JP2004037572A - Method for forming image by using silver halide color photographic sensitive material and silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming an image by which stable photographic performance can always be obtained even when ultrafast processing is carried out, and to provide a silver halide color photographic sensitive material to be used for the method, in particular, a silver halide color photographic sensitive material suitable for color print. <P>SOLUTION: The method for forming an image is carried out by exposing a silver halide color photographic sensitive material in the form of an image and then developing colors. At least one layer of silver halide emulsion layers contains a silver halide emulsion containing at least one kind of metal complex expressed by general formula (1) and/or at least one kind of metal complex expressed by general formula (1) and having ≥90 mol% silver chloride content. The color developing is started within 9 seconds after imagewise exposure of the silver halide photographic sensitive material, and the development is carried out within 28 seconds. General formula (1) [IrX<SP>I</SP><SB>n</SB>L<SP>I</SP><SB>(6-n)</SB>]<SP>m</SP>, wherein X<SP>I</SP>is a halogen ion or pseudohalogen ion and L<SP>I</SP>is a desired ligand different from X<SP>I</SP>. <P>COPYRIGHT: (C)2004,JPO

Description

【０１０７】
本発明において用いられるシアン、マゼンタ及びイエローカプラーとしては、その他、特開昭６２−２１５２７２号公報の第９１頁右上欄４行目〜１２１頁左上欄６行目、特開平２−３３１４４号公報の第３頁右上欄１４行目〜１８頁左上欄末行目と第３０頁右上欄６行目〜３５頁右下欄１１行目やＥＰ０３５５，６６０Ａ２号明細書の第４頁１５行目〜２７行目、５頁３０行目〜２８頁末行目、４５頁２９行目〜３１行目、４７頁２３行目〜６３頁５０行目に記載のカプラーも有用である。
また、本発明はＷＯ９８／３３７６０号の一般式（ＩＩ）及び（ＩＩＩ）、特開平１０−２２１８２５号公報の一般式（Ｄ）で表される化合物を添加してもよく、好ましい。
【０１０８】
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。
【０１０９】
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。
【０１１０】
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、本願にそのまま適用され、本願の明細書の一部として好ましく取り込まれる。
【０１１１】
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。
【０１１２】
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。
【０１１３】
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。
【０１１４】
感光材料には、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。
【０１１５】
感光材料には、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。
【０１１６】
感光材料に用いることのできる結合剤又は保護コロイドとしては、ゼラチンを用いることが有利であるが、それ以外の親水性コロイドを単独であるいはゼラチンとともに用いることができる。好ましいゼラチンとしては、鉄、銅、亜鉛、マンガン等の不純物として含有される重金属は、好ましくは５ｐｐｍ以下、更に好ましくは３ｐｐｍ以下である。また、感光材料中に含まれるカルシウム量は、好ましくは２０ｍｇ／ｍ^２以下、更に好ましくは１０ｍｇ／ｍ^２以下、最も好ましくは５ｍｇ／ｍ^２以下である。
【０１１７】
感光材料には、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。
【０１１８】
感光材料における写真構成層中の総塗設ゼラチン量は３ｇ／ｍ^２以上６ｇ／ｍ^２以下であることが好ましく、３ｇ／ｍ^２以上５ｇ／ｍ^２以下であることが更に好ましい。また、超迅速処理した場合でも、現像進行性、及び定着漂白性、残色を満足するために、写真構成層全体の膜厚が３μｍ〜７．５μｍであることが好ましく、更に３μｍ〜６．５μｍであることが好ましい。乾燥膜厚の評価方法は、乾燥膜剥離前後の膜厚の変化、あるいは断面の光学顕微鏡や電子顕微鏡での観察により測定することができる。本発明において、現像進行性と乾燥速度を上げることを両立するために、膨潤膜厚が８μｍ〜１９μｍであることが好ましく、更に９μｍ〜１８μｍであることが好ましい。膨潤膜厚の測定としては、３５℃の水溶液中に乾燥した感光材料を浸し、膨潤して十分平衡に達した状態で打点方法にて測定することができる。感光材料における写真構成中の総塗設銀量は、０．２ｇ／ｍ^２〜０．５ｇ／ｍ^２であることが好ましく、０．２ｇ／ｍ^２〜０．４５ｇ／ｍ^２であることが更に好ましく、０．２ｇ／ｍ^２〜０．４０ｇ／ｍ^２であることが最も好ましい。
【０１１９】
感光材料には、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／ｍ^２、好ましくは１×１０^−４〜１×１０^−１ｇ／ｍ^２、更に好ましくは１×１０^−３〜１×１０^−２ｇ／ｍ^２である。
【０１２０】
以下、上記ハロゲン化銀カラー写真感光材料を用いた画像形成方法について説明する。
感光材料は、画像情報に応じて光を照射される露光工程と、前記光照射された感光材料を現像する現像工程とにより、画像を形成することができる。
【０１２１】
感光材料は、通常のネガプリンターを用いたプリントシステムに使用される以外に、陰極線（ＣＲＴ）を用いた走査露光方式にも適している。陰極線管露光装置は、レーザーを用いた装置に比べて、簡便でかつコンパクトであり、低コストになる。また、光軸や色の調整も容易である。画像露光に用いる陰極線管には、必要に応じてスペクトル領域に発光を示す各種発光体が用いられる。例えば赤色発光体、緑色発光体、青色発光体のいずれか１種、あるいは２種以上が混合されて用いられる。スペクトル領域は、上記の赤、緑、青に限定されず、黄色、橙色、紫色或いは赤外領域に発光する蛍光体も用いられる。特に、これらの発光体を混合して白色に発光する陰極線管がしばしば用いられる。
【０１２２】
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。
【０１２３】
感光材料は、ガスレーザー、発光ダイオード、半導体レーザー、半導体レーザーあるいは半導体レーザーを励起光源に用いた固体レーザーと非線形光学結晶を組合わせた第二高調波発光光源（ＳＨＧ）等の単色高密度光を用いたデジタル走査露光方式が好ましく使用される。システムをコンパクトで、安価なものにするために半導体レーザー、半導体レーザーあるいは固体レーザーと非線形光学結晶を組合わせた第二高調波発生光源（ＳＨＧ）を使用することが好ましい。特にコンパクトで、安価、更に寿命が長く安定性が高い装置を設計するためには半導体レーザーの使用が好ましく、露光光源の少なくとも一つは半導体レーザーを使用することが好ましい。
【０１２４】
このような走査露光光源を使用する場合、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。
【０１２５】
感光材料は、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（株）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ＬｉＮｂＯ_３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ＬｉＮｂＯ_３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。
【０１２６】
感光材料は、以下の公知資料に記載の露光、現像システムと組み合わせることで好ましく用いることができる。前記現像システムとしては、特開平１０−３３３２５３号公報に記載の自動プリント並びに現像システム、特開２０００−１０２０６号公報に記載の感光材料搬送装置、特開平１１−２１５３１２号公報に記載の画像読取装置を含む記録システム、特開平１１−８８６１９号公報並びに特開平１０−２０２９５０号公報に記載のカラー画像記録方式からなる露光システム、特開平１０−２１０２０６号公報に記載の遠隔診断方式を含むデジタルフォトプリントシステム、及び特願平１０−１５９１８７号公報に記載の画像記録装置を含むフォトプリントシステムが挙げられる。
【０１２７】
感光材料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。
【０１２８】
感光材料をプリンター露光する際、米国特許第４，８８０，７２６号明細書に記載のバンドストップフィルターを用いることが好ましい。これによって光混色が取り除かれ、色再現性が著しく向上する。
本発明においては、欧州特許ＥＰ０７８９２７０Ａ１明細書や同ＥＰ０７８９４８０Ａ１号明細書に記載のように、画像情報を付与する前に、予め、黄色のマイクロドットパターンを前露光し、複写規制を施しても構わない。
【０１２９】
感光材料の現像処理には、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。
【０１３０】
本発明では、上記感光材料を使用し、露光してから９秒以内に発色現像を開始し、該発色現像が２８秒以内に行われる。
ここで、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。
【０１３１】
また、発色現像時間は２８秒以下（好ましくは２８秒以下６秒以上）が好ましく、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（または漂白、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、漂白定着時間は好ましくは３０秒以下（好ましくは３０秒以下６秒以上）が好ましく、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。
【０１３２】
なお、発色現像時間とは、感光材料が発色現像液中に入ってから次の処理工程の漂白定着液に入るまでの時間をいう。例えば、自動現像機などで処理される場合には、感光材料が発色現像液中に浸漬されている時間（いわゆる液中時間）と、感光材料が発色現像液を離れ次の処理工程の漂白定着浴に向けて空気中を搬送されている時間（いわゆる空中時間）との両者の合計を発色現像時間という。同様に、漂白定着時間とは、感光材料が漂白定着液中に入ってから次の水洗又は安定浴に入るまでの時間をいう。また、水洗又は安定化時間とは、感光材料が水洗又は安定化液中に入ってから乾燥工程に向けて液中にある時間（いわゆる液中時間）をいう。
【０１３３】
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。
【０１３４】
【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。
【０１３５】
［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ｐＨ５．５、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、Ｋ_４［Ｒｕ（ＣＮ）_６］水溶液を出来上がりのハロゲン化銀１モルあたりＲｕ量が３×１０^−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、Ｋ_２［ＩｒＣｌ_６］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０．３モル％になるように添加した。４０℃で脱塩処理を施した後、石灰処理ゼラチン１６８ｇを加え、ｐＨ５．５、ｐＣｌ１．８に調整した。得られた粒子は球相当径０．５１μｍ、変動係数９％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２×１０^−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２．７×１０^−４モル、増感色素Ｂをハロゲン化銀１モルあたり１．４×１０^−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２．７×１０^−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２．７×１０^−４モル、臭化カリウムをハロゲン化銀１モルあたり２．７×１０^−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。
【０１３６】
【化１】

