JP3986149B2 - Color photosensitive material, method for producing color filter using the same, and color filter - Google Patents

Description

【００５６】
式（VII)中、Ｒ₄はアルキル基、シクロアルキル基、アリール基、アルコキシ基、シクロアルキルオキシ基、アリールオキシ基、ヘテロ環基、アルキルアミノ基、シクロアルキルアミノ基、アルールアミノ基、ヘテロ環アミノ基、アルキルカルバモイル基、シクロアルキルカルバモイル基、アリールカルバモイル基、アルキルスルファモイル基、シクロアルキルスルファモイル基またはアリールスルファモイル基を表し、これらの基の好ましい炭素数、具体例はＲ₄₀で説明したそれらの基と同じ意味を表す。Ｒ₅およびＲ₆はそれぞれ独立に水素原子または置換基を表し、Ｒ₄₀と同じ意味の基を表す。＊は（ＴＩＭＥ）_n −（Ｌ₁)_m −（ＹＤＹＥ）と結合する位置を表す。
【００５７】
【化２】

【００５８】
式(VIII)中、Ｒ₇はＲ₄と同じ意味の基を表し、Ｍ₁は縮合したベンゼン環と共に５員、６員または７員環を形成するために必要な非金属原子群を表す。＊は（ＴＩＭＥ）_n −（Ｌ₁)_m ―（ＹＤＹＥ）との結合位置を表す。
【００５９】
【化３】

【００６０】
式（IX）中、Ｒ₈はアルキル基、シクロアルキル基、アリール基、ヘテロ環基、アルコキシ基、シクロアルキルオキシ基、アリールオキシ基、ヘテロ環オキシ基、アルキルアミノ基、シクロアルキルアミノ基またはアリールアミノ基を表し、これらの基の好ましい炭素数および具体例はＲ₄₀で説明したのと同じ意味の基を表す。Ｌ₄およびＬ₅はそれぞれ独立に−ＣＯ−または−ＳＯ₂−を表し、Ｒ₉は水素原子、アルキル基、シクロアルキル基、アリール基またはヘテロ環基を表し、これらの基の好ましい炭素数および具体例はＲ₄₀で説明したのと同じ意味の基を表す。Ｒ₁₀はアルキル基、シクロアルキル基、アリール基またはヘテロ環基を表し、Ｒ₁₁は置換基を表す。Ｒ₁₀およびＲ₁₁のこれらの基の好ましい炭素数および具体例はＲ₄₀で説明したのと同じ意味の基を表す。ｐは０〜３の整数を表す。＊は（ＴＩＭＥ）_n −（Ｌ₁)_m ―（ＹＤＹＥ）との結合位置を表す。
【００６１】
【化４】

【００６２】
式（Ｘ）中、Ｒ₁₂およびＲ₁₃はそれぞれ独立に水素原子又は置換基を表し、Ｒ₄₀と同じ意味の基を表す。Ｍ₂は縮合したピロール環と共に５員、６員または７員環を形成するために必要な非金属原子群を表す。＊は（ＴＩＭＥ）_n −（Ｌ₁)_m ―（ＹＤＹＥ）との結合位置を表す。
【００６３】
次に、一般式（VII)〜一般式（Ｘ）で表されるカプラー残基の好ましい範囲について説明する。
【００６４】
一般式（VII)で表されるカプラー残基のＲ₄は、アルキル基、シクロアルキル基、アリール基、アルコキシ基、シクロアルキルオキシ基、ヘテロ環基、アルキルアミノ基、シクロアルキルアミノ基、アリールアミノ基、ヘテロ環アミノ基が好ましく、アルキル基、シクロアルキル基、アリール基、アルコキシ基、シクロアルキルオキシ基がさらに好ましい。最も好ましくはアルキル基、シクロアルキル基、アリール基、アルコキシ基が挙げられる。
【００６５】
Ｒ₅はハロゲン原子、アルキル基、シクロアルキル基、アリール基、アルコキシ基、シクロアルキルオキシ基、アリールオキシ基、アルキルチオ基、シクロアルキルチオ基、アリールチオ基、カルバモイル基、アミノ基、アニリノ基、ヘテロ環アミノ基、カルボンアミド基、ウレイド基、アルコキシカルボニルアミノ基、シクロアルキルオキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルホンアミド基、スルファモイルアミノ基、アルキルチオ基、シクロアルキルチオ基、アリールチオ基、ヘテロ環チオ基、ホスフィノイルアミノ基が好ましく、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、アルコキシ基、シクロアルキルオキシ基、アリールオキシ基、カルボンアミド基、ウレイド基、アルコキシカルボニルアミノ基、シクロアルキルオキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルホンアミド基、ホスフィノイルアミノ基がさらに好ましい。最も好ましくはアルキル基、アルコキシ基、カルボンアミド基、ウレイド基、アルコキシカルボニルアミノ基、シクロアルキルオキシカルボニルアミノ基が挙げられる。
【００６６】
Ｒ₆は水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、アルコキシ基、シクロアルキルオキシ基、アリールオキシ基、アルキルチオ基、シクロアルキルチオ基、アリールチオ基、カルバモイル基、アミノ基、アニリノ基、ヘテロ環アミノ基、カルボンアミド基、ウレイド基、アルコキシカルボニルアミノ基、シクロアルキルオキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルホンアミド基、スルファモイルアミノ基、アルキルチオ基、シクロアルキルチオ基、アリールチオ基、ヘテロ環チオ基、ホスフィノイルアミノ基が好ましく、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アリールオキシ基、カルボンアミド基、アルコキシカルボニルアミノ基、シクロアルキルオキシカルボニルアミノ、ホスフィノイルアミノ基がさらに好ましい。最も好ましくは、水素原子、ハロゲン原子、カルボンアミド基が挙げられる。
【００６７】
次に一般式(VIII)で表されるカプラー残基の好ましい範囲について説明する。Ｒ₇はアルキル基、シクロアルキル基、アリール基、アルコキシ基、シクロアルキルオキシ基、ヘテロ環基、アルキルアミノ基、シクロアルキルアミノ基、アリールアミノ基、ヘテロ環アミノ基が好ましく、アルキル基、シクロアルキル基、アリール基、アルコキシ基、シクロアルキルオキシ基がさらに好ましい。最も好ましくはアルキル基、シクロアルキル基、アルコキシ基が挙げられる。
Ｍ₁は縮合したベンゼン環と共に５員、６員または７員環の飽和環が好ましい。
【００６８】
次に一般式（IX）で表されるカプラー残基の好ましい範囲について説明する。Ｒ₈はアルキル基、シクロアルキル基、アリール基、ヘテロ環基、アルコキシ基、シクロアルキルオキシ基、アルキルアミノ基、シクロアルキルアミノ基が好ましく、アルキル基、シクロアルキル基、アリール基、アルコキシ基、シクロアルキルオキシ基、アルキルアミノ基がさらに好ましい。最も好ましくはアルキル基、シクロアルキル基、アルコキシ基が挙げられる。
Ｌ₄は−ＣＯ−が好ましい。
【００６９】
Ｒ₉は水素原子、アルキル基、シクロアルキル基、アリール基が好ましく、水素原子が最も好ましい。
Ｒ₁₀はアルキル基、シクロアルキル基、アリール基が好ましく、アルキル基、シクロアルキル基がさらに好ましい。最も好ましくはアルキル基が挙げられる。
【００７０】
Ｒ₁₁はハロゲン原子、アルキル基、シクロアルキル基、アリール基、アルコキシ基、シクロアルキルオキシ基、アリールオキシ基、アルキルチオ基、シクロアルキルチオ基、アリールチオ基、ヘテロ環チオ、カルボンアミド基、スルホンアミド基、カルバモイル基、スルファモイル基、イミド基、スルホニル基、ヒドロキシ基、アミノ基、カルボキシル基が好ましく、ハロゲン原子、アルコキシ基、シクロアルキルオキシ基、カルボンアミド基、スルホンアミド基、カルバモイル基、スルファモイル基、ヒドロキシ基、カルボキシル基がさらに好ましい。最も好ましくはハロゲン原子、カルボンアミド基、ヒドロキシ基、カルボキシル基、スルホンアミド基がさらに好ましい。最も好ましくはハロゲン原子が挙げられる。
ｐは０又は１が好ましく、０が最も好ましい。
【００７１】
次に一般式（Ｘ）で表されるカプラー残基の好ましい範囲について説明する。Ｒ₁₂はシアノ基、アルキルオキシカルボニル基、シクロアルキルオキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、シクロアルキルスルホニル基、アリールスルホニル基、ヘテロ環基、アシル基、スルファモイル基、ホスホニル基、ホスフィノイルアミノ基、イミド基、またはパーフロロアルキル基が好ましく、シアノ基、アルキルオキシカルボニル基、シクロアルキルオキシカルボニル基、カルバモイル基、アルキルスルホニル基、シクロアルキルスルホニル基、アリールスルホニル基、スルファモイル基、ホスホニル基、パーフロロアルキル基がさらに好ましい。最も好ましくはシアノ基、アルキルオキシカルボニル基、シクロアルキルオキシカルボニル基、アルキルスルホニル基、シクロアルキルスルホニル基、アリールスルホニル基、パーフロロアルキル基が挙げられる。
【００７２】
Ｒ₁₃はシアノ基、アルキルオキシカルボニル基、シクロアルキルオキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、シクロアルキルスルホニル基、アリールスルホニル基、ヘテロ環基、アシル基、スルファモイル基、ホスホニル基、ホスフィノイルアミノ基、イミド基、またはパーフロロアルキル基が好ましく、シアノ基、アルキルオキシカルボニル基、シクロアルキルオキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、シクロアルキルスルホニル基、アリールスルホニル基、スルファモイル基、ホスホニル基、パーフロロアルキル基がさらに好ましく、最も好ましくはシアノ基、シクロアルキルオキシカルボニル基、アルキルスルホニル基、シクロアルキルスルホニル基、アリールスルホニル基、スルファモイル基、ホスホニル基が挙げられる。
【００７３】
Ｍ₂はピロール環と共に５員又は６員環を形成するために必要な非金属原子群をが好ましく、５員環がさらに好ましく、１，２，４−トリアゾール環の形成するために必要な原子群がが最も好ましい。
【００７４】
一般式(VIII)および一般式（Ｘ）で表されるカプラー残基が好ましく、堅牢性の点では一般式(VIII)のカプラー残基が好ましく、色相の点では一般式（Ｘ）で表されるカプラー残基が好ましい。
【００７５】
以下に一般式（VII)〜一般式（Ｘ）で表されるカプラー残基の具体例を示すが本発明はこれらによって限定されない。
【００７６】
【化５】

【００７７】
【化６】

【００７８】
【化７】

【００７９】
【化８】

【００８０】
【化９】

【００８１】
ＴＩＭＥ基について詳しく説明する。
ＴＩＭＥで示される基は、現像処理時に一般式（Ｉ）におけるＴＩＭＥの左側の結合が開裂した後、その右側に結合する基を開裂することが可能なタイミング基であればいずれでもよい。例えば、米国特許第４，１４６，３９６号、同４，６５２，５１６号または同４，６９８，２９７号に記載のあるヘエミアセタールの開裂反応を利用する基、米国特許第４，２４８，９６２号、同４，８４７，１８５号、同４，８５７，４４０号または同５，２６２，２９１号に記載のある分子内求核置換反応を利用して開裂反応を起こさせるタイミング基、米国特許第４，４０９，３２３号もしくは同４，４２１，８４５号に記載のある電子移動反応を利用して開裂反応を起こさせるタイミング基、米国特許第４，５４６，０７３号に記載のあるイミノケタールの加水分解反応を利用して開裂反応を起こさせる基、英国特許第１，５３１，９２７号に記載のあるエステルの加水分解反応を利用して開裂反応を起こさせる基、または欧州公開特許第０５７２０８４号もしくは同０６８４５１２号に記載の亜硫酸イオンとの反応を利用して開裂反応を起こさせる基が挙げられる。
【００８２】
一般式（Ｉ）においてｎが２以上であるとき複数個のＴＩＭＥは同じものまたは異なるものを表す。好ましいＴＩＭＥとしては下記一般式（Ｔ−１）、（Ｔ−２）または（Ｔ−３）が挙げられる。
【００８３】
一般式（Ｔ−１） ＊−Ｗ−（Ｙ₁＝Ｙ₂）_j−Ｃ（Ｒ₇₁）（Ｒ₇₂）−＊＊
一般式（Ｔ−２） ＊−Ｗ−ＣＯ−＊＊
一般式（Ｔ−３） ＊−Ｗ−ＬＩＮＫ−Ｅ−＊＊
【００８４】
これらの式中、＊は一般式（Ｉ）におけるＴＩＭＥの左側の基に結合する位置を表し、＊＊は一般式（Ｉ）におけるＴＩＭＥの右側の基が結合する位置を表し、Ｗは酸素原子、硫黄原子または＞Ｎ−Ｒ₇₃を表し、Ｙ₁およびＹ₂は各々置換もしくは無置換のメチンまたは窒素原子を表し、ｊは０、１または２を表し、Ｒ₇₁およびＲ₇₂はＲ₄₁と同じ意味の基を表し、Ｒ₇₃はＲ₄₃と同じ意味の基を表す。Ｙ₁およびＹ₂が置換メチンを表すときその置換基はＲ₄₀と同じ意味の基を表す。ここで、Ｙ₁およびＹ₂が置換メチンを表すときその置換基、Ｒ₇₁、Ｒ₇₂、およびＲ₇₃の各々の任意の２つの置換基が互いに連結して環状構造（例えば、ベンゼン環、ピラゾール環）を形成してもよい。一般式（Ｔ−３）においてＥは求電子基を表し、ＬＩＮＫはＷとＥとが分子内求核置換反応することができる様に立体的に関係づける連結基を表す。一般式（Ｉ）で表される化合物のＱ₁部が色素を形成した後に流出する場合には、ｎは１、２、または３を表し、少なくとも一つにはＴＩＭＥ基中に炭素数１０〜５０の耐拡散性の基を有することが好ましい。
一般式（Ｔ−１）で示されるＴＩＭＥの具体例としては例えば以下のものである。
【００８５】
【化１０】

【００８６】
一般式（Ｔ−２）で示されるＴＩＭＥの具体例としては例えば以下のものである。
【００８７】
【化１１】

【００８８】
一般式（Ｔ−３）で示されるＴＩＭＥの具体例としては例えば以下のものである。
【００８９】
【化１２】

【００９０】
一般式（Ｉ）においてｎが２以上の時の（ＴＩＭＥ）_n の具体例、およびその他のタイミング基の例としては以下のものが挙げられる。
【００９１】
【化１３】

【００９２】
ｎは０、１または２が好ましく、０または１が更に好ましい。
【００９３】
次に、一般式（Ｘ）で表されるカラードカプラーのＬ₁及びｍについて説明する。
Ｌ₁は二価の連結基を表し、例えば、アルキレン基、シクロアルキレン基、アラルキレン基、アルケニレン基、アリーレン基、−Ｏ−、−Ｓ−、−Ｎ（Ｒ₁₄）−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮ（Ｒ₁₅）−、−ＳＯ−、−ＳＯ₂−、−ＳＯ₂Ｎ（Ｒ₁₄）−、−Ｎ（Ｒ₁₄）ＣＯＮ（Ｒ₁₅）−、−Ｎ（Ｒ₁₄）ＳＯ₂Ｎ（Ｒ₁₅）−、−ＣＯＮ（Ｒ₁₄）ＣＯ−、−ＣＯＮ（Ｒ₁₅）ＳＯ₂−、−Ｎ（Ｒ₁₄）ＣＯＯ−が挙げられる。Ｒ₁₄及びＲ₁₅はそれぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、ヘテロ環基を表し、前記のＲ₄₀で説明した水素原子、アルキル基、シクロアルキル基、アリール基、ヘテロ環基と同じ意味の基である。上記の自由結合手は一方がＱ₁基またはＴＩＭＥ基と結合し、他方がＹＤＹＥ基と結合している。ｍは０、１、２、又は３を表す。ｍが複数の場合には同一の連結基であってもよく異なっていてもよい。好ましくは０または１である。
【００９４】
次に（ＹＤＹＥ）で表されるイエロー色素残基についてを説明する。
（ＹＤＹＥ）はイエロー色素残基を表し、ハロゲン化銀写真感光材料に使用されるイエローカプラーと現像主薬の酸化体とのカップリングにより得られるイエロー色素残基（例えば、イエロー色素形成カプラーとしてはピバロイルアセトアニリド型、ベンゾイルアセトアニリド型、マロンジエステル型、マロンジアミド型、ジベンゾイルメタン型、ベンゾチアゾリルアセトアミド型、マロンエステルモノアミド型、ベンゾオキサゾリルアセトアミド型、ベンゾイミダゾリルアセトアミド型、ベンゾチアゾリルアセトアミド型、シクロアルカノイルアセトアミド型、インドリン−２−イルアセトアミド型、米国特許５，０２１，３３２号に記載されたキナゾリン−４−オン−２−イルアセトアミド型、同５，０２１，３３０号に記載されたベンゾ１，２，４−チアジアジン−１，１−ジオキシド−３−イルアセトアミド型、、欧州特許４２１２２１Ａ号に記載されたカプラー、米国特許５，４５５，１４９号に記載されたカプラー、及び欧州公開特許０６２２６７３号に記載されたカプラー等が挙げられる。
【００９５】
また、現像主薬としては、写真業界では公知のものであり、現像主薬の具体例はT.H.James「The Theory of the Photographic Process」第４版２９１〜３３４頁及び３５３〜３６１頁に記載されている。特に好ましい現像主薬はｐ−フェニレンジアミン誘導体である）、色素ハンドブック １９８６年（講談社）に記載のイエロー色素、化学便覧応用編改定３版１９８０年（丸善）に記載のイエロー色素、アジン系色素、アゾ系色素、アゾメチン系色素、キノフタロン系色素、ニトロ系色素、ナフトール系色素、ジオキサジン系色素、キノンイミン系色素、キノン系色素等の残基が挙げられる。
【００９６】
ＹＤＹＥはアルカノイルアセトアミド型、シクロアルカノイルアセトアミド型、ベンゾイルアセトアミド型、またはインドリン−２−イルアセトアミド型とｐ−フェニレンジアミン誘導体の酸化体とのカップリングにより得られるイエロー色素残基、アゾ系色素残基、アゾメチン系色素残基、アジン系色素、キノフタロン系色素残基、キノン系色素残基が好ましく、アルカノイルアセトアミド型、シクロアルカノイルアセトアミド型、ベンゾイルアセトアミド型、またはインドリン−２−イルアセトアミド型とｐ−フェニレンジアミン誘導体の酸化体とのカップリングにより得られるイエロー色素残基、アゾ系色素、アジン系色素、キノフタロン系色素が更に好ましい。
【００９７】
次に、一般式（II）で表されるイエローカラードシアン発色カプラーについて説明する。
一般式（II）のＡ₁は、前記一般式（Ｉ）のＱ₁で説明したシアンカプラー残基と同じ意味の基を表し、Ｒ₁はアリール基またはヘテロ環基を表し、アリール基およびヘテロ環基は置換基を有していてもよく、その置換基は前記のＲ₄₀で説明した基と同じ意味の基である。Ｒ₁はアリール基が好ましい。
【００９８】
次に、一般式（III)で表されるマゼンタカラードシアン発色カプラーについて説明する。
Ｑ₂は前記一般式（Ｉ）のＱ₁で説明したシアンカプラー残基と同じ意味の基を表し、その好ましい範囲についても前記一般式（Ｉ）と同様である。
ＴＩＭＥ基、ｎおよびｍは前記一般式（Ｉ）で述べた通りである。
Ｌ₂は前記一般式（Ｉ）のＬ₁で説明した基と同じ意味の基を表す。
【００９９】
（ＭＤＹＥ）は処理液中に流出可能なマゼンタ色素残基を表し、ハロゲン化銀写真感光材料に使用されるマゼンタカプラーと現像主薬の酸化体とのカップリングにより得られるマゼンタ色素残基。例えば、マゼンタ色素形成カプラーとしては、５−ピラゾロン型、１Ｈ−ピラゾロ〔１，５−ａ〕ベンズイミダゾール型、１Ｈ−ピラゾロ〔５，１−ｃ〕〔１，２，４〕トリアゾール型、１Ｈ−ピラゾロ〔１，５−ｂ〕〔１，２，４〕トリアゾール型、１Ｈ−イミダゾ〔１，２−ｂ〕ピラゾール型、シアノアセトフェノン型、ＷＯ９３／０１５２３に記載された活性プロペン型、ＷＯ９３／０７５３４に記載されたエナミン型、１Ｈ−イミダゾ〔１，２−ｂ〕〔１，２，４〕トリアゾール型のカプラー残基、および米国特許第４，８７１，６５２号に記載されたカプラー残基が挙げられ、現像主薬としては、例えば、写真業界では公知のものであり、現像主薬の具体例はT.H.James「The Theory of the Photographic Process」第４版２９１〜３３４頁及び３５３〜３６１頁に記載されている。特に好ましい現像主薬はｐ−フェニレンジアミン誘導体である）。さらに（ＭＤＹＥ）は色素ハンドブック １９８６年（講談社）に記載のマゼンタ色素残基、化学便覧応用編改定３版１９８０年（丸善）に記載のマゼンタ色素残基、例えば、アジン系色素、アゾ系色素、アゾメチン系色素の残基が挙げられる。
【０１００】
次に、一般式（IV）で表されるマゼンタカラードシアン発色カプラーについて説明する。
Ａ₂は前記一般式（Ｉ）のＱ₁で説明したシアンカプラー残基と同じ意味の基を表し、その好ましい範囲についても一般式（Ｉ）で述べたのと同義である。Ｒ２はアリール基またはヘテロ環基を表し、アリール基およびヘテロ環基は置換基を有していてもよく、その置換基は前記のＲ₄₀で説明した基と同じ意味の基である。
【０１０１】
次に、一般式（Ｖ）で表されるイエローカラードマゼンタ発色カプラーについて説明する。
ＴＩＭＥ、ｎ、ｍ、および（ＹＤＹＥ）は前記一般式（Ｉ）で説明したそれと同じ意味の基を表す。Ｌ₃は前記一般式（Ｉ）で説明したＬ₁と同じ意味の基を表す。
【０１０２】
Ｑ₃はマゼンタカプラー残基を表し、例えば、５−ピラゾロン型、１Ｈ−ピラゾロ〔１，５−ａ〕ベンズイミダゾール型、１Ｈ−ピラゾロ〔５，１−ｃ〕〔１，２，４〕トリアゾール型、１Ｈ−ピラゾロ〔１，５−ｂ〕〔１，２，４〕トリアゾール型、１Ｈ−イミダゾ〔１，２，ｂ〕ピラゾール型、シアノアセトフェノン型、ＷＯ９３／０１５２３号に記載の活性プロペン型、ＷＯ９３／０７５３４号に記載のエナミン型、１Ｈ−イミダゾ〔１，２−ｂ〕〔１，２，４〕トリアゾール型、および米国特許第４，８７１，６５２号に記載されたカプラーの残基等が挙げられる。
【０１０３】
Ｑ₃は好ましくは下記一般式（XI）で表される。
【０１０４】
【化１４】

