JP2004037986A - Radiation sensitive composition for color filter, color filter and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive composition for a color filter with excellent surface smoothness and adhesion of pixels and excellent developability. <P>SOLUTION: The radiation sensitive resin composition for the color filter contains (A) pigment, (B) alkali soluble resin, (C) polyfunctional monomer, (D) a radiation sensitive polymerization initiator and (E) a solvent, wherein (A) the pigment is dispersed in a solution composed by dissolving a part or all of (B) the alkali soluble resin in a part or all of (E) the solvent beforehand, and wherein (B) the alkali soluble resin used when dispersing the pigment beforehand contains the alkali soluble resin having a group -NR<SB>2</SB>(where each R indicates mutually independently hydrogen atoms, 1-18C alkyl group, 2-18C alkenyl group, 2-18C alkynyl group, allyl group or 6-18C aryl group). <P>COPYRIGHT: (C)2004,JPO

Description

【００７３】
、下記式（２）で表される化合物
【化２】

【００７４】
等が好ましく、特に、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレートおよびジペンタエリスリトールヘキサアクリレートが、画素強度が高く、画素の表面平滑性に優れ、かつ未露光部の基板上および遮光層上に地汚れ、膜残り等を発生し難い点で好ましい。
前記多官能性単量体は、単独でまたは２種以上を混合して使用することができる。
【００７５】
また、本発明においては、場合により、前記多官能性単量体と共に、単官能性単量体を併用することもできる。
このような単官能性単量体の具体例としては、前記アミノ基含有アルカリ可溶性樹脂（Ｉ）〜（ＩＩＩ）について例示したアミノ基含有エチレン性不飽和単量体、カルボキシル基を有するエチレン性不飽和単量体、Ｎ位−置換マレイミドやその他の共重合可能なエチレン性不飽和単量体のほか、商品名で、Ｍ−５３００、Ｍ−５４００（商品名、東亞合成（株）製）等を挙げることができる。
これらの単官能性単量体は、単独でまたは２種以上を混合して使用することができる。
単官能性単量体の使用割合は、多官能性単量体と単官能性単量体との合計に対して、通常、９０重量％以下、好ましくは５０重量％以下である。この場合、単官能性単量体の使用割合が９０重量％を超えると、得られる画素の強度や表面平滑性が不十分となるおそれがある。
【００７６】
本発明における多官能性単量体と単官能性単量体との合計使用量は、（Ｂ）成分１００重量部に対して、通常、５〜５００重量部、好ましくは２０〜３００重量部である。この場合、前記合計使用量が５重量部未満では、画素の強度や表面平滑性が低下する傾向があり、一方５００重量部を超えると、例えば、アルカリ現像性が低下したり、未露光部の基板上あるいは遮光層上に地汚れ、膜残り等が発生しやすくなる傾向がある。
【００７７】
（Ｄ）光重合開始剤
本発明における光重合開始剤とは、可視光線、紫外線、遠紫外線、電子線、Ｘ線等の露光により分解または結合の開裂を生じ、ラジカル、カチオン、アニオン等の前記（Ｃ）多官能性単量体の重合を開始することができる活性種を発生する化合物を意味する。
このような光重合開始剤としては、ビイミダゾール系化合物、ベンゾイン系化合物、アセトフェノン系化合物、ベンゾフェノン系化合物、α−ジケトン系化合物、多核キノン系化合物、キサントン系化合物、トリアジン系化合物等を挙げることができる。
【００７８】
前記ビイミダゾール系化合物の具体例としては、２，２’−ビス（２−クロロフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、２，２’−ビス（２−ブロモフェニル）−４，４’，５，５’−テトラキス（４−エトキシカルボニルフェニル）−１，２’−ビイミダゾール、２，２’−ビス（２，４−ジクロロフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、２，２’−ビス（２，４，６−トリクロロフェニル）−４，４’，５，５’−テトラフェニル−１，
２’−ビイミダゾール、２，２’−ビス（２，４−ジブロモフェニル）−４，
４’，５，５’−テトラフェニル−１，２’−ビイミダゾール、２，２’−ビス（２，４，６−トリブロモフェニル）−４，４’，５，５’−テトラフェニル−１，２’−ビイミダゾール等を挙げることができる。
これらのビイミダゾール系化合物は、溶剤に対する溶解性に優れ、未溶解物、析出物等の異物を生じることがなく、しかも感度が高く、少ないエネルギー量の露光により硬化反応を十分進行させるとともに、コントラストが高く、未露光部で硬化反応が生じることがないため、露光後の塗膜は、現像液に対して不溶性の硬化部分と、現像液に対して高い溶解性を有する未硬化部分とに明確に区分され、これにより、アンダーカットのない画素パターンが所定の配列に従って配置された高精細な画素アレイを形成することができる。
【００７９】
また、前記ベンゾイン系化合物の具体例としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインｉ−プロピルエーテル、ベンゾインｉ−ブチルエーテル、メチル−２−ベンゾイルベンゾエート等を挙げることができる。
また、前記アセトフェノン系化合物の具体例としては、２，２−ジメトキシ−２−フェニルアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−（４−ｉ−プロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、２，２−ジメトキシアセトフェノン、２，２−ジエトキシアセトフェノン、２−メチル−（４−メチルチオフェニル）−２−モルフォリノ−１−プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン等を挙げることができる。
【００８０】
また、前記ベンゾフェノン系化合物の具体例としては、４，４’−ビス（ジメチルアミノ）ベンゾフェノン、４，４’−ビス（ジエチルアミノ）ベンゾフェノン等を挙げることができる。
また、前記α−ジケトン系化合物の具体例としては、ジアセチル、ジベンゾイル、メチルベンゾイルホルメート等を挙げることができる。
また、前記多核キノン系化合物の具体例としては、アントラキノン、２−エチルアントラキノン、２−ｔ−ブチルアントラキノン、１，４−ナフトキノン等を挙げることができる。
また、前記キサントン系化合物の具体例としては、キサントン、チオキサントン、２−クロロチオキサントン等を挙げることができる。
【００８１】
さらに、前記トリアジン系化合物の具体例としては、１，３，５−トリス（トリクロロメチル）−ｓ−トリアジン、１，３−ビス（トリクロロメチル）−５−（２−クロロフェニル）−ｓ−トリアジン、１，３−ビス（トリクロロメチル）−５−（４−クロロフェニル）−ｓ−トリアジン、１，３−ビス（トリクロロメチル）−５−（２−メトキシフェニル）−ｓ−トリアジン、１，３−ビス（トリクロロメチル）−５−（４−メトキシフェニル）−ｓ−トリアジン、２−（２−フリルエチリデン）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（４−メトキシスチリル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（３，４−ジメトキシスチリル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（４−メトキシナフチル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（２−ブロモ−４−メチルフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（２−チオフェニルエチリデン）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン等を挙げることができる。
【００８２】
前記光重合開始剤は、単独でまたは２種以上を混合して使用することができる。
本発明における光重合開始剤の使用量は、（Ｃ）多官能性単量体と場合により使用される多官能性単量体の合計１００重量部に対して、通常、０．０１〜２００重量部、好ましくは１〜１２０重量部、さらに好ましくは１〜１００重量部である。この場合、光重合開始剤の使用量が０．０１重量部未満では、露光による硬化が不十分となり、画素パターンが所定の配列に従って配置された画素アレイを得ることが困難となるおそれがあり、一方２００重量部を超えると、形成された画素が現像時に基板から脱落しやすくなり、また未露光部の基板上あるいは遮光層上に地汚れ、膜残り等を生じやすくなる。
さらに、本発明においては、前記光重合開始剤と共に、必要に応じて、増感剤、硬化促進剤や高分子光架橋・増感剤等の１種以上を併用することもできる。
【００８３】
（Ｅ）溶媒
本発明における溶媒は、感放射線性組成物を構成する前記（Ａ）〜（Ｄ）成分や後述する添加剤成分を分散または溶解し、かつこれらの成分と反応せず、適度の揮発性を有するものである限り、特に限定されるものではないが、その例としては、
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−ｎ−プロピルエーテル、エチレングリコールモノ−ｎ−ブチルエーテル、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−ｎ−プロピルエーテル、ジエチレングリコールモノ−ｎ−ブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ−ｎ−プロピルエーテル、プロピレングリコールモノ−ｎ−ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノ−ｎ−プロピルエーテル、ジプロピレングリコールモノ−ｎ−ブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル等の（ポリ）アルキレングリコールモノアルキルエーテル類；
エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチ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等の（ポリ）アルキレングリコールモノアルキルエーテルアセテート類；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メチルエチルエーテル、ジエチレングリコールジエチルエーテル、テトラヒドロフラン等の他のエーテル類；
【００８４】
メチルエチルケトン、シクロヘキサノン、２−ヘプタノン、３−ヘプタノン等のケトン類；
２−ヒドロキシプロピオン酸メチル、２−ヒドロキシプロピオン酸エチル等の乳酸アルキルエステル類；
