JP4044796B2 - Silver halide photographic material - Google Patents

Description

【００８５】
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号公報の第９１頁右上欄４行目〜１２１頁左上欄６行目、特開平２−３３１４４号公報の第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号明細書の第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号公報の一般式（Ｄ）で表される化合物を添加してもよく、好ましい。
【００８６】
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号公報の一般式（Ｉ）又は（II）で表されるカプラー及び特開平６−３４７９６０号公報の一般式（Ｉ）で表されるカプラー並びにこれらの公報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号公報に記載の一般式（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号明細書、同第４，９１６，０５１号明細書に記載の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号公報、同８−３１１３６０号公報、同８−３３９０６０号公報に記載の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。
【００８７】
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（中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（中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号明細書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。
【００８８】
なお、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、該公報の段落番号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。
【００８９】
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号公報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号公報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号公報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号明細書や同第２９４，７８５Ａ号明細書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号公報に記載の一般式（Ｍ−Ｉ）で表されるピラゾロアゾールカプラーが好ましく、該公報の段落番号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号明細書、同第８８４６４０号明細書に記載の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。
【００９０】
また、イエロー色素形成カプラー(単に、「イエローカプラー」という場合がある）としては、前記表中に記載の化合物の他に、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号明細書、同第９５３８７１Ａ１号明細書、同第９５３８７２Ａ１号明細書、同第９５３８７３Ａ１号明細書、同第９５３８７４Ａ１号明細書、同第９５３８７５Ａ１号明細書等に記載のピロール−２又は３−イル若しくはインドール−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。その中でも、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特に好ましい。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。
【００９１】
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号明細書）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。
【００９２】
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公報等に記載のものが好ましい。
例えば、特開平５−３３３５０１号公報に記載の高分子量のレドックス化合物、ＷＯ９８／３３７６０号明細書、米国特許第４，９２３，７８７号明細書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号公報、特開平１０−２８２６１５号公報及び独国特許第１９６２９１４２Ａ１号明細書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号明細書、欧州特許第８３９６２３Ａ１号明細書、欧州特許第８４２９７５Ａ１号明細書、独国特許第１９８０６８４６Ａ１号明細書及び仏国特許第２７６０４６０Ａ１号明細書等に記載のレドックス化合物を用いることも好ましい。
【００９３】
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、以下の公報等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号公報、同５５−１５２７７６号公報、特開平５−１９７０７４号公報、同５−２３２６３０号公報、同５−３０７２３２号公報、同６−２１１８１３号公報、同８−５３４２７号公報、同８−２３４３６４号公報、同８−２３９３６８号公報、同９−３１０６７号公報、同１０−１１５８９８号公報、同１０−１４７５７７号公報、同１０−１８２６２１号公報、独国特許第１９７３９７９７Ａ号明細書、欧州特許第７１１８０４Ａ号明細書及び特表平８−５０１２９１号公報等に記載されている化合物を使用できる。
【００９４】
本発明の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／ｍ²以下、更に好ましくは１０ｍｇ／ｍ²以下、最も好ましくは５ｍｇ／ｍ²以下である。
【００９５】
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。
【００９６】
本発明における写真構成層構成層中の総塗設ゼラチン量は３ｇ／ｍ^２以上６ｇ／ｍ^２以下であることが好ましく、３ｇ／ｍ^２以上５ｇ／ｍ^２以下であることが更に好ましい。また、超迅速処理した場合でも、現像進行性、及び定着漂白性、残色を満足するために、写真構成層全体の膜厚が３μｍ〜７．５μｍであることが好ましく、更に３μｍ〜６．５μｍであることが好ましい。乾燥膜厚の評価方法は、乾燥膜剥離前後の膜厚の変化、あるいは断面の光学顕微鏡や電子顕微鏡での観察により測定することができる。本発明において、現像進行性と乾燥速度を上げることを両立するために、膨潤膜厚が８μｍ〜１９μｍであることが好ましく、更に９μｍ〜１８μｍであることが好ましい。膨潤膜厚の測定としては、３５℃の水溶液中に乾燥した感光材料を浸し、膨潤して十分平衡に達した状態で打点方法にて測定することができる。本発明における塗布銀量は、０．２ｇ／ｍ^２〜０．５ｇ／ｍ^２であることが好ましく、０．２ｇ／ｍ^２〜０．４５ｇ／ｍ^２であることが更に好ましく、０．２ｇ／ｍ^２〜０．４０ｇ／ｍ^２であることが最も好ましい。
【００９７】
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号公報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構わないが、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／ｍ²、好ましくは１×１０^-4〜１×１０^-1ｇ／ｍ²、更に好ましくは１×１０^-3〜１×１０^-2ｇ／ｍ²である。
【００９８】
本発明の感光材料は、画像情報に応じて光を照射される露光工程と、前記光照射された感光材料を現像する現像工程とにより、画像を形成することができる。本発明の感光材料は、通常のネガプリンターを用いたプリントシステムに使用される以外に、陰極線（ＣＲＴ）を用いた走査露光方式にも適している。陰極線管露光装置は、レーザーを用いた装置に比べて、簡便でかつコンパクトであり、低コストになる。また、光軸や色の調整も容易である。画像露光に用いる陰極線管には、必要に応じてスペクトル領域に発光を示す各種発光体が用いられる。例えば赤色発光体、緑色発光体、青色発光体のいずれか１種、あるいは２種以上が混合されて用いられる。スペクトル領域は、上記の赤、緑、青に限定されず、黄色、橙色、紫色或いは赤外領域に発光する蛍光体も用いられる。特に、これらの発光体を混合して白色に発光する陰極線管がしばしば用いられる。
【００９９】
感光材料が異なる分光感度分布を有する複数の感光性層を持ち、陰極性管も複数のスペクトル領域の発光を示す蛍光体を有する場合には、複数の色を一度に露光、即ち陰極線管に複数の色の画像信号を入力して管面から発光させてもよい。各色ごとの画像信号を順次入力して各色の発光を順次行わせ、その色以外の色をカットするフィルムを通して露光する方法（面順次露光）を採ってもよく、一般には、面順次露光の方が、高解像度の陰極線管を用いることができるため、高画質化のためには好ましい。
【０１００】
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。
【０１０１】
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。このような走査露光における露光時間は、画素密度を４００ｄｐｉとした場合の画素サイズを露光する時間として定義すると、好ましい露光時間としては１０^-4秒以下、更に好ましくは１０^-6秒以下である。
【０１０２】
本発明をハロゲン化銀カラー写真感光材料に適用する場合、発光波長４２０ｎｍ〜４６０ｎｍの青色レーザーのコヒーレント光により像様露光することが好ましい。青色レーザーの中でも、青色半導体レーザーを用いることが特に好ましい。
レーザー光源として具体的には、波長４３０〜４５０ｎｍの青色半導体レーザー（２００１年３月 第４８回応用物理学関係連合講演会で日亜化学発表）、半導体レーザー（発振波長 約９４０ｎｍ）を導波路状の反転ドメイン構造を有するＬｉＮｂＯ₃のＳＨＧ結晶により波長変換して取り出した約４７０ｎｍの青色レーザー、半導体レーザー（発振波長 約１０６０ｎｍ）を導波路状の反転ドメイン構造を有するＬｉＮｂＯ₃のＳＨＧ結晶により波長変換して取り出した約５３０ｎｍの緑色レーザー、波長約６８５ｎｍの赤色半導体レーザー（日立タイプＮｏ．ＨＬ６７３８ＭＧ）、波長約６５０ｎｍの赤色半導体レーザー（日立タイプＮｏ．ＨＬ６５０１ＭＧ）などが好ましく用いられる。
【０１０３】
本発明のハロゲン化銀写真感光材料は、以下の公知資料に記載の露光、現像システムと組み合わせることで好ましく用いることができる。前記現像システムとしては、特開平１０−３３３２５３号公報に記載の自動プリント並びに現像システム、特開２０００−１０２０６号公報に記載の感光材料搬送装置、特開平１１−２１５３１２号公報に記載の画像読取装置を含む記録システム、特開平１１−８８６１９号公報並びに特開平１０−２０２９５０号公報に記載のカラー画像記録方式からなる露光システム、特開平１０−２１０２０６号公報に記載の遠隔診断方式を含むデジタルフォトプリントシステム、及び特願平１０−１５９１８７号公報に記載の画像記録装置を含むフォトプリントシステムが挙げられる。
【０１０４】
本発明に適用できる好ましい走査露光方式については、前記の表に掲示した公報に詳しく記載されている。
【０１０５】
本発明の感光材料をプリンター露光する際、米国特許第４，８８０，７２６号明細書に記載のバンドストップフィルターを用いることが好ましい。これによって光混色が取り除かれ、色再現性が著しく向上する。
本発明においては、欧州特許ＥＰ０７８９２７０Ａ１明細書や同ＥＰ０７８９４８０Ａ１号明細書に記載のように、画像情報を付与する前に、予め、黄色のマイクロドットパターンを前露光し、複写規制を施しても構わない。
【０１０６】
本発明の感光材料の処理には、特開平２−２０７２５０号公報の第２６頁右下欄１行目〜３４頁右上欄９行目、及び特開平４−９７３５５号公報の第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公報に記載の化合物が好ましく用いられる。
【０１０７】
本発明は迅速処理適性を有する感光材料として適用される。発色現像時間は２８秒以下、好ましくは２５秒以下６秒以上、より好ましくは２０秒以下６秒以上である。同様に、漂白定着時間は好ましくは３０秒以下、更に好ましくは２５秒以下６秒以上、より好ましくは２０秒以下６秒以上である。また、水洗又は安定化時間は、好ましくは６０秒以下、更に好ましくは４０秒以下６秒以上である。なお、発色現像時間とは、感光材料が発色現像液中に入ってから次の処理工程の漂白定着液に入るまでの時間をいう。例えば、自動現像機などで処理される場合には、感光材料が発色現像液中に浸漬されている時間（いわゆる液中時間）と、感光材料が発色現像液を離れ次の処理工程の漂白定着浴に向けて空気中を搬送されている時間（いわゆる空中時間）との両者の合計を発色現像時間という。同様に、漂白定着時間とは、感光材料が漂白定着液中に入ってから次の水洗又は安定浴に入るまでの時間をいう。また、水洗又は安定化時間とは、感光材料が水洗又は安定化液中に入ってから乾燥工程に向けて液中にある時間（いわゆる液中時間）をいう。
【０１０８】
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号公報、同９−１５２６８６号公報、同９−１５２６９３号公報、同９−２１１８１４号公報、同９−１６０１９３号公報に記載されたヒドラジン型化合物が好ましい。
【０１０９】
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号公報、同９−１５２６９５号公報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。
【０１１０】
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号公報に記載されたものを用いることができる。
【０１１１】
【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、本発明はこれらに限定されるものではない。
【０１１２】
実施例１
（乳剤Ｂ−Ｈの調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．５５μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が８０％の時点から９０％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり３モル％）およびＫ₄［Ｒｕ(ＣＮ)₆］を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．３モル％）を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムと増感色素Ａおよび増感色素Ｂを添加し、増感剤として硫化金コロイド分散物を用い最適になるように熟成した。更に１−フェニル−５−メルカプトテトラゾールおよび１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールを添加した。このようにして得られた乳剤を、乳剤Ｂ−Ｈとした。
【０１１３】
【化１】

【０１１４】
（乳剤Ｂ−Ｌの調製）
乳剤Ｂ−Ｈとは、硝酸銀と塩化ナトリウムの添加速度のみを変えて、球相当径０．４５μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。得られた乳剤を、乳剤Ｂ−Ｌとした。
【０１１５】
（乳剤Ｇ−１の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．４０μｍ、変動係数１０％の立方体高塩化銀乳剤（塩化銀含有率９５．８モル％）を調製した。但し、硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ(ＣＮ)₆］を添加した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり４モル％）を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．２モル％）を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムを添加し、増感剤として硫化金コロイド分散物を用い最適になるように熟成した。更に増感色素Ｃ、１−フェニル−５−メルカプトテトラゾール、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールおよび臭化カリウムを添加した。このようにして得られた乳剤を、乳剤Ｇ−１とした。
【０１１６】
【化２】

【０１１７】
（乳剤Ｇ−２の調製）
乳剤Ｇ−１とは、硝酸銀の添加が９２％の時点から９７％の時点にかけて、Ｋ_２［Ｉｒ（５−メチルチアゾール）Ｃｌ_５］を出来上がりのハロゲン化銀１モルあたりＩｒ量が５×１０^−７モルになる量を添加したことのみ異なる乳剤（塩化銀含有率９５．８モル％）を調製し、これを乳剤Ｇ−２とした。
【０１１８】
（乳剤Ｇ−３の調製）
乳剤Ｇ−１とは、硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ₃［ＲｈＢｒ₆］を出来上がりのハロゲン化銀１モルあたりＲｈ量が１×１０^−８モルになる量を添加したことのみ異なる乳剤（塩化銀含有率９５．８モル％）を調製し、乳剤Ｇ−３とした。
【０１１９】
（乳剤Ｇ−４の調製）
乳剤Ｇ−１とは、硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ₃［ＲｈＢｒ₆］を出来上がりのハロゲン化銀１モルあたりＲｈ量が３×１０^−８モルになる量添加したことのみ異なる乳剤（塩化銀含有率９５．８モル％）を調製し、乳剤Ｇ−４とした。
【０１２０】
（乳剤Ｇ−５の調製）
乳剤Ｇ−１とは、硝酸銀と塩化ナトリウムの添加速度のみを変えて、球相当径０．３５μｍ、変動係数１０％の立方体高塩化銀乳剤（塩化銀含有率９５．８モル％）を調製した。得られた乳剤を、乳剤Ｇ−５とした。
【０１２１】
（乳剤Ｇ−６の調製）
乳剤Ｇ−５とは、硝酸銀の添加が９２％の時点から９７％の時点にかけて、Ｋ_２［Ｉｒ（５−メチルチアゾール）Ｃｌ_５］を出来上がりのハロゲン化銀１モルあたりＩｒ量が１×１０^−６モルになる量を添加したことのみ異なる乳剤（塩化銀含有率９５．８モル％）を調製し、これを乳剤Ｇ−６とした。
【０１２２】
（乳剤Ｇ−７の調製）
乳剤Ｇ−５とは、硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ₃［ＲｈＢｒ₆］を出来上がりのハロゲン化銀１モルあたりＲｈ量が２．７×１０^−８モルになる量添加したことのみ異なる乳剤（塩化銀含有率９５．８モル％）を調製し、乳剤Ｇ−７とした。
【０１２３】
（乳剤Ｇ−８の調製）
乳剤Ｇ−１とは、硝酸銀と塩化ナトリウムの添加速度のみを変えて、球相当径０．２９μｍ、変動係数１０％の立方体高塩化銀乳剤（塩化銀含有率９５．８モル％）を調製した。得られた乳剤を、乳剤Ｇ−８とした。
【０１２４】
（乳剤Ｇ−９の調製）
乳剤Ｇ−８とは、硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ₃［ＲｈＢｒ₆］を出来上がりのハロゲン化銀１モルあたりＲｈ量が８×１０^−９モルになる量添加したことのみ異なる乳剤（塩化銀含有率９５．８モル％）を調製し、乳剤Ｇ−９とした。
【０１２５】
（乳剤Ｒ−Ｈの調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．３５μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ(ＣＮ)₆］を添加した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり４．３モル％）を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．１５モル％）を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムを添加し、硫黄増感剤としてチオ硫酸ナトリウム５水和物と金増感剤としてビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオラート）オーレート（Ｉ）テトラフルオロボレートを用い最適になるように熟成した。更に増感色素Ｈ、１−フェニル−５−メルカプトテトラゾール、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾール、化合物Ｉおよび臭化カリウムを添加した。このようにして得られた乳剤を、乳剤Ｒ−Ｈとした。
【０１２６】
【化３】

