JP4785222B2 - Color filter pigment, process for producing the same, color filter coloring composition using the same, and color filter - Google Patents

Description

［Ｘ：直接結合、−ＣＨ_２ＮＨＣＯＣＨ_２−、−ＳＯ_２ＮＨ−、−ＣＯＮＨＯＣＨ_２ＮＨ−、または−（ＣＨ_２）_q ＮＨ−を表す。
Ｒ_１、Ｒ_２：それぞれ独立に、置換されてもよい飽和もしくは不飽和のアルキル基、またはＲ_１、Ｒ_２で窒素、酸素もしくは硫黄原子を含む置換されてもよい複素環を表す。］
【化２】

［Ｚ：直接結合、−ＳＯ₂−、−ＣＯ−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−（ＣＨ₂）_q −、−ＳＯ₂ＮＨ−、−ＣＯＮＨ−、−ＣＨ₂ＮＨＣＯＣＨ₂ＮＨ−、または−（ＣＨ₂）_qＮＨ−を表す。ただし、ｑは１〜１０の整数を表す。
Ｒ₃ 、Ｒ₄ 、Ｒ₅ 、Ｒ₆ ：それぞれ独立に、水素原子、置換されてもよい飽和もしくは不飽和のアルキル基、またはアリール基を表す。
Ｒ₇ ：置換されてもよい飽和もしくは不飽和のアルキル基またはアリール基を表す。］
また、本発明は、ジケトピロロピロール系顔料（Ａ）、水酸基、カルボキシル基、スルホン酸基、カルバモイル基、スルホンアミド基、あるいは下記一般式で示される塩基性置換基を有するキナクリドン誘導体および／またはジケトピロロピロール誘導体からなる色素誘導体（Ｂ）、水溶性無機塩（Ｃ）、および水溶性無機塩（Ｃ）を実質的に溶解しない水溶性有機溶剤（Ｄ）を含む混合物を混練した後、水溶性無機塩（Ｃ）と水溶性有機溶剤（Ｄ）を除去することを特徴とするカラーフィルタ用顔料の製造方法である。
【化３】

［Ｘ：直接結合、−ＣＨ_２ＮＨＣＯＣＨ_２−、−ＳＯ_２ＮＨ−、−ＣＯＮＨＯＣＨ_２ＮＨ−、または−（ＣＨ_２）_q ＮＨ−を表す。
Ｒ_１、Ｒ_２：それぞれ独立に、置換されてもよい飽和もしくは不飽和のアルキル基、またはＲ_１、Ｒ_２で窒素、酸素もしくは硫黄原子を含む置換されてもよい複素環を表す。］
【化４】

［Ｚ：直接結合、−ＳＯ₂−、−ＣＯ−、−ＣＨ₂ＮＨＣＯＣＨ₂−、−（ＣＨ₂）_q −、−ＳＯ₂ＮＨ−、−ＣＯＮＨ−、−ＣＨ₂ＮＨＣＯＣＨ₂ＮＨ−、または−（ＣＨ₂）_qＮＨ−を表す。ただし、ｑは１〜１０の整数を表す。
Ｒ₃ 、Ｒ₄ 、Ｒ₅ 、Ｒ₆ ：それぞれ独立に、水素原子、置換されてもよい飽和もしくは不飽和のアルキル基、またはアリール基を表す。
Ｒ₇ ：置換されてもよい飽和もしくは不飽和のアルキル基またはアリール基を表す。］
また、本発明は、上記カラーフィルタ用顔料を透明樹脂に分散してなることを特徴とするカラーフィルタ用着色組成物である。
また、本発明は、上記カラーフィルタ用着色組成物を用いて形成された画素を具備することを特徴とするカラーフィルタである。
【００１１】
【発明の実施の形態】
本発明のカラーフィルタ用顔料は、具体的には、ジケトピロロピロール系顔料（Ａ）、色素誘導体（Ｂ）、水溶性無機塩（Ｃ）、および水溶性無機塩（Ｃ）を実質的に溶解しない水溶性有機溶剤（Ｄ）を含む混合物をニーダー等で機械的に混練した後、水中に投入しハイスピードミキサー等で攪拌してスラリー状とし、次いでこのスラリーを濾過、水洗することにより水溶性無機塩（Ｃ）と水溶性有機溶剤（Ｄ）を除去して製造される。
【００１２】
ジケトピロロピロール（以下、ＤＰＰという）系顔料（Ａ）は、下記一般式で表される構造の赤〜橙色の顔料で、優れた耐光性、耐熱性を有している。
下記一般式で表されるＤＰＰ系顔料の具体例をカラーインデックスナンバーで示すと、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２５４、２５５、２６４およびＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｏｒａｎｇｅ ７１が挙げられる。
【００１３】
【化１】

【００１４】
色素誘導体（Ｂ）は、キナクリドン誘導体および／またはＤＰＰ誘導体からなる。これらの色素誘導体は、ＤＰＰ系またはキナクリドン系色素の分子に置換基を導入した化合物であり、ソルトミリング時のＤＰＰ系顔料の結晶成長を抑制する働きをするものである。ＤＰＰ系またはキナクリドン系色素を母体骨格とする色素誘導体は、特にＤＰＰ系顔料の結晶成長を抑制する効果が高いため好ましい。
また、色素誘導体としては、ＤＰＰ系顔料の色相に対する影響の少ない、黄色、橙色、赤色の色相を有するものが好適に用いられる。
【００１５】
ＤＰＰ系またはキナクリドン系色素に導入する置換基は、水酸基、カルボキシル基、スルホン酸基、カルバモイル基、スルホンアミド基、あるいは下記一般式で示される塩基性置換基である。
【化５】

Ｘ：直接結合、−ＣＨ_２ＮＨＣＯＣＨ_２−、−ＳＯ_２ＮＨ−、−ＣＯＮＨＯＣＨ_２ＮＨ−、または−（ＣＨ_２）_q ＮＨ−を表す。
Ｒ_１、Ｒ_２：それぞれ独立に、置換されてもよい飽和もしくは不飽和のアルキル基、またはＲ_１、Ｒ_２で窒素、酸素もしくは硫黄原子を含む置換されてもよい複素環を表す。
【００１６】
【化３】