【０１３７】
（乳剤Ｂ−２の調製）
乳剤Ｂ−１とは、硝酸銀の添加が８０％の時点から９０％の時点にかけて添加するＫ_４［Ｒｕ（ＣＮ）_６］水溶液に代えて、Ｋ_４［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３×１０^−５モルになる量を添加したことのみ異なる乳剤を調製し、これを乳剤Ｂ−２とした。
【０１３８】
（乳剤Ｂ−３の調製）
乳剤Ｂ−１とは、硝酸銀の添加が８０％の時点から９０％の時点にかけて添加するＫ_４［Ｒｕ（ＣＮ）_６］水溶液に代えて、Ｋ_４［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３×１０^−５モルになる量を添加し、硝酸銀の添加が８２％の時点から８８％の時点にかけて添加するＫ_２［ＩｒＣｌ_６］水溶液の量を出来上がりのハロゲン化銀１モルあたりＩｒ量が３．６×１０^−８モルになる量に変更し、同じく硝酸銀の添加が８２％の時点から８８％の時点にかけて、Ｋ_２［ＩｒＢｒ_６］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４．０×１０^−８モルになる量を添加したことのみ異なる乳剤を調製し、これを乳剤Ｂ−３とした。
【０１３９】
（乳剤Ｂ−４の調製）
乳剤Ｂ−１とは、硝酸銀の添加が８２％の時点から８８％の時点にかけて添加するＫ_２［ＩｒＣｌ_６］水溶液の量を出来上がりのハロゲン化銀１モルあたりＩｒ量が３．６×１０^−８モルになる量に変更し、更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ_２［Ｉｒ（Ｈ_２Ｏ）Ｃｌ_５］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１．６×１０^−６モルになる量を添加したことのみ異なる乳剤を調製し、これを乳剤Ｂ−４とした。
【０１４０】
（乳剤Ｂ−５の調製）
乳剤Ｂ−１とは、硝酸銀の添加が８２％の時点から８８％の時点にかけて添加するＫ_２［ＩｒＣｌ_６］水溶液の量を出来上がりのハロゲン化銀１モルあたりＩｒ量が１．２×１０^−８モルになる量に変更し、更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ_２［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ_５］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１．０×１０^−６モルになる量を添加したことのみ異なる乳剤を調製し、これを乳剤Ｂ−５とした。
【０１４１】
（乳剤Ｂ−６の調製）
乳剤Ｂ−１とは、硝酸銀の添加が８２％の時点から８８％の時点にかけて添加するＫ_２［ＩｒＣｌ_６］水溶液の量を出来上がりのハロゲン化銀１モルあたりＩｒ量が８．０×１０^−９モルになる量に変更し、更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ_２［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ_５］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８．０×１０^−６モルになる量およびＫ_２［Ｉｒ（Ｈ_２Ｏ）Ｃｌ_５］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１．１×１０^−６モルになる量を添加したことのみ異なる乳剤を調製し、これを乳剤Ｂ−６とした。
【０１４２】
（乳剤Ｂ−７の調製）
乳剤Ｂ−１とは、硝酸銀の添加が８２％の時点から８８％の時点にかけて添加するＫ_２［ＩｒＣｌ_６］水溶液の量を出来上がりのハロゲン化銀１モルあたりＩｒ量が１．０×１０^−８モルになる量に変更し、同じく硝酸銀の添加が８２％の時点から８８％の時点にかけて、Ｋ_２［Ｉｒ（２−ｃｈｌｏｒｏ−５−ｆｌｕｏｒｏｔｈｉａｄｉａｚｏｌｅ）Ｃｌ_５］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７．２×１０^−７モルになる量を添加したことのみ異なる乳剤を調製し、これを乳剤Ｂ−７とした。
【０１４３】
（乳剤Ｂ−８の調製）
乳剤Ｂ−１とは、硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ_３［ＲｈＢｒ_６］水溶液を出来上がりのハロゲン化銀１モルあたりＲｈ量が５．３×１０^−９モルになる量を添加し、硝酸銀の添加が８２％の時点から８８％の時点にかけて添加するＫ_２［ＩｒＣｌ_６］水溶液の量を出来上がりのハロゲン化銀１モルあたりＩｒ量が３．６×１０^−８モルになる量に変更したことのみ異なる乳剤を調製し、これを乳剤Ｂ−８とした。
【０１４４】
（乳剤Ｂ−９の調製）
乳剤Ｂ−１とは、硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｃｓ_２［Ｏｓ（ＮＯ）Ｃｌ_５］水溶液を出来上がりのハロゲン化銀１モルあたりＯｓ量が４．１×１０^−９モルになる量を添加し、硝酸銀の添加が８２％の時点から８８％の時点にかけて添加するＫ_２［ＩｒＣｌ_６］水溶液の量を出来上がりのハロゲン化銀１モルあたりＩｒ量が３．６×１０^−８モルになる量に変更したことのみ異なる乳剤を調製し、これを乳剤Ｂ−９とした。
【０１４５】
（乳剤Ｂ−１０の調製）
乳剤Ｂ−１とは、硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ_３［ＲｈＢｒ_６］水溶液を出来上がりのハロゲン化銀１モルあたりＲｈ量が４．１×１０^−９モルになる量を添加し、硝酸銀の添加が８２％の時点から８８％の時点にかけて添加するＫ_２［ＩｒＣｌ_６］水溶液の量を出来上がりのハロゲン化銀１モルあたりＩｒ量が８．０×１０^−９モルになる量に変更し、更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ_２［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ_５］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８．０×１０^−７モルになる量およびＫ_２［Ｉｒ（Ｈ_２Ｏ）Ｃｌ_５］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７．０×１０^−７モルになる量を添加したことのみ異なる乳剤を調製し、これを乳剤Ｂ−１０とした。
【０１４６】
（乳剤Ｂ−１１の調製）
乳剤Ｂ−１とは、硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ_３［ＲｈＢｒ_６］水溶液を出来上がりのハロゲン化銀１モルあたりＲｈ量が５．３×１０^−９モルになる量を添加し、硝酸銀の添加が８０％の時点から９０％の時点にかけて添加するＫ_４［Ｒｕ（ＣＮ）_６］水溶液に代えて、Ｋ_４［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３×１０^−５モルになる量を添加し、硝酸銀の添加が８２％の時点から８８％の時点にかけて添加するＫ_２［ＩｒＣｌ_６］水溶液の量を出来上がりのハロゲン化銀１モルあたりＩｒ量が３．６×１０^−８モルになる量に変更したことのみ異なる乳剤を調製し、これを乳剤Ｂ−１１とした。
【０１４７】
（乳剤Ｂ−１２の調製）
乳剤Ｂ−１とは、硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ_３［ＲｈＢｒ_６］水溶液を出来上がりのハロゲン化銀１モルあたりＲｈ量が５．３×１０^−９モルになる量を添加し、硝酸銀の添加が８０％の時点から９０％の時点にかけて添加するＫ_４［Ｒｕ（ＣＮ）_６］水溶液に代えて、Ｋ_４［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３×１０^−５モルになる量を添加し、硝酸銀の添加が８２％の時点から８８％の時点にかけて添加するＫ_２［ＩｒＣｌ_６］水溶液の量を出来上がりのハロゲン化銀１モルあたりＩｒ量が２．０×１０^−８モルになる量に変更し、同じく硝酸銀の添加が８２％の時点から８８％の時点にかけて、Ｋ_２［ＩｒＢｒ_６］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３．０×１０^−８モルになる量を添加したことのみ異なる乳剤を調製し、これを乳剤Ｂ−１２とした。
【０１４８】
（乳剤Ｂ−１３の調製）
乳剤Ｂ−１とは、硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｃｓ_２［Ｏｓ（ＮＯ）Ｃｌ_５］水溶液を出来上がりのハロゲン化銀１モルあたりＯｓ量が４．１×１０^−９モルになる量を添加し、硝酸銀の添加が８２％の時点から８８％の時点にかけて添加するＫ_２［ＩｒＣｌ_６］水溶液の量を出来上がりのハロゲン化銀１モルあたりＩｒ量が８．０×１０^−９モルになる量に変更し、更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ_２［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ_５］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７．２×１０^−７モルになる量を添加したことのみ異なる乳剤を調製し、これを乳剤Ｂ−１３とした。
【０１４９】
（乳剤Ｂ−１４の調製）
乳剤Ｂ−１とは、硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ_３［ＲｈＢｒ_６］水溶液を出来上がりのハロゲン化銀１モルあたりＲｈ量が５．３×１０^−９モルになる量を添加し、硝酸銀の添加が８０％の時点から９０％の時点にかけて添加するＫ_４［Ｒｕ（ＣＮ）_６］水溶液に代えて、Ｋ_４［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３×１０^−５モルになる量を添加し、硝酸銀の添加が８２％の時点から８８％の時点にかけて添加するＫ_２［ＩｒＣｌ_６］水溶液の量を出来上がりのハロゲン化銀１モルあたりＩｒ量が６．０×１０^−９モルになる量に変更し、同じく硝酸銀の添加が８２％の時点から８８％の時点にかけて、Ｋ_２［Ｉｒ（２−ｃｈｌｏｒｏ−５−ｆｌｕｏｒｏｔｈｉａｄｉａｚｏｌｅ）Ｃｌ_５］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５．２×１０^−７モルになる量を添加し、更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ_２［Ｉｒ（Ｈ_２Ｏ）Ｃｌ_５］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１．０×１０^−６モルになる量を添加したことのみ異なる乳剤を調製し、これを乳剤Ｂ−１４とした。
【０１５０】
（乳剤Ｇ−１の調製）
石灰処理ゼラチン３％水溶液１０００ｍｌをｐＨ５．５、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４０℃で同時に添加混合した。硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ_３［ＲｈＢｒ_６］水溶液を出来上がりのハロゲン化銀１モルあたりＲｈ量が５．８×１０^−９モルになる量を添加した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウムを出来上がりのハロゲン化銀１モルあたり４．３モル％になる量を激しく混合しながら添加した。硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ_４［Ｒｕ（ＣＮ）_６］水溶液を出来上がりのハロゲン化銀１モルあたりＲｕ量が３．０×１０^−５モルになる量を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ_２［ＩｒＣｌ_６］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５．０×１０^−８モルになる量を添加した。更に硝酸銀の添加が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０．１５モル％になる量を激しく混合しながら添加した。硝酸銀の添加が９２％の時点から９５％の時点にかけて、Ｋ_２［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ_５］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５．０×１０^−７モルになる量を添加した。更に、硝酸銀の添加が９５％の時点から９８％の時点にかけて、Ｋ_２［Ｉｒ（Ｈ_２Ｏ）Ｃｌ_５］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５．０×１０^−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１６８ｇを加え、ｐＨ５．５、ｐＣｌ１．８に調整した。得られた粒子は球相当径０．３５・香Ａ変動係数９％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２×１０^−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金チオグルコースを用い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６×１０^−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２×１０^−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８×１０^−４モル、臭化カリウムをハロゲン化銀１モルあたり７×１０^−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。
【０１５１】
【化２】

【０１５２】
（乳剤Ｒ−１の調製）
石灰処理ゼラチン３％水溶液１０００ｍｌをｐＨ５．５、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４０℃で同時に添加混合した。硝酸銀の添加が６０％の時点から８０％の時点にかけて、Ｋ_３［ＲｈＢｒ_６］水溶液を出来上がりのハロゲン化銀１モルあたりＲｈ量が５．８×１０^−９モルになる量を添加した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウムを出来上がりのハロゲン化銀１モルあたり４．３モル％になる量を激しく混合しながら添加した。硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ_４［Ｒｕ（ＣＮ）_６］水溶液を出来上がりのハロゲン化銀１モルあたりＲｕ量が３×１０^−５モルになる量を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ_２［ＩｒＣｌ_６］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５×１０^−９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０．１モル％になる量を激しく混合しながら添加した。硝酸銀の添加が９２％の時点から９５％の時点にかけて、Ｋ_２［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ_５］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５×１０^−７モルになる量を添加した。更に、硝酸銀の添加が９５％の時点から９８％の時点にかけて、Ｋ_２［Ｉｒ（Ｈ_２Ｏ）Ｃｌ_５］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５×１０^−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１６８ｇを加え、ｐＨ５．５、ｐＣｌ１．８に調整した。得られた粒子は球相当径０．３５μｍ、変動係数９％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２×１０^−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Ｈをハロゲン化銀１モルあたり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２×１０^−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８×１０^−４モル、化合物Ｉをハロゲン化銀１モルあたり１×１０^−３モル、臭化カリウムをハロゲン化銀１モルあたり７×１０^−３モル添加した。このようにして得られた乳剤を、乳剤Ｒ−１とした。
【０１５３】
【化３】

【０１５４】
【化４】

【０１５５】
（試料）
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。
【０１５６】
−第一層用塗布液調製−
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。
【０１５７】
−第二層〜第七層用塗布液調製−
第二層〜第七層用の塗布液も第一層塗布液と同様の方法で調製した。各層のゼラチン硬化剤としては、１−オキシ−３，５−ジクロロ−ｓ−トリアジンナトリウム塩（Ｈ−１）、（Ｈ−２）、（Ｈ−３）を用いた。また、各層にＡｂ−１、Ａｂ−２、Ａｂ−３、及びＡｂ−４をそれぞれ全量が１５．０ｍｇ／ｍ^２、６０．０ｍｇ／ｍ^２、５．０ｍｇ／ｍ^２及び１０．０ｍｇ／ｍ^２となるように添加した。
【０１５８】
【化５】

【０１５９】
【化６】

【０１６０】
また、緑感性乳剤層および赤感性乳剤層に対し、１−フェニル−５−メルカプトテトラゾールを、それぞれハロゲン化銀１モル当り１．０×１０^−３モルおよび５．９×１０^−４モル添加した。さらに、第二層、第四層および第六層にも１−フェニル−５−メルカプトテトラゾールを、それぞれ０．２ｍｇ／ｍ^２、０．２ｍｇ／ｍ^２および０．６ｍｇ／ｍ^２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／ｍ^２添加した。また、第二層、第四層および第六層にカテコール−３，５−ジスルホン酸二ナトリウムをそれぞれ６ｍｇ／ｍ^２、６ｍｇ／ｍ^２、１８ｍｇ／ｍ^２となるように添加した。また、イラジエーション防止のために、以下の染料（カッコ内は塗布量を表す）を添加した。
【０１６１】
【化７】

【０１６２】
（層構成）
以下に、各層の構成を示す。数字は塗布量（ｇ／ｍ^２）を表す。ハロゲン化銀乳剤は、銀換算塗布量を表す。
支持体
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（ＴｉＯ_２；含有率１６質量％、ＺｎＯ；含有率４質量％）と蛍光増白剤（４，４’−ビス（５−メチルベンゾオキサゾリル）スチルベン。含有率０．０３質量％）、青味染料（群青）を含む］
第一層（青感性乳剤層）
乳剤Ｂ−１　　　　　　　　　　　　　　　　　　　　　　０．１９
ゼラチン　　　　　　　　　　　　　　　　　　　　　　　１．００
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
【０１６３】
第二層（混色防止層）
ゼラチン　　　　　　　　　　　　　　　　　　　　　　　０．５０
混色防止剤（Ｃｐｄ−４）　　　　　　　　　　　　　　　０．０５
色像安定剤（Ｃｐｄ−５）　　　　　　　　　　　　　　　０．０１
色像安定剤（Ｃｐｄ−６）　　　　　　　　　　　　　　　０．０６
色像安定剤（Ｃｐｄ−７）　　　　　　　　　　　　　　　０．０１
溶媒（Ｓｏｌｖ−１）　　　　　　　　　　　　　　　　　０．０３
溶媒（Ｓｏｌｖ−２）　　　　　　　　　　　　　　　　　０．１１
【０１６４】
第三層（緑感性乳剤層）
乳剤Ｇ−１　　　　　　　　　　　　　　　　　　　　　　０．１２
ゼラチン　　　　　　　　　　　　　　　　　　　　　　　１．３６
マゼンタカプラー（ＥｘＭ）　　　　　　　　　　　　　　０．１５
紫外線吸収剤（ＵＶ−Ａ）　　　　　　　　　　　　　　　０．１４
色像安定剤（Ｃｐｄ−２）　　　　　　　　　　　　　　　０．０２
色像安定剤（Ｃｐｄ−４）　　　　　　　　　　　　　　　０．００２
色像安定剤（Ｃｐｄ−６）　　　　　　　　　　　　　　　０．０９
色像安定剤（Ｃｐｄ−８）　　　　　　　　　　　　　　　０．０２
色像安定剤（Ｃｐｄ−９）　　　　　　　　　　　　　　　０．０３
色像安定剤（Ｃｐｄ−１０）　　　　　　　　　　　　　　０．０１
色像安定剤（Ｃｐｄ−１１）　　　　　　　　　　　　　　０．０００１
溶媒（Ｓｏｌｖ−３）　　　　　　　　　　　　　　　　　０．１１
溶媒（Ｓｏｌｖ−４）　　　　　　　　　　　　　　　　　０．２２
溶媒（Ｓｏｌｖ−５）　　　　　　　　　　　　　　　　　０．２０
【０１６５】
第四層（混色防止層）
ゼラチン　　　　　　　　　　　　　　　　　　　　　　　０．３６
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
【０１６６】
第五層（赤感性乳剤層）
乳剤Ｒ−１　　　　　　　　　　　　　　　　　　　　　　０．１０
ゼラチン　　　　　　　　　　　　　　　　　　　　　　　１．１１
シアンカプラー（ＥｘＣ−２）　　　　　　　　　　　　　０．１３
シアンカプラー（ＥｘＣ−３）　　　　　　　　　　　　　０．０３
色像安定剤（Ｃｐｄ−１）　　　　　　　　　　　　　　　０．０５
色像安定剤（Ｃｐｄ−６）　　　　　　　　　　　　　　　０．０６
色像安定剤（Ｃｐｄ−７）　　　　　　　　　　　　　　　０．０２
色像安定剤（Ｃｐｄ−９）　　　　　　　　　　　　　　　０．０４
色像安定剤（Ｃｐｄ−１０）　　　　　　　　　　　　　　０．０１
色像安定剤（Ｃｐｄ−１４）　　　　　　　　　　　　　　０．０１
色像安定剤（Ｃｐｄ−１５）　　　　　　　　　　　　　　０．１２
色像安定剤（Ｃｐｄ−１６）　　　　　　　　　　　　　　０．０３
色像安定剤（Ｃｐｄ−１７）　　　　　　　　　　　　　　０．０９
色像安定剤（Ｃｐｄ−１８）　　　　　　　　　　　　　　０．０７
溶媒（Ｓｏｌｖ−５）　　　　　　　　　　　　　　　　　０．１５
溶媒（Ｓｏｌｖ−８）　　　　　　　　　　　　　　　　　０．０５
【０１６７】
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
【０１６８】
【化８】

【０１６９】
【化９】

【０１７０】
【化１０】

【０１７１】
【化１１】

【０１７２】
【化１２】

【０１７３】
【化１３】

【０１７４】
【化１４】

【０１７５】
【化１５】

【０１７６】
【化１６】

【０１７７】
【化１７】

【０１７８】
以上のようにして得られた試料を、試料１０１とした。試料１０１とは青感性乳剤層の乳剤をそれぞれ表２のように替えた試料も同様に作製し試料１０２から１１４とした。
【０１７９】
【表２】

【０１８０】
これらの試料の写真特性を調べるために以下のような実験を行った。
各塗布試料を１０℃３０％ＲＨの雰囲気下に置き、高照度露光用感光計（山下電装（株）製ＨＩＥ型）を用いて、グレー発色のセンシトメトリー用の１０^−６秒高照度階調露光を与えた。露光した試料は、露光してから３秒後、９秒後、あるいは３０秒後に以下に示す発色現像処理を行なった。
【０１８１】
以下に処理工程を示す。
［処理］
下記処理工程にて使用した発色現像補充液の容量が発色現像タンク容量の０．５倍となるまで試料１１０を用いて連続処理を行った。
【０１８２】

