JP3807108B2 - Radiation sensitive composition for color filter - Google Patents

Description

【００３６】
前記多官能性単量体は、単独でまたは２種以上を混合して使用することができる。
また、本発明においては、場合により、前記多官能性単量体と共に、単官能性単量体を併用することもできる。
このような単官能性単量体の具体例としては、共重合体（Ｂ１）について例示した単官能性単量体（ｂ２）や前記他の単官能性単量体のほか、市販品として、Ｍ−５４００、Ｍ−５６００（商品名、東亞合成（株）製）等を挙げることができる。
これらの単官能性単量体は、単独でまたは２種以上を混合して使用することができる。
前記単官能性単量体の使用割合は、多官能性単量体と単官能性単量体との合計に対して、通常、９０重量％以下、好ましくは０〜５０重量％である。この場合、単官能性単量体の使用割合が９０重量％を超えると、得られる画素の強度や表面平滑性が不十分となるおそれがある。
本発明における多官能性単量体と単官能性単量体との合計の使用量は、（Ｂ）アルカリ可溶性樹脂１００重量部に対して、通常、５〜５００重量部、好ましくは２０〜３００重量部である。この場合、前記使用量が５重量部未満では、画素の強度や表面平滑性が低下する傾向があり、一方５００重量部を超えると、例えば、アルカリ現像性が低下したり、未露光部の基板上あるいは遮光層上に地汚れ、膜残り等が発生しやすくなる傾向がある。
【００３７】
（Ｄ）光重合開始剤
本発明における光重合開始剤とは、可視光線、紫外線、遠紫外線、電子線、Ｘ線等の露光により分解または結合の開裂を生じ、ラジカル、カチオン、アニオン等の、前記（Ｃ）多官能性単量体の重合を開始することができる活性種を発生する化合物を意味する。
このような光重合開始剤としては、下記式（２）、式（３）または式（４）で表される主要骨格を少なくとも１種有するイミダゾール系化合物のほか、ベンゾイン系化合物、アセトフェノン系化合物、ベンゾフェノン系化合物、α−ジケトン系化合物、多核キノン系化合物、キサントン系化合物、トリアジン系化合物等を挙げることができる。
【００３８】
【化２】

【００３９】
【化３】

【００４０】
【化４】

【００４１】
前記ビイミダゾール系化合物の具体例としては、
２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラキス（４−メトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラキス（４−フェノキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５，５’−テトラキス（４−メトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５，５’−テトラキス（４−フェノキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２，４，６−トリクロロフェニル）−４，４’，５，５’−テトラキス（４−メトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２，４，６−トリクロロフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２，４，６−トリクロロフェニル）−４，４’，５，５’−テトラキス（４−フェノキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−ブロモフェニル）−４，４’，５，５’−テトラキス（４−メトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−ブロモフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−ブロモフェニル）−４，４’，５，５’−テトラキス（４−フェノキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２，４−ジブロモフェニル）−４，４’，５，５’−テトラキス（４−メトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２，４−ジブロモフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２，４−ジブロモフェニル）−４，４’，５，５’−テトラキス（４−フェノキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２，４，６−トリブロモフェニル）−４，４’，５，５’−テトラキス（４−メトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２，４，６−トリブロモフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２，４，６−トリブロモフェニル）−４，４’，５，５’−テトラキス（４−フェノキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−シアノフェニル）−４，４’，５．５’−テトラキス（４−メトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−シアノフェニル）−４，４’，５．５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−シアノフェニル）−４，４’，５，５’−テトラキス（４−フェノキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−メチルフェニル）−４，４’，５，５’−テトラキス（４−メトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−メチルフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−メチルフェニル）−４，４’，５，５’−テトラキス（４−フェノキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−エチルフェニル）−４，４’，５，５’−テトラキス（４−メトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−エチルフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−エチルフェニル）−４，４’，５，５’−テトラキス（４−フェノキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−フェニルフェニル）−４，４’，５，５’−テトラキス（４−メトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−フェニルフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、
２，２’−ビス（２−フェニルフェニル）−４，４’，５，５’−テトラキス（４−フェノキシカルボニルフェニル）−１，２’−ビイミダゾール、
【００４２】
２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２，４，６−トリクロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２−ブロモフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２，４−ジブロモフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２，４，６−トリブロモフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２−シアノフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２，４−ジシアノフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２，４，６−トリシアノフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２−メチルフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２，４−ジメチルフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２，４，６−トリメチルフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２−エチルフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２，４−ジエチルフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２，４，６−トリエチルフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２−フェニルフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２，４−ジフェニルフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、
２，２’−ビス（２，４，６−トリフェニルフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール
等を挙げることができる。
【００４３】
これらのビイミダゾール系化合物のうち、特に、２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、２，２’−ビス（２−ブロモフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、２，２’−ビス（２，４，６−トリクロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、２，２’−ビス（２，４−ジブロモフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾールおよび２，２’−ビス（２，４，６−トリブロモフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾールが好ましい。
前記ビイミダゾール系化合物は、溶剤に対する溶解性に優れ、未溶解物、析出物等の異物を生じることがなく、しかも感度が高く、少ないエネルギー量の露光により硬化反応を十分進行させるとともに、コントラストが高く、未露光部で硬化反応が生じることがないため、露光後の塗膜は、現像液に対して不溶性の硬化部分と、現像液に対して高い溶解性を有する未硬化部分とに明確に区分され、これにより、アンダーカットのない画素パターンが所定の配列に従って配置された高精細な画素アレイを形成することができる。
