JP2004157478A - Silver halide color photographic sensitive material and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material suitable for a print for advertizing exhibition, giving high image density in digital exposure for a laser printer or the like, and is capable of reducing a hue change in a joint part at the time of making a large-sized advertisement. <P>SOLUTION: The silver halide color photographic sensitive material has at least one each of yellow, magenta and cyan image forming layers on a transparent support. When the silver halide color photographic sensitive material is surface-exposed for an exposure time of 10<SP>-4</SP>sec, the maximum transmission density of each layer is ≥3.0, and when the sensitive material is processed by starting color development after the lapse of 30 min following exposure of the photosensitive material, with an exposure amount which gives a density of 1.0 when the sensitive material is processed by starting color development after the lapse of 5 min following exposure, the transmission density is set to be in the range of 0.95 to 1.05. <P>COPYRIGHT: (C)2004,JPO

Description

【００５７】
本発明において用いられるシアン、マゼンタ及びイエローカプラーとしては、その他、特開昭６２−２１５２７２号の第９１頁右上欄４行目〜１２１頁左上欄６行目、特開平２−３３１４４号の第３頁右上欄１４行目〜１８頁左上欄末行目と第３０頁右上欄６行目〜３５頁右下欄１１行目やＥＰ０３５５，６６０Ａ２号の第４頁１５行目〜２７行目、５頁３０行目〜２８頁末行目、４５頁２９行目〜３１行目、４７頁２３行目〜６３頁５０行目に記載のカプラーも有用である。
また、本発明はＷＯ９８／３３７６０号の一般式（ＩＩ）及び（ＩＩＩ）、特開平１０−２２１８２５号の一般式（Ｄ）で表される化合物を添加してもよく、好ましい。
【００５８】
本発明に使用可能なシアン色素形成カプラー（単に、「シアンカプラー」という場合がある）としては、ピロロトリアゾール系カプラーが好ましく用いられ、特開平５−３１３３２４号の一般式（Ｉ）又は（ＩＩ）で表されるカプラー及び特開平６−３４７９６０号の一般式（Ｉ）で表されるカプラー並びにこれらの特許に記載されている例示カプラーが特に好ましい。また、フェノール系、ナフトール系のシアンカプラーも好ましく、例えば、特開平１０−３３３２９７号に記載の一般式（ＡＤＦ）で表されるシアンカプラーが好ましい。上記以外のシアンカプラーとしては、欧州特許ＥＰ０４８８２４８号明細書及びＥＰ０４９１１９７Ａ１号明細書に記載のピロロアゾール型シアンカプラー、米国特許第５，８８８，７１６号に記載の２，５−ジアシルアミノフェノールカプラー、米国特許第４，８７３，１８３号、同第４，９１６，０５１号に記載の６位に電子吸引性基、水素結合基を有するピラゾロアゾール型シアンカプラー、特に、特開平８−１７１１８５号、同８−３１１３６０号、同８−３３９０６０号に記載の６位にカルバモイル基を有するピラゾロアゾール型シアンカプラーも好ましい。
【００５９】
また、特開平２−３３１４４号公報に記載のジフェニルイミダゾール系シアンカプラーの他に、欧州特許ＥＰ０３３３１８５Ａ２号明細書に記載の３−ヒドロキシピリジン系シアンカプラー（なかでも具体例として列挙されたカプラー（４２）の４当量カプラーに塩素離脱基をもたせて２当量化したものや、カプラー（６）や（９）が特に好ましい）や特開昭６４−３２２６０号公報に記載された環状活性メチレン系シアンカプラー（なかでも具体例として列挙されたカプラー例３、８、３４が特に好ましい）、欧州特許ＥＰ０４５６２２６Ａ１号明細書に記載のピロロピラゾール型シアンカプラー、欧州特許ＥＰ０４８４９０９号に記載のピロロイミダゾール型シアンカプラーを使用することもできる。
【００６０】
尚、これらのシアンカプラーのうち、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シアンカプラーが特に好ましく、該特許の段落番号００１２〜００５９の記載は例示シアンカプラー（１）〜（４７）を含め、本願にそのまま適用され、本願の明細書の一部として好ましく取り込まれる。
【００６１】
本発明に用いられるマゼンタ色素形成カプラー（単に、「マゼンタカプラー」という場合がある）としては、前記の表の公知文献に記載されたような５−ピラゾロン系マゼンタカプラーやピラゾロアゾール系マゼンタカプラーが用いられるが、中でも色相や画像安定性発色性等の点で特開昭６１−６５２４５号に記載されたような２級又は３級アルキル基がピラゾロトリアゾール環の２、３又は６位に直結したピラゾロトリアゾールカプラー、特開昭６１−６５２４６号に記載されたような分子内にスルホンアミド基を含んだピラゾロアゾールカプラー、特開昭６１−１４７２５４号に記載されたようなアルコキシフェニルスルホンアミドバラスト基を持つピラゾロアゾールカプラーや欧州特許第２２６，８４９Ａ号や同第２９４，７８５Ａ号に記載されたような６位にアルコキシ基やアリールオキシ基をもつピラゾロアゾールカプラーの使用が好ましい。特に、マゼンタカプラーとしては特開平８−１２２９８４号に記載の一般式（Ｍ−Ｉ）で表されるピラゾロアゾールカプラーが好ましく、該特許の段落番号０００９〜００２６はそのまま本願に適用され、本願の明細書の一部として取り込まれる。これに加えて、欧州特許第８５４３８４号、同第８８４６４０号に記載の３位と６位の両方に立体障害基を有するピラゾロアゾールカプラーも好ましく用いられる。
【００６２】
また、イエロー色素形成カプラー（本明細書において、単に「イエローカプラー」という場合がある）としては、欧州特許ＥＰ０４４７９６９Ａ１号明細書に記載のアシル基に３〜５員の環状構造を有するアシルアセトアミド型イエローカプラー、欧州特許ＥＰ０４８２５５２Ａ１号明細書に記載の環状構造を有するマロンジアニリド型イエローカプラー、欧州公開特許第９５３８７０Ａ１号、同第９５３８７１Ａ１号、同第９５３８７２Ａ１号、同第９５３８７３Ａ１号、同第９５３８７４Ａ１号、同第９５３８７５Ａ１号等に記載のピロール−２又は３−イルもしくはインドール−２又は３−イルカルボニル酢酸アニリド系カプラー、米国特許第５，１１８，５９９号明細書に記載されたジオキサン構造を有するアシルアセトアミド型イエローカプラーが好ましく用いられる。その中では、アシル基が１−アルキルシクロプロパン−１−カルボニル基であるアシルアセトアミド型イエローカプラー、アニリドの一方がインドリン環を構成するマロンジアニリド型イエローカプラーの使用が好ましい。これらのカプラーは、単独あるいは併用することができる。
【００６３】
本発明に使用するカプラーは、前出表中記載の高沸点有機溶媒の存在下で（又は不存在下で）ローダブルラテックスポリマー（例えば米国特許第４，２０３，７１６号）に含浸させて、又は水不溶性かつ有機溶媒可溶性のポリマーとともに溶かして親水性コロイド水溶液に乳化分散させることが好ましい。好ましく用いることのできる水不溶性かつ有機溶媒可溶性のポリマーは、米国特許第４，８５７，４４９号明細書の第７欄〜１５欄及び国際公開ＷＯ８８／００７２３号明細書の第１２頁〜３０頁に記載の単独重合体又は共重合体が挙げられる。より好ましくはメタクリレート系あるいはアクリルアミド系ポリマー、特にアクリルアミド系ポリマーの使用が色像安定性等の上で好ましい。
【００６４】
本発明においては公知の混色防止剤を用いることができるが、その中でも以下に挙げる特許に記載のものが好ましい。
例えば、特開平５−３３３５０１号に記載の高分子量のレドックス化合物、ＷＯ９８／３３７６０号、米国特許第４，９２３，７８７号等に記載のフェニドンやヒドラジン系化合物、特開平５−２４９６３７号、特開平１０−２８２６１５号及び独国特許第１９６２９１４２Ａ１号等に記載のホワイトカプラーを用いることができる。また、特に現像液のｐＨを上げ、現像の迅速化を行う場合には独国特許第１９６１８７８６Ａ１号、欧州特許第８３９６２３Ａ１号、欧州特許第８４２９７５Ａ１号、独国特許１９８０６８４６Ａ１号及び仏国特許第２７６０４６０Ａ１号等に記載のレドックス化合物を用いることも好ましい。
【００６５】
本発明においては紫外線吸収剤としてモル吸光係数の高いトリアジン骨核を有する化合物を用いることが好ましく、例えば、以下の特許に記載の化合物を用いることができる。これらは、感光性層又は／及び非感光性に好ましく添加される。例えば、特開昭４６−３３３５号、同５５−１５２７７６号、特開平５−１９７０７４号、同５−２３２６３０号、同５−３０７２３２号、同６−２１１８１３号、同８−５３４２７号、同８−２３４３６４号、同８−２３９３６８号、同９−３１０６７号、同１０−１１５８９８号、同１０−１４７５７７号、同１０−１８２６２１号、独国特許第１９７３９７９７Ａ号、欧州特許第７１１８０４Ａ号及び特表平８−５０１２９１号等に記載されている化合物を使用できる。
【００６６】
本発明に係わる感光材料に用いることのできる結合剤又は保護コロイドとしては、ゼラチンを用いることが有利であるが、それ以外の親水性コロイドを単独であるいはゼラチンとともに用いることができる。好ましいゼラチンとしては、鉄、銅、亜鉛、マンガン等の不純物として含有される重金属は、好ましくは５ｐｐｍ以下、更に好ましくは３ｐｐｍ以下である。また、感光材料中に含まれるカルシウム量は、好ましくは２０ｍｇ／ｍ^２以下、更に好ましくは１０ｍｇ／ｍ^２以下、最も好ましくは５ｍｇ／ｍ^２以下である。
【００６７】
本発明においては、親水性コロイド層中に繁殖して画像を劣化させる各種の黴や細菌を防ぐために、特開昭６３−２７１２４７号公報に記載のような防菌・防黴剤を添加するのが好ましい。さらに、感光材料の被膜ｐＨは４．０〜７．０が好ましく、より好ましくは４．０〜６．５である。
【００６８】
本発明においては、感光材料の塗布安定性向上、静電気発生防止、帯電量調節等の点から界面活性剤を感光材料に添加することができる。界面活性剤としてはアニオン系界面活性剤、カチオン系界面活性剤、ベタイン系界面活性剤、ノニオン系界面活性剤があり、例えば特開平５−３３３４９２号に記載のものが挙げられる。本発明に用いる界面活性剤としてはフッ素原子含有の界面活性剤が好ましい。特に、フッ素原子含有界面活性剤を好ましく用いることができる。これらのフッ素原子含有界面活性剤は単独で用いても、従来公知の他の界面活性剤と併用してもかまわないが、好ましくは従来公知の他の界面活性剤との併用である。これらの界面活性剤の感光材料への添加量は特に限定されるものではないが、一般的には、１×１０^−５〜１ｇ／ｍ^２、好ましくは１×１０^−４〜１×１０^−１ｇ／ｍ^２、更に好ましくは１×１０^−３〜１×１０^−２ｇ／ｍ^２である。
【００６９】
本発明の感光材料は、ガスレーザー、発光ダイオード、半導体レーザー、半導体レーザーあるいは半導体レーザーを励起光源に用いた固体レーザーと非線形光学結晶を組合わせた第二高調波発光光源（ＳＨＧ）等の単色高密度光を用いたデジタル走査露光方式が好ましく使用される。システムをコンパクトで、安価なものにするために半導体レーザー、半導体レーザーあるいは固体レーザーと非線形光学結晶を組合わせた第二高調波発生光源（ＳＨＧ）を使用することが好ましい。特にコンパクトで、安価、更に寿命が長く安定性が高い装置を設計するためには半導体レーザーの使用が好ましく、露光光源の少なくとも一つは半導体レーザーを使用することが好ましい。
【００７０】
このような走査露光光源を使用する場合、本発明の感光材料の分光感度極大波長は、使用する走査露光用光源の波長により任意に設定することができる。半導体レーザーを励起光源に用いた固体レーザーあるいは半導体レーザーと非線形光学結晶を組合わせて得られるＳＨＧ光源では、レーザーの発振波長を半分にできるので、青色光、緑色光が得られる。従って、感光材料の分光感度極大は通常の青、緑、赤の３つの波長領域に持たせることが可能である。
【００７１】
本発明に使用される透過支持体としては、実質的に透明な支持体であればいずれでも構わないが、例えばセルロースナイトレートフィルムやポリエチレンテレフタレートフイルム、ポリカーボネートフイルム、ポリスチレンフイルム、ポリプロピレンフイルムなどの透明な基体が用いられる。このうち、好ましくはポリエチレンテレフタレートフィルムである。
【００７２】
透過支持体の厚みについては、特に制限がないが、好ましくは１５０〜２５０μｍ、更に好ましくは１６０μｍ〜２００μｍである。
なお、透過支持体とは、光の透過率が９０％以上である支持体である。透過率に関しては、米国特許第６，２４８，４８３Ｂ１号に詳細に記載されている。
【００７３】
本発明における支持体は乳剤層および／または裏面にアンチハレーション層を塗設してもよい。このアンチハレーション層に含有して用いられる光吸収物質としては、各種の無機物質、染料がある。無機物質としては、例えばコロイド状の金属を用いることができ、好ましくはコロイド銀、コロイドマンガンなどであり、更に好ましくはコロイド銀である。染料としては、その使用目的に応じた良好な分光吸収特性を有すること、写真処理液中で完全に脱色されること、写真乳剤に対してカブリ、減感などの悪影響を与えないことなどの諸条件を満足しなければならない。この様な染料には、オキソノール染料、ヘミオキソノール染料、スチリル染料、メロシアニン染料、シアニン染料およびアゾ染料があげられるが、なかでもオキソノール染料、ヘミオキソノール染料およびメロシアニン染料が有用である。
【００７４】
本発明のハロゲン化銀カラー写真感光材料には、画像のシャープネス等を向上させる目的で親水性コロイド層に、欧州特許ＥＰ０，３３７，４９０Ａ２号の第２７〜７６頁に記載の、処理により脱色可能な染料（なかでもオキソノール系染料）を含有させるのが好ましい。
【００７５】
本発明のハロゲン化銀カラー写真感光材料には、イラジエーションやハレーションを防止したり、セーフライト安全性等を向上させる目的で親水性コロイド層に、欧州特許ＥＰ０３３７４９０Ａ２号明細書の第２７〜７６頁に記載の、処理により脱色可能な染料（中でもオキソノール染料、シアニン染料）を添加することが好ましい。さらに、欧州特許ＥＰ０８１９９７７号明細書に記載の染料も本発明に好ましく添加される。これらの水溶性染料の中には使用量を増やすと色分離やセーフライト安全性を悪化するものもある。色分離を悪化させないで使用できる染料としては、特開平５−１２７３２４号、同５−１２７３２５号、同５−２１６１８５号に記載された水溶性染料が好ましい。
【００７６】
本発明の感光材料の処理には、特開平２−２０７２５０号の第２６頁右下欄１行目〜３４頁右上欄９行目、及び特開平４−９７３５５号の第５頁左上欄１７行目〜１８頁右下欄２０行目に記載の処理素材や処理方法が好ましく適用できる。また、この現像液に使用する保恒剤としては、前記の表に掲示した特許に記載の化合物が好ましく用いられる。
【００７７】
処理剤のケミカルとしては、富士写真フイルム社製ＣＰ４５Ｘ、ＣＰ４７Ｌ、ＣＰ４８Ｓイーストマンコダック社製ＲＡ−１００、ＲＡ−４等が適用できる。
【００７８】
発色現像液には公知もしくは市販のジアミノスチルベン系蛍光増白剤を用いることができる。公知のビストリアジニルジアミノスチルベンジスルホン酸化合物としては例えば特開平６−３２９９３６、特開平７−１４０６２５号または特開平１０−１０４８０９号に記載の化合物が好ましい。市販の化合物は、例えば「染色ノート」第１９版（色染社）Ｐ．１６５〜Ｐ．１６８に記載されており、ここに記載されている製品のなかでも Ｂｌａｎｋｏｐｈｏｒ ＵＷｌｉｑ、Ｂｌａｎｋｏｐｈｏｒ ＲＥＵまたはＨａｋｋｏｌ ＢＲＫ が好ましい。また次に示す化合物も好ましく用いることができる。
【００７９】
【化１】

