JP4210455B2 - Photocurable coloring composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable coloring composition which shows a high transmittance especially regarding green color and provides an excellent color reproducibility, and a color filter. <P>SOLUTION: The photocurable coloring composition contains an alkali-soluble resin, a colorant, a photosensitive polymer component, a photoinitiator and a solvent. The composition gives a coating film having a film thickness of &le;2.2 &mu;m and a y value of &ge;0.65 in CIE chromaticity coordinate. The colorant comprises a mixture of green and yellow pigments, wherein the green pigment is C.I. Pigment Green 7 and the yellow pigment is C.I. Pigment Yellow 180 and/or C.I. Pigment Yellow 185. <P>COPYRIGHT: (C)2003,JPO

Description

【００４７】
一般式ＩＶ中：
Ｗは、置換された又は無置換のアリール基を、Ｘは水素原子、アルキル基又はアリール基を表す。
Ｙは、弗素原子、塩素原子又は臭素原子を表す。
ｎは、１〜３の整数を表す。
一般式ＩＶの具体的な化合物としては、２−トリクロロメチル−５−スチリル−１，３，４−オキサジアゾール、２−トリクロロメチル−５−（ｐ−シアノスチリル）−１，３，４−オキサジアゾール、２−トリクロロメチル−５−（ｐ−メトキシスチリル）−１，３，４−オキサジアゾール等が挙げられる。
【００４８】
ハロメチル−ｓ−トリアジン系化合物としては、特公昭５９−１２８１号公報に記載の下記一般式Ｖに示されるビニル−ハロメチル−ｓ−トリアジン化合物、特開昭５３−１３３４２８号公報に記載の下記一般式ＶＩに示される２−（ナフト−１−イル）−４，６−ビス−ハロメチル−ｓ−トリアジン化合物及び下記一般式VIIで示される４−（ｐ−アミノフェニル）−２，６−ジ−ハロメチル−ｓ−トリアジン化合物が挙げられる。
【００４９】
【化２】

【００５０】
一般式Ｖ中：
Ｑは、Ｂｒ又はＣｌを表す。
Ｐは、−ＣＱ₃（Ｑは上記と同義である）、−ＮＨ₂、−ＮＨＲ、−Ｎ（Ｒ）₂、又は−ＯＲ（ここで、Ｒはフェニル又はアルキル基を示す）を表す。
Ｗは、置換されていてもよい芳香族基、置換されていてもよい複素環式基、又は下記一般式ＶＡで表される一価の基を表す。
【００５１】
【化３】

【００５２】
一般式ＶＡ中、Ｚは−Ｏ−又は−Ｓ−であり、Ｒは上記と同義である。
【００５３】
【化４】

【００５４】
一般式ＶＩ中：
Ｘは、Ｂｒ又はＣｌを表す。
ｍ、ｎは０〜３の整数である。
Ｒ'は、下記一般式ＶＩＡで示され基を表す。
【００５５】
【化５】

【００５６】
（上記一般式ＶＩＡ中、Ｒ₁は水素原子又はＯＲc（Ｒc はアルキル、シクロアルキル、アルケニル、アリール基）、Ｒ₂はＣｌ，Ｂｒ、アルキル、アルケニル、アリール、又はアルコキシ基を表す。）
【００５７】
【化６】

【００５８】
一般式VII中：
Ｒ₁、Ｒ₂は、同一または異なって、水素原子、アルキル基、置換アルキル基、アリール基、置換アリール基、下記一般式VIIＡ又はVIIＢで示される基を表す。
Ｒ₃、Ｒ₄は、同一または異なって、水素原子、ハロゲン原子、アルキル基、アルコキシ基を表す。
Ｘ、Ｙは、同一または異なって、Ｃｌ又はＢｒを表す。
ｍ、ｎは、同一または異なって、０、１又は２を表す。
【００５９】
【化７】

【００６０】
一般式VIIＡ及びVIIＢ中、Ｒ₅、Ｒ₆、Ｒ₇は、アルキル基、置換アルキル基、アリール基、置換アリール基を表す。置換アルキル基及び置換アリール基における置換基の例としては、フェニル基等のアリール基、ハロゲン原子、アルコキシ基、カルボアルコキシ基、カルボアリールオキシ基、アシル基、ニトロ基、ジアルキルアミノ基、スルホニル誘導体等が挙げられる。
【００６１】
一般式VIIにおいて、Ｒ₁とＲ₂がそれらと結合している窒素原子と共に非金属原子からなる異節環を形成してもよく、その場合、異節環としては下記に示されるものが挙げられる。
【００６２】
【化８】

【００６３】
一般式Ｖの具体的な例としては、２，４−ビス（トリクロロメチル）−６−ｐ−メトキシスチリル−ｓ−トリアジン、２，４−ビス（トリクロロメチル）−６−（１−ｐ−ジメチルアミノフェニル−１，３−ブタジエニル）−ｓ−トリアジン、２−トリクロロメチル−４−アミノ−６−ｐ−メトキシスチリル−ｓ−トリアジン等が挙げられる。
【００６４】
一般式ＶＩの具体的な例としては、２−（ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（４−メトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（４−エトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（４−ブトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−〔４−（２−メトキシエチル）−ナフト−１−イル〕−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−〔４−（２−エトキシエチル）−ナフト−１−イル〕−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−〔４−（２−ブトキシエチル）−ナフト−１−イル〕−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（２−メトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（６−メトキシ−５−メチル−ナフト−２−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（６−メトキシ−ナフト−２−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（５−メトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（４，７−ジメトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（６−エトキシ−ナフト−２−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（４，５−ジメトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン等が挙げられる。
【００６５】
一般式VIIの具体例としては、４−〔ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−メチル−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−メチル−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｐ−Ｎ，Ｎ−ジ（フェニル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｐ−Ｎ−クロロエチルカルボニルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｐ−Ｎ−（ｐ−メトキシフェニル）カルボニルアミノフェニル〕２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−ブロモ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−クロロ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−フロロ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−ブロモ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−クロロ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−フロロ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−ブロモ−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−クロロ−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−フロロ−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−ブロモ−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−クロロ−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−フロロ−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｍ−ブロモ−ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｍ−クロロ−ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｍ−フロロ−ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｏ−ブロモ−ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｏ−クロロ−ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｏ−フロロ−ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｍ−ブロモ−ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｍ−クロロ−ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｍ−フロロ−ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｏ−ブロモ−ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｏ−クロロ−ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｏ−フロロ−ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、等が挙げられる。
【００６６】
これら開始剤には増感剤を併用することができる。その具体例として、ベンゾイン、ベンゾインメチルエーテル、ベンゾイン、９−フルオレノン、２−クロロ−９−フルオレノン、２−メチル−９−フルオレノン、９−アントロン、２−ブロモ−９−アントロン、２−エチル−９−アントロン、９，１０−アントラキノン、２−エチル−９，１０−アントラキノン、２−ｔ−ブチル−９，１０−アントラキノン、２，６−ジクロロ−９，１０−アントラキノン、キサントン、２−メチルキサントン、２−メトキシキサントン、２−メトキシキサントン、チオキサントン、ベンジル、ジベンザルアセトン、ｐ−（ジメチルアミノ）フェニルスチリルケトン、ｐ−（ジメチルアミノ）フェニル−ｐ−メチルスチリルケトン、ベンゾフェノン、ｐ−（ジメチルアミノ）ベンゾフェノン（またはミヒラーケトン）、ｐ−（ジエチルアミノ）ベンゾフェノン、ベンゾアントロン等や特公昭５１−４８５１６号公報記載のベンゾチアゾール系化合物が挙げられる。
【００６７】
又、上記３−アリール置換クマリン化合物は、例えば下記一般式VIIIで示される化合物である。
【００６８】
【化９】

