JP3826561B2 - Resin composition for inkjet color filter and method for producing color filter - Google Patents

Description

【００３３】
〔一般式（１）において、Ｘは水素原子、ハロゲン原子、シアノ基、炭素数１〜４のアルキル基または炭素数６〜９のアリール基を示し、Ａは−COO-Ｒ（但し、Ｒは炭素数１〜４のアルキル基または炭素数６〜９のアリール基を示す。）を示し、ｍは１〜３の整数であり、ｎは１〜３の整数である。〕
【００３４】
【化２】

【００３５】
〔一般式（２）において、Ｘ¹ 、Ｘ² およびＸ³ は相互に独立に水素原子、ハロゲン原子、シアノ基、炭素数１〜４のアルキル基または炭素数６〜９のアリール基を示す。但し、Ｘ¹ 、Ｘ² およびＸ³ の２個以上が同時に水素原子をとることはない。〕
【００３６】
一般式（１）および一般式（２）のＸ、Ｘ¹ 、Ｘ² およびＸ³ において、ハロゲン原子としては、例えば、塩素原子、臭素原子、よう素原子等を挙げることができ、炭素数１〜４のアルキル基としては、例えばメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基を挙げることができ、炭素数６〜９のアリール基としては、例えばフェニル基、ｏ−トリル基、ｍ−トリル基、ｐ−トリル基等を挙げることができる。
また、一般式（１）のＡで示される−COO-ＲにおけるＲとしては、Ｘについて例示した炭素数１〜４のアルキル基および炭素数６〜９のアリール基と同様の基を挙げることができる。
【００３７】
一般式（１）および一般式（２）は、２個のイミダゾール単位が１位または２位で相互に結合した構造を一般的に表している。したがって、ビイミダゾール系化合物（１）およびビイミダゾール系化合物（２）は、それらの主要骨格が下記式（３）〜（５）に相当する化合物の単独あるいは２種以上の混合物である。
【００３８】
【化３】

【００３９】
ビイミダゾール系化合物（１）およびビイミダゾール系化合物（２）の具体例を示すと、次のとおりである。
ビイミダゾール系化合物（１）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−エトキシカルボニルフェニル）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）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）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）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）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）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）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）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）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）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）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）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）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）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）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）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）ビイミダゾール
等を挙げることができる。
【００４０】
また、ビイミダゾール系化合物（２）としては、
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’−テトラフェニルビイミダゾール
等を挙げることができる。
【００４１】
これらの化合物のうち、ビイミダゾール系化合物（１）としては、特に、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）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）ビイミダゾールが好ましく、またビイミダゾール系化合物（２）としては、特に、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’−テトラフェニルビイミダゾールが好ましい。
【００４２】
ビイミダゾール系化合物（１）およびビイミダゾール系化合物（２）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放射線照射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、放射線未照射部で硬化反応が生じることがないため、優れたカラーフィルタを形成することができるものである。
本発明において、ビイミダゾール系化合物（１）およびビイミダゾール系化合物（２）は、それぞれ単独でまたは２種以上を混合して使用することができ、またビイミダゾール系化合物（１）とビイミダゾール系化合物（２）とを併用することができる。
本発明におけるビイミダゾール系化合物（１）とビイミダゾール系化合物（２）との合計の使用割合は、（Ｃ）多官能性単量体を使用しない場合、（Ｂ）バインダー樹脂１００重量部に対して、通常、０．０１〜５０重量部、好ましくは０．５〜３０重量部、特に好ましくは０．５〜１０重量部であり、また（Ｃ）多官能性単量体を使用する場合、（Ｃ）多官能性単量体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１〜５０重量部である。この場合、これらの化合物の合計の使用割合を前記範囲内とすることにより、パターン形状、基板との接着性等に優れた画素を形成することができる。
【００４３】
また、本発明においては、（Ｄ）光重合開始剤成分として、ビイミダゾール系化合物（１）および／またはビイミダゾール系化合物（２）と共に、他の光ラジカル発生剤、増感剤、硬化促進剤等や、高分子化合物からなる光架橋剤あるいは光増感剤（以下、「高分子光架橋・増感剤」という。）の１種以上を併用することもできる。
前記他の光ラジカル発生剤としては、例えば、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−（４−イソプロピルフェニル）−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、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−２−フェニルアセトフェノン、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、ベンゾフェノン、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、２，４−ジエチルチオキサントン、３，３−ジメチル−４−メトキシベンゾフェノン、４−アジドベンズアルデヒド、４−アジドアセトフェノン、４−アジドベンザルアセトフェノン、アジドピレン、４−ジアゾジフェニルアミン、４−ジアゾ−４’−メトキシジフェニルアミン、４−ジアゾ−３−メトキシジフェニルアミン、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルフォスフィンオキサイド、ジベンゾイル、ベンゾインイソブチルエーテル、Ｎ−フェニルチオアクリドン、トリフェニルピリリウムパークロレート等を挙げることができる。これらの他の光ラジカル発生剤は、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。
【００４４】
前記増感剤としては、例えば、４−ジエチルアミノアセトフェノン、４−ジメチルアミノプロピオフェノン、エチル−４−ジメチルアミノベンゾエート、２−エチルヘキシル−１，４−ジメチルアミノベンゾエート、２，５−ビス（４’−ジエチルアミノベンザル）シクロヘキサノン、７−ジエチルアミノ−３−（４−ジエチルアミノベンゾイル）クマリン、４−（ジエチルアミノ）カルコン等を挙げることができる。
これらの増感剤は、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。
前記硬化促進剤としては、例えば、２−メルカプトベンゾイミダゾール、２−メルカプトベンゾチアゾール、２−メルカプトベンゾオキサゾール、２，５−ジメルカプト−１，３，４−チアジアゾール、２−メルカプト−４，６−ジメチルアミノピリジン等の連鎖移動剤を挙げることができる。
これらの硬化促進剤は、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。
【００４５】
前記他の光ラジカル発生剤、増感剤および硬化促進剤のうち、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、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、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）ベンゾフェノンおよび２−メルカプトベンゾチアゾールが、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。
【００４６】
本発明においては、（Ｄ）光重合開始剤として、特に、ビイミダゾール系化合物（１）および／またはビイミダゾール系化合物（２）と、ベンゾフェノン系の他の光ラジカル発生剤および／またはチアゾール系の硬化促進剤とを組み合わせて使用することが好ましい。
前記特に好ましい組み合わせの具体例としては、
２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）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）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）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−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）ビイミダゾール／４，４’−ビス（ジメチルアミノ）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−メルカプトベンゾチアゾール、
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−ジブロモフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール／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（２，４，６−トリクロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール／４，４’−ビス（ジメチルアミノ）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−メルカプトベンゾチアゾール
等を挙げることができる。
本発明における他の光ラジカル発生剤の使用割合は、（Ｄ）光重合開始剤全体の８０重量％以下であることが好ましく、また増感剤および／または硬化促進剤の使用割合は、（Ｄ）光重合開始剤全体の８０重量％以下であることが好ましい。
【００４７】
さらに、前記高分子光架橋・増感剤は、光架橋剤あるいは光増感剤として機能しうる官能基を主鎖および／または側鎖中に有する高分子化合物であり、その例としては、４−アジドベンズアルデヒドとポリビニルアルコールとの縮合物、４−アジドベンズアルデヒドとフェノールノボラック樹脂との縮合物、４−（メタ）アクリロイルフェニルシンナモイルエステルの（共）重合体、１，４−ポリブタジエン、１，２−ポリブタジエン等を挙げることができる。
これらの高分子光架橋・増感剤は、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。
本発明における高分子光架橋・増感剤の使用割合は、ビイミダゾール系化合物（１）および／またはビイミダゾール系化合物（２）１００重量部に対して、通常、２００重量部以下、好ましくは１８０重量部以下である。
【００４８】
（Ｅ）他の添加剤
本発明における樹脂組成物は、必要に応じて、種々の他の添加剤を含有することもできる。
前記他の添加剤としては、例えば、
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、ポリフロロアルキルアクリレート等の高分子化合物；
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；
以下商品名で、エフトップＥＦ３０１、同ＥＦ３０３、同ＥＦ３５２（以上、新秋田化成（株）製）、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７８Ｋ（以上、大日本インキ化学工業（株）製）、フロラードＦＣ４３０、同ＦＣ４３１（以上、住友スリーエム（株）製）、アサヒガードＡＧ７１０、サーフロンＳ−３８２、同ＳＣ−１０１、同ＳＣ−１０２、同ＳＣ−１０３、同ＳＣ−１０４、同ＳＣ−１０５、同ＳＣ−１０６（以上、旭硝子（株）製）、ＫＰ３４１（信越化学工業（株）製）、ポリフローＮｏ．７５、同Ｎｏ．９５（以上、共栄社油脂化学工業（株）製）等の界面活性剤
等を挙げることができる。
【００４９】
また、本発明における樹脂組成物は、熱酸発生剤や酸架橋剤を含有することができる。
前記熱酸発生剤は、加熱により酸を発生する成分であり、その例としては、スルホニウム塩、ベンゾチアゾリウム塩、アンモニウム塩、ホスホニウム塩等のオニウム塩を挙げることができ、特に、スルホニウム塩およびベンゾチアゾリウム塩が好ましい。
前記スルホニウム塩としては、下記式（６）で表される化合物（以下、「スルホニウム塩（６）」という。）が好ましい。
【００５０】
【化４】

