JP2004205573A - Silver halide color photosensitive material and developing processing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photosensitive material having superior color reproducibility of yellow particularly such color reproducibility that its hue is made very close to that of a target image without incurring deterioration of lightness and saturation, and to provide a processing method for the same. <P>SOLUTION: The silver halide color photosensitive material has at least one silver halide emulsion layer on a support. At least one coupler represented by formula (1) is contained in the silver halide emulsion layer, wherein L represents -N(R<SB>5</SB>)C(=O)-, -C(=O)N(R<SB>5</SB>)-, -N(R<SB>5</SB>)S(=O)<SB>2</SB>-, -S(=O)<SB>2</SB>N(R<SB>5</SB>)-, -N(R<SB>5</SB>)S(=O)-, -S(=O)N(R<SB>5</SB>)-, -C(=O)O-, -OC(=O)- or the like. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００５０】
【化５】

【００５１】
【化６】

【００５２】
【化７】

【００５３】
【化８】

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【化９】

【００５５】
【化１０】

【００５６】
【化１１】

【００５７】
【化１２】

【００５８】
本発明の感光材料に用いられるイエローカプラーは、特開平１０−１８６６０１号、あるいは特開平５−１１４１６号等に記載の方法に準じて合成することができる。
【００５９】
次に、一般式（Ｗ）で表される化合物について説明する。
一般式（Ｗ）で表される化合物におけるＲ₁₁、Ｒ₁₂で表される置換基としては特に制限はないが、一般式（１）におけるＲ₄で表される置換基と同様の基を挙げることができる。Ｒ₁₁、Ｒ₁₂として好ましくはアリール基、アルキル基であり、好ましくはアルキル基である。好ましいアルキル基としては炭素数１〜１６，更に好ましくは１〜８、特に好ましくは１〜４の置換、もしくは無置換のアルキル基である。置換基としてはアルコキシ基、スルホン酸基、エチレンオキシ基などが挙げられる。Ｒ₁₁、Ｒ₁₂で表されるアルキル基としては具体的には、メチル基、プロピル基、ｉｓｏ−プロピル基、オクチル基、３−ヒドロキシプロピル基、２−スルホエチル基、２−（２−ヒドロキシエトキシ）エチル基等が挙げられる。Ｒ₁₁，Ｒ₁₂として特に好ましくは水素原子、２−ヒドロキシエチル基、２−スルホエチル基などである。
【００６０】
一般式（Ｗ）で表される化合物におけるＲ₁₃、Ｒ₁₄で表される置換もしくは無置換のアルキル基としては、Ｒ₁₁、Ｒ₁₂と同様のものを好ましく用いることができる。
【００６１】
一般式（Ｗ）で表される化合物におけるＲ₁₅、Ｒ₁₆で表される置換基は前記一般式（Ｗ−Ｒ）で表され、一般式（Ｗ−Ｒ）中のＡは水素原子、ヒドロキシル基、ヒドロキシメチル基、２−ヒドロキシエチル基、１−ヒドロキシエチル基、３−ヒドロキシプロピル基、２−ヒドロキシプロピル基、１−ヒドロキシプロピル基のいずれかを表し、４つのＡは同一でも異なっていてもよい。Ｒ₁₅及びＲ₁₆で表される基としては、ヒドロキシル基を少なくとも一つ以上含有することが好ましい。
【００６２】
一般式（Ｗ）で表される化合物におけるＲ₁₁及びＲ₁₂がいずれも、同時に水素原子であるか、またはＲ₁₃及びＲ₁₄がいずれも、同時に水素原子であることが好ましく、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃及びＲ₁₄がいずれも、同時に水素原子であることが特に好ましい。
【００６３】
一般式（Ｗ）で表される化合物におけるＲｗで表される基は、前記一般式（Ｗ−Ｒ）で表される基、または−ＣＨ₂ＣＨ₂ＳＯ₃Ｍである。Ｒｗで表される基として好ましくは、−ＣＨ₂ＣＨ₂ＳＯ₃Ｍである。
【００６４】
一般式（Ｗ）で表される化合物におけるＭで表されるアルカリ金属原子、アルカリ土類金属原子、の中で特に好ましいのはＮａ、及びＫである。アンモニウム基としてはテトラアルキルアンモニウム基が好ましく、例えばテトラブチルアンモニウムが挙げられる。
【００６５】
一般式（Ｗ）で表される化合物におけるＭとして最も好ましくは、Ｎａ、及びＫである。
【００６６】
次に、本発明に関わる化合物である前記一般式（Ｗ）で表される化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。
【００６７】
【化１３】