【０１８３】
各処理液の組成は以下の通りである。

【０１８４】

【０１８５】

【０１８６】
【化１８】

【０１８７】
同様に露光した試料について、露光してから３秒後、９秒後あるいは３０秒後に、上記に示した発色現像処理において発色現像時間を３０秒に変更したことのみ異なる発色現像処理を行なった。更に、各塗布試料を３０℃３０％ＲＨの雰囲気下に置き、同様の実験を繰り返した。
【０１８８】
処理後の各試料のイエロー発色濃度を測定し、１０^−６秒高照度露光の特性曲線を得た。１０℃３０％ＲＨ雰囲気下、露光３秒後に１６秒の発色現像を行なった場合に発色濃度０．７を与える露光量において、露光９秒後に１６秒の発色現像を行なった場合の０．７からの濃度変化をΔＤ（１０℃、３″→９″、１６″）とした。１０℃３０％ＲＨ雰囲気下、露光９秒後に１６秒の発色現像を行なった場合に発色濃度０．７を与える露光量において、露光３０秒後に１６秒の発色現像を行なった場合の０．７からの濃度変化をΔＤ（１０℃、９″→３０″、１６″）とした。
１０℃３０％ＲＨ雰囲気下、露光３秒後に３０秒の発色現像を行なった場合に発色濃度０．７を与える露光量において、露光９秒後に３０秒の発色現像を行なった場合の０．７からの濃度変化をΔＤ（１０℃、３″→９″、３０″）とした。１０℃３０％ＲＨ雰囲気下、露光９秒後に３０秒の発色現像を行なった場合に発色濃度０．７を与える露光量において、露光３０秒後に３０秒の発色現像を行なった場合の０．７からの濃度変化をΔＤ（１０℃、９″→３０″、３０″）とした。
【０１８９】
１０℃３０％ＲＨ雰囲気下露光３秒後に１６秒の発色現像を行なった場合に発色濃度０．７を与える露光量において、３０℃３０％ＲＨ雰囲気下露光３秒後に１６秒の発色現像を行なった場合の０．７からの濃度変化をΔＤ（１０℃→３０℃、３″、１６″）とした。１０℃３０％ＲＨ雰囲気下露光３０秒後に１６秒の発色現像を行なった場合に発色濃度０．７を与える露光量において、３０℃３０％ＲＨ雰囲気下露光３０秒後に１６秒の発色現像を行なった場合の０．７からの濃度変化をΔＤ（１０℃→３０℃、３０″、１６″）とした。
１０℃３０％ＲＨ雰囲気下露光３秒後に３０秒の発色現像を行なった場合に発色濃度０．７を与える露光量において、３０℃３０％ＲＨ雰囲気下露光３秒後に３０秒の発色現像を行なった場合の０．７からの濃度変化をΔＤ（１０℃→３０℃、３″、３０″）とした。１０℃３０％ＲＨ雰囲気下露光３０秒後に３０秒の発色現像を行なった場合に発色濃度０．７を与える露光量において、３０℃３０％ＲＨ雰囲気下露光３０秒後に３０秒の発色現像を行なった場合の０．７からの濃度変化をΔＤ（１０℃→３０℃、３０″、３０″）とした。
【０１９０】
これらの評価の結果を表３および表４に示した。各ΔＤの値が小さいほどプリント濃度が安定で好ましい。
【０１９１】
【表３】

【０１９２】
【表４】

【０１９３】
表３および表４の結果から明らかなように、試料１０１〜１０３を短時間潜像かつ短時間発色現像の条件で処理した場合には、潜像時間の変化や露光環境温度の変化で写真濃度の変化が大きくなり安定なプリント濃度が得られないが（比較例）、試料１０４〜１１４を短時間潜像かつ短時間発色現像の条件で処理した場合には、潜像時間の変化や露光環境温度の変化で写真濃度の変化は大きくならず、安定なプリント濃度が得られることがわかる（本発明）。
【０１９４】
［実施例２］
これらの試料のレーザー走査露光における安定性を調べるために以下のような実験を行った。
レーザー光源としては、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１０６０ｎｍ）を導波路状の反転ドメイン構造を有するＬｉＮｂＯ_３のＳＨＧ結晶により波長変換して取り出した約５３０ｎｍの緑色レーザーおよび波長約６５０ｎｍの赤色半導体レーザー（日立タイプＮｏ．ＨＬ６５０１ＭＧ）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１０℃３０％ＲＨの環境下で、Ａ４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０．７になるようなグレー発色の均一露光を与えた。
【０１９５】
露光した各試料に対し、実施例１と同様の発色現像処理を行なった。均一露光したＡ４試料の先端部は露光後約３秒で発色現像が開始され、後端部は露光後約９秒で発色現像が開始されている。発色現像時間は１６秒とした。
【０１９６】
処理後の各試料の先端部と後端部のイエロー発色濃度を測定し、差ΔＤ_Ｙを読み取った。差ΔＤ_Ｙが正の場合は、先端から後端にかけて濃度が増加していることを示す。結果を表５に示した。
【０１９７】
【表５】

【０１９８】
表５の結果から明らかなように、試料１０４〜１１４にレーザー走査露光し、短時間潜像時間で迅速処理を行なった場合でも、プリント先端部と後端部の色味変化が少なく、安定な品質が得られることがわかる。
【０１９９】
［実施例３］
試料１０１とは、写真構成層を下記のように変えて薄層化した試料を作製した。
第一層（青感性乳剤層）
乳剤Ｂ−１　　　　　　　　　　　　　　　　　　　　　　０．１４
ゼラチン　　　　　　　　　　　　　　　　　　　　　　　０．７５
イエローカプラー（ＥｘＹ−２）　　　　　　　　　　　　０．３４
色像安定剤（Ｃｐｄ−１）　　　　　　　　　　　　　　　０．０４
色像安定剤（Ｃｐｄ−２）　　　　　　　　　　　　　　　０．０２
色像安定剤（Ｃｐｄ−３）　　　　　　　　　　　　　　　０．０４
色像安定剤（Ｃｐｄ−８）　　　　　　　　　　　　　　　０．０１
溶媒（Ｓｏｌｖ−１）　　　　　　　　　　　　　　　　　０．１３
【０２００】
第二層（混色防止層）
ゼラチン　　　　　　　　　　　　　　　　　　　　　　　０．６０
混色防止剤（Ｃｐｄ−１９）　　　　　　　　　　　　　　０．０９
色像安定剤（Ｃｐｄ−５）　　　　　　　　　　　　　　　０．００７
色像安定剤（Ｃｐｄ−７）　　　　　　　　　　　　　　　０．００７
紫外線吸収剤（ＵＶ−Ｃ）　　　　　　　　　　　　　　　０．０５
溶媒（Ｓｏｌｖ−５）　　　　　　　　　　　　　　　　　０．１１
【０２０１】
第三層（緑感性乳剤層）
乳剤Ｇ−１　　　　　　　　　　　　　　　　　　　　　　０．１２
ゼラチン　　　　　　　　　　　　　　　　　　　　　　　０．７３
マゼンタカプラー（ＥｘＭ）　　　　　　　　　　　　　　０．１５
紫外線吸収剤（ＵＶ−Ａ）　　　　　　　　　　　　　　　０．０５
色像安定剤（Ｃｐｄ−２）　　　　　　　　　　　　　　　０．０２
色像安定剤（Ｃｐｄ−７）　　　　　　　　　　　　　　　０．００８
色像安定剤（Ｃｐｄ−８）　　　　　　　　　　　　　　　０．０７
色像安定剤（Ｃｐｄ−９）　　　　　　　　　　　　　　　０．０３
色像安定剤（Ｃｐｄ−１０）　　　　　　　　　　　　　　０．００９
色像安定剤（Ｃｐｄ−１１）　　　　　　　　　　　　　　０．０００１
溶媒（Ｓｏｌｖ−３）　　　　　　　　　　　　　　　　　０．０６
溶媒（Ｓｏｌｖ−４）　　　　　　　　　　　　　　　　　０．１１
溶媒（Ｓｏｌｖ−５）　　　　　　　　　　　　　　　　　０．０６
【０２０２】
第四層（混色防止層）
ゼラチン　　　　　　　　　　　　　　　　　　　　　　　０．４８
混色防止層（Ｃｐｄ−４）　　　　　　　　　　　　　　　０．０７
色像安定剤（Ｃｐｄ−５）　　　　　　　　　　　　　　　０．００６
色像安定剤（Ｃｐｄ−７）　　　　　　　　　　　　　　　０．００６
紫外線吸収剤（ＵＶ−Ｃ）　　　　　　　　　　　　　　　０．０４
溶媒（Ｓｏｌｖ−５）　　　　　　　　　　　　　　　　　０．０９
【０２０３】
第五層（赤感性乳剤層）
乳剤Ｒ−１　　　　　　　　　　　　　　　　　　　　　　０．１０
ゼラチン　　　　　　　　　　　　　　　　　　　　　　　０．５９
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−７）　　　　　　　　　　　　　　　０．０１
色像安定剤（Ｃｐｄ−９）　　　　　　　　　　　　　　　０．０４
色像安定剤（Ｃｐｄ−１５）　　　　　　　　　　　　　　０．１９
色像安定剤（Ｃｐｄ−１８）　　　　　　　　　　　　　　０．０４
紫外線吸収剤（ＵＶ−７）　　　　　　　　　　　　　　　０．０２
溶媒（Ｓｏｌｖ−５）　　　　　　　　　　　　　　　　　０．０９
【０２０４】
第六層（紫外線吸収層）
ゼラチン　　　　　　　　　　　　　　　　　　　　　　　０．３２
紫外線吸収剤（ＵＶ−Ｃ）　　　　　　　　　　　　　　　０．４２
溶媒（Ｓｏｌｖ−７）　　　　　　　　　　　　　　　　　０．０８
第七層（保護層）
ゼラチン　　　　　　　　　　　　　　　　　　　　　　　０．７０
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　　　　　　　　　　　　　　　　　　　　０．０１
界面活性剤（Ｃｐｄ−１３）　　　　　　　　　　　　　　０．０１
ポリジメチルシロキサン　　　　　　　　　　　　　　　　０．０１
二酸化珪素　　　　　　　　　　　　　　　　　　　　　　０．００３
【０２０５】
【化１９】

【０２０６】
以上のようにして得られた試料を、試料２０１とした。試料２０１とは青感性乳剤層の乳剤をそれぞれ表６のように替えた試料も同様に作製し試料２０２から２１４とした。これらの試料に実施例２と同じレーザー走査露光および処理を行い、ΔＤ_Ｙを読み取った。結果を表６に示す。
【０２０７】
【表６】

