JP3619288B2 - Color image forming method - Google Patents

Description

【０００７】
一般式（Ｉ）中Ｒ_１ 、Ｒ_２ 、Ｒ_３ 及びＲ_４ はそれぞれ同じでも異なっても良く、アルキル基、アリール基、水素原子、アルコキシカルボニル基、アシルアミノ基、スルホンアミド基、またカルバモイル基を表し、それぞれがさらに置換されていても良い。ただし、置換アルキル基としてはスルホラン−３−イル基を含まない。
【０００８】
【化４】

【０００９】
一般式（II）中、Ｒ₅ は水素原子またはアルキル基を表し、Ｒ₆ 、Ｒ₇ は各々独立に無置換アルキル基、またはアルコキシル基で置換されたアルキル基を表す。
（２）像状露光後、芳香族第一級アミン現像主薬を含有する処理液で発色現像する前に、ｐＨが８．０以上の処理液による前浴処理をすることを特徴とする前項（１）に記載のカラー画像形成方法。
（３）前記一般式（Ｉ）においてＲ _３ 、Ｒ _４ のうちの少なくとも１つがパラ位がカルボキシル基により置換されたフェニル基であることを特徴とする前項（１）または（２）に記載のカラー画像形成方法。
（４）前記一般式（ II ）においてＲ _５ がアルキル基であることを特徴とする全項（１）〜（３）のいずれか１項に記載のカラー画像形成方法。
（５）前記一般式（ II ）においてＲ _５ がメチル基であることを特徴とする全項（１）〜（３）のいずれか１項に記載のカラー画像形成方法。
（６）前記一般式（ II ）においてＲ _６ およびＲ _７ がともに無置換アルキル基であることを特徴とする前項（４）または（５）に記載のカラー画像形成方法。
（７）前記支持体が透明支持体であることを特徴とする前項（１）〜（６）のいずれか１項に記載のカラー画像形成方法。
（８）塗布銀量が１．０ｇ／ｍ ^２ 以上２．０ｇ／ｍ ^２ 以下であることを特徴とする前項（１）〜（７）のいずれか１項に記載のカラー画像形成方法。
（９）ゼラチン塗布量が６．５ｇ／ｍ ^２ 以上１４．０ｇ／ｍ ^２ 以下であることを特徴とする前項（１）〜（８）のいずれか１項に記載のカラー画像形成方法。
（１０）前記ハロゲン化銀カラー写真感光材料が、映画用カラーポジフイルムであることを特徴とする前項（１）〜（９）のいずれか１項に記載のカラー画像形成方法。
（１１）透明支持体上に、前記染料の固体分散物含有親水性コロイド層が塗設され、その上層の支持体から遠い側にイエロー発色ハロゲン化銀乳剤層、マゼンタ発色ハロゲン化銀乳剤層及びシアン発色ハロゲン化銀乳剤層が塗設されていることを特徴とする前項（１）〜（１０）のいずれか１項に記載のカラー画像形成方法。
（１２）支持体側から順に青感色性層、赤感色性層、緑感色性層の順に設置されることを特徴とする前項（１）〜（１１）のいずれか１項に記載のカラー画像形成方法。
【００１０】
次に本発明に用いられる一般式（Ｉ）の染料について詳細に説明する。
一般式（Ｉ）においてＲ_１ 、Ｒ_２ 、Ｒ_３ 及びＲ_４ はそれぞれ同じでも異なってもよく、アルキル基、アリール基、水素原子、アルコキシカルボニル基、アシルアミノ基、スルホンアミド基又はカルバモイル基を表わし、それぞれが更に置換されていても良い。但し、置換アルキル基の場合はスルホラン−３−イル基を除く。これらの置換基のなかで、好ましいのは、炭素原子数６〜１４のアリール基又は炭素原子数１〜８のアルキル基である。アリール基の例としては、例えば、フェニル基、ニトロフェニル基、アミノフェニル基、アルキルスルホンアミドフェニル基、カルボキシフェニル基、シアノフェニル基、トリル基などが挙げられる。またアルキル基の場合には、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、シクロヘキシル基などが挙げられる。アルキル基としては、直鎖又は分岐の無置換アルキル基が好ましい。また、更に好ましくは、Ｒ_３ 及びＲ_４ のうち少なくとも１つがパラ位がカルボキシル基により置換されたフェニル基である。また、Ｒ_１ 〜Ｒ_４ の置換基は、一般式（Ｉ）の化合物がｐＨ＝１０．０において水溶性になるように選ばれるのが好ましい。具体的には水への溶解度が約０．１重量％以上となる置換基の組合せが好ましい。
以下に、本発明に用いられる一般式（Ｉ）で表わされる化合物の具体例を記載するが、これらに限定されるものではない。
【００１１】
【化５】

【００１２】
本発明で用いられる、染料の固体微粒子分散物は、公知の方法で調製できる。製造法の詳細は、機能性顔料応用技術（シーエムシー刊、１９９１年）などに記載されている。
本発明において固体染料とは室温（２５℃）で固体の染料をいい、好ましくは融点が６０℃以上のものをいう。
メディア分散は一般的な方法の一つである。この方法では染料粉末またはそのウエットケーキと呼ばれる水や有機溶媒で湿った状態の染料を、水性スラリーにし、公知の粉砕機（例えばボールミル、振動ボールミル、遊星ボールミル、縦型サンドミル、ローラーミル、ピンミル、コボールミル、キャディーミル、横型サンドミル、アトライター等）を用いて、分散メディア（スチールボール、セラミックボール、ガラスビーズ、アルミナビーズ、ジルコニアシリケートビーズ、ジルコニアビーズ、オタワサンドなど）の存在下で機械力によって粉砕する。これらのうち、ビーズの平均直径は好ましくは２ｍｍないし０．３ｍｍ、より好ましくは１ｍｍないし０．３ｍｍ、さらに好ましくは０．５ｍｍないし０．３ｍｍのものが用いられる。これらの他にジェットミル、ロールミル、ホモジナイザー、コロイドミルやデゾルバーによって粉砕する方法や、超音波分散機による粉砕方法も用いることができる。
また米国特許２，８７０，０１２号に開示されているように、均一溶液に溶解した後、貧溶媒を加えて固体微粒子を析出させたり、例えば特開平３−１８２７４３号に開示されているように、アルカリ溶液に溶解した後ｐＨを下げることで、固体微粒子を析出させる方法も用いることが出来る。
これらの固体微粒子分散物を調製するときは、分散助剤を存在させるのが好ましい。従来より開示されてきた分散助剤としては、アルキルフェノキシエトキシスルホン酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、アルキル硫酸エステル塩、アルキルスルホコハク酸塩、ナトリウムオレイルメチルタウライド、ナフタレンスルホン酸のホルムアルデヒド縮重物、ポリアクリル酸、ポリメタクリル酸、マレイン酸アクリル酸共重合物、カルボキシメチルセルロース、硫酸セルロース等のアニオン系分散剤、ポリオキシエチレンアルキルエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステルなどのノニオン系分散剤、カチオン系分散剤やベタイン系分散剤があげられる。
【００１３】
以下に好ましく用いることのできる分散助剤の例を挙げるが、本発明が、これらに限定されるものではない。
【００１４】
【表１】

