JP4181345B2 - Image forming method and silver halide color photographic light-sensitive material - Google Patents

Description

【０１１２】
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ＷＯ−９８／３３７６０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。
【０１１３】
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特許に記載されている例示カプラーが特に好ましい。また、フェノール系、ナフトール系のシアンカプラーも好ましく、例えば、特開平１０−３３３２９７号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。
【０１１４】
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。
【０１１５】
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、該特許の段落番号００１２〜００５９の記載は例示シアンカプラー（１）〜（４７）を含め、本発明にそのまま適用され、
本明細書の一部として好ましく取り込まれる。
【０１１６】
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、該特許の段落番号０００９〜００２６はそのまま本願に適用され、本願の明細書の一部として取り込まれる。これに加えて、欧州特許第８５４３８４号明細書、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。
【０１１７】
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。
【０１１８】
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。
【０１１９】
本発明においては公知の混色防止剤を用いることができるが、その中でも以下に挙げる特許に記載のものが好ましい。
例えば、特開平５−３３３５０１号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。
【０１２０】
本発明においては、紫外線吸収剤としてモル吸光係数の高いトリアジン骨核を有する化合物を用いることが好ましく、例えば、以下の特許に記載の化合物を用いることができる。これらは、感光性層又は／及び非感光性に好ましく添加される。例えば、特開昭４６−３３３５号公報、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。
【０１２１】
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。
【０１２２】
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。
【０１２３】
本発明において、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３．０μｍ〜７．５μｍであることが好ましく、更に３．０μｍ〜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。
【０１２４】
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。
【０１２５】
本発明においては、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。特に、本発明は、迅速処理適性、即ち、像様露光後９秒以下で発色現像を開始し、該発色現像が２８秒以内の発色現像時間で行われることにより画像形成される迅速処理に対する適性を有する。
【０１２６】
本発明においては、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。
【０１２７】
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。
【０１２８】
本発明においては、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。
【０１２９】
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。
【０１３０】
本発明において、感光材料を、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。
【０１３１】
本発明においては、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。
【０１３２】
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特許に詳しく記載されている。
【０１３３】
本発明の感光材料をプリンター露光する際には、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。
【０１３４】
本発明における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特許に記載の化合物が好ましく用いられる。
【０１３５】
本発明の画像形成方法は、特に迅速処理適性を有するハロゲン化銀カラー写真感光材料の画像形成方法であり、前述したハロゲン化銀カラー写真感光材料を使用して像様露光し、該露光後９秒以内で発色現像を開始し、該発色現像が２８秒以内の発色現像時間で行われる。
【０１３６】
本発明において、露光から発色現像の開始までの時間は、９秒以内であるが、好ましくは９秒以下０．１秒以上の範囲内、より好ましくは９秒以下１秒以上の範囲内、更に好ましくは９秒以下２秒以上の範囲内である。
【０１３７】
また、発色現像時間は２８秒以内であるが、好ましくは２８秒以下６秒以上、より好ましくは２５秒以下６秒以上、更に好ましくは２０秒以下６秒以上である。発色現像後は、漂白定着（又は漂白、定着）後、水洗又は安定化工程、乾燥工程を行うのが好ましい。ここで、漂白定着時間としては、好ましくは３０秒以下（好ましくは３０秒以下６秒以上、より好ましくは２５秒以下６秒以上、更に好ましくは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（好ましくは６０秒以下６秒以上、更に好ましくは４０秒以下６秒以上）である。
【０１３８】
なお、本発明において、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。
【０１３９】
本発明は、上記のように潜像時間が短く、かつ迅速処理を行った場合であっても、本発明の目的が効果的に達成される。
【０１４０】
本発明において、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が知られている。しかしながら、本発明においては、従来のアルカリ剤と現像薬（特にｐ−フェニレンジアミン系カラー現像主薬）を含む発色現像液で現像する方法に適用されるものである。また、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にも適用されない。本発明は、インフラが整った既存の現像処理方式において、効果を発現するものである。
【０１４１】
【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。
【０１４２】
実施例１
（乳剤Ｂ−１の調製）
石灰処理ゼラチン３％水溶液１０００ｍｌをｐＨ３．５、ｐＣｌ１．７に調整し、硝酸銀を２．１２モル含む水溶液と塩化ナトリウムを２．２モル含む水溶液を激しく攪拌しながら５０℃で同時に添加混合した。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を、出来上がりのハロゲン化銀１モルあたり３モル％になるように添加した。同じく硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｆｅ（ＣＮ）₆］水溶液を出来上がりのハロゲン化銀１モルあたりＦｅ量が２．５×１０^-5モルになる量を添加した。硝酸銀の添加が８２％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］水溶液を出来上がりのハロゲン化銀１モルあたりＩｒ量が５．３×１０^-8モルになる量を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム水溶液を、出来上がりのハロゲン化銀１モルあたりＩ量が０．２５モル％になるように、及びＫ₂［Ｉｒ（Ｈ₂Ｏ）Ｃｌ₅］水溶液を出来上がりのハロゲン化銀１モル当たりＩｒ量が８．０×１０^-7モルになる量を添加した。４０℃で脱塩処理を施した後、石灰処理ゼラチン１５０ｇを加え、ｐＨ５．５、ｐＣｌ１．９に調整した。得られた粒子は球相当径０．７３μｍ、変動係数８．５％の立方体塩臭沃化銀乳剤であった。
この乳剤を４０℃で溶解し、チオスルフォン酸ナトリウムをハロゲン化銀１モルあたり１．５×１０^-5モル添加し、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６０℃にて最適になるように熟成した。４０℃に降温後、増感色素Ａをハロゲン化銀１モルあたり１．９×１０^-4モル、増感色素Ｂをハロゲン化銀１モルあたり１．０×１０^-4モル、１−フェニル−５−メルカプトテトラゾールをハロゲン化銀１モルあたり２．０×１０^-4モル、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をハロゲン化銀１モルあたり２．０×１０^-4モル、臭化カリウムをハロゲン化銀１モルあたり１．８×１０^-3モル添加した。このようにして得られた乳剤を、乳剤Ｂ−１とした。
【０１４３】
【化１】

【０１４４】
（乳剤Ｂ−２〜Ｂ−４の調製）
乳剤Ｂ−１に対し、同時に添加する硝酸銀と塩化ナトリウムの添加速度を変え、添加するＫ₄［Ｆｅ（ＣＮ）₆］、Ｋ₂［ＩｒＣｌ₆］及びＫ₂［Ｉｒ（Ｈ₂Ｏ）Ｃｌ₅］の量及び脱塩処理後に添加する各種化合物の量を変更する以外は同様にして乳剤Ｂ−２〜Ｂ−４を得た。乳剤Ｂ−２、Ｂ−３及びＢ−４は球相当径が各々０．６８μｍ、０．３３μｍ及び０．２７μｍ、変動係数が各々８．３％、９．５％及び１０．３％の立方体塩臭沃化銀乳剤であった。
【０１４５】
（乳剤Ｇ−１の調製）
乳剤Ｂ−１に対し、同時に添加する硝酸銀と塩化ナトリウムの添加速度及び温度を変え、Ｋ₄［Ｆｅ（ＣＮ）₆］水溶液を硝酸銀の添加が７５％の時点から９０％の時点にかけて添加するように変更し、Ｋ₂［ＩｒＣｌ₆］水溶液を硝酸銀の添加が７７％の時点から８８％の時点にかけて添加するよう変更し、更に添加するＫ₄［Ｆｅ（ＣＮ）₆］、Ｋ₂［ＩｒＣｌ₆］及びＫ₂［Ｉｒ（Ｈ₂Ｏ）Ｃｌ₅］の量を変更し、４０℃で脱塩処理を施した後、石灰ゼラチン１５０ｇを加え、ｐＨ５．５、ｐＣｌ１．９に調整した。得られた粒子の球相当径は０．４４μｍ、変動係数９．３％の立方体塩臭沃化銀乳剤であった。
この乳剤を４０℃で溶解し、チオスルフォン酸ナトリウムをハロゲン化銀１モルあたり１．５×１０^-5モル添加し、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６０℃にて最適になるように熟成した。４０℃に降温後、増感色素Ｃをハロゲン化銀１モルあたり７．２×１０^-4モル、１−フェニル−５−メルカプトテトラゾールをハロゲン化銀１モルあたり２．２×１０^-4モル、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をハロゲン化銀１モルあたり９×１０^-4モル、臭化カリウムをハロゲン化銀１モルあたり８×１０^-3モル添加した。このようにして得られた乳剤を、乳剤Ｇ−１とした。
【０１４６】
【化２】

【０１４７】
（乳剤Ｇ−２〜Ｇ−４の調製）
乳剤Ｇ−１に対し、同時に添加する硝酸銀と塩化ナトリウムの添加速度を変え、添加するＫ₄［Ｆｅ（ＣＮ）₆］、Ｋ₂［ＩｒＣｌ₆］及びＫ₂［Ｉｒ（Ｈ₂Ｏ）Ｃｌ₅］の量及び脱塩処理後に添加する各種化合物の量を変更する以外は同様にして乳剤Ｇ−２〜Ｇ−４を得た。乳剤Ｇ−２、Ｇ−３及びＧ−４は球相当径が各々０．３９μｍ、０．２２μｍ及び０．１９μｍ、変動係数が各々９．０％、１２．５％及び１１．０％の立方体塩臭沃化銀乳剤であった。
【０１４８】
（乳剤Ｒ−１〜Ｒ−４の調製）
乳剤Ｇ−１〜Ｇ−４に対し、増感色素Ｃの代わりに下記増感色素Ｈ及び化合物Ｉを用い、増感色素及び化合物Ｉの量を変更する以外は同様にして、乳剤Ｒ−１〜Ｒ−４を得た。乳剤Ｒ−１、Ｒ−２、Ｒ−３及びＲ−４は球相当径が各々０．４３μｍ、０．３８μｍ、０．２３μｍ及び０．１８μｍ、変動係数が各々９．７％、９．１％、１１．８％及び１２．５％の立方体塩臭沃化銀乳剤であった。
【０１４９】
【化３】

