JP4116831B2 - Image forming method using silver halide color photographic light-sensitive material - Google Patents

Description

【０１０１】
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。
【０１０２】
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。
【０１０３】
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。
【０１０４】
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。
【０１０５】
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。
【０１０６】
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。
【０１０７】
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。
【０１０８】
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。
【０１０９】
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。
【０１１０】
感光材料に用いることのできる結合剤又は保護コロイドとしては、ゼラチンを用いることが有利であるが、それ以外の親水性コロイドを単独であるいはゼラチンとともに用いることができる。好ましいゼラチンとしては、鉄、銅、亜鉛、マンガン等の不純物として含有される重金属は、好ましくは５ｐｐｍ以下、更に好ましくは３ｐｐｍ以下である。また、感光材料中に含まれるカルシウム量は、好ましくは２０ｍｇ／ｍ²以下、更に好ましくは１０ｍｇ／ｍ²以下、最も好ましくは５ｍｇ／ｍ²以下である。
【０１１１】
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。
【０１１２】
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層中の総塗設銀量は、本発明においては、０．２ｇ／ｍ^２〜０．５ｇ／ｍ^２であるが、０．２ｇ／ｍ^２〜０．４５ｇ／ｍ^２であることが好ましく、０．２ｇ／ｍ^２〜０．４０ｇ／ｍ^２であることが最も好ましい。なお、本発明においては、イエロー色素形成カプラー含有ハロゲン化銀乳剤層の塗設銀量は０．１〜０．２３ｇ／ｍ ^２ である。
【０１１３】
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／ｍ²、好ましくは１×１０^-4〜１×１０^-1ｇ／ｍ²、更に好ましくは１×１０^-3〜１×１０^-2ｇ／ｍ²である。
【０１１４】
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。
【０１１５】
本発明では、上記感光材料を使用し、露光光源の少なくとも１つが発光波長４２０ｎｍ〜４６０ｎｍの青色レーザーである露光光源で走査露光する。これは、青色レーザーのコヒーレント光により像様露光するものであり、該発光波長で露光した場合に本願の効果を効果的に発現する。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。発光波長は４３０ｎｍ〜４５０ｎｍであることが、本発明の効果を際立たせる意味で好ましい。
【０１１６】
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。
【０１１７】
このような走査露光光源を使用する場合、本発明の感光材料の分光感度極大波長は、使用する走査露光用光源の波長により任意に設定することができる。半導体レーザーを励起光源に用いた固体レーザーあるいは半導体レーザーと非線形光学結晶を組合わせて得られるＳＨＧ光源では、レーザーの発振波長を半分にできるので、青色光、緑色光が得られる。従って、感光材料の分光感度極大は通常の青、緑、赤の３つの波長領域に持たせることが可能である。このような走査露光における露光時間は、画素密度を４００ｄｐｉとした場合の画素サイズを露光する時間として定義すると、好ましい露光時間としては１０^-4秒以下、更に好ましくは１０^-6秒以下である。
【０１１８】
本発明においては、レーザー光源として、波長４３０〜４６０ｎｍ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）を使用するものであるが、これとともに使用するレーザー光源としては具体的には、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。
【０１１９】
なお、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。
【０１２０】
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。
【０１２１】
本発明では、上記感光材料を使用し、上述のように露光してから９秒以内に発色現像を開始しする。
上記において、露光から発色現像の開始までの時間（いわゆる潜像時間）は９秒以内（好ましくは９秒以下０．１秒以上の範囲内）であり、このような短時間で発色現像した場合に、本発明の効果が発現する。より好ましくは６秒以内（６秒以下０．１秒以上の範囲内）の時間で大きな効果が得られる。露光装置と処理機が分離独立したシステムでは、潜像時間は長くなるために本発明の効果は発現しない。露光装置と処理機が合体したプリンターで、トータルのプリント時間を迅速にしたシステムにおいて、本発明の効果が発現する。
【０１２２】
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。
【０１２３】
本発明に適用できる好ましい走査露光方式については、前記の表に掲示した特許に詳しく記載されている。
【０１２４】
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。
【０１２５】
感光材料の処理には、特開平２−２０７２５０号公報の第２６頁右下欄１行目〜３４頁右上欄９行目、及び特開平４−９７３５５号公報の第５頁左上欄１７行目〜１８頁右下欄２０行目に記載の処理素材や処理方法が好ましく適用できる。また、この現像液に使用する保恒剤としては、前記の表に掲示した特許に記載の化合物が好ましく用いられる。
【０１２６】
本発明は迅速処理適性を有する感光材料としても適用される。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。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。
【０１２７】
感光材料を露光後、現像する方法としては、従来のアルカリ剤と現像主薬を含む現像液で現像する方法、現像主薬を感光材料に内蔵し、現像主薬を含まないアルカリ液などのアクチベーター液で現像する方法などの湿式方式のほか、処理液を用いない熱現像方式などを用いることができる。特に、アクチベーター方法は、現像主薬を処理液に含まないため、処理液の管理や取扱いが容易であり、また廃液処理時の負荷が少なく環境保全上の点からも好ましい方法である。
アクチベーター方法において、感光材料中に内蔵される現像主薬又はその前駆体としては、例えば、特開平８−２３４３８８号公報、同９−１５２６８６号公報、同９−１５２６９３号公報、同９−２１１８１４号公報、同９−１６０１９３号公報に記載されたヒドラジン型化合物が好ましい。
【０１２８】
また、感光材料の塗布銀量を低減し、過酸化水素を用いた画像増幅処理（補力処理）する現像方法も好ましく用いられる。特に、この方法をアクチベーター方法に用いることは好ましい。具体的には、特開平８−２９７３５４号公報、同９−１５２６９５号公報に記載された過酸化水素を含むアクチベーター液を用いた画像形成方法が好ましく用いられる。前記アクチベーター方法において、アクチベーター液で処理後、通常脱銀処理されるが、低銀量の感光材料を用いた画像増幅処理方法では、脱銀処理を省略し、水洗又は安定化処理といった簡易な方法を行うことができる。また、感光材料から画像情報をスキャナー等で読み取る方式では、撮影用感光材料などの様に高銀量の感光材料を用いた場合でも、脱銀処理を不要とする処理形態を採用することができる。
【０１２９】
本発明で用いられるアクチベーター液、脱銀液（漂白／定着液）、水洗及び安定化液の処理素材や処理方法は公知のものを用いることができる。好ましくは、リサーチ・ディスクロージャーＩｔｅｍ ３６５４４（１９９４年９月）第５３６頁〜第５４１頁、特開平８−２３４３８８号公報に記載されたものを用いることができる。
【０１３０】
【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。
【０１３１】
実施例１
（乳剤Ｂ−１の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．５４μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が８０％の時点から９０％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり２．５モル％）およびＫ₄［Ｒｕ（ＣＮ）₆］を出来上がりのハロゲン化銀１モルあたりＲｕ量が２×１０^-5モルになる量添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を出来上がりのハロゲン化銀１モルあたりＩｒ量が４．８×１０^-8モルになる量を添加した。硝酸銀の添加が９４％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．３モル％）を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムと増感色素Ａおよび増感色素Ｂを添加し、増感剤として硫化金コロイド分散物を用い最適になるように熟成した。更に１−フェニル−５−メルカプトテトラゾールおよび１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールを添加した。このようにして得られた乳剤を、乳剤Ｂ−１とした。
【０１３２】
【化１】

【０１３３】
（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Ｋ₄［Ｒｕ（ＣＮ）₆］水溶液に代えて、Ｋ₄［Ｆｅ（ＣＮ）₆］水溶液を出来上がりのハロゲン化銀１モルあたりＦｅ量が２×１０^-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。
【０１３４】
（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Ｋ₄［Ｒｕ（ＣＮ）₆］水溶液に代えて、Ｋ₄［Ｆｅ（ＣＮ）₆］水溶液を出来上がりのハロゲン化銀１モルあたりＦｅ量が２×１０^-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Ｋ₂［ＩｒＣｌ₆］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２．３×１０^-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、Ｋ₂［ＩｒＢｒ₆］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３．６×１０^-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。
【０１３５】
（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Ｋ₂［ＩｒＣｌ₆］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２．３×１０^-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、Ｋ₂［Ｉｒ（Ｈ₂Ｏ）Ｃｌ₅］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３．２×１０^-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。
【０１３６】
（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Ｋ₂［ＩｒＣｌ₆］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、更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ₅］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６．７×１０^-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−５とした。
【０１３７】
（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Ｋ₂［ＩｒＣｌ₆］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、更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ₅］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５．４×１０^-7モルになる量およびＫ₂［Ｉｒ（Ｈ₂Ｏ）Ｃｌ₅］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２．２×１０^-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。
【０１３８】
（乳剤Ｂ−７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、Ｋ₃［ＲｈＢｒ₆］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３．２×１０^-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Ｋ₂［ＩｒＣｌ₆］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２．３×１０^-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−７とした。
【０１３９】
（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、Ｃｓ₂［Ｏｓ（ＮＯ）Ｃｌ₅］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３．１×１０^-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Ｋ₂［ＩｒＣｌ₆］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２．３×１０^-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。
【０１４０】
（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、Ｋ₃［ＲｈＢｒ₆］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２．５×１０^-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Ｋ₂［ＩｒＣｌ₆］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、更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ₅］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５．４×１０^-7モルになる量およびＫ₂［Ｉｒ（Ｈ₂Ｏ）Ｃｌ₅］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２．２×１０^-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−９とした。
【０１４１】
（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、Ｋ₃［ＲｈＢｒ₆］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３．２×１０^-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Ｋ₄［Ｒｕ（ＣＮ）₆］水溶液に代えて、Ｋ₄［Ｆｅ（ＣＮ）₆］水溶液を出来上がりのハロゲン化銀１モルあたりＦｅ量が２×１０^-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Ｋ₂［ＩｒＣｌ₆］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２．３×１０^-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−１０とした。
【０１４２】
（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、Ｋ₃［ＲｈＢｒ₆］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３．２×１０^-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Ｋ₄［Ｒｕ（ＣＮ）₆］水溶液に代えて、Ｋ₄［Ｆｅ（ＣＮ）₆］水溶液を出来上がりのハロゲン化銀１モルあたりＦｅ量が２×１０^-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Ｋ₂［ＩｒＣｌ₆］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１．６×１０^-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、Ｋ₂［ＩｒＢｒ₆］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２．３×１０^-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−１１とした。
【０１４３】
（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、Ｃｓ₂［Ｏｓ（ＮＯ）Ｃｌ₅］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３．１×１０^-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Ｋ₂［ＩｒＣｌ₆］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、更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ₅］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ことのみ異なる乳剤を調製し、これを乳剤Ｂ−１２とした。
【０１４４】
（乳剤Ｇ−１の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．４０μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ（ＣＮ）₆］を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８０％の時点から１００％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり４モル％）を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を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。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．２モル％）を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムを添加し、増感剤として硫化金コロイド分散物を用い最適になるように熟成した。更に増感色素Ｃ、１−フェニル−５−メルカプトテトラゾール、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールおよび臭化カリウムを添加した。このようにして得られた乳剤を、乳剤Ｇ−１とした。
【０１４５】
【化２】

【０１４６】
（乳剤Ｒ−１の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．３５μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ（ＣＮ）₆］を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８０％の時点から１００％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり４．３モル％）を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を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（出来上がりのハロゲン化銀１モルあたり０．１５モル％）を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムを添加し、硫黄増感剤としてチオ硫酸ナトリウム５水和物と金増感剤としてビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオラート）オーレート（I）テトラフルオロボレートを用い最適になるように熟成した。更に増感色素Ｈ、１−フェニル−５−メルカプトテトラゾール、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾール、化合物Ｉおよび臭化カリウムを添加した。このようにして得られた乳剤を、乳剤Ｒ−１とした。
【０１４７】
【化３】

