JP2004191806A - Silver halide photosensitive material and dot area image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photosensitive material which ensures a small variation of properties with passage of time from dispersion to coating and a small variation of performance between production lots and in each lot, is excellent in spectral absorption of a magenta dye at long wavelength and in color tone reproduction of magenta, and ensures a small color tone variation of a magenta image due to long-term storage of the silver halide photosensitive material, and to provide a dot area image forming method using the same. <P>SOLUTION: The silver halide photosensitive material has on a support a pyrazoloazole type magenta coupler-containing layer containing a silver halide emulsion having an average silver chloride content of ≥95% and a yellow coupler represented by formula (1), wherein the magenta coupler-containing layer also contains a compound represented by formula (HP). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００６５】
式中、Ｒ¹及びＲ²は各々水素原子又は置換基を表し、同一でも異なっていてもよく、また互いに結合して環を形成していてもよく、Ｘは水素原子又は発色現像主薬の酸化体とカップリングする時に脱離し得る基を表す。
【００６６】
Ｒ¹で表される置換基及びＲ²で表される置換基としては下記一般式（Ｖ）で表されるものが好ましい。
【００６７】
【化６】

【００６８】
式中、Ｒ¹¹、Ｒ¹²及びＲ¹³は各々水素原子又は置換基を表し、Ｒ¹¹、Ｒ¹²及びＲ¹³のうちの一つのみが水素原子であることはなく、また互いに結合して環を形成していてもよい。
【００６９】
前記一般式（Ｖ）におけるＲ¹¹、Ｒ¹²、及びＲ¹³で表される置換基としては特に制限はなく、アルキル、アルキニル、アルケニル、シクロアルキル、アリール、アシル、アミノ、アニリノ、アシルアミノ、カルバモイル、ウレイド、スルホニル、スルフィニル、スルホンアミド、スルファモイル、アルキルチオ、アリールチオ、シアノ、ヒドロキシ、アルコキシ、アリールオキシ、アシルオキシ、カルバモイルオキシ、スルファモイルオキシ、スルホニルオキシ、等の各基、あるいはハロゲン原子、複素環基等が挙げられ、これらの基はさらに置換可能な基で置換されていてもよい。
【００７０】
前記一般式（Ｖ）におけるＲ¹¹、Ｒ¹²及びＲ¹³として、好ましくは、水素原子、アルキル、シクロアルキル、アリール、アシル、アシルオキシ、スルホニル等の各基が挙げられる。
【００７１】
前記一般式（III）及び一般式（IV）における、Ｘで表される発色現像主薬の酸化体とカップリングするときに脱離し得る基としては、例えば、ハロゲン原子、アルコキシ、アリールオキシ、複素環オキシ、アシルオキシ、スルホニルオキシ、アルコキシカルボニル、アリールオキシカルボニル、アルキルオキザリルオキシ、アルキルチオ、アリールチオ、複素環チオ、アシルアミノ、スルホンアミド、Ｎ原子で結合した含窒素複素環、等の各基を挙げることができる。該Ｘとして、好ましくは、水素原子、ハロゲン原子、アルコキシ基、アリールオキシ基及びアリールチオ基が挙げられ、更に好ましくは水素原子、ハロゲン原子等が挙げられる。
【００７２】
以下に本発明に係るピラゾロアゾール系マゼンタカプラーの具体例を示すが、これらに限定されるものではない。
【００７３】
【化７】

【００７４】
【化８】

【００７５】
【化９】

【００７６】
【化１０】

【００７７】
【化１１】

【００７８】
【化１２】

【００７９】
【化１３】

【００８０】
【化１４】

【００８１】
【化１５】

【００８２】
【化１６】

【００８３】
【化１７】

【００８４】
本発明に係るピラゾロアゾール系マゼンタカプラーは本発明の効果を損なわない範囲において、他の種類のマゼンタカプラーと併用することもでき、通常ハロゲン化銀１モル当たり１×１０^-3モル〜１モル、好ましくは１×１０^-2モル〜８×１０^-1モルの範囲で用いることができる。
【００８５】
本発明のハロゲン化銀感光材料の特徴の一つは、一般式（Ｉ）で表されるイエローカプラーをピラゾロアゾールマゼンタカプラー含有層に含有させる事にある。
【００８６】
前記一般式（Ｉ）の式中、Ｒ₁₁で表されるアルキル基としては、例えば、メチル、エチル、ｉ−プロピル、ｔ−ブチル、ドデシル等の各基が挙げられる。これらのアルキル基は更に置換基を有してもよく、該置換基としては、例えば、ハロゲン原子、アリール基、アルコキシ基、アリールオキシ基、アルキルスルホニル基、アシルアミノ基及びヒドロキシル基等が挙げられる。Ｒ₁₁で表されるシクロアルキル基としては、シクロプロピル、シクロヘキシル及びアダマンチル等の各基が挙げられる。Ｒ₁₁で表されるアミノ基は置換アミノ基を含み、ジエチルアミノ、ジ−ｉ−オクチルアミノ、アニリノ等の各基が挙げられる。これらのアミノ基は更に置換基を有してもよく、該置換基としては、前記Ｒ₁₁で表されるアルキル基の置換基と同様の置換基が挙げられる。Ｒ₁₁で表される複素環基としては、モルホリノ基、インドリン−１−イル基等が挙げられる。Ｒ₁₁として好ましくはアルキル基であり、特にｔ−ブチル基が好ましい。
【００８７】
Ｒ₁₂が表す置換基としては、カルボキシル基、さらに更に置換されていてもよいアリールスルホニル基、スルファモイル基、オキシカルボニル基を挙げることができる。
【００８８】
Ｘ₁で表されるアルコキシ基としては、メトキシ、エトキシ、ｉ−プロポキシ、ブトキシ、デシルオキシ、ドデシルオキシ等の各基が挙げられ、アリールオキシ基としてはフェノキシ基が代表的である。
【００８９】
Ｙ₁で表されるアシルアミノ基としては、パルミトイルアミノ、ステアロイルアミノ、２−（２，４−ジ−ｔ−ペンチルフェノキシ）ブタノイルアミノ等の各基が挙げられる。
【００９０】
Ｒ₁₁、Ｘ₁及びＹ₁の何れか一つは耐拡散性基てあり、Ｒ₁₁、Ｘ₁及びＹ₁の炭素数の総和が１２以上であることが好ましい。
【００９１】
以下に一般式（Ｉ）で表されるイエローカプラーの具体例を挙げるが本発明はこれに限定されるものではない。
【００９２】
【化１８】

【００９３】
【化１９】

【００９４】
【化２０】

【００９５】
請求項３または４に記載の発明の特徴の一つは、更に一般式（II）で表されるイエローカプラーをマゼンタ画像形成層に含有させる事にある。
【００９６】
前記一般式（II）の式中、Ｒ₂₁で表される基としては前記一般式（Ｉ）のＲ₁₁と同じものが挙げられる。
【００９７】
Ｒ₂₂で表される炭素数２以上の直鎖又は分岐の無置換アルキル基としては、例えば、エチル、プロピル、ｉ−プロピル、ブチル、ヘキシル等の各基が挙げられる。好ましくは直鎖の無置換アルキル基であり、更に好ましくは炭素数４以上の直鎖の無置換アルキル基である。
【００９８】
Ｘ₂で表されるアルコキシ基又はアリールオキシ基としては、前記一般式（Ｉ）のＸ₁と同じものが挙げられる。
【００９９】
Ｙ₂で表されるアシルアミノ基としては、前記一般式（Ｉ）のＹ₁と同じものが挙げられる。
【０１００】
Ｒ₂₁、Ｘ₂及びＹ₂の何れか一つは耐拡散性基てあり、Ｒ₂₁、Ｘ₂及びＹ₂の炭素数の総和が１２以上であることが好ましい。
【０１０１】
以下に一般式（II）で表されるイエローカプラーの具体例を挙げるが本発明はこれに限定されるものではない。
【０１０２】
【化２１】

【０１０３】
【化２２】

【０１０４】
【化２３】

【０１０５】
【化２４】

【０１０６】
本発明のハロゲン化銀感光材料においてシアン画像形成層中に含有されるシアンカプラーとしては、公知のフェノール系、ナフトール系又はイミダゾール系、アゾール系カプラーを用いることができる。例えば、アルキル基、アシルアミノ基、或いはウレイド基などを置換したフェノール系カプラー、５−アミノナフトール骨格から形成されるナフトール系カプラー、離脱基として酸素原子を導入した２当量型ナフトール系カプラーなどが代表される。このうち好ましい化合物としては特開平６−９５２８３号１３ページ記載の一般式［Ｃ−Ｉ］、［Ｃ−II］が挙げられる。アゾール系カプラーとしては特開平８−１７１１８５号２ページ記載の一般式〔Ｉ〕もしくは〔II〕で表されるカプラーを挙げることができる。
【０１０７】
該シアンカプラーは通常ハロゲン化銀乳剤層において、ハロゲン化銀１モル当たり１×１０^-3〜１モル、好ましくは１×１０^-2〜８×１０^-1モルの範囲で用いることができる。
【０１０８】
本発明のハロゲン化銀感光材料においてイエロー画像形成層中に含有されるイエローカプラーとしては、公知のアシルアセトアニリド系カプラー等を好ましく用いることができる。
【０１０９】
該イエローカプラーの具体例としては、例えば特開平３−２４１３４５号の５頁〜９頁に記載の化合物、Ｙ−Ｉ−１〜Ｙ−Ｉ−５５で表される化合物、もしくは特開平３−２０９４６６号の１１〜１４頁に記載の化合物、Ｙ−１〜Ｙ−３０で示される化合物、特開平６−９５２８３号２１ページ記載の一般式〔Ｙ−Ｉ〕で表される化合物、特開平１０−１８６６０１号２ページ記載の一般式〔Ｉ〕もしくは〔II〕で表される化合物、特開２０００−１１２０９０号２ページ記載の一般式〔Ｉ〕で表されるカプラーを挙げることができる。
【０１１０】
本発明のハロゲン化銀感光材料により形成されるイエロー画像の分光吸収のλｍａｘは４２５ｎｍ以上であることが好ましく、λＬ０．２は５１５ｎｍ以下であることが好ましい。λＬ０．２とは、画像色素の分光吸光度曲線において、最大吸光度が１．０である時、最大吸光度を示す波長よりも長波で、吸光度が０．２となる波長をいう。この量は画像色素の長波側の不要吸収の大きさを示す目安となる量であり、λｍａｘに近い波長であるほど不要吸収が小さく好ましいことを表す。
【０１１１】
該イエローカプラーは通常ハロゲン化銀乳剤層において、ハロゲン化銀１モル当たり１×１０^-3〜１モル、好ましくは１×１０^-2〜８×１０^-1モルの範囲で用いることができる。
【０１１２】
請求項１または３に記載の発明の特徴の一つは、マゼンタカプラー含有層に前記一般式（ＨＰ）で表される化合物を含有することにある。
【０１１３】
一般式（ＨＰ）において、Ｒ₁は３級アルキル基（例えばｔ−ブチル基、ｔ−ペンチル基、ｔ−オクチル基等）を示し、好ましくはｔ−ブチル基である。Ｒ₂は１級または２級アルキル基（例えばメチル基、エチル基、イソプロピル基等）を表し、好ましくはメチル基である。但し、Ｒ₂は置換基により置換されていてもよいが、フェニル基によって置換されることはない。Ｒ₃、Ｒ₄及びＲ₅はアルキル基（例えばメチル基、エチル基、ブチル基、ドデシル基等）アルコキシカルボニル基（例えば、エトキシカルボニル基等）、フェノキシカルボニル基（例えば、２，４−ジ−ｔ−ブチルフェノキシカルボニル基等）、アルコキシ基（例えば、２−エチルヘキシルオキシ基等）、フェノキシ基（例えば４−（２−エチルヘキシル）フェノキシ基、４−ドデシル−フェノキシ基等）、フェニルチオ基（例えば３−ｔブチル、４−ヒドロキシ、５−メチルフェニルチオ基等）を表す。
【０１１４】
又、上記Ｒ₁ないしＲ₅で表される基は、置換基により置換されていても良い。又、一般式（ＨＰ）で表される化合物は、構造式中に１級、２級または３級アミノ基を含有しない化合物または、アシルアミノ基を含有しない化合物であり、さらには構造式中に、１級、２級または３級アミノ基を含有しない化合物がより好ましい。またＲ₄で表される基がアルキル基であることが好ましい。
【０１１５】
Ｒ₄で表される基は、下記の連結基を含む基であることが、より好ましい。
【０１１６】
【化２５】

【０１１７】
（式中、Ｒ₆、Ｒ₆′、Ｒ₇、Ｒ₇′、Ｒ₈、Ｒ₈′、Ｒ₉及びＲ₉′は各々水素原子、アルキル基、フェニル基を表す。）
一般式（ＨＰ）で表される化合物のうち、好ましい化合物としては下記一般式（ＨＰ−Ａ）及び（ＨＰ−Ｂ）で表される化合物である。
【０１１８】
【化２６】

【０１１９】
式中、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅は一般式（ＨＰ）のＲ₁ないしＲ₅と同義である。Ｒ₁₁はアルキレン基（例えばエチレン基、イソブチレン基）を表す。
【０１２０】
一般式（ＨＰ）で表される化合物のうち、より好ましい化合物は下記一般式（ＨＰ−ａ）及び（ＨＰ−ｂ）で表される化合物である。
【０１２１】
【化２７】

【０１２２】
上記一般式（ＨＰ−ａ）及び（ＨＰ−ｂ）において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₅は一般式（ＨＰ−Ａ）及び（ＨＰ−Ｂ）のＲ₁ないしＲ₅と同義であり、Ｒ₁₁及びＲ₁₂は一般式（ＨＰ−Ａ）のＲ₁₁と同義である。
【０１２３】
一般式（ＨＰ）で表される化合物は、他の退色防止剤と併用することもできる。
【０１２４】
次に、一般式（ＨＰ）で表される化合物の具体例を示すが、本発明はこれらに限定されるものではない。
【０１２５】
【化２８】

【０１２６】
【化２９】

【０１２７】
【化３０】

【０１２８】
【化３１】

【０１２９】
【化３２】

【０１３０】
一般式（ＨＰ）で表される化合物はマゼンタカプラー１モルあたり１×１０^-3〜１モルの量で含有することが好ましい。
【０１３１】
請求項２または４に記載の発明の特徴の一つは、前記一般式（Ｕ）で表される化合物をピラゾロアゾール系マゼンタカプラー含有層に含有することにある。
【０１３２】
前記一般式（Ｕ）において、Ｒ_U1は水素原子、ハロゲン原子、アルコキシ基が好ましく、Ｒ_U2及びＲ_U3は各々、水素原子、アルキル基が好ましく、Ｒ_U4は水素原子、アルコキシ基、アシルアミノ基、ウレイド基が好ましい。
【０１３３】
以下に、一般式（Ｕ）で表される化合物（紫外線吸収剤）の具体的化合物例を挙げるが、本発明はこれらに限定されない。
【０１３４】
【化３３】