【０１２７】
【化４】

【０１２８】
（乳剤Ｒ−Ｌの調製）
乳剤Ｒ−Ｈとは、硝酸銀と塩化ナトリウムの添加速度のみを変えて、球相当径０．２８μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。得られた乳剤を、乳剤Ｒ−Ｌとした。
【０１２９】
乳剤Ｇ−１からＧ−９の感度を調べるために、以下の試料を作製した。
【０１３０】
紙の両面をポリエチレン樹脂で被覆してなる支持体の表面に、コロナ放電処理を施した後、ドデシルベンゼンスルホン酸ナトリウムを含むゼラチン下塗層を設け、さらに第一層〜第七層の写真構成層を順次塗設して、以下に示す層構成のハロゲン化銀カラー写真感光材料の試料を作製した。各写真構成層用の塗布液は、以下のようにして調製した。
【０１３１】
第一層塗布液調製
イエローカプラー（ＥｘＹ）５７ｇ、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２２０ｇ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、前記乳化分散物Ａと乳剤Ｂ−Ｈ及びＢ−Ｌ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。
【０１３２】
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／ｍ²、６０．０ｍｇ／ｍ²、５．０ｍｇ／ｍ²及び１０．０ｍｇ／ｍ²となるように添加した。
【０１３３】
【化５】

【０１３４】
【化６】

【０１３５】
また、緑感性乳剤層および赤感性乳剤層に対し、１−フェニル−５−メルカプトテトラゾールを、それぞれハロゲン化銀１モル当り１．０×１０^-3モルおよび５．９×１０^-4モル添加した。さらに、第二層、第四層および第六層にも１−フェニル−５−メルカプトテトラゾールを、それぞれ０．２ｍｇ／ｍ²、０．２ｍｇ／ｍ²および０．６ｍｇ／ｍ²となるように添加した。
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／ｍ²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／ｍ²、６ｍｇ／ｍ²、１８ｍｇ／ｍ²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。
【０１３６】
【化７】

【０１３７】
（層構成）
以下に、各層の構成を示す。数字は塗布量（ｇ／ｍ²）を表す。ハロゲン化銀乳剤は、銀換算塗布量を表す。
支持体
ポリエチレン樹脂ラミネート紙
［第一層側のポリエチレン樹脂に白色顔料（ＴｉＯ₂；含有率１６質量％、ＺｎＯ；含有率４質量％）と蛍光増白剤（４，４’−ビス（５−メチルベンゾオキサゾリル）スチルベン。含有率０．０３質量％）、青味染料（群青）を含む］
第一層（青感性乳剤層）
乳剤Ｂ−Ｈ ０．０９
乳剤Ｂ−Ｌ ０．１０
ゼラチン １．００
イエローカプラー（ＥｘＹ−１） ０．４６
色像安定剤（Ｃｐｄ−１） ０．０６
色像安定剤（Ｃｐｄ−２） ０．０３
色像安定剤（Ｃｐｄ−３） ０．０６
色像安定剤（Ｃｐｄ−８） ０．０２
溶媒（Ｓｏｌｖ−１） ０．１７
【０１３８】
第二層（混色防止層）
ゼラチン ０．５０
混色防止剤（Ｃｐｄ−４） ０．０５
色像安定剤（Ｃｐｄ−５） ０．０１
色像安定剤（Ｃｐｄ−６） ０．０６
色像安定剤（Ｃｐｄ−７） ０．０１
溶媒（Ｓｏｌｖ−１） ０．０３
溶媒（Ｓｏｌｖ−２） ０．１１
【０１３９】
第三層（緑感性乳剤層）
乳剤Ｇ−１ ０．１２
ゼラチン １．３６
マゼンタカプラー（ＥｘＭ） ０．１５
紫外線吸収剤（ＵＶ−Ａ） ０．１４
色像安定剤（Ｃｐｄ−２） ０．０２
色像安定剤（Ｃｐｄ−４） ０．００２
色像安定剤（Ｃｐｄ−６） ０．０９
色像安定剤（Ｃｐｄ−８） ０．０２
色像安定剤（Ｃｐｄ−９） ０．０３
色像安定剤（Ｃｐｄ−１０） ０．０１
色像安定剤（Ｃｐｄ−１１） ０．０００１
溶媒（Ｓｏｌｖ−３） ０．１１
溶媒（Ｓｏｌｖ−４） ０．２２
溶媒（Ｓｏｌｖ−５） ０．２０
【０１４０】
第四層（混色防止層）
ゼラチン ０．３６
混色防止剤（Ｃｐｄ−４） ０．０３
色像安定剤（Ｃｐｄ−５） ０．００６
色像安定剤（Ｃｐｄ−６） ０．０５
色像安定剤（Ｃｐｄ−７） ０．００４
溶媒（Ｓｏｌｖ−１） ０．０２
溶媒（Ｓｏｌｖ−２） ０．０８
【０１４１】
第五層（赤感性乳剤層）
乳剤Ｒ−Ｈ ０．０５
乳剤Ｒ−Ｌ ０．０５
ゼラチン １．１１
シアンカプラー（ＥｘＣ−２） ０．１３
シアンカプラー（ＥｘＣ−３） ０．０３
色像安定剤（Ｃｐｄ−１） ０．０５
色像安定剤（Ｃｐｄ−６） ０．０６
色像安定剤（Ｃｐｄ−７） ０．０２
色像安定剤（Ｃｐｄ−９） ０．０４
色像安定剤（Ｃｐｄ−１０） ０．０１
色像安定剤（Ｃｐｄ−１４） ０．０１
色像安定剤（Ｃｐｄ−１５） ０．１２
色像安定剤（Ｃｐｄ−１６） ０．０３
色像安定剤（Ｃｐｄ−１７） ０．０９
色像安定剤（Ｃｐｄ−１８） ０．０７
溶媒（Ｓｏｌｖ−５） ０．１５
溶媒（Ｓｏｌｖ−８） ０．０５
【０１４２】
第六層（紫外線吸収層）
ゼラチン ０．４６
紫外線吸収剤（ＵＶ−Ｂ） ０．４５
化合物（Ｓ１−４） ０．００１５
溶媒（Ｓｏｌｖ−７） ０．２５
第七層（保護層）
ゼラチン １．００
ポリビニルアルコールのアクリル変性共重合体
（変性度１７％） ０．０４
流動パラフィン ０．０２
界面活性剤（Ｃｐｄ−１３） ０．０１
【０１４３】
【化８】

【０１４４】
【化９】

【０１４５】
【化１０】

【０１４６】
【化１１】

【０１４７】
【化１２】

【０１４８】
【化１３】

【０１４９】
【化１４】

【０１５０】
【化１５】

【０１５１】
【化１６】

【０１５２】
【化１７】

【０１５３】
以上のようにして得られた試料を、試料１０１とした。乳剤Ｇ−１からＧ−９の感度を調べるために、試料１０１とは緑感性乳剤層の乳剤をそれぞれ表２のように替えた試料も同様に作製し試料１０２から１０９とした。
【０１５４】
【表２】

【０１５５】
各塗布試料を１０℃３０％ＲＨの雰囲気下に置き、高照度露光用感光計（山下電装（株）製ＨＩＥ型）を用いて、緑色フィルターを通してセンシトメトリー用の１０^−４秒高照度階調露光を与えた。露光した試料は、露光の６秒後に以下に示す発色現像処理を行なった。
【０１５６】
以下に処理工程を示す。
［処理］
下記処理工程にて使用した発色現像補充液の容量が発色現像タンク容量の０．５倍となるまで連続処理を行った。
【０１５７】
処理工程 温度 時間 補充量^*
発色現像 ４５．０℃ １６秒 ４５ｍＬ
漂白定着 ４０．０℃ １６秒 ３５ｍＬ
リンス（１） ４０．０℃ ８秒 −
リンス（２） ４０．０℃ ８秒 −
リンス（３）＊＊４０．０℃ ８秒 −
リンス（４）＊＊３８．０℃ ８秒 １２１ｍＬ
乾燥 ８０．０℃ １６秒
（注）＊感光材料１ｍ²あたりの補充量
＊＊富士写真フイルム（株）製リンスクリーニングシステムＲＣ５０Ｄ（商品名）をリンス（３）に装着し、リンス（３）からリンス液を取り出してポンプにより逆浸透モジュール（ＲＣ５０Ｄ）へ送る。同槽で送られた透過水はリンス（４）に供給し、濃縮液はリンス（３）に戻す。逆浸透モジュールへの透過水量は５０〜３００ｍＬ／分を維持するようにポンプ圧を調整し、１日１０時間温調循環させた。リンスは（１）から（４）への４タンク向流方式とした。
【０１５８】
各処理液の組成は以下の通りである。
[発色現像液] [タンク液] ［補充液］
水 ８００ｍＬ ６００ｍL
蛍光増白剤（ＦＬ−１） ５．０ｇ ８．５ｇ
トリイソプロパノールアミン ８．８ｇ ８．８ｇ
ｐ−トルエンスルホン酸ナトリウム ２０．０ｇ ２０．０ｇ
エチレンジアミン４酢酸 ４．０ｇ ４．０ｇ
亜硫酸ナトリウム ０．１０ｇ ０．５０ｇ
塩化カリウム １０．０ｇ −
４，５−ジヒドロキシベンゼン−
１，３−ジスルホン酸ナトリウム ０．５０ｇ ０．５０ｇ
ジナトリウム−Ｎ，Ｎ−ビス（スルホナート
エチル）ヒドロキシルアミン ８．５ｇ １４．５ｇ
４−アミノ−３−メチル−Ｎ−エチル−Ｎ−
（β−メタンスルホンアミドエチル）アニリン
・３／２硫酸塩・モノハイドレード １０．０ｇ ２２．０ｇ
炭酸カリウム ２６．３ｇ ２６．３ｇ
水を加えて全量 １０００ｍＬ １０００ｍＬ
ｐＨ（２５℃、硫酸とＫＯＨで調整）１０．３５ １２．６
【０１５９】

【０１６０】
[リンス液] [タンク液] [補充液]
塩素化イソシアヌール酸ナトリウム ０．０２ｇ ０．０２ｇ
脱イオン水（電導度５μＳ／ｃｍ以下）１０００ｍＬ １０００ｍＬ
ｐＨ（２５℃） ６．５ ６．５
【０１６１】
【化１８】

【０１６２】
処理後の各試料のマゼンタ発色濃度を測定し、１０^−４秒高照度露光の特性曲線を得た。各試料の発色濃度０．７を与えるに要する露光量Ｅの対数から、各乳剤の感度を読み取った。感度は、乳剤Ｇ−１の感度との相対値をｌｏｇＥで表した。値が負の程、感度が低いことを表す。結果を表２に示した。それぞれのサイズで一般式（Ｉ）あるいは（II）に該当する金属錯体を含有しない乳剤Ｇ−１、Ｇ−５およびＧ−８の感度と、金属錯体を含有する乳剤の感度差が、金属錯体による減感度である。
【０１６３】
更に、乳剤Ｇ−１からＧ−８の中から２種類を混合することによる写真性能を調べるために、試料１０１とは緑感性乳剤層の乳剤をそれぞれ表３のように２種類の混合に替えた試料を作製し試料１１０から１２１とした。２種類の乳剤の銀換算塗布量は、それぞれ０．０６（ｇ／ｍ^２）とした。
【０１６４】
これらの試料の写真特性を調べるために以下のような実験を行った。
各塗布試料を２０℃３０％ＲＨの雰囲気下に置き、高照度露光用感光計（山下電装（株）製ＨＩＥ型）を用いて、グレーのセンシトメトリー用の１０^−６秒高照度階調露光を与えた。露光した試料は、露光の６秒後あるいは６０秒後に上記の発色現像時間が１６秒の処理を行なった。同様に露光した試料について、露光してから６秒後あるいは６０秒後に、発色現像時間を２６秒に変更したことのみ異なる処理を行なった。更に、上記の発色現像液１Ｌ当たり漂白定着液を０．５ｍｌ混入した発色現像液を調製し、同様に露光した試料について、露光してから６秒後あるいは６０秒後に、この発色現像液で発色現像時間が１６秒の処理を行なった。
【０１６５】
処理後の各試料のマゼンタ発色反射濃度を測定し、１０^−６秒高照度露光の特性曲線を得た。
以下階調γは、発色濃度０．３を与えるに要する露光量から、ｌｏｇＥで０．５多い露光量における発色濃度Ｄを読み取り、（Ｄ−０．３）／０．５として算出した。各試料について、露光６秒後に１６秒間の通常の発色現像を行なった場合のγを算出した。レーザー走査露光によるデジタル露光の場合、この値は２．２±０．２の範囲が好ましく、算出した各試料のγと最適中心階調２．２との差を最適階調からのずれΔγ１とした。正の値は最適中心階調より硬調であることを表し、負の値は軟調であることを表す。絶対値が０．２以内であることが好ましい。
【０１６６】
各試料について、露光６秒後に１６秒間の通常の発色現像を行なった場合のγと、露光６秒後に２６秒間の通常の発色現像を行なった場合のγを読み取り、その差をΔγ２とした。正の値は現像時間の延長で硬調になることを表す。絶対値が小さいほど処理要因の変動によっても階調が安定で好ましいことを表す。また各試料について、露光６秒後に１６秒間の通常の発色現像を行なった場合のγと、露光６秒後に漂白定着液が混入した発色現像で１６秒間の発色現像を行なった場合のγを読み取りその差をΔγ３とした。正の値は漂白定着液の混入で硬調になることを表す。絶対値が小さいほど漂白定着液の混入によって階調が安定で好ましいことを表す。
得られた結果を表３に示した。
【０１６７】
【表３】