【００１５】
【表２】

【００１６】
【表３】

【００１７】
【表４】

【００１８】
【表５】

【００１９】
本発明において、本発明の染料に対する上記分散助剤の使用量は重量比で好ましくは０．０１〜２．５０、より好ましくは０．０５〜０．５である。
【００２０】
また固体微粒子分散物の調製時に分散物の安定化や低粘化の目的でポリビニルアルコール、ポリビニルピロリドン、ポリエチレングリコール、多糖類、ゼラチンなどの親水性コロイドを共存させることもできる。
これらの親水性コロイドは単独で用いても複数種のものを併用してもよいが、染料に対して固型分として重量比で通常０．０１〜１０．０、より好ましくは０．０３〜５．０の量で用いることができる。
【００２１】
写真感光材料として染料の微粒子を含有してなる層を設けるには、このようにして得た微粒子を適当なバインダー中に分散させることによってほぼ均一な粒子の固体分散物として調製した後、これを所望の支持体上に塗設することによって設けることが出来る。
上記バインダーは感光性乳剤層や、非感光性層に用いることができる親水性のコロイドであれば特に制限はないが、通常ゼラチンまたはポリビニルアルコールやポリアクリルアミド等の合成ポリマーが用いられる。
固体分散物中の微粒子は、平均粒子径０．００５μｍないし１０μｍ、好ましくは０．０１μｍないし１μｍ、より好ましくは０．０１μｍないし０．７μｍであることが好ましい。
本発明で用いる染料の固体微粒子分散物は、ハロゲン化銀写真感光材料において、染料の色相に応じて非感光性親水性コロイド層（例えば、フィルター層、ハレーション防止層、クロースオーバーカットフィルター層）に含有されるのが好ましいが、該非感光性層が複数層設けられている態様の感光材料においては、これらの複数層に含有させることもできる。
本発明の固体微粒子分散物中の染料濃度は０．１ないし５０重量％、好ましくは２ないし３０重量％である。写真感光材料中の染料の使用量はその色相、作用などによって異なるが、通常１〜１０００ｍｇ／ｍ^２ 、好ましくは５〜３００ｍｇ／ｍ^２ 、より好ましくは５〜２００ｍｇ／ｍ^２ である。
本発明においてハロゲン化銀カラー写真感光材料のマゼンタ発色性ハロゲン化銀乳剤層中のマゼンタカプラーに対する銀の比率はモル換算で３．５以上９．０以下、好ましくは４．０〜８．０である。マゼンタカプラーの添加量は通常と特に異ならないが、感光材料１ｍ^２ 当りで、０．０１〜１０ミリモル／ｍ^２ 、好ましくは０．０５〜５ミリモル／ｍ^２ 、特に好ましくは０．１〜２ミリモル／ｍ^２ とする。
【００２２】
本発明が適用できるカラー感光材料の構成は、透明または反射支持体上にイエロー発色性ハロゲン化銀乳剤層、マゼンタ発色性ハロゲン化銀乳剤層及びシアン発色性ハロゲン化銀乳剤層と非感光性層（親水性コロイド層）が設けられていればよい。好ましくは透明支持体上に、染料の微粒子分散物含有親水性コロイド層が塗設され、その上層の支持体から遠い側に上記ハロゲン化銀乳剤層が塗設されている構成である。上記イエロー、マゼンタ及びシアン発色性ハロゲン化銀乳剤層は青色光、緑色光、および赤色光の何れかに感色性を有する単位感光性層であり、感光性層の配列が、支持体側から順に青感色性層、赤感色性層、緑感色性層の順に設置されるのが好ましい。上記のハロゲン化銀感光性層の間および最上層、最下層には非感光性層を設けてもよい。これらには、後述のカプラー、ＤＩＲ化合物、混色防止剤等が含まれていてもよい。各単位感光性層を複数のハロゲン化銀乳剤層で構成する場合には、ＤＥ１，１２１，４７０あるいはＧＢ９２３，０４５に記載されているように高感度乳剤層、低感度乳剤層の２層を、支持体に向かって順次感光度が低くなる様に配列するのが好ましい。また、特開昭５７−１１２７５１、同６２−２００３５０、同６２−２０６５４１、６２−２０６５４３に記載されているように支持体より離れた側に低感度乳剤層、支持体に近い側に高感度乳剤層を設置してもよい。
【００２３】
本発明において用いられる好ましいハロゲン化銀は約０．５モル％から１００モル％の臭化銀を含む、塩臭化銀、臭化銀、もしくはヨウ塩臭化銀である。本発明において処理ムラ発生防止の点からは少なくとも一層が塩化銀含有率が９５モル％以上で残りが臭化銀（沃化銀）である乳剤を含むのが好ましい。
写真乳剤中のハロゲン化銀粒子は、立方体、八面体、十四面体のような規則的な結晶を有するもの、球状、板状のような変則的な結晶形を有するもの、双晶面などの結晶欠陥を有するもの、あるいはそれらの複合形でもよいが、なかでも立方体が好ましい。
ハロゲン化銀の粒径は、約０．２μｍ以下の微粒子でも投影面積直径が約１０μｍに至るまでの大サイズ粒子でもよく、多分散乳剤でも単分散乳剤でもよいが、単分散乳剤（変動係数０．２０以下）が好ましい。
本発明に使用できるハロゲン化銀写真乳剤は、例えばリサーチ・ディスクロージャー（以下、ＲＤと略す）Ｎｏ．１７６４３（１９７８年１２月），２２〜２３頁，“Ｉ．乳剤製造（Ｅｍｕｌｓｉｏｎ ｐｒｅｐａｒａｔｉｏｎ ａｎｄ
ｔｙｐｅｓ）”、および同Ｎｏ．１８７１６（１９７９年１１月），６４８頁、同Ｎｏ．３０７１０５（１９８９年１１月），８６３〜８６５頁、およびグラフキデ著「写真の物理と化学」，ポールモンテル社刊（Ｐ．Ｇｌａｆｋｉｄｅｓ，Ｃｈｅｍｉｅ ｅｔ Ｐｈｉｓｉｑｕｅ Ｐｈｏｔｏｇｒａｐｈｉｑｕｅ，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）、ゼリクマンら著「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）などに記載された方法を用いて調製することができる。
【００２４】
ＵＳ３，５７４，６２８、同３，６５５，３９４およびＧＢ１，４１３，７４８に記載された単分散乳剤が好ましい。
また、アスペクト比が約３以上であるような平板状粒子も本発明に使用できる。平板状粒子は、ガトフ著、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）；ＵＳ４，４３４，２２６、同４，４１４，３１０、同４，４３３，０４８、同４，４３９，５２０およびＧＢ２，１１２，１５７、特開昭５９−１６２５４０号等に記載の方法により簡単に調製することができる。
結晶構造は一様なものでも、内部と外部とが異質なハロゲン組成からなるものでもよく、層状構造をなしていてもよい。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、例えばロダン銀、酸化鉛などのハロゲン化銀以外の化合物と接合されていてもよい。また種々の結晶形の粒子の混合物を用いてもよい。
【００２５】
ハロゲン化銀乳剤は、通常、物理熟成、化学熟成および分光増感を行ったものを使用する。このような工程で使用される添加剤はＲＤＮｏ．１７６４３、同Ｎｏ．１８７１６および同Ｎｏ．３０７１０５に記載されており、その該当箇所を後掲の表にまとめた。
本発明の感光材料には、感光性ハロゲン化銀乳剤の粒子サイズ、粒子サイズ分布、ハロゲン組成、粒子の形状、感度の少なくとも１つの特性の異なる２種類以上の乳剤を、同一層中に混合して使用することができる。
本発明の感光材料の塗布銀量は、２．０ｇ／ｍ^２ 以下が好ましく、１．８ｇ／ｍ^２ 以下が最も好ましい。塗布銀量の好ましい下限としては約１．０ｇ／ｍ^２ 以上である。
【００２６】
本発明に使用できる写真用添加剤もＲＤに記載されており、下記の表に関連する記載箇所を示した。

