JP4092376B2 - Photosensitive colored resin composition, method for producing the same, and method for producing color filter - Google Patents

Abstract

PURPOSE: A photosensitive colored resin composition, its preparation method and a method for preparing a color filter are provided, to improve the uniformity of coating thickness, the liquid saving property and the transmittance and to broaden the development latitude. CONSTITUTION: The photosensitive colored resin composition comprises 30-60 wt% (in solid component) of a colorant; 10-50 wt% (in solid component) of an alkali-soluble resin A; a photosensitive polymerizable component; a photopolymerization initiator; and a solvent. The alkali-soluble resin A is a copolymer comprising essentially at least one acid component monomer selected from the group consisting of maleic anhydride, acryl acid, methacrylic acid and fumaric acid; alkyl polyoxyethylene (meth)acrylate; and benzyl (meth)acrylate.

Description

【００５６】
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。
【００５７】
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。
【００５８】
【化２】

【００５９】
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。
ｎは、０〜３の整数を表す。
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。
【００６０】
【化３】

【００６１】
一般式ＶＡ中、Ｚは−Ｏ−又は−Ｓ−であり、Ｒは上記と同義である。
【００６２】
【化４】

【００６３】
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。
【００６４】
【化５】

【００６５】
（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。）
【００６６】
【化６】

【００６７】
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。
【００６８】
【化７】

【００６９】
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。
【００７０】
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。
【００７１】
【化８】

【００７２】
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。
【００７３】
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。
【００７４】
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。
【００７５】
これら開始剤には以下の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。
【００７６】
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。
【００７７】
【化９】

【００７８】
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。
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。
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。
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。
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。
【００７９】
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。
【００８０】
【化１０】