【０１０５】
式（XI）中、Ｒ₁₆は水素原子または置換基を表し、Ｚ₁およびＺ₂はそれぞれ独立に−Ｎ＝または−Ｃ（Ｒ₁₇）＝を表す。＊は（ＴＩＭＥ）_n −（Ｌ）_m ―ＹＤＹＥとの結合位置を表す。
Ｒ₁₆はＲ₄₀と同じ意味の基を表し、Ｒ₁₇はＲ₄₁と同じ意味の基を表す。
【０１０６】
Ｒ₁₆としては、アルキル基、シクロアルキル基、アルケニル基、アリール基、ヘテロ環基、アルコキシ基、シクロアルキルオキシ基、アリールオキシ基、ヘテロ環オキシ基、シアノ基、シリル基、シリルオキシ基、アシルオキシ基、アルコキシカルボニルオキシ基、シクロアルキルオキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、カルバモイルオキシ基、スルファモイルオキシ基、アルカンスルホニルオキシ基、アレーンスルホニルオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、シクロアルキルオキシカルボニル基、カルバモイル基、アミノ基、アニリノ基、ヘテロ環アミノ基、カルボンアミド基、ウレイド基、イミド基、アルコキシカルボニルアミノ基、シクロアルキルオキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルホンアミド基、スルファモイルアミノ基、アゾ基、カルボキシル基、アルキルチオ基、シクロアルキルチオ基、アリールチオ基、ヘテロ環チオ基、アルキルスルフィニル基、アレーンスルフィニル基、アルカンスルホニル基、アレーンスルホニル基、アルコキシスルホニル基、シクロアルキルオキシスルホニル基、アリールオキシスルホニル基、スルファモイル基、スルホ基、ホスホニル基、ホスフィノイルアミノ基が好ましく、アルキル基、シクロアルキル基、アルケニル基、アリール基、ヘテロ環基、アルコキシ基、シクロアルキルオキシ基、アリールオキシ基、ヘテロ環オキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、シクロアルキルオキシカルボニル基、カルバモイル基、アミノ基、アニリノ基、カルボンアミド基、ウレイド基、アルコキシカルボニルアミノ基、シクロアルキルオキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルホンアミド基が更に好ましい。最も好ましくはアルキル基、シクロアルキル基、アリール基、アルコキシ基、シクロアルキルオキシ基、アリールオキシ基、アニリノ基等が挙げられる。
【０１０７】
以下にＱ₃で表されるマゼンタカプラー残基の具体例を示すが本発明はこれらに限定されない。
【０１０８】
【化１５】

【０１０９】
【化１６】

【０１１０】
【化１７】

【０１１１】
次に、一般式（VI）で表されるイエローカラードマゼンタ発色カプラーについて説明する。
Ａ₃は前記一般式（Ｖ）のＱ₃で説明したマゼンタカプラー残基と同じ意味の基を表す。、Ｒ₃はアリール基またはヘテロ環基を表し、それらの基は置換基を有していてもよくその置換基はＲ₄₀で説明した置換基を表す。
【０１１２】
以下の一般式（Ｉ）〜一般式（VI）で表される本発明のカラードカプラーの具体例を示すが、本発明はこれらに限定されない。
一般式（Ｉ）で表されるカプラーの具体例を以下に示す。
【０１１３】
【化１８】

【０１１４】
【化１９】

【０１１５】
【化２０】

【０１１６】
【化２１】

【０１１７】
【化２２】

【０１１８】
一般式（II）で表されるカプラーの具体例を以下に示す。
【０１１９】
【化２３】

【０１２０】
【化２４】

【０１２１】
【化２５】

【０１２２】
一般式（III)で表されるカプラーの具体例を以下に示す。
【０１２３】
【化２６】

【０１２４】
【化２７】

【０１２５】
【化２８】

【０１２６】
【化２９】

【０１２７】
一般式（IV）で表されるカプラーの具体例を以下に示す。
【０１２８】
【化３０】

【０１２９】
一般式（Ｖ）で表されるカプラーの具体例を以下に示す。
【０１３０】
【化３１】

【０１３１】
【化３２】

【０１３２】
【化３３】

【０１３３】
一般式（VI）で表されるカプラーの具体例を以下に示す。
【０１３４】
【化３４】

【０１３５】
【化３５】

【０１３６】
次に、これらのカプラーの一般的な合成方法について説明する。
一般式（VII)で表されるカプラー残基の合成は、ハロゲン化銀感光材料の分野においては種々の方法が知られている。例えば、特公昭５９−４５１４２号、同６０−３７４５９に記載されている方法に従って容易に合成できる。
一般式(VIII)で示されるカプラー残基の合成は、例えば、特公平４−７３４３３号、米国特許第４，３２７，１７３号に記載されている方法に従って合成できる。一般式（IX）で示されるカプラー残基の合成は、例えば、欧州特許公開第１６１６２６号に記載されている方法に従って合成できる。
一般式（Ｘ）で示されるカプラー残基の合成は、例えば、欧州特許公開第０７１４８９２号に記載されている方法に従って合成できる。
一般式（XI）で示されるカプラー残基の合成は、特公平４−７９３５０号、特開平２−５９５８４号、導３−２２０２９２号に記載されている方法に従って合成できる。
【０１３７】
一般式（Ｉ）、一般式（III)及び一般式（Ｖ）で表されるＴＩＭＥ基を有する本発明の色素放出カプラーの合成は、米国特許第４，２４８，９６２号、同４，８５７，４４０、同５，０２１，３２２号、同５，２５６，５２３号、ヨーロッパ公告特許第０２９９７２６号、同０３４８１３９号、同０３５４５３２号、同０４３８１５０号、同０４９９２７９号、ヨーロッパ公開特許第０５１４８９６号、同０５９４２５６号、同０５２３４２３号、同０５２０４９６号、同０５７６０５２号、同０５７６０８７号、同０５７６０８８号、同０５７６０８９号、同０５７６１８２号、特公昭６３−３９８８９号、同６３−６１６５６号、特公平５−１８０９５号、特開平７−１３３２５９号、および特開平６−１３０５９４号等に記載されている方法と同様な方法により合成することができる。
【０１３８】
一般式（II）、一般式（IV）及び一般式（VI）で表されるカラードカプラーの合成は、芳香族アミン又はヘテロ環アミン類に亜硝酸塩類、亜硝酸エステル類またはニトロシル硫酸等のジアゾ化剤を作用させて芳香族ジアゾニウム塩又はヘテロ環ジアゾニウム塩を合成した後、前記の文献に従って合成したカプラーとカップリング反応を行うことによって容易に合成することができる。
【０１３９】
本発明の感光材料に使用できるハロゲン化銀粒子は、塩化銀、沃塩化銀、塩臭化銀、沃塩臭化銀である。好ましくは、塩化銀含有率が５０モル％以上である。更に好ましくは、塩化銀含有率が８０モル％以上である。沃化銀含有率は、２モル％以下が好ましいが、より好ましくは１モル％以下である。更に好ましくは、０．５モル％以下である。
【０１４０】
本発明で使用されるハロゲン化銀乳剤は、表面潜像型であっても、内部潜像型であっても良い。内部潜像型乳剤は、造核剤や光カブラセ剤とを組み合わせて直接反転乳剤として使用される。また、結晶構造は一様なものでも、粒子内部と粒子表面でで異なるハロゲン組成を持っている多重構造粒子であってもよい。また、エピタキシャル接合によって組成の異なるハロゲン化銀が接合されていてもよく、更に例えばロダン銀、酸化鉛等のハロゲン化銀以外の化合物と接合されていてもよい。
【０１４１】
特に、本発明で使用される高塩化銀乳剤においては、臭化銀局在相を、層状もしくは非層状にハロゲン化銀内部および／または表面に有する構造のものも使用できる。上記局在相のハロゲン組成は、臭化銀含有率が少なくとも２０モル％の物が好ましく、３０モル％を越えるものが好ましい。臭素銀局在相の臭素銀含有率は、Ｘ線解析等で分析される。例えば、シー アール ベリイ、エス ジェイマリノ（C.R.Berry, S.J.Marino)著フォトグラフィックサイエンス アンド テクノロジー（Photogaphic Science and Technology）２巻１４９頁（１９５５）および同４巻22頁（１９５７）にＸ線解析法のハロゲン化銀粒子位への適用法が記載されている。臭素化銀局在相は、粒子内部、粒子表面のエッジ、コーナー、あるいは面上にあることができる。好ましい例としては、粒子コーナー部にエピタキシャル接合したものが挙げられる。
【０１４２】
本発明に使用するハロゲン化銀粒子の平均粒径は、できるだけ低銀量で比表面積が大きく、高い現像活性を得るために、０．０５〜０．９μｍが好ましく、平均粒径の場合は厚みが０．０５〜０．９μｍが好ましく、特に０．１〜０．５μｍが好ましい。狭い粒子サイズ分布を有する単分散乳剤を用いてもよい。単分散乳剤は、例えば、粒子数あるいは重量で平均粒子サイズの±３０％以内に全粒子の８０％以上が入るような粒子サイズ分布を有するハロゲン化銀乳剤である。また、変動係数で２０％以下、特に１５％以下の単分散ハロゲン化銀乳剤であってもよい。広い粒子サイズを有する多分散乳剤を用いてもよい。
【０１４３】
本発明に使用できるハロゲン化銀乳剤は、例えば、リサーチ・ディスクロージャー（ＲＤ）誌、１７６巻NO.17643（１９７８年１２月）、２２〜２３頁、“Ｉ．乳剤製造（Emulsion Preparation and types）”及び同No.１８７１６（１９７９年１１月）、６４８頁、グラフキデ著「写真と物理と化学」、ポールモンテル社刊（P.Glafkides , Chemic et Phisique Phtographique,(Paul Montel,1967)）、ダフィン著「写真乳剤化学」、フォーカルプレス社刊（G.F.Duffin, Photographic Emulsion Chemistry,(Focal Press, 1966))、ゼリクマン著「写真乳剤の製造と塗布」、フォーカルプレス社刊（V.L.Zelikman et al , Making and Coating Photographic Emulsion, (Focal Press, 1964)）等に記載されている方法を用いて調整することができる。
【０１４４】
米国特許第３，５７４，６２８号、同３，６５５，３９４号及び英国特許第１，４１３，７４８号等に記載された単分散乳剤も好ましい。また、アスペクト比が５以上であるような平板状粒子も本発明に使用できる。平板粒子はガフト著、フォトグラフィック・サイエンス・アンド・エンジニアリング（Gutoff, Photographic Science and Engineering）、第１４巻、２４８〜２５７頁（１９７０年）、米国特許第４，４３４，２２６、同４，４１４，３１０号、同４，４３３，０４８号、同４，４３９，５２０号及び英国特許第２，１１２，１５７号等に記載されている方法により簡単に調整することができる。また、種々の結晶形の粒子の混合物を用いてもよい。
【０１４５】
感光性ハロゲンか銀乳剤は通常は化学増感されたハロゲン化銀乳剤である。本発明の感光性ハロゲン化銀乳剤の化学増感には、通常型感光材料用乳剤で公知の硫黄増感、セレン増感、テルル増感などのカルコゲン増感法、金、白金、パラヂウムなどを用いる貴金属増感法および還元増感法などを単独または組み合わせてもちいることもできる（例えば、特開平３−１１０５５５号、同５−２４１２６７号等）。これらの化学増感を含窒素複素環化合物の存在下で行うこともできる（特開昭６２−２５３１５９号）。また、後述するカブリ防止剤を化学増感終了後に添加することができる。具体的には、特開平５−４５８３３号、特開昭６２−４０４４６号記載の方法を用いることができる。
【０１４６】
化学増感時のｐＨは好ましくは５．３〜１０．５、より好ましくは５．５〜８．５であり、ｐＡｇは好ましくは６．０〜１０．５、入り好ましくは６．８〜９．０である。
本発明において使用される感光性ハロゲン化銀乳剤の塗布量は、銀換算１ｍｇないし１０ｍｇ／ｍ²である。
【０１４７】
本発明に用いられる感光性ハロゲン化銀に緑感性、赤感性、赤外感性の感色性を持たせるためには、感光性ハロゲン化銀乳剤をメチン色素類、その他によって分光増感する。また、必要に応じて青感性乳剤に分光増感してもよい。
用いられる色素には、シアニン色素、メロシアニン色素、複合シアニン色素、複合メロシアニン色素、ホロポーラーシアニン色素、ヘミシアニン色素、スチリル色素、ヘミオキソノール色素等が用いられる。
具体的には、米国特許第４，６１７，２５７号、特開昭５９−１８０５５０号、同６４−１３５４６号、特開平５−４５８２８号、同５−４５８３４号等に記載の増感色素が挙げられる。
これらの増感色素は単独に用いてもよいが、それらの組み合わせを用いてもよく、増感色素の組み合わせは特に、強色増感や分光感度の波長調節の目的でしばしば用いられる。
【０１４８】
増感色素とともに、それ自身分光増感作用を持たない色素あるいは可視光を実質的に吸収しない化合物であって、強色増感を示す化合物を乳剤中に含んでも良い（例えば、米国特許第３，６１５，６４１号、特開昭６３−２３１４５号等に記載のもの）。
これらの増感色素を乳剤中に添加する時期は化学熟成時もしくは其の前後でもよいし、米国特許第４，１８３，７５６号、同４，２２５，６６５号に従ってハロゲン化銀粒子の形成前後でもよい。また、これらの増感色素や強色増感剤は、メタノール等の有機溶媒の溶液、ゼラチンなどの分散物あるいは界面活性剤の溶液で添加すればよい。添加量は、一般にハロゲン化銀１モル当たり１０^-8ないし１０^-2モル程度である。
【０１４９】
この様な工程で使用される添加剤は、前記のＲＤＮｏ．１７６４３、同Ｎｏ．１８７１６および同Ｎｏ．３０７１０５に記載されており、其の該当箇所を下記の表にまとめる。
【０１５０】

【０１５１】
本発明で使用しうるカラー現像薬は、ハロゲン化銀を現像することにより生成した現像薬の酸化体がカプラーとカップリング反応して色素を形成するものであればよく、写真業界で公知のものである。カラー現像薬の具体例は T.H.James「The Theory of the Photographic Process」第４版２９１〜３３４頁および３５３〜３６１頁に記載されている。特に好ましいカラー現像薬はｐ−フェニレンジアミン誘導体である。
【０１５２】
本発明には前記本発明のカプラーとともに、公知の種々のカプラーを併用することができる。本発明に併用できるイエローカプラーとしては、例えば、ピバロイルアセトアニリド型、ベンゾイルアセトアニリド型、マロンジエステル型、マロンジアミド型、ジベンゾイルメタン型、エンゾチアゾリルアセトアミド型、マロンエステルモノアミド型、ベンゾオキサゾリルアセトアミド型、ベンゾイミダゾリルアセトアミド型、ベンゾチアゾリルアセトアミド型、シクロアルカノイルアセトアミド型、インドリン−２−イルアセトアミド型、米国特許５，０２１，３３２号に記載されたベンゾ−１，２，４−チアジアジン−１，１−ジオキシド−３−イルアセトアミド型、欧州特許４２１２２１Ａ号に記載されたカプラー、米国特許５，４５５，１４９号に記載されたカプラー、および欧州公開特許０６２２６７３号に記載されたカプラー等が挙げられる。
【０１５３】
本発明に併用できるマゼンタカプラーとしては、例えば、５−ピラゾロン型、１Ｈ−ピラゾロ〔１，５−ａ〕ベンズイミダゾール型、１Ｈ−ピラゾロ〔５，１−ｃ〕〔１，２，４〕トリアゾール型、１Ｈ−ピラゾロ〔１，５−ｂ〕〔１，２，４〕トリアゾール型、１Ｈ−イミダゾ〔１，２−ｂ〕ピラゾール型、シアノアセトフェノン型、ＷＯ９３／０１５２３号に記載された活性プロペン型、ＷＯ９３／０７５３４に記載されたエナミン型、１Ｈ−イミダゾ〔１，２−ｂ〕〔１，２，４〕トリアゾール型、および米国特許第４，８７１，６５２号に記載されたカプラー等が挙げられる。
【０１５４】
本発明に併用できるシアンカプラーとしては、例えば、フェノール型、ナフトール型、欧州特許公開第２４９４５３号に記載された２，５−ジフェニルイミダゾール型、１Ｈ−ピロロ〔１，２，−ｂ〕〔１，２，４〕トリアゾール型、１Ｈ−ピロロ〔２，１−ｃ〕〔１，２，４〕トリアゾール型、特開平４−１８８１３７号、同４−１９０３３４７号に記載されたピロール型、特開平１−３１５７３６号に記載された３−ヒドロキシピリジン型、米国特許第５，１６４，２８９号に記載されたピロロピラゾール型、特開平４−１７４４２９号に記載されたピロロイミダゾール型、米国特許第４，９５０，５８５号に記載されたピラゾロピリミジン型、特開平４−２０４７３０号に記載されたピロロトリアジン型、米国特許第４，７４６，６０２号に記載されたカプラー、同５，１０４，７８３号に記載されたカプラー、および欧州特許第０５５６７００号に記載されたカプラー等が挙げられる。
【０１５５】
更に実質的に色を残さないカプラーを併用してもよく、例えば、インダノン型、アセトフェノン型、欧州特許第４４３５５３０Ａ号、同４４４５０１Ａ号、特開平６−１３８６１２号、同６−８２９９５号、同６−８２９９６号、および同６−８２９９８号に記載されているカプラー等が挙げられる。
【０１５６】
前述したイエローカプラー、マゼンタカプラー、シアンカプラー及び実質的に色を残さないカプラー等は、イエロー色、マゼンタ色及びシアン色の各々の混合により再現される赤色、青色及び緑色の各色相の透過濃度を調整するために有効に用いられる。
【０１５７】
本発明には前述したカプラー以外にも下記の様な種々のカプラーを併用することができる。例えば、ポリマー化された色素形成カプラーとしては、米国特許第３，４５１，８２０号、同４，０８０，２１１号、同４，３６７，２８２号、英国特許第２，１０２，１３７号に記載されている。
カプリングに伴って写真的に有用な残基を放出するカプラーもまた本発明で好ましく使用できる。現像抑制剤を放出するＤＩＲカプラーは、前述のＲＤ１７６４３、VII〜Ｆ項に記載された特許、特開昭５７−１５１９４４号、同５７−１５４２３４号、同６０−１８４２４８号、米国特許第４，２４８，９６２号に記載されたものが好ましい。
現像時に画像状に造核剤もしくは現像促進剤を放出するカプラーとしては、英国特許第２，０９７，１４０号、同２，１３１，１８８号、特開昭５９−１５７６３８号、同５９−１７０８４０号に記載されているカプラーが好ましい。
【０１５８】
その他に、本発明に用いることのできるカプラーとしては、米国特許第４，１３０，４２７号に記載の競争カプラー、米国特許第４，２８３，４７２号、同４，３３８，３９３号、同４，３１０，６１８号に記載の多当量カプラー、特開昭６０−１８５９５０号等に記載のＤＩＲレドックス化合物放出カプラー等が挙げられる。
【０１５９】
また、黒補正用のカプラーはイエロー、マゼンタ、シアンに発色するものでなくても、例えば、オレンジ、褐色、紫色、黒色等に発色するものでもよい。
本発明において各ハロゲン化銀乳剤層中のハロゲン化銀対カプラーの当量比は０．５以上１００以下であり、好ましくは１以上１０以下であり、更に好ましくは１以上３以下が好ましい。特に平均粒子サイズ（平板粒子の場合には厚みで規定）が０．９μｍ以下、特に０．５μｍ以下のハロゲン化銀乳剤を用いる場合は１以上２以下がより好ましい。ここで言う当量比とは、カプラーを全て発色させるのに必要なハロゲン化銀の理論量を当量比１とし、例えば、理論量の２倍量のハロゲン化銀を塗布する場合には当量比は２である。すなわち２当量カプラーを使用する場合、カプラー１モルに対して塗布銀量が２モルであるとき、当量比は１であり、塗布銀量が４モルのとき、当量比は２である。
【０１６０】
本発明に併用する前記カプラーは、種々の公知の分散法により感光材料に導入できる。
水中油滴分散法に用いられる高沸点溶媒の例は米国特許第２，３２２，０２７号等に記載されている。高沸点溶媒はの量はカプラー１ｇに対して１０ｇ以下、好ましくは５ｇ以下、より好ましくは１ｇ〜０．１ｇである。またｈ，バインダー１ｇに対して２ｇ以下、好ましくは１ｇ以下、より好ましくはｏ．５ｇ以下である。水中油滴分散法で得られるカプラー分散物（カプラー乳化物）のサイズは０．０５μｍ〜０．９μｍ、好ましくは０．１μｍ〜０．５μｍである。
【０１６１】
ラテックス分散法の工程、効果、および含浸用等テックスの具体例は、米国特許第４，１９９，３６３号、西独特許出願（ＯＬＳ）第２，５４１，２７４号および同２，５４１，２３０号等に記載されている。
本発明にかかわる感光材料には、カプラーを含有する層に欧州公開特許ＥＰ０，２７７，５８９号に記載の様な色像保存性改良化合物を使用するのが好ましい。特にピラゾロアゾール系マゼンタカプラーとの併用が好ましい。
【０１６２】
すなわち、発色現像後に残存する芳香族系現像主薬と反応して、化学的に不活性でかつ実質的に無色の化合物を生成する化合物（Ｆ）および／または発色現像処理後に残存する芳香族系現像主薬の酸化対と反応して、化学的に不活性でかつ実質的に無色の化合物を生成する化合物（Ｇ）を同時にまたは単独で用いることが、ステインの発生、その他の副作用を防止する上で好ましい。
【０１６３】
本発明にかかわる感光材料のハロゲン化銀乳剤層や中間層には、色カブリ防止剤または褪色防止剤として、ヒドロキノン誘導体、アミノフェノール誘導体、没食子酸誘導体、アスコルビン酸誘導体等を含有してもよい。これらの化合物の中で、１６０℃〜２００℃に加熱してもステインの発生し難いものが好ましい。
【０１６４】
また、シアン色素像の熱および特に光による劣化を防止するためには、シアン発色層およびそれに隣接する両側の層に紫外線吸収剤を導入することが効果的である。
紫外線吸収剤としては、アリール基で置換されたベンゾトリアゾール化合物（例えば、米国特許第３，５３３，７９４号や同３，３５２，６８１号に記載の化合物）、ベンゾフェノン系化合物（例えば、特開昭４６−２７８４号に記載の化合物）、ケイ皮酸エステル化合物（例えば、米国特許第３，７０５，８０５号や同３，７０７，３９５号に記載の化合物）、ブタジエン系化合物（例えば、米国特許第４，０４５，２２９号に記載の化合物）あるいはベンズオキサゾール系化合物（例えば、米国特許第３，４０６，０７０号や、同４，２７１，３０７号に記載の化合物）を用いることができる。紫外線吸収性のカプラー（例えば、α−ナフトール系のシアン色像形成カプラー）や紫外線吸収性のポリマー等を用いてもよい。これらの紫外線吸収剤は特定の層に媒染されていてもよい。中でも前記のアリール基で置換されたベンゾトリアゾール系の化合物が好ましい。
【０１６５】
また、本発明にかかわる感光材料には、親水性コロイド層中に繁殖して画像を劣化させる各種のカビや細菌を防ぐために、特開昭６３−２７１２４７号に記載の様な防菌防カビ剤を添加するのが好ましい。
【０１６６】
本発明の感光材料のハロゲン化銀乳剤層や中間層、保護層に用いることができるバインダーまたは保護コロイドとしては、ゼラチンを用いるのが有利であるが、それ以外の親水性ポリマーも用いることができる。親水性ポリマーとしては、例えば、ポリビニルアルコール、ポリビニルアルコール部分アセタール、ポリビニルブチラール、ポリ−Ｎ−ビニルピロリドン、ポリアクリル酸、ポリアクリルアミド、ポリビニルイミダゾール、ポリビニルピラゾール、カラギーナン、アラビアゴム、さらにヒドロキシアルキルセルロース、カルボキシメチルセルロース、セルロース硫酸エステル、セルロースアセテート水素フタレートおよびアルギン酸ナトリウム等のセルロース誘導の単一あるいは共重合体が挙げられる。
【０１６７】
また、ゼラチンと他の高分子グラフトポリマーでもよく、ゼラチン−グラフトポリマーとしては、ゼラチンにアクリル酸、メタクリル酸、それらのエステル、アミド等の誘導体、アクリロニトリル、スチレン等のビニル系モノマーの単一または共重合体をグラフトさせた物を用いることができる。ことに、ゼラチンとある程度相溶性のあるポリマーー、例えば、アクリル酸、メタクリル酸、アクリルアミド、メタクリルアミド、ヒドロキシアルキルメタクリレート等の重合体とのグラフトポリマーが好ましい。これらの例は米国特許第２，７６３，６２５号、同２，８３１，７６７号、同２，９５６，８８４号、特開昭５６−６５１３３号等に記載がある。
代表的な合成親水性高分子物質としては、例えば、西独特許出願（ＯＬＳ）２，３１２，７０８号、米国特許第３，６２０，７５１号、同３，８７９，２０５号特公昭４３−７５６１号に記載のものも使用できる。
前記の親水性ポリマーは単独で使用してもよいし、２種以上を併用してもよい。
【０１６８】
ゼラチンとしては、アルカリ処理、酸処理、酵素処理のいずれかを施したもの、あるいはこれらの混合物を用いてもよい。また、ゼラチンに例えば、版ハライド、酸無水物、イソシアネート類、ブロモ酢酸、アルカンサルトン、ビニルスルホンアミド類、マレインイミド類、ポリアルキレンオキシド類、エポキシ化合物、等種々の化合物を反応させて得られるゼラチン誘導体も用いられる。ゼラチン誘導体の具体例は、米国特許第２，６１４，９２８号、同３，１３２，９４５号、同３，１８６，８４６号、同３，３１２，５５３号、英国特許第８６１，４１４号、同１，０３３，１８９号、同１，００５，７８４号、特公昭４２−２６８４５号等に記載されている。
【０１６９】
本発明に用いる感光材料における全バインダー量は３〜１０ｇ／ｍ²が好ましく、各ハロゲン化銀乳剤層や中間層等のバインダー含有量は１層当たり０．１〜１．５ｇ／ｍ²が好ましく、特に、０．２〜１．０ｇが好ましい。
【０１７０】
本発明に用いる支持体は光透過性基板であることが望ましいが、特開平７−２４４２１２号に記載のように、別の支持体上に塗布したハロゲン化銀乳剤層を光透過性基板上に転写密着させて、カラーフィルター用感光材料を形成してもよい。この場合には支持体は必ずしも光透過性である必要はなく、例えば、支持体のバック面にカーボンブラック等を塗布したものでもよい。
尚、この場合に設けられる剥離層や、バック層のバインダー量は、上記の「全バインダー量」には算入しない。
【０１７１】
光透過性基板を構成する素材の例としては、光学的に等方性で、耐熱性に優れているものが望ましく、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリスチレン、ポリカーボネエート、ポリエーテルスルホン、酢酸セルロース、ポリアリレート、ソーダガラス、ホウ珪酸ガラス、石英等が挙げられる。
【０１７２】
これらの素材で構成される基板の表面は必要に応じて下塗り処理されてもい。さらにッグロー放電、コロナ放電、紫外線照射等の処理を施してもよい。
ほか理透過性基板は、板状、シート状あるいはフィルム状等の形態で使用することができる。基板の厚みは、用途および材質により適宜に設定できるが、一般には０．０１〜１０ｍｍである。例えば、ガラス基板のときは厚みが０．３〜３ｍｍの範囲である。
【０１７３】
本発明に用いる感光材料は、前述のＲＤ．Ｎｏ．１７６４３の２８〜２９頁、および同Ｎｏ．１８７１６の６５１左欄〜右欄等に記載された通常の方法により発色現像することによりマイクロカラーフィルターを得る。
例えば、発色現像処理工程、脱銀処理工程、水洗処理工程が行われる。脱銀処理工程では、漂白液を用いた漂白工程と定着液を用いた定着工程の代わりに、漂白定着液を用いた漂白定着処理工程を行うこともできるし、漂白処理工程、定着処理工程、漂白定着処理工程を任意の順に組み合わせてもよい。水洗処理工程の代わりに安定化工程を行ってもよいし、水洗処理工程の後に安定化工程を行ってもよい。また、発色現像、漂白、定着を１浴中で行う１浴現像漂白定着処理液を用いたモノバス処理工程を行うこともできる。これらの処理工程に組み合わせて、前硬膜処理工程、その中和工程、停止定着処理工程、後硬膜処理工程、調整工程、補力工程等を行ってもよい。これらの処理において、発色現像処理工程の代わりに、いわゆるアクチベーター処理工程を行ってもよい。後硬膜処理工程で用いられる硬膜剤としてはアルデヒド類、ビニルスルホン類、カルボジイミド類、アルミミョウバン、クロムミョウバン類等の写真業界で公知の方法が挙げられる。好ましくはグルタルアルデヒド（または／および）アルミミョウバン、またはホルマリン（または／および）アルミミョウバンが挙げられる。
また、特開昭７−１５９６１０号等に記載のごとく、内部潜像型オートポジ乳剤を用いて、造核剤や光カブラセとを組み合わせて発色現像処理および脱銀処理を行ってもよい。
【０１７４】
現像処理装置としては、通常の写真処理に使用する現像処理機を用いることができる。また、ガラス基板等のハードな支持体の場合には、ガラス乾板用の現像処理機もしくは、特開平７−５６０１５号記載のような現像処理装置を用いることができる。
【０１７５】
本発明に適用される露光方法としては、マスクを通した面露光方式やスキャニング露光方式がある。スキャニング方式としては、ライン（スリット）スキャニングやレーザー露光等によるポイントスキャニング方式が適用できる。
光源としては、タングステン灯、ハロゲン灯、蛍光灯、水銀灯、レーザー光、発光ダイオード灯が用いられる。特に、ハロゲン灯、蛍光灯（３波長蛍光灯）レーザー光が好ましい。
本発明に適用できる別の露光方法としては、特開平８−２０１６１６号に記載のように本発明により作製したカラーフィルターを組み込む予定の液晶表示パネルを用い、色フィルターと組み合わせて順次３回露光する方法もある。
【０１７６】
本発明の方法により製造されたカラーフィルターは、最外層に耐熱性、耐水性、耐光性、ガスバリアー性、高比電気抵抗率を有する樹脂を保護層（オーバーコート層）として塗設することができる。かかる樹脂の例は米国特許第４，６９８，２９５号、同４，６６８，６０１号、欧州特許出願ＥＰ−１７９，６３６Ａ号、同５５６，８１０Ａ号、特開平３−１６３４１６号、同３−１８８１５３号、同５−７８４４３号、同１−２７６１０１号、特開昭６０−２１６３０７、同６３−２１８７７１号等に記載されている。
【０１７７】
本発明により製造されたカラーフィルターは更に蒸着被覆、例えば、真空蒸着またはスパッタりング法により透明電極を設けることができる。更にその上にはポリイミド樹脂等の配向膜を設けることができる。また、カラーフィルターの光透過性の基板の乳剤面とは反対側の面には、偏光板や位相差フィルムを設置してもよい。
【０１７８】
本発明のカラーフィルターを用いたカラー液晶表示装置（ＬＣＤ）について述べる。
図１１に液晶表示の断面略図の一例を示す。ガラス基板１上に本実施例によって作製したカラーフィルター２の表面は図面に示していないが前記の樹脂で被覆され、保護層が形成されている。その保護層上に透明電極（例えば、ＩＴＯ電極）３が真空成膜装置を用いて付着している。透明電極３はＴＦＴの様な三端子スイッチングアレイを用いるアクティブマトリックス駆動ＬＣＤでは全面一体電極として形成され、単純マトリックス駆動ＬＣＤやＭＩＭのような二端子スイッチングアレイを用いるアクティブマトリックス駆動ＬＣＤではストライプ電極として通常形成される。この透明電極３の上には液晶分子を整列させるためにポリイミド等の配向膜４が配置される。
【０１７９】
一方、液晶層５、スパーサー（図示していない）およびシール材６を挟んで向側のガラス基板７上にも透明電極（例えばＩＴＯ）８およびその上に配向膜４が配置される。透明電極８はＴＦＴの様な三端子スイッチングアレイを用いるアクティブマトリックス駆動ＬＣＤではＴＦＴ素子で接続された画素電極であり、ＳＴＮの様な単純マトリックス駆動ＬＣＤではストライプ電極であり、透明電極３と直行して配置されている。
【０１８０】
Ｒ，Ｇ，Ｂ各画素間には通常ブラックマトリックス９が形成され、コントラストや色純度の向上が図られている。ブラックマトリックス９は本発明の様にＲ，Ｇ，Ｂの各画素と同時に形成することもできるし、クロム膜やカーボン膜等を別途形成することもできる。また、ガラス基板１および７の背面には偏光板１０および１１を設置する。各ガラス基板と偏光板の間には位相補償フィルム（図示していない）を設置することもできる。
カラーフィルターを用いるＬＣＤの光透過率は小さいので、通常カラーフィルターと色再現性に整合成のとれた光源としてバックライト１２を設置する。
【０１８１】
光透過性基板としてガラス基板に代えて、ガスバリヤー層やハードコート層を設置したプラスチックフィルム基板を用いることができる。
カラーＬＣＤやその製造方法についての詳細は、松本正一・角田市良共著「液晶の基礎と応用」（１９９１年 工業調査会発行）、日経マイクロデバイス編「フラットパネル・ディスプレイ １９９４」（１９９３年 日経ＢＰ社発行）、特開平１−１１４８２０号等に記載されている。
【０１８２】
本発明の一般式（Ｉ）および一般式（II）で表される赤またはマゼンタカラードカプラー、およびそれらのカプラーと現像主薬の酸化体とから得られる色素を従来から知られているカラーフィルターの作製方法において使用し、該カプラーおよび色素を含有するカラーフィルターを作製することもできる。
【０１８３】
例えば、（１）天然高分子のゼラチン、カゼインや合成高分子のＰＶＡ、ＰＶＰ、アクリル等を感光化させたものを基板上に塗布し、フォトマスクを用いて紫外線で露光した後、現像し、次いで本発明のカプラーおよび／または現像主薬の酸化体とのカップリングから得られる色素で染色する染色法、（２）予め本発明のカプラーおよび／または現像主薬の酸化体とのカップリングにより得られる色素を用いて調色したフォトレジストを基板上に塗布し、染色法と同様に露光現像する顔料分散法（フォトリソ法）、（３）ＩＴＯをフォトリソ法で所定のパターンになるようにエィチングし、これを電極として電気泳動法で、本発明のカプラーおよび／または現像主薬の酸化体とのカップリングにより得られる色素を電極に膜形成する電着法、および（４）印刷法等においてカラーフィルターを形成することができる。
【０１８４】
【実施例】
以下に本発明の具体的実施例を述べるが、本発明の実施の態様はこれらに限定されない。
【０１８５】
実施例１及び比較例１〜２
感光性ハロゲン化銀乳剤（Ｉ）の調整法について述べる。
よく撹袢している第１表に示す組成のゼラチン水溶液を、第２表に示す（Ｉ）液を１分間添加する。（Ｉ）液添加開始２０秒後に（II）液を４０秒間で添加し、その後、（III)液と（IV）液を４分間かけて同時に添加した。
【０１８６】
【表１】