２−ヒドロキシ−２−メチルプロピオン酸エチル、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、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２−ヒドロキシ−３−メチルブタン酸メチル、３−メチル−３−メトキシブチルアセテート、３−メチル−３−メトキシブチルプロピオネート、酢酸エチル、酢酸ｎ−プロピル、酢酸ｉ−プロピル、酢酸ｎ−ブチル、酢酸ｉ−ブチル、ぎ酸ｎ−アミル、酢酸ｉ−アミル、プロピオン酸ｎ−ブチル、酪酸エチル、酪酸ｎ−プロピル、酪酸ｉ−プロピル、酪酸ｎ−ブチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸ｎ−プロピル、アセト酢酸メチル、アセト酢酸エチル、２−オキソブタン酸エチル等の他のエステル類；
トルエン、キシレン等の芳香族炭化水素類；
Ｎ−メチルピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド類
等を挙げることができる。
【００８５】
これらの溶媒のうち、溶解性、顔料分散性、塗布性等の観点から、エチ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メチルエーテル、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、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メチルエチルエーテル、シクロヘキサノン、２−ヘプタノン、３−ヘプタノン、２−ヒドロキシプロピオン酸エチル、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、３−メチル−３−メトキシブチルプロピオネート、酢酸ｎ−ブチル、酢酸ｉ−ブチル、ぎ酸ｎ−アミル、酢酸ｉ−アミル、プロピオン酸ｎ−ブチル、酪酸エチル、酪酸ｉ−プロピル、酪酸ｎ−ブチル、ピルビン酸エチル等が好ましい。
前記溶媒は、単独でまたは２種以上を混合して使用することができる。
【００８６】
さらに、前記溶媒と共に、ベンジルエチルエーテル、ジヘキシルエーテル、アセトニルアセトン、イソホロン、カプロン酸、カプリル酸、１−オクタノール、１−ノナノール、ベンジルアルコール、酢酸ベンジル、安息香酸エチル、しゅう酸ジエチル、マレイン酸ジエチル、γ−ブチロラクトン、炭酸エチレン、炭酸プロピレン、エチレングリコールモノフェニルエーテルアセテート等の高沸点溶媒を併用することもできる。
これらの高沸点溶媒のうち、γ−ブチロラクトン等が好ましい。
前記高沸点溶媒は、単独でまたは２種以上を混合して使用することができる。
【００８７】
本発明における溶媒の使用量は、特に限定されるものではないが、得られる感放射線性組成物の塗布性、安定性等の観点から、当該組成物の溶媒を除いた各成分の合計濃度が、通常、５〜５０重量％、好ましくは１０〜４０重量％となる量が望ましい。
【００８８】
添加剤
本発明のカラーフィルタ用感放射線性組成物は、必要に応じて、種々の添加剤を含有することもできる。
前記添加剤としては、カラーフィルタ用感放射線性組成物のアルカリ現像液に対する溶解性をより改善し、かつ現像後の未溶解物の残存をより抑制する作用を示す有機酸を挙げることができる。
このような有機酸としては、分子中に１個以上のカルボキシル基を有する、脂肪族カルボン酸あるいはフェニル基含有カルボン酸が好ましい。
【００８９】
前記脂肪族カルボン酸としては、例えば、
ぎ酸、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、カプリル酸等のモノカルボン酸類；
しゅう酸、マロン酸、こはく酸、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、メチルこはく酸、テトラメチルこはく酸、シクロヘキサンジカルボン酸、イタコン酸、シトラコン酸、マレイン酸、フマル酸、メサコン酸等のジカルボン酸類；
トリカルバリル酸、アコニット酸、カンホロン酸等のトリカルボン酸類
等を挙げることができる。
【００９０】
また、前記フェニル基含有カルボン酸としては、カルボキシル基が直接フェニル基に結合した芳香族カルボン酸や、カルボキシル基が炭素鎖を介してフェニル基に結合したカルボン酸等を挙げることができ、それらの例としては、
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類；
フタル酸、イソフタル酸、テレフタル酸等の芳香族ジカルボン酸類；
トリメリット酸、トリメシン酸、メロファン酸、ピロメリット酸等の３価以上の芳香族ポリカルボン酸類や、
フェニル酢酸、ヒドロアトロパ酸、ヒドロけい皮酸、マンデル酸、フェニルこはく酸、アトロパ酸、けい皮酸、シンナミリデン酸、クマル酸、ウンベル酸
等を挙げることができる。
【００９１】
これらの有機酸のうち、マロン酸、アジピン酸、イタコン酸、シトラコン酸、フマル酸、メサコン酸、フタル酸等の脂肪族ジカルボン酸類および芳香族ジカルボン酸類が、アルカリ溶解性、後述する溶媒に対する溶解性、未露光部の基板上あるいは遮光層上における地汚れや膜残りの防止等の観点から好ましい。
前記有機酸は、単独でまたは２種以上を混合して使用することができる。
有機酸の使用量は、感放射線性組成物全体に対して、通常、１０重量％以下、好ましくは５重量％以下、さらに好ましくは１重量％以下である。この場合、有機酸の使用量が１０重量％を超えると、形成された画素の基板に対する密着性が低下する傾向がある。
【００９２】
また、前記有機酸以外の添加剤の具体例としては、
銅フタロシアニン誘導体等の青色顔料誘導体や黄色顔料誘導体等の分散助剤；
ガラス、アルミナ等の充填剤；
ポリビニルアルコール、ポリエチレングリコールモノアルキルエーテル類、ポリ（フロロアルキルアクリレート）類等の高分子化合物；
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類等の紫外線吸収剤；
ポリアクリル酸ナトリウム等の凝集防止剤；
エポキシ化合物、メラミン化合物、ビスアジド化合物等の熱架橋剤
等を挙げることができる。
【００９３】
本発明のカラーフィルタ用感放射線性組成物は、前記課題として挙げた画素の表面平滑性、密着性および現像性を本質的に解決できるものである。
画素の表面平滑性は、下記数式（１）
【００９４】
【数１】

〔但し、Ｒａ　は画素の中心線に沿う平均粗度（Å）、Ｌは測定長さ、ｙは画素の中心線から粗度曲線までの距離（Å）、ｘは測定長さ方向における位置座標である。〕
で定義されるＲａ値により評価することができる。
【００９５】
Ｒａ値の上限は、従来では５０Å程度で十分とされていたが、現在では３０Å以下とすることが求められている。
本発明のカラーフィルタ用感放射線性組成物を用いることにより、画素のＲａ値を、通常、３０Å以下、好ましくは２０Å以下とすることが可能となり、▲１▼画素と液晶との接触面積が大きくなることによる着色層から液晶への不純物の滲み出し、▲２▼画素表面の荒れによる液晶の配向不良等の悪影響等を極めて適切に抑制でき、焼き付けや表示ムラなどの表示不良を生じることがなく、極めて高品質のカラー液晶表示素子等を得ることができる。
【００９６】
カラーフィルタ用感放射線性組成物の調製方法
本発明のカラーフィルタ用感放射線性組成物は、前述したようにして、（Ａ）顔料を予め（Ｂ）アミノ基含有アルカリ可溶性樹脂を含有するアルカリ可溶性樹脂の一部または全部が（Ｅ）溶媒の一部または全部に溶解してなる溶液中に分散させ、得られた顔料分散液を、（Ｃ）多官能性単量体および（Ｄ）光重合開始剤と共に、必要に応じて（Ｂ）アルカリ可溶性樹脂の残部および（Ｅ）溶媒の残部を添加して、混合することによって調製することができる。
顔料分散工程後の各成分の混合方法は、特に限定されるものではなく、常法により実施することができる。
【００９７】
カラーフィルタの形成方法
次に、本発明のカラーフィルタ用感放射線性組成物を用いて、カラーフィルタを形成する方法について説明する。
基板の表面上に、必要に応じて、画素を形成する部分を区画するように遮光層を形成し、この基板上に、例えば赤色の顔料が分散された感放射線性組成物の液状組成物を塗布したのち、プレベークを行って溶剤を蒸発させ、塗膜を形成する。次いで、この塗膜にフォトマスクを介して放射線を露光したのち、アルカリ現像液を用いて現像して、塗膜の未露光部を溶解除去し、その後ポストベークすることにより、赤色の画素パターンが所定の配列で配置された画素アレイを形成する。
また、緑色または青色の顔料が分散された各感放射線性組成物の液状組成物を用い、前記と同様にして、各液状組成物の塗布、プレベーク、露光および現像を行い、その後ポストベークを行って、緑色の画素アレイおよび青色の画素アレイを同一基板上に形成することにより、赤色、緑色および青色の三原色の画素アレイが基板上に配置されたカラーフィルタを得る。但し、カラーフィルタを形成する際の各色の画素パターンの形成順序は、前記に限定されるものではない。
【００９８】
カラーフィルタを形成する際に使用される基板としては、例えば、ガラス、シリコン、ポリカーボネート、ポリエステル、芳香族ポリアミド、ポリアミドイミド、ポリイミド等を挙げることができる。これらの基板には、所望により、シランカップリング剤等による薬品処理、プラズマ処理、イオンプレーティング、スパッタリング、気相反応法、真空蒸着等の適宜の前処理を施しておくこともできる。
感放射線性組成物の液状組成物を基板に塗布する際には、回転塗布、流延塗布、ロール塗布等の適宜の塗布法を採用することができる。
塗布厚さは、乾燥後の膜厚として、通常、０．１〜１０μｍ、好ましくは０．２〜５．０μｍ、特に好ましくは０．２〜３．０μｍである。
カラーフィルタを作製する際に使用される放射線としては、例えば、可視光線、紫外線、遠紫外線、電子線、Ｘ線等を使用することができるが、波長が１９０〜４５０ｎｍの範囲にある放射線が好ましい。
放射線の露光量は、好ましくは１０〜１０，０００Ｊ／ｍ^２である。
【００９９】
また、前記アルカリ現像液としては、例えば、炭酸ナトリウム、水酸化ナトリウム、水酸化カリウム、テトラメチルアンモニウムハイドロオキサイド、コリン、１，８−ジアザビシクロ−［５．４．０］−７−ウンデセン、１，５−ジアザビシクロ−［４．３．０］−５−ノネン等の水溶液が好ましい。
前記アルカリ現像液には、例えばメタノール、エタノール等の水溶性有機溶剤や界面活性剤等を適量添加することもできる。なお、アルカリ現像後は、通常、水洗する。
現像処理法としては、シャワー現像法、スプレー現像法、ディップ（浸漬）現像法、パドル（液盛り）現像法等を適用することができ、現像条件は、常温で５〜３００秒が好ましい。
【０１００】
本発明のカラーフィルタ用感放射線性組成物から形成されたカラーフィルタは、例えば、透過型あるいは反射型のカラー液晶表示素子、カラー撮像管素子、カラーセンサー等に極めて有用であり、またカラー液晶表示素子の場合、薄膜トランジスター（ＴＦＴ）方式カラー液晶表示装置の駆動用基板上に画素を形成するためにも好適に使用することができる。
【０１０１】
【発明の実施の形態】
本発明のカラーフィルタ用感放射線性組成物は、前記（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）および（Ｅ）成分を含有し、かつ（Ａ）成分が予め（Ｂ）成分の一部または全部を（Ｅ）成分の一部または全部に溶解してなる溶液中に分散されているものであるが、本発明における好ましい組成物は、下記（イ）〜（ニ）のとおりである。
（イ）　（Ｂ）成分がアミノ基含有アルカリ可溶性樹脂（Ｉ）、アミノ基含有アルカリ可溶性樹脂（ＩＩ）およびアミノ基含有アルカリ可溶性樹脂（ＩＩＩ）の群から選ばれる少なくとも１　種を含有するカラーフィルタ用感放射線性組成物。
（ロ）　（Ｂ）成分を構成するアミノ基含有アルカリ可溶性樹脂（ＩＩ）およびアミノ基含有アルカリ可溶性樹脂（ＩＩＩ）におけるマクロモノマーがポリメチルメタクリレートマクロモノマーおよびポリ（メチルメタクリレート／２−ヒドロキシエチルメタクリレート）マクロモノマーの群から選ばれる少なくとも１種からなるアルカリ可溶性共重合体である前記（イ）のカラーフィルタ用感放射線性組成物。
（ハ）　（Ｃ）成分がトリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレートおよびジペンタエリスリトールヘキサアクリレートの群から選ばれる少なくとも１種からなる前記（イ）または（ロ）のカラーフィルタ用感放射線性組成物。