【００５１】
〔式（６）において、R¹、R²およびR³は相互に独立に炭素数１〜５の１価の炭化水素基もしくはその置換誘導体、または炭素数６〜１０のアリール基もしくはその置換誘導体を示し、かつR¹、R²およびR³の少なくとも１つは炭素数６〜１０のアリール基またはその置換誘導体であり、 X^- は１価のアニオンを示す。〕
【００５２】
スルホニウム塩（６）の具体例としては、
４−アセトフェニルジメチルスルホニウムヘキサフルオロアンチモネート、４−アセトキシフェニルジメチルスルホニウムヘキサフルオロアルセネート、ジメチル−４−（ベンジルオキシカルボニルオキシ）フェニルスルホニウムヘキサフルオロアンチモネート、ジメチル−４−（ベンゾイルオキシ）フェニルスルホニウムヘキサフルオロアンチモネート、ジメチル−４−（ベンゾイルオキシ）フェニルスルホニウムヘキサフルオロアルセネート、ジメチル−３−クロロ−４−アセトキシフェニルスルホニウムヘキサフルオロアンチモネート等のアルキルスルホニウム塩類；
ベンジル−４−ヒドロキシフェニルメチルスルホニウムヘキサフルオロアンチモネート、ベンジル−４−ヒドロキシフェニルメチルスルホニウムヘキサフルオロホスフェート、４−アセトキシフェニルベンジルメチルスルホニウムヘキサフルオロアンチモネート、ベンジル−４−メトキシフェニルメチルスルホニウムヘキサフルオロアンチモネート、ベンジル−２−メチル−４−ヒドロキシフェニルメチルスルホニウムヘキサフルオロアンチモネート、ベンジル−３−クロロ−４−ヒドロキシフェニルメチルスルホニウムヘキサフルオロアルセネート、４−メトキシベンジル−４−ヒドロキシフェニルメチルスルホニウムヘキサフルオロホスフェート等のモノベンジルスルホニウム塩類；
【００５３】
ジベンジル−４−ヒドロキシフェニルスルホニウムヘキサフルオロアンチモネート、ジベンジル−４−ヒドロキシフェニルスルホニウムヘキサフルオロホスフェート、４−アセトキシフェニルジベンジルスルホニウムヘキサフルオロアンチモネート、ジベンジル−４−メトキシフェニルスルホニウムヘキサフルオロアンチモネート、ジベンジル−３−クロロ−４−ヒドロキシフェニルスルホニウムヘキサフルオロアルセネート、ジベンジル−３−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニルスルホニウムヘキサフルオロアンチモネート、ベンジル−４−メトキシベンジル−４−ヒドロキシフェニルスルホニウムヘキサフルオロホスフェート等のジベンジルスルホニウム塩類；
ｐ−クロロベンジル−４−ヒドロキシフェニルメチルスルホニウムヘキサフルオロアンチモネート、ｐ−ニトロベンジル−４−ヒドロキシフェニルメチルスルホニウムヘキサフルオロアンチモネート、ｐ−クロロベンジル−４−ヒドロキシフェニルメチルスルホニウムヘキサフルオロホスフェート、ｐ−ニトロベンジル−３−メチル−４−ヒドロキシフェニルメチルスルホニウムヘキサフルオロアンチモネート、３,５−ジクロロベンジル−４−ヒドロキシフェニルメチルスルホニウムヘキサフルオロアンチモネート、ｏ−クロロベンジル−３−クロロ−４−ヒドロキシフェニルメチルスルホニウムヘキサフルオロアンチモネート等の置換ベンジルスルホニウム塩類
等を挙げることができる。
【００５４】
また、前記ベンゾチアゾニウム塩の具体例としては、３−ベンジルベンゾチアゾリウムヘキサフルオロアンチモネート、３−ベンジルベンゾチアゾリウムヘキサフルオロホスフェート、３−ベンジルベンゾチアゾリウムテトラフルオロボレート、３−（ｐ−メトキシベンジル）ベンゾチアゾリウムヘキサフルオロアンチモネート、３−ベンジル−２−メチルチオベンゾチアゾリウムヘキサフルオロアンチモネート、３−ベンジル−５−クロロベンゾチアゾリウムヘキサフルオロアンチモネート等のベンジルベンゾチアゾリウム塩類を挙げることができる。
【００５５】
前記スルホニウム塩（６）およびベンゾチアゾリウム塩のうち、４−アセトキシフェニルジメチルスルホニウムヘキサフルオロアルセネート、ベンジル−４−ヒドロキシフェニルメチルスルホニウムヘキサフルオロアンチモネート、４−アセトキシフェニルベンジルメチルスルホニウムヘキサフルオロアンチモネート、ジベンジル−４−ヒドロキシフェニルスルホニウムヘキサフルオロアンチモネート、４−アセトキシフェニルジベンジルスルホニウムヘキサフルオロアンチモネート、３−ベンジルベンゾチアゾリウムヘキサフルオロアンチモネート等が好ましい。これらの化合物の市販品には、サンエイドＳＩ−Ｌ８５、同ＳＩ−Ｌ１１０、同ＳＩ−Ｌ１４５、同ＳＩ−Ｌ１５０、同ＳＩ−Ｌ１６０（以上、三新化学工業（株）製）等がある。
前記熱酸発生剤は、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。
【００５６】
前記酸架橋剤は、下記式
−CH₂OR
（式中、R は水素原子または炭素原子数が、通常、１〜６、好ましくは１〜４のアルキル基を示す。）
で表される１価の有機基（以下、「メチロール（エーテル）基」という。）を、一分子中に好ましくは２個以上有する化合物であり、好ましくは該１価の有機基が窒素原子に結合した化合物、即ちＮ−メチロール基および／またはＮ−アルコキシメチル基を有する化合物からなる。酸架橋剤が一分子中にメチロール（エーテル）基を２個以上有するとき、各メチロール（エーテル）基は相互に同一でも異なってもよい。
酸架橋剤は、（Ｂ）バインダー樹脂がカルボキシル基を有する場合、酸架橋剤中のメチロール（エーテル）基が、熱酸発生剤から発生した酸の存在下で、（Ｂ）バインダー樹脂中のカルボキシル基と反応して、架橋構造を形成する成分である。
このような酸架橋剤として、例えば、
下記一般式（７）
【００５７】
【化５】

【００５８】
〔一般式（７）において、R⁴〜R⁹は相互に独立に炭素原子数が、通常、１〜６、好ましくは１〜４のアルキル基を示す。〕
で表されるN,N,N,N,N,N-ヘキサ（アルコキシメチル）メラミン等のアルコキシメチル化メラミン類、
下記一般式（８）
【００５９】
【化６】