【００８１】
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。
【００８２】
【化１１】

【００８３】
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。
【００８４】
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。
【００８５】
開始剤の使用量は、感光性着色樹脂組成物の全固形分の０．１〜１０．０質量％、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。
【００８６】
〔V〕溶剤
本発明の感光性着色樹脂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、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。
【００８７】
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。
【００８８】
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。
【００８９】
〔VI〕フッ素系有機化合物
本発明の感光性着色樹脂組成物には、更にフッ素含有率が３〜４０質量％、好ましくは５〜３０質量％、より好ましくは７〜２５質量％であるフッ素系有機化合物を含有するのが望ましい。
フッ素系有機化合物のフッ素含有率が低いと、塗布厚均一性や省液性において充分な効果が得られず、また逆に含有率が大きすぎると、組成物中への溶解性が不十分となる。
本発明においてフッ素系有機化合物を含有させることにより、塗布液としての液特性を改良することができ、塗布厚の均一性や省液性を改良することができる。特に、基板への濡れ特性が向上し、少量の液量でも厚みムラのない均一な膜厚の塗膜を得ることができる。
【００９０】
この様なフッ素系有機化合物としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７（以上、大日本インキ株式会社製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１(以上、住友スリーエム株式会社製）、サーフロンＳ−３８２、同ＳＣ−１０１、同ＳＣ−１０３、同ＳＣ−１０４、同ＳＣ−１０５、同ＳＣ１０６８、同ＳＣ−３８１、同ＳＣ−３８３、同Ｓ３９３、同ＫＨ−４０（以上、旭硝子株式会社製）等が挙げられる。
中でも、メガファックＦ１７７、メガファックＦ１４３、メガファックＲ３０等が好ましい。
【００９１】
前記フッ素系有機化合物の中でも、下記（I）式で表される構造の化合物が特に好ましい。
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。
【００９２】
本発明の組成物中にさらに上記式（I)で表されるフッ素系有機化合物を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、上記フッ素系有機化合物は、本発明の感光性組着色樹脂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。
また、塗布液としての流動性を改良し、基板と塗布液との界面張力を低下せしめて、基板への濡れ性を改良し、もって数μｍ程度の薄膜であっても厚みムラが小さい塗布膜を得ることができる。特に、塗布膜が薄くなると、塗布ムラや厚みムラ、更には塗布面で液切れをおこしやすいスリット塗布に対して、良好な結果をもたらす。
【００９３】
本発明において式（I)で表される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０．００１〜２．０質量％であり、より好ましくは０．０５５〜１．０質量％、最も好ましくは０．００３〜０．５質量％である。
【００９４】
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。
【００９５】
〔VII〕その他の成分
本発明の感光性着色樹脂組成物には、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。
【００９６】
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；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）；
【００９７】
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。
【００９８】
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。
【００９９】
本発明の感光性着色樹脂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。
【０１００】
〔VII〕本発明の組成物の製造方法及び使用方法
本発明の感光性着色樹脂組成物は、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。
尚、混合分散工程は、混練分散とそれに続けて行う微分散処理からなるのが好ましいが、混練分散を省略することも可能である。
【０１０１】
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を混練分散処理後の粘度が１０,０００ｍＰａ・ｓ以上、望ましくは１００，０００ｍＰａ・ｓ以上の比較的高粘度になるように混練分散処理し、次いで前記アルカリ可溶性樹脂Ａを添加して、微分散処理後の粘度が１,０００ｍＰａ・ｓ以下、望ましくは１００ｍＰａ・ｓ以下の比較的低粘度になるように微分散処理することである。
【０１０２】
混練分散工程では、原料の着色剤の粒子表面をビヒクルの樹脂成分を主体とした構成成分との濡れを促進し、着色剤粒子と空気の固体／気体界面から、着色剤粒子とビヒクル溶液の固体／溶液界面に変換する。微分散工程では、ガラスやセラミックの微粒の分散用メディアと共に混合攪拌することにより、着色剤粒子を一次粒子に近い微小な状態にまで分散する。従って、混練分散工程では着色剤
粒子表面が形成する界面を空気から溶液に変換する必要があるので、強い剪断力圧縮力が必要となり、それにふさわしい混練機、被混練物は高粘度のものが望ましく、一方、微分散工程では粒子を微小な状態にまで均一に安定に分布させることが必要となり、凝集している着色剤粒子に衝撃力と剪断力を不要するような分散機と、比較的低い被分散物は比較的低粘度であることが望ましい。
【０１０３】
本発明の感光性着色樹脂組成物を用いて、例えば、カラーフィルターを作成するための混練分散工程は、先ず有機顔料やカーボンブラック等の着色剤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。
【０１０４】
本発明の感光性着色樹脂組成物を、直接または他の層を介して基板に回転塗布、スリット塗布、流延塗布、ロール塗布等の塗布方法により塗布して、感放射線性組成物層を形成し、所定のマスクパターンを介して露光し、光照射された塗布膜部分だけを硬化させ、現像液で現像することによって、各色（３色あるいは４色）の画素からなるパターン状皮膜を形成し、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、ｉ線等の紫外線が好ましく用いられる。
次いでアルカリ現像処理を行うことにより、上記露光により光未照射部分をアルカリ水溶液に溶出させ、光硬化した部分だけが残る。現像液としては、光未照射部の感光性層を溶解し、一方光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。
次いで、余剰の現像液を洗浄除去し、乾燥を施した後に、５０℃〜２４０℃の温度で加熱処理（ポストベーク）を行う。このように各色ごとに前記工程を順次繰り返して硬化皮膜を製造することができる。これによりカラーフィルターが得られる。
【０１０５】
基板としては、例えば液晶表示素子等に用いられる無アルカリガラス、ソーダガラス、パイレックスガラス、石英ガラス及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。さらに、プラスチック基板も可能である。これらの基板上には、通常、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。
【０１０６】
プラスチック基板の原材料としては、光学特性、耐熱性、機械的強度などの点から（１）アモルファスポリオレフィン、（２）ポリエーテルスルホン、（３）ポリグルタルイミド、（４）ポリカーボネート、（５）ポリエチレンテレフタレート、（６）ポリエチレンナフタレート、（７）ノルボルネンポリマー、（８）ビスアニリンフルオレンをジアミン成分としたポリイミド、（９）ビスフェノールフルオレンと２塩基酸からなるポリエステルなどが挙げられる。この中でも（２）ポリエーテルスルホン、（４）ポリカーボネート、（５）ポリエチレンテレフタレート、及び（７）ノルボルネンポリマーが好ましい。上記原材料は特にＬＣＤ用途において好ましい。
プラスチック基板に求められる特性としては、低熱膨張（カラーフィルター作成時の硬化処理に伴う表示精度の劣化防止）、ガスバリヤー性（液晶の安定性確保）、光透過率や光学等方性などの光学特性、表面平滑性などがある。熱膨張に関しては熱膨張係数が１０^-4以下であることが好ましい。
また、プラスチック基板にはその表面にガスバリヤー層及び／又は耐溶剤性層を有していることが好ましい。
【０１０７】
基板上に塗布された本発明の感光性着色樹脂組成物層の乾燥（プリベーク）は、ホットプレート、オーブン等で５０℃〜１４０℃の温度で１０〜３００秒で行うことができる。
【０１０８】
本発明の感光性着色樹脂組成物の塗布厚み（乾燥後）は、一般的に０．３〜５．０μｍ、望ましくは０．５〜３．５μｍ、最も望ましくは１．０〜２．５μｍである。
【０１０９】
現像液としては、本発明の感光性着色樹脂組成物を溶解し、一方放射線照射部を溶解しない組成物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合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。
現像温度としては通常２０℃〜３０℃であり、現像時間としては２０〜９０秒である。
【０１１０】
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、炭酸水素ナトリウム、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、１，８−ジアザビシクロ−［５，４，０］−７−ウンデセ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（リンス）する。
【０１１１】
ポストベークは、硬化を完全なものとするための現像後の加熱であり、通常約２００℃〜２２０℃の加熱（ハードベーク）を行う。
このポストベーク処理は、現像後の塗布膜を、上記条件になるようにホットプレートやコンベクションオーブン（熱風循環式乾燥機）、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。
【０１１２】
本発明の感光性着色樹脂組成物の用途として、主にカラーフィルターへの用途を主体に述べてきたが、カラーフィルターの画素間に設けられるブラックマトリックスにも適用できることは勿論である。ブラックマトリックスは、本発明の組成物にカーボンブラック、チタンブラックなどの黒色の着色剤を添加した組成物を光露光、アルカリ現像し、更にその後、ポストベークして膜の硬化を促進させて形成させることができる。
カラーフィルター用各種構成部品としては、上記カラーフィルター本体（着色層）やブラックマトリックスの他にスペーサー、保護層、コンタクトホール形成層などにも適用できる。更に、本発明の着色樹脂組成物は、上記カラーフィルター用各種構成部品以外にも、ＣＯＢ（チップオンボード）のポッティング用封止剤やＬＣＤ用シール剤としても用いることが可能である。
【０１１３】
【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よっていささかも限定されて解釈されるものではない。
【０１１４】
感光性着色樹脂組成物の調製
・Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２５４ ２７質量部
・Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １３９ ４質量部
・下記表１に示された樹脂Ｂ１もしくはＢ２（実施例１及び
比較例１は樹脂Ａのみ）のプロピレングリコールモノメチル
エーテルアセテート溶液 （固形分５０％）
２２質量部
・分散剤（ＢＹＫ社 ＢＹ−１６１） ２質量部
上記各成分を３本ロールで混練分散処理をし、次いで
・下記表１に示された樹脂Ａのプロピレングリコールモノメチル
エーテルアセテート溶液（固形分５０％） ２２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（溶剤）２００質量部
を加え、サンドミルで一昼夜微分散処理をした。
【０１１５】
次いで、下記成分を添加し、攪拌混合して感光性着色樹脂組成物（レジスト液）を調製した。
・ジペンタエリスリトールペンタ、ヘキサアクリレート ２０質量部
・４−［ｏ−ブロモ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニル）アミノフェニル］
２、６−ジ（トリクロロメチル）−Ｓ−トリアジン（光重合開始剤）１質量部
・界面活性剤 ＢＡＳＦ社 テトロニック １５０Ｒ１ ０．５質量部
・フッ素系化合物 ＤＩＣ社 メガファック Ｆ−１４３ 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（溶剤）１５０質量部
尚、上記工程において混練後及び分散後各々の分散液粘度を表１に示す。
【０１１６】
実施例１〜１１及び比較例１〜５
上記で得られた各組成物を下記の方法で、塗布厚均一性、液使用量、塗布ムラ、現像ラチチュード、及び、透過率について評価した。
【０１１７】
（１）＜スピンコート＞塗布厚均一性：
５５０ｍｍ×６５０ｍｍのガらス基板上に上記調製したレジスト液３０ｇを中央滴下し、６００ｒｐｍでスピンコートした。塗布基板の中央部から、対角線方向に縁から３００ｍｍ内側の部分までの厚みを測定した。塗布厚みムラを下式で表し、％で表示した。
厚みムラ＝（中央部の厚み−縁部３０ｍｍ内側の厚み）／中央部の厚み
（２）＜スピンコート＞塗液使用量：
５５０ｍｍ×６５０ｍｍのガラス基板上に上記調製したレジスト液２０〜４０ｇを中央滴下し８００ｒｐｍでスピンコートしたときに、最縁部の一部が塗布されなくなる最小液量を測定した。
【０１１８】
（３）＜スリット塗布＞塗布ムラ：
スリット間隙が５０μｍの塗布有効幅が２０ｍｍのスリットヘッドを備えたスリット塗布装置を用いて、乾燥後の塗膜厚が２μｍになるようにスリットと基板間の間隙を調節して、５０ｍｍ／秒の塗布スピードで各実施例・比較例の感光性着色樹脂組成物の塗布液を、幅２３０ｍｍ、長さ３００ｍｍ、厚み０．７ｍｍの矩形状ガラス基板上に塗布し、塗布幅２１ｍｍ、長さ２６０ｍｍの塗布面を得た。
塗布後、ホットプレートで、９０℃、６０秒間プリベークした後、塗布面のスジ状のムラの本数を肉眼で計算した。
塗布面にスジ状のムラが全くないものを○、１〜５本のものを△、６本以上のｍのを×として評価した。
【０１１９】
（４）現像ラチチュード：
上記調製したレジスト液を、乾燥後の膜厚が１．５μｍとなるようにガラス基板（Corning1737）にスピンコートし、オーブンを用いて９０℃で６０秒間プリベークした後、２０μｍの線幅を持つマスクで２００ｍｊ/ｃｍ²の露光（照度は２０ｍＷ/ｃｍ²）をし、アルカリ現像液ＣＤ（富士フイルムアーチ（株）製）の１０％希釈液で３０℃で現像した。現像時間は１０〜１００秒まで１０秒刻みで実施した。線幅が安定して残存する現像秒数を現像ラチチュードとして表わした。（５）透過率：
上記調製したレジスト液をスピンコートした基板の色度値を、大塚電子（株）製ＭＣＰＤ−２０００を用いて測定し、Ｘ値が０．６４０の時のＹ値で比較した。Ｙ値が大きいほど透過率が大きい。
以上の結果を表１及び表２に示す。
【０１２０】
【表１】