【００４４】
また、前記ベンゾイン系化合物の具体例としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインｉ−プロピルエーテル、ベンゾインｉ−ブチルエーテル、メチル−２−ベンゾイルベンゾエート等を挙げることができる。
前記アセトフェノン系化合物の具体例としては、２，２−ジメトキシ−２−フェニルアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−（４−ｉ−プロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、２，２−ジメトキシアセトフェノン、２，２−ジエトキシアセトフェノン、２−メチル−（４−メチルチオフェニル）−２−モルフォリノ−１−プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン等を挙げることができる。
前記ベンゾフェノン系化合物の具体例としては、４，４’−ビス（ジメチルアミノ）ベンゾフェノン、４，４’−ビス（ジエチルアミノ）ベンゾフェノン等を挙げることができる。
前記α−ジケトン系化合物の具体例としては、ジアセチル、ジベンゾイル、メチルベンゾイルホルメート等を挙げることができる。
前記多核キノン系化合物の具体例としては、アントラキノン、２−エチルアントラキノン、２−ｔ−ブチルアントラキノン、１，４−ナフトキノン等を挙げることができる。
前記キサントン系化合物の具体例としては、キサントン、チオキサントン、２−クロロチオキサントン等を挙げることができる。
前記トリアジン系化合物の具体例としては、１，３，５−トリス（トリクロロメチル）−ｓ−トリアジン、１，３−ビス（トリクロロメチル）−５−（２’−クロロフェニル）−ｓ−トリアジン、１，３−ビス（トリクロロメチル）−５−（４’−クロロフェニル）−ｓ−トリアジン、１，３−ビス（トリクロロメチル）−５−（２’−メトキシフェニル）−ｓ−トリアジン、１，３−ビス（トリクロロメチル）−５−（４’−メトキシフェニル）−ｓ−トリアジン、２−（２’−フリルエチリデン）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（４’−メトキシスチリル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（３’，４’−ジメトキシスチリル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（４’−メトキシナフチル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（２’−ブロモ−４’−メチルフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（２’−チオフェニルエチリデン）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン等を挙げることができる。
【００４５】
これらの光重合開始剤は、単独でまたは２種以上を混合して使用することができる。
本発明における光重合開始剤の使用量は、（Ｃ）多官能性単量体と場合により使用される単官能性単量体の合計１００重量部に対して、通常、０．０１〜２００重量部、好ましくは１〜１２０重量部、特に好ましくは１〜１００重量部である。この場合、光重合開始剤の使用量が０．０１重量部未満では、露光による硬化が不十分となり、画素パターンが所定の配列に従って配置された画素アレイを得ることが困難となるおそれがあり、一方２００重量部を超えると、形成された画素が現像時に基板から脱落しやすくなり、また未露光部の基板上あるいは遮光層上に地汚れ、膜残り等を生じやすくなる。
さらに、本発明においては、前記光重合開始剤と共に、必要に応じて、増感剤、硬化促進剤あるいは高分子光架橋・増感剤の１種以上を併用することもできる。
【００４６】
本発明においては、光重合開始剤として、特に、ビイミダゾール系化合物とアセトフェノン系化合物および／またはベンゾフェノン系化合物とを組み合わせて使用することが、形成された画素が現像時に基板から脱落し難く、画素強度および感度も高い点で好ましい。
本発明において、光重合開始剤としてビイミダゾール系化合物と他の成分とを併用する場合、他の成分の使用割合は、光重合開始剤全体の８０重量％以下であることが好ましい。
ここで、本発明における特に好ましい光重合開始剤を、その構成成分の組み合わせとして示すと、下記のものを挙げることができる。
２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール／４，４’−ビス（ジエチルアミノ）ベンゾフェノン、
２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール／４，４’−ビス（ジエチルアミノ）ベンゾフェノン／２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン、
２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール／４，４’−ビス（ジエチルアミノ）ベンゾフェノン／１−ヒドロキシシクロヘキシルフェニルケトン、
２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール／４，４’−ビス（ジエチルアミノ）ベンゾフェノン、
２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール／４，４’−ビス（ジエチルアミノ）ベンゾフェノン／２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン、
２，２’−ビス（２，４−ジブロモフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール／４，４’−ビス（ジエチルアミノ）ベンゾフェノン／２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン、
２，２’−ビス（２，４−ジブロモフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール／４，４’−ビス（ジエチルアミノ）ベンゾフェノン／１−ヒドロキシシクロヘキシルフェニルケトン。
【００４７】
添加剤
本発明のカラーフィルタ用感放射線性組成物は、必要に応じて種々の添加剤を含有することもできる。
前記添加剤としては、カラーフィルタ用感放射線性組成物のアルカリ現像液に対する溶解性をより改善し、かつ現像後の未溶解物の残存をより抑制する作用を示す有機酸を挙げることができる。
このような有機酸としては、分子量が１，０００以下である、脂肪族カルボン酸あるいはフェニル基含有カルボン酸が好ましい。
前記脂肪族カルボン酸の具体例としては、
ぎ酸、酢酸、プロピオン酸、酪酸、吉草酸、ピバル酸、カプロン酸、ジエチル酢酸、エナント酸、カプリル酸等のモノカルボン酸類；
しゅう酸、マロン酸、こはく酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ブラシル酸、メチルマロン酸、エチルマロン酸、ジメチルマロン酸、メチルこはく酸、テトラメチルこはく酸、シクロヘキサンジカルボン酸、イタコン酸、シトラコン酸、マレイン酸、フマル酸、メサコン酸等のジカルボン酸類；
トリカルバリル酸、アコニット酸、カンホロン酸等のトリカルボン酸類
等を挙げることができる。
また、前記フェニル基含有カルボン酸としては、カルボキシル基が直接フェニル基に結合した芳香族カルボン酸や、カルボキシル基が炭素鎖を介してフェニル基に結合したカルボン酸等を挙げることができ、それらの具体例としては、
安息香酸、トルイル酸、クミン酸、ヘメリト酸、メシチレン酸等の芳香族モノカルボン酸類；
フタル酸、イソフタル酸、テレフタル酸等の芳香族ジカルボン酸類；
トリメリット酸、トリメシン酸、メロファン酸、ピロメリット酸等の３価以上の芳香族ポリカルボン酸類や、
フェニル酢酸、ヒドロアトロパ酸、ヒドロけい皮酸、マンデル酸、フェニルこはく酸、アトロパ酸、けい皮酸、シンナミリデン酸、クマル酸、ウンベル酸
等を挙げることができる。
これらの有機酸のうち、マロン酸、アジピン酸、イタコン酸、シトラコン酸、フマル酸、メサコン酸、フタル酸等の脂肪族ジカルボン酸類および芳香族ジカルボン酸類が、アルカリ溶解性、後述する溶媒に対する溶解性、未露光部の基板上あるいは遮光層上における地汚れや膜残りの防止等の観点から好ましい。
前記有機酸は、単独でまたは２種以上を混合して使用することができる。
有機酸の使用量は、感放射線性組成物全体に対して、通常、１０重量％以下、好ましくは５重量％以下、さらに好ましくは１重量％以下である。この場合、有機酸の使用量が１０重量％を超えると、形成された画素の基板に対する密着性が低下する傾向がある。
【００４８】
また、前記有機酸以外の添加剤の具体例としては、
銅フタロシアニン誘導体等の青色顔料誘導体や黄色顔料誘導体等の分散助剤；
ガラス、アルミナ等の充填剤；
ポリビニルアルコール、ポリエチレングリコールモノアルキルエーテル類、ポリ（フロロアルキルアクリレート）類等の高分子化合物；
ノニオン系、カチオン系、アニオン系等の界面活性剤；
ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−クロロプロピルメチルジメトキシシラン、３−クロロプロピルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシラン等の密着促進剤；
２，２−チオビス（４−メチル−６−ｔ−ブチルフェノール）、２，６−ジ−ｔ−ブチルフェノール等の酸化防止剤；
２−（３−ｔ−ブチル−５−メチル−２−ヒドロキシフェニル）−５−クロロベンゾトリアゾール、アルコキシベンゾフェノン類等の紫外線吸収剤；
ポリアクリル酸ナトリウム等の凝集防止剤；
エポキシ化合物、メラミン化合物、ビスアジド化合物等の熱架橋剤
等を挙げることができる。
【００４９】
溶媒
本発明のカラーフィルタ用感放射線性組成物は、前記（Ａ）〜（Ｄ）成分を必須成分とし、必要に応じて前記添加剤成分を含有するが、通常、溶媒を配合して液状組成物として調製される。
前記溶媒としては、感放射線性組成物を構成する（Ａ）〜（Ｄ）成分や添加剤成分を分散または溶解し、かつこれらの成分と反応せず、適度の揮発性を有するものである限り、適宜に選択して使用することができる。
このような溶媒の具体例としては、
