JP2004302148A - Silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having good dimensional stability in a stable processing system. <P>SOLUTION: In the silver halide photographic sensitive material including at least one silver halide emulsion layer on a support and a back layer on a surface opposite to the surface with the emulsion layer, an undercoat layer containing a clay compound coated with an organic substance is present between the support and the emulsion layer or between the support and the back layer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００５５】
式中、Ｒ^２０は脂肪族基、芳香族基、またはヘテロ環基を表し、Ｒ^１０は水素原子またはブロック基を表し、Ｇ^１０は−ＣＯ−、−ＣＯＣＯ−、−Ｃ（＝Ｓ）−、−ＳＯ_２−、−ＳＯ−、−ＰＯ（Ｒ^３０）−基（Ｒ^３０はＲ^１０に定義した基と同じ範囲内より選ばれ、Ｒ^１０と異なっていてもよい。）、またはイミノメチレン基を表す。Ａ^１０、Ａ^２０はともに水素原子、あるいは一方が水素原子で他方が置換もしくは無置換のアルキルスルホニル基、または置換もしくは無置換のアリールスルホニル基、または置換もしくは無置換のアシル基を表す。
【００５６】
一般式（Ｄ）において、Ｒ^２０で表される脂肪族基は好ましくは炭素数１〜３０の置換もしくは無置換の、直鎖、分岐または環状のアルキル基、アルケニル基、アルキニル基である。
一般式（Ｄ）において、Ｒ^２０で表される芳香族基は単環もしくは縮合環のアリール基で、例えばベンゼン環、ナフタレン環が挙げられる。Ｒ^２０で表されるヘテロ環基としては、単環または縮合環の、飽和もしくは不飽和の、芳香族または非芳香族のヘテロ環基で、例えば、ピリジン環、ピリミジン環、イミダゾール環、ピラゾール環、キノリン環、イソキノリン環、ベンズイミダゾール環、チアゾール環、ベンゾチアゾール環、ピペリジン環、トリアジン環等が挙げられる。
Ｒ^２０として好ましいものはアリール基であり、特に好ましくはフェニル基である。
【００５７】
Ｒ^２０が示す基は置換されていてもよく、代表的な置換基としては例えばハロゲン原子（フッ素原子、塩素原子、臭素原子、または沃素原子）、アルキル基（アラルキル基、シクロアルキル基、活性メチン基等を含む）、アルケニル基、アルキニル基、アリール基、複素環基、４級化された窒素原子を含むヘテロ環基（例えばピリジニオ基）、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、カルボキシ基またはその塩、スルホニルカルバモイル基、アシルカルバモイル基、スルファモイルカルバモイル基、カルバゾイル基、オキサリル基、オキサモイル基、シアノ基、チオカルバモイル基、ヒドロキシ基、アルコキシ基（エチレンオキシ基もしくはプロピレンオキシ基単位を繰り返し含む基を含む）、アリールオキシ基、ヘテロ環オキシ基、アシルオキシ基、（アルコキシもしくはアリールオキシ）カルボニルオキシ基、カルバモイルオキシ基、スルホニルオキシ基、アミノ基、（アルキル、アリール、またはヘテロ環）アミノ基、Ｎ−置換の含窒素ヘテロ環基、アシルアミノ基、スルホンアミド基、ウレイド基、チオウレイド基、イソチオウレイド基、イミド基、（アルコキシもしくはアリールオキシ）カルボニルアミノ基、スルファモイルアミノ基、セミカルバジド基、チオセミカルバジド基、ヒドラジノ基、４級のアンモニオ基、オキサモイルアミノ基、（アルキルもしくはアリール）スルホニルウレイド基、アシルウレイド基、Ｎ−アシルスルファモイルアミノ基、ニトロ基、メルカプト基、（アルキル，アリール，またはヘテロ環）チオ基、（アルキルまたはアリール）スルホニル基、（アルキルまたはアリール）スルフィニル基、スルホ基またはその塩、スルファモイル基、Ｎ−アシルスルファモイル基、スルホニルスルファモイル基またはその塩、リン酸アミドもしくはリン酸エステル構造を含む基、等が挙げられる。
これら置換基は、これらの置換基でさらに置換されていてもよい。
【００５８】
Ｒ^２０が有していてもよい置換基として好ましくは、炭素数１〜３０のアルキル基（活性メチレン基を含む）、アラルキル基、ヘテロ環基、置換アミノ基、アシルアミノ基、スルホンアミド基、ウレイド基、スルファモイルアミノ基、イミド基、チオウレイド基、リン酸アミド基、ヒドロキシ基、アルコキシ基、アリールオキシ基、アシルオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、カルボキシ基（その塩を含む）、（アルキル、アリール、またはヘテロ環）チオ基、スルホ基（その塩を含む）、スルファモイル基、ハロゲン原子、シアノ基、ニトロ基等が挙げられる。
【００５９】
一般式（Ｄ）において、Ｒ^１０は水素原子またはブロック基を表すが、ブロック基とは具体的に、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基、アルコキシ基、アリールオキシ基、アミノ基またはヒドラジノ基を表す。
【００６０】
Ｒ^１０で表されるアルキル基として好ましくは、炭素数１〜１０のアルキル基であり、例えばメチル基、トリフルオロメチル基、ジフルオロメチル基、２−カルボキシテトラフルオロエチル基、ピリジニオメチル基、ジフルオロメトキシメチル基、ジフルオロカルボキシメチル基、３−ヒドロキシプロピル基、メタンスルホンアミドメチル基、ベンゼンスルホンアミドメチル基、ヒドロキシメチル基、メトキシメチル基、メチルチオメチル基、フェニルスルホニルメチル基、ｏ−ヒドロキシベンジル基などが挙げられる。アルケニル基として好ましくは炭素数１〜１０のアルケニル基であり、例えばビニル基、２，２−ジシアノビニル基、２−エトキシカルボニルビニル基、２−トリフルオロ−２−メトキシカルボニルビニル基等が挙げられる。アルキニル基として好ましくは炭素数１〜１０のアルキニル基であり、例えばエチニル基、２−メトキシカルボニルエチニル基等が挙げられる。アリール基としては単環または縮合環のアリール基が好ましく、ベンゼン環を含むものが特に好ましい。例えばフェニル基、３，５−ジクロロフェニル基、２−メタンスルホンアミドフェニル基、２−カルバモイルフェニル基、４−シアノフェニル基、２−ヒドロキシメチルフェニル基などが挙げられる。
【００６１】
ヘテロ環基として好ましくは、少なくとも１つの窒素、酸素、および硫黄原子を含む５〜６員の、飽和または不飽和の、単環または縮合環のヘテロ環基で、４級化された窒素原子を含むヘテロ環基であってもよく、例えばモルホリノ基、ピペリジノ基（Ｎ−置換）、ピペラジノ基、イミダゾリル基、インダゾリル基（４−ニトロインダゾリル基等）、ピラゾリル基、トリアゾリル基、ベンゾイミダゾリル基、テトラゾリル基、ピリジル基、ピリジニオ基（Ｎ−メチル−３−ピリジニオ基等）、キノリニオ基、キノリル基などがある。モルホリノ基、ピペリジノ基、ピリジル基、ピリジニオ基等が特に好ましい。
【００６２】
アルコキシ基としては炭素数１〜８のアルコキシ基が好ましく、例えばメトキシ基、２−ヒドロキシエトキシ基、ベンジルオキシ基等が挙げられる。アリールオキシ基としてはフェノキシ基が好ましく、アミノ基としては無置換アミノ基、および炭素数１〜１０のアルキルアミノ基、アリールアミノ基、または飽和もしくは不飽和のヘテロ環アミノ基（４級化された窒素原子を含む含窒素ヘテロ環基を含む）が好ましい。アミノ基の例としては、２，２，６，６−テトラメチルピペリジン−４−イルアミノ基、プロピルアミノ基、２−ヒドロキシエチルアミノ基、アニリノ基、ｏ−ヒドロキシアニリノ基、５−ベンゾトリアゾリルアミノ基、Ｎ−ベンジル−３−ピリジニオアミノ基等が挙げられる。ヒドラジノ基としては置換もしくは無置換のヒドラジノ基、または置換もしくは無置換のフェニルヒドラジノ基（４−ベンゼンスルホンアミドフェニルヒドラジノ基など）が特に好ましい。
【００６３】
Ｒ^１０で表される基は置換されていてもよく、好ましい置換基としてはＲ^２０の置換基として例示したものがあてはまる。
【００６４】
一般式（Ｄ）においてＲ^１０はＧ^１０−Ｒ^１０の部分を残余分子から分裂させ、−Ｇ^１０−Ｒ^１０部分の原子を含む環式構造を生成させる環化反応を生起するようなものであってもよく、その例としては、例えば特開昭６３−２９７５１号公報などに記載のものが挙げられる。
【００６５】
一般式（Ｄ）で表されるヒドラジン誘導体は、ハロゲン化銀に対して吸着する吸着性の基が組み込まれていてもよい。かかる吸着基としては、アルキルチオ基、アリールチオ基、チオ尿素基、チオアミド基、メルカプト複素環基、トリアゾール基などの米国特許第４，３８５，１０８号明細書、同第４，４５９，３４７号明細書、特開昭５９−１９５２３３号公報、同５９−２００２３１号公報、同５９−２０１０４５号公報、同５９−２０１０４６号公報、同５９−２０１０４７号公報、同５９−２０１０４８号公報、同５９−２０１０４９号公報、特開昭６１−１７０７３３号公報、同６１−２７０７４４号公報、同６２−９４８号公報、同６３−２３４２４４号公報、同６３−２３４２４５号公報、同６３−２３４２４６号公報に記載された基が挙げられる。またこれらハロゲン化銀への吸着基は、プレカーサー化されていてもよい。その様なプレカーサーとしては、特開平２−２８５３４４号公報に記載された基が挙げられる。
【００６６】
一般式（Ｄ）のＲ^１０またはＲ^２０はその中にカプラー等の不動性写真用添加剤において常用されているバラスト基またはポリマーが組み込まれているものでもよい。本発明においてバラスト基とは、６以上の炭素数を有する、直鎖もしくは分岐の、アルキル基（またはアルキレン基）、アルコキシ基（またはアルキレンオキシ基）、アルキルアミノ基（またはアルキレンアミノ基）、アルキルチオ基、あるいはこれらを部分構造として有する基を表し、さらに好ましくは炭素数７以上で炭素数２４以下の、直鎖もしくは分岐の、アルキル基（またはアルキレン基）、アルコキシ基（またはアルキレンオキシ基）、アルキルアミノ基（またはアルキレンアミノ基）、アルキルチオ基、あるいはこれらを部分構造として有する基を表す。またポリマーとしては、例えば特開平１−１００５３０号公報に記載のものが挙げられる。
【００６７】
一般式（Ｄ）のＲ^１０またはＲ^２０は、置換基としてヒドラジノ基を複数個含んでいてもよく、この時一般式（Ｄ）で表される化合物は、ヒドラジノ基に関しての多量体を表し、具体的には例えば特開昭６４−８６１３４号公報、特開平４−１６９３８号公報、特開平５−１９７０９１号公報、国際公開ＷＯ９５−３２４５２号公報、国際公開ＷＯ９５−３２４５３号公報、特開平９−１７９２２９号公報、特開平９−２３５２６４号公報、特開平９−２３５２６５号公報、特開平９−２３５２６６号公報、特開平９−２３５２６７号公報等に記載された化合物が挙げられる。
【００６８】
一般式（Ｄ）のＲ^１０またはＲ^２０は、その中に、カチオン性基（具体的には、４級のアンモニオ基を含む基、４級化されたリン原子を含む基、または４級化された窒素原子を含む含窒素ヘテロ環基等）、エチレンオキシ基もしくはプロピレンオキシ基の繰り返し単位を含む基、（アルキル、アリール、またはヘテロ環）チオ基、あるいは解離性基（アルカリ性の現像液で解離しうる酸性度の低いプロトンを有する基もしくは部分構造、あるいはまたその塩を意味し、具体的には、例えばカルボキシル基（−ＣＯＯＨ）、スルホ基（−ＳＯ_３Ｈ）、ホスホン酸基（−ＰＯ_３Ｈ）、リン酸基（−ＯＰＯ_３Ｈ）、ヒドロキシ基（−ＯＨ基）、メルカプト基（−ＳＨ）、−ＳＯ_２ＮＨ_２基、Ｎ−置換のスルホンアミド基（−ＳＯ_２ＮＨ−基、−ＣＯＮＨＳＯ_２−基、−ＣＯＮＨＳＯ_２ＮＨ−基、−ＮＨＣＯＮＨＳＯ_２−基、−ＳＯ_２ＮＨＳＯ_２−基）、−ＣＯＮＨＣＯ−基、活性メチレン基、含窒素ヘテロ環基に内在する−ＮＨ−基、またはこれらの塩等）が含まれていてもよい。これらの基が含まれる例としては、例えば特開平７−２３４４７１号公報、特開平５−３３３４６６号公報、特開平６−１９０３２号公報、特開平６−１９０３１号公報、特開平５−４５７６１号公報、米国特許第４，９９４，３６５号明細書、米国特許第４，９８８，６０４号明細書、特開平７−２５９２４０号公報、特開平７−５６１０号公報、特開平７−２４４３４８号公報、独特許４００６０３２号明細書、特開平１１−７０９３号公報等に記載の化合物が挙げられる。
【００６９】
一般式（Ｄ）においてＡ^１０、Ａ^２０は水素原子、炭素数２０以下のアルキルまたはアリールスルホニル基（好ましくはフェニルスルホニル基、またはハメットの置換基定数の和が−０．５以上となるように置換されたフェニルスルホニル基）、炭素数２０以下のアシル基（好ましくはベンゾイル基、またはハメットの置換基定数の和が−０．５以上となるように置換されたベンゾイル基、あるいは直鎖、分岐、または環状の置換もしくは無置換の脂肪族アシル基（ここに置換基としては、例えばハロゲン原子、エーテル基、スルホンアミド基、カルボンアミド基、ヒドロキシ基、カルボキシ基、スルホ基等が挙げられる））である。Ａ^１０、Ａ^２０としては水素原子が最も好ましい。
【００７０】
次に、本発明において特に好ましく用いられるヒドラジン誘導体について述べる。
Ｒ^２０は置換フェニル基が特に好ましく、置換基としてはスルホンアミド基、アシルアミノ基、ウレイド基、カルバモイル基、チオウレイド基、イソチオウレイド基、スルファモイルアミノ基、Ｎ−アシルスルファモイルアミノ基等が特に好ましく、さらにスルホンアミド基、ウレイド基が好ましく、スルホンアミド基が最も好ましい。
一般式（Ｄ）で表されるヒドラジン誘導体は、Ｒ^２０またはＲ^１０に、置換基として、直接または間接的に、バラスト基、ハロゲン化銀への吸着基、４級のアンモニオ基を含む基、４級化された窒素原子を含む含窒素ヘテロ環基、エチレンオキシ基の繰り返し単位を含む基、（アルキル、アリール、またはヘテロ環）チオ基、アルカリ性の現像処理液中で解離しうる解離性基、もしくは多量体を形成しうるヒドラジノ基（−ＮＨＮＨ−Ｇ^１０−Ｒ^１０で表される基）の少なくとも１つが置換されていることが特に好ましい。さらには、Ｒ^２０の置換基として、直接または間接的に、前述の何れか１つの基を有することが好ましく、最も好ましいのは、Ｒ^２０がベンゼンスルホンアミド基で置換されたフェニル基を表し、そのベンゼンスルホンアミド基のベンゼン環上の置換基として、直接または間接的に、前述の何れか１つの基を有する場合である。
【００７１】
Ｒ^１０で表される基のうち好ましいものは、Ｇ^１０が−ＣＯ−基の場合には、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基、またはヘテロ環基であり、さらに好ましくは水素原子、アルキル基、置換アリール基（置換基としては電子吸引性基またはｏ−ヒドロキシメチル基が特に好ましい）であり、最も好ましくは水素原子またはアルキル基である。
Ｇ^１０が−ＣＯＣＯ−基の場合にはアルコキシ基、アリールオキシ基、アミノ基が好ましく、特に置換アミノ基、詳しくはアルキルアミノ基、アリールアミノ基、または飽和もしくは不飽和のヘテロ環アミノ基が好ましい。
またＧ^１０が−ＳＯ_２−基の場合には、Ｒ^１０はアルキル基、アリール基または置換アミノ基が好ましい。
【００７２】
一般式（Ｄ）においてＧ^１０は好ましくは−ＣＯ−基または−ＣＯＣＯ−基であり、特に好ましくは−ＣＯ−基である。
【００７３】
次に一般式（Ｄ）で示される化合物の具体例を以下に示す。ただし、本発明で用いることができる化合物は、以下の具体例に限定されるものではない。
【００７４】
【化４】