【０１４８】
【化４】

【０１４９】
（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。
【０１５０】
−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。
【０１５１】
−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／ｍ²、６０．０ｍｇ／ｍ²、５．０ｍｇ／ｍ²及び１０．０ｍｇ／ｍ²となるように添加した。
【０１５２】
【化５】

【０１５３】
【化６】

【０１５４】
また、緑感性乳剤層および赤感性乳剤層に対し、１−フェニル−５−メルカプトテトラゾールを、それぞれハロゲン化銀１モル当り１．０×１０^-3モルおよび５．９×１０^-4モル添加した。さらに、第二層、第四層および第六層にも１−フェニル−５−メルカプトテトラゾールを、それぞれ０．２ｍｇ／ｍ²、０．２ｍｇ／ｍ²および０．６ｍｇ／ｍ²となるように添加した。
赤感性乳剤層にメタクリル酸とアクリル酸ブチルの共重合体ラテックス（質量比１：１、平均分子量２０００００〜４０００００）を０．０５ｇ／ｍ²添加した。また、第二層、第四層および第六層にカテコール−３，５−ジスルホン酸二ナトリウムをそれぞれ６ｍｇ／ｍ²、６ｍｇ／ｍ²、１８ｍｇ／ｍ²となるように添加した。また、イラジエーション防止のために、以下の染料（カッコ内は塗布量を表す）を添加した。
【０１５５】
【化７】

【０１５６】
（層構成）
以下に、各層の構成を示す。数字は塗布量（ｇ／ｍ²）を表す。ハロゲン化銀乳剤は、銀換算塗布量を表す。
支持体
ポリエチレン樹脂ラミネート紙
［第一層側のポリエチレン樹脂に白色顔料（ＴｉＯ₂；含有率１６質量％、ＺｎＯ；含有率４質量％）と蛍光増白剤（４，４'−ビス（５−メチルベンゾオキサゾリル）スチルベン。含有率０．０３質量％）、青味染料（群青）を含む］
第一層（青感性乳剤層）
乳剤Ｂ−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
【０１５７】
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
【０１５８】
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
【０１５９】
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
【０１６０】
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
【０１６１】
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
【０１６２】
【化８】

【０１６３】
【化９】

【０１６４】
【化１０】

【０１６５】
【化１１】

【０１６６】
【化１２】

【０１６７】
【化１３】

【０１６８】
【化１４】

【０１６９】
【化１５】

【０１７０】
【化１６】

【０１７１】
【化１７】

【０１７２】
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１１２とした。
【０１７３】
【表２】

【０１７４】
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２種類の光源で実験を行った。
【０１７５】
（光源Ａ）
レーザー光源としては、半導体レーザー（発振波長 約９４０ｎｍ）を導波路状の反転ドメイン構造を有するＬｉＮｂＯ₃のＳＨＧ結晶により波長変換して取り出した約４７０ｎｍの青色レーザー、半導体レーザー（発振波長 約１０６０ｎｍ）を導波路状の反転ドメイン構造を有するＬｉＮｂＯ₃のＳＨＧ結晶により波長変換して取り出した約５３０ｎｍの緑色レーザーおよび波長約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。
【０１７６】
（光源Ｂ）
光源Ａとは、約４７０ｎｍの青色レーザーの代わりに、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（株）発表）を用いたことのみ異なる光源。
【０１７７】
光源Ａまたは光源Ｂを用いて、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０．８になるようなグレー発色の均一露光を与えた。
露光した各試料に対し、下記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４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。
【０１７８】
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。
【０１７９】
処理工程 温度 時間 補充量^*
発色現像 ４５．０℃ １６秒 ４５ｍＬ
漂白定着 ４０．０℃ １６秒 ３５ｍＬ
リンス（１） ４０．０℃ ８秒 −
リンス（２） ４０．０℃ ８秒 −
リンス（３）＊＊４０．０℃ ８秒 −
リンス（４）＊＊３８．０℃ ８秒 １２１ｍＬ
乾燥 ８０．０℃ １６秒
（注）＊感光材料１ｍ²あたりの補充量
＊＊富士写真フイルム（株）製リンスクリーニングシステムＲＣ５０Ｄをリンス（３）に装着し、リンス（３）からリンス液を取り出してポンプにより逆浸透モジュール（ＲＣ５０Ｄ）へ送る。同槽で送られた透過水はリンス（４）に供給し、濃縮液はリンス（３）に戻す。逆浸透モジュールへの透過水量は５０〜３００ｍＬ／分を維持するようにポンプ圧を調整し、１日１０時間温調循環させた。リンスは（１）から（４）への４タンク向流方式とした。
【０１８０】
各処理液の組成は以下の通りである。
[発色現像液] [タンク液] ［補充液］
水 ８００ｍＬ ６００ｍL
蛍光増白剤（ＦＬ−１） ５．０ｇ ８．５ｇ
トリイソプロパノールアミン ８．８ｇ ８．８ｇ
ｐ−トルエンスルホン酸ナトリウム ２０．０ｇ ２０．０ｇ
エチレンジアミン４酢酸 ４．０ｇ ４．０ｇ
亜硫酸ナトリウム ０．１０ｇ ０．５０ｇ
塩化カリウム １０．０ｇ −
４，５−ジヒドロキシベンゼン−
１，３−ジスルホン酸ナトリウム ０．５０ｇ ０．５０ｇ
ジナトリウム−Ｎ，Ｎ−ビス（スルホナート
エチル）ヒドロキシルアミン ８．５ｇ １４．５ｇ
４−アミノ−３−メチル−Ｎ−エチル−Ｎ−
（β−メタンスルホンアミドエチル）アニリン
・３／２硫酸塩・モノハイドレード １０．０ｇ ２２．０ｇ
炭酸カリウム ２６．３ｇ ２６．３ｇ
水を加えて全量 １０００ｍＬ １０００ｍＬ
ｐＨ（２５℃、硫酸とＫＯＨで調整）１０．３５ １２．６
【０１８１】

【０１８２】
[リンス液] [タンク液] [補充液]
塩素化イソシアヌール酸ナトリウム ０．０２ｇ ０．０２ｇ
脱イオン水（電導度５μＳ／ｃｍ以下）１０００ｍＬ １０００ｍＬ
ｐＨ（２５） ６．５ ６．５
【０１８３】
【化１８】

【０１８４】
同様に露光した試料について、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。
【０１８５】
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。光源Ａを用い１０℃３０％ＲＨの雰囲気下で発色現像時間１６秒で行なった場合の結果をΔＤ_Y（Ａ，１０℃，１６”）で示した。同様にΔＤ_Y（Ｂ，１０℃，１６”）、ΔＤ_Y（Ａ，３０℃，１６”）、ΔＤ_Y（Ｂ，３０℃，１６”）、ΔＤ_Y（Ａ，１０℃，３０”）、ΔＤ_Y（Ｂ，１０℃，３０”）、ΔＤ_Y（Ａ，３０℃，３０”）およびΔＤ_Y（Ｂ，３０℃，３０”）を求めた。なお、「”」は「秒」を意味する。
これらの結果を表３に示した。
【０１８６】
【表３】