【０１８７】
【表２】

【０１８８】
【化３６】

【０１８９】
常法により、水洗、脱塩（沈降材（ａ）を用いてｐＨ４．０で行った）後、脱灰処理ゼラチン２２ｇを加えて分散した。ｐＨ６．０に調整した後、塩化ナトリウム１０％水溶液を４ｃｃ加え、さらに、防腐剤▲１▼を７０ｍｇを加え、粒子サイズ０．１５μｍの塩化銀乳剤を得る。この乳剤の収量は６３０ｇであった。
【０１９０】
【化３７】

【０１９１】
ハロゲン化銀乳剤（II）の調整法について述べる。
ゼラチン水溶液および（III)液と（IV）液の組成を第３表、第４表の様に変更した以外は、ハロゲン化銀乳剤（Ｉ）と同様にして、塩化銀含有率７０モル％の塩臭化銀乳剤を調整した。粒子サイズは０．１８μｍであった。
【０１９２】
【表３】

【０１９３】
【表４】

【０１９４】
（比較例１）
バック層としてカーボンブラックをポリ塩化ビニルに分散させて塗布した厚さ１００μｍのポリエチレンテレフタレート支持体にゼラチン下引きを施し、その上に以下に示す構成の第１層から第１０層を多層同時塗布し、比較用カラー感光材料１Ａを作製した。以下に成分と塗布量（ｇ／ｍ²単位）を示す。尚、ハロゲン化銀については銀換算の塗布量を示す。
【０１９５】

【０１９６】
第２層（ゼラチン隣接層）
ゼラチン ・・・０．５０
【０１９７】

【０１９８】
第４層（中間層）
ゼラチン ・・・０．３８
混色防止剤（Ｃｐｄ−７） ・・・０．０９
混色防止剤（Ｃｐｄ−１０） ・・・０．０２
高沸点溶媒（Ｓｏｌｖ−１） ・・・０．０３
高沸点溶媒（Ｓｏｌｖ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−５） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−４） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−６） ・・・０．０２
ポリマー（Ｃｐｄ−８） ・・・０．０４
【０１９９】

【０２００】
第６層（中間層）
ゼラチン ・・・０．３８
混色防止剤（Ｃｐｄ−７） ・・・０．０９
混色防止剤（Ｃｐｄ−１０） ・・・０．０２
高沸点溶媒（Ｓｏｌｖ−１） ・・・０．０３
高沸点溶媒（Ｓｏｌｖ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−５） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−４） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−６） ・・・０．０２
ポリマー（Ｃｐｄ−８） ・・・０．０４
イエロー染料（ＹＦ−１） ・・・０．１７
【０２０１】

【０２０２】
第８層（中間層）
ゼラチン ・・・０．３８
混色防止剤（Ｃｐｄ−７） ・・・０．０９
混色防止剤（Ｃｐｄ−１０） ・・・０．０２
高沸点溶媒（Ｓｏｌｖ−１） ・・・０．０３
高沸点溶媒（Ｓｏｌｖ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−５） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−４） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−６） ・・・０．０２
ポリマー（Ｃｐｄ−８） ・・・０．０４
イラジエーション防止染料（Ｄｙｅ−１） ・・・０．００５
イラジエーション防止染料（Ｄｙｅ−２） ・・・０．０２
【０２０３】

【０２０４】
第１０層（中間層）
ゼラチン ・・・０．７０
ハレーション防止染料（微粒子分散） ・・・０．１５
カルボキシメチルセルロース ・・・０．０５
ポリマー（Ｃｐｄ−１２） ・・・０．１４
界面活性剤（Ｃｐｄ−１３） ・・・０．０３
硬膜剤（Ｈ−１） ・・・０．１２
【０２０５】
各層には乳化分散助剤としてドデシイルベンゼンスルホン酸ナトリウム、補助溶媒として酢酸エチル、塗布助剤として界面活性剤（Ｃｐｄ−１４）を、さらに、増粘剤としてポリスチレンスルホン酸カリウムを用いた。
【０２０６】
【化３８】

【０２０７】
【化３９】

【０２０８】
【化４０】

【０２０９】
【化４１】

【０２１０】
【化４２】

【０２１１】
【化４３】

【０２１２】
（実施例１）
バック層としてカーボンブラックをポリ塩化ビニルに分散させて塗布した厚さ１００μｍのポリエチレンテレフタレート支持体にゼラチン下引きを施し、その上に以下に示す構成の第１層から第９層を多層同時塗布し、本発明のカラー感光材料２Ａを作製した。以下に成分と塗布量（ｇ／ｍ²単位）を示す。尚ハロゲン化銀については銀換算の塗布量を示す。
【０２１３】

【０２１４】
第２層（ゼラチン隣接層）
ゼラチン ・・・０．５０
【０２１５】

【０２１６】
第４層（中間層）
ゼラチン ・・・０．３８
混色防止剤（Ｃｐｄ−７） ・・・０．０７
混色防止剤（Ｃｐｄ−１０） ・・・０．０２
高沸点溶媒（Ｓｏｌｖ−１） ・・・０．０３
高沸点溶媒（Ｓｏｌｖ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−５） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−４） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−６） ・・・０．０２
ポリマー（Ｃｐｄ−８） ・・・０．０４
【０２１７】

【０２１８】
第６層（中間層）
ゼラチン ・・・０．３８
混色防止剤（Ｃｐｄ−７） ・・・０．０９
混色防止剤（Ｃｐｄ−１０） ・・・０．０２
高沸点溶媒（Ｓｏｌｖ−１） ・・・０．０３
高沸点溶媒（Ｓｏｌｖ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−５） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−４） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−６） ・・・０．０２
ポリマー（Ｃｐｄ−８） ・・・０．０４
【０２１９】

【０２２０】
第８層（中間層）
ゼラチン ・・・０．３４
高沸点溶媒（Ｓｏｌｖ−１） ・・・０．０３
高沸点溶媒（Ｓｏｌｖ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−５） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−４） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−６） ・・・０．０２
ポリマー（Ｃｐｄ−８） ・・・０．０４
【０２２１】
第９層（保護層）
ゼラチン ・・・０．７０
ハレーション防止染料（微粒子分散） ・・・０．１５
カルボキシメチルセルロース ・・・０．０５
ポリマー（Ｃｐｄ−１２） ・・・０．１４
界面活性剤（Ｃｐｄ−１３） ・・・０．０３
硬膜剤（Ｈ−１） ・・・０．１２
【０２２２】
更に、カラー感光材料２Ａの第３層の例示カプラーＹＣ−６を、例示カプラーＹＣ−７、ＹＣ−９、ＹＣ−１３とそれぞれ等モルに置き換えた以外は感光材料２Ａと同様にして感光材料２Ｂ〜２Ｄを作製した。感光材料２Ｃの第７層のＭＣ−１をＭＣ−３に等モル置き換えた以外は感光材料２Ｃと同様にして感光材料２Ｅを作製した。この感光材料２Ｅの第３層のＹＣ−９を、ＹＣ−１３、ＹＣ−１９、ＹＣ−２５にそれぞれ等モル置き換えた以外は感光材料２Ｅと同様にして感光材料２Ｆ〜２Ｈを作製した。この感光材料２Ｈの第７層のＭＣ−３を、ＭＣ−６、ＭＣ−８、ＭＣ−１２にそれぞれに等モル置き換えた以外は感光材料２Ｈと同様にして感光材料２Ｉ〜２Ｋを作製した。
【０２２３】
また、感光材料２Ｅの第３層に例示カプラーＹＣ−９を、ＹＣ−９に対して1/2倍モルのＹＣ−６と1/4倍モルのシアンカプラーＥｘＣ−１とに置き換えた以外は感光材料２Ｅと同様にして感光材料２Ｌを作製した。感光材料２Ｌの第３層のＹＣ−６を、ＹＣ−９に等モル置き換えた以外は感光材料２Ｌと同様にして感光材料２Ｍを作製した。感光材料２Ｅの第３層のＹＣ−９を、ＹＣ−９に対して1/2倍モルのＹＣ−１８に置き換えた以外は感光材料２Ｅと同様にして感光材料２Ｎを作製した。感光材料２Ｅの第３層のＹＣ−９を、ＹＣ−１に等モル置換えて、更に等モルのＹＣ−２４を追加した以外は感光材料２Ｅと同様にして感光材料２Ｏを作製した。また、感光材料２Ｅの第３層のＹＣ−９を、ＹＣ−２に等モル置換えて、更に等モルのＹＣ−３１を追加した以外は感光材料２Ｅと同様にして感光材料２Ｏを作製した。
【０２２４】
（比較例２）
更に、カラー感光材料２Ａの第３層のＹＣ−６を、比較カプラーＡに等モル置換えた以外は感光材料２Ａと同様にして比較用カラー感光材料３Ａを作製した。また、感光材料３Ａの第７層のＭＣ−１を比較カプラーＢに等モル置き換えた以外は感光材料３Ａと同様にして感光材料３Ｂを作製した。
【０２２５】
【化４４】

【０２２６】
一方、光透過性基板として厚さ１．１ｍｍの透明なアルカリガラス（２０ｃｍ×３０ｃｍ）を用いて、その表面にゼラチンとコロイダルシリカ（平均粒子サイズ７〜９μｍ）を重量比で１：３に混合し、界面活性剤としてサポニンを加えて塗布した。乾膜の塗布膜厚は０．２μｍであった。
【０２２７】
上記光透過基板の塗布面に前述の各種カラー感光材料の保護層とを密着させた。その後、密着面の温度が１３０℃になるように温度設定をしたラミネーターを用いて線速０．４５ｍ／分で通過させた。ほぼ室温に冷却した後、感光材料の支持体を剥離とともに乳剤面から引き剥がした。基板上に第２層から上の乳剤面が一様に密着しており白抜けは見られなかった。
【０２２８】
以上のようにして作成した比較用試料１Ａの乳剤層を有する基板に乳剤面側から図 １１に示すマスクフィルターと感光材料の分光感度に合致した色フィルターを重ねてタングステン光を用いて順次４回露光した。また、本発明の試料２Ａ〜２Ｐ及び比較用試料３Ａ及び３Ｂの乳剤を有する基板に乳剤面側から図４に示すＢ及びＧ光露光用マスクフィルターと白灯またはＩＲ光露光用マスクフィルターと感光材料の分光感度に合致した色フィルターを重ねてタングステン光を用いて順次３回露光した。露光済み基板を下記の工程に従い現像処理し、１回の操作でＢ、Ｇ、Ｒの三色及び黒色に発色したカラーフィルターを作成した。
【０２２９】
（処理工程） （温度） （時間）
硬膜処理 ３８℃ ３分
水洗−１ ３５℃ １分
発色現像 ３８℃ ８０秒
漂白定着 ３８℃ ９０秒
水洗−２ ３５℃ ４０秒
水洗−３ ３５℃ ４０秒
乾燥 ６０℃ ２分
【０２３０】
各処理液の組成は、以下の通りである。
〔硬膜液〕
硫酸ナトリウム（無水） １６０．０ｇ
炭酸ナトリウム（無水） ４．６ｇ
グリオキザール・プロピレングリコール付加物（５５％） ２０．０ｍｌ
水を加えて１リットル ｐＨ（２５℃）＝９．５
【０２３１】

【０２３２】
〔漂白定着液〕
水 ６００ｍｌ
チオ硫酸アンモニウム（７５０ｇ／リットル） ９３ｍｌ
亜硫酸アンモニウム ４０．０ｇ
臭化アンモニウム ２５．０ｇ
エチレンジアミン４酢酸・第二鉄アンモニウム ５５．０ｇ
エチレンジアミン４酢酸 ５．０ｇ
硝酸（６７％） ３０．０ｇ
水を加えて １リットル ｐＨ（２５℃）＝５．８
【０２３３】
〔水洗水〕
導伝率５μＳ以下の脱イオン水
【０２３４】
比較用試料１Ａおよび本発明の試料２Ａ〜２Ｐから得られたカラーフィルターは色濁りが無く分光透過性に優れたＲＧＢ及び高濃度の黒色のブラックストライプを有していたが、比較用試料３Ａおよび３Ｂから得られるカラーフィルターはいずれも青色、緑色の透過率が低く不十分であった。
【０２３５】
次に、各カラーフィルターの熱ステインおよび光堅牢性を評価した。
１８０℃のオーブンに１時間放置した後、青色画素部の透過率（波長４５０ｎｍ）を測定して熱ステインを評価した。各感光材料の加熱前の試料の透過率を１００とした時の加熱後の透過率の相対値を表５に示す。
【０２３６】
また、Ｘｅ退色試験機（８５０００ルックス １０日間）を用いて光堅牢性の評価を行った。各感光材料のＸｅ光照射前のＧ中のシアン濃度、及びＲ中のマゼンタ濃度を１００とし、光退色試験を行った。各感光材料のＧ中のシアン濃度及びマゼンタ濃度の低下率を各色素の残存率とした。結果を表５に示す。
【０２３７】
【表５】

【０２３８】
表５の結果から判るように、比較用試料１Ａにおいては残存カプラーに起因する熱ステインの発生が多く、その結果青色部の透過率が低下している。本発明のカプラーを用いた試料２Ａ〜２Ｐにおいては、熱ステインの発生が少ないために青色部および緑色部の透過率の低下が少なく優れていることが判る。また、表５の結果から、本発明のカプラーを用いた試料では、緑色部のシアン成分の堅牢性に優れ、また、赤色部のマゼンタ成分の光堅牢性に優れることが判る。
【０２３９】
実施例２
バック層としてカーボンブラックをポリ塩化ビニルに分散させて塗布した厚さ１００μｍのポリエチレンテレフタレート支持体にゼラチン下引きを施し、その上に以下に示す構成の第１層から第９層を多層同時塗布しカラー感光材料４Ａを作製した。以下に成分と塗布量（ｇ／ｍ²単位）を示す。尚ハロゲン化銀については銀換算の塗布量を示す。
【０２４０】

【０２４１】
第２層（ゼラチン隣接層）
ゼラチン ・・・０．５０
【０２４２】

【０２４３】
第４層（中間層）
ゼラチン ・・・０．３８
混色防止剤（Ｃｐｄ−７） ・・・０．０７
混色防止剤（Ｃｐｄ−１０） ・・・０．０２
高沸点溶媒（Ｓｏｌｖ−１） ・・・０．０３
高沸点溶媒（Ｓｏｌｖ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−５） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−４） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−６） ・・・０．０２
ポリマー（Ｃｐｄ−８） ・・・０．０４
【０２４４】

