JP2005043528A - Area coverage modulation image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an area coverage modulation image forming method excellent in color tone reproducibility and dot reproducibility. <P>SOLUTION: The area coverage modulation image forming method by which halftone dots are reproduced as aggregates of minimum unit (dot) of image formation using a silver halide color photosensitive material, is characterised in that the silver halide color photosensitive material contains a dye forming coupler represented by formula (a-1) or (a-2). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

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本発明に係る一般式（ａ−１）及び一般式（ａ−２）で表されるイエローカプラーは、例えば、米国特許５，４５５，１４９号明細書、米国特許公開２００３−６４３３２号明細書等に記載の方法に従って合成することができる。
【００５７】
本発明に係るハロゲン化銀カラー感光材料においては、本発明に係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、本発明に係るイエローカプラーは、他の種類のカプラーと併用することもできる。本発明に係るハロゲン化銀カラー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で用いられる方法及び技術が、同様に適用される。
【００５８】
本発明に係る一般式（ａ−１）または一般式（ａ−２）で表されるイエローカプラーの添加層としては、特に制限はないが、３種以上の発色層を有するハロゲン化銀カラー感光材料においては、支持体に最も近接した位置にある発色層（以下、画像形成層ともいう）に、本発明に係る一般式（ａ−１）または（ａ−２）で表される色素形成カプラーを含有することが好ましい。
【００５９】
本発明に係るハロゲン化銀カラー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号公報の２ページに記載の一般式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、欧州公開特許第０，２７３，７１２号の６〜２１頁に記載されている化合物Ｍ−１〜Ｍ−６１及び同第０，２３５，９１３号の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。
【００６０】
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、総マゼンタカプラー量としては、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。
【００６１】
本発明に係るハロゲン化銀カラー感光材料において、形成されるマゼンタ画像の分光吸収のλ_ｍａｘは５３０〜５６０ｎｍであることが好ましく、またλＬ_０．２は、５８０〜６３５ｎｍであることが好ましい。λＬ_０．２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、λ_ｍａｘ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。
【００６２】
本発明に係るハロゲン化銀カラー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。本発明に係るハロゲン化銀カラー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。本発明に係るハロゲン化銀カラー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、例えば、特開平８−３１４０７９号公報の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。
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本発明に係るハロゲン化銀カラー感光材料において、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号公報の１３ページに記載の一般式［Ｃ−Ｉ］、［Ｃ−ＩＩ］で表される化合物が挙げられる。
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アゾール系カプラーとしては、特開平８−１７１１８５号公報の２ページに記載の一般式〔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号公報に記載の一般式（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。
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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。
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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号公報の２２ページに記載の一般式［ＨＢＳ−Ｉ］で示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公報の２２ページに記載の一般式［ＨＢＳ−ＩＩ］で示される化合物である。
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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号公報の３ページに記載の一般式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号公報に記載の一般式ＩＩＩＢで示されるフェノール系化合物、特開昭６４−９０４４５号公報に記載の一般式Ａで示されるアミン系化合物、特開昭６２−１８２７４１号公報に記載の一般式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号号公報に記載の一般式Ｉ′で示される化合物および特開平５−１１４１７号公報に記載の一般式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。
【００６８】
本発明に係るハロゲン化銀カラー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際に、水中油滴型乳化分散法を用いる場合、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組み入れてもよい。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でき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４−２６５９７５号公報の５ページに記載の（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、２種以上の高沸点有機溶媒を併用することもできる。
【００６９】
本発明に係るハロゲン化銀カラー感光材料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において、高濃度に臭化銀を含有する部分は、いわゆるコア・シェル型ハロゲン化銀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。
【００７０】
本発明に係るハロゲン化銀カラー感光材料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。これにより、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領域での軟調化が防止されることが期待される。
【００７１】
このような目的で用いることのでき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できる。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。
【００７２】
これらの金属化合物の特性として、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。これらの化合物は、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号公報の４〜５ページに詳しい記載がある。
【００７３】
ハロゲン化銀乳剤中に重金属イオンを含有させる方法としては、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。
【００７４】
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。前記重金属イオンのハロゲン化銀乳剤中への添加量は、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。
【００７５】
本発明に用いられるハロゲン化銀粒子の形状は、任意のものを用いることができる。好ましい例の１つは、（１００）面を結晶表面として有する立方体である。また、米国特許第４，１８３，７５６号、同第４，２２５，６６６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。更に、双晶面を有する粒子を用いてもよい。
【００７６】
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画像形成層に添加することが特に好ましい。
【００７７】
本発明に用いられるハロゲン化銀粒子の粒径としては、特に制限はないが、迅速処理性適性及び到達感度や、他の写真性能を考慮すると、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。
【００７８】
この粒径は、ハロゲン化銀粒子の投影面積か、あるいは直径近似値を使ってこれを測定して求めることができる。ハロゲン化銀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。
【００７９】
本発明に用いられるハロゲン化銀粒子の粒径分布は、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、変動係数が０．１５以下の単分散乳剤を２種以上、同一画像形成層に添加することである。ここでいう変動係数とは、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。
【００８０】
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。
【００８１】
ハロゲン化銀乳剤の調製装置、調製方法としては、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。
【００８２】
本発明に用いられるハロゲン化銀乳剤は、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。該ハロゲン化銀粒子は、一時に成長させたものであってもよいし、種粒子を調製した後で成長させてもよい。種粒子を調製す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。
【００８３】
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。
【００８４】
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、ドイツ公開特許第２，９２１，１６４号等に記載されている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させて添加する装置、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。
【００８５】
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。
【００８６】
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等を適宜組み合わせて用いることができる。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できるが、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。
【００８７】
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適宜変更することが好ましいが、概ねハロゲン化銀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モルの範囲である。
【００８８】
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^−４〜１×１０^−８モルであることが好ましい。更に好ましくは１×１０^−５〜１×１０^−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もできる。
【００８９】
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。
【００９０】
本発明に係るハロゲン化銀カラー感光材料には、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こともできる。該ハロゲン化銀乳剤は、１種または、２種以上の増感色素を組み合わせて含有する。
【００９１】
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。
【００９２】
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。
【００９３】
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。
【００９４】
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。
【００９５】
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号公報の第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。
【００９６】
また、これらの分散装置を用いるに際し、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。
【００９７】
本発明に用いられるハロゲン化銀乳剤は、１種または、２種以上の増感色素を組み合わせて含有してもよい。
【００９８】
本発明に用いられるハロゲン化銀乳剤には、ハロゲン化銀カラー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できる。この様な目的で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号公報の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、更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号公報の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任意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^−５〜５×１０^−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^−６〜１×１０^−２モル程度の量が好ましく、１×１０^−５〜５×１０^−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^−６〜１×１０^−１モル程度の量が好ましく、１×１０^−５〜１×１０^−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、塗布皮膜中の含有量として、１ｍ^２当り１×１０^−９〜１×１０^−３モル程度の量が好ましい。
【００９９】
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できる。例えば、特開平２−１４６０３６号公報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。
【０１００】
本発明に係るハロゲン化銀カラー感光材料には、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できるが、特に、可視域に吸収を有する染料としては、特開平３−２５１８４０号公報の３０８ページに記載のＡＩ−１〜１１の染料および特開平６−３７７０号公報に記載の染料が好ましく用いられる。
【０１０１】
本発明に係るハロゲン化銀カラー感光材料は、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。
【０１０２】
本発明に用いられるハロゲン化銀カラー感光材料では、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０．１〜５０ｇ／ｍ^２の範囲であり、更に好ましくは０．２〜５ｇ／ｍ^２の範囲である。
【０１０３】
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。
【０１０４】
本発明に係るハロゲン化銀カラー感光材料中に、蛍光増白剤を添加することで白地性をより改良できる点で好ましい。蛍光増白剤は、紫外線を吸収して可視光の蛍光を発することのできる化合物であれば特に制限はないが、分子中に少なくとも１個以上のスルホン酸基を有するジアミノスチルベン系化合物であり、これらの化合物には、増感色素のハロゲン化銀カラー感光材料外への溶出を促進する効果もあり好ましい。他の好ましい一つの形態は、蛍光増白効果を有する固体微粒子化合物である。
【０１０５】
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号に記載の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。これら界面活性剤を用いて乳化された油溶性添加剤の分散液は、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。
【０１０６】
本発明に係るハロゲン化銀カラー感光材料には、現像主薬酸化体と反応する化合物をハロゲン化銀乳剤層間に設けた中間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直接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、更に好ましくは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号に記載の一般式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。
【０１０７】
本発明に係るハロゲン化銀カラー感光材料中には、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号に記載の一般式ＩＩＩ−３で示される化合物、特開昭６４−６６６４６号に記載の一般式ＩＩＩで示される化合物、特開昭６３−１８７２４０号に記載のＵＶ−１Ｌ〜ＵＶ−２７Ｌ、特開平４−１６３３号に記載の一般式Ｉで示される化合物、特開平５−１６５１４４号に記載の一般式（Ｉ）、（ＩＩ）で示される化合物が挙げられる。
【０１０８】
本発明に係るハロゲン化銀カラー感光材料には、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が挙げられる。
【０１０９】
本発明に係るハロゲン化銀カラー感光材料には、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、例えば、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。
【０１１０】
これらバインダーに対する硬膜剤としては、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号に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号に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、ハロゲン化銀カラー感光材料または処理後のハロゲン化銀カラー感光材料表面の物性を改良するため、保護層に、例えば、特開平６−１１８５４３号や特開平２−７３２５０号に記載の滑り剤やマット剤を添加することが好ましい。
【０１１１】
本発明に係るハロゲン化銀カラー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、例えば、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。
【０１１２】
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／ｍ^２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おいては、取り扱い感覚を印刷用紙に近づけるため、１３０ｇ／ｍ^２以下の原紙が好ましく用いられ、更に７０〜１２０ｇ／ｍ^２の原紙が好ましく用いられる。
【０１１３】
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。
【０１１４】
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、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、クレイ等が挙げられる。白色顔料として好ましくは、硫酸バリウム、酸化チタンである。
【０１１５】
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、鮮鋭性を改良する観点からは１３質量％以上が好ましく、更には１５質量％以上が好ましい。
【０１１６】
紙支持体の両面を被覆する耐水性樹脂層における白色顔料の分散度は、特開平２−２８６４０号公報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。
【０１１７】
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。樹脂層を複数層とし、ハロゲン化銀乳剤層と接する面側に白色顔料を高濃度で含有させると鮮鋭性の向上効果が大きく、プルーフ用画像を形成するのに好ましい形態の１つである。
【０１１８】
また、支持体の中心面平均粗さ（ＳＲａ）の値としては０．１５μｍ以下、更には０．１２μｍ以下でことが、光沢性がよいという効果が得られる観点から好ましい。
【０１１９】
本発明に用いられるハロゲン化銀カラー感光材料は、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付与するための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。
【０１２０】
ハロゲン化銀乳剤を用いたハロゲン化銀カラー感光材料の塗布に際して、塗布性を向上させる目的で、増粘剤を用いてもよい。塗布方法としては、２種以上の層を同時に塗布することのできるエクストルージョンコーティングまたはカーテンコーティングが特に有用である。
【０１２１】
次いで、本発明の面積階調画像形成方法の詳細について説明する。
本発明の面積階調画像形成方法に用いられる露光装置において、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できるが、レーザーまたは発光ダイオード（以下、ＬＥＤと記す）がより好ましく用いられる。
【０１２２】
レーザーとしては、半導体レーザー（以下、ＬＤと記す）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は、ＬＤを用いるのが有利である。
【０１２３】
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。
【０１２４】
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。
【０１２５】
ＬＥＤとしては、ＬＤと同様の組成を有する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。
【０１２６】
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。
【０１２７】
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。
【０１２８】
光源として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。
【０１２９】
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。
【０１３０】
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。
【０１３１】
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。
【０１３２】
このような光で画像を描くには、ハロゲン化銀カラー感光材料上を光束が走査する必要があるが、ハロゲン化銀カラー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、いわゆる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カラー感光材料を密着させて露光する、いわゆ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カラー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、いわゆ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観点から、円筒外面走査方式がより好ましく用いられる。
【０１３３】
円筒外面走査方式で露光を行うには、ハロゲン化銀カラー感光材料を正確に円筒状のドラムに密着されなければならない。この密着を確実に行なうためには、正確に位置合わせして搬送する必要がある。本発明に用いられるハロゲン化銀カラー感光材料は、露光する側の面（ハロゲン化銀乳剤層塗設面側）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カラー感光材料に用いられる支持体としては、適正な剛度があり、テーバー剛度で０．８〜４．０が好ましい。
【０１３４】
露光ドラム径は、露光するハロゲン化銀カラー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。露光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ハロゲン化銀カラー感光材料の感度などにより、適切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。
【０１３５】
露光ドラムへのハロゲン化銀カラー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ハロゲン化銀カラー感光材料の大きさに応じて多数設けておき、ハロゲン化銀カラー感光材料を吸引して密着させることもできる。ハロゲン化銀カラー感光材料を露光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。
【０１３６】
次いで、現像処理について説明する。
本発明において、発色現像処理で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。
【０１３７】
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、発色現像液は任意の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。
【０１３８】
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より好ましい。
【０１３９】
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、更に２５秒以内の範囲で行うことが更に好ましい。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できる。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。
【０１４０】
本発明に係る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。なお、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。
【０１４１】
本発明に係る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は好ましい。特に、発色現像液、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、概ね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。
【０１４２】
本発明に係るハロゲン化銀カラー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ハロゲン化銀カラー感光材料を挟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、ベルトにハロゲン化銀カラー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ハロゲン化銀カラー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。大量にハロゲン化銀カラー感光材料を処理する場合には、自動現像機を用いてランニング処理されるのが通常であるが、この際、処理量に応じて補充を行う補充液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、この方法としては、公開技報９４−１６９３５号に記載の方法が最も好ましい。
【０１４３】
【実施例】
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
【０１４４】
実施例１
《ハロゲン化銀カラー感光材料の作製》
〔試料１０１の作製〕
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に記載の構成からなる各層を、酸化チタンを含有するポリエチレン層面側に塗設し、更に裏面側にはゼラチン６．００ｇ／ｍ^２、シリカマット剤０．６５ｇ／ｍ^２を含む層を塗設した多層ハロゲン化銀カラー感光材料である試料１０１を作製した。
【０１４５】
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／ｍ^２となるように添加した。
【０１４６】
【表１】

