nitrogen gas inlet tube, a thermometer, and a reflux condenser was charged with 53 parts of 4-α-cumylphenol and 23 parts of a Lewis acid catalyst (Galleon Earth, manufactured by Mizusawa Chemical Industry Co., Ltd.) and stirred. Below, the inside of the system was replaced with nitrogen gas, and the temperature was raised to 90 ° C. At the same temperature, 410 parts of an ethanol block of 3-isopropenyl-α, α-dimethylbenzyl isocyanate was added dropwise over 3 hours, and the mixture was further reacted at the same temperature for 5 hours. After cooling to 30 ° C., the catalyst was filtered off to add 7 mol of 3-isopropenyl-α, α-dimethylbenzyl isocyanate ethanol block to 1 mol of 4-α-cumylphenol (number average). 463 parts (molecular weight 1,900) (B0-1) were obtained. (B0-1) with EO added (EO content 45%) 31.1 parts, polyethylene glycol (number average molecular weight 6,000) 66.2 parts and hexamethylene diisocyanate (hereinafter abbreviated as HDI) 2.6 parts Was reacted at 80 ° C. for 3 hours to obtain 100 parts of a reactive surfactant [B-1] having an oxyethylene unit content of 66% by weight and a weight average molecular weight of 27,000.
[0112]
Production Example 2
Hydroxyl group-containing hydrocarbon [styrene 2 mol and 3-isopropenyl-α, α-dimethylbenzyl isocyanate ethanol block 5 mol 5 mol obtained by the same Friedel-Crafts reaction as in Production Example 1 Addition of EO to 1 mol of cumylphenol (EO content: 10%); number average molecular weight 1,800] 16.5 parts, polyethylene glycol (number average molecular weight 9,000) 81.4 parts and TDI2 .2 parts were reacted at 80 ° C. for 3 hours to obtain 100 parts of a reactive surfactant [B-2] having an oxyethylene unit content of 80% by weight and a weight average molecular weight of 33,000.
[0113]
Production Example 3
Hydroxyl group-containing hydrocarbon [styrene (7 mol) and 2-mol ethanol block of 3-isopropenyl-α, α-dimethylbenzyl isocyanate) obtained by the Friedel-Crafts reaction similar to Production Example 1 were converted to 4-α- EO added to 1 mol of cumylphenol (EO content: 10%); number average molecular weight 2,000] 32.1 parts, polyethylene glycol (number average molecular weight 3,000) 61.6 parts and IPDI6 8.8 parts was reacted at 80 ° C. for 3 hours to obtain 100 parts of a reactive surfactant [B-3] having an oxyethylene unit content of 60% by weight and a weight average molecular weight of 15,000.
[0114]
Production Example 4
Hydroxyl group-containing hydrocarbon obtained by the same Friedel-Crafts reaction as in Production Example 1 [styrene obtained by adding 5 mol of styrene and 1 mol of styrene-p-glycidyl ether to 1 mol of phenol and adding EO ( EO content 40%); 10.5 parts of number average molecular weight 1,000], 87.1 parts of polyethylene glycol (number average molecular weight 9,000) and 2.3 parts of HDI are reacted at 80 ° C. for 3 hours, and oxyethylene unit content 80 parts by weight of a reactive surfactant [B-4] having a weight average molecular weight of 31,000 was obtained in an amount of 100 parts.
[0115]
Production Example 5
Hydroxyl group-containing hydrocarbon [styrene 3 mol, 3-isopropenyl-α, α-dimethylbenzyl isocyanate 3 mol, and 2,3-diglycidyloxy] obtained by the same Friedel-Crafts reaction as in Production Example 1. Styrene added to 1 mol of 4-α-cumylphenol with EO added (EO content 5%); number average molecular weight 1,300] 29.4 parts, polyethylene glycol (number average molecular weight 3,000) 65.1 parts and HDI 5.5 parts were reacted at 80 ° C. for 3 hours to obtain 100 parts of a reactive surfactant [B-5] having an oxyethylene unit content of 26% by weight and a weight average molecular weight of 12,000.
