JP4378487B2 - Thickener composition - Google Patents

Description

［式中、Ｘ、Ｚは、ナフチル基、アントリル基、ピレニル基、炭素数６〜２４の炭化水素基から選ばれる基であり、Ｘ、Ｚの少なくとも一方はナフチル基、アントリル基、ピレニル基から選ばれる基である。Ｙはジイソシアネ−ト化合物から導かれる２価の有機残基であり、ＯＲ、ＯＲ’、ＯＲ”は炭素数２〜４のオキシアルキレン基であり、ａ、ｂ、ｄは１〜５００の整数であり、ｃは１以上の整数である。］
【０００６】
また、本発明は上記の増粘剤組成物を０．０１〜１０重量％配合してなる水系エマルションである。
【０００７】
さらに、本発明は上記の増粘剤組成物を０．０１〜１０重量％配合してなる水系エマルション塗料である。
【０００８】
【発明の実施の形態】
本発明の一般式（１）中のＸ、Ｚは、ナフチル基、アントリル基、ピレニル基、炭素数６〜２４の炭化水素基から選ばれる基であり、Ｘ、Ｚの少なくとも一方はナフチル基、アントリル基、ピレニル基から選ばれる基である。Ｘ、Ｚの組み合わせとしては、例えば両方がナフチル基の場合、両方がアントリル基の場合、両方がピレニル基の場合、一方がナフチル基で他方がアントリル基の場合、一方がナフチル基で他方がピレニル基の場合、一方がアントリル基で他方がピレニル基の場合、一方がナフチル基で他方が炭素数６〜２４の炭化水素基の場合、一方がアントリル基で他方が炭素数６〜２４の炭化水素基の場合、一方がピレニル基で他方が炭素数６〜２４の炭化水素基の場合などがあげられる。炭素数６〜２４の炭化水素基としては、例えば、飽和炭化水素基、不飽和炭化水素基、直鎖炭化水素基、分枝炭化水素基、脂肪族炭化水素基、環式炭化水素基、芳香族炭化水素基などがあげられる。これらのうち好ましくは両方がナフチル基の場合、一方がナフチル基で他方がアントリル基の場合、一方がナフチル基で他方がピレニル基の場合、一方がナフチル基で他方が炭素数６〜２４の炭化水素基の場合である。
【０００９】
本発明の一般式（１）中のＹはジイソシアネ−ト化合物から導かれる２価の有機残基であり、ジイソシアネ−ト化合物としては特に限定されない。ジイソシアネ−ト化合物としては例えば、脂肪族系ジイソシアネ−ト化合物、芳香族系ジイソシアネ−ト化合物、脂環族系ジイソシアネ−ト化合物などがあげられる。
【００１０】
脂肪族系ジイソシアネ−ト化合物としては例えば、メチレンジイソシアネ−ト、ジメチレンジイソシアネ−ト、トリメチレンジイソシアネ−ト、テトラメチレンジイソシアネ−ト、ペンタメチレンジイソシアネ−ト、ヘキサメチレンジイソシアネ−ト、ヘプタメチレンジイソシアネ−ト、オクタメチレンジイソシアネ−ト、ノナメチレンジイソシアネ−ト、デカメチレンジイソシアネ−ト、ジプロピルエ−テルジイソシアネ−ト、２，２−ジメチルペンタンジイソシアネ−ト、３−メトキシヘキサンジイソシアネ−ト、２，２，４−トリメチルペンタンジイソシアネ−ト、３−ブトキシヘキサンジイソシアネ−ト、１，４−ブチレングリコ−ルジプロピルエ−テルジイソシアネ−ト、メタキシリレンジイソシアネ−ト、パラキシリレンジイソシアネ−ト、テトラメチルキシリレンジイソシアネ−トなどがあげられる。
【００１１】
芳香族系ジイソシアネ−ト化合物としては例えば、メタフェニレンジイソシアネ−ト、パラフェニレンジイソシアネ−ト、２，４−トリレンジイソシアネ−ト、２，６−トリレンジイソシアネ−ト、ジメチルベンゼンジイソシアネ−ト、エチルベンゼンジイソシアネ−ト、イソプロピルベンゼンジイソシアネ−ト、ビフェニルジイソシアネ−ト、トリジンジイソシアネ−ト、３，３’−ジメトキシビフェニルジイソシアネ−ト、ナフタレンジイソシアネ−ト、４，４’−ジフェニルメタンジイソシアネ−ト、２，２’−ジメチルジフェニルメタン−４，４’−ジイソシアネ−ト、３，３’−ジメトキシジフェニルメタン−４，４’−ジイソシアネ−ト、４，４’−ジメトキシジフェニルメタン−３，３’−ジイソシアネ−ト、４，４’−ジエトキシジフェニルメタン−３，３’−ジイソシアネ−ト、２，２’−ジメチル−５，５’−ジメトキシジフェニルメタン−４，４’−ジイソシアネ−トなどがあげられる。
【００１２】
脂環族系ジイソシアネ−ト化合物としては例えば、シクロヘキシルジイソシアネ−ト、水添キシリレンジイソシアネ−ト、イソホロンジイソシアネ−ト、ジシクロヘキシルメタン−４，４’−ジイソシアネ−トなどがあげられる。
【００１３】
本発明の一般式（１）中のＯＲ、ＯＲ’、ＯＲ”は炭素数２〜４のオキシアルキレン基である。炭素数が２未満および４を越えると増粘性が低下する。炭素数２〜４のオキシアルキレン基としてはオキシエチレン基、オキシプロピレン基およびオキシブチレン基などがあげられる。これらのうちオキシエチレン基は必須である。オキシエチレン基の割合は、好ましくは全オキシアルキレン基の６０重量％以上、さらに好ましくは全オキシアルキレン基の８０重量％以上、特に好ましくは全オキシアルキレン基の９０重量％以上である。オキシエチレン基が６０重量％未満では増粘性が低下する。ＯＲ、ＯＲ’、ＯＲ”は２種以上のオキシアルキレン基をブロックまたはランダムに繋いだものでも良い。（ＯＲ）ａ、（ＯＲ’）ｂ、（ＯＲ”）ｄは同種でもよく、異種の組み合わせでもよい。
【００１４】
本発明の一般式（１）中のａ、ｂ、ｄは各々、ＯＲ、ＯＲ’、ＯＲ”の繰り返し単位を表わし、１〜５００の整数であり、好ましくは２〜４００であり、さらに好ましくは２〜３００である。１未満および５００を越えると増粘性が低下する。
【００１５】

内の繰り返し単位を表わし、１以上の整数である。
【００１６】
本発明の増粘剤を合成する方法としては、公知のウレタン化反応を用いて合成することができる。例えばポリエ−テルモノオ−ル、ポリエ−テルジオ−ルおよびジイソシアネ−トを２〜１０時間反応して合成できる。例えば、ポリエ−テルモノオ−ル、ポリエ−テルジオ−ルおよびジイソシアネ−トから合成する場合、一括仕込みによる合成方法でもよく、またポリエ−テルジオ−ルとジイソシアネ−トを反応させた後ポリエ−テルモノオ−ルと反応させ合成する方法、あるいはポリエ−テルモノオ−ルとジイソシアネ−トを反応させた後ポリエ−テルジオ−ルと反応させ合成する方法でもよい。反応により副生成物ができる場合があるが副生成物との混合物で使用できる。
【００１７】
反応温度は４０〜１３０℃であり好ましくは７０〜１００℃である。４０℃未満では反応が遅く時間がかかりすぎる欠点があり、また、１３０℃より高い温度では異常な副反応が起こり好ましくない。
【００１８】
これらの反応において、必要に応じて使用される溶剤は活性水素を含有しないことを要し、例えば芳香族系溶剤としてトルエン、キシレンなど、脂肪族系溶剤として石油エ−テル、ｎ−ヘキサンなど、脂環式系溶剤としてシクロヘキサン、シクロヘキサノン、デカリンなど、ハロゲン含有溶剤としてクロロホルム、四塩化炭素、エチレンジクロライド、クロルベンゼンなど、エステル系溶剤として酢酸エチル、酢酸ブチル、酢酸ペンチルなど、ケトン系溶剤としてメチルエチルケトン、ジエチルケトン、メチルイソブチルケトンなどがあげられる。
【００１９】