Ｚ：直接結合、−ＳＯ₂ −、−ＣＯ−、−ＣＨ₂ ＮＨＣＯＣＨ₂ −、−（ＣＨ₂ ）_q −、−ＳＯ₂ ＮＨ−、−ＣＯＮＨ−、−ＣＨ₂ ＮＨＣＯＣＨ₂ ＮＨ−、または−（ＣＨ₂ ）_q ＮＨ−を表す。ただし、ｑは１〜１０の整数を表す。
Ｒ₃ 、Ｒ₄ 、Ｒ₅ 、Ｒ₆ ：それぞれ独立に、水素原子、置換されてもよい飽和もしくは不飽和のアルキル基、またはアリール基を表す。
Ｒ₇ ：置換されてもよい飽和もしくは不飽和のアルキル基またはアリール基を表す。
【００１７】
ＤＰＰ系顔料（Ａ）、色素誘導体（Ｂ）、水溶性無機塩（Ｃ）、および水溶性有機溶剤（Ｄ）の混合物を混練する（ソルトミリングする）際に用いる色素誘導体（Ｂ）の量は、特に限定はされないが、ＤＰＰ系顔料に対して０．５〜２０重量％、特に２〜１５％重量％が好ましい。なお、色素誘導体（Ｂ）は分散剤としての効果も有するため、透明樹脂ワニス中への分散性もよいものを選択するのが好ましいが、結晶成長防止効果の高い色素誘導体と、他の色素誘導体または色素誘導体以外の分散剤とを組み合わせてもよい。色素誘導体以外の分散剤としては、リシノール酸や１２−ヒドロキシステアリン酸の縮合物、塩基性高分子化合物、酸基を含む共重合体、脂肪酸エステル類、脂肪族ポリアミン／ポリエステルグラフト重合体、ポリエチレン／ポリプロピレン付加重合体等の、いわゆる樹脂型分散剤を用いることができる。これらの分散剤は、ソルトミリング処理時、あるいは透明樹脂ワニスへのソルトミリング処理顔料の分散時に用いられる。
【００１８】
水溶性無機塩（Ｃ）は、破砕助剤として働くものであり、ソルトミリング時に無機塩の硬度の高さを利用してＤＰＰ系顔料が破砕され、ＤＰＰ系顔料の一次粒子が微細化される。無機塩（Ｃ）は、水に溶解するものであれば特に限定されず、塩化ナトリウム、塩化バリウム、塩化カリウム、硫酸ナトリウム等を用いることができるが、価格の点から塩化ナトリウム（食塩）を用いるのが好ましい。
ソルトミリングする際に用いる無機塩（Ｃ）の量は、処理効率と生産効率の両面から、ＤＰＰ系顔料の１〜２０重量倍、特に３〜１０重量倍であることが好ましい。ＤＰＰ系顔料に対する無機塩の量比が大きいほど微細化効率が高いが、１回の顔料の処理量が少なくなるためである。
【００１９】
水溶性有機溶剤（Ｄ）は、ＤＰＰ系顔料（Ａ）、色素誘導体（Ｂ）および水溶性無機塩（Ｃ）を湿潤する働きをするものであり、水に溶解（混和）し、かつ用いる無機塩（Ｃ）を実質的に溶解しないものであれば特に限定されない。但し、ソルトミリング時に温度が上昇し、溶剤が蒸発し易い状態になるため、安全性の点から、沸点１２０℃以上の高沸点溶剤が好ましい。水溶性有機溶剤（Ｄ）としては、例えば、２−メトキシエタノール、２−ブトキシエタノール、２−（イソペンチルオキシ）エタノール、２−（ヘキシルオキシ）エタノール、ジエチレングリコール、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコール、トリエチレングリコールモノメチルエーテル、液状のポリエチレングリコール、１−メトキシ−２−プロパノール、１−エトキシ−２−プロパノール、ジプロピレングリコール、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、液状のポリプロピレングリコール等が用いられる。
【００２０】
ソルトミリング時には、微細化されたＤＰＰ系顔料を乾燥する際の強い凝集を防止し、容易に透明樹脂に分散できるようにするため、樹脂を併用することができる。ソルトミリング時に樹脂を併用することにより、柔らかい粉体顔料を得ることができる。ソルトミリングに用いる樹脂としては、室温で固体で、水不溶性で、かつ上記有機溶剤に少なくとも一部可溶であるものが好ましく、天然樹脂、変性天然樹脂、合成樹脂、天然樹脂で変性された合成樹脂等が用いられる。天然樹脂としてはロジンが代表的で、変性天然樹脂としてはロジン誘導体、繊維素誘導体、ゴム誘導体、タンパク誘導体およびそれらのオリゴマーが用いられる。合成樹脂としては、エポキシ樹脂、アクリル樹脂、マレイン酸樹脂、ブチラール樹脂、ポリエステル樹脂、メラミン樹脂、フェノール樹脂、ポリウレタン樹脂、ポリアマイド樹脂等が挙げられる。天然樹脂で変性された合成樹脂としてはロジン変性マレイン酸樹脂、ロジン変性フェノール樹脂等が挙げられる。樹脂の使用量は、ＤＰＰ系顔料に対して５〜１００重量％の範囲であることが好ましい。
【００２１】
ソルトミリング時には、上記樹脂の他に、顔料分散助剤、可塑剤等の添加剤あるいは一般に体質顔料として用いられている炭酸カルシウム、硫酸バリウム、シリカ等の無機顔料を併用してもよい。また、色相を調整するために他の顔料と混合して処理を行ってもよい。
【００２２】
本発明の顔料を透明樹脂に分散することにより、カラーフィルタの製造に用いられる着色組成物が得られる。顔料と透明樹脂とは、固形分重量比において、１：４〜１０：１の割合で配合される。
顔料の透明樹脂への分散には、三本ロールミル、二本ロールミル、サンドミル、ニーダー等の各種分散手段を使用できる。また、これらの分散を良好とするために、適宜、各種界面活性剤、色素誘導体等の分散助剤を添加できる。分散助剤は、顔料の分散に優れ、分散後の顔料の再凝集を防止する効果が大きいので、分散助剤を用いて顔料を透明樹脂に分散してなる着色組成物を用いた場合には、透明性に優れたカラーフィルタが得られる。
【００２３】
透明樹脂は、可視光領域の４００〜７００ｎｍの全波長領域において透過率が８０％以上、好ましくは９５％以上の樹脂である。透明樹脂としては、熱硬化性樹脂、熱可塑性樹脂、感光性樹脂や、放射線照射により硬化して樹脂と同様の塗膜を形成するモノマー、オリゴマー等があり、これらを単独または２種以上混合して用いることができる。また、紫外線照射により着色組成物の硬化を行うときには、光開始剤等が用いられる。
しかしながら、カラーフィルタの製造における後の工程において、高温加熱の処理が行われるため、加熱処理においても耐性のよい樹脂を用いることが必要とされる。また、後の工程において種々の溶剤や薬品による処理も行われるため、形成された画像の耐溶剤性や耐薬品性も必要とされる。
【００２４】
熱硬化性樹脂や熱可塑性樹脂としては、例えば, ブチラール樹脂、スチレンーマレイン酸共重合体、塩素化ポリエチレン、塩素化ポリプロピレン、ポリ塩化ビニル、塩化ビニルー酢酸ビニル共重合体、ポリ酢酸ビニル、ポリウレタン系樹脂、フェノール樹脂、ポリエステル樹脂、アクリル系樹脂、アルキッド樹脂、スチレン樹脂、ポリアミド樹脂、ゴム系樹脂、環化ゴム、エポキシ樹脂、セルロース類、ポリブタジエン、ポリイミド樹脂、ベンゾグアナミン樹脂、メラミン樹脂、尿素樹脂等が挙げられる。
【００２５】
感光性樹脂としては、水酸基、カルボキシル基、アミノ基等の反応性の置換基を有する線状高分子にイソシアネート基、アルデヒド基、エポキシ基等を介して、（メタ）アクリル化合物、ケイヒ酸等の光架橋性基を導入した樹脂が用いられる。また、スチレン−無水マレイン酸共重合物やα−オレフィン−無水マレイン酸共重合物等の酸無水物を含む線状高分子をヒドロキシアルキル（メタ）アクリレート等の水酸基を有する（メタ）アクリル化合物によりハーフエステル化した重合物も用いられる。
【００２６】
放射線照射により硬化して樹脂と同様の塗膜を形成するモノマー、オリゴマーとしては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートのカプロラクトン付加物のヘキサ（メタ）アクリレート等の各種アクリル酸エステルおよびメタクリル酸エステル、アクリル酸、メタクリル酸、（メタ）アクリルアミド、N-ヒドロキシメチル（メタ）アクリルアミド、スチレン、酢酸ビニル、アクリロニトリル、メラミン（メタ）アクリレート、エポキシ（メタ）アクリレートプレポリマー等が挙げられる。
【００２７】
光開始剤としては、４−フェノキシジクロロアセトフェノン、４−ｔ−ブチル−ジクロロアセトフェノン、ジエトキシアセトフェノン、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１オン、１−ヒドロキシシクロヘキシルフェニルケトン、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−オン等のアセトフェノン系光開始剤、、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンジルジメチルケタール等のベンゾイン系、ベンゾフェノン系光開始剤、ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４−フェニルベンゾフェノン、ヒドロキシベンゾフェノン、アクリル化ベンゾフェノン、４−ベンゾイル−４’−メチルジフェニルサルファイド等のベンゾフェノン系光開始剤、チオキサンソン、２−クロルチオキサンソン、２−メチルチオキサンソン、イソプロピルチオキサンソン、２，４−ジイソプロピルチオキサンソン等のチオキサンソン系光開始剤、２，４，６−トリクロロ−ｓ−トリアジン、２−フェニル−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（ｐ−メトキシフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（ｐ−トリル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−ピペニル−−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２，４−−ビス（トリクロロメチル）−６−スチリルｓ−トリアジン、２−（ナフト−１−イル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２−（４−メトキシ−ナフト−１−イル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２，４−トリクロロメチル−（ピペロニル）−６−トリアジン、２，４−トリクロロメチル（４’−メトキシスチリル）−６−トリアジン等のトリアジン系光開始剤およびカルバゾール系光開始剤、イミダゾール系光開始剤等の化合物が用いられる。
【００２８】
上記光開始剤は、単独あるいは２種以上混合して用いるが、増感剤として、α−アシロキシムエステル、アシルフォスフィンオキサイド、メチルフェニルグリオキシレート、ベンジル、９，１０−フェナンスレンキノン、カンファーキノン、エチルアンスラキノン、４，４’−ジエチルイソフタロフェノン、３，３’，４，４’−テトラ（ｔ−ブチルパーオキシカルボニル）ベンゾフェノン、４，４’−ジエチルアミノベンゾフェノン等の化合物を併用することもできる。
【００２９】
カラーフィルタ用着色組成物には、着色剤を充分に分散させ、ガラス基板上に乾燥膜厚が０．２〜５μｍとなるように塗布するために溶剤を用いることができる。溶剤としては、例えばシクロヘキサノン、エチルセロソルブアセテート、ブチルセロソルブアセテート、１−メトキシ−２−プロピルアセテート、ジエチレングリコールジメチルエーテル、エチルベンゼン、エチレングリコールジエチルエーテル、キシレン、エチルセロソルブ、メチル−ｎアミルケトン、プロピレングリコールモノメチルエーテルトルエン、メチルエチルケトン、酢酸エチル、メタノール、エタノール、イソプロピルアルコール、ブタノール、イソブチルケトン、石油系溶剤等が挙げられ、これらを単独もしくは混合して用いる。
【００３０】
本発明のカラーフィルタ用着色組成物は、グラビアオフセット用印刷インキ、水無しオフセット印刷インキ、シルクスクリーン印刷用インキ、溶剤現像型あるいはアルカリ現像型着色レジスト剤のようなものにすることができる。
これらの印刷インキ、着色レジスト剤等は、遠心分離、焼結フィルタ、メンブレンフィルタ等の手段にて５μｍ以上の粗大粒子、好ましくは１μｍ以上の粗大粒子さらに好ましくは、０．５μｍ以上の粗大粒子および混入した塵の除去を行い製造する。
【００３１】
上記印刷インキは、印刷と乾燥を繰り返すだけでパターン化された各色の画素が形成できるため、カラーフィルタの製造法としては、低コストで量産性に優れている。さらに、印刷技術の発展により高い寸法精度および平滑度を有する微細パターンの印刷を行うことができる。印刷によりカラーフィルタを製造する場合には、印刷機上でのインキの流動性の制御が重要であり、分散剤や体質顔料によるインキ粘度の調整を行うこともできる。
【００３２】
溶剤現像型あるいはアルカリ現像型着色レジスト剤は、ガラス板等の透明基板上に、スピンコート、スリットコート、ロールコート等の塗布方法により塗布される。次いで、フォトマスクを介して紫外線露光を行い、未露光部を溶剤またはアルカリ現像液で洗い流して所望のパターン形成したのち、同様の操作を他の色について繰り返して各色の画素を具備するカラーフィルタを製造する。この製造法は、フォトリソグラフィー法と呼ばれ、上記印刷法より精度の高いカラーフィルタが製造できる。
【００３３】
アルカリ現像液としては、炭酸ソーダ、苛性ソーダ等の水溶液が使用され、ジメチルベンジルアミン、トリエタノールアミン等の有機塩基を用いることもできる。また、消泡剤や界面活性剤を添加することもできる。
なお，紫外線露光感度を上げるために、上記着色レジスト剤を塗布乾燥後、水溶性あるいはアルカリ水溶性樹脂、例えばポリビニルアルコールや水溶性アクリル樹脂等を塗布乾燥し酸素による重合阻害を防止する膜を形成した後、紫外線露光を行うこともできる。
【００３４】
顔料を用いるカラーフィルタの製造法としては、上記の他に電着法、転写法などがあるが、本発明の着色組成物は、いずれの方法にも用いることができる。なお、電着法は透明基板上に形成した透明導電膜を利用して、コロイド粒子の電気泳動により着色材を透明導電膜の上に電着形成することでカラーフィルタを製造する方法である。また、転写法は剥離性の転写ベースシートの表面に、あらかじめカラーフィルタ層を形成しておき、このカラーフィルタ層を所望の透明基板に転写させる方法である。
【００３５】
以下、本発明を実施例に基づいて説明するが、本発明はこれによって限定されるものではない。なお、実施例および比較例中、部とは重量部を、％とは重量％をそれぞれ示す。また、顔料の一次粒子径は、透過型電子顕微鏡で観察して測定し、比表面積はＢＥＴ法で測定した。
実施例に先立ち、実施例で用いた色素誘導体を表１に示す。
【００３６】
【表１】