【０１８７】
表３の結果から明らかなように、試料１０１〜１０に光源Ｂを用いて露光した場合には、プリント先端部と後端部の色味変化が大きく、品質が安定しないことがわかる（比較例）。一方、試料１０４〜１１２に光源Ｂを用いて露光した場合には、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（本発明）。この効果は、４４０ｎｍ〜４８０ｎｍの青色レーザにより露光し、発色現像時間が短い場合に顕著である現れることがわかる。尚、露光後発色現像が開始されるまでの時間を１０秒以上十分に放置した場合には、試料１０１〜１０でも色味変化は小さかった。
【０１８８】
［実施例２］
（乳剤Ｂ−Ｈ１の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．５３μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が８０％の時点から９０％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり２モル％）およびＫ₄［Ｒｕ（ＣＮ）₆］を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．２３モル％）を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムと増感色素Ａおよび増感色素Ｂを添加し、増感剤としてチオグルコース金を用い最適になるように熟成した。更に１−フェニル−５−メルカプトテトラゾールおよび１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールを添加した。このようにして得られた乳剤を、乳剤Ｂ−Ｈ１とした。
【０１８９】
（乳剤Ｂ−Ｌ１の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．４３μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。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（出来上がりのハロゲン化銀１モルあたり２モル％）およびＫ₄［Ｒｕ（ＣＮ）₆］を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．２３モル％）を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムと増感色素Ａおよび増感色素Ｂを添加し、増感剤としてチオグルコース金を用い最適になるように熟成した。更に１−フェニル−５−メルカプトテトラゾールおよび１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールを添加した。このようにして得られた乳剤を、乳剤Ｂ−Ｌ１とした。
【０１９０】
（乳剤Ｂ−Ｈ２の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．５５μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が５０％の時点から８０％の時点にかけて、Ｃｓ₂［ＯｓＣｌ₅（ＮＯ）］を出来上がりのハロゲン化銀１モルあたりＯｓ量が２×１０^-9モルになる量添加した。硝酸銀の添加が８０％の時点から９０％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり３モル％）およびＫ₄［Ｒｕ（ＣＮ）₆］を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．３１モル％）を添加した。更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ₅］を出来上がりのハロゲン化銀１モルあたりＩｒ量が２×１０^-7モルになる量を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムと増感色素Ａおよび増感色素Ｂを添加し、増感剤としてチオグルコース金を用い最適になるように熟成した。更に１−フェニル−５−メルカプトテトラゾールおよび１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールを添加した。このようにして得られた乳剤を、乳剤Ｂ−Ｈ２とした。
【０１９１】
（乳剤Ｂ−Ｌ２の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．４５μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が５０％の時点から８０％の時点にかけて、Ｃｓ₂［ＯｓＣｌ₅（ＮＯ）］を出来上がりのハロゲン化銀１モルあたりＯｓ量が５×１０^-9モルになる量添加した。硝酸銀の添加が８０％の時点から９０％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり３モル％）およびＫ₄［Ｒｕ(ＣＮ)₆］を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．３１モル％）を添加した。更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ₅］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。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムと増感色素Ａおよび増感色素Ｂを添加し、増感剤としてチオグルコース金を用い最適になるように熟成した。更に１−フェニル−５−メルカプトテトラゾールおよび１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールを添加した。このようにして得られた乳剤を、乳剤Ｂ−Ｌ２とした。
【０１９２】
（乳剤Ｇ−Ｈ１の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．３８μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ（ＣＮ）₆］を添加した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり３モル％）を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．１５モル％）を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムを添加し、増感剤として硫化金コロイド分散物を用い最適になるように熟成した。更に増感色素Ｃ、１−フェニル−５−メルカプトテトラゾール、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールおよび臭化カリウムを添加した。このようにして得られた乳剤を、乳剤Ｇ−Ｈ１とした。
【０１９３】
（乳剤Ｇ−Ｌ１の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．２８μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ（ＣＮ）₆］を添加した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり３モル％）を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．１５モル％）を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムを添加し、増感剤として硫化金コロイド分散物を用い最適になるように熟成した。更に増感色素Ｃ、１−フェニル−５−メルカプトテトラゾール、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールおよび臭化カリウムを添加した。このようにして得られた乳剤を、乳剤Ｇ−Ｌ１とした。
【０１９４】
（乳剤Ｇ−Ｈ２の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．３９μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が５０％の時点から８０％の時点にかけて、Ｃｓ₂［ＯｓＣｌ₅（ＮＯ）］を出来上がりのハロゲン化銀１モルあたりＯｓ量が２×１０^-8モルになる量添加した。硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ（ＣＮ）₆］を添加した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり３モル％）を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．２モル％）を添加した。更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ₅］を出来上がりのハロゲン化銀１モルあたりＩｒ量が４×１０^-7モルになる量を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムを添加し、増感剤として硫化金コロイド分散物を用い最適になるように熟成した。更に増感色素Ｃ、１−フェニル−５−メルカプトテトラゾール、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールおよび臭化カリウムを添加した。このようにして得られた乳剤を、乳剤Ｇ−Ｈ２とした。
【０１９５】
（乳剤Ｇ−Ｌ２の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．２９μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が５０％の時点から８０％の時点にかけて、Ｃｓ₂［ＯｓＣｌ₅（ＮＯ）］を出来上がりのハロゲン化銀１モルあたりＯｓ量が６×１０^-8モルになる量添加した。硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ（ＣＮ）₆］を添加した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり３モル％）を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．２モル％）を添加した。更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ₅］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^-6モルになる量を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムを添加し、増感剤として硫化金コロイド分散物を用い最適になるように熟成した。更に増感色素Ｃ、１−フェニル−５−メルカプトテトラゾール、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールおよび臭化カリウムを添加した。このようにして得られた乳剤を、乳剤Ｇ−Ｌ２とした。
【０１９６】
（乳剤Ｒ−Ｈ１の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．３８μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ（ＣＮ）₆］を添加した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり３モル％）を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．１５モル％）を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムを添加し、硫黄増感剤としてチオ硫酸ナトリウム５水和物と金増感剤としてビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオラート）オーレート（I）テトラフルオロボレートを用い最適になるように熟成した。更に増感色素Ｈ、１−フェニル−５−メルカプトテトラゾール、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾール、化合物Ｉおよび臭化カリウムを添加した。このようにして得られた乳剤を、乳剤Ｒ−Ｈ１とした。
【０１９７】
（乳剤Ｒ−Ｌ１の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．２８μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ（ＣＮ）₆］を添加した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり３モル％）を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．１５モル％）を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムを添加し、硫黄増感剤としてチオ硫酸ナトリウム５水和物と金増感剤としてビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオラート）オーレート（I）テトラフルオロボレートを用い最適になるように熟成した。更に増感色素Ｈ、１−フェニル−５−メルカプトテトラゾール、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾール、化合物Ｉおよび臭化カリウムを添加した。このようにして得られた乳剤を、乳剤Ｒ−Ｌ１とした。
【０１９８】
（乳剤Ｒ−Ｈ２の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．３９μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が５０％の時点から８０％の時点にかけて、Ｃｓ₂［ＯｓＣｌ₅（ＮＯ）］を出来上がりのハロゲン化銀１モルあたりＯｓ量が２×１０^-8モルになる量添加した。硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ（ＣＮ）₆］を添加した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり３モル％）を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．２モル％）を添加した。更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ₅］を出来上がりのハロゲン化銀１モルあたりＩｒ量が４×１０^-7モルになる量を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムを添加し、硫黄増感剤としてチオ硫酸ナトリウム５水和物と金増感剤としてビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオラート）オーレート（I）テトラフルオロボレートを用い最適になるように熟成した。更に増感色素Ｈ、１−フェニル−５−メルカプトテトラゾール、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾール、化合物Ｉおよび臭化カリウムを添加した。このようにして得られた乳剤を、乳剤Ｒ−Ｈ２とした。
【０１９９】
（乳剤Ｒ−Ｌ２の調製）
攪拌したゼラチン水溶液中に、硝酸銀と塩化ナトリウムを同時添加して混合する定法で、球相当径０．２９μｍ、変動係数１０％の立方体高塩化銀乳剤を調製した。但し、硝酸銀の添加が５０％の時点から８０％の時点にかけて、Ｃｓ₂［ＯｓＣｌ₅（ＮＯ）］を出来上がりのハロゲン化銀１モルあたりＯｓ量が６×１０^-8モルになる量添加した。硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ（ＣＮ）₆］を添加した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウム（出来上がりのハロゲン化銀１モルあたり３モル％）を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］を添加した。硝酸銀の添加が９０％終了した時点で沃化カリウム（出来上がりのハロゲン化銀１モルあたり０．２モル％）を添加した。更に硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ（５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ）Ｃｌ₅］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^-6モルになる量を添加した。得られた乳剤に脱塩処理を施した後、ゼラチンを加え再分散した。この乳剤にベンゼンチオスルフォン酸ナトリウムを添加し、硫黄増感剤としてチオ硫酸ナトリウム５水和物と金増感剤としてビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオラート）オーレート（I）テトラフルオロボレートを用い最適になるように熟成した。更に増感色素Ｈ、１−フェニル−５−メルカプトテトラゾール、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾール、化合物Ｉおよび臭化カリウムを添加した。このようにして得られた乳剤を、乳剤Ｒ−Ｌ２とした。
【０２００】
以上の乳剤を用いて下記の試料を作製した。
第一層（青感性乳剤層）
乳剤Ｂ−Ｈ１ ０．０７
乳剤Ｂ−Ｌ１ ０．０７
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
【０２０１】
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
【０２０２】
第三層（緑感性乳剤層）
乳剤Ｇ−Ｈ１ ０．０６
乳剤Ｇ−Ｌ１ ０．０６
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
【０２０３】
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
【０２０４】
第五層（赤感性乳剤層）
乳剤Ｒ−Ｈ１ ０．０５
乳剤Ｒ−Ｌ１ ０．０５
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
【０２０５】
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
【０２０６】
【化１９】

【０２０７】
以上のようにして得られた試料を、試料２０１とした。試料２０１とは乳剤Ｂ−Ｈ１、Ｂ−Ｌ１、Ｇ−Ｈ１、Ｇ−Ｌ１、Ｒ−Ｈ１およびＲ−Ｌ１を、それぞれ乳剤Ｂ−Ｈ２、Ｂ−Ｌ２、Ｇ−Ｈ２、Ｇ−Ｌ２、Ｒ−Ｈ２およびＲ−Ｌ２に替えた試料も同様に作製し試料２０２とした。
【０２０８】
これらの試料に実施例１と同じく光源Ａおよび光源Ｂを用いてレーザー走査露光および処理を行い、ΔＤ_Yを読み取った。得られた結果を表４に示す。
【０２０９】
【表４】

