JP2004176000A - Pigment dispersion liquid and photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition and a pigment dispersion liquid giving a green color layer of NTSC color specification of a color filter at a practical film thickness and the ordinary amount of the colorant. <P>SOLUTION: The pigment dispersion liquid contains at least one kind of blue pigment as a green coloring component. As an alternative, the pigment dispersion liquid contains at least one kind of yellow pigment as a green coloring component. <P>COPYRIGHT: (C)2004,JPO

Description

【００５８】
（式（Ｉ）中、Ｒは水素原子又はメチル基の何れかを示し、ｎは０〜２０の整数である。）
【００５９】
式（ＩＩ）：
【化２】

【００６０】
（式（ＩＩ）中、ｎは１以上の整数）
【００６１】
式（ＩＩＩ）：
【化３】

【００６２】
（式（ＩＩＩ）中、ｎは１以上の整数）
式（ＩＶ）：
【化４】

【００６３】
（式（ＩＶ）中、Ｒ_１及びＲ２は水素原子、炭素数１〜５のアルキル基又はハロゲン原子を、ｎは１〜５の数を示す。Ａは４価の有機残基を、Ｘは１以上の数を示す。）
【００６４】
式（Ｖ）：
【化５】

【００６５】
（式（Ｖ）中、ＲはＨ又は低級アルキル基、Ｒ’はＨ又はメチル基を示す。ｎ＝０〜２０の整数である。）
【００６６】
以上の材料をディゾルバー型撹拌機、ターボ型撹拌機、二軸式撹拌機等の撹拌機を用いて混和して感光性樹脂組成物とするか、或いは２本ロールミル、３本ロールミル、サンドミル、ペイントシェーカー等の分散機を用いて混練して感光性樹脂組成物とするが、その際に用いられる前述した有機溶剤の好ましい量は通常、全固形分の５０〜２００重量％である。
【００６７】
この感光性樹脂組成物は、一般に感光性着色組成物あるいは顔料分散レジストと呼ばれるもので、溶剤中に顔料が分散され、さらにバインダー樹脂と呼ばれる共重合体、光重合性モノマー、及び光重合開始剤、また任意にその他の添加剤が、溶解又は分散されている。
例えば、熱により硬化しうる樹脂、キノンジアジド化合物、架橋剤及び顔料を含有してなるポジ型レジスト組成物；酸により硬化しうる樹脂、キノンジアジド化合物、光酸発生剤、架橋剤及び顔料を含有してなるポジ型レジスト組成物が上げられる。
熱又は酸により硬化しうる樹脂としては、例えばフェノール性水酸基もしくはカルボキシル基を有する樹脂、或いはＪ． Ｐｈｏｔｏｐｏｌｙｍ． Ｓｃｉ． Ｔｅｃｈｎｏｌ． ｖｏｌ．３，Ｎｏ．３（１９９０） の第２３５ 〜２４７ 頁に記載されているようなヒドロキシスチレン構造を含む共重合体、即ち、ｐ−ヒドロキシスチレンとｐ−アセトキシメチルスチレンとの共重合体等が挙げられる。カルボキシル基を有する樹脂としては、例えばポリメタクリレートとマレイン酸無水物との共重合体等が挙げられる。上記フェノール性水酸基を有する樹脂としては、例えばアルカリ可溶性のフェノール樹脂もしくはノボラック樹脂等が挙げられる。ノボラック樹脂としては、例えばフェノール類とアルデヒド類とを酸触媒の存在下に縮合して得られるものが挙げられる。フェノール類としては、例えばフェノール、クレゾール（ｍ−クレゾール、ｐ−クレゾール等）、エチルフェノール、２−ｔ−ブチル−５−メチル−フェノール、ブチルフェノール、キシレノール、フェニルフェノール、カテコール、レゾルシノール、ピロガロール、ナフトール、ビスフェノールＣもしくはビスフェノールＡ等が挙げられる。これらのフェノール類は単独で、又は２種以上組み合わせて用いられる。アルデヒド類としては、例えばホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒドもしくはベンズアルデヒド等の脂肪族又は芳香族アルデヒドが挙げられる。フェノール性水酸基を有する樹脂等の、熱又は酸により硬化しうる樹脂は必要により、分別等の手段を用いて分子量分布を調節してもよい。又、ビスフェノールＡもしくはビスフェノールＣ等のフェノール類を熱又は酸により硬化しうる樹脂に添加してもよい。
【００６８】
架橋剤としては、例えば下式−（ＣＨ_２ ）ｓ ＯＲ（式中、Ｒは水素原子又は低級アルキル基を表わし、ｓは１〜４の整数を表わす。）で示される基を有する化合物及びメラミンが挙げられる。上式で示される基を有する化合物としては、例えば下式
【００６９】
【化６】

【００７０】
〔式中、Ｚは−ＮＲ_１ Ｒ_２ 又はフェニル基を表わす。Ｒ_１〜Ｒ_６ はこれらの中、少なくとも１つが−（ＣＨ_２ ）ｓ ＯＨ又は−（ＣＨ_２ ）ｓ ＯＲ_７を表わすという条件付きで各々、水素原子、−（ＣＨ_２ ）ｓ ＯＨ又は−（ＣＨ_２ ）ｓ ＯＲ_７ を表わす。Ｒ_７は低級アルキル基を表わす。ｓは１〜４の整数を表わす。〕で示される化合物、或いは下式
【００７１】
【化７】

【００７２】
【化８】

【００７３】
で示される化合物等が挙げられる。Ｒ及びＲ_７ で表わされる低級アルキル基としてはメチル、エチル、ｎ−プロピル又はｎ−ブチル基が挙げられ、好ましいアルキル基としてはメチル又はエチル基が挙げられる。式（ｉ）〜（ｉｉ）で示される化合物は各々、ｐ−クレゾール又はｔ−ブチルフェノールを塩基性条件下でホルムアルデヒドと縮合させることにより製造することができる。又、式（ｉｉｉ）〜（ｖｉ）で示される化合物は特開平１−２９３３３９号公報に記載された公知化合物である。式−（ＣＨ_２ ）ｓ ＯＲで示される基を有する、好ましい化合物としては、例えばヘキサメトキシメチロール化メラミン、ヘキサメトキシエチロール化メラミン又はヘキサメトキシプロピロール化メラミン等が挙げられる。
【００７４】
光酸発生剤としては光により直接もしくは間接的に酸を発生するものであれば特に限定されないが、例えば特開平４−１６３５５２号公報に記載されているトリハロメチルトリアジン系化合物、特開平１−５７７７７ 号公報に記載されているジスルホン化合物、下式、Ｒ_８−ＳＯ_２ −ＳＯ_２ −Ｒ_９ −ＳＯ_２ −ＳＯ_２ −Ｒ_１０（式中、Ｒ_８ 及びＲ_１０は各々独立して置換されていてもよいアリール、アラルキル、アルキル、シクロアルキル又は複素環基を表わし、Ｒ_９は置換されていてもよいアリールを表わす。）で示される化合物、特開平１−２９３３３９号公報に記載されているスルホン酸エステル基を含む光酸発生剤、下式ＣＦ_３−ＳＯ_２ Ｏ−（ＣＨ_２ ）ｎ −Ｙ（式中、Ｙは置換されていてもよいアリール基をｎは０又は１を表わす。）で示される化合物、下式ＣＦ_３−ＳＯ_２ Ｏ−〔Ｃ（Ｙ_１ ）（Ｙ_２ ）〕ｍ −Ｃ（Ｏ）−Ｙ_３ （式中、Ｙ_１及びＹ_２ は各々独立して置換されていてもよいアルキル、アルコキシもしくはアリール基を、Ｙ_３ は置換されていてもよいアリール基を、ｍは１又は２を、各々表わす。）で示される化合物、下式ＣＦ_３−ＳＯ_２ Ｏ−Ｎ（Ｙ_４ ）−Ｃ（Ｏ）−Ｙ_５ （式中、Ｙ_４ は置換されていてもよいアルキル基を、Ｙ_５は置換されていてもよいアリール基を、各々表わす。）で示される化合物、下式ＣＦ_３ −ＳＯ_２ Ｏ−Ｎ＝Ｃ（Ｙ_６）（Ｙ_７ ）（式中、Ｙ_６ は水素原子又は置換されていてもよいアルキルもしくはアリール基を、Ｙ_７は置換されていてもよいアリール基を、各々表わす。）で示される化合物、下式
【００７５】
【化９】

