JP2004117838A - Silver halide emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic emulsion having high sensitivity and excellent in graininess. <P>SOLUTION: In the silver halide emulsion comprising a dispersion medium and silver halide grains, ≥50% of the total projected area of the silver halide grains is occupied by silver halide grains satisfying the following conditions (a), (b) and (c): (a) tabular silver halide grains whose principal planes are (111) faces; (b) an epitaxial bonding part has been formed in at least one of the corners of each tabular grain; (c) when the epitaxial bonding part is divided into a part (A1) whose silver bromide content is <40 mol% and a part (A2) whose silver bromide content is ≥40 mol%, the part A1 exists in the interior of the epitaxial bonding part but does not exist in the surface. <P>COPYRIGHT: (C)2004,JPO

Description

【０１３７】
一般式（１）および（２）において、Ｗ_５１、Ｗ_５２はスルホ基または水素原子を表す。但し、Ｗ_５１、Ｗ_５２の少なくとも１つはスルホ基を表す。スルホ基は一般にはナトリウム、カリウムのようなアルカリ金属塩、またはアンモニウム塩等の水可溶性塩である。好ましい化合物として具体的には、３，５−ジスルホカテコ−ルジナトリウム塩、４−スルホカテコ−ルアンモニウム塩、２，３−ジヒドロキシ−７−スルホナフタレンナトリウム塩、２，３−ジヒドロキシ−６，７−ジスルホナフタレンカリウム塩等があげられる。
【０１３８】
還元増感剤の添加量は乳剤製造条件に依存するので添加量を選ぶ必要があるが、ハロゲン化銀１モル当り１０^−７〜１０^−１モルの範囲が適当である。還元増感剤は水あるいはアルコール類、グリコール類、ケトン類、エステル類、アミド類などの溶媒に溶かし粒子成長中に添加される。
【０１３９】
本発明の乳剤の製造工程中に銀に対する酸化剤を用いることが好ましい。銀に対する酸化剤とは、金属銀に作用して銀イオンに変換せしめる作用を有する化合物をいう。特にハロゲン化銀粒子の形成過程および化学増感過程において副生するきわめて微小な銀粒子を、銀イオンに変換せしめる化合物が有効である。ここで生成する銀イオンは、例えば、ハロゲン化銀、硫化銀、セレン化銀のような水に難溶の銀塩を形成してもよく、又、硝酸銀のような水に易溶の銀塩を形成してもよい。銀に対する酸化剤は、無機物であっても、有機物であってもよい。無機の酸化剤としては、例えば、オゾン、過酸化水素およびその付加物（例えば、ＮａＢＯ_２・Ｈ_２Ｏ_２・３Ｈ_２Ｏ、２ＮａＣＯ_３・３Ｈ_２Ｏ_２、Ｎａ_４Ｐ_２Ｏ_７・２Ｈ_２Ｏ_２、２Ｎａ_２ＳＯ_４・Ｈ_２Ｏ_２・２Ｈ_２Ｏ）、ペルオキシ酸塩（例えば、Ｋ_２Ｓ_２Ｏ_８、Ｋ_２Ｃ_２Ｏ_６、Ｋ_２Ｐ_２Ｏ_８）、ペルオキシ錯体化合物（例えば、Ｋ_２［Ｔｉ（Ｏ_２）Ｃ_２Ｏ_４］・３Ｈ_２Ｏ、４Ｋ_２ＳＯ_４・Ｔｉ（Ｏ_２）ＯＨ・ＳＯ_４・２Ｈ_２Ｏ、Ｎａ_３［ＶＯ（Ｏ_２）（Ｃ_２Ｈ_４）_２］・６Ｈ_２Ｏ）、過マンガン酸塩（例えば、ＫＭｎＯ_４）、クロム酸塩（例えば、Ｋ_２Ｃｒ_２Ｏ_７）のような酸素酸塩、沃素や臭素のようなハロゲン元素、過ハロゲン酸塩（例えば、過沃素酸カリウム）、高原子価の金属の塩（例えば、ヘキサシアノ第二鉄酸カリウム）およびチオスルフォン酸塩がある。
【０１４０】
また、有機の酸化剤としては、ｐ−キノンのようなキノン類、過酢酸や過安息香酸のような有機過酸化物、活性ハロゲンを放出する化合物（例えば、Ｎ−ブロムサクシンイミド、クロラミンＴ、クロラミンＢ）が例として挙げられる。
【０１４１】
本発明において好ましい酸化剤は、オゾン、過酸化水素およびその付加物、ハロゲン元素、チオスルフォン酸塩の無機酸化剤及びキノン類の有機酸化剤である。前述の還元増感と銀に対する酸化剤を併用するのは好ましい態様である。酸化剤を用いたのち還元増感を施こす方法、その逆方法あるいは両者を同時に共存させる方法のなかから選んで用いることができる。これらの方法は粒子形成工程でも化学増感工程でも選んで用いることができる。
【０１４２】
本発明の写真乳剤には、感光材料の製造工程、保存中あるいは写真処理中のかぶりを防止し、あるいは写真性能を安定化させる目的で、種々の化合物を含有させることができる。すなわちチアゾール類、例えば、ベンゾチアゾリウム塩、ニトロイミダゾール類、ニトロベンズイミダゾール類、クロロベンズイミダゾール類、ブロモベンズイミダゾール類、メルカプトチアゾール類、メルカプトベンゾチアゾール類、メルカプトベンズイミダゾール類、メルカプトチアジアゾール類、アミノトリアゾール類、ベンゾトリアゾール類、ニトロベンゾトリアゾール類、メルカプトテトラゾール類（特に１−フェニル−５−メルカプトテトラゾール）；メルカプトピリミジン類；メルカプトトリアジン類；例えば、オキサドリンチオンのようなチオケト化合物；アザインデン類、例えば、トリアザインデン類、テトラアザインデン類（特に４−ヒドロキシ置換（１，３，３ａ，７）チトラアザインデン類）、ペンタアザインデン類のようなかぶり防止剤または安定剤として知られた、多くの化合物を加えることができる。例えば、米国特許第３，９５４，４７４号、同第３，９８２，９４７号明細書、特公昭５２−２８６６０号公報に記載されたものを用いることができる。好ましい化合物の一つに特開昭６３−２１２９３２号公報に記載された化合物がある。かぶり防止剤および安定剤は粒子形成前、粒子形成中、粒子形成後、水洗工程、水洗後の分散時、化学増感前、化学増感中、化学増感後、塗布前のいろいろな時期に目的に応じて添加することができる。乳剤調製中に添加して本来のかぶり防止および安定化効果を発現する以外に、粒子の晶癖を制御する、粒子サイズを小さくする、粒子の溶解性を減少させる、化学増感を制御する、色素の配列を制御するなど多目的に用いることができる。
【０１４３】
本発明の写真乳剤は、メチン色素類その他によって分光増感されることが本発明の効果を発揮するのに好ましい。用いられる色素には、シアニン色素、メロシアニン色素、複合シアニン色素、複合メロシアニン色素、ホロポーラーシアニン色素、ヘミシアニン色素、スチリル色素およびヘミオキソノール色素が包含される。特に有用な色素は、シアニン色素、メロシアニン色素、および複合メロシアニン色素に属する色素である。これらの色素類には、塩基性複素環核としてシアニン色素類に通常利用される核のいずれをも適用できる。すなわち、例えば、ピロリン核、オキサゾリン核、チオゾリン核、ピロール核、オキサゾール核、チアゾール核、セレナゾール核、イミダゾール核、テトラゾール核、ピリジン核；これらの核に脂環式炭化水素環が融合した核；及びこれらの核に芳香族炭化水素環が融合した核、即ち、例えば、インドレニン核、ベンゾインドレニン核、インドール核、ベンゾオキサドール核、ナフトオキサゾール核、ベンゾチアゾール核、ナフトチアゾール核、ベンゾセレナゾール核、ベンゾイミダゾール核、キノリン核が適用できる。これらの核は炭素原子上に置換基を有していてもよい。
【０１４４】
メロシアニン色素または複合メロシアニン色素にはケトメチレン構造を有する核として、例えば、ピラゾリン−５−オン核、チオヒダントイン核、２−チオオキサゾリジン−２，４−ジオン核、チアゾリジン−２，４−ジオン核、ローダニン核、チオバルビツール酸核の５〜６員複素環核を適用することができる。
【０１４５】
これらの増感色素は単独に用いてもよいが、それらの組み合わせを用いてもよく、増感色素の組み合わせは特に、強色増感の目的でしばしば用いられる。その代表例は米国特許第２，６８８，５４５号、同第２，９７７，２２９号、同第３，３９７，０６０号、同第３，５２２，０５２号、同第３，５２７，６４１号、同第３，６１７，２９３号、同第３，６２８，９６４号、同第３，６６６，４８０号、同第３，６７２，８９８号、同第３，６７９，４２８号、同第３，７０３，３７７号、同第３，７６９，３０１号、同第３，８１４，６０９号、同第３，８３７，８６２号、同第４，０２６，７０７号、英国特許第１，３４４，２８１号、同第１，５０７，８０３号、特公昭４３−４９３６号、同５３−１２３７５号、特開昭５２−１１０６１８号、同５２−１０９９２５号の各明細書及び公報に記載されている。
【０１４６】
増感色素とともに、それ自身分光増感作用をもたない色素あるいは可視光を実質的に吸収しない物質であって、強色増感を示す物質を乳剤中に含んでもよい。増感色素を乳剤中に添加する時期は、これまで有用であると知られている乳剤調製の如何なる段階であってもよい。もっとも普通には化学増感の完了後塗布前までの時期に行なわれるが、米国特許第３，６２８，９６９号、および同第４，２２５，６６６号明細書に記載されているように化学増感剤と同時期に添加し分光増感を化学増感と同時に行なうことも、特開昭５８−１１３９２８号公報に記載されているように化学増感に先立って行なうこともでき、またハロゲン化銀粒子沈澱生成の完了前に添加し分光増感を開始することもできる。更にまた米国特許第４，２２５，６６６号明細書に教示されているようにこれらの前記化合物を分けて添加すること、即ちこれらの化合物の一部を化学増感に先立って添加し、残部を化学増感の後で添加することも可能であり、米国特許第４，１８３，７５６号明細書に開示されている方法を始めとしてハロゲン化銀粒子形成中のどの時期であってもよい。添加量は、ハロゲン化銀１モル当り、４×１０^−６〜８×１０^−３モルで用いることができる。
【０１４７】
更に、本発明は分光増感色素で光吸収率を向上させる技術と併用することが好ましい。例えば、分子間力を利用することで増感色素をハロゲン化銀粒子表面へ単層飽和吸着（すなわち１層吸着）より多く吸着させたり、２つ以上の別々に共役しておらず共有結合で連結された発色団を有する、いわゆる連結色素を吸着させることである。その中でも、以下に示した特許公報及び明細書に記載されている技術と併用することが好ましい。特開平１０−２３９７８９号、特開平１１−１３３５３１号、特開２０００−２６７２１６号、特開２０００−２７５７７２号、特開２００１−７５２２２号、特開２００１−７５２４７号、特開２００１−７５２２１号、特開２００１−７５２２６号、特開２００１−７５２２３号、特開２００１−２５５６１５号、特開２００２−２３２９４号、特開平１０−１７１０５８号、特開平１０−１８６５５９号、特開平１０−１９７９８０号、特開２０００−８１６７８号、特開２００１−５１３２号、特開２００１−１６６４１３号、特開２００２−４９１１３号、特開昭６４−９１１３４号、特開平１０−１１０１０７号、特開平１０−１７１０５８号、特開平１０−２２６７５８号、特開平１０−３０７３５８号、特開平１０−３０７３５９号、特開平１０−３１０７１５号、特開２０００−２３１１７４号、特開２０００−２３１１７２号、特開２０００−２３１１７３号、特開２００１−３５６４４２号、欧州特許第９８５９６５Ａ号、欧州特許第９８５９６４Ａ号、欧州特許第９８５９６６Ａ号、欧州特許第９８５９６７Ａ号、欧州特許第１０８５３７２Ａ号、欧州特許第１０８５３７３Ａ号、欧州特許第１１７２６８８Ａ号、欧州特許第１１９９５９５Ａ号、欧州特許第８８７７００Ａ１号。
【０１４８】
更に以下に示した特許公報に記載されている技術と併用することが好ましい。特開平１０−２３９７８９号、特開２００１−７５２２２号、特開平１０−１７１０５８号。
【０１４９】
フラグメント化可能な電子供与性増感剤を用いることもよい。電子供与性増感剤は、米国特許第５，７４７，２３５号、同５，７４７，２３６号、同６，０５４，２６０号、５，９９４，０５１号、欧州特許第７８６６９２Ａ１、同８９３７３２Ａ１、特開平２０００−１８１００１号、同２０００−１８０９９９号、同２０００−１８１００２号、同２０００−１８１０００号、同２０００−２２１６２６号、同２０００―２２１６２８号の各明細書及び公報に記載されている。フラグメント化可能な電子供与性増感剤は感光材料製造工程中のいかなる場合にも使用してよい。例えば粒子形成時、脱塩工程、化学増感時、塗布前などである。またこれらの工程中の複数回に分けて添加することもできる。本発明の化合物は、水、メタノール、エタノールなどの水可溶性溶媒またはこれらの混合溶媒に溶解して添加することが好ましい。水に溶解する場合、ｐＨを高くまたは低くした方が溶解度が上がる化合物については、ｐＨを高くまたは低くして溶解し、これを添加してもよい。フラグメント化可能な電子供与性増感剤は、乳剤層中に使用するのが好ましいが、乳剤層と共に保護層や中間層に添加しておき、塗布時に拡散させてもよい。本発明の化合物の添加時期は増感色素の前後を問わず、それぞれ好ましくはハロゲン化銀１モル当り、１×１０^−９〜５×１０^−２モル、更に好ましくは１×１０^−８〜２×１０^−３モルの割合でハロゲン化銀乳剤層に含有する。
【０１５０】
フラグメント化可能な電子供与性増感剤を用いる時は、保存性改良剤を用いることが好ましい。保存性改良剤は、特開平１１−１１９３６４号、特開２００１−４２４６６号の各公報に記載されている化合物を用いることが好ましい。
【０１５１】
本発明の乳剤は、あらゆる感光材料に用いることができるが、多層カラー写真感光材料に用いることが好ましい。多層カラー写真感光材料の青感層に用いることがさらに好ましく、多層カラー写真感光材料の最高感青感光層に用いることが最も好ましい。このとき、沃化銀含有率が高い場合は特に、青色光の吸収量の増加、および平板形状に起因する増感色素吸着量の増加に基づく青色光の吸収量の増加による高い感度／粒状比が得られる。加えて、粒子の投影面積径の単分散性の向上、および粒子間の沃化銀含有率分布の低下により、高い感度／粒状比、圧力特性の改良、保存経時特性の改良および処理依存性の改良が達成できる。さらに、平板形状により光の散乱が低下し、下層のシャープネスが良化する。
【０１５２】
本発明のハロゲン化銀乳剤を用いて製造される感光材料がカラー写真感光材料の場合は、支持体上に青感色性層、緑感色性層、赤感色性層のハロゲン化銀乳剤層の少なくとも１層が設けられていればよく、ハロゲン化銀乳剤層および非感光性層の層数および層順に特に制限はない。典型的な例としては、支持体上に、実質的に感色性は同じであるが感光度の異なる複数のハロゲン化銀乳剤層から成る感色性層を少なくとも１つ有するハロゲン化銀写真感光材料であり、該感光性層は青色光、緑色光、および赤色光の何れかに感色性を有する単位感光性層であり、多層ハロゲン化銀カラー写真感光材料においては、一般に単位感光性層の配列が、支持体側から順に赤感色性層、緑感色性層、青感色性層の順に設置される。しかし、目的に応じて上記設置順が逆であっても、また同一感色性層中に異なる感光性層が挾まれたような設置順をもとり得る。
上記のハロゲン化銀感光性層の間および最上層、最下層には各層の中間層等の非感光性層を設けてもよい。
【０１５３】
該中間層には、特開昭６１−４３７４８号、同５９−１１３４３８号、同５９−１１３４４０号、同６１−２００３７号、同６１−２００３８号の各公報に記載されるようなカプラー、ＤＩＲ化合物が含まれていてもよく、通常用いられるように混色防止剤を含んでいてもよい。
【０１５４】
各単位感光性層を構成する複数のハロゲン化銀乳剤層は、西独特許第１，１２１，４７０号あるいは英国特許第９２３，０４５号明細書に記載されるように高感度乳剤層、低感度乳剤層の２層構成を好ましく用いることができる。通常は、支持体に向かって順次感光度が低くなる様に配列するのが好ましく、また各ハロゲン乳剤層の間には非感光性層が設けられていてもよい。また、特開昭５７−１１２７５１号、同６２−２００３５０号、同６２−２０６５４１号、同６２−２０６５４３号の各公報に記載されているように支持体より離れた側に低感度乳剤層、支持体に近い側に高感度乳剤層を設置してもよい。
【０１５５】
具体例として支持体から最も遠い側から、例えば低感度青感光性層（ＢＬ）／高感度青感光性層（ＢＨ）／高感度緑感光性層（ＧＨ）／低感度緑感光性層（ＧＬ）／高感度赤感光性層（ＲＨ）／低感度赤感光性層（ＲＬ）の順、またはＢＨ／ＢＬ／ＧＬ／ＧＨ／ＲＨ／ＲＬの順、またはＢＨ／ＢＬ／ＧＨ／ＧＬ／ＲＬ／ＲＨの順等に設置することができる。
【０１５６】
また特公昭５５−３４９３２号公報に記載されているように、支持体から最も遠い側から青感光性層／ＧＨ／ＲＨ／ＧＬ／ＲＬの順に配列することもできる。また特開昭５６−２５７３８号、同６２−６３９３６号公報に記載されているように、支持体から最も遠い側から青感光性層／ＧＬ／ＲＬ／ＧＨ／ＲＨの順に設置することもできる。
【０１５７】
また特公昭４９−１５４９５号公報に記載されているように上層を最も感光度の高いハロゲン化銀乳剤層、中層をそれよりも低い感光度のハロゲン化銀乳剤層、下層を中層よりも更に感光度の低いハロゲン化銀乳剤層を配置し、支持体に向かって感光度が順次低められた感光度の異なる３層から構成される配列が挙げられる。このような感光度の異なる３層から構成される場合でも、特開昭５９−２０２４６４号公報に記載されているように、同一感色性層中において支持体より離れた側から中感度乳剤層／高感度乳剤層／低感度乳剤層の順に配置されてもよい。
【０１５８】
その他、高感度乳剤層／低感度乳剤層／中感度乳剤層、あるいは低感度乳剤層／中感度乳剤層／高感度乳剤層などの順に配置されていてもよい。
また、４層以上の場合にも、上記の如く配列を変えてよい。
【０１５９】
また、露光処理後に像形成しないハロゲン化銀平板粒子を含んだ層を配置しても良い。この乳剤層は、本発明請求項１記載の乳剤層に隣接していなくても良いが、隣接しているほうが好ましく、本発明請求項１記載の乳剤層に対して支持体に近いように配置されることが好ましい。像形成しないハロゲン化銀平板粒子は具体的には、粒子厚みは０．０２μｍ以上０．２μｍ以下が好ましく、０．０５μｍ以上０．１５μｍ以下がさらに好ましい。粒子サイズは、０．０５μｍ以上２．０μｍ以下が好ましく、０．１μｍ以上１．５μｍ以下がさらに好ましい。また、ハロゲン化銀粒子の平均沃化銀含有率は全Ａｇ量に対して３モル％以下が好ましく、さらに２モル％以下が好ましい。像形成しないハロゲン化銀乳剤は、基本的に化学像感処理を施していないことが好ましいが、色素やハロゲン化銀粒子の安定化のためにハロゲン化銀吸着物質が吸着していても良い。像形成しないハロゲン化銀乳剤層において像形成しないハロゲン化銀粒子はＡｇ換算で０．１ｇ／ｍ^２以上２．０ｇ／ｍ^２以下が含まれていることが好ましく、０．２ｇ／ｍ^２以上１．０ｇ／ｍ^２以下がさらに好ましい。像形成しないハロゲン化銀平板粒子は、特開２０００−３０５２２８号、および特開２０００−３１４９４０号公報に記載されているように特定の波長の光を反射するように平板粒子の厚みを設定しても良い。具体的には、像形成しない乳剤層が指示体側に隣接した本発明の請求項１記載の乳剤層が感光する波長域に強い反射を持つような厚みを持った平板粒子を用いても良い。ただし、このように特定の波長を反射するように厚み設定しなくても良い。
上記のように、それぞれの感光材料の目的に応じて種々の層構成、配列を選択することができる。
【０１６０】
本発明に関する感光材料には、前記の種々の添加剤が用いられるが、それ以外にも目的に応じて種々の添加剤を用いることができる。
これらの添加剤は、より詳しくはリサーチ・ディスクロージャー　Ｉｔｅｍ　１７６４３（１９７８年１２月）、同　Ｉｔｅｍ　１８７１６（１９７９年１１月）および同　Ｉｔｅｍ　３０８１１９（１９８９年１２月）に記載されており、その該当個所を後掲の表にまとめて示した。
【０１６１】