【００７５】
【化５】

【００７６】
【化６】

【００７７】
【化７】

【００７８】
【化８】

【００７９】
【化９】

【００８０】
【化１０】

【００８１】
【化１１】

【００８２】
【化１２】

【００８３】
【化１３】

【００８４】
【化１４】

【００８５】
【化１５】

【００８６】
【化１６】

【００８７】
【化１７】

【００８８】
【化１８】

【００８９】
【化１９】

【００９０】
【化２０】

【００９１】
【化２１】

【００９２】
【化２２】

【００９３】
【化２３】

【００９４】
【化２４】

【００９５】
【化２５】

【００９６】
【化２６】

【００９７】
【化２７】

【００９８】
【化２８】

【００９９】
【化２９】

【０１００】
【化３０】

【０１０１】
【化３１】

【０１０２】
【化３２】

【０１０３】
【化３３】

【０１０４】
本発明に用いられるヒドラジン誘導体としては、上記のものの他に、下記のヒドラジン誘導体も好ましく用いられる。本発明に用いられるヒドラジン誘導体はまた、下記の公報に記載された種々の方法により合成することができる。
【０１０５】
特公平６−７７１３８号公報に記載の（化１）で表される化合物で、具体的には同公報３頁、４頁に記載の化合物；特公平６−９３０８２号公報に記載の一般式（Ｉ）で表される化合物で、具体的には同公報８頁〜１８頁に記載の１〜３８の化合物；特開平６−２３０４９７号公報に記載の一般式（４）、一般式（５）および一般式（６）で表される化合物で、具体的には同公報２５頁、２６頁に記載の化合物４−１〜化合物４−１０、２８頁〜３６頁に記載の化合物５−１〜５−４２、および３９頁、４０頁に記載の化合物６−１〜化合物６−７；特開平６−２８９５２０号公報に記載の一般式（１）および一般式（２）で表される化合物で、具体的には同公報５頁〜７頁に記載の化合物１−１）〜１−１７）および２−１）；特開平６−３１３９３６号公報に記載の（化２）および（化３）で表される化合物で、具体的には同公報６頁〜１９頁に記載の化合物；特開平６−３１３９５１号公報に記載の（化１）で表される化合物で、具体的には同公報３頁〜５頁に記載の化合物；特開平７−５６１０号公報に記載の一般式（Ｉ）で表される化合物で、具体的には同公報５頁〜１０頁に記載の化合物Ｉ−１〜Ｉ−３８；特開平７−７７７８３号公報に記載の一般式（ＩＩ）で表される化合物で、具体的には同公報１０頁〜２７頁に記載の化合物ＩＩ−１〜ＩＩ−１０２；特開平７−１０４４２６号公報に記載の一般式（Ｈ）および一般式（Ｈａ）で表される化合物で、具体的には同公報８頁〜１５頁に記載の化合物Ｈ−１〜Ｈ−４４；特開平９−２２０８２号公報に記載の、ヒドラジン基の近傍にアニオン性基またはヒドラジンの水素原子と分子内水素結合を形成するノニオン性基を有することを特徴とする化合物で、特に一般式（Ａ）、一般式（Ｂ）、一般式（Ｃ）、一般式（Ｄ）、一般式（Ｅ）、一般式（Ｆ）で表される化合物で、具体的には同公報に記載の化合物Ｎ−１〜Ｎ−３０；特開平９−２２０８２号公報に記載の一般式（１）で表される化合物で、具体的には同公報に記載の化合物Ｄ−１〜Ｄ−５５を挙げることができる。この他、国際公開ＷＯ９５−３２４５２号公報、国際公開ＷＯ９５−３２４５３号公報、特開平９−１７９２２９号公報、特開平９−２３５２６４号公報、特開平９−２３５２６５号公報、特開平９−２３５２６６号公報、特開平９−２３５２６７号公報、特開平９−３１９０１９号公報、特開平９−３１９０２０号公報、特開平１０−１３０２７５号公報、特開平１１−７０９３号公報、特開平６−３３２０９６号公報、特開平７−２０９７８９号公報、特開平８−６１９３号公報、特開平８−２４８５４９号公報、特開平８−２４８５５０号公報、特開平８−２６２６０９号公報、特開平８−３１４０４４号公報、特開平８−３２８１８４号公報、特開平９−８０６６７号公報、特開平９−１２７６３２号公報、特開平９−１４６２０８号公報、特開平９−１６０１５６号公報、特開平１０−１６１２６０号公報、特開平１０−２２１８００号公報、特開平１０−２１３８７１号公報、特開平１０−２５４０８２号公報、特開平１０−２５４０８８号公報、特開平７−１２０８６４号公報、特開平７−２４４３４８号公報、特開平７−３３３７７３号公報、特開平８−３６２３２号公報、特開平８−３６２３３号公報、特開平８−３６２３４号公報、特開平８−３６２３５号公報、特開平８−２７２０２２号公報、特開平９−２２０８３号公報、特開平９−２２０８４号公報、特開平９−５４３８１号公報、特開平１０−１７５９４６号公報記載のヒドラジン誘導体も挙げることができる。
【０１０６】
本発明においてヒドラジン系造核剤は、適当な水混和性有機溶媒、例えばアルコール類（メタノール、エタノール、プロパノール、フッ素化アルコール）、ケトン類（アセトン、メチルエチルケトン）、ジメチルホルムアミド、ジメチルスルホキシド、メチルセルソルブなどに溶解して用いることができる。
また、既によく知られている乳化分散法によって、ジブチルフタレート、トリクレジルフォスフェート、グリセリルトリアセテートあるいはジエチルフタレートなどのオイル、酢酸エチルやシクロヘキサノンなどの補助溶媒を用いて溶解し、機械的に乳化分散物を作製して用いることができる。あるいは固体分散法として知られている方法によって、ヒドラジン誘導体の粉末を水の中にボールミル、コロイドミル、あるいは超音波によって分散して用いることもできる。
【０１０７】
本発明においてヒドラジン系造核剤は、支持体に対してハロゲン化銀乳剤層側であればどの層に添加してもよい。例えば、ハロゲン化銀乳剤層、あるいは他の親水性コロイド層に添加することができるが、ハロゲン化銀乳剤層あるいはそれに隣接する親水性コロイド層に添加することが好ましい。また、２種類以上のヒドラジン系造核剤を併用して使用することもできる。
本発明における造核剤の添加量は、ハロゲン化銀１ｍｏｌに対し１×１０^−５〜１×１０^−２ｍｏｌが好ましく、１×１０^−５〜５×１０^−３ｍｏｌがより好ましく、２×１０^−５〜５×１０^−３ｍｏｌが最も好ましい。
【０１０８】
本発明のハロゲン化銀写真感光材料中には、造核促進剤を内蔵することができる。
本発明に用いられる造核促進剤としては、アミン誘導体、オニウム塩、ジスルフィド誘導体またはヒドロキシメチル誘導体などが挙げられる。具体的には、特開平７−７７７８３号公報４８頁２行〜３７行に記載の化合物で、具体的には４９頁〜５８頁に記載の化合物Ａ−１）〜Ａ−７３）；特開平７−８４３３１号公報に記載の（化２１）、（化２２）および（化２３）で表される化合物で、具体的には同公報６頁〜８頁に記載の化合物；特開平７−１０４４２６号公報に記載の一般式〔Ｎａ〕および一般式〔Ｎｂ〕で表される化合物で、具体的には同公報１６頁〜２０頁に記載のＮａ−１〜Ｎａ−２２の化合物およびＮｂ−１〜Ｎｂ−１２の化合物；特開平８−２７２０２３号公報に記載の一般式（１）、一般式（２）、一般式（３）、一般式（４）、一般式（５）、一般式（６）および一般式（７）で表される化合物で、具体的には同公報に記載の１−１〜１−１９の化合物、２−１〜２−２２の化合物、３−１〜３−３６の化合物、４−１〜４−５の化合物、５−１〜５−４１の化合物、６−１〜６−５８の化合物、および７−１〜７−３８の化合物；特開平９−２９７３７７号公報のｐ５５、カラム１０８の８行〜ｐ６９、カラム１３６の４４行までに記載の造核促進剤を挙げることができる。
【０１０９】
本発明に用いられる造核促進剤としては、下記の一般式（ａ）〜一般式（ｆ）で表される４級塩化合物が好ましく、特に一般式（ｂ）で表される化合物が最も好ましい。
【０１１０】
【化３４】

【０１１１】
【化３５】

【０１１２】
一般式（ａ）においてＱ^１は窒素原子またはリン原子を表し、Ｒ^１００、Ｒ^１１０、Ｒ^１２０はそれぞれ脂肪族基、芳香族基またはヘテロ環基を表し、これらは互いに結合して環状構造を形成してもよい。ＭはＭに含まれる炭素原子でＱ^１と結合するｍ^１０価の有機基を表し、ここにｍ^１０は１〜４の整数を表す。
一般式（ｂ）、一般式（ｃ）、または一般式（ｄ）において、Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ａ^５はそれぞれ、４級化された窒素原子を含む不飽和ヘテロ環を完成させるための有機残基を表し、Ｌ^１０およびＬ^２０は２価の連結基を表し、Ｒ^１１１、Ｒ^２２２、Ｒ^３３３は置換基を表す。
一般式（ａ）、一般式（ｂ）、一般式（ｃ）、または一般式（ｄ）で表される４級塩化合物は、分子内にエチレンオキシ基またはプロピレンオキシ基の繰り返し単位を、計２０個以上有しているが、これは複数箇所にまたがって有していてもよい。
【０１１３】
一般式（ｅ）においてＱ^２は窒素原子またはリン原子を表す。Ｒ^２００、Ｒ^２１０、Ｒ^２２０は一般式（ａ）のＲ^１００、Ｒ^１１０、Ｒ^１２０と同義の基を表す。
一般式（ｆ）においてＡ^６は一般式（ｂ）におけるＡ^１またはＡ^２と同義の基を表す。但しＡ^６が形成する含窒素不飽和ヘテロ環は置換基を有してもよいが、置換基上に１級の水酸基を有することはない。一般式（ｅ）および一般式（ｆ）においてＬ^３０はアルキレン基を表し、Ｙは−Ｃ（＝Ｏ）−または−ＳＯ_２−を表し、Ｌ^４０は少なくとも１つの親水性基を含有する２価の連結基を表す。
一般式（ａ）〜一般式（ｆ）においてＸ^ｎ−は、ｎ価の対アニオンを表し、ｎは１〜３の整数を表す。但し、分子内に別にアニオン基を有し、（Ｑ^１）^＋、（Ｑ^２）^＋またはＮ^＋と分子内塩を形成する場合、Ｘ^ｎ−は必要ない。
【０１１４】
一般式（ａ）においてＲ^１００、Ｒ^１１０、Ｒ^１２０で表される脂肪族基とは、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、オクチル基、２−エチルヘキシル基、ドデシル基、ヘキサデシル基、オクタデシル基などの直鎖または分枝状のアルキル基；置換もしくは無置換のベンジル基などのアラルキル基；シクロプロピル基、シクロペンチル基、シクロヘキシル基などのシクロアルキル基；アリル基、ビニル基、５−ヘキセニル基などのアルケニル基；シクロペンテニル基、シクロヘキセニル基などのシクロアルケニル基；フェニルエチニル基等のアルキニル基が挙げられる。芳香族基としてはフェニル基、ナフチル基、フエナントリル基などのアリール基が、またヘテロ環基としては、ピリジル基、キノリル基、フリル基、イミダゾリル基、チアゾリル基、チアジアゾリル基、ベンゾトリアゾリル基、ベンゾチアゾリル基、モルホリル基、ピリミジル基、ピロリジル基などが挙げられる。
【０１１５】
これらの基上に置換した置換基の例としては、Ｒ^１００、Ｒ^１１０、Ｒ^１２０で表される基の他に、フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子、ニトロ基、（アルキルもしくはアリール）アミノ基、アルコキシ基、アリールオキシ基、（アルキルまたはアリール）チオ基、カルボンアミド基、カルバモイル基、ウレイド基、チオウレイド基、スルホニルウレイド基、スルホンアミド基、スルファモイル基、ヒドロキシル基、スルホニル基、カルボキシル基（カルボキシラートを含む）、スルホ基（スルホナートを含む）、シアノ基、オキシカルボニル基、アシル基、ヘテロ環基（４級化された窒素原子を含むヘテロ環基を含む）等が挙げられる。これら置換基はこれら置換基でさらに置換されていてもよい。
一般式（ａ）のＲ^１００、Ｒ^１１０、Ｒ^１２０で表される基は、互いに結合して環状構造を形成していてもよい。
【０１１６】
一般式（ａ）のＭで表される基の例としては、ｍ^１０が１を表す時、Ｒ^１００、Ｒ^１１０、Ｒ^１２０と同義の基が挙げられる。ｍ^１０が２以上の整数を表す時、ＭはＭに含まれる炭素原子でＱ^１と結合するｍ^１０価の連結基を表し、具体的には、アルキレン基、アリーレン基、ヘテロ環基、さらにはこれらの基と−ＣＯ−基、−Ｏ−基、−Ｎ（ＲＮ）−基、−Ｓ−基、−ＳＯ−基、−ＳＯ_２−、−Ｐ＝Ｏ−基を組みあわせて形成されるｍ^１０価の連結基を表す（ＲＮは水素原子またはＲ^１００、Ｒ^１１０、Ｒ^１２０と同義の基を表し、分子内に複数のＲＮが存在する時、これらは同じであっても異なっていてもよく、さらには互いに結合していてもよい）。Ｍは任意の置換基を有していてもよく、その置換基としては、Ｒ^１００、Ｒ^１１０、Ｒ^１２０で表される基が有していてもよい置換基と同じものが挙げられる。
【０１１７】
一般式（ａ）においてＲ^１００、Ｒ^１１０、Ｒ^１２０は、好ましくは炭素数２０以下の基であり、Ｑ^１がリン原子を表す時、炭素数１５以下のアリール基が特に好ましく、Ｑ^１が窒素原子を表す時、炭素数１５以下のアルキル基、アラルキル基、アリール基が特に好ましい。ｍ^１０は１または２が好ましく、ｍ^１０が１を表す時、Ｍは好ましくは炭素数２０以下の基であり、総炭素数１５以下のアルキル基、アラルキル基、またはアリール基が特に好ましい。ｍ^１０が２を表す時、Ｍで表される２価の有機基は、好ましくはアルキレン基、アリーレン基、さらにはこれらの基と−ＣＯ−基、−Ｏ−基、−Ｎ（ＲＮ）−基、−Ｓ−基、−ＳＯ_２−基を組みあわせて形成される２価の基である。ｍ^１０が２を表す時、ＭはＭに含まれる炭素原子でＱ^１と結合する総炭素数２０以下の２価の基であることが好ましい。なおＭ、あるいはＲ^１００、Ｒ^１１０、Ｒ^１２０が、エチレンオキシ基もしくはプロピレンオキシ基の繰り返し単位を複数個含む場合、以上述べた総炭素数の好ましい範囲は、その限りではない。またｍ^１０が２以上の整数を表す時、分子内にＲ^１００、Ｒ^１１０、Ｒ^１２０はそれぞれ複数存在するが、その複数のＲ^１００、Ｒ^１１０、Ｒ^１２０はそれぞれ同じであっても異なっていてもよい。
【０１１８】
一般式（ａ）で表される４級塩化合物は、分子内にエチレンオキシ基またはプロピレンオキシ基の繰り返し単位を計２０個以上有するが、これは１箇所に置換されていても、あるいは複数箇所にまたがって置換されていてもよい。ｍ^１０が２以上の整数を表す時、Ｍで表される連結基に、エチレンオキシ基またはプロピレンオキシ基の繰り返し単位を計２０個以上有していることがより好ましい。
【０１１９】
一般式（ｂ）、一般式（ｃ）または一般式（ｄ）において、Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ａ^５は４級化された窒素原子を含む、置換または無置換の不飽和ヘテロ環を完成させるための有機残基を表し、炭素原子、酸素原子、窒素原子、硫黄原子および水素原子を含んでもよく、さらにベンゼン環が縮環してもかまわない。
Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ａ^５が形成する不飽和ヘテロ環の例としては、ピリジン環、キノリン環、イソキノリン環、イミダゾール環、チアゾール環、チアジアゾール環、ベンゾトリアゾール環、ベンゾチアゾール環、ピリミジン環、ピラゾール環などを挙げることができる。特に好ましくは、ピリジン環、キノリン環、イソキノリン環である。
Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ａ^５が４級化された窒素原子と共に形成する不飽和ヘテロ環は、置換基を有していてもよい。この場合の置換基の例としては、一般式（ａ）のＲ^１００、Ｒ^１１０、Ｒ^１２０で表される基が有していてもよい置換基と同じものが挙げられる。置換基として好ましくは、ハロゲン原子（特に塩素原子）、炭素数２０以下のアリール基（特にフェニル基が好ましい）、アルキル基、アルキニル基、カルバモイル基、（アルキルもしくはアリール）アミノ基、（アルキルもしくはアリール）オキシカルボニル基、アルコキシ基、アリールオキシ基、（アルキルもしくはアリール）チオ基、ヒドロキシ基、メルカプト基、カルボンアミド基、スルホンアミド基、スルホ基（スルホナートを含む）、カルボキシル基（カルボキシラートを含む）、シアノ基、等が挙げられる。特に好ましくは、フェニル基、アルキルアミノ基、カルボンアミド基、塩素原子、アルキルチオ基等であり、最も好ましくはフェニル基である。
【０１２０】
Ｌ^１０、Ｌ^２０で表される２価の連結基は、アルキレン、アリーレン、アルケニレン、アルキニレン、２価のヘテロ環基、−ＳＯ_２−、−ＳＯ−、−Ｏ−、−Ｓ−、−Ｎ（ＲＮ’）−、−Ｃ（＝Ｏ）−、−ＰＯ−を単独または組合せて構成されるものが好ましい。ただしＲＮ’はアルキル基、アラルキル基、アリール基、水素原子を表す。Ｌ^１０、Ｌ^２０で表される２価の連結基は任意の置換基を有していてもよい。置換基の例としては、一般式（ａ）のＲ^１００、Ｒ^１１０、Ｒ^１２０で表される基が有していてもよい置換基と同じものが挙げられる。Ｌ^１０、Ｌ^２０の特に好ましい例として、アルキレン、アリーレン、−Ｃ（＝Ｏ）−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−Ｎ（ＲＮ’）−を単独または組合せて構成されるものを挙げることができる。
【０１２１】
Ｒ^１１１、Ｒ^２２２、Ｒ^３３３は炭素数１〜２０のアルキル基またはアラルキル基が好ましく、各々同じでも異なっていてもよい。Ｒ^１１１、Ｒ^２２２、Ｒ^３３３は置換基を有していてもよく、置換基としては、一般式（ａ）のＲ^１００、Ｒ^１１０、Ｒ^１２０で表される基が有していてもよい置換基と同じものが挙げられる。特に好ましくは、Ｒ^１１１、Ｒ^２２２、Ｒ^３３３は各々炭素数１〜１０のアルキル基またはアラルキル基である。その好ましい置換基の例としては、カルバモイル基、オキシカルボニル基、アシル基、アリール基、スルホ基（スルホナートを含む）、カルボキシル基（カルボキシラートを含む）、ヒドロキシ基、（アルキルまたはアリール）アミノ基、アルコキシ基を挙げることができる。
但しＲ^１１１、Ｒ^２２２、Ｒ^３３３にエチレンオキシ基またはプロピレンオキシ基の繰り返し単位を複数個含む場合、以上のＲ^１１１、Ｒ^２２２、Ｒ^３３３について述べた炭素数の好ましい範囲は、その限りではない。
【０１２２】
一般式（ｂ）または一般式（ｃ）で表される４級塩化合物は、分子内にエチレンオキシ基またはプロピレンオキシ基の繰り返し単位を計２０個以上有するが、これは１箇所に置換されていても、あるいは複数箇所に置換されていてもよく、Ａ^１、Ａ^２、Ａ^３、Ａ^４、Ｒ^１１１、Ｒ^２２２、Ｌ^１０、Ｌ^２０のいずれに置換されていてもよいが、好ましくは、Ｌ^１０またはＬ^２０で表される連結基に、エチレンオキシ基またはプロピレンオキシ基の繰り返し単位を計２０個以上有していることが好ましい。
【０１２３】
一般式（ｄ）で表される４級塩化合物は、分子内にエチレンオキシ基またはプロピレンオキシ基の繰り返し単位を計２０個以上有するが、これは１箇所に置換されていても、あるいは複数箇所に置換されていてもよく、Ａ^５またはＲ^３３３の何れに置換されていてもよいが、好ましくは、Ｒ^３３３で表される基に、エチレンオキシ基またはプロピレンオキシ基の繰り返し単位を計２０個以上有していることが好ましい。
【０１２４】
一般式（ａ）、一般式（ｂ）、一般式（ｃ）、および一般式（ｄ）で表される４級塩化合物は、エチレンオキシ基とプロピレンオキシ基とを、同時に繰り返し含んでいてもよい。またエチレンオキシ基またはプロピレンオキシ基の繰り返し単位を複数個含む場合に、繰り返し個数は、厳密に１つの値を取っていても、あるいは平均値として与えられてもよく、後者の場合、４級塩化合物としては、ある程度の分子量分布を持つ、混合物となる。
本発明においてはエチレンオキシ基の繰り返し単位を計２０個以上有する場合がより好ましく、さらに計２０個〜計６７個有する場合が好ましい。
【０１２５】
一般式（ｅ）においてＱ^２、Ｒ^２００、Ｒ^２１０、Ｒ^２２０は、それぞれ一般式（ａ）におけるＱ^１、Ｒ^１００、Ｒ^１１０、Ｒ^１２０と同義の基を表し、その好ましい範囲もまた同じである。
一般式（ｆ）においてＡ^６は、一般式（ｂ）におけるＡ^１またはＡ^２と同義の基を表し、その好ましい範囲もまた同じである。但し、一般式（ｆ）のＡ^６が４級化された窒素原子と共に形成する含窒素不飽和ヘテロ環は、置換基を有していてもよいが、１級の水酸基を含む置換基を有することはない。
【０１２６】
一般式（ｅ）および一般式（ｆ）においてＬ^３０はアルキレン基を表す。アルキレン基としては、直鎖、分岐、あるいは環状の、置換または無置換のアルキレン基で、炭素数１〜２０のものが好ましい。またエチレン基に代表される飽和のもののみならず、−ＣＨ_２Ｃ_６Ｈ_４ＣＨ_２−や−ＣＨ_２ＣＨ＝ＣＨＣＨ_２−に代表される不飽和の基が含まれているものでもよい。またＬ^３０が置換基を有する時、その置換基としては一般式（ａ）のＲ^１００、Ｒ^１１０、Ｒ^１２０で表される基が有していてもよい置換基の例が挙げられる。
Ｌ^３０としては炭素数が１〜１０の、直鎖または分岐の飽和の基が好ましい。さらに好ましくは、置換もしくは無置換の、メチレン基、エチレン基、トリメチレン基で、特に好ましくは置換もしくは無置換の、メチレン基またはエチレン基で、最も好ましくは置換もしくは無置換のメチレン基である。
【０１２７】
一般式（ｅ）および一般式（ｆ）においてＬ^４０は、少なくとも１つの親水性基を有する２価の連結基を表す。ここに親水性基とは−ＳＯ_２−、−ＳＯ−、−Ｏ−、−Ｐ（＝Ｏ）＝、−Ｃ（＝Ｏ）−、−ＣＯＮＨ−、−ＳＯ_２ＮＨ−、−ＮＨＳＯ_２ＮＨ−、−ＮＨＣＯＮＨ−、アミノ基、グアジニノ基、アンモニオ基、４級化された窒素原子を含むヘテロ環基の各基、あるいはこれらの基の組み合わせからなる基を表す。これらの親水性基とアルキレン基、アルケニレン基、アリーレン基、へテロ環基を適宜組み合わせてＬ^４０が構成される。
Ｌ^４０を構成するアルキレン基、アリーレン基、アルケニレン基、へテロ環基等の基は、置換基を有していてもよい。置換基としては、一般式（ａ）のＲ^１００、Ｒ^１１０、Ｒ^１２０で表される基が有していてもよい置換基の例と同じものが挙げられる。
Ｌ^４０において親水性基はＬ^４０を分断する形態で存在していても、Ｌ^４０上の置換基の一部として存在していてもよいが、Ｌ^４０を分断する形態で存在していることがより好ましい。例えば−Ｃ（＝Ｏ）−、−ＳＯ_２−、−ＳＯ−、−Ｏ−、−Ｐ（＝Ｏ）＝、−ＣＯＮＨ−、−ＳＯ_２ＮＨ−、−ＮＨＳＯ_２ＮＨ−、−ＮＨＣＯＮＨ−、カチオン性基（具体的には窒素またはリンの４級塩構造、あるいは４級化された窒素原子を含む含窒素ヘテロ環）、アミノ基、グアジニノ基の各基、あるいはこれらの基の組み合わせからなる２価の基が、Ｌ^４０を分断する形態で存在している場合である。
【０１２８】
Ｌ^４０が有する親水性基として好ましい例の１つは、エーテル結合とアルキレン基を組み合わせた、エチレンオキシ基やプロピレンオキシ基の繰り返し単位を複数個有する基である。その重合度または平均重合度は、２〜６７個が好ましい。
Ｌ^４０が有する親水性基としてはまた、−ＳＯ_２−、−ＳＯ−、−Ｏ−、−Ｐ（＝Ｏ）＝、−Ｃ（＝Ｏ）−、−ＣＯＮＨ−、−ＳＯ_２ＮＨ−、−ＮＨＳＯ_２ＮＨ−、−ＮＨＣＯＮＨ−、アミノ基、グアジニノ基、アンモニオ基、４級化された窒素原子を含むヘテロ環基等の基を組み合わせた結果として、あるいはまたはＬ^４０の有する置換基として、解離性基を含む場合も好ましい。ここで解離性基とは、アルカリ性の現像液で解離しうる酸性度の低いプロトンを有する基もしくは部分構造、あるいはまたその塩を意味し、具体的には、例えばカルボキシ基（−ＣＯＯＨ）、スルホ基（−ＳＯ_３Ｈ）、ホスホン酸基（−ＰＯ_３Ｈ）、リン酸基（−ＯＰＯ_３Ｈ）、ヒドロキシ基（−ＯＨ基）、メルカプト基（−ＳＨ）、−ＳＯ_２ＮＨ_２基、Ｎ−置換のスルホンアミド基（−ＳＯ_２ＮＨ−基、−ＣＯＮＨＳＯ_２−基、−ＳＯ_２ＮＨＳＯ_２−基）、−ＣＯＮＨＣＯ−基、活性メチレン基、含窒素ヘテロ環基に内在する−ＮＨ−基、またはこれらの塩のことである。
【０１２９】
Ｌ^４０は好ましくはアルキレン基またはアリーレン基と、−Ｃ（＝Ｏ）−、−ＳＯ_２−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ_２ＮＨ−、−ＮＨＳＯ_２ＮＨ−、−ＮＨＣＯＮＨ−、およびアミノ基を適宜組み合わせたものが用いられる。より好ましくは炭素数２〜５のアルキレン基と−Ｃ（＝Ｏ）−、−ＳＯ_２−、−Ｏ−、−ＣＯＮＨ−、−ＳＯ_２ＮＨ−、−ＮＨＳＯ_２ＮＨ−、−ＮＨＣＯＮＨ−を適宜組み合わせたものが用いられる。
Ｙは−Ｃ（＝Ｏ）−または−ＳＯ_２−を表す。好ましくは−Ｃ（＝Ｏ）−が用いられる。
【０１３０】
一般式（ａ）〜一般式（ｆ）においてＸ^ｎ−で表される対アニオンの例としては、塩素イオン、臭素イオン、ヨウ素イオンなどのハロゲンイオン、アセテートイオン、オキサレートイオン、フマレートイオン、ベンゾエートイオンなどのカルボキシレートイオン、ｐ−トルエンスルホネート、メタンスルホネート、ブタンスルホネート、ベンゼンスルホネートなどのスルホネートイオン、硫酸イオン、過塩素酸イオン、炭酸イオン、硝酸イオン等が挙げられる。
Ｘ^ｎ−で表される対アニオンとしては、ハロゲンイオン、カルボキシレートイオン、スルホネートイオン、硫酸イオンが好ましく、ｎは１または２が好ましい。Ｘ^ｎ−としては、クロロイオンまたはブロモイオンが特に好ましく、クロロイオンが最も好ましい。
ただし、分子内に別にアニオン基を有し、（Ｑ^１）^＋、（Ｑ^２）^＋またはＮ^＋と分子内塩を形成する場合、Ｘ^ｎ−は必要ない。
【０１３１】
本発明で用いる４級塩化合物としては、一般式（ｂ）、一般式（ｃ）、一般式（ｆ）で表される４級塩化合物がより好ましく、中でも一般式（ｂ）および一般式（ｆ）で表される４級塩化合物が特に好ましい。さらに一般式（ｂ）においては、Ｌ^１０で表される連結基にエチレンオキシ基の繰り返し単位を２０個以上有する場合が好ましく、さらに２０個〜６７個有する場合が特に好ましい。また一般式（ｆ）においては、Ａ^６が形成する不飽和へテロ環化合物が４−フェニルピリジン、イソキノリン、キノリンを表す時が特に好ましい。
【０１３２】
次に一般式（ａ）〜一般式（ｆ）で表される４級塩化合物の具体例を示す。以下において、Ｐｈはフェニル基を表す。ただし本発明は以下の化合物例によって限定されるものではない。
【０１３３】
【化３６】