【０１５０】
【化４】

【０１５１】
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。
【０１５２】
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−１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。
【０１５３】
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。
【０１５４】
【化５】

【０１５５】
【化６】

【０１５６】
また、緑感性乳剤層及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モル及び５．９×１０^-4モル添加した。さらに、第二層、第四層及び第六層にも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及び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、第四層及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。
【０１５７】
【化７】

【０１５８】
（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（イエロー画像形成青感性乳剤層）
乳剤Ｂ−１ ０．２４
ゼラチン １．０８
イエローカプラー（ＥｘＹ） 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
【０１５９】
第二層（混色防止層）
ゼラチン ０．５５
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
【０１６０】
第三層（マゼンタ画像形成緑感性乳剤層）
乳剤Ｇ−１ ０．１５
ゼラチン １．４２
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
【０１６１】
第四層（混色防止層）
ゼラチン ０．４０
混色防止層（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
【０１６２】
第五層（シアン画像形成赤感性乳剤層）
乳剤Ｒ−１ ０．１３
ゼラチン １．２０
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
【０１６３】
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
【０１６４】
【化８】

【０１６５】
【化９】

【０１６６】
【化１０】

【０１６７】
【化１１】

【０１６８】
【化１２】

【０１６９】
【化１３】

【０１７０】
【化１４】

【０１７１】
【化１５】

【０１７２】
【化１６】

【０１７３】
【化１７】

【０１７６】
試料１０１のデジタル露光及び処理方式による迅速化適性を調べるために以下のような実験を行った。
露光光源としては、波長約４４０ｎｍの青色半導体レーザー（２００１年３月第４８回応用物理学会関係連合講演会で日亜化学（株）発表）、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の緑色レーザー及び波長約６５０ｎｍの赤色半導体レーザー（日立タイプＮｏ．ＨＬ６５０１ＧＭ）を用いた。３色のそれぞれのレーザー光はポリゴンミラーにより走査方向に対して垂直方向に移動し、試料上に、順次走査露光できるようにした。半導体レーザーの温度による光量変動は、ペルチェ素子を利用して温度が一定に保たれることで抑えられている。実効的なビーム径は、８０μｍで、走査ピッチは４２．３μｍ（６００ｄｐｉ）であり、１画素あたりの平均露光時間は、１．７×１０^-7秒であった。この露光方式により、縦１２ｃｍ×横８．９ｃｍサイズの試料にイエロー、マゼンタ、シアンの発色濃度がおおよそ同等になるようなグレー発色の階調露光を与えた後、試料を自動搬送して以下に示す発色現像処理Ａ及びＢを行った。
【０１７７】
［処理Ａ］
試料１０１を、下記処理工程にてカラー現像タンク容量の２倍補充するまで、連続処理（ランニングテスト）を行った。

＊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をリンス３に装着し、リンス３からリンス液を取り出し、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。なお、リンスは１から４へのタンク向流方式とした。
【０１７８】
各処理液の組成は以下の通りである。

【０１７９】

【０１８０】

【０１８１】
以下に処理工程Ｂを示す。
［処理Ｂ］
試料１０１を、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（ランニングテスト）を行った。
【０１８２】
処理工程 温度 時間 補充量^*
発色現像 ４２．０℃ ２７秒 ４５ｍＬ
なお、漂白定着工程以降は各工程の処理液の組成、温度、時間及び補充量を含めて処理Ａと同様である。
＊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。
【０１８３】
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） ４．０ｇ ６．８ｇ
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 ８．０ｇ −
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 ７．５ｇ １６．５ｇ
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
【０１８４】
【化１８】

【０１８５】
＜評価＞
試料１０１の写真特性を調べるために以下のような実験を行った。
なお、試料を露光してから処理液に入るまでの時間については、露光後の試料の搬送速度を変えることにより、６０秒後、９秒後、あるいは３秒後に設定した。
【０１８６】
−発色濃度−
処理後の各試料のイエロー、マゼンタ及びシアン濃度を測定し、特性曲線を得た。発色濃度０．７を与える露光量（Ｅ１）を各試料について求めた。また、Ｅ１の１０倍の露光量（Ｅ２）における発色濃度（Ｄ２）を各試料において求めた。処理Ａ及び処理Ｂの各々の処理において、発色現像液１０００ｍＬ当たり、漂白定着液を０．３ｍＬ添加して同様の露光及び処理を行い、先ほど求めた露光量（Ｅ１）に対応する発色濃度（Ｄ１）を求めた。発色現像液に漂白定着液が入った場合の濃度変化（（Ｄ１）−０．７）の値を求めた。この値が小さいほど処理安定性が良いことを示す。
【０１８７】
−筋状むら−
デジタルカメラで記録されたデジタル情報を用いて、各試料に前記デジタル露光装置による露光、前記処理Ａ又は処理Ｂを行いカラープリントを作製した。露光してから処理液に入るまでの時間を前記と同様にして、６０秒後、９秒後、あるいは３秒後に設定した。各条件ごとにカラープリントを１０枚ずつ作製し、目視により筋状のむらを観察し、以下のように評価した。
Ａ 筋状のむらはほとんどなく非常に良好である。
Ｂ 筋状のむらがわずかに見える試料が１０枚中１〜３枚ある。
Ｃ 筋状のむらがはっきりと見える試料が１０枚中１〜３枚あり、カラープリント品質として劣る。
Ｄ ほとんどの試料にすじ状のむらがはっきりと見え、カラープリント品質として許容できない。
【０１９２】
試料１０１に対し、第一層中の乳剤Ｂ−１を、Ｂ−２とＢ−３をブレンドしたもの（ハロゲン化銀量当たりＢ−２対Ｂ−３が４対６）に変更し、第三層中の乳剤Ｇ−１を、Ｇ−２とＧ−３をブレンドしたもの（ハロゲン化銀量当たりＧ−２対Ｇ−３が３対７）に変更し、かつ第五層中の乳剤Ｒ−１を、Ｒ−２とＲ−３をブレンドしたもの（ハロゲン化銀量当たりＲ−２対Ｒ−３が７対３）に変更した以外は同様にして試料２０１を作製した。試料２０１に対して、ゼラチン及び銀塗設量を表５のように変えた試料２０２及び２０３を、また試料１０１に対してゼラチン及び銀塗設量を表５のように変更した試料２０４を作製した。
【０１９３】
【表５】

【０１９４】
表５に示した試料について、処理工程を下記の処理Ｃに変更する以外は露光方法、露光から発色現像までの時間及び評価方法を上述の試料１０１と同様にして実験を行った。
【０１９５】
以下に処理工程を示す。
［処理Ｃ］
試料２０１〜２０４、及び１０１について、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。
【０１９６】
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
＊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。
【０１９７】
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
【０１９８】