【０１４７】
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
ＨＱ−４：２，５−ジ−ｔ−ブチルハイドロキノン
ＰＶＰ：ポリビニルピロリドン
【０１４８】
【化１３】

【０１４９】
【化１４】

【０１５０】
【化１５】

【０１５１】
上記試料１０１の作製に用いた各感光性ハロゲン化銀乳剤は、以下の方法に従って調製した。
【０１５２】
（青感光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号公報に記載の方法に従って行い、ｐＨ制御は硫酸または水酸化ナトリウム水溶液を用いて行った。
【０１５３】
〈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に仕上げた
〈Ｂ液〉
硝酸銀 １０ｇ
水を加えて ２００ｍｌに仕上げた
〈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に仕上げた
〈Ｄ液〉
硝酸銀 ３００ｇ
水を加えて ６００ｍｌに仕上げた
添加終了後、花王アトラス社製のデモールＮの５％水溶液と硫酸マグネシウムの２０％水溶液と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％の単分散立方体の乳剤ＥＭＰ−１０１を得た。
【０１５４】
上記乳剤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、青感光性ハロゲン化銀乳剤Ｅｍ−Ｂ１０１を得た。
【０１５５】
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、上記乳剤ＥＭＰ−１０１の調製において、（Ａ液）と（Ｂ液）の添加時間、及び（Ｃ液）と（Ｄ液）の添加時間とをそれぞれ変更した以外は同様にして、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％の単分散立方体の乳剤ＥＭＰ−１０２を得た。
【０１５６】
上記青感光性ハロゲン化銀乳剤Ｅｍ−Ｂ１０１の調製において、乳剤ＥＭＰ−１０１に代えて、乳剤ＥＭＰ−１０２を用いた以外同様にして、青感光性ハロゲン化銀乳剤Ｅｍ−Ｂ１０２を調製し、Ｅｍ−Ｂ１０１とＥｍ−Ｂ１０２の１：１の混合物を第７層で用いる青感光性ハロゲン化銀乳剤とした。
【０１５７】
（緑感性ハロゲン化銀乳剤の調製）
上記乳剤ＥＭＰ−１０１の調製において、（Ａ液）と（Ｂ液）の添加時間、及び（Ｃ液）と（Ｄ液）の添加時間とをそれぞれ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％の単分散立方体の乳剤ＥＭＰ−１０３を得た。
【０１５８】
上記乳剤ＥＭＰ−１０２に対し、下記化合物を用い５５℃にて最適に化学増感を行い、緑感光性ハロゲン化銀乳剤Ｅｍ−Ｇ１０１を得た。
【０１５９】
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 １×１０^−４モル／モルＡｇＸ
増感色素：ＧＳ−２ １×１０^−４モル／モルＡｇＸ
増感色素：ＧＳ−３ ２×１０^−４モル／モルＡｇＸ
塩化ナトリウム ０．５ｇ／モルＡｇＸ
次いで、上記乳剤ＥＭＰ−１０３の調製において、（Ａ液）と（Ｂ液）の添加時間、及び（Ｃ液）と（Ｄ液）の添加時間をそれぞれ変更した以外は同様にして、平均粒径０．５０μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体の乳剤ＥＭＰ−１０４を得た。
【０１６０】
上記緑感光性ハロゲン化銀乳剤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緑感光性ハロゲン化銀乳剤Ｅｍ−Ｇ１０２を調製し、Ｅｍ−Ｇ１０１とＥｍ−Ｇ１０２の１：１の混合物を第５層で用いた緑感光性ハロゲン化銀乳剤とした。
【０１６１】
（赤感性ハロゲン化銀乳剤の調製）
前記調製した乳剤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、赤感光性ハロゲン化銀乳剤Ｅｍ−Ｒ１０１を得た。
【０１６２】
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、前記調製した乳剤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、赤感光性ハロゲン化銀乳剤Ｅｍ−Ｒ１０２を得た。
【０１６３】
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
上記調製した赤感光性ハロゲン化銀乳剤Ｅｍ−Ｒ１０１と赤感光性ハロゲン化銀乳剤Ｅｍ−Ｒ１０２の１：１の混合物を、第３層の赤感光性ハロゲン化銀乳剤として用いた。
【０１６４】
上記各感光性ハロゲン化銀乳剤の調製に用いた添加剤の詳細は、以下の通りである。
【０１６５】
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
【０１６６】
【化１６】

【０１６７】
〔試料１０２〜１０４の作製〕
上記試料１０１の作製において、第７層で用いたイエローカプラー（Ｙ−１）を、表２に記載のイエローカプラー種及び添加量に変更した以外は同様にして、試料１０２〜１０４を作製した。
【０１６８】
《面積階調画像の形成》
〔画像露光〕
上記作製した試料１０１〜１０４に、イエロー版として０〜１００％のグラデーション画像を、スクリーン線数１７５線のＡＭスクリーニング方式、ＦＡＩＲＤＯＴ（大日本スクリーン製造社製）、Ｓｔａｃｃａｔｏ（クレオジャパン社製）の３方式で展開した画像データを、デジタルコンセンサス プロシステム（コニカメディカルアンドグラフィック（株）社製）で出力した。
【０１６９】
露光条件は、イエロー濃度が１．０なる条件で出力を行った。ＤＧ（ドットゲイン）はそれぞれのスクリーン方式で印刷した際に比較となる印刷物と、Ｍｕｒｒｙ−Ｄａｖｉｅｓ式で求めたＤＧとが同じようになるように、ＬＵＴを調整して出力を行った。
【０１７０】
〔現像処理〕
現像処理は以下に示す条件で行った。
【０１７１】
処理工程 処理温度 処理時間 補充量（ｍｌ／ｍ^２）
発色現像 ４０．０±０．３℃ １２０秒 ８０ｍｌ
漂白定着 ３９．０±０．５℃ ９０秒 １２０ｍｌ
安定化 ３０〜３４℃ ６０秒 １５０ｍｌ
乾燥 ６０〜８０℃ ３０秒
上記各処理工程で使用した処理液は、以下の通りである。
【０１７２】
〈発色現像液タンク液と補充液〉