[0116]
Production Example 6
Hydroxyl group-containing hydrocarbon [5 mol of styrene and 2 mol of 3-isopropenyl-α, α-dimethylbenzyl isocyanate ethanol block obtained by the Friedel-Crafts reaction in the same manner as in Production Example 1 was used to prepare 4-α-cure. 16.4 parts of sulfuric anhydride was added little by little to 86.4 parts of a substance obtained by adding PO to a substance added to 1 mol of millphenol (PO content: 15%); After reacting at 80 ° C. for 3 hours, the mixture was neutralized with sodium hydroxide to obtain 100 parts of a reactive surfactant [B-6] having a hydrophilic group content of 16% by weight and a weight average molecular weight of 8,000.
[0117]
Production Example 7
To a product obtained by adding 7 mol of a methyl ethyl ketone oxime block of a hydroxyl group-containing hydrocarbon [3-isopropenyl-α, α-dimethylbenzyl isocyanate] to 1 mol of phenol, obtained by the same Friedel-Crafts reaction as in Production Example 1. EO added (EO content 10%); number average molecular weight 1,800] 52.6 parts of glacial acetic acid and 52.6 parts of sodium dichromate dihydrate were reacted at 15 ° C for 5 hours. A carboxylic acid was reacted with 44 parts of aminoethylethanolamine at 230 ° C. for 12 hours to obtain 100 parts of a reactive surfactant [B-7] having a hydrophilic group content of 27% by weight and a weight average molecular weight of 5,800.
[0118]
Production Example 8
Hydroxyl group-containing hydrocarbon obtained by the same Friedel-Crafts reaction as in Production Example 1 [5 mol of styrene and 2 mol of ethanol block of 3-isopropenyl-α, α-dimethylbenzyl isocyanate are added to 1 mol of phenol. PO (addition: 15%); number average molecular weight 7,200] To 51.4 parts, 15.2 parts of acrylonitrile was added dropwise at 60 ° C. for 1 hour in the presence of 0.5 part of potassium hydroxide. Thereafter, in 300 parts of methanol, 0.2 part of cobalt was reacted at 80 ° C. for 6 hours using hydrogen gas to obtain 66.4 parts of an amino group-containing hydrocarbon (B0-6). (B0-6) was reacted with 10.6 parts of sodium hydroxide and 24.5 parts of methyl chloride at 150 ° C. for 6 hours to form tertiary ammonium, and then 73.6 parts of a 30% aqueous solution of sodium monochloroacetate was added at 70 ° C. The reaction was carried out for 5 hours to obtain 100 parts of a reactive surfactant [B-8] having a hydrophilic group content of 21% by weight and a weight average molecular weight of 8,000.
[0119]
Comparative Production Example 1
19.3 parts of polyoxyalkylene monol [styrene obtained by adding 7 mol of 4-styrene-added ethylene oxide to styrene (EO content: 60%); number average molecular weight: 1,500], polyethylene glycol (number average molecular weight: 6) (000) and 3.3 parts of HDI were reacted at 80 ° C. for 3 hours to obtain 100 parts of a surfactant [B′-9] having a hydrophilic group content of 77% by weight and a weight average molecular weight of 18,000.
[0120]
Preparation of acrylic hydroxy functional resin
250 parts of xylene were placed in the reactor and heated to 100 ° C., then the mixture in the following proportions was added dropwise for about 3 hours. The reaction during that time was performed under a nitrogen atmosphere. After the completion of the dropwise addition, the reaction was continued at 100 ° C. for 2 hours.
(1) Styrene 23 parts
(2) Methyl methacrylate 23 parts
(3) 20 parts of butyl acrylate
(4) 33 parts of hydroxyethyl acrylate
(5) Peroxy D (manufactured by NOF Corporation, peroxide) 1 part
After completion of the reaction, the organic solvent and the residual monomer were removed by distillation under reduced pressure, and then vacuum drying was performed to obtain an acrylic hydroxy-functional resin [acrylic resin 1] having a hydroxyl equivalent of 420 and a weight average molecular weight of 30,000.
The above [acrylic resin 1] 59 parts and MEK oxime-blocked HDI isocyanurate (Duranate, manufactured by Asahi Kasei Co., Ltd.) 41 parts were kneaded using a heating kneader at 100 ° C., and then pulverized to about 5 μm. [Acrylic resin 2] having a diameter of 7 μm and a ratio of major axis / minor axis of 1.2 was obtained.