【００８０】
本発明においては、特に漂白定着液にＢｒやＩなどハロゲン化物イオンを含有することが、現像液から漂白定着液に入る際に生じる画像ムラを防止し、定着能に優れ未発色部の白地の硫化銀等による汚染を防止する点から好ましい。本発明の漂白定着液においては残存銀による着色汚染を防止し本発明の目的を達成する目的から、臭化物イオン濃度が０〜１．０モル／Ｌ、より好ましくは０．０１〜０．３モル／Ｌであることが好ましい。また同様の目的から沃化物イオン濃度を含有してもよく、好ましい沃化物イオン濃度は０〜０．１モル／Ｌであり、より好ましくは０．００１〜０．０１モル／Ｌである。
【００８１】
本発明の感光材料を露光後、現像する方法としては、従来のアルカリ剤と現像主薬を含む現像液で現像する方法、現像主薬を感光材料に内蔵し、現像主薬を含まないアルカリ液などのアクチベーター液で現像する方法などの湿式方式のほか、処理液を用いない熱現像方式などを用いることができる。特に、アクチベーター方法は、現像主薬を処理液に含まないため、処理液の管理や取扱いが容易であり、また廃液処理時の負荷が少なく環境保全上の点からも好ましい方法である。
アクチベーター方法において、感光材料中に内蔵される現像主薬又はその前駆体としては、例えば、特開平８−２３４３８８号、同９−１５２６８６号、同９−１５２６９３号、同９−２１１８１４号、同９−１６０１９３号に記載されたヒドラジン型化合物が好ましい。
【００８２】
また、感光材料の塗布銀量を低減し、過酸化水素を用いた画像増幅処理（補力処理）する現像方法も好ましく用いられる。特に、この方法をアクチベーター方法に用いることは好ましい。具体的には、特開平８−２９７３５４号、同９−１５２６９５号に記載された過酸化水素を含むアクチベーター液を用いた画像形成方法が好ましく用いられる。前記アクチベーター方法において、アクチベーター液で処理後、通常脱銀処理されるが、低銀量の感光材料を用いた画像増幅処理方法では、脱銀処理を省略し、水洗又は安定化処理といった簡易な方法を行うことができる。また、感光材料から画像情報をスキャナー等で読み取る方式では、撮影用感光材料などの様に高銀量の感光材料を用いた場合でも、脱銀処理を不要とする処理形態を採用することができる。
【００８３】
本発明で用いられるアクチベーター液、脱銀液（漂白／定着液）、水洗及び安定化液の処理素材や処理方法は公知のものを用いることができる。好ましくは、リサーチ・ディスクロージャーＩｔｅｍ ３６５４４（１９９４年９月）第５３６頁〜第５４１頁、特開平８−２３４３８８号に記載されたものを用いることができる。
【００８４】
【実施例】
以下に本発明を実施例によって具体的に説明するが、本発明はこれに限定されるものではない。
【００８５】
［実施例１］
（本発明の青感層乳剤Ａ−１、２の調整）
５．７質量％の脱イオンゼラチンを含む脱イオン蒸留水１．０６リットルにＮａＣｌの１０％溶液を４６．３ｍｌを加え、さらにＨ_２ＳＯ_４（１Ｎ）を４６．４ｍｌを添加し、さらに下記化合物（Ｘ）で示される化合物を０．０１２ｇ添加した後に６０℃にを液温度を調整したところで、高速攪拌を行いながら、直ちに硝酸銀０．１モルとＮａＣｌ０．１モルを１０分間かけて反応容器中に添加した。引き続き、１．５モルの硝酸銀とＮａＣｌ溶液を６０分間かけて初期添加速度に対し最終添加速度が、４倍になるように流量加速法で添加した。次に、０．２モル％の硝酸銀とＮａＣｌ溶液を一定添加速度で、６分間かけて添加した。このとき、ＮａＣｌ溶液には、Ｋ_３ＩｒＣｌ_５（Ｈ_２Ｏ）を全銀量に対して５×１０^−７モルになる量添加して、アコ化イリジウムを粒子中にドープした。
さらに０．２モルの硝酸銀と０．１８モルのＮａＣｌ並びに０．０２モルのＫＢｒ溶液を６分間かけて添加した。このときハロゲン水溶液中に、全銀量に対して０．５×１０^−５モルに相当するＫ_４Ｒｕ（ＣＮ）_６とＫ_４Ｆｅ（ＣＮ）_６を各々溶解してハロゲン化銀粒子に添加した。
また、この最終段の粒子成長中に、全銀量に対し、０．００１モルに相当するＫＩ水溶液を反応容器中に１分間かけて添加した。添加開始の位置は、全粒子形成の９３％が終了した時点から開始した。
その後４０℃にて下記化合物（Ｙ）の沈降剤を加え、ｐＨを３．５付近に調整して脱塩、水洗を行った。
【００８６】
【化２】

【００８７】
脱塩水洗後の乳剤に、脱イオンゼラチンとＮａＣｌ水溶液、並びにＮａＯＨ水溶液を加え、５０℃に昇温してｐＡｇ７．６、ｐＨ５．６に調整した。
このようにして、塩化銀９８．９モル％ 臭化銀１モル％ 沃化銀０．１モル％のハロゲン組成からなる、平均辺長０．７０μｍ、辺長の変動係数８％のハロゲン化銀立方体粒子を含むゼラチン得た。
【００８８】
上記乳剤粒子を６０℃に維持して、分光増感色素−１および２をそれぞれ２．５×１０^−４モル／Ａｇモルと２．０×１０^−４モル／Ａｇモル添加した。さらに、チオスルフォン酸化合物−１を１×１０^−５モル／Ａｇモル添加し、平均粒子径０．０５μｍの臭化銀９０モル％ 塩化銀１０モル％で六塩化イリジウムをドープした微粒子乳剤を添加して、１０分間熟成した。さらに平均粒子径０．０５μｍの臭化銀４０モル％ 塩化銀６０モル％の微粒子を添加し１０分間熟成した。微粒子は溶解し、これによりホストの立方体粒子の臭化銀含有率は、１．３モルに増加した。また六塩化イリジウムは、１×１０^−７モル／Ａｇモルドープされた。
【００８９】
引き続き、チオ硫酸ナトリウム １×１０^−５モル／Ａｇモルと金増感剤−１を２×１０^−５モルを添加した。そして直ちに、６０℃に昇温し、引き続き４０分間熟成し、その後５０℃に降温した。降温後直ちに、メルカプト化合物−１、２をそれぞれ６×１０^−４モル／Ａｇモルになるように添加した。この後１０分間の熟成後、ＫＢｒ水溶液を銀に対して、０．００８モルになるように添加し、１０分間の熟成後、降温して収納した。
この様にして、青感層用高感側乳剤Ａ−１を作成した。
上記乳剤調整方法と粒子形成中の温度以外は、全く同様にして、平均辺長０．５５μｍ、辺長の変動係数９％の立方体粒子を形成した。粒子形成中の温度は５５℃であった。
分光増感ならびに化学増感は、比表面積を合わせる補正（辺長比０．７／０．５５＝１．２７倍）を行なった量で実施し、青感層用低感側乳剤Ａ―２を作成した。
【００９０】
【化３】

【００９１】
（比較用青感層乳剤Ｂ−１、２の調整）
乳剤Ａ−１と調整条件を下記のごとく変更した以外は、乳剤Ｂ−１、２の調整条件と同様にして比較青感層用高感側乳剤Ｂ−１、比較青感層用低感側乳剤Ｂ−２を作製した。
乳剤Ａ−１の乳剤調整条件の中で、粒子形成時の温度を６８℃とすることで、粒子サイズを平均辺長０．８５μｍにした。辺長の変動係数は１２％であった。また、粒子形成最終段階のヨウドイオン導入を止めＣｌイオンに置き換えた。従って粒子形成時終了時のハロゲン組成は、塩化銀９９モル％ 臭化銀１モル％である。分光増感色素−１および分光増感色素−２の添加量は、乳剤Ａ−１の調整時の１．２５倍にした。チオスルフォン酸−１は等量使用した。
【００９２】
さらに化学増感は、以下のように変更した。平均粒子径０．０５μｍの臭化銀９０モル％ 塩化銀１０モル％で六塩化イリジウムをドープした微粒子乳剤を添加して、１０分間熟成した。さらに平均粒子径０．０５μｍの臭化銀４０モル％塩化銀６０モル％の微粒子を添加し、１０分間熟成した。微粒子は溶解し、これによりホストの立方体粒子の臭化銀含有率は、２．０モル％に増加した。また六塩化イリジウムは、２×１０^−７モル／Ａｇモルドープされた。
【００９３】
引き続き、チオ硫酸ナトリウム１×１０^−５モル／Ａｇモルを添加した。そして直ちに、５５℃に昇温し、引き続き７０分間熟成し、その後５０℃に降温した。金増感剤は添加しなかった。降温後直ちに、メルカプト化合物−１、２をそれぞれ４×１０^−４モル／Ａｇモルになるように添加した。この後、１０分間の熟成後、ＫＢｒ水溶液を銀に対して０．０１０モルになるように添加し、１０分間の熟成後、降温して収納した。
このようにして、比較青感層用高感側乳剤Ｂ−１を作製した。
【００９４】
乳剤Ｂ−１と同様にして、ただし、粒子形成時の温度を下げることで、平均辺長０．６８μｍ、辺長の変動係数１２％の粒子を形成した。分光増感、化学増感剤は、表面積の比率を考慮して乳剤Ｂ−１に対し、１．２５倍とし、比較青感層用低感側乳剤Ｂ―２を作成した。
【００９５】
（本発明の緑感層用乳剤Ｃ−１、２の調整）
乳剤Ａ−１と粒子形成時の温度を下げ並びに増感色素の種類を下記のごとく変更する以外は、乳剤Ａ−１、２の調整条件と同様にして緑感層乳剤用高感側乳剤Ｃ−１、緑感層用低感側乳剤Ｃ−２を作成した。
粒子サイズは高感側乳剤Ｃ−１が平均辺長０．４０μｍ、低感側乳剤Ｃ−２が平均辺長０．３０μｍであり、その変動係数は、いずれも８％であった。
【００９６】
【化４】