【００３７】
（アクリル樹脂の合成）
反応容器にシクロヘキサノン８００部を入れ、容器に窒素ガスを注入しながら１００℃に加熱して、同温度で下記モノマーおよび熱重合開始剤の混合物を１時間かけて滴下して重合反応を行った。
スチレン ６０．０部
メタクリル酸 ６０．０部
メタクリル酸メチル ６５．０部
メタクリル酸ブチル ６５．０部
アゾビスイソブチロニトリル １０．０部
滴下後さらに１００℃で３時間反応させた後、アゾビスイソブチロニトリル２．０部をシクロヘキサノン５０部で溶解させたものを添加し、さらに１００℃で１時間反応を続けて樹脂溶液を合成した。
室温まで冷却した後、樹脂溶液約２ｇをサンプリングして１８０℃、２０分加熱乾燥して不揮発分を測定し、先に合成した樹脂溶液に不揮発分が２０％となるようにシクロヘキサノンを添加してアクリル樹脂溶液を調製した。
【００３８】
［実施例１］
ＤＰＰ顔料（チバスペシャルティケミカルズ社製「イルガジンＤＰＰ ＲＥＤＢＯ」、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ ＲＥＤ２５４）１５２部、色素誘導体（ａ）８部、塩化ナトリウム１６００部、およびジエチレングリコール１９０部をステンレス製１ガロンニーダー（井上製作所社製）に仕込み、６０℃で１０時間混練した。つぎにこの混合物を３リットルの温水に投入し、約８０℃に加熱しながらハイスピードミキサーで約１時間攪拌してスラリー状とし、濾過、水洗をくりかえして塩化ナトリウムおよび溶剤を除いた後、８０℃で１昼夜乾燥し、１５６．８部のカラーフィルタ用顔料（一次粒子径３０〜４０nm、比表面積８０m²/g）を得た。
【００３９】
［実施例２］
ＤＰＰ顔料をチバスペシャルティケミカルズ社製ＤＰＰ顔料「イルガジンＤＰＰスカーレットＥＫ」（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ ＲＥＤ２５５）に、色素誘導体（ａ）を色素誘導体（ｂ）に代えた以外は、実施例１と同様の操作を行い１５８．７部のカラーフィルタ用顔料（一次粒子径４０〜５０nm、比表面積６８m²/g）を得た。
【００４０】
［実施例３］
色素誘導体（ａ）を色素誘導体（ｃ）に代えた以外は、実施例１と同様の操作を行い１５６．０部のカラーフィルタ用顔料（一次粒子径３０〜４０nm、比表面積８０m²/g）を得た。
［実施例４］
ＤＰＰ顔料の量を１５２部から１４４部に代え、色素誘導体（ａ）８部を色素誘導体（ｄ）１６部に代えた以外は、実施例１と同様の操作を行い１５６．６部のカラーフィルタ用顔料（一次粒子径２０〜３０nm、比表面積８５m²/g）を得た。
【００４１】
［実施例５］
色素誘導体（ａ）を色素誘導体（ｄ）に代え、混練時の温度を６０℃から９０℃に変更した以外は、実施例１と同様の操作を行い１５６．０部のカラーフィルタ用顔料（一次粒子径３０〜５０nm、比表面積７１m²/g）を得た。
［実施例６］
色素誘導体（ａ）を色素誘導体（ｄ）に代えた以外は、実施例１と同様の操作を行い１５６．５部のカラーフィルタ用顔料（一次粒子径３０〜４０nm、比表面積７９m²/g）を得た。
【００４２】
［実施例７］
ＤＰＰ顔料の量を１５２部から１５５．２部に代え、色素誘導体（ａ）８部を色素誘導体（ｄ）４．８部に代えた以外は、実施例１と同様の操作を行い１５６．４部のカラーフィルタ用顔料（一次粒子径３０〜５０nm、比表面積７２m²/g）を得た。
［実施例８］
ＤＰＰ顔料「イルガジンＤＰＰ ＲＥＤ ＢＯ」１９０部、色素誘導体（ｄ）１０部、塩化ナトリウム２０００部、およびジエチレングリコール２４０部をステンレス製１ガロンニーダーに仕込み、６０℃で１０時間混練した。実施例１と同様にして精製、乾燥を行い、１９４．２部のカラーフィルタ用顔料（一次粒子径３０〜５０nm、比表面積７２m²/g）を得た。
【００４３】
［実施例９］
色素誘導体（ａ）を色素誘導体（ｅ）に代えた以外は、実施例１と同様の操作を行い１５４．８部のカラーフィルタ用顔料（一次粒子径３０〜４０nm、比表面積７９m²/g）を得た。
［実施例１０］
ＤＰＰ顔料をチバスペシャルティケミカルズ社製ＤＰＰ顔料「クロモフタールＤＰＰ オレンジＴＲ」（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ ＯＲＡＮＧＥ７１）に、色素誘導体（ａ）を色素誘導体（ｅ）に代えた以外は、実施例１と同様の操作を行い１５６．０部のカラーフィルタ用顔料（一次粒子径４０〜５０nm、比表面積７３m²/g）を得た。
【００４４】
［実施例１１］
色素誘導体（ａ）を色素誘導体（ｆ）に代えた以外は、実施例１と同様の操作を行い１５６．５部のカラーフィルタ用顔料（一次粒子径３０〜４０nm、比表面積８２m²/g）を得た。
［実施例１２］
ＤＰＰ顔料をチバスペシャルティケミカルズ社製ＤＰＰ顔料「イルガジン ＤＰＰ ルビンＴＲ」（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ ＲＥＤ２６４）に、色素誘導体（ａ）を色素誘導体（ｆ）に代えた以外は、実施例１と同様の操作を行い１５６．５部のカラーフィルタ用顔料（一次粒子径４０〜５０nm、比表面積７３m²/g）を得た。
【００４５】
［実施例１３］
色素誘導体（ａ）を色素誘導体（ｇ）に代えた以外は、実施例１と同様の操作を行い１５６．５部のカラーフィルタ用顔料（一次粒子径３０〜４０nm、比表面積７７m²/g）を得た。
［実施例１４］
色素誘導体（ａ）を色素誘導体（ｈ）に代えた以外は、実施例１と同様の操作を行い１５６．０部のカラーフィルタ用顔料（一次粒子径３０〜４０nm、比表面積８０m²/g）を得た。
【００４６】
［実施例１５］
ＤＰＰ顔料をチバスペシャルティケミカルズ社製ＤＰＰ顔料「イルガジンＤＰＰスカーレットＥＫ」（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ ＲＥＤ２５５）に、色素誘導体（ａ）を色素誘導体（ｉ）に代えた以外は、実施例１と同様の操作を行い１５７．２部のカラーフィルタ用顔料（一次粒子径４０〜５０nm、比表面積７０m²/g）を得た。
【００４７】
［実施例１６］
ＤＰＰ顔料をチバスペシャルティケミカルズ社製ＤＰＰ顔料「イルガジン ＤＰＰ ルビンＴＲ」（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ ＲＥＤ２６４）に、色素誘導体（ａ）を色素誘導体（ｊ）に代えた以外は、実施例１と同様の操作を行い１５６．４部のカラーフィルタ用顔料（一次粒子径３０〜４０nm、比表面積８１m²/g）を得た。
【００４８】
［実施例１７］
ＤＰＰ顔料をチバスペシャルティケミカルズ社製ＤＰＰ顔料「クロモフタールＤＰＰ オレンジＴＲ」（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ ＯＲＡＮＧＥ７１）に、色素誘導体（ａ）を色素誘導体（ｋ）に代えた以外は、実施例１と同様の操作を行い１５６．６部のカラーフィルタ用顔料（一次粒子径３０〜４０nm、比表面積８１m²/g）を得た。
【００４９】
［実施例１８］
ＤＰＰ顔料、色素誘導体（ａ）、塩化ナトリウムおよびジエチレングリコールを混練する際に、マレイン酸樹脂（荒川化学工業社製「マルキード Ｎｏ．３２」）８部を加えた以外は、実施例１と同様の操作を行い１５９．１部のカラーフィルタ用顔料（一次粒子径３０〜４０nm、比表面積８７m²/g）を得た。
【００５０】
［比較例２］
色素誘導体（ｂ）を除いた以外は、実施例２と同様の操作を行い１４９．０部の処理顔料（一次粒子径１００〜２００nm、比表面積４５m²/g）を得た。
【００５１】
［比較例３］
色素誘導体（ｆ）をマレイン酸樹脂（荒川化学工業社製「マルキード Ｎｏ．３２」）８部に代えた以外は、実施例１２と同様の操作を行い１５７．０部の処理顔料（一次粒子径４０〜６０nm、比表面積７８m²/g）を得た。
［比較例４］
色素誘導体（ｅ）をエポキシ樹脂（油化シェルエポキシ社製「エピコート１００４」）８部に代えた以外は、実施例１０と同様の操作を行い１５８．２部の処理顔料（一次粒子径６０〜７０nm、比表面積７８m²/g）を得た。
【００５２】
［比較例５］
未処理のＤＰＰ顔料（チバスペシャルティケミカルズ社製「イルガフォー ＲＥＤ Ｂ−ＣＦ」、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ ＲＥＤ２５４、一次粒子径４０〜６０nm、比表面積８５m²/g）
［比較例６］
未処理のＤＰＰ顔料（チバスペシャルティケミカルズ社製「イルガジンＤＰＰＲＥＤ ＢＯ」、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ ＲＥＤ２５４、一次粒子径２００〜６００nm、比表面積２５m²/g）
【００５３】
［比較例７］
未処理のＤＰＰ顔料（チバスペシャルティケミカルズ社製「イルガジンＤＰＰスカーレットＥＫ」、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ ＲＥＤ２５５、一次粒子径２００〜４００nm、比表面積３０m²/g）
［比較例８］
未処理のＤＰＰ顔料（チバスペシャルティケミカルズ社製「イルガジンＤＰＰルビンＴＲ」、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ ＲＥＤ２６４、一次粒子径４０〜１００nm、比表面積７０m²/g）
［比較例９］
未処理のＤＰＰ顔料（チバスペシャルティケミカルズ社製「クロモフタール ＤＰＰ オレンジＴＲ」、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ ＯＲＡＮＧＥ７１、一次粒子径４０〜２００nm、比表面積７８m²/g）
【００５４】
実施例および比較例で得られた顔料を含む下記組成の混合物を均一に撹拌混合した後、１μｍのフィルタで濾過してアルカリ現像型感光性着色組成物を作製した。
顔料 ４．５部
上記アクリル樹脂溶液 ２４．０部
トリメチロールプロパントリアクリレート ５．４部
（新中村化学社製「ＮＫエステルＡＴＭＰＴ」）
光開始剤（チバガイギー社製「イルガキュアー９０７」） ０．３部
増感剤（保土ヶ谷化学社製「ＥＡＢ−Ｆ」） ０．２部
シクロヘキサノン ６５．１部
【００５５】
得られた感光性着色組成物を用いて、下記の方法で透明基板上に色材層を形成し、色材層の分光透過率、色度、表面状態、およびＮＭＰ耐性を評価した。結果を表２に示す。
１００ｍｍ×１００ｍｍ、１．１ｍｍ厚のガラス基板上に、得られた感光性着色組成物をスピンコーターを用いて５００ｒｐｍ、１０００ｒｐｍ、１５００ｒｐｍ、２０００ｒｐｍの回転数で塗布し、色材層の膜厚が異なる４種の塗布基板を得た。次に、７０℃で２０分乾燥後、超高圧水銀ランプを用いて、積算光量１５０ｍＪで紫外線露光を行った。露光後２３０℃で１時間加熱して放冷後、顕微分光光度計（オリンパス光学社製「ＯＳＰ−ＳＰ１００」）を用いてＣ光源での色度（Ｙ，ｘ，ｙ）を測定した。４組の色度・分光測定結果から４００〜７００ｎｍ波長の分光透過率の最小値が１％になる時の最大透過率、Ｙ、ｘおよびｙを求めた。さらに１０００ｒｐｍの塗布基板の表面状態を光学顕微鏡（オリンパス光学社製「ＢＸ６０」）で観察した。観察後、塗布基板をＮＭＰに３０分浸漬・乾燥後顕微分光光度計にて塗布基板色度測定し、浸漬前後の色差ΔＥを求め、塗布基板のＮＭＰ耐性を評価した。
【００５６】
【表２】

