JP2004109423A - Colored photosensitive resin composition - Google Patents

Abstract

[Problem] To provide a colored photosensitive resin composition capable of preparing a highly sensitive colored photosensitive resin composition in a short time even if a coloring material is contained at a high concentration, and to provide a surface smoothness, a pattern shape and a pattern using the same. Providing high-quality color filters with excellent brightness.
The photopolymerization initiator contains (A) a binder resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a coloring material, and (E) a solvent. A colored photosensitive resin composition containing an imidazole compound and (E) at least one aliphatic cyclic ketone solvent selected from the group consisting of cyclopentanone and cyclohexanone as a solvent and propylene glycol monoalkyl ether acetate, (1) The powder X-ray diffraction pattern of the imidazole compound is diffracted at least in the range of 9.7 ° to 9.9 ° and in the range of 10.0 ° to 10.2 ° in 2θ angle of Cu-Kα characteristic X-ray diffraction. A colored photosensitive resin composition having a peak.
[Selection diagram] None

Description

（式中、Ｒ^１〜Ｒ^８は、それぞれ独立して、水素原子、またはハロゲン、炭素数炭素数１〜６の置換されていてもよいアルキル基、炭素数１〜６の置換されていてもよいシクロアルキル基、炭素数１〜６の置換されていてもよいフェニル基、炭素数１〜６の置換されていてもよいアルコキシ基を示し、Ｘは、−ＮＲ^９−、−Ｏ−、−Ｓ−を示し、Ｒ^９は、水素原子、炭素数１〜６の置換されていてもよいアルキル基を示す。）
【００２０】
さらに、（３）光重合開始助剤を併用することで、得られる着色感光性樹脂組成物は更に高感度となり、これを用いてカラーフィルタを形成する際の生産性が向上するので、好ましい。
【００２１】
本発明の着色感光性樹脂組成物に含まれるビイミダゾール化合物としては、２，２’−ビス（２−クロロフェニル）―４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（２、３−ジクロロフェニル）―４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（２−クロロフェニル）―４，４’，５，５’−テトラフェニルビイミダゾール、２，２’−ビス（２−クロロフェニル）―４，４’，５，５’−テトラ（アルコキシフェニル）ビイミダゾール、２，２’−ビス（２−クロロフェニル）―４，４’，５，５’−テトラ（ジアルコキシフェニル）ビイミダゾール、２，２’−ビス（２−クロロフェニル）―４，４’，５，５’−テトラ（トリアルコキシフェニル）ビイミダゾール、４，４’５，５’−位のフェニル基がカルボアルコキシ基により置換されているイミダゾール化合物などが挙げられ、好ましくは２，２’−ビス（２−クロロフェニル）―４，４’，５，５’−テトラフェニルビイミダゾールである。
【００２２】
（Ｃ）光重合開始剤として（１）に加えてさらに、（２）アセトフェノン化合物、トリアジン化合物、チオール化合物および式（Ｉ）で表される化合物のうち少なくとも１種を含有することができる。
【００２３】
アセトフェノン化合物としては、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、好ましくは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−オンが挙げられる。
トリアジン化合物としては、２，４−ビス（トリクロロメチル）−６−（４−メトキシフェニル）−１，３，５−トリアジン、
２，４−ビス（トリクロロメチル）−６−（４−メトキシナフチル）−１，３，５−トリアジン、
２，４−ビス（トリクロロメチル）−６−ピペロニル−１，３，５−トリアジン、
２，４−ビス（トリクロロメチル）−６−（４−メトキシスチリル）−１，３，５−トリアジン、
２，４−ビス（トリクロロメチル）−６−〔２−（５−メチルフラン−２−イル）エテニル〕−１，３，５−トリアジン、
２，４−ビス（トリクロロメチル）−６−〔２−（フラン−２−イル）エテニル〕−１，３，５−トリアジン、
２，４−ビス（トリクロロメチル）−６−〔２−（４−ジエチルアミノ−２−メチルフェニル）エテニル〕−１，３，５−トリアジン、
２，４−ビス（トリクロロメチル）−６−〔２−（３，４−ジメトキシフェニル）エテニル〕−１，３，５−トリアジンなどが挙げられ、好ましくは２，４−ビス（トリクロロメチル）−６−ピペロニル−１，３，５−トリアジン、
２，４−ビス（トリクロロメチル）−６−（４−メトキシスチリル）−１，３，５−トリアジン等が挙げられる。
チオール化合物としては、分子中にチオール基を有する化合物であり、チオール基を一個有するチオール化合物として、２−メルカプトベンゾチアゾール、２−メルカプトベンゾオキサゾール等の他、脂肪族基にチオール基を複数有する脂肪族多官能チオール化合物が好ましい。本発明に使用される脂肪族多官能チオールの例としては、ヘキサンジチーオル、デカンジチオール、１，４−ジメチルメルカプトベンゼン、ブタンジオールビスチオプロピオネート、ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、トリメチロールプロパントリスチオグリコレ−ト、ブタンジオールビスチオプロピオネート、トリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネートおよび、これらの他に、多価ヒドロキシ化合物のチオグリコレート、チオプロピオネートなどが挙げられ、好ましくはトリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリスチオグリコレートおよびペンタエリスリトールテトラキスチオプロピオネートなどが挙げられ、とりわけ好ましくはペンタエリスリトールテトラキスチオプロピオネートが挙げられる。
式（Ｉ）で表される化合物としては、Ｎ−フェニルグリシン、フェノキシ酢酸、フェニルチオ酢酸、メチルフェニルチオ酢酸、エチルフェニルチオ酢酸、メチルエチルフェニルチオ酢酸、ジメチルフェニルチオ酢酸、メトキシフェニルチオ酢酸、ジメトキシフェニルチオ酢酸、クロロフェニルチオ酢酸、ジクロロフェニルチオ酢酸などが挙げられ、好ましくはジクロロフェニルチオ酢酸、フェニルチオ酢酸が挙げられる。
【００２４】
また、本発明の効果を損なわない程度であれば、この分野で通常用いられている光重合開始剤を併用することができる。光重合開始剤としては、例えば、ベンゾイン系、ベンゾフェノン系、チオキサントン系、アントラセン系、およびその他の開始剤が挙げられる。より具体的には以下のような化合物を挙げることができ、これらをそれぞれ単独で、又は２種以上組み合わせて用いることができる。
【００２５】
（ｃ）ベンゾフェノン系
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。
【００２６】
（ｄ）チオキサントン系
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。
【００２７】
（ｆ）アントラセン系
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。
【００２８】
（ｇ）その他
２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキシド、
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。
【００２９】
また、光重合開始剤に（３）光重合開始助剤を組み合わせて用いることもできる。光重合開始助剤としては、アミン化合物が好ましく、アミン化合物は芳香族アミン化合物がより好ましい。光重合開始助剤の具体例としては、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などの脂肪族アミン化合物、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）ベンゾフェノンのような芳香族アミン化合物が挙げられる。
【００３０】
（Ｃ）光重合開始剤において、（Ａ）バインダー樹脂および（Ｂ）光重合性モノマーの合計１００質量部に対し、ビイミダゾール化合物は、通常０．１〜４０質量部、好ましくは１〜３０質量部の範囲で含有される。
（２）アセトフェノン化合物、トリアジン化合物、チオール化合物および式（Ｉ）で表される化合物の１種もしくは２種以上用いる場合はその合計量が、前記の基準で、好ましくは０．１〜４０質量部、より好ましくは１〜３０質量部の範囲で含有される。
（３）光重合開始助剤は、前記の基準で好ましくは０．０１〜４０質量部、より好ましくは０．１〜３０質量部の範囲で含まれる。
また、前記のビイミダゾール化合物、（２）アセトフェノン化合物、トリアジン化合物、チオール化合物および式（Ｉ）で表される化合物のうち少なくとも１種の化合物の合計量は、前記の基準で、通常０．１〜５０質量部、好ましくは１〜４０質量部の範囲で含有される。前記の化合物の合計量が、前記の範囲にあると、着色感光性樹脂組成物が高感度となり、前記の着色感光性樹脂組成物を用いて形成した画素部の強度や、前記の画素の表面における平滑性が良好になる傾向があり、好ましい。
前記のビイミダゾール化合物の量および（２）アセトフェノン化合物、トリアジン化合物、チオール化合物および式（Ｉ）で表される化合物のうち少なくとも１種の化合物の量に加えて、（３）光重合開始助剤の量が前記の範囲にあると、また（１）〜（３）の合計量が前記の範囲にあると、得られる着色感光性樹脂組成物の感度がさらに高くなり、前記の着色感光性樹脂組成物を用いて形成するカラーフィルタの生産性が向上する傾向にあり、好ましい。
【００３１】
（Ｄ）着色材料は、通常顔料であり、顔料分散レジストに通常用いられる有機顔料又は無機顔料であることができる。無機顔料としては、金属酸化物や金属錯塩のような金属化合物が挙げられ、具体的には、鉄、コバルト、アルミニウム、カドミウム、鉛、銅、チタン、マグネシウム、クロム、亜鉛、アンチモンなどの金属の酸化物又は複合金属酸化物が挙げられる。また有機顔料として具体的には、カラーインデックス（Ｃｏｌｏｕｒ　Ｉｎｄｅｘ）（Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ　出版）で、ピグメント（Ｐｉｇｍｅｎｔ）　に分類されている化合物が挙げられる。より具体的には、以下のようなカラーインデックス（Ｃ．Ｉ．）番号の化合物が挙げられるが、これらに限定されるわけではない。