【００９７】
増感色素Ｄをハロゲン化銀１モル当り、大サイズ乳剤（高感側乳剤Ｃ−１）に対しては３．０×１０^−４モル、小サイズ乳剤（低感側乳剤Ｃ−２）に対しては３．６×１０^−４モル、また、増感色素Ｅをハロゲン化銀１モル当り、大サイズ乳剤に対しては４．０×１０^−５モル、小サイズ乳剤に対しては７．０×１０^−５モル添加した。
【００９８】
（比較緑感層用乳剤Ｄ−１、２の調整）
乳剤Ｂ−１と粒子形成時の温度を下げ、並びに増感色素の種類を変更した以外は、乳剤Ｂ−１、２の調整条件と同様にして比較緑感層用高感側乳剤Ｄ−１、比較緑感層用低感側乳剤Ｄ−２を作製した。
粒子サイズは高感側乳剤Ｄ−１が平均辺長０．５０μｍ、低感側乳剤Ｄ−２が平均辺長０．４０μｍであり、その変動係数はいずれも１０％であった。
また、増感色素Ｄをハロゲン化銀１モル当り、大サイズ乳剤（高感側乳剤Ｄ−１）に対しては４．０×１０^−４モル、小サイズ乳剤（低感側乳剤Ｄ−２）に対しては４．５×１０^−４モル、また、増感色素Ｅをハロゲン化銀１モル当り、大サイズ乳剤に対しては５．０×１０^−５モル、小サイズ乳剤に対しては８．８×１０^−５モル添加した。
【００９９】
（本発明の赤感層用乳剤Ｅ−１、２の調整）
乳剤Ａ−１と粒子形成時の温度を下げ並びに増感色素の種類を下記のごとく変える以外は、乳剤Ａ−１、２の調整条件と同様にして赤感層用高感側乳剤Ｅ−１、赤感層用低感側乳剤Ｅ−２を作成した。
粒子サイズは高感側乳剤Ｅ−１が、平均辺長０．３８μｍ、低感側乳剤Ｅ−２が、平均辺長０．３２μｍであり、辺長の変動係数は、各々９％と１０％であった。
【０１００】
【化５】

【０１０１】
増感色素ＧおよびＨをそれぞれ、ハロゲン化銀１モル当り、大サイズ乳剤（高感側乳剤Ｅ−１）に対しては８．０×１０^−５モル、小サイズ乳剤（低感側乳剤Ｅ−２）に対しては１０．７×１０^−５モル添加した。
さらに、以下の化合物Ｉを赤感性乳剤層にハロゲン化銀１モル当たり３．０×１０^−３モル添加した。
【０１０２】
【化６】

【０１０３】
（比較赤感層用乳剤Ｆ−１、２の調整）
乳剤Ｂ−１と粒子形成時の温度を下げ、並びに増感色素の種類を変更した以外は、乳剤Ｂ−１、２の調整条件と同様にして比較赤感層用高感側乳剤Ｆ−１、比較赤感層用低感側乳剤Ｆ−２を作製した。
粒子サイズは高感側乳剤Ｆ−１が、平均辺長０．５７μｍ、低感側乳剤Ｆ−２が、平均辺長０．４３μｍであり、辺長の変動係数は、各々９％と１０％であった。
また、増感色素ＧおよびＨをそれぞれ、ハロゲン化銀１モル当り、大サイズ乳剤（高感側乳剤Ｆ−１）に対しては１．０×１０^−４モル、小サイズ乳剤（低感側乳剤Ｆ−２）に対しては１．３４×１０^−４モル添加した。さらに、化合物Ｉを赤感性乳剤層にハロゲン化銀１モル当たり３．０×１０^−３モル添加した。
【０１０４】
（本発明の青感層用乳剤Ｇ−１、２の調整）
乳剤Ａ−１、２とは、それぞれ硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ_３ＲｈＢｒ_６の水溶液を出来上がりのハロゲン化銀１モル当たりＲｈ量が２．７×１０^−９になる量を添加したことのみ異なる乳剤を調整し、これらをそれぞれ青感層用高感側乳剤Ｇ−１、青感層用低感側乳剤Ｇ−２とした。粒子の平均辺長および辺長の変動係数は対応する乳剤Ａ−１、２と同じであった。
【０１０５】
（本発明の緑感層用乳剤Ｈ−１、２の調整）
乳剤Ｃ−１、２とは、それぞれ硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ_３ＲｈＢｒ_６の水溶液を出来上がりのハロゲン化銀１モル当たりＲｈ量が４．７×１０^−９になる量を添加したことのみ異なる乳剤を調整し、これらをそれぞれ緑感層用高感側乳剤Ｈ−１、緑感層用低感側乳剤Ｈ−２とした。粒子の平均辺長および辺長の変動係数は対応する乳剤Ｃ−１、２と同じであった。
【０１０６】
（本発明の赤感層用乳剤Ｉ−１、２の調整）
乳剤Ｅ−１、２とは、それぞれ硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ_３ＲｈＢｒ_６の水溶液を出来上がりのハロゲン化銀１モル当たりＲｈ量が６．７×１０^−９になる量を添加したことのみ異なる乳剤を調整し、これらをそれぞれ赤感層用高感側乳剤Ｉ−１、赤感層用低感側乳剤Ｉ−２とした。粒子の平均辺長および辺長の変動係数は対応する乳剤Ｅ−１、２と同じであった。
【０１０７】
第一層塗布液調製
イエローカプラー（ＥｘＹ）６１．９ｇ、色像安定剤（Ｃｐｄ−１）７ｇ、色像安定剤（Ｃｐｄ−２）４ｇ、色像安定剤（Ｃｐｄ−３）７ｇ、色像安定剤（Ｃｐｄ−８）２ｇを溶媒（Ｓｏｌｖ−１）２１ｇ及び酢酸エチル８０ｍｌに溶解し、この液を４ｇのドデシルベンゼンスルホン酸ナトリウムを含む２３．５質量％ゼラチン水溶液２９４ｇ中に高速攪拌乳化機（ディゾルバー）で乳化分散し、水を加えて９００ｇの乳化分散物Ａを調製した。
一方、上記乳化分散物Ａと前記乳剤Ａ−１、Ａ−２を混合溶解し、後記組成となるように第一層塗布液を調製した。乳剤塗布量は、銀量換算塗布量を示す。
【０１０８】
第二層〜第七層用の塗布液も第一層塗布液と同様の方法で調製した。各層のゼラチン硬化剤としては、１−オキシ−３，５−ジクロロ−ｓ−トリアジンナトリウム塩（Ｈ−１）、（Ｈ−２）、（Ｈ−３）を用いた。また、各層にＡｂ−１、Ａｂ−２、Ａｂ−３及びＡｂ−４をそれぞれ全量が１５．０ｍｇ／ｍ^２、６０．０ｍｇ／ｍ^２、５．０ｍｇ／ｍ^２及び１０．０ｍｇ／ｍ^２となるように添加した。
【０１０９】
【化７】

【０１１０】
【化８】

【０１１１】
また、１−（３−メチルウレイドフェニル）−５−メルカプトテトラゾールを、第二層、第四層、第六層および第七層に、それぞれ０．２ｍｇ／ｍ^２、０．２ｍｇ／ｍ^２、０．６ｍｇ／ｍ^２、０．１ｍｇ／ｍ^２となるように添加した。
また、青感性乳剤層および緑感性乳剤層に対し、４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを、それぞれハロゲン化銀１モル当たり、１×１０^−４モル、２×１０^−４モル添加した。
また、赤感性乳剤層にメタクリル酸とアクリル酸ブチルの共重合体ラテックス（質量比１：１、平均分子量２０００００〜４０００００）を０．０５ｇ／ｍ^２を添加した。
また第二層、第四層および第六層にカテコール−３，５−ジスルホン酸二ナトリウムをそれぞれ６ｍｇ／ｍ^２、６ｍｇ／ｍ^２、１８ｍｇ／ｍ^２となるように添加した。
また、イラジエーション防止のために、以下の染料（カッコ内は塗布量を表す）を添加した。
【０１１２】
【化９】

【０１１３】
（層構成）
以下に、各層の構成を示す。数字は塗布量（ｇ／ｍ^２）を表す。ハロゲン化銀乳剤は、銀換算塗布量を表す。
支持体
支持体として、厚さ１８０μｍの透明なポリエチレンテレフタレートの乳剤と反対側に、ゼラチン６．２ｇ／ｍ^２、下記染料−１、染料−２および染料−３をそれぞれ０．０７ｇ／ｍ^２、０．０４ｇ／ｍ^２、０．０９５ｇ／ｍ^２および紫外線吸収剤（ＵＶ−Ｂ）を０．３１ｇ／ｍ^２、界面活性剤（Ｃｐｄ−１３）を０．０３ｇ／ｍ^２塗設したものを用いた。
【０１１４】
【化１０】

【０１１５】

【０１１６】

【０１１７】

【０１１８】

【０１１９】

【０１２０】

【０１２１】
【化１１】

【０１２２】
【化１２】

【０１２３】
【化１３】

【０１２４】
【化１４】

【０１２５】
【化１５】

【０１２６】
【化１６】

【０１２７】
【化１７】

【０１２８】
【化１８】

【０１２９】
【化１９】

【０１３０】
【化２０】

【０１３１】
現像処理工程は、富士写真フイルム（株）製カラーペーパー用現像処理プロセスＣＰ−４５Ｘを使用し、下記の条件で行なった。
富士カラーペーパー用現像処理プロセスＣＰ−４５Ｘ
処理工程 処理温度 処理時間 補充量
発色現像 ３５±０．３℃ １１０秒 ３７０ｍＬ／ｍ^２
漂白定着 ３３〜３７℃ １１０秒 ４９４ｍＬ／ｍ^２
水洗 ２４〜３４℃ ２２０秒 ３〜１０Ｌ／ｍ^２
乾燥 ５０〜７０℃ ３分
【０１３２】
以上のようにして試料１０１１を作成した。続いて、試料１０１１に対して、乳剤および乳剤含有層の塗布量を表２のように変更した各試料を作成した。
【０１３３】
【表２】

【０１３４】
露光
このようにして作成した試料をキセノンフラッシュ光源（発光時間１０^−４秒に調整）により露光した後、露光後５分で前記発色現像処理を行なった。露光時には得られる画像が最低濃度から最高濃度の範囲を含むように濃度補正フィルター（ＣＣフィルター）を必要に応じて使用した。また、同じ露光量でイエロー、マゼンタ及びシアンのステータスＡ透過濃度が１．０になるようにＣＣフィルターを必要に応じて使用して調整した。
次に、上記条件と同じ露光条件で露光した試料を露光後３０分で発色現像処理を行なった。これらの試料を、同じ露光量の位置が隣り合わせになるように貼り合わせ、高濃度部の黒の締りと貼り合わせ部のつながりの良さについて１０名の官能評価を行い、５段階（５：良、１：悪、とした５段階で、４以上が許容内）の評価を行なった。この結果を表３に示す。
【０１３５】
【表３】

【０１３６】
表３より明らかなように、本発明の試料は比較試料と比較し、いずれも黒の締り及び接合適性で顕著に優れ、これらの両方の特性を満足させることができることが明らかである。
【０１３７】
［実施例２］
実施例で使用した試料１００１、１０１１、１０２１に対し、下記の露光を行なった。
Ｄｕｒｓｔ社製のレーザー露光機Ｌａｍｂｄａ７６を用いて走査露光を行なった。ユーザーが予め設定する最大透過濃度を表４のように設定し、２１段のグレーパッチを含むキャリブレーション用画像を用いてキャリブレーションを行なった。表４に示した回数のキャリブレーションを繰返すことにより、２１段の各々のグレーパッチにおいて露光装置が示す目標濃度に収束した。キャリブレーションを行なう際は、露光後５分で発色現像処理を開始するように条件を揃えた。
【０１３８】
【表４】