また必要に応じてウレタン化反応に使用される触媒としては、例えばアミン系化合物としてトリエチルアミン、トリエチレンジアミン、ヘプタメチルジエチレントリアミン、Ｎ−メチルモルホリン、ベンジルトリエチルアンモニウムハイドロオキサイドなど、金属含有化合物として塩化第１スズ、塩化第２スズ、オクチル酸スズ、オクチル酸鉛、ジブチルチンジラウレ−ト、ナフテン酸コバルト、ナフテン酸鉛、ナフテン酸カリウム、三塩化アンチモンなどがあげられる。触媒添加量は仕込み全重量に対し、０．００１〜１重量％である。また添加方法は通常反応初期に加えるが反応中に分割して添加してもよい。
【００２０】
次に本発明の増粘剤組成物を配合してなる水系エマルションおよび水系エマルション塗料について説明する。
【００２１】
本発明の水系エマルションは、増粘剤組成物を水系エマルションに対して０．０１〜１０重量％配合したものであり、好ましくは０．０５〜５重量％配合したものである。配合量が０．０１重量％未満では増粘効果が発現せず、１０重量％を越えると増粘し過ぎる。
【００２２】
本発明の水系エマルション塗料は、増粘剤組成物を水系エマルション塗料に対して０．０１〜１０重量％配合したものであり、好ましくは０．０５〜５重量％配合したものである。配合量が０．０１重量％未満では増粘効果が発現せず、１０重量％を越えると増粘し過ぎる。
【００２３】
本発明の増粘剤組成物の添加方法としては、水系エマルション塗料および水系エマルションに直接配合してもよく、また添加前に適当な粘度になるように水あるいは溶剤で増粘剤を希釈してから配合してもよい。また例えばエマルション塗料に対してはグラインディングステ−ジ（混練工程）に添加してもよく、レットダウンステ−ジ（調整工程）に添加してもよい。
【００２４】
本発明の増粘剤組成物を用いることができる水系エマルションとしてはアクリル系樹脂エマルション、酢酸ビニル系樹脂エマルション、塩化ビニル系樹脂エマルション、アクリルスチレン系樹脂エマルション、シリコン樹脂エマルション、ウレタン樹脂エマルション、エポキシ樹脂エマルション、フッ素樹脂エマルション、ＳＢラテックス、ＳＢＲラテックス、ＡＢＳラテックス、ＮＢＲラテックス、ＣＲラテックスなどがあげられる。
【００２５】
本発明の増粘剤組成物を用いることができる水系エマルション塗料は通常水系エマルション、顔料、水、添加剤からなる。水系エマルションとしてはアクリル系樹脂エマルション、酢酸ビニル系樹脂エマルション、塩化ビニル系樹脂エマルション、アクリルスチレン系樹脂エマルション、シリコン樹脂エマルション、ウレタン樹脂エマルション、エポキシ樹脂エマルション、フッ素樹脂エマルション、ＳＢラテックス、ＳＢＲラテックス、ＡＢＳラテックス、ＮＢＲラテックス、ＣＲラテックスなどがあげられる。顔料としては炭酸カルシウム、酸化チタン、サチンホワイト、硫酸バリウム、タルク、酸化亜鉛、石膏、シリカ、フェライトなどの無機顔料、ポリスチレン系プラスチックピグメントなどの有機顔料があげられる。水系エマルション塗料の製造方法としては、ボ−ルミル、サンドグラインドミルなどを用いて顔料を分散し（グラインディングステ−ジ）、その後水系エマルションを配合（レットダウンステ−ジ）し製造する。
【００２６】
本発明の増粘剤組成物が有用な用途としては水系エマルションおよび水系エマルション塗料以外に、紙、革および繊維工業に対する水系コ−ティング剤、洗浄剤、接着剤、ワックス、磨き剤、化粧品、洗面用化粧品、医薬品、農薬などがあげられる。
【００２７】
【実施例】
以下、実施例により本発明を更に説明するが、本発明はこれに限定されるものではない。文中に部または％とあるのは重量部または重量％の意味である。
【００２８】
（実施例Ａ〜Ｏ）
製造例Ａ〜Ｏにより本発明の実施例Ａ〜Ｏの増粘剤組成物を得た。
【００２９】
（製造例Ａ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル６０００（分子量６０００）を４２０部、α−ナフト−ルにエチレンオキサイドを２０モル付加したポリエ−テルモノオ−ルを１４３部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しヘキサメチレンジイソシアネ−トを２３．５部加え、窒素気流下８５〜９０℃でイソシアネ−ト含量が０％になるまで反応させ（３時間）、淡黄色粘稠液状の反応生成物（実施例Ａ）を得た。
【００３０】
（製造例Ｂ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル６０００（分子量６０００）を４８０部、β−ナフト−ルにエチレンオキサイドを５モル付加したポリエ−テルモノオ−ルを５８部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しトリレンジイソシアネ−トを２７．８部加え、窒素気流下８０〜８５℃でイソシアネ−ト含量が０％になるまで反応させ（２時間）、淡黄色粘稠液状の反応生成物（実施例Ｂ）を得た。
【００３１】
（製造例Ｃ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル６０００（分子量６０００）を４２０部、γ−アントロ−ルにエチレンオキサイドを２０モル付加したポリエ−テルモノオ−ルを１５０部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しキシリレンジイソシアネ−トを２６．３部加え、窒素気流下９０〜９５℃でイソシアネ−ト含量が０％になるまで反応させ（３時間）、淡黄色粘稠液状の反応生成物（実施例Ｃ）を得た。
【００３２】
（製造例Ｄ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル１００００（分子量１００００）を５００部、ヒドロキシピレンにエチレンオキサイドを１０モル付加したポリエ−テルモノオ−ルを６６部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しトリレンジイソシアネ−トを１７．４部加え、窒素気流下８０〜８５℃でイソシアネ−ト含量が０％になるまで反応させ（２時間）、淡黄色粘稠液状の反応生成物（実施例Ｄ）を得た。
【００３３】
（製造例Ｅ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル６０００（分子量６０００）を４８０部、α−ナフト−ルにエチレンオキサイドを３０モル付加したポリエ−テルモノオ−ルを１１７部、α−アントロ−ルにエチレンオキサイドを２０モル付加したポリエ−テルモノオ−ルを８６部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しヘキサメチレンジイソシアネ−トを２６．９部加え、窒素気流下８５〜９０℃でイソシアネ−ト含量が０％になるまで反応させ（３時間）、淡黄色粘稠液状の反応生成物（実施例Ｅ）を得た。
【００３４】
（製造例Ｆ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル６０００（分子量６０００）を４８０部、α−ナフト−ルにエチレンオキサイドを２０モル付加したポリエ−テルモノオ−ルを８２部、ｎ−セチルアルコ−ルにエチレンオキサイドを５０モル付加したポリエ−テルモノオ−ルを１９５部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却し水添キシリレンジイソシアネ−トを３０．７部加え、窒素気流下８５〜９０℃でイソシアネ−ト含量が０％になるまで反応させ（３時間）、淡黄色粘稠液状の反応生成物（実施例Ｆ）を得た。