【００３２】
Ｃ．Ｉ．ピグメントイエロー　２０，　２４，　３１，　５３，　８３，　８６，　９３，　９４，　１０９，　１１０，　１１７，　１２５，　１３７，　１３８，　１３９，　１４７，　１４８，　１５０，　１５３，　１５４，　１６６および１７３；
Ｃ．Ｉ．ピグメントオレンジ　１３，　３１，　３６，　３８，　４０，　４２，　４３，　５１，　５５，　５９，　６１，　６４　６５および７１；
Ｃ．Ｉ．ピグメントレッド　９，　９７，　１０５，　１２２，　１２３，　１４４，　１４９，　１６６，　１６８，　１７６，　　１７７，　１８０，　１９２，　２１５，　２１６，　２２４，　２４２および２５４；
Ｃ．Ｉ．ピグメントバイオレット　１４，　１９，　２３，　２９，　３２，　３３，　３６，　３７および３８；
Ｃ．Ｉ．ピグメントブルー　１５（１５：３，　１５：４，　１５：６　など），　２１，　２２，　２８，　６０および６４；
Ｃ．Ｉ．ピグメントグリーン　７，　１０，　１５，　２５，　３６および４７；
Ｃ．Ｉ．ピグメントブラウン　２８；
Ｃ．Ｉ．ピグメントブラック　１および７など。
【００３３】
これらの（Ｄ）着色材料は、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。（Ｄ）着色材料は、着色感光性樹脂組成物中の全固形分量を基準に、通常５〜６５質量％、好ましくは１０〜６０質量％の範囲で用いられる。
（Ｄ）着色材料の含有量が、前記の基準で、５〜５５質量部の範囲であると、薄膜にしても画素の色濃度が十分であり、現像時に非画素部の抜け性が低下することがないため、残渣が発生しにくい傾向があり、好ましい。
【００３４】
（Ｅ）溶剤は、プロピレングリコールモノアルキルエーテルアセテートとしては、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等が挙げられ、脂肪族環状ケトン系溶剤としては、シクロペンタノン、シクロヘキサノンが好ましい。さらに、本発明の効果を損なわなければ他の溶剤を併用することもできる。他の溶剤としては、この分野で用いられている各種のものであることができる。その具体例としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテルおよびエチレングリコールモノブチルエーテルのようなエチレングリコールモノアルキルエーテル類；
ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテルおよびジエチレングリコールジブチルエーテルのようなジエチレングリコールジアルキルエーテル類；
メチルセロソルブアセテートおよびエチルセロソルブアセテートのようなエチレングリコールアルキルエーテルアセテート類；
メトキシブチルアセテートおよびメトキシペンチルアセテートのようなアルキレングリコールアルキルエーテルアセテート類；
ベンゼン、トルエン、キシレンおよびメシチレンのような芳香族炭化水素類；
メチルエチルケトン、アセトン、メチルアミルケトン、メチルイソブチルケトンのようなケトン類；
エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコールおよびグリセリンのようなアルコール類；
３−エトキシプロピオン酸エチルおよび３−メトキシプロピオン酸メチルのようなエステル類；
γ−ブチロラクトンのような環状エステル類などが挙げられる。
これらの併用できる他の溶剤は、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。
（Ｅ）溶剤の使用量は、それを含む着色感光性樹脂組成物全体の量を基準に、通常６０〜９０質量％、好ましくは７０〜８５質量％である。（Ｅ）溶剤の含有量が、前記の基準で０．１〜５０質量部の範囲であると、塗布性が良好になる傾向があり、好ましい。また、脂肪族環状ケトン系溶剤の量は、全溶剤中の５〜６０質量％、好ましくは、１０〜５０質量％である。前記の範囲であると着色感光性樹脂組成物を短時間に調製できる。
【００３５】
本発明の着色感光性樹脂組成物には、必要に応じて、充填剤、他の高分子化合物、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（Ｆ）添加剤を混合使用することもできる。
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、ポリフルオロアルキルアクリレートなどを用いることができる。
顔料分散剤としては、市販の顔料分散剤を用いることができ、例えば、シリコーン系、フッ素系、エステル系、カチオン系、アニオン系、ノニオン系、両性などの界面活性剤などが挙げられ、それぞれ単独でまたは２種以上を組み合わせて用いられる。前記の界面活性剤の例としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリエチレングリコールジエステル類、ソルビタン脂肪酸エステル類、脂肪酸変性ポリエステル類、３級アミン変性ポリウレタン類、ポリエチレンイミン類等のほか、商品名でＫＰ（信越化学工業（株）製）、ポリフロー（共栄化学（株）製）、エフトップ（トーケムプロダクツ社製）、メガファックス（大日本インキ化学工業（株）製）、フロラード（住友スリーエム（株）製）、アサヒガード、サーフロン（以上、旭硝子（株）製）、ソルスパース（ゼネカ（株）製）、ＥＦＫＡ（ＥＦＫＡ　ＣＨＥＭＩＣＡＬＳ社製）、ＰＢ８２１（味の素（株）製）などが挙げられる。
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挙げられる。
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挙げられる。
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挙げられる。
他の高分子化合物として具体的には、エポキシ樹脂などの熱硬化性樹脂やポリエステル、ポリウレタン等の熱可塑性樹脂が挙げられる。
また凝集剤として具体的には、ポリアクリル酸ナトリウムなどが挙げられる。
【００３６】
本発明の着色感光性樹脂組成物は、例えば、以下のようにして調製することができる。すなわち、（Ｄ）着色材料を予め（Ｅ）溶剤と混合し、着色材料の平均粒子径が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、必要に応じて顔料分散剤が使用され、また（Ａ）バインダー樹脂の一部又は全部が配合されることもある。得られた分散液（ミルベース）に、（Ａ）バインダー樹脂の残り、（Ｂ）光重合性モノマーおよび（Ｃ）光重合開始剤、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、目的の着色感光性樹脂組成物を得る。
【００３７】
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材上に塗布し、光硬化および現像を行って、ブラックマトリックス又は着色画像とすることができる。まず、この組成物を基板（通常はガラス）上にスピンコートし、加熱乾燥（プリベーク）することにより溶剤を除去して、平滑な塗膜を得る。このときの塗膜の厚さは、およそ１〜３μｍ程度である。このようにして得られた塗膜に、目的のブラックマトリックス又は画像を形成するためのネガ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、かつ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が好ましい。さらにこの後、硬化の終了した塗膜を希アルカリ水溶液に接触させて非露光部を溶解させ、現像することにより、目的とするブラックマトリックス又は画像が得られる。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。
【００３８】
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、無機およ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。これらの無機およ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質量％の範囲であり、より好ましくは０．０３〜５質量％である。
【００３９】
またアルカリ現像液中の界面活性剤は、ノニオン系界面活性剤、アニオン系界面活性剤又はカチ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質量％の範囲、好ましくは０．０５〜８質量％、より好ましくは０．１〜５質量％である。
【００４０】
以上のような着色感光性樹脂組成物の塗布、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、感光性樹脂組成物中の着色材料の色に相当する画素又はブラックマトリックスが得られ、さらにこれらの操作を、カラーフィルタに必要とされる色の数だけ繰り返すことにより、カラーフィルタが得られる。すなわち、カラーフィルタは通常、ブラックマトリックス並びに、赤、緑および青の三原色画素を基板上に配置したものであるが、ある色に相当する着色材料を含む本発明の着色感光性樹脂組成物を用いて上記の操作を行うことにより、その色のブラックマトリックス又は画素を得て、他の色についても所望の色に相当する着色材料を含む本発明の着色感光性樹脂組成物を用いて同様の操作を行い、ブラックマトリックスおよび三原色画素を基板上に配置することができる。もちろん、ブラックマトリックスおよび三原色のうちいずれか一色、二色又は三色にのみ、本発明の感光性樹脂組成物を適用することも可能である。なお、遮光層であるブラックマトリックスは、例えば、クロム層などで形成されることもあるので、この場合にはもちろん、ブラックマトリックスの形成に本発明の着色感光性樹脂組成物を用いる必要はない。
【００４１】
そして、本発明の感光液を用いて製造されたカラーフィルタは、面内の膜厚差が小さく、例えば１〜３μｍの膜厚で、面内膜厚差を０．１５μｍ以下、さらには０．０５μｍ以下とすることができる。したがって、こうして得られるカラーフィルタは、平滑性および透明性に優れたものであり、またこれをカラー液晶表示装置に組み込むことにより、優れた品質の液晶パネルを高い歩留りで製造することができる。
【００４２】
【実施例】
上記において、本発明の実施の形態について説明を行なったが、上記に開示された本発明の実施の形態は、あくまで例示であって、本発明の範囲はこれらの実施の形態に限定されない。本発明の範囲は、特許請求の範囲によって示され、さらに特許請求の範囲の記載と均等の意味　および範囲内でのすべての変更を含むものである。以下、実施例によって本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。例中、含有量ないし使用量を表す％および部は、特にことわらないかぎり質量基準である。
【００４３】
実施例１
表１に記載の各成分のうち、予め顔料とポリエステル系顔料分散剤の各全量を、溶剤である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部分量と混合し、ビーズミルを用いて顔料を十分に分散させ、これに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残量を含む残りの成分を加えて混合し、着色感光性樹脂組成物を得た。
【００４４】
【表１】