表４の結果から明らかなように、試料２０２に光源Ｂを用いて露光すると、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。
【０２１０】
【発明の効果】
以上、本発明によれば、発光波長４２０ｎｍ〜４６０ｎｍの青色レーザーを用い走査露光し、短い潜像時間で発色現像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 using a silver halide color photographic light-sensitive material suitable for an inexpensive laser light source.To the lawIn particular, image formation using a silver halide color photographic material that provides stable performance when scanning exposure is performed using an inexpensive laser light source and development processing is performed after a short latent image time.To the lawRelated.
[0002]
[Prior art]
In recent years, there has been a remarkable spread of digitization in the field of color printing using color photographic paper. For example, the digital exposure method using laser scanning exposure is an analog that directly prints with a color printer from a processed color negative film. Compared to the exposure method, it shows a dramatic increase in the penetration rate. Such a digital exposure method is characterized in that high image quality can be obtained by performing image processing, and plays an extremely important role in improving the quality of color prints using color photographic paper. In addition, with the rapid spread of digital cameras, it is also an important factor that simple and high-quality color prints can be obtained from these electronic recording media, and it is thought that these will lead to further dramatic spread.
[0003]
On the other hand, as a color printing method, technologies such as an ink jet method, a sublimation type method, and color xerography have advanced, and are being recognized as a color printing method, such as improving the quality of photographs. Among these, the characteristics of the digital exposure method using color photographic paper are high image quality, high productivity, and high image robustness. These features can be further extended to make higher quality photographs easier. It is desired to provide it at a lower cost. In particular, if you receive a digital camera recording medium at a store, finish a high-quality print within a short time of about a few minutes and return it on the spot, that is, if you can provide a one-stop service for color printing, color printing using color photographic paper The advantage of printing is increasing. In addition, if the rapid processing of color photographic paper is improved, it is possible to use a printing device that is smaller and cheaper but has high productivity, and that one-stop services for color printing can be expected to become increasingly popular. In view of these points, it is particularly important to improve the rapid processability of color photographic paper.
[0004]
To enable one-stop service for color printing using color photographic paper, various methods such as shortening the exposure time, shortening the so-called latent image time from exposure to processing start, shortening the time from processing to drying, etc. Consideration from various viewpoints is necessary, and 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 in the case of a normal printer capability used at a store, there is almost no problem. The latent image time is designed to be as short as possible with a printer. In addition, the time from processing to drying has been shortened, and proposals have been made for rapid processing based on the processing solution composition, processing temperature, stirring conditions of the processing solution, ironing of the photosensitive material, devising the drying method, and the like. ing.
[0005]
On the other hand, digital images are written on color photographic paper by laser scanning exposure. Conventionally, as a blue laser light source, a method of converting a gas laser or a semiconductor laser having a longer oscillation wavelength to a shorter wavelength using an SHG element has been used. The former has a larger exposure device, and the latter can be reduced in size to some extent, but there is a limit to reducing the cost of the printer and further downsizing. In recent years, blue semiconductor lasers with wavelengths of 430 to 460 nm that do not use SHG elements (announced by Nichia Chemical Co., Ltd. at the 48th Applied Physics Related Conference in March 2001) have been developed, and the possibility of cost reduction of printers Increased.
[0006]
For the above-mentioned purpose, we studied scanning a color photographic paper with a blue semiconductor laser and performing a short latent image time within 9 seconds and color development within a short time within 28 seconds. 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. We have made various studies to solve this problem, and have found that a silver halide emulsion used for color photographic paper can be solved by containing a specific metal complex.
[0007]
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.
[0008]
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.
[0009]
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.
[0010]
However, in these known techniques, instability of photographic characteristics and improvement thereof are discussed when color photographic paper is subjected to scanning exposure with a blue laser and color development processing is performed with a short latent image time of 9 seconds or less. Absent.
[0011]
[Problems to be solved by the invention]
  The problem to be solved by the present invention is an image forming method in which stable photographic performance is always obtained even when a blue laser having an emission wavelength of 420 nm to 460 nm is used for scanning exposure and color development processing is performed in a short latent image time.The lawIs to provide. Image formation using silver halide color photographic materials especially suitable for color printingThe lawIs to provide.
[0012]
[Means for Solving the Problems]
  As a result of intensive studies, the present inventors have found that the above problem 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,
  Halogenation in which at least one of the yellow dye-forming coupler-containing silver halide emulsion layers contains at least one selected from metal complexes represented by the following general formula (I) and the silver chloride content is 90 mol% or more Including silver emulsion,The amount of silver coated on the yellow dye-forming coupler-containing silver halide emulsion layer is 0.1 to 0.23 g / m. ² And the total silver coating amount of the silver halide color photographic light-sensitive material is 0.2 to 0.5 g / m. ² And
  And the silver halide color photographic light-sensitive material is a blue light having an emission wavelength of 420 nm to 460 nm.semiconductorAn image forming method comprising performing scanning exposure with an exposure light source which is a laser, and starting color development within 9 seconds after the scanning exposure.
[0013]
Formula (I)
[IrX^I _nL^I _(6-n)]^m
(In the general formula (I), X^IRepresents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L^IIs X^IRepresents an arbitrary ligand different from n, n represents 3, 4 or 5, and m represents 5-, 4-, 3-, 2-, 1-, 0, or 1+. )
[0014]
  (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,
  Halogenation in which at least one of the yellow dye-forming coupler-containing silver halide emulsion layers contains at least one selected from metal complexes represented by the following general formula (II) and the silver chloride content is 90 mol% or more Including silver emulsion,The amount of silver coated on the yellow dye-forming coupler-containing silver halide emulsion layer is 0.1 to 0.23 g / m. ² And the total silver coating amount of the silver halide color photographic light-sensitive material is 0.2 to 0.5 g / m. ² And
  And the silver halide color photographic light-sensitive material is a blue light having an emission wavelength of 420 nm to 460 nm.semiconductorAn image forming method comprising performing scanning exposure using an exposure light source which is a laser, and starting color development within 9 seconds after the scanning exposure.
  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+. )
[0015]
  (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 metal complexes represented by the following general formula (I) and at least one metal complex represented by the following general formula (II) in at least one of the yellow dye-forming coupler-containing silver halide emulsion layers A silver halide emulsion containing at least one kind and having a silver chloride content of 90 mol% or more,The amount of silver coated on the yellow dye-forming coupler-containing silver halide emulsion layer is 0.1 to 0.23 g / m. ² And the total silver coating amount of the silver halide color photographic light-sensitive material is 0.2 to 0.5 g / m. ² And
  And the silver halide color photographic light-sensitive material is a blue light having an emission wavelength of 420 nm to 460 nm.semiconductorAn image forming method comprising performing scanning exposure using an exposure light source which is a laser, and starting color development within 9 seconds after the scanning exposure.
  Formula (I)
    [IrX^I _nL^I _(6-n)]^m
  (In the general formula (I), X^IRepresents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L^IIs X^IRepresents an arbitrary ligand different from n, 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+. )
[0016]
  (4)The total silver coating amount of the silver halide color photographic light-sensitive material is 0.2 to 0.41 g / m. ² The image forming method according to claim 1, wherein the image forming method is an image forming method.
[0017]
  (5) Silver halide emulsion of the above-mentioned yellow dye-forming coupler-containing silver halide emulsion layerNone ofIt is a silver halide emulsion having a sphere equivalent diameter of 0.7 μm or less (1) to (4)Of any one ofImage forming method.
[0018]
  (6) The silver halide emulsion of the yellow dye-forming coupler-containing silver halide emulsion layer contains 0.02 to 1 mol% of silver iodide (1) to (5)Of any one ofImage forming method.
[0019]
  (7) The silver halide emulsion of the yellow dye-forming coupler-containing silver halide emulsion layer has a silver iodide-containing phase at any position of 85 to 100% of the grain volume as measured from the inside of the silver halide grains. (6) The image forming method according to (6).
[0020]
  (8) The image forming method according to (7), wherein a silver bromide-containing phase is present inside the silver iodide-containing phase..
[0021]
  (9) The image forming method according to (8), wherein the silver iodide-containing phase and the silver bromide-containing phase are adjacent to each other..
[0022]
  (10) The image forming method as described in any one of (7) to (9), wherein the silver iodide-containing phase has a maximum iodide ion concentration on the surface of silver halide grains..
[0023]
  (11) All the silver halide emulsions of the magenta and cyan dye-forming coupler-containing silver halide emulsion layers are silver halide emulsions having a sphere equivalent diameter of 0.4 μm or less (1) to (10) The image forming method according to any one of the above.
[0024]
  (12) All of the silver halide emulsions in the yellow dye-forming coupler-containing silver halide emulsion layer are silver halide emulsions having a sphere equivalent diameter of 0.6 μm or less. Image forming method.
[0025]
  (13)The image forming method according to any one of (1) to (12), wherein all six ligands contain an iridium complex composed of Cl, Br, or I together with the metal complex..
[0026]
  (14)The color development processing time is within 28 seconds (1) to (13)Of any one ofImage forming method.
[0030]
DETAILED DESCRIPTION OF THE INVENTION
  The present invention is described in detail below.
  In the present invention, a silver halide color photographic light-sensitive material described later is used, and at least one of the exposure light sources is a blue light having an emission wavelength of 420 nm to 460 nm.semiconductorAn image forming method in which color development is started within 9 seconds after scanning exposure with an exposure light source that is a laser.In lawis there. In the present invention, the silver halide color photographic light-sensitive material described later is bluesemiconductorScan exposure using laser, color development processing in a short latent image timeTheWhen performed, stable photographic performance is always obtained.
[0031]
Hereinafter, an image forming method will be described together with a description of a silver halide color photographic light-sensitive material (hereinafter simply referred to as “photosensitive material”) applied to the present invention.
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, wherein the metal is represented by the following general formula (I) in at least one of the yellow dye-forming coupler-containing silver halide emulsion layers A silver halide emulsion containing a complex and / or a metal complex represented by the general formula (II) and having a silver chloride content of 90 mol% or more is contained.
[0032]
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.
[0033]
In addition to the yellow coloring layer, magenta coloring layer, and cyan coloring layer, the photosensitive material may optionally have an antihalation layer, an intermediate layer, and a colored layer as a hydrophilic colloid layer to be described later.
[0034]
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.
[0035]
Formula (I)
[IrX^I _nL^I _(6-n)]^m
In general formula (I), X^IRepresents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L^IIs X^IRepresents an arbitrary ligand different from. n represents 3, 4 or 5, 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)_Three ^-), Cyanate ion (OCN)^-), Thunderate ion (ONC)^-), Azide ion (N_Three ^-) And the like.
[0036]
X^IPreferred are fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, isocyanate ion, thiocyanate ion, nitrate ion, nitrite ion, or azide ion, among which chloride ion, And bromide ions are particularly preferred. L^IThere is no particular limitation, and it may be an inorganic compound or an organic compound, and may be charged or uncharged, but is preferably an uncharged inorganic compound or organic compound.
[0037]
Among the metal complexes represented by the general formula (I), the metal complexes represented by the following general formula (IA) or (IB) are preferable. Among these, a metal complex represented by the general formula (IB) is more preferable.
[0038]
General formula (IA)
[IrX^IA _nL^IA _(6-n)]^m
In general formula (IA), X^IARepresents a pseudohalogen ion other than a halogen ion or a cyanate ion, and L^IAIs X^IARepresents any inorganic ligand different from. 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 are water, OCN, ammonia, phosphine, and carbonyl, with water being particularly preferred.
[0039]
General formula (IB)
[IrX^IB _nL^IB _(6-n)]^m
In general formula (IB), X^IBRepresents a pseudohalogen ion other than a halogen ion or a cyanate ion. L^IBRepresents a ligand in which a chain or cyclic hydrocarbon is used as a parent structure, or a carbon or hydrogen atom in a part of the parent structure is replaced with another atom or atomic group. n represents 3, 4 or 5, 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 a compound containing at least one nitrogen atom and at least one sulfur atom in the 5-membered ring skeleton. preferable.
[0040]
Among the metal complexes represented by the general formula (IB), the metal complexes represented by the following general formula (IC) are more preferable.
[0041]
General formula (IC)
[IrX^{I c} _nL^{I c} _(6-n)]^m
In general formula (IC), X^{I c}Represents a pseudohalogen ion other than a halogen ion or a cyanate ion. L^{I c}Is 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^{I c}Is X in the general formula (I)^IThe preferred range is also the same.
L^{I c}The substituent on the carbon atom in the inner ring skeleton is preferably a substituent having a smaller volume than the n-propyl group. Substituents include methyl, ethyl, methoxy, ethoxy, cyano, isocyano, cyanato, isocyanato, thiocyanato, isothiocyanato, formyl, thioformyl, hydroxy, mercapto, amino, hydrazino Group, azido group, nitro group, nitroso group, hydroxyamino group, carboxyl group, carbamoyl group, fluoro group, chloro group, bromo group and iodo group are preferred.
[0042]
Among the metal complexes represented by the general formula (IC), a metal complex represented by the following general formula (ID) is more preferable.
[0043]
General formula (ID)
[IrX^ID _nL^ID _(6-n)]^m
In general formula (ID), X^IDRepresents a pseudohalogen ion other than a halogen ion or a cyanate ion. L^IDIs a 5-membered ring ligand and represents a ligand containing at least two nitrogen atoms and at least one sulfur atom in the ring skeleton, and may have an arbitrary substituent on a carbon atom in the ring skeleton . n represents 3, 4 or 5, 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. Substituents are preferably halogen atoms (fluorine, chlorine, bromine, iodine), methoxy group, ethoxy group, carboxyl group, methoxycarboxyl group, acyl group, acetyl group, chloroformyl group, mercapto group, methylthio group, thioformyl group, thio Carboxy group, dithiocarboxy group, sulfino group, sulfo group, sulfamoyl group, methylamino group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, hydroxyamino group, hydroxyimino group, carbamoyl group, nitroso Group, nitro group, hydrazino group, hydrazono group or azide group, more preferably halogen atom (fluorine, chlorine, bromine, iodine), chloroformyl group, sulfino group, sulfo group, sulfamoyl group, isocyano group, cyanato group , Isocyanato groups, thiocyanato groups, isothiocyanato group, hydroxyimino group, nitroso group, nitro group, or an azido group. Of these, chlorine, bromine, chloroformyl group, isocyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group and isothiocyanato group are particularly preferable.
[0044]
In the general formulas (I) to (ID), n is preferably 4 or 5, and m is preferably 4-, 3-, 2-, 1-, 0, or 1+, more preferably 2-, Or 1-.
[0045]
Although the preferable specific example of the metal complex represented with general formula (I) below is given, this invention is not limited to these.
[IrCl_Five(H₂O)]^2-
[IrCl_Four(H₂O)₂]^-
[IrCl_Five(H₂O)]^-
[IrCl_Four(H₂O)₂]⁰
[IrCl_Five(OH)]^3-
[IrCl_Four(OH)₂]^2-
[IrCl_Five(OH)]^2-
[IrCl_Four(OH)₂]^2-
[IrCl_Five(O)]^Four-
[IrCl_Four(O)₂]^Five-
[IrCl_Five(O)]^3-
[IrCl_Four(O)₂]^Four-
[IrBr_Five(H₂O)]^2-
[IrBr_Four(H₂O)₂]^-
[IrBr_Five(H₂O)]^-
[IrBr_Four(H₂O)₂]⁰
[IrBr_Five(OH)]^3-
[IrBr_Four(OH)₂]^2-
[IrBr_Five(OH)]^2-
[IrBr_Four(OH)₂]^2-
[IrBr_Five(O)]^Four-
[IrBr_Four(O)₂]^Five-
[IrBr_Five(O)]^3-
[IrBr_Four(O)₂]^Four-
[IrCl_Five(OCN)]^3-
[IrBr_Five(OCN)]^3-
[IrCl_Five(thiazole)]^2-
[IrCl_Four(thiazole)₂]^-
[IrCl_Three(thiazole)_Three]⁰
[IrBr_Five(thiazole)]^2-
[IrBr_Four(thiazole)₂]^-
[IrBr_Three(thiazole)_Three]⁰
[IrCl_Five(5-methylthiazole)]^2-
[IrCl_Four(5-methylthiazole)₂]^-
[IrBr_Five(5-methylthiazole)]^2-
[IrBr_Four(5-methylthiazole)₂]^-
[IrCl_Five(5-chlorothiadizole)]^2-
[IrCl_Four(5-chlorothiadizole)₂]^-
[IrBr_Five(5-chlorothiadizole)]^2-
[IrBr_Four(5-chlorothiadizole)₂]^-
[IrCl_Five(2-chloro-5-fluorothiadiazole)]^2-
[IrCl_Four(2-chloro-5-fluorothiadiazole)₂]^-
[IrBr_Five(2-chloro-5-fluorothiadiazole)]^2-
[IrBr_Four(2-chloro-5-fluorothiadiazole)₂]^-
[IrCl_Five(2-Bromo-5-chlorothiadiazole)]^2-
[IrCl_Four(2-Bromo-5-chlorothiadiazole)₂]^-
[IrBr_Five(2-Bromo-5-chlorothiadiazole)]^2-
[IrBr_Four(2-Bromo-5-chlorothiadiazole)₂]^-
Among these, [IrCl_Five(5-methylthiazole)]^2-Or [IrCl_Five(2-chloro-5-fluorothiadiazole)]^2-Is preferred.
[0046]
Next, the metal complex represented by the general formula (II) will be described.
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+.
X^IIIs preferably a fluoride ion, a chloride ion, a bromide ion, or an iodide ion, and particularly preferably a chloride ion and a bromide ion. 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.
[0047]
Among the metal complexes represented by the general formula (II), the metal complexes represented by the following general formula (IIA) are preferable.
[0048]
General 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.
[0049]
Although the preferable specific example of a metal complex represented by general formula (II) below is given, this invention is not limited to these.
[ReCl₆]^2-
[ReCl_Five (NO)]^2-
[RuCl₆]^2-
[RuCl₆]^3-
[RuCl_Five (NO)]^2-
[RuCl_Five (NS)]^2-
[RuBr_Five (NS)]^2-
[OsCl₆]^Four-
[OsCl_Five (NO)]^2-
[OsBr_Five (NS)]^2-
[RhCl₆]^3-
[RhCl_Five(H₂O)]^2-
[RhCl_Four(H₂O)₂]^-
[RhBr₆]^3-
[RhBr_Five(H₂O)]^2-
[RhBr_Four(H₂O)₂]^-
[PdCl₆]^2-
[PtCl₆]^2-
Among these, [OsCl_Five (NO)]^2-Or [RhBr₆]^3-Is preferred.
[0050]
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.^-TenFrom mole to 1 × 10^-3Mole addition is preferred, 1 × 10^-8From mole to 1 × 10^-FiveMost preferably, it is added in a molar amount. The metal complex represented by the general formula (II) is 1 × 10 5 per mol of silver during grain formation.^-11From mole to 1 × 10^-6Mole addition is preferred, 1 × 10^-9From mole to 1 × 10^-7Most preferably, it is added in a molar amount.
[0051]
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.
[0052]
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.
[0053]
Hereinafter, 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 a {111} plane. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle.
[0054]
In the silver halide emulsion, the silver chloride content is preferably 90 mol% or more (in the case of the silver halide emulsion of the yellow dye-forming coupler-containing silver halide emulsion layer, the silver chloride content is 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.
[0055]
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
[0056]
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.
[0057]
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.
[0058]
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.
[0059]
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.
[0060]
In order to incorporate silver bromide or silver iodide into the 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.
[0061]
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%.
[0062]
Distribution of bromide or iodide ion concentration in the depth direction in the particle is measured by etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using TRIFT II type TOF-SIMS manufactured by Phi Evans. it can. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan. When the emulsion grains are analyzed by the etching / TOF-SIMS method, it is possible to analyze that iodide ions ooze out toward the grain surface even when the addition of the iodide salt solution is finished inside the grains. The emulsion of the present invention is analyzed by etching / TOF-SIMS method, and it is preferable that iodide ions have a maximum concentration on the grain surface, and the iodide ion concentration is attenuated toward the inside. It is preferable to have a concentration maximum inside. The local concentration of silver bromide can also be measured by X-ray diffraction if the silver bromide content is somewhat high.
[0063]
In this specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. The emulsion of the present invention is preferably composed of grains having a monodispersed grain size distribution. The variation system number of the sphere equivalent diameter of all the particles of the present invention is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. The variation coefficient of the equivalent sphere diameter is expressed as a percentage of the standard deviation of the equivalent sphere diameter of each particle with respect to the average equivalent sphere diameter. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating.
[0064]
In the silver halide emulsion, the equivalent sphere diameter of the silver halide emulsion in the yellow dye-forming coupler-containing silver halide emulsion layer is preferably 0.7 μm or less (preferably 0.7 μm to 0.10 μm). More preferably, it is 6 μm (preferably 0.6 μm to 0.15 μm) or less, and most preferably 0.5 μm or less (preferably 0.5 μm to 0.15 μm). The sphere equivalent diameter of the silver halide emulsion layer 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 the grains be silver halide grains defined in the present invention, and preferably 80% or more. More preferably, it is 90% or more.
[0065]
In addition to the iridium complex represented by the general formula (I) and / or, the specific silver halide grains in the silver halide emulsion further contain an iridium complex in which all six ligands consist of Cl, Br or I only. can do. 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).
[0066]
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-
[0067]
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.
[0068]
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^-FourMost preferably, it is added in a molar amount.
[0069]
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.
[0070]
Examples of the gold (I) compound having an organic ligand (organic compound) include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, such as bis (1,4,5-trimethyl-1, 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate, organomercaptogold (I) complexes described in JP-A-11-218870, such as potassium bis (1- [3- (2-sulfonate benzamide) ) Phenyl] -5-mercaptotetrazole potassium salt) Aurate (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^-FourIs a mole.
[0071]
Colloidal gold sulfide can also be used. The manufacturing method thereof is Research Disclosure (37154), Solid State Ionics 79, 60-66, 1995, Compt. Rend.Hebt.Seances Acad.Sci.Sect.B, 263, 1328, published in 1966. The Research Disclosure describes a method using a thiocyanate ion in the production of colloidal gold sulfide, but a thioether compound such as methionine or thiodiethanol can be used instead.
[0072]
Various sizes of colloidal gold sulfide can be used, and those having an average particle size of 50 nm or less are preferred, an average particle size of 10 nm or less is more preferred, and an average particle size of 3 nm or less is even more preferred. This particle size can be measured from a TEM photograph. The composition of colloidal gold sulfide is Au₂S₁But, Au₂S₁~ Au₂S₂Such a composition with excess sulfur may be used, and a composition with excess sulfur is preferred. Au₂S_1.1~ Au₂S_1.8Is more preferable.
[0073]
The composition analysis of the colloidal gold sulfide can be obtained, for example, by taking out gold sulfide particles and determining the gold content and sulfur content by using an analysis method such as ICP or iodometry, respectively. If gold ions and sulfur ions (including hydrogen sulfide and its salts) dissolved in the liquid phase are present in the gold sulfide colloid, the composition analysis of the gold sulfide colloid particles will be affected. The analysis is performed after separation. The amount of colloidal gold sulfide can vary widely depending on the case, but 5 × 10 5 as gold atoms per mole of silver halide.^-7~ 5x10^-3Mole, preferably 5 × 10^-6~ 5x10^-FourIs a mole.
[0074]
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, it produces AgAuS when Ch is S, AgAuSe when Ch is Se, and AgAuTe when Ch is Te. It has the characteristic which is easy to make it. Examples of such a compound include those in which L is an acyl group, and other examples include compounds represented by the following general formulas (AuCh1), (AuCh2), and (AuCh3).
[0075]
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 bond to each other to form a ring.
[0076]
In the compound represented by the general formula (AuCh 1), Ch is preferably a sulfur atom or a selenium atom, X is preferably an oxygen atom or a sulfur atom, R₁Is preferably an alkyl group or an aryl group. Examples of more specific compounds include Au (I) salts of thiosugar (gold thioglucose such as α-gold thioglucose, gold peracetylthioglucose, gold thiomannose, gold thiogalactose, gold thioarabinose, etc.), 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.
[0077]
General formula (AuCh 2)
W₁W₂C = CR_ThreeChAu
Here, Au represents Au (I), Ch represents a sulfur atom, selenium atom or tellurium atom, R_ThreeAnd W₂Represents a substituent (for example, a hydrogen atom, a halogen atom, and an organic group such as an alkyl group, an aryl group, or a heterocyclic group), and W₁Is Hammett's substituent constant σ_pAn electron-withdrawing group having a positive value is represented. R_ThreeAnd W₁, R_ThreeAnd W₂ , W₁And W₂May combine with each other to form a ring.
[0078]
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 R_ThreeIs preferably a hydrogen atom or an alkyl group, and W₁And W₂Is Hammett's substituent constant σ_pAn electron withdrawing group having a value of 0.2 or more is preferred. Examples of more specific compounds include (NC)₂C = CHSAu, (CH_ThreeOCO)₂C = CHSAu, CH_ThreeCO (CH_ThreeOCO) C = CHSAu and the like.
[0079]
General formula (AuCh 3)
W_Three-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, W_ThreeIs Hammett's substituent constant σ_pAn electron-withdrawing group having a positive value is represented.
[0080]
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 W_ThreeIs 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^-FourIs a mole.
[0081]
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. May be. It is particularly preferable to combine with sulfur sensitization and selenium sensitization.
[0082]
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. As specific examples of these compounds, those described on pages 39 to 72 of JP-A-62-215272 are preferably used. Further, 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (the aryl residue has at least one electron-withdrawing group) are also preferably used.
[0083]
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.
[0084]
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.
[0085]
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.
[0086]
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.
[0087]
In the present invention, more preferred reflective supports include those having a polyolefin layer having fine pores on the paper substrate on the side on which the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case preferably the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side does not have micropores (eg, polypropylene, polyethylene) and is on a paper substrate. More preferred is a polyolefin (for example, polypropylene or polyethylene) having micropores on the near side. The density of the multi-layer or single-layer polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 0.40 to 1.0 g / ml, more preferably 0.50 to 0.70 g / ml. The thickness of the multilayer or single layer of polyolefin positioned between the paper substrate and the photographic composition layer is preferably 10 to 100 μm, and more preferably 15 to 70 μm. Further, the ratio of the thickness of the polyolefin layer to the paper substrate is preferably 0.05 to 0.2, more preferably 0.1 to 0.15.
[0088]
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.
[0089]
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.
[0090]
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.
[0091]
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.
[0092]
In the photosensitive material, for the purpose of improving the sharpness of an image, a hydrophilic colloid layer is coated with a dye (especially an oxonol-based dye) described in pages 27 to 76 of EP 0,337,490A2 specification. 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.
[0093]
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.
[0094]
In 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 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.
[0095]
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.
[0096]
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.
[0097]
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.
[0098]
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.
[0099]
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.
[0100]
[Table 1]

