JP4280435B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

【００２４】
式中、Ｚ₁₀₁ とＺ₁₀₂ はそれぞれ含窒素複素環核を形成するに必要な原子団を表す。含窒素複素環核としては、複素原子として窒素原子およびその他、硫黄原子、酸素原子、セレン原子、又はテルル原子を含む５〜６員環核が好ましい。ただし、これらの環にはさらに縮合環が結合していてもよく、またさらに置換基が結合していてもよい。前記の含窒素複素環核の具体例としては、チアゾール核、ベンゾチアゾール核、ナフトチアゾール核、セレナゾール核、ベンゾセレナゾール核、ナフトセレナゾール核、オキサゾール核、ベンゾオキサゾール核、ナフトオキサゾール核、イミダゾール核、ベンズイミダゾール核、ナフトイミダゾール核、４−キノリン核、ピロリン核、ピリジン核、テトラゾール核、インドレニン核、ベンズインドレニン核、インドール核、テルラゾール核、ベンゾテルラゾール核、ナフトテルラゾール核などを挙げることができる。Ｒ₁₀₁ とＲ₁₀₂ はそれぞれアルキル基、アルケニル基、アルキニル基またはアラルキル基を表す。これらの基および以下に述べる基はそれぞれその置換体を含む意味で用いられている。例えば、アルキル基を例にして述べると、無置換及び置換アルキル基を含み、これらの基は直鎖でも分岐でもあるいは環状でもよい。アルキル基の炭素数好ましくは１〜８である。
【００２５】
また、置換アルキル基の置換基の具体例としては、ハロゲン原子（フッ素、塩基、臭素、沃素など）、シアノ基、アルコキシ基、置換または無置換アミノ基、カルボン酸基、スルホン酸基、水酸基などを挙げることができ、これらの１個でまたは複数が組み合って置換していてもよい。アルケニル基の具体例としては、ビニルメチル基を挙げることができる。アラルキル基の具体例としては、ベンジル基やフェネチル基を挙げることができる。
ｍ₁₀₁ は１を表す。Ｒ₁₀₃ は水素原子、低級アルキル基、アラルキル基またはアリール基を表す。前記のアリール基の具体例としては、置換または無置換フェニル基を挙げることができる。Ｒ₁₀₄ は水素原子を表す。
ｊ₁₀₁ 、ｋ₁₀₁ は０または１を表し、Ｘ^- ₁₀₁ は酸アニオンを表し、ｎ₁₀₁ は０または１を表す。
次に一般式（Ｉ）で表される化合物の具体例を挙げる。しかし、これに限られるものではない。
【００２６】
【化２】

【００２７】
【化３】

【００２８】
【化４】

【００２９】
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モルあたり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〜５．０×１０^-3モルの範囲である。
【００３０】
本発明に用いるハロゲン化銀乳剤は、通常化学増感を施される。化学増感法については、不安定硫黄化合物の添加に代表される硫黄増感、金増感に代表される貴金属増感、あるいは還元増感等を単独もしくは併用して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。このうち、特に、金増感を施したものであることが好ましい。金増感を施すことにより、レーザー光等によって走査露光したときの写真性能の変動を更に小さくすることができるからである。
【００３１】
本発明に用いられるハロゲン化銀乳剤に金増感を施すには、種々の無機金化合物や無機配位子を有する金（Ｉ）錯体及び有機配位子を有する金（Ｉ）化合物を利用することができる。無機金化合物としては、例えば塩化金酸もしくはその塩、無機配位子を有する金（Ｉ）錯体としては、例えばジチオシアン酸金（Ｉ）カリウム等のジチオシアン酸金化合物やジチオ硫酸金（Ｉ）３ナトリウム等のジチオ硫酸金化合物等の化合物を用いることができる。
【００３２】
有機配位子を有する金（Ｉ）化合物としては、特開平４-２６７２４９号に記載のビス金（Ｉ）メソイオン複素環類、例えば四フッ化硼酸金（Ｉ）ビス（1,4,5-トリメチル-1,2,4-トリアゾリウム-3-チオラート）、特開平１１-２１８８７０号に記載の有機メルカプト金（Ｉ）錯体、例えばカリウム ビス（1-[3-(2-スルホナートベンズアミド）フェニル]-5-メルカプトテトラゾールカリウム塩）オーレート（Ｉ）５水和物、特開平４-２６８５５０号に記載の窒素化合物アニオンが配位した金（Ｉ）化合物、例えば、ビス（1-メチルヒダントイナート）金（Ｉ）ナトリウム塩四水和物、を用いることができる。また、米国特許第３、５０３、７４９号に記載されている金（Ｉ）チオレート化合物、特開平８-６９０７４号、特開平８-６９０７５号、特開平９-２６９５５４号に記載の金化合物、米国特許第５６２０８４１号、同５９１２１１２号、同５６２０８４１号、同５９３９２４５号、同５９１２１１１号に記載の化合物も用いることができる。
これらの化合物の添加量は場合に応じて広範囲に変わり得るがハロゲン化銀１モルあたり５×１０^-7〜５×１０^-3モル、好ましくは５×１０^-6〜５×１０^-4モルである。
【００３３】
また、コロイド状硫化金を用いることも可能であり、その製造方法はリサーチ・ディスクロージャー（Reserch Disclosure,37154)、ソリッド ステート イオニクス（Solid State Ionics ）第７９巻、６０〜６６頁、１９９５年刊、Compt.Rend.Hebt.Seances Acad.Sci.Sect.B第２６３巻、１３２８頁、１９６６年刊等に記載されている。コロイド状硫化金としてさまざまなサイズのものを利用でき、粒径５０nm以下のものも用いることができる。添加量は場合に応じて広範囲に変わり得るがハロゲン化銀１モルあたり金原子として５×１０^-7〜５×１０^-3モル、好ましくは５×１０^-6〜５×１０^-4モルである。
本発明においては、金増感を更に他の増感法、例えば硫黄増感、セレン増感、テルル増感、還元増感あるいは金化合物以外を用いた貴金属増感等と組み合わせてもよい。
【００３４】
本発明のハロゲン化銀カラー写真感光材料には、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。
【００３５】
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。紙基体およ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、紙基体およ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０．０５〜０．５が好ましく、０．１〜０．２がさらに好ましい。
【００３６】
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また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。本発明の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、およびＥＰ０８８００６６号に記載されている例が挙げられる。
【００３７】
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、蛍光増白剤は感光材料の親水性コロイド層中に分散してもよい。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、ピラゾリン系が用いることができ、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。
反射型支持体としては、透過型支持体、また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、鏡面反射性または第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。
【００３８】
また、本発明に係わる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。
【００３９】
本発明に係わる感光材料には、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。
【００４０】
本発明に係わる感光材料には、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。
【００４１】
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良い。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。
【００４２】
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、たとえば、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。
【００４３】
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およ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。
【００４４】
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−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かまわないが、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また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−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、マゼンタおよびシアンのそれぞれの発色性層は２層または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。
【００４５】
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）および写真構成層（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。
【００４６】
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またはカブリ防止剤、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、イエローカプラーおよびその乳化分散法、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、表１〜２の特許に記載のものが特に好ましく適用できる。
【００４７】
【表１】

【００４８】
【表２】

【００４９】
本発明において用いられるシアン、マゼンタおよ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の一般式（II）および（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良く、好ましい。
【００５０】
以下に更に具体的に説明する。
本発明に使用しうるシアンカプラーとしては、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および特開平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。
【００５１】
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。
【００５２】
本発明に用いられるマゼンタカプラーとしては、前記の表の公知文献に記載されたような５−ピラゾロン系マゼンタカプラーやピラゾロアゾール系マゼンタカプラーが用いられるが、中でも色相や画像安定性、発色性等の点で特開昭６１−６５２４５号に記載されたような２級又は３級アルキル基がピラゾロトリアゾール環の２、３又は６位に直結したピラゾロトリアゾールカプラー、特開昭６１−６５２４６号に記載されたような分子内にスルホンアミド基を含んだピラゾロアゾールカプラー、特開昭６１−１４７２５４号に記載されたようなアルコキシフェニルスルホンアミドバラスト基を持つピラゾロアゾールカプラーや欧州特許第２２６，８４９Ａ号や同第２９４，７８５Ａ号に記載されたような６位にアルコキシ基やアリールオキシ基をもつピラゾロアゾールカプラーの使用が好ましい。
特に、マゼンタカプラーとしては特開平８−１２２９８４号に記載の一般式（Ｍ−Ｉ）で表されるピラゾロアゾールカプラーが好ましく、該特許の段落番号０００９〜００２６はそのまま本願に適用され、本願の明細書の一部として取り込まれる。
これに加えて、欧州特許第８５４３８４号、同第８８４６４０号に記載の３位と６位の両方に立体障害基を有するピラゾロアゾールカプラーも好ましく用いられる。
【００５３】
また、イエローカプラーとしては、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、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。
【００５４】
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（または不存在下で）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、また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また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。
【００５５】
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号および独国特許第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号および仏国特許第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。
【００５６】
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。
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号および特表平８−５０１２９１号等に記載されている化合物である。
【００５７】
本発明に係わる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。
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。
【００５８】
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。
【００５９】
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。
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かまわないが、好ましくは従来公知の他の界面活性剤との併用である。
【００６０】
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。
【００６１】
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）を採っても良く、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。
【００６２】
本発明の感光材料は、ガスレーザー、発光ダイオード、半導体レーザー、半導体レーザーあるいは半導体レーザーを励起光源に用いた固体レーザーと非線形光学結晶を組合わせた第二高調波発光光源（ＳＨＧ）等の単色高密度光を用いたデジタル走査露光方式が好ましく使用される。システムをコンパクトで、安価なものにするために半導体レーザー、半導体レーザーあるいは固体レーザーと非線形光学結晶を組合わせた第二高調波発生光源（ＳＨＧ）を使用することが好ましい。特にコンパクトで、安価、更に寿命が長く安定性が高い装置を設計するためには半導体レーザーの使用が好ましく、露光光源の少なくとも一つは半導体レーザーを使用することが好ましい。
【００６３】
このような走査露光光源を使用する場合、本発明の感光材料の分光感度極大波長は、使用する走査露光用光源の波長により任意に設定することができる。半導体レーザーを励起光源に用いた固体レーザーあるいは半導体レーザーと非線形光学結晶を組合わせて得られるＳＨＧ光源では、レーザーの発振波長を半分にできるので、青色光、緑色光が得られる。従って、感光材料の分光感度極大は通常の青、緑、赤の３つの波長領域に持たせることが可能である。
このような走査露光における露光時間は、画素密度を４００ｄｐｉとした場合の画素サイズを露光する時間として定義すると、好ましい露光時間としては１０^-4秒以下、更に好ましくは１０^-6秒以下である。
【００６４】
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。
また本発明の感光材料を処理するには、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。
【００６５】
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。
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。
【００６６】
本発明において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。
【００６７】
本発明の感光材料を露光後、現像する方法としては、従来のアルカリ剤と現像主薬を含む現像液で現像する方法、現像主薬を感光材料に内蔵し、現像主薬を含まないアルカリ液などのアクチベーター液で現像する方法などの湿式方式のほか、処理液を用いない熱現像方式などを用いることができる。特に、アクチベーター方法は、現像主薬を処理液に含まないため、処理液の管理や取扱いが容易であり、また廃液処理時の負荷が少なく環境保全上の点からも好ましい方法である。アクチベーター方法において、感光材料中に内蔵される現像主薬また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。
【００６８】
また、感光材料の塗布銀量を低減し、過酸化水素を用いた画像増幅処理（補力処理）する現像方法も好ましく用いられる。特に、この方法をアクチベーター方法に用いることは好ましい。具体的には、特開平８−２９７３５４号、同９−１５２６９５号に記載された過酸化水素を含むアクチベーター液を用いた画像形成方法が好ましく用いられる。
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、水洗また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。
【００６９】
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）、水洗およ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。
【００７０】
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。
【００７１】
本発明の感光材料は、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。
・特開平１０−３３３２５３に記載の自動プリント並びに現像システム
・特開２０００−１０２０６に記載の感光材料搬送装置
・特開平１１−２１５３１２に記載の画像読取装置を含む記録システム
・特開平１１−８８６１９並びに特開平１０−２０２９５０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
【００７２】
【実施例】
実施例１
（乳剤Ａの調製）
石灰処理ゼラチンの３％水溶液に塩化ナトリウム３．３ｇを加え、１Ｎの硫酸４２．８ｍｌと１，８−ジヒドロキシ−３，６−ジチアオクタン（１％水溶液）を２５ｍｌ添加した。この水溶液に硝酸銀２．１２モル含む水溶液と塩化ナトリウムを２．１８モル含む水溶液とを激しく撹拌しながら６８℃で添加混合した。その後４０℃にて沈降水洗を行い脱塩を施した。さらに石灰処理ゼラチン１６８．０ｇを加え、乳剤のｐＨとｐＡｇをそれぞれ５．６と７．３に調整した。電子顕微鏡写真から、粒子の形状は立方体であり、平均粒子サイズは０．７６μｍ、変動係数は１０％であった。
【００７３】
（乳剤Ｂの調製）
乳剤粒子形成において全銀量の９５〜１００％を添加する段階（表面５％シェル）で、０．００４モルの沃化物イオンを含む沃化銀微粒子乳剤を添加したことを除いて、乳剤Ａの調製方法に従った。用いた沃化銀微粒子乳剤の調製は、特開平１０−４３５７０号明細書に記載の攪拌混合器で行った。得られた粒子の形状は、電子顕微鏡写真から粒子頂点の丸みが非常に少ない立方体であった。
（乳剤Ｃの調製）０．００４モルの沃化物イオンを含む沃化銀微粒子乳剤の添加時期を全銀量の９１〜９６％を添加する段階に変更したことを除いて、乳剤Ｂの調製方法に従った。粒子の形状は乳剤Ｂと同様であった。
（乳剤Ｄの調製）０．００４モルの沃化物イオンを含む沃化銀微粒子乳剤の添加時期を全銀量の８５〜９０％を添加する段階に変更したことを除いて、乳剤Ｂの調製方法に従った。粒子の形状は乳剤Ｂと同様であった。
（乳剤Ｅの調製）０．００４モルの沃化物イオンを含む沃化銀微粒子乳剤の添加時期を全銀量の８０〜８５％を添加する段階に変更したことを除いて、乳剤Ｂの調製方法に従った。粒子の形状は乳剤Ｂと同様であった。
（乳剤Ｆの調製）乳剤粒子形成において全銀量の９５〜９６％を添加する段階で、０．００４モルの沃化カリウム水溶液を添加したことを除いて、乳剤Ａの調製方法に従った。得られた粒子の形状は、電子顕微鏡写真から粒子頂点の丸みが非常に少ない立方体であった。
（乳剤Ｇの調製）乳剤粒子形成において全銀量の８５〜８６％を添加する段階で、０．００４モルの沃化カリウム水溶液を添加したことを除いて、乳剤Ａの調製方法に従った。得られた粒子の形状は、電子顕微鏡写真から粒子頂点の丸みが非常に少ない立方体であった。
【００７４】
実験１：粒子内の沃化物イオンの含有率分布測定
上記の乳剤Ｂ〜Ｇのハロゲン化銀粒子について、粒子内の深さ方向のヨード分布をエッチング/ＴＯＦ−ＳＩＭＳ法により調べた。解析の試料は以下のように調製した。乳剤を温水を添加し、ゼラチンを溶解させた後に、粒子とゼラチンを遠心分離させて、沈降した粒子をSi基板上に塗布した。この塗布試料に対してエッチング/ＴＯＦ−ＳＩＭＳ測定を行う。照射するガリウムイオンによるダメージを防ぐために、試料を−１２０℃以下に冷却した。分析面積は６０μｍ²であり、エッチング面積は２４０μｍ²である。エッチング速度は塩化銀蒸着膜を用いて評価した。１回のエッチングによりおよそ０.５〜１nmの深さの分析を行い、エッチングを繰返すことによっておよそ１００nmまでの深さの分析を行った。沃化物の２次イオンは負イオン測定モードで分析した。沃化物のエッチング/ＴＯＦ−ＳＩＭＳ測定後に、正イオン測定モードで銀の２次イオン測定を一定時間だけ行い、沃化物の２次イオン(Ｉ^-)強度を銀の２次イオン(Ａｇ⁺)強度で規格化することで試料中の粒子数を補正した。
【００７５】
図２〜図７から本発明で粒子の内側で沃化物イオンの添加を終了した乳剤は、粒子表面まで沃化物イオンが存在することがわかる。また本発明の塩沃化銀乳剤は、粒子内部の沃化物イオン含有率が表面から深さ方向に減衰する分布を示す。
【００７６】
上記の乳剤Ａ〜Ｇに金増感剤（コロイド状硫化金）６×１０^-5モル／モルＡｇ、青感性分光増感色素（Ａ）３．１×１０^-4モル／モルＡｇを添加し、６０℃にて最適に化学増感及び分光増感し、さらに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４．４×１０^-4モル／モルＡｇを添加して、乳剤Ａ’〜Ｇ’を調製した。
【００７７】
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（１０１）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。
【００７８】
第一層塗布液調製
イエローカプラー（ＥｘＹ）５７ｇ、色像安定剤（Ｃｐｄ−１）７ｇ、色像安定剤（Ｃｐｄ−２）４ｇ、色像安定剤（Ｃｐｄ−３）７ｇ、色像安定剤（Ｃｐｄ−８）２ｇを溶媒（Ｓｏｌｖ−１）２１ｇ及び酢酸エチル８０ｍｌに溶解し、この液を４ｇのドデシルベンゼンスルホン酸ナトリウムを含む２３．５重量％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Ａ’とを混合溶解し、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。
【００７９】
第二層〜第七層用の塗布液も第一層塗布液と同様の方法で調製した。各層のゼラチン硬化剤としては、１−オキシ−３，５−ジクロロ−ｓ−トリアジンナトリウム塩（Ｈ−１）、（Ｈ−２）、（Ｈ−３）を用いた。また、各層にＡｂ−１、Ａｂ−２、Ａｂ−３、及びＡｂ−４をそれぞれ全量が１５．０ｍｇ／ｍ²、６０．０ｍｇ／ｍ²，５．０ｍｇ／ｍ²及び１０．０ｍｇ／ｍ²となるように添加した。
【００８０】
【化５】