【０１３５】
【化３４】

【０１３６】
前記一般式（Ｕ）の化合物は、その融点が−５０〜１３０℃であることが好ましく、より好ましくは−５０〜１００℃である。また、一般式（Ｕ）の化合物はマゼンタカプラー１モルあたり１×１０^-3〜１モルの量で含有することが好ましい。
【０１３７】
該マゼンタ色画像、シアン色画像、及びイエロー色画像の分光吸収特性を調整するために、色調調整作用を有する化合物を添加する事が好ましい。このための化合物としては、特開平６−９５２８３号２２ページ記載の一般式［ＨＢＳ−Ｉ］に記載されるリン酸エステル系化合物、［ＨＢＳ−II］で示されるホスフィンオキサイド系化合物が好ましく、より好ましくは同号２２ページ記載の一般式［ＨＢＳ−II］で示される化合物である。
【０１３８】
本発明のハロゲン化銀感光材料においてハロゲン化銀乳剤層は支持体上に積層塗布されるが支持体からの順番はどのような順番でもよい。この他に必要に応じ中間層、フィルター層、保護層等を配置することができる。
【０１３９】
前記マゼンタ、シアン、イエローの各カプラーには、形成された色素画像の光、熱、湿度等による褪色を防止するため褪色防止剤を併用することができる。好ましい化合物としては、特開平２−６６５４１号３ページ記載の一般式ＩおよびIIで示されるフェニルエーテル系化合物、特開平３−１７４１５０号記載の一般式IIIＢで示されるフェノール系化合物、特開平６４−９０４４５号記載の一般式Ａで示されるアミン系化合物、特開昭６２−１８２７４１号記載の一般式XII、XIII、XIV、XVで示される金属錯体が特にマゼンタ色素用として好ましい。また特開平１−１９６０４９号記載の一般式Ｉ’で示される化合物および特開平５−１１４１７号記載の一般式IIで示される化合物が特にイエロー、シアン色素用として好ましい。
【０１４０】
本発明のハロゲン化銀感光材料に用いられるステイン防止剤やその他の有機化合物を添加するのに水中油滴型乳化分散法を用いる場合には、通常、沸点１５０℃以上の水不溶性高沸点有機溶媒に、必要に応じて低沸点及び／または水溶性有機溶媒を併用して溶解し、ゼラチン水溶液などの親水性バインダー中に界面活性剤を用いて乳化分散する。分散手段としては、撹拌機、ホモジナイザー、コロイドミル、フロージェットミキサー、超音波分散機等を用いることができる。分散後、または、分散と同時に低沸点有機溶媒を除去する工程を入れてもよい。ステイン防止剤等を溶解して分散するために用いることの出来る高沸点有機溶媒としては、トリクレジルホスフェート、トリオクチルホスフェート等のリン酸エステル類、トリオクチルホスフィンオキサイド等のホスフィンオキサイド類、特開平４−２６５，９７５号５ページ記載の（ａ−ｉ）〜（ａ−ｘ）を代表とする高級アルコール系化合物等が好ましく用いられる。また高沸点有機溶媒の誘電率としては３．５〜７．０である事が好ましい。また二種以上の高沸点有機溶媒を併用することもできる。
【０１４１】
本発明の感光材料に用いられる写真用添加剤の分散や塗布時の表面張力調整のため用いられる界面活性剤として好ましい化合物としては、１分子中に炭素数８〜３０の疎水性基とスルホン酸基またはその塩を含有するものが挙げられる。具体的には特開昭６４−２６８５４号記載のＡ−１〜Ａ−１１が挙げられる。またアルキル基に弗素原子を置換した界面活性剤も好ましく用いられる。これらの分散液は通常ハロゲン化銀乳剤を含有する塗布液に添加されるが、分散後塗布液に添加されるまでの時間、および塗布液に添加後塗布までの時間は短いほうがよく各々１０時間以内が好ましく、３時間以内、２０分以内がより好ましい。
【０１４２】
本発明のハロゲン化銀感光材料には、現像主薬酸化体と反応する化合物を感光層と感光層の間の層に添加して色濁りを防止したりまたハロゲン化銀乳剤層に添加してカブリ等を改良する事が好ましい。このための化合物としてはハイドロキノン誘導体が好ましく、さらに好ましくは２，５−ジ−ｔ−オクチルハイドロキノンのようなジアルキルハイドロキノンである。特に好ましい化合物は特開平４−１３３０５６号記載の一般式IIで示される化合物であり、同号１３〜１４ページ記載の化合物II−１〜II−１４および１７ページ記載の化合物１が挙げられる。
【０１４３】
本発明の感光材料中には紫外線吸収剤を添加してスタチックカブリを防止したり色素画像の耐光性を改良することが好ましい。好ましい紫外線吸収剤としてはベンゾトリアゾール類が挙げられ、特に好ましい化合物としては特開平１−２５０９４４号記載の一般式III−３で示される化合物、特開昭６４−６６６４６号記載の一般式IIIで示される化合物、特開昭６３−１８７２４０号記載のＵＶ−１Ｌ〜ＵＶ−２７Ｌ、特開平４−１６３３号記載の一般式Ｉで示される化合物、特開平５−１６５１４４号記載の一般式（Ｉ）、（II）で示される化合物が挙げられる。
【０１４４】
本発明の感光材料には、油溶性染料や顔料を含有すると白地性が改良され好ましい。油溶性染料の代表的具体例は、特開平２−８４２号８ページ〜９ページに記載の化合物１〜２７が挙げられる。
【０１４５】
本発明のハロゲン化銀感光材料には、バインダーとしてゼラチンを用いることが有利であるが、必要に応じて他のゼラチン、ゼラチン誘導体、ゼラチンと他の高分子のグラフトポリマー、ゼラチン以外のタンパク質、糖誘導体、セルロース誘導体、単一あるいは共重合体のごとき合成親水性高分子物質等の親水性コロイドも用いることができる。
【０１４６】
これらバインダーの硬膜剤としてはビニルスルホン型硬膜剤やクロロトリアジン型硬膜剤を単独または併用して使用する事が好ましい。特開昭６１−２４９０５４号、同６１−２４５１５３号記載の化合物を使用する事が好ましい。また写真性能や画像保存性に悪影響するカビや細菌の繁殖を防ぐためコロイド層中に特開平３−１５７６４６号記載のような防腐剤および抗カビ剤を添加する事が好ましい。また感光材料または処理後の試料の表面の物性を改良するため保護層に特開平６−１１８５４３号や特開平２−７３２５０号記載の滑り剤やマット剤を添加する事が好ましい。
【０１４７】
本発明の感光材料に用いる支持体としては、どのような材質を用いてもよく、ポリエチレンやポリエチレンテレフタレートで被覆した紙、天然パルプや合成パルプからなる紙支持体、塩化ビニルシート、白色顔料を含有してもよいポリプロピレン、ポリエチレンテレフタレート支持体、バライタ紙などを用いることができる。なかでも、原紙の両面に耐水性樹脂被覆層を有する支持体が好ましい。耐水性樹脂としてはポリエチレンやポリエチレンテレフタレートまたはそれらのコポリマーが好ましい。
【０１４８】
紙の表面に耐水性樹脂被覆層を有する支持体は、通常、５０〜３００ｇ／ｍ²の質量を有する表面の平滑なものが用いられるが、プルーフ画像を得る目的に対しては、取り扱いの感覚を印刷用紙に近づけるため、１３０ｇ／ｍ²以下の原紙が好ましく用いられ、さらに７０〜１２０ｇ／ｍ²の原紙が好ましく用いられる。
【０１４９】
本発明に用いられる支持体としては、ランダムな凹凸を有するものであっても平滑なものであっても好ましく用いることができる。
【０１５０】
支持体に用いられる白色顔料としては、無機及び／または有機の白色顔料を用いることができ、好ましくは無機の白色顔料が用いられる。例えば硫酸バリウム等のアルカリ土類金属の硫酸塩、炭酸カルシウム等のアルカリ土類金属の炭酸塩、微粉ケイ酸、合成ケイ酸塩等のシリカ類、ケイ酸カルシウム、アルミナ、アルミナ水和物、酸化チタン、酸化亜鉛、タルク、クレイ等が挙げられる。白色顔料は好ましくは硫酸バリウム、酸化チタンである。
【０１５１】
支持体の表面の耐水性樹脂層中に含有される白色顔料の量は、鮮鋭性を改良するうえで１３質量％以上が好ましく、さらには１５質量％が好ましい。
【０１５２】
本発明に係る紙支持体の耐水性樹脂層中の白色顔料の分散度は、特開平２−２８６４０号に記載の方法で測定することができる。この方法で測定したときに、白色顔料の分散度が前記公報に記載の変動係数として０．２０以下であることが好ましく、０．１５以下であることがより好ましい。
【０１５３】
本発明に用いられる両面に耐水性樹脂層を有する紙支持体の樹脂層は、１層であってもよいし、複数層からなってもよい。複数層とし、乳剤層と接する方に白色顔料を高濃度で含有させると鮮鋭性の向上が大きく、プルーフ用画像を形成するのに好ましい。
【０１５４】
また支持体の中心面平均粗さ（ＳＲａ）の値が０．１５μｍ以下、さらには０．１２μｍ以下であるほうが光沢性がよいという効果が得られより好ましい。
【０１５５】
本発明の感光材料は、必要に応じて支持体表面にコロナ放電、紫外線照射、火炎処理等を施した後、直接または下塗層（支持体表面の接着性、帯電防止性、寸度安定性、耐摩擦性、硬さ、ハレーション防止性、摩擦特性及び／またはその他の特性を向上するための１または２以上の下塗層）を介して塗布されていてもよい。
【０１５６】
ハロゲン化銀乳剤を用いた感光材料の塗布に際して、塗布性を向上させるために増粘剤を用いてもよい。塗布法としては２種以上の層を同時に塗布することの出来るエクストルージョンコーティング及びカーテンコーティングが特に有用である。
【０１５７】
本発明に用いられる露光装置の露光光源は、公知のものをいずれも好ましく用いることが出来るが、レーザーまたは発光ダイオード（以下ＬＥＤと表す）がより好ましく用いられる。
【０１５８】
レーザーとしては半導体レーザー（以下、ＬＤと表す）がコンパクトであること、光源の寿命が長いことから好ましく用いられる。また、ＬＤはＤＶＤ、音楽用ＣＤの光ピックアップ、ＰＯＳシステム用バーコードスキャナ等の用途や光通信等の用途に用いられており、安価であり、かつ比較的高出力のものが得られるという長所を有している。ＬＤの具体的な例としては、アルミニウム・ガリウム・インジウム・ヒ素（６５０ｎｍ）、インジウム・ガリウム・リン（〜７００ｎｍ）、ガリウム・ヒ素・リン（６１０〜９００ｎｍ）、ガリウム・アルミニウム・ヒ素（７６０〜８５０ｎｍ）等を挙げることができる。最近では、青光を発振するレーザーも開発されているが、現状では、６１０ｎｍよりも長波の光源としてＬＤを用いるのが有利である。
【０１５９】
ＳＨＧ素子を有するレーザー光源としては、ＬＤ、ＹＡＧレーザーから発振される光をＳＨＧ素子により半分の波長の光に変換して放出させるものであり、可視光が得られることから適当な光源がない緑〜青の領域の光源として用いられる。この種の光源の例としては、ＹＡＧレーザーにＳＨＧ素子を組み合わせたもの（５３２ｎｍ）等がある。
【０１６０】
ガスレーザーとしては、ヘリウム・カドミウムレーザー（約４４２ｎｍ）、アルゴンイオンレーザー（約５１４ｎｍ）、ヘリウムネオンレーザー（約５４４ｎｍ、６３３ｎｍ）等が挙げられる。
【０１６１】
ＬＥＤとしては、ＬＤと同様の組成をもつものが知られているが、青〜赤外まで種々のものが実用化されている。
【０１６２】
本発明に用いられる露光光源としては、各レーザーを単独で用いてもよいし、これらを組合せ、マルチビームとして用いてもよい。ＬＤの場合には、例えば１０個のＬＤを並べることにより１０本の光束からなるビームが得られる。一方、ヘリウムネオンレーザーのような場合、レーザーから発した光をビームセパレーターで例えば１０本の光束に分割する。
【０１６３】
露光用光源の強度変化は、ＬＤ、ＬＥＤのような場合には、個々の素子に流れる電流値を変化させる直接変調を行うことができる。ＬＤの場合には、ＡＯＭ（音響光学変調器）のような素子を用いて強度を変化させてもよい。ガスレーザーの場合には、ＡＯＭ、ＥＯＭ（電気光学変調器）等のデバイスを用いるのが一般である。
【０１６４】
光源にＬＥＤを用いる場合には、光量が弱ければ、複数の素子で同一の画素を重複して露光する方法を用いてもよい。
【０１６５】
また、これらに代わる光源として有機発光素子を用いてもよく、これらについては、例えば、特開２０００−２５８８４６号等に記載されている。
【０１６６】
本願発明において面積階調画像とは、画像上の濃淡を個々の画素の色の濃淡で表現するのではなく、特定の濃度に発色した部分の面積の大小で表現するものであり、網点と同義である。
【０１６７】
通常面積階調露光であればＹ、Ｍ、Ｃ、墨の発色をさせることで目的を達することもできる。より好ましくは、墨に加えてＭ、Ｃ等の単色が発色したことを識別するには、３値以上の露光量を使い分けて露光する事が好ましい。印刷においては、特別な色の版を用いることがあるが、これを再現するためには、４値以上の露光量を使い分けて露光する事が好ましい。
【０１６８】
デジタルデータに基づき面積階調画像を形成するシステムでは、網点をさらに小さな単位（ここではこれをドットと表現した）に分割し、この画素を適切な露光量で露光する事によってその集合体として網点を再現することが可能である。例えとして簡単な例を挙げれば、１つの網点が１００個のドットで構成されるのであれば、５０個のドットを現像可能なように露光する事により網％が５０％の網点を形成する事ができる。
【０１６９】
本発明のハロゲン化銀感光材料は、上記デジタルデータに基づく面積階調画像の形成に対して好ましく用いることができる。この方式においては、比較的高濃度の領域を使用するため、発色性の低下は特性に大きな影響を与える。また、このような系では高照度短時間露光が行われるためハロゲン化銀乳剤の特性としても高濃度域で濃度が出にくい。このため、このようなデジタルカラープルーフでは本発明の効果を好ましく用いることができる。
【０１７０】
レーザー光源の場合には、ビーム径は２５μｍ以下であることが好ましく、６〜２２μｍがより好ましい。６μｍより小さいと画質的には好ましいが、調整が困難であったり、処理速度が低下したりする。一方、２５μｍより大きいとムラが大きくなり、画像の鮮鋭性も劣化する。ビーム径を最適化する事によってムラのない高精細の画像の書き込みを高速で行うことができる。
【０１７１】
このような光で画像を描くには、ハロゲン化銀感光材料上を光束が走査する必要があるが、感光材料を円筒状のドラムに巻き付けこれを高速に回転しながら回転方向に直角な方向に光束を動かす円筒外面走査方式をとってもよく、円筒状の窪みにハロゲン化銀感光材料を密着させて露光する円筒内面走査方式も好ましく用いることができる。多面体ミラーを高速で回転させこれによって搬送されるハロゲン化銀感光材料を搬送方向に対して直角に光束を移動して露光する平面走査方式をとってもよい。高画質であり、かつ大きな画像を得るには円筒外面走査方式がより好ましく用いられる。
【０１７２】
円筒外面走査方式での露光を行うには、ハロゲン化銀感光材料は正確に円筒状のドラムに密着されなければならない。これが的確に行われるためには、正確に位置合わせされて搬送される必要がある。ハロゲン化銀感光材料は露光する側の面が外側に巻かれたものがより的確に位置合わせでき、好ましく用いることができる。同様な観点から、ハロゲン化銀感光材料に用いられる支持体は適正な剛度があり、テーバー剛度で０．８〜４．０が好ましい。
【０１７３】
ドラム径は、露光するハロゲン化銀感光材料の大きさに適合させて任意に設定することができる。ドラムの回転数も任意に設定できるがレーザー光のビーム径、エネルギー強度、書き込みパターンや感光材料の感度などにより適当な回転数を選択することができる。生産性の観点からは、より高速な回転で走査露光できる方が好ましいが、具体的には１分間に２００〜３０００回転が好ましく用いられる。
【０１７４】
ドラムへのハロゲン化銀感光材料の固定方法は、機械的な手段によって固定させてもよいし、ドラム表面に吸引できる微小な穴を感光材料の大きさに応じて多数設けておき、感光材料を吸引して密着させることもできる。感光材料をドラムにできるだけ密着させることが画像ムラ等のトラブルを防ぐには重要である。
【０１７５】
本発明において用いられる芳香族一級アミン現像主薬としては、公知の化合物を用いることができる。これらの化合物の例として下記の化合物を挙げることができる。
ＣＤ−１） Ｎ，Ｎ−ジエチル−ｐ−フェニレンジアミン
ＣＤ−２） ２−アミノ−５−ジエチルアミノトルエン
ＣＤ−３） ２−アミノ−５−（Ｎ−エチル−Ｎ−ラウリルアミノ）トルエン
ＣＤ−４） ４−（Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アミノ）アニリン
ＣＤ−５） ２−メチル−４−（Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アミノ）アニリン
ＣＤ−６） 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
ＣＤ−７） Ｎ−（２−アミノ−５−ジエチルアミノフェニルエチル）メタンスルホンアミド
ＣＤ−８） Ｎ，Ｎ−ジメチル−ｐ−フェニレンジアミン
ＣＤ−９） ４−アミノ−３−メチル−Ｎ−エチル−Ｎ−メトキシエチルアニリン
ＣＤ−１０） ４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−エトキシエチル）アニリン
ＣＤ−１１） ４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（γ−ヒドロキシプロピル）アニリン
本発明においては、上記は色現像液を任意のｐＨ域で使用できるが、迅速処理の観点からｐＨ９．５〜１３．０であることが好ましく、より好ましくはｐＨ９．８〜１２．０の範囲で用いられる。
【０１７６】
発色現像の処理温度は、３５℃以上、７０℃以下が好ましい。温度が高いほど短時間の処理が可能であり好ましいが、処理液の安定性からはあまり高くない方が好ましく、３７℃以上６０℃以下で処理することが好ましい。
【０１７７】
発色現像時間は、従来一般には３分３０秒程度で行われているが、本発明では４０秒以内が好ましく、さらに２５秒以内の範囲で行うことがさらに好ましい。
【０１７８】
発色現像液には、前記の発色現像主薬に加えて、既知の現像液成分化合物を添加することが出来る。通常、ｐＨ緩衝作用を有するアルカリ剤、塩化物イオン、ベンゾトリアゾール類等の現像抑制剤、保恒剤、キレート剤などが用いられる。
【０１７９】
ハロゲン化銀感光材料は、発色現像後、漂白処理及び定着処理を施される。漂白処理は定着処理と同時に行なってもよい。定着処理の後は、通常は水洗処理が行なわれる。また、水洗処理の代替として、安定化処理を行なってもよい。
【０１８０】
ハロゲン化銀感光材料の現像処理に用いる現像処理装置としては、処理槽に配置されたローラーに感光材料をはさんで搬送するローラートランスポートタイプであっても、ベルトに感光材料を固定して搬送するエンドレスベルト方式であってもよいが、処理槽をスリット状に形成して、この処理槽に処理液を供給するとともに感光材料を搬送する方式や処理液を噴霧状にするスプレー方式、処理液を含浸させた担体との接触によるウエッブ方式、粘性処理液による方式なども用いることができる。大量に処理する場合には、自動現像機を用いてランニング処理されるのが、通常だがこの際、補充液の補充量は少ない程好ましく、環境適性等より最も好ましい処理形態は、補充方法として錠剤の形態で処理剤を添加することであり、公開技報９４−１６９３５に記載の方法が最も好ましい。
【０１８１】
【実施例】
以下、実施例を挙げて本発明を具体的に説明するが、本発明の態様はこれに限定されない。
【０１８２】
実施例１
片面に高密度ポリエチレンを、もう一方の面にアナターゼ型酸化チタンを１５質量％の含有量で分散して含む溶融ポリエチレンをラミネートした、１ｍ²当たりの質量が１１５ｇのポリエチレンラミネート紙反射支持体（テーバー剛度＝３．５、ＰＹ値＝２．７μｍ）上に、下記表１に示す層構成の各層を酸化チタンを含有するポリエチレン層の側に塗設し、更に裏面側にはゼラチン６．００ｇ／ｍ²、シリカマット剤０．６５ｇ／ｍ²を塗設した多層ハロゲン化銀感光材料試料Ｎｏ．１０１を作製した。
【０１８３】
カプラーは高沸点溶媒に溶解して超音波分散し、分散物として添加したが、この時、界面活性剤として（ＳＵ−１）を用いた。又、硬膜剤として（Ｈ−１）、（Ｈ−２）を添加した。塗布助剤としては、界面活性剤（ＳＵ−２）、（ＳＵ−３）を添加し、表面張力を調整した。また各層に（Ｆ−１）を全量が０．０４ｇ／ｍ²となるように添加した。
【０１８４】
【表１】