[0121]
Preparation of polyester resin
200 parts of neopentyl glycol, 93 parts of ethylene glycol and 355 parts of terephthalic acid were charged into the reactor, and the reaction was allowed to proceed for 2 hours while heating at 230 ° C. to distill off generated water. Thereafter, 0.2 parts of dibutyltin oxide is added, and the reaction is continued until the acid value becomes 0.5 or less, whereby the weight average molecular weight of 14,000 having hydroxyl groups at both ends used for the coating film of the present invention. Thus, a polyester resin [Polyester Resin 1] having a hydroxyl value of 16.5 mgKOH / g was obtained.
93 parts of [Polyester Resin 1] obtained above and 7 parts of MEK oxime-blocked HDI isocyanurate (Duranate, manufactured by Asahi Kasei) are kneaded at 100 ° C. using a heating kneader, and then pulverized to about 5 μm to obtain an average particle diameter of 5 μm. [Polyester resin 2] having a diameter of 7 μm and a ratio of major axis / minor axis of 1.2 was obtained.
[0122]
Preparation example of dispersion
Reactive surfactants [B-1] to [B-8] obtained in Production Examples 1 to 8, surfactant [B'-9] obtained in Comparative Production Example 1, low molecular weight surfactant [B'-10] (EO adduct of octylphenol, number average molecular weight 1,000) and PVA [B'-11] (partially saponified polyvinyl alcohol, polymerization degree 1,700, saponification degree 88%) Parts were dispersed in 100 parts of water to obtain a dispersion. These are designated as [Dispersion 1] to [Dispersion 11].
[0123]
Examples 1 to 8, Comparative Examples 1 to 3
In a beaker, 59 parts of [acrylic resin 1], 41 parts of MEK oxime-blocked HDI isocyanurate (manufactured by Asahi Kasei Corporation, duranate), and 100 parts of tetrahydrofuran are mixed, and these are mixed in [dispersion liquid 1] to [dispersion liquid]. 11] After adding to 100 parts, the mixture was mixed for 1 minute at 9,000 rpm using an ultra disperser (manufactured by Yamato Scientific Co., Ltd.) to obtain an average particle size of 5 μm. After mixing, this mixed solution was put into a four-necked flask equipped with a stirring bar and a thermometer, and the solvent was removed at 25 ° C. under reduced pressure for 10 hours. Next, 0.1 part of a urethane-forming catalyst (“TEDA”, manufactured by Tosoh Corporation), 0.1 part of a light-resistant stabilizer (“DIC-TBS”, manufactured by Dainippon Ink and Chemicals, Inc.), and a viscoelasticity imparting agent (“SN thickener-651”) (Manufactured by San Nopco Co.) was added to obtain a slurry coating having an average particle diameter of dispersed particles, a ratio of major axis / minor axis, and viscosity as shown in Table 1.
[0124]
Examples 9 to 16, Comparative Examples 4 to 6
To 100 parts of [dispersion 1] to [dispersion 11] obtained according to the dispersion preparation example, 100 parts of [acrylic resin 2] of the acrylic hydroxy-functional resin fine powder obtained above was added, and the mixture was added to Ultra. Using a disperser (manufactured by Yamato Scientific Co., Ltd.), the mixture was mixed at 9,000 rpm for 1 minute. Then, 0.1 part of a urethanization catalyst ("TEDA", manufactured by Tosoh Corporation) and 0.1 part of a light stabilizer ("DIC-TBS", manufactured by Dainippon Ink and Chemicals, Inc.) were added. A slurry paint having an average particle size, a ratio of major axis / minor axis, and viscosity was obtained.
[0125]
Examples 17 to 24, Comparative Examples 7 to 9
In a beaker, 93 parts of [polyester resin 1], 7 parts of MEK oxime-blocked HDI isocyanurate (manufactured by Asahi Kasei, duranate), and 100 parts of tetrahydrofuran are mixed, and these are dispersed in [dispersion liquid 1] to [dispersion liquid]. 11] After adding to 100 parts, the mixture was mixed for 1 minute at 9,000 rpm using an ultra disperser (manufactured by Yamato Scientific Co., Ltd.) to obtain an average particle size of 5 μm. After mixing, this mixed solution was put into a four-necked flask equipped with a stirring bar and a thermometer, and the solvent was removed at 25 ° C. under reduced pressure for 10 hours. Next, 0.1 part of a urethane-forming catalyst (“TEDA”, manufactured by Tosoh Corporation), 0.1 part of a light-resistant stabilizer (“DIC-TBS”, manufactured by Dainippon Ink and Chemicals, Inc.), and a viscoelasticity imparting agent (“SN thickener-651”) (Manufactured by San Nopco Co.) was added to obtain a slurry paint having an average particle diameter of dispersed particles, a ratio of major axis / minor axis, and viscosity as shown in Table 3.
