JP4226795B2 - Silver halide emulsion and silver halide photographic light-sensitive material - Google Patents

Description

【００６０】
【化２】

【００６１】
一般式（Ｉ）で表される化合物は、公知の方法、例えば、インオーガニック・アンド・ニュークリア・ケミストリー・レターズ（ＩＮＯＲＧ．ＮＵＣＬ．ＣＨＥＭ．ＬＥＴＴＥＲＳＶＯＬ．１０、６４１頁、１９７４年）、トランジションメタル・ケミストリー（ＴｒａｎｓｉｔｉｏｎＭｅｔ．Ｃｈｅｍ．１，２４８頁、１９７６年）、アクタ・クリスタログラフィカ（Ａｃｔａ．Ｃｒｙｓｔ．Ｂ３２、３３２１頁、１９７６年）、特開平８−６９０７５号、特公昭４５−８８３１号、欧州特許９１５３７１Ａ１号、特開平６−１１７８８号、特開平６−５０１７８９号、特開平４−２６７２４９号、及び、特開平９−１１８６８５号等を参考にして合成できる。
【００６２】
次に、一般式（Ｉ）で表される化合物の具体例を示すが、本発明はこれらに限定されない。
【００６３】
【化３】

【００６４】
【化４】

【００６５】
【化５】

【００６６】
本発明における金増感は、通常、金増感剤を添加し、高温（好ましくは、４０℃以上）で乳剤を一定時間攪拌する事により行われる。金増感剤の添加量は、種々の条件により異なるが、目安としてはハロゲン化銀１モル当たり１×１０^-7モル以上１×１０^-4モル以下が好ましい。
【００６７】
本発明において金増感剤としては、以上の化合物以外に、通常用いられる金化合物（例えば、塩化金酸塩、カリウムクロロオーレート、オーリックトリクロライド、カリウムオーリックチオシアネート、カリウムヨードオーレート、テトラシアノオーリックアシッド、アンモニウムオーロチオシアネート、ピリジルトリクロロゴールド等）を併用することができる。
【００６８】
本発明のハロゲン化銀乳剤は、金増感以外に他の化学増感を併用することができる。併用しうる化学増感法としては、硫黄増感、セレン増感、テルル増感、金以外の貴金属増感、あるいは還元増感等を用いることができる。化学増感に用いられる化合物については、特開昭６２−２１５２７２号の第１８頁右下欄から第２２頁右上欄に記載のものが好ましく用いられる。
【００６９】
本発明のハロゲン化銀乳剤には、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する、あるいは写真性能を安定化させる目的で種々の化合物あるいはそれ等の前駆体を添加することができる。これらの化合物の具体例は、特開昭６２−２１５２７２号公報明細書の第３９頁〜第７２頁に記載のものが好ましく用いられる。更にＥＰ０４４７６４７号に記載された５−アリールアミノ−１，２，３，４−チアトリアゾール化合物（該アリール残基には少なくとも一つの電子吸引性基を持つ）も好ましく用いられる。
【００７０】
また、本発明において、ハロゲン化銀乳剤の保存性を高めるため、特開平１１−１０９５７６号公報に記載のヒドロキサム酸誘導体、特開平１１−３２７０９４号公報に記載のカルボニル基に隣接して、両端がアミノ基もしくはヒドロキシル基が置換した二重結合を有す環状ケトン類（特に一般式（Ｓ１）で表されるもので、段落番号００３６〜００７１は本願の明細書に取り込むことができる。）、特開平１１−１４３０１１号公報に記載のスルホ置換のカテコールやハイドロキノン類（例えば、４，５−ジヒドロキシ−１，３−ベンゼンジスルホン酸、２，５−ジヒドロキシ−１，４−ベンゼンジスルホン酸、３，４−ジヒドロキシベンゼンスルホン酸、２，３−ジヒドロキシベンゼンスルホン酸、２，５−ジヒドロキシベンゼンスルホン酸、３，４，５−トリヒドロキシベンゼンスルホン酸及びこれらの塩など）、米国特許第５，５５６，７４１号明細書の一般式（Ａ）で表されるヒドロキシルアミン類（米国特許第５，５５６，７４１号の第４欄の第５６行〜第１１欄の第２２行の記載は本願においても好ましく適用され、本願の明細書の一部として取り込まれる）、特開平１１−１０２０４５号公報の一般式（Ｉ）〜（III）で表される水溶性還元剤は本発明においても好ましく使用される。
【００７１】
また、本発明のハロゲン化銀乳剤には、所望の光波長域に感光性を示す、いわゆる分光感度を付与する目的で、分光増感色素を含有させることができる。青、緑、赤領域の分光増感に用いられる分光増感色素としては例えば、Ｆ．Ｍ．Ｈａｒｍｅｒ著 Ｈｅｔｅｒｏｃｙｃｌｉｃ ｃｏｍｐｏｕｎｄｓ−Ｃｙａｎｉｎｅｄｙｅｓ ａｎｄ ｒｅｌａｔｅｄ ｃｏｍｐｏｕｎｄｓ （Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ ［Ｎｅｗ Ｙｏｒｋ，Ｌｏｎｄｏｎ］ 社刊１９６４年）に記載されているものを挙げることができる。具体的な化合物の例ならびに分光増感法は、前出の特開昭６２−２１５２７２号公報の第２２頁右上欄〜第３８頁に記載のものが好ましく用いられる。また、特に塩化銀含有率の高いハロゲン化銀乳剤粒子の赤感光性分光増感色素としては特開平３−１２３３４０号公報に記載された分光増感色素が安定性、吸着の強さ、露光の温度依存性等の観点から非常に好ましい。
【００７２】
これらの分光増感色素の添加量は場合に応じて広範囲にわたり、ハロゲン化銀１モル当り、０．５×１０^-6モル〜１．０×１０^-2モルの範囲が好ましい。更に好ましくは、１．０×１０^-6モル〜５．０×０^-3モルの範囲である。
【００７３】
次に、本発明のハロゲン化銀写真感光材料について説明する。
本発明のハロゲン化銀写真感光材料は黒白でもカラーでも構わないが、好ましくは、ハロゲン化銀カラー写真感光材料に本発明のハロゲン化銀乳剤が使用される。
本発明のハロゲン化銀乳剤が好ましく用いられるハロゲン化銀カラー写真感光材料（以下、単に「感光材料」という場合がある）は、支持体上に、イエロー色素形成カプラーを含有するハロゲン化銀乳剤層と、マゼンタ色素形成カプラーを含有するハロゲン化銀乳剤層と、シアン色素形成カプラーを含有するハロゲン化銀乳剤層とをそれぞれ少なくとも一層有するハロゲン化銀カラー写真感光材料において、前記ハロゲン化銀乳剤層のうち少なくとも一層が、本発明のハロゲン化銀乳剤を含有することを特徴とする。本発明において、前記イエロー色素形成カプラーを含有するハロゲン化銀乳剤層はイエロー発色層として、前記マゼンタ色素形成カプラーを含有するハロゲン化銀乳剤層はマゼンタ発色層として、及び前記シアン色素形成カプラーを含有するハロゲン化銀乳剤層はシアン発色層として機能する。該イエロー発色層、マゼンタ発色層及びシアン発色層に各々含有されるハロゲン化銀乳剤は、相互に異なる波長領域の光（例えば、青色領域、緑色領域及び赤色領域の光）に対して、感光性を有しているのが好ましい。
【００７４】
本発明の感光材料は、前記イエロー発色層、マゼンタ発色層及びシアン発色層以外にも、所望により後述する親水性コロイド層、アンチハレーション層、中間層及び着色層を有していてもよい。
【００７５】
本発明の感光材料には、従来公知の写真用素材や添加剤を使用できる。
例えば写真用支持体としては、透過型支持体や反射型支持体を用いることができる。透過型支持体としては、セルロースナイトレートフィルムやポリエチレンテレフタレートなどの透明フィルム、更には２，６−ナフタレンジカルボン酸（ＮＤＣＡ）とエチレングリコール（ＥＧ）とのポリエステルやＮＤＣＡとテレフタル酸とＥＧとのポリエステル等に磁性層などの情報記録層を設けたものが好ましく用いられる。反射型支持体としては特に複数のポリエチレン層やポリエステル層でラミネートされ、このような耐水性樹脂層（ラミネート層）の少なくとも一層に酸化チタン等の白色顔料を含有する反射支持体が好ましい。
【００７６】
本発明においてさらに好ましい反射支持体としては、ハロゲン化銀乳剤層を設ける側の紙基体上に微小空孔を有するポリオレフィン層を有しているものが挙げられる。ポリオレフィン層は多層から成っていてもよく、その場合、好ましくはハロゲン化銀乳剤層側のゼラチン層に隣接するポリオレフィン層は微小空孔を有さず（例えばポリプロピレン、ポリエチレン）、紙基体上に近い側に微小空孔を有するポリオレフィン（例えばポリプロピレン、ポリエチレン）から成るものがより好ましい。紙基体及び写真構成層の間に位置するこれら多層もしくは一層のポリオレフィン層の密度は０．４０〜１．０ｇ／ｍｌであることが好ましく、０．５０〜０．７０ｇ／ｍｌがより好ましい。また、紙基体及び写真構成層の間に位置するこれら多層もしくは一層のポリオレフィン層の厚さは１０〜１００μｍが好ましく、１５〜７０μｍがさらに好ましい。また、ポリオレフィン層と紙基体の厚さの比は０．０５〜０．２が好ましく、０．１〜０．１５がさらに好ましい。
【００７７】
また、上記紙基体の写真構成層とは逆側（裏面）にポリオレフィン層を設けることも、反射支持体の剛性を高める点から好ましく、この場合、裏面のポリオレフィン層は表面が艶消しされたポリエチレン又はポリプロピレンが好ましく、ポリプロピレンがより好ましい。裏面のポリオレフィン層は５〜５０μｍが好ましく、１０〜３０μｍがより好ましく、さらに密度が０．７〜１．１ｇ／ｍｌであることが好ましい。本発明における反射支持体において、紙基体上に設けるポリオレフィン層に関する好ましい態様については、特開平１０−３３３２７７号、同１０−３３３２７８号、同１１−５２５１３号、同１１−６５０２４号、ＥＰ０８８００６５号、及びＥＰ０８８００６６号に記載されている例が挙げられる。
【００７８】
更に前記の耐水性樹脂層中には蛍光増白剤を含有するのが好ましい。また、前記蛍光増白剤を分散含有する親水性コロイド層を、別途形成してもよい。前記蛍光増白剤として、好ましくは、ベンゾオキサゾール系、クマリン系、ピラゾリン系を用いることができ、更に好ましくは、ベンゾオキサゾリルナフタレン系及びベンゾオキサゾリルスチルベン系の蛍光増白剤である。使用量は、特に限定されていないが、好ましくは１〜１００ｍｇ／ｍ²である。耐水性樹脂に混合する場合の混合比は、好ましくは樹脂に対して０．０００５〜３質量％であり、更に好ましくは０．００１〜０．５質量％である。
【００７９】
反射型支持体としては、透過型支持体、又は上記のような反射型支持体上に、白色顔料を含有する親水性コロイド層を塗設したものでもよい。また、反射型支持体は、鏡面反射性又は第２種拡散反射性の金属表面をもつ支持体であってもよい。
【００８０】
また、本発明の感光材料に用いられる支持体としては、ディスプレイ用に白色ポリエステル系支持体又は白色顔料を含む層がハロゲン化銀乳剤層を有する側の支持体上に設けられた支持体を用いてもよい。更に鮮鋭性を改良するために、アンチハレーション層を支持体のハロゲン化銀乳剤層塗布側又は裏面に塗設するのが好ましい。特に反射光でも透過光でもディスプレイが観賞できるように、支持体の透過濃度を０．３５〜０．８の範囲に設定するのが好ましい。
【００８１】
本発明の感光材料には、画像のシャープネス等を向上させる目的で親水性コロイド層に、欧州特許ＥＰ０，３３７，４９０Ａ２号の第２７〜７６頁に記載の、処理により脱色可能な染料（なかでもオキソノール系染料）を感光材料の６８０ｎｍに於ける光学反射濃度が０．７０以上になるように添加したり、支持体の耐水性樹脂層中に２〜４価のアルコール類（例えばトリメチロールエタン）等で表面処理された酸化チタンを１２質量％以上（より好ましくは１４質量％以上）含有させるのが好ましい。
【００８２】
本発明の感光材料には、イラジエーションやハレーションを防止したり、セーフライト安全性等を向上させる目的で親水性コロイド層に、欧州特許ＥＰ０３３７４９０Ａ２号明細書の第２７〜７６頁に記載の、処理により脱色可能な染料（中でもオキソノール染料、シアニン染料）を添加することが好ましい。さらに、欧州特許ＥＰ０８１９９７７号明細書に記載の染料も本発明に好ましく添加される。これらの水溶性染料の中には使用量を増やすと色分離やセーフライト安全性を悪化するものもある。色分離を悪化させないで使用できる染料としては、特開平５−１２７３２４号、同５−１２７３２５号、同５−２１６１８５号に記載された水溶性染料が好ましい。
【００８３】
本発明においては、水溶性染料の代わり、あるいは水溶性染料と併用しての処理で脱色可能な着色層が用いられる。用いられる処理で脱色可能な着色層は、乳剤層に直かに接してもよく、ゼラチンやハイドロキノンなどの処理混色防止剤を含む中間層を介して接するように配置されていてもよい。この着色層は、着色された色と同種の原色に発色する乳剤層の下層（支持体側）に設置されることが好ましい。各原色毎に対応する着色層を全て個々に設置することも、このうちに一部のみを任意に選んで設置することも可能である。また複数の原色域に対応する着色を行った着色層を設置することも可能である。着色層の光学反射濃度は、露光に使用する波長域（通常のプリンター露光においては４００ｎｍ〜７００ｎｍの可視光領域、走査露光の場合には使用する走査露光光源の波長）において最も光学濃度の高い波長における光学濃度値が０．２以上３．０以下であることが好ましい。さらに好ましくは０．５以上２．５以下、特に０．８以上２．０以下が好ましい。
【００８４】
着色層を形成するためには、従来公知の方法が適用できる。例えば、特開平２−２８２２４４号３頁右上欄から８頁に記載された染料や、特開平３−７９３１号３頁右上欄から１１頁左下欄に記載された染料のように固体微粒子分散体の状態で親水性コロイド層に含有させる方法、アニオン性色素をカチオンポリマーに媒染する方法、色素をハロゲン化銀等の微粒子に吸着させて層中に固定する方法、特開平１−２３９５４４号に記載されているようなコロイド銀を使用する方法などである。色素の微粉末を固体状で分散する方法としては、例えば、少なくともｐＨ６以下では実質的に水不溶性であるが、少なくともｐＨ８以上では実質的に水溶性である微粉末染料を含有させる方法が特開平２−３０８２４４号の第４〜１３頁に記載されている。また、例えば、アニオン性色素をカチオンポリマーに媒染する方法としては、特開平２−８４６３７号の第１８〜２６頁に記載されている。光吸収剤としてのコロイド銀の調製法については米国特許第２，６８８，６０１号、同３，４５９，５６３号に示されている。これらの方法のなかで微粉末染料を含有させる方法、コロイド銀を使用する方法などが好ましい。
【００８５】
本発明のハロゲン化銀写真感光材料は、カラーネガフィルム、カラーポジフィルム、カラー反転フィルム、カラー反転印画紙、カラー印画紙等に用いられるが、中でもカラー印画紙として用いるのが好ましい。カラー印画紙は、イエロー発色性ハロゲン化銀乳剤層、マゼンタ発色性ハロゲン化銀乳剤層及びシアン発色性ハロゲン化銀乳剤層をそれぞれ少なくとも１層ずつ有してなることが好ましく、一般には、これらのハロゲン化銀乳剤層は支持体から近い順にイエロー発色性ハロゲン化銀乳剤層、マゼンタ発色性ハロゲン化銀乳剤層、シアン発色性ハロゲン化銀乳剤層である。
【００８６】
しかしながら、これとは異なった層構成を取っても構わない。
イエローカプラーを含有するハロゲン化銀乳剤層は支持体上のいずれの位置に配置されても構わないが、該イエローカプラー含有層にハロゲン化銀平板粒子を含有する場合は、マゼンタカプラー含有ハロゲン化銀乳剤層又はシアンカプラー含有ハロゲン化銀乳剤層の少なくとも一層よりも支持体から離れた位置に塗設されていることが好ましい。また、発色現像促進、脱銀促進、増感色素による残色の低減の観点からは、イエローカプラー含有ハロゲン化銀乳剤層は他のハロゲン化銀乳剤層より、支持体から最も離れた位置に塗設されていることが好ましい。更に、Ｂｌｉｘ退色の低減の観点からはシアンカプラー含有ハロゲン化銀乳剤層は他のハロゲン化銀乳剤層の中央の層が好ましく、光退色の低減の観点からはシアンカプラー含有ハロゲン化銀乳剤層は最下層が好ましい。また、イエロー、マゼンタ及びシアンのそれぞれの発色性層は２層又は３層からなってもよい。例えば、特開平４−７５０５５号、同９−１１４０３５号、同１０−２４６９４０号、米国特許第５，５７６，１５９号等に記載のように、ハロゲン化銀乳剤を含有しないカプラー層をハロゲン化銀乳剤層に隣接して設け、発色層とすることも好ましい。
【００８７】
本発明において適用されるハロゲン化銀乳剤やその他の素材（添加剤など）及び写真構成層（層配置など）、並びにこの感光材料を処理するために適用される処理法や処理用添加剤としては、特開昭６２−２１５２７２号、特開平２−３３１４４号、欧州特許ＥＰ０，３５５，６６０Ａ２号に記載されているもの、特に欧州特許ＥＰ０，３５５，６６０Ａ２号に記載されているものが好ましく用いられる。更には、特開平５−３４８８９号、同４−３５９２４９号、同４−３１３７５３号、同４−２７０３４４号、同５−６６５２７号、同４−３４５４８号、同４−１４５４３３号、同２−８５４号、同１−１５８４３１号、同２−９０１４５号、同３−１９４５３９号、同２−９３６４１号、欧州特許公開第０５２０４５７Ａ２号等に記載のハロゲン化銀カラー写真感光材料やその処理方法も好ましい。
【００８８】
特に、本発明においては、前記の反射型支持体やハロゲン化銀乳剤、更にはハロゲン化銀粒子中にドープされる異種金属イオン種、ハロゲン化銀乳剤の保存安定剤又はカブリ防止剤、化学増感法（増感剤）、分光増感法（分光増感剤）、シアン、マゼンタ、イエローカプラー及びその乳化分散法、色像保存性改良剤（ステイン防止剤や褪色防止剤）、染料（着色層）、ゼラチン種、感光材料の層構成や感光材料の被膜ｐＨなどについては、下記表１に示す特許の各箇所に記載のものが特に好ましく適用できる。
【００８９】
【表１】