【０１３４】
【化３７】

【０１３５】
【化３８】

【０１３６】
【化３９】

【０１３７】
【化４０】

【０１３８】
【化４１】

【０１３９】
【化４２】

【０１４０】
【化４３】

【０１４１】
一般式（ａ）〜一般式（ｆ）で表される４級塩化合物は、公知の方法により容易に合成することができる。
【０１４２】
本発明に使用できる造核促進剤は、適当な水混和性有機溶媒、例えばアルコール類（メタノール、エタノール、プロパノール、フッ素化アルコール）、ケトン類（アセトン、メチルエチルケトン）、ジメチルホルムアミド、ジメチルスルホキシド、メチルセルソルブなどに溶解して用いることができる。
【０１４３】
また、既によく知られている乳化分散法によって、ジブチルフタレート、トリクレジルフォスフェート、グリセリルトリアセテートあるいはジエチルフタレートなどのオイル、酢酸エチルやシクロヘキサノンなどの補助溶媒を用いて溶解し、機械的に乳化分散物を作製して用いることができる。あるいは固体分散法として知られている方法によって、造核促進剤の粉末を水の中にボールミル、コロイドミル、あるいは超音波によって分散し用いることができる。
【０１４４】
本発明に使用できる造核促進剤は、支持体に対してハロゲン化銀乳剤層側のハロゲン化銀乳剤を含まない親水性コロイド層からなる非感光層に添加することが好ましく、特に該ハロゲン化銀乳剤層と支持体の間の親水性コロイド層からなる非感光層に添加することが好ましい。
造核促進剤の添加量はハロゲン化銀１ｍｏｌに対し１×１０^−６〜２×１０^−２ｍｏｌが好ましく、１×１０^−５〜２×１０^−２ｍｏｌがより好ましく、２×１０^−５〜１×１０^−２ｍｏｌが最も好ましい。また、２種類以上の造核促進剤を併用して使用することもできる。
【０１４５】
本発明のハロゲン化銀写真感光材料に用いられる各種添加剤に関しては、特に制限はなく、例えば、特開平３−３９９４８号公報第１０頁右下１１行目〜同公報第１２頁左下５行目に記載のポリヒドロキシベンゼン化合物（具体的には、同公報に記載の化合物（ＩＩＩ）−１〜２５の化合物）；特開平１−１１８８３２号公報に記載の一般式（Ｉ）で表される実質的には可視域に吸収極大を持たない化合物（具体的には、同公報に記載の化合物Ｉ−１〜Ｉ−２６の化合物）；特開平２−１０３５３６号公報第１７頁右下１９行目〜同公報１８頁右上４行目に記載のカブリ防止剤；特開平２−１０３５３６号公報第１８頁左下１２行目〜同頁左下２０行目に記載のポリマーラテックス；特開平９−１７９２２８号公報に記載の一般式（Ｉ）で表される活性メチレン基を有するポリマーラテックス（具体的には同公報に記載の化合物Ｉ−１〜Ｉ−１６）；特開平９−１７９２２８号公報に記載のコア／シェル構造を有するポリマーラテックス（具体的には同公報に記載の化合物Ｐ−１〜Ｐ−５５）；特開平７−１０４４１３号公報第１４頁左１行目〜同頁右３０行目に記載の酸性ポリマーラテックス（具体的には同公報１５頁に記載の化合物ＩＩ−１）〜ＩＩ−９））；特開平２−１０３５３６号公報第１９頁左上１５行目〜同公報１９頁右上１５行目に記載のマット剤、滑り剤、可塑剤；特開平２−１０３５３６号公報第１８頁右上５行目〜同頁右上１７行目に記載の硬膜剤；特開平２−１０３５３６号公報第１８頁右下６行目〜同公報１９頁左上１行目に記載の酸基を有する化合物；特開平２−１８５４２号公報第２頁左下１３行目〜同公報第３頁右上７行目に記載の導電性物質（具体的には、同公報第２頁右下２行目〜同頁右下１０行目に記載の金属酸化物、および同公報に記載の化合物Ｐ−１〜Ｐ−７の導電性高分子化合物）；特開平２−１０３５３６号公報第１７頁右下１行目〜同頁右上１８行目に記載の水溶性染料；特開平９−１７９２４３号公報記載の一般式（ＦＡ）、一般式（ＦＡ１）、一般式（ＦＡ２）、一般式（ＦＡ３）で表される固体分散染料（具体的には同公報記載の化合物Ｆ１〜Ｆ３４、特開平７−１５２１１２号公報記載の（ＩＩ−２）〜（ＩＩ−２４）、特開平７−１５２１１２号公報記載の（ＩＩＩ−５）〜（ＩＩＩ−１８）、特開平７−１５２１１２号公報記載の（ＩＶ−２）〜（ＩＶ−７）、特開平２−２９４６３８号公報および特開平５−１１３８２号公報に記載の固体分散染料）；特開平５ー２７４８１６号公報に記載の酸化されることにより現像抑制剤を放出しうるレドックス化合物、好ましくは同公報に記載の一般式（Ｒ−１）、一般式（Ｒ−２）、一般式（Ｒ−３）で表されるレドックス化合物（具体的には、同公報に記載の化合物Ｒ−１〜Ｒ−６８の化合物）；特開平２−１８５４２号公報第３頁右下１行目〜２０行目に記載のバインダーを挙げることができる。
【０１４６】
本発明のハロゲン化銀写真感光材料の乳剤層および保護層を含めた親水性コロイド層の膨潤率は８０〜１５０％の範囲が好ましく、より好ましくは９０〜１４０％の範囲である。親水性コロイド層の膨潤率は、ハロゲン化銀写真感光材料における乳剤層および保護層を含めた親水性コロイド層の厚み（ｄ_０）を測定し，該ハロゲン化銀写真感光材料を２５℃の蒸留水に１分間浸漬し、膨潤した厚み（Δｄ）を測定し、膨潤率（％）＝（Δｄ÷ｄ_０）×１００の計算式によって求める。
【０１４７】
本発明のハロゲン化銀写真感光材料のハロゲン化銀乳剤層が塗布されている側の膜面ｐＨは７．５以下であることが好ましく、４．５〜６．０であることがより好ましく、４．８〜６．０であることがさらに好ましい。４．５未満であると乳剤層の硬膜進行が遅くなる傾向がある。
【０１４８】
本発明の実施に際して用いうる支持体としては、例えばバライタ紙、ポリエチレン被覆紙、ポリプロピレン合成紙、ガラス板、セルロースアセテート、セルロースナイトレート、例えばポリエチレンテレフタレートなどのポリエステルフィルムを挙げることができる。これらの支持体は、それぞれハロゲン化銀写真感光材料の使用目的に応じて適宜選択される。
また、特開平７−２３４４７８号公報、および米国特許第５，５５８，９７９号明細書に記載のシンジオタクチック構造を有するスチレン系重合体からなる支持体も好ましく用いられる。
【０１４９】
以下に本発明のハロゲン化銀写真感光材料に用いることができる現像液、定着液などの処理剤および処理方法等について述べるが、言うまでもなく本発明は以下の記述および具体例に限定されるものではない。
【０１５０】
本発明のハロゲン化銀写真感光材料の現像処理には、公知の方法のいずれを用いることもできる。また、現像処理液としては公知のものを用いることができる。
【０１５１】
本発明に使用する現像液（以下、現像開始液および現像補充液の双方をまとめて現像液という。）に用いる現像主薬には特別な制限はないが、ジヒドロキシベンゼン類や、アスコルビン酸誘導体、ハイドロキノンモノスルホン酸塩を含むことが好ましく、単独使用でも併用でもよい。特に、ジヒドロキシベンゼン系現像主薬およびこれと超加成性を示す補助現像主薬を含有することが好ましく、ジヒドロキシベンゼン類やアスコルビン酸誘導体と１−フェニル−３−ピラゾリドン類の組み合わせ、またはジヒドロキシベンゼン類やアスコルビン酸誘導体とｐ−アミノフェノール類の組み合わせなどを挙げることができる。
本発明に用いる現像主薬において、ジヒドロキシベンゼン現像主薬としてはハイドロキノン、クロロハイドロキノン、イソプロピルハイドロキノン、メチルハイドロキノンなどがあるが、特にハイドロキノンが好ましい。またアスコルビン酸誘導体現像主薬としては、アスコルビン酸およびイソアスコルビン酸とそれらの塩があるが、特にエリソルビン酸ナトリウムが素材コストの点から好ましい。
【０１５２】
本発明に用いる１−フェニル−３−ピラゾリドンまたはその誘導体の現像主薬としては、１−フェニル−３−ピラゾリドン、１−フェニル−４、４−ジメチル−３−ピラゾリドン、１−フェニル−４−メチル−４−ヒドロキシメチル−３−ピラゾリドンなどがある。
本発明に用いるｐ−アミノフェノール系現像主薬としてＮ−メチル−ｐ−アミノフェノール、ｐ−アミノフェノール、Ｎ−（β−ヒドロキシフェニル）−ｐ−アミノフェノール、Ｎ−（４−ヒドロキシフェニル）グリシン、ｏ−メトキシ−ｐ−（Ｎ、Ｎ−ジメチルアミノ）フェノール、ｏ−メトキシ−ｐ−（Ｎ−メチルアミノ）フェノールなどがあるが、なかでもＮ−メチル−ｐ−アミノフェノール、または特開平９−２９７３７７号公報および特開平９−２９７３７８号公報に記載のアミノフェノール類が好ましい。
【０１５３】
ジヒドロキシベンゼン系現像主薬は通常０．０５ｍｏｌ／Ｌ〜０．８ｍｏｌ／Ｌの量で用いられるのが好ましい。またジヒドロキシベンゼン類と１−フェニル−３−ピラゾリドン類またはｐ−アミノフェノール類の組み合わせを用いる場合には前者を０．０５ｍｏｌ／Ｌ〜０．６ｍｏｌ／Ｌ、好ましくは０．１０ｍｏｌ／Ｌ〜０．５ｍｏｌ／Ｌ、後者を０．０６ｍｏｌ／Ｌ以下、好ましくは０．０３ｍｏｌ／Ｌ〜０．００３ｍｏｌ／Ｌの量で用いるのが好ましい。
【０１５４】
アスコルビン酸誘導体現像主薬は、通常０．０１ｍｏｌ／Ｌ〜０．５ｍｏｌ／Ｌの量で用いられるのが好ましく、０．０５ｍｏｌ／Ｌ〜０．３ｍｏｌ／Ｌがより好ましい。またアスコルビン酸誘導体と１−フェニル−３−ピラゾリドン類もしくはｐ−アミノフェノール類の組み合わせを用いる場合にはアスコルビン酸誘導体を０．０１ｍｏｌ／Ｌ〜０．５ｍｏｌ／Ｌ、１−フェニル−３−ピラゾリドン類もしくはｐ−アミノフェノール類を０．００５ｍｏｌ／Ｌ〜０．２ｍｏｌ／Ｌの量で用いるのが好ましい。
【０１５５】
本発明のハロゲン化銀写真感光材料を処理する際の現像液には、通常用いられる添加剤（例えば現像主薬、アルカリ剤、ｐＨ緩衝剤、保恒剤、キレート剤等）を含有させることができる。以下にこれらの具体例を示すが、本発明で用いることができるものはこれらに限定されるものではない。
現像処理する際の現像液に用いられる緩衝剤としては、炭酸塩、特開昭６２−１８６２５９号公報に記載のほう酸、特開昭６０−９３４３３号公報に記載の糖類（例えばサッカロース）、オキシム類（例えばアセトオキシム）、フェノール類（例えば５−スルホサリチル酸）、第３リン酸塩（例えばナトリウム塩、カリウム塩）などが用いられ、好ましくは炭酸塩が用いられる。緩衝剤、特に炭酸塩の使用量は、好ましくは０．０５ｍｏｌ／Ｌ以上、特に０．０８〜１．０ｍｏｌ／Ｌである。
【０１５６】
本発明においては、現像開始液および現像補充液の双方が、該液１Ｌに０．１ｍｏｌの水酸化ナトリウムを加えたときのｐＨ上昇が０．８以下であることが好ましい。使用する現像開始液ないし現像補充液がこの性質を有することを確かめる方法としては、試験する現像開始液ないし現像補充液のｐＨを１０．５に合わせ、ついでこの液１Ｌに水酸化ナトリウムを０．１ｍｏｌ添加し、この時の液のｐＨ値を測定し、ｐＨ値の上昇が０．８以下であれば上記に規定した性質を有すると判定する。本発明では特に、上記試験を行った時のｐＨ値の上昇が０．７以下である現像開始液および現像補充液を用いることが好ましい。
【０１５７】
本発明に用いられる保恒剤としては亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸リチウム、亜硫酸アンモニウム、重亜硫酸ナトリウム、メタ重亜硫酸カリウム、ホルムアルデヒド重亜硫酸ナトリウムなどがある。亜硫酸塩は好ましくは０．２ｍｏｌ／Ｌ以上、特に０．３ｍｏｌ／Ｌ以上用いられるが、あまりに多量添加すると現像液中の銀汚れの原因になるので、上限は１．２ｍｏｌ／Ｌとするのが望ましい。特に好ましくは、０．３５〜０．７ｍｏｌ／Ｌである。
ジヒドロキシベンゼン系現像主薬の保恒剤として、亜硫酸塩と併用して前記のアスコルビン酸誘導体を少量使用してもよい。なかでも素材コストの点からエリソルビン酸ナトリウムを用いることが好ましい。添加量はジヒドロキシベンゼン系現像主薬に対して、ｍｏｌ比で０．０３〜０．１２の範囲が好ましく、特に好ましくは０．０５〜０．１０の範囲である。保恒剤としてアスコルビン酸誘導体を使用する場合には現像液中にホウ素化合物を含まないことが好ましい。
【０１５８】
上記以外に用いられる添加剤としては、臭化ナトリウム、臭化カリウムのような現像抑制剤、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ジメチルホルムアミドのような有機溶剤、ジエタノールアミン、トリエタノールアミンなどのアルカノールアミン、イミダゾールまたはその誘導体等の現像促進剤、ヘテロ環メルカプト化合物（例えば３−（５−メルカプトテトラゾール−１−イル）ベンゼンスルホン酸ナトリウム、１−フェニル−５−メルカプトテトラゾールなど）、特開昭６２−２１２６５１号公報に記載の化合物を物理現像ムラ防止剤として添加することもできる。
また、メルカプト系化合物、インダゾール系化合物、ベンゾトリアゾール系化合物、ベンゾイミダゾール系化合物をカブリ防止剤または黒ポツ（ｂｌａｃｋ ｐｅｐｐｅｒ）防止剤として含んでもよい。具体的には、５−ニトロインダゾール、５−ｐ−ニトロベンゾイルアミノインダゾール、１−メチル−５−ニトロインダゾール、６−ニトロインダゾール、３−メチル−５−ニトロインダゾール、５−ニトロベンゾイミダゾール、２−イソプロピル−５−ニトロベンゾイミダゾール、５−ニトロベンゾトリアゾール、４−（（２−メルカプト−１、３、４−チアジアゾール−２−イル）チオ）ブタンスルホン酸ナトリウム、５−アミノ−１、３、４−チアジアゾール−２−チオール、メチルベンゾトリアゾール、５−メチルベンゾトリアゾール、２−メルカプトベンゾトリアゾールなどを挙げることができる。これらの添加剤の量は、通常現像液１Ｌあたり０．０１〜１０ｍｍｏｌであり、より好ましくは０．１〜２ｍｍｏｌである。
【０１５９】
さらに本発明で用いられる現像液中には各種の有機、無機のキレート剤を単独または併用で用いることができる。
無機キレート剤としては例えば、テトラポリリン酸ナトリウム、ヘキサメタリン酸ナトリウムなどを用いることができる。
一方、有機キレート剤としては、主に有機カルボン酸、アミノポリカルボン酸、有機ホスホン酸、アミノホスホン酸および有機ホスホノカルボン酸を用いることができる。
有機カルボン酸としては例えば、アクリル酸、シュウ酸、マロン酸、コハク酸、グルタル酸、グルコン酸、アジピン酸、ピメリン酸、アシエライン酸、セバチン酸、ノナンジカルボン酸、デカンジカルボン酸、ウンデカンジカルボン酸、マレイン酸、イタコン酸、リンゴ酸、クエン酸、酒石酸などを挙げることができる。
【０１６０】
アミノポリカルボン酸としては例えば、イミノ二酢酸、ニトリロ三酢酸、ニトリロ三プロピオン酸、エチレンジアミンモノヒドロキシエチル三酢酸、エチレンジアミン四酢酸、グリコールエーテル四酢酸、１、２−ジアミノプロパン四酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラミン六酢酸、１、３−ジアミノ−２−プロパノール四酢酸、グリコールエーテルジアミン四酢酸、その他特開昭５２−２５６３２号公報、同５５−６７７４７号公報、同５７−１０２６２４号公報、および特公昭５３−４０９００号公報に記載の化合物を挙げることができる。
【０１６１】
有機ホスホン酸としては、例えば米国特許第３，２１４，４５４号明細書、同第３，７９４，５９１号明細書および西独特許公開第２２２７３６９号公報等に記載のヒドロキシアルキリデン−ジホスホン酸やリサーチ・ディスクロージャー第１８１巻、Ｉｔｅｍ １８１７０（１９７９年５月号）等に記載の化合物が挙げられる。
アミノホスホン酸としては、例えばアミノトリス（メチレンホスホン酸）、エチレンジアミンテトラメチレンホスホン酸、アミノトリメチレンホスホン酸等が挙げられるが、その他上記リサーチ・ディスクロージャー１８１７０、特開昭５７−２０８５５４号公報、同５４−６１１２５号公報、同５５−２９８８３号公報、同５６−９７３４７号公報等に記載の化合物も挙げることができる。
【０１６２】
有機ホスホノカルボン酸としては、例えば特開昭５２−１０２７２６号公報、同５３−４２７３０号公報、同５４−１２１１２７号公報、同５５−４０２４号公報、同５５−４０２５号公報、同５５−１２６２４１号公報、同５５−６５９５５号公報、同５５−６５９５６号公報および前述のリサーチ・ディスクロージャー１８１７０等に記載の化合物を挙げることができる。
【０１６３】
これらの有機および／または無機のキレート剤は、前述のものに限定されるものではない。また、アルカリ金属塩やアンモニウム塩の形で使用してもよい。これらのキレート剤の添加量としては、現像液１Ｌあたり好ましくは、１×１０^−４〜１×１０^−１ｍｏｌ、より好ましくは１×１０^−３〜１×１０^−２ｍｏｌである。
【０１６４】
さらに、現像液中に銀汚れ防止剤として、例えば特開昭５６−２４３４７号公報、特公昭５６−４６５８５号公報、特公昭６２−２８４９号公報、特開平４−３６２９４２号公報、特開平８−６２１５号公報に記載の化合物の他、メルカプト基を１つ以上有するトリアジン（例えば特公平６−２３８３０号公報、特開平３−２８２４５７号公報、特開平７−１７５１７８号公報に記載の化合物）、メルカプト基を１つ以上有するピリミジン（例えば２−メルカプトピリミジン、２、６−ジメルカプトピリミジン、２、４−ジメルカプトピリミジン、５、６−ジアミノ−２、４−ジメルカプトピリミジン、２、４、６−トリメルカプトピリミジン、特開平９−２７４２８９号公報記載の化合物など）、メルカプト基を１つ以上有するピリジン（例えば２−メルカプトピリジン、２、６−ジメルカプトピリジン、３、５−ジメルカプトピリジン、２、４、６−トリメルカプトピリジン、特開平７−２４８５８７号公報に記載の化合物など）、メルカプト基を１つ以上有するピラジン（例えば２−メルカプトピラジン、２、６−ジメルカプトピラジン、２、３−ジメルカプトピラジン、２、３、５−トリメルカプトピラジンなど）、メルカプト基を１つ以上有するピリダジン（例えば３−メルカプトピリダジン、３、４−ジメルカプトピリダジン、３、５−ジメルカプトピリダジン、３、４、６−トリメルカプトピリダジンなど）、特開平７−１７５１７７号公報に記載の化合物、米国特許第５，４５７，０１１号明細書に記載のポリオキシアルキルホスホン酸エステルなどを用いることができる。これらの銀汚れ防止剤は単独または複数の併用で用いることができ、添加量は現像液１Ｌあたり０．０５〜１０ｍｍｏｌが好ましく、０．１〜５ｍｍｏｌがより好ましい。
