JP4428880B2 - Coloring composition and photosensitive coloring composition - Google Patents

Description

【００４３】
〔式（Ａ）中、Ｖ₀ は−ＣＯＯ−、−ＯＣＯ−、−ＣＨ₂ ＯＣＯ−、−ＣＨ₂ ＣＯＯ−、−Ｏ−、−ＳＯ₂ −、−ＣＯ−、−ＣＯＮＨＣＯＯ−、−ＣＯＮＨＣＯＮＨ−、−ＣＯＮＨＳＯ₂ −、−ＣＯＮ（Ｐ₃ ）−、−ＳＯ₂ Ｎ（Ｐ₃ ）−又は−Ｃ₆ Ｈ₄ −を表わす（Ｐ₃ は、水素原子又は炭化水素基を表わす）。
ｃ₁ 、ｃ₂ は、互いに同じでも異なってもよく、水素原子、ハロゲン原子、シアノ基、炭化水素基、−ＣＯＯ−Ｚ′又は炭化水素を介した−ＣＯＯ−Ｚ′（Ｚ′は水素原子又は置換されてもよい炭化水素基を示す）を表わす。〕
【００４４】
【化２】

【００４５】
〔式（IIａ）又は（IIｂ）中、Ｖ₁ は、式（Ａ）中のＶ₀ と同義である。Ｑ₁ は、炭素数１〜１８個の脂肪族基又は炭素数６〜１２個の芳香族基を表わす。ｄ₁ 、ｄ₂ は、互いに同じでも異なってもよく、式（Ａ）中のｃ₁ 、ｃ₂ と同義である。Ｑ₀ は−ＣＮ又は−Ｃ₆ Ｈ₄ −Ｔを表わす。ここでＴは水素原子、ハロゲン原子、炭化水素基、アルコキシ基又は−ＣＯＯＺ″（Ｚ″はアルキル基、アラルキル基又はアリール基を示す）を表わす。〕
【００４６】
【化３】

【００４７】
〔式(III）中、Ｖ₂は、式（IIａ）中のＶ₁と同義である。Ｑ₂ は、式（IIａ）中のＱ₁ と同義である。ｅ₁ 、ｅ₂ は互いに同じでも異なってもよく、式（Ａ）中のｃ₁ 、ｃ₂ と同義である。〕
【００４８】
【化４】

【００４９】
〔式（IV）中、Ｒ₁ 、Ｒ₂ は各々同じでも異なってもよく、水素原子又は炭素数１〜１８個の置換されてもよい炭化水素基を表し、またＲ₁ とＲ₂ が、−Ｏ−、−Ｓ−、−ＮＲ₃ −（ここでＲ₃ は水素原子又は炭素数１〜１２個の炭化水素基を表す）を介して互いに結合して環を形成してもよい。〕
【００５０】
また、結着樹脂として、特開平１０−２０４９６号公報に記載の下記ポリマーも用いることができる。そのポリマーは、下記一般式（Ｋ）で示されるモノマーと少なくとも酸性基を有するモノマーとの共重合反応によって得られるポリマーである。
【００５１】
【化５】

【００５２】
式（Ｋ）中、Ｒは水素原子又はメチル基を表し、Ｒ₁ 〜Ｒ₅ は各々独立に水素原子、ハロゲン原子、シアノ基、アルキル基又はアリール基を表す。
【００５３】
上記結着樹脂は、好ましくは重量平均分子量が１×１０⁴ 以上の重合体が好ましく、より好ましくは重量平均分子量が２×１０⁴ 〜５×１０⁵ である。
上記結着樹脂の組成物中の使用量は、組成物中の全固形分に対して０．０１〜６０重量％が好ましく、より好ましくは０．５〜３０重量％である。
【００５４】
本発明の組成物を調製する際に使用する（Ｃ）溶剤としては、エステル類、例えば酢酸エチル、酢酸−ｎ−ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、アルキルエステル類、乳酸メチル、乳酸エチル、オキシ酢酸メチル、オキシ酢酸エチル、オキシ酢酸ブチル、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル、
【００５５】
３−オキシプロピオン酸メチル、３−オキシプロピオン酸エチルなどの３−オキシプロピオン酸アルキルエステル類；３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、２−オキシプロピオン酸メチル、２−オキシプロピオン酸エチル、２−オキシプロピオン酸プロピル、２−メトキシプロピオン酸メチル、２−メトキシプロピオン酸エチル、２−メトキシプロピオン酸プロピル、２−エトキシプロピオン酸メチル、２−エトキシプロピオン酸エチル、２−オキシ−２−メチルプロピオン酸メチル、２−オキシ−２−メチルプロピオン酸エチル、２−メトキシ−２−メチルプロピオン酸メチル、２−エトキシ−２−メチルプロピオン酸エチル、
【００５６】
ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２−オキソブタン酸メチル、２−オキソブタン酸エチル等；エーテル類、例えばジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、
【００５７】
プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート等；ケトン類、例えばメチルエチルケトン、シクロヘキサノン、２−ヘプタノン、３−ヘプタノン等；芳香族炭化水素類、例えばトルエン、キシレシ等が挙げられる。
【００５８】
これらのうち、３−エトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメテルエーテル、酢酸ブチル、３−メトキシプロピオン酸メチル、２−ヘプタノン、シクロヘキサノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテルアセテート等が好ましく用いられる。
溶剤は、通常、組成物全量中、２０〜９０重量％の範囲で添加される。
【００５９】
次に、（Ｄ）感放射線性組成物について説明する。
本発明の感放射線性組成物としては、重合性モノマーと光重合開始剤とから少なくとも構成される。
例えば、重合性モノマーとして、
（１）少なくとも１個の付加重合可能なエチレン基を有する、常圧下で１００℃以上の沸点を持つエチレン性不飽和基を持つ化合物、
光重合開始剤として、
（２）ハロメチルオキサジアゾール化合物、ハロメチル−ｓ−トリアジン化合物から選択された少なくとも一つの活性ハロゲン化合物、および３−アリール置換クマリン化合物、及びロフィン２量体
を挙げることができる。
【００６０】
（１）として、少なくとも１個の付加重合可能なエチレン性不飽和基をもち、沸点が常圧で１００℃以上の化合物としては、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、等の単官能のアクリレートやメタアクリレート；ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（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、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ヘキサ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイロキシエチル）イソシアヌレート、グリセリンやトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後（メタ）アクリレート化したもの、特公昭４８−４１７０８号、特公昭５０−６０３４号、特開昭５１−３７１９３号各公報に記載されているようなウレタンアクリレート類、特開昭４８−６４１８３号、特公昭４９−４３１９１号、特公昭５２−３０４９０号各公報に記載されているポリエステルアクリレート類、エポキシ樹脂と（メタ）アクリル酸の反応生成物であるエポキシアクリレート類等の多官能のアクリレートやメタアクリレートをあげることが出来る。更に、日本接着協会誌Ｖol．２０、Ｎo.７、３００〜３０８頁に光硬化性モノマー及びオリゴマーとして紹介されているものも使用できる。
また、下記一般式（Ｂ−１）あるいは（Ｂ−２）で示される化合物も使用することができる。
【００６１】
【化６】

【００６２】
（式（Ｂ−１）、（Ｂ−２）中、Ｂは、各々独立に、−（ＣＨ₂ＣＨ₂Ｏ）−および−（ＣＨ₂ＣＨ（ＣＨ₃）Ｏ）−のいずれかを表し；Ｘは、各々独立に、アクリロイル基、メタクリロイル基および水素原子のいずれかを表し、しかも、式（Ｂ−１）中、アクリロイル基およびメタクリロイル基の合計は５個または６個であり、式（Ｂ−２）中のそれは３個または４個であり；ｎは，各々独立に０〜６の整数を表し、しかも各ｎの合計は３〜２４であり；ｍは、各々独立に０〜６の整数を表し、しかも各ｍの合計は２〜１６である。）
【００６３】
これらの放射線重合性モノマーまたはオリゴマーは、本発明の組成物が放射線の照射を得て接着性を有する塗膜を形成し得るならば本発明の目的および効果を損なわない範囲で任意の割合で使用できる。使用量は感放射線性組成物の全固形分に対し５〜９０重量％、好ましくは１０〜５０重量％である。
【００６４】
（２）のハロメチルオキサジアゾールやハロメチル−ｓ−トリアジン等の活性ハロゲン化合物としては、特公昭５７−６０９６号公報に記載の下記一般式Ｉで示される２−ハロメチル−５−ビニル−１，３，４−オキサジアゾール化合物が挙げられる。
【００６５】
【化７】

【００６６】
ここでＷは、置換された又は無置換のアリール基を、Ｘは水素原子、アルキル基又はアリール基を、Ｙは弗素原子、塩素原子又は臭素原子を、ｎは１〜３の整数を表わす。
具体的な化合物としては、２−トリクロロメチル−５−スチリル−１，３，４−オキサジアゾール、２−トリクロロメチル−５−（ｐ−シアノスチリル）−１，３，４−オキサジアゾール、２−トリクロロメチル−５−（ｐ−メトキシスチリル）−１，３，４−オキサジアゾール等が挙げられる。
ハロメチル−ｓ−トリアジン系化合物の光重合開始剤としては、特公昭５９−１２８１号公報に記載の下記一般式IIに示されるビニル−ハロメチル−ｓ−トリアジン化合物、特開昭５３−１３３４２８号公報に記載の下記一般式IIIに示される２−（ナフト−１−イル）−４，６−ビス−ハロメチル−ｓ−トリアジン化合物及び下記一般式IVに示される４−（ｐ−アミノフェニル）−２，６−ジ−ハロメチル−ｓ−トリアジン化合物が挙げられる。
【００６７】
【化８】

【００６８】
ここでＱはＢｒ、Ｃｌを表し、Ｐは−ＣＱ₃ ，−ＮＨ₂ 、−ＮＨＲ、−Ｎ（Ｒ）₂ 、−ＯＲ（ただしＲはフェニル又はアルキル基）、Ｗは任意に置換された芳香族、複素環式核又は下記一般式IIＡで示されるものである。ここで、Ｚは−Ｏ−又は−Ｓ−である。
【００６９】
【化９】