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ−ｎ−プロピルエーテル、エチレングリコールモノ−ｎ−ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ−ｎ−プロピルエーテル、ジエチレングリコールモノ−ｎ−ブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ−ｎ−プロピルエーテル、プロピレングリコールモノ−ｎ−ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノ−ｎ−プロピルエーテル、ジプロピレングリコールモノ−ｎ−ブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル等の（ポリ）アルキレングリコールモノアルキルエーテル類；
エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等の（ポリ）アルキレングリコールモノアルキルエーテルアセテート類；
ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジエチルエーテル、テトラヒドロフラン等の他のエーテル類；
メチルエチルケトン、シクロヘキサノン、２−ヘプタノン、３−ヘプタノン等のケトン類；
２−ヒドロキシプロピオン酸メチル、２−ヒドロキシプロピオン酸エチル等の乳酸アルキルエステル類；
２−ヒドロキシ−２−メチルプロピオン酸エチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２−ヒドロキシ−３−メチルブタン酸メチル、３−メチル−３−メトキシブチルアセテート、３−メチル−３−メトキシブチルプロピオネート、酢酸エチル、酢酸ｎ−プロピル、酢酸ｉ−プロピル、酢酸ｎ−ブチル、酢酸ｉ−ブチル、ぎ酸ｎ−アミル、酢酸ｉ−アミル、プロピオン酸ｎ−ブチル、酪酸エチル、酪酸ｎ−プロピル、酪酸ｉ−プロピル、酪酸ｎ−ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸ｎ−プロピル、アセト酢酸メチル、アセト酢酸エチル、２−オキソブタン酸エチル等の他のエステル類；
トルエン、キシレン等の芳香族炭化水素類；
Ｎ−メチルピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド類
等を挙げることができる。
【００５０】
これらの溶媒のうち、溶解性、顔料分散性、塗布性等の観点から、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル、シクロヘキサノン、２−ヘプタノン、３−ヘプタノン、２−ヒドロキシプロピオン酸エチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、３−メチル−３−メトキシブチルプロピオネート、酢酸ｎ−ブチル、酢酸ｉ−ブチル、ぎ酸ｎ−アミル、酢酸ｉ−アミル、プロピオン酸ｎ−ブチル、酪酸エチル、酪酸ｉ−プロピル、酪酸ｎ−ブチル、ピルビン酸エチル等が好ましい。
前記溶媒は、単独でまたは２種以上を混合して使用することができる。
【００５１】
さらに、前記溶媒と共に、ベンジルエチルエーテル、ジヘキシルエーテル、アセトニルアセトン、イソホロン、カプロン酸、カプリル酸、１−オクタノール、１−ノナノール、ベンジルアルコール、酢酸ベンジル、安息香酸エチル、しゅう酸ジエチル、マレイン酸ジエチル、γ−ブチロラクトン、炭酸エチレン、炭酸プロピレン、エチレングリコールモノフェニルエーテルアセテート等の高沸点溶媒を併用することもできる。
これらの高沸点溶媒のうち、γ−ブチロラクトン等が好ましい。
前記高沸点溶媒は、単独でまたは２種以上を混合して使用することができる。溶媒の使用量は、特に限定されるものではないが、得られる感放射線性組成物の塗布性、安定性等の観点から、当該組成物の溶媒を除いた各成分の合計濃度が、通常、５〜５０重量％、好ましくは１０〜４０重量％となる量が望ましい。
【００５２】
カラーフィルタの形成方法
次に、本発明のカラーフィルタ用感放射線性組成物を用いて、カラーフィルタを形成する方法について説明する。
まず、基板の表面上に、必要に応じて、画素を形成する部分を区画するように遮光層を形成し、この基板上に、例えば赤色の顔料が分散された感放射線性組成物の液状組成物を塗布したのち、プレベークを行って溶剤を蒸発させ、塗膜を形成する。次いで、この塗膜にフォトマスクを介して放射線を露光したのち、アルカリ現像液を用いて現像して、塗膜の未露光部を溶解除去し、その後ポストベークすることにより、赤色の画素パターンが所定の配列で配置された画素アレイを形成する。
その後、緑色または青色の顔料が分散された各感放射線性組成物の液状組成物を用い、前記と同様にして、各液状組成物の塗布、プレベーク、露光および現像を行い、その後ポストベークを行って、緑色の画素アレイおよび青色の画素アレイを同一基板上に順次形成することにより、赤色、緑色および青色の三原色の画素アレイが基板上に配置されたカラーフィルタを得る。
カラーフィルタを形成する際に使用される基板としては、例えば、ガラス、シリコン、ポリカーボネート、ポリエステル、芳香族ポリアミド、ポリアミドイミド、ポリイミド等を挙げることができる。これらの基板には、所望により、シランカップリング剤等による薬品処理、プラズマ処理、イオンプレーティング、スパッタリング、気相反応法、真空蒸着等の適宜の前処理を施しておくこともできる。
感放射線性組成物の液状組成物を基板に塗布する際には、回転塗布、流延塗布、ロール塗布等の適宜の塗布法を採用することができる。
塗布厚さは、乾燥後の膜厚として、通常、０．１〜１０μｍ、好ましくは０．２〜５．０μｍ、特に好ましくは０．２〜３．０μｍである。
カラーフィルタを作製する際に使用される放射線としては、例えば、可視光線、紫外線、遠紫外線、電子線、Ｘ線等を使用することができるが、波長が１９０〜４５０ｎｍの範囲にある放射線が好ましい。
放射線の照射エネルギー量は、好ましくは１〜１０００ｍＪ／ｃｍ² である。
また、前記アルカリ現像液としては、例えば、炭酸ナトリウム、水酸化ナトリウム、水酸化カリウム、テトラメチルアンモニウムハイドロオキサイド、コリン、１，８−ジアザビシクロ−［５．４．０］−７−ウンデセン、１，５−ジアザビシクロ−［４．３．０］−５−ノネン等の水溶液が好ましい。
前記アルカリ現像液には、例えばメタノール、エタノール等の水溶性有機溶剤や界面活性剤等を適量添加することもできる。
現像処理法としては、シャワー現像法、スプレー現像法、ディップ（浸漬）現像法、パドル（液盛り）現像法等を適用することができ、現像条件は、常温で５〜３００秒が好ましい。
なお、アルカリ現像後は、通常、水洗する。
このようにして形成されたカラーフィルタは、例えば、透過型あるいは反射型のカラー液晶表示装置、カラー撮像管素子、カラーセンサー等に極めて有用である。
【００５３】
【発明の実施の形態】
本発明のカラーフィルタ用感放射線性組成物は、前記（Ａ）〜（Ｄ）成分を必須成分として含有するものであるが、特に好ましい組成物を具体的に例示すると、下記（イ）〜（ト）のとおりである。
（イ） （Ｂ）アルカリ可溶性樹脂がアルカリ可溶性樹脂（Ｉ）を含み、（Ｄ）光重合開始剤が２，２’−ビス（２−クロルフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾールおよび２，２’−ビス（２−ブロモフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾールの群から選ばれる１種以上のビイミダゾール系化合物を含むカラーフィルタ用感放射線性組成物。
（ロ） （Ｂ）アルカリ可溶性樹脂がアルカリ可溶性樹脂（Ｉ）を含み、（Ｄ）光重合開始剤が２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５、５’−テトラフェニル−１，２’−ビイミダゾール、２，２’−ビス（２，４，６−トリクロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、２，２’−ビス（２，４−ジブロモフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾールおよび２，２’−ビス（２，４，６−トリブロモフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾールの群から選ばれる１種以上のビイミダゾール系化合物を含むカラーフィルタ用感放射線性組成物。
（ハ） （Ｄ）光重合開始剤がさらに、アセトフェノン系化合物および／またはベンゾフェノン系化合物を含む前記（イ）または（ロ）のカラーフィルタ用感放射線性組成物。
（ニ） （Ｂ）アルカリ可溶性樹脂（Ｉ）がアルカリ可溶性樹脂（Ｉａ）、アルカリ可溶性樹脂（Ｉｂ）、アルカリ可溶性樹脂（Ｉｃ）およびアルカリ可溶性樹脂（Ｉｄ）の群から選ばれる少なくとも１種の樹脂を含む前記（イ）、（ロ）または（ハ）のカラーフィルタ用感放射線性組成物。
（ホ） アルカリ可溶性樹脂（Ｉ）中の単官能性単量体（ｂ１）が、こはく酸モノ（２−アクリロイロキシエチル）および／またはこはく酸モノ（２−メタクリロイロキシエチル）を含む前記（イ）、（ロ）、（ハ）または（ニ）のカラーフィルタ用感放射線性組成物。
（ヘ） （Ｃ）多官能性単量体がトリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレートおよびジペンタエリスリトールヘキサアクリレートの群から選ばれる少なくとも１種からなる前記（イ）、（ロ）、（ハ）、（ニ）または（ホ）のカラーフィルタ用感放射線性組成物。
（ト） （Ａ）着色剤が有機顔料を含む前記（イ）、（ロ）、（ハ）、（ニ）、（ホ）または（ヘ）のカラーフィルタ用感放射線性組成物。
【００５４】
以下、実施例を挙げて本発明の実施の形態をさらに具体的に説明する。但し、本発明は、下記実施例に限定されるものではない。
【実施例】
実施例１
（Ａ）着色剤としてC.I.ピグメントレッド１７７を１２０重量部、（Ｂ）アルカリ可溶性樹脂としてメタクリル酸／こはく酸モノ（２−アクリロイロキシエチル）／スチレン／ベンジルメタクリレート／グリセロールモノメタクリレート／Ｎ−フェニルマレイミド共重合体（共重合重量比＝１５．０／１０．０／１１．２／３５．０／１０．０／１８．８、重量平均分子量＝２０，０００）６０重量部、（Ｃ）多官能性単量体としてジペンタエリスリトールヘキサアクリレート４０重量部、（Ｄ）光重合開始剤として２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール１０重量部と４，４’−ビス（ジエチルアミノ）ベンゾフェノン１０重量部と２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン５０重量部、および溶媒として３−エトキシプロピオン酸エチル１０００重量部を混合して、感放射線性組成物の液状組成物（１）を調製した。液状組成物（１）の顔料濃度は、全固形分の約４３重量％であった。
−カラーフィルタの形成−
液状組成物（１）を、表面にナトリウムイオンの溶出を防止するＳｉＯ₂ 膜が形成されたソーダガラス基板表面上に、スピンコーターを用いて塗布したのち、８０℃で１０分間プレベークを行って、膜厚２．０μｍの塗膜を形成した。
