JP4041671B2 - Silver halide emulsion and silver halide color photographic light-sensitive material using the same - Google Patents

Description

【００７４】
【化２】

【００７５】
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。
【００７６】
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。
【００７７】
【化３】

【００７８】
【化４】

【００７９】
【化５】

【００８０】
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。
【００８１】
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。
【００８２】
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。
【００８３】
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。
【００８４】
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。
【００８５】
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。
【００８６】
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。
【００８７】
次に、本発明のハロゲン化銀カラー写真感光材料について説明する。
本発明の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、支持体上にそれぞれ少なくとも一層の青感性ハロゲン化銀乳剤層、緑感性ハロゲン化乳剤層、及び赤感性ハロゲン化乳剤層を有し、青感性ハロゲン化銀乳剤層、緑感性ハロゲン化乳剤層、及び赤感性ハロゲン化乳剤層の少なくとも１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。
【００８８】
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は、支持体上に、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、感光性を有する、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ものが好ましい。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。
【００８９】
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。
【００９０】
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。
【００９１】
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。
【００９２】
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。
【００９３】
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。
【００９４】
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。
【００９５】
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。
【００９６】
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。
【００９７】
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。
【００９８】
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。
【００９９】
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。
【０１００】
本発明のハロゲン化銀カラー写真感光材料は、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。
【０１０１】
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。
【０１０２】
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。
【０１０３】
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。
【０１０４】
【表１】

【０１０５】
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。
【０１０６】
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。
【０１０７】
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。
【０１０８】
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。
【０１０９】
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位と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。
【０１１０】
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。
【０１１１】
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。
【０１１２】
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。
【０１１３】
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。
【０１１４】
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。
【０１１５】
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。
【０１１６】
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。
【０１１７】
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。
【０１１８】
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。
【０１１９】
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と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と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。
【０１２０】
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と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。
【０１２１】
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。
【０１２２】
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。
【０１２３】
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。
【０１２４】
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。
【０１２５】
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。
【０１２６】
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と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。
【０１２７】
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のが好ましい。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。
【０１２８】
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。
【０１２９】
【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。
【０１３０】
［実施例１］
（乳剤Ｂ−１の調製）
石灰処理ゼラチン３％水溶液１０００ｍｌをｐＨ５．５、ｐＣｌ１．７に調整し、硝酸銀を２．１２モル含む水溶液と塩化ナトリウムを２．２モル含む水溶液と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モルとなるように添加した。また、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モルになるように添加した。さらに、硝酸銀の添加が９２％の時点から９８％の時点にかけて、Ｋ₂［Ｉｒ(５−ｍｅｔｈｙｌｔｈｉａｚｏｌｅ)Ｃｌ₅］水溶液を出来上がりのハロゲン化銀１モルあたりＩｒ量が１×１０^-6モルになるように添加した。
４０℃で脱塩処理を施した後、石灰処理ゼラチン１６８ｇを加え、ｐＨ５．５、ｐＣｌ１．８に調整した。得られた粒子は球相当径０．７５μｍ、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上記（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、下記増感色素Ａをハロゲン化銀１モルあたり２×１０^-4モル、下記増感色素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。
【０１３１】
【化６】

【０１３２】
（乳剤Ｂ−２の調製）
上記乳剤Ｂ−１の調製において、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、かつＫ₂［ＩｒＣｌ₆］水溶液の添加時期を臭化カリウムの添加と合わせたこと以外は、上記乳剤Ｂ−１と同様にして乳剤を調製した。得られた粒子は球相当径０．７５μｍ、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−２とした。
【０１３３】
（乳剤Ｂ−３の調製）
上記乳剤Ｂ−１の調製において、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、かつＫ₂［ＩｒＣｌ₆］水溶液の添加時期を臭化カリウムの添加と合わせたこと以外は、上記乳剤Ｂ−１と同様にして乳剤を調製した。得られた粒子は球相当径０．７５μｍ、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。
【０１３４】
（乳剤Ｂ−４の調製）
上記乳剤Ｂ−１の調製において、硝酸銀の添加が７０％の時点から８０％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、かつＫ₂［ＩｒＣｌ₆］水溶液の添加時期を臭化カリウムの添加と合わせたこと以外は、上記乳剤Ｂ−１と同様にして乳剤を調製した。得られた粒子は球相当径０．７５μｍ、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。
【０１３５】
（乳剤Ｂ−５の調製）
上記乳剤Ｂ−１の調製において、硝酸銀の添加が５０％の時点から６０％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、かつＫ₂［ＩｒＣｌ₆］水溶液の添加時期を臭化カリウムの添加と合わせたこと以外は、上記乳剤Ｂ−１と同様にして乳剤を調製した。得られた粒子は球相当径０．７５μｍ、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。
【０１３６】
（乳剤Ｂ−６の調製）
上記乳剤Ｂ−１の調製において、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、かつＫ₂［ＩｒＣｌ₆］水溶液の添加時期を臭化カリウムの添加と合わせ、次に続く硝酸銀と塩化ナトリウムとの添加温度を４０℃に下げたこと以外は、上記乳剤Ｂ-1と同様にして乳剤を調製した。得られた粒子は球相当径０．７５μｍ、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−６とした。
【０１３７】
（乳剤Ｂ−７の調製）
上記乳剤Ｂ−１の調製において、硝酸銀の添加が８０％の時点から９０％の時点にかけて、添加温度を４０℃に下げながら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、かつＫ₂［ＩｒＣｌ₆］水溶液の添加時期を臭化カリウムの添加と合わせ、次に続く硝酸銀と塩化ナトリウムとの添加温度を４０℃に維持したこと以外は、上記乳剤Ｂ−１と同様にして乳剤を調製した。得られた粒子は球相当径０．７５μｍ、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−７とした。
【０１３８】
（乳剤Ｂ−８の調製）
上記乳剤Ｂ−１の調製において、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、かつＫ₂［ＩｒＣｌ₆］水溶液の添加時期を臭化カリウムの添加と合わせ、更に硝酸銀の添加が９９％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０．１モル％になる量を添加したこと以外は、上記乳剤Ｂ−１と同様にして乳剤を調製した。得られた粒子は球相当径０．７５μｍ、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−８とした。
【０１３９】
（乳剤Ｂ−９の調製）
上記乳剤Ｂ−１の調製において、硝酸銀の添加が８０％の時点から９０％の時点にかけて、出来上がりのハロゲン化銀１モルあたり２モル％になる量の臭化物イオンを含むハロゲン化銀微粒子を添加し、かつＫ₂［ＩｒＣｌ₆］水溶液の添加をハロゲン化銀微粒子に含有させて行ったこと以外は、上記乳剤Ｂ−１と同様にして乳剤を調製した。得られた粒子は球相当径０．７５μｍ、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−９とした。
【０１４０】
（乳剤Ｇ−１の調製）
石灰処理ゼラチン３％水溶液１０００ｍｌをｐＨ５．５、ｐＣｌ１．７に調整し、硝酸銀を２．１２モル含む水溶液と塩化ナトリウムを２．２モル含む水溶液とを激しく攪拌しながら４５℃で同時に添加混合した。硝酸銀の添加が８０％の時点から９０％の時点にかけて、臭化カリウムを出来上がりのハロゲン化銀１モルあたり２モル％になる量を激しく混合しながら添加した。また、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。さらに、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９５％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５×１０^-7モルになる量を添加した。更に、硝酸銀の添加が９５％の時点から９８％の時点にかけて、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５×１０^-7モルになる量を添加した。４０℃で脱塩処理を施した後、石灰処理ゼラチン１６８ｇを加え、ｐＨ５．５、ｐＣｌ１．８に調整した。得られた粒子は球相当径０．３５μｍ、変動係数１０％の立方体塩化銀乳剤であった。
【０１４１】
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上記（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、下記増感色素Ｄをハロゲン化銀１モルあたり６×１０^-4モル、１−フェニル−５−メルカプトテトラゾールをハロゲン化銀１モルあたり２×１０^-4モル、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールをハロゲン化銀１モルあたり８×１０^-4モル、臭化カリウムをハロゲン化銀１モルあたり７×１０^-3モル添加した。このようにして得られた乳剤を、乳剤Ｇ−１とした。
【０１４２】
【化７】