（ニ）　（Ａ）成分が有機顔料および／またはカーボンブラックである前記（イ）、（ロ）または（ハ）のカラーフィルタ用感放射線性組成物。
【０１０２】
本発明における好ましいカラーフィルタは、
（ホ）　前記（イ）〜（ニ）の何れかのカラーフィルタ用感放射線性組成物から形成されてなるカラーフィルタ、
からなり、また、本発明におけるさらに好ましいカラーフィルタは、
（ヘ）　前記（イ）〜（ニ）の何れかのカラーフィルタ用感放射線性組成物から形成されてなり、画素のＲａ値が３０Å以下であるカラーフィルタ、
からなる。
本発明における好ましいカラー液晶表示素子は、
（ト）　前記（ホ）または（ヘ）のカラーフィルタを具備するカラー液晶表示素子、
からなる。
【０１０３】
【実施例】
以下、実施例を挙げて本発明の実施の形態をさらに具体的に説明する。但し、本発明は、下記実施例に限定されるものではない。
実施例１
（Ａ）成分としてＣ．Ｉ．ピグメントグリーン３６を６０重量部およびＣ．Ｉ．ピグメントイエロー１５０を３０重量部、（Ｂ）成分として２−Ｎ，Ｎ−ジエチルアミノエチルメタクリレート／メタクリル酸／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／２−ヒドロキシエチルメタクリレート共重合体（共重合重量比＝１５／１５／１０／４５／１５、Ｍｗ＝１０，０００）９０重量部、（Ｅ）成分としてプロピレングリコールモノメチルエーテルアセテート２００重量部の混合物をビーズミルで処理して顔料を分散させて、顔料分散液を調製した。この顔料分散液の調製に際しては、ビーズの充填率を６０容量％、混合物の充填率をミル容量の４０％、分散時間を３時間とした。
次いで、得られた顔料分散液を、（Ｃ）成分としてジペンタエリスリトールヘキサアクリレート６０重量部、（Ｄ）成分として２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタン−１−オン５０重量部、（Ｅ）成分として３−エトキシプロピオン酸エチル１，５００重量部と混合して、感放射線性組成物の液状組成物を調製した。
【０１０４】
次いで、前記液状組成物を、表面にナトリウムイオンの溶出を防止する
ＳｉＯ_２膜が形成されたソーダガラス基板表面上に、スピンコーターを用いて塗布したのち、８０℃で１０分間プレベークを行って、膜厚２．０μｍの塗膜を形成した。その後、この基板を室温に冷却したのち、高圧水銀ランプを用い、フォトマスク（１Ｌ３Ｓのライン・アンド・スペースパターン）を介して、塗膜に３６５ｎｍ、４０５ｎｍおよび４３６ｎｍの各波長を含む紫外線を１，０００Ｊ／ｍ^２の露光量で露光した。その後、この基板を２３℃の０．０４重量％水酸化カリウム水溶液に１分間浸漬して、現像したのち、超純水で洗浄して、風乾した。その後、２３０℃のクリーンオーブン内で３０分間ポストベークを行なって、基板上に緑色のストライプ状カラーフィルタを形成した。
【０１０５】
得られた基板を光学顕微鏡により観察したところ、ライン幅１０μｍ以上のパターンは全て基板に密着しており、未露光部の基板上に残渣が認められなかった。また、この基板を投光器を用いて観察したところ、未露光部の基板上に地汚れも認められなかった。また、画素のＲａ値は２２Åであり、表面平滑性が極めて優れていた。さらに、この基板の未露光部表面を、エタノールを含ませたトレシー（商品名、東レ（株）製レンズクリーナー））にて１０回擦ったところ、トレシーが緑色に着色されることはなかった。
【０１０６】
実施例２
実施例１において、（Ａ）成分としてＣ．Ｉ．ピグメントブルー１５：６を９０重量部、（Ｂ）成分として２−Ｎ，Ｎ−ジエチルアミノエチルメタクリレート／メタクリル酸／Ｎ−フェニルマレイミド／ポリメチルメタクリレートマクロモノマー／スチレン／ベンジルメタクリレート共重合体（共重合重量比＝２０／１０／２０／１５／２０／１５、Ｍｗ＝１５，０００）９０重量部、（Ｅ）成分としてプロピレングリコールモノメチルエーテルアセテート２００重量部の混合物を、実施例１と同様にして、ビーズミルで処理して顔料を分散させることにより、顔料分散液を調製した以外は、実施例１と同様にして、感放射線性組成物の液状組成物を調製して、基板上に青色のストライプ状カラーフィルタを形成した。
【０１０７】
得られた基板を光学顕微鏡により観察したところ、ライン幅１０μｍ以上のパターンは全て基板に密着しており、未露光部の基板上に残渣が認められなかった。また、この基板を投光器を用いて観察したところ、未露光部の基板上に地汚れも認められなかった。また、画素のＲａ値は２０Åであり、表面平滑性が極めて優れていた。さらに、この基板の未露光部表面を、エタノールを含ませたトレシー（商品名、東レ（株）製レンズクリーナー））にて１０回擦ったところ、トレシーが緑色に着色されることはなかった。
【０１０８】
実施例３
実施例１において、（Ａ）成分としてＣ．Ｉ．ピグメントレッド１７７を１００重量部、（Ｂ）成分として２−Ｎ，Ｎ−ジエチルアミノエチルメタクリレート／メタクリル酸／Ｎ−フェニルマレイミド／グリセロールモノメタクリレート／スチレン／ベンジルメタクリレート共重合体（共重合重量比＝２０／１５／２０／１０／１５／２０、Ｍｗ＝２８，０００）９０重量部、（Ｅ）成分としてプロピレングリコールモノメチルエーテルアセテート２００重量部の混合物を、実施例１と同様にして、ビーズミルで処理して顔料を分散させることにより、顔料分散液を調製した以外は、実施例１と同様にして、感放射線性組成物の液状組成物を調製して、基板上に赤色のストライプ状カラーフィルタを形成した。
【０１０９】
得られた基板を光学顕微鏡により観察したところ、ライン幅１０μｍ以上のパターンは全て基板に密着しており、未露光部の基板上に残渣が認められなかった。また、この基板を投光器を用いて観察したところ、未露光部の基板上に地汚れも認められなかった。また、画素のＲａ値は２３Åであり、表面平滑性が極めて優れていた。さらに、この基板の未露光部表面を、エタノールを含ませたトレシー（商品名、東レ（株）製レンズクリーナー））にて１０回擦ったところ、トレシーが緑色に着色されることはなかった。
【０１１０】
実施例４
実施例１において、（Ａ）成分としてＣ．Ｉ．ピグメントブルー１５：６を９０重量部、（Ｂ）成分として２−Ｎ，Ｎ−ジエチルアミノエチルメタクリレート／メタクリル酸／Ｎ−フェニルマレイミド／ポリ（メチルメタクリレート／２−ヒドロキシエチルメタクリレート）マクロモノマー／ポリメチルメタクリレートマクロモノマー／スチレン／ベンジルメタクリレート共重合体（共重合重量比＝２０／２０／２０／１０／１０／１０／１０、Ｍｗ＝１７，０００）９０重量部、（Ｅ）成分としてプロピレングリコールモノメチルエーテルアセテート２００重量部の混合物を、実施例１と同様にして、ビーズミルで処理して顔料を分散させることにより、顔料分散液を調製した以外は、実施例１と同様にして、感放射線性組成物の液状組成物を調製して、基板上に赤色のストライプ状カラーフィルタを形成した。
【０１１１】
得られた基板を光学顕微鏡により観察したところ、ライン幅１０μｍ以上のパターンは全て基板に密着しており、未露光部の基板上に残渣が認められなかった。また、この基板を投光器を用いて観察したところ、未露光部の基板上に地汚れも認められなかった。また、画素のＲａ値は１９Åであり、表面平滑性が極めて優れていた。さらに、この基板の未露光部表面を、エタノールを含ませたトレシー（商品名、東レ（株）製レンズクリーナー））にて１０回擦ったところ、トレシーが緑色に着色されることはなかった。
【０１１２】
比較例１
実施例１の（Ｂ）成分に代えて、アルカリ可溶性樹脂としてメタクリル酸／２−ヒドロキシエチルメタクリレート／ベンジルメタクリレート／ポリメチルメタクリレートマクロモノマー共重合体（共重合重量比＝１５／１５／６０／１０、Ｍｗ＝２０，０００）９０重量部を用いた以外は、実施例１と同様にして、感放射線性組成物の液状組成物を調製して、基板上に緑色のストライプ状カラーフィルタを形成した。
得られた基板を光学顕微鏡により観察したところ、ライン幅２５μｍ以上のパターンは基板に密着していたが、ライン幅２０μｍ以下のパターンは基板から剥離しており、未露光部の基板上に若干の残渣が認められた。また、この基板を投光器を用いて観察したところ、未露光部の基板上に多少の地汚れが認められた。また、画素のＲａ値は３９Åであり、表面平滑性がやや劣っていた。さらに、この基板の未露光部表面を、エタノールを含ませたトレシー（商品名、東レ（株）製レンズクリーナー））にて５回擦ったところ、トレシーが緑色に着色されることはなかったが、１０回擦ったところ、トレシーが緑色に着色された。
【０１１３】
比較例２
実施例１において、顔料分散液の調製時に、ビーズミルによる分散処理の代わりに攪拌羽根による混合処理を行った以外は、実施例１と同様にして、感放射線性組成物の液状組成物を調製して、基板上に緑色のストライプ状カラーフィルタを形成した。
得られた基板を光学顕微鏡により観察したところ、ライン幅３０μｍ以下のパターンは基板から剥離していた。また、この基板を投光器を用いて観察したところ、未露光部の基板上に地汚れが認められた。また、画素のＲａ値は６３Åであり、表面平滑性が劣っていた。さらに、この基板の未露光部表面を、エタノールを含ませたトレシー（商品名、東レ（株）製レンズクリーナー））にて５回擦ったところ、トレシーが緑色に着色された。
【０１１４】
比較例３
実施例１において、予め（Ａ）成分、（Ｂ）成分および（Ｅ）成分を混合しないで、（Ａ）〜（Ｅ）の各成分を一時に混合することにより、感放射線性組成物の液状組成物を調製した以外は、実施例１と同様にして、基板上に緑色のストライプ状カラーフィルタを形成した。
得られた基板を光学顕微鏡により観察したところ、ライン幅４０μｍ以下のパターンは基板から剥離しており、未露光部の基板上に多量の残渣が認められた。また、この基板を投光器を用いて観察したところ、未露光部の基板上に著しい地汚れが認められた。また、画素のＲａ値は８８Åであり、表面平滑性が極めて劣っていた。さらに、この基板の未露光部表面を、エタノールを含ませたトレシー（商品名、東レ（株）製レンズクリーナー））にて１回擦ったところ、トレシーが緑色に着色された。
【０１１５】
【発明の効果】
本発明のカラーフィルター用感放射線性組成物は、（Ａ）顔料が予め特定の（Ｂ）アルカリ可溶性樹脂が（Ｅ）溶媒に溶解してなる溶液中に分散されていることにより、表面平滑性と基板および遮光層への密着性に優れた画素を形成することができ、しかも現像時に未露光部の基板上および遮光層上に残渣および地汚れを生じることがないという優れた特性を有する。したがって、本発明のカラーフィルター用感放射線性組成物は、電子工業分野におけるカラー液晶表示素子用カラーフィルターを始めとする各種のカラーフィルターの製造に極めて好適に使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a radiation-sensitive composition for a color filter for forming a color filter used for a transmissive or reflective color liquid crystal display element, a color image pickup tube element, and the like, a color filter formed from the composition, And a color liquid crystal display device including the color filter.
[0002]
[Prior art]
Conventionally, when manufacturing a color filter using a radiation-sensitive composition, the radiation-sensitive composition is applied on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed, dried, and then dried. The film is exposed to a desired pattern and developed to obtain pixels of each color.