【０１２１】
【表２】

【０１２２】
表中の記号の説明
Acr(EO)_n: CH₃(OC₂H₄)_nOCOC(CH₃)=CHR
BzMA: ベンジルメタクリレート
St: スチレン
AA: アクリル酸
MAA: メタクリル酸
HEMA: ヒドロキシエチルメタクリレート
また、表中の分子量は、ＧＰＣによるポリスチレン換算質量平均分子量である。
【０１２３】
本発明の感光性着色樹脂組成物は、スピンコートによる塗布厚均一性並びに省液性（液使用量）やスリット塗布による耐塗布ムラ性、更に透過率及び現像ラチチュードのいずれの点においても優れていた。特に、従来塗布ムラや塗布膜厚均一性の面で問題があったスリット塗布においても良好な特性を奏する。また、本発明の感光性着色樹脂組成物には構成成分として着色剤、感光性重合成分、光重合開始剤、溶剤及びアルカリ可溶性樹脂として特定の３元共重合体を含有していればよいが、更にアルカリ可溶性樹脂として特定の他の共重合体及び／又はフッ素系有機化合物を含有することによってより良好な物性を得ることができる。
【０１２４】
【発明の効果】
本発明の感光性着色樹脂組成物は、高顔料濃度、高固形分濃度であっても塗布性に優れ、しかも現像ラチチュードが広くプロセス許容性に優れ、更にまた透過率も向上できる。加えて少ない塗液の使用で基板表面全域を塗布することができる。
従って、本発明の組成物から、液晶表示素子や固体撮像素子に用いられるカラーフィルターをプロセス上の困難性が少なく、高品質かつ低コストで作製することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photosensitive colored resin composition suitable for producing a color filter for use in a liquid crystal display device or a solid-state imaging device, a method for producing the same, and a method for producing a color filter. The present invention relates to a photosensitive colored resin composition having improved uniformity and liquid-saving property, a method for producing the same, and a method for producing a color filter.
[0002]
[Prior art]
Color filters are indispensable components for liquid crystal panels. Compared to CRT as a display device, it is compact and has the same or better performance, and is replacing CRT as a display device for TV screens, personal computer screens, and others.
However, liquid crystal display devices are expensive, and in order to overcome the competition with CRTs, it is essential to make them inexpensive.
[0003]
In order to reduce the price of the liquid crystal display device, in addition to reducing the price of each component such as a color filter and a glass substrate, an improvement in yield without causing defective products is required. In the case of a color filter, it is essential to reduce the amount of the coating solution of the photosensitive colored resin composition. In addition, improving the yield of color filter manufacturing can be one means of reducing the price. In order to improve the yield, it is necessary to produce more color filters in a single process. Specifically, a photosensitive colored resin composition is applied on a larger substrate to produce a larger color filter. This can be done by manufacturing the filter and then cutting it to the desired size.
However, if the amount of the coating liquid is reduced as it is or coating is performed on a large substrate, coating unevenness occurs. Most of the coating unevenness is thickness unevenness, and in order to overcome this, it is necessary to improve the fluidity of the liquid and make it difficult for the coating unevenness to occur even with a small amount of liquid.
As a means for improving the fluidity of the coating solution, the viscosity of the coating solution is generally lowered by lowering the molecular weight of the polymer or increasing the solubility in a solvent. However, simply lowering the viscosity is a problem in that uneven thickness tends to occur at the center and the periphery of the coated substrate.
[0004]
As described above, in order to reduce the amount of the coating liquid of the photosensitive colored resin composition and improve the yield, even when the amount of the coating liquid is small or when it is applied to a large substrate, there is no unevenness in the thickness. It is desired that it can be applied.
[0005]
In addition, the photosensitive colored resin composition is generally required to have a wide range of proper development time in development performed after exposure, that is, a wide development latitude and excellent process tolerance. However, as the area to be processed at the same time or the display panel becomes larger as described above, the time difference immersed in the developer at the top and the end of the substrate increases, and the development time varies. For this reason, the development unevenness is enlarged and the pattern size is different. Therefore, a photosensitive colored resin composition having a wider development latitude is demanded.
[0006]
Also, the method of applying the photosensitive colored resin composition to the substrate is excellent in spin coating because it can uniformly and accurately apply a thin film of 1 to 3 μm, and is widely used in the production of color filters. Yes. Further, in recent years, a rectangular shape having a slit (gap) of several tens of microns at the tip thereof disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 6-339656) and Patent Document 2 (Japanese Patent Laid-Open No. 11-90295). With a coating head having a length corresponding to the coating width of the substrate, the clearance (gap) between the substrate and the substrate is maintained at several tens to several hundreds of microns, and the substrate and the coating head have a constant relative speed, and a predetermined discharge amount. There is a slit coating method in which a coating liquid supplied from a slit is coated on a substrate, which is employed as another coating method for creating a color filter. This slit coating has less liquid loss than spin coating, the coating liquid does not fly and the cleaning process is reduced, the scattered liquid components do not re-enter the coating film, and the rotation start-up stop time Therefore, there are advantages that the tact time can be shortened and the application to a large substrate is easy. Therefore, it is suitable for the production of a color filter for a large-screen liquid crystal display device, and is expected as an advantageous coating method for reducing the amount of coating liquid.
[0007]
However, in slit coating, there is a problem with the system itself that it is difficult to maintain the coating condition of the coating liquid discharged from the slit outlet over the entire coating width, and therefore, uneven coating tends to occur and the width direction Therefore, it is difficult to obtain a uniform coating film thickness, and the uniformity of the coating film may be lacking.
[0008]
For this reason, attempts have been made to improve the fluidity and viscoelastic properties of the coating solution in order to obtain a uniform coating film without unevenness. As described above, the molecular weight of the polymer is reduced, or the polymer is dissolved in a solvent. Means such as selection of a polymer having excellent properties and use of a fluorosurfactant have been proposed, but it has not been sufficient to improve the above problems.
[0009]
On the other hand, as a photosensitive resin composition for a color filter having an improved resin component, for example, in Patent Document 3 (Japanese Patent No. 2665696), (meth) acrylic acid and ethylene oxide molecular chains are used as pigment dispersing binders. It is described that the uniformity and transparency of the color filter obtained can be improved by using a copolymer having (meth) acrylate and styrene derivatives as monomer components. Patent Document 4 (Japanese Patent Application Laid-Open No. 10-204321) describes an invention of a black matrix composition with improved light-shielding properties, adhesion, and resistivity. Copolymerization of styrene and maleic anhydride. A copolymer is disclosed in which the ester component of the maleic anhydride half ester is polyethylene glycol monoacrylate.
Patent Document 5 (Japanese Patent Laid-Open No. 10-87769) discloses a color filter by using a resin composition containing an unsaturated group-containing resin obtained by reacting an epoxy (meth) acrylate with a polybasic acid anhydride. An invention for improving developability, pattern accuracy and the like is disclosed, and polyethylene glycol mono (meth) acrylate is described as an unsaturated group-containing component.
[0010]
Further, Patent Document 6 (Japanese Patent Laid-Open No. 11-323143), Patent Document 7 (Japanese Patent Laid-Open No. 2000-227513), and Patent Document 8 (Japanese Patent Laid-Open No. 2001-269564) describe application of a composition for a color filter. The use of a fluorosurfactant to improve suitability is disclosed.
However, the improvement of the polymer used as the binder and the conventional technique using the fluorosurfactant reduce the amount of the coating solution, improve the yield, and further improve the film thickness uniformity of the obtained coating solution. It wasn't enough to make it happen. In particular, it was further insufficient for the slit coating method.
[0011]
[Patent Document 1]
JP-A-6-339656
[Patent Document 2]
JP-A-11-90295
[Patent Document 3]
Japanese Patent No. 2665696
[Patent Document 4]