【００８１】
緑及び赤感性乳剤層の塩臭化銀乳剤には、以下の分光増感色素をそれぞれ用いた。
緑感性乳剤層
【００８２】
【化６】

【００８３】
（増感色素Ｄをハロゲン化銀１モル当り、大サイズ乳剤に対しては３．０×１０^-4モル、小サイズ乳剤に対しては３．６×１０^-4モル、また、増感色素Ｅをハロゲン化銀１モル当り、大サイズ乳剤に対しては４．０×１０^-5モル、小サイズ乳剤に対しては７．０×１０^-5モル、また、増感色素Ｆをハロゲン化銀１モル当り、大サイズ乳剤に対しては２．０×１０^-4モル、小サイズ乳剤に対しては２．８×１０^-4モル添加した。）
赤感性乳剤層
【００８４】
【化７】

【００８５】
（増感色素ＧおよびＨをそれぞれ、ハロゲン化銀１モル当り、大サイズ乳剤に対しては８．０×１０^-5モル、小サイズ乳剤に対しては１０．７×１０^-5モル添加した。）
さらに、以下の化合物Ｉを赤感性乳剤層にハロゲン化銀１モル当たり３．０×１０^-3モル添加した。）
【００８６】
【化８】

【００８７】
また、青感性乳剤層、緑感性乳剤層および赤感性乳剤層に対し、１−（３−メチルウレイドフェニル）−５−メルカプトテトラゾールを、それぞれハロゲン化銀１モル当り３．３×１０^-4モル、１．０×１０^-3モルおよび５．９×１０^-4モル添加した。
さらに、第二層、第四層、第六層および第七層にも、それぞれ０．２ｍｇ／ｍ²、０．２ｍｇ／ｍ²、０．６ｍｇ／ｍ²、０．１ｍｇ／ｍ²となるように添加した。
また、青感性乳剤層および緑感性乳剤層に対し、４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを、それぞれハロゲン化銀１モル当たり、１×１０^-4モル、２×１０^-4モル添加した。
また、赤感性乳剤層にメタクリル酸とアクリル酸ブチルの共重合体ラテックス（重量比１：１、平均分子量２０００００〜４０００００）を０．０５ｇ／ｍ²を添加した。
また第二層、第四層および第六層にカテコール−３，５−ジスルホン酸二ナトリウムをそれぞれ６ｍｇ／ｍ²、６ｍｇ／ｍ²、１８ｍｇ／ｍ²となるように添加した。
また、イラジエーション防止のために、以下の染料（カッコ内は塗布量を表す）を添加した。
【００８８】
【化９】

【００８９】
（層構成）
以下に、各層の構成を示す。数字は塗布量（ｇ／ｍ²）を表す。ハロゲン化銀乳剤は、銀換算塗布量を表す。
支持体
ポリエチレン樹脂ラミネート紙
［第一層側のポリエチレン樹脂に白色顔料（ＴｉＯ₂；含有率１６重量％、ＺｎＯ；含有率４重量％）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重量％）、青味染料（群青）を含む］
第一層（青感性乳剤層）
乳剤Ａ 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
【００９０】
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
【００９１】

【００９２】
第四層（混色防止層）
ゼラチン ０．７１
混色防止剤（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
【００９３】

【００９４】
第六層（紫外線吸収層）
ゼラチン ０．４６
紫外線吸収剤（ＵＶ−Ｂ） ０．４５
化合物（Ｓ１−４） ０．００１５
溶媒（Ｓｏｌｖ−７） ０．２５
第七層（保護層）
ゼラチン １．００
ポリビニルアルコールのアクリル変性共重合体
（変性度１７％） ０．０４
流動パラフィン ０．０２
界面活性剤（Ｃｐｄ−１３） ０．０１
【００９５】
【化１０】

【００９６】
【化１１】

【００９７】
【化１２】

【００９８】
【化１３】

【００９９】
【化１４】

【０１００】
【化１５】

【０１０１】
【化１６】

【０１０２】
【化１７】

【０１０３】
【化１８】

【０１０４】
【化１９】

【０１０５】
同様にして試料（１０１）の乳剤Ａ’を乳剤Ｂ’〜Ｇ’に変更した試料（１０２）〜（１０７）を作製した。
【０１０６】
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。
実験２：センシトメトリー
各塗布試料に対して感光計（富士写真フイルム（株）製ＦＷＨ型）を用いて、センシトメトリー用の階調露光を与えた。ＳＰ−１フィルターを装着し低照度１０秒間露光した。
また、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。ＳＰ−１フィルターを装着し、高照度１０^-4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。
【０１０７】
以下に処理工程を示す。
［処理Ａ］
上記感光材料１０１を１２７ｍｍ巾のロール状に加工し、富士写真フイルム（株）製ミニラボプリンタープロセッサー ＰＰ１２５８ＡＲを用いて像様露光後、下記処理工程にてカラー現像タンク容量の２倍補充するまで、連続処理（ランニングテスト）を行った。このランニング液を用いた処理を処理Ａとした。
処理工程 温 度 時 間 補充量^*
カラー現像 ３８．５℃ ４５秒 ４５ミリリットル
漂白定着 ３８．０℃ ４５秒 ３５ミリリットル
リンス（１） ３８．０℃ ２０秒 −
リンス（２） ３８．０℃ ２０秒 −
リンス（３）＊＊ ３８．０℃ ２０秒 −
リンス（４）＊＊ ３８．０℃ ３０秒 １２１ミリリットル
＊感光材料１ｍ²当たりの補充量
＊＊富士写真フイルム社製 リンスクリーニングシステムＲＣ５０Ｄをリンス（３）に装置し、リンス（３）からリンス液を取り出し、ポンプにより逆浸透膜モジュール（ＲＣ５０Ｄ）へ送る。同槽で得られた透過水はリンス（４）に供給し、濃縮水はリンス（３）に戻す。逆浸透モジュールへの透過水量は５０〜３００ミリリットル／分を維持するようにポンプ圧を調整し、１日１０時間温調循環させた。
（リンスは（１）から（４）へのタンク向流方式とした。）
【０１０８】
各処理液の組成は以下の通りである。

【０１０９】

【０１１０】

【０１１１】
処理後の各試料のイエロー発色濃度を測定し、乳剤Ａ’〜Ｇ’の被り濃度と１０秒露光低照度感度、１０^-4秒露光高照度感度をそれぞれ求めた。感度は、最低発色濃度より１．０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（１０１）の現像処理した感度を１００としたときの相対値で表わした。これらの結果をまとめて表３に示す。
【０１１２】
【表３】

【０１１３】
表１と図２〜図７から、本発明の塩沃化銀乳剤が粒子内部の沃化物イオン含有率が表面から深さ方向に減衰する分布を有することで、より高感度であり高照度の相反則特性に優れていることがわかる。また粒子の９８％を形成する以前に沃化物イオンの添加を終了した本発明乳剤は、低かぶりでかつ高感度な乳剤であることを示した。図２〜図７は各々乳剤Ｂ〜Ｇの前記分布を表している。
【０１１４】
実施例２
（乳剤Ｈの調製）
石灰処理ゼラチンの５％水溶液に塩化ナトリウム５．６ｇを加え、１Ｎの硫酸４２．８ｍｌとＮ，Ｎ’−ジメチルイミダゾリジン−２−チオン（１％水溶液）を１．１ｍｌ添加した。この水溶液に硝酸銀０．２１モル含む水溶液と塩化ナトリウムを０．２１モル含む水溶液とを撹拌しながら６１℃で添加混合した。続いて６１℃を維持したまま、硝酸銀１．２７モルを含む水溶液と塩化ナトリウムを１．２７モルと全銀量あたり１×１０^-8モルのK₂[Ru(NO)Cl₅]の遷移金属錯体を含む水溶液とを撹拌しながら添加混合し、更に硝酸銀０．２１モル含む水溶液と塩化ナトリウムを０．２１モル含む水溶液とを撹拌しながら添加混合し、続いて硝酸銀０．２１モルを含む水溶液と塩化ナトリウムを０．２１モルと全銀量あたり２×１０^-5モルのK₄[Ru(CN)₅]の遷移金属錯体を含む水溶液とを撹拌しながら添加混合した。更に６１℃のまま硝酸銀０．０２モル含む水溶液と塩化ナトリウムを０．０２モル含む水溶液撹拌しながら添加混合した。続いて硝酸銀０．１１モルを含む水溶液と塩化ナトリウムを０．１１モルと全銀量あたり２×１０^-6モルのK₂[Ir(H₂O)Cl₅]の遷移金属錯体を含む水溶液とを撹拌しながら添加混合し、続いて硝酸銀０．０４モルを含む水溶液と塩化ナトリウムを０．０４モルと全銀量あたり４×１０^-8モルのK₂[IrCl₆]の遷移金属錯体を含む水溶液とを撹拌しながら添加混合し、硝酸銀０．０４モル含む水溶液と塩化ナトリウムを０．０４モル含む水溶液とを撹拌しながら６１℃で添加混合した。その後４０℃にて沈降水洗を行い脱塩を施した。さらに石灰処理ゼラチン１６８．０ｇを加え、乳剤のｐＨとｐＡｇをそれぞれ５．６と７．３に調整した。電子顕微鏡写真から、粒子の形状は立方体であり、平均粒子サイズは０．６２μｍ、変動係数は１０％であった。
この乳剤に金増感剤（四フッ化硼酸金（Ｉ）ビス（1,4,5-トリメチル-1,2,4-トリアゾリウム-3-チオラート））１．５×１０^-5モル／モルＡｇ、硫黄増感剤（チオ硫酸ナトリウム）６×１０^-7モル／モルＡｇ、青感性分光増感色素（Ａ及びＢ）２．３×１０^-4モル／モルＡｇ及び１．５×１０^-4モル／モルＡｇを添加し、６０℃にて最適に化学増感及び分光増感し、さらに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４．４×１０^-4モル／モルＡｇを添加した。
【０１１５】
（乳剤Ｊの調製）乳剤粒子形成において全銀量の９０〜９１％を添加する段階で、０．００６モルの沃化カリウム水溶液を添加したことを除いて、乳剤Ｈの調製方法に従った。得られた粒子の形状は、電子顕微鏡写真から粒子頂点の丸みが非常に少ない立方体であった。
（乳剤Ｋの調製）K₂[IrCl₆]の遷移金属錯体を添加しないことを除いて、乳剤Ｊの調製方法に従った。粒子の形状は、乳剤Ｊと同様であった。
（乳剤Ｑの調製）乳剤粒子形成において全銀量の９０〜９５％を添加する段階で、０．００６モルの沃化物イオンを含む沃化銀微粒子乳剤を添加し、K₂[Ir(H₂O)Cl₅]をK₂[Ir(5-methylthiazole)Cl₅]に変更したことを除いて、乳剤Ｈの調製方法に従った。用いた沃化銀微粒子乳剤の調製は、特開平１０−４３５７０号明細書に記載の攪拌混合器で行った。得られた粒子の形状は、電子顕微鏡写真から粒子頂点の丸みが非常に少ない立方体であった。
（乳剤Ｒの調製）化学増感過程において青感性分光増感色素を増感色素Ｃに変更したことを除いて乳剤Ｑの調製方法に従った。粒子形状は乳剤Ｐと同様であった。
上記Ｊ、Ｋ、ＱおよびＲの乳剤に対し、実施例１の実験１を行ったところ実施例１の本発明乳剤と同様に、粒子内部の沃化物イオン含有率が表面から深さ方向に減衰する分布を示した。
【０１１６】
【化２０】