[0101]
Other examples of cyan, magenta and yellow couplers used in the present invention include those described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144. Page 3, upper right column, line 14 to page 18, upper left column, last line, page 30, upper right column, line 6 to page 35, lower right column, line 11 and page 0, line 15 to 27 of EP0355,660A2. Couplers described in the 5th line, 5th page, 30th line to 28th page, 45th page, 29th line to 31st line, 47th page, 23rd line to 63rd page, 50th line are also useful.
In the present invention, compounds represented by the general formulas (II) and (III) of WO 98/33760 and the general formula (D) of JP-A-10-221825 may be added.
[0102]
As a cyan dye-forming coupler (sometimes simply referred to as “cyan coupler”) that can be used in the present invention, a pyrrolotriazole coupler is preferably used, and is represented by the general formula (I) or (II) of JP-A-5-313324. ), Couplers represented by general formula (I) of JP-A-6-347960, and exemplified couplers described in these patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Other cyan couplers include pyrroloazole-type cyan couplers described in European Patents EP0488248 and EP0491197A1, 2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716, US Pyrazoloazole-type cyan couplers having an electron-withdrawing group and a hydrogen-bonding group at the 6-position described in Japanese Patent Nos. 4,873,183 and 4,916,051 are disclosed. Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A Nos. 171185, 8-31360, and 8-339060 are also preferable.
[0103]
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.
[0104]
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.
[0105]
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.
[0106]
Further, as yellow dye-forming couplers (sometimes simply referred to as “yellow couplers”), in addition to the compounds described in the above table, a 3- to 5-membered cyclic group is added to the acyl group described in EP 0447969A1. An acylacetamide type yellow coupler having a structure, a malondianilide type yellow coupler having a cyclic structure described in European Patent EP 0482552A1, European Patent Publications Nos. Pyrrole-2 or 3-yl or indole-2 or 3-ylcarbonylacetic acid anilide type couplers described in U.S. Pat. Nos. 5,953,873, 953874, 1,953875A1, etc. Described in US Pat. No. 5,118,599 An acylacetamide type yellow coupler having a dioxane structure is preferably used. Among them, the use of an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring is particularly preferred. These couplers can be used alone or in combination.
[0107]
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.
[0108]
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 and the like are also preferably used.
[0109]
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.
[0110]
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.
[0111]
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.
[0112]
  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 coated in the photographic composition layer in the photosensitive material isIn the present invention,0.2g / m²~ 0.5g / m²IsBut0.2 g / m²~ 0.45g / m²BePreferPreferably, 0.2g / m²~ 0.40g / m²Most preferably.In the present invention, the silver coating amount of the yellow dye-forming coupler-containing silver halide emulsion layer is 0.1 to 0.23 g / m. ² It is.
[0113]
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^-Five~ 1g / m², Preferably 1 × 10^-Four~ 1x10^-1g / m²More preferably 1 × 10^-3~ 1x10^-2g / m²It is.
[0114]
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 development process in which the photosensitive material irradiated with light is developed.
[0115]
In the present invention, the above photosensitive material is used, and at least one of the exposure light sources is scanned and exposed with an exposure light source that is a blue laser having an emission wavelength of 420 nm to 460 nm. This is an image-like exposure using coherent light of a blue laser, and the effects of the present application are effectively exhibited when exposed at the emission wavelength. Among blue lasers, it is particularly preferable to use a blue semiconductor laser. The emission wavelength is preferably 430 nm to 450 nm in the sense that the effects of the present invention are conspicuous.
[0116]
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.
[0117]
When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green, and red. When the exposure time in such scanning exposure is defined as the exposure time of the pixel size when the pixel density is 400 dpi, a preferable exposure time is 10^-FourSeconds or less, more preferably 10^-6Less than a second.
[0118]
  In the present invention, a laser light source is used.AndBlue semiconductor laser with a wavelength of 430 to 460 nm (announced by Nichia Chemical Co., Ltd. at the 48th Applied Physics Related Conference in March 2001)As a laser light source to be used with this, specifically,LiNbO with a semiconductor laser (oscillation wavelength of about 1060 nm) having a waveguide inversion domain structure₃Preferably, 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 .
[0119]
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.
[0120]
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.
[0121]
In the present invention, the above light-sensitive material is used, and color development is started within 9 seconds after exposure as described above.
In the above, the time from exposure to the start of color development (so-called latent image time) is within 9 seconds (preferably within the range of 9 seconds or less and 0.1 seconds or more). In addition, the effect of the present invention is manifested. More preferably, a great effect can be obtained within 6 seconds (within 6 seconds or less and 0.1 seconds or more). In a system in which the exposure apparatus and the processor are separated and independent, the latent image time becomes long, so the effects of the present invention are not exhibited. The effect of the present invention is manifested in a system in which the exposure apparatus and the processing machine are combined to speed up the total printing time.
[0122]
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.
[0123]
Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above.
[0124]
In the present invention, as described in European Patents EP0789270A1 and EP0789480A1, the yellow microdot pattern may be pre-exposed in advance and copy control may be performed before image information is added. .
[0125]
In the 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 on page 20 at the 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.
[0126]
The present invention is also applied as a light-sensitive material having rapid processing suitability. 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. 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.
[0127]
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 heat developing method that does not use a processing solution can be used. In particular, the activator method is a preferable method from the viewpoint of environmental protection because it does not contain a developing agent in the processing solution, so that the processing solution can be easily managed and handled, and the load during processing of the waste liquid is small.
In the activator method, as a developing agent or a precursor thereof incorporated in the photosensitive material, for example, JP-A-8-234388, JP-A-9-152686, JP-A-9-152893, and JP-A-9-212814. The hydrazine type compounds described in JP-A-9-160193 are preferred.
[0128]
Further, a developing method in which the amount of silver applied to the photosensitive material is reduced and image amplification processing (compensation processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, an image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and 9-152695 is preferably used. In the activator method, after processing with an activator solution, desilvering is usually performed. However, in the image amplification processing method using a low silver amount of light-sensitive material, desilvering is omitted and washing or stabilization is simplified. Can be done. Further, in a method of reading image information from a photosensitive material with a scanner or the like, it is possible to adopt a processing form that does not require a desilvering process even when a high silver amount photosensitive material such as a photographic photosensitive material is used.
[0129]
For the activator solution, desilvering solution (bleaching / fixing solution), water washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, those described in Research Disclosure Item 36544 (September 1994), pages 536 to 541 and JP-A-8-234388 can be used.
[0130]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0131]
Example 1
(Preparation of emulsion B-1)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.54 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, potassium bromide (2.5 mol% per mol of the finished silver halide) and K were added from the time when the addition of silver nitrate was 80% to 90%._Four[Ru (CN)₆The amount of Ru per mole of the finished silver halide is 2 × 10^-FiveMolar 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 4.8 × 10^-8Molar amounts were added. When 94% of the addition of silver nitrate was completed, potassium iodide (0.3 mol% per mol of the finished silver halide) was added. The obtained emulsion was desalted and then re-dispersed with gelatin. To this emulsion, sodium benzenethiosulfonate, sensitizing dye A and sensitizing dye B were added, and ripened to be optimal using a gold sulfide colloidal dispersion as a sensitizer. Further 1-phenyl-5-mercaptotetrazole and 1- (5-methylureidophenyl) -5-mercaptotetrazole were added. The emulsion thus obtained was designated as Emulsion B-1.
[0132]
[Chemical 1]