【００９０】
本発明において用いられるシアン、マゼンタ及びイエローカプラーとしては、その他、特開昭６２−２１５２７２号の第９１頁右上欄４行目〜１２１頁左上欄６行目、特開平２−３３１４４号の第３頁右上欄１４行目〜１８頁左上欄末行目と第３０頁右上欄６行目〜３５頁右下欄１１行目やＥＰ０３５５，６６０Ａ２号の第４頁１５行目〜２７行目、５頁３０行目〜２８頁末行目、４５頁２９行目〜３１行目、４７頁２３行目〜６３頁５０行目に記載のカプラーも有用である。
また、本発明はＷＯ−９８／３３７６０号の一般式（II）及び（III）、特開平１０−２２１８２５号の一般式（Ｄ）で表される化合物を添加してもよく、好ましい。
【００９１】
本発明に使用可能なシアン色素形成カプラー（単に、「シアンカプラー」という場合がある）としては、ピロロトリアゾール系カプラーが好ましく用いられ、特開平５−３１３３２４号の一般式（Ｉ）又は（II）で表されるカプラー及び特開平６−３４７９６０号の一般式（Ｉ）で表されるカプラー並びにこれらの特許に記載されている例示カプラーが特に好ましい。また、フェノール系、ナフトール系のシアンカプラーも好ましく、例えば、特開平１０−３３３２９７号に記載の一般式（ＡＤＦ）で表されるシアンカプラーが好ましい。上記以外のシアンカプラーとしては、欧州特許ＥＰ０４８８２４８号明細書及びＥＰ０４９１１９７Ａ１号明細書に記載のピロロアゾール型シアンカプラー、米国特許第５，８８８，７１６号に記載の２，５−ジアシルアミノフェノールカプラー、米国特許第４，８７３，１８３号、同第４，９１６，０５１号に記載の６位に電子吸引性基、水素結合基を有するピラゾロアゾール型シアンカプラー、特に、特開平８−１７１１８５号、同８−３１１３６０号、同８−３３９０６０号に記載の６位にカルバモイル基を有するピラゾロアゾール型シアンカプラーも好ましい。
【００９２】
また、特開平２−３３１４４号公報に記載のジフェニルイミダゾール系シアンカプラーの他に、欧州特許ＥＰ０３３３１８５Ａ２号明細書に記載の３−ヒドロキシピリジン系シアンカプラー（なかでも具体例として列挙されたカプラー（４２）の４当量カプラーに塩素離脱基をもたせて２当量化したものや、カプラー（６）や（９）が特に好ましい）や特開昭６４−３２２６０号公報に記載された環状活性メチレン系シアンカプラー（なかでも具体例として列挙されたカプラー例３、８、３４が特に好ましい）、欧州特許ＥＰ０４５６２２６Ａ１号明細書に記載のピロロピラゾール型シアンカプラー、欧州特許ＥＰ０４８４９０９号に記載のピロロイミダゾール型シアンカプラーを使用することもできる。
【００９３】
尚、これらのシアンカプラーのうち、特開平１１−２８２１３８号公報に記載の一般式（Ｉ）で表されるピロロアゾール系シアンカプラーが特に好ましく、該特許の段落番号００１２〜００５９の記載は例示シアンカプラー（１）〜（４７）を含め、本願にそのまま適用され、本願の明細書の一部として好ましく取り込まれる。
【００９４】
本発明に用いられるマゼンタ色素形成カプラー（単に、「マゼンタカプラー」という場合がある）としては、前記の表の公知文献に記載されたような５−ピラゾロン系マゼンタカプラーやピラゾロアゾール系マゼンタカプラーが用いられるが、中でも色相や画像安定性、発色性等の点で特開昭６１−６５２４５号に記載されたような２級又は３級アルキル基がピラゾロトリアゾール環の２、３又は６位に直結したピラゾロトリアゾールカプラー、特開昭６１−６５２４６号に記載されたような分子内にスルホンアミド基を含んだピラゾロアゾールカプラー、特開昭６１−１４７２５４号に記載されたようなアルコキシフェニルスルホンアミドバラスト基を持つピラゾロアゾールカプラーや欧州特許第２２６，８４９Ａ号や同第２９４，７８５Ａ号に記載されたような６位にアルコキシ基やアリールオキシ基をもつピラゾロアゾールカプラーの使用が好ましい。特に、マゼンタカプラーとしては特開平８−１２２９８４号に記載の一般式（Ｍ−Ｉ）で表されるピラゾロアゾールカプラーが好ましく、該特許の段落番号０００９〜００２６はそのまま本願に適用され、本願の明細書の一部として取り込まれる。これに加えて、欧州特許第８５４３８４号、同第８８４６４０号に記載の３位と６位の両方に立体障害基を有するピラゾロアゾールカプラーも好ましく用いられる。
【００９５】
また、イエロー色素形成カプラー(単に、「イエローカプラー」という場合がある）としては、前記表中に記載の化合物の他に、欧州特許ＥＰ０４４７９６９Ａ１号明細書に記載のアシル基に３〜５員の環状構造を有するアシルアセトアミド型イエローカプラー、欧州特許ＥＰ０４８２５５２Ａ１号明細書に記載の環状構造を有するマロンジアニリド型イエローカプラー、欧州公開特許第９５３８７０Ａ１号、同第９５３８７１Ａ１号、同第９５３８７２Ａ１号、同第９５３８７３Ａ１号、同第９５３８７４Ａ１号、同第９５３８７５Ａ１号等に記載のピロール−２又は３−イルもしくはインドール−２又は３−イルカルボニル酢酸アニリド系カプラー、米国特許第５，１１８，５９９号明細書に記載されたジオキサン構造を有するアシルアセトアミド型イエローカプラーが好ましく用いられる。その中でも、アシル基が１−アルキルシクロプロパン−１−カルボニル基であるアシルアセトアミド型イエローカプラー、アニリドの一方がインドリン環を構成するマロンジアニリド型イエローカプラーの使用が特に好ましい。これらのカプラーは、単独あるいは併用することができる。
【００９６】
本発明に使用するカプラーは、前出表中記載の高沸点有機溶媒の存在下で（又は不存在下で）ローダブルラテックスポリマー（例えば米国特許第４，２０３，７１６号）に含浸させて、又は水不溶性かつ有機溶媒可溶性のポリマーとともに溶かして親水性コロイド水溶液に乳化分散させることが好ましい。好ましく用いることのできる水不溶性かつ有機溶媒可溶性のポリマーは、米国特許第４，８５７，４４９号明細書の第７欄〜１５欄及び国際公開ＷＯ８８／００７２３号明細書の第１２頁〜３０頁に記載の単独重合体又は共重合体が挙げられる。より好ましくはメタクリレート系あるいはアクリルアミド系ポリマー、特にアクリルアミド系ポリマーの使用が色像安定性等の上で好ましい。
【００９７】
本発明においては公知の混色防止剤を用いることができるが、その中でも以下に挙げる特許に記載のものが好ましい。
例えば、特開平５−３３３５０１号に記載の高分子量のレドックス化合物、ＷＯ９８／３３７６０号、米国特許第４，９２３，７８７号等に記載のフェニドンやヒドラジン系化合物、特開平５−２４９６３７号、特開平１０−２８２６１５号及び独国特許第１９６２９１４２Ａ１号等に記載のホワイトカプラーを用いることができる。また、特に現像液のｐＨを上げ、現像の迅速化を行う場合には独国特許第１９６１８７８６Ａ１号、欧州特許第８３９６２３Ａ１号、欧州特許第８４２９７５Ａ１号、独国特許１９８０６８４６Ａ１号及び仏国特許第２７６０４６０Ａ１号等に記載のレドックス化合物を用いることも好ましい。
【００９８】
本発明においては紫外線吸収剤としてモル吸光係数の高いトリアジン骨核を有する化合物を用いることが好ましく、例えば、以下の特許に記載の化合物を用いることができる。これらは、感光性層又は／及び非感光性に好ましく添加される。例えば、特開昭４６−３３３５号、同５５−１５２７７６号、特開平５−１９７０７４号、同５−２３２６３０号、同５−３０７２３２号、同６−２１１８１３号、同８−５３４２７号、同８−２３４３６４号、同８−２３９３６８号、同９−３１０６７号、同１０−１１５８９８号、同１０−１４７５７７号、同１０−１８２６２１号、独国特許第１９７３９７９７Ａ号、欧州特許第７１１８０４Ａ号及び特表平８−５０１２９１号等に記載されている化合物を使用できる。
【００９９】
本発明の感光材料に用いることのできる結合剤又は保護コロイドとしては、ゼラチンを用いることが有利であるが、それ以外の親水性コロイドを単独であるいはゼラチンとともに用いることができる。好ましいゼラチンとしては、鉄、銅、亜鉛、マンガン等の不純物として含有される重金属は、好ましくは５ｐｐｍ以下、更に好ましくは３ｐｐｍ以下である。また、感光材料中に含まれるカルシウム量は、好ましくは２０ｍｇ／ｍ²以下、更に好ましくは１０ｍｇ／ｍ²以下、最も好ましくは５ｍｇ／ｍ²以下である。
【０１００】
本発明においては、親水性コロイド層中に繁殖して画像を劣化させる各種の黴や細菌を防ぐために、特開昭６３−２７１２４７号公報に記載のような防菌・防黴剤を添加するのが好ましい。さらに、感光材料の被膜ｐＨは４．０〜７．０が好ましく、より好ましくは４．０〜６．５である。
【０１０１】
本発明においては、感光材料の塗布安定性向上、静電気発生防止、帯電量調節等の点から界面活性剤を感光材料に添加することができる。界面活性剤としてはアニオン系界面活性剤、カチオン系界面活性剤、ベタイン系界面活性剤、ノニオン系界面活性剤があり、例えば特開平５−３３３４９２号に記載のものが挙げられる。本発明に用いる界面活性剤としてはフッ素原子含有の界面活性剤が好ましい。特に、フッ素原子含有界面活性剤を好ましく用いることができる。これらのフッ素原子含有界面活性剤は単独で用いても、従来公知の他の界面活性剤と併用しても構わないが、好ましくは従来公知の他の界面活性剤との併用である。これらの界面活性剤の感光材料への添加量は特に限定されるものではないが、一般的には、１×１０^-5〜１ｇ／ｍ²、好ましくは１×１０^-4〜１×１０^-1ｇ／ｍ²、更に好ましくは１×１０^-3〜１×１０^-2ｇ／ｍ²である。
【０１０２】
本発明の感光材料は、画像情報に応じて光を照射される露光工程と、前記光照射された感光材料を現像する現像工程とにより、画像を形成することができる。本発明の感光材料は、通常のネガプリンターを用いたプリントシステムに使用される以外に、陰極線（ＣＲＴ）を用いた走査露光方式にも適している。陰極線管露光装置は、レーザーを用いた装置に比べて、簡便でかつコンパクトであり、低コストになる。また、光軸や色の調整も容易である。画像露光に用いる陰極線管には、必要に応じてスペクトル領域に発光を示す各種発光体が用いられる。例えば赤色発光体、緑色発光体、青色発光体のいずれか１種、あるいは２種以上が混合されて用いられる。スペクトル領域は、上記の赤、緑、青に限定されず、黄色、橙色、紫色或いは赤外領域に発光する蛍光体も用いられる。特に、これらの発光体を混合して白色に発光する陰極線管がしばしば用いられる。
【０１０３】
感光材料が異なる分光感度分布を有する複数の感光性層を持ち、陰極性管も複数のスペクトル領域の発光を示す蛍光体を有する場合には、複数の色を一度に露光、即ち陰極線管に複数の色の画像信号を入力して管面から発光させてもよい。各色ごとの画像信号を順次入力して各色の発光を順次行わせ、その色以外の色をカットするフィルムを通して露光する方法（面順次露光）を採ってもよく、一般には、面順次露光の方が、高解像度の陰極線管を用いることができるため、高画質化のためには好ましい。
【０１０４】
本発明の感光材料は、ガスレーザー、発光ダイオード、半導体レーザー、半導体レーザーあるいは半導体レーザーを励起光源に用いた固体レーザーと非線形光学結晶を組合わせた第二高調波発光光源（ＳＨＧ）等の単色高密度光を用いたデジタル走査露光方式が好ましく使用される。システムをコンパクトで、安価なものにするために半導体レーザー、半導体レーザーあるいは固体レーザーと非線形光学結晶を組合わせた第二高調波発生光源（ＳＨＧ）を使用することが好ましい。特にコンパクトで、安価、更に寿命が長く安定性が高い装置を設計するためには半導体レーザーの使用が好ましく、露光光源の少なくとも一つは半導体レーザーを使用することが好ましい。
【０１０５】
このような走査露光光源を使用する場合、本発明の感光材料の分光感度極大波長は、使用する走査露光用光源の波長により任意に設定することができる。半導体レーザーを励起光源に用いた固体レーザーあるいは半導体レーザーと非線形光学結晶を組合わせて得られるＳＨＧ光源では、レーザーの発振波長を半分にできるので、青色光、緑色光が得られる。従って、感光材料の分光感度極大は通常の青、緑、赤の３つの波長領域に持たせることが可能である。このような走査露光における露光時間は、画素密度を４００ｄｐｉとした場合の画素サイズを露光する時間として定義すると、好ましい露光時間としては１０^-4秒以下、更に好ましくは１０^-6秒以下である。
【０１０６】
本発明のハロゲン化銀カラー写真感光材料は、以下の公知資料に記載の露光、現像システムと組み合わせることで好ましく用いることができる。前記現像システムとしては、特開平１０−３３３２５３号に記載の自動プリント並びに現像システム、特開２０００−１０２０６号に記載の感光材料搬送装置、特開平１１−２１５３１２号に記載の画像読取装置を含む記録システム、特開平１１−８８６１９号並びに特開平１０−２０２９５０号に記載のカラー画像記録方式からなる露光システム、特開平１０−２１０２０６号に記載の遠隔診断方式を含むデジタルフォトプリントシステム、及び特願平１０−１５９１８７号に記載の画像記録装置を含むフォトプリントシステムが挙げられる。
【０１０７】
本発明に適用できる好ましい走査露光方式については、前記の表に掲示した特許に詳しく記載されている。
【０１０８】
本発明の感光材料をプリンター露光する際、米国特許第４，８８０，７２６号に記載のバンドストップフィルターを用いることが好ましい。これによって光混色が取り除かれ、色再現性が著しく向上する。
本発明においては、欧州特許ＥＰ０７８９２７０Ａ１や同ＥＰ０７８９４８０Ａ１号に記載のように、画像情報を付与する前に、予め、黄色のマイクロドットパターンを前露光し、複写規制を施しても構わない。
【０１０９】
本発明の感光材料の処理には、特開平２−２０７２５０号の第２６頁右下欄１行目〜３４頁右上欄９行目、及び特開平４−９７３５５号の第５頁左上欄１７行目〜１８頁右下欄２０行目に記載の処理素材や処理方法が好ましく適用できる。また、この現像液に使用する保恒剤としては、前記の表に掲示した特許に記載の化合物が好ましく用いられる。
【０１１０】
本発明は迅速処理適性を有する感光材料にも好ましく適用される。迅速処理を行う場合には、発色現像時間は好ましくは６０秒以下、更に好ましくは５０秒以下６秒以上、より好ましくは３０秒以下６秒以上である。同様に、漂白定着時間は好ましくは６０秒以下、更に好ましくは５０秒以下６秒以上、より好ましくは３０秒以下６秒以上である。また、水洗又は安定化時間は、好ましくは１５０秒以下、更に好ましくは１３０秒以下６秒以上である。
尚、発色現像時間とは、感光材料が発色現像液中に入ってから次の処理工程の漂白定着液に入るまでの時間をいう。例えば、自動現像機などで処理される場合には、感光材料が発色現像液中に浸漬されている時間（いわゆる液中時間）と、感光材料が発色現像液を離れ、次の処理工程の漂白定着浴に向けて空気中を搬送されている時間（いわゆる空中時間）との両者の合計を発色現像時間という。同様に、漂白定着時間とは、感光材料が漂白定着液中に入ってから次の水洗又は安定浴に入るまでの時間をいう。また、水洗又は安定化時間とは、感光材料が水洗又は安定化液中に入ってから乾燥工程に向けて液中にある時間（いわゆる液中時間）をいう。
【０１１１】
本発明の感光材料を露光後、現像する方法としては、従来のアルカリ剤と現像主薬を含む現像液で現像する方法、現像主薬を感光材料に内蔵し、現像主薬を含まないアルカリ液などのアクチベーター液で現像する方法などの湿式方式のほか、処理液を用いない熱現像方式などを用いることができる。特に、アクチベーター方法は、現像主薬を処理液に含まないため、処理液の管理や取扱いが容易であり、また廃液処理時の負荷が少なく環境保全上の点からも好ましい方法である。アクチベーター方法において、感光材料中に内蔵される現像主薬又はその前駆体としては、例えば、特開平８−２３４３８８号、同９−１５２６８６号、同９−１５２６９３号、同９−２１１８１４号、同９−１６０１９３号に記載されたヒドラジン型化合物が好ましい。
【０１１２】
また、感光材料の塗布銀量を低減し、過酸化水素を用いた画像増幅処理（補力処理）する現像方法も好ましく用いられる。特に、この方法をアクチベーター方法に用いることは好ましい。具体的には、特開平８−２９７３５４号、同９−１５２６９５号に記載された過酸化水素を含むアクチベーター液を用いた画像形成方法が好ましく用いられる。前記アクチベーター方法において、アクチベーター液で処理後、通常脱銀処理されるが、低銀量の感光材料を用いた画像増幅処理方法では、脱銀処理を省略し、水洗又は安定化処理といった簡易な方法を行うことができる。また、感光材料から画像情報をスキャナー等で読み取る方式では、撮影用感光材料などの様に高銀量の感光材料を用いた場合でも、脱銀処理を不要とする処理形態を採用することができる。
【０１１３】
本発明で用いられるアクチベーター液、脱銀液（漂白／定着液）、水洗及び安定化液の処理素材や処理方法は公知のものを用いることができる。好ましくは、リサーチ・ディスクロージャーItem ３６５４４（１９９４年９月）第５３６頁〜第５４１頁、特開平８−２３４３８８号に記載されたものを用いることができる。
【０１１４】
【実施例】
以下に、本発明を実施例によって具体的に説明するが、本発明はこれらに限定されるものではない。
【０１１５】
実施例１
（乳剤Ｂ−１の調製）
石灰処理ゼラチン３％水溶液１０００ｍｌをｐＨ３．３、ｐＣｌ１．７に調整し、硝酸銀を２．１２モル含む水溶液と塩化ナトリウムを２．２モル含む水溶液を激しく攪拌しながら６６℃で同時に添加混合した。硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ(ＣＮ)₆］水溶液を出来上がりのハロゲン化銀１モルあたりＲｕ量が３×１０^-5モルになる量を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］水溶液を出来上がりのハロゲン化銀１モルあたりＩｒ量が３×１０^-8モルになる量を添加した。硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ(Ｈ₂Ｏ)Ｃｌ₅］水溶液を出来上がりのハロゲン化銀１モルあたりＩｒ量が１×１０^-6モルになる量を添加した。４０℃で脱塩処理を施した後、石灰処理ゼラチン1６８ｇを加え、ｐＨ５．７、ｐＣｌ１．８に調整した。得られた粒子は辺長０．６μｍ、変動係数１１％の立方体塩化銀乳剤であった。
この乳剤を４０℃で溶解し、チオスルフォン酸ナトリウムをハロゲン化銀１モルあたり２×１０^-5モル添加し、硫黄増感剤としてチオ硫酸ナトリウム５水和物と金増感剤として（Ｓ−２）を用い６０℃にて最適になるように熟成した。４０℃に降温後、増感色素Ａをハロゲン化銀１モルあたり２×１０^-4モル、増感色素Ｂをハロゲン化銀１モルあたり１×１０^-4モル、１−フェニル−５−メルカプトテトラゾールをハロゲン化銀１モルあたり２×１０^-4モル、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールをハロゲン化銀１モルあたり２×１０^-4モル、臭化カリウムをハロゲン化銀１モルあたり２×１０^-3モル添加した。このようにして得られた乳剤を、乳剤Ｂ−１とした。
【０１１６】
【化６】