JP-A-10-204321
[Patent Document 5]
JP-A-10-87769
[Patent Document 6]
JP 11-323143 A
[Patent Document 7]
JP 2000-227513 A
[Patent Document 8]
JP 2001-269564 A
[0012]
[Problems to be solved by the invention]
An object of the present invention is to provide a photosensitive colored resin composition having excellent coating thickness uniformity and liquid-saving properties, improved transmittance, wide development latitude and excellent process tolerance, and a method for producing the same and a color filter. It is to provide a method.
In particular, the present invention is to provide a photosensitive colored resin composition having excellent flow characteristics as a coating solution even in slit coating that can be easily applied to a large substrate, a method for producing the same, and a method for producing a color filter. .
[0013]
[Means for Solving the Problems]
According to this invention, the photosensitive coloring resin composition of the following structure, its manufacturing method, and the manufacturing method of a color filter are provided, and the said objective is achieved.
[0014]
  In the photosensitive colored resin composition containing (1) a) a colorant, (b) an alkali-soluble resin A, (c) a photosensitive polymerization component, (d) a photopolymerization initiator, and (e) a solvent, the alkali The soluble resin A is at least (i) at least one acid component monomer selected from maleic anhydride, acrylic acid, methacrylic acid, and fumaric acid; (ii) Acr (EO)_n: CH_Three(OC₂H_Four)_nOCOC (CH_Three) = CHR (however,, RIs HOr CH ₃ Represents.n is, When R is H,2-15R is CH ₃ 4 or 9And (iii) a photosensitive colored resin composition characterized by being a copolymer comprising benzyl (meth) acrylate.
[0015]
  (2) (i) acid component monomer in the alkali-soluble resin A, (ii)The Acr (EO) _n And (iii) the composition mass ratio of benzyl (meth) acrylate is from 10 to 25/5 to 25/50 to 85, and the polystyrene-reduced mass average molecular weight (Mw) is from 3,000 to 50,000. The photosensitive colored resin composition as described in (1) above, which is characterized by the following.
[0016]
(3) The content of the colorant in the solid content of the photosensitive colored resin composition is 30 to 60% by mass, and the content of the alkali-soluble resin A is 10 to 50% by mass. The photosensitive colored resin composition according to (1) or (2).
(4) The photosensitive colored resin composition further comprises an alkali-soluble resin B1 which is a copolymer comprising (i) (meth) acrylic acid and (ii) benzyl methacrylate. -The photosensitive colored resin composition in any one of said (3).
(5) The photosensitive colored resin composition further comprises an alkali-soluble resin B2 which is a copolymer comprising (i) (meth) acrylic acid, (ii) benzyl methacrylate, and (iii) hydroxyethyl (meth) acrylate. The photosensitive colored resin composition as described in any one of (1) to (3) above, which is contained.
(6) In the solid content of the photosensitive colored resin composition, the content of the colorant is 30 to 60% by mass, and the content of the alkali-soluble resin (the sum of A, B1, and B2) is 10 to 10 in total. It is 50 mass%, The photosensitive coloring resin composition in any one of said (1)-(5) characterized by the above-mentioned.
[0017]
(7) The photosensitive colored resin composition further contains a fluorine-based organic compound having a fluorine content of 3 to 40% by mass, according to any one of (1) to (6), Photosensitive coloring resin composition.
(8) The photosensitive colored resin composition as described in (7) above, wherein the fluorine-based organic compound is represented by the following formula (I).
C₈F₁₇SO₂N (R₁) CH₂CH₂O (CH₂CH₂O)_nR₂      (I)
In formula (I), R₁And R₂Each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 30.
[0018]
(9) Alkali-soluble resin B1 which is a copolymer comprising (meth) acrylic acid and benzyl methacrylate as a colorant or an alkali which is a copolymer comprising (meth) acrylic acid, benzyl methacrylate and hydroxyethyl (meth) acrylate Kneading and dispersing together with the soluble resin B2 at a viscosity of 10,000 mPa · s or more, then adding the alkali-soluble resin A to the kneaded dispersion and finely dispersing it at a viscosity of 1,000 mPa · s or less. The manufacturing method of the photosensitive colored resin composition as described in said (1).
(10) A coating film is formed by applying the photosensitive colored resin composition according to any one of (1) to (8) above on a substrate by slit coating directly or through another layer, and then prebaked. A method for producing a color filter in which pattern exposure and alkali development are sequentially performed.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
In order to achieve the above object of the present invention, the present invention improves the characteristics of the photosensitive colored resin composition as a coating liquid by incorporating the alkali-soluble resin A into the photosensitive colored resin composition. Furthermore, the dispersion stability of a colorant such as an organic pigment is improved by containing the alkali-soluble resin B1 or the alkali-soluble resin B2 in the composition.
By including a fluorine-based organic compound having a fluorine content of 3 to 40% by mass in the photosensitive colored resin composition of the present invention, the properties of the composition as a coating liquid can be further improved. Further, after kneading and dispersing the composition containing the alkali-soluble resin B1 or the alkali-soluble resin B2, the dispersion of the colorant is promoted by adding and finely dispersing the alkali-soluble resin A, and the composition finally obtained The dispersion stability of the colorant particles in the product is also increased.
The photosensitive colored resin composition of the present invention is suitable for a slit coating method that is excellent in terms of liquid-saving and coating on a large substrate, and causes problems in coating unevenness and coating film thickness uniformity. Easy slit coating is performed well, and a color filter having excellent characteristics can be obtained.
Hereinafter, the compounding component used for the photosensitive coloring resin composition of this invention and the usage method of this composition are demonstrated.
[0020]
The photosensitive colored resin composition of the present invention comprises (a) a colorant, (b) an alkali-soluble resin A, (c) a photosensitive polymerization component, (d) a photopolymerization initiator, and (e) a solvent as essential components. Composed.
[0021]
[I] Alkali-soluble resin
  The (b) alkali-soluble resin A used in the composition of the present invention was selected from at least (i) maleic anhydride (MAA), acrylic acid (AA), methacrylic acid (MA), and fumaric acid (FA). At least one acid component monomer, (ii)Acr (EO) _n And (iii) a copolymer comprising benzyl (meth) acrylate.
[0022]
  (I) acid component monomer in the alkali-soluble resin A, (ii)Acr (EO)_n ,And (iii) Composition mass ratio of benzyl (meth) acrylate (BzMA) becomes like this. Preferably it is 10-25 / 5-25 / 50-85, More preferably, it is 15-20 / 5-5 / 20 / 60-80. Moreover, as polystyrene-reduced mass average molecular weight (Mw) by GPC of alkali-soluble resin A, Preferably it is 3,000-50,000, More preferably, it is 5,000-30,000.
[0023]
  (I) If the compositional mass ratio of the acid component monomer is less than the above range, the alkali solubility tends to decrease, and if it exceeds the above range, the solubility in the solvent tends to decrease.
  (Ii)Acr (EO) _n If the composition mass ratio is less than the above range, the photosensitive colored resin composition coating solution is not sufficiently spread on the substrate, and the present invention tends not to be effectively achieved. Moreover, since it exists in the tendency for the dispersibility of a coloring agent to fall when it exceeds the said range, it is unpreferable.
  (Iii) If the compositional mass ratio of benzyl (meth) acrylate (BzMA) is less than the above range, the dispersion stability of the colorant and the solubility in the composition tend to decrease, such being undesirable. On the other hand, when the above range is exceeded, the alkali development suitability of the coating film is lowered, which is not preferable.
[0024]
  (Ii) Acr (EO)_n ,n is 2 to 15, preferably 2 to 10, particularly preferably 4 to 10.