【００６９】
Ｒ₈は水素原子、炭素数１〜８のアルキル基、炭素数６〜１０のアリール基（好ましくは水素原子、メチル基、エチル基、プロピル基、ブチル基）を、Ｒ₉は水素原子、炭素数１〜８のアルキル基、炭素数６〜１０のアリール基、下記一般式VIIIＡで示される基（好ましくはメチル基、エチル基、プロピル基、ブチル基、一般式VIIIＡで示される基、特に好ましくは一般式VIIIＡで示される基）を表す。
【００７０】
Ｒ₁₀、Ｒ₁₁はそれぞれ水素原子、炭素数１〜８のアルキル基（例えばメチル基、エチル基、プロピル基、ブチル基、オクチル基）、炭素数１〜８のハロアルキル基（例えばクロロメチル基、フロロメチル基、トリフロロメチル基など）、炭素数１〜８のアルコキシ基（例えばメトキシ基、エトキシ基、ブトキシ基）、置換されてもよい炭素数６〜１０のアリール基（例えばフェニル基）、アミノ基、−Ｎ（Ｒ₁₆)(Ｒ₁₇）、ハロゲン原子（例えばＣｌ、Ｂｒ，Ｆ）を表す。好ましくは水素原子、メチル基、エチル基、メトキシ基、フェニル基、−Ｎ（Ｒ₁₆)(Ｒ₁₇）、Ｃｌである。
【００７１】
Ｒ₁₂は、置換されてもよい炭素数６〜１６のアリール基（例えばフェニル基、ナフチル基、トリル基、クミル基）を表す。置換基としてはアミノ基、−Ｎ（Ｒ₁₆)(Ｒ₁₇）、炭素数１〜８のアルキル基（例えばメチル基、エチル基、プロピル基、ブチル基、オクチル基）、炭素数１〜８のハロアルキル基（例えばクロロメチル基、フロロメチル基、トリフロロメチル基など）、炭素数１〜８のアルコキシ基（例えばメトキシ基、エトキシ基、ブトキシ基）、ヒドロキシ基、シアノ基、ハロゲン原子（例えばＣｌ、Ｂｒ，Ｆ）が挙げられる。
【００７２】
Ｒ₁₃、Ｒ₁₄、Ｒ₁₆、Ｒ₁₇は、同一または異なって、それぞれ水素原子、炭素数１〜８のアルキル基（例えばメチル基、エチル基、プロピル基、ブチル基、オクチル基）を表す。Ｒ₁₃とＲ₁₄及びＲ₁₆とＲ₁₇は、互いに結合し窒素原子とともに複素環（例えばピペリジン環、ピペラジン環、モルホリン環、ピラゾール環、ジアゾール環、トリアゾール環、ベンゾトリアゾール環等）を形成してもよい。
【００７３】
Ｒ₁₅は、水素原子、炭素数１〜８のアルキル基（例えばメチル基、エチル基、プロピル基、ブチル基、オクチル基）、炭素数１〜８のアルコキシ基（例えばメトキシ基、エトキシ基、ブトキシ基）、置換されてもよい炭素数６〜１０のアリール基（例えばフェニル基）、アミノ基、Ｎ（Ｒ₁₆)(Ｒ₁₇）、ハロゲン原子（例えばＣｌ、Ｂｒ，Ｆ）を表す。Ｚｂは＝Ｏ、＝Ｓあるいは＝Ｃ（Ｒ₁₈)(Ｒ₁₉）を表す。好ましくは＝Ｏ、＝Ｓ、＝Ｃ（ＣＮ)₂であり、特に好ましくは＝Ｏである。Ｒ₁₈、Ｒ₁₉は、同一または異なって、シアノ基、−ＣＯＯＲ₂₀、−ＣＯＲ₂₁を表す。Ｒ₂₀、Ｒ₂₁はそれぞれ炭素数１〜８のアルキル基（例えばメチル基、エチル基、プロピル基、ブチル基、オクチル基）、炭素数１〜８のハロアルキル基（例えばクロロメチル基、フロロメチル基、トリフロロメチル基など）、置換されてもよい炭素数６〜１０のアリール基（例えばフェニル基）を表す。
【００７４】
特に好ましい３−アリール置換クマリン化合物は一般式IXで示される｛（ｓ−トリアジン−２−イル）アミノ｝−３−アリールクマリン化合物類である。
【００７５】
【化１０】