【００７６】
で示されるオニウム塩類等があげられる。
【００７７】
キノンジアジド化合物としては、例えばｏ−ナフトキノンジアジド−５−スルホン酸エステル又はスルホン酸アミド、或いはｏ−ナフトキノンジアジド−４−スルホン酸エステル又はスルホン酸アミド等が挙げられる。これらのエステル又はアミドは、例えば特開平２−８４６５０ 及び特開平３−４９４３７ 号公報に一般式（Ｉ）で記載されているフェノール化合物等を用いて公知の方法により製造することができる。
【００７８】
熱又は酸により硬化しうる樹脂及び架橋剤は通常、溶剤中に各々２〜５０及び２〜３０重量％程度の割合で溶解させる。キノンジアジド化合物、光酸発生剤及び顔料の使用量は通常、上記の樹脂及び架橋剤の溶液に対して各々、２〜３０、２〜３０及び２〜５０重量％程度の割合で添加する。又、ポジ型レジスト組成物には、例えば均一な塗布性を付与するための平滑剤或いは顔料を分散させるための分散剤等の当該技術分野で慣用されている各種の添加剤を加えることもできる。
【００７９】
ポジ型レジストは露光によりアルカリ現像液に対する溶解度に差が生ずることを利用して、露光部が除去され、未露光部がポジ型着色パターンとして残存するものである。即ち、上記キノンジアジド化合物は露光により分解してアルカリ現像液に可溶となるが、一方、未露光部では上記樹脂のアルカリ現像液に対する溶解を抑制するように作用する。そして、未露光部を全面露光した際、残存したキノンジアジド化合物は分解され、一方、光酸発生剤が含まれている場合に、これは酸を発生してポジ型着色パターンを硬化させる作用を有する。露光には、例えば水銀ランプ等の紫外線、遠紫外線、電子線もしくはＸ線等が用いられる。
【００８０】
バインダー樹脂は、未露光塗膜にアルカリ現像性を付与し、また顔料の分散媒として作用するものであり、本発明ではかかるバインダー樹脂として、（メタ）アクリル酸を一つのモノマーとする共重合体（Ｂ）が用いられる。本明細書でいう（メタ）アクリル酸とは、アクリル酸又はメタクリル酸を意味し、その他、例えば（メタ）アクリレートという場合も同様に、アクリレート又はメタクリレートを意味する。この共重合体（Ｂ）は通常、（メタ）アクリル酸とそれに共重合可能な他のモノマーとの共重合によって得られ、（メタ）アクリル酸由来のカルボキシル基を含有することになる。
【００８１】
（メタ）アクリル酸に共重合可能なモノマーは、重合性炭素−炭素不飽和結合を有する化合物である。具体的には、スチレンやα−メチルスチレン、ビニルトルエンのような芳香族ビニル化合物、メチル（メタ）アクリレートやエチル（メタ）アクリレート、ブチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレートのような不飽和カルボン酸アルキルエステル、アミノエチルアクリレートのような不飽和カルボン酸アミノアルキルエステル、グリシジル（メタ）アクリレートのような不飽和カルボン酸グリシジルエステル、酢酸ビニルやプロピオン酸ビニルのようなカルボン酸ビニルエステル、（メタ）アクリロニトリルやα−クロロアクリロニトリルのようなシアン化ビニル化合物、クロトン酸やイタコン酸、マレイン酸、フマル酸のような（メタ）アクリル酸以外の不飽和カルボン酸などが挙げられる。これらのモノマーは、それぞれ単独で又は２種以上組み合わせて、（メタ）アクリル酸と共重合させることができる。
【００８２】
（メタ）アクリル酸を一つのモノマーとする適当な共重合体の例として、（メタ）アクリル酸／ベンジル（メタ）アクリレート共重合体、（メタ）アクリル酸／ベンジル（メタ）アクリレート／スチレン共重合体、（メタ）アクリル酸／メチルメタクリレート共重合体、（メタ）アクリル酸／メチルメタクリレート／スチレン共重合体などを挙げることができる。また、このような（メタ）アクリル酸を一つのモノマーとする共重合体の側鎖が、感光性基を有する化合物で変成されたものも、本発明でいう（メタ）アクリル酸を一つのモノマーとする共重合体（Ｂ）に包含される。
【００８３】
共重合体（Ｂ）は、ポリスチレン換算重量平均分子量が ５，０００〜４００，０００ の範囲にあるのが好ましく、さらには １０，０００〜３００，０００の範囲の重量平均分子量を有するのがより好ましい。この共重合体（Ｂ）は、感光性着色組成物中の全固形分量を基準に、一般には５〜９０重量％、好ましくは２０〜７０重量％の範囲で含有される。
【００８４】
光重合性モノマー（Ｃ）は、光及び光重合開始剤の作用によって重合を起こす化合物であり、一般には、重合性炭素−炭素不飽和結合を有する化合物がこれに該当する。この光重合性モノマー（Ｃ）は、単官能モノマーの他、２官能、その他の多官能モノマーであることができる。単官能モノマーの具体例としては、ノニルフェニルカルビトールアクリレート、２−ヒドロキシ−３−フェノキシプロピルアクリレート、２−エチルヘキシルカルビトールアクリレート、２−ヒドロキシエチルアクリレート、Ｎ−ビニルピロリドンなどが挙げられる。また、２官能モノマーの具体例としては、
１，６−ヘキサンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ビスフェノールＡのビス（アクリロイロキシエチル）エーテル、３−メチルペンタンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレートなどが、その他の多官能モノマーの具体例としては、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリス（メタクリロイロキシエチル）イソシアヌレートなどが挙げられる。光重合性モノマー（Ｃ）も、それぞれ単独で、又は２種以上組み合わせて用いることができる。光重合性モノマー（Ｃ）は、感光性着色組成物中の全固形分重量を基準に、一般的には５〜９０重量％の範囲で、好ましくは２０〜７０重量％の範囲で含有される。
【００８５】
光重合性モノマー（Ｃ）としては特に、アクリル基（ＣＨ２＝ＣＨＣＯ−） を有し、化合物の単位重量あたりのアクリル基の数が多いもの、換言すれば、アクリル基１当量あたりの化合物のグラム数で表されるアクリル基当量の小さいものが好ましく、なかでも、アクリル基当量が１００以下の化合物が好ましく用いられる。場合により、このようなアクリル基当量の小さいモノマーを、他のモノマーと組み合わせて用いることもできる。アクリル基当量が大きくなると、そこから得られる乾燥塗膜を露光、現像した際に、感度不足を招きやすく、カラーフィルターの生産性低下につながる可能性がある。このようにアクリル基当量の小さい化合物であるためには、２官能以上の多官能モノマーが好ましいことになる。アクリル基当量が１００以下のモノマーには、エチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレートなどが包含され、とりわけ、トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリレート又はジペンタエリスリトールヘキサアクリレートが好ましく用いられる。
【００８６】
光重合開始剤（Ｄ）はこの分野で通常用いられているものであり、例えば、アセトフェノン系、ベンゾイン系、ベンゾフェノン系、チオキサントン系、その他の開始剤が挙げられる。アセトフェノン系開始剤の具体例としては、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンジルジメチルケタール、２−ヒドロキシ−１−〔４−（２−ヒドロキシエトキシ）フェニル〕−２−メチルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−（４−メチルチオフェニル）−２−モルホリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）ブタン−１−オン、２−ヒドロキシ−２−メチル−１−〔４−（１−メチルビニル）フェニル〕プロパン−１−オンのオリゴマーなどが挙げられ、ベンゾイン系開始剤の具体例としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテルなどが挙げられ、ベンゾフェノン系開始剤の具体例としては、ベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、４−ベンゾイル−４′−メチルジフェニルサルファイド、３，３′，４，４′−テトラ（ｔｅｒｔ−ブチルパーオキシカルボニル）ベンゾフェノン、２，４，６−トリメチルベンゾフェノンなどが挙げられ、チオキサントン系開始剤の具体例としては、２−イソプロピルチオキサントン、４−イソプロピルチオキサントン、２，４−ジエチルチオキサントン、２，４−ジクロロチオキサントン、１−クロロ−４−プロポキシチオキサントンなどが挙げられ、その他の開始剤の具体例としては、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、２，２′−ビス（ｏ−クロロフェニル）−４，４′，５，５′−テトラフェニル−１，２′−ビイミダゾール、１０−ブチル−２−クロロアクリドン、２−エチルアントラキノン、ベンジル、９，１０−フェナンスレンキノン、カンファーキノン、フェニルグリオキシル酸メチル、チタノセン化合物などが挙げられる。これらの光重合開始剤も、それぞれ単独で、又は２種以上組み合わせて用いることができる。
【００８７】
また、光重合開始剤に光開始助剤を組み合わせて用いることもできる。光開始助剤としては、例えばアミン系のものやアルコキシアントラセン系のものが挙げられ、その具体例には、トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン、４−ジメチルアミノ安息香酸メチル、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸イソアミル、４−ジメチルアミノ安息香酸２−エチルヘキシル、安息香酸２−ジメチルアミノエチル、Ｎ，Ｎ−ジメチルパラトルイジン、４，４′−ビス（ジメチルアミノ）ベンゾフェノン（通称ミヒラーズケトン）、４，４′−ビス（ジエチルアミノ）ベンゾフェノン、９，１０−ジメトキシアントラセン、２−エチル−９，１０−ジメトキシアントラセン、９，１０−ジエトキシアントラセン、２−エチル−９，１０−ジエトキシアントラセンなどが包含される。これら光開始助剤も、それぞれ単独で、又は２種以上組み合わせて用いることができる。
【００８８】
光重合開始剤及び任意成分である光開始助剤は、合計量として、共重合体（Ｂ）と光重合性モノマー（Ｃ）の合計１００重量部に対して、一般には３〜５０重量部の範囲で、好ましくは５〜４０重量部の範囲で含有される。
【００８９】
溶剤は、この分野で用いられる各種のものであることができる。具体例としては、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸プロピル、プロピオン酸ブチル、ピルビン酸エチル、３−メ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のようなエステル類；アセトン、メチルエチルケトン、メチルアミルケトン、ジイソブチルケトン、シクロペンタノン、シクロヘキサノンのようなケトン類；３−メトキシブチルアセテート、プロピレングリコールモノメチルエーテルアセテートのようなグリコールエーテルエステル類；ベンゼン、トルエン、ｏ−、ｍ−又はｐ−キシレンのような芳香族炭化水素類などが挙げられる。これらの溶剤は、それぞれ単独で、又は２種類以上混合して用いることができる。溶剤の使用量は、それを含む感光性着色組成物全体の量を基準に、好ましくは６０〜９０重量％、より好ましくは７０〜８５重量％である。
【００９０】
本発明に係る感光性着色組成物はまた、必要に応じて、充填剤、他の高分子化合物、界面活性剤（顔料分散剤）、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止材などの添加剤を含有することもできる。充填剤として具体的には、ガラス、シリカ、アルミナなどが、他の高分子化合物として具体的には、ポリビニルアルコール、ポリアクリル酸、ポリエチレングリコールモノアルキルエーテル、ポリフロロアルキルアクリレートなどが、界面活性剤（顔料分散剤）としては、ノニオン系、カチオン系、アニオン系などの各種のものが、密着促進剤として具体的には、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−メタクリロイ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などが、酸化防止剤として具体的には、２，２′−チオビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノールなどが、紫外線吸収剤として具体的には、２−（３−ｔｅｒｔ−ブチル−２−ヒドロキシ−５−メチルフェニル）−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などが、また凝集防止剤として具体的には、ポリアクリル酸ナトリウムなどが、それぞれ挙げられる。
【００９１】
本発明のカラーフィルターを製造するにあたっては、以上のような各成分を含む感光性着色組成物を用いるが、その不揮発分の酸価を２５〜６０ｍｇ ＫＯＨ／ｇの範囲に調整するのが望ましい。ここでいう酸価は、この感光性着色組成物中の不揮発分１ｇ、すなわち溶剤を除く成分１ｇ中に含まれる酸性基を中和するのに要する水酸化カリウムの量（ｍｇ）と定義することができる。この酸価は、共重合体（Ｂ）中のカルボキシル基によって大きく影響されるが、その他の成分にも影響され、特に顔料分散剤を用いる場合はその種類にも影響されるので、通常は滴定によって決定される。この酸価があまり低くなると、それから形成された乾燥塗膜の現像液に対する溶解性が低くなり、溶解不良により現像残渣が多くなる。一方、この酸価があまり大きくなると、現像時に溶解成分が現像液に溶けすぎて、残った不溶成分が現像残渣となって現れてくる。いずれの場合も、現像残渣が遮光層部分と透明ガラス部分に発生し、密着力の低下や色再現性の低下につながる。
【００９２】
この感光性着色組成物は、例えば以下のようにして調製できる。すなわち、顔料（Ａ）を予め溶剤（Ｆ）と混合し、顔料の平均粒子径が０．２μｍ以下程度となるまで、ビーズミルなどを用いて分散させる。この際、必要に応じて分散剤が使用され、また共重合体（Ｂ）の一部又は全部が配合されることもある。得られた顔料分散液に、共重合体（Ｂ）の残り、光重合性モノマー（Ｃ）、光重合開始剤（Ｄ）、必要に応じて使用されるその他の成分、さらには必要により追加の溶剤を、所定の濃度となるように添加し、目的の感光性着色組成物を得る。
【００９３】
この感光性着色組成物は、基板表面に均一な厚さで塗布され、かつ均一な乾燥塗膜を与えるためには、その２５℃における粘度が、３〜２０ｍＰａ・ｓ の範囲にあるのが好ましい。また、チキソトロピー性が適当な範囲にあるのも好ましく、具体的には、Ｒ型粘度計を用い、ローター回転数５ｒｐｍで測定した粘度をＸとし、ローター回転数２０ｒｐｍ で測定した粘度をＹとしたときに、Ｘ／Ｙで表されるチキソトロピー性が、０．９〜１．５の範囲にあるのが好ましい。粘度やチキソトロピー性が上記範囲を外れる場合には、塗布する際の面内膜厚分布が大きくなったり、ムラが発生したりする傾向にある。
【００９４】
こうして調製された感光性樹脂組成物は、例えば以下のようにして基板上に塗布され、光硬化及び現像を経て着色画素となる。まずこの組成物を、遮光層がパターン形成された透明基板（通常はガラス）上に、バーコーター、スピンコーター、スリットを備えた省液型スピンコーターなどを用いて塗布し、加熱乾燥（プリベーク）して、平滑な乾燥塗膜を得る。このときの塗膜の膜厚は、通常３μｍ以下であり、好ましくは１〜２μｍ 程度である。得られた塗膜に、目的の画素を形成するためのネガ型フォトマスクを介して紫外線を照射する。この際、露光部全体に均一に平行光線が照射され、マスクと基板の正確な位置合わせが行われるよう、マスクアライナーなどの装置を使用するのも有効である。さらにこの後、光硬化の終了した塗膜をアルカリ性水溶液に接触させて未露光部を溶解させ、現像することにより、目的とする画素が得られる。現像後、必要に応じて１５０〜２３０℃で１０〜６０分程度の後硬化（ポストベーク）を施すこともできる。
【００９５】
パターニング露光後の現像に使用する現像液は、通常、アルカリ性化合物と界面活性剤を含む水溶液である。アルカリ性化合物は、無機及び有機のアルカリ性化合物のいずれでもよい。無機アルカリ性化合物の具体例としては、水酸化ナトリウム、水酸化カリウム、燐酸水素二ナトリウム、燐酸二水素ナトリウム、燐酸水素二アンモニウム、燐酸二水素アンモニウム、燐酸二水素カリウム、ケイ酸ナトリウム、ケイ酸カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、ホウ酸ナトリウム、ホウ酸カリウム、アンモニアなどが挙げられる。また、有機アルカリ性化合物の具体例としては、テトラメチルアンモニウムヒドロキシド、２−ヒドロキシエチルトリメチルアンモニウムヒドロキシド、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、エタノールアミンなどが挙げられる。これらの無機及び有機アルカリ性化合物は、それぞれ単独で又は２種以上組み合わせて用いることができる。アルカリ現像液中のアルカリ性化合物の好ましい濃度は、０．０１〜１０重量％の範囲であり、より好ましくは０．０５〜５重量％である。
【００９６】
また界面活性剤は、ノニオン系界面活性剤、カチオン系界面活性剤又はアニオン系界面活性剤のいずれでもよい。ノニオン系界面活性剤の具体例としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアリールエーテル、ポリオキシエチレンアルキルアリールエーテル、その他のポリオキシエチレン誘導体、オキシエチレン／オキシプロピレンブロックコポリマー、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンアルキルアミンなどが挙げられる。アニオン系界面活性剤の具体例としては、ラウリルアルコール硫酸エステルナトリウムやオレイルアルコール硫酸エステルナトリウムのような高級アルコール硫酸エステル塩類、ラウリル硫酸ナトリウムやラウリル硫酸アンモニウムのようなアルキル硫酸塩類、ドデシルベンゼンスルホン酸ナトリウムやドデシルナフタレンスルホン酸ナトリウムのようなアルキルアリールスルホン酸塩類などが挙げられる。カチオン系界面活性剤の具体例としては、ステアリルアミン塩酸塩やラウリルトリメチルアンモニウムクロライドのようなアミン塩又は第四級アンモニウム塩などが挙げられる。これらの界面活性剤は、それぞれ単独で用いることも、また２種以上組み合わせて用いることもできる。アルカリ現像液中の界面活性剤の濃度は、通常０．０１〜１０重量％の範囲、好ましくは０．０５〜８重量％、より好ましくは０．１〜５重量％である。
【００９７】
上述した本発明の感光性樹脂組成物の調製には、上述した本発明の顔料分散液を予め調製しておき、（ａ）〜（ｄ）以外の成分と配合するのが顔料の分散性の点からは望ましいがこれに限定されるものではなく、各成分の配合順序、混合方法も限定されるものではない。
【００９８】
以上説明した本発明の感光性樹脂組成物をレジスト液として用い、これを基板に塗布し加熱硬化してカラーフィルターを形成することができる。より具体的には前述した顔料分散レジスト法の工程により行うのが一般的である。基板への塗布は、回転塗布、ロール塗布等の塗布方法により塗布してレジスト層を形成し、所定のマスクパターンを介して▲３▼の露光を行い、現像液で▲４▼の現像を行うことによって着色されたパターンを形成する。
【００９９】
露光の際に使用される光線としては、一般に紫外領域のもの、特に３４０〜４６０ ｎｍが好ましく用いられる。
基板としては、一般にはガラス基板、例えば液晶表示素子等に用いられるソーダガラス、パイレックスガラス、石英ガラスおよびこれらに透明導電膜を付着させたものの他、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も挙げられる。これらの基板は、一般的には各画素を隔離するブラックストライプが形成されている。
【０１００】
現像液としては、塗料組成物を溶解し、一方紫外線照射部を溶解しない組成物であれば如何なるものも用いることができる。具体的には種々の有機溶剤の組み合わせやアルカリ性の水溶液を用いることができる。
【０１０１】
本発明の感光性樹脂組成物を用いた液晶パネルの形成は、例えば以下の方法で行うことができる。前述の感光性樹脂組成物を用いて、透明パネルの内面側に、赤色、緑色、青色の光をそれぞれ選択的に透過させる三種類のカラーフィルターを所定パターンでスクリーン印刷し、さらにこれら三種類のカラーフィルター層の内面側に、各々の色の蛍光体層をスクリーン印刷により形成する、いわゆるスクリーン印刷法により液晶パネルを形成することができる。
【０１０２】
また、熱転写用基材シートの表面に剥離層を形成し、前記剥離層の表面に赤色蛍光体層、緑色蛍光体層、青色蛍光体層を形成し、さらに前記各色の蛍光体層の表面に、本発明の感光性樹脂組成物を用いて各々赤色、緑色、青色の光をそれぞれ選択的に透過させる三種類のカラーフィルターを、各色の蛍光体層に対応して形成し、さらに前記カラーフィルターの表面に熱シール剤層を形成して転写シートを形成し、前記転写シートの熱シール剤層を透明パネルに密着させて熱転写印刷を行うことにより透明パネルの内面にカラーフィルター付き蛍光体層を形成する、いわゆる熱転写印刷法により液晶パネルを形成することができる。
基体に、酸により硬化しうる樹脂、キノンジアジド化合物、光酸発生剤、架橋剤、顔料及び溶剤を含む組成物を塗布後、溶剤を蒸発させる。マスクを通した露光により露光部のキノンジアジド化合物及び光酸発生剤を分解する。現像後、未露光部のポジ型着色パターンを得る。この未露光部のポジ型着色パターンを全面露光することにより硬化させる。全面露光を行ってパターンを硬化させる本発明方法は、カラーフィルターの耐溶剤性を高める。
【０１０３】
以上のような感光性着色組成物の塗布、乾燥、得られる乾燥塗膜へのパターニング露光、そして現像という各操作を経て、感光性着色組成物中の顔料の色に相当する画素が得られ、さらにこれらの操作を、カラーフィルターに必要とされる色の数だけ繰り返すことにより、カラーフィルターが得られる。
【０１０４】
【実施例】
以下、実施例により本発明を更に具体的に説明する。なお、「部」、「％」は特にことわりのない限り各々、「重量部」、「重量％」をあらわす。
まず、表−１及び表−２に示す処方で、ブルーＡ〜Ｃ、グリーンＤ及びＥ、イエローａ〜ｄの分散液を作製した。分散液の作製は、常法に従いメディアミルにより、分散粒径５０〜２００ｎｍ、３．０〜３０．０ｍＰａとなるよう調整した。表中の数字は「部」を示す。
表中の分散剤ａは、市販のポリエステル系の分散剤であり、ＰＧＭＥＡはプロピレングリコールモノメチルエーテルアセテートの略称である。
【０１０５】
【表１】