【０１３９】
キャリブレーションが終了した後、その露光条件で最高濃度と最低濃度を含む画像評価用画像を露光後、５分で発色現像処理を開始した試料の最高濃度を測定し、さらに高濃度部を用いた画像の黒の締りに関して、１０名の官能評価を行い、５段階（５：良、１：悪、とした５段階で、４以上が許容内）の評価を行なった。また、同じ露光条件で露光後３０分で発色現像を開始した試料を作成し、それと上記露光後５分で処理した試料とを、同じ露光量のグレーパッチ同士が隣り合わせになるように貼り合わせ、貼り合わせ部のつながりの良さについても同様に１０名の官能評価を行い、５段階（５：良、１：悪、とした５段階で、４以上が許容内）の評価を行なった。この結果を表５に示す。
【０１４０】
【表５】

【０１４１】
表５より明らかなように、本発明の感光材料１０１１、１０２１を使用した試料２００４〜２００７は、いずれも黒の締り及び接合適性で顕著に優れていることがわかる。これに対し、比較感光材料１００１を使用した試料２００１〜２００３においては、いずれも接合適性に不十分であり、特に試料２００１、２００２においては、予め透過最高濃度を２．８０以上に設定してキャリブレーションを行なっても、接合適性に不十分であることがわかる。
【０１４２】
【発明の効果】
以上、本発明によれば、広告展示用プリントに好適なハロゲン化銀カラー写真感光材料を提供することができる。特に高い画像濃度による鮮やかな画像が得られ、かつ広告展示用プリントに重要な画像の貼り合わせにおいて優れた品質のハロゲン化銀カラー写真感光材料を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide color photographic light-sensitive material, and in particular, high density, high image quality, and further, stable quality by having little change in density with respect to time fluctuation until color development after exposure. The present invention relates to a silver halide color photographic light-sensitive material that realizes an improvement in productivity.
[0002]
[Prior art]
In recent years, display advertisements using large color photographic prints, ink jet prints, and the like are increasing. As these exhibition methods, for example, there are a method of viewing an image formed on a support with light irradiated from the image side (reflection method), and a method of viewing with light irradiated from the back side of the image (transmission method), It is known that the latter transmission method can provide a clearer image under specific conditions such as indoors or outdoors at night. As a transmissive image forming material / method used for such applications, there are a printing method, an ink jet method, and a silver salt method. Although the printing method is advantageous for mass production, the ink jet method or the silver salt method is more preferable in the field of display advertisements in which various kinds of images are displayed in a relatively small amount. While the inkjet method is accelerating the increase in convenience, the silver salt method is an advertisement for silver salt color photographic prints due to high image quality performance and high image stability due to high contrast and rich gradation reproducibility. It still has an advantage in the industry.
[0003]
On the other hand, with the development of computer technology in recent years, it has become relatively easy to process (image processing) on a computer a digital image read by a scanner or the like. Further, as a method for exposing the digital image information to a photosensitive material, an image forming method in which scanning exposure is performed with a light source having a high light intensity such as a laser light source or an LED is rapidly increasing. With the spread of laser printers and digital prints in recent years, this image forming method has become common, and it is always required to provide a photosensitive material having characteristics suitable for laser exposure and digital exposure. The advertisement display print needs to provide a more vivid image for its use, and a higher image density is required.
[0004]
In addition, the larger the size of the exhibition advertisement, the greater the advertising effect. Therefore, the photosensitive material for exhibition advertisement is required to be used in a large format. For this reason, a considerably large exposure apparatus is used, but the size of the exposure apparatus is limited due to the limitation of the size of the photosensitive material. Therefore, when a large format exceeding the size limit is required, two or more photosensitive materials are joined and displayed. On the other hand, in a transmission type photosensitive material, a higher density and higher quality image is required. However, when creating a large-size advertisement that satisfies this requirement and exceeds the size limit of the photosensitive material, if two or more sheets are pasted together, the image of the joint portion is poorly connected, and a large-sized advertisement that looks good is displayed. I found out I couldn't get it. Patent Document 1 discloses that a bright image can be provided by increasing the density, but does not mention at all such a problem of bonding suitability (change in color of the bonded portion) and a solution thereof.
In a transmission type photosensitive material that is uniquely used as a large format display advertisement by such a pasting, maintaining a high image quality at a high density and reducing the color change by the pasting has been conventionally However, the performance of the photosensitive material is insufficient, and improvement has been demanded.
[0005]
[Patent Document 1]
JP 2001-249433 A
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and it is an object of the present invention to solve the above conventional problems and achieve the following objects. That is,
An object of the present invention is to provide a silver halide color photographic light-sensitive material suitable for prints for advertisement display. More specifically, the present invention provides a silver halide color photographic light-sensitive material that is suitable for advertisement display prints that obtain a high image density in digital exposure such as a laser printer and have little change in the color of the joint when producing large format advertisements. is there.
[0007]
[Means for Solving the Problems]
In the case where the present inventors are exposed under the same conditions, when the instability of the performance of the photosensitive material with respect to the fluctuation factors after exposure is to obtain an image having a high density, particularly a high density of 3.0 or more, It was found that it is reflected more remarkably than before. In large-scale laser printers in recent years, a roll-shaped photosensitive material is often scanned and exposed continuously over several meters. After the exposed photosensitive material is taken up again, this time, with the exposure end as the head, Since color development processing is performed, the time from exposure to development processing in a single operation can vary from a few minutes to a few tens of minutes, but the performance fluctuation at that time is high density, particularly 3.0 or more Therefore, the present invention is large when an image having a high density is to be obtained and appears as a large color change at the joint when the image is connected.
That is, the means for solving the above problems are as follows.
(1) A silver halide color photographic material having at least one yellow color image forming layer, magenta color image forming layer, and cyan color image forming layer on a transparent support, with an exposure time of 10^-4When the surface exposure for 2 seconds was performed, the maximum transmission density of each layer was 3.0 or more, and when the photosensitive material was processed by starting color development 5 minutes after exposure, the density was 1.0. A silver halide color photographic light-sensitive material having a transmission density of 0.95 or more and 1.05 or less when the light-sensitive material is developed and processed 30 minutes after exposure at an exposure amount giving
(2) A silver chloride content of 95 mol containing at least one selected from metal complexes represented by the following general formula (I) in at least one of the silver halide emulsion layers of the silver halide color photographic material. The silver halide color photographic light-sensitive material as described in (1), wherein the silver halide emulsion material comprises at least% silver chloride emulsion grains.
Formula (I)
[MX^I _nL^I _(6-n)]^m
In general formula (I), M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, and X^IRepresents a halogen ion, L^IIs X^IRepresents an arbitrary ligand different from. n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0 or 1+.
(3) An image forming method in which color development processing is performed after scanning exposure with a light beam, and the apparatus used for scanning exposure outputs a calibration image and measures the density to set a transmission maximum that is set in advance. (1) or (2) characterized in that it is an apparatus accompanied by a function for calibrating the density and the gray tone exposure condition that reaches that density, and the preset maximum transmission density is 2.8 or more. An image forming method using the silver halide color photographic light-sensitive material described in 1).
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
First, exposure will be described.
In the present invention, “exposure time 10 for obtaining the maximum transmission density”.^-4“Surface exposure in seconds” means 10 for one surface.^-4Seconds (1 × 10 in this specification)^-410 seconds^-4It means that the exposure is given so as to have an exposure time of 2 seconds). That is, 10^-4This means using a xenon flash light source adjusted to emit light in seconds, and combining this with an optical wedge and color filter to give the photosensitive material the exposure necessary to obtain the highest density from the lowest density. . At this time, the CC filter so that the image obtained after the color development processing described later includes a range from the lowest density to the highest density and the status A transmission density of yellow, magenta and cyan becomes 1.0 at the same exposure amount. Adjustments can be made using a (color correction filter) as necessary to obtain a gray image.
[0009]
Next, the transmission density will be described.
In the present invention, the transmission density is determined using a color paper development process CP-45X manufactured by Fuji Photo Film Co., Ltd., and the color development time is extended to 110 seconds. As the developing processor, a CSR24100 developing machine manufactured by Noritz was used. The condition of the developing solution can fluctuate due to various factors, so it is difficult to maintain certain conditions. However, a transparent display film, which is a color paper, is 40 to 60 m daily.²In the running processing state to be processed, the solution was replenished in accordance with the recommended values of technical information of Fuji Photo Film Co., Ltd. In the present invention, the color development processing of the transmissive color display film was performed under the following conditions.
[0010]
Development process CP-45X for Fuji color paper
Processing process Processing temperature Processing time Replenishment amount
Color development 35 ± 0.3 ° C 110 seconds 370 mL / m²
Bleach fixing 33-37 ° C 110 seconds 494mL / m²
Washing with water 24 to 34 ° C 220 seconds 3 to 10 L / m²
Dry 50-70 ° C 3 minutes
[0011]
The status A transmission density of each of yellow, magenta, and cyan of the processed sample can be measured and obtained. The measurement was performed using X-rite 310 manufactured by X-rite.
It is necessary to set conditions in advance so that an image obtained by exposure and development processing through an optical wedge has a range from the lowest density to the highest density. As a result, the characteristic curve showing the transmission density with respect to the exposure amount can include the lowest density to the highest density. The maximum concentration at that time is the maximum transmission density (also referred to as the maximum transmission density) in the present invention.
[0012]
An exposure time of 10 with a xenon flash light source through an optical wedge on the photosensitive material^-4In the present invention, when the second gray surface exposure is performed, the maximum transmission density of each layer is 3.0 or more. The maximum transmission density of each layer is preferably in the range of 3.0 to 4.0, more preferably in the range of 3.2 to 4.0, and still more preferably in the range of 3.3 to 3.8. If it is lower than 3.0, satisfactory image quality cannot be obtained in terms of black tightening. On the other hand, even if it is higher than 4.0, the effect of further improving the image quality is small. However, in order to obtain a high density, the coating amount of the emulsion and the dye-forming coupler has to be increased considerably, and the development delay in the lower layer and unevenness in processing are caused. This causes problems such as the above.
[0013]
The light-sensitive material of the present invention is further developed by starting color development 30 minutes after exposure of the light-sensitive material at an exposure amount giving a transmission density of 1.0 when color development processing is started 5 minutes after exposure. The processed transmission density is in the range of 0.95 to 1.05. Preferably it is the range of 0.97 to 1.03, More preferably, it is the range of 0.99 to 1.01.
Thus, when a large advertisement is produced by laminating a high-density photosensitive material, it is possible to prevent a sense of discomfort at the joint.
[0014]
Scan exposure with a light beam is usually performed by a combination of line exposure (raster exposure: main scan) with a light beam and relative movement (sub-scan) of the photosensitive material in a direction perpendicular to the line exposure direction. Is common. The scanning exposure using a light beam here means exposure using a laser, LED, or the like as a light source. For example, a photosensitive material is fixed to the outer periphery or inner periphery of a cylindrical drum, the main scanning is performed by rotating the drum while irradiating a light beam, and at the same time, the light source is moved perpendicularly to the drum rotation direction. In this way, the sub-scanning method (drum method) or the rotating polygon mirror is irradiated with a light beam to scan the reflected beam horizontally with the rotation direction of the polygon mirror (main scanning). A method of performing sub-scanning (polygon method) by transporting perpendicularly to the rotation direction is often used. In addition, when using an exposure apparatus in which a plurality of light sources are arranged in an array larger than the width of the photosensitive material to be exposed, it can be considered that the portion corresponding to the main scan is replaced with the array light source, and the scanning according to the present invention. It can be included in the exposure.
[0015]
Next, calibration will be described.
The calibration in the present invention means a function in which a user sets a target density in the scanning exposure apparatus, and the apparatus determines an exposure condition according to the target density, and an operation for the determination. The calibration image is an image including gray patches having different densities in order to obtain information necessary for calibration.
[0016]
The inventors have used an exposure time of 10 to obtain the maximum density.^-4The characteristic value of the image obtained by performing the surface exposure for 2 seconds and then performing the color development processing is close to the characteristics of the image obtained by performing the scanning exposure using the light beam and developing after the exposure. It has been found that it shows a good correlation with the characteristics of image quality created by scanning exposure with a beam.
[0017]
Next, the metal complex represented by the following general formula (I) preferably used in the present invention will be described.
Formula (I)
[MX^I _nL^I _(6-n)]^m
In general formula (I), M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt, and X^IRepresents a halogen ion, L^IIs X^IRepresents an arbitrary ligand different from. n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0 or 1+.
X^IIs a fluoride ion, a chloride ion, a bromide ion or an iodide ion, and among them, a chloride ion and a bromide ion are preferable.
L^IMay be an inorganic compound or an organic compound, and may be charged or uncharged, but is preferably an uncharged inorganic compound. L^IPreferably H₂O, OH, O, NO or NS, more preferably H₂O, NO or NS.
[0018]
Among the metal complexes represented by the general formula (I), the metal complexes represented by the following general formula (IA) are preferable.
[0019]
Formula (IA)
[M^IAX^IA _nL^IA _(6-n)]^m
In general formula (IA), M^IARepresents Re, Ru, Os or Rh, and X^IARepresents a halogen ion, L^IAIs M^IAIs Re, Ru or Os, it represents NO or NS;^IAH is Rh₂O, OH or O is represented. n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0 or 1+. X^IAIs X in the general formula (I)^IThe preferred range is also the same.
[0020]
Although the preferable specific example of a metal complex represented with general formula (I) below is given, this invention is not limited to these.
[0021]
[ReCl₆]^2-
[ReCl₅(NO)]^2-
[RuCl₆]^2-
[RuCl₅]^3-
[RuCl₅(NO)]^2-
[RuCl₅(NS)]^2-
[RuBr₅(NS)]^2-
[OsCl₆]^3-
[OsCl₅(NO)]^2-
[OsBr₅(NS)]^2-
[RhCl₆]^2-
[RhCl₅(H₂O)]^2-
[RhCl₄(H₂O)₂]⁻
[RhBr₆]^3-
[RhBr₅(H₂O)]^2-
[RhBr₄(H₂O)₂]⁻
[PdCl₆]^2-
[PtCl₆]^2-
[0022]
The metal complex mentioned above is an anion, and when a salt is formed with a cation, the metal complex that is easily dissolved in water as the counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do. The metal complex represented by the general formula (I) is 1 × 10 5 per mol of silver during grain formation.^-11From mole to 1 × 10^-6Mole addition is preferred, 1 × 10^-9From mole to 1 × 10^-7Most preferably, it is added in a molar amount.
[0023]
The above metal complex is added directly to the reaction solution at the time of silver halide grain formation, added to an aqueous halide solution for forming silver halide grains, or other solution, and added to the grain formation reaction solution. It is preferable to incorporate it into the silver halide grains by adding them. It is also preferable to physically ripen the fine particles in which the metal complex is previously incorporated in the grains and to incorporate them in the silver halide grains. Further, these methods can be combined and contained in the silver halide grains.
[0024]
When these metal complexes are incorporated into silver halide grains, they can be uniformly present inside the grains. As described, it is also preferable to exist only in the particle surface layer, and it is also preferable to add a layer containing no metal complex to the particle surface where the metal complex exists only inside the particle. Further, as described in US Pat. Nos. 5,252,451 and 5,256,530, the particle surface phase is modified by physical ripening with fine particles in which metal complexes are incorporated. It is also preferable. Further, these methods can be used in combination, and a plurality of types of metal complexes may be incorporated in one silver halide grain.
[0025]
The silver halide color photographic light-sensitive material of the present invention will be described in detail below.
The amount of silver halide used (for example, the coating amount) in the silver halide color photographic light-sensitive material of the present invention is 0.40 to 2.0 g / m.²Is more preferable, and 0.60 to 1.7 g / m is more preferable.²It is.
[0026]
In the present invention, the ratio of the oil-soluble component amount to the hydrophilic binder amount in the photographic composition layer can be arbitrarily set. A preferable ratio in the photographic constituent layer other than the protective layer is 0.05 to 1.50, more preferably 0.10 to 1.40, and most preferably 0.20 to 1.30 in terms of mass ratio. By optimizing the ratio of each layer, film strength, scratch resistance, and curl characteristics can be adjusted.
In the silver halide color photographic light-sensitive material of the present invention, the total coated gelatin amount is preferably specified, and the total gelatin coating amount is 5.0 to 25 g / m.², Preferably 8.0 to 18 g / m²It is.
[0027]