【０１６２】
また、ホルムアルデヒドガスによる写真性能の劣化を防止するために、米国特許４，４１１，９８７号や同第４，４３５，５０３号明細書に記載されたホルムアルデヒドと反応して、固定化できる化合物を感光材料に添加することが好ましい。
【０１６３】
本発明には種々のカラーカプラーを使用することができ、その具体例は前出のリサーチ・ディスクロージャーＮｏ．１７６４３、ＶＩＩ−Ｃ〜Ｇ、および同Ｎｏ．３０７１０５、ＶＩＩ−Ｃ〜Ｇに記載された特許に記載されている。
【０１６４】
イエローカプラーとしては、例えば米国特許第３，９３３，５０１号、同第４，０２２，６２０号、同第４，３２６，０２４号、同第４，４０１，７５２号、同第４，２４８，９６１号、特公昭５８−１０７３９号、英国特許第１，４２５，０２０号、同第１，４７６，７６０号、米国特許第３，９７３，９６８号、同第４，３１４，０２３号、同第４，５１１，６４９号、欧州特許第２４９，４７３Ａ号、等に記載のものが好ましい。
【０１６５】
マゼンタカプラーとしては５−ピラゾロン系及びピラゾロアゾール系の化合物が好ましく、米国特許第４，３１０，６１９号、同第４，３５１，８９７号、欧州特許第７３，６３６号、米国特許第３，０６１，４３２号、同第３，７２５，０６７号、リサーチ・ディスクロージャーＮｏ．２４２２０（１９８４年６月）、特開昭６０−３３５５２号、リサーチ・ディスクロージャーＮｏ．２４２３０（１９８４年６月）、特開昭６０−４３６５９号、同６１−７２２３８号、同６０−３５７３０号、同５５−１１８０３４号、同６０−１８５９５１号、米国特許第４，５００，６３０号、同第４，５４０，６５４号、同第４，５５６，６３０号、国際公開ＷＯ８８／０４７９５号に記載のものが特に好ましい。
【０１６６】
シアンカプラーとしては、フェノール系及びナフトール系カプラーが挙げられ、米国特許第４，０５２，２１２号、同第４，１４６，３９６号、同第４，２２８，２３３号、同第４，２９６，２００号、同第２，３６９，９２９号、同第２，８０１，１７１号、同第２，７７２，１６２号、同第２，８９５，８２６号、同第３，７７２，００２号、同第３，７５８，３０８号、同第４，３３４，０１１号、同第４，３２７，１７３号、西独特許公開第３，３２９，７２９号、欧州特許第１２１，３６５Ａ号、同第２４９，４５３Ａ号、米国特許第３，４４６，６２２号、同第４，３３３，９９９号、同第４，７７５，６１６号、同第４，４５１，５５９号、同第４，４２７，７６７号、同第４，６９０，８８９号、同第４，２５４，２１２号、同第４，２９６，１９９号、特開昭６１−４２６５８号等に記載のものが好ましい。
【０１６７】
ポリマー化された色素形成カプラーの典型例は、米国特許第３，４５１，８２０号、同第４，０８０，２１１号、同第４，３６７，２８２号、同第４，４０９，３２０号、同第４，５７６，９１０号、英国特許第２，１０２，１３７号、欧州特許第３４１，１８８Ａ号等の明細書に記載されている。
【０１６８】
発色色素が適度な拡散性を有するカプラーとしては、米国特許第４，３６６，２３７号、英国特許第２，１２５，５７０号、欧州特許第９６，５７０号、西独特許（公開）第３，２３４，５３３号の明細書に記載のものが好ましい。
【０１６９】
発色色素の不要吸収を補正するためのカラード・カプラーは、リサーチ・ディスクロージャーＮｏ．１７６４３のＶＩＩ−Ｇ項、同Ｎｏ．３０７１０５のＶＩＩ−Ｇ項、米国特許第４，１６３，６７０号、特公昭５７−３９４１３号、米国特許第４，００４，９２９号、同第４，１３８，２５８号、英国特許第１，１４６，３６８号明細書に記載のものが好ましい。また、米国特許第４，７７４，１８１号明細書に記載のカップリング時に放出された蛍光色素により発色色素の不要吸収を補正するカプラーや、米国特許第４，７７７，１２０号明細書に記載の現像主薬と反応して色素を形成しうる色素プレカーサー基を離脱基として有するカプラーを用いることも好ましい。
【０１７０】
カップリングに伴って写真的に有用な残基を放出する化合物もまた本発明で好ましく使用できる。現像抑制剤を放出するＤＩＲカプラーは、前述のＲＤ１７６４３、ＶＩＩ−Ｆ項及び同Ｎｏ．３０７１０５、ＶＩＩ−Ｆ項に記載された特許、特開昭５７−１５１９４４号、同５７−１５４２３４号、同６０−１８４２４８号、同６３−３７３４６号、同６３−３７３５０号の各公報、米国特許第４，２４８，９６２号、同第４，７８２，０１２号の各明細書に記載されたものが好ましい。
【０１７１】
現像時に画像状に造核剤もしくは現像促進剤を放出するカプラーとしては、英国特許第２，０９７，１４０号、同第２，１３１，１８８号明細書、特開昭５９−１５７６３８号、同５９−１７０８４０号公報に記載のものが好ましい。また、特開昭６０−１０７０２９号、同６０−２５２３４０号、特開平１−４４９４０号、同１−４５６８７号の各公報に記載の現像主薬の酸化体との酸化還元反応により、かぶらせ剤、現像促進剤、ハロゲン化銀溶剤等を放出する化合物も好ましい。
【０１７２】
その他、本発明の感光材料に用いることのできる化合物としては、米国特許第４，１３０，４２７号明細書等に記載の競争カプラー、米国特許第４，２８３，４７２号、同第４，３３８，３９３号、同第４，３１０，６１８号明細書等に記載の多当量カプラー、特開昭６０−１８５９５０号、特開昭６２−２４２５２号公報等に記載のＤＩＲレドックス化合物放出カプラー、ＤＩＲカプラー放出カプラー、ＤＩＲカプラー放出レドックス化合物もしくはＤＩＲレドックス放出レドックス化合物、欧州特許第１７３，３０２Ａ号、同第３１３，３０８Ａ号明細書に記載の離脱後復色する色素を放出するカプラー、ＲＤ．Ｎｏ．１１４４９、同２４２４１、特開昭６１−２０１２４７号公報等に記載の漂白促進剤放出カプラー、米国特許第４，５５５，４７７号明細書等に記載のリガンド放出カプラー、特開昭６３−７５７４７号公報に記載のロイコ色素を放出するカプラー、米国特許第４，７７４，１８１号明細書に記載の蛍光色素を放出するカプラーが挙げられる。
【０１７３】
本発明に使用するカプラーは、種々の公知の分散方法により感光材料に導入できる。
水中油滴分散法に用いられる高沸点溶媒の例は、例えば、米国特許第２，３２２，０２７号明細書に記載されている。
【０１７４】
水中油滴分散法に用いられる常圧での沸点が１７５℃以上の高沸点有機溶剤の具体例としては、フタル酸エステル類（例えば、ジブチルフタレート、ジシクロヘキシルフタレート、ジ−２−エチルヘキシルフタレート、デシルフタレート、ビス（２，４−ジ−ｔｅｒｔ−アミルフェニル）フタレート、ビス（２，４−ジ−ｔｅｒｔ−アミルフェニル）イソフタレート、ビス（１，１−ジエチルプロピル）フタレート）；リン酸またはホスホン酸のエステル類（例えば、トリフェニルホスフェート、トリクレジルホスフェート、２−エチルヘキシルジフェニルホスフェート、トリシクロヘキシルホスフェート、トリ−２−エチルヘキシルホスフェート、トリドデシルホスフェート、トリブトキシエチルホスフェート、トリクロロプロピルホスフェート、ジ−２−エチルヘキシルフェニルホスホネート）；安息香酸エステル類（例えば、２−エチルヘキシルベンゾエート、ドデシルベンゾエート、２−エチルヘキシル−ｐ−ヒドロキシベンゾエート）；アミド類（例えば、Ｎ，Ｎ−ジエチルドデカンアミド、Ｎ，Ｎ−ジエチルラウリルアミド、Ｎ−テトラデシルピロリドン）；アルコール類またはフェノール類（例えば、イソステアリルアルコール、２，４−ジ−ｔｅｒｔ−アミルフェノール）；脂肪族カルボン酸エステル類（例えば、ビス（２−エチルヘキシル）セバケート、ジオクチルアゼレート、グリセロールトリブチレート、イソステアリルラクテート、トリオクチルシトレート）；アニリン誘導体（例えば、Ｎ，Ｎ−ジブチル−２−ブトキシ−５−ｔｅｒｔ−オクチルアニリン）；炭化水素類（例えば、パラフィン、ドデシルベンゼン、ジイソプロピルナフタレン）を例示することができる。また補助溶剤としては、例えば、沸点が約３０℃以上、好ましくは５０℃以上かつ約１６０℃以下の有機溶剤が使用でき、典型例としては、例えば、酢酸エチル、酢酸ブチル、プロピオン酸エチル、メチルエチルケトン、シクロヘキサノン、２−エトキシエチルアセテート、ジメチルホルムアミドが挙げられる。
【０１７５】
ラテックス分散法の工程、効果および含浸用ラテックスの具体例は、例えば、米国特許第４，１９９，３６３号、西独特許出願（ＯＬＳ）第２，５４１，２７４号および、同第２，５４１，２３０号明細書に記載されている。
【０１７６】
本発明のカラー感光材料中には、フェネチルアルコールや特開昭６３−２５７７４７号、同６２−２７２２４８号、および特開平１−８０９４１号公報に記載の、例えば、１，２−ベンズイソチアゾリン−３−オン、ｎ−ブチル−ｐ−ヒドロキシベンゾエート、フェノール、４−クロル−３，５−ジメチルフェノール、２−フェノキシエタノール、２−（４−チアゾリル）ベンゾイミダゾールのような各種の防腐剤もしくは防黴剤を添加することが好ましい。
【０１７７】
本発明の乳剤は種々のカラー感光材料に適用することができる。例えば、一般用もしくは映画用のカラーネガフィルム、スライド用もしくはテレビ用のカラー反転フィルム、カラーペーパー、カラーポジフィルムおよびカラー反転ペーパーを代表例として挙げることができる。本発明は、カラーデュープ用フィルムにも特に好ましく使用できる。
【０１７８】
本発明の乳剤を含有する感光材料に使用できる適当な支持体は、例えば、前述のＲＤ．Ｎｏ．１７６４３の２８頁、同Ｎｏ．１８７１６の６４７頁右欄から６４８頁左欄、および同Ｎｏ．３０７１０５の８７９頁に記載されている。
【０１７９】
本発明の乳剤を含有する感光材料は、乳剤層を有する側の全親水性コロイド層の膜厚の総和が２８μｍ以下であることが好ましく、２３μｍ以下がより好ましく、１８μｍ以下が更に好ましく、１６μｍ以下が特に好ましい。また膜膨潤速度Ｔ_１／２が３０秒以下が好ましく、２０秒以下がより好ましい。ここでの膜厚は、２５℃相対湿度５５％調湿下（２日）で測定した膜厚を意味する。また、膜膨潤速度Ｔ_１／２は当該技術分野において公知の手法に従って測定することができ、例えばエー・グリーン（Ａ．Ｇｒｅｅｎ）らによりフォトグラフィック・サイエンス・アンド・エンジニアリング（Ｐｈｏｔｏｇｒ．Ｓｃｉ．Ｅｎｇ．）、１９巻、２号、１２４〜１２９頁に記載の型のスエロメーター（膨潤計）を使用することにより測定できる。なお、Ｔ_１／２は発色現像液で３０℃、３分１５秒処理した時に到達する最大膨潤膜厚の９０％を飽和膜厚とし、飽和膜厚の１／２に到達するまでの時間と定義する。
【０１８０】
膜膨潤速度Ｔ_１／２は、バインダーとしてのゼラチンに硬膜剤を加えること、あるいは塗布後の経時条件を変えることによって調整することができる。
【０１８１】
本発明の乳剤を含有する感光材料は、乳剤層を有する側の反対側に、乾燥膜厚の総和が２μｍ〜２０μｍの親水性コロイド層（バック層と称す）を設けることが好ましい。このバック層には、例えば、前述の光吸収剤、フィルター染料、紫外線吸収剤、スタチック防止剤、硬膜剤、バインダー、可塑剤、潤滑剤、塗布助剤、表面活性剤を含有させることが好ましい。このバック層の膨潤率は１５０〜５００％が好ましい。
【０１８２】
本発明に従ったカラー写真感光材料は、前述のＲＤ．Ｎｏ．１７６４３の２８〜２９頁、同Ｎｏ．１８７１６の６５１頁左欄〜右欄、および同Ｎｏ．３０７１０５の８８０〜８８１頁に記載された通常の方法によって現像処理することができる。
【０１８３】
本発明の乳剤を含有する感光材料の現像処理に用いる発色現像液は、好ましくは芳香族第一級アミン系発色現像主薬を主成分とするアルカリ性水溶液である。この発色現像主薬としては、アミノフェノール系化合物も有用であるが、ｐ−フェニレンジアミン系化合物が好ましく使用され、その代表例としては３−メチル−４−アミノ−Ｎ，Ｎジエチルアニリン、３−メチル−４−アミノ−Ｎ−エチル−Ｎ−β−ヒドロキシエチルアニリン、３−メチル−４−アミノ−Ｎ−エチル−Ｎ−β−メタンスルホンアミドエチルアニリン、３−メチル−４−アミノ−Ｎ−エチル−β−メトキシエチルアニリン、及びこれらの硫酸塩、塩酸塩もしくはｐ−トルエンスルホン酸塩などが挙げられる。これらの中で、特に、３−メチル−４−アミノ−Ｎ−エチル−Ｎ−β−ヒドロキシエチルアニリンの硫酸塩が好ましい。これらの化合物は目的に応じ２種以上併用することもできる。
【０１８４】
発色現像液は、例えば、アルカリ金属の炭酸塩、ホウ酸塩もしくはリン酸塩のようなｐＨ緩衝剤、塩化物塩、臭化物塩、沃化物塩、ベンズイミダゾール類、ベンゾチアゾール類もしくはメルカプト化合物のような現像抑制剤またはかぶり防止剤を含むのが一般的である。また必要に応じて、ヒドロキシルアミン、ジエチルヒドロキシルアミン、亜硫酸塩、Ｎ，Ｎ−ビスカルボキシメチルヒドラジンの如きヒドラジン類、フェニルセミカルバジド類、トリエタノールアミン、カテコールスルホン酸類の如き各種保恒剤；エチレングリコール、ジエチレングリコールのような有機溶剤；ベンジルアルコール、ポリエチレングリコール、四級アンモニウム塩、アミン類のような現像促進剤；色素形成カプラー、競争カプラー、１−フェニル−３−ピラゾリドンのような補助現像主薬；粘性付与剤；アミノポリカルボン酸、アミノポリホスホン酸、アルキルホスホン酸、ホスホノカルボン酸に代表されるような各種キレート剤を用いることができる。キレート剤としては、例えば、エチレンジアミン四酢酸、ニトリル三酢酸、ジエチレントリアミン五酢酸、シクロヘキサンジアミン四酢酸、ヒドロキシエチルイミノジ酢酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、ニトリロ−Ｎ，Ｎ，Ｎ−トリメチレンホスホン酸、エチレンジアミン−Ｎ，Ｎ，Ｎ，Ｎ−テトラメチレンホスホン酸、エチレンジアミン−ジ（ｏ−ヒドロキシフェニル酢酸）及びそれらの塩を代表例として挙げることができる。
【０１８５】
反転処理を実施する場合は、通常黒白現像を行なってから発色現像する。この黒白現像液には、例えば、ハイドロキノンのようなジヒドロキシベンゼン類、例えば、１−フェニル−３−ピラゾリドンのような３−ピラゾリドン類、または例えば、Ｎ−メチル−ｐ−アミノフェノールのようなアミノフェノール類の公知の黒白現像主薬を単独であるいは組み合わせて用いることができる。これらの発色現像液及び黒白現像液のｐＨは、９〜１２であることが一般的である。また、これらの現像液の補充量は、処理するカラー写真感光材料にもよるが、一般に感光材料１平方メートル当たり３Ｌ以下であり、補充液中の臭化物イオン濃度を低減させておくことにより５００ミリリットル（以下、ミリリットルを「ｍＬ」とも表記する。）以下にすることもできる。補充量を低減する場合には、処理液の空気との接触面積を小さくすることによって液の蒸発、空気酸化を防止することが好ましい。
【０１８６】
処理槽での写真処理液と空気との接触面積は、以下に定義する開口率で表わすことができる。即ち、
開口率＝［処理液と空気との接触面積（ｃｍ^２）］÷［処理液の容量（ｃｍ^３）］
上記の開口率は０．１以下であることが好ましく、より好ましくは０．００１〜０．０５である。このように開口率を低減させる方法としては、処理槽の写真処理液面に、例えば浮き蓋のような遮蔽物を設ける方法に加えて、特開平１−８２０３３号公報に記載された可動蓋を用いる方法、特開昭６３−２１６０５０号公報に記載されたスリット現像処理方法を挙げることができる。開口率を低減させることは、発色現像及び黒白現像の両工程のみならず、後続の諸工程、例えば、漂白、漂白定着、定着、水洗、安定化の全ての工程において適用することが好ましい。また、現像液中の臭化物イオンの蓄積を抑える手段を用いることにより、補充量を低減することもできる。
【０１８７】
発色現像処理の時間は通常２〜５分の間で設定されるが、高温高ｐＨとし、かつ発色現像主薬を高濃度に使用することにより、更に処理時間の短縮を図ることもできる。
【０１８８】
発色現像後の写真乳剤層は通常漂白処理される。漂白処理は定着処理と同時に行なわれてもよいし（漂白定着処理）、個別に行なわれてもよい。更に処理の迅速化を図るため、漂白処理後に漂白定着処理する処理方法でもよい。さらに、二槽の連続した漂白定着浴で処理すること、漂白定着処理の前に定着処理すること、又は漂白定着処理後に漂白処理することも目的に応じ任意に実施できる。漂白剤としては、例えば、鉄（ＩＩＩ）のような多価金属の化合物、過酸類（特に、過硫酸ソーダは映画用カラーネガフィルムに適する）、キノン類、ニトロ化合物が用いられる。代表的漂白剤としては、鉄（ＩＩＩ）の有機錯塩、例えば、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、シクロヘキサンジアミン四酢酸、メチルイミノ二酢酸、１，３−ジアミノプロパン四酢酸、グリコールエーテルジアミン四酢酸のようなアミノポリカルボン酸類との錯塩、または、例えば、クエン酸、酒石酸、リンゴ酸との錯塩を用いることができる。これらのうち、エチレンジアミン四酢酸鉄（ＩＩＩ）錯塩、及び１，３−ジアミノプロパン四酢酸鉄（ＩＩＩ）錯塩をはじめとするアミノポリカルボン酸鉄（ＩＩＩ）錯塩は、迅速処理と環境汚染防止の観点から好ましい。さらに、アミノボリカルボン酸鉄（ＩＩＩ）錯塩は、漂白液においても、漂白定着液においても特に有用である。これらのアミノポリカルボン酸鉄（ＩＩＩ）錯塩を用いた漂白液又は漂白定着液のｐＨは通常４．０〜８であるが、処理の迅速化のためにさらに低いｐＨで処理することもできる。
【０１８９】
漂白液、漂白定着液及びそれらの前浴には、必要に応じて漂白促進剤を使用することができる。有用な漂白促進剤の具体例は、次の明細書に記載されている：例えば、米国特許第３，８９３，８５８号、西独特許第１，２９０，８１２号、同第２，０５９，９８８号、特開昭５３−３２７３６号、同５３−５７８３１号、同５３−３７４１８号、同５３−７２６２３号、同５３−９５６３０号、同５３−９５６３１号、同５３−１０４２３２号、同５３−１２４４２４号、同５３−１４１６２３号、同５３−１８４２６号、リサーチ・ディスクロージャーＮｏ．１７１２９号（１９７８号７月）に記載のメルカプト基またはジスルフィド基を有する化合物；特開昭５１−１４０１２９号に記載のチアゾリジン誘導体；特公昭４５−８５０６号、特開昭５２−２０８３２号、同５３−３２７３５号、米国特許第３，７０６，５６１号に記載のチオ尿素誘導体、西独特許第１，１２７，７１５号、特開昭５８−１６２３５号に記載の沃化物塩；西独特許第９６６，４１０号、同第２，７４８，４３０号に記載のポリオキシエチレン化合物類；特公昭４５−８８３６号に記載のポリアミン化合物；その他特開昭４９−４０９４３号、同４９−５９６４４号、同５３−９４９２７号、同５４−３５７２７号、同５５−２６５０６号、同５８−１６３９４０号記載の化合物；臭化物イオン等が使用できる。なかでも、メルカプト基またはジスルフィド基を有する化合物が促進効果が大きい観点で好ましく、特に米国特許第３，８９３，８５８号明細書、西独特許第１，２９０，８１２号明細書、特開昭５３−９５６３０号公報に記載の化合物が好ましい。更に、米国特許第４，５５２，８８４号明細書に記載の化合物も好ましい。これらの漂白促進剤は感材中に添加してもよい。撮影用のカラー感光材料を漂白定着するときに、これらの漂白促進剤は特に有効である。
【０１９０】
漂白液や漂白定着液には上記の化合物の他に、漂白ステインを防止する目的で有機酸を含有させることが好ましい。特に好ましい有機酸は、酸解離定数（ｐＫａ）が２〜５である化合物で、具体的には、例えば、酢酸、プロピオン酸、ヒドロキシ酢酸を挙げることができる。
【０１９１】
定着液や漂白定着液に用いられる定着剤としては、例えば、チオ硫酸塩、チオシアン酸塩、チオエーテル系化合物、チオ尿素類、多量の沃化物塩を挙げることができる。このなかではチオ硫酸塩の使用が一般的であり、特にチオ硫酸アンモニウムが最も広範に使用できる。また、チオ硫酸塩と、例えば、チオシアン酸塩、チオエーテル系化合物、チオ尿素の併用も好ましい。定着液や漂白定着液の保恒剤としては、亜硫酸塩、重亜硫酸塩、カルボニル重亜硫酸付加物あるいは欧州特許第２９４，７６９Ａ号明細書に記載のスルフィン酸化合物が好ましい。更に、定着液や漂白定着液には、液の安定化の目的で、各種アミノポリカルボン酸類や有機ホスホン酸類の添加が好ましい。
【０１９２】
本発明において、定着液または漂白定着液には、ｐＨ調整のためにｐＫａが６．０〜９．０の化合物、好ましくはイミダゾール、１−メチルイミダゾール、１−エチルイミダゾール、２−メチルイミダゾールの如きイミダゾール類を０．１〜１０モル／Ｌ添加することが好ましい。
【０１９３】
脱銀工程の時間の合計は、脱銀不良が生じない範囲で短い方が好ましい。好ましい時間は１分〜３分、更に好ましくは１分〜２分である。また、処理温度は２５℃〜５０℃、好ましくは３５℃〜４５℃である。好ましい温度範囲においては脱銀速度が向上し、かつ処理後のステイン発生が有効に防止される。
【０１９４】
脱銀工程においては、撹拌ができるだけ強化されていることが好ましい。撹拌強化の具体的な方法としては、特開昭６２−１８３４６０号公報に記載の感光材料の乳剤面に処理液の噴流を衝突させる方法や、特開昭６２−１８３４６１号公報に回転手段を用いて撹拌効果を上げる方法が挙げられる。更には、液中に設けられたワイパーブレードと乳剤面を接触させながら感光材料を移動させ、乳剤表面を乱流化することによってより撹拌効果を向上させる方法や、処理液全体の循環流量を増加させる方法が挙げられる。このような撹拌向上手段は、漂白液、漂白定着液、定着液のいずれにおいても有効である。撹拌の向上は、乳剤膜中への漂白剤および、定着剤の供給を速め、結果として脱銀速度を高めるものと考えられる。また、前記の撹拌向上手段は漂白促進剤を使用した場合により有効であり、促進効果を著しく増加させたり、漂白促進剤により定着阻害作用を解消させることができる。
【０１９５】
本発明の乳剤を含有する感光材料の現像に用いられる自動現像機は、特開昭６０−１９１２５７号、同６０−１９１２５８号、同６０−１９１２５９号公報に記載の感光材料搬送手段を有していることが好ましい。前記の特開昭６０−１９１２５７号公報に記載のとおり、このような搬送手段は前浴から後浴への処理液の持込みを著しく削減でき、処理液の性能劣化を防止する効果が高い。このような効果は、各工程における処理時間の短縮や処理液補充量の低減に特に有効である。
【０１９６】
本発明の乳剤を含有するハロゲン化銀カラー写真感光材料は、脱銀処理後、水洗及び／又は安定工程を経るのが一般的である。水洗工程での水洗水量は、感光材料の特性（例えば、カプラーのような使用素材による）、用途、更には、例えば、水洗水温、水洗タンクの数（段数）、向流、順流のような補充方式、その他種々の条件に応じて広範囲に設定し得る。このうち、多段向流方式における水洗タンク数と水量の関係は、Ｊｏｕｒｎａｌ　ｏｆ　ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｍｏｔｉｏｎ　Ｐｉｃｔｕｒｅ　ａｎｄ　Ｔｅｌｅｖｉｓｉｏｎ　Ｅｎｇｉｎｅｅｒｓ　第６４巻、Ｐ．２４８〜２５３（１９５５年５月号）に記載の方法で求めることができる。
【０１９７】
前記文献に記載の多段向流方式によれば、水洗水量を大幅に減少し得るが、タンク内における水の滞留時間の増加によりバクテリアが繁殖し、生成した浮遊物が感光材料に付着するというような問題が生じる。本発明のカラー感光材料の処理おいては、このような問題の解決策として、特開昭６２−２８８８３８号公報に記載のカルシウムイオン、マグネシウムイオンを低減させる方法を極めて有効に用いることができる。また、特開昭５７−８５４２号公報に記載の、例えば、イソチアゾロン化合物やサイアベンダゾール類、塩素化イソシアヌール酸ナトリウムのような塩素系殺菌剤、その他、例えば、ベンゾトリアゾールのような、堀口博著「防菌防黴剤の化学」（１９８６年）三共出版、衛生技術会編「微生物の滅菌、殺菌、防黴技術」（１９８２年）工業技術会、日本防菌防黴学会編「防菌防黴剤事典」（１９８６年）に記載の殺菌剤を用いることもできる。
【０１９８】
本発明の乳剤を含有する感光材料の処理おける水洗水のｐＨは、４〜９、好ましくは５〜８である。水洗水温および水洗時間も、例えば感光材料の特性、用途に応じて種々設定し得るが、一般には、１５〜４５℃で２０秒〜１０分、好ましくは２５〜４０℃で３０秒〜５分の範囲が選択される。更に、本発明の感光材料は、上記水洗に代えて、直接安定液によって処理することもできる。このような安定化処理においては、特開昭５７−８５４３号、同５８−１４８３４号、同６０−２２０３４５号の各公報に記載の公知の方法はすべて用いることができる。
【０１９９】
また、前記水洗処理に続いて、更に安定化処理する場合もある。その例として、撮影用カラー感光材料の最終浴として使用される、色素安定化剤と界面活性剤を含有する安定浴を挙げることができる。色素安定化剤としては、例えば、ホルマリンやグルタルアルデヒドのようなアルデヒド類、Ｎ−メチロール化合物、ヘキサメチレンテトラミンあるいはアルデヒド亜硫酸酸付加物を挙げることができる。この安定浴にも、各種キレート剤や防黴剤を加えることができる。
【０２００】
上記水洗及び／又は安定液の補充に伴うオーバーフロー液は脱銀工程のような他の工程において再利用することもできる。
例えば自動現像機を用いた処理において、上記の各処理液が蒸発により濃縮化する場合には、水を加えて濃縮補正することが好ましい。
【０２０１】
本発明の乳剤を含有するハロゲン化銀カラー写真感光材料には、処理の簡略化及び迅速化の目的で発色現像主薬を内蔵させてもよい。内蔵させるためには、発色現像主薬の各種プレカーサーを用いるのが好ましい。例えば、米国特許第３，３４２，５９７号明細書に記載のインドアニリン系化合物、例えば、同第３，３４２，５９９号明細書、リサーチ・ディスクロージャーＮｏ．１４，８５０及び同Ｎｏ．１５，１５９に記載のシッフ塩基型化合物、同Ｎｏ．１３，９２４に記載のアルドール化合物、米国特許第３，７１９，４９２号明細書に記載の金属塩錯体、特開昭５３−１３５６２８号公報に記載のウレタン系化合物を挙げることができる。
【０２０２】
本発明の乳剤を含有するハロゲン化銀カラー感光材料は、必要に応じて、発色現像を促進する目的で、各種の１−フェニル−３−ピラゾリドン類を内蔵してもよい。典型的な化合物は、例えば、特開昭５６−６４３３９号、同５７−１４４５４７号、および同５８−１１５４３８号公報に記載されている。
【０２０３】
本発明における各種処理液は、１０℃〜５０℃において使用される。通常は３３℃〜３８℃の温度が標準的であるが、より高温にして処理を促進し処理時間を短縮したり、逆により低温にして画質の向上や処理液の安定性の改良を達成することができる。
【０２０４】
また、本発明の乳剤を含有するハロゲン化銀感光材料は、米国特許第４，５００，６２６号明細書、特開昭６０−１３３４４９号、同５９−２１８４４３号、同６１−２３８０５６号公報、欧州特許第２１０，６６０Ａ２号明細書などに記載されている熱現像感光材料にも適用できる。
【０２０５】
また、本発明の乳剤を含有するハロゲン化銀カラー写真感光材料は、特公平２−３２６１５号、実公平３−３９７８４号公報などに記載されているレンズ付きフィルムユニットに適用した場合に、より効果を発現しやすく有効である。
【０２０６】
【実施例】
以下に実施例をもって本発明を具体的に説明する。但し、本発明はこれらの実施例に限定されるものではない。
【０２０７】
（実施例１）
以下の製法によりハロゲン化銀種乳剤、およびハロゲン化銀乳剤Ｅｍ−Ａ１〜Ｅｍ−Ａ１１を調製した。
（種乳剤の調製）
特開平１０−２９３３７２号公報の実施例２に記載されたハロゲン化銀平板粒子の調製方法を参考にした。ＫＢｒを０．３８ｇ、および低分子量ゼラチン（重量平均分子量約１５０００）を０．４ｇ含有する分散媒溶液１Ｌを反応容器に４０℃に保ち、それを撹拌しながら０．２９ｍｏｌ／ＬのＡｇＮＯ_３水溶液と０．２９ｍｏｌ／ＬのＫＢｒ水溶液を各々２０ｍＬずつ、同時に４０秒間かけて添加した。添加後１０％ＫＢｒ溶液２２ｍＬを添加した後、７５℃に昇温した。昇温後トリメリット化ゼラチン３５ｇと水２５０ｍＬからなるゼラチン水溶液（６０℃）を分散媒溶液に添加した。この際、ｐＨは６．０に調整した。この後、１．２ｍｏｌ／ＬのＡｇＮＯ_３水溶液と１．２ｍｏｌ／ＬのＫＢｒ水溶液が同時に添加した。この時、添加されるＡｇＮＯ_３に対して沃化銀が４ｍｏｌ％になる量の沃化銀微粒子を同時に添加した。この際、分散媒のｐＢｒは２．６４に保った。水洗した後、ゼラチンを加えｐＨ，５．７、ｐＡｇ，８．８、乳剤１ｋｇ当たりの銀換算の質量１３１．８ｇ、ゼラチン質量６４．１ｇに調整し、種乳剤とした。得られた乳剤中には、全投影面積の９７％が平板粒子で占められており、かつその平板粒子の平均沃化銀含有率は４モル％、平均球相当径は０．６μｍ、平均アスペクト比は２９であった。
【０２０８】
（Ｅｍ−Ａ１）
＜ホスト平板粒子の形成＞
トリメリット化率９７％のトリメリット化ゼラチンを４６ｇ、ＫＢｒを１．７ｇ含む水溶液１２１１ｍＬを７５℃に保ち激しく攪拌した。前述した種乳剤を１５１ｇ加えた後、変成シリコンオイル（日本ユニカー株式会社製品、Ｌ７６０２）を０．３ｇ添加した。Ｈ_２ＳＯ_４を添加してｐＨを５．５に調整した後、ＡｇＮＯ_３を７．０ｇ含む水溶液６７．６ｍＬとＫＩを４モル％含むＫＢｒとＫＩの混合水溶液をダブルジェット法で最終流量が初期流量の５．１倍になるように流量加速して６分間に渡り添加した。この時、銀電位を飽和カロメル電極に対して＋０ｍＶに保った。ベンゼンチオスルホン酸ナトリウム２ｍｇと二酸化チオ尿素２ｍｇを添加した後、反応容器外に設置した攪拌装置にＡｇＮＯ_３を１７０ｇ含む水溶液７６２ｍＬとＫＢｒを１１４．２ｇ、ＫＩを６．６ｇおよび重量平均分子量約２００００のゼラチンを７６．２ｇ含んだ水溶液７６２ｍＬを同時に添加して沃化銀含有率４モル％の沃臭化銀微粒子（平均球相当径：０．０１６μｍ）を調製しながら反応容器内に沃臭化銀微粒子を１２０分間にわたり添加した。この時、銀電位を飽和カロメル電極に対して−３０ｍＶに保った。ＡｇＮＯ_３を５８．５ｇ含む水溶液１３１ｍＬとＫＩを４モル％含むＫＢｒとＫＩの混合水溶液をダブルジェット法で３０分間にわたり添加した。この時、銀電位を飽和カロメル電極に対して最初の２０分間は＋２０ｍＶに、残りの１０分間は＋１２０ｍＶに保った。
【０２０９】
＜エピタキシャルの形成＞
前記、＜ホスト平板粒子の形成＞に引き続き、５０℃に降温した後、０．３％ＫＩ水溶液１３８ｍＬを添加し、増感色素１、２および３を添加した。その後、２０分間５０℃で保持して撹拌を行った後、ＡｇＮＯ_３を２１．３ｇ含む水溶液１３３．１ｍＬとＮａＣｌを４．３８ｇ、ＫＢｒを５．９５ｇ含む水溶液１５０ｍＬと沃化銀微粒子０．００５ｍｏｌを含む溶液を同時に添加した。この際、添加されるＡｇＮＯ_３の１ｍｏｌに対して８．０×１０^−４ｍｏｌのＫ_４［ＲｕＣＮ_６］を存在させた。その後、増感色素１、２および３を添加した。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。化合物１および２を添加した後、５３℃に昇温した。増感色素１、２および３を添加した後、チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金（Ｉ））テトラフルオロボレイト、チオ硫酸ナトリウム、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで、最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。得られたハロゲン化銀粒子の特徴を表１に示す。
【０２１０】
【化２】