【０１８５】
ＳＵ−１：トリ−ｉ−プロピルナフタレンスルホン酸ナトリウム
ＳＵ−２：スルホ琥珀酸ジ（２−エチルヘキシル）・ナトリウム塩
ＳＵ−３：スルホ琥珀酸ジ（２，２，３，３，４，４，５，５−オクタフルオロペンチル）・ナトリウム塩
Ｈ−１：テトラキス（ビニルスルホニルメチル）メタン
Ｈ−２：２，４−ジクロロ−６−ヒドロキシ−ｓ−トリアジン・ナトリウム
ＨＱ−１：２，５−ジ−ｔ−オクチルハイドロキノン
ＨＱ−２：２，５−ジ（（１，１−ジメチル−４−ヘキシルオキシカルボニル）ブチル）ハイドロキノン
ＨＱ−３：２，５−ジ−ｓｅｃ−ドデシルハイドロキノンと２，５−ジ−ｓｅｃテトラデシルハイドロキノンと２−ｓｅｃ−ドデシル−５−ｓｅｃ−テトラデシルハイドロキノンの質量比１：１：２の混合物
ＳＯ−１：トリオクチルホスフィンオキサイド
ＳＯ−２：ジ（ｉ−デシル）フタレート
ＳＯ−３：オレイルアルコール
ＳＯ−４：トリクレジルホスフェート
ＰＶＰ：ポリビニルピロリドン
【０１８６】
【化３５】

【０１８７】
【化３６】

【０１８８】
【化３７】

【０１８９】
（青感光性ハロゲン化銀乳剤の調製）
４０℃に保温した２％ゼラチン水溶液１リットル中に下記（Ａ液）及び（Ｂ液）をｐＡｇ＝７．３、ｐＨ＝３．０に制御しつつ同時添加し、更に下記（Ｃ液）及び（Ｄ液）をｐＡｇ＝８．０、ｐＨ＝５．５に制御しつつ同時添加した。この時、ｐＡｇの制御は特開昭５９−４５４３７号記載の方法により行い、ｐＨの制御は硫酸又は水酸化ナトリウム水溶液を用いて行った。
（Ａ液）
塩化ナトリウム ３．４２ｇ
臭化カリウム ０．０３ｇ
水を加えて ２００ｍｌ
（Ｂ液）
硝酸銀 １０ｇ
水を加えて ２００ｍｌ
（Ｃ液）
塩化ナトリウム １０２．７ｇ
ヘキサクロロイリジウム（IV）酸カリウム ４×１０^-8モル
ヘキサシアノ鉄（II）酸カリウム ２×１０^-5モル
臭化カリウム １．０ｇ
水を加えて ６００ｍｌ
（Ｄ液）
硝酸銀 ３００ｇ
水を加えて ６００ｍｌ
添加終了後、花王アトラス社製デモールＮの５％水溶液と硫酸マグネシウムの２０％水溶液を用いて脱塩を行った後、ゼラチン水溶液と混合して平均粒径０．７１μｍ、粒径分布の変動係数０．０７、塩化銀含有率９９．５モル％の単分散立方体乳剤ＥＭＰ−１０１を得た。
【０１９０】
上記（ＥＭＰ−１０１）に対し、下記化合物を用い６０℃にて最適に化学増感を行い、青感光性ハロゲン化銀乳剤（Ｅｍ−Ｂ１０１）を得た。
【０１９１】
チオ硫酸ナトリウム ０．８ｍｇ／モルＡｇＸ
塩化金酸 ０．５ｍｇ／モルＡｇＸ
安定剤ＳＴＡＢ−１ ３×１０^-4モル／モルＡｇＸ
安定剤ＳＴＡＢ−２ ３×１０^-4モル／モルＡｇＸ
安定剤ＳＴＡＢ−３ ３×１０^-4モル／モルＡｇＸ
増感色素ＢＳ−１ ４×１０^-4モル／モルＡｇＸ
増感色素ＢＳ−２ １×１０^-4モル／モルＡｇＸ
臭化カリウム ０．２ｇ／モルＡｇＸ
次いでＥＭＰ−１０１の調製において、（Ａ液）と（Ｂ液）の添加時間および（Ｃ液）と（Ｄ液）の添加時間を変更した以外はＥＭＰ−１０１と同様にして平均粒径０．６４μｍ、粒径分布の変動係数０．０７、塩化銀含有率９９．５モル％の単分散立方体乳剤ＥＭＰ−１０２を得た。Ｅｍ−Ｂ１０１の調製においてＥＭＰ−１０１に代えてＥＭＰ−１０２を用いた以外同様にしてＥｍ−Ｂ１０２を得、Ｅｍ−Ｂ１０１と１０２の１：１の混合物を青感光性ハロゲン化銀乳剤として使用した。
【０１９２】
（緑感光性ハロゲン化銀乳剤の調製）
ＥＭＰ−１０１の調製において（Ａ液）及び（Ｂ液）、（Ｃ液）及び（Ｄ液）の添加時間を変更した以外は同様にして平均粒径０．４０μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体乳剤（ＥＭＰ−１０３）を得た。
【０１９３】
上記ＥＭＰ−１０３に対し、下記化合物を用い５５℃にて最適に化学増感を行い、緑感光性ハロゲン化銀乳剤（Ｅｍ−Ｇ１０１）を得た。
【０１９４】
チオ硫酸ナトリウム １．５ｍｇ／モルＡｇＸ
塩化金酸 １．０ｍｇ／モルＡｇＸ
安定剤ＳＴＡＢ−１ ３×１０^-4モル／モルＡｇＸ
安定剤ＳＴＡＢ−２ ３×１０^-4モル／モルＡｇＸ
安定剤ＳＴＡＢ−３ ３×１０^-4モル／モルＡｇＸ
増感色素ＧＳ−１ ２×１０^-4モル／モルＡｇＸ
増感色素ＧＳ−２ ２×１０^-4モル／モルＡｇＸ
塩化ナトリウム ０．５ｇ／モルＡｇＸ
次いでＥＭＰ−１０３の調製において、（Ａ液）と（Ｂ液）の添加時間および（Ｃ液）と（Ｄ液）の添加時間を変更した以外はＥＭＰ−１０３と同様にして平均粒径０．５０μｍ、変動係数０．０８、塩化銀含有率９９．５％の単分散立方体乳剤ＥＭＰ−１０４を得た。Ｅｍ−Ｇ１０１の調製においてＥＭＰ−１０３に代えてＥＭＰ−１０４を用いた以外同様にしてＥｍ−Ｇ１０２を得、Ｅｍ−Ｇ１０１と１０２の１：１の混合物を緑感光性ハロゲン化銀乳剤として使用した。
【０１９５】
（赤感光性ハロゲン化銀乳剤の調製）
前記ＥＭＰ−１０３に対し、下記化合物を用い６０℃にて最適に化学増感を行い、赤感光性ハロゲン化銀乳剤（Ｅｍ−Ｒ１０１）を得た。
【０１９６】
チオ硫酸ナトリウム １．８ｍｇ／モルＡｇＸ
塩化金酸 ２．０ｍｇ／モルＡｇＸ
安定剤ＳＴＡＢ−１ ２×１０^-4モル／モルＡｇＸ
安定剤ＳＴＡＢ−２ ２×１０^-4モル／モルＡｇＸ
安定剤ＳＴＡＢ−３ ２×１０^-4モル／モルＡｇＸ
安定剤ＳＴＡＢ−４ １×１０^-4モル／モルＡｇＸ
増感色素ＲＳ−１ １×１０^-4モル／モルＡｇＸ
増感色素ＲＳ−２ １×１０^-4モル／モルＡｇＸ
強色増感剤ＳＳ−１ ２×１０^-4モル／モルＡｇＸ
次に（Ｅｍ−Ｒ１０１）の調製において下記化合物を用いて６０℃にて最適に化学増感を行い、赤感光性ハロゲン化銀乳剤（Ｅｍ−Ｒ１０２）を得た。
【０１９７】
チオ硫酸ナトリウム １．８ｍｇ／モルＡｇＸ
塩化金酸 ２．０ｍｇ／モルＡｇＸ
安定剤ＳＴＡＢ−１ ２×１０^-4モル／モルＡｇＸ
安定剤ＳＴＡＢ−２ ２×１０^-4モル／モルＡｇＸ
安定剤ＳＴＡＢ−３ ２×１０^-4モル／モルＡｇＸ
安定剤ＳＴＡＢ−４ １×１０^-4モル／モルＡｇＸ
増感色素ＲＳ−１ ２×１０^-4モル／モルＡｇＸ
増感色素ＲＳ−２ ２×１０^-4モル／モルＡｇＸ
強色増感剤ＳＳ−１ ２×１０^-4モル／モルＡｇＸ
Ｅｍ−Ｒ１０１とＥｍ−Ｒ１０２の１：１の混合物を赤感性乳剤として使用した。
【０１９８】
ＳＴＡＢ−１：１−フェニル−５−メルカプトテトラゾール
ＳＴＡＢ−２：１−（４−エトキシフェニル）−５−メルカプトテトラゾール
ＳＴＡＢ−３：１−（３−アセトアミドフェニル）−５−メルカプトテトラゾール
ＳＴＡＢ−４：ｐ−トルエンチオスルホン酸
【０１９９】
【化３８】