【００２７】
本発明の感光材料には種々の色素形成カプラーを使用することができるが、以下のカプラーが特に好ましい。
イエローカプラー：ＥＰ５０２，４２４Ａの式（Ｉ），（ＩＩ）で表わされるカプラー；ＥＰ５１３，４９６Ａの式（１），（２）で表わされるカプラー（特に１８頁のＹ−２８）；特開平５−３０７２４８の請求項１の一般式（Ｉ）で表わされるカプラー；ＵＳ５，０６６，５７６のカラム１の４５〜５５行の一般式（Ｉ）で表わされるカプラー；特開平４−２７４４２５の段落０００８の一般式（Ｉ）で表わされるカプラー；ＥＰ４９８，３８１Ａ１の４０頁のクレーム１に記載のカプラー（特に１８頁のＤ−３５）；ＥＰ４４７，９６９Ａ１の４頁の式（Ｙ）で表わされるカプラー（特にＹ−１（１７頁），Ｙ−５４（４１頁））；ＵＳ４，４７６，２１９のカラム７の３６〜５８行の式（ＩＩ）〜（ＩＶ）で表わされるカプラー（特にＩＩ−１７，１９（カラム１７），ＩＩ−２４（カラム１９））。
マゼンタカプラー；特開平３−３９７３７（Ｌ−５７（１１頁右下），Ｌ−６８（１２頁右下），Ｌ−７７（１３頁右下））；ＥＰ４５６，２５７のＡ−４−６３（１３４頁），Ａ−４−７３，−７５（１３９頁）；ＥＰ４８６，９６５のＭ−４，−６（２６頁），Ｍ−７（２７頁）；特開平６−４３６１１の段落００２４のＭ−４５；特開平５−２０４１０６の段落００３６のＭ−１；特開平４−３６２６３１の段落０２３７のＭ−２２。
シアンカプラー：特開平４−２０４８４３のＣＸ−１，３，４，５，１１，１２，１４，１５（１４〜１６頁）；特開平４−４３３４５のＣ−７，１０（３５頁），３４，３５（３７頁），（Ｉ−１），（Ｉ−１７）（４２〜４３頁）；特開平６−６７３８５の請求項１の一般式（Ｉａ）または（Ｉｂ）で表わされるカプラー。
ポリマーカプラー：特開平２−４４３４５のＰ−１，Ｐ−５（１１頁）。
【００２８】
発色色素が適度な拡散性を有するカプラーとしては、ＵＳ４，３６６，２３７、ＧＢ２，１２５，５７０、ＥＰ９６，８７３Ｂ、ＤＥ３，２３４，５３３に記載のものが好ましい。
発色色素の不要吸収を補正するためのカプラーは、ＥＰ４５６，２５７Ａ１の５頁に記載の式（ＣＩ），（ＣＩＩ），（ＣＩＩＩ ），（ＣＩＶ）で表わされるイエローカラードシアンカプラー（特に８４頁のＹＣ−８６）、該ＥＰに記載のイエローカラードマゼンタカプラーＥｘＭ−７（２０２頁）、ＥＸ−１（２４９頁）、ＥＸ−７（２５１頁）、ＵＳ４，８３３，０６９に記載のマゼンタカラードシアンカプラーＣＣ−９（カラム８）、ＣＣ−１３（カラム１０）、ＵＳ４，８３７，１３６の（２）（カラム８）、ＷＯ９２／１１５７５のクレーム１の式（Ａ）で表わされる無色のマスキングカプラー（特に３６〜４５頁の例示化合物）が好ましい。
【００２９】
現像主薬酸化体と反応して写真的に有用な化合物残基を放出する化合物（カプラーを含む）としては、以下のものが挙げられる。現像抑制剤放出化合物：ＥＰ３７８，２３６Ａ１の１１頁に記載の式（Ｉ），（ＩＩ），（ＩＩＩ） ，（ＩＶ）で表わされる化合物（特にＴ−１０１（３０頁），Ｔ−１０４（３１頁），Ｔ−１１３（３６頁），Ｔ−１３１（４５頁），Ｔ−１４４（５１頁），Ｔ−１５８（５８頁））、ＥＰ４３６，９３８Ａ２の７頁に記載の式（Ｉ）で表わされる化合物（特にＤ−４９（５１頁））、特開平５−３０７２４８の式（１）で表わされる化合物（特に段落００２７の（２３））、ＥＰ４４０，１９５Ａ２の５〜６頁に記載の式（Ｉ），（ＩＩ），（ＩＩＩ） で表わされる化合物（特に２９頁のＩ−（１））；漂白促進剤放出化合物：ＥＰ３１０，１２５Ａ２の５頁の式（Ｉ），（Ｉ′）で表わされる化合物（特に６１頁の（６０），（６１））及び特開平６−５９４１１の請求項１の式（Ｉ）で表わされる化合物（特に段落００２２の（７））；リガンド放出化合物：ＵＳ４，５５５，４７８のクレーム１に記載のＬＩＧ−Ｘで表わされる化合物（特にカラム１２の２１〜４１行目の化合物）；ロイコ色素放出化合物：ＵＳ４，７４９，６４１のカラム３〜８の化合物１〜６；蛍光色素放出化合物：ＵＳ４，７７４，１８１のクレーム１のＣＯＵＰ−ＤＹＥで表わされる化合物（特にカラム７〜１０の化合物１〜１１）；現像促進剤又はカブラセ剤放出化合物：ＵＳ４，６５６，１２３のカラム３の式（１），（２），（３）で表わされる化合物（特にカラム２５の（Ｉ−２２））及びＥＰ４５０，６３７Ａ２の７５頁３６〜３８行目のＥｘＺＫ−２；離脱して初めて色素となる基を放出する化合物：ＵＳ４，８５７，４４７のクレーム１の式（Ｉ）で表わされる化合物（特にカラム２５〜３６のＹ−１〜Ｙ−１９）。
【００３０】
カプラー以外の添加剤としては、以下のものが好ましい。
油溶性有機化合物の分散媒：特開昭６２−２１５２７２のＰ−３，５，１６，１９，２５，３０，４２，４９，５４，５５，６６，８１，８５，８６，９３（１４０〜１４４頁）；油溶性有機化合物の含浸用ラテックス：ＵＳ４，１９９，３６３に記載のラテックス；現像主薬酸化体スカベンジャー：ＵＳ４，９７８，６０６のカラム２の５４〜６２行の式（Ｉ）で表わされる化合物（特にＩ−（１），（２），（６），（１２）（カラム４〜５））、ＵＳ４，９２３，７８７のカラム２の５〜１０行の式（特に化合物１（カラム３））；ステイン防止剤：ＥＰ２９８，３２１Ａの４頁３０〜３３行の式（Ｉ）〜（ＩＩＩ） 、特にＩ−４７，７２、ＩＩＩ −１，２７（２４〜４８頁）；褪色防止剤：ＥＰ２９８，３２１ＡのＡ−６，７，２０，２１，２３，２４，２５，２６，３０，３７，４０，４２，４８，６３，９０，９２，９４，１６４（６９〜１１８頁）、ＵＳ５，１２２，４４４のカラム２５〜３８のＩＩ−１〜ＩＩＩ −２３、特にＩＩＩ −１０，ＥＰ４７１，３４７Ａの８〜１２頁のＩ−１〜ＩＩＩ −４、特にＩＩ−２、ＵＳ５，１３９，９３１のカラム３２〜４０のＡ−１〜４８、特にＡ−３９，４２；発色増強剤または混色防止剤の使用量を低減させる素材：ＥＰ４１１，３２４Ａの５〜２４頁のＩ−１〜ＩＩ−１５、特にＩ−４６；ホルマリンスカベンジャー：ＥＰ４７７，９３２Ａの２４〜２９頁のＳＣＶ−１〜２８、特にＳＣＶ−８；硬膜剤：特開平１−２１４８４５の１７頁のＨ−１，４，６，８，１４、ＵＳ４，６１８，５７３のカラム１３〜２３の式（ＶＩＩ ）〜（ＸＩＩ ）で表わされる化合物（Ｈ−１〜５４）、特開平２−２１４８５２の８頁右下の式（６）で表わされる化合物（Ｈ−１〜７６）、特にＨ−１４、ＵＳ３，３２５，２８７のクレーム１に記載の化合物；現像抑制剤プレカーサー：特開昭６２−１６８１３９のＰ−２４，３７，３９（６〜７頁）；ＵＳ５，０１９，４９２のクレーム１に記載の化合物、特にカラム７の２８，２９；防腐剤、防黴剤：ＵＳ４，９２３，７９０のカラム３〜１５のＩ−１〜ＩＩＩ −４３、特にＩＩ−１，９，１０，１８，ＩＩＩ −２５；安定剤、かぶり防止剤：ＵＳ４，９２３，７９３のカラム６〜１６のＩ−１〜（１４）、特にＩ−１，６０，（２），（１３）、ＵＳ４，９５２，４８３のカラム２５〜３２の化合物１〜６５、特に３６：化学増感剤：トリフェニルホスフィンセレニド、特開平５−４０３２４の化合物５０；染料：特開平３−１５６４５０の１５〜１８頁のａ−１〜ｂ−２０、特にａ−１，１２，１８，２７，３５，３６，ｂ−５，２７〜２９頁のＶ−１〜２３、特にＶ−１、ＥＰ４４５，６２７Ａの３３〜５５頁のＦ−Ｉ−１〜Ｆ−ＩＩ−４３、特にＦ−Ｉ−１１，Ｆ−ＩＩ−８、ＥＰ４５７，１５３Ａの１７〜２８頁のＩＩＩ −１〜３６、特にＩＩＩ −１，３、ＷＯ８８／０４７９４の８〜２６のＤｙｅ−１〜１２４の微結晶分散体、ＥＰ３１９，９９９Ａの６〜１１頁の化合物１〜２２、特に化合物１、ＥＰ５１９，３０６Ａの式（１）ないし（３）で表わされる化合物Ｄ−１〜８７（３〜２８頁）、ＵＳ４，２６８，６２２の式（Ｉ）で表わされる化合物１〜２２（カラム３〜１０）、ＵＳ４，９２３，７８８の式（Ｉ）で表わされる化合物（１）〜（３１）（カラム２〜９）；ＵＶ吸収剤：特開昭４６−３３３５の式（１）で表わされる化合物（１８ｂ）〜（１８ｒ），１０１〜４２７（６〜９頁）、ＥＰ５２０，９３８Ａの式（Ｉ）で表わされる化合物（３）〜（６６）（１０〜４４頁）及び式（ＩＩＩ） で表わされる化合物ＨＢＴ−１〜１０（１４頁）、ＥＰ５２１，８２３Ａの式（１）で表わされる化合物（１）〜（３１）（カラム２〜９）。
【００３１】
本発明の感光材料は、乳剤層を有する側の全親水性コロイド層の膜厚の総和が２８μｍ以下であることが好ましく、２３μｍ以下がより好ましく、１８μｍ以下が更に好ましく、１６μｍ以下が特に好ましい。この好ましい下限としては１０μｍ以上である。また、ゼラチン塗布量としては、６．０〜２０．０ｇ／ｍ^２ が好ましく、更に好ましくは６．５〜１４．０ｇ／ｍ^２ である。また膜膨潤速度Ｔ_１／２ は３０秒以下が好ましく、２０秒以下がより好ましい。Ｔ_１／２ は、発色現像液で３０℃、３分１５秒処理した時に到達する最大膨潤膜厚の９０％を飽和膜厚としたとき、その膜厚が１／２に到達するまでの時間と定義する。膜厚は、２５℃相対湿度５５％調湿下（２日）で測定した膜厚を意味し、Ｔ_１／２ は、エー・グリーン（Ａ．Ｇｒｅｅｎ）らの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（Ｐｈｏｔｏｇｒ．Ｓｃｉ．Ｅｎｇ．），１９巻、２，１２４〜１２９頁に記載の型のスエロメーター（膨潤計）を使用することにより測定できる。Ｔ_１／２ は、バインダーとしてのゼラチンに硬膜剤を加えること、あるいは塗布後の経時条件を変えることによって調整することができる。また、膨潤率は１５０〜４００％が好ましい。膨潤率とは、さきに述べた条件下での最大膨潤膜厚から、式：（最大膨潤膜厚−膜厚）／膜厚により計算できる。
上記のような膜厚、Ｔ_１／２ や膨潤率に調整することによって、迅速処理をより効果的に行うことができる。すなわち、処理ムラや最大発色濃度の変動をより効果的に抑制できる。
本発明のハロゲン化銀感光材料に使用しうる支持体としては、ガラス板、紙（中性紙や酸性紙をポリエチレンやポリエステルなどの樹脂でラミネートした紙、バライタ紙、ポリプロピレン系合成紙などを含む）、プラスチックフィルムまたはシート（ポリエチレンテレフタレート、ポリエチレン−２，６−ナフタレンジカルボキシレート、三酢酸セルロースや硝酸セルロースなどのポリエステル；ポリ塩化ビニルなどの樹脂など）など、親水性コロイド層を塗布できる支持体なら、いかなる透過性、半透過性、又は反射性の支持体でも用いることができる。
本発明が好ましく適用される映画用カラーポジフィルムには、透明プラスチックフィルムが好ましく用いられる。
【００３２】
本発明の感光材料は、未露光状態での高温高湿下の保存後の階調変化を低減するために、感材の被膜ｐＨが４．５〜６．８であることが好ましく、更に好ましくは５．０〜６．５である。被膜ｐＨの測定方法は特開平３−４２２２号に記載されている。また処理ムラの低減の観点からは、フッ素系の界面活性剤を用いるのが好ましく、具体的化合物としては特開平３−１２７０５２号や欧州特許公開ＥＰ−０６０２４２８号等に記載のものを用いることができる。また感光材料中のカルシウム含量は処理ムラの低減の観点からは０〜５０ｍｇ／ｍ^２ が好ましく、更に好ましくは０〜２５ｍｇ／ｍ^２ である。
【００３３】
次に本発明の一般式（ＩＩ）の化合物について述べる。一般式（ＩＩ）においてＲ_５ はメチル基である場合が好ましい。Ｒ_６ およびＲ_７ は無置換アルキル基である場合が好ましく、特にエチル基である場合が好ましい。以下に具体的化合物例を示すが、本発明がこれらに限定されるものではない。
【００３４】
【化６】