【００７０】
一般式III 中、ＸはＢｒ、Ｃｌを表し、ｍ、ｎは０〜３の整数であり、Ｒは一般式III Ａで示される。Ｒ₁ はＨ又はＯＲ（Ｒはアルキル、シクロアルキル、アルケニル、アリール基）、Ｒ₂ はＣｌ、Ｂｒ、アルキル、アルケニル、アリール又はアルコキシ基を表す。
【００７１】
【化１０】

【００７２】
一般式ＩＶ中、Ｒ₁ 、Ｒ₂ は−Ｈ、アルキル基、置換アルキル基、アリール基、置換アリール基又は下記一般式IVＡ、IVＢで示される。Ｒ₃ 、Ｒ₄ は−Ｈ、ハロゲン原子、アルキル基、アルコキシ基を表す。
【００７３】
【化１１】

【００７４】
ここでＲ₅ 、Ｒ₆ 、Ｒ₇ は各々アルキル基、置換アルキル基、アリール基、置換アリール基を表す。置換アルキル基及び置換アリール基の例としては、フェニル基等のアリール基、ハロゲン原子、アルコキシ基、カルボアルコキシ基、カルボアリールオキシ基、アシル基、ニトロ基、ジアルキルアミノ基、スルホニル誘導体等が挙げられる。Ｘは−Ｃｌ，−Ｂｒを示し、ｍ、ｎは０、１又は２を表す。
【００７５】
Ｒ₁ とＲ₂ がそれと結合せる窒素原子と共に非金属原子からなる異節環を形成する場合、異節環としては下記に示されるものが挙げられる。
【００７６】
【化１２】

【００７７】
一般式IIの具体的な例としては、２，４−ビス（トリクロロメチル）−６−ｐ−メトキシスチリル−ｓ−トリアジン、２，４−ビス（トリクロロメチル）−６−（１−ｐ−ジメチルアミノフェニル−１，３−ブタジエニル）−ｓ−トリアジン、２−トリクロロメチル−４−アミノ−６−ｐ−メトキシスチリル−ｓ−トリアジン等が挙げられる。
【００７８】
一般式IIIの具体的な例としては、２−（ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（４−メトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（４−エトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（４−ブトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−〔４−（２−メトキシエチル）−ナフト−１−イル〕−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−〔４−（２−エトキシエチル）−ナフト−１−イル〕−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−〔４−（２−ブトキシエチル）−ナフト−１−イル〕−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（２−メトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（６−メトキシ−５−メチル−ナフト−２−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（６−メトキシ−ナフト−２−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（５−メトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（４，７−ジメトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（６−エトキシ−ナフト−２−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン、２−（４，５−ジメトキシ−ナフト−１−イル）−４，６−ビス−トリクロロメチル−ｓ−トリアジン等が挙げられる。
【００７９】
一般式IVの具体例としては、４−〔ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−メチル−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−メチル−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｐ−Ｎ，Ｎ−ジ（フェニル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｐ−Ｎ−クロロエチルカルボニルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｐ−Ｎ−（ｐ−メトキシフェニル）カルボニルアミノフェニル〕２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−ブロモ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−クロロ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−フロロ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−ブロモ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−クロロ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−フロロ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニルメチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−ブロモ−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｏ−クロロ−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、
【００８０】
４−〔ｏ−フロロ−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−ブロモ−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−クロロ−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−〔ｍ−フロロ−ｐ−Ｎ，Ｎ−ジ（クロロエチル）アミノフェニル〕−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｍ−ブロモ−ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｍ−クロロ−ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｍ−フロロ−ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｏ−ブロモ−ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｏ−クロロ−ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｏ−フロロ−ｐ−Ｎ−エトキシカルボニルメチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｍ−ブロモ−ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｍ−クロロ−ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｍ−フロロ−ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｏ−ブロモ−ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｏ−クロロ−ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、４−（ｏ−フロロ−ｐ−Ｎ−クロロエチルアミノフェニル）−２，６−ジ（トリクロロメチル）−ｓ−トリアジン、等が挙げられる。
【００８１】
これら開始剤には以下の増感剤を併用することができる。
その具体例として、ベンゾイン、ベンゾインメチルエーテル、ベンゾイン、９−フルオレノン、２−クロロ−９−フルオレノン、２−メチル−９−フルオレノン、９−アントロン、２−ブロモ−９−アントロン、２−エチル−９−アントロン、９，１０−アントラキノン、２−エチル−９，１０−アントラキノン、２−ｔ−ブチル−９，１０−アントラキノン、２，６−ジクロロ−９，１０−アントラキノン、キサントン、２−メチルキサントン、２−メトキシキサントン、２−メトキシキサントン、チオキサントン、ベンジル、ジベンザルアセトン、ｐ−（ジメチルアミノ）フェニルスチリルケトン、ｐ−（ジメチルアミノ）フェニル−ｐ−メチルスチリルケトン、ベンゾフェノン、ｐ−（ジメチルアミノ）ベンゾフェノン（またはミヒラーケトン）、ｐ−（ジエチルアミノ）ベンゾフェノン、ベンゾアントロン等や特公昭５１−４８５１６号公報記載のベンゾチアゾール系化合物が挙げられる。
【００８２】
３−アリール置換クマリン化合物は、下記一般式Ｖで示される化合物を指す。Ｒ₈は水素原子、炭素数１〜８個のアルキル基、炭素数６〜１０個のアリール基（好ましくは水素原子、メチル基、エチル基、プロピル基、ブチル基）を、Ｒ₉ は水素原子、炭素数１〜８個のアルキル基、炭素数６〜１０個のアリール基、下記一般式ＶＡで示される基（好ましくはメチル基、エチル基、プロピル基、ブチル基、一般式ＶＡで示される基、特に好ましくは一般式ＶＡで示される基）を表す。
Ｒ₁₀、Ｒ₁₁はそれぞれ水素原子、炭素数１〜８個のアルキル基（例えばメチル基、エチル基、プロピル基、ブチル基、オクチル基）、炭素数１〜８個のハロアルキル基（例えばクロロメチル基、フロロメチル基、トリフロロメチル基など）、炭素数１〜８個のアルコキシ基（例えばメトキシ基、エトキシ基、ブトキシ基）、置換されてもよい炭素数６〜１０個のアリール基（例えばフェニル基）、アミノ基、−Ｎ（Ｒ₁₆)(Ｒ₁₇）、ハロゲン（例えば−Ｃｌ、−Ｂｒ，−Ｆ）を表す。好ましくは水素原子、メチル基、エチル基、メトキシ基、フェニル基、−Ｎ（Ｒ₁₆)(Ｒ₁₇）、−Ｃｌである。
【００８３】
Ｒ₁₂は置換されてもよい炭素数６〜１６個のアリール基（例えばフェニル基、ナフチル基、トリル基、クミル基）を表す。置換基としてはアミノ基、−Ｎ（Ｒ₁₆)(Ｒ₁₇）、炭素数１〜８個のアルキル基（例えばメチル基、エチル基、プロピル基、ブチル基、オクチル基）、炭素数１〜８個のハロアルキル基（例えばクロロメチル基、フロロメチル基、トリフロロメチル基など）、炭素数１〜８個のアルコキシ基（例えばメトキシ基、エトキシ基、ブトキシ基）、ヒドロキシ基、シアノ基、ハロゲン（例えば−Ｃｌ、−Ｂｒ，−Ｆ）が挙げられる。
Ｒ₁₃、Ｒ₁₄、Ｒ₁₆、Ｒ₁₇はそれぞれ水素原子、炭素数１〜８個のアルキル基（例えばメチル基、エチル基、プロピル基、ブチル基、オクチル基）を表す。Ｒ₁₃とＲ₁₄及びＲ₁₆とＲ₁₇はまた互いに結合し窒素原子とともに複素環（例えばピペリジン環、ピペラジン環、モルホリン環、ピラゾール環、ジアゾール環、トリアゾール環、ベンゾトリアゾール環等）を形成してもよい。
Ｒ₁₅は水素原子、炭素数１〜８個のアルキル基（例えばメチル基、エチル基、プロピル基、ブチル基、オクチル基）、炭素数１〜８個のアルコキシ基（例えばメトキシ基、エトキシ基、ブトキシ基）、置換されてもよい炭素数６〜１０個のアリール基（例えばフェニル基）、アミノ基、−Ｎ（Ｒ₁₆)(Ｒ₁₇）、ハロゲン（例えば−Ｃｌ、−Ｂｒ，−Ｆ）を表す。
Ｚｂは＝Ｏ、＝Ｓあるいは＝Ｃ（Ｒ₁₈)(Ｒ₁₉）を表す。好ましくは＝Ｏ、＝Ｓ、＝Ｃ（ＣＮ)₂であり、特に好ましくは＝Ｏである。
Ｒ₁₈、Ｒ₁₉はそれぞれ、シアノ基、−ＣＯＯＲ₂₀、−ＣＯＲ₂₁を表す。Ｒ₂₀、Ｒ₂₁はそれぞれ炭素数１〜８個のアルキル基（例えばメチル基、エチル基、プロピル基、ブチル基、オクチル基）、炭素数１〜８個のハロアルキル基（例えばクロロメチル基、フロロメチル基、トリフロロメチル基など）、置換されてもよい炭素数６〜１０個のアリール基（例えばフェニル基）を表す。
【００８４】
特に好ましい３−アリール置換クマリン化合物は一般式VIで示される｛（ｓ−トリアジン−２−イル）アミノ｝−３−アリールクマリン化合物類である。
【００８５】
【化１３】

【００８６】
ロフィン二量体とは２個のロフィン残基からなる２，４，５−トリフェニルイミダゾリル二量体を意味し、その基本構造を下記に示す。
【００８７】
【化１４】

【００８８】
その具体例としては、２−（ｏ−クロルフェニル）−４，５−ジフェニルイミダゾリル二量体、２−（ｏ−フルオロフェニル）−４，５−ジフェニルイミダゾリル二量体、２−（ｏ−メトキシフェニル）−４，５−ジフェニルイミダゾリル二量体、２−（ｐ−メトキシフェニル）−４，５−ジフェニルイミダゾリル二量体、２−（ｐ−ジメトキシフェニル）−４，５−ジフェニルイミダゾリル二量体、２−（２，４−ジメトキシフェニル）−４，５−ジフェニルイミダゾリル二量体、２−（ｐ−メチルメルカプトフェニル）−４，５−ジフェニルイミダゾリル二量体等が挙げられる。
【００８９】
本発明において光重合開始剤としては、下記一般式（Ｃ）〜（Ｈ）、（Ｊ）も使用することができる。
【００９０】
【化１５】