【００４５】
上記各成分のうち、予め顔料と顔料分散剤の各全量を、溶剤であるプロピレングリコールモノメチルエーテルアセテートが、顔料および顔料分散剤の合計量に対して８０質量％となる量で混合し、ビーズミルを用いて顔料を十分に分散させ、図１の粉末Ｘ線回折図に示すピークを有する２，２’−ビス（２−クロロフェニル）―４，４’，５，５’−テトラフェニルビイミダゾール（図１のピークの説明については、表３および表４に示した。）および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残量を含むその他の成分を加えて混合し、着色感光性樹脂組成物を得た。
【００４６】
２インチ角のコーニング社製＃７０５９ガラス基板を、中性洗剤、水およびアルコールで順次洗浄してから乾燥した。このガラス基板上に、上で調製した着色感光性樹脂組成物（表１）をスピンコートし、次にクリーンオーブン中、１００℃で３分間プリベークした。冷却後、このレジスト塗布基板と石英ガラス製フォトマスク（透過率を１〜１００％の範囲で階段状に変化させるパターンと１μｍから５０μｍまでのライン／スペースパターンを有する）との間隔を１００μｍとし、ウシオ電機（株）製の超高圧水銀ランプを用いて大気雰囲気下、５０ｍＪ／ｃｍ^２の露光量で光照射した。その後、非イオン系界面活性剤０．１２％と水酸化カリウム０．０４％を含む水系現像液に上記塗膜を室温で所定時間浸漬して現像し、水洗後、２２０℃で３０分間ポストベークを行った。そして、プリベーク後、現像後およびポストベーク後の基板表面を観察し、以下の項目について結果を表２に示した。
【００４７】
実施例２
実施例１において、シクロヘキサノンをシクロペンタノンに変更する以外は、実施例１と同様の操作を行った。
比較例１
【００４８】
実施例１において、シクロヘキサノンをプロピレングリコールモノメチルエーテルアセテートに変更する以外は、実施例１と同様の操作を行ったが、均一な着色感光性樹脂組成物が得られなかった。
【００４９】
【表２】