【００７６】
ロフィン二量体は２個のロフィン残基からなる２，４，５−トリフェニルイミダゾリル二量体を意味し、その基本構造を下記に示す。
【００７７】
【化１１】

【００７８】
その具体例としては、２−（ｏ−クロルフェニル）−４，５−ジフェニルイミダゾリル二量体、２−（ｏ−フルオロフェニル）−４，５−ジフェニルイミダゾリル二量体、２−（ｏ−メトキシフェニル）−４，５−ジフェニルイミダゾリル二量体、２−（ｐ−メトキシフェニル）−４，５−ジフェニルイミダゾリル二量体、２−（ｐ−ジメトキシフェニル）−４，５−ジフェニルイミダゾリル二量体、２−（２，４−ジメトキシフェニル）−４，５−ジフェニルイミダゾリル二量体、２−（ｐ−メチルメルカプトフェニル）−４，５−ジフェニルイミダゾリル二量体等が挙げられる。
【００７９】
本発明では、以上の開始剤の他に他の公知のものも使用することができる。
例えば、米国特許第２，３６７，６６０号明細書に開示されているビシナールポリケトルアルドニル化合物、米国特許第２，３６７，６６１号および第２，３６７，６７０号明細書に開示されているα−カルボニル化合物、米国特許第２，４４８，８２８号明細書に開示されているアシロインエーテル、米国特許第２，７２２，５１２号明細書に開示されているα−炭化水素で置換された芳香族アシロイン化合物、米国特許第３，０４６，１２７号および第２，９５１，７５８号明細書に開示されている多核キノン化合物、米国特許第３，５４９，３６７号明細書に開示されているトリアリルイミダゾールダイマー／ｐ−アミノフェニルケトンの組合せ、特公昭５１−４８５１６号公報に開示されているベンゾチアゾール系化合物／トリハロメチール−ｓ−トリアジン系化合物等が挙げられる。
また、旭電化(株）製アデカオプトマーＳＰ−１５０、同１５１、同１７０、同１７１、同Ｎ−１７１７、同Ｎ１４１４等も重合開始剤として使用できる。
【００８０】
光重合開始剤の使用量は、好ましくは光硬化性着色組成物の全固形分の０．１〜１０．０質量％、より好ましくは０．５〜５．０質量％である。開始剤の使用量が０．１質量％より少ないと重合が進み難く、また、１０．０質量％を超えると膜強度が弱くなる傾向がある。
【００８１】
〔V〕溶剤
本発明の光硬化性着色組成物を調製する際に使用する溶剤としては、エステル類、例えば酢酸エチル、酢酸−ｎ−ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、アルキルエステル類、乳酸メチル、乳酸エチル、オキシ酢酸メチル、オキシ酢酸エチル、オキシ酢酸ブチル、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、３−オキシプロピオン酸メチル、３−オキシプロピオン酸エチルなどの３−オキシプロピオン酸アルキルエステル類；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、２−オキシプロピオン酸メチル、２−オキシプロピオン酸エチル、２−オキシプロピオン酸プロピル、２−メトキシプロピオン酸メチル、２−メトキシプロピオン酸エチル、２−メトキシプロピオン酸プロピル、２−エトキシプロピオン酸メチル、２−エトキシプロピオン酸エチル、２−オキシ−２−メチルプロピオン酸メチル、２−オキシ−２−メチルプロピオン酸エチル、２−メトキシ−２−メチルプロピオン酸メチル、２−エトキシ−２−メチルプロピオン酸エチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２−オキソブタン酸メチル、２−オキソブタン酸エチル等；エーテル類、例えばジエチレングリコールジメチルエーテル、テトラヒドロフラン、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、メチルセロソルブアセテート、エチルセロソルブアセテート、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ブチルエーテル、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート等；ケトン類、例えば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；芳香族炭化水素類、例えばトルエン、キシレシ等が挙げられる。
【００８２】
これらのうち、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、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメテルエーテル、酢酸ブチル、３−メトキシプロピオン酸メチル、２−ヘプタノン、シクロヘキサノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテルアセテート等が好ましく用いられる。
【００８３】
これらの溶剤は、単独で用いてもあるいは２種以上組み合わせて用いてもよい。
【００８４】
〔VI〕フッ素系化合物
本発明の光硬化性着色組成物には、更に下記の式（I）で表されるフッ素系化合物を含有することが好ましい。
Ｃ₈Ｆ₁₇ＳＯ₂Ｎ（Ｒ₁）ＣＨ₂ＣＨ₂Ｏ（ＣＨ₂ＣＨ₂Ｏ）_nＲ₂ （I）
式（I）中、Ｒ₁及びＲ₂は各々水素原子または炭素数１〜４のアルキル基を表し、ｎは２〜３０の整数を表す。
式（I)において、好ましくはＲ₁はメチル基、エチル基またはiso-プロピル基であり、Ｒ₂は水素原子である。ｎの好ましい範囲は１０〜２５であり、特に好ましい範囲は１０〜２０である。
【００８５】
上記式（I)で表されるフッ素系化合物としては、例えば、大日本インキ化学工業（株）製 メガファック Ｆ−１４１（ｎ＝５）、Ｆ−１４２（ｎ＝１０）、Ｆ−１４３（ｎ＝１５）、Ｆ−１４４（ｎ＝２０）を挙げることができる。
【００８６】
また、本発明の光硬化性着色組成物には、下記一般式（１）〜（４）から選択される少なくとも１種のフッ素系化合物を含有するのも好ましい。特には、下記一般式（１）及び（２）で表される化合物が好ましい。
Ｒ^f1−Ｘ−（ＣＨ₂ＣＨ₂Ｏ）_nＲ¹ （１）
Ｒ^f1−Ｘ−（ＣＨ₂ＣＨ₂Ｏ）_nＲ^f2 （２）
Ｒ^f1−Ｘ−（ＣＨ₂ＣＨ₂Ｏ）_n（ＣＨ₂ＣＨ₂ＣＨ₂Ｏ）_m−Ｒ¹ （３）
Ｒ^f1−Ｘ−（ＣＨ₂ＣＨ₂Ｏ）_n（ＣＨ₂ＣＨ₂ＣＨ₂Ｏ）_m−Ｒ^f2 （４）
【００８７】
式中、Ｒ¹は、炭素数１〜１８、好ましくは炭素数１〜１０、より好ましくは炭素数１〜４のアルキル基を表し、これらアルキル基は飽和アルキル基であっても、不飽和アルキル基であってもよい。また、これらアルキル基は直鎖構造であっても、分岐構造であってもよいが、分岐構造であるのが好ましい。
アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ヘプチル基、ヘキシル基、オクチル基、ノニル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコサニル基、ドコサニル基、２−クロロエチル基、２−ブロモエチル基、２−シアノエチル基、２−メトキシカルボニルエチル基、２−メトキシエチル基、３−ブロモプロピル基等が挙げられる。
また、これらアルキル基はハロゲン原子、アシル基、アミノ基、シアノ基、アルキル基、アルコキシ基、アルキルもしくはハロアルキルで置換されてもよいアリール基、アミド基等で置換されていてもよい。
【００８８】
Ｒ^f1及びＲ^f2はそれぞれ独立して、炭素数１〜１８、好ましくは炭素数２〜１２、より好ましくは炭素数４〜１０のパーフロロ基を表し、これらパーフロロ基は飽和であっても、不飽和であってもよい。また、これらパーフロロ基は直鎖構造であっても、分岐構造であってもよいが、本発明の感光性着色樹脂組成物にあっては、特に分岐構造が好ましい。尚、Ｒ^f1とＲ^f2は、互いに同じであっても、異なっていてもよい。
これらパーフロロ基としては、例えば、パーフロロノネニル、パーフロロメチル、パーフロロプロピレン、パーフロロノネニル、パーフロロ安息香酸、パーフロロプロピレン、パーフロロプロピル、パーフロロ（９−メチルオクチル）、パーフロロメチルオクチル、パーフロロブチル、パーフロロ３−メチルブチル、パーフロロヘキシル、パーフロロオクチル、パーフロロ−７−オクチルエチル、フロロヘプチル、パーフロロオクチル、パーフロロデシル、パーフロロブチル、等が挙げられる。
また、これらのパーフロロ基は、ハロゲン原子、アシル基、アミノ基、シアノ基、アルキル基、アルコキシ基、アルキルもしくはハロアルキルで置換されてもよいアリール基、アミド基等で置換されていてもよい。
本発明において、これらフッ素系化合物は、Ｒ^f1又はＲ¹の少なくとも一方が分岐構造である化合物であるのが好ましい。
【００８９】
ｎは１〜４０の整数、好ましくは４〜２５の整数を表し、ｍは０〜４０の整数、好ましくは０〜２５の整数を表す。
−Ｘ−は、−（ＣＨ₂）_l−（ここで、ｌは１〜１０、好ましくは１〜５の整数である。）、−ＣＯ−Ｏ−、−Ｏ−、−ＮＨＣＯ−、又は−ＮＨＣＯＯ−を表す。
【００９０】
本発明の組成物中に上記特定のフッ素系化合物を更に含有させることにより、組成物の液特性はさらに改良される。すなわち、塗布液としての流動性が良くなり、塗布工程で使用されるスピンコーターのノズルや配管、容器中での液の付着性が改良され、汚れとして残る残渣を殆どなくすことができるので、塗布液の切り替え時に洗浄に要する洗浄液の量や作業時間を軽減でき、工程適性が改良される。尚、上記フッ素系化合物は、本発明の感光性組成物中でノニオン系の界面活性剤として作用しているものと考えられる。
【００９１】
本発明において上記一般式（Ｉ）並びに（１）〜（４）で表される化合物は、単独で用いてもよいし、２種以上組み合わせて用いてもよい。尚、２種以上とは、同じ一般式で表される、異なる化合物を２種以上使用する場合、及び異なる一般式で表される化合物を２種以上使用する場合の両者を含む。
本発明においてこれら特定のフッ素系化合物の添加量としては、全塗布溶液に対し好ましくは０．０１〜２．０質量％であり、より好ましくは０．１〜１．０質量％である。
【００９２】
〔VII〕その他の成分
本発明の光硬化性着色組成物には、必要に応じて各種添加物、例えば充填剤、上記アルカリ可溶性樹脂以外の高分子化合物、上記以外の界面活性剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することかできる。