  If the number n of repetitions is less than the above range, a development residue is likely to occur after development with an alkaline developer, and conversely, if it exceeds the above range, the fluidity of the composition as a coating solution decreases, This is a problem because uneven coating tends to occur and the uniformity of the coating film thickness and the liquid-saving property tend to decrease.
[0025]
In the composition of the present invention, in addition to the alkali-soluble resin A, an alkali-soluble resin B1 that is a copolymer comprising (i) (meth) acrylic acid and (ii) benzyl methacrylate, or ( An alkali-soluble resin B2 which is a copolymer comprising i) (meth) acrylic acid, (ii) benzyl methacrylate, and (iii) hydroxyethyl (meth) acrylate can be contained.
In the present invention, the alkali-soluble resin B1 and the alkali-soluble resin B2 are effective in the dispersion stability of the colorant. When the photosensitive colored resin composition of the present invention is produced, when the kneading and dispersing treatment is performed prior to the fine dispersion treatment of the colorant, the alkali-soluble resin B1 or the alkali-soluble resin B2 is incorporated into the aggregate of the colorants. By applying a strong shearing force, the dispersion can be promoted, and the dispersion stability of the colorant in the composition finally obtained through the subsequent fine dispersion treatment can be enhanced.
The content of the alkali-soluble resin B1 and the alkali-soluble resin B2 in the photosensitive colored resin composition is preferably 50% by mass or less of the total amount of the alkali-soluble resin.
[0026]
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. If the content of the alkali-soluble resin is too small in the composition of the present invention, alkali development tends not to proceed. On the other hand, if the amount is too large, the viscosity of the coating solution increases, the coating thickness uniformity is deteriorated and uneven coating tends to occur, and the development latitude tends to decrease.
[0027]
[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.
[0028]
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.
[0029]
As an organic pigment,
C.I.Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199,;
C.I.Pigment Orange 36, 38, 43, 71;
C.I.Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177,209, 220, 224, 242, 254, 255, 264, 270;
C.I.Pigment Violet 19, 23, 32, 39;
C.I.Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C.I.Pigment Green 7, 36, 37;
C.I.Pigment Brown 25, 28;
C.I.Pigment Black 1, 7;
Examples thereof include carbon black.
[0030]
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.
[0031]
Although the following can be mentioned as a pigment which can be preferably used in this invention, It is not limited to these.
[0032]
C.I.Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C.I.Pigment Orange 36, 71,
C.I.Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C.I.Pigment Violet 19, 23, 32,
C.I.Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C.I.Pigment Black 1
[0033]
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.
[0034]
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. The mass ratio of the green pigment to the yellow pigment was 100: 5 to 100: 150. If the ratio is less than 100: 5, the light transmittance from 400 nm to 450 nm cannot be suppressed, and the color purity cannot be increased. When the ratio exceeded 100: 150, the dominant wavelength became longer and the deviation from the NTSC target hue increased. A more preferred mass ratio is in the range of 100: 30 to 100: 120.
[0035]
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.
[0036]
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.
[0037]
Further, as the pigment for the black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, and the case of carbon and titanium carbon is good. The mass ratio was in the range of 100: 0 to 100: 60. When the ratio is 100: 61 or more, the dispersion stability tends to decrease.
[0038]
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.
[0039]
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.
[0040]
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, after a pigment and a resin or resin solution are mixed, a high shear (shearing force) is applied.
In this method, the pigment is treated by kneading the pigment and the resin and coating the resin on the surface of the pigment. The pigment particles aggregated in this process are dispersed from the lower order aggregates to the primary particles.
[0041]
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 provided as a photosensitive colored resin composition.
[0042]
In the present invention, when the colorant is a dye, it is uniformly dissolved in the composition to obtain a photosensitive colored resin composition.
The dye that can be used as the colorant constituting the photosensitive colored resin composition of 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 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.
The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.
[0043]
In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be suitably used from the viewpoint of completely removing the binder and / or dye by development.
In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.
[0044]
The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, other in the composition. It is selected in consideration of all the required performances such as interaction with the components, light resistance and heat resistance.
Although the specific example of the said acidic dye is given to the following, it is not limited to these. For example,
acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83, 86 , 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3, 5, , 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18 , 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 6 6, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; and derivatives of these dyes.
[0045]
Among these, the acid dyes include acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; acid orange 8, 51, 56, Acid red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217; acid violet 7; acid yellow 17, 25, 29 34, 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; acidgreen 25 and the like and derivatives of these dyes are preferred.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.
[0046]
As the acid dye derivative, an inorganic salt of an acid dye having an acid group such as a sulfonic acid or a carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, and the like can be used and dissolved as a composition solution. Although it is not particularly limited as long as it can be used, solubility, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like are required. Are selected in consideration of all of the above.
[0047]
Although the coloring agent content rate in the total solid of the photosensitive coloring resin composition of this invention is not specifically limited, Preferably it is 30-60 mass%. If the amount of the colorant is too small, an appropriate chromaticity as a color filter tends not to be obtained. On the other hand, if the amount is too large, the photocuring does not proceed sufficiently and the strength as a film is lowered, and the development latitude during alkali development tends to be narrow.
[0048]
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) ), (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 Geneca 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.
[0049]
[III] Photopolymerization component
Next, the photosensitive polymerization component used in the photosensitive colored resin 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.
[0050]
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 ly (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.
[0051]
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.
[0052]
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 amount of these photosensitive polymerization components used is preferably 20 to 200% by mass, more preferably 50 to 120% by mass, based on 100 of the total solid content of the photosensitive colored resin composition. If the amount of the photosensitive polymerization component used is too small or more than the above range, it is not preferable because curing is insufficient.
[0053]
[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.
[0054]
Among the active halogen compounds such as halomethyloxadiazole and halomethyl-s-triazine, the halomethyloxadiazole compound is 2-halomethyl-5 represented by the following general formula IV described in JP-B-57-6096. -Vinyl-1,3,4-oxadiazole compounds are mentioned.
[0055]
[Chemical 1]