[0133]
(Preparation of emulsion B-2)
Emulsion B-1 is K added when silver nitrate is added from 80% to 90%._Four[Ru (CN)₆] K instead of aqueous solution_Four[Fe (CN)₆The amount of Fe per mole of the finished silver halide is 2 × 10^-FiveAn emulsion differing only in the addition of a molar amount was prepared as Emulsion B-2.
[0134]
(Preparation of emulsion B-3)
Emulsion B-1 is K added when silver nitrate is added from 80% to 90%._Four[Ru (CN)₆] K instead of aqueous solution_Four[Fe (CN)₆The amount of Fe per mole of the finished silver halide is 2 × 10^-FiveM 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 2.3 × 10 3 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 3.6 × 10^-8An emulsion was prepared which differed only in the addition of a molar amount, and was designated as emulsion B-3.
[0135]
(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 2.3 × 10 3 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) Cl_FiveThe amount of Ir per mole of the finished silver halide is 3.2 × 10^-6An emulsion differing only in the addition of a molar amount was prepared as Emulsion B-4.
[0136]
(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 1.0 × 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 92% to 98%, K₂[Ir (5-methylthiazole) Cl_FiveThe amount of Ir per mole of the finished silver halide is 6.7 × 10^-7An emulsion was prepared which differed only in the addition of a molar amount, and was designated as emulsion B-5.
[0137]
(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 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 92% to 98%, K₂[Ir (5-methylthiazole) Cl_FiveThe amount of Ir per mol of the finished silver halide is 5.4 × 10^-7Molar amount and K₂[Ir (H₂O) Cl_FiveThe amount of Ir per mol of the finished silver halide is 2.2 × 10^-6An emulsion was prepared which differed only in the addition of a molar amount, and was designated as emulsion B-6.
[0138]
(Preparation of emulsion B-7)
Emulsion B-1 means that from the point of 60% to 80% addition of silver nitrate,_Three[RhBr₆The amount of Rh per mole of the finished silver halide is 3.2 × 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 2.3 × 10 3 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-7.
[0139]
(Preparation of emulsion B-8)
Emulsion B-1 refers to Cs from the 60% to 80% addition of silver nitrate.₂[Os (NO) Cl_FiveThe amount of Os per mol of the finished silver halide is 3.1 × 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 2.3 × 10 3 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.
[0140]
(Preparation of emulsion B-9)
Emulsion B-1 means that from the point of 60% to 80% addition of silver nitrate,_Three[RhBr₆The amount of Rh per mol of the finished silver halide is 2.5 × 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 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 92% to 98%, K₂[Ir (5-methylthiazole) Cl_FiveThe amount of Ir per mol of the finished silver halide is 5.4 × 10^-7Molar amount and K₂[Ir (H₂O) Cl_FiveThe amount of Ir per mol of the finished silver halide is 2.2 × 10^-6An emulsion differing only in the addition of a molar amount was prepared as Emulsion B-9.
[0141]
(Preparation of emulsion B-10)
Emulsion B-1 means that from the point of 60% to 80% addition of silver nitrate,_Three[RhBr₆The amount of Rh per mole of the finished silver halide is 3.2 × 10^-9Add an amount to make a mole, and add from the point of 80% to 90% of the addition of silver nitrate_Four[Ru (CN)₆] K instead of aqueous solution_Four[Fe (CN)₆The amount of Fe per mole of the finished silver halide is 2 × 10^-FiveM 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 2.3 × 10 3 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-10.
[0142]
(Preparation of emulsion B-11)
Emulsion B-1 means that from the point of 60% to 80% addition of silver nitrate,_Three[RhBr₆The amount of Rh per mole of the finished silver halide is 3.2 × 10^-9Add an amount to make a mole, and add from the point of 80% to 90% of the addition of silver nitrate_Four[Ru (CN)₆] K instead of aqueous solution_Four[Fe (CN)₆The amount of Fe per mole of the finished silver halide is 2 × 10^-FiveM 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 Ir is 1.6 × 10 6 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 2.3 × 10^-8An emulsion was prepared which differed only in the addition of a molar amount, and this was designated as emulsion B-11.
[0143]
(Preparation of emulsion B-12)
Emulsion B-1 refers to Cs from the 60% to 80% addition of silver nitrate.₂[Os (NO) Cl_FiveThe amount of Os per mol of the finished silver halide is 3.1 × 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 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 92% to 98%, K₂[Ir (5-methylthiazole) Cl_FiveThe amount of Ir per mol of the finished silver halide is 5.0 × 10^-7An emulsion was prepared which differed only in the addition of a molar amount, and was designated as emulsion B-12.
[0144]
(Preparation of emulsion G-1)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.40 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 80% to 90%, K_Four[Ru (CN)₆] The amount of Ru per mole of the finished silver halide is 3.0 × 10^-FiveMolar amounts were added. Potassium bromide (4 mol% per mol of finished silver halide) was added from the 80% to 100% addition of silver nitrate. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆The amount of Ir per mol of the finished silver halide is 5.0 × 10^-8Molar amounts were added. When the addition of silver nitrate was completed 90%, potassium iodide (0.2 mol% per mol of finished silver halide) was added. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium benzenethiosulfonate was added to this emulsion, and gold sulfide colloidal dispersion was used as a sensitizer, and ripened to be optimal. Further, sensitizing dye C, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole and potassium bromide were added. The emulsion thus obtained was designated as Emulsion G-1.
[0145]
[Chemical 2]

[0146]
(Preparation of emulsion R-1)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.35 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 80% to 90%, K_Four[Ru (CN)₆The amount of Ru per mole of the finished silver halide is 3 × 10^-FiveMolar amounts were added. Potassium bromide (4.3 mol% per mol of the finished silver halide) was added from the 80% to 100% addition of silver nitrate. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆The amount of Ir per mole of the finished silver halide is 5 × 10^-9Molar amounts were added. When the addition of silver nitrate was completed 90%, potassium iodide (0.15 mol% per mol of the finished silver halide) was added. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium benzenethiosulfonate was added to this emulsion, sodium thiosulfate pentahydrate as a sulfur sensitizer, and bis (1,4,5-trimethyl-1,2,4-triazolium-3- Optimal aging with thiolate) orate (I) tetrafluoroborate. Further, sensitizing dye H, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound I and potassium bromide were added. The emulsion thus obtained was designated as Emulsion R-1.
[0147]
[Chemical Formula 3]

[0148]
[Formula 4]

[0149]
(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. 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.
[0150]
-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.
[0151]
-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.
[0152]
[Chemical formula 5]

[0153]
[Chemical 6]

[0154]
Further, 1-phenyl-5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 1.0 × 10 6 per mole of silver halide.^-3Moles and 5.9 × 10^-FourMole was added. Furthermore, 1-phenyl-5-mercaptotetrazole was added to the second layer, the fourth layer, and the sixth layer, respectively, at 0.2 mg / m 2.²0.2 mg / m²And 0.6 mg / m²It added so that it might become.
Copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200000-400000) is 0.05 g / m on the red sensitive emulsion layer.²Added. Further, disodium catechol-3,5-disulfonate was added to the second layer, the fourth layer, and the sixth layer, respectively, at 6 mg / m.²6 mg / m²18 mg / m²It added so that it might become. In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).
[0155]
[Chemical 7]