In the silver halide color photographic light-sensitive material according to the present invention, gelatin is used as a hydrophilic binder. If necessary, other gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose A hydrophilic colloid such as a synthetic hydrophilic polymer such as a derivative, a single substance or a copolymer can also be used in combination with gelatin. The gelatin used in the silver halide color photographic light-sensitive material according to the present invention may be either lime-processed gelatin or acid-processed gelatin, or may be gelatin manufactured using any raw material such as cow bone, cow skin, or pig skin. Preferred is lime-processed gelatin made from beef bone and pig skin.
[0028]
In the present invention, the preferred film thickness of the photographic composition layer is 22.0 μm or less, 3.0 μm or more, preferably 20.0 μm or less, 4.0 μm or more, and most preferably 18.0 μm or less, 8.0 μm or more. In the present invention, the film thickness of the photographic constituent layer represents the unprocessed thickness of the photographic constituent layer above the support. Specifically, it can be determined by any of the following methods. First, it is obtained by cutting a silver halide color photographic light-sensitive material perpendicularly to a support and observing the cut surface with an electron microscope. As the second method, the coating amount of each component in the photographic composition layer (g / m²) And specific gravity. The specific gravity is 1.34 g / ml for typical gelatin used for photography and 5.59 g / ml for silver chloride grains. It can also be measured for other lipophilic additives. The film thickness can be calculated.
[0029]
The silver halide color photographic light-sensitive material of the present invention will be further described.
The silver halide color photographic light-sensitive material of the present invention (hereinafter sometimes simply referred to as “photosensitive material”) includes, in addition to the yellow color developing layer, the magenta color developing layer, and the cyan color developing layer, a hydrophilic colloid layer, an anti-coloring layer described later, You may have a halation layer, an intermediate | middle layer, and a colored layer.
[0030]
The silver halide emulsion preferably used in the present invention will be described in detail below.
The silver halide grains in the silver halide emulsion used in the present invention are preferably substantially cubic or tetradecahedral crystal grains having {100} faces (these grains have rounded vertices and higher order faces. Or tabular grains having an aspect ratio of 2 or more in which 50% or more of the total projected area is composed of {100} faces or {111} faces. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle. In the present invention, cubic particles, tabular grains having a {100} plane as a main plane, or tabular grains having a {111} plane as a main plane are preferably applied.
[0031]
As the silver halide emulsion used in the present invention, a silver chloride, silver bromide, silver iodobromide, silver (iodo) bromide emulsion or the like is used. In the present invention, at least one silver halide emulsion layer is used. Contains a silver halide emulsion having a silver chloride content of 95 mol% or more. In the present invention, it is preferable that all silver halide emulsion layers are silver halide emulsions having a silver chloride content of 95 mol% or more. The silver halide emulsion used in the present invention is preferably a silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide emulsion having a silver chloride content of 95 mol% or more, and further contains a silver chloride content. Is preferably a silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide emulsion having a mol ratio of 98 mol% or more. Among such silver halide emulsions, 0.01 to 0.50 mol%, more preferably 0.05 to 0.40 mol% of a silver iodochloride phase per mol of total silver in the shell portion of silver halide grains. Those having the above are preferred because high sensitivity is obtained and they are excellent in high illumination exposure suitability. Further, a silver halide grain having a silver bromide localized phase of 0.2 to 5 mol% per mol of total silver, more preferably 0.5 to 3 mol% per mol of silver gives high sensitivity, and This is particularly preferable because the photographic performance can be stabilized.
[0032]
The emulsion of the present invention preferably contains silver iodide. For the introduction of iodide ions, an iodide salt solution may be added alone, or an iodide salt solution may be added together with the addition of a silver salt solution and a high chloride salt solution. In the latter case, the iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the iodide salt and the high chloride salt. The iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth iodide salt. Alternatively, iodide can be introduced by cleaving iodide ions from organic molecules described in US Pat. No. 5,389,508. As another iodide ion source, fine silver iodide grains can be used.
[0033]
The addition of the iodide salt solution may be concentrated at one time of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining an emulsion with high sensitivity and low covering. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 80%. The addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, so that an emulsion with higher sensitivity and lower covering can be obtained.
[0034]
The distribution of iodide ion concentration in the depth direction in the grains can be measured by etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using TRIFT II type TOF-SIMS manufactured by Phi Evans. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection, Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan. When the emulsion grains are analyzed by the etching / TOF-SIMS method, it is possible to analyze that iodide ions ooze out toward the grain surface even when the addition of the iodide salt solution is finished inside the grains. When the emulsion of the present invention contains silver iodide, the iodide ion has a concentration maximum on the grain surface and the iodide ion concentration is attenuated inward by analysis by etching / TOF-SIMS method. Is preferred.
[0035]
The emulsion in the light-sensitive material of the present invention preferably has a silver bromide localized layer.
When the emulsion of the present invention contains a silver bromide localized phase, it is preferable to produce a silver bromide localized phase having a silver bromide content of at least 10 mol% or more by epitaxial growth on the grain surface. Moreover, it is preferable to have the outermost layer shell portion having a silver bromide content of 1 mol% or more in the vicinity of the surface layer.
The silver bromide content of the silver bromide localized phase is preferably in the range of 1 to 80 mol%, and most preferably in the range of 5 to 70 mol%. The silver bromide localized phase is preferably composed of 0.1 to 30 mol% of silver constituting the silver halide grains in the present invention, and is preferably composed of 0.3 to 20 mol% of silver. More preferably, it is configured. The silver bromide localized phase preferably contains a Group VIII metal complex ion such as an iridium ion. The amount of these compounds added varies over a wide range depending on the purpose, but it is 10 per mol of silver halide.^-9-10^-2Mole is preferred.
[0036]
In the present invention, it is preferable to add a transition metal ion in the process of forming and / or growing silver halide grains and incorporate the metal ions into and / or on the surface of the silver halide grains. As the metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, iridium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any of the above metal ions of iron, ruthenium, iridium, osmium, lead, cadmium, or zinc, and a plurality of types of ligands are used as one complex. It is also preferred to use it in the molecule.
[0037]
Among these, the silver halide emulsion of the present invention particularly preferably has iridium ions having at least one organic ligand for the purpose of improving high intensity reciprocity law failure.
When an organic compound is used as a ligand, it is common to other transition metals, but preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered ring or a 6-membered ring. The heterocyclic compound can be mentioned. More preferred organic compounds are compounds having a nitrogen atom, phosphorus atom, oxygen atom or sulfur atom in the molecule as a coordination atom to the metal, most preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds are used as a basic skeleton and substituents are introduced into them are also preferable.
Among these, 5 methylthiazole is particularly preferably used as a preferred ligand for iridium ions among thiazole ligands.
[0038]
As a combination of a metal ion and a ligand, a combination of iron ion, ruthenium ion and cyanide ion is preferable. In these compounds, cyanide ions preferably account for a majority of the coordination number to iron or ruthenium as the central metal, and the remaining coordination sites are thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, pyrazine. Or preferably 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. These complexes with cyanide ions as ligands are 1 × 10 5 per mole of silver during grain formation.^-8From mole to 1 × 10^-2Mole addition is preferred, 1 × 10^-6From mole to 5 × 10^-4Most preferably, it is added in a molar amount.
[0039]
As the iridium ion, not only an organic ligand but also a fluoride ion, a chloride ion, a bromide ion, or an iodide ion, among them, a chloride ion or a bromide ion is preferably used. As the iridium complex, the following specific compounds can be used in addition to those having the above-mentioned organic ligands.
[IrCl₆]^3-, [IrCl₆]^2-, [IrCl₅(H₂O)]^2-, [IrCl₅(H₂O)]⁻, [IrCl₄(H₂O)₂]⁻, [IrCl₄(H₂O)₂]⁰, [IrCl₃(H₂O)₃]⁰, [IrCl₃(H₂O)₃]⁺, [IrBr₆]^3-, [IrBr₆]^2-, [IrBr₅(H₂O)]^2-, [IrBr₅(H₂O)]⁻, [IrBr₄(H₂O)₂]⁻, [IrBr₄(H₂O)₂]⁰, [IrBr₃(H₂O)₃]⁰And [IrBr₃(H₂O)₃]⁺It is.
[0040]
These iridium complexes are 1 × 10 5 per mole of silver during grain formation.^-10From mole to 1 × 10^-3Mole addition is preferred, 1 × 10^-8From mole to 1 × 10^-5Most preferably, it is added in a molar amount. When ruthenium and osmium are used as the central metals, it is also preferable to use nitrosyl ions, thionitrosyl ions, or water molecules and chloride ions as ligands. More preferably, a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex is formed, and a hexachloro complex is also preferably formed. These complexes are 1 x 10 per mole of silver during grain formation.^-10From mole to 1 × 10^-6It is preferable to add a molar amount, more preferably 1 × 10^-9From mole to 1 × 10^-6The molar addition.
[0041]
In the present invention, the above complex is added directly to the reaction solution at the time of silver halide grain formation, added to an aqueous halide solution for forming silver halide grains, or added to other solutions to obtain a grain formation reaction. It is preferably incorporated into the silver halide grains by adding to the solution. Furthermore, it is also preferable that these methods are combined and contained in the silver halide grains.
[0042]
When these complexes are incorporated into silver halide grains, it is preferable that they be uniformly present inside the grains, but these are disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to make it exist only in the particle surface layer, and it is also preferable to add a layer containing no complex only on the particle surface and containing no complex on the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, the particle surface phase may be modified by physical ripening with fine particles incorporating the complex in the particles. preferable. Furthermore, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, and the silver chloride layer, the silver chlorobromide layer, the silver bromide layer, the silver iodochloride layer, and the silver iodobromide layer should each contain the complex. Is also preferable.
[0043]
The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grains and the number average thereof) is 0.01 μm to 2 μm. Is preferred.
The particle size distribution is preferably a so-called monodispersed material having a coefficient of variation (the standard deviation of the particle size distribution divided by the average particle size) of 20% or less, desirably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating.
[0044]
Various compounds or precursors thereof are added to the silver halide emulsion used in the present invention for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. be able to. Specific examples of these compounds are preferably those described in pages 39 to 72 of the above-mentioned JP-A-62-215272. Further, 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (the aryl residue has at least one electron-withdrawing group) are also preferably used.
[0045]
In the present invention, in order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A No. 11-109576 and the carbonyl group described in JP-A No. 11-327094 are adjacent to both ends of an amino group. Alternatively, cyclic ketones having a double bond substituted with a hydroxyl group (particularly those represented by the general formula (S1), paragraph numbers 0036 to 0071 can be incorporated in the specification of the present application), JP-A-11 -143011, sulfo-substituted catechol and hydroquinones (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzene) Sulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4 5-and tri-hydroxy benzenesulfonic acid and salts thereof), water-soluble reducing agents represented by the general formula of JP-A-11-102045 (I) ~ (III) is also preferably used in the present invention.
[0046]
Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range for each layer of emulsion in the light-sensitive material of the present invention.
Examples of spectral sensitizing dyes used for spectral sensitization in the blue, green and red regions in the light-sensitive material of the present invention include F.I. M.M. Examples include those described in Harmer's Heterocyclic compounds-Cyanine dyes and related compounds (John Wiley & Sons [New York, London, 1964)]. As specific examples of compounds and spectral sensitization, those described in JP-A-62-215272, page 22, right upper column to page 38 are preferably used. In particular, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, the strength of adsorption, and the exposure temperature. This is very preferable from the viewpoint of dependency and the like.
[0047]
The addition amount of these spectral sensitizing dyes varies widely depending on the case, and 0.5 × 10 5 per mol of silver halide.^-6Mol ~ 1.0 × 10^-2A molar range is preferred. More preferably, 1.0 × 10^-6Mol ~ 5.0 × 10^-3The range of moles.
[0048]
The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding chemical sensitization, sulfur sensitization represented by addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, right lower column to page 22, upper right column are preferably used. Of these, gold sensitization is particularly preferred. This is because by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with laser light or the like can be further reduced.
[0049]
In order to perform gold sensitization on the silver halide emulsion used in the present invention, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands are used. be able to. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate such as gold (I) potassium dithiocyanate or gold (I) 3 dithiosulfate. It is preferable to use a compound such as a gold dithiosulfate compound such as sodium.
[0050]
Examples of the gold (I) compound having an organic ligand include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, such as gold (I) tetrafluoroborate bis (1,4,5- Trimethyl-1,2,4-triazolium-3-thiolate), organomercaptogold (I) complexes described in JP-A-11-218870, such as potassium bis (1- [3- (2-sulfonatebenzoamido) phenyl] -5-mercaptotetrazole potassium salt) orate (I) pentahydrate, gold (I) compound coordinated with nitrogen compound anion described in JP-A-4-268550, for example, bis (1-methylhydantoinato) Gold (I) sodium salt tetrahydrate can be used. Further, gold (I) thiolate compounds described in US Pat. No. 3,503,749, gold compounds described in JP-A-8-69074, JP-A-8-69075, and JP-A-9-269554, The compounds described in Patent Nos. 5,620,841, 5,912,112, 5,620,841, 5,939,245, and 5,912,111 are also used. be able to.
The amount of these compounds added may vary widely depending on the case, but is 5 × 10 5 per mole of silver halide.^-7~ 5x10^-3Mole, preferably 5 × 10^-6~ 5x10^-4Is a mole.
[0051]
Colloidal gold sulfide can also be used. The manufacturing method thereof is Research Disclosure (37154), Solid State Ionics Vol. 79, 60-66, 1995, Compt. Rend. Hebt. Seans Acad. Sci. Sect. B, 263, p. 1328, published in 1966. Various sizes of colloidal gold sulfide can be used, and those having a particle size of 50 nm or less can also be used. The amount added can vary widely depending on the case, but 5 × 10 5 as gold atoms per mole of silver halide.^-7~ 5x10^-3Mole, preferably 5 × 10^-6~ 5x10^-4Is a mole.
In the present invention, gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using other than gold compounds.
[0052]
The silver halide color photographic light-sensitive material of the present invention comprises at least one yellow color-forming silver halide emulsion layer, magenta color-forming silver halide emulsion layer, and cyan color-forming silver halide emulsion layer. Generally, these silver halide emulsion layers are a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer, and a cyan color-forming silver halide emulsion layer in the order from the support.
However, a different layer structure may be used.
[0053]
The silver halide emulsion layer containing the yellow-coupler may be disposed at any position on the support. However, from the viewpoint of color development acceleration, desilvering acceleration, and reduction of residual color by sensitizing dye, The coupler-containing silver halide emulsion layer is preferably coated at a position farthest from the support than the other silver halide emulsion layers. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably the center layer of other silver halide emulsion layers, and from the viewpoint of reducing photobleaching, the cyan coupler-containing silver halide emulsion layer is The lowest layer is preferred. Each of the color developing layers of yellow, magenta and cyan may be composed of two layers or three layers. For example, as described in JP-A-4-75055, 9-1114035, 10-246940, US Pat. No. 5,576,159, etc., a coupler layer containing no silver halide emulsion is used as a silver halide. It is also preferable to provide a color developing layer adjacent to the emulsion layer.
[0054]
As silver halide emulsions and other materials (additives, etc.) and photographic composition layers (layer arrangement, etc.) applied in the present invention, and processing methods and processing additives applied to process this photosensitive material, JP-A-62-215272, JP-A-2-33144, and those described in European Patent EP0,355,660A2, particularly those described in European Patent EP0,355,660A2 are preferably used. . Furthermore, JP-A-5-34889, JP-A-4-359249, JP-A-4-313733, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433, JP-A-2-854. The silver halide color photographic light-sensitive materials and the processing methods thereof described in JP-A Nos. 1-158431, 2-90145, 3-194539, 2-93641, and European Patent Publication No. 0520457A2 are also preferable.
[0055]
In particular, in the present invention, silver halide emulsions, further different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization methods (sensitizers) , Spectral sensitization (spectral sensitizer), cyan, magenta, yellow coupler and its emulsifying dispersion method, color image preservability improver (stain inhibitor and anti-fading agent), dye (colored layer), gelatin species, photosensitive Regarding the layer structure of the material, the coating pH of the photosensitive material, and the like, those described in each part of the patent shown in the following table can be particularly preferably applied.
[0056]
[Table 1]