【００９１】
式（Ｃ）〜（Ｈ）中、Ｒ₁ は各々独立に、水素原子、水酸基、炭素数１〜３個のアルキル基又はアルコキシ基を示し、Ｒ₂ 及びＲ₃ は、各々独立に水素原子又は炭素数１〜３個のアルコキシ基を示し、Ｒ₂ あるいはＲ₃ のいずれか一方はアルコキシ基であり、Ｒ₄ は水素原子、炭素数１〜３個のアルキル基又はアルコキシ基を示し、Ｒ₅ 及びＲ₆ は各々独立に炭素数１〜３個のアルキル基を示し、Ｒ₇ は水素原子、水酸基、炭素数１〜３個のアルキル基又はアルコキシ基を示す。Ｔは、下記式、
【００９２】
【化１６】

【００９３】
で示される基を示す。ｍは１〜３の整数、ｎは１〜４の整数を示す。
【００９４】
【化１７】

【００９５】
式（Ｊ）中、ｎは１または２であり、
Ａｒ₁ はｎが１のときフェニル基または塩素原子、臭素原子、ヒドロキシ基、−ＳＲ⁹ 、−Ｒ¹⁰、−ＯＲ¹⁰、−ＳＲ¹⁰、−ＳＯ₂Ｒ¹⁰、−Ｓ−フェニル、−Ｏ−フェニルもしくはモルホリノ基で置換されたフェニル基を表わし（Ｒ¹⁰は炭素原子数１ないし９のアルキル基を表す）、Ａｒ₁ はｎが２のとき、フェニレン−Ｔ−フェニレン基（Ｔは−Ｏ−、−Ｓ−または−ＣＨ₂ −を表わす）を表わす。Ｒ⁹ は水素原子、置換基を有していてもよい炭素原子数１ないし１２のアルキル基、炭素原子数３ないし６のアルケニル基、シクロヘキシル基、フェニルアルキル基、フェニルヒドロキシアルキル基、置換基を有していてもよいフェニル基、トリル基、−ＣＨ₂ −ＣＨ₂ ＯＨ、−ＣＨ₂ ＣＨ₂ −ＯＯＣ−ＣＨ＝ＣＨ₂ 、−ＣＨ₂ −ＣＯＯＲ¹¹（Ｒ¹¹は炭素原子数１ないし９のアルキル基を表す）、−ＣＨ₂ ＣＨ₂ −ＣＯＯＲ¹²（Ｒ¹²は炭素原子数１ないし４のアルキル基を表す）、
【００９６】
【化１８】

【００９７】
を表し、
Ｒ¹ 、Ｒ² は同じでも異なってもよく、−ＣＯＯＲ¹²（Ｒ¹²は前記と同義である）で置換されうる炭素原子数１ないし８のアルキル基、または炭素原子数７ないし９のフェニルアルキル基を表わし、またＲ¹ とＲ² は一緒になって炭素原子数４ないし６のアルキレン基を表わしてもよい、
Ｘはモルホリノ基、−Ｎ（Ｒ⁴ ）（Ｒ⁵ ）、−ＯＲ⁶ もしくは−Ｏ−Ｓｉ（Ｒ⁷)( Ｒ⁸ ）₂ を表わし、
Ｒ⁴、Ｒ⁵は同じでも異なってもよく、炭素原子数１ないし１２のアルキル基、−ＯＲ¹⁰で置換された炭素原子数２ないし４のアルキル基、またはアリル基を表わし、Ｒ⁴ とＲ⁵ は一緒になって、−Ｏ−、−ＮＨ−もしくは−Ｎ（Ｒ¹⁰）−を介していてもよい炭素原子数４ないし５のアルキレン基を表わし、
Ｒ⁶ は水素原子、炭素原子数１ないし１２のアルキル基、アリル基、または炭素原子数７ないし９のフェニルアルキル基を表わし、
Ｒ⁷ とＲ⁸ は同じでも異なってもよく、炭素原子数１ないし４のアルキル基またはフェニル基を表わす。
【００９８】
本発明では、以上の開始剤の他に他の公知のものも使用することができる。
米国特許第２，３６７，６６０号明細書に開示されているビシナールポリケトルアルドニル化合物、米国特許第２，３６７，６６１号および第２，３６７，６７０号明細書に開示されているα−カルボニル化合物、米国特許第２，４４８，８２８号明細書に開示されているアシロインエーテル、米国特許第２，７２２，５１２号明細書に開示されているα−炭化水素で置換された芳香族アシロイン化合物、米国特許第３，０４６，１２７号および第２，９５１，７５８号明細書に開示されている多核キノン化合物、米国特許第３，５４９，３６７号明細書に開示されているトリアリルイミダゾールダイマー／ｐ−アミノフェニルケトンの組合せ、特公昭５１−４８５１６号公報に開示されているベンゾチアゾール系化合物／トリハロメチール−ｓ−トリアジン系化合物。
【００９９】
開始剤の使用量はモノマー固形分に対し、０．０１重量％〜５０重量％、好ましくは１重量％〜２０重量％である。開始剤の使用量が０．０１重量％より少ないと重合が進み難く、また、５０重量％を超えると重合率は大きくなるが分子量が低くなり膜強度が弱くなる。
【０１００】
本発明の組成物には、必要に応じて各種添加物、例えば充填剤、上記以外の高分子化合物、界面活性剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することかできる。
【０１０１】
これらの添加物の具体例としては、ガラス、アルミナ等の充填剤；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等のバインダーポリマー（Ａ）以外の高分子化合物；ノニオン系、カチオン系、アニオン系等の界面活性剤；ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−クロロプロピルメチルジメトキシシラン、３−クロロプロピルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシラン等の密着促進剤；２，２−チオビス（４−メチル−６−ｔ−ブチルフェノール）、２，６−ジ−ｔ−ブチルフェノール等の酸化防止剤：２−（３−ｔ−ブチル−５−メチル−２−ヒドロキシフェニル）−５−クロロベンゾトリアゾール、アルコキシベンゾフェノン等の紫外線吸収剤；およびポリアクリル酸ナトリウム等の凝集防止剤を挙げることができる。
【０１０２】
また、放射線未照射部のアルカリ溶解性を促進し、本発明の組成物の現像性の更なる向上を図る場合には、本発明の組成物に有機カルボン酸、好ましくは分子量１０００以下の低分子量有機カルボン酸の添加を行うことができる。具体的には、例えばギ酸、酢酸、プロピオン酸、酪酸、吉草酸、ピバル酸、カプロン酸、ジエチル酢酸、エナント酸、カプリル酸等の脂肪族モノカルボン酸；シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ブラシル酸、メチルマロン酸、エチルマロン酸、ジメチルマロン酸、メチルコハク酸、テトラメチルコハク酸、シトラコン酸等の脂肪族ジカルボン酸；トリカルバリル酸、アコニット酸、カンホロン酸等の脂肪族トリカルボン酸；安息香酸、トルイル酸、クミン酸、ヘメリト酸、メシチレン酸等の芳香族モノカルボン酸；フタル酸、イソフタル酸、テレフタル酸、トリメリト酸、トリメシン酸、メロファン酸、ピロメリト酸等の芳香族ポリカルボン酸；フェニル酢酸、ヒドロアトロパ酸、ヒドロケイ皮酸、マンデル酸、フェニルコハク酸、アトロパ酸、ケイ皮酸、ケイ皮酸メチル、ケイ皮酸ベンジル、シンナミリデン酢酸、クマル酸、ウンベル酸等のその他のカルボン酸が挙げられる。
【０１０３】
本発明では必ずしも必要ではないが、顔料の分散性を向上させる分散剤を添加することができる。これらの分散剤としては、多くの種類の分散剤が用いられるが、例えば、フタロシアニン誘導体（市販品ＥＦＫＡ−７４５（森下産業製））；オルガノシロキサンポリマーＫＰ３４１（信越化学工業製）、（メタ）アクリル酸系（共）重合体ポリフローＮo.７５、Ｎo.９０、Ｎo.９５（共栄社油脂化学工業製）、Ｗ００１（裕商製）等のカチオン系界面活性剤；ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル等のノニオン系界面活性剤；エフトップＥＦ３０１、ＥＦ３０３、ＥＦ３５２（新秋田化成製）、メガファックＦ１７１、Ｆ１７２、Ｆ１７３（大日本インキ製）、フロラードＦＣ４３０、ＦＣ４３１（住友スリーエム製）、アサヒガードＡＧ７１０、サーフロンＳ３８２、ＳＣ−１０１、ＳＣ−１０２、ＳＣ−１０３、ＳＣ−１０４、ＳＣ−１０５、ＳＣ−１０６８（旭硝子製）等のフッ素系界面活性剤；Ｗ００４、Ｗ００５、Ｗ０１７（裕商製）等のアニオン系界面活性剤；ＥＦＫＡ−４６、ＥＦＫＡ−４７、ＥＦＫＡ−４７ＥＡ、ＥＦＫＡポリマー１００、ＥＦＫＡポリマー４００、ＥＦＫＡポリマー４０１、ＥＦＫＡポリマー４５０（以上森下産業製）、ディスパースエイド６、ディスパースエイド８、ディスパースエイド１５、ディスパースエイド９１００（サンノプコ製）等の高分子分散剤；ソルスパース３０００、５０００、９０００、１２０００、１３２４０、１３９４０、１７０００、２００００、２４０００、２６０００、２８０００などの各種ソルスパース分散剤（ゼネカ株式会社製）；その他イソネットＳ−２０（三洋化成製）が挙げられる。
【０１０４】
これらの分散剤は、単独で用いてもよくまた２種以上組み合わせて用いてもよい。このような分散剤は、顔料分散液中に、通常顔料１００重量部に対して０．１〜５０重量部の量で用いられる。
本発明の感放射線性組成物には以上の他に、更に、熱重合防止剤を加えておくことが好ましく、例えば、ハイドロキノン、ｐ−メトキシフェノール、ジ−ｔ−ブチル−ｐ−クレゾール、ピロガロール、ｔ−ブチルカテコール、ベンゾキノン、４，４′−チオビス（３−メチル−６−ｔ−ブチルフェノール）、２，２′−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２−メルカプトベンゾイミダゾール等が有用である。
【０１０５】
本発明に係わる着色組成物は、前記の（Ａ）顔料、（Ｂ）結着樹脂および（Ｃ）溶剤を含有するものであり、インクジェット用インキ、カラーフィルタ用インキとして使用することができる。
【０１０６】
本発明に係わる感光性着色組成物は、前記の（Ａ）顔料、（Ｂ）結着樹脂、（Ｃ）溶剤および（Ｄ）感放射線性組成物を含有するものであり、カラーフィルタを作製する際に使用することができる。
【０１０７】
本発明の感光性着色組成物は、基板に回転塗布、流延塗布、ロール塗布等の塗布方法により塗布して感光性組成物層を形成し、所定のマスクパターンを介して露光し、現像液で現像することによって、着色されたパターンを形成する。この際に使用される放射線としては、特にｇ線、ｉ線等の紫外線が好ましく用いられる。
【０１０８】
基板としては、例えば液晶表示素子等に用いられるソーダガラス、パイレックスガラス、石英ガラスおよびこれらに透明導電膜を付着させたものや、固体撮像素子等に用いられる光電変換素子基板、例えばシリコン基板等が挙げられる。これらの基板は、一般的には各画素を隔離するブラックストライプが形成されている。
【０１０９】
現像液としては、本発明の感光性着色組成物を溶解し、一方放射線照射部を溶解しない組成物であればいかなるものも用いることができる。具体的には種々の有機溶剤の組み合わせやアルカリ性の水溶液を用いることができる。
有機溶剤としては、本発明の組成物を調整する際に使用される前述の溶剤が挙げられる。
【０１１０】
アルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム，硅酸ナトリウム、メタ硅酸ナトリウム、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８−ジアザビシクロ−〔５，４，０〕−７−ウンデセン等のアルカリ性化合物を、濃度が０．００１〜１０重量％、好ましくは０．０１〜１重量％となるように溶解したアルカリ性水溶液が使用される。なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、一般に、現像後、水で洗浄する。
【０１１１】
【実施例】
以下、実施例及び比較例をあげて本発明を具体的に説明する。なお、文中、部とあるのは、重量部である。
分散液１
ＰＲ−２４２単独分散液の調製
・ＰＲ−２４２ １００部
・ベンジルメタクリレート／メタクリル酸／2-ヒドロキシエチルメタクリレート
（５０／２５／２５モル比、重量平均分子量（２０，０００） ５０部
・シクロヘキサノン ５０部
・プロピレングリコールモノメチルエーテルアセテート １５０部
を３本ロールミルで混練した。
得られた混練物を粉砕した後、顔料濃度が１３wt％になるよう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を加え、顔料分散剤としてディスパーエイド１６３（ビックケミー社製顔料分散剤）を顔料に対し１０ｗｔ％を添加しビーズミル（ダイノミル：シンマルエンタープライゼス社製分散機）で分散した。ここで得られた分散液を室内に３日放置した後の分散状況と遠心透過式による平均粒子径を測定した。表１に結果を示す。
【０１１２】
分散液２〜６
各種顔料の単独分散液の調製
ＰＲ−２４２を各種顔料に置き換え、分散剤をＥＦＫＡ−４６（ＥＦＫＡ社製顔料分散剤）にした以外は同様にして各種顔料の分散液を調製した。
上記と同様にして分散状況と平均粒子経を測定した。結果を表１に示す。
【０１１３】
【表１】