【０１１７】
（乳剤Ｂ−２の調製）
乳剤Ｂ−１とは、硝酸銀の添加が９０％終了した時点で、沃化カリウム水溶液を出来上がりのハロゲン化銀１モルあたりＩ量が０．２モル％になる量を激しく混合しながら添加したことのみ異なる乳剤を調製した。得られた粒子は辺長０．６μｍ、変動係数１１％の立方体沃塩化銀乳剤であった。このようにして得られた乳剤を、乳剤Ｂ−２とした。
得られた乳剤Ｂ−２の沃化物イオン濃度分布を、エッチング／ＴＯＦ−ＳＩＭＳ法で分析したところ、沃化物イオンは粒子表面で濃度極大を有し、内側に向けて濃度が減衰していることが分かった。沃化物塩溶液の添加を粒子の内側（硝酸銀の添加で９０％の位置）で終了しても、粒子表面に向けて沃化物イオンがしみ出している。できあがりの粒子形態は乳剤Ｂ−１とＢ−２でほとんど差がなく、乳剤Ｂ−２は、沃化銀含有相が粒子最表面に層状に形成された沃塩化銀粒子を含有していると考えられる。
【０１１８】
（乳剤Ｂ−３の調製）
乳剤Ｂ−１とは、硝酸銀の添加が８０％の時点から９０％の時点にかけて、臭化カリウムを出来上がりのハロゲン化銀１モルあたり２モル％になる量を激しく混合しながら添加したことのみ異なる乳剤を調製した。得られた粒子は辺長０．６μｍ、変動係数１１％の立方体臭塩化銀乳剤であった。このようにして得られた乳剤を、乳剤Ｂ−３とした。
得られた乳剤Ｂ−３の臭化物イオン濃度分布を、エッチング／ＴＯＦ−ＳＩＭＳ法で分析したところ、臭化物イオンは粒子内部で濃度極大を有していることが分かった。臭化物塩溶液の添加を行った粒子の内側（硝酸銀の添加で８０％〜９０％の位置）に臭化銀含有相ができていることを示している。できあがりの粒子形態は乳剤Ｂ−１とＢ−３でほとんど差がなく、乳剤Ｂ−３は、臭化銀含有相が粒子内部に層状に形成された臭塩化銀粒子を含有していると考えられる。
【０１１９】
（乳剤Ｂ−４の調製）
乳剤Ｂ−１とは、硝酸銀の添加が９０％の時点から１００％の時点にかけて、臭化カリウムを出来上がりのハロゲン化銀１モルあたり２モル％になる量を激しく混合しながら添加したことのみ異なる乳剤を調製した。得られた粒子は辺長０．６μｍ、変動係数１１％の立方体臭塩化銀乳剤であった。このようにして得られた乳剤を、乳剤Ｂ−４とした。
得られた乳剤Ｂ−４の臭化物イオン濃度分布を、エッチング／ＴＯＦ−ＳＩＭＳ法で分析したところ、臭化物イオンは主に表面近傍に分布していることが分かった。臭化物塩溶液の添加を行った粒子の表面近傍に（硝酸銀の添加で９０％〜１００％の位置）に臭化銀含有相ができていることを示している。できあがりの粒子形態は乳剤Ｂ−１とＢ−４でほとんど差がなく、乳剤Ｂ−４は、臭化銀含有相が表面近傍に層状に形成された臭塩化銀粒子を含有していると考えられる。
【０１２０】
（乳剤Ｂ−５の調製）
乳剤Ｂ−１とは、硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウムを出来上がりのハロゲン化銀１モルあたり４モル％になる量を激しく混合しながら添加したことのみ異なる乳剤を調製した。得られた粒子は辺長０．６μｍ、変動係数１１％の立方体臭塩化銀乳剤であった。このようにして得られた乳剤を、乳剤Ｂ−５とした。
得られた乳剤Ｂ−５の臭化物イオン濃度分布を、エッチング／ＴＯＦ−ＳＩＭＳ法で分析したところ、臭化物イオンは粒子内部から表面にかけて分布していることが分かった。臭化物塩溶液の添加を行った粒子の内側から表面にかけて（硝酸銀の添加で８０％〜１００％の位置）に臭化銀含有相ができていることを示している。できあがりの粒子形態は乳剤Ｂ−１とＢ−５でほとんど差がなく、乳剤Ｂ−５は、臭化銀含有相が粒子内部から表面にかけて層状に形成された臭塩化銀粒子を含有していると考えられる。
【０１２１】
(乳剤Ｂ−６の調製)
乳剤Ｂ−１とは、硝酸銀の添加が８０％の時点から９０％の時点にかけて、臭化カリウムを出来上がりのハロゲン化銀１モルあたり２モル％になる量を激しく混合しながら添加し、更に硝酸銀の添加が９０％終了した時点で、沃化カリウム水溶液を出来上がりのハロゲン化銀１モルあたりＩ量が０．２モル％になる量を激しく混合しながら添加したことのみ異なる乳剤を調製した。得られた粒子は辺長０．６μｍ、変動係数１１％の立方体沃臭塩化銀乳剤であった。このようにして得られた乳剤を、乳剤Ｂ−６とした。
得られた乳剤Ｂ−６の沃化物イオンおよび臭化物イオン濃度分布を、エッチング／ＴＯＦ−ＳＩＭＳ法で分析したところ、沃化物イオンは粒子表面で濃度極大を有し、内側に向けて濃度が減衰しているのに対し、臭化物イオンは粒子内部で濃度極大を有していることが分かった。沃化物塩溶液の添加を粒子の内側（硝酸銀の添加で９０％の位置）で終了しても、沃化物イオンは粒子表面に向けてしみ出しているが、臭化銀含有相は臭化物塩溶液の添加を行った粒子の内側（硝酸銀の添加で８０％〜９０％の位置）にできていることを示している。できあがりの粒子形態は乳剤Ｂ−１とＢ−６でほとんど差がなく、乳剤Ｂ−６は、臭化銀含有相が粒子内部に層状に形成され、沃化銀含有相が粒子最表面に層状に形成された沃臭塩化銀粒子を含有していると考えられる。
【０１２２】
（乳剤Ｂ−７の調製）
乳剤Ｂ−１とは、硝酸銀の添加が９０％終了した時点で、沃化カリウム水溶液を出来上がりのハロゲン化銀１モルあたりＩ量が０．２モル％になる量を激しく混合しながら添加し、更に硝酸銀の添加が９０％の時点から１００％の時点にかけて、臭化カリウムを出来上がりのハロゲン化銀１モルあたり２モル％になる量を激しく混合しながら添加したことのみ異なる乳剤を調製した。得られた粒子は辺長０．６μｍ、変動係数１１％の立方体沃臭塩化銀乳剤であった。このようにして得られた乳剤を、乳剤Ｂ−７とした。
得られた乳剤Ｂ−７の沃化物イオンおよび臭化物イオン濃度分布を、エッチング／ＴＯＦ−ＳＩＭＳ法で分析したところ、沃化物イオンは粒子表面で濃度極大を有し、内側に向けて濃度が減衰しており、臭化物イオンも主に表面近傍に分布していることが分かった。沃化物塩溶液の添加を粒子の内側（硝酸銀の添加で９０％の位置）で終了しても、沃化物イオンは粒子表面に向けてしみ出しているが、臭化銀含有相は臭化物塩溶液の添加を行った粒子の表面近傍に（硝酸銀の添加で９０％〜１００％の位置）にできていることを示している。できあがりの粒子形態は乳剤Ｂ−１とＢ−７でほとんど差がなく、乳剤Ｂ−７は、臭化銀含有相および沃化銀含有相が共に表面に層状に形成された沃臭塩化銀粒子を含有していると考えられる。
【０１２３】
（乳剤Ｂ−８の調製）
乳剤Ｂ−１とは、硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウムを出来上がりのハロゲン化銀１モルあたり４モル％になる量を激しく混合しながら添加し、更に硝酸銀の添加が９０％終了した時点で、沃化カリウム水溶液を出来上がりのハロゲン化銀１モルあたりＩ量が０．２モル％になる量を激しく混合しながら添加したことのみ異なる乳剤を調製した。得られた粒子は辺長０．６μｍ、変動係数１１％の立方体沃臭塩化銀乳剤であった。このようにして得られた乳剤を、乳剤Ｂ−８とした。
得られた乳剤Ｂ−８の沃化物イオンおよび臭化物イオン濃度分布を、エッチング／ＴＯＦ−ＳＩＭＳ法で分析したところ、沃化物イオンは粒子表面で濃度極大を有し、内側に向けて濃度が減衰しているのに対し、臭化物イオンは粒子内部から表面にかけて分布していることが分かった。沃化物塩溶液の添加を粒子の内側（硝酸銀の添加で９０％の位置）で終了しても、沃化物イオンは粒子表面に向けてしみ出しているが、臭化銀含有相は臭化物塩溶液の添加を行った粒子の内側から表面にかけて（硝酸銀の添加で８０％〜１００％の位置）できていることを示している。できあがりの粒子形態は乳剤Ｂ−１とＢ−８でほとんど差がなく、乳剤Ｂ−８は、臭化銀含有相が粒子内部から表面にかけて層状に形成され、沃化銀含有相が粒子最表面に層状に形成された沃臭塩化銀粒子を含有していると考えられる。
【０１２４】
紙の両面をポリエチレン樹脂で被覆してなる支持体の表面に、コロナ放電処理を施した後、ドデシルベンゼンスルホン酸ナトリウムを含むゼラチン下塗層を設け、さらに第一層〜第七層の写真構成層を順次塗設して、以下に示す層構成のハロゲン化銀カラー写真感光材料の試料を作製した。各写真構成層用の塗布液は、以下のようにして調製した。
【０１２５】
第一層塗布液調製
イエローカプラー（ＥｘＹ）５７ｇ、色像安定剤（Ｃｐｄ−１）７ｇ、色像安定剤（Ｃｐｄ−２）４ｇ、色像安定剤（Ｃｐｄ−３）７ｇ、色像安定剤（Ｃｐｄ−８）２ｇを溶媒（Ｓｏｌｖ−１）２１ｇ及び酢酸エチル８０ｍｌに溶解し、この液を４ｇのドデシルベンゼンスルホン酸ナトリウムを含む２３．５質量％ゼラチン水溶液２２０ｇ中に高速攪拌乳化機（ディゾルバー）で乳化分散し、水を加えて９００ｇの乳化分散物Ａを調製した。
一方、前記乳化分散物Ａと乳剤Ｂ−１を混合溶解し、後記組成となるように第一層塗布液を調製した。乳剤塗布量は、銀量換算塗布量を示す。
【０１２６】
第二層〜第七層用の塗布液も第一層塗布液と同様の方法で調製した。各層のゼラチン硬化剤としては、１−オキシ−３，５−ジクロロ−ｓ−トリアジンナトリウム塩（Ｈ−１）、（Ｈ−２）、（Ｈ−３）を用いた。また、各層にＡｂ−１、Ａｂ−２、Ａｂ−３、及びＡｂ−４をそれぞれ全量が１５．０ｍｇ／ｍ²、６０．０ｍｇ／ｍ²、５．０ｍｇ／ｍ²及び１０．０ｍｇ／ｍ²となるように添加した。
【０１２７】
【化７】

【０１２８】
【化８】

【０１２９】
緑及び赤感性乳剤層の臭塩化銀乳剤には、以下の分光増感色素をそれぞれ用いた。
緑感性乳剤層
【０１３０】
【化９】

【０１３１】
（増感色素Ｄをハロゲン化銀１モル当り、大サイズ乳剤に対しては３．０×１０^-4モル、小サイズ乳剤に対しては３．６×１０^-4モル、また、増感色素Ｅをハロゲン化銀１モル当り、大サイズ乳剤に対しては４．０×１０^-5モル、小サイズ乳剤に対しては７．０×１０^-5モル、また、増感色素Ｆをハロゲン化銀１モル当り、大サイズ乳剤に対しては２．０×１０^-4モル、小サイズ乳剤に対しては２．８×１０^-4モル添加した。）
赤感性乳剤層
【０１３２】
【化１０】

【０１３３】
（増感色素ＧおよびＨをそれぞれ、ハロゲン化銀１モル当り、大サイズ乳剤に対しては８．０×１０^-5モル、小サイズ乳剤に対しては１０．７×１０^-5モル添加した。さらに、以下の化合物Ｉを赤感性乳剤層にハロゲン化銀１モル当たり３．０×１０^-3モル添加した。）
【０１３４】
【化１１】

【０１３５】
また、緑感性乳剤層および赤感性乳剤層に対し、１−（３−メチルウレイドフェニル）−５−メルカプトテトラゾールを、それぞれハロゲン化銀１モル当り１．０×１０^-3モルおよび５．９×１０^-4モル添加した。
さらに、第二層、第四層、第六層および第七層にも、それぞれ０．２ｍｇ／ｍ²、０．２ｍｇ／ｍ²、０．６ｍｇ／ｍ²、０．１ｍｇ／ｍ²となるように添加した。
また、青感性乳剤層および緑感性乳剤層に対し、４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを、それぞれハロゲン化銀１モル当たり、１×１０^-4モル、２×１０^-4モル添加した。
また、赤感性乳剤層にメタクリル酸とアクリル酸ブチルの共重合体ラテックス（質量比１：１、平均分子量２０００００〜４０００００）を０．０５ｇ／ｍ²添加した。
また、第二層、第四層および第六層にカテコール−３，５−ジスルホン酸二ナトリウムをそれぞれ６ｍｇ／ｍ²、６ｍｇ／ｍ²、１８ｍｇ／ｍ²となるように添加した。
また、イラジエーション防止のために、以下の染料（カッコ内は塗布量を表す）を添加した。
【０１３６】
【化１２】

【０１３７】
（層構成）
以下に、各層の構成を示す。数字は塗布量（ｇ／ｍ²）を表す。ハロゲン化銀乳剤は、銀換算塗布量を表す。
支持体
ポリエチレン樹脂ラミネート紙
［第一層側のポリエチレン樹脂に白色顔料（ＴｉＯ₂；含有率１６質量％、ＺｎＯ；含有率４質量％）と蛍光増白剤（４，４’−ビス（５−メチルベンゾオキサゾリル）スチルベン。含有率０．０３質量％）、青味染料（群青）を含む］
第一層（青感性乳剤層）
乳剤Ｂ−１ ０．２４
ゼラチン １．２５
イエローカプラー（ＥｘＹ） ０．５７
色像安定剤（Ｃｐｄ−１） ０．０７
色像安定剤（Ｃｐｄ−２） ０．０４
色像安定剤（Ｃｐｄ−３） ０．０７
色像安定剤（Ｃｐｄ−８） ０．０２
溶媒（Ｓｏｌｖ−１） ０．２１
【０１３８】
第二層（混色防止層）
ゼラチン ０．９９
混色防止剤（Ｃｐｄ−４） ０．０９
色像安定剤（Ｃｐｄ−５） ０．０１８
色像安定剤（Ｃｐｄ−６） ０．１３
色像安定剤（Ｃｐｄ−７） ０．０１
溶媒（Ｓｏｌｖ−１） ０．０６
溶媒（Ｓｏｌｖ−２） ０．２２
【０１３９】

【０１４０】
第四層（混色防止層）
ゼラチン ０．７１
混色防止層（Ｃｐｄ−４） ０．０６
色像安定剤（Ｃｐｄ−５） ０．０１３
色像安定剤（Ｃｐｄ−６） ０．１０
色像安定剤（Ｃｐｄ−７） ０．００７
溶媒（Ｓｏｌｖ−１） ０．０４
溶媒（Ｓｏｌｖ−２） ０．１６
【０１４１】

【０１４２】
第六層（紫外線吸収層）
ゼラチン ０．４６
紫外線吸収剤（ＵＶ−Ｂ） ０．４５
化合物（Ｓ１−４） ０．００１５
溶媒（Ｓｏｌｖ−７） ０．２５
第七層（保護層）
ゼラチン １．００
ポリビニルアルコールのアクリル変性共重合体
（変性度１７％） ０．０４
流動パラフィン ０．０２
界面活性剤（Ｃｐｄ−１３） ０．０１
【０１４３】
【化１３】

【０１４４】
【化１４】

【０１４５】
【化１５】

【０１４６】
【化１６】

【０１４７】
【化１７】

【０１４８】
【化１８】

【０１４９】
【化１９】

【０１５０】
【化２０】

【０１５１】
【化２１】

【０１５２】
【化２２】

【０１５３】
以上のようにして得られた試料を、試料Ｂ−１とした。試料Ｂ−１とは青感性乳剤層の乳剤Ｂ−１を乳剤Ｂ−２からＢ−８まで替えた試料も同様に作製し、それぞれ試料Ｂ−２からＢ−８とした。
【０１５４】
これらの試料の写真特性を調べるために以下のような実験を行った。
各塗布試料に対して高照度露光用感光計（山下電装（株）製ＨＩＥ型）を用いて、センシトメトリー用の階調露光を与えた。富士写真フイルム（株）製ＳＰ−１フィルターを装着し、高照度１０^-6秒間露光した。
露光後は、以下に示す発色現像処理Ａを行った。
【０１５５】
以下に処理工程を示す。
［処理Ａ］
上記感光材料の試料を１２７ｍｍ巾のロール状に加工し、富士写真フイルム（株）製ミニラボプリンタープロセッサー ＰＰ１２５８ＡＲを用いて像様露光後、下記処理工程にてカラー現像タンク容量の２倍補充するまで、連続処理（ランニングテスト）を行った。このランニング液を用いた処理を処理Ａとした。
処理工程 温 度 時 間 補充量^*
カラー現像 ３８．５℃ ４５秒 ４５ミリリットル
漂白定着 ３８．０℃ ４５秒 ３５ミリリットル
リンス（１） ３８．０℃ ２０秒 −
リンス（２） ３８．０℃ ２０秒 −
リンス（３） ＊＊３８．０℃ ２０秒 −
リンス（４） ＊＊３８．０℃ ３０秒 １２１ミリリットル
＊感光材料１ｍ²当たりの補充量
＊＊富士写真フイルム社製 リンスクリーニングシステムＲＣ５０Ｄをリンス（３）に装置し、リンス（３）からリンス液を取り出し、ポンプにより逆浸透膜モジュール（ＲＣ５０Ｄ）へ送る。同槽で得られた透過水はリンス（４）に供給し、濃縮水はリンス（３）に戻す。逆浸透モジュールへの透過水量は５０〜３００ミリリットル／分を維持するようにポンプ圧を調整し、１日１０時間温調循環させた。
（リンスは（１）から（４）へのタンク向流方式とした。）
【０１５６】
各処理液の組成は以下の通りである。

【０１５７】

【０１５８】

【０１５９】
処理後の各試料のイエロー発色濃度を測定し、１０^-6秒露光高照度露光の特性曲線を得た。感度は、最低発色濃度より０．７高い発色濃度を与える露光量の逆数をもって規定し、試料Ｂ−１の感度を１００としたときの相対値で表した。また、濃度０．５と濃度２．０の点を結ぶ直線の傾きから階調を求めた。結果を表２に示した。
【０１６０】
【表２】