【０２００】
【化３９】

【０２０１】
【化４０】

【０２０２】
さらに、下記表２に示すように第３層中のイエローカプラーを変更し、マゼンタカプラー分散液を作製してから塗布するまでの時間を表２記載のように各試料共、１時間、１２時間、２４時間と変化させた以外は、試料Ｎｏ．１０１と同様にして試料Ｎｏ．１０２〜１１２を作製した。また各試料は二つに取り分け、一方を生試料とし、もう一方を５０℃の環境に５日間さらして経時試料とした。
【０２０３】
【表２】

【０２０４】
光源としてＢのＬＥＤを主走査方向に５個並べ露光のタイミングを少しづつ遅延させることによって同じ場所を５個のＬＥＤで露光出来るように調整した。また、副走査方向にも２０個のＬＥＤを並べ隣接する２０画素分の露光が１度に出来る露光ヘッドを準備した。Ｇ、Ｒも同様にＬＥＤを組み合わせて露光ヘッドを準備した。各ビームの径は約１０μｍで、この間隔でビームを配列し、副走査のピッチは約２００μｍとした。この時の１画素当たりの露光時間は０．１×１０^-6秒であった。
【０２０５】
前記試料Ｎｏ．１０１〜１１２をＲの光源の露光量を適宜変化して露光後、下記の現像処理を行った。
【０２０６】

水を加えて全量を１リットルとし、タンク液はｐＨ＝１０．２に、補充液はｐＨ＝１０．５に調整する。
【０２０７】

水を加えて全量を１リットルとし、炭酸カリウム又は氷酢酸でｐＨ＝５．０に調整する。
【０２０８】

水を加えて全量を１リットルとし、硫酸又はアンモニア水でｐＨ＝７．５に調整する。
【０２０９】
得られた色素画像をエックスライト社製５０８型濃度計を用いＧ濃度を測定し、分散から塗布までの停滞による発色の低下を求めた。発色の低下は、停滞が１時間の試料のＧ濃度が１．６となる露光量における各試料の濃度を１．６からの低下の大きさとして評価した。分光特性はステータスＴを用いた。
【０２１０】
また、色調の測定には、ミノルタ社製分光測色計ＣＭ−２０２２を用い、照明と受光の幾何条件ｄ−０、キセノンパルス光源を用いて測光し、２°視野補助標準の光Ｄ₅₀でのＬ^*ａ^*ｂ^*の値を求めた。経時による色調の変化は、Ｇ濃度が１．６となるパッチのｂ^*の変化（Δｂ^*）を経時していない試料を基準として表示した。同時に、１０ｎｍおきの分光吸収データから５４０ｎｍの吸収が１．８となるように規格化したときの６００ｎｍの吸収を求め、イエローカプラーの種類違いでの長波の吸収の上昇を抑える効果を評価した。
【０２１１】
得られた結果を下記表３に示した。
【０２１２】
【表３】

【０２１３】
表３から明らかなように、一般式（Ｉ）で表されるイエローカプラーをマゼンタ発色層に用いた場合には、一般式（II）で表されるイエローカプラーを使用した場合に比べて６００ｎｍの吸光度によって表されるマゼンタ中のシアン成分が少なく良好な色調を示すことがわかる。一方、経時保存でのΔｂ^*は一般式（Ｉ）を使用した試料で大きく、一般式（II）で表されるイエローカプラーを用いた場合には小さいことがわかる。また、分散液を停滞した場合の発色の低下に関しても、両者に若干の差は見られるが、充分に改善できたレベルではないことがわかる。
【０２１４】
実施例２
実施例１において、表４示すように第３層に一般式（ＨＰ）で表される添加剤を各０．１５ｇ／ｍ²添加し、さらにイエローカプラー成分を変更し、マゼンタカプラー分散液を作製してから塗布するまでの時間を各試料共、１時間、１２時間、２４時間と変化させ、試料Ｎｏ．１１３〜１４２を作製した。また各試料は二つに取り分け、一方を生試料とし、もう一方を５０℃の環境に５日間さらして経時試料とした。
【０２１５】
【表４】

【０２１６】
【化４１】

【０２１７】
実施例１と同様にして得られた色素画像を実施例１と同様にして経時保存でのΔｂ^*、６００ｎｍで表されるマゼンタ中のシアン成分、分散停滞での発色低下について評価した。
【０２１８】
得られた評価結果を表５に示す（尚、実施例１で作製した試料Ｎｏ．１０１〜１０３（比較例）について上記と同様にして求めた評価結果についても示す）。
【０２１９】
【表５】

【０２２０】
表５から明らかなように、本発明の請求項１または３の発明の構成、即ち、マゼンタカプラー中にイエローカプラーを共存させた系において一般式（ＨＰ）で表される添加剤を用いることにより、カプラー分散液の分散から塗布までの停滞時間が長くなっても発色の低下を著しく低く抑えることができ、経時保存でのΔｂ^*も小さくできていることがわかる。また、一般式（ＨＰ）と類似の化合物ではあるが、比較化合物Ａ〜Ｃを添加剤として用いた場合には、発色低下、Δｂ^*を抑える効果を得ることができていない。また、これらの添加剤は一般式（II）で表されるイエローカプラーを併用した系においてもカプラー分散液の停滞時間での発色低下には効果があるが、この場合６００ｎｍの吸光度によって表されるマゼンタ中のシアン成分が大きくなってしまう。一方、一般式（Ｉ）、（II）のイエローカプラーを併用した場合には、６００ｎｍの吸光度によって表されるマゼンタ中のシアン成分は小さくなるが、経時でのΔｂ＊、分散液停滞での発色濃度低下はまだ大きいことがわかる。中でも、本発明の請求項３の発明の構成、即ち、一般式（Ｉ）のイエローカプラーと一般式（II）のイエローカプラーを本発明の一般式（ＨＰ）で表される添加剤と併用することにより、６００ｎｍの吸光度を小さく保つことができたうえ、経時保存でのΔｂ^*、分散液停滞での発色濃度低下も更に小さく抑えることができており、より効果が大きいことがわかる。
【０２２１】
実施例３
実施例１において、表６に示すように第３層に一般式（Ｕ）で表される添加剤を各０．１５ｇ／ｍ²添加し、さらにイエローカプラー成分を変更し、マゼンタカプラー分散液を作製してから塗布するまでの時間を各試料共、１時間、１２時間、２４時間と変化させ、試料Ｎｏ．１４３〜１５７を作製した。また各試料は二つに取り分け、一方を生試料とし、もう一方を５０℃の環境に５日間さらして経時試料とした。
【０２２２】
【表６】

【０２２３】
実施例１と同様にして得られた色素画像を実施例１と同様にして経時保存でのΔｂ^*、６００ｎｍで表されるマゼンタ中のシアン成分、分散停滞での発色低下について評価した。
【０２２４】
得られた評価結果を表７に示す（尚、実施例１で作製した試料Ｎｏ．１０１〜１０３（比較例）、および実施例２で作製した試料Ｎｏ．１２５〜１２７（比較例）について上記と同様にして求めた評価結果についても示す）。
【０２２５】
【表７】