【０２４５】
第６層（中間層）
ゼラチン ・・・０．３８
混色防止剤（Ｃｐｄ−７） ・・・０．０９
混色防止剤（Ｃｐｄ−１０） ・・・０．０２
高沸点溶媒（Ｓｏｌｖ−１） ・・・０．０３
高沸点溶媒（Ｓｏｌｖ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−５） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−４） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−６） ・・・０．０２
ポリマー（Ｃｐｄ−８） ・・・０．０４
【０２４６】

【０２４７】
第８層（中間層）
ゼラチン ・・・０．３４
高沸点溶媒（Ｓｏｌｖ−１） ・・・０．０３
高沸点溶媒（Ｓｏｌｖ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−５） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−４） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−６） ・・・０．０２
ポリマー（Ｃｐｄ−８） ・・・０．０４
【０２４８】
第９層（保護層）
ゼラチン ・・・０．７０
ハレーション防止染料（微粒子分散） ・・・０．１５
カルボキシメチルセルロース ・・・０．０５
ポリマー（Ｃｐｄ−１２） ・・・０．１４
界面活性剤（Ｃｐｄ−１３） ・・・０．０３
硬膜剤（Ｈ−１） ・・・０．１２
【０２４９】
感光材料４Ａの第３層のＹＣ−６を、ＹＣ−１８、ＹＣ−１９、ＹＣ−２５とそれぞれ等モル置き換えた以外は感光材料４Ａと同様にして感光材料４Ｂ〜４Ｄを作製した。感光材料４Ｂの第７層のＹＭ−１を、ＹＭ−３、ＹＭ−５、ＹＭ−１３にそれぞれ等モル置き換えた以外は感光材料４Ｂと同様にして感光材料４Ｅ〜４Ｇを作製した。感光材料４Ａの第３層のＹＣ−６を、ＹＣ−１８に等モル置換え、更に等モルのＹＭ−２４、ＹＭ−３１をそれぞれ加えた以外は感光材料４Ａと同様にして感光材料４Ｈおよび４Ｉを作製した。感光材料４Ｈの第７層にＹＭ−１と等モルのＹＭ−１６、ＹＭ−１９をそれぞれ加えた以外は感光材料４Ｈと同様にして感光材料４Ｊ及び４Ｋを作製した。感光材料４Ｊの第３層のＹＣ−１８とＹＣ−２４を、４．４×１０^-4モルのＹＣ−６と２．２×１０^-4モルのＥｘＣ−１に置換えた以外は感光材料４Ｊと同様にして感光材料４Ｌを作製した。感光材料４Ａの第３層のＹＣ−６を比較カプラーＡに等モル置き換えた以外は感光材料４Ａと同様にして比較用感光材料３Ｃを作製した。また、感光材料３Ｃの第７層のＹＭ−１を比較カプラーＣに等モル置き換えた以外は感光材料３Ｃと同様にして比較用感光材料３Ｄを作製した。
【０２５０】
【化４５】

【０２５１】
この様にして作製した感光材料４Ａ〜４Ｌ、３Ｃおよび３Ｄを実施例１と同様の方法に従って、乳剤層を光透過性基板として厚さ１．１ｍｍの透明なアルカリガラスに転写させた。以上の用にした作製した４Ａ〜４Ｌ、３Ｃおよび３Ｄの乳剤を有する基板に乳剤面側から図７に示すＢ光露光用、Ｇ光露光用マスクフィルター及び白灯露光またはＩＲ光露光用マスクフィルターと感光材料の分光感度に合致した色フィルターを重ねてタングステン光を用いて順次３回露光した。露光済み基板を前述した工程に従い現像、脱銀、水洗処理し、１回の操作でＢ，Ｇ，Ｒの三色及び黒色に発色したカラーフィルターを作成した。
【０２５２】
実施例１と同様の方法に従って熱ステイン及び光堅牢性の評価を行った結果を表６に示す。実施例１と同様な傾向の結果が得られ、本発明のカプラーを有するカラーフィルターが優れていることが明らかとなった。
【０２５３】
【表６】

【０２５４】
実施例３
バック層としてカーボンブラックをポリ塩化ビニルに分散させて塗布した厚さ１００μｍのポリエチレンテレフタレート支持体にゼラチン下引きを施し、その上に以下に示す構成の第１層から第９層を多層同時塗布しカラー感光材料５Ａを作製した。以下に成分と塗布量（ｇ／ｍ²単位）を示す。尚ハロゲン化銀については銀換算の塗布量を示す。
【０２５５】

【０２５６】
第２層（ゼラチン隣接層）
ゼラチン ・・・０．５０
【０２５７】

【０２５８】
第４層（中間層）
ゼラチン ・・・０．３８
混色防止剤（Ｃｐｄ−７） ・・・０．０７
混色防止剤（Ｃｐｄ−１０） ・・・０．０２
高沸点溶媒（Ｓｏｌｖ−１） ・・・０．０３
高沸点溶媒（Ｓｏｌｖ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−５） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−４） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−６） ・・・０．０２
ポリマー（Ｃｐｄ−８） ・・・０．０４
【０２５９】

【０２６０】
第６層（中間層）
ゼラチン ・・・０．３８
混色防止剤（Ｃｐｄ−７） ・・・０．０９
混色防止剤（Ｃｐｄ−１０） ・・・０．０２
高沸点溶媒（Ｓｏｌｖ−１） ・・・０．０３
高沸点溶媒（Ｓｏｌｖ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−５） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−４） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−６） ・・・０．０２
ポリマー（Ｃｐｄ−８） ・・・０．０４
【０２６１】

【０２６２】
第８層（中間層）
ゼラチン ・・・０．３４
高沸点溶媒（Ｓｏｌｖ−１） ・・・０．０３
高沸点溶媒（Ｓｏｌｖ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−５） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−４） ・・・０．０２
紫外線吸収剤（Ｃｐｄ−３） ・・・０．０１
紫外線吸収剤（Ｃｐｄ−６） ・・・０．０２
ポリマー（Ｃｐｄ−８） ・・・０．０４
【０２６３】
第９層（保護層）
ゼラチン ・・・０．７０
ハレーション防止染料（微粒子分散） ・・・０．１５
カルボキシメチルセルロース ・・・０．０５
ポリマー（Ｃｐｄ−１２） ・・・０．１４
界面活性剤（Ｃｐｄ−１３） ・・・０．０３
硬膜剤（Ｈ−１） ・・・０．１２
【０２６４】
感光材料５Ａの第３層のＭＣ−１を、ＭＣ−３、ＭＣ−６、ＭＣ−８にそれぞれ等モル置き換えた以外は感光材料５Ａと同様に感光材料５Ｂ〜５Ｄを作製した。感光材料５Ｂの第７層のＹＭ−１を、ＹＭ−１２、ＹＭ−１３、ＹＭ−１４、ＹＭ−１５にそれぞれ等モルに置き換えた以外は感光材料５Ｂと同様に感光材料５Ｅ〜５Ｈを作製した。感光材料５Ｆの第３層のＭＣ−３を、等モルのＭＣ−８と置換え、更に１／３モルのＭＣ−１８を加えた以外は感光材料５Ｆと同様に感光材料５Ｉを作製した。また、感光材料５Ｉの第７層にＹＭ−１３と等モルのＹＭ−１６を加えた以外は感光材料５Ｉと同様に感光材料５Ｊを作製した。
一方、感光材料５Ａの第３層のカプラーＭＣ−１を比較カプラーＢに等モル置き換えた以外は感光材料５Ａと同様にして比較用感光材料３Ｅを作製した。また、感光材料３Ｅの第７層のカプラーＹＭ−１を比較カプラーＣに等モル置き換えた以外は感光材料３Ｅと同様にして比較用感光材料３Ｆを作製した。
【０２６５】
この様にして作製した感光材料５Ａ〜５Ｊ、３Ｅおよび３Ｆを実施例１と同様の方法に従って、乳剤層を、光透過性基板として厚さ１．１ｍｍの透明なアルカリガラスに転写させた。以上の用にした作製した５Ａ〜５Ｊの乳剤を有する基板に乳剤面側から図１０に示すＢ光露光用、Ｇ光露光用マスクフィルターと白灯露光用マスクフィルターと感光材料の分光感度に合致した色フィルターを重ねてタングステン光を用いて順次３回露光した。露光済み基板を前述した工程に従い現像処理、脱銀、水洗処理し、１回の操作でＢ、Ｇ、Ｒの三色及び黒色に発色したカラーフィルターを作成した。
【０２６６】
実施例１と同様の方法に従って熱ステイン及び光堅牢性の評価を行った結果を表７に示す。実施例１と同様な傾向の結果が得られ、本発明のカプラーを有するカラーフィルターが優れていることが判った。
【０２６７】
【表７】

【０２６８】
実施例４
裏面にポリプロピレンの保護膜（２０μｍ）をラミネートした光学的に等方な厚さ８０μｍのポリアリレート基板にグロー放電処理を施し、写真乳剤層との接着を良くするために、ＳＢＲラテックス層およびゼラチン層の２層を塗設した。この上に実施例１の剥離層（第１層）と第２層（ゼラチン隣接層）を除去し、その他の層の構成を逆にした層構成で、同時多層塗布し、実施例１と同様な露光、現像、定着、漂白、水洗、乾燥処理をしてフィルム基板のカラーフィルターを作製した。この様にして得られたカラーフィルター層の上に下記の組成物を乾燥膜状態で２．５μｍとなるように塗布、乾燥、紫外線硬化して保護層を設けた。得られたカラーフィルターはカラーフィルター層と保護層との密着性、耐薬品性は良好であった。この様にして作製した試料を実施例１と同様にして、熱ステインおよび光堅牢性を評価した結果、実施例１と同じ傾向の結果が得られ本発明のカプラーを用いたカラーフィルターが熱ステインの発生が少なく光堅牢性に優れることが判った。
【０２６９】
〔オーバーコート組成物処方〕
モノマー（１） ７７．４ｗｔ％
モノマー（２） ７．７
ポリマーＣＡＢ５３１（Eastman Chemical社製） １１．７
光重合開始剤 ２．４
増感剤 ０．８
塗布用希釈溶媒（ＭＥＫ） −
【０２７０】
【化４６】