[0057]
Other examples of the cyan, magenta and yellow couplers used in the present invention include those described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144, No. 3; Page 14 upper right column 14th line to 18th page upper left column last line, page 30 upper right column 6th line to page 35 lower right column 11th line, EP0355,660A2 page 4, 15th line to 27th line, 5th page Couplers described on page 30 to the end of page 28, page 45, line 29 to line 31, page 47, line 23 to page 63, line 50 are also useful.
In the present invention, compounds represented by general formulas (II) and (III) of WO 98/33760 and general formula (D) of JP-A No. 10-221825 may be preferably added.
[0058]
As a cyan dye-forming coupler that can be used in the present invention (sometimes simply referred to as “cyan coupler”), a pyrrolotriazole-based coupler is preferably used, and a general formula (I) or (II) of JP-A-5-313324 And couplers represented by the general formula (I) of JP-A-6-347960 and exemplified couplers described in these patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Other cyan couplers include pyrroloazole type cyan couplers described in European Patents EP 0488248 and EP 0491197A1, 2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716, US Pyrazoloazole type cyan couplers having an electron withdrawing group and a hydrogen bonding group at the 6-position described in Japanese Patent Nos. 4,873,183 and 4,916,051, particularly JP-A-8-171185, Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A Nos. 8-311360 and 8-339060 are also preferable.
[0059]
In addition to diphenylimidazole cyan couplers described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in European Patent EP 0333185A2 (among others, couplers (42) listed as specific examples) And a cyclic active methylene-based cyan coupler described in JP-A No. 64-32260, which is obtained by adding a chlorine-eliminating group to a 4-equivalent coupler, and couplers (6) and (9) are particularly preferable. Of these, coupler examples 3, 8, and 34 listed as specific examples are particularly preferred), pyrrolopyrazole type cyan couplers described in EP 0456226A1 and pyrroloimidazole type cyan couplers described in EP 0484909 are used. You can also.
[0060]
Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred. The couplers (1) to (47) are applied to the present application as they are, and are preferably incorporated as part of the specification of the present application.
[0061]
Examples of the magenta dye-forming coupler used in the present invention (sometimes simply referred to as “magenta coupler”) include 5-pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers described in the publicly known literatures in the above table. Among them, a secondary or tertiary alkyl group as described in JP-A-61-65245 is directly connected to the 2, 3, or 6 position of the pyrazolotriazole ring, particularly in terms of hue, image stability and color development. Pyrazolotriazole couplers, pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-61-65246, and alkoxyphenylsulfonamides as described in JP-A-61-147254 Pyrazoloazole couplers having ballast groups and European Patent Nos. 226,849A and 294,785A Use of pyrazoloazole couplers preferably have an alkoxy group or an aryloxy group at the 6-position as described in. In particular, the magenta coupler is preferably a pyrazoloazole coupler represented by the general formula (M-I) described in JP-A-8-122984. Paragraph Nos. 0009 to 0026 of the patent are directly applied to the present application. Incorporated as part of the specification. In addition, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in European Patent Nos. 854384 and 844640 are also preferably used.
[0062]
Further, as a yellow dye-forming coupler (in this specification, sometimes simply referred to as “yellow coupler”), an acylacetamide type yellow having a 3- to 5-membered cyclic structure in an acyl group described in European Patent EP 0447969A1 Coupler, a malondianilide type yellow coupler having a cyclic structure described in European Patent EP 0 482 552 A1, European Published Patent Nos. Pyrrole-2 or 3-yl or indol-2 or 3-ylcarbonylacetic acid anilide couplers described in US Pat. No. 953875A1, etc., acylacetamide type having a dioxane structure described in US Pat. No. 5,118,599 B Low coupler is preferably used. Among them, it is preferable to use an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring. These couplers can be used alone or in combination.
[0063]
The coupler used in the present invention is impregnated with a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvent described in the preceding table, Alternatively, it is preferably dissolved together with a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15, and International Publication WO 88/00723, pages 12 to 30. The described homopolymers or copolymers are mentioned. More preferably, use of a methacrylate or acrylamide polymer, particularly an acrylamide polymer is preferred in view of color image stability.
[0064]
In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable.
For example, high molecular weight redox compounds described in JP-A-5-333501, phenidone and hydrazine compounds described in WO98 / 33760, U.S. Pat. No. 4,923,787, JP-A-5-249637, White couplers described in JP-A-10-282615 and German Patent No. 19629142A1 can be used. In particular, in the case of increasing the pH of the developing solution and speeding up development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 842975A1, German Patent No. 19804646A1 and French Patent No. 2760460A1 It is also preferable to use the redox compound described in the above.
[0065]
In the present invention, a compound having a triazine skeleton with a high molar extinction coefficient is preferably used as the ultraviolet absorber, and for example, compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or non-photosensitive. For example, JP-A-46-3335, JP-A-55-15276, JP-A-5-197004, JP-A-5-232630, JP-A-5-307232, JP-A-6-21813, JP-A-8-53427, and 8- No. 234364, No. 8-239368, No. 9-310667, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. 19739797A, European Patent No. The compounds described in 501291 etc. can be used.
[0066]
As the binder or protective colloid that can be used in the light-sensitive material according to the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As a preferable gelatin, the heavy metal contained as impurities such as iron, copper, zinc and manganese is preferably 5 ppm or less, more preferably 3 ppm or less. The amount of calcium contained in the photosensitive material is preferably 20 mg / m.²Or less, more preferably 10 mg / m²Or less, most preferably 5 mg / m²It is as follows.
[0067]
In the present invention, an antibacterial / antifungal agent as described in JP-A-63-271247 is added in order to prevent various wrinkles and bacteria that propagate in the hydrophilic colloid layer and degrade the image. Is preferred. Further, the film pH of the photosensitive material is preferably 4.0 to 7.0, more preferably 4.0 to 6.5.
[0068]
In the present invention, a surfactant can be added to the photosensitive material from the viewpoints of improving the coating stability of the photosensitive material, preventing the generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but generally 1 × 10 10^-5~ 1g / m², Preferably 1 × 10^-4~ 1x10^-1g / m²More preferably 1 × 10^-3~ 1x10^-2g / m²It is.
[0069]
The photosensitive material of the present invention is a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) using a combination of a solid state laser using a semiconductor laser and a nonlinear optical crystal. A digital scanning exposure method using density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.
[0070]
When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In an SHG light source obtained by combining a solid-state laser using a semiconductor laser as an excitation light source or a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green and red.
[0071]
The transmission support used in the present invention may be any support as long as it is a substantially transparent support. For example, a transparent support such as a cellulose nitrate film, a polyethylene terephthalate film, a polycarbonate film, a polystyrene film, or a polypropylene film. A substrate is used. Among these, a polyethylene terephthalate film is preferable.
[0072]
Although there is no restriction | limiting in particular about the thickness of a permeation | transmission support body, Preferably it is 150-250 micrometers, More preferably, it is 160 micrometers-200 micrometers.
The transmissive support is a support having a light transmittance of 90% or more. The transmittance is described in detail in US Pat. No. 6,248,483B1.
[0073]
The support in the present invention may be provided with an antihalation layer on the emulsion layer and / or the back surface. Examples of the light absorbing material used in the antihalation layer include various inorganic materials and dyes. As the inorganic substance, for example, a colloidal metal can be used, preferably colloidal silver, colloidal manganese or the like, and more preferably colloidal silver. As dyes, there are various properties such as having good spectral absorption characteristics according to the purpose of use, being completely decolorized in photographic processing solutions, and having no adverse effects such as fogging and desensitization on photographic emulsions. Must meet the conditions. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.
[0074]
In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloid layer can be decolored by processing described in pages 27 to 76 of European Patent EP0,337,490A2 for the purpose of improving the sharpness of an image. It is preferable to contain a simple dye (especially an oxonol dye).
[0075]
In the silver halide color photographic light-sensitive material of the present invention, a hydrophilic colloid layer is formed on pages 27 to 76 of EP 0337490 A2 for the purpose of preventing irradiation and halation or improving safetylight safety. It is preferable to add a dye (in particular, an oxonol dye or a cyanine dye) which can be decolorized by treatment as described in 1. Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes degrade color separation and safelight safety when the amount used is increased. As the dye that can be used without deteriorating color separation, water-soluble dyes described in JP-A Nos. 5-127324, 5-127325, and 5-216185 are preferable.
[0076]
In the processing of the photosensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17 The processing materials and processing methods described in the 20th page, lower right column, line 20 are preferably applicable. Further, as the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.
[0077]
As chemicals for treatment agents, CP45X, CP47L, CP48S manufactured by Fuji Photo Film Co., Ltd., RA-100, RA-4 manufactured by Eastman Kodak Co., etc. can be applied.
[0078]
A known or commercially available diaminostilbene fluorescent whitening agent can be used for the color developer. As the known bistriazinyldiaminostilbene disulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625 or JP-A-10-104809 are preferable. Commercially available compounds are disclosed in, for example, “Dyeing Note” 19th Edition (Color Dyeing) P.A. 165-P. Among the products described herein, Blankophor UWiq, Blankophor REU or Hakkol BRK are preferred. The following compounds can also be preferably used.
[0079]
[Chemical 1]