【０２０８】
表６の結果から明らかなように、試料２０４〜２１４にレーザー走査露光し、短時間潜像時間で迅速処理を行なった場合には、プリント先端部と後端部の色味変化が少なく、安定な品質が得られることがわかる。
【０２０９】
【発明の効果】
以上、本発明によれば、超迅速処理を行なった場合にも常に安定した写真性能が得られる画像形成方法、及びこれに適用されるハロゲン化銀カラー写真感光材料、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を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an image forming method using a silver halide color photographic light-sensitive material and a silver halide color photographic light-sensitive material, and more particularly, to an image forming method and a halogenation using a silver halide color photographic light-sensitive material suitable for rapid processing. The present invention relates to a silver photographic color photographic material, and more particularly, to an image forming method and a silver halide color photographic photographic material using a silver halide color photographic material capable of obtaining stable performance when processed rapidly.
[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, for example, to improve photographic image quality. 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 it has been proposed from each viewpoint. 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.
[0005]
For the above-mentioned purpose, we have examined color printing paper with a short latent image time of 9 seconds or less and color development in a short time of 28 seconds or less. However, it has been found that the color of the obtained print is not stable, and even if the same print is repeatedly baked, the color varies from print to print. Further, it has been found that such instability of color is remarkable when laser scanning exposure is performed. We have made various studies to solve this problem, and have found that it can be solved by including a specific metal complex in the silver halide emulsion used for color photographic paper.
[0006]
As a silver halide emulsion used for color photographic paper, a silver halide emulsion having a high silver chloride content is used because of a demand for rapid processability. It is disclosed that a silver halide emulsion having a high silver chloride content contains various metal complexes. It is known to dope Ir complexes in order to improve the high illuminance failure of silver chloride emulsions and to obtain a high gradation even at high illuminance. For example, Japanese Patent Publication No. 7-34103 discloses that a problem of latent image sensitization can be solved by providing a localized phase having a high silver bromide content and doping it with an Ir complex. US Pat. No. 4,933,272 discloses that low illuminance failure can be reduced by containing a metal complex containing NO or NS as a ligand. US Pat. Nos. 5,360,712, 5,457,021, and 5,462,849 disclose a reciprocity law by including a metal complex containing a specific organic ligand as a ligand. It is disclosed that failure can be reduced. U.S. Patent Nos. 5,372,926, 5,255,630, 5,255,451, 5,597,686, 5,480,771, No. 474,888, No. 5,500,335, No. 5,783,373 and No. 5,783,378 are highly salified with combinations of Ir complexes and metal complexes containing NO as a ligand. It is disclosed that performance such as reciprocity characteristics of silver emulsion can be improved. JP-A Nos. 2000-250156, 2001-92066, and 2002-31866 disclose emulsion techniques that have excellent latent image stability after exposure using a combination of an Ir complex and an Rh complex.
[0007]
JP-A-58-95736, 58-108533, 60-222844, 60-222845, 62-253143, 62-253144, 62-253166, 62-254139 63-46440, 63-46441, 63-89840, U.S. Pat.Nos. 4,820,624, 4,865,962, 5,399,475, 5 , 284, 743 and the like disclose that high sensitivity can be obtained by locally incorporating a phase having a high silver bromide content in various forms in an emulsion having a high silver chloride content.
[0008]
In US Pat. Nos. 5,726,005 and 5,736,310, emulsions containing I having a maximum concentration on the subsurface of high silver chloride emulsions provide emulsions with high sensitivity and low illuminance failure. It is disclosed that it can be obtained. In the examples of European Patent EP 0,928,988A, a specific compound is contained in a particle that formed an I band at 93% of the particle formation, thereby causing reciprocity failure, temperature dependence and pressure characteristics during exposure. It is disclosed that an excellent emulsion can be obtained.
[0009]
However, these known techniques do not discuss improvement in instability of photographic characteristics when the latent image time is 9 seconds or less and color development is performed in a short time of 28 seconds or less.
[0010]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a silver halide color photographic light-sensitive material and an image forming method capable of always obtaining stable photographic performance even when ultra-rapid processing is performed by overcoming the above-mentioned problems. That is. Another object of the present invention is to provide a silver halide color photographic light-sensitive material particularly suitable for color printing and an image forming method.
[0011]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means.
(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 the support An image forming method in which color development is performed after imagewise exposure of a silver halide color photographic light-sensitive material having a photographic composition layer comprising one layer,
A silver halide emulsion having a silver chloride content of 90 mol% or more containing at least one selected from metal complexes represented by the following general formula (I) in at least one of the silver halide emulsion layers;
An image forming method comprising: starting color development within 9 seconds after imagewise exposing the silver halide color photographic material, and performing the color development within 28 seconds.
Formula (I)
[IrX^I _nL^I _(6-n)]^m
(In the general formula (I), X^IRepresents a halogen ion or a pseudo-halogen ion, and L^IIs X^IRepresents an arbitrary ligand different from n, n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+. )
[0012]
(2) At least each of 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 the support An image forming method in which color development is performed after imagewise exposure of a silver halide color photographic light-sensitive material having a photographic composition layer comprising one layer,
Including at least one silver halide emulsion containing at least one selected from metal complexes represented by the following general formula (II) and having a silver chloride content of 90 mol% or more in at least one of the silver halide emulsion layers,
An image forming method comprising: starting color development within 9 seconds after imagewise exposing the silver halide color photographic material, and performing the color development within 28 seconds.
Formula (II)
[MX^II _nL^II _(6-n)]^m
(In the general formula (II), M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, and X^IIRepresents a halogen ion, L^IIIs X^IIRepresents an arbitrary ligand different from, n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0, or 1+. )
[0013]
(3) At least each of 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 the support An image forming method in which color development is performed after imagewise exposure of a silver halide color photographic light-sensitive material having a photographic composition layer comprising one layer,
At least one selected from a metal complex represented by the following general formula (I) and at least one selected from a metal complex represented by the following general formula (II) in at least one layer of the silver halide emulsion layer: A silver halide emulsion having a silver chloride content of 90 mol% or more,
An image forming method, wherein color development is started within 9 seconds after imagewise exposure of the silver halide color photographic light-sensitive material, and the color development is performed within 28 seconds.
Formula (I)
[IrX^I _nL^I _(6-n)]^m
(In the general formula (I), X^IRepresents a halogen ion or a pseudo-halogen ion, and L^IIs X^IRepresents an arbitrary ligand different from n, n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+. )
Formula (II)
[MX^II _nL^II _(6-n)]^m
(In the general formula (II), M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, and X^IIRepresents a halogen ion, L^IIIs X^IIRepresents an arbitrary ligand different from, n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0, or 1+. )
[0014]
(4) A silver halide color photographic light-sensitive material for rapid processing, in which color development is started within 9 seconds after imagewise exposure, and the color development is performed within 28 seconds to form an image. ,
The silver halide color photographic light-sensitive material comprises a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer and a non-photosensitive material on a support. Having a photographic composition layer comprising at least one each of the hydrophilic colloid layers,
And at least one of the silver halide emulsion layers contains a silver halide emulsion containing at least one selected from metal complexes represented by the following general formula (I) and having a silver chloride content of 90 mol% or more. A silver halide color photographic light-sensitive material characterized by the above.
Formula (I)
[IrX^I _nL^I _(6-n)]^m
(In the general formula (I), X^IRepresents a halogen ion or a pseudo-halogen ion, and L^IIs X^IRepresents an arbitrary ligand different from n, n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+. )
[0015]
(5) A silver halide color photographic light-sensitive material for rapid processing, wherein color development is started within 9 seconds after imagewise exposure, and the color development is carried out within 28 seconds to form an image. ,
The silver halide color photographic light-sensitive material comprises a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer and a non-photosensitive material on a support. Having a photographic composition layer comprising at least one each of the hydrophilic colloid layers,
And at least one of the silver halide emulsion layers contains a silver halide emulsion containing at least one selected from metal complexes represented by the following general formula (II) and having a silver chloride content of 90 mol% or more. A silver halide color photographic light-sensitive material characterized by the above.
Formula (II)
[MX^II _nL^II _(6-n)]^m
(In the general formula (II), M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, and X^IIRepresents a halogen ion, L^IIIs X^IIRepresents an arbitrary ligand different from, n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0, or 1+. )
[0016]
(6) A silver halide color photographic light-sensitive material for rapid processing, wherein color development is started within 9 seconds after imagewise exposure, and the color development is carried out within 28 seconds to form an image. ,
The silver halide color photographic light-sensitive material comprises a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer and a non-photosensitive material on a support. Having a photographic composition layer comprising at least one each of the hydrophilic colloid layers,
And at least one selected from a metal complex represented by the following general formula (I) and at least one selected from a metal complex represented by the following general formula (II) in at least one of the silver halide emulsion layers: A silver halide color photographic light-sensitive material containing a silver halide emulsion containing 90 mol% or more of silver chloride.
Formula (I)
[IrX^I _nL^I _(6-n)]^m
(In the general formula (I), X^IRepresents a halogen ion or a pseudo-halogen ion, and L^IIs X^IRepresents an arbitrary ligand different from n, n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+. )
Formula (II)
[MX^II _nL^II _(6-n)]^m
(In the general formula (II), M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, and X^IIRepresents a halogen ion, L^IIIs X^IIRepresents an arbitrary ligand different from, n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0, or 1+. )
[0017]
(7) The silver halide color described in (4) or (6), wherein the metal complex represented by the general formula (I) is a metal complex represented by the following general formula (IA) Photosensitive material.
Formula (IA)
[IrX^IA _nL^IA _(6-n)]^m
(In the general formula (IA), X^IARepresents a halogen ion or a pseudo-halogen ion, and L^IAIs X^IARepresents an arbitrary inorganic ligand different from n, n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+. )
[0018]
(8) The silver halide color as described in (4) or (6), wherein the metal complex represented by the general formula (I) is a metal complex represented by the following general formula (IB) Photosensitive material.
Formula (IB)
[IrX^IB _nL^IB _(6-n)]^m
(In the general formula (IB), X^IBRepresents a halogen ion or a pseudo-halogen ion, and 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, and n is 3, 4 Or 5 and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+. )
[0019]
(9) The silver halide color as described in (4) or (6), wherein the metal complex represented by the general formula (I) is a metal complex represented by the following general formula (IC) Photosensitive material.
General formula (IC)
[IrX^IC _nL^IC _(6-n)]^m
(In the general formula (IC), X^ICRepresents a halogen ion or a pseudo-halogen ion, and L^ICIs a 5-membered ring ligand and represents a ligand containing at least one nitrogen atom and at least one sulfur atom in the ring skeleton, and may have an arbitrary substituent on a carbon atom in the ring skeleton . n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+. )
[0020]
(10) The silver halide color as described in (4) or (6), wherein the metal complex represented by the general formula (I) is a metal complex represented by the following general formula (ID) Photosensitive material.
General formula (ID)
[IrX^ID _nL^ID _(6-n)]^m
(In general formula (ID), X^IDRepresents a halogen ion or a pseudo-halogen ion, and L^IDIs a 5-membered ring ligand and represents a ligand containing at least two nitrogen atoms and at least one sulfur atom in the ring skeleton, and may have an arbitrary substituent on a carbon atom in the ring skeleton . n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+. )
[0021]
(11) The silver halide color as described in (5) or (6), wherein the metal complex represented by the general formula (II) is a metal complex represented by the following general formula (IIA) Photosensitive material.
Formula (IIA)
[M^IIAX^IIA _nL^IIA _(6-n)]^m
(In the general formula (IIA), M^IIARepresents Re, Ru, Os or Rh, and 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 m represents 4-, 3-, 2-, 1-, 0, or 1+. )
[0022]
(12) In the above (6), the metal complex represented by the general formula (I) is a metal complex represented by the general formula (IA), and the metal complex represented by the general formula (II) The silver halide color photographic light-sensitive material as described in (6), which is a metal complex represented by the general formula (IIA).
[0023]
(13) In the above (6), the metal complex represented by the general formula (I) is a metal complex represented by the general formula (IB), and the metal complex represented by the general formula (II) The silver halide color photographic light-sensitive material as described in (6), which is a metal complex represented by the general formula (IIA).
[0024]
(14) In the above (6), the metal complex represented by the general formula (I) is a metal complex represented by the general formula (IC), and the metal complex represented by the general formula (II) The silver halide color photographic light-sensitive material as described in (6), which is a metal complex represented by the general formula (IIA).
[0025]
(15) In the above (6), the metal complex represented by the general formula (I) is a metal complex represented by the general formula (ID), and the metal complex represented by the general formula (II) is The silver halide color photographic light-sensitive material as described in (6), which is a metal complex represented by the general formula (IIA).
[0026]
(16) The total coated silver amount in the photographic composition layer is 0.2 g / m.²0.5 g / m²The silver halide color photographic light-sensitive material as described in any one of (4) to (15), which is:
[0027]
(17) The total coated gelatin amount in the photographic composition layer is 3 g / m.²6 g / m or more²The silver halide color photographic light-sensitive material as described in any one of (4) to (16), wherein:
[0028]
(18) Any one of (4) to (17), wherein the silver halide emulsion in the yellow dye-forming coupler-containing silver halide emulsion layer is a silver halide emulsion having a sphere equivalent diameter of 0.6 μm or less. The silver halide color photographic light-sensitive material as described in the above item.
[0029]
(19) The silver halide emulsion in the silver halide emulsion layer further contains 0.1 to 7 mol% of silver bromide, and the silver bromide concentration is higher than the surroundings in the silver halide emulsion grains. The silver halide color photographic light-sensitive material as described in any one of (4) to (18), wherein a high silver bromide-containing phase is formed.
[0030]
(20) The silver halide emulsion in the silver halide emulsion layer contains 0.02 to 1 mol% of silver iodide and forms a silver iodide-containing phase having a higher silver iodide concentration than the surroundings. The silver halide color photographic light-sensitive material as described in any one of (4) to (19), wherein:
[0031]
(21) An image forming method, wherein the silver halide color photographic light-sensitive material according to any one of (4) to (20) is imagewise exposed by laser scanning exposure.
[0032]
(22) The silver halide color photographic light-sensitive material according to any one of (4) to (20) is imagewise exposed by scanning exposure using a blue semiconductor laser having an emission wavelength of 420 nm to 460 nm. Image forming method.
[0033]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The present invention uses a silver halide color photographic light-sensitive material described later, starts color development within 9 seconds after imagewise exposure, and the color development is carried out within 28 seconds. It is a silver halide color photographic light-sensitive material applicable to such rapid processing. In the present invention, when a silver halide color photographic light-sensitive material described later is subjected to a rapid processing as described above with a short latent image time, a stable photographic performance can always be obtained.
[0034]
Hereinafter, an image forming method will be described together with a description of a silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as “photosensitive material”) applied to the present invention.
[0035]
The light-sensitive material comprises 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 having a photographic constituent layer comprising at least one layer, and in at least one of the silver halide emulsion layers, a metal complex represented by the following general formula (I) or / And a silver halide emulsion containing a metal complex represented by the general formula (II) and having a silver chloride content of 90 mol% or more.
[0036]
The silver halide emulsion layer containing the yellow dye-forming coupler is a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler is a magenta coloring layer, and the silver halide containing the cyan dye-forming coupler. The emulsion layer functions as a cyan coloring layer. The silver halide emulsions contained in the yellow coloring layer, the magenta coloring layer and the cyan coloring layer, respectively, are sensitive to light in different wavelength regions (for example, light in the blue region, green region and red region). It is preferable to have.
[0037]
In addition to the yellow coloring layer, magenta coloring layer, and cyan coloring layer, the photosensitive material may have an antihalation layer, an intermediate layer, and a colored layer as a hydrophilic colloid layer to be described later if desired.
[0038]
Hereinafter, the metal complex represented by the general formula (I) or (II) will be described. First, the metal complex represented by the general formula (I) will be described.
[0039]
Formula (I)
[IrX^I _nL^I _(6-n)]^m
In general formula (I), X^IRepresents a halogen ion or a pseudo-halogen ion, and L^IIs X^IRepresents an arbitrary ligand different from n, n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+.
In the above, the pseudohalogen (halogenoid) ion is an ion having properties similar to a halogen ion. For example, a cyanide ion (CN)⁻), Thiocyanate ion (SCN)⁻), Selenocyanate ion (SeCN)⁻), Tellurocyanate ion (TeCN)⁻), Azidodithiocarbonate ion (SCSN)₃ ⁻), Cyanate ion (OCN)⁻), Thunderate ion (ONC)⁻), Azide ion (N₃ ⁻) And the like.
[0040]
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.
[0041]
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 among these, a metal complex represented by the general formula (IB) is more preferable.
[0042]
Formula (IA)
[IrX^IA _nL^IA _(6-n)]^m
In general formula (IA), X^IARepresents a halogen ion or a pseudo-halogen ion, and L^IAIs X^IARepresents an arbitrary inorganic ligand different from n, n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+.
X^IAIs X in the general formula (I)^IThe preferred range is also the same.
L^IAPreferred is water, OCN, ammonia, phosphine, or carbonyl, with water being particularly preferred.
[0043]
Formula (IB)
[IrX^IB _nL^IB _(6-n)]^m
In general formula (IB), X^IBRepresents a halogen ion or a pseudo-halogen ion, and L^IBRepresents a ligand in which a chain or cyclic hydrocarbon is a parent structure, or a carbon or hydrogen atom in a part of the parent structure is replaced with another atom or atomic group, and n is 3, 4 Or 5 and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+.
X^IBIs X in the general formula (I)^IThe preferred range is also the same.
L^IBRepresents a ligand in which a chain or cyclic hydrocarbon is a parent structure, or a carbon or hydrogen atom in a part of the parent structure is replaced with another atom or atomic group, and a cyanide ion is exclude.
L^IBIs preferably a heterocyclic compound. More preferably, it is a complex having a 5-membered ring compound as a ligand, and among the 5-membered ring compounds, it is further a compound containing at least one nitrogen atom and at least one sulfur atom in a 5-membered ring skeleton. preferable.
[0044]
Among the metal complexes represented by the general formula (IB), the metal complex represented by the following general formula (IC) is more preferable.
[0045]
General formula (IC)
[IrX^IC _nL^IC _(6-n)]^m
X^ICRepresents a halogen ion or a pseudo-halogen ion, and L^ICIs a 5-membered ring ligand and represents a ligand containing at least one nitrogen atom and at least one sulfur atom in the ring skeleton, and may have an arbitrary substituent on a carbon atom in the ring skeleton . n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+.
X^ICIs X in the general formula (I)^IThe preferred range is also the same.
L^ICThe substituent on the carbon atom in the inner ring skeleton is preferably a substituent having a smaller volume than the n-propyl group. 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, and a hydroxy group. And a mercapto group, an amino group, a hydrazino group, an azide group, a nitro group, a nitroso group, a hydroxyamino group, a carboxyl group, a carbamoyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
[0046]
Among the metal complexes of the general formula (IC), a metal complex represented by the following general formula (ID) is more preferable.
[0047]
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, and L^IDIs a 5-membered ring ligand and represents a ligand containing at least two nitrogen atoms and at least one sulfur atom in the ring skeleton, and may have an arbitrary substituent on a carbon atom in the ring skeleton . n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+.
X^IDIs X in the general formula (I)^IThe preferred range is also the same.
L^IDAs a compound having thiadiazole as a skeleton, a substituent other than hydrogen is preferably bonded to a carbon atom in the compound. The substituent is preferably a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxy group (preferably methoxy, ethoxy), a carboxyl group, an alkoxycarbonyl group (preferably methoxycarbonyl), an acyl group (preferably Is 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 , Isocyanato group, isocyanato group, isocyanato group, thiocyanato group, isothiocyanato group, hydroxyamino group, hydroxyimino group, carbamoyl group, nitroso group, nitro group, hydrazino group, hydrazono group or azide group, More preferably, a halogen atom, a chloroformyl group, a sulfino group, a sulfo group, a sulfamoyl group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a hydroxyimino group, a nitroso group, a nitro group, or an azido group is there. Of these, a chlorine atom, a bromine atom, a chloroformyl group, an isocyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, and an isothiocyanato group are particularly preferable.
[0048]
In general formulas (I) to (ID), n is preferably 4 or 5, m is preferably 4-, 3-, 2-, 1-, 0, or 1+, and more preferably 2-, Or 1-.
[0049]
Although the preferable specific example of a metal complex represented with general formula (I) below is given, this invention is not limited to these.
[0050]
[IrCl₅(H₂O)]^2-
[IrCl₄(H₂O)₂]⁻
[IrCl₅(H₂O)]⁻
[IrCl₄(H₂O)₂]⁰
[IrCl₅(OH)]^3-
[IrCl₄(OH)₂]^2-
[IrCl₅(OH)]^2-
[IrCl₄(OH)₂]^2-
[IrCl₅(O)]^4-
[IrCl₄(O)₂]^5-
[IrCl₅(O)]^3-
[IrCl₄(O)₂]^4-
[IrBr₅(H₂O)]^2-
[IrBr₄(H₂O)₂]⁻
[IrBr₅(H₂O)]⁻
[IrBr₄(H₂O)₂]⁰
[IrBr₅(OH)]^3-
[IrBr₄(OH)₂]^2-
[IrBr₅(OH)]^2-
[IrBr₄(OH)₂]^2-
[IrBr₅(O)]^4-
[IrBr₄(O)₂]^5-
[IrBr₅(O)]^3-
[IrBr₄(O)₂]^4-
[IrCl₅(OCN)]^3-
[IrBr₅(OCN)]^3-
[IrCl₅(Thiazole)]^2-
[IrCl₄(Thiazole)₂]⁻
[IrCl₃(Thiazole)₃]⁰
[IrBr₅(Thiazole)]^2-
[IrBr₄(Thiazole)₂]⁻
[IrBr₃(Thiazole)₃]⁰
[IrCl₅(5-methylthiazole)]^2-
[IrCl₄(5-methylthiazole)₂]⁻
[IrBr₅(5-methylthiazole)]^2-
[IrBr₄(5-methylthiazole)₂]⁻
[IrCl₅(5-chlorothiazole)]^2-
[IrCl₄(5-chlorothiazole)₂]⁻
[IrBr₅(5-chlorothiazole)]^2-
[IrBr₄(5-chlorothiazole)₂]⁻
[IrCl₅(2-chloro-5-fluorothiadiazole)]^2-
[IrCl₄(2-chloro-5-fluorothiadiazole)₂]⁻
[IrBr₅(2-chloro-5-fluorothiadiazole)]^2-
[IrBr₄(2-chloro-5-fluorothiadiazole)₂]⁻
[IrCl₅(2-Bromo-5-chlorothiazole)]^2-
[IrCl₄(2-Bromo-5-chlorothiadiazole)₂]⁻
[IrBr₅(2-Bromo-5-chlorothiazole)]^2-
[IrBr₄(2-Bromo-5-chlorothiadiazole)₂]⁻
[0051]
Next, the metal complex represented by the following general formula (II) will be described.
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, and X^IIRepresents a halogen ion, L^IIIs X^IIRepresents an arbitrary ligand different from, n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0, or 1+.
X^IIIs a fluoride ion, a chloride ion, a bromide ion, or an iodide ion, and among them, a chloride ion and a bromide ion are particularly preferable. L^IIMay be an inorganic compound or an organic compound, and may be charged or uncharged, but is preferably an uncharged inorganic compound. L^IIPreferably H₂0, NO or NS.
[0052]
Among the metal complexes represented by the general formula (II), metal complexes represented by the following general formula (IIA) are preferable.
[0053]
Formula (IIA)
[M^IIAX^IIA _nL^IIA _(6-n)]^m
In general formula (IIA), M^IIARepresents Re, Ru, Os or Rh, and 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 m represents 4-, 3-, 2-, 1-, 0, or 1+.
X^IIAIs X in the general formula (II)^IIThe preferred range is also the same.
[0054]
Hereinafter, although the preferable specific example of a metal complex represented by general formula (II) is given, this invention is not limited to these.
[0055]
[ReCl₆]^2-
[ReCl₅(NO)]^2-
[RuCl₆]^2-
[RuCl₆]^3-
[RuCl₅(NO)]^2-
[RuCl₅(NS)]^2-
[RuBr₅(NS)]^2-
[OsCl₆]^4-
[OsCl₅(NO)]^2-
[OsBr₅(NS)]^2-
[RhCl₆]^3-
[RhCl₅(H₂O)]^2-
[RhCl₄(H₂O)₂]⁻
[RhBr₆]^3-
[RhBr₅(H₂O)]^2-
[RhBr₄(H₂O)₂]⁻
[PdCl₆]^2-
[PtCl₆]^2-
[0056]
The metal complex mentioned above is an anion, and when a salt is formed with a cation, the metal complex that is easily dissolved in water as the counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do. The metal complex represented by the general formula (I) is 1 × 10 5 per mol of silver during grain formation.^-10From mole to 1 × 10^-3Mole addition is preferred, 1 × 10^-8From mole to 1 × 10^-5Most preferably, it is added in a molar amount. 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.
[0057]
The above metal complex is added directly to the reaction solution at the time of silver halide grain formation, added to an aqueous halide solution for forming silver halide grains, or other solution, and added to the grain formation reaction solution. It is preferable to incorporate it into the silver halide grains by adding them. It is also preferable to physically ripen the fine particles in which the metal complex 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.
[0058]
When these metal complexes are incorporated into silver halide grains, they can be uniformly present inside the grains, but disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to exist 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 US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Further, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain.
[0059]
Next, the silver halide emulsion will be described.
The silver halide emulsion contains specific silver halide grains. The particle shape is not particularly limited, but is substantially a cubic or tetradecahedral crystal particle having {100} faces (they may have rounded particle vertices and may have higher-order faces), 8 It is preferable that the crystal grain of a plane body and the main surface consist of a tabular grain having an aspect ratio of 3 or more and comprising a {100} plane or {111} plane. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle.
[0060]
The silver chloride content of the silver halide emulsion needs to be 90 mol% or more. From the viewpoint of rapid processability, the silver chloride content is preferably 93 mol% or more, more preferably 95 mol% or more. The silver bromide content is preferably 0.1 to 7 mol%, more preferably 0.5 to 5 mol%, since it is a high contrast and has excellent latent image stability. The silver iodide content is preferably 0.02-1 mol%, more preferably 0.05-0.50 mol%, and more preferably 0.07-0. 40 mol% is most preferred. The specific silver halide grains of the present invention are preferably silver iodobromochloride grains, more preferably silver iodobromochloride grains having the above halogen composition.
[0061]
The specific silver halide grains in the silver halide emulsion preferably have a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than the surroundings. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide or silver iodide-containing phase may form a layer having a substantially constant width at a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more, more preferably 10 to 80 mol%, and most preferably 15 to 50 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Most preferred. Further, a plurality of such silver bromide or silver iodide-containing phases may be formed in layers in each grain, and the silver bromide or silver iodide content may be different, but at least one of each. It is necessary to have a contained phase of
[0062]
It is important that the silver bromide-containing phase or the silver iodide-containing phase of the silver halide emulsion 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.
[0063]
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 of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in a layered manner so as to have a silver iodide concentration maximum on the surface of the grain. Such a silver bromide-containing phase or silver iodide-containing phase is composed of a silver amount of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the silver content is 3% or more and 15% or less.
[0064]
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.
[0065]
The silver bromide content or silver iodide content necessary for exhibiting the effects of the present invention such as high sensitivity and high contrast is such that the silver bromide-containing phase or silver iodide-containing phase is formed inside the grain. There is a risk that the amount of silver chloride may be reduced more than necessary, and the rapid processability may be impaired. Therefore, in order to concentrate these functions for controlling the photographic action near the surface in the grain, the silver bromide-containing phase and the silver iodide-containing phase are preferably adjacent to each other. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume as measured from the inside, and the silver iodide-containing phase is any of the positions at 85% to 100% of the grain volume. It is preferable to form it. Further, the silver bromide-containing phase is formed at any position from 70% to 95% of the grain volume, and the silver iodide-containing phase is further formed at any position from 90% to 100% of the grain volume. preferable.
[0066]
In order to incorporate silver bromide or silver iodide into a silver halide emulsion, bromide or iodide ions can be introduced by adding a bromide salt or an iodide salt solution alone, or by adding a silver salt solution and a high chloride salt. Along with the addition of the solution, a bromide salt or iodide salt solution may be added. In the latter case, bromide salt or iodide salt solution and high chloride salt solution may be added separately or as a mixed solution of bromide salt or iodide salt and high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can 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.
[0067]
The addition of the bromide salt or iodide salt solution may be concentrated at one time of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining an emulsion with high sensitivity and low covering. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. Further, the addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, so that an emulsion with higher sensitivity and lower covering can be obtained.
On the other hand, the addition of the bromide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70%.
[0068]
Distribution of bromide or iodide ion concentration in the depth direction in the grain is measured by etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using TRIFT II type TOF-SIMS manufactured by Phi Evans. it can. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan. When the emulsion grains are analyzed by the etching / TOF-SIMS method, it is possible to analyze that iodide ions ooze out toward the grain surface even when the addition of the iodide salt solution is finished inside the grains. The emulsion of the present invention is analyzed by etching / TOF-SIMS method, and it is preferable that iodide ions have a maximum concentration on the grain surface, and the iodide ion concentration is attenuated toward the inside. It is preferable to have a concentration maximum inside. The local concentration of silver bromide can also be measured by X-ray diffraction if the silver bromide content is somewhat high.
[0069]
In this specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. The silver halide emulsion is preferably composed of grains having a monodispersed grain size distribution. The variation system number of the sphere equivalent diameter of all silver halide grains in the silver halide emulsion is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. The variation coefficient of the equivalent sphere diameter is expressed as a percentage of the standard deviation of the equivalent sphere diameter of each particle with respect to the average equivalent sphere diameter. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating.
[0070]
In the silver halide emulsion, the sphere equivalent diameter of the silver halide emulsion of the yellow dye-forming coupler-containing silver halide emulsion layer is preferably 0.6 μm or less (preferably 0.6 μm to 0.15 μm). More preferably, it is 5 μm or less (preferably 0.5 μm to 0.15 μm), and most preferably 0.4 μm or less (preferably 0.4 μm to 0.20 μm). The sphere equivalent diameter of the silver halide emulsion layers containing the magenta dye-forming coupler-containing silver halide emulsion layer and cyan dye-forming coupler-containing silver halide emulsion layer should be 0.5 μm or less (preferably 0.5 μm to 0.1 μm). Is preferably 0.4 μm or less (preferably 0.4 μm to 0.1 μm), and most preferably 0.3 μm or less (preferably 0.3 μm to 0.1 μm). In this specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. Particles with a sphere equivalent diameter of 0.6 μm correspond to cubic particles with a side length of about 0.48 μm, particles with a sphere equivalent diameter of 0.5 μm correspond to cubic particles with a side length of about 0.40 μm, and a sphere equivalent diameter of 0.4 μm. These particles correspond to cubic particles having a side length of about 0.32 μm, and particles having a sphere equivalent diameter of 0.3 μm correspond to cubic particles having a side length of about 0.24 μm. The silver halide emulsion of the present invention may contain silver halide grains other than the silver halide grains (that is, specific silver halide grains) contained in the silver halide emulsion defined in the present invention. However, the silver halide emulsion defined in the present invention requires that 50% or more of the total projected area of all grains be silver halide grains as defined in the present invention, and preferably 80% or more. More preferably, it is 90% or more.
[0071]
In addition to the iridium complex represented by the general formula (I) and / or the general formula (II), the specific silver halide grains in the silver halide emulsion include all six ligands from Cl, Br or I alone. The iridium complex may be further contained. In this case, Cl, Br, or I may be mixed in the hexacoordinate complex. It is particularly preferable that the iridium complex having Cl, Br or I as a ligand is contained in the silver bromide-containing phase in order to obtain a high gradation at high illumination exposure. These iridium metal complexes are preferably used in combination with the iridium metal complex represented by the general formula (I).
[0072]
Specific examples of iridium complexes in which all six ligands are Cl, Br, or I are given below, but are not limited thereto.
[IrCl₆]^2-
[IrCl₆]^3-
[IrBr₆]^2-
[IrBr₆]^3-
[IrI₆]^3-
[0073]
In addition to the metal complexes described above, the silver halide emulsion can be doped with other metal ions inside and / or on the surface of the silver halide grains. As a metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any of the above metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and a plurality of kinds of ligands are contained in one complex molecule. It is also preferable to use it. An organic compound can also be used as the ligand, and preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom in the molecule as a coordination atom to the metal, particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds are used as a basic skeleton and substituents are introduced into them are also preferable.
[0074]
A combination of metal ions and ligands is preferably a combination of iron ions, ruthenium ions and cyanide ions. In the present invention, it is preferable to use the above-described metal complex and these compounds in combination. In these compounds, the cyanide ion preferably accounts for a majority of the coordination number to iron or ruthenium as the central metal, and the remaining coordination sites are thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, It is preferably occupied by pyrazine or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. These complexes with cyanide ions as ligands are 1 × 10 5 per mole of silver during grain formation.^-8From mole to 1 × 10^-2Mole addition is preferred, 1 × 10^-6From mole to 5 × 10^-4Most preferably, it is added in a molar amount.
[0075]
The silver halide emulsion 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.
[0076]
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, for example, potassium bis (1- [3- (2-sulfonatenatebenzamide) ) Phenyl] -5-mercaptotetrazole potassium salt) orate (I) pentahydrate, gold (I) compound coordinated with nitrogen compound anion described in JP-A-4-268550, for example, bis (1-methylhydan Toinert) gold (I) sodium salt tetrahydrate can be used. The gold (I) compound having these organic ligands may be synthesized in advance and isolated, or may be mixed with an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof). Can be added to the emulsion without generation and isolation. Furthermore, an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof) may be added separately to the emulsion to generate a gold (I) compound having an organic ligand in the emulsion.
Further, gold (I) thiolate compounds described in US Pat. No. 3,503,749, gold compounds described in JP-A-8-69074, JP-A-8-69075, and JP-A-9-269554, The compounds described in Patent Nos. 5,620,841, 5,912,112, 5,620,841, 5,939,245, and 5,912,111 are also used. be able to.
The amount of these compounds added may vary widely depending on the case, but is 5 × 10 5 per mole of silver halide.^-7~ 5x10^-3Mole, preferably 5 × 10^-6~ 5x10^-4Is a mole.
[0077]
Colloidal gold sulfide can also be used. The manufacturing method thereof is Research Disclosure (Research Disclosure, 37154), Solid State Ionics, Vol. 79, 60-66, 1995, Compt. Rend. Hebt. Seans Acad. Sci. Sect. B 263, 1328, 1966, etc. The Research Disclosure describes a method using thiocyanate ions in the production of colloidal gold sulfide, but a thioether compound such as methionine or thiodiethanol can be used instead.
[0078]
Various sizes of colloidal gold sulfide can be used, those having an average particle diameter of 50 nm or less are preferred, average particle diameters of 10 nm or less are more preferred, and average particle diameters of 3 nm or less are even more preferred. 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.
[0079]
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 gold atoms per mole of silver halide.^-7~ 5x10^-3Mole, preferably 5 × 10^-6~ 5x10^-4Is a mole.
[0080]
In addition to gold sensitization, chalcogen sensitization can be performed with the same molecule.⁻Can be used. Here, Au represents Au (I), and Ch represents a sulfur atom, a selenium atom, or a tellurium atom. AuCh⁻Examples of the molecule capable of releasing a include a gold compound represented by AuCh-L. Here, L represents an atomic group constituting a molecule by binding to AuCh. Further, one or more ligands may be coordinated with Au together with Ch-L. In addition, when the gold compound represented by AuCh-L is reacted in a solvent in the presence of silver ions, AgAuS is produced when Ch is S, AgAuSe is produced when Ch is Se, and AgAuTe is produced 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, and other examples include compounds represented by the following general formulas (AuCh1), (AuCh2), and (AuCh3).
[0081]
General formula (AuCh 1)
R₁-X-M-ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, selenium atom, or tellurium atom, M represents a substituted or unsubstituted methylene group, X represents an oxygen atom, sulfur atom, selenium atom, or 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 be bonded to each other to form a ring.
[0082]
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, and 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.
[0083]
General formula (AuCh 2)
W₁W₂C = CR₃ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, selenium atom or tellurium atom, R₃And W₂Represents a substituent (for example, a hydrogen atom, a halogen atom, and an organic group such as an alkyl group, an aryl group, a heterocyclic group), and W₁Is Hammett's substituent constant σ_pAn electron-withdrawing group having a positive value is represented. R₃And W₁, R₃And W₂W₁And W₂May combine with each other to form a ring.
[0084]
In the compound represented by the general formula (AuCh 2), one in which Ch is a sulfur atom or a selenium atom is preferred, and R₃Is preferably a hydrogen atom or an alkyl group, and W₁And W₂Is Hammett's substituent constant σ_pAn electron withdrawing group having a value of 0.2 or more is preferred. Examples of more specific compounds include (NC)₂C = CHSAu, (CH₃OCO)₂C = CHSAu, CH₃CO (CH₃OCO) C = CHSAu and the like.
[0085]
General formula (AuCh 3)
W₃-E-ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, selenium atom or tellurium atom, E represents a substituted or unsubstituted ethylene group, W₃Is Hammett's substituent constant σ_pAn electron-withdrawing group having a positive value is represented.
[0086]
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 a Hammett's substituent constant σ._pIt is preferably an ethylene group having an electron-withdrawing group having a positive value, and W₃Is Hammett's substituent constant σ_pAn electron withdrawing group having a value of 0.2 or more is preferred. The amount of these compounds added may vary widely depending on the case, but is 5 × 10 5 per mole of silver halide.^-7~ 5x10^-3Moles, preferably 3 × 10^-6~ 3x10^-4Is a mole.
[0087]
In silver halide emulsions, the above gold sensitization is further combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization or noble metal sensitization using other than gold compounds. Also good. It is particularly preferable to combine with sulfur sensitization and selenium sensitization.
[0088]
Various compounds or precursors thereof can be added to the silver halide emulsion for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. Specific examples of these compounds are preferably those described on pages 39 to 72 of JP-A-62-215272. Further, 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (the aryl residue has at least one electron-withdrawing group) are also preferably used.
[0089]
In order to improve the storage stability of the silver halide emulsion, the silver halide emulsion is adjacent to the hydroxamic acid derivative described in JP-A No. 11-109576 and the carbonyl group described in JP-A No. 11-327094. Are cyclic ketones having a double bond substituted with an amino group or a hydroxyl group (in particular, those represented by the general formula (S1), and paragraph numbers 0036 to 0071 can be incorporated in the present specification). Sulfo-substituted catechol and hydroquinones described in JP-A-11-143011 (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3, 4-dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid Acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), hydroxylamines represented by the general formula (A) in US Pat. No. 5,556,741 (US Pat. No. 556,741 column 4, line 56 to column 11, line 22 is preferably applied to the present application and is incorporated as part of the present specification), Japanese Patent Application Laid-Open No. 11-102045. The water-soluble reducing agents represented by the general formulas (I) to (III) in the publication are also preferably used in the present invention.
[0090]
The silver halide emulsion may contain a spectral sensitizing dye for the purpose of imparting so-called spectral sensitivity that exhibits 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.
[0091]
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.
[0092]
Hereinafter, preferred embodiments applied to the photosensitive material will be described.
Conventionally known photographic materials and additives can be used for the photosensitive material.
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.
[0093]
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 the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no 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.
[0094]
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.
[0095]
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.
[0096]
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.
[0097]
Further, as the support used for the photosensitive material, a white polyester support or a support provided with a layer containing a white pigment on a support having a silver halide emulsion layer may be used for display. . 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.
[0098]
In the light-sensitive material, for the purpose of improving the sharpness of an image, a hydrophilic colloid layer is coated with a dye (in particular, an oxonol-based dye) described in pages 27 to 76 of European Patent EP0,337,490A2. Dyes) such that the optical reflection density at 680 nm of the photosensitive material is 0.70 or more, or in the water-resistant resin layer of the support with 2- to 4-valent alcohols (for example, trimethylolethane). It is preferable to contain 12% by mass or more (more preferably 14% by mass or more) of the surface-treated titanium oxide.
[0099]
The photosensitive material can be decolorized by processing as described in pages 27 to 76 of EP 0337490A2 in the hydrophilic colloid layer for the purpose of preventing irradiation and halation, and improving safetylight safety. It is preferable to add various dyes (especially oxonol dyes and cyanine dyes). 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.
[0100]
For the light-sensitive material, a colored layer that can be decolored by processing in combination with a water-soluble dye or in combination with a 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, it is 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.
[0101]
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.
[0102]
The photosensitive material is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc., among which it is preferably used as a color photographic paper. The color photographic paper preferably has at least one yellow color-forming silver halide emulsion layer, magenta color-forming silver halide emulsion layer, and cyan color-forming silver halide emulsion layer. The silver halide emulsion layer is a yellow color forming silver halide emulsion layer, a magenta color forming silver halide emulsion layer, and a cyan color forming silver halide emulsion layer in order from the support.
[0103]
However, a different layer structure may be used.
The silver halide emulsion layer containing a yellow coupler may be disposed at any position on the support. However, when the yellow coupler-containing layer contains silver halide tabular grains, a magenta coupler-containing silver halide is contained. It is preferably coated at a position farther from the support than at least one emulsion layer or cyan coupler-containing silver halide emulsion layer. Further, from the viewpoints of accelerating color development, accelerating desilvering, and reducing residual color by sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated at a position farthest from the support than other silver halide emulsion layers. It is preferable to be provided. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably the center layer of other silver halide emulsion layers, and from the viewpoint of reducing photobleaching, cyan coupler-containing silver halide emulsion layers. Is preferably the lowermost layer. Each of the color developing layers of yellow, magenta and cyan may be composed of two layers or three layers. For example, couplers containing no silver halide emulsion as described in JP-A-4-75055, JP-A-9-1114035, JP-A-10-246940, US Pat. No. 5,576,159, etc. It is also preferable to provide a layer adjacent to the silver halide emulsion layer to form a color developing layer.
[0104]
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.
[0105]
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.
[0106]
[Table 1]