【００６８】
【化１４】

【００６９】
【化１５】

【００７０】
【化１６】

【００７１】
【化１７】

【００７２】
【化１８】

【００７３】
【化１９】

【００７４】
【化２０】

【００７５】
本発明の感光材料の処理方法に用いられる一般式（Ｗ）で表される化合物は、特開２００１−２８１８２３号に記載の方法に準じて合成することができる。
【００７６】
本発明の感光材料に用いられるイエローカプラーは通常ハロゲン化銀１モル当り１×１０^-3モル〜１モル、好ましくは１×１０^-2モル〜８×１０^-1モルの範囲で用いることができる。また本発明のカプラーは他の種類のカプラーと併用することもできる。本発明の感光材料に用いられるカプラーには、通常の色素形成カプラーにて用いられる方法及び技術が、同様に適用される。
【００７７】
本発明に係る感光材料に用いられるマゼンタカプラーとしては、特開平８−３２８２１０号２ページ記載の一般式Ｍ−ＩもしくはＭ−IIで示される化合物が好ましい。好ましい化合物の具体例としては、同号６ページから１６ページに記載のＭＣＰ−１〜ＭＣＰ−４１を挙げることができる。更に他の具体例としては欧州公開特許０２７３７１２号６〜２１頁に記載されている化合物Ｍ−１〜Ｍ−６１及び同０２３５９１３号３６〜９２頁に記載されている化合物１〜２２３の中の上述の代表的具体例以外のものがある。
【００７８】
該マゼンタカプラーは他の種類のマゼンタカプラーと併用することもでき、通常ハロゲン化銀１モル当たり１×１０^-3モル〜１モル、好ましくは１×１０^-2モル〜８×１０^-1モルの範囲で用いることができる。
【００７９】
本発明に係る感光材料において形成されるマゼンタ画像の分光吸収のλｍａｘは５３０〜５６０ｎｍであることが好ましく、またλＬ０．２は、５８０〜６３５ｎｍであることが好ましい。λＬ０．２とは、画像色素の分光吸光度曲線において、最大吸光度が１．０である時、最大吸光度を示す波長よりも長波で、吸光度が０．２となる波長をいう。この量は画像色素の長波側の不要吸収の大きさを示す目安となる量であり、λｍａｘに近い波長であるほど不要吸収が小さく好ましいことを表す。
【００８０】
本発明に係るハロゲン化銀感光材料のマゼンタ画像形成層には、マゼンタカプラーに加えてイエローカプラーが含有されることが好ましい。本発明の感光材料のマゼンタ画像形成性層に含有させる好ましいイエローカプラーとしては、公知のピバロイルアセトアニリド型もしくはベンゾイルアセトアニリド型等のカプラーが挙げられる。本発明の感光材料のマゼンタ画像形成性層に含有させる好ましいイエローカプラーの具体例としては特開平８−３１４０７９号６〜１５ページ右欄に記載のＹＣＰ−１〜ＹＣＰ−３９で表されるカプラーが挙げられるが、もちろんこれらに限定されるものではない。
【００８１】
本発明に係る感光材料においてシアン画像形成層中に含有されるシアンカプラーとしては、公知のフェノール系、ナフトール系又はイミダゾール系、アゾール系カプラーを用いることができる。例えば、アルキル基、アシルアミノ基、或いはウレイド基などを置換したフェノール系カプラー、５−アミノナフトール骨格から形成されるナフトール系カプラー、離脱基として酸素原子を導入した２当量型ナフトール系カプラーなどが代表される。このうち好ましい化合物としては特開平６−９５２８３号１３ページ記載の一般式［Ｃ−Ｉ］、［Ｃ−II］が挙げられる。
【００８２】
アゾール系カプラーとしては特開平８−１７１１８５号２ページ記載の一般式〔Ｉ〕もしくは〔II〕で表されるピラゾロアゾール系カプラー、または特開平１１−２８２１３８号に記載の一般式（Ｉ）で表されるピロロアゾール系カプラーを挙げることができる。
【００８３】
該シアンカプラーは通常ハロゲン化銀乳剤層において、ハロゲン化銀１モル当たり１×１０^-3〜１モル、好ましくは１×１０^-2〜８×１０^-1モルの範囲で用いることができる。
【００８４】
該マゼンタ色画像、シアン色画像、及びイエロー色画像の分光吸収特性を調整するために、色調調整作用を有する化合物を添加することが好ましい。このための化合物としては、特開平６−９５２８３号２２ページ記載の一般式［ＨＢＳ−Ｉ］に記載されるリン酸エステル系化合物、［ＨＢＳ−II］で示されるホスフィンオキサイド系化合物が好ましく、より好ましくは同号２２ページ記載の一般式［ＨＢＳ−II］で示される化合物である。
【００８５】
前記マゼンタ、シアン、イエローの各カプラーには、形成された色素画像の光、熱、湿度等による褪色を防止するため褪色防止剤を併用することができる。好ましい化合物としては、特開平２−６６５４１号３ページ記載の一般式ＩおよびIIで示されるフェニルエーテル系化合物、特開平３−１７４１５０号記載の一般式IIIＢで示されるフェノール系化合物、特開平６４−９０４４５号記載の一般式Ａで示されるアミン系化合物、特開昭６２−１８２７４１号記載の一般式XII、XIII、XIV、XVで示される金属錯体が特にマゼンタ色素用として好ましい。また特開平１−１９６０４９号記載の一般式Ｉ’で示される化合物および特開平５−１１４１７号記載の一般式IIで示される化合物が特にイエロー、シアン色素用として好ましい。
【００８６】
本発明に係るハロゲン化銀感光材料に用いられるステイン防止剤やその他の有機化合物を添加するのに水中油滴型乳化分散法を用いる場合には、通常、沸点１５０℃以上の水不溶性高沸点有機溶媒に、必要に応じて低沸点及び／または水溶性有機溶媒を併用して溶解し、ゼラチン水溶液などの親水性バインダー中に界面活性剤を用いて乳化分散する。分散手段としては、撹拌機、ホモジナイザー、コロイドミル、フロージェットミキサー、超音波分散機等を用いることができる。分散後、または、分散と同時に低沸点有機溶媒を除去する工程を入れてもよい。ステイン防止剤等を溶解して分散するために用いることの出来る高沸点有機溶媒としては、トリクレジルホスフェート、トリオクチルホスフェート等のリン酸エステル類、トリオクチルホスフィンオキサイド等のホスフィンオキサイド類、特開平４−２６５，９７５号５ページ記載の（ａ−ｉ）〜（ａ−ｘ）を代表とする高級アルコール系化合物等が好ましく用いられる。また高沸点有機溶媒の誘電率としては３．５〜７．０であることが好ましい。また二種以上の高沸点有機溶媒を併用することもできる。
【００８７】
本発明に用いられるハロゲン化銀乳剤としては、９５モル％以上が塩化銀からなるハロゲン化銀乳剤が好ましく、塩化銀、塩臭化銀、塩沃臭化銀、塩沃化銀等任意のハロゲン組成を有するものが用いられる。中でも、塩化銀を９５モル％以上含有する塩臭化銀、中でも臭化銀を高濃度に含有する部分を有するハロゲン化銀乳剤が好ましく用いられ、また、表面近傍に沃化銀を０．０５〜０．５モル％含有する塩沃化銀も好ましく用いられる。臭化銀を高濃度に含有する部分を有するハロゲン化銀乳剤の、高濃度に臭化銀を含有する部分は、いわゆるコア・シェル乳剤であってもよいし、完全な層を形成せず単に部分的に組成の異なる領域が存在するだけのいわゆるエピタキシー接合した領域を形成していてもよい。臭化銀が高濃度に存在する部分は、ハロゲン化銀粒子の表面の結晶粒子の頂点に形成されることが特に好ましい。また、組成は連続的に変化してもよいし不連続に変化してもよい。
【００８８】
本発明に用いられるネガ型ハロゲン化銀乳剤には重金属イオンを含有させるのが有利である。これによっていわゆる相反則不軌が改良され、高照度露光での減感が防止されたりシャドー側での軟調化が防止されることが期待される。このような目的に用いることの出来る重金属イオンとしては、鉄、イリジウム、白金、パラジウム、ニッケル、ロジウム、オスミウム、ルテニウム、コバルト等の第８〜１０族金属や、カドミウム、亜鉛、水銀などの第１２族遷移金属や、鉛、レニウム、モリブデン、タングステン、ガリウム、クロムの各イオンを挙げることができる。中でも鉄、イリジウム、白金、ルテニウム、ガリウム、オスミウムの金属イオンが好ましい。これらの金属イオンは、塩や、錯塩の形でハロゲン化銀乳剤に添加することが出来る。前記重金属イオンが錯体を形成する場合には、その配位子としてシアン化物イオン、チオシアン酸イオン、シアン酸イオン、塩化物イオン、臭化物イオン、沃化物イオン、カルボニル、ニトロシル、アンモニア、１，２，４−トリアゾール、チアゾール等を挙げることができる。中でも、塩化物イオン、臭化物イオン等が好ましい。これらの配位子は単独であっても複数の配位子が併用されてもよい。
【００８９】
これらの金属化合物は、ハロゲン化銀乳剤粒子に含有させた時の電子トラップの深さとして特徴づけることもできる。深さが０．２ｅＶ以下の浅い電子トラップを与える化合物としては第２鉛イオンまたは、シアノ配位子を有する化合物を挙げることができ、相反則不軌特に低照度不軌を改良するのに有効である。また、深さが０．３５ｅＶ以上の深い電子トラップを与える化合物としては、ハロゲン化物イオンやニトロシル配位子を有するＩｒ、Ｒｈ、Ｒｕ化合物を挙げることができる。これらは高照度相反則不軌を改良する上で好ましく用いることが出来る。深さが０．２ｅＶ以下の浅い電子トラップを与える化合物と深さが０．３５ｅＶ以上の深い電子トラップを与える化合物を併用することも好ましい形態である。これら化合物については特開２０００−２１４５６１号４〜５ページに詳しい記載がある。
【００９０】
ハロゲン化銀乳剤に重金属イオンを含有させるためには、該重金属化合物をハロゲン化銀粒子の形成前、ハロゲン化銀粒子の形成中、ハロゲン化銀粒子の形成後の物理熟成中の各工程の任意の場所で添加すればよい。
【００９１】
重金属化合物をハロゲン化物塩と一緒に溶解して粒子形成工程の全体或いは一部にわたって連続的に添加することができる。また、あらかじめこれらの重金属化合物を含有するハロゲン化銀微粒子を形成しておいて、これを添加することによって調製することもできる。前記重金属イオンをハロゲン化銀乳剤中に添加するときの量はハロゲン化銀１モル当り１×１０^-9モル以上、１×１０^-2モル以下がより好ましく、特に１×１０^-8モル以上５×１０^-5モル以下が好ましい。
【００９２】
本発明に用いられる粒子の形状は任意のものを用いることが出来る。好ましい一つの例は、（１００）面を結晶表面として有する立方体である。また、米国特許４１８３７５６号、同４２２５６６６号、特開昭５５−２６５８９号、特公昭５５−４２７３７号や、ザ・ジャーナル・オブ・フォトグラフィック・サイエンス（Ｊ．Ｐｈｏｔｏｇｒ．Ｓｃｉ．）２１、３９（１９７３）等の文献に記載された方法等により、八面体、十四面体、十二面体等の形状を有する粒子をつくり、これを用いることもできる。さらに、双晶面を有する粒子を用いてもよい。
【００９３】
本発明に用いられる粒子は、単一の形状からなる粒子が好ましく用いられるが、単分散のハロゲン化銀乳剤を二種以上同一層に添加することが特に好ましい。
【００９４】
本発明に用いられる粒子の粒径は特に制限はないが、迅速処理性及び、感度など、他の写真性能などを考慮すると好ましくは、０．１〜１．２μｍ、更に好ましくは、０．２〜１．０μｍの範囲である。
【００９５】
この粒径は、粒子の投影面積か直径近似値を使ってこれを測定することができる。粒子が実質的に均一形状である場合は、粒径分布は直径か投影面積としてかなり正確にこれを表すことができる。
【００９６】
本発明に用いられるハロゲン化銀粒子の粒径の分布は、好ましくは変動係数が０．２２以下、更に好ましくは０．１５以下の単分散ハロゲン化銀粒子であり、特に好ましくは変動係数０．１５以下の単分散乳剤を２種以上同一層に添加することである。ここで変動係数は、粒径分布の広さを表す係数であり、次式によって定義される。
【００９７】
変動係数＝Ｓ／Ｒ
（ここに、Ｓ は粒径分布の標準偏差、Ｒ は平均粒径を表す。）
ハロゲン化銀乳剤の調製装置、方法としては、当業界において公知の種々の方法を用いることができる。
【００９８】
本発明に用いられる乳剤は、酸性法、中性法、アンモニア法の何れで得られたものであってもよい。該粒子は一時に成長させたものであってもよいし、種粒子を作った後で成長させてもよい。種粒子を作る方法と成長させる方法は同じであっても、異なってもよい。
【００９９】
また、可溶性銀塩と可溶性ハロゲン化物塩を反応させる形式としては、順混合法、逆混合法、同時混合法、それらの組合せなど、いずれでもよいが、同時混合法で得られたものが好ましい。更に同時混合法の一形式として特開昭５４−４８５２１号等に記載されているｐＡｇコントロールド・ダブルジェット法を用いることもできる。
【０１００】
また、特開昭５７−９２５２３号、同５７−９２５２４号等に記載の反応母液中に配置された添加装置から水溶性銀塩及び水溶性ハロゲン化物塩水溶液を供給する装置、ドイツ公開特許２９２１１６４号等に記載された水溶性銀塩及び水溶性ハロゲン化物塩水溶液を連続的に濃度変化して添加する装置、特公昭５６−５０１７７６号等に記載の反応器外に反応母液を取り出し、限外濾過法で濃縮することによりハロゲン化銀粒子間の距離を一定に保ちながら粒子形成を行なう装置などを用いてもよい。
【０１０１】
更に必要で有ればチオエーテル等のハロゲン化銀溶剤を用いてもよい。また、メルカプト基を有する化合物、含窒素ヘテロ環化合物または増感色素のような化合物をハロゲン化銀粒子の形成時、または、粒子形成終了の後に添加して用いてもよい。
【０１０２】
本発明に用いられるネガ型ハロゲン化銀乳剤は、金化合物を用いる増感法、カルコゲン増感剤を用いる増感法を組み合わせて用いることが出来る。カルコゲン増感剤としては、イオウ増感剤、セレン増感剤、テルル増感剤などを用いることが出来るが、イオウ増感剤が好ましい。イオウ増感剤としてはチオ硫酸塩、トリエチルチオ尿素、アリルチオカルバミドチオ尿素、アリルイソチアシアネート、シスチン、ｐ−トルエンチオスルホン酸塩、ローダニン、無機イオウ等が挙げられる。
【０１０３】
イオウ増感剤の添加量としては、適用されるハロゲン化銀乳剤の種類や期待する効果の大きさなどにより変えることが好ましいが、ハロゲン化銀１モル当たり５×１０^-10〜５×１０^-5モルの範囲、好ましくは５×１０^-8〜３×１０^-5モルの範囲が好ましい。
【０１０４】
金増感剤としては、塩化金酸、硫化金等の他各種の金錯体として添加することができる。用いられる配位子化合物としては、ジメチルローダニン、チオシアン酸、メルカプトテトラゾール、メルカプトトリアゾール等を挙げることができる。金化合物の使用量は、ハロゲン化銀乳剤の種類、使用する化合物の種類、熟成条件などによって一様ではないが、通常はハロゲン化銀１モル当たり１×１０^-4モル〜１×１０^-8モルであることが好ましい。更に好ましくは１×１０^-5モル〜１×１０^-8モルである。これらの化合物は、増感剤としてではなく、塗布液の調製段階などで種々の目的で添加することができる。
【０１０５】
本発明に用いられるネガ型ハロゲン化銀乳剤の化学増感法としては、還元増感法を用いてもよい。
【０１０６】
本発明に用いられるハロゲン化銀乳剤には、ハロゲン化銀感光材料の調製工程中に生じるカブリを防止したり、保存中の性能変動を小さくしたり、現像時に生じるカブリを防止する目的で公知のカブリ防止剤、安定剤を用いることが出来る。こうした目的に用いることのできる好ましい化合物の例として、特開平２−１４６０３６号７ページ下欄に記載された一般式（II）で表される含窒素複素環メルカプト化合物を挙げることができ、さらに好ましい具体的な化合物としては、同公報の８ページに記載の（IIａ−１）〜（IIａ−８）、（IIｂ−１）〜（IIｂ−７）の化合物や、特開２０００−２６７２３５号８ページ右欄３２〜３６行目に記載の化合物を挙げることができる。これらの化合物は、その目的に応じて、ハロゲン化銀乳剤粒子の調製工程、化学増感工程、化学増感工程の終了時、塗布液調製工程などの工程で添加される。これらの化合物の存在下に化学増感を行う場合には、ハロゲン化銀１モル当り１×１０^-5モル〜５×１０^-4モル程度の量で好ましく用いられる。化学増感終了時に添加する場合には、ハロゲン化銀１モル当り１×１０^-6モル〜１×１０^-2モル程度の量が好ましく、１×１０^-5モル〜５×１０^-3モルがより好ましい。塗布液調製工程において、ハロゲン化銀乳剤層に添加する場合には、ハロゲン化銀１モル当り１×１０^-6モル〜１×１０^-1モル程度の量が好ましく、１×１０^-5モル〜１×１０^-2モルがより好ましい。またハロゲン化銀乳剤層以外の層に添加する場合には、塗布被膜中の量が、１ｍ²当り１×１０^-9モル〜１×１０^-3モル程度の量が好ましい。
【０１０７】
本発明に用いられるハロゲン化銀乳剤には、種々の目的で他の添加剤を加えることが出来る。例えば、特開平２−１４６，０３６号に具体的に記載されているＡ−２０、Ｃ−１、Ｃ−９、Ｃ−１４、Ｃ−１５、Ｃ−１６、Ｃ−４０等のジスルフィド、ポリスルフィド化合物、Ｄ−１、Ｄ−３、Ｄ−６、Ｄ−８等のチオスルホン酸化合物、無機イオウ等を用いることが好ましい。
【０１０８】
本発明に用いられる写真感光材料には、イラジエーション防止やハレーション防止の目的で種々の波長域に吸収を有する染料を用いることができる。この目的で、公知の化合物をいずれも用いることが出来るが、特に、可視域に吸収を有する染料としては、特開平３−２５１８４０号３０８ページに記載のＡＩ−１〜１１の染料および特開平６−３７７０号記載の染料が好ましく用いられる。
【０１０９】
本発明に係るハロゲン化銀感光材料は、ハロゲン化銀乳剤層のうち最も支持体に近いハロゲン化銀乳剤層より支持体に近い側に少なくとも１層の耐拡散性化合物で着色された親水性コロイド層を有することが好ましい。着色物質としては染料またはそれ以外の有機、無機の着色物質を用いることができる。
【０１１０】
本発明に用いられるハロゲン化銀感光材料は、ハロゲン化銀乳剤層のうち最も支持体に近いハロゲン化銀乳剤層より支持体に近い側に少なくとも１層の着色された親水性コロイド層を有することが好ましく、該層に白色顔料を含有していてもよい。例えばルチル型二酸化チタン、アナターゼ型二酸化チタン、硫酸バリウム、ステアリン酸バリウム、シリカ、アルミナ、酸化ジルコニウム、カオリン等を用いることができるが、種々の理由から、中でも二酸化チタンが好ましい。白色顔料は処理液が浸透できるような例えばゼラチン等の親水性コロイドの水溶液バインダー中に分散される。白色顔料の塗布付量は好ましくは０．１ｇ／ｍ²〜５０ｇ／ｍ²の範囲であり、更に好ましくは０．２ｇ／ｍ²〜５ｇ／ｍ²の範囲である。
【０１１１】
支持体と、支持体から最も近いハロゲン化銀乳剤層との間には、白色顔料含有層の他に必要に応じて下塗り層、あるいは任意の位置に中間層等の非感光性親水性コロイド層を設けることができる。
【０１１２】
本発明に用いられるハロゲン化銀感光材料には、適宜蛍光増白効果を有する化合物や、処理後のステインを低減するような化合物を添加することが好ましい。添加する化合物としては一般式（Ｗ）で表される化合物が特に好ましく、添加する層としては特に、支持体に近い層に添加することが好ましく、また、前記白色顔料を含有する層に添加することも好ましい。
【０１１３】
本発明に係るハロゲン化銀感光材料には、４００〜９００ｎｍの波長域の特定領域に分光増感されたハロゲン化銀乳剤を含む層を有する。該ハロゲン化銀乳剤は一種または、二種以上の増感色素を組み合わせて含有する。
【０１１４】
本発明に用いられるハロゲン化銀乳剤に用いる分光増感色素としては、公知の化合物をいずれも用いることができるが、青感光性増感色素としては、特開平３−２５１８４０号２８ページに記載のＢＳ−１〜８を単独でまたは組み合わせて好ましく用いることができる。緑感光性増感色素としては、同公報２８ページに記載のＧＳ−１〜５が好ましく用いられる。赤感光性増感色素としては同公報２９ページに記載のＲＳ−１〜８が好ましく用いられる。
【０１１５】
これらの増感色素の添加時期としては、ハロゲン化銀粒子形成から化学増感終了までの任意の時期でよい。また、これらの色素の添加方法としては、水またはメタノール、エタノール、フッ素化アルコール、アセトン、ジメチルホルムアミド等の水と混和性の有機溶媒に溶解して溶液として添加してもよいし、増感色素を密度が１．０ｇ／ｍｌより大きい、水混和性溶媒の溶液または、乳化物、懸濁液として添加してもよい。
【０１１６】
増感色素の分散方法としては、高速撹拌型分散機を用いて水系中に機械的に１μｍ以下の微粒子に粉砕・分散する方法以外に、特開昭５８−１０５１４１号に記載のようにｐＨ６〜８、６０〜８０℃の条件下で水系中において機械的に１μｍ以下の微粒子に粉砕・分散する方法、特公昭６０−６４９６号に記載の表面張力を３．８×１０^-2Ｎ／ｍ以下に抑える界面活性剤の存在下に分散する方法、特開昭５０−８０８２６号に記載の実質的に水を含まず、ｐＫａが５を上回らない酸に溶解し、該溶解液を水性液に添加分散し、この分散物をハロゲン化銀乳剤に添加する方法等を用いることができる。
【０１１７】
分散に用いる分散媒としては水が好ましいが、少量の有機溶媒を含ませて溶解性を調整したり、ゼラチン等の親水性コロイドを添加して分散液の安定性を高めることもできる。
【０１１８】
分散液を調製するのに用いることのできる分散装置としては、例えば、特開平４−１２５６３１号公報第１図に記載の高速撹拌型分散機の他、ボールミル、サンドミル、超音波分散機等を挙げることができる。
【０１１９】
また、これらの分散装置を用いるに当たって、特開平４−１２５６３２号に記載のように、あらかじめ乾式粉砕などの前処理を施した後、湿式分散を行う等の方法をとってもよい。
【０１２０】
本発明に用いられるハロゲン化銀乳剤は一種または、二種以上の増感色素を組み合わせて含有してもよい。
【０１２１】
本発明に係る感光材料に用いられる写真用添加剤の分散や塗布時の表面張力調整のため用いられる界面活性剤として好ましい化合物としては、１分子中に炭素数８〜３０の疎水性基とスルホン酸基またはその塩を含有するものが挙げられる。具体的には特開昭６４−２６８５４号記載のＡ−１〜Ａ−１１が挙げられる。またアルキル基に弗素原子を置換した界面活性剤も好ましく用いられる。これらの分散液は通常ハロゲン化銀乳剤を含有する塗布液に添加されるが、分散後塗布液に添加されるまでの時間、および塗布液に添加後塗布までの時間は短いほうがよく各々１０時間以内が好ましく、３時間以内、２０分以内がより好ましい。
【０１２２】
本発明に係るハロゲン化銀感光材料には、現像主薬酸化体と反応する化合物を感光層と感光層の間の層に添加して色濁りを防止したりまたハロゲン化銀乳剤層に添加してカブリ等を改良することが好ましい。このための化合物としてはハイドロキノン誘導体が好ましく、さらに好ましくは２，５−ジ−ｔ−オクチルハイドロキノンのようなジアルキルハイドロキノンである。特に好ましい化合物は特開平４−１３３０５６号記載の一般式IIで示される化合物であり、同号１３〜１４ページ記載の化合物II−１〜II−１４および１７ページ記載の化合物１が挙げられる。
【０１２３】
本発明に係る感光材料中には紫外線吸収剤を添加してスタチックカブリを防止したり色素画像の耐光性を改良することが好ましい。好ましい紫外線吸収剤としてはベンゾトリアゾール類が挙げられ、特に好ましい化合物としては特開平１−２５０９４４号記載の一般式III−３で示される化合物、特開昭６４−６６６４６号記載の一般式IIIで示される化合物、特開昭６３−１８７２４０号記載のＵＶ−１Ｌ〜ＵＶ−２７Ｌ、特開平４−１６３３号記載の一般式Ｉで示される化合物、特開平５−１６５１４４号記載の一般式（Ｉ）、（II）で示される化合物が挙げられる。
【０１２４】
本発明に係る感光材料には、油溶性染料や顔料を含有すると白地性が改良され好ましい。油溶性染料の代表的具体例は、特開平２−８４２号８ページ〜９ページに記載の化合物１〜２７があげられる。
【０１２５】
本発明に係るハロゲン化銀感光材料には、バインダーとしてゼラチンを用いることが有利であるが、必要に応じて他のゼラチン、ゼラチン誘導体、ゼラチンと他の高分子のグラフトポリマー、ゼラチン以外のタンパク質、糖誘導体、セルロース誘導体、単一あるいは共重合体のごとき合成親水性高分子物質等の親水性コロイドも用いることができる。
【０１２６】
これらバインダーの硬膜剤としてはビニルスルホン型硬膜剤やクロロトリアジン型硬膜剤を単独または併用して使用することが好ましい。特開昭６１−２４９０５４号、同６１−２４５１５３号記載の化合物を使用することが好ましい。また写真性能や画像保存性に悪影響するカビや細菌の繁殖を防ぐためコロイド層中に特開平３−１５７６４６号記載のような防腐剤および抗カビ剤を添加することが好ましい。また感光材料または処理後の試料の表面の物性を改良するため保護層に特開平６−１１８５４３号や特開平２−７３２５０号記載の滑り剤やマット剤を添加することが好ましい。
【０１２７】
本発明に係る感光材料に用いる支持体としては、どのような材質を用いてもよく、ポリエチレンやポリエチレンテレフタレートで被覆した紙、天然パルプや合成パルプからなる紙支持体、塩化ビニルシート、白色顔料を含有してもよいポリプロピレン、ポリエチレンテレフタレート支持体、バライタ紙などを用いることができる。なかでも、原紙の両面に耐水性樹脂被覆層を有する支持体が好ましい。耐水性樹脂としてはポリエチレンやポリエチレンテレフタレートまたはそれらのコポリマーが好ましい。
【０１２８】
紙の表面に耐水性樹脂被覆層を有する支持体は、通常、５０〜３００ｇ／ｍ²の質量を有する表面の平滑なものが用いられるが、プルーフ画像を得る目的に対しては、取り扱いの感覚を印刷用紙に近づけるため、１３０ｇ／ｍ²以下の原紙が好ましく用いられ、さらに７０〜１２０ｇ／ｍ²の原紙が好ましく用いられる。
【０１２９】
本発明に用いられる支持体としては、ランダムな凹凸を有するものであっても平滑なものであっても好ましく用いることができる。
【０１３０】
支持体に用いられる白色顔料としては、無機及び／または有機の白色顔料を用いることができ、好ましくは無機の白色顔料が用いられる。例えば硫酸バリウム等のアルカリ土類金属の硫酸塩、炭酸カルシウム等のアルカリ土類金属の炭酸塩、微粉ケイ酸、合成ケイ酸塩等のシリカ類、ケイ酸カルシウム、アルミナ、アルミナ水和物、酸化チタン、酸化亜鉛、タルク、クレイ等があげられる。白色顔料は好ましくは硫酸バリウム、酸化チタンである。
【０１３１】
支持体の表面の耐水性樹脂層中に含有される白色顔料の量は、鮮鋭性を改良するうえで１３質量％以上が好ましく、さらには１５質量％が好ましい。
【０１３２】
本発明に係る紙支持体の耐水性樹脂層中の白色顔料の分散度は、特開平２−２８６４０号に記載の方法で測定することができる。この方法で測定したときに、白色顔料の分散度が前記公報に記載の変動係数として０．２０以下であることが好ましく、０．１５以下であることがより好ましい。
【０１３３】
本発明に用いられる両面に耐水性樹脂層を有する紙支持体の樹脂層は、１層であってもよいし、複数層からなってもよい。複数層とし、乳剤層と接する方に白色顔料を高濃度で含有させると鮮鋭性の向上が大きく、プルーフ用画像を形成するのに好ましい。
【０１３４】
また支持体の中心面平均粗さ（ＳＲａ）の値が０．１５μｍ以下、さらには０．１２μｍ以下であるほうが光沢性がよいという効果が得られより好ましい。
【０１３５】
本発明に用いられる写真感光材料は、必要に応じて支持体表面にコロナ放電、紫外線照射、火炎処理等を施した後、直接または下塗層（支持体表面の接着性、帯電防止性、寸度安定性、耐摩擦性、硬さ、ハレーション防止性、摩擦特性及び／またはその他の特性を向上するための１または２以上の下塗層）を介して塗布されていてもよい。
【０１３６】
ハロゲン化銀乳剤を用いた写真感光材料の塗布に際して、塗布性を向上させるために増粘剤を用いてもよい。塗布法としては２種以上の層を同時に塗布することの出来るエクストルージョンコーティング及びカーテンコーティングが特に有用である。
【０１３７】
本発明に用いられる露光装置の露光光源は、公知のものをいずれも好ましく用いることが出来るが、レーザーまたは発光ダイオード（以下ＬＥＤと表す）がより好ましく用いられる。
【０１３８】
レーザーとしては半導体レーザー（以下、ＬＤと表す）がコンパクトであること、光源の寿命が長いことから好ましく用いられる。また、ＬＤはＤＶＤ、音楽用ＣＤの光ピックアップ、ＰＯＳシステム用バーコードスキャナ等の用途や光通信等の用途に用いられており、安価であり、かつ比較的高出力のものが得られるという長所を有している。ＬＤの具体的な例としては、アルミニウム・ガリウム・インジウム・ヒ素（６５０ｎｍ）、インジウム・ガリウム・リン（〜７００ｎｍ）、ガリウム・ヒ素・リン（６１０〜９００ｎｍ）、ガリウム・アルミニウム・ヒ素（７６０〜８５０ｎｍ）等を挙げることができる。最近では、青光を発振するレーザーも開発されているが、現状では、６１０ｎｍよりも長波の光源としてＬＤを用いるのが有利である。
【０１３９】
ＳＨＧ素子を有するレーザー光源としては、ＬＤ、ＹＡＧレーザーから発振される光をＳＨＧ素子により半分の波長の光に変換して放出させるものであり、可視光が得られることから適当な光源がない緑〜青の領域の光源として用いられる。この種の光源の例としては、ＹＡＧレーザーにＳＨＧ素子を組み合わせたもの（５３２ｎｍ）等がある。
【０１４０】
ガスレーザーとしては、ヘリウム・カドミウムレーザー（約４４２ｎｍ）、アルゴンイオンレーザー（約５１４ｎｍ）、ヘリウムネオンレーザー（約５４４ｎｍ、６３３ｎｍ）等が挙げられる。
【０１４１】
ＬＥＤとしては、ＬＤと同様の組成をもつものが知られているが、青〜赤外まで種々のものが実用化されている。
【０１４２】
本発明に用いられる露光光源としては、各レーザーを単独で用いてもよいし、これらを組合せ、マルチビームとして用いてもよい。ＬＤの場合には、例えば１０個のＬＤを並べることにより１０本の光束からなるビームが得られる。一方、ヘリウムネオンレーザーのような場合、レーザーから発した光をビームセパレーターで例えば１０本の光束に分割する。
【０１４３】
露光用光源の強度変化は、ＬＤ、ＬＥＤのような場合には、個々の素子に流れる電流値を変化させる直接変調を行うことができる。ＬＤの場合には、ＡＯＭ（音響光学変調器）のような素子を用いて強度を変化させてもよい。ガスレーザーの場合には、ＡＯＭ、ＥＯＭ（電気光学変調器）等のデバイスを用いるのが一般である。
【０１４４】
光源にＬＥＤを用いる場合には、光量が弱ければ、複数の素子で同一の画素を重複して露光する方法を用いてもよい。
【０１４５】
また、これらに代わる光源として有機発光素子を用いてもよく、これらについては、例えば、特開２０００−２５８８４６号等に記載されている。
【０１４６】
本願発明において面積階調画像という言葉を用いているが、これは画像上の濃淡を個々の画素の色の濃淡で表現するのではなく、特定の濃度に発色した部分の面積の大小で表現するものであり、網点と同義と考えてよい。
【０１４７】
通常面積階調露光であればＹ、Ｍ、Ｃ、墨の発色をさせることで目的を達することもできる。より好ましくは、墨に加えてＭ、Ｃ等の単色が発色したことを識別するには、３値以上の露光量を使い分けて露光することが好ましい。印刷においては、特別な色の版を用いることがあるが、これを再現するためには、４値以上の露光量を使い分けて露光することが好ましい。
【０１４８】
レーザー光源の場合には、ビーム径は２５μｍ以下であることが好ましく、６〜２２μｍがより好ましい。６μｍより小さいと画質的には好ましいが、調整が困難であったり、処理速度が低下したりする。一方、２５μｍより大きいとムラが大きくなり、画像の鮮鋭性も劣化する。ビーム径を最適化することによってムラのない高精細の画像の書き込みを高速で行うことができる。
【０１４９】
このような光で画像を描くには、ハロゲン化銀感光材料上を光束が走査する必要があるが、感光材料を円筒状のドラムに巻き付けこれを高速に回転しながら回転方向に直角な方向に光束を動かす円筒外面走査方式をとってもよく、円筒状の窪みにハロゲン化銀感光材料を密着させて露光する円筒内面走査方式も好ましく用いることができる。多面体ミラーを高速で回転させこれによって搬送されるハロゲン化銀感光材料を搬送方向に対して直角に光束を移動して露光する平面走査方式をとってもよい。高画質であり、かつ大きな画像を得るには円筒外面走査方式がより好ましく用いられる。
【０１５０】
円筒外面走査方式での露光を行うには、ハロゲン化銀感光材料は正確に円筒状のドラムに密着されなければならない。これが的確に行われるためには、正確に位置合わせされて搬送される必要がある。本発明に用いられるハロゲン化銀感光材料は露光する側の面が外側に巻かれたものがより的確に位置合わせでき、好ましく用いることができる。同様な観点から、本発明に用いられるハロゲン化銀感光材料に用いられる支持体は適正な剛度があり、テーバー剛度で０．８〜４．０が好ましい。
【０１５１】
ドラム径は、露光するハロゲン化銀感光材料の大きさに適合させて任意に設定することができる。ドラムの回転数も任意に設定できるがレーザー光のビーム径、エネルギー強度、書き込みパターンや感光材料の感度などにより適当な回転数を選択することができる。生産性の観点からは、より高速な回転で走査露光できる方が好ましいが、具体的には１分間に２００〜３０００回転が好ましく用いられる。
【０１５２】
ドラムへのハロゲン化銀感光材料の固定方法は、機械的な手段によって固定させてもよいし、ドラム表面に吸引できる微小な穴を感光材料の大きさに応じて多数設けておき、感光材料を吸引して密着させることもできる。感光材料をドラムにできるだけ密着させることが画像ムラ等のトラブルを防ぐには重要である。
【０１５３】
本発明において用いられる芳香族一級アミン現像主薬としては、公知の化合物を用いることができる。これらの化合物の例として下記の化合物を上げることができる。
ＣＤ−１） Ｎ，Ｎ−ジエチル−ｐ−フェニレンジアミン
ＣＤ−２） ２−アミノ−５−ジエチルアミノトルエン
ＣＤ−３） ２−アミノ−５−（Ｎ−エチル−Ｎ−ラウリルアミノ）トルエン
ＣＤ−４） ４−（Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アミノ）アニリン
ＣＤ−５） ２−メチル−４−（Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アミノ）アニリン
ＣＤ−６） ４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−（メタンスルホンアミド）エチル）アニリン
ＣＤ−７） Ｎ−（２−アミノ−５−ジエチルアミノフェニルエチル）メタンスルホンアミド
ＣＤ−８） Ｎ，Ｎ−ジメチル−ｐ−フェニレンジアミン
ＣＤ−９） ４−アミノ−３−メチル−Ｎ−エチル−Ｎ−メトキシエチルアニリン
ＣＤ−１０） ４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−エトキシエチル）アニリン
ＣＤ−１１） ４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（γ−ヒドロキシプロピル）アニリン
本発明においては、上記は色現像液を任意のｐＨ域で使用できるが、迅速処理の観点からｐＨ９．５〜１３．０であることが好ましく、より好ましくはｐＨ９．８〜１２．０の範囲で用いられる。
【０１５４】
本発明に係る発色現像の処理温度は、３５℃以上、７０℃以下が好ましい。温度が高いほど短時間の処理が可能であり好ましいが、処理液の安定性からはあまり高くない方が好ましく、３７℃以上６０℃以下で処理することが好ましい。
【０１５５】
発色現像時間は、従来一般には３分３０秒程度で行われているが、本発明では４０秒以内が好ましく、さらに２５秒以内の範囲で行うことがさらに好ましい。
【０１５６】
発色現像液には、前記の発色現像主薬に加えて、既知の現像液成分化合物を添加することが出来る。通常、ｐＨ緩衝作用を有するアルカリ剤、塩化物イオン、ベンゾトリアゾール類等の現像抑制剤、保恒剤、キレート剤などが用いられる。
【０１５７】
本発明のハロゲン化銀カラー感光材料は、発色現像後、漂白処理及び定着処理を施される。漂白処理は定着処理と同時に行なってもよい。定着処理の後は、通常は水洗処理が行なわれる。また、水洗処理の代替として、安定化処理を行なってもよい。
【０１５８】
本発明のハロゲン化銀カラー感光材料の処理方法では、現像液、漂白定着液、安定化処理液のいずれにも適宜蛍光増白効果を有する化合物や、処理後のステインを低減するような化合物を添加することが好ましい。特に一般式（Ｗ）で表される化合物を現像液、漂白定着液への添加が好ましい。添加量としては、溶解可能であり、かつ目的とする効果が得られるものであれば特に制限はないが、１ｇ／Ｌ以上２０ｇ／Ｌ以下が好ましく、５ｇ／Ｌ以上１０ｇ／Ｌが特に好ましい。
【０１５９】
本発明のハロゲン化銀感光材料の現像処理に用いる現像処理装置としては、処理槽に配置されたローラーに感光材料をはさんで搬送するローラートランスポートタイプであっても、ベルトに感光材料を固定して搬送するエンドレスベルト方式であってもよいが、処理槽をスリット状に形成して、この処理槽に処理液を供給するとともに感光材料を搬送する方式や処理液を噴霧状にするスプレー方式、処理液を含浸させた担体との接触によるウエッブ方式、粘性処理液による方式なども用いることができる。大量に処理する場合には、自動現像機を用いてランニング処理されるのが、通常だがこの際、補充液の補充量は少ない程好ましく、環境適性等より最も好ましい処理形態は、補充方法として錠剤の形態で処理剤を添加することであり、公開技報９４−１６９３５に記載の方法が最も好ましい。
【０１６０】
【実施例】
以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらの態様に限定されるものではない。
【０１６１】
実施例１
片面に高密度ポリエチレンを、もう一方の面にアナターゼ型酸化チタンを１５質量％の含有量で分散して含む溶融ポリエチレンをラミネートした、平米当たりの質量が１１５ｇのポリエチレンラミネート紙反射支持体（テーバー剛度＝３．５、ＰＹ値＝２．７μｍ）上に、下記表１に示す層構成の各層を酸化チタンを含有するポリエチレン層の側に塗設し、更に裏面側にはゼラチン６．００ｇ／ｍ²、シリカマット剤０．６５ｇ／ｍ²を塗設した多層ハロゲン化銀感光材料試料番号１０１を作製した。
【０１６２】
カプラーは高沸点溶媒に溶解して超音波分散し、分散物として添加したが、この時、界面活性剤として（ＳＵ−１）を用いた。又、硬膜剤として（Ｈ−１）、（Ｈ−２）を添加した。塗布助剤としては、界面活性剤（ＳＵ−２）、（ＳＵ−３）を添加し、表面張力を調整した。また各層に（Ｆ−１）を全量が０．０４ｇ／ｍ²となるように添加した。
【０１６３】
【表１】