[0080]
In the present invention, the inclusion of halide ions such as Br and I in the bleach-fixing solution in particular prevents image unevenness when entering the bleach-fixing solution from the developer, has excellent fixing ability, and has a white background of the uncolored portion. This is preferable from the viewpoint of preventing contamination by silver sulfide or the like. In the bleach-fixing solution of the present invention, the bromide ion concentration is 0 to 1.0 mol / L, more preferably 0.01 to 0.3 mol, for the purpose of preventing the color contamination by residual silver and achieving the object of the present invention. / L is preferable. Further, for the same purpose, an iodide ion concentration may be contained, and a preferable iodide ion concentration is 0 to 0.1 mol / L, more preferably 0.001 to 0.01 mol / L.
[0081]
The light-sensitive material of the present invention can be developed after exposure using a conventional developing method containing an alkali agent and a developing agent, an activator such as an alkaline solution containing the developing agent in the photosensitive material and not containing the developing agent. In addition to a wet method such as a method of developing with a beta solution, a thermal development method that does not use a processing solution can be used. In particular, the activator method is a preferable method from the viewpoint of environmental protection because it does not contain a developing agent in the processing solution, so that the processing solution can be easily managed and handled, and the load during processing of the waste liquid is small.
In the activator method, examples of the developing agent incorporated in the light-sensitive material or a precursor thereof include, for example, JP-A-8-234388, JP-A-9-152686, JP-A-9-152893, JP-A-9-2111814, and JP-A-9-21814. The hydrazine type compound described in -160193 is preferable.
[0082]
Further, a developing method in which the amount of silver applied to the photosensitive material is reduced and image amplification processing (compensation processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, an image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and 9-152695 is preferably used. In the activator method, after processing with an activator solution, desilvering is usually performed. However, in the image amplification processing method using a low silver amount of light-sensitive material, desilvering is omitted and washing or stabilization is simplified. Can be done. Further, in a method of reading image information from a photosensitive material with a scanner or the like, it is possible to adopt a processing form that does not require a desilvering process even when a high silver amount photosensitive material such as a photographic photosensitive material is used.
[0083]
For the activator solution, desilvering solution (bleaching / fixing solution), water washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, those described in Research Disclosure Item 36544 (September 1994), pages 536 to 541 and JP-A-8-234388 can be used.
[0084]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
[0085]
[Example 1]
(Preparation of blue-sensitive layer emulsions A-1 and A-2 of the present invention)
Add 46.3 ml of a 10% solution of NaCl to 1.06 liters of deionized distilled water containing 5.7% by weight of deionized gelatin.₂SO₄46.4 ml of (1N) was added, 0.012 g of the compound represented by the following compound (X) was further added, and the liquid temperature was adjusted to 60 ° C. Mole and 0.1 mol of NaCl were added into the reaction vessel over 10 minutes. Subsequently, 1.5 mol of silver nitrate and NaCl solution were added over 60 minutes by the flow rate acceleration method so that the final addition rate was 4 times the initial addition rate. Next, 0.2 mol% silver nitrate and NaCl solution were added at a constant addition rate over 6 minutes. At this time, the NaCl solution contains K₃IrCl₅(H₂O) 5 × 10 with respect to total silver^-7Molar amounts were added and the particles were doped with iridium aquoide.
Further, 0.2 mol of silver nitrate, 0.18 mol of NaCl and 0.02 mol of KBr solution were added over 6 minutes. At this time, in the halogen aqueous solution, 0.5 × 10^-5K equivalent to mole₄Ru (CN)₆And K₄Fe (CN)₆Were dissolved and added to the silver halide grains.
In addition, during the final stage grain growth, an aqueous KI solution corresponding to 0.001 mol relative to the total silver amount was added to the reaction vessel over 1 minute. The position of the addition start was started when 93% of the total particle formation was completed.
Thereafter, a precipitation agent of the following compound (Y) was added at 40 ° C., and the pH was adjusted to around 3.5, followed by desalting and washing with water.
[0086]
[Chemical 2]

[0087]
Deionized gelatin, an aqueous NaCl solution and an aqueous NaOH solution were added to the emulsion after washing with desalted water, and the mixture was heated to 50 ° C. and adjusted to pAg 7.6 and pH 5.6.
Thus, a silver halide having an average side length of 0.70 μm and a side length coefficient of variation of 8%, comprising a halogen composition of 98.9 mol% of silver chloride, 1 mol% of silver bromide, and 0.1 mol% of silver iodide. Gelatin containing cubic particles was obtained.
[0088]
The emulsion grains were maintained at 60 ° C., and spectral sensitizing dyes 1 and 2 were each 2.5 × 10^-4Mol / Ag mol and 2.0 × 10^-4Mol / Ag mol was added. Further, 1 × 10 of thiosulfonic acid compound-1^-5A fine grain emulsion of 90 mol% silver bromide and 10 mol% silver chloride doped with iridium hexachloride and having an average grain size of 0.05 μm was added and ripened for 10 minutes. Further, fine grains of 40 mol% silver bromide and 60 mol% silver chloride having an average grain diameter of 0.05 μm were added and ripened for 10 minutes. The fine grains dissolved, thereby increasing the silver bromide content of the host cubic grains to 1.3 moles. Moreover, iridium hexachloride is 1 × 10^-7Mol / Ag mole dope.
[0089]
Subsequently, sodium thiosulfate 1 × 10^-5Mol × Ag mol and gold sensitizer-1 2 × 10^-5Mole was added. Immediately after that, the temperature was raised to 60 ° C., followed by aging for 40 minutes, and then the temperature was lowered to 50 ° C. Immediately after the temperature was lowered, 6 × 10 each of mercapto compounds-1 and 2 were added.^-4Mole / Ag mol was added. Thereafter, after ripening for 10 minutes, the KBr aqueous solution was added to 0.008 mol with respect to silver, and after aging for 10 minutes, the temperature was lowered and stored.
In this way, a high-sensitivity emulsion A-1 for blue-sensitive layer was prepared.
Cubic grains having an average side length of 0.55 μm and a side length variation coefficient of 9% were formed in the same manner except for the emulsion preparation method and the temperature during grain formation. The temperature during grain formation was 55 ° C.
Spectral sensitization and chemical sensitization were carried out with an amount adjusted to match the specific surface area (side length ratio 0.7 / 0.55 = 1.27 times), and the low-sensitive emulsion A-2 for the blue-sensitive layer It was created.
[0090]
[Chemical 3]

[0091]
(Adjustment of comparative blue-sensitive emulsions B-1 and B-2)
Except for changing the adjustment conditions of Emulsion A-1 as follows, the same as the adjustment conditions for Emulsions B-1 and B-2, the sensitive side emulsion for comparative blue sensitive layer Emulsion B-1, the insensitive side for comparative blue sensitive layer Emulsion B-2 was prepared.
Under the emulsion preparation conditions of Emulsion A-1, the grain size was adjusted to 68 ° C. to make the grain size an average side length of 0.85 μm. The variation coefficient of the side length was 12%. In addition, the introduction of iodine ions at the final stage of grain formation was stopped and replaced with Cl ions. Therefore, the halogen composition at the end of grain formation is 99 mol% of silver chloride and 1 mol% of silver bromide. The amount of spectral sensitizing dye-1 and spectral sensitizing dye-2 added was 1.25 times that in the preparation of emulsion A-1. An equal amount of thiosulfonic acid-1 was used.
[0092]
Furthermore, the chemical sensitization was changed as follows. A fine grain emulsion of 90 mol% silver bromide having an average grain size of 0.05 μm and doped with iridium hexachloride with 10 mol% of silver chloride was added and ripened for 10 minutes. Further, fine grains of 40 mol% silver bromide and 60 mol% silver chloride having an average grain diameter of 0.05 μm were added and ripened for 10 minutes. The fine grains dissolved, thereby increasing the silver bromide content of the host cubic grains to 2.0 mol%. In addition, iridium hexachloride is 2 × 10^-7Mol / Ag mole dope.
[0093]
Subsequently, sodium thiosulfate 1 × 10^-5Mole / Ag mol was added. Immediately after that, the temperature was raised to 55 ° C., followed by aging for 70 minutes, and then the temperature was lowered to 50 ° C. No gold sensitizer was added. Immediately after the temperature was lowered, 4 × 10 each of mercapto compounds-1 and 2 were added.^-4Mole / Ag mol was added. Thereafter, after aging for 10 minutes, an aqueous KBr solution was added so as to be 0.010 mol relative to silver, and after aging for 10 minutes, the temperature was lowered and stored.
In this way, a high-sensitivity emulsion B-1 for a comparative blue-sensitive layer was prepared.
[0094]
As in Emulsion B-1, except that the temperature during grain formation was lowered to form grains having an average side length of 0.68 μm and a side length variation coefficient of 12%. Spectral sensitization and chemical sensitizers were made 1.25 times the emulsion B-1 in consideration of the surface area ratio to prepare a low-sensitive emulsion B-2 for the comparative blue-sensitive layer.
[0095]
(Preparation of emulsion C-1 and green emulsion 2 of the present invention)
Except for lowering the temperature at the time of grain formation with Emulsion A-1 and changing the type of sensitizing dye as described below, the high-sensitivity emulsion C for green-sensitive layer emulsions was prepared in the same manner as the adjustment conditions for Emulsions A-1 and A-2. -1, low sensitivity side emulsion C-2 for green sensitive layer was prepared.
The grain size of the high-sensitivity emulsion C-1 was 0.40 [mu] m on the average side length, the low-sensitivity emulsion C-2 was 0.30 [mu] m on the average side, and the coefficient of variation was 8%.
[0096]
[Formula 4]