【０１９９】
[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
【０２００】
【化１９】

【０２０１】
以上の結果を表６に示す。
【表６】

【０２０２】
表６の結果から明らかなように、本発明の粒子サイズのハロゲン化銀乳剤を含む試料２０３は、発色現像時間の短い処理Ｃにおいても露光から発色現像までの時間が短い場合に良好な性能を示すことがわかる。
試料に塗設するゼラチン量及び銀量を減量した場合にも良好な性能が示されており、コストを低減できる点で有用であることが分かる。
さらに、含まれるハロゲン化銀乳剤の粒子サイズが本発明の範囲外である試料１０１及び２０４においては前述の効果がないことから、ハロゲン化銀乳剤の粒子サイズを、本発明の範囲とすることで特異的に良好な性能を示すことが明らかである。
【０２０３】
【発明の効果】
本発明によれば、超迅速処理を行った場合であっても、高品質で常に安定した性能が得られるハロゲン化銀カラー写真感光材料及び画像形成方法、特にカラープリントに適したハロゲン化銀カラー写真感光材料及び画像形成方法を提供することことができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an image forming method and a silver halide color photographic light-sensitive material. More specifically, the present invention relates to an image forming method using a silver halide color photographic light-sensitive material suitable for ultra-rapid processing and capable of always obtaining high quality and stable performance. And a silver halide color photographic light-sensitive material.
[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]
To enable one-stop service for color printing using color photographic paper, various methods such as shortening the exposure time, shortening the so-called latent image time from exposure to processing start, shortening the time from processing to drying, etc. Consideration from various viewpoints is necessary, and proposals have been made from various viewpoints.
Among these, the time required for exposure of one print is very short compared to the other, and it is hardly a problem in the case of a normal printer capability used at a store. 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.
In addition to improving productivity, the stability of color print quality is also important. In general, the quality of prints changes with rapid processing, so it is important to design color photographic paper suitable for rapid processing.
[0005]
In the digital exposure method, since the exposure time per pixel is short and the exposure illuminance is high, it is important to improve the silver halide emulsion performance with a high silver chloride content under high illumination exposure. 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 localized phase having a high silver bromide content is provided and doped with an Ir complex to solve the latent image sensitization problem. Yes.
In addition, each specification of US Pat. Nos. 5,360,712, 5,457,021, and 5,462,849 contains a metal complex containing a specific organic ligand as a ligand. It is disclosed that reciprocity failure can be reduced by making it.
U.S. Patent Nos. 5,372,926, 5,255,630, 5,255,451, 5,597,686, 5,480,771, Nos. 474,888, 5,500,335, 5,783,373 and 5,783,378 include Ir complexes and metal complexes containing NO as a ligand. It is disclosed that performance such as reciprocity characteristics of high silver chloride emulsions can be improved by combination. JP-A-2000-250156, 2001-92066, and 2002-31866 disclose emulsion techniques having excellent latent image stability after exposure using a combination of an Ir complex and an Rh complex.
[0006]
U.S. Pat. Nos. 5,726,005 and 5,736,310 disclose high sensitivity and high illuminance failure by an emulsion containing I having a concentration maximum on the subsurface of a high silver chloride emulsion. It is disclosed that an emulsion having a small amount 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. In the examples of JP-A-2000-250178, a silver halide light-sensitive material in which a high silver chloride emulsion contains a periodic group VIII metal ion and the gelatin coating amount is reduced is subjected to short-term color development. It is disclosed that rapid processability, residual color and sharpness are improved.
[0007]
However, when the present inventors examined processing of a color photographic paper with a short latent image time after scanning exposure for the above purpose, streaky irregularities were produced. It has been found that such streak unevenness can be improved by reducing the emulsion grain size, but the resulting printed image density variation may increase. The variation in print image density is caused by slight mixing of the bleach-fixing solution in the color developer, and such contamination can occur in an actual color printing laboratory and needs to be improved. Further, when a combination of color development processing for a shorter time was examined, there was a problem that the color density was further lowered.
[0008]
Further, the above-mentioned known technique does not specifically discuss improvement of photographic characteristics when short color image development is performed for a short latent image time.
[0009]
[Problems to be solved by the invention]
An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention provides a silver halide color photographic light-sensitive material and an image forming method capable of always obtaining high-quality and stable performance even when ultra-rapid processing is performed, particularly a silver halide color suitable for color printing. An object is to provide a photographic material and an image forming method.
[0010]
[Means for Solving the Problems]
Means for solving the above problems are as follows.
[0011]
  <1> A yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer, and a non-photosensitive hydrophilic colloid layer on a support. A silver halide color photographic light-sensitive material provided with photographic constituent layers each having at least one layer is an image forming method for color development after imagewise exposure,
  All the silver halide emulsions in the yellow dye-forming coupler-containing silver halide emulsion layer have an average sphere equivalent diameter of 0.70 μm to 0.30 μm and a variation coefficient of the equivalent sphere diameter of 20 %, And a silver halide emulsion comprising cubic or tetradecahedral silver halide grains having {100} faces, and at least one layer of the silver halide emulsion layer containing the yellow, magenta, and cyan dye-forming coupler, Including silver halide grains having a silver chloride content of 90 mol% or more,The total silver coating amount in the photographic composition layer is 0.41 g / m. ² ~ 0.20g / m ² And
  Color development is started within 9 seconds after the exposure,
  The color development is performed with a color development time of 28 seconds or less.UThis is an image forming method.
[0012]
  <2> Magenta dye-forming coupler-containing silver halide emulsion layerAll the silver halide emulsions inThe average spherical equivalent diameter of silver halide grains is,0.40 μm to 0.20 μmThus, a silver halide emulsion comprising cubic or tetradecahedral silver halide grains having a sphere equivalent diameter variation coefficient of 20% or less and having {100} facesThe image forming method as described in <1> above, wherein
[0013]
  <3> SaidAll of the silver halide emulsions in the cyan dye-forming coupler-containing silver halide emulsion layer have an average equivalent sphere diameter of silver halide grains of 0.40 μm to 0.20 μm and a variation coefficient of the equivalent sphere diameter of 20 % Or less and a silver halide emulsion comprising cubic or tetradecahedral silver halide grains having {100} faces <1> or <2>The image forming method described in 1.
[0014]
  <4> saidAt least one of the silver halide emulsion layers has a silver chloride content of 90 mol% or more, and the silver iodide-containing phase is any of 85% to 100% of the grain volume as measured from the inside of the silver halide grains. Any one of <1> to <3>, comprising a silver halide emulsion composed of cubic or tetradecahedral silver halide grains having {100} planes arranged in a layer at such a position TermThe image forming method described in 1.
[0015]
  <5> The silver halide emulsionHas a silver bromide-containing phase inside the silver iodide-containing phase <4>The image forming method described in 1.
[0016]
  <6><4> or <5>, wherein the silver halide emulsion contains a compound represented by the following general formula (I).
  Formula (I)
    [IrX ^I _n L ^I _(6-n) ] ^m
In general formula (I), X ^I Represents a halogen ion or a pseudohalogen ion. L ^I X ^I Represents an arbitrary ligand different from. n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0 or 1+.
[0017]
  <7> Said<6> The image forming method according to <6>, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (IA) or (IB).
  Formula (IA)
[IrX ^IA _n L ^IA _{( 6- n)} ] ^m
In general formula (IA), X ^IA Represents a halogen ion or a pseudohalogen ion. L ^IA X ^IA Represents any inorganic ligand different from. n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0 or 1+.
  Formula (IB)
    [IrX ^IB _n L ^IB _(6-n) ] ^m
In general formula (IB), X ^IB Represents a halogen ion or a pseudohalogen ion. L ^IB Represents a ligand in which a chain or cyclic hydrocarbon is used as a parent structure, or a carbon atom or hydrogen atom in a part of the parent structure is replaced with another atom or atomic group. n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0 or 1+.
[0018]
  <8> SaidL in the general formula (IA) ^IA Is water, L in the general formula (IB) ^IB 8 is a 5-membered ring ligand containing at least one nitrogen atom and at least one sulfur atom as ring skeleton-forming atoms.It is.
[0019]
  <9> saidThe compound represented by the general formula (I) is a compound represented by the general formula (IA), and L in the general formula (IA) ^IA <7>, wherein the image forming method is water.It is.
[0020]
  <10> said<7>-<9> The image forming method according to any one of <7> to <9>, wherein the silver iodide-containing phase contains a compound represented by the general formula (IA) or (IB)It is.
[0021]
  <11> At least one of the silver halide emulsion layers<1> to <10>, wherein the silver halide emulsion of (1) to (10) has a silver bromide-containing phase containing an iridium hexacoordination complex in which all six ligands are Cl, Br or I only. The image forming method according to claim 1It is.
[0022]
  <12> The image forming method described in any one of <4> to <11>, wherein the silver halide emulsion is a yellow dye-forming coupler-containing silver halide emulsion.
<13> The image forming method according to any one of <4> to <12>, wherein the silver halide emulsion is a silver halide emulsion containing a magenta dye-forming coupler.
<14> The image forming method according to any one of <4> to <13>, wherein the silver halide emulsion is a cyan dye-forming coupler-containing silver halide emulsion.
[0023]
  <15> Any one of <1> to <14>, wherein the silver halide emulsion in any one of the silver halide emulsion layers comprises a gold (I) compound having an organic ligand. The image forming method according to claim 1.
[0024]
  <16> The image forming method according to claim 15, wherein the gold (I) compound having the organic ligand is a bisgold (I) mesoionic heterocycle.
[0025]
  <17> Each of the silver halide emulsion layers contains at least two monodispersed emulsions having a coefficient of variation of the equivalent sphere diameter of silver halide grains of 20% or less. <1> to <16> The image forming method according to any one of the above.
[0026]
  <18> The total gelatin coating amount in the photographic composition layer is 6.0 g / m.²~ 3.0 g / m²The image forming method according to any one of <1> to <17>, wherein.
[0027]
  <19> The blue light exposure is performed with a blue semiconductor laser having a wavelength of 430 to 450 nm. <1> to <18The image forming method according to any one of the above.
[0028]
  <20> A silver halide color photographic light-sensitive material for rapid processing which starts color development within 9 seconds after exposure and forms an image by performing the color development within a color development time of within 28 seconds,
  The silver halide color photographic light-sensitive material comprises, on a support, a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer, and a non-photosensitive material. Provided with a photographic composition layer each having at least one photosensitive hydrophilic colloid layer,
  All the silver halide emulsions in the yellow dye-forming coupler-containing silver halide emulsion layer have an average sphere equivalent diameter of 0.70 μm to 0.30 μm and a variation coefficient of the equivalent sphere diameter of 20 %, And a silver halide emulsion comprising cubic or tetradecahedral silver halide grains having {100} faces,
  At least one of the yellow, magenta and cyan dye-forming coupler-containing silver halide emulsion layers contains silver halide grains having a silver chloride content of 90 mol% or more.The total silver coating amount in the photographic composition layer is 0.41 g / m. ² ~ 0.20g / m ² IsThis is a silver halide color photographic light-sensitive material.
[0029]
DETAILED DESCRIPTION OF THE INVENTION
The image forming method using the silver halide color photographic light-sensitive material of the present invention and the silver halide color photographic light-sensitive material will be described in detail below.
First, the silver halide color photographic light-sensitive material of the present invention (hereinafter referred to as “photosensitive material” as appropriate) will be described.
[0030]
[Silver halide color photographic material]
  The silver halide color photographic light-sensitive material of the present invention is a rapid processing silver halide which starts color development within 9 seconds after exposure and forms an image by performing the color development within a color development time of 28 seconds or less. A color photographic material,
  The silver halide color photographic light-sensitive material comprises, on a support, a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer, and a non-photosensitive material. Provided with a photographic composition layer each having at least one photosensitive hydrophilic colloid layer,
  All the silver halide emulsions in the yellow dye-forming coupler-containing silver halide emulsion layer have an average sphere equivalent diameter of 0.70 μm to 0.30 μm and a variation coefficient of the equivalent sphere diameter of 20 %, And a silver halide emulsion comprising cubic or tetradecahedral silver halide grains having {100} faces,
  At least one of the yellow, magenta and cyan dye-forming coupler-containing silver halide emulsion layers contains silver halide grains having a silver chloride content of 90 mol% or more.The total silver coating amount in the photographic composition layer is 0.41 g / m. ² ~ 0.20g / m ² IsIt is characterized by that.
[0031]
In the present invention, the yellow dye-forming coupler-containing silver halide emulsion layer is a yellow coloring layer (yellow image forming layer), and the magenta dye-forming coupler-containing silver halide emulsion layer is a magenta coloring layer (magenta image forming layer). The cyan dye-forming-plurer-containing silver halide emulsion layer functions as a cyan coloring layer (cyan image-forming layer).
As silver halide emulsions contained in the yellow coloring layer, the magenta coloring layer, and the cyan coloring layer, respectively, with respect to light in different wavelength regions (for example, light in a blue region, a green region, and a red region), It preferably has photosensitivity.
[0032]
The light-sensitive material of the present invention needs to have at least one non-photosensitive hydrophilic colloid layer together with the yellow, magenta, and cyan dye-forming coupler-containing silver halide emulsion layers. The antihalation layer, the intermediate layer, the colored layer, and the like are selected as desired.
[0033]
  The silver halide emulsion in the invention will be described.
  The silver halide emulsion used in the present invention contains the specific silver halide grains described below. The grain shape of the silver halide grains in the present invention is not particularly limited, but is substantially a cubic or tetradecahedral crystal grain having {100} faces (these grains have rounded vertices and higher order faces. May be included), octahedral crystal grains, and the main surface is preferably composed of tabular grains having an aspect ratio of 3 or more and comprising {100} faces or {111} faces. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle. The silver halide grains in the present invention are more preferably cubic, tetrahedral grains or tabular grains having an aspect ratio of 3 or more.
  In the present invention, the silver halide emulsion in the yellow dye-forming coupler-containing silver halide emulsion layer is a cube or tetrahedron having silver halide grains having {100} faces.
[0034]
As the silver halide emulsion used in the present invention, an emulsion containing silver halide grains having a specific silver halide content is used as described above. The silver chloride content needs to be 90 mol% or more, and is preferably 93 mol% or more, and more preferably 95 mol% or more from the viewpoint of rapid processability.
The silver bromide content is preferably from 0.1 to 7 mol%, more preferably from 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 to 1 mol%, more preferably 0.05 to 0.50 mol%, more preferably 0.07 to 0.40 mol% is most preferred.
The silver halide grains contained in the silver halide emulsion used in the present invention are preferably silver iodobromochloride grains, and more preferably silver iodobromochloride grains having the above halogen composition. Moreover, it is preferable that the silver halide grains in all the image forming layers are silver halide grains having the specific halogen composition.
[0035]
The silver halide grains in the silver halide emulsion used in 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 site 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 preferable to have a contained phase of
[0036]
It is important that the silver bromide-containing phase or the silver iodide-containing phase of the silver halide emulsion used in 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.
[0037]
In the present invention, when the silver halide emulsion 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 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.
[0038]
In the present invention, the silver halide emulsion 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.
[0039]
The silver bromide content or silver iodide content necessary for exhibiting the effects of the present invention increases as the silver bromide-containing phase or silver iodide-containing phase is formed inside the grain, and more than necessary. There is a risk that the silver chloride content is reduced and the rapid processability is 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.
[0040]
In the present invention, the introduction of bromide or iodide ions to contain silver bromide or silver iodide in the silver halide emulsion may be carried out by adding a bromide salt or iodide salt solution alone, or A bromide salt or iodide salt solution may be added together with the addition of the high chloride salt solution. In the latter case, the bromide salt or iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of bromide salt, 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 an iodide salt. Alternatively, it can 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.
[0041]
The addition of the bromide salt or iodide salt solution may be concentrated during a period 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%.
[0042]
The distribution of bromide or iodide ion concentration in the depth direction in the grains is determined 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 be measured. 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 according to 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 decreases 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.
[0043]
As the silver halide emulsion used in the present invention, an emulsion containing silver halide grains having a specific average sphere equivalent diameter is used in order to maintain the color density in rapid processing and to improve streak unevenness. In particular, in the case of a silver halide emulsion layer containing a yellow dye-forming coupler, the silver halide grains in the emulsion layer must be 0.70 μm to 0.30 μm, and 0.68 μm to 0.32 μm. Preferably there is.
In the case of a silver halide emulsion layer containing a magenta dye-forming coupler and a silver halide emulsion layer containing a cyan dye-forming coupler, the average sphere equivalent diameter of silver halide grains in the emulsion layer is 0.40 μm to 0. It is preferably 20 μm, more preferably 0.38 μm to 0.22 μm.
[0044]
In this specification, the sphere equivalent 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. The 4 μm particles correspond to cubic particles having a side length of about 0.32 μm, and the sphere equivalent diameter of 0.3 μm corresponds to cubic particles having a side length of about 0.24 μm.
The average equivalent sphere diameter is the average sphere equivalent diameter of all silver halide grains contained in the silver halide emulsion of the present invention.
[0045]
  The silver halide grains contained in the silver halide emulsion used in the present invention are preferably composed of grains having a monodisperse grain size distribution. The variation number of sphere equivalent diameters of all silver halide grains contained in the silver halide emulsion of the present invention is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. preferable. 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, the above monodispersed emulsion is blended and used in the same layer for the purpose of obtaining a wide latitude, or a monodispersed emulsion in which a plurality of yellow, magenta or cyan image forming layers are provided and each layer has a different equivalent sphere diameter. It is also preferable to carry out multilayer coating using each of these.
  In the present invention, the silver halide emulsions in the yellow dye-forming coupler-containing silver halide emulsion layer are all silver halide emulsions having a sphere equivalent diameter variation coefficient of 20% or less and a {100} plane. A silver halide emulsion comprising cubic or tetradecahedral silver halide grains having
[0046]
The halogenated emulsion used in the present invention may contain silver halide grains other than the silver halide grains defined in the present invention (that is, specific silver halide grains). However, in the silver halide grains defined in the present invention, 50% or more of the total projected area of all silver halide grains is preferably silver halide grains defined in the present invention, and 80% or more. Is more preferable, and it is still more preferable that it is 90% or more.
[0047]
In the present invention, the total gelatin coating amount in the photographic composition layer is 6.0 g / m.²~ 3.0 g / m²It is preferable in that the effect of the present invention is effectively exhibited, and 5.5 g / m.²~ 3.5g / m²More preferably.
[0048]
  In the present invention, the total silver coating amount in the photographic composition layer is:0.41g / m²~ 0.20g / m²InBut,0.41g / m²~ 0.24g / m²BePreferGood.
[0049]