【０１６４】
ＳＵ−１：トリ−ｉ−プロピルナフタレンスルホン酸ナトリウム
ＳＵ−２：スルホ琥珀酸ジ（２−エチルヘキシル）・ナトリウム塩
ＳＵ−３：スルホ琥珀酸ジ（２，２，３，３，４，４，５，５−オクタフルオロペンチル）・ナトリウム塩
Ｈ−１：テトラキス（ビニルスルホニルメチル）メタン
Ｈ−２：２，４−ジクロロ−６−ヒドロキシ−ｓ−トリアジン・ナトリウム
ＨＱ−１：２，５−ジ−ｔ−オクチルハイドロキノン
ＨＱ−２：２，５−ジ（（１，１−ジメチル−４−ヘキシルオキシカルボニル）ブチル）ハイドロキノン
ＨＱ−３：２，５−ジ−ｓｅｃ−ドデシルハイドロキノンと２，５−ジ−ｓｅｃテトラデシルハイドロキノンと２−ｓｅｃ−ドデシル−５−ｓｅｃ−テトラデシルハイドロキノンの質量比１：１：２の混合物
ＳＯ−１：トリオクチルホスフィンオキサイド
ＳＯ−２：ジ（ｉ−デシル）フタレート
ＳＯ−３：オレイルアルコール
ＳＯ−４：トリクレジルホスフェート
ＰＶＰ ：ポリビニルピロリドン
【０１６５】
【化２１】

【０１６６】
【化２２】

【０１６７】
【化２３】

【０１６８】
（青感性ハロゲン化銀乳剤の調製）
４０℃に保温した２％ゼラチン水溶液１リットル中に下記（Ａ液）及び（Ｂ液）をｐＡｇ＝７．３、ｐＨ＝３．０に制御しつつ同時添加し、更に下記（Ｃ液）及び（Ｄ液）をｐＡｇ＝８．０、ｐＨ＝５．５に制御しつつ同時添加した。この時、ｐＡｇの制御は特開昭５９−４５４３７号記載の方法により行い、ｐＨの制御は硫酸又は水酸化ナトリウム水溶液を用いて行った。
（Ａ液）
塩化ナトリウム ３．４２ｇ
臭化カリウム ０．０３ｇ
水を加えて ２００ｍｌ
（Ｂ液）
硝酸銀 １０ｇ
水を加えて ２００ｍｌ
（Ｃ液）
塩化ナトリウム １０２．７ｇ
ヘキサクロロイリジウム（IV）酸カリウム ４×１０^-8モル
ヘキサシアノ鉄（II）酸カリウム ２×１０^-5モル
臭化カリウム １．０ｇ
水を加えて ６００ｍｌ
（Ｄ液）
硝酸銀 ３００ｇ
水を加えて ６００ｍｌ
添加終了後、花王アトラス社製デモールＮの５％水溶液と硫酸マグネシウムの２０％水溶液を用いて脱塩を行った後、ゼラチン水溶液と混合して平均粒径０．７１μｍ、粒径分布の変動係数０．０７、塩化銀含有率９９．５モル％の単分散立方体乳剤ＥＭＰ−１０１を得た。
【０１６９】
上記（ＥＭＰ−１０１）に対し、下記化合物を用い６０℃にて最適に化学増感を行い、Ｅｍ−Ｂ１０１を得た。
【０１７０】
チオ硫酸ナトリウム ０．８ｍｇ／モルＡｇＸ
塩化金酸 ０．５ｍｇ／モルＡｇＸ
安定剤 ＳＴＡＢ−１ ３×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−２ ３×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−３ ３×１０^-4モル／モルＡｇＸ
増感色素 ＢＳ−１ ４×１０^-4モル／モルＡｇＸ
増感色素 ＢＳ−２ １×１０^-4モル／モルＡｇＸ
臭化カリウム ０．２ｇ／モルＡｇＸ
次いでＥＭＰ−１０１の調製において、（Ａ液）と（Ｂ液）の添加時間および（Ｃ液）と（Ｄ液）の添加時間を変更した以外はＥＭＰ−１０１と同様にして平均粒径０．６４μｍ、粒径分布の変動係数０．０７、塩化銀含有率９９．５モル％の単分散立方体乳剤ＥＭＰ−１０２を得た。Ｅｍ−Ｂ１０１の調製においてＥＭＰ−１０１に代えてＥＭＰ−１０２を用いた以外同様にしてＥｍ−Ｂ１０２を得、Ｅｍ−Ｂ１０１とＥｍ−Ｂ１０２の１：１の混合物を青感性ハロゲン化銀乳剤として使用した。
（緑感性ハロゲン化銀乳剤の調製）
ＥＭＰ−１０１の調製において（Ａ液）及び（Ｂ液）、（Ｃ液）及び（Ｄ液）の添加時間を変更した以外は同様にして平均粒径０．４０μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体乳剤（ＥＭＰ−１０３）を得た。
【０１７１】
上記ＥＭＰ−１０３に対し、下記化合物を用い５５℃にて最適に化学増感を行い、Ｅｍ−Ｇ１０１を得た。
【０１７２】
チオ硫酸ナトリウム １．５ｍｇ／モルＡｇＸ
塩化金酸 １．０ｍｇ／モルＡｇＸ
安定剤 ＳＴＡＢ−１ ３×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−２ ３×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−３ ３×１０^-4モル／モルＡｇＸ
増感色素 ＧＳ−１ ２×１０^-4モル／モルＡｇＸ
増感色素 ＧＳ−２ ２×１０^-4モル／モルＡｇＸ
塩化ナトリウム ０．５ｇ／モルＡｇＸ
次いでＥＭＰ−１０３の調製において、（Ａ液）と（Ｂ液）の添加時間および（Ｃ液）と（Ｄ液）の添加時間を変更した以外はＥＭＰ−１０３と同様にして平均粒径０．５０μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体乳剤ＥＭＰ−１０４を得た。Ｅｍ−Ｇ１０１の調製においてＥＭＰ−１０３に代えてＥＭＰ−１０４を用いた以外同様にしてＥｍ−Ｇ１０２を得、Ｅｍ−Ｇ１０１とＥｍ−Ｇ１０２の１：１の混合物を緑感性ハロゲン化銀乳剤として使用した。
（赤感性ハロゲン化銀乳剤の調製）
前記ＥＭＰ−１０３に対し、下記化合物を用い６０℃にて最適に化学増感を行い、Ｅｍ−Ｒ１０１を得た。
【０１７３】
チオ硫酸ナトリウム １．８ｍｇ／モルＡｇＸ
塩化金酸 ２．０ｍｇ／モルＡｇＸ
安定剤 ＳＴＡＢ−１ ２×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−２ ２×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−３ ２×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−４ １×１０^-4モル／モルＡｇＸ
増感色素 ＲＳ−１ １×１０^-4モル／モルＡｇＸ
増感色素 ＲＳ−２ １×１０^-4モル／モルＡｇＸ
強色増感剤ＳＳ−１ ２×１０^-4モル／モルＡｇＸ
次に（Ｅｍ−Ｒ１０１）の調製において下記化合物を用いて６０℃にて最適に化学増感を行い、Ｅｍ−Ｒ１０２を得た。
【０１７４】
チオ硫酸ナトリウム １．８ｍｇ／モルＡｇＸ
塩化金酸 ２．０ｍｇ／モルＡｇＸ
安定剤 ＳＴＡＢ−１ ２×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−２ ２×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−３ ２×１０^-4モル／モルＡｇＸ
安定剤 ＳＴＡＢ−４ １×１０^-4モル／モルＡｇＸ
増感色素 ＲＳ−１ ２×１０^-4モル／モルＡｇＸ
増感色素 ＲＳ−２ ２×１０^-4モル／モルＡｇＸ
強色増感剤ＳＳ−１ ２×１０^-4モル／モルＡｇＸ
ＳＴＡＢ−１：１−フェニル−５−メルカプトテトラゾール
ＳＴＡＢ−２：１−（４−エトキシフェニル）−５−メルカプトテトラゾール
ＳＴＡＢ−３：１−（３−アセトアミドフェニル）−５−メルカプトテトラゾール
ＳＴＡＢ−４：ｐ−トルエンチオスルホン酸
Ｅｍ−Ｒ１０１とＥｍ−Ｒ１０２の１：１の混合物を赤感性ハロゲン化銀乳剤として使用した。
【０１７５】
【化２４】