【００５０】
表中の注釈の説明
＊１：室温下、撹拌のみで均一な着色感光性樹脂組成物を調製できる場合：○、室温下、撹拌のみで均一な着色感光性樹脂組成物を調製できない場合：×
＊２：現像しても表面荒れがないパターンを形成するために必要な最低必要露光量を示す。
＊３：現像工程を省略して作製した塗膜部のＣ光源、２度視野のＣＩＥ色度（ｘ、ｙ、Ｙ）を顕微分光測光装置（ＯＳＰ−ＳＰ２００；オリンパス販売（株）製）により測定した。同一色度（ｘ，ｙ）において、Ｙ値が大きいほど明度が高いことを示す。（０．２８２、０．６０６）に色度を合わせた。
＊４：露光量３０ｍＪ／ｃｍ^２で露光し、現像およびポストベーク（２２０℃×２０分）後の画素断面を走査型電子顕微鏡（Ｓ−４１００；（株）日立製作所製）を用いて観察した。（逆テーパー形状でない形状；○、逆テーパー形状；×）
＊５：評価に至らなかった；−
【００５１】
表２から、本発明の特定のビイミダゾール化合物および特定の溶剤の組み合わせを含む実施例１および２に記載の着色感光性樹脂組成物は、室温下での撹拌のみで均一な溶液を調製することができたことがわかる。これを用いてカラーフィルタを形成する際には未溶解物が異物としてカラーフィルタ上に残存することがないので、カラーフィルタの歩留まりおよび生産性を低下させることがない。一方、本発明における特定のビイミダゾール化合物および特定の溶剤の組み合わせを含まない比較例１の着色感光性樹脂組成物では、室温下での撹拌のみでは均一な着色感光性樹脂組成物が得られず、未溶解物が残存したので、この着色感光性樹脂組成物を用いてカラーフィルタを形成する際には未溶解物が異物としてカラーフィルタ上に残存し、カラーフィルタの歩留まりおよび生産性を低下させる可能性がある。
【００５２】
【表３】