【０１６１】
表２の結果から明らかなように、本発明の臭化銀含有相と沃化銀含有相がそれぞれ層状に形成されている沃臭塩化銀乳剤を青感光性乳剤層に含有した試料Ｂ−６、Ｂ−７およびＢ−８は、青感光性が著しく高感度で硬調であることが認められた。
【０１６２】
実施例２
（乳剤Ｇ−１の調製）
石灰処理ゼラチン３％水溶液１０００ｍｌをｐＨ３．３、ｐＣｌ１．７に調整し、硝酸銀を２．１２モル含む水溶液と塩化ナトリウムを２．２モル含む水溶液を激しく攪拌しながら５６℃で同時に添加混合した。硝酸銀の添加が８０％の時点から９０％の時点にかけて、Ｋ₄［Ｒｕ(ＣＮ)₆］水溶液を出来上がりのハロゲン化銀１モルあたりＲｕ量が５×１０^-5モルになる量を添加した。硝酸銀の添加が８３％の時点から８８％の時点にかけて、Ｋ₂［ＩｒＣｌ₆］水溶液を出来上がりのハロゲン化銀１モルあたりＩｒ量が５×１０^-8モルになる量を添加した。硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ(５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ)Ｃｌ₅］水溶液を出来上がりのハロゲン化銀１モルあたりＩｒ量が１×１０^-6モルになる量を添加した。４０℃で脱塩処理を施した後、石灰処理ゼラチン1６８ｇを加え、ｐＨ５．７、ｐＣｌ１．８に調整した。得られた粒子は辺長０．４μｍ、変動係数１１％の立方体塩化銀乳剤であった。
この乳剤を４０℃で溶解し、チオスルフォン酸ナトリウムをハロゲン化銀１モルあたり２×１０^-5モル添加し、硫黄増感剤としてチオ硫酸ナトリウム５水和物と金増感剤として（Ｓ−２）を用い６０℃にて最適になるように熟成した。４０℃に降温後、増感色素Ｄをハロゲン化銀１モルあたり５×１０^-4モル、１−フェニル−５−メルカプトテトラゾールをハロゲン化銀１モルあたり２×１０^-4モル、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールをハロゲン化銀１モルあたり４×１０^-4モル、臭化カリウムをハロゲン化銀１モルあたり７×１０^-3モル添加した。このようにして得られた乳剤を、乳剤Ｇ−１とした。
【０１６３】
（乳剤Ｇ−２の調製）
乳剤Ｇ−１とは、硝酸銀の添加が９０％終了した時点で、沃化カリウム水溶液を出来上がりのハロゲン化銀１モルあたりＩ量が０．３モル％になる量を激しく混合しながら添加したことのみ異なる乳剤を調製した。得られた粒子は辺長０．４μｍ、変動係数１１％の立方体沃塩化銀乳剤であった。このようにして得られた乳剤を、乳剤Ｇ−２とした。
【０１６４】
（乳剤Ｇ−３の調製）
乳剤Ｇ−１とは、硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウムを出来上がりのハロゲン化銀１モルあたり４モル％になる量を激しく混合しながら添加したことのみ異なる乳剤を調製した。得られた粒子は辺長０．４μｍ、変動係数１１％の立方体臭塩化銀乳剤であった。このようにして得られた乳剤を、乳剤Ｇ−３とした。
【０１６５】
（乳剤Ｇ−４の調製）
乳剤Ｇ−１とは、硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウムを出来上がりのハロゲン化銀１モルあたり４モル％になる量を激しく混合しながら添加し、更に硝酸銀の添加が９０％終了した時点で、沃化カリウム水溶液を出来上がりのハロゲン化銀１モルあたりＩ量が０．３モル％になる量を激しく混合しながら添加したことのみ異なる乳剤を調製した。得られた粒子は辺長０．４μｍ、変動係数１１％の立方体沃臭塩化銀乳剤であった。このようにして得られた乳剤を、乳剤Ｇ−４とした。
乳剤Ｇ−４粒子の深さ方向への臭化物および沃化物イオン濃度の分布を、エッチング／ＴＯＦ−ＳＩＭＳ法により測定した。結果を図１に示す。沃化物塩溶液の添加を粒子の内側で終了しても、沃化物イオンは粒子表面に向けてしみ出し、最表面に濃度極大を有し、内側に向けて濃度が減衰している。一方、臭化物イオンは粒子内部で濃度極大を有している。これから、臭化銀含有相が沃化銀含有相よりも粒子の内側にそれぞれ層状に形成されていると考えられる。
【０１６６】
実施例１の試料とは、層構成を下記のように変えて薄層化した試料を作製した。
試料の作製
第一層（青感性乳剤層）
乳剤Ｂ−１ ０．２４
ゼラチン １．２５
イエローカプラー（ＥｘＹ） ０．５７
色像安定剤（Ｃｐｄ−１） ０．０７
色像安定剤（Ｃｐｄ−２） ０．０４
色像安定剤（Ｃｐｄ−３） ０．０７
色像安定剤（Ｃｐｄ−８） ０．０２
溶媒（Ｓｏｌｖ−１） ０．２１
【０１６７】
第二層（混色防止層）
ゼラチン ０．６０
混色防止剤（Ｃｐｄ−１９） ０．０９
色像安定剤（Ｃｐｄ−５） ０．００７
色像安定剤（Ｃｐｄ−７） ０．００７
紫外線吸収剤（ＵＶ−Ｃ） ０．０５
溶媒（Ｓｏｌｖ−５） ０．１１
【０１６８】
第三層（緑感性乳剤層）
乳剤Ｇ−１ ０．１４
ゼラチン ０．７３
マゼンタカプラー（ＥｘＭ） ０．１５
紫外線吸収剤（ＵＶ−Ａ） ０．０５
色像安定剤（Ｃｐｄ−２） ０．０２
色像安定剤（Ｃｐｄ−７） ０．００８
色像安定剤（Ｃｐｄ−８） ０．０７
色像安定剤（Ｃｐｄ−９） ０．０３
色像安定剤（Ｃｐｄ−１０） ０．００９
色像安定剤（Ｃｐｄ−１１） ０．０００１
溶媒（Ｓｏｌｖ−３） ０．０６
溶媒（Ｓｏｌｖ−４） ０．１１
溶媒（Ｓｏｌｖ−５） ０．０６
【０１６９】
第四層（混色防止層）
ゼラチン ０．４８
混色防止層（Ｃｐｄ−４） ０．０７
色像安定剤（Ｃｐｄ−５） ０．００６
色像安定剤（Ｃｐｄ−７） ０．００６
紫外線吸収剤（ＵＶ−Ｃ） ０．０４
溶媒（Ｓｏｌｖ−５） ０．０９
【０１７０】
第五層（赤感性乳剤層）
臭塩化銀乳剤Ｃ（試料Ｂ−１と同じ乳剤） ０．１２
ゼラチン ０．５９
シアンカプラー（ＥｘＣ−２） ０．１３
シアンカプラー（ＥｘＣ−３） ０．０３
色像安定剤（Ｃｐｄ−７） ０．０１
色像安定剤（Ｃｐｄ−９） ０．０４
色像安定剤（Ｃｐｄ−１５） ０．１９
色像安定剤（Ｃｐｄ−１８） ０．０４
紫外線吸収剤（ＵＶ−７） ０．０２
溶媒（Ｓｏｌｖ−５） ０．０９
【０１７１】
第六層（紫外線吸収層）
ゼラチン ０．３２
紫外線吸収剤（ＵＶ−Ｃ） ０．４２
溶媒（Ｓｏｌｖ−７） ０．０８
第七層（保護層）
ゼラチン ０．７０
ポリビニルアルコールのアクリル変性共重合体
（変性度１７％） ０．０４
流動パラフィン ０．０１
界面活性剤（Ｃｐｄ−１３） ０．０１
ポリジメチルシロキサン ０．０１
二酸化珪素 ０．００３
【０１７２】
緑感性乳剤層の乳剤として上記の乳剤Ｇ−１を用いた試料を、試料Ｇ−１とした。試料Ｇ−１とは緑感性乳剤層の乳剤Ｇ−１を乳剤Ｇ−２からＧ−４まで替えた試料も同様に作製し、それぞれ試料Ｇ−２からＧ−４とした。
【０１７３】
これらの試料の写真特性を調べるために以下のような実験を行った。
各塗布試料に対して高照度露光用感光計（山下電装（株）製ＨＩＥ型）を用いて、センシトメトリー用の階調露光を与えた。富士写真フイルム（株）製ＳＰ−２フィルターを装着し、高照度１０^-6秒間露光した。
【０１７４】
露光された各試料に対し、発色現像処理は以下に示す現像処理Ｂに従い、超迅速処理を行った。
【０１７５】
［処理Ｂ］
上記感光材料の試料を１２７ｍｍ幅のロール状に加工し、処理時間、処理温度を変えられるように富士写真フイルム（株）製ミニラボプリンタープロセッサーＰＰ３５０を改造した実験処理装置を用いて感光材料試料に平均濃度のネガティブフイルムから像様露光を行い、下記処理工程にて使用した発色現像補充液の容量が発色現像タンク容量の０．５倍となるまで連続処理（ランニングテスト）を行った。
【０１７６】
処理工程 温度 時間 補充量^*
発色現像 ４５．０℃ １５秒 ４５ｍＬ
漂白定着 ４０．０℃ １５秒 ３５ｍＬ
リンス１ ４０．０℃ ８秒 −
リンス２ ４０．０℃ ８秒 −
リンス３ ＊＊ ４０．０℃ ８秒 −
リンス４ ３８．０℃ ８秒 １２１ｍＬ
乾燥 ８０．０℃ １５秒
（注）＊感光材料１ｍ²あたりの補充量
＊＊富士写真フイルム（株）製リンスクリーニングシステムＲＣ５０Ｄをリンス（３）に装着し、リンス（３）からリンス液を取り出してポンプにより逆浸透モジュール（ＲＣ５０Ｄ）へ送る。同槽で送られた透過水はリンスに供給し、濃縮液はリンス（３）に戻す。逆浸透モジュールへの透過水量は５０〜３００ｍＬ／分を維持するようにポンプ圧を調整し、１日１０時間温調循環させた。リンスは（１）から（４）への４タンク向流方式とした。
【０１７７】
各処理液の組成は以下の通りである。
[発色現像液] [タンク液] ［補充液］
水 ８００ｍＬ ６００ｍL
蛍光増白剤（ＦＬ−１） ５．０ｇ ８．５ｇ
トリイソプロパノールアミン ８．８ｇ ８．８ｇ
ｐ−トルエンスルホン酸ナトリウム ２０．０ｇ ２０．０ｇ
エチレンジアミン４酢酸 ４．０ｇ ４．０ｇ
亜硫酸ナトリウム ０．１０ｇ ０．５０ｇ
塩化カリウム １０．０ｇ −
４，５−ジヒドロキシベンゼン−
１，３−ジスルホン酸ナトリウム ０．５０ｇ ０．５０ｇ
ジナトリウム−Ｎ，Ｎ−ビス（スルホナート
エチル）ヒドロキシルアミン ８．５ｇ １４．５ｇ
４−アミノ−３−メチル−Ｎ−エチル−Ｎ−
（β−メタンスルホンアミドエチル）アニリン
・３／２硫酸塩・モノハイドレード １０．０ｇ ２２．０ｇ
炭酸カリウム ２６．３ｇ ２６．３ｇ
水を加えて全量 １０００ｍＬ １０００ｍＬ
ｐＨ（２５℃、硫酸とＫＯＨで調整）１０．３５ １２．６
【０１７８】

【０１７９】
[リンス液] [タンク液] [補充液]
塩素化イソシアヌール酸ナトリウム ０．０２ｇ ０．０２ｇ
脱イオン水（電導度５μＳ／ｃｍ以下）１０００ｍＬ １０００ｍＬ
ｐＨ（２５℃） ６．５ ６．５
【０１８０】
【化２３】

【０１８１】
処理後の各試料のマゼンタ発色濃度を測定し、１０^-6秒露光高照度露光の特性曲線を得た。感度は、最低発色濃度より０．７高い発色濃度を与える露光量の逆数をもって規定し、試料Ｇ−１の感度を１００としたときの相対値で表した。また、濃度０．５と濃度２．０の点を結ぶ直線の傾きから階調を求めた。
また、潜像保存性を調べるために、露光後１０秒後に処理を開始した場合と、露光後１０分後に処理を開始した場合の特性曲線を求め、１０秒後に処理を開始した場合に濃度１．０を与える露光量での濃度変化を調べた。更に露光温湿度依存性を調べるために、１０℃５５％の雰囲気で露光し１０秒後に処理を開始した場合と、３０℃３０％の雰囲気で露光し１０秒後に処理を開始した場合の特性曲線を求め、１０℃５５％の雰囲気で露光し１０秒後に処理を開始した場合に濃度１．０を与える露光量での濃度変化を調べた。これらの結果を表３に示した。
【０１８２】
【表３】