水を加えて全量を１リットルとし、タンク液はｐＨ＝１０．０に、補充液はｐＨ＝１０．６に調整した。
【０１７３】
〈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に調整した。
【０１７４】
〈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（チノパールＳＦＰ） 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に調整した。
【０１７５】
〔画像評価〕
（色調再現性の評価）
上記形成した画像について、ミノルタ社製の分光測色計ＣＭ−２０２２を用いて、照明と受光の幾何条件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でのＬ^＊ａ^＊ｂ^＊の値を求め、（社）日本印刷学会標準化委員会が作製したＪａｐａｎ ｃｏｌｏｒ 色再現印刷 ２００１ アート紙のＹ１００％パッチとの色差（ΔＥ）を求め、これを色調再現性の尺度とした。
【０１７６】
なお、上記評価において、イエロー濃度は、エックスライト社製５０８型濃度計を用いて、フィルターとしてステータスＴにより測定した。
【０１７７】
（網点再現性の評価）
上記方法に従って、各方式で小点、大点、トーンジャンプ（表中には、ＴＪと略記）の画像を出力した試料と、各方式で印刷した基準サンプルとを比較し、得られた各面積階調画像を目視観察し、下記の基準に則り網点再現性の評価を行った。
【０１７８】
○：基準サンプルである印刷物に対する再現性が高い
△：基準サンプルである印刷物と若干異なるが、許容範囲内にある
×：基準サンプルである印刷物とは明らかに差異が認められ、実用上問題がある
以上により得られた結果を、表２に示す。
【０１７９】
【表２】

【０１８０】
表２の結果より明らかなように、本発明の一般式（ａ−１）または（ａ−２）で表されるイエローカプラーを含有するハロゲン化銀カラー感光材料を用いた本発明の面積階調画像形成方法により作成した画像は、比較例に対し、色調再現性に優れ、かつ各種方式により出力した網点画像の網点再現性に優れていることが分かる。
【０１８１】
実施例２
特開２００１−１３３９２２号公報の実施例１に記載の試料１０１の調製において、第１層で用いたイエローカプラー（Ｙ−１）を、実施例１に記載の第７層で用いた各イエローカプラーを表３に記載のように変更した以外は同様にして、試料２０１〜２０４を作製した。更に、試料２０２において、第１層（青感光性層：イエローカプラー含有層）と第３層（緑感光性層：マゼンタカプラー含有層）の配置を入れ替えた以外は同様にして、試料２０５を作製した。
【０１８２】
この様にして作製した各試料を、露光した後、特開２００１−３５６４５６号号公報の段落〔０１６０〕〜同〔０１６４〕に記載の現像処理Ａにより現像を行い実施例１と同様の方法で、色調再現性及び網点再現性（ＦＡＩＲＤＯＴのみ）の評価を行い、得られた結果を表３に示す。
【０１８３】
【表３】