However, the color filter manufactured in this manner is liable to cause residue and background stains on the unexposed substrate or the light shielding layer during development, and the surface smoothness of post-baked pixels after development. There was a problem that the adhesion of the formed pixel to the substrate or the light shielding layer was not sufficient, and the physical properties of the coating film were inferior. The degree of such a tendency tends to increase as the pigment concentration contained in the radiation-sensitive composition increases. In particular, the degree of deterioration of the surface smoothness of the pixel increases as the pigment concentration increases. It was difficult to achieve.
In order to solve such a problem, the present inventors already have (A) a pigment, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation-sensitive polymerization initiator, and ( E) In a radiation sensitive composition for a color filter containing a solvent, (A) a pigment is previously dissolved in (B) a part or all of the alkali-soluble resin (E) in part or all of the solvent. It is found that it is effective to disperse in However, in recent years, the demand for display quality of color liquid crystal display elements has become stricter, and accordingly, higher performance has been required in terms of pixel surface smoothness, adhesion to a substrate, developability, and the like. .
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a radiation sensitive composition for a color filter that has excellent surface smoothness and adhesiveness of a pixel and has excellent developability, more specifically, to the surface smoothness of a pixel and a substrate and a light shielding layer. It is an object of the present invention to provide a radiation sensitive composition for a color filter that is excellent in adhesion and that does not cause residue and background stains on an unexposed portion of a substrate and a light shielding layer during development.
[0004]
[Means for Solving the Problems]
According to the present invention, the problem is
(A) a pigment, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation-sensitive polymerization initiator, and (E) a solvent. A radiation-sensitive composition for a color filter in which part or all of a soluble resin is dispersed in a solution obtained by dissolving part or all of (E) a solvent, and is used when a pigment is predispersed. (B) the alkali-soluble resin is a group —NR₂(However, each R is independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an allyl group, or an aryl having 6 to 18 carbon atoms. A radiation-sensitive composition for a color filter, comprising an alkali-soluble resin having a group)
Achieved by:
[0005]
The present invention is described in detail below.
(A) Pigment
The pigment in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the obtained color filter, and may be an organic pigment or an inorganic pigment.
Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index numbers. Can be mentioned.
C. I. Pigment yellow 83, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 185;
C. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
[0006]
C. I. Pigment red 177, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 245, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 265; C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60;
C. I. Pigment green 7, C.I. I. Pigment green 36;
C. I. Pigment black 1, C.I. I. Pigment Black 7.
[0007]
Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and oxidation. Examples thereof include chrome green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.
The pigment in the present invention is preferably an organic pigment and / or carbon black having high color development and high heat resistance since the color filter is required to have high precision color development and heat resistance.
In this invention, a pigment can be used individually or in mixture of 2 or more types.
Moreover, in this invention, you may use together a dye, a natural pigment | dye, etc. as needed.
[0008]
The pigment can be used by modifying the particle surface with a polymer in advance. Examples of the polymer that modifies the particle surface of the pigment include polymers described in JP-A-8-259876 and various polymers or oligomers for dispersing pigments on the market.
[0009]
In the present invention, the pigment is dispersed in advance in a solution in which part or all of the alkali-soluble resin containing the (B) amino group-containing alkali-soluble resin described below is dissolved in part or all of the solvent (E) described later. Has been.
In the present invention, when a part of the alkali-soluble resin containing the (B) amino group-containing alkali-soluble resin is used at the time of pigment dispersion, the amino-group-containing alkali-soluble resin and the radiation-sensitive composition are used. The amino group-containing alkali-soluble resin may be the same as or different from the amino group-containing alkali-soluble resin. Examples of the amino group-containing alkali-soluble resin used at the time of pigment dispersion include the amino group-containing alkali-soluble resin (I) and amino group-containing alkali-soluble resin described later. Resin (II), amino group-containing alkali-soluble resin (III) and the like are preferable. In the above case, if necessary, an alkali-soluble resin other than the amino-group-containing alkali-soluble resin can be used at the time of pigment dispersion and preparation of the radiation-sensitive composition. The alkali-soluble resin other than the alkali-soluble resin may be the same or different when the pigment is dispersed and when the radiation-sensitive composition is prepared.
The alkali-soluble resins other than the amino group-containing alkali-soluble resin and the amino group-containing alkali-soluble resin used at the time of pigment dispersion can be used alone or in admixture of two or more.
[0010]
The amount of component (B) used at the time of pigment dispersion can be appropriately selected as long as the pigment can be uniformly dispersed in the solution, but is usually 30 to 500 parts by weight, preferably 100 parts by weight of pigment. 50 to 300 parts by weight, more preferably 70 to 200 parts by weight.
[0011]
Moreover, in this invention, when using a part of (E) solvent at the time of pigment dispersion, the (E) solvent used partially, and the remainder (E) used at the time of preparation of a radiation sensitive composition The solvent may be the same as or different from the solvent, but the solvent (E) used at the time of pigment dispersion includes ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Chill, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, butyric acid n-butyl, ethyl pyruvate and the like are preferable.
The (E) solvent used at the time of pigment dispersion can be used alone or in admixture of two or more.
[0012]
The amount of the component (E) used in dispersing the pigment can be appropriately selected as long as the pigment can be uniformly dispersed in the solution, but is usually 50 to 2,000 parts by weight with respect to 100 parts by weight of the pigment. Preferably it is 100-1,000 weight part.
[0013]
In dispersing the pigment, by using the component (B) and the component (E) in an amount within the above range, a favorable dispersion state of the pigment can be achieved, and a radiation-sensitive composition having excellent adhesion to the substrate and the light shielding layer. Thus, a pixel having excellent surface smoothness and the like can be formed.
[0014]
As a pigment dispersion method, an appropriate method can be adopted as long as the pigment can be uniformly dispersed in the solution, but a method in which pigment particles are pulverized or finely dispersed at the time of pigment dispersion, for example, a bead mill, a roll mill, etc. A method of dispersing with a disperser such as the above can be suitably employed.
When the pigment dispersion is performed using a bead mill, for example, glass beads or titania beads having a diameter of 0.5 to 10 mm are used, the pigment, the component (B) and the component (E) are mixed, and other cases may be used. The mixed liquid to which the pigment dispersant is added can be put into a bead mill.
The filling rate of the beads is usually 50 to 80% by volume, the input amount of the mixed solution is usually about 20 to 50% of the mill capacity, and the dispersion time is usually about 2 to 4 hours. The pigment dispersion by the bead mill is preferably carried out while cooling with cooling water or the like.
In addition, when the pigment dispersion is performed using a roll mill, for example, a two-roll mill, a three-roll mill, or the like is used, and the pigment, the component (B) and the component (E) are mixed. The liquid mixture to which the agent is added can be put into a roll mill.
The roll interval of the roll mill is preferably 10 μm or less, the shearing force is usually about 108 dyn / second, and the dispersion time is usually about 2 to 4 hours.
[0015]
At the time of pigment dispersion in the present invention, (B) an alkali-soluble resin containing an amino group-containing alkali-soluble resin is acting extremely effectively as a dispersant for the pigment, such as developability of the radiation-sensitive composition and physical properties of the coating film. From the viewpoint, it is desirable not to use a pigment dispersant other than the component (B) (hereinafter referred to as “other pigment dispersant”), but other pigment dispersants may be used in combination.
Other pigment dispersants include, for example, polycarboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, ammonium salts and alkylamine salts of polycarboxylic acids such as polyacrylic acid; hydroxyl group-containing polyacrylic acid esters Hydroxyl group-containing polycarboxylic acid esters and modified products thereof such as polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; reaction of poly (lower alkyleneimine) with free carboxyl group-containing polyesters In addition to the amide and salts thereof obtained by the following, Disperbyk-101, -130, -140, -160, -160, -161, -162, -163, -164, and -165 -166, -170, -171, -182 (above, Big Chemie Pan Corporation); EFKA-47, -47EA, -48, -49, -100, -400, -400 (above, EFKA CHEMICALS); Solsperse 12000, 13240, 13940, the same 17000, the same 20000, the same 24000GR, the same 27000, the same 28000 (manufactured by Zeneca Co., Ltd.); PB711, PB821 (manufactured by Ajinomoto Co., Inc.), and the like.
[0016]
As other pigment dispersants other than those described above, surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine can be used.
Examples of such surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Polyoxyethylene alkylphenyl ethers such as polyethylene glycol dilaurate, polyethylene glycol diesters such as polyethylene glycol distearate, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines and the following Under the trade name KP (manufactured by Shin-Etsu Chemical Co., Ltd.); Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.); Ftop (manufactured by Tochem Products); Mega Akku (manufactured by Dainippon Ink and Chemicals, Inc.); (manufactured by Sumitomo 3M) Fluorad; Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.) and the like.
These other pigment dispersants can be used alone or in admixture of two or more.
[0017]
A pigment derivative obtained by treating a pigment with an acid, a base, a polymer or the like can also be used in combination with another pigment dispersant.
Examples of such pigment derivatives include blue pigment derivatives such as copper phthalocyanine derivatives and yellow pigment derivatives.
These pigment derivatives can be used alone or in admixture of two or more.
The total amount of other pigment dispersants and pigment derivatives used is usually 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of the pigment.
[0018]
In the present invention, the average particle diameter of the pigment dispersed as described above is preferably 0.01 to 1.0 μm, more preferably 0.05 to 0.5 μm.
[0019]
(B) Alkali-soluble resin
The alkali-soluble resin in the present invention is the group -NR.₂And an alkali-soluble resin (hereinafter referred to as “amino group-containing alkali-soluble resin”).
The amino group-containing alkali-soluble resin is not particularly limited as long as it has sufficient alkali-solubility and acts effectively as a dispersant and a binder for the pigment (A). Addition polymerization system, polycondensation Any one of a polyaddition system or a polyaddition system may be used. Preferred amino group-containing alkali-soluble resins include, for example,
(I) said group -NR₂Ethylenically unsaturated monomer (hereinafter referred to as “amino group-containing ethylenically unsaturated monomer”), ethylenically unsaturated monomer having carboxyl group, N-substituted maleimide and other copolymers Copolymer of possible monomers (hereinafter referred to as “amino group-containing alkali-soluble resin (I)”);
(II) A copolymer of an amino group-containing ethylenically unsaturated monomer, an ethylenically unsaturated monomer having a carboxyl group, a macromonomer and other copolymerizable monomers (hereinafter referred to as “amino group-containing alkali”). Soluble resin (II) ”);
(III) Copolymers of amino group-containing ethylenically unsaturated monomer, ethylenically unsaturated monomer having a carboxyl group, N-substituted maleimide, macromonomer and other copolymerizable monomers (hereinafter referred to as , "Amino group-containing alkali-soluble resin (III)")
Etc.
[0020]
The macromonomer here refers to a monomer having an ethylenically unsaturated bond at one end of a polymer molecular chain.
In the amino group-containing alkali-soluble resin (I), amino group-containing alkali-soluble resin (II) and amino group-containing alkali-soluble resin (III), “other copolymerizable ethylenically unsaturated monomers” It does not include amino group-containing ethylenically unsaturated monomers, ethylenically unsaturated monomers having a carboxyl group, N-substituted maleimides and macromonomers.