【００９３】
これらの添加物の具体例としては、ガラス、アルミナ等の充填剤；イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体、酸性セルロース誘導体、水酸基を有するポリマーに酸無水物を付加させたもの、アルコール可溶性ナイロン、ビスフェノールＡとエピクロルヒドリンから形成されたフェノキシ樹脂などのアルカリ可溶の樹脂；ノニオン系、カチン系、アニオン系等の界面活性剤、具体的にはフタロシアニン誘導体（市販品ＥＦＫＡ−７４５（森下産業製））；オルガノシロキサンポリマーＫＰ３４１（信越化学工業製）、（メタ）アクリル酸系（共）重合体ポリフローＮo.７５、Ｎo.９０、Ｎo.９５（共栄社油脂化学工業製）、Ｗ００１（裕商製）等のカチオン系界面活性剤；ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル（ＢＡＳＦ社製 プルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１等のノニオン系界面活性剤；エフトップＥＦ３０１、ＥＦ３０３、ＥＦ３５２（新秋田化成製）等のフッ素系界面活性剤；Ｗ００４、Ｗ００５、Ｗ０１７（裕商製）等のアニオン系界面活性剤；ＥＦＫＡ−４６、ＥＦＫＡ−４７、ＥＦＫＡ−４７ＥＡ、ＥＦＫＡポリマー１００、ＥＦＫＡポリマー４００、ＥＦＫＡポリマー４０１、ＥＦＫＡポリマー４５０（以上森下産業製）、ディスパースエイド６、ディスパースエイド８、ディスパースエイド１５、ディスパースエイド９１００（サンノプコ製）等の高分子分散剤；ソルスパース３０００、５０００、９０００、１２０００、１３２４０、１３９４０、１７０００、２４０００、２６０００、２８０００などの各種ソルスパース分散剤（ゼネカ株式会社製）；アデカプルロニックＬ３１，Ｆ３８，Ｌ４２，Ｌ４４，Ｌ６１，Ｌ６４，Ｆ６８，Ｌ７２，Ｐ９５，Ｆ７７，Ｐ８４，Ｆ８７、Ｐ９４，Ｌ１０１，Ｐ１０３，Ｆ１０８、Ｌ１２１、Ｐ−１２３（旭電化製）およびイソネットＳ−２０（三洋化成製）；
【００９４】
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；
およびポリアクリル酸ナトリウム等の凝集防止剤を挙げることができる。
【００９５】
また、放射線未照射部のアルカリ溶解性を促進し、本発明の組成物の現像性の更なる向上を図る場合には、本発明の組成物に有機カルボン酸、好ましくは分子量１０００以下の低分子量有機カルボン酸の添加を行うことができる。具体的には、例えばギ酸、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、カプリル酸等の脂肪族モノカルボン酸；シュウ酸、マロン酸、コハク酸、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、メチルコハク酸、テトラメチルコハク酸、シトラコン酸等の脂肪族ジカルボン酸；トリカルバリル酸、アコニット酸、カンホロン酸等の脂肪族トリカルボン酸；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；フタル酸、イソフタル酸、テレフタル酸、トリメリト酸、トリメシン酸、メロファン酸、ピロメリト酸等の芳香族ポリカルボン酸；フェニル酢酸、ヒドロアトロパ酸、ヒドロケイ皮酸、マンデル酸、フェニルコハク酸、アトロパ酸、ケイ皮酸、ケイ皮酸メチル、ケイ皮酸ベンジル、シンナミリデン酢酸、クマル酸、ウンベル酸等のその他のカルボン酸が挙げられる。
【００９６】
本発明の光硬化性着色組成物には以上の他に、更に、熱重合防止剤を加えておくことが好ましく、例えば、ハイドロキノン、ｐ−メトキシフェノール、ジ−ｔ−ブチル−ｐ−クレゾール、ピロガロール、ｔ−ブチルカテコール、ベンゾキノン、４，４′−チオビス（３−メチル−６−ｔ−ブチルフェノール）、２，２'−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２−メルカプトベンゾイミダゾール等が有用である。
【００９７】
〔VII〕本発明の組成物の使用方法
本発明の光硬化性着色組成物は、着色剤、アルカリ可溶性樹脂、感光性重合成分、光重合開始剤、さらに必要に応じて用いられるフッ素系化合物及びその他の添加剤を溶剤と混合し各種の混合機、分散機を使用して混合分散することによって調製することができる。
【００９８】
本発明の組成物の好ましい製造方法としては、着色剤に（メタ）アクリル酸及びベンジルメタクリレートからなる共重合体であるアルカリ可溶性樹脂Ｂ１または（メタ）アクリル酸、ベンジルメタクリレート、及びヒドロキシエチル（メタ）アクリレートからなる共重合体であるアルカリ可溶性樹脂Ｂ２を１０,０００ｍＰａ・ｓ以上の粘度で混練分散させ、次いで前記アルカリ可溶性樹脂Ａを添加して１,０００ｍＰａ・ｓ以下の粘度で微分散処理することである。
【００９９】
混練分散工程は、先ず顔料と分散剤若しくは表面処理剤、本発明の樹脂Ｂ１若しくはＢ２（樹脂Ｂ１、Ｂ２いずれも使用しない場合は樹脂Ａの一部または全部）及び溶剤で混練する。混練に使用する機械は二本ロール、三本ロール、ボールミル、トロンミル、ディスパー、ニーダー、コニーダー、ホモジナイザー、ブレンダー、単軸および２軸の押出機等であり、強い剪断力を与えながら分散する。次いで、溶剤及び本発明の樹脂Ａ（混練工程で使用した残部）を加えて、主として縦型若しくは横型のサンドグラインダー、ピンミル、スリットミル、超音波分散機等を使用し、０．１〜１ｍｍの粒径のガラス、ジルコニア等でできたビーズで分散する。尚、この混練工程を省くことも可能である。その場合には、顔料と分散剤若しくは表面処理剤、本発明の樹脂Ｂ１若しくはＢ２（いずれも使用しない場合は樹脂Ａの一部または全部）及び溶剤でビーズ分散を行う。この場合には混練工程での残りの樹脂Ａは分散の途中で添加することが好ましい。
尚、混練、分散についての詳細はT.C. Patton著"Paint Flow and Pigment Dispersion"（1964年 John Wiley and Sons社刊）等にも記載されている。
【０１００】
本発明の光硬化性着色組成物は、基板に回転塗布、流延塗布、ロール塗布等の塗布方法により塗布、乾燥して感放射線性層を形成し、所定のマスクパターンを介して露光し、現像液で現像することによって、カラーフィルターを製造することができる。この際に使用される放射線としては、特にｇ線、ｈ線、ｉ線等の紫外線が好ましく用いられる。
本発明においては、この様にして製造されたカラーフィルターであって、塗布膜の膜厚が２．２μｍ以下で、かつＣＩＥ色度座標のｙ値が０．６５以上であることを特徴とするカラーフィルターも提供される。膜厚及びｙ値については、上記組成物について説明したのと同様である。
【０１０１】
基板としては、例えば液晶表示素子等に用いられるソーダガラス、パイレックスガラス、石英ガラスおよびこれらに透明導電膜を付着させたものや、固体撮像素子等に用いられる光電変換素子基板、例えばシリコン基板等が挙げられる。これらの基板は、一般的には各画素を隔離するブラックストライプが形成されている。
【０１０２】
現像液としては、放射線未照射部の感放射線性層を溶解し、一方放射線照射部を溶解しないものであればいかなるものも用いることができる。具体的には種々の有機溶剤の組み合わせやアルカリ性の水溶液を用いることができる。有機溶剤としては、本発明の組成物を調製する際に使用される前述の溶剤が挙げられる。
【０１０３】
アルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム，硅酸ナトリウム、メタ硅酸ナトリウム、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、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、ピペリジン等のアルカリ性化合物を、濃度が０．００１〜１０質量％、好ましくは０．０１〜１質量％となるように溶解したアルカリ性水溶液が使用される。なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、一般に、現像後、水で洗浄する。
【０１０４】
【実施例】
以下、本発明を実施例により更に具体的に説明するが、本発明は以下の実施例に限定されるものではない。
（実施例１）
・ベンジルメタクリレート・メタクリル酸共重合体 ８０質量部
（重量平均分子量 ３００００； 酸価 １２０）
・Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｇｒｅｅｎ ７ １００質量部
・Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １８５ ３０質量部
・プロピレングリコールモノメチルエーテルアセテート ５００質量部
を、サンドミルで一昼夜分散した。
【０１０５】
次いで、下記の成分を添加した。
・ジペンタエリスリト−ルヘキサアクリレ−ト ８０質量部
・４−［ｏ−ブロモ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニル） ５質量部
アミノフェニル］２、６−ジ（トリクロロメチル）
−Ｓ− トリアジン
・７−［｛４−クロロ−６−（ジエチルアミノ）−Ｓ−トリアジン ２質量部
−２−イル｝アミノ］−３−フェニルクマリン
・ハイドロキノンモノメチルエーテル ０．０１質量部
・プロピレングリコールモノメチルエーテルアセテート ５００質量部
【０１０６】
上記各成分を均一に混合後、孔径５μｍのフィルターで濾過し、本発明の光硬化性着色組成物を得た。この組成物を、カラーフィルター用のガラス基板にスピンコーターで乾燥膜厚が２．２μｍとなるように塗布し１２０℃で２分間乾燥させたところ、緑色の均一な塗膜が得られた。
【０１０７】
次に未露光の上記塗膜につき、色度計（大塚電子（株）社製）により、ＣＩＥ色度（ｘ値，ｙ値）を測定した。結果を表１に示した。
【０１０８】
（実施例２〜６及び比較例１〜４）
実施例１において、顔料の種類及び配合割合を表１に記載される通りに変更した以外は、実施例１と同様に行った。結果も併せて表１に示した。
【０１０９】
【表１】