その後、この基板を室温に冷却したのち、高圧水銀ランプを用い、フォトマスクを介して、塗膜に３６５ｎｍ、４０５ｎｍおよび４３６ｎｍの各波長を含む紫外線を１００ｍＪ／ｃｍ² の露光量で露光した。次いで、この基板を２３℃の０．０４重量％水酸化カリウム水溶液に１分間浸漬して、現像したのち、超純水で洗浄し、風乾した。その後、２３０℃のクリーンオーブン内で３０分間ポストベークを行なって、基板上に赤色のストライプ状カラーフィルタを形成した。
得られたカラーフィルタを光学顕微鏡により観察したところ、未露光部の基板上に現像残渣が認められず、また投光器を用いて観察したところ、未露光部の基板上に地汚れも認められなかった。さらに、このカラーフィルタの未露光部の基板表面を、エタノールを含ませたトレシー（商品名、東レ（株）製レンズクリーナー））にて１０回擦ったところ、トレシーが赤色に着色されることはなかった。しかも、このカラーフィルタの画素と基板との密着性も優れていた。
【００５５】
実施例２
（Ａ）着色剤としてC.I.ピグメントレッド１７７を１２０重量部、（Ｂ）アルカリ可溶性樹脂としてメタクリル酸／こはく酸モノ（２−アクリロイロキシエチル）／スチレン／２−ヒドロキシエチルメタクリレート／ベンジルメタクリレート／Ｎ−フェニルマレイミド共重合体（共重合重量比＝１５．０／１０．０／１１．２／１０．０／３５．０／１８．８、重量平均分子量＝２５，０００）６０重量部、（Ｃ）多官能性単量体としてジペンタエリスリトールヘキサアクリレート４０重量部、（Ｄ）光重合開始剤として２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール１０重量部と４，４’−ビス（ジエチルアミノ）ベンゾフェノン１０重量部と２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン５０重量部、および溶媒として３−エトキシプロピオン酸エチル１０００重量部を混合して、感放射線性組成物の液状組成物（２）を調製した。液状組成物（２）の顔料濃度は、全固形分の約４３重量％であった。
−カラーフィルタの形成−
液状組成物（１）の代わりに液状組成物（２）を用いた以外は、実施例１と同様にして、赤色のストライプ状カラーフィルタを形成した。
得られたカラーフィルタを光学顕微鏡により観察したところ、未露光部の基板上に現像残渣が認められず、また投光器を用いて観察したところ、未露光部の基板上に地汚れも認められなかった。さらに、このカラーフィルタの未露光部の基板表面を、エタノールを含ませたトレシーにて１０回擦ったところ、トレシーが赤色に着色されることはなかった。しかも、このカラーフィルタの画素と基板との密着性も優れていた。
【００５６】
実施例３
（Ａ）着色剤としてC.I.ピグメントグリーン３６を１１０重量部、（Ｂ）アルカリ可溶性樹脂としてメタクリル酸／こはく酸モノ（２−アクリロイロキシエチル）／ベンジルメタクリレート／グリセロールモノメタクリレート共重合体（共重合重量比＝１５．０／１０．０／６０．０／１５．０、重量平均分子量＝３０，０００）６０重量部、（Ｃ）多官能性単量体としてジペンタエリスリトールヘキサアクリレート４０重量部、（Ｄ）光重合開始剤として２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール１０重量部と４，４’−ビス（ジエチルアミノ）ベンゾフェノン１０重量部と２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン５０重量部、および溶媒としてプロピレングリコールモノメチルエーテルアセテート１０００重量部を混合して、感放射線性組成物の液状組成物（３）を調製した。液状組成物（３）の顔料濃度は、全固形分の約４１重量％であった。
−カラーフィルタの形成−
液状組成物（１）の代わりに液状組成物（３）を用いた以外は、実施例１と同様にして、緑色のストライプ状カラーフィルタを形成した。
得られたカラーフィルタを光学顕微鏡により観察したところ、未露光部の基板上に現像残渣が認められず、また投光器を用いて観察したところ、未露光部の基板上に地汚れも認められなかった。さらに、このカラーフィルタの未露光部の基板表面を、エタノールを含ませたトレシーにて１０回擦ったところ、トレシーが赤色に着色されることはなかった。しかも、このカラーフィルタの画素と基板との密着性も優れていた。
【００５７】
実施例４
（Ａ）着色剤としてC.I.ピグメントブルー１５を１００重量部、（Ｂ）アルカリ可溶性樹脂としてメタクリル酸／こはく酸モノ（２−アクリロイロキシエチル）／スチレン／２−ヒドロキシエチルメタクリレート／ベンジルメタクリレート／Ｎ−フェニルマレイミド共重合体（共重合重量比＝１５．０／１０．０／１１．２／１０．０／３５．０／１８．８、重量平均分子量＝３５，０００）６０重量部、（Ｃ）多官能性単量体としてジペンタエリスリトールヘキサアクリレート４０重量部、（Ｄ）光重合開始剤として２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール１０重量部と４，４’−ビス（ジエチルアミノ）ベンゾフェノン１０重量部と２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン５０重量部、および溶媒として３−エトキシプロピオン酸エチル１０００重量部を混合して、感放射線性組成物の液状組成物（４）を調製した。液状組成物（４）の顔料濃度は、全固形分の約３８重量％であった。
−カラーフィルタの形成−
液状組成物（１）の代わりに液状組成物（４）を用いた以外は、実施例１と同様にして、青色のストライプ状カラーフィルタを形成した。
得られたカラーフィルタを光学顕微鏡により観察したところ、未露光部の基板上に現像残渣が認められず、また投光器を用いて観察したところ、未露光部の基板上に地汚れも認められなかった。さらに、このカラーフィルタの未露光部の基板表面を、エタノールを含ませたトレシーにて１０回擦ったところ、トレシーが赤色に着色されることはなかった。しかも、このカラーフィルタの画素と基板との密着性も優れていた。
【００５８】
比較例１
実施例１の（Ｂ）アルカリ可溶性樹脂６０重量部に代えて、アルカリ可溶性樹脂としてメタクリル酸／２−ヒドロキシエチルメタクリレート／ベンジルメタクリレート共重合体（共重合重量比＝１５／１５／７０、重量平均分子量＝２８，０００）６０重量部を用いた以外は、実施例１と同様にして、感放射線性組成物の液状組成物の調製して、基板上に赤色のストライプ状カラーフィルタを形成した。
得られたカラーフィルタを光学顕微鏡により観察したところ、未露光部の基板上に残渣が認められ、また投光器を用いて観察したところ、未露光部の基板上に地汚れも認められた。さらに、このカラーフィルタの未露光部の基板表面を、エタノールを含ませたトレシーにて１０回擦ったところ、トレシーが赤色に着色した。
【００５９】
【発明の効果】
本発明のカラーフィルター用感放射線性組成物は、顔料を高濃度で含む場合でも優れた現像性を示し、現像時に未露光部の基板上および遮光層上に残渣および地汚れを生じることがなく、かつ基板および遮光層への密着性に優れた画素を与えることができる。
したがって、本発明のカラーフィルター用感放射線性組成物は、電子工業分野におけるカラー液晶表示装置用カラーフィルターを始めとする各種のカラーフィルターの製造に極めて好適に使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a radiation-sensitive composition for a color filter for forming a color filter used for a transmissive or reflective color liquid crystal display device, a color image pickup tube element, and the like. The present invention relates to a radiation sensitive composition for a color filter.
[0002]
[Prior art]
Conventionally, when manufacturing a color filter using a radiation-sensitive composition, the radiation-sensitive composition is applied on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed, dried, and then dried. The film is irradiated with radiation in a desired pattern (hereinafter referred to as “exposure”) and developed to obtain pixels of each color. The color filter thus produced has a problem that a residue and a background stain are likely to occur on the unexposed substrate or the light-shielding layer during development, and the degree thereof is included in the radiation-sensitive composition. As the pigment concentration increased, it tended to become significant, and it was difficult to achieve a sufficient color concentration.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a radiation sensitive composition for a color filter that exhibits good developability even when a pigment is contained at a high concentration, specifically, a residue and a ground on an unexposed substrate and a light shielding layer during development. An object of the present invention is to provide a novel radiation sensitive composition for a color filter which does not cause contamination and gives a pixel having excellent adhesion to a substrate and a light shielding layer.