【０１８４】
表３の結果より明らかなように、本発明の一般式（ａ−１）または（ａ−２）で表されるイエローカプラーを含有するハロゲン化銀カラー感光材料を用いた本発明の面積階調画像形成方法により作成した画像は、比較例に対し、色調再現性及び網点再現性に優れていることが分かる。更に、支持体に最も近接した位置に配置された感光性層に、本発明の一般式（ａ−１）または（ａ−２）を含むイエローカプラーを添加することにより、その効果がより発揮されていることが分かる。
【０１８５】
【発明の効果】
本発明により、色調再現性及び網点再現性に優れた面積階調画像形成方法を提供することができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for forming an area gradation image of a silver halide color light-sensitive material (color proof) for confirming the finished product in advance.
[0002]
[Prior art]
Silver halide color light-sensitive materials are actively used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. The silver halide color light-sensitive material having such characteristics is not only in the field of photography for general photography, but also in the field of printing, the field of so-called color proofing for checking the state of the finished printed matter in the middle of printing. But it is becoming widely used.
[0003]
In the field of color proofing, a color image edited on a computer is output to a printing film, and the developed film is subjected to separation exposure while appropriately replacing the film, whereby yellow (Y), magenta (M), cyan ( Each color image of C) is formed, and an image of the final printed matter is formed on color photographic paper, thereby determining the layout and color suitability 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, and in such a case, a color image can be obtained directly from the data on the computer without using a film. It was desired.
[0005]
For this purpose, various methods such as a sublimation type / melting heat transfer method, an electrophotographic method, and an ink jet method have been tried. However, a method capable of obtaining a high-quality image is expensive and inferior in productivity. In addition, there is a disadvantage that the image quality is inferior in a method that is low in cost and excellent in productivity.
[0006]
The system using silver halide color light-sensitive materials enables high-quality image formation, such as the ability to form accurate halftone images due to excellent sharpness, etc. On the other hand, continuous development processing is possible as described above. High productivity can be realized from the standpoints that images can be simultaneously written to a plurality of color image forming units.
[0007]
In recent years, digitization has progressed in the field of printing, and there is an increasing demand for obtaining an image directly from data in a computer. For the above-described reasons, for example, a halogen as disclosed in JP-A-2001-235816. Silver halide color light-sensitive materials are beginning to be used advantageously in this field.
[0008]
While ordinary silver halide color light-sensitive materials form images with continuous gradation, silver halide color light-sensitive materials used for proofing applications form images with area gradations based on halftone dots. Different performance is required as a performance for image quality. In other words, for image reproduction of halftone dots, characteristics such as reproducibility of small dots, reproducibility of large dots, and tone jumps in gradation from small dots to large dots are important. Reproducibility was desired. Further, in recent years, as a halftone dot forming method, an FM screening method and a hybrid screening method have become widespread instead of the conventional AM screening method. These screening methods are characterized by high-definition image reproduction, but as a feature of the halftone dot formation method, area gradations are formed with smaller halftone dots than the AM screening method, and in particular, advanced halftone dot reproduction is possible. It is requested. As a silver halide color light-sensitive material for proof suitable for these screening methods, for example, a silver halide color light-sensitive material described in JP-A-8-314081 is known, but such a method is not perfect. In particular, 10 by a high-intensity light source such as a laser often used in a DDCP (Direct Digital Color Proof) method for directly forming an image from digital data. ^-5 There has been a demand for faithful reproducibility of an FM screening method area gradation image by extremely short scanning exposure of less than a second.
[0009]
On the other hand, the most commonly used color image forming method as a silver halide color light-sensitive material is an oxidized aromatic primary amine color developing agent and coupler using exposed silver halide as an oxidizing agent. Is reacted to form indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and similar dyes. In such an image forming method, a method of reproducing a color image by a subtractive color method is used. In general, a color image is formed by changing the generation amount of three colors of yellow, magenta, and cyan. Yes. Of these, acylacetanilide couplers are widely used as color developing couplers used for forming yellow dye images. Benzoylacetanilide type compounds with good color development are preferred for silver halide color photosensitive materials for photography, and pivaloyl acetanilide type compounds with excellent color tone are preferred for ornamental silver halide color photosensitive materials. ing.
[0010]
The basic properties required for these couplers are: excellent spectral absorption characteristics of the dye formed, high dye formation speed, high color density, and light, heat, It is desired to have various properties such as high fastness to moisture. In particular, as a coupler used in the area gradation image forming method, faithful halftone dot reproducibility is desired. Such faithful halftone dot reproducibility is determined by complex interactions such as diffusion of oxidized color developing agent, diffusion of couplers, and respective reaction rates and lifetime of active species. However, at present, no detailed examination has been made from the viewpoint of coupler types and halftone dot reproducibility.
[0011]
As a result of intensive studies on the above problems, the present inventor is known as a yellow coupler with improved color reproducibility, high color developability and light fastness, for example, as described in JP-A-63-123047. It was found that yellow couplers having an alkoxy group at the 2-position and an acylamino group at the 5-position of the anilide moiety have problems in reproducibility of the area gradation image by halftone dots such as small dot reproduction and tone jump. .
[0012]
Conventional yellow dye-forming couplers have low color reproducibility and low extinction coefficient of the dyes formed, so a large amount of couplers and silver halides are required to obtain the required color density, and as a result, silver halide There are problems such as an increase in the cost of the color light-sensitive material, an increase in film thickness, and a decrease in the sharpness of the resulting color image. As a coupler for solving this problem, an acetanilide type coupler (for example, see Patent Document 1) in which a pyrimidin-4-one in which an alkyl group having 1 to 6 carbon atoms is substituted with a nitrogen atom is bonded, and a substituted alkyl group is used. An acetanilide-type coupler to which a substituted pyrimidin-4-one is bonded (for example, see Patent Document 2), and an acetanilide-type coupler to which an aryl group or heterocyclic group-substituted pyrimidin-4-one is bonded (for example, a patent) Reference 3) is also an acetanilide coupler to which a pyrimidin-4-one introduced with a divalent linking group such as a heteroatom is bonded (for example, refer to Patent Document 4). Acetanilide type couplers to which pyrimidin-4-one substituted with an alkyl group is bonded (see, for example, Patent Document 5). Proposed is, color reproducibility and light resistance are further improved. However, the couplers described in each of these patent documents are silent about the effect when an image is formed by area gradation.
[0013]
Furthermore, for the purpose of further improving the color reproduction of yellow, an acetanilide type coupler to which [1,2,4] thiadiazine-1,1-dioxide is bonded has been proposed (see, for example, Patent Document 6) and used for proofing. However, the color tone of the printing ink is slightly reddish, which is not preferable for proof use.
[0014]
[Patent Document 1]
US Pat. No. 5,455,149
[0015]
[Patent Document 2]
JP 2002-296740 A
[0016]
[Patent Document 3]
JP 2002-296671 A
[0017]
[Patent Document 4]
JP 2002-318442 A
[0018]
[Patent Document 5]
JP 2002-318443 A
[0019]
[Patent Document 6]
JP 2002-351023 A
[0020]
[Problems to be solved by the invention]
The present invention has been made in view of the above problems, and a first object of the present invention is to provide an area gradation image forming method excellent in color tone reproducibility. A second object of the present invention is to provide an area gradation image forming method excellent in halftone dot reproducibility.
[0021]
[Means for Solving the Problems]
The above object of the present invention has been achieved by the following constitution.
[0022]
1. An area gradation image forming method for reproducing halftone dots as an aggregate of minimum units (dots) for image formation using a silver halide color light-sensitive material, wherein the silver halide color light-sensitive material has the general formula (a) -1) or a dye-forming coupler represented by (a-2).
[0023]
2. 2. The area gradation image forming method according to claim 1, wherein an area gradation image is formed using an FM screening method.
[0024]
3. The silver halide color light-sensitive material has three or more color-developing layers on a support, and the color-developing layer located closest to the support is represented by the general formula (a-1) or (a-2 3. The area gradation image forming method according to 1 or 2 above, which comprises a dye-forming coupler represented by formula (1):
[0025]
4). 4. The area gradation image formation according to any one of 1 to 3 above, wherein Z in the general formula (a-1) is a residue that forms a 3H-pyrimidin-4-one ring. Method.
[0026]
5. 4. The area gradation image formation according to any one of 1 to 3 above, wherein Z in the general formula (a-2) is a residue forming a 1H-pyrimidin-4-one ring. Method.
[0027]
The present invention will be described in detail below.
In the present invention, the term area gradation image is used, but this is not expressed by the shading of the color of each pixel, but by the size of the area of the color developed at a specific density. It can be considered synonymous with halftone dots. The halftone dots used for normal printing are arranged at equal intervals according to the number of screen lines, and the shade of the image is expressed by the size of the arranged halftone dots. On the other hand, a method of expressing the density of an image by the density of fine dots of a certain size arranged in a pseudo-random arrangement is called an “FM (Frequency Modulation) screen”. Further, the halftone dots are arranged at equal intervals according to the number of screen lines, and the method may be referred to as an “AM (Amplitude Modulation) screen”.
[0028]
The characteristics of the FM screening method include rich expressiveness of details, the absence of moire and rosetta, and low quality degradation even when output at a coarse resolution. In this method, it is necessary to print minute halftone dots, but in the method of printing on the conventional silver halide color light-sensitive material and printing on the PS plate, the fluctuation of halftone dots in the process is large and practical. It didn't happen. However, a method of outputting directly to a printing plate such as a computer-to-plate (CTP) has come into practical use and has attracted attention again. Screening methods include crystal raster (Agfa), velvet screen (UGRA / FOGRA / KOHAN), Landot (Dainippon Screen Mfg.), Diamond screen (Heidelberg), Staccato (Cleo). Various methods have been proposed by various manufacturers such as Japan).
[0029]
In recent years, as described in Journal of the Japan Printing Society, Vol. 40, page 71 (2003), in order to improve the flat screen graininess and the difficulty of printing, which are disadvantages of the FM screening method, we devised an arrangement of halftone dots. New screening methods such as Staccato (manufactured by Creo Japan Co., Ltd.) and FAIRDOT (manufactured by Dainippon Screen Mfg. Co., Ltd.) in which the AM method and the FM method are hybridized have been developed.
[0030]
The present invention relates to a method for forming an image with area gradation, and various screening methods can be used. An FM screening method and FM / AM hybrid screening for forming an area gradation image with a small halftone dot. By the method, the effect of the present invention is remarkably exhibited.
[0031]
In the area gradation image forming method of the present invention, the silver halide color light-sensitive material to be used contains the dye-forming coupler represented by the general formula (a-1) or (a-2). .
[0032]
First, the dye forming couplers represented by the general formulas (a-1) and (a-2) according to the present invention will be described.
[0033]
In the general formula (a-1) and general formula (a-2), R represents a substituent, and the substituent represented by R is not particularly limited. For example, an alkyl group (for example, a methyl group) , Isopropyl, (t) butyl, cyclohexyl, dodecyl, etc.), alkenyl (eg, vinyl, allyl), alkynyl (eg, propargyl), aryl, (eg, phenyl, naphthyl) Group), heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, tetrazolyl group, etc.), halogen atom (for example, Chlorine atom, fluorine atom, etc.), alkoxy group (for example, methoxy group, propyloxy group, pentyloxy group, cyclohexyl) Oxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), heterocyclic oxy group (eg pyridyloxy group, tetrahydropyranyloxy group etc.), alkoxycarbonyl group (eg ethyloxycarbonyl group, Octyloxycarbonyl group, etc.), aryloxycarbonyl groups (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamido groups (eg, methylsulfonylamino group, ethylsulfonylamino group, cyclohexylsulfonylamino group, dodecylsulfonylamino group) Group, phenylsulfonylamino group, etc.), sulfamoyl group (for example, aminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, octylaminosulfonyl group, phenylaminosulfonyl group) 2-pyridylaminosulfonyl group, etc.), ureido group (eg, methylureido group, ethylureido group, cyclohexylureido group, octylureido group, phenylureido group, naphthylureido group, etc.), acyl group (eg, acetyl group, propylcarbonyl group) Cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, phenylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, octylcarbonyloxy group, phenylcarbonyloxy group, etc.) Carbamoyl group (for example, aminocarbonyl group, dimethylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, phenylaminocarbonyl group, 2 -Pyridylaminocarbonyl group etc.), acylamino group (eg methylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, 2-ethylhexylcarbonylamino group, dodecylcarbonylamino group, naphthylcarbonylamino group etc.), alkylsulfonyl group or An arylsulfonyl group (for example, ethylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, 2-pyridylamino group, etc.), cyano group, nitro group, sulfo group, carboxyl group, hydroxyl group and the like. It may be further substituted by a substituent described above.
[0034]
The group represented by R is preferably an alkyl group or an aryl group, and more preferably an alkyl group having 2 to 24 carbon atoms in total, including a substituent further substituted on R, or similarly a total carbon number of 6 to 24 aryl groups. The group represented by R is particularly preferably an alkyl group having 2 to 18 carbon atoms in total including a substituent further substituted on R, or an aryl group having 6 to 18 carbon atoms in the same manner. Here, the group substituted for R may include a hetero atom, and the total number of carbon atoms does not include the number of hetero atoms.
[0035]
In general formula (a-1) and general formula (a-2), R 'represents a substituent, and n represents an integer of 0 to 4. n is preferably 0-2.
[0036]
There is no restriction | limiting in particular as a substituent represented by R ', The group synonymous with the group enumerated by description of the said R can be mentioned. R ′ is preferably an acylamino group, a sulfonylamino group, an oxycarbonyl group and the like.
[0037]
X represents a hydrogen atom or a substituent. Examples of the substituent represented by X include the same groups as those described above for R ′. X is preferably an alkoxy group, an aryloxy group, a halogen atom, an amino group, an acylamino group, a ureido group or a sulfonamide group, more preferably an alkoxy group, an aryloxy group, a halogen atom or an acylamino group.
[0038]
Z represents an atomic group necessary for forming a nitrogen-containing 6-membered ring or 7-membered ring together with the —C (═O) —N—C═N— moiety.
[0039]
Examples of the nitrogen-containing 6-membered ring formed by Z include pyrimidin-4-one, 1,3-diazine-4,6-dione, [1,3,5] triazin-2-one, [1,2, 4] Triazin-5-one and the like.
[0040]
Examples of the nitrogen-containing 7-membered ring formed by Z include 1,3-diazepin-4-one, 1,3-diazepin-5-one, and the like.
[0041]
Z is preferably a 6-membered ring, and the 6-membered ring is preferably a residue that forms a pyrimidin-4-one ring, and Z in the general formula (a-1) represents a 3H-pyrimidin-4-one ring. It is preferably a residue to be formed, and Z in the general formula (a-2) is more preferably a residue that forms a 1H-pyrimidin-4-one ring.
[0042]
That is, Z is -C (-R ₂ ) = C (-R ₃ ) -CO-. R ₂ , R ₃ Are bonded to each other to form a 5- to 7-membered ring together with the —C═C— moiety, or each independently represents a hydrogen atom or a substituent. R ₂ , R ₃ Are bonded to each other to form a —C═C— moiety, preferably a 5- to 7-membered alicyclic, aromatic, or heterocyclic ring, such as a benzene ring, a pyrazole ring, a furan ring, a thiophene ring, Examples include a cyclopentene ring and a cyclohexene ring. More preferably, the ring is a 6-membered aromatic ring, most preferably a benzene ring. R ₂ , R ₃ When represents a substituent, these may be the same or different, and examples of the substituent include the same groups as the substituents described for R ′ described above.
[0043]
In the general formula (a-1) and the general formula (a-2), A represents a hydrogen atom or a group that can be removed upon coupling with an oxidized form of a developing agent. Examples of the group capable of leaving upon coupling with an oxidized form of the developing agent represented by A include, for example, a phenoxy group, an alkoxy group, an acyloxy group, a carbamoyl group, a sulfonyl group, or a nitrogen-containing heterocyclic group (for example, an imidazolyl group). , Pyrazolyl group, or hydantoinyl group). These groups represented by A can also have a substituent. Examples of the substituent are the same as those represented by R ′ in the general formula (a-1) and general formula (a-2). The group can be mentioned. More specifically, those having the same meaning as the group represented by W described in paragraphs [0033] to [0043] of JP-A-8-29932 can be exemplified.
[0044]
Specific examples of the yellow dye-forming couplers represented by the general formula (a-1) and general formula (a-2) of the present invention are shown below, but the present invention is not limited thereto.
[0045]
[Chemical 2]

[0046]
[Chemical 3]

[0047]
[Formula 4]

[0048]
[Chemical formula 5]

[0049]
[Chemical 6]

[0050]
[Chemical 7]

[0051]
[Chemical 8]

[0052]
[Chemical 9]