【００３５】
（製造例Ｇ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル６０００（分子量６０００）を５４０部、β−ナフト−ルにエチレンオキサイドを５モル付加したポリエ−テルモノオ−ルを３３部、炭素数１５のセカンダリ−アルコ−ルにエチレンオキサイドを１０モル付加したポリエ−テルモノオ−ルを６０部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しヘキサメチレンジイソシアネ−トを３０．２部加え、窒素気流下８５〜９０℃でイソシアネ−ト含量が０％になるまで反応させ（３時間）、淡黄色粘稠液状の反応生成物（実施例Ｇ）を得た。
【００３６】
（製造例Ｈ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル１３０００（分子量１３０００）を６５０部、α−ナフト−ルにエチレンオキサイドを２０モル付加したポリエ−テルモノオ−ルを５１部、ノニルフェノ−ルにエチレンオキサイドを５モル付加したポリエ−テルモノオ−ルを２２部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しトリレンジイソシアネ−トを１７．４部加え、窒素気流下８０〜８５℃でイソシアネ−ト含量が０％になるまで反応させ（２時間）、淡黄色粘稠液状の反応生成物（実施例Ｈ）を得た。
【００３７】
（製造例Ｉ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル６０００（分子量６０００）を３６０部、β−ナフト−ルにエチレンオキサイドを５モル付加したポリエ−テルモノオ−ルを２２部、スチレン化フェノ−ルにエチレンオキサイドを１００モル付加したポリエ−テルモノオ−ルを２８２部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しヘキサメチレンジイソシアネ−トを２０．２部加え、窒素気流下８５〜９０℃でイソシアネ−ト含量が０％になるまで反応させ（３時間）、淡黄色粘稠液状の反応生成物（実施例Ｉ）を得た。
【００３８】
（製造例Ｊ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル６０００（分子量６０００）を４２０部、α−ナフト−ルにエチレンオキサイドを２０モル付加したポリエ−テルモノオ−ルを８６部、オクタデシルアルコ−ルにエチレンオキサイドを５０モル付加したポリエ−テルモノオ−ルを１３８部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しキシリレンジイソシアネ−トを２６．３部加え、窒素気流下９０〜９５℃でイソシアネ−ト含量が０％になるまで反応させ（３時間）、淡黄色粘稠液状の反応生成物（実施例Ｊ）を得た。
【００３９】
（製造例Ｋ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル１３０００（分子量１３０００）を５２０部、α−ナフト−ルにエチレンオキサイドを２０モル付加したポリエ−テルモノオ−ルを５７部、ノニルフェノ−ルにエチレンオキサイドを５モル付加したポリエ−テルモノオ−ルを１０．６部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しトリレンジイソシアネ−トを１３．９部加え、窒素気流下８０〜８５℃でイソシアネ−ト含量が０％になるまで反応させ（２時間）、淡黄色粘稠液状の反応生成物（実施例Ｋ）を得た。
【００４０】
（製造例Ｌ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル６０００（分子量６０００）を４２０部、β−ナフト−ルにエチレンオキサイドを５モル付加したポリエ−テルモノオ−ルを３６部、スチレン化フェノ−ルにエチレンオキサイドを５０モル付加したポリエ−テルモノオ−ルを１０５部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しヘキサメチレンジイソシアネ−トを２３．５部加え、窒素気流下８５〜９０℃でイソシアネ−ト含量が０％になるまで反応させ（３時間）、淡黄色粘稠液状の反応生成物（実施例Ｌ）を得た。
【００４１】
（製造例Ｍ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル１０００（分子量１０００）を１５部、α−ナフト−ルにエチレンオキサイドを４５０モル付加したポリエ−テルモノオ−ルを５９８部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しヘキサメチレンジイソシアネ−トを２．５部加え、窒素気流下８５〜９０℃でイソシアネ−ト含量が０％になるまで反応させ（３時間）、淡黄色粘稠液状の反応生成物（実施例Ｍ）を得た。
【００４２】
（製造例Ｎ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、エチレンオキサイドとプロピレンオキサイドを重量比８２：１８の割合でランダム共重合させた分子量６４４０のポリエ−テルジオ−ルを５１５部、β−ナフト−ルにエチレンオキサイドを５モル付加したポリエ−テルモノオ−ルを５８部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しトリレンジイソシアネ−トを１３．９部加え、窒素気流下８０〜８５℃でイソシアネ−ト含量が０％になるまで反応させ（２時間）、淡黄色粘稠液状の反応生成物（実施例Ｎ）を得た。
【００４３】
（製造例Ｏ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、エチレンオキサイドとブチレンオキサイドを重量比８８：１２の割合でランダム共重合させた分子量６０００のポリエ−テルジオ−ルを４８０部、γ−アントロ−ルにエチレンオキサイドを２０モル付加したポリエ−テルモノオ−ルを１７２部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しキシリレンジイソシアネ−トを１５部加え、窒素気流下８５〜９０℃でイソシアネ−ト含量が０％になるまで反応させ（２時間）、淡黄色粘稠液状の反応生成物（実施例Ｏ）を得た。
【００４４】
（比較品Ｐ〜Ｒ）
製造例Ｐ〜Ｒにより本発明の比較例Ｍ〜Ｓの増粘剤組成物を得た。
【００４５】
（製造例Ｐ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル６０００（分子量６０００）を４８０部、ｎ−セチルアルコ−ルにエチレンオキサイドを３０モル付加したポリエ−テルモノオ−ルを２５０部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しヘキサメチレンジイソシアネ−トを２６．９部加え、窒素気流下８５〜９０℃でイソシアネ−ト含量が０％になるまで反応させ（３時間）、淡黄色粘稠液状の反応生成物（比較例Ｐ）を得た。
【００４６】