[0004]
[Means for Solving the Problems]
  The present invention
(A) Colorant, (B) Dicarboxylic acid mono (2-acryloyloxyethyl) and dicarboxylic acid mono (2-methacryloyloxyethyl)MonofunctionalMonomer(B1), a monofunctional monomer (b2) having one or more carboxyl groups other than the monofunctional monomer (b1), and other than the aboveA color filter comprising an alkali-soluble resin containing a copolymer with a copolymerizable monofunctional monomer, (C) a polyfunctional monomer, and (D) a photopolymerization initiator Radiation sensitive composition for
Consists of.
[0005]
The present invention is described in detail below.
(A) Colorant
The colorant in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the obtained color filter, and may be an organic colorant or an inorganic colorant.
The organic colorant specifically means a dye, an organic pigment, a natural pigment, and the like, and the inorganic colorant specifically means an inorganic salt other than an inorganic pigment, an inorganic salt called an extender pigment, Since the color filter is required to have high-definition color development and heat resistance, the colorant in the present invention is preferably a colorant having high color developability and high heat resistance, in particular, a colorant having high heat decomposition resistance. Organic colorants, particularly preferably organic pigments are used.
Examples of the organic pigment include compounds classified as Pigment in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following Color Index (CI) numbers. What is attached can be mentioned.
[0006]
CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment ..... DOO Yellow 155, C.I Pigment Yellow 156, C.I Pigment Yellow 166, C.I Pigment Yellow 168, C.I Pigment Yellow 175, C.I Pigment Yellow 185;
[0007]
CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73;
C.I. pigment violet 1, C.I. pigment violet 19, C.I. pigment violet 23, C.I. pigment violet 29, C.I. pigment violet 32, C.I. pigment violet 36, C.I. pigment violet 38;
[0008]
CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57: 2, CI Pigment Red 58: 2, CI Pigment Red 58 : 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI pigmentless 97, CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 77, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red . 64, C.I Pigment Red 265;
[0009]
C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 60;
C.I. Pigment Green 7, C.I. Pigment Green 36;
C.I. Pigment Brown 23, C.I. Pigment Brown 25;
C.I. Pigment Black 1, Pigment Black 7.
These organic pigments can be used alone or in admixture of two or more.
[0010]
Specific examples of the inorganic colorant include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, Examples thereof include chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.
These inorganic colorants can be used alone or in admixture of two or more.
[0011]
In the present invention, each colorant can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the colorant surface include polymers described in JP-A-8-259876 and various commercially available polymers or oligomers for dispersing pigments.
Further, the colorant in the present invention can be used together with a dispersant as desired.
Examples of such a dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.
Specific examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like Polyoxyethylene alkylphenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate;
In addition to sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; polyethyleneimines, etc., the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Tochem Products), MegaFac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), etc. be able to.
These surfactants can be used alone or in admixture of two or more.
The usage-amount of surfactant is 50 parts weight or less normally with respect to 100 weight part of coloring agents, Preferably it is 0-30 weight part.
[0012]
(B) Alkali-soluble resin
  The alkali-soluble resin in the present invention is selected from the group of dicarboxylic acid mono (2-acryloyloxyethyl) and dicarboxylic acid mono (2-methacryloyloxyethyl).MonofunctionalMonomer(B1), a monofunctional monomer (b2) having one or more carboxyl groups other than the monofunctional monomer (b1), and other than the aboveCopolymerizable monofunctional monomer(Hereinafter referred to as “other monofunctional monomers”.)And a copolymer (hereinafter referred to as “copolymer (B1)”).
  Examples of the dicarboxylic acid in the monofunctional monomer (b1) include aliphatic dicarboxylic acids having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. Acids: Aliphatic dicarboxylic acids having 7 to 24 carbon atoms, preferably 8 to 14 carbon atoms such as hexahydrophthalic acid, hexahydroisophthalic acid and hexahydroterephthalic acid; Carbon numbers such as phthalic acid, isophthalic acid and terephthalic acid Examples thereof include aromatic dicarboxylic acids having 8 to 24, preferably 8 to 14 carbon atoms.
  Among these dicarboxylic acids, aliphatic dicarboxylic acids having 4 to 8 carbon atoms are preferable, and succinic acid is particularly preferable.
  In this invention, a monofunctional monomer (b1) can be used individually or in mixture of 2 or more types.
[0013]
  Moreover, as a monofunctional monomer (b2), for example,
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like;
A trivalent or higher unsaturated polycarboxylic acid or anhydride thereof,
ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate
Etc.
  These monofunctional monomers (b2) can be used alone or in admixture of two or more.
[0014]
Examples of other monofunctional monomers include:
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, indene, o-vinylbenzylmethyl ether Aromatic vinyl compounds such as m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl Methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl Acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy Tyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate , 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate , Toxipropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2-hydroxy- Unsaturated carboxylic esters such as 3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate;
2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl Unsaturated carboxylic acid aminoalkyl esters such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether;
Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. be able to.
These other monofunctional monomers can be used alone or in admixture of two or more.
[0015]
  As the copolymer (B1), in particular,At least oneMonofunctional monomer containing monofunctional monomer (b1) and acrylic acid and / or methacrylic acid as essential components, and optionally containing ω-carboxypolycaprolactone monoacrylate and / or ω-carboxypolycaprolactone monomethacrylate Body (b2), styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-phenylmaleimide , A copolymer with at least one selected from the group consisting of polystyrene macromonomer and polymethyl methacrylate macromonomer (hereinafter referred to as “alkaline acceptable”). Soluble resin (I) ”) is preferred.
[0016]
As specific examples of the alkali-soluble resin (I),
(Meth) acrylic acid / monofunctional monomer (b1) / styrene copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / polystyrene macromonomer copolymer,
Or
(Meth) acrylic acid / monofunctional monomer (b1) / polymethyl methacrylate macromonomer copolymer
A terpolymer (hereinafter referred to as “alkali-soluble resin (Ia)”);
[0017]
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
[0018]
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / N-phenylmaleimide copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / polystyrene macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / N-phenylmaleimide / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / N-phenylmaleimide / polystyrene macromonomer copolymer,
Or
(Meth) acrylic acid / monofunctional monomer (b1) / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer
A quaternary copolymer (hereinafter referred to as “alkali-soluble resin (Ib)”);
[0019]
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / methyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / methyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / styrene / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / methyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / methyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
[0020]
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / styrene / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / styrene / N-phenylmaleimide copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / styrene / polystyrene macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / styrene / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / N-phenylmaleimide / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / N-phenylmaleimide / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
[0021]
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
[0022]
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / methyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer,
[0023]
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
[0024]
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
[0025]
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / benzyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
[0026]
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / benzyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / phenyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / phenyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / N-phenylmaleimide / polystyrene macromonomer copolymer or
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer
A five-component copolymer (hereinafter referred to as “alkali-soluble resin (Ic)”);
[0027]
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
[0028]
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate / glycerol mono (meth) acrylate / polystyrene macromonomer copolymer
Or
(Meth) acrylic acid / monofunctional monomer (b1) / styrene / phenyl (meth) acrylate / glycerol mono (meth) acrylate / polymethyl methacrylate macromonomer copolymer
A six-component copolymer (hereinafter referred to as “alkali-soluble resin (Id)”).
Etc.
[0029]
  In the present invention, among the alkali-soluble resin (Ia), alkali-soluble resin (Ib), alkali-soluble resin (Ic) and alkali-soluble resin (Id), those monofunctional monomers (b1) are succinic acid. Particularly preferred are resins that are mono (2-acryloyloxyethyl) and / or succinic acid mono (2-methacryloyloxyethyl).
  The copolymerization ratio of the monofunctional monomer (b1) in the copolymer (B1) is usually 5 to 35% by weight, preferably 10 to 25% by weight. In this case, if the copolymerization ratio of the monofunctional monomer (b1) is less than 5% by weight, there is a risk of causing residue, background stains, etc. on the unexposed portion of the substrate or the light shielding layer, while 35% by weight If it exceeds, the formed pixels tend to drop off from the substrate during development with an alkaline developer.