[0053]
Embedded image

[0054]
Embedded image

[0055]
Embedded image

[0056]
Examples of yellow couplers represented by the general formula (a-1) and the general formula (a-2) according to the present invention include, for example, US Pat. No. 5,455,149, US Patent Publication No. 2003-64332, and the like. It can be synthesized according to the method described in 1.
[0057]
In the silver halide color light-sensitive material according to the present invention, the yellow coupler according to the present invention is usually 1 × 10 per 1 mole of silver halide. ^-3 Mol to 1 mol, preferably 1 × 10 ^-2 Mol ~ 8x10 ^-1 It can be used in a molar range. The yellow coupler according to the present invention can be used in combination with other types of couplers. For the couplers used in the silver halide color light-sensitive material according to the present invention, the methods and techniques used in ordinary dye-forming couplers are similarly applied.
[0058]
The additive layer of the yellow coupler represented by formula (a-1) or formula (a-2) according to the present invention is not particularly limited, but is a silver halide color photosensitive having three or more coloring layers. In the material, a dye-forming coupler represented by the general formula (a-1) or (a-2) according to the present invention is formed on a color developing layer (hereinafter also referred to as an image forming layer) located closest to the support. It is preferable to contain.
[0059]
As the magenta coupler used in the silver halide color light-sensitive material according to the present invention, a compound represented by the 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. Furthermore, as other specific examples, compounds M-1 to M-61 described on pages 6 to 21 of European Patent 0,273,712 and 36 to 92 of 0,235,913 are disclosed. Among the compounds 1-223 described on the page are those other than the representative examples described above.
[0060]
The magenta coupler can also be used in combination with other types of magenta couplers. Usually, the total amount of magenta coupler is 1 × 10 6 per mole of silver halide. ^-3 Mol to 1 mol, preferably 1 × 10 ^-2 Mol ~ 8x10 ^-1 It can be used in a molar range.
[0061]
In the silver halide color light-sensitive material according to the present invention, the spectral absorption λ of the magenta image to be formed _max Is preferably 530 to 560 nm, and λL _0.2 Is preferably 580 to 635 nm. λL _0.2 In the spectral absorbance curve of an image dye, when the maximum absorbance is 1.0, the wavelength is longer than the wavelength indicating the maximum absorbance and the absorbance is 0.2. This amount is a reference amount indicating the magnitude of unnecessary absorption on the long wave side of the image dye, and λ _max It indicates that the closer to the wavelength, the less unnecessary absorption is preferable.
[0062]
The magenta image forming layer of the silver halide color photographic 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 silver halide color light-sensitive material according to the present invention include known pivaloyl acetanilide type or benzoyl acetanilide type couplers. Specific examples of preferable yellow couplers to be contained in the magenta image-forming layer of the silver halide color photographic material according to the present invention include, for example, YCP-1 described on the right column on pages 6 to 15 of JP-A-8-314079. Although couplers represented by ˜YCP-39 are mentioned, of course, it is not limited to these.
[0063]
In the silver halide color light-sensitive material according to the present invention, as the cyan coupler contained in the cyan image forming layer, a known phenol-based, naphthol-based, imidazole-based or azole-based coupler can be used. For example, phenol couplers substituted with alkyl groups, acylamino groups, or ureido groups, naphthol couplers formed from a 5-aminonaphthol skeleton, and 2-equivalent naphthol couplers introduced with an oxygen atom as a leaving group are representative. The Among these, preferred compounds include compounds represented by the general formulas [CI] and [C-II] described on page 13 of JP-A-6-95283.
[0064]
Examples of the azole coupler include a pyrazoloazole coupler represented by the general formula [I] or [II] described on page 2 of JP-A-8-171185, or JP-A-11-282138. Examples thereof include pyrroloazole couplers represented by the general formula (I).
[0065]
The cyan coupler is usually 1 × 10 5 per mole of silver halide in a silver halide emulsion layer. ^-3 ~ 1 mole, preferably 1 x 10 ^-2 ~ 8x10 ^-1 It can be used in a molar range.
[0066]
In order to adjust the spectral absorption characteristics of the magenta color image, cyan color image, and yellow color image, it is preferable to add a compound having a color tone adjusting action. As the compound for this purpose, a phosphate ester compound represented by the general formula [HBS-I] and a phosphine oxide compound represented by [HBS-II] described on page 22 of JP-A-6-95283 are preferred. More preferably, it is a compound represented by the general formula [HBS-II] described on page 22 of the same publication.
[0067]
Each of the magenta, cyan, and yellow couplers can be used in combination with an anti-fading agent for preventing fading of the formed dye image due to light, heat, humidity, and the like. Preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, and phenolic compounds represented by general formula IIIB described in JP-A-3-174150. An amine compound represented by the general formula A described in JP-A No. 64-90445, and a metal complex represented by the general formulas XII, XIII, XIV, XV described in JP-A No. 62-182741 are particularly preferable. Preferred for magenta dyes. Further, the compound represented by the general formula I ′ described in JP-A-1-196049 and the compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.
[0068]
When using an oil-in-water emulsion dispersion method when adding an anti-stain agent or other organic compound used in the silver halide color photographic material according to the present invention, it is usually a water-insoluble high-boiling organic material having a boiling point of 150 ° C. or higher. If necessary, the solvent is dissolved in combination with a low boiling point and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low boiling organic solvent after the dispersion or simultaneously with the dispersion may be incorporated. Examples of the high-boiling organic solvent that can be used for dissolving and dispersing the stain inhibitor include phosphate esters 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 JP-A 4-265975 are preferably used. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.
[0069]
The silver halide emulsion used in the silver halide color light-sensitive material according to the present invention is preferably a silver halide emulsion comprising 95 mol% or more of silver chloride. Silver chloride, silver chlorobromide, silver chloroiodobromide, Those having an arbitrary halogen composition such as silver chloroiodide are used. Among them, a silver chlorobromide containing 95 mol% or more of silver chloride, a silver halide emulsion having a portion containing a high concentration of silver bromide is particularly preferably used, and 0.05% of silver iodide is present in the vicinity of the surface. Silver chloroiodide containing ˜0.5 mol% is also preferably used. In a silver halide emulsion having a portion containing a high concentration of silver bromide, the portion containing a high concentration of silver bromide may be a so-called core-shell type silver halide emulsion, or a complete layer A so-called epitaxy-bonded region may be formed in which only regions having different compositions are present without being formed. The portion where silver bromide is present at a high concentration is particularly preferably formed at the apex of the crystal grain on the surface of the silver halide grain. Further, the composition may change continuously or discontinuously.
[0070]
The negative silver halide emulsion used in the silver halide color light-sensitive material according to the present invention preferably contains heavy metal ions. This is expected to improve so-called reciprocity failure and prevent desensitization in high-illuminance exposure and prevent softening in the shadow region.
[0071]
Heavy metal ions that can be used for such purposes include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, and twelfth metals such as cadmium, zinc, and mercury. Group transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be given. Of these, 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, as its ligand, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, 1, 2, 4-triazole, thiazole, etc. can be mentioned. Of these, chloride ion, bromide ion and the like are preferable. These ligands may be used alone or in combination with a plurality of ligands.
[0072]
The characteristics of these metal compounds can also be characterized as the depth of electron traps when incorporated 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 compounds having a second lead ion or a cyano ligand, which are effective in improving reciprocity failure, particularly low-illuminance failure. is there. In addition, examples of the compound that provides a deep electron trap having a depth of 0.35 eV or more include Ir, Rh, and Ru compounds having halide ions and nitrosyl ligands. These compounds can be preferably used for improving high intensity reciprocity failure. It is also preferable to use a compound that provides a shallow electron trap having a depth of 0.2 eV or less and a compound that provides a deep electron trap having a depth of 0.35 eV or more in combination. These compounds are described in detail in pages 4 to 5 of JP-A No. 2000-214561.
[0073]
As a method of containing heavy metal ions in the silver halide emulsion, the heavy metal compound is added to each step before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. What is necessary is just to add in arbitrary places.
[0074]
The heavy metal compound can be dissolved together with the halide salt and added continuously throughout the grain formation process. It can also be prepared by forming silver halide fine particles containing these heavy metal compounds in advance and adding them. The amount of heavy metal ions added to the silver halide emulsion is 1 × 10 5 per mole of silver halide. ^-9 Mole or more, 1 × 10 ^-2 Mole or less is preferable, particularly 1 × 10 ^-8 More than mole 5 × 10 ^-5 Molar or less is preferable.
[0075]
Any silver halide grains can be 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, 4,225,666, JP-A-55-26589, JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973), etc., particles having an octahedron, tetrahedron, dodecahedron, etc. can be produced and used. Furthermore, particles having twin planes may be used.
[0076]
The grains used in the present invention are preferably grains having a single shape, but it is particularly preferred to add two or more monodispersed silver halide emulsions to the same image forming layer.
[0077]
The particle size of the silver halide grains used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably in consideration of suitability for rapid processability and reaching sensitivity, and other photographic performance. Is in the range of 0.2 to 1.0 μm.
[0078]
This grain size can be determined by measuring the projected area of the silver halide grains or using an approximate diameter. If the silver halide grains are substantially uniform in shape, the particle size distribution can be expressed fairly accurately as a diameter or projected area.
[0079]
The grain size distribution of the silver halide grains used in the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably a coefficient of variation of 0. .2 or more monodispersed emulsions of 15 or less are added to the same image forming layer. The variation coefficient here is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.
[0080]
Coefficient of variation = S / R
Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.
[0081]
As a silver halide emulsion preparation apparatus and preparation method, various methods known in the art can be used.
[0082]
The silver halide emulsion used in the present invention may be obtained by any of the acidic method, neutral method and ammonia method. The silver halide grains may be grown at a time, or may be grown after preparing seed grains. The method for preparing the seed particles and the method for growing them may be the same or different.
[0083]
Further, the form of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferred. Furthermore, as one form of the simultaneous mixing method, the pAg controlled double jet method described in JP-A No. 54-48521 can be used.
[0084]