【０１４３】
（乳剤Ｒ−１の調製）
石灰処理ゼラチン３％水溶液１０００ｍｌをｐＨ５．５、ｐＣｌ１．７に調整し、硝酸銀を２．１２モル含む水溶液と塩化ナトリウムを２．２モル含む水溶液とを激しく攪拌しながら４５℃で同時に添加混合した。硝酸銀の添加が８０％の時点から１００％の時点にかけて、臭化カリウムを出来上がりのハロゲン化銀１モルあたり４モル％になる量を激しく混合しながら添加した。また、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。さらに、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９０％終了した時点で、沃化カリウム水溶液を出来上がりのハロゲン化銀１モルあたりＩ量が０．１モル％になる量を激しく混合しながら添加した。硝酸銀の添加が９２％の時点から９５％の時点にかけて、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５×１０^-7モルになる量を添加した。更に、硝酸銀の添加が９５％の時点から９８％の時点にかけて、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５×１０^-7モルになる量を添加した。
【０１４４】
４０℃で脱塩処理を施した後、石灰処理ゼラチン１６８ｇを加え、ｐＨ５．５、ｐＣｌ１．８に調整した。得られた粒子は球相当径０．３５μｍ、変動係数１０％の立方体沃臭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上記（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、下記増感色素Ｈをハロゲン化銀１モルあたり２×１０^-4モル、１−フェニル−５−メルカプトテトラゾールをハロゲン化銀１モルあたり２×１０^-4モル、１−（５−メチルウレイドフェニル）−５−メルカプトテトラゾールをハロゲン化銀１モルあたり８×１０^-4モル、化合物Ｉをハロゲン化銀１モルあたり１×１０^-3モル、臭化カリウムをハロゲン化銀１モルあたり７×１０^-3モル添加した。このようにして得られた乳剤を、乳剤Ｒ−１とした。
【０１４５】
【化８】

【０１４６】
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。
【０１４７】
（第一層塗布液の調製）
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。
【０１４８】
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。各層のゼラチン硬膜剤としては、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、各層に防腐剤（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。
【０１４９】
【化９】

【０１５０】
【化１０】

【０１５１】
また、緑感性乳剤層及び赤感性乳剤層に対し、１−フェニル−５−メルカプトテトラゾールを、それぞれハロゲン化銀１モル当り１．０×１０^-3モル及び５．９×１０^-4モル添加した。さらに、第二層、第四層及び第六層にも１−フェニル−５−メルカプトテトラゾールを、それぞれ０．２ｍｇ／ｍ²、０．２ｍｇ／ｍ²及び０．６ｍｇ／ｍ²となるように添加した。
赤感性乳剤層にメタクリル酸とアクリル酸ブチルとの共重合体ラテックス（質量比１：１、平均分子量２０００００〜４０００００）を０．０５ｇ／ｍ²添加した。また、第二層、第四層及び第六層にカテコール−３，５−ジスルホン酸二ナトリウムをそれぞれ６ｍｇ／ｍ²、６ｍｇ／ｍ²、１８ｍｇ／ｍ²となるように添加した。また、イラジエーション防止のために、以下の染料（カッコ内は塗布量を表す）を添加した。
【０１５２】
【化１１】

【０１５３】
（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。
【０１５４】
〈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］
【０１５５】
〈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
【０１５６】
〈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
【０１５７】
〈第三層（緑感性乳剤層）〉
・乳剤Ｇ−１ ０．１４
・ゼラチン １．３６
・マゼンタカプラー（ＥｘＭ） ０．１５
・紫外線吸収剤（ＵＶ−Ａ） ０．１４
・色像安定剤（Ｃｐｄ−２） ０．０２
・色像安定剤（Ｃｐｄ−４） ０．００２
・色像安定剤（Ｃｐｄ−６） ０．０９
・色像安定剤（Ｃｐｄ−８） ０．０２
・色像安定剤（Ｃｐｄ−９） ０．０３
・色像安定剤（Ｃｐｄ−１０） ０．０１
・色像安定剤（Ｃｐｄ−１１） ０．０００１
・溶媒（Ｓｏｌｖ−３） ０．１１
・溶媒（Ｓｏｌｖ−４） ０．２２
・溶媒（Ｓｏｌｖ−５） ０．２０
【０１５８】
〈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
【０１５９】
〈第五層（赤感性乳剤層）〉
・乳剤Ｒ−１ ０．１２
・ゼラチン １．１１
・シアンカプラー（ＥｘＣ−２） ０．１３
・シアンカプラー（ＥｘＣ−３） ０．０３
・色像安定剤（Ｃｐｄ−１） ０．０５
・色像安定剤（Ｃｐｄ−６） ０．０６
・色像安定剤（Ｃｐｄ−７） ０．０２
・色像安定剤（Ｃｐｄ−９） ０．０４
・色像安定剤（Ｃｐｄ−１０） ０．０１
・色像安定剤（Ｃｐｄ−１４） ０．０１
・色像安定剤（Ｃｐｄ−１５） ０．１２
・色像安定剤（Ｃｐｄ−１６） ０．０３
・色像安定剤（Ｃｐｄ−１７） ０．０９
・色像安定剤（Ｃｐｄ−１８） ０．０７
・溶媒（Ｓｏｌｖ−５） ０．１５
・溶媒（Ｓｏｌｖ−８） ０．０５
【０１６０】
〈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
【０１６１】

【０１６２】
【化１２】

【０１６３】
【化１３】

【０１６４】
【化１４】

【０１６５】
【化１５】

【０１６６】
【化１６】

【０１６７】
【化１７】

【０１６８】
【化１８】

【０１６９】
【化１９】

【０１７０】
【化２０】

【０１７１】
【化２１】

【０１７２】
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をそれぞれ乳剤Ｂ−２からＢ−９まで代えた試料も同様に作製し、それぞれ試料Ｂ−２からＢ−９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。
露光後は、以下に示す発色現像処理Ａを行った。
【０１７４】
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／４５ｍＬ
漂白定着 ３８．０℃／４５秒／３５ｍＬ
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／１２１ｍＬ
（注）＊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５０〜３００ｍＬ／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。尚、リンスは（１）から（４）へのタンク向流方式とした。
【０１７５】
各処理液の組成は以下の通りである。

【０１７６】

【０１７７】

【０１７８】
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１．５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。濃度１．５と濃度２．０と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、２０℃・相対湿度５５％の環境下で露光後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１．５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℃・相対湿度５５％の雰囲気で露光し５秒後に処理を開始した場合と、３０℃・相対湿度３０％の雰囲気で露光し５秒後に処理を開始した場合の特性曲線を求め、１０℃・相対湿度５５％の雰囲気で露光し５秒後に処理を開始した場合に濃度１．５を与える露光量での濃度変化を調べた。結果を表２に示す。また臭化銀含有相をエッチング／ＴＯＦ−ＳＩＭＳで分析し、得られたパラメータ値の結果も合わせて表２に示した。パラメータ値の詳細は図２に示すとおりである。
【０１７９】
【表２】

【０１８０】
表２の結果から明らかなように、本発明における臭化銀含有相が形成されている臭塩化銀乳剤を青感光性乳剤層に含有した試料Ｂ−３からＢ−７およびＢ−９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。
【０１８１】
［実施例２］
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。
【０１８２】
試料の作製
〈第一層（青感性乳剤層）〉
・乳剤Ｂ−１ ０．１４
・ゼラチン ０．７５
・イエローカプラー（ＥｘＹ） ０．３４
・色像安定剤（Ｃｐｄ−１） ０．０４
・色像安定剤（Ｃｐｄ−２） ０．０２
・色像安定剤（Ｃｐｄ−３） ０．０４
・色像安定剤（Ｃｐｄ−８） ０．０１
・溶媒（Ｓｏｌｖ−１） ０．１３
【０１８３】
〈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
【０１８４】
〈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
【０１８５】
〈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
【０１８６】
〈第五層（赤感性乳剤層）〉
・乳剤Ｒ−１ 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
【０１８７】
〈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
【０１８８】

【０１８９】
青感性乳剤層の乳剤として上記の乳剤Ｂ−１を用いた試料を、試料Ｂ−２１とした。試料Ｂ−１とは青感性乳剤層の乳剤Ｂ−１を乳剤Ｂ−９に替えた試料も同様に作製し、試料Ｂ−２９とした。
【０１９０】
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。
【０１９１】
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。
【０１９２】
［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。
【０１９３】
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。
【０１９４】
各処理液の組成は以下の通りである。

【０１９５】
【化２２】

【０１９６】

【０１９７】

【０１９８】
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１．５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１．５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、２０℃５５％の環境下で露光後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１．５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５秒後に処理を開始した場合と、３０℃３０％の雰囲気で露光し５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５秒後に処理を開始した場合に濃度１．５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に示す。
【０１９９】
【表３】