[0056]
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.
[0057]
Examples of the halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds represented by the following general formula V described in JP-B-59-1281, and the following general formulas 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.
[0058]
[Chemical formula 2]

[0059]
In general formula V:
Q represents Br or Cl.
P is -CQ_Three(Q is as defined above), -NH₂, -NHR, -N (R)₂Or -OR (wherein R represents a phenyl or alkyl group).
n represents an integer of 0 to 3.
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.
[0060]
[Chemical Formula 3]

[0061]
In the general formula VA, Z is —O— or —S—, and R is as defined above.
[0062]
[Formula 4]

[0063]
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.
[0064]
[Chemical formula 5]

[0065]
(In the above general formula VIA, R₁Is a hydrogen atom or ORc (Rc is an alkyl, cycloalkyl, alkenyl, aryl group), R₂Represents a Cl, Br, alkyl, alkenyl, aryl, or alkoxy group. )
[0066]
[Chemical 6]

[0067]
In general formula VII:
R₁, R₂Are 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_FourAre 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.
[0068]
[Chemical 7]

[0069]
In general formulas VIIA and VIIB, R_Five, R₆, R₇Represents 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.
[0070]
In general formula VII, R₁And R₂May 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.
[0071]
[Chemical 8]

[0072]
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.
[0073]
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.
[0074]
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.
[0075]
The following sensitizers can be used in combination with these initiators. 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.
[0076]
Moreover, the said 3-aryl substituted coumarin compound is a compound shown, for example by the following general formula VIII.
[0077]
[Chemical 9]

[0078]
R₈Is 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), R₉Is 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).
R_Ten, R₁₁Are 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 ( R₁₆) (R₁₇), 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 (R₁₆) (R₁₇), Cl.
R₁₂Represents 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 (R₁₆) (R₁₇), 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).
R₁₃, R₁₄, R₁₆, R₁₇Are 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). R₁₃And R₁₄And R₁₆And R₁₇May 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.
R₁₅Are 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 (R₁₆) (R₁₇), A halogen atom (for example, Cl, Br, F). Zb is = O, = S or = C (R₁₈) (R₁₉). Preferably = O, = S, = C (CN)₂And particularly preferably = O. R₁₈, R₁₉Are the same or different and each represents a cyano group, -COOR₂₀, -COR_{twenty one}Represents. R₂₀, 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).
[0079]
Particularly preferred 3-aryl-substituted coumarin compounds are {(s-triazin-2-yl) amino} -3-arylcoumarin compounds represented by the general formula IX.
[0080]
Embedded image

[0081]
Lophine dimer means 2,4,5-triphenylimidazolyl dimer composed of two lophine residues, and its basic structure is shown below.
[0082]
Embedded image