Further, an apparatus for supplying a water-soluble silver salt and a water-soluble halide salt aqueous solution from an adding apparatus disposed in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Patent No. 2 , 921,164, etc., an apparatus for continuously adding an aqueous solution of a water-soluble silver salt and a water-soluble halide salt, the reaction mother liquor outside the reactor described in JP-B-56-501776, etc. An apparatus for forming grains while keeping the distance between the silver halide grains constant by taking out and concentrating by ultrafiltration may be used.
[0085]
Further, 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 at the time of forming silver halide grains or after the completion of grain formation.
[0086]
The negative silver halide emulsion used in the present invention can be appropriately combined with a sensitizing method using a gold compound, a sensitizing method using a chalcogen sensitizer, and the like. As the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, triethylthiourea, allylthiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.
[0087]
The addition amount of the sulfur sensitizer is preferably changed as appropriate depending on the type of silver halide emulsion to be applied, the expected effect, and the like, but is generally 5 × 10 5 per mole of silver halide. ^-10 ~ 5x10 ^-5 In the molar range, preferably 5 × 10 ^-8 ~ 3x10 ^-5 The range of moles.
[0088]
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 gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but usually 1 × 10 6 per mole of silver halide. ^-4 ~ 1x10 ^-8 Mole is preferred. More preferably 1 × 10 ^-5 ~ 1x10 ^-8 Is a mole. These compounds can also be added for various purposes not as a sensitizer but at the stage of preparing a coating solution.
[0089]
As a chemical sensitization method for the negative silver halide emulsion used in the present invention, a reduction sensitization method may be used.
[0090]
The silver halide color light-sensitive material according to the present invention may have a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.
[0091]
As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, it is described in JP-A-3-251840, page 28. BS-1 to 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to 8 described in page 29 of the same publication are preferably used.
[0092]
These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization. In addition, these dyes may be added as a solution by dissolving in water or an organic solvent miscible with water such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide, or a sensitizing dye. May be added as a water miscible solvent solution, emulsion or suspension having a density greater than 1.0 g / ml.
[0093]
As a method for dispersing the sensitizing dye, in addition to a method of mechanically pulverizing and dispersing fine particles having a size of 1 μm or less in an aqueous system using a high-speed stirring type disperser, a pH of 6 to 5 as described in JP-A-58-105141 is used. 8, a method of mechanically pulverizing and dispersing fine particles having a size of 1 μm or less in an aqueous system at a temperature of 60 to 80 ° C. ^-2 A method of dispersing in the presence of a surfactant that suppresses N / m or less, a method described in JP-A-50-80826, which is substantially free of water and is dissolved in an acid whose pKa is not higher than 5, A method of adding and dispersing in an aqueous liquid and adding this dispersion to a silver halide emulsion can be used.
[0094]
The dispersion medium used for dispersion is preferably water, but a small amount of an organic solvent can be added to adjust the solubility, or a hydrophilic colloid such as gelatin can be added to improve the stability of the dispersion.
[0095]
Examples of the dispersion apparatus that can be used to prepare the dispersion include, for example, a ball mill, a sand mill, an ultrasonic disperser, and the like, in addition to the high-speed stirring disperser described in FIG. 1 of JP-A-4-125561. Can be mentioned.
[0096]
Further, when using these dispersing devices, as described in JP-A-4-125632, a pre-treatment such as dry pulverization may be performed in advance, followed by wet dispersion.
[0097]
The silver halide emulsion used in the present invention may contain one or a combination of two or more sensitizing dyes.
[0098]
In the silver halide emulsion used in the present invention, for the purpose of preventing fogging that occurs during the preparation process of the silver halide color light-sensitive material, reducing performance fluctuation during storage, and preventing fogging during development, Known antifoggants and stabilizers can be used. Examples of preferable compounds that can be used for such purposes include nitrogen-containing heterocyclic mercapto compounds represented by the general formula (II) described in the lower column on page 7 of JP-A-2-14636. Specific examples of preferred compounds are (IIa-1) to (IIa-8), (IIb-1) to (IIb-7) described on page 8 of the same publication, and JP-A 2000- No. 267235, page 8, right column, lines 32 to 36, can be mentioned. Depending on the purpose, these compounds are added at any step such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, or a coating solution preparation step. When chemical sensitization is performed in the presence of these compounds, 1 × 10 6 per mole of silver halide. ^-5 ~ 5x10 ^-4 It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 x 10 per mole of silver halide ^-6 ~ 1x10 ^-2 A molar amount is preferred, 1 × 10 ^-5 ~ 5x10 ^-3 Mole is more preferred. In the coating solution preparation step, when added to the silver halide emulsion layer, 1 × 10 5 per mole of silver halide. ^-6 ~ 1x10 ^-1 A molar amount is preferred, 1 × 10 ^-5 ~ 1x10 ^-2 Mole is more preferred. When added to a layer other than the silver halide emulsion layer, the content in the coating film is 1 m. ² 1 × 10 per ^-9 ~ 1x10 ^-3 A molar amount is preferred.
[0099]
Other additives can be added to the silver halide emulsion used in the present invention for various purposes. For example, disulfides and polysulfide compounds such as A-20, C-1, C-9, C-14, C-15, C-16, C-40 and the like specifically described in JP-A-2-146036 It is preferable to use thiosulfonic acid compounds such as D-1, D-3, D-6 and D-8, inorganic sulfur and the like.
[0100]
In the silver halide color light-sensitive material according to 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 known compound can be used. In particular, as dyes having absorption in the visible region, the dyes of AI-1 to 11 described in JP-A-3-251840, page 308, and special dyes can be used. The dyes described in Kaihei 6-3770 are preferably used.
[0101]
The silver halide color light-sensitive material according to the present invention comprises a hydrophilic layer colored with at least one diffusion-resistant compound on the side closer to the support than the silver halide emulsion layer closest to the support. It is preferable to have a conductive colloid layer. As the coloring substance, a dye or other organic or inorganic coloring substance can be used.
[0102]
In the silver halide color light-sensitive material used in the present invention, among the silver halide emulsion layers, at least one colored hydrophilic colloid layer is closer to the support than the silver halide emulsion layer closest to the support. And 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, and titanium dioxide is particularly preferable for various reasons. The white pigment is dispersed in a hydrophilic colloid aqueous solution binder such as gelatin so that the treatment liquid can penetrate. The amount of white pigment applied is preferably 0.1 to 50 g / m. ² More preferably 0.2 to 5 g / m. ² Range.
[0103]
Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment-containing layer, if necessary, an undercoat layer or a non-light-sensitive hydrophilic layer such as an intermediate layer at an arbitrary position. A colloid layer can be provided.
[0104]
Addition of a fluorescent brightening agent to the silver halide color light-sensitive material according to the present invention is preferable in that the white background can be further improved. The fluorescent whitening agent is not particularly limited as long as it is a compound that can absorb ultraviolet rays and emit visible light fluorescence, but is a diaminostilbene compound having at least one sulfonic acid group in the molecule, These compounds are preferable because they have an effect of promoting the elution of the sensitizing dye out of the silver halide color light-sensitive material. Another preferred form is a solid particulate compound having a fluorescent whitening effect.
[0105]
As a preferable compound as a surfactant used for dispersion of photographic additives used in the light-sensitive material according to the present invention and adjustment of surface tension during coating, a hydrophobic group having 8 to 30 carbon atoms and sulfone in one molecule. The thing containing an acid group or its salt is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. A dispersion of an oil-soluble additive emulsified with these surfactants is usually added to a coating solution containing a silver halide emulsion. The time from application to application to application is preferably short, preferably within 10 hours, and more preferably within 3 hours and within 20 minutes.
[0106]
In the silver halide color light-sensitive material according to the present invention, a compound that reacts with an oxidized developer is added to an intermediate layer provided between silver halide emulsion layers to prevent color turbidity. It is preferable to improve fog and the like by directly adding to. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, including compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17. .
[0107]
In the silver halide color photographic material according to the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of the dye image. Preferred ultraviolet absorbers include benzotriazoles. Particularly preferred compounds include compounds represented by general formula III-3 described in JP-A-1-250944, and general formulas described in JP-A-64-66646. Compounds represented by III, UV-1L to UV-27L described in JP-A-63-187240, compounds represented by general formula I described in JP-A-4-1633, and compounds described in JP-A-5-165144 Examples include compounds represented by general formulas (I) and (II).
[0108]
The silver halide color light-sensitive material according to the present invention preferably contains an oil-soluble dye or pigment because the white background is improved. Typical examples of oil-soluble dyes include compounds 1-27 described in JP-A-2-842, pages 8-9.
[0109]
In the silver halide color light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder, but other gelatins, for example, gelatin derivatives, gelatin and other polymer graft polymers, other than gelatin as necessary. It is also possible to use hydrophilic colloids such as synthetic hydrophilic polymer substances such as proteins, sugar derivatives, cellulose derivatives, and single or copolymers.
[0110]
As a hardener for these binders, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination. It is preferable to use the compounds described in JP-A-61-249054 and JP-A-61-245153. In order to prevent the growth of mold and bacteria that adversely affect photographic performance and image storage stability, 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 improve the physical properties of the surface of the silver halide color light-sensitive material or the processed silver halide color light-sensitive material, for example, a slipping agent described in JP-A-6-118543 and JP-A-2-73250 is used as a protective layer. It is preferable to add a matting agent.
[0111]
As the support used for the silver halide color light-sensitive material according to the present invention, any material may be used. For example, paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, chloride A vinyl sheet, polypropylene that may contain a white pigment, a polyethylene terephthalate support, baryta paper, or the like can be used. Especially, the support body which has a water-resistant resin coating layer on both surfaces of a base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.
[0112]
The support having a water-resistant resin coating layer on the paper surface is usually 50 to 300 g / m. ² However, for the purpose of obtaining a proof image, in order to bring the handling feeling closer to the printing paper, 130 g / m ² The following base paper is preferably used, and further 70 to 120 g / m. ² The base paper is preferably used.
[0113]
The support used in the present invention can be preferably used even if it has random irregularities or is smooth.
[0114]
As the white pigment used for the support, inorganic and / or organic white pigments can be used, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfates such as barium sulfate, calcium carbonate Examples thereof include carbonates of alkaline earth metals such as silicas, silicas such as finely divided silicic acid and synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc and clay. Preferred white pigments are barium sulfate and titanium oxide.