【０１７６】
【化２５】

【０１７７】
【化２６】

【０１７８】
このようにして得られた試料１０１について、第７層のイエローカプラーを、表３に示すものに等モル入れ替えた試料１０２〜１１５も作製した。
【０１７９】
ここで露光方法について説明する。
（露光方法Ａ）
連続的に濃度が変化しているウエッジを介し、適当な色フィルター及びＮＤフィルターを用いてハロゲンランプを光源とする青色光で、０．５秒の露光時間による露光で、現像処理後に試料面内に白地部と最大発色濃度部が両方とも充分な面積で得られる方法。
【０１８０】
得られた試料１０１〜１１５を用いて、前記露光方法Ａで露光した。
露光後、下記に示す方法で現像処理を行った。これを処理方法（ａ）−３７とする。
【０１８１】
処理工程 処 理 温 度 時間 補充量
発色現像 ３７．０±０．３℃ １２０秒 ２００ｍｌ
漂白定着 ３７．０±０．５℃ ９０秒 １５０ｍｌ
安定化 ３０〜３４℃ ６０秒 ４００ｍｌ
乾 燥 ６０〜８０℃ ３０秒
発色現像液開始液及び補充液 開始液 補充液
トリエチレンジアミン ３．０ｇ ４．０ｇ
ジエチレングリコール ６．０ｇ ８．０ｇ
臭化カリウム ０．１５ｇ ０．２ｇ
塩化カリウム ３．５ｇ ０．２ｇ
亜硫酸カリウム ０．３ｇ ０．４ｇ
Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）
−４−アミノアニリン硫酸塩 ３．０ｇ ４．０ｇ
Ｎ，Ｎ−ジスルホエチルヒドロキシルアミン １５．０ｇ ２０．０ｇ
トリエタノールアミン ６．０ｇ ８．０ｇ
ジエチレントリアミン五酢酸ナトリウム塩 １．５ｇ ２．０ｇ
炭酸カリウム ３０ｇ ４０ｇ
水を加えて全量を１リットルとし、タンク液はｐＨ＝１０．２に、補充液はｐＨ＝１０．５に調整する。
【０１８２】
漂白定着液タンク液及び補充液
ジエチレントリアミン五酢酸第二鉄アンモニウム２水塩 ６５ｇ
ジエチレントリアミン五酢酸 ３ｇ
チオ硫酸アンモニウム（７０％水溶液） １００ｍｌ
２−アミノ−５−メルカプト−１，３，４−チアジアゾール ２．０ｇ
亜硫酸アンモニウム（４０％水溶液） ２７．５ｍｌ
水を加えて全量を１リットルとし、炭酸カリウム又は氷酢酸でｐＨ＝５．０に調整する。
【０１８３】
安定化液タンク液及び補充液
ｏ−フェニルフェノール １．０ｇ
５−クロロ−２−メチル−４−イソチアゾリン−３−オン ０．０２ｇ
２−メチル−４−イソチアゾリン−３−オン ０．０２ｇ
ジエチレングリコール １．０ｇ
蛍光増白剤（ＷＣ−２） ２．０ｇ
１−ヒドロキシエチリデン−１，１−ジホスホン酸 １．８ｇ
硫酸亜鉛 ０．５ｇ
硫酸マグネシウム・７水塩 ０．２ｇ
ＰＶＰ（ポリビニルピロリドン） １．０ｇ
アンモニア水（水酸化アンモニウム２５％水溶液） ２．５ｇ
ニトリロ三酢酸・三ナトリウム塩 １．５ｇ
水を加えて全量を１リットルとし、硫酸又はアンモニア水でｐＨ＝７．５に調整する。
【０１８４】
【化２７】

【０１８５】
ＷＣ−２：特開平９−２１１８２１号に記載の化合物
前記処理方法（ａ）−３７に対し、現像温度を３９℃としたものを、処理方法（ａ）−３９とする。
【０１８６】
露光方法Ａ、及び処理方法（ａ）−３７によって得られた色素画像をミノルタ（株）社製分光測色器ＣＭ−２０２２を用い、各々色差が最小となる濃度点において、Ｌ^*ａ^*ｂ^*の値を求め、色差ΔＥａｂ^*を計算した。色のターゲットとしては、（社）日本印刷産業機械工業会、ＩＳＯ／ＴＣ１３０国内委員会作製、Ｊａｐａｎ Ｃｏｌｏｒ色再現印刷２００１、アート紙、ＩＳＯ１２６４７パターンのＹ１００％を用いた。
【０１８７】
ＣＭ−２０２２による測色に関しては照明と受光の幾何条件はｄ−０、キセノンパルス光源を用いて測光し、２°視野、補助標準の光Ｄ５０を用いた。濃度についてはＸ−ｒｉｔｅ社製分光濃度計５０８型を用い、４５°環式照明０°受光の条件で、ＳｔａｔｕｓはＴを用いた。結果を表２に示す。
【０１８８】
【表２】

【０１８９】
【化２８】

【０１９０】
Ｙ−４：特開平１０−１８６６０１号記載のカプラーＹＩ−６
Ｙ−５：特開平５−１１４１６号記載のカプラー（４２）
表２に示す結果より明らかに本発明の感光材料では、イエローの色再現性において印刷物への近似度が高いことがわかる。アニリノ基の５位に置換した短い連結基に直接アリール基が置換したタイプの一般式（１）の化合物が優れており、特に（１）−４（試料１０５）、（１）−１０（試料１０７）、（１）−２７（試料１１３）は比較のカプラーを用いた試料に比べ、印刷物への近似度が高く、かつ優れた発色性を示している。すなわち一般式（１）のＲ₂が分岐のアルコキシ基であり、かつＲ₁がアルキル基であるものが特に好ましいことがわかる。また、Ｌで表される連結基は−ＮＨＣＯ−、−ＳＯ₂ＮＨ−が特に好ましいこともわかる。
【０１９１】
実施例２
実施例１に作製し、露光・現像処理した試料１０１から１１５について、白地部の明度を測定した。比較のカプラーＹ−１＋Ｙ−２を用いた試料１０１、及び比較のカプラーＹ−４、及びＹ−５を用いた試料１０２、及び１０３に対し、本発明のカプラーを含有する感光材料においてその白地に対する影響を同一の処理条件のもとで評価した。白地の評価としては前記Ｊａｐａｎ Ｃｏｌｏｒ色再現印刷２００１のＹ０％の点との明度の差で行った。結果を表３に示す。
【０１９２】
【表３】

【０１９３】
表３より明らかに、本発明の感光材料では、カプラーのみを新規なものとするだけでも、白地の明度が向上し、より印刷物に近似する効果があることがわかる。特に好ましいカプラーとしては、（１）−４（試料１０５）、（１）−１０（試料１０７）等が優れていることもわかる。また、（１）−２７（試料１１３）、（１）−３３（試料１１５）も優れていることがわかる。
【０１９４】
実施例３
前記処理方法（ａ）−３７に対し、安定化液中の蛍光増白剤（ＷＣ−２）を除き、発色現像液に表５に示す化合物と量を添加した処理液を用いて、試料１０１、１０２、１０５、１０９、１１１、１１４について、各々実施例２と同様の評価を行った。結果を表４に示す。
【０１９５】
【表４】

【０１９６】
表４より明らかに、本発明の感光材料では比較の感光材料に対し、いかなる処理方法においても白地の明度が印刷物に近似していることがわかる。特にカプラー（１）−４を用いた試料１０５の白地の明度が高いこともわかる。また、比較の蛍光増白剤ＷＣ−１あるいはＷＣ−２を添加した現像液で処理する処理方法（ＷＣ１）−３７、（ＷＣ１）−３７ｂあるいは（ＷＣ２）−３７、（ＷＣ２）−３７ｂよりも、一般式（Ｗ）で表される本発明の化合物を添加した処理液による処理方法が、より好ましいこともわかる。特に一般式（Ｗ）の化合物のトリアジン環上の２つのアミノ基において、一方のアミノ基の置換基がエタンスルホン酸ナトリウムであり、かつもう一方のアミノ基の置換基がポリオキシエチレン基であるものがさらに好ましく、さらに両方のアミノ基の２つの置換基のうち各々残りが、無置換すなわち水素である（Ｗ）−３がより好ましいことがわかり、試料１０５との組み合わせでより白地の明度に与える効果として顕著である。
【０１９７】
実施例４
実施例３における試料１０１、１０２、１０５、１０９、１１１、１１４を用い、Ａ２サイズの大きさで各々の試料において露光はせず、表５に示す処理方法による現像処理のみ行った。得られた試料のｂ^*値を測定した。測定はＡ２サイズの長辺を４０点、短辺を３０点に分割し、４０点×３０点＝１２００点で行い、そのバラツキを示す標準偏差を求め、白地のｂ^*の同一画像面内の安定性について評価した。結果を表５に示す。
【０１９８】
【表５】

【０１９９】
表５より明らかに、一般式（１）で表されるカプラーを用いた本発明の感光材料には比較の感光材料に対し、白地のイエロー（青）成分の大小を表すｂ^*値の面内のバラツキにおいて改善されていることがわかる。特にカプラー（１）−４を用いた試料１０５は、そのバラツキが小さく、さらに一般式（Ｗ）で表される化合物を用いた処理液による処理方法で処理した場合により効果が明確であることもわかる。一般式（Ｗ）の化合物においては特に、トリアジン環上の２つのアミノ基において、一方のアミノ基の置換基がエタンスルホン酸ナトリウムであり、かつもう一方のアミノ基の置換基がポリオキシエチレン基であるものがさらに好ましく、さらに両方のアミノ基の２つの置換基のうち各々残りが、無置換すなわち水素である（Ｗ）−３がより好ましいことがわかり、試料１０５との組み合わせでより白地の面内のバラツキの抑制が顕著である。
【０２００】
実施例５
実施例４における試料１０１、１０２、１０５、１０９、１１１、１１４を用い、Ａ２サイズの大きさで各々の試料において露光はせず、表６に示す現像温度３９℃における処理方法による現像処理のみ行った。実施例４と同様の方法で得られた試料のｂ^*値を測定し、そのバラツキを計算した。実施例４における現像温度３７℃の結果と合わせて評価した。結果を表６に示す。
【０２０１】
【表６】

【０２０２】
表６より明らかに、一般式（１）で表されるカプラーを用いた本発明の感光材料は比較の感光材料に対し、現像温度条件が変化して活性になった場合においても、その白地のイエロー（青）成分の大小を表すｂ^*値の面内のバラツキにおいて変動が少なく、極めて優れていることがわかる。特に一般式（Ｗ）で表される化合物を用いた処理液による処理方法で処理した場合により効果が明確であることもわかる。
【０２０３】
実施例６
実施例１における試料１０１から１１５を用いて、各々Ａ４サイズの大きさで、露光はせずに処理方法（ａ）−３７により現像処理した。得られた白地試料について、晴天屋外の正午頃の太陽光、３波長蛍光灯、白色蛍光灯、クリプトン型白熱電球の下で観察した。５０人の被験者により、印刷本紙（アート紙）との差を目視評価した。評価は２段階で近似しているかいないかで判断し、各々の光源下において印刷本紙と並べて観察した時、近似していると感じた人の数の割合を計算した。結果を表７に示す。
【０２０４】
【表７】

【０２０５】
表７の結果より明らかに、本発明の感光材料による白地は、印刷本紙との近似においてその光源依存性と言う点で改良がみられ、カプラー（１）−１０（試料１０７）が好ましく、また（１）−１７（試料１０８）、（１）−２７（試料１１３）も好ましいことがわかる。すなわち一般式（１）のＲ₂が分岐のアルコキシ基であり、かつＲ₁がアルキル基であるものが特に好ましいことがわかる。またＲ₃が分岐のアルコキシ基であるものも好ましいことがわかる。
【０２０６】
実施例７
前記試料１０１（比較）及び１０５（本発明）について、実施例３で用いた処理方法の一部の処理方法を用いて、実施例６と同様の評価を行った。結果を表８（試料１０１、比較）、及び表９（試料１０５、本発明）に示す。
【０２０７】
【表８】

【０２０８】
【表９】

【０２０９】
表８及び表９の結果より明らかに、本発明の感光材料を特定のトリアジニルスチルベン系化合物を添加した現像液で現像処理することにより、あらゆる光源下における白地の見え方の差が減少していることがわかる。特に一般式（Ｗ）の化合物のトリアジン環上の２つのアミノ基において、一方のアミノ基の置換基がエタンスルホン酸ナトリウムであり、かつもう一方のアミノ基の置換基がポリオキシエチレン基であるものがさらに好ましく、さらに両方のアミノ基の２つの置換基のうち各々残りが、無置換すなわち水素である（Ｗ）−３がより好ましいことがわかる。
【０２１０】
実施例８
前記試料１０１及び１０５、１１１について、第１層に化合物ＷＣ−２及び（Ｗ）−３を各々０．２ｇ／ｍ²添加した試料２０１、３０１、２０５、３０５、２１１、３１１を作製した。試料１０１、１０５、１１１、２０１、２０５、２１１、３０１、３０５、３１１について、各々Ａ４サイズの大きさで、露光はせずに前記処理方法（ａ）−３７で処理した。実施例５と同様の評価を行った。結果を表１０に示す。
【０２１１】
【表１０】

【０２１２】
表１０より明らかに、一般式（１）で表されるカプラーを含有する感光材料中において、蛍光増白効果を有する化合物を感光材料に含有させることにより、出力される白地がさらにあらゆる光源下において見え方の差がさらに減少することがわかる。さらには一般式（Ｗ）で表される化合物を含有することが、より好ましいこともわかる。試料３０５と３１１を比較することにより、特に好ましくは一般式（１）で表される化合物のＲ₁がアルキル基である場合であることもわかる。
【０２１３】
実施例９
前記試料１０１及び１０５、１１０について、第１層に化合物ＷＣ−２及び（Ｗ）−３を各々０．２ｇ／ｍ²添加した試料２０１、３０１、２０５、３０５、２１０、３１０を作製した。試料１０１、１０５、１１０、２０１、２０５、２１０、３０１、３０５、３１０について、各々Ａ４サイズの大きさで、露光はせずに前記処理方法（ＷＣ２）−３７、（Ｗ３）−３７、（Ｗ２７）−３７により処理した後、実施例７と同様の評価を行った。結果を表１１、表１２及び表１３に示す。
【０２１４】
【表１１】