【０１０６】
【表２】

【０１０７】
（実施例１〜８、比較例１〜５）
表−１、表−２で作製した分散液を用いて、表−３、表−４に示す配合処方にてグリーン色相の顔料分散液を調色、作製した。表中の数字は「部」を示す。
【０１０８】
【表３】

【０１０９】
【表４】

【０１１０】
（評価方法及び評価結果）
各々の分散液について、Ｃ光源を用いて測定した、ＸＹＺ表色系色度図における色度座標（ｘ、ｙ）の内、ｙを０．７１０とした時の着色層の必要膜厚とｘ値、及びそのときの明度（Ｙ値）の各項目について評価した。
【０１１１】
各評価項目については、以下の方法で評価した。
各顔料分散液を用いて以下の配合処方により感光性樹脂組成物を調製した。
【０１１２】
〔配合処方〕
顔料分散液 １００部
感光性高分子 ５．９２部
アクリルモノマー（ジペンタエリスリトールヘキサアクリレート） ５．７２部
光重合開始剤１ １．３７部
光重合開始剤２ ０．６９部
ＰＧＭＥＡ １８７部
【０１１３】
（なお、感光性高分子は、（メタ）アクリル樹脂（ベンジルメタクリレート／メタクリル酸共重合体）（ベンジルメタクリレート：メタクリル酸の重量比は８０：２０であり、重量平均分子量は２５，４００）である。アクリルモノマー（ジペンタエリスリトールヘキサアクリレート）は日本化薬（株）製「ＫＡＹＡＲＡＤＤＰＨＡ」（商品名）、光重合開始剤１はＣｈｉｂａ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌｓ社製「イルガキュアー９０７」（商品名）、光重合開始剤２は日本化薬（株）製「カヤキュアーＤＥＴＸ−Ｓ」であり、ＰＧＭＥＡはプロピレングリコールモノメチルエーテルアセテートの略号である。）
【０１１４】
得られた感光性樹脂組成物を用い、コーニングジャパン社製＃１７３７ガラス基板表面上に、スピンコーターで所要膜厚に塗布した後、１１０℃で２分４０秒、乾燥した後、冷却した。さらに、フォトマスクを通して高圧水銀ランプで１５０ｍＪ／ｃｍ^２の紫外線で露光した後、０．０５％水酸化カリウム及び０．２％ブチルナフタレンスルホン酸ナトリウムを含むアルカリ性水溶液で現像した。
得られた塗付ガラス基板を、ｄａｔａｃｏｌｏｒ社製ＳＰＥＣＴＲＡＦＬＡＳＨＳＦ６００にてＣ光源、２゜視野の条件で色度測定を行い、所定の色度が得られるまで、上記操作を繰り返した。
なお、所定色度が得られたガラス基板についてＫＬＡテンコール社製サーフェスプロファイラーＰ−１０にて膜厚測定を行い、所定の色度を得られる膜厚を測定、比較した。結果を表−５に示す。
【０１１５】
【表５】