【０１８３】
表３の結果から明らかなように、本発明の臭化銀含有相と沃化銀含有相がそれぞれ層状に形成されている沃臭塩化銀乳剤を緑感光性乳剤層に含有した試料Ｇ−４は、緑感光性が著しく高感度で硬調であり、潜像保存性や露光温湿度依存性に優れることが認められた。
更に、試料Ｇ−４において、第一層の乳剤Ｂ−１を乳剤Ｂ−８に変えたことのみ異なる試料Ｇ−４’を作製し、上記の評価を行った結果、試料Ｇ−４とほぼ同様の結果が得られた。
【０１８４】
実施例３
実施例２の試料を用いて、レーザー走査露光によって画像形成を行った。
レーザー光源としては、半導体レーザーＧａＡｌＡｓ（発振波長 ８０８．５ｎｍ）を励起光源としたＹＡＧ固体レーザー（発振波長 ９４６ｎｍ）を反転ドメイン構造を有するＬｉＮｂＯ₃のＳＨＧ結晶により波長変換して取り出した４７３ｎｍと、半導体レーザーＧａＡｌＡｓ（発振波長 ８０８．７ｎｍ）を励起光源としたＹＶＯ₄固体レーザー（発振波長 １０６４ｎｍ）を反転ドメイン構造を有するＬｉＮｂＯ₃のＳＨＧ結晶により波長変換して取り出した５３２ｎｍと、ＡｌＧａＩｎＰ（発振波長 約６８０ｎｍ：松下電産製タイプＮｏ．ＬＮ９Ｒ２０）とを用いた。３色のそれぞれのレーザー光はポリゴンミラーにより走査方向に対して垂直方向に移動し、試料上に、順次走査露光できるようにした。半導体レーザーの温度による光量変動は、ペルチェ素子を利用して温度が一定に保たれることで抑えられている。実効的なビーム径は、８０μｍで、走査ピッチは４２．３μｍ（６００ｄｐｉ）であり、１画素あたりの平均露光時間は、１．７×１０^-7秒であった。
露光後、発色現像処理Ｂにより処理を行ったところ、実施例２での高照度露光の結果と同様、本発明の試料Ｇ−４は、緑感層が高い感度と階調を示し、また、本発明の試料Ｇ−４’は、青感層と緑感層が高い感度と階調を示し、いずれもレーザー走査露光を用いた画像形成にも適していることが分かった。
【０１８５】
【発明の効果】
本発明によれば、レーザー走査露光のようなデジタル露光においても高感度で硬調な階調が得られるハロゲン化銀乳剤およびそれを用いたハロゲン化銀写真感光材料を得ることができる。更に、本発明によれば、潜像保存性、露光温湿度依存性に優れたハロゲン化銀乳剤およびそれを用いたハロゲン化銀写真感光材料を得ることができる。
【図面の簡単な説明】
【図１】 実施例２における乳剤Ｇ−４粒子の深さ方向への臭化物および沃化物イオン濃度の分布を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide emulsion and a silver halide photographic light-sensitive material, and more specifically, a silver halide emulsion capable of obtaining a high-sensitivity and high-contrast gradation even in digital exposure such as laser scanning exposure, and the silver halide emulsion. The present invention relates to the silver halide photographic material used.
[0002]
[Prior art]
In recent years, there has been a remarkable spread of digitization in the field of color printing using color photographic paper. For example, the digital exposure method using laser scanning exposure is an analog that directly prints with a color printer from a processed color negative film. Compared to the exposure method, it shows a dramatic increase in the penetration rate. Such a digital exposure method is characterized in that high image quality can be obtained by performing image processing, and plays an extremely important role in improving the quality of color prints using color photographic paper. In addition, with the rapid spread of digital cameras, it is also an important factor that simple and high-quality color prints can be obtained from these electronic recording media, and it is thought that these will lead to further dramatic spread.
[0003]
On the other hand, as a color printing method, technologies such as an ink jet method, a sublimation type method, and color xerography have advanced, and are being recognized as a color printing method, for example, to improve photographic image quality. Among these, the characteristics of the digital exposure method using color photographic paper are high image quality, high productivity, and high image robustness. It is desired to provide it at a lower cost.
As a silver halide emulsion used for color photographic paper, a silver halide emulsion having a high silver chloride content is used mainly because of a demand for rapid processability to enhance productivity. Such a silver halide emulsion having a high silver chloride content generally tends to cause low softness in high-illuminance exposure such as laser scanning exposure, and various techniques for improving this point have been disclosed.
[0004]
It is known to dope iridium to improve the high intensity failure of silver chloride emulsions. However, silver chloride emulsions doped with iridium are known to cause latent image sensitization in a short time after exposure. For example, Japanese Patent Publication No. 7-34103 discloses a localized phase having a high silver bromide content. It is disclosed that the problem of latent image sensitization can be solved by doping iridium therein. The silver halide emulsion prepared by this method has high sensitivity and high contrast even when exposed to relatively high illuminance of about 1/100 seconds, and does not cause a problem of latent image sensitization, but is required by a digital exposure method using laser scanning exposure. When trying to maintain high sensitivity up to 1 μs ultra-high illumination exposure, the problem that hard gradation is difficult to obtain was revealed. U.S. Pat. No. 5,691,119 discloses a method for making a high-intensity gradation high-contrast by a method for preparing an emulsion having a localized phase with a high silver bromide content, but the effect is sufficient. In addition, there is a drawback that the performance is not stabilized by repeated preparation.
[0005]
U.S. Pat. Nos. 5,783,373 and 5,783,378 disclose methods of reducing high contrast and enhancing contrast using at least three types of dopants. However, a high gradation can be obtained because a dopant having a desensitizing and high gradation effect is used, which is in principle incompatible with high sensitivity.
[0006]
In US Pat. Nos. 5,726,005 and 5,736,310, an emulsion containing I having a maximum concentration on the subsurface of a high silver chloride emulsion provides an emulsion with high sensitivity and low illuminance failure. It is disclosed that it can be obtained. As a result, the higher the illuminance exposure, the higher the sensitivity, but the gray level is very soft and it is not suitable for digital exposure with a limited dynamic range of light quantity.
[0007]
JP-A-58-95736, 58-108533, 60-222844, 60-222845, 62-253143, 62-253144, 62-253166, 62-254139 63-46440, 63-46441, 63-89840, U.S. Pat.Nos. 4,820,624, 4,865,962, 5,399,475, 5 , 284, 743 and the like disclose that high sensitivity can be obtained by locally incorporating a phase having a high silver bromide content in various forms in an emulsion having a high silver chloride content. However, it is not disclosed that an emulsion containing a silver bromide-containing phase and a silver iodide-containing phase has a specific high contrast effect in ultra-high illumination exposure such as laser scanning exposure.
[0008]
US Pat. No. 5,049,485 discloses that high sensitivity and high contrast can be obtained by chemical sensitization with an Au (I) compound coordinated with a meso ion. US Pat. No. 5,945,270 discloses that high sensitivity and high contrast can be obtained by chemical sensitization with an Au (I) compound coordinated with a mercapto containing a water-soluble group. Although these are known to be relatively stable Au (I) compounds, they are emulsions containing a silver bromide-containing phase and a silver iodide-containing phase, and have a specific high-contrast effect in high-light exposure. That is not disclosed.
[0009]
[Problems to be solved by the invention]
The first problem to be solved by the present invention is to provide a silver halide emulsion capable of obtaining a high-sensitivity and high-contrast gradation without causing a reduction in sensitivity and softening even in digital exposure such as laser scanning exposure, and a It is to provide a silver halide photographic material used.
Furthermore, the second problem to be solved by the present invention is to provide a silver halide emulsion excellent in latent image storage stability and exposure temperature / humidity dependency, and a silver halide photographic light-sensitive material using the same.
[0010]
[Means for Solving the Problems]
  Means for solving the above problems are as follows. That is,
<1> A silver bromide-containing phase and a silver iodide-containing phase are each formed in layers,The silver bromide-containing phase has a silver content of 3% to 15% of the silver halide grain volume;And silver chloride content is 90 mol% or moreIn a cube or tetrahedron having a {100} plane, the circle diameter equivalent to the projected area of the particles is larger than 0.1 μm and not larger than 2 μm.A silver halide emulsion comprising silver halide grains.
<2>The silver halide emulsion according to <1>, wherein the silver bromide-containing phase is formed only at a position of 70% to 95% of the grain volume as measured from the inside of the silver halide grain.
<3> The silver bromide-containing phase is formed inside the grain with respect to the silver iodide-containing phase <1>Or <2>The silver halide emulsion described in (1).
<4> The silver bromide-containing phase and the silver iodide-containing phase are formed adjacent to each other <1> toAny of <3>The silver halide emulsion described in (1).
<5>The silver halide emulsion according to any one of <1> to <4>, which has a silver iodide-containing phase on the surface of the silver halide grains.
<6> The electron release time of the silver halide grains is 10^-5<1> to <10 seconds from 10 seconds5>Or a silver halide emulsion according to any one of the above.
<7The silver halide grains include a hexacoordinate complex having Ir as a central metal having Cl, Br, or I as a ligand.6>Or a silver halide emulsion according to any one of the above.
<8The hexacoordination complex is contained in a silver bromide-containing phase <7>The silver halide emulsion described in (1).
<9> The silver halide grains include a hexacoordination complex having Ir as a central metal having at least one non-halogen as a ligand <1> to <8>Or a silver halide emulsion according to any one of the above.
<10>The silver halide grains have at least one H-coordination complex having iridium as a central metal. ₂ The silver halide emulsion according to any one of <1> to <8>, having O, OH, O, OCN, thiazole or substituted thiazole as a ligand.
<11> The oxidation potential of the latent image of the silver halide emulsion is more noble than 70 mV <1> to <10>Or a silver halide emulsion according to any one of the above.
<12> The silver halide emulsion is gold sensitized <1> to <111>Or a silver halide emulsion according to any one of the above.
<13> The silver halide emulsion contains colloidal gold sulfide or gold complex stability constant log β₂Is sensitized with a gold sensitizer of 21 to 3512>The silver halide emulsion described in (1).
<14>The silver halide emulsion has a gold complex stability constant log β ₂ Is a silver halide emulsion as described in <12>, which is gold-sensitized with a gold sensitizer represented by the following general formula (I) having a molecular weight of 21 or more and 35 or less.
Formula (I)
    {(L ¹ ) _x (Au) _y (L ² ) _z ・ Q _q } _p
In general formula (I), L ¹ And L ² Is log β ₂ Represents a compound having a value between 21 and 35. Q represents a counter anion or counter cation necessary for neutralizing the charge of the compound, x and z represent an integer of 0 to 4, y and p represent 1 or 2, and q includes a decimal number 0 Represents a value of ~ 1. However, neither x nor z is 0.
<15>The silver halide emulsion according to any one of <1> to <14>, wherein the silver halide emulsion is a silver halide emulsion for a silver halide color photographic light-sensitive material.Is.
<16>At least one silver halide emulsion layer containing a yellow dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a cyan dye-forming coupler are provided on the support. Silver halide color photographic feel In optical materials, <1> ~ <14>A silver halide photographic light-sensitive material comprising the silver halide emulsion described in any of the above.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
  The present invention is described in detail below.
  The silver halide emulsion of the present invention contains specific silver halide grains. Particle shape of this particleIs {Cubic or tetrahedral crystal grains with 100} planes (these may have rounded vertices and higher order planes)It is.
[0012]
As the silver halide emulsion of the present invention, an emulsion containing specific silver halide grains is used. The silver chloride content needs to be 90 mol% or more, and from the viewpoint of rapid processability, the silver chloride content is preferably 93 mol% or more, and more preferably 95 mol% or more. The silver bromide content is preferably 0.1 to 7 mol%, more preferably 0.5 to 5 mol%, since it is a high contrast and has excellent latent image stability. The silver iodide content is preferably 0.02-1 mol%, more preferably 0.05-0.50 mol%, and more preferably 0.07-0. 40 mol% is most preferred.
The specific silver halide grains of the present invention are preferably silver iodobromochloride grains, more preferably silver iodobromochloride grains having the above halogen composition.
[0013]
The specific silver halide grains in the silver halide emulsion of the present invention have a silver bromide-containing phase and a silver iodide-containing phase. Here, the silver bromide or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than the surroundings. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide or silver iodide-containing phase may form a layer having a substantially constant width at a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more, more preferably 10 to 80 mol%, and most preferably 15 to 50 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Most preferred. Further, a plurality of such silver bromide or silver iodide-containing phases may be formed in layers in each grain, and the silver bromide or silver iodide content may be different, but at least one of each. It is necessary to have a contained phase of
[0014]
It is important that the silver bromide-containing phase and the silver iodide-containing phase of the silver halide emulsion of the present invention are layered so as to surround each grain. In one preferred embodiment, the silver bromide-containing phase or the silver iodide-containing phase formed in layers so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains in each phase. However, in the silver bromide-containing phase or silver iodide-containing phase that are layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain, and the concentration distribution You may have. For example, when a silver bromide-containing phase or silver iodide-containing phase is formed in a layer so as to surround the grain in the vicinity of the grain surface, the silver bromide or silver iodide concentration at the grain corner or edge is different from the main surface. There is a case. In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, the silver bromide-containing phase that is completely isolated in a specific part of the surface of the grain and does not surround the grain Alternatively, there may be a silver iodide containing phase.
[0015]
  Such a silver bromide-containing phase or silver iodide-containing phase is composed of a silver amount of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. Preferably 3% or more and 15% or less of silver.. However, in the present invention, the silver bromide-containing phase needs to be composed of a silver amount of 3% to 15% of the grain volume.
[0016]
The silver bromide-containing phase and the silver iodide-containing phase of the silver halide emulsion of the present invention may be in the same place or in different places of the grain, but it is easier to control grain formation in different places. This is preferable. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, iodide added during the formation of high silver chloride grains tends to ooze out on the grain surface than bromide, so the silver iodide-containing phase tends to be formed near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different locations in the grain, the silver bromide-containing phase is preferably formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.
[0017]
The silver bromide content or silver iodide content necessary for exhibiting the effects of the present invention such as high sensitivity and high contrast is such that the silver bromide-containing phase or silver iodide-containing phase is formed inside the grain. There is a risk that the amount of silver chloride may be reduced more than necessary, and the rapid processability may be impaired. Therefore, in order to concentrate these functions for controlling the photographic action near the surface in the grain, the silver bromide-containing phase and the silver iodide-containing phase are preferably adjacent to each other. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume as measured from the inside, and the silver iodide-containing phase is any of the positions at 85% to 100% of the grain volume. It is preferable to form it. Further, the silver bromide-containing phase is formed at any position from 70% to 95% of the grain volume, and the silver iodide-containing phase is further formed at any position from 90% to 100% of the grain volume. preferable.
[0018]
Introducing bromide or iodide ions to contain silver bromide or silver iodide in the silver halide emulsion of the present invention may be carried out by adding a bromide salt or iodide salt solution alone, Along with the addition of the chloride salt solution, a bromide salt or iodide salt solution may be added. In the latter case, bromide salt or iodide salt solution and high chloride salt solution may be added separately or as a mixed solution of bromide salt or iodide salt and high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ions or iodide ions from organic molecules described in US Pat. No. 5,389,508. As another bromide or iodide ion source, fine silver bromide grains or fine silver iodide grains can also be used.
[0019]
The addition of the bromide salt or iodide salt solution may be concentrated at one time of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining an emulsion with high sensitivity and low covering. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. Further, the addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, so that an emulsion with higher sensitivity and lower covering can be obtained.
On the other hand, the addition of the bromide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70%.
[0020]
Distribution of bromide or iodide ion concentration in the depth direction in the grain is measured by etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using TRIFT II type TOF-SIMS manufactured by Phi Evans. it can. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan. When the emulsion grains are analyzed by the etching / TOF-SIMS method, it is possible to analyze that iodide ions ooze out toward the grain surface even when the addition of the iodide salt solution is finished inside the grains. The emulsion of the present invention is analyzed by etching / TOF-SIMS method, and it is preferable that iodide ions have a maximum concentration on the grain surface, and the iodide ion concentration is attenuated toward the inside. It is preferable to have a concentration maximum inside. The local concentration of silver bromide can also be measured by X-ray diffraction if the silver bromide content is somewhat high.
[0021]
The electron release time of the silver halide emulsion of the present invention is 10^-FivePreferably between 2 and 10 seconds. Here, the electron slow release time is the time until photoelectrons generated in a silver halide crystal are captured by an electron trap in the crystal and emitted again when the silver halide emulsion is exposed. . Electronic sustained release time is 10^-FiveIf it is shorter than 2 seconds, it is difficult to obtain a high-sensitivity and high-contrast gradation in high-illuminance exposure, and if it is longer than 10 seconds, a problem of latent image sensitization occurs before processing in a short time after exposure. Electron sustained release time is 10^-FourMore preferably between 10 seconds and 10 seconds.^-3Most preferred is between 1 second and 1 second.
[0022]
The electron sustained release time can be measured by a double pulse photoconduction method. Using a microwave photoconductive method or a radio wave photoconductive method, a first short-time exposure is given, and then a second short-time exposure is given after a certain time. Electrons are trapped in the electron trap in the silver halide crystal by the first exposure, and if the second exposure is applied immediately after that, the electron trap is clogged, so that the second photoconductive signal is increased. When the interval between the two exposures is sufficiently set and the electrons captured by the electron trap in the first exposure have already been emitted, the second photoconductive signal has almost returned to its original size. By changing the exposure interval twice and taking the exposure interval dependency of the second photoconductive signal intensity, it is possible to measure how the second photoconductive signal intensity decreases with the exposure interval. This represents the sustained release time of photoelectrons from the electron trap. The sustained release of electrons may continue to occur continuously for a certain period of time after exposure.^-FiveIt is preferred that sustained release is observed between 1 second and 10 seconds. 10^-FourMore preferably, sustained release is observed between 1 second and 10 seconds.^-3More preferably, sustained release is observed between 1 second and 1 second.
[0023]
The specific silver halide grains in the silver halide emulsion of the present invention preferably contain iridium. As the iridium compound, a 6-coordination complex having 6 ligands and having iridium as a central metal is preferable because it can be uniformly incorporated into a silver halide crystal. As one preferred embodiment of the iridium used in the present invention, a hexacoordinate complex having Ir as a central metal having Cl, Br or I as a ligand is preferred, and Ir comprising all six ligands consisting of Cl, Br or I is preferred. A hexacoordinate complex as a central metal is more preferable. In this case, Cl, Br, or I may be mixed in the hexacoordinate complex. It is particularly preferable that a hexacoordinate complex having Ir as a central metal having Cl, Br, or I as a ligand is contained in a silver bromide-containing phase in order to obtain a high gradation at high illumination exposure.
[0024]
Specific examples of the 6-coordination complex in which all six ligands are composed of Cl, Br or I and having Ir as a central metal are given below, but iridium in the present invention is not limited to these.
[IrCl₆]^2-
[IrCl₆]^3-
[IrBr₆]^2-
[IrBr₆]^3-
[IrI₆]^3-
[0025]
As a different preferred embodiment of iridium used in the present invention, a hexacoordination complex having Ir as a central metal having at least one non-halogen as a ligand is preferred, and H₂Preferred is a hexacoordination complex having Ir as a central metal having O, OH, O, OCN, thiazole or substituted thiazole as a ligand, and at least one H₂More preferred is a hexacoordinated complex having Ir as a central metal, wherein O, OH, O, OCN, thiazole or substituted thiazole is used as a ligand, and the remaining ligand is Cl, Br or I. Further, a hexacoordinate complex having 1 or 2 5-methylthiazole as a ligand and the remaining ligand of Cl, Br or I and having Ir as a central metal is most preferable.
[0026]
Below, at least one H₂Specific examples of 6-coordination complexes having O, OH, O, OCN, thiazole or substituted thiazole as a ligand and the remaining ligand of which is composed of Cl, Br or I as a central metal are given below. It is not limited to these.
[0027]
[Ir (H₂O) Cl_Five]^2-
[Ir (H₂O)₂Cl_Four]^-
[Ir (H₂O) Br_Five]^2-
[Ir (H₂O)₂Br_Four]^-
[Ir (OH) Cl_Five]^3-
[Ir (OH)₂Cl_Four]^3-
[Ir (OH) Br_Five]^3-
[Ir (OH)₂Br_Four]^3-
[Ir (O) Cl_Five]^Four-
[Ir (O)₂Cl_Four]^Five-
[Ir (O) Br_Five]^Four-
[Ir (O)₂Br_Four]^Five-
[Ir (OCN) Cl_Five]^3-
[Ir (OCN) Br_Five]^3-
[Ir (thiazole) Cl_Five]^2-
[Ir (thiazole)₂Cl_Four]^-
[Ir (thiazole) Br_Five]^2-
[Ir (thiazole)₂Br_Four]^-
[Ir (5-methylthiazole) Cl_Five]^2-
[Ir (5-methylthiazole)₂Cl_Four]^-
[Ir (5-methylthiazole) Br_Five]^2-
[Ir (5-methylthiazole)₂Br_Four]^-
[0028]
An object of the present invention is to provide a six-coordinate complex having Ir as a central metal, in which all six ligands are Cl, Br or I, or at least one H₂By using either one of six-coordinate complexes having O, OH, O, OCN, thiazole or substituted thiazole as a ligand, and the remaining ligand consisting of Cl, Br or I and having Ir as a central metal. Preferably achieved. However, in order to further enhance the effect of the present invention, all six ligands have a six-coordination complex centered on Ir consisting of Cl, Br or I, and at least one H₂It is preferable to use together a 6-coordination complex having Ir as a central metal, wherein O, OH, O, OCN, thiazole or substituted thiazole is used as a ligand and the remaining ligand is Cl, Br or I. Furthermore, at least one H₂A hexacoordinate complex having Ir as a central metal, which is composed of O, OH, O, OCN, thiazole or substituted thiazole as a ligand, and the remaining ligand is Cl, Br or I, has two types of ligands (H₂It is preferable to use a complex composed of one kind from O, OH, O, OCN, thiazole or substituted thiazole and one kind from Cl, Br or I).
[0029]
The metal complex mentioned above is an anion, and when it forms a salt with a cation, the one that is easily dissolved in water as its counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do. These iridium complexes are 1 x 10 per mole of silver during grain formation.^-TenFrom mole to 1 × 10^-3It is preferable to add 1 mol.^-8From mole to 1 × 10^-FiveMost preferably, it is added in a molar amount.
[0030]
In the present invention, the above-mentioned iridium complex is added directly to the reaction solution at the time of silver halide grain formation, or added to an aqueous halide solution for forming silver halide grains, or to other solutions to form grains. It is preferably incorporated into the silver halide grains by adding to the reaction solution. It is also preferable to physically ripen the fine particles in which the iridium complex is previously incorporated in the grains and to incorporate them into the silver halide grains. Further, these methods can be combined and contained in the silver halide grains.
[0031]
When these complexes are incorporated into silver halide grains, they may be uniformly present inside the grains, but are disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to exist only in the particle surface layer, and it is also preferable to add a layer containing no complex only on the particle surface and containing no complex on the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Further, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, but a hexacoordinate complex having Ir as a central metal, in which all six ligands are Cl, Br, or I, has a silver bromide concentration maximum. It is preferable to contain.
[0032]
In the present invention, in addition to iridium, other metal ions can be doped inside and / or on the surface of silver halide grains. As a metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any of the above metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and a plurality of kinds of ligands are contained in one complex molecule. It is also preferable to use it. An organic compound can also be used as the ligand, and preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom in the molecule as a coordination atom to the metal, particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds are used as a basic skeleton and substituents are introduced into them are also preferable.
[0033]
A combination of metal ions and ligands is preferably a combination of iron ions, ruthenium ions and cyanide ions. In the present invention, it is preferable to use iridium and these compounds in combination. In these compounds, the cyanide ion preferably accounts for a majority of the coordination number to iron or ruthenium as the central metal, and the remaining coordination sites are thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, It is preferably occupied by pyrazine or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. These cyanide ion-ligand complexes are 1 x 10 per mole of silver during grain formation.^-8From mole to 1 × 10^-2It is preferable to add 1 mol.^-6From mole to 5 × 10^-FourMost preferably, it is added in a molar amount. When ruthenium and osmium are used as the central metals, it is also preferable to use nitrosyl ions, thionitrosyl ions, or water molecules and chloride ions together as ligands. More preferably, a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex is formed, and a hexachloro complex is also preferably formed. These complexes are 1 x 10 per mole of silver during grain formation.^-TenFrom mole to 1 × 10^-6Mole addition is preferred, more preferably 1 × 10^-9From mole to 1 × 10^-6The molar addition.
[0034]
  The average grain size of the silver halide grains contained in the silver halide emulsion of the present invention (the grain diameter is defined as the diameter of a circle equivalent to the projected area of the grains and the number average thereof) is 0.1.Bigger2 μmIs. The particle size distribution is preferably a so-called monodispersed material having a coefficient of variation (the standard deviation of the particle size distribution divided by the average particle size) of 20% or less, desirably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating.
[0035]
The silver halide emulsion of the present invention may contain silver halide grains other than the silver halide grains (that is, specific silver halide grains) contained in the silver halide emulsion defined in the present invention. However, the silver halide grains contained in the silver halide emulsion defined in the present invention is preferably 50% or more, more preferably 80% or more, per projected area of all silver halide grains in the silver halide emulsion. More preferably.
[0036]
The oxidation potential of the latent image of the silver halide emulsion of the present invention is preferably nobler than 70 mV, and more preferably nobler than 100 mV. That the oxidation potential of the latent image is nobler than 70 mV means that the oxidation resistance of the latent image is relatively strong. The oxidation potential of the latent image can be measured by a method described in a known document such as Photographic Sensitivity (Oxford University Press, Tadaki Tani 1995) page 103. Specifically, a silver halide emulsion coating is exposed to a gradation of 0.1 seconds and immersed in an oxidation-reduction bath at various potentials before development to examine the potential at which the latent image is bleached. is there.
[0037]
The silver halide emulsion of the present invention is usually subjected to chemical sensitization. Regarding chemical sensitization, sulfur sensitization represented by addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, right lower column to page 22, upper right column are preferably used. Of these, gold sensitization is particularly preferred. This is because by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with laser light or the like can be further reduced.
[0038]
In order to sensitize the silver halide emulsion of the present invention to gold sensitization, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands can be used. it can. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate such as gold (I) potassium dithiocyanate or gold (I) 3 dithiosulfate. Compounds such as gold dithiosulfate compounds such as sodium can be used.
[0039]
The silver halide emulsion of the present invention contains colloidal gold sulfide or gold complex stability constant log β₂Is preferably sensitized with a gold sensitizer of 21 to 35. Colloidal gold sulfide is produced by Research Disclosure, 37154, Solid State Ionics 79, 60-66, 1995, Compt. Rend. Hebt. Seances Acad. Sci. Sect. .B 263, p. 1328, published in 1966. Various sizes of colloidal gold sulfide can be used, and those having a particle size of 50 nm or less can also be used. The amount added can vary widely depending on the case, but 5 × 10 5 as gold atoms per mole of silver halide.^-7~ 5x10^-3Mole, preferably 5 × 10^-6~ 5x10^-FourIs a mole. In the present invention, gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using other than gold compounds.
[0040]
Below, the complex stability constant of gold log β₂Will be described below.
Gold complex stability constant logβ₂Is measured by Comprehensive Coordination Chemistry (Chapter 55, 864, 1987), Encyclopedia of Electrochemistry, The Elements. IV-3, 1975), Journal of the Royal Netherlands Chemical Society, 101, 164, 1982), and references thereof. The measurement method is applied, the measurement temperature is 25 ° C, the pH is potassium dihydrogen phosphate / hydrogen phosphate It is adjusted to 6.0 with disodium buffer, and the ionic strength is log β from the value of the gold potential under the condition of 0.1 M (KBr).₂Is obtained by calculation. Log β of thiocyanate ion in this measurement method₂The value of 20.5 is 20.5, and the value described in the literature (Comprehensive Coordination Chemistry, 1987, Chapter 55, page 864, Table 2), a value close to 20, is obtained.
[0041]
Gold complex stability constant log β in the present invention₂The gold sensitizer having a valence of 21 or more and 35 or less is preferably represented by the following general formula (I).
Formula (I) {(L¹)_x(Au)_y(L²)_z・ Q_q}_p
[0042]
In general formula (I), L¹And L²Is log β₂Represents a compound having a value between 21 and 35. Preferred are compounds contained between 22 and 31, more preferred are compounds contained between 24 and 28.
[0043]
L¹And L²Is, for example, a compound containing at least one unstable sulfur group capable of reacting with silver halide to form silver sulfide, a hydantoin compound, a thioether compound, a mesoionic compound, -SR ', a heterocyclic compound, a phosphine compound Represents an amino acid derivative, a sugar derivative, or a thiocyano group, which may be the same as or different from each other. Here, R ′ represents an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, a thiocarbamoyl group, or a sulfonyl group.
Q represents a counter anion or counter cation necessary for neutralizing the charge of the compound, x and z represent an integer of 0 to 4, y and p represent 1 or 2, and q includes a decimal number 0 Represents a value of ~ 1. However, neither x nor z is 0.
[0044]
The compound represented by the general formula (I) is preferably L¹And L²A compound containing at least one labile sulfur group capable of reacting with silver halide to form silver sulfide, a hydantoin compound, a thioether compound, a mesoionic compound, -SR ', a heterocyclic compound, or a phosphine compound. X, y and z each represent 1.
[0045]
More preferably, the compound represented by formula (I) is L¹And L²Represents a compound containing at least one labile sulfur group capable of reacting with silver halide to form silver sulfide, a mesoionic compound, or -SR ', wherein x, y, z, and p are each 1 To express.
[0046]
Hereinafter, the gold compound represented by the general formula (I) will be described in more detail.
In general formula (I), L¹And L²Examples of the compound having an unstable sulfur group that can generate silver sulfide by reacting with silver halide represented by the formula: thioketones (for example, thioureas, thioamides, or rhodanines), thiophosphate And thiosulfuric acid.
[0047]
A compound containing at least one unstable sulfur group capable of reacting with silver halide to produce silver sulfide preferably represents thioketones (preferably thioureas, thioamides, etc.) and thiosulfuric acids. .
[0048]
Next, in general formula (I), L¹And L²Examples of the hydantoin compound represented by the formula include unsubstituted hydantoin, N-methylhydantoin and the like, and the thioether compound contains 1 to 8 thio groups, which are substituted or unsubstituted linear or A branched alkylene group (for example, ethylene, triethylene, etc.) or a chain or cyclic thioether linked by a phenylene group (for example, bishydroxyethyl thioether, 3,6-dithia-1,8-octanediol, 1,4 , 8,11-tetrathiacyclotetradecane) and the like, and mesoionic compounds include mesoionic-3-mercapto-1,2,4-triazoles (for example, mesoionic-1,4,5-trimethyl-). 3-mercapto-1,2,4-triazole and the like.
[0049]
Next, in general formula (I), L¹And L²When -SR 'represents, the aliphatic hydrocarbon group represented by R' is a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl). , N-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 1,5-dimethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n- Hexadecyl, hydroxyethyl, hydroxypropyl, 2,3-dihydroxypropyl, carboxymethyl, carboxyethyl, sodium sulfoethyl, diethylaminoethyl, diethylaminopropyl, butoxypropyl, ethoxyethoxyethyl, n-hexyloxypropyl, etc.), carbon number 3 18 substituted or unsubstituted cyclic alkyl groups (eg Cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, cyclododecyl, etc.), alkenyl groups having 2 to 16 carbon atoms (for example, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups having 2 to 10 carbon atoms ( For example, propargyl, 3-pentynyl and the like), aralkyl groups having 6 to 16 carbon atoms (for example, benzyl and the like) and the like, and aryl groups include substituted or unsubstituted phenyl groups and naphthyl groups having 6 to 20 carbon atoms. (For example, unsubstituted phenyl, unsubstituted naphthyl, 3,5-dimethylphenyl, 4-butoxyphenyl, 4-dimethylaminophenyl, 2-carboxyphenyl, etc.) and the like. Examples of the heterocyclic group include substituted or unsubstituted A nitrogen-containing hetero 5-membered ring (for example, imidazolyl, 1,2,4-triazolyl) Tetrazolyl, oxadiazolyl, thiadiazolyl, benzimidazolyl, purinyl, etc.), substituted or unsubstituted nitrogen-containing hetero 6-membered ring (for example, pyridyl, piperidyl, 1,3,5-triazino, 4,6-dimercapto-1,3,5- Triazino, etc.), furyl group, thienyl group, etc., examples of the acyl group include acetyl, benzoyl, etc., examples of the carbamoyl group include dimethylcarbamoyl, and examples of the thiocarbamoyl group include, for example, diethylthiocarbamoyl Examples of the sulfonyl group include substituted or unsubstituted alkylsulfonyl groups having 1 to 10 carbon atoms (for example, methanesulfonyl, ethanesulfonyl, etc.), substituted or unsubstituted phenylsulfonyl groups having 6 to 16 carbon atoms ( For example, phenylsulfo Le etc.).
[0050]
L¹And L²R— is preferably an aryl group or a heterocyclic group, more preferably a heterocyclic group, still more preferably a 5-membered or 6-membered nitrogen-containing heterocyclic group, A nitrogen-containing heterocyclic group substituted with a water-soluble group (for example, sulfo, carboxy, hydroxy, amino, etc.) is preferable.
[0051]
In general formula (I), L¹And L²As the heterocyclic compound represented by the formula, substituted or unsubstituted nitrogen-containing hetero five-membered rings (for example, pyrroles, imidazoles, pyrazoles, 1,2,3-triazoles, 1,2,4-triazoles) , Tetrazoles, oxazoles, isoxazoles, isothiazoles, oxadiazoles, thiadiazoles, pyrrolidines, pyrrolines, imidazolidines, imidazolines, pyrazolidines, pyrazolines, hydantoins, etc.), and Heterocycles containing 5-membered rings (indoles, isoindoles, indolizines, indazoles, benzimidazoles, purines, benzotriazoles, carbazoles, tetraazaindenes, benzothiazoles, indolines, etc. ), Substituted or unsubstituted nitrogen-containing hetero 6-membered (For example, pyridines, pyrazines, pyrimidines, pyridazines, triazines, thiadiazines, piperidines, piperazines, morpholines, etc.) and heterocycles containing the 6-membered ring (for example, quinolines, Isoquinolines, phthalazines, naphthyridines, quinoxalines, quinazolines, pteridines, phenaziridines, acridines, phenanthrolines, phenazines, etc.), substituted or unsubstituted furans, substituted or unsubstituted thiophenes, benzothia Examples include zoliums.
[0052]
L¹And L²Preferably, the heterocyclic compound represented by the formula is an unsaturated nitrogen-containing hetero 5-membered or 6-membered ring or a heterocyclic ring containing it, such as pyrroles, imidazoles, pyrazoles, 1, 2,4-triazoles, oxadiazoles, thiadiazoles, imidazolines, indoles, indolizines, indazoles, benzimidazoles, purines, benzotriazoles, carbazoles, tetraazaindenes, benzothiazoles Pyridines, pyrazines, pyrimidines, pyridazines, triazines, quinolines, isoquinolines, phthalazines and the like, and also heterocyclic compounds known in the art as antifoggants (eg, indazoles). , Benzimidazoles, benzotriazoles, teto Azaindenes, etc.) is preferable.
[0053]
In general formula (I), L¹And L²As the phosphine compound represented by formula (1), an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heterocyclic group (for example, pyridyl), a substituted or unsubstituted amino group (for example, dimethyl) Amino), and / or phosphines substituted with an alkyloxy group (for example, methyloxy, ethyloxy, etc.), preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. Substituted with phosphines (eg, triphenylphosphine, triethylphosphine, etc.).
[0054]
Furthermore, the above, L¹And L²The mesoionic compound represented by the formula, —SR ′, and the heterocyclic compound are substituted with an unstable sulfur group (for example, thioureido group) that can react with silver halide to form silver sulfide. It is preferable.
[0055]
In addition, L in the above general formula (I)¹, L²The compound represented by the formula (1) may further have as many substituents as possible, and examples of the substituent include a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), an aliphatic hydrocarbon group (for example, Methyl, ethyl, isopropyl, n-propyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl etc.), alkenyl group (eg allyl, 2-butenyl, 3-pentenyl etc.), alkynyl group (eg propargyl, 3-pentynyl etc.) ), Aralkyl groups (eg benzyl, phenethyl etc.), aryl groups (eg phenyl, naphthyl, 4-methylphenyl etc.), heterocyclic groups (eg pyridyl, furyl, imidazolyl, piperidinyl, morpholyl etc.), alkyloxy groups (eg methoxy) , Ethoxy, butoxy, 2-ethylhexyloxy, ethoxyethoxy Methoxyethoxy etc.), aryloxy groups (eg phenoxy, 2-naphthyloxy etc.), amino groups (eg unsubstituted amino, dimethylamino, diethylamino, dipropylamino, dibutylamino, ethylamino, dibenzylamino, anilino etc.), Acylamino group (eg acetylamino, benzoylamino etc.), ureido group (eg unsubstituted ureido, N-methylureido, N-phenylureido etc.), thioureido group (eg unsubstituted thioureido, N-methylthioureido, N-phenylthioureido) Etc.), selenureido groups (eg unsubstituted selenoureido etc.), phosphine selenide groups (eg diphenylphosphine selenide etc.), tellurolide groups (eg unsubstituted telurolide etc.), urethane groups (eg methoxycarbonylamino, Nonoxycarbonylamino, etc.), sulfonamido groups (eg, methylsulfonamide, phenylsulfonamide, etc.), sulfamoyl groups (eg, unsubstituted sulfamoyl groups, N, N-dimethylsulfamoyl, N-phenylsulfamoyl, etc.), carbamoyl Groups (for example, unsubstituted carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl, etc.), sulfonyl groups (for example, methanesulfonyl, p-toluenesulfonyl, etc.), sulfinyl groups (for example, methylsulfinyl, phenylsulfinyl, etc.), alkyloxycarbonyl Groups (for example, methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (for example, phenoxycarbonyl, etc.), acyl groups (for example, acetyl, benzoyl, formyl, pivaloyl, etc.), acyloxy groups (For example, acetoxy, benzoyloxy, etc.), phosphoric acid amide group (for example, N, N-diethylphosphoric acid amide, etc.), alkylthio group (for example, methylthio, ethylthio, etc.), arylthio group (for example, phenylthio, etc.), cyano group, sulfo group Thiosulfonic acid group, sulfinic acid group, carboxy group, hydroxy group, mercapto group, phosphono group, nitro group, sulfino group, ammonio group (for example, trimethylammonio group), phosphonio group, hydrazino group, thiazolino group, silyloxy group (t -Butyldimethylsilyloxy, t-butyldiphenylsilyloxy) and the like. When there are two or more substituents, they may be the same or different.
[0056]
Next, Q and q in the general formula (I) will be described.
In the general formula (I), the counter anion represented by Q is a halogenium ion (for example, F^-, Cl^-, Br^-, I^-), Tetrafluoroborate ion (BF_Four ^-), Hexafluorophosphate ion (PF)₆ ^-), Sulfate ion (SO_Four ^2-), Aryl sulfonate ions (eg, p-toluene sulfonate ion, naphthalene-2,5-disulfonate ion, etc.), carboxy ions (eg, acetate ion, trifluoroacetate ion, oxalate ion, benzoate ion, etc.) and the like. The counter cations represented by Q include alkali metal ions (for example, lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, etc.), alkaline earth metal ions (for example, magnesium ions, calcium ions, etc.), Substituted or unsubstituted ammonium ion (eg, unsubstituted ammonium ion, triethylammonium, tetramethylammonium, etc.), substituted or unsubstituted pyridinium ion (eg, unsubstituted pyridinium ion, 4-phenylpyridinium) Ion etc.) and the like, further, include proton. Q is the number of Q for neutralizing the charge of the compound and represents a value from 0 to 1, and the value may be a decimal number.
[0057]
The counter anion represented by Q is preferably a halogenium ion (for example, Cl^-, Br^-), Tetrafluoroborate ion, hexafluorophosphate ion, sulfate ion, preferably as a counter cation represented by Q, an alkali metal ion (for example, sodium ion, potassium ion, rubidium ion, cesium ion, etc.), substituted or An unsubstituted ammonium ion (for example, an unsubstituted ammonium ion, triethylammonium, tetramethylammonium, etc.) or a proton.
[0058]
Below, L¹Or L²Although the specific example of a compound represented by this is shown, this invention is not limited to these. The numbers in parentheses are logβ₂Indicates the value.
[0059]
[Chemical 1]