[0083]
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.
[0084]
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.
[0085]
The usage-amount of an initiator is 0.1-10.0 mass% of the total solid of a photosensitive coloring resin composition, Preferably it is 0.5-5.0 mass%. When the amount of the initiator used is less than 0.1% by mass, the polymerization is difficult to proceed, and when it exceeds 10.0% by mass, the film strength is weakened.
[0086]
[V] Solvent
Examples of the solvent used in preparing the photosensitive colored resin 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, -Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Ethyl ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyrubin Methyl acetate, 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 Nomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylesi.
[0087]
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.
[0088]
These solvents may be used alone or in combination of two or more.
[0089]
[VI] Fluorine organic compounds
The photosensitive colored resin composition of the present invention further contains a fluorine-based organic compound having a fluorine content of 3 to 40% by mass, preferably 5 to 30% by mass, more preferably 7 to 25% by mass. desirable.
If the fluorine content of the fluorine-based organic compound is low, sufficient effects cannot be obtained in coating thickness uniformity and liquid-saving properties. Conversely, if the content is too large, the solubility in the composition is insufficient. Become.
By containing a fluorinated organic compound in the present invention, the liquid characteristics as a coating liquid can be improved, and the uniformity of the coating thickness and the liquid-saving property can be improved. In particular, the wettability to the substrate is improved, and a coating film having a uniform film thickness with no thickness unevenness can be obtained even with a small amount of liquid.
[0090]
Examples of such fluorinated organic compounds include MegaFuck F171, F172, F173, F173, F177, F141, F142, F143, F144, R30, and F437 (above, Dainippon Ink Co., Ltd.). ), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.) and the like.
Of these, MegaFuck F177, MegaFuck F143, MegaFuck R30, and the like are preferable.
[0091]
Among the fluorine-based organic compounds, compounds having a structure represented by the following formula (I) are particularly preferable.
C₈F₁₇SO₂N (R₁) CH₂CH₂O (CH₂CH₂O)_nR₂      (I)
In formula (I), R₁And R₂Each 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 R₁Is a methyl group, an ethyl group or an iso-propyl group, and R₂Is a hydrogen atom. The preferable range of n is 10-25, and the particularly preferable range is 10-20.
[0092]
By further including the fluorine-based organic compound represented by the above formula (I) 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 organic compound is acting as a nonionic surfactant in the photosensitive group coloring resin composition of this invention.
In addition, the fluidity of the coating solution is improved, the interfacial tension between the substrate and the coating solution is lowered, the wettability to the substrate is improved, and even a thin film of about several μm has a small thickness unevenness. Can be obtained. In particular, when the coating film is thin, good results are obtained for coating application, thickness unevenness, and slit coating that easily causes liquid breakage on the coating surface.
[0093]
In the present invention, the amount of the fluorine-based compound represented by the formula (I) is preferably 0.001 to 2.0% by mass, more preferably 0.055 to 1.0% by mass with respect to the total coating solution. %, Most preferably 0.003 to 0.5 mass%.
[0094]
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).
[0095]
[VII] Other ingredients
In the photosensitive colored resin composition of the present invention, various additives as necessary, for example, fillers, polymer compounds other than the alkali-soluble resins, surfactants other than the above, adhesion promoters, antioxidants, ultraviolet rays Absorbers, anti-aggregation agents and the like can be blended.
[0096]
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. Specifically, a phthalocyanine derivative (commercially available product EFKA-745 (manufactured by Morishita Sangyo)); 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; 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, and 150R1; anionic surfactants such as W004, W005, and W017 (manufactured by Yusho) EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 4; Polymer dispersing agents such as 50 (manufactured by Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940 17000, 24000, 26000, 28000, etc. (manufactured by Zeneca Corporation); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101 , P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei);
[0097]
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.
[0098]
In addition, when promoting the alkali solubility in 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 having a 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.
[0099]
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the photosensitive colored resin 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.
[0100]
[VII] Method for producing and using the composition of the present invention
The photosensitive colored resin composition of the present invention is prepared by mixing a colorant, an alkali-soluble resin, a photosensitive polymerization component, a photopolymerization initiator, and other additives used as necessary with a solvent, various mixers, dispersions It can be prepared by mixing and dispersing using a machine.
The mixing and dispersing step preferably includes kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.
[0101]
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. The alkali-soluble resin B2, which is a copolymer of acrylate, is kneaded and dispersed so that the viscosity after the kneading and dispersing treatment is 10,000 mPa · s or higher, desirably 100,000 mPa · s or higher, and then The alkali-soluble resin A is added, and the dispersion after the fine dispersion treatment is finely dispersed so that the viscosity becomes 1,000 mPa · s or less, preferably 100 mPa · s or less.
[0102]
In the kneading and dispersing step, the surface of the colorant particles of the raw material is promoted to be wetted with the structural component mainly composed of the resin component of the vehicle, and the colorant particles and the solid of the vehicle solution are solidified from the solid / gas interface between the colorant particles and the air. / Convert to solution interface. In the fine dispersion step, the colorant particles are dispersed to a fine state close to the primary particles by mixing and stirring together with a dispersion medium for fine particles of glass or ceramic. Therefore, in the kneading and dispersing step, the colorant
Since it is necessary to convert the interface formed by the particle surface from air to a solution, a strong shearing force and compression force are required, and the kneading machine and the material to be kneaded are preferably those with high viscosity. Must be uniformly distributed even to a minute state, and a dispersing machine that does not require impact force and shear force on the agglomerated colorant particles, and a relatively low dispersion material has a relatively low viscosity. It is desirable that
[0103]
For example, in the kneading and dispersing step for producing a color filter using the photosensitive colored resin composition of the present invention, first, a colorant such as an organic pigment and carbon black and a dispersant or a surface treatment agent, the resin B1 of the present invention is used. Alternatively, K2 is kneaded with B2 (part or all of resin A when neither resin B1 nor B2 is used) and a solvent. 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 strong shearing force. Next, the solvent and the resin A of the present invention (the remainder 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 also described in “Paint Flow and Pigment Dispersion” by T.C. Patton (published by John Wiley and Sons, 1964).
[0104]
The photosensitive colored resin composition of the present invention is applied to the substrate directly or via another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, etc. to form a radiation sensitive composition layer Then, it is exposed through a predetermined mask pattern, only the coated film portion irradiated with light is cured, and developed with a developer, thereby forming a patterned film composed of pixels of each color (three colors or four colors). Color filters can be manufactured. As radiation used at this time, ultraviolet rays such as g-line and i-line are particularly preferably used.
Next, by performing an alkali development treatment, the light-irradiated portion is eluted in the alkaline aqueous solution by the exposure, and only the photocured portion remains. Any developer can be used as long as it dissolves the light-irradiated portion of the photosensitive layer but does not dissolve the light-irradiated portion.
Next, after the excess developer is washed away and dried, heat treatment (post-bake) is performed at a temperature of 50 ° C. to 240 ° C. Thus, the said process can be repeated sequentially for every color, and a cured film can be manufactured. Thereby, a color filter is obtained.
[0105]
As the substrate, for example, non-alkali glass, 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, photoelectric conversion element substrates used for solid-state imaging elements, for example, A silicon substrate etc. are mentioned. Furthermore, a plastic substrate is also possible. On these substrates, usually, black stripes for isolating each pixel are formed.
[0106]
Raw materials for plastic substrates include (1) amorphous polyolefin, (2) polyethersulfone, (3) polyglutarimide, (4) polycarbonate, and (5) polyethylene terephthalate in terms of optical properties, heat resistance, mechanical strength, etc. , (6) polyethylene naphthalate, (7) norbornene polymer, (8) polyimide using bisaniline fluorene as a diamine component, and (9) polyester composed of bisphenol fluorene and dibasic acid. Among these, (2) polyethersulfone, (4) polycarbonate, (5) polyethylene terephthalate, and (7) norbornene polymer are preferable. Such raw materials are particularly preferred for LCD applications.
The properties required for plastic substrates include low thermal expansion (preventing deterioration of display accuracy associated with the curing process during color filter creation), gas barrier properties (ensuring liquid crystal stability), optical transmittance and optical isotropy, etc. Characteristics, surface smoothness, etc. Regarding thermal expansion, the thermal expansion coefficient is 10^-FourThe following is preferable.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.
[0107]
Drying (pre-baking) of the photosensitive colored resin composition layer of the present invention applied on the substrate can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, oven or the like.
[0108]
The coating thickness (after drying) of the photosensitive colored resin composition of the present invention is generally 0.3 to 5.0 μm, desirably 0.5 to 3.5 μm, most desirably 1.0 to 2.5 μm. is there.
[0109]
Any developer can be used as long as it dissolves the photosensitive colored resin composition of the present invention and does not dissolve the radiation irradiated portion. 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.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.
[0110]
Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxy Concentrations of alkaline compounds such as do, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are 0.001 to 10% by mass, preferably 0.01 to 1% by mass An alkaline aqueous solution dissolved so as to be used is used. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans (rinse) with water after image development.
[0111]
Post-baking is heating after development to complete curing, and is usually performed at about 200 ° C. to 220 ° C. (hard baking).
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.
[0112]
As the application of the photosensitive colored resin composition of the present invention, the application mainly to a color filter has been mainly described, but it is needless to say that it can be applied to a black matrix provided between pixels of a color filter. The black matrix is formed by photo-exposure and alkali development of a composition obtained by adding a black colorant such as carbon black or titanium black to the composition of the present invention, and then post-baking to promote film curing. be able to.
Various components for color filters can be applied to spacers, protective layers, contact hole forming layers and the like in addition to the color filter body (colored layer) and the black matrix. Furthermore, the colored resin composition of the present invention can be used as a sealing agent for potting of COB (chip on board) and a sealing agent for LCD, in addition to the above-mentioned various components for color filters.
[0113]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
[0114]
Preparation of photosensitive colored resin composition
・ C. I. Pigment Red 254 27 parts by mass
・ C. I. Pigment Yellow 139 4 parts by mass
-Resin B1 or B2 shown in Table 1 below (Example 1 and
Comparative example 1 is resin A only) propylene glycol monomethyl
Ether acetate solution (solid content 50%)
22 parts by mass
・ Dispersant (BYK BY-161) 2 parts by mass
The above components are kneaded and dispersed with three rolls, and then
-Propylene glycol monomethyl resin A shown in Table 1 below
Ether acetate solution (solid content 50%) 22 parts by mass
・ 200 parts by mass of propylene glycol monomethyl ether acetate (solvent)
And finely dispersed in a sand mill day and night.
[0115]
Next, the following components were added and mixed by stirring to prepare a photosensitive colored resin composition (resist solution).
・ Dipentaerythritol penta, hexaacrylate 20 parts by mass
4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl]
1,6-di (trichloromethyl) -S-triazine (photopolymerization initiator) 1 part by mass
・ Surfactant BASF Tetronic 150R1 0.5 parts by mass
・ Fluorine compound DIC Corporation MegaFuck F-143 0.01 parts by mass
・ 150 parts by mass of propylene glycol monomethyl ether acetate (solvent)
The viscosity of each dispersion after kneading and dispersing in the above step is shown in Table 1.
[0116]
Examples 1-11 and Comparative Examples 1-5
Each composition obtained above was evaluated for coating thickness uniformity, liquid usage, coating unevenness, development latitude, and transmittance by the following methods.
[0117]
(1) <Spin coating> Uniform coating thickness:
On the glass substrate of 550 mm × 650 mm, 30 g of the resist solution prepared above was dropped at the center and spin coated at 600 rpm. The thickness from the central part of the coated substrate to the part 300 mm inside from the edge in the diagonal direction was measured. The coating thickness unevenness was expressed by the following formula and expressed in%.
Unevenness of thickness = (thickness of the central part−thickness inside the edge 30 mm) / thickness of the central part
(2) <Spin coating> Coating liquid usage:
When the resist solution 20 to 40 g prepared above was dropped onto a 550 mm × 650 mm glass substrate at the center and spin-coated at 800 rpm, the minimum amount of liquid at which part of the outermost edge was not applied was measured.
[0118]
(3) <Slit application> Application unevenness:
Using a slit coating apparatus equipped with a slit head having a slit gap of 50 μm and an effective coating width of 20 mm, the gap between the slit and the substrate is adjusted so that the coating thickness after drying becomes 2 μm, and 50 mm / sec. The coating solution of the photosensitive colored resin composition of each example / comparative example was coated on a rectangular glass substrate having a width of 230 mm, a length of 300 mm, and a thickness of 0.7 mm at a coating speed, and a coating width of 21 mm and a length of 260 mm. A coated surface was obtained.
After the application, the film was pre-baked at 90 ° C. for 60 seconds with a hot plate, and the number of streaky irregularities on the coated surface was calculated with the naked eye.
Evaluation was made on the case where there was no stripe-like unevenness on the coated surface, ◯ for 1-5 pieces, and x for 6 or more pieces.
[0119]
(4) Development latitude:
The prepared resist solution is spin-coated on a glass substrate (Corning 1737) so that the film thickness after drying is 1.5 μm, pre-baked at 90 ° C. for 60 seconds using an oven, and then a mask having a line width of 20 μm. 200mj / cm²Exposure (illuminance is 20 mW / cm²And developed at 30 ° C. with a 10% diluted solution of an alkaline developer CD (manufactured by Fuji Film Arch Co., Ltd.). Development time was 10 seconds to 10 to 100 seconds. The number of development seconds in which the line width remained stable was expressed as development latitude. (5) Transmittance:
The chromaticity value of the substrate on which the resist solution prepared above was spin-coated was measured using MCPD-2000 manufactured by Otsuka Electronics Co., Ltd., and compared with the Y value when the X value was 0.640. The greater the Y value, the greater the transmittance.
The above results are shown in Tables 1 and 2.
[0120]
[Table 1]