The electron release time of the silver halide grains contained in the silver halide emulsion used in the present invention is 10^-FiveIt is preferably between 10 seconds. Here, the electron slow release time is the time until photoelectrons generated in a silver halide crystal are captured by an electron trap in the crystal and emitted again when the silver halide emulsion is exposed. . Electronic sustained release time is 10^-FiveIf it is shorter than 2 seconds, it is difficult to obtain a high-sensitivity and high-contrast gradation in high-illuminance exposure. Electron sustained release time is 10^-FourMore preferably between 10 seconds and 10 seconds.^-3Most preferred is between 1 second and 1 second.
[0050]
The electron sustained release time can be measured by a double pulse photoconduction method. Using a microwave photoconductive method or a radio wave photoconductive method, a first short-time exposure is given, and after a certain time, a second short-time exposure is given. Electrons are trapped in the electron trap in the silver halide crystal by the first exposure, and if the second exposure is applied immediately after that, the electron trap is clogged, so that the second photoconductive signal is increased. When the interval between the two exposures is sufficiently set and the electrons captured by the electron trap in the first exposure have already been emitted, the second photoconductive signal has almost returned to its original size. If the exposure interval dependency of the second photoconductive signal intensity is changed by changing the two exposure intervals, it can be measured how the second photoconductive signal intensity decreases with the exposure interval. This represents the sustained release time of photoelectrons from the electron trap. Although the sustained release of electrons may continue to occur continuously for a certain period of time after exposure,^-FiveIt is preferred that sustained release is observed between 1 second and 10 seconds. 10^-FourMore preferably, sustained release is observed between 10 seconds and 10 seconds.^-3More preferably, sustained release is observed between 1 second and 1 second.
[0051]
The silver halide emulsion used in the present invention preferably contains a compound represented by the following general formula (I) (hereinafter also referred to as a metal complex).
Formula (I)
[IrX^I _nL^I _(6-n)]^m
In general formula (I), X^IRepresents a halogen ion or a pseudohalogen ion. L^IX^IRepresents an arbitrary ligand different from. n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0 or 1+.
[0052]
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)_Three ^-), Cyanate ion (OCN)^-), Thunderate ion (ONC)^-), Azide ion (N_Three ^-) And the like.
[0053]
X^IPreferred are fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, isocyanate ion, thiocyanate ion, hydroxide ion, nitrate ion, nitrite ion, or azide ion. Of these, chloride ions and bromide ions are particularly preferable. 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.
[0054]
Among the metal complexes represented by the general formula (I), a metal complex represented by the following general formula (IA) or (IB) is preferable, and a metal complex represented by the following general formula (IB) is more preferable. .
Formula (IA)
[IrX^IA _nL^IA _(6-n)]^m
In general formula (IA), X^IARepresents a halogen ion or a pseudohalogen ion. L^IAX^IARepresents any inorganic ligand different from. n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0 or 1+.
X^IAThe halogen ion or pseudo-halogen ion represented by the formula:^IIs the same.
L^IAAs preferred, water, OCN, ammonia, phosphine and carbonyl are preferred, and water is particularly preferred.
[0055]
Formula (IB)
[IrX^IB _nL^IB _(6-n)]^m
In general formula (IB), X^IBRepresents a halogen ion or a pseudohalogen ion. L^IBRepresents a ligand in which a chain or cyclic hydrocarbon is used as a parent structure, or a carbon atom or hydrogen atom in a part of the parent structure is replaced with another atom or atomic group. n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0 or 1+.
[0056]
X^IBThe halogen ion or pseudo-halogen ion represented by the formula:^IIs the same.
L^IBRepresents a ligand in which a chain or cyclic hydrocarbon is a base structure, or a carbon or hydrogen atom in a part of the base structure is replaced with another atom or atomic group, but a cyanide ion Is not included. L^IBIs preferably a heterocyclic compound.
The metal complex represented by the general formula (IB) is more preferably a metal complex having a five-membered ring compound as a ligand, and among the five-membered ring compounds, at least one nitrogen atom and at least one sulfur atom are included. More preferably, it is a compound contained in a 5-membered ring skeleton.
[0057]
Among the metal complexes represented by the general formula (IB), a preferable compound can be represented by the following general formula (IC).
General formula (IC)
General formula (IC)
[IrX^{I c} _nL^{I c} _(6-n)]^m
In general formula (IC), X^{I c}Represents a halogen ion or a pseudohalogen ion. L^{I c}Represents a ligand comprising at least one nitrogen atom and at least one sulfur atom as a skeleton-forming atom of the 5-membered ring, and in the 5-membered ring skeleton, An arbitrary substituent may be present on the carbon atom. n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0 or 1+.
[0058]
X^{I c}The halogen ion or pseudohalogen ion represented by X is X in the general formula (I).^IIs the same.
L^{I c}In the five-membered ring ligand represented by the formula (1), the substituent on the carbon atom in the five-membered ring skeleton is preferably a substituent having a smaller volume than the n-propyl group. Examples of the substituent include an alkyl group (preferably methyl, ethyl), an alkoxy group (preferably methoxy, ethoxy), a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a formyl group, a thioformyl group, Hydroxy group, mercapto group, amino group, hydrazino group, azide group, nitro group, nitroso group, hydroxyamino group, carboxyl group, carbamoyl group, fluorine atom, chlorine atom, bromine atom and iodine atom are preferred.
[0059]
Among the metal complexes represented by the general formula (IC), a metal complex represented by the following general formula (ID) is more preferable.
General formula (ID)
[IrX^ID _nL^ID _(6-n)]^m
X in the general formula (ID)^IDRepresents a halogen ion or a pseudo-halogen ion. L^IDRepresents a ligand comprising at least two nitrogen atoms and at least one sulfur atom as a skeleton-forming atom of the 5-membered ring, An arbitrary substituent may be present on the carbon atom. n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0 or 1+.
[0060]
X^IDThe halogen ion or pseudo-halogen ion represented by the formula:^IIs the same.
L^IDIs preferably a compound having a thiadiazole as a skeleton, and a substituent other than hydrogen is preferably bonded to a carbon atom in the compound. The substituent is preferably a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group (preferably methoxy, ethoxy), carboxyl group, alkoxycarbonyl group (preferably methoxycarboxyl), acyl group ( Preferably acetyl, chloroformyl), mercapto group, alkylthio group (preferably methylthio), thioformyl group, thiocarboxy group, dithiocarboxy group, sulfino group, sulfo group, sulfamoyl group, alkylamino group (preferably methylamino), 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, Preferably, a halogen atom, chloroformyl group, sulfino group, a sulfo group, a sulfamoyl group, an isocyano group, a cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, hydroxyimino group, nitroso group, nitro group, or an azido group. Of these, chlorine, bromine atom, chloroformyl group, isocyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group and isothiocyanato group are particularly preferable.
[0061]
In the general formulas (I) to (ID), n is preferably 4 or 5, and m is preferably 4-, 3-, 2-, 1-, 0 or 1+, more preferably 2- Or 1-.
[0062]
Although the preferable specific example of a metal complex represented with general formula (I) below is given, this invention is not limited to these.
[0063]
[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-
[0064]
[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-
[0065]
[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]^-
[0066]
[IrCl_Five(5-chlorothiadizole)]^2-
[IrCl_Four(5-chlorothiadizole)₂]^-
[IrBr_Five(5-chlorothiadizole)]^2-
[IrBr_Four(5-chlorothiadizole)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]^-
[0067]
In the present invention, the silver halide grains may further contain an iridium compound other than the iridium compound (the compound represented by the general formula (I)) as described above. As such another iridium compound, a 6-coordination complex having 6 ligands (ligands) and having iridium as a central metal is preferable because it can be uniformly incorporated into a silver halide crystal. As a preferred embodiment of the other iridium compound used in the present invention, a hexacoordinate complex having iridium as a central metal having only Cl, Br or I as a ligand is more preferred. In this case, Cl, Br, or I may be mixed in the hexacoordination complex. It is particularly preferable that the hexacoordinate complex having iridium as a central metal having Cl, Br or I as a ligand as a central metal is contained in a silver bromide-containing phase in order to obtain a high gradation in high-illuminance exposure.
These other iridium metal complexes are preferably used in combination with the iridium metal complex which is a compound represented by the general formula (I).
[0068]
Specific examples of 6-coordination complexes having iridium as a central metal in which all six ligands have Cl, Br, or I as ligands are listed below, but other iridium complexes that can be used in the present invention are listed below. It is not limited.
[0069]
[IrCl₆]^2-
[IrCl₆]^3-
[IrBr₆]^2-
[IrBr₆]^3-
[IrI₆]^3-
[0070]
In the present invention, it is also preferable that a silver halide emulsion contains a compound represented by the following general formula (II) (hereinafter also referred to as a metal complex).
Formula (II)
[MX^II _nL^II _(6-n)]^m
In general formula (II), M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd, or Pt. X^IIRepresents a halogen ion and L^IIIs X^IIRepresents an arbitrary ligand different from. n represents 3, 4, 5 or 6, and represents 4-, 3-, 2-, 1-, 0 or 1+.
[0071]
X^IIExamples of the halogen ion represented by the formula include fluorine ion, chlorine ion, bromine ion or iodine ion, with chlorine ion and bromine ion being particularly preferred.
L^IIThe ligand represented by may 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.
[0072]
Among the metal complexes represented by the general formula (II), the metal complexes represented by the following general formula (IIA) are preferable.
General formula (IIA)
[M^IIAX^IIA _nL^IIA _(6-n)]^m
In general formula (IIA), M^IIARepresents Re, Ru, Os or Rh. X^IIARepresents a halogen ion. L^IIAIs M^IIAIs Re, Ru or Os, it represents NO or NS;^IIAH is Rh₂O, OH or O is represented. n represents 3, 4, 5 or 6, and represents 4-, 3-, 2-, 1-, 0 or 1+.
[0073]
Although the preferable specific example of a metal complex represented with 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-
[0074]
The metal complex mentioned above is an anion, and when a salt is formed with a cation, the metal complex that is easily dissolved in water as the counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do.
[0075]
The metal complex represented by the general formula (I) is 1 × 10 10 per mole of silver during silver halide grain formation.^-TenFrom mole to 1 × 10^-3Mole addition is preferred, 1 × 10^-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^-6Mole addition is preferred, 1 × 10^-9From mole to 1 × 10^-7Most preferably, it is added in a molar amount.
In addition, in this invention, combined use with the metal complex represented by general formula (I) and the metal complex represented by general formula (II) is a preferable aspect.
[0076]
In the present invention, the above metal complex is added directly to the reaction solution at the time of silver halide grain formation, or is added to an aqueous halide solution for forming silver halide grains, or other solution. It is preferably incorporated into the silver halide grains by adding to the forming 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.
[0077]
When these metal complexes are incorporated into silver halide grains, they can be uniformly present inside the grains, but each of JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437 discloses. As disclosed, it is also preferable to be present only in the particle surface layer, and it is also preferable to add a layer containing the complex only inside the particle and not containing the complex on the particle surface. Further, as disclosed in the specifications of US Pat. Nos. 5,252,451 and 5,256,530, the particle surface phase is improved by physical ripening with fine particles incorporating the complex in the particles. It is also preferable to improve the quality. Furthermore, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, but the 6-coordination complex in which all six ligands are iridium consisting of Cl, Br or I is also a central metal has a silver bromide concentration maximum. It is preferable to contain.
[0078]
In the present invention, in addition to the metal complex, other metal ions can be doped inside and / or on the surface of the silver halide grains. As the metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, 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 types of ligands are used in one complex molecule. It is also preferable to use it. Moreover, an organic compound can also be used as a ligand, and a preferable organic compound includes a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More preferred organic compounds are compounds having a nitrogen atom, phosphorus atom, oxygen atom or sulfur atom in the molecule as a coordination atom to the metal, and particularly preferred are furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds having these compounds as a basic skeleton and having a substituent introduced thereto are also preferred.
[0079]
A combination of a metal ion and a ligand is preferably a combination of an iron ion, a ruthenium ion, and a cyanide ion.
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 complexes with cyanide ions as ligands are 1 × 10 5 per mole of silver during grain formation.^-8From mole to 1 × 10^-2Mole addition is preferred, 1 × 10^-6From mole to 5 × 10^-FourMost preferably, it is added in a molar amount. When ruthenium and osmium are the central metals, it is also preferable to use nitrosyl ions, thionitrosyl ions, or water molecules and chloride ions together as ligands. More preferably, a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex is formed, and a hexachloro complex is also preferably formed. These complexes are 1 × 10 5 per mole of silver during grain formation.^-TenFrom mole to 1 × 10^-6It is preferable to add a molar amount, more preferably 1 × 10^-9From mole to 1 × 10^-6The molar addition.
[0080]
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.
[0081]
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-sulfo Natobenzamido) phenyl] -5-mercaptotetrazole potassium salt) aurate (I) pentahydrate, gold (I) compound coordinated with nitrogen compound anion described in JP-A-4-268550, for example, bis (1 -Methylhydantoinato) gold (I) sodium salt tetrahydrate can be used. 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.
Also described in the gold (I) thiolate compounds described in US Pat. No. 3,503,749, JP-A-8-69074, JP-A-8-69075, and JP-A-9-269554. Of gold compounds, U.S. Pat. Nos. 5,620,841, 5,912,112, 5,620,841, 5,939,245, and 5,912,111. The compounds described in each specification can also be used.
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^-FourIs a mole.
[0082]
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.
[0083]
As colloidal gold sulfide, those having various sizes can be used, those having an average particle diameter of 50 nm or less are preferable, average particle diameter of 10 nm or less is more preferable, and average particle diameter of 3 nm or less is more preferable. This particle size can be measured from a TEM photograph. The composition of colloidal gold sulfide is Au₂S₁However, 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^-FourIs a mole.
[0084]
In addition to the gold sensitization described above, chalcogen sensitization can be performed with the same molecule, and AuCh^-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, when the gold compound represented by AuCh-L is reacted in a solvent in the presence of silver ions, it produces AgAuS when Ch is S, AgAuSe when Ch is Se, and AgAuTe when Ch is Te. It has the characteristic which is easy to make it.
Examples of such a compound include those in which L is an acyl group. In addition, compounds represented by the following general formula (AuCh 1), general formula (AuCh 2), and general formula (AuCh 3) Is mentioned.
[0085]
General formula (AuCh 1)
R₁-X-M-ChAu
In the general formula (AuCh 1), Au represents Au (I), Ch represents a sulfur atom, a selenium atom, or a tellurium atom, M represents a substituted or unsubstituted methylene group, and X represents an oxygen atom or a sulfur atom. , Selenium atom, or NR₂Represents 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.
Where R₂Represents a hydrogen atom or a substituent (for example, an organic group such as an alkyl group, an aryl group, and a heterocyclic group). Also R₁And M may bond to each other to form a ring.
[0086]
In the compound represented by the general formula (AuCh 1), 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.
[0087]
General formula (AuCh 2)
W₁W₂C = CR_ThreeChAu
In the general formula (AuCh 2), Au represents Au (I), Ch represents a sulfur atom, a selenium atom or a tellurium atom, R_ThreeAnd 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. R_ThreeAnd W₁, R_ThreeAnd W₂, W₁And W₂May combine with each other to form a ring.
[0088]
In the compound represented by the general formula (AuCh 2), a compound in which Ch is a sulfur atom or a selenium atom is preferable._ThreeIs 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 (NC)₂C = CHSAu, (CH_ThreeOCO)₂C = CHSAu, CH_ThreeCO (CH_ThreeOCO) C = CHSAu and the like.
[0089]
General formula (AuCh 3)
W_Three-E-ChAu
In the general formula (AuCh 3), Au represents Au (I), Ch represents a sulfur atom, a selenium atom, or a tellurium atom, E represents a substituted or unsubstituted ethylene group, W_ThreeIs Hammett's substituent constant σ_pAn electron-withdrawing group having a positive value is represented.
[0090]
In the compound represented by the general formula (AuCh 3), it is preferable that Ch is a sulfur atom or a selenium atom, and E is Hammett's substituent constant σ._pIt is preferably an ethylene group having an electron-withdrawing group having a positive value, and W_ThreeIs Hammett's substituent constant σ_pAn electron withdrawing group having a value of 0.2 or more is preferred.
[0091]
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^-FourIs a mole.
[0092]
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.
[0093]
In the silver halide emulsion used in the present invention, various compounds or precursors thereof are added for the purpose of preventing fogging during the production process, storage or photographic processing of the photosensitive 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.
[0094]
In the present invention, in order to improve the storage stability of the silver halide emulsion, both the hydroxamic acid derivative described in JP-A-11-109576 and the carbonyl group described in JP-A-11-327094 are adjacent to both ends. Are cyclic ketones having a double bond substituted with an amino group or a hydroxyl group (particularly those represented by the general formula (S1), and paragraph numbers [0036] to [0071] are incorporated in the specification of the present application. 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-benzenedisulfone) Acid, 3,4-dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzene Sulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), hydroxylamines represented by general formula (A) of US Pat. No. 5,556,741 (US Pat. No. 5,556,741 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). The water-soluble reducing agents represented by the general formulas (I) to (III) of the publication are also preferably used in the present invention.
[0095]
The silver halide emulsion used in 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.
[0096]
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.
[0097]
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.
[0098]
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.
[0099]
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.
[0100]
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.
[0101]
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.
[0102]
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.
[0103]
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.
[0104]
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.
[0105]
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.
[0106]
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.
[0107]
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 silver halide emulsion layer containing a yellow dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a cyan dye-forming coupler. Generally, these silver halide emulsion layers are a silver halide emulsion layer containing a yellow dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a cyan dye-forming coupler in order from the support. is there.
[0108]
However, a different layer structure may be used.
The yellow dye-forming coupler-containing silver halide emulsion layer may be disposed at any position on the support. However, when the yellow dye-forming coupler-containing silver halide emulsion layer contains silver halide tabular grains. The silver halide emulsion layer containing a magenta yellow dye-forming coupler or the silver halide emulsion layer containing a cyan yellow dye-forming coupler is preferably coated at a position farther from the support.
Further, from the viewpoint of color development acceleration, desilvering acceleration, and reduction of residual color by sensitizing dye, the yellow dye-forming coupler-containing silver halide emulsion layer is located farthest from the support from the other silver halide emulsion layers. It is preferable that it is coated. Further, from the viewpoint of reducing Blix fading, the yellow dye-forming coupler-containing silver halide emulsion layer is preferably the center layer of other silver halide emulsion layers, and from the viewpoint of reducing photobleaching, yellow dye-forming coupler-containing halogen The lowermost silver halide emulsion layer is preferred. Each of the yellow, magenta and cyan dye-forming coupler-containing silver halide emulsion layers may be composed of two 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.
[0109]
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.
[0110]
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), gelatin type, layer structure of the photosensitive material, and coating pH of the photosensitive material, those described in each part of the patent shown in Table 1 below are particularly preferably applied.
[0111]
[Table 1]