また、溶解助剤として特開昭６１−２６７７５９号公報記載の化合物を用いることができる。
さらに必要に応じて色調剤、界面活性剤、消泡剤、硬膜剤等を含んでもよい。
【０１６５】
現像液の好ましいｐＨは９．０〜１２．０であり、特に好ましくは９．０〜１１．０、さらに好ましくは９．５〜１１．０の範囲である。ｐＨ調整に用いるアルカリ剤には通常の水溶性無機アルカリ金属塩（例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム等）を用いることができる。
【０１６６】
現像液のカチオンとしては、ナトリウムイオンに比べてカリウムイオンの方が現像抑制をせず、またフリンジと呼ばれる黒化部のまわりのギザギザが少ない。さらに、濃縮液として保存する場合には一般にカリウム塩のほうが溶解度が高く好ましい。しかしながら、定着液においてはカリウムイオンは銀イオンと同程度に定着阻害をすることから、現像液のカリウムイオン濃度が高いと、ハロゲン化銀写真感光材料により現像液が持ち込まれることにより定着液中のカリウムイオン濃度が高くなり、好ましくない。以上のことから現像液におけるカリウムイオンとナトリウムイオンのｍｏｌ比率は２０：８０〜８０：２０の間であることが好ましい。カリウムイオンとナトリウムイオンの比率は、ｐＨ緩衝剤、ｐＨ調整剤、保恒剤、キレート剤などの対カチオンで、上記の範囲で任意に調整できる。
【０１６７】
現像液の補充量は、ハロゲン化銀写真感光材料１ｍ^２につき４７０ｍｌ以下であり、３０〜３２５ｍｌが好ましい。現像補充液は、現像開始液と同一の組成および／または濃度を有していてもよいし、開始液と異なる組成および／または濃度を有していてもよい。
【０１６８】
本発明における定着処理剤の定着剤としては、チオ硫酸アンモニウム、チオ硫酸ナトリウム、チオ硫酸ナトリウムアンモニウムが使用できる。定着剤の使用量は適宜変えることができるが、一般には約０．７〜約３．０ｍｏｌ／Ｌである。
【０１６９】
本発明における定着液は、硬膜剤として作用する水溶性アルミニウム塩、水溶性クロム塩を含んでもよく、水溶性アルミニウム塩が好ましい。それには例えば塩化アルミニウム、硫酸アルミニウム、カリ明礬、硫酸アルミニウムアンモニウム、硝酸アルミニウム、乳酸アルミニウムなどがある。これらは使用液におけるアルミニウムイオン濃度として、０．０１〜０．１５ｍｏｌ／Ｌで含まれることが好ましい。
なお、定着液を濃縮液または固形剤として保存する場合、硬膜剤などを別パートとした複数のパーツで構成してもよいし、すべての成分を含む一剤型の構成としてもよい。
【０１７０】
定着処理剤には所望により保恒剤（例えば亜硫酸塩、重亜硫酸塩、メタ重亜硫酸塩などを０．０１５ｍｏｌ／Ｌ以上、好ましくは０．０２ｍｏｌ／Ｌ〜０．３ｍｏｌ／Ｌ）、ｐＨ緩衝剤（例えば酢酸、酢酸ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、リン酸、コハク酸、アジピン酸などを０．１ｍｏｌ／Ｌ〜１ｍｏｌ／Ｌ、好ましくは０．２ｍｏｌ／Ｌ〜０．７ｍｏｌ／Ｌ）、アルミニウム安定化能や硬水軟化能のある化合物（例えばグルコン酸、イミノジ酢酸、５−スルホサリチル酸、グルコヘプタン酸、リンゴ酸、酒石酸、クエン酸、シュウ酸、マレイン酸、グリコール酸、安息香酸、サリチル酸、タイロン、アスコルビン酸、グルタル酸、アスパラギン酸、グリシン、システイン、エチレンジアミン四酢酸、ニトリロ三酢酸やこれらの誘導体およびこれらの塩、糖類などを０．００１ｍｏｌ／Ｌ〜０．５ｍｏｌ／Ｌ、好ましくは０．００５ｍｏｌ／Ｌ〜０．３ｍｏｌ／Ｌ）を含むことができが、近年の環境保護の点からホウ素系化合物は含まない方がよい。
【０１７１】
このほか、特開昭６２−７８５５１号公報に記載の化合物、ｐＨ調整剤（例えば水酸化ナトリウム、アンモニア、硫酸など）、界面活性剤、湿潤剤、定着促進剤等も含むことができる。界面活性剤としては、例えば硫酸化物スルホン酸化物などのアニオン界面活性剤、ポリエチレン系界面活性剤、特開昭５７−６８４０号公報記載の両性界面活性剤が挙げられ、公知の消泡剤を使用することもできる。湿潤剤としては、アルカノールアミン、アルキレングリコール等がある。定着促進剤としては、特開平６−３０８６８１号公報に記載のアルキルおよびアリル置換されたチオスルホン酸およびその塩や、特公昭４５−３５７５４号公報、同５８−１２２５３５号公報、同５８−１２２５３６号公報記載のチオ尿素誘導体、分子内に３重結合を有するアルコール、米国特許第４，１２６，４５９号明細書記載のチオエーテル化合物、特開昭６４−４７３９号公報、特開平１−４７３９号公報、同１−１５９６４５号公報および同３−１０１７２８号公報に記載のメルカプト化合物、同４−１７０５３９号公報に記載のメソイオン化合物、チオシアン酸塩を含むことができる。
【０１７２】
本発明における定着液のｐＨは４．０以上であることが好ましく、４．５〜６．０であることがより好ましい。定着液のｐＨは処理により現像液が混入して上昇するが、この場合のｐＨは、硬膜定着液では６．０以下であることが好ましく、５．７以下であることがより好ましく、また、無硬膜定着液においては７．０以下であることが好ましく、６．７以下であることがより好ましい。
【０１７３】
定着液の補充量は、ハロゲン化銀写真感光材料１ｍ^２につき５００ｍｌ以下であることが好ましく、３９０ｍｌ以下であることがより好ましく、８０〜３２５ｍｌであることが特に好ましい。補充液は、開始液と同一の組成および／または濃度を有していてもよいし、開始液と異なる組成および／または濃度を有していてもよい。
【０１７４】
定着液は電解銀回収などの公知の定着液再生方法により再生使用することができる。再生装置としては、例えば富士写真フイルム（株）製ＦＳ−２０００などがある。
また、活性炭などの吸着フィルターを使用して、色素などを除去することも好ましい。
【０１７５】
本発明における現像および定着処理剤が液剤の場合、例えば特開昭６１−７３１４７号公報に記載されたような、酸素透過性の低い包材で保管することが好ましい。さらにこれらの液が濃縮液の場合、所定の濃度になるように、濃縮液１部に対して水０．２〜３部の割合で希釈して使用される。
【０１７６】
本発明における現像処理剤および定着処理剤は固形にしても液剤同様の結果が得られる。以下に固形処理剤について説明する。
本発明では、固形剤として、公知の形態（粉状、粒状、顆粒状、塊状、錠剤、コンパクター、ブリケット、板状、棒状、ペースト状など）を有するものが使用できる。これらの固形剤は、接触して互いに反応する成分を分離するために、水溶性のコーティング剤やフィルムで被覆してもよいし、複数の層構成にして互いに反応する成分を分離してもよく、これらを併用してもよい。
【０１７７】
被覆剤、造粒助剤としては公知のものが使用できるが、ポリビニルピロリドン、ポリエチレングリコール、ポリスチレンスルホン酸、ビニル系化合物を用いることが好ましい。この他、特開平５−４５８０５号公報カラム２の４８行〜カラム３の１３行目を参考にすることができる。
【０１７８】
複数の層構成にする場合は、接触しても反応しない成分を互いに反応する成分の間にはさんだ構成にして錠剤やブリケット等に加工してもよいし、公知の形態の成分を同様の層構成にして包装してもよい。これらの方法は、例えば特開昭６１−２５９９２１号公報、同４−１６８４１号公報、同４−７８８４８号公報、同５−９３９９１号公報等に示されている。
【０１７９】
固形処理剤の嵩密度は、０．５〜６．０ｇ／ｃｍ^３が好ましく、特に錠剤は１．０〜５．０ｇ／ｃｍ^３が好ましく、顆粒は０．５〜１．５ｇ／ｃｍ^３が好ましい。
【０１８０】
本発明における固形処理剤の製法は、公知のいずれの方法を用いることができる。例えば、特開昭６１−２５９９２１号公報、特開平４−１５６４１号公報、特開平４−１６８４１号公報、同４−３２８３７号公報、同４−７８８４８号公報、同５−９３９９１号公報、同４−８５５３３号公報、同４−８５５３４号公報、同４−８５５３５号公報、同５−１３４３６２号公報、同５−１９７０７０号公報、同５−２０４０９８号公報、同５−２２４３６１号公報、同６−１３８６０４号公報、同６−１３８６０５号公報、同８−２８６３２９号公報等を参考にすることができる。
【０１８１】
より具体的には転動造粒法、押し出し造粒法、圧縮造粒法、解砕造粒法、撹拌造粒法、スプレードライ法、溶解凝固法、ブリケッティング法、ローラーコンパクティング法等を用いることができる。
【０１８２】
本発明における固形剤は、表面状態（平滑、多孔質等）や部分的に厚みを変えたり、中空状のドーナツ型にしたりして溶解性を調節することもできる。さらに、複数の造粒物に異なった溶解性を与えたり、溶解性の異なる素材の溶解度を合わせるために、複数の形状をとることも可能である。また、表面と内部で組成の異なる多層の造粒物でもよい。
【０１８３】
固形剤の包材は、酸素および水分透過性の低い材質が好ましく、包材の形状は袋状、筒状、箱状などの公知のものが使用できる。また、特開平６−２４２５８５号公報〜同６−２４２５８８号公報、同６−２４７４３２号公報、同６−２４７４４８号公報、同６−３０１１８９号公報、同７−５６６４号公報、同７−５６６６号公報〜同７−５６６９号公報に開示されているような折り畳み可能な形状にすることも、廃包材の保管スペース削減のためには好ましい。これらの包材は、処理剤の取り出し口にスクリューキャップや、プルトップ、アルミシールをつけたり、包材をヒートシールしてもよいが、このほかの公知のものを使用してもよく、特に限定はしない。さらに環境保全上、廃包材をリサイクルまたはリユースすることが好ましい。
【０１８４】
固形処理剤の溶解および補充の方法としては特に限定はなく、公知の方法を使用することができる。これらの方法としては例えば、撹拌機能を有する溶解装置で一定量を溶解し補充する方法、特開平９−８０７１８号公報に記載されているような溶解部分と完成液をストックする部分とを有する溶解装置で溶解し、ストック部から補充する方法、特開平５−１１９４５４号公報、同６−１９１０２号公報、同７−２６１３５７号公報に記載されているような自動現像機の循環系に処理剤を投入して溶解・補充する方法、溶解槽を内蔵する自動現像機でハロゲン化銀写真感光材料の処理に応じて処理剤を投入し溶解する方法などがあるが、このほかの公知のいずれの方法を用いることもできる。また処理剤の投入は、人手で行ってもよいし、特開平９−１３８４９５号公報に記載されているような開封機構を有する溶解装置や自動現像機で自動開封、自動投入してもよく、作業環境の点からは後者が好ましい。具体的には取り出し口を突き破る方法、はがす方法、切り取る方法、押し切る方法や、特開平６−１９１０２号公報、同６−９５３３１号公報に記載の方法などがある。
【０１８５】
現像、定着処理が済んだハロゲン化銀写真感光材料は、ついで水洗または安定化処理される（以下特に断らない限り、安定化処理を含めて水洗といい、これらに使用する液を、水または水洗水という）。水洗に使用される水は、水道水でもイオン交換水でも蒸留水でも安定化液でもよい。これらの補充量は、一般的にはハロゲン化銀写真感光材料１ｍ^２あたり約８Ｌ〜約１７Ｌであるが、それ以下の補充量で行うこともできる。特に３Ｌ以下の補充量（０も含む。すなわち、ため水水洗）では、節水処理が可能となるのみならず、自動現像機設置の配管を不要とすることもできる。水洗を低補充量で行う場合は、特開昭６３−１８３５０号公報、同６２−２８７２５２号公報等に記載のスクイズローラー、クロスオーバーローラーの洗浄槽を設けることがより好ましい。また、少量水洗時に問題となる公害負荷低減や、水垢防止のために種々の酸化剤（例えばオゾン、過酸化水素、次亜塩素酸ナトリウム、活性ハロゲン、二酸化塩素、炭酸ナトリウム過酸化水素塩など）添加やフィルター濾過を組み合わせてもよい。
【０１８６】
水洗の補充量を少なくする方法として、古くより多段向流方式（例えば２段、３段等）が知られており、水洗補充量はハロゲン化銀写真感光材料１ｍ^２あたり５０〜２００ｍｌが好ましい。この効果は、独立多段方式（向流にせず、多段の水洗槽に個別に新液を補充する方法）でも同様に得られる。
【０１８７】
さらに、水洗工程に水垢防止手段を施してもよい。水垢防止手段としては公知のものを使用することができ、特に限定はしないが、防ばい剤（いわゆる水垢防止剤）を添加する方法、通電する方法、紫外線または赤外線や遠赤外線を照射する方法、磁場をかける方法、超音波処理する方法、熱をかける方法、未使用時にタンクを空にする方法などがある。これらの水垢防止手段は、ハロゲン化銀写真感光材料の処理に応じてなされてもよいし、使用状況に関係なく一定間隔で行われてもよいし、夜間など処理の行われない期間のみ施してもよい。またあらかじめ水洗水に施しておいて、これを補充してもよい。さらには、一定期間ごとに異なる水垢防止手段を行うことも、耐性菌の発生を抑える上では好ましい。
節水水垢防止装置としては、富士フイルム社製装置ＡＣ−１０００と水垢防止剤として富士フイルム社製ＡＢ−５を用いてもよく特開平１１−２３１４８５号公報の方法を用いてもよい。
防ばい剤としては特に限定はなく公知のものが使用できる。前述の酸化剤の他例えばグルタルアルデヒド、アミノポリカルボン酸等のキレート剤、カチオン性界面活性剤、メルカプトピリジンオキシド（例えば２−メルカプトピリジン−Ｎ−オキシドなど）などがあり、単独使用でも複数の併用でもよい。
通電する方法としては、特開平３−２２４６８５号公報、同３−２２４６８７号公報、同４−１６２８０号公報、同４−１８９８０号公報などに記載の方法が使用できる。
【０１８８】
このほか、水泡ムラ防止や汚れ転写防止のために、公知の水溶性界面活性剤や消泡剤を添加してもよい。また、ハロゲン化銀写真感光材料から溶出した染料による汚染防止に、特開昭６３−１６３４５６号公報に記載の色素吸着剤を水洗系に設置してもよい。
【０１８９】
水洗工程からのオーバーフロー液の一部または全部は、特開昭６０−２３５１３３号公報に記載されているように、定着能を有する処理液に混合利用することもできる。また微生物処理（例えば硫黄酸化菌、活性汚泥処理や微生物を活性炭やセラミック等の多孔質担体に担持させたフィルターによる処理等）や、通電や酸化剤による酸化処理をして、生物化学的酸素要求量（ＢＯＤ）、化学的酸素要求量（ＣＯＤ）、沃素消費量等を低減してから排水したり、銀と親和性のあるポリマーを用いたフィルターやトリメルカプトトリアジン等の難溶性銀錯体を形成する化合物を添加して銀を沈降させてフィルター濾過するなどし、排水中の銀濃度を低下させることも、自然環境保全の観点から好ましい。
【０１９０】
また、水洗処理に続いて安定化処理する場合もあり、その例として特開平２−２０１３５７号公報、同２−１３２４３５号公報、同１−１０２５５３号公報、特開昭４６−４４４４６号公報に記載の化合物を含有した浴をハロゲン化銀写真感光材料の最終浴として使用してもよい。この安定浴にも必要に応じてアンモニウム化合物、Ｂｉ、Ａｌ等の金属化合物、蛍光増白剤、各種キレート剤、膜ｐＨ調節剤、硬膜剤、殺菌剤、防ばい剤、アルカノールアミンや界面活性剤を加えることもできる。
【０１９１】
水洗、安定化浴に添加する防ばい剤等の添加剤および安定化剤は、前述の現像、定着処理剤同様に固形剤とすることもできる。
【０１９２】
本発明に使用する現像液、定着液、水洗水、安定化液の廃液は焼却処分することが好ましい。また、これらの廃液は例えば特公平７−８３８６７号公報、米国特許第５，４３９，５６０明細書等に記載されているような濃縮装置で濃縮液化または固化させてから処分することも可能である。
【０１９３】
処理剤の補充量を低減する場合には、処理槽の開口面積を小さくして液の蒸発、空気酸化を防止することが好ましい。ローラー搬送型の自動現像機については米国特許第３，０２５，７７９明細書、同第３，５４５，９７１明細書などに記載されており、本明細書においては単にローラー搬送型自動現像機として言及する。この自現機は現像、定着、水洗および乾燥の四工程からなっており、本発明のハロゲン化銀写真感光材料を処理する際も、他の工程（例えば停止工程）を除外しないが、この四工程を踏襲するのが最も好ましい。さらに、現像定着間および／または定着水洗間にリンス浴、水洗槽や洗浄槽を設けてもよい。
【０１９４】
本発明のハロゲン化銀写真感光材料を現像処理する際には、処理開始から乾燥後まで（ｄｒｙ ｔｏ ｄｒｙ）を２５〜１６０秒で行うことが好ましく、現像および定着時間は４０秒以下であることが好ましく、６〜３５秒であることがより好ましく、各液の温度は２５〜５０℃が好ましく、３０〜４０℃が好ましい。水洗の温度および時間は０〜５０℃で４０秒以下が好ましい。この方法によれば、現像、定着および水洗されたハロゲン化銀写真感光材料は水洗水を絞りきる、すなわちスクイズローラーを経て乾燥してもよい。乾燥は約４０〜約１００℃で行われ、乾燥時間は周囲の状態によって適宜変えられる。乾燥方法は公知のいずれの方法も用いることができ特に限定はないが、温風乾燥や、特開平４−１５５３４号公報、同５−２２５６号公報、同５−２８９２９４号公報に開示されているようなヒートローラー乾燥、遠赤外線による乾燥などがあり、複数の方法を併用してもよい。
【０１９５】
【実施例】
以下に実施例と比較例を挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。また、実施例中の「部」は特に示さない限り質量部を示す。
【０１９６】
＜実施例１＞
《乳剤Ａの調製》
１液
水 ７５０ｍｌ
ゼラチン ２０ｇ
塩化ナトリウム ３ｇ
１，３−ジメチルイミダゾリジン−２−チオン ２０ｍｇ
ベンゼンチオスルホン酸ナトリウム １０ｍｇ
クエン酸 ０．７ｇ
【０１９７】
２液
水 ３００ｍｌ
硝酸銀 １５０ｇ
【０１９８】