【０１１０】
表１中、
ＰＧ７： C.I. Pigment Green 7
ＰＧ３６： C.I. Pigment Green 36
ＰＹ１８５：C.I. Pigment Yellow 185
ＰＹ１８０：C.I. Pigment Yellow 180
ＰＹ１５０：C.I. Pigment Yellow 150
【０１１１】
【発明の効果】
本発明の光硬化性着色組成物は、特に緑色に関して透過率が高く、色再現性の優れたカラーフィルターを与えることができ、その結果液晶デイスプレイの画像を鮮明とし、かつ輝度を向上させ色安定性を確保することが可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photocurable coloring composition suitable for producing a color filter used for a liquid crystal display device or a solid-state imaging device, and a color filter, and particularly, a photocurable coloring composition having high color reproducibility with respect to green color, And a color filter.
[0002]
[Prior art]
A color filter is an essential component of a liquid crystal display (LCD) panel. The liquid crystal display is very compact and is equivalent to or better than the CRT display in terms of performance, and the CRT display is being replaced by a liquid crystal display as a television screen, a personal computer screen, and other display devices.
[0003]
However, since the image of the liquid crystal display has a lower green transmittance than red and blue, the color reproducibility of the green color is low, and the color reproduction range as the liquid crystal display is narrowed.
[0004]
For this reason, attempts have been made to improve the transmittance of the green color filter for the purpose of sharpening the liquid crystal display image. For example, it is known that the light transmittance at 540 nm of a backlight light source is improved by using a yellow pigment such as CI Pigment Yellow 139 and a green pigment such as CI Pigment Green 36 together.
[0005]
Japanese Patent Application Laid-Open No. 10-142969 uses a binder resin containing a quaternary ammonium salt monomer as a copolymerization component in order to improve pigment dispersion and enable fine particle dispersion of the pigment in the composition. A radiation sensitive coloring composition for a color filter is disclosed, and CI Pigment Green 7 is exemplified as a green pigment and CI Pigment Yellow 185 is exemplified as a yellow pigment.
Japanese Patent Application Laid-Open No. 9-203808 discloses a composition for a color filter in which the lightness and saturation are improved by defining the absorbance for light having wavelengths of 460 nm and 540 nm, respectively, and CI Pigment Green 7 as a green pigment. CI Pigment Yellow 180 and 185 are exemplified as yellow pigments, respectively.
However, the compositions described in the above patents are not sufficient in terms of transmittance and color reproducibility especially for green color, and further improvement of color reproducibility for green color is necessary.
[0006]
As a method for solving this problem, Japanese Patent Laid-Open No. 10-160928 discloses a green color filter that can form a green color filter having a light transmittance of 540 nm of 70% or more and a light transmittance of 490 nm of 50 to 90%. A coating composition has been proposed, and a color filter having a chromaticity coordinate y value of 0.520 using CI Pigment Yellow 185 as a yellow pigment and CI Pigment Green 7 as a green pigment is disclosed. However, the present situation is that a color filter having sufficiently high color reproducibility has not been obtained even when this composition is used.
[0007]
On the other hand, a composition for a color filter using a copolymer as an alkali-soluble resin is known. For example, Japanese Patent Laid-Open No. 6-95378 discloses a photocurable coloring composition for a color filter that can use water as a solvent, and a binder containing diethylene glycol monomethacrylate as a copolymerization monomer component is used. Japanese Patent Application Laid-Open No. 2000-194132 relates to a colored photosensitive resin composition for a color filter in which the development time is shortened and the tact time is appropriate, and a co-polymer having an oxyethylene skeleton in the side chain as a composition component. A polymer is disclosed. Further, CI Pigment Green 7 is exemplified as a pigment.
Furthermore, Japanese Patent No. 2665696 discloses a polymerizable composition for a color filter using a ternary copolymer having polyethylene glycol alkyl ether (meth) acrylate as a copolymerization component as a pigment dispersion binder. CI Pgiment Green 7 is exemplified as the pigment.
[0008]
In recent years, with the widespread use of liquid crystal display devices, their uses have been extended to various monitors and TVs. At the same time, improvement in color reproducibility is desired. In order to meet the demand, the appearance of a color filter with high transparency and high color density is expected. However, when the film thickness of the color filter is reduced in order to improve transparency, there is a problem that the color density is lowered. This problem is particularly noticeable for green, and there is a problem that the color reproduction rate is low and the color reproduction range as a display is narrow. In particular, when the film thickness of the composition as a color filter is 2.5 μm or less, it is more difficult to get rid of the above trade-off, and y in CIE chromaticity coordinates exceeds 0.6. It was extremely difficult.
[0009]
[Problems to be solved by the invention]
An object of the present invention is to provide a photocurable coloring composition and a color filter that have a high transmittance particularly with respect to green and can improve color reproducibility.
[0010]
[Means for Solving the Problems]
According to the present invention, a photocurable coloring composition and a color filter having the following constitution are provided to achieve the above object.
[0011]
(1) In a photocurable coloring composition containing an alkali-soluble resin, a colorant, a photosensitive polymerization component, a photopolymerization initiator, and a solvent, the film thickness is 2.2 μm or less, and y in CIE chromaticity coordinates A photocurable coloring composition characterized in that a coating film having a value of 0.65 or more can be formed.
[0012]
(2) The colorant comprises a mixture of a green pigment and a yellow pigment, and the green pigment is C.I. I. Pigment Green 7 and the yellow pigment is C.I. I. Pigment yellow 180 and / or C.I. I. It is pigment yellow 185, The photocurable coloring composition as described in said (1) characterized by the above-mentioned.
(3) The mixing ratio of the green pigment and the yellow pigment (green pigment: yellow pigment) is 1: 0.2 to 1: 3.5 by mass ratio, as described in (2) above Photocurable coloring composition.
(4) The photocurable coloring composition according to any one of (1) to (3), wherein the photopolymerization initiator is a halomethyl-S-triazine compound.
[0013]
(5) The photocurable coloring composition as described in any one of (1) to (4) above, wherein the alkali-soluble resin comprises at least one of the following resin A, resin B1 or B2. .
Resin A: (i) At least one acid component monomer selected from maleic anhydride, acrylic acid, methacrylic acid, and fumaric acid, (ii) alkylpolyoxyethylene (meth) acrylate, and (iii) benzyl (meth) Copolymer made of acrylate
Resin B1: a copolymer comprising (i) (meth) acrylic acid and (ii) benzyl methacrylate
Resin B2: a copolymer comprising (i) (meth) acrylic acid, (ii) benzyl methacrylate, and (iii) hydroxyethyl (meth) acrylate
[0014]
(6) The photocurable coloring composition according to any one of (1) to (5) above is applied onto a substrate and dried to form a coating film, and then pattern exposure is performed on the coating film. Color filter obtained by sequential development.
[0015]
The present inventors have found that a specific combination of a green pigment and a yellow pigment is particularly effective to achieve the object of the present invention, and in particular to enhance the color reproducibility of green. Furthermore, in order to obtain a color filter with excellent color reproducibility, it has been found that it is important to improve the fluidity of the photocurable composition. Moreover, the objective of this invention can be achieved more effectively by using specific copolymer resin as alkali-soluble resin.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The photocurable coloring composition of the present invention comprises an alkali-soluble resin, a colorant, a photosensitive polymerization component, a photopolymerization initiator, and a solvent as essential components.
And it is required that the coating film obtained by sequentially applying the composition on the substrate, drying, pattern exposure, phenomenon, and curing can have specific characteristics.
[0017]
Although the curing method of the photocurable coloring composition will be described in detail later, the thickness of the obtained coating film is 2.2 μm or less, preferably 2 μm or less. If the thickness of the coating film is too thick, a problem occurs.
[0018]
Further, the y value of the CIE chromaticity coordinates is required to be 0.65 or more, and preferably 0.65 ≦ y ≦ 0.71. If the y value is too low, there arises a problem that the color reproducibility is lowered.
On the other hand, the x value of the CIE chromaticity coordinates is not particularly limited, but preferably 0.14 ≦ x ≦ 0.34.
[0019]
Hereinafter, the compounding component used for the photocurable coloring composition of this invention and the usage method of this composition are demonstrated.
[I] Alkali-soluble resin
The alkali-soluble resin used in the composition of the present invention is not particularly limited, but preferably comprises at least one of the following resin A, resin B1 or B2.
Resin A: (i) At least one acid component monomer selected from maleic anhydride, acrylic acid, methacrylic acid, and fumaric acid, (ii) alkylpolyoxyethylene (meth) acrylate, and (iii) benzyl (meth) Copolymer made of acrylate
Resin B1: a copolymer comprising (i) (meth) acrylic acid and (ii) benzyl methacrylate
Resin B2: a copolymer comprising (i) (meth) acrylic acid, (ii) benzyl methacrylate, and (iii) hydroxyethyl (meth) acrylate
[0020]
In the present invention, the object of the present invention can be achieved more effectively by using a copolymer of the above resin as an alkali-soluble resin.
[0021]
In the alkali-soluble resin A, the composition mass ratio of (i) acid component monomer, (ii) alkylpolyoxyethylene (meth) acrylate, and (iii) benzyl (meth) acrylate is preferably 10-25 / 5-25 / 50-85, More preferably, it is 15-20 / 5-5 / 20-80. The polystyrene-reduced mass average molecular weight (Mw) of the alkali-soluble resin A is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
[0022]
[II] Colorant
As the colorant that can be used in the present invention, various conventionally known dyes and pigments can be used singly or in combination.
[0023]
The dye that can be used in the present invention is not particularly limited, and conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 Dyes disclosed in JP-A-6-194828 can be used. As chemical structure, dyes such as pyrazole azo, anilino azo, triphenyl methane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine are used. it can. In particular, since the curable composition can be cured at a relatively low temperature, even a dye that is inferior in heat resistance compared to a pigment can be used at a high temperature during post-baking to impart durability to the cured film. It is possible to reduce problems such as decomposition even when exposed to water.
[0024]
As the pigment that can be used in the present invention, conventionally known various inorganic pigments or organic pigments can be used. Also, considering that it is preferable that the pigment has a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment that is as fine as possible. However, in consideration of handling properties, the average particle size is preferably 0.01 μm. A pigment having a thickness of ˜0.1 μm, more preferably 0.01 μm to 0.05 μm is used. Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts, specifically metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. And composite oxides of the above metals.
[0025]
As an organic pigment,
CIPigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
CIPigment Orange 36, 38, 43, 71;
CIPigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177,209, 220, 224, 242, 254, 255, 264, 270;
CIPigment Violet 19, 23, 32, 39;
CIPigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CIPigment Green 7, 36, 37;
CIPigment Brown 25, 28;
CIPigment Black 1, 7;
Examples thereof include carbon black.
[0026]
In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the composition of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an effect.
[0027]
Although the following can be mentioned as a pigment which can be preferably used in this invention, It is not limited to these.
[0028]
CIPigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185;
CIPigment Orange 36, 71;
CIPigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264;
CIPigment Violet 19, 23, 32;
CIPigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CIPigment Black 1.
[0029]
These organic pigments are used alone or in various combinations in order to increase color purity. Specific examples are shown below. Red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them and disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylene red pigments Etc. are used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224 and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Pigment yellow 83 or C.I. I. Mixing with Pigment Yellow 139 was good. The mass ratio of the red pigment to the yellow pigment was good from 100: 5 to 100: 50. Below 100: 4, the light transmittance from 400 nm to 500 nm could not be suppressed, and the color purity could not be increased. At 100: 51 or more, the dominant wavelength became shorter and the deviation from the NTSC target hue became large. In particular, the range of 100: 30 to 100: 30 was optimal. In the case of a combination of red pigments, it is adjusted according to the chromaticity.
[0030]
As the green pigment, a halogenated phthalocyanine pigment alone or a mixture with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment is used. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 was good.
[0031]
As the colorant used in the composition of the present invention, a mixture of a green pigment and a yellow pigment is particularly preferable. I. Pigment Green-7 and the yellow pigment is C.I. I. Pigment yellow 180 and / or C.I. I. Pigment Yellow 185 is particularly preferable in order to improve the color reproducibility of green.
The mixing ratio of the green pigment and the yellow pigment (green pigment: yellow pigment) is not limited, but is preferably 1: 0.2 to 1: 3.5 by mass ratio, more preferably 1: 0.2-1: 2.0, most preferably 1: 0.3-1: 1.5. By setting the green and yellow pigments within this range, the color filter obtained from the photocurable coloring composition of the present invention can be made more excellent in color reproducibility.
[0032]
As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. I. Pigment blue 15: 6 and C.I. I. Mixing with Pigment Violet 23 was good. The mass ratio of the blue pigment to the purple pigment is preferably 100: 30 to 100: 0, more preferably 100: 10 or less.
[0033]
Further, a pigment-containing photosensitive resin having good dispersibility and dispersion stability by using a powdered processed pigment in which the above pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer and an ethyl cellulose resin. Can be obtained.
[0034]
The pigment treatment method will be described below. Generally, these pigments are supplied after drying by various methods after synthesis. Usually, it is dried from an aqueous medium and supplied as a powder. However, since water requires a large latent heat of vaporization for drying, a large amount of heat energy is given to dry it to form a powder. Therefore, the pigment usually forms an aggregate (secondary particle) in which primary particles are aggregated.
[0035]
It is not easy to disperse pigments forming such aggregates in fine particles. Therefore, it is preferable to treat the pigment with various resins in advance. Examples of these resins include the alkali-soluble resins described above. As a processing method, there are a flushing process, a kneading method using a kneader, an extruder, a ball mill, a two or three roll mill, and the like. Among these, a flushing process or a kneading method using two or three roll mills is suitable for fine particle formation.
[0036]
The flushing treatment is usually a method in which an aqueous dispersion of pigment and a resin solution dissolved in a solvent immiscible with water are mixed, the pigment is extracted from an aqueous medium into an organic medium, and the pigment is treated with a resin. According to this method, since the pigment is not dried, the aggregation of the pigment can be prevented and the dispersion becomes easy. In kneading with a two or three roll mill, the pigment and resin or resin solution are mixed, and then the pigment and resin are kneaded while applying a high shear (shearing force), thereby coating the resin on the pigment surface. , A method for treating pigments. The pigment particles aggregated in this process are dispersed from the lower order aggregates to the primary particles.
[0037]
In the present invention, processed pigments previously treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin or the like can also be used conveniently. In the present invention, the processed pigment treated with the above-mentioned various resins is preferably a powder, paste, pellet, or paste in which the resin and the pigment are uniformly dispersed. Further, a non-uniform lump in which the resin is gelled is not preferable. The colored dispersion thus obtained is mixed with a photosensitive component and used as a photocurable coloring composition.
[0038]
Although the coloring agent content rate in the total solid of the photocurable coloring composition of this invention is not specifically limited, Preferably it is 30-60 mass%. Moreover, the resin content of the composition when the alkali-soluble resin A is used alone as the alkali-soluble resin is preferably 10 to 50% by mass, more preferably 10 to 40% by mass in the total solid content, and the alkali-soluble When the resin B1 or B2 is used in combination, the total resin content of the composition is preferably 10 to 50% by mass.
[0039]
In the present invention, conventionally known pigment dispersants and surfactants can be added for the purpose of improving the dispersibility of the pigment. As these dispersants, many kinds of compounds are used. For example, a phthalocyanine derivative (commercial product EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Geneca); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) ), (Meth) acrylic acid-based (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho), and other cationic surfactants; polyoxyethylene Nonionic series such as lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester Activating agents: Anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (above (Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by Sannopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, Various Solsperse dispersants (manufactured by Zeneca Corporation) such as 24000, 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L 01, P103, F108, L121, P-123 (manufactured by Asahi Denka) and Isonetto S-20 (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
[0040]
[III] Photopolymerization component
Next, the photosensitive polymerization component used in the photocurable coloring composition of the present invention will be described.
As the photosensitive polymerization component, a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or higher under normal pressure is preferable. An acrylate compound is more preferable.
[0041]
Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meta ) Monofunctional acrylates and methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, Poly (meth) of pentaerythritol or dipentaerythritol after addition of ethylene oxide or propylene oxide to polyfunctional alcohols such as ri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane Acrylates, urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49 -Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid described in JP-B No. 43191 and JP-B-52-30490 I can do it. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used.
[0042]
Further, a compound obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol and then (meth) acrylated is described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. These can also be used as photosensitive polymerization components.
[0043]
Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and a structure in which these acryloyl groups are interposed via ethylene glycol or propylene glycol residues are preferable. These oligomer types are also used. These photosensitive polymerization components can be used alone or in combination of two or more. The usage-amount of these photosensitive polymerization components becomes like this. Preferably it is 20-200 mass% with respect to the total solid content 100 of a photocurable coloring composition, More preferably, it is 50-120 mass%.
[0044]
[IV] Photopolymerization initiator
Examples of the photopolymerization initiator include active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, 3-aryl-substituted coumarin compounds, and at least one lophine dimer. Particularly, halomethyl- It is preferably an s-triazine compound.
These compounds are described in detail below.
[0045]
Among active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, halomethyloxadiazole compounds include 2-halomethyl-5 represented by the following general formula IV described in JP-B-57-6096. -A vinyl-1,3,4-oxadiazole compound is mentioned.
[0046]
[Chemical 1]