[0021]
In the amino group-containing alkali-soluble resin (I), amino group-containing alkali-soluble resin (II) and amino group-containing alkali-soluble resin (III), the amino group-containing ethylenically unsaturated monomer is, for example,
2-aminoethyl (meth) acrylate, 2-N-methylaminoethyl (meth) acrylate, 2-N-ethylaminoethyl (meth) acrylate, 2-N, N-dimethylaminoethyl (meth) acrylate, 2-N , N-diethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-N-methylaminopropyl (meth) acrylate, 2-N-ethylaminopropyl (meth) acrylate, 2-N, N-dimethyl Aminopropyl (meth) acrylate, 2-N, N-diethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-N-methylaminopropyl (meth) acrylate, 3-N-ethylaminopropyl (meth) ) Acrylate, 3-N, N-dimethylaminopropi (Meth) acrylate, 3-N, N- diethylaminopropyl (meth) aminoalkyl group-containing unsaturated carboxylic acid esters such as acrylate;
[0022]
N-2-aminoethyl (meth) acrylamide, N- (2-N′-methylaminoethyl) (meth) acrylamide, N- (2-N′-ethylaminoethyl) (meth) acrylamide, N- (2- Aminoalkyl group-containing unsaturated amides such as N ′, N′-dimethylaminoethyl) (meth) acrylamide, N- (2-N ′, N′-diethylaminoethyl) (meth) acrylamide;
Amino group-containing aromatic vinyl compounds such as 4-aminostyrene, 4-N-methylaminostyrene, 4-N-ethylaminostyrene, 4-N, N-dimethylaminostyrene, 4-N, N-diethylaminostyrene
Etc.
[0023]
Of these amino group-containing ethylenically unsaturated monomers, aminoalkyl group-containing unsaturated carboxylic acid esters are preferred, and in particular, 2-aminoethyl (meth) acrylate and 2-N-ethylaminoethyl (meth) acrylate. 2-N, N-diethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate and the like are preferable.
The amino group-containing ethylenically unsaturated monomers can be used alone or in admixture of two or more.
[0024]
Examples of the ethylenically unsaturated monomer having a carboxyl group include:
(Meth) acrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], monocarboxylic acids such as ω-carboxypolycaprolactone mono (meth) acrylate;
Dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid;
Trivalent or higher polyvalent carboxylic acids (anhydrides)
Etc.
Of these ethylenically unsaturated monomers having a carboxyl group, (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate and the like are preferable.
The said ethylenically unsaturated monomer which has a carboxyl group can be used individually or in mixture of 2 or more types.
[0025]
Examples of the N-substituted maleimide include N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N In addition to N-position aryl-substituted maleimide such as -m-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, N -Cyclohexylmaleimide etc. can be mentioned.
Of these N-substituted maleimides, N-phenylmaleimide, Np-hydroxyphenylmaleimide, N-cyclohexylmaleimide and the like are preferable.
The N-substituted maleimides can be used alone or in admixture of two or more.
[0026]
Moreover, as a polymer molecular chain in a macromonomer, for example, polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, Mention may be made of molecular chains such as polycaprolactone, polyoxyethylene, polysiloxane and the like.
[0027]
The macromonomer is obtained, for example, by reacting a precursor polymer having an appropriate functional group at one end of the polymer molecular chain with an ethylenically unsaturated compound having a complementary functional group capable of reacting with the functional group. Can be synthesized.
The precursor polymer having the functional group can be obtained by, for example, living anion polymerization, living cationic polymerization, living polymer terminal modification reaction, telechelic polymer synthesis, and the like, and polyaddition resins having terminal functional groups, A polycondensation resin can also be used as the precursor polymer.
Examples of the ethylenically unsaturated compound having a complementary functional group include ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, acid chlorides of the ethylenically unsaturated carboxylic acids, aminoalkyl esters, hydroxy Derivatives such as alkyl esters and glycidyl esters, p-aminostyrene, vinyl glycidyl ether, allyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. are appropriately selected and used according to the type of functional group in the precursor polymer. be able to.
[0028]
As the macromonomer in the present invention, a macromonomer having an ethylenically unsaturated bond, preferably a (meth) acryloyl group (hereinafter referred to as “polymethylmethacrylate macromonomer”), methyl at one end of the polymethylmethacrylate molecular chain. A macromonomer having an ethylenically unsaturated bond, preferably an acryloyl group or a methacryloyl group at one end of a molecular chain of a methacrylate / 2-hydroxyethyl methacrylate copolymer (hereinafter referred to as “poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macro” Monomer ")) is desirable.
The said macromonomer can be used individually or in mixture of 2 or more types.
[0029]
Furthermore, as the other copolymerizable ethylenically unsaturated monomer, for example,
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, indene, p-vinylbenzylmethyl ether , Aromatic vinyl compounds such as p-vinylbenzyl glycidyl ether;
Indene (derivatives) such as indene and 1-methylindene;
[0030]
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxydiethylene gluco- (Meth) acrylates, other unsaturated carboxylic acid esters such as methoxy triethylene glycol (meth) acrylate, glycerol mono (meth) acrylate;
[0031]
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; vinyl acetates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Other unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene
Etc.
[0032]
Among these other copolymerizable ethylenically unsaturated monomers, styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono ( A (meth) acrylate etc. are preferable.
The other copolymerizable ethylenically unsaturated monomers can be used alone or in admixture of two or more.
[0033]
In the present invention, specific examples of the preferred amino group-containing alkali-soluble resin (I) include
2-N, N-diethylaminoethyl acrylate / methacrylic acid / N-phenylmaleimide / styrene / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl acrylate / methacrylic acid / N-phenylmaleimide / styrene / phenyl methacrylate copolymer,
2-N, N-diethylaminoethyl acrylate / methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / styrene / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl acrylate / methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenylmaleimide / styrene / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl acrylate copolymer / methacrylic acid / N-phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate
Etc.
[0034]
In the amino group-containing alkali-soluble resin (I), the copolymerization ratio of the amino group-containing ethylenically unsaturated monomer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio of the amino group-containing ethylenically unsaturated monomer is less than 5% by weight, the dispersibility of the pigment tends to be lowered. There is a possibility that the solubility is lowered and a residue or a background stain is generated on the unexposed substrate or the light shielding layer.
[0035]
Moreover, the copolymerization ratio of the ethylenically unsaturated monomer having a carboxyl group is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio of the unsaturated monomer having a carboxyl group is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkali developer tends to be lowered, whereas it exceeds 50% by weight. When developing with an alkaline developer, the formed pixel tends to drop off from the substrate and the film surface of the pixel tends to be rough.
[0036]
The copolymerization ratio of the N-substituted maleimide is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the N-substituted maleimide is less than 5% by weight, the heat resistance of the resulting pixel tends to decrease, whereas if it exceeds 50% by weight, the alkali solubility of the resulting copolymer decreases. As a result, there is a possibility that a residue or a background stain may be generated on the unexposed portion of the substrate or the light shielding layer.
[0037]
The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC) of the amino group-containing alkali-soluble resin (I) is usually 1,000 to 1,000,000, preferably It is 2,000 to 500,000, more preferably 3,000 to 100,000.
[0038]
The amino group-containing alkali-soluble resin (I) having a copolymerization ratio of each monomer and Mw as described above has a high pigment dispersion ability and excellent solubility in an alkali developer, and is obtained from the same. The cured product is excellent in various physical properties, and the radiation-sensitive composition using the amino group-containing alkali-soluble resin (I) has very little undissolved material remaining after development with an alkali developer. Background stains and film residue in areas other than the area where pixels are formed are unlikely to occur, and pixels obtained from the composition are not excessively dissolved in an alkaline developer and have excellent adhesion to the substrate. And has no risk of falling off the substrate.
[0039]
Moreover, as a specific example of preferable amino group containing alkali-soluble resin (II),
2-N, N-diethylaminoethyl acrylate / methacrylic acid / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / benzyl acrylate copolymer,
2-N, N-diethylaminoethyl acrylate / methacrylic acid / polymethyl methacrylate macromonomer / benzyl acrylate copolymer,
2-N, N-diethylaminoethyl acrylate / methacrylic acid / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / methyl acrylate copolymer,
2-N, N-diethylaminoethyl acrylate / methacrylic acid / polymethyl methacrylate macromonomer / methyl acrylate copolymer,
2-N, N-diethylaminoethyl acrylate / methacrylic acid / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / benzyl methacrylate copolymer,
[0040]
2-N, N-diethylaminoethyl acrylate / methacrylic acid / polymethyl methacrylate macromonomer / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl acrylate / methacrylic acid / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / methyl methacrylate copolymer,
2-N, N-diethylaminoethyl acrylate / methacrylic acid / polymethyl methacrylate macromonomer / methyl methacrylate copolymer,
2-N, N-diethylaminoethyl acrylate / methacrylic acid / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl acrylate / methacrylic acid / polymethyl methacrylate macromonomer / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer,
[0041]
2-N, N-diethylaminoethyl acrylate / acrylic acid / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl acrylate / acrylic acid / polymethyl methacrylate macromonomer / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl acrylate / acrylic acid / 2-hydroxyethyl methacrylate / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl acrylate / acrylic acid / polymethyl methacrylate macromonomer / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer
Etc.
[0042]
In the amino group-containing alkali-soluble resin (II), the copolymerization ratio of the amino group-containing ethylenically unsaturated monomer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio of the amino group-containing ethylenically unsaturated monomer is less than 5% by weight, the dispersibility of the pigment tends to be lowered. There is a possibility that the solubility is lowered and a residue or a background stain is generated on the unexposed substrate or the light shielding layer.
[0043]
Moreover, the copolymerization ratio of the ethylenically unsaturated monomer having a carboxyl group is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkaline developer tends to decrease, whereas if it exceeds 50% by weight. When developing with an alkali developer, the formed pixel tends to drop off from the substrate and the film surface of the pixel tends to be rough.
[0044]
The copolymerization ratio of the macromonomer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the macromonomer is less than 5% by weight, the dispersibility of the pigment tends to be lowered. On the other hand, if it exceeds 50% by weight, the alkali solubility of the resulting copolymer is lowered, and the unexposed There is a risk that residue or background contamination may occur on the substrate or the light shielding layer.
[0045]
The Mw of the amino group-containing alkali-soluble resin (II) is usually 1,000 to 1,000,000, preferably 2,000 to 500,000, more preferably 3,000 to 100,000.
[0046]
The amino group-containing alkali-soluble resin (II) having a copolymerization ratio of each monomer and Mw as described above has a high pigment dispersing ability and excellent solubility in an alkali developer, and is obtained therefrom. The cured product is excellent in various physical properties, and the radiation-sensitive composition using the amino group-containing alkali-soluble resin (II) has very little undissolved material remaining after development with an alkali developer. Background stains and film residue in areas other than the area where pixels are formed are unlikely to occur, and pixels obtained from the composition are not excessively dissolved in an alkaline developer and have excellent adhesion to the substrate. And has no risk of falling off the substrate.