【０１１６】
比較例１〜５からわかるように、ＮＴＳＣ規格の緑色の色度規格である（ｘ，ｙ）（０．２１０，０．７１０）を満足する着色層にグリーン顔料と黄色顔料の調色を用いた場合、３μｍ以上というカラーフィルターの着色層として不適切な膜厚となってしまうのに対し、実施例１〜８が示すように、本発明で規定する特定の顔料構造物を使用することによって、着色剤添加量の増量を伴うことなく、３μｍ以下の実用的な膜厚にて、所望の色度を持った着色層を得ることが出来る。
【０１１７】
【発明の効果】
従来の着色剤添加量で、実用的な膜厚にてカラーフィルターのＮＴＳＣ色度規格のグリーン着色層を得ることの出来る感光性樹脂組成物及び顔料分散液であり、これらを使用することで、色再現性に優れた液晶カラーフィルターを得ることが出来る。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention is useful as a photosensitive resin composition for forming a color filter for forming a color material layer of a color filter and a pigment dispersion used for the same, a photosensitive resin composition and a pigment dispersion, and formed using these. And related color filters.
[0002]
[Prior art]
A color filter used for a liquid crystal display, an imaging device, or the like is generally formed by forming three primary color pixels of red, green, and blue and a black matrix that is a light shielding layer provided between these pixels on a transparent substrate such as glass. Being manufactured. These pixels and the black matrix are formed by applying a photosensitive coloring composition on a substrate, heating and drying (prebaking) to form a coating film, irradiating the coating film with ultraviolet rays, exposing the coating film, and further developing. It is formed by post-curing (post-baking) and removing unexposed portions by alkali washing.
[0003]
Currently, liquid crystal display devices using the above color filters are being developed for desktop monitors in addition to conventional notebook PCs. Further, recently, a large-sized liquid crystal television having further improved color reproducibility of a desktop monitor has been developed, and colors close to the color reproduction range of a CRT are being reproduced. Here, the color reproduction range is represented by an area ratio of a triangle connecting the red, green, and blue chromaticity coordinates in the XYZ color system chromaticity diagram with respect to the NTSC (National Television System Committee) standard. The color reproduction range of the CRT is about 70% of the NTSC standard. The color characteristics of the CRT are as follows. The chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram of red, green, and blue are red (0.640, 0.330) and green (0.290, 0), respectively. .600) and blue (0.150, 0.060), which are almost equal to the EBU (European Broadcasting Union) standard, but a display having a color reproduction range according to the EBU standard is particularly poor in the color reproduction range of the green region, and printed matter is poor. It was difficult to display such a colorful display. The color reproduction is wider than the EBU standard, and the above-mentioned NTSC standard is a good standard. Red, green, blue, and chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram of each color are red ( 0.670, 0.330), green (0.210, 0.710), and blue (0.140, 0.080).
[0004]
[Problems to be solved by the invention]
In order to manufacture a liquid crystal display device with a wide color reproduction range, it is conceivable to increase the thickness of the pixels of the color filter to increase the color density. However, if the color filter for conventional desktop monitors or liquid crystal televisions is made thicker to expand the color reproduction range to the same level as the NTSC standard, the film thickness becomes larger than the practical range, particularly for the green coloring layer. In addition, the level difference on the surface of the color filter becomes large, and disconnection of ITO and poor alignment of liquid crystal may occur. In addition, a pixel having a large film thickness is difficult to form a pattern, and the taper becomes large, so that the resolution may be reduced or a crack may occur (for example, see Patent Document 1).
[0005]
For forming a colored layer of a color filter in a liquid crystal display device having a low color reproducibility as conventionally produced, that is, a liquid crystal display device having a color reproducibility of 72% or less (EBU standard) in NTSC ratio, particularly for forming a green pixel. It is known that the toning is performed by combining a pigment green (hereinafter abbreviated as PG) 36 with a pigment yellow (hereinafter abbreviated as PY) 150 or PY138 (for example, see Patent Document 2). Further, it is known to form a green pixel of a color filter in a liquid crystal display device requiring color reproducibility near the EBU standard by combining PG7 with PY83 or PY150 (for example, toning). Patent Document 1). However, when a liquid crystal display device having a wider color reproducibility, especially a liquid crystal display device having a color reproducibility of 80% or more of the NTSC ratio is to be manufactured using a combination of these pigments, the pixel thickness of the color filter becomes large. Too much, the step on the surface of the color filter becomes large, and disconnection of ITO and poor liquid crystal alignment may occur. Further, it is difficult to form a pattern in a pixel having a large thickness, and the taper becomes large, so that the resolution may be reduced or a crack may be generated.
[0006]
[Patent Document 1]
JP 2002-258,267 A
[Patent Document 2]
Japanese Patent No. 3,005,185
[0007]
It is also conceivable that increasing the colorant content in the photosensitive coloring composition that forms the pixels may correspond to the expansion of the color reproduction range, but this will lead to a significant decrease in the amount of the photosensitive resin component, and the original resin The performance cannot be exhibited, and poor adhesion to a glass substrate, deterioration of coating film properties, poor developability, etc. will occur.
[0008]
In order to solve the above-mentioned problems, a color filter having a green coloring layer realizing high color reproducibility with a practical film thickness and a colorant addition amount has been desired. An object of the present invention is to provide a pigment dispersion liquid and a photosensitive resin composition that achieve high color reproducibility equivalent to NTSC with a practical film thickness and a colorant addition amount, and have been made in view of the drawbacks of the related art. To provide.
[0009]
[Means for Solving the Problems]
The present inventors have made intensive studies in view of the above problems. As a result, by using a pigment dispersion using a specific pigment as a colorant, high color reproducibility equivalent to NTSC is realized in a practical film thickness and colorant addition amount, and further, the photosensitive resin composition The present inventors have found that a product having excellent developability can be obtained when the above-mentioned conditions are satisfied. That is, the present invention
(1) a pigment dispersion, comprising as a green coloring component at least one selected from blue pigments;
(2) The pigment dispersion according to the above (1), wherein the pigment dispersion contains at least one selected from yellow pigments as a green coloring component.
(3) When a photosensitive resin component is blended and applied to a substrate and cured to form a color filter,
[0010]
The chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram measured using the C light source satisfy the respective expressions of 0.150 ≦ x ≦ 0.280 and 0.650 ≦ y ≦ 0.770. The pigment dispersion according to the above (1) or (2), wherein the green colored layer can be formed with a film thickness of 3 μm or less,
(4) The pigment dispersion according to any one of the above (1) to (3), further containing a dispersant,
(5) The pigment dispersion according to any one of the above (1) to (4), which is a pigment dispersion for a color filter,
(6) a photosensitive resin composition obtained by mixing a photosensitive resin component with the pigment dispersion according to any one of the above (1) to (5);
(7) The photosensitive resin composition according to the above (6), which is a photosensitive resin composition for a color filter,
[0011]
(8) a photosensitive resin composition comprising, as a green coloring component, at least one selected from blue pigments;
(9) The photosensitive resin composition as described in (8) above, which contains at least one kind selected from yellow pigments as a green coloring component.
(10) When a photosensitive resin component is blended, applied to a substrate, and cured to form a color filter, the chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram measured using a C light source are as follows. Any of (6) to (9) above, wherein a green colored layer satisfying each of the following expressions: 0.150 ≦ x ≦ 0.280 and 0.650 ≦ y ≦ 0.770 can be formed with a film thickness of 3 μm or less. The photosensitive resin composition according to,
[0012]
(11) a color filter obtained by applying and curing the photosensitive resin composition according to any one of (6) to (10) on a substrate;
(12) The chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram measured using the C light source are 0.150 ≦ x ≦ 0.280 and 0.650 ≦ y ≦ 0.770. A color filter having a green coloring layer having a thickness of 3 μm or less that satisfies the formula:
(13) A liquid crystal panel comprising the color filter according to (11) or (12),
Exists.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[0014]
<Pigment>
The pigment dispersion and the photosensitive resin composition of the present invention are characterized by containing a specific pigment as a green coloring component.
[0015]
That is, it is characterized by containing at least one selected from blue pigments. The blue pigment is not particularly limited, but typical examples of the blue pigment include, for example, Pigment Blue (hereinafter abbreviated as PB) 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 21, 22, 60, 64, 76, etc., and these can be used alone or in combination of two or more.
[0016]
In the present invention, it is extremely desirable to include a yellow pigment in addition to the above-mentioned blue pigment as a green coloring component. It is preferable to use a color toned using a blue pigment and a yellow pigment for a green pixel, because a thin film can be formed significantly. The yellow pigment is not particularly limited, but typical examples of the yellow pigment include, for example, PY1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31 , 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81 , 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 126, 127, 128, 129 , 138, 139, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 76,177,179,180,181,182,185,187,191: 1,199 and the like, they may be used alone or in admixture of two or more.
[0017]
Among the above blue pigments, in particular, the toning is performed by including at least one of PB15 (15: 1, 15: 3, 15: 4, 15: 6, etc.), PB16, and PB76. In particular, it is more preferable that the color is adjusted to include at least one of PB15: 3, PB15: 4, and PB76.
In addition, it is preferable to perform toning including at least one of PY12, PY13, PY17, PY83, PY109, PY110, PY138, PY139, PY150, and PY185 among the above-mentioned yellow pigments. , PY150, and the like. However, it is preferable to use PY138 in combination with another yellow pigment for thinning in a high color purity region. Specifically, a combination containing both PB15: 3 and PY139, a combination containing PB15: 3, PY83 and PY139, a combination containing PB15: 3, PY83 and PY150, a combination containing PB15: 3, PY83 and PY138, A combination including PB15: 3 and PY83 can be more preferably used.
It should be noted that a small amount of PG7, PG36 or the like may be added as a green pigment for adjusting the color tone within a range that does not hinder the thinning of the colored layer.
[0018]
When toning is performed using PB15: 3 or PB16 as a coloring component of a green pixel, the weight ratio of PB15: 3 or PB16 in all the pigments is preferably 20 to 60%, and more preferably 25 to 55%. Is more preferred. When toning is performed using PB76, the weight ratio of PB76 in all the pigments is preferably 40 to 80%, and more preferably 45 to 75%. These blue pigments may be used in combination of two or more. If the addition amount of the blue pigment is less than the above, the coloring power is reduced and the pixel film thickness is increased, which is not preferable. If the addition amount is more than the above, the tint becomes bluish and may not be suitable as a green pixel. When toning is performed using PY83 as a yellow pigment for green toning, the weight ratio of PY83 in all the pigments is preferably from 10 to 70%, more preferably from 15 to 65%. When toning is performed using PY138, the weight ratio of PY138 in all the pigments is preferably 5 to 30%, and more preferably 5 to 25%. When toning is performed using PY139, the weight ratio of PY139 in all the pigments is preferably 10 to 80%, more preferably 10 to 70%, and even more preferably 15 to 65%. When toning is performed using PY150, the weight ratio of PY150 in all the pigments is preferably 5 to 50%, more preferably 5 to 40%, and still more preferably 10 to 40%. These yellow pigments may be used in combination of two or more.
[0019]
The above-mentioned pigment may have been subjected to a surface treatment such as a rosin treatment, an acid group treatment and a basic treatment, if necessary. In addition, the primary particle diameter of the pigment is required to be transparent due to the characteristics of the color filter, and is preferably 200 nm or less, which is half or less the wavelength of visible light, more preferably 150 nm or less, and particularly preferably 100 nm or less. This is preferable in order to increase the transmittance and the brightness when the color filter is manufactured.
[0020]
The pigment is used in an amount of preferably 5 to 60% by weight, more preferably 10 to 50% by weight, based on the total solid content in the photosensitive composition.
[0021]
<Dispersion medium>
The pigment dispersion and the photosensitive resin composition of the present invention contain a dispersion medium as a component. The dispersion medium used here is not particularly limited, and any medium generally used for color filters can be used.
For example, as a solvent, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, cyclohexanone, Examples include ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, ethyl pyruvate, and dimethylformamide. These solvents can be used alone or in combination of two or more.
[0022]
Examples of the dispersion medium used herein include cellosolve acetate solvents such as cellosolve acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methoxypropyl acetate, and 2-methoxyethyl acetate, 3-ethoxyethyl propionate, and propylene. Organic solvents such as hydrocarbon compounds having an ether bond and an ester bond such as glycol monomethyl ether propionate, water, and the like are preferably used.
[0023]
Although the amount of the dispersion medium is not limited, the concentration of the pigment in the dispersion liquid is generally 5 to 50% by weight, preferably in consideration of easy mixing with the resin composition described later and dispersion stability. Adjust so as to be 10 to 30% by weight. It is particularly preferably adjusted to be 10 to 20% by weight.
[0024]
Further, a dispersant and a dispersion aid may be added.
[0025]
<Dispersant>
The dispersant used in the present invention is not particularly limited as long as it can be dissolved in the dispersion medium.
[0026]
Representative examples of such dispersants include, for example, in organic solvent systems, polyurethanes, carboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters and modified products thereof, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with a polyester having a free carboxylic acid group Water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol and polyvinylpyrrolidone Water-soluble polymer compound: sodium lauryl sulfate, poly Xylethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanol lauryl sulfate Amines, anionic surfactants such as ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer monoethanolamine, and polyoxyethylene alkyl ether phosphate; polyoxyethylene Lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polio Nonionic surfactants such as ciethylene sorbitan monostearate and polyethylene glycol monolaurate; amphoteric surfactants such as alkyl betaines such as alkyl dimethylaminoacetic acid betaines and alkyl imidazolines; these may be used alone or in combination of two or more. Can be used in combination.
[0027]
Among these, a dispersant having an amine structure is particularly preferable because of its excellent dispersibility. Examples of the dispersant having such an amine structure include Solsperse series manufactured by Avicia, Disperbyk series manufactured by BYK Chemie, and Efka series manufactured by Efka. The amine value is preferably from 1 to 100 mg KOH / g, and more preferably from 10 to 40 mg KOH / g.
The amount of the dispersant is usually not more than 50 parts by weight, preferably not more than 30 parts by weight, based on 100 parts by weight of the pigment.
[0028]
If necessary, a compound such as a known dispersing aid may be added. These compounds mediate between the pigment and the dispersant, and are considered to have a function of electrically and chemically adsorbing the pigment surface and the dispersant to improve the dispersion stability.
[0029]
Examples of such a dispersing agent include a polycarboxylic acid type polymer activator, an anionic activator such as a polysulfonic acid type polymer activator, and a nonionic activator such as polyoxyethylene and polyoxylen broloc polymer. Although preferred, anthraquinone, phthalocyanine, metal phthalocyanine, quinacridone, azochelate, azo, isoindolinone, pyranthrone, indanthrone, anthrapyrimidine, dibromoanthanthrone, flavanthrone are preferred. A pigment derivative having an organic pigment such as a perylene-based, perylene-based, perinone-based, quinophthalone-based, thioindigo-based, or dioxazine-based as a base, and having introduced a substituent such as a hydroxyl group, a carboxyl group, a sulfonic acid group, a carbonamide group, or a sulfonamide group No. Of these, phthalocyanine-based and metal phthalocyanine sulfonamide compounds are particularly effective.
[0030]