【０１１４】
○：分散直後と分散後の粘度変化が殆ど観察されない。粘度測定値の変化が２倍未満の変化
○△：分散直後と分散後の粘度変化が少ない。粘度測定値の変化が２倍から５倍未満の変化
×：分散直後と分散後の粘度変化が大きいか固まってしまう場合。粘度測定値の変化が５倍以上の変化
【０１１５】
実施例１
＜ソルトミリング＞
ＰＲ-２４２ ５０部、ＰＲ-２５４ ５０部、塩化ナトリウム１０００部、及びジエチレングリコール１５０部をニーダーに仕込、内容物温度を４０〜５０℃に保ちながら１０時間摩砕処理を行った。得られた内容物を７５℃に加温した２５００部の２．２％硫酸水溶液中に投入して２時間の撹拌処理を行った後、濾過、水洗をして塩化ナトリウム、ジエチレングリコールを除去し、更に７５℃の熱風乾燥機中で２０時間乾燥処理を加えることでＰＲ-２４２とＰＲ-２５４の混合顔料を得た。
【０１１６】
＜湿式分散＞
・上記混合顔料 １００部
・ベンジルメタクリレート／メタクリル酸／２-ヒドロキシエチルメタクリレート
（５０／２５／２５モル比、重量平均分子量（２０，０００） ７０部
・シクロヘキサノン １３０部
・プロピレングリコールモノメチルエーテルアセテート １４０部
を３本ロールミルで混練した。
【０１１７】
得られた混練物を粉砕した後、顔料濃度が１５wt％になるよう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を加え、顔料分散剤としてディスパーエイド１６３（ビックケミー社製顔料分散剤）およびＥＦＫＡ−４６（ＥＦＫＡ社製顔料分散剤）を顔料に対し各々１０ｗｔ％添加しビーズミル（ダイノミル：シンマルエンタープライゼス社製分散機）で分散して着色組成物を製造した。
ここで得られた着色組成物を室内に３日放置した後の分散状況と遠心透過式による平均粒子径を測定した。表２に結果を示す。
【０１１８】
実施例２〜９（但し、実施例４、６及び７は、参考例である。）
実施例１における顔料を表２に示した顔料に変更した以外は同様にして、混合顔料を分散させた着色組成物を製造した。得られた着色組成物の評価結果を表２に示す。
使用した顔料：
ＰＲ−２４２（ Sandorin Scarlet 4RF、クラリアント（Clariant）社製）
ＰＲ−２５４（CROMOPHTAL DPP Ｒｅｄ ＢＰ、チバ・スペシャルティー社製）
ＰＲ−１７７（Cromophtal Red A2B”、チバ・スペシャルティ・ケミカルズ社製）
ＰＹ−１３９（Paliotol Yellow D1819、 ビーエーエスエフ（BASF）社製）
ＰＹ−１５０（Bayplast Yellow 5GN01、BAYER社製）
ＰＹ−１３８（Paliotol Yellow D0960ビーエーエスエフ（BASF）社製）
【０１１９】
【表２】

【０１２０】
○：分散直後と分散後の粘度変化が殆ど観察されない。粘度測定値の変化が２倍未満の変化
○△：分散直後と分散後の粘度変化が少ない。粘度測定値の変化が２倍から５倍未満の変化
×：分散直後と分散後の粘度変化が大きいか固まってしまう場合。粘度測定値の変化が５倍以上の変化
【０１２１】
比較例１〜７
前記ＰＲ−２４２単独分散液（分散液１）と各種顔料単独分散液（分散液２〜６）とを単に混合した場合の結果を表３に示す。
【０１２２】
【表３】