【０１１７】
実施例１と全く同じ層構成で、第一層目の乳剤を乳剤Ｈ〜ＫおよびＱ、Ｒに置き換えて、試料（２０１）〜（２０５）を作製した。この試料に対し実施例１の実験２及び下記の実験３を行った
【０１１８】
実験３：露光後の潜像安定性
各試料に対して、前記１０^-4秒高照度露光後から処理Ａまでの時間を変えて、センシトメトリーを測定し、60分後処理と7秒後処理の感度の差を求めた。
これらの結果をまとめて、表４に示した。
【０１１９】
【表４】

【０１２０】
表４から、本発明の塩沃化銀乳剤が高感度で低かぶりな乳剤であり、かつ露光後の潜像安定性に優れていることがわかる。
【０１２１】
実施例３
（乳剤Ｌの調製）実施例２に記載の乳剤Ｈの調製法を基にして、Ｎ，Ｎ’−ジメチルイミダゾリジン−２−チオン（１％水溶液）の添加を除いて同様に粒子形成を行った。電子顕微鏡写真から、粒子の形状は立方体であり、平均粒子サイズは０．３８μｍ、変動係数は８％であった。
この乳剤に金増感剤（四フッ化硼酸金（Ｉ）ビス（1,4,5-トリメチル-1,2,4-トリアゾリウム-3-チオラート））２．４×１０^-5モル／モルＡｇ、硫黄増感剤（チオ硫酸ナトリウム）１×１０^-7モル／モルＡｇ、緑感性分光増感色素（Ｄ、Ｅ及びＦ）３．６×１０^-4モル／モルＡｇ、７．０×１０^-5モル／モルＡｇ及び２．８×１０^-4モル／モルＡｇを添加し、６０℃にて最適に化学増感及び分光増感し、さらに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４．４×１０^-4モル／モルＡｇを添加した
（乳剤Ｍの調製）乳剤粒子形成において全銀量の９０〜９１％を添加する段階で、０．００２モルの沃化カリウム水溶液を添加したことを除いて、乳剤Ｌの調製方法に従った。
得られた粒子の形状は、電子顕微鏡写真から粒子頂点の丸みが非常に少ない立方体でたった。
（乳剤Ｎの調製）K₂[IrCl₆]の遷移金属錯体を添加しないことを除いて、乳剤Ｍの調製方法に従った。粒子形状は、乳剤Ｍと同様であった。
（乳剤Ｐの調製）乳剤粒子形成において全銀量の９０〜９５％を添加する段階で、０．００２モルの沃化物イオンを含む沃化銀微粒子乳剤を添加したことを除いて、乳剤Ｌの調製方法に従った。用いた沃化銀微粒子乳剤の調製は、特開平１０−４３５７０号明細書に記載の攪拌混合器で行った。得られた粒子の形状は、電子顕微鏡写真から粒子頂点の丸みが非常に少ない立方体であった。
上記Ｍ、Ｎ及びＰの乳剤に対し、実施例１の実験１を行ったところ実施例１の本発明乳剤と同様に、粒子内部の沃化物イオン含有率が表面から深さ方向に減衰する分布を示した。
【０１２２】
実施例２の層構成で、第三層の緑感性乳剤Em−１を上記の乳剤Ｌ〜Ｎ及びＰに置き換えて試料（３０１）〜（３０４）を作製した。この試料に対して実施例２と同様の処理を施し、処理後の各試料のマゼンタ発色濃度を測定し、実施例２の実験２及び３の評価を行った。これらの結果をまとめて表５に示す。
【０１２３】
【表５】

【０１２４】
表５から、本発明の塩沃化銀乳剤が高感度で低かぶりな乳剤であり、かつ露光後の潜像安定性に優れていることがわかる。
【０１２５】
実施例４
層構成を下記のように変えて薄層化した試料を調製し、この試料に対し実施例１の実験２及び３を行った。
層構成は試料（４０１）で示す。なお、試料（４０２）〜（４０５）は試料（４０１）の乳剤Ｈを乳剤Ｊ、Ｋ、Ｑ、Ｒにそれぞれ変更したものである。
結果は実施例１の結果と同様に、この結果から、薄層化した試料の超迅速処理でも本発明の効果が確かめられた。
【０１２６】
試料４０１の作製
第一層（青感性乳剤層）
乳剤Ｈ 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
【０１２７】
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
【０１２８】
第三層（緑感性乳剤層）
塩臭化銀乳剤Ｂ（試料１０１と同じ乳剤） 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
【０１２９】
第四層（混色防止層）
ゼラチン ０．４８
混色防止剤（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
【０１３０】
第五層（赤感性乳剤層）
塩臭化銀乳剤Ｃ（試料１０１と同じ乳剤） ０．１２
ゼラチン ０．５９
シアンカプラー（ＥｘＣ−２） ０．１３
シアンカプラー（ＥｘＣ−３） ０．０３
色像安定剤（Ｃｐｄ−７） ０．０１
色像安定剤（Ｃｐｄ−９） ０．０４
色像安定剤（Ｃｐｄ−１５） ０．１９
色像安定剤（Ｃｐｄ−１８） ０．０４
紫外線吸収剤（ＵＶ−７） ０．０２
溶媒（Ｓｏｌｖ−５） ０．０９
【０１３１】
第六層（紫外線吸収層）
ゼラチン ０．３２
紫外線吸収剤（ＵＶ−Ｃ） ０．４２
溶媒（Ｓｏｌｖ−７） ０．０８
第七層（保護層）
ゼラチン ０．７０
ポリビニルアルコールのアクリル変性共重合体
（変性度１７％） ０．０４
流動パラフィン ０．０１
界面活性剤（Ｃｐｄ−１３） ０．０１
ポリジメチルシロキサン ０．０１
二酸化珪素 ０．００３
【０１３２】
作製された各試料は、実施例１の実験２及び３と同様に露光し、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。
【０１３３】
［処理Ｂ］
上記の感光材料を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。
【０１３４】
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℃ 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ををリンス（３）に装着し、リンス（３）からリンス液を取り出してポンプにより逆浸透モジュール（ＲＣ５０Ｄ）へ送る。同槽で送られた透過水はリンス（４）に供給し、濃縮液はリンス（３）に戻す。逆浸透モジュールへの透過水量は５０〜３００ｍＬ／分を維持するようにポンプ圧を調整し、１日１０時間温調循環させた。リンスは（１）から（４）への４タンク向流方式とした。
【０１３５】
各処理液の組成は以下の通りである。
[発色現像液] [タンク液］ ［補充液］
水 ８００ｍＬ ６００ｍＬ
蛍光増白剤（ＦＬ−１） ５．０ｇ ８．５ｇ
トリイソプロパノールアミン ８．８ｇ ８．８ｇ
ｐ−トルエンスルホン酸ナトリウム ２０．０ｇ ２０．０ｇ
エチレンジアミン４酢酸 ４．０ｇ ４．０ｇ
亜硫酸ナトリウム ０．１０ｇ ０．５０ｇ
塩化カリウム １０．０ｇ −
４，５−ジヒドロキシベンゼン−
１，３−ジスルホン酸ナトリウム ０．５０ｇ ０．５０ｇ
ジナトリウム−Ｎ，Ｎ−ビス（スルホナート
エチル）ヒドロキシルアミン ８．５ｇ １４．５ｇ
４−アミノ−３−メチル−Ｎ−エチル−Ｎ−
（β−メタンスルホンアミドエチル）アニリン
・３／２硫酸塩・モノハイドレード １０．０ｇ ２２．０ｇ
炭酸カリウム ２６．３ｇ ２６．３ｇ
水を加えて全量 １０００ｍＬ １０００ｍＬ
ｐＨ（２５℃、硫酸とＫＯＨで調整） １０．３５ １２．６
【０１３６】
[漂白定着液] [タンク液] [補充液]
水 ８００ｍＬ ８００ｍＬ
チオ硫酸アンモニウム（７５０ｇ／ｍＬ） １０７ｍＬ ２１４ｍＬ
コハク酸 ２９．５ｇ ５９．０ｇ
エチレンジアミン４酢酸鉄（III）アンモニウム ４７．０ｇ ９４．０ｇ
エチレンジアミン４酢酸 １．４ｇ ２．８ｇ
硝酸（６７％） １７．５ｇ ３５．０ｇ
イミダゾール １４．６ｇ ２９．２ｇ
亜硫酸アンモニウム １６．０ｇ ３２．０ｇ
メタ重亜硫酸カリウム ２３．１ｇ ４６．２ｇ
水を加えて全量 １０００ｍＬ １０００ｍＬ
ｐＨ（２５℃、硝酸とアンモニア水で調整） ６．００ ６．００
【０１３７】
[リンス液] [タンク液] [補充液]
塩素化イソシアヌール酸ナトリウム ０．０２ｇ ０．０２ｇ
脱イオン水（電導度５μｓ／ｃｍ以下） １０００ｍＬ １０００ｍＬ
ｐＨ（２５℃） ６．５ ６．５
【０１３８】
【化２１】