[0097]
Sensitizing dye D per mole of silver halide is 3.0 x 10 for a large size emulsion (high sensitivity emulsion C-1).^-43.6 × 10 for a mole, small size emulsion (low sensitivity emulsion C-2)^-4Mol, and Sensitizing Dye E per mol of silver halide, 4.0 × 10 for large size emulsions^-57.0 x 10 for molar, small emulsions^-5Mole was added.
[0098]
(Adjustment of comparative green-sensitive emulsion D-1 and 2)
Comparative green sensitive layer emulsion D-1 in the same manner as the preparation conditions of emulsions B-1 and B-2 except that the temperature at the time of grain formation with emulsion B-1 was lowered and the type of sensitizing dye was changed. A low-sensitive emulsion D-2 for a comparative green-sensitive layer was prepared.
The grain size of the high-sensitivity emulsion D-1 was 0.50 [mu] m on the average side length, the low-sensitivity emulsion D-2 was 0.40 [mu] m on the average side, and the variation coefficient thereof was 10%.
Further, the sensitizing dye D is 4.0 × 10 per 1 mol of silver halide for a large-size emulsion (high-sensitivity emulsion D-1).^-44.5 x 10 for mole, small size emulsion (low sensitive emulsion D-2)^-4Moles, and sensitizing dye E per mole of silver halide, 5.0 × 10 5 for large size emulsions.^-58.8 × 10 for small, small emulsions^-5Mole was added.
[0099]
(Preparation of emulsion E-1 and 2 for red-sensitive layer of the present invention)
Except for lowering the temperature at the time of grain formation with Emulsion A-1 and changing the kind of sensitizing dye as follows, the sensitive emulsion for red sensitive layer E-1 was used in the same manner as for Emulsions A-1 and A-2. A low-sensitive emulsion E-2 for the red-sensitive layer was prepared.
The grain size of the high-sensitivity emulsion E-1 is 0.38 μm on the average side length, and the average side length is 0.32 μm on the low-sensitivity emulsion E-2. The coefficient of variation of the side length is 9% and 10%, respectively. Met.
[0100]
[Chemical formula 5]

[0101]
Sensitizing dyes G and H, respectively, per 8.0 moles of silver halide, 8.0 × 10 8 for large size emulsions (high sensitivity side emulsion E-1)^-510.7 × 10 for mole, small size emulsion (low sensitive emulsion E-2)^-5Mole was added.
Further, the following compound I was added to the red-sensitive emulsion layer at 3.0 × 10 6 per mole of silver halide.^-3Mole was added.
[0102]
[Chemical 6]

[0103]
(Adjustment of comparative red-sensitive emulsions F-1 and F-2)
Comparative red-sensitive layer Emulsion F-1 in the same manner as Emulsions B-1 and B-2 except that the temperature at the time of grain formation with Emulsion B-1 was lowered and the type of sensitizing dye was changed. A low-sensitive emulsion F-2 for a comparative red-sensitive layer was prepared.
The grain size of the high-sensitivity emulsion F-1 is 0.57 μm on the average side length, and the average side length is 0.43 μm on the low-sensitivity side emulsion F-2. The coefficient of variation of the side length is 9% and 10%, respectively. Met.
Further, each of sensitizing dyes G and H per 1.0 mol of silver halide is 1.0 × 10 6 for a large-size emulsion (high-sensitivity emulsion F-1).^-41.34 × 10 for a mole, small size emulsion (low sensitive emulsion F-2)^-4Mole was added. Further, Compound I was added to the red-sensitive emulsion layer at 3.0 × 10 6 per mole of silver halide.^-3Mole was added.
[0104]
(Preparation of emulsion G-1 and 2 for blue-sensitive layer of the present invention)
Emulsions A-1 and A-2 each have a K value from the point of 60% to 80% addition of silver nitrate.₃RhBr₆The Rh content per mole of the finished silver halide was 2.7 × 10^-9Emulsions differing only in the amount added were prepared, and these were designated as blue sensitive layer high sensitive side emulsion G-1 and blue sensitive layer low sensitive side emulsion G-2, respectively. The average side length of the grains and the coefficient of variation of the side length were the same as those of the corresponding emulsions A-1 and A-2.
[0105]
(Preparation of Emulsion H-1 and 2 for Green Sensitive Layer of the Present Invention)
Emulsions C-1 and C-2 each had a K K addition from 60% to 80%.₃RhBr₆The Rh content per mole of the finished silver halide is 4.7 × 10^-9Emulsions differing only in the amount added were prepared, and these were designated as green sensitive layer high sensitive emulsion H-1 and green sensitive layer low sensitive emulsion H-2, respectively. The average side length of the grains and the coefficient of variation of the side length were the same as those of the corresponding emulsions C-1 and C-2.
[0106]
(Preparation of emulsions I-1 and 2 for red-sensitive layer of the present invention)
Emulsions E-1 and E2 each have a K value from 60% to 80% addition of silver nitrate.₃RhBr₆Rh amount per mole of the finished silver halide is 6.7 × 10^-9Emulsions differing only in the amount added were prepared, and these were designated as red-sensitive layer high-sensitivity emulsion I-1 and red-sensitive layer low-sensitivity emulsion I-2, respectively. The average side length of the grains and the coefficient of variation of the side length were the same as those of the corresponding emulsions E-1 and E-2.
[0107]
First layer coating preparation
Yellow coupler (ExY) 61.9 g, color image stabilizer (Cpd-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) ) 2 g was dissolved in 21 g of solvent (Solv-1) and 80 ml of ethyl acetate, and this liquid was emulsified and dispersed in 294 g of a 23.5 mass% gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate by a high-speed stirring emulsifier (dissolver). Then, water was added to prepare 900 g of emulsified dispersion A.
On the other hand, the emulsified dispersion A and the emulsions A-1 and A-2 were mixed and dissolved to prepare a first layer coating solution having a composition described later. The emulsion coating amount indicates the silver coating amount.
[0108]
The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. Moreover, the total amount of Ab-1, Ab-2, Ab-3 and Ab-4 is 15.0 mg / m in each layer.²60.0 mg / m²5.0 mg / m²And 10.0 mg / m²It added so that it might become.
[0109]
[Chemical 7]

[0110]
[Chemical 8]

[0111]
In addition, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the second layer, the fourth layer, the sixth layer, and the seventh layer, respectively, at 0.2 mg / m 2.²0.2 mg / m²0.6 mg / m²0.1 mg / m²It added so that it might become.
Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, respectively, at 1 × 10 6 per 1 mol of silver halide.^-4Mol, 2 × 10^-4Mole was added.
Further, a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200000-400000) is 0.05 g / m on the red sensitive emulsion layer.²Was added.
Further, disodium catechol-3,5-disulfonate was added to the second layer, the fourth layer, and the sixth layer, respectively, at 6 mg / m.²6 mg / m²18 mg / m²It added so that it might become.
In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).
[0112]
[Chemical 9]

[0113]
(Layer structure)
The structure of each layer is shown below. Numbers are application amount (g / m²). The silver halide emulsion represents a coating amount in terms of silver.
Support
As a support, on the side opposite to the transparent polyethylene terephthalate emulsion having a thickness of 180 μm, 6.2 g / m of gelatin was used.²The following dye-1, dye-2 and dye-3 were each 0.07 g / m.²0.04 g / m²0.095 g / m²And UV absorber (UV-B) 0.31 g / m², 0.03 g / m of surfactant (Cpd-13)²The coated one was used.
[0114]
Embedded image

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]
Embedded image

[0122]
Embedded image

[0123]
Embedded image

[0124]
Embedded image

[0125]
Embedded image

[0126]
Embedded image

[0127]
Embedded image

[0128]
Embedded image

[0129]
Embedded image

[0130]
Embedded image

[0131]
The development process was performed under the following conditions using a color paper development process CP-45X manufactured by Fuji Photo Film Co., Ltd.
Development process CP-45X for Fuji color paper
Processing process Processing temperature Processing time Replenishment amount
Color development 35 ± 0.3 ° C 110 seconds 370 mL / m²
Bleach fixing 33-37 ° C 110 seconds 494mL / m²
Washing with water 24 to 34 ° C 220 seconds 3 to 10 L / m²
Dry 50-70 ° C 3 minutes
[0132]
Sample 1011 was prepared as described above. Subsequently, samples were prepared by changing the coating amounts of the emulsion and the emulsion-containing layer as shown in Table 2 with respect to Sample 1011.
[0133]
[Table 2]

[0134]
exposure
A sample prepared in this manner was used as a xenon flash light source (light emission time of 10^-4The color development processing was performed 5 minutes after the exposure. A density correction filter (CC filter) was used as necessary so that the image obtained at the time of exposure contained a range from the lowest density to the highest density. Further, the CC filter was adjusted as necessary so that the status A transmission density of yellow, magenta and cyan would be 1.0 at the same exposure amount.
Next, a color development process was performed on a sample exposed under the same exposure conditions as described above 30 minutes after the exposure. These samples are bonded so that the positions of the same exposure amount are adjacent to each other, and sensory evaluation of 10 persons is performed on the blackness of the high density portion and the connection between the bonded portions, and five levels (5: good, 1: Evaluation was made in 5 stages, which were bad, with 4 or more within the allowable range. The results are shown in Table 3.
[0135]
[Table 3]

[0136]
As is clear from Table 3, it is clear that the samples of the present invention are significantly superior in black tightening and bonding suitability as compared with the comparative samples, and can satisfy both of these characteristics.
[0137]
[Example 2]
The samples 1001, 1011, and 1021 used in the examples were subjected to the following exposure.
Scanning exposure was performed using a laser exposure machine Lambda76 manufactured by Durst. The maximum transmission density preset by the user was set as shown in Table 4, and calibration was performed using a calibration image including 21 levels of gray patches. By repeating the number of calibrations shown in Table 4, each gray patch in the 21 stages converged to the target density indicated by the exposure apparatus. When performing the calibration, the conditions were set so that the color development processing started 5 minutes after the exposure.
[0138]
[Table 4]

[0139]
After the calibration is completed, the image for image evaluation including the highest density and the lowest density under the exposure conditions is exposed, and then the highest density of the sample that has started the color development processing is measured in 5 minutes, and the high density portion is used. Sensory evaluation of 10 persons was performed regarding black tightening of an image, and evaluation was performed on a 5-level scale (5: good, 1: bad, 4 or more are acceptable). In addition, a sample which started color development in 30 minutes after exposure under the same exposure conditions was prepared, and the sample processed in 5 minutes after exposure was bonded so that the gray patches having the same exposure amount were adjacent to each other, Similarly, the sensory evaluation of 10 persons was performed on the goodness of the connection of the bonded portions, and the evaluation was made on a 5-grade scale (5: good, 1: bad, 4 or more are acceptable). The results are shown in Table 5.
[0140]
[Table 5]

[0141]
As is apparent from Table 5, it can be seen that the samples 2004 to 2007 using the photosensitive materials 1011 and 1021 of the present invention are remarkably excellent in black tightening and bonding suitability. On the other hand, the samples 2001 to 2003 using the comparative photosensitive material 1001 have insufficient bonding suitability. In particular, the samples 2001 and 2002 are calibrated by setting the maximum transmission density to 2.80 or more in advance. It can be seen that the bonding suitability is insufficient even if the bonding is performed.
[0142]
【The invention's effect】
As described above, according to the present invention, a silver halide color photographic light-sensitive material suitable for advertisement display prints can be provided. In particular, a vivid image having a high image density can be obtained, and a silver halide color photographic light-sensitive material having an excellent quality can be provided in laminating images important for advertisement display prints.

Claims (3)

A silver halide color photographic light-sensitive material having at least one yellow image forming layer, magenta image forming layer, and cyan image forming layer on a transparent support, and was subjected to surface exposure with an exposure time of ^10-4 seconds. At this time, the maximum transmission density of each layer is 3.0 or more, and the photosensitive material is exposed at an exposure amount that gives a density of 1.0 when the photosensitive material is developed and processed 5 minutes after exposure. A silver halide color photographic light-sensitive material having a transmission density of 0.95 or more and 1.05 or less when the material is developed and processed 30 minutes after exposure. At least one silver halide emulsion layer of the silver halide color photographic light-sensitive material contains at least one selected from metal complexes represented by the following general formula (I) and has a silver chloride content of 95 mol% or more. 2. The silver halide color photographic light-sensitive material according to claim 1, comprising silver chloride emulsion grains.
Formula (I)
_{^{[MX I n L I (6}} -n)] m
In the general formula (I), M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, X ^I represents a halogen ion, and L ^I represents an arbitrary arrangement different from X ^I. Represents a quantifier. n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0 or 1+. An image forming method in which color development processing is performed after scanning exposure with a light beam, and the apparatus used for scanning exposure outputs a calibration image and measures the density, and sets the maximum transmission density set in advance. 3. The halogen according to claim 1, wherein the apparatus has a function of calibrating exposure conditions of gray gradations reaching density, and has a preset maximum transmission density of 2.8 or more. An image forming method using a silver halide color photographic light-sensitive material.