[0047]
In general formula IV:
W represents a substituted or unsubstituted aryl group, and X represents a hydrogen atom, an alkyl group or an aryl group.
Y represents a fluorine atom, a chlorine atom or a bromine atom.
n represents an integer of 1 to 3.
Specific compounds of the general formula IV include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4- Examples include oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole.
[0048]
Examples of the halomethyl-s-triazine compound include a vinyl-halomethyl-s-triazine compound represented by the following general formula V described in JP-B-59-1281, and the following general formula described in JP-A-53-133428. 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by VI and 4- (p-aminophenyl) -2,6-di-halomethyl represented by the following general formula VII -S-triazine compound is mentioned.
[0049]
[Chemical formula 2]

[0050]
In general formula V:
Q represents Br or Cl.
P is -CQ _Three (Q is as defined above), -NH ₂ , -NHR, -N (R) ₂ Or -OR (wherein R represents a phenyl or alkyl group).
W represents an aromatic group which may be substituted, a heterocyclic group which may be substituted, or a monovalent group represented by the following general formula VA.
[0051]
[Chemical 3]

[0052]
In the general formula VA, Z is —O— or —S—, and R is as defined above.
[0053]
[Formula 4]

[0054]
In general formula VI:
X represents Br or Cl.
m and n are integers of 0-3.
R ′ represents a group represented by the following general formula VIA.
[0055]
[Chemical formula 5]

[0056]
(In the above general formula VIA, R ₁ Is a hydrogen atom or ORc (Rc is an alkyl, cycloalkyl, alkenyl, aryl group), R ₂ Represents a Cl, Br, alkyl, alkenyl, aryl, or alkoxy group. )
[0057]
[Chemical 6]

[0058]
In general formula VII:
R ₁ , R ₂ Are the same or different and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a group represented by the following general formula VIIA or VIIB.
R _Three , R _Four Are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.
X and Y are the same or different and each represents Cl or Br.
m and n are the same or different and represent 0, 1 or 2.
[0059]
[Chemical 7]

[0060]
In general formulas VIIA and VIIB, R _Five , R ₆ , R ₇ Represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Examples of substituents in substituted alkyl groups and substituted aryl groups include aryl groups such as phenyl groups, halogen atoms, alkoxy groups, carboalkoxy groups, carboaryloxy groups, acyl groups, nitro groups, dialkylamino groups, sulfonyl derivatives, etc. Is mentioned.
[0061]
In general formula VII, R ₁ And R ₂ May form a heterocycle consisting of a nonmetallic atom together with a nitrogen atom bonded to them, and in this case, examples of the heterocycle include those shown below.
[0062]
[Chemical 8]