[0112]
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, which is preferable.
[0113]
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 patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Other cyan couplers include pyrroloazole-type cyan couplers described in European Patents 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.
[0114]
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.
[0115]
Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred. Including the couplers (1) to (47), the present invention is applied as it is,
Preferably incorporated as part of this specification.
[0116]
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 patent 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.
[0117]
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.
[0118]
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.
[0119]
In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable.
For example, high molecular weight redox compounds described in JP-A-5-333501, phenidone and hydrazine compounds described in WO98 / 33760, 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 of increasing the pH of the developer to speed up development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 842975A1, German Patent No. 180686846A1 And redox compounds described in French Patent No. 2760460A1 and the like are also preferably used.
[0120]
In the present invention, it is preferable to use a compound having a triazine skeleton with a high molar extinction coefficient as an ultraviolet absorber, and for example, compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or non-photosensitive. For example, JP-A-46-3335, JP-A-55-15276, JP-A-5-197074, 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.
[0121]
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.
[0122]
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.
[0123]
In the present invention, the film thickness of the entire photographic constituent layer is preferably 3.0 μm to 7.5 μm, more preferably 3.0 μm to 6.5 μm in order to satisfy development progress, fixing bleachability, and residual color. It is preferable that 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.
[0124]
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.
[0125]
In the present invention, an image can be formed by an exposure process in which light is irradiated according to image information and a development process in which the light-sensitive photosensitive material is developed. In particular, the present invention is suitable for rapid processing, that is, suitability for rapid processing in which color development is started in 9 seconds or less after imagewise exposure, and the color development is performed in a color development time of 28 seconds or less. Have
[0126]
The present invention is suitable for a scanning exposure method 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.
[0127]
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.
[0128]
In the present invention, monochromatic high-density light such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic emission light source (SHG) combining a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. The digital scanning exposure method using 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.
[0129]
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.
[0130]
In the present invention, the photosensitive material is preferably subjected to 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 .
[0131]
In the present invention, it 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.
[0132]
Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above.
[0133]
When the photosensitive 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. .
[0134]
In the processing of the light-sensitive material in the present invention, page 26, lower right column, line 1 to page 34, upper right column, line 9 of JP-A-2-207250, and page 5, upper left column of JP-A-4-97355. The processing materials and processing methods described in the 17th line to the 18th page, lower right column, 20th line are preferably applicable. Further, as the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.
[0135]
The image forming method of the present invention is an image forming method of a silver halide color photographic light-sensitive material having particularly rapid processing suitability, and imagewise exposure is performed using the above-described silver halide color photographic light-sensitive material. Color development is started within a second, and the color development is performed with a color development time within 28 seconds.
[0136]
In the present invention, the time from exposure to the start of color development is 9 seconds or less, preferably 9 seconds or less and 0.1 seconds or more, more preferably 9 seconds or less and 1 second or more, Preferably, it is within the range of 9 seconds or less and 2 seconds or more.
[0137]
The color development time is 28 seconds or less, preferably 28 seconds or less and 6 seconds or more, more preferably 25 seconds or less and 6 seconds or more, and further preferably 20 seconds or less and 6 seconds or more. After color development, it is preferable to carry out a water washing or stabilization process and a drying process after bleach-fixing (or bleaching and fixing). Here, the bleach-fixing time is preferably 30 seconds or less (preferably 30 seconds or less and 6 seconds or more, more preferably 25 seconds or less and 6 seconds or more, and further preferably 20 seconds or less and 6 seconds or more). Further, the washing time or the stabilization time is preferably 60 seconds or less (preferably 60 seconds or less and 6 seconds or more, more preferably 40 seconds or less and 6 seconds or more).
[0138]
In the present invention, the color development time means 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.
[0139]
As described above, the present invention can effectively achieve the object of the present invention even when the latent image time is short and rapid processing is performed.
[0140]
In the present invention, the light-sensitive material is developed after exposure with a conventional developing method containing a developing agent containing an alkali agent and a developing agent, a developing agent containing a developing agent in the photosensitive material, and an alkali solution containing no developing agent. In addition to wet methods such as a method of developing with an activator solution, a thermal development method that does not use a processing solution is known. However, the present invention is applied to a conventional method of developing with a color developer containing an alkali agent and a developer (particularly a p-phenylenediamine color developing agent). Further, the present invention is not applied to the image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and 9-152695. The present invention exhibits an effect in an existing development processing system with a well-equipped infrastructure.
[0141]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0142]
Example 1
(Preparation of emulsion B-1)
1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 3.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were simultaneously added and mixed at 50 ° C. with vigorous stirring. From 80% to 90% addition of silver nitrate, potassium bromide was added to 3 mol% per mole of finished silver halide. Similarly, when the addition of silver nitrate is 80% to 90%, K_Four[Fe (CN)₆The amount of Fe per mol of the finished silver halide is 2.5 × 10^-FiveMolar amounts were added. From the time when the addition of silver nitrate was 82% to the time of 88%,₂[IrCl₆The amount of Ir per mole of the finished silver halide is 5.3 × 10^-8Molar amounts were added. When 90% of the addition of silver nitrate was completed, the aqueous potassium iodide solution was adjusted so that the amount of I per mol of the finished silver halide was 0.25 mol%, and K₂[Ir (H₂O) Cl_FiveThe Ir amount per mole of the finished silver halide is 8.0 × 10^-7Molar amounts were added. After desalting at 40 ° C., 150 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl 1.9. The obtained grain was a cubic silver chlorobromoiodide emulsion having a sphere equivalent diameter of 0.73 μm and a coefficient of variation of 8.5%.
The emulsion was dissolved at 40 ° C. and sodium thiosulfonate was added at 1.5 × 10 5 per mole of silver halide.^-FiveMole added, sodium thiosulfate pentahydrate as sulfur sensitizer and bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) aurate (I) tetrafluoro as gold sensitizer Borate was used for aging at 60 ° C. After the temperature was lowered to 40 ° C., sensitizing dye A was added to 1.9 × 10 10^-FourMol, Sensitizing dye B 1.0 × 10 6 per mol of silver halide^-FourMole, 1-phenyl-5-mercaptotetrazole, 2.0 × 10 5 per mole of silver halide^-FourMol, 1- (5-methylureidophenyl) -5-mercaptotetrazole, 2.0 × 10 5 per mole of silver halide^-FourMole, potassium bromide 1.8 × 10 6 per mole of silver halide^-3Mole was added. The emulsion thus obtained was designated as Emulsion B-1.
[0143]
[Chemical 1]