【０２１５】
【表１２】

【０２１６】
【表１３】

【０２１７】
表１１から表１３より明らかに、一般式（１）で表されるカプラーを含有する本発明の感光材料に、蛍光増白効果を有する化合物を感光材料に含有させ、さらに蛍光増白効果を有する化合物を添加した発色現像液による処理方法により処理することにより、さらに出力される白地の光源による見え方の差が減少していることがわかる。特に、一般式（１）で表されるカプラーを含有する本発明の感光材料が一般式（Ｗ）で表される化合物を含有し、更に一般式（Ｗ）で表される化合物を添加した発色現像液による処理方法により処理することにより、大幅に出力される白地の光源による見え方の差が減少していることがわかる。
【０２１８】
また一般式（１）で表されるカプラーとしては、Ｒ₁がアルキル基であることがより好ましいこともわかる。
【０２１９】
【発明の効果】
本発明の構成により、優れたイエローの色再現性、特に明度、彩度の低下を招くことなく色相が目標とする画像に極めて近似した色再現性を有するハロゲン化銀カラー感光材料を提供することができた。さらには明度が高く、同一面内のバラツキが少なく、いかなる光源下においても同様に観察され、印刷本紙との見え方において乖離の少ない優れた白地が再現されるハロゲン化銀カラー感光材料の処理方法を提供することができた。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention improves the color reproduction of yellow in a silver halide color light-sensitive material, provides an image very similar to printing, and stably realizes this. Furthermore, the present invention provides an excellent white background which is high in brightness, approximates to printing paper, and is similarly observed under any light source, and provides a color proof compatible with yellow color reproducibility.
[0002]
[Prior art]
Silver halide color light-sensitive materials have high sensitivity, excellent color reproducibility, and are suitable for continuous processing, so they are finished in the middle of printing not only in the field of photography but also in the field of printing. Has become widely used in the field of so-called proofs for checking the state of printed matter.
[0003]
In the field of proofing, an image edited on a computer is output to a printing film, and the developed film is appropriately exposed and separated and exposed to light to produce yellow (Y), magenta (M), and cyan (C). By forming an image and forming an image of the final printed matter on color photographic paper, it has been performed to determine the suitability of the layout and color of the final printed matter.
[0004]
Recently, a method of directly outputting an image edited on a computer to a printing plate has gradually become widespread. In such a case, it is desired to obtain a color image directly from the data on the computer without using a film. In rare cases, a system using a silver halide photosensitive material enables high-quality image formation such as accurate dot image formation due to excellent sharpness, etc., but also allows continuous processing as described above. In addition, since images can be simultaneously written in a plurality of color image forming units, high productivity can be realized.
[0005]
A system that forms an area gradation image based on digital data divides a halftone dot into smaller units (here, these are expressed as pixels), and exposes the pixels with an appropriate exposure amount to form an aggregate. It is possible to reproduce halftone dots. As a simple example, if one halftone dot is composed of 100 pixels, 50% of the halftone dots are formed by exposing 50 pixels so that they can be developed. can do.
[0006]
Actually, the coloring density and the area of the coloring region change depending on the exposure amount, the exposure beam diameter, and the like, and the dot% actually measured using the densitometer differs from the number of exposed pixels. In practice, after setting the exposure amount and beam diameter to appropriate areas, the number of pixels to be exposed is appropriately changed, and the work of finely adjusting the exposure amount is repeated. The conditions will be adjusted so that the dot gain is reproduced.
[0007]
In addition to the technical development of an exposure system using such silver halide color light-sensitive materials, various efforts have been made over the years to bring the color reproduction obtained from silver halide color light-sensitive materials as close as possible to printed matter. Was. In particular, the demand for the color development and color reproduction technology of yellow is high, and the conventionally used acylacetoanilide type yellow coupler has a sharp tone on the long-wave side of the spectral spectrum of the coloring dye, and has a color tone with many reddish components. It was pointed out that there was a large deviation from the color tone of the printed matter. Further, Japanese Patent Application Laid-Open No. 2002-122969 proposes to apply a commonly used color developing agent for an ornamental color photographic system to a color proofing application, but the reddishness is further increased due to the properties of the compound. In addition, the color reproducibility of yellow is deteriorated. Furthermore, in order to adjust the hue, a technique of adding a coupler having a different hue from yellow, which develops an image-like color in the yellow color-forming layer, has been disclosed, but an essential improvement means for reducing both lightness and chroma. Nevertheless, improvements were still desired.
[0008]
On the other hand, a yellow coupler for silver halide color photography having a specific structure has been proposed. For example, an acylacetanilide-type yellow coupler having a characteristic acyl moiety (see, for example, Patent Document 2) and a malondiamide-type yellow coupler (see, for example, Patent Documents 1 and 6) are known. For the purpose of improving reproducibility, light fastness and the like, an acylacetanilide type in which the 2-position substituent of the anilide moiety has a characteristic (for example, see Patent Document 3) has been proposed. In particular, there is a proposal that when used together with a specific high-boiling organic solvent, it can be preferably applied to a silver halide color photosensitive material for color proofing (for example, see Patent Document 2).
[0009]
On the other hand, in order to prevent the white background of the silver halide color light-sensitive material after the development processing from being stained, a technique of adding a fluorescent brightener to the light-sensitive material or the processing solution is known. A silver halide emulsion color-sensitized with a specific carbocyanine dye having a condensed oxazole ring as a basic mother nucleus and a silver halide photosensitive material containing a specific surfactant are used as 4,4'-diaminostilbene disulfonic acid There has been proposed a method for processing a silver halide color photographic light-sensitive material which undergoes color development in the presence of a derivative fluorescent whitening agent, and discloses that this can reduce contamination caused by the remaining sensitizing dye ( For example, see Patent Document 4). However, it is known that the remaining of a coloring substance such as a sensitizing dye also changes depending on the structure of the sensitizing dye and the characteristics of the oil phase material used in the color photographic material. In fact, according to the study of the present inventors, when a yellow coupler represented by the general formula (1) of the present invention which gives a yellow color reproduction very similar to a printed matter is used, a white background which is an uncolored portion is removed. Although it provides superior effects compared to conventional compounds, residual color contamination still remains due to simple cyanine dyes having a fused thiazole nucleus, fused oxazole nuclei, fused imidazole nuclei, and carbocyanine dyes having a fused thiazole nucleus. It turned out to be. It has also been found that these compounds cannot be improved by the compounds described in the above publication.
[0010]
In addition, for the purpose of improving the precipitation property in the processing solution and reducing the white background contamination, it has been proposed to add a triazinylstilbene compound having a specific substituent on the triazine ring to the processing solution. (For example, see Patent Document 5). As a result of intensive studies, the inventors of the present invention have found that, when employing the yellow coupler of the general formula (1) having a specific structure, a treatment containing a triazinylstilbene-based compound described in the same item having the specific substituent and described above. It was found that the residual color of the above-mentioned sensitizing dye was significantly improved when treated with the solution, and an excellent white background which was extremely high in brightness and similarly observed under any light source was obtained. That is, the present inventors have found that it is possible to provide a photosensitive material and a processing method for the photosensitive material, which can achieve both the color reproducibility of a yellow image and an excellent white background. Furthermore, they have found that the same effect can be obtained by adding the triazinylstilbene compound having a specific substituent to a light-sensitive material. It has been found that a further effect can be obtained by adding the above compound and treating with a treating solution containing the same compound. A light-sensitive material containing a yellow coupler having a specific structure represented by the general formula (1) or a light-sensitive material containing a compound represented by the general formula (W) is replaced with a compound represented by the general formula (W). The treatment with the treatment liquid to be added is not described in any prior art documents including the aforementioned prior art documents.
[0011]
[Patent Document 1]
JP-A-5-11416
[0012]
[Patent Document 2]
JP-A-8-29932
[0013]
[Patent Document 3]
JP-A-10-186601
[0014]
[Patent Document 4]
JP-A-59-72444
[0015]
[Patent Document 5]
JP 2001-281823 A
[0016]
[Patent Document 6]
JP-A-2002-296638
[0017]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a silver halide color light-sensitive material having excellent color reproducibility of yellow, in particular, color reproducibility extremely close to a target image with a hue without lowering of lightness and chroma. It is in. Another object of the present invention is to provide a method for processing a silver halide color light-sensitive material which has high brightness and reproduces an excellent white background which is also observed under any light source.
[0018]
[Means for Solving the Problems]
The above object of the present invention can be achieved by the following configurations.
[0019]
(1) In a silver halide color photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer contains at least one coupler represented by the formula (1). Silver halide color light-sensitive material.
[0020]
(2) In the compound represented by the general formula (1), R ₁ Is a substituted or unsubstituted aliphatic group; _Two Is an alkoxy group or an aryloxy group, and the divalent linking group represented by L is -N (R _Five ) C (= O)-, -C (= O) N (R _Five )-, -N (R _Five ) S (= O) _Two -, -S (= O) _Two N (R _Five (1) The silver halide color light-sensitive material as described in (1), which is selected from any of-, -C (= O) O- and -OC (= O)-.
[0021]
(3) In the compound represented by the general formula (1), R _Three (1) or (2), wherein the group represented by is an alkoxy group, an aryloxy group, or a halogen atom, and the group represented by X is a group which is eliminated by a nitrogen atom. Silver halide color photosensitive material.
[0022]
(4) The silver halide according to (1), (2) or (3), wherein the compound represented by the general formula (W) is contained in any one of layers constituting the photosensitive material. Color photosensitive material.
[0023]
(5) Processing the silver halide color light-sensitive material according to any one of the above (1) to (4) with a processing solution containing at least one compound represented by the general formula (W). Characteristic processing method of silver halide color light-sensitive material.
[0024]
(6) In the compound represented by the general formula (W) contained in the treatment liquid, ₁₁ And R ₁₂ Any of the substituents represented by is a hydrogen atom; ₁₃ And R ₁₄ 6. The method according to claim 5, wherein all of the substituents represented by are hydrogen atoms.
[0025]
Hereinafter, the present invention will be described in more detail.
First, the coupler represented by the general formula (1) will be described.
[0026]
R in the compound represented by the general formula (1) ₁ Among the groups represented by, examples of the substituted or unsubstituted aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group. Specific examples include an iso-propyl machine, a t-butyl group, a neopentyl group, a trifluoromethyl group, a pentafluoroethyl group, a cyclohexyl group, a cyclopropyl group, and an adamantyl group. R ₁ The group represented by is preferably an alkyl group, and among the alkyl groups, a t-butyl group, a trifluoromethyl group and the like are preferable, and a t-butyl group is more preferable.
[0027]
Similarly R ₁ Examples of the substituted or unsubstituted aromatic group represented by are a phenyl group, a 4-methoxyphenyl group, a naphthyl group, a 2-aminonaphthyl group and the like. Similarly R ₁ Among the groups represented by, examples of the substituted or unsubstituted heterocyclic group include a pyrrolyl group, a furyl group, a benzofuryl group, a benzopyrrolyl group, a thienyl group, an imidazolyl group, an oxazolyl group, a pyrimidinyl group, and a benzimidazolyl group.
[0028]
Similarly R ₁ Examples of the alkyloxy group represented by include a methoxy group, an ethoxy group, and a pentyloxy group. Similarly R ₁ Examples of the aryloxy group represented by include a phenoxy group, a 4-chlorophenoxy group, and a naphthyloxy group.
[0029]
Similarly R ₁ Examples of the amino group represented by include a diethylamino group, a 2-ethylhexylamino group, an indazolinyl group, and a pyrazolyl group.
[0030]
R in the compound represented by the general formula (1) ₁ Of the groups represented by, are preferably an alkyl group and an aryl group, and more preferably an alkyl group. Preferred examples of the alkyl group include a t-butyl group, an adamantyl group and a cyclopropyl group, and the most preferred is a t-butyl group.
[0031]
R in the compound represented by the general formula (1) _Two The group represented by ₁ And the same as those described in the above. Further R _Two Examples of the halogen atom represented by include fluorine, chlorine, bromine, and iodine. R _Two The halogen atom represented by is preferably chlorine.
[0032]
R in the compound represented by the general formula (1) _Two Of the groups represented by, preferred are alkoxy groups and aryloxy groups, and more preferred are alkoxy groups. Preferred examples of the alkoxy group include a methoxy group, an ethoxy group, an iso-propyloxy group, a tetradecyloxy group, and a dodecyloxy group, and more preferred is an iso-propyloxy group.
[0033]
R in the compound represented by the general formula (1) _Three The group represented by _Two And the same as those described in the above.
[0034]
R in the compound represented by the general formula (1) _Three Of the groups represented by, preferred are an alkoxy group and an aryloxy group, and more preferred are an alkoxy group, an aryloxy group and a halogen atom. Preferred examples of the alkoxy group include a methoxy group, an ethoxy group, an iso-propyloxy group, a tetradecyloxy group, and a dodecyloxy group, and more preferred are a methoxy group and an iso-propyloxy group. R _Three Preferably, the aryloxy group represented by is a phenoxy group, a 4-methoxyphenyloxy group, or the like. R _Three The halogen atom represented by preferably represents fluorine, chlorine and the like, and is more preferably chlorine.
[0035]
R in the compound represented by the general formula (1) _Four As the group represented by, any group can be substituted as long as it can be substituted on a benzene ring, and typical examples include, for example, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc. And a halogen atom, cycloalkenyl, alkynyl, heterocyclic ring, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, Carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thiou Id, carboxy, hydroxy, mercapto, nitro, each group such as sulfo, spiro compound residue, bridged hydrocarbon compound residue and the like are also mentioned. These groups may further have a substituent.
[0036]
n represents an integer of 0 to 4, and when n is 2 to 4, a plurality of R _Four May be the same or different, and may combine with each other to form a ring.
[0037]
The divalent linking group represented by L in the compound represented by the general formula (1) includes -N (R _Five ) CO-, -CON (R _Five )-, -N (R _Five ) SO _Two -, -SO _Two N (R _Five )-, -N (R _Five ) SO-, -SON (R _Five )-, -COO-, -OCO-, -OP (= O) (O) _Two -, -N (R _Five ) P (= O) (O) _Two Represents a group selected from any of the following.
[0038]
The divalent linking group represented by L is preferably -N (R _Five ) CO-, -CON (R _Five )-, -N (R _Five ) SO _Two -, -SO _Two N (R _Five )-, -C (= O) O- and -OC (= O)-, and more preferably -N (R _Five ) CO-, -N (R _Five ) SO _Two -.
[0039]
R in the linking group represented by L _Five Represents a hydrogen atom or a substituent; _Five Examples of the substituent represented by include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like, and in addition, a halogen atom, cycloalkenyl, alkynyl, heterocyclic, Sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino , Aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxy, hydroxy, mercapto, nitro, sulfo, etc. A spiro compound residue, bridged hydrocarbon compound residue and the like are also mentioned. These groups may further have a substituent.
[0040]
R _Five The substituent represented by is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group. Preferred examples of the alkyl group include an ethyl group, a 2-ethylhexyl group, a 2-carboxyethyl group, and a 2-hydroxyethyl group.
[0041]
The linking group represented by L in the compound represented by the general formula (1) is -SO _Two When NH-, R ₁ Is not an amino group.
[0042]
An atom represented by X in the compound represented by the general formula (1), which is eliminated by coupling with an oxidized form of a color developing agent, as a group which is eliminated by a nitrogen atom, and which is eliminated by an oxygen atom Groups, groups capable of leaving with a sulfur atom, halogen atoms, hydrogen atoms and the like. Examples of the group leaving at a nitrogen atom include succinimide, phthalimide, pyrrole, pyrazole, 1,2,4-triazole, tetrazole, benzotriazole, imidazoline-2,4-dione, oxazolidin-2,4-dione, indole, Examples include a heterocyclic group such as benzopyrazole, 2-pyridone, and 2-pyrimidone; a carbonamide group such as a trifluoroacetamide group; a sulfonamide group such as a methanesulfonamide group; and an arylazo group such as a naphthylazo group.
[0043]
The group capable of leaving at a nitrogen atom is preferably a heterocyclic group, and preferably a heterocyclic group such as 1,2,4-triazole, imidazoline-2,4-dione, oxazolidine-2,4-dione. .
[0044]
Examples of the group which is eliminated by an oxygen atom include an aryloxy group such as a phenyloxy group, a 4-methoxycarbonylphenyloxy group, and a 4-arylsulfonylphenyloxy group.
[0045]
Examples of the group capable of leaving by a sulfur atom include an arylthio group such as a phenylthio group.
[0046]
Examples of the halogen atom include a chlorine atom and a bromine atom.
Further, these groups may have further substituents as long as they can be substituted. X may be a photographically useful group.
[0047]
X is preferably a group capable of leaving with a nitrogen atom or an oxygen atom, and more preferably a group capable of leaving with a nitrogen atom.
[0048]
Next, specific examples of the coupler represented by the general formula (1), which is a compound according to the present invention, are shown below, but the present invention is not limited thereto.
[0049]
Embedded image