【０２００】
表３の結果から明らかなように、本発明の臭化銀含有相が形成されている臭塩化銀乳剤を青感光性乳剤層に含有した試料Ｂ−２９は、青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。
【０２０１】
［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、波長約４４０ｎｍの青色半導体レーザー（2001年3月第48回応用物理学関係連合講演会で日亜化学発表）、半導体レーザー（発振波長 約１０６０ｎｍ）を導波路状の反転ドメイン構造を有するＬｉＮｂＯ₃のＳＨＧ結晶により波長変換して取り出した約５３０ｎｍの緑色レーザー及び波長約６５０ｎｍの赤色半導体レーザー（日立タイプＮｏ．ＨＬ６５０１ＭＧ）を用いた。３色のそれぞれのレーザー光はポリゴンミラーにより走査方向に対して垂直方向に移動し、試料上に、順次走査露光できるようにした。半導体レーザーの温度による光量変動は、ペルチェ素子を利用して温度が一定に保たれることで抑えられている。実効的なビーム径は、８０μｍで、走査ピッチは４２．３μｍ（６００ｄｐｉ）であり、１画素あたりの平均露光時間は、１．７×１０^-7秒であった。
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Ｂ−２９は、青感層が高い感度と階調を示し、また、本発明の試料Ｂ−２９は、赤感層も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。
【０２０２】
【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及びそれを用いたハロゲン化銀カラー写真感光材料を得ることができる。また、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及びそれを用いたハロゲン化銀カラー写真感光材料を得ることができる。更に、本発明によれば、迅速処理性に優れ、発色効率が高いことから低コストのハロゲン化銀カラー写真感光材料を提供することができる。
【図面の簡単な説明】
【図１】 本発明における塩臭化銀粒子中の臭化銀含有率曲線の一例を示すグラフである。
【図２】 本発明における臭化銀含有相の各種パラメータ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. Specifically, the silver halide emulsion is suitable for rapid processing, and can provide a high-sensitivity and high gradation even in digital exposure such as laser scanning exposure, and the silver halide emulsion. The present invention relates to a silver halide color photographic light-sensitive material using a silver halide emulsion.
[0002]
[Prior art]
In recent years, there has been a remarkable spread of digitization in the field of color printing using color photographic paper. For example, the digital exposure method using laser scanning exposure is an analog that directly prints with a color printer from a processed color negative film. Compared to the exposure method, it shows a dramatic increase in the penetration rate. Such a digital exposure method is characterized in that high image quality can be obtained by performing image processing, and plays an extremely important role in improving the quality of color prints using color photographic paper. In addition, with the rapid spread of digital cameras, it is also an important factor that simple and high-quality color prints can be obtained from these electronic recording media, and it is thought that these will lead to further dramatic spread.
[0003]
On the other hand, as a color printing method, technologies such as an ink jet method, a sublimation type method, and color xerography have advanced, and are being recognized as a color printing method, such as improving the quality of photographs. Among these, the characteristics of the digital exposure method using color photographic paper are high image quality, high productivity, and high image robustness. Taking advantage of these features, it is easier to make higher-quality photos. It is desired to provide it at low 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.
[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 providing a (silver bromide-containing layer) and doping iridium therein. The silver halide emulsion prepared by this method has high sensitivity and high contrast even at a relatively high illumination exposure of about 1/100 second, and does not cause a problem of latent image sensitization, but is required by a digital exposure method by 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 a method for reducing high-intensity failure 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]
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, Japanese Patent No. 284,743 discloses that high sensitivity can be obtained by including a phase having a high silver bromide content in various forms in an emulsion having a high silver chloride content. However, these silver bromide-containing phases have not been optimized to the distribution inside the grains, and the effect has been insufficient in ultra-high illumination exposure such as laser scanning exposure.
[0007]
[Problems to be solved by the invention]
  The present invention tries to solveTaskDoes not cause low sensitivity or soft gradation even in digital exposure such as laser scanning exposure, and high sensitivity and high gradation can be obtained.AndA silver halide emulsion excellent in latent image storage stability and exposure temperature / humidity dependency, and a silver halide color photographic light-sensitive material using the same.
  FurtherIn addition,An object of the present invention is to provide a low-cost silver halide color photographic light-sensitive material because of its excellent rapid processability and high color development efficiency.
[0008]
[Means for Solving the Problems]
  As a result of extensive studies by the present inventors, the above object is achieved by the following <1> to <1.18It has been found that it can be effectively achieved by the method described in>. That is,
<1> In a silver halide emulsion comprising silver halide grains having a silver chloride content of 90 mol% or more, the silver halide grains are cubic orThe main plane is composed of (100) planesIt is a tetrahedral grain, and has a maximum point at which the silver bromide content reaches a maximum at any position of 50% to 98% of the grain volume as measured from the inside of the silver halide grain. It is a silver halide emulsion characterized by having a silver bromide-containing phase in which the silver bromide content decreases toward the surface and the internal direction of the silver halide grains.
[0013]
<2> The silver bromide content F on the surface of the silver halide grains satisfies F ≦ 0.9 × M with respect to the silver bromide content M at the maximum point.<1>Silver halide emulsion.
[0014]
<3> The silver bromide-containing phase is the absolute value of the slope of the tangent line of the silver bromide content curve at the position where the maximum value of the silver halide grains is attenuated to the surface and / or the interior of the grains. The value is 0.1 to 50 mol% / nm <1>Or <2>Silver halide emulsion.
[0015]
<4The distance d1 from the maximum point in the silver bromide-containing phase to a position showing a half value of the maximum concentration in the surface direction of the silver halide grains is the maximum concentration in the internal direction of the silver halide grains from the maximum point. <1> to <1>, characterized in that it is smaller than the distance d2 to the position showing the half value of<3>The silver halide emulsion according to any one of the above.
[0016]
<5> The sum (d1 + d2) of the distance d1 and the distance d2 satisfies (d1 + d2) /R≦0.2 with respect to the radius R of the silver halide grains.<4>Silver halide emulsion.
[0017]
<6> The silver bromide content at the maximum point of the silver bromide-containing phase is 5 to 95 mol% <1> to<5>The silver halide emulsion according to any one of the above.
<7The silver bromide-containing phase is composed of a silver amount of 3% to 30% of the silver halide grain volume.<6>The silver halide emulsion according to any one of the above.
<8> The local silver bromide content of the silver bromide-containing phase is 5 mol% or more <1> to<7>The silver halide emulsion according to any one of the above.
[0019]
<9> The silver halide grains contain one or more transition metal complexes <1> to <18The silver halide emulsion according to any one of
<10> The transition metal complex is H₂It is a transition metal complex having at least one ligand selected from O, OH, O, OCN, thiazole and substituted thiazole, and containing a hexacoordination complex having iridium as a central metal <9> Silver halide emulsion.
<11> The transition metal complex is H₂At least one hexacoordination complex having at least one ligand selected from O, OH, O, OCN, thiazole and substituted thiazole and having iridium as a central metal, and iron, ruthenium, osmium, lead, And at least one metal complex selected from cadmium and zinc,9> Silver halide emulsion.
[0020]
<12> The silver bromide-containing phase contains one or more transition metal complexes <1> to <11The silver halide emulsion according to any one of
<13> The transition metal complex is characterized in that all of the six ligands are selected from Cl, Br and I, and is at least one of six-coordinate complexes having iridium as a central metal. <12> Silver halide emulsion.
<14<1> to <1>, wherein the silver halide grains are silver sensitized silver halide grains13The silver halide emulsion according to any one of
<15> The silver bromide-containing phase contains an aqueous solution of a water-soluble silver salt and bromide ions in a mixing vessel provided in addition to a reaction vessel that causes nucleation and / or grain growth of silver halide grains. <1> to <1, characterized by being formed using silver halide fine grains containing silver bromide formed by supplying and mixing an aqueous solution of halide.14The silver halide emulsion according to any one of
<16The average projected grain size of the silver halide fine particles containing silver bromide is less than 0.06 μm,15> Silver halide emulsion.
[0021]
<17> The silver bromide-containing phase is formed using silver halide fine particles containing silver bromide containing one or more transition metal complexes formed in the mixing vessel <15> Or <16> Silver halide emulsion.
[0022]
<18> In the silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red-sensitive silver halide emulsion layer, respectively, on the support, the blue-sensitive silver halide At least one of the emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer comprises <1> to <17> A silver halide color photographic light-sensitive material comprising the silver halide emulsion of any one of the above.
[0023]
DETAILED DESCRIPTION OF THE INVENTION
  The present invention is described in detail below.
  The silver halide emulsion of the present invention is a silver halide emulsion comprising silver halide grains having a silver chloride content of 90 mol% or more, wherein the silver halide grains are cubic orThe main plane is composed of (100) planesIt is a tetrahedral grain, and has a maximum point at which the silver bromide content reaches a maximum at any position of 50% to 98% of the grain volume as measured from the inside of the silver halide grain. It has a silver bromide-containing phase in which the silver bromide content decreases toward the surface and the internal direction of the silver halide grains.
  The silver halide emulsion of the present invention has the silver bromide-containing phase having a maximum point on the inner side of the silver halide grains, so that when used in a silver halide color photographic light-sensitive material, it is like laser scanning exposure. Even in digital exposure, high sensitivity and high gradation can be obtained without causing a reduction in sensitivity and softening. In addition, the silver halide color photographic light-sensitive material using the halogenated emulsion of the present invention is excellent in latent image storage stability and exposure temperature / humidity dependency, and also has excellent rapid processing properties and high color development efficiency. is there.
[0024]
  The silver halide emulsion of the present invention contains the specific silver halide grains described above. The particle shape of the particle is a cube or a tetrahedron, and a substantially (100) face cube orThe main plane is composed of (100) planesThese are tetrahedral crystal grains (they may have rounded grain vertices and higher-order faces).
[0025]
  As the silver halide emulsion of the present invention, specific silver halide grainsChildIncluding emulsions are used. the abovehalogenThe silver chloride content in the silver halide grains needs to be 90 mol% or more, and from the viewpoint of rapid processability, the silver chloride content is preferably 93 mol% or more, more preferably 95 mol% or more. Also, abovehalogenThe silver bromide content in the silver halide grains 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. Also abovehalogenThe silver halide grains may contain silver iodide.
[0026]
  Specific silver halide grains in the silver halide emulsion of the present inventionThe child is, The inside (here "inside"halogenIt means a portion occupying 98% of the volume from the center of the total volume of silver halide grains. )Any one of the positions of 50% or more of the particle volume measured from the inside of the particleHave a silver bromide-containing phase. Here, the “silver bromide-containing phase” means a site where the concentration of silver bromide is higher than the surroundings, and has a maximum point at which the silver bromide content is maximum. Such a silver bromide-containing phase may form a layer having a substantially constant width at a certain portion in the grain. The maximum point of the silver bromide-containing phase refers to the midpoint of the interval where the concentration is continuous. 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%. Further, a plurality of such silver bromide-containing phases may be present in layers in the grains.
[0027]
  In the silver bromide-containing phase in the present invention, the halogen composition around it may change continuously or may change abruptly. Preferably, in the silver bromide content curve that decays from the maximum point of the silver bromide-containing phase toward the grain surface and / or the inside of the grain as shown in FIG. 1, half the silver bromide content M at the maximum point. The absolute values (| a | and | a '|) of the slopes of tangent lines (straight lines A and A' in FIG. 1) at positions X and X ′ showing 0.1 to 50 mol% / nm, more preferably 1 to 20 mol% / nm. Here is the “silver bromide content curve”halogenThe curve which shows the silver bromide content rate with respect to the depth direction of the grain in the internal direction of a silver halide grain.
[0028]
  MaFurther, the silver bromide content F of the surface of the silver halide grains (here, “surface” means a portion excluding the “inside” of the silver halide grains) is the silver bromide at the maximum point. Compared with the content M, F ≦ 0.9 × M is preferably satisfied, and F ≦ 0.7 × M is more preferable.
[0029]
As shown in FIG. 1, the silver bromide-containing phase in the present invention is a distance d1 (distance in the grain surface direction) between the concentration maximum position (maximum point) of bromide ions and the positions X and X ′ showing the half value of the maximum concentration. And d2 (distance in the particle internal direction) is preferably d1 <d2, and more preferably d1 <0.5 × d2. The total of d1 and d2 preferably satisfies (d1 + d2) /R≦0.2 with respect to the particle radius R, and more preferably satisfies (d1 + d2) /R≦0.1. The silver bromide content at the maximum point of the silver bromide-containing phase is preferably 5 to 95 mol%, more preferably 10 to 80 mol%.