（製造例Ｑ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル２００００（分子量２００００）を６００部、ノニルフェノ−ルにエチレンオキサイドを５０モル付加したポリエ−テルモノオ−ルを１４５部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しトリレンジイソシアネ−トを１０．４部加え、窒素気流下８０〜８５℃でイソシアネ−ト含量が０％になるまで反応させ（２時間）、淡黄色粘稠液状の反応生成物（比較例Ｑ）を得た。
【００４７】
（製造例Ｒ）
温度計、窒素導入管および高粘度用攪拌機を付した容量１０００ｍｌの４つ口フラスコに、ポリエチレングリコ−ル６０００（分子量６０００）を４８０部、スチレン化フェノ−ルにエチレンオキサイドを５モル付加したポリエ−テルモノオ−ルを１８９部入れ、低圧下（５〜１０ｍｍＨｇ）にて８０〜９０℃で３時間脱水し、系の水分含量を０．０３％とした。次いで、７０℃に冷却しトリレンジイソシアネ−トを２７．８部加え、窒素気流下８０〜８５℃でイソシアネ−ト含量が０％になるまで反応させ（２時間）、淡黄色粘稠液状の反応生成物（比較例Ｒ）を得た。
【００４８】
実施例Ａ〜Ｏ、比較例Ｐ〜Ｒの性能を以下の方法により評価した。結果を表１、表２および表３に示した。
【００４９】
本発明の実施例Ａ〜Ｏ、比較例Ｐ〜Ｒの増粘剤４０部、ブチルトリグリコ−ルエ−テル２０部と水４０部を均一配合し各々の増粘剤溶液を得た。
【００５０】
評価例１：水系エマルション塗料での増粘性評価
二酸化チタン〔石原産業（株）製、Ｒ−６３０〕２５０重量部、分散剤〔サンノプコ（株）製、ＳＮディスパ−サント５０４０〕１０重量部、消泡剤〔ヘンケルＫＧａＡ製、デヒドラン１６２０〕０．５重量部、消泡剤〔サンノプコ（株）製、ＳＮデフォ−マ−３８０〕８重量部、防腐剤〔サンノプコ（株）製、ノプコサイドＳＮ−２１５〕１重量部、水１６０重量部、単層弾性塗料用エマルション（アクリルスチレン系）５３０重量部、エチレングリコ−ル１０重量部、造膜助剤〔イ−ストマンケミカルカンパニ−製、テキサノ−ル〕２０重量部、増粘剤溶液１５重量部なる配合の水系エマルション塗料を作成した。その後作成塗料を２５℃に温調した後、２０ｒｐｍでの粘度（（株）トキメックＢＨ型粘度計）を測定した。
【００５１】
【表１】

【００５２】
評価例２：水系エマルション塗料での調色性評価
評価例１で使用した塗料１００重量部、消泡剤〔サンノプコ（株）製、ＳＮデフォ−マ−３８０〕０．５重量部、色顔料４重量部なる配合で、卓上ホモジナイザ−にて３０００ｒｐｍで１０分攪拌し均一化した。この塗料をロ−ラ−にてスレ−ト板に塗布し、Ａ、タッチアップテスト（１回塗りした塗膜が乾燥後、一部に刷毛による上塗りを行う）Ｂ、ラビングテスト（塗膜面を指でこする）Ｃ、スポッティングテスト（塗膜の別の部分に塗料を少量落とし、スレ−ト板を傾けて塗料を垂れさせる）を行い乾燥後、１回塗りの塗膜面との色の差異を観察した。色顔料として黒顔料（カ−ボンブラク）、青顔料（フタロシアニンブル−）を用いた。
【００５３】
【表２】

【００５４】
【表３】

【００５５】
【発明の効果】
本発明の効果は、調色性に優れた新規な増粘剤組成物並びに当該増粘剤を配合してなる水系エマルション塗料、水系エマルションを提供したことにある。本発明の増粘剤を配合してなる水系エマルション塗料を使用した場合、ロ−ラ−塗装、スプレ−塗装、ハケ塗りなどの塗装方法により塗膜の色目が変わることがなく、また経日による重ね塗りによって色目が変わることがないなど塗膜の美観を阻害しないという特徴を有する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thickener composition. More particularly, the present invention relates to a thickener composition useful for water-based emulsions and water-based emulsion paints.
[0002]
[Prior art]
Conventionally, natural products, semi-synthetic products (such as hydroxyethyl cellulose), and synthetic products are known as thickeners. Among synthetic products, many are known such as polyacrylic acid and polyoxyalkylene glycol derivatives. For example, when these thickeners are used for water-based emulsion paints, natural products, semi-synthetic products, and polyacrylic acid systems have poor leveling properties, and polyoxyalkylene glycol derivatives are used to impart leveling properties. ing. Many known polyoxyalkylene glycol derivatives include urethane-modified polyoxyalkylene glycol, ester-modified polyoxyalkylene glycol, and epoxy-modified polyoxyalkylene glycol. (Japanese Patent Publication No. 52-25840, Japanese Patent Publication No. 1-55292, Japanese Patent Application Laid-Open No. 58-213074, Japanese Patent Application Laid-Open No. 58-164671)
[0003]
[Problems to be solved by the invention]
Conventional polyoxyalkylene glycol derivatives have the drawback of inhibiting the toning properties of the paint when used in aqueous emulsion paints. For example, when applying a water-based single-layer elastic paint blended with a conventional thickener, the color of the coating changes depending on the coating method such as roller coating, spray coating, brush coating, etc. There was a defect that obstructed the aesthetics of the coating film, such as the color change depending on.