【０１２３】
○：分散直後と分散後の粘度変化が殆ど観察されない。粘度測定値の変化が２倍未満の変化
○△：分散直後と分散後の粘度変化が少ない。粘度測定値の変化が２倍から５倍未満の変化
×：分散直後と分散後の粘度変化が大きいか固まってしまう場合。粘度測定値の変化が５倍以上の変化
【０１２４】
以上の結果から、ＰＲ−２４２と他の顔料を湿式分散時に共存させ分散を行うと、微細化分散が可能でかつ分散後の粘度変化が少ない分散液が調製できることが明らかである。
これに対して、ＰＲ−２４２の単独分散液と他の顔料の単独分散液を単に混合するだけでは、ＰＲ−２４２の分散の悪さに引きずられた結果しか得られない。
【０１２５】
実施例１０
実施例１の着色組成物を用いて、下記の感光性着色組成物を作製し、カラーフィルター用ガラス基板に膜厚が１．７μｍとなるように塗布した。２．５ｋｗの超高圧水銀灯を使用しマスクを通して１００ｍｊ／ｃｍ²の露光量で照射した後、０．２５重量％の炭酸ナトリウム水溶液で２５℃３０秒現像したところ、赤色顔料として、ＰＲ−２４２を使用することにより、明度の向上した赤画像を得ることができた。
【０１２６】
感光性着色組成物
・実施例１の着色組成物 ３００部
・ペンタエリスリトールテトラアクリレート ４０部
・４−｛ｏ−ブロモ−ｐ−Ｎ，Ｎ−ジ（エトキシカルボニル） ０．６部
アミノフェニル｝２，６−ジ（トリクロロメチル）−Ｓ−
トリアジン
・イルガキュア９０７ ０．８部
・ハイドロキノンモノメチルエーテル ０．０２部
・プロピレングリコールモノメチルエーテルアセテート １００部
【０１２７】
【発明の効果】
本発明に係わる着色組成物は、顔料が微細化されて安定に分散しており、粘度変化が少なく、明度が高いため、インクジェット用インキ及びカラーフィルター用感光性組成物として好適に用いることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a coloring composition such as an inkjet ink, and a photosensitive coloring composition suitable for producing a color filter used for a printing plate, a liquid crystal display element, a solid-state imaging element, and the like.
[0002]
[Prior art]
As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known. The dyeing method is a method for producing a color filter by dyeing a dyed substrate made of a natural resin such as gelatin, mulled or casein or a synthetic resin such as amine-modified polyvinyl alcohol with a dye such as an acid dye.
[0003]
In dyeing methods, there are problems with light resistance, heat resistance, moisture resistance, etc. due to the use of dyes, and it is difficult to uniformly control dyeing and fixing properties on a large screen, and color unevenness is likely to occur. At this time, there is a problem that a dye-resistant layer is required and the process is complicated. In the electrodeposition method, a transparent electrode is formed in a predetermined pattern in advance, and a color filter is formed by ionizing a resin containing a pigment dissolved or dispersed in a solvent and applying a voltage to form a colored image in a pattern. It is a manufacturing method.
[0004]
In the electrodeposition method, in addition to the transparent electrode for display, a photolitho process including film formation and an etching process of a transparent electrode for forming a color filter is necessary. In this case, if there is a short circuit, a line defect occurs and the yield decreases. In addition to the stripe arrangement, for example, it is difficult to apply to a mosaic arrangement, and it is difficult to manage the transparent electrode.
[0005]
The printing method is a simple method for producing a color filter by printing such as offset printing using an ink in which a pigment is dispersed in a thermosetting resin or an ultraviolet curable resin. However, since the usable ink has a high viscosity, filtering is difficult. In addition, defects due to dust, foreign matter, and gelled portions of the ink binder are likely to occur, and there are problems in positional accuracy, line width accuracy, and planar smoothness associated with printing accuracy.
[0006]
The pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. This method is stable to light and heat due to the use of pigments, and is patterned by the photolithographic method, so it is suitable for the production of color filters for large-screen, high-definition color displays with sufficient positional accuracy. is there.
[0007]
In order to produce a color filter by the pigment dispersion method, a radiation-sensitive composition is applied on a glass substrate with a spin coater or roll coater and dried to form a coating film, and the coating film is subjected to pattern exposure and development. A colored pixel is obtained, and this operation is performed for each color to obtain a color filter.
Examples of the pigment dispersion method include JP-A-1-102469, JP-A-1-152499, JP-A-2-181704, JP-A-2-199403, JP-A-4-76062, JP-A-5-73411, JP-A-5-73411. JP-A-6-184482 and JP-A-7-140654 disclose negative photosensitive compositions using a photopolymerizable monomer and a photopolymerization initiator as an alkali-soluble resin.
[0008]
However, in recent years, liquid crystal display elements have been required to have higher definition, lower power consumption of backlight, and higher luminance, and further increase in transmittance and contrast of color filters is desired.
[0009]
In JP-A-8-6242, as a new method that does not require pigment dispersion, after the molecularly dispersed pigment precursor is imaged, the pigment precursor is converted into a pigment by a chemical method, a thermal method, a photolytic method, or the like. Is disclosed (latent pigment). In this method, satisfactory results are not obtained because pigmentation performed by a chemical method, a thermal method, a photolytic method or the like is not sufficient. In particular, since the degree of pigmentation varies depending on the temperature, the color tone varies depending on the heating temperature. Accordingly, the heat resistance is not sufficient and it is not at a stage where it can be practically used.
[0010]
Conventionally, as described in JP-A-1-254918, JP-A-2-153353, etc., dianthraquinone pigments (PR-177 etc.) have been mainly used as red pigments. It was. However, even this pigment cannot meet the above-mentioned demands in recent years, and the transmittance does not increase even if it is finely dispersed.
As a new red pigment replacing PR-177, PR-254 described in JP-A-10-227911, JP-A-11-217514, and JP-A-11-231516 has been proposed. In the case of PR-254, although it was effective to increase the transmittance to some extent, it was not sufficient.
[0011]
In JP-A-11-14824, a red composition for a color filter containing PR-242 as a red main pigment which is yellowish from CI Pigment Red 177 and has a rising wavelength of transmission spectrum in the range of 530 to 560 nm. Has been proposed. In this case, although there is an effect in increasing the transmittance, it is difficult to disperse PR-242 and the actual situation is that it cannot be put into practical use as a coloring composition for a color filter.
[0012]
That is, PR-242 is very difficult to disperse in order to obtain a colored composition, and the obtained dispersion temporarily exhibits fluidity after dispersion, but immediately aggregates to increase viscosity and decrease fluidity. . This dispersion solidifies over time and does not exhibit the original fluidity, and the particle size increases significantly. Moreover, what is called thixotropy that flows when a force is applied even if it does not completely harden is set. Despite the addition of various dispersants and innovations in the dispersion method, satisfactory dispersions have not been obtained.
[0013]
Therefore, when a colored composition or a photosensitive colored composition using this dispersion is applied using a rotary coater (spinner), the uniformity of the coating film thickness is poor. In addition, the colored composition and the photosensitive colored composition change in viscosity with time or change in thixotropy, and even when applied under the same conditions, the same film thickness cannot be obtained. In particular, when used for a color filter, the uniformity of chromaticity on the same substrate is poor (in-plane variation is large), and the change in chromaticity for each substrate is large, so the problem is enormous and not practical.
[0014]
[Problems to be solved by the invention]
As a result of various attempts to stably disperse PR-242, the present inventor has found that dispersibility can be improved by simultaneously dispersing PR-242 and other pigments, thereby completing the present invention.
That is, in the present invention, PR-242 is used as a red pigment, and PR-242 and other pigments are dispersed simultaneously to disperse PR-242 finely and stably, with little change in viscosity and high brightness. It is in providing a composition and a photosensitive coloring composition.
[0015]
[Means for Solving the Problems]
  This invention solves the said subject, and has the following structures.
(1) In a colored composition containing (A) a pigment, (B) a binder resin, and (C) a solvent, (A) the pigment is C.I. I. Pigment Red 242 and one or more red pigments and / or yellow pigments.Mix and do salt milling at the same time,at the same timeWetThe average particle size of the pigment is dispersed.0.02-0.14 μmThe coloring composition characterized by being.
(2) In the photosensitive coloring composition containing (A) a pigment, (B) a binder resin, (C) a solvent, and (D) a radiation-sensitive composition, (A) the pigment is C.I. I. Pigment Red 242 and one or more red pigments and / or yellow pigments.Mix and do salt milling at the same time,at the same timeWetThe average particle size of the pigment is dispersed.0.02-0.14 μmThe photosensitive coloring composition characterized by the above-mentioned.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
(A) Pigment
The pigment used in the present invention is C.I. I. Pigment Red 242 (a pigment specified by a color index, hereinafter also referred to as PR-242) and one or more red pigments and / or yellow pigments are simultaneously dispersed, and an average particle size is 0.01. ~ 0.3 μm.
[0017]
In the present invention, C.I. I. Examples of the red pigment used in combination with Pigment Red 242 include C.I. I. Pigment Red 1-18, 21-23, 31, 32, 37, 38, 41, 48: 1 to 48: 5, 49, 49: 1 to 49: 3, 50: 1, 51: 1, 52: 1, 52: 2, 53, 53: 1, 53:-, 57: 1, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64, 64: 1, 66-68, 81: 1, 81: 3, 83: 1, 88-90, 95, 111, 112, 114, 117, 119, 122, 123, 136, 144, 146-151, 164, 166, 168-172, 175-179, 181, 184, 185, 187, 188, 190, 192, 194, 200, 202, 204, 206-214, 216, 220-224, 226, 237-240, 242, 243, 245, 247, 247: 1, 248, 25 1-258, 260-262, 264 etc. are mentioned.
Among these, C.I. I. Preferred red pigments used in combination with Pigment Red 242 include C.I. I. Pigment Red 5, 9, 10, 17, 21, 22, 48: 1, 48: 2, 48: 3, 48: 4, 52: 2, 89, 117, 119, 166, 177, 188, 190, 208, 209, 216, 224, 226, 254, 264 and the like.
[0018]
In the present invention, C.I. I. Examples of yellow pigments used in combination with Pigment Red 242 include C.I. I. Pigment Yellow 1, 2, 3, 5, 6, 10, 12, 13, 14, 16, 17, 24, 49, 55, 60, 61, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 104, 106, 108-111, 113, 114, 116, 117, 120, 121, 123, 124, 126-130, 133, 136, 138, 139, 147, 148, 150 to 155, 165 to 177, 179 to 183, 185, 187, 188, 190 to 194, etc. Among these, the light transmittance at 470 nm is 10%. In the following, a yellow pigment having a light transmittance at 535 nm of 80% or more is preferable. I. Pigment Yellow 93, 110, 129, 138, 150, 185 and the like.
[0019]
Examples of the combination of pigments include a combination of PR-242 and a red pigment, a combination of PR-242 and a yellow pigment, and a combination of PR-242, a red pigment, and a yellow pigment.
[0020]
The ratio (weight ratio) between PR-242 and other pigments may be 1: 9 to 9: 1, preferably 3: 7 to 7: 3.
[0021]
Examples of the method of simultaneously dispersing PR-242 and other pigments include a method of simultaneously dispersing during wet dispersion.
<Wet dispersion>
In the present invention, wet dispersion usually means mixing at least two pigments described above together with a solvent, a binder resin to be contained in the composition of the present invention, and other additives, and dispersing the pigment in the solvent. However, this includes the case where the pigment is mixed with at least a solvent and the pigment is dispersed in the solvent. In this case, other components are added and mixed after the wet dispersion. However, it is preferable to disperse the pigment by mixing it with at least a solvent and a binder resin.
[0022]
In the present invention, PR-242 can be finely and stably dispersed by simultaneously dispersing PR-242 and one or more red pigments and / or yellow pigments during wet dispersion.
[0023]
For wet dispersion, conventionally known kneaders, mixers, dispersers, and the like can be used. Examples thereof include a sand mill such as a homogenizer, a kneader, a ball mill, a two or three roll mill, a paint shaker, a sand grinder, and a dyno mill.
[0024]
As a preferred preparation method, first, a solvent is added to the pigment and the binder resin and mixed uniformly, and then kneaded while heating using two or three rolls as necessary to sufficiently blend the pigment and the binder resin. There is a method for obtaining a uniform colored body.
The kneading time may normally be several minutes to several hours.
Next, a solvent is added to the obtained colored product, and a dispersant and various additives are added as necessary, and dispersion is performed using various sand mills such as a dyno mill using a ball mill or glass beads as a dispersion medium. At this time, the smaller the diameter of the glass beads, the smaller the dispersion. At this time, a dispersion result with good reproducibility can be obtained by controlling the temperature of the dispersion liquid constant.
The dispersion obtained here can remove coarse particles by centrifugation or decantation as necessary.
[0025]
The colored dispersion containing the pigment thus obtained is mixed with a binder resin, a solvent, and a radiation sensitive compound, and used as a colored composition.
[0026]
<Salt milling>
Further, it is particularly preferable that the two or more pigment pigments (PR-242 and one or more red pigments and / or yellow pigments) described above are ground by salt milling before wet dispersion.
In salt milling, an organic pigment is mixed with a water-soluble inorganic salt and a water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt, and the mixture is mechanically kneaded and ground (hereinafter, this process is referred to as salt milling). After that, the pigment is refined by removing the water-soluble inorganic salt and the water-soluble organic solvent, and this is a method known as pigment refinement by pigment manufacturers and pigment processing manufacturers.
At the time of salt milling, a soluble resin that is dissolved or partially dissolved in a water-soluble organic solvent, a dispersant, or the like can be used in combination.
[0027]
The salt milling will be described in more detail. In this method, a small amount of a water-soluble organic solvent is added as a wetting agent to a mixture of an organic pigment and a water-soluble inorganic salt, and the mixture is kneaded strongly with a kneader or the like, and then the mixture is put into water. Then, the mixture is stirred with a homogenizer, a high speed mixer or the like to form a slurry. Next, the water-soluble inorganic salt and the water-soluble organic solvent are removed from the slurry by filtration, washing with water, and the like, and dried as necessary to obtain a finer pigment.
[0028]
Further, when the pigment particles are ground by salt milling, the ground surface is very active, and pigment crystals may grow depending on the pigment type or salt milling conditions. In order to suppress the crystal growth and advance the miniaturization, it is effective to use a material that is easily adsorbed on the active ground surface. Therefore, by using a soluble resin or dispersant that is at least partially soluble in the water-soluble organic solvent during salt milling, a treated pigment that is finer and has less aggregation of the pigment when dried can be obtained.
As the dispersant, a compound generally referred to as a pigment dispersant, for example, a surfactant, a pigment derivative, a resin-type dispersant, and the like can be used.
[0029]
Further, as a method for preventing pigment aggregation during drying, an alkali-soluble resin dissolved in an alkaline aqueous solution is added to the above slurry, and after sufficiently stirring and mixing, the alkali-soluble resin is neutralized with an acidic aqueous solution such as hydrochloric acid or sulfuric acid. It is also possible to prevent dry agglomeration by depositing in water or by adding an aqueous solution of a water-soluble polyvalent metal salt such as calcium chloride or barium chloride to precipitate an alkali-soluble resin and depositing it on the pigment.
[0030]
In the present invention, PR-242 can be finely and stably dispersed by simultaneously performing this salt milling by mixing PR-242 and another pigment.
[0031]
Although the water-soluble inorganic salt used for the said process will not be specifically limited if it is water-soluble, It is preferable to use salt (sodium chloride) from the point of cost. As for the ratio of the pigment to the water-soluble inorganic salt, if the ratio of the water-soluble inorganic salt is increased, the efficiency of miniaturization of the pigment is improved, but the productivity is lowered because the amount of the pigment is reduced. Therefore, in general, the water-soluble inorganic salt is used in an amount of 1 to 20 parts by weight, preferably about 2 to 10 parts by weight, based on 1 part by weight of the pigment.
[0032]
The wetting agent is added so that the pigment and the water-soluble inorganic salt are uniformly solidified. Depending on the blending ratio of the pigment and the water-soluble inorganic salt, it is usually 40% by weight to the pigment. An amount in the range of 400% by weight is used.
[0033]
The water-soluble organic solvent as the wetting agent is not particularly limited as long as it is water-soluble and does not dissolve the water-soluble inorganic salt. However, the temperature rises during salt milling, and the solvent easily evaporates. From this point, a high boiling point solvent is preferable. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene Glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low Molecular weight polypropylene glycol or the like is used.
[0034]
The soluble resin used in combination with the water-soluble organic solvent during salt milling is preferably solid at room temperature, insoluble in water, and at least partially soluble in the water-soluble organic solvent used as a wetting agent during salt milling Natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. In the case of a dried treated pigment, the soluble resin used is preferably solid at room temperature. However, when salt milling is performed using two or more kinds of resins in combination, even if a partially liquid resin is used and the mixture is solid at room temperature, no problem occurs even if the treated pigment is dried.
[0035]
The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.
[0036]
The colored composition of the present invention is not only used as an inkjet ink or a color filter ink, but also imparts photosensitivity to form a photosensitive colored composition (also referred to as a colored composition including the photosensitive colored composition). It can be used for manufacturing color filters. In other words, this is a method for producing a color filter by dispersing a pigment in a photopolymerizable or photocrosslinkable medium, pattern exposing, and removing the unexposed portion with a developer, and is widely used at present. However, when this method is used, a resin that is insoluble in the developer has an adverse effect on development, so this must be taken into consideration when selecting a soluble resin. Those that dissolve are preferred. In general, an alkaline developer is used as the developer. Therefore, as the soluble resin, it is preferable to use a (meth) acrylic resin, a rosin resin, a maleic acid resin, or the like containing (meth) acrylic acid soluble in alkali. However, even if it is an alkali-insoluble resin, if the amount is limited to 20% by weight or less, preferably 10% by weight or less in the nonvolatile content of the colored resist agent, the developability is not substantially affected.
[0037]
In the present invention, the average particle of the pigment (A) dispersed in the coloring composition by wet dispersion or salt milling and wet dispersionDiameterIs set to 0.01 to 0.3 μm, preferably 0.02 to 0.3 μm, and more preferably 0.02 to 0.2 μm.
The average particle size of the pigment can be measured by, for example, a centrifugal transmission particle size measuring device CAPA-700 (Horiba Seisakusho).
[0038]
(A) The pigment concentration in the total solid component of the coloring composition of the pigment is preferably 5% by weight to 80% by weight. If the film thickness is less than 5% by weight, the color purity cannot be improved unless the film thickness is 10 μm or more, which may cause a practical problem. If it exceeds 80% by weight, problems such as scumming of non-image areas and film residue may occur. Preferably it is 10 to 60% by weight.
[0039]
Next, (B) the binder resin will be described.
In the colored composition of the present invention, the following alkali-soluble resin and graft copolymer can be used as the binder resin.
These alkali-soluble binder resins are preferably linear organic high molecular polymers that are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048, There are maleic acid copolymers, partially esterified maleic acid copolymers and the like, and similarly there are acidic cellulose derivatives having a carboxylic acid in the side chain. In addition, a polymer in which an acid anhydride is added to a polymer having a hydroxyl group is also useful. Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are preferred. In addition, 2-hydroxyethyl methacrylate, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful as the water-soluble polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
[0040]
Further, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer described in JP-A-7-140654 / Benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Is also useful.
[0041]
In addition, as a binder resin and a pigment dispersant, a graft copolymer as described below described in JP-A-10-254133 can be used.
At least (1) the polymer main chain containing at least one of the polymer components represented by the following general formulas (IIa) and (IIb) is represented by the following general formula (A) only at one terminal. Weight average molecular weight 3 × 10 formed by bonding a polymerizable double bond group^FourThe following monofunctional macromonomer, (2) a monomer represented by the following general formula (III), (3) a quaternary ammonium salt monomer, and (4) an unsubstituted or substituted acid amide represented by the following general formula (IV) A copolymer comprising at least a monomer having at least one group in the molecule.
[0042]
[Chemical 1]