[0126]
Examples 25 to 32, Comparative Examples 10 to 12
To 100 parts of [dispersion liquid 1] to [dispersion liquid 11] obtained according to the dispersion preparation example, 100 parts of the above-obtained polyester-based hydroxy functional resin fine powder [polyester resin 2] was added. Using a disperser (manufactured by Yamato Scientific Co., Ltd.), the mixture was mixed at 9,000 rpm for 1 minute. Next, 0.1 part of a urethanization catalyst (“TEDA”, manufactured by Tosoh Corporation) and 0.1 part of a light stabilizer (“DIC-TBS”, manufactured by Dainippon Ink and Chemicals, Inc.) were added. A slurry paint having an average particle size, a ratio of major axis / minor axis, and viscosity was obtained.
[0127]
Each of the slurry paints obtained by the above method was evaluated by the following test methods. The results are shown in Tables 1, 2, 3 and 4.
[0128]
(Preparation of test pieces)
The obtained slurry paint was spray-coated on a zinc phosphate-treated steel sheet, pre-baked at 60 ° C. for 10 minutes, and then baked and dried at 160 ° C. for 10 minutes to obtain a coating film having a thickness of 0.03 mm.
(Test method)
Water resistance evaluation: The coating film obtained above was immersed in water at 80 ° C. for 120 hours, cooled slowly at 20 ° C. for 3 hours, wiped with a cloth, and observed for appearance.
○: No change from appearance before immersion
×: appearance defects such as wrinkles, cracks, swelling, and peeling occurred
Measurement of dissolution rate: The coating film obtained above was immersed in water at 25 ° C. for 1 hour, the film after water immersion was dried at 60 ° C. for 1 hour, and the weight was compared with the weight of the film before immersion. The rate of decrease was measured and defined as the dissolution rate.
Measurement of coating film strength: The surface hardness of the coating film obtained above was measured using a Fisher hardness meter (Fisher Scope H100V manufactured by Fisher Instruments). (Load: 0.4-100mN, indentation depth: 5μm) This test method can numerically calculate the coating hardness of the paint with high accuracy, and in a single test, the coating hardness, Young's modulus, etc. Elements can be evaluated. The strength of the coating film can be evaluated by measuring the surface hardness.
Evaluation of dispersibility: The obtained slurry paint was centrifuged at 6,000 rpm for 15 minutes using a centrifuge, and the sedimentation state of the dispersed resin was visually determined.
：: Dispersion appearance is almost the same before and after centrifugation
Δ: Part of the dispersion sedimented due to centrifugation
×: Dispersion completely settled by centrifugation
[0129]
[Table 1]

[0130]
[Table 2]

[0131]
[Table 3]

[0132]
[Table 4]

[0133]
【The invention's effect】
The water-dispersed powder slurry coating of the present invention contains an active hydrogen group because it contains at least one group selected from the group consisting of an isocyanate group, a blocked isocyanate group and an epoxy group in the molecule. When the resin is dispersed, the cured film has excellent film properties such as water resistance while exhibiting excellent film strength. In addition, when the paint is stored, the dispersion stability of the resin is excellent.
Due to the above effects, the water-dispersed powder slurry paint of the present invention is extremely useful for paints on automobiles, buildings, industrial machines, and the like.