[0004]
[Means for Solving the Problems]
An object of this invention is to provide the thickener composition excellent in toning property, and the water-system emulsion and water-system emulsion coating material which mix | blend the said thickener.
[0005]
As a result of intensive studies, the present inventors have found that a polyether compound having a specific structure meets the above-mentioned purpose, and have reached the present invention. That is, the thickener composition of the present invention is characterized by containing one or more compounds represented by the general formula (1).

[In the formula, X and Z are groups selected from a naphthyl group, an anthryl group, a pyrenyl group, and a hydrocarbon group having 6 to 24 carbon atoms, and at least one of X and Z is a naphthyl group, an anthryl group, or a pyrenyl group. The group to be selected. Y is a divalent organic residue derived from a diisocyanate compound, OR, OR ′ and OR ″ are oxyalkylene groups having 2 to 4 carbon atoms, and a, b and d are integers of 1 to 500. And c is an integer of 1 or more.]
[0006]
Moreover, this invention is an aqueous | water-based emulsion formed by mix | blending 0.01-10 weight% of said thickener composition.
[0007]
Furthermore, the present invention is a water-based emulsion paint obtained by blending the above thickener composition in an amount of 0.01 to 10% by weight.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
X and Z in the general formula (1) of the present invention are groups selected from a naphthyl group, an anthryl group, a pyrenyl group, and a hydrocarbon group having 6 to 24 carbon atoms, and at least one of X and Z is a naphthyl group, It is a group selected from an anthryl group and a pyrenyl group. Examples of combinations of X and Z include, for example, when both are naphthyl groups, when both are anthryl groups, when both are pyrenyl groups, when one is a naphthyl group and the other is an anthryl group, one is a naphthyl group and the other is pyrenyl. Group, when one is an anthryl group and the other is a pyrenyl group, when one is a naphthyl group and the other is a hydrocarbon group having 6 to 24 carbon atoms, one is an anthryl group and the other is a hydrocarbon having 6 to 24 carbon atoms. In the case of a group, one is a pyrenyl group and the other is a hydrocarbon group having 6 to 24 carbon atoms. Examples of the hydrocarbon group having 6 to 24 carbon atoms include a saturated hydrocarbon group, an unsaturated hydrocarbon group, a linear hydrocarbon group, a branched hydrocarbon group, an aliphatic hydrocarbon group, a cyclic hydrocarbon group, and an aromatic Group hydrocarbon group and the like. Of these, when both are naphthyl groups, one is a naphthyl group and the other is an anthryl group, one is a naphthyl group and the other is a pyrenyl group, one is a naphthyl group and the other is a carbon atom having 6 to 24 carbon atoms. This is the case with a hydrogen group.
[0009]
Y in the general formula (1) of the present invention is a divalent organic residue derived from a diisocyanate compound, and is not particularly limited as a diisocyanate compound. Examples of the diisocyanate compound include an aliphatic diisocyanate compound, an aromatic diisocyanate compound, an alicyclic diisocyanate compound, and the like.
[0010]
Examples of the aliphatic diisocyanate compound include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and hexamethylene diisocyanate. Methylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethyl Pentane diisocyanate, 3-methoxyhexane diisocyanate, 2,2,4-trimethylpentane diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether Terdiisocyanate, metaxylylene diisocyanate, paraxylylene diisote Ane - DOO, tetramethyl xylylene diisocyanate - such DOO and the like.
[0011]
Examples of aromatic diisocyanate compounds include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and dimethyl. Benzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 3,3'-dimethoxybiphenyl diisocyanate, naphthalene Diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate 4,4′-dimethoxydiphenylmethane-3,3′-diisocyanate, 4,4′-diethoxydiphe Rumetan 3,3' diisocyanate - DOO, 2,2'-dimethyl-5,5'-dimethoxy-4,4'-diisocyanate - such DOO and the like.
[0012]
Examples of the alicyclic diisocyanate compound include cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate and the like. .
[0013]
In the general formula (1) of the present invention, OR, OR ′ and OR ″ are oxyalkylene groups having 2 to 4 carbon atoms. When the carbon number is less than 2 and exceeds 4, the viscosity increases. Examples of the oxyalkylene group 4 include an oxyethylene group, an oxypropylene group, an oxybutylene group, etc. Of these, the oxyethylene group is essential, and the proportion of the oxyethylene group is preferably 60% by weight of the total oxyalkylene group. % Or more, more preferably 80% by weight or more of all oxyalkylene groups, particularly preferably 90% by weight or more of all oxyalkylene groups. , OR "may be one in which two or more oxyalkylene groups are connected in a block or randomly. (OR) a, (OR ′) b, and (OR ″) d may be the same or different combinations.
[0014]
In the general formula (1) of the present invention, a, b, and d each represent a repeating unit of OR, OR ′, OR ″, an integer of 1 to 500, preferably 2 to 400, and more preferably. It is 2 to 300. If it is less than 1 and exceeds 500, the thickening is reduced.
[0015]

Represents a repeating unit, and is an integer of 1 or more.
[0016]
As a method of synthesizing the thickener of the present invention, it can be synthesized using a known urethanization reaction. For example, it can be synthesized by reacting polyether monool, polyether diol and diisocyanate for 2 to 10 hours. For example, when synthesizing from polyether monool, polyether terdiol and diisocyanate, a synthesis method by batch preparation may be used, and after reacting the polyether terdiol and diisocyanate, the polyether monool is reacted. It may be a method of synthesizing by reacting with benzene, or a method of synthesizing by reacting with polyether monool and diisocyanate and then reacting with polyether diol. The reaction may produce a by-product, but it can be used in a mixture with the by-product.
[0017]
The reaction temperature is 40 to 130 ° C, preferably 70 to 100 ° C. If it is less than 40 ° C., there is a drawback that the reaction is slow and takes too much time, and if it is higher than 130 ° C., an abnormal side reaction occurs, which is not preferable.
[0018]
In these reactions, it is necessary that the solvent used as necessary does not contain active hydrogen, such as toluene and xylene as aromatic solvents, petroleum ether, n-hexane, etc. as aliphatic solvents, Cyclohexane, cyclohexanone, decalin, etc. as alicyclic solvents, chloroform, carbon tetrachloride, ethylene dichloride, chlorobenzene, etc. as halogen-containing solvents, ethyl acetate, butyl acetate, pentyl acetate, etc. as ester solvents, methyl ethyl ketone as ketone solvents, Examples thereof include diethyl ketone and methyl isobutyl ketone.