[0107]
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 general formulas (II) and (III) of WO 98/33760 and general formula (D) of JP-A-10-221825 may be preferably added.
[0108]
As a cyan dye-forming coupler that can be used in the present invention (sometimes simply referred to as “cyan coupler”), a pyrrolotriazole-based coupler is preferably used, and the general formula (I) or (II) described in JP-A-5-313324 is used. ), 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.
[0109]
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.
[0110]
Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred. The couplers (1) to (47) are applied to the present application as they are, and are preferably incorporated as part of the specification of the present application.
[0111]
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.
[0112]
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 European Patent EP 0447969A1. An acylacetamide type yellow coupler having a structure, a malondianilide type yellow coupler having a cyclic structure described in European Patent EP 0 482 552 A1, European Patent Publication Nos. 935870A1, 953871A1, and 957,72A1 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 the specification of 5,118,599 Acylacetamide yellow couplers having a 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.
[0113]
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.
[0114]
As the light-sensitive material, known color mixing inhibitors can be used. 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 are also preferable.
[0115]
In the light-sensitive material, it is preferable to use a compound having a triazine skeleton with a high molar extinction coefficient as an ultraviolet absorber. 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.
[0116]
Gelatin is advantageously used as the binder or protective colloid that can be used in the light-sensitive material, 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.
[0117]
An antibacterial / antifungal agent as described in JP-A-63-271247 is added to the photosensitive material 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.
[0118]
The total amount of gelatin coated in the photographic composition layer in the photosensitive material is 3 g / m.²6 g / m or more²Preferably, it is 3g / m or less.²5 g / m or more²More preferably, it is as follows. Further, even in the case of ultra-rapid processing, in order to satisfy development progress, fixing bleachability and residual color, the film thickness of the entire photographic constituent layer is preferably 3 μm to 7.5 μm, and more preferably 3 μm to 6. It is preferably 5 μm. The dry film thickness can be measured by measuring the change in film thickness before and after peeling the dry film, or by observing the cross section with an optical microscope or an electron microscope. In the present invention, the swelling film thickness is preferably 8 μm to 19 μm, and more preferably 9 μm to 18 μm, in order to achieve both development progress and increase in the drying speed. The swollen film thickness can be measured by the dot method in a state where the dried photosensitive material is immersed in an aqueous solution at 35 ° C. and swelled to reach a sufficient equilibrium. The total amount of silver applied in the photographic composition of the photosensitive material is 0.2 g / m.²~ 0.5g / m²Is preferably 0.2 g / m²~ 0.45g / m²More preferably, 0.2 g / m²~ 0.40g / m²Most preferably.
[0119]
In the photosensitive material, a surfactant can be added to the photosensitive material from the viewpoints of improving the coating stability, preventing the generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but generally 1 × 10 10^-5~ 1g / m², Preferably 1 × 10^-4~ 1x10^-1g / m²More preferably 1 × 10^-3~ 1x10^-2g / m²It is.
[0120]
Hereinafter, an image forming method using the silver halide color photographic light-sensitive material will be described.
The photosensitive material can form an image by an exposure process in which light is irradiated according to image information and a developing process in which the photosensitive material irradiated with light is developed.
[0121]
The photosensitive material 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.
[0122]
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.
[0123]
Photosensitive materials are monochromatic high-density light such as gas lasers, light-emitting diodes, semiconductor lasers, semiconductor lasers, or second harmonic light-emitting light sources (SHG) that combine nonlinear optical crystals with solid-state lasers that use semiconductor lasers as excitation light sources. The digital scanning exposure method used 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.
[0124]
When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In an SHG light source obtained by combining a solid-state laser using a semiconductor laser as an excitation light source or a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green and red. When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferred exposure time is 10^-4Seconds or less, more preferably 10^-6Less than a second.
[0125]
The photosensitive material is preferably imagewise exposed with coherent light of a blue laser 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 Co., Ltd. at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (oscillation wavelength of about 940 nm) LiNbO having waveguide-like inversion domain structure₃LiNbO having an inverted domain structure in the form of a waveguide of about 470 nm blue laser and semiconductor laser (oscillation wavelength: about 1060 nm) extracted by wavelength conversion with SHG crystal₃Preferably, 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 .
[0126]
The photosensitive material can be preferably used in combination with the exposure and development systems described in the following known documents. 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.
[0127]
The preferred scanning exposure method applicable to the photosensitive material is described in detail in the patents listed in the above table.
[0128]
When the photosensitive material 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 restrictions may be applied before image information is added. .
[0129]
In the development processing of the photosensitive material, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17 The processing materials and processing methods described in the 20th page, lower right column, line 20 are preferably applicable. Further, as the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.
[0130]
In the present invention, the above light-sensitive material is used, and color development is started within 9 seconds after exposure, and the color development is performed within 28 seconds.
Here, 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, and still more preferably. Within 9 seconds or less and 2 seconds or more.
[0131]
The color development time is preferably 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.
[0132]
The color development time is the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, when processed by an automatic developing machine, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leaves the color developer and is bleach-fixed in the next processing step. The total of both the time during which air is conveyed toward the bath (so-called air time) is called color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The water washing or stabilization time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the water washing or stabilizing liquid.
[0133]
As a method for developing the photosensitive material after exposure, the conventional developing method using a developer containing an alkaline agent and a developing agent, or an activator solution such as an alkaline solution containing the developing agent in the photosensitive material and not containing the developing agent. In addition to a wet method such as a developing method, 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.
[0134]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0135]
[Example 1]
(Preparation of emulsion B-1)
1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 5.5 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%, K₄[Ru (CN)₆] The amount of Ru per mol of finished silver halide is 3 × 10^-5Molar 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, an aqueous potassium iodide solution was added so that the amount of I was 0.3 mol% per mol of the finished silver halide. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grain was a cubic silver chlorobromoiodide emulsion having a sphere equivalent diameter of 0.51 μm and a coefficient of variation of 9%.
The emulsion was dissolved at 40 ° C. and sodium thiosulfonate was added at 2 × 10 5 per mole of silver halide.^-5Mole 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 2.7 × 10 6 per mole of silver halide.^-4Mol, sensitizing dye B 1.4 × 10 6 per mol of silver halide^-4Mol, 1-phenyl-5-mercaptotetrazole 2.7 × 10 5 per mole of silver halide^-4Mol, 1- (5-methylureidophenyl) -5-mercaptotetrazole, 2.7 × 10 5 per mole of silver halide^-4Mol, potassium bromide 2.7 × 10 6 per mole of silver halide^-3Mole was added. The emulsion thus obtained was designated as Emulsion B-1.
[0136]
[Chemical 1]