【０１６８】
表３より、本発明の乳剤を混合することでレーザー走査露光によるデジタル露光に適した階調が得られ、なおかつ処理要因の変動によってもその階調が安定に保たれることが分かる。但し、表には示さなかったが、いずれの試料も露光後６０秒後に発色現像を開始した場合には、階調変動は安定であった。
【０１９３】
【発明の効果】
本発明のハロゲン化銀写真感光材料は、レーザー走査露光によるデジタル露光に適し、超迅速処理を行なった場合にも常に安定した写真性能を得ることができ、特にカラープリントに好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide true light-sensitive material, and more particularly to a high-contrast silver halide photographic light-sensitive material suitable for rapid processing, and more particularly to a silver halide photographic light-sensitive material capable of obtaining stable performance when rapidly processed.
[0002]
[Prior art]
In recent years, there has been a remarkable spread of digitization in the field of color printing using color photographic paper. For example, the digital exposure method using laser scanning exposure is an analog that directly prints with a color printer from a processed color negative film. Compared to the exposure method, it shows a dramatic increase in the penetration rate. Such a digital exposure method is characterized in that high image quality can be obtained by performing image processing, and plays an extremely important role in improving the quality of color prints using color photographic paper. In addition, with the rapid spread of digital cameras, it is also an important factor that simple and high-quality color prints can be obtained from these electronic recording media, and it is thought that these will lead to further dramatic spread.
[0003]
On the other hand, as a color printing method, technologies such as an ink jet method, a sublimation type method, and color xerography have advanced, and are being recognized as a color printing method, such as improving the quality of photographs. Among these, the characteristics of the digital exposure method using color photographic paper are high image quality, high productivity, and high image robustness. These features can be further extended to make higher quality photographs easier. It is desired to provide it at a lower cost. In particular, if you receive a digital camera recording medium at a store, finish a high-quality print within a short time of about a few minutes and return it on the spot, that is, if you can provide a one-stop service for color printing, color printing using color photographic paper The advantage of printing is increasing. In addition, if the rapid processing of color photographic paper is improved, it is possible to use a printing device that is smaller and cheaper but has high productivity, and that one-stop services for color printing can be expected to become increasingly popular. In view of these points, it is particularly important to improve the rapid processability of color photographic paper.
[0004]
When performing digital exposure by laser scanning exposure on color photographic paper, the color photographic paper preferably has an appropriate gradation. If the gradation is too hard, color irregularities such as banding and shading are likely to occur, and a picture with a highlighted highlight is likely to appear. Conversely, if the gradation is too soft, it becomes difficult to cover the reproduction range from the toes to the high density within the dynamic range of the emission intensity of the laser light source. In order to enable one-stop service for color printing using color photographic paper, shortening the exposure time, shortening the so-called latent image time from exposure to processing start, shortening the time from processing to drying, etc. Therefore, it has been necessary to study from various viewpoints. Among these, the time required for exposure of one print is very short compared to the other, and in the case of a normal printer capability used at a store, there is almost no problem. The latent image time is designed to be as short as possible with a printer. In addition, the time from processing to drying has been shortened, and proposals have been made for rapid processing based on the processing solution composition, processing temperature, stirring conditions of the processing solution, ironing of the photosensitive material, devising the drying method, and the like. ing.
[0005]
For the above-mentioned purpose, we have examined color printing paper with a short latent image time of 9 seconds or less and color development in a short time of 28 seconds or less. However, if two types of emulsions with different sensitivity depending on the particle size are mixed in the same color development layer so that an appropriate gradation can be obtained by digital exposure by laser scanning exposure, the resulting print will vary in the composition of the color developer. According to the results, it was found that the color density variation of the shoulder portion of the characteristic curve is large, and stable performance cannot be obtained. Further, it has been found that such instability is remarkable when laser scanning exposure is performed. We have made various studies in order to solve this problem, and found that it can be solved by mixing at least two types of silver halide emulsions containing a specific metal complex in the silver halide emulsion layer.
[0006]
JP-A-10-307364 discloses a photographic element containing at least two types of emulsions, wherein the two types of grains are the same, and at least one of them is treated with a compound that reduces the sensitivity. Specific disulfide compounds are listed as compounds that lower the sensitivity. As a result, emulsions with different sensitivities can be easily prepared, and the amount of sensitizing dyes and chemical sensitizing reagents used can be reduced compared with the case of making emulsions with low sensitivity by reducing the grain size, thereby reducing costs. Disclosed.
[0007]
Japanese Patent Application Laid-Open Nos. 3-192346 and 3-241342 disclose that emulsions having different iridium contents by 40% or more are mixed and used. Thus, it is disclosed that an image in which the sensitivity gradation is not easily changed by a change in exposure illuminance can be formed.
[0008]
As a silver halide emulsion used for color photographic paper, a silver halide emulsion having a high silver chloride content is used because of a demand for rapid processability. It is disclosed that a silver halide emulsion having a high silver chloride content contains various metal complexes. It is known to dope Ir complexes in order to improve the high illuminance failure of silver chloride emulsions and to obtain a high gradation even at high illuminance. For example, Japanese Patent Publication No. 7-34103 discloses that a problem of latent image sensitization can be solved by providing a localized phase having a high silver bromide content and doping it with an Ir complex. US Pat. No. 4,933,272 discloses that low illuminance failure can be reduced by containing a metal complex containing NO or NS as a ligand. US Pat. Nos. 5,360,712, 5,457,021, and 5,462,849 disclose a reciprocity law by including a metal complex containing a specific organic ligand as a ligand. It is disclosed that failure can be reduced. U.S. Patent Nos. 5,372,926, 5,255,630, 5,255,451, 5,597,686, 5,480,771, No. 474,888, No. 5,500,335, No. 5,783,373 and No. 5,783,378 are highly salified with combinations of Ir complexes and metal complexes containing NO as a ligand. It is disclosed that performance such as reciprocity characteristics of silver emulsion can be improved. JP-A Nos. 2000-250156, 2001-92066, and 2002-31866 disclose emulsion techniques that have excellent latent image stability after exposure using a combination of an Ir complex and an Rh complex.
[0009]
JP-A-58-95736, 58-108533, 60-222844, 60-222845, 62-253143, 62-253144, 62-253166, 62-254139 63-46440, 63-46441, 63-89840, U.S. Pat.Nos. 4,820,624, 4,865,962, 5,399,475, 5 , 284, 743 and the like disclose that high sensitivity can be obtained by locally incorporating a phase having a high silver bromide content in various forms in an emulsion having a high silver chloride content.
[0010]
In US Pat. Nos. 5,726,005 and 5,736,310, emulsions containing I having a maximum concentration on the subsurface of high silver chloride emulsions provide emulsions with high sensitivity and low illuminance failure. It is disclosed that it can be obtained. In the examples of European Patent EP 0,928,988A, a specific compound is contained in a particle that formed an I band at 93% of the particle formation, thereby causing reciprocity failure, temperature dependence and pressure characteristics during exposure. It is disclosed that an excellent emulsion can be obtained.
[0011]
However, in these known techniques, there is a latent image time of 9 seconds or less and color development in a short time of 28 seconds or less while having an appropriate gradation by digital exposure by laser scanning exposure. However, it is not disclosed that the instability of photographic characteristics is improved by including at least two emulsions containing a specific metal complex.
[0012]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to overcome the above-mentioned problems, and is suitable for digital exposure by laser scanning exposure, and can always provide stable photographic performance even when rapid processing is performed. The object is to provide a silver halide color photographic light-sensitive material suitable for materials, particularly color printing.
[0013]
[Means for Solving the Problems]
  Means for solving the above problems are as follows.
(1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least two types of silver chloride contents having different sensitivities are 90 mol% or more in the silver halide emulsion layer. A silver halide emulsion, and at least one of the silver halide emulsionsOneIs a silver halide emulsion containing at least one selected from metal complexes represented by the following general formula (I)(1) The content per mole of at least one silver halide selected from the metal complexes represented by the general formula (I) or the average content per silver halide grain is high sensitivity. There are more emulsions on the low-sensitivity side than emulsions on the side, or (2) the desensitization due to at least one selected from the metal complex represented by the general formula (I) is higher than the emulsion on the high-sensitivity side The emulsion on the low sensitivity side is largerA silver halide photographic light-sensitive material characterized by the above.
  Formula (I)
    [IrX^I _nL^I _(6-n)]^m
  Where X^IRepresents a halogen ion or pseudo-halogen ion (except cyanate ion), and L^IIs X^IRepresents any ligand different from n, n represents 3, 4 or 5, m represents the charge of the metal complex and is 5-, 4-, 3-, 2-, 1-, 0 or 1+ .
(2) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer has at least two types of silver chloride contents having different sensitivities of 90 mol% or more. A silver halide emulsion, and at least one of the silver halide emulsionsOneIs a silver halide emulsion containing at least one selected from metal complexes represented by the following general formula (II)(1) The content per mole of at least one silver halide selected from the metal complex represented by the general formula (II) or the average content per silver halide grain is high sensitivity. There are more emulsions on the low-sensitivity side than emulsions on the side, or (2) the desensitization due to at least one selected from the metal complex represented by the general formula (II) is higher than that on the emulsion on the high-sensitivity side The emulsion on the low sensitivity side is largerA silver halide photographic light-sensitive material characterized by the above.
  Formula (II)
    [MX^II _nL^II _(6-n)]^m
  In the formula, M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, and X^IIRepresents a halogen ion, L^IIIs X^IIRepresents an arbitrary ligand different from. n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and is 4-, 3-, 2-, 1-, 0 or 1+.
[0014]
(3) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least two types of silver chloride contents having different sensitivities are 90 mol% or more in the silver halide emulsion layer. A silver halide emulsion, and at least one of the silver halide emulsionsOneIs a silver halide emulsion containing at least one selected from metal complexes represented by the following general formula (I) and at least one selected from metal complexes represented by the following general formula (II):(1) Content per mole of at least one silver halide selected from the metal complexes represented by the general formula (I) or (II) or average content per silver halide grain However, there are more emulsions on the low sensitivity side than emulsions on the high sensitivity side, or (2) the desensitization due to at least one selected from the metal complexes represented by the general formula (I) or (II) The emulsion on the low sensitivity side is larger than the emulsion on the high sensitivity sideA silver halide photographic light-sensitive material characterized by the above.
  Formula (I)
    [IrX^I _nL^I _(6-n)]^m
  Where X^IRepresents a halogen ion or pseudo-halogen ion (except cyanate ion), and L^IIs X^IRepresents any ligand different from n, n represents 3, 4 or 5, m represents the charge of the metal complex and is 5-, 4-, 3-, 2-, 1-, 0 or 1+ .
  Formula (II)
    [MX^II _nL^II _(6-n)]^m
  In the formula, M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, and X^IIRepresents a halogen ion, L^IIIs X^IIRepresents an arbitrary ligand different from. n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and is 4-, 3-, 2-, 1-, 0 or 1+.
[0015]
(4) In the two types of silver halide emulsions having different sensitivities, the content per mole of at least one silver halide selected from the metal complexes represented by the general formula (I) is high sensitivity side. 4. The silver halide photographic light-sensitive material as described in any one of (1) or (3), wherein the emulsion on the lower sensitivity side is more than the emulsion in (1).
(5) In the two types of silver halide emulsions having different sensitivities, the average content per grain of at least one silver halide grain selected from the metal complexes represented by the general formula (I) is high. The silver halide photographic light-sensitive material according to any one of (1), (3) and (4), wherein there are more emulsions on the low sensitivity side than emulsions on the sensitivity side.
(6) In the two types of silver halide emulsions having different sensitivities, the desensitization due to at least one selected from the metal complexes represented by the general formula (I) is less sensitive than the sensitive emulsion. The silver halide photographic light-sensitive material as described in any one of (1), (3), (4) or (5), wherein the emulsion (1) is larger.
[0016]
(7) In the two types of silver halide emulsions having different sensitivities, the content per mole of at least one silver halide selected from the metal complexes represented by the general formula (II) is high sensitivity side. 4. The silver halide photographic light-sensitive material as described in any one of (2) or (3), wherein the emulsion on the lower sensitivity side is more than the emulsion of (2).
(8) In the two types of silver halide emulsions having different sensitivities, the average content per grain of at least one silver halide grain selected from the metal complexes represented by the general formula (II) is high. The silver halide photographic light-sensitive material as described in any one of (2), (3) and (7), wherein there are more emulsions on the low sensitivity side than emulsions on the sensitivity side.
(9) In the above-described two types of silver halide emulsions having different sensitivities, the desensitization due to at least one selected from the metal complex represented by the general formula (II) is less sensitive than the sensitive emulsion. The silver halide photographic light-sensitive material as described in any one of (2), (3), (7) or (8), wherein the emulsion (2) is larger.
(10) The two types of silver halide emulsions having different sensitivities are silver halide emulsions containing silver halide grains having a sphere equivalent diameter of 0.6 μm or less. (1) to (9 ). The silver halide photographic light-sensitive material according to any one of items 1).
[0017]
(11) The metal complex represented by the general formula (I) is a metal complex represented by the following general formula (IA): (1), (3), (4), (5 ) Or (6) The silver halide photographic light-sensitive material according to any one of (6).
Formula (IA)
[IrX^IA _nL^IA _(6-n)]^m
Where X^IARepresents a halogen ion or pseudo-halogen ion (except cyanate ion), and L^IAIs X^IARepresents any inorganic ligand different from. n represents 3, 4 or 5, m represents the charge of the metal complex, and is 5-, 4-, 3-, 2-, 1-, 0 or 1+.
(12) The metal complex represented by the general formula (I) is a metal complex represented by the following general formula (IB): (1), (3), (4), (5 ) Or (6) The silver halide photographic light-sensitive material according to any one of (6).
Formula (IB)
[IrX^IB _nL^IB _(6-n)]^m
Where X^IBRepresents a halogen ion or pseudo-halogen ion (except cyanate ion), and L^IBRepresents a ligand in which a chain or cyclic hydrocarbon is used as a parent structure, or a carbon or hydrogen atom in a part of the parent structure is replaced with another atom or atomic group. n represents 3, 4 or 5, m represents the charge of the metal complex, and is 5-, 4-, 3-, 2-, 1-, 0 or 1+.
[0018]
(13) The metal complex represented by the general formula (I) is a metal complex represented by the following general formula (IC): (1), (3), (4), (5 ) Or (6) The silver halide photographic light-sensitive material according to any one of (6).
General formula (IC)
[IrX^IC _nL^IC _(6-n)]^m
Where X^ICRepresents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L^ICIs a 5-membered ring ligand and represents a ligand containing at least one nitrogen atom and at least one sulfur atom in the ring skeleton, and may have an arbitrary substituent on a carbon atom in the ring skeleton . n represents 3, 4 or 5, m represents the charge of the metal complex, and is 5-, 4-, 3-, 2-, 1-, 0 or 1+.
(14) The metal complex represented by the general formula (I) is a metal complex represented by the following general formula (ID): (1), (3), (4), (5 ) Or (6) The silver halide photographic light-sensitive material according to any one of (6).
General formula (ID)
[IrX^ID _nL^ID _(6-n)]^m
Where X^IDRepresents a halogen ion or a pseudohalogen ion (excluding a cyanate ion). L^IDIs a 5-membered ring ligand and represents a ligand containing at least two nitrogen atoms and at least one sulfur atom in the ring skeleton, and may have an arbitrary substituent on a carbon atom in the ring skeleton . n represents 3, 4 or 5, m represents the charge of the metal complex, and is 5-, 4-, 3-, 2-, 1-, 0 or 1+.
[0019]
(15) The metal complex represented by the general formula (II) is a metal complex represented by the following general formula (IIA): (2), (3), (7), (8 ) Or (9). The silver halide photographic light-sensitive material according to any one of (9).
General formula (IIA)
[M^{II A}X^{II A} _nL^{II A} _(6-n)]^m
Where M^{II A}Represents Re, Ru, Os or Rh, and X^{II A}Represents a halogen ion. L^{II A}Is M^{II A}Is Re, Ru or Os, it represents NO or NS;^{II A}H is Rh₂O, OH or O is represented. n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and is 4-, 3-, 2-, 1-, 0 or 1+.
(16) The total silver coating amount of the silver halide photographic light-sensitive material is 0.2 g / m.²0.5 g / m²The silver halide photographic light-sensitive material as described in any one of (1) to (15), which is:
(17) The total coated gelatin amount of the silver halide photographic light-sensitive material is 3 g / m.²6 g / m or more²The silver halide photographic light-sensitive material as described in any one of (1) to (16), which is:
(18) The above silver halide photographic light-sensitive material comprises a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, and a cyan dye-forming coupler-containing silver halide emulsion layer on a reflective support. The silver halide photographic light-sensitive material as described in any one of (1) to (17), which is a silver halide color photographic light-sensitive material having at least one layer each.
[0020]
(19) Rapid processing halogen which starts color development within 9 seconds after imagewise exposure of the silver halide photographic material and forms the image by performing the color development within 28 seconds. The silver halide photographic light-sensitive material as described in any one of (1) to (18), which is a silver halide color photographic light-sensitive material.
(20) The silver halide photographic light-sensitive material as described in (19), wherein the silver halide emulsion of the yellow dye-forming coupler-containing silver halide emulsion layer is a silver halide emulsion having a sphere equivalent diameter of 0.6 μm or less. .
(21) A silver bromide-containing phase in which at least one of the silver halide emulsions in the silver halide emulsion layer contains 0.1 to 7 mol% of silver bromide and the silver bromide concentration is higher than the surroundings. The silver halide photographic light-sensitive material as described in any one of (1) to (20), which is formed.
(22) A silver iodide-containing phase in which at least one of the silver halide emulsions in the silver halide emulsion layer contains 0.02 to 1 mol% of silver iodide and the silver iodide concentration is higher than the surroundings. The silver halide photographic light-sensitive material as described in any one of (1) to (21), which is formed.
[0021]
(23) The silver halide photographic material according to any one of items (1) to (22), wherein the silver halide photographic material is imagewise exposed by laser scanning exposure. Photosensitive material.
(24) The silver halide photographic light-sensitive material according to any one of items (1) to (23), which is imagewise exposed by scanning exposure using a blue semiconductor laser having an emission wavelength of 420 nm to 460 nm. A silver halide photographic light-sensitive material for digital exposure.
(25) An image forming method, wherein the silver halide photographic light-sensitive material according to any one of (1) to (22) is imagewise exposed by laser scanning exposure.
(26) The silver halide photographic light-sensitive material described in any one of items (1) to (23) is imagewise exposed by scanning exposure using a blue semiconductor laser having an emission wavelength of 420 nm to 460 nm. Image forming method.
[0022]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0023]
The metal complex represented by the general formula (I) used in the present invention will be described. In general formula (I), X^IRepresents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L^IIs X^IRepresents an arbitrary ligand different from. n represents 3, 4 or 5, m represents the charge of the metal complex and is 5-, 4-, 3-, 2-, 1-, 0 or 1+, preferably 4-, 3-, 2- , 1-, 0 or 1+.
Where 3-5 X^IMay be the same or different from each other, and L^IIf there are multiple, there are multiple L^IMay be the same as or different from each other.
In the above, the pseudohalogen (halogenoid) ion is an ion having properties similar to a halogen ion. For example, a cyanide ion (CN)⁻), Thiocyanate ion (SCN)⁻), Selenocyanate ion (SeCN)⁻), Tellurocyanate ion (TeCN)⁻), Azidodithiocarbonate ion (SCSN)₃ ⁻), Thunderate ion (ONC)⁻), Azide ion (N₃ ⁻) And the like.
X^IPreferred are fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, isocyanate ion, thiocyanate ion, nitrate ion, nitrite ion, or azide ion, among which chloride ion, And bromide ions are particularly preferred. L^IThere is no particular limitation, and it may be an inorganic compound or an organic compound, and may be charged or uncharged, but is preferably an uncharged inorganic compound or organic compound.
[0024]
Among the metal complexes of the general formula (I), the metal complex represented by the general formula (IA) or (IB) is preferable. Among these, the metal complex represented by general formula (IB) is more preferable.
In the general formula (IA), X^IAIs X in the general formula (I)^IThe preferred range is also the same. L^IAPreferred are water, OCN, ammonia, phosphine, and carbonyl, with water being particularly preferred.
Where 3-5 X^IAMay be the same or different from each other, and L^IAIf there are multiple, there are multiple L^IAMay be the same as or different from each other.
[0025]
In the general formula (IB), X^IBIs X in the general formula (I)^IThe preferred range is also the same. L^IBRepresents a ligand in which a chain or cyclic hydrocarbon is a parent structure, or a carbon or hydrogen atom in a part of the parent structure is replaced with another atom or atomic group, and a cyanide ion is exclude. L^IBIs preferably a heterocyclic compound. More preferably, it is a complex having a five-membered ring compound as a ligand, and among the five-membered ring compounds, it is a compound containing at least one nitrogen atom and at least one sulfur atom in the five-membered ring skeleton. preferable.
Where 3-5 X^IBMay be the same or different from each other, and L^IBIf there are multiple, there are multiple L^IBMay be the same as or different from each other.
[0026]
Among the metal complexes represented by the general formula (IB), the metal complex represented by the general formula (IC) is more preferable.
In the general formula (IC), X^ICIs X in the general formula (I)^IThe preferred range is also the same. L^ICThe substituent on the carbon atom in the inner ring skeleton is preferably a substituent having a smaller volume than the n-propyl group. As a substituent, methyl group, ethyl group, methoxy group, ethoxy group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, formyl group, thioformyl group, hydroxy group, mercapto group, amino group, hydrazino group Azido group, nitro group, nitroso group, hydroxyamino group, carboxyl group, carbamoyl group, fluoro group, chloro group, bromo group and iodo group are preferred.
Where 3-5 X^ICMay be the same or different from each other, and L^ICIf there are multiple, there are multiple L^ICMay be the same as or different from each other.
[0027]
Among the metal complexes of the general formula (IC), the metal complex represented by the general formula (ID) is more preferable.
In the general formula (ID), X^IDIs X in the general formula (I)^IThe preferred range is also the same. L^IDAs a compound having thiadiazole as a skeleton, a substituent other than hydrogen is preferably bonded to a carbon atom in the compound. Preferred substituents are halogen atoms (fluorine, chlorine, bromine, iodine), methoxy group, ethoxy group, carboxyl group, methoxycarboxyl group, acyl group, acetyl group, chloroformyl group, mercapto group, methylthio group, thioformyl group, thiol Carboxy group, dithiocarboxy group, sulfino group, sulfo group, sulfamoyl group, methylamino group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, hydroxyamino group, hydroxyimino group, carbamoyl group, nitroso Group, nitro group, hydrazino group, hydrazono group or azide group, more preferably halogen atom (fluorine, chlorine, bromine, iodine), chloroformyl group, sulfino group, sulfo group, sulfamoyl group, isocyano group, cyanato group ,I It is a soocyanato group, a thiocyanato group, an isothiocyanato group, a hydroxyimino group, a nitroso group, a nitro group, or an azide group. Of these, chlorine, bromine, chloroformyl group, isocyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group and isothiocyanato group are particularly preferable. n is preferably 4 or 5, and m is preferably -2 or -1.
Where 3-5 X^IDMay be the same or different from each other, and L^IDIf there are multiple, there are multiple L^IDMay be the same as or different from each other.
[0028]
Although the preferable specific example of a metal complex represented with general formula (I) below is given, this invention is not limited to these.
[IrCl_Five(H₂O)]^2-
[IrCl_Four(H₂O)₂]^-
[IrCl_Five(H₂O)]^-
[IrCl_Four(H₂O)₂]⁰
[IrCl_Five(OH)]^3-
[IrCl_Four(OH)₂]^2-
[IrCl_Five(OH)]^2-
[IrCl_Four(OH)₂]^2-
[IrCl_Five(O)]^Four-
[IrCl_Four(O)₂]^Five-
[IrCl_Five(O)]^3-
[IrCl_Four(O)₂]^Four-
[IrBr_Five(H₂O)]^2-
[IrBr_Four(H₂O)₂]^-
[IrBr_Five(H₂O)]^-
[IrBr_Four(H₂O)₂]⁰
[IrBr_Five(OH)]^3-
[IrBr_Four(OH)₂]^2-
[IrBr_Five(OH)]^2-
[IrBr_Four(OH)₂]^2-
[IrBr_Five(O)]^Four-
[IrBr_Four(O)₂]^Five-
[IrBr_Five(O)]^3-
[IrBr_Four(O)₂]^Four-
[IrCl_Five(OCN)]^3-
[IrBr_Five(OCN)]^3-
[IrCl_Five(Thiazole)]^2-
[IrCl_Four(Thiazole)₂]^-
[IrCl_Three(Thiazole)_Three]⁰
[IrBr_Five(Thiazole)]^2-
[IrBr_Four(Thiazole)₂]^-
[IrBr_Three(Thiazole)_Three]⁰
[IrCl_Five(5-methylthiazole)]^2-
[IrCl_Four(5-methylthiazole)₂]^-
[IrBr_Five(5-methylthiazole)]^2-
[IrBr_Four(5-methylthiazole)₂]^-
[IrCl_Five(5-chlorothiadiazole)]^2-
[IrCl_Four(5-chlorothiadiazole)₂]^-
[IrBr_Five(5-chlorothiadiazole)]^2-
[IrBr_Four(5-chlorothiadiazole)₂]^-
[IrCl_Five(2-Chloro-5-fluorothiadiazole)]^2-
[IrCl_Four(2-Chloro-5-fluorothiadiazole)₂]^-
[IrBr_Five(2-Chloro-5-fluorothiadiazole)]^2-
[IrBr_Four(2-Chloro-5-fluorothiadiazole)₂]^-
[IrCl_Five(2-Bromo-5-chlorothiadiazole)]^2-
[IrCl_Four(2-Bromo-5-chlorothiadiazole)₂]^-
[IrBr_Five(2-Bromo-5-chlorothiadiazole)]^2-
[IrBr_Four(2-Bromo-5-chlorothiadiazole)₂]^-
Among these, [IrCl_Five(5-methylthiazole)]^2-Or [IrCl_Five(2-Chloro-5-fluorothiadiazole)]^2-Is preferred.
[0029]
The metal complex represented by the general formula (II) used in the present invention will be described. In the general formula (II), X^IIIs a fluoride ion, a chloride ion, a bromide ion, or an iodide ion, and among them, a chloride ion and a bromide ion are particularly preferable. L^IIMay be an inorganic compound or an organic compound, and may be charged or uncharged, but is preferably an uncharged inorganic compound. L^IIPreferably H₂O, NO or NS.
Where 3-6 X^IIMay be the same or different from each other, and L^IIIf there are multiple, there are multiple L^IIMay be the same as or different from each other.
[0030]
Among the metal complexes of the general formula (II), the metal complex represented by the general formula (IIA) is preferable.
In the general formula (IIA), X^{II A}Is X in the general formula (II)^IIThe preferred range is also the same. n is preferably 4 to 6, and m is preferably 3-, 2-, 1-.
Where 3-6 X^{II A}May be the same or different from each other, and L^{II A}If there are multiple, there are multiple L^{II A}May be the same as or different from each other.
[0031]
Although the preferable specific example of a metal complex represented by general formula (II) below is given, this invention is not limited to these.
[ReCl₆]^2-
[ReCl_Five (NO)]^2-
[RuCl₆]^2-
[RuCl₆]^3-
[RuCl_Five (NO)]^2-
[RuCl_Five (NS)]^2-
[RuBr_Five (NS)]^2-
[OsCl₆]^Four-
[OsCl_Five (NO)]^2-
[OsBr_Five (NS)]^2-
[RhCl₆]^3-
[RhCl_Five(H₂O)]^2-
[RhCl_Four(H₂O)₂]^-
[RhBr₆]^3-
[RhBr_Five(H₂O)]^2-
[RhBr_Four(H₂O)₂]^-
[PdCl₆]^2-
[PtCl₆]^2-
Among these, [OsCl_Five (NO)]^2-Or [RhBr₆]^3-Is preferred.
[0032]
When the metal complex mentioned above is an anion, when a salt is formed with a cation, the one 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 silver mole during the formation of silver halide grains.^-TenFrom mole to 1 × 10^-3It is preferable to add 1 mol.^-8From mole to 1 × 10^-FiveMost preferably, it is added in a molar amount. The metal complex represented by the general formula (II) is 1 × 10 5 per mol of silver during grain formation.^-11From mole to 1 × 10^-6It is preferable to add 1 mol.^-9From mole to 1 × 10^-7Most preferably, it is added in a molar amount.
[0033]
In the present invention, the above metal complex is added directly to the reaction solution at the time of silver halide grain formation, or added to an aqueous halide solution for forming silver halide grains, or in other solutions to form grains. It is preferably incorporated into the silver halide grains by adding to the reaction solution. It is also preferable to physically ripen the fine particles in which the metal complex has been 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.
[0034]
When these metal complexes are incorporated into silver halide grains, they can be uniformly present inside the grains, but disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to be present only in the particle surface layer, and it is also preferable to add a layer that does not contain a complex on the particle surface while the complex exists only in the particle interior. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Further, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain.
[0035]
In the present invention, it is necessary that the silver halide emulsion layer contains at least two types of silver halide emulsions having different silver chloride contents having a sensitivity of 90 mol% or more. Two or more types of silver halide emulsions having different sensitivities may be used, but two or three types are preferable in the design of the photosensitive material. When three or more types of silver halide emulsions having different sensitivities are used, the present invention is applied to any two types of silver halide emulsions. The two types of silver halide emulsions may be different in the type and amount of grain size, halogen composition and structure, sensitizing dye, chemical sensitizer, antifoggant and the like. However, two types of silver halide emulsions having a silver chloride content of 90 mol% or more must have different sensitivities. The sensitivity is 10 depending on the composition of the photosensitive material used.^-4When the imagewise exposure is performed for 2 seconds and the development processing used is performed, the log E is preferably 0.05 to 0.8, more preferably 0.15 to 0.5.
[0036]
It is preferable that at least two types of silver halide emulsions having different silver chloride contents of 90 mol% or more with different sensitivities are mixed in the same silver halide emulsion layer. However, emulsions having different sensitivities are in separate emulsion layers. It may be painted separately. However, these layers are required to have almost the same color sensitivity and color hue. Here, in the case of a color photographic light-sensitive material, substantially equal color sensitivities are, for example, blue color sensitivities, green color sensitivities, or red color sensitivities. Good. In the case of a color photographic light-sensitive material, for example, yellow color development, magenta color development, or cyan color development, and the color development hues may be different within the range.