【０２１１】
【化３】

【０２１２】
【化４】

【０２１３】
【化５】

【０２１４】
【化６】

【０２１５】
【化７】

【０２１６】
【化８】

【０２１７】
（Ｅｍ−Ａ２）
＜ホスト平板粒子の形成＞
（Ｅｍ−Ａ１）の＜ホスト平板粒子の形成＞と同様に行った。
【０２１８】
＜エピタキシャルの形成＞
前記、＜ホスト平板粒子の形成＞に引き続き、５０℃に降温した後、０．３％ＫＩ水溶液１３８ｍＬを添加し、増感色素１、２および３を添加した。その後２０分間５０℃で保持して撹拌を行った後、ＮａＣｌを８．０５ｇ含む水溶液１４０ｍＬを添加した。その後、ＡｇＮＯ_３を２１．３ｇ含む水溶液１３３．１ｍＬを添加した。この際、添加されるＡｇＮＯ_３の１ｍｏｌに対して８．０×１０^−４ｍｏｌのＫ_４［ＲｕＣＮ_６］を存在させた。その後直ちに、ＫＢｒを５．９６ｇ含む水溶液１９．９ｍＬと沃化銀微粒子０．００５ｍｏｌを含む溶液を添加した。その後、増感色素１、２および３を添加した。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。化合物１、２および３を添加した後、５３℃に昇温した。増感色素１、２および３を添加した後、チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金（Ｉ））テトラフルオロボレイト、チオ硫酸ナトリウム、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで、最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。得られたハロゲン化銀粒子の特徴を表１に示す。
【０２１９】
（Ｅｍ−Ａ３）
＜ホスト平板粒子の形成＞
（Ｅｍ−Ａ１）の＜ホスト平板粒子の形成＞と同様に行った。
【０２２０】
＜エピタキシャルの形成＞
前記、＜ホスト平板粒子の形成＞に引き続き、５０℃に降温した後、０．３％ＫＩ水溶液１３８ｍＬを添加し、増感色素１、２および３を添加した。その後２０分間５０℃で保持して撹拌を行った後、ＮａＣｌを８．０５ｇ含む水溶液１４０ｍＬを添加した。その後、ＡｇＮＯ_３を２１．３ｇ含む水溶液１３３．１ｍＬとＫＢｒを５．９６ｇ含む水溶液１９．９ｍＬと沃化銀微粒子０．００５ｍｏｌを含む溶液を添加した。この際、添加されるＡｇＮＯ_３の１ｍｏｌに対して８．０×１０^−４ｍｏｌのＫ_４［ＲｕＣＮ_６］を存在させた。その後、増感色素１、２および３を添加した。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。化合物１および２を添加した後、５３℃に昇温した。増感色素１、２および３を添加した後、チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金（Ｉ））テトラフルオロボレイト、チオ硫酸ナトリウム、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで、最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
得られたハロゲン化銀粒子の特徴を表１に示す。
【０２２１】
（Ｅｍ−Ａ４）
＜ホスト平板粒子の形成＞
（Ｅｍ−Ａ１）の＜ホスト平板粒子の形成＞と同様に行った。
【０２２２】
＜エピタキシャルの形成＞
前記、＜ホスト平板粒子の形成＞に引き続き、５０℃に降温した後、０．３％ＫＩ水溶液１３８ｍＬを添加し、増感色素１、２および３を添加した。その後２０分間５０℃で保持して撹拌を行った後、ＮａＣｌを８．０５ｇ含む水溶液１４０ｍＬを添加した。その後、ＡｇＮＯ_３を１２．８ｇ含む水溶液７９．９ｍを添加した。この際、同時に反応容器とは別の混合装置内にＡｇＮＯ_３を８．５ｇ含む水溶液５３．１ｍＬとゼラチンを３．５ｇとＫＢｒを６．５５ｇ含む水溶液７０ｍＬとを同時に添加して調製した臭化銀微粒子（平均球相当径：０．０３１μｍ）乳剤を反応容器に添加した。この際、添加されるＡｇＮＯ_３の１ｍｏｌに対して８．０×１０^−４ｍｏｌのＫ_４［ＲｕＣＮ_６］を存在させた。その後、増感色素１、２および３を添加した。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。化合物１および２を添加した後、５３℃に昇温した。さらに増感色素１、２および３を添加した後、チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金（Ｉ））テトラフルオロボレイト、チオ硫酸ナトリウム、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで、最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
得られたハロゲン化銀粒子の特徴を表１に示す。
【０２２３】
（Ｅｍ−Ａ５）
＜ホスト平板粒子の形成＞
（Ｅｍ−Ａ１）の＜ホスト平板粒子の形成＞と同様に行った。
【０２２４】
＜エピタキシャルの形成＞
前記、＜ホスト平板粒子の形成＞に引き続き、５０℃に降温した後、０．３％ＫＩ水溶液１３８ｍＬを添加し、増感色素１、２および３を添加した。その後２０分間５０℃で保持して撹拌を行った後、ＮａＣｌを８．０５ｇ含む水溶液１４０ｍＬを添加した。その後、ＡｇＮＯ_３を１２．８ｇ含む水溶液７９．９ｍを添加した。その後、反応容器とは別の混合装置内にＡｇＮＯ_３を８．５ｇ含む水溶液５３．１ｍＬとゼラチンを３．５ｇとＫＢｒを６．５５ｇ含む水溶液７０ｍＬとを同時に添加して調製した臭化銀微粒子（平均球相当径：０．０３１μｍ）乳剤を反応容器に添加した。この際、添加されるＡｇＮＯ_３の１ｍｏｌに対して８．０×１０^−４ｍｏｌのＫ_４［ＲｕＣＮ_６］を存在させた。その後、増感色素１、２および３を添加した。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。化合物１および２を添加した後、５３℃に昇温した。さらに増感色素１、２および３を添加した後、チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金（Ｉ））テトラフルオロボレイト、チオ硫酸ナトリウム、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで、最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
得られたハロゲン化銀粒子の特徴を表１に示す。
【０２２５】
（Ｅｍ−Ａ６）
＜ホスト平板粒子の形成＞
（Ｅｍ−Ａ１）の＜ホスト平板粒子の形成＞と同様に行った。
【０２２６】
＜エピタキシャルの形成＞
前記、＜ホスト平板粒子の形成＞に引き続き、５０℃に降温した後、０．３％ＫＩ水溶液１３８ｍＬを添加し、増感色素１、２および３を添加した。その後２０分間５０℃で保持して撹拌を行った後、ＮａＣｌを８．０５ｇ含む水溶液１４０ｍＬを添加した。その後、ＡｇＮＯ_３を１２．８ｇ含む水溶液７９．９ｍＬを添加した。この際、添加されるＡｇＮＯ_３の１ｍｏｌに対して８．０×１０^−４ｍｏｌのＫ_４［ＲｕＣＮ_６］を存在させた。その後、増感色素１、２および３を添加した。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。化合物１および２を添加した後、５３℃に昇温した。その後あらかじめ調製した沃塩臭化銀微粒子（銀量にして、０．０５ｍｏｌ、平均塩化銀含有率１０ｍｏｌ％、平均沃化銀含有率５ｍｏｌ％、平均球相当径：０．１１μｍ）を添加した。さらに増感色素１、２および３を添加した後、チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金（Ｉ））テトラフルオロボレイト、チオ硫酸ナトリウム、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで、最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
得られたハロゲン化銀粒子の特徴を表１に示す。
【０２２７】
（Ｅｍ−Ａ７）
＜ホスト平板粒子の形成＞
（Ｅｍ−Ａ１）の＜ホスト平板粒子の形成＞と同様に行った。
【０２２８】
＜エピタキシャルの形成＞
前記、＜ホスト平板粒子の形成＞に引き続き、５０℃に降温した後、０．３％ＫＩ水溶液１３８ｍＬを添加し、増感色素１、２および３を添加した。その後２０分間５０℃で保持して撹拌を行った後、ＮａＣｌを８．０５ｇ含む水溶液１４０ｍＬを添加した。その後、ＡｇＮＯ_３を１２．８ｇ含む水溶液７９．９ｍＬを添加した。その際同時に、あらかじめ調製した沃塩臭化銀微粒子（銀量にして、０．０５ｍｏｌ、平均塩化銀含有率１０ｍｏｌ％、平均沃化銀含有率５ｍｏｌ％、平均球相当径：０．１１μｍ）を反応容器に添加した。この際、添加されるＡｇＮＯ_３の１ｍｏｌに対して８．０×１０^−４ｍｏｌのＫ_４［ＲｕＣＮ_６］を存在させた。その後、増感色素１、２および３を添加した。その後、この乳剤を特開２００２−１２２９５２号公報の本文及び実施例２に記載の限外濾過法で脱塩した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。化合物１および２を添加した後、５３℃に昇温した。さらに増感色素１、２および３を添加した後、チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金（Ｉ））テトラフルオロボレイト、チオ硫酸ナトリウム、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで、最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
得られたハロゲン化銀粒子の特徴を表１に示す。
【０２２９】
（Ｅｍ−Ａ８）
＜ホスト平板粒子の形成＞
（Ｅｍ−Ａ１）の＜ホスト平板粒子の形成＞と同様に行った。
【０２３０】
＜エピタキシャルの形成＞
前記、＜ホスト平板粒子の形成＞に引き続き、５０℃に降温した後、０．３％ＫＩ水溶液１３８ｍＬを添加し、増感色素１、２および３を添加した。その後２０分間５０℃で保持して撹拌を行った後、ＮａＣｌを８．０５ｇ含む水溶液１４０ｍＬを添加した。その後、ＡｇＮＯ_３を１２．８ｇ含む水溶液７９．９ｍＬを添加した。その際同時に、あらかじめ調製した沃塩臭化銀微粒子（銀量にして、０．０５ｍｏｌ、平均塩化銀含有率１０ｍｏｌ％、平均沃化銀含有率５ｍｏｌ％、平均球相当径：０．１１μｍ）を反応容器に添加した。この際、添加されるＡｇＮＯ_３の１ｍｏｌに対して８．０×１０^−４ｍｏｌのＫ_４［ＲｕＣＮ_６］を存在させた。その後、増感色素１、２および３を添加した。水洗した後、ゼラチンを添加し４０℃でｐＨ５．８、ｐＡｇ８．７に調整した。化合物１および２を添加した後、５３℃に昇温した。さらに増感色素１、２および３を添加した後、チオシアン酸カリウム、ビス（１，４，５−トリメチル−１，２，４−トリアゾリウム−３−チオレート金（Ｉ））テトラフルオロボレイト、チオ硫酸ナトリウム、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで、最適に化学増感するとは、増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
得られたハロゲン化銀粒子の特徴を表１に示す。
【０２３１】
（Ｅｍ−Ａ９）
Ｅｍ−Ａ８と同様に乳剤を調製した。化合物１および２を添加した後、６０℃に昇温した。増感色素１、２および３を添加した後に、チオシアン酸カリウム、塩化金酸、チオ硫酸ナトリウム、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで、最適に化学増感するとは，増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
【０２３２】
（Ｅｍ−Ａ１０）
Ｅｍ−Ａ８と同様に乳剤を調製した。化合物１および２を添加した後、６０℃に昇温した。増感色素１、２および３を添加した後に、チオシアン酸カリウム、塩化金酸、カルボキシメチルトリメチルチオ尿素、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感終了時に化合物３および化合物４を添加した。ここで、最適に化学増感するとは，増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
【０２３３】
（Ｅｍ−Ａ１１）
Ｅｍ−Ａ８と同様に乳剤を調製した。化合物１および２を添加した後、６０℃に昇温した。増感色素１、２および３を添加した後に，チオシアン酸カリウム、塩化金酸，カルボキシメチルトリメチルチオ尿素、Ｎ，Ｎ−ジメチルセレノウレアを添加し最適に化学増感した。化学増感時に化合物５を１×１０^−４ｍｏｌ／ｍｏｌＡｇ添加した。化学増感終了時に化合物３および化合物４を添加した。ここで，最適に化学増感するとは，増感色素ならびに各化合物をハロゲン化銀１モルあたり１０^−１から１０^−８モルの添加量範囲から選択したことを意味する。
【０２３４】
【化９】

【０２３５】
このようにして得られたハロゲン化銀乳剤Ｅｍ−Ａ１〜Ａ１１の特性を表１に示す。
【０２３６】
【表１】

【０２３７】
下塗り層を設けてある三酢酸セルロースフィルム支持体に、各乳剤を４０℃で３０分間溶解経時した後、下記に示すような塗布条件で、前記の乳剤Ｅｍ−Ａ１〜Ａ１１の塗布を行ない、試料１０１〜１１１を作成した。
【０２３８】

【０２３９】
【化１０】

【０２４０】
【化１１】

【０２４１】
これらの試料を４０℃、相対湿度７０％の条件下で１４時間硬膜処理を施した。その後、連続ウェッジを通して１　／１００　秒間露光を行い、下記の現像処理を行なった試料を緑色フィルターで濃度測定することにより写真感度を求めた。また、粒状を求めた。
現像は富士写真フイルム社製自動現像機ＦＰ−３６２Ｂを用いて以下の工程にしたがって行った。
【０２４２】
処理工程及び処理液組成を以下に示す。

＊補充量は感光材料３５ｍｍ幅１．１ｍ当たり（２４Ｅｘ．１本相当）
安定液は（３）→（２）→（１）への向流方式であり、定着液も（２）から（１）へ向流配管で接続されている。また、安定液（２）のタンク液を定着液（２）へ補充量相当１５ｍＬを流入している。更に、発色現像液は下記処方の発色現像液（Ａ）補充液及び発色現像液（Ｂ）補充液をそれぞれ補充量相当１２ｍＬと３ｍＬに分割して合計１５ｍＬとして補充している。なお、現像液の漂白工程への持ち込み量、漂白液の定着工程への持ち込み量及び定着液の水洗工程への持ち込み量は何れも感光材料３５ｍｍ幅１．１ｍ当たり２．０ｍＬであった。また、クロスオーバーの時間は何れも６秒であり、この時間は前工程の処理時間に包含される。
【０２４３】
以下に処理液の組成を示す。

上記タンク液は前記（発色現像液（Ａ））混合後の組成を示す。
【０２４５】

【０２４６】

【０２４７】

【０２４８】
前記の方法で評価を行った結果を、表２に示す。感度はかぶり濃度プラス０．２の濃度に到達するのに必要な露光量の逆数の相対値で表示した。
【０２４９】
【表２】

【０２５０】
（実施例２）
多層カラー感光材料における本発明の効果を示す。
１）支持体
本実施例で用いた支持体は、下記の方法により作成した。
ポリエチレン−２，６−ナフタレートポリマー１００質量部と紫外線吸収剤としてＴｉｎｕｖｉｎ　Ｐ．３２６（チバ・ガイギーＣｉｂａ−Ｇｅｉｇｙ社製）２質量部とを乾燥した後、３００℃にて溶融後、Ｔ型ダイから押し出し、１４０℃で３．３倍の縦延伸を行い、続いて１３０℃で３．３倍の横延伸を行い、さらに２５０℃で６秒間熱固定して厚さ９０μｍのＰＥＮ（ポリエチレンナフタレート）フィルムを得た。なお、このＰＥＮフィルムにはブルー染料、マゼンタ染料及びイエロー染料（公開技法：公技番号９４−６０２３号記載のＩ−１、Ｉ−４、Ｉ−６、Ｉ−２４、Ｉ−２６、Ｉ−２７、ＩＩ−５）を適当量添加した。さらに、直径２０ｃｍのステンレス巻き芯に巻き付けて、１１０℃、４８時間の熱履歴を与え、巻き癖のつきにくい支持体とした。
【０２５１】
２）下塗層の塗設
上記支持体は、その両面にコロナ放電処理、ＵＶ放電処理、さらにグロー放電処理をした後、それぞれの面にゼラチン０．１ｇ／ｍ^２、ソウジウムα−スルホジ−２−エチルヘキシルサクシネート０．０１ｇ／ｍ^２、サリチル酸０．０４ｇ／ｍ^２、ｐ−クロロフェノール０．２ｇ／ｍ^２、（ＣＨ_２＝ＣＨＳＯ_２ＣＨ_２ＣＨ_２ＮＨＣＯ）_２ＣＨ_２０．０１２ｇ／ｍ^２、ポリアミド−エピクロルヒドリン重縮合物０．０２ｇ／ｍ^２の下塗液を塗布して（１０ｍＬ／ｍ^２、バーコーター使用）、下塗層を延伸時高温面側に設けた。乾燥は１１５℃、６分実施した（乾燥ゾーンのローラーや搬送装置はすべて１１５℃となっている）。
【０２５２】
３）バック層の塗設
下塗後の上記支持体の片方の面にバック層として下記組成の帯電防止層、磁気記録層さらに滑り層を塗設した。
３−１）帯電防止層の塗設
平均粒径０．００５μｍの酸化スズ−酸化アンチモン複合物の比抵抗は５Ω・ｃｍの微粒子粉末の分散物（２次凝集粒子径約０．０８μｍ）を０．２ｇ／ｍ^２、ゼラチン０．０５ｇ／ｍ^２、（ＣＨ_２＝ＣＨＳＯ_２ＣＨ_２ＣＨ_２ＮＨＣＯ）_２ＣＨ_２　０．０２ｇ／ｍ^２、ポリ（重合度１０）オキシエチレン−ｐ−ノニルフェノール　０．００５ｇ／ｍ^２及びレゾルシンと塗布した。
【０２５３】
３−２）磁気記録層の塗設
３−ポリ（重合度１５）オキシエチレン−プロピルオキシトリメトキシシラン（１５質量％）で被覆処理されたコバルト−γ−酸化鉄（比表面積４３ｍ^２／ｇ、長軸０．１４μｍ、単軸０．０３μｍ、飽和磁化８９Ａｍ^２／ｋｇ、Ｆｅ^＋２／Ｆｅ^＋３＝６／９４、表面は酸化アルミ酸化珪素で酸化鉄の２質量％で処理されている）０．０６ｇ／ｍ^２をジアセチルセルロース１．２ｇ／ｍ^２（酸化鉄の分散はオープンニーダーとサンドミルで実施した）、硬化剤としてＣ_２Ｈ_５Ｃ（ＣＨ_２ＯＣＯＮＨ−Ｃ_６Ｈ_３（ＣＨ_３）ＮＣＯ）_３０．３ｇ／ｍ^２を、溶媒としてアセトン、メ　チルエチルケトン、シクロヘキサノンを用いてバーコーターで塗布し、膜厚１．２μｍの磁気記録層を得た。マット剤としてシリカ粒子（０．３μｍ）と３−ポリ（重合度１５）オキシエチレン−プロピルオキシトリメトキシシラン（１５質量％）で処理被覆された研磨剤の酸化アルミ（０．１５μｍ）をそれぞれ１０ｍｇ／ｍ^２となるように添加した。乾燥は１１５℃、６分実施した（乾燥ゾーンの　ローラーや搬送装置はすべて１１５℃）。Ｘ−ライト（ブルーフィルター）での磁気記録層のＤ^Ｂの色濃度増加分は約０．１、また磁気記録層の飽和磁化モーメントは４．２Ａｍ^２／ｋｇ、保磁力７．３×１０^４Ａ／ｍ、角形比は６５％であった。
【０２５４】
３−３）滑り層の調製
ジアセチルセルロース（２５ｍｇ／ｍ^２）、Ｃ_６Ｈ_１３ＣＨ（ＯＨ）Ｃ_１０Ｈ_２０ＣＯＯＣ_４０Ｈ_８１（化合物ａ，６ｍｇ／ｍ^２）／Ｃ_５０Ｈ_１０１Ｏ（ＣＨ_２ＣＨ_２Ｏ）_１６Ｈ（化合物ｂ，９ｍｇ／ｍ^２）混合物を塗布した。なお、この混合物は、キシレン／プロピレンモノメチルエーテル（１／１）中で１０５℃で溶融し、常温のプロピレンモノメチルエーテル（１０倍量）に注加分散して作製した後、アセトン中で分散物（平均粒径０．０１μｍ）にしてから添加した。マット剤としてシリカ粒子（０．３μｍ）と研磨剤の３−ポリ（重合度１５）オキシエチレンプロピルオキシトリメトキシシラン（１５質量％）で被覆された酸化アルミ（０．１５μｍ）をそれぞれ１５ｍｇ／ｍ^２となるように添加した。乾燥は１１５℃、６分行った（乾燥ゾーンのローラーや搬送装置はすべて１１５℃）。滑り層は、動摩擦係数０．０６（５ｍｍφのステンレス硬球、荷重１００ｇ、スピード６ｃｍ／分）、静摩擦係数０．０７（クリップ法）、また後述する乳剤面と滑り層の動摩擦係数も０．１２と優れた特性であった。
【０２５５】
４）感光層の塗設
次に、前記で得られたバック層の反対側に、下記組成の各層を重層塗布し、カラーネガ感光材料である試料２０１〜２１１を作成した。すなわち、第６層における塩沃臭化銀乳剤Ｅｍ−Ａ１をそれぞれ乳剤Ｅｍ−Ａ１〜Ｅｍ−Ａ１１に置きかえることにより、各々試料２０１〜２１１を作成した。
【０２５６】
（感光層の組成）
各層に使用する素材の主なものは下記のように分類されている；
ＥｘＣ：シアンカプラー　　　　　　ＵＶ　：紫外線吸収剤
ＥｘＭ：マゼンタカプラー　　　　　ＨＢＳ：高沸点有機溶剤
ＥｘＹ：イエローカプラー　　　　　Ｈ　　：ゼラチン硬化剤
（具体的な化合物は以下の記載で、記号の次に数値が付けられ、後ろに化学式が挙げられている）
各成分に対応する数字は、ｇ／ｍ^２単位で表した塗布量を示し、ハロゲン化銀については銀換算の塗布量を示す。
【０２５７】