【００６０】
〔一般式（８）において、 R¹⁰〜R¹³ は相互に独立に炭素原子数が、通常、１〜６、好ましくは１〜４のアルキル基を示す。〕
で示されるN,N,N,N-テトラ（アルコキシメチル）グリコールウリル等のアルコキシメチル化グリコールウリル類
等を挙げることができる。
また、酸架橋剤として、尿素−ホルムアルデヒド樹脂、チオ尿素−ホルムアルデヒド樹脂、メラミン−ホルムアルデヒド樹脂、グアナミン−ホルムアルデヒド樹脂、ベンゾグアナミン−ホルムアルデヒド樹脂、グリコールウリル−ホルムアルデヒド樹脂、ポリビニルフェノール類等に、メチロール（エーテル）基を導入した化合物を使用することもできる。
【００６１】
前記酸架橋剤のうち、アルコキシメチル化メラミン類およびアルコキシメチル化グリコールウリル類が好ましく、特にアルコキシメチル化メラミン類が好ましい。また、架橋性、耐熱性および耐溶剤性のバランスに優れ、低誘電率の硬化物が得られる点から、アルコキシメチル化メラミン類（α）とアルコキシメチル化グリコールウリル類（β）とを、重量比〔（α）／（β）〕として、好ましくは５／９５〜９５／５、さらに好ましくは１０／９０〜９０／１０の割合で混合した架橋剤も特に好ましく使用することができる。
【００６２】
（Ｆ）溶剤
本発明における樹脂組成物は、溶剤を含有する液状組成物として使用される。
前記溶剤は、ジエチレングリコールモノ−ｎ−ブチルエーテルアセテートからなる。
【００６３】
溶剤の使用割合は、（Ｂ）バインダー樹脂１００重量部に対して、１００〜１００００重量部、好ましくは５００〜５０００重量部である。
【００６４】
カラーフィルタの製造方法
次に、本発明のインクジェット方式カラーフィルタ用樹脂組成物を用いて、カラーフィルタを製造する方法について説明する。
まず、放射線の照射により硬化する感放射線性樹脂組成物を透明基板に塗布したのち、プリベーク（ＰＢ）を行い溶剤を蒸発させて、塗膜を形成する。この場合のＰＢの条件は、例えば、加熱温度が５０〜１５０℃程度、加熱時間が３０〜６００秒程度である。その後、この塗膜にフォトマスクを介して放射線を照射したのち、ポストエキスポジャーベーク（ＰＥＢ）を行い、その後アルカリ現像液により現像処理を行って、塗膜の放射線未照射部を溶解除去することにより、周囲に隔壁を有する所定形状の隔壁パターンが所定の配列にしたがって配置されたパターンアレイを形成する。この場合のＰＥＢの条件は、例えば、加熱温度が５０〜１５０℃程度、加熱時間が３０〜６００秒程度であり、放射線の照射条件は、例えば１〜５００ｍＪ／ｃｍ² 程度である。また、現像条件は、例えば１０〜３００秒程度であり、現像方法としては、例えば、液盛り法、ディッピング法、振動浸漬法等を採用することができる。また、現像後にさらにポストベークを行ってもよく、その条件は、例えば、加熱温度が１５０〜２８０℃程度、加熱時間が３分〜２時間程度である。
【００６５】
次いで、本発明のインクジェット方式カラーフィルタ用樹脂組成物を用いて、例えば、赤色、緑色または青色の該樹脂組成物を順次各隔壁パターン内にインクジェット方式により吐出させ、場合によりその後放射線を照射する。この場合の放射線の照射条件は、例えば、１〜５００ｍＪ／ｃｍ² 程度であり、樹脂組成物の吐出速度は、例えば、０．０１〜１００ｍ／秒程度である。その後、ベークを行って、赤色、緑色、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。この場合のベークの条件は、例えば、加熱温度が１５０〜２８０℃程度、加熱時間が３分〜２時間程度である。
【００６６】
カラーフィルタを製造する際に使用される透明基板としては、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。また、これらの透明基板には、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。
カラーフィルタを製造する際に使用される感放射線性樹脂組成物としては、例えば、前記（Ｂ）、（Ｃ）および（Ｄ）成分を含有し、場合により前記（Ａ）成分、（Ｅ）成分あるいは（Ｆ）成分の少なくとも１種をさらに含有する組成物等を使用することができる。
感放射線性樹脂組成物を透明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、ＰＢ後の膜厚として、通常、０．１〜１０μｍ、好ましくは０．５〜３．０μｍである。
隔壁パターンを形成する際に使用される放射線としては、可視光線、紫外線、遠紫外線、Ｘ線、電子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。
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、硅素ナトリウム、メタ硅素ナトリウム、アンモニア水、エチルアミン、ｎ−プロピルアミン、ジエチルアミン、ジ−ｎ−プロピルアミン、トリエチルアミン、メチルジエチルアミン、ジメチルエタノールアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、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。なお、アルカリ現像液による現像後は、通常、水洗する。
【００６７】
このようなカラーフィルタの製造方法は、画素形成工程が簡便であり、かつコストも低く、工業的に極めて有利である。
本発明のインクジェット方式カラーフィルタ用樹脂組成物を用いて製造されたカラーフィルタは、例えば、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。
【００６８】
【発明の実施の形態】
本発明のインクジェット方式カラーフィルタ用樹脂組成物は、（Ａ）着色剤、（Ｂ）バインダー樹脂および（Ｆ）溶剤を必須の成分とし、場合により、（Ｃ）多官能性単量体、（Ｄ）光重合開始剤あるいは（Ｅ）他の添加剤も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）〜（ホ）のとおりである。
（イ） （Ｂ）成分がカルボキシル基含有共重合体（Ｂ１）および／またはＮ位−置換マレイミド共重合体（Ｂ２）を含有するインクジェット方式カラーフィルタ用樹脂組成物。
【００６９】
（ロ） （Ｂ）成分であるカルボキシル基含有共重合体（Ｂ１）がメタクリル酸／ベンジルメタクリレート共重合体、メタクリル酸／メチルメタクリレート／スチレン共重合体、メタクリル酸／ベンジルメタクリレート／スチレン共重合体、メタクリル酸／メチルメタクリレート／ポリスチレンマクロモノマー共重合体、メタクリル酸／メチルメタクリレート／ポリメチルメタクリレートマクロモノマー共重合体、メタクリル酸／ベンジルメタクリレート／ポリスチレンマクロモノマー共重合体、メタクリル酸／ベンジルメタクリレート／ポリメチルメタクリレートマクロモノマー共重合体、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／ポリスチレンマクロモノマー共重合体およびメタクリル酸／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／ポリメチルメタクリレートマクロモノマー共重合体の群から選ばれる少なくとも１種からなり、Ｎ位−置換マレイミド共重合体（Ｂ２）がＮ−フェニルマレイミド／メタクリル酸／スチレン／アリルアクリレート共重合体、Ｎ−フェニルマレイミド／メタクリル酸／スチレン／アリルメタアクリレート共重合体、Ｎ−フェニルマレイミド／メタクリル酸／スチレン／ベンジルメタクリレート共重合体、Ｎ−フェニルマレイミド／メタクリル酸／スチレン／フェニルメタクリレート共重合体、Ｎ−フェニルマレイミド／メタクリル酸／スチレン／ベンジルメタクリレート／ポリスチレンマクロモノマー共重合体、Ｎ−フェニルマレイミド／メタクリル酸／スチレン／ベンジルメタクリレート／ポリメチルメタクリレートマクロモノマー共重合体、Ｎ−フェニルマレイミド／メタクリル酸／スチレン／フェニルメタクリレート／ポリスチレンマクロモノマー共重合体、Ｎ−フェニルマレイミド／メタクリル酸／スチレン／フェニルメタクリレート／ポリメチルメタクリレートマクロモノマー共重合体、Ｎ−フェニルマレイミド／メタクリル酸／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／ポリスチレンマクロモノマー共重合体、Ｎ−フェニルマレイミド／メタクリル酸／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／ポリメチルメタクリレートマクロモノマー共重合体、Ｎ−フェニルマレイミド／メタクリル酸／スチレン／２−ヒドロキシエチルメタクリレート／フェニルメタクリレート／ポリスチレンマクロモノマー共重合体、Ｎ−フェニルマレイミド／メタクリル酸／スチレン／２−ヒドロキシエチルメタクリレート／フェニルメタクリレート／ポリメチルメタクリレートマクロモノマー共重合体の群から選ばれる少なくとも１種を含有する、前記（イ）記載のインクジェット方式カラーフィルタ用樹脂組成物。
【００７０】
（ハ） （Ｃ）成分がトリメチロールプロパントリアクリレート、ジペンタエリスリトールペンタ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種を含有する、前記（イ）または（ロ）記載のインクジェット方式カラーフィルタ用樹脂組成物。
（ニ） （Ａ）成分が有機顔料を含有する前記（イ）、（ロ）または（ハ）記載のインクジェット方式カラーフィルタ用樹脂組成物。
【００７１】
（ホ） （Ｄ）成分が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）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）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）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−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）ビイミダゾール／４，４’−ビス（ジメチルアミノ）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−メルカプトベンゾチアゾール、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−ジブロモフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール／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および２，２’−ビス（２，４，６−トリクロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾール／４，４’−ビス（ジメチルアミノ）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−メルカプトベンゾチアゾールの群から選ばれる少なくとも１種を含有する、前記（イ）、（ロ）、（ハ）または（ニ）記載のインクジェット方式カラーフィルタ用樹脂組成物。
【００７３】
【実施例】
以下、実施例を挙げて、本発明をさらに具体的に説明する。但し、本発明は、これらの実施例に何ら制約されるものではない。
【００７４】
実施例１
（Ａ）成分として、C.I.ピグメントレッド１７７を６５重量部、（Ｂ）成分として、メタクリル酸／ベンジルメタクリレート／ポリスチレンマクロモノマー共重合体（共重合重量比＝２５／６５／１０、重量平均分子量＝５５，０００）５０重量部、（Ｃ）成分として、ジペンタエリスリトールペンタアクリレート４０重量部、（Ｆ）成分として、ジエチレングリコールモノ−ｎ−ブチルエーテルアセテート８００重量部を混合して、赤色に着色された樹脂組成物を調製した。
別に、表面にナトリウムイオンの溶出を防止するシリカ(SiO₂)膜が形成されたソーダガラス製透明基板の表面上に、感放射線性樹脂組成物を塗布したのち、ホットプレート上にて１１０℃で２分間ＰＢを行い溶剤を蒸発させて、塗膜を形成した。その後、この塗膜にフォトマスクを介して放射線を４０ｍＪ／ｃｍ² 照射して、１１０℃で２分間ＰＥＢを行ったのち、アルカリ現像液により２５℃で１分間現像処理を行い、塗膜の放射線未照射部を溶解除去し、さらに２００℃で３０分間ポストベークを行うことによって、画素パターンを形成する部分を区画するように、隔壁パターンを形成した。
次いで、前記樹脂組成物を隔壁パターン内にインクジェット方式により吐出したのち、２００℃のオーブン内で１時間ベークを行って、赤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た。
得られたカラーフィルタは、画素の表面平滑性に優れ、画素の膜厚バラツキが２％未満であり、かつ色ムラを生ずることもなく、優れた特性を有するものであった。
また、このときの隔壁パターンと前記樹脂組成物との接触角（樹脂組成物が基板表面に接触してから１分以内に測定された値）は、約５０度であった。
【００７５】
実施例２
（Ａ）成分として、C.I.ピグメントレッド１７７を６５重量部、（Ｂ）成分として、メタクリル酸／ベンジルメタクリレート／ポリスチレンマクロモノマー共重合体（共重合重量比＝２５／６５／１０、重量平均分子量＝５５，０００）５０重量部、（Ｃ）成分として、ジペンタエリスリトールペンタアクリレート４０重量部、（Ｅ）成分として、メガファックＦ１７２を１．５重量部、（Ｆ）成分として、ジエチレングリコールモノ−ｎ−ブチルエーテルアセテート８００重量部を混合して、赤色に着色された樹脂組成物を調製した。
別に、表面にナトリウムイオンの溶出を防止するシリカ(SiO₂)膜が形成されたソーダガラス製透明基板の表面上に、感放射線性樹脂組成物を塗布したのち、ホットプレート上にて１１０℃で２分間ＰＢを行い溶剤を蒸発させて、塗膜を形成した。その後、この塗膜にフォトマスクを介して放射線を４０ｍＪ／ｃｍ² 照射して、１１０℃で２分間ＰＥＢを行ったのち、アルカリ現像液により２５℃で１分間現像処理を行い、塗膜の放射線未照射部を溶解除去し、さらに２００℃で３０分間ポストベークを行うことによって、画素パターンを形成する部分を区画するように、隔壁パターンを形成した。
次いで、前記樹脂組成物を隔壁パターン内にインクジェット方式により吐出したのち、２００℃のオーブン内で１時間ベークを行って、赤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た。
得られたカラーフィルタは、画素の表面平滑性に優れ、画素の膜厚バラツキが２％未満であり、かつ色ムラを生ずることもなく、優れた特性を有するものであった。
また、このときの隔壁パターンと前記樹脂組成物との接触角（樹脂組成物が基板表面に接触してから１分以内に測定された値）は、約５０度であった。
【００７６】
実施例３
（Ａ）成分として、C.I.ピグメントレッド１７７を６５重量部、（Ｂ）成分として、メタクリル酸／ベンジルメタクリレート／ポリスチレンマクロモノマー共重合体（共重合重量比＝２５／６５／１０、重量平均分子量＝５５，０００）５０重量部、（Ｃ）成分として、ジペンタエリスリトールペンタアクリレート４０重量部、（Ｄ）成分として、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）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、（Ｆ）成分として、ジエチレングリコールモノ−ｎ−ブチルエーテルアセテート８００重量部を混合して、赤色に着色された樹脂組成物を調製した。
別に、表面にナトリウムイオンの溶出を防止するシリカ(SiO₂)膜が形成されたソーダガラス製透明基板の表面上に、感放射線性樹脂組成物を塗布したのち、ホットプレート上にて１１０℃で２分間ＰＢを行い溶剤を蒸発させて、塗膜を形成した。その後、この塗膜にフォトマスクを介して放射線を４０ｍＪ／ｃｍ² 照射して、１１０℃で２分間ＰＥＢを行ったのち、アルカリ現像液により２５℃で１分間現像処理を行い、塗膜の放射線未照射部を溶解除去し、さらに２００℃で３０分間ポストベークを行うことによって、画素パターンを形成する部分を区画するように、隔壁パターンを形成した。
次いで、前記樹脂組成物を隔壁パターン内にインクジェット方式により吐出したのち、放射線を４０ｍＪ／ｃｍ² 照射し、その後２００℃のオーブン内で１時間ベークを行って、赤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た。
得られたカラーフィルタは、画素の表面平滑性に優れ、画素の膜厚バラツキが２％未満であり、かつ色ムラを生ずることもなく、優れた特性を有するものであった。
また、このときの隔壁パターンと前記樹脂組成物との接触角（樹脂組成物が基板表面に接触してから１分以内に測定された値）は、約５０度であった。
【００７７】
【発明の効果】
本発明のインクジェット方式カラーフィルタ用樹脂組成物は、画素パターンを形成する際にインクジェット方式を用いるものであり、優れた特性を有するカラーフィルタを、簡便な画素形成工程により低コストで製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition for an ink jet type color filter for producing a color filter used for a color liquid crystal display device, a color image pickup tube element and the like by an ink jet method, Color filter, ink-jet color filter manufacturing method, and color liquid crystal display deviceAbout.
[0002]
[Prior art]