【０１３９】
実施例５
試料（４０１）〜（４０５）を用いて、レーザー走査露光によって画像形成を行った。
レーザー光源としては、半導体レーザーＧａＡｌＡｓ（発振波長 ８０８．５ｎｍ）を励起光源としたＹＡＧ固体レーザー（発振波長 ９４６ｎｍ）を反転ドメイン構造を有するＬｉＮｂＯ₃のＳＨＧ結晶により波長変換して取り出した４７３ｎｍと、半導体レーザーＧａＡｌＡｓ（発振波長 ８０８．７ｎｍ）を励起光源としたＹＶＯ₄固体レーザー（発振波長 １０６４ｎｍ）を反転ドメイン構造を有するＬｉＮｂＯ₃のＳＨＧ結晶により波長変換して取り出した５３２ｎｍと、ＡｌＧａＩｎＰ（発振波長 約６８０ｎｍ：松下電産製タイプＮｏ．ＬＮ９Ｒ２０）とを用いた。３色のそれぞれのレーザー光はポリゴンミラーにより走査方向に対して垂直方向に移動し、試料上に、順次走査露光できるようにした。半導体レーザーの温度による光量変動は、ペルチェ素子を利用して温度が一定に保たれることで抑えられている。実効的なビーム径は、８０μｍで、走査ピッチは４２．３μｍ（６００ｄｐｉ）であり、１画素あたりの平均露光時間は、１．７×１０^-7秒であった。
露光後、発色現像処理Ｂにより処理を行ったところ、実施例２での高照度露光の結果と同様、本発明の試料（４０２）〜（４０５）は高い感度を示し、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。
【０１４０】
【発明の効果】
本発明のハロゲン化銀カラー写真感光材料により、高感度、低カブリで、高照度での相反則特性に優れ、かつ露光後処理までの経時による感度及び階調変化が小さい効果が得られた。
【図面の簡単な説明】
【図１】エッチング/ＴＯＦ−ＳＩＭＳ法による解析用グラフを表す。
【図２】ＴＯＦ−ＳＩＭＳ法によるハロゲン化銀粒子内の深さ方向の沃化物イオンの含有率分布を表す。
【図３】ＴＯＦ−ＳＩＭＳ法によるハロゲン化銀粒子内の深さ方向の沃化物イオンの含有率分布を表す。
【図４】ＴＯＦ−ＳＩＭＳ法によるハロゲン化銀粒子内の深さ方向の沃化物イオンの含有率分布を表す。
【図５】ＴＯＦ−ＳＩＭＳ法によるハロゲン化銀粒子内の深さ方向の沃化物イオンの含有率分布を表す。
【図６】ＴＯＦ−ＳＩＭＳ法によるハロゲン化銀粒子内の深さ方向の沃化物イオンの含有率分布を表す。
【図７】ＴＯＦ−ＳＩＭＳ法によるハロゲン化銀粒子内の深さ方向の沃化物イオンの含有率分布を表す。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to silver halideColor photographic materialA silver halide emulsion having high sensitivity but low fog, excellent reciprocity characteristics at high illuminance, and small sensitivity fluctuation and gradation fluctuation due to time fluctuation until post-exposure processing, a method for producing the same, and a halogen using the same The present invention relates to a silver halide color photographic light-sensitive material.
[0002]
[Prior art]
In recent years, in color photographic paper, demands for performance such as high sensitivity, stable processing, high image quality, and rapid development processing have been significantly increased. To increase the sensitivity of silver chloride emulsions, a method in which bromide ions are mainly contained in emulsion grains has been studied so far. For example, European Patent No. 0295439 discloses a method in which bromide ions are contained in the surface portion of a particle, and US Pat. No. 5,252,454 discloses that a bromide concentration formed by epitaxy on the particle surface is at least 20 mol%. A method for incorporating a localized phase is disclosed in US Pat. No. 5,252,456, in which a fine grain emulsion is blended with a larger high silver chloride host grain emulsion and Ostwald ripened to bromide rich on the grain surface. There are methods by which phases are formed. On the other hand, iodide ions are also contained in the silver chloride emulsion grains, thereby increasing the sensitivity. However, there have been few examples aimed at increasing the sensitivity so far, and as represented by the above cited patents, the inclusion of iodide ions is generally allowed or avoided at a low concentration.
[0003]
Some examples of increasing the sensitivity by containing iodide ions in a high silver chloride emulsion are given below. U.S. Pat. Nos. 5,264,337, 5,292,632, and 5,314,798 describe that iodide is contained inside the grains in the late stage of grain formation of high silver chloride {100} tabular grains. Is contained in a band shape. U.S. Pat. No. 5,275,930 showed an example of epitaxy deposition using a combination of bromide ions and a low proportion of iodide ions at the corners of tabular grains. JP-A-8-220681, JP-A-8-234340, JP-A-8-220684, JP-A-8-240879, and JP-A-8-234345 are commonly used for the preparation of host high silver chloride emulsion grains. The method of containing iodide ions has been devised, and a high chloride layer not intentionally containing iodide is intentionally formed on the iodide-containing layer having the maximum iodide ion concentration on the subsurface of the emulsion grains. It is characterized by.
[0004]
When iodide ions are mixed with silver chloride, interstitial silver ions inside the grains remarkably increase. Therefore, the increase in sensitivity by iodide ions is considered to promote the formation of photosensitive nuclei by the increase of interstitial silver ions. In the above-cited patents, the layer containing iodide is not on the surface, or is limited to the corner portion, so that the effect of increasing the sensitivity cannot be maximized. On the other hand, when iodide ions are contained only on the outermost surface of the grains, the iodide ions adsorbed on the outermost surface after the grains are formed are unstable to the silver chloride layer by subsequent treatment such as chemical sensitization. Since it causes incorporation, fogging is likely to occur, making it inappropriate for high sensitivity.
[0005]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is a silver halide emulsion having high sensitivity but low fog, excellent reciprocity characteristics at high illuminance, and low sensitivity fluctuation and gradation fluctuation due to time fluctuation until post-exposure processing, and a method for producing the same And a silver halide color photographic light-sensitive material using the same.
[0006]
[Means for Solving the Problems]
  As a result of intensive studies by the inventor, the above object is as follows (1) to (16It has been found that it can be effectively achieved by the method described in (1). That is,
(1) 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 halogen At least one silver halide emulsion of a silver halide emulsion layer, a green sensitive silver halide emulsion layer, and a red sensitive silver halide emulsion layer is a silver chloroiodide grain or silver chloroiodobromide having a silver chloride content of 90 mol% or more. A silver halide emulsion comprising grains, wherein the surface of the silver chloroiodide grains or silver chloroiodobromide grains is a silver iodide-containing layer, and the silver iodide content is attenuated in the depth direction from the grain surface A cube having an average particle size (average diameter of circle equivalent to the projected area of the particle) of 0.1 μm to 0.76 μm and having a {100} plane. Silver halide color pictures Light material.
(2) 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 halogen At least one silver halide emulsion of a silver halide emulsion layer, a green sensitive silver halide emulsion layer, and a red sensitive silver halide emulsion layer is a silver chloroiodide grain or silver chloroiodobromide having a silver chloride content of 90 mol% or more. A silver halide emulsion comprising grains, wherein the silver chloroiodide grains or silver chloroiodobromide grains have a layer having a silver iodide content that attenuates in the depth direction from the grain surface over the entire surface of the silver halide grains. A silver halide having a mean grain size (average diameter of circle equivalent to projected area of grain) of 0.1 μm to 0.76 μm and having a {100} plane Color photographic Fee.
(3) A silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on the support. At least one silver halide emulsion of a silver halide emulsion layer, a green sensitive silver halide emulsion layer, and a red sensitive silver halide emulsion layer is a silver chloroiodide grain or silver chloroiodobromide having a silver chloride content of 90 mol% or more. A silver halide emulsion comprising grains, wherein the surface of the silver chloroiodide grains or silver chloroiodobromide grains is a silver iodide-containing layer, and the iodide is attenuated exponentially in the depth direction from the grain surface. It is a cube having a layer having a silver content, an average particle size (average of the diameter of a circle equivalent to the projected area of the particle) of 0.1 μm to 0.76 μm, and having a {100} plane. Silver halide Over photographic light-sensitive material.
(4) The silver halide color photograph as described in any one of (1) to (3) above, wherein the layer containing silver iodide on the grain surface is a layer made of silver iodochloride. Photosensitive material.
(5) The average grain size (average of the diameter of a circle equivalent to the projected area of the grain) of the silver halide grains is 0.1 μm to 0.62 μm, (1) to (4) Or a silver halide color photographic light-sensitive material according to any one of the above.
(6(1) to (1) above, wherein the introduction of iodide ions is completed in a manner that ends before forming 98% of the grain volume.5Or a silver halide color photographic light-sensitive material according to any one of the above.
(7(1) to (1) above, characterized in that the introduction of iodide ions is prepared by a method starting outside 80% of the grain volume and ending before forming 98%.5Or a silver halide color photographic light-sensitive material according to any one of the above.
(8(1) to (1) above, wherein the introduction of iodide ions is carried out using silver halide fine grains containing silver iodide.7Or a silver halide color photographic light-sensitive material according to any one of the above.
(9) Halogenation for use in a silver halide color photographic material having 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 on the support. The silver emulsion layer is a silver halide emulsion composed of silver chloroiodide grains or silver chloroiodobromide grains having a silver chloride content of 90 mol% or more, and the introduction of iodide ions is halogenated. A mixing vessel is provided separately from the reaction vessel for causing nucleation and / or grain growth of silver halide grains, and an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide containing iodide ions are supplied into the mixing vessel. Using silver halide fine grains containing silver iodide formed by mixing, the silver halide fine grains are started outside 80% of the silver halide grain volume to form 98%. And a layer having a silver iodide content that attenuates in the depth direction from the surface of the silver halide grain, and has an average grain size (average of the diameter of a circle equivalent to the projected area of the grain). ) Is 0.1 to 0.76 μm and is a cube having a {100} plane, a silver halide color photographic light-sensitive material.
(10The above-mentioned (characterized in that the size of the silver halide fine particles containing silver iodide is 0.001 to 0.06 μm.8Or (9Silver halide color photographic light-sensitive material as described in 1).
(11The silver chloroiodide grains or silver chloroiodobromide grains contain one or more kinds, preferably four or more kinds of transition metal complexes.10Or a silver halide color photographic light-sensitive material according to any one of the above.
(12The silver chloroiodide grains or silver chloroiodobromide grains contain one or more transition metal complexes, and the transition metal complex has water or a 5- or 6-membered heterocyclic compound as a ligand. (1) to (1) above,10Or a silver halide color photographic light-sensitive material according to any one of the above.
(13) The silver chloroiodide grains or the silver chloroiodobromide grains are represented by [IrCl_Five(H₂O)]^2-, [IrCl_Five(H₂O)]^-, [IrCl_Four(H₂O)₂]^-, [IrCl_Four(H₂O)₂]⁰, [IrCl_Three(H₂O)_Three]⁰, [IrCl_Three(H₂O)_Three]⁺, [IrBr_Five(H₂O)]^2-, [IrBr_Five(H₂O)]^-, [IrBr_Four(H₂O)₂]^-, [IrBr_Four(H₂O)₂]⁰, [IrBr_Three(H₂O)_Three]⁰, [IrBr_Three(H₂O)_Three]⁺, [IrCl_Five(thiazole)]^2-, [IrCl_Five(5-methylthiazole)]^2-, [IrBr_Five(thiazole)]^2-, [IrBr_Five(5-methylthiazole)]^2-And [IrCl_Four(thiazole)₂]^-(1) to (1) above, which contain a transition metal complex selected from10Or a silver halide color photographic light-sensitive material according to any one of the above.
(14(1) to (1) above, wherein the iodide ion content is 0.1 mol% or more based on the total silver amount of all emulsion grains.13Or a silver halide color photographic light-sensitive material according to any one of the above.
(15(1) to (1) above, wherein the iodide ion content is 0.06 mol% or more with respect to the total silver amount of all the emulsion grains and spectrally sensitized with a trimethine cyanine dye.14Or a silver halide color photographic light-sensitive material according to any one of the above.
(16(Ii) The iodide content is 0.06 mol% or more based on the total silver content of all emulsion grains, and the central metal of at least one transition metal complex is ruthenium or osmium ( 1) to (15Or a silver halide color photographic light-sensitive material according to any one of the above.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
  The present invention is described in detail below. The silver halide grains in the silver halide emulsion used in the present invention are, {Cubic with 100} facesthe body'sCrystal grains (these grains may have rounded vertices and higher-order surfaces)It is.
[0008]
As the silver halide emulsion used in the present invention, a silver chloroiodide emulsion or a silver chloroiodobromide emulsion having a silver chloride content of 90 mol% or more is used. From the viewpoint of rapid processability, the silver chloride content is A silver chloroiodide emulsion or silver chloroiodobromide emulsion of 95 mol% or more is preferred, and a silver chloroiodide emulsion or silver chloroiodobromide emulsion having a silver chloride content of 98 mol% or more is more preferred. Among such silver halide emulsions, the content of iodide ions contained in the silver halide grains is 0.01 to 1.0 mol%, more preferably 0.05 to 0.80 mol, per mol of total silver. %, Most preferably having a silver iodochloride phase containing from 0.25 to 0.60 mol% of iodide ions is preferred because high sensitivity is obtained and the exposure to high illumination is excellent. Further, a silver halide grain having a silver bromide localized phase of 0.2 to 5 mol% per mol of total silver, more preferably 0.5 to 3 mol% per mol of silver gives high sensitivity, and This is particularly preferable because the photographic performance can be stabilized.
[0009]
For the introduction of iodide ions, an iodide salt solution may be added alone, or an iodide salt solution may be added together with the addition of a silver salt solution and a high chloride salt solution. The latter is more preferable because iodide ions are uniformly introduced into the former, so that the photographic performance can be stabilized. In the latter case, it is best to use an iodide salt solution and a high chloride salt solution separately, or they may be added as a mixed solution of an iodide salt and a high chloride salt. The iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth iodide salt. Alternatively, iodide can be introduced by cleaving iodide ions from organic molecules described in US Pat. No. 5,389,508. As another iodide ion source, silver halide fine particles containing silver iodide can be used. The silver halide fine particles can be formed by using a mixing vessel described in the specification of JP-A-10-43570 separately from a reaction vessel for causing nucleation and / or grain growth of silver halide grains. An aqueous solution of an aqueous silver salt and an iodide salt solution (if necessary, a halide salt solution other than iodide, separately or as a mixed solution of iodide salt and other halide salt) are introduced into the mixing container, and iodine is added. Silver halide fine particles containing silver halide are formed. The silver halide fine particles containing silver iodide 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, release of iodide ions is suppressed. Therefore, the average projected grain size of the silver halide fine grains containing silver iodide used is preferably 0.001 to 0.06 μm, more preferably 0.001 to 0.04 μm, and most preferably 0.001 to 0.02 μm. The introduction of iodide ions by silver halide fine particles containing silver iodide may also be added alone to the reaction vessel or in combination with the addition of the silver salt solution and the high chloride salt solution. In the method using silver halide fine grains containing silver iodide, iodide ions tend to be introduced more uniformly than those using an aqueous iodide salt solution.
[0010]
Addition of an iodide salt solution or silver halide fine grains containing silver iodide may be concentrated during one period of grain formation or may be carried out over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining an emulsion with high sensitivity and low covering. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 80%. The addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution can be completed slightly inside from the grain surface to form a layer having a silver iodide content that attenuates in the depth direction from the high silver chloride emulsion grain surface of the present invention. An emulsion with higher sensitivity and lower covering can be obtained.
There is no particular limitation on the method of attenuation of the silver iodide content in the silver iodide-containing layer. For example, even in the type of emulsion D, C, F, G, which will be described later in Example 1 As shown in FIG. Preferably, it is a type that attenuates in series as in the former.
[0011]
The distribution of iodide ion content in the depth direction in the grains can be measured by etching / TOF-SIMS (Time of Flight, Secondary Ion Mass Spectrometry) method, for example, using TRIFTII 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 particle surface is etched with gallium ions in a TOF-SIMS apparatus, and after etching, iodide ion is detected by performing mass analysis of the extreme surface by the TOF-SIMS method. By repeating etching and TOF-SIMS measurement, the content distribution of iodide ions in the depth direction in the grains was evaluated. An etching rate is obtained in advance, and the depth position is determined by converting the time required for etching into the etched depth. The depth resolution of this etching / TOF-SIMS method is about several nm. FIG. 1 is an example of analysis results obtained by etching / TOF-SIMS of grains in which iodide solution was added at the end of 92% of grain formation and iodide was introduced into the grains. In the figure, the measurement results at the region where the etching time is short and at the extreme surface of the particles are enlarged, and the intensity change of fragment ions observed in addition to iodide ions is also shown. Accompanying etching, derived from organic matter such as gelatin remaining on the particle surface¹³CH^-The secondary ionic strength (Δ) decreases. Only after organic substances such as gelatin are removed by etching, secondary ions such as chloride ions (◇) and iodide ions (○) derived from silver halide grains are detected. Therefore, the outermost surface of the grain is the dotted line portion shown in the figure, and the depth direction distribution of the iodide ion content was evaluated from this point.
[0012]
When the emulsion of the present invention contains a silver bromide localized phase, it is preferable to produce a silver bromide localized phase having a silver bromide content of at least 10 mol% or more by epitaxial growth on the grain surface. The silver bromide content of the silver bromide localized phase is preferably in the range of 10 to 60 mol%, and most preferably in the range of 20 to 50 mol%. The silver bromide localized phase is preferably composed of 0.1 to 5 mol% of silver constituting the silver halide grains in the present invention, and is preferably composed of 0.3 to 4 mol% of silver. More preferably, it is configured. The silver bromide localized phases include primary iridium (III) chloride, primary iridium (III) bromide, secondary iridium chloride (IV), sodium hexachloroiridium (III), potassium hexachloroiridium (IV) It is preferable to contain a Group VIII metal complex ion such as hexaammineiridium (IV) salt, trioxalatoiridium (III) salt, or trioxalatoiridium (IV) salt. The amount of these compounds added varies over a wide range depending on the purpose, but it is 10 per mol of silver halide.^-9-10^-2Mole is preferred.
[0013]
In the present invention, transition metal ions can be added in the process of forming and / or growing silver halide grains, and the metal ions can be incorporated into and / or on the surface of the silver halide grains. As the metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, iridium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any one of the above metal ions of iron, ruthenium, iridium, osmium, lead, cadmium, or zinc. It is also preferred to use it in the molecule. An organic compound can also be used as a ligand, and preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More preferred organic compounds are compounds having a nitrogen atom, phosphorus atom, oxygen atom or sulfur atom in the molecule as a coordination atom to the metal, most 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.
[0014]
A combination of metal ions and ligands is preferably a combination of iron ions, ruthenium ions and cyanide ions. 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 thiocyan, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, pyrazine. Or preferably 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. These complexes with cyanide ions as ligands are 1 x 10 per mole of silver during grain formation.^-8From mole to 1 × 10^-2It is preferable to add 1 mol.^-6From mole to 5 × 10^-FourMost preferably, it is added in a molar amount. When iridium is used as the central metal, the ligand is preferably a fluoride ion, a chloride ion, a bromide ion, or an iodide ion. Among them, a chloride ion or a bromide ion is preferably used. Specifically preferred as the iridium complex is [IrCl₆]^3-, [IrCl₆]^2-, [IrCl_Five(H₂O)]^2-, [IrCl_Five(H₂O)]^-, [IrCl_Four(H₂O)₂]^-, [IrCl_Four(H₂O)₂]⁰, [IrCl_Three(H₂O)_Three]⁰, [IrCl_Three(H₂O)_Three]⁺, [IrBr₆]^3-, [IrBr₆]^2-, [IrBr_Five(H₂O)]^2-, [IrBr_Five(H₂O)]^-, [IrBr_Four(H₂O)₂]^-, [IrBr_Four(H₂O)₂]⁰, [IrBr_Three(H₂O)_Three]⁰, [IrBr_Three(H₂O)_Three]⁺, [IrCl_Five(thiazole)]^2-, [IrCl_Five(5-methylthiazole)]^2-, [IrBr_Five(thiazole)]^2-, [IrBr_Five(5-methylthiazole)]^2-, [IrCl_Four(thiazole)₂]^-And [IrCl_Five(OCN)]^3-It is. These iridium complexes are 1x10 per mole of silver during grain formation.^-TenFrom mole to 1 × 10^-3It is preferable to add 1 mol.^-8From mole to 1 × 10^-FiveMost preferably, it is added in a molar amount. 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 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 1x10 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.
[0015]
The silver chloroiodide emulsion or silver chloroiodobromide emulsion of the present invention uses a combination of a plurality of transition metal complexes to provide higher sensitivity, lower gradation of the gradation of the low density portion, and reciprocity characteristics at high illuminance. Can be obtained. It is preferable to use at least three types of transition metal complexes for the purpose of high sensitivity, high contrast, and reciprocity law improvement, and four or more types of transition metal complexes in order to obtain an emulsion having a wide range of reciprocity law characteristics. It is more preferable to use Further, in order to increase the gradation of the low concentration portion, it is most preferable that at least one of the complexes to be used is a transition metal complex having ruthenium or osmium as a central metal.
[0016]
In the present invention, the above complex is added directly to the reaction solution at the time of silver halide grain formation, added to an aqueous halide solution for forming silver halide grains, or added to other solutions to obtain a grain formation reaction. It is preferably incorporated into the silver halide grains by adding to the solution. Furthermore, it is also preferable that these methods are combined and contained in the silver halide grains.
[0017]
When these complexes are incorporated into silver halide grains, it is preferable that they be uniformly present inside the grains, but these are disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to make it 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, the particle surface phase may be modified by physical ripening with fine particles incorporating the complex in the particles. preferable. Furthermore, 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, and the silver chloride layer, the silver chlorobromide layer, the silver bromide layer, the silver iodochloride layer, and the silver iodobromide layer should each contain the complex. Is also preferable.
[0018]
  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 μm to0.76μmIn Although0.1 μm to 0.7 μm is preferable. More preferably, they are 0.1 micrometer-0.38 micrometer, and 0.1 micrometer-0.2 micrometer are the most preferable.
  The particle size distribution is preferably a so-called monodispersed material having a coefficient of variation (the standard deviation of the particle size distribution divided by the average particle size) of 20% or less, desirably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating.
[0019]
Various compounds or precursors thereof are added to the silver halide emulsion used in the present invention for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. be able to. Specific examples of these compounds are preferably those described in pages 39 to 72 of the above-mentioned JP-A-62-215272. Further, 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (the aryl residue has at least one electron-withdrawing group) are also preferably used.
[0020]
In the present invention, in order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A No. 11-109576 and the carbonyl group described in JP-A No. 11-327094 are adjacent to both ends of an amino group Alternatively, cyclic ketones having a double bond substituted with a hydroxyl group (particularly those represented by the general formula (S1), paragraph numbers 0036 to 0071 can be incorporated in the specification of the present application), JP-A-11 -143011, sulfo-substituted catechol and hydroquinones (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzene) Sulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4 5-and tri-hydroxy benzenesulfonic acid and salts thereof), water-soluble reducing agents represented by the general formula of JP-A-11-102045 (I) ~ (III) is also preferably used in the present invention.
[0021]
Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range for each layer of emulsion in the light-sensitive material of the present invention.
In the light-sensitive material of the present invention, examples of spectral sensitizing dyes used for spectral sensitization in the blue, green, and red regions include, for example, Heterocyclic compounds-Cyanine dyes and related compounds (John Wiley & Sons [New York, London] by FM Harmer). (Published in 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. In particular, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, the strength of adsorption, and the exposure temperature. This is very preferable from the viewpoint of dependency and the like.
[0022]
The spectral sensitizing dye in the green region is preferably a trimethine cyanine dye represented by the following general formula (I), and most preferably an oxatrimethine cyanine dye or an oxazolotrimethine cyanine dye.
[0023]
[Chemical 1]