[0050]
Embedded image

[0051]
Embedded image

[0052]
Embedded image

[0053]
Embedded image

[0054]
Embedded image

[0055]
Embedded image

[0056]
Embedded image

[0057]
Embedded image

[0058]
The yellow coupler used in the light-sensitive material of the present invention can be synthesized according to the method described in JP-A-10-186601 or JP-A-5-11416.
[0059]
Next, the compound represented by Formula (W) will be described.
R in the compound represented by the general formula (W) ₁₁ , R ₁₂ The substituent represented by is not particularly limited, but R in the general formula (1) _Four And the same groups as the substituents represented by. R ₁₁ , R ₁₂ Are preferably an aryl group and an alkyl group, and more preferably an alkyl group. Preferred alkyl groups are substituted or unsubstituted alkyl groups having 1 to 16, more preferably 1 to 8, and particularly preferably 1 to 4 carbon atoms. Examples of the substituent include an alkoxy group, a sulfonic group, and an ethyleneoxy group. R ₁₁ , R ₁₂ Specific examples of the alkyl group represented by are a methyl group, a propyl group, an iso-propyl group, an octyl group, a 3-hydroxypropyl group, a 2-sulfoethyl group, a 2- (2-hydroxyethoxy) ethyl group, and the like. No. R ₁₁ , R ₁₂ And particularly preferably a hydrogen atom, a 2-hydroxyethyl group, a 2-sulfoethyl group and the like.
[0060]
R in the compound represented by the general formula (W) ₁₃ , R ₁₄ As the substituted or unsubstituted alkyl group represented by ₁₁ , R ₁₂ The same one as described above can be preferably used.
[0061]
R in the compound represented by the general formula (W) _Fifteen , R ₁₆ Is represented by the general formula (WR), wherein A in the general formula (WR) is a hydrogen atom, a hydroxyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl Represents one of a group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 1-hydroxypropyl group, and four A's may be the same or different. R _Fifteen And R ₁₆ The group represented by preferably contains at least one hydroxyl group.
[0062]
R in the compound represented by the general formula (W) ₁₁ And R ₁₂ Are simultaneously a hydrogen atom, or R ₁₃ And R ₁₄ Is preferably a hydrogen atom at the same time, ₁₁ , R ₁₂ , R ₁₃ And R ₁₄ Is particularly preferably a hydrogen atom at the same time.
[0063]
The group represented by Rw in the compound represented by formula (W) is a group represented by formula (WR) or -CH _Two CH _Two SO _Three M. The group represented by Rw is preferably -CH _Two CH _Two SO _Three M.
[0064]
Of the alkali metal atoms and alkaline earth metal atoms represented by M in the compound represented by formula (W), particularly preferred are Na and K. As the ammonium group, a tetraalkylammonium group is preferable, and examples thereof include tetrabutylammonium.
[0065]
Most preferably, M is Na and K in the compound represented by the general formula (W).
[0066]
Next, specific examples of the compound represented by the general formula (W), which is a compound according to the present invention, are shown below, but the present invention is not limited thereto.
[0067]
Embedded image

[0068]
Embedded image

[0069]
Embedded image

[0070]
Embedded image

[0071]
Embedded image

[0072]
Embedded image

[0073]
Embedded image

[0074]
Embedded image

[0075]
The compound represented by formula (W) used in the method for processing a light-sensitive material of the present invention can be synthesized according to the method described in JP-A-2001-281823.
[0076]
The yellow coupler used in the light-sensitive material of the present invention is usually 1 × 10 5 per mol of silver halide. ^-3 Mol to 1 mol, preferably 1 × 10 ^-2 Mol ~ 8 x 10 ^-1 It can be used in the molar range. Further, the coupler of the present invention can be used in combination with other types of couplers. For the coupler used in the light-sensitive material of the present invention, the methods and techniques used for ordinary dye-forming couplers are similarly applied.
[0077]
As the magenta coupler used in the light-sensitive material according to the present invention, a compound represented by general formula MI or M-II described on page 2 of JP-A-8-328210 is preferable. Specific examples of preferred compounds include MCP-1 to MCP-41 described on pages 6 to 16 of the same publication. Still other specific examples include compounds M-1 to M-61 described in EP-A-0273712, pp. 6-21, and compounds 1-223 described in JP-A-0235913, pp. 36-92. There are other than the typical specific examples.
[0078]
The magenta coupler can be used in combination with other types of magenta couplers, and usually 1 × 10 5 per mol of silver halide. ^-3 Mol to 1 mol, preferably 1 × 10 ^-2 Mol ~ 8 x 10 ^-1 It can be used in the molar range.
[0079]
[Lambda] max of the spectral absorption of the magenta image formed in the photosensitive material according to the present invention is preferably 530 to 560 nm, and [lambda] L0.2 is preferably 580 to 635 nm. [lambda] L0.2 refers to a wavelength which is longer than the wavelength showing the maximum absorbance and has an absorbance of 0.2 when the maximum absorbance is 1.0 in the spectral absorbance curve of the image dye. This amount is an indication of the magnitude of the unnecessary absorption on the long-wave side of the image dye, and it is preferable that the wavelength is closer to λmax because the unnecessary absorption is smaller.
[0080]
The magenta image forming layer of the silver halide light-sensitive material according to the present invention preferably contains a yellow coupler in addition to the magenta coupler. Preferred yellow couplers to be contained in the magenta image-forming layer of the light-sensitive material of the present invention include known pivaloylacetanilide type and benzoylacetanilide type couplers. Specific examples of preferred yellow couplers to be contained in the magenta image-forming layer of the light-sensitive material of the present invention include couplers represented by YCP-1 to YCP-39 described in JP-A-8-314079, right column, pages 6 to 15. However, the present invention is not limited to these.
[0081]
As the cyan coupler contained in the cyan image forming layer in the photosensitive material according to the present invention, a known phenol-based, naphthol-based, imidazole-based, or azole-based coupler can be used. For example, a phenol coupler substituted with an alkyl group, an acylamino group or a ureido group, a naphthol coupler formed from a 5-aminonaphthol skeleton, a 2-equivalent naphthol coupler having an oxygen atom introduced as a leaving group, and the like are represented. You. Among these, preferred compounds include the general formulas [C-I] and [C-II] described on page 13 of JP-A-6-95283.
[0082]
As the azole coupler, a pyrazoloazole coupler represented by the general formula [I] or [II] described on page 2 of JP-A-8-171185, or a general formula (I) described in JP-A-11-282138. Examples include the pyrroloazole couplers represented.
[0083]
The cyan coupler is usually used in the silver halide emulsion layer in an amount of 1 × 10 5 per mol of silver halide. ^-3 ~ 1 mol, preferably 1 × 10 ^-2 ~ 8 × 10 ^-1 It can be used in the molar range.
[0084]
In order to adjust the spectral absorption characteristics of the magenta image, the cyan image, and the yellow image, it is preferable to add a compound having a color tone adjusting action. As the compound for this, a phosphoric ester compound represented by the general formula [HBS-I] described on page 22 of JP-A-6-95283 and a phosphine oxide compound represented by [HBS-II] are preferable. Preferred are compounds represented by the general formula [HBS-II] described on page 22 of the same publication.
[0085]
An anti-fading agent can be used in combination with each of the magenta, cyan, and yellow couplers to prevent fading of the formed dye image due to light, heat, humidity, and the like. Preferable compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, and JP-A 64-64. Amine compounds represented by the general formula A described in JP 90445 and metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP-A-62-182741 are particularly preferable for magenta dyes. Compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.
[0086]
When an oil-in-water emulsion dispersion method is used to add a stain inhibitor or other organic compound used in the silver halide light-sensitive material according to the present invention, a water-insoluble high-boiling organic compound having a boiling point of 150 ° C or higher is usually used. If necessary, a low-boiling point and / or water-soluble organic solvent is used in combination in the solvent, and the mixture is dissolved and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high-boiling organic solvents that can be used for dissolving and dispersing the stain inhibitor and the like include phosphates such as tricresyl phosphate and trioctyl phosphate; phosphine oxides such as trioctyl phosphine oxide; Higher alcohol compounds represented by (ai) to (ax) described on page 5 of 4-265,975 are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Two or more high boiling organic solvents can be used in combination.
[0087]
As the silver halide emulsion used in the present invention, a silver halide emulsion comprising 95% by mole or more of silver chloride is preferable, and any halogen such as silver chloride, silver chlorobromide, silver chloroiodobromide and silver chloroiodide can be used. Those having a composition are used. Among them, a silver chlorobromide containing 95 mol% or more of silver chloride, particularly a silver halide emulsion having a portion containing silver bromide in a high concentration is preferably used. Silver chloroiodide containing about 0.5 mol% is also preferably used. In the silver halide emulsion having a portion containing silver bromide at a high concentration, the portion containing silver bromide at a high concentration may be a so-called core-shell emulsion or may be simply formed without forming a complete layer. A so-called epitaxy junction region in which only a region having a partially different composition may exist may be formed. It is particularly preferable that the portion where silver bromide exists at a high concentration is formed at the top of crystal grains on the surface of silver halide grains. Further, the composition may change continuously or may change discontinuously.
[0088]
It is advantageous that the negative working silver halide emulsion used in the present invention contains a heavy metal ion. This is expected to improve so-called reciprocity failure and prevent desensitization in high-illuminance exposure and softening on the shadow side. Examples of heavy metal ions that can be used for such purposes include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; and twelfth metals such as cadmium, zinc, and mercury. Group transition metals and each ion of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be mentioned. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium, and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When the heavy metal ion forms a complex, its ligand is cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, 1, 2, 4-triazole, thiazole and the like can be mentioned. Among them, chloride ion, bromide ion and the like are preferable. These ligands may be used alone or in combination of a plurality of ligands.
[0089]
These metal compounds can also be characterized as the depth of electron traps when contained in silver halide emulsion grains. Examples of the compound that gives a shallow electron trap having a depth of 0.2 eV or less include a second lead ion or a compound having a cyano ligand, which is effective for improving reciprocity failure, particularly low illumination failure. . Examples of the compound that gives a deep electron trap having a depth of 0.35 eV or more include halide ions and Ir, Rh, and Ru compounds having a nitrosyl ligand. These can be preferably used for improving high-illuminance reciprocity failure. It is also a preferable embodiment to use a compound that gives a shallow electron trap with a depth of 0.2 eV or less and a compound that gives a deep electron trap with a depth of 0.35 eV or more. These compounds are described in detail in JP-A-2000-214561, pp. 4-5.
[0090]
In order to allow the silver halide emulsion to contain heavy metal ions, the heavy metal compound may be added to any of the steps during physical ripening before formation of silver halide grains, during formation of silver halide grains, and during physical ripening after formation of silver halide grains. May be added at the location.
[0091]
The heavy metal compound can be dissolved together with the halide salt and added continuously over the whole or a part of the grain formation process. Alternatively, it can be prepared by forming silver halide fine particles containing these heavy metal compounds in advance and adding them. The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 5 per mole of silver halide. ^-9 1 x 10 or more ^-2 Mol or less, more preferably 1 × 10 ^-8 5 x 10 or more ^-Five Molar or less is preferred.
[0092]
Any shape can be used for the particles used in the present invention. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973) ), Particles having an octahedral, tetradecahedral, dodecahedral or other shape can be prepared and used. Further, particles having a twin plane may be used.
[0093]
As the grains used in the present invention, grains having a single shape are preferably used, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.
[0094]
The particle size of the particles used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.2 to 1.2 μm in consideration of other photographic properties such as rapid processing property and sensitivity. １．０1.0 μm.
[0095]
This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can represent this fairly accurately as diameter or projected area.
[0096]
The distribution of the grain size of the silver halide grains used in the present invention is preferably a monodispersed silver halide grain having a variation coefficient of 0.22 or less, more preferably 0.15 or less, and particularly preferably a variation coefficient of 0.1. The addition of two or more monodispersed emulsions of 15 or less to the same layer. Here, the variation coefficient is a coefficient representing the width of the particle size distribution, and is defined by the following equation.
[0097]
Coefficient of variation = S / R
(Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.
[0098]
The emulsion used in the present invention may be obtained by any of the acidic method, neutral method, and ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method for producing the seed particles and the method for growing the seed particles may be the same or different.
[0099]
The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. Further, as one form of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.
[0100]
Further, a device for supplying a water-soluble silver salt and a water-soluble halide salt solution from an addition device arranged in a reaction mother liquor described in JP-A-57-92523, JP-A-57-92524, etc. A device for continuously changing the concentration of an aqueous solution of a water-soluble silver salt and a water-soluble halide salt described in, for example, the reaction mother liquor is taken out of the reactor described in JP-B-56-501776, and subjected to ultrafiltration. An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by a method may be used.
[0101]
If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.
[0102]
The negative-working silver halide emulsion used in the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer. As the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used, but a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, triethylthiourea, allylthiocarbamide thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur.
[0103]
The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the expected effect size, and the like. ^-Ten ~ 5 × 10 ^-Five Molar range, preferably 5 × 10 ^-8 ~ 3 × 10 ^-Five A molar range is preferred.
[0104]
As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of the gold compound used is not uniform depending on the type of the silver halide emulsion, the type of the compound to be used, the ripening conditions, etc., but usually 1 × 10 5 per mol of the silver halide. ^-Four Mol ~ 1 x 10 ^-8 Preferably it is molar. More preferably 1 × 10 ^-Five Mol ~ 1 x 10 ^-8 Is a mole. These compounds can be added not for sensitizers but for various purposes at the stage of preparing a coating solution.
[0105]
The chemical sensitization of the negative silver halide emulsion used in the present invention may be a reduction sensitization.
[0106]
The silver halide emulsion used in the present invention is known for the purpose of preventing fogging generated during the step of preparing a silver halide light-sensitive material, reducing performance fluctuation during storage, and preventing fogging generated during development. Antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such purposes include the nitrogen-containing heterocyclic mercapto compounds represented by the general formula (II) described in the lower section of page 7 of JP-A-2-14636, and more preferred. Specific examples of the compound include compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and JP-A-2000-267235, page 8 The compounds described in the right column, lines 32 to 36, can be mentioned. These compounds are added according to the purpose in the steps of preparing silver halide emulsion grains, chemical sensitizing step, finishing the chemical sensitizing step, and preparing a coating solution. When chemical sensitization is performed in the presence of these compounds, 1 × 10 5 ^-Five Mol to 5 × 10 ^-Four It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10 ^-6 Mol ~ 1 x 10 ^-2 Molar amounts are preferred, and 1 × 10 ^-Five Mol to 5 × 10 ^-3 Molar is more preferred. In the step of preparing a coating solution, when adding to the silver halide emulsion layer, 1 × 10 ^-6 Mol ~ 1 x 10 ^-1 Molar amounts are preferred, and 1 × 10 ^-Five Mol ~ 1 x 10 ^-2 Molar is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 m ^Two 1 × 10 per ^-9 Mol ~ 1 x 10 ^-3 Molar amounts are preferred.
[0107]
The silver halide emulsion used in the present invention may contain other additives for various purposes. For example, disulfides and polysulfides such as A-20, C-1, C-9, C-14, C-15, C-16 and C-40 specifically described in JP-A-2-146,036 It is preferable to use compounds, thiosulfonic acid compounds such as D-1, D-3, D-6 and D-8, inorganic sulfur and the like.
[0108]
In the photographic light-sensitive material used in the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. In particular, as dyes having absorption in the visible region, dyes of AI-1 to 11 described in JP-A-3-251840, p. The dyes described in JP-A-3770 are preferably used.
[0109]
The silver halide light-sensitive material according to the present invention comprises a hydrophilic colloid colored with at least one layer of a diffusion-resistant compound on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. It is preferred to have a layer. As the coloring substance, a dye or another organic or inorganic coloring substance can be used.
[0110]
The silver halide light-sensitive material used in the present invention has at least one colored hydrophilic colloid layer on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. And the layer may contain a white pigment. For example, rutile-type titanium dioxide, anatase-type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin, and the like can be used, but among them, titanium dioxide is preferable for various reasons. The white pigment is dispersed in an aqueous binder of a hydrophilic colloid such as gelatin, which allows the processing liquid to penetrate. The coating amount of the white pigment is preferably 0.1 g / m ^Two ~ 50g / m ^Two And more preferably 0.2 g / m ^Two ~ 5g / m ^Two Range.
[0111]
Between the support and the silver halide emulsion layer closest to the support, a non-photosensitive hydrophilic colloid layer such as an undercoat layer or an intermediate layer may be provided at any position in addition to the white pigment-containing layer, if necessary. Can be provided.
[0112]
It is preferable to add a compound having a fluorescent whitening effect or a compound that reduces stain after processing to the silver halide light-sensitive material used in the present invention. As the compound to be added, a compound represented by the general formula (W) is particularly preferable. As a layer to be added, it is particularly preferable to add the compound to a layer close to the support, and to add to the layer containing the white pigment. It is also preferred.
[0113]
The silver halide light-sensitive material according to the present invention has a layer containing a silver halide emulsion spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.
[0114]
As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compounds can be used. Examples of the blue sensitizing dye include those described in JP-A-3-251840, page 28. BS-1 to BS-8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. As the red-sensitive sensitizing dye, RS-1 to 8 described on page 29 of the same publication are preferably used.
[0115]
These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization. In addition, as a method for adding these dyes, water or an organic solvent miscible with water such as methanol, ethanol, fluorinated alcohol, acetone, and dimethylformamide may be added as a solution, or a sensitizing dye may be added. May be added as a solution, emulsion or suspension in a water-miscible solvent having a density of more than 1.0 g / ml.
[0116]
As a method of dispersing the sensitizing dye, a method of mechanically pulverizing and dispersing the sensitizing dye into fine particles of 1 μm or less in an aqueous system using a high-speed stirring type dispersing machine may be used. 8, a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system at 60 to 80 ° C., the surface tension described in JP-B-60-6496 being 3.8 × 10 ^-2 A method of dispersing in the presence of a surfactant suppressed to not more than N / m, dissolving in an acid substantially free of water and having a pKa not exceeding 5 as described in JP-A-50-80826, A method of adding and dispersing in an aqueous liquid and adding this dispersion to a silver halide emulsion can be used.
[0117]
Water is preferable as a dispersion medium used for dispersion, but the solubility may be adjusted by adding a small amount of an organic solvent, or the stability of the dispersion may be increased by adding a hydrophilic colloid such as gelatin.
[0118]
Examples of the dispersing device that can be used to prepare the dispersion include a high-speed stirring type dispersing device shown in FIG. 1 of JP-A-4-125563, a ball mill, a sand mill, an ultrasonic dispersing device, and the like. be able to.
[0119]
When using these dispersing apparatuses, a method of performing a pre-treatment such as dry pulverization in advance and then performing a wet dispersing method as described in JP-A-4-125632 may be employed.
[0120]
The silver halide emulsion used in the present invention may contain one kind or a combination of two or more kinds of sensitizing dyes.
[0121]
Preferred compounds as a surfactant used for dispersing a photographic additive used in the photosensitive material according to the present invention and adjusting a surface tension at the time of coating include a hydrophobic group having 8 to 30 carbon atoms in one molecule and a sulfone. Those containing an acid group or a salt thereof are mentioned. Specific examples include A-1 to A-11 described in JP-A-64-26854. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating after the addition to the coating solution are preferably as short as 10 hours each. Within 3 hours, more preferably within 20 minutes.
[0122]
In the silver halide light-sensitive material according to the present invention, a compound that reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity or to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, and more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17.
[0123]
It is preferable to add an ultraviolet absorber to the light-sensitive material according to the present invention to prevent static fog or improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are those represented by the general formula III-3 described in JP-A-1-250944 and those represented by the general formula III described in JP-A-64-66646. Compounds described in JP-A-63-187240, compounds represented by the general formula I described in JP-A-4-1633, compounds represented by the general formula (I) described in JP-A-5-165144, The compound shown by (II) is mentioned.
[0124]
It is preferable that the light-sensitive material according to the present invention contains an oil-soluble dye or pigment because whiteness is improved. Representative specific examples of oil-soluble dyes include compounds 1 to 27 described in JP-A-2-842, pp. 8-9.
[0125]
In the silver halide light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder.If necessary, other gelatin, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, A hydrophilic colloid such as a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.
[0126]
As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. It is preferable to use the compounds described in JP-A-61-249054 and JP-A-61-245153. It is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the light-sensitive material or the processed sample.
[0127]
As the support used in the photosensitive material according to the present invention, any material may be used, and paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, a vinyl chloride sheet, a white pigment, Polypropylene, polyethylene terephthalate support, baryta paper and the like which may be contained can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.
[0128]
A support having a water-resistant resin coating layer on the surface of paper is usually 50 to 300 g / m2. ^Two Is used. For the purpose of obtaining a proof image, in order to bring the feeling of handling closer to printing paper, 130 g / m2 is used. ^Two The following base papers are preferably used, and 70 to 120 g / m ^Two Base paper is preferably used.
[0129]
The support used in the present invention can be preferably used regardless of whether it has random irregularities or is smooth.
[0130]
As the white pigment used for the support, an inorganic and / or organic white pigment can be used, and an inorganic white pigment is preferably used. For example, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, silicas such as finely divided silica, synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.
[0131]
The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass, in order to improve sharpness.
[0132]
The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the variation coefficient described in the above-mentioned publication.
[0133]
The resin layer of the paper support having a water-resistant resin layer on both sides used in the present invention may be a single layer or a plurality of layers. It is preferable to form a plurality of layers and to include a white pigment at a high concentration in contact with the emulsion layer, because sharpness is greatly improved and a proofing image is formed.
[0134]
Further, it is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, and more preferably 0.12 μm or less, since the effect of good gloss is obtained.
[0135]
The photographic light-sensitive material used in the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion, antistatic property, It may be applied via one or more undercoat layers for improving degree stability, friction resistance, hardness, antihalation property, frictional properties and / or other properties.
[0136]
When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.
[0137]
As the exposure light source of the exposure apparatus used in the present invention, any known light source can be preferably used, but a laser or a light emitting diode (hereinafter, referred to as LED) is more preferably used.
[0138]
As a laser, a semiconductor laser (hereinafter, referred to as an LD) is preferably used because it is compact and the life of the light source is long. In addition, LDs are used for applications such as optical pickups for DVDs and music CDs, barcode scanners for POS systems, and for applications such as optical communication, and have the advantage of being inexpensive and having a relatively high output. have. Specific examples of LD include aluminum gallium indium arsenide (650 nm), indium gallium phosphorus (リ ン 700 nm), gallium arsenic phosphorus (610 to 900 nm), and gallium aluminum arsenide (760 to 850 nm). ) And the like. Recently, a laser emitting blue light has been developed, but at present, it is advantageous to use an LD as a light source having a longer wavelength than 610 nm.
[0139]
As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted into half-wavelength light by the SHG element and emitted. Since a visible light is obtained, there is no green light source. Used as a light source in the blue region. As an example of this type of light source, there is a combination of a YAG laser and an SHG element (532 nm).
[0140]
Examples of the gas laser include a helium-cadmium laser (about 442 nm), an argon ion laser (about 514 nm), and a helium neon laser (about 544 nm and 633 nm).
[0141]
As an LED, an LED having a composition similar to that of an LD is known, but various LEDs from blue to infrared have been put to practical use.
[0142]
As an exposure light source used in the present invention, each laser may be used alone, or a combination thereof may be used as a multi-beam. In the case of an LD, for example, by arranging ten LDs, a beam composed of ten light beams can be obtained. On the other hand, in the case of a helium neon laser, the light emitted from the laser is split into, for example, ten light beams by a beam separator.
[0143]
In the case of an LD or LED, the intensity of the exposure light source can be directly modulated by changing the value of the current flowing through each element. In the case of an LD, the intensity may be changed using an element such as an AOM (acoustic optical modulator). In the case of a gas laser, a device such as an AOM or an EOM (electro-optic modulator) is generally used.
[0144]
When an LED is used as a light source, a method may be used in which the same pixel is repeatedly exposed by a plurality of elements as long as the amount of light is weak.
[0145]
Organic light-emitting elements may be used as light sources instead of these, and these are described, for example, in JP-A-2000-258846.
[0146]
In the present invention, the term "area gradation image" is used. However, this is not expressed by the density of the color of each pixel but by the size of the area of a portion colored to a specific density. And may be considered synonymous with halftone dots.
[0147]
In the case of normal area gradation exposure, the purpose can be achieved by developing Y, M, C, and black. More preferably, in order to identify that a single color such as M or C has developed in addition to black, it is preferable to perform exposure by appropriately using three or more exposure values. In printing, a plate of a special color may be used, but in order to reproduce this, it is preferable to use four or more levels of exposure.
[0148]
In the case of a laser light source, the beam diameter is preferably 25 μm or less, more preferably 6 to 22 μm. Although smaller than 6 μm is preferable in terms of image quality, adjustment is difficult and processing speed is reduced. On the other hand, if it is larger than 25 μm, the unevenness increases and the sharpness of the image deteriorates. By optimizing the beam diameter, writing of a high-definition image without unevenness can be performed at high speed.
[0149]
To draw an image with such light, it is necessary for the light beam to scan over the silver halide photosensitive material.However, the photosensitive material is wound around a cylindrical drum and rotated at high speed in a direction perpendicular to the rotation direction. A cylindrical outer surface scanning method in which a light beam is moved may be used, and a cylindrical inner surface scanning method in which a silver halide photosensitive material is brought into close contact with a cylindrical recess and exposed is preferably used. A plane scanning method may be adopted in which the polyhedral mirror is rotated at a high speed and the silver halide light-sensitive material conveyed thereby is exposed by moving a light beam at right angles to the conveying direction. In order to obtain a high quality and large image, a cylindrical outer surface scanning method is more preferably used.
[0150]
In order to perform exposure by the cylindrical outer surface scanning method, the silver halide photosensitive material must be accurately brought into close contact with a cylindrical drum. In order for this to be performed properly, it is necessary that the wafer be transported while being accurately aligned. The silver halide light-sensitive material used in the present invention is preferably used when the surface on the side to be exposed is rolled outward, so that the alignment can be more accurately performed. From the same viewpoint, the support used for the silver halide light-sensitive material used in the present invention has appropriate rigidity, and preferably has a Taber rigidity of 0.8 to 4.0.
[0151]
The drum diameter can be arbitrarily set in accordance with the size of the silver halide photosensitive material to be exposed. The number of rotations of the drum can be set arbitrarily, but an appropriate number of rotations can be selected according to the beam diameter of the laser beam, the energy intensity, the writing pattern, the sensitivity of the photosensitive material, and the like. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at higher rotation speed, but specifically, 200 to 3000 rotations per minute is preferably used.
[0152]
The method of fixing the silver halide photosensitive material to the drum may be fixed by mechanical means, or a large number of fine holes that can be suctioned on the drum surface are provided according to the size of the photosensitive material, and the photosensitive material is fixed. It can also be brought into close contact by suction. It is important to make the photosensitive material as close as possible to the drum in order to prevent troubles such as uneven images.
[0153]
Known compounds can be used as the aromatic primary amine developing agent used in the present invention. The following compounds can be mentioned as examples of these compounds.
CD-1) N, N-diethyl-p-phenylenediamine
CD-2) 2-Amino-5-diethylaminotoluene
CD-3) 2-Amino-5- (N-ethyl-N-laurylamino) toluene
CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline
CD-5) 2-Methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline
CD-6) 4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) aniline
CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide
CD-8) N, N-dimethyl-p-phenylenediamine
CD-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline
CD-10) 4-Amino-3-methyl-N-ethyl-N- (β-ethoxyethyl) aniline
CD-11) 4-Amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline
In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is preferably from 9.5 to 13.0, more preferably from 9.8 to 12.0. Used in
[0154]
The processing temperature of color development according to the present invention is preferably 35 ° C. or more and 70 ° C. or less. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.
[0155]
Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.
[0156]
A known developer component compound can be added to the color developing solution in addition to the above color developing agent. Usually, an alkali agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazoles, a preservative, a chelating agent and the like are used.
[0157]
The silver halide color light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed.
[0158]
In the method for processing a silver halide color light-sensitive material of the present invention, a compound having a fluorescent whitening effect or a compound capable of reducing stain after processing is appropriately used in any of a developing solution, a bleach-fixing solution, and a stabilizing processing solution. It is preferred to add. In particular, it is preferable to add the compound represented by formula (W) to a developer or a bleach-fix solution. The amount of addition is not particularly limited as long as it can be dissolved and the desired effect can be obtained, but is preferably 1 g / L or more and 20 g / L or less, particularly preferably 5 g / L or more and 10 g / L.
[0159]
The developing apparatus used for developing the silver halide light-sensitive material of the present invention is a roller transport type in which the light-sensitive material is conveyed between rollers arranged in a processing tank, and the light-sensitive material is fixed to a belt. An endless belt method may be used, in which the processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is transported, or a spray method in which the processing liquid is sprayed. Alternatively, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can be used. When processing in large quantities, it is usual to run using an automatic developing machine, but at this time, the smaller the replenishment amount of the replenisher, the more preferable the replenishment amount is. And the method described in JP-A-94-16935 is most preferable.
[0160]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these embodiments.
[0161]
Example 1
A high-density polyethylene on one side laminated with molten polyethylene containing anatase-type titanium oxide dispersed at a content of 15% by mass on the other side. = 3.5, PY value = 2.7 μm), and each layer having the layer constitution shown in the following Table 1 was applied on the side of the polyethylene layer containing titanium oxide, and further on the back side, gelatin was 6.00 g / m 2. ^Two , Silica matting agent 0.65 g / m ^Two A multilayer silver halide photosensitive material sample No. 101 coated with was prepared.
[0162]
The coupler was dissolved in a high-boiling-point solvent, ultrasonically dispersed, and added as a dispersion. At this time, (SU-1) was used as a surfactant. (H-1) and (H-2) were added as hardeners. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The total amount of (F-1) was 0.04 g / m in each layer. ^Two Was added so that
[0163]
[Table 1]