[0115]
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 or more from the viewpoint of improving sharpness.
[0116]
The degree of dispersion of the white pigment in the water-resistant resin layer covering both sides of the paper support 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 coefficient of variation described in the above publication.
[0117]
The resin layer of the paper support having water-resistant resin layers on both sides used in the present invention may be a single layer or a plurality of layers. When the resin layer is made into a plurality of layers and a white pigment is contained at a high concentration on the surface side in contact with the silver halide emulsion layer, the sharpness improving effect is great, which is one of the preferred forms for forming a proof image.
[0118]
Further, the value of the center plane average roughness (SRa) of the support is preferably 0.15 μm or less, more preferably 0.12 μm or less from the viewpoint of obtaining the effect of good gloss.
[0119]
The silver halide color light-sensitive material used in the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and directly or undercoat layer (adhesion of the support surface, antistatic property). Or one or more subbing layers for imparting properties, dimensional stability, friction resistance, hardness, antihalation properties, frictional properties and / or other properties.
[0120]
In coating a silver halide color light-sensitive material using a silver halide emulsion, a thickener may be used for the purpose of improving the coating property. As the application method, extrusion coating or curtain coating capable of simultaneously applying two or more layers is particularly useful.
[0121]
Next, details of the area gradation image forming method of the present invention will be described.
In the exposure apparatus used in the area gradation image forming method of the present invention, any known exposure light source can be preferably used, but a laser or a light emitting diode (hereinafter referred to as LED) is more preferably used.
[0122]
As the laser, a semiconductor laser (hereinafter referred to as LD) is preferably used because it is compact and has a long light source life. LDs are used for applications such as DVDs, optical pickups for music CDs, barcode scanners for POS systems, optical communications, etc., and they are inexpensive and can provide relatively high output. have. Specific examples of LD include aluminum, gallium, indium, arsenic (650 nm), indium, gallium, phosphorus (up to 700 nm), gallium, arsenic, phosphorus (610-900 nm), gallium, aluminum, arsenic (760-850 nm). And the like. Recently, a laser that oscillates blue light has been developed. However, at present, it is advantageous to use an LD as a light source having a wavelength longer than 610 nm.
[0123]
As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted into a half-wavelength light by an SHG element and emitted, and a green light having no appropriate light source is obtained because visible light is obtained. ~ Used as a light source in the blue region. An example of this type of light source is a YAG laser combined with an SHG element (532 nm).
[0124]
Examples of the gas laser include a helium / cadmium laser (about 442 nm), an argon ion laser (about 514 nm), a helium neon laser (about 544 nm and 633 nm), and the like.
[0125]
LEDs having the same composition as LD are known, but various LEDs from blue to infrared have been put into practical use.
[0126]
As the exposure light source used in the present invention, each laser may be used alone, or may be used in combination as a multi-beam. In the case of an LD, for example, a beam composed of 10 luminous fluxes can be obtained by arranging 10 LDs. On the other hand, in the case of a helium neon laser, light emitted from the laser is divided into, for example, 10 light beams by a beam separator.
[0127]
The intensity change of the exposure light source can be directly modulated to change the value of the current flowing through each element in the case of an LD or LED. In the case of an LD, the intensity may be changed using an element such as an AOM (acousto-optic modulator). In the case of a gas laser, devices such as AOM and EOM (electro-optic modulator) are generally used.
[0128]
When an LED is used as the light source, a method of exposing the same pixel with a plurality of elements may be used as long as the amount of light is weak.
[0129]
Moreover, you may use an organic light emitting element as a light source which replaces these, These are described in Unexamined-Japanese-Patent No. 2000-258846 etc., for example.
[0130]
Usually, in the case of area gradation exposure, the purpose can be achieved by causing Y, M, C, and black to be colored. 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 using different exposure amounts of three or more values. In printing, a special color plate may be used, but in order to reproduce this, it is preferable to perform exposure using different exposure values of four or more values.
[0131]
In the case of a laser light source, the beam diameter is preferably 25 μm or less, more preferably 6 to 22 μm. If it is smaller than 6 μm, it is preferable in terms of image quality, but adjustment is difficult or the processing speed decreases. On the other hand, if it is larger than 25 μm, unevenness increases and the sharpness of the image also deteriorates. By optimizing the beam diameter, high-definition images without unevenness can be written at high speed.
[0132]
In order to draw an image with such light, it is necessary to scan the silver halide color photosensitive material with a light beam. The silver halide color photosensitive material is wound around a cylindrical drum and rotated while rotating at high speed. A so-called cylindrical outer surface scanning method in which the light beam is moved in a direction perpendicular to the direction may be employed, and a so-called cylindrical inner surface scanning method in which a silver halide color photosensitive material is exposed in close contact with a cylindrical depression may be preferably used. A so-called plane scanning method may be employed in which the polyhedral mirror is rotated at a high speed, and the silver halide color photosensitive material conveyed thereby is exposed by moving the light beam perpendicular to the conveying direction. From the viewpoint of high image quality and obtaining a large image, the cylindrical outer surface scanning method is more preferably used.
[0133]
In order to perform exposure by the cylindrical outer surface scanning method, the silver halide color photosensitive material must be brought into close contact with the cylindrical drum accurately. In order to reliably perform this close contact, it is necessary to accurately align and transport. The silver halide color light-sensitive material used in the present invention can be preferably used because the surface on the side to be exposed (the side on which the silver halide emulsion layer is coated) can be more accurately aligned. From the same viewpoint, the support used for the silver halide color photographic material used in the present invention has an appropriate rigidity, and a Taber rigidity of 0.8 to 4.0 is preferable.
[0134]
The diameter of the exposure drum can be arbitrarily set according to the size of the silver halide color photosensitive material to be exposed. The number of rotations of the exposure drum can be arbitrarily set, but an appropriate number of rotations can be selected depending on the beam diameter of the laser beam, the energy intensity, the writing pattern, the sensitivity of the silver halide color photosensitive material, and the like. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at a higher rotation speed. Specifically, 200 to 3000 rotations per minute is preferably used.
[0135]
The silver halide color photosensitive material can be fixed to the exposure drum by mechanical means, or a large number of fine holes that can be sucked on the drum surface are provided according to the size of the silver halide color photosensitive material. In addition, the silver halide color light-sensitive material can be attracted and adhered. Adhering the silver halide color photosensitive material to the exposure drum as much as possible is important to prevent troubles such as image unevenness.
[0136]
Next, the development process will be described.
In the present invention, known compounds can be used as the aromatic primary amine developing agent used in the color development processing. Examples of these compounds include the following compounds.
[0137]
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 color developer can be used in any pH range, but is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0 from the viewpoint of rapid processing. It is done.
[0138]
The processing temperature for color development according to the present invention is preferably 35 ° C. or higher and 70 ° C. or lower. The higher the temperature, the shorter the treatment is possible and the better. However, it is preferable that the temperature is not so high from the stability of the treatment liquid, and the treatment is more preferably performed at 37 ° C or higher and 60 ° C or lower.
[0139]
The color development time is generally about 3 minutes 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds. In addition to the above color developing agent, a known developer component compound can be added to the color developer. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chloride ions and benzotriazoles, a preservative and a chelating agent are used.
[0140]
The silver halide color light-sensitive material according to 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. Moreover, you may perform a stabilization process as an alternative to a washing process.
[0141]
In the method for processing a silver halide color light-sensitive material according to the present invention, a compound having a fluorescent whitening effect or a stain after processing is appropriately reduced in any of a developer, a bleach-fixing solution, and a stabilizing processing solution. It is preferred to add the compound. In particular, addition to a color developer and a bleach-fix solution is preferable. The addition amount 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, preferably 5 g / L or more and 10 g / L. Is particularly preferred.
[0142]
The development processing apparatus used for the development processing of the silver halide color photosensitive material according to the present invention may be a belt transport type that conveys the silver halide color photosensitive material sandwiched between rollers disposed in a processing tank, or a belt. The endless belt method may be used in which the silver halide color photographic material is fixed and transported to the substrate. However, the processing tank is formed in a slit shape, the processing solution is supplied to the processing tank, and the silver halide color photographic material is supplied. A transport method, a spray method in which the treatment liquid is sprayed, a web method by contact with a carrier impregnated with the treatment liquid, a method using a viscous treatment liquid, and the like can also be used. When processing a large amount of silver halide color light-sensitive material, it is usually performed using an automatic developing machine. In this case, it is preferable that the amount of replenisher to be replenished according to the processing amount is smaller. The most preferable treatment form in view of environmental suitability and the like is to add a treatment agent in the form of a tablet as a replenishment method, and as this method, the method described in published technical report No. 94-16935 is most preferred.
[0143]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these.
[0144]
Example 1
<< Preparation of silver halide color photosensitive material >>
[Preparation of Sample 101]
A polyethylene laminated paper reflective support (Taber stiffness) with a mass per square meter of 115 g of laminated high-density polyethylene on one side and molten polyethylene containing 15% by mass of anatase-type titanium oxide dispersed on the other side. = 3.5, PY value = 2.7 μm), each layer having the structure shown in Table 1 below was coated on the side of the polyethylene layer containing titanium oxide, and further on the back side, gelatin 6.00 g / m ² Silica matting agent 0.65 g / m ² Sample 101, which is a multilayer silver halide color light-sensitive material coated with a layer containing silver, was prepared.
[0145]
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. Moreover, (H-1) and (H-2) were added as a hardening agent. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension. Moreover, the total amount of (F-1) in each layer is 0.04 g / m. ² It added so that it might become.
[0146]
[Table 1]