[0024]
Where Z₁₀₁And Z₁₀₂Each represents an atomic group necessary to form a nitrogen-containing heterocyclic nucleus. The nitrogen-containing heterocyclic nucleus is preferably a 5- or 6-membered cyclic nucleus containing a nitrogen atom as a hetero atom and other sulfur, oxygen, selenium, or tellurium atoms. However, a condensed ring may be further bonded to these rings, and a substituent may be further bonded. Specific examples of the nitrogen-containing heterocyclic nucleus include thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, imidazole nucleus. Benzimidazole nucleus, naphthimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, benzindolenine nucleus, indole nucleus, tellurazole nucleus, benzotelrazole nucleus, naphthotelrazole nucleus, etc. be able to. R₁₀₁And R₁₀₂Each represents an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group. These groups and the groups described below are each used in the sense of including their substituents. For example, taking an alkyl group as an example, it includes unsubstituted and substituted alkyl groups, and these groups may be linear, branched or cyclic. The carbon number of the alkyl group is preferably 1-8.
[0025]
Specific examples of the substituent of the substituted alkyl group include a halogen atom (fluorine, base, bromine, iodine, etc.), cyano group, alkoxy group, substituted or unsubstituted amino group, carboxylic acid group, sulfonic acid group, hydroxyl group, etc. These may be substituted by one or more of them. Specific examples of the alkenyl group include a vinylmethyl group. Specific examples of the aralkyl group include a benzyl group and a phenethyl group.
m₁₀₁Represents 1. R₁₀₃Represents a hydrogen atom, a lower alkyl group, an aralkyl group or an aryl group. Specific examples of the aryl group include a substituted or unsubstituted phenyl group. R₁₀₄Represents a hydrogen atom.
j₁₀₁, K₁₀₁Represents 0 or 1, X^- ₁₀₁Represents an acid anion and n₁₀₁Represents 0 or 1.
Next, specific examples of the compound represented by formula (I) will be given. However, it is not limited to this.
[0026]
[Chemical formula 2]

[0027]
[Chemical 3]

[0028]
[Formula 4]

[0029]
The addition amount of these spectral sensitizing dyes varies widely depending on the case, and 0.5 × 10 5 per mol of silver halide.^-6Mol ~ 1.0 × 10^-2A molar range is preferred. More preferably, 1.0 × 10^-6Mol ~ 5.0 × 10^-3The range of moles.
[0030]
The silver halide emulsion used in 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.
[0031]
In order to perform gold sensitization on the silver halide emulsion used in the present invention, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands are used. be able to. 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.
[0032]
Examples of the gold (I) compound having an organic ligand include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, such as gold (I) tetrafluoroborate bis (1,4,5- Trimethyl-1,2,4-triazolium-3-thiolate), organic mercaptogold (I) complexes described in JP-A-11-218870, such as potassium bis (1- [3- (2-sulfonatebenzamide) phenyl] -5-mercaptotetrazole potassium salt) Aurate (I) pentahydrate, gold (I) compound coordinated with nitrogen compound anion described in JP-A-4-268550, for example, bis (1-methylhydantoinato) Gold (I) sodium salt tetrahydrate can be used. Further, gold (I) thiolate compounds described in US Pat. No. 3,503,749, gold compounds described in JP-A-8-69074, JP-A-8-69075, and JP-A-9-269554, The compounds described in Japanese Patent Nos. 5620841, 5912112, 5620841, 5939245, and 5912111 can also be used.
The amount of these compounds added may vary widely depending on the case, but is 5 × 10 5 per mole of silver halide.^-7~ 5x10^-3Mole, preferably 5 × 10^-6~ 5x10^-FourIs a mole.
[0033]
Colloidal gold sulfide can also be used. The manufacturing method thereof is Research Disclosure (37154), Solid State Ionics 79, 60-66, 1995, Compt. Rend.Hebt.Seances Acad.Sci.Sect.B, 263, 1328, published in 1966. 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 may 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.
[0034]
  Silver halide of the present inventionColorConventionally known photographic materials and additives can be used for the photographic light-sensitive material.
  For example, a transmissive support or a reflective support can be used as the photographic support. As the transparent support, transparent films such as cellulose nitrate film and polyethylene terephthalate, polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), and polyester of NDCA, terephthalic acid and EG For example, an information recording layer such as a magnetic layer is preferably used. As the reflective support, a reflective support that is laminated with a plurality of polyethylene layers or polyester layers and contains a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminate layers) is preferable.
[0035]
In the present invention, more preferred reflective supports include those having a polyolefin layer having fine pores on the paper substrate on the side on which the silver halide emulsion layer is provided. The polyolefin layer may be composed of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no micropores (eg, polypropylene, polyethylene) and is close to the paper substrate. More preferred is a polyolefin (for example, polypropylene or polyethylene) having micropores on the side. The density of the multi-layer or single-layer polyolefin layer located between the paper substrate and the photographic constituent layer is preferably 0.40 to 1.0 g / ml, and more preferably 0.50 to 0.70 g / ml. In addition, the thickness of the multilayer or single polyolefin layer located between the paper substrate and the photographic constituent 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 0.5, and more preferably 0.1 to 0.2.
[0036]
In addition, it is also preferable to provide a polyolefin layer on the opposite side (back side) of the photographic constituent layer of the paper substrate from the viewpoint of increasing the rigidity of the reflective support. In this case, the back side polyolefin layer is a polyethylene whose surface is matte Alternatively, polypropylene is preferable, and polypropylene is more preferable. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support of the present invention, preferred embodiments 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.
[0037]
Furthermore, it is preferable to contain a fluorescent brightening agent in the water-resistant resin layer. Further, the fluorescent brightener may be dispersed in the hydrophilic colloid layer of the photosensitive material. 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 is 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.
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 reflective or second-type diffuse reflective metallic surface.
[0038]
The support used for the light-sensitive material according to the present invention is a support provided on a support having a white polyester-based support or a layer containing a white pigment on the side having a silver halide emulsion layer. It may be used. 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.
[0039]
In the light-sensitive material according to the present invention, for the purpose of improving the sharpness of an image or the like, a dye which can be decolored by processing as described in pages 27 to 76 of European Patent EP0,337,490A2 is added to a hydrophilic colloid layer (among others). However, an oxonol dye) is added so that the optical reflection density at 680 nm of the photosensitive material is 0.70 or more, or a divalent to tetravalent alcohol (such as trimethylolethane) is added to the water-resistant resin layer of the support. ) Etc. It is preferable to contain 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated.
[0040]
The photosensitive material according to the present invention has a hydrophilic colloid layer for preventing irradiation and halation or improving safety light safety, etc., described on pages 27 to 76 of EP 0337490A2, It is preferable to add a dye (in particular, an oxonol dye or a cyanine dye) that can be decolored by treatment. 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.
[0041]
In the present invention, a colored layer that can be decolored by treatment in place of the water-soluble dye or in combination with the water-soluble dye is used. The colored layer that can be decolored by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably placed under the emulsion layer (support side) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to select and install only some of them. It is also possible to install a colored layer that has been colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength having the highest optical density in the wavelength range used for exposure (visible light range of 400 nm to 700 nm for normal printer exposure, wavelength of the scanning exposure light source used for scanning exposure). The optical density value at is preferably 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.
[0042]
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 is 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.
[0043]
  Silver halide of the present inventionColorPhotosensitive materials are used for color negative films, color positive films, color reversal films, color reversal photographic papers, color photographic papers, etc., among which color photographic papers are preferred.
  The color photographic paper preferably has at least one yellow color-developing silver halide emulsion layer, magenta color-developing silver halide emulsion layer, and cyan color-developing 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.
[0044]
However, a different layer structure may be used.
The silver halide emulsion layer containing the yellow-coupler may be disposed at any position on the support. If the yellow coupler-containing layer contains silver halide tabular grains, a magenta coupler-containing halogenated emulsion layer may be used. It is preferably coated at a position farther from the support than at least one silver emulsion layer or cyan coupler-containing silver halide emulsion layer. From the viewpoint of promoting color development, promoting desilvering, and reducing residual color by sensitizing dye, the yellow coupler-containing silver halide emulsion layer is located farthest from the support than the other silver halide emulsion layers. It is preferable that it is coated. 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. Further, each of the color forming 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.
[0045]
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.
[0046]
In particular, in the present invention, the above-mentioned reflective support and silver halide emulsion, further different metal ion species doped in 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, coating film pH of the photosensitive material, etc., those described in the patents in Tables 1 and 2 are particularly preferably applicable.
[0047]
[Table 1]