[0164]
SU-1: sodium tri-i-propylnaphthalenesulfonate
SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt
SU-3: di (2,2,3,3,4,4,5,5-octafluoropentyl) sodium salt of sulfosuccinate
H-1: tetrakis (vinylsulfonylmethyl) methane
H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium
HQ-1: 2,5-di-t-octylhydroquinone
HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone
HQ-3: a mixture of 2,5-di-sec-dodecylhydroquinone, 2,5-di-sectetradecylhydroquinone and 2-sec-dodecyl-5-sec-tetradecylhydroquinone at a mass ratio of 1: 1: 2.
SO-1: trioctylphosphine oxide
SO-2: di (i-decyl) phthalate
SO-3: Oleyl alcohol
SO-4: tricresyl phosphate
PVP: polyvinylpyrrolidone
[0165]
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[0166]
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[0167]
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[0168]
(Preparation of blue-sensitive silver halide emulsion)
The following (Solution A) and (Solution B) were simultaneously added to one liter of a 2% aqueous gelatin solution kept at 40 ° C. while controlling pAg = 7.3 and pH = 3.0, and the following (Solution C) and (Solution D) was added simultaneously while controlling pAg = 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.
(A liquid)
3.42 g of sodium chloride
Potassium bromide 0.03g
200 ml with water
(B liquid)
Silver nitrate 10g
200 ml with water
(Liquid C)
Sodium chloride 102.7g
Potassium hexachloroiridate (IV) 4 × 10 ^-8 Mole
Potassium hexacyanoferrate (II) 2 × 10 ^-Five Mole
1.0 g of potassium bromide
600 ml with water
(D liquid)
Silver nitrate 300g
600 ml with water
After completion of the addition, desalting is performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd., and then mixed with an aqueous gelatin solution to have an average particle diameter of 0.71 μm and a coefficient of variation of particle diameter distribution. A monodispersed cubic emulsion EMP-101 having a silver chloride content of 0.07 and a silver chloride content of 99.5 mol% was obtained.
[0169]
The above compound (EMP-101) was optimally subjected to chemical sensitization at 60 ° C. using the following compounds to obtain Em-B101.
[0170]
Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer STAB-1 3 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-2 3 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-3 3 × 10 ^-Four Mol / mol AgX
Sensitizing dye BS-1 4 × 10 ^-Four Mol / mol AgX
Sensitizing dye BS-2 1 × 10 ^-Four Mol / mol AgX
Potassium bromide 0.2 g / mol AgX
Next, in the preparation of EMP-101, the average particle diameter was adjusted in the same manner as in EMP-101 except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A monodispersed cubic emulsion EMP-102 having a size of 64 μm, a coefficient of variation in particle size distribution of 0.07 and a silver chloride content of 99.5 mol% was obtained. Em-B102 was obtained in the same manner as in the preparation of Em-B101 except that EMP-102 was used instead of EMP-101, and a 1: 1 mixture of Em-B101 and Em-B102 was used as a blue-sensitive silver halide emulsion. did.
(Preparation of green-sensitive silver halide emulsion)
In the preparation of EMP-101, the average particle diameter was 0.40 μm, the variation coefficient was 0.08, and the chloride was changed in the same manner except that the addition time of (Solution A) and (Solution B), (Solution C) and (Solution D) was changed. A monodispersed cubic emulsion (EMP-103) having a silver content of 99.5% was obtained.
[0171]
The above-mentioned EMP-103 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds to obtain Em-G101.
[0172]
Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer STAB-1 3 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-2 3 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-3 3 × 10 ^-Four Mol / mol AgX
Sensitizing dye GS-1 2 × 10 ^-Four Mol / mol AgX
Sensitizing dye GS-2 2 × 10 ^-Four Mol / mol AgX
Sodium chloride 0.5g / mol AgX
Next, in the preparation of EMP-103, the average particle size was adjusted in the same manner as in EMP-103 except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A monodispersed cubic emulsion EMP-104 having a thickness of 50 µm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained. Em-G102 was obtained in the same manner as in the preparation of Em-G101 except that EMP-104 was used instead of EMP-103, and a 1: 1 mixture of Em-G101 and Em-G102 was used as a green-sensitive silver halide emulsion. did.
(Preparation of red-sensitive silver halide emulsion)
The EMP-103 was optimally chemically sensitized at 60 ° C. using the following compounds to obtain Em-R101.
[0173]
Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer STAB-1 2 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-2 2 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-3 2 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-4 1 × 10 ^-Four Mol / mol AgX
Sensitizing dye RS-1 1 × 10 ^-Four Mol / mol AgX
Sensitizing dye RS-2 1 × 10 ^-Four Mol / mol AgX
Supersensitizer SS-1 2 × 10 ^-Four Mol / mol AgX
Next, in the preparation of (Em-R101), the following compounds were optimally subjected to chemical sensitization at 60 ° C. to obtain Em-R102.
[0174]
Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer STAB-1 2 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-2 2 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-3 2 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-4 1 × 10 ^-Four Mol / mol AgX
Sensitizing dye RS-1 2 × 10 ^-Four Mol / mol AgX
Sensitizing dye RS-2 2 × 10 ^-Four Mol / mol AgX
Supersensitizer SS-1 2 × 10 ^-Four Mol / mol AgX
STAB-1: 1-phenyl-5-mercaptotetrazole
STAB-2: 1- (4-ethoxyphenyl) -5-mercaptotetrazole
STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole
STAB-4: p-toluenethiosulfonic acid
A 1: 1 mixture of Em-R101 and Em-R102 was used as a red-sensitive silver halide emulsion.
[0175]
Embedded image