[0063]
Specific examples of general formula V include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethyl). And aminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like.
[0064]
Specific examples of general formula VI include 2- (naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) ) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [ 4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4, 6-bis-trichloromethyl-s-to Azine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy- Naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, etc. Can be mentioned.
[0065]
Specific examples of the general formula VII include 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-p -N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p- N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s- Riazine, 4- [p-N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine, 4- [p-N- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N -Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2, 6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) ) -S-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo -PN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) Aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N -Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di ( Trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro- p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2 , 6-Di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m Chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (Trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-p- N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -S-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-to Azine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o- Chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloro Methyl) -s-triazine, and the like.
[0066]
These initiators can be used in combination with a sensitizer. Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) ) Benzophenone (or Mihira) Ketone), p- (diethylamino) benzophenone, benzothiazole compounds of benzanthrone like and Sho 51-48516 JP thereof.
[0067]
Moreover, the said 3-aryl substituted coumarin compound is a compound shown, for example by the following general formula VIII.
[0068]
[Chemical 9]

[0069]
R ₈ Is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms (preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group), R ₉ Is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a group represented by the following general formula VIIIA (preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a general formula VIIIA Group, particularly preferably a group represented by the general formula VIIIA).
[0070]
R _Ten , R ₁₁ Are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), and a haloalkyl group having 1 to 8 carbon atoms (for example, chloromethyl group, fluoromethyl group, trifluoro). Methyl group, etc.), C1-C8 alkoxy group (for example, methoxy group, ethoxy group, butoxy group), C6-C10 aryl group (for example, phenyl group) which may be substituted, amino group, -N ( R ₁₆ ) (R ₁₇ ), A halogen atom (for example, Cl, Br, F). Preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group, -N (R ₁₆ ) (R ₁₇ ), Cl.
[0071]
R ₁₂ Represents an optionally substituted aryl group having 6 to 16 carbon atoms (for example, phenyl group, naphthyl group, tolyl group, cumyl group). As the substituent, an amino group, -N (R ₁₆ ) (R ₁₇ ), An alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), haloalkyl group having 1 to 8 carbon atoms (for example, chloromethyl group, fluoromethyl group, trifluoromethyl group, etc.) ), An alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group), hydroxy group, cyano group, and halogen atom (for example, Cl, Br, F).
[0072]
R ₁₃ , R ₁₄ , R ₁₆ , R ₁₇ Are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group). R ₁₃ And R ₁₄ And R ₁₆ And R ₁₇ May combine with each other to form a heterocyclic ring (for example, a piperidine ring, a piperazine ring, a morpholine ring, a pyrazole ring, a diazole ring, a triazole ring, a benzotriazole ring, etc.) together with a nitrogen atom.
[0073]
R ₁₅ Are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group) , An optionally substituted aryl group having 6 to 10 carbon atoms (for example, phenyl group), amino group, N (R ₁₆ ) (R ₁₇ ), A halogen atom (for example, Cl, Br, F). Zb is = O, = S or = C (R ₁₈ ) (R ₁₉ ). Preferably = O, = S, = C (CN) ₂ And particularly preferably = O. R ₁₈ , R ₁₉ Are the same or different and each represents a cyano group, -COOR ₂₀ , -COR _{twenty one} Represents. R ₂₀ , R _{twenty one} Are each an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), haloalkyl group having 1 to 8 carbon atoms (for example, chloromethyl group, fluoromethyl group, trifluoromethyl group, etc.) ), An optionally substituted aryl group having 6 to 10 carbon atoms (for example, a phenyl group).
[0074]
Particularly preferred 3-aryl-substituted coumarin compounds are {(s-triazin-2-yl) amino} -3-arylcoumarin compounds represented by the general formula IX.
[0075]
[Chemical Formula 10]

[0076]
Lophine dimer means 2,4,5-triphenylimidazolyl dimer composed of two lophine residues, and its basic structure is shown below.
[0077]
Embedded image