[0048]
[Table 2]

[0049]
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 No. 10-221825 may be added.
[0050]
More specific description will be given below.
As the cyan coupler that can be used in the present invention, a pyrrolotriazole coupler is preferably used. A coupler represented by the general formula (I) or (II) of JP-A-5-313324 and a general coupler of JP-A-6-347960 The couplers represented by formula (I) and the exemplified couplers described in these patents are particularly preferred.
Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable.
Other cyan couplers include pyrroloazole-type cyan couplers described in European Patents EP0488248 and EP0491197A1, 2,5-diacylaminophenol couplers described in US Pat. No. 5,888,716, US Pyrazoloazole type cyan couplers having an electron withdrawing group and a hydrogen bonding group at the 6-position described in Japanese Patent Nos. 4,873,183 and 4,916,051, particularly JP-A-8-171185, Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A Nos. 8-311360 and 8-339060 are also preferable.
[0051]
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.
[0052]
As the magenta coupler used in the present invention, 5-pyrazolone-based magenta couplers and pyrazoloazole-based magenta couplers described in the above-mentioned publicly known documents are used, and among them, hue, image stability, color developability, etc. A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly connected to the 2, 3 or 6 position of the pyrazolotriazole ring as described in JP-A-61-65245, JP-A-61-65246 A pyrazoloazole coupler having a sulfonamide group in the molecule as described in JP-A-61-147254, a pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group as described in JP-A No. 61-147254, and European Patent No. 226. , 849A and 294,785A, the 6-position is an alkoxy group or aryloxy. Use of pyrazoloazole couplers having a group.
In particular, the magenta coupler is preferably a pyrazoloazole coupler represented by the general formula (M-I) described in JP-A-8-122984. Paragraph Nos. 0009 to 0026 of the patent are directly applied to the present application. Incorporated as part of the specification.
In addition, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in European Patent Nos. 854384 and 844640 are also preferably used.
[0053]
Further, as yellow couplers, in addition to the compounds described in the above table, acylacetamide type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group described in European Patent EP 0447969A1, European Patent EP 0482552A1 A malondianilide type yellow coupler having a cyclic structure described in the book and an acylacetamide type yellow coupler having a dioxane structure described in US Pat. No. 5,118,599 are 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.
[0054]
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 above table, Alternatively, it is preferably dissolved together with a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.
Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15, and International Publication WO 88/00723, pages 12 to 30. The homopolymers or copolymers mentioned are mentioned. More preferably, use of a methacrylate or acrylamide polymer, particularly an acrylamide polymer is preferred in view of color image stability.
[0055]
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 developer to speed up the 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.
[0056]
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.
JP-A-46-3335, JP-A-55-152776, JP-A-5-197004, JP-A-5-232630, JP-A-5-307232, JP-A-6-21813, JP-A-8-53427, JP-A-8-234364 No. 8-239368, No. 9-31067, No. 10-115898, No. 10-147777, No. 10-182621, German Patent No. 19739797A, European Patent No. 711804A, and Japanese Patent Laid-Open No. 8-501291. It is a compound described in No. etc.
[0057]
As the binder or protective colloid that can be used in the light-sensitive material according to 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.
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.
[0058]
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.
[0059]
The amount of these surfactants added to the photosensitive material is not particularly limited, but is generally 1 × 10.^-Five~ 1g / m², Preferably 1 × 10^-Four~ 1x10^-1g / m²More preferably 1 × 10^-3~ 1x10^-2g / m²It is.
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.
[0060]
The photosensitive material of the present invention is suitable for a scanning exposure system using a cathode ray (CRT) in addition to being used in a printing system using a normal negative printer. The cathode ray tube exposure apparatus is simpler and more compact and less expensive than an apparatus using a laser. Also, the adjustment of the optical axis and color is easy.
As the cathode ray tube used for image exposure, various light emitters that emit light in the spectral region are used as necessary. For example, a red light emitter, a green light emitter, or a blue light emitter may be used alone or in combination. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in the yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.
[0061]
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, causing each color to emit light sequentially, and exposing through a film that cuts 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.
[0062]
The photosensitive material of the present invention is a monochromatic high light source such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic light source (SHG) using a combination of a solid state laser using a semiconductor laser and a nonlinear optical crystal. A digital scanning exposure method using density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.
[0063]
When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green, and red.
When the exposure time in such scanning exposure is defined as the exposure time of the pixel size when the pixel density is 400 dpi, a preferable exposure time is 10^-FourSeconds or less, more preferably 10^-6Less than a second.
[0064]
Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above.
In order to process 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. The processing materials and processing methods described in the 17th line to the 18th page, lower right column, 20th line are preferably applicable. Further, as the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.
[0065]
The present invention is preferably applied to a light-sensitive material having rapid processing suitability.
The color development time refers to the time from when the light-sensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, when processed by an automatic developing machine, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leaves the color developer and is bleach-fixed in the next processing step. The total of both the time during which air is conveyed toward the bath (so-called air time) is called color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The water washing or stabilization time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the water washing or stabilizing liquid.
[0066]
When rapid processing is carried out in the present invention, 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.
[0067]
The light-sensitive material of the present invention can be developed after exposure using a conventional developing method containing an alkali agent and a developing agent, an activator such as an alkaline solution containing the developing agent in the photosensitive material and not containing the developing agent. In addition to a wet method such as a method of developing with a beta solution, a thermal development method without using a processing solution can be used. In particular, the activator method is a preferable method from the viewpoint of environmental protection because it does not contain a developing agent in the processing solution, so that the processing solution can be easily managed and handled, and the load during processing of the waste liquid is small. In the activator method, as the developing agent incorporated in the light-sensitive material or a precursor thereof, for example, JP-A-8-234388, JP-A-9-152686, JP-A-9-152893, JP-A-9-212814, The hydrazine type compound described in -160193 is preferable.
[0068]
Further, a developing method in which the amount of silver applied to the photosensitive material is reduced and image amplification processing (compensation processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, an image forming method using an activator solution containing hydrogen peroxide described in JP-A-8-297354 and 9-152695 is preferably used.
In the activator method, desilvering is usually performed after processing with an activator solution, but in the image amplification processing method using a low silver amount of light-sensitive material, desilvering is omitted, and simple washing such as washing or stabilization is performed. The method 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.
[0069]
For the activator solution, desilvering solution (bleaching / fixing solution), water washing and stabilizing solution used in the present invention, known materials and 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.
[0070]
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.
[0071]
The light-sensitive material of the present invention can be preferably used in combination with the exposure and development systems described in the following known materials.
-Automatic printing and developing system described in JP-A-10-333253
-Photosensitive material conveying apparatus described in JP-A-2000-10206
A recording system including an image reading device described in JP-A-11-215312
An exposure system comprising a color image recording system described in JP-A-11-88619 and JP-A-10-202950
A digital photo print system including a remote diagnosis system described in JP-A-10-210206
[0072]
【Example】
Example 1
(Preparation of emulsion A)
3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 42.8 ml of 1N sulfuric acid and 25 ml of 1,8-dihydroxy-3,6-dithiaoctane (1% aqueous solution) were added. An aqueous solution containing 2.12 mol of silver nitrate and an aqueous solution containing 2.18 mol of sodium chloride were added to and mixed at 68 ° C. with vigorous stirring. Thereafter, it was washed with sedimentation water at 40 ° C. for desalting. Further, 168.0 g of lime-processed gelatin was added, and the pH and pAg of the emulsion were adjusted to 5.6 and 7.3, respectively. From the electron micrograph, the particle shape was cubic, the average particle size was 0.76 μm, and the coefficient of variation was 10%.
[0073]
(Preparation of emulsion B)
In the emulsion grain formation, 95 to 100% of the total silver amount (surface 5% shell) was added, except that a silver iodide fine grain emulsion containing 0.004 mol of iodide ions was added. The preparation method was followed. The silver iodide fine grain emulsion used was prepared by a stirring mixer described in JP-A-10-43570. The shape of the obtained particle was a cube with very little roundness of the particle vertex from the electron micrograph.
(Preparation of Emulsion C) A method for preparing Emulsion B, except that the addition time of the silver iodide fine grain emulsion containing 0.004 moles of iodide ions was changed to a stage where 91 to 96% of the total silver amount was added. Followed. The shape of the grains was the same as that of Emulsion B.
(Preparation of Emulsion D) A method for preparing Emulsion B, except that the addition time of the silver iodide fine grain emulsion containing 0.004 moles of iodide ions was changed to the step of adding 85 to 90% of the total silver amount. Followed. The shape of the grains was the same as that of Emulsion B.
(Preparation of Emulsion E) A method for preparing Emulsion B, except that the addition time of the silver iodide fine grain emulsion containing 0.004 moles of iodide ions was changed to a stage in which 80 to 85% of the total silver amount was added. Followed. The shape of the grains was the same as that of Emulsion B.
(Preparation of Emulsion F) The preparation method of Emulsion A was followed except that 0.004 mol of potassium iodide aqueous solution was added at the stage of adding 95 to 96% of the total silver amount in the formation of emulsion grains. The shape of the obtained particle was a cube with very little roundness of the particle vertex from the electron micrograph.
(Preparation of Emulsion G) The emulsion A was prepared in the same manner as the emulsion A except that 0.004 mol of potassium iodide aqueous solution was added at the stage of adding 85 to 86% of the total silver amount in the formation of emulsion grains. The shape of the obtained particle was a cube with very little roundness of the particle vertex from the electron micrograph.
[0074]
Experiment 1: Content distribution measurement of iodide ion in grain
Regarding the silver halide grains of the above emulsions B to G, the iodine distribution in the depth direction in the grains was examined by etching / TOF-SIMS method. Samples for analysis were prepared as follows. After warm water was added to the emulsion to dissolve gelatin, the particles and gelatin were centrifuged, and the precipitated particles were coated on a Si substrate. Etching / TOF-SIMS measurement is performed on the coated sample. In order to prevent damage by gallium ions to be irradiated, the sample was cooled to −120 ° C. or lower. Analysis area is 60μm²Etching area is 240 μm²It is. The etching rate was evaluated using a silver chloride deposited film. A depth of approximately 0.5 to 1 nm was analyzed by one etching, and a depth of approximately 100 nm was analyzed by repeating etching. Iodide secondary ions were analyzed in negative ion measurement mode. After the etching of iodide / TOF-SIMS, the secondary ion of silver was measured for a certain time in the positive ion measurement mode, and the secondary ion of iodide (I^-) Strength of secondary ion of silver (Ag⁺) The number of particles in the sample was corrected by normalizing with intensity.
[0075]
2 to 7, it can be seen that iodide ions are present up to the grain surface in the emulsion in which the addition of iodide ions is completed inside the grains in the present invention. In addition, the silver chloroiodide emulsion of the present invention exhibits a distribution in which the iodide ion content in the grain attenuates in the depth direction from the surface.
[0076]
Gold sensitizer (colloidal gold sulfide) 6 × 10 in the above emulsions A to G^-FiveMol / mol Ag, blue-sensitive spectral sensitizing dye (A) 3.1 × 10^-FourMol / mol Ag was added, and chemical sensitization and spectral sensitization were optimally performed at 60 ° C., and 1- (5-methylureidophenyl) -5-mercaptotetrazole 4.4 × 10^-FourEmulsions A 'to G' were prepared with the addition of mol / mol Ag.
[0077]
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 (101) 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.
[0078]
First layer coating preparation
57 g of yellow coupler (ExY), 7 g of color image stabilizer (Cpd-1), 4 g of color image stabilizer (Cpd-2), 7 g of color image stabilizer (Cpd-3), 2 g of color image stabilizer (Cpd-8) Was dissolved in 21 g of a solvent (Solv-1) and 80 ml of ethyl acetate, and this liquid was emulsified and dispersed in 220 g of a 23.5 wt% 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 A ′ 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.
[0079]
The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. Moreover, the total amount of Ab-1, Ab-2, Ab-3, and Ab-4 is 15.0 mg / m in each layer.²60.0 mg / m², 5.0 mg / m²And 10.0 mg / m²It added so that it might become.
[0080]
[Chemical formula 5]