[0144]
(Preparation of emulsions B-2 to B-4)
To emulsion B-1, change the addition rate of silver nitrate and sodium chloride added simultaneously, and add K_Four[Fe (CN)₆], K₂[IrCl₆] And K₂[Ir (H₂O) Cl_Five] And emulsions B-2 to B-4 were obtained in the same manner except that the amount of each compound added after the desalting treatment was changed. Emulsions B-2, B-3, and B-4 have cubic equivalent diameters of 0.68 μm, 0.33 μm, and 0.27 μm, respectively, and coefficients of variation of 8.3%, 9.5%, and 10.3%, respectively. It was a silver chlorobromoiodide emulsion.
[0145]
(Preparation of emulsion G-1)
To emulsion B-1, change the addition rate and temperature of silver nitrate and sodium chloride added simultaneously,_Four[Fe (CN)₆] The aqueous solution was changed so that the addition of silver nitrate was performed from 75% to 90%.₂[IrCl₆] Change the aqueous solution to be added from the point of 77% to 88% of addition of silver nitrate, and add further_Four[Fe (CN)₆], K₂[IrCl₆] And K₂[Ir (H₂O) Cl_Five], And after desalting at 40 ° C., 150 g of lime gelatin was added to adjust the pH to 5.5 and pCl 1.9. The resulting grain was a cubic silver chlorobromoiodide emulsion having a sphere equivalent diameter of 0.44 μm and a coefficient of variation of 9.3%.
The emulsion was dissolved at 40 ° C. and sodium thiosulfonate was added at 1.5 × 10 5 per mole of silver halide.^-FiveMole added, sodium thiosulfate pentahydrate as sulfur sensitizer and bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) aurate (I) tetrafluoro as gold sensitizer Borate was used for aging at 60 ° C. After the temperature was lowered to 40 ° C., sensitizing dye C was added to 7.2 × 10 6 per mol of silver halide.^-FourMol, 1-phenyl-5-mercaptotetrazole, 2.2 × 10 6 per mole of silver halide^-FourMole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, 9 × 10 6 per mole of silver halide^-FourMole, potassium bromide 8 × 10 8 per mole of silver halide^-3Mole was added. The emulsion thus obtained was designated as Emulsion G-1.
[0146]
[Chemical 2]