【００３５】
本発明においては、感光材料が発色現像処理される前に、ｐＨ＝８．０以上、好ましくは１１以下の処理浴による前浴処理をすることが処理時の発色濃度ムラを抑制するという点で好ましい。前浴のｐＨは８．０以上が好ましく更に好ましくは８．５以上である。ｐＨの調節には炭酸ナトリウム及び炭酸水素ナトリウム等を混合して用いることが好ましい。また、前浴には亜硫酸ナトリウム、塩化ナトリウム、臭化ナトリウム、ヨウ化カリウム等の薬品を添加すると処理時の発色濃度ムラの低減に特に有効である。
前浴の処理時間は１８０秒〜５秒、好ましくは６０秒〜１０秒である。前浴の処理温度は特に制限はないが通常１５℃〜４５℃、好ましくは２５℃〜４０℃である。
【００３６】
【実施例】
【００３７】
実施例１
下塗りを施したポリエチレンテレフタレートフイルム支持体（厚さ１２０μｍ、乳剤面の反対側にカーボンブラックを含有したレジン層を透過濃度１．０になるように塗設してある）に、下記に示すように組成の各層を重層塗布し、多層カラー感光材料である試料１０１を作製した。
（層構成）
以下に各層の組成を示す。数字は塗布量（ｇ／ｍ^２ ）を表す。ハロゲン化銀乳剤はハロゲン化銀換算塗布量を表す。
【００３８】

ここで使用した化合物を以下に示す。
【００３９】
【化７】

【００４０】
【化８】

【００４１】
【化９】

【００４２】
各層のゼラチン硬化剤としては、１，１′−［メチレンビス（スルホニル）］ビス−エーテルをゼラチンに対して１．５重量％用いた。
またイラジエーション防止のために、乳剤層に下記の染料（かっこ内は塗布量を表す）を添加した。
【００４３】
【化１０】

【００４４】
＜染料の固体分散物の作製＞
例示化合物（Ｉ−１）を約６４ｇとり５００ｍｌの水を加え撹拌し染料の粗分散液を作った。この粗分散液に撹拌しながら４ＮのＮａＯＨを滴下しｐＨ＝９．０になるよう調節した。最終的に染料濃度が８％となるよう水を加え、均一な水溶液を得た。
容積１リットルの容器で温度を４６℃に一定に制御しながら以下の方法で染料の固体分散物を作製した。まず２００ｇの１０重量％のゼラチン水溶液に分散助剤０．１９ｇ（例示化合物ＤＡ−５）と硝酸カリウム０．３０ｇを加え均一に溶解した。このときのｐＨは５．７であった。このゼラチン水溶液に上記ｐＨ＝９．０に調節した染料水溶液１１．０ｍｌと０．２ＮのＨ_２ ＳＯ_４ 水溶液３０．０ｍｌを加え１５分撹拌した。このとき最終的に得られた染料の固体分散物のｐＨは５．２であった。この固体分散物の粒径は平均０．５μｍであった。以下の実施例においても特に断わらない限り粒径はこれに合わせた。
表６に示したその他の染料の固体分散物も同様にして調製した。
【００４５】
次に試料１０１に対し、支持体裏面のレジン層を除去し、その替りに下記の導電性ポリマー、界面活性剤、五酸化二バナジウムの針状結晶（０．１５ｇ／ｍ^２ ）、およびアンチモンをドープした酸化スズ微粒子（０．１０ｇ／ｍ^２ ）を含有するコロイド層を設け、他方支持体表面と第一層の間に１．００ｇ／ｍ^２ ゼラチンをバインダーとして含む染料の固体微粒子分散物含有層を設けたことだけが異なる試料１０２〜１１０を作製した。
試料１０２〜１１０は、マゼンタ発色性、緑感光性乳剤層の塩臭化銀乳剤とマゼンタカプラーの比率（Ａｇ／Ｃｐ比）はモル換算で４．３であり、感光材料の被膜ｐＨは６．１０、カルシウムイオン含量は１５ｍｇ／ｍ^２ であった。
【００４６】
【化１１】

【００４７】
次に２５℃−６０％ＲＨで７日間保存した試料１０４に対して、感光計を用い塗布銀量の約３０％が現像されるようなグレー露光を与え、各浴のタンク容量が５リットルの自動現像機を用い以下の処理工程で発色現像液の補充量がタンク容量の２倍になるまでランニング処理を行なった。
【００４８】

各処理液の組成を以下に示す。

【００４９】
【化１２】

【００５０】
次に、上記１０１〜１１０の試料を用い以下の評価を行なった。
（鮮鋭度の評価）
鮮鋭度の評価は視覚上影響の大きいマゼンタ色像に対して行なった。
各試料は塗布後２５℃６０％ＲＨに７日保存したもの及び４０℃７０％ＲＨに７日保存したものを用い、保存条件による鮮鋭度の差を調べた。
各試料に対して、緑色フイルター及び鮮鋭度測定用光学ウエッジを通して感光計（富士写真フイルム製ＦＷＨ型、光源の色温度３２００Ｋ）を用い露光を与え、上記ランニング処理後の液を用いて発色現像処理を行なった。
処理が終了した試料はＣＴＦの測定を行い、ＣＴＦ値０．８を与える空間周波数（本／ｍｍ）をもって鮮鋭度を評価した。値が大きいほど鮮鋭度が高いことを示す。
【００５１】
（処理ムラの評価）
まず試料１０１〜１１０に対して、感光計を用い塗布銀量の約５０％が現像されるようなグレー露光を与えた。このときの試料は２５℃６０％ＲＨに７日間保存したものを用いた。
次に、上記処理工程において、現像主薬の種類を表７及び表８の様に変更した処理を行なった。
処理済の試料を５０ｃｍの長さに裁断し、マゼンタの透過濃度を測定した。処理ムラは、以下の式に従い評価した。
処理ムラ＝４×（濃度ばらつきの標準偏差）／（平均濃度）×１００（％）
この値は小さい程好ましく、官能評価では６．０％以下が許容であった。
【００５２】
（最大発色濃度変動（ΔＤ_ｍａｘ ）の評価）
試料１０１〜１１０に対して、５００ルックスで１０秒の白色光の均一露光を与え、実質全てのハロゲン化銀乳剤が感光して現像されるような露光を与えた。このときの試料は２５℃６０ＲＨ％に７日間保存したものを用いた。次に上記処理工程において、現像主薬の種類を表７及び表８の様に変更したランニング処理を行なった。
また、ランニング後の発色現像液に亜硫酸ナトリウムを２．０ｇ／リットルの量加え同様の処理を行なった。処理済の試料を５０ｃｍの長さに裁断し、マゼンタの透過濃度を測定し平均値を求めた。最大発色濃度変動（ΔＤ_ｍａｘ ）は以下の式に従い評価した。
ΔＤ_ｍａｘ ＝（ランニング処理液でのマゼンタ濃度）−（ランニング処理液に亜硫酸ナトリウムを追添した場合のマゼンタ濃度）
この値は０に近い程処理変動がなく好ましい。
表６、表７及び表８にこれらの評価結果をまとめて示す。
【００５３】
【表６】

【００５４】
【表７】

【００５５】
【表８】

【００５６】
表６によれば、本発明による一般式（Ｉ）の染料の固体分散物を用いることにより、感光材料の保存条件によらずまたカーボンブラックを含む黒色の廃液を出すことなく従来のレジンバックを有する試料と同等以上の鮮鋭度を有する試料が得られることが判る。又、本発明外の比較用染料では両保存条件で満足な鮮鋭度を有する試料は得られないことが判る。
また、表７及び表８によれば本発明による染料の固体分散物を用いると現像主薬の種類により処理ムラの発生は大きく異なり、本発明による現像主薬を用いた場合にのみ処理ムラの程度が小さいことが判る。
従って、鮮鋭度を高く保ち、かつ処理ムラを抑えるには、本発明による染料の固体分散物と本発明による現像主薬を用いることが必須であることが判る。
【００５７】
実施例２
実施例１の試料１０４において、第五層のマゼンタ発色性緑感性乳剤層の塩臭化銀乳剤とマゼンタカプラーの比率（Ａｇ／Ｃｐ比）および総ゼラチン塗布量を表９の様に変更した試料２０１〜２１７を作製した。
塩臭化銀乳剤とマゼンタカプラーの比率（Ａｇ／Ｃｐ比）の変更に際しては、最大発色濃度が一定となるように塗布銀量の絶対値を調節した。また塩臭化銀乳剤の増減に伴いＣｐｄ−３を、またマゼンタカプラーの増減に伴い溶媒（Ｓｏｌｖ−１）と（Ｃｐｄ−６）を同じ割合で変化させた。総ゼラチン塗布量の変更に際しては、各写真構成層のゼラチンを同じ割合で増減させた。
【００５８】
次に、これらの試料を用いて以下の評価を行なった。
【００５９】
（階調変動の評価）
各試料を塗布後２５℃６０％ＲＨに７日保存したもの及び４０℃７０％ＲＨに３０日保存したものを用い保存条件による階調変動の評価を行なった。各試料に対して、緑色フイルターを通して感光計（富士写真フイルム製ＦＷＨ型、光源の色温度３２００Ｋ）を用い２万ルックスで１／１００秒の階調露光を与え、実施例１の鮮鋭度評価に用いたランニング液で処理を行なった。処理後のサンプルのマゼンタの透過濃度を測定し、階調変化（γ４０℃／γ２５℃）を算出した。この値γ４０℃／γ２５℃は１に近い程階調変化が少なく好ましい。
ここでγは、２５℃に保存した試料及び４０℃に保存した試料それぞれについて濃度２．０を与える点よりｌｏｇスケールで０．５高照度露光を与えたときの高濃度部の階調であり、以下の式で求めた。
【００６０】
γ＝｛（濃度２．０を与える点よりｌｏｇスケールで０．５高照度の点の濃度）−２．０｝／０．５
【００６１】
（処理時発色濃度ムラの評価）
実施例１に準じて行なった。
【００６２】
表９にこれらの評価をまとめて示す。
【００６３】
【表９】