[0030]
It is important that the silver bromide-containing phase of the silver halide emulsion of the present invention is layered so as to surround the grains. In one preferred embodiment, the silver bromide-containing phase formed in a layer so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains. However, in the silver bromide-containing phase that is layered so as to surround the grain, the maximum point or the minimum point of the silver bromide concentration may exist in the circumferential direction of the grain and may have a concentration distribution. For example, when a silver bromide-containing phase is formed in a layer so as to surround the grain in the vicinity of the grain surface, the silver bromide concentration at the grain corner or edge may be different from the main surface. Further, apart from the silver bromide-containing phase that is layered so as to surround the grain, there may be a silver bromide-containing phase that exists completely in a specific portion on the surface of the grain and does not surround the grain.
[0031]
In the silver halide emulsion of the present invention, the silver bromide-containing phase is preferably formed in layers so that the silver bromide concentration maximum is present inside the grains. Such a silver bromide-containing phase is preferably composed of a silver amount of 3% or more and 30% or less of the grain volume in order to increase the local concentration with a smaller silver bromide content. More preferably, it is composed of a silver amount of not more than%.
[0032]
  The silver bromide content necessary for expressing the effects of the present invention such as high sensitivity and high contrast is increased as the silver bromide-containing phase is formed inside the grains, and the silver chloride content is more than necessary. May degrade the rapid processing performance. Therefore, in order to aggregate these functions controlling photographic action close to the surface within the grain, the silver bromide-containing phase is measured from the inside to 50% to98%Formed in one of the positionsIt is mandatory to doFurther, it is more preferable to form it at any position of 70% to 95% of the particle volume.
[0033]
The introduction of bromide ions to contain silver bromide in the silver halide emulsion of the present invention can be carried out by adding a bromide salt solution alone or in combination with addition of a silver salt solution and a high chloride salt solution. May be added. In the latter case, the bromide salt solution and the high chloride salt solution may be added separately or as a mixed solution of bromide salt and high chloride salt. The bromide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt. Alternatively, it can be introduced by cleaving bromide ions from organic molecules described in US Pat. No. 5,389,508.
[0034]
As another bromide ion source, silver halide fine grains containing silver bromide can be used. The silver halide fine particles containing silver bromide are mixed using a mixing vessel described in the specification of JP-A-10-43570, etc., separately from a reaction vessel for causing nucleation and / or grain growth of silver halide grains. It can be formed by supplying and mixing an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide containing bromide ions. In the mixing vessel, an aqueous solution of a water-soluble silver salt and a bromide salt solution and a high chloride salt solution are introduced separately, or a mixed solution of a bromide salt and a high chloride salt is introduced, and a halogen containing silver bromide is introduced. Form silver halide fine particles. The silver halide fine particles containing silver bromide formed in the mixing vessel are preferably added to the reaction vessel immediately after formation. This is because the grain size of the silver halide fine grains is increased by Ostwald ripening after the formation, thereby making it difficult to dissolve in the reaction vessel, and as a result, the release of bromide ions is suppressed. For this reason, the average projected particle size of the silver halide fine particles containing silver bromide is preferably less than 0.06 μm, more preferably 0.001 to 0.06 μm, and further 0.001 to 0.04 μm. Preferably, 0.001 to 0.02 μm is most preferable. The introduction of bromide ions by the silver halide fine particles containing silver bromide may be added to the reaction vessel alone or in addition to the addition of the silver salt solution and the high chloride salt solution. . In addition, you may use what has the 1 or more types of transition metal complex mentioned later as a silver halide fine particle containing the said silver bromide.
In addition, by using the silver halide fine particles containing silver bromide as a silver bromide ion source, silver chlorobromide having a silver bromide-containing phase that is more uniform between grains (small variation between grains) Emulsion grains can be obtained.
[0035]
Addition of bromide ions (addition of bromide salt solution or addition of silver halide fine grains containing silver bromide) may be concentrated during a period of grain formation or may be performed over a certain period of time. . Addition of bromide ions is preferably performed outside 50% of the particle volume, more preferably outside 70%.
[0036]
The distribution of bromide ion concentration in the depth direction in the particles can be 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. 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. The emulsion of the present invention is preferably analyzed by etching / TOF-SIMS method, and bromide ions preferably have a maximum concentration inside the grains. The local concentration of silver bromide can also be measured by X-ray diffraction if the silver bromide content is somewhat high.
[0037]
In this specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle. The silver halide emulsion of the present invention is preferably composed of grains having a monodispersed grain size distribution. The variation system of the equivalent sphere diameter of all the grains in the silver halide emulsion of the present invention is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less. The variation coefficient of the equivalent sphere diameter is expressed as a percentage of the standard deviation of the equivalent sphere diameter of each particle with respect to the average equivalent sphere diameter. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating.
[0038]
  The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grains and the number average thereof) is 0.1 to 2 μm The thickness is preferably 0.1 μm to 0.7 μm. More preferably, they are 0.1 micrometer-0.38 micrometer, and 0.1 micrometer-0.2 micrometer are the most preferable. The silver halide emulsion of the present invention contains silver halide grains contained in the silver halide emulsion defined in the present invention (that is, specific silver halide grains).Child)Silver halide grains other than those may be included. However, the silver halide emulsion defined in the present invention requires that 50% or more of the total projected area of all the grains be silver halide grains defined in the present invention, and preferably 80% or more. More preferably, it is 90% or more.
[0039]
  Specific silver halide grains in the silver halide emulsion of the present inventionThe child isIt is preferable to contain one or more transition metal complexes, and it is more preferable to contain one or more transition metal complexes in the silver bromide-containing phase. As the transition metal complex, an iridium compound is particularly preferable. 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 a preferred embodiment of 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 comprising 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 containing 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.
[0040]
As a specific example of a hexacoordination complex in which all six ligands are composed of Cl, Br or I and whose center metal is Ir, [IrCl₆]^2-, [IrCl₆]^3-, [IrBr₆]^2-, [IrBr₆]^3-, [IrI₆]^3-Is mentioned. However, iridium in the present invention is not limited to these.
[0041]
As a different preferred embodiment of iridium used in the present invention, a hexacoordinate complex having Ir as a central metal having at least one ligand other than halogen or cyan is preferable.₂Preferred 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 hexacoordination 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 hexacoordination complex having 1 or 2 5-methylthiazole as a ligand and the remaining ligand of which is composed of Cl, Br or I and having Ir as a central metal is most preferable.
[0042]
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 being Cl, Br or I as a central metal are given below. It is not limited to these.
[0043]
[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]^-
[0044]
An object of the present invention is to provide a hexacoordinate complex in which all six ligands are composed of Cl, Br, or I and have Ir as a central metal, or Ir that has at least one ligand other than halogen or cyan. This is more preferably achieved by using either one of the coordination complexes alone. 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 Ir having at least one ligand other than halogen or cyan. It is preferable to use together a 6-coordination complex having a central metal. Furthermore, at least one H₂A hexacoordinated complex having Ir as a central metal and comprising O, OH, O, OCN, thiazole or substituted thiazole as a ligand, and the remaining ligand consisting of 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).
[0045]
The metal complex mentioned above is an anion, and when a salt is formed with a cation, the metal complex that is easily dissolved in water as the counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do. These iridium complexes are 1 x 10 per mole of silver during grain formation.^-TenMol ~ 1 × 10^-3It is preferable to add 1 mol.^-8Mol ~ 1 × 10^-FiveMost preferably, it is added in a molar amount.
[0046]
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.
[0047]
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 the hexacoordinate complex having Ir as the central metal, in which all six ligands are Cl, Br or I, has a silver bromide concentration maximum. It is preferable to contain.
[0048]
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 the other metal ions, transition metal ions are preferable, and among them, iron, ruthenium, osmium, lead, cadmium, or zinc is preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any of the above metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and a plurality of types of ligands are used in one complex molecule. It is also preferable to use it. Moreover, an organic compound can also be used as a ligand, and a preferable organic compound includes a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More 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.
[0049]
A combination of a metal ion and a ligand is preferably a combination of an iron ion or ruthenium ion and a cyanide ion. In the present invention, it is preferable to use iridium in combination with these compounds. 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.^-8Mol ~ 1 × 10^-2It is preferable to add 1 mol.^-6Mol ~ 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.
[0050]
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.
[0051]
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.
[0052]
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.
[0053]
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.
[0054]
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.
[0055]
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
[0056]
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.
[0057]
L¹And L²For example, a compound containing at least one unstable sulfur group capable of reacting with silver halide to produce 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 represents 0 including a decimal number. Represents a value of ~ 1. However, neither x nor z is 0.
[0058]
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.
[0059]
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 each represents 1. To express.
[0060]
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.
[0061]
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. .
[0062]
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.
[0063]
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 (e.g. Ropropyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, cyclododecyl and the like), an alkenyl group having 2 to 16 carbon atoms (for example, allyl, 2-butenyl, 3-pentenyl and the like), an alkynyl group 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 examples of the heterocyclic group include substituted or unsubstituted Nitrogen hetero 5-membered rings (eg, imidazolyl, 1,2,4-triazolyl, teto Zolyl, 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, or 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, phenylsulfonyl etc.) Can be mentioned.
[0064]
L¹And L²-SR 'represented by general formula (1), R' 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.
[0065]
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 ring (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, benzothiazo And the like.
[0066]
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 as antifoggants in the art (for example, indazoles). , Benzimidazoles, benzotriazoles, tetra Zainden, etc.) is preferable.
[0067]
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. Phosphines substituted with (for example, triphenylphosphine, triethylphosphine, etc.) and the like.
[0068]
Furthermore, the above, L¹And L²The mesoionic compound represented by the formula, —SR ′, and the heterocyclic compound are substituted with unstable sulfur groups (for example, thioureido groups) that can react with silver halide to form silver sulfide. It is preferable.
[0069]
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.
[0070]
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.
[0071]
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.
[0072]
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.
[0073]
[Chemical 1]