  The copolymerization ratio of the monofunctional monomer (b2) is usually 5 to 50% by weight, preferably 10 to 40% by weight, and the copolymerization ratio of other unsaturated monomers is usually It is 15 to 90% by weight, preferably 35 to 80% by weight. In this case, if the copolymerization ratio of the monofunctional monomer (b2) is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkaline developer tends to be lowered, whereas it exceeds 50% by weight. When developing with an alkaline developer, the formed pixel tends to drop off from the substrate and the film surface of the pixel tends to be rough. The copolymer (B1) containing the monofunctional monomer (b2) at the specific copolymerization ratio together with the monofunctional monomer (b1) has excellent solubility in an alkali developer. The radiation-sensitive composition using the copolymer as a binder has very little undissolved material remaining after development with an alkaline developer, and the residue on the unexposed portion of the substrate or the light shielding layer, Background stains and the like hardly occur, and the pixel obtained from the composition does not excessively dissolve in an alkaline developer, has excellent adhesion to the substrate, and does not fall off the substrate. It becomes a thing.
  The said copolymer (B1) can be used individually or in mixture of 2 or more types.
[0030]
  In the present invention, in some cases, other alkali-soluble resins can be used in combination with the copolymer (B1).
  As said other alkali-soluble resin, resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group, can be mentioned, for example.
  As such another alkali-soluble resin, a resin having a carboxyl group is preferable, and more preferably the monofunctional monomer (b2) exemplified for the copolymer (B1) and the other monofunctional monomer. In particular, a monofunctional monomer containing acrylic acid and / or methacrylic acid as an essential component, and optionally containing ω-carboxypolycaprolactone monoacrylate and / or ω-carboxypolycaprolactone monomethacrylate (B2), styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, glycerol monoacrylate, glycerol monomer A copolymer (hereinafter referred to as “alkali-soluble resin (II)”) with at least one selected from the group of tacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer is preferred.
[0031]
As a specific example of the alkali-soluble resin (II),
(Meth) acrylic acid / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
Methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / styrene / benzyl methacrylate / glycerol (meth) acrylate / N-phenylmaleimide copolymer
Etc.
These alkali-soluble resins (II) can be used alone or in admixture of two or more.
The amount of the resin used when the other alkali-soluble resin is used is usually 50% by weight or less, preferably 30% by weight or less based on the total amount of the alkali-soluble resin. In this case, if the amount of the other alkali-soluble resin used exceeds 50% by weight, residues, background stains, etc. tend to occur on the unexposed substrate or the light shielding layer.
[0032]
The alkali-soluble resin in the present invention contains the copolymer (B1) as an essential component, but the polystyrene-converted weight average measured by gel permeation chromatography (GPC; elution solvent tetrahydrofuran) of each component constituting the alkali-soluble resin. The molecular weight (hereinafter simply referred to as “weight average molecular weight”) is preferably 3,000 to 300,000, particularly preferably 5,000 to 100,000. By using such an alkali-soluble resin having a specific weight average molecular weight, a radiation-sensitive composition excellent in developability can be obtained, thereby forming a pixel having a sharp pattern edge, Residues, background stains, film residues, and the like are less likely to occur on the unexposed substrate or the light shielding layer during development.
The usage-amount of the alkali-soluble resin in this invention is 10-1000 weight part normally with respect to 100 weight part of (A) coloring agents, Preferably it is 20-500 weight part. In this case, if the amount of the alkali-soluble resin used is less than 10 parts by weight, for example, alkali developability may be reduced, or residues, background stains, etc. may be generated on the unexposed part of the substrate or on the light shielding layer. If it exceeds 1000 parts by weight, the colorant concentration is relatively lowered, so that it may be difficult to achieve the target color density as a thin film.
[0033]
(C) Multifunctional monomer
The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.
Diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like and their dicarboxylic acid modified products;
Oligoacrylates or oligomethacrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, and spirane resin;
Diacrylates or dimethacrylates of hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone,
Tris (2-acryloyloxyethyl) phosphate, Tris (2-methacryloyloxyethyl) phosphate
Etc.
[0034]
Among these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferable. Specifically, trimethylolpropane triacrylate, trimethylolpropane triacrylate are preferable. Methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, the following formula (1 ) Are preferred, and in particular, trimethylolpropane triacrylate, pentaerythritol Lumpur triacrylate and dipentaerythritol hexaacrylate, high pixel intensities, excellent smoothness of the pixel surface and the substrate or on stain on the light-shielding layer in the unexposed portion, are unlikely to generate film residue and the like.
[0035]
[Chemical 1]

[0036]
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.
Moreover, in this invention, a monofunctional monomer can also be used together with the said polyfunctional monomer depending on the case.
As a specific example of such a monofunctional monomer, in addition to the monofunctional monomer (b2) exemplified for the copolymer (B1) and the other monofunctional monomers, M-5400, M-5600 (trade name, manufactured by Toagosei Co., Ltd.) and the like can be mentioned.
These monofunctional monomers can be used alone or in admixture of two or more.
The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 0 to 50% by weight, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the usage ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the obtained pixel may be insufficient.
The total amount of the polyfunctional monomer and monofunctional monomer used in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts per 100 parts by weight of the (B) alkali-soluble resin. Parts by weight. In this case, if the amount used is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to be reduced. On the other hand, if it exceeds 500 parts by weight, for example, the alkali developability is lowered, or the substrate in the unexposed part. There is a tendency that background stains, film residue, etc. are likely to occur on or on the light shielding layer.
[0037]
(D) Photopolymerization initiator
In the present invention, the photopolymerization initiator is decomposed or cleaved by exposure to visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like, and the above-mentioned (C) polyfunctionality such as radical, cation, anion, etc. A compound that generates an active species capable of initiating monomer polymerization.
As such a photopolymerization initiator, in addition to an imidazole compound having at least one main skeleton represented by the following formula (2), formula (3) or formula (4), a benzoin compound, an acetophenone compound, Examples include benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, triazine compounds, and the like.
[0038]
[Chemical 2]

[0039]
[Chemical Formula 3]

[0040]
[Formula 4]

[0041]
As a specific example of the biimidazole compound,
2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-cyanophenyl) -4,4 ', 5.5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-cyanophenyl) -4,4 ', 5.5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-cyanophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole,
[0042]
2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2-cyanophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2,4-dicyanophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2,4,6-tricyanophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2,4-dimethylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2,4,6-trimethylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2,4-diethylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2,4,6-triethylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2,4-diphenylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis (2,4,6-triphenylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole
Etc.
[0043]
Among these biimidazole compounds, in particular, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole and 2 , 2'-bis (2,4,6-trib Mofeniru) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole are preferred.
The biimidazole compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved substances and precipitates, has high sensitivity, sufficiently advances the curing reaction by exposure with a small amount of energy, and has a contrast. It is high and does not cause a curing reaction in the unexposed area, so the coated film after exposure is clearly divided into a hardened part insoluble in the developer and an uncured part having high solubility in the developer Accordingly, a high-definition pixel array in which pixel patterns without undercuts are arranged according to a predetermined arrangement can be formed.
[0044]
Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin i-propyl ether, benzoin i-butyl ether, and methyl-2-benzoylbenzoate.
Specific examples of the acetophenone compound include 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- (4-i-propylphenyl) -2. -Hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2- Methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexylphenyl Ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and the like.
Specific examples of the benzophenone compounds include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone.
Specific examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoylformate, and the like.
Specific examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone and the like.
Specific examples of the xanthone compound include xanthone, thioxanthone, 2-chlorothioxanthone and the like.
Specific examples of the triazine compound include 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1 , 3-bis (trichloromethyl) -5- (4′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-methoxyphenyl) -s-triazine, 1,3- Bis (trichloromethyl) -5- (4′-methoxyphenyl) -s-triazine, 2- (2′-furylethylidene) -4,6-bis (trichloromethyl) -s-triazine, 2- (4′- Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-tri Gin, 2- (4′-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2′-bromo-4′-methylphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2'-thiophenylethylidene) -4,6-bis (trichloromethyl) -s-triazine, etc. can be mentioned.
[0045]
These photopolymerization initiators can be used alone or in admixture of two or more.
The amount of the photopolymerization initiator used in the present invention is usually 0.01 to 200 weights per 100 parts by weight of the total of (C) the polyfunctional monomer and optionally used monofunctional monomer. Parts, preferably 1 to 120 parts by weight, particularly preferably 1 to 100 parts by weight. In this case, if the amount of the photopolymerization initiator used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a pixel array in which pixel patterns are arranged according to a predetermined arrangement, On the other hand, when the amount exceeds 200 parts by weight, the formed pixels are liable to fall off the substrate during development, and background stains, film residues, etc. are likely to occur on the unexposed portion of the substrate or on the light shielding layer.