Color filters used in color liquid crystal display devices (LCDs) and color image pickup tubes are generally irradiated with radiation through a photomask on a radiation-sensitive resin coating to cure the radiation-emitting portion, and then develop. Then, after removing the part of the coating that has not been irradiated with radiation to form a pattern, a method of dyeing (dyeing method) or a composition in which a red, green or blue colorant is dispersed in a radiation sensitive resin It is manufactured by a photolithography method that sequentially uses and performs coating film formation, radiation irradiation, and development processing in the same manner as described above. However, these methods have problems such as a complicated pixel formation process and high cost.
[0003]
[Problems to be solved by the invention]
The present invention has been made in consideration of the above-mentioned circumstances in the prior art, and the problem is that a resin composition used for manufacturing a color filter by an inkjet method with a simple pixel formation process and low cost., And method for producing color filter by ink jet method using the resin compositionIs to provide.
[0004]
[Means for Solving the Problems]
  The present invention
(A) A resin composition containing a colorant, (B) a binder resin, and (F) a solvent, wherein the component (F) is composed of diethylene glycol mono-n-butyl ether acetate, and the proportion of the component (F) used is (B) Resin composition for ink jet color filter, which is 100 to 10,000 parts by weight with respect to 100 parts by weight of component,
Consists of.
  The present invention also provides
The inkjet color filter resin composition is ejected by an inkjet method into each of the partition patterns of a transparent substrate on which a pattern array in which partition patterns of a predetermined shape are arranged according to a predetermined arrangement is applied, and then radiation is sometimes applied. Then, by baking, a color filter manufacturing method comprising a step of forming a pixel array on the substrate,
Consists of.
[0005]
The present invention will be 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 color filter, and may be an organic colorant or an inorganic colorant.
The organic colorant specifically means dyes, organic pigments, natural pigments, and the like, and the inorganic colorant specifically means inorganic salts in addition to inorganic pigments. However, since the color filter is required to have high-precision color development and heat resistance, the colorant in the present invention is a colorant having high color development and high heat resistance, particularly coloring with high heat decomposition resistance. An organic colorant, especially an organic pigment is preferred.
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. 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;
[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 pigment or extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron (III) oxide), cadmium red, ultramarine blue, Examples include bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.
In this invention, a coloring agent can be used individually or in mixture of 2 or more types.
[0011]
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.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene alkyl phenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes and the following trade names: KP (Shin-Etsu Chemical Industry), Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), F Top (manufactured by Tochem Products), MegaFuck (manufactured by Dainippon Ink and Chemicals) Lard (Sumitomo 3M), mention may be made of Asahi guard, Sarfron (manufactured by Asahi Glass Co., Ltd.), and the like.
These surfactants can be used alone or in admixture of two or more.
The amount of the surfactant used is usually 50 parts by weight or less, preferably 1 to 30 parts by weight with respect to 100 parts by weight of the colorant.
[0012]
(B) Binder resin
As the binder resin in the present invention, an appropriate resin can be used as long as it acts as a binder for the colorant.
A preferred binder resin in the present invention is a polymer containing a carboxyl group, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter simply referred to as “carboxyl group-containing unsaturated monomer”). ) And other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as “other unsaturated monomers (b1)”) (hereinafter referred to as “carboxyl group-containing copolymer (B1)”). ) ").
[0013]
As the carboxyl group-containing unsaturated monomer, for example,
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid;
Trivalent or higher unsaturated polycarboxylic acids (anhydrides);
2 such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), etc. Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids having higher valences,
ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate
Etc.
These carboxyl group-containing ethylenically unsaturated monomers can be used alone or in admixture of two or more.
[0014]
Moreover, as another unsaturated monomer (b1), for example,
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;
[0015]
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 or unsaturated imides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide, maleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
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, polysiloxane, etc.
Etc.
These other unsaturated monomers (b1) can be used alone or in admixture of two or more.
[0016]
  As the carboxyl group-containing copolymer (B1),(I)With acrylic acid and / or methacrylic acid( ii)A copolymer with at least one selected from the group of methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer and polymethyl methacrylate macromonomer is preferred. .
[0017]
As a specific example of a preferable carboxyl group-containing copolymer (B1),
Acrylic acid / benzyl acrylate copolymer, acrylic acid / methyl acrylate / styrene copolymer, acrylic acid / benzyl acrylate / styrene copolymer, acrylic acid / methyl acrylate / polystyrene macromonomer copolymer, acrylic acid / methyl acrylate / Polymethylmethacrylate macromonomer copolymer, acrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polystyrene Macromonomer copolymer, acrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethyl methacrylate macromonomer copolymer,
Acrylic acid / benzyl methacrylate copolymer, acrylic acid / methyl methacrylate / styrene copolymer, acrylic acid / benzyl methacrylate / styrene copolymer, acrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / methyl methacrylate / Polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene Macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate mac Monomer copolymers
Acrylic acid copolymers such as;
[0018]
Methacrylic acid / benzyl acrylate copolymer, methacrylic acid / methyl acrylate / styrene copolymer, methacrylic acid / benzyl acrylate / styrene copolymer, methacrylic acid / methyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl acrylate / Polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polystyrene Macromonomer copolymer, methacrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethyl methacrylate Ma copolymer,
Methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / methyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl methacrylate / Polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene Macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl Takuri rate macromonomer copolymer
Methacrylic acid copolymers such as
Etc.
[0019]
Among these carboxyl group-containing copolymers (B1), methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / methyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / Methyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer Polymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxy Chill methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymers.
The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer (B1) is usually 5 to 50% by weight, preferably 10 to 40% by weight.
In this invention, a carboxyl group-containing copolymer (B1) can be used individually or in mixture of 2 or more types.
[0020]
Another preferred binder resin in the present invention is an N-substituted maleimide and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as “other unsaturated monomer (b2)”). (Hereinafter, referred to as “N-position-substituted maleimide copolymer (B2)”).