[0156]
(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
[0157]
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
[0158]
Third layer (green sensitive emulsion layer)
Emulsion G-1 0.12
Gelatin 1.36
Magenta coupler (ExM) 0.15
Ultraviolet absorber (UV-A) 0.14
Color image stabilizer (Cpd-2) 0.02
Color image stabilizer (Cpd-4) 0.002
Color image stabilizer (Cpd-6) 0.09
Color image stabilizer (Cpd-8) 0.02
Color image stabilizer (Cpd-9) 0.03
Color image stabilizer (Cpd-10) 0.01
Color image stabilizer (Cpd-11) 0.0001
Solvent (Solv-3) 0.11
Solvent (Solv-4) 0.22
Solvent (Solv-5) 0.20
[0159]
Fourth layer (color mixing prevention layer)
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
[0160]
5th layer (red-sensitive emulsion layer)
Emulsion R-1 0.10
Gelatin 1.11
Cyan coupler (ExC-2) 0.13
Cyan coupler (ExC-3) 0.03
Color image stabilizer (Cpd-1) 0.05
Color image stabilizer (Cpd-6) 0.06
Color image stabilizer (Cpd-7) 0.02
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.01
Color image stabilizer (Cpd-14) 0.01
Color image stabilizer (Cpd-15) 0.12
Color image stabilizer (Cpd-16) 0.03
Color image stabilizer (Cpd-17) 0.09
Color image stabilizer (Cpd-18) 0.07
Solvent (Solv-5) 0.15
Solvent (Solv-8) 0.05
[0161]
Sixth layer (UV absorbing layer)
Gelatin 0.46
Ultraviolet absorber (UV-B) 0.45
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.25
Seventh layer (protective layer)
Gelatin 1.00
Acrylic-modified copolymer of polyvinyl alcohol
(Degree of modification 17%) 0.04
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.01
[0162]
[Chemical 8]

[0163]
[Chemical 9]

[0164]
Embedded image

[0165]
Embedded image

[0166]
Embedded image

[0167]
Embedded image

[0168]
Embedded image

[0169]
Embedded image

[0170]
Embedded image

[0171]
Embedded image

[0172]
The sample obtained as described above was designated as Sample 101. Samples 101 were prepared in the same manner as samples 101 except that the emulsions in the blue-sensitive emulsion layer were changed as shown in Table 2.
[0173]
[Table 2]

[0174]
In order to investigate the stability of these samples in laser scanning exposure, experiments were conducted with the following two types of light sources.
[0175]
(Light source A)
As a laser light source, a semiconductor laser (oscillation wavelength of about 940 nm) is LiNbO having a waveguide-like inversion domain structure._ThreeLiNbO with an inverted domain structure in the form of a waveguide using a blue laser of about 470 nm and a semiconductor laser (oscillation wavelength of about 1060 nm) extracted by wavelength conversion using SHG crystal_ThreeA green laser having a wavelength of about 530 nm and a red semiconductor laser having a wavelength of about 650 nm (Hitachi type No. HL6501MG) extracted from the SHG crystal were used. The laser beams of the three colors are moved in the direction perpendicular to the scanning direction by the polygon mirror so that the sample can be sequentially scanned and exposed. Variation in the amount of light due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter is 80 μm, the scanning pitch is 42.3 μm (600 dpi), and the average exposure time per pixel is 1.7 × 10.^-7Second.
[0176]
(Light source B)
The light source A is only the use of a blue semiconductor laser with a wavelength of about 440 nm (announced by Nichia Chemical Co., Ltd. at the 48th Applied Physics Relations Conference in March 2001) instead of a blue laser of about 470 nm. Different light sources.
[0177]
Using a light source A or a light source B, under an environment of 10 ° C. and 30% RH, a gray-colored uniform exposure was performed on an A4 size sample so that the color density of yellow, magenta, and cyan was approximately 0.8.
The following color development processing was performed on each exposed sample. Color development is started about 4 seconds after the exposure of the uniformly exposed A4 sample, and color development is started about 9 seconds after the exposure.
[0178]
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.
[0179]
Processing temperature Temperature Time Replenishment amount^*
Color development 45.0 ℃ 16 seconds 45mL
Bleach fixing 40.0 ℃ 16 seconds 35mL
Rinse (1) 40.0 ° C 8 seconds-
Rinse (2) 40.0 ° C 8 seconds-
Rinse (3) ** 40.0 ° C 8 seconds-
Rinse (4) ** 38.0 ° C 8 sec 121mL
Drying 80.0 ° C 16 seconds
(Note) * Sensitive material 1m²Replenishment amount per
** Mount a phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. on the rinse (3), take out the rinse solution from the rinse (3), and send it to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse (4), and the concentrate is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours per day. The rinsing was a 4-tank countercurrent system from (1) to (4).
[0180]
The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
Water 800mL 600mL
Optical brightening agent (FL-1) 5.0 g 8.5 g
Triisopropanolamine 8.8g 8.8g
Sodium p-toluenesulfonate 20.0 g 20.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.50g
Potassium chloride 10.0 g −
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.50 g 0.50 g
Disodium-N, N-bis (sulfonate
Ethyl) hydroxylamine 8.5 g 14.5 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline
・ 3/2 sulfate ・ Monohydrate 10.0g 22.0g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.35 12.6
[0181]

[0182]
[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL
pH (25) 6.5 6.5
[0183]
Embedded image

[0184]
Similarly exposed samples were subjected to a color development process that was different from the color development process described above except that the color development time was changed to 30 seconds. Further, each coated sample was placed in an atmosphere of 30 ° C. and 30% RH, and the same experiment was repeated.
[0185]
Measure the yellow color density of the front and rear ends of each sample after processing, and find the difference ΔD_YI read. Difference ΔD_YA positive value indicates that the concentration increases from the front end to the rear end. ΔD is the result when the color development time is 16 seconds under the atmosphere of 10 ° C. and 30% RH using the light source A._Y(A, 10 ° C., 16 ″). Similarly, ΔD_Y(B, 10 ° C., 16 ″), ΔD_Y(A, 30 ° C., 16 ″), ΔD_Y(B, 30 ° C., 16 ″), ΔD_Y(A, 10 ° C, 30 "), ΔD_Y(B, 10 ° C., 30 ″), ΔD_Y(A, 30 ° C., 30 ″) and ΔD_Y(B, 30 ° C., 30 ″). “” ”Means“ second ”.
These results are shown in Table 3.
[0186]
[Table 3]