[0047]
As specific examples of the amino group-containing alkali-soluble resin (III),
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / styrene / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / polymethyl methacrylate macromonomer / styrene / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / styrene / phenyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / polymethyl methacrylate macromonomer / styrene / phenyl methacrylate copolymer,
[0048]
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / polymethyl methacrylate macromonomer / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / polymethyl methacrylate macromonomer / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate copolymer,
[0049]
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / styrene / benzyl methacrylate copolymer Coalescence,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / polymethyl methacrylate macromonomer / styrene / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / styrene / phenyl methacrylate copolymer Coalescence,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / polymethyl methacrylate macromonomer / styrene / phenyl methacrylate copolymer
[0050]
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / styrene / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer / styrene / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / styrene / phenyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer / styrene / phenyl methacrylate copolymer,
[0051]
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / styrene / glycerol monomethacrylate / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / polymethyl methacrylate macromonomer / styrene / glycerol monomethacrylate / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / styrene / glycerol monomethacrylate / phenyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / polymethyl methacrylate macromonomer / styrene / glycerol monomethacrylate / phenyl methacrylate copolymer
[0052]
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / polymethyl methacrylate macromonomer / styrene / benzyl methacrylate copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / polymethyl methacrylate macromonomer / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate Coalescence,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / polymethyl methacrylate macromonomer / styrene / Benzyl methacrylate copolymer,
[0053]
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / ω-carboxypolycaprolactone monoacrylate / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / polymethyl methacrylate macromonomer / styrene / benzyl methacrylate Copolymer,
2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / polymethyl methacrylate macromonomer / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer
Etc.
[0054]
In the amino group-containing alkali-soluble resin (III), the copolymerization ratio of the amino group-containing ethylenically unsaturated monomer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio of the amino group-containing ethylenically unsaturated monomer is less than 5% by weight, the dispersibility of the pigment tends to be lowered. There is a possibility that the solubility is lowered and a residue or a background stain is generated on the unexposed substrate or the light shielding layer.
[0055]
Moreover, the copolymerization ratio of the ethylenically unsaturated monomer having a carboxyl group is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkaline developer tends to decrease, whereas if it exceeds 50% by weight. When developing with an alkali developer, the formed pixel tends to drop off from the substrate and the film surface of the pixel tends to be rough.
[0056]
The copolymerization ratio of the N-substituted maleimide is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the N-substituted maleimide is less than 5% by weight, the heat resistance of the resulting pixel tends to decrease, whereas if it exceeds 50% by weight, the alkali solubility of the resulting copolymer decreases. As a result, there is a possibility that a residue or a background stain may be generated on the unexposed portion of the substrate or the light shielding layer.
[0057]
The copolymerization ratio of the macromonomer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the macromonomer is less than 5% by weight, the dispersibility of the pigment tends to be lowered. On the other hand, if it exceeds 50% by weight, the alkali solubility of the resulting copolymer is lowered, and the unexposed There is a risk that residue or background contamination may occur on the substrate or the light shielding layer.
[0058]
The Mw of the amino group-containing alkali-soluble resin (III) is usually 1,000 to 1,000,000, preferably 2,000 to 500,000, more preferably 3,000 to 100,000.
[0059]
The amino group-containing alkali-soluble resin (III) having a copolymerization ratio of each monomer and Mw as described above has a high pigment dispersion ability and excellent solubility in an alkali developer, and is obtained therefrom. The cured product is also excellent in various physical properties, and the radiation-sensitive composition using the amino group-containing alkali-soluble resin (III) has very little undissolved material remaining after development with an alkali developer. Background stains and film residue in areas other than the area where pixels are formed are unlikely to occur, and pixels obtained from the composition are not excessively dissolved in an alkaline developer and have excellent adhesion to the substrate. And has no risk of falling off the substrate.
[0060]
The amino group-containing alkali-soluble resin in the present invention is more preferably an amino group-containing alkali-soluble resin (II) or an amino group-containing alkali-soluble resin (III), and particularly preferably, the macromonomer is a polymethyl methacrylate macromonomer. And an amino group-containing alkali-soluble resin (II) and an amino group-containing alkali-soluble resin (III), which are at least one selected from the group of poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomers.
In this invention, an amino group containing alkali-soluble resin can be used individually or in mixture of 2 or more types.
[0061]
Also, alkali-soluble resins other than the amino group-containing alkali-soluble resins (I) to (III) (hereinafter referred to as “other alkali-soluble resins”) are copolymerized with an ethylenically unsaturated monomer having a carboxyl group. A copolymer with another possible monomer (hereinafter referred to as “alkali-soluble resin (i)”) is preferable.
Specific examples of preferable alkali-soluble resin (i) include
Acrylic acid / benzyl acrylate copolymer,
Acrylic acid / benzyl acrylate / styrene copolymer,
Acrylic acid / methyl acrylate / styrene copolymer,
Acrylic acid / benzyl methacrylate copolymer,
Acrylic acid / benzyl methacrylate / styrene copolymer,
Acrylic acid / methyl methacrylate / styrene copolymer,
Methacrylic acid / benzyl acrylate copolymer,
Methacrylic acid / benzyl acrylate / styrene copolymer,
Methacrylic acid / methyl acrylate / styrene copolymer,
Methacrylic acid / benzyl methacrylate copolymer,
Methacrylic acid / benzyl methacrylate / styrene copolymer,
Methacrylic acid / methyl methacrylate / styrene copolymer
[0062]
Acrylic acid / benzyl acrylate / 2-hydroxyethyl acrylate copolymer,
Acrylic acid / benzyl methacrylate / 2-hydroxyethyl acrylate copolymer,
Acrylic acid / benzyl acrylate / 2-hydroxyethyl methacrylate copolymer,
Acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer,
Acrylic acid / N-phenylmaleimide / benzyl acrylate / styrene copolymer,
Acrylic acid / N-phenylmaleimide / benzyl methacrylate / styrene copolymer,
Methacrylic acid / benzyl acrylate / 2-hydroxyethyl acrylate copolymer,
Methacrylic acid / benzyl methacrylate / 2-hydroxyethyl acrylate copolymer,
Methacrylic acid / benzyl acrylate / 2-hydroxyethyl methacrylate copolymer,
Methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer,
Methacrylic acid / N-phenylmaleimide / benzyl acrylate / styrene copolymer,
Methacrylic acid / N-phenylmaleimide / benzyl methacrylate / styrene copolymer,
[0063]
Acrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / styrene / allyl acrylate copolymer,
Acrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / styrene / allyl acrylate copolymer,
Acrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / styrene / allyl methacrylate copolymer,
Acrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / styrene / allyl methacrylate copolymer,
Methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / styrene / allyl acrylate copolymer,
Methacrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / styrene / allyl acrylate copolymer,
Methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / styrene / allyl methacrylate copolymer,
Methacrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / styrene / allyl methacrylate copolymer,
[0064]
Acrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / benzyl acrylate / styrene copolymer,
Acrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / benzyl acrylate / styrene copolymer,
Acrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / benzyl methacrylate / styrene copolymer,
Acrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / benzyl methacrylate / styrene copolymer,
Methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / benzyl acrylate / styrene copolymer,
Methacrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / benzyl acrylate / styrene copolymer,
Methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / N-phenylmaleimide / benzyl methacrylate / styrene copolymer,
Methacrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / benzyl methacrylate / styrene copolymer,
[0065]
Acrylic acid / N-phenylmaleimide / benzyl acrylate / glycerol monoacrylate / styrene copolymer,
Acrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monoacrylate / styrene copolymer,
Acrylic acid / N-phenylmaleimide / benzyl acrylate / glycerol monomethacrylate / styrene copolymer,
Acrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monomethacrylate / styrene copolymer,
Methacrylic acid / N-phenylmaleimide / benzyl acrylate / glycerol monoacrylate / styrene copolymer,
Methacrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monoacrylate / styrene copolymer,
Methacrylic acid / N-phenylmaleimide / benzyl acrylate / glycerol monomethacrylate / styrene copolymer,
Methacrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monomethacrylate / styrene copolymer
Etc.
[0066]
In the alkali-soluble resin (i), the copolymerization ratio of the ethylenically unsaturated monomer having a carboxyl group is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkaline developer tends to decrease, whereas if it exceeds 50% by weight. When developing with an alkali developer, the formed pixel tends to drop off from the substrate and the film surface of the pixel tends to be rough.
[0067]
Mw of alkali-soluble resin (i) is 1,000-1,000,000 normally, Preferably it is 2,000-500,000, More preferably, it is 3,000-100,000.
In the present invention, other alkali-soluble resins can be used alone or in admixture of two or more.
The ratio of the other alkali-soluble resin used in the present invention is preferably 50% by weight or less, more preferably 30% by weight or less, based on the entire alkali-soluble resin.
[0068]
The total amount of the alkali-soluble resin used in the present invention is usually 30 to 500 parts by weight, preferably 50 to 300 parts by weight with respect to 100 parts by weight of component (A). In this invention, the radiation sensitive composition excellent in the adhesiveness to a board | substrate and a light shielding layer, developability, etc. can be obtained by using (B) component in the quantity of this range.
[0069]
In the present invention, the pigment is previously dispersed in a solution in which part or all of the alkali-soluble resin (B) containing the amino group-containing alkali-soluble resin is dissolved in part or all of the solvent (E). More specifically, the use mode of the component (B) in the present invention is as follows.
(1) A mode in which a part of the alkali-soluble resin constituting the radiation-sensitive composition is used at the time of pigment dispersion and the remaining part is used at the time of preparing the radiation-sensitive composition:
In this embodiment, the alkali-soluble resin used at the time of pigment dispersion may consist of (a) an amino group-containing alkali-soluble resin alone or (b) a mixture of an amino group-containing alkali-soluble resin and another alkali-soluble resin. In the case of (b), the proportion of other alkali-soluble resin used is preferably 50% by weight or less, more preferably 30% by weight or less. Moreover, about the alkali-soluble resin used at the time of preparation of a radiation sensitive composition, (a) In the case of only an amino group-containing alkali-soluble resin, (b) a mixture of an amino group-containing alkali-soluble resin and another alkali-soluble resin Or (c) other alkali-soluble resins may be used alone. In the case of (b), the use ratio of the other alkali-soluble resins is preferably 50% by weight or less, more preferably 30% by weight or less.
(2) A mode in which all of the alkali-soluble resin constituting the radiation-sensitive composition is used at the time of pigment dispersion:
In this embodiment, the alkali-soluble resin may consist of (i) an amino group-containing alkali-soluble resin alone or (b) a mixture of an amino group-containing alkali-soluble resin and another alkali-soluble resin. The use ratio of the other alkali-soluble resin in is preferably 50% by weight or less, more preferably 30% by weight or less.
[0070]
(C) Multifunctional monomer
The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
In addition to di (meth) acrylates of hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, and both ends hydroxypolycaprolactone,
Tris [2- (meth) acryloyloxyethyl] phosphate
Etc.
[0071]
Among these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having a valence of 3 or more and their dicarboxylic acid-modified products are preferable, and specifically, trimethylolpropane triacrylate, trimethylolpropane triacrylate. Methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, the following formula (1 Compound represented by
[0072]
[Chemical 1]

[0073]
And a compound represented by the following formula (2):
[Chemical 2]

[0074]
In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high pixel strength, excellent pixel surface smoothness, and are uncoated on the substrate and the light-shielding layer. This is preferable in that stains and film residues are hardly generated.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.