[0074]
[Chemical formula 2]

[0075]
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.
[0076]
Next, although the specific example of a compound represented by general formula (I) is shown, this invention is not limited to these.
[0077]
[Chemical Formula 3]

[0078]
[Formula 4]

[0079]
[Chemical formula 5]

[0080]
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.
[0081]
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.
[0082]
The silver halide emulsion of the present invention can be used in combination with other chemical sensitization in addition to gold sensitization. Examples of 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.
[0083]
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.
[0084]
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 into the present specification. ), Sulfo-substituted catechols 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-dihydroxybenzene Sulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), hydroxylamines represented by general formula (A) in US Pat. No. 5,556,741 (US Pat. No. 556, 741, the fourth column, line 56 to eleventh column, 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.
[0085]
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-Cyanines 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.
[0086]
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.
[0087]
Next, the silver halide color photographic light-sensitive material of the present invention will be described.
The silver halide color photographic light-sensitive material of the present invention (hereinafter sometimes referred to simply as “light-sensitive material”) has at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red on the support. It has a light sensitive emulsion layer, and at least one of a blue sensitive silver halide emulsion layer, a green sensitive halogenated emulsion layer, and a red sensitive halogenated emulsion layer contains the silver halide emulsion of the present invention. To do.
[0088]
The silver halide color photographic light-sensitive material in which the silver halide emulsion of the present invention is preferably used has a wavelength different from each other on the support (for example, light in the blue region, green region and red region). At least one photosensitive silver halide emulsion layer containing a yellow dye-forming coupler, 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. What has is preferable. 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.
[0089]
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.
[0090]
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. Transparent supports such as cellulose nitrate film and polyethylene terephthalate, as well as 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 a water-resistant resin layer (laminate layer) is preferable.
[0091]
In the present invention, more preferred reflective supports include those having a polyolefin layer having fine pores on the paper substrate on the side on which the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no micropores (eg polypropylene, polyethylene) and is 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, 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.
[0092]
In addition, it is also preferable to provide a polyolefin layer on the opposite side (back surface) to the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflective support. In this case, the back surface polyolefin layer has a matte polyethylene surface. Alternatively, polypropylene is preferable, and polypropylene is more preferable. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support of the present invention, preferred embodiments relating to 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.
[0093]
Furthermore, it is preferable to contain a fluorescent brightening agent in the water-resistant resin layer. Further, a hydrophilic colloid layer containing the fluorescent brightening agent in a dispersed manner may be separately formed. As the optical brightener, benzoxazole-based, coumarin-based, and pyrazoline-based compounds can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based fluorescent whitening agents are more preferable. The amount used is not particularly limited, but preferably 1 to 100 mg / m.²It is. The mixing ratio in the case of mixing with a water resistant resin is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass with respect to the resin.
[0094]
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.
[0095]
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.
[0096]
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.
[0097]
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.
[0098]
In the present invention, a colored layer that can be decolored by treatment in place of the water-soluble dye or in combination with the water-soluble dye is used. The colored layer that can be decolored by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably placed under the emulsion layer (support side) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to select and install only some of them. It is also possible to install a colored layer that has been colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength having the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm for normal printer exposure, wavelength of the scanning exposure light source used for scanning exposure). The optical density value at is preferably 0.2 or more and 3.0 or less. More preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.
[0099]
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.
[0100]
The silver halide color 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.
[0101]
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.
[0102]
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.
[0103]
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.
[0104]
[Table 1]