[0147]
(Preparation of emulsions G-2 to G-4)
Change the addition rate of silver nitrate and sodium chloride added simultaneously to emulsion G-1 and add K_Four[Fe (CN)₆], K₂[IrCl₆] And K₂[Ir (H₂O) Cl_Five] And emulsions G-2 to G-4 were obtained in the same manner except that the amount of each compound added after the desalting treatment was changed. Emulsions G-2, G-3, and G-4 have cube equivalent diameters of 0.39 μm, 0.22 μm, and 0.19 μm, respectively, and coefficients of variation of 9.0%, 12.5%, and 11.0%, respectively. It was a silver chlorobromoiodide emulsion.
[0148]
(Preparation of emulsions R-1 to R-4)
In the same manner as Emulsions G-1 to G-4, except that the following sensitizing dye H and compound I were used in place of sensitizing dye C and the amounts of sensitizing dye and compound I were changed, emulsion R-1 ~ R-4 was obtained. Emulsions R-1, R-2, R-3 and R-4 have sphere equivalent diameters of 0.43 μm, 0.38 μm, 0.23 μm and 0.18 μm, respectively, and variation coefficients of 9.7% and 9.1 respectively. %, 11.8% and 12.5% cubic silver chlorobromoiodide emulsions.
[0149]
[Chemical 3]

[0150]
[Formula 4]

[0151]
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.
[0152]
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 the emulsion B-1 were mixed and dissolved, and a first layer coating solution was prepared so as to have the composition described later. The emulsion coating amount indicates the silver coating amount.
[0153]
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.
[0154]
[Chemical formula 5]

[0155]
[Chemical 6]

[0156]
In addition, 1-phenyl-5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer at 1.0 × 10 5 per mole of silver halide, respectively.^-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).
[0157]
[Chemical 7]

[0158]
(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 (yellow image forming blue sensitive emulsion layer)
Emulsion B-1 0.24
Gelatin 1.08
Yellow coupler (ExY) 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
[0159]
Second layer (color mixing prevention layer)
Gelatin 0.55
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
[0160]
Third layer (magenta image-forming green sensitive emulsion layer)
Emulsion G-1 0.15
Gelatin 1.42
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
[0161]
Fourth layer (color mixing prevention layer)
Gelatin 0.40
Color mixing prevention layer (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
[0162]
5th layer (Cyan image forming red sensitive emulsion layer)
Emulsion R-1 0.13
Gelatin 1.20
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
[0163]
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
[0164]
[Chemical 8]

[0165]
[Chemical 9]

[0166]
[Chemical Formula 10]

[0167]
Embedded image

[0168]
Embedded image

[0169]
Embedded image

[0170]
Embedded image

[0171]
Embedded image

[0172]
Embedded image

[0173]
Embedded image

[0176]
  TrialFee101In order to investigate the suitability for speeding up by the digital exposure and processing method, the following experiment was conducted.
  As an exposure light source, a blue semiconductor laser with a wavelength of about 440 nm (announced by Nichia Chemical Co., Ltd. at the 48th Japan Society for Applied Physics Conference in March 2001), a semiconductor laser (with an oscillation wavelength of about 1060 nm in the form of a waveguide) LiNbO with domain structure_ThreeA green laser having a wavelength of about 530 nm and a red semiconductor laser having a wavelength of about 650 nm (Hitachi type No. HL6501GM) taken out by converting the wavelength with an SHG crystal. The laser beams of the three colors are moved in the direction perpendicular to the scanning direction by the polygon mirror so that the sample can be sequentially scanned and exposed. Variation in the amount of light due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter is 80 μm, the scanning pitch is 42.3 μm (600 dpi), and the average exposure time per pixel is 1.7 × 10.^-7Second. With this exposure method, a gray color tone exposure is applied to a sample with a size of 12 cm in length and 8.9 cm in width so that the color densities of yellow, magenta, and cyan are approximately equal. The color development processes A and B shown are carried out.
[0177]
[Processing A]
  TrialFee 101Continuous processing (running test) was performed until the color developing tank capacity was replenished twice in the following processing steps.

* Photosensitive material 1m²Replenishment amount per
** Attach a rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. to 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 concentrated solution 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. In addition, the rinsing was a tank countercurrent system from 1 to 4.
[0178]
The composition of each treatment liquid is as follows.