Claims (15)

An aqueous medium contains fine particles (A) comprising a resin (a1) having active hydrogen and a reactive surfactant (B) having an isocyanate group and / or an epoxy group which may be blocked. A water-dispersed powder slurry coating characterized by the following. The water-dispersed powder slurry coating according to claim 1, further comprising a curing agent (a2). The said reactive surfactant (B) contains the hydrophobic part which has a C6-C100 hydrocarbon group which has an aromatic ring, and an isocyanate group and / or an epoxy group which may be blocked. Or a water-dispersed powder slurry coating according to 2. The water according to any one of claims 1 to 3, wherein the reactive surfactant (B) has, as a hydrophilic part, at least one selected from the group consisting of an oxyethylene unit, an anionic group, a cationic group, and an amphoteric ionic group. Dispersed powder slurry paint. The reactive surfactant (B) is a monohydric phenol or a monovalent aromatic alcohol (b1) and a vinyl monomer (b2) having an isocyanate group which may be blocked and / or a vinyl monomer having an epoxy group (B2 ′) or an alkylene oxide adduct thereof (b3), an organic diisocyanate (b4), and a diol and / or diamine (b5) having a polyoxyalkylene chain containing a polyoxyethylene unit. The water-dispersed powder slurry coating according to claim 3 or 4, comprising a urethane resin (L) having an isocyanate group and / or an epoxy group which may be blocked, which is a main component. The water-dispersed powder slurry paint according to claim 5, wherein the reactive surfactant (B) comprises one or more compounds represented by the following general formula (1).

[Wherein Q is a monovalent phenol or a monovalent aromatic alcohol (b1) and a vinyl monomer (b2) having an isocyanate group which may be blocked and / or a vinyl monomer (b2 ′) having an epoxy group. G represents a residue of an organic diisocyanate (b4) which may have a urea bond, X represents O or NH, J represents a residue of a diol and / or diamine (b5) having a polyoxyalkylene chain containing a polyoxyethylene unit, and Z represents hydrogen, a group represented by -COO-Q, or -CO-Y ｛Y represents —OR ¹ (R ¹ : a residue of a monohydric alcohol having 1 to 18 carbon atoms) or —NR ² R ³ (R ² : a hydrocarbon group having 1 to 18 carbon atoms or a hydrocarbon group having 1 to 16 carbon atoms) Hi Rokishiarukiru group, ^{R 3:} hydrogen, a} is a carbon number 1 to 18 hydrocarbon group or a hydroxyalkyl group having 1 to 16 carbon atoms), representing respectively. m is an integer of 1 to 500. ] 7. The vinyl monomer (b2) is 3-isopropenyl-α, α-dimethylbenzyl isocyanate or 3-ethylenyl-α, α-dimethylbenzyl isocyanate in which an isocyanate group may be blocked. A water-dispersed powder slurry paint as described in the above. 8. The reactive surfactant (B) according to any one of claims 4 to 7, wherein the hydrophilic part contains oxyethylene units as hydrophilic parts in an amount of 20% by weight or more and 90% by weight or less based on the weight of the reactive surfactant (B). A water-dispersed powder slurry paint as described in the above. The reactive surfactant (B) is a monohydric phenol or a monovalent aromatic alcohol (b1) and a vinyl monomer (b2) having an isocyanate group which may be blocked and / or a vinyl monomer having an epoxy group (B2 ′), a residue (b3 ′) of an alkylene oxide adduct thereof and at least one ionic group selected from the group consisting of an anionic group, a cationic group, and an amphoteric ionic group. The water-dispersed powder slurry coating according to claim 3 or 4, wherein The reactive surfactant (B) has at least one group selected from the group consisting of an anionic group, a cationic group, and a zwitterionic group as a hydrophilic part based on the weight of the reactive surfactant (B). The water-dispersed powder slurry coating according to any one of claims 4 to 9, which contains 0.1 wt% or more and 50 wt% or less. The water-dispersed powder slurry coating according to any one of claims 1 to 10, wherein the resin (a1) is at least one selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin, and an epoxy resin. The water-dispersed powder slurry coating according to any one of claims 1 to 11, wherein the fine particles (A) have an average particle size of 0.1 µm or more and 50 µm or less. The water-dispersed powder slurry coating according to any one of claims 1 to 12, wherein the fine particles (A) have a spherical shape having a major axis / minor axis ratio of 1.0 to 1.5. The water-dispersed powder slurry coating according to any one of claims 1 to 13, wherein the fine particles (A) are obtained by dispersing a solvent solution of the resin (a1) in water and removing the solvent. A coating film obtained by applying and baking the water-dispersed powder slurry coating material according to any one of claims 1 to 14.