[0037]
At least one of the silver halide emulsions having at least two silver chloride contents with different sensitivities of 90 mol% or more contains at least one of the above metal complexes. Both of the two types of silver halide emulsions having different sensitivities preferably contain the above metal complex, and more preferably all the silver halide emulsions in the silver halide emulsion layer contain the above metal complex.
[0038]
  At least two types of silver halide emulsions having different silver chloride contents with different sensitivities, the content of the above metal complex per mole of silver halide is lower on the lower sensitivity side than on the higher sensitivity side. EmulsionTheManyMake OrThe average content per grain is lower for the emulsion on the low sensitivity side than for the emulsion on the high sensitivity side.TheManyMakeIn these cases, the above-mentioned metal complex may not be contained in the high-sensitivity emulsion, but is preferably contained in a smaller amount than the emulsion on the low-sensitivity side.
[0039]
  OrIn silver halide emulsions having a silver chloride content of 90 mol% or more with different sensitivity, at least two kinds of sensitivity, the desensitization by the above metal complex is more effective for the emulsion on the low sensitivity side than the emulsion on the high sensitivity side.TheBigI'll be happy.Here, the desensitization by the metal complex represents the sensitivity difference when the corresponding metal complex is not contained in the same emulsion and the sensitivity difference when it is contained, with the desensitization direction being positive. Also oneOneIn the case of an emulsion not containing the corresponding metal complex, the desensitization is 0. The desensitivity of each of the emulsion on the high sensitivity side and the emulsion on the low sensitivity side is preferably 0 to 0.8, and more preferably 0.1 to 0.5 in terms of log E. The desensitization due to the corresponding metal complex in the emulsion on the low sensitivity side is preferably 0.1 to 0.8 larger in log E than that of the emulsion on the high sensitivity side, more preferably 0.1 to 0.5 larger. preferable.
[0040]
The silver halide emulsion of the present invention contains specific silver halide grains. The particle shape is not particularly limited, but is substantially a cubic or tetradecahedral crystal particle having {100} faces (they may have rounded particle vertices and may have higher-order faces), 8 It is preferable that the crystal grain of a plane body and the main surface consist of a tabular grain having an aspect ratio of 3 or more and comprising a {100} plane or a {111} plane. 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.
[0041]
The silver chloride content needs to be 90 mol% or more, and from the viewpoint of rapid processability, the silver chloride content is preferably 93 mol% or more, and more preferably 95 mol% or more. The silver bromide content is preferably 0.1 to 7 mol%, more preferably 0.5 to 5 mol%, since it is a high contrast and has excellent latent image stability. The silver iodide content is preferably 0.02-1 mol%, more preferably 0.05-0.50 mol%, and more preferably 0.07-0. 40 mol% is most preferred. The specific silver halide grains of the present invention are preferably silver iodobromochloride grains, more preferably silver iodobromochloride grains having the above halogen composition.
[0042]
The specific silver halide grains in the silver halide emulsion of the present invention preferably have a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than the surroundings. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide or silver iodide-containing phase may form a layer having a substantially constant width at a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more, more preferably 10 to 80 mol%, and most preferably 15 to 50 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Most preferred. Further, a plurality of such silver bromide or silver iodide-containing phases may be formed in layers in each grain, and the silver bromide or silver iodide content may be different, but at least one of each. It is necessary to have a contained phase of
[0043]
It is important that the silver bromide-containing phase or the silver iodide-containing phase of the silver halide emulsion of the present invention is layered so as to surround each grain. In one preferred embodiment, the silver bromide-containing phase or the silver iodide-containing phase formed in layers so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains in each phase. However, in the silver bromide-containing phase or silver iodide-containing phase that are layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain, and the concentration distribution You may have. For example, when a silver bromide-containing phase or silver iodide-containing phase is formed in a layer so as to surround the grain in the vicinity of the grain surface, the silver bromide or silver iodide concentration at the grain corner or edge is different from the main surface. There is a case. In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, the silver bromide-containing phase that is completely isolated in a specific part of the surface of the grain and does not surround the grain Alternatively, there may be a silver iodide containing phase.
[0044]
When the silver halide emulsion of the present invention contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in a layered manner so as to have a silver bromide concentration maximum inside the grain. Further, when the silver halide emulsion of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in a layered manner so as to have a silver iodide concentration maximum on the surface of the grain. Such a silver bromide-containing phase or silver iodide-containing phase is composed of a silver amount of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the silver content is 3% or more and 15% or less.
[0045]
The silver halide emulsion of the present invention preferably contains both a silver bromide-containing phase and a silver iodide-containing phase. In this case, the silver bromide-containing phase and the silver iodide-containing phase may be at the same place or different places in the grain, but it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are in different places from the viewpoint of facilitating control of grain formation. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, iodide added during the formation of high silver chloride grains tends to ooze out on the grain surface than bromide, so the silver iodide-containing phase tends to be formed near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different locations in the grain, the silver bromide-containing phase is preferably formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.
[0046]
The silver bromide content or silver iodide content necessary for exhibiting the effects of the present invention such as high sensitivity and high contrast is such that the silver bromide-containing phase or silver iodide-containing phase is formed inside the grain. There is a risk that the amount of silver chloride may be reduced more than necessary, and the rapid processability may be impaired. Therefore, in order to concentrate these functions for controlling the photographic action near the surface in the grain, the silver bromide-containing phase and the silver iodide-containing phase are preferably adjacent to each other. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume as measured from the inside, and the silver iodide-containing phase is any of the positions at 85% to 100% of the grain volume. It is preferable to form it. Further, the silver bromide-containing phase is formed at any position from 70% to 95% of the grain volume, and the silver iodide-containing phase is further formed at any position from 90% to 100% of the grain volume. preferable.
[0047]
Introducing bromide or iodide ions to contain silver bromide or silver iodide in the silver halide emulsion of the present invention can be carried out by adding a bromide salt or iodide salt solution alone, Along with the addition of the chloride salt solution, a bromide salt or iodide salt solution may be added. In the latter case, bromide salt or iodide salt solution and high chloride salt solution may be added separately or as a mixed solution of bromide salt or iodide salt and high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can also be introduced by cleaving bromide ions or iodide ions from organic molecules described in US Pat. No. 5,389,508. As another bromide or iodide ion source, fine silver bromide grains or fine silver iodide grains can also be used.
[0048]
The addition of the bromide salt or 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 85%. Further, 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.
On the other hand, the addition of the bromide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70%.
[0049]
Distribution of bromide or iodide ion concentration in the depth direction in the particle is 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. it can. 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. The emulsion of the present invention is analyzed by etching / TOF-SIMS method, and it is preferable that iodide ions have a maximum concentration on the grain surface, and the iodide ion concentration is attenuated toward the inside. It is preferable to have a concentration maximum inside. The local concentration of silver bromide can also be measured by X-ray diffraction if the silver bromide content is somewhat high.
[0050]
In this specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. The emulsion of the present invention is preferably composed of grains having a monodispersed grain size distribution. The variation system number of the sphere equivalent diameter of all the particles of the present invention is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. The variation coefficient of the equivalent sphere diameter is expressed as a percentage of the standard deviation of the equivalent sphere diameter of each particle with respect to the average equivalent sphere diameter. 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.
[0051]
The present invention provides a silver halide color photographic material having at least one each of a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, and a cyan dye-forming coupler-containing silver halide emulsion layer. When applied, the sphere equivalent diameter of the silver halide emulsion of the yellow dye-forming coupler-containing silver halide emulsion layer is preferably 0.6 μm or less, more preferably 0.5 μm or less, and 0.4 μm or less. Most preferably. The sphere equivalent diameter of the silver halide emulsion of the magenta dye-forming coupler-containing silver halide emulsion layer and the cyan dye-forming coupler-containing silver halide emulsion layer is preferably 0.5 μm or less, and preferably 0.4 μm or less. More preferably, it is most preferably 0.3 μm or less. In this specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. Particles with a sphere equivalent diameter of 0.6 μm correspond to cubic particles with a side length of about 0.48 μm, particles with a sphere equivalent diameter of 0.5 μm correspond to cubic particles with a side length of about 0.40 μm, and a sphere equivalent diameter of 0.4 μm. These particles correspond to cubic particles having a side length of about 0.32 μm, and particles having a sphere equivalent diameter of 0.3 μm correspond to cubic particles having a side length of about 0.24 μm. The silver halide emulsion of the present invention may contain silver halide grains other than the silver halide grains (that is, specific silver halide grains) contained in the silver halide emulsion defined in the present invention. However, the silver halide emulsion defined in the present invention requires that 50% or more of the total projected area of all the grains be silver halide grains defined in the present invention, and preferably 80% or more. More preferably, it is 90% or more.
[0052]
The specific silver halide grains in the silver halide emulsion of the present invention further contain an iridium complex in which all six ligands are composed of Cl, Br or I in addition to the iridium complex represented by the general formula (I). be able to. In this case, Cl, Br, or I may be mixed in the hexacoordinate complex. It is particularly preferable that the iridium complex having Cl, Br or I as a ligand is contained in the silver bromide-containing phase in order to obtain a high gradation at high illumination exposure.
[0053]
Specific examples of iridium complexes in which all six ligands are Cl, Br, or I are given below, but are not limited thereto.
[IrCl₆]^2-
[IrCl₆]^3-
[IrBr₆]^2-
[IrBr₆]^3-
[IrI₆]^3-
[0054]
In the present invention, in addition to the metal complexes described above, other metal ions can be doped inside and / or on the surface of silver halide grains. As a metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, 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, osmium, lead, cadmium, or zinc, and a plurality of kinds of ligands are contained in one complex molecule. It is also preferable to use it. An organic compound can also be used as the ligand, and preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom in the molecule as a coordination atom to the metal, particularly 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.
[0055]
A combination of metal ions and ligands is preferably a combination of iron ions, ruthenium ions and cyanide ions. In the present invention, it is preferable to use the above-described metal complex and these compounds in combination. In these compounds, the cyanide ion preferably accounts 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, It is preferably occupied by pyrazine or 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 cyanide ion-ligand complexes are 1 x 10 per mole of silver during grain formation.^-8From mole to 1 × 10^-2It is preferable to add 1 mol.^-6From mole to 5 × 10^-FourMost preferably, it is added in a molar amount.
[0056]
The silver halide emulsion used in the present invention is preferably subjected to gold sensitization known in the art. This is because gold sensitization can increase the sensitivity of the emulsion, and can reduce variations in photographic performance when scanning exposure is performed with laser light or the like. For gold sensitization, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands can be used. 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. Compounds such as gold dithiosulfate compounds such as sodium can be used.
[0057]
Examples of the gold (I) compound having an organic ligand (organic compound) include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, such as bis (1,4,5-trimethyl-1, 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate, organomercaptogold (I) complexes described in JP-A-11-218870, such as potassium bis (1- [3- (2-sulfonate benzamide) ) 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-methylhydan Toinert) gold (I) sodium salt tetrahydrate can be used. The gold (I) compound having these organic ligands may be synthesized in advance and isolated, or may be mixed with an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof). Can be added to the emulsion without generation and isolation. Furthermore, an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof) may be added separately to the emulsion to generate a gold (I) compound having an organic ligand in the emulsion.
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.
[0058]
Colloidal gold sulfide can also be used. The manufacturing method thereof is Research Disclosure (37154), Solid State Ionics 79, 60-66, 1995, Compt. Rend.Hebt.Seances Acad.Sci.Sect.B, 263, 1328, published in 1966. The Research Disclosure describes a method using a thiocyanate ion in the production of colloidal gold sulfide, but a thioether compound such as methionine or thiodiethanol can be used instead.
Various sizes of colloidal gold sulfide can be used, and those having an average particle size of 50 nm or less are preferred, an average particle size of 10 nm or less is more preferred, and an average particle size of 3 nm or less is even more preferred. This particle size can be measured from a TEM photograph. The composition of colloidal gold sulfide is Au₂S₁But, Au₂S₁~ Au₂S₂Such a composition with excess sulfur may be used, and a composition with excess sulfur is preferred. Au₂S_1.1~ Au₂S_1.8Is more preferable.
The composition analysis of the colloidal gold sulfide can be obtained, for example, by taking out gold sulfide particles and determining the gold content and sulfur content by using an analysis method such as ICP or iodometry, respectively. If gold ions and sulfur ions (including hydrogen sulfide and its salts) dissolved in the liquid phase are present in the gold sulfide colloid, the composition analysis of the gold sulfide colloid particles will be affected. The analysis is performed after separation. The amount of colloidal gold sulfide 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.
[0059]
In addition to gold sensitization, chalcogen sensitization can be performed with the same molecule.⁻Can be used. Here, Au represents Au (I), and Ch represents a sulfur atom, a selenium atom, or a tellurium atom. AuCh⁻Examples of the molecule capable of releasing a include a gold compound represented by AuCh-L. Here, L represents an atomic group constituting a molecule by binding to AuCh. Further, one or more ligands may be coordinated with Au together with Ch-L. In addition, the gold compound represented by AuCh-L is likely to generate AgAuS when Ch is S, AgAuSe when Ch is Se, and AgAuTe when Ch is Te when reacted in a solvent in the presence of silver ions. It is what has. Examples of such a compound include those in which L is an acyl group. In addition, compounds represented by the following general formula (AuCh1), general formula (AuCh2), and general formula (AuCh3) are exemplified. .
[0060]
General formula (AuCh1)
R₁-X-M-ChAu
In the formula, Au represents Au (I), Ch represents a sulfur atom, selenium atom or tellurium atom, M represents a substituted or unsubstituted methylene group, X represents an oxygen atom, sulfur atom, selenium atom or NR.₂Represents R₁Represents an atomic group (for example, an organic group such as an alkyl group, an aryl group, and a heterocyclic group) that forms a molecule by binding to X, and R₂Represents a hydrogen atom or a substituent (for example, an organic group such as an alkyl group, an aryl group, and a heterocyclic group). R₁And M may combine with each other to form a ring.
In the compound represented by the general formula (AuCh1), Ch is preferably a sulfur atom or a selenium atom, X is preferably an oxygen atom or a sulfur atom, R₁Is preferably an alkyl group or an aryl group. Examples of more specific compounds include Au (I) salts of thiosugars (gold thioglucose such as α-gold thioglucose, gold peracetylthioglucose, gold thiomannose, gold thiogalactose, and gold thioarabinose), seleno Au (I) salts of sugars (gold peracetylselenoglucose, gold peracetylselenomannose, etc.), Au (I) salts of tellurosugar, and the like. Here, thio sugar, seleno sugar, and telluro sugar represent compounds in which the anomeric hydroxyl group of the sugar is replaced with an SH group, a SeH group, or a TeH group, respectively.
[0061]
General formula (AuCh2)
W₁W₂C = CR₃ChAu
In the formula, Au represents Au (I), Ch represents a sulfur atom, a selenium atom or a tellurium atom, R₃And W₂Represents a substituent (for example, a hydrogen atom, a halogen atom, and an organic group such as an alkyl group, an aryl group, or a heterocyclic group), and W₁Is Hammett's substituent constant σ_pAn electron-withdrawing group having a positive value is represented. R₃And W₁, R₃And W₂, W₁And W₂May combine with each other to form a ring.
In the compound represented by the general formula (AuCh2), one in which Ch is a sulfur atom or a selenium atom is preferred, and R₃Is preferably a hydrogen atom or an alkyl group, and W₁And W₂Is Hammett's substituent constant σ_pAn electron withdrawing group having a value of 0.2 or more is preferred. Examples of more specific compounds include (CN)₂C = CHSAu, (CH₃OCO)₂C = CHSAu, CH₃CO (CH₃OCO) C = CHSAu and the like.
[0062]
General formula (AuCh3)
W₃-E-ChAu
In the formula, Au represents Au (I), Ch represents a sulfur atom, selenium atom or tellurium atom, E represents a substituted or unsubstituted ethylene group, W₃Is Hammett's substituent constant σ_pAn electron-withdrawing group having a positive value is represented.
In the compound represented by the general formula (AuCh3), it is preferable that Ch is a sulfur atom or a selenium atom, and E is a Hammett's substituent constant σ._pIt is preferably an ethylene group having an electron-withdrawing group having a positive value, and W₃Is Hammett's substituent constant σ_pAn electron withdrawing group having a value of 0.2 or more is preferred.
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^-3Moles, preferably 3 × 10^-6~ 3x10^-4Is a mole.
[0063]
In the present invention, the above 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. . It is particularly preferable to combine with sulfur sensitization and selenium sensitization.
[0064]
To the silver halide emulsion of the present invention, various compounds or precursors thereof may be added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. Can do. As specific examples of these compounds, those described on pages 39 to 72 of JP-A-62-215272 are preferably used. 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.
[0065]
In the present invention, in order to enhance the storage stability of the silver halide emulsion, both ends are adjacent to the hydroxamic acid derivative described in JP-A-11-109576 and the carbonyl group described in JP-A-11-327094. Cyclic ketones having a double bond substituted with an amino group or 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), particularly Sulfo-substituted catechol and hydroquinones described in JP-A-11-143011 (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4 -Dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid Acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), hydroxylamines represented by the general formula (A) in US Pat. No. 5,556,741 (US Pat. No. 556,741 column 4, line 56 to column 11, line 22 is preferably applied to the present application and is incorporated as part of the present specification), Japanese Patent Application Laid-Open No. 11-102045. The water-soluble reducing agents represented by the general formulas (I) to (III) in the publication are also preferably used in the present invention.
[0066]
The silver halide emulsion of the present invention may contain a spectral sensitizing dye for the purpose of imparting so-called spectral sensitivity exhibiting photosensitivity in a desired light wavelength range. Examples of spectral sensitizing dyes used for spectral sensitization in the blue, green, and red regions 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. Further, as a red-sensitive spectral sensitizing dye of silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, adsorbed, and exposed. This is very preferable from the viewpoint of temperature dependency.
[0067]
The addition amount of these spectral sensitizing dyes varies widely depending on the case, and is 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.
[0068]
The silver halide color photographic light-sensitive material of the present invention (hereinafter sometimes simply referred to as “light-sensitive material”) contains a silver halide emulsion layer containing a yellow dye-forming coupler and a magenta dye-forming coupler on a support. The silver halide emulsion layer preferably contains at least one silver halide emulsion layer containing a cyan dye-forming coupler, and at least one of the silver halide emulsion layers contains the silver halide emulsion of the present invention. It is preferable to contain. In the present invention, the silver halide emulsion layer containing the yellow dye-forming coupler contains a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler contains a magenta coloring layer, and the cyan dye-forming coupler. The silver halide emulsion layer functions as a cyan color-developing layer. The silver halide emulsions contained in the yellow coloring layer, the magenta coloring layer and the cyan coloring layer, respectively, are sensitive to light in different wavelength regions (for example, light in the blue region, green region and red region). It is preferable to have.
[0069]
The light-sensitive material of the present invention may have a hydrophilic colloid layer, an antihalation layer, an intermediate layer, and a colored layer, which will be described later, if desired, in addition to the yellow coloring layer, magenta coloring layer, and cyan coloring layer.
[0070]
Conventionally known photographic materials and additives can be used in the light-sensitive material of the present invention.
For example, as the photographic support, a transmissive support or a reflective support can be used. As the transmissive support, transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), NDCA, terephthalic acid and EG are used. A polyester provided with an information recording layer such as a magnetic layer is preferably used. As the reflective support, a reflective support that is laminated with a plurality of polyethylene layers or polyester layers and contains a white pigment such as titanium oxide in at least one layer of such a water-resistant resin layer (laminate layer) is preferable.
[0071]
In the present invention, more preferred reflective supports include those having a polyolefin layer having fine pores on the paper substrate on the side on which the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case preferably the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side does not have micropores (eg, polypropylene, polyethylene) and is on a paper substrate. More preferred is a polyolefin (for example, polypropylene or polyethylene) having micropores on the near side. The density of the multi-layer or single-layer polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 0.40 to 1.0 g / ml, more preferably 0.50 to 0.70 g / ml. The thickness of the multilayer or single layer of polyolefin positioned between the paper substrate and the photographic composition layer is preferably 10 to 100 μm, and more preferably 15 to 70 μm. Further, the ratio of the thickness of the polyolefin layer to the paper substrate is preferably 0.05 to 0.2, more preferably 0.1 to 0.15.
[0072]
In addition, it is also preferable to provide a polyolefin layer on the opposite side (back surface) to the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflective support. In this case, the back surface polyolefin layer has a matte polyethylene surface. Alternatively, polypropylene is preferable, and polypropylene is more preferable. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support in the present invention, preferred embodiments relating to the polyolefin layer provided on the paper substrate are disclosed in JP-A-10-333277, JP-A-10-333278, JP-A-11-52513, and JP-A-11-65024. Examples are described in EP0880065 and EP0880066.
[0073]
Furthermore, it is preferable to contain a fluorescent brightening agent in the water-resistant resin layer. Further, a hydrophilic colloid layer containing the fluorescent brightening agent in a dispersed manner may be separately formed. As the optical brightener, benzoxazole-based, coumarin-based, and pyrazoline-based compounds can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based fluorescent whitening agents are more preferable. The amount used is not particularly limited, but preferably 1 to 100 mg / m.²It is. The mixing ratio in the case of mixing with a water resistant resin is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass with respect to the resin.
[0074]
The reflective support may be a transmissive support or a reflective colloid coated with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a specular or second-type diffuse reflective metal surface.
[0075]
Further, as a support used in the light-sensitive material of the present invention, a white polyester support or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer is used for a display. May be. In order to further improve the sharpness, an antihalation layer is preferably coated on the silver halide emulsion layer coating side or the back surface of the support. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with either reflected light or transmitted light.
[0076]
In the light-sensitive material of the present invention, a dye which can be decolored by processing as described in pages 27 to 76 of European Patent EP0,337,490A2 is applied to a hydrophilic colloid layer for the purpose of improving the sharpness of an image. Among them, oxonol dyes are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or divalent to tetravalent alcohols (for example, trimethylolethane) are added to the water-resistant resin layer of the support. ) Etc. It is preferable to contain 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated.
[0077]
In the light-sensitive material of the present invention, the processing described in pages 27 to 76 of EP 0337490 A2 is carried out on the hydrophilic colloid layer for the purpose of preventing irradiation and halation or improving the safety light safety. It is preferable to add a decolorizable dye (in particular, an oxonol dye or a cyanine dye). 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 a 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.
[0078]
In the present invention, a colored layer that can be decolored by treatment in place of the water-soluble dye or in combination with the water-soluble dye is used. The colored layer that can be decolored by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably placed under the emulsion layer (support side) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to select and install only some of them. It is also possible to install a colored layer that has been colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength having the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm for normal printer exposure, wavelength of the scanning exposure light source used for scanning exposure). The optical density value at is preferably 0.2 or more and 3.0 or less. More preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.
[0079]
In order to form the colored layer, a conventionally known method can be applied. For example, the dyes described in JP-A-2-282244, page 3 from the upper right column to page 8, and the dyes described in JP-A-3-7931, page 3 from upper right column to page 11, lower left column are solid. A method of incorporating a hydrophilic colloid layer in the form of a fine particle dispersion, a method of mordanting an anionic dye into a cationic polymer, a method of adsorbing a dye to fine particles such as silver halide and fixing it in the layer, JP-A-1-239544 For example, a method using colloidal silver as described in Japanese Patent Publication. As a method of dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Application Laid-Open No. Hei. No. 2-308244, pages 4 to 13. Further, for example, a method for mordanting an anionic dye into a cationic polymer is described on pages 18 to 26 of JP-A-2-84737. US Pat. Nos. 2,688,601 and 3,459,563 show preparation methods for colloidal silver as a light absorber. Among these methods, a method of containing a fine powder dye and a method of using colloidal silver are preferable.
[0080]
The silver halide photographic light-sensitive material of the present invention is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc., among which it is preferably used as a color photographic paper. The color photographic paper preferably has 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. The silver halide emulsion layer is 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 order from the support.
[0081]
However, a different layer structure may be used.
The silver halide emulsion layer containing a yellow coupler may be disposed at any position on the support. However, when the yellow coupler-containing layer contains silver halide tabular grains, a magenta coupler-containing silver halide is contained. It is preferably coated at a position farther from the support than at least one emulsion layer or cyan coupler-containing silver halide emulsion layer. Further, from the viewpoints of accelerating color development, accelerating desilvering, and reducing residual color by sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated at a position farthest from the support than other silver halide emulsion layers. It is preferable to be provided. 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, cyan coupler-containing silver halide emulsion layers. Is preferably the lowermost layer. Each of the color developing layers of yellow, magenta and cyan may be composed of two layers or three layers. For example, couplers containing no silver halide emulsion as described in JP-A-4-75055, JP-A-9-1114035, JP-A-10-246940, US Pat. No. 5,576,159, etc. It is also preferable to provide a layer adjacent to the silver halide emulsion layer to form a color developing layer.
[0082]
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, Disclosed in JP-A-62-215272, JP-A-2-33144, European Patent EP0,355,660A2, and particularly 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. No. 2-854, No. 1-158431, No. 2-90145, No. 3-194539, No. 2-93641, EP-A-0520457A2, and the like. A silver halide color photographic light-sensitive material and a processing method thereof are also preferable.
[0083]
In particular, in the present invention, the reflection type support and silver halide emulsion described above, further different metal ion species doped in the silver halide grains, storage stabilizer or antifoggant for silver halide emulsion, chemical enhancement, Sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsifying dispersion method, color image preservability improving agent (stain inhibitor and anti-fading agent), dye (coloring) As for the layer), the gelatin type, the layer structure of the photosensitive material, the coating pH of the photosensitive material, and the like, those described in each part of the publication shown in Table 1 below are particularly preferably applicable.
[0084]
[Table 1]