【００５７】
色素誘導体を用いてソルトミリング処理した実施例１〜１７のＤＰＰ系顔料を透明樹脂に分散してなる感光性着色組成物を用いて形成された色材層は、顔料が微細化され分散状態が良好なため、いずれも最小透過率を同一にしたとき最大透過率が高くなっている。すなわち、不要な光を遮断し必要な光をより多く透過させる、カラーフィルターとして優れた特性を有している。例えば、ソルトミリング処理しないＤＰＰ系顔料「イルガジンＤＰＰ ＲＥＤ ＢＯ」（比較例６）を用いて形成された色材層の最大透過率が８７％であるに対し、実施例1 、３〜９では、色材層の最大透過率が９５〜９９％と飛躍的に向上している。
【００５８】
これは、同じＣ．Ｉ．Ｐｉｇｍｅｎｔ ＲＥＤ２５４で微細化タイプのＢ−ＣＦ（比較例５）を用いた場合よりも高い。また、色素誘導体なしでＤＰＰ系顔料「イルガジンＤＰＰ ＲＥＤ ＢＯ」をソルトミリング処理した比較例１では、最大透過率が７９％と未処理の場合より不透明になっている。一次粒子径が比較例１の方が大きいことから、色素誘導体なしでソルトミリングした場合には、結ＤＰＰ系顔料が晶成長することがわかる。
また、耐熱性に関して、比較例では２３０℃の加熱で塗膜表面に５〜１０μｍ程度の突起が認められるのに対し、実施例１〜１７の塗膜表面では観察されない。また、ＮＭＰ耐性では比較例のΔＥが３〜４であるのに対し実施例はいずれもΔＥ＝１前後と色変化が小さく、ＮＭＰ耐性が高いことを示している。
【００５９】
【発明の効果】
本発明により、結晶成長を抑制して微細なジケトピロロピロール系顔料が得られるようになった。また、本発明の顔料を用いることにより、高い透明性とＮＭＰ耐性を有する優れた画素を具備するカラーフィルタが得られるようになった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a pigment used for a color filter used in a color liquid crystal display device and a solid-state imaging device, a method for producing the same, a coloring composition using the pigment, and a color filter using the coloring composition.
[0002]
[Prior art]
Color filters are those in which two or more kinds of fine bands (stripes) of different hues are arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or in which fine pixels are arranged in a constant vertical and horizontal arrangement. It has become. The pixels are as fine as several tens to several hundreds of microns, and are arranged regularly in a predetermined arrangement for each hue.
A color filter is used in a color liquid crystal display device. In general, a transparent electrode for driving a liquid crystal is formed on the color filter by vapor deposition or sputtering, and the liquid crystal is oriented in a certain direction on the transparent electrode. The alignment film is formed. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.
[0003]
Therefore, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used. The color filter is mainly produced by the following two methods. Is manufactured.
In the first method, a dispersion of a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass, the solvent is removed by drying, a pattern exposure of one filter color is performed, and then an unexposed portion is obtained. The color filter can be manufactured by repeating the same operation for all the filter colors in order after forming a first color pattern by applying a process such as heating if necessary.
[0004]
In the second method, a dispersion of a pigment in a transparent resin solution is applied to a transparent substrate such as glass, the solvent is removed by drying, and then a resist such as a positive resist is applied on the coating film. Perform pattern exposure of two filter colors, develop to form a resist pattern, use this as an etching resist, remove the pigment dispersion coating without the resist pattern with an etchant, peel the resist coating, and remove the first color A color filter can be manufactured by repeating the same operation sequentially for all the filter colors after forming the above pattern and applying a treatment such as heating if necessary. Note that the development of the resist and the etching of the pigment-dispersed coating film can be performed simultaneously.
[0005]
In the above method, a dianthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment, and the like have been conventionally used for producing a red filter. In particular, diketopyrrolopyrrole pigments have high brightness, are excellent in light resistance, and heat resistance, and therefore are increasingly used as color filter pigments. However, there is a strong demand for pigments with higher brightness. To that end, it is necessary to further refine the primary particle size of diketopyrrolopyrrole pigments to improve transparency.
[0006]
On the other hand, as a method for refining the primary particle diameter of a pigment, Japanese Patent Application Laid-Open No. 7-13016 discloses a pigment, a synthetic resin that is solid and water-insoluble at room temperature, a water-soluble inorganic salt such as sodium chloride, and the synthetic resin. After mechanically kneading with a kneader or the like together with a water-soluble organic solvent that at least partially dissolves (hereinafter, kneading a mixture containing a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is called salt milling), There is a method of removing inorganic salts and organic solvents by washing with water. In this method, the primary particle pulverization and crystal growth occur in parallel with each other, so that a pigment with a small surface area is obtained in the end although the particle size distribution is narrow and the average particle size is small. This method is suitable for applications where a pigment having a large diameter needs to be dispersed at a high concentration.
[0007]
However, since the diketopyrrolopyrrole pigment has a structure containing> NH and C = O as a control, it has the property of easily growing crystals due to hydrogen bonding, and the diketopyrrolopyrrole pigment alone is subjected to salt milling treatment. In this case, there is a problem that the crystal growth is more advanced than the pulverization of the primary particles, and the particle size is increased, and the pigment has not been suitable for the salt milling process.
An alignment film is formed on the color filter via a transparent electrode. Polyimide is generally used as the alignment film material, and solubility such as N-methylpyrrolidone (hereinafter referred to as NMP) is used. An alignment film is formed by applying a solution in which polyamic acid, which is a polyimide precursor, is dissolved in a very high basic solvent.
However, a red filter using a conventional diketopyrrolopyrrole pigment has a drawback that its resistance to NMP is insufficient.
[0008]
[Problems to be solved by the invention]
The present invention relates to a pigment for a color filter that provides a red filter having excellent heat resistance and light resistance, high brightness, and good resistance to NMP, a method for producing the same, a coloring composition for a color filter using the same, and a color filter For the purpose of provision.
[0009]
[Means for Solving the Problems]
As a result of continuing intensive studies to solve the above problems, the present inventors have suppressed the crystal growth of the diketopyrrolopyrrole pigment by using the dye derivative when salt milling the diketopyrrolopyrrole pigment. The inventors have found that a pigment having a fine primary particle can be obtained, and that a red filter formed using the pigment has good resistance to NMP, leading to the present invention.
The reason why the red filter formed using the diketopyrrolopyrrole pigment formed by salt milling in the presence of the dye derivative has good resistance to NMP is not clear, but the shape of the primary particles of the obtained pigment It is considered that this is because the surface area is small for a small primary particle diameter as described above.
[0010]
That is, the present invention provides a diketopyrrolopyrrole pigment (A), It consists of a quinacridone derivative and / or a diketopyrrolopyrrole derivative having a hydroxyl group, a carboxyl group, a sulfonic acid group, a carbamoyl group, a sulfonamide group, or a basic substituent represented by the following general formula After kneading a mixture containing a pigment derivative (B), a water-soluble inorganic salt (C), and a water-soluble organic solvent (D) that does not substantially dissolve the water-soluble inorganic salt (C), the water-soluble inorganic salt (C) And a water-soluble organic solvent (D).
[Chemical 1]