【００６４】
表９によれば、保存条件差による階調変動は、Ａｇ／Ｃｐ比が高いと悪化傾向で１０．０以上で極端に悪くなる。一方処理時の発色濃度ムラはＡｇ／Ｃｐ比が低いと悪化傾向で３．０以下で大きく悪化する。以上の様に階調変動と発色濃度ムラの両方を満足させるためには本発明のＡｇ／Ｃｐ比が必須であることが判る。また総ゼラチン塗布量が１４ｇ／ｍ^２ 以下で処理ムラが低減されており、特に８〜１３ｇ／ｍ^２ の範囲が好ましいことが判る。
【００６５】
実施例３
実施例１の試料１０４を用い、実施例１のプレバス液及び発色現像主薬種を以下の様に変更し、実施例１に準じて処理を行い、処理ムラの評価を行なった。
評価結果を表１０に示す。
【００６６】
【表１０】

【００６７】
表１０によれば、本発明の染料の固体分散物を用いて発生する処理ムラは、本発明の現像主薬を用いると改良され、しかもｐＨ＝８．０以上のプレバス浴を用いた場合には更にその効果が著しいことが判る。
【００６８】
【発明の効果】
本発明のカラー画像形成方法によれば、高湿度下での鮮鋭度の劣化や階調変動がなく、しかも処理液の組成による発色濃度の変動が小さく、また処理ムラの発生も抑制される。さらに本発明のカラー画像形成方法によれば写真処理時に黒色の廃液が発生せず、廃液処理の負荷を軽減できる。[0001]
[Industrial application fields]
The present invention relates to a color image forming method using a silver halide color photographic light-sensitive material. More specifically, the ratio of magenta coupler and silver contained in a magenta color-forming layer is defined, and a solid fine particle dispersion of a dye is used as a photographic constituent layer. In a color image forming method in which a silver halide color photographic light-sensitive material contained therein is processed with a processing solution containing an aromatic primary amine developing agent, there is a change in photographic properties after long-term storage of the light-sensitive material in an unexposed state. The present invention relates to a color image forming method in which the occurrence of processing unevenness is reduced.
[0002]
[Prior art]
In a silver halide color photographic light-sensitive material, a photographic emulsion layer or other hydrophilic colloid layer is often colored for the purpose of absorbing light of a specific wavelength. Such a colored layer is called a filter layer, an antihalation layer, a crossover cut layer or the like depending on the purpose. In order to prevent irradiation, the photographic emulsion layer is also colored.
In particular, for the purpose of preventing halation, conventionally, a resin layer containing carbon black has been provided on the back surface of a transparent support, or a hydrophilic colloid layer containing black or yellow colloidal silver has been provided. In the case of using a resin layer containing carbon black, a process for removing the resin layer at the time of processing is necessary. In addition, in order to treat the black waste liquid containing carbon black generated at that time, it is necessary to take measures such as precipitating and removing carbon black, or diluting with a large amount of water and discarding it. It is. On the other hand, when colloidal silver is used, if a sufficient amount is used to prevent halation, the total amount of silver in the light-sensitive material increases, increasing the load on the bleaching bath and fixing bath, and desilvering due to variations in the processing solution composition. It may disappear. When colloidal silver is used in the coupler-containing layer or its adjacent layer, the colloidal silver may become a nucleus of dissolution physical development and cause fogging. Furthermore, in the case of a color positive film for movies in particular, a silver image is used for the sound track, and colloidal silver cannot be used for the purpose of preventing halation.
[0003]
As a method for solving the above method, a method of dyeing a specific layer using a solid fine particle dispersion of a dye which contains a dissociable group in a molecule and is insoluble in water in a non-dissociated state is excellent. No. -120030, No. 56-12639, No. 55-155350, No. 55-155351, No. 63-27838, No. 63-197943, No. 52-92716, No. 64-40827, and JP-A No. 2-40827. 282244, European Patent Publications EP-015601, 323729, 274723, 276656, 299435, International Publication WO88 / 04794, and the like. This type of dye is not dyed to a specific hydrophilic colloid layer and diffused to other layers during storage of the light-sensitive material before processing. Further, it is decolorized in the photographic processing process without deteriorating the processing solution.
[0004]
[Problems to be solved by the invention]
However, when the solid fine particle dispersion of the above dye is incorporated into a photographic light-sensitive material and the unexposed light-sensitive material is stored under high humidity, the absorbance of the dye decreases and the sharpness after processing decreases. It was found that softening occurred at the high concentration part. Further, it has been found that the color density varies due to the variation of the processing solution composition, and color density unevenness occurs particularly in the high density part. The conventional technique has not found any means for solving such photographic fluctuations and processing unevenness.
Accordingly, a first object of the present invention is to provide a color image forming method which uses a silver halide photographic light-sensitive material using a solid fine particle dispersion of a dye and which has a small waste liquid processing load. The second purpose is that there is no deterioration in sharpness or gradation even after storage of unexposed photosensitive material under high humidity for a long period of time. It is an object of the present invention to provide a color image forming method in which the occurrence of the above is suppressed.
[0005]
[Means for Solving the Problems]
As a result of intensive studies, the present inventor has found that the above problems can be solved by the following means (1) and (2).
(1) A silver halide color photographic material containing a solid fine particle dispersion of yellow, magenta, cyan dye-forming coupler and dye in a photographic composition layer is exposed imagewise and then contains an aromatic primary amine developing agent. In the color image forming method in which color development processing is performed with the processing solution, the ratio of silver to magenta coupler in the magenta color-forming silver halide emulsion layer of the silver halide color photographic light-sensitive material is 3.5 or more and 9.0 in terms of mole. And a color image wherein the dye is a compound represented by the following general formula (I) and the aromatic primary amine developing agent is represented by the following general formula (II): Forming method.
[0006]
[Chemical 3]

[0007]
R in general formula (I)₁  , R₂  , R₃  And R₄  Each may be the same or different and each represents an alkyl group, an aryl group, a hydrogen atom, an alkoxycarbonyl group, an acylamino group, a sulfonamido group, or a carbamoyl group, and each may be further substituted. However, the substituted alkyl group does not include a sulfolane-3-yl group.
[0008]
[Formula 4]

[0009]
In general formula (II), R_FiveRepresents a hydrogen atom or an alkyl group, R₆, R₇Each independently represents an unsubstituted alkyl group or an alkyl group substituted with an alkoxyl group.
(2) After the imagewise exposure, before color development with a processing solution containing an aromatic primary amine developing agent, a pre-bath treatment with a processing solution having a pH of 8.0 or more is performed. The color image forming method according to 1).
(3) R in the general formula (I) ₃ , R ₄ The color image forming method as described in (1) or (2) above, wherein at least one of them is a phenyl group substituted at the para position by a carboxyl group.
(4) General formula ( II ) R ₅ The color image forming method according to any one of (1) to (3), wherein is an alkyl group.
(5) General formula ( II ) R ₅ The color image forming method according to any one of (1) to (3), wherein is a methyl group.
(6) The general formula ( II ) R ₆ And R ₇ The color image forming method as described in (4) or (5) above, wherein both are unsubstituted alkyl groups.
(7) The color image forming method described in any one of (1) to (6) above, wherein the support is a transparent support.
(8) The applied silver amount is 1.0 g / m ² 2.0 g / m ² The color image forming method according to any one of (1) to (7), wherein:
(9) Gelatin coating amount is 6.5 g / m ² 14.0 g / m ² The color image forming method according to any one of the above items (1) to (8), which is as follows.
(10) The color image forming method as described in any one of (1) to (9) above, wherein the silver halide color photographic light-sensitive material is a color positive film for movies.
(11) A hydrophilic colloid layer containing a solid dispersion of the dye is coated on a transparent support, and a yellow-colored silver halide emulsion layer, a magenta-colored silver halide emulsion layer, 11. The color image forming method as described in any one of (1) to (10) above, wherein a cyan color developing silver halide emulsion layer is provided.
(12) The blue color-sensitive layer, the red color-sensitive layer, and the green color-sensitive layer are installed in this order from the support side, and any one of (1) to (11) above Color image forming method.
[0010]
Next, the dye of the general formula (I) used in the present invention will be described in detail.
R in general formula (I)₁  , R₂  , R₃  And R₄  Each may be the same or different and each represents an alkyl group, an aryl group, a hydrogen atom, an alkoxycarbonyl group, an acylamino group, a sulfonamide group or a carbamoyl group, and each may be further substituted. However, in the case of a substituted alkyl group, a sulfolan-3-yl group is excluded. Among these substituents, an aryl group having 6 to 14 carbon atoms or an alkyl group having 1 to 8 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a nitrophenyl group, an aminophenyl group, an alkylsulfonamidophenyl group, a carboxyphenyl group, a cyanophenyl group, and a tolyl group. In the case of an alkyl group, examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a cyclohexyl group. As the alkyl group, a linear or branched unsubstituted alkyl group is preferable. More preferably, R₃  And R₄  At least one of them is a phenyl group substituted at the para position by a carboxyl group. R₁  ~ R₄  Is preferably selected so that the compound of general formula (I) is water-soluble at pH = 10.0. Specifically, a combination of substituents having a solubility in water of about 0.1% by weight or more is preferable.
Specific examples of the compound represented by the general formula (I) used in the present invention are described below, but are not limited thereto.
[0011]
[Chemical formula 5]