[0043]
[In formula (A), V₀Is —COO—, —OCO—, —CH₂OCO-, -CH₂COO-, -O-, -SO₂-, -CO-, -CONHCOO-, -CONHCONH-, -CONHSO₂-, -CON (P_Three)-, -SO₂N (P_Three)-Or -C₆H_Four-Represents (P_ThreeRepresents a hydrogen atom or a hydrocarbon group.
c₁, C₂May be the same or different from each other, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ', or -COO-Z' via a hydrocarbon (Z 'may be a hydrogen atom or substituted). Represents a good hydrocarbon group). ]
[0044]
[Chemical 2]

[0045]
[In formula (IIa) or (IIb), V₁Is V in the formula (A).₀It is synonymous with. Q₁Represents an aliphatic group having 1 to 18 carbon atoms or an aromatic group having 6 to 12 carbon atoms. d₁, D₂May be the same as or different from each other, and c in formula (A)₁, C₂It is synonymous with. Q₀Is -CN or -C₆H_FourRepresents -T. Here, T represents a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group or —COOZ ″ (Z ″ represents an alkyl group, an aralkyl group or an aryl group). ]
[0046]
[Chemical Formula 3]

[0047]
[In formula (III), V₂Is V in formula (IIa)₁It is synonymous with. Q₂Q in formula (IIa)₁It is synonymous with. e₁, E₂May be the same or different from each other, and c in formula (A)₁, C₂It is synonymous with. ]
[0048]
[Formula 4]

[0049]
[In formula (IV), R₁, R₂May be the same or different and each represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 18 carbon atoms;₁And R₂-O-, -S-, -NR_Three-(Where R_ThreeMay be bonded to each other via a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms to form a ring. ]
[0050]
In addition, as the binder resin, the following polymers described in JP-A-10-20496 can also be used. The polymer is a polymer obtained by a copolymerization reaction of a monomer represented by the following general formula (K) and a monomer having at least an acidic group.
[0051]
[Chemical formula 5]

[0052]
In the formula (K), R represents a hydrogen atom or a methyl group, and R₁~ R_FiveEach independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an aryl group.
[0053]
The binder resin preferably has a weight average molecular weight of 1 × 10.^FourThe above polymers are preferred, more preferably a weight average molecular weight of 2 × 10^Four~ 5x10^FiveIt is.
The amount of the binder resin used in the composition is preferably 0.01 to 60% by weight, more preferably 0.5 to 30% by weight, based on the total solid content in the composition.
[0054]
(C) The solvent used in preparing the composition of the present invention includes esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate and isopropyl butyrate. , Ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate,
[0055]
3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate , Ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionic acid ethyl,
[0056]
Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,
[0057]
Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; aromatic hydrocarbons such as toluene and xyle .
[0058]
Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used.
The solvent is usually added in the range of 20 to 90% by weight based on the total amount of the composition.
[0059]
Next, (D) a radiation sensitive composition is demonstrated.
The radiation sensitive composition of the present invention comprises at least a polymerizable monomer and a photopolymerization initiator.
For example, as a polymerizable monomer,
(1) a compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure, having at least one addition-polymerizable ethylene group;
As a photopolymerization initiator,
(2) at least one active halogen compound selected from a halomethyloxadiazole compound, a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, and a lophine dimer
Can be mentioned.
[0060]
As (1), as a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and then (meth) acrylate after addition of ethylene oxide or propylene oxide. Urethane acrylates as described in JP-A-50-6034 and JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid can be mentioned. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used.
Moreover, the compound shown by the following general formula (B-1) or (B-2) can also be used.
[0061]
[Chemical 6]