[0105]
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.
[0106]
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 EP 0488248 and EP 0491197A1, 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.
[0107]
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.
[0108]
Of these cyan couplers, pyrroloazole cyan couplers represented by general formula (I) described in JP-A No. 11-282138 are particularly preferred. The description including the exemplified cyan couplers (1) to (47) is applied to the present application as it is, and is preferably incorporated as part of the specification of the present application.
[0109]
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, and paragraph numbers [0009] to [0026] of the patent are directly applied to the present application. And is incorporated as part of the specification of the present application. 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.
[0110]
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.
[0111]
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.
[0112]
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.
[0113]
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-5-197004, JP-A-5-232630, JP-A-5-307232, JP-A-6-21813, 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.
[0114]
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.
[0115]
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.
[0116]
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.
[0117]
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, any one of red light emitters, green light emitters, and blue light emitters, or a mixture of two or more thereof may be used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.
[0118]
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.
[0119]
The photosensitive material of the present invention is a monochromatic material such as a second harmonic light source (SHG) in which a solid laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a semiconductor laser as a pumping light source and a nonlinear optical crystal is combined. A digital scanning exposure method using high-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) in which a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal are combined. 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.
[0120]
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 state 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.
[0121]
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.
[0122]
Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above.
[0123]
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.
[0124]
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.
[0125]
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.
[0126]
As a method for developing the light-sensitive material of the present invention after exposure, a conventional method of developing with a developer containing an alkaline agent and a developing agent, a developing agent containing the developing agent in the photosensitive material, and an alkali solution containing no developing agent, etc. In addition to a wet method such as a method of developing with an activator solution, a thermal development method that does not use a processing solution can be used. In particular, the activator method is a preferable method from the viewpoint of environmental protection because it does not contain a developing agent in the processing solution, so that the processing solution can be easily managed and handled, and the load during processing of the waste liquid is small.
In the activator method, 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.
[0127]
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, this method is preferably used as an 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.
[0128]
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.
[0129]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[0130]
[Example 1]
(Preparation of emulsion B-1)
1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were simultaneously added and mixed at 66 ° C. with vigorous stirring. . From the point of 80% to 90% addition of silver nitrate,_Four[Ru (CN)₆The aqueous solution has a Ru amount of 3 × 10 5 per mole of the finished silver halide.^-FiveIt added so that it might become a mole. In addition, from the time when the addition of silver nitrate was 83% to 88%, K₂[IrCl₆The amount of Ir per mol of the finished silver halide is 3 × 10^-8It added so that it might become a mole. Furthermore, from the time when the addition of silver nitrate is 92% to the time when 98%,₂[Ir (5-methylthiazole) Cl_FiveThe amount of Ir per mole of the finished silver halide is 1 × 10^-6It added so that it might become a mole.
After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grain was a cubic silver chloride emulsion having a sphere equivalent diameter of 0.75 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. using sodium thiosulfate pentahydrate as a sulfur sensitizer and the above (S-2) as a gold sensitizer. After the temperature was lowered to 40 ° C., the following sensitizing dye A was added at 2 × 10 2 per mole of silver halide.^-FourMol, the following 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.
[0131]
[Chemical 6]

[0132]
(Preparation of emulsion B-2)
In the preparation of the emulsion B-1, from 90% to 100% addition of silver nitrate, potassium bromide was added in an amount of 2 mol% per mol of the finished silver halide with vigorous mixing. And K₂[IrCl₆An emulsion was prepared in the same manner as Emulsion B-1, except that the addition of the aqueous solution was combined with the addition of potassium bromide. The obtained grain was a cubic silver bromochloride emulsion having a sphere equivalent diameter of 0.75 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-2.
[0133]
(Preparation of emulsion B-3)
In the preparation of the emulsion B-1, from the time when the addition of silver nitrate was 80% to 90%, potassium bromide was added in an amount of 2 mol% per mol of the finished silver halide with vigorous mixing. And K₂[IrCl₆An emulsion was prepared in the same manner as Emulsion B-1, except that the addition of the aqueous solution was combined with the addition of potassium bromide. The obtained grain was a cubic silver bromochloride emulsion having a sphere equivalent diameter of 0.75 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-3.
[0134]
(Preparation of emulsion B-4)
In the preparation of the emulsion B-1, from the time point when the addition of silver nitrate is 70% to 80%, potassium bromide is added in an amount of 2 mol% per mol of the finished silver halide while vigorously mixing. And K₂[IrCl₆An emulsion was prepared in the same manner as Emulsion B-1, except that the addition of the aqueous solution was combined with the addition of potassium bromide. The obtained grain was a cubic silver bromochloride emulsion having a sphere equivalent diameter of 0.75 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-4.
[0135]
(Preparation of emulsion B-5)
In the preparation of the emulsion B-1, from the time when the addition of silver nitrate was 50% to 60%, potassium bromide was added in an amount of 2 mol% per mol of the finished silver halide with vigorous mixing. And K₂[IrCl₆An emulsion was prepared in the same manner as Emulsion B-1, except that the addition of the aqueous solution was combined with the addition of potassium bromide. The obtained grain was a cubic silver bromochloride emulsion having a sphere equivalent diameter of 0.75 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-5.
[0136]
(Preparation of emulsion B-6)
In the preparation of the emulsion B-1, from the time when the addition of silver nitrate was 80% to 90%, potassium bromide was added in an amount of 2 mol% per mol of the finished silver halide with vigorous mixing. And K₂[IrCl₆An emulsion was prepared in the same manner as Emulsion B-1, except that the addition time of the aqueous solution was matched with the addition of potassium bromide and the subsequent addition temperature of silver nitrate and sodium chloride was lowered to 40 ° C. The obtained grain was a cubic silver bromochloride emulsion having a sphere equivalent diameter of 0.75 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-6.
[0137]
(Preparation of emulsion B-7)
In the preparation of the emulsion B-1, the amount of potassium bromide is 2 mol% per mol of the finished silver halide while the addition temperature is lowered to 40 ° C. from the point of 80% to 90% of the addition of silver nitrate. With vigorous mixing and K₂[IrCl₆The emulsion was prepared in the same manner as Emulsion B-1, except that the addition time of the aqueous solution was matched with the addition of potassium bromide, and the subsequent addition temperature of silver nitrate and sodium chloride was maintained at 40 ° C. The obtained grain was a cubic silver bromochloride emulsion having a sphere equivalent diameter of 0.75 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-7.
[0138]
(Preparation of emulsion B-8)
In the preparation of the emulsion B-1, from the time when the addition of silver nitrate was 80% to 90%, potassium bromide was added in an amount of 2 mol% per mol of the finished silver halide with vigorous mixing. And K₂[IrCl₆The amount of addition of the aqueous solution is combined with the addition of potassium bromide, and the amount of potassium bromide is 0.1 mol% per mol of the finished silver halide from 99% to 100% addition of silver nitrate. An emulsion was prepared in the same manner as Emulsion B-1, except that was added. The obtained grain was a cubic silver bromochloride emulsion having a sphere equivalent diameter of 0.75 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-8.
[0139]
(Preparation of emulsion B-9)
In the preparation of the emulsion B-1, silver halide fine particles containing bromide ions in an amount of 2 mol% per 1 mol of the finished silver halide were added from the time when the addition of silver nitrate was 80% to 90%. And K₂[IrCl₆An emulsion was prepared in the same manner as Emulsion B-1, except that the aqueous solution was added to the silver halide fine grains. The obtained grain was a cubic silver bromochloride emulsion having a sphere equivalent diameter of 0.75 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-9.
[0140]
(Preparation of emulsion G-1)
1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were simultaneously added and mixed at 45 ° C. with vigorous stirring. . From 80% to 90% addition of silver nitrate, potassium bromide was added in vigorous mixing in an amount of 2 mol% per mole of finished silver halide. In addition, from the time when the addition of silver nitrate is 80% to 90%, K_Four[Ru (CN)₆] The amount of Ru per mol of finished silver halide is 3 × 10^-FiveMolar amounts were added. Furthermore, from the time when the addition of silver nitrate was 83% to 88%, K₂[IrCl₆The amount of Ir per mole of the finished silver halide is 5 × 10^-8Molar amounts were added. From 92% to 95% addition of silver nitrate, K₂[Ir (5-methylthiazole) Cl_Five] The amount of Ir per mol of the finished silver halide is 5 × 10^-7Molar amounts were added. Furthermore, from the time when the addition of silver nitrate is 95% to 98%, K₂[Ir (H₂O) Cl_Five] The amount of Ir per mol of the finished silver halide is 5 × 10^-7Molar amounts were added. After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were cubic silver chloride emulsions having a sphere equivalent diameter of 0.35 μm and a coefficient of variation of 10%.
[0141]
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. using sodium thiosulfate pentahydrate as a sulfur sensitizer and the above (S-2) as a gold sensitizer. After the temperature was lowered to 40 ° C., the following sensitizing dye D was added at 6 × 10 6 per mol of silver halide.^-FourMol, 1-phenyl-5-mercaptotetrazole, 2 × 10 5 per mole of silver halide^-FourMol, 1- (5-methylureidophenyl) -5-mercaptotetrazole, 8 × 10 8 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.
[0142]
[Chemical 7]