[0012]
The solid fine particle dispersion of the dye used in the present invention can be prepared by a known method. Details of the production method are described in functional pigment application technology (published by CMC, 1991).
In the present invention, the solid dye means a dye which is solid at room temperature (25 ° C.), and preferably has a melting point of 60 ° C. or higher.
Media distribution is one of the common methods. In this method, the dye powder or its wet cake, which is a dye powder, is wet with water or an organic solvent, is converted into an aqueous slurry, and a known pulverizer (for example, ball mill, vibration ball mill, planetary ball mill, vertical sand mill, roller mill, pin mill, Using a coball mill, caddy mill, horizontal sand mill, attritor, etc.) and grinding by mechanical force in the presence of dispersion media (steel balls, ceramic balls, glass beads, alumina beads, zirconia silicate beads, zirconia beads, Ottawa sand, etc.) To do. Among these, beads having an average diameter of preferably 2 mm to 0.3 mm, more preferably 1 mm to 0.3 mm, and still more preferably 0.5 mm to 0.3 mm are used. In addition to these, a method of pulverizing with a jet mill, a roll mill, a homogenizer, a colloid mill or a dissolver, and a pulverizing method with an ultrasonic disperser can also be used.
Further, as disclosed in U.S. Pat. No. 2,870,012, after dissolving in a uniform solution, a poor solvent is added to precipitate solid fine particles. For example, as disclosed in JP-A-3-182743. A method of precipitating solid fine particles by lowering the pH after dissolving in an alkaline solution can also be used.
When preparing these solid fine particle dispersions, it is preferable that a dispersion aid is present. Dispersing aids that have been disclosed in the past include alkyl phenoxy ethoxy sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate ester salt, alkyl sulfosuccinate, sodium oleyl methyl taurate, naphthalene sulfonic acid. Denatured formaldehyde, polyacrylic acid, polymethacrylic acid, maleic acid acrylic acid copolymer, anionic dispersants such as carboxymethyl cellulose and cellulose sulfate, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Nonionic dispersants, cationic dispersants and betaine dispersants.
[0013]
Examples of the dispersion aid that can be preferably used are shown below, but the present invention is not limited thereto.
[0014]
[Table 1]

[0015]
[Table 2]

[0016]
[Table 3]

[0017]
[Table 4]

[0018]
[Table 5]

[0019]
In this invention, the usage-amount of the said dispersion adjuvant with respect to the dye of this invention becomes like this. Preferably it is 0.01-2.50, More preferably, it is 0.05-0.5.
[0020]
In addition, hydrophilic colloids such as polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polysaccharides and gelatin can be coexisted for the purpose of stabilizing the dispersion and reducing the viscosity when preparing the solid fine particle dispersion.
These hydrophilic colloids may be used alone or in combination of two or more kinds, but usually 0.01 to 10.0, more preferably 0.03 to 0.03 by weight as a solid component with respect to the dye. It can be used in an amount of 5.0.
[0021]
In order to provide a layer containing fine dye particles as a photographic light-sensitive material, the fine particles thus obtained are dispersed in a suitable binder to prepare a solid dispersion of substantially uniform particles. It can be provided by coating on a desired support.
The binder is not particularly limited as long as it is a hydrophilic colloid that can be used in a photosensitive emulsion layer or a non-photosensitive layer, but usually a gelatin or a synthetic polymer such as polyvinyl alcohol or polyacrylamide is used.
The fine particles in the solid dispersion preferably have an average particle size of 0.005 μm to 10 μm, preferably 0.01 μm to 1 μm, more preferably 0.01 μm to 0.7 μm.
In the silver halide photographic material, the solid fine particle dispersion of the dye used in the present invention is applied to a non-photosensitive hydrophilic colloid layer (for example, a filter layer, an antihalation layer, a close-over cut filter layer) according to the hue of the dye. Although it is preferable to contain, in the photosensitive material of the aspect in which this non-photosensitive layer is provided in multiple layers, it can also be contained in these multiple layers.
The dye concentration in the solid fine particle dispersion of the present invention is 0.1 to 50% by weight, preferably 2 to 30% by weight. The amount of dye used in the photographic light-sensitive material varies depending on the hue, action, etc., but is usually 1-1000 mg / m²  , Preferably 5 to 300 mg / m²  , More preferably 5 to 200 mg / m²  It is.
In the present invention, the ratio of silver to magenta coupler in the magenta color-forming silver halide emulsion layer of the silver halide color photographic light-sensitive material is 3.5 or more and 9.0 or less, preferably 4.0 to 8.0 in terms of mole. is there. The addition amount of magenta coupler is not particularly different from usual, but the photosensitive material 1m²  Per unit, 0.01 to 10 mmol / m²  , Preferably 0.05 to 5 mmol / m²  , Particularly preferably 0.1 to 2 mmol / m²  And
[0022]
The composition of the color light-sensitive material to which the present invention can be applied includes a yellow color-developing silver halide emulsion layer, a magenta color-developing silver halide emulsion layer, and a cyan color-developing silver halide emulsion layer and a non-photosensitive layer on a transparent or reflective support. (Hydrophilic colloid layer) may be provided. Preferably, a hydrophilic colloid layer containing a fine particle dispersion of a dye is coated on a transparent support, and the silver halide emulsion layer is coated on the side farther from the support. The yellow, magenta and cyan color-developing silver halide emulsion layers are unit photosensitive layers having color sensitivity to any of blue light, green light, and red light, and the arrangement of the photosensitive layers is in order from the support side. The blue color-sensitive layer, the red color-sensitive layer, and the green color-sensitive layer are preferably installed in this order. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain couplers, DIR compounds, color mixing inhibitors and the like described later. When each unit photosensitive layer is composed of a plurality of silver halide emulsion layers, two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in DE 1,121,470 or GB 923,045, It is preferable to arrange so that the photosensitivity decreases sequentially toward the support. Further, as described in JP-A-57-112751, 62-200350, 62-206541 and 62-206543, a low-sensitivity emulsion layer is provided on the side away from the support, and a high-sensitivity emulsion is provided on the side close to the support. Layers may be installed.
[0023]
The preferred silver halide used in the present invention is silver chlorobromide, silver bromide, or silver iodochlorobromide containing from about 0.5 mol% to 100 mol% of silver bromide. In the present invention, it is preferable that at least one layer contains an emulsion having a silver chloride content of 95 mol% or more and the rest being silver bromide (silver iodide) from the viewpoint of preventing the occurrence of processing unevenness.
Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedrons, tetradecahedrons, irregular crystal shapes such as spheres and plates, twin planes, etc. However, a cube is preferable.
The grain size of silver halide may be fine grains having a diameter of about 0.2 μm or less or large size grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. .20 or less) is preferable.
Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and"
), and No. 18716 (November 1979), 648, No. 307105 (November 1989), 863-865, and Grafkide, "Physics and Chemistry of Photography", published by Paul Monter (P. Glafkides, Chemie et Physique Photographic, Paul Montel, 1967), “Photoemulsion Chemistry” by Duffin, published by Focal Press (G. F. Duffin, Photographic Chemistry, 19). Emulsion production and coating ", published by Focal Press (VL Zelikman, et al., Making and Coating Photographic Emulsion). Focal Press, 1964) can be prepared using the methods described, for example.
[0024]
Monodisperse emulsions described in US Pat. Nos. 3,574,628, 3,655,394 and GB 1,413,748 are preferred.
Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering, Vol. 14, 248-257 (1970); US 4,434,226, 4,414,310, 4,433,048, 4,439,520 and GB2,112,157, and JP-A-59-162540.
The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, or a layered structure may be formed. Silver halides having different compositions may be bonded by epitaxial bonding, and may be bonded to a compound other than silver halide, such as rhodium silver or lead oxide. A mixture of particles having various crystal forms may be used.
[0025]
As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are usually used. The additive used in such a process is RDNo. 17643, ibid. 18716 and No. 1 307105, and the corresponding sections are summarized in the table below.
In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used.
The silver coating amount of the light-sensitive material of the present invention is 2.0 g / m.²The following is preferred, 1.8 g / m²The following are most preferred. A preferable lower limit of the amount of silver applied is about 1.0 g / m.²  That's it.
[0026]
Photographic additives that can be used in the present invention are also described in the RD, and the relevant locations are shown in the following table.