[0062]
(In formulas (B-1) and (B-2), each B is independently-(CH₂CH₂O)-and-(CH₂CH (CH_ThreeX) each independently represents an acryloyl group, a methacryloyl group or a hydrogen atom, and in formula (B-1), the total of the acryloyl group and the methacryloyl group is 5 Or n in the formula (B-2); each n independently represents an integer of 0 to 6, and the sum of each n is 3 to 24; Each m independently represents an integer of 0 to 6, and the total of each m is 2 to 16. )
[0063]
These radiation-polymerizable monomers or oligomers are used in any proportion within a range that does not impair the purpose and effect of the present invention, provided that the composition of the present invention can form a coating film having adhesiveness upon irradiation with radiation. it can. The amount used is 5 to 90% by weight, preferably 10 to 50% by weight, based on the total solid content of the radiation-sensitive composition.
[0064]
Examples of the active halogen compound (2) such as halomethyloxadiazole and halomethyl-s-triazine include 2-halomethyl-5-vinyl-1, which is represented by the following general formula I described in JP-B-57-6096. 3,4-oxadiazole compounds are mentioned.
[0065]
[Chemical 7]

[0066]
Here, W represents a substituted or unsubstituted aryl group, X represents a hydrogen atom, an alkyl group or an aryl group, Y represents a fluorine atom, a chlorine atom or a bromine atom, and n represents an integer of 1 to 3.
Specific compounds include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, And 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole.
As a photopolymerization initiator of a halomethyl-s-triazine compound, a vinyl-halomethyl-s-triazine compound represented by the following general formula II described in JP-B-59-1281, JP-A-53-133428, 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by the following general formula III and 4- (p-aminophenyl) -2 represented by the following general formula IV, A 6-di-halomethyl-s-triazine compound may be mentioned.
[0067]
[Chemical 8]

[0068]
Here, Q represents Br and Cl, and P represents -CQ._Three, -NH₂, -NHR, -N (R)₂, -OR (where R is a phenyl or alkyl group), W is an optionally substituted aromatic, heterocyclic nucleus or the following general formula IIA. Here, Z is —O— or —S—.
[0069]
[Chemical 9]

[0070]
In general formula III, X represents Br and Cl, m and n are integers of 0 to 3, and R is represented by general formula IIIA. R₁Is H or OR (R is an alkyl, cycloalkyl, alkenyl, aryl group), R₂Represents a Cl, Br, alkyl, alkenyl, aryl or alkoxy group.
[0071]
[Chemical Formula 10]

[0072]
In general formula IV, R₁, R₂Is represented by —H, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or the following general formulas IVA and IVB. R_Three, R_FourRepresents -H, a halogen atom, an alkyl group or an alkoxy group.
[0073]
Embedded image

[0074]
Where R_Five, R₆, R₇Each represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Examples of substituted alkyl groups and substituted aryl groups include aryl groups such as phenyl groups, halogen atoms, alkoxy groups, carboalkoxy groups, carboaryloxy groups, acyl groups, nitro groups, dialkylamino groups, sulfonyl derivatives, and the like. . X represents —Cl, —Br, and m and n represent 0, 1 or 2.
[0075]
R₁And R₂When a heterocycle consisting of a nonmetallic atom is formed together with a nitrogen atom to be bonded to it, examples of the heterocycle include those shown below.
[0076]
Embedded image

[0077]
Specific examples of general formula II include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethyl). And aminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like.
[0078]
Specific examples of general formula III include 2- (naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4, 6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) ) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [ 4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4, 6-bis-trichloromethyl-s-tri Gin, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6 -Bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy- Naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, etc. Can be mentioned.
[0079]
Specific examples of general formula IV include 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-p -N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p- N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s- Riazine, 4- [p-N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6 -Di (trichloromethyl) -s-triazine, 4- [p-N- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [m-N, N -Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2, 6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) ) -S-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo -PN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) Aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,
[0080]
4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di ( Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN -Ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxy) Carbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s- Triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloro) Ethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.
[0081]
The following sensitizers can be used in combination with these initiators.
Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) ) Benzophenone (or Mihira) Ketone), p- (diethylamino) benzophenone, benzothiazole compounds of benzanthrone like and Sho 51-48516 JP thereof.
[0082]
The 3-aryl substituted coumarin compound refers to a compound represented by the following general formula V. R₈Is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms (preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group), R₉Is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a group represented by the following general formula VA (preferably a methyl group, ethyl group, propyl group, butyl group, general formula VA A group represented by formula (VA), particularly preferably a group represented by the general formula VA).
R_Ten, R₁₁Are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), haloalkyl group having 1 to 8 carbon atoms (for example, chloromethyl group, fluoromethyl group, A trifluoromethyl group), an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, or a butoxy group), an aryl group having 6 to 10 carbon atoms that may be substituted (for example, a phenyl group), an amino group , -N (R₁₆) (R₁₇), Halogen (for example, -Cl, -Br, -F). Preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group, -N (R₁₆) (R₁₇), -Cl.
[0083]
R₁₂Represents an optionally substituted aryl group having 6 to 16 carbon atoms (for example, phenyl group, naphthyl group, tolyl group, cumyl group). As the substituent, an amino group, -N (R₁₆) (R₁₇), An alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), haloalkyl group having 1 to 8 carbon atoms (for example, chloromethyl group, fluoromethyl group, trifluoromethyl). Group), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group), hydroxy group, cyano group, and halogen (for example, -Cl, -Br, -F).
R₁₃, R₁₄, R₁₆, R₁₇Represents a hydrogen atom and an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group). R₁₃And R₁₄And R₁₆And R₁₇May combine with each other to form a heterocyclic ring (for example, a piperidine ring, a piperazine ring, a morpholine ring, a pyrazole ring, a diazole ring, a triazole ring, or a benzotriazole ring) together with a nitrogen atom.
R₁₅Is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy group, ethoxy group, butoxy group) ), An optionally substituted aryl group having 6 to 10 carbon atoms (for example, phenyl group), amino group, -N (R₁₆) (R₁₇), Halogen (for example, -Cl, -Br, -F).
Zb is = O, = S or = C (R₁₈) (R₁₉). Preferably = O, = S, = C (CN)₂And particularly preferably = O.
R₁₈, R₁₉Are each a cyano group, -COOR₂₀, -COR_{twenty one}Represents. R₂₀, R_{twenty one}Are each an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group), haloalkyl group having 1 to 8 carbon atoms (for example, chloromethyl group, fluoromethyl group, trifluoromethyl). Group), an aryl group having 6 to 10 carbon atoms (for example, a phenyl group) which may be substituted.
[0084]
Particularly preferred 3-aryl-substituted coumarin compounds are {(s-triazin-2-yl) amino} -3-arylcoumarin compounds represented by general formula VI.
[0085]
Embedded image

[0086]
The lophine dimer means a 2,4,5-triphenylimidazolyl dimer composed of two lophine residues, and its basic structure is shown below.
[0087]
Embedded image

[0088]
Specific examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxy). Phenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, and the like.
[0089]
In the present invention, the following general formulas (C) to (H) and (J) can also be used as the photopolymerization initiator.
[0090]
Embedded image

[0091]
In formulas (C) to (H), R₁Each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group;₂And R_ThreeEach independently represents a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms;₂Or R_ThreeAny one of these is an alkoxy group, and R_FourRepresents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, and R_FiveAnd R₆Each independently represents an alkyl group having 1 to 3 carbon atoms, R₇Represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group. T is the following formula:
[0092]
Embedded image

[0093]
The group shown by is shown. m represents an integer of 1 to 3, and n represents an integer of 1 to 4.
[0094]
Embedded image

[0095]
In formula (J), n is 1 or 2,
Ar₁Is a phenyl group, a chlorine atom, a bromine atom, a hydroxy group, or -SR when n is 1⁹, -R^Ten, -OR^Ten, -SR^Ten, -SO₂R^Ten, -S-phenyl, -O-phenyl or a phenyl group substituted with a morpholino group (R^TenRepresents an alkyl group having 1 to 9 carbon atoms), Ar₁When n is 2, phenylene-T-phenylene group (T is —O—, —S— or —CH₂Represents-). R⁹Has a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cyclohexyl group, a phenylalkyl group, a phenylhydroxyalkyl group, and a substituent. Optionally phenyl group, tolyl group, -CH₂-CH₂OH, -CH₂CH₂-OOC-CH = CH₂, -CH₂-COOR¹¹(R¹¹Represents an alkyl group having 1 to 9 carbon atoms), -CH₂CH₂-COOR¹²(R¹²Represents an alkyl group having 1 to 4 carbon atoms),
[0096]
Embedded image