[0137]
(Preparation of emulsion B-2)
Emulsion B-1 is K added when silver nitrate is added from 80% to 90%.₄[Ru (CN)₆] K instead of aqueous solution₄[Fe (CN)₆The amount of Fe per mol of the finished silver halide is 3 × 10^-5An emulsion differing only in the addition of a molar amount was prepared as Emulsion B-2.
[0138]
(Preparation of emulsion B-3)
Emulsion B-1 is K added when silver nitrate is added from 80% to 90%.₄[Ru (CN)₆] K instead of aqueous solution₄[Fe (CN)₆The amount of Fe per mol of the finished silver halide is 3 × 10^-5M is added in a molar amount and added from the point when the addition of silver nitrate is 82% to the point when 88%.₂[IrCl₆The amount of the aqueous solution is 3.6 × 10 5 Ir per mol of the finished silver halide.^-8The amount was changed to a molar amount, and from the time when the addition of silver nitrate was 82% to 88%,₂[IrBr₆The amount of Ir per mol of the finished silver halide is 4.0 × 10^-8An emulsion was prepared which differed only in the addition of a molar amount, and was designated as emulsion B-3.
[0139]
(Preparation of emulsion B-4)
Emulsion B-1 is K added when silver nitrate is added from 82% to 88%.₂[IrCl₆The amount of the aqueous solution is 3.6 × 10 5 Ir per mol of the finished silver halide.^-8The amount was changed to a molar amount, and from the time when the addition of silver nitrate was 92% to 98%, K₂[Ir (H₂O) Cl₅The amount of Ir per mol of the finished silver halide is 1.6 × 10^-6An emulsion differing only in the addition of a molar amount was prepared as Emulsion B-4.
[0140]
(Preparation of emulsion B-5)
Emulsion B-1 is K added when silver nitrate is added from 82% to 88%.₂[IrCl₆The amount of aqueous solution is 1.2 × 10 Ir per mol of the finished silver halide.^-8The amount was changed to a molar amount, and from the time when the addition of silver nitrate was 92% to 98%, K₂[Ir (5-methylthiazole) Cl₅The amount of Ir per mol of the finished silver halide is 1.0 × 10^-6An emulsion was prepared which differed only in the addition of a molar amount, and was designated as emulsion B-5.
[0141]
(Preparation of emulsion B-6)
Emulsion B-1 is K added when silver nitrate is added from 82% to 88%.₂[IrCl₆The amount of the aqueous solution is 8.0 × 10 Ir based on the amount of the finished silver halide.^-9The amount was changed to a molar amount, and from the time when the addition of silver nitrate was 92% to 98%, K₂[Ir (5-methylthiazole) Cl₅The amount of Ir per mol of the finished silver halide is 8.0 × 10^-6Molar amount and K₂[Ir (H₂O) Cl₅The amount of Ir per mol of the finished silver halide is 1.1 × 10^-6An emulsion was prepared which differed only in the addition of a molar amount, and was designated as emulsion B-6.
[0142]
(Preparation of emulsion B-7)
Emulsion B-1 is K added when silver nitrate is added from 82% to 88%.₂[IrCl₆The amount of aqueous solution is 1.0 × 10 5 Ir based on 1 mol of the finished silver halide.^-8The amount was changed to a molar amount, and from the time when the addition of silver nitrate was 82% to 88%,₂[Ir (2-chloro-5-fluorothiazole) Cl₅The amount of Ir per mol of the finished silver halide is 7.2 × 10^-7An emulsion was prepared which differed only in the addition of a molar amount, and this was designated as emulsion B-7.
[0143]
(Preparation of emulsion B-8)
Emulsion B-1 means that from the point of 60% to 80% addition of silver nitrate,₃[RhBr₆The amount of Rh per mol of the finished silver halide is 5.3 × 10^-9M is added in a molar amount and added from the point when the addition of silver nitrate is 82% to the point when 88%.₂[IrCl₆The amount of the aqueous solution is 3.6 × 10 5 Ir per mol of the finished silver halide.^-8An emulsion differing only in the amount changed to a molar amount was prepared, and this was designated as emulsion B-8.
[0144]
(Preparation of emulsion B-9)
Emulsion B-1 refers to Cs from the 60% to 80% addition of silver nitrate.₂[Os (NO) Cl₅The amount of Os per mol of the finished silver halide is 4.1 × 10^-9M is added in a molar amount and added from the point when the addition of silver nitrate is 82% to the point when 88%.₂[IrCl₆The amount of the aqueous solution is 3.6 × 10 5 Ir per mol of the finished silver halide.^-8An emulsion differing only in the amount changed to a molar amount was prepared, and this was designated as emulsion B-9.
[0145]
(Preparation of emulsion B-10)
Emulsion B-1 means that from the point of 60% to 80% addition of silver nitrate,₃[RhBr₆The amount of Rh per mol of the finished silver halide is 4.1 × 10^-9M is added in a molar amount and added from the point when the addition of silver nitrate is 82% to the point when 88%.₂[IrCl₆The amount of aqueous solution is 8.0 × 10 Ir based on the mole of the finished silver halide.^-9The amount was changed to a molar amount, and from the time when the addition of silver nitrate was 92% to 98%, K₂[Ir (5-methylthiazole) Cl₅The amount of Ir per mol of the finished silver halide is 8.0 × 10^-7Molar amount and K₂[Ir (H₂O) Cl₅The amount of Ir per mol of the finished silver halide is 7.0 × 10^-7An emulsion was prepared which differed only in the addition of a molar amount, and was designated as emulsion B-10.
[0146]
(Preparation of emulsion B-11)
Emulsion B-1 means that from the point of 60% to 80% addition of silver nitrate,₃[RhBr₆The amount of Rh per mol of the finished silver halide is 5.3 × 10^-9Add an amount to make a mole, and add from the point of 80% to 90% of the addition of silver nitrate₄[Ru (CN)₆] K instead of aqueous solution₄[Fe (CN)₆The amount of Fe per mol of the finished silver halide is 3 × 10^-5M is added in a molar amount and added from the point when the addition of silver nitrate is 82% to the point when 88%.₂[IrCl₆The amount of the aqueous solution is 3.6 × 10 5 Ir per mol of the finished silver halide.^-8An emulsion differing only in the amount changed to a molar amount was prepared, and this was designated as emulsion B-11.
[0147]
(Preparation of emulsion B-12)
Emulsion B-1 means that from the point of 60% to 80% addition of silver nitrate,₃[RhBr₆The amount of Rh per mol of the finished silver halide is 5.3 × 10^-9Add an amount to make a mole, and add from the point of 80% to 90% of the addition of silver nitrate₄[Ru (CN)₆] K instead of aqueous solution₄[Fe (CN)₆The amount of Fe per mol of the finished silver halide is 3 × 10^-5M is added in a molar amount and added from the point when the addition of silver nitrate is 82% to the point when 88%.₂[IrCl₆The amount of the aqueous solution is 2.0 × 10 Ir based on 1 mol of the finished silver halide.^-8The amount was changed to a molar amount, and from the time when the addition of silver nitrate was 82% to 88%,₂[IrBr₆The amount of Ir per mol of the finished silver halide is 3.0 × 10^-8An emulsion was prepared which differed only in the addition of a molar amount, and was designated as emulsion B-12.
[0148]
(Preparation of emulsion B-13)
Emulsion B-1 refers to Cs from the 60% to 80% addition of silver nitrate.₂[Os (NO) Cl₅The amount of Os per mol of the finished silver halide is 4.1 × 10^-9M is added in a molar amount and added from the point when the addition of silver nitrate is 82% to the point when 88%.₂[IrCl₆The amount of aqueous solution is 8.0 × 10 Ir based on the mole of the finished silver halide.^-9The amount was changed to a molar amount, and from the time when the addition of silver nitrate was 92% to 98%, K₂[Ir (5-methylthiazole) Cl₅The amount of Ir per mol of the finished silver halide is 7.2 × 10^-7An emulsion was prepared which differed only in the addition of a molar amount, and was designated as emulsion B-13.
[0149]
(Preparation of emulsion B-14)
Emulsion B-1 means that from the point of 60% to 80% addition of silver nitrate,₃[RhBr₆The amount of Rh per mol of the finished silver halide is 5.3 × 10^-9Add an amount to make a mole, and add from the point of 80% to 90% of the addition of silver nitrate₄[Ru (CN)₆] K instead of aqueous solution₄[Fe (CN)₆The amount of Fe per mol of the finished silver halide is 3 × 10^-5M is added in a molar amount and added from the point when the addition of silver nitrate is 82% to the point when 88%.₂[IrCl₆The amount of the aqueous solution is 6.0 × 10 Ir based on 1 mol of the finished silver halide.^-9The amount was changed to a molar amount, and from the time when the addition of silver nitrate was 82% to 88%,₂[Ir (2-chloro-5-fluorothiazole) Cl₅The amount of Ir per mole of the finished silver halide is 5.2 × 10^-7Molar amounts are added, and silver nitrate is added from 92% to 98%.₂[Ir (H₂O) Cl₅The amount of Ir per mol of the finished silver halide is 1.0 × 10^-6An emulsion was prepared which differed only in the addition of a molar amount, and was designated as emulsion B-14.
[0150]
(Preparation of emulsion G-1)
1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 5.5 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 40 ° C. with vigorous stirring. From the point of 60% to 80% addition of silver nitrate,₃[RhBr₆The amount of Rh per mol of finished silver halide is 5.8 × 10^-9Molar amounts were added. From 80% to 100% addition of silver nitrate, potassium bromide was added in vigorous mixing in an amount of 4.3 mol% per mole of finished silver halide. From the point of 80% to 90% addition of silver nitrate,₄[Ru (CN)₆] The amount of Ru per mol of the finished silver halide is 3.0 × 10^-5Molar amounts were added. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆The amount of Ir per mol of the finished silver halide is 5.0 × 10^-8Molar amounts were added. Further, when 90% of the addition of silver nitrate was completed, an aqueous potassium iodide solution was added while vigorously mixing in an amount such that the amount of I was 0.15 mol% per mol of the finished silver halide. From 92% to 95% addition of silver nitrate, K₂[Ir (5-methylthiazole) Cl₅The amount of Ir per mol of the finished silver halide is 5.0 × 10^-7Molar amounts were added. Furthermore, from the time when the addition of silver nitrate is 95% to 98%, K₂[Ir (H₂O) Cl₅The amount of Ir per mol of the finished silver halide is 5.0 × 10^-7Molar amounts were added. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were cubic silver chlorobromoiodide emulsions having a sphere equivalent diameter of 0.35 and an incense A variation coefficient of 9%.
The emulsion was dissolved at 40 ° C. and sodium thiosulfonate was added at 2 × 10 5 per mole of silver halide.^-5Mole was added, and aging was performed at 60 ° C. optimally using sodium thiosulfate pentahydrate as a sulfur sensitizer and gold thioglucose as a gold sensitizer. After cooling to 40 ° C., sensitizing dye C was added at 6 × 10 6 per mole of silver halide.^-4Mol, 1-phenyl-5-mercaptotetrazole, 2 × 10 5 per mole of silver halide^-4Mole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, 8 × 10 8 per mole of silver halide^-4Moles of potassium bromide, 7 x 10 per mole of silver halide^-3Mole was added. The emulsion thus obtained was designated as Emulsion G-1.
[0151]
[Chemical 2]