[0027]
Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable.
Yellow couplers: couplers represented by formulas (I) and (II) of EP502,424A; couplers represented by formulas (1) and (2) of EP513,496A (especially Y-28 on page 18); 307248, the coupler represented by the general formula (I) of claim 1; US Pat. No. 5,066,576, column 1, line 45 to 55, the coupler represented by the general formula (I); A coupler represented by formula (I); a coupler according to claim 1 of page 40 of EP498,381A1 (especially D-35 of page 18); a coupler represented by formula (Y) of page 4 of EP447,969A1 (especially Y -1 (page 17), Y-54 (page 41)); couplers represented by formulas (II) to (IV) in columns 7 to 58 of US Pat. II-17, 19 (column 17), II-24 (column 19)).
Magenta coupler; JP-A-3-39737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13)); A-4-63 of EP456,257 ( 134), A-4-73, -75 (page 139); M-4, -6 (page 26), M-7 (page 27) of EP486,965; M in paragraph 0024 of JP-A-6-43611; -45; M-1 of paragraph 0036 of JP-A-5-204106; M-22 of paragraph 0237 of JP-A-4-362631.
Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14-16) of JP-A-4-204843; C-7,10 (page 35), 34 of JP-A-4-43345 35 (page 37), (I-1), (I-17) (pages 42 to 43); a coupler represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385.
Polymer coupler: P-1, P-5 (page 11) of JP-A-2-44345.
[0028]
As couplers in which the coloring dye has an appropriate diffusibility, those described in US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B, DE 3,234,533 are preferable.
A coupler for correcting unwanted absorption of the coloring dye is a yellow colored cyan coupler represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP456,257A1 (particularly, page 84). YC-86), yellow colored magenta coupler described in EP, ExM-7 (page 202), EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler described in US Pat. No. 4,833,069 CC-9 (column 8), CC-13 (column 10), US 4,837, 136 (2) (column 8), colorless masking coupler represented by formula (A) of claim 1 of WO 92/11575 (particularly Exemplified compounds on pages 36 to 45) are preferred.
[0029]
Examples of the compounds (including couplers) that release a photographically useful compound residue by reacting with oxidized developing agent include the following. Development inhibitor releasing compounds: compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of EP378, 236A1 (particularly T-101 (page 30), T-104 (31) Page), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP 436, 938A2, page 7; Compounds represented (especially D-49 (page 51)), compounds represented by formula (1) of JP-A-5-307248 (especially paragraph (23) of paragraph 0027), formulas described on pages 5 to 6 of EP440, 195A2 Compounds represented by (I), (II), (III) (especially I- (1) on page 29); Bleach accelerator releasing compounds: in formulas (I) and (I ') on page 5 of EP310, 125A2 The compounds represented (especially (60) on page 61, (61 )) And the compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly paragraph (0022) of paragraph 0022); ligand releasing compound: LIG-X according to claim 1 of US 4,555,478 Compounds represented (especially compounds in columns 21-41 of column 12); leuco dye releasing compounds: compounds 1-6 of columns 3-8 of US 4,749,641; fluorescent dye releasing compounds: claims of US 4,774,181 1 compound represented by COUP-DYE (especially compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: formula (1), (2), (column 3 of US 4,656,123) 3) (especially (I-22) in column 25) and ExZK-2 on page 75, lines 36 to 38 of EP450, 637A2; Release the compounds: compounds represented by US4,857,447 claim 1 of the formula (I) (Y-1~Y-19, especially columns 25-36).
[0030]
As additives other than couplers, the following are preferable.
Oil-soluble organic compound dispersion medium: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 of JP-A-62-215272 (140-144) Page); Latex for impregnation of oil-soluble organic compound: Latex described in US Pat. No. 4,199,363; Oxidant scavenger for developing agent: Compound represented by formula (I) in columns 2 to 54 of US Pat. No. 4,978,606 (Especially I- (1), (2), (6), (12) (columns 4-5)), US Pat. No. 4,923,787, column 2, line 5-10 (particularly compound 1 (column 3) ); Stain inhibitor: Formulas (I) to (III) on page 4, lines 30 to 33 of EP298,321A, in particular I-47,72, III-1,27 (pages 24 to 48); Antifading agent: EP298 , 321A A-6, 7, 2 0, 21, 23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69-118), US 5,122,444, columns 25-38 II -1 to III-23, especially III-10, EP471, 347A, pages 8-12, I-1 to III-4, especially II-2, US 5,139,931, columns 32-40, A-1 to 48. In particular, A-39, 42; Materials that reduce the amount of color-enhancing agent or color mixing inhibitor used: EP411, 324A, pages 5-24, I-1 to II-15, especially I-46; formalin scavenger: EP477, 932A, pages 24 to 29, SCV-1 to 28, in particular SCV-8; hardener: H-1,4,6,8,14, JP 4,618,573, column 17 of JP-A-1-214845. 13-2 Compounds (H-1 to 54) represented by formulas (VII) to (XII), compounds (H-1 to 76) represented by formula (6) at the lower right of page 8 of JP-A-2-214852, particularly H -14, compound described in claim 1 of US Pat. No. 3,325,287; development inhibitor precursor: P-24, 37, 39 (pages 6 to 7) of JP-A-62-168139; claim 1 of US Pat. No. 5,019,492 Compounds 28, 29 of column 7, especially preservatives, fungicides: US Pat. No. 4,923,790 columns 3-15 I-1 to III-43, in particular II-1,9,10,18, III-25; Stabilizer, antifoggant: I-1 to (14) of columns 6 to 16 of US 4,923,793, in particular I-1,60, (2), (13), US 4,952,483 Compounds 1-65 of columns 25-32 of 36: Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; Dye: a-1 to b-20 on pages 15-18 of JP-A-3-156450, in particular a-1,12 18, 27, 35, 36, b-5, pages 27 to 29, V-1 to 23, particularly V-1, EP445, 627A, pages 33 to 55, F-1 to F-II-43, In particular, F-11, F-II-8, EP457, 153A, pages 17-28, III-1 to 36, especially III-1,3, WO88 / 04794, 8-26, Dye-1 to 124 Crystalline dispersion, compounds 1 to 22 on pages 6 to 11 of EP319, 999A, in particular compound 1, compounds D-1 to 87 represented by formulas (1) to (3) of EP519,306A (pages 3 to 28), Table of formula (I) of US 4,268,622 Compounds 1 to 22 (columns 3 to 10), compounds (1) to (31) (columns 2 to 9) represented by the formula (I) of US 4,923,788; Compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by formula (1) of -3335, and compounds (3) to (66) (10) represented by formula (I) of EP520 and 938A -44) and compounds HBT-1-10 represented by formula (III) (page 14), compounds (1)-(31) represented by formula (1) of EP521,823A (columns 2-9).
[0031]
In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the side having an emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and particularly preferably 16 μm or less. The preferable lower limit is 10 μm or more. The gelatin coating amount is 6.0 to 20.0 g / m.²  Is preferable, and more preferably 6.5 to 14.0 g / m.²  It is. In addition, membrane swelling speed T_1/2Is preferably 30 seconds or shorter, and more preferably 20 seconds or shorter. T_1/2Is defined as the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness that is reached at 30 ° C. for 3 minutes and 15 seconds with a color developer is defined as the saturated film thickness. The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days)._1/2Is a spherometer of the type described in A. Green et al., Photographic Science and Engineering (Photogr. Sci. Eng.), Vol. 19, pp. 2,124-129. Can be measured. T_1/2Can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness.
Film thickness as above, T_1/2  By adjusting to the swelling rate, rapid processing can be performed more effectively. That is, it is possible to more effectively suppress processing unevenness and fluctuations in the maximum color density.
Supports that can be used in the silver halide light-sensitive material of the present invention include glass plates, paper (paper obtained by laminating neutral paper or acid paper with a resin such as polyethylene or polyester, baryta paper, polypropylene synthetic paper, etc. ), Plastic films or sheets (polyethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, polyesters such as cellulose triacetate and cellulose nitrate; resins such as polyvinyl chloride), etc. Any transmissive, translucent, or reflective support can be used.
A transparent plastic film is preferably used for the color positive film for movies to which the present invention is preferably applied.
[0032]
The light-sensitive material of the present invention preferably has a coating pH of 4.5 to 6.8, more preferably, in order to reduce gradation change after storage under high temperature and high humidity in an unexposed state. Is 5.0 to 6.5. A method for measuring the coating pH is described in JP-A-3-4222. Further, from the viewpoint of reducing treatment unevenness, it is preferable to use a fluorine-based surfactant, and as specific compounds, those described in JP-A Nos. 3-127052 and EP-0602428 can be used. it can. The calcium content in the light-sensitive material is 0 to 50 mg / m from the viewpoint of reducing processing unevenness.²  Is more preferable, and more preferably 0 to 25 mg / m.²  It is.
[0033]
Next, the compound of the general formula (II) of the present invention will be described. R in general formula (II)₅  Is preferably a methyl group. R₆  And R₇  Is preferably an unsubstituted alkyl group, particularly preferably an ethyl group. Although the example of a specific compound is shown below, this invention is not limited to these.
[0034]
[Chemical 6]

[0035]
In the present invention, before the light-sensitive material is color-developed, pre-bath treatment with a treatment bath having a pH of 8.0 or more, preferably 11 or less suppresses uneven color density during processing. preferable. The pH of the prebath is preferably 8.0 or higher, more preferably 8.5 or higher. For adjusting the pH, it is preferable to use a mixture of sodium carbonate and sodium bicarbonate. In addition, adding chemicals such as sodium sulfite, sodium chloride, sodium bromide, potassium iodide to the pre-bath is particularly effective in reducing uneven color density during processing.
The prebath treatment time is 180 seconds to 5 seconds, preferably 60 seconds to 10 seconds. The treatment temperature of the prebath is not particularly limited, but is usually 15 ° C to 45 ° C, preferably 25 ° C to 40 ° C.
[0036]
【Example】
[0037]
Example 1
As shown below, an undercoated polyethylene terephthalate film support (thickness 120 μm, resin layer containing carbon black on the opposite side of the emulsion surface is coated to a transmission density of 1.0) Each layer of the composition was applied in multiple layers to prepare Sample 101 which is a multilayer color photosensitive material.
(Layer structure)
The composition of each layer is shown below. Numbers are application amount (g / m²  ). The silver halide emulsion represents a coating amount in terms of silver halide.
[0038]

The compounds used here are shown below.
[0039]
[Chemical 7]

[0040]
[Chemical 8]

[0041]
[Chemical 9]

[0042]
As a gelatin hardener for each layer, 1,1 ′-[methylenebis (sulfonyl)] bis-ether was used at 1.5% by weight based on gelatin.
In order to prevent irradiation, the following dyes (the coating amount is shown in parentheses) were added to the emulsion layer.
[0043]
[Chemical Formula 10]

[0044]
<Preparation of solid dispersion of dye>
About 64 g of Exemplified Compound (I-1) was taken and 500 ml of water was added and stirred to prepare a crude dye dispersion. While stirring the crude dispersion, 4N NaOH was added dropwise to adjust the pH to 9.0. Finally, water was added so that the dye concentration was 8% to obtain a uniform aqueous solution.
A solid dispersion of the dye was prepared by the following method while controlling the temperature at 46 ° C. constant in a 1 liter container. First, 0.19 g of a dispersion aid (Exemplary Compound DA-5) and 0.30 g of potassium nitrate were added to 200 g of a 10% by weight gelatin aqueous solution and uniformly dissolved. The pH at this time was 5.7. To this gelatin aqueous solution, 11.0 ml of a dye aqueous solution adjusted to pH = 9.0 and 0.2N H₂  SO₄  30.0 ml of an aqueous solution was added and stirred for 15 minutes. At this time, the pH of the finally obtained solid dispersion of the dye was 5.2. The average particle size of the solid dispersion was 0.5 μm. In the following examples, the particle size was adjusted to this unless otherwise specified.
Solid dispersions of other dyes shown in Table 6 were similarly prepared.
[0045]
Next, the resin layer on the back surface of the support was removed from the sample 101. Instead, the following conductive polymer, surfactant, and acicular crystals of divanadium pentoxide (0.15 g / m²  ), And tin oxide fine particles doped with antimony (0.10 g / m²  ), And 1.00 g / m between the support surface and the first layer.²  Samples 102 to 110 differing only in that a solid fine particle dispersion-containing layer of a dye containing gelatin as a binder was provided.
In Samples 102 to 110, the ratio (Ag / Cp ratio) between the silver chlorobromide emulsion and the magenta coupler in the magenta color developing and green photosensitive emulsion layer was 4.3 in terms of mole, and the coating pH of the photosensitive material was 6. 10 、 Calcium ion content is 15mg / m²  Met.
[0046]
Embedded image

[0047]
Next, the sample 104 stored for 7 days at 25 ° C.-60% RH was given a gray exposure so that about 30% of the applied silver amount was developed using a sensitometer, and the tank capacity of each bath was 5 liters. Using an automatic developing machine, running processing was performed in the following processing steps until the replenishment amount of the color developer became twice the tank capacity.
[0048]

The composition of each treatment liquid is shown below.