【０２２６】
表７から明らかなように、本発明の請求項２または４の発明の構成、即ち、マゼンタカプラー中にイエローカプラーを共存させた系において一般式（Ｕ）で表される添加剤を用いることにより、カプラー分散液の分散から塗布までの停滞時間が長くなっても発色の低下を著しく低く抑えることができ、経時保存でのΔｂ＊も小さくできていることがわかる。また、実施例２と同様に一般式（II）で表されるイエローカプラーを併用した系においてもカプラー分散液の停滞時間での発色低下には効果があるが、この場合も６００ｎｍの吸光度によって表されるマゼンタ中のシアン成分が大きくなってしまう。中でも、本発明の請求項４の発明の構成、即ち、一般式（Ｉ）のイエローカプラーと一般式（II）のイエローカプラーを本発明の一般式（Ｕ）で表される添加剤と併用することにより、６００ｎｍの吸光度を小さく保つことができたうえ、経時保存でのΔｂ^*、分散液停滞での発色濃度低下も更に小さく抑えることができており、より効果が大きいことがわかる。
【０２２７】
実施例４
実施例１〜３で得られた試料のから、比較として試料１０１と１０３を、本発明として試料１３４と１３６、試料１４０と１４２、試料１４６と１４８、試料１５５と１５７をそれぞれ選択し、生試料、経時試料それぞれについて実施例１で使用したものと同じ露光装置を用いて一画素あたり０．１×１０^-6秒で、Ｙ＝０．９５、Ｍ＝１．６、Ｃ＝１．５となる光源の強度で、ＪＩＳ Ｘ９２０１−１９９５高精細カラーディジタル標準画像ＳＣＩＤの中から、Ｎ１（ポートレート）、Ｎ３（果物籠）、Ｎ４（ワインと食器）の画像をそれぞれ露光した。
【０２２８】
得られた画像を標準印刷物と比較して、プルーフとしての実用性を評価したところ、比較として選択した試料１０１については所望の画質を得られているが、試料１０３については女性の肌の再現、果物の色味などにおいて全体的に赤みが不足し、プルーフ用材料としてはロット変動が大きすぎるものであった。また、試料１０１と１０３の経時試料の画像については全体的に色調が変化していることが見て取れる。一方、本発明として選択した各試料についてはどの画像を露光した場合においても問題の無いレベルを保っており、安定した色再現を持つプルーフ材料を得られたことが確認できた。
【０２２９】
【発明の効果】
本発明により、製造ロット間、ロット内の性能変動が小さく、マゼンタの色調再現に優れ、かつ経時保存による色調変動が少ないハロゲン化銀感光材料およびそれを用いた面積階調画像形成方法を提供できた。より詳細には、分散から塗布までの時間の変化に対して特性の変動が小さく、マゼンタ色素の長波長の分光吸収特性に優れ、かつハロゲン化銀感光材料を経時保存することによるマゼンタ画像の色調変動が小さいハロゲン化銀感光材料およびそれを用いた面積階調画像形成方法を提供できた。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a silver halide light-sensitive material in which the variation in performance among production lots, the variation in performance within each lot is small, the color tone of magenta is excellent, and the variation in color tone due to storage over time is small. Silver halide light-sensitive material which exhibits a small change in characteristics with respect to the change in time, has excellent long-wavelength spectral absorption characteristics of a magenta dye, and has a small color tone change of a magenta image due to storage of the silver halide light-sensitive material over time. Things.
[0002]
[Prior art]
Silver halide light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) are widely used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. Due to these characteristics, silver halide light-sensitive materials have been widely used not only in the field of photography but also in the field of printing, in the field of so-called proofing for checking the state of the finished printed matter in the middle of printing. ing.
[0003]
In the field of proofing, an image edited on a computer is output to a printing film, and the developed film is appropriately replaced and subjected to decomposing exposure to obtain yellow (Y), magenta (M), and cyan (C). By forming an image and forming an image of the final printed matter on color photographic paper, it has been performed to determine the suitability of the layout and color of the final printed matter.
[0004]
Recently, a method of directly outputting an image edited on a computer to a printing plate has gradually become widespread. In such a case, it is desired to obtain a color image directly from the data on the computer without using a film. Had been rare.
[0005]
For this purpose, various methods such as sublimation type / fusion heat transfer method, electrophotographic method, and ink jet method have been tried, but the method of obtaining high quality images is expensive and the productivity is inferior. There is a disadvantage that the system which is low in cost and has high productivity has poor image quality. A system using a silver halide photosensitive material enables high-quality image formation, such as formation of an accurate halftone image, due to excellent sharpness and the like, while continuous processing is possible as described above. In addition, since images can be simultaneously written in a plurality of color image forming units, high productivity can be realized.
[0006]
In recent years, in the field of printing, so-called digitization has progressed, and there has been an increasing demand for obtaining images directly from data in a computer. For the reasons described above, silver halide photosensitive materials have begun to be advantageously used in this field.
[0007]
Japanese Patent Application Laid-Open No. 2001-305701 (Patent Document 1) discloses an image forming method that independently adjusts the density and dot gain using a directly modulated LED as a light source, and produces a proof image having a small difference from a printed image. It discloses that it can be easily obtained, and also discloses that a yellow coupler is used in combination with a pyrazoloazole coupler in Examples. However, the Y coupler used in combination is not the coupler represented by the general formula (I) according to the present invention, and there is no description about the merits and demerits of using the coupler, and there is no suggestion about a solution to the problem. It has not been.
[0008]
JP-A-2-139542 (Patent Document 2) discloses that a color tone preferable as a proof can be reproduced by including a coupler having two kinds of hues in the same photosensitive silver halide emulsion layer. A technique using both a magenta coupler and a yellow coupler is disclosed. Compared with the magenta dye of the printing ink and color paper, the printing ink has a reddish color tone, so it discloses that such a combination is preferable, but according to the study of the present inventors, the present invention has It has been clarified that the use of the yellow coupler represented by the general formula (I) in combination reduces the long-wavelength absorption of the magenta dye and enables a more preferable color to be reproduced. The publication does not mention this phenomenon at all. In addition, in the system using this coupler in combination, when the dispersion of the coupler was stagnated, a phenomenon was observed in which the chromaticity was reduced with time and the photographic performance changed, but such a problem was not mentioned at all, There was no suggestion.
[0009]
JP-A-2001-324785 (Patent Document 3) discloses that a photosensitive silver halide emulsion layer contains a main coupler, and a non-photosensitive layer adjacent to the photosensitive silver halide emulsion layer contains an auxiliary coupler. The difference between the maximum absorption wavelengths of the coloring dye obtained from the main coupler and the coloring dye obtained from the auxiliary coupler contained in the adjacent non-photosensitive emulsion layer is at least 70 nm or more, and the main coupler and the auxiliary coupler have the same high wavelength. The silver halide color photographic light-sensitive material characterized by being contained together with the boiling point organic solvent can improve the variation over time of the magenta color tone which is similar to a printed matter and after development processing, and can uniformly reproduce a black image. Disclosed are examples of a magenta coupler as a main coupler and a yellow coupler as an auxiliary coupler. In this case, a magenta hue close to the printed image can be obtained, but by using the yellow coupler represented by the general formula (I) according to the present invention in combination, the absorption of a long wavelength of the magenta dye is reduced and a more preferable color is reproduced. What is possible is that, when the coupler dispersion is stagnated, the chromogenic property decreases with time and the photographic performance changes, and the color tone of magenta changes to bluish when the unexposed photosensitive material is stored over time. Nothing was said about it, nor was there any suggestion about a solution.
[0010]
Japanese Patent Application Laid-Open No. 2002-131878 (Patent Document 4) discloses that a silver halide emulsion containing a specific magenta coupler and a specific sensitizing dye is contained in the same layer so that a light-sensitive material stored over time can be subjected to running processing. It is disclosed that the fluctuation of the dot gain and the fluctuation of the color tone which occur in the image are suppressed. In this publication, a yellow coupler is contained in a magenta coupler-containing layer, and a compound described in the yellow coupler represented by formula (1) or (2) according to the present invention is used in a yellow image forming layer. A silver halide light-sensitive material is disclosed, but nothing is mentioned about the above three problems.
[0011]
Japanese Patent Application Laid-Open No. 62-180366 (Patent Document 5) discloses that the use of a compound represented by the general formula (HP) according to the present invention in combination with a magenta coupler reduces the storage stability of a magenta dye image and the increase in stain. It is disclosed to be improved. Also, JP-A-7-306509 (Patent Document 6) and JP-A-2001-147509 (Patent Document 7) disclose a compound represented by the general formula (HP) according to the present invention in a magenta coupler-containing layer in Examples. However, the magenta image forming layer does not contain a yellow coupler, and therefore does not mention any problem that occurs with a specific combination of a magenta coupler and a yellow coupler. There was no suggestion.
[0012]
JP-A-6-266077 discloses that a silver halide photosensitive material containing at least one of the compounds represented by formula (HP) according to the present invention is 6 × 10 ^-2 It discloses that development with a color developing solution containing not less than mol / l of chloride improves color development and whiteness, and improves image storability and sweat resistance even during rapid processing over time. . However, as the layer in which the compound represented by the general formula (HP) according to the present invention is present, only the layer containing the yellow coupler and the layer containing the cyan coupler are described, and the use in the layer containing the magenta coupler is not described. Not touched, and also only discloses that it is used in the yellow coupler containing layer in the examples, and does not disclose any problem of the change in color developing property that occurs in a magenta coupler dispersion using a specific yellow coupler in combination, No suggestion. Further, in the examples of the above publication, the magenta coupler-containing layer contains a compound structurally similar to the compound represented by the general formula (HP) according to the present invention (R in the general formula (HP)). _Two Is a hydrogen atom), but the effects of the present invention could not be obtained as shown in Examples of the present invention.
[0013]
JP-A-7-306509 discloses that a magenta image forming layer contains a specific magenta coupler, a high-boiling organic solvent having a dielectric constant of 6.0 or less and a refractive index of 1.50 or less, and a benzotriazole-based ultraviolet absorber. It discloses that a preferable magenta hue and a sufficient coloring density of yellow can be obtained. JP-A-2001-147509 discloses that the use of a specific pyrazolotriazole-based coupler suppresses a change in gradation that occurs when a photosensitive material is stored for a long time and then subjected to a running process. And that it is preferable to use 2- (2'-hydroxyphenyl) benzotriazole in combination. Disclose that the particle size dependence is reduced while the particle size tends to increase. In addition, it discloses that when the coating liquid is stagnated, the lower layer has a behavior of lowering the color density of yellow, which is solved. The benzotriazole compounds described in the publication include the compound represented by the general formula (U) according to the present invention. However, these publications disclose that the magenta image forming layer contains a yellow coupler as described above. No, therefore, no mention was made of the problems which occur with certain magenta and yellow coupler combinations, and no suggestion was made of a solution.
[0014]
[Patent Document 1]
JP 2001-305701 A
[0015]
[Patent Document 2]
JP-A-2-139542
[0016]
[Patent Document 3]
JP 2001-324785 A
[0017]
[Patent Document 4]
JP-A-2002-131878
[0018]
[Patent Document 5]
JP-A-62-180366
[0019]
[Patent Document 6]
JP-A-7-306509
[0020]
[Patent Document 7]
JP 2001-147509 A
[0021]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a silver halide having a small variation in performance between production lots, within a lot, an excellent color reproduction of magenta, and a small variation in color due to storage over time. Provided is a photosensitive material and an area gradation image forming method using the same. More specifically, the variation in characteristics is small with respect to a change in time from dispersion to coating, and a long-wavelength spectral absorption of a magenta dye is provided. An object of the present invention is to provide a silver halide light-sensitive material having excellent characteristics and exhibiting a small change in the color tone of a magenta image due to storage of the silver halide light-sensitive material over time, and an area gradation image forming method using the same.
[0022]
[Means for Solving the Problems]
The above object of the present invention is achieved by the following configurations.
[0023]
1. Silver halide having a silver halide emulsion having an average silver chloride content of 95% or more on a support and a pyrazoloazole-based magenta coupler-containing layer containing a yellow coupler represented by formula (I) A silver halide photosensitive material, wherein the magenta coupler-containing layer contains a compound represented by formula (HP).
[0024]
2. Silver halide having a silver halide emulsion having an average silver chloride content of 95% or more on a support and a pyrazoloazole-based magenta coupler-containing layer containing a yellow coupler represented by formula (I) A silver halide photosensitive material, wherein the magenta coupler-containing layer contains a compound represented by the general formula (U).
[0025]
3. Silver halide having a silver halide emulsion having an average silver chloride content of 95% or more on a support and a pyrazoloazole-based magenta coupler-containing layer containing a yellow coupler represented by formula (I) A silver halide photosensitive material, wherein the magenta coupler-containing layer contains a yellow coupler represented by formula (II) and a compound represented by formula (HP).
[0026]
4. Silver halide having a silver halide emulsion having an average silver chloride content of 95% or more on a support and a pyrazoloazole-based magenta coupler-containing layer containing a yellow coupler represented by formula (I) A silver halide light-sensitive material, wherein the magenta coupler-containing layer contains a yellow coupler represented by formula (II) and a compound represented by formula (U).
[0027]
5. A silver halide light-sensitive material having at least one silver halide emulsion layer on a support is 1 × 10 5 per pixel. ^-9 ~ 1 × 10 ^-3 An area gradation image forming method comprising performing scanning exposure with an exposure time of seconds, wherein the silver halide photosensitive material is the silver halide photosensitive material according to any one of the above items 1 to 4. Area gradation image forming method.
[0028]
Hereinafter, the present invention will be described in detail.
The silver halide emulsion contained in the pyrazoloazole-based magenta coupler-containing layer of the silver halide light-sensitive material of the present invention is a silver halide emulsion having an average silver chloride content of 95% or more, that is, an average silver chloride content of 95%. % Of silver halide grains. As long as this condition is satisfied, silver halide, silver chlorobromide, silver chloroiodobromide, silver chloroiodide and the like having an arbitrary halogen composition are used. Among them, a silver chlorobromide containing 95 mol% or more of silver chloride, particularly a silver halide emulsion having a portion containing silver bromide in a high concentration is preferably used. Silver chloroiodide containing about 0.5 mol% is also preferably used. In the silver halide emulsion having a portion containing silver bromide at a high concentration, the portion containing silver bromide at a high concentration may be a so-called core-shell emulsion or may be simply formed without forming a complete layer. A so-called epitaxy junction region in which only a region having a partially different composition may exist may be formed. It is particularly preferable that the portion where silver bromide exists at a high concentration is formed at the top of crystal grains on the surface of silver halide grains. Further, the composition may change continuously or may change discontinuously. When such an emulsion is used, rapid processing is possible and is less susceptible to fluctuations due to processing conditions.
[0029]
It is advantageous that the silver halide emulsion used in the present invention (hereinafter also referred to as a negative silver halide emulsion) contains heavy metal ions. This is expected to improve so-called reciprocity failure and prevent desensitization in high-illuminance exposure and softening on the shadow side. Examples of heavy metal ions that can be used for such purposes include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; and twelfth metals such as cadmium, zinc, and mercury. Group transition metals and each ion of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be mentioned. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium, and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When the heavy metal ion forms a complex, its ligand is cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, 1, 2, 4-triazole, thiazole and the like can be mentioned. Among them, chloride ion, bromide ion and the like are preferable. These ligands may be used alone or in combination of a plurality of ligands.
[0030]
These metal compounds can also be characterized as the depth of electron traps when contained in silver halide emulsion grains. Examples of the compound that gives a shallow electron trap having a depth of 0.2 eV or less include a second lead ion or a compound having a cyano ligand, which is effective for improving reciprocity failure, particularly low illumination failure. . Examples of the compound that gives a deep electron trap having a depth of 0.35 eV or more include halide ions and Ir, Rh, and Ru compounds having a nitrosyl ligand. These can be preferably used for improving high-illuminance reciprocity failure. It is also a preferable embodiment to use a compound that gives a shallow electron trap with a depth of 0.2 eV or less and a compound that gives a deep electron trap with a depth of 0.35 eV or more. These compounds are described in detail in JP-A-2000-214561, pp. 4-5.
[0031]
In order to allow the silver halide emulsion to contain heavy metal ions, the heavy metal compound may be added to any of the steps during physical ripening before formation of silver halide grains, during formation of silver halide grains, and during physical ripening after formation of silver halide grains. May be added at the location.
[0032]
The heavy metal compound can be dissolved together with the halide salt and added continuously over the whole or a part of the grain formation process. Alternatively, it can be prepared by forming silver halide fine particles containing these heavy metal compounds in advance and adding them. The amount of the heavy metal ion added to the silver halide emulsion is 1 × 10 5 per mole of silver halide. ^-9 1 x 10 or more ^-2 Mol or less, more preferably 1 × 10 ^-8 5 x 10 or more ^-Five Molar or less is preferred.
[0033]
The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973) ), Particles having an octahedral, tetradecahedral, dodecahedral or other shape can be prepared and used. Further, particles having a twin plane may be used.
[0034]
As the silver halide grains used in the present invention, grains having a single shape are preferably used, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.
[0035]
The particle size of the silver halide grains used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, and more preferably, in consideration of other photographic properties such as rapid processing property and sensitivity. It is in the range of 0.2 to 1.0 μm.
[0036]
This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can represent this fairly accurately as diameter or projected area.
[0037]