【０２５８】
第２層（第２ハレーション防止層）
黒色コロイド銀　　　　　　　　　　　　　　　銀　　　０．０６６
ゼラチン　　　　　　　　　　　　　　　　　　　　　　０．４０７
ＥｘＭ−１　　　　　　　　　　　　　　　　　　　　　０．０５０
ＥｘＦ−１　　　　　　　　　　　　　　　　　　　　　２．０×１０^−３
ＨＢＳ−１　　　　　　　　　　　　　　　　　　　　　０．０７４
固体分散染料　ＥｘＦ−２　　　　　　　　　　　　　　０．０１５
固体分散染料　ＥｘＦ−３　　　　　　　　　　　　　　０．０２０
【０２５９】

【０２６０】
第４層（低感度赤感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｍ　　　　　　　　　　　　銀　　０．０６５
沃臭化銀乳剤Ｅｍ−Ｎ　　　　　　　　　　　　銀　　０．１００
沃臭化銀乳剤Ｅｍ−Ｏ　　　　　　　　　　　　銀　　０．１５８
ＥｘＣ−１　　　　　　　　　　　　　　　　　　　　０．１０９
ＥｘＣ−３　　　　　　　　　　　　　　　　　　　　０．０４４
ＥｘＣ−４　　　　　　　　　　　　　　　　　　　　０．０７２
ＥｘＣ−５　　　　　　　　　　　　　　　　　　　　０．０１１
ＥｘＣ−６　　　　　　　　　　　　　　　　　　　　０．００３
ＥｘＣ−８　　　　　　　　　　　　　　　　　　　　０．０３
Ｃｐｄ−２　　　　　　　　　　　　　　　　　　　　０．０２５
Ｃｐｄ−４　　　　　　　　　　　　　　　　　　　　０．０２５
ＨＢＳ−１　　　　　　　　　　　　　　　　　　　　０．１７
ゼラチン　　　　　　　　　　　　　　　　　　　　　０．８０
【０２６１】
第５層（中感度赤感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｋ　　　　　　　　　　　　銀　　０．２１
沃臭化銀乳剤Ｅｍ−Ｌ　　　　　　　　　　　　銀　　０．６２
ＥｘＣ−１　　　　　　　　　　　　　　　　　　　　０．１４
ＥｘＣ−２　　　　　　　　　　　　　　　　　　　　０．０２６
ＥｘＣ−３　　　　　　　　　　　　　　　　　　　　０．０２０
ＥｘＣ−４　　　　　　　　　　　　　　　　　　　　０．１２
ＥｘＣ−５　　　　　　　　　　　　　　　　　　　　０．０１６
ＥｘＣ−６　　　　　　　　　　　　　　　　　　　　０．００７
ＥｘＣ−８　　　　　　　　　　　　　　　　　　　　０．０３
Ｃｐｄ−２　　　　　　　　　　　　　　　　　　　　０．０３６
Ｃｐｄ−４　　　　　　　　　　　　　　　　　　　　０．０２８
ＨＢＳ−１　　　　　　　　　　　　　　　　　　　　０．１６
ゼラチン　　　　　　　　　　　　　　　　　　　　　１．１８
【０２６２】
第６層（高感度赤感乳剤層）
塩沃臭化銀乳剤（実施例１のＥｍ−Ａ１）　　　銀　　１．６７
ＥｘＣ−１　　　　　　　　　　　　　　　　　　　　０．１８
ＥｘＣ−３　　　　　　　　　　　　　　　　　　　　０．０７
ＥｘＣ−６　　　　　　　　　　　　　　　　　　　　０．０４７
Ｃｐｄ−２　　　　　　　　　　　　　　　　　　　　０．０４６
Ｃｐｄ−４　　　　　　　　　　　　　　　　　　　　０．０７７
ＨＢＳ−１　　　　　　　　　　　　　　　　　　　　０．３７
ゼラチン　　　　　　　　　　　　　　　　　　　　　２．１２
【０２６３】
第７層（中間層）
Ｃｐｄ−１　　　　　　　　　　　　　　　　　　　　０．０８９
固体分散染料ＥｘＦ−４　　　　　　　　　　　　　　０．０３０
ＨＢＳ−１　　　　　　　　　　　　　　　　　　　　０．０５０
ポリエチルアクリレートラテックス　　　　　　　　　０．８３
ゼラチン　　　　　　　　　　　　　　　　　　　　　０．８４
【０２６４】
第８層（重層効果ドナー層（赤感層へ重層効果を与える層））
沃臭化銀乳剤Ｅｍ−Ｅ　　　　　　　　　　　　銀　　０．５６０
Ｃｐｄ−４　　　　　　　　　　　　　　　　　　　　０．０３０
ＥｘＭ−２　　　　　　　　　　　　　　　　　　　　０．０９６
ＥｘＭ−３　　　　　　　　　　　　　　　　　　　　０．０２８
ＥｘＹ−１　　　　　　　　　　　　　　　　　　　　０．０３１
ＥｘＧ−１　　　　　　　　　　　　　　　　　　　　０．００６
ＨＢＳ−１　　　　　　　　　　　　　　　　　　　　０．０８５
ＨＢＳ−３　　　　　　　　　　　　　　　　　　　　０．００３
ゼラチン　　　　　　　　　　　　　　　　　　　　　０．５８
【０２６５】
第９層（低感度緑感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｇ　　　　　　　　　　　　銀　　０．３９
沃臭化銀乳剤Ｅｍ−Ｈ　　　　　　　　　　　　銀　　０．２８
沃臭化銀乳剤Ｅｍ−Ｉ　　　　　　　　　　　　銀　　０．３５
ＥｘＭ−２　　　　　　　　　　　　　　　　　　　　０．３６
ＥｘＭ−３　　　　　　　　　　　　　　　　　　　　０．０４５
ＥｘＧ−１　　　　　　　　　　　　　　　　　　　　０．００５
ＨＢＳ−１　　　　　　　　　　　　　　　　　　　　０．２８
ＨＢＳ−２　　　　　　　　　　　　　　　　　　　　０．０１
Ｓ−２　　　　　　　　　　　　　　　　　　　　　　０．２７
ゼラチン　　　　　　　　　　　　　　　　　　　　　１．３９
【０２６６】
第１０層（中感度緑感乳剤層）
沃臭化銀乳剤Ｅｍ−Ｆ　　　　　　　　　　　　銀　　０．２０
沃臭化銀乳剤Ｅｍ−Ｇ　　　　　　　　　　　　銀　　０．２５
ＥｘＣ−６　　　　　　　　　　　　　　　　　　　　０．００９
ＥｘＣ−８　　　　　　　　　　　　　　　　　　　　０．０１
ＥｘＭ−２　　　　　　　　　　　　　　　　　　　　０．０３１
ＥｘＭ−３　　　　　　　　　　　　　　　　　　　　０．０２９
ＥｘＹ−１　　　　　　　　　　　　　　　　　　　　０．００６
ＥｘＭ−４　　　　　　　　　　　　　　　　　　　　０．０２８
ＥｘＧ−１　　　　　　　　　　　　　　　　　　　　０．００５
ＨＢＳ−１　　　　　　　　　　　　　　　　　　　　０．０６４
ＨＢＳ−２　　　　　　　　　　　　　　　　　　　　２．１×１０^−３
ゼラチン　　　　　　　　　　　　　　　　　　　　　０．４４
【０２６７】
第１１層（高感度緑感乳剤層）
乳剤Ｅｍ−Ｐ　　　　　　　　　　　　　　　　銀　　１．２００
ＥｘＣ−６　　　　　　　　　　　　　　　　　　　　０．００４
ＥｘＣ−８　　　　　　　　　　　　　　　　　　　　０．０１
ＥｘＭ−１　　　　　　　　　　　　　　　　　　　　０．０１６
ＥｘＭ−３　　　　　　　　　　　　　　　　　　　　０．０３６
ＥｘＭ−４　　　　　　　　　　　　　　　　　　　　０．０２０
ＥｘＭ−５　　　　　　　　　　　　　　　　　　　　０．００４
ＥｘＹ−５　　　　　　　　　　　　　　　　　　　　０．００８
ＥｘＭ−２　　　　　　　　　　　　　　　　　　　　０．０１３
Ｃｐｄ−４　　　　　　　　　　　　　　　　　　　　０．００７
ＨＢＳ−１　　　　　　　　　　　　　　　　　　　　０．１８
ポリエチルアクリレートラテックス　　　　　　　　　０．０９９
ゼラチン　　　　　　　　　　　　　　　　　　　　　１．１１
【０２６８】
第１２層（イエローフィルター層）
黄色コロイド銀　　　　　　　　　　　　　　　銀　　０．０４７
Ｃｐｄ−１　　　　　　　　　　　　　　　　　　　　０．１６
固体分散染料ＥｘＦ−５　　　　　　　　　　　　　　０．０１０
固体分散染料ＥｘＦ−６　　　　　　　　　　　　　　０．０１０
ＨＢＳ−１　　　　　　　　　　　　　　　　　　　　０．０８２
ゼラチン　　　　　　　　　　　　　　　　　　　　　１．０５７
【０２６９】
第１３層（低感度青感乳剤層）
Ｅｍ−Ｂ　　　　　　　　　　　　　　　　　　銀　　０．１８
Ｅｍ−Ｃ　　　　　　　　　　　　　　　　　　銀　　０．２０
Ｅｍ−Ｄ　　　　　　　　　　　　　　　　　　銀　　０．０７
ＥｘＣ−１　　　　　　　　　　　　　　　　　　　　０．０４１
ＥｘＹ−１　　　　　　　　　　　　　　　　　　　　０．０３５
ＥｘＹ−２　　　　　　　　　　　　　　　　　　　　０．７１
ＥｘＹ−３　　　　　　　　　　　　　　　　　　　　０．１０
ＥｘＹ−４　　　　　　　　　　　　　　　　　　　　０．００５
Ｃｐｄ−２　　　　　　　　　　　　　　　　　　　　０．１０
Ｃｐｄ−３　　　　　　　　　　　　　　　　　　　　４．０×１０^−３
ＨＢＳ−１　　　　　　　　　　　　　　　　　　　　０．２４
ゼラチン　　　　　　　　　　　　　　　　　　　　　１．４１
【０２７０】
第１４層（高感度青感乳剤層）
Ｅｍ−Ａ　　　　　　　　　　　　　　　　　　銀　　０．７５
ＥｘＣ−１　　　　　　　　　　　　　　　　　　　　０．０１３
ＥｘＹ−２　　　　　　　　　　　　　　　　　　　　０．３１
ＥｘＹ−３　　　　　　　　　　　　　　　　　　　　０．０５
ＥｘＹ−６　　　　　　　　　　　　　　　　　　　　０．０６２
Ｃｐｄ−２　　　　　　　　　　　　　　　　　　　　０．０７５
Ｃｐｄ−３　　　　　　　　　　　　　　　　　　　　１．０×１０^−３
ＨＢＳ−１　　　　　　　　　　　　　　　　　　　　０．１０
ゼラチン　　　　　　　　　　　　　　　　　　　　　０．９１
【０２７１】

【０２７２】
第１６層（第２保護層）
Ｈ−１　　　　　　　　　　　　　　　　　　　　　０．４０
Ｂ−１（直径１．７μｍ）　　　　　　　　　　　　５．０×１０^−２
Ｂ−２（直径１．７μｍ）　　　　　　　　　　　　０．１５
Ｂ−３　　　　　　　　　　　　　　　　　　　　　０．０５
Ｓ−１　　　　　　　　　　　　　　　　　　　　　０．２０
ゼラチン　　　　　　　　　　　　　　　　　　　　０．７５
【０２７３】
更に、各層に適宜、保存性、処理性、圧力耐性、防黴・防菌性、帯電防止性、および塗布性を向上する目的で、Ｗ−１ないしＷ−６、Ｂ−４ないしＢ−６、Ｆ−１ないしＦ−１７及び、鉄塩、鉛塩、金塩、白金塩、パラジウム塩、イリジウム塩、ルテニウム塩、ロジウム塩が含有されている。
ハロゲン化銀乳剤Ｅｍ−Ａ〜Ｐの特性を表３に示す。これらの乳剤については、特開２００１−９２０５７号公報の実施例に記載のＥｍ−Ａ〜Ｐおよび特開２００１−９２０５９号公報の実施例に記載のＥｍ−Ａ〜Ｏの乳剤調製法を基に粒子形成条件を適宜変更し調製している。
【０２７４】
【表３】

【０２７５】
有機固体分散染料の調製
下記、ＥｘＦ−３を次の方法で分散した。即ち、水２１．７ｍＬ及び５％水溶液のｐ−オクチルフェノキシエトキシエトキシエタンスルホン酸ソーダ３ｍＬ並びに５％水溶液のｐ−オクチルフェノキシポリオキシエチレンエーテル（重合度１０）０．５ｇとを７００ｍＬのポットミルに入れ、染料ＥｘＦ−３を５．０ｇと酸化ジルコニウムビーズ（直径１ｍｍ）５００ｍＬを添加して内容物を２時間分散した。この分散には中央工機製のＢＯ型振動ボールミルを用いた。分散後、内容物を取り出し、１２．５％ゼラチン水溶液８ｇに添加し、ビーズを濾過して除き、染料のゼラチン分散物を得た。染料微粒子の平均粒径は０．４４μｍであった。
【０２７６】
同様にして、ＥｘＦ−４の固体分散物を得た。染料微粒子の平均粒径は、０．２４μｍであった。ＥｘＦ−２は欧州特許出願公開（ＥＰ）第５４９，４８９Ａ号明細書の実施例１に記載の微小析出（Ｍｉｃｒｏｐｒｅｃｉｐｉｔａｔｉｏｎ）分散方法により分散した。平均粒径は０．０６μｍであった。
【０２７７】
ＥｘＦ−６の固体分散物を以下の方法で分散した。
水を１８％含むＥｘＦ−６のウェットケーキ２８００ｇに４０００ｇの水及びＷ−２の３％溶液を３７６ｇ加えて攪拌し、ＥｘＦ−６の濃度３２％のスラリーとした。次にアイメックス（株）製ウルトラビスコミル（ＵＶＭ−２）に平均粒径０．５ｍｍのジルコニアビーズを１７００ｍＬ充填し、スラリーを通して周速約１０ｍ／ｓｅｃ、吐出量０．５Ｌ／ｍｉｎで８時間粉砕した。平均粒径は、０．４５μｍであった。
上記各層の形成に用いた化合物は、以下に示すとおりである。
【０２７８】
【化１２】

【０２７９】
【化１３】

【０２８０】
【化１４】

【０２８１】
【化１５】

【０２８２】
【化１６】

【０２８３】
【化１７】

【０２８４】
【化１８】

【０２８５】
【化１９】

【０２８６】
【化２０】

【０２８７】
【化２１】

【０２８８】
【化２２】

【０２８９】
【化２３】

【０２９０】
【化２４】

【０２９１】
【化２５】

【０２９２】
【化２６】

【０２９３】
【化２７】

【０２９４】
本発明における特定写真感度の決定方法は、ＪＩＳ　Ｋ　７６１４−１９８１に準じたものであり、異なる点は、現像処理をセンシトメトリ用露光後３０分以上６時間以内に完了させる点、および現像処理を下記に示すフジカラー処理方法ＣＮ−１６による点にある。その他は、実質的にＪＩＳ記載の測定方法と同一である。
【０２９５】
処理方法は、実施例１に記載の現像方法と同様の処理を行った。試験条件、露光、濃度測定、特定写真感度の決定は、特開昭６３−２２６６５０号公報に記載されている方法と同様の方法とした。
【０２９６】
試料２０１〜２１１に対して前記処理を施した。処理済の試料を赤色フィルターで濃度測定することにより写真性能の評価を行った。得られた結果を表４に示す。
【０２９７】
【表４】