Examples of the N-substituent in the N-substituted maleimide include a (Cyclo) alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and these groups. Among these N-substituents, aryl groups having 6 to 20 carbon atoms and substituted derivatives thereof are preferable.
[0021]
Specific examples of the N-substituted maleimide include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, N N- (cyclo) alkyl-substituted maleimides such as -n-pentylmaleimide, Nn-hexylmaleimide, N-cyclohexylmaleimide, N-4-methylcyclohexylmaleimide, N-4-chlorocyclohexylmaleimide, and their substitution Derivatives;
N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methyl N-aryl-substituted maleimides such as phenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, Np-chlorophenylmaleimide, and substituted derivatives thereof;
N-benzylmaleimide, N-phenethylmaleimide, N-o-hydroxybenzylmaleimide, Nm-hydroxybenzylmaleimide, Np-hydroxybenzylmaleimide, N-o-methylbenzylmaleimide, Nm-methylbenzylmaleimide, N-aralkyl-substituted maleimides such as Np-methylbenzylmaleimide, N-o-methoxybenzylmaleimide, Nm-methoxybenzylmaleimide, Np-methoxybenzylmaleimide, Np-chlorobenzylmaleimide, These substituted derivatives
Etc.
[0022]
Of these N-substituted maleimides, N-cyclohexylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenyl Maleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide are preferred.
The N-substituted maleimides can be used alone or in admixture of two or more.
[0023]
The other unsaturated monomer (b2) is not limited as long as it can be copolymerized with the N-substituted maleimide, but one or more of the carboxyl group-containing unsaturated monomers and the other A monomer mixture containing at least one unsaturated monomer (b1) is preferred.
[0024]
  As the N-substituted maleimide copolymer (B2), a copolymer of N-phenylmaleimide is preferable, and N-phenylmaleimide, a carboxyl group-containing unsaturated monomer, and other unsaturated monomers ( a copolymer with b1),(I)N-phenylmaleimide;( ii)Acrylic acid and / or methacrylic acid,(iii) With styrene,( iv)Co-polymerization with at least one selected from the group consisting of methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer. Polymers are preferred.
[0025]
Specific examples of preferred N-substituted maleimide copolymers (B2) include
N-phenylmaleimide / methacrylic acid / styrene / allyl acrylate copolymer,
N-phenylmaleimide / methacrylic acid / styrene / allyl methacrylate copolymer,
N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate copolymer,
N-phenylmaleimide / methacrylic acid / styrene / phenyl methacrylate copolymer,
N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate / polystyrene macromonomer copolymer,
N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer,
N-phenylmaleimide / methacrylic acid / styrene / phenyl methacrylate / polystyrene macromonomer copolymer,
N-phenylmaleimide / methacrylic acid / styrene / phenyl methacrylate / polymethyl methacrylate macromonomer copolymer,
N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer,
N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer,
N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate / polystyrene macromonomer copolymer,
N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate / polymethyl methacrylate macromonomer copolymer
Etc.
[0026]
The copolymerization ratio of the N-substituted maleimide in the N-substituted maleimide copolymer (B2) is usually 5 to 50% by weight, preferably 10 to 40% by weight.
When the N-substituted maleimide copolymer is a copolymer of an N-substituted maleimide, a carboxyl group-containing unsaturated monomer, and another unsaturated monomer (b1), the carboxyl group-containing unsaturated The copolymerization ratio of the monomer is usually 5 to 50% by weight, preferably 10 to 40% by weight, and the copolymerization ratio of the other unsaturated monomer (b1) is usually 10 to 90% by weight. , Preferably 20 to 80% by weight.
In the present invention, the N-position-substituted maleimide copolymer (B2) can be used alone or in admixture of two or more.
[0027]
The polystyrene-converted weight average molecular weight (hereinafter simply referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC; elution solvent tetrahydrofuran) of each resin component constituting the binder resin in the present invention is preferably 3, 000 to 300,000, particularly preferably 5,000 to 100,000.
The ratio of the binder resin used in the present invention is usually 10 to 1000 parts by weight, preferably 20 to 500 parts by weight, with respect to 100 parts by weight of the (A) colorant. In this case, if the use ratio of the binder resin is less than 10 parts by weight, for example, there is a tendency for the ink dischargeability and film hardness to decrease, whereas if it exceeds 1000 parts by weight, the colorant concentration relatively decreases, It may be difficult to achieve the target color density as a thin film.
[0028]
(C) Multifunctional monomer
The resin composition in the present invention can contain a polyfunctional monomer having two or more polymerizable ethylenically unsaturated bonds as a crosslinkable monomer component.
Examples of the polyfunctional monomer include diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Polyacrylate or dimethacrylate of polyalkylene glycol such as polyethylene glycol or polypropylene glycol; Polyacrylate or polymethacrylate of trihydric or higher polyhydric alcohol such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol; polyester, epoxy Oligoacrylates or oligomethacrylates such as resins, urethane resins, alkyd resins, silicone resins, and spirane resins; diacrylates of hydroxylated polymers at both ends such as hydroxypolybutadiene at both ends, hydroxypolyisoprene at both ends, and hydroxypolycaprolactone at both ends Or dimethacrylates, tris (2-acryloyloxyethyl) phosphate, tris (2-methacryloyloxy) Ethyl) phosphate, and the like can be given.
[0029]
Among these polyfunctional monomers, polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol Trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like are preferable, and trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate have a pixel intensity of It is preferable in that it is high and the smoothness of the pixel surface is excellent.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.
The use ratio of the polyfunctional monomer in the present invention is usually 500 parts by weight or less, preferably 20 to 300 parts by weight, with respect to 100 parts by weight of the (B) binder resin. In this case, when the usage ratio of the polyfunctional monomer exceeds 500 parts by weight, the ink dischargeability tends to be lowered.
[0030]
In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable ethylenically unsaturated bond.
Specific examples of such monofunctional monomers include methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, Methoxydipropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, succinic acid 2-acryloyloxyethyl, succinic acid 2- Methacryloyloxyethyl, ω-carbo Sheet - polycaprolactone monoacrylate, .omega.-carboxy - can be exemplified polycaprolactone monomethacrylate or the like, commercially, M-5300 can be cited (trade name, manufactured by Toagosei Co., Ltd.) and the like.
These monofunctional monomers can be used alone or in admixture of two or more.
The proportion of the monofunctional monomer used in the present invention is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer.
[0031]
(D) Photopolymerization initiator
The resin composition in the present invention can impart radiation curability by blending a photopolymerization initiator.
Here, the radiation means that containing visible light, ultraviolet rays, far ultraviolet rays, X-rays, electron beams and the like.
Examples of the photopolymerization initiator include a compound represented by the following general formula (1) (hereinafter referred to as “biimidazole compound (1)”) and a compound represented by the following general formula (2) (hereinafter, “ A component containing at least one biimidazole compound selected from the group of “biimidazole compound (2)”) is preferable.
[0032]
[Chemical 1]