[0019]
Moreover, as a catalyst used for a urethanation reaction as needed, for example, stannous chloride as a metal-containing compound such as triethylamine, triethylenediamine, heptamethyldiethylenetriamine, N-methylmorpholine, benzyltriethylammonium hydroxide as an amine compound. Stannic chloride, tin octylate, lead octylate, dibutyltin dilaurate, cobalt naphthenate, lead naphthenate, potassium naphthenate, antimony trichloride and the like. The amount of the catalyst added is 0.001 to 1% by weight based on the total weight of the charge. Although the addition method is usually added at the initial stage of the reaction, it may be added in portions during the reaction.
[0020]
Next, the water-based emulsion and water-based emulsion paint formed by blending the thickener composition of the present invention will be described.
[0021]
The aqueous emulsion of the present invention contains 0.01 to 10% by weight, preferably 0.05 to 5% by weight, of the thickener composition based on the aqueous emulsion. If the blending amount is less than 0.01% by weight, the thickening effect is not exhibited, and if it exceeds 10% by weight, the viscosity increases excessively.
[0022]
The water-based emulsion paint of the present invention contains 0.01 to 10% by weight, preferably 0.05 to 5% by weight of the thickener composition based on the water-based emulsion paint. If the blending amount is less than 0.01% by weight, the thickening effect is not exhibited, and if it exceeds 10% by weight, the viscosity increases excessively.
[0023]
As a method for adding the thickener composition of the present invention, the thickener composition may be directly blended into the water-based emulsion paint and the water-based emulsion, or the thickener is diluted with water or a solvent to obtain an appropriate viscosity before addition. You may mix from. Further, for example, it may be added to the grinding stage (kneading step) for the emulsion paint, or may be added to the let-down stage (adjustment step).
[0024]
The water-based emulsion in which the thickener composition of the present invention can be used is an acrylic resin emulsion, vinyl acetate resin emulsion, vinyl chloride resin emulsion, acrylic styrene resin emulsion, silicon resin emulsion, urethane resin emulsion, epoxy resin Emulsions, fluororesin emulsions, SB latex, SBR latex, ABS latex, NBR latex, CR latex and the like can be mentioned.
[0025]
The water-based emulsion paint in which the thickener composition of the present invention can be used usually comprises a water-based emulsion, a pigment, water and additives. Water-based emulsions include acrylic resin emulsion, vinyl acetate resin emulsion, vinyl chloride resin emulsion, acrylic styrene resin emulsion, silicon resin emulsion, urethane resin emulsion, epoxy resin emulsion, fluororesin emulsion, SB latex, SBR latex, ABS Latex, NBR latex, CR latex and the like can be mentioned. Examples of the pigment include inorganic pigments such as calcium carbonate, titanium oxide, satin white, barium sulfate, talc, zinc oxide, gypsum, silica, and ferrite, and organic pigments such as polystyrene-based plastic pigments. As a method for producing a water-based emulsion paint, a ball mill, a sand grind mill or the like is used to disperse the pigment (grinding stage), and then a water-based emulsion is blended (let-down stage).
[0026]
In addition to water-based emulsions and water-based emulsion paints, the thickener composition of the present invention is useful for water-based coating agents for paper, leather and textile industries, cleaning agents, adhesives, waxes, polishing agents, cosmetics, and face wash. Cosmetics, pharmaceuticals, and agricultural chemicals.
[0027]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In the text, “part” or “%” means “part by weight” or “% by weight”.
[0028]
(Examples A to O)
The thickener compositions of Examples A to O of the present invention were obtained by Production Examples A to O.
[0029]
(Production Example A)
Polyethylene glycol 6000 (molecular weight 6000) 420 parts and α-naphthol 20 moles of ethylene oxide were added to a 1000 ml four-necked flask equipped with a thermometer, nitrogen inlet tube and stirrer for high viscosity. -143 parts of termonool was put and dehydrated under low pressure (5 to 10 mmHg) at 80 to 90 ° C for 3 hours to make the water content of the system 0.03%. Next, the mixture was cooled to 70 ° C., 23.5 parts of hexamethylene diisocyanate was added, and the reaction was continued at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). A liquid reaction product (Example A) was obtained.
[0030]
(Production Example B)
Polyethylene glycol 6000 (molecular weight 6000) 480 parts and β-naphthol 5 mol of ethylene oxide were added to a 1000 ml four-necked flask equipped with a thermometer, nitrogen inlet tube and stirrer for high viscosity. -58 parts of termonool was added and dehydrated under low pressure (5 to 10 mmHg) at 80 to 90 ° C for 3 hours to adjust the water content of the system to 0.03%. Next, the mixture was cooled to 70 ° C., 27.8 parts of tolylene diisocyanate was added, and the reaction was carried out at 80 to 85 ° C. under a nitrogen stream until the isocyanate content became 0% (2 hours). The reaction product (Example B) was obtained.
[0031]
(Production Example C)
Polyethylene glycol 6000 (molecular weight 6000) 420 parts and γ-anthrol 20 moles of ethylene oxide were added to a 1000 ml four-necked flask equipped with a thermometer, nitrogen inlet tube and stirrer for high viscosity. -150 parts of termonool was added and dehydrated under low pressure (5 to 10 mmHg) at 80 to 90 ° C for 3 hours to make the water content of the system 0.03%. Next, the mixture was cooled to 70 ° C., 26.3 parts of xylylene diisocyanate was added, and the reaction was continued at 90 to 95 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). The reaction product (Example C) was obtained.
[0032]
(Production Example D)
Polyether monoo in which 500 parts of polyethylene glycol 10000 (molecular weight 10,000) and 10 moles of ethylene oxide are added to hydroxypyrene in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. 66 parts was added and dehydrated under low pressure (5 to 10 mmHg) at 80 to 90 ° C. for 3 hours to adjust the water content of the system to 0.03%. Next, the mixture was cooled to 70 ° C., 17.4 parts of tolylene diisocyanate was added, and the mixture was allowed to react at 80 to 85 ° C. under a nitrogen stream until the isocyanate content became 0% (2 hours). The reaction product (Example D) was obtained.