[0143]
(Preparation of emulsion R-1)
1000 ml of 3% aqueous solution of lime-processed gelatin was adjusted to pH 5.5 and pCl 1.7, and an aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.2 mol of sodium chloride were simultaneously added and mixed at 45 ° C. with vigorous stirring. . From 80% to 100% addition of silver nitrate, potassium bromide was added in vigorous mixing in an amount of 4 mol% per mole of finished silver halide. In addition, from the time when the addition of silver nitrate is 80% to 90%, K_Four[Ru (CN)₆] The amount of Ru per mol of finished silver halide is 3 × 10^-FiveMolar amounts were added. Furthermore, from the time when the addition of silver nitrate was 83% to 88%, K₂[IrCl₆The amount of Ir per mole of the finished silver halide is 5 × 10^-8Molar amounts were added. When 90% of the addition of silver nitrate was completed, an aqueous potassium iodide solution was added while vigorously mixing in an amount such that the amount of I was 0.1 mol% per mol of the finished silver halide. From 92% to 95% addition of silver nitrate, K₂[Ir (5-methylthiazole) Cl_Five] The amount of Ir per mol of the finished silver halide is 5 × 10^-7Molar amounts were added. Furthermore, from the time when the addition of silver nitrate is 95% to 98%, K₂[Ir (H₂O) Cl_Five] The amount of Ir per mol of the finished silver halide is 5 × 10^-7Molar amounts were added.
[0144]
After desalting at 40 ° C., 168 g of lime-processed gelatin was added to adjust the pH to 5.5 and pCl1.8. The obtained grains were cubic silver iodobromochloride emulsions having a sphere equivalent diameter of 0.35 μm and a coefficient of variation of 10%.
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. using sodium thiosulfate pentahydrate as a sulfur sensitizer and (S-2) as a gold sensitizer. After the temperature was lowered to 40 ° C., the following sensitizing dye H was added at 2 × 10 2 per mole of silver halide.^-FourMol, 1-phenyl-5-mercaptotetrazole, 2 × 10 5 per mole of silver halide^-FourMol, 1- (5-methylureidophenyl) -5-mercaptotetrazole, 8 × 10 8 per mole of silver halide^-FourMoles of Compound I 1 × 10 5 per mole of silver halide^-3Moles of potassium bromide, 7 x 10 per mole of silver halide^-3Mole was added. The emulsion thus obtained was designated as Emulsion R-1.
[0145]
[Chemical 8]

[0146]
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.
[0147]
(Preparation of first layer coating solution)
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.
[0148]
The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. In addition, the preservatives (Ab-1), (Ab-2), (Ab-3), and (Ab-4) were added to each layer in a total amount of 15.0 mg / m.²60.0 mg / m²5.0 mg / m²And 10.0 mg / m²It added so that it might become.
[0149]
[Chemical 9]

[0150]
Embedded image

[0151]
In addition, 1-phenyl-5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer at 1.0 × 10 5 per mole of silver halide, respectively.^-3Moles and 5.9 × 10^-FourMole was added. Furthermore, 1-phenyl-5-mercaptotetrazole was added to the second layer, the fourth layer, and the sixth layer, respectively, at 0.2 mg / m 2.²0.2 mg / m²And 0.6 mg / m²It added so that it might become.
Copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200000-400000) is 0.05 g / m on the red sensitive emulsion layer.²Added. Further, disodium catechol-3,5-disulfonate was added to the second layer, the fourth layer, and the sixth layer, respectively, at 6 mg / m.²6 mg / m²18 mg / m²It added so that it might become. In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).
[0152]
Embedded image

[0153]
(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.
[0154]
<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)]
[0155]
<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
[0156]
<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
[0157]
<Third layer (green sensitive emulsion layer)>
Emulsion G-1 0.14
Gelatin 1.36
・ Magenta coupler (ExM) 0.15
・ Ultraviolet absorber (UV-A) 0.14
Color image stabilizer (Cpd-2) 0.02
Color image stabilizer (Cpd-4) 0.002
-Color image stabilizer (Cpd-6) 0.09
-Color image stabilizer (Cpd-8) 0.02
-Color image stabilizer (Cpd-9) 0.03
-Color image stabilizer (Cpd-10) 0.01
Color image stabilizer (Cpd-11) 0.0001
・ Solvent (Solv-3) 0.11
・ Solvent (Solv-4) 0.22
・ Solvent (Solv-5) 0.20
[0158]
<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
[0159]
<Fifth layer (red-sensitive emulsion layer)>
Emulsion R-1 0.12
Gelatin 1.11
-Cyan coupler (ExC-2) 0.13
・ Cyan coupler (ExC-3) 0.03
-Color image stabilizer (Cpd-1) 0.05
-Color image stabilizer (Cpd-6) 0.06
-Color image stabilizer (Cpd-7) 0.02
-Color image stabilizer (Cpd-9) 0.04
-Color image stabilizer (Cpd-10) 0.01
-Color image stabilizer (Cpd-14) 0.01
Color image stabilizer (Cpd-15) 0.12
-Color image stabilizer (Cpd-16) 0.03
-Color image stabilizer (Cpd-17) 0.09
-Color image stabilizer (Cpd-18) 0.07
-Solvent (Solv-5) 0.15
・ Solvent (Solv-8) 0.05
[0160]
<Sixth layer (UV absorbing layer)>
・ Gelatin 0.46
・ Ultraviolet absorber (UV-B) 0.45
Compound (S1-4) 0.0015
・ Solvent (Solv-7) 0.25
[0161]

[0162]
Embedded image

[0163]
Embedded image

[0164]
Embedded image

[0165]
Embedded image

[0166]
Embedded image

[0167]
Embedded image

[0168]
Embedded image

[0169]
Embedded image

[0170]
Embedded image

[0171]
Embedded image

[0172]
The sample obtained as described above was designated as Sample B-1. Samples B-1 were prepared in the same manner as samples B-2 to B-9 except that emulsion B-1 in the blue-sensitive emulsion layer was replaced with emulsions B-2 to B-9, respectively.
[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.
After the exposure, the following color development processing A was performed.
[0174]
The processing steps are shown below.
[Processing A]
The sample of the photosensitive material is processed into a 127 mm wide 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.
Process (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
(Note) * Sensitive 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 per day. In addition, the tank counter-current system from (1) to (4) was used for rinsing.
[0175]
The composition of each treatment liquid is as follows.

[0176]

[0177]

[0178]
  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 1.5 higher than the minimum color density, and expressed as a relative value when the sensitivity of Sample B-1 was 100. The gradation was obtained from the slope of the straight line connecting the points of density 1.5 and density 2.0. Further, in order to investigate the latent image storage stability, a characteristic curve is obtained when processing is started 10 seconds after exposure in an environment of 20 ° C. and relative humidity 55%, and when processing is started 10 minutes after exposure, A change in density at an exposure amount giving a density of 1.5 when processing was started after 10 seconds was examined. Furthermore, in order to investigate the dependency on exposure temperature and humidity, the exposure was started in an atmosphere of 10 ° C./55% relative humidity and the processing was started after 5 seconds, and the exposure was performed in an atmosphere of 30 ° C./relative humidity 30% and the processing was performed after 5 seconds. A characteristic curve was obtained at the start, and exposure was performed in an atmosphere of 10 ° C. and relative humidity 55%, and the change in density at an exposure amount giving a density of 1.5 when the process was started after 5 seconds was examined. The results are shown in Table 2. The silver bromide-containing phase was analyzed by etching / TOF-SIMS, and the results of the parameter values obtained are also shown in Table 2. For details on parameter valuesFIG.As shown in
[0179]
[Table 2]

[0180]
  As is apparent from the results in Table 2, from Sample B-3 containing a silver bromochloride emulsion in which a silver bromide-containing phase in the present invention is formed in a blue-sensitive emulsion layer.B-7 andB-9 was recognized to have extremely high blue sensitivity and high contrast.
[0181]
[Example 2]
The sample of Example 1 was prepared by changing the layer configuration as follows to make a thin layer.
[0182]
Sample preparation
<First layer (blue sensitive emulsion layer)>
Emulsion B-1 0.14
・ Gelatin 0.75
・ Yellow coupler (ExY) 0.34
-Color image stabilizer (Cpd-1) 0.04
Color image stabilizer (Cpd-2) 0.02
-Color image stabilizer (Cpd-3) 0.04
-Color image stabilizer (Cpd-8) 0.01
Solvent (Solv-1) 0.13
[0183]
<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
[0184]
<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
[0185]
<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
・ Ultraviolet absorber (UV-C) 0.04
-Solvent (Solv-5) 0.09
[0186]
<Fifth layer (red-sensitive emulsion layer)>
Emulsion R-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
・ Ultraviolet absorber (UV-7) 0.02
-Solvent (Solv-5) 0.09
[0187]
<Sixth layer (UV absorbing layer)>
・ Gelatin 0.32
・ Ultraviolet absorber (UV-C) 0.42
-Solvent (Solv-7) 0.08
[0188]