[0075]
Moreover, in this invention, a monofunctional monomer can also be used together with the said polyfunctional monomer depending on the case.
Specific examples of such monofunctional monomers include amino group-containing ethylenically unsaturated monomers exemplified for the amino group-containing alkali-soluble resins (I) to (III), and ethylenically unsaturated monomers having a carboxyl group. In addition to saturated monomers, N-substituted maleimides and other copolymerizable ethylenically unsaturated monomers, trade names such as M-5300, M-5400 (trade names, manufactured by Toagosei Co., Ltd.), etc. Can be mentioned.
These monofunctional monomers can be used alone or in admixture of two or more.
The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the obtained pixel may be insufficient.
[0076]
The total use amount of the polyfunctional monomer and the monofunctional monomer in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the component (B). is there. In this case, if the total use amount is less than 5 parts by weight, the strength and surface smoothness of the pixel tend to be reduced. On the other hand, if it exceeds 500 parts by weight, for example, alkali developability may be reduced, or There is a tendency that soiling, film residue, etc. are likely to occur on the substrate or the light shielding layer.
[0077]
(D) Photopolymerization initiator
In the present invention, the photopolymerization initiator is decomposed or cleaved by exposure to visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. A compound that generates an active species capable of initiating polymerization of a monomer.
Examples of such photopolymerization initiators include biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, triazine compounds, and the like. it can.
[0078]
Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenyl-1,
2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,
4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl- 1, 2'-biimidazole and the like can be mentioned.
These biimidazole compounds are excellent in solubility in solvents, do not produce foreign substances such as undissolved materials and precipitates, are highly sensitive, and sufficiently advance the curing reaction by exposure with a small amount of energy, and contrast. The coating film after exposure is clearly divided into a hardened part that is insoluble in the developer and an uncured part that has high solubility in the developer. Thus, a high-definition pixel array in which pixel patterns without undercuts are arranged according to a predetermined arrangement can be formed.
[0079]
Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin i-propyl ether, benzoin i-butyl ether, and methyl-2-benzoylbenzoate.
Specific examples of the acetophenone compound include 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- (4-i-propylphenyl). 2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxy Examples include cyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and the like. Kill.
[0080]
Specific examples of the benzophenone compounds include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone.
Specific examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoyl formate, and the like.
Specific examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone, and the like.
Specific examples of the xanthone compound include xanthone, thioxanthone, and 2-chlorothioxanthone.
[0081]
Furthermore, specific examples of the triazine compound include 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2-methoxyphenyl) -s-triazine, 1,3-bis (Trichloromethyl) -5- (4-methoxyphenyl) -s-triazine, 2- (2-furylethylidene) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxystyryl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, -(4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2-bromo-4-methylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(2-thiophenylethylidene) -4,6-bis (trichloromethyl) -s-triazine and the like can be mentioned.
[0082]
The said photoinitiator can be used individually or in mixture of 2 or more types.
The amount of the photopolymerization initiator used in the present invention is usually 0.01 to 200 weights per 100 parts by weight of the total of the (C) polyfunctional monomer and the optionally used polyfunctional monomer. Parts, preferably 1 to 120 parts by weight, more preferably 1 to 100 parts by weight. In this case, if the amount of the photopolymerization initiator used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a pixel array in which pixel patterns are arranged according to a predetermined arrangement, On the other hand, when the amount exceeds 200 parts by weight, the formed pixels are liable to fall off the substrate during development, and background stains, film residues, etc. are likely to occur on the unexposed portion of the substrate or on the light shielding layer.
Furthermore, in the present invention, one or more of a sensitizer, a curing accelerator and a polymer photocrosslinking / sensitizer can be used in combination with the photopolymerization initiator as necessary.
[0083]
(E) Solvent
The solvent in the present invention disperses or dissolves the components (A) to (D) constituting the radiation-sensitive composition and additive components described later, and does not react with these components and has appropriate volatility. As long as it is, it is not particularly limited.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;
(Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol Other ethers such as dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
[0084]
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl 3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate Butyl, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate , Methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate Other esters;
Aromatic hydrocarbons such as toluene and xylene;
Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide
Etc.
[0085]
Among these solvents, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl from the viewpoints of solubility, pigment dispersibility, coatability, etc. Ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropio Nate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-probutyrate Le, butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.
[0086]
Further, together with the solvent, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate , Γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate and other high boiling point solvents can be used in combination.
Of these high boiling solvents, γ-butyrolactone and the like are preferred.
The high boiling point solvents can be used alone or in admixture of two or more.
[0087]
The amount of the solvent used in the present invention is not particularly limited, but the total concentration of each component excluding the solvent of the composition is from the viewpoint of applicability, stability and the like of the resulting radiation-sensitive composition. The amount is usually 5 to 50% by weight, preferably 10 to 40% by weight.
[0088]
Additive
The radiation sensitive composition for a color filter of the present invention can contain various additives as required.
Examples of the additive include organic acids that have the effect of further improving the solubility of the radiation-sensitive composition for color filters in an alkaline developer and further suppressing the remaining undissolved material after development.
Such an organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in the molecule.
[0089]
Examples of the aliphatic carboxylic acid include
Monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid
Etc.
[0090]
Examples of the phenyl group-containing carboxylic acid include aromatic carboxylic acids in which a carboxyl group is directly bonded to a phenyl group, and carboxylic acids in which a carboxyl group is bonded to a phenyl group via a carbon chain. For example,
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, umberic acid
Etc.
[0091]
Among these organic acids, aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, and phthalic acid are alkali-soluble and soluble in solvents described later. From the standpoint of preventing background contamination and film residue on the unexposed portion of the substrate or the light shielding layer.
The organic acids can be used alone or in admixture of two or more.
The amount of the organic acid used is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less based on the whole radiation-sensitive composition. In this case, when the amount of the organic acid used exceeds 10% by weight, the adhesion of the formed pixel to the substrate tends to be lowered.
[0092]
As specific examples of additives other than the organic acid,
Dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives;
Fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, poly (fluoroalkyl acrylates);
Nonionic, cationic and anionic surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Thermal crosslinking agents such as epoxy compounds, melamine compounds, and bisazide compounds
Etc.
[0093]
The radiation sensitive composition for color filters of the present invention can essentially solve the surface smoothness, adhesion and developability of the pixels mentioned as the above-mentioned problems.
The surface smoothness of the pixel is expressed by the following formula (1).
[0094]
[Expression 1]

[However, Ra is the average roughness along the pixel center line (中心), L is the measurement length, y is the distance from the pixel center line to the roughness curve (Å), and x is the position coordinate in the measurement length direction. It is. ]
It can be evaluated by the Ra value defined by
[0095]
Conventionally, the upper limit of the Ra value was about 50%, but now it is required to be 30% or less.
By using the radiation sensitive composition for a color filter of the present invention, the Ra value of the pixel can be usually 30 mm or less, preferably 20 mm or less, and (1) the contact area between the pixel and the liquid crystal is large. As a result, impurities can seep out from the colored layer to the liquid crystal, and (2) adverse effects such as poor alignment of the liquid crystal due to the rough surface of the pixel can be suppressed appropriately, and display defects such as image sticking and display unevenness can be prevented. An extremely high-quality color liquid crystal display element can be obtained.
[0096]
Method for preparing radiation-sensitive composition for color filter
As described above, the radiation-sensitive composition for a color filter of the present invention is a solvent in which a part or all of an alkali-soluble resin containing (A) a pigment in advance and (B) an amino group-containing alkali-soluble resin is (E) a solvent. The pigment dispersion liquid is dispersed in a solution in which it is dissolved in a part or all of (A), together with (C) a polyfunctional monomer and (D) a photopolymerization initiator, if necessary (B) It can be prepared by adding the remainder of the alkali-soluble resin and the remainder of the solvent (E) and mixing.
The mixing method of each component after a pigment dispersion process is not specifically limited, It can implement by a conventional method.
[0097]
Method for forming color filter
Next, a method for forming a color filter using the radiation sensitive composition for a color filter of the present invention will be described.
On the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming a pixel, and a liquid composition of a radiation sensitive composition in which, for example, a red pigment is dispersed is formed on the substrate. After coating, pre-baking is performed to evaporate the solvent and form a coating film. Next, the coating film is exposed to radiation through a photomask and then developed with an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to form a red pixel pattern. A pixel array arranged in a predetermined arrangement is formed.
In addition, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, each liquid composition is applied, pre-baked, exposed and developed in the same manner as described above, and then post-baked. By forming the green pixel array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green, and blue are arranged on the substrate is obtained. However, the order of forming the pixel patterns of the respective colors when forming the color filter is not limited to the above.
[0098]
Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When the liquid composition of the radiation sensitive composition is applied to the substrate, an appropriate application method such as spin coating, cast coating, roll coating or the like can be employed.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 5.0 μm, particularly preferably 0.2 to 3.0 μm, as the film thickness after drying.
As the radiation used when producing the color filter, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable. .
The exposure dose of radiation is preferably 10 to 10,000 J / m²It is.
[0099]
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied, and the development conditions are preferably 5 to 300 seconds at room temperature.
[0100]
The color filter formed from the radiation-sensitive composition for a color filter of the present invention is extremely useful for, for example, a transmissive or reflective color liquid crystal display element, a color imaging tube element, a color sensor, and the like, and a color liquid crystal display. In the case of an element, it can be suitably used for forming a pixel on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device.
[0101]
DETAILED DESCRIPTION OF THE INVENTION
The radiation sensitive composition for a color filter of the present invention contains the components (A), (B), (C), (D) and (E), and the component (A) is the component (B) in advance. A part or all of the component (E) is dispersed in a solution obtained by dissolving part or all of the component (E). Preferred compositions in the present invention are as shown in the following (a) to (d). is there.
(A) Color filter wherein component (B) contains at least one selected from the group consisting of amino group-containing alkali-soluble resin (I), amino group-containing alkali-soluble resin (II) and amino group-containing alkali-soluble resin (III) Radiation sensitive composition.
(B) The macromonomer in the amino group-containing alkali-soluble resin (II) and amino group-containing alkali-soluble resin (III) constituting the component (B) is polymethyl methacrylate macromonomer and poly (methyl methacrylate / 2-hydroxyethyl methacrylate). The radiation sensitive composition for a color filter according to the above (a), which is an alkali-soluble copolymer comprising at least one selected from the group of macromonomers.
(C) The radiation sensitive composition for color filters of (A) or (B) above, wherein the component (C) is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate. object.
(D) The radiation sensitive composition for a color filter according to (a), (b) or (c) above, wherein the component (A) is an organic pigment and / or carbon black.
[0102]
Preferred color filters in the present invention are:
(E) a color filter formed from the radiation sensitive composition for a color filter according to any one of (a) to (d) above;
Further, a more preferable color filter in the present invention is
(F) A color filter formed from the radiation sensitive composition for a color filter according to any one of (a) to (d) above, and having a pixel Ra value of 30 mm or less,
Consists of.
Preferred color liquid crystal display elements in the present invention are:
(G) a color liquid crystal display device comprising the color filter of (e) or (f),
Consists of.