【００５３】
【表４】

【００５４】
【発明の効果】
本発明の着色感光性樹脂組成物は、着色材料を高濃度で含有しても、感度に優れる。また、本発明の着色感光性樹脂組成物により得られる着色画素は、表面平滑性、パターン形状、および明度に優れる。したがって、本発明の着色感光性樹脂組成物を顔料分散レジストとして使用し、カラーフィルタを作製する場合、歩留まりおよび生産性を低下させることがなく、かつ高品質なカラーフィルタを得ることができる。
【図面の簡単な説明】
【図１】実施例１、実施例２および比較例１で用いた２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラフェニルビイミダゾールのＸ線回折図を示す。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a colored photosensitive resin composition suitable for a resist for forming a colored image (hereinafter, may be referred to as a pixel) used in a color liquid crystal display device, an imaging device, or the like.
[0002]
[Prior art]
2. Description of the Related Art A color filter in a color liquid crystal display device, an image sensor, or the like is usually manufactured by forming three primary color pixels of red, green, and blue on a substrate such as glass or a silicon wafer. Further, it is usual to provide a black matrix for shielding light between these pixels. Then, in order to form pixels of these colors, a resist solution containing a pigment corresponding to each color is uniformly applied by a spin coater on a substrate on which a light-shielding layer is patterned, and then heated and dried (prebaked). A method of exposing and developing the coating film is adopted, and an image of each color is obtained by repeating these operations for each color required for the color filter. As such a resist, a composition containing a photopolymerizable monomer and a photopolymerization initiator together with a pigment and a binder resin is often used. In addition, a resist containing a black pigment may be used for forming a black matrix.
[0003]
Since the photopolymerization initiator used in such a resist affects the properties and quality required for producing a color filter, those having high sensitivity, the surface smoothness of the produced color filter, the pattern shape and the resistance are high. Those with excellent chemical properties and those with high reliability are being studied. Examples thereof include a colored photosensitive resin composition using a triazine-based compound, a mixture of a triazine-based compound and an imidazole-based compound, and a mixture of a triazine-based compound, an imidazole-based compound, and an aminoacetophenone-based compound or benzophenone. (For example, see Patent Documents 1 to 3 and the like). Regarding further increase in sensitivity, a polyfunctional thiol compound, a mixture of at least one selected from biimidazole compounds, titanocene compounds, triazine compounds and oxadiazole compounds, 2-piperonyl-4,6-bis (trichloromethyl) -s- A triazine, and a mixture of the above triazine compound, a biimidazole compound, and a hydrogen donor have been proposed (see, for example, Patent Documents 4 and 5). The colored photosensitive resin composition containing these triazine-based compounds as a photopolymerization initiator component has the above-mentioned advantages, but as a disadvantage, it takes a long time to dissolve the biimidazole compound due to its low solubility in a solvent. In addition, there is a problem that undissolved components are easily generated as residues in the resist coating film.
[0004]
[Patent Document 1] JP-A-6-201913, page 2, left column, second line to line 5 [Patent Document 2] JP-A-6-324484, page 2 left column, second line to line 7 [Patent Document 3] Japanese Patent Application Laid-Open No. Hei 7-261014, page 2, left column, second line to line 7 [Patent Document 4] Japanese Patent Application Laid-Open No. Hei 10-253815, page 2, left column, second line to line 10 [Patent Document 5] No. 221675, page 2, left column, second line, line 29
[Problems to be solved by the invention]
An object of the present invention is to provide a colored photosensitive resin composition capable of preparing a highly sensitive colored photosensitive resin composition in a short time even if the coloring material is contained at a high concentration. Another object of the present invention is to provide a high-quality color filter having excellent surface smoothness, pattern shape, and brightness by using a colored pixel formed using the colored photosensitive resin composition.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to develop a new colored photosensitive resin composition that solves the above-mentioned problems, and as a result, a colored photosensitive resin composition obtained by combining a biimidazole compound having a specific crystal form with a specific solvent. The present inventors have found that an object can solve the above-mentioned problem, and have reached the present invention.
That is, the present invention comprises (A) a binder resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, (D) a coloring material, and (E) a solvent, and at least (C) a photopolymerization initiator. In a colored photosensitive resin composition containing a biimidazole compound and (E) an aliphatic cyclic ketone solvent and propylene glycol monoalkyl ether acetate as a solvent, the (1) powder X-ray diffraction pattern of the biimidazole compound is Cu- Kα characteristic X-ray diffraction has diffraction peaks at least in a range of 9.7 ° to 9.9 ° and a range of 10.0 ° to 10.2 ° in 2θ angle, and the aliphatic cyclic ketone solvent is A colored photosensitive resin composition which is at least one solvent selected from the group consisting of pentanone and cyclohexanone; Or applied on the layer formed of the solid content of the previously formed colored photosensitive resin composition, removing volatile components from the applied colored photosensitive resin composition layer, and exposing the layer through a photomask. The present invention also provides a method of forming a pattern to be developed, a color filter including the pattern formed by the above method, and a liquid crystal display device using the color filter.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[0008]
The colored photosensitive resin composition of the present invention is mainly used as a pigment-dispersed resist, and is usually a pigment (D) a coloring material, (A) a binder resin, (B) a photopolymerizable monomer, (C) As a photopolymerization initiator, (1) the powder X-ray diffraction pattern is in a range of at least 9.7 ° to 9.9 ° and 10.0 ° to 10.2 in 2θ angle of Cu-Kα characteristic X-ray diffraction. ° containing a biimidazole compound each having a diffraction peak in the range, each component is dissolved or dispersed in a solvent containing at least one solvent selected from the group consisting of cyclopentanone and cyclohexanone and a propylene glycol monoalkyl ether acetate Have been.
[0009]
(A) The binder resin has alkali solubility and acts as a dispersion medium for the coloring material. As the binder resin used in the present invention, a polymer containing a structural unit derived from an unsaturated carboxylic acid is preferable. As the binder resin, a resin obtained by copolymerizing an unsaturated carboxylic acid and another monomer copolymerizable therewith is more preferable.
[0010]
Specific examples of the structural unit derived from the unsaturated carboxylic acid include a structural unit derived from acrylic acid and a structural unit derived from methacrylic acid. Acrylic acid and methacrylic acid can be used alone or in combination. Further, in addition to these acrylic acid and methacrylic acid, at least one carboxylic acid selected from the group consisting of other unsaturated carboxylic acids and unsaturated carboxylic anhydrides such as crotonic acid, itaconic acid, maleic acid and fumaric acid. An acid can be used in combination. Further, a monomer containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid, can be used in combination.
[0011]
The binder resin used in the present invention is preferably a resin obtained from a structural unit derived from an unsaturated carboxylic acid as described above and a structural unit copolymerizable with the structural unit derived from the unsaturated carboxylic acid. As the constituent unit copolymerizable with the constituent unit derived from the unsaturated carboxylic acid, a constituent unit derived from an acrylate ester is preferably mentioned.
[0012]
Examples of the structural unit derived from an acrylate ester include an acrylate compound. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and 2-hydroxyethyl Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as (meth) acrylate and aminoethyl (meth) acrylate;
Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) ) Acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, tricyclodecyl (meth) acrylate, tricyclodecyloxyethyl (meth) acrylate , Adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pinenyl (meth) acrylate, dicyclope Esters including thenyl (meth) acrylate and alicyclic group of unsaturated carboxylic acids such as dicyclopentenyl oxyethyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Unsaturated carboxylic acid oxetane esters such as oxetane (meth) acrylate;
Examples include monosaturated carboxylic esters of glycols such as oligoethylene glycol monoalkyl (meth) acrylate, and preferred examples include methyl (meth) acrylate and benzyl (meth) acrylate.
[0013]
More preferably, in the above copolymer, another monomer copolymerizable with the unsaturated carboxylic acid and the acrylate ester can be used. Structural units derived from the other monomers include aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene;
Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;
Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;
And maleimide compounds such as N-phenylmaleimide.
These may be used alone or in combination of two or more in the production of the binder resin (A).
Further, if necessary, an unsaturated compound other than the acrylate ester may be used in combination.
[0014]
Among these other structural units, (meth) acrylic acid esters, especially unsubstituted or substituted alkyl esters of (meth) acrylic acid and esters containing alicyclic groups of (meth) acrylic acid are advantageously used.
[0015]
(A) In the binder resin, the structural unit derived from the unsaturated carboxylic acid is usually present in the range of 10 to 50% by mass, preferably 15 to 40% by mass of all the structural units of the copolymer. preferable. When the structural unit derived from the unsaturated carboxylic acid is from 10 to 50% by mass based on the above criteria, the solubility in the developing solution is sufficient, so that no residue is generated on the unexposed portion of the substrate. This is preferable because there is no tendency for the pixel portion of the exposed portion to be reduced in film thickness at the time of development and the whole pixel does not peel off.
[0016]
(A) The binder resin preferably has a weight average molecular weight in terms of polystyrene of from 10,000 to 100,000, more preferably from 15,000 to 50,000. (A) When the weight average molecular weight of the binder resin is in the range of 10,000 to 100,000, it is difficult to reduce the film thickness during development, and the non-pixel portion tends to have good removability during development. .
This (A) binder resin is contained in an amount of usually 5 to 90% by mass, preferably 10 to 70% by mass, based on the total solid content in the resist composition. (A) When the amount of the binder resin is 5 to 90% by mass based on the above-mentioned standard, the solubility in a developing solution is sufficient, and a development residue is hardly generated on a substrate in a non-pixel portion. This is preferable because film reduction of the pixel portion hardly occurs and the non-pixel portion tends to have good removability.
[0017]
The photopolymerizable monomer (B) contained in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described below. It can be a 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.
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, and bisphenol A. Bis (acryloyloxyethyl) ether, 3-methylpentanediol di (meth) acrylate, and the like.
Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate and the like. Among them, a bifunctional or higher polyfunctional monomer is preferably used.
(B) The photopolymerizable monomer is usually 1 to 60 parts by mass, preferably 5 to 5 parts by mass, based on 100 parts by mass of the total of (A) the binder resin and (B) the photopolymerizable monomer in the colored photosensitive resin composition. It is contained in the range of 50 parts by mass. (B) When the content of the photopolymerizable monomer is in the range of 1 to 60 parts by mass on the basis of the above, the strength and smoothness of the pixel portion tend to be good, which is preferable.
[0018]
Next, the (C) photopolymerization initiator contained in the colored photosensitive resin composition of the present invention comprises at least a (1) powder X-ray diffraction pattern of the (C) biimidazole compound whose Cu-Kα characteristic X-ray diffraction Biimidazole compounds having diffraction peaks in at least a range of 9.7 ° to 9.9 ° and a range of 10.0 ° to 10.2 ° at a 2θ angle are included. The colored photosensitive resin composition containing the above-mentioned biimidazole compound is preferable because it has high sensitivity and the surface formed by using the colored photosensitive resin composition has good surface smoothness.
In addition, when at least one of (2) an acetophenone compound, a triazine compound, a thiol compound and a compound represented by the formula (I) is contained in addition to (1), the obtained colored photosensitive resin composition has a higher performance. Sensitivity is preferred.
[0019]