[0081]
The following spectral sensitizing dyes were used for the silver chlorobromide emulsions in the green and red sensitive emulsion layers, respectively.
Green sensitive emulsion layer
[0082]
[Chemical 6]

[0083]
(Sensitizing dye D per mole of silver halide, 3.0 x 10 for large size emulsions^-Four3.6 × 10 for small, small emulsions^-FourMol, and Sensitizing Dye E per mol of silver halide, 4.0 × 10 for large size emulsions^-Five7.0 x 10 for molar, small emulsions^-FiveMole, and sensitizing dye F per mole of silver halide, and 2.0 × 10 5 for large size emulsions.^-Four2.8 × 10 for small, small emulsions^-FourMole was added. )
Red sensitive emulsion layer
[0084]
[Chemical 7]

[0085]
(Sensitizing dyes G and H are each 8.0 moles per mole of silver halide and 8.0 × 10 for large size emulsions.^-Five10.7 × 10 for small, small emulsions^-FiveMole was added. )
Further, the following compound I was added to the red-sensitive emulsion layer at 3.0 × 10 6 per mole of silver halide.^-3Mole was added. )
[0086]
[Chemical 8]

[0087]
Further, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, respectively, at 3.3 × 10 3 per mole of silver halide.^-FourMol, 1.0 × 10^-3Moles and 5.9 × 10^-FourMole was added.
In addition, the second layer, the fourth layer, the sixth layer, and the seventh layer are each 0.2 mg / m 2.²0.2 mg / m²0.6 mg / m²0.1 mg / m²It added so that it might become.
Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, respectively, at 1 × 10 6 per 1 mol of silver halide.^-FourMol, 2 × 10^-FourMole was added.
Further, a copolymer latex of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 200,000 to 400,000) is 0.05 g / m on the red sensitive emulsion layer.²Was added.
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).
[0088]
[Chemical 9]

[0089]
(Layer structure)
The structure of each layer is shown below. Numbers are application amount (g / m²). The silver halide emulsion represents a coating amount in terms of silver.
Support
Polyethylene resin laminated paper
[White pigment (TiO 2 on the first layer side polyethylene resin)₂Content of 16% by weight, ZnO; content of 4% by weight) and optical brightener (4,4'-bis (5-methylbenzoxazolyl) stilbene, content of 0.03% by weight), bluish dye (Including ultramarine)]
First layer (blue sensitive emulsion layer)
Emulsion A 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
[0090]
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
[0091]

[0092]
Fourth layer (color mixing prevention layer)
Gelatin 0.71
Color mixing inhibitor (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
[0093]

[0094]
Sixth layer (UV absorbing layer)
Gelatin 0.46
Ultraviolet absorber (UV-B) 0.45
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.25
Seventh layer (protective layer)
Gelatin 1.00
Acrylic-modified copolymer of polyvinyl alcohol
(Degree of modification 17%) 0.04
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.01
[0095]
[Chemical Formula 10]

[0096]
Embedded image

[0097]
Embedded image

[0098]
Embedded image

[0099]
Embedded image

[0100]
Embedded image

[0101]
Embedded image

[0102]
Embedded image

[0103]
Embedded image

[0104]
Embedded image

[0105]
Similarly, Samples (102) to (107) were prepared by changing Emulsion A 'of Sample (101) to Emulsions B' to G '.
[0106]
In order to examine the photographic characteristics of these samples, the following experiment was conducted.
Experiment 2: Sensitometry
Each coated sample was subjected to gradation exposure for sensitometry using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.). An SP-1 filter was attached and exposed for 10 seconds with low illumination.
Further, gradation exposure for sensitometry was given using a high-illuminance exposure photometer (HIE type manufactured by Yamashita Denso Co., Ltd.). Wearing SP-1 filter, high illumination 10^-FourExposure for 2 seconds.
After the exposure, the following color development processing A was performed.
[0107]
The processing steps are shown below.
[Processing A]
The photosensitive material 101 is processed into a 127 mm width roll, and after imagewise exposure using a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd. Processing (running test) was performed. The treatment using this running liquid was designated as treatment A.
Processing temperature Temperature Time Replenishment amount^*
Color development 38.5 ° C 45 seconds 45 ml
Bleach fixing 38.0 ° C 45 seconds 35 ml
Rinse (1) 38.0 ° C. 20 seconds −
Rinse (2) 38.0 ° C. 20 seconds −
Rinse (3) ** 38.0 ° C. 20 seconds −
Rinse (4) ** 38.0 ° C 30 seconds 121 ml
* Photosensitive material 1m²Replenishment amount per
** A phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. is installed in the rinse (3), the rinse solution is taken out from the rinse (3), and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day.
(The rinsing was a counter-current tank system from (1) to (4).)
[0108]
The composition of each treatment liquid is as follows.

[0109]

[0110]

[0111]
The yellow color density of each sample after processing was measured, and the fog density of emulsions A 'to G' and the 10-second exposure low illuminance sensitivity, 10^-FourSecond exposure high illuminance sensitivity was obtained. The sensitivity was defined by the reciprocal of the exposure amount giving a color density higher by 1.0 than the minimum color density, and expressed as a relative value when the sensitivity of the development processing of the sample (101) was 100. These results are summarized in Table 3.
[0112]
[Table 3]

[0113]
From Table 1 and FIGS. 2 to 7, the silver chloroiodide emulsion of the present invention has a distribution in which the iodide ion content in the grains attenuates in the depth direction from the surface, so that the sensitivity is higher and the illuminance is higher. It turns out that it is excellent in the reciprocity law characteristic. In addition, the emulsion of the present invention in which the addition of iodide ions was completed before 98% of the grains were formed showed a low fog and high sensitivity. 2 to 7 show the distributions of emulsions B to G, respectively.
[0114]
Example 2
(Preparation of emulsion H)
To a 5% aqueous solution of lime-processed gelatin, 5.6 g of sodium chloride was added, and 42.8 ml of 1N sulfuric acid and 1.1 ml of N, N′-dimethylimidazolidine-2-thione (1% aqueous solution) were added. An aqueous solution containing 0.21 mol of silver nitrate and an aqueous solution containing 0.21 mol of sodium chloride were added to and mixed at 61 ° C. with stirring. Subsequently, while maintaining the temperature at 61 ° C., 1.27 mol of an aqueous solution containing 1.27 mol of silver nitrate and 1.27 mol of sodium chloride and 1 × 10 per total silver amount^-8Mole K₂[Ru (NO) Cl_FiveAnd an aqueous solution containing 0.21 mol of silver nitrate and an aqueous solution containing 0.21 mol of sodium chloride are added and mixed with stirring, followed by 0.21 mol of silver nitrate. 0.21 mol of an aqueous solution containing mol and sodium chloride and 2 × 10 2 per total silver^-FiveMole K_Four[Ru (CN)_FiveAnd an aqueous solution containing a transition metal complex of Furthermore, the aqueous solution containing 0.02 mol of silver nitrate and the aqueous solution containing 0.02 mol of sodium chloride were added and mixed while stirring at 61 ° C. Subsequently, an aqueous solution containing 0.11 mol of silver nitrate and 0.11 mol of sodium chloride and 2 × 10 per total silver amount^-6Mole K₂[Ir (H₂O) Cl_FiveAnd an aqueous solution containing a transition metal complex in an aqueous solution containing 0.04 mol of silver nitrate and 0.04 mol of sodium chloride and 4 × 10 4 per total silver amount.^-8Mole K₂[IrCl₆And an aqueous solution containing 0.04 mol of silver nitrate and an aqueous solution containing 0.04 mol of sodium chloride were added and mixed at 61 ° C. with stirring. Thereafter, it was washed with sedimentation water at 40 ° C. for desalting. Further, 168.0 g of lime-processed gelatin was added, and the pH and pAg of the emulsion were adjusted to 5.6 and 7.3, respectively. From the electron micrograph, the particle shape was cubic, the average particle size was 0.62 μm, and the coefficient of variation was 10%.
Gold sensitizer (gold (I) tetrafluoroborate bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate)) 1.5 × 10 5 was added to this emulsion.^-FiveMol / mol Ag, sulfur sensitizer (sodium thiosulfate) 6 × 10^-7Mol / mol Ag, blue-sensitive spectral sensitizing dye (A and B) 2.3 × 10^-FourMol / mol Ag and 1.5 × 10^-FourMol / mol Ag was added, and chemical sensitization and spectral sensitization were optimally performed at 60 ° C., and 1- (5-methylureidophenyl) -5-mercaptotetrazole 4.4 × 10^-FourMole / mole Ag was added.
[0115]
(Preparation of Emulsion J) The method for preparing Emulsion H was followed except that 0.006 mol of potassium iodide aqueous solution was added at the stage of adding 90 to 91% of the total silver amount in the formation of emulsion grains. The shape of the obtained particle was a cube with very little roundness of the particle vertex from the electron micrograph.
(Preparation of emulsion K) K₂[IrCl₆The method for preparing Emulsion J was followed except that the transition metal complex was not added. The shape of the grains was the same as that of Emulsion J.
(Preparation of Emulsion Q) In the step of adding 90 to 95% of the total silver amount in the formation of emulsion grains, a silver iodide fine grain emulsion containing 0.006 mol of iodide ions was added, and K₂[Ir (H₂O) Cl_Five] K₂[Ir (5-methylthiazole) Cl_FiveThe method for preparing Emulsion H was followed except for the change to The silver iodide fine grain emulsion used was prepared by a stirring mixer described in JP-A-10-43570. The shape of the obtained particle was a cube with very little roundness of the particle vertex from the electron micrograph.
(Preparation of Emulsion R) The preparation method of Emulsion Q was followed except that the blue-sensitive spectral sensitizing dye was changed to sensitizing dye C in the chemical sensitization process. The grain shape was the same as emulsion P.
Experiment 1 of Example 1 was performed on the above J, K, Q and R emulsions. As in the case of the emulsion of the present invention of Example 1, the iodide ion content in the grains was attenuated in the depth direction from the surface. Distribution was shown.
[0116]
Embedded image

[0117]
Samples (201) to (205) were prepared by replacing the first emulsion with emulsions H to K, Q, and R with exactly the same layer structure as in Example 1. Experiment 2 in Example 1 and Experiment 3 below were performed on this sample.
[0118]
Experiment 3: Stability of latent image after exposure
For each sample, the 10^-FourSensitometry was measured by changing the time from second high illumination exposure to treatment A, and the difference in sensitivity between the 60 minute post treatment and the 7 second post treatment was determined.
These results are summarized in Table 4.
[0119]
[Table 4]

[0120]
From Table 4, it can be seen that the silver chloroiodide emulsion of the present invention is a high-sensitivity and low-fogging emulsion and has excellent latent image stability after exposure.
[0121]
Example 3
(Preparation of Emulsion L) Based on the preparation method of Emulsion H described in Example 2, grain formation was performed in the same manner except for the addition of N, N′-dimethylimidazolidine-2-thione (1% aqueous solution). It was. From the electron micrograph, the shape of the particles was cubic, the average particle size was 0.38 μm, and the coefficient of variation was 8%.
Gold sensitizer (gold (I) tetrafluoroborate bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate)) 2.4 × 10 4 was added to this emulsion.^-FiveMol / mol Ag, sulfur sensitizer (sodium thiosulfate) 1 × 10^-7Mol / mol Ag, green sensitive spectral sensitizing dye (D, E and F) 3.6 × 10^-FourMol / mol Ag, 7.0 × 10^-FiveMol / mol Ag and 2.8 × 10^-FourMol / mol Ag was added, and chemical sensitization and spectral sensitization were optimally performed at 60 ° C., and 1- (5-methylureidophenyl) -5-mercaptotetrazole 4.4 × 10^-FourMol / mol Ag was added
(Preparation of Emulsion M) The emulsion L was prepared in the same manner as in the emulsion L formation except that 0.002 mol of potassium iodide aqueous solution was added at the stage of adding 90 to 91% of the total silver amount.
The shape of the obtained particles was a cube with very little roundness at the top of the particle from an electron micrograph.
(Preparation of emulsion N) K₂[IrCl₆The method for preparing Emulsion M was followed except that the transition metal complex was not added. The grain shape was the same as that of Emulsion M.
(Preparation of Emulsion P) Except for adding a silver iodide fine grain emulsion containing 0.002 mol of iodide ions at the stage of adding 90 to 95% of the total silver amount in the formation of emulsion grains, The preparation method was followed. The silver iodide fine grain emulsion used was prepared by a stirring mixer described in JP-A-10-43570. The shape of the obtained particle was a cube with very little roundness of the particle vertex from the electron micrograph.
Experiment 1 of Example 1 was performed on the above M, N, and P emulsions. As in the case of the emulsion of the present invention of Example 1, the distribution of iodide ion content inside the grains attenuated in the depth direction from the surface. showed that.
[0122]
Samples (301) to (304) were prepared by replacing the green-sensitive emulsion Em-1 in the third layer with the above emulsions L to N and P in the layer structure of Example 2. This sample was subjected to the same treatment as in Example 2, the magenta color density of each sample after the treatment was measured, and the experiments 2 and 3 of Example 2 were evaluated. These results are summarized in Table 5.
[0123]
[Table 5]