[0033]
(Production Example E)
Polyethylene glycol 6000 (molecular weight: 6000) added to 480 parts of polyethylene glycol 6000 (molecular weight: 6000) and 30 mol of ethylene oxide to α-naphthol in a 1000 ml four-necked flask equipped with a thermometer, nitrogen inlet tube and stirrer for high viscosity. -117 parts of termonool, 86 parts of polyether monool having 20 moles of ethylene oxide added to α-anthrol, and dehydrated at 80-90 ° C under low pressure (5-10 mmHg) for 3 hours, The water content of the system was 0.03%. Next, the mixture was cooled to 70 ° C., 26.9 parts of hexamethylene diisocyanate was added, and the reaction was continued at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). A liquid reaction product (Example E) was obtained.
[0034]
(Production Example F)
Polyethylene glycol 6000 (molecular weight 6000) 480 parts and α-naphthol 20 moles of ethylene oxide were added to a 1000 ml four-necked flask equipped with a thermometer, nitrogen inlet tube and stirrer for high viscosity. -82 parts of termonool, 195 parts of polyether monool obtained by adding 50 mol of ethylene oxide to n-cetyl alcohol, and dehydrating at 80-90 ° C under low pressure (5-10 mmHg) for 3 hours, The water content of the system was 0.03%. Next, the mixture was cooled to 70 ° C., 30.7 parts of hydrogenated xylylene diisocyanate was added, and the reaction was continued at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). A viscous liquid reaction product (Example F) was obtained.
[0035]
(Production Example G)
Polyethylene glycol 6000 (molecular weight 6000) added to 540 parts polyethylene glycol 6000 (molecular weight 6000 parts) and 5 moles of ethylene oxide to β-naphthol in a 1000 ml four-necked flask equipped with a thermometer, nitrogen inlet tube and high viscosity stirrer. -33 parts of termonool, 60 parts of polyether monool having 10 moles of ethylene oxide added to a secondary alcohol having 15 carbon atoms, and 3 at 80 to 90 ° C under low pressure (5 to 10 mmHg). The water content of the system was adjusted to 0.03% by time dehydration. Next, the mixture was cooled to 70 ° C., 30.2 parts of hexamethylene diisocyanate was added, and the mixture was reacted at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). A liquid reaction product (Example G) was obtained.
[0036]
(Production Example H)
Polyethylene glycol 13000 (molecular weight 13000) 650 parts polyethylene glycol 20 moles of ethylene oxide added to a 1000 ml four-necked flask equipped with a thermometer, nitrogen inlet tube and high viscosity stirrer. -51 parts of termonool and 22 parts of polyether monool obtained by adding 5 moles of ethylene oxide to nonylphenol were dehydrated at 80-90 ° C for 3 hours under low pressure (5-10 mmHg). The water content was 0.03%. Next, the mixture was cooled to 70 ° C., 17.4 parts of tolylene diisocyanate was added, and the mixture was allowed to react at 80 to 85 ° C. under a nitrogen stream until the isocyanate content became 0% (2 hours). Of the reaction product (Example H).
[0037]
(Production Example I)
Polyethylene glycol obtained by adding 360 parts of polyethylene glycol 6000 (molecular weight 6000) and 5 mol of ethylene oxide to β-naphthol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. -22 parts of termonool, 282 parts of polyether monool obtained by adding 100 mol of ethylene oxide to styrenated phenol, and dehydrated at 80-90 ° C for 3 hours under low pressure (5-10 mmHg); The water content of the system was 0.03%. Next, the mixture was cooled to 70 ° C., 20.2 parts of hexamethylene diisocyanate was added, and the reaction was continued at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). A liquid reaction product (Example I) was obtained.
[0038]
(Production Example J)
Polyethylene glycol 6000 (molecular weight 6000) 420 parts and α-naphthol 20 moles of ethylene oxide were added to a 1000 ml four-necked flask equipped with a thermometer, nitrogen inlet tube and stirrer for high viscosity. -86 parts of termonool, 138 parts of polyether monool obtained by adding 50 mol of ethylene oxide to octadecyl alcohol, dehydrated at 80 to 90 ° C for 3 hours under low pressure (5 to 10 mmHg), The water content was 0.03%. Next, the mixture was cooled to 70 ° C., 26.3 parts of xylylene diisocyanate was added, and the reaction was continued at 90 to 95 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). The reaction product (Example J) was obtained.
[0039]
(Production Example K)
Polyethylene glycol in which 520 parts of polyethylene glycol 13000 (molecular weight 13000) and 20 mol of ethylene oxide were added to α-naphthol were added to a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. -57 parts of termonool, 10.6 parts of polyether monool obtained by adding 5 moles of ethylene oxide to nonylphenol, and dehydrated at 80-90 ° C under low pressure (5-10 mmHg) for 3 hours, The water content of the system was 0.03%. Next, the mixture was cooled to 70 ° C., 13.9 parts of tolylene diisocyanate was added, and the reaction was carried out at 80 to 85 ° C. under a nitrogen stream until the isocyanate content became 0% (2 hours). The reaction product (Example K) was obtained.
[0040]
(Production Example L)
Polyethylene glycol 6000 (molecular weight 6000) 420 parts and β-naphthol 5 moles of ethylene oxide were added to a 1000 ml four-necked flask equipped with a thermometer, nitrogen inlet tube and stirrer for high viscosity. -36 parts of termonool, 105 parts of polyether monool having 50 moles of ethylene oxide added to styrenated phenol, dehydrated at 80-90 ° C for 3 hours under low pressure (5-10 mmHg), The water content of the system was 0.03%. Next, the mixture was cooled to 70 ° C., 23.5 parts of hexamethylene diisocyanate was added, and the reaction was continued at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). A liquid reaction product (Example L) was obtained.
[0041]
(Production Example M)
Polyethylene glycol in which 15 parts of polyethylene glycol 1000 (molecular weight 1000) and 450 moles of ethylene oxide were added to α-naphthol in a 1000 ml four-necked flask equipped with a thermometer, nitrogen inlet tube and stirrer for high viscosity. -598 parts of termonool was added and dehydrated under low pressure (5 to 10 mmHg) at 80 to 90 ° C for 3 hours to make the water content of the system 0.03%. Next, the mixture was cooled to 70 ° C., 2.5 parts of hexamethylene diisocyanate was added, and the mixture was reacted at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). A liquid reaction product (Example M) was obtained.
[0042]
(Production Example N)
Polyetherdiol having a molecular weight of 6440 obtained by random copolymerization of ethylene oxide and propylene oxide in a weight ratio of 82:18 to a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. Was added to 58 parts of polyether monool obtained by adding 5 moles of ethylene oxide to β-naphthol, and dehydrated at 80 to 90 ° C. for 3 hours under low pressure (5 to 10 mmHg). Was 0.03%. Next, the mixture was cooled to 70 ° C., 13.9 parts of tolylene diisocyanate was added, and the reaction was carried out at 80 to 85 ° C. under a nitrogen stream until the isocyanate content became 0% (2 hours). The reaction product (Example N) was obtained.