[0121]
[Table 2]

[0122]
Explanation of symbols in the table
Acr (EO)_n: CH_Three(OC₂H_Four)_nOCOC (CH_Three) = CHR
BzMA: benzyl methacrylate
St: Styrene
AA: Acrylic acid
MAA: Methacrylic acid
HEMA: Hydroxyethyl methacrylate
Moreover, the molecular weight in a table | surface is a polystyrene conversion mass mean molecular weight by GPC.
[0123]
The photosensitive colored resin composition of the present invention is excellent in both coating thickness uniformity by spin coating, liquid saving (liquid usage), coating unevenness by slit coating, and transmittance and development latitude. It was. In particular, good characteristics are also obtained in slit coating, which has been problematic in terms of coating unevenness and coating film thickness uniformity. Further, the photosensitive colored resin composition of the present invention may contain a specific ternary copolymer as a colorant, a photosensitive polymerization component, a photopolymerization initiator, a solvent and an alkali-soluble resin as constituent components. Further, by containing a specific other copolymer and / or a fluorinated organic compound as an alkali-soluble resin, better physical properties can be obtained.
[0124]
【The invention's effect】
The photosensitive colored resin composition of the present invention is excellent in coating property even at high pigment concentration and high solid content concentration, has wide development latitude and excellent process tolerance, and can further improve the transmittance. In addition, the entire surface of the substrate can be applied with a small amount of coating liquid.
Therefore, from the composition of the present invention, a color filter used for a liquid crystal display device or a solid-state imaging device can be produced with high quality and low cost with little process difficulty.

Claims (10)

In the photosensitive colored resin composition containing (a) a colorant, (b) an alkali-soluble resin A, (c) a photosensitive polymerization component, (d) a photopolymerization initiator, and (e) a solvent, the alkali-soluble resin A is at least (i) at least one acid component monomer selected from maleic anhydride, acrylic acid, methacrylic acid, and fumaric acid, (ii) Acr (EO) _n : CH ₃ (OC ₂ H ₄ ) _n OCOC ( CH ₃₎ = CHR (where, R is H or an CH _3. n, is when R is H, 2-15, when R is CH _3, represents a 4 or 9), and (iii ) A photosensitive colored resin composition, which is a copolymer composed of benzyl (meth) acrylate. In the alkali-soluble resin A, the composition mass ratio of (i) the acid component monomer, (ii) the Acr (EO) _n , and (iii) benzyl (meth) acrylate is 10-25 / 5 to 25 / 50-85. The photosensitive colored resin composition according to claim 1, which has a polystyrene-reduced mass average molecular weight (Mw) of 3,000 to 50,000. The content of the colorant in the solid content of the photosensitive colored resin composition is 30 to 60% by mass, and the content of the alkali-soluble resin A is 10 to 50% by mass. Item 3. The photosensitive colored resin composition according to Item 1 or 2. The photosensitive coloring resin composition further contains an alkali-soluble resin B1 which is a copolymer comprising (i) (meth) acrylic acid and (ii) benzyl methacrylate. The photosensitive coloring resin composition of any one of these. The photosensitive colored resin composition further contains an alkali-soluble resin B2 that is a copolymer comprising (i) (meth) acrylic acid, (ii) benzyl methacrylate, and (iii) hydroxyethyl (meth) acrylate. The photosensitive coloring resin composition of any one of Claims 1-3 characterized by these. In the solid content of the photosensitive colored resin composition, the content of the colorant is 30 to 60% by mass, and the content of the alkali-soluble resin (the sum of A, B1, and B2) is 10 to 50% by mass in total. The photosensitive colored resin composition according to claim 1, wherein the composition is a photosensitive colored resin composition. The photosensitive colored resin according to claim 1, wherein the photosensitive colored resin composition further contains a fluorine-based organic compound having a fluorine content of 3 to 40% by mass. Composition. The photosensitive colored resin composition according to claim 7, wherein the fluorine-based organic compound is 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 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 30. Alkali-soluble resin B1 which is a copolymer comprising (meth) acrylic acid and benzyl methacrylate or an alkali-soluble resin B2 which is a copolymer comprising (meth) acrylic acid, benzyl methacrylate and hydroxyethyl (meth) acrylate And kneading and dispersing with a viscosity of 10,000 mPa · s or more, and then adding the alkali-soluble resin A to the kneaded dispersion and finely dispersing with a viscosity of 1,000 mPa · s or less. The manufacturing method of the photosensitive coloring resin composition as described in any one of. A coating film is formed by applying the photosensitive colored resin composition according to any one of claims 1 to 8 on a substrate by slit coating directly or through another layer, and then prebaking, pattern exposure, and alkali development. The manufacturing method of the color filter which performs sequentially.