[X: direct bond, -CH ₂ NHCOCH ₂ -, -SO ₂ NH-, -CONHOCH ₂ NH- or-(CH ₂ ) _q NH- is represented.
R ₁ , R ₂ : Each independently a saturated or unsaturated alkyl group which may be substituted, or R ₁ , R ₂ Represents an optionally substituted heterocyclic ring containing a nitrogen, oxygen or sulfur atom. ]
[Chemical 2]

[Z: direct bond, -SO ₂ -, -CO-, -CH ₂ NHCOCH ₂ -,-(CH ₂ ) _q -, -SO ₂ NH-, -CONH-, -CH ₂ NHCOCH ₂ NH- or-(CH ₂ ) _q NH- is represented. However, q represents the integer of 1-10.
R _Three , R _Four , R _Five , R ₆ : Each independently represents a hydrogen atom, an optionally substituted saturated or unsaturated alkyl group, or an aryl group.
R ₇ : Represents an optionally substituted saturated or unsaturated alkyl group or aryl group. ]
The present invention also provides: From diketopyrrolopyrrole pigment (A), hydroxyl group, carboxyl group, sulfonic acid group, carbamoyl group, sulfonamide group, or a quinacridone derivative and / or diketopyrrolopyrrole derivative having a basic substituent represented by the following general formula After kneading a mixture containing a water-soluble organic solvent (D) that does not substantially dissolve the dye derivative (B), the water-soluble inorganic salt (C), and the water-soluble inorganic salt (C), the water-soluble inorganic salt (C ) And water-soluble organic solvent (D) are removed. It is a manufacturing method of the pigment for color filters.
[Chemical 3]

[X: direct bond, -CH ₂ NHCOCH ₂ -, -SO ₂ NH-, -CONHOCH ₂ NH- or-(CH ₂ ) _q NH- is represented.
R ₁ , R ₂ : Each independently a saturated or unsaturated alkyl group which may be substituted, or R ₁ , R ₂ Represents an optionally substituted heterocyclic ring containing a nitrogen, oxygen or sulfur atom. ]
[Formula 4]