[0147]
SU-1: Sodium tri-i-propylnaphthalenesulfonate
SU-2: sulfosuccinic acid di (2-ethylhexyl) sodium salt
SU-3: Sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) sodium salt
H-1: Tetrakis (vinylsulfonylmethyl) methane
H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium
HQ-1: 2,5-di-t-octyl hydroquinone
HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone
HQ-3: Mixture of mass ratio 1: 1: 2 of 2,5-di-sec-dodecyl hydroquinone, 2,5-di-sec tetradecyl hydroquinone and 2-sec-dodecyl-5-sec-tetradecyl hydroquinone
HQ-4: 2,5-di-t-butylhydroquinone
PVP: Polyvinylpyrrolidone
[0148]
Embedded image

[0149]
Embedded image

[0150]
Embedded image

[0151]
Each photosensitive silver halide emulsion used for the preparation of Sample 101 was prepared according to the following method.
[0152]
(Preparation of blue-sensitive silver halide emulsion)
In 1 liter of 2% gelatin aqueous solution kept at 40 ° C., the following (A solution) and (B solution) were simultaneously added while controlling pAg = 7.3 and pH = 3.0, and the following (C solution) And (Liquid D) were simultaneously added while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled according to the method described in JP-A-59-45437, and pH was controlled using sulfuric acid or a sodium hydroxide aqueous solution.
[0153]
<Liquid A>
Sodium chloride 3.42g
Potassium bromide 0.03g
Add water to finish 200ml
<Liquid B>
Silver nitrate 10g
Add water to finish 200ml
<C liquid>
Sodium chloride 102.7g
Hexachloroiridium (IV) potassium 4 × 10 ^-8 Mole
Potassium hexacyanoferrate (II) 2 × 10 ^-5 Mole
Potassium bromide 1.0g
Add water to finish 600ml
<D liquid>
300 g of silver nitrate
Add water to finish 600ml
After completion of the addition, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous magnesium sulfate manufactured by Kao Atlas, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.71 μm. A monodispersed cubic emulsion EMP-101 having a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% was obtained.
[0154]
The emulsion EMP-101 was optimally chemically sensitized at 60 ° C. using the following compounds to obtain a blue-sensitive silver halide emulsion Em-B101.
[0155]
Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer: STAB-1 3 × 10 ^-4 Mole / Mole AgX
Stabilizer: STAB-2 3 × 10 ^-4 Mole / Mole AgX
Stabilizer: STAB-3 3 × 10 ^-4 Mole / Mole AgX
Sensitizing dye: BS-1 4 × 10 ^-4 Mole / Mole AgX
Sensitizing dye: BS-2 1 × 10 ^-4 Mole / Mole AgX
Potassium bromide 0.2g / mol AgX
Next, in the preparation of the emulsion EMP-101, the average grain size was changed in the same manner except that the addition times of (A liquid) and (B liquid) and (C liquid) and (D liquid) were changed. A monodispersed cubic emulsion EMP-102 having a diameter of 0.64 μm, a coefficient of variation of grain size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained.
[0156]
A blue-sensitive silver halide emulsion Em-B102 was prepared in the same manner as in the preparation of the blue-sensitive silver halide emulsion Em-B101, except that the emulsion EMP-102 was used instead of the emulsion EMP-101. A blue-sensitive silver halide emulsion using a 1: 1 mixture of -B101 and Em-B102 in the seventh layer was prepared.
[0157]
(Preparation of green sensitive silver halide emulsion)
In the preparation of the emulsion EMP-101, the average particle size of 0 was similarly obtained except that the addition time of (A liquid) and (B liquid) and the addition time of (C liquid) and (D liquid) were changed. A monodispersed cubic emulsion EMP-103 having a thickness of .40 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.
[0158]
The emulsion EMP-102 was optimally chemically sensitized at 55 ° C. using the following compound to obtain a green photosensitive silver halide emulsion Em-G101.
[0159]
Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer: STAB-1 3 × 10 ^-4 Mole / Mole AgX
Stabilizer: STAB-2 3 × 10 ^-4 Mole / Mole AgX
Stabilizer: STAB-3 3 × 10 ^-4 Mole / Mole AgX
Sensitizing dye: GS-1 1 × 10 ^-4 Mole / Mole AgX
Sensitizing dye: GS-2 1 × 10 ^-4 Mole / Mole AgX
Sensitizing dye: GS-3 2 × 10 ^-4 Mole / Mole AgX
Sodium chloride 0.5g / mol AgX
Next, in the preparation of the emulsion EMP-103, the average particle size was changed in the same manner except that the addition times of (A liquid) and (B liquid) and (C liquid) and (D liquid) were changed. A monodispersed cubic emulsion EMP-104 having a 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.
[0160]
A green-sensitive silver halide emulsion Em-G102 was prepared in the same manner as in the preparation of the green-sensitive silver halide emulsion Em-G101, except that EMP-104 was used instead of EMP-103. Em-G101 and Em -A green-sensitive silver halide emulsion using a 1: 1 mixture of G102 in the fifth layer.
[0161]
(Preparation of red-sensitive silver halide emulsion)
The prepared emulsion EMP-103 was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion Em-R101.
[0162]
Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 2 × 10 ^-4 Mole / Mole AgX
Stabilizer: STAB-2 2 × 10 ^-4 Mole / Mole AgX
Stabilizer: STAB-3 2 × 10 ^-4 Mole / Mole AgX
Stabilizer: STAB-4 1 × 10 ^-4 Mole / Mole AgX
Sensitizing dye: RS-1 1 × 10 ^-4 Mole / Mole AgX
Sensitizing dye: RS-2 1 × 10 ^-4 Mole / Mole AgX
Supersensitizer: SS-1 2 × 10 ^-4 Mole / Mole AgX
Next, the prepared emulsion EMP-103 was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion Em-R102.
[0163]
Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 2 × 10 ^-4 Mole / Mole AgX
Stabilizer: STAB-2 2 × 10 ^-4 Mole / Mole AgX
Stabilizer: STAB-3 2 × 10 ^-4 Mole / Mole AgX
Stabilizer: STAB-4 1 × 10 ^-4 Mole / Mole AgX
Sensitizing dye: RS-1 2 × 10 ^-4 Mole / Mole AgX
Sensitizing dye: RS-2 2 × 10 ^-4 Mole / Mole AgX
Supersensitizer: SS-1 2 × 10 ^-4 Mole / Mole AgX
A 1: 1 mixture of the red-sensitive silver halide emulsion Em-R101 and the red-sensitive silver halide emulsion Em-R102 prepared above was used as the red-sensitive silver halide emulsion for the third layer.
[0164]
Details of the additives used in the preparation of each of the above photosensitive silver halide emulsions are as follows.
[0165]
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
[0166]
Embedded image

[0167]
[Production of Samples 102 to 104]
Samples 102 to 104 were prepared in the same manner as in the preparation of Sample 101 except that the yellow coupler (Y-1) used in the seventh layer was changed to the yellow coupler types and addition amounts shown in Table 2.
[0168]
<< Formation of area gradation image >>
(Image exposure)
For the prepared samples 101 to 104, a gradation image of 0 to 100% as a yellow plate is obtained by using an AM screening method with 175 screen lines, FAIRDOT (Dainippon Screen Mfg. Co., Ltd.), and Staccato (Creo Japan Co., Ltd.) 3 The image data developed by the method was output using a digital consensus pro system (manufactured by Konica Medical and Graphic Co., Ltd.).
[0169]
The exposure was performed under the condition that the yellow density was 1.0. The DG (dot gain) was output by adjusting the LUT so that the printed material to be compared when printing by each screen method was the same as the DG obtained by the Murry-Davies equation.
[0170]
[Development processing]
Development processing was performed under the following conditions.
[0171]
Treatment process Treatment temperature Treatment time Replenishment volume (ml / m ² )
Color development 40.0 ± 0.3 ° C 120 seconds 80ml
Bleach fixing 39.0 ± 0.5 ℃ 90 seconds 120ml
Stabilization 30-34 ° C 60 seconds 150ml
Dry 60-80 ° C 30 seconds
The treatment liquids used in the above treatment steps are as follows.
[0172]
<Color developer tank solution and replenisher>

Water was added to adjust the total volume to 1 liter, the tank solution was adjusted to pH = 10.0, and the replenisher solution was adjusted to pH = 10.6.
[0173]
<Bleach fixer tank solution and replenisher>
65 g of diethylenetriaminepentaacetic acid ferric ammonium dihydrate
Diethylenetriaminepentaacetic acid 3g
Ammonium thiosulfate (70% aqueous solution) 100 ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40% aqueous solution) 27.5 ml
Water was added to make the total volume 1 liter, and the pH was adjusted to 5.0 with potassium carbonate or glacial acetic acid.
[0174]
<Stabilizing liquid tank liquid and replenisher liquid>
o-Phenylphenol 1.0g
5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-Methyl-4-isothiazolin-3-one 0.02 g
Diethylene glycol 1.0g
Fluorescent brightener (Chinopearl SFP) 2.0g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
Zinc sulfate 0.5g
Magnesium sulfate heptahydrate 0.2g
PVP (Polyvinylpyrrolidone) 1.0g
Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5g
Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia.
[0175]
(Image evaluation)
(Evaluation of color tone reproducibility)
The above formed image is measured using a spectrophotometer CM-2022 manufactured by Minolta Co., Ltd., and measured using a geometric condition d-0 for illumination and light reception, a xenon pulse light source, and light D50 of 2 ° visual field auxiliary standard. L ^* a ^* b ^* The color difference (ΔE) with the Y100% patch of art paper, which was prepared by the Japan Printing Society Standardization Committee (Japan), was used as a measure of color tone reproducibility.
[0176]
In the above evaluation, the yellow density was measured with a status T as a filter using an X-Rite 508 type densitometer.
[0177]
(Evaluation of halftone dot reproducibility)
According to the above method, each area obtained by comparing a sample that outputs an image of small dots, large dots, and tone jump (abbreviated as TJ in the table) with each method and a reference sample printed with each method. The gradation image was visually observed, and the halftone dot reproducibility was evaluated according to the following criteria.
[0178]
○: High reproducibility for the printed material as the reference sample
Δ: Slightly different from the printed material as the reference sample, but within the allowable range
×: Clearly different from the printed material that is the reference sample, there are practical problems
The results obtained as described above are shown in Table 2.
[0179]
[Table 2]

[0180]
As is clear from the results in Table 2, the area gradation of the present invention using the silver halide color photosensitive material containing the yellow coupler represented by the general formula (a-1) or (a-2) of the present invention. It can be seen that the image created by the image forming method is superior in color tone reproducibility as compared to the comparative example, and is excellent in halftone dot reproducibility of the halftone image output by various methods.
[0181]
Example 2
In the preparation of Sample 101 described in Example 1 of JP-A-2001-133922, each yellow coupler used in the seventh layer described in Example 1 was used as the yellow coupler (Y-1) used in the first layer. Samples 201 to 204 were prepared in the same manner except that was changed as shown in Table 3. Further, in the sample 202, a sample 205 was produced in the same manner except that the arrangement of the first layer (blue photosensitive layer: yellow coupler-containing layer) and the third layer (green photosensitive layer: magenta coupler-containing layer) was changed. did.
[0182]
Each sample prepared in this manner was exposed and developed by the development process A described in paragraphs [0160] to [0164] of JP-A No. 2001-356456, in the same manner as in Example 1. Evaluation of color tone reproducibility and halftone dot reproducibility (FAIRDOT only) was performed, and the obtained results are shown in Table 3.
[0183]
[Table 3]

[0184]
As is apparent from the results in Table 3, the area gradation of the present invention using the silver halide color photosensitive material containing the yellow coupler represented by the general formula (a-1) or (a-2) of the present invention. It can be seen that the image created by the image forming method is superior in color tone reproducibility and halftone dot reproducibility compared to the comparative example. Further, by adding a yellow coupler containing the general formula (a-1) or (a-2) of the present invention to the photosensitive layer disposed at the position closest to the support, the effect is further exhibited. I understand that
[0185]
【The invention's effect】
According to the present invention, an area gradation image forming method excellent in color tone reproducibility and halftone dot reproducibility could be provided.

Claims (5)

An area gradation image forming method for reproducing halftone dots as an aggregate of minimum units (dots) for image formation using a silver halide color photosensitive material, wherein the silver halide color photosensitive material has the following general formula (a -1) or a dye-forming coupler represented by (a-2).

[In the above general formulas (a-1) and (a-2), R represents a substituent, and Z represents a nitrogen-containing 6-membered ring or 7 together with —C (═O) —N—C═N— moiety. This represents a group of carbon atoms necessary to form a member ring. R 'represents a substituent, n represents an integer of 0 to 4, and X represents a hydrogen atom or a substituent. A represents a hydrogen atom or a group capable of leaving when coupling with an oxidized form of a color developing agent. ] 2. The area gradation image forming method according to claim 1, wherein the area gradation image is formed by using an FM screening method. The silver halide color light-sensitive material has three or more color-developing layers on a support, and the color-developing layer located closest to the support is represented by the general formula (a-1) or (a-2 The area gradation image forming method according to claim 1, further comprising a dye-forming coupler represented by the formula: The area gradation image formation according to any one of claims 1 to 3, wherein Z in the general formula (a-1) is a residue forming a 3H-pyrimidin-4-one ring. Method. The area gradation image formation according to any one of claims 1 to 3, wherein Z in the general formula (a-2) is a residue forming a 1H-pyrimidin-4-one ring. Method.