[0033]
[In General Formula (1), X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, A represents —COO—R (where R represents Represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms.), M is an integer of 1 to 3, and n is an integer of 1 to 3. ]
[0034]
[Chemical 2]

[0035]
[In General Formula (2), X¹, X²And X^ThreeEach independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms. However, X¹, X²And X^ThreeTwo or more of these do not take a hydrogen atom at the same time. ]
[0036]
X and X in the general formula (1) and the general formula (2)¹, X²And X^ThreeExamples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and i- Examples thereof include a propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, and a t-butyl group. Examples of the aryl group having 6 to 9 carbon atoms include a phenyl group, an o-tolyl group, and m- A tolyl group, p-tolyl group, etc. can be mentioned.
Examples of R in —COO—R represented by A in formula (1) include the same groups as the alkyl groups having 1 to 4 carbon atoms and aryl groups having 6 to 9 carbon atoms exemplified for X. it can.
[0037]
General formula (1) and general formula (2) generally represent a structure in which two imidazole units are bonded to each other at the 1-position or 2-position. Accordingly, the biimidazole compound (1) and the biimidazole compound (2) are single or a mixture of two or more compounds whose main skeletons correspond to the following formulas (3) to (5).
[0038]
[Chemical Formula 3]

[0039]
Specific examples of the biimidazole compound (1) and the biimidazole compound (2) are as follows.
As biimidazole compound (1),
2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole,
2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole,
2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole,
2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole,
2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole,
2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole,
2,2'-bis (2-cyanophenyl) -4,4 ', 5.5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole,
2,2'-bis (2-cyanophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole,
2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole,
2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole,
2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole,
2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole,
2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole,
2,2'-bis (2-ethylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole,
2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole,
2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole,
2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) biimidazole
Etc.
[0040]
In addition, as the biimidazole compound (2),
2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4-dicyanophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4,6-tricyanophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4-dimethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4,6-trimethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4-diethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4,6-triethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4-diphenylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole,
2,2'-bis (2,4,6-triphenylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole
Etc.
[0041]
Of these compounds, the biimidazole compound (1) is particularly 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biphenyl. Imidazole and 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole are preferable, and the biimidazole compound (2) is particularly preferable. 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′- Scan (2,4,6-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole are preferred.
[0042]
The biimidazole compound (1) and the biimidazole compound (2) are excellent in solubility in solvents, do not produce foreign matters such as undissolved substances and precipitates, and have high sensitivity and irradiation with a small amount of energy. As a result, the curing reaction is sufficiently advanced, the contrast is high, and the curing reaction does not occur in the non-irradiated part, so that an excellent color filter can be formed.
In the present invention, the biimidazole compound (1) and the biimidazole compound (2) can be used alone or in admixture of two or more, and the biimidazole compound (1) and the biimidazole compound can be used. Compound (2) can be used in combination.
The total use ratio of the biimidazole compound (1) and the biimidazole compound (2) in the present invention is based on (B) 100 parts by weight of the binder resin when the polyfunctional monomer is not used. In general, it is 0.01 to 50 parts by weight, preferably 0.5 to 30 parts by weight, particularly preferably 0.5 to 10 parts by weight, and when (C) a polyfunctional monomer is used, (C) It is 0.01-200 weight part normally with respect to 100 weight part of polyfunctional monomers, Preferably it is 1-120 weight part, Most preferably, it is 1-50 weight part. In this case, by setting the total use ratio of these compounds within the above range, a pixel excellent in pattern shape, adhesion to the substrate, and the like can be formed.
[0043]
Further, in the present invention, (D) as a photopolymerization initiator component, other photoradical generators, sensitizers, curing accelerators together with biimidazole compound (1) and / or biimidazole compound (2). In addition, one or more photocrosslinking agents or photosensitizers composed of a polymer compound (hereinafter referred to as “polymer photocrosslinking / sensitizer”) can be used in combination.
Examples of the other photo radical generator include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, benzophenone, 4,4′-bis (dimethylamino) benzophenone 4,4′-bis (diethylamino) benzophenone, 2,4-diethylthioxanthone, 3 3-dimethyl-4-methoxybenzophenone, 4-azidobenzaldehyde, 4-azidoacetophenone, 4-azidobenzalacetophenone, azidopyrene, 4-diazodiphenylamine, 4-diazo-4'-methoxydiphenylamine, 4-diazo-3-methoxy Examples thereof include diphenylamine, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, dibenzoyl, benzoin isobutyl ether, N-phenylthioacridone, and triphenylpyrylium perchlorate. These other photo radical generators can be used alone or in admixture of two or more.
[0044]
Examples of the sensitizer include 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate, and 2,5-bis (4 ′ -Diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like.
These sensitizers can be used alone or in admixture of two or more.
Examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-4,6-dimethyl. Examples include chain transfer agents such as aminopyridine.
These curing accelerators can be used alone or in admixture of two or more.
[0045]
Among the other photo radical generators, sensitizers and curing accelerators, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl- (4-methylthiophenyl) -2-morpholino- 1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (Diethylamino) benzophenone and 2-mercaptobenzothiazole are preferable in that the formed pixels are difficult to drop off from the substrate during development, and the pixel intensity and sensitivity are high.
[0046]
In the present invention, (D) as photopolymerization initiator, in particular, biimidazole compound (1) and / or biimidazole compound (2), other photoradical generators of benzophenone and / or thiazole compounds. It is preferable to use in combination with a curing accelerator.
As a specific example of the particularly preferable combination,
2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole / 4,4'-bis (diethylamino) benzophenone,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) 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) biimidazole / 4,4′-bis (diethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone ,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole / 4,4′-bis (dimethylamino) benzophenone / 1-hydroxycyclohexylphenyl Ketone / 2-mercaptobenzothiazole,
2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole / 4,4'-bis (diethylamino) benzophenone,
2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole / 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'-tetraphenylbiimidazole / 4,4'-bis (diethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone,
2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole / 4,4′-bis (dimethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone / 2-mercaptobenzothiazole
Etc.
The proportion of other photoradical generator used in the present invention is preferably 80% by weight or less of the total amount of (D) photopolymerization initiator, and the proportion of sensitizer and / or curing accelerator used is (D ) 80% by weight or less of the whole photopolymerization initiator is preferable.
[0047]
Further, the polymer photocrosslinking / sensitizing agent is a polymer compound having a functional group capable of functioning as a photocrosslinking agent or a photosensitizer in the main chain and / or side chain. -Condensate of azidobenzaldehyde and polyvinyl alcohol, condensate of 4-azidobenzaldehyde and phenol novolac resin, (co) polymer of 4- (meth) acryloylphenyl cinnamoyl ester, 1,4-polybutadiene, 1,2 -Polybutadiene etc. can be mentioned.
These polymer photocrosslinking / sensitizing agents can be used alone or in admixture of two or more.
The proportion of the polymer photocrosslinking / sensitizer used in the present invention is usually 200 parts by weight or less, preferably 180 parts per 100 parts by weight of the biimidazole compound (1) and / or biimidazole compound (2). Less than parts by weight.
[0048]
(E) Other additives
The resin composition in the present invention may contain various other additives as necessary.
Examples of the other additive include:
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 ether, polyfluoroalkyl acrylate;
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, alkoxybenzophenone;
Anti-agglomeration agents such as sodium polyacrylate;
The following product names are F-top EF301, EF303, EF352 (above, Shin-Akita Kasei Co., Ltd.), MegaFuck F171, F172, F173, F173K (above, Dainippon Ink & Chemicals, Inc.) ), FLORAD FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-104 105, SC-106 (manufactured by Asahi Glass Co., Ltd.), KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, manufactured by Kyoeisha Yushi Chemical Co., Ltd.)
Etc.
[0049]
Moreover, the resin composition in this invention can contain a thermal acid generator and an acid crosslinking agent.
The thermal acid generator is a component that generates an acid by heating, and examples thereof include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, phosphonium salts, and particularly sulfonium salts. And benzothiazolium salts are preferred.
As the sulfonium salt, a compound represented by the following formula (6) (hereinafter referred to as “sulfonium salt (6)”) is preferable.
[0050]
[Formula 4]