[Z: direct bond, -SO ₂ -, -CO-, -CH ₂ NHCOCH ₂ -,-(CH ₂ ) _q -, -SO ₂ NH-, -CONH-, -CH ₂ NHCOCH ₂ NH- or-(CH ₂ ) _q NH- is represented. However, q represents the integer of 1-10.
R _Three , R _Four , R _Five , R ₆ : Each independently represents a hydrogen atom, an optionally substituted saturated or unsaturated alkyl group, or an aryl group.
R ₇ : Represents an optionally substituted saturated or unsaturated alkyl group or aryl group. ]
The present invention also provides a color filter coloring composition comprising the color filter pigment dispersed in a transparent resin.
Moreover, this invention comprises the pixel formed using the said coloring composition for color filters, It is a color filter characterized by the above-mentioned.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Specifically, the color filter pigment of the present invention substantially comprises a diketopyrrolopyrrole pigment (A), a dye derivative (B), a water-soluble inorganic salt (C), and a water-soluble inorganic salt (C). A mixture containing a water-soluble organic solvent (D) that does not dissolve is mechanically kneaded with a kneader or the like, then poured into water and stirred with a high-speed mixer or the like to form a slurry, and then the slurry is filtered and washed with water. It is produced by removing the water-soluble inorganic salt (C) and the water-soluble organic solvent (D).
[0012]
The diketopyrrolopyrrole (hereinafter referred to as DPP) pigment (A) is a red to orange pigment having a structure represented by the following general formula, and has excellent light resistance and heat resistance.
Specific examples of DPP pigments represented by the following general formula are represented by color index numbers. I. Pigment Red 254, 255, 264 and C.I. I. Pigment Orange 71.
[0013]
[Chemical 1]

[0014]
The pigment derivative (B) is composed of a quinacridone derivative and / or a DPP derivative. These dye derivatives are compounds in which substituents are introduced into the molecules of a DPP-type or quinacridone-type dye, and function to suppress crystal growth of the DPP-type pigment during salt milling. A dye derivative having a DPP-type or quinacridone-type dye as a base skeleton is particularly preferable because it has a high effect of suppressing crystal growth of the DPP-type pigment.
Further, as the pigment derivative, those having yellow, orange and red hues which have little influence on the hue of the DPP pigment are preferably used.
[0015]
The substituent introduced into the DPP-type or quinacridone-type dye is a hydroxyl group, a carboxyl group, a sulfonic acid group, a carbamoyl group, a sulfonamide group, or a basic substituent represented by the following general formula.
[Chemical formula 5]

X: direct bond, —CH ₂ NHCOCH ₂ -, -SO ₂ NH-, -CONHOCH ₂ NH- or-(CH ₂ ) _q NH- is represented.
R ₁ , R ₂ : Each independently a saturated or unsaturated alkyl group which may be substituted, or R ₁ , R ₂ Represents an optionally substituted heterocyclic ring containing a nitrogen, oxygen or sulfur atom.
[0016]
[Chemical 3]

Z: direct bond, -SO ₂ -, -CO-, -CH ₂ NHCOCH ₂ -,-(CH ₂ ) _q -, -SO ₂ NH-, -CONH-, -CH ₂ NHCOCH ₂ NH- or-(CH ₂ ) _q NH- is represented. However, q represents the integer of 1-10.
R _Three , R _Four , R _Five , R ₆ : Each independently represents a hydrogen atom, an optionally substituted saturated or unsaturated alkyl group, or an aryl group.
R ₇ : Represents an optionally substituted saturated or unsaturated alkyl group or aryl group.
[0017]
The amount of the pigment derivative (B) used when kneading (salt milling) a mixture of the DPP pigment (A), the pigment derivative (B), the water-soluble inorganic salt (C), and the water-soluble organic solvent (D) is Although not particularly limited, it is preferably 0.5 to 20% by weight, particularly 2 to 15% by weight, based on the DPP pigment. In addition, since the pigment derivative (B) also has an effect as a dispersant, it is preferable to select a pigment derivative having good dispersibility in the transparent resin varnish. Or you may combine with dispersing agents other than a pigment derivative. Dispersants other than pigment derivatives include condensates of ricinoleic acid and 12-hydroxystearic acid, basic polymer compounds, copolymers containing acid groups, fatty acid esters, aliphatic polyamine / polyester graft polymers, polyethylene / So-called resin-type dispersants such as polypropylene addition polymers can be used. These dispersants are used at the time of salt milling treatment or at the time of dispersing the salt milling treatment pigment in the transparent resin varnish.
[0018]
The water-soluble inorganic salt (C) serves as a crushing aid, and the DPP pigment is crushed using the high hardness of the inorganic salt during salt milling, and the primary particles of the DPP pigment are refined. . The inorganic salt (C) is not particularly limited as long as it is soluble in water, and sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used, but sodium chloride (salt) is used from the viewpoint of price. Is preferred.
The amount of the inorganic salt (C) used for salt milling is preferably 1 to 20 times by weight, particularly 3 to 10 times by weight of the DPP pigment, from the viewpoint of both processing efficiency and production efficiency. This is because the finer efficiency is higher as the amount ratio of the inorganic salt to the DPP pigment is larger, but the processing amount of one pigment is reduced.
[0019]
The water-soluble organic solvent (D) functions to wet the DPP pigment (A), the dye derivative (B), and the water-soluble inorganic salt (C), and is an inorganic substance that is dissolved (mixed) in water and used. There is no particular limitation as long as it does not substantially dissolve the salt (C). However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent easily evaporates. Examples of the water-soluble organic solvent (D) include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid Polypropylene glycol or the like is used.
[0020]
At the time of salt milling, a resin can be used in combination in order to prevent strong agglomeration at the time of drying the miniaturized DPP pigment and to allow easy dispersion in the transparent resin. By using a resin together during salt milling, a soft powder pigment can be obtained. The resin used for salt milling is preferably a resin that is solid at room temperature, insoluble in water, and at least partially soluble in the above organic solvent. Natural resin, modified natural resin, synthetic resin, synthetic resin modified with natural resin Resin or the like is used. As the natural resin, rosin is representative, and as the modified natural resin, rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof are used. Examples of the synthetic resin include epoxy resin, acrylic resin, maleic acid resin, butyral resin, polyester resin, melamine resin, phenol resin, polyurethane resin, and polyamide resin. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins. The amount of the resin used is preferably in the range of 5 to 100% by weight with respect to the DPP pigment.
[0021]
At the time of salt milling, in addition to the above resins, additives such as pigment dispersion aids and plasticizers, or inorganic pigments such as calcium carbonate, barium sulfate and silica generally used as extender pigments may be used in combination. Moreover, in order to adjust a hue, you may mix and process with another pigment.
[0022]
By dispersing the pigment of the present invention in a transparent resin, a colored composition used for producing a color filter can be obtained. The pigment and the transparent resin are blended at a ratio of 1: 4 to 10: 1 in the solid content weight ratio.
Various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, and a kneader can be used for dispersing the pigment in the transparent resin. Moreover, in order to make these dispersion | distribution favorable, dispersion | distribution adjuvants, such as various surfactant and a pigment derivative, can be added suitably. The dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing the pigment in a transparent resin using the dispersion aid is used. A color filter having excellent transparency can be obtained.
[0023]
The transparent resin is a resin having a transmittance of 80% or more, preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Transparent resins include thermosetting resins, thermoplastic resins, photosensitive resins, and monomers, oligomers, etc. that form a coating film similar to the resin when cured by radiation irradiation. These can be used alone or in combination. Can be used. Moreover, when hardening a coloring composition by ultraviolet irradiation, a photoinitiator etc. are used.
However, since a high-temperature heating process is performed in a later process in the production of the color filter, it is necessary to use a resin having good resistance even in the heating process. In addition, since processing with various solvents and chemicals is also performed in a later process, the solvent resistance and chemical resistance of the formed image are also required.
[0024]
Examples of thermosetting resins and thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane series. Resin, phenol resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, cellulose, polybutadiene, polyimide resin, benzoguanamine resin, melamine resin, urea resin, etc. Can be mentioned.
[0025]
As the photosensitive resin, a (meth) acrylic compound, cinnamic acid, or the like is bonded to a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group via an isocyanate group, an aldehyde group, an epoxy group, or the like. A resin into which a photocrosslinkable group is introduced is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified polymers can also be used.
[0026]
Monomers and oligomers that are cured by radiation irradiation to form a coating film similar to a resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) ) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, hexa (meth) acrylate of caprolactone adduct of dipentaerythritol hexa (meth) acrylate, etc. Acrylic acid ester and methacrylic acid ester, acrylic acid, methacrylic acid, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, styrene, vinyl acetate, acrylonitrile Melamine (meth) acrylate, epoxy (meth) acrylate prepolymer, and the like.
[0027]
As photoinitiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1one, 1-hydroxycyclohexyl Acetophenone photoinitiators such as phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin series such as benzyl dimethyl ketal, benzophenone series photoinitiator, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, -Benzophenone photoinitiators such as benzoyl-4'-methyldiphenyl sulfide, thioxanthone light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 --Bis (trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (to Chloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine , 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine and other compounds such as triazine photoinitiators and carbazole photoinitiators and imidazole photoinitiators are used.
[0028]
The photoinitiator may be used alone or in combination of two or more. As a sensitizer, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, Combined use of compounds such as camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone You can also
[0029]
In the coloring composition for a color filter, a solvent can be used in order to sufficiently disperse the coloring agent and apply it on the glass substrate so that the dry film thickness is 0.2 to 5 μm. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination.
[0030]
The coloring composition for a color filter of the present invention can be a gravure offset printing ink, a waterless offset printing ink, a silk screen printing ink, a solvent developing type or an alkali developing type coloring resist agent.
These printing inks, coloring resist agents and the like are coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, and coarse particles by means of centrifugation, sintered filter, membrane filter and the like. It is manufactured by removing the mixed dust.
[0031]
Since the printing ink can form patterned pixels of each color simply by repeating printing and drying, it is low cost and excellent in mass productivity as a method for producing a color filter. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In the case of producing a color filter by printing, it is important to control the fluidity of the ink on the printing press, and the ink viscosity can be adjusted with a dispersant or extender pigment.
[0032]
The solvent development type or alkali development type coloring resist agent is applied on a transparent substrate such as a glass plate by a coating method such as spin coating, slit coating or roll coating. Next, UV exposure is performed through a photomask, and the unexposed portion is washed away with a solvent or an alkali developer to form a desired pattern. Then, the same operation is repeated for other colors to obtain a color filter having pixels of each color. To manufacture. This manufacturing method is called a photolithography method, and a color filter with higher accuracy than the printing method can be manufactured.
[0033]
As the alkaline developer, an aqueous solution such as sodium carbonate or caustic soda is used, and an organic base such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist agent, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.
[0034]
As a method for producing a color filter using a pigment, in addition to the above, there are an electrodeposition method, a transfer method, and the like, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and electrodepositing a coloring material on the transparent conductive film by electrophoresis of colloidal particles. The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.
[0035]
EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited by this. In Examples and Comparative Examples, “part” means “part by weight” and “%” means “% by weight”. The primary particle diameter of the pigment was measured by observation with a transmission electron microscope, and the specific surface area was measured by the BET method.
Prior to the examples, the pigment derivatives used in the examples are shown in Table 1.
[0036]
[Table 1]