【０２９８】
表４より、本発明の乳剤を用いた試料は比較試料に対して、粒状性を改良しつつ、高感度を達成している。
【図面の簡単な説明】
【図１】図１は、平面模式図。
【図２】図２は、図１の（ａ）−（ｂ）線における断面模式図。
【符号の説明】
１…平板粒子、２…エピタキシャル接合部、３…ホスト平板状粒子部分、
Ａ１…臭化銀含有率４０モル％未満の部分
Ａ２…臭化銀含有率４０モル％以上の部分[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide emulsion having an excellent sensitivity / grain ratio.
[0002]
[Prior art]
In recent years, silver halide color photographic light-sensitive materials have been steadily spreading the use of film in the high-sensitivity area since the release of “Seirun 800,” a lens-equipped film that achieves both high sensitivity and high image quality. . Such high film sensitivity can be achieved by shooting without using a strobe in a dark room, shooting with a high-speed shutter using a telephoto lens such as sports photography, and shooting that requires long exposure such as astronomical photography. The imaging area in the material can be expanded, and as a result, there are great benefits for the user. Therefore, increasing the sensitivity of the film is one of the eternal themes imposed on the industry.
[0003]
In order to increase the sensitivity of a photosensitive material, it is a common practice in the industry to increase the size of silver halide grains as a photosensitive element and to use it in combination with other sensitivity enhancement techniques.
Increasing the silver halide grain size increases the sensitivity to a certain extent, but as long as the silver halide content is kept constant, the reduction in the number of silver halide grains, that is, the number of development starting points is inevitably reduced. It has the disadvantage that it is reduced and the graininess is greatly impaired.
[0004]
On the other hand, silver halide tabular grains (hereinafter also referred to as “tabular grains”) have many advantages, and thus have been widely used in the field. Tabular grains have a large specific surface area and can increase the amount of adsorption of sensitizing dyes that contribute to light absorption to silver halide grains. As a result, even if the grain size is small, sufficient light absorption can be achieved, and graininess Will not be significantly damaged. However, tabular grains having a small thickness generally have a low efficiency in forming a latent image, so that sensitivity for light absorption cannot be obtained. Technological development for increasing the efficiency and increasing the sensitivity of latent image formation has been intensively studied in this technical field. For example, as a technique for increasing the sensitivity of tabular grains, a sensitization method using an epitaxial junction has been disclosed (see, for example, Patent Document 1).
[0005]
However, even with the technology described in the above patent application specifications, “sensitivity enhancement” is insufficient, and in developing a higher sensitivity photographic material, a new technology for enhancing the sensitivity of tabular grains has been proposed. It was strongly desired. The present invention realizes high sensitivity that cannot be achieved by the prior art, and further improves graininess.
[0006]
[Patent Document 1]
JP 2001-235821 A
[0007]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems of the prior art and aims to provide a silver halide photographic emulsion having high sensitivity and excellent graininess.
[0008]
[Means for Solving the Problems]
As a result of earnest research, the above-mentioned problems have been achieved by the following (1) to (6).
(1) In a silver halide emulsion containing a dispersion medium and silver halide grains, 50% or more of the total projected area of the silver halide grains satisfies the following (a), (b), and (c) A silver halide emulsion characterized by being occupied by silver halide grains.
(A) Silver halide tabular grains having a main plane of (111) plane
(B) An epitaxial junction is formed in at least one corner of the tabular grain.
(C) When the epitaxial junction is divided into a part (A1) having a silver bromide content of less than 40 mol% and a part (A2) having a silver bromide content of 40 mol% or more, the A1 part is epitaxial. Present inside the joint, not present on the surface
[0009]
(2) Halogen characterized in that 50% or more of the total projected area of the silver halide grains is occupied by silver halide grains satisfying the following (d) in addition to the above (a) to (c) Silver halide emulsion.
(D) Aspect ratio is 8 or more
[0010]
(3) Halogen characterized in that 50% or more of the total projected area of the silver halide grains is occupied by silver halide grains satisfying the following (e) in addition to the above (a) to (c) Silver halide emulsion.
(E) Sphere equivalent diameter is 1.0 μm or more
[0011]
(4) Halogen in which 50% or more of the total projected area of silver halide grains is occupied by silver halide grains satisfying the following (f) in addition to (a) to (c) above Silver halide emulsion.
(F) A1 part silver amount accounts for 1 to 50% of the silver amount of the epitaxial junction
[0012]
(5) A halogen characterized in that 50% or more of the total projected area of the silver halide grains is occupied by silver halide grains satisfying the following (g) in addition to the above (a) to (c) Silver halide emulsion.
(G) A1 part has a silver chloride content of 50% or more
[0013]
(6) Halogen characterized in that 50% or more of the total projected area of the silver halide grains is occupied by silver halide grains satisfying the above (e) in addition to the above (a) to (d) Silver halide emulsion.
[0014]
(7) Halogen characterized in that 50% or more of the total projected area of silver halide grains is occupied by silver halide grains satisfying (f) in addition to (a) to (d) above Silver halide emulsion.
[0015]
(8) Halogen characterized in that 50% or more of the total projected area of the silver halide grains is occupied by silver halide grains satisfying the above (g) in addition to the above (a) to (d) Silver halide emulsion.
[0016]
(9) 50% or more of the total projected area of the silver halide grains is occupied by the silver halide grains satisfying the above (f) in addition to the above (a) to (c) and (e). Characteristic silver halide emulsion.
[0017]
(10) 50% or more of the total projected area of the silver halide grains is occupied by the silver halide grains satisfying the above (g) in addition to the above (a) to (c) and (e). Characteristic silver halide emulsion.
[0018]
(11) 50% or more of the total projected area of the silver halide grains is occupied by the silver halide grains satisfying the above (g) in addition to the above (a) to (c) and (f). Characteristic silver halide emulsion.
[0019]
(12) A halogen characterized in that 50% or more of the total projected area of the silver halide grains is occupied by the silver halide grains satisfying the above (f) in addition to the above (a) to (e) Silver halide emulsion.
[0020]
(13) Halogen characterized in that 50% or more of the total projected area of the silver halide grains is occupied by silver halide grains satisfying the above (g) in addition to the above (a) to (e) Silver halide emulsion.
[0021]
(14) 50% or more of the total projected area of the silver halide grains is occupied by the silver halide grains satisfying the above (g) in addition to the above (a) to (d) and (f). Characteristic silver halide emulsion.
[0022]
(15) A silver halide emulsion characterized in that 50% or more of the total projected area of silver halide grains is occupied by silver halide grains satisfying (a) to (g).
[0023]
(16) In the silver halide photographic light-sensitive material having at least one silver halide emulsion layer on the support, the halogen described in any one of (1) to (15) in at least one of the emulsion layers. A silver halide photographic material containing a silver halide emulsion.
[0024]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in more detail.
The halogen composition of the silver halide grains of the present invention is preferably silver chlorobromide or silver iodochlorobromide.
[0025]
The silver iodide content in the silver halide grains of the present invention is preferably from 1 mol% to 25 mol%, more preferably from 3 mol% to 20 mol%, based on the total silver amount in the grains. The silver chloride content is preferably 1 mol% or more and 20 mol% or less, and more preferably 2 mol% or more and 10 mol% or less with respect to the total silver amount in the grain.
[0026]
In the emulsion of the present invention, the relative standard deviation of the silver iodide content distribution between silver halide grains is preferably 20% or less. More preferably, it is 10% or less. The relative standard deviation of the silver iodide content between grains can be easily determined by using the EPMA method (Electron-Probe Micro Analyzer method). In this method, a sample in which emulsion grains are well dispersed so as not to contact each other is prepared and irradiated with an electron beam. Elemental analysis of extremely small parts can be performed by X-ray analysis by electron beam excitation. Using this method, the halogen composition of individual grains can be determined by determining the characteristic X-ray intensity of silver and iodine emitted from each grain. If the halogen composition is confirmed by the EPMA method for at least 100 grains, it can be determined whether or not the emulsion is an emulsion according to the present invention. The relative standard deviation of the silver iodide content is a value obtained by dividing the standard deviation of the silver iodide content distribution obtained for at least 100 grains by the average silver iodide content and multiplying by 100.
[0027]
The emulsion of the present invention preferably has a relative standard deviation of the silver chloride content distribution between grains of 20% or less. More preferably, it is 10% or less. The measurement method is the same as that described above.
[0028]
The emulsion of the present invention preferably contains monodispersed silver halide grains. The variation coefficient of the equivalent sphere diameter of all the silver halide grains constituting the emulsion of the present invention is preferably 30% or less, more preferably 25% or less. The equivalent sphere diameter is the diameter of a sphere having a volume equal to the volume of each particle. The coefficient of variation is a value obtained by dividing the standard deviation of the equivalent diameter distribution obtained for at least 100 silver halide grains in the emulsion by the average equivalent diameter and multiplying by 100.
[0029]
FIG. 1 shows a plan view of a grain in which hexagonal tabular grains 1 which are one embodiment of the emulsion according to the present invention have epitaxial junctions 2 formed at six corners, one by one. It is not limited to this. FIG. 2 shows a schematic diagram of a cross section taken along (a)-(b) in the plan view of FIG. 1, but the present invention is not limited to this.
[0030]
The silver halide grain 1 of the present invention comprises a host tabular grain portion 3 and an epitaxial junction portion 2 formed at a corner portion of the tabular grain.
[0031]
First, the host tabular grain portion will be described.
[0032]
In the present invention, tabular grains (hereinafter also referred to as “tabular grains”) refer to silver halide grains having two opposite parallel (111) major planes. The tabular grain of the present invention has one twin plane or two or more parallel twin planes. The twin plane means the (111) plane when ions at all lattice points are mirror images on both sides of the (111) plane. The tabular grains have a triangular shape, a hexagonal shape, or a round shape in which they are round when the grains are viewed from the vertical direction from the main plane, and have outer surfaces parallel to each other.
[0033]
In the tabular grains of the present invention, hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.5 to 1 preferably occupy 100 to 50% of the total number of grains. More preferably 100 to 70%, still more preferably 100 to 80%. In the emulsion of the present invention, more preferably, hexagonal tabular grains having an adjacent side ratio (maximum side length / minimum side length) of 1.2 to 1 occupy 100 to 50% of the total number of grains. More preferably, it accounts for 100 to 70%, particularly preferably 100 to 80%.
[0034]
The tabular grain spacing of the tabular grains contained in the emulsion of the present invention is 0.012 μm or less as described in US Pat. No. 5,219,720, or as described in JP-A-5-249585. (111) Main plane distance / twin plane distance may be 15 or more, and may be selected according to the purpose.
[0035]
As for the projected area diameter and thickness of the tabular grains, the diameter (projected area diameter) and thickness of a circle having an area equal to the projected area of each grain are obtained by taking a transmission electron micrograph by the replica method. In this case, the thickness is calculated from the length of the shadow of the replica.
[0036]
The tabular grains preferably have a projected area diameter of 2.0 to 20.0 μm, more preferably 3.0 to 10.0 μm. The equivalent sphere diameter is preferably 0.6 μm or more and 5.0 μm or less, and more preferably 1.0 μm or more and 4 μm or less. The equivalent sphere diameter is the diameter of a sphere having a volume equal to the volume of each particle. The aspect ratio is preferably 8 or more and 100 or less, more preferably 10 or more and 50 or less. The aspect ratio is a value obtained by dividing the projected area diameter of a grain by the thickness of the grain.
[0037]
The variation coefficient of the projected area diameter of the tabular grains in the silver halide emulsion of the present invention is preferably 35% or less, more preferably 30% or less. Further, the variation coefficient of the thickness of the tabular grain is preferably 30% or less, and more preferably 25% or less. The coefficient of variation is the value obtained by dividing the standard deviation of the equivalent diameter distribution of individual silver halide grains by the average equivalent diameter, or the value obtained by dividing the standard deviation of the thickness distribution of individual silver halide tabular grains by the average thickness. The value multiplied by.
[0038]
Further, the variation coefficient of the tabular grain twin plane spacing distribution in the silver halide emulsion of the present invention is preferably 25 to 3%, more preferably 20 to 3%, still more preferably 15 to 3%. The variation coefficient of the twin plane spacing distribution is a value obtained by dividing the thickness variation (standard deviation) of the twin plane spacing of each tabular grain by the average twin plane spacing. If the variation coefficient of the twin plane spacing distribution of the tabular grains exceeds 25%, it is not preferable in terms of homogeneity between grains. Also, it is difficult to prepare an emulsion of less than 3%.
[0039]
In the present invention, the silver iodide content in the silver halide tabular grains is preferably 2 mol% or more and 25 mol% or less, more preferably 5 mol% or more and 20 mol% or less with respect to the total silver amount in the grains. The silver chloride content is preferably 0.5 mol% or more and 10 mol% or less with respect to the total silver amount in the grain.
[0040]
In the silver halide tabular grains in the present invention, the (100) plane area with respect to the average side area determined from the average projected area diameter and average thickness of all grains is preferably 10% or more with respect to the side area. . Specifically, 20% or more and 100% or less is more preferable, and 30% or more and 80% or less is more preferable. The side surface refers to a portion sandwiched between two parallel main planes, and the average projected area diameter and average thickness of all particles are measured by transmission electron micrograph photography by the replica method described above. Can be sought. The crystal plane of the tabular grain is T.W. Tani et al. J. Img. Sci, 29, 165-171 (1985) can be used. Specifically, the ratio of the (100) plane to the (111) plane is obtained by this method, and the ratio of the (100) plane can be obtained from this ratio.
[0041]
The silver halide tabular grains contained in the emulsion of the present invention may preferably have a so-called core / shell structure comprising a core portion having different silver iodide contents and a shell surrounding the core portion. . The shell part may surround the entire core part, may surround only the side surfaces of the tabular grains of the core part, or may surround only the main flat surface part. The number of shells may be one or two or more. When the number of shells is two or more, the shell outside the core is called the first shell, the shell outside the first shell is called the second shell, and the shells outside the following are called the third shell and the fourth shell in order. . In this specification, “outermost layer” refers to the outermost shell.
[0042]
The core part is preferably 30% or more and 50% or less, and more preferably 40% or more and 60% or less, based on the total amount of silver used for grain formation. The average content of iodine with respect to the amount of silver in the core may be basically 0 mol% or more and below the solid solution limit, but more preferably 1 mol% or more and 25 mol% or less. The shell portion may be divided into several layers as described above. The average silver iodide content of each layer of the shell part is preferably 1 mol% or more and less than the solid solution limit, and more preferably 2 mol% or more and 20 mol% or less.
[0043]
The silver iodide content (I1) of the tabular grain main plane and the silver iodide content (I2) of the side surface of the tabular grain may be (1) I1 = I2, (2) I1> I2, or (3) I1. <I2 is also acceptable. The relationship (1) to (3) can be designed according to the purpose. I1 and I2 refer to the silver iodide content of the silver halide phase from the surface to a depth of 5 nm.
[0044]
Examples of the method for measuring the silver iodide content include the following methods. The tabular grain is cut into a ring perpendicular to the main plane and measured by irradiating an electron beam from the cross-sectional direction. That is, the emulsion sampled during grain formation, the final grain emulsion after grain formation, or the grains taken out from the photosensitive material by centrifugation are coated on a triacetyl cellulose support, and the resin is used to wrap the grains. Buried. An about 50 nm-thick section is cut from this sample with an ultramicrotome and placed on a copper mesh with a support film.
[0045]
A predetermined portion of the grain is subjected to a point analysis with a spot diameter (diameter) reduced to 2 nm or less using an analytical electron microscope to measure the silver iodide content. The silver iodide content can be calculated by treating silver halide grains having a known content as a calibration curve in the same manner and obtaining the ratio of Ag intensity to I intensity in advance. A field emission electron gun with a higher electron density than the one using thermoelectrons is suitable as the analytical electron source for the analytical electron microscope. By narrowing the spot diameter to 1 nm or less, the halogen composition in a minute part can be easily analyzed. it can. The measured values of I1 and I2 of the individual silver halide grains are measured at 10 or more locations at regular intervals for the main plane portion and the side portion, and the average value is used.
[0046]
The core part preferably does not contain dislocation lines, and the shell part may not contain dislocation lines, but preferably contains 10 or more dislocation lines per grain.
[0047]
Next, the epitaxial junction will be described.
The silver halide emulsion of the present invention comprises a silver halide tabular host grain portion having 50% or more of the total projected area and an epitaxial junction formed on at least one corner portion of the host grain. Become. Epitaxial bonding is that the crystal | crystallization which protruded outside is joined to the tabular grain surface. The composition of the epitaxial junction may be the same as that of the silver halide tabular host grain, but is preferably not the same. Specific examples include AgBr, AgCl, AgI, AgBrI, AgClI, AgBrCl, AgBrClI, AgSCN, and AgBrCl and AgBrClI are preferable. The position of the epitaxial junction is preferably the corner of the tabular grain. The corner portion refers to a portion where a circle having a radius r and a tabular grain overlap each other from a triangular or hexagonal apex when the tabular grain is viewed from the vertical direction. Here, r is the length of y% of the length connecting the center and vertex of the tabular grain, and y is 2% or more and 50% or less, preferably 5% or more and 30% or less. When the shape of the main surface of the tabular grain is a rounded triangular shape or hexagonal shape, the vertex of the main surface is the vertex of a virtual triangle or hexagonal side formed by extending each side.
[0048]
The number of epitaxial junctions may be at least at one corner, may be at a plurality of corners, preferably at three or more corners, and at six corners. Most preferred. In the case where the epitaxial junction is formed at the corner portion at the same time on the two main planes, the epitaxial junctions on both sides are combined and counted as one.
[0049]
As shown in FIG. 2, the epitaxial junction 2 of the present invention includes a portion having a silver bromide content of less than 40 mol% (A1 portion) and a portion having a silver bromide content of 40% or more (A2 portion). ) And have. The A1 portion and the A2 portion are in contact with each other to form one epitaxial junction. The present invention is characterized in that the A1 portion exists inside the epitaxial junction and does not exist on the surface. Here, the inside of the epitaxial junction means a region deeper than 5 nm from the surface. In the present invention, as long as the requirements specified in the present invention are satisfied, a plurality of (A1 part) and (A2 part) may exist in one epitaxial junction.
[0050]
Furthermore, the silver amount of A1 part is preferably 1 to 50%, more preferably 3 to 40% of the silver amount of the epitaxial junction. Further, it is preferable that the portion A1 has a portion having a silver chloride content of 50 mol% or more, and more preferably a portion having 60 mol% or more. The part having a silver chloride content of 50 mol% or more may be present anywhere in part A1. Moreover, 1-50% of the amount of epitaxial silver is preferable, and 3-40% of the amount of silver of the part whose silver chloride content rate is 50 mol% or more is more preferable.
[0051]
The halogen composition of the epitaxial junction is examined by analytical electron microscopy. In the present invention, tabular grains are sliced perpendicularly to the main plane by the following method, and measurement is performed by irradiating an electron beam from the cross-sectional direction. That is, the emulsion sampled during grain formation, the final grain emulsion after grain formation, or the grains taken out from the photosensitive material by centrifugation are coated on a triacetyl cellulose support, and the resin is used to wrap the grains. Buried. An about 50 nm-thick section is cut from this sample with an ultramicrotome and placed on a copper mesh with a support film.
[0052]
A predetermined portion of the grain is subjected to point analysis with a spot diameter (diameter) reduced to 2 nm or less using an analytical electron microscope to measure the silver bromide content and the silver chloride content. The silver bromide content and the silver chloride content can be calculated by treating silver halide grains having a known content as a calibration curve in the same manner and obtaining the ratios of Ag intensity, Br intensity, and Cl intensity in advance. A field emission electron gun with a higher electron density than the one using thermoelectrons is suitable as the analytical electron source for the analytical electron microscope. By narrowing the spot diameter to 1 nm or less, the halogen composition in a minute part can be easily analyzed. it can.
[0053]
As for the shape of the epitaxial junction, a {100} plane, a {111} plane, and a {110} plane may appear on the surface of the epitaxial junction, or a plurality of them may appear. Further, it may have an irregular shape in which a higher-order surface appears.
[0054]
The amount of silver in the epitaxial junction (when there are multiple epitaxial junctions, the total of them) is the total amount of silver in one grain, that is, the amount of silver in the silver halide host tabular grain and the amount of silver in the epitaxial junction Is preferably 3% to 50%, more preferably 5% to 30%.
[0055]
The amount of silver in the epitaxial junction can also be estimated from an electron micrograph. In that case, the amount of silver in the epitaxial junction can be determined by multiplying the area of the epitaxial junction as viewed from the main plane direction of the grain by the thickness of the epitaxial junction as viewed from the grain cross-sectional direction.
[0056]
The observation from the grain cross-sectional direction can be carried out from the grain side face direction by cutting the tabular grains perpendicularly to the main plane by the following method. That is, the tabular grains are sampled during grain formation, and after gelatin is removed by centrifugation, the grains are coated on a triacetyl cellulose support, and the grains are embedded using a resin. A section having a thickness of about 50 nm is cut from this sample with an ultramicrotome and placed on a copper mesh provided with a support film, and observed using a transmission electron microscope.
[0057]
Alternatively, a method may be used in which the amount of silver is estimated by dissolving the particles with a solvent using the difference in solubility due to the difference in the halogen composition between the epitaxial junction and the host grain. In that case, dissolve either the epitaxial junction or the host particle part with the weaker solvent with the weaker solvent first, measure the amount of silver by atomic absorption measurement, etc., and dissolve the remaining part with the solvent to reduce the amount of silver. It can be obtained by measuring.
[0058]
Below, the preparation method of a silver halide grain is demonstrated. As a method for preparing a silver halide emulsion, a method in which after forming silver halide nuclei and further growing silver halide grains to obtain grains of a desired size, the present invention is also the same. There is no replacement. The tabular grain formation includes at least nucleation, ripening, and growth steps. This process is described in detail in US Pat. No. 4,945,037. The growth step is a step of growing silver halide grain nuclei by adding an aqueous silver salt solution and a halogen salt solution to the reaction vessel by a double jet method, but is not limited thereto. A method of controlling pAg in the reaction solution in the growth by the double jet method can also be used.
[0059]
Next, the method for preparing the silver halide emulsion of the present invention will be described in detail.
The preparation process of the present invention includes a core part forming process ((a) process), a subsequent shell part forming process ((b) process), and an epitaxial junction forming process ((c) process). Basically, it is preferable to perform all the steps (a), (b), and (c), but the step (b) may not be provided.
[0060]
First, step (a), which is a step of forming the core portion, will be described. The core portion forming process can be manufactured through a process generally well known in the field, that is, a process of nucleation process-aging process-growth process. Hereinafter, nucleation, ripening, growth, and each process will be described.
[0061]
1. Nucleation process Tabular grain nucleation is generally performed by adding a silver salt aqueous solution and an alkali halide aqueous solution to a reaction vessel holding an aqueous solution of a protective colloid, or a protective colloid solution containing an alkali halide. A single jet method is used in which a silver salt aqueous solution is added. Moreover, the method of adding aqueous alkali halide solution to the protective colloid solution containing a silver salt as needed can also be used. Further, if necessary, a protective colloid solution, a silver salt solution, and an alkali halide aqueous solution are added to a mixer disclosed in JP-A-2-44335, and immediately transferred to a reaction vessel, thereby transferring tabular grains. Nucleation can also be performed. Further, as disclosed in US Pat. No. 5,104,786, nucleation is performed by passing an aqueous solution containing an alkali halide and a protective colloid solution through a pipe and adding an aqueous silver salt solution thereto. You can also.
[0062]
Gelatin is used as the protective colloid, but natural polymers and synthetic polymers other than gelatin can be used as well. The types of gelatin include alkali-treated gelatin, oxidized gelatin obtained by oxidizing methionine groups in gelatin molecules with hydrogen peroxide, etc. (methionine content 40 μmol / g or less), amino group-modified gelatin (eg, phthalated gelatin, trimellitized) Gelatin, succinylated gelatin, maleated gelatin, esterified gelatin), and low molecular weight gelatin (weight average molecular weight: 3000 to 40,000) are used. Japanese Patent Publication No. 5-12696 can be referred to for oxidized gelatin, and Japanese Patent Publications Nos. 8-82883 and 11-143002 can be referred to for amino group-modified gelatin. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. In addition, natural polymers are disclosed in Japanese Patent Publication No. 7-11550, Research Disclosure Vol. 17643 (December 1978).
[0063]
In nucleation, it is usually preferred that an excess of halogen salt is present before and / or during nucleation. The excess halogen salt in this case is Cl⁻, Br⁻, I⁻These may be used alone or in combination. In the present invention, Cl⁻Is preferably present. The total halogen salt concentration is preferably 3 × 10^-5mol / liter to 0.1 mol / liter, more preferably 3 × 10^-4mol / liter or more and 0.01 mol / liter or less (hereinafter, the liter is also expressed as “L”).
[0064]
The halogen composition in the halide solution added at the time of nucleation is Br.⁻, Cl⁻, I⁻These may be used alone or in combination. In the present invention, Cl⁻In this case, the silver chloride content in the nucleated silver halide nucleus is preferably 5 mol% or more and 100 mol% or less, more preferably 10 mol% or more and 80 mol% or less.
[0065]
The protective colloid may be dissolved in an aqueous alkali halide solution added at the time of nucleation. The temperature during nucleation is preferably from 5 to 60 ° C, but more preferably from 5 to 48 ° C when producing fine tabular grains having an average particle size of 0.5 µm or less. The pH of the dispersion medium is preferably 4 or more and 8 or less when amino group-modified gelatin is used, but preferably 2 or more and 8 or less when other gelatin is used.
[0066]
2. Aging process In the nucleation, fine particles other than tabular grains (especially octahedral and single twin grains) are also formed. Before entering the growth process described below, it is necessary to eliminate grains other than tabular grains to obtain nuclei having a shape to be tabular grains and having good monodispersity. In order to make this possible, it is well known to perform Ostwald ripening following nucleation.
[0067]
Immediately after nucleation, pBr is adjusted, and then the temperature is increased and ripening is performed until the hexagonal tabular grain ratio reaches the maximum. At this time, a protective colloid solution may be additionally added. In this case, the concentration of the protective colloid with respect to the dispersion medium solution is preferably 10% by mass or less. As the additional protective colloid used at this time, the above-mentioned alkali-treated gelatin, amino group-modified gelatin, oxidized gelatin, low molecular weight gelatin, natural polymer, or synthetic polymer is used. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used.
[0068]
The aging temperature is preferably 40 to 80 ° C, more preferably 50 to 80 ° C, and pBr is 1.2 to 3.0. The pH is preferably 4 or more and 8 or less when amino group-modified gelatin is present, but is preferably 2 or more and 8 or less for other gelatins.
[0069]
At this time, a silver halide solvent may be added so that grains other than the tabular grains disappear quickly. In this case, the concentration of the silver halide solvent is preferably 0.3 mol / L or less, and more preferably 0.2 mol / L or less. Thus, it is aged so as to be almost 100% tabular grains only.
[0070]
After the ripening, if the silver halide solvent is unnecessary in the next growth process, the silver halide solvent is removed as follows.
[0071]
(I) NH₃In the case of alkaline silver halide solvents such as₃Ag like⁺It is invalidated by adding an acid with a high solubility product.
(Ii) In the case of a thioether-based silver halide solvent, as described in JP-A-60-136736, H₂O₂It is invalidated by adding an oxidizing agent such as.
[0072]
In the method for producing an emulsion of the present invention, the end of the ripening step is a grain other than tabular grains whose main plane is hexagonal or triangular and has at least two twin planes (regular and single twin grains) ) Refers to the time when it disappears. The disappearance of grains other than tabular grains having a hexagonal or triangular main plane and having at least two twin planes can be confirmed by observing a TEM image of a replica of the grains.
[0073]
In the aging step, an over-aging step described in JP-A-11-174606 may be provided as necessary. The over-ripening step is a step of erasing tabular grains having a slow anisotropic growth speed by further aging the tabular grains themselves after ripening (ripening step) until the hexagonal tabular grain ratio reaches the maximum. When the number of tabular grains obtained in the aging step is 100, it is preferable to reduce the number of tabular grains to 90 or less, and more preferably to 60 or more and 80 or less by the over-ripening step.
[0074]
In the method for producing an emulsion of the present invention, conditions such as pBr and temperature in the overripening step can be set to be the same as those in the ripening step. In the overripening step, a silver halide solvent can be added in the same manner as in the ripening step, and the type, concentration, etc. can be set to be the same as those in the ripening step.
[0075]
3. Growth Process It is preferable to keep pBr in the crystal growth period following the ripening process at 1.4 to 3.5. When the concentration of the protective colloid in the dispersion medium solution before entering the growth process is low (1% by mass or less), the protective colloid may be additionally added. In addition, protective colloids may be added during the growth process. The timing of additional addition may be any time during the growth process. The protective colloid concentration in the dispersion medium solution is preferably 1 to 10% by mass. As the protective colloid used at this time, the above-mentioned alkali-treated gelatin, amino group-modified gelatin, oxidized gelatin, natural polymer, or synthetic polymer is used. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. The pH during growth is preferably 4 to 8 or less when amino group-modified gelatin is present, and 2 to 8 is preferable otherwise. Ag during crystal growth⁺The halogen ion addition rate is preferably 20 to 100%, preferably 30 to 100% of the crystal critical growth rate. In this case, the addition rate of silver ions and halogen ions is increased as the crystal grows. In this case, as described in JP-B-48-36890 and JP-A-52-16364, silver salts and halogen salts are used. The addition rate of the aqueous solution may be increased, and the concentration of the aqueous solution may be increased.
[0076]
When performing the double jet method in which a silver salt aqueous solution and a halogen salt aqueous solution are added simultaneously, in order to prevent the introduction of growth dislocation due to heterogeneous iodine, it is possible to improve the stirring of the reaction vessel and dilute the concentration of the added solution. preferable.
[0077]
A method of adding silver iodide fine particles prepared outside the reaction vessel simultaneously with the addition of the silver salt aqueous solution and the halogen salt aqueous solution is more preferable, and it is preferable that at least 50% or more of the total silver amount is grown by this method. At this time, the growth temperature is preferably 50 ° C. or higher and 90 ° C. or lower, and more preferably 60 ° C. or higher and 85 ° C. or lower. The silver iodide fine particles to be added may be prepared in advance or may be added while continuously preparing. JP-A-10-43570 can be referred to for the preparation method in this case.
[0078]
The average grain size of the silver iodide fine particles to be added is 0.01 μm or more and 0.1 μm or less, preferably 0.02 μm or more and 0.08 μm or less. The iodine composition of the host grains can be changed depending on the amount of silver iodide fine grains to be added.
[0079]
Further, silver iodobromide fine particles may be added in place of the addition of the silver salt aqueous solution and the halogen salt aqueous solution. At this time, by making the iodine amount of the fine particles equal to the iodine amount of the desired host particles, host particles having a desired iodine composition can be obtained. The silver iodobromide fine particles may be prepared in advance, but it is preferable to add them while preparing them continuously outside the reaction vessel. JP-A-10-43570 can be referred to for the preparation method. The average grain size of the silver iodobromide fine particles to be added is 0.005 μm or more and 0.05 μm or less, preferably 0.01 μm or more and 0.03 μm or less. The temperature during growth is 60 ° C. or higher and 90 ° C. or lower, preferably 70 ° C. or higher and 85 ° C. or lower.
[0080]
Further, the above ion addition method, silver iodide fine particle addition method, and silver iodobromide fine particle addition method may be combined.
[0081]
Next, the process (b) which is a shell part is demonstrated.
The shell part may surround the entire core part, may surround only the side surfaces of the tabular grains of the core part, or may surround only the main flat surface part. The number of shells may be one or two or more. When the number of shells is two or more, the shell outside the core is called the first shell, the shell outside the first shell is called the second shell, and the shells outside the following are called the third shell and the fourth shell in order. . In this specification, “outermost layer” refers to the outermost shell.
[0082]
The shell part may be divided into several layers as described above. The average silver iodide content of each layer of the shell part is preferably 1 mol% or more and less than the solid solution limit, and more preferably 2 mol% or more and 20 mol% or less.
[0083]
However, the average silver iodide content of the shell portion immediately before the outermost layer may be 20 mol% or more and 100 mol% or less.
[0084]
In this case, as is apparent from the average silver iodide content, silver iodide can be precipitated in addition to the silver iodobromide mixed crystal during shell formation. In either case, normally, silver iodide disappears and all changes to a silver iodobromide mixed crystal upon formation of the next outermost shell.
[0085]
For the growth of the shell, basically, an aqueous silver nitrate solution and an aqueous halogen solution containing iodide and bromide are added by the double jet method. Alternatively, an aqueous silver nitrate solution and an aqueous halogen solution containing iodide are added by the double jet method. Alternatively, an aqueous halogen solution containing iodide is added by the single jet method.
[0086]
Further, there is a method in which silver iodobromide or silver iodide fine grains are added and ripened and dissolved. Further, as a preferred method, there is a method in which silver iodide fine particles are added, and thereafter an aqueous silver nitrate solution or an aqueous silver nitrate solution and an aqueous halogen solution are added.
[0087]
Further, by using the iodide ion releasing agent described in US Pat. No. 5,496,694, a silver halide phase containing silver iodide can be formed while abruptly generating iodide ions.
Any of the above methods may be used, or a combination thereof may be used.
[0088]
The silver iodide fine grain emulsion may be substantially silver iodide and may contain silver chloride as long as it can form a mixed crystal. 100% silver iodide is preferred. Silver iodide may preferably have β-form, γ-form and α-form or α-form-like structure as described in US Pat. No. 4,672,026 in its crystal structure. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine particles may be formed just before the addition described in the specification of US Pat. No. 5,004,679 or the like, or may be one that has undergone a normal water washing step. The silver iodide fine particles can be easily formed by the method described in US Pat. No. 4,672,026. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, in which the pI value at the time of grain formation is kept constant, is preferred. Where pI is I in the system⁻It is the logarithm of the reciprocal of the ion concentration. The type, concentration, presence / absence of silver halide solvent, type, concentration, etc. of the protective colloid agent such as temperature, pI, pH, and gelatin are not particularly limited, but the grain size is preferably 0.1 μm or less, more preferably 0. 0.07 μm or less.
[0089]
The silver iodobromide fine particles may be prepared in advance as described above, but it is preferable to add them while preparing them continuously outside the reaction vessel. JP-A-10-43570 can be referred to for the preparation method. The grain size of the silver iodobromide fine particles to be added is 0.005 μm or more and 0.05 μm or less, preferably 0.01 μm or more and 0.03 μm or less.
[0090]
Silver iodobromide fine grains and silver iodide fine grains are preferably added continuously during shell formation, but in the case of shell formation immediately before the outermost layer, silver iodide fine grains are preferably added rapidly.
[0091]
With respect to iodide ion release, for example, JP-B-7-11549, JP-A-5-341418, JP-A-5-346631, JP-A-5-323487, JP-A-6-11780, JP-A-6-11781, and JP-A-6-11787. No. 6-11784, 6-27564, 6-138595, 6-230495, 6-242527, 6-250309, 6-250310, 6-250311, 6-250313, 6-258745, 6-273766, 6-313933, 7-219102, 8-62754, 8-95181, U.S. Pat.No. 5,389,508, 5,418,124, 5,482,826, 5,496,694, 5,498,516, 5,580,713, 5, It is preferable to use a method of releasing iodide ions from the iodide ion-releasing agent by reaction with an alkali or a nucleophilic agent described in JP and specification, such as No. 27,664. Regarding the iodide ion releasing agent, it is preferable to use the specific compounds and the usage thereof described in the above patent application.
[0092]
(B) Although dislocation lines do not have to exist in the part of the step, it is more preferable that they exist. The dislocation lines are preferably present in the vicinity of the edge portion or the corner portion of the tabular grain. The vicinity of the edge part means the outer peripheral part (edge part) of six sides of the tabular grain and the inner part thereof. The vicinity of the corner is a three-dimensional circle surrounded by the perpendicular and the side when a perpendicular is drawn from the point of x% from the center of the straight line connecting the center of the particle to each vertex. It is a part of. The value of x is preferably 50 or more and less than 100, more preferably 75 or more and less than 100. The average number of dislocation lines present in the vicinity of the edge or corner is preferably 10 or more per particle. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and it can be clearly distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.
[0093]
The tabular grains of the present invention desirably have a uniform dislocation line quantity distribution between grains. In the emulsion of the present invention, the silver halide hexagonal tabular grains containing 10 or more dislocation lines per grain preferably occupy 100 to 50% of the projected area of all grains, more preferably 100 to 70%, especially Preferably it occupies 100 to 90%. If it is less than 50%, it is not preferable in terms of homogeneity between particles.
[0094]
Next, the epitaxial junction forming step which is the step (c) will be described. Regarding the formation of silver halide epitaxial junctions on tabular grains, as described in U.S. Pat. No. 4,435,501, iodide ions, aminoazaindene adsorbed on the surface of tabular grains, or spectroscopy. It has been shown that a silver salt epitaxial junction can be formed at a site selected by a site director such as a sensitizing dye, such as a side surface or a corner of a tabular grain. JP-A-8-69069 discloses that a silver salt epitaxial junction is formed at a selected portion of an ultrathin host tabular grain, and this epitaxial phase is optimally sensitized to achieve high sensitivity. .
[0095]
In the present invention, the tabular grains are sensitized in the same manner as in these methods. However, in the present invention, the epitaxial junction is composed of a portion having a silver bromide content of less than 40 mol% and silver bromide. It is characterized in that the portion having a content of 40 mol% or more and the portion having a silver bromide content of less than 40 mol% is present inside the epitaxial junction and not on the surface. Further sensitivity enhancement is achieved.
[0096]
In the present invention, the site director used for forming the epitaxial junction may be aminoazaindene or spectral sensitizing dye, or may be iodide ion or thiocyanate ion. These can be used properly or combined according to the purpose.
[0097]
By changing the amount of sensitizing dye, iodide ion, and thiocyanate ion, the site where the silver salt epitaxial junction is formed is limited to the main plane, side, or corner of the tabular grain. You can also combine them. The addition amount of aminoazaindene, iodide ion, thiocyanate ion, and spectral sensitizing dye used as a site director is appropriately selected according to the silver amount, surface area, and epitaxial junction formation site of the silver halide tabular grain used. It is preferable to do. 30-70 degreeC is preferable and, as for the temperature which forms a silver salt epitaxial junction part, 35-60 degreeC is still more preferable. In this case, the pAg is preferably 9.0 or less, and more preferably 8.0 or less. The pH is preferably from 3.0 to 8.0, more preferably from 4.0 to 7.0. In this way, by appropriately selecting the type, addition amount, and epitaxial deposition conditions (temperature, pAg, pH, etc.) of the site director, an epitaxial junction of silver salt at the main plane, side, or corner of the tabular grain Can be selectively formed.
[0098]
After adding the site director, the epitaxial junction may be formed by adding the silver salt aqueous solution and the halogen salt aqueous solution at the same time. Alternatively, the silver salt aqueous solution may be added after the halogen salt aqueous solution is added. Further, after adding the halogen salt aqueous solution, the silver salt aqueous solution and the halogen salt aqueous solution may be added simultaneously.
[0099]
The epitaxial junction formation may be performed several times by changing the pAg and pH at the time of epitaxial junction formation, or may be performed several times by changing the halogen salt composition. In particular, it is preferable to perform the epitaxial junction formation in several times by changing the halogen composition.
[0100]
When an epitaxial junction is formed by changing the halogen composition, the silver salt aqueous solution and the halogen salt aqueous solution may be added simultaneously, or only the halogen salt aqueous solution may be added. And a halogen salt aqueous solution may be added simultaneously. Further, a silver halide aqueous solution and a halogen salt aqueous solution are mixed with a mixing device separate from the reaction solution to form silver halide fine particles, and then the fine particles are added to the reaction vessel to continue forming the epitaxial junction. Then, the silver halide fine particles prepared in advance may be added to the reaction vessel to continue the formation of the epitaxial junction.
[0101]
The epitaxial junction formation step may be performed continuously after the tabular grain formation, may be performed after the tabular grain formation and once washed / redispersed, or may be performed before chemical sensitization.
[0102]
Formation of the epitaxial junction divided into several times may be performed continuously in the silver halide formation step, may be performed after washing / redispersion with water, or may be performed before chemical sensitization. Moreover, you may divide before and after washing / redispersion.
[0103]
Although dislocation lines may not exist in the epitaxial junction, it is more preferable that dislocation lines exist. The average number of dislocation lines present is preferably 10 or more per grain. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and it can be clearly distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.
[0104]
It is further preferable to introduce a “dopant (metal complex)” as described in JP-A-8-69069 into the epitaxial junction. Specifically, it is preferable that a 6-cyano metal complex is doped when the epitaxial junction is formed. Among the 6 cyano metal complexes, those containing iron, ruthenium, osmium, cobalt, rhodium, iridium or chromium are preferred. The amount of metal complex added is 10 per mole of silver halide.^-910^-2Preferably in the molar range, 10 per mole of silver halide.^-810^-4More preferably, it is in the molar range. The metal complex can be added by dissolving in water or an organic solvent. The organic solvent is preferably miscible with water. Examples of the organic solvent include alcohols, ethers, glycols, ketones, esters, and amides.
[0105]
As the protective colloid used in preparing the emulsion of the present invention, it is advantageous to use the gelatin described above, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives Various synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinylpyrazole, or a single or copolymer Substances can be used.
[0106]
The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. Gelatin is used as the protective colloid, but natural polymers and synthetic polymers other than gelatin can be used as well. The types of gelatin include alkali-treated gelatin, oxidized gelatin obtained by oxidizing methionine groups in gelatin molecules with hydrogen peroxide, etc. (methionine content 40 μmol / g or less), amino group-modified gelatin (eg, phthalated gelatin, trimellitized) Gelatin, succinylated gelatin, maleated gelatin, esterified gelatin) are used. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. In addition, natural polymers are disclosed in Japanese Patent Publication No. 7-11550, Research Disclosure Vol. 17643 (December 1978). The temperature for washing with water can be selected according to the purpose, but is preferably selected within the range of 5 ° C to 50 ° C. Although pH at the time of water washing can also be chosen according to the objective, it is preferred to choose between 2-10. More preferably, it is the range of 3-8. Although pAg at the time of washing can also be selected according to the purpose, it is preferable to select between 5 and 10. The washing method can be selected from a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, an ion exchange method, and an ultrafiltration method. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like can be selected.
[0107]
The emulsion of the present invention is preferably subjected to ultrafiltration salt removal and / or concentration.
The term “ultrafiltration” refers to M.I. Used according to the definition given in “Ultrafiltration Handbook” by Cheyan (published in Technological Publishers, 1986). In this filtration method, a membrane is generally used, and this membrane allows unnecessary substances to pass through. For example, in the production process of a silver halide emulsion, it is a purification method using a film that passes unnecessary salts and the like without passing required substances such as silver halide grains.
[0108]
The ultrafiltration method also includes washing and / or concentrating the silver halide emulsion to remove excess soluble salts. These are passed through a silver halide emulsion dispersed through a pressurized ultrafiltration module, excess salts are passed through a semipermeable membrane, and a residue (emulsion) consisting of silver halide grains and a dispersant. To be done.
[0109]
This selective separation is accomplished by hydraulically pressing the solution against a synthetic semipermeable membrane that is designed to selectively pass all molecules below a certain size and leave larger molecules remaining. The In the present invention, the pressure of the silver halide emulsion in contact with the ultrafiltration membrane is 1 to 10 kg / cm.²It is preferable that
[0110]
Silver halide and excess salts precipitated in the peptizer are fed into the container by well-known means. This liquid is then pumped through the flow meter into the ultrafiltration module and excess salts are removed as permeate while the residue is refluxed into the container during the recycle mode of operation. In another approach, many ultrafiltration modes can be connected in series so that residue from the previous module is fed into the inlet line of the next module.
[0111]
Prior to the subsequent flow of liquid through each module, this liquid can be re-diluted with a solvent for washing purposes, and in other ways the solution need not be re-diluted for the purpose of concentration. .
[0112]
The ultrafiltration is preferably carried out by circulating the dispersion in the reaction vessel in contact with the semipermeable ultrafiltration membrane so that a pressure difference occurs across the semipermeable ultrafiltration membrane. Membranes can only penetrate molecules below a certain size and suitable membranes containing pores sized to retain larger molecules and silver halide in the dispersion are about 500-300,000. , Preferably from those exhibiting a transmission cutoff in the molecular weight range of about 500 to 100,000.
[0113]
The pressure of the dispersion in contact with the ultrafiltration membrane can vary over a wide range. Typically, the pressure in the reaction vessel in contact with the ultrafiltration membrane is about 7.0 kg / cm.²The outlet pressure of the stagnant is about 0.7 kg / cm²It is as follows. The pressure differential across the membrane is typically about 2.8-4.2 kg / cm.²It is. Of course, it is within the skill of the art to operate at pressures outside these ranges depending on the structure of the reaction vessel and ultrafiltration membrane, the viscosity of the dispersion, the concentration of the retentate and the desired retentate purity. .
[0114]
The membrane used for ultrafiltration is typically an anisotropic membrane comprising a very thin layer having a very fine porous structure supported on a thicker porous structure layer. These useful membranes include various polymeric substances such as polyvinyl chloride, polyvinyl carboxylate, polyvinyl formate, polyvinyl acetate, polyvinyl alcohol, polysulfone, polyvinyl ether, polyacrylamide, polyacrylonitrile, polymethacrylamide, polyimide. Polyesters, polyfluoroalkylenes such as polytetrafluoroethylene, and polyvinylidene fluoride, and cellulosic polymers such as cellulose and cellulose esters such as cellulose acetate, cellulose butyrate and cellulose acetate butyrate.
[0115]
In the formation of the particles of the present invention, for example, JP-A-5-173268, JP-A-5-173269, JP-A-5-173270, JP-A-5-173271, JP-A-6-202258, and JP-A-7-175147. The described polyalkylene oxide block copolymers or the polyalkylene oxide copolymers described, for example, in US Pat. No. 3,089,578 may be present. The time when the compound is present may be any time during the preparation of the particles, but the effect is great when used at an early stage of particle formation.
[0116]
In preparation of the emulsion of the present invention, for example, at the time of grain formation, desalting step, chemical sensitization, or before coating, it is preferable to have a metal ion salt present before coating. When the particles are doped, it is preferably added after the formation of the particles, before the completion of the chemical sensitization after the formation of the particles when used as a particle sensitizer or a chemical sensitizer. A method of doping the entire particle and a method of doping only the core portion or the shell portion of the particle can also be selected. For example, Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, and Bi can be used. These metals can be added in the form of a salt that can be dissolved during particle formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydrate salt, hexacoordinated complex salt, and tetracoordinated complex salt. For example, CdBr₂, CdCl₂, Cd (NO₃)₂, Pb (NO₃)₂, Pb (CH₃COO)₂, K₄[Fe (CN)₆], (NH₄)₄[Fe (CN)₆], K₂IrCl₆, (NH₄)₃RhCl₆, K₄Ru (CN)₆Can be given. The ligand of the coordination compound can be selected from halo, aqua, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may be used in combination of two or more.
[0117]
The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding an aqueous hydrogen halide solution (for example, HCl, HBr) or an alkali halide (for example, KCl, NaCl, KBr, NaBr) can be used. Moreover, you may add an acid, an alkali, etc. as needed. The metal compound can be added to the reaction vessel before the particle formation or can be added during the particle formation. In addition, water-soluble silver salt (for example, AgNO₃) Or an aqueous alkali halide solution (for example, NaCl, KBr, KI) and can be added continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.
[0118]
It may be useful to add a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031. In addition to S, Se, and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.
[0119]
The silver halide grains of the present invention have a chalcogen sensitization such as sulfur sensitization, selenium sensitization or tellurium sensitization; noble metal sensitization such as gold sensitization or palladium sensitization; It can be applied in any step of the manufacturing process. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are types that embed chemical sensitization nuclei inside the particles, types that embed in a shallow position from the particle surface, or types that make chemical sensitization nuclei on the surface. In the emulsion of the present invention, the location of chemical sensitization nuclei can be selected according to the purpose, but generally preferred is the case where at least one chemical sensitization nucleus is formed in the vicinity of the surface.
[0120]
One chemical sensitization that can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, by TH James, The Theory of Photographic Process, 4th edition, published by McMillan, 1977, (TH James, The Theory of the Photographic Process, 4th ed, McCillan, 1977) pages 67-76 can be used. Research Disclosure, 120, April, 1974, 12008; Research Disclosure, 34, June, 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, No. 3,772,031, No. 3,857, 11, as described in US Pat. Nos. 3,901,714, 4,266,018, and 3,904,415, and British Patent 1,315,755. At pAg 5-10, pH 5-8, and temperature 30-80 ° C., sulfur, selenium, tellurium, gold, platinum, palladium, iridium, or a combination of these sensitizers can be used. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, iridium and the like can be used, and gold sensitization, palladium sensitization and the combined use of both are particularly preferable.
[0121]
In gold sensitization, P.I. Gold salts described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure 307, 307105, and the like can be used.
[0122]
Specifically, in addition to chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, US Pat. No. 2,642,361 (such as gold sulfide and gold selenide), 3503749 (such as gold thiolate having a water-soluble group), No. 5049484 (bis (methylhydantoinato) gold complex, etc.), No. 5049485 (mesoionic thiolate gold complex, such as 1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold complex) ), Macrocyclic heterocyclic complexes of 5252455 and 5391727, 5620841, 5700571, 5759760, 5759761, 5912111, 5912112, 5939245, JP-A-1-147537 No., 8-69074, No. 8-69075, No. -269554, Japanese Patent Publication No. 45-29274, East German Patent DD-264524A, 264525A, 265474A, 298321A, JP-A-2001-75214, 2001-75215, 2001-75216, 2001-75217 In addition, gold compounds described in publications and specifications such as 2001-75218 can also be used.
[0123]
The palladium compound means a palladium divalent salt or a tetravalent salt. Preferred palladium compounds are R₂PdX₆Or R₂PdX₄It is represented by Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.
[0124]
Specifically, K₂PdCl₄, (NH₄)₂PdCl₆, Na₂PdCl₄, (NH₄)₂PdCl₄, Li₂PdCl₄, Na₂PdCl₆Or K₂PdBr₄Is preferred. Gold compounds and palladium compounds are preferably used in combination with thiocyanate or selenocyanate.
[0125]
In sulfur sensitization, unstable sulfur compounds are used. The unstable sulfur compounds described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure 307, 307105, and the like can be used.
[0126]
Specifically, thiosulfate (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-ethyl-N ′-(4-methyl-2-thiazolyl) thiourea, dicarboxymethyl- Dimethylthiourea, carboxymethyl-trimethylthiourea), thioamides (eg, thioacetamide), rhodanines (eg, diethylrhodanine, 5-benzylidene-N-ethylrhodanine), phosphine sulfides (eg, trimethylphosphine) Sulfide), thiohydantoins, 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg, dimorpholine disulfide, cystine, hexathiocan-thione), mercapto compounds (eg, cysteine), polythionates, Elemental Such known sulfur compounds and active gelatin, such as yellow may also be used. Particularly preferred are thiosulfates, thioureas, phosphine sulfides and rhodanines.
[0127]
In selenium sensitization, unstable selenium compounds are used, and Japanese Patent Publication Nos. 43-13489, 44-15748, JP-A-4-25832, 4-109340, 4-271341, and 5-40324. 5-11385, 6-51415, 6-175258, 6-180478, 6-208184, 6-208186, 6-317867, 7-92599, Selenium compounds described in publications such as 7-98483 and 7-140579 can be used.
[0128]
Specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (for example, selenoamide, N, N -Diethylphenylselenamide), phosphine selenides (eg triphenylphosphine selenide, pentafluorophenyl-triphenylphosphine selenide), selenophosphates (eg tri-p-tolylselenophosphate, Tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids, selenoesters (for example, methoxyphenylselenocarboxy-2,2-dimethoxycyclohexa) Ester), or the like may be used diacylselenides. Furthermore, non-labile selenium compounds described in Japanese Patent Publication Nos. 46-4553 and 52-34492, such as selenious acid, selenocyanic acids (for example, potassium selenocyanate), selenazoles, selenides and the like are also used. be able to. In particular, phosphine selenides, selenoureas, selenoesters and selenocyanic acids are preferred.
[0129]
In tellurium sensitization, an unstable tellurium compound is used, and JP-A-4-224595, JP-A-4-271341, JP-A-4-3333043, JP-A-5-303157, JP-A-6-27573, JP-A-6-175258, The unstable tellurium compounds described in publications such as JP-A-6-180476, JP-A-6-208184, JP-A-6-208186, JP-A-6-317867, and JP-A-7-140579 can be used.
[0130]
Specifically, phosphine tellurides (for example, butyl-diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxydiphenylphosphine telluride), diacyl (di) tellurides ( For example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (N-phenyl-N-benzylcarbamoyl) telluride, bis ( Ethoxycarbonyl) telluride), telluroureas (for example, N, N′-dimethylethylenetellurourea, N, N′-diphenylethylenetellurourea) telluramides, telluroesters, etc. may be used.
[0131]
Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, and JP-A-58-126526. And the above-mentioned “Photo Emulsion Chemistry” by Duffin, pages 138 to 143.
[0132]
The amount of the gold sensitizer or chalcogen sensitizer used in the present invention varies depending on the silver halide grains used, chemical sensitization conditions, etc., but it is 10 per mole of silver halide.^-8-10^-2Moles, preferably 10^-7-10^-3It is about a mole.
[0133]
It is preferred to subject the silver halide emulsion of the present invention to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.
[0134]
Here, reduction sensitization means a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in a low pAg atmosphere called silver ripening, and a pH of 8 to 11 called high pH ripening. Either a method of growing or aging in an atmosphere of high pH can be selected. Two or more methods can be used in combination.
The method of adding a reduction sensitizer is a preferable method in that the level of reduction sensitization can be finely adjusted.
[0135]
Examples of reduction sensitizers include stannous salts, ascorbic acid and derivatives thereof, hydroquinone and derivatives thereof, catechol and derivatives thereof, hydroxylamine and derivatives thereof, amines and polyamines, hydrazine and derivatives thereof, paraphenylenediamine and Examples thereof include formamidine sulfinic acid (thiourea dioxide), silane compounds, and borane compounds. These reduction sensitizers can be selected and used in the reduction sensitization of the present invention, and two or more compounds can be used in combination. Regarding the method of reduction sensitization, U.S. Pat. Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777, 3,930, As for the method disclosed in the specification of No. 867 and the like, and the method of using the reducing agent, the method disclosed in Japanese Patent Publication Nos. 57-33572, 58-1410, and JP-A 57-179835 is used. Can be used. Catechol and its derivatives, hydroxylamine and its derivatives, and formamidine sulfinic acid (thiourea dioxide) are preferred compounds as reduction sensitizers. The following general formulas (1) and (2) are also preferred reduction sensitizers.
[0136]
[Chemical 1]