[0176]
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[0177]
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[0178]
With respect to the thus obtained sample 101, samples 102 to 115 were also prepared in which the yellow coupler of the seventh layer was replaced with the one shown in Table 3 in an equimolar amount.
[0179]
Here, the exposure method will be described.
(Exposure method A)
Through a wedge whose density is continuously changing, using an appropriate color filter and ND filter, exposure to blue light from a halogen lamp as a light source for an exposure time of 0.5 seconds, after the development processing, within the sample surface A method in which both a white background portion and a maximum color density portion can be obtained with a sufficient area.
[0180]
Using the samples 101 to 115 obtained, exposure was performed by the exposure method A.
After the exposure, development processing was performed by the following method. This is referred to as processing method (a) -37.
[0181]
Treatment process Treatment temperature Time Replenishment amount
Color development 37.0 ± 0.3 ° C 120 seconds 200ml
Bleaching and fixing 37.0 ± 0.5 ° C 90 seconds 150ml
Stabilization 30-34 ° C 60 seconds 400ml
Drying 60-80 ° C 30 seconds
Color developer start solution and replenisher start solution Replenisher
Triethylenediamine 3.0 g 4.0 g
Diethylene glycol 6.0 g 8.0 g
Potassium bromide 0.15g 0.2g
Potassium chloride 3.5g 0.2g
Potassium sulfite 0.3g 0.4g
N-ethyl-N- (β-hydroxyethyl)
-4-Aminoaniline sulfate 3.0 g 4.0 g
N, N-disulfoethylhydroxylamine 15.0 g 20.0 g
Triethanolamine 6.0 g 8.0 g
Diethylenetriaminepentaacetic acid sodium salt 1.5g 2.0g
Potassium carbonate 30g 40g
The total volume is adjusted to 1 liter by adding water, and the tank solution is adjusted to pH = 10.2 and the replenisher is adjusted to pH = 10.5.
[0182]
Bleach-fixer tank solution and replenisher
Diethylenetriaminepentaacetic acid ammonium ferric dihydrate 65g
3 g of diethylenetriaminepentaacetic acid
Ammonium thiosulfate (70% aqueous solution) 100ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40% aqueous solution) 27.5ml
The total volume is made up to 1 liter by adding water and adjusted to pH = 5.0 with potassium carbonate or glacial acetic acid.
[0183]
Stabilizing solution tank solution and replenisher solution
1.0 g of o-phenylphenol
5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-methyl-4-isothiazolin-3-one 0.02 g
1.0 g of diethylene glycol
Optical brightener (WC-2) 2.0g
1.8 g of 1-hydroxyethylidene-1,1-diphosphonic acid
0.5 g of zinc sulfate
Magnesium sulfate heptahydrate 0.2g
PVP (polyvinyl pyrrolidone) 1.0 g
Aqueous ammonia (25% aqueous solution of ammonium hydroxide) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5g
The total volume is adjusted to 1 liter by adding water and adjusted to pH = 7.5 with sulfuric acid or aqueous ammonia.
[0184]
Embedded image

[0185]
WC-2: Compound described in JP-A-9-212821
The processing method (a) -39 in which the developing temperature is 39 ° C. in comparison with the processing method (a) -37 is described.
[0186]
The dye image obtained by the exposure method A and the processing method (a) -37 was measured using Minolta Co., Ltd. spectral colorimeter CM-2022 at each of the density points at which the color difference was minimum. ^* a ^* b ^* Of the color difference ΔEab ^* Was calculated. As color targets, Japan Printing Industrial Machinery Manufacturers Association, ISO / TC130 National Committee production, Japan Color color reproduction printing 2001, art paper, Y100% of ISO12647 pattern Y were used.
[0187]
Regarding colorimetry by CM-2022, the geometric condition of illumination and light reception was d-0, photometry was performed using a xenon pulse light source, and a 2 ° field of view and auxiliary standard light D50 were used. Regarding the density, a spectrodensitometer 508 manufactured by X-rite was used, and T was used as the Status under the condition of 45 ° annular illumination and 0 ° light reception. Table 2 shows the results.
[0188]
[Table 2]

[0189]
Embedded image

[0190]
Y-4: Coupler YI-6 described in JP-A-10-186601
Y-5: Coupler (42) described in JP-A-5-11416
The results shown in Table 2 clearly show that the photographic material of the present invention has a high degree of similarity to the printed matter in the color reproducibility of yellow. Compounds of the general formula (1) of the type in which the aryl group is directly substituted on the short linking group substituted on the 5-position of the anilino group are excellent, particularly (1) -4 (sample 105), (1) -10 (sample 107) and (1) -27 (sample 113) have a higher degree of approximation to printed matter and show excellent color development as compared with the sample using the comparative coupler. That is, R in the general formula (1) _Two Is a branched alkoxy group, and R ₁ Is particularly preferably an alkyl group. The linking group represented by L is -NHCO-, -SO _Two It can also be seen that NH- is particularly preferred.
[0191]
Example 2
With respect to the samples 101 to 115 produced in Example 1 and exposed and developed, the brightness of the white background was measured. In contrast to Sample 101 using the coupler Y-1 + Y-2 for comparison and Samples 102 and 103 using the couplers Y-4 and Y-5 for comparison, the light-sensitive material containing the coupler of the present invention was used for a white background. The effect was evaluated under the same processing conditions. The white background was evaluated based on the difference in brightness from the Y0% point of the Japan Color color reproduction print 2001. Table 3 shows the results.
[0192]
[Table 3]

[0193]
It is apparent from Table 3 that the light-sensitive material of the present invention has an effect of improving the brightness of a white background and making it more similar to a printed matter even if only the coupler is novel. As particularly preferable couplers, (1) -4 (sample 105) and (1) -10 (sample 107) are excellent. It is also found that (1) -27 (sample 113) and (1) -33 (sample 115) are also excellent.
[0194]
Example 3
In contrast to the above-mentioned processing method (a) -37, Sample 101 was prepared by using a processing solution obtained by adding the compounds and amounts shown in Table 5 to the color developing solution except for the fluorescent whitening agent (WC-2) in the stabilizing solution. , 102, 105, 109, 111, and 114 were evaluated in the same manner as in Example 2. Table 4 shows the results.
[0195]
[Table 4]

[0196]
It is apparent from Table 4 that the light-sensitive material of the present invention has a white background that is close to that of a printed material in any processing method as compared with the comparative light-sensitive material. In particular, it can be seen that the brightness of the white background of the sample 105 using the coupler (1) -4 is high. Also, the processing method (WC1) -37, (WC1) -37b or (WC2) -37, or (WC2) -37b, which is performed with a developer to which a comparative brightener WC-1 or WC-2 is added, is used. It can also be seen that a treatment method using a treatment solution to which the compound of the present invention represented by the general formula (W) is added is more preferable. In particular, in the two amino groups on the triazine ring of the compound of the formula (W), one of the amino group substituents is sodium ethanesulfonate and the other amino group substituent is a polyoxyethylene group. (W) -3 in which the rest of each of the two substituents of both amino groups is unsubstituted, that is, hydrogen, is more preferable. The effect is remarkable.
[0197]
Example 4
Using the samples 101, 102, 105, 109, 111, and 114 in Example 3, each sample having the size of A2 was not exposed, and only the developing process by the processing method shown in Table 5 was performed. B of the obtained sample ^* The value was measured. The measurement was performed by dividing the long side of the A2 size into 40 points and the short side into 30 points, and performing 40 points × 30 points = 1200 points. The standard deviation indicating the variation was obtained. ^* Was evaluated for stability in the same image plane. Table 5 shows the results.
[0198]
[Table 5]

[0199]
As is apparent from Table 5, the light-sensitive material of the present invention using the coupler represented by the general formula (1) shows the magnitude of the yellow (blue) component on a white background as compared with the comparative light-sensitive material. ^* It can be seen that the in-plane variation of the values is improved. In particular, the sample 105 using the coupler (1) -4 has a small variation, and the effect is more apparent when the sample is treated by a treatment method using a treatment solution using the compound represented by the general formula (W). Understand. In the compound of the formula (W), particularly, in two amino groups on the triazine ring, one of the amino group substituents is sodium ethanesulfonate and the other amino group substituent is a polyoxyethylene group. (W) -3 in which the remaining two of the two substituents of both amino groups are unsubstituted, that is, hydrogen, is more preferable. The in-plane variation is remarkably suppressed.
[0200]
Example 5
Using the samples 101, 102, 105, 109, 111, and 114 in Example 4, each sample was not exposed at the size of A2 size, and only the developing process by the processing method at the developing temperature of 39 ° C. shown in Table 6 was performed. Was. B of a sample obtained in the same manner as in Example 4. ^* The values were measured and the variation was calculated. The evaluation was performed together with the result at the developing temperature of 37 ° C. in Example 4. Table 6 shows the results.
[0201]
[Table 6]

[0202]
It is apparent from Table 6 that the photosensitive material of the present invention using the coupler represented by the general formula (1) has a white background even when the developing material is activated due to a change in the developing temperature condition. B indicating the size of the yellow (blue) component ^* It can be seen that there is little variation in the in-plane variation of the values, and it is extremely excellent. In particular, it can be seen that the effect is clearer when the treatment is performed by a treatment method using a treatment solution using the compound represented by the general formula (W).
[0203]
Example 6
Each of the samples 101 to 115 in Example 1 was subjected to a developing process using a processing method (a) -37 without exposure to A4 size. The obtained white background sample was observed under sunlight at around noon on a sunny day, under a three-wavelength fluorescent lamp, a white fluorescent lamp, and a krypton-type incandescent lamp. The difference from the actual printing paper (art paper) was visually evaluated by 50 subjects. The evaluation was made in two steps based on whether or not the two were approximated, and the ratio of the number of people who felt the similarity when each was observed side by side with the printing paper under each light source was calculated. Table 7 shows the results.
[0204]
[Table 7]

[0205]
It is apparent from the results in Table 7 that the white background of the photosensitive material of the present invention is improved in terms of its light source dependence in the approximation to the printing paper, and coupler (1) -10 (sample 107) is preferable. It can be seen that (1) -17 (sample 108) and (1) -27 (sample 113) are also preferable. That is, R in the general formula (1) _Two Is a branched alkoxy group, and R ₁ Is particularly preferably an alkyl group. Also R _Three Is a branched alkoxy group.
[0206]
Example 7
The same evaluation as in Example 6 was performed on Samples 101 (Comparative) and 105 (Invention) by using some of the processing methods used in Example 3. The results are shown in Table 8 (sample 101, comparison) and Table 9 (sample 105, the present invention).
[0207]
[Table 8]

[0208]
[Table 9]

[0209]
It is clear from the results in Tables 8 and 9 that the difference in the appearance of a white background under any light source is reduced by developing the light-sensitive material of the present invention with a developer containing a specific triazinylstilbene compound. You can see that it is. In particular, in the two amino groups on the triazine ring of the compound of the formula (W), one of the amino group substituents is sodium ethanesulfonate and the other amino group substituent is a polyoxyethylene group. It is understood that (W) -3 in which the rest of each of the two substituents of both amino groups is unsubstituted, that is, hydrogen is more preferable.
[0210]
Example 8
For the samples 101, 105, and 111, the first layer was coated with the compound WC-2 and (W) -3 at 0.2 g / m 2 each. ^Two The added samples 201, 301, 205, 305, 211, and 311 were produced. Each of the samples 101, 105, 111, 201, 205, 211, 301, 305, and 311 was processed in the above-mentioned processing method (a) -37 without exposure to A4 size. The same evaluation as in Example 5 was performed. Table 10 shows the results.
[0211]
[Table 10]

[0212]
It is clear from Table 10 that in the light-sensitive material containing the coupler represented by the general formula (1), by adding a compound having a fluorescent whitening effect to the light-sensitive material, the output white background can be further reduced under any light source. It can be seen that the difference in appearance is further reduced. Further, it is found that it is more preferable to contain the compound represented by the general formula (W). By comparing Samples 305 and 311, it is particularly preferable that the R ₁ Is an alkyl group.
[0213]
Example 9
Regarding the samples 101, 105, and 110, the compounds WC-2 and (W) -3 were each added to the first layer at 0.2 g / m ^Two Samples 201, 301, 205, 305, 210, and 310 were added. Samples 101, 105, 110, 201, 205, 210, 301, 305, and 310 were each A4-sized, and were not exposed to the above-mentioned processing methods (WC2) -37, (W3) -37, and (W27). ) -37, the same evaluation as in Example 7 was performed. The results are shown in Tables 11, 12 and 13.
[0214]
[Table 11]

[0215]
[Table 12]

[0216]
[Table 13]

[0219]
As is clear from Tables 11 to 13, a compound having a fluorescent whitening effect is added to the light-sensitive material of the present invention containing the coupler represented by the general formula (1), and the compound further has a fluorescent whitening effect. It can be seen that the difference in the appearance of the white background, which is further output, by the light source is reduced by the processing using the color developing solution containing the compound. In particular, the light-sensitive material of the present invention containing a coupler represented by the general formula (1) contains a compound represented by the general formula (W), and further contains a compound represented by the general formula (W). It can be seen that the difference in the appearance of the white background, which is greatly output, by the light source is reduced by the processing with the processing method using the developer.
[0218]
Further, as the coupler represented by the general formula (1), R ₁ Is more preferably an alkyl group.
[0219]
【The invention's effect】
By the constitution of the present invention, it is possible to provide a silver halide color light-sensitive material having excellent yellow color reproducibility, in particular, color reproducibility having a hue extremely close to a target image without lowering of lightness and chroma. Was completed. Furthermore, a method for processing a silver halide color light-sensitive material that has high brightness, has little variation within the same plane, is similarly observed under any light source, and reproduces an excellent white background with little deviation in the appearance of printed paper. Could be provided.

Claims (6)

A silver halide color light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains at least one coupler represented by the following general formula (1). Silver halide color photosensitive material.

(Wherein, R ₁ represents a substituted or unsubstituted aliphatic group, aromatic group, heterocyclic group, alkoxy group, aryloxy group, amino group, and R ₂ and R ₃ represent a substituted or unsubstituted group. Represents an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, or a halogen atom, R ₄ represents a substituent, n represents an integer of 0 to 4, and n represents 2 to In the case of any integer of ₄ , the groups represented by R ₄ may be the same or different, and may be bonded to each other to form a ring, and L is —N (R ₅ ) C (= O) -, - C (= O) N (R 5) -, - N (R 5) S (= O) 2 -, - S (= O) 2 N (R 5) -, - N (R 5 ) S (= O) -, - S (= O) N (R 5) -, - C (= O) O -, - OC (= O) -, - OP (= O) (O) 2 -, _{-N (R 5) P (=} O) (O ₂ -. Represents a linking group selected from any one of, R ₅ is .X represents a hydrogen atom or a substituent represents a group capable of leaving upon reaction with an oxidation product of a color developing agent, however, R ₁ is an amino group in it, L simultaneously -S (= O) it is not a ₂ NH-.) In the compound represented by the general formula (1), the group represented by R ₁ is a substituted or unsubstituted aliphatic group, and the substituent represented by R ₂ is an alkoxy group or an aryloxy group. There, a divalent linking group is -N represented by _{L (R 5) C (=} O) -, - C (= O) N (R 5) -, - N (R 5) S (= O) _{2. The method according} to claim 1, wherein the compound is selected from any of _2- , -S (= O) ₂ N (R ₅ )-, -C (= O) O-, and -OC (= O)-. Silver halide color photosensitive material. In the compound represented by the general formula (1), the group represented by R ₃ is an alkoxy group, an aryloxy group, or a halogen atom, and the group represented by X is a group eliminated by a nitrogen atom. The silver halide color light-sensitive material according to claim 1 or 2, wherein 4. The silver halide color light-sensitive material according to claim 1, wherein a compound represented by the following general formula (W) is contained in any of the layers constituting the light-sensitive material.

(Wherein, R ₁₁ and R ₁₂ each independently represent a hydrogen atom or a substituent, R ₁₃ and R ₁₄ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ₁₅ and R ₁₆ each independently represent represent a group represented by the following general formula (W-R), Rw represents a hydrogen atom, a group represented by the following general formula (W-R), or _{-CH 2 CH 2 SO 3 M,} M is Represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or a pyridinium group. R ₁₃ and R ₁₅ , or R ₁₄ and R ₁₆ may be bonded to each other to form a ring.)

(In the formula, A represents any one of a hydrogen atom, a hydroxyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 1-hydroxypropyl group. , A may be the same or different. F, h, and j represent 1 or 2, and g, i, and k represent 0 or 1.) 5. The silver halide color light-sensitive material according to claim 1, which is treated with a processing solution containing at least one compound represented by the formula (W). A method for developing a color photosensitive material. In the compound represented by the general formula (W) contained in the treatment liquid, the substituents represented by R ₁₁ and R ₁₂ are all hydrogen atoms, or the substituents represented by R ₁₃ and R ₁₄ 6. The method for developing a silver halide color light-sensitive material according to claim 5, wherein all the groups are hydrogen atoms.