(Wherein, R ^{1 to} R ⁸ each independently represent a hydrogen atom, a halogen, an alkyl group which may be substituted having 1 to 6 carbon atoms, or a substituted alkyl group which has 1 to 6 carbon atoms. good cycloalkyl group, an optionally substituted phenyl group having 1 to 6 carbon atoms, show an alkoxy group which may be substituted having 1 to 6 carbon atoms, X ^{is, -NR 9 -, - O -} , - Represents S-, and R ⁹ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.)
[0020]
Further, the use of (3) a photopolymerization initiation aid is preferable because the resulting colored photosensitive resin composition has higher sensitivity, and the productivity when forming a color filter using the same is improved.
[0021]
Examples of the biimidazole compound contained in the colored photosensitive resin composition of the present invention include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′- Bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5 5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxyphenyl) biimidazole, 4,4′5,5 '-Position phenyl group It includes such imidazole compounds which are substituted by Kokishi group, preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.
[0022]
(C) As a photopolymerization initiator, in addition to (1), at least one of (2) an acetophenone compound, a triazine compound, a thiol compound and a compound represented by the formula (I) can be further contained.
[0023]
As acetophenone compounds, diethoxyacetophenone,
2-hydroxy-2-methyl-1-phenylpropan-1-one,
Benzyl dimethyl ketal,
2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one,
1-hydroxycyclohexyl phenyl ketone,
2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one,
2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one,
Examples include oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and preferably 2-methyl-1- (4-methylthiophenyl) -2- Morpholinopropan-1-one,
2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one.
Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine,
2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine,
2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine,
2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine,
2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine,
2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine,
2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine,
2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like, preferably 2,4-bis (trichloromethyl)- 6-piperonyl-1,3,5-triazine,
2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine and the like.
As the thiol compound, a compound having a thiol group in the molecule is used. As the thiol compound having one thiol group, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, etc. Group polyfunctional thiol compounds are preferred. Examples of the aliphatic polyfunctional thiol used in the present invention include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bis Thioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis Thioglycolate, trishydroxyethyltristhiopropionate and, in addition to these, thioglycolate of polyhydric hydroxy compounds, thiopropionate, and the like, preferably Trimethylolpropane tris thiopropionate, trimethylolpropane tris thioglycolate and pentaerythritol tetrakis thiopropionate and the like, especially preferably pentaerythritol tetrakis thiopropionate.
Compounds represented by formula (I) include N-phenylglycine, phenoxyacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxy Examples thereof include phenylthioacetic acid, chlorophenylthioacetic acid, and dichlorophenylthioacetic acid, and preferably include dichlorophenylthioacetic acid and phenylthioacetic acid.
[0024]
Further, as long as the effects of the present invention are not impaired, a photopolymerization initiator generally used in this field can be used in combination. Examples of the photopolymerization initiator include benzoin-based, benzophenone-based, thioxanthone-based, anthracene-based, and other initiators. More specifically, the following compounds can be mentioned, and these can be used alone or in combination of two or more.
[0025]
(C) benzophenone-based benzophenone,
methyl o-benzoylbenzoate,
4-phenylbenzophenone,
4-benzoyl-4'-methyldiphenyl sulfide,
3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone,
2,4,6-trimethylbenzophenone and the like.
[0026]
(D) thioxanthone 2-isopropylthioxanthone,
4-isopropylthioxanthone,
2,4-diethylthioxanthone,
2,4-dichlorothioxanthone,
1-chloro-4-propoxythioxanthone and the like.
[0027]
(F) anthracene 9,10-dimethoxyanthracene,
2-ethyl-9,10-dimethoxyanthracene,
9,10-diethoxyanthracene,
2-ethyl-9,10-diethoxyanthracene and the like.
[0028]
(G) other 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
10-butyl-2-chloroacridone,
2-ethylanthraquinone,
Benzyl,
9,10-phenanthrenequinone,
Camphor quinone,
Methyl phenylglyoxylate,
Titanocene compounds and the like.
[0029]
Further, the photopolymerization initiator may be used in combination with (3) a photopolymerization initiation auxiliary agent. As the photopolymerization initiation aid, an amine compound is preferable, and the amine compound is more preferably an aromatic amine compound. Specific examples of the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. Isoamyl, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis And aromatic amine compounds such as (diethylamino) benzophenone.
[0030]
In the (C) photopolymerization initiator, the biimidazole compound is usually 0.1 to 40 parts by mass, preferably 1 to 30 parts by mass, based on 100 parts by mass of the total of (A) the binder resin and (B) the photopolymerizable monomer. Parts.
(2) When one or more of the acetophenone compound, the triazine compound, the thiol compound and the compound represented by the formula (I) are used, the total amount thereof is preferably 0.1 to 40 parts by mass based on the above criteria. , More preferably in the range of 1 to 30 parts by mass.
(3) The photopolymerization initiation aid is contained preferably in the range of 0.01 to 40 parts by mass, more preferably in the range of 0.1 to 30 parts by mass based on the above criteria.
In addition, the total amount of at least one of the biimidazole compound, the (2) acetophenone compound, the triazine compound, the thiol compound, and the compound represented by the formula (I) is usually 0.1% based on the aforementioned criteria. To 50 parts by mass, preferably 1 to 40 parts by mass. When the total amount of the compounds is within the above range, the colored photosensitive resin composition has high sensitivity, the strength of a pixel portion formed using the colored photosensitive resin composition, and the surface of the pixel. Is preferable because the smoothness tends to be good.
In addition to the amount of the biimidazole compound and (2) the amount of at least one of the acetophenone compound, the triazine compound, the thiol compound and the compound represented by the formula (I), (3) a photopolymerization initiation aid When the amount is within the above range, and when the total amount of (1) to (3) is within the above range, the sensitivity of the obtained colored photosensitive resin composition is further increased, and the above colored photosensitive resin is obtained. The productivity of a color filter formed using the composition tends to be improved, which is preferable.
[0031]
(D) The coloring material is usually a pigment, and may be an organic pigment or an inorganic pigment usually used for a pigment-dispersed resist. Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts.Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony metals Oxides or composite metal oxides are mentioned. Specific examples of the organic pigment include compounds classified as Pigment in the Color Index (published by The Society of Dysers and Colorists). More specifically, compounds having the following color index (CI) numbers are included, but are not limited thereto.
[0032]
C. I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166 and 173;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64 65 and 71;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242 and 254;
C. I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C. I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 22, 28, 60 and 64;
C. I. Pigment Green 7, 10, 15, 25, 36 and 47;
C. I. Pigment brown 28;
C. I. Pigment Black 1 and 7, and the like.
[0033]
These (D) coloring materials can be used alone or in combination of two or more. (D) The coloring material is used in an amount of usually 5 to 65% by mass, preferably 10 to 60% by mass, based on the total solid content in the colored photosensitive resin composition.
(D) When the content of the coloring material is in the range of 5 to 55 parts by mass on the basis of the above, the color density of the pixel is sufficient even if it is a thin film, and the removability of the non-pixel portion decreases during development. Therefore, there is a tendency that a residue hardly occurs, which is preferable.
[0034]
(E) As the solvent, propylene glycol monoalkyl ether acetate includes propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like. As the aliphatic cyclic ketone solvent, cyclopentane Nonone and cyclohexanone are preferred. Furthermore, other solvents can be used in combination as long as the effects of the present invention are not impaired. As other solvents, various solvents used in this field can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates, such as methyl cellosolve acetate and ethyl cellosolve acetate;
Alkylene glycol alkyl ether acetates such as methoxybutyl acetate and methoxypentyl acetate;
Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;
Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;
and cyclic esters such as γ-butyrolactone.
These other solvents that can be used in combination can be used alone or in combination of two or more.
The amount of the solvent (E) to be used is generally 60 to 90% by mass, preferably 70 to 85% by mass, based on the total amount of the colored photosensitive resin composition containing the solvent. When the content of the solvent (E) is in the range of 0.1 to 50 parts by mass on the basis of the above, coating properties tend to be good, which is preferable. Further, the amount of the aliphatic cyclic ketone solvent is 5 to 60% by mass, preferably 10 to 50% by mass in the total solvent. Within the above range, the colored photosensitive resin composition can be prepared in a short time.
[0035]
The colored photosensitive resin composition of the present invention may contain, if necessary, a filler, another polymer compound, a pigment dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomeration agent, and the like. Additives can be mixed and used.
Specific examples of the filler include glass, silica, and alumina, and specific examples of the other polymer compound include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. .
As the pigment dispersant, a commercially available pigment dispersant can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. Or a combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethylene imines In addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by Tochem Products), Megafax (manufactured by Dainippon Ink and Chemicals, Inc.) ), Florard (manufactured by Sumitomo 3M Ltd.), Asahi Guard, Surflon (above, manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Zeneca Corporation), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto Co., Ltd.) ).
Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples include ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.
Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the other polymer compound include a thermosetting resin such as an epoxy resin and a thermoplastic resin such as polyester and polyurethane.
Specific examples of the coagulant include sodium polyacrylate.
[0036]
The colored photosensitive resin composition of the present invention can be prepared, for example, as follows. That is, (D) the coloring material is previously mixed with the (E) solvent, and dispersed using a bead mill or the like until the coloring material has an average particle size of about 0.2 μm or less. At this time, a pigment dispersant is used as needed, and (A) a part or all of the binder resin may be blended. To the obtained dispersion (mill base), (A) the remaining binder resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator, other components used as needed, and further, if necessary, To obtain a desired colored photosensitive resin composition.
[0037]
The photosensitive resin composition thus prepared can be applied to a substrate as described below, and subjected to photocuring and development to form a black matrix or a colored image. First, the composition is spin-coated on a substrate (usually glass) and dried by heating (prebaking) to remove the solvent, thereby obtaining a smooth coating film. The thickness of the coating film at this time is about 1 to 3 μm. The coating film thus obtained is irradiated with ultraviolet rays through a target black matrix or a negative mask for forming an image. At this time, it is preferable to use a device such as a mask aligner so that the entire exposed portion is uniformly irradiated with parallel light beams and accurate alignment between the mask and the substrate is performed. Further, after this, the cured coating film is brought into contact with a dilute alkaline aqueous solution to dissolve and develop the non-exposed portions, thereby obtaining a desired black matrix or image. After development, post-curing (post-baking) at 150 to 230 [deg.] C. for about 10 to 60 minutes can be performed as necessary.
[0038]
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 mass, more preferably 0.03 to 5% by mass.
[0039]
The surfactant in the alkali developer may be any one of a nonionic surfactant, an anionic surfactant and a cationic 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 generally in the range of 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.
[0040]
Application of the colored photosensitive resin composition as described above, drying, patterning exposure to the obtained dried coating film, and through each operation of development, pixels or black corresponding to the color of the coloring material in the photosensitive resin composition A matrix is obtained, and these operations are repeated by the number of colors required for the color filter to obtain a color filter. That is, the color filter is usually a black matrix, and three primary color pixels of red, green and blue are arranged on the substrate, but using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a certain color. By performing the above operation, a black matrix or pixel of that color is obtained, and the same operation is performed using the colored photosensitive resin composition of the present invention containing a coloring material corresponding to a desired color also for other colors. To arrange the black matrix and the three primary color pixels on the substrate. Of course, the photosensitive resin composition of the present invention can be applied to only one, two or three of the black matrix and the three primary colors. In addition, since the black matrix which is the light-shielding layer may be formed of, for example, a chromium layer, it is not necessary to use the colored photosensitive resin composition of the present invention for forming the black matrix in this case.
[0041]
The color filter produced using the photosensitive solution of the present invention has a small in-plane film thickness difference, for example, a film thickness of 1 to 3 μm, an in-plane film thickness difference of 0.15 μm or less, and more preferably 0.1 μm or less. It can be not more than 05 μm. Therefore, the color filter thus obtained is excellent in smoothness and transparency, and by incorporating it into a color liquid crystal display device, a liquid crystal panel of excellent quality can be manufactured with a high yield.
[0042]
【Example】
Although the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the appended claims, and includes all modifications within the meaning and scope equivalent to the description of the claims. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, percentages and parts representing the content or the use amount are based on mass unless otherwise specified.
[0043]
Example 1
Among the components shown in Table 1, the total amount of each of the pigment and the polyester-based pigment dispersant was previously mixed with a partial amount of propylene glycol monomethyl ether acetate as a solvent, and the pigment was sufficiently dispersed using a bead mill. The remaining components including the remaining amount of propylene glycol monomethyl ether acetate were added thereto and mixed to obtain a colored photosensitive resin composition.
[0044]
[Table 1]