[0179]

[0180]

[0181]
  Processing step B is shown below.
[Process B]
  Sample 101Continuous processing (running test) 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.
[0182]
Processing temperature Temperature Time Replenishment amount^*
Color development 42.0 ℃ 27 seconds 45mL
The process after the bleach-fixing process is the same as the process A including the composition, temperature, time and replenishment amount of the processing liquid in each process.
* Photosensitive material 1m²Replenishment amount per
** Attach a rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. to 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 concentrated solution 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 counterflow system from 1 to 4.
[0183]
The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
Water 800mL 600mL
Optical brightener (FL-1) 4.0 g 6.8 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 8.0g −
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 ・ Monohydride 7.5g 16.5g
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
[0184]
Embedded image

[0185]
<Evaluation>
  TrialFee101In order to investigate the photographic characteristics, the following experiment was conducted.
  In addition, TryThe time from exposure of the material to entering the processing solution was set after 60 seconds, 9 seconds, or 3 seconds by changing the conveyance speed of the exposed sample.
[0186]
-Color density-
The yellow, magenta and cyan densities of each sample after treatment were measured to obtain characteristic curves. The exposure amount (E1) that gives a color density of 0.7 was determined for each sample. Further, the color density (D2) at an exposure amount (E2) 10 times that of E1 was determined for each sample. In each of the processing A and processing B, 0.3 mL of bleach-fixing solution is added per 1000 mL of the color developing solution, and the same exposure and processing are performed, and the color density (D1) corresponding to the exposure amount (E1) obtained above is obtained. ) The value of density change ((D1) -0.7) when the bleach-fixing solution was contained in the color developer was determined. The smaller this value, the better the processing stability.
[0187]
-Streaky-
Using the digital information recorded by the digital camera, each sample was subjected to exposure by the digital exposure apparatus, the process A or the process B to produce a color print. The time from exposure to entry into the processing solution was set in the same manner as described above after 60 seconds, 9 seconds, or 3 seconds. Ten color prints were prepared for each condition, and streaky irregularities were visually observed and evaluated as follows.
A There are almost no streaks, and it is very good.
B There are 1 to 3 samples out of 10 in which the stripe-like unevenness is slightly visible.
C There are 1 to 3 samples out of 10 in which stripes are clearly visible, and the color print quality is inferior.
D The streaks appear clearly in most samples, which is unacceptable for color print quality.
[0192]
  TrialFor emulsion 101, the emulsion B-1 in the first layer was changed to a blend of B-2 and B-3 (B-2 to B-3 was 4 to 6 per silver halide amount). Emulsion G-1 in the third layer was changed to a blend of G-2 and G-3 (G-2 to G-3 3: 7 per silver halide amount), and emulsion in the fifth layer Sample 201 was prepared in the same manner except that R-1 was changed to a blend of R-2 and R-3 (R-2 to R-3 was 7 to 3 per silver halide amount). Samples 202 and 203 in which the gelatin and silver coating amounts were changed as shown in Table 5 with respect to the sample 201 and samples 204 in which the gelatin and silver coating amounts were changed as shown in Table 5 relative to the sample 101 were prepared. did.
[0193]
[Table 5]

[0194]
  For the samples shown in Table 5, the exposure method, the time from exposure to color development, and the evaluation method are the same except that the processing step is changed to the following processing C.Sample 101 described aboveThe experiment was conducted in the same manner as above.
[0195]
The processing steps are shown below.
[Process C]
Samples 201 to 204 and 101 were continuously processed until the volume of the color developer replenisher used in the following processing steps was 0.5 times the color developer tank volume.
[0196]
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 seconds 121mL
Drying 80.0 ° C 16 seconds
* Photosensitive material 1m²Replenishment amount per
** Attach a rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. to 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 concentrated solution 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 counterflow system from 1 to 4.
[0197]
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
[0198]

[0199]
[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
[0200]
Embedded image

[0201]
  The results are shown in Table 6.
[Table 6]

[0202]
  As is apparent from the results in Table 6, the samples containing the silver halide emulsion of the grain size of the present invention were tested.Fee 203 is, DepartureIt can be seen that even in Process C having a short color development time, good performance is exhibited when the time from exposure to color development is short.
  TrialEven when the amount of gelatin and the amount of silver applied to the material is reduced, good performance is shown, and it can be seen that it is useful in that the cost can be reduced.
  Furthermore, since the above effects are not obtained in Samples 101 and 204 in which the grain size of the silver halide emulsion contained is outside the scope of the present invention, the grain size of the silver halide emulsion is within the scope of the present invention. It is clear that the performance is specifically good.
[0203]
【The invention's effect】
According to the present invention, even when ultra-rapid processing is performed, a silver halide color photographic light-sensitive material and an image forming method capable of always obtaining high quality and stable performance, particularly a silver halide color suitable for color printing. Photosensitive materials and image forming methods can be provided.

Claims (20)

At least a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer, and a non-photosensitive hydrophilic colloid layer are each provided on the support. A silver halide color photographic light-sensitive material provided with a photographic composition layer having one layer at a time, an image forming method for color development after imagewise exposure,
All the silver halide emulsions in the yellow dye-forming coupler-containing silver halide emulsion layer have a silver halide grain average sphere equivalent diameter of 0.70 μm to 0.30 μm and a coefficient of variation of the sphere equivalent diameter of 20 %, And a silver halide emulsion comprising cubic or tetradecahedral silver halide grains having {100} faces, and at least one layer of the silver halide emulsion layer containing the yellow, magenta, and cyan dye-forming coupler, silver chloride content comprises 90 mole% or more silver halide grains, the total silver coating amount of the photographic constituent layers ^is a 0.41g / ^{m 2} ~0.20g / m 2 the exposure after 9 seconds Start color development within
Image forming method and performing emitting color development in color development time within 28 seconds.   All the silver halide emulsions in the magenta dye-forming coupler-containing silver halide emulsion layer have an average equivalent spherical diameter of the silver halide grains of 0.40 μm to 0.20 μm, and the variation coefficient of the equivalent spherical diameter is 2. The image forming method according to claim 1, wherein the image forming method is a silver halide emulsion comprising cubic or tetradecahedral silver halide grains having a {100} plane of 20% or less.   All the silver halide emulsions in the cyan dye-forming coupler-containing silver halide emulsion layer have an average sphere equivalent diameter of silver halide grains of 0.40 μm to 0.20 μm, and the coefficient of variation of the sphere equivalent diameter is 3. The image forming method according to claim 1, wherein the image forming method is a silver halide emulsion comprising cubic or tetradecahedral silver halide grains having a {100} plane of 20% or less.   In at least one of the silver halide emulsion layers, the silver chloride content is 90 mol% or more, and the silver iodide-containing phase is 85% to 100% of the grain volume as measured from the inside of the silver halide grains. 4. A silver halide emulsion comprising a cubic or tetradecahedral silver halide grain having a {100} plane and arranged in a layer at any position. The image forming method described in 1.   The image forming method according to claim 4, wherein the silver halide emulsion has a silver bromide-containing phase inside the silver iodide-containing phase. 6. The image forming method according to claim 4, wherein the silver halide emulsion contains a compound represented by the following general formula (I).
Formula (I)
_{^{[IrX I n L I (6}} -n)] m
In the general formula ^(I), X I represents a halogen ion or a pseudohalogen ion. L ^I represents an arbitrary ligand different from X ^I. n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. The image forming method according to claim 6, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (IA) or (IB).
Formula (IA)
[IrX ^IA _n L ^IA _{( 6- n)} ] ^m
In the general formula (IA), ^XIA represents a halogen ion or a pseudohalogen ion. L ^IA represents any inorganic ligand different from X ^IA . n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0 or 1+.
Formula (IB)
[IrX ^IB _n L ^IB _(6-n) ] ^m
In the general formula (IB), X ^IB represents a halogen ion or a pseudohalogen ion. ^LIB represents a ligand in which a chain or cyclic hydrocarbon is a base structure, or a carbon atom or a hydrogen atom of a part of the base structure is replaced with another atom or atomic group . n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0 or 1+. Wherein L ^IA in the general formula (IA) is water, L ^IB in Formula (IB) is 5-membered ring ligand containing at least one sulfur atom and at least one nitrogen atom as the ring skeleton-forming atoms The image forming method according to claim 7, wherein: The compound represented by the general formula (I) is a compound represented by the general formula (IA), and L ^IA in the general formula (IA) is water. The image forming method described.   The image forming method according to any one of claims 7 to 9, wherein the compound represented by the general formula (IA) or (IB) is contained in the silver iodide-containing phase.   At least one silver halide emulsion in the silver halide emulsion layer has a silver bromide-containing phase containing an iridium hexacoordination complex in which all six ligands are all Cl, Br, or I. The image forming method according to claim 1.   The image forming method according to any one of claims 4 to 11, wherein the silver halide emulsion is a silver halide emulsion containing a yellow dye-forming coupler.   The image forming method according to any one of claims 4 to 12, wherein the silver halide emulsion is a silver halide emulsion containing a magenta dye-forming coupler.   14. The image forming method according to claim 4, wherein the silver halide emulsion is a cyan halide emulsion containing a cyan dye-forming coupler.   15. The silver halide emulsion in any one of the silver halide emulsion layers is formed by adding a gold (I) compound having an organic ligand. Image forming method.   The image forming method according to claim 15, wherein the gold (I) compound having an organic ligand is a bisgold (I) mesoionic heterocycle.   17. Each of the silver halide emulsion layers contains at least two monodispersed emulsions having a variation coefficient of equivalent sphere diameter of silver halide grains of 20% or less. The image forming method described in 1. The total gelatin coating amount of the photographic constituent layers ^is, the image forming method according to any one of claims 1 to 17, characterized in that the ^{6.0g / m 2 ~3.0g / m 2} . The image forming method according to any one of claims 1 to 18, the exposure of the blue light, and carrying out a blue semiconductor laser with a wavelength of 430～450Nm. A silver halide color photographic light-sensitive material for rapid processing which starts color development within 9 seconds after exposure and forms an image by performing the color development within a color development time of 28 seconds,
The silver halide color photographic light-sensitive material comprises, on a support, a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer, and a non-photosensitive material. Provided with a photographic composition layer each having at least one photosensitive hydrophilic colloid layer,
All the silver halide emulsions in the yellow dye-forming coupler-containing silver halide emulsion layer have an average sphere equivalent diameter of 0.70 μm to 0.30 μm and a variation coefficient of the equivalent sphere diameter of 20 %, And a silver halide emulsion comprising cubic or tetradecahedral silver halide grains having {100} faces,
The yellow, magenta, and in at least one layer of the cyan dye-forming coupler-containing silver halide emulsion layer, a silver chloride content viewing contains 90 mol% or more silver halide grains, the total silver coating amount of the photographic constituent layers ^but silver halide color photographic material, which is a ^{0.41g / m 2 ~0.20g / m 2} .