[0060]
[Chemical formula 2]

[0061]
The compound represented by the general formula (I) can be obtained by a known method such as Inorganic and Nuclear Chemistry Letters (INORG.NUCL.CHEM.LETTERSVOL.10, 641, 1974), Transition Metal Chemistry (TransitionMet. Chem. 1, 248, 1976), Acta crystallographica (Acta. Cryst. B32, 3321, 1976), JP-A-8-69075, Japanese Patent Publication No. 45-8831, European Patent 915371A1 , JP-A-6-11788, JP-A-6-501789, JP-A-4-267249, JP-A-9-118865, and the like.
[0062]
Next, although the specific example of a compound represented by general formula (I) is shown, this invention is not limited to these.
[0063]
[Chemical 3]

[0064]
[Formula 4]

[0065]
[Chemical formula 5]

[0066]
The gold sensitization in the present invention is usually performed by adding a gold sensitizer and stirring the emulsion for a predetermined time at a high temperature (preferably 40 ° C. or higher). The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is 1 × 10 5 per mole of silver halide.^-71 x 10 moles or more^-FourMolar or less is preferable.
[0067]
In the present invention, as a gold sensitizer, in addition to the above-mentioned compounds, commonly used gold compounds (for example, chloroaurate, potassium chloroaurate, auric trichloride, potassium aurithiocyanate, potassium iodoaurate, tetracyanoauric) Acid, ammonium aurothiocyanate, pyridyltrichlorogold, etc.) can be used in combination.
[0068]
The silver halide emulsion of the present invention can be used in combination with other chemical sensitization in addition to gold sensitization. Chemical sensitization methods that can be used in combination include sulfur sensitization, selenium sensitization, tellurium sensitization, sensitization of noble metals other than gold, or reduction sensitization. As compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, right lower column to page 22, upper right column are preferably used.
[0069]
To the silver halide emulsion of the present invention, various compounds or precursors thereof may be added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. Can do. As specific examples of these compounds, those described in pages 39 to 72 of JP-A-62-215272 are preferably used. Further, 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (the aryl residue has at least one electron-withdrawing group) are also preferably used.
[0070]
In the present invention, in order to enhance the storage stability of the silver halide emulsion, both ends are adjacent to the hydroxamic acid derivative described in JP-A-11-109576 and the carbonyl group described in JP-A-11-327094. Cyclic ketones having a double bond substituted with an amino group or a hydroxyl group (particularly those represented by the general formula (S1), paragraph numbers 0036 to 0071 can be incorporated in the present specification), particularly Sulfo-substituted catechol and hydroquinones described in JP-A-11-143011 (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4 -Dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid Acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), hydroxylamines represented by the general formula (A) in US Pat. No. 5,556,741 (US Pat. No. 556,741 column 4, line 56 to column 11, line 22 is preferably applied to the present application and is incorporated as part of the specification of the present application), Japanese Patent Application Laid-Open No. 11-102045. The water-soluble reducing agents represented by the general formulas (I) to (III) are also preferably used in the present invention.
[0071]
The silver halide emulsion of the present invention may contain a spectral sensitizing dye for the purpose of imparting so-called spectral sensitivity exhibiting photosensitivity in a desired light wavelength range. Examples of spectral sensitizing dyes used for spectral sensitization in the blue, green and red regions include F.I. M.M. Examples include those described in Harmer's Heterocyclic compounds-Cyanedines and related compounds (John Wiley & Sons [New York, London, 1964)]. As specific examples of compounds and spectral sensitization, those described in JP-A-62-215272, page 22, right upper column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye of silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, adsorbed, and exposed. This is very preferable from the viewpoint of temperature dependency.
[0072]
The addition amount of these spectral sensitizing dyes varies widely depending on the case, and is 0.5 × 10 5 per mol of silver halide.^-6Mol ~ 1.0 × 10^-2A molar range is preferred. More preferably, 1.0 × 10^-6Mol ~ 5.0 × 0^-3The range of moles.
[0073]
Next, the silver halide photographic light-sensitive material of the present invention will be described.
The silver halide photographic light-sensitive material of the present invention may be black-and-white or color. Preferably, the silver halide emulsion of the present invention is used for the silver halide color photographic light-sensitive material.
A silver halide color photographic light-sensitive material in which the silver halide emulsion of the present invention is preferably used (hereinafter sometimes simply referred to as “photosensitive material”) is a silver halide emulsion layer containing a yellow dye-forming coupler on a support. A silver halide color photographic material having at least one silver halide emulsion layer containing a magenta dye-forming coupler and a silver halide emulsion layer containing a cyan dye-forming coupler. Among them, at least one layer contains the silver halide emulsion of the present invention. In the present invention, the silver halide emulsion layer containing the yellow dye-forming coupler contains a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler contains a magenta coloring layer, and the cyan dye-forming coupler. The silver halide emulsion layer functions as a cyan color-developing layer. The silver halide emulsion contained in each of the yellow coloring layer, the magenta coloring layer, and the cyan coloring layer is sensitive to light in different wavelength regions (for example, light in the blue region, green region, and red region). It is preferable to have.
[0074]
The light-sensitive material of the present invention may have a hydrophilic colloid layer, an antihalation layer, an intermediate layer, and a colored layer, which will be described later, if desired, in addition to the yellow coloring layer, magenta coloring layer, and cyan coloring layer.
[0075]
Conventionally known photographic materials and additives can be used in the light-sensitive material of the present invention.
For example, a transmissive support or a reflective support can be used as the photographic support. As the transparent support, transparent films such as cellulose nitrate film and polyethylene terephthalate, polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), and polyester of NDCA, terephthalic acid and EG For example, an information recording layer such as a magnetic layer is preferably used. As the reflective support, a reflective support that is laminated with a plurality of polyethylene layers or polyester layers and contains a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminate layers) is preferable.
[0076]
In the present invention, more preferred reflective supports include those having a polyolefin layer having fine pores on the paper substrate on the side on which the silver halide emulsion layer is provided. The polyolefin layer may be composed of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no micropores (eg, polypropylene, polyethylene) and is close to the paper substrate. More preferred is a polyolefin (for example, polypropylene or polyethylene) having micropores on the side. The density of the multi-layer or single-layer polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 0.40 to 1.0 g / ml, and more preferably 0.50 to 0.70 g / ml. The thickness of the multilayer or single polyolefin layer located between the paper substrate and the photographic composition layer is preferably 10 to 100 μm, more preferably 15 to 70 μm. Further, the ratio of the thickness of the polyolefin layer to the paper substrate is preferably 0.05 to 0.2, more preferably 0.1 to 0.15.
[0077]
In addition, it is also preferable to provide a polyolefin layer on the opposite side (back side) of the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflective support. In this case, the back side polyolefin layer is a polyethylene whose surface is matte Alternatively, polypropylene is preferable, and polypropylene is more preferable. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support of the present invention, preferred embodiments regarding the polyolefin layer provided on the paper substrate are described in JP-A Nos. 10-333277, 10-333278, 11-52513, 11-65024, EP0880065, and Examples are described in EP 0880066.
[0078]
Furthermore, it is preferable to contain a fluorescent brightening agent in the water-resistant resin layer. Further, a hydrophilic colloid layer containing the fluorescent brightening agent in a dispersed manner may be separately formed. As the optical brightener, benzoxazole-based, coumarin-based and pyrazoline-based compounds can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based fluorescent brighteners are more preferable. The amount used is not particularly limited, but preferably 1 to 100 mg / m.²It is. The mixing ratio in the case of mixing with a water resistant resin is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass with respect to the resin.
[0079]
The reflective support may be a transmissive support or a reflective colloid coated with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a specular or second-type diffuse reflective metal surface.
[0080]
Further, as a support used in the light-sensitive material of the present invention, a white polyester support or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer is used for a display. May be. In order to further improve the sharpness, an antihalation layer is preferably coated on the silver halide emulsion layer coating side or the back surface of the support. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with either reflected light or transmitted light.
[0081]
In the light-sensitive material of the present invention, for the purpose of improving the sharpness of an image, a hydrophilic colloid layer is coated with a dye that can be decolored by processing as described in pages 27 to 76 of European Patent EP0,337,490A2. Oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or a divalent to tetravalent alcohol (for example, trimethylolethane) is added to the water-resistant resin layer of the support. It is preferable to contain 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated with the above.
[0082]
In the light-sensitive material of the present invention, the processing described in pages 27 to 76 of EP 0337490 A2 is carried out on the hydrophilic colloid layer for the purpose of preventing irradiation and halation or improving the safety light safety. It is preferable to add a decolorizable dye (in particular, an oxonol dye or a cyanine dye). Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes degrade color separation and safelight safety when the amount used is increased. As the dye that can be used without deteriorating color separation, water-soluble dyes described in JP-A Nos. 5-127324, 5-127325, and 5-216185 are preferable.
[0083]
In the present invention, a colored layer that can be decolored by treatment in place of the water-soluble dye or in combination with the water-soluble dye is used. The colored layer that can be decolored by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably placed under the emulsion layer (support side) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to select and install only some of them. It is also possible to install a colored layer that has been colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength having the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm for normal printer exposure, wavelength of the scanning exposure light source used for scanning exposure). The optical density value at is preferably 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.
[0084]
In order to form the colored layer, a conventionally known method can be applied. For example, the dyes described in JP-A-2-282244, page 3, upper right column to page 8 and those described in JP-A-3-7931, page 3, upper right column to page 11, lower left column, can be used for solid fine particle dispersions. Described in JP-A-1-239544, a method of incorporating a hydrophilic colloid layer in a state, a method of mordanting an anionic dye into a cationic polymer, a method of adsorbing a dye to fine particles such as silver halide and fixing it in the layer Such as using colloidal silver. As a method of dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Application Laid-Open No. Hei. 2-308244, pages 4-13. Further, for example, a method for mordanting an anionic dye into a cationic polymer is described on pages 18 to 26 of JP-A-2-84737. US Pat. Nos. 2,688,601 and 3,459,563 show methods for preparing colloidal silver as a light absorber. Among these methods, a method of containing a fine powder dye and a method of using colloidal silver are preferable.
[0085]
The silver halide photographic light-sensitive material of the present invention is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc., among which it is preferably used as a color photographic paper. The color photographic paper preferably has at least one yellow color-forming silver halide emulsion layer, magenta color-forming silver halide emulsion layer, and cyan color-forming silver halide emulsion layer. The silver halide emulsion layer is a yellow color forming silver halide emulsion layer, a magenta color forming silver halide emulsion layer, and a cyan color forming silver halide emulsion layer in order from the support.
[0086]
However, a different layer structure may be used.
The silver halide emulsion layer containing a yellow coupler may be disposed at any position on the support. However, when the yellow coupler-containing layer contains silver halide tabular grains, a magenta coupler-containing silver halide is contained. It is preferably coated at a position farther from the support than at least one emulsion layer or cyan coupler-containing silver halide emulsion layer. Further, from the viewpoints of accelerating color development, accelerating desilvering, and reducing residual color by sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated at a position farthest from the support than other silver halide emulsion layers. It is preferable to be provided. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably the center layer of other silver halide emulsion layers, and from the viewpoint of reducing photobleaching, the cyan coupler-containing silver halide emulsion layer is The lowest layer is preferred. Each of the color developing layers of yellow, magenta and cyan may be composed of two layers or three layers. For example, as described in JP-A-4-75055, 9-1114035, 10-246940, US Pat. No. 5,576,159, etc., a coupler layer containing no silver halide emulsion is used as a silver halide. It is also preferable to provide a color developing layer adjacent to the emulsion layer.
[0087]
As silver halide emulsions and other materials (additives, etc.) and photographic composition layers (layer arrangement, etc.) applied in the present invention, and processing methods and processing additives applied to process this photosensitive material, JP-A-62-215272, JP-A-2-33144, and those described in European Patent EP0,355,660A2, particularly those described in European Patent EP0,355,660A2 are preferably used. . Furthermore, JP-A-5-34889, JP-A-4-359249, JP-A-4-313733, JP-A-4-270344, JP-A-5-66527, JP-A-4-34548, JP-A-4-145433, JP-A-2-854. The silver halide color photographic light-sensitive materials and the processing methods thereof described in JP-A Nos. 1-158431, 2-90145, 3-194539, 2-93641, and European Patent Publication No. 0520457A2 are also preferable.
[0088]
In particular, in the present invention, the reflection type support and silver halide emulsion described above, further different metal ion species doped in the silver halide grains, storage stabilizer or antifoggant for silver halide emulsion, chemical enhancement, Sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsifying dispersion method, color image preservability improving agent (stain inhibitor and anti-fading agent), dye (coloring) As for the layer), gelatin type, layer structure of the photosensitive material, and coating pH of the photosensitive material, those described in each part of the patent shown in Table 1 below are particularly preferably applied.
[0089]
[Table 1]