[0085]
Other examples of 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. Page 3, upper right column, line 14 to page 18, upper left column, last line, page 30, upper right column, line 6 to page 35, lower right column, line 11 and page 0, line 15 to 27 of EP0355,660A2. Couplers described in the 5th line, 5th page, 30th line to 28th page, 45th page, 29th line to 31st line, 47th page, 23rd line to 63rd page, 50th line are also useful.
In the present invention, compounds represented by the general formulas (II) and (III) of WO 98/33760 and the general formula (D) of JP-A-10-221825 may be added.
[0086]
As a cyan dye-forming coupler (sometimes simply referred to as “cyan coupler”) that can be used in the present invention, a pyrrolotriazole coupler is preferably used, and is represented by the general formula (I) or (II) of JP-A-5-313324. ), Couplers represented by general formula (I) of JP-A-6-347960, and exemplified couplers described in these publications 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 EP0488248 and EP0491197A1, 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 are disclosed. Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A Nos. 171185, 8-31360, and 8-339060 are also preferable.
[0087]
Further, in addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine cyan coupler described in European Patent EP 0333185A2 (among others of the coupler (42) listed as a specific example). A 4-equivalent coupler having a chlorine leaving group to give 2 equivalents, couplers (6) and (9) are particularly preferred) and cyclic active methylene-based cyan couplers described in JP-A 64-32260 (among others) Examples of couplers 3, 8, and 34 listed as specific examples are particularly preferred), pyrrolopyrazole cyan couplers described in EP 0456226A1, and pyrroloimidazole cyan couplers described in EP 0484909 are used. You can also.
[0088]
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.
[0089]
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 the 2, 3, or 6 position of the pyrazolotriazole ring among them in terms of hue, image stability, color developability, etc. A pyrazolotriazole coupler directly connected to a pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246, as described in JP-A-61-147254 Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group, European Patent No. 226,849A, Use of pyrazoloazole couplers having a 6-position alkoxy or aryloxy group as described in the 294,785A Pat are preferred. 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 publication are directly applied to the present application. As part of the specification. In addition to this, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in EP 854384 and EP 844640 are also preferably used.
[0090]
Further, as yellow dye-forming couplers (sometimes simply referred to as “yellow couplers”), in addition to the compounds described in the above table, a 3- to 5-membered cyclic group is added to the acyl group described in EP 0447969A1. An acylacetamide type yellow coupler having a structure, a malondianilide type yellow coupler having a cyclic structure described in European Patent EP 0482552A1, European Patent Publications Nos. Pyrrole-2 or 3-yl or indole-2 or 3-ylcarbonylacetic acid anilide type couplers described in U.S. Pat. Nos. 5,953,873, 953874, 1,953875A1, etc. Described in US Pat. No. 5,118,599 An acylacetamide type yellow coupler having a dioxane structure is preferably used. Among them, the use of 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 is particularly preferred. These couplers can be used alone or in combination.
[0091]
The coupler used in the present invention is impregnated into 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 above 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.
[0092]
In the present invention, known color mixing inhibitors can be used, and among them, those described in the following publications are preferred.
For example, high molecular weight redox compounds described in JP-A-5-333501, phenidone and hydrazine compounds described in WO98 / 33760, US Pat. No. 4,923,787, etc. White couplers described in Japanese Patent No. 249637, Japanese Patent Application Laid-Open No. 10-282615, German Patent No. 19629142A1, and the like can be used. In particular, in the case where the pH of the developer is increased to speed up the development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 842975A1, German Patent No. 1,806,846 A1. It is also preferable to use a redox compound described in the specification and the specification of French Patent No. 2760460A1.
[0093]
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 publications and the like 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-5-197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-218131, and 8- No. 53427, No. 8-234364, No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. The compounds described in the specification of 19739797A, European Patent No. 711804A and JP-A-8-501291 can be used.
[0094]
As the binder or protective colloid that can be used in the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or in combination 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.
[0095]
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.
[0096]
In the present invention, the total amount of gelatin coated in the photographic constituent layer constituent layer is 3 g / m.²6 g / m or more²Preferably, it is 3g / m or less.²5 g / m or more²More preferably, it is as follows. Further, even in the case of ultra-rapid processing, in order to satisfy development progress, fixing bleachability and residual color, the film thickness of the entire photographic constituent layer is preferably 3 μm to 7.5 μm, and more preferably 3 μm to 6. It is preferably 5 μm. The dry film thickness can be measured by measuring the change in film thickness before and after peeling the dry film, or by observing the cross section with an optical microscope or an electron microscope. In the present invention, the swelling film thickness is preferably 8 μm to 19 μm, and more preferably 9 μm to 18 μm, in order to achieve both development progress and increase in the drying speed. The swollen film thickness can be measured by the dot method in a state where the dried photosensitive material is immersed in an aqueous solution at 35 ° C. and swelled to reach a sufficient equilibrium. The silver coating amount in the present invention is 0.2 g / m.²~ 0.5g / m²Is preferably 0.2 g / m²~ 0.45g / m²More preferably, 0.2 g / m²~ 0.40g / m²Most preferably.
[0097]
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^-Five~ 1g / m², Preferably 1 × 10^-Four~ 1x10^-1g / m²More preferably 1 × 10^-3~ 1x10^-2g / m²It is.
[0098]
The photosensitive material of the present invention can form an image by an exposure process in which light is irradiated according to image information and a development process in which the photosensitive material irradiated with light is developed. The photosensitive material of the present invention is suitable for a scanning exposure system using a cathode ray (CRT) in addition to being used in a printing system using a normal negative printer. The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, any one of red light emitters, green light emitters, and blue light emitters, or a mixture of two or more thereof may be used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.
[0099]
When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions, and the cathode tube also has a phosphor exhibiting light emission in a plurality of spectral regions, a plurality of colors are exposed at the same time, that is, a plurality of colors are applied to the cathode ray tube. It is also possible to emit light from the tube surface by inputting a color image signal. A method of sequentially inputting image signals for each color to cause each color to emit light sequentially and exposing through a film that cuts the colors other than that color (surface sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for improving image quality.
[0100]
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.
[0101]
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 a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining 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. When the exposure time in such scanning exposure is defined as the exposure time of the pixel size when the pixel density is 400 dpi, a preferable exposure time is 10^-FourSeconds or less, more preferably 10^-6Less than a second.
[0102]
When the present invention is applied to a silver halide color photographic light-sensitive material, it is preferable to perform imagewise exposure with a blue laser coherent light having an emission wavelength of 420 nm to 460 nm. Among blue lasers, it is particularly preferable to use a blue semiconductor laser.
Specifically, as a laser light source, a blue semiconductor laser having a wavelength of 430 to 450 nm (announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001) and a semiconductor laser (oscillation wavelength of about 940 nm) in a waveguide shape LiNbO having an inverted domain structure of_ThreeLiNbO with an inverted domain structure in the form of a waveguide using a blue laser of about 470 nm and a semiconductor laser (oscillation wavelength of about 1060 nm) extracted by wavelength conversion using SHG crystal_ThreePreferably, a green laser with a wavelength of about 530 nm, a red semiconductor laser with a wavelength of about 685 nm (Hitachi type No. HL6738MG), a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL6501MG), etc., which are taken out by SHG crystal of .
[0103]
The silver halide photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development systems described in the following known materials. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, a photosensitive material conveying apparatus described in JP-A-2000-10206, and an image reading apparatus described in JP-A-11-215312. , An exposure system comprising a color image recording system described in JP-A-11-88619 and JP-A-10-202950, and a digital photo print including a remote diagnosis system described in JP-A-10-210206 And a photo print system including an image recording apparatus described in Japanese Patent Application No. 10-159187.
[0104]
The preferred scanning exposure method applicable to the present invention is described in detail in the publications listed in the above table.
[0105]
When the light-sensitive material of the present invention is subjected to printer exposure, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. This removes light color mixing and remarkably improves color reproducibility.
In the present invention, as described in European Patents EP0789270A1 and EP0789480A1, the yellow microdot pattern may be pre-exposed in advance and copy control may be performed before image information is added. .
[0106]
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. The processing materials and processing methods described in the 17th line to the 18th page, lower right column, line 20 are preferably applicable. As the preservative used in the developer, compounds described in the publications listed in the above table are preferably used.
[0107]
The present invention is applied as a light-sensitive material having rapid processing suitability. The color development time is 28 seconds or shorter, preferably 25 seconds or shorter and 6 seconds or longer, more preferably 20 seconds or shorter and 6 seconds or longer. Similarly, the bleach-fixing time is preferably 30 seconds or shorter, more preferably 25 seconds or shorter and 6 seconds or longer, more preferably 20 seconds or shorter and 6 seconds or longer. The washing or stabilizing time is preferably 60 seconds or shorter, more preferably 40 seconds or shorter and 6 seconds or longer. The color development time is the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, when processed by an automatic developing machine, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leaves the color developer and is bleach-fixed in the next processing step. The total of both the time during which air is conveyed toward the bath (so-called air time) is called color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The water washing or stabilization time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the water washing or stabilizing liquid.
[0108]
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, as a developing agent or a precursor thereof incorporated in the photosensitive material, for example, JP-A-8-234388, JP-A-9-152686, JP-A-9-152893, and JP-A-9-212814. The hydrazine type compounds described in JP-A-9-160193 are preferred.
[0109]
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.
[0110]
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.
[0111]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0112]
Example 1
(Preparation of emulsion BH)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.55 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, potassium bromide (3 mol% per mol of the finished silver halide) and K were added from the time when the addition of silver nitrate was 80% to 90%._Four[Ru (CN)₆] Was added. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.3 mol% per mol of the finished silver halide) was added. The obtained emulsion was desalted and then re-dispersed with gelatin. To this emulsion, sodium benzenethiosulfonate, sensitizing dye A and sensitizing dye B were added, and ripened to be optimal using a gold sulfide colloidal dispersion as a sensitizer. Further 1-phenyl-5-mercaptotetrazole and 1- (5-methylureidophenyl) -5-mercaptotetrazole were added. The emulsion thus obtained was named Emulsion BH.
[0113]
[Chemical 1]