[0037]
(Synthesis of acrylic resin)
A reaction vessel was charged with 800 parts of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
60.0 parts of styrene
Methacrylic acid 60.0 parts
Methyl methacrylate 65.0 parts
65.0 parts butyl methacrylate
Azobisisobutyronitrile 10.0 parts
After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to synthesize a resin solution. did.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution was prepared.
[0038]
[Example 1]
DPP pigment ("Irgazine DPP REDBO" manufactured by Ciba Specialty Chemicals, CI Pigment RED254) 152 parts, 8 parts of pigment derivative (a), 1600 parts of sodium chloride, and 190 parts of diethylene glycol 1 gallon kneader (Inoue Seisakusho) And kneaded at 60 ° C. for 10 hours. Next, the mixture is poured into 3 liters of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and solvent, and then 80 After drying for 1 day at 15 ° C., 156.8 parts of pigment for color filter (primary particle size 30-40 nm, specific surface area 80 m ² / g).
[0039]
[Example 2]
The same procedure as in Example 1 except that the DPP pigment was changed to the DPP pigment “Irgazine DPP Scarlet EK” (CI Pigment RED255) manufactured by Ciba Specialty Chemicals, and the pigment derivative (a) was replaced with the pigment derivative (b). 158.7 parts of color filter pigment (primary particle size 40-50 nm, specific surface area 68 m ² / g).
[0040]
[Example 3]
The same procedure as in Example 1 was carried out except that the pigment derivative (a) was replaced with the pigment derivative (c), and 156.0 parts of a pigment for color filter (primary particle diameter of 30 to 40 nm, specific surface area of 80 m) ² / g).
[Example 4]
The same procedure as in Example 1 was carried out except that the amount of DPP pigment was changed from 152 parts to 144 parts, and 8 parts of the dye derivative (a) was changed to 16 parts of the dye derivative (d). Pigment (primary particle size 20-30 nm, specific surface area 85 m ² / g).
[0041]
[Example 5]
The same procedure as in Example 1 was conducted except that the pigment derivative (a) was replaced by the pigment derivative (d) and the kneading temperature was changed from 60 ° C. to 90 ° C. Particle size 30-50nm, specific surface area 71m ² / g).
[Example 6]
The same operation as in Example 1 was carried out except that the pigment derivative (a) was replaced with the pigment derivative (d), and 156.5 parts of a pigment for a color filter (primary particle size 30 to 40 nm, specific surface area 79 m) ² / g).
[0042]
[Example 7]
The same procedure as in Example 1 was performed except that the amount of DPP pigment was changed from 152 parts to 155.2 parts, and 8 parts of the dye derivative (a) was changed to 4.8 parts of the dye derivative (d). Part of color filter pigment (primary particle size 30-50 nm, specific surface area 72 m ² / g).
[Example 8]
190 parts of the DPP pigment “Irgazine DPP RED BO”, 10 parts of the dye derivative (d), 2000 parts of sodium chloride, and 240 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader and kneaded at 60 ° C. for 10 hours. Purification and drying were carried out in the same manner as in Example 1, and 194.2 parts of color filter pigment (primary particle diameter of 30 to 50 nm, specific surface area of 72 m). ² / g).
[0043]
[Example 9]
The same procedure as in Example 1 was carried out except that the pigment derivative (a) was replaced with the pigment derivative (e), and 154.8 parts of a pigment for a color filter (primary particle size 30 to 40 nm, specific surface area 79 m) ² / g).
[Example 10]
The same operation as in Example 1 except that the DPP pigment was changed to the DPP pigment “chromoftal DPP orange TR” (CI Pigment ORANGE 71) manufactured by Ciba Specialty Chemicals, and the dye derivative (a) was changed to the dye derivative (e). 156.0 parts of pigment for color filter (primary particle size 40-50 nm, specific surface area 73 m ² / g).
[0044]
[Example 11]
The same procedure as in Example 1 was conducted except that the pigment derivative (a) was replaced with the pigment derivative (f), and 156.5 parts of a pigment for a color filter (primary particle diameter of 30 to 40 nm, specific surface area of 82 m) ² / g).
[Example 12]
The same operation as in Example 1 except that the DPP pigment was changed to the DPP pigment “Irgazine DPP Rubin TR” (CI Pigment RED264) manufactured by Ciba Specialty Chemicals, and the pigment derivative (a) was replaced with the pigment derivative (f). 156.5 parts of color filter pigment (primary particle size 40-50 nm, specific surface area 73 m ² / g).
[0045]
[Example 13]
The same procedure as in Example 1 was conducted except that the pigment derivative (a) was replaced with the pigment derivative (g), and 156.5 parts of a pigment for a color filter (primary particle size 30 to 40 nm, specific surface area 77 m) ² / g).
[Example 14]
The same procedure as in Example 1 was conducted except that the pigment derivative (a) was replaced with the pigment derivative (h), and 156.0 parts of a pigment for a color filter (primary particle diameter of 30 to 40 nm, specific surface area of 80 m) ² / g).
[0046]
[Example 15]
The same procedure as in Example 1 except that the DPP pigment was changed to the DPP pigment “Irgazine DPP Scarlet EK” (CI Pigment RED255) manufactured by Ciba Specialty Chemicals, and the pigment derivative (a) was replaced with the pigment derivative (i). 157.2 parts of color filter pigment (primary particle size 40-50 nm, specific surface area 70 m ² / g).
[0047]
[Example 16]
The same procedure as in Example 1 except that the DPP pigment was changed to the DPP pigment “Irgazine DPP Rubin TR” (CI Pigment RED264) manufactured by Ciba Specialty Chemicals, and the pigment derivative (a) was replaced with the pigment derivative (j). 156.4 parts of color filter pigment (primary particle size 30-40 nm, specific surface area 81 m ² / g).
[0048]
[Example 17]
The same operation as in Example 1 except that the DPP pigment was changed to the DPP pigment “chromoftal DPP orange TR” (CI Pigment ORANGE 71) manufactured by Ciba Specialty Chemicals, and the dye derivative (a) was changed to the dye derivative (k). 156.6 parts of color filter pigment (primary particle size 30-40 nm, specific surface area 81 m ² / g).
[0049]
[Example 18]
When kneading the DPP pigment, the dye derivative (a), sodium chloride and diethylene glycol, the same operation as in Example 1 except that 8 parts of a maleic acid resin (“Marquide No. 32” manufactured by Arakawa Chemical Industries, Ltd.) was added. 159.1 parts of color filter pigment (primary particle size 30-40 nm, specific surface area 87 m ² / g).
[0050]
[Comparative Example 2]
Except for the dye derivative (b), the same operation as in Example 2 was carried out to prepare 149.0 parts of treated pigment (primary particle diameter of 100 to 200 nm, specific surface area of 45 m). ² / g).
[0051]
[Comparative Example 3]
157.0 parts of treated pigment (primary particle diameter) was obtained by performing the same operation as in Example 12 except that the dye derivative (f) was replaced with 8 parts of a maleic acid resin (“Marquide No. 32” manufactured by Arakawa Chemical Industries, Ltd.). 40-60nm, specific surface area 78m ² / g).
[Comparative Example 4]
Except that the pigment derivative (e) was replaced with 8 parts of an epoxy resin (“Epicoat 1004” manufactured by Yuka Shell Epoxy Co., Ltd.), the same operation as in Example 10 was carried out to obtain 158.2 parts of treated pigment (primary particle size of 60 to 70 nm, specific surface area 78 m ² / g).
[0052]
[Comparative Example 5]
Untreated DPP pigment ("Irgafor RED B-CF" manufactured by Ciba Specialty Chemicals, CI Pigment RED254, primary particle size 40-60 nm, specific surface area 85 m ² / g)
[Comparative Example 6]
Untreated DPP pigment (“Irgazine DPPRED BO” manufactured by Ciba Specialty Chemicals, CI Pigment RED254, primary particle size 200 to 600 nm, specific surface area 25 m ² / g)
[0053]
[Comparative Example 7]
Untreated DPP pigment ("Irgazine DPP Scarlet EK" manufactured by Ciba Specialty Chemicals, CI Pigment RED255, primary particle size 200 to 400 nm, specific surface area 30 m ² / g)
[Comparative Example 8]
Untreated DPP pigment ("Irgazine DPP Rubin TR" manufactured by Ciba Specialty Chemicals, CI Pigment RED264, primary particle size 40-100 nm, specific surface area 70 m ² / g)
[Comparative Example 9]
Untreated DPP pigment (“Chromophthal DPP Orange TR” manufactured by Ciba Specialty Chemicals, CI Pigment ORANGE 71, primary particle size 40 to 200 nm, specific surface area 78 m ² / g)
[0054]
Mixtures having the following compositions containing the pigments obtained in Examples and Comparative Examples were uniformly stirred and mixed, and then filtered through a 1 μm filter to prepare an alkali developing type photosensitive coloring composition.
4.5 parts of pigment
24.0 parts of the above acrylic resin solution
5.4 parts of trimethylolpropane triacrylate
(Shin Nakamura Chemical "NK Ester ATMPT")
Photoinitiator ("Irgacure 907" manufactured by Ciba Geigy) 0.3 parts
Sensitizer (Hoabaya Chemical "EAB-F") 0.2 parts
65.1 parts cyclohexanone
[0055]
Using the resulting photosensitive coloring composition, a color material layer was formed on a transparent substrate by the following method, and the spectral transmittance, chromaticity, surface state, and NMP resistance of the color material layer were evaluated. The results are shown in Table 2.
The obtained photosensitive coloring composition is applied on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at 500 rpm, 1000 rpm, 1500 rpm, 2000 rpm, and the thickness of the color material layer is different. Four types of coated substrates were obtained. Next, after drying at 70 ° C. for 20 minutes, ultraviolet exposure was performed with an integrated light amount of 150 mJ using an ultrahigh pressure mercury lamp. After exposure, the mixture was heated at 230 ° C. for 1 hour and allowed to cool, and then the chromaticity (Y, x, y) with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). From the four sets of chromaticity / spectral measurement results, the maximum transmittance, Y, x, and y when the minimum value of the spectral transmittance at a wavelength of 400 to 700 nm was 1% were determined. Furthermore, the surface state of the coated substrate at 1000 rpm was observed with an optical microscope (“BX60” manufactured by Olympus Optical Co., Ltd.). After observation, the coated substrate was dipped in NMP for 30 minutes and dried, and then the coated substrate chromaticity was measured with a microspectrophotometer, the color difference ΔE before and after immersion was determined, and the NMP resistance of the coated substrate was evaluated.
[0056]
[Table 2]