[0051]
[In formula (6), R¹, R²And R^ThreeAre each independently a monovalent hydrocarbon group having 1 to 5 carbon atoms or a substituted derivative thereof, or an aryl group having 6 to 10 carbon atoms or a substituted derivative thereof, and R¹, R²And R^ThreeAt least one of them is an aryl group having 6 to 10 carbon atoms or a substituted derivative thereof;^-Represents a monovalent anion. ]
[0052]
Specific examples of the sulfonium salt (6) include
4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexamonate Alkylsulfonium salts such as fluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate;
Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, Benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc. Monobenzylsulfonium salts;
[0053]
Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3 -Chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate Dibenzylsulfonium salts such as;
p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitro Benzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium Substituted benzylsulfonium salts such as hexafluoroantimonate
Etc.
[0054]
Specific examples of the benzothiazonium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, 3- Benzylbenzo such as (p-methoxybenzyl) benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazolium hexafluoroantimonate Mention may be made of thiazolium salts.
[0055]
Of the sulfonium salt (6) and benzothiazolium salt, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate , Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylTheBenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate, and the like are preferable. Commercial products of these compounds include Sun-Aid SI-L85, SI-L110, SI-L145, SI-L150, SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.).
The thermal acid generators can be used alone or in admixture of two or more.
[0056]
The acid crosslinking agent has the following formula:
−CH₂OR
(Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms.)
Is preferably a compound having two or more monovalent organic groups (hereinafter referred to as “methylol (ether) group”) in one molecule, and preferably the monovalent organic group is a nitrogen atom. It is composed of a bonded compound, that is, a compound having an N-methylol group and / or an N-alkoxymethyl group. When the acid crosslinking agent has two or more methylol (ether) groups in one molecule, each methylol (ether) group may be the same as or different from each other.
In the case where the acid crosslinking agent has (B) the binder resin has a carboxyl group, the methylol (ether) group in the acid crosslinking agent is in the presence of an acid generated from the thermal acid generator, and (B) the carboxyl in the binder resin. It is a component that reacts with a group to form a crosslinked structure.
As such an acid crosslinking agent, for example,
The following general formula (7)
[0057]
[Chemical formula 5]

[0058]
[In the general formula (7), R^Four~ R⁹Independently represent an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms. ]
Alkoxymethylated melamines such as N, N, N, N, N, N-hexa (alkoxymethyl) melamine represented by
The following general formula (8)
[0059]
[Chemical 6]