【０１９９】
３液に用いるＫ_３ＩｒＣｌ_６（０．００５％）、（ＮＨ_４）_３［ＲｈＣｌ_５（Ｈ_２Ｏ）］（０．００１％）は、粉末をそれぞれＫＣｌの２０％水溶液、ＮａＣｌの２０％水溶液に溶解し、４０℃で１２０分間加熱して調製した。
【０２００】
３８℃、ｐＨ４．５に保たれた１液に、２液と３液の各々９０％に相当する量を攪拌しながら同時に２０分間にわたって加え、０．２１μｍの核粒子を形成した。続いて下記４液、５液を８分間にわたって加え、さらに、２液と３液の残りの１０％の量を２分間にわたって加え、０．２３μｍまで成長させた。さらに、ヨウ化カリウム０．１５ｇを加え５分間熟成し粒子形成を終了した。
【０２０１】
４液
水 １００ｍｌ
硝酸銀 ５０ｇ
【０２０２】
５液
水 １００ｍｌ
塩化ナトリウム １３ｇ
臭化カリウム １１ｇ
Ｋ_４［Ｆｅ（ＣＮ）_６］・３Ｈ_２Ｏ（黄血塩） ８．０ｘ１０^−７ｍｏｌ／Ａｇｍｏｌ
【０２０３】
その後、常法にしたがってフロキュレーション法によって水洗した。具体的には、温度を３５℃に下げ、下記に示すアニオン性沈降剤−１を３ｇ加え、硫酸を用いてハロゲン化銀が沈降するまでｐＨを下げた（ｐＨ３．２±０．２の範囲であった）。次に上澄み液を約３Ｌ除去した（第一水洗）。さらに３Ｌの蒸留水を加えてから、ハロゲン化銀が沈降するまで硫酸を加えた。再度上澄み液を３Ｌ除去した（第二水洗）。第二水洗と同じ操作をさらに１回繰り返し（第三水洗）て水洗・脱塩行程を終了した。水洗・脱塩後の乳剤にゼラチン４５ｇを加え、ｐＨ５．６、ｐＡｇ７．５に調整し、ベンゼンチオスルホン酸ナトリウム１０ｍｇ、ベンゼンチオスルフィン酸ナトリウム３ｍｇ、チオ硫酸ナトリウム５水和物１５ｍｇと塩化金酸４．０ｍｇを加え５５℃にて最適感度を得るように化学増感を施し、安定剤として４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラアザインデン１００ｍｇと防腐剤（ＩＣＩ（株）製、プロキセル）１００ｍｇを加えた。
最終的に臭化銀を３０ｍｏｌ％、沃化銀を０．０８ｍｏｌ％含む平均粒子サイズ０．２４μｍ、変動係数９％のヨウ塩臭化銀立方体粒子乳剤を得た。最終的に乳剤として、ｐＨ＝５．７、ｐＡｇ＝７．５、電導度＝４０μＳ／ｍ、密度＝１．２〜１．２５ｘ１０^３ｋｇ／ｍ^３、粘度＝５０ｍＰａ・ｓとなった。また、金属錯体が含まれている内部の銀モル量は、全銀量の９２．５％であった。
【０２０４】
【化４４】

【０２０５】
《乳剤Ｂの調製》
乳剤Ａに対し、臭化銀を５５ｍｏｌ％、平均粒子サイズ０．２１μｍ、Ｋ_４［Ｆｅ（ＣＮ）_６］・３Ｈ_２Ｏ（黄血塩）のドープ量を３．０ｘ１０^−５ｍｏｌ／Ａｇｍｏｌに変更する以外は乳剤Ａと同様に調製した。なお、ハロゲン組成の調整は３液、および５液の塩化ナトリウム、臭化カリウムの添加量を、粒子サイズの調整は１液の塩化ナトリウムの添加量、調製温度を変更することにより行った。
【０２０６】
《塗布液の作製》
本実施例で調製するハロゲン化銀写真感光材料は、下記に示す両面が塩化ビニリデンを含む防湿層下塗りからなるポリエチレンテレフタレートフィルム支持体の一面に、ＵＬ層／乳剤層／保護層下層／保護層上層を形成し、その反対面に導電層／バック層を形成した構造を有する。
以下に各層を形成するために用いた塗布液の組成を示す。
【０２０７】
ＵＬ層塗布液
ゼラチン ０．５ｇ／ｍ^２
ポリエチルアクリレートラテックス １５０ｍｇ／ｍ^２
化合物（Ｃｐｄ−７） ４０ｍｇ／ｍ^２
化合物（Ｃｐｄ−１４） １０ｍｇ／ｍ^２
５−メチルベンゾトリアゾール ２０ｍｇ／ｍ^２
防腐剤（ＩＣＩ（株）製、プロキセル） １．５ｍｇ／ｍ^２
【０２０８】

クエン酸を用いて塗布液ｐＨを５．６に調整した。
このようにして調製した乳剤層塗布液を下記支持体上に銀量２．９ｇ／ｍ^２、ゼラチン量１．２ｇ／ｍ^２になるように塗布した。
【０２０９】
【化４５】

【０２１０】
保護層下層塗布液
ゼラチン ０．５ｇ／ｍ^２
化合物（Ｃｐｄ−１２） １５ｍｇ／ｍ^２
１，５−ジヒドロキシ−２−ベンズアルドキシム １０ｍｇ／ｍ^２
ポリエチルアクリレートラテックス １５０ｍｇ／ｍ^２
化合物（Ｃｐｄ−１３） ３ｍｇ／ｍ^２
化合物（Ｃｐｄ−２０） ５ｍｇ／ｍ^２
防腐剤（ＩＣＩ（株）製、プロキセル） １．５ｍｇ／ｍ^２
【０２１１】

なお、各層の塗布液には、下記増粘剤Ｚを加えて粘度調整した。
【０２１２】
【化４６】

【０２１３】

【０２１４】

【０２１５】
【化４７】

【０２１６】
《支持体》
二軸延伸したポリエチレンテレフタレート支持体（厚み１７５μｍ）の両面に下記組成の下塗層第１層塗布液、下塗層第２層塗布液および下塗層第３層塗布液を支持体に近い側から順に第１層、第２層、第３層を塗布した。
【０２１７】
下塗層１層塗布液
モンモリロナイト（クニミネ工業（株）製クニピアＧ）４部を２００部の水に分散させ、これにｎ−ドデシルトリメチルアンモニウムクロリド２．５部を加え、室温で１時間攪拌した。これを水で充分洗浄しながらメンブレンフィルターを用いて吸引濾過し、１００℃で２４時間真空乾燥し、有機アンモニウム塩で被覆した有機モンモリロナイトを得た。さらに、得られた有機モンモリロナイト２部、水分散性ポリエステル樹脂（２，６−ナフタレンジカルボン酸／エチレングリコール／スルホテレフタル酸ナトリウム共重合物）１００部を水に１０質量％になるように分散し、下塗り層形成用塗布液とした。
上記下塗り層形成用塗布液を乾燥後の厚みが０．５μｍになるように塗布した（サンプルＮｏ．１）。
【０２１８】

さらに、１０質量％のＫＯＨを加え、ｐＨ＝６に調整した塗布液を乾燥温度１８０℃で２分間乾燥した後の乾燥膜厚が０．９μｍになる様に塗布した。
【０２１９】
下塗層第３層塗布液
ゼラチン １ｇ
メチルセルロース ０．０５ｇ
化合物（Ｃｐｄ−２２） ０．０２ｇ
Ｃ_１２Ｈ_２５Ｏ（ＣＨ_２ＣＨ_２Ｏ）_１０Ｈ ０．０３ｇ
防腐剤（ＩＣＩ（株）製、プロキセル） ３．５×１０^−３ｇ
酢酸 ０．２ｇ
水 合計量が１００ｇになる量
この塗布液を乾燥温度１７０℃で２分間乾燥した後の乾燥膜厚が０．１μｍになる様に塗布した。
【０２２０】
サンプルＮｏ．２〜６は、支持体上に塗設する下塗り第１層に添加するフィラーの分散時間、塗布厚みを表１に示した通りに変更し、それ以外はサンプルＮｏ．１と同様の方法で作製した。
【０２２１】
サンプルＮｏ．７は、下塗り層に含まれるフィラーを平均一次粒子サイズ５ｎｍのエアロジルに変更した以外はサンプルＮｏ．１と同様の方法で作製した。
【０２２２】
サンプルＮｏ．８は、下塗層第１層を設けないこと以外はサンプルＮｏ．１と同様の方法で作製した。
【０２２３】
サンプルＮｏ．９は、下塗層第１層にフィラーを含まないこと以外はサンプルＮｏ．１と同様の方法で作製した。
【化４８】

【０２２４】
《支持体上への塗布方法》
上記下塗層を施した支持体上に、まず乳剤面側として支持体に近い側よりＵＬ層、乳剤層、保護層下層、保護層上層の順に４層を、３５℃に保ちながらスライドビードコーター方式により硬膜剤液を加えつつ同時重層塗布し、冷風セットゾーン（５℃）を通過させた後、乳剤面とは反対側に支持体に近い側より、導電層、バック層の順に、カーテンコーター方式により硬膜剤液を加えながら同時重層塗布し、冷風セットゾーン（５℃）を通過させた。各々のセットゾーンを通過した時点では、塗布液は充分なセット性を示した。引き続き乾燥ゾーンにて両面を同時に下記乾燥条件にて乾燥した。なお、バック面側を塗布した後、巻き取りまではローラー、その他には一切無接触の状態で搬送した。この時の塗布速度は２００ｍ／ｍｉｎであった。
【０２２５】
《乾燥条件》
セット後、水／ゼラチンの質量比が８００％になるまで３０℃の乾燥風で乾燥し、８００％から２００％になるまでを３５℃相対湿度３０％の乾燥風で乾燥させ、そのまま風を当て、表面温度３４℃となった時点（乾燥終了と見なす）から３０秒後に、４８℃相対湿度２％の空気で１分間乾燥した。この時、乾燥時間は乾燥開始から水／ゼラチン比８００％までが５０秒、８００％から２００％までが３５秒、２００％から乾燥終了までが５秒であった。
【０２２６】
このハロゲン化銀写真感光材料を２５℃相対湿度５５％で巻き取り、次いで同環境下で裁断し、６時間調湿したバリアー袋に、２５℃相対湿度５０％で８時間調湿した後、２５℃相対湿度５０％で２時間調湿してある厚紙と共に密閉し、表１に示すサンプルＮｏ．１〜９を作製した。
バリアー袋内の湿度を測定したところ４５％であった。また、得られた試料の乳剤層側の膜面ｐＨは５．５〜５．８、バック側の膜面ｐＨは６．０〜６．５であった。なお、乳剤層側およびバック層側の吸収スペクトルは図１に示す通りであった。
【０２２７】
《評価》
＜下塗り層中のフィラーの厚みおよびアスペクト比の測定＞
測定する粒子を含みかつ縦横方向の少なくともどちらかに３．２倍以上延伸したフィルムをミクロトームでスライスし、切片を日立製作所製透過型電子顕微鏡（ＴＥＭ Ｈ−８００型）で２〜３万倍で観察し、その切片に見える少なくとも３０個以上の粒子の板径と厚みを測定して、その比をアスペクト比とした。
【０２２８】
＜寸法変化率の測定＞
得られたサンプルについて、部屋の環境湿度が変化した場合の寸法変化を次の方法で測定した。試料に２００ｍｍの間隔を置いて直径８ｍｍの孔を２個あけ、下記現像処理を行った。処理済み試料を２５℃、相対湿度６０％の部屋に２４時間放置した後、１／１０００ｍｍ精度のピンゲージ法を用いて２個の孔の間隔を２５℃、相対湿度６０％の部屋で正確に測定した。この時の長さをＸｍｍとした。次いで、処理済み試料を２５℃、相対湿度４０％の部屋に即座に移し、１５分後および４時間放置した後の長さをＹｍｍとした。部屋の環境湿度が変化した場合の寸法変化率（％）を（Ｙ−Ｘ）×１００／２００（％）で評価した。
【０２２９】
＜現像処理方法＞
現像液（富士写真フイルム（株）製、ＱＲ−Ｄ１）と定着液（富士写真フイルム（株）製、ＮＦ−１）を使用し、自動現像機（富士写真フイルム（株）製、ＦＧ−６８０ＡＧ）を用い、３５℃３０秒の現像条件で処理した。その時の乾燥温度は４５℃であった。
【０２３０】
【表１】