[0152]
(Preparation of emulsion R-1)
1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 5.5 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 40 ° C. with vigorous stirring. From the point of 60% to 80% addition of silver nitrate,₃[RhBr₆The amount of Rh per mol of finished silver halide is 5.8 × 10^-9Molar amounts were added. From 80% to 100% addition of silver nitrate, potassium bromide was added in vigorous mixing in an amount of 4.3 mol% per mole of finished silver halide. From the point of 80% to 90% addition of silver nitrate,₄[Ru (CN)₆] The amount of Ru per mol of finished silver halide is 3 × 10^-5Molar amounts were added. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆The amount of Ir per mole of the finished silver halide is 5 × 10^-9Molar amounts were added. When 90% of the addition of silver nitrate was completed, an aqueous potassium iodide solution was added while vigorously mixing in an amount such that the amount of I was 0.1 mol% per mol of the finished silver halide. From 92% to 95% addition of silver nitrate, K₂[Ir (5-methylthiazole) Cl₅The amount of Ir per mole of the finished silver halide is 5 × 10^-7Molar amounts were added. Furthermore, from the time when the addition of silver nitrate is 95% to 98%, K₂[Ir (H₂O) Cl₅The amount of Ir per mole of the finished silver halide is 5 × 10^-7Molar amounts were added. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were cubic silver chlorobromoiodide emulsions having an equivalent sphere diameter of 0.35 μm and a coefficient of variation of 9%.
The emulsion was dissolved at 40 ° C. and sodium thiosulfonate was added at 2 × 10 5 per mole of silver halide.^-5Mole 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 cooling to 40 ° C., sensitizing dye H was added at 2 × 10 2 per mole of silver halide^-4Mol, 1-phenyl-5-mercaptotetrazole, 2 × 10 5 per mole of silver halide^-4Mole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, 8 × 10 8 per mole of silver halide^-4Moles of Compound I 1 × 10 5 per mole of silver halide^-3Moles of potassium bromide, 7 x 10 per mole of silver halide^-3Mole was added. The emulsion thus obtained was designated as Emulsion R-1.
[0153]
[Chemical 3]

[0154]
[Formula 4]

[0155]
(sample)
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, and the photographic composition of the first to seventh layers 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.
[0156]
-Preparation of coating solution for first layer-
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.
[0157]
-Preparation of coating solution for second to seventh layers-
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.
[0158]
[Chemical formula 5]

[0159]
[Chemical 6]

[0160]
Further, 1-phenyl-5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 1.0 × 10 6 per mole of silver halide.^-3Moles and 5.9 × 10^-4Mole 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).
[0161]
[Chemical 7]

[0162]
(Layer structure)
The structure of each layer is shown below. Numbers are application amount (g / m²). The silver halide emulsion represents a coating amount in terms of silver.
Support
Polyethylene resin laminated paper
[White pigment (TiO 2 on the first layer side polyethylene resin)₂Content 16% by mass, ZnO; content 4% by mass) and optical brightener (4,4′-bis (5-methylbenzoxazolyl) stilbene, content 0.03% by mass), bluish dye (Including ultramarine)]
First layer (blue sensitive emulsion layer)
Emulsion B-1 0.19
Gelatin 1.00
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
[0163]
Second layer (color mixing prevention layer)
Gelatin 0.50
Color mixing inhibitor (Cpd-4) 0.05
Color image stabilizer (Cpd-5) 0.01
Color image stabilizer (Cpd-6) 0.06
Color image stabilizer (Cpd-7) 0.01
Solvent (Solv-1) 0.03
Solvent (Solv-2) 0.11
[0164]
Third layer (green sensitive emulsion layer)
Emulsion G-1 0.10.12
Gelatin 2015 1.36
Magenta coupler (ExM) 0.15
Ultraviolet absorber (UV-A) 0.14
Color image stabilizer (Cpd-2) 0.02
Color image stabilizer (Cpd-4) 0.002
Color image stabilizer (Cpd-6) 0.09
Color image stabilizer (Cpd-8) 0.02
Color image stabilizer (Cpd-9) 0.03
Color image stabilizer (Cpd-10) 0.01
Color image stabilizer (Cpd-11), 0.0001
Solvent (Solv-3) 0.11
Solvent (Solv-4) 0.22
Solvent (Solv-5) 0.20
[0165]
Fourth layer (color mixing prevention layer)
Gelatin gelatin 0.36
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
[0166]
5th layer (red-sensitive emulsion layer)
Emulsion R-1 0.10 0.10
Gelatin 2015 1.11
Cyan coupler (ExC-2) 0.13
Cyan coupler (ExC-3) 0.03
Color image stabilizer (Cpd-1) 0.05
Color image stabilizer (Cpd-6) 0.06
Color image stabilizer (Cpd-7) 0.02
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.01
Color image stabilizer (Cpd-14) 0.01
Color image stabilizer (Cpd-15) 0.12
Color image stabilizer (Cpd-16) 0.03
Color image stabilizer (Cpd-17) 0.09
Color image stabilizer (Cpd-18) 0.07
Solvent (Solv-5) 0.15
Solvent (Solv-8) 0.05
[0167]
Sixth layer (UV absorbing layer)
Gelatin 4.00.46
Ultraviolet absorber (UV-B) 0.45
Compound (S1-4): 0.0015
Solvent (Solv-7) 0.25 0.25
Seventh layer (protective layer)
Gelatin 1.00
Acrylic-modified copolymer of polyvinyl alcohol
(Denatured 17%) 0.00.04
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.01
[0168]
[Chemical 8]

[0169]
[Chemical 9]

[0170]
Embedded image

[0171]
Embedded image

[0172]
Embedded image

[0173]
Embedded image

[0174]
Embedded image

[0175]
Embedded image

[0176]
Embedded image

[0177]
Embedded image

[0178]
The sample obtained as described above was designated as Sample 101. Samples 101 to 114 were prepared in the same manner as samples 101 except that the blue-sensitive emulsion layer emulsions were changed as shown in Table 2.
[0179]
[Table 2]

[0180]
In order to examine the photographic characteristics of these samples, the following experiment was conducted.
Each coated sample was placed in an atmosphere of 10 ° C. and 30% RH, and 10 for gray color sensitometry using a high intensity exposure photometer (HIE type manufactured by Yamashita Denso Co., Ltd.).^-6Second high intensity gradation exposure was given. The exposed sample was subjected to the following color development processing 3 seconds, 9 seconds, or 30 seconds after exposure.
[0181]
The processing steps are shown below.
[processing]
The sample 110 was continuously processed 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]

[0183]
The composition of each treatment liquid is as follows.