[0090]
Other examples of the cyan, magenta and yellow couplers used in the present invention include those described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144, No. 3; Page 14 upper right column 14th line to 18th page upper left column last line, page 30 upper right column 6th line to page 35 lower right column 11th line, EP0355,660A2 page 4, 15th line to 27th line, 5th page Couplers described on page 30 to the end of page 28, page 45, line 29 to line 31, page 47, line 23 to page 63, line 50 are also useful.
In the present invention, compounds represented by general formulas (II) and (III) of WO-98 / 33760 and general formula (D) of JP-A-10-221825 may be preferably added.
[0091]
As a cyan dye-forming coupler (sometimes simply referred to as “cyan coupler”) that can be used in the present invention, a pyrrolotriazole coupler is preferably used, and is represented by the general formula (I) or (II) of JP-A-5-313324. And couplers represented by general formula (I) of JP-A-6-347960 and the exemplified couplers described in these patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Other cyan couplers include pyrroloazole-type cyan couplers described in European Patents EP0488248 and EP0491197A1, 2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716, US Pyrazoloazole type cyan couplers having an electron withdrawing group and a hydrogen bonding group at the 6-position described in Japanese Patent Nos. 4,873,183 and 4,916,051, particularly JP-A-8-171185, Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A Nos. 8-311360 and 8-339060 are also preferable.
[0092]
In addition to diphenylimidazole cyan couplers described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in European Patent EP 0333185A2 (among others, couplers (42) listed as specific examples) And a cyclic active methylene-based cyan coupler described in JP-A No. 64-32260, which is obtained by adding a chlorine-eliminating group to a 4-equivalent coupler, and couplers (6) and (9) are particularly preferable. Of these, coupler examples 3, 8, and 34 listed as specific examples are particularly preferred), pyrrolopyrazole type cyan couplers described in EP 0456226A1 and pyrroloimidazole type cyan couplers described in EP 0484909 are used. You can also.
[0093]
Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred. The couplers (1) to (47) are applied to the present application as they are, and are preferably incorporated as part of the specification of the present application.
[0094]
Examples of the magenta dye-forming coupler used in the present invention (sometimes simply referred to as “magenta coupler”) include 5-pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers described in the publicly known literatures in the above table. Among them, a secondary or tertiary alkyl group as described in JP-A-61-65245 is located at the 2, 3, or 6 position of the pyrazolotriazole ring, particularly in terms of hue, image stability, color developability and the like. Directly linked pyrazolotriazole couplers, pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-61-65246, and alkoxyphenyl sulfones as described in JP-A-61-147254 Pyrazoloazole couplers having amide ballast groups and European Patent Nos. 226,849A and 294,785 Use of pyrazoloazole couplers having an alkoxy group or an aryloxy group at the 6-position as described in JP. In particular, the magenta coupler is preferably a pyrazoloazole coupler represented by the general formula (M-I) described in JP-A-8-122984. Paragraph Nos. 0009 to 0026 of the patent are directly applied to the present application. Incorporated as part of the specification. In addition, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in European Patent Nos. 854384 and 844640 are also preferably used.
[0095]
Further, as yellow dye-forming couplers (sometimes simply referred to as “yellow couplers”), in addition to the compounds described in the above table, a 3- to 5-membered cyclic group is added to the acyl group described in EP 0447969A1. An acylacetamide type yellow coupler having a structure, a malondianilide type yellow coupler having a cyclic structure described in European Patent EP 0482552A1, European Patents 935870A1, 953871A1, 953872A1, and 953873A1 Pyrrole-2 or 3-yl or indol-2 or 3-ylcarbonylacetic acid anilide couplers described in US Pat. No. 5,118,599, US Pat. No. 5,118,599, and the like. Acyl acetate having dioxane structure A toamide type yellow coupler is preferably used. Among them, the use of an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring is particularly preferred. These couplers can be used alone or in combination.
[0096]
The coupler used in the present invention is impregnated with a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvent described in the preceding table, Alternatively, it is preferably dissolved together with a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15, and International Publication WO 88/00723, pages 12 to 30. The described homopolymers or copolymers are mentioned. More preferably, use of a methacrylate or acrylamide polymer, particularly an acrylamide polymer is preferred in view of color image stability.
[0097]
In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable.
For example, high molecular weight redox compounds described in JP-A-5-333501, phenidone and hydrazine compounds described in WO98 / 33760, U.S. Pat. No. 4,923,787, JP-A-5-249637, White couplers described in JP-A-10-282615 and German Patent No. 19629142A1 can be used. In particular, in the case of increasing the pH of the developing solution and speeding up development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 842975A1, German Patent No. 19804646A1 and French Patent No. 2760460A1 It is also preferable to use the redox compound described in the above.
[0098]
In the present invention, a compound having a triazine skeleton with a high molar extinction coefficient is preferably used as the ultraviolet absorber, and for example, compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or non-photosensitive. For example, JP-A-46-3335, JP-A-55-15276, JP-A-5-197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-2111813, JP-A-8-53427, and 8- No. 234364, No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. 19739797A, European Patent No. The compounds described in 501291 etc. can be used.
[0099]
As the binder or protective colloid that can be used in the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or in combination with gelatin. As a preferable gelatin, the heavy metal contained as impurities such as iron, copper, zinc and manganese is preferably 5 ppm or less, more preferably 3 ppm or less. The amount of calcium contained in the photosensitive material is preferably 20 mg / m.²Or less, more preferably 10 mg / m²Or less, most preferably 5 mg / m²It is as follows.
[0100]
In the present invention, an antibacterial / antifungal agent as described in JP-A-63-271247 is added in order to prevent various wrinkles and bacteria that propagate in the hydrophilic colloid layer and degrade the image. Is preferred. Further, the film pH of the photosensitive material is preferably 4.0 to 7.0, more preferably 4.0 to 6.5.
[0101]
In the present invention, a surfactant can be added to the photosensitive material from the viewpoints of improving the coating stability of the photosensitive material, preventing the generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but generally 1 × 10 10^-Five~ 1g / m², Preferably 1 × 10^-Four~ 1x10^-1g / m²More preferably 1 × 10^-3~ 1x10^-2g / m²It is.
[0102]
The photosensitive material of the present invention can form an image by an exposure process in which light is irradiated according to image information and a development process in which the photosensitive material irradiated with light is developed. The photosensitive material of the present invention is suitable for a scanning exposure system using a cathode ray (CRT) in addition to being used in a printing system using a normal negative printer. The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy. As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, a red light emitter, a green light emitter, or a blue light emitter may be used alone or in combination. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.
[0103]
When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions, and the cathode tube also has a phosphor exhibiting light emission in a plurality of spectral regions, a plurality of colors are exposed at the same time, that is, a plurality of colors are applied to the cathode ray tube. It is also possible to emit light from the tube surface by inputting a color image signal. A method of sequentially inputting image signals for each color to cause each color to emit light sequentially and exposing through a film that cuts the colors other than that color (surface sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for improving image quality.
[0104]
The photosensitive material of the present invention is a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) using a combination of a solid state laser using a semiconductor laser and a nonlinear optical crystal. A digital scanning exposure method using density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.
[0105]
When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green, and red. When the exposure time in such scanning exposure is defined as the exposure time of the pixel size when the pixel density is 400 dpi, a preferable exposure time is 10^-FourSeconds or less, more preferably 10^-6Less than a second.
[0106]
The silver halide color photographic light-sensitive material of the present invention can be preferably used in combination with the exposure and development system described in the following known documents. The developing system includes an automatic printing and developing system described in JP-A-10-333253, a photosensitive material conveying apparatus described in JP-A-2000-10206, and an image reading apparatus described in JP-A-11-215312. System, an exposure system comprising a color image recording system described in JP-A-11-88619 and JP-A-10-202950, a digital photo print system including a remote diagnosis system described in JP-A-10-210206, and Japanese Patent Application No. A photo print system including the image recording apparatus described in No. 10-159187 can be given.
[0107]
Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above.
[0108]
When the light-sensitive material of the present invention is subjected to printer exposure, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. This removes light color mixing and remarkably improves color reproducibility.
In the present invention, as described in European Patents EP0789270A1 and EP0789480A1, before giving image information, a yellow microdot pattern may be pre-exposed and copy restrictions may be applied.
[0109]
In the processing of the photosensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, line 17 The processing materials and processing methods described in the 20th page, lower right column, line 20 are preferably applicable. Further, as the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.
[0110]
The present invention is preferably applied to a light-sensitive material having rapid processing suitability. In the case of rapid processing, the color development time is preferably 60 seconds or shorter, more preferably 50 seconds or shorter and 6 seconds or longer, more preferably 30 seconds or shorter and 6 seconds or longer. Similarly, the bleach-fixing time is preferably 60 seconds or shorter, more preferably 50 seconds or shorter and 6 seconds or longer, more preferably 30 seconds or shorter and 6 seconds or longer. Further, the washing time or stabilization time is preferably 150 seconds or shorter, more preferably 130 seconds or shorter and 6 seconds or longer.
The color development time refers to the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leave the color developer and are bleached in the next processing step. The sum of both the time during which the toner is conveyed in the air toward the fixing bath (so-called air time) is referred to as color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The water washing or stabilization time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the water washing or stabilizing liquid.
[0111]
The light-sensitive material of the present invention can be developed after exposure using a conventional developing method containing an alkali agent and a developing agent, an activator such as an alkaline solution containing the developing agent in the photosensitive material and not containing the developing agent. In addition to a wet method such as a method of developing with a beta solution, a thermal development method without using a processing solution can be used. In particular, the activator method is a preferable method from the viewpoint of environmental protection because it does not contain a developing agent in the processing solution, so that the processing solution can be easily managed and handled, and the load during processing of the waste liquid is small. In the activator method, examples of the developing agent incorporated in the light-sensitive material or a precursor thereof include, for example, JP-A-8-234388, JP-A-9-152686, JP-A-9-152893, JP-A-9-2111814, and JP-A-9-21814. The hydrazine type compound described in -160193 is preferable.
[0112]
Further, a developing method in which the amount of silver applied to the photosensitive material is reduced and image amplification processing (compensation processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, an image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and 9-152695 is preferably used. In the activator method, after processing with an activator solution, desilvering is usually performed. However, in the image amplification processing method using a low silver amount of light-sensitive material, desilvering is omitted and washing or stabilization is simplified. Can be done. Further, in a method of reading image information from a photosensitive material with a scanner or the like, it is possible to adopt a processing form that does not require a desilvering process even when a high silver amount photosensitive material such as a photographic photosensitive material is used.
[0113]
For the activator solution, desilvering solution (bleaching / fixing solution), water washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, those described in Research Disclosure Item 36544 (September 1994), pages 536 to 541 and JP-A-8-234388 can be used.
[0114]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0115]
Example 1
(Preparation of emulsion B-1)
1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 3.3 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were simultaneously added and mixed at 66 ° C. with vigorous stirring. From the point of 80% to 90% addition of silver nitrate,_Four[Ru (CN)₆] The amount of Ru per mol of finished silver halide is 3 × 10^-FiveMolar amounts were added. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆The amount of Ir per mol of the finished silver halide is 3 × 10^-8Molar amounts were added. From the point when the addition of silver nitrate is 92% to the point when it is 98%,₂[Ir (H₂O) Cl_FiveThe amount of Ir per mole of the finished silver halide is 1 × 10^-6Molar amounts were added. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.7 and pCl1.8. The obtained grains were cubic silver chloride emulsions having a side length of 0.6 μm and a coefficient of variation of 11%.
The emulsion was dissolved at 40 ° C. and sodium thiosulfonate was added at 2 × 10 5 per mole of silver halide.^-FiveMole was added, and aging was performed at 60 ° C. optimally using sodium thiosulfate pentahydrate as a sulfur sensitizer and (S-2) as a gold sensitizer. After cooling to 40 ° C., sensitizing dye A was added at 2 × 10 2 per mole of silver halide.^-FourMol, sensitizing dye B 1 × 10 5 per mol of silver halide^-FourMol, 1-phenyl-5-mercaptotetrazole, 2 × 10 5 per mole of silver halide^-FourMole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, 2 × 10 2 per mole of silver halide^-FourMol, potassium bromide 2 × 10 2 per mol of silver halide^-3Mole was added. The emulsion thus obtained was designated as Emulsion B-1.
[0116]
[Chemical 6]

[0117]
(Preparation of emulsion B-2)
Emulsion B-1 means that when 90% of the addition of silver nitrate was completed, an aqueous potassium iodide solution was added while vigorously mixing in an amount of 0.2 mol% per mol of the resulting silver halide. Only different emulsions were prepared. The obtained grains were cubic silver iodochloride emulsions having a side length of 0.6 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-2.
When the iodide ion concentration distribution of the obtained emulsion B-2 was analyzed by the etching / TOF-SIMS method, the iodide ion had a maximum concentration on the grain surface and the concentration decreased toward the inside. I understood. Even when the addition of the iodide salt solution is completed inside the grains (position of 90% by the addition of silver nitrate), iodide ions ooze out toward the grain surfaces. The resulting grain morphology is almost the same between Emulsions B-1 and B-2, and Emulsion B-2 contains silver iodochloride grains in which the silver iodide-containing phase is layered on the outermost surface of the grains. Conceivable.
[0118]
(Preparation of emulsion B-3)
It differs from Emulsion B-1 only in the addition of potassium bromide in an amount of 2 mol% per mol of the finished silver halide with vigorous mixing from the 80% to 90% addition of silver nitrate. An emulsion was prepared. The obtained grains were cubic silver bromochloride emulsions having a side length of 0.6 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-3.
When the bromide ion concentration distribution of the obtained emulsion B-3 was analyzed by the etching / TOF-SIMS method, it was found that bromide ions had a maximum concentration inside the grains. It shows that a silver bromide-containing phase is formed inside the grain to which the bromide salt solution has been added (position of 80% to 90% by the addition of silver nitrate). The resulting grain morphology is hardly different between Emulsions B-1 and B-3, and Emulsion B-3 is considered to contain silver bromochloride grains in which the silver bromide-containing phase is formed in layers inside the grains. It is done.
[0119]
(Preparation of emulsion B-4)
It differs from Emulsion B-1 only in that the amount of potassium bromide added at 2% by mole per mole of the finished silver halide was vigorously mixed from 90% to 100%. An emulsion was prepared. The obtained grains were cubic silver bromochloride emulsions having a side length of 0.6 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-4.
When the bromide ion concentration distribution of the obtained emulsion B-4 was analyzed by the etching / TOF-SIMS method, it was found that bromide ions were mainly distributed in the vicinity of the surface. It shows that a silver bromide-containing phase is formed in the vicinity of the surface of the grain to which the bromide salt solution has been added (position of 90% to 100% by the addition of silver nitrate). The resulting grain morphology is almost the same between Emulsions B-1 and B-4, and Emulsion B-4 is considered to contain silver bromochloride grains in which the silver bromide-containing phase is formed in the vicinity of the surface in layers. It is done.
[0120]
(Preparation of emulsion B-5)
It differs from Emulsion B-1 only in the addition of potassium bromide in an amount of 4 mol% per mol of the finished silver halide while vigorously mixing from the point of 80% to 100% addition of silver nitrate. An emulsion was prepared. The obtained grains were cubic silver bromochloride emulsions having a side length of 0.6 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-5.
When the bromide ion concentration distribution of the obtained emulsion B-5 was analyzed by etching / TOF-SIMS method, it was found that bromide ions were distributed from the inside of the grain to the surface. This shows that a silver bromide-containing phase is formed from the inside to the surface of the grain to which the bromide salt solution has been added (position of 80% to 100% by the addition of silver nitrate). The resulting grain morphology is almost the same between Emulsions B-1 and B-5, and Emulsion B-5 contains silver bromochloride grains in which the silver bromide-containing phase is formed in layers from the grain interior to the surface. it is conceivable that.
[0121]
(Preparation of emulsion B-6)
Emulsion B-1 is an addition of potassium bromide in an amount of 2 mol% per mol of the finished silver halide while vigorously mixing from 80% to 90% addition of silver nitrate. When the addition of 90% was completed, different emulsions were prepared, except that an aqueous potassium iodide solution was added with vigorous mixing in an amount of 0.2 mol% per mol of the finished silver halide. The obtained grains were cubic silver iodobromochloride emulsions having a side length of 0.6 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-6.
When the iodide ion and bromide ion concentration distribution of the obtained emulsion B-6 was analyzed by the etching / TOF-SIMS method, the iodide ion had a concentration maximum on the grain surface and the concentration decreased toward the inside. In contrast, bromide ions were found to have a concentration maximum within the grain. Even if the addition of the iodide salt solution is completed inside the grain (position of 90% by addition of silver nitrate), iodide ions are oozed out toward the grain surface, but the silver bromide-containing phase is a bromide salt solution. It is shown that it is formed inside the grain to which the addition of (1) is performed (position of 80% to 90% by addition of silver nitrate). The resulting grain morphology is almost the same between Emulsions B-1 and B-6. In Emulsion B-6, the silver bromide-containing phase is formed in layers inside the grains, and the silver iodide-containing phase is layered on the outermost surface of the grains. It is considered that the silver bromoiodide grains formed in this were contained.
[0122]
(Preparation of emulsion B-7)
Emulsion B-1 is the addition of an aqueous potassium iodide solution in which the amount of I is 0.2 mol% per mol of the finished silver halide with vigorous mixing when 90% of the addition of silver nitrate is completed. Further, emulsions were prepared which differed only in that potassium bromide was added in an amount of 2 mol% per mol of the finished silver halide while vigorously mixing from 90% to 100%. The obtained grains were cubic silver iodobromochloride emulsions having a side length of 0.6 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-7.
When the iodide ion and bromide ion concentration distribution of the obtained emulsion B-7 was analyzed by the etching / TOF-SIMS method, the iodide ion had a concentration maximum on the grain surface and the concentration decreased toward the inside. It was found that bromide ions were mainly distributed near the surface. Even when the addition of the iodide salt solution is completed inside the grains (position of 90% by the addition of silver nitrate), iodide ions ooze out toward the grain surface, but the silver bromide-containing phase is the bromide salt solution. In the vicinity of the surface of the grain subjected to the addition of (a position of 90% to 100% by the addition of silver nitrate). The resulting grain morphology is almost the same between Emulsions B-1 and B-7. Emulsion B-7 is a silver iodobromochloride grain in which both a silver bromide-containing phase and a silver iodide-containing phase are layered on the surface. It is thought that it contains.
[0123]
(Preparation of emulsion B-8)
Emulsion B-1 is an addition of potassium bromide in an amount of 4 mol% per mol of the finished silver halide while vigorously mixing from 80% to 100% addition of silver nitrate. When the addition of 90% was completed, emulsions differing only in that an aqueous potassium iodide solution was added while vigorously mixing in an amount of 0.2 mol% per mol of the finished silver halide. The obtained grains were cubic silver iodobromochloride emulsion having a side length of 0.6 μm and a coefficient of variation of 11%. The emulsion thus obtained was named Emulsion B-8.
When the iodide ion and bromide ion concentration distribution of the obtained emulsion B-8 was analyzed by the etching / TOF-SIMS method, the iodide ion had a concentration maximum on the grain surface and the concentration decreased toward the inside. On the other hand, it was found that bromide ions were distributed from the inside of the grain to the surface. Even when the addition of the iodide salt solution is completed inside the grains (position of 90% by the addition of silver nitrate), iodide ions ooze out toward the grain surface, but the silver bromide-containing phase is the bromide salt solution. It is shown that it is made from the inner side to the surface (position of 80% to 100% by the addition of silver nitrate) of the grains subjected to the addition of. The resulting grain morphology is almost the same between emulsions B-1 and B-8. In emulsion B-8, the silver bromide-containing phase is formed in layers from the inside of the grain to the surface, and the silver iodide-containing phase is the outermost surface of the grain. The silver iodobromochloride grains formed in a layer are considered to be contained.
[0124]
After the corona discharge treatment is applied to the surface of the support formed by coating both sides of the paper with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate is provided. The layers were sequentially coated to prepare a sample of a silver halide color photographic light-sensitive material having the following layer structure. The coating solution for each photographic constituent layer was prepared as follows.
[0125]
First layer coating preparation
57 g of yellow coupler (ExY), 7 g of color image stabilizer (Cpd-1), 4 g of color image stabilizer (Cpd-2), 7 g of color image stabilizer (Cpd-3), 2 g of color image stabilizer (Cpd-8) Is dissolved in 21 g of a solvent (Solv-1) and 80 ml of ethyl acetate, and this liquid is emulsified and dispersed in 220 g of a 23.5% by weight gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate with a high-speed stirring emulsifier (dissolver). 900 g of emulsified dispersion A was prepared by adding water.
On the other hand, the emulsified dispersion A and the emulsion B-1 were mixed and dissolved, and a first layer coating solution was prepared so as to have the composition described later. The emulsion coating amount indicates the silver coating amount.
[0126]
The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. Moreover, the total amount of Ab-1, Ab-2, Ab-3, and Ab-4 is 15.0 mg / m in each layer.²60.0 mg / m²5.0 mg / m²And 10.0 mg / m²It added so that it might become.
[0127]
[Chemical 7]

[0128]
[Chemical 8]

[0129]
The following spectral sensitizing dyes were used in the silver bromochloride emulsions of the green and red sensitive emulsion layers, respectively.
Green sensitive emulsion layer
[0130]
[Chemical 9]

[0131]
(Sensitizing dye D per mole of silver halide, 3.0 x 10 for large size emulsions^-Four3.6 × 10 for small, small emulsions^-FourMol, and Sensitizing Dye E per mol of silver halide, 4.0 × 10 for large size emulsions^-Five7.0 x 10 for molar, small emulsions^-FiveMole, and sensitizing dye F per mole of silver halide, and 2.0 × 10 5 for large size emulsions.^-Four2.8 × 10 for small, small emulsions^-FourMole was added. )
Red sensitive emulsion layer
[0132]
[Chemical Formula 10]