Furthermore, in the present invention, one or more of a sensitizer, a curing accelerator or a polymer photocrosslinking / sensitizer can be used in combination with the photopolymerization initiator as necessary.
[0046]
In the present invention, it is particularly preferable to use a combination of a biimidazole compound and an acetophenone compound and / or a benzophenone compound as a photopolymerization initiator. It is preferable in terms of high strength and sensitivity.
In the present invention, when a biimidazole compound and another component are used in combination as a photopolymerization initiator, the usage ratio of the other component is preferably 80% by weight or less of the entire photopolymerization initiator.
Here, when the particularly preferable photopolymerization initiator in the present invention is shown as a combination of its constituent components, the following can be mentioned.
2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole / 4,4'-bis (diethylamino) benzophenone,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole / 4,4′-bis (diethylamino) benzophenone / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole / 4,4′-bis (diethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone,
2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole / 4,4'-bis (diethylamino) benzophenone,
2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole / 4,4′-bis (diethylamino) benzophenone / 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one,
2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole / 4,4′-bis (diethylamino) benzophenone / 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one,
2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole / 4,4′-bis (diethylamino) benzophenone / 1-hydroxy Cyclohexyl phenyl ketone.
[0047]
Additive
The radiation sensitive composition for a color filter of the present invention can contain various additives as necessary.
Examples of the additive include organic acids that have the effect of further improving the solubility of the radiation-sensitive composition for color filters in an alkaline developer and further suppressing the remaining undissolved material after development.
As such an organic acid, an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having a molecular weight of 1,000 or less is preferable.
Specific examples of the aliphatic carboxylic acid include
Monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid
Etc.
Examples of the phenyl group-containing carboxylic acid include aromatic carboxylic acids in which a carboxyl group is directly bonded to a phenyl group, and carboxylic acids in which a carboxyl group is bonded to a phenyl group via a carbon chain. As a specific example,
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, umberic acid
Etc.
Among these organic acids, aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, and phthalic acid are alkali-soluble and soluble in solvents described later. From the standpoint of preventing background contamination and film residue on the unexposed portion of the substrate or the light shielding layer.
The organic acids can be used alone or in admixture of two or more.
The amount of the organic acid used is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less based on the whole radiation-sensitive composition. In this case, when the amount of the organic acid used exceeds 10% by weight, the adhesion of the formed pixel to the substrate tends to be lowered.
[0048]
As specific examples of additives other than the organic acid,
Dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives;
Fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, poly (fluoroalkyl acrylates);
Nonionic, cationic and anionic surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Thermal crosslinking agents such as epoxy compounds, melamine compounds, and bisazide compounds
Etc.
[0049]
solvent
The radiation sensitive composition for a color filter of the present invention comprises the components (A) to (D) as essential components, and optionally contains the additive component. Usually, the composition is a liquid composition containing a solvent. As prepared.
As the solvent, the components (A) to (D) and additive components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components and have appropriate volatility. Can be appropriately selected and used.
Specific examples of such solvents include
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;
(Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl 3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate Butyl, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate , Methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate Other esters;
Aromatic hydrocarbons such as toluene and xylene;
Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide
Etc.
[0050]
Among these solvents, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl from the viewpoints of solubility, pigment dispersibility, coatability, etc. Ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropio Nate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-probutyrate Le, butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.
[0051]
Further, together with the solvent, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate , Γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate and other high boiling point solvents can be used in combination.
Of these high boiling solvents, γ-butyrolactone and the like are preferred.
The high boiling point solvents can be used alone or in admixture of two or more. The amount of the solvent used is not particularly limited, but the total concentration of each component excluding the solvent of the composition is usually from the viewpoint of applicability, stability, etc. of the resulting radiation-sensitive composition. An amount of 5 to 50% by weight, preferably 10 to 40% by weight, is desirable.
[0052]
Method for forming color filter
Next, a method for forming a color filter using the radiation sensitive composition for a color filter of the present invention will be described.
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming pixels, and a liquid composition of a radiation sensitive composition in which, for example, a red pigment is dispersed on the substrate. After applying the material, pre-baking is performed to evaporate the solvent and form a coating film. Next, the coating film is exposed to radiation through a photomask and then developed with an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to form a red pixel pattern. A pixel array arranged in a predetermined arrangement is formed.
Then, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, the liquid composition is applied, pre-baked, exposed and developed in the same manner as described above, and then post-baked. By sequentially forming the green pixel array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green, and blue are arranged on the substrate is obtained.
Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When the liquid composition of the radiation sensitive composition is applied to the substrate, an appropriate application method such as spin coating, cast coating, roll coating or the like can be employed.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 5.0 μm, particularly preferably 0.2 to 3.0 μm, as the film thickness after drying.
As the radiation used when producing the color filter, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable. .
The amount of radiation irradiation energy is preferably 1 to 1000 mJ / cm.²It is.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied, and the development conditions are preferably 5 to 300 seconds at room temperature.
In addition, it is usually washed with water after alkali development.
The color filter thus formed is extremely useful for, for example, a transmissive or reflective color liquid crystal display device, a color imaging tube element, a color sensor, and the like.
[0053]
DETAILED DESCRIPTION OF THE INVENTION
The radiation sensitive composition for a color filter of the present invention contains the components (A) to (D) as essential components. Specific examples of particularly preferred compositions are the following (a) to ( G).
(A) (B) The alkali-soluble resin contains the alkali-soluble resin (I), and (D) the photopolymerization initiator is 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-. Tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole and 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1 A radiation-sensitive composition for a color filter comprising at least one biimidazole compound selected from the group of 2,2′-biimidazole.
(B) (B) The alkali-soluble resin contains the alkali-soluble resin (I), and (D) the photopolymerization initiator is 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5 ′. -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis (2,4,6-tri (Bromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole-containing radiation-sensitive composition containing at least one biimidazole compound selected from the group of biimidazoles.
(C) (D) The radiation sensitive composition for color filters according to (A) or (B) above, wherein the photopolymerization initiator further contains an acetophenone compound and / or a benzophenone compound.
(D) (B) At least one resin selected from the group consisting of alkali-soluble resin (I), alkali-soluble resin (Ia), alkali-soluble resin (Ib), alkali-soluble resin (Ic), and alkali-soluble resin (Id) The radiation sensitive composition for a color filter according to the above (a), (b) or (c).
(E) The monofunctional monomer (b1) in the alkali-soluble resin (I) contains succinic acid mono (2-acryloyloxyethyl) and / or succinic acid mono (2-methacryloyloxyethyl). (A), (b), (c) or (d) a radiation-sensitive composition for a color filter;
(F) (C) The above-mentioned (i), (b), (c) wherein the polyfunctional monomer is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate. ), (D) or (e) a radiation sensitive composition for a color filter.
(G) (A) The radiation sensitive composition for a color filter according to (A), (B), (C), (D), (E) or (F), wherein the colorant contains an organic pigment.
[0054]
Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
【Example】
Example 1
(A) 120 parts by weight of CI pigment red 177 as a colorant, (B) methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenylmaleimide as an alkali-soluble resin 60 parts by weight of copolymer (copolymerization weight ratio = 15.0 / 10.0 / 11.2 / 35.0 / 10.0 / 18.8, weight average molecular weight = 20,000), (C) polyfunctional 40 parts by weight of dipentaerythritol hexaacrylate as a photopolymerizable monomer, and (2) 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1 as a photopolymerization initiator , 2′-biimidazole 10 parts by weight, 4,4′-bis (diethylamino) benzophenone 10 parts by weight and 2-benzyl-2-dimethylamino 50 parts by weight of non-1- (4-morpholinophenyl) butan-1-one and 1000 parts by weight of ethyl 3-ethoxypropionate as a solvent were mixed to prepare a liquid composition (1) of a radiation sensitive composition. Prepared. The pigment concentration of the liquid composition (1) was about 43% by weight of the total solid content.
-Formation of color filters-
SiO which prevents the elution of sodium ions on the surface of the liquid composition (1)₂On the surface of the soda glass substrate on which the film was formed, it was applied using a spin coater and then pre-baked at 80 ° C. for 10 minutes to form a coating film having a thickness of 2.0 μm.