The distribution of the grain size of the silver halide grains used in the present invention is preferably a monodispersed silver halide grain having a variation coefficient of 0.22 or less, more preferably 0.15 or less, and particularly preferably a variation coefficient of 0.1 or less. That is, two or more monodispersed emulsions of 15 or less are added to the same layer. Here, the variation coefficient is a coefficient representing the width of the particle size distribution, and is defined by the following equation.
[0038]
Coefficient of variation = S / R
(Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.
[0039]
The emulsion used in the present invention may be obtained by any of the acidic method, neutral method, and ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method for producing the seed particles and the method for growing the seed particles may be the same or different.
[0040]
The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. Further, as one form of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.
[0041]
Further, a device for supplying a water-soluble silver salt and a water-soluble halide salt solution from an addition device arranged in a reaction mother liquor described in JP-A-57-92523, JP-A-57-92524, etc. A device for continuously changing the concentration of an aqueous solution of a water-soluble silver salt and a water-soluble halide salt described in, for example, the reaction mother liquor is taken out of the reactor described in JP-B-56-501776, and subjected to ultrafiltration. An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by a method may be used.
[0042]
If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.
[0043]
The negative-working silver halide emulsion used in the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer. As the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used, but a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, triethylthiourea, allylthiocarbamide thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur.
[0044]
The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the expected effect size, and the like. ^-Ten ~ 5 × 10 ^-Five Molar range, preferably 5 × 10 ^-8 ~ 3 × 10 ^-Five A molar range is preferred.
[0045]
As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of the gold compound used is not uniform depending on the type of the silver halide emulsion, the type of the compound to be used, the ripening conditions, etc., but usually 1 × 10 5 per mol of the silver halide. ^-Four Mol ~ 1 x 10 ^-8 Preferably it is molar. More preferably 1 × 10 ^-Five Mol ~ 1 x 10 ^-8 Is a mole. These compounds can be added not for sensitizers but for various purposes at the stage of preparing a coating solution.
[0046]
The chemical sensitization of the negative silver halide emulsion used in the present invention may be a reduction sensitization.
[0047]
The silver halide emulsion used in the present invention is known for the purpose of preventing fogging generated during the step of preparing a silver halide light-sensitive material, reducing performance fluctuation during storage, and preventing fogging generated during development. Antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such purposes include the nitrogen-containing heterocyclic mercapto compounds represented by the general formula (II) described in the lower section of page 7 of JP-A-2-14636, and more preferred. Specific examples of the compound include compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and JP-A-2000-267235, page 8 The compounds described in the right column, lines 32 to 36, can be mentioned. These compounds are added according to the purpose in the steps of preparing silver halide emulsion grains, chemical sensitizing step, finishing the chemical sensitizing step, and preparing a coating solution. When chemical sensitization is performed in the presence of these compounds, 1 × 10 5 ^-Five Mol to 5 × 10 ^-Four It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10 ^-6 Mol ~ 1 x 10 ^-2 Molar amounts are preferred, and 1 × 10 ^-Five Mol to 5 × 10 ^-3 Molar is more preferred. In the step of preparing a coating solution, when adding to the silver halide emulsion layer, 1 × 10 ^-6 Mol ~ 1 x 10 ^-1 Molar amounts are preferred, and 1 × 10 ^-Five Mol ~ 1 x 10 ^-2 Molar is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 m ^Two 1 × 10 per ^-9 Mol ~ 1 x 10 ^-3 Molar amounts are preferred.
[0048]
The silver halide emulsion used in the present invention may contain other additives for various purposes. For example, disulfides and polysulfides such as A-20, C-1, C-9, C-14, C-15, C-16 and C-40 specifically described in JP-A-2-146,036 It is preferable to use compounds, thiosulfonic acid compounds such as D-1, D-3, D-6 and D-8, inorganic sulfur and the like.
[0049]
In the silver halide light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. In particular, as dyes having absorption in the visible region, dyes of AI-1 to 11 described in JP-A-3-251840, p. The dyes described in JP-A-3770 are preferably used.
[0050]
The silver halide light-sensitive material of the present invention comprises at least one hydrophilic colloid layer colored with a diffusion-resistant compound on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. It is preferable to have As the coloring substance, a dye or another organic or inorganic coloring substance can be used.
[0051]
The silver halide light-sensitive material of the present invention preferably has at least one colored hydrophilic colloid layer on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. The layer may contain a white pigment. For example, rutile-type titanium dioxide, anatase-type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin, and the like can be used, but among them, titanium dioxide is preferable for various reasons. The white pigment is dispersed in an aqueous binder of a hydrophilic colloid such as gelatin, which allows the processing liquid to penetrate. The coating amount of the white pigment is preferably 0.1 g / m ^Two ~ 50g / m ^Two And more preferably 0.2 g / m ^Two ~ 5g / m ^Two Range.
[0052]
Between the support and the silver halide emulsion layer closest to the support, a non-photosensitive hydrophilic colloid layer such as an undercoat layer or an intermediate layer may be provided at any position in addition to the white pigment-containing layer, if necessary. Can be provided.
[0053]
It is preferable to add a fluorescent whitening agent to the silver halide light-sensitive material of the present invention since whiteness can be further improved. The fluorescent whitening agent is not particularly limited as long as it is a compound capable of absorbing ultraviolet light and emitting visible light fluorescence, but is a diaminostilbene-based compound having at least one sulfonic acid group in a molecule. These compounds also have the effect of promoting the elution of the sensitizing dye out of the light-sensitive material, and are therefore preferable. Another preferred embodiment is a solid particulate compound having a fluorescent whitening effect.
[0054]
The silver halide light-sensitive material of the present invention has a layer containing a silver halide emulsion spectrally sensitized to a specific region in a wavelength region of 400 to 900 nm. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.
[0055]
As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compounds can be used. Examples of the blue sensitizing dye include those described in JP-A-3-251840, page 28. BS-1 to BS-8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. As the red-sensitive sensitizing dye, RS-1 to 8 described on page 29 of the same publication are preferably used.
[0056]
These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization. In addition, as a method for adding these dyes, water or an organic solvent miscible with water such as methanol, ethanol, fluorinated alcohol, acetone, and dimethylformamide may be added as a solution, or a sensitizing dye may be added. May be added as a solution, emulsion or suspension in a water-miscible solvent having a density of more than 1.0 g / ml.
[0057]
As a method of dispersing the sensitizing dye, a method of mechanically pulverizing and dispersing the sensitizing dye into fine particles of 1 μm or less in an aqueous system using a high-speed stirring type dispersing machine may be used. 8, a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system at 60 to 80 ° C., the surface tension described in JP-B-60-6496 being 3.8 × 10 ^-2 A method of dispersing in the presence of a surfactant suppressed to not more than N / m, dissolving in an acid substantially free of water and having a pKa not exceeding 5 as described in JP-A-50-80826, A method of adding and dispersing in an aqueous liquid and adding this dispersion to a silver halide emulsion can be used.
[0058]
Water is preferable as a dispersion medium used for dispersion, but the solubility may be adjusted by adding a small amount of an organic solvent, or the stability of the dispersion may be increased by adding a hydrophilic colloid such as gelatin.
[0059]
Examples of the dispersing device that can be used to prepare the dispersion include a high-speed stirring type dispersing device shown in FIG. 1 of JP-A-4-125563, a ball mill, a sand mill, an ultrasonic dispersing device, and the like. be able to.
[0060]
When using these dispersing apparatuses, a method of performing a pre-treatment such as dry pulverization in advance and then performing a wet dispersing method as described in JP-A-4-125632 may be employed.
[0061]
The silver halide emulsion used in the present invention may contain one kind or a combination of two or more kinds of sensitizing dyes.
[0062]
As the coupler used in the silver halide light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent is used. Although it can also be used, particularly typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a wavelength. Typical are those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in the range of 600 to 750 nm.
[0063]
One of the features of the silver halide light-sensitive material of the present invention is that it has a magenta coupler-containing layer containing a pyrazoloazole-based magenta coupler as a magenta coupler. As the pyrazoloazole-based magenta coupler according to the present invention, compounds represented by the following general formulas (III) and (IV) are preferable.
[0064]
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[0065]
Where R ¹ And R ^Two Each represents a hydrogen atom or a substituent, which may be the same or different, or may be bonded to each other to form a ring, and X is eliminated when coupled with a hydrogen atom or an oxidized form of a color developing agent. Represents a group to be obtained.
[0066]
R ¹ And a substituent represented by ^Two The substituent represented by is preferably a substituent represented by the following general formula (V).
[0067]
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[0068]
Where R ¹¹ , R ¹² And R ¹³ Each represents a hydrogen atom or a substituent; ¹¹ , R ¹² And R ¹³ Only one of them is not a hydrogen atom, and may be bonded to each other to form a ring.
[0069]
R in the general formula (V) ¹¹ , R ¹² , And R ¹³ There is no particular limitation on the substituent represented by , Hydroxy, alkoxy, aryloxy, acyloxy, carbamoyloxy, sulfamoyloxy, sulfonyloxy, etc., or a halogen atom, a heterocyclic group, etc., and these groups are further substituted with a substitutable group. May be.
[0070]
R in the general formula (V) ¹¹ , R ¹² And R ¹³ Preferably, each group such as a hydrogen atom, alkyl, cycloalkyl, aryl, acyl, acyloxy, sulfonyl and the like can be mentioned.
[0071]
In the general formulas (III) and (IV), examples of the group capable of leaving upon coupling with the oxidized form of the color developing agent represented by X include, for example, a halogen atom, an alkoxy, an aryloxy, a heterocyclic ring Examples of groups include oxy, acyloxy, sulfonyloxy, alkoxycarbonyl, aryloxycarbonyl, alkyloxalyloxy, alkylthio, arylthio, heterocyclic thio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by an N atom, and the like. it can. X is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, or an arylthio group, and more preferably a hydrogen atom, a halogen atom, or the like.
[0072]
Hereinafter, specific examples of the pyrazoloazole-based magenta coupler according to the present invention will be shown, but the present invention is not limited thereto.
[0073]
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[0074]
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[0075]
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[0076]
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[0077]
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[0078]
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[0079]
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[0080]
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[0081]
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[0082]
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[0083]
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[0084]
The pyrazoloazole-based magenta coupler according to the present invention can be used in combination with other types of magenta couplers as long as the effects of the present invention are not impaired. ^-3 Mol to 1 mol, preferably 1 × 10 ^-2 Mol ~ 8 x 10 ^-1 It can be used in the molar range.
[0085]
One of the features of the silver halide light-sensitive material of the present invention resides in that a yellow coupler represented by the general formula (I) is contained in a layer containing a pyrazoloazole magenta coupler.
[0086]
In the above formula (I), R ₁₁ Examples of the alkyl group represented by include groups such as methyl, ethyl, i-propyl, t-butyl, and dodecyl. These alkyl groups may further have a substituent, and examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an acylamino group, and a hydroxyl group. R ₁₁ Examples of the cycloalkyl group represented by include cyclopropyl, cyclohexyl, and adamantyl. R ₁₁ The amino group represented by represents a substituted amino group, and includes groups such as diethylamino, di-i-octylamino, and anilino. These amino groups may further have a substituent. ₁₁ And the same substituents as the substituents of the alkyl group represented by R ₁₁ Examples of the heterocyclic group represented by include a morpholino group and an indoline-1-yl group. R ₁₁ Is preferably an alkyl group, and particularly preferably a t-butyl group.
[0087]
R ₁₂ Examples of the substituent represented by include a carboxyl group, an optionally further substituted arylsulfonyl group, a sulfamoyl group, and an oxycarbonyl group.
[0088]
X ₁ Examples of the alkoxy group represented by are methoxy, ethoxy, i-propoxy, butoxy, decyloxy, dodecyloxy, and the like, and a typical example of the aryloxy group is a phenoxy group.
[0089]
Y ₁ Examples of the acylamino group represented by include palmitoylamino, stearoylamino, and 2- (2,4-di-t-pentylphenoxy) butanoylamino.
[0090]
R ₁₁ , X ₁ And Y ₁ Is a diffusion-resistant group, and R ₁₁ , X ₁ And Y ₁ Is preferably 12 or more.
[0091]
Specific examples of the yellow coupler represented by the general formula (I) are shown below, but the invention is not limited thereto.
[0092]
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[0093]
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[0094]
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[0095]
One of the features of the invention described in claim 3 or 4 is that the yellow coupler represented by the general formula (II) is further contained in the magenta image forming layer.
[0096]
In the general formula (II), R _{twenty one} Represented by the general formula (I) ₁₁ And the same.
[0097]
R _{twenty two} Examples of the linear or branched unsubstituted alkyl group having 2 or more carbon atoms represented by are ethyl, propyl, i-propyl, butyl, hexyl and the like. It is preferably a straight-chain unsubstituted alkyl group, and more preferably a straight-chain unsubstituted alkyl group having 4 or more carbon atoms.
[0098]
X _Two As the alkoxy group or the aryloxy group represented by the general formula (I), X ₁ And the same.
[0099]
Y _Two The acylamino group represented by the general formula (I) ₁ And the same.
[0100]
R _{twenty one} , X _Two And Y _Two Is a diffusion-resistant group, and R _{twenty one} , X _Two And Y _Two Is preferably 12 or more.
[0101]
Specific examples of the yellow coupler represented by the general formula (II) are shown below, but the present invention is not limited thereto.
[0102]
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[0103]
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[0104]
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[0105]
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[0106]
As the cyan coupler contained in the cyan image forming layer in the silver halide light-sensitive material of the present invention, a known phenol, naphthol, imidazole or azole coupler can be used. For example, a phenol coupler substituted with an alkyl group, an acylamino group or a ureido group, a naphthol coupler formed from a 5-aminonaphthol skeleton, a 2-equivalent naphthol coupler having an oxygen atom introduced as a leaving group, and the like are represented. You. Among these, preferred compounds include the general formulas [C-I] and [C-II] described on page 13 of JP-A-6-95283. As the azole coupler, there can be mentioned a coupler represented by formula (I) or (II) described on page 2 of JP-A-8-171185.
[0107]
The cyan coupler is usually used in the silver halide emulsion layer in an amount of 1 × 10 5 per mol of silver halide. ^-3 ~ 1 mol, preferably 1 × 10 ^-2 ~ 8 × 10 ^-1 It can be used in the molar range.
[0108]
As the yellow coupler contained in the yellow image forming layer in the silver halide light-sensitive material of the present invention, a known acylacetanilide-based coupler or the like can be preferably used.
[0109]
Specific examples of the yellow coupler include compounds described on pages 5 to 9 of JP-A-3-241345, compounds represented by Y-I-1 to Y-I-55, and JP-A-3-209466. Compounds described on pages 11 to 14, Y-1 to Y-30, compounds represented by the general formula [Y-I] described on page 21 of JP-A-6-95283, Compounds represented by general formula [I] or [II] described on page 2 of 186601, and couplers represented by general formula [I] described on page 2 of JP-A-2000-112090 can be exemplified.
[0110]
The spectral absorption λmax of the yellow image formed by the silver halide light-sensitive material of the present invention is preferably 425 nm or more, and λL0.2 is preferably 515 nm or less. [lambda] L0.2 refers to a wavelength which is longer than the wavelength showing the maximum absorbance and has an absorbance of 0.2 when the maximum absorbance is 1.0 in the spectral absorbance curve of the image dye. This amount is an indication of the magnitude of the unnecessary absorption on the long-wave side of the image dye, and it is preferable that the wavelength is closer to λmax because the unnecessary absorption is smaller.
[0111]
The yellow coupler is usually used in the silver halide emulsion layer in an amount of 1 × 10 5 per mole of silver halide. ^-3 ~ 1 mol, preferably 1 × 10 ^-2 ~ 8 × 10 ^-1 It can be used in the molar range.
[0112]
One of the features of the invention described in claim 1 or 3 is that the magenta coupler-containing layer contains the compound represented by the general formula (HP).
[0113]
In the general formula (HP), R ₁ Represents a tertiary alkyl group (for example, t-butyl group, t-pentyl group, t-octyl group and the like), and is preferably a t-butyl group. R _Two Represents a primary or secondary alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, etc.), and is preferably a methyl group. Where R _Two May be substituted by a substituent, but is not substituted by a phenyl group. R _Three , R _Four And R _Five Is an alkyl group (eg, methyl group, ethyl group, butyl group, dodecyl group, etc.), an alkoxycarbonyl group (eg, ethoxycarbonyl group, etc.), a phenoxycarbonyl group (eg, 2,4-di-t-butylphenoxycarbonyl group, etc.) An alkoxy group (e.g., 2-ethylhexyloxy group), a phenoxy group (e.g., 4- (2-ethylhexyl) phenoxy group, 4-dodecyl-phenoxy group, etc.), a phenylthio group (e.g., 3-tbutyl, 4-hydroxy, A 5-methylphenylthio group).
[0114]
The above R ₁ Or R _Five The group represented by may be substituted by a substituent. Further, the compound represented by the general formula (HP) is a compound not containing a primary, secondary or tertiary amino group in the structural formula or a compound not containing an acylamino group. Compounds containing no primary, secondary or tertiary amino groups are more preferred. Also R _Four The group represented by is preferably an alkyl group.