[0049]
Embedded image

[0050]
Next, the following evaluation was performed using the samples 101 to 110 described above.
(Evaluation of sharpness)
The sharpness was evaluated for a magenta color image having a large visual effect.
Each sample was stored for 7 days at 25 ° C. and 60% RH after coating, and stored for 7 days at 40 ° C. and 70% RH, and the difference in sharpness depending on the storage conditions was examined.
Each sample was exposed using a sensitometer (FWH type manufactured by Fuji Photo Film, light source color temperature 3200K) through a green filter and an optical wedge for sharpness measurement, and color development processing was performed using the solution after the running processing. Was done.
The sample after the treatment was subjected to CTF measurement, and the sharpness was evaluated at a spatial frequency (lines / mm) giving a CTF value of 0.8. A larger value indicates higher sharpness.
[0051]
(Evaluation of processing unevenness)
First, samples 101 to 110 were subjected to gray exposure so that about 50% of the applied silver amount was developed using a photometer. The sample used at this time was stored at 25 ° C. and 60% RH for 7 days.
Next, in the above processing steps, processing was performed in which the type of developing agent was changed as shown in Tables 7 and 8.
The treated sample was cut into a length of 50 cm, and the transmission density of magenta was measured. The treatment unevenness was evaluated according to the following formula.
Processing unevenness = 4 × (standard deviation of density variation) / (average density) × 100 (%)
This value is preferably as small as possible, and 6.0% or less was acceptable in sensory evaluation.
[0052]
(Maximum color density fluctuation (ΔD_max  )Evaluation of)
Samples 101 to 110 were subjected to uniform exposure to white light at 500 lux for 10 seconds to expose substantially all of the silver halide emulsion. The sample used at this time was stored at 25 ° C. and 60 RH% for 7 days. Next, in the above processing steps, running processing was performed in which the type of developing agent was changed as shown in Tables 7 and 8.
Further, the same processing was performed by adding 2.0 g / liter of sodium sulfite to the color developer after running. The processed sample was cut into a length of 50 cm, and the transmission density of magenta was measured to obtain an average value. Maximum color density fluctuation (ΔD_max  ) Was evaluated according to the following formula.
ΔD_max  = (Magenta concentration in running solution)-(Magenta concentration when sodium sulfite is added to running solution)
This value is preferably as close to 0 as there is no processing fluctuation.
Tables 6, 7 and 8 collectively show the evaluation results.
[0053]
[Table 6]

[0054]
[Table 7]

[0055]
[Table 8]

[0056]
According to Table 6, by using the solid dispersion of the dye of the general formula (I) according to the present invention, a conventional resin bag can be obtained without depending on the storage conditions of the photosensitive material and without producing a black waste liquid containing carbon black. It can be seen that a sample having a sharpness equal to or higher than that of the sample is obtained. It can also be seen that a sample having satisfactory sharpness under both storage conditions cannot be obtained with a comparative dye outside the present invention.
Further, according to Tables 7 and 8, when the solid dispersion of the dye according to the present invention is used, the occurrence of processing unevenness varies greatly depending on the type of the developing agent. It turns out that it is small.
Accordingly, it can be seen that it is essential to use the solid dispersion of the dye according to the present invention and the developing agent according to the present invention in order to keep the sharpness high and suppress the processing unevenness.
[0057]
Example 2
In the sample 104 of Example 1, the ratio of the silver chlorobromide emulsion to the magenta coupler (Ag / Cp ratio) and the total gelatin coating amount in the fifth magenta color-forming green sensitive emulsion layer were changed as shown in Table 9. 201-217 were produced.
When changing the ratio of silver chlorobromide emulsion to magenta coupler (Ag / Cp ratio), the absolute value of the coating silver amount was adjusted so that the maximum color density was constant. Further, Cpd-3 was changed at the same ratio as the silver chlorobromide emulsion was increased and decreased, and the solvents (Solv-1) and (Cpd-6) were changed at the same ratio as the magenta coupler was increased and decreased. When changing the total gelatin coating amount, the gelatin of each photographic constituent layer was increased or decreased at the same rate.
[0058]
Next, the following evaluation was performed using these samples.
[0059]
(Evaluation of gradation fluctuation)
Each sample was coated and stored at 25 ° C. and 60% RH for 7 days and at 40 ° C. and 70% RH for 30 days, and the gradation variation was evaluated according to the storage conditions. Each sample was subjected to 1/100 second gradation exposure at 20,000 lux using a sensitometer (FWH type manufactured by Fuji Photo Film, light source color temperature 3200K) through a green filter. The treatment was performed with the running liquid used. The magenta transmission density of the treated sample was measured, and the gradation change (γ40 ° C./γ25° C.) was calculated. The value γ40 ° C./γ25° C. is preferably as close to 1 as the change in gradation is small.
Here, γ is the gradation of the high density portion when 0.5 high illuminance exposure is given on a log scale from the point of giving density 2.0 for each of the sample stored at 25 ° C. and the sample stored at 40 ° C. The following formula was used.
[0060]
γ = {(density at a point of 0.5 high illuminance on the log scale from the point giving density 2.0) −2.0} /0.5
[0061]
(Evaluation of uneven color density during processing)
It carried out according to Example 1.
[0062]
Table 9 summarizes these evaluations.
[0063]
[Table 9]

[0064]
According to Table 9, the gradation fluctuation due to the difference in the storage conditions becomes worse when the Ag / Cp ratio is high, and becomes extremely worse at 10.0 or more. On the other hand, the color density unevenness during processing tends to deteriorate when the Ag / Cp ratio is low, and is greatly deteriorated at 3.0 or less. As described above, it can be understood that the Ag / Cp ratio of the present invention is indispensable in order to satisfy both the gradation fluctuation and the color density unevenness. The total gelatin coating amount is 14 g / m.²  Processing unevenness is reduced in the following, especially 8 to 13 g / m.²  It can be seen that the range of is preferable.
[0065]
Example 3
Using the sample 104 of Example 1, the pre-bass solution and the color developing agent type of Example 1 were changed as follows, processing was performed according to Example 1, and processing unevenness was evaluated.
Table 10 shows the evaluation results.
[0066]
[Table 10]

[0067]
According to Table 10, the processing unevenness generated using the solid dispersion of the dye of the present invention was improved when the developing agent of the present invention was used, and when a pre-bath bath having a pH of 8.0 or more was used. Furthermore, it turns out that the effect is remarkable.
[0068]
【The invention's effect】
According to the color image forming method of the present invention, there is no deterioration in sharpness or gradation change under high humidity, and the change in color density due to the composition of the processing liquid is small, and the occurrence of processing unevenness is also suppressed. Furthermore, according to the color image forming method of the present invention, black waste liquid is not generated during photographic processing, and the burden of waste liquid processing can be reduced.

Claims (12)

A processing solution containing an aromatic primary amine developing agent after imagewise exposing a silver halide color photographic light-sensitive material containing a solid fine particle dispersion of yellow, magenta, cyan dye-forming coupler and dye in a photographic constituent layer In the color image forming method in which color development processing is carried out at a ratio of silver to magenta coupler in the magenta color-forming silver halide emulsion layer of the silver halide color photographic light-sensitive material is 3.5 or more and 9.0 or less in terms of mole. A color image forming method, wherein the dye is a compound represented by the following general formula (I), and the aromatic primary amine developing agent is represented by the following general formula (II).

In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents an alkyl group, an aryl group, a hydrogen atom, an alkoxycarbonyl group, an acylamino group, a sulfonamido group, or a carbamoyl group. Each of which may be further substituted. However, the substituted alkyl group does not include a sulfolane-3-yl group.

In general formula (II), R ₅ represents a hydrogen atom or an alkyl group, and R ₆ and R ₇ each independently represents an unsubstituted alkyl group or an alkyl group substituted with an alkoxyl group. 2. A pre-bath treatment with a processing solution having a pH of 8.0 or more is carried out after imagewise exposure and before color development with a processing solution containing an aromatic primary amine developing agent. Color image forming method. In the general formula (I), R ₃ , R ₄ The color image forming method according to claim 1, wherein at least one of them is a phenyl group substituted at the para position with a carboxyl group. General formula ( II ) R ₅ The color image forming method according to claim 1, wherein is an alkyl group. General formula ( II ) R ₅ The color image forming method according to claim 1, wherein is a methyl group. General formula ( II ) R ₆ And R ₇ 6. The color image forming method according to claim 4, wherein both are unsubstituted alkyl groups. The color image forming method according to claim 1, wherein the support is a transparent support. The amount of silver applied is 1.0 g / m ² 2.0 g / m ² The color image forming method according to claim 1, wherein: Gelatin coating amount is 6.5 g / m ² 14.0 g / m ² The color image forming method according to claim 1, wherein the color image forming method is as follows. 10. The color image forming method according to claim 1, wherein the silver halide color photographic light-sensitive material is a color positive film for movies. A hydrophilic colloid layer containing the solid dispersion of the dye is coated on a transparent support, and a yellow color developing silver halide emulsion layer, a magenta color developing silver halide emulsion layer, and a cyan color forming halogen are provided on the side farther from the support. The color image forming method according to any one of claims 1 to 10, wherein a silver halide emulsion layer is provided. The color image forming method according to any one of claims 1 to 11, wherein a blue color-sensitive layer, a red color-sensitive layer, and a green color-sensitive layer are disposed in this order from the support side.