Thereafter, after cooling the substrate to room temperature, ultraviolet rays containing wavelengths of 365 nm, 405 nm, and 436 nm are applied to the coating film through a photomask using a high-pressure mercury lamp at 100 mJ / cm.²The exposure amount was as follows. Next, the substrate was immersed in a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried. Thereafter, post-baking was performed in a clean oven at 230 ° C. for 30 minutes to form a red striped color filter on the substrate.
When the obtained color filter was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and when observed using a projector, no ground stain was observed on the unexposed portion of the substrate. . Furthermore, when the substrate surface of the unexposed portion of this color filter is rubbed 10 times with a Toraysee (trade name, manufactured by Toray Industries, Inc.) containing ethanol, the Toraysee is colored red. There wasn't. Moreover, the adhesion between the color filter pixels and the substrate was also excellent.
[0055]
Example 2
(A) 120 parts by weight of CI Pigment Red 177 as a colorant, (B) methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / N- 60 parts by weight of phenylmaleimide copolymer (copolymerization weight ratio = 15.0 / 10.0 / 11.2 / 10.0 / 35.0 / 18.8, weight average molecular weight = 25,000), (C) 40 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl as a photopolymerization initiator -1,2'-biimidazole 10 parts by weight, 4,4'-bis (diethylamino) benzophenone 10 parts by weight and 2-benzyl-2-dimethyl Mixing 50 parts by weight of amino-1- (4-morpholinophenyl) butan-1-one and 1000 parts by weight of ethyl 3-ethoxypropionate as a solvent, a liquid composition (2) of the radiation sensitive composition is obtained. Prepared. The pigment concentration of the liquid composition (2) was about 43% by weight of the total solid content.
-Formation of color filters-
A red striped color filter was formed in the same manner as in Example 1 except that the liquid composition (2) was used instead of the liquid composition (1).
When the obtained color filter was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and when observed using a projector, no ground stain was observed on the unexposed portion of the substrate. . Further, when the substrate surface of the unexposed portion of the color filter was rubbed 10 times with a tray containing ethanol, the tray was not colored red. Moreover, the adhesion between the color filter pixels and the substrate was also excellent.
[0056]
Example 3
(A) 110 parts by weight of CI pigment green 36 as a colorant, (B) methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymerization weight) as an alkali-soluble resin Ratio = 15.0 / 10.0 / 60.0 / 15.0, weight average molecular weight = 30,000) 60 parts by weight, (C) 40 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, ( D) As a photopolymerization initiator, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole 10 parts by weight and 4,4′- 10 parts by weight of bis (diethylamino) benzophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one 5 A liquid composition (3) of a radiation sensitive composition was prepared by mixing 0 part by weight and 1000 parts by weight of propylene glycol monomethyl ether acetate as a solvent. The pigment concentration of the liquid composition (3) was about 41% by weight of the total solid content.
-Formation of color filters-
A green striped color filter was formed in the same manner as in Example 1 except that the liquid composition (3) was used instead of the liquid composition (1).
When the obtained color filter was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and when observed using a projector, no ground stain was observed on the unexposed portion of the substrate. . Further, when the substrate surface of the unexposed portion of the color filter was rubbed 10 times with a tray containing ethanol, the tray was not colored red. Moreover, the adhesion between the color filter pixels and the substrate was also excellent.
[0057]
Example 4
(A) 100 parts by weight of CI pigment blue 15 as a colorant, (B) methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / N- 60 parts by weight of phenylmaleimide copolymer (copolymerization weight ratio = 15.0 / 10.0 / 11.2 / 10.0 / 35.0 / 18.8, weight average molecular weight = 35,000), (C) 40 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl as a photopolymerization initiator -10 'part by weight of 1,2'-biimidazole, 10 parts by weight of 4,4'-bis (diethylamino) benzophenone and 2-benzyl-2-dimethyla Mixing 50 parts by weight of Mino-1- (4-morpholinophenyl) butan-1-one and 1000 parts by weight of ethyl 3-ethoxypropionate as a solvent, a liquid composition (4) of the radiation-sensitive composition was obtained. Prepared. The pigment concentration of the liquid composition (4) was about 38% by weight of the total solid content.
-Formation of color filters-
A blue striped color filter was formed in the same manner as in Example 1 except that the liquid composition (4) was used instead of the liquid composition (1).
When the obtained color filter was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and when observed using a projector, no ground stain was observed on the unexposed portion of the substrate. . Further, when the substrate surface of the unexposed portion of the color filter was rubbed 10 times with a tray containing ethanol, the tray was not colored red. Moreover, the adhesion between the color filter pixels and the substrate was also excellent.
[0058]
Comparative Example 1
Instead of 60 parts by weight of the alkali-soluble resin (B) in Example 1, a methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymerization weight ratio = 15/15/70, weight average molecular weight) as an alkali-soluble resin = 28,000) A liquid composition of a radiation sensitive composition was prepared in the same manner as in Example 1 except that 60 parts by weight were used, and a red stripe color filter was formed on the substrate.
When the obtained color filter was observed with an optical microscope, a residue was observed on the unexposed portion of the substrate, and when observed using a projector, ground stain was also observed on the unexposed portion of the substrate. Further, when the substrate surface of the unexposed portion of the color filter was rubbed 10 times with a tray containing ethanol, the tray was colored red.
[0059]
【The invention's effect】
The radiation sensitive composition for a color filter of the present invention exhibits excellent developability even when a pigment is contained at a high concentration, and does not cause residue and background staining on the unexposed substrate and the light shielding layer during development. In addition, a pixel excellent in adhesion to the substrate and the light shielding layer can be provided.
Therefore, the radiation sensitive composition for color filters of the present invention can be used very suitably for the production of various color filters including color filters for color liquid crystal display devices in the electronic industry.

Claims (9)

(A) a colorant, (B) a monofunctional monomer (b1) selected from the group of dicarboxylic acid mono (2-acryloyloxyethyl) and dicarboxylic acid mono (2-methacryloyloxyethyl ), and monofunctional Alkali-soluble, comprising a copolymer of a monofunctional monomer (b2) having one or more carboxyl groups other than the polymerizable monomer (b1) and a copolymerizable monofunctional monomer other than those described above A radiation-sensitive composition for a color filter, comprising a resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. (B) The alkali-soluble resin contains at least one monofunctional monomer (b1) and acrylic acid and / or methacrylic acid as essential components, and optionally ω-carboxypolycaprolactone monoacrylate and / or ω-carboxypolyester. Monofunctional monomer (b2) containing caprolactone monomethacrylate and styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, glycerol A small amount selected from the group of monoacrylate, glycerol monomethacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethylmethacrylate macromonomer A copolymer with at least one kind, and (D) a photopolymerization initiator is 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) ) -1,2′-biimidazole and 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole The radiation-sensitive composition for a color filter according to claim 1, comprising at least one biimidazole compound selected from the group. (B) The alkali-soluble resin contains a monofunctional monomer (b1) and acrylic acid and / or methacrylic acid as essential components, and optionally ω-carboxypolycaprolactone monoacrylate and / or ω-carboxypolycaprolactone monomethacrylate. Monofunctional monomer (b2) and styrene, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, glycerol monoacrylate, glycerol Co-polymerization with at least one selected from the group consisting of monomethacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethylmethacrylate macromonomer. (D) a photopolymerization initiator comprising 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,5'- The radiation sensitive composition for a color filter according to claim 1, comprising at least one biimidazole compound selected from the group of tetraphenyl-1,2'-biimidazole.   (D) The radiation sensitive composition for color filters according to claim 2 or 3, wherein the photopolymerization initiator further contains an acetophenone compound and / or a benzophenone compound.   (B) The dicarboxylic acid mono (2-acryloyloxyethyl) in the alkali-soluble resin contains succinic acid mono (2-acryloyloxyethyl), and (B) the dicarboxylic acid mono (2-methacryloyl in the alkali-soluble resin). The radiation-sensitive composition for a color filter according to any one of claims 1 to 4, wherein (roxyethyl) contains succinic acid mono (2-methacryloyloxyethyl).   (C) The color filter according to any one of claims 1 to 5, wherein the polyfunctional monomer is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. Radiation sensitive composition.   (A) The radiation sensitive composition for color filters in any one of Claims 1-6 in which a coloring agent contains an organic pigment.   The color filter which has a pixel formed from the radiation sensitive composition for color filters in any one of Claims 1-7.   A color liquid crystal display device comprising the color filter according to claim 8.