[0115]
R _Four The group represented by is more preferably a group containing the following linking group.
[0116]
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[0117]
(Where R ₆ , R ₆ ', R ₇ , R ₇ ', R ₈ , R ₈ ', R ₉ And R ₉ 'Represents a hydrogen atom, an alkyl group, or a phenyl group, respectively. )
Among the compounds represented by formula (HP), preferred compounds are compounds represented by the following formulas (HP-A) and (HP-B).
[0118]
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[0119]
Where R ₁ , R _Two , R _Three , R _Four , R _Five Is R of the general formula (HP) ₁ Or R _Five Is synonymous with R ₁₁ Represents an alkylene group (for example, an ethylene group or an isobutylene group).
[0120]
Among the compounds represented by formula (HP), more preferred compounds are compounds represented by the following formulas (HP-a) and (HP-b).
[0121]
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[0122]
In the general formulas (HP-a) and (HP-b), R ₁ , R _Two , R _Three , R _Five Is R in the general formulas (HP-A) and (HP-B) ₁ Or R _Five Is synonymous with ₁₁ And R ₁₂ Is R of the general formula (HP-A) ₁₁ Is synonymous with
[0123]
The compound represented by formula (HP) can be used in combination with another anti-fading agent.
[0124]
Next, specific examples of the compound represented by Formula (HP) are shown, but the present invention is not limited thereto.
[0125]
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[0126]
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[0127]
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[0128]
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[0129]
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[0130]
The compound represented by the general formula (HP) is 1 × 10 ^-3 It is preferable to contain it in an amount of 1 mol.
[0131]
One of the features of the invention described in claim 2 or 4 resides in that the compound represented by the general formula (U) is contained in the pyrazoloazole-based magenta coupler-containing layer.
[0132]
In the general formula (U), R _U1 Is preferably a hydrogen atom, a halogen atom or an alkoxy group; _U2 And R _U3 Each is preferably a hydrogen atom or an alkyl group; _U4 Is preferably a hydrogen atom, an alkoxy group, an acylamino group, or a ureido group.
[0133]
Hereinafter, specific examples of the compound (ultraviolet absorber) represented by the general formula (U) will be given, but the present invention is not limited thereto.
[0134]
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[0135]
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[0136]
The compound of the general formula (U) preferably has a melting point of -50 to 130C, more preferably -50 to 100C. The compound of the general formula (U) is used in an amount of 1 × 10 ^-3 It is preferable to contain it in an amount of 1 mol.
[0137]
In order to adjust the spectral absorption characteristics of the magenta image, the cyan image, and the yellow image, it is preferable to add a compound having a color tone adjusting action. As the compound for this, a phosphoric ester compound represented by the general formula [HBS-I] described on page 22 of JP-A-6-95283 and a phosphine oxide compound represented by [HBS-II] are preferable. Preferred are compounds represented by the general formula [HBS-II] described on page 22 of the same publication.
[0138]
In the silver halide light-sensitive material of the present invention, the silver halide emulsion layer is laminated and coated on a support, but the order from the support may be any order. In addition, an intermediate layer, a filter layer, a protective layer, and the like can be provided as necessary.
[0139]
An anti-fading agent can be used in combination with each of the magenta, cyan, and yellow couplers to prevent fading of the formed dye image due to light, heat, humidity, and the like. Preferable compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, and JP-A 64-64. Amine compounds represented by the general formula A described in JP 90445 and metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP-A-62-182741 are particularly preferable for magenta dyes. Compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.
[0140]
When an oil-in-water type emulsification dispersion method is used to add the stain inhibitor and other organic compounds used in the silver halide light-sensitive material of the present invention, a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C or higher is usually used. Then, if necessary, a low-boiling point and / or water-soluble organic solvent is used in combination to dissolve, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high-boiling organic solvents that can be used for dissolving and dispersing the stain inhibitor and the like include phosphates such as tricresyl phosphate and trioctyl phosphate; phosphine oxides such as trioctyl phosphine oxide; Higher alcohol compounds represented by (ai) to (ax) described on page 5 of 4-265,975 are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Two or more high boiling organic solvents can be used in combination.
[0141]
Preferred compounds as a surfactant used for dispersing a photographic additive used in the light-sensitive material of the present invention and adjusting a surface tension at the time of coating include a hydrophobic group having 8 to 30 carbon atoms in one molecule and a sulfonic acid. And those containing a group or a salt thereof. Specific examples include A-1 to A-11 described in JP-A-64-26854. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating after the addition to the coating solution are preferably as short as 10 hours each. Within 3 hours, more preferably within 20 minutes.
[0142]
In the silver halide light-sensitive material of the present invention, a compound that reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or is added to a silver halide emulsion layer to prevent fog. It is preferable to improve the above. The compound for this purpose is preferably a hydroquinone derivative, and more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17.
[0143]
It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog or improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are those represented by the general formula III-3 described in JP-A-1-250944 and those represented by the general formula III described in JP-A-64-66646. Compounds described in JP-A-63-187240, compounds represented by the general formula I described in JP-A-4-1633, compounds represented by the general formula (I) described in JP-A-5-165144, The compound shown by (II) is mentioned.
[0144]
It is preferable that the light-sensitive material of the present invention contains an oil-soluble dye or pigment because whiteness is improved. Representative specific examples of the oil-soluble dyes include compounds 1 to 27 described in JP-A-2-842, pp. 8-9.
[0145]
It is advantageous to use gelatin as a binder in the silver halide light-sensitive material of the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, A hydrophilic colloid such as a derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.
[0146]
As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. It is preferable to use the compounds described in JP-A-61-249054 and JP-A-61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.
[0147]
As the support used for the light-sensitive material of the present invention, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, a vinyl chloride sheet, and a white pigment. For example, a polypropylene, polyethylene terephthalate support, baryta paper, or the like may be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.
[0148]
A support having a water-resistant resin coating layer on the surface of paper is usually 50 to 300 g / m2. ^Two Is used. For the purpose of obtaining a proof image, in order to bring the feeling of handling closer to printing paper, 130 g / m2 is used. ^Two The following base papers are preferably used, and 70 to 120 g / m ^Two Base paper is preferably used.
[0149]
The support used in the present invention can be preferably used regardless of whether it has random irregularities or is smooth.
[0150]
As the white pigment used for the support, an inorganic and / or organic white pigment can be used, and an inorganic white pigment is preferably used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.
[0151]
The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass, in order to improve sharpness.
[0152]
The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the variation coefficient described in the above-mentioned publication.
[0153]
The resin layer of the paper support having a water-resistant resin layer on both sides used in the present invention may be a single layer or a plurality of layers. It is preferable to form a plurality of layers and to include a white pigment at a high concentration in contact with the emulsion layer, because sharpness is greatly improved and a proofing image is formed.
[0154]
Further, it is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, and more preferably 0.12 μm or less, since the effect of good gloss is obtained.
[0155]
The light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, directly or undercoating (adhesion, antistatic property, dimensional stability of the support surface). , One or more undercoating layers for improving rub resistance, hardness, antihalation property, frictional properties and / or other properties).
[0156]
When coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.
[0157]
As the exposure light source of the exposure apparatus used in the present invention, any known light source can be preferably used, but a laser or a light emitting diode (hereinafter, referred to as LED) is more preferably used.
[0158]
As a laser, a semiconductor laser (hereinafter, referred to as an LD) is preferably used because it is compact and the life of the light source is long. In addition, LDs are used for applications such as optical pickups for DVDs and music CDs, barcode scanners for POS systems, and for applications such as optical communication, and have the advantage of being inexpensive and having a relatively high output. have. Specific examples of LD include aluminum gallium indium arsenide (650 nm), indium gallium phosphorus (リ ン 700 nm), gallium arsenic phosphorus (610 to 900 nm), and gallium aluminum arsenide (760 to 850 nm). ) And the like. Recently, a laser emitting blue light has been developed, but at present, it is advantageous to use an LD as a light source having a longer wavelength than 610 nm.
[0159]
As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted into half-wavelength light by the SHG element and emitted. Since a visible light is obtained, there is no green light source. Used as a light source in the blue region. As an example of this type of light source, there is a combination of a YAG laser and an SHG element (532 nm).
[0160]
Examples of the gas laser include a helium-cadmium laser (about 442 nm), an argon ion laser (about 514 nm), and a helium neon laser (about 544 nm and 633 nm).
[0161]
As an LED, an LED having a composition similar to that of an LD is known, but various LEDs from blue to infrared have been put to practical use.
[0162]
As an exposure light source used in the present invention, each laser may be used alone, or a combination thereof may be used as a multi-beam. In the case of an LD, for example, by arranging ten LDs, a beam composed of ten light beams can be obtained. On the other hand, in the case of a helium neon laser, the light emitted from the laser is split into, for example, ten light beams by a beam separator.
[0163]
In the case of an LD or LED, the intensity of the exposure light source can be directly modulated by changing the value of the current flowing through each element. In the case of an LD, the intensity may be changed using an element such as an AOM (acoustic optical modulator). In the case of a gas laser, a device such as an AOM or an EOM (electro-optic modulator) is generally used.
[0164]
When an LED is used as a light source, a method may be used in which the same pixel is repeatedly exposed by a plurality of elements as long as the amount of light is weak.
[0165]
Organic light-emitting elements may be used as light sources instead of these, and these are described, for example, in JP-A-2000-258846.
[0166]
In the invention of the present application, the area gradation image does not express the shading on the image by the shading of the color of each pixel, but expresses it by the size of the area of a portion colored to a specific density. It is synonymous.
[0167]
In the case of normal area gradation exposure, the purpose can be achieved by developing Y, M, C, and black. More preferably, in order to identify that a single color such as M or C has developed in addition to black, it is preferable to use three or more different exposure amounts for exposure. In printing, a plate of a special color may be used, but in order to reproduce this, it is preferable to use four or more values of exposure for different exposures.
[0168]
In a system that forms an area gradation image based on digital data, a halftone dot is divided into smaller units (here, these are expressed as dots), and these pixels are exposed at an appropriate exposure amount to form an aggregate. It is possible to reproduce halftone dots. As a simple example, if one halftone dot is composed of 100 dots, 50% halftone dot is formed by exposing 50 dots to developable. You can do it.
[0169]
The silver halide light-sensitive material of the present invention can be preferably used for forming an area gradation image based on the digital data. In this method, since a relatively high-density region is used, a decrease in color development has a significant effect on characteristics. Further, in such a system, since high-intensity short-time exposure is performed, the density of a silver halide emulsion is hardly obtained in a high-density region. Therefore, in such a digital color proof, the effects of the present invention can be preferably used.
[0170]
In the case of a laser light source, the beam diameter is preferably 25 μm or less, more preferably 6 to 22 μm. Although smaller than 6 μm is preferable in terms of image quality, adjustment is difficult and processing speed is reduced. On the other hand, if it is larger than 25 μm, the unevenness increases and the sharpness of the image deteriorates. By optimizing the beam diameter, writing of a high-definition image without unevenness can be performed at high speed.
[0171]
To draw an image with such light, it is necessary for the light beam to scan over the silver halide photosensitive material.However, the photosensitive material is wound around a cylindrical drum and rotated at high speed in a direction perpendicular to the rotation direction. A cylindrical outer surface scanning method in which a light beam is moved may be used, and a cylindrical inner surface scanning method in which a silver halide photosensitive material is brought into close contact with a cylindrical recess and exposed is preferably used. A plane scanning method may be adopted in which the polyhedral mirror is rotated at a high speed and the silver halide light-sensitive material conveyed thereby is exposed by moving a light beam at right angles to the conveying direction. In order to obtain a high quality and large image, a cylindrical outer surface scanning method is more preferably used.
[0172]
In order to perform exposure by the cylindrical outer surface scanning method, the silver halide photosensitive material must be accurately brought into close contact with a cylindrical drum. In order for this to be performed properly, it is necessary that the wafer be transported while being accurately aligned. The silver halide light-sensitive material having the surface on the exposed side wound outward can be more accurately positioned and can be preferably used. From the same viewpoint, the support used for the silver halide light-sensitive material has appropriate rigidity, and preferably has a Taber rigidity of 0.8 to 4.0.
[0173]
The drum diameter can be arbitrarily set in accordance with the size of the silver halide photosensitive material to be exposed. The number of rotations of the drum can be set arbitrarily, but an appropriate number of rotations can be selected according to the beam diameter of the laser beam, the energy intensity, the writing pattern, the sensitivity of the photosensitive material, and the like. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at higher rotation speed, but specifically, 200 to 3000 rotations per minute is preferably used.
[0174]
The method of fixing the silver halide photosensitive material to the drum may be fixed by mechanical means, or a large number of fine holes that can be suctioned on the drum surface are provided according to the size of the photosensitive material, and the photosensitive material is fixed. It can also be brought into close contact by suction. It is important to make the photosensitive material as close as possible to the drum in order to prevent troubles such as uneven images.
[0175]
Known compounds can be used as the aromatic primary amine developing agent used in the present invention. The following compounds can be mentioned as examples of these compounds.
CD-1) N, N-diethyl-p-phenylenediamine
CD-2) 2-Amino-5-diethylaminotoluene
CD-3) 2-Amino-5- (N-ethyl-N-laurylamino) toluene
CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline
CD-5) 2-Methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline
CD-6) 4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) aniline
CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide
CD-8) N, N-dimethyl-p-phenylenediamine
CD-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline
CD-10) 4-Amino-3-methyl-N-ethyl-N- (β-ethoxyethyl) aniline
CD-11) 4-Amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline
In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is preferably from 9.5 to 13.0, more preferably from 9.8 to 12.0. Used in
[0176]
The processing temperature for color development is preferably 35 ° C. or more and 70 ° C. or less. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.
[0177]
Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.
[0178]
A known developer component compound can be added to the color developing solution in addition to the above color developing agent. Usually, an alkali agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazoles, a preservative, a chelating agent and the like are used.
[0179]
The silver halide photosensitive material is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed.
[0180]
As a developing apparatus used for developing silver halide photosensitive material, even if it is a roller transport type in which the photosensitive material is transported between rollers arranged in a processing tank, the photosensitive material is fixed and transported on a belt. The processing tank may be formed in a slit shape, and the processing liquid may be supplied to the processing tank and the photosensitive material may be conveyed. A web system by contact with a carrier impregnated with, a system using a viscous treatment liquid, and the like can also be used. When processing in large quantities, it is usual to run using an automatic developing machine, but at this time, the smaller the replenishment amount of the replenisher, the more preferable the replenishment amount is. And the method described in JP-A-94-16935 is most preferable.
[0181]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but embodiments of the present invention are not limited thereto.
[0182]
Example 1
One side was laminated with high-density polyethylene on one side, and fused polyethylene containing anatase-type titanium oxide dispersed in a content of 15% by mass on the other side. ^Two Each layer having the layer composition shown in Table 1 below was placed on the polyethylene layer containing titanium oxide on a polyethylene-laminated paper reflective support (Taver rigidity = 3.5, PY value = 2.7 μm) having a mass per unit of 115 g. Coated and gelatin 6.00 g / m2 on the backside ^Two , Silica matting agent 0.65 g / m ^Two The multilayer silver halide photosensitive material sample No. 101 was produced.
[0183]
The coupler was dissolved in a high-boiling-point solvent, ultrasonically dispersed, and added as a dispersion. At this time, (SU-1) was used as a surfactant. (H-1) and (H-2) were added as hardeners. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The total amount of (F-1) was 0.04 g / m in each layer. ^Two Was added so that
[0184]
[Table 1]