The method for preparing the dispersion is not particularly limited. It is desirable that the above components are mixed in advance to prepare a pigment dispersion, and a resin component is blended therein. By preparing a pigment dispersion in advance and achieving a desired degree of dispersion, it becomes easy to uniformly disperse the pigment in the resin composition.
[0031]
The dispersing means for preparing the pigment dispersion is not particularly limited. Generally, a pigment and a dispersant are mixed in a dispersion medium, a medium such as glass beads and zirconia beads is added, and the mixture is dispersed by a media mill such as a paint conditioner, a ball mill, and a sand grinder. Also, the dispersion can be carried out using a kneader, a two-roll, a three-roll, a homogenizer system, a jet mill, an ultrasonic wave or the like. A plurality of these dispersing means may be combined.
[0032]
The degree of dispersion is preferably adjusted so that the dispersed particle size of the pigment is 50 to 300 nm, preferably 50 to 200 nm. The dispersed particle size here is, for example, an average particle size obtained by a known laser Doppler type particle size measuring device.
The viscosity of the dispersion is preferably adjusted to 3.0 to 200.0 mPa · s, more preferably 3.0 to 100.0 mPa · s, and still more preferably 3.0 to 30.0 mPa · s.
The viscosity here is the viscosity of the dispersion at a liquid temperature of 25 ° C., obtained from a known cone plate type viscosity type.
[0033]
If the dispersion is insufficient and the dispersion particle size is larger than the above range, undispersed pigments called coarse particles remain, which may cause a defect in the filtering step and adversely affect the surface roughness of the pixel.
On the other hand, when the state is excessively dispersed, which is called overdispersion, a problem arises in an increase in dispersion viscosity and dispersion stability, which may adversely affect the coating properties of the photosensitive resin composition and the development characteristics.
In addition, even if there are coarse particles with insufficient dispersion, they can be removed by filtering and adjusted to the above-mentioned range of dispersed particle diameter. Further, even when the dispersion is sufficient, it is desirable to perform filtering for the purpose of removing foreign substances in the system, and the filtering may be performed using a normal filter.
[0034]
Thus, the pigment dispersion for a color filter of the present invention can be obtained. Here, the pigment dispersion for a color filter is a pigment dispersion used for forming pixels of a color filter.
In order to form a pixel of a color filter, it is a general process to apply a pixel to a transparent substrate, expose and cure the pixel as described below, in addition to the pigment described above, a photosensitive resin component. It is generally used as a contained photosensitive resin composition. The photosensitive resin composition of the present invention contains at least the pigment described above and a photosensitive resin component. Further, if necessary, a binder resin may be contained, and generally a solvent component is also contained. A so-called color filter forming resist photosensitive resin composition corresponds to various pigment-containing compositions used for forming pixels of a color filter.
[0035]
(Photopolymerization initiator)
In order to cure the photosensitive resin composition by exposure, a photopolymerization initiator that absorbs light and generates radicals is generally contained. Examples of the photopolymerization initiator include benzyl; benzoin ether; benzoin isobutyl ether; benzoin isobutyl ether; benzophenone; benzoyl benzoic acid; methyl benzoyl benzoate; 4-benzoyl-4'-methyldiphenyl sulfide; One or more of various known photopolymerization initiators in the photosensitive resin composition such as n-butoxyel-4-methylaminobenzoate; 2-chlorothioxanthone may be appropriately selected and used.
[0036]
(Photosensitive resin component)
The photosensitive resin component is not particularly limited as long as it is a photosensitive photocrosslinkable or photopolymerizable compound that is cured by the action of a photopolymerization initiator. For example, a photopolymerizable compound having at least one ethylenically unsaturated double bond as described in JP-A-11-14822 is typical.
[0037]
Examples of the photopolymerizable compound having at least one ethylenically unsaturated double bond that can be used include the following compounds.
[0038]
Photocrosslinkable or photopolymerizable monomers, oligomers, and prepolymers include ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, ethylene glycol dimethacrylate, pentaerythritol triacrylate, hydroxyethyl methacrylate, ethylene glycol dimethacrylate, Esters of acrylic acid or methacrylic acid of monohydric or polyhydric alcohol such as pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate; condensation of polyhydric alcohol and monobasic acid Obtained by reacting (meth) acrylic acid with polyester prepolymer obtained by (Meth) acrylate; polyurethane (meth) acrylate obtained by reacting a compound having a polyol group and two isocyanate groups with (meth) acrylic acid; bisphenol A epoxy resin, bisphenol F epoxy resin, novolak Epoxy resins such as epoxy resin, polycarboxylic acid glycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenolmethane epoxy resin, dihydroxybenzene epoxy resin and (meth) acrylic acid And a usual photopolymerizable resin such as an epoxy (meth) acrylate obtained by reacting
[0039]
These radically polymerizable monomers having an ethylenically unsaturated double bond can be used alone or in combination of two or more. For example, 2-ethyl, 2-butylpropanediol diacrylate, pentaerythritol tetraacrylate , Dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, polyoxyethylated trimethylolpropane triacrylate, tris (2-acryloyloxyethyl) isocyanurate, 1,4-diisopropenylbenzene, 1,4- Dihydroxybenzene methacrylate, decamethylene glycol diacrylate, ethylene glycol diacrylate, triethylene glycol acrylate, trimethylolpropane triacrylate, diallyl fumarate, etc. It is below. In particular, 2-butylpropanediol diacrylate, pentaerythritol tetraacrylate, dipentaeristol pentaacrylate, or polyoxyethylated trimethylolpropane triacrylate is preferred.
[0040]
Among these photopolymerizable compounds, compounds having an average molecular weight of 1000 or more have a very high photopolymerization rate, and it is particularly useful to incorporate these compounds into the photosensitive resin composition.
In particular, a photopolymerizable compound having an acidic group such as a carboxyl group and an ethylenically unsaturated double bond is preferably used. These compounds are extremely useful in increasing the content of the photopolymerizable compound having an ethylenically unsaturated double bond in the photosensitive resin, increasing the polymerization rate under atmospheric exposure, and enabling aqueous development. .
[0041]
Specific examples of the photopolymerizable compound having both an acidic group such as a carboxyl group and an ethylenically unsaturated double bond include bisphenol A epoxy resin, bisphenol F epoxy resin, novolak epoxy resin, and glycidyl polycarboxylate. Ester, polyol glycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenolmethane epoxy resin, dihydroxybenzene epoxy resin and other epoxy groups and hydroxy groups obtained by reacting (meth) acrylic acid Epoxy (meth) acrylate-carboxylic acid adducts can be copolymerized with maleic anhydride by reacting with acid anhydrides, and can be copolymerized with monomers such as ethylene, propene, isobutylene, styrene, vinylphenol, acrylic acid, acrylic acid esters and acrylamide. A half-esterified compound obtained by reacting the maleic anhydride part of the polymer with an acrylate having an alcoholic hydroxy group such as hydroxyethyl acrylate or an acrylate having an epoxy group such as glycidyl methacrylate Acrylic acid, acrylic acid ester and hydroxyethyl acrylate And a compound obtained by further reacting acrylic acid with an -OH group of an acrylate copolymer having an alcoholic hydroxy group.
[0042]
It is preferable to prepare the photosensitive resin composition so that the ratio of the photopolymerizable compound is 60% or more.
[0043]
(Binder resin)
The binder resin is generally an organic polymer substance that plays a role of a binder for improving a photopolymerizable layer such as compatibility, film forming property, developability, adhesiveness, etc., for example, as disclosed in JP-A-10-253,820. And JP-A-11-14,822.
[0044]
Specific examples include the following compounds.
Polyolefin polymers such as polyethylene, polypropylene and polyisobutylene; diene polymers such as polybutadiene and polyisoprene; polymers having a conjugated polyene structure such as polyacetylene polymers and polyphenylene polymers; polyvinyl chloride, polystyrene, vinyl acetate, polyvinyl alcohol, Vinyl polymers such as polyacrylic acid, polyacrylic acid ester, polyacrylamide, polyacrylonitrile, and polyvinyl phenol; polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyether ketone, polyether such as polyacetal; novolak resin, resol resin, etc. Phenolic resin; polyethylene terephthalate, polyphenolphthalein terephthalate, polycarbonate Polyesters such as alkyd resins and unsaturated polyester resins; polyamides such as nylon-6, nylon 66, water-soluble nylon and polyphenylene amide; polypeptides such as gelatin and casein; novolak epoxy resins, bisphenol epoxy resins, novolak epoxy acrylates and acid anhydrides Resins such as modified resins and modified products thereof; polyurethanes, polyimides, melamine resins, urea resins, polyimidazoles, polyoxazoles, polypyrroles, polyanilines, polysulfides, polysulfones, celluloses and the like.
[0045]
For example, a copolymer of (meth) acrylic acid and an alkyl ester of (meth) acrylic acid (for example, a methyl group, an ethyl group, a butyl group, etc.); Copolymers with basic acid anhydrides may be mentioned. Further, a high molecular compound containing a carboxylic acid, a hydroxy group, an amino group, a carboxylic amide group, a sulfonamide group, or the like in a molecule is also included.
[0046]
Among these organic polymer substances, a photosensitive resin composition containing a resin having a carboxyl group, a phenolic hydroxyl group, or the like in a resin side chain or a main chain is preferable from the viewpoint of preventing pollution since it can be alkali-developed. In particular, a resin having a carboxyl group, for example, an acrylic acid (co) polymer, a styrene / maleic anhydride resin, an acid anhydride-modified resin of novolak epoxy acrylate, and the like are preferable because of high alkali developability.
[0047]
Further, acrylic resins are preferred because of their excellent developability, and various copolymers can be obtained by selecting various monomers, and thus are preferred from the viewpoint of performance and production control. More specifically, examples of the acrylic resin containing a carboxyl group include (meth) acrylic acid, (maleic anhydride) and the like, for example, various resins exemplified in JP-A-10-253,820.
[0048]
The added amount of these binder resins is preferably 40% by weight or less, particularly preferably 5 to 30% by weight of the total solid content. More preferably, the amount is 15 to 30% by weight. If the amount is less than 5% by weight, the adhesion strength between the substrate and the pattern is reduced, and if it exceeds 30% by weight, the photosensitivity is reduced.
For the purpose of improving heat resistance, an epoxy compound such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, and glycidyl polycarboxylate may be used. It is considered that the combination of an epoxy compound and a compound having a carboxylic acid reacts and crosslinks to improve heat resistance.
[0049]
(solvent)
The solvent to be used is not particularly limited, and the same solvent as that used for obtaining the pigment dispersion may be used. Further, as a diluting solvent for improving the workability during the preparation of the photosensitive resin composition, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, ethyl carbitol acetate, diglyme, cyclohexanone, propylene glycol monomethyl ether acetate And organic solvents such as lactic acid esters.
[0050]
In addition, a silane coupling agent and a titanate coupling agent for improving the adhesion to the substrate as required, a fluorine-based, silicon-based, hydrocarbon-based surfactant and an ultraviolet absorber for improving the smoothness of the film. And various additives such as an antioxidant.
[0051]
Specific examples of the photosensitive resin composition include various kinds of known so-called resist compositions which are used for forming pixels of a color filter. For example, either a polyfunctional acrylate monomer or a polyfunctional methacrylate monomer, an organic polymer binder, and a photopolymerization initiator composed of at least one selected from halomethyloxadiazole-based compounds and halomethyl-s-triazine-based compounds. (JP-B-6-95211), a photosensitive resin containing a photopolymerization initiator that absorbs light to generate radicals and a monomer that is cured by the action of the photopolymerization initiator. And more preferably those containing an organic polymer substance as a binder in order to improve the photopolymerizable layer such as compatibility, film forming property, developability, adhesiveness, etc. From the viewpoint of prevention, it is preferable to have a carboxyl group or a phenolic hydroxyl group in the resin side chain or main chain as an organic polymer substance as a preferable one Fatty acid-containing monomers that are cured by the action of the photopolymerization initiator. Known monomers such as monomers that undergo radical polymerization by the action of radicals generated by the photopolymerization initiator and monomers that undergo addition condensation by the action of acids generated from the photopolymerization initiator. And a resist containing a combination of an acrylic resin containing a carboxyl group and an acrylic monomer (Japanese Patent Application Laid-Open No. 10-253,820).
[0052]
Further, a polymer compound used in a photosensitive resin composition containing a binder resin, a monomer having an ethylenically unsaturated double bond, and a photopolymerization initiator described in JP-A-11-14,822. A photopolymerization initiation system that absorbs light to generate a radical, and a compound (ethylenic compound) having at least one addition-polymerizable ethylenically unsaturated double bond in which polymerization is induced by the radical; A photopolymerizable composition (Japanese Unexamined Patent Publication No. 11-80,584) containing an organic polymer substance (binder resin) and a dispersant as required, a copolymer containing hydroxystyrene as a main component, a crosslinking agent , A copolymer containing a photoacid generator and carbon black, wherein the copolymer containing hydroxystyrene as a main component has a hydroxystyrene unit content of at least 50 mol%, A photosensitive composition containing a copolymer containing 5 to 30 mol% of a monomer unit having an acid group (JP-A-11-24269); (A) condensation of phenols having cresol with aldehydes (B) acid-crosslinkable methylolated melamine resin, and (C) a photosensitive resin composition containing a halogen-containing triazine compound having a specific structure and capable of absorbing light to generate an acid. No. Hei 11-143,056).
[0053]
A photosensitive resin composition containing a hindered phenolic antioxidant (Japanese Patent Application Laid-Open No. 2002-22925), and a photosensitive resin obtained by introducing a carboxyl group into a molecule to impart water solubility. Epoxy resins having two or more epoxy groups in one molecule such as novolak type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, etc. Carboxyl group-containing epoxy (meth) acrylate obtained by reacting an acid anhydride with a hydroxyl group generated when reacting with an unsaturated monobasic acid such as (meth) acrylic acid, copolymerizable with maleic anhydride Ethylene, propylene, isobretine, styrene, vinylphenol, (meth) acrylic acid, Compounds obtained by half-esterification by reacting (meth) acrylate having an alcoholic hydroxyl group such as hydroxyethyl (meth) acrylate with the maleic anhydride part of a copolymer with a monomer such as acrylate or acrylamide, or trimethylol Examples thereof include half-esterified products of a hydroxyl group-containing (meth) acrylate such as propane di (meth) acrylate and pentaerythritol tri (meth) acrylate with an acid anhydride (Japanese Patent Application Laid-Open No. 8-337,736).
[0054]
In recent years, a cardo-type polymer known as a polymer material having high heat resistance, solvent solubility, high transparency, high refractive index, low birefringence, and high gas permeability is a photosensitive resin component used for forming a color filter. Also known as The cardo type polymer is a general term for polymers having a structure in which a cyclic group is directly bonded to a polymer main chain. However, the presence of a bulky substituent in the main chain results in (1) rotation constraint of the polymer main chain, (2) conformational regulation of the main chain and side chain, (3) inhibition of intermolecular packing, (4) increase in aromaticity due to introduction of an aromatic substituent on the side chain, and the like, and furthermore, characteristics in physical properties It is said to exhibit higher gas permeability in addition to high heat resistance, solvent solubility, high transparency, high refractive index, low birefringence, and the like.
[0055]
Such cardo-type polymers, in particular, cardo-type polymers having a fluorene skeleton represented by the following formulas (III) to (VII) have been proposed as photosensitive resins for color filters (Japanese Patent Publication No. Hei 7 (1994)). -35,426, JP-A-7-48424, JP-A-9-241,339, JP-A-9-241,340, JP-A-9-304,929, JP-A-9-325 , 494, JP-A-9-328,534), and such a cardo type polymer can be particularly preferably used as a photosensitive resin component in the photosensitive resin composition of the present invention.
[0056]
Formula (I):
[0057]
Embedded image