[0184]

[0185]

[0186]
Embedded image

[0187]
Similarly exposed samples were subjected to a color development process 3 seconds, 9 seconds or 30 seconds after exposure, except that the color development time was changed to 30 seconds in the color development process described above. Further, each coated sample was placed in an atmosphere of 30 ° C. and 30% RH, and the same experiment was repeated.
[0188]
The yellow color density of each sample after treatment was measured, and 10^-6A characteristic curve of second high illumination exposure was obtained. Under an atmosphere of 10 ° C. and 30% RH, an exposure amount giving a color density of 0.7 when the color development is performed for 16 seconds after the exposure for 3 seconds, and 0.7 when the color development for 16 seconds is performed after the exposure of 9 seconds. The change in density from A was ΔD (10 ° C., 3 ″ → 9 ″, 16 ″). When color development was performed for 16 seconds after exposure for 9 seconds in an atmosphere of 10 ° C. and 30% RH, a color density of 0.7 was obtained. In the exposure amount to be given, the density change from 0.7 when color development for 16 seconds was performed after 30 seconds of exposure was defined as ΔD (10 ° C., 9 ″ → 30 ″, 16 ″).
Under an atmosphere of 10 ° C. and 30% RH, an exposure amount giving a color density of 0.7 when 3 seconds of color development is carried out after 3 seconds of exposure is 0.7 when color development of 30 seconds is carried out after 9 seconds of exposure. The change in density from the image was ΔD (10 ° C., 3 ″ → 9 ″, 30 ″). When color development was performed for 30 seconds after exposure for 9 seconds in an atmosphere of 10 ° C. and 30% RH, a color density of 0.7 was obtained. At the exposure amount to be given, the density change from 0.7 in the case of color development for 30 seconds after 30 seconds of exposure was defined as ΔD (10 ° C., 9 ″ → 30 ″, 30 ″).
[0189]
At an exposure amount giving a color density of 0.7 when 3 seconds exposure is performed after 3 seconds exposure at 10 ° C. and 30% RH atmosphere, color development is performed after 16 seconds exposure at 30 ° C. and 30% RH atmosphere after 16 seconds. The change in density from 0.7 was ΔD (10 ° C. → 30 ° C., 3 ″, 16 ″). Color development is performed for 16 seconds after 30 seconds exposure at 30 ° C. and 30% RH at an exposure amount giving a color density of 0.7 when color development is performed for 16 seconds after 30 seconds exposure at 10 ° C. and 30% RH. In this case, the change in density from 0.7 was ΔD (10 ° C. → 30 ° C., 30 ″, 16 ″).
At an exposure amount giving a color density of 0.7 when 3 seconds of color development is performed after 3 seconds of exposure at 10 ° C. and 30% RH atmosphere, color development of 30 seconds is performed after 3 seconds of exposure at 30 ° C. and 30% RH atmosphere. In this case, the change in density from 0.7 was ΔD (10 ° C. → 30 ° C., 3 ″, 30 ″). Color development of 30 seconds after 30 seconds of exposure at 30 ° C. and 30% RH is performed at an exposure amount giving a color density of 0.7 when 30 seconds of color development is performed after 30 seconds of exposure at 10 ° C. and 30% RH. In this case, the change in density from 0.7 was ΔD (10 ° C. → 30 ° C., 30 ″, 30 ″).
[0190]
The results of these evaluations are shown in Tables 3 and 4. The smaller the value of each ΔD, the more stable and preferable print density.
[0191]
[Table 3]

[0192]
[Table 4]

[0193]
As is apparent from the results of Tables 3 and 4, when samples 101 to 103 were processed under the conditions of a short-time latent image and short-time color development, the photographic density was changed due to a change in the latent image time and a change in exposure environment temperature. However, when the samples 104 to 114 are processed under the conditions of a short-time latent image and short-time color development, the change of the latent image time and the exposure environment are not obtained. It can be seen that the change in temperature does not increase the change in photographic density, and a stable print density can be obtained (the present invention).
[0194]
[Example 2]
In order to investigate the stability of these samples in laser scanning exposure, the following experiment was conducted.
As a laser light source, a blue semiconductor laser with a wavelength of about 440 nm (announced by Nichia Chemical at the 48th Applied Physics-related Conference in March 2001), a semiconductor laser (oscillation wavelength of about 1060 nm) with a waveguide-like inversion domain structure LiNbO with₃A green laser with a wavelength of about 530 nm and a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL6501MG) 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 a polygon mirror so that the sample can be sequentially scanned and exposed. The light quantity fluctuation 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. By this exposure method, under the environment of 10 ° C. and 30% RH, a gray-colored uniform exposure was given to the A4 size sample so that the color density of yellow, magenta, and cyan was approximately 0.7.
[0195]
Each exposed sample was subjected to the same color development processing as in Example 1. Color development is started about 3 seconds after the exposure of the uniformly exposed A4 sample, and color development is started about 9 seconds after the exposure. The color development time was 16 seconds.
[0196]
The yellow color density of the front and rear ends of each sample after processing is measured, and the difference ΔD_YI read. Difference ΔD_YA positive value indicates that the concentration increases from the front end to the rear end. The results are shown in Table 5.
[0197]
[Table 5]

[0198]
As is clear from the results in Table 5, even when the samples 104 to 114 are subjected to laser scanning exposure and subjected to rapid processing with a short latent image time, there is little change in color at the leading edge and trailing edge of the print, and stable. It turns out that quality is obtained.
[0199]
[Example 3]
Sample 101 was prepared by changing the photographic composition layer as described below to make it thinner.
First layer (blue sensitive emulsion layer)
Emulsion B-1 0.14 0.1
Gelatin 0.75 0.75
Yellow coupler (ExY-2) 0.34
Color image stabilizer (Cpd-1) 0.04
Color image stabilizer (Cpd-2) 0.02
Color image stabilizer (Cpd-3) 0.04
Color image stabilizer (Cpd-8) 0.01
Solvent (Solv-1) 0.13
[0200]
Second layer (color mixing prevention layer)
Gelatin gelatin 0.60
Color mixing inhibitor (Cpd-19) 0.09
Color image stabilizer (Cpd-5) 0.007
Color image stabilizer (Cpd-7) 0.007
Ultraviolet absorber (UV-C) 0.05
Solvent (Solv-5) 0.11
[0201]
Third layer (green sensitive emulsion layer)
Emulsion G-1 0.10.12
Gelatin 0.73 0.7
Magenta coupler (ExM) 0.15
Ultraviolet absorber (UV-A) 0.05
Color image stabilizer (Cpd-2) 0.02
Color image stabilizer (Cpd-7) 0.008
Color image stabilizer (Cpd-8) 0.07
Color image stabilizer (Cpd-9) 0.03
Color image stabilizer (Cpd-10) 0.009
Color image stabilizer (Cpd-11), 0.0001
Solvent (Solv-3) 0.06
Solvent (Solv-4) 0.11
Solvent (Solv-5) 0.06
[0202]
Fourth layer (color mixing prevention layer)
Gelatin gelatin 0.48
Color mixing prevention layer (Cpd-4) 0.07
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-7) 0.006
Ultraviolet absorber (UV-C) 0.04
Solvent (Solv-5) 0.09
[0203]
5th layer (red-sensitive emulsion layer)
Emulsion R-1 0.10 0.10
Gelatin 0.59
Cyan coupler (ExC-2) 0.13
Cyan coupler (ExC-3) 0.03
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-15) 0.19
Color image stabilizer (Cpd-18) 0.04
UV absorber (UV-7) 0.02
Solvent (Solv-5) 0.09
[0204]
Sixth layer (UV absorbing layer)
Gelatin gelatin 0.32
Ultraviolet absorber (UV-C) 0.42
Solvent (Solv-7) 0.08
Seventh layer (protective layer)
Gelatin gelatin 0.70
Acrylic-modified copolymer of polyvinyl alcohol
(Denatured 17%) 0.00.04
Liquid paraffin 0.01
Surfactant (Cpd-13) 0.01
Polydimethylsiloxane 0.01 0.01
Silicon dioxide, 0.003, silicon dioxide
[0205]
Embedded image

[0206]
The sample obtained as described above was designated as Sample 201. Samples 201 were prepared in the same manner as samples 201 except that the emulsion of the blue-sensitive emulsion layer was changed as shown in Table 6. These samples were subjected to the same laser scanning exposure and processing as in Example 2, and ΔD_YI read. The results are shown in Table 6.
[0207]
[Table 6]

[0208]
As is apparent from the results in Table 6, when samples 204 to 214 were exposed to laser scanning and subjected to rapid processing with a short latent image time, there was little change in the color of the print leading edge and trailing edge, and the stability It can be seen that a good quality can be obtained.
[0209]
【The invention's effect】
As described above, according to the present invention, an image forming method capable of always obtaining stable photographic performance even when ultra-rapid processing is performed, and a silver halide color photographic light-sensitive material applied thereto, particularly a halogen suitable for color printing. A silver halide color photographic light-sensitive material can be provided.

Claims (9)

At least one layer each containing 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 the support. An image forming method for color development after imagewise exposing a silver halide color photographic light-sensitive material having a photographic composition layer comprising:
At least one of the silver halide emulsion layers contains a silver halide emulsion containing at least one selected from metal complexes represented by the following general formula (I) and having a silver chloride content of 90 mol% or more. ,
An image forming method comprising: starting color development within 9 seconds after imagewise exposing the silver halide color photographic material, and performing the color development within 28 seconds.
Formula (I)
^{_{[IrX I n L I (6}} -n)] m
(In the general formula (I), X ^I represents a halogen ion or 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+.) At least one layer each containing 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 the support. An image forming method for color development after imagewise exposing a silver halide color photographic light-sensitive material having a photographic composition layer comprising:
Including at least one silver halide emulsion containing at least one selected from metal complexes represented by the following general formula (II) and having a silver chloride content of 90 mol% or more in at least one of the silver halide emulsion layers,
An image forming method comprising: starting color development within 9 seconds after imagewise exposing the silver halide color photographic material, and performing the color development within 28 seconds.
Formula (II)
[MX ^II _n L ^II _(6-n) ] ^m
(In the general formula (II), M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, X ^II represents a halogen ion, and L ^II is an arbitrary element different from X ^II. Represents a ligand, n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0, or 1+. At least one layer each containing 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 the support. An image forming method for color development after imagewise exposing a silver halide color photographic light-sensitive material having a photographic composition layer comprising:
In at least one of the silver halide emulsion layers, at least one selected from metal complexes represented by the following general formula (I) and at least one selected from metal complexes represented by the following general formula (II): Containing a silver halide emulsion having a silver chloride content of 90 mol% or more,
An image forming method comprising: starting color development within 9 seconds after imagewise exposing the silver halide color photographic material, and performing the color development within 28 seconds.
Formula (I)
^{_{[IrX I n L I (6}} -n)] m
(In the general formula (I), X ^I represents a halogen ion or 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+.)
Formula (II)
[MX ^II _n L ^II _(6-n) ] ^m
(In the general formula (II), M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, X ^II represents a halogen ion, and L ^II is an arbitrary element different from X ^II. Represents a ligand, n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0, or 1+. A silver halide color photographic light-sensitive material for rapid processing which starts color development within 9 seconds after imagewise exposure and forms an image by performing the color development within a time of 28 seconds,
The silver halide color photographic light-sensitive material comprises a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer and a non-photosensitive material on a support. Having a photographic composition layer comprising at least one each of the hydrophilic colloid layers,
And at least one of the silver halide emulsion layers contains a silver halide emulsion containing at least one selected from metal complexes represented by the following general formula (I) and having a silver chloride content of 90 mol% or more. A silver halide color photographic light-sensitive material characterized by the above.
Formula (I)
^{_{[IrX I n L I (6}} -n)] m
(In the general formula (I), X ^I represents a halogen ion or 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+.) A silver halide color photographic light-sensitive material for rapid processing which starts color development within 9 seconds after imagewise exposure and forms an image by performing the color development within a time of 28 seconds,
The silver halide color photographic light-sensitive material comprises a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer and a non-photosensitive material on a support. Having a photographic composition layer comprising at least one each of the hydrophilic colloid layers,
And at least one of the silver halide emulsion layers contains a silver halide emulsion containing at least one selected from metal complexes represented by the following general formula (II) and having a silver chloride content of 90 mol% or more. A silver halide color photographic light-sensitive material characterized by the above.
Formula (II)
[MX ^II _n L ^II _(6-n) ] ^m
(In the general formula (II), M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, X ^II represents a halogen ion, and L ^II is an arbitrary element different from X ^II. Represents a ligand, n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0, or 1+. A silver halide color photographic light-sensitive material for rapid processing which starts color development within 9 seconds after imagewise exposure and forms an image by performing the color development within a time of 28 seconds,
The silver halide color photographic light-sensitive material comprises a yellow dye-forming coupler-containing silver halide emulsion layer, a magenta dye-forming coupler-containing silver halide emulsion layer, a cyan dye-forming coupler-containing silver halide emulsion layer and a non-photosensitive material on a support. Having a photographic composition layer comprising at least one each of the hydrophilic colloid layers,
And at least one selected from a metal complex represented by the following general formula (I) and at least one selected from a metal complex represented by the following general formula (II) in at least one of the silver halide emulsion layers: A silver halide color photographic light-sensitive material containing a silver halide emulsion containing 90 mol% or more of silver chloride.
Formula (I)
^{_{[IrX I n L I (6}} -n)] m
(In the general formula (I), X ^I represents a halogen ion or 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+.)
Formula (II)
[MX ^II _n L ^II _(6-n) ] ^m
(In the general formula (II), M represents Cr, Mo, Re, Fe, Ru, Os, Co, Rh, Pd or Pt, X ^II represents a halogen ion, and L ^II is an arbitrary element different from X ^II. Represents a ligand, n represents 3, 4, 5 or 6, and m represents 4-, 3-, 2-, 1-, 0, or 1+. 7. The silver halide color according to claim 4, wherein the total silver coating amount in the photographic composition layer is 0.2 g / m ² or more and 0.5 g / m ² or less. Photosensitive material. The silver halide color photographic light-sensitive material according to any one of claims 4 to 7, wherein the total amount of gelatin coated in the photographic composition layer is 3 g / m ² or more and 6 g / m ² or less. 9. The halogen according to claim 4, wherein the silver halide emulsion of the yellow dye-forming coupler-containing silver halide emulsion layer is a silver halide emulsion having a sphere equivalent diameter of 0.6 μm or less. Silver halide color photographic material.