[0124]
From Table 5, it can be seen that the silver chloroiodide emulsion of the present invention is a high-sensitivity and low-fogging emulsion and has excellent latent image stability after exposure.
[0125]
Example 4
A thinned sample was prepared by changing the layer configuration as follows, and Experiments 2 and 3 of Example 1 were performed on this sample.
The layer configuration is indicated by sample (401). Samples (402) to (405) are obtained by changing the emulsion H of the sample (401) to emulsions J, K, Q, and R, respectively.
The result is the same as the result of Example 1, and from this result, the effect of the present invention was confirmed even in the ultra-rapid processing of the thinned sample.
[0126]
Preparation of sample 401
First layer (blue sensitive emulsion layer)
Emulsion H 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
[0127]
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
[0128]
Third layer (green sensitive emulsion layer)
Silver chlorobromide emulsion B (same emulsion as sample 101) 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
[0129]
Fourth layer (color mixing prevention layer)
Gelatin 0.48
Color mixing inhibitor (Cpd-4) 0.07
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-7) 0.006
UV absorber (UV-C) 0.04
Solvent (Solv-5) 0.09
[0130]
5th layer (red-sensitive emulsion layer)
Silver chlorobromide emulsion C (same emulsion as sample 101) 0.12
Gelatin 0.59
Cyan coupler (ExC-2) 0.13
Cyan coupler (ExC-3) 0.03
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-15) 0.19
Color image stabilizer (Cpd-18) 0.04
UV absorber (UV-7) 0.02
Solvent (Solv-5) 0.09
[0131]
Sixth layer (UV absorbing layer)
Gelatin 0.32
Ultraviolet absorber (UV-C) 0.42
Solvent (Solv-7) 0.08
Seventh layer (protective layer)
Gelatin 0.70
Acrylic-modified copolymer of polyvinyl alcohol
(Degree of modification 17%) 0.04
Liquid paraffin 0.01
Surfactant (Cpd-13) 0.01
Polydimethylsiloxane 0.01
Silicon dioxide 0.003
[0132]
Each of the prepared samples was exposed in the same manner as in Experiments 2 and 3 in Example 1, and the color development processing was performed in a super-rapid manner according to the development processing B shown below.
[0133]
[Process B]
The above photosensitive material is processed into a 127 mm width roll, and an experimental processing device modified from Fuji Photo Film's minilab printer processor PP350 so that the processing time and processing temperature can be changed, the average density of the photosensitive material sample is measured. Imagewise exposure was performed from the negative 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.
[0134]
Processing temperature Temperature Time Replenishment amount *
Color development 45.0 ℃ 15 seconds 45mL
Bleach fixing 40.0 ℃ 15 seconds 35mL
Rinse (1) 40.0 ° C 8 seconds
Rinse (2) 40.0 ° C 8 seconds
Rinse (3) ** 40.0 ° C 8 seconds
Rinse (4) ** 38.0 ° C 8 sec 121mL
Drying 80 ℃ 15 seconds
(note)
* Photosensitive material 1m²Replenishment amount per
** Attach a rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. to the rinse (3), take out the rinse solution from the rinse (3), and send it to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse (4), and the concentrate is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours per day. The rinsing was a 4-tank countercurrent system from (1) to (4).
[0135]
The composition of each treatment liquid is as follows.
[Color developer] [Tank solution] [Replenisher]
Water 800mL 600mL
Optical brightening agent (FL-1) 5.0 g 8.5 g
Triisopropanolamine 8.8g 8.8g
Sodium p-toluenesulfonate 20.0 g 20.0 g
Ethylenediaminetetraacetic acid 4.0 g 4.0 g
Sodium sulfite 0.10g 0.50g
Potassium chloride 10.0 g −
4,5-dihydroxybenzene-
Sodium 1,3-disulfonate 0.50 g 0.50 g
Disodium-N, N-bis (sulfonate
Ethyl) hydroxylamine 8.5 g 14.5 g
4-Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline
・ 3/2 sulfate ・ Monohydrate 10.0g 22.0g
Potassium carbonate 26.3g 26.3g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with sulfuric acid and KOH at 25 ° C.) 10.35 12.6
[0136]
[Bleaching fixer] [Tank solution] [Replenisher]
800 ml of water 800 ml
Ammonium thiosulfate (750 g / mL) 107 mL 214 mL
Succinic acid 29.5g 59.0g
Ethylenediamine tetraammonium iron (III) acetate 47.0 g 94.0 g
Ethylenediaminetetraacetic acid 1.4 g 2.8 g
Nitric acid (67%) 17.5g 35.0g
Imidazole 14.6g 29.2g
Ammonium sulfite 16.0 g 32.0 g
Potassium metabisulfite 23.1g 46.2g
Add water for a total volume of 1000 mL 1000 mL
pH (adjusted with 25 ° C, nitric acid and aqueous ammonia) 6.00 6.00
[0137]
[Rinse solution] [Tank solution] [Replenisher solution]
Chlorinated isocyanurate sodium 0.02g 0.02g
Deionized water (conductivity 5 μs / cm or less) 1000 mL 1000 mL
pH (25 ° C.) 6.5 6.5
[0138]
Embedded image

[0139]
Example 5
Images were formed by laser scanning exposure using samples (401) to (405).
As a laser light source, a YAG solid-state laser (oscillation wavelength 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength 808.5 nm) as an excitation light source is a LiNbO having an inverted domain structure._ThreeYVO using an excitation light source of 473 nm extracted by wavelength conversion with an SHG crystal and a semiconductor laser GaAlAs (oscillation wavelength 808.7 nm)_FourLiNbO with an inversion domain structure from a solid-state laser (oscillation wavelength 1064 nm)_Three532 nm extracted by wavelength conversion using SHG crystal and AlGaInP (oscillation wavelength: about 680 nm: type No. LN9R20 manufactured by Matsushita Electric Industrial Co., Ltd.) were used. The laser beams of the three colors are moved in the direction perpendicular to the scanning direction by a polygon mirror so that the sample can be sequentially scanned and exposed. The light quantity fluctuation due to the temperature of the semiconductor laser is suppressed by keeping the temperature constant using a Peltier element. The effective beam diameter is 80 μm, the scanning pitch is 42.3 μm (600 dpi), and the average exposure time per pixel is 1.7 × 10.^-7Second.
After the exposure, the color development process B was performed. As in the result of the high illuminance exposure in Example 2, the samples (402) to (405) of the present invention showed high sensitivity, and laser scanning exposure was used. It was found to be suitable for image formation.
[0140]
【The invention's effect】
  Silver halide of the present inventionColor photographic materialAs a result, an effect of high sensitivity, low fog, excellent reciprocity characteristics at high illuminance, and small sensitivity and gradation change with time until post-exposure processing was obtained.
[Brief description of the drawings]
FIG. 1 shows a graph for analysis by an etching / TOF-SIMS method.
FIG. 2 shows the content distribution of iodide ions in the depth direction in silver halide grains by TOF-SIMS method.
FIG. 3 shows the content distribution of iodide ions in the depth direction in silver halide grains by TOF-SIMS method.
FIG. 4 represents the content distribution of iodide ions in the depth direction in silver halide grains by TOF-SIMS method.
FIG. 5 shows the content distribution of iodide ions in the depth direction in silver halide grains by TOF-SIMS method.
FIG. 6 shows the content distribution of iodide ions in the depth direction in silver halide grains by TOF-SIMS method.
FIG. 7 shows the content distribution of iodide ions in the depth direction in silver halide grains by TOF-SIMS method.

Claims (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 silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is composed of silver chloroiodide grains or silver chloroiodobromide grains having a silver chloride content of 90 mol% or more. A silver halide emulsion, wherein the surface of the silver chloroiodide grains or silver chloroiodobromide grains is a silver iodide-containing layer and has a silver iodide content that attenuates in the depth direction from the grain surface And having an average grain size (average diameter of circle equivalent to the projected area of the grain) of 0.1 μm to 0.76 μm and a cube having a {100} plane Silver color photographic light-sensitive material .   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 silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is composed of silver chloroiodide grains or silver chloroiodobromide grains having a silver chloride content of 90 mol% or more. A silver halide emulsion, wherein the silver chloroiodide grains or silver chloroiodobromide grains have a layer having a silver iodide content that attenuates in the depth direction from the grain surface, over the entire surface of the silver halide grains, Silver halide color photographic light-sensitive material having an average grain size (average of diameters of circles equivalent to the projected area of grains) of 0.1 μm to 0.76 μm and a cube having {100} faces material.   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 silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is composed of silver chloroiodide grains or silver chloroiodobromide grains having a silver chloride content of 90 mol% or more. A silver halide emulsion, wherein the surface of the silver chloroiodide grains or silver chloroiodobromide grains is a silver iodide-containing layer, and the silver iodide content is attenuated exponentially in the depth direction from the grain surface A cube having an average particle size (average diameter of circle equivalent to the projected area of the particle) of 0.1 μm to 0.76 μm and having a {100} plane. Silver halide color pictures Photosensitive material.   4. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver iodide-containing layer on the grain surface is a layer made of silver iodochloride.   The average grain size (average of the diameter of a circle equivalent to the projected area of the grain) of the silver halide grains is 0.1 μm to 0.62 μm. A silver halide color photographic light-sensitive material as described in 1. The silver halide color photographic material as claimed in any one of claims 1 to 5, the introduction of iodide ions, characterized in that it is prepared in a way that ends prior to forming 98% of the particles by volume. The introduction of iodide ions is started at the outer than 80% of the particles volume, halogen according to any one of claims 1 to 5, characterized in that it is prepared in a way that ends prior to forming 98% Silver halide color photographic material. The silver halide color photographic material according to any one of claims 1 to 7 , wherein the introduction of iodide ions is carried out using silver halide fine grains containing silver iodide.   Silver halide for use in a silver halide color photographic material having 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 on a support An emulsion layer, wherein the silver halide emulsion is a silver halide emulsion composed of silver chloroiodide grains or silver chloroiodobromide grains having a silver chloride content of 90 mol% or more, and the introduction of iodide ions is a halide. A mixing vessel is provided separately from the reaction vessel for causing silver particle nucleation and / or grain growth, and an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide containing iodide ions are supplied into the mixing vessel. Using silver halide fine particles containing silver iodide formed by mixing, the silver halide fine particles are started outside 80% of the silver halide particle volume to form 98%. Prepared by the above-described method, having a layer having a silver iodide content that attenuates in the depth direction from the surface of the silver halide grain, and an average grain size (average of the diameter of the circle equivalent to the projected area of the grain) A silver halide color photographic light-sensitive material characterized in that it is a cube having a {100} plane and a thickness of 0.1 μm to 0.76 μm. The silver halide color photographic material according to claim 8 or 9 , wherein the silver halide fine particles containing silver iodide have a size of 0.001 to 0.06 µm. The silver halide color photographic material as claimed in any one of claims 1 to 10, wherein the silver chloroiodide grains or the silver chloroiodobromide grains, characterized in that it contains one or more transition metal complexes. The silver chloroiodide grains or silver chloroiodobromide grains contain one or more kinds of transition metal complexes, and the transition metal complexes have water or a 5-membered or 6-membered heterocyclic compound as a ligand. The silver halide color photographic light-sensitive material according to any one of claims 1 to 10 , wherein: The silver chloroiodide grains or silver chloroiodobromide grains are [IrCl ₅ (H ₂ O)] ²⁻ , [IrCl ₅ (H ₂ O)] ⁻ , [IrCl ₄ (H ₂ O) ₂ ] ⁻ , [IrCl ₄ (H ₂ O) ₂ ] ⁰ , [IrCl ₃ (H ₂ O) ₃ ] ⁰ , [IrCl ₃ (H ₂ O) ₃ ] ⁺ , [IrBr ₅ (H ₂ O)] ^2- , [IrBr ₅ (H ₂ O)] ^- , [IrBr ₄ (H ₂ O) ₂ ] ^- , [IrBr ₄ (H ₂ O) ₂ ] ⁰ , [IrBr ₃ (H ₂ O) ₃ ] ⁰ , [IrBr ₃ (H ₂ O) ₃ ] ⁺ , [IrCl ₅ (thiazole)] ^2- , [IrCl ₅ (5-methylthiazole)] ^2- , [IrBr ₅ (thiazole)] ^2- , [IrBr ₅ (5-methylthiazole)] ^2- and _{[IrCl 4 (thiazole) 2]} - silver halide color photographic material as claimed in any one of claims 1 to 10, characterized in that it contains a transition metal complex selected from. The silver halide color photographic material as claimed in any one of claims 1 to 13, the content of iodide ions, characterized in that at least 0.1 mol%, based on total silver of the whole emulsion grains . The content of iodide ions is 0.06 mol% or more of the total silver of the whole emulsion grains, claim 1-14, characterized in that it is spectrally sensitized with trimethinecyanine dye 2. A silver halide color photographic light-sensitive material as described in item 1. 2. The content of iodide ions is 0.06 mol% or more based on the total silver amount of all emulsion grains, and the central metal of at least one transition metal complex is ruthenium or osmium. The silver halide color photographic light-sensitive material according to any one of? 15 .

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