[0078]
Specific examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxy). Phenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, and the like.
[0079]
In the present invention, other known compounds can be used in addition to the above initiators.
For example, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, aromatics substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, triallyl disclosed in US Pat. No. 3,549,367 Combination of imidazole dimer / p-aminophenyl ketone, benzothiazole compound / trihalome disclosed in Japanese Patent Publication No. 51-48516 Thial-s-triazine compounds are exemplified.
Further, Adeka optomer SP-150, 151, 170, 171, N-1717, N1414, etc. manufactured by Asahi Denka Co., Ltd. can be used as the polymerization initiator.
[0080]
The usage-amount of a photoinitiator becomes like this. Preferably it is 0.1-10.0 mass% of the total solid of a photocurable coloring composition, More preferably, it is 0.5-5.0 mass%. When the amount of the initiator used is less than 0.1% by mass, the polymerization hardly proceeds, and when it exceeds 10.0% by mass, the film strength tends to be weakened.
[0081]
[V] Solvent
Examples of the solvent used in preparing the photocurable coloring composition of the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, and butyric acid. Isopropyl, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl, 2 Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyruvic acid Methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol Methyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether Acetates, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xyles and the like.
[0082]
Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used.
[0083]
These solvents may be used alone or in combination of two or more.
[0084]
[VI] Fluorine compounds
It is preferable that the photocurable coloring composition of the present invention further contains a fluorine-based compound represented by the following formula (I).
C ₈ F ₁₇ SO ₂ N (R ₁ ) CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n R ₂ (I)
In formula (I), R ₁ And R ₂ Each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 30.
In the formula (I), preferably R ₁ Is a methyl group, an ethyl group or an iso-propyl group, and R ₂ Is a hydrogen atom. The preferable range of n is 10-25, and the particularly preferable range is 10-20.
[0085]
Examples of the fluorine-based compound represented by the above formula (I) include Megafac F-141 (n = 5), F-142 (n = 10), F-143 (manufactured by Dainippon Ink and Chemicals, Inc.). n = 15) and F-144 (n = 20).
[0086]
In addition, the photocurable coloring composition of the present invention preferably contains at least one fluorine-based compound selected from the following general formulas (1) to (4). In particular, compounds represented by the following general formulas (1) and (2) are preferred.
R ^f1 -X- (CH ₂ CH ₂ O) _n R ¹ (1)
R ^f1 -X- (CH ₂ CH ₂ O) _n R ^f2 (2)
R ^f1 -X- (CH ₂ CH ₂ O) _n (CH ₂ CH ₂ CH ₂ O) _m -R ¹ (3)
R ^f1 -X- (CH ₂ CH ₂ O) _n (CH ₂ CH ₂ CH ₂ O) _m -R ^f2 (4)
[0087]
Where R ¹ Represents an alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and these alkyl groups may be saturated alkyl groups or unsaturated alkyl groups. Good. These alkyl groups may have a linear structure or a branched structure, but a branched structure is preferred.
Examples of the alkyl group include methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosanyl. Group, docosanyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group and the like.
These alkyl groups may be substituted with a halogen atom, an acyl group, an amino group, a cyano group, an alkyl group, an alkoxy group, an aryl group that may be substituted with alkyl or haloalkyl, an amide group, or the like.
[0088]
R ^f1 And R ^f2 Each independently represents a perfluoro group having 1 to 18 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and these perfluoro groups may be saturated or unsaturated. Good. These perfluoro groups may have a linear structure or a branched structure, but a branched structure is particularly preferred in the photosensitive colored resin composition of the present invention. R ^f1 And R ^f2 May be the same as or different from each other.
Examples of these perfluoro groups include perfluorononenyl, perfluoromethyl, perfluoropropylene, perfluorononenyl, perfluorobenzoic acid, perfluoropropylene, perfluoropropyl, perfluoro (9-methyloctyl), and perfluoromethyloctyl. Perfluorobutyl, perfluoro-3-methylbutyl, perfluorohexyl, perfluorooctyl, perfluoro-7-octylethyl, fluoroheptyl, perfluorooctyl, perfluorodecyl, perfluorobutyl, and the like.
Further, these perfluoro groups may be substituted with a halogen atom, an acyl group, an amino group, a cyano group, an alkyl group, an alkoxy group, an aryl group which may be substituted with alkyl or haloalkyl, an amide group, or the like.
In the present invention, these fluorine compounds are R ^f1 Or R ¹ It is preferable that at least one of the compounds has a branched structure.
[0089]
n represents an integer of 1 to 40, preferably an integer of 4 to 25, and m represents an integer of 0 to 40, preferably an integer of 0 to 25.
-X- is-(CH ₂ ) _l -(Wherein l is an integer of 1 to 10, preferably 1 to 5), -CO-O-, -O-, -NHCO-, or -NHCOO-.
[0090]
By further containing the specific fluorine-based compound in the composition of the present invention, the liquid properties of the composition are further improved. In other words, the fluidity of the coating liquid is improved, the adhesion of the liquid in the spin coater nozzle and pipes and containers used in the coating process is improved, and the residue remaining as dirt can be almost eliminated. The amount of cleaning liquid required for cleaning at the time of switching the liquid and the working time can be reduced, and process suitability is improved. In addition, it is thought that the said fluorine-type compound is acting as a nonionic surfactant in the photosensitive composition of this invention.
[0091]
In the present invention, the compounds represented by the general formula (I) and (1) to (4) may be used alone or in combination of two or more. In addition, 2 or more types includes both the case where two or more different compounds represented by the same general formula are used, and the case where two or more types of compounds represented by different general formulas are used.
In the present invention, the addition amount of these specific fluorine-based compounds is preferably 0.01 to 2.0% by mass, more preferably 0.1 to 1.0% by mass with respect to the total coating solution.
[0092]
[VII] Other ingredients
In the photocurable coloring composition of the present invention, various additives, for example, a filler, a polymer compound other than the alkali-soluble resin, a surfactant other than the above, an adhesion promoter, an antioxidant, an ultraviolet ray are included as necessary. Absorbers, anti-aggregation agents and the like can be blended.
[0093]
Specific examples of these additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, hydroxyl group A polymer having an acid anhydride added thereto, an alcohol-soluble nylon, an alkali-soluble resin such as a phenoxy resin formed from bisphenol A and epichlorohydrin; a nonionic, a kachin-based, an anionic surfactant, etc. Phthalocyanine derivatives (commercially available products EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No .95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho), and other cationic surfactants; polyoxy Tylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, manufactured by BASF) Nonionic surfactants such as L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1; Fluorine series such as F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei) Surfactant: Anionic surfactant such as W004, W005, W017 (manufactured by Yusho); EFKA-46, EFKA-47, EFKA-47EA, EFK Polymer dispersing agents such as polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by Sannopco) Various Solsperse dispersants (manufactured by Geneca Corporation) such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka) and Isonet S-20 (manufactured by Sanyo Chemical);
[0094]
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;
And an aggregation inhibitor such as sodium polyacrylate.
[0095]
In addition, when promoting the alkali solubility of the unirradiated part and further improving the developability of the composition of the present invention, the composition of the present invention is an organic carboxylic acid, preferably a low molecular weight of 1000 or less. An organic carboxylic acid can be added. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.
[0096]
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the photocurable coloring composition of the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol. , T-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. Is useful.
[0097]
[VII] Method of using the composition of the present invention
The photocurable coloring composition of the present invention comprises a colorant, an alkali-soluble resin, a photosensitive polymerization component, a photopolymerization initiator, a fluorine compound used as necessary, and And Other additives can be mixed with a solvent and mixed and dispersed using various mixers and dispersers.
[0098]
As a preferable production method of the composition of the present invention, alkali-soluble resin B1 or (meth) acrylic acid, benzyl methacrylate, and hydroxyethyl (meth), which is a copolymer comprising (meth) acrylic acid and benzyl methacrylate as a colorant, are used. Kneading and dispersing the alkali-soluble resin B2 which is a copolymer made of acrylate with a viscosity of 10,000 mPa · s or more, and then adding the alkali-soluble resin A and finely dispersing with a viscosity of 1,000 mPa · s or less. It is.
[0099]
In the kneading and dispersing step, first, the pigment and the dispersant or the surface treatment agent, the resin B1 or B2 of the present invention (a part or all of the resin A when neither of the resins B1 and B2 are used) and a solvent are kneaded. The machines used for kneading are two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, single-screw and twin-screw extruders, etc., which disperse while giving a strong shearing force. Next, the solvent and the resin A of the present invention (the balance used in the kneading step) were added, and a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc. were mainly used, and 0.1-1 mm Disperse with beads made of glass or zirconia of particle size. It is possible to omit this kneading step. In that case, beads are dispersed with a pigment and a dispersant or a surface treatment agent, the resin B1 or B2 of the present invention (a part or all of the resin A if none is used), and a solvent. In this case, it is preferable to add the remaining resin A in the kneading step during the dispersion.
Details of kneading and dispersing are described in TC Patton "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, 1964) and the like.
[0100]
The photocurable coloring composition of the present invention is applied to a substrate by a coating method such as spin coating, cast coating, roll coating, and the like to form a radiation-sensitive layer, and is exposed through a predetermined mask pattern. A color filter can be manufactured by developing with a developing solution. As radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.
In the present invention, the color filter manufactured as described above is characterized in that the film thickness of the coating film is 2.2 μm or less and the y value of CIE chromaticity coordinates is 0.65 or more. A color filter is also provided. The film thickness and y value are the same as those described for the composition.
[0101]
Examples of the substrate include soda glass, pyrex glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, and photoelectric conversion element substrates used for solid-state imaging elements such as silicon substrates. Can be mentioned. These substrates are generally formed with black stripes that isolate pixels.
[0102]
Any developer can be used as long as it dissolves the radiation-sensitive layer in the non-irradiated part, but does not dissolve the irradiated part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. Examples of the organic solvent include the aforementioned solvents used in preparing the composition of the present invention.
[0103]
Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, An alkaline aqueous solution in which an alkaline compound such as pyrrole or piperidine is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.
[0104]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.
Example 1
・ 80 parts by mass of benzyl methacrylate / methacrylic acid copolymer
(Weight average molecular weight 30000; acid value 120)
・ C. I. Pigment Green 7 100 parts by mass
・ C. I. Pigment Yellow 185 30 parts by mass
・ 500 parts by mass of propylene glycol monomethyl ether acetate
Was dispersed day and night in a sand mill.
[0105]
The following ingredients were then added:
・ 80 parts by mass of dipentaerythritol hexaacrylate
4- [o-bromo-pN, N-di (ethoxycarbonyl) 5 parts by mass
Aminophenyl] 2,6-di (trichloromethyl)
-S-triazine
・ 7-[{4-Chloro-6- (diethylamino) -S-triazine 2 parts by mass
-2-yl} amino] -3-phenylcoumarin
・ 0.01 parts by mass of hydroquinone monomethyl ether
・ 500 parts by mass of propylene glycol monomethyl ether acetate
[0106]
The above components were uniformly mixed and then filtered through a filter having a pore size of 5 μm to obtain a photocurable coloring composition of the present invention. When this composition was applied to a glass substrate for a color filter with a spin coater so that the dry film thickness was 2.2 μm and dried at 120 ° C. for 2 minutes, a uniform green coating film was obtained.
[0107]
Next, the CIE chromaticity (x value, y value) was measured for the unexposed coating film with a chromaticity meter (manufactured by Otsuka Electronics Co., Ltd.). The results are shown in Table 1.
[0108]
(Examples 2-6 and Comparative Examples 1-4)
In Example 1, it carried out like Example 1 except having changed the kind and mixture ratio of the pigment as described in Table 1. The results are also shown in Table 1.
[0109]
[Table 1]

[0110]
In Table 1,
PG7: CI Pigment Green 7
PG36: CI Pigment Green 36
PY185: CI Pigment Yellow 185
PY180: CI Pigment Yellow 180
PY150: CI Pigment Yellow 150
[0111]
【The invention's effect】
The photocurable coloring composition of the present invention can provide a color filter having high transmittance especially for green and excellent color reproducibility. As a result, the image of the liquid crystal display is sharpened and the luminance is improved and the color is stable. It becomes possible to ensure the sex.

Claims (4)

In a photocurable coloring composition containing an alkali-soluble resin, a colorant, a photosensitive polymerization component, a photopolymerization initiator, and a solvent, the film thickness is 2.2 μm or less, and the CIE chromaticity coordinate y value is 0. .65 above the is a photocurable colored composition that give to form a coating film,
The colorant comprises a mixture of a green pigment and a yellow pigment, and the green pigment is C.I. I. Pigment Green 7 and the yellow pigment is C.I. I. Pigment yellow 180 and / or C.I. I. Pigment Yellow 185, and the photopolymerization initiator is a halomethyl-S-triazine compound. 2. The photocurable coloring according to claim 1 , wherein a mixing ratio of the green pigment and the yellow pigment (green pigment: yellow pigment) is 1: 0.2 to 1: 3.5 by mass ratio. Composition. The photocurable coloring composition according to claim 1 or 2 , wherein the alkali-soluble resin comprises at least one of the following resin A, resin B1 or B2.
Resin A: (i) At least one acid component monomer selected from maleic anhydride, acrylic acid, methacrylic acid, and fumaric acid, (ii) alkylpolyoxyethylene (meth) acrylate, and (iii) benzyl (meth) Copolymer resin B1: acrylate copolymer resin B1: (i) (meth) acrylic acid and (ii) benzyl methacrylate copolymer resin B2: (i) (meth) acrylic acid, (ii) benzyl methacrylate, and (iii) Copolymer made of hydroxyethyl (meth) acrylate The photocurable coloring composition according to any one of claims 1 to 3 is coated on a substrate and dried to form a coating film, and then pattern exposure and development are sequentially performed on the coating film. The obtained color filter having a green coating film having a dry film thickness of 2.2 μm or less and a y value of CIE chromaticity coordinates of 0.65 or more .