[0058]
(In the formula (I), R represents either a hydrogen atom or a methyl group, and n is an integer of 0 to 20.)
[0059]
Formula (II):
Embedded image

[0060]
(In the formula (II), n is an integer of 1 or more.)
[0061]
Formula (III):
Embedded image

[0062]
(In the formula (III), n is an integer of 1 or more)
Formula (IV):
Embedded image

[0063]
(In the formula (IV), R ₁ And R2 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and n represents a number of 1 to 5. A represents a tetravalent organic residue, and X represents a number of 1 or more. )
[0064]
Formula (V):
Embedded image

[0065]
(In the formula (V), R represents H or a lower alkyl group, R ′ represents H or a methyl group, and n is an integer of 0 to 20.)
[0066]
The above-mentioned materials are mixed using a stirrer such as a dissolver type stirrer, a turbo type stirrer, and a twin-screw stirrer to obtain a photosensitive resin composition, or a two-roll mill, a three-roll mill, a sand mill, and a paint. The photosensitive resin composition is kneaded using a disperser such as a shaker, and the preferable amount of the above-mentioned organic solvent used at that time is usually 50 to 200% by weight of the total solids.
[0067]
This photosensitive resin composition is generally called a photosensitive coloring composition or a pigment-dispersed resist, in which a pigment is dispersed in a solvent, and a copolymer called a binder resin, a photopolymerizable monomer, and a photopolymerization initiator. , And optionally other additives, are dissolved or dispersed.
For example, a positive resist composition comprising a heat-curable resin, a quinonediazide compound, a crosslinking agent and a pigment; containing an acid-curable resin, a quinonediazide compound, a photoacid generator, a crosslinking agent and a pigment Positive resist compositions.
Examples of the resin which can be cured by heat or acid include a resin having a phenolic hydroxyl group or a carboxyl group, or a resin having a phenolic hydroxyl group or a carboxyl group. Photopolym. Sci. Technol. vol. 3, No. 3 (1990), pp. 235-247, that is, a copolymer containing a hydroxystyrene structure, that is, a copolymer of p-hydroxystyrene and p-acetoxymethylstyrene, and the like. Examples of the resin having a carboxyl group include a copolymer of polymethacrylate and maleic anhydride. Examples of the resin having a phenolic hydroxyl group include an alkali-soluble phenol resin and a novolak resin. Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol (m-cresol, p-cresol, etc.), ethylphenol, 2-t-butyl-5-methyl-phenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, Bisphenol C and bisphenol A are exemplified. These phenols are used alone or in combination of two or more. Aldehydes include, for example, aliphatic or aromatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde or benzaldehyde. If necessary, a resin that can be cured by heat or acid, such as a resin having a phenolic hydroxyl group, may be used to adjust the molecular weight distribution by using a means such as fractionation. Further, a phenol such as bisphenol A or bisphenol C may be added to a resin which can be cured by heat or acid.
[0068]
As the crosslinking agent, for example, the following formula-(CH ₂ ) S OR (wherein, R represents a hydrogen atom or a lower alkyl group, and s represents an integer of 1 to 4), and melamine. As the compound having a group represented by the above formula, for example,
[0069]
Embedded image

[0070]
Wherein Z is -NR ₁ R ₂ Or a phenyl group. R ₁ ~ R ₆ Is at least one of them,-(CH ₂ ) S OH or-(CH ₂ ) S OR ₇ A hydrogen atom,-(CH ₂ ) S OH or-(CH ₂ ) S OR ₇ Represents R ₇ Represents a lower alkyl group. s represents an integer of 1 to 4. Or a compound represented by the following formula:
[0071]
Embedded image