【０２３１】
＜評価結果＞
有機物で被覆された粘土化合物を含む下塗り層を有するサンプルＮｏ．１〜７は、優れた寸法安定性を有していた。特に、厚みが０．５〜５ｎｍでアスペクト比が５０〜１００００の範囲の有機物で被覆された粘土化合物を含むサンプルＮｏ．１〜６が優れていた。
下塗り第１層を有しないサンプルＮｏ．７、下塗り層にフィラーを含まないサンプルＮｏ．８は、寸法安定性に劣っていた。
【０２３２】
【発明の効果】
本発明によれば、寸法安定性に優れたハロゲン化銀写真感光材料を提供することができる。
【図面の簡単な説明】
【図１】本発明の一実施態様に係るハロゲン化銀写真感光材料について、乳剤層側およびバック層側の吸収スペクトルを示したものである。
【符合の説明】
縦軸は吸光度（０．１間隔）を示し、横軸は３５０ｎｍ〜９００ｎｍまでの波長を示す。実線は乳剤層側の吸収スペクトルを示し、破線はバック層側の吸収スペクトルを示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material and an IC printed circuit board photographic material used in a photolithography process.
[0002]
[Prior art]
Integrated circuits (ICs) support today's advanced information society from a hardware perspective. The reason why the IC is used is because it has features such as high speed, high reliability, low power, low price, high functionality, light weight and small size. By the way, in the case of photographic photosensitive material, for example, printing plate-making photosensitive material, especially IC printed circuit board use, high reliability is required, and one of them is taken up. For example, with the help of computer-aided design (CAD), a circuit diagram is produced, and this is photographed on a photographic material at the same magnification or reduced, developed, and fixed to produce a negative. Normally, a mercury lamp is used as a light source. Using this negative as a mask, a resist-coated copper plate (or copper foil) is subjected to contact exposure or reduced projection exposure, and the resist is chemically changed by ultraviolet rays emitted from the mercury lamp. There are negative and positive resists. The former is a type in which the part exposed to ultraviolet rays remains undissolved in the next development process, and the part that does not hit dissolves in the developer. The reverse type. In any case, the negative image reproducibility of the photographic photosensitive material (stability in the development process) when the contact exposure or reduced projection exposure is performed on the copper plate (or copper foil) coated with the resist using the negative of the photographic photosensitive material as a mask. ) And dimensional stability over time after the production of the negative image is important.
[0003]
In the photographic plate making process in the graphic arts field, a continuous tone photographic image is converted into a so-called halftone dot image that expresses the shading of the image by the size of the halftone dot area, and this is combined with an image in which characters and line drawings are photographed. The method of making is done. The silver halide photographic light-sensitive material used for such applications has ultra-high contrast photographic characteristics that can clearly distinguish between image areas and non-image areas in order to improve the reproducibility of characters, line drawings, and halftone images. Has been required to have. Silver halide photographic light-sensitive materials with such ultra-high contrast photographic characteristics are higher in density (experimental density is higher) at the exposure amount that gives the same halftone percentage when laser exposure is performed compared to soft ones. Therefore, the suitability for exposure to a resist is remarkably improved for IC printed circuit board applications.
[0004]
As a system that meets such demands, a silver halide photographic light-sensitive material composed of silver chlorobromide is processed with a hydroquinone developer having an extremely low effective concentration of sulfite ions, thereby forming an image having high contrast. A so-called lith development system is known. However, in this method, since the concentration of sulfite ions in the developer is low, the developer is extremely unstable against air oxidation, and the developer must be replenished in large quantities to keep the liquid activity stable. .
[0005]
For example, Patent Documents 1 to 13 disclose an image forming system that eliminates the instability of image formation in a lith development system and obtains ultrahigh contrast photographic characteristics by processing with a developer having good storage stability. System. These are surface latent image type silver halide photographic light-sensitive materials to which a hydrazine derivative is added, developed hydroquinone / methol or hydroquinone / phenidone having a pH of 11.0 to 12.3 and containing 0.15 mol / L or more of a sulfite preservative. This system forms a super-high contrast negative image with a gamma exceeding 10 by processing with a developing solution as a main agent. According to this method, photographic characteristics with super high contrast and high practical density can be obtained, and a high concentration of sulfite can be added to the developer, so that the stability of the developer against air oxidation is the conventional lith developer. Compared to a drastic improvement.
[0006]
In order to form a sufficiently ultra-high contrast image with a hydrazine derivative, it was necessary to process with a developer having a pH of 11 or more, usually 11.5 or more. Although it is possible to improve the stability of the developer by a high concentration of sulfite preservative, it is necessary to use a developer having a high pH value as described above in order to obtain a super high contrast photographic image. In addition, even if a preservative is present, the developer is easily oxidized by air and is unstable. Therefore, attempts have been made to achieve a super high contrast image at a lower pH in order to further improve the stability.
For example, Patent Documents 14 to 22 disclose a method using a highly active hydrazine derivative and a nucleation accelerator in order to obtain an ultrahigh contrast image having a high practical density using a developer having a pH of less than 11.0. Yes. However, the silver halide photographic material used in such an image forming system has a processing stability problem such as the activity of the hydrazine derivative and the nucleation accelerator is changed due to fatigue of the processing solution, and the sensitivity varies. In particular, IC printed circuit board photographic light-sensitive materials have a high practical density, and a stable image forming system has been desired.
[0007]
On the other hand, a silver halide photographic light-sensitive material generally has at least one layer of photographic light-sensitive material on a plastic film support composed of a fiber polymer represented by triacetyl cellulose and a polyester polymer represented by polyethylene terephthalate. Manufactured by applying layers. Polyethylene terephthalate film has excellent mechanical properties, dimensional stability, and high productivity, and is considered to be a substitute for triacetyl cellulose. Halogens for bright rooms, scanners, facsimiles, IC printed circuit boards, etc. Used in silver halide photographic materials. However, the length of polyethylene terephthalate film changes due to water absorption and dehydration at ambient humidity, and the dimensional stability is insufficient. As a technique for improving this, Patent Document 23 and the like disclose a technique of providing a polyvinyl chloride barrier layer in order to reduce a dimensional change due to moisture absorption of a support. However, when a polyvinylidene chloride layer is provided on the support, the dechlorination gradually proceeds due to long-term storage, so that the image turns yellow, and further, dimensional changes occur over time. There was a problem. For this reason, there has been a demand for a technique that does not cause dimensional changes due to humidity changes.
[0008]
[Patent Document 1] US Pat. No. 4,166,742
[Patent Document 2] US Pat. No. 4,168,977
[Patent Document 3] US Pat. No. 4,221,857
[Patent Document 4] US Pat. No. 4,224,401
[Patent Document 5] US Pat. No. 4,243,739
[Patent Document 6] US Pat. No. 4,269,922
[Patent Document 7] US Pat. No. 4,272,606
[Patent Document 8] US Pat. No. 4,311,781
[Patent Document 9] US Pat. No. 4,332,878
[Patent Document 10] US Pat. No. 4,618,574
[Patent Document 11] US Pat. No. 4,634,661
[Patent Document 12] US Pat. No. 4,681,836
[Patent Document 13] US Pat. No. 5,650,746
[Patent Document 14] US Pat. No. 4,269,929 (Japanese Patent Laid-Open No. 61-267759)
[Patent Document 15] US Pat. No. 4,737,452 (Japanese Patent Laid-Open No. 60-179734)
[Patent Document 16] US Pat. No. 5,104,769
[Patent Document 17] US Pat. No. 4,798,780
[Patent Document 18] JP-A-1-179939
[Patent Document 19] JP-A-1-179940
[Patent Document 20] US Pat. No. 4,998,604
[Patent Document 21] US Pat. No. 4,994,365
[Patent Document 22] JP-A-8-272023
[Patent Document 23] Japanese Patent Laid-Open No. 63-304249
[0009]
[Problems to be solved by the invention]
In view of these problems of the prior art, an object of the present invention is to provide a silver halide photographic light-sensitive material having good dimensional stability in a stable processing system.
[0010]
[Means for Solving the Problems]
As a result of extensive studies, the present inventor has found that at least one silver halide emulsion layer on the support and a silver halide photographic light-sensitive material having a back layer on the side opposite to the surface having the emulsion layer (emulsion surface). A silver halide photographic light-sensitive material comprising an undercoat layer containing a clay compound coated with an organic substance between the support and the emulsion layer or between the support and the back layer. As a result, the present invention has been reached. The clay compound coated with the organic material preferably has a thickness of 0.5 to 5 nm and an aspect ratio of 50 to 10,000. Further, the silver halide photographic light-sensitive material of the present invention has an optical density of 0.1 to 1.. 5 preferably has a characteristic curve having a gamma of 4.0 or more.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The silver halide photographic light-sensitive material of the present invention will be described in detail below. In the present specification, “to” means a range including numerical values described before and after that as a minimum value and a maximum value, respectively.
[0012]
The silver halide photographic light-sensitive material of the present invention is characterized by having an undercoat layer containing a clay compound coated with an organic substance between the support and the emulsion layer or between the support and the back layer.
The clay compound coated with an organic substance contained in the undercoat layer preferably has an aspect ratio of 50 to 10,000 and a thickness of 0.5 to 5 nm. For example, a compound obtained by allowing an organic onium ion to act on a layered silicate compound ( Hereinafter, it is also referred to as “organic onium-treated compound”.
[0013]
In the present invention, the reason why the desired effect can be obtained by including a clay compound coated with an organic substance in the undercoat layer is considered as follows. When the resin component is adsorbed on the filler in the undercoat layer, the mobility (ease of movement) is lowered, and the dimensional stability of the undercoat layer and the entire photosensitive material is considered to be improved. Here, it is considered that the higher the dispersibility of the filler contained in the undercoat layer, the more resin components adsorbed on the filler, that is, the hard-to-move polymer, so that the dimensional stability can be further improved.
[0014]
In the silver halide photographic light-sensitive material of the present invention, the organic onium-treated compound contained in the undercoat layer has a structure completely different from the μm-sized aggregate structure in which the layered silicate compound before processing has a multilayered structure. Have That is, when the layered silicate compound is treated with organic onium ions, organic onium ions having affinity with the resin are introduced between the layers. Thereby, the interlayer of the layered silicate compound is expanded, and can be dispersed in the form of very fine and independent flakes in the resin, showing extremely excellent dispersibility.
[0015]
In the present invention, by providing an undercoat layer containing such an organic onium-treated compound having excellent dispersibility as a filler, the silver halide photographic light sensitive to small variations in temperature expansion coefficient and humidity expansion coefficient is excellent in dimensional stability. Material can be obtained.
[0016]
The layered silicate compound is mainly composed of a tetrahedral sheet of silicon oxide and an octahedral sheet of metal hydroxide, and examples thereof include smectite clay, swellable mica, and swellable vermiculite.
The smectite clay is represented by the general formula: X_0.2~_0.6Y₂~₃Z₄O₁₀(OH)₂・ NH₂O (where X is at least one selected from the group consisting of K, Na, 1 / 2Ca, and 1 / 2Mg, and Y is composed of Mg, Fe, Mn, Ni, Zn, Li, Al, and Cr) One or more selected from the group, and Z is one or more selected from the group consisting of Si and Al.₂O represents a water molecule bonded to an interlayer ion, and n represents a natural or synthesized one that varies significantly depending on the interlayer ion and relative humidity. Specific examples of the smectite group clay include, for example, montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, sauconite, stevensite, bentonite, and the like, or a substitution product, a derivative thereof, or a mixture thereof. It is done.
[0017]
Further, the swellable mica has a general formula: X_0.5~_1.0Y₂~₃(Z₄O₁₀) (F, OH)₂(However, X is at least one selected from the group consisting of Li, Na, K, Rb, Ca, Ba, and Sr, and Y is selected from the group consisting of Mg, Fe, Ni, Mn, Al, and Li) Z is one or more selected from the group consisting of Si, Ge, Al, Fe, and B.), and is natural or synthesized.
These are water, a polar solvent that is compatible with water at an arbitrary ratio, and a material that swells in a mixed solvent of water and the polar solvent. For example, Li-type teniolite, Na-type teniolite, Li-type four Examples thereof include silicon mica, Na-type tetrasilicon mica, and the like, substituted products, derivatives, and mixtures thereof.
[0018]
Further, the swellable vermiculite is classified into a trioctahedral type and a dioctahedral type, and a general formula: (Mg, Fe, Al)₂~₃(Si_4-XAl_X) O₁₀(OH)₂・ (M⁺, 1 / 2M²⁺)_X・ NH₂O (wherein M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, X = 0.6 to 0.9, and n = 3.5 to 5).
[0019]
The above-mentioned layered silicate compounds can be used alone or in combination of two or more. The crystal structure of the layered silicate compound is preferably high in purity, which is regularly stacked in the c-axis direction, but so-called mixed layered minerals in which the crystal period is disturbed and a plurality of types of crystal structures are mixed can also be used.
[0020]
The organic onium ion used in the present invention has a structure represented by ammonium ions, phosphonium ions, sulfonium ions, and onium ions derived from heteroaromatic rings. In the presence of onium ions, an organic structure having a small intermolecular force can be introduced between the layers of the negatively charged layered silicate compound, and the affinity between the layered silicate compound and the resin can be increased. Organic onium ions include alkylamine ions such as laurylamine ions and myristylamine ions, diethylmethyl (polypropylene oxide) ammonium ions, and ammonium ions having both alkyl groups and glycol chains such as dimethylbis (polyethylene glycol) ammonium ions. Etc.
[0021]
In the present invention, for example, tetraethylammonium chloride, n-dodecyltrimethylammonium chloride, or dimethyldistearylammonium chloride is used as an ammonium ion source as a compound used for supplying organic onium ions to the layered silicate compound. And ethyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, and tetraethylphosphonium bromide can be used as the phosphonium ion source, and trimethylsulfonium iodide and triphenylsulfonium bromide can be used as the sulfonium ion source. Can do.
[0022]
A layered silicate compound treated with such an organic onium ion is a known technique for reacting an organic onium ion with a layered clay mineral containing a negative layer lattice and an exchangeable cation (Japanese Patent Publication No. 61-5492, Japanese Patent Laid-Open No. 60-42451).
[0023]
0.5-5 nm is preferable, as for the thickness of the clay compound coat | covered with said organic substance, More preferably, it is 0.7-4 nm, More preferably, it is 0.8-2 nm.
When the thickness is less than 0.5 nm, the plate-like particles can no longer exist, and when the thickness exceeds 5 nm, the surface of the support tends to be roughened.
[0024]
The aspect ratio of the clay compound coated with the organic material is preferably 50 to 10,000, more preferably 60 to 5000, and still more preferably 70 to 1000.
Here, the “aspect ratio” refers to the ratio (average particle size / thickness) between the average particle size and the thickness of the filler. If the aspect ratio is less than 50, the effect of the plate-like particles cannot be obtained, and if the aspect ratio exceeds 10,000, the surface of the support becomes rough.
[0025]
In the present invention, the thickness and aspect ratio of the clay compound coated with the organic substance contained in the undercoat layer are determined by dispersing the particles with a disperser that is subjected to high shear, such as a homomixer, when the clay compound is coated with the organic compound. It can be adjusted by dispersing.
[0026]
As binder for undercoat layer, polyester resin, polyamide resin, polyamideimide resin, polyurethane resin, vinyl chloride resin, vinylidene chloride resin, phenol resin, epoxy resin, urea resin, melamine resin, formaldehyde resin, silicone resin, starch, Modified starch compound, alginate compound, casein, gelatin, pullulan, dextran, chitin, chitosan, rubber latex, gum arabic, funori, natural gum, dextrin, modified cellulose resin, polyvinyl alcohol resin, polyethylene oxide, polyacrylic acid resin, Solvent-soluble substances such as polyvinylpyrrolidone, polyethyleneimine, polyvinyl ether, polymaleic acid copolymer, polyacrylamide, and alkyd resin can be used. It is particularly preferable to introduce a carboxyl group or a sulfonic acid metal base into the above binder for the purpose of further improving the adhesion.
[0027]
There is no particular limitation on the silver halide for the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention. Silver chloride, silver chlorobromide, silver bromide, silver iodochlorobromide and silver iodobromide can be used, but silver chlorobromide and silver iodochlorobromide containing 30 mol% or more of silver chloride should be used. Is preferred. The shape of the silver halide grains may be any of a cube, a tetrahedron, an octahedron, an indeterminate shape and a plate shape, but a cube is preferred. The average grain size of silver halide is preferably 0.1 μm to 0.7 μm, more preferably 0.1 to 0.5 μm. Further, the coefficient of variation represented by {(standard deviation of particle size) / (average particle size)} × 100 is preferably 15% or less, more preferably 10% or less and a narrow particle size distribution.
The silver halide grains may be composed of a single phase having a uniform inner layer and surface layer, or may be composed of phases different from each other. Moreover, you may have the localized layer from which a halogen composition differs in the inside or the surface of a particle | grain.
[0028]
The photographic emulsion used in the present invention is P.I. Grafkides, Chimie et Physique Photographic (published by Paul Montel, 1967), G.K. F. Dufin, Photographic Emulsion Chemistry (published by The Focal Press, 1966), V.C. L. It can be prepared using a method described in, for example, Making and Coating Photographic Emulsion (published by The Formal Press, 1964) by Zelikman et al.
That is, either an acidic method or a neutral method may be used. Further, as a method of reacting the soluble silver salt and the soluble halogen salt, any one of a one-side mixing method, a simultaneous mixing method, a combination thereof, and the like may be used. A method (so-called back mixing method) in which grains are formed in the presence of excess silver ions can also be used.
[0029]
As one type of the simultaneous mixing method, a method of keeping pAg in a liquid phase in which silver halide is generated, that is, a so-called controlled double jet method can be used. In particular, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether or tetrasubstituted thiourea. More preferred as a silver halide solvent is a tetrasubstituted thiourea compound, which is described in JP-A-53-82408 and JP-A-55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The addition amount of the silver halide solvent varies depending on the type of compound used, the target grain size, and the halogen composition, but it is 10 per mol of silver halide.^-5-10^-2mol is preferred.
[0030]
In the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal type and a narrow grain size distribution. The silver halide used in the present invention It is a useful tool for making emulsions.
Further, in order to make the grain size uniform, as described in British Patent No. 1,535,016, Japanese Patent Publication No. 48-36890, No. 52-16364, silver nitrate or halogenated A method of changing the alkali addition rate according to the particle growth rate, or a method of changing the concentration of the aqueous solution as described in British Patent No. 4,242,445 and JP-A-55-158124 It is preferable to grow quickly in a range not exceeding the critical saturation.
[0031]
The silver halide emulsion used in the present invention contains a metal complex containing one or more cyanide ligands in an amount of 1 × 10 5 per mol of silver in silver halide.^-6It is preferable to contain more than mol. 5 x 10 per mol of silver in silver halide^-6mol ~ 1 × 10^-2It is preferable to contain mol. Furthermore, 5 × 10 5 per mol of silver in the silver halide.^-6mol-5 × 10^-3It is particularly preferable to contain mol. The metal complex containing one or more cyanide ligands used in the present invention is added in the form of a water-soluble complex salt. Particularly preferred is a hexacoordination complex represented by the following formula.
[M (CN)_n1L_6-n1]^n-
Here, M represents a metal belonging to Group V to VIII, and Ru, Re, Os, and Fe are particularly preferable. L represents a ligand other than a cyanide compound, and a halide ligand, a nitrosyl ligand, a thionitrosyl ligand and the like are preferable. n1 represents 1 to 6, and n represents 0, 1, 2, 3 or 4. n1 is preferably 6. In this case, the counter ion has no significance and ammonium or alkali metal ions are used. Specific examples of the complex used in the present invention are shown below, but the complex that can be used in the present invention is not limited to these.
[0032]
[Chemical 1]
[Re (NO) (CN)₅]^2-  [Re (O)₂(CN)₄]^3-
[Os (NO) (CN)₅]^2-  [Os (CN)₆]^4-
[Os (O)₂(CN)₄]^4-
[Ru (CN)₆]^4-          [Fe (CN)₆]^4-
[0033]
The metal complex used in the present invention may be present anywhere in the silver halide grains, but is preferably present inside the silver halide crystal. Most preferably, the silver halide crystals are present in the interior containing 99 mol% or less, preferably 95 mol% or less, and more preferably 0 to 95 mol% of silver in each silver halide crystal. For this purpose, it is preferable to form photosensitive silver halide grains in multiple layers as in the examples described later.
[0034]
In order to achieve high contrast and low fog in addition to a metal complex containing one or more cyanide ligands, the silver halide emulsion used in the present invention is composed of rhodium compounds, iridium compounds, rhenium compounds, ruthenium compounds. It is preferable to contain an osmium compound or the like.
[0035]
As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a halogen, amines, oxalato, ako, etc. as a ligand, such as a hexachlororhodium (III) complex salt, a pentachloroacorodium complex salt, a tetrachlorodiaco salt Examples include rhodium complex salts, hexabromorhodium (III) complex salts, hexaamine rhodium (III) complex salts, and trizalatrodium (III) complex salts. These rhodium compounds are used by dissolving in water or an appropriate solvent, and are generally used in order to stabilize the rhodium compound solution, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, odorous acid, hydrofluoric acid). Or a method of adding an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add another silver halide grain previously doped with rhodium and dissolve it at the time of silver halide preparation.
[0036]
Rhenium, ruthenium, and osmium used in the present invention are water-soluble complex salts described in JP-A-63-2042, JP-A-1-2855941, JP-A-2-20852, JP-A-2-20855, and the like. Added in the form. Particularly preferred is a hexacoordination complex represented by the following formula.
[ML₆]^n-
Here, M represents Ru, Re, or Os, L represents a ligand, and n represents 0, 1, 2, 3, or 4. In this case, the counter ion has no significance and ammonium or alkali metal ions are used. Preferred ligands include halide ligands, nitrosyl ligands, thionitrosyl ligands and the like. Specific examples of the complex used in the present invention are shown below, but the complex that can be used in the present invention is not limited to these.
[0037]
[Chemical 2]
[ReCl₆]^3-                [ReBr₆]^3-
[ReCl₅(NO)]^2-        [Re (NS) Br₅]^2-
[RuCl₆]^3-                [RuCl₄(H₂O)₂]^1-
[RuCl₅(NO)]^2-        [RuBr₅(NS)]^2-
[Ru (CO)₃Cl₃]^2-      [Ru (CO) Cl₅]^2-
[Ru (CO) Br₅]^2-        [OsCl₆]^3-
[OsCl₅(NO)]^2-        [Os (NS) Br₅]^2-
[0038]
The amount of these compounds added is 1 × 10 5 per mol of silver halide.^-9mol ~ 1 × 10^-5The range of mol is preferred, particularly preferably 1 × 10^-8mol ~ 1 × 10^-6mol.
Examples of the iridium compound used in the present invention include hexachloroiridium, hexabromoiridium, hexaammineiridium, and pentachloronitrosyliridium.
[0039]
The silver halide emulsion used in the present invention is preferably chemically sensitized. Known methods such as a sulfur sensitizing method, a selenium sensitizing method, a tellurium sensitizing method, and a noble metal sensitizing method can be used, and they can be used alone or in combination. When used in combination, for example, sulfur sensitizing method and gold sensitizing method, sulfur sensitizing method and selenium sensitizing method and gold sensitizing method, sulfur sensitizing method and tellurium sensitizing method and gold sensitizing method, etc. Is preferred.
[0040]
The sulfur sensitization used in the present invention is usually performed by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. Known compounds can be used as the sulfur sensitizer, for example, various sulfur compounds such as thiosulfate, thioureas, thiazoles, rhodanines, etc. in addition to sulfur compounds contained in gelatin. be able to. Preferred sulfur compounds are thiosulfate and thiourea compounds. As the thiourea compound, a specific tetra-substituted thiourea compound described in US Pat. No. 4,810,626 is particularly preferable. The amount of sulfur sensitizer added varies under various conditions such as pH during chemical ripening, temperature, and the size of silver halide grains, but it is 10 per mol of silver halide.^-7-10^-2mol, more preferably 10^-5-10^-3mol.
[0041]
A known selenium compound can be used as the selenium sensitizer used in the present invention. That is, it is usually carried out by adding unstable and / or non-labile selenium compounds and stirring the emulsion at a high temperature of 40 ° C. or higher for a predetermined time. As the unstable selenium compound, compounds described in JP-B Nos. 44-15748, 43-13489, JP-A-4-109240, and JP-A-4-324855 can be used. In particular, it is preferable to use compounds represented by general formulas (VIII) and (IX) in JP-A-4-324855.
[0042]
The tellurium sensitizer used in the present invention is a compound that forms silver telluride presumed to be a sensitization nucleus on the surface or inside of a silver halide grain. The silver telluride formation rate in the silver halide emulsion can be tested by the method described in JP-A-5-313284.
Specifically, US Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211, No. 1,121,496, No. 1,295,462, No. 1,396,696, Canadian Patent No. 800,958, JP-A-4-204640, No. 4-271341, No. 4-3333043, No. 5-303157, Journal of Chemical Society, Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid. 1102 (1979), ibid 645 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. Soc. Perkin. Trans.) 1, 2191 (1980), S. Compounds described in The Chemistry of Organic Serenium and Tellunium Compounds, Vol1 (1986), Vol2 (1987), edited by S. Patai, The Chemistry of Organic Selenium and Tellurium Companies be able to. In particular, compounds represented by general formulas (II), (III) and (IV) in JP-A-4-324855 are preferred.
[0043]
The amount of selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains used, chemical ripening conditions, etc., but is generally 10 per mol of silver halide.^-8-10^-2mol, preferably 10^-7-10^-3About mol is used. The conditions for chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C.
Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, iridium and the like, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and the like, and 10 per mol of silver halide.^-7-10^-2About mol can be used.
In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt or the like may coexist in the process of silver halide grain formation or physical ripening.
[0044]
In the present invention, reduction sensitization can be used. As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used.
A thiosulfonic acid compound may be added to the silver halide emulsion used in the present invention by the method described in EP 293,917A.
In the silver halide photographic light-sensitive material of the present invention, 1 to 3 types of silver halide emulsions are preferably used. When two or more kinds are used in combination, those having different average particle sizes, those having different halogen compositions, those containing different amounts and types of metal complexes, those having different crystal habits, those having different chemical sensitization conditions, sensitivity It is preferable to use a combination of different ones. In particular, in order to obtain high contrast, as described in JP-A-6-324426, it is preferable to apply an emulsion with higher sensitivity as it is closer to the support.
[0045]
The photosensitive silver halide emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light by a sensitizing dye. Furthermore, compounds of general formula [I] described in JP-A No. 55-45015 and compounds of general formula [I] described in JP-A No. 9-160185 are preferred, and in particular, JP-A No. 9-160185. The compounds of the general formula [I] described in the publication No. are preferred. Specifically, from the compounds (1) to (19) described in JP-A-55-45015, the compounds I-1 to I-40 and I-56 described in JP-A-9-160185 The compound of I-85 etc. can be mentioned.
[0046]
As other sensitizing dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used.
Other useful sensitizing dyes used in the present invention are described in or cited in, for example, RESEARCH DISCLOSURE Item 17643IV-A (December 1978, p.23) and Item 18341X (August 1979, p.437). It is described in.
In particular, a sensitizing dye having spectral sensitivity suitable for spectral characteristics of light sources of various scanners, imagesetters and plate making cameras can be advantageously selected.
[0047]
For example, for A) an argon laser light source, compounds (I) -1 to (I) -8 described in JP-A-60-162247, I-1 described in JP-A-2-48653 To I-28 compounds, I-1 to I-13 compounds described in JP-A-4-330434, Examples 1 to 14 compounds described in US Pat. No. 2,161,331, West German Patent 936, Compounds Nos. 1 to 7 described in the specification of No. 071, B) Helium-neon laser light source, compounds of I-1 to I-38 described in JP-A-54-18726, JP-A-6-75322 Japanese Patent Publication No. 55-39818 for compounds of I-1 to I-35 described in Japanese Patent Publication No. JP-A-7-287338 and compounds of I-1 to I-34 described in Japanese Unexamined Patent Publication No. 7-287338, C) LED light sources Described in 1 to 20, compounds of I-1 to I-37 described in JP-A-62-284343 and compounds of I-1 to I-34 described in JP-A-7-287338, D) semiconductor laser For light sources, compounds of I-1 to I-12 described in JP-A-59-191032, compounds of I-1 to I-22 described in JP-A-60-80841, and JP-A-4 Compounds I-1 to I-29 described in JP-A-335342 and compounds I-1 to I-18 described in JP-A-59-192242, E) Tungsten and xenon light sources of plate-making cameras In addition to the above-mentioned compounds, compounds I-41 to I-55 and I-86 to I-97 described in JP-A-9-160185 and 4 described in JP-A-6-242547 Compound of 4-S from A, compounds of 5-Q from 5-A, such as the compounds of the 6-T from 6-A can also be advantageously selected.
[0048]
These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. Along with the sensitizing dye, the emulsion itself may contain a dye having no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization.
Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Research Disclosure) 176, 17643 (published in December, 1978), page 23, IV, or These are described in JP-B-49-25500, JP-A-43-4933, JP-A-59-19032 and JP-A-59-192242.
[0049]
Two or more sensitizing dyes used in the present invention may be used in combination. In order to add the sensitizing dye into the silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2, 2, 3, 3 -Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion.
Further, as disclosed in US Pat. No. 3,469,987, etc., a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. As disclosed in Japanese Patent Publication Nos. 44-23389, 44-27555, 57-22091, etc., a dye is dissolved in an acid and the solution is added to the emulsion. As disclosed in US Pat. Nos. 3,822,135, 4,006,025, and the like. A method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant to the emulsion, as disclosed in JP-A-53-102733 and 58-105141, in a hydrophilic colloid. Dye A method of adding the dispersion into the emulsion, and dissolving the dye using a compound that shifts red as disclosed in JP-A-51-74624, and adding the solution to the emulsion It is also possible to use a method of In addition, ultrasonic waves can be used for the solution.
[0050]
The time when the sensitizing dye used in the present invention is added to the silver halide emulsion may be during any step of emulsion preparation that has been found to be useful so far. For example, U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, and JP-A-58. As disclosed in JP-A-184142, JP-A-60-196749, etc., chemical ripening is performed during the silver halide grain formation step or / and before the desalting, during and / or after the desalting step. As long as it is before the start of the emulsion, as disclosed in Japanese Patent Application Laid-Open No. 58-11939, etc., immediately before chemical ripening or during the process, after chemical ripening and before coating, the emulsion is not coated. It may be added in the process at any time. Further, as disclosed in US Pat. No. 4,225,666, JP-A-58-7629, etc., the same compound can be used alone or in combination with a compound having a different structure, for example, a particle forming step. It may be added separately during the chemical ripening process or after completion of chemical ripening, or may be added separately before or during chemical ripening or after completion of chemical ripening. You may change and add the kind of combination.
[0051]
In the present invention, the addition amount of the sensitizing dye varies depending on the shape, size, halogen composition, method and degree of chemical sensitization of silver halide grains, the type of antifoggant, etc., but 4 × 10 4 per mol of silver halide. It can be used at −6 to 8 × 10 −3 mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, an addition amount of 2 × 10 −7 to 3.5 × 10 −6 mol per 1 m 2 of surface area of the silver halide grain is preferable, and 6.5 The addition amount of x10-7 to 2.0x10-6 mol is more preferable.
[0052]
The silver halide photographic light-sensitive material of the present invention has a characteristic curve with a gamma of 4.0 or more, preferably 5.0 to 100, more preferably 5.0 to 30.
In the present invention, “gamma” is an optical density of 0.1 and 1 in a characteristic curve shown on an orthogonal coordinate axis having the same unit length represented by an optical density (y-axis) and a common logarithmic exposure (x-axis). 5 is a gradient when a straight line is drawn at two points. That is, tan θ is expressed as θ where the angle formed by the straight line and the x axis is θ.
In the present invention, in order to obtain a characteristic curve, a developer (manufactured by Fuji Photo Film Co., Ltd., QR-D¹) And a fixing solution (NF-1 manufactured by Fuji Photo Film Co., Ltd.), a silver halide photographic light-sensitive material is developed at 35 ° C. for 30 seconds under an automatic developing machine (FG-Photo by Fuji Photo Film Co., Ltd.). 680AG).
[0053]
There are various methods for obtaining a silver halide photographic light-sensitive material having the characteristic curve defined in the present invention. For example, a silver halide emulsion containing a heavy metal (for example, a metal belonging to Group VIII) capable of realizing a high contrast is used. Can adjust the gamma of the silver halide photographic material. In particular, a silver halide emulsion containing a rhodium compound, an iridium compound, a ruthenium compound or the like is preferably used. Moreover, it is also preferable to contain at least one compound such as a hydrazine derivative, an amine compound, or a phosphonium compound as a nucleating agent on the side including the emulsion layer.
[0054]
The silver halide photographic light-sensitive material of the present invention can contain a hydrazine compound as a nucleating agent. In particular, a hydrazine derivative represented by the following general formula (D) is preferable.
Formula (D)
[Chemical 3]