[0103]
【Example】
Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Example 1
As component (A), C.I. I. 60 parts by weight of CI Pigment Green 36 and C.I. I. 30 parts by weight of Pigment Yellow 150, 2-N, N-diethylaminoethyl methacrylate / methacrylic acid / polymethyl methacrylate macromonomer / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer (copolymerization weight ratio = 15) as component (B) / 15/10/45/15, Mw = 10,000) 90 parts by weight, and (E) component 200 parts by weight of propylene glycol monomethyl ether acetate is treated with a bead mill to disperse the pigment. Prepared. In preparing this pigment dispersion, the filling rate of beads was 60% by volume, the filling rate of the mixture was 40% of the mill volume, and the dispersion time was 3 hours.
Next, the obtained pigment dispersion was mixed with 60 parts by weight of dipentaerythritol hexaacrylate as component (C) and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane as component (D). A liquid composition of radiation sensitive composition was prepared by mixing 50 parts by weight of 1-one and 1,500 parts by weight of ethyl 3-ethoxypropionate as component (E).
[0104]
Next, the liquid composition prevents the elution of sodium ions on the surface.
SiO₂On the surface of the soda glass substrate on which the film was formed, it was applied using a spin coater and then pre-baked at 80 ° C. for 10 minutes to form a coating film having a thickness of 2.0 μm. Thereafter, after cooling the substrate to room temperature, using a high-pressure mercury lamp, ultraviolet rays containing wavelengths of 365 nm, 405 nm, and 436 nm are applied to the coating film through a photomask (1L3S line and space pattern). 000J / m²The exposure amount was as follows. Thereafter, the substrate was immersed in a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried. Thereafter, post-baking was performed in a clean oven at 230 ° C. for 30 minutes to form a green striped color filter on the substrate.
[0105]
When the obtained board | substrate was observed with the optical microscope, all the patterns with a line width of 10 micrometers or more were closely_contact | adhered to the board | substrate, and the residue was not recognized on the board | substrate of an unexposed part. Moreover, when this board | substrate was observed using the light projector, the ground dirt was not recognized on the board | substrate of an unexposed part. Further, the Ra value of the pixel was 22 mm, and the surface smoothness was extremely excellent. Further, when the surface of the unexposed portion of the substrate was rubbed 10 times with a Toraysee (trade name, manufactured by Toray Industries, Inc.) containing ethanol, the Toraysee was not colored green.
[0106]
Example 2
In Example 1, C.I. I. 90 parts by weight of CI Pigment Blue 15: 6, 2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / polymethyl methacrylate macromonomer / styrene / benzyl methacrylate copolymer (copolymerization weight) as component (B) Ratio = 20/10/20/15/20/15, Mw = 15,000) 90 parts by weight and (E) component 200 parts by weight of propylene glycol monomethyl ether acetate A liquid composition of a radiation sensitive composition was prepared in the same manner as in Example 1 except that a pigment dispersion was prepared by dispersing the pigment by treatment with a blue striped color on the substrate. A filter was formed.
[0107]
When the obtained board | substrate was observed with the optical microscope, all the patterns with a line width of 10 micrometers or more were closely_contact | adhered to the board | substrate, and the residue was not recognized on the board | substrate of an unexposed part. Moreover, when this board | substrate was observed using the light projector, the ground dirt was not recognized on the board | substrate of an unexposed part. Further, the Ra value of the pixel was 20%, and the surface smoothness was extremely excellent. Further, when the surface of the unexposed portion of the substrate was rubbed 10 times with a Toraysee (trade name, manufactured by Toray Industries, Inc.) containing ethanol, the Toraysee was not colored green.
[0108]
Example 3
In Example 1, C.I. I. 100 parts by weight of Pigment Red 177, and as component (B) 2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / glycerol monomethacrylate / styrene / benzyl methacrylate copolymer (copolymerization weight ratio = 20 / 15/20/10/15/20, Mw = 28,000) A mixture of 90 parts by weight and 200 parts by weight of propylene glycol monomethyl ether acetate as component (E) was treated with a bead mill in the same manner as in Example 1. A liquid composition of a radiation sensitive composition was prepared in the same manner as in Example 1 except that a pigment dispersion was prepared by dispersing the pigment, and a red stripe color filter was formed on the substrate. .
[0109]
When the obtained board | substrate was observed with the optical microscope, all the patterns with a line width of 10 micrometers or more were closely_contact | adhered to the board | substrate, and the residue was not recognized on the board | substrate of an unexposed part. Moreover, when this board | substrate was observed using the light projector, the ground dirt was not recognized on the board | substrate of an unexposed part. Further, the Ra value of the pixel was 23 mm, and the surface smoothness was extremely excellent. Further, when the surface of the unexposed portion of the substrate was rubbed 10 times with a Toraysee (trade name, manufactured by Toray Industries, Inc.) containing ethanol, the Toraysee was not colored green.
[0110]
Example 4
In Example 1, C.I. I. 90 parts by weight of Pigment Blue 15: 6, and as component (B) 2-N, N-diethylaminoethyl methacrylate / methacrylic acid / N-phenylmaleimide / poly (methyl methacrylate / 2-hydroxyethyl methacrylate) macromonomer / polymethyl methacrylate 90 parts by weight of a macromonomer / styrene / benzyl methacrylate copolymer (copolymerization weight ratio = 20/20/20/10/10/10/10, Mw = 17,000), propylene glycol monomethyl ether acetate as component (E) 200 parts by weight of the mixture was treated with a bead mill in the same manner as in Example 1 to prepare a pigment dispersion by dispersing the pigment. A liquid composition is prepared and a red striped cap is formed on the substrate. It was formed over filter.
[0111]
When the obtained board | substrate was observed with the optical microscope, all the patterns with a line width of 10 micrometers or more were closely_contact | adhered to the board | substrate, and the residue was not recognized on the board | substrate of an unexposed part. Moreover, when this board | substrate was observed using the light projector, the ground dirt was not recognized on the board | substrate of an unexposed part. The Ra value of the pixel was 19%, and the surface smoothness was extremely excellent. Further, when the surface of the unexposed portion of the substrate was rubbed 10 times with a Toraysee (trade name, manufactured by Toray Industries, Inc.) containing ethanol, the Toraysee was not colored green.
[0112]
Comparative Example 1
Instead of the component (B) in Example 1, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer (copolymerization weight ratio = 15/15/60/10, as an alkali-soluble resin, (Mw = 20,000) A liquid composition of a radiation sensitive composition was prepared in the same manner as in Example 1 except that 90 parts by weight were used, and a green stripe color filter was formed on the substrate.
When the obtained substrate was observed with an optical microscope, a pattern with a line width of 25 μm or more was in close contact with the substrate, but a pattern with a line width of 20 μm or less was peeled off from the substrate, and a slight amount was observed on the unexposed portion of the substrate. A residue was observed. Further, when this substrate was observed using a projector, some background contamination was observed on the unexposed substrate. Further, the Ra value of the pixel was 39 mm, and the surface smoothness was slightly inferior. Furthermore, when the surface of the unexposed portion of the substrate was rubbed 5 times with a tresy containing ethanol (trade name, lens cleaner manufactured by Toray Industries, Inc.), the tresy was not colored green. After rubbing 10 times, Toraysee was colored green.
[0113]
Comparative Example 2
In Example 1, a liquid composition of a radiation sensitive composition was prepared in the same manner as in Example 1 except that, when the pigment dispersion was prepared, a mixing process using a stirring blade was performed instead of the dispersion process using a bead mill. Thus, a green striped color filter was formed on the substrate.
When the obtained substrate was observed with an optical microscope, the pattern having a line width of 30 μm or less was peeled from the substrate. Moreover, when this board | substrate was observed using the projector, ground dirt was recognized on the board | substrate of an unexposed part. Further, the Ra value of the pixel was 63 mm, and the surface smoothness was inferior. Further, when the surface of the unexposed portion of the substrate was rubbed five times with a Toraysee (trade name, manufactured by Toray Industries, Inc.) containing ethanol, the Toraysee was colored green.
[0114]
Comparative Example 3
In Example 1, by mixing the components (A) to (E) at a time without previously mixing the components (A), (B), and (E), the radiation-sensitive composition was liquefied. A green striped color filter was formed on the substrate in the same manner as in Example 1 except that the composition was prepared.
When the obtained substrate was observed with an optical microscope, the pattern having a line width of 40 μm or less was peeled from the substrate, and a large amount of residue was observed on the unexposed portion of the substrate. In addition, when this substrate was observed using a projector, significant ground contamination was observed on the unexposed portion of the substrate. Further, the Ra value of the pixel was 88%, and the surface smoothness was extremely inferior. Further, when the surface of the unexposed portion of the substrate was rubbed once with a Toraysee (trade name, lens cleaner manufactured by Toray Industries, Inc.) containing ethanol, the Toraysee was colored green.
[0115]
【The invention's effect】
The radiation sensitive composition for a color filter of the present invention has surface smoothness by dispersing (A) a pigment in advance in a solution obtained by dissolving a specific (B) alkali-soluble resin in (E) a solvent. In addition, a pixel having excellent adhesion to the substrate and the light-shielding layer can be formed, and there is an excellent characteristic that no residue and background stains are generated on the substrate and the light-shielding layer in the unexposed area during development. Therefore, the radiation sensitive composition for color filters of the present invention can be used very suitably for the production of various color filters including color filters for color liquid crystal display elements in the electronic industry.

Claims (5)

(A) a pigment, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation-sensitive polymerization initiator, and (E) a solvent. A radiation sensitive composition for a color filter in which a part or all of a soluble resin is dispersed in a solution obtained by dissolving part or all of (E) a solvent, and is used when a pigment is predispersed. (B) the alkali-soluble resin is a group —NR ₂ (where each R is independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkynyl group having 2 to 18 carbon atoms). A radiation-sensitive composition for a color filter, comprising an alkali-soluble resin having a group, an allyl group, or an aryl group having 6 to 18 carbon atoms. The alkali-soluble resin having the group —NR _{2 according} to claim 1 in the component (B) is (I) an ethylenically unsaturated monomer having the group —NR ₂ and an ethylenically unsaturated monomer having a carboxyl group. body, N- position alkali-soluble copolymer of a substituted maleimide and other copolymerizable monomer, (II) an ethylenically unsaturated monomer having a base -NR _2, ethylenically unsaturated having a carboxyl group monomer, alkali-soluble copolymer of the macromonomer and the other copolymerizable monomer, and (III) an ethylenically unsaturated monomer having a base -NR _2, ethylenically unsaturated having a carboxyl group It contains at least one selected from the group of alkali-soluble copolymers of monomers, N-substituted maleimides, macromonomers and other copolymerizable monomers. The radiation sensitive composition for a color filter according to claim 1. The macromonomer in the alkali-soluble copolymer constituting the component (B) is a macromonomer and / or methyl methacrylate / 2-hydroxyethyl methacrylate copolymer molecule having an ethylenically unsaturated bond at one end of the polymethyl methacrylate molecular chain. The radiation sensitive composition for a color filter according to claim 2, comprising a macromonomer having an ethylenically unsaturated bond at one end of the chain. The color filter formed from the radiation sensitive composition for color filters in any one of Claims 1-3. A color liquid crystal display device comprising the color filter according to claim 4.