【０２７１】
【発明の効果】
本発明のカラードカプラーを用いることにより、色濁りが無く分光透過性に優れたＲＧＢ及び高濃度の黒色のブラックストライプを有するカラーフィルターを簡便な層構成及び露光方法で作製できることが判った。また、熱ステインの発生が少なく、さらにシアン、およびマゼンタ成分の光堅牢性が向上し、本発明のカプラーが優れていることが明らかとなった。
【図面の簡単な説明】
【図１】マイクロカラーフィルターを形成するのに用いることができるマスターカラーフィルターの一態様を示す模式図である。
【図２】本発明のマイクロカラーフィルターの一態様を示す模式図である。
【図３】本発明のマイクロカラーフィルターの一態様を示す模式図である。
【図４】マイクロカラーフィルターを形成するのに用いることができるマスクフィルターの一態様を示す模式図である。
【図５】マイクロカラーフィルターを形成するのに用いることができるマスターカラーフィルターの一態様を示す模式図である。
【図６】本発明のマイクロカラーフィルターの一態様を示す模式図である。
【図７】マイクロカラーフィルターを形成するのに用いることができるマスクフィルターの一態様を示す模式図である。
【図８】マイクロカラーフィルターを形成するのに用いることができるマスターカラーフィルターの一態様を示す模式図である。
【図９】本発明のマイクロカラーフィルターの一態様を示す模式図である。
【図１０】マイクロカラーフィルターを形成するのに用いることができるマスクフィルターの一態様を示す模式図である。
【図１１】マイクロカラーフィルターを形成するのに用いることができるマスクフィルターの一態様を示す模式図である。
【図１２】本発明のカラーフィルターを用いたカラー液晶表示装置（ＬＣＤ）の断面図の一例である。
【符号の説明】
図１２における符号を説明する。
１、７ ガラス基板
２ ＲＧＢカラーフィルター
３、８ 透明電極
４ 配向膜
５ 液晶
６ シール剤
９ ブラックマトリックス
１０、１１ 偏向板
１２ バックライト[0001]
BACKGROUND OF THE INVENTION
The present invention is a silver halide color light-sensitive material suitable for producing a color filter having a thin film thickness, improving the swelling of a gelatin film with water, and further excellent in spectral transmission characteristics, heat fastness and light fastness, The present invention relates to a method for producing a color filter using the same and a color filter produced by the production method.
[0002]
[Prior art]
The color filter is used for a color face plate for CRT display, a photoelectric conversion element plate for copying, a filter for a single-tube color TV camera, a flat panel display using liquid crystal, a color solid-state image sensor, and the like.
Normally used color filters are configured by regularly arranging the three primary colors of red, green and blue, but there are also filters having four or more hues as required. For example, a color filter for an imaging tube or a color filter for a liquid crystal display device requires a black pattern (black matrix) for various purposes. Specific arrangement methods for red, green, and blue include mosaic and delta arrangement, which can be selected as necessary.
[0003]
Conventionally known methods for producing color filters include vapor deposition, dyeing, printing, pigment dispersion, electrodeposition, resist electrodeposition transfer, and the like. However, these methods have the disadvantages of a sugar that requires a complicated manufacturing process, is prone to pinholes and scratches, has a poor yield, and does not produce a system.
[0004]
In order to eliminate these disadvantages, an external development method using a silver halide light-sensitive material (for example, JP-A No. 55-6342) and an internal development method (for example, JP-A Nos. 62-148952 and 62) are disclosed. No. 71950) was studied.
[0005]
[Problems to be solved by the invention]
However, the former method requires color development at least three times, and it is difficult to say that the processing steps are simple. Further, it has been found that the latter method has a large film thickness and has problems such as a problem that the film is peeled off during the rubbing process or a disconnection is likely to occur in the LCD panel manufacturing process. In particular, the internal color light-sensitive material has a problem in that it has a large number of light-sensitive layers and the film thickness is large, and it is difficult to obtain a clear pattern.
[0006]
For example, when a color filter is used in a color liquid crystal display device or the like, it must go through steps such as coating of a protective film, vapor deposition of a transparent electrode, and coating of an alignment film. Degree stability is important. In particular, since color filters using silver halide light-sensitive materials use a gelatin film, the gelatin film swells and shrinks during the process of using water such as an alkaline aqueous solution and an acidic aqueous solution during patterning of the transparent electrode. There were problems such as disconnection, and improvements were desired.
[0007]
In the production of a color filter using an inner color photosensitive material, for example, when forming a blue pixel, the color of a magenta coupler and a cyan coupler is used, and when forming a green pixel, a cyan coupler and a yellow coupler are used. In the case of forming a red pixel using the above color development, a method utilizing the color development of a magenta coupler and a yellow coupler is known. When these couplers are added to the same layer to form blue, green and red colors, there is a problem that the light fastness of one of the dyes is lowered, and improvement of the light fastness is desired. In order to improve the fastness, there is a method in which each coupler is separated into different layers. However, the manufacturing process is complicated, and a simpler manufacturing method is desired.
[0008]
Further, in the method using these couplers, the occurrence of stain due to heat is observed due to remaining couplers that are not used as dyes, for example, yellow couplers in the blue part, magenta couplers in the green part, and cyan couplers in the red part. There is a problem that the transmittance of blue and green is lowered, and an improvement has been desired.
[0009]
On the other hand, a method for producing a color filter using a colored coupler in a silver halide light-sensitive material is disclosed in Japanese Patent Application Laid-Open No. 55-111003, and the couplers described in these are at blue, green and red wavelengths. The transmittance was low and an improvement was desired. In addition, improvements in heat fastness and light fastness have been desired.
[0010]
Accordingly, a first object of the present invention is to provide a color filter having a thin film thickness and a clear pattern. The second object is to provide a color filter excellent in light transmittance by a simpler method. A third object is to provide a color filter excellent in heat and light fastness. A fourth object is to provide a method for manufacturing a color filter which does not require a complicated process and hardly causes defects in the LCD panel manufacturing process and is suitable for mass production.
[0011]
[Means for Solving the Problems]
  It has been found that the above object of the present invention is achieved by the following (i) to (iii). That is, (i) any one of the three primary colors of cyan, magenta, and yellow subtractive colors, and any of the other two primary colors through a coupling reaction with an oxidant of the color developing agent A silver halide emulsion layer (1) containing a colored coupler (1a) that produces a dye having one color, and a color reaction different from that of the emulsion layer, and a coupling reaction from the colored coupler (1a) The color of the dye produced by the above-mentioned color coupler (1a) is coupled with the oxidized color developing agent having one of the three primary colors other than the two primary colors before the coupling reaction of the colored coupler (1a). And a silver halide emulsion layer (2) containing a colored coupler (1b) for producing a dye having the same color as that of the dye produced by the coupling reaction from the colored coupler (1a).And an emulsion layer having a color sensitivity different from these two emulsion layers,
The layer is a layer containing a coupler that corrects the color so that the transmission density is substantially black with a transmission density of 2.5 or more.The color photosensitive material to be used, and the surface of the color photosensitive material are divided into a number of parts, a part of which is not exposed, and the other part is exposed with light having a wavelength at which only the emulsion layer (1) is exposed, The remaining portion comprises at least color development, desilvering, and water washing steps after exposure to light having a wavelength that only the emulsion layer (2) is exposed to, and thereby a method for producing a color filter, and thereby The resulting color filter.
[0012]
  (Ii) any one of the three primary colors of cyan, magenta and yellow, and any one of the other two primary colors through a coupling reaction with the oxidized color developing agent A silver halide emulsion layer (1) containing a colored coupler (1a) that produces a dye having a color, and a color before the coupling reaction of the colored coupler (1a) having a color sensitivity different from that of the emulsion layer The color of the dye produced by the coupling reaction from the colored coupler (1a) by the coupling reaction with the oxidized form of the color developing agent and the color before the coupling reaction of the colored coupler (1a) A silver halide emulsion layer (3) containing a colored coupler (1c) that produces a dye of one of the three primary colors.In addition, these two emulsion layers have an emulsion layer having a color sensitivity different from that of the two emulsion layers, and the layer contains a coupler for correcting the color so that the transmission density is substantially black of 2.5 or more. Characterized by being layeredThe color light-sensitive material and the surface of the color light-sensitive material are divided into a number of parts, a part of which is exposed to light having a wavelength that only the emulsion layer (1) is sensitive to, and the other part is the emulsion layer (3 ) Is exposed to light having a wavelength at which light is exposed, and the remaining portions are exposed to light having a wavelength at which both the emulsion layer (1) and the emulsion layer (3) are exposed, and then at least color development, desilvering and washing with water. A method for producing a color filter, comprising: and a color filter obtained thereby.
[0013]
  (Iii) Any one of the three primary colors of cyan, magenta and yellow, and one of the other two primary colors by a coupling reaction with an oxidized form of the color developing agent. A silver halide emulsion layer (2) containing a colored coupler (1b) for producing a colored dye and a color sensitivity different from that of the emulsion layer, and produced from the colored coupler (1b) by a coupling reaction It has one color among the three primary colors other than the two colors of the color of the dye and the colored coupler (1b) before the coupling reaction, and the coupling reaction with the oxidant of the color developing agent A silver halide emulsion layer (3) containing a colored coupler (1c) that produces a dye having the same color as the color before the coupling reaction of the colored coupler (1b).In addition, these two emulsion layers have an emulsion layer having a color sensitivity different from that of the two emulsion layers, and the layer contains a coupler for correcting the color so that the transmission density is substantially black of 2.5 or more. Characterized by being layeredThe color photosensitive material to be used, and the surface of the photosensitive material are divided into a number of parts, some of which are not exposed, and the other part is exposed with light having a wavelength at which only the emulsion layer (2) is exposed. The remaining portion is exposed to light having a wavelength at which both the emulsion layer (2) and the emulsion layer (3) are exposed, and then subjected to at least color development, desilvering, and water washing, and a method for producing a color filter, Color filter obtained by this.
[0014]
Colored couplers are compounds that have a certain color before color development, but lose the original color through a coupling reaction with an oxidized form of the color developing agent to produce a dye having a different color.
[0015]
As a colored coupler suitable for use in the present invention,
(1) Although it itself has a yellow color, it loses its original color by a coupling reaction with an oxidized form of a color developing agent and develops a cyan color {denoted as Y- (C)}
(2) Although it itself has a yellow color, it loses its original color by a coupling reaction with an oxidized form of a color developing agent and develops a magenta color {denoted as Y- (M)} ,
(3) Although it has a magenta color itself, it loses its original color by a coupling reaction with an oxidized form of a color developing agent, and develops cyan color {denoted as M- (C)} ,
(4) Although itself has a magenta color, it loses its original color by a coupling reaction with an oxidized form of a color developing agent and develops a yellow color (denoted as M- (Y)) ,
(5) Although it itself has a cyan color, it loses its original color by a coupling reaction with an oxidized form of a color developing agent and develops a yellow color {denoted as C- (Y)} ,
(6) Although it itself has a cyan color, it loses its original color by a coupling reaction with an oxidized form of a color developing agent and develops a magenta color {denoted as C- (M)}
There are six possible ways.
[0016]
The first embodiment of the present invention (embodiment (i) described above) for forming a multi-color filter having at least a red, blue and green pixel pattern is, for example, Y- (C) and M- ( The case where two colored couplers represented by C) are used will be described. This first embodiment has on a support at least two silver halide emulsion layers having maximum spectral sensitivity at different wavelengths of the spectrum, and a silver halide emulsion layer (α having maximum spectral sensitivity at the first wavelength) ) Contains a compound of Y- (C), and the silver halide emulsion layer (β) having the maximum spectral sensitivity at the second wavelength has a constitution containing the compound of M- (C). .
[0017]
When the silver halide light-sensitive material of the first embodiment is exposed to the first wavelength, the color development process causes the Y- (C) compound to couple with the oxidized color developing agent in the emulsion layer (α). A cyan dye formed by reaction is formed, and a blue color is formed by mixing with the magenta color of the M- (C) compound itself in the emulsion layer (β). In the portion exposed at the second wavelength, a cyan color is formed in the emulsion layer (β) by color development, and this cyan color and the yellow color of the Y- (C) compound itself in the emulsion layer (α) are mixed. A green color is obtained. In the unexposed portion, a red color is obtained in which the yellow color of the Y- (C) compound itself in the emulsion layer (α) and the magenta color of the M- (C) compound itself in the emulsion layer (β) are mixed. Cyan dye formed when Y- (C) compound undergoes coupling reaction with oxidant of color developing agent in emulsion layer (α) when exposed to light having a wavelength obtained by adding the first wavelength and the second wavelength In the emulsion layer (β), a cyan dye formed by the coupling reaction of the compound of M- (C) with the oxidized color developing agent is formed at both the first wavelength and the second wavelength. A cyan color is obtained in the exposed portion.
[0018]
Therefore, a multi-color filter having a red part, a blue part and a green part is formed by irradiating the above-mentioned silver halide photosensitive material with light of the first wavelength and the second wavelength simultaneously or sequentially in a pattern. it can. Most simply, the emulsion layer (α) is blue sensitive and the emulsion layer (β) is green sensitive (emulsion layer (α) or emulsion layer (β) may be red sensitive), as shown in FIG. 2 has a blue pixel pattern, a green pixel pattern, and a black pixel pattern, and the remaining portion is subjected to one-shot exposure through a transparent master color filter and subjected to color development, desilvering treatment, and water washing treatment, as shown in FIG. Various color filters can be obtained.
[0019]
In the color filter thus obtained, a black stripe portion as shown in FIG. 3 and each pixel of red, blue and green are formed by forming a black stripe portion using a chromium film or a carbon film by a known method. A color filter having a pattern can be obtained.
[0020]
Alternatively, as shown in FIG. 4, there are three types of mask patterns (each having a light transmitting portion corresponding to a blue pixel pattern and a green pixel pattern and a black (light-shielding) pixel pattern) and a color matching the spectral sensitivity. A color filter as shown in FIG. 2 is exposed to blue light, green light and white light (or light obtained by adding blue and green light) using a filter, and is subjected to color development, desilvering treatment, and water washing treatment. Get. By forming a black stripe portion using a chromium film or a carbon film by a known method, a color filter having a black stripe portion and red, blue, and green pixel patterns as shown in FIG. 3 can be obtained.
[0021]
The second embodiment of the present invention (embodiment (ii) above) for forming a multi-color filter having at least a red, blue and green pixel pattern is, for example, Y- (C) and Y- (M) 2 A case where a colored coupler of a kind is used will be described. This second embodiment has on a support at least two silver halide emulsion layers having maximum spectral sensitivity at different wavelengths of the spectrum, and a silver halide emulsion layer (α ) Contains the compound Y- (C), and the silver halide emulsion layer (β) having the maximum spectral sensitivity at the second wavelength has a constitution containing the compound Y- (M). .
[0022]
When the silver halide photosensitive material of the second embodiment is exposed to the first wavelength, the color development processing causes the Y- (C) compound to couple with the oxidized color developing agent in the emulsion layer (α). A cyan dye formed by the reaction is formed, and a green color is formed by mixing with the yellow color of the Y- (M) compound itself in the emulsion layer (β). In the part exposed at the second wavelength, a magenta color is formed in the emulsion layer (β) when the Y- (M) compound is coupled with an oxidized form of the color developing agent upon color development, A red color is obtained by mixing this magenta color with the yellow color of the Y- (C) compound itself of the emulsion layer (α). In the portion exposed at both the first wavelength and the second wavelength, when color development is performed, the Y- (C) compound is formed in the emulsion layer (α) by a coupling reaction with an oxidized form of the color developing agent. A cyan dye is formed, and a magenta dye is formed in the emulsion layer (β) by the coupling reaction of the Y- (M) compound with an oxidized form of a color developing agent. Is obtained.
[0023]
Therefore, a multi-color filter having a red part, a blue part and a green part is formed by irradiating the above-mentioned silver halide photosensitive material with light of the first wavelength and the second wavelength simultaneously or sequentially in a pattern. it can. In the simplest case, the emulsion layer (α) is made blue sensitive and the emulsion layer (β) is made green sensitive (the emulsion layer (α) or the emulsion layer (β) may be made red sensitive), as shown in FIG. Blue pixel pattern, green pixel pattern, and colorless and transparent pixel pattern, and the rest is black by shading through a master color filter, and one-shot exposure is performed by color development, desilvering, and water washing. A color filter as shown in FIG. 6 can be obtained.
[0024]
In the color filter thus obtained, a black stripe portion as shown in FIG. 3 and each pixel of red, blue and green are formed by forming a black stripe portion using a chromium film or a carbon film by a known method. A color filter having a pattern can be obtained.
[0025]
Alternatively, blue and green light exposure is performed using a mask filter for B light exposure and G light exposure as shown in FIG. 7 and a color filter that matches spectral sensitivity, and color development, desilvering treatment, and water washing are performed. By performing the processing, a color filter as shown in FIG. 6 is obtained. Also, a color having a black stripe portion and red, blue, and green pixel patterns as shown in FIG. 3 by forming a black stripe portion on the color filter using a chromium film or a carbon film by a known method. A filter can be obtained.
[0026]
A third embodiment (embodiment (iii) above) for forming a multi-color filter having at least a red, blue and green pixel pattern is made of, for example, two kinds of colored M- (C) and Y- (M). A case where a coupler is used will be described. This third embodiment has on the support at least two silver halide emulsion layers having a maximum spectral sensitivity at different wavelengths of the spectrum, and a silver halide emulsion layer (α ) Contains the compound of M- (C), and the silver halide emulsion layer (β) having the maximum spectral sensitivity at the second wavelength has a constitution containing the compound of Y- (M). .
[0027]
When the silver halide light-sensitive material of the third embodiment is exposed at the first wavelength, the color development processing causes the M- (C) compound to couple with the oxidized color developing agent in the emulsion layer (α). A cyan dye formed by the reaction is formed, and a green color is formed by mixing with the yellow color of the Y- (M) compound itself in the emulsion layer (β). In the portion exposed to light mixed with the first wavelength and the second wavelength, the color development process causes the M- (C) compound to undergo a coupling reaction with the oxidant of the color developing agent in the emulsion layer (α). A cyan dye is formed, and a magenta color is formed in the emulsion layer (β) by the coupling reaction of the Y- (M) compound with an oxidized form of the color developing agent. The cyan and magenta colors are formed. To form a blue color. In the portion exposed to light of the second wavelength, when color development is performed, a compound of Y- (M) is coupled with an oxidized form of a color developing agent in the emulsion layer (β) to obtain a magenta dye. A magenta color is obtained by mixing with the magenta color of the M- (C) compound itself of the layer (α). The unexposed part is a red color in which the magenta color of the M- (C) compound itself contained in the emulsion layer (α) and the yellow color of the Y- (M) compound itself in the emulsion layer (β) are mixed. It is formed.
[0028]
Therefore, a multi-color filter having a red part, a blue part and a green part is formed by irradiating the above-mentioned silver halide photosensitive material with light of the first wavelength and the second wavelength simultaneously or sequentially in a pattern. it can. In the simplest case, the emulsion layer (α) is made blue sensitive and the emulsion layer (β) is made green sensitive (the emulsion layer (α) or the emulsion layer (β) may be made red sensitive), as shown in FIG. Blue pixel pattern, black (light-shielding) pixel pattern, and colorless and transparent pixel pattern, and the rest is subjected to one-shot exposure through a master color filter colored green, and then subjected to color development, desilvering treatment, and water washing treatment As a result, a color filter as shown in FIG. 9 can be obtained.
[0029]
In the color filter thus obtained, a black stripe portion as shown in FIG. 3 and each pixel of red, blue and green are formed by forming a black stripe portion using a chromium film or a carbon film by a known method. A color filter having a pattern can be obtained. As another method, blue and green light exposure is performed using a B light exposure mask pattern, a G light exposure mask pattern, and a color filter that matches the spectral sensitivity as shown in FIG. A color filter as shown in FIG. 9 is obtained by performing a water washing treatment. Also, a color having a black stripe portion and red, blue, and green pixel patterns as shown in FIG. 3 by forming a black stripe portion on the color filter using a chromium film or a carbon film by a known method. A filter can be obtained.
[0030]
  In the various aspects described above,In the present invention,Furthermore, an emulsion layer (γ) having a maximum spectral sensitivity at a third wavelength (for example, red light or infrared light) is provided, and the transmission density of all colored couplers contained in the emulsion layers (α) and (β), or Substantially black (END ≧ 2....) In which the sum of the transmission density of the dye obtained from the coupling reaction with the oxidized color developing agent and the transmission density of the dye obtained from the emulsion layer (γ) is 2.5 or more. 5) Contains a coupler that corrects the color so thatLet TheThe emulsion layer (γ) may be composed of two or more unit layers. In this case, an intermediate layer between other adjacent silver halide emulsion layers can be removed by appropriately selecting the layer constitution of each unit layer and the contained coupler. The coupler for color correction may be the same as or different from the coupler used in the emulsion layers (α) and (β). For this silver halide photosensitive material, in addition to the exposure described above, the light of the fourth wavelength (for example, red light or infrared light) corresponds to the black stripe (the white lamp in FIGS. 4, 7 and 10). By applying color development, desilvering treatment, and water washing treatment, a color filter colored in red, green, blue and high density black can be obtained.
[0031]
The present invention is not limited only to the above-described various embodiments, and other than these, a combination of a colored coupler, a photosensitive layer, and an exposure wavelength is possible.
[0032]
The silver halide light-sensitive material of the various aspects described above may be provided with an undercoat layer, an intermediate layer, a bleachable yellow filter layer, a protective layer, an ultraviolet absorbing layer, or the like as necessary.
[0033]
In the present invention, the colored coupler (1a) is a compound represented by the following general formula (I) or (II), and the colored coupler (1b) is represented by the following general formula (III) or (IV). As the colored coupler (1c), a compound represented by the following general formula (V) or general formula (VI) is particularly preferably used.
[0034]
The compounds of the general formulas (I) and (II) are themselves dyes having a yellow color. These compounds have a function of losing the original color by a coupling reaction with an oxidant of the color developing agent to develop a cyan color. The compounds of the general formulas (III) and (IV) are themselves dyes having a magenta color. These compounds have a function of losing the original color by a coupling reaction with an oxidant of the color developing agent to develop a cyan color. The compounds of the general formulas (V) and (VI) are also dyes having a yellow color. These compounds have a function of losing the original color by a coupling reaction with an oxidant of the color developing agent to develop a magenta color.
[0035]
Formula (I)
Q₁-(TIME)_n-(L₁)_m-(YDYE)
[0036]
In formula (I), Q₁Represents a coupler residue that forms a cyan dye by a coupling reaction with an oxidized form of a color developing agent, and TIME represents Q by a coupling reaction with an oxidized form of a developing agent.₁After leaving more (TIME)_n-1-(L₁)_m-Timing group for cleaving (YDYE), or after leaving TIME (TIME)_n-2-(L₁)_m-Represents a timing group for cleaving (YDYE). n represents 0, 1, 2, or 3. When n is 2 or more, the plurality of TIMEs are the same or different. L₁Represents a divalent linking group, (YDYE) represents a yellow dye residue capable of flowing out into the processing liquid, and m represents 0, 1, 2, or 3.
[0037]
Formula (II)
A₁-N = N-R₁
[0038]
In formula (II), A₁Represents a coupler residue that forms a cyan dye by coupling with an oxidized form of a color developing agent;₁Represents an aryl group or a heterocyclic group.
[0039]
General formula (III)
Q₂-(TIME)_n-(L₂)_m-(MDYE)
[0040]
In formula (III), Q₂Represents a coupler residue that forms a cyan dye by coupling with an oxidized form of a developing agent. TIME represents Q by a coupling reaction with an oxidized form of a developing agent.₂After leaving more (TIME)_n-1-(L₂)_m-Timing group to cleave (MDYE), or after leaving TIME (TIME)_n-2-(L₂)_m-Represents a timing group for cleaving (MDYE). n represents 0, 1, 2, or 3. When n is 2 or more, the plurality of TIMEs are the same or different. L₂Represents a divalent linking group, (MDYE) represents a magenta dye residue capable of flowing out into the processing solution, and m represents 0, 1, 2, or 3.
[0041]
Formula (IV)
A₂-N = N-R₂
[0042]
In formula (IV), A₂Represents a coupler residue that forms a cyan dye by coupling with an oxidized form of a developing agent;₂Represents an aryl group or a heterocyclic group.
[0043]
General formula (V)
Q_Three-(TIME)_n-(L_Three)_m-(YDYE)
[0044]
In formula (V), Q_ThreeRepresents a coupler residue that forms a magenta dye by coupling with an oxidized form of a developing agent, and TIME represents Q by a coupling reaction with an oxidized form of the developing agent._ThreeAfter leaving more (TIME)_n-1-(L_Three)_m-Timing group for cleaving (YDYE), or after leaving TIME (TIME)_n-2-(L_Three)_m-Represents a timing group for cleaving (YDYE). n represents 0, 1, 2, or 3. When n is 2 or more, the plurality of TIMEs are the same or different. L_ThreeRepresents a divalent linking group, (YDYE) represents a yellow dye residue capable of flowing out into the processing liquid, and m represents 0, 1, 2, or 3.
[0045]
General formula (VI)
A_Three-N = N-R_Three
[0046]
In formula (VI), A_ThreeRepresents a coupler residue that forms a magenta dye by coupling with an oxidized form of a developing agent, and R_ThreeRepresents an aryl group or a heterocyclic group.
[0047]
The colored couplers represented by formulas (I) to (VI) will be described in more detail. In the above formula, Q₁~ Q_Three, TIME, (YDYE), (MDYE), A₁~ A_ThreeAnd R₁~ R_ThreeIn the case of containing non-diffusible groups, the total number of carbon atoms thereof is selected to be 8 to 60, preferably 10 to 40. In other cases, the total number of carbon atoms is preferably 15 or less. In the case of a bis-type, telomer-type or polymer-type coupler, any of the above-described substituents represents a divalent group and connects repeating units. In this case, the carbon number range may be out of the range.
[0048]
In the following description, R₄₀Is a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine), an alkyl group (preferably a linear or branched alkyl group having 1 to 40 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, 1-octyl, tridecyl), cycloalkyl group (preferably a cycloalkyl group having 3 to 40 carbon atoms, such as cyclopropyl, 1-ethylcyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl) ), An alkenyl group (preferably an alkenyl group having 2 to 40 carbon atoms such as vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 32 carbon atoms such as phenyl 1-naphthyl, 2-naphthyl), a heterocyclic group (preferably a 5- to 8-membered ring having 1 to 32 carbon atoms) Cyclic groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl), cyano group, silyl Group (preferably a silyl group having 3 to 40 carbon atoms, for example, trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, carboxyl group, nitro group, alkoxy group (preferably Is an alkoxy group having 1 to 40 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy), a cycloalkyloxy group (preferably a cyclohexane having 3 to 8 carbon atoms). An alkyloxy group such as cyclopentyloxy, cyclohexyl Acyloxy), an aryloxy group (preferably an aryloxy group having 6 to 40 carbon atoms, e.g., phenoxy, 2-naphthoxy),
[0049]
Heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 40 carbon atoms, such as 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy, 2-furyloxy), silyloxy group (preferably carbon number A silyloxy group having 1 to 40, for example, trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably an acyloxy group having 2 to 40 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy, Dodecanoyloxy), alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 45 carbon atoms, such as ethoxycarbonyloxy, 2-ethylhexyloxycarbonyloxy, t-butoxycarbonyloxy), cycloalkyl An oxycarbonyloxy group (preferably a cycloalkyloxycarbonyloxy group having 4 to 40 carbon atoms, such as cyclohexyloxycarbonyloxy), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 40 carbon atoms, For example, phenoxycarbonyloxy), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 40 carbon atoms such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, 1-morpholinocarbamoyloxy), sulfa Moyloxy group (preferably a sulfamoyloxy group having 1 to 40 carbon atoms, such as N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), alkanesulfonyloxy group (preferably 1 carbon atom) ~ 0 alkanesulfonyloxy group, for example, methanesulfonyloxy, hexadecanesulfonyloxy), arenesulfonyloxy group (preferably an arenesulfonyloxy group having 6 to 40 carbon atoms, for example, benzenesulfonyloxy), acyl group (preferably An acyl group having 1 to 40 carbon atoms, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl),
[0050]
An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 40 carbon atoms, for example, a methoxycarbonyl group, for example, methoxycarbonyl, ethoxycarbonyl, 2-ethylhexyloxycarbonyl, octadecyloxycarbonyl), a cycloalkyloxycarbonyl group (preferably Is a cycloalkyloxycarbonyl group having 4 to 40 carbon atoms such as cyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 40 carbon atoms such as phenoxycarbonyl), a carbamoyl group (preferably Is a carbamoyl group having 1 to 40 carbon atoms such as carbamoyl, N, N-dibutylcarbamoyl, N-ethyl-N-octylcarbamoyl, N-propylcarbamoyl), amino group ( Preferably, it is an amino group having 40 or less carbon atoms, such as amino, methylamino, N, N-dioctylamino, tetradecylamino, octadecylamino), an anilino group (preferably an anilino group having 6 to 40 carbon atoms, Anilino, N-methylanilino), a heterocyclic amino group (preferably a heterocyclic amine group having 1 to 40 carbon atoms, such as 4-pyridylamino), a carbonamido group (preferably a carbonamido group having 2 to 40 carbon atoms). For example, acetamide, benzamide, tetradecanamide), ureido group (preferably a ureido group having 1 to 40 carbon atoms, for example, N, N-dimethylureido, N-phenylureido), imide group (preferably 40 or less carbon atoms). For example, N-succinimide, N-phthalimide, hexadecenyls Cinimide), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 40 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino), cycloalkyloxycarbonylamino group (Preferably a cycloalkyloxycarbonylamino group having 4 to 40 carbon atoms, such as cyclohexyloxycarbonylamino), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 40 carbon atoms, such as phenoxycarbonyl) Amino), a sulfonamide group (preferably a sulfonamide group having 1 to 40 carbon atoms, methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecans Sulfamoylamino group (preferably a sulfamoylamino group having 1 to 40 carbon atoms, N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), azo group ( Preferably it is a C1-C40 noazo group, for example, phenylazo, naphthylazo, thiazolylazo, oxazolylazo, imidazolylazo, pyrazolylazo),
[0051]
An alkylthio group (preferably an alkylthio group having 1 to 40 carbon atoms, for example, ethylthio, octylthio), a cycloalkylthio group (preferably a cycloalkylthio group having 3 to 40 carbon atoms, for example, cyclohexylthio), an arylthio group (preferably An arylthio group having 6 to 40 carbon atoms, for example, phenylthio, naphthylthio), a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 40 carbon atoms, such as 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 40 carbon atoms, for example, dodecanesulfinyl group), an arenesulfinyl group (preferably an arenesulfinyl group having 6 to 40 carbon atoms, for example, Benzenesulfinyl), alkane A sulfonyl group (preferably an alkanesulfonyl group having 1 to 40 carbon atoms such as methanesulfonyl or octanesulfonyl), an arenesulfonyl group (preferably an arenesulfonyl group having 6 to 40 carbon atoms such as benzenesulfonyl or 1-naphthalene) Sulfonyl), an alkoxysulfonyl group (preferably an alkoxysulfonyl group having 1 to 40 carbon atoms, for example, methoxysulfonyl, ethoxysulfonyl), a cycloalkyloxysulfonyl group (preferably a cycloalkyloxysulfonyl group having 3 to 40 carbon atoms, For example, cyclopropyloxysulfonyl), aryloxysulfonyl group (preferably an aryloxysulfonyl group having 6 to 40 carbon atoms, such as phenoxysulfonyl, p-methylphenoxysulfonyl), sulfamoyl (Preferably a sulfamoyl group having 40 or less carbon atoms, for example, sulfamoyl, N, N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), sulfo group, phosphonyl group (preferably having 1 to 40 carbon atoms) A phosphonyl group of phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl) and a phosphinoylamino group (for example, diethoxyphosphinoylamino, dioctyloxyphosphinoylamino).
[0052]
R₄₁Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and preferred carbon number and specific examples of these groups are R₄₀This is the same as described in.
[0053]
R₄₂Is a cyano group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, cycloalkylsulfonyl group, arylsulfonyl group, heterocyclic group, acyl group, sulfamoyl group, phosphonyl group, Represents a phynoylamino group, an imide group, or a perfluoroalkyl group, and the preferred carbon number and specific examples of these groups are R₄₀This is the same as explained in.
R₄₃Represents an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkanesulfonyl group or an arenesulfonyl group, and preferred carbon number and specific examples of these groups are R₄₀This is the same as described in.
[0054]
Q of the coupler represented by the general formula (I)₁, TIME, L₁, (YDYE), n and m will be described in detail.
Q₁Represents a cyan coupler residue represented by the following general formula (VII), general formula (VIII), general formula (IX) or general formula (X).
[0055]
[Chemical 1]

[0056]
In formula (VII), R_FourIs an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heterocyclic group, an alkylamino group, a cycloalkylamino group, an arylamino group, a heterocyclic amino group, an alkylcarbamoyl group, a cyclo Represents an alkylcarbamoyl group, an arylcarbamoyl group, an alkylsulfamoyl group, a cycloalkylsulfamoyl group or an arylsulfamoyl group, and the preferred carbon number of these groups, specific examples are R₄₀It represents the same meaning as those groups described in. R_FiveAnd R₆Each independently represents a hydrogen atom or a substituent, and R₄₀Represents a group having the same meaning as * (TIME)_n-(L₁)_m-Represents the position of binding to (YDYE).
[0057]
[Chemical 2]

[0058]
In formula (VIII), R₇Is R_FourRepresents a group having the same meaning as M₁Represents a group of nonmetallic atoms necessary for forming a 5-membered, 6-membered or 7-membered ring with a condensed benzene ring. * (TIME)_n-(L₁)_m-Represents a bonding position with (YDYE).
[0059]
[Chemical 3]

[0060]
In formula (IX), R₈Represents an alkyl group, cycloalkyl group, aryl group, heterocyclic group, alkoxy group, cycloalkyloxy group, aryloxy group, heterocyclic oxy group, alkylamino group, cycloalkylamino group or arylamino group, and these groups Preferred carbon number and specific example of R are R₄₀Represents a group having the same meaning as described above. L_FourAnd L_FiveAre each independently -CO- or -SO₂-Represents R₉Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and preferred carbon number and specific examples of these groups are R₄₀Represents a group having the same meaning as described above. R_TenRepresents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R₁₁Represents a substituent. R_TenAnd R₁₁Preferred carbon numbers and specific examples of these groups are R₄₀Represents a group having the same meaning as described above. p represents an integer of 0 to 3. * (TIME)_n-(L₁)_m-Represents a bonding position with (YDYE).
[0061]
[Formula 4]

[0062]
In formula (X), R₁₂And R₁₃Each independently represents a hydrogen atom or a substituent, and R₄₀Represents a group having the same meaning as M₂Represents a group of non-metallic atoms necessary for forming a 5-membered, 6-membered or 7-membered ring with a fused pyrrole ring. * (TIME)_n-(L₁)_m-Represents a bonding position with (YDYE).
[0063]
Next, the preferable range of the coupler residue represented by the general formula (VII) to the general formula (X) will be described.
[0064]
R of the coupler residue represented by the general formula (VII)_FourIs preferably an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, a heterocyclic group, an alkylamino group, a cycloalkylamino group, an arylamino group or a heterocyclic amino group, and an alkyl group or a cycloalkyl group More preferred are an aryl group, an alkoxy group, and a cycloalkyloxy group. Most preferably, an alkyl group, a cycloalkyl group, an aryl group, and an alkoxy group are mentioned.
[0065]
R_FiveIs a halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, cycloalkyloxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, carbamoyl group, amino group, anilino group, heterocyclic amino group, Carbonamido group, ureido group, alkoxycarbonylamino group, cycloalkyloxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfamoylamino group, alkylthio group, cycloalkylthio group, arylthio group, heterocyclic thio group, A phosphinoylamino group is preferable, and a halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, cycloalkyloxy group, aryloxy group, carbonamido group, ureido group, alkoxycarbonyl Amino group, a cycloalkyloxy group, an aryloxycarbonylamino group, a sulfonamido group, a phosphinoylamino group more preferred. Most preferably, an alkyl group, an alkoxy group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, and a cycloalkyloxycarbonylamino group are exemplified.
[0066]
R₆Is a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, cycloalkyloxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, carbamoyl group, amino group, anilino group, heterocyclic ring Amino group, carbonamido group, ureido group, alkoxycarbonylamino group, cycloalkyloxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, sulfamoylamino group, alkylthio group, cycloalkylthio group, arylthio group, heterocycle Thio group and phosphinoylamino group are preferable, and hydrogen atom, halogen atom, alkyl group, alkoxy group, aryloxy group, carbonamido group, alkoxycarbonylamino group, cycloalkyloxycarbonylamino More preferably phosphinoylamino group. Most preferably, a hydrogen atom, a halogen atom, and a carbonamido group are mentioned.
[0067]
Next, a preferred range of the coupler residue represented by the general formula (VIII) will be described. R₇Is preferably an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, a heterocyclic group, an alkylamino group, a cycloalkylamino group, an arylamino group or a heterocyclic amino group, an alkyl group, a cycloalkyl group, An aryl group, an alkoxy group, and a cycloalkyloxy group are more preferable. Most preferably, an alkyl group, a cycloalkyl group, and an alkoxy group are mentioned.
M₁Is preferably a 5-membered, 6-membered or 7-membered saturated ring together with a condensed benzene ring.
[0068]
Next, a preferred range of the coupler residue represented by the general formula (IX) will be described. R₈Is preferably an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an alkylamino group or a cycloalkylamino group, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group. More preferably an alkylamino group. Most preferably, an alkyl group, a cycloalkyl group, and an alkoxy group are mentioned.
L_FourIs preferably -CO-.
[0069]
R₉Is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and most preferably a hydrogen atom.
R_TenIs preferably an alkyl group, a cycloalkyl group or an aryl group, more preferably an alkyl group or a cycloalkyl group. Most preferably, an alkyl group is mentioned.
[0070]
R₁₁Is a halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, cycloalkyloxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, heterocyclic thio, carbonamido group, sulfonamido group, carbamoyl group , Sulfamoyl group, imide group, sulfonyl group, hydroxy group, amino group, carboxyl group are preferred, halogen atom, alkoxy group, cycloalkyloxy group, carbonamido group, sulfonamido group, carbamoyl group, sulfamoyl group, hydroxy group, carboxyl More preferred are groups. Most preferably, a halogen atom, a carbonamido group, a hydroxy group, a carboxyl group, or a sulfonamido group is more preferred. Most preferably, a halogen atom is mentioned.
p is preferably 0 or 1, and most preferably 0.
[0071]
Next, a preferred range of the coupler residue represented by the general formula (X) will be described. R₁₂Is a cyano group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, cycloalkylsulfonyl group, arylsulfonyl group, heterocyclic group, acyl group, sulfamoyl group, phosphonyl group, Phynoylamino group, imide group or perfluoroalkyl group is preferable, cyano group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, carbamoyl group, alkylsulfonyl group, cycloalkylsulfonyl group, arylsulfonyl group, sulfamoyl group, phosphonyl. And a perfluoroalkyl group are more preferable. Most preferably, a cyano group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an arylsulfonyl group, and a perfluoroalkyl group are exemplified.
[0072]
R₁₃Is a cyano group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, cycloalkylsulfonyl group, arylsulfonyl group, heterocyclic group, acyl group, sulfamoyl group, phosphonyl group, A finoylamino group, an imide group or a perfluoroalkyl group is preferred, and a cyano group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an arylsulfonyl group. , Sulfamoyl group, phosphonyl group, and perfluoroalkyl group are more preferable, and cyano group, cycloalkyloxycarbonyl group, alkylsulfonyl group, cycloalkyl group are most preferable. A sulfonyl group, an arylsulfonyl group, a sulfamoyl group, and a phosphonyl group.
[0073]
M₂Is preferably a nonmetallic atom group necessary for forming a 5-membered or 6-membered ring together with a pyrrole ring, more preferably a 5-membered ring, and an atomic group required for forming a 1,2,4-triazole ring. Is most preferred.
[0074]
The coupler residues represented by the general formula (VIII) and the general formula (X) are preferable, the coupler residue of the general formula (VIII) is preferable in terms of fastness, and the coupler residue represented by the general formula (X) in terms of hue. The coupler residue is preferred.
[0075]
Specific examples of the coupler residues represented by general formula (VII) to general formula (X) are shown below, but the present invention is not limited thereto.
[0076]
[Chemical formula 5]