[0045]
Among the above components, the total amount of each of the pigment and the pigment dispersant is previously mixed in an amount such that propylene glycol monomethyl ether acetate, which is a solvent, is 80% by mass based on the total amount of the pigment and the pigment dispersant. 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole having a peak shown in the powder X-ray diffraction diagram of FIG. The description of peak 1 is shown in Tables 3 and 4.) and other components including the remaining amount of propylene glycol monomethyl ether acetate were added and mixed to obtain a colored photosensitive resin composition.
[0046]
A 2-inch square # 7059 glass substrate manufactured by Corning Incorporated was washed sequentially with a neutral detergent, water and alcohol, and then dried. The colored photosensitive resin composition prepared above (Table 1) was spin-coated on this glass substrate, and then prebaked at 100 ° C. for 3 minutes in a clean oven. After cooling, the distance between the resist-coated substrate and a quartz glass photomask (having a pattern in which the transmittance changes stepwise in the range of 1 to 100% and a line / space pattern from 1 μm to 50 μm) is set to 100 μm. Irradiation was carried out using an ultra-high pressure mercury lamp manufactured by Ushio Inc. at an exposure amount of 50 mJ / cm ^{2 in} an air atmosphere. Thereafter, the coating film is immersed in a water-based developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at room temperature for a predetermined time to be developed, washed with water, and post-baked at 220 ° C. for 30 minutes. Was done. The surface of the substrate after pre-baking, development and post-baking was observed, and the results for the following items are shown in Table 2.
[0047]
Example 2
The same operation as in Example 1 was performed, except that cyclohexanone was changed to cyclopentanone in Example 1.
Comparative Example 1
[0048]
Example 1 was repeated except that cyclohexanone was changed to propylene glycol monomethyl ether acetate, but a uniform colored photosensitive resin composition was not obtained.
[0049]
[Table 2]