[0055]
Where R²⁰Represents an aliphatic group, an aromatic group, or a heterocyclic group, and R¹⁰Represents a hydrogen atom or a blocking group, and G¹⁰-CO-, -COCO-, -C (= S)-, -SO₂-, -SO-, -PO (R³⁰) -Group (R³⁰Is R¹⁰Selected from the same range as defined for¹⁰And may be different. ) Or an iminomethylene group. A¹⁰, A²⁰Both represent a hydrogen atom, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.
[0056]
In general formula (D), R²⁰Is preferably a substituted or unsubstituted, linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 1 to 30 carbon atoms.
In general formula (D), R²⁰Is a monocyclic or condensed aryl group, and examples thereof include a benzene ring and a naphthalene ring. R²⁰The heterocyclic group represented by the formula is a monocyclic or condensed ring, saturated or unsaturated, aromatic or non-aromatic heterocyclic group such as a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline. Ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, piperidine ring, triazine ring and the like.
R²⁰Preferred is an aryl group, and particularly preferred is a phenyl group.
[0057]
R²⁰The group represented by may be substituted. Typical examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, or iodine atom), alkyl group (aralkyl group, cycloalkyl group, active methine group, etc.) ), An alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (for example, a pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (ethyleneoxy group or propyleneoxy group unit ), Allyl Oxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino group, N-substituted nitrogen-containing Heterocyclic group, acylamino group, sulfonamide group, ureido group, thioureido group, isothioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4 Primary ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, N-acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocycle) thio , (Alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, N-acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, phosphoric acid amide or phosphoric acid ester And a group containing a structure.
These substituents may be further substituted with these substituents.
[0058]
R²⁰As the substituent that may have, an alkyl group having 1 to 30 carbon atoms (including an active methylene group), an aralkyl group, a heterocyclic group, a substituted amino group, an acylamino group, a sulfonamide group, a ureido group, Sulfamoylamino group, imide group, thioureido group, phosphoric acid amide group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group (salts thereof) ), (Alkyl, aryl, or heterocyclic) thio group, sulfo group (including salts thereof), sulfamoyl group, halogen atom, cyano group, nitro group and the like.
[0059]
In general formula (D), R¹⁰Represents a hydrogen atom or a blocking group, and the blocking group specifically represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, or a hydrazino group.
[0060]
R¹⁰Is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, a trifluoromethyl group, a difluoromethyl group, a 2-carboxytetrafluoroethyl group, a pyridiniomethyl group, a difluoromethoxymethyl group, Examples include difluorocarboxymethyl group, 3-hydroxypropyl group, methanesulfonamidomethyl group, benzenesulfonamidomethyl group, hydroxymethyl group, methoxymethyl group, methylthiomethyl group, phenylsulfonylmethyl group, o-hydroxybenzyl group and the like. The alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, and examples thereof include a vinyl group, 2,2-dicyanovinyl group, 2-ethoxycarbonylvinyl group, 2-trifluoro-2-methoxycarbonylvinyl group and the like. . The alkynyl group is preferably an alkynyl group having 1 to 10 carbon atoms, and examples thereof include an ethynyl group and a 2-methoxycarbonylethynyl group. As the aryl group, a monocyclic or condensed ring aryl group is preferable, and a group containing a benzene ring is particularly preferable. Examples thereof include a phenyl group, 3,5-dichlorophenyl group, 2-methanesulfonamidophenyl group, 2-carbamoylphenyl group, 4-cyanophenyl group, 2-hydroxymethylphenyl group and the like.
[0061]
The heterocyclic group is preferably a 5- to 6-membered saturated or unsaturated monocyclic or condensed heterocyclic group containing at least one nitrogen, oxygen and sulfur atom, and a quaternized nitrogen atom. A morpholino group, piperidino group (N-substituted), piperazino group, imidazolyl group, indazolyl group (4-nitroindazolyl group, etc.), pyrazolyl group, triazolyl group, benzoimidazolyl group, Examples include a tetrazolyl group, a pyridyl group, a pyridinio group (such as N-methyl-3-pyridinio group), a quinolinio group, and a quinolyl group. A morpholino group, piperidino group, pyridyl group, pyridinio group and the like are particularly preferable.
[0062]
As an alkoxy group, a C1-C8 alkoxy group is preferable, for example, a methoxy group, 2-hydroxyethoxy group, a benzyloxy group etc. are mentioned. The aryloxy group is preferably a phenoxy group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, an arylamino group, or a saturated or unsaturated heterocyclic amino group (quaternized). A nitrogen-containing heterocyclic group containing a nitrogen atom) is preferred. Examples of amino groups include 2,2,6,6-tetramethylpiperidin-4-ylamino group, propylamino group, 2-hydroxyethylamino group, anilino group, o-hydroxyanilino group, 5-benzotriazolyl. A ruamino group, an N-benzyl-3-pyridinioamino group, and the like. As the hydrazino group, a substituted or unsubstituted hydrazino group or a substituted or unsubstituted phenylhydrazino group (such as 4-benzenesulfonamidophenylhydrazino group) is particularly preferable.
[0063]
R¹⁰The group represented by may be substituted, and preferred substituents are R²⁰Examples of the substituents in FIG.
[0064]
R in general formula (D)¹⁰Is G¹⁰-R¹⁰-G from the remaining molecules, -G¹⁰-R¹⁰A cyclization reaction that generates a cyclic structure containing a partial atom may occur, and examples thereof include those described in JP-A-63-29751.
[0065]
The hydrazine derivative represented by the general formula (D) may incorporate an adsorptive group that adsorbs to silver halide. Such adsorbing groups include alkylthio groups, arylthio groups, thiourea groups, thioamide groups, mercaptoheterocyclic groups, triazole groups and the like in U.S. Pat. Nos. 4,385,108 and 4,459,347. JP-A-59-195233, 59-200231, 59-201045, 59-201046, 59-201047, 59-201048, 59-201049. Japanese Patent Laid-Open Nos. 61-170733, 61-270744, 62-948, 63-234244, 63-234245, 63-234246 Is mentioned. Further, these adsorbing groups to silver halide may be made into a precursor. Examples of such a precursor include groups described in JP-A-2-285344.
[0066]
R in the general formula (D)¹⁰Or R²⁰May be incorporated with ballast groups or polymers commonly used in immobile photographic additives such as couplers. In the present invention, the ballast group is a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group), alkylamino group (or alkyleneamino group), alkylthio having 6 or more carbon atoms. Group or a group having these as a partial structure, and more preferably a linear or branched alkyl group (or alkylene group), alkoxy group (or alkyleneoxy group) having 7 to 24 carbon atoms, An alkylamino group (or alkyleneamino group), an alkylthio group, or a group having these as a partial structure is represented. Examples of the polymer include those described in JP-A-1-100530.
[0067]
R in the general formula (D)¹⁰Or R²⁰May contain a plurality of hydrazino groups as substituents. At this time, the compound represented by the general formula (D) represents a multimer related to the hydrazino group, specifically, for example, JP-A-64-86134. No. 4, JP-A-4-16938, JP-A-5-97091, International Publication WO95-32452, International Publication WO95-32453, JP-A-9-179229, JP-A-9-235264 And compounds described in JP-A-9-235265, JP-A-9-235266, JP-A-9-235267, and the like.
[0068]
R in the general formula (D)¹⁰Or R²⁰In which a cationic group (specifically, a group containing a quaternary ammonio group, a group containing a quaternized phosphorus atom, or a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom) Etc.), a group containing a repeating unit of an ethyleneoxy group or a propyleneoxy group, a (alkyl, aryl, or heterocyclic) thio group, or a dissociable group (a group having a low acidity proton that can be dissociated by an alkaline developer) Or a partial structure, or a salt thereof. Specifically, for example, a carboxyl group (—COOH), a sulfo group (—SOOH)₃H), a phosphonic acid group (—PO₃H), phosphate group (-OPO₃H), hydroxy group (—OH group), mercapto group (—SH), —SO₂NH₂Group, N-substituted sulfonamide group (-SO₂NH-group, -CONHSO₂-Group, -CONHSO₂NH-group, -NHCONHSO₂-Group, -SO₂NHSO₂-Groups), -CONHCO- groups, active methylene groups, -NH- groups inherent in nitrogen-containing heterocyclic groups, or salts thereof may be included. Examples of these groups include JP-A-7-234471, JP-A-5-333466, JP-A-6-19032, JP-A-6-19031, and JP-A-5-45761. U.S. Pat. No. 4,994,365, U.S. Pat. No. 4,988,604, JP-A-7-259240, JP-A-7-5610, JP-A-7-244348, German Examples include compounds described in Japanese Patent No. 4006032, Japanese Patent Application Laid-Open No. 11-7093 and the like.
[0069]
In the general formula (D), A¹⁰, A²⁰Is a hydrogen atom, an alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants is −0.5 or more), carbon number 20 The following acyl groups (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more, or a linear, branched, or cyclic substituted or unsubstituted aliphatic group An acyl group (in this case, examples of the substituent include a halogen atom, an ether group, a sulfonamide group, a carbonamido group, a hydroxy group, a carboxy group, and a sulfo group). A¹⁰, A²⁰Is most preferably a hydrogen atom.
[0070]
Next, hydrazine derivatives particularly preferably used in the present invention will be described.
R²⁰Is particularly preferably a substituted phenyl group, and the substituent is particularly preferably a sulfonamido group, an acylamino group, a ureido group, a carbamoyl group, a thioureido group, an isothioureido group, a sulfamoylamino group, an N-acylsulfamoylamino group, Furthermore, a sulfonamide group and a ureido group are preferable, and a sulfonamide group is most preferable.
The hydrazine derivative represented by the general formula (D) is R²⁰Or R¹⁰In addition, as a substituent, directly or indirectly, a ballast group, a silver halide adsorbing group, a group containing a quaternary ammonio group, a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom, an ethyleneoxy group A group containing a repeating unit, an (alkyl, aryl, or heterocyclic) thio group, a dissociable group capable of dissociating in an alkaline developing solution, or a hydrazino group capable of forming a multimer (-NHNH-G¹⁰-R¹⁰It is particularly preferred that at least one of the groups represented by Furthermore, R²⁰It is preferable to have any one of the above-mentioned groups directly or indirectly as a substituent, and most preferably R²⁰Represents a phenyl group substituted with a benzenesulfonamide group, and has one of the aforementioned groups directly or indirectly as a substituent on the benzene ring of the benzenesulfonamide group.
[0071]
R¹⁰Preferred among the groups represented by¹⁰Is a —CO— group, a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, more preferably a hydrogen atom, an alkyl group, a substituted aryl group (the substituent is an electron An attractive group or an o-hydroxymethyl group is particularly preferred), and a hydrogen atom or an alkyl group is most preferred.
G¹⁰When is a —COCO— group, an alkoxy group, an aryloxy group, and an amino group are preferable, and a substituted amino group, specifically an alkylamino group, an arylamino group, or a saturated or unsaturated heterocyclic amino group is preferable.
G¹⁰-SO₂-In the case of a group, R¹⁰Is preferably an alkyl group, an aryl group or a substituted amino group.
[0072]
In general formula (D), G¹⁰Is preferably a —CO— group or a —COCO— group, particularly preferably a —CO— group.
[0073]
Next, specific examples of the compound represented by the general formula (D) are shown below. However, the compounds that can be used in the present invention are not limited to the following specific examples.
[0074]
[Formula 4]

[0075]
[Chemical formula 5]

[0076]
[Chemical 6]

[0077]
[Chemical 7]

[0078]
[Chemical 8]

[0079]
[Chemical 9]