[0114]
(Preparation of emulsion B-L)
Emulsion B-H was prepared by changing only the addition rate of silver nitrate and sodium chloride to prepare a cubic high silver chloride emulsion having a sphere equivalent diameter of 0.45 μm and a coefficient of variation of 10%. The resulting emulsion was designated as Emulsion BL.
[0115]
(Preparation of emulsion G-1)
A cubic high silver chloride emulsion (silver chloride content 95.8 mol%) with a spherical equivalent diameter of 0.40 μm and a coefficient of variation of 10% is obtained by a conventional method in which silver nitrate and sodium chloride are simultaneously added and mixed in a stirred gelatin aqueous solution. Prepared. However, when the addition of silver nitrate is 80% to 90%, K_Four[Ru (CN)₆] Was added. Potassium bromide (4 mol% per mol of finished silver halide) was added from the 80% to 100% addition of silver nitrate. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.2 mol% per mol of finished silver halide) was added. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium benzenethiosulfonate was added to this emulsion, and gold sulfide colloidal dispersion was used as a sensitizer, and ripened to be optimal. Further, sensitizing dye C, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole and potassium bromide were added. The emulsion thus obtained was designated as Emulsion G-1.
[0116]
[Chemical formula 2]

[0117]
(Preparation of emulsion G-2)
Emulsion G-1 refers to the addition of silver nitrate from 92% to 97%.₂[Ir (5-methylthiazole) Cl₅The amount of Ir per mole of the finished silver halide is 5 × 10^-7Emulsions (silver chloride content 95.8 mol%) differing only in the addition of moles were prepared, and this was designated as Emulsion G-2.
[0118]
(Preparation of emulsion G-3)
Emulsion G-1 refers to the addition of silver nitrate from 60% to 80%._Three[RhBr₆] The Rh amount per mole of the finished silver halide is 1 × 10^-8Emulsion (silver chloride content: 95.8 mol%) differing only in the amount to be added was prepared as Emulsion G-3.
[0119]
(Preparation of emulsion G-4)
Emulsion G-1 refers to the addition of silver nitrate from 60% to 80%._Three[RhBr₆The amount of Rh per mole of the finished silver halide is 3 × 10^-8Emulsions (silver chloride content 95.8 mol%) differing only in the amount to be added were prepared as Emulsion G-4.
[0120]
(Preparation of emulsion G-5)
Emulsion G-1 was prepared by changing only the addition rate of silver nitrate and sodium chloride to prepare a cubic high silver chloride emulsion (silver chloride content 95.8 mol%) having a sphere equivalent diameter of 0.35 μm and a coefficient of variation of 10%. . The resulting emulsion was designated as Emulsion G-5.
[0121]
(Preparation of emulsion G-6)
Emulsion G-5 is defined as K K from 92% to 97% addition of silver nitrate.₂[Ir (5-methylthiazole) Cl₅The amount of Ir per mole of the finished silver halide is 1 × 10^-6Emulsions (silver chloride content 95.8 mol%) differing only in the addition of moles were prepared, and this was designated as Emulsion G-6.
[0122]
(Preparation of emulsion G-7)
Emulsion G-5 means that from the point when the addition of silver nitrate is 60% to the point when it is 80%, K_Three[RhBr₆The Rh content per mole of the finished silver halide is 2.7 × 10^-8Emulsion (silver chloride content 95.8 mol%) differing only in the amount added to make a mole was prepared as Emulsion G-7.
[0123]
(Preparation of emulsion G-8)
Emulsion G-1 was prepared by changing only the addition rate of silver nitrate and sodium chloride to prepare a cubic high silver chloride emulsion (silver chloride content 95.8 mol%) having a sphere equivalent diameter of 0.29 μm and a coefficient of variation of 10%. . The resulting emulsion was designated as Emulsion G-8.
[0124]
(Preparation of emulsion G-9)
Emulsion G-8 is defined as K K from the point when the addition of silver nitrate is 60% to 80%._Three[RhBr₆] The Rh amount per mole of the finished silver halide is 8 × 10^-9Emulsion (silver chloride content: 95.8 mol%) differing only in the amount added to make a mole was prepared as Emulsion G-9.
[0125]
(Preparation of emulsion RH)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.35 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 80% to 90%, K_Four[Ru (CN)₆] Was added. Potassium bromide (4.3 mol% per mol of the finished silver halide) was added from the 80% to 100% addition of silver nitrate. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.15 mol% per mol of the finished silver halide) was added. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium benzenethiosulfonate was added to this emulsion, sodium thiosulfate pentahydrate as a sulfur sensitizer, and bis (1,4,5-trimethyl-1,2,4-triazolium-3- Optimal aging with thiolate) aurate (I) tetrafluoroborate. Further, sensitizing dye H, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound I and potassium bromide were added. The emulsion thus obtained was named Emulsion RH.
[0126]
[Chemical Formula 3]