[0077]
[Chemical 6]

[0078]
[Chemical 7]

[0079]
[Chemical 8]

[0080]
[Chemical 9]

[0081]
The TIME group will be described in detail.
The group represented by TIME may be any timing group that can cleave the group bonded to the right side after the bond on the left side of TIME in general formula (I) is cleaved during development processing. For example, groups utilizing the cleavage reaction of hemiacetal described in U.S. Pat. Nos. 4,146,396, 4,652,516 or 4,698,297, U.S. Pat. No. 4,248,962 No. 4,847,185, 4,857,440 or 5,262,291, a timing group for causing a cleavage reaction using an intramolecular nucleophilic substitution reaction, US Pat. Timing group for causing cleavage reaction using the electron transfer reaction described in US Pat. No. 4,409,323 or US Pat. No. 4,421,845, hydrolysis of iminoketal described in US Pat. No. 4,546,073 A group that causes a cleavage reaction using a reaction, a group that causes a cleavage reaction using a hydrolysis reaction of an ester described in British Patent No. 1,531,927, or published in Europe Utilizing the reaction of the sulfite ions according to Patent or Nos 0684512 No. 0572084 includes a group causing a cleavage reaction by.
[0082]
In the general formula (I), when n is 2 or more, the plurality of TIMEs are the same or different. Preferable TIME includes the following general formula (T-1), (T-2) or (T-3).
[0083]
Formula (T-1) * -W- (Y₁= Y₂)_j-C (R₇₁) (R₇₂)-**
General formula (T-2) * -W-CO-**
General formula (T-3) * -W-LINK-E-**
[0084]
In these formulas, * represents the position bonded to the left group of TIME in the general formula (I), ** represents the position bonded to the right group of TIME in the general formula (I), and W represents an oxygen atom. , Sulfur atom or> N-R₇₃Y₁And Y₂Each represents a substituted or unsubstituted methine or nitrogen atom, j represents 0, 1 or 2;₇₁And R₇₂Is R₄₁Represents a group having the same meaning as R₇₃Is R₄₃Represents a group having the same meaning as Y₁And Y₂When represents a substituted methine, the substituent is R₄₀Represents a group having the same meaning as Where Y₁And Y₂When represents a substituted methine, the substituent, R₇₁, R₇₂And R₇₃Any two substituents may be linked to each other to form a cyclic structure (for example, a benzene ring or a pyrazole ring). In the general formula (T-3), E represents an electrophilic group, and LINK represents a linking group that is sterically related so that W and E can undergo an intramolecular nucleophilic substitution reaction. Q of the compound represented by the general formula (I)₁When the part flows out after forming the dye, n represents 1, 2, or 3, and at least one of them preferably has a diffusion-resistant group having 10 to 50 carbon atoms in the TIME group.
Specific examples of TIME represented by the general formula (T-1) include the following.
[0085]
[Chemical Formula 10]

[0086]
Specific examples of TIME represented by the general formula (T-2) include the following.
[0087]
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[0088]
Specific examples of TIME represented by the general formula (T-3) include the following.
[0089]
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[0090]
When n is 2 or more in general formula (I) (TIME)_nSpecific examples of these and examples of other timing groups include the following.
[0091]
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[0092]
n is preferably 0, 1 or 2, more preferably 0 or 1.
[0093]
Next, L of the colored coupler represented by the general formula (X)₁And m will be described.
L₁Represents a divalent linking group. For example, an alkylene group, a cycloalkylene group, an aralkylene group, an alkenylene group, an arylene group, -O-, -S-, -N (R₁₄)-, -CO-, -COO-, -CON (R₁₅)-, -SO-, -SO₂-, -SO₂N (R₁₄)-, -N (R₁₄) CON (R₁₅)-, -N (R₁₄) SO₂N (R₁₅)-, -CON (R₁₄) CO-, -CON (R₁₅) SO₂-, -N (R₁₄) COO-. R₁₄And R₁₅Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group;₄₀It is a group having the same meaning as the hydrogen atom, alkyl group, cycloalkyl group, aryl group, and heterocyclic group described in 1. One of the above free bonds is Q₁A group or a TIME group is bonded, and the other is bonded to a YDYE group. m represents 0, 1, 2, or 3; When m is plural, they may be the same linking group or different. Preferably 0 or 1.
[0094]
Next, the yellow dye residue represented by (YDYE) will be described.
(YDYE) represents a yellow dye residue. A yellow dye residue obtained by coupling a yellow coupler used in a silver halide photographic light-sensitive material and an oxidized form of a developing agent (for example, a yellow dye-forming coupler is a dye). Valoyl acetanilide type, benzoyl acetanilide type, malon diester type, malon diamide type, dibenzoyl methane type, benzothiazolylacetamide type, malon ester monoamide type, benzoxazolylacetamide type, benzoimidazolyl acetamide type, benzothiazolylacetamide Type, cycloalkanoylacetamide type, indoline-2-ylacetamide type, quinazolin-4-one-2-ylacetamide type described in US Pat. No. 5,021,332, described in US Pat. No. 5,021,330 Ben 1,2,4-thiadiazine-1,1-dioxide-3-ylacetamide type, couplers described in European Patent No. 421221A, couplers described in US Pat. No. 5,455,149, and European Published Patent No. 0622673 And the couplers described in the issue.
[0095]
Further, developing agents are known in the photographic industry, and specific examples of developing agents are described in T.H. James “The Theory of the Photographic Process”, 4th edition, pages 291-334 and 353-361. A particularly preferred developing agent is a p-phenylenediamine derivative), a yellow dye described in Dye Handbook 1986 (Kodansha), a yellow dye, an azine dye, an azo dye described in Chemical Handbook Application Edition 3980 (Maruzen) Residues such as azo dyes, azomethine dyes, quinophthalone dyes, nitro dyes, naphthol dyes, dioxazine dyes, quinoneimine dyes, and quinone dyes.
[0096]
YDYE is a yellow dye residue, an azo dye residue obtained by coupling an alkanoylacetamide type, a cycloalkanoylacetamide type, a benzoylacetamide type, or an indoline-2-ylacetamide type and an oxidized form of a p-phenylenediamine derivative, Azomethine dye residues, azine dyes, quinophthalone dye residues, and quinone dye residues are preferred, and alkanoyl acetamide type, cycloalkanoyl acetamide type, benzoylacetamide type, or indoline-2-ylacetamide type and p-phenylenediamine More preferred are yellow dye residues, azo dyes, azine dyes, and quinophthalone dyes obtained by coupling derivatives with oxidants.
[0097]
Next, the yellow colored cyan coloring coupler represented by the general formula (II) will be described.
A in general formula (II)₁Is Q in the general formula (I)₁Represents a group having the same meaning as the cyan coupler residue described in the above, and R₁Represents an aryl group or a heterocyclic group, and the aryl group and the heterocyclic group may have a substituent, and the substituent is the above-mentioned R₄₀It is a group having the same meaning as the group described in 1. R₁Is preferably an aryl group.
[0098]
Next, the magenta colored cyan coloring coupler represented by the general formula (III) will be described.
Q₂Is Q in the general formula (I)₁Represents a group having the same meaning as the cyan coupler residue described above, and a preferred range thereof is the same as that of the general formula (I).
The TIME groups, n and m are as described in the general formula (I).
L₂Is L in the general formula (I)₁Represents a group having the same meaning as the group described above.
[0099]
(MDYE) represents a magenta dye residue that can flow out into the processing solution, and is a magenta dye residue obtained by coupling a magenta coupler used in a silver halide photographic light-sensitive material and an oxidized form of a developing agent. For example, magenta dye-forming couplers include 5-pyrazolone type, 1H-pyrazolo [1,5-a] benzimidazole type, 1H-pyrazolo [5,1-c] [1,2,4] triazole type, 1H- Pyrazolo [1,5-b] [1,2,4] triazole type, 1H-imidazo [1,2-b] pyrazole type, cyanoacetophenone type, active propene type described in WO93 / 01523, WO93 / 07534 The enamine type 1H-imidazo [1,2-b] [1,2,4] triazole type coupler residues described and the coupler residues described in US Pat. No. 4,871,652 The developing agent is, for example, known in the photographic industry. Specific examples of the developing agent are THJames “The Theory of the Photographic Process” 4th edition, pages 291 to 334 and 3 Pp. 3-361. Particularly preferred developing agents are p-phenylenediamine derivatives). Further, (MDYE) is a magenta dye residue described in Dye Handbook 1986 (Kodansha), a magenta dye residue described in Chemical Handbook Application Edition 3rd Edition 1980 (Maruzen), for example, an azine dye, an azo dye, Examples include residues of azomethine dyes.
[0100]
Next, the magenta colored cyan coloring coupler represented by the general formula (IV) will be described.
A₂Is Q in the general formula (I)₁Represents a group having the same meaning as the cyan coupler residue described in the above, and the preferred range thereof is also the same as described in the general formula (I). R2 represents an aryl group or a heterocyclic group, and the aryl group and the heterocyclic group may have a substituent, and the substituent is the above-described R₄₀It is a group having the same meaning as the group described in 1.
[0101]
Next, the yellow colored magenta coloring coupler represented by the general formula (V) will be described.
TIME, n, m, and (YDYE) represent a group having the same meaning as that described in the general formula (I). L_ThreeIs L described in the general formula (I).₁Represents a group having the same meaning as
[0102]
Q_ThreeRepresents a magenta coupler residue, for example, 5-pyrazolone type, 1H-pyrazolo [1,5-a] benzimidazole type, 1H-pyrazolo [5,1-c] [1,2,4] triazole type, 1H -Pyrazolo [1,5-b] [1,2,4] triazole type, 1H-imidazo [1,2, b] pyrazole type, cyanoacetophenone type, active propene type described in WO93 / 01523, WO93 / 07534 Enamine type, 1H-imidazo [1,2-b] [1,2,4] triazole type described in US Pat. No. 4,871,652 and the residue of the coupler described in US Pat. No. 4,871,652.
[0103]
Q_ThreeIs preferably represented by the following general formula (XI).
[0104]
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[0105]
In formula (XI), R₁₆Represents a hydrogen atom or a substituent, and Z₁And Z₂Are independently -N = or -C (R₁₇) =. * (TIME)_n-(L)_m-Represents the bonding position with YDYE.
R₁₆Is R₄₀Represents a group having the same meaning as R₁₇Is R₄₁Represents a group having the same meaning as
[0106]
R₁₆As, alkyl group, cycloalkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, cycloalkyloxy group, aryloxy group, heterocyclic oxy group, cyano group, silyl group, silyloxy group, acyloxy group, alkoxy Carbonyloxy, cycloalkyloxycarbonyloxy, aryloxycarbonyloxy, carbamoyloxy, sulfamoyloxy, alkanesulfonyloxy, arenesulfonyloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, cyclo Alkyloxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, cycloalkyloxycarbonylamino Group, aryloxycarbonylamino group, sulfonamido group, sulfamoylamino group, azo group, carboxyl group, alkylthio group, cycloalkylthio group, arylthio group, heterocyclic thio group, alkylsulfinyl group, arenesulfinyl group, alkanesulfonyl group An arenesulfonyl group, an alkoxysulfonyl group, a cycloalkyloxysulfonyl group, an aryloxysulfonyl group, a sulfamoyl group, a sulfo group, a phosphonyl group, and a phosphinoylamino group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, Heterocyclic group, alkoxy group, cycloalkyloxy group, aryloxy group, heterocyclic oxy group, alkoxycarbonyl group, aryloxycarbonyl group, cycloalkyloxycarbonyl group, carbamo Group, an amino group, an anilino group, a carbonamido group, a ureido group, an alkoxycarbonylamino group, a cycloalkyloxy group, an aryloxycarbonylamino group, a sulfonamide group is more preferable. Most preferably, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an anilino group and the like can be mentioned.
[0107]
Q below_ThreeSpecific examples of the magenta coupler residue represented by formula (I) are shown below, but the present invention is not limited thereto.
[0108]
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[0109]
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[0110]
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[0111]
Next, the yellow colored magenta coloring coupler represented by the general formula (VI) will be described.
A_ThreeIs Q in the general formula (V)_ThreeIt represents a group having the same meaning as the magenta coupler residue described in 1. , R_ThreeRepresents an aryl group or a heterocyclic group, and these groups may have a substituent, and the substituent is R₄₀Represents the substituent described in the above.
[0112]
Although the specific example of the colored coupler of this invention represented by the following general formula (I)-general formula (VI) is shown, this invention is not limited to these.
Specific examples of the coupler represented by the general formula (I) are shown below.
[0113]
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[0114]
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[0115]
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[0116]
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[0117]
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[0118]
Specific examples of the coupler represented by the general formula (II) are shown below.
[0119]
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[0120]
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[0121]
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[0122]
Specific examples of the coupler represented by the general formula (III) are shown below.
[0123]
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[0124]
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[0125]
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[0126]
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[0127]
Specific examples of the coupler represented by the general formula (IV) are shown below.
[0128]
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[0129]
Specific examples of the coupler represented by the general formula (V) are shown below.
[0130]
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[0131]
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[0132]
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[0133]
Specific examples of the coupler represented by the general formula (VI) are shown below.
[0134]
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[0135]
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[0136]
Next, a general method for synthesizing these couplers will be described.
Various methods for synthesizing the coupler residue represented by the general formula (VII) are known in the field of silver halide light-sensitive materials. For example, it can be easily synthesized according to the method described in JP-B-59-45142 and JP-A-60-37459.
The coupler residue represented by the general formula (VIII) can be synthesized according to the methods described in, for example, Japanese Patent Publication No. 4-73433 and US Pat. No. 4,327,173. The synthesis of the coupler residue represented by the general formula (IX) can be performed, for example, according to the method described in European Patent Publication 161626.
The synthesis of the coupler residue represented by the general formula (X) can be performed, for example, according to the method described in EP0714892.
The coupler residue represented by the general formula (XI) can be synthesized according to the methods described in JP-B-4-79350, JP-A-2-59584, and No. 3-220292.
[0137]
Synthesis of the dye-releasing coupler of the present invention having a TIME group represented by general formula (I), general formula (III) and general formula (V) is disclosed in U.S. Pat. Nos. 4,248,962 and 4,857, No. 440, No. 5,021,322, No. 5,256,523, European Patent Nos. 0299726, No. 0348139, No. 0354532, No. 0438150, No. 0499279, European Patent Nos. 0514896, No. 0594256 No. 0523423, No. 0520496, No. 0576052, No. 0576087, No. 057660, No. 0576089, No. 0576182, No. 63-39889, No. 63-61656, No. 5-18095, JP-A-7-133259, JP-A-6-130594, etc. It can be synthesized by a method similar to the method.
[0138]
The synthesis of colored couplers represented by general formula (II), general formula (IV) and general formula (VI) is carried out by using aromatic amines or heterocyclic amines as well as diazos such as nitrites, nitrites or nitrosylsulfuric acid. After synthesizing an aromatic diazonium salt or heterocyclic diazonium salt by acting an agent, it can be easily synthesized by performing a coupling reaction with a coupler synthesized according to the above-mentioned literature.
[0139]
Silver halide grains that can be used in the light-sensitive material of the present invention are silver chloride, silver iodochloride, silver chlorobromide, and silver iodochlorobromide. Preferably, the silver chloride content is 50 mol% or more. More preferably, the silver chloride content is 80 mol% or more. The silver iodide content is preferably 2 mol% or less, more preferably 1 mol% or less. More preferably, it is 0.5 mol% or less.
[0140]
The silver halide emulsion used in the present invention may be a surface latent image type or an internal latent image type. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging agent. Further, the crystal structure may be uniform, or it may be a multi-structure particle having a different halogen composition between the inside of the grain and the grain surface. Further, silver halides having different compositions may be bonded by epitaxial bonding, and further, for example, may be bonded to a compound other than silver halide such as rhodium silver or lead oxide.
[0141]
In particular, in the high silver chloride emulsion used in the present invention, a structure having a silver bromide localized phase in a layered or non-layered manner inside and / or on the surface of silver halide can be used. The halogen composition of the localized phase is preferably a silver bromide content of at least 20 mol%, more preferably more than 30 mol%. The silver bromine content of the silver bromide localized phase is analyzed by X-ray analysis or the like. For example, X-ray analysis methods are described in Photographic Science and Technology, Vol. 2, pages 149 (1955) and Vol. 4, pages 22 (1957), by CR Berry, SJMarino. A method of application to the silver halide grain position is described. The silver bromide localized phase can be inside the grain, at the edge, corner or face of the grain surface. Preferable examples include those epitaxially bonded to the grain corners.
[0142]
The average grain size of the silver halide grains used in the present invention is preferably 0.05 to 0.9 μm in order to obtain a high development activity with a low silver amount and a large specific surface area. Is preferably 0.05 to 0.9 μm, particularly preferably 0.1 to 0.5 μm. Monodispersed emulsions having a narrow grain size distribution may be used. The monodispersed emulsion is, for example, a silver halide emulsion having a grain size distribution in which 80% or more of all grains fall within ± 30% of the average grain size in terms of the number of grains or weight. Further, it may be a monodispersed silver halide emulsion having a variation coefficient of 20% or less, particularly 15% or less. A polydisperse emulsion having a wide grain size may be used.
[0143]
Examples of silver halide emulsions that can be used in the present invention include Research Disclosure (RD), Vol. 176, No. 17643 (December, 1978), pages 22 to 23, “I. Emulsion Preparation and Types”. And No. 18716 (November 1979), page 648, “Photograph, Physics and Chemistry” by Grafkide, published by Paul Montel (P. Glafkides, Chemic et Phisique Phtographique, (Paul Montel, 1967)) Photographic Emulsion Chemistry, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry, (Focal Press, 1966)), "Production and Coating of Photoemulsions" by Zerikman, published by Focal Press (VLZelikman et al, Making and Coating Photographic Emulsion, (Focal Press, 1964)) and the like.
[0144]
Monodispersed emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described by Gaft, Photographic Science and Engineering, Vol. 14, pages 248-257 (1970), U.S. Pat. Nos. 4,434,226 and 4,414. No. 310, No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157 can be used for easy adjustment. Further, a mixture of particles having various crystal forms may be used.
[0145]
The photosensitive halogen or silver emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a known chalcogen sensitizing method such as sulfur sensitization, selenium sensitization, tellurium sensitization, etc., gold, platinum, palladium, etc., for emulsions for ordinary photosensitive materials The noble metal sensitizing method and reduction sensitizing method used may be used alone or in combination (for example, JP-A-3-110555, JP-A-5-241267, etc.). Such chemical sensitization can also be performed in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-Open No. 62-253159). Further, an antifoggant described later can be added after completion of chemical sensitization. Specifically, the methods described in JP-A-5-45833 and JP-A-62-240446 can be used.
[0146]
The pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0 to 10.5, preferably 6.8 to 9 .0.
The coating amount of the photosensitive silver halide emulsion used in the present invention is 1 mg to 10 mg / m2 in terms of silver.²It is.
[0147]
In order to give the photosensitive silver halide used in the present invention green sensitivity, red sensitivity, and infrared sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with methine dyes and the like. If necessary, the blue-sensitive emulsion may be spectrally sensitized.
Examples of the dye used include a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, and a hemioxonol dye.
Specific examples include sensitizing dyes described in U.S. Pat. No. 4,617,257, JP-A-59-180550, JP-A-64-13546, JP-A-5-45828, and 5-45834. It is done.
These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used for the purpose of supersensitization or wavelength adjustment of spectral sensitivity.
[0148]
In addition to the sensitizing dye, a dye which itself does not have spectral sensitizing action or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3, 615, 641, JP-A 63-23145, etc.).
These sensitizing dyes may be added to the emulsion during or after chemical ripening, or before or after the formation of silver halide grains according to US Pat. Nos. 4,183,756 and 4,225,665. Good. These sensitizing dyes and supersensitizers may be added in a solution of an organic solvent such as methanol, a dispersion such as gelatin, or a surfactant solution. The amount added is generally 10 per mole of silver halide.^-810^-2It is about a mole.
[0149]
The additive used in such a process is the RDNo. 17643, ibid. 18716 and No. 1 307105, and the corresponding parts are summarized in the following table.
[0150]