[0080]
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[0081]
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[0082]
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[0083]
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[0084]
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[0085]
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[0086]
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[0087]
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[0088]
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[0089]
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[0090]
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[0091]
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[0092]
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[0093]
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[0094]
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[0095]
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[0096]
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[0097]
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[0098]
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[0099]
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[0100]
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[0101]
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[0102]
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[0103]
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[0104]
As the hydrazine derivative used in the present invention, the following hydrazine derivatives are preferably used in addition to the above. The hydrazine derivative used in the present invention can also be synthesized by various methods described in the following publications.
[0105]
A compound represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, a compound described on pages 3 and 4 of the same publication; a general formula described in JP-B-6-93082 ( A compound represented by I), specifically, compounds 1 to 38 described on pages 8 to 18 of the same publication; general formulas (4) and (5) described in JP-A-6-230497; And compounds represented by formula (6), specifically, compound 4-1 to compound 4-10 described on pages 25 and 26 of the same publication, compound 5-1 to pages 28 to 36, and 5-42, and compounds 6-1 to 6-7 described on pages 39 and 40; compounds represented by general formula (1) and general formula (2) described in JP-A-6-289520. Specifically, compounds 1-1) to 1-17) and 2-1) described in pages 5 to 7 of the same publication; Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-13936, specifically, compounds described on pages 6 to 19 of the same publication; (Chemical formulas described in JP-A-6-313951) 1), specifically the compounds described on pages 3 to 5 of the publication; compounds represented by the general formula (I) described in JP-A-7-5610, specifically Is a compound represented by the general formula (II) described in JP-A-7-77783, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same publication; specifically, page 10 of the same publication. Compounds II-1 to II-102 described on page 27; compounds represented by general formula (H) and general formula (Ha) described in JP-A-7-104426; Compounds H-1 to H-44 described on pages 15 to 15; hydrides described in JP-A-9-22082 A compound having an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of the gin group, particularly the general formula (A), the general formula (B), the general formula ( C), compounds represented by general formula (D), general formula (E), and general formula (F), specifically, compounds N-1 to N-30 described in the same publication; JP-A-9-22082 In particular, compounds represented by the general formula (1) described in the Japanese Patent Publication No., specifically, compounds D-1 to D-55 described in the same publication can be given. In addition, International Publication No. WO95-32452, International Publication No. WO95-32453, Japanese Unexamined Patent Publication No. 9-179229, Japanese Unexamined Patent Publication No. 9-235264, Japanese Unexamined Patent Publication No. 9-235265, Japanese Unexamined Patent Publication No. 9-235266. JP-A-9-235267, JP-A-9-319019, JP-A-9-319020, JP-A-10-130275, JP-A-11-7093, JP-A-6-332096, JP-A-7-209789, JP-A-8-6193, JP-A-8-248549, JP-A-8-248550, JP-A-8-262609, JP-A-8-314044, JP-A-8 -328184, JP-A-9-80667, JP-A-9-127632, JP-A-9-146208 Gazette, JP-A-9-160156, JP-A-10-161260, JP-A-10-221800, JP-A-10-213871, JP-A-10-254082, JP-A-10-254088, JP-A-7-120864, JP-A-7-244348, JP-A-7-333773, JP-A-8-36232, JP-A-8-36233, JP-A-8-36234, JP The hydrazine derivatives described in JP-A-8-36235, JP-A-8-272202, JP-A-9-22083, JP-A-9-22084, JP-A-9-54381, and JP-A-10-175946 are also used. Can be mentioned.
[0106]
In the present invention, the hydrazine-based nucleating agent is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve. It can be used by dissolving it in
In addition, using a well-known emulsification dispersion method, it is dissolved using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be made and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.
[0107]
In the present invention, the hydrazine nucleating agent may be added to any layer as long as it is on the silver halide emulsion layer side with respect to the support. For example, it can be added to a silver halide emulsion layer or another hydrophilic colloid layer, but it is preferably added to a silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto. Two or more hydrazine nucleating agents can be used in combination.
The addition amount of the nucleating agent in the present invention is 1 × 10 with respect to 1 mol of silver halide.^-5~ 1x10^-2mol is preferred, 1 × 10^-5~ 5x10^-3mol is more preferred, 2 × 10^-5~ 5x10^-3Most preferred is mol.
[0108]
A nucleation accelerator can be incorporated in the silver halide photographic light-sensitive material of the present invention.
Examples of the nucleation accelerator used in the present invention include amine derivatives, onium salts, disulfide derivatives, and hydroxymethyl derivatives. Specifically, compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, compounds A-1) to A-73) described on pages 49 to 58; Compounds represented by (Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 23) described in JP-A-7-84331, specifically, compounds described on pages 6 to 8 of the publication; JP-A-7-104426 Compounds represented by the general formula [Na] and general formula [Nb] described in the Japanese Patent Publication No. To Nb-12 compounds: general formula (1), general formula (2), general formula (3), general formula (4), general formula (5), general formula (described in JP-A-8-272023) 6) and a compound represented by the general formula (7), specifically, compounds 1-1 to 1-19 described in the publication, -1 to 2-22, 3-1 to 3-36, 4-1 to 4-5, 5-1 to 5-41, 6-1 to 6-58, and Compounds 7-1 to 7-38; nucleation accelerators described in JP-A-9-297377, p55, column 108, line 8 to p69, column 136, line 44.
[0109]
As the nucleation accelerator used in the present invention, quaternary salt compounds represented by the following general formulas (a) to (f) are preferable, and compounds represented by the general formula (b) are most preferable. .
[0110]
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[0111]
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[0112]
Q in general formula (a)¹Represents a nitrogen atom or a phosphorus atom, and R¹⁰⁰, R¹¹⁰, R¹²⁰Each represents an aliphatic group, an aromatic group or a heterocyclic group, which may be bonded to each other to form a cyclic structure. M is a carbon atom contained in M and Q¹M to combine with¹⁰Valent organic group, where m¹⁰Represents an integer of 1 to 4.
In general formula (b), general formula (c), or general formula (d), A¹, A², A³, A⁴, A⁵Each represents an organic residue for completing an unsaturated heterocycle containing a quaternized nitrogen atom;¹⁰And L²⁰Represents a divalent linking group and R¹¹¹, R²²², R³³³Represents a substituent.
The quaternary salt compound represented by the general formula (a), the general formula (b), the general formula (c), or the general formula (d) has a repeating unit of ethyleneoxy group or propyleneoxy group in the molecule. Although it has 20 or more, you may have over two or more places.
[0113]
Q in general formula (e)²Represents a nitrogen atom or a phosphorus atom. R²⁰⁰, R²¹⁰, R²²⁰Is R in the general formula (a)¹⁰⁰, R¹¹⁰, R¹²⁰Represents a group having the same meaning as
In general formula (f), A⁶Is A in the general formula (b)¹Or A²Represents a group having the same meaning as However, A⁶The nitrogen-containing unsaturated heterocycle formed by may have a substituent but does not have a primary hydroxyl group on the substituent. L in general formula (e) and general formula (f)³⁰Represents an alkylene group, and Y represents —C (═O) — or —SO.₂-Represents L⁴⁰Represents a divalent linking group containing at least one hydrophilic group.
In general formula (a) to general formula (f), X^n-Represents an n-valent counter anion, and n represents an integer of 1 to 3. However, it has an anionic group separately in the molecule and (Q¹)⁺, (Q²)⁺Or N⁺When forming an internal salt with X^n-Is not necessary.
[0114]
R in the general formula (a)¹⁰⁰, R¹¹⁰, R¹²⁰Is an methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, or a hexadecyl group. Straight chain or branched alkyl group such as octadecyl group; aralkyl group such as substituted or unsubstituted benzyl group; cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group; allyl group, vinyl group, 5 An alkenyl group such as a hexenyl group; a cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group; and an alkynyl group such as a phenylethynyl group. Aromatic groups include aryl groups such as phenyl, naphthyl, and phenanthryl groups, and heterocyclic groups include pyridyl, quinolyl, furyl, imidazolyl, thiazolyl, thiadiazolyl, benzotriazolyl, Examples thereof include a benzothiazolyl group, a morpholyl group, a pyrimidyl group, and a pyrrolidyl group.
[0115]
Examples of substituents substituted on these groups include R¹⁰⁰, R¹¹⁰, R¹²⁰In addition to the group represented by the above, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group, (alkyl or aryl) amino group, alkoxy group, aryloxy group, (alkyl or aryl) thio group , Carbonamido group, carbamoyl group, ureido group, thioureido group, sulfonylureido group, sulfonamido group, sulfamoyl group, hydroxyl group, sulfonyl group, carboxyl group (including carboxylate), sulfo group (including sulfonate), cyano group , An oxycarbonyl group, an acyl group, a heterocyclic group (including a heterocyclic group containing a quaternized nitrogen atom), and the like. These substituents may be further substituted with these substituents.
R in the general formula (a)¹⁰⁰, R¹¹⁰, R¹²⁰May be bonded to each other to form a cyclic structure.
[0116]
Examples of the group represented by M in the general formula (a) include m¹⁰R represents 1, R¹⁰⁰, R¹¹⁰, R¹²⁰And a group having the same meaning. m¹⁰Is an integer of 2 or more, M is a carbon atom contained in M and Q¹M to combine with¹⁰Represents a valent linking group, specifically, an alkylene group, an arylene group, a heterocyclic group, and these groups and a —CO— group, —O— group, —N (RN) — group, —S— group. , -SO- group, -SO₂M formed by combining-, -P = O- groups¹⁰Represents a valent linking group (RN represents a hydrogen atom or R¹⁰⁰, R¹¹⁰, R¹²⁰And when there are a plurality of RNs in the molecule, these may be the same or different and may be bonded to each other). M may have an arbitrary substituent, and examples of the substituent include R¹⁰⁰, R¹¹⁰, R¹²⁰The same thing as the substituent which the group represented by this may have is mentioned.
[0117]
R in the general formula (a)¹⁰⁰, R¹¹⁰, R¹²⁰Is preferably a group having 20 or less carbon atoms, and Q¹Is particularly preferably an aryl group having 15 or less carbon atoms,¹When represents a nitrogen atom, an alkyl group, aralkyl group or aryl group having 15 or less carbon atoms is particularly preferred. m¹⁰Is preferably 1 or 2, m¹⁰When M represents 1, M is preferably a group having 20 or less carbon atoms, and an alkyl group, an aralkyl group or an aryl group having a total carbon number of 15 or less is particularly preferable. m¹⁰When D represents 2, the divalent organic group represented by M is preferably an alkylene group, an arylene group, and these groups and a —CO— group, —O— group, —N (RN) — group, -S-group, -SO₂-A divalent group formed by combining groups. m¹⁰Is 2 and M is a carbon atom contained in M and Q¹It is preferably a divalent group having a total carbon number of 20 or less that binds to M or R¹⁰⁰, R¹¹⁰, R¹²⁰However, when a plurality of repeating units of ethyleneoxy group or propyleneoxy group are contained, the preferred range of the total carbon number described above is not limited thereto. M¹⁰When R represents an integer of 2 or more, R in the molecule¹⁰⁰, R¹¹⁰, R¹²⁰Each has a plurality of R, but the plurality of R¹⁰⁰, R¹¹⁰, R¹²⁰May be the same or different.
[0118]
The quaternary salt compound represented by the general formula (a) has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group in the molecule, which may be substituted at one place or plural places. It may be substituted across. m¹⁰When represents an integer of 2 or more, the linking group represented by M preferably has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group.
[0119]
In general formula (b), general formula (c) or general formula (d), A¹, A², A³, A⁴, A⁵Represents an organic residue for completing a substituted or unsubstituted unsaturated heterocycle containing a quaternized nitrogen atom, which may contain carbon, oxygen, nitrogen, sulfur and hydrogen atoms; Further, the benzene ring may be condensed.
A¹, A², A³, A⁴, A⁵Examples of the unsaturated heterocycle formed by may include pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, thiazole ring, thiadiazole ring, benzotriazole ring, benzothiazole ring, pyrimidine ring, pyrazole ring and the like. Particularly preferred are a pyridine ring, a quinoline ring and an isoquinoline ring.
A¹, A², A³, A⁴, A⁵The unsaturated heterocyclic ring formed with quaternized nitrogen atom may have a substituent. Examples of the substituent in this case include R in the general formula (a)¹⁰⁰, R¹¹⁰, R¹²⁰The same thing as the substituent which the group represented by this may have is mentioned. The substituent is preferably a halogen atom (particularly a chlorine atom), an aryl group having 20 or less carbon atoms (particularly a phenyl group is preferred), an alkyl group, an alkynyl group, a carbamoyl group, an (alkyl or aryl) amino group, (alkyl or aryl). ) Oxycarbonyl group, alkoxy group, aryloxy group, (alkyl or aryl) thio group, hydroxy group, mercapto group, carbonamido group, sulfonamido group, sulfo group (including sulfonate), carboxyl group (including carboxylate) , A cyano group, and the like. Particularly preferred are a phenyl group, an alkylamino group, a carbonamido group, a chlorine atom, an alkylthio group and the like, and most preferred is a phenyl group.
[0120]
L¹⁰, L²⁰The divalent linking group represented by the formula: alkylene, arylene, alkenylene, alkynylene, divalent heterocyclic group, -SO₂Those constituted by-, -SO-, -O-, -S-, -N (RN ')-, -C (= O)-, -PO- alone or in combination are preferred. However, RN 'represents an alkyl group, an aralkyl group, an aryl group, or a hydrogen atom. L¹⁰, L²⁰The divalent linking group represented by may have an arbitrary substituent. Examples of the substituent include R in the general formula (a)¹⁰⁰, R¹¹⁰, R¹²⁰The same thing as the substituent which the group represented by this may have is mentioned. L¹⁰, L²⁰Particularly preferred examples of are alkylene, arylene, -C (= O)-, -O-, -S-, -SO.₂Examples thereof include those constituted by-or -N (RN ')-alone or in combination.
[0121]
R¹¹¹, R²²², R³³³Is preferably an alkyl group having 1 to 20 carbon atoms or an aralkyl group, which may be the same or different. R¹¹¹, R²²², R³³³May have a substituent, and examples of the substituent include R in the general formula (a).¹⁰⁰, R¹¹⁰, R¹²⁰The same thing as the substituent which the group represented by this may have is mentioned. Particularly preferably, R¹¹¹, R²²², R³³³Are each an alkyl group having 1 to 10 carbon atoms or an aralkyl group. Examples of preferable substituents include carbamoyl group, oxycarbonyl group, acyl group, aryl group, sulfo group (including sulfonate), carboxyl group (including carboxylate), hydroxy group, (alkyl or aryl) amino group, An alkoxy group can be mentioned.
However, R¹¹¹, R²²², R³³³When a plurality of repeating units of ethyleneoxy group or propyleneoxy group are contained in¹¹¹, R²²², R³³³The preferred range of the carbon number described for is not limited thereto.
[0122]
The quaternary salt compound represented by the general formula (b) or the general formula (c) has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group in the molecule, but this is substituted at one place. Or may be substituted at multiple locations, A¹, A², A³, A⁴, R¹¹¹, R²²², L¹⁰, L²⁰Any of the above may be substituted, but preferably L¹⁰Or L²⁰It is preferable that the connecting group represented by the formula has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group.
[0123]
The quaternary salt compound represented by the general formula (d) has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group in the molecule, which may be substituted at one place or at plural places. May be substituted with A⁵Or R³³³May be substituted, but preferably R³³³It is preferable that the group represented by the formula has a total of 20 or more repeating units of ethyleneoxy group or propyleneoxy group.
[0124]
The quaternary salt compounds represented by the general formula (a), the general formula (b), the general formula (c), and the general formula (d) may repeatedly contain an ethyleneoxy group and a propyleneoxy group at the same time. Good. In the case where a plurality of repeating units of ethyleneoxy group or propyleneoxy group are contained, the number of repeating units may take exactly one value or may be given as an average value. The compound is a mixture having a certain molecular weight distribution.
In the present invention, it is more preferable to have a total of 20 or more repeating units of ethyleneoxy group, and it is more preferable to have a total of 20 to 67 total units.
[0125]
Q in general formula (e)², R²⁰⁰, R²¹⁰, R²²⁰Are Q in the general formula (a), respectively.¹, R¹⁰⁰, R¹¹⁰, R¹²⁰Represents a group having the same meaning, and the preferred range thereof is also the same.
In general formula (f), A⁶Is A in the general formula (b)¹Or A²Represents a group having the same meaning, and the preferred range thereof is also the same. However, A in the general formula (f)⁶The nitrogen-containing unsaturated heterocyclic ring formed together with the quaternized nitrogen atom may have a substituent, but does not have a substituent containing a primary hydroxyl group.
[0126]
L in general formula (e) and general formula (f)³⁰Represents an alkylene group. The alkylene group is preferably a linear, branched, or cyclic, substituted or unsubstituted alkylene group having 1 to 20 carbon atoms. Further, not only saturated ones typified by ethylene groups, but also -CH₂C₆H₄CH₂-Or -CH₂CH = CHCH₂An unsaturated group represented by-may be contained. L³⁰Has a substituent, the substituent is R in the general formula (a).¹⁰⁰, R¹¹⁰, R¹²⁰The example of the substituent which the group represented by may have is given.
L³⁰Is preferably a linear or branched saturated group having 1 to 10 carbon atoms. More preferred is a substituted or unsubstituted methylene group, ethylene group or trimethylene group, particularly preferred is a substituted or unsubstituted methylene group or ethylene group, and most preferred is a substituted or unsubstituted methylene group.
[0127]
L in general formula (e) and general formula (f)⁴⁰Represents a divalent linking group having at least one hydrophilic group. Here, the hydrophilic group is -SO.₂-, -SO-, -O-, -P (= O) =, -C (= O)-, -CONH-, -SO₂NH-, -NHSO₂NH—, —NHCONH—, an amino group, a guanidino group, an ammonio group, a group of a heterocyclic group containing a quaternized nitrogen atom, or a combination of these groups. A combination of these hydrophilic groups and alkylene groups, alkenylene groups, arylene groups, and heterocyclic groups as appropriate.⁴⁰Is configured.
L⁴⁰A group such as an alkylene group, an arylene group, an alkenylene group, a heterocyclic group, or the like constituting R 1 may have a substituent. As the substituent, R in the general formula (a)¹⁰⁰, R¹¹⁰, R¹²⁰The same thing as the example of the substituent which the group represented by this may have is mentioned.
L⁴⁰The hydrophilic group is L⁴⁰Even if it exists in a form that divides⁴⁰L may be present as part of the above substituents, but L⁴⁰It is more preferable that it exists in the form which interrupts. For example, -C (= O)-, -SO₂-, -SO-, -O-, -P (= O) =, -CONH-, -SO₂NH-, -NHSO₂NH—, —NHCONH—, a cationic group (specifically, a quaternary salt structure of nitrogen or phosphorus, or a nitrogen-containing heterocycle containing a quaternized nitrogen atom), an amino group, a guanidino group, or A divalent group consisting of a combination of these groups is L⁴⁰It is a case where it exists in the form which divides.
[0128]
L⁴⁰One of preferable examples of the hydrophilic group possessed by is a group having a plurality of repeating units of an ethyleneoxy group or a propyleneoxy group, in which an ether bond and an alkylene group are combined. The polymerization degree or average polymerization degree is preferably 2 to 67.
L⁴⁰As the hydrophilic group possessed by —SO—₂-, -SO-, -O-, -P (= O) =, -C (= O)-, -CONH-, -SO₂NH-, -NHSO₂NH-, -NHCONH-, amino group, guadinino group, ammonio group, as a result of combining groups such as a quaternized nitrogen-containing heterocyclic group, or L⁴⁰It is also preferable that the substituent has a dissociable group. Here, the dissociable group means a group or a partial structure having a low acidity proton that can be dissociated with an alkaline developer, or a salt thereof. Group (-SO₃H), a phosphonic acid group (—PO₃H), phosphate group (-OPO₃H), hydroxy group (—OH group), mercapto group (—SH), —SO₂NH₂Group, N-substituted sulfonamide group (-SO₂NH-group, -CONHSO₂-Group, -SO₂NHSO₂-Groups), -CONHCO- groups, active methylene groups, -NH- groups inherent in nitrogen-containing heterocyclic groups, or salts thereof.
[0129]
L⁴⁰Is preferably an alkylene group or an arylene group, -C (= O)-, -SO₂-, -O-, -CONH-, -SO₂NH-, -NHSO₂A combination of NH-, -NHCONH-, and an amino group as appropriate is used. More preferably, an alkylene group having 2 to 5 carbon atoms and —C (═O) — or —SO.₂-, -O-, -CONH-, -SO₂NH-, -NHSO₂A combination of NH- and -NHCONH- as appropriate is used.
Y is -C (= O)-or -SO₂-Represents. Preferably -C (= O)-is used.
[0130]
In general formula (a) to general formula (f), X^n-Examples of the counter anion represented by the formula are halogen ions such as chlorine ion, bromine ion and iodine ion, carboxylate ions such as acetate ion, oxalate ion, fumarate ion and benzoate ion, p-toluenesulfonate, methanesulfonate Sulfonate ions such as butane sulfonate and benzene sulfonate, sulfate ions, perchlorate ions, carbonate ions and nitrate ions.
X^n-Is preferably a halogen ion, a carboxylate ion, a sulfonate ion, or a sulfate ion, and n is preferably 1 or 2. X^n-Is particularly preferably a chloro ion or a bromo ion, and most preferably a chloro ion.
However, it has an anionic group separately in the molecule and (Q¹)⁺, (Q²)⁺Or N⁺When forming an internal salt with X^n-Is not necessary.
[0131]
The quaternary salt compound used in the present invention is more preferably a quaternary salt compound represented by general formula (b), general formula (c), or general formula (f), among which general formula (b) and general formula ( The quaternary salt compound represented by f) is particularly preferred. Furthermore, in the general formula (b), L¹⁰Is preferably 20 or more repeating units of ethyleneoxy group, more preferably 20 to 67 repeating units. In general formula (f), A⁶It is particularly preferred when the unsaturated heterocyclic compound formed by 4-phenylpyridine, isoquinoline or quinoline.
[0132]
Next, specific examples of the quaternary salt compounds represented by the general formulas (a) to (f) are shown. In the following, Ph represents a phenyl group. However, the present invention is not limited by the following compound examples.
[0133]
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[0134]
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[0135]
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[0136]
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[0137]
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[0138]
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[0139]
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[0140]
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[0141]
The quaternary salt compounds represented by the general formulas (a) to (f) can be easily synthesized by known methods.
[0142]
Nucleation promoters that can be used in the present invention include suitable water-miscible organic solvents such as alcohols (methanol, ethanol, propanol, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cell. It can be used by dissolving in a solve.
[0143]
In addition, using a well-known emulsification dispersion method, it is dissolved using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be made and used. Alternatively, the nucleation accelerator powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.
[0144]
The nucleation accelerator that can be used in the present invention is preferably added to a non-light-sensitive layer composed of a hydrophilic colloid layer not containing a silver halide emulsion on the side of the silver halide emulsion layer with respect to the support. It is preferably added to a non-photosensitive layer comprising a hydrophilic colloid layer between the silver emulsion layer and the support.
The addition amount of the nucleation accelerator is 1 × 10 with respect to 1 mol of silver halide.^-6~ 2x10^-2mol is preferred, 1 × 10^-5~ 2x10^-2mol is more preferred, 2 × 10^-5~ 1x10^-2Most preferred is mol. Two or more kinds of nucleation accelerators can be used in combination.
[0145]
Various additives used in the silver halide photographic light-sensitive material of the present invention are not particularly limited. For example, JP-A-3-39948, page 10, lower right line 11 to page 12, lower left line 5, line. (Specifically, compounds of compounds (III) -1 to 25 described in the publication); a substance represented by the general formula (I) described in JP-A 1-118832 Specifically, a compound having no absorption maximum in the visible range (specifically, compounds I-1 to I-26 described in the same publication); JP-A-2-103536, page 17, lower right, line 19 Antifoggant described in page 4, upper right line, page 18; polymer latex described in JP-A-2-103536, page 18, lower left line 12 to page, lower left line 20; JP-A-9-179228 Represented by the general formula (I) described in Polymer latex having an active methylene group (specifically, compounds I-1 to I-16 described in the publication); Polymer latex having a core / shell structure described in JP-A-9-179228 (specifically, Are compounds P-1 to P-55 described in the above publication; acidic polymer latex described in JP-A-7-104413, page 14, left line 1 to right line 30 (specifically, the same document) Compounds II-1) to II-9)) described on page 15; Matte agents, slip agents and plastics described in JP-A-2-103536, page 19, upper left line 15 to