[0060]
[In the general formula (8), R^Ten~ R¹³Independently represent an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms. ]
Alkoxymethylated glycolurils such as N, N, N, N-tetra (alkoxymethyl) glycoluril represented by
Etc.
In addition, as an acid crosslinking agent, urea-formaldehyde resin, thiourea-formaldehyde resin, melamine-formaldehyde resin, guanamine-formaldehyde resin, benzoguanamine-formaldehyde resin, glycoluril-formaldehyde resin, polyvinylphenols, etc., methylol (ether) group It is also possible to use a compound into which is introduced.
[0061]
Of the acid crosslinking agents, alkoxymethylated melamines and alkoxymethylated glycolurils are preferred, and alkoxymethylated melamines are particularly preferred. In addition, the weight of alkoxymethylated melamines (α) and alkoxymethylated glycolurils (β) is excellent in weight because it has an excellent balance of crosslinkability, heat resistance and solvent resistance, and a cured product having a low dielectric constant can be obtained. The ratio [(α) / (β)] is preferably 5/95 to 95/5, more preferably 10/90 to 90/10.
[0062]
(F) Solvent
  The resin composition in the present invention is used as a liquid composition containing a solvent.
  The solvent is composed of diethylene glycol mono-n-butyl ether acetate.
[0063]
  The use ratio of the solvent is 100 to 10000 parts by weight, preferably 500 to 5000 parts by weight with respect to 100 parts by weight of the (B) binder resin.
[0064]
Manufacturing method of color filter
Next, a method for producing a color filter using the ink composition color filter resin composition of the present invention will be described.
First, after applying the radiation sensitive resin composition which hardens | cures by irradiation of a radiation to a transparent substrate, prebaking (PB) is performed and a solvent is evaporated, A coating film is formed. The PB conditions in this case are, for example, a heating temperature of about 50 to 150 ° C. and a heating time of about 30 to 600 seconds. Then, after irradiating the coating film with radiation through a photomask, post-exposure baking (PEB) is performed, and then development processing is performed with an alkali developer to dissolve and remove the unirradiated portion of the coating film. As a result, a pattern array is formed in which barrier rib patterns having a predetermined shape having barrier ribs around are arranged according to a predetermined arrangement. The PEB conditions in this case are, for example, a heating temperature of about 50 to 150 ° C., a heating time of about 30 to 600 seconds, and a radiation irradiation condition of, for example, 1 to 500 mJ / cm.²Degree. The developing condition is, for example, about 10 to 300 seconds. As the developing method, for example, a liquid piling method, a dipping method, a vibration dipping method, or the like can be employed. Further, post-baking may be performed after development, and the conditions are, for example, a heating temperature of about 150 to 280 ° C. and a heating time of about 3 minutes to 2 hours.
[0065]
Next, using the resin composition for an ink jet color filter of the present invention, for example, the red, green, or blue resin composition is sequentially ejected into each partition pattern by an ink jet method, and then irradiated with radiation in some cases. The radiation irradiation conditions in this case are, for example, 1 to 500 mJ / cm.²The discharge speed of the resin composition is, for example, about 0.01 to 100 m / second. Thereafter, baking is performed to obtain a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on the substrate. The baking conditions in this case are, for example, a heating temperature of about 150 to 280 ° C. and a heating time of about 3 minutes to 2 hours.
[0066]
Examples of the transparent substrate used when producing the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. Further, these transparent substrates can be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. .
As a radiation sensitive resin composition used when manufacturing a color filter, for example, it contains the components (B), (C) and (D), and optionally the components (A) and (E). Or the composition etc. which further contain at least 1 sort (s) of (F) component can be used.
When the radiation-sensitive resin composition is applied to the transparent 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 0.5 to 3.0 μm, as the film thickness after PB.
Visible rays, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, and the like can be used as the radiation used when forming the partition wall pattern, but radiation having a wavelength in the range of 190 to 450 nm is preferable.
Examples of the alkaline developer include sodium carbonate, sodium hydroxide, potassium hydroxide, sodium silicon, sodium metasilicon, ammonia water, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo An aqueous solution such as [4.3.0] -5-nonene is preferred.
For example, 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. In addition, after development with an alkaline developer, it is usually washed with water.
[0067]
Such a manufacturing method of a color filter is very advantageous industrially because the pixel forming process is simple and the cost is low.
The color filter manufactured using the resin composition for an inkjet color filter of the present invention is extremely useful for, for example, a color liquid crystal display device, a color imaging tube element, a color sensor, and the like.
[0068]
DETAILED DESCRIPTION OF THE INVENTION
  The resin composition for an ink jet color filter of the present invention comprises (A) a colorant.,(B) Binder resinAnd (F) solventIs an essential component, and optionally contains (C) a polyfunctional monomer, (D) a photopolymerization initiator, or (E) other additives. Illustratively, the following (I) ~ (Ho).
(A) Resin composition for inkjet color filter, wherein component (B) contains carboxyl group-containing copolymer (B1) and / or N-position-substituted maleimide copolymer (B2).
[0069]
(B) The carboxyl group-containing copolymer (B1) as the component (B) is a methacrylic acid / benzyl methacrylate copolymer, a methacrylic acid / methyl methacrylate / styrene copolymer, a methacrylic acid / benzyl methacrylate / styrene copolymer, Methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate Macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer and methacrylic acid / 2- It consists of at least one selected from the group of roxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, and the N-position-substituted maleimide copolymer (B2) is N-phenylmaleimide / methacrylic acid / styrene / allyl acrylate. Copolymer, N-phenylmaleimide / methacrylic acid / styrene / allyl methacrylate copolymer, N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate copolymer, N-phenylmaleimide / methacrylic acid / styrene / phenyl methacrylate copolymer Polymer, N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate / Polymethyl methacrylate macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / phenyl methacrylate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / phenyl methacrylate / polymethyl methacrylate macromonomer Copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / poly Methyl methacrylate macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / Containing at least one selected from the group consisting of a phenyl methacrylate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate / polymethyl methacrylate macromonomer copolymer, (A) The resin composition for ink-jet color filters as described.
[0070]
(C) The ink jet color according to (A) or (B) above, wherein the component (C) contains at least one selected from the group consisting of trimethylolpropane triacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. Filter resin composition.
(D) The resin composition for an inkjet color filter according to (A), (B) or (C), wherein the component (A) contains an organic pigment.
[0071]
(E) The component (D) is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) biimidazole / 4
4′-bis (diethylamino) benzophenone, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) 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) biimidazole / 4,4′-bis (diethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′- Tetrakis (4-ethoxycarbonylphenyl) biimidazole / 4,4′-bis (dimethylamino) benzopheno / 1-hydroxycyclohexyl phenyl ketone / 2-mercaptobenzothiazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole / 4,4′-bis ( Diethylamino) benzophenone, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole / 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'-tetraphenylbiimidazole / 4 , 4′-bis (diethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone and 2,2′-bis (2,4,6- (Lichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole / 4,4′-bis (dimethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone / 2-mercaptobenzothiazole The resin composition for inkjet color filters according to the above (A), (B), (C) or (D), which contains a seed.
[0073]
【Example】
  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
[0074]
Example1
  As component (A), 65 parts by weight of CI Pigment Red 177 and as component (B), a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 25/65/10, weight average molecular weight = 55). , 000) 50 parts by weight, (C) component as dipentaerythritol pentaacrylate 40 parts by weight, (F) component as diethylene glycol mono-n-butyl ether acetate 800 parts by weight, and a resin composition colored in red A product was prepared.
  Separately, silica (SiO2) that prevents elution of sodium ions on the surface₂) After coating the radiation-sensitive resin composition on the surface of the soda glass transparent substrate on which the film was formed, PB was performed on a hot plate at 110 ° C. for 2 minutes to evaporate the solvent, thereby forming a coating film did. Then, radiation was applied to this coating film through a photomask at 40 mJ / cm.²Irradiate and perform PEB at 110 ° C. for 2 minutes, then develop with an alkaline developer at 25 ° C. for 1 minute, dissolve and remove the unirradiated part of the coating film, and further post-bake at 200 ° C. for 30 minutes. By carrying out, the partition pattern was formed so that the part which forms a pixel pattern might be divided.
  Next, the resin composition was ejected into the partition pattern by an ink jet method, and then baked in an oven at 200 ° C. for 1 hour to obtain a color filter in which a red pixel array was arranged on the substrate.
  The obtained color filter was excellent in the surface smoothness of the pixel, the film thickness variation of the pixel was less than 2%, and had excellent characteristics without causing color unevenness.
  Further, the contact angle between the partition pattern and the resin composition at this time (value measured within 1 minute after the resin composition contacted the substrate surface) was about 50 degrees.
[0075]
Example2
  As component (A), 65 parts by weight of CI Pigment Red 177 and as component (B), a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 25/65/10, weight average molecular weight = 55). , 000) 50 parts by weight, (C) as component, 40 parts by weight of dipentaerythritol pentaacrylate, (E) as component, 1.5 parts by weight of Megafac F172, and (F) as component, diethylene glycol mono-n-butyl ether A resin composition colored in red was prepared by mixing 800 parts by weight of acetate.
  Separately, silica (SiO2) that prevents elution of sodium ions on the surface₂) After coating the radiation-sensitive resin composition on the surface of the soda glass transparent substrate on which the film was formed, PB was performed on a hot plate at 110 ° C. for 2 minutes to evaporate the solvent, thereby forming a coating film did. Then, radiation was applied to this coating film through a photomask at 40 mJ / cm.²Irradiate and perform PEB at 110 ° C. for 2 minutes, then develop with an alkaline developer at 25 ° C. for 1 minute, dissolve and remove the unirradiated part of the coating film, and further post-bake at 200 ° C. for 30 minutes. By carrying out, the partition pattern was formed so that the part which forms a pixel pattern might be divided.
  Next, the resin composition was ejected into the partition pattern by an ink jet method, and then baked in an oven at 200 ° C. for 1 hour to obtain a color filter in which a red pixel array was arranged on the substrate.
  The obtained color filter was excellent in the surface smoothness of the pixel, the film thickness variation of the pixel was less than 2%, and had excellent characteristics without causing color unevenness.
  Further, the contact angle between the partition pattern and the resin composition at this time (value measured within 1 minute after the resin composition contacted the substrate surface) was about 50 degrees.
[0076]
Example3
  As component (A), 65 parts by weight of CI Pigment Red 177 and as component (B), a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 25/65/10, weight average molecular weight = 55). , 000) 50 parts by weight, (C) component as dipentaerythritol pentaacrylate 40 parts by weight, (D) component as 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′- 10 parts by weight of tetrakis (4-ethoxycarbonylphenyl) biimidazole, 10 parts by weight of 4,4′-bis (diethylamino) benzophenone, and 800 parts by weight of diethylene glycol mono-n-butyl ether acetate as component (F) A colored resin composition was prepared.
  Separately, silica (SiO2) that prevents elution of sodium ions on the surface₂) After coating the radiation-sensitive resin composition on the surface of the soda glass transparent substrate on which the film was formed, PB was performed on a hot plate at 110 ° C. for 2 minutes to evaporate the solvent, thereby forming a coating film did. Then, radiation was applied to this coating film through a photomask at 40 mJ / cm.²Irradiate and perform PEB at 110 ° C. for 2 minutes, then develop with an alkaline developer at 25 ° C. for 1 minute, dissolve and remove the unirradiated part of the coating film, and further post-bake at 200 ° C. for 30 minutes. By carrying out, the partition pattern was formed so that the part which forms a pixel pattern might be divided.
  Next, after the resin composition is ejected into the partition pattern by an ink jet method, the radiation is 40 mJ / cm.²Irradiation was then performed in an oven at 200 ° C. for 1 hour to obtain a color filter in which a red pixel array was arranged on the substrate.
  The obtained color filter was excellent in the surface smoothness of the pixel, the film thickness variation of the pixel was less than 2%, and had excellent characteristics without causing color unevenness.
  Further, the contact angle between the partition pattern and the resin composition at this time (value measured within 1 minute after the resin composition contacted the substrate surface) was about 50 degrees.
[0077]
【The invention's effect】
The resin composition for an ink-jet color filter of the present invention uses an ink-jet method when forming a pixel pattern, and a color filter having excellent characteristics can be produced at a low cost by a simple pixel forming process. it can.

Claims (6)

  (A) A resin composition containing a colorant, (B) a binder resin, and (F) a solvent, wherein the component (F) is composed of diethylene glycol mono-n-butyl ether acetate, and the proportion of the component (F) used is (B) The resin composition for inkjet type color filters which is 100-10000 weight part with respect to 100 weight part of component.   Component (B) is a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer and / or N-substituted maleimide and others The resin composition for an inkjet color filter according to claim 1, wherein the resin composition is a copolymer with a copolymerizable monomer.   The inkjet color according to claim 1 or 2, further comprising (C) a polyfunctional monomer having two or more polymerizable ethylenically unsaturated bonds and (D) a photopolymerization initiator. Filter resin composition.   The resin composition for an inkjet color filter according to claim 3, wherein the component (C) contains at least one selected from the group of trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.   Component (D) is 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole / 4,4′-bis (diethylamino) benzophenone, 2 , 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole / 4,4′-bis (diethylamino) benzophenone / 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) butan-1-one, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole / 4,4′-bis (diethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone, 2,2′-bis (2-chlorophenol) Nyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole / 4,4′-bis (dimethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone / 2-mercaptobenzothiazole, 2 , 2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole / 4,4′-bis (diethylamino) benzophenone, 2,2′-bis (2,4- Dibromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole / 4,4′-bis (diethylamino) benzophenone / 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane- 1-one, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenylbiimi Sol / 4,4′-bis (diethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone and 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenylbi The inkjet system according to claim 3 or 4, which contains at least one selected from the group consisting of imidazole / 4,4'-bis (dimethylamino) benzophenone / 1-hydroxycyclohexyl phenyl ketone / 2-mercaptobenzothiazole. Resin composition for color filter. The ink jet color filter resin composition according to any one of claims 1 to 5 , in each partition wall pattern of a transparent substrate on which a pattern array in which partition walls having a predetermined shape are arranged according to a predetermined arrangement is an inkjet system. A method for producing a color filter comprising a step of forming a pixel array on a substrate by performing a baking process after ejecting the film and optionally irradiating with radiation.