[0043]
(Production Example O)
Polyetherdiol having a molecular weight of 6000, obtained by random copolymerization of ethylene oxide and butylene oxide in a weight ratio of 88:12 to a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. 480 parts, 172 parts of polyether monool having 20 moles of ethylene oxide added to γ-anthrol, dehydrated at 80 to 90 ° C. for 3 hours under low pressure (5 to 10 mmHg), and water content of the system Was 0.03%. Next, it is cooled to 70 ° C., 15 parts of xylylene diisocyanate is added, and the reaction is carried out in a nitrogen stream at 85 to 90 ° C. until the isocyanate content becomes 0% (2 hours). The product (Example O) was obtained.
[0044]
(Comparison products P ~ R)
Thickener compositions of Comparative Examples MS of the present invention were obtained by Production Examples PR.
[0045]
(Production Example P)
Polyethylene glycol 6000 (molecular weight 6000) added to 480 parts of polyethylene glycol 6000 (molecular weight 6000) and 30 mol of ethylene oxide to n-cetyl alcohol in a 1000 ml four-necked flask equipped with a thermometer, nitrogen inlet tube and stirrer for high viscosity. -250 parts of termonool was added and dehydrated under low pressure (5 to 10 mmHg) at 80 to 90 ° C for 3 hours to make the water content of the system 0.03%. Next, the mixture was cooled to 70 ° C., 26.9 parts of hexamethylene diisocyanate was added, and the reaction was continued at 85 to 90 ° C. under a nitrogen stream until the isocyanate content became 0% (3 hours). A liquid reaction product (Comparative Example P) was obtained.
[0046]
(Production Example Q)
Polyether monoo in which 600 parts of polyethylene glycol 20000 (molecular weight 20000) and 50 moles of ethylene oxide were added to nonylphenol in a 1000 ml four-necked flask equipped with a thermometer, nitrogen inlet tube and stirrer for high viscosity. -145 parts was added and dehydrated under low pressure (5 to 10 mmHg) at 80 to 90 ° C for 3 hours to make the water content of the system 0.03%. Next, the mixture was cooled to 70 ° C., 10.4 parts of tolylene diisocyanate was added, and the reaction was carried out at 80 to 85 ° C. under a nitrogen stream until the isocyanate content became 0% (2 hours). The reaction product (Comparative Example Q) was obtained.
[0047]
(Production Example R)
Polyethylene having 4,000 parts of polyethylene glycol 6000 (molecular weight 6000) and 5 mol of ethylene oxide added to styrenated phenol in a 1000 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer for high viscosity. -189 parts of termonool was added and dehydrated under low pressure (5 to 10 mmHg) at 80 to 90 ° C for 3 hours to make the water content of the system 0.03%. Next, the mixture was cooled to 70 ° C., 27.8 parts of tolylene diisocyanate was added, and the reaction was carried out at 80 to 85 ° C. under a nitrogen stream until the isocyanate content became 0% (2 hours). The reaction product (Comparative Example R) was obtained.
[0048]
The performances of Examples A to O and Comparative Examples P to R were evaluated by the following methods. The results are shown in Table 1, Table 2 and Table 3.
[0049]
40 parts of the thickener of Examples A to O and Comparative Examples P to R of the present invention, 20 parts of butyltriglycol ether and 40 parts of water were uniformly blended to obtain respective thickener solutions.
[0050]
Evaluation Example 1: Evaluation of Thickening with Water-based Emulsion Paint Titanium Dioxide [Ishihara Sangyo Co., Ltd., R-630] 250 parts by weight, Dispersant [San Nopco Co., Ltd., SN Disperser Santo 5040] 10 parts by weight 0.5 parts by weight of foaming agent [manufactured by Henkel KGaA, Dehydran 1620], 8 parts by weight of antifoaming agent [manufactured by San Nopco, SN deformer-380], preservative [manufactured by San Nopco, Nopcoside SN-215 1 part by weight, 160 parts by weight of water, 530 parts by weight of emulsion for single-layer elastic paint (acrylic styrene), 10 parts by weight of ethylene glycol, film-forming aid [Texanol, manufactured by Eastman Chemical Company] A water-based emulsion paint having a composition of 20 parts by weight and 15 parts by weight of a thickener solution was prepared. Thereafter, the temperature of the prepared paint was adjusted to 25 ° C., and then the viscosity at 20 rpm (Tokimec BH viscometer) was measured.
[0051]
[Table 1]

[0052]
Evaluation Example 2: Toning Evaluation with Water-Based Emulsion Paint 100 parts by weight of paint used in Evaluation Example 1, antifoaming agent [manufactured by Sannopco, SN deformer-380] 0.5 part by weight, color pigment 4 In a composition of parts by weight, the mixture was homogenized by stirring at 3000 rpm for 10 minutes with a desktop homogenizer. This paint is applied to a slate plate with a roller, and A, a touch-up test (the coated film once coated is dried and then partially coated with a brush) B, a rubbing test (coated surface) C) Spotting test (drop a small amount of paint on another part of the paint film, tilt the plate and let the paint sag), and after drying, the color of the paint film once applied The difference was observed. A black pigment (carbon black) and a blue pigment (phthalocyanine blue) were used as color pigments.
[0053]
[Table 2]

[0054]
[Table 3]

[0055]
【The invention's effect】
The effect of the present invention is to provide a novel thickener composition excellent in toning properties, and an aqueous emulsion paint and aqueous emulsion formed by blending the thickener. When the water-based emulsion paint comprising the thickener of the present invention is used, the color of the coating film does not change depending on the coating method such as roller coating, spray coating, brush coating, etc. It has the feature that it does not hinder the aesthetics of the coating film, such as the color does not change by repeated coating.

Claims (3)

A thickener composition comprising one or more compounds represented by the general formula (1).

[In the formula, X and Z are groups selected from a naphthyl group, an anthryl group, a pyrenyl group, and a hydrocarbon group having 6 to 24 carbon atoms, and at least one of X and Z is a naphthyl group, an anthryl group, or a pyrenyl group. The group to be selected. Y is a divalent organic residue derived from a diisocyanate compound, OR, OR ′ and OR ″ are oxyalkylene groups having 2 to 4 carbon atoms, and a, b and d are integers of 1 to 500. And c is an integer of 1 or more.] An aqueous emulsion comprising 0.01 to 10% by weight of the thickener composition according to claim 1. A water-based emulsion paint comprising 0.01 to 10% by weight of the thickener composition according to claim 1.