[0151]
The color developer that can be used in the present invention is not particularly limited as long as an oxidized form of the developer produced by developing the silver halide forms a dye by a coupling reaction with a coupler to form a dye. It is. Specific examples of the color developer are described in T.H. James “The Theory of the Photographic Process”, 4th edition, pages 291 to 334 and pages 353 to 361. Particularly preferred color developers are p-phenylenediamine derivatives.
[0152]
In the present invention, various known couplers can be used in combination with the coupler of the present invention. Examples of yellow couplers that can be used in combination with the present invention include pivaloyl acetanilide type, benzoyl acetanilide type, malon diester type, malon diamide type, dibenzoylmethane type, enzothiazolylacetamide type, malon ester monoamide type, benzoxazolyl Benzoacetamide type, benzimidazolylacetamide type, benzothiazolylacetamide type, cycloalkanoylacetamide type, indoline-2-ylacetamide type, benzo-1,2,4-thiadiazine described in US Pat. No. 5,021,332 1,1-dioxide-3-ylacetamide type, coupler described in European Patent No. 421221A, coupler described in US Pat. No. 5,455,149, and coupler described in European Patent Publication No. 0622673 And the like.
[0153]
Examples of magenta couplers that can be used in combination with the present invention include 5-pyrazolone type, 1H-pyrazolo [1,5-a] benzimidazole type, 1H-pyrazolo [5,1-c] [1,2,4] triazole type. 1H-pyrazolo [1,5-b] [1,2,4] triazole type, 1H-imidazo [1,2-b] pyrazole type, cyanoacetophenone type, active propene type described in WO 93/01523, Examples include enamine type described in WO93 / 07534, 1H-imidazo [1,2-b] [1,2,4] triazole type, and couplers described in US Pat. No. 4,871,652.
[0154]
Examples of cyan couplers that can be used in combination with the present invention include phenol type, naphthol type, 2,5-diphenylimidazole type, 1H-pyrrolo [1,2, -b] [1, 2,4] triazole type, 1H-pyrrolo [2,1-c] [1,2,4] triazole type, pyrrole type described in JP-A-4-188137 and 4-1903347, JP-A-1- No. 315736, 3-hydroxypyridine type, U.S. Pat. No. 5,164,289, pyrrolopyrazole type, JP-A-4-174429, pyrroloimidazole type, U.S. Pat. No. 4,950, No. 585, pyrazolopyrimidine type described in JP-A-4-204730, pyrrolotriazine type, US Pat. No. 4,746,60 Couplers described in JP, couplers described in Nos. 5,104,783, and European have been couplers described in Japanese Patent No. 0556700 can be cited.
[0155]
Further, couplers which do not substantially leave color may be used in combination, for example, indanone type, acetophenone type, European Patent Nos. 4435530A and 444501A, JP-A Nos. 6-138612, 6-82955 and 6- And couplers described in JP-A-82996 and JP-A-6-82998.
[0156]
The yellow couplers, magenta couplers, cyan couplers and couplers that do not substantially leave the color described above have transmission densities of red, blue, and green hues reproduced by mixing yellow, magenta, and cyan. Effectively used to adjust.
[0157]
In addition to the couplers described above, the following various couplers can be used in the present invention. For example, polymerized dye-forming couplers are described in U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and British Patent 2,102,137. ing.
Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the aforementioned RD17643, patents described in paragraphs VII to F, JP-A-57-151944, 57-154234, 60-184248, U.S. Pat. No. 4,248. , 962 are preferred.
As couplers for releasing a nucleating agent or a development accelerator in an image state during development, British Patent Nos. 2,097,140, 2,131,188, JP-A-59-157638, and 59-170840 are disclosed. The couplers described in 1 are preferred.
[0158]
Other couplers that can be used in the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. Nos. 4,283,472, 4,338,393, 4, Examples include a multi-equivalent coupler described in 310,618 and a DIR redox compound releasing coupler described in JP-A-60-185950.
[0159]
Further, the coupler for black correction does not have to be colored in yellow, magenta, cyan, but may be colored in orange, brown, purple, black, or the like.
In the present invention, the equivalent ratio of silver halide to coupler in each silver halide emulsion layer is 0.5 or more and 100 or less, preferably 1 or more and 10 or less, more preferably 1 or more and 3 or less. In particular, when a silver halide emulsion having an average grain size (specified by thickness in the case of tabular grains) is 0.9 μm or less, particularly 0.5 μm or less, it is more preferably 1 or more and 2 or less. The equivalent ratio mentioned here means that the theoretical amount of silver halide necessary for coloring all the couplers is equivalent ratio 1, and for example, when applying a silver halide twice the theoretical amount, the equivalent ratio is 2. That is, when a 2-equivalent coupler is used, the equivalent ratio is 1 when the amount of coated silver is 2 moles per mole of coupler, and the equivalent ratio is 2 when the amount of coated silver is 4 moles.
[0160]
The coupler used in combination with the present invention can be introduced into the photosensitive material by various known dispersion methods.
Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The amount of the high boiling point solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, relative to 1 g of the coupler. H, 2 g or less, preferably 1 g or less, more preferably o. 5 g or less. The size of the coupler dispersion (coupler emulsion) obtained by the oil-in-water dispersion method is 0.05 μm to 0.9 μm, preferably 0.1 μm to 0.5 μm.
[0161]
Specific examples of texes such as the steps, effects, and impregnation of latex dispersion method include US Pat. No. 4,199,363, West German Patent Applications (OLS) Nos. 2,541,274 and 2,541,230, etc. It is described in.
In the light-sensitive material according to the present invention, it is preferred to use a color image preservability improving compound as described in European Patent EP 0,277,589 in the layer containing a coupler. In particular, the combined use with a pyrazoloazole-based magenta coupler is preferable.
[0162]
That is, the compound (F) which reacts with the aromatic developing agent remaining after color development to produce a chemically inert and substantially colorless compound and / or the aromatic development remaining after color development processing In order to prevent the occurrence of stains and other side effects, it is possible to use the compound (G) which reacts with the oxidation pair of the active ingredient to produce a chemically inactive and substantially colorless compound at the same time or alone. preferable.
[0163]
The silver halide emulsion layer and the intermediate layer of the light-sensitive material according to the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant or antifading agent. Among these compounds, those which do not easily generate stain even when heated to 160 ° C. to 200 ° C. are preferable.
[0164]
In order to prevent deterioration of the cyan dye image due to heat and particularly light, it is effective to introduce an ultraviolet absorber into the cyan color developing layer and the layers on both sides adjacent thereto.
Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, compounds described in US Pat. Nos. 3,533,794 and 3,352,681), benzophenone compounds (for example, JP 46-2784), cinnamate compounds (for example, compounds described in US Pat. Nos. 3,705,805 and 3,707,395), butadiene-based compounds (for example, US Pat. 4,045,229) or benzoxazole compounds (for example, compounds described in US Pat. Nos. 3,406,070 and 4,271,307) can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan image forming coupler) or an ultraviolet-absorbing polymer may be used. These ultraviolet absorbers may be mordanted in a specific layer. Of these, benzotriazole-based compounds substituted with the aryl group are preferred.
[0165]
In addition, the light-sensitive material according to the present invention has an antibacterial and antifungal agent as described in JP-A-63-271247 in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and degrade the image. Is preferably added.
[0166]
As the binder or protective colloid that can be used in the silver halide emulsion layer, intermediate layer and protective layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic polymers can also be used. . Examples of the hydrophilic polymer include polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl butyral, poly-N-vinyl pyrrolidone, polyacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, carrageenan, gum arabic, hydroxyalkyl cellulose, carboxy Examples include cellulose-derived mono- or copolymers such as methyl cellulose, cellulose sulfate, cellulose acetate hydrogen phthalate and sodium alginate.
[0167]
Gelatin and other polymer graft polymers may also be used. As the gelatin-graft polymer, gelatin is a single or co-polymer of acrylic monomers, methacrylic acids, derivatives thereof such as esters and amides, and vinyl monomers such as acrylonitrile and styrene. A grafted polymer can be used. In particular, a polymer having a certain degree of compatibility with gelatin, for example, a graft polymer with a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, and hydroxyalkyl methacrylate is preferable. Examples of these are described in U.S. Pat. Nos. 2,763,625, 2,831,767, 2,956,884, and JP-A-56-65133.
Typical synthetic hydrophilic polymer materials include, for example, West German Patent Application (OLS) 2,312,708, U.S. Pat. Nos. 3,620,751, 3,879,205, Japanese Patent Publication No. 43-7561. Those described in (1) can also be used.
Said hydrophilic polymer may be used independently and may use 2 or more types together.
[0168]
As gelatin, those subjected to any of alkali treatment, acid treatment and enzyme treatment, or a mixture thereof may be used. Also obtained by reacting gelatin with various compounds such as plate halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultone, vinylsulfonamides, maleimides, polyalkylene oxides, epoxy compounds and the like. Gelatin derivatives are also used. Specific examples of the gelatin derivatives are US Pat. Nos. 2,614,928, 3,132,945, 3,186,846, 3,312,553, British Patent 861,414, Nos. 1,033,189, 1,005,784, and Japanese Patent Publication No. 42-26845.
[0169]
The total binder amount in the light-sensitive material used in the present invention is 3 to 10 g / m.²The binder content of each silver halide emulsion layer or intermediate layer is preferably 0.1 to 1.5 g / m per layer.²Is preferable, and 0.2 to 1.0 g is particularly preferable.
[0170]
The support used in the present invention is preferably a light-transmitting substrate. However, as described in JP-A-7-244212, a silver halide emulsion layer coated on another support is formed on the light-transmitting substrate. A color filter photosensitive material may be formed by transfer adhesion. In this case, the support does not necessarily need to be light-transmitting, and for example, a back surface of the support coated with carbon black or the like may be used.
Note that the amount of binder in the release layer and the back layer provided in this case is not included in the above “total amount of binder”.
[0171]
Examples of the material constituting the light-transmitting substrate are desirably optically isotropic and excellent in heat resistance, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone. , Cellulose acetate, polyarylate, soda glass, borosilicate glass, quartz and the like.
[0172]
The surface of the substrate composed of these materials may be undercoated as necessary. Furthermore, you may perform processes, such as a Glow discharge, a corona discharge, and ultraviolet irradiation.
In addition, the transparent substrate can be used in the form of a plate, a sheet, or a film. Although the thickness of a board | substrate can be set suitably by a use and a material, generally it is 0.01-10 mm. For example, in the case of a glass substrate, the thickness is in the range of 0.3 to 3 mm.
[0173]
The photosensitive material used in the present invention is the RD. No. 17643, pages 28-29, and A micro color filter is obtained by color development by a conventional method described in the left column to the right column of 651 of No. 18716.
For example, a color developing process, a desilvering process, and a washing process are performed. In the desilvering process, instead of the bleaching process using the bleaching solution and the fixing process using the fixing solution, a bleach-fixing processing step using the bleach-fixing solution can be performed, the bleaching process step, the fixing process step, The bleach-fixing process steps may be combined in any order. A stabilization process may be performed instead of the water washing treatment process, or a stabilization process may be performed after the water washing treatment process. Further, a monobasic processing step using a one-bath development bleach-fixing processing solution in which color development, bleaching and fixing are performed in one bath can also be performed. In combination with these treatment steps, a pre-curing treatment step, a neutralization step, a stop fixing treatment step, a post-curing treatment step, an adjustment step, a reinforcing step, and the like may be performed. In these processes, a so-called activator process may be performed instead of the color development process. Examples of the hardening agent used in the post-curing treatment step include methods known in the photographic industry such as aldehydes, vinyl sulfones, carbodiimides, aluminum alum, and chrome alum. Preferably, glutaraldehyde (or / and) alum or formalin (or / and) alum is used.
Further, as described in JP-A-7-159610, an internal latent image type auto positive emulsion may be used for color development processing and desilvering processing in combination with a nucleating agent or optical fogging.
[0174]
As the development processing apparatus, a development processing machine used for normal photographic processing can be used. In the case of a hard support such as a glass substrate, a development processor for a glass dry plate or a development processing apparatus as described in JP-A-7-56015 can be used.
[0175]
As an exposure method applied to the present invention, there are a surface exposure method through a mask and a scanning exposure method. As the scanning method, a point scanning method such as line (slit) scanning or laser exposure can be applied.
As the light source, a tungsten lamp, a halogen lamp, a fluorescent lamp, a mercury lamp, a laser beam, and a light emitting diode lamp are used. In particular, a halogen lamp and a fluorescent lamp (three-wavelength fluorescent lamp) laser light are preferable.
As another exposure method applicable to the present invention, a liquid crystal display panel to be incorporated with a color filter produced according to the present invention as described in JP-A-8-201616 is used, and sequentially exposed three times in combination with the color filter. There is also a method.
[0176]
In the color filter manufactured by the method of the present invention, a resin having heat resistance, water resistance, light resistance, gas barrier properties, and high specific electrical resistivity can be coated on the outermost layer as a protective layer (overcoat layer). it can. Examples of such resins are U.S. Pat. Nos. 4,698,295, 4,668,601, European Patent Applications EP-179,636A, 556,810A, JP-A-3-163416, and 3-188153. No. 5-78443, No. 1-276101, JP-A-60-216307, No. 63-218771 and the like.
[0177]
The color filter produced according to the present invention can be further provided with a transparent electrode by vapor deposition coating, for example, vacuum deposition or sputtering. Further, an alignment film such as a polyimide resin can be provided thereon. Further, a polarizing plate or a retardation film may be provided on the surface of the color filter opposite to the emulsion surface of the light-transmitting substrate.
[0178]
A color liquid crystal display (LCD) using the color filter of the present invention will be described.
FIG. 11 shows an example of a schematic sectional view of a liquid crystal display. Although the surface of the color filter 2 produced by the present Example on the glass substrate 1 is not shown in figure, it is coat | covered with the said resin and the protective layer is formed. A transparent electrode (for example, ITO electrode) 3 is attached on the protective layer using a vacuum film forming apparatus. The transparent electrode 3 is formed as an all-in-one electrode in an active matrix drive LCD using a three-terminal switching array such as a TFT, and is usually used as a stripe electrode in an active matrix drive LCD using a two-terminal switching array such as a simple matrix drive LCD or MIM. It is formed. An alignment film 4 such as polyimide is disposed on the transparent electrode 3 to align liquid crystal molecules.
[0179]
On the other hand, the transparent electrode (for example, ITO) 8 and the alignment film 4 are disposed on the glass substrate 7 on the opposite side with the liquid crystal layer 5, the spacer (not shown) and the sealing material 6 interposed therebetween. The transparent electrode 8 is a pixel electrode connected by a TFT element in an active matrix drive LCD using a three-terminal switching array such as a TFT, and is a stripe electrode in a simple matrix drive LCD such as an STN and is orthogonal to the transparent electrode 3. Are arranged.
[0180]
A black matrix 9 is usually formed between the R, G, and B pixels to improve contrast and color purity. The black matrix 9 can be formed simultaneously with the R, G, and B pixels as in the present invention, or a chromium film, a carbon film, or the like can be separately formed. In addition, polarizing plates 10 and 11 are provided on the back surfaces of the glass substrates 1 and 7. A phase compensation film (not shown) can be installed between each glass substrate and the polarizing plate.
Since the light transmittance of the LCD using the color filter is small, the backlight 12 is installed as a light source consistent with the color reproducibility of the normal color filter.
[0181]
Instead of the glass substrate, a plastic film substrate provided with a gas barrier layer or a hard coat layer can be used as the light transmissive substrate.
For details on color LCDs and their manufacturing methods, see Shoichi Matsumoto and Ryoji Kakuda, “Fundamentals and Applications of Liquid Crystals” (published by the Industrial Research Council in 1991), Nikkei Microdevices “Flat Panel Display 1994” (1993 Nikkei) Published by BP), JP-A-1-114820, and the like.
[0182]
Preparation of Color Filters Known from the Red or Magenta Colored Couplers Represented by General Formulas (I) and (II) of the Present Invention, and Dyes Obtained from These Couplers and Oxidized Developers It can also be used in the method to make a color filter containing the coupler and dye.
[0183]
For example, (1) a natural polymer gelatin, casein, or a synthetic polymer PVA, PVP, acrylic or the like is applied on a substrate, exposed to ultraviolet rays using a photomask, developed, Next, a dyeing method of dyeing with a dye obtained by coupling with an oxidized form of the coupler and / or developing agent of the present invention, (2) obtained in advance by coupling with an oxidized form of the coupler and / or developing agent of the present invention. Apply a photoresist toned with a dye on a substrate, and apply a pigment dispersion method (photolitho method) that exposes and develops in the same manner as the dyeing method. (3) Etching ITO into a predetermined pattern by the photolitho method, Electrophoresis using this as an electrode, and electrodeposition in which a dye obtained by coupling with the coupler of the present invention and / or an oxidized form of a developing agent is formed on an electrode, In and (4) printing method can form a color filter.
[0184]
【Example】
Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.
[0185]
Example 1 and Comparative Examples 1-2
A method for preparing the photosensitive silver halide emulsion (I) will be described.
A gelatin aqueous solution having the composition shown in Table 1 which is well stirred is added to the solution (I) shown in Table 2 for 1 minute. (I) The liquid (II) was added in 40 seconds 20 seconds after the start of liquid addition, and then the liquids (III) and (IV) were added simultaneously over 4 minutes.
[0186]
[Table 1]

[0187]
[Table 2]

[0188]
Embedded image

[0189]
After washing with water and desalting (performed using a sedimentation material (a) at pH 4.0) by a conventional method, 22 g of decalcified gelatin was added and dispersed. After adjusting the pH to 6.0, 4 cc of a 10% aqueous solution of sodium chloride is added, and 70 mg of preservative (1) is added to obtain a silver chloride emulsion having a grain size of 0.15 μm. The yield of this emulsion was 630 g.
[0190]
Embedded image

[0191]
The method for preparing the silver halide emulsion (II) will be described.
A silver chloride content of 70 mol% was obtained in the same manner as the silver halide emulsion (I) except that the composition of the aqueous gelatin solution and the solutions (III) and (IV) were changed as shown in Tables 3 and 4. A silver chlorobromide emulsion was prepared. The particle size was 0.18 μm.
[0192]
[Table 3]

[0193]
[Table 4]

[0194]
(Comparative Example 1)
Gelatin subbing is applied to a polyethylene terephthalate support having a thickness of 100 μm coated with carbon black dispersed in polyvinyl chloride as a back layer, and the first to tenth layers having the following constitutions are simultaneously coated on the substrate. A comparative color photosensitive material 1A was prepared. Ingredients and application amount (g / m²Unit). In addition, about silver halide, the coating amount of silver conversion is shown.
[0195]

[0196]
Second layer (adjacent layer of gelatin)
Gelatin ・ ・ ・ 0.50
[0197]

[0198]
Fourth layer (intermediate layer)
Gelatin ・ ・ ・ 0.38
Color mixing inhibitor (Cpd-7) ... 0.09
Color mixing inhibitor (Cpd-10) ... 0.02
High boiling point solvent (Solv-1) 0.03
High boiling point solvent (Solv-3) 0.01
Ultraviolet absorber (Cpd-5) ... 0.02
Ultraviolet absorber (Cpd-4) ... 0.02
UV absorber (Cpd-3) 0.01
UV absorber (Cpd-6) 0.02
Polymer (Cpd-8) ... 0.04
[0199]

[0200]
6th layer (intermediate layer)
Gelatin ・ ・ ・ 0.38
Color mixing inhibitor (Cpd-7) ... 0.09
Color mixing inhibitor (Cpd-10) ... 0.02
High boiling point solvent (Solv-1) 0.03
High boiling point solvent (Solv-3) 0.01
Ultraviolet absorber (Cpd-5) ... 0.02
Ultraviolet absorber (Cpd-4) ... 0.02
UV absorber (Cpd-3) 0.01
UV absorber (Cpd-6) 0.02
Polymer (Cpd-8) ... 0.04
Yellow dye (YF-1) ... 0.17
[0201]

[0202]
8th layer (intermediate layer)
Gelatin ・ ・ ・ 0.38
Color mixing inhibitor (Cpd-7) ... 0.09
Color mixing inhibitor (Cpd-10) ... 0.02
High boiling point solvent (Solv-1) 0.03
High boiling point solvent (Solv-3) 0.01
Ultraviolet absorber (Cpd-5) ... 0.02
Ultraviolet absorber (Cpd-4) ... 0.02
UV absorber (Cpd-3) 0.01
UV absorber (Cpd-6) 0.02
Polymer (Cpd-8) ... 0.04
Irradiation preventing dye (Dye-1) 0.005
Irradiation preventing dye (Dye-2) ・ ・ ・ 0.02
[0203]

[0204]
10th layer (intermediate layer)
Gelatin ・ ・ ・ 0.70
Antihalation dye (fine particle dispersion) ... 0.15
Carboxymethylcellulose ... 0.05
Polymer (Cpd-12) ... 0.14
Surfactant (Cpd-13) ... 0.03
Hardener (H-1) ... 0.12
[0205]
In each layer, sodium dodecyl benzene sulfonate as an emulsifying dispersion aid, ethyl acetate as an auxiliary solvent, a surfactant (Cpd-14) as a coating aid, and potassium polystyrene sulfonate as a thickener were used.
[0206]
Embedded image

[0207]
Embedded image

[0208]
Embedded image

[0209]
Embedded image

[0210]
Embedded image

[0211]
Embedded image

[0212]
Example 1
Gelatin subbing is applied to a polyethylene terephthalate support having a thickness of 100 μm coated with carbon black dispersed in polyvinyl chloride as a back layer, and the first to ninth layers having the following constitutions are simultaneously coated thereon. A color photosensitive material 2A of the present invention was prepared. Ingredients and application amount (g / m²Unit). In addition, about silver halide, the coating amount of silver conversion is shown.
[0213]

[0214]
Second layer (adjacent layer of gelatin)
Gelatin ・ ・ ・ 0.50
[0215]

[0216]
Fourth layer (intermediate layer)
Gelatin ・ ・ ・ 0.38
Color mixing inhibitor (Cpd-7) 0.07
Color mixing inhibitor (Cpd-10) ... 0.02
High boiling point solvent (Solv-1) 0.03
High boiling point solvent (Solv-3) 0.01
Ultraviolet absorber (Cpd-5) ... 0.02
Ultraviolet absorber (Cpd-4) ... 0.02
UV absorber (Cpd-3) 0.01
UV absorber (Cpd-6) 0.02
Polymer (Cpd-8) ... 0.04
[0217]

[0218]
6th layer (intermediate layer)
Gelatin ・ ・ ・ 0.38
Color mixing inhibitor (Cpd-7) ... 0.09
Color mixing inhibitor (Cpd-10) ... 0.02
High boiling point solvent (Solv-1) 0.03
High boiling point solvent (Solv-3) 0.01
Ultraviolet absorber (Cpd-5) ... 0.02
Ultraviolet absorber (Cpd-4) ... 0.02
UV absorber (Cpd-3) 0.01
UV absorber (Cpd-6) 0.02
Polymer (Cpd-8) ... 0.04
[0219]

[0220]
8th layer (intermediate layer)
Gelatin ・ ・ ・ 0.34
High boiling point solvent (Solv-1) 0.03
High boiling point solvent (Solv-3) 0.01
Ultraviolet absorber (Cpd-5) ... 0.02
Ultraviolet absorber (Cpd-4) ... 0.02
UV absorber (Cpd-3) 0.01
UV absorber (Cpd-6) 0.02
Polymer (Cpd-8) ... 0.04
[0221]
9th layer (protective layer)
Gelatin ・ ・ ・ 0.70
Antihalation dye (fine particle dispersion) ... 0.15
Carboxymethylcellulose ... 0.05
Polymer (Cpd-12) ... 0.14
Surfactant (Cpd-13) ... 0.03
Hardener (H-1) ... 0.12
[0222]
Further, the photosensitive material 2B is the same as the photosensitive material 2A except that the exemplary coupler YC-6 in the third layer of the color photosensitive material 2A is replaced by equimolar amounts with the exemplary couplers YC-7, YC-9, and YC-13. ˜2D was made. A photosensitive material 2E was produced in the same manner as the photosensitive material 2C, except that the equimolar amount of MC-1 in the seventh layer of the photosensitive material 2C was replaced with MC-3. Photosensitive materials 2F to 2H were prepared in the same manner as the photosensitive material 2E, except that equimolar amounts of YC-9 in the third layer of the photosensitive material 2E were replaced with YC-13, YC-19, and YC-25, respectively. Photosensitive materials 2I to 2K were prepared in the same manner as the photosensitive material 2H, except that equimolar amounts of MC-7 in the seventh layer of the photosensitive material 2H were replaced with MC-6, MC-8, and MC-12, respectively.
[0223]
Except that the exemplified coupler YC-9 is replaced with 1/2 times mole of YC-6 and 1/4 times mole of cyan coupler ExC-1 with respect to YC-9 in the third layer of the photosensitive material 2E. Photosensitive material 2L was prepared in the same manner as photosensitive material 2E. Photosensitive material 2M was prepared in the same manner as photosensitive material 2L except that equimolar amount of YC-6 in the third layer of photosensitive material 2L was replaced with YC-9. Photosensitive material 2N was prepared in the same manner as photosensitive material 2E, except that YC-9 in the third layer of photosensitive material 2E was replaced with 1/2 mole of YC-18 with respect to YC-9. Photosensitive material 2O was produced in the same manner as photosensitive material 2E, except that YC-9 in the third layer of photosensitive material 2E was replaced by equimolar amount with YC-1, and further equimolar YC-24 was added. A photosensitive material 2O was prepared in the same manner as the photosensitive material 2E, except that YC-9 in the third layer of the photosensitive material 2E was replaced with an equivalent mole of YC-2, and an equivalent mole of YC-31 was further added.
[0224]
(Comparative Example 2)
Further, a comparative color photosensitive material 3A was prepared in the same manner as the photosensitive material 2A, except that equimolar substitution of YC-6 in the third layer of the color photosensitive material 2A with the comparative coupler A was performed. A photosensitive material 3B was prepared in the same manner as the photosensitive material 3A except that equimolar replacement of MC-1 in the seventh layer of the photosensitive material 3A with the comparative coupler B was performed.
[0225]
Embedded image