[0185]
SU-1: sodium tri-i-propylnaphthalenesulfonate
SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt
SU-3: di (2,2,3,3,4,4,5,5-octafluoropentyl) sodium salt of sulfosuccinate
H-1: tetrakis (vinylsulfonylmethyl) methane
H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium
HQ-1: 2,5-di-t-octylhydroquinone
HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone
HQ-3: a mixture of 2,5-di-sec-dodecylhydroquinone, 2,5-di-sectetradecylhydroquinone and 2-sec-dodecyl-5-sec-tetradecylhydroquinone at a mass ratio of 1: 1: 2.
SO-1: trioctylphosphine oxide
SO-2: di (i-decyl) phthalate
SO-3: Oleyl alcohol
SO-4: tricresyl phosphate
PVP: polyvinylpyrrolidone
[0186]
Embedded image

[0187]
Embedded image

[0188]
Embedded image

[0189]
(Preparation of blue-sensitive silver halide emulsion)
The following (Solution A) and (Solution B) were simultaneously added to one liter of a 2% aqueous gelatin solution kept at 40 ° C. while controlling pAg = 7.3 and pH = 3.0, and the following (Solution C) and (Solution D) was added simultaneously while controlling pAg = 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.
(A liquid)
3.42 g of sodium chloride
Potassium bromide 0.03g
200 ml with water
(B liquid)
Silver nitrate 10g
200 ml with water
(Liquid C)
Sodium chloride 102.7g
Potassium hexachloroiridate (IV) 4 × 10 ^-8 Mole
Potassium hexacyanoferrate (II) 2 × 10 ^-Five Mole
1.0 g of potassium bromide
600 ml with water
(D liquid)
Silver nitrate 300g
600 ml with water
After completion of the addition, desalting is performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd., and then mixed with an aqueous gelatin solution to have an average particle diameter of 0.71 μm and a coefficient of variation of particle diameter distribution. A monodispersed cubic emulsion EMP-101 having a silver chloride content of 0.07 and a silver chloride content of 99.5 mol% was obtained.
[0190]
The above (EMP-101) was optimally chemically sensitized at 60 ° C. using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B101).
[0191]
Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer STAB-1 3 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-2 3 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-3 3 × 10 ^-Four Mol / mol AgX
Sensitizing dye BS-1 4 × 10 ^-Four Mol / mol AgX
Sensitizing dye BS-2 1 × 10 ^-Four Mol / mol AgX
Potassium bromide 0.2 g / mol AgX
Next, in the preparation of EMP-101, the average particle diameter was adjusted in the same manner as in EMP-101 except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A monodispersed cubic emulsion EMP-102 having a size of 64 μm, a coefficient of variation in particle size distribution of 0.07 and a silver chloride content of 99.5 mol% was obtained. Em-B102 was obtained in the same manner as in the preparation of Em-B101 except that EMP-102 was used instead of EMP-101, and a 1: 1 mixture of Em-B101 and 102 was used as a blue-sensitive silver halide emulsion. .
[0192]
(Preparation of green photosensitive silver halide emulsion)
In the preparation of EMP-101, the average particle diameter was 0.40 μm, the variation coefficient was 0.08, and the chloride was changed in the same manner except that the addition time of (Solution A) and (Solution B), (Solution C) and (Solution D) was changed. A monodispersed cubic emulsion (EMP-103) having a silver content of 99.5% was obtained.
[0193]
The above-mentioned EMP-103 was optimally chemically sensitized at 55 ° C. using the following compounds to obtain a green-sensitive silver halide emulsion (Em-G101).
[0194]
Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer STAB-1 3 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-2 3 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-3 3 × 10 ^-Four Mol / mol AgX
Sensitizing dye GS-1 2 × 10 ^-Four Mol / mol AgX
Sensitizing dye GS-2 2 × 10 ^-Four Mol / mol AgX
Sodium chloride 0.5g / mol AgX
Next, in the preparation of EMP-103, the average particle size was adjusted in the same manner as in EMP-103 except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. A monodispersed cubic emulsion EMP-104 having a thickness of 50 µm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained. Em-G102 was obtained in the same manner as in the preparation of Em-G101 except that EMP-104 was used instead of EMP-103, and a 1: 1 mixture of Em-G101 and 102 was used as a green-sensitive silver halide emulsion. .
[0195]
(Preparation of red-sensitive silver halide emulsion)
The EMP-103 was optimally chemically sensitized at 60 ° C. using the following compounds to obtain a red-sensitive silver halide emulsion (Em-R101).
[0196]
Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer STAB-1 2 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-2 2 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-3 2 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-4 1 × 10 ^-Four Mol / mol AgX
Sensitizing dye RS-1 1 × 10 ^-Four Mol / mol AgX
Sensitizing dye RS-2 1 × 10 ^-Four Mol / mol AgX
Supersensitizer SS-1 2 × 10 ^-Four Mol / mol AgX
Next, in the preparation of (Em-R101), the following compounds were optimally chemically sensitized at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-R102).
[0197]
Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer STAB-1 2 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-2 2 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-3 2 × 10 ^-Four Mol / mol AgX
Stabilizer STAB-4 1 × 10 ^-Four Mol / mol AgX
Sensitizing dye RS-1 2 × 10 ^-Four Mol / mol AgX
Sensitizing dye RS-2 2 × 10 ^-Four Mol / mol AgX
Supersensitizer SS-1 2 × 10 ^-Four Mol / mol AgX
A 1: 1 mixture of Em-R101 and Em-R102 was used as a red-sensitive emulsion.
[0198]
STAB-1: 1-phenyl-5-mercaptotetrazole
STAB-2: 1- (4-ethoxyphenyl) -5-mercaptotetrazole
STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole
STAB-4: p-toluenethiosulfonic acid
[0199]
Embedded image

[0200]
Embedded image

[0201]
Embedded image

[0202]
Further, as shown in Table 2 below, the yellow coupler in the third layer was changed, and the time from preparation of the magenta coupler dispersion to application was 1 hour and 12 hours for each sample as shown in Table 2. , 24 hours. Sample No. 101 in the same manner as in Sample No. 101. 102 to 112 were produced. Each sample was divided into two samples, one of which was used as a raw sample, and the other was exposed to an environment at 50 ° C. for 5 days to obtain a sample over time.
[0203]
[Table 2]

[0204]
Five LEDs of B as a light source were arranged in the main scanning direction, and the timing of the exposure was gradually delayed so that the same location could be exposed by the five LEDs. In addition, an exposure head was prepared in which 20 LEDs were arranged in the sub-scanning direction and exposure for 20 adjacent pixels could be performed at one time. For G and R, exposure heads were prepared by combining LEDs in the same manner. The diameter of each beam was about 10 μm, the beams were arranged at this interval, and the sub-scanning pitch was about 200 μm. At this time, the exposure time per pixel is 0.1 × 10 ^-6 Seconds.
[0205]
The sample No. After exposing 101 to 112 by appropriately changing the exposure amount of the R light source, the following development processing was performed.
[0206]

The total volume is adjusted to 1 liter by adding water, and the tank solution is adjusted to pH = 10.2 and the replenisher is adjusted to pH = 10.5.
[0207]

The total volume is made up to 1 liter by adding water and adjusted to pH = 5.0 with potassium carbonate or glacial acetic acid.
[0208]

The total volume is adjusted to 1 liter by adding water and adjusted to pH = 7.5 with sulfuric acid or aqueous ammonia.
[0209]
The obtained dye image was measured for G density using a 508 type densitometer manufactured by X-Rite, and a decrease in color development due to stagnation from dispersion to coating was determined. The decrease in color development was evaluated as the magnitude of the decrease in density of each sample from 1.6 at an exposure amount at which the G density of the sample in which the stagnation was 1 hour was 1.6. Status T was used as the spectral characteristic.
[0210]
The color tone was measured using a spectrophotometer CM-2022 manufactured by Minolta Co., Ltd., using a geometric condition of illumination and light reception d-0 and photometry using a xenon pulse light source. ₅₀ L in ^* a ^* b ^* Was determined. The change in the color tone with the lapse of time is represented by b in the patch where the G density is 1.6. ^* Change (Δb ^* ) Are shown based on the sample that has not aged. At the same time, the absorption at 600 nm when the absorption at 540 nm was normalized so that the absorption at 540 nm was 1.8 was obtained from the spectral absorption data every 10 nm, and the effect of suppressing the increase in the absorption of long wave due to the difference in the type of the yellow coupler was evaluated.
[0211]
The results obtained are shown in Table 3 below.
[0212]
[Table 3]

[0213]
As is clear from Table 3, when the yellow coupler represented by the general formula (I) is used in the magenta color-forming layer, the yellow coupler having a wavelength of 600 nm is used as compared with the case where the yellow coupler represented by the general formula (II) is used. It can be seen that there is little cyan component in magenta represented by the absorbance and good color tone is exhibited. On the other hand, Δb ^* Is large in the sample using the general formula (I), and small when the yellow coupler represented by the general formula (II) is used. Also, regarding the reduction in color development when the dispersion liquid is stagnated, although there is a slight difference between the two, it can be seen that the level is not sufficiently improved.
[0214]
Example 2
In Example 1, as shown in Table 4, an additive represented by the general formula (HP) was added to the third layer in an amount of 0.15 g / m 2. ^Two After adding the yellow coupler component, the time from the preparation of the magenta coupler dispersion to the application was changed to 1 hour, 12 hours and 24 hours for each sample. 113 to 142 were produced. Each sample was divided into two samples, one of which was used as a raw sample, and the other was exposed to an environment at 50 ° C. for 5 days to obtain a sample over time.
[0215]
[Table 4]

[0216]
Embedded image

[0219]
The dye image obtained in the same manner as in Example 1 was used to store Δb ^* , 600 nm, a cyan component in magenta, and a reduction in color development due to stagnant dispersion.
[0218]
The obtained evaluation results are shown in Table 5 (note that the evaluation results obtained in the same manner as above for Sample Nos. 101 to 103 (Comparative Examples) produced in Example 1 are also shown).
[0219]
[Table 5]

[0220]
As is apparent from Table 5, the constitution of the invention according to claim 1 or 3 of the present invention, that is, by using the additive represented by the general formula (HP) in a system in which a yellow coupler coexists in a magenta coupler Even when the stagnation time from the dispersion of the coupler dispersion to the application is long, the decrease in color development can be suppressed to a remarkably low level. ^* It can be seen that is also made smaller. In addition, although the compound is similar to the general formula (HP), when the comparative compounds A to C are used as additives, the color development decreases, Δb ^* Has not been able to obtain the effect. Further, these additives are effective in reducing the color development during the stagnation time of the coupler dispersion even in a system in which the yellow coupler represented by the general formula (II) is used in combination. In this case, the additive is represented by the absorbance at 600 nm. The cyan component in magenta increases. On the other hand, when the yellow couplers of the general formulas (I) and (II) are used together, the cyan component in magenta represented by the absorbance at 600 nm becomes smaller, but Δb * with time and color development with stagnation of the dispersion liquid. It can be seen that the concentration decrease is still large. Among them, the constitution of the invention of claim 3 of the present invention, that is, the yellow coupler of the general formula (I) and the yellow coupler of the general formula (II) are used in combination with the additive represented by the general formula (HP) of the present invention. As a result, the absorbance at 600 nm could be kept small, and Δb ^* In addition, the decrease in the color density due to the stagnation of the dispersion can be further suppressed, and it can be seen that the effect is greater.
[0221]
Example 3
In Example 1, as shown in Table 6, an additive represented by the general formula (U) was added to the third layer in an amount of 0.15 g / m. ^Two After adding the yellow coupler component, the time from the preparation of the magenta coupler dispersion to the application was changed to 1 hour, 12 hours and 24 hours for each sample. 143 to 157 were produced. Each sample was divided into two samples, one of which was used as a raw sample, and the other was exposed to an environment at 50 ° C. for 5 days to obtain a sample over time.
[0222]
[Table 6]

[0223]
The dye image obtained in the same manner as in Example 1 was used to store Δb ^* , 600 nm, a cyan component in magenta, and a reduction in color development due to stagnant dispersion.
[0224]
The obtained evaluation results are shown in Table 7 (note that Sample Nos. 101 to 103 (Comparative Example) manufactured in Example 1 and Samples Nos. 125 to 127 (Comparative Example) manufactured in Example 2 had the same results as above. Evaluation results obtained in a similar manner are also shown).
[0225]
[Table 7]

[0226]
As is apparent from Table 7, the constitution of the invention of claim 2 or 4 of the present invention, that is, by using an additive represented by the general formula (U) in a system in which a yellow coupler coexists in a magenta coupler. Further, it can be seen that even if the stagnation time from the dispersion of the coupler dispersion to the application is long, the reduction in color development can be suppressed to a very low level, and the Δb * during storage with time can be reduced. In the same manner as in Example 2, a system in which a yellow coupler represented by the general formula (II) is used in combination has an effect of reducing the color development during the stagnation time of the coupler dispersion. The cyan component in magenta becomes large. Above all, the constitution of the invention of claim 4 of the present invention, that is, the yellow coupler of the general formula (I) and the yellow coupler of the general formula (II) are used in combination with the additive represented by the general formula (U) of the present invention. As a result, the absorbance at 600 nm could be kept small, and Δb ^* In addition, the decrease in the color density due to the stagnation of the dispersion can be further suppressed, and it can be seen that the effect is greater.
[0227]
Example 4
From the samples obtained in Examples 1 to 3, Samples 101 and 103 were selected for comparison, Samples 134 and 136, Samples 140 and 142, Samples 146 and 148, and Samples 155 and 157 were selected as the present invention. Using the same exposure apparatus as used in Example 1 for each of the aged samples, 0.1 × 10 ^-6 At a light source intensity of Y = 0.95, M = 1.6, and C = 1.5 in seconds, N1 (portrait) and N3 (portrait) are selected from JIS X9201-1995 high definition color digital standard image SCID. Images of fruit basket) and N4 (wine and tableware) were respectively exposed.
[0228]
The obtained image was compared with a standard printed matter to evaluate its practicality as a proof. As a result, the desired image quality was obtained for the sample 101 selected for comparison, but the reproduction of the female skin was obtained for the sample 103. The redness was insufficient as a whole in the color and the like of the fruit, and the lot fluctuation was too large as a proofing material. In addition, it can be seen that the color of the images of the time-lapse samples of the samples 101 and 103 has changed as a whole. On the other hand, with respect to each sample selected as the present invention, no problem was maintained even when any image was exposed, and it was confirmed that a proof material having stable color reproduction was obtained.
[0229]
【The invention's effect】
According to the present invention, it is possible to provide a silver halide light-sensitive material having a small variation in performance between production lots, within a lot, excellent color tone reproduction of magenta, and little variation in color tone due to storage over time, and an area gradation image forming method using the same. Was. More specifically, the characteristics change is small with respect to the change in the time from dispersion to coating, the spectral absorption characteristics of the magenta dye at long wavelengths are excellent, and the color tone of the magenta image by storing the silver halide photosensitive material over time A silver halide photosensitive material with small fluctuation and an area gradation image forming method using the same can be provided.

Claims (5)

Silver halide having a silver halide emulsion having an average silver chloride content of 95% or more and a pyrazoloazole-based magenta coupler-containing layer containing a yellow coupler represented by the following general formula (I) on a support A silver halide photosensitive material, wherein the magenta coupler-containing layer contains a compound represented by the following general formula (HP).

(Wherein, R ₁₁ represents an alkyl group, a cycloalkyl group, an amino group, or a heterocyclic group, R ₁₂ represents a substituent, X ₁ represents a chlorine atom, an alkoxy group, or an aryloxy group. Y ₁ represents acylamino represents a group or a chlorine atom, n1 when .n1 is 2 or more represents an integer of 0 to 4, a plurality of Y ₁ may be the same or different.)

(Wherein, R ₁ represents a tertiary alkyl group, R ₂ represents a primary or secondary alkyl group, provided that R ₂ is not substituted by a phenyl group. R ₃ , R ₄ and R ₅ Represents an alkyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, an alkoxy group, a phenoxy group or a phenylthio group.) Silver halide comprising a support having thereon a silver halide emulsion having an average silver chloride content of 95% or more and a pyrazoloazole-based magenta coupler-containing layer containing a yellow coupler represented by formula (I). A silver halide photosensitive material, wherein the magenta coupler-containing layer contains a compound represented by the following general formula (U).

(Wherein, R _U1 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group; R _U2 and R _U3 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group; _U4 represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamide group or a ureido group. Silver halide comprising a support having thereon a silver halide emulsion having an average silver chloride content of 95% or more and a pyrazoloazole-based magenta coupler-containing layer containing a yellow coupler represented by formula (I). A silver halide photosensitive material, wherein the magenta coupler-containing layer contains a yellow coupler represented by the following formula (II) and a compound represented by the above formula (HP).

(Wherein, R ₂₁ represents an alkyl group, a cycloalkyl group, an amino group, or a heterocyclic group; R ₂₂ represents a linear or branched unsubstituted alkyl group having 2 or more carbon atoms; X ₂ represents a chlorine atom, an alkoxy group; .Y ₂ represents a group or an aryloxy group an acylamino group or a chlorine atom, n2 when .n2 is 2 or more represents an integer of 0 to 4, a plurality of Y2 may be the same or different.) Silver halide comprising a support having thereon a silver halide emulsion having an average silver chloride content of 95% or more and a pyrazoloazole-based magenta coupler-containing layer containing a yellow coupler represented by formula (I). A silver halide photosensitive material, wherein the magenta coupler-containing layer contains a yellow coupler represented by formula (II) and a compound represented by formula (U). Area exposure wherein a silver halide photosensitive material having at least one silver halide emulsion layer on a support is exposed by scanning at an exposure time of 1 × 10 ^-9 to 1 × 10 ^-3 seconds per pixel. An area gradation image forming method, wherein the silver halide photosensitive material is the silver halide photosensitive material according to any one of claims 1 to 4.