[0133]
(Sensitizing dyes G and H are each 8.0 moles per mole of silver halide and 8.0 × 10 for large size emulsions.^-Five10.7 × 10 for small, small emulsions^-FiveMole was added. Further, the following compound I was added to the red-sensitive emulsion layer at 3.0 × 10 6 per mole of silver halide.^-3Mole was added. )
[0134]
Embedded image

[0135]
In addition, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 1.0 × 10 6 per mol of silver halide.^-3Moles and 5.9 × 10^-FourMole was added.
In addition, the second layer, the fourth layer, the sixth layer, and the seventh layer are each 0.2 mg / m 2.²0.2 mg / m²0.6 mg / m²0.1 mg / m²It added so that it might become.
Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, respectively, at 1 × 10 6 per 1 mol of silver halide.^-FourMol, 2 × 10^-FourMole was added.
Further, a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200,000 to 400,000) is 0.05 g / m on the red sensitive emulsion layer.²Added.
Further, disodium catechol-3,5-disulfonate was added to the second layer, the fourth layer, and the sixth layer, respectively, at 6 mg / m.²6 mg / m²18 mg / m²It added so that it might become.
In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).
[0136]
Embedded image

[0137]
(Layer structure)
The structure of each layer is shown below. Numbers are application amount (g / m²). The silver halide emulsion represents a coating amount in terms of silver.
Support
Polyethylene resin laminated paper
[White pigment (TiO 2 on the first layer side polyethylene resin)₂Content 16% by mass, ZnO; content 4% by mass) and optical brightener (4,4′-bis (5-methylbenzoxazolyl) stilbene, content 0.03% by mass), bluish dye (Including ultramarine)]
First layer (blue sensitive emulsion layer)
Emulsion B-1 0.24
Gelatin 1.25
Yellow coupler (ExY) 0.57
Color image stabilizer (Cpd-1) 0.07
Color image stabilizer (Cpd-2) 0.04
Color image stabilizer (Cpd-3) 0.07
Color image stabilizer (Cpd-8) 0.02
Solvent (Solv-1) 0.21
[0138]
Second layer (color mixing prevention layer)
Gelatin 0.99
Color mixing inhibitor (Cpd-4) 0.09
Color image stabilizer (Cpd-5) 0.018
Color image stabilizer (Cpd-6) 0.13
Color image stabilizer (Cpd-7) 0.01
Solvent (Solv-1) 0.06
Solvent (Solv-2) 0.22
[0139]

[0140]
Fourth layer (color mixing prevention layer)
Gelatin 0.71
Color mixing prevention layer (Cpd-4) 0.06
Color image stabilizer (Cpd-5) 0.013
Color image stabilizer (Cpd-6) 0.10
Color image stabilizer (Cpd-7) 0.007
Solvent (Solv-1) 0.04
Solvent (Solv-2) 0.16
[0141]

[0142]
Sixth layer (UV absorbing layer)
Gelatin 0.46
Ultraviolet absorber (UV-B) 0.45
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.25
Seventh layer (protective layer)
Gelatin 1.00
Acrylic-modified copolymer of polyvinyl alcohol
(Degree of modification 17%) 0.04
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.01
[0143]
Embedded image

[0144]
Embedded image

[0145]
Embedded image

[0146]
Embedded image

[0147]
Embedded image

[0148]
Embedded image

[0149]
Embedded image

[0150]
Embedded image

[0151]
Embedded image

[0152]
Embedded image

[0153]
The sample obtained as described above was designated as Sample B-1. Samples B-1 were prepared in the same manner as samples B-2 to B-8 except that emulsion B-1 in the blue-sensitive emulsion layer was changed from emulsions B-2 to B-8.
[0154]
In order to examine the photographic characteristics of these samples, the following experiment was conducted.
Each coated sample was subjected to gradation exposure for sensitometry using a high-illuminance exposure photometer (HIE type manufactured by Yamashita Denso Co., Ltd.). Mounted with SP-1 filter manufactured by Fuji Photo Film Co., Ltd., high illuminance 10^-6Exposure for 2 seconds.
After the exposure, the following color development processing A was performed.
[0155]
The processing steps are shown below.
[Processing A]
The sample of the above photosensitive material is processed into a 127 mm width roll, and after imagewise exposure using a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd. Continuous processing (running test) was performed. The treatment using this running liquid was designated as treatment A.
Processing temperature Temperature Time Replenishment amount^*
Color development 38.5 ° C 45 seconds 45 ml
Bleach fixing 38.0 ° C 45 seconds 35 ml
Rinse (1) 38.0 ° C. 20 seconds −
Rinse (2) 38.0 ° C. 20 seconds −
Rinse (3) ** 38.0 ° C 20 seconds-
Rinse (4) ** 38.0 ° C 30 seconds 121 ml
* Photosensitive material 1m²Replenishment amount per
** A phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. is installed in the rinse (3), the rinse solution is taken out from the rinse (3), and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day.
(The rinsing was a counter-current tank system from (1) to (4).)
[0156]
The composition of each treatment liquid is as follows.

[0157]

[0158]

[0159]
The yellow color density of each sample after treatment was measured, and 10^-6A characteristic curve of second exposure high illumination exposure was obtained. The sensitivity was defined by the reciprocal of the exposure amount giving a color density 0.7 higher than the minimum color density, and expressed as a relative value when the sensitivity of Sample B-1 was 100. Also, the gradation was obtained from the slope of a straight line connecting the points of density 0.5 and density 2.0. The results are shown in Table 2.
[0160]
[Table 2]

[0161]
As is apparent from the results in Table 2, Sample B-6 containing a silver iodobromochloride emulsion in which the silver bromide-containing phase and the silver iodide-containing phase of the present invention are formed in layers in the blue-sensitive emulsion layer. , B-7 and B-8 were found to have extremely high blue sensitivity and high contrast.
[0162]
Example 2
(Preparation of emulsion G-1)
1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 3.3 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were simultaneously added and mixed at 56 ° C. with vigorous stirring. From the point of 80% to 90% addition of silver nitrate,_Four[Ru (CN)₆] The amount of Ru per mol of finished silver halide is 5 × 10^-FiveMolar amounts were added. From the point of 83% to 88% addition of silver nitrate,₂[IrCl₆The amount of Ir per mole of the finished silver halide is 5 × 10^-8Molar amounts were added. From the point when the addition of silver nitrate is 92% to the point when it is 98%,₂[Ir (5-methylthiazole) Cl_FiveThe amount of Ir per mole of the finished silver halide is 1 × 10^-6Molar amounts were added. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.7 and pCl1.8. The obtained grains were cubic silver chloride emulsions having a side length of 0.4 μm and a coefficient of variation of 11%.
The emulsion was dissolved at 40 ° C. and sodium thiosulfonate was added at 2 × 10 5 per mole of silver halide.^-FiveMole was added, and aging was performed at 60 ° C. optimally using sodium thiosulfate pentahydrate as a sulfur sensitizer and (S-2) as a gold sensitizer. After cooling to 40 ° C., sensitizing dye D was added at 5 × 10 5 per mole of silver halide.^-FourMol, 1-phenyl-5-mercaptotetrazole, 2 × 10 5 per mole of silver halide^-FourMole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, 4 × 10 4 per mole of silver halide^-FourMoles of potassium bromide, 7 x 10 per mole of silver halide^-3Mole was added. The emulsion thus obtained was designated as Emulsion G-1.
[0163]
(Preparation of emulsion G-2)
Emulsion G-1 means that when 90% of the addition of silver nitrate has been completed, an aqueous potassium iodide solution was added while vigorously mixing in an amount such that the amount of I was 0.3 mol% per mol of the finished silver halide. Only different emulsions were prepared. The obtained grains were cubic silver iodochloride emulsions having a side length of 0.4 μm and a variation coefficient of 11%. The emulsion thus obtained was designated as Emulsion G-2.
[0164]
(Preparation of emulsion G-3)
It differs from Emulsion G-1 only in the addition of potassium bromide in an amount of 4 mol% per mol of the finished silver halide while vigorously mixing from the point of 80% to 100% addition of silver nitrate. An emulsion was prepared. The obtained grains were cubic silver bromochloride emulsions having a side length of 0.4 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion G-3.
[0165]
(Preparation of emulsion G-4)
Emulsion G-1 is the addition of potassium bromide in an amount of 4 mol% per mol of the finished silver halide while vigorously mixing from 80% to 100% addition of silver nitrate. When the addition of 90% was completed, different emulsions were prepared, except that an aqueous potassium iodide solution was added while vigorously mixing in an amount such that the amount of I was 0.3 mol% per mol of the finished silver halide. The obtained grains were cubic silver iodobromochloride emulsions having a side length of 0.4 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion G-4.
The distribution of bromide and iodide ion concentrations in the depth direction of emulsion G-4 grains was measured by etching / TOF-SIMS method. The results are shown in FIG. Even when the addition of the iodide salt solution is completed inside the grains, the iodide ions ooze out toward the grain surface, have a maximum concentration on the outermost surface, and the concentration attenuates toward the inside. On the other hand, bromide ions have a maximum concentration inside the grain. From this, it is considered that the silver bromide-containing phase is formed in a layered manner inside the grain than the silver iodide-containing phase.
[0166]
The sample of Example 1 was prepared by changing the layer configuration as follows to make a thin layer.
Sample preparation
First layer (blue sensitive emulsion layer)
Emulsion B-1 0.24
Gelatin 1.25
Yellow coupler (ExY) 0.57
Color image stabilizer (Cpd-1) 0.07
Color image stabilizer (Cpd-2) 0.04
Color image stabilizer (Cpd-3) 0.07
Color image stabilizer (Cpd-8) 0.02
Solvent (Solv-1) 0.21
[0167]
Second layer (color mixing prevention layer)
Gelatin 0.60
Color mixing inhibitor (Cpd-19) 0.09
Color image stabilizer (Cpd-5) 0.007
Color image stabilizer (Cpd-7) 0.007
Ultraviolet absorber (UV-C) 0.05
Solvent (Solv-5) 0.11
[0168]
Third layer (green sensitive emulsion layer)
Emulsion G-1 0.14
Gelatin 0.73
Magenta coupler (ExM) 0.15
Ultraviolet absorber (UV-A) 0.05
Color image stabilizer (Cpd-2) 0.02
Color image stabilizer (Cpd-7) 0.008
Color image stabilizer (Cpd-8) 0.07
Color image stabilizer (Cpd-9) 0.03
Color image stabilizer (Cpd-10) 0.009
Color image stabilizer (Cpd-11) 0.0001
Solvent (Solv-3) 0.06
Solvent (Solv-4) 0.11
Solvent (Solv-5) 0.06
[0169]
Fourth layer (color mixing prevention layer)
Gelatin 0.48
Color mixing prevention layer (Cpd-4) 0.07
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-7) 0.006
UV absorber (UV-C) 0.04
Solvent (Solv-5) 0.09
[0170]
5th layer (red-sensitive emulsion layer)
Silver bromochloride emulsion C (same emulsion as sample B-1) 0.12
Gelatin 0.59
Cyan coupler (ExC-2) 0.13
Cyan coupler (ExC-3) 0.03
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-15) 0.19
Color image stabilizer (Cpd-18) 0.04
UV absorber (UV-7) 0.02
Solvent (Solv-5) 0.09
[0171]
Sixth layer (UV absorbing layer)
Gelatin 0.32
Ultraviolet absorber (UV-C) 0.42
Solvent (Solv-7) 0.08
Seventh layer (protective layer)
Gelatin 0.70
Acrylic-modified copolymer of polyvinyl alcohol
(Degree of modification 17%) 0.04
Liquid paraffin 0.01
Surfactant (Cpd-13) 0.01
Polydimethylsiloxane 0.01
Silicon dioxide 0.003
[0172]
A sample using the above emulsion G-1 as an emulsion of the green sensitive emulsion layer was designated as sample G-1. Samples G-1 were prepared in the same manner as samples G-2 to G-4 except that the emulsion G-1 in the green sensitive emulsion layer was changed from emulsions G-2 to G-4.
[0173]
In order to examine the photographic characteristics of these samples, the following experiment was conducted.
Each coated sample was subjected to gradation exposure for sensitometry using a high-illuminance exposure photometer (HIE type manufactured by Yamashita Denso Co., Ltd.). Wearing SP-2 filter made by Fuji Photo Film Co., Ltd., high illuminance 10^-6Exposure for 2 seconds.
[0174]
For each of the exposed samples, the color development processing was performed ultra-rapid processing according to the following development processing B.
[0175]
[Process B]
The above photosensitive material sample was processed into a 127 mm wide roll, and the average of the photosensitive material sample was measured using an experimental processing device modified from Fuji Photo Film's minilab printer processor PP350 so that the processing time and processing temperature could be changed. Imagewise exposure was performed from a negative density film, and continuous processing (running test) was performed until the volume of the color developer replenisher used in the following processing steps was 0.5 times the volume of the color developer tank.
[0176]
Processing temperature Temperature Time Replenishment amount^*
Color development 45.0 ℃ 15 seconds 45mL
Bleach fixing 40.0 ℃ 15 seconds 35mL
Rinse 1 40.0 ° C 8 seconds-
Rinse 2 40.0 ° C 8 seconds-
Rinse 3 ** 40.0 ° C 8 seconds-
Rinse 4 38.0 ° C 8 seconds 121mL
Drying 80.0 ℃ 15 seconds
(Note) * Sensitive material 1m²Replenishment amount per
** Mount a phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. on the rinse (3), take out the rinse solution from the rinse (3), and send it to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse, and the concentrate is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours per day. The rinsing was a 4-tank countercurrent system from (1) to (4).
[0177]
The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
Water 800mL 600mL
Optical brightening agent (FL-1) 5.0 g 8.5 g
Triisopropanolamine 8.8g 8.8g
Sodium p-toluenesulfonate 20.0 g 20.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.50g
Potassium chloride 10.0 g −
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.50 g 0.50 g
Disodium-N, N-bis (sulfonate
Ethyl) hydroxylamine 8.5 g 14.5 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline
・ 3/2 sulfate ・ Monohydrate 10.0g 22.0g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.35 12.6
[0178]

[0179]
[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL
pH (25 ° C.) 6.5 6.5
[0180]
Embedded image

[0181]
The magenta color density of each sample after treatment was measured, and 10^-6A characteristic curve of second exposure high illumination exposure was obtained. Sensitivity was defined by the reciprocal of the exposure amount giving a color density 0.7 higher than the minimum color density, and expressed as a relative value when the sensitivity of sample G-1 was 100. Also, the gradation was obtained from the slope of a straight line connecting the points of density 0.5 and density 2.0.
Further, in order to examine the latent image storage stability, a characteristic curve is obtained when processing is started 10 seconds after exposure and when processing is started 10 minutes after exposure, and density is 1 when processing is started 10 seconds later. The change in density at the exposure dose giving 0.0 was examined. Furthermore, in order to investigate the dependency on exposure temperature and humidity, characteristic curves when the exposure is started at 10 ° C. and 55% atmosphere and the processing is started after 10 seconds and when the exposure is started at 30 ° C. and 30% atmosphere and the processing is started after 10 seconds The change in density at an exposure amount giving a density of 1.0 when the exposure was performed in an atmosphere of 10 ° C. and 55% and processing was started after 10 seconds was examined. These results are shown in Table 3.
[0182]
[Table 3]

[0183]
As apparent from the results in Table 3, Sample G-4 containing the silver iodobromochloride emulsion in which the silver bromide-containing phase and the silver iodide-containing phase of the present invention are formed in layers in the green photosensitive emulsion layer. The green photosensitivity was remarkably high sensitivity and high contrast, and it was confirmed that the latent image storage stability and exposure temperature / humidity dependency were excellent.
Further, a sample G-4 ′ different from sample G-4 except that emulsion B-1 in the first layer was changed to emulsion B-8 was prepared, and the above evaluation was made. Similar results were obtained.
[0184]
Example 3
Using the sample of Example 2, image formation was performed by laser scanning exposure.
As a laser light source, a YAG solid-state laser (oscillation wavelength 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength 808.5 nm) as an excitation light source is a LiNbO having an inverted domain structure._ThreeYVO using an excitation light source of 473 nm extracted by wavelength conversion with an SHG crystal and a semiconductor laser GaAlAs (oscillation wavelength 808.7 nm)_FourLiNbO with an inversion domain structure from a solid-state laser (oscillation wavelength 1064 nm)_Three532 nm extracted by wavelength conversion using SHG crystal and AlGaInP (oscillation wavelength: about 680 nm: type No. LN9R20 manufactured by Matsushita Electric Industrial Co., Ltd.) were used. The laser beams of the three colors are moved in the direction perpendicular to the scanning direction by a polygon mirror so that the sample can be sequentially scanned and exposed. The light quantity fluctuation due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter is 80 μm, the scanning pitch is 42.3 μm (600 dpi), and the average exposure time per pixel is 1.7 × 10.^-7Second.
After the exposure, the color development processing B was performed. As a result of the high illumination exposure in Example 2, the sample G-4 of the present invention showed a high sensitivity and gradation in the green-sensitive layer, Sample G-4 ′ of the present invention showed high sensitivity and gradation in the blue-sensitive layer and the green-sensitive layer, and both were found to be suitable for image formation using laser scanning exposure.
[0185]
【The invention's effect】
According to the present invention, a silver halide emulsion capable of obtaining a high-sensitivity and high gradation even in digital exposure such as laser scanning exposure and a silver halide photographic light-sensitive material using the same can be obtained. Furthermore, according to the present invention, a silver halide emulsion excellent in latent image storage stability and exposure temperature / humidity dependency and a silver halide photographic light-sensitive material using the same can be obtained.
[Brief description of the drawings]
1 is a graph showing the distribution of bromide and iodide ion concentrations in the depth direction of emulsion G-4 grains in Example 2. FIG.

Claims (16)

A silver bromide-containing phase and a silver iodide-containing phase are respectively formed in layers, and the silver bromide-containing phase has a silver content of 3% to 15% of the silver halide grain volume, and a silver chloride content of 90 %. Silver halide characterized by containing silver halide grains having a circular diameter equivalent to the projected area of the grains larger than 0.1 μm and not larger than 2 μm in a cube or tetrahedron having a mol% of at least {100} face emulsion. 2. The silver halide emulsion according to claim 1, wherein the silver bromide-containing phase is formed only at a position of 70% to 95% of the grain volume as measured from the inside of the silver halide grain. The silver halide emulsion according to claim 1 or 2 , wherein the silver bromide-containing phase is formed on the inner side of the grain than the silver iodide-containing phase. The silver halide emulsion according to any one of claims 1 to 3, wherein the silver bromide-containing phase and the silver iodide-containing phase are formed adjacent to each other . The silver halide emulsion according to any one of claims 1 to 4, which has a silver iodide-containing phase on the surface of the silver halide grains. The silver halide emulsion according to any one of the silver halide claims 1 to 5 electron slow release time is 10 seconds from 10 ^-5 seconds particles. It said silver halide grains, Cl, silver halide emulsion according to any one of claims 1 to 6 including the 6-coordinate complex, of which central metal is Ir having a Br or I as ligands. The silver halide emulsion according to claim 7 , wherein the hexacoordinate complex is contained in a silver bromide-containing phase. It said silver halide grains, the silver halide emulsion according to any one of claims 1 to 8 including a 6-coordinate complex having a central metal Ir having at least one non-halogen as a ligand. The silver halide grains are composed of at least one H-coordination complex having iridium as a central metal. ₂ The silver halide emulsion according to any one of claims 1 to 8, which has O, OH, O, OCN, thiazole or substituted thiazole as a ligand. The silver halide emulsion according to any one of the silver halide Claims 1 to 10 oxidation potential of the latent image emulsion is nobler than 70 mV. The silver halide emulsion according to any one of the silver halide emulsion according to claim which is gold sensitization 1 to claim 11. It said silver halide emulsion, the silver halide emulsion of claim 12, the complex stability constant Logbeta ₂ of colloidal gold sulfide or gold is gold sensitization at 21 or more and 35 or less of the gold sensitizer. The silver halide emulsion has a gold complex stability constant log β ₂ The silver halide emulsion according to claim 12, which is gold sensitized with a gold sensitizer represented by the following general formula (I) of 21 to 35.
Formula (I)
{(L ¹ ) _x (Au) _y (L ² ) _z ・ Q _q } _p
In general formula (I), L ¹ And L ² Is log β ₂ Represents a compound having a value between 21 and 35. Q represents a counter anion or counter cation necessary for neutralizing the charge of the compound, x and z represent an integer of 0 to 4, y and p represent 1 or 2, and q includes a decimal number 0 Represents a value of ~ 1. However, neither x nor z is 0. The silver halide emulsion according to any one of claims 1 to 14, wherein the silver halide emulsion is a silver halide emulsion for a silver halide color photographic light-sensitive material. At least one silver halide emulsion layer containing a yellow dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a cyan dye-forming coupler are each provided on the support. a silver halide color photographic light-sensitive material having a silver halide photographic light-sensitive material characterized by containing a silver halide emulsion according to any one of claims 1 to 14.

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