[0057]
The colorant layer formed using the photosensitive coloring composition obtained by dispersing the DPP pigments of Examples 1 to 17 in which a salt derivative is treated with a pigment derivative in a transparent resin has a finely dispersed pigment and a dispersed state. Since both are good, the maximum transmittance is high when the minimum transmittance is the same. That is, it has excellent characteristics as a color filter that blocks unnecessary light and transmits more necessary light. For example, the maximum transmittance of the color material layer formed using the DPP pigment “Irgazine DPP RED BO” (Comparative Example 6) that is not subjected to salt milling is 87%, whereas in Examples 1 and 3 to 9, The maximum transmittance of the color material layer is dramatically improved to 95 to 99%.
[0058]
This is the same as C.I. I. It is higher than the case of using the refinement type B-CF (Comparative Example 5) in Pigment RED254. Further, in Comparative Example 1 in which the DPP pigment “Irgazine DPP RED BO” was subjected to the salt milling treatment without the pigment derivative, the maximum transmittance was 79%, which is more opaque than the untreated case. Since the primary particle diameter of Comparative Example 1 is larger, it can be seen that when salt milling is performed without a pigment derivative, the DPP pigment crystal grows.
Moreover, about heat resistance, although a protrusion of about 5-10 micrometers is recognized on the coating-film surface by a 230 degreeC heating in a comparative example, it is not observed on the coating-film surface of Examples 1-17. Further, in the case of NMP tolerance, ΔE of the comparative example is 3 to 4, whereas in all the examples, the color change is as small as around ΔE = 1, indicating that the NMP tolerance is high.
[0059]
【The invention's effect】
According to the present invention, a fine diketopyrrolopyrrole pigment can be obtained while suppressing crystal growth. In addition, by using the pigment of the present invention, a color filter having excellent pixels having high transparency and NMP resistance can be obtained.

Claims (4)

From diketopyrrolopyrrole pigment (A), hydroxyl group, carboxyl group, sulfonic acid group, carbamoyl group, sulfonamide group, or a quinacridone derivative and / or diketopyrrolopyrrole derivative having a basic substituent represented by the following general formula comprising pigment derivative (B), water-soluble inorganic salt (C), and after the water-soluble inorganic salt (C) were kneaded mixture containing a water-soluble organic solvent which does not substantially dissolve (D), water-soluble inorganic salt (C And a water-soluble organic solvent (D).

[X: a direct _{bond, -CH 2 NHCOCH 2 -, -} SO 2 NH -, - CONHOCH 2 NH-, or - represents a _(CH 2) _q NH-.
R ₁ and R ₂ each independently represents a saturated or unsaturated alkyl group that may be substituted, or a heterocyclic ring that may contain a nitrogen, oxygen, or sulfur atom in R ₁ or R ₂ . ]

[Z: a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - (CH 2) q -, - SO 2 NH -, - CONH -, - CH 2 NHCOCH 2 NH-, or - (CH ₂ ) _q NH— However, q represents the integer of 1-10.
R ₃ , R ₄ , R ₅ , R ₆ each independently represents a hydrogen atom, a saturated or unsaturated alkyl group which may be substituted, or an aryl group.
R ₇ represents a saturated or unsaturated alkyl group or aryl group which may be substituted. ] From diketopyrrolopyrrole pigment (A), hydroxyl group, carboxyl group, sulfonic acid group, carbamoyl group, sulfonamide group, or a quinacridone derivative and / or diketopyrrolopyrrole derivative having a basic substituent represented by the following general formula After kneading a mixture containing a water-soluble organic solvent (D) that does not substantially dissolve the dye derivative (B), the water-soluble inorganic salt (C), and the water-soluble inorganic salt (C), the water-soluble inorganic salt (C And a water-soluble organic solvent (D) are removed .

[X: a direct _{bond, -CH 2 NHCOCH 2 -, -} SO 2 NH -, - CONHOCH 2 NH-, or - represents a _(CH 2) _q NH-.
R ₁ and R ₂ each independently represents a saturated or unsaturated alkyl group that may be substituted, or a heterocyclic ring that may contain a nitrogen, oxygen, or sulfur atom in R ₁ or R ₂ . ]

[Z: a direct _{bond, -SO 2 -, - CO -} , - CH 2 NHCOCH 2 -, - (CH 2) q -, - SO 2 NH -, - CONH -, - CH 2 NHCOCH 2 NH-, or - (CH ₂ ) _q NH— However, q represents the integer of 1-10.
R ₃ , R ₄ , R ₅ , R ₆ each independently represents a hydrogen atom, a saturated or unsaturated alkyl group which may be substituted, or an aryl group.
R ₇ represents a saturated or unsaturated alkyl group or aryl group which may be substituted. ] A color filter coloring composition comprising the color filter pigment according to claim 1 dispersed in a transparent resin. A color filter comprising a pixel formed using the coloring composition for a color filter according to claim 3.