[0137]
In general formulas (1) and (2), W₅₁, W₅₂Represents a sulfo group or a hydrogen atom. However, W₅₁, W₅₂At least one of represents a sulfo group. The sulfo group is generally an alkali metal salt such as sodium or potassium, or a water-soluble salt such as an ammonium salt. Specific examples of preferable compounds include 3,5-disulfocatechol disodium salt, 4-sulfocatechol ammonium salt, 2,3-dihydroxy-7-sulfonaphthalene sodium salt, 2,3-dihydroxy-6,7-di And sulfonaphthalene potassium salt.
[0138]
Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but it is 10 per mol of silver halide.^-7-10^-1A molar range is suitable. The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during particle growth.
[0139]
It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver refers to a compound having an action of acting on metallic silver and converting it into silver ions. Particularly effective are compounds capable of converting extremely fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions. The silver ions generated here may form, for example, a silver salt that is hardly soluble in water such as silver halide, silver sulfide, or silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. May be formed. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO).₂・ H₂O₂・ 3H₂O, 2NaCO₃・ 3H₂O₂, Na₄P₂O₇・ 2H₂O₂2Na₂SO₄・ H₂O₂・ 2H₂O), peroxyacid salts (eg K₂S₂O₈, K₂C₂O₆, K₂P₂O₈), Peroxy complex compounds (for example, K₂[Ti (O₂) C₂O₄] 3H₂O, 4K₂SO₄・ Ti (O₂) OH / SO₄・ 2H₂O, Na₃[VO (O₂) (C₂H₄)₂] 6H₂O), permanganate (eg KMnO)₄), Chromate (eg, K₂Cr₂O₇) Oxygenates, halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), high valent metal salts (eg potassium hexacyanoferrate) and thiosulfone There is an acid salt.
[0140]
Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromosuccinimide, chloramine T, An example is chloramine B).
[0141]
Preferred oxidizing agents in the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizers of thiosulfonates, and organic oxidizers of quinones. It is a preferred embodiment to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver. The method can be selected from a method of applying reduction sensitization after using an oxidizing agent, a reverse method thereof, or a method of simultaneously coexisting both. These methods can be selected and used in either the particle formation step or the chemical sensitization step.
[0142]
The photographic emulsion of the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; , Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7) chitraazaindenes), pentaazaindene Known as antifoggants or stabilizers, such as, it can be added to many compounds. For example, those described in US Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is the compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, water washing process, dispersion after water washing, chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to the original antifogging and stabilizing effect added during emulsion preparation, control grain habit, reduce grain size, decrease grain solubility, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.
[0143]
The photographic emulsion of the present invention is preferably spectrally sensitized with methine dyes or the like in order to exhibit the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole Nuclei, benzimidazole nuclei and quinoline nuclei are applicable. These nuclei may have a substituent on the carbon atom.
[0144]
The merocyanine dye or the complex merocyanine dye has, as a nucleus having a ketomethylene structure, for example, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine A 5- or 6-membered heterocyclic nucleus of a nucleus or a thiobarbituric acid nucleus can be applied.
[0145]
These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703 377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Application Laid-Open Nos. 52-110618, and 52-109925.
[0146]
Along with the sensitizing dye, the emulsion itself may contain a dye having no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization. The timing when the sensitizing dye is added to the emulsion may be at any stage of emulsion preparation that has been known to be useful so far. Most commonly, it is carried out after completion of chemical sensitization and before application, but as described in U.S. Pat. Nos. 3,628,969 and 4,225,666. Spectral sensitization can be performed simultaneously with chemical sensitization by adding at the same time as the sensitizer, or can be performed prior to chemical sensitization as described in JP-A-58-113928. Spectral sensitization can be started by adding before completion of silver particle precipitation. Furthermore, as taught in U.S. Pat. No. 4,225,666, these said compounds are added separately, i.e. some of these compounds are added prior to chemical sensitization and the remainder It can be added after chemical sensitization, and may be at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756. The amount added is 4 x 10 per mole of silver halide.^-6~ 8x10^-3Can be used in moles.
[0147]
Furthermore, the present invention is preferably used in combination with a technique for improving light absorption with a spectral sensitizing dye. For example, by utilizing intermolecular force, more sensitizing dyes can be adsorbed on the surface of silver halide grains than monolayer saturated adsorption (ie, single layer adsorption), or two or more separate conjugates can be covalently bonded. Adsorption of so-called linked dyes with linked chromophores. Among these, it is preferable to use together with the technique described in the following patent publications and specifications. JP-A-10-239789, JP-A-11-133531, JP-A-2000-267216, JP-A-2000-275772, JP-A-2001-75222, JP-A-2001-75247, JP-A-2001-75221, JP 2001-75226, JP 2001-75223, JP 2001-255615, JP 2002-23294, JP 10-171058, JP 10-186559, JP 10-197980, JP JP 2000-81678, JP 2001-5132, JP 2001-166413, JP 2002-49113, JP 64-91134, JP 10-110107, JP 10-11058, JP 10-226758, JP-A-10-307358, JP-A-10-307 59, JP-A-10-310715, JP-A-2000-231174, JP-A-2000-231172, JP-A-2000-231173, JP-A-2001-356442, European Patent 985965A, European Patent 985964A, European Patent No. 985966A, European Patent No. 985967A, European Patent No. 1085372A, European Patent No. 1085373A, European Patent No. 1172688A, European Patent No. 1199595A, European Patent No. 887700A1.
[0148]
Furthermore, it is preferable to use together with the technique described in the patent gazette shown below. JP-A-10-239789, JP-A-2001-75222, JP-A-10-171058.
[0149]
A fragmentable electron donating sensitizer may be used. Electron donating sensitizers are disclosed in U.S. Pat. Nos. 5,747,235, 5,747,236, 6,054,260, 5,994,051, European Patent Nos. 786692A1 and 893732A1, It is described in the specifications and publications of Kaihei 2000-181001, 2000-180999, 2000-181002, 2000-181000, 2000-221626, 2000-221628. The fragmentable electron donating sensitizer may be used at any time during the production process of the photosensitive material. For example, at the time of particle formation, desalting step, chemical sensitization, and before coating. Moreover, it can also add in several steps in these processes. The compound of the present invention is preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound having higher solubility when the pH is increased or decreased may be dissolved at a higher or lower pH and added. The fragmentable electron donating sensitizer is preferably used in the emulsion layer, but may be added to the protective layer or intermediate layer together with the emulsion layer and diffused during coating. The timing of addition of the compound of the present invention is preferably before or after the sensitizing dye, and preferably 1 × 10 5 per mole of silver halide.^-9~ 5x10^-2Mole, more preferably 1 × 10^-8~ 2x10^-3It is contained in the silver halide emulsion layer in a molar ratio.
[0150]
When an electron donating sensitizer capable of fragmentation is used, it is preferable to use a preservability improving agent. As the preservability improver, it is preferable to use compounds described in JP-A Nos. 11-119364 and 2001-42466.
[0151]
The emulsion of the present invention can be used for any photosensitive material, but is preferably used for a multilayer color photographic photosensitive material. It is more preferably used for the blue-sensitive layer of the multilayer color photographic light-sensitive material, and most preferably used for the highest blue-sensitive layer of the multilayer color photographic light-sensitive material. At this time, especially when the silver iodide content is high, a high sensitivity / granularity ratio due to an increase in blue light absorption and an increase in blue light absorption based on an increase in sensitizing dye adsorption due to the plate shape. Is obtained. In addition, by improving the monodispersity of the projected area diameter of the grains and decreasing the silver iodide content distribution between grains, the high sensitivity / grain ratio, improved pressure characteristics, improved storage aging characteristics and processing dependency Improvements can be achieved. Further, the scattering of light is reduced by the flat plate shape, and the sharpness of the lower layer is improved.
[0152]
When the light-sensitive material produced using the silver halide emulsion of the present invention is a color photographic light-sensitive material, a silver halide emulsion having a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. There is no particular limitation on the number and order of the silver halide emulsion layer and the non-light-sensitive layer as long as at least one layer is provided. A typical example is a silver halide photographic light-sensitive material having at least one color-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layer is generally used. Are arranged in the order of the red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are contained in the same color-sensitive layer.
A non-photosensitive layer such as an intermediate layer of each layer may be provided between the above-described silver halide photosensitive layers and in the uppermost layer and the lowermost layer.
[0153]
The intermediate layer includes couplers and DIR compounds as described in JP-A Nos. 61-43748, 59-113438, 59-113440, 61-20037, and 61-20038. May be included, and a color mixing inhibitor may be included as normally used.
[0154]
A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high-sensitivity emulsion layer and a low-sensitivity emulsion as described in West German Patent 1,121,470 or British Patent 923,045. A two-layer structure of layers can be preferably used. In general, it is preferable that the photosensitivity is gradually decreased toward the support, and a non-photosensitive layer may be provided between the halogen emulsion layers. Further, as described in JP-A-57-112751, 62-200350, 62-206541 and 62-206543, a low-sensitivity emulsion layer is formed on the side away from the support. A high-sensitivity emulsion layer may be provided on the side close to the body.
[0155]
As a specific example, from the side farthest from the support, for example, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL ) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / It can be installed in the order of RH.
[0156]
Further, as described in JP-B-55-34932, it can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the blue photosensitive layer / GL / RL / GH / RH may be installed in this order from the side farthest from the support.
[0157]
In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged, and an arrangement composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitive emulsion layer from the side away from the support in the same color-sensitive layer. They may be arranged in the order of / high sensitivity emulsion layer / low sensitivity emulsion layer.
[0158]
In addition, they may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer, or low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer.
Further, the arrangement may be changed as described above even when there are four or more layers.
[0159]
Further, a layer containing silver halide tabular grains that do not form an image after exposure processing may be disposed. The emulsion layer does not have to be adjacent to the emulsion layer according to claim 1 of the present invention, but is preferably adjacent to the emulsion layer according to claim 1 of the present invention so as to be close to the support. It is preferred that Specifically, the silver halide tabular grains that do not form an image preferably have a grain thickness of 0.02 μm to 0.2 μm, and more preferably 0.05 μm to 0.15 μm. The particle size is preferably from 0.05 μm to 2.0 μm, more preferably from 0.1 μm to 1.5 μm. Further, the average silver iodide content of the silver halide grains is preferably 3 mol% or less, more preferably 2 mol% or less, based on the total Ag amount. The silver halide emulsion that does not form an image is preferably basically not subjected to chemical image processing, but a silver halide adsorbing material may be adsorbed to stabilize the dye or silver halide grains. Silver halide grains not forming an image in a silver halide emulsion layer not forming an image are 0.1 g / m in terms of Ag.²2.0 g / m²It is preferable that the following is contained, 0.2 g / m²1.0 g / m or more²The following is more preferable. The silver halide tabular grains that do not form an image are formed by setting the thickness of the tabular grains so as to reflect light of a specific wavelength as described in JP-A-2000-305228 and JP-A-2000-314940. Also good. Specifically, tabular grains having such a thickness that the emulsion layer according to claim 1 of the present invention, in which the emulsion layer where no image is formed, is adjacent to the indicator, has strong reflection in the wavelength range to which light is exposed may be used. However, the thickness need not be set so as to reflect a specific wavelength.
As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.
[0160]
The above-mentioned various additives are used in the light-sensitive material according to the present invention, but various additives can be used depending on the purpose.
These additives are described in more detail in Research Disclosure Item 17643 (December 1978), Item 18716 (November 1979) and Item 308119 (December 1989). These are summarized in the table below.
[0161]