[0072]
Embedded image

[0073]
And the like. R and R ₇ The lower alkyl group represented by is a methyl, ethyl, n-propyl or n-butyl group, and the preferable alkyl group is a methyl or ethyl group. Each of the compounds represented by the formulas (i) to (ii) can be produced by condensing p-cresol or t-butylphenol with formaldehyde under basic conditions. The compounds represented by formulas (iii) to (vi) are known compounds described in JP-A-1-293339. Formula-(CH ₂ Examples of preferred compounds having a group represented by sOR include hexamethoxymethylolated melamine, hexamethoxyethylolated melamine, and hexamethoxypropylolated melamine.
[0074]
The photoacid generator is not particularly limited as long as it generates an acid directly or indirectly by light. For example, trihalomethyltriazine compounds described in JP-A-4-163552, JP-A-1-57777 Compound disclosed in Japanese Patent Application Publication No. ₈ -SO ₂ -SO ₂ -R ₉ -SO ₂ -SO ₂ -R ₁₀ (Where R ₈ And R ₁₀ Each independently represents an optionally substituted aryl, aralkyl, alkyl, cycloalkyl or heterocyclic group; ₉ Represents an optionally substituted aryl. ), A photoacid generator having a sulfonic acid ester group described in JP-A-1-293339, CF ₃ -SO ₂ O- (CH ₂ A compound represented by the formula CF, wherein Y is an aryl group which may be substituted, and n represents 0 or 1. ₃ -SO ₂ O- [C (Y ₁ ) (Y ₂ )] M-C (O) -Y ₃ (Where Y ₁ And Y ₂ Each independently represents an alkyl, alkoxy or aryl group which may be substituted, ₃ Represents an aryl group which may be substituted, and m represents 1 or 2. A compound of the formula CF ₃ -SO ₂ ON (Y ₄ ) -C (O) -Y ₅ (Where Y ₄ Is an optionally substituted alkyl group, and Y is ₅ Represents an aryl group which may be substituted. A compound of the formula CF ₃ -SO ₂ ON = C (Y ₆ ) (Y ₇ ) (Where Y ₆ Represents a hydrogen atom or an optionally substituted alkyl or aryl group, ₇ Represents an aryl group which may be substituted. ), A compound represented by the following formula:
[0075]
Embedded image

[0076]
And the like.
[0077]
Examples of the quinonediazide compound include o-naphthoquinonediazide-5-sulfonic acid ester or sulfonamide, or o-naphthoquinonediazide-4-sulfonic acid ester or sulfonamide. These esters or amides can be produced by a known method using, for example, a phenol compound described in the general formula (I) in JP-A-2-84650 and JP-A-3-49437.
[0078]
The resin curable by heat or acid and the crosslinking agent are usually dissolved in a solvent at a ratio of about 2 to 50 and about 2 to 30% by weight, respectively. The amounts of the quinonediazide compound, the photoacid generator and the pigment are usually about 2 to 30, 2 to 30 and 2 to 50% by weight, respectively, based on the solution of the resin and the crosslinking agent. In addition, various additives commonly used in the art such as a smoothing agent for imparting uniform coating properties or a dispersing agent for dispersing a pigment may be added to the positive resist composition. .
[0079]
Positive resists are those in which exposed portions are removed and unexposed portions remain as a positive colored pattern, utilizing the fact that a difference in solubility in an alkali developing solution is caused by exposure. That is, the quinonediazide compound is decomposed by exposure to light and becomes soluble in an alkali developer, while the unexposed portion acts to suppress the dissolution of the resin in the alkali developer. Then, when the unexposed portion is entirely exposed, the remaining quinonediazide compound is decomposed, while, when a photoacid generator is contained, this has the effect of generating an acid and curing the positive-type colored pattern. . For the exposure, for example, an ultraviolet ray such as a mercury lamp, a far ultraviolet ray, an electron beam or an X-ray is used.
[0080]
The binder resin imparts alkali developability to the unexposed coating film and acts as a dispersion medium for the pigment. In the present invention, a copolymer containing (meth) acrylic acid as one monomer is used as the binder resin. (B) is used. The (meth) acrylic acid referred to in the present specification means acrylic acid or methacrylic acid. In addition, for example, similarly to (meth) acrylate, it means acrylate or methacrylate. This copolymer (B) is usually obtained by copolymerization of (meth) acrylic acid and another monomer copolymerizable therewith, and contains a carboxyl group derived from (meth) acrylic acid.
[0081]
The monomer copolymerizable with (meth) acrylic acid is a compound having a polymerizable carbon-carbon unsaturated bond. Specifically, styrene, α-methylstyrene, aromatic vinyl compounds such as vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl Of unsaturated carboxylic acid alkyl esters such as (meth) acrylate, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate, vinyl acetate and vinyl propionate; Carboxylic acid vinyl esters, vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile, and unsaturated carboxylic acids other than (meth) acrylic acid such as crotonic acid, itaconic acid, maleic acid, and fumaric acid. Is mentioned. These monomers can be copolymerized with (meth) acrylic acid alone or in combination of two or more.
[0082]
Examples of suitable copolymers using (meth) acrylic acid as one monomer include (meth) acrylic acid / benzyl (meth) acrylate copolymer and (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer. And a (meth) acrylic acid / methyl methacrylate / styrene copolymer. Further, such a copolymer having (meth) acrylic acid as one monomer, in which the side chain is modified with a compound having a photosensitive group, is also referred to in the present invention as (meth) acrylic acid as one monomer. Is included in the copolymer (B).
[0083]
The copolymer (B) preferably has a weight average molecular weight in the range of 5,000 to 400,000 in terms of polystyrene, and more preferably has a weight average molecular weight in the range of 10,000 to 300,000. . The copolymer (B) is generally contained in an amount of 5 to 90% by weight, preferably 20 to 70% by weight, based on the total solid content in the photosensitive coloring composition.
[0084]
The photopolymerizable monomer (C) is a compound that undergoes polymerization by the action of light and a photopolymerization initiator, and generally corresponds to a compound having a polymerizable carbon-carbon unsaturated bond. The photopolymerizable monomer (C) may be a monofunctional monomer, a difunctional or other polyfunctional monomer. Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. Further, specific examples of the bifunctional monomer include:
1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and the like, and specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate. Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (methacryloyloxyethyl) ethyl Cyanurate and the like. The photopolymerizable monomers (C) can also be used alone or in combination of two or more. The photopolymerizable monomer (C) is generally contained in the range of 5 to 90% by weight, preferably in the range of 20 to 70% by weight, based on the total solid content in the photosensitive coloring composition. .
[0085]
In particular, the photopolymerizable monomer (C) has an acrylic group (CH2 = CHCO-) and has a large number of acrylic groups per unit weight of the compound, in other words, a gram of the compound per equivalent of the acrylic group. A compound having a small acrylic group equivalent expressed by a number is preferable, and among them, a compound having an acrylic group equivalent of 100 or less is preferably used. In some cases, such a monomer having a small acrylic group equivalent can be used in combination with another monomer. When the acrylic group equivalent is increased, when the dried coating film obtained therefrom is exposed and developed, sensitivity tends to be insufficient, which may lead to a reduction in the productivity of the color filter. In order to be a compound having a small acrylic group equivalent, a polyfunctional monomer having two or more functional groups is preferable. The monomer having an acrylic group equivalent of 100 or less includes ethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like, among others, trimethylolpropane triacrylate, Pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate is preferably used.
[0086]
The photopolymerization initiator (D) is commonly used in this field, and examples thereof include acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, and other initiators. Specific examples of the acetophenone-based initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) Phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- Oligomers of 1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one; Specific examples of the agent include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin. Examples include zoin isopropyl ether and benzoin isobutyl ether. Specific examples of the benzophenone-based initiator include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3, Examples thereof include 3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone. Specific examples of the thioxanthone-based initiator include 2-isopropylthioxanthone and 4-isopropyl Thioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. Specific examples of other initiators include 2,4,6-trimethylbenzoyldiphthane. Nylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethyl Examples include anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like. These photopolymerization initiators can be used alone or in combination of two or more.
[0087]
Further, a photoinitiator can be used in combination with a photopolymerization initiator. Examples of the photoinitiating aid include amine-based and alkoxyanthracene-based ones, and specific examples thereof include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. Ethyl aminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (Commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10- Diethoxyant Sen, etc. are included. These photoinitiating assistants can also be used alone or in combination of two or more.
[0088]
The photopolymerization initiator and the optional photoinitiator are generally added in an amount of 3 to 50 parts by weight based on 100 parts by weight of the copolymer (B) and the photopolymerizable monomer (C) in total. In the range, preferably in the range of 5 to 40 parts by weight.
[0089]
The solvent can be any of those used in this field. Specific examples include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, ethyl pyruvate, methyl 3-methoxypropionate, Esters such as ethyl 3-ethoxypropionate; ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone and cyclohexanone; glycol ethers such as 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate Esters; aromatic hydrocarbons such as benzene, toluene, o-, m- or p-xylene; These solvents can be used alone or in combination of two or more. The amount of the solvent to be used is preferably 60 to 90% by weight, more preferably 70 to 85% by weight, based on the total amount of the photosensitive coloring composition containing the solvent.
[0090]
The photosensitive coloring composition according to the present invention may also contain, if necessary, a filler, another polymer compound, a surfactant (pigment dispersant), an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-agglomeration material. And the like. Specific examples of the filler include glass, silica, and alumina, and specific examples of other polymer compounds include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. As the (pigment dispersant), various types such as nonionic, cationic, and anionic are used. Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane. N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyl Methoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxy Examples of the antioxidant include silane and the like, specifically, 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, etc. Specific examples of the agent include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and specific examples of the aggregation inhibitor include polyacrylic acid. Sodium and the like.
[0091]
In producing the color filter of the present invention, a photosensitive coloring composition containing each of the above components is used, and the acid value of the nonvolatile component is desirably adjusted to a range of 25 to 60 mg KOH / g. The acid value as used herein is defined as the amount (mg) of potassium hydroxide required to neutralize the acidic groups contained in 1 g of the nonvolatile components in the photosensitive coloring composition, that is, 1 g of the components excluding the solvent. Can be. This acid value is greatly affected by the carboxyl group in the copolymer (B), but is also affected by other components, especially when a pigment dispersant is used. Is determined by If the acid value is too low, the solubility of the dried coating film formed therefrom in the developing solution will be low, and the development residue will increase due to poor dissolution. On the other hand, when the acid value is too large, the dissolved components are excessively dissolved in the developing solution during development, and the remaining insoluble components appear as development residues. In any case, development residues are generated in the light-shielding layer portion and the transparent glass portion, leading to a decrease in adhesion and a decrease in color reproducibility.
[0092]
This photosensitive coloring composition can be prepared, for example, as follows. That is, the pigment (A) is previously mixed with the solvent (F) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, a dispersant is used as needed, and a part or all of the copolymer (B) may be blended. In the obtained pigment dispersion, the remainder of the copolymer (B), the photopolymerizable monomer (C), the photopolymerization initiator (D), other components used as needed, and further additional A solvent is added so as to have a predetermined concentration to obtain a desired photosensitive coloring composition.
[0093]
This photosensitive coloring composition is preferably applied to the substrate surface in a uniform thickness, and in order to give a uniform dried coating film, the viscosity at 25 ° C. is preferably in the range of 3 to 20 mPa · s. . It is also preferable that the thixotropic property is in an appropriate range. Specifically, using a R-type viscometer, the viscosity measured at a rotor speed of 5 rpm is X, and the viscosity measured at a rotor speed of 20 rpm is Y. Sometimes, the thixotropy represented by X / Y is preferably in the range of 0.9 to 1.5. If the viscosity or thixotropy is out of the above range, the in-plane film thickness distribution at the time of coating tends to be large or unevenness tends to occur.
[0094]
The photosensitive resin composition thus prepared is applied on a substrate, for example, as follows, and becomes a colored pixel through photo-curing and development. First, this composition is applied on a transparent substrate (usually glass) on which a light-shielding layer is patterned by using a bar coater, a spin coater, a liquid-saving spin coater having a slit, and the like, and is dried by heating (prebaking). Thus, a smooth dried coating film is obtained. At this time, the thickness of the coating film is usually 3 μm or less, preferably about 1 to 2 μm. The obtained coating film is irradiated with ultraviolet rays through a negative photomask for forming a target pixel. At this time, it is also effective to use a device such as a mask aligner so that the entire exposed portion is uniformly irradiated with parallel rays and accurate alignment between the mask and the substrate is performed. Further, after that, the photo-cured coating film is brought into contact with an alkaline aqueous solution to dissolve and develop the unexposed portions, thereby obtaining target pixels. After development, post-curing (post-baking) at 150 to 230 [deg.] C. for about 10 to 60 minutes can be performed as necessary.
[0095]
The developer used for the development after the patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be any of inorganic and organic alkaline compounds. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Examples include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. And the like. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The preferred concentration of the alkaline compound in the alkaline developer is in the range of 0.01 to 10% by weight, more preferably 0.05 to 5% by weight.
[0096]
The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like can be mentioned. Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates such as sodium dodecylnaphthalene sulfonate, and the like. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants can be used alone or in combination of two or more. The concentration of the surfactant in the alkali developer is usually in the range of 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight.
[0097]
In preparing the above-described photosensitive resin composition of the present invention, the pigment dispersion of the present invention described above is prepared in advance, and is mixed with components other than (a) to (d). Although desirable from the point of view, the present invention is not limited thereto, and the order of mixing and the method of mixing the components are not limited.
[0098]
A color filter can be formed by using the photosensitive resin composition of the present invention described above as a resist solution, applying the resist solution to a substrate, and curing by heating. More specifically, it is generally carried out by the above-described step of the pigment dispersion resist method. The coating on the substrate is performed by a coating method such as spin coating, roll coating or the like to form a resist layer, and exposure (3) is performed through a predetermined mask pattern, and development (4) is performed with a developing solution. Thus, a colored pattern is formed.
[0099]
As the light beam used in the exposure, light in the ultraviolet region, particularly 340 to 460 nm, is preferably used.
As the substrate, in general, a glass substrate, for example, soda glass used for a liquid crystal display device and the like, Pyrex glass, quartz glass and those obtained by attaching a transparent conductive film to these, as well as a photoelectric conversion element substrate used for a solid-state imaging device and the like, For example, a silicon substrate may be used. These substrates are generally formed with black stripes for isolating each pixel.
[0100]
Any developer can be used as long as it dissolves the coating composition and does not dissolve the ultraviolet irradiation part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
[0101]
A liquid crystal panel using the photosensitive resin composition of the present invention can be formed, for example, by the following method. Using the above-described photosensitive resin composition, on the inner surface side of the transparent panel, three types of color filters that selectively transmit red, green, and blue light, respectively, are screen-printed in a predetermined pattern, and these three types are further printed. A liquid crystal panel can be formed by a so-called screen printing method in which phosphor layers of each color are formed on the inner surface side of the color filter layer by screen printing.
[0102]
Further, a release layer is formed on the surface of the substrate sheet for thermal transfer, and a red phosphor layer, a green phosphor layer, and a blue phosphor layer are formed on the surface of the release layer, and further on the surface of the phosphor layer of each color. Using the photosensitive resin composition of the present invention, three types of color filters for selectively transmitting red, green, and blue light, respectively, are formed corresponding to the phosphor layers of each color, and the color filter is further formed. A heat sealing agent layer is formed on the surface of the transfer sheet to form a transfer sheet, and the heat sealing agent layer of the transfer sheet is adhered to the transparent panel to perform heat transfer printing, thereby forming a phosphor layer with a color filter on the inner surface of the transparent panel. A liquid crystal panel can be formed by a so-called thermal transfer printing method.
After applying a composition containing a resin curable by an acid, a quinonediazide compound, a photoacid generator, a crosslinking agent, a pigment, and a solvent to the substrate, the solvent is evaporated. Exposure through the mask decomposes the quinonediazide compound and the photoacid generator in the exposed area. After development, an unexposed portion of a positive colored pattern is obtained. The unexposed portion of the positive colored pattern is cured by exposing the entire surface. The method of the present invention in which the pattern is cured by performing overall exposure increases the solvent resistance of the color filter.
[0103]
Application of the photosensitive coloring composition as described above, drying, patterning exposure to the obtained dried coating film, and through each operation of development, a pixel corresponding to the color of the pigment in the photosensitive coloring composition is obtained, Further, by repeating these operations by the number of colors required for the color filter, a color filter can be obtained.
[0104]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. “Parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.
First, dispersions of blues A to C, greens D and E, and yellows a to d were prepared according to the formulations shown in Tables 1 and 2. The dispersion was prepared by a media mill according to a conventional method so as to have a dispersion particle diameter of 50 to 200 nm and 3.0 to 30.0 mPa. The numbers in the table indicate "parts".
Dispersant a in the table is a commercially available polyester-based dispersant, and PGMEA is an abbreviation for propylene glycol monomethyl ether acetate.
[0105]
[Table 1]