[0050]
Explanation of the notes in the table * 1: When a uniform colored photosensitive resin composition can be prepared only by stirring at room temperature: ○, When a uniform colored photosensitive resin composition cannot be prepared only by stirring at room temperature: ×
* 2: Indicates the minimum exposure required to form a pattern without surface roughness even when developed.
* 3: The CIE chromaticity (x, y, Y) of the 2 degree field of view of the C light source of the coating film portion prepared without the development step was measured by a microspectrophotometer (OSP-SP200; manufactured by Olympus Sales Co., Ltd.). It was measured. At the same chromaticity (x, y), the larger the Y value, the higher the brightness. The chromaticity was adjusted to (0.282, 0.606).
* 4: Exposure was performed at an exposure amount of 30 mJ / cm ² , and the cross section of the pixel after development and post-baking (220 ° C. × 20 minutes) was observed using a scanning electron microscope (S-4100; manufactured by Hitachi, Ltd.). . (Shape without reverse taper shape; ○, reverse taper shape; ×)
* 5: Not evaluated;-
[0051]
From Table 2, the colored photosensitive resin compositions described in Examples 1 and 2 containing a specific biimidazole compound of the present invention and a specific solvent combination can be prepared into a uniform solution only by stirring at room temperature. It turns out that was completed. When a color filter is formed using this, undissolved matter does not remain as foreign matter on the color filter, so that the yield and productivity of the color filter are not reduced. On the other hand, in the colored photosensitive resin composition of Comparative Example 1 which does not contain the combination of the specific biimidazole compound and the specific solvent in the present invention, a uniform colored photosensitive resin composition cannot be obtained only by stirring at room temperature. When the color filter is formed using this colored photosensitive resin composition, the undissolved matter remains on the color filter as a foreign substance when the colored photosensitive resin composition is used, which reduces the yield and productivity of the color filter. there is a possibility.
[0052]
[Table 3]

[0053]
[Table 4]

[0054]
【The invention's effect】
The colored photosensitive resin composition of the present invention has excellent sensitivity even when a colored material is contained at a high concentration. Moreover, the colored pixel obtained by the colored photosensitive resin composition of the present invention is excellent in surface smoothness, pattern shape, and brightness. Therefore, when a colored filter is produced by using the colored photosensitive resin composition of the present invention as a pigment-dispersed resist, a high-quality color filter can be obtained without lowering the yield and productivity.
[Brief description of the drawings]
FIG. 1 is an X-ray diffraction diagram of 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole used in Example 1, Example 2 and Comparative Example 1. Show.

Claims (9)

(A) a binder resin,
(B) a photopolymerizable monomer,
(C) a photopolymerization initiator,
It contains (D) a coloring material and (E) a solvent, (C) contains at least a biimidazole compound as a photopolymerization initiator, and (E) contains an aliphatic cyclic ketone solvent and propylene glycol monoalkyl ether acetate as a solvent. In the colored photosensitive resin composition, the (1) powder X-ray diffraction pattern of the biimidazole compound is in a range of at least 9.7 ° to 9.9 ° and 10.0 ° to 2 ° angle of Cu-Kα characteristic X-ray diffraction. A colored photosensitive resin composition having a diffraction peak in the range of 10.2 °, and wherein the aliphatic cyclic ketone solvent is at least one solvent selected from the group consisting of cyclopentanone and cyclohexanone. The colored photosensitive resin composition according to claim 1, wherein the biimidazole compound is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole. (C) The photopolymerization initiator further comprises (2) at least one compound selected from the group consisting of an acetophenone compound, a triazine compound, a thiol compound and a compound represented by the formula (I). The colored photosensitive resin composition according to claim 1.

(Wherein, R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an optionally substituted alkyl group having 1 to 6 carbon atoms) cycloalkyl group, an optionally substituted phenyl group, an alkoxy group which may be substituted having 1 to 6 carbon atoms having 1 to 6 carbon atoms, X is, -NR 9 ^-, - O-, or - Represents S-, and R ⁹ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.) The colored photosensitive resin composition according to any one of claims 1 to 3, wherein (A) the binder resin is a polymer containing a structural unit derived from an unsaturated carboxylic acid. The colored photosensitive resin composition according to any one of claims 1 to 4, wherein (A) the binder resin is a copolymer containing a structural unit derived from an unsaturated carboxylic acid and a structural unit derived from a (meth) acrylate compound. object. The colored photosensitive resin composition according to any one of claims 1 to 5, further comprising (3) a photopolymerization initiation aid. The colored photosensitive resin composition according to any one of claims 1 to 6, which is applied on a substrate or a layer formed of a solid content of the colored photosensitive resin composition formed earlier, and volatilized from the applied colored photosensitive resin composition layer. A method for forming a pattern in which components are removed, the layer is exposed through a photomask, and developed. A color filter comprising a pattern formed by the method according to claim 7. A liquid crystal display device using the color filter according to claim 8.

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