[0127]
[Formula 4]

[0128]
(Preparation of emulsion RL)
Emulsion RH was a cubic high silver chloride emulsion having a sphere equivalent diameter of 0.28 μm and a coefficient of variation of 10% by changing only the addition rate of silver nitrate and sodium chloride. The resulting emulsion was designated as Emulsion RL.
[0129]
In order to examine the sensitivity of emulsions G-1 to G-9, the following samples were prepared.
[0130]
After the corona discharge treatment is applied to the surface of the support formed by coating both sides of the paper with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate is provided. The layers were sequentially coated to prepare a sample of a silver halide color photographic light-sensitive material having the following layer structure. The coating solution for each photographic constituent layer was prepared as follows.
[0131]
First layer coating preparation
57 g of yellow coupler (ExY), 7 g of color image stabilizer (Cpd-1), 4 g of color image stabilizer (Cpd-2), 7 g of color image stabilizer (Cpd-3), 2 g of color image stabilizer (Cpd-8) Is dissolved in 21 g of a solvent (Solv-1) and 80 ml of ethyl acetate, and this liquid is emulsified and dispersed in 220 g of a 23.5% by weight gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate with a high-speed stirring emulsifier (dissolver). 900 g of emulsified dispersion A was prepared by adding water.
On the other hand, the emulsified dispersion A and emulsions BH and BL 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.
[0132]
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.
[0133]
[Chemical formula 5]

[0134]
[Chemical 6]

[0135]
Further, 1-phenyl-5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 1.0 × 10 6 per mole of silver halide.^-3Moles and 5.9 × 10^-FourMole was added. Furthermore, 1-phenyl-5-mercaptotetrazole was added to the second layer, the fourth layer, and the sixth layer, respectively, at 0.2 mg / m 2.²0.2 mg / m²And 0.6 mg / m²It added so that it might become.
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.²Added. 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).
[0136]
[Chemical 7]