[0106]
[Table 2]

[0107]
(Examples 1 to 8, Comparative Examples 1 to 5)
Using the dispersions prepared in Tables 1 and 2, a pigment dispersion having a green hue was toned and prepared according to the formulation shown in Tables 3 and 4. The numbers in the table indicate "parts".
[0108]
[Table 3]

[0109]
[Table 4]

[0110]
(Evaluation method and evaluation result)
For each of the dispersions, the required film thickness of the colored layer and x when y is 0.710 in the chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram measured using a C light source The values and the respective items of the lightness (Y value) at that time were evaluated.
[0111]
Each evaluation item was evaluated by the following method.
Using each pigment dispersion, a photosensitive resin composition was prepared according to the following formulation.
[0112]
(Formulation)
100 parts of pigment dispersion
5.92 parts of photosensitive polymer
5.72 parts of acrylic monomer (dipentaerythritol hexaacrylate)
1.37 parts of photopolymerization initiator 1
Photopolymerization initiator 2 0.69 parts
187 copies of PGMEA
[0113]
(The photosensitive polymer is a (meth) acrylic resin (benzyl methacrylate / methacrylic acid copolymer) (the weight ratio of benzyl methacrylate: methacrylic acid is 80:20, and the weight average molecular weight is 25,400). The acrylic monomer (dipentaerythritol hexaacrylate) is “KAYARDADDPHA” (trade name) manufactured by Nippon Kayaku Co., Ltd., and the photopolymerization initiator 1 is “Irgacure 907” (trade name) manufactured by Chiba Specialty Chemicals, and photopolymerization is started. Agent 2 is "Kayacure DETX-S" manufactured by Nippon Kayaku Co., Ltd., and PGMEA is an abbreviation for propylene glycol monomethyl ether acetate.)
[0114]
The obtained photosensitive resin composition was applied on a # 1737 glass substrate manufactured by Corning Japan Co., Ltd. with a spin coater to a required thickness, dried at 110 ° C. for 2 minutes and 40 seconds, and then cooled. Further, through a photomask, a high-pressure mercury lamp is used for 150 mJ / cm. ² And then developed with an alkaline aqueous solution containing 0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate.
The obtained coated glass substrate was subjected to chromaticity measurement using SPECTRAFLASHSF600 manufactured by datacolor under the conditions of a C light source and a 2 ° visual field, and the above operation was repeated until a predetermined chromaticity was obtained.
The film thickness of the glass substrate having the predetermined chromaticity was measured by using a surface profiler P-10 manufactured by KLA Tencor, and the film thickness at which the predetermined chromaticity was obtained was measured and compared. The results are shown in Table-5.
[0115]
[Table 5]

[0116]
As can be seen from Comparative Examples 1 to 5, the toning of the green pigment and the yellow pigment was used for the colored layer satisfying the green chromaticity standard (x, y) (0.210, 0.710) of the NTSC standard. In contrast, when the thickness is 3 μm or more, the film thickness becomes unsuitable as a colored layer of the color filter. On the other hand, as shown in Examples 1 to 8, by using a specific pigment structure defined in the present invention A colored layer having a desired chromaticity can be obtained with a practical film thickness of 3 μm or less without increasing the amount of the coloring agent added.
[0117]
【The invention's effect】
With a conventional colorant addition amount, a photosensitive resin composition and a pigment dispersion that can obtain a green color layer of NTSC chromaticity standard of a color filter with a practical film thickness, and by using these, A liquid crystal color filter having excellent color reproducibility can be obtained.

Claims (13)

A pigment dispersion containing at least one selected from blue pigments as a green coloring component. The pigment dispersion according to claim 1, wherein the green color component includes at least one selected from yellow pigments. When a photosensitive resin component is blended, applied to a substrate, and cured to form a color filter, the chromaticity coordinate (x, y) in the XYZ color system chromaticity diagram measured using a C light source is 0.150. 3. The pigment dispersion according to claim 1, wherein a green colored layer satisfying each of the following expressions: ≦ x ≦ 0.280 and 0.650 ≦ y ≦ 0.770 can be formed with a film thickness of 3 μm or less. 4. The pigment dispersion according to any one of claims 1 to 3, further comprising a dispersant. The pigment dispersion according to any one of claims 1 to 4, which is a pigment dispersion for a color filter. A photosensitive resin composition obtained by mixing a photosensitive resin component with the pigment dispersion according to claim 1. The photosensitive resin composition according to claim 6, which is a photosensitive resin composition for a color filter. A photosensitive resin composition comprising, as a green coloring component, at least one selected from blue pigments. 9. The photosensitive resin composition according to claim 8, comprising at least one selected from yellow pigments as a green coloring component. 10. When a photosensitive resin component is blended, applied to a substrate, and cured to form a color filter, the chromaticity coordinate (x, y) in the XYZ color system chromaticity diagram measured using a C light source is 0.150. The photosensitive resin according to any one of claims 6 to 9, wherein a green colored layer that satisfies each of the following expressions: ≤ x ≤ 0.280 and 0.650 ≤ y ≤ 0.770 can be formed with a film thickness of 3 µm or less. Composition. A color filter formed by applying and curing the photosensitive resin composition according to claim 6 on a substrate. The chromaticity coordinates (x, y) in the XYZ color system chromaticity diagram measured using the C light source satisfy the respective expressions of 0.150 ≦ x ≦ 0.280 and 0.650 ≦ y ≦ 0.770. A color filter having a green coloring layer having a thickness of 3 μm or less. A liquid crystal panel comprising the color filter according to claim 11.