[0162]
In order to prevent deterioration of photographic performance due to formaldehyde gas, compounds that can be immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 are sensitized. It is preferable to add to the material.
[0163]
Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 1 described above. 17643, VII-CG and G. 307105, described in the patents described in VII-CG.
[0164]
Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat. No. 3,973,968, No. 4,314,023, No. 4 511,649, European Patent No. 249,473A, and the like.
[0165]
The magenta coupler is preferably a 5-pyrazolone compound or a pyrazoloazole compound. US Pat. Nos. 4,310,619, 4,351,897, EP 73,636, US Pat. No. 061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-35730, 55-1118034, 60-185951, US Pat. No. 4,500,630, Nos. 4,540,654, 4,556,630, and International Publication WO88 / 04795 are particularly preferable.
[0166]
Examples of cyan couplers include phenolic and naphtholic couplers, U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200. No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3 758,308, 4,334,011, 4,327,173, West German Patent Publication 3,329,729, European Patents 121,365A, 249,453A, U.S. Pat.Nos. 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4, No. 690,889, No. 4,254,212 The No. 4,296,199, are preferred according to JP-61-42658 or the like.
[0167]
Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320, No. 4,576,910, British Patent No. 2,102,137, European Patent No. 341,188A and the like.
[0168]
As couplers in which the coloring dye has an appropriate diffusibility, U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, West German Patent (Publication) 3,234 , 533 is preferred.
[0169]
A colored coupler for correcting unwanted absorption of a coloring dye is Research Disclosure No. No. 17643, item VII-G, ibid. No. 307105, VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. No. 4,138,258, British Patent 1,146, The one described in the specification of 368 is preferable. In addition, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye emitted during coupling described in US Pat. No. 4,774,181, and a coupler described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye.
[0170]
Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention. DIR couplers that release a development inhibitor include the above-mentioned RD17643, item VII-F and No. 307105, patents described in paragraph VII-F, JP-A 57-151944, 57-154234, 60-184248, 63-37346, 63-37350, US Pat. Those described in the respective specifications of 4,248,962 and 4,782,012 are preferred.
[0171]
As couplers for releasing a nucleating agent or a development accelerator in the form of an image during development, British Patent Nos. 2,097,140 and 2,131,188, JP-A-59-157638, 59 The thing of -170840 gazette is preferable. Further, a fogging agent is obtained by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-45687. Also preferred are compounds that release development accelerators, silver halide solvents, and the like.
[0172]
Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and the like, US Pat. Nos. 4,283,472, 4,338, No. 393, No. 4,310,618, etc. Multi-equivalent couplers, JP-A-60-185950, JP-A-62-24252, etc., DIR redox compound releasing couplers, DIR couplers releasing Couplers, DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds, couplers that release dyes that recolor after withdrawal as described in EP 173,302A, 313,308A, RD. No. No. 11449, No. 24241, bleach accelerator releasing coupler described in JP-A-61-201247, ligand releasing coupler described in US Pat. No. 4,555,477, JP-A-63-75747, etc. And couplers that emit fluorescent dyes described in US Pat. No. 4,774,181.
[0173]
The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods.
Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027.
[0174]
Specific examples of high-boiling organic solvents having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). Bis (2,4-di-tert-amylphenyl) phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); phosphoric acid or phosphonic acid Esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate Benzoates (eg 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate); amides (eg N, N-diethyldodecanamide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone); alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amylphenol); aliphatic carboxylic acid esters (eg, bis ( 2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octylanily) ); Hydrocarbons (e.g., can be exemplified paraffin, dodecylbenzene, and diisopropylnaphthalene). As the auxiliary solvent, for example, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone. , Cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.
[0175]
Examples of latex dispersion process steps, effects and impregnating latexes are described in, for example, US Pat. No. 4,199,363, West German Patent Application (OLS) No. 2,541,274, and No. 2,541,230. It is described in the specification.
[0176]
Examples of the color light-sensitive material of the present invention include phenethyl alcohol, and those described in JP-A-63-257747, JP-A-62-272248, and JP-A-1-80941, for example, 1,2-benzisothiazoline-3- Add various preservatives or fungicides such as ON, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole It is preferable to do.
[0177]
The emulsion of the present invention can be applied to various color light-sensitive materials. For example, color negative films for general use or movies, color reversal films for slides or television, color paper, color positive film and color reversal paper can be given as representative examples. The present invention can be particularly preferably used for a film for color duplication.
[0178]
Suitable supports that can be used for the light-sensitive material containing the emulsion of the present invention include, for example, the aforementioned RD. No. 17643, page 28, ibid. No. 18716, page 647, right column to page 648, left column, and 307105, page 879.
[0179]
In the light-sensitive material containing the emulsion of the present invention, the total thickness of all hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and 16 μm or less. Is particularly preferred. In addition, membrane swelling speed T_1/2Is preferably 30 seconds or shorter, and more preferably 20 seconds or shorter. The film thickness here means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days). Also, the membrane swelling speed T_1/2Can be measured according to techniques known in the art, such as Photographic Science and Engineering (Vol. Sci. Eng.), Vol. 19, No. 2, 124 by A. Green et al. It can be measured by using a spherometer of the type described on page 129. T_1/2Is defined as the time required to reach 90% of the maximum swelled film thickness when it is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds, and to reach 1/2 of the saturated film thickness.
[0180]
Membrane swelling speed T_1/2Can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating.
[0181]
The photosensitive material containing the emulsion of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains, for example, the above-described light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. . The swelling ratio of the back layer is preferably 150 to 500%.
[0182]
The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pp. 28-29, ibid. No. 18716, page 651, left column to right column; 307105, pages 880-881, and can be developed by a conventional method.
[0183]
The color developer used for the development processing of the light-sensitive material containing the emulsion of the present invention is preferably an alkaline aqueous solution mainly composed of an aromatic primary amine color developing agent. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N diethylaniline, 3-methyl -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl -Β-methoxyethylaniline, and sulfates, hydrochlorides, or p-toluenesulfonates of these. Of these, sulfate of 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline is particularly preferable. These compounds may be used in combination of two or more depending on the purpose.
[0184]
Color developers include, for example, pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It is common to include a development inhibitor or an antifogging agent. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catecholsulfonic acids; ethylene glycol, Organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines; dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity imparting Agents: Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid can be used. Examples of chelating agents include ethylenediaminetetraacetic acid, nitrile triacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N- Typical examples include trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.
[0185]
When the reversal process is performed, color development is usually performed after black and white development. This black-and-white developer includes, for example, dihydroxybenzenes such as hydroquinone, for example 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Known black-and-white developing agents can be used alone or in combination. The pH of these color developers and black-and-white developers is generally 9-12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 L or less per square meter of the light-sensitive material. By reducing the bromide ion concentration in the replenishing solution, 500 ml ( In the following, milliliters are also referred to as “mL”.) When reducing the replenishment amount, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing liquid with air.
[0186]
The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is,
Opening ratio = [contact area between treatment liquid and air (cm²)] ÷ [Volume of processing solution (cm³]]
The opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to a method of providing a shielding object such as a floating lid on the photographic processing liquid surface of the processing tank, a movable lid described in JP-A-1-82033 is used. Examples thereof include a slit developing method described in JP-A No. 63-216005. The reduction of the aperture ratio is preferably applied not only in both color development and black-and-white development but also in subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilization. Further, the replenishment amount can be reduced by using a means for suppressing the accumulation of bromide ions in the developer.
[0187]
The color development time is usually set between 2 and 5 minutes, but the processing time can be further shortened by setting the temperature and pH to a high value and using the color developing agent at a high concentration.
[0188]
The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleaching and fixing process) or may be performed individually. Further, in order to speed up the processing, a processing method of performing bleach-fixing processing after the bleaching processing may be used. Further, depending on the purpose, it is possible to carry out the treatment in two continuous bleach-fixing baths, the fixing treatment before the bleach-fixing treatment, or the bleaching treatment after the bleach-fixing treatment. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (III), peracids (especially sodium persulfate is suitable for a color negative film for movies), quinones and nitro compounds are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid. Complex salts with aminopolycarboxylic acids or complex salts with, for example, citric acid, tartaric acid and malic acid can be used. Of these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are the viewpoints of rapid processing and prevention of environmental pollution. To preferred. Furthermore, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) complex salts of aminopolycarboxylic acid is usually 4.0 to 8. However, the processing can be performed at a lower pH in order to speed up the processing.
[0189]
A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath, if necessary. Specific examples of useful bleach accelerators are described in the following specifications: for example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, and 2,059,988. JP-A-53-32736, 53-57831, 53-37418, 53-72623, 53-95630, 53-95631, 53-104232, 53-124424. 53-141623, 53-18426, Research Disclosure No. Compounds having mercapto groups or disulfide groups described in JP-A No. 17129 (July 1978); thiazolidine derivatives described in JP-A No. 51-14129; JP-B Nos. 45-8506, 52-20832 and 53 No. -32735, a thiourea derivative described in US Pat. No. 3,706,561, an iodide salt described in West German Patent No. 1,127,715 and JP-A No. 58-16235; West German Patent No. 966,410 No. 2,748,430; polyoxyethylene compounds described in JP-B No. 45-8836; other JP-A Nos. 49-40943, 49-59644, 53-94927 No., 54-35727, 55-26506, 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect. In particular, US Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53- The compounds described in Japanese Patent No. 95630 are preferred. Furthermore, the compounds described in US Pat. No. 4,552,884 are also preferable. These bleach accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when a color light-sensitive material for photography is bleach-fixed.
[0190]
In addition to the above compounds, the bleaching solution or the bleach-fixing solution preferably contains an organic acid for the purpose of preventing bleaching stains. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specific examples include acetic acid, propionic acid, and hydroxyacetic acid.
[0191]
Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Of these, thiosulfate is generally used, and ammonium thiosulfate is most widely used. Further, a combination of thiosulfate and, for example, thiocyanate, thioether compound, or thiourea is also preferable. As a preservative for a fixing solution or a bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.
[0192]
In the present invention, the fixing solution or bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, etc. It is preferable to add imidazoles in an amount of 0.1 to 10 mol / L.
[0193]
The total desilvering time is preferably as short as possible without causing desilvering failure. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved, and the occurrence of stain after the treatment is effectively prevented.
[0194]
In the desilvering step, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening the stirring include a method of causing a jet of a processing solution to collide with the emulsion surface of a photosensitive material described in JP-A-62-183460, and a rotating means in JP-A-62-183461. To increase the stirring effect. Furthermore, the photosensitive material is moved while the wiper blade provided in the solution is in contact with the emulsion surface, and the emulsion surface is turbulent to improve the stirring effect, and the circulation flow rate of the entire processing solution is increased. The method of letting it be mentioned. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution, and the fixing solution. The improvement in stirring is considered to speed up the supply of the bleaching agent and the fixing agent into the emulsion film and consequently increase the desilvering rate. Further, the above stirring improving means is more effective when a bleaching accelerator is used, and the acceleration effect can be remarkably increased or the fixing inhibiting action can be eliminated by the bleaching accelerator.
[0195]
An automatic developing machine used for developing a photosensitive material containing the emulsion of the present invention has the photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. Preferably it is. As described in JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the processing liquid from the pre-bath to the post-bath and is highly effective in preventing the performance deterioration of the processing liquid. Such an effect is particularly effective in shortening the processing time in each process and reducing the replenishment amount of the processing liquid.
[0196]
The silver halide color photographic light-sensitive material containing the emulsion of the present invention is generally subjected to a washing and / or stabilizing process after desilvering. The amount of water to be washed in the washing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the application, and further, for example, the temperature of the washing water, the number of washing tanks (number of stages), replenishment such as countercurrent and forward flow A wide range can be set according to the system and other various conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is as follows: Journal of the Society of Motion Picture and Television Engineers, Vol. 248 to 253 (May 1955).
[0197]
According to the multi-stage countercurrent system described in the above-mentioned document, the amount of water to be washed can be greatly reduced. However, bacteria are propagated due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, as described in JP-A-57-8542, for example, isothiazolone compounds, siabendazoles, chlorinated bactericides such as chlorinated sodium isocyanurate, and others such as benzotriazole, Hiroshi Horiguchi. "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan The disinfectant described in “Enamel Antibacterial Encyclopedia” (1986) can also be used.
[0198]
The pH of the washing water in the processing of the light-sensitive material containing the emulsion of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be variously set depending on, for example, the characteristics and application of the photosensitive material. In general, the washing water temperature and washing time are 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. A range is selected. Furthermore, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the water washing. In such stabilization treatment, all known methods described in JP-A-57-8543, 58-14834 and 60-220345 can be used.
[0199]
Further, a stabilization treatment may be further performed following the water washing treatment. Examples thereof include a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.
[0200]
The overflow liquid accompanying the washing and / or replenishment of the stabilizing liquid can be reused in other processes such as a desilvering process.
For example, in the processing using an automatic developing machine, when each of the above processing solutions is concentrated by evaporation, it is preferable to correct the concentration by adding water.
[0201]
The silver halide color photographic light-sensitive material containing the emulsion of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate them, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in US Pat. No. 3,342,597, for example, US Pat. No. 3,342,599, Research Disclosure No. 14,850 and No. No. 15,159, Schiff base type compounds, And aldol compounds described in US Pat. No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628.
[0202]
The silver halide color photographic material containing the emulsion of the present invention may incorporate various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development, if necessary. Typical compounds are described, for example, in JP-A Nos. 56-64339, 57-144547, and 58-115438.
[0203]
The various processing liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but the temperature is increased to accelerate the processing and shorten the processing time, or conversely, the temperature is lowered to achieve an improvement in image quality and stability of the processing solution. be able to.
[0204]
Further, silver halide light-sensitive materials containing the emulsion of the present invention are disclosed in US Pat. No. 4,500,626, JP-A-60-133449, 59-218443, 61-238056, European The present invention can also be applied to a photothermographic material described in Japanese Patent No. 210,660A2.
[0205]
The silver halide color photographic light-sensitive material containing the emulsion of the present invention is more effective when applied to a film unit with a lens described in JP-B-2-32615, JP-B-3-39784. It is easy to express and is effective.
[0206]
【Example】
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples.
[0207]
Example 1
Silver halide seed emulsions and silver halide emulsions Em-A1 to Em-A11 were prepared by the following production method.
(Preparation of seed emulsion)
The method for preparing silver halide tabular grains described in Example 2 of JP-A-10-293372 was referred to. 1 L of a dispersion medium solution containing 0.38 g of KBr and 0.4 g of low molecular weight gelatin (weight average molecular weight of about 15000) was kept at 40 ° C. in a reaction vessel, and 0.29 mol / L AgNO 2 was stirred while stirring.₃20 mL each of the aqueous solution and 0.29 mol / L KBr aqueous solution were added simultaneously over 40 seconds. After the addition, 22 mL of 10% KBr solution was added, and the temperature was raised to 75 ° C. After the temperature rise, an aqueous gelatin solution (60 ° C.) consisting of 35 g of trimellitated gelatin and 250 mL of water was added to the dispersion medium solution. At this time, the pH was adjusted to 6.0. After this, 1.2 mol / L AgNO₃An aqueous solution and a 1.2 mol / L KBr aqueous solution were added simultaneously. At this time, AgNO added₃The silver iodide fine grains were added at the same time so that the silver iodide content was 4 mol%. At this time, the pBr of the dispersion medium was kept at 2.64. After washing with water, gelatin was added to adjust the pH to 5.7, pAg, 8.8, the mass in terms of silver per kg of emulsion of 131.8 g, and the gelatin mass of 64.1 g to obtain a seed emulsion. In the obtained emulsion, 97% of the total projected area is occupied by tabular grains, and the average silver iodide content of the tabular grains is 4 mol%, the average sphere equivalent diameter is 0.6 μm, and the average aspect ratio. The ratio was 29.
[0208]
(Em-A1)
<Formation of host tabular grains>
1211 mL of an aqueous solution containing 46 g of trimellitated gelatin having a trimellitization rate of 97% and 1.7 g of KBr was kept at 75 ° C. and vigorously stirred. After adding 151 g of the seed emulsion described above, 0.3 g of modified silicon oil (product of Nippon Unicar Co., Ltd., L7602) was added. H₂SO₄After adjusting pH to 5.5, AgNO₃7.0 g of an aqueous solution containing 4 g of KI and a mixed aqueous solution of KBr and KI containing 4 mol% of KI were added over 6 minutes by accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate by the double jet method. did. At this time, the silver potential was kept at +0 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, AgNO2 was added to the stirring device installed outside the reaction vessel.₃172 mL of an aqueous solution containing 170 g of KBr and 762 mL of an aqueous solution containing 76.2 g of gelatin having a KBr of 114.2 g, KI of 6.6 g, and a weight average molecular weight of about 20,000 were added simultaneously. While preparing silver fine particles (average sphere equivalent diameter: 0.016 μm), silver iodobromide fine particles were added to the reaction vessel over 120 minutes. At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode. AgNO₃And an aqueous solution containing 4 mol% of KI and a mixed solution of KBr and KI containing 4 mol% were added over 30 minutes by the double jet method. At this time, the silver potential was kept at +20 mV for the first 20 minutes and +120 mV for the remaining 10 minutes with respect to the saturated calomel electrode.
[0209]
<Epitaxial formation>
Subsequent to <Formation of host tabular grains>, after cooling to 50 ° C., 138 mL of 0.3% KI aqueous solution was added, and sensitizing dyes 1, 2 and 3 were added. Then, after stirring for 20 minutes at 50 ° C., AgNO₃133.1 mL of an aqueous solution containing 21.3 g, 150 mL of an aqueous solution containing 4.38 g of NaCl and 5.95 g of KBr, and a solution containing 0.005 mol of silver iodide fine particles were added simultaneously. At this time, AgNO to be added₃8.0 × 10 to 1 mol of^-4mol K₄[RuCN₆] Was present. Thereafter, sensitizing dyes 1, 2 and 3 were added. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C. After adding compounds 1 and 2, the temperature was raised to 53 ° C. After addition of sensitizing dyes 1, 2 and 3, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold (I)) tetrafluoroborate, thiosulfuric acid Sodium, N, N-dimethylselenourea was added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are mixed at 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount. Table 1 shows the characteristics of the obtained silver halide grains.
[0210]
[Chemical 2]

[0211]
[Chemical 3]

[0212]
[Formula 4]

[0213]
[Chemical formula 5]

[0214]
[Chemical 6]

[0215]
[Chemical 7]

[0216]
[Chemical 8]