[0187]
As is clear from the results in Table 3, when the samples 101 to 10 are exposed using the light source B, it can be seen that the color change between the leading edge and the trailing edge is large and the quality is not stable (Comparative Example). ). On the other hand, when the samples 104 to 112 are exposed using the light source B, it can be seen that there is little color change between the leading edge and the trailing edge of the print, and stable quality is obtained (the present invention). It can be seen that this effect is prominent when exposed by a blue laser of 440 nm to 480 nm and the color development time is short. In addition, when the time until the color development was started after the exposure was sufficiently left for 10 seconds or more, even in the samples 101 to 10, the color change was small.
[0188]
[Example 2]
(Preparation of emulsion B-H1)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.53 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, potassium bromide (2 mol% per mol of the finished silver halide) and K from the time when the addition of silver nitrate was 80% to 90%_Four[Ru (CN)₆] Was added. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.23 mol% per mol of the finished silver halide) was added. The obtained emulsion was desalted and then re-dispersed with gelatin. To this emulsion, sodium benzenethiosulfonate, sensitizing dye A and sensitizing dye B were added, and ripened to be optimal using gold thioglucose as a sensitizer. Further 1-phenyl-5-mercaptotetrazole and 1- (5-methylureidophenyl) -5-mercaptotetrazole were added. The emulsion thus obtained was named Emulsion B-H1.
[0189]
(Preparation of emulsion B-L1)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.43 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. From 80% to 90% addition of silver nitrate, potassium bromide (2 mole% per mole of finished silver halide) and K_Four[Ru (CN)₆] Was added. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.23 mol% per mol of the finished silver halide) was added. The obtained emulsion was desalted and then re-dispersed with gelatin. To this emulsion, sodium benzenethiosulfonate, sensitizing dye A and sensitizing dye B were added, and ripened to be optimal using gold thioglucose as a sensitizer. Further 1-phenyl-5-mercaptotetrazole and 1- (5-methylureidophenyl) -5-mercaptotetrazole were added. The emulsion thus obtained was named Emulsion B-L1.
[0190]
(Preparation of emulsion B-H2)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.55 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 50% to 80%, Cs₂[OsCl_Five(NO)] is 2 × 10 Os per mole of finished silver halide.^-9Molar amounts were added. From 80% to 90% addition of silver nitrate, potassium bromide (3 mole% per mole of finished silver halide) and K_Four[Ru (CN)₆] Was added. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.31 mol% per mol of finished silver halide) was added. Furthermore, when the addition of silver nitrate was 92% to 98%, K₂[Ir (5-methylthiazole) Cl_FiveThe amount of Ir per mole of the finished silver halide is 2 × 10^-7Molar amounts were added. The obtained emulsion was desalted and then re-dispersed with gelatin. To this emulsion, sodium benzenethiosulfonate, sensitizing dye A and sensitizing dye B were added, and ripened to be optimal using gold thioglucose as a sensitizer. Further 1-phenyl-5-mercaptotetrazole and 1- (5-methylureidophenyl) -5-mercaptotetrazole were added. The emulsion thus obtained was named Emulsion B-H2.
[0191]
(Preparation of emulsion B-L2)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.45 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 50% to 80%, Cs₂[OsCl_Five(NO)] is 5 × 10 5 per gram of the finished silver halide.^-9Molar amounts were added. From 80% to 90% addition of silver nitrate, potassium bromide (3 mole% per mole of finished silver halide) and K_Four[Ru (CN)₆] Was added. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.31 mol% per mol of finished silver halide) was added. Furthermore, when the addition of silver nitrate was 92% to 98%, K₂[Ir (5-methylthiazole) Cl_FiveThe amount of Ir per mole of the finished silver halide is 5 × 10^-7Molar amounts were added. The obtained emulsion was desalted and then re-dispersed with gelatin. To this emulsion, sodium benzenethiosulfonate, sensitizing dye A and sensitizing dye B were added, and ripened to be optimal using gold thioglucose as a sensitizer. Further 1-phenyl-5-mercaptotetrazole and 1- (5-methylureidophenyl) -5-mercaptotetrazole were added. The emulsion thus obtained was named Emulsion B-L2.
[0192]
(Preparation of emulsion G-H1)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.38 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 80% to 90%, K_Four[Ru (CN)₆] Was added. Potassium bromide (3 mol% per mol of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.15 mol% per mol of the finished silver halide) was added. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium benzenethiosulfonate was added to this emulsion, and gold sulfide colloidal dispersion was used as a sensitizer, and ripened to be optimal. Further, sensitizing dye C, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole and potassium bromide were added. The emulsion thus obtained was named Emulsion G-H1.
[0193]
(Preparation of emulsion G-L1)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.28 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 80% to 90%, K_Four[Ru (CN)₆] Was added. Potassium bromide (3 mol% per mol of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.15 mol% per mol of the finished silver halide) was added. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium benzenethiosulfonate was added to this emulsion, and gold sulfide colloidal dispersion was used as a sensitizer, and ripened to be optimal. Further, sensitizing dye C, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole and potassium bromide were added. The emulsion thus obtained was named Emulsion G-L1.
[0194]
(Preparation of emulsion G-H2)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.39 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 50% to 80%, Cs₂[OsCl_Five(NO)] is 2 × 10 Os per mole of finished silver halide.^-8Molar amounts were added. From the point of 80% to 90% addition of silver nitrate,_Four[Ru (CN)₆] Was added. Potassium bromide (3 mol% per mol of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.2 mol% per mol of finished silver halide) was added. Furthermore, when the addition of silver nitrate was 92% to 98%, K₂[Ir (5-methylthiazole) Cl_FiveThe amount of Ir per mole of the finished silver halide is 4 × 10^-7Molar amounts were added. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium benzenethiosulfonate was added to this emulsion, and gold sulfide colloidal dispersion was used as a sensitizer, and ripened to be optimal. Further, sensitizing dye C, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole and potassium bromide were added. The emulsion thus obtained was named Emulsion G-H2.
[0195]
(Preparation of emulsion G-L2)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.29 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 50% to 80%, Cs₂[OsCl_Five(NO)] is 6 × 10 Os per mole of finished silver halide.^-8Molar amounts were added. From the point of 80% to 90% addition of silver nitrate,_Four[Ru (CN)₆] Was added. Potassium bromide (3 mol% per mol of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.2 mol% per mol of finished silver halide) was added. Furthermore, when the addition of silver nitrate was 92% to 98%, K₂[Ir (5-methylthiazole) Cl_FiveThe amount of Ir per mole of the finished silver halide is 1.2 × 10^-6Molar amounts were added. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium benzenethiosulfonate was added to this emulsion, and gold sulfide colloidal dispersion was used as a sensitizer, and ripened to be optimal. Further, sensitizing dye C, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole and potassium bromide were added. The emulsion thus obtained was named Emulsion G-L2.
[0196]
(Preparation of emulsion R-H1)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.38 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 80% to 90%, K_Four[Ru (CN)₆] Was added. Potassium bromide (3 mol% per mol of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.15 mol% per mol of the finished silver halide) was added. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium benzenethiosulfonate was added to this emulsion, sodium thiosulfate pentahydrate as a sulfur sensitizer, and bis (1,4,5-trimethyl-1,2,4-triazolium-3- Optimal aging with thiolate) orate (I) tetrafluoroborate. Further, sensitizing dye H, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound I and potassium bromide were added. The emulsion thus obtained was named Emulsion R-H1.
[0197]
(Preparation of emulsion R-L1)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.28 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 80% to 90%, K_Four[Ru (CN)₆] Was added. Potassium bromide (3 mol% per mol of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.15 mol% per mol of the finished silver halide) was added. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium benzenethiosulfonate was added to this emulsion, sodium thiosulfate pentahydrate as a sulfur sensitizer, and bis (1,4,5-trimethyl-1,2,4-triazolium-3- Optimal aging with thiolate) orate (I) tetrafluoroborate. Further, sensitizing dye H, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound I and potassium bromide were added. The emulsion thus obtained was designated as Emulsion R-L1.
[0198]
(Preparation of emulsion R-H2)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.39 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 50% to 80%, Cs₂[OsCl_Five(NO)] is 2 × 10 Os per mole of finished silver halide.^-8Molar amounts were added. From the point of 80% to 90% addition of silver nitrate,_Four[Ru (CN)₆] Was added. Potassium bromide (3 mol% per mol of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.2 mol% per mol of finished silver halide) was added. Furthermore, when the addition of silver nitrate was 92% to 98%, K₂[Ir (5-methylthiazole) Cl_FiveThe amount of Ir per mole of the finished silver halide is 4 × 10^-7Molar amounts were added. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium benzenethiosulfonate was added to this emulsion, sodium thiosulfate pentahydrate as a sulfur sensitizer, and bis (1,4,5-trimethyl-1,2,4-triazolium-3- Optimal aging with thiolate) orate (I) tetrafluoroborate. Further, sensitizing dye H, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound I and potassium bromide were added. The emulsion thus obtained was named Emulsion R-H2.
[0199]
(Preparation of emulsion R-L2)
A cubic high silver chloride emulsion having a sphere equivalent diameter of 0.29 μm and a coefficient of variation of 10% was prepared by a conventional method in which silver nitrate and sodium chloride were simultaneously added and mixed in a stirred gelatin aqueous solution. However, when the addition of silver nitrate is 50% to 80%, Cs₂[OsCl_Five(NO)] is 6 x 10 Os per mole of finished silver halide.^-8Molar amounts were added. From the point of 80% to 90% addition of silver nitrate,_Four[Ru (CN)₆] Was added. Potassium bromide (3 mol% per mol of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆] Was added. When the addition of silver nitrate was completed 90%, potassium iodide (0.2 mol% per mol of finished silver halide) was added. Furthermore, when the addition of silver nitrate was 92% to 98%, K₂[Ir (5-methylthiazole) Cl_FiveThe amount of Ir per mole of the finished silver halide is 1.2 × 10^-6Molar amounts were added. The obtained emulsion was desalted and then re-dispersed with gelatin. Sodium benzenethiosulfonate was added to this emulsion, sodium thiosulfate pentahydrate as a sulfur sensitizer, and bis (1,4,5-trimethyl-1,2,4-triazolium-3- Optimal aging with thiolate) orate (I) tetrafluoroborate. Further, sensitizing dye H, 1-phenyl-5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound I and potassium bromide were added. The emulsion thus obtained was designated as Emulsion RL2.
[0200]
The following samples were prepared using the above emulsions.
First layer (blue sensitive emulsion layer)
Emulsion B-H1 0.07
Emulsion B-L1 0.07
Gelatin 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
[0201]
Second layer (color mixing prevention layer)
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
[0202]
Third layer (green sensitive emulsion layer)
Emulsion G-H1 0.06
Emulsion G-L1 0.06
Gelatin 0.73
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
[0203]
Fourth layer (color mixing prevention layer)
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
UV absorber (UV-C) 0.04
Solvent (Solv-5) 0.09
[0204]
5th layer (red-sensitive emulsion layer)
Emulsion R-H1 0.05
Emulsion R-L1 0.05
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
[0205]
Sixth layer (UV absorbing layer)
Gelatin 0.32
Ultraviolet absorber (UV-C) 0.42
Solvent (Solv-7) 0.08
Seventh layer (protective layer)
Gelatin 0.70
Acrylic-modified copolymer of polyvinyl alcohol
(Degree of modification 17%) 0.04
Liquid paraffin 0.01
Surfactant (Cpd-13) 0.01
Polydimethylsiloxane 0.01
Silicon dioxide 0.003
[0206]
Embedded image

[0207]
The sample obtained as described above was designated as Sample 201. Sample 201 is emulsions B-H1, B-L1, G-H1, G-L1, R-H1, and R-L1, respectively, and emulsions B-H2, B-L2, G-H2, G-L2, and R- A sample replaced with H2 and R-L2 was prepared in the same manner as sample 202.
[0208]
These samples were subjected to laser scanning exposure and processing using light source A and light source B as in Example 1, and ΔD_YI read. The results obtained are shown in Table 4.
[0209]
[Table 4]

As is apparent from the results in Table 4, it can be seen that when the sample 202 is exposed using the light source B, the color change between the front end and the rear end of the print is small and stable quality can be obtained.
[0210]
【The invention's effect】
  As described above, according to the present invention, an image forming method that always provides stable photographic performance even when a blue laser having an emission wavelength of 420 nm to 460 nm is used for scanning exposure and color development processing is performed in a short latent image time.The lawCan be provided.

Claims (14)

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. An image forming method for color development after imagewise exposing a silver halide color photographic light-sensitive material having a photographic composition layer comprising:
Halogenated in which at least one of the yellow dye-forming coupler-containing silver halide emulsion layers contains at least one selected from the metal complex represented by the following general formula (I) and the silver chloride content is 90 mol% or more The silver coating amount of the silver halide emulsion layer containing the yellow dye-forming coupler is 0.1 to 0.23 g / m ² and the total silver coating amount of the silver halide color photographic material Is 0.2 to 0.5 g / m ² ,
The silver halide color photographic light-sensitive material is scanned and exposed with an exposure light source in which at least one of the exposure light sources is a blue semiconductor laser having an emission wavelength of 420 nm to 460 nm, and color development is started within 9 seconds after the scanning exposure. An image forming method.
Formula (I)
_{^{[IrX I n L I (6}} -n)] m
(In the general formula (I), X ^I represents a pseudohalogen ion other than a halogen ion or a cyanate ion, L ^I represents an arbitrary ligand different from X ^I, and n represents 3, 4 or 5) 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. An image forming method for color development after imagewise exposing a silver halide color photographic light-sensitive material having a photographic composition layer comprising:
Halogenation in which at least one of the yellow dye-forming coupler-containing silver halide emulsion layers contains at least one selected from metal complexes represented by the following general formula (II) and the silver chloride content is 90 mol% or more The silver coating amount of the silver halide emulsion layer containing the yellow dye-forming coupler is 0.1 to 0.23 g / m ² and the total silver coating amount of the silver halide color photographic material Is 0.2 to 0.5 g / m ² ,
The silver halide color photographic light-sensitive material is subjected to scanning exposure using an exposure light source in which at least one of the exposure light sources is a blue semiconductor laser having an emission wavelength of 420 nm to 460 nm, and color development is started within 9 seconds after the scanning exposure. An image forming method.
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. 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 selected from metal complexes represented by the following general formula (I) and at least one metal complex represented by the following general formula (II) in at least one of the yellow dye-forming coupler-containing silver halide emulsion layers The silver halide emulsion containing at least one kind and having a silver chloride content of 90 mol% or more, and the coating silver amount of the yellow dye-forming coupler-containing silver halide emulsion layer is 0.1 to 0.23 g / m ² and the total coated silver amount of the silver halide color photographic light-sensitive material is 0.2 to 0.5 g / m ² ,
The silver halide color photographic light-sensitive material is subjected to scanning exposure using an exposure light source in which at least one of the exposure light sources is a blue semiconductor laser having an emission wavelength of 420 nm to 460 nm, and color development is started within 9 seconds after the scanning exposure. An image forming method.
Formula (I)
_{^{[IrX I n L I (6}} -n)] m
(In the general formula (I), X ^I represents a pseudohalogen ion other than a halogen ion or a cyanate ion, L ^I represents an arbitrary ligand different from X ^I, and n represents 3, 4 or 5) 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+. The total silver coating amount of the silver halide color photographic light-sensitive material is 0.2 to 0.41 g / m. ² The image forming method according to claim 1, wherein the image forming method is an image forming method. 5. The silver halide emulsion according to claim 1 , wherein each of the silver halide emulsions in the yellow dye-forming coupler-containing silver halide emulsion layer is a silver halide emulsion having a sphere equivalent diameter of 0.7 μm or less. The image forming method described. 6. The image forming method according to claim 1 , wherein the silver halide emulsion of the yellow dye-forming coupler-containing silver halide emulsion layer contains 0.02 to 1 mol% of silver iodide. . The silver halide emulsion of the yellow dye-forming coupler-containing silver halide emulsion layer has a silver iodide-containing phase at any position of 85 to 100% of the grain volume as measured from the inside of the silver halide grains. The image forming method according to claim 6 . The image forming method according to claim 7, further comprising a silver bromide-containing phase inside the silver iodide-containing phase . 9. The image forming method according to claim 8, wherein the silver iodide-containing phase and the silver bromide-containing phase are adjacent to each other . 10. The image forming method according to claim 7, wherein the silver iodide-containing phase has a maximum iodide ion concentration on the surface of silver halide grains . 11. The silver halide emulsion according to claim 1, wherein all the silver halide emulsions in the magenta and cyan dye-forming coupler-containing silver halide emulsion layer are silver halide emulsions having a sphere equivalent diameter of 0.4 μm or less. The image forming method described in 1 . 12. The image formation according to claim 11, wherein any of the silver halide emulsions 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. Way . The image forming method according to claim 1, wherein all six ligands contain an iridium complex composed of Cl, Br, or I together with the metal complex . 14. The image forming method according to claim 1 , wherein the color development processing time is within 28 seconds.