[0137]
(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
Polyethylene resin laminated paper
[White pigment (TiO 2 on the first layer side polyethylene resin)₂Content 16% by mass, ZnO; content 4% by mass) and optical brightener (4,4′-bis (5-methylbenzoxazolyl) stilbene, content 0.03% by mass), bluish dye (Including ultramarine)]
First layer (blue sensitive emulsion layer)
Emulsion B-H 0.09
Emulsion BL 0.10
Gelatin 1.00
Yellow coupler (ExY-1) 0.46
Color image stabilizer (Cpd-1) 0.06
Color image stabilizer (Cpd-2) 0.03
Color image stabilizer (Cpd-3) 0.06
Color image stabilizer (Cpd-8) 0.02
Solvent (Solv-1) 0.17
[0138]
Second layer (color mixing prevention layer)
Gelatin 0.50
Color mixing inhibitor (Cpd-4) 0.05
Color image stabilizer (Cpd-5) 0.01
Color image stabilizer (Cpd-6) 0.06
Color image stabilizer (Cpd-7) 0.01
Solvent (Solv-1) 0.03
Solvent (Solv-2) 0.11
[0139]
Third layer (green sensitive emulsion layer)
Emulsion G-1 0.12
Gelatin 1.36
Magenta coupler (ExM) 0.15
Ultraviolet absorber (UV-A) 0.14
Color image stabilizer (Cpd-2) 0.02
Color image stabilizer (Cpd-4) 0.002
Color image stabilizer (Cpd-6) 0.09
Color image stabilizer (Cpd-8) 0.02
Color image stabilizer (Cpd-9) 0.03
Color image stabilizer (Cpd-10) 0.01
Color image stabilizer (Cpd-11) 0.0001
Solvent (Solv-3) 0.11
Solvent (Solv-4) 0.22
Solvent (Solv-5) 0.20
[0140]
Fourth layer (color mixing prevention layer)
Gelatin 0.36
Color mixing inhibitor (Cpd-4) 0.03
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-6) 0.05
Color image stabilizer (Cpd-7) 0.004
Solvent (Solv-1) 0.02
Solvent (Solv-2) 0.08
[0141]
5th layer (red-sensitive emulsion layer)
Emulsion R-H 0.05
Emulsion RL 0.05
Gelatin 1.11
Cyan coupler (ExC-2) 0.13
Cyan coupler (ExC-3) 0.03
Color image stabilizer (Cpd-1) 0.05
Color image stabilizer (Cpd-6) 0.06
Color image stabilizer (Cpd-7) 0.02
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.01
Color image stabilizer (Cpd-14) 0.01
Color image stabilizer (Cpd-15) 0.12
Color image stabilizer (Cpd-16) 0.03
Color image stabilizer (Cpd-17) 0.09
Color image stabilizer (Cpd-18) 0.07
Solvent (Solv-5) 0.15
Solvent (Solv-8) 0.05
[0142]
Sixth layer (UV absorbing layer)
Gelatin 0.46
Ultraviolet absorber (UV-B) 0.45
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.25
Seventh layer (protective layer)
Gelatin 1.00
Acrylic-modified copolymer of polyvinyl alcohol
(Degree of modification 17%) 0.04
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.01
[0143]
[Chemical 8]

[0144]
[Chemical 9]

[0145]
Embedded image

[0146]
Embedded image

[0147]
Embedded image

[0148]
Embedded image

[0149]
Embedded image

[0150]
Embedded image

[0151]
Embedded image

[0152]
Embedded image

[0153]
The sample obtained as described above was designated as Sample 101. In order to examine the sensitivities of emulsions G-1 to G-9, samples 101 and 109 were prepared in the same manner as samples 101 except that the green-sensitive emulsion layers were changed as shown in Table 2.
[0154]
[Table 2]

[0155]
Each coated sample was placed in an atmosphere of 10 ° C. and 30% RH, and the sensitometric 10 was passed through a green filter using a high-illuminance exposure photometer (HIE type manufactured by Yamashita Denso Co., Ltd.).^-4Second high intensity gradation exposure was given. The exposed sample was subjected to the color development processing described below 6 seconds after the exposure.
[0156]
The processing steps are shown below.
[processing]
Continuous processing was performed until the volume of the color developer replenisher used in the following processing steps was 0.5 times the volume of the color developer tank.
[0157]
Processing temperature Temperature Time Replenishment amount^*
Color development 45.0 ℃ 16 seconds 45mL
Bleach fixing 40.0 ℃ 16 seconds 35mL
Rinse (1) 40.0 ° C 8 seconds-
Rinse (2) 40.0 ° C 8 seconds-
Rinse (3) ** 40.0 ° C 8 seconds-
Rinse (4) ** 38.0 ° C 8 sec 121mL
Drying 80.0 ° C 16 seconds
(Note) * Sensitive material 1m²Replenishment amount per
** Mount a phosphorus screening system RC50D (trade name) manufactured by Fuji Photo Film Co., Ltd. on the rinse (3), take out the rinse solution from the rinse (3), and send it to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse (4), and the concentrate is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours per day. The rinsing was a 4-tank countercurrent system from (1) to (4).
[0158]
The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
Water 800mL 600mL
Optical brightening agent (FL-1) 5.0 g 8.5 g
Triisopropanolamine 8.8g 8.8g
Sodium p-toluenesulfonate 20.0 g 20.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.50g
Potassium chloride 10.0 g −
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.50 g 0.50 g
Disodium-N, N-bis (sulfonate
Ethyl) hydroxylamine 8.5 g 14.5 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline
・ 3/2 sulfate ・ Monohydrate 10.0g 22.0g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.35 12.6
[0159]

[0160]
[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL
pH (25 ° C.) 6.5 6.5
[0161]
Embedded image

[0162]
The magenta color density of each sample after treatment was measured, and 10^-4A characteristic curve of second high illumination exposure was obtained. The sensitivity of each emulsion was read from the logarithm of the exposure amount E required to give a color density of 0.7 for each sample. Sensitivity was expressed as logE relative to the sensitivity of Emulsion G-1. A negative value indicates that the sensitivity is low. The results are shown in Table 2. The difference in sensitivity between the emulsions G-1, G-5, and G-8 that do not contain the metal complex corresponding to the general formula (I) or (II) in each size and the sensitivity of the emulsion containing the metal complex is the metal complex. Is the desensitization.
[0163]
  Furthermore, emulsions G-1 to G-8In order to examine the photographic performance by mixing two types of samples, samples 101 and 110 were prepared by changing the green-sensitive emulsion layer emulsion to two types of mixing as shown in Table 3, respectively.1It was. The coating amount in terms of silver of the two types of emulsions was 0.06 (g / m²).
[0164]
In order to examine the photographic characteristics of these samples, the following experiment was conducted.
Each coated sample was placed in an atmosphere of 20 ° C. and 30% RH, and a high-intensity exposure sensitometer (HIE type manufactured by Yamashita Denso Co., Ltd.) was used.^-6Second high intensity gradation exposure was given. The exposed sample was processed with the above color development time of 16 seconds after 6 seconds or 60 seconds of exposure. Similarly exposed samples were processed differently only after changing the color development time to 26 seconds 6 seconds or 60 seconds after exposure. Further, a color developer containing 0.5 ml of bleach-fixing solution per liter of the color developer described above was prepared, and the sample exposed in the same manner was developed with this color developer 6 or 60 seconds after exposure. Processing with a development time of 16 seconds was performed.
[0165]
The magenta color reflection density of each sample after treatment was measured, and 10^-6A characteristic curve of second high illumination exposure was obtained.
Hereinafter, the gradation γ is calculated as (D−0.3) /0.5 by reading the color density D at an exposure amount 0.5 higher by logE from the exposure amount required to give the color density 0.3. For each sample, γ in the case of performing normal color development for 16 seconds after exposure for 6 seconds was calculated. In the case of digital exposure by laser scanning exposure, this value is preferably in the range of 2.2 ± 0.2, and the difference between the calculated γ of each sample and the optimum central gradation 2.2 is the deviation Δγ1 from the optimum gradation. did. A positive value indicates that the tone is harder than the optimum center tone, and a negative value indicates that the tone is soft. The absolute value is preferably within 0.2.
[0166]
For each sample, γ in the case of normal color development for 16 seconds after exposure for 6 seconds and γ in the case of normal color development for 26 seconds after exposure for 6 seconds were read, and the difference between them was Δγ2. A positive value indicates that the development becomes harder by extending the development time. The smaller the absolute value, the more stable and preferable the gradation is even when the processing factor fluctuates. For each sample, γ when normal color development was performed for 16 seconds after exposure for 6 seconds and γ when color development was performed for 16 seconds with bleach-fixing solution mixed after exposure for 6 seconds were read. The difference was designated as Δγ3. A positive value indicates that the tone becomes hard due to the mixing of the bleach-fixing solution. The smaller the absolute value, the more stable and preferable the gradation is due to the mixing of the bleach-fixing solution.
The obtained results are shown in Table 3.
[0167]
[Table 3]

[0168]
  From Table 3, it can be seen that by mixing the emulsion of the present invention, a gradation suitable for digital exposure by laser scanning exposure can be obtained, and that the gradation can be kept stable even when the processing factor varies.. HoweverHowever, although not shown in the table, the gradation fluctuation was stable when color development was started 60 seconds after exposure for any of the samples.
[0193]
【The invention's effect】
The silver halide photographic light-sensitive material of the present invention is suitable for digital exposure by laser scanning exposure, can always obtain stable photographic performance even when subjected to ultra-rapid processing, and is particularly suitable for color printing.

Claims (10)

A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains at least two types of silver chloride having different silver chloride contents of 90 mol% or more. containing emulsions, and I silver halide emulsion der containing at least one at least one of said silver halide emulsion is selected from a metal complex represented by the following general formula (I), (1) the The content per mole of at least one silver halide selected from the metal complexes represented by formula (I) or the average content per silver halide grain is lower than that of the emulsion on the high sensitivity side. The emulsion on the side of the lower side is more sensitive than the emulsion on the side of higher sensitivity, wherein the emulsion on the side is more or (2) at least one selected from the metal complexes represented by formula (I) especially that there is large Silver halide photographic light-sensitive material to be.
Formula (I)
^{_{[IrX I n L I (6}} -n)] m
In which X ^I represents a halogen ion or pseudo-halogen ion (except cyanate ion), L ^I represents any ligand different from X ^I , n represents 3, 4 or 5; m represents the charge of the metal complex and is 5-, 4-, 3-, 2-, 1-, 0, or 1+. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer has at least two types of silver chloride contents having different silver chloride contents of 90 mol% or more. containing emulsions, and I silver halide emulsion der containing at least one at least one of said silver halide emulsion is selected from a metal complex represented by the following general formula (II), (1) the The content per mol of at least one silver halide selected from the metal complexes represented by the general formula (II) or the average content per silver halide grain is lower than that of the emulsion on the high sensitivity side. The emulsion on the side having a higher sensitivity or (2) at least one selected from the metal complex represented by the general formula (II) has a lower sensitivity than an emulsion on the higher sensitivity side. this is great The silver halide photographic material according to claim.
Formula (II)
[MX ^II _n L ^II _(6-n) ] ^m
In the formula, M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, X ^II represents a halogen ion, and L ^II represents an arbitrary ligand different from X ^II. . n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and is 4-, 3-, 2-, 1-, 0 or 1+. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains at least two types of silver chloride having different silver chloride contents of 90 mol% or more. containing emulsion, and at least one of said silver halide emulsion is selected from a metal complex represented by at least one the following general formula selected from the metal complex represented by the following general formula (I) (II) What halide emulsion der containing at least one, (1) content of at least one silver halide per mole selected from the metal complex represented by the general formula (I) or (II) Alternatively, the average content per silver halide grain is higher in the low-sensitivity emulsion than in the high-sensitivity emulsion, or (2) represented by the general formula (I) or (II) metal The silver halide photographic light-sensitive material reduced sensitivity due to at least one selected from the body, characterized in that towards the low sensitivity side emulsion is greater than the emulsion sensitive side.
Formula (I)
^{_{[IrX I n L I (6}} -n)] m
In which X ^I represents a halogen ion or pseudo-halogen ion (except cyanate ion), L ^I represents any ligand different from X ^I , n represents 3, 4 or 5; m represents the charge of the metal complex and is 5-, 4-, 3-, 2-, 1-, 0, or 1+.
Formula (II)
[MX ^II _n L ^II _(6-n) ] ^m
In the formula, M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, X ^II represents a halogen ion, and L ^II represents an arbitrary ligand different from X ^II. . n represents 3, 4, 5 or 6, m represents the charge of the metal complex, and is 4-, 3-, 2-, 1-, 0 or 1+.   In the two types of silver halide emulsions having different sensitivities, the content per mole of at least one silver halide selected from the metal complexes represented by the general formula (I) is higher than that of the emulsion on the high sensitivity side. The silver halide photographic light-sensitive material according to claim 1 or 3, wherein there are more emulsions on the low sensitivity side.   In the two types of silver halide emulsions having different sensitivities, the average content per grain of at least one silver halide grain selected from the metal complexes represented by the general formula (I) is higher on the high sensitivity side. 5. The silver halide photographic light-sensitive material according to claim 1, wherein there are more emulsions on the lower sensitivity side than emulsions.   In the two types of silver halide emulsions having different sensitivities, the desensitization due to at least one selected from the metal complexes represented by the general formula (I) is lower than that of the emulsion on the high sensitivity side. The silver halide photographic light-sensitive material according to claim 1, 3, 4, or 5, wherein the silver halide photographic light-sensitive material is larger.   In the two types of silver halide emulsions having different sensitivities, the content per mole of at least one silver halide selected from the metal complexes represented by the general formula (II) is higher than that of the emulsion on the high sensitivity side. The silver halide photographic light-sensitive material according to claim 2 or 3, wherein there are more emulsions on the low sensitivity side.   In the two types of silver halide emulsions having different sensitivities, the average content per grain of at least one silver halide grain selected from the metal complexes represented by the general formula (II) is higher on the high sensitivity side. 8. The silver halide photographic light-sensitive material according to claim 2, wherein there are more emulsions on the lower sensitivity side than emulsions.   In the two types of silver halide emulsions having different sensitivities, the desensitization due to at least one selected from the metal complexes represented by the general formula (II) is lower than that of the emulsion on the high sensitivity side. The silver halide photographic light-sensitive material according to claim 2, 3, 7, or 8, wherein the silver halide photographic light-sensitive material is larger.   10. The silver halide emulsion according to claim 1, wherein each of the two types of silver halide emulsions having different sensitivities is a silver halide emulsion containing silver halide grains having an equivalent sphere diameter of 0.6 [mu] m or less. The silver halide photographic light-sensitive material described in the item.