[0217]
(Em-A2)
<Formation of host tabular grains>
This was carried out in the same manner as in <Em-A1> <Formation of host tabular grains>.
[0218]
<Epitaxial formation>
Subsequent to <Formation of host tabular grains>, after cooling to 50 ° C., 138 mL of 0.3% KI aqueous solution was added, and sensitizing dyes 1, 2 and 3 were added. Thereafter, the mixture was stirred for 20 minutes at 50 ° C., and then 140 mL of an aqueous solution containing 8.05 g of NaCl was added. Then AgNO₃133.1 mL of an aqueous solution containing 21.3 g of was added. At this time, AgNO to be added₃8.0 × 10 to 1 mol of^-4mol K₄[RuCN₆] Was present. Immediately thereafter, 19.9 mL of an aqueous solution containing 5.96 g of KBr and a solution containing 0.005 mol of silver iodide fine particles were added. Thereafter, sensitizing dyes 1, 2 and 3 were added. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C. After adding compounds 1, 2 and 3, the temperature was raised to 53 ° C. After addition of sensitizing dyes 1, 2 and 3, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold (I)) tetrafluoroborate, thiosulfuric acid Sodium, N, N-dimethylselenourea was added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are mixed at 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount. Table 1 shows the characteristics of the obtained silver halide grains.
[0219]
(Em-A3)
<Formation of host tabular grains>
This was carried out in the same manner as in <Em-A1> <Formation of host tabular grains>.
[0220]
<Epitaxial formation>
Subsequent to <Formation of host tabular grains>, after cooling to 50 ° C., 138 mL of 0.3% KI aqueous solution was added, and sensitizing dyes 1, 2 and 3 were added. Thereafter, the mixture was stirred for 20 minutes at 50 ° C., and then 140 mL of an aqueous solution containing 8.05 g of NaCl was added. Then AgNO₃A solution containing 133.1 mL of an aqueous solution containing 21.3 g, 19.9 mL of an aqueous solution containing 5.96 g of KBr, and 0.005 mol of silver iodide fine particles was added. At this time, AgNO to be added₃8.0 × 10 to 1 mol of^-4mol K₄[RuCN₆] Was present. Thereafter, sensitizing dyes 1, 2 and 3 were added. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C. After adding compounds 1 and 2, the temperature was raised to 53 ° C. After addition of sensitizing dyes 1, 2 and 3, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold (I)) tetrafluoroborate, thiosulfuric acid Sodium, N, N-dimethylselenourea was added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are mixed at 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
Table 1 shows the characteristics of the obtained silver halide grains.
[0221]
(Em-A4)
<Formation of host tabular grains>
This was carried out in the same manner as in <Em-A1> <Formation of host tabular grains>.
[0222]
<Epitaxial formation>
Subsequent to <Formation of host tabular grains>, after cooling to 50 ° C., 138 mL of 0.3% KI aqueous solution was added, and sensitizing dyes 1, 2 and 3 were added. Thereafter, the mixture was stirred for 20 minutes at 50 ° C., and then 140 mL of an aqueous solution containing 8.05 g of NaCl was added. Then AgNO₃79.9m of an aqueous solution containing 12.8g of was added. At the same time, the AgNO 2 is mixed in a mixing device separate from the reaction vessel.₃Of silver bromide (average sphere equivalent diameter: 0.031 μm) emulsion prepared by simultaneously adding 53.1 mL of 8.5 g of aqueous solution, 3.5 g of gelatin and 70 mL of aqueous solution containing 6.55 g of KBr Added to. At this time, AgNO to be added₃8.0 × 10 to 1 mol of^-4mol K₄[RuCN₆] Was present. Thereafter, sensitizing dyes 1, 2 and 3 were added. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C. After adding compounds 1 and 2, the temperature was raised to 53 ° C. After further addition of sensitizing dyes 1, 2 and 3, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold (I)) tetrafluoroborate, thio Sodium sulfate and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are mixed at 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
Table 1 shows the characteristics of the obtained silver halide grains.
[0223]
(Em-A5)
<Formation of host tabular grains>
This was carried out in the same manner as in <Em-A1> <Formation of host tabular grains>.
[0224]
<Epitaxial formation>
Subsequent to <Formation of host tabular grains>, after cooling to 50 ° C., 138 mL of 0.3% KI aqueous solution was added, and sensitizing dyes 1, 2 and 3 were added. Thereafter, the mixture was stirred for 20 minutes at 50 ° C., and then 140 mL of an aqueous solution containing 8.05 g of NaCl was added. Then AgNO₃79.9m of an aqueous solution containing 12.8g of was added. Thereafter, AgNO 2 is mixed in a mixing apparatus separate from the reaction vessel.₃Of silver bromide (average sphere equivalent diameter: 0.031 μm) emulsion prepared by simultaneously adding 53.1 mL of 8.5 g of aqueous solution, 3.5 g of gelatin and 70 mL of aqueous solution containing 6.55 g of KBr Added to. At this time, AgNO to be added₃8.0 × 10 to 1 mol of^-4mol K₄[RuCN₆] Was present. Thereafter, sensitizing dyes 1, 2 and 3 were added. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C. After adding compounds 1 and 2, the temperature was raised to 53 ° C. After further addition of sensitizing dyes 1, 2 and 3, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold (I)) tetrafluoroborate, thio Sodium sulfate and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are mixed at 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
Table 1 shows the characteristics of the obtained silver halide grains.
[0225]
(Em-A6)
<Formation of host tabular grains>
This was carried out in the same manner as in <Em-A1> <Formation of host tabular grains>.
[0226]
<Epitaxial formation>
Subsequent to <Formation of host tabular grains>, after cooling to 50 ° C., 138 mL of 0.3% KI aqueous solution was added, and sensitizing dyes 1, 2 and 3 were added. Thereafter, the mixture was stirred for 20 minutes at 50 ° C., and then 140 mL of an aqueous solution containing 8.05 g of NaCl was added. Then AgNO₃79.9 mL of an aqueous solution containing 12.8 g of was added. At this time, AgNO to be added₃8.0 × 10 to 1 mol of^-4mol K₄[RuCN₆] Was present. Thereafter, sensitizing dyes 1, 2 and 3 were added. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C. After adding compounds 1 and 2, the temperature was raised to 53 ° C. Thereafter, silver iodochlorobromide fine particles (in terms of silver amount, 0.05 mol, average silver chloride content of 10 mol%, average silver iodide content of 5 mol%, average sphere equivalent diameter: 0.11 μm) were added. After further addition of sensitizing dyes 1, 2 and 3, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold (I)) tetrafluoroborate, thio Sodium sulfate and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are mixed at 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
Table 1 shows the characteristics of the obtained silver halide grains.
[0227]
(Em-A7)
<Formation of host tabular grains>
This was carried out in the same manner as in <Em-A1> <Formation of host tabular grains>.
[0228]
<Epitaxial formation>
Subsequent to <Formation of host tabular grains>, after cooling to 50 ° C., 138 mL of 0.3% KI aqueous solution was added, and sensitizing dyes 1, 2 and 3 were added. Thereafter, the mixture was stirred for 20 minutes at 50 ° C., and then 140 mL of an aqueous solution containing 8.05 g of NaCl was added. Then AgNO₃79.9 mL of an aqueous solution containing 12.8 g of was added. At the same time, silver iodochlorobromide fine particles (0.05 mol, average silver chloride content 10 mol%, average silver iodide content 5 mol%, average sphere equivalent diameter: 0.11 μm) prepared in advance were prepared. Added to the reaction vessel. At this time, AgNO to be added₃8.0 × 10 to 1 mol of^-4mol K₄[RuCN₆] Was present. Thereafter, sensitizing dyes 1, 2 and 3 were added. Thereafter, this emulsion was desalted by the ultrafiltration method described in JP-A-2002-122952 and in Example 2, and then gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C. After adding compounds 1 and 2, the temperature was raised to 53 ° C. After further addition of sensitizing dyes 1, 2 and 3, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold (I)) tetrafluoroborate, thio Sodium sulfate and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are mixed at 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
Table 1 shows the characteristics of the obtained silver halide grains.
[0229]
(Em-A8)
<Formation of host tabular grains>
This was carried out in the same manner as in <Em-A1> <Formation of host tabular grains>.
[0230]
<Epitaxial formation>
Subsequent to <Formation of host tabular grains>, after cooling to 50 ° C., 138 mL of 0.3% KI aqueous solution was added, and sensitizing dyes 1, 2 and 3 were added. Thereafter, the mixture was stirred for 20 minutes at 50 ° C., and then 140 mL of an aqueous solution containing 8.05 g of NaCl was added. Then AgNO₃79.9 mL of an aqueous solution containing 12.8 g of was added. At the same time, silver iodochlorobromide fine particles (0.05 mol, average silver chloride content 10 mol%, average silver iodide content 5 mol%, average sphere equivalent diameter: 0.11 μm) prepared in advance were prepared. Added to the reaction vessel. At this time, AgNO to be added₃8.0 × 10 to 1 mol of^-4mol K₄[RuCN₆] Was present. Thereafter, sensitizing dyes 1, 2 and 3 were added. After washing with water, gelatin was added to adjust the pH to 5.8 and pAg 8.7 at 40 ° C. After adding compounds 1 and 2, the temperature was raised to 53 ° C. After further addition of sensitizing dyes 1, 2 and 3, potassium thiocyanate, bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold (I)) tetrafluoroborate, thio Sodium sulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are mixed at 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
Table 1 shows the characteristics of the obtained silver halide grains.
[0231]
(Em-A9)
An emulsion was prepared in the same manner as Em-A8. After adding compounds 1 and 2, the temperature was raised to 60 ° C. After the addition of sensitizing dyes 1, 2 and 3, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are added at a rate of 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0232]
(Em-A10)
An emulsion was prepared in the same manner as Em-A8. After adding compounds 1 and 2, the temperature was raised to 60 ° C. After addition of sensitizing dyes 1, 2 and 3, potassium thiocyanate, chloroauric acid, carboxymethyltrimethylthiourea, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are added at a rate of 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0233]
(Em-A11)
An emulsion was prepared in the same manner as Em-A8. After adding compounds 1 and 2, the temperature was raised to 60 ° C. After addition of sensitizing dyes 1, 2 and 3, potassium thiocyanate, chloroauric acid, carboxymethyltrimethylthiourea and N, N-dimethylselenourea were added for optimum chemical sensitization. 1 × 10 for compound 5 during chemical sensitization^-4mol / mol Ag was added. Compound 3 and compound 4 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound are added at a rate of 10 per mole of silver halide.^-1To 10^-8It means that it was selected from the range of molar addition amount.
[0234]
[Chemical 9]

[0235]
Table 1 shows the characteristics of the silver halide emulsions Em-A1 to A11 thus obtained.
[0236]
[Table 1]

[0237]
After each emulsion was dissolved for 30 minutes at 40 ° C. on a cellulose triacetate film support provided with an undercoat layer, the emulsions Em-A1 to A11 were coated under the coating conditions as shown below. 101-111 were created.
[0238]

[0239]
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[0240]
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[0241]
These samples were subjected to hardening for 14 hours under conditions of 40 ° C. and 70% relative humidity. Thereafter, exposure was performed for 1/100 second through a continuous wedge, and the photographic sensitivity was determined by measuring the density of a sample subjected to the following development processing with a green filter. Moreover, the granularity was calculated | required.
Development was performed according to the following process using an automatic processor FP-362B manufactured by Fuji Photo Film Co., Ltd.
[0242]
The treatment process and the treatment liquid composition are shown below.

* Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1)
The stabilizing liquid is a countercurrent system from (3) → (2) → (1), and the fixing liquid is also connected from (2) to (1) by countercurrent piping. Further, 15 mL of the replenishment amount corresponding to the tank liquid of the stabilizing liquid (2) is flowing into the fixing liquid (2). Further, the color developer is replenished as a total of 15 mL by dividing the color developer (A) replenisher and color developer (B) replenisher of the following formulation into 12 mL and 3 mL, respectively, corresponding to the replenishment amount. The amount of the developer brought into the bleaching process, the amount of the bleaching solution brought into the fixing step, and the amount of the fixing solution brought into the water washing step were all 2.0 mL per 1.1 mm width of the photosensitive material 35 mm. The crossover time is 6 seconds, and this time is included in the processing time of the previous process.
[0243]
The composition of the treatment liquid is shown below.

The tank solution shows the composition after mixing the (color developer (A)).
[0245]

[0246]

[0247]

[0248]
Table 2 shows the results of evaluation by the above method. The sensitivity is expressed as a relative value of the reciprocal of the exposure amount necessary to reach a fog density plus 0.2.
[0249]
[Table 2]

[0250]
(Example 2)
The effect of the present invention in a multilayer color light-sensitive material is shown.
1) Support
The support used in this example was prepared by the following method.
100 parts by mass of polyethylene-2,6-naphthalate polymer and Tinuvin P.I. 326 (manufactured by Ciba-Geigy Ciba-Geigy) was dried, melted at 300 ° C, extruded from a T-die, and stretched 3.3 times at 140 ° C, followed by 130 ° C. The film was stretched by 3.3 times and further heat-fixed at 250 ° C. for 6 seconds to obtain a PEN (polyethylene naphthalate) film having a thickness of 90 μm. The PEN film has a blue dye, a magenta dye, and a yellow dye (public techniques: I-1, I-4, I-6, I-24, I-26, I- 27, II-5) was added in an appropriate amount. Furthermore, it was wound around a stainless steel core having a diameter of 20 cm to give a thermal history of 110 ° C. and 48 hours, thereby providing a support that is difficult to curl.
[0251]
2) Application of undercoat layer
The support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides, and then gelatin 0.1 g / m on each side.²Sodium α-sulfodi-2-ethylhexyl succinate 0.01 g / m², Salicylic acid 0.04 g / m²P-chlorophenol 0.2 g / m², (CH₂= CHSO₂CH₂CH₂NHCO)₂CH₂0.012 g / m², Polyamide-epichlorohydrin polycondensate 0.02 g / m²Apply a primer solution (10 mL / m², Using a bar coater), an undercoat layer was provided on the high-temperature surface side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).
[0252]
3) Coating the back layer
An antistatic layer having the following composition, a magnetic recording layer, and a sliding layer were coated as a back layer on one surface of the support after the undercoating.
3-1) Application of antistatic layer
The specific resistance of the tin oxide-antimony oxide composite having an average particle size of 0.005 μm is 0.2 g / m of a dispersion of fine particle powder (secondary aggregate particle size of about 0.08 μm) of 5 Ω · cm.², Gelatin 0.05g / m², (CH₂= CHSO₂CH₂CH₂NHCO)₂CH₂0.02g / m², Poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.005 g / m²And coated with resorcin.
[0253]
3-2) Coating of magnetic recording layer
Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) (specific surface area 43 m²/ G, long axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 Am²/ Kg, Fe⁺²/ Fe⁺³= 6/94, the surface is treated with aluminum oxide silicon oxide with 2% by mass of iron oxide) 0.06 g / m²Diacetylcellulose 1.2 g / m²(Iron oxide was dispersed with an open kneader and sand mill)₂H₅C (CH₂OCONH-C₆H₃(CH₃) NCO)₃0.3 g / m²Was coated with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. 10 mg each of abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) as a matting agent / M²It added so that it might become. Drying was performed at 115 ° C. for 6 minutes (all rollers and conveyors in the drying zone were 115 ° C.). D of magnetic recording layer with X-light (blue filter)^BThe increase in color density is about 0.1, and the saturation magnetization moment of the magnetic recording layer is 4.2 Am²/ Kg, coercive force 7.3 × 10⁴A / m, the squareness ratio was 65%.
[0254]
3-3) Preparation of sliding layer
Diacetylcellulose (25mg / m²), C₆H₁₃CH (OH) C₁₀H₂₀COOC₄₀H₈₁(Compound a, 6 mg / m²) / C₅₀H₁₀₁O (CH₂CH₂O)₁₆H (Compound b, 9 mg / m²) The mixture was applied. This mixture was prepared by melting at 105 ° C. in xylene / propylene monomethyl ether (1/1), pouring and dispersing in propylene monomethyl ether at room temperature (10-fold amount), and then dispersing the dispersion ( The average particle size was 0.01 μm) and then added. 15 mg / m each of aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (polymerization degree 15) oxyethylenepropyloxytrimethoxysilane (15% by mass) as a matting agent²It added so that it might become. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 115 ° C.). The sliding layer has a dynamic friction coefficient of 0.06 (5 mmφ stainless hard ball, load of 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clipping method), and the dynamic friction coefficient of the emulsion surface and sliding layer described later is also 0.12. Excellent characteristics.
[0255]
4) Coating of photosensitive layer
Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in layers to prepare samples 201 to 211 as color negative photosensitive materials. That is, samples 201 to 211 were prepared by replacing the silver chloroiodobromide emulsion Em-A1 in the sixth layer with the emulsions Em-A1 to Em-A11, respectively.
[0256]
(Composition of photosensitive layer)
The main materials used in each layer are classified as follows:
ExC: Cyan coupler UV: UV absorber
ExM: Magenta coupler HBS: High boiling point organic solvent
ExY: Yellow coupler H: Gelatin hardener
(Specific compounds are described below, followed by a numerical value followed by a chemical formula.)
The number corresponding to each component is g / m²The coating amount expressed in units is shown. For silver halide, the coating amount in terms of silver is shown.
[0257]

[0258]
Second layer (second antihalation layer)
Black colloidal silver silver 0.066
Gelatin: 0.407
ExM-1 0.05050
ExF-1 2.0 2.0 × 10^-3
HBS-1 0.074
Solid disperse dye ExF-2 0.015
Solid disperse dye ExF-3 0.020
[0259]

[0260]
4th layer (low sensitivity red sensitive emulsion layer)
Silver iodobromide emulsion Em-M Silver 0.065
Silver iodobromide emulsion Em-N Silver 0.100
Silver iodobromide emulsion Em-O Silver 0.158
ExC-1 0.10.109
ExC-3 0.044
ExC-4 0.072
ExC-5: 0.011
ExC-6 0.003 0.00
ExC-8 0.03 0.0
Cpd-2: 0.025
Cpd-4: 0.025
HBS-1 0.10.17
Gelatin 0.80
[0261]
5th layer (medium sensitivity red emulsion layer)
Silver iodobromide emulsion Em-K silver 0.21
Silver iodobromide emulsion Em-L Silver 0.62
ExC-1 0.10.14
ExC-2 0.026
ExC-3 0.020
ExC-4 0.10.12
ExC-5: 0.016
ExC-6 0.007 0.00
ExC-8 0.03 0.0
Cpd-2: 0.036
Cpd-4: 0.028
HBS-1 0.10.16
Gelatin Gr 1.18
[0262]
6th layer (high-sensitivity red-sensitive emulsion layer)
Silver chloroiodobromide emulsion (Em-A1 of Example 1) Silver 1.67
ExC-1 0.18 0.18
ExC-3 0.07
ExC-6 excel 0.047
Cpd-2: 0.046
Cpd-4: 0.077
HBS-1 0.37
Gelatin 2.5.12
[0263]
7th layer (intermediate layer)
Cpd-1: 0.089
Solid disperse dye ExF-4 0.030
HBS-1 0.050
Polyethyl acrylate latex 0.83
Gelatin 0.84
[0264]
Eighth layer (Multilayer effect donor layer (layer that gives a multilayer effect to the red-sensitive layer))
Silver iodobromide emulsion Em-E Silver 0.560
Cpd-4: 0.030
ExM-2, 0.096
ExM-3 0.028 0.028
ExY-1 0.031
ExG-1 <0.006>
HBS-1 0.00.085
HBS-3 0.003 0.00
Gelatin 0.58
[0265]
9th layer (low sensitivity green emulsion layer)
Silver iodobromide emulsion Em-G Silver 0.39
Silver iodobromide emulsion Em-H silver 0.28
Silver iodobromide emulsion Em-I Silver 0.35
ExM-2 0.36
ExM-3 0.045 0.045
ExG-1 0.005 0.00
HBS-1 0.20.28
HBS-2: 0.01 0.01
S-2 0.20.27
Gelatin 1.39 1.39
[0266]
10th layer (medium sensitive green sensitive emulsion layer)
Silver iodobromide emulsion Em-F silver 0.20
Silver iodobromide emulsion Em-G Silver 0.25
ExC-6 0.009 0.00
ExC-8, 0.01, 0.01
ExM-2 0.031
ExM-3 excel 0.029
ExY-1 0.006 0.00
ExM-4 0.028
ExG-1 0.005 0.00
HBS-1 0.00.064
HBS-2 2.1 x10^-3
Gelatin 0.44
[0267]
11th layer (high sensitivity green emulsion layer)
Emulsion Em-P Silver 1.200
ExC-6 0.004
ExC-8, 0.01, 0.01
ExM-1 .0.016
ExM-3 excel 0.036
ExM-4 0.020
ExM-5, 0.004
ExY-5, 0.008
ExM-2 excel 0.013
Cpd-4: 0.007
HBS-1 0.18 0.18
Polyethyl acrylate latex 0.099
Gelatin 1.1.1
[0268]
12th layer (yellow filter layer)
Yellow colloidal silver silver 0.047
Cpd-1 0.16 0.16
Solid dispersion dye ExF-5 0.010
Solid disperse dye ExF-6 0.010
HBS-1 0.00.082
Gelatin 1.057
[0269]
13th layer (low sensitivity blue-sensitive emulsion layer)
Em-B Bonus Silver 0.18
Em-C, Silver, 0.20
Em-D: Silver 0.07
ExC-1 0.041
ExY-1 0.035 0.035
ExY-2 0.71 0.71
ExY-3 0.10 0.10
ExY-4 0.005 0.00
Cpd-2 0.10 0.10
Cpd-3 4.0 4.0 × 10^-3
HBS-1 0.20.24
Gelatin 4.11
[0270]
14th layer (high sensitivity blue-sensitive emulsion layer)
Em-A, Silver 0.75
ExC-1 excel 0.013
ExY-2 0.31
ExY-3 0.05
ExY-6 excel 0.062
Cpd-2: 0.075
Cpd-3 1.0 1.0 × 10 Cpd-3^-3
HBS-1 0.10 0.10
Gelatin: 0.91
[0271]

[0272]
16th layer (second protective layer)
H-1 0.40 0.4
B-1 (1.7 μm diameter) 5.0 x 10^-2
B-2 (1.7 μm diameter) 0.15
B-3 0.05 0.05
S-1 0.20.20
Gelatin 0.75 0.75
[0273]
Furthermore, W-1 to W-6, B-4 to B-6 are appropriately added to each layer for the purpose of improving storage stability, processability, pressure resistance, antifungal / antibacterial properties, antistatic properties, and coating properties. , F-1 to F-17, and iron, lead, gold, platinum, palladium, iridium, ruthenium, and rhodium salts.
Table 3 shows the characteristics of the silver halide emulsions Em-A to P. These emulsions are based on the emulsion preparation methods Em-A to P described in Examples of JP-A No. 2001-92057 and Em-A to O described in Examples of JP-A No. 2001-92059. The particle formation conditions are appropriately changed and prepared.
[0274]
[Table 3]

[0275]
Preparation of organic solid disperse dyes
The following ExF-3 was dispersed by the following method. That is, 21.7 mL of water and 3 mL of 5% aqueous p-octylphenoxyethoxyethoxyethane sulfonate and 0.5 g of 5% aqueous p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700 mL pot mill. Then, 5.0 g of dye ExF-3 and 500 mL of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. A BO-type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After dispersion, the contents were taken out and added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles was 0.44 μm.
[0276]
Similarly, a solid dispersion of ExF-4 was obtained. The average particle size of the fine dye particles was 0.24 μm. ExF-2 was dispersed by the microprecipitation dispersion method described in Example 1 of EP 549,489A. The average particle size was 0.06 μm.
[0277]
A solid dispersion of ExF-6 was dispersed by the following method.
To 2800 g of ExF-6 wet cake containing 18% of water, 376 g of 4000 g of water and a 3% solution of W-2 was added and stirred to obtain a slurry of ExF-6 having a concentration of 32%. Next, 1700 mL of zirconia beads having an average particle diameter of 0.5 mm was filled in Ultraviscomil (UVM-2) manufactured by Imex Co., Ltd., and pulverized for 8 hours through the slurry at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 L / min. did. The average particle size was 0.45 μm.
The compounds used for forming each of the above layers are as shown below.
[0278]
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[0279]
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[0280]
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[0281]
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[0282]
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[0283]
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[0284]
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[0285]
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[0286]
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[0287]
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[0288]
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[0289]
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[0290]
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[0291]
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[0292]
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[0293]
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[0294]
The method for determining the specific photosensitivity in the present invention is in accordance with JIS K 7614-1981. The difference is that the development processing is completed within 30 minutes to 6 hours after exposure for sensitometry, and the development processing is as follows. The method is based on the Fuji color processing method CN-16. Others are substantially the same as the measurement method described in JIS.
[0295]
The processing method was the same as the development method described in Example 1. Test conditions, exposure, density measurement, and determination of specific photographic sensitivity were the same as those described in JP-A-63-226650.
[0296]
The said process was performed with respect to the samples 201-211. Photographic performance was evaluated by measuring the density of the processed sample with a red filter. Table 4 shows the obtained results.
[0297]
[Table 4]

[0298]
From Table 4, the sample using the emulsion of the present invention achieved high sensitivity while improving the graininess compared to the comparative sample.
[Brief description of the drawings]
FIG. 1 is a schematic plan view.
FIG. 2 is a schematic sectional view taken along line (a)-(b) in FIG.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Tabular grain, 2 ... Epitaxial junction part, 3 ... Host tabular grain part,
A1: Silver bromide content less than 40 mol%
A2: Silver bromide content 40 mol% or more

Claims (1)

Silver halide emulsion containing a dispersion medium and silver halide grains, wherein 50% or more of the total projected area of the silver halide grains satisfies the following (a), (b), and (c) A silver halide emulsion characterized in that it is occupied by
(A) a silver halide tabular grain whose main plane is the (111) plane; (b) an epitaxial junction is formed in at least one of the corners of the tabular grain; and (c) the epitaxial junction is an odor. When the silver halide content is divided into a part (A1) having a silver bromide content of less than 40 mol% and a part (A2) having a silver bromide content of 40 mol% or more, the A1 part exists inside the epitaxial junction and Does not exist

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