[0226]
On the other hand, transparent alkali glass (20 cm × 30 cm) having a thickness of 1.1 mm is used as a light-transmitting substrate, and gelatin and colloidal silica (average particle size: 7 to 9 μm) are mixed at a weight ratio of 1: 3 on the surface. Then, saponin was added as a surfactant and applied. The coating thickness of the dry film was 0.2 μm.
[0227]
The protective layers of the above-described various color photosensitive materials were adhered to the coated surface of the light transmitting substrate. Then, it was made to pass at a linear velocity of 0.45 m / min using a laminator whose temperature was set so that the temperature of the contact surface became 130 ° C. After cooling to about room temperature, the support of the photosensitive material was peeled off from the emulsion surface along with peeling. The upper emulsion surface from the second layer was uniformly adhered on the substrate, and no white spots were observed.
[0228]
The mask filter shown in FIG. 11 and the color filter matching the spectral sensitivity of the photosensitive material are superimposed on the substrate having the emulsion layer of the comparative sample 1A prepared as described above from the emulsion surface side, and successively four times using tungsten light. Exposed. Also, a B and G light exposure mask filter and a white light or IR light exposure mask filter shown in FIG. 4 are exposed to the substrate having the emulsions of Samples 2A to 2P of the present invention and Comparative Samples 3A and 3B from the emulsion surface side. The color filters matched to the spectral sensitivity of the material were layered and exposed sequentially three times using tungsten light. The exposed substrate was developed according to the following steps, and a color filter that developed three colors of B, G, and R and black in one operation was created.
[0229]
(Processing process) (Temperature) (Time)
Dura treatment 38 ° C 3 minutes
Washing -1 35 ℃ 1 minute
Color development 38 ° C 80 seconds
Bleach fixing 38 ° C 90 seconds
Rinsing-2 35 ℃ 40 seconds
Rinsing-3 35 ° C 40 seconds
Dry 60 ° C 2 minutes
[0230]
The composition of each processing solution is as follows.
[Hardener]
Sodium sulfate (anhydrous) 160.0g
Sodium carbonate (anhydrous) 4.6g
Glyoxal propylene glycol adduct (55%) 20.0 ml
1 liter with water pH (25 ° C.) = 9.5
[0231]

[0232]
[Bleaching Fixer]
600 ml of water
Ammonium thiosulfate (750 g / liter) 93 ml
Ammonium sulfite 40.0g
Ammonium bromide 25.0g
Ethylenediaminetetraacetic acid / ferric ammonium 55.0g
Ethylenediaminetetraacetic acid 5.0 g
Nitric acid (67%) 30.0g
Add 1 liter of water pH (25 ° C) = 5.8
[0233]
[Washing water]
Deionized water with a conductivity of 5μS or less
[0234]
The color filters obtained from the comparative sample 1A and the inventive samples 2A to 2P had RGB and high density black black stripes having no color turbidity and excellent spectral transmittance. All of the color filters obtained from 3B had low blue and green transmittances and were insufficient.
[0235]
Next, the thermal stain and light fastness of each color filter were evaluated.
After leaving in an oven at 180 ° C. for 1 hour, the transmittance (wavelength 450 nm) of the blue pixel portion was measured to evaluate thermal stain. Table 5 shows the relative values of the transmittance after heating when the transmittance of the sample before heating of each photosensitive material is 100.
[0236]
  Moreover, light fastness was evaluated using a Xe fading tester (85000 lux for 10 days). For each photosensitive material, the cyan density in G and the magenta density in R before Xe light irradiation are set to 100, and the light emission is reduced.colorA test was conducted. The decreasing rate of cyan density and magenta density in G of each photosensitive material was defined as the residual rate of each dye. The results are shown in Table 5.
[0237]
[Table 5]

[0238]
As can be seen from the results in Table 5, in the comparative sample 1A, heat stains due to the remaining couplers are often generated, and as a result, the transmittance of the blue portion is lowered. It can be seen that Samples 2A to 2P using the coupler of the present invention are excellent in that the transmittance of the blue part and the green part is little lowered because of less heat stain. From the results of Table 5, it can be seen that the sample using the coupler of the present invention is excellent in the fastness of the cyan component in the green part and the light fastness of the magenta component in the red part.
[0239]
Example 2
Gelatin subbing is applied to a 100 μm-thick polyethylene terephthalate support coated with carbon black dispersed in polyvinyl chloride as a back layer, and the first to ninth layers having the following constitutions are simultaneously coated on the substrate. A color photosensitive material 4A was prepared. Ingredients and application amount (g / m²Unit). In addition, about silver halide, the coating amount of silver conversion is shown.
[0240]

[0241]
Second layer (adjacent layer of gelatin)
Gelatin ・ ・ ・ 0.50
[0242]

[0243]
Fourth layer (intermediate layer)
Gelatin ・ ・ ・ 0.38
Color mixing inhibitor (Cpd-7) 0.07
Color mixing inhibitor (Cpd-10) ... 0.02
High boiling point solvent (Solv-1) 0.03
High boiling point solvent (Solv-3) 0.01
Ultraviolet absorber (Cpd-5) ... 0.02
Ultraviolet absorber (Cpd-4) ... 0.02
UV absorber (Cpd-3) 0.01
UV absorber (Cpd-6) 0.02
Polymer (Cpd-8) ... 0.04
[0244]

[0245]
6th layer (intermediate layer)
Gelatin ・ ・ ・ 0.38
Color mixing inhibitor (Cpd-7) ... 0.09
Color mixing inhibitor (Cpd-10) ... 0.02
High boiling point solvent (Solv-1) 0.03
High boiling point solvent (Solv-3) 0.01
Ultraviolet absorber (Cpd-5) ... 0.02
Ultraviolet absorber (Cpd-4) ... 0.02
UV absorber (Cpd-3) 0.01
UV absorber (Cpd-6) 0.02
Polymer (Cpd-8) ... 0.04
[0246]

[0247]
8th layer (intermediate layer)
Gelatin ・ ・ ・ 0.34
High boiling point solvent (Solv-1) 0.03
High boiling point solvent (Solv-3) 0.01
Ultraviolet absorber (Cpd-5) ... 0.02
Ultraviolet absorber (Cpd-4) ... 0.02
UV absorber (Cpd-3) 0.01
UV absorber (Cpd-6) 0.02
Polymer (Cpd-8) ... 0.04
[0248]
9th layer (protective layer)
Gelatin ・ ・ ・ 0.70
Antihalation dye (fine particle dispersion) ... 0.15
Carboxymethylcellulose ... 0.05
Polymer (Cpd-12) ... 0.14
Surfactant (Cpd-13) ... 0.03
Hardener (H-1) ... 0.12
[0249]
Photosensitive materials 4B to 4D were prepared in the same manner as the photosensitive material 4A, except that YC-6 in the third layer of the photosensitive material 4A was replaced with equimolar amounts of YC-18, YC-19, and YC-25. Photosensitive materials 4E to 4G were prepared in the same manner as the photosensitive material 4B except that equimolar amounts of YM-1 in the seventh layer of the photosensitive material 4B were replaced with YM-3, YM-5, and YM-13, respectively. Photosensitive materials 4H and 4I were the same as photosensitive material 4A except that YC-6 in the third layer of photosensitive material 4A was replaced by equimolar amount with YC-18 and further equimolar amounts of YM-24 and YM-31 were added. Was made. Photosensitive materials 4J and 4K were prepared in the same manner as the photosensitive material 4H, except that YM-1 and equimolar amounts of YM-16 and YM-19 were added to the seventh layer of the photosensitive material 4H. YC-18 and YC-24 of the third layer of the photosensitive material 4J are 4.4 × 10 4^-FourMole YC-6 and 2.2 × 10^-FourA photosensitive material 4L was prepared in the same manner as the photosensitive material 4J, except that the molar amount was changed to ExC-1. A comparative photosensitive material 3C was prepared in the same manner as the photosensitive material 4A except that equimolar amount of YC-6 in the third layer of the photosensitive material 4A was replaced with the comparative coupler A. A comparative photosensitive material 3D was prepared in the same manner as the photosensitive material 3C, except that equimolar amount of YM-1 in the seventh layer of the photosensitive material 3C was replaced with the comparative coupler C.
[0250]
Embedded image

[0251]
The photosensitive materials 4A to 4L, 3C and 3D thus prepared were transferred to a transparent alkali glass having a thickness of 1.1 mm using the emulsion layer as a light-transmitting substrate in the same manner as in Example 1. 7 for the B light exposure, G light exposure mask filter and white light exposure or IR light exposure mask filter shown in FIG. And a color filter matched with the spectral sensitivity of the photosensitive material were overlaid and sequentially exposed three times using tungsten light. The exposed substrate was developed, desilvered, and washed with water according to the steps described above, and a color filter that developed three colors of B, G, and R and black in one operation was prepared.
[0252]
Table 6 shows the results of the evaluation of thermal stain and light fastness according to the same method as in Example 1. Results similar to those in Example 1 were obtained, and it was revealed that the color filter having the coupler of the present invention was excellent.
[0253]
[Table 6]

[0254]
Example 3
Gelatin subbing is applied to a 100 μm-thick polyethylene terephthalate support coated with carbon black dispersed in polyvinyl chloride as a back layer, and the first to ninth layers having the following constitutions are simultaneously coated on the substrate. A color photosensitive material 5A was prepared. Ingredients and application amount (g / m²Unit). In addition, about silver halide, the coating amount of silver conversion is shown.
[0255]

[0256]
Second layer (adjacent layer of gelatin)
Gelatin ・ ・ ・ 0.50
[0257]

[0258]
Fourth layer (intermediate layer)
Gelatin ・ ・ ・ 0.38
Color mixing inhibitor (Cpd-7) 0.07
Color mixing inhibitor (Cpd-10) ... 0.02
High boiling point solvent (Solv-1) 0.03
High boiling point solvent (Solv-3) 0.01
Ultraviolet absorber (Cpd-5) ... 0.02
Ultraviolet absorber (Cpd-4) ... 0.02
UV absorber (Cpd-3) 0.01
UV absorber (Cpd-6) 0.02
Polymer (Cpd-8) ... 0.04
[0259]

[0260]
6th layer (intermediate layer)
Gelatin ・ ・ ・ 0.38
Color mixing inhibitor (Cpd-7) ... 0.09
Color mixing inhibitor (Cpd-10) ... 0.02
High boiling point solvent (Solv-1) 0.03
High boiling point solvent (Solv-3) 0.01
Ultraviolet absorber (Cpd-5) ... 0.02
Ultraviolet absorber (Cpd-4) ... 0.02
UV absorber (Cpd-3) 0.01
UV absorber (Cpd-6) 0.02
Polymer (Cpd-8) ... 0.04
[0261]

[0262]
8th layer (intermediate layer)
Gelatin ・ ・ ・ 0.34
High boiling point solvent (Solv-1) 0.03
High boiling point solvent (Solv-3) 0.01
Ultraviolet absorber (Cpd-5) ... 0.02
Ultraviolet absorber (Cpd-4) ... 0.02
UV absorber (Cpd-3) 0.01
UV absorber (Cpd-6) 0.02
Polymer (Cpd-8) ... 0.04
[0263]
9th layer (protective layer)
Gelatin ・ ・ ・ 0.70
Antihalation dye (fine particle dispersion) ... 0.15
Carboxymethylcellulose ... 0.05
Polymer (Cpd-12) ... 0.14
Surfactant (Cpd-13) ... 0.03
Hardener (H-1) ... 0.12
[0264]
Photosensitive materials 5B to 5D were prepared in the same manner as the photosensitive material 5A except that equimolar amounts of MC-3 in the third layer of the photosensitive material 5A were replaced with MC-3, MC-6, and MC-8, respectively. Photosensitive materials 5E to 5H were prepared in the same manner as the photosensitive material 5B, except that YM-1 in the seventh layer of the photosensitive material 5B was replaced with equimolar amounts of YM-12, YM-13, YM-14, and YM-15. did. Photosensitive material 5I was prepared in the same manner as photosensitive material 5F, except that MC-3 in the third layer of photosensitive material 5F was replaced with equimolar MC-8, and 1/3 mole of MC-18 was further added. A photosensitive material 5J was prepared in the same manner as the photosensitive material 5I except that YM-16 and an equimolar amount of YM-16 were added to the seventh layer of the photosensitive material 5I.
On the other hand, a comparative photosensitive material 3E was prepared in the same manner as the photosensitive material 5A, except that the equimolar amount of the coupler MC-1 in the third layer of the photosensitive material 5A was replaced with the comparative coupler B. A comparative photosensitive material 3F was prepared in the same manner as the photosensitive material 3E, except that the equimolar amount of the coupler YM-1 in the seventh layer of the photosensitive material 3E was replaced with the comparative coupler C.
[0265]
In the same manner as in Example 1, the emulsion layers were transferred to a transparent alkali glass having a thickness of 1.1 mm as the light-sensitive materials 5A to 5J, 3E and 3F produced in this manner. Match the spectral sensitivity of the photosensitive material with the B light exposure mask, the G light exposure mask filter, and the white light exposure mask filter shown in FIG. 10 on the substrate having the 5A-5J emulsion prepared as described above from the emulsion surface side. The obtained color filters were overlaid and sequentially exposed three times using tungsten light. The exposed substrate was developed, desilvered, and washed with water according to the steps described above to produce a color filter that developed three colors of B, G, and R and black in one operation.
[0266]
Table 7 shows the results of evaluation of thermal stain and light fastness according to the same method as in Example 1. Results similar to those of Example 1 were obtained, and it was found that the color filter having the coupler of the present invention was excellent.
[0267]
[Table 7]

[0268]
Example 4
An SBR latex layer and a gelatin layer are used to improve adhesion to a photographic emulsion layer by applying glow discharge treatment to an optically isotropic 80 μm thick polyarylate substrate laminated with a polypropylene protective film (20 μm) on the back side. Two layers of were coated. On top of this, the release layer (first layer) and the second layer (gelatin adjacent layer) of Example 1 were removed, and other layers were reversed, and simultaneous multilayer coating was carried out in the same manner as in Example 1. The film substrate color filter was prepared by performing various exposure, development, fixing, bleaching, washing with water, and drying treatments. On the color filter layer thus obtained, the following composition was applied in a dry film state so as to be 2.5 μm, dried and UV-cured to provide a protective layer. The obtained color filter had good adhesion and chemical resistance between the color filter layer and the protective layer. As a result of evaluating the thermal stain and the light fastness of the sample thus prepared in the same manner as in Example 1, the result having the same tendency as in Example 1 was obtained, and the color filter using the coupler of the present invention was thermally stained. It was found that the light fastness is excellent and the light fastness is excellent.
[0269]
[Overcoat composition prescription]
Monomer (1) 77.4 wt%
Monomer (2) 7.7
Polymer CAB531 (Eastman Chemical Co.) 11.7
Photopolymerization initiator 2.4
Sensitizer 0.8
Dilution solvent for coating (MEK) −
[0270]
Embedded image

[0271]
【The invention's effect】
It has been found that by using the colored coupler of the present invention, a color filter having RGB and high density black black stripes with no spectral turbidity and excellent spectral transmittance can be produced with a simple layer structure and exposure method. In addition, the occurrence of thermal stain was small, the light fastness of cyan and magenta components was improved, and it was revealed that the coupler of the present invention is excellent.
[Brief description of the drawings]
FIG. 1 is a schematic view showing one embodiment of a master color filter that can be used to form a micro color filter.
FIG. 2 is a schematic view showing one embodiment of a micro color filter of the present invention.
FIG. 3 is a schematic view showing one embodiment of a micro color filter of the present invention.
FIG. 4 is a schematic view showing one embodiment of a mask filter that can be used to form a micro color filter.
FIG. 5 is a schematic view showing one embodiment of a master color filter that can be used to form a micro color filter.
FIG. 6 is a schematic view showing one embodiment of a micro color filter of the present invention.
FIG. 7 is a schematic diagram showing one embodiment of a mask filter that can be used to form a micro color filter.
FIG. 8 is a schematic view showing one embodiment of a master color filter that can be used to form a micro color filter.
FIG. 9 is a schematic view showing one embodiment of a micro color filter of the present invention.
FIG. 10 is a schematic view showing one embodiment of a mask filter that can be used to form a micro color filter.
FIG. 11 is a schematic view showing one embodiment of a mask filter that can be used to form a micro color filter.
FIG. 12 is an example of a cross-sectional view of a color liquid crystal display device (LCD) using the color filter of the present invention.
[Explanation of symbols]
Reference numerals in FIG. 12 will be described.
1, 7 Glass substrate
2 RGB color filters
3, 8 Transparent electrode
4 Alignment film
5 Liquid crystal
6 Sealant
9 Black matrix
10, 11 Deflection plate
12 Backlight

Claims (10)

Any one of the three primary colors of cyan, magenta and yellow subtractive colors, and any one of the other two primary colors by coupling reaction with the oxidized color developing agent. A silver halide emulsion layer (1) containing a colored coupler (1a) that produces a dye having a color sensitivity, and a dye having a color sensitivity different from that of the emulsion layer and produced from the colored coupler (1a) by a coupling reaction The colored coupler (1a) has one of the three primary colors other than the two primary colors before the coupling reaction of the colored coupler (1a), and the colored coupler reacts with an oxidant of the color developing agent. possess from (1a) silver halide emulsion layer containing a colored coupler (1b) to generate the same color of the dye and the color of the dye formed by a coupling reaction of (2), further of these One emulsion layer has an emulsion layer having a color sensitivity different from that of the other emulsion layer, and the layer contains a coupler for color correction so that the transmission density is substantially black with a transmission density of 2.5 or more. color light-sensitive material to be. Cyan, magenta, and yellow subtractive color Any one of the three primary colors, and any one of the other two primary colors through a coupling reaction with the oxidized color developing agent. A silver halide emulsion layer (1) containing a colored coupler (1a) for forming a dye, and a color sensitivity different from that of the emulsion layer, and the same color as that before the coupling reaction of the colored coupler (1a) The color of the dye produced by the coupling reaction from the colored coupler (1a) by the coupling reaction with the oxidized form of the color developing agent and the color before the coupling reaction of the colored coupler (1a) silver halide emulsion layer containing a colored coupler (1c) to produce one color of the dye in the subtractive color method three primary non (3) possess a news these two emulsion layers different Having an emulsion layer having a color sensitivity that, color light-sensitive material said layer, characterized in that the transmission density is a layer containing a coupler which color correction such that 2.5 or more substantially black . It has one of the three primary colors of cyan, magenta and yellow, and any one of the other two primary colors through a coupling reaction with the oxidized color developing agent. A silver halide emulsion layer (2) containing a colored coupler (1b) for forming a dye, and a color of the dye having a color sensitivity different from that of the emulsion layer and generated from the colored coupler (1b) by a coupling reaction The color coupler (1b) has a color reduction method other than the two colors before the coupling reaction, and one of the three primary colors, and the color coupler (1b) undergoes a coupling reaction with an oxidant of the color developing agent. silver halide emulsion layer containing a colored coupler (1c) that generates the same color of the dye with the coupling reaction previous color 1b) (3) and a further different color-sensitive to these two emulsion layers Having an emulsion layer having a color light-sensitive material said layer, characterized in that the transmission density is a layer containing a coupler which color correction such that 2.5 or more substantially black. The colored coupler (1a) itself has a yellow color and loses its original color by a coupling reaction with a color developing agent to develop a cyan color, and is represented by the following general formula (I) or general formula (II) The colored coupler (1b), which itself has a magenta color, loses its original color by a coupling reaction with a color developing agent and develops a cyan color. The coupler represented by formula (IV), the colored coupler (1c), which itself has a yellow color, loses its original color by a coupling reaction with a color developing agent and develops a magenta color color light-sensitive material according to claim 1, characterized in that the coupler represented by formula (V) or formula (VI).
Formula (I)
_{Q 1 - (TIME) n -} (L 1) m - (YDYE)
In formula (I), Q ₁ represents a coupler residue that forms a cyan dye by a coupling reaction with an oxidized form of a color developing agent, and TIME is released from Q ₁ by a coupling reaction with an oxidized form of a developing agent. Timing group that later cleaves (TIME) _n-1- (L ₁ ) _m- (YDYE), or timing group that cleaves (TIME) _n-2- (L ₁ ) _m- (YDYE) after leaving TIME Represents. n represents 0, 1, 2 or 3. When n is 2 or more, the plurality of TIMEs are the same or different. L ₁ represents a divalent linking group, (YDYE) represents a yellow dye residue that can flow out into the processing solution, and m represents 0, 1, 2, or 3.
Formula (II)
A ₁ −N = N−R ₁
In the formula (II), A ₁ represents a coupler residue that forms a cyan dye by coupling with an oxidized form of a color developing agent, and R ₁ represents an aryl group or a heterocyclic group.
General formula (III)
_{Q 2 - (TIME) n -} (L 2) m - (MDYE)
In formula (III), Q ₂ represents a coupler residue that forms a cyan dye by coupling with an oxidized form of the developing agent, and TIME is released from Q ₂ by a coupling reaction with the oxidized form of the developing agent ( TIME) represents a timing group that cleaves _n-1- (L ₂ ) _m- (MDYE), or a timing group that cleaves (TIME) _n-2- (L ₂ ) _m- (MDYE) after leaving TIME. . n represents 0, 1, 2 or 3. When n is 2 or more, the plurality of TIMEs are the same or different. L ₂ represents a divalent linking group, (MDYE) represents a magenta dye residue capable of flowing into the processing solution, and m represents 0, 1, 2, or 3.
Formula (IV)
A ₂ -N = N-R ₂
In the formula (IV), A ₂ represents a coupler residue that forms a cyan dye by coupling with an oxidized form of a developing agent, and R ₂ represents an aryl group or a heterocyclic group.
General formula (V)
_{Q 3 - (TIME) n -} (L 3) m - (YDYE)
In formula (V), Q ₃ represents a coupler residue that forms a magenta dye by coupling with an oxidized form of the developing agent, and TIME is released from Q ₃ by a coupling reaction with the oxidized form of the developing agent ( TIME) represents a timing group that cleaves _n-1- (L ₃ ) _m- (YDYE), or a timing group that cleaves (TIME) _n-2- (L ₃ ) _m- (YDYE) after leaving TIME. . n represents 0, 1, 2 or 3. When n is 2 or more, the plurality of TIMEs are the same or different. L ₃ represents a divalent linking group, (YDYE) represents a yellow dye residue that can flow out into the processing solution, and m represents 0, 1, 2, or 3.
General formula (VI)
A ₃ -N = N-R ₃
In the formula (VI), A ₃ represents a coupler residue that forms a magenta dye by coupling with an oxidized form of a developing agent, and R ₃ represents an aryl group or a heterocyclic group. The color light-sensitive material, a color light-sensitive material according to any one of claims 1-4, characterized in that the color light-sensitive material used in the manufacture of color filters. The surface of the color light-sensitive material according to claim 1 is divided into a number of parts, some of which are not exposed, and the other part is exposed with light having a wavelength at which only the emulsion layer (1) is exposed. The method comprises the steps of at least color development, desilvering, and washing with water after exposure to light having a wavelength at which only the emulsion layer (2) is exposed. The surface of the color light-sensitive material according to claim 2 is divided into a number of parts, some of which are exposed to light having a wavelength that only the emulsion layer (1) is sensitive to, and the other part is only the emulsion layer (3). Is exposed to light having a wavelength at which the emulsion layer (1) and the emulsion layer (3) are exposed to light having a wavelength at which both the emulsion layer (1) and the emulsion layer (3) are exposed, and then includes at least color development, desilvering and washing with water. A method for producing a color filter, comprising: The surface of the light-sensitive material according to claim 3 is divided into a number of parts, some of which are not exposed, and the other part is exposed with light of a wavelength that only the emulsion layer (2) is exposed to, and the remainder A method for producing a color filter characterized in that the part is subjected to at least color development, desilvering, and washing treatment after exposure to light having a wavelength at which both the emulsion layer (2) and the emulsion layer (3) are exposed. A color filter characterized in that it is manufactured by the manufacturing method according to any one of claims 6-8. A coupler colored couplers (1a) is represented by the general formula of claim 4 (I) or formula (II), a colored coupler (1b) is the general formula of claim 4 (III) or general a coupler represented by formula (IV), according to claim, characterized in that colored couplers (1c) is a coupler represented by the general formula described (V) or formula (VI) in claim 4 9 the color filter according to.

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