[0097]
Represents
R¹, R²May be the same or different, -COOR¹²(R¹²Represents an alkyl group having 1 to 8 carbon atoms, or a phenylalkyl group having 7 to 9 carbon atoms, and R¹And R²Together may represent an alkylene group having 4 to 6 carbon atoms,
X is a morpholino group, -N (R^Four) (R^Five), -OR⁶Or -O-Si (R⁷) (R⁸)₂Represents
R^Four, R^FiveMay be the same or different, an alkyl group having 1 to 12 carbon atoms, -OR^TenRepresents an alkyl group having 2 to 4 carbon atoms or an allyl group substituted with^FourAnd R^FiveTogether, —O—, —NH— or —N (R^Ten)-Represents an optionally substituted alkylene group having 4 to 5 carbon atoms,
R⁶Represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group, or a phenylalkyl group having 7 to 9 carbon atoms;
R⁷And R⁸May be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.
[0098]
In the present invention, other known compounds can be used in addition to the above initiators.
Vicinal polykettle aldonyl compounds disclosed in US Pat. No. 2,367,660, α-disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, aromatic acyloin substituted with α-hydrocarbons disclosed in US Pat. No. 2,722,512 Compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, triallylimidazole dimers disclosed in US Pat. No. 3,549,367 / P-aminophenyl ketone combination, benzothiazole compound disclosed in Japanese Patent Publication No. 51-48516 / trihalomethyl- s-triazine compounds.
[0099]
The amount of the initiator used is 0.01% to 50% by weight, preferably 1% to 20% by weight, based on the monomer solid content. When the amount of the initiator used is less than 0.01% by weight, the polymerization is difficult to proceed, and when it exceeds 50% by weight, the polymerization rate increases but the molecular weight decreases and the film strength decreases.
[0100]
In the composition of the present invention, various additives such as fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like are blended as necessary. I can do it.
[0101]
Specific examples of these additives include fillers such as glass and alumina; polymer compounds other than the binder polymer (A) such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; , Cationic and anionic surfactants; 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- Epoxy cyclohexyl) Adhesion promoters such as titrimethylsilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4 -Methyl-6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, UV absorbers such as alkoxybenzophenone; and anti-aggregation agents such as sodium polyacrylate.
[0102]
In addition, when promoting the alkali solubility in the unirradiated part and further improving the developability of the composition of the present invention, the composition of the present invention is an organic carboxylic acid, preferably a low molecular weight having a molecular weight of 1000 or less. An organic carboxylic acid can be added. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.
[0103]
In the present invention, a dispersant that improves the dispersibility of the pigment can be added, although this is not always necessary. As these dispersants, many types of dispersants are used. For example, phthalocyanine derivatives (commercially available products EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic Cationic surfactants such as acid-based (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho); polyoxyethylene lauryl ether, polyoxyethylene Nonionic surfactants such as stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; F-top EF301, E 303, EF352 (manufactured by Shin-Akita Kasei), Megafac F171, F172, F173 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC-101, SC-102, SC -103, SC-104, SC-105, SC-1068 (manufactured by Asahi Glass); fluorine-based surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA-46, EFKA- 47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by Sannopco) ) Polymer Powders; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 20000, 24000, 26000, 28000, and other various Solsperse dispersants (manufactured by Geneca Co., Ltd.); and other Isonet S-20 (manufactured by Sanyo Kasei). .
[0104]
These dispersants may be used alone or in combination of two or more. Such a dispersant is usually used in the pigment dispersion in an amount of 0.1 to 50 parts by weight with respect to 100 parts by weight of the pigment.
In addition to the above, it is preferable to add a thermal polymerization inhibitor in addition to the above, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, etc. Useful.
[0105]
The colored composition according to the present invention contains the above-mentioned (A) pigment, (B) binder resin, and (C) solvent, and can be used as ink for inkjet and color filter.
[0106]
The photosensitive coloring composition according to the present invention contains the (A) pigment, (B) binder resin, (C) solvent, and (D) radiation-sensitive composition, and produces a color filter. Can be used when.
[0107]
The photosensitive coloring composition of the present invention is applied to a substrate by a coating method such as spin coating, casting coating, roll coating or the like to form a photosensitive composition layer, exposed through a predetermined mask pattern, and a developer. A colored pattern is formed by developing with. As radiation used at this time, ultraviolet rays such as g-line and i-line are particularly preferably used.
[0108]
Examples of the substrate include soda glass, pyrex glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, and photoelectric conversion element substrates used for solid-state imaging elements such as silicon substrates. Can be mentioned. These substrates are generally formed with black stripes that isolate pixels.
[0109]
Any developer can be used as long as it dissolves the photosensitive coloring composition of the present invention and does not dissolve the radiation irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
Examples of the organic solvent include the aforementioned solvents used in preparing the composition of the present invention.
[0110]
Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Alkaline compounds such as pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are added so that the concentration is 0.001 to 10% by weight, preferably 0.01 to 1% by weight. A dissolved alkaline aqueous solution is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.
[0111]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In the text, “part” means “part by weight”.
Dispersion 1
Preparation of PR-242 single dispersion
・ PR-242 100 parts
・ Benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate
(50/25/25 molar ratio, weight average molecular weight (20,000) 50 parts
・ 50 parts of cyclohexanone
・ Propylene glycol monomethyl ether acetate 150 parts
Was kneaded with a three-roll mill.
After the obtained kneaded material is pulverized, propylene glycol monomethyl ether acetate is added so that the pigment concentration is 13 wt%, and Disperse 163 (Pig Dispersant manufactured by Big Chemie) is added as a pigment dispersant to the pigment at 10 wt%. The dispersion was carried out using a bead mill (Dynomill: Disperser manufactured by Shinmaru Enterprises). The dispersion obtained after leaving the dispersion in a room for 3 days and the average particle size by centrifugal permeation were measured. Table 1 shows the results.
[0112]
Dispersions 2-6
Preparation of single dispersion of various pigments
Various pigment dispersions were prepared in the same manner except that PR-242 was replaced with various pigments and the dispersant was changed to EFKA-46 (pigment dispersant manufactured by EFKA).
The dispersion state and the average particle size were measured in the same manner as described above. The results are shown in Table 1.
[0113]
[Table 1]

[0114]
○: Almost no change in viscosity immediately after dispersion and after dispersion. Change in viscosity measured value is less than double
○ △: Little change in viscosity immediately after dispersion and after dispersion. Change in viscosity measurement from 2 to less than 5 times
X: The viscosity change immediately after dispersion and after dispersion is large or hardened. Viscosity measurement value change more than 5 times change
[0115]
Example 1
<Salt milling>
50 parts of PR-242, 50 parts of PR-254, 1000 parts of sodium chloride, and 150 parts of diethylene glycol were charged into a kneader, and milled for 10 hours while maintaining the temperature of the content at 40 to 50 ° C. The obtained contents were put into 2500 parts of 2.2% sulfuric acid aqueous solution heated to 75 ° C. and stirred for 2 hours, followed by filtration and washing to remove sodium chloride and diethylene glycol. Furthermore, a mixed pigment of PR-242 and PR-254 was obtained by adding a drying treatment in a hot air dryer at 75 ° C. for 20 hours.
[0116]
<Wet dispersion>
・ 100 parts of the above mixed pigment
・ Benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate
(50/25/25 molar ratio, weight average molecular weight (20,000) 70 parts
・ Cyclohexanone 130 parts
・ 140 parts of propylene glycol monomethyl ether acetate
Was kneaded with a three-roll mill.
[0117]
After the obtained kneaded material was pulverized, propylene glycol monomethyl ether acetate was added so that the pigment concentration was 15 wt%, and Disperseid 163 (a pigment dispersant manufactured by Big Chemie) and EFKA-46 (manufactured by EFKA) were used as pigment dispersants. A pigment composition was added to each pigment in an amount of 10 wt% and dispersed with a bead mill (Dynomill: Disperser manufactured by Shinmaru Enterprises) to produce a colored composition.
The dispersion state after the colored composition obtained here was left in the room for 3 days and the average particle diameter by the centrifugal permeation method were measured. Table 2 shows the results.
[0118]
  Examples 2-9(However, Examples 4, 6 and 7 are reference examples.)
  A colored composition in which the mixed pigment was dispersed was produced in the same manner except that the pigment in Example 1 was changed to the pigment shown in Table 2. The evaluation results of the obtained colored composition are shown in Table 2.
  Used pigments:
PR-242 (Sandorin Scarlet 4RF, manufactured by Clariant)
PR-254 (CROMOPHTAL DPP Red BP, manufactured by Ciba Specialty)
PR-177 (Cromophtal Red A2B ", manufactured by Ciba Specialty Chemicals)
PY-139 (Paliotol Yellow D1819, manufactured by BASF)
PY-150 (Bayplast Yellow 5GN01, manufactured by BAYER)
PY-138 (Paliotol Yellow D0960 manufactured by BASF)
[0119]
[Table 2]

[0120]
○: Almost no change in viscosity immediately after dispersion and after dispersion. Change in viscosity measured value is less than double
○ △: Little change in viscosity immediately after dispersion and after dispersion. Change in viscosity measurement from 2 to less than 5 times
X: The viscosity change immediately after dispersion and after dispersion is large or hardened. Viscosity measurement value change more than 5 times change
[0121]
Comparative Examples 1-7
Table 3 shows the results when the PR-242 single dispersion (dispersion 1) and various pigment single dispersions (dispersions 2 to 6) are simply mixed.
[0122]
[Table 3]

[0123]
○: Almost no change in viscosity immediately after dispersion and after dispersion. Change in viscosity measured value is less than double
○ △: Little change in viscosity immediately after dispersion and after dispersion. Change in viscosity measurement from 2 to less than 5 times
X: The viscosity change immediately after dispersion and after dispersion is large or hardened. Viscosity measurement value change more than 5 times change
[0124]
From the above results, it is apparent that when PR-242 and other pigments are coexisted during wet dispersion and dispersion is performed, a dispersion capable of being finely dispersed and having little change in viscosity after dispersion can be prepared.
On the other hand, if the PR-242 single dispersion and the other pigment single dispersion are simply mixed, only the result dragged by the poor dispersion of PR-242 is obtained.
[0125]
Example 10
The following photosensitive coloring composition was produced using the coloring composition of Example 1, and it apply | coated to the glass substrate for color filters so that a film thickness might be set to 1.7 micrometers. 100mj / cm through a mask using 2.5kw ultra high pressure mercury lamp²After being irradiated with an exposure amount of 0.25 wt.% And developed with a 0.25 wt% sodium carbonate aqueous solution at 25 ° C. for 30 seconds, a red image with improved brightness can be obtained by using PR-242 as a red pigment. It was.
[0126]
Photosensitive coloring composition
-300 parts of the colored composition of Example 1
・ Pentaerythritol tetraacrylate 40 parts
4- {o-bromo-pN, N-di (ethoxycarbonyl) 0.6 parts
Aminophenyl} 2,6-di (trichloromethyl) -S-
Triazine
・ Irgacure 907 0.8 parts
Hydroquinone monomethyl ether 0.02 part
・ Propylene glycol monomethyl ether acetate 100 parts
[0127]
【The invention's effect】
The colored composition according to the present invention can be suitably used as a photosensitive composition for ink-jet inks and color filters because the pigment is finely dispersed and stably dispersed, has little viscosity change, and has high brightness. .

Claims (2)

In the coloring composition containing (A) a pigment, (B) a binder resin, and (C) a solvent, (A) the pigment is C.I. I. Pigment Red 242 and one or more red pigments and / or yellow pigments are mixed and simultaneously subjected to salt milling and wet dispersed at the same time, and the average particle size of the pigment is 0.02 to 0.14 μm. A coloring composition characterized by the above. In the photosensitive coloring composition containing (A) a pigment, (B) a binder resin, (C) a solvent, and (D) a radiation-sensitive composition, (A) the pigment is C.I. I. Pigment Red 242 and one or more red pigments and / or yellow pigments are mixed and simultaneously subjected to salt milling and wet dispersed at the same time, and the average particle size of the pigment is 0.02 to 0.14 μm. The photosensitive coloring composition characterized by these.