[0189]
A sample using the above emulsion B-1 as the emulsion of the blue-sensitive emulsion layer was designated as Sample B-21. Sample B-1 was prepared in the same manner as Sample B-29 by replacing emulsion B-1 in the blue-sensitive emulsion layer with emulsion B-9.
[0190]
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.
[0191]
For each of the exposed samples, the color development processing was performed ultra-rapid processing according to the following development processing B.
[0192]
[Process B]
The above photosensitive material sample was processed into a 127 mm width roll, and the average of the photosensitive material sample was measured using an experimental processing device in which a minilab printer processor PP350 manufactured by Fuji Photo Film Co., Ltd. was modified 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.
[0193]
Process (temperature / time / replenishment amount)^*)
Color development 45.0 ℃ / 15sec / 45mL
Bleach fixing 40.0 ° C / 15 sec / 35 mL
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 / 121 mL
Drying 80.0 ° C / 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).
[0194]
The composition of each treatment liquid is as follows.

[0195]
Embedded image

[0196]

[0197]

[0198]
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 1.5 higher than the minimum color density, and expressed as a relative value when the sensitivity of Sample B-1 was 100. Further, the gradation was obtained from the slope of the straight line connecting the points of density 1.5 and density 2.0.
Further, in order to investigate the latent image storage stability, a characteristic curve is obtained when processing is started 10 seconds after exposure in an environment of 20 ° C. and 55% and when processing is started 10 minutes after exposure, and after 10 seconds. A change in density at an exposure amount giving a density of 1.5 when processing was started was examined. Furthermore, in order to investigate the dependency on exposure temperature and humidity, characteristic curves when the exposure is started in an atmosphere of 10 ° C. and 55% and the processing is started after 5 seconds and when the exposure is started in an atmosphere of 30 ° C. and 30% and the processing is started after 5 seconds. The change in density at an exposure amount giving a density of 1.5 when the exposure was started in an atmosphere of 10 ° C. and 55% and processing was started after 5 seconds was examined. These results are shown in Table 3.
[0199]
[Table 3]

[0200]
As is apparent from the results in Table 3, Sample B-29 containing the silver bromochloride emulsion in which the silver bromide-containing phase of the present invention is formed in the blue-sensitive emulsion layer has extremely high blue sensitivity and high sensitivity. It was a high contrast, and it was recognized that the latent image storage stability and exposure temperature / humidity dependency were excellent.
[0201]
[Example 3]
Using the sample of Example 2, image formation was performed by laser scanning exposure.
As a laser light source, a blue semiconductor laser having a wavelength of about 440 nm (announced by Nichia Chemical at the 48th Applied Physics Related Conference in March 2001) and a semiconductor laser (oscillation wavelength of about 1060 nm) in a waveguide-like inverted domain structure LiNbO with_ThreeA green laser with a wavelength of about 530 nm and a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL6501MG) taken out by SHG crystal of SHG were used. The laser beams of the three colors are moved in the direction perpendicular to the scanning direction by the polygon mirror so that the sample can be sequentially scanned and exposed. Variation in the amount of light due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter is 80 μm, the scanning pitch is 42.3 μm (600 dpi), and the average exposure time per pixel is 1.7 × 10.^-7Second.
After the exposure, the color development processing B was performed. As a result of the high illumination exposure in Example 2, the sample B-29 of the present invention showed a high sensitivity and gradation in the blue-sensitive layer. Sample B-29 of the present invention also showed high sensitivity and gradation in the red-sensitive layer, and it was found that both were suitable for image formation using laser scanning exposure.
[0202]
【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 color photographic light-sensitive material using the same can be obtained. Further, according to the present invention, a silver halide emulsion excellent in latent image storage stability and exposure temperature / humidity dependency and a silver halide color photographic light-sensitive material using the same can be obtained. Furthermore, according to the present invention, it is possible to provide a low-cost silver halide color photographic light-sensitive material because of its excellent rapid processability and high coloring efficiency.
[Brief description of the drawings]
FIG. 1 is a graph showing an example of a silver bromide content curve in silver chlorobromide grains in the present invention.
FIG. 2 is a graph showing various parameters of a silver bromide-containing phase in the present invention.

Claims (18)

In a silver halide emulsion comprising silver halide grains having a silver chloride content of 90 mol% or more, the silver halide grains are tetrahedral grains having a cubic or principal plane composed of (100) planes , and the silver halide grains The silver bromide content has a local maximum point at any position of 50% to 98% of the grain volume as measured from the inside, and from the local maximum point to the surface and the internal direction of the silver halide grain. A silver halide emulsion characterized by having a silver bromide-containing phase in which the silver bromide content decreases.   2. The halogenated halide according to claim 1, wherein the silver bromide content F on the surface of the silver halide grains satisfies F ≦ 0.9 × M with respect to the silver bromide content M at the maximum point. Silver emulsion.   The silver bromide-containing phase is the absolute value of the slope of the tangential line of the silver bromide content curve at the position where the silver halide grain decays into the surface of the grain and / or the interior of the grain and shows half the maximum concentration. The silver halide emulsion according to claim 1 or 2, wherein the silver halide emulsion is 0.1 to 50 mol% / nm.   A distance d1 from the maximum point in the silver bromide-containing phase to a position showing a half value of the maximum concentration in the surface direction of the silver halide grains is a maximum concentration in the internal direction of the silver halide grains from the maximum point. The silver halide emulsion according to any one of claims 1 to 3, wherein the silver halide emulsion is smaller than a distance d2 to a position showing a half value.   5. The silver halide according to claim 4, wherein a sum (d1 + d2) of the distance d1 and the distance d2 satisfies (d1 + d2) /R≦0.2 with respect to a radius R of the silver halide grains. emulsion.   The silver halide emulsion according to any one of claims 1 to 5, wherein a silver bromide content at the maximum point of the silver bromide-containing phase is 5 to 95 mol%.   The silver halide emulsion according to any one of claims 1 to 6, wherein the silver bromide-containing phase comprises a silver amount of 3% to 30% of the silver halide grain volume. .   The silver halide emulsion according to any one of claims 1 to 7, wherein a local silver bromide content of the silver bromide-containing phase is 5 mol% or more. The silver halide emulsion according to any one of claims 1 to 8 , wherein the silver halide grains contain one or more transition metal complexes. The transition metal complex has at least one ligand selected from H ₂ O, OH, O, OCN, thiazole and substituted thiazole, and contains a 6-coordination complex having iridium as a central metal The silver halide emulsion according to claim 9 , wherein The transition metal complex has at least one ligand selected from H ₂ O, OH, O, OCN, thiazole and substituted thiazole, and at least one hexacoordinated complex having iridium as a central metal; The silver halide emulsion according to claim 9 , comprising at least one metal complex selected from iron, ruthenium, osmium, lead, cadmium and zinc. The silver halide emulsion according to any one of claims 1 to 11 , wherein the silver bromide-containing phase contains one or more transition metal complexes. The transition metal complex is a ligand in which all six ligands are selected from Cl, Br and I, and is at least one of six-coordinate complexes having iridium as a central metal. Item 13. A silver halide emulsion according to Item 12 . The silver halide emulsion according to any one of claims 1 to 13 , wherein the silver halide grains are gold-sensitized silver halide grains. A water-soluble halogen containing an aqueous solution of a water-soluble silver salt and a bromide ion in a mixing vessel provided in addition to a reaction vessel in which the silver bromide-containing phase causes nucleation and / or grain growth of silver halide grains. The silver halide emulsion according to any one of claims 1 to 14 , wherein the silver halide emulsion is formed by using silver halide fine grains containing silver bromide formed by supplying and mixing an aqueous solution of a halide. . 16. The silver halide emulsion according to claim 15 , wherein the silver halide fine grains containing silver bromide have an average projected particle diameter of less than 0.06 [mu] m. The silver bromide-containing phase, the mixture containing one or more transition metal complexes formed with the container using a silver halide fine particles containing the silver bromide is characterized by being formed according to claim 15 or 16. A silver halide emulsion according to item 16 . In a silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red-sensitive silver halide emulsion layer, respectively, on the support, the blue-sensitive silver halide emulsion At least one of the layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer contains the silver halide emulsion according to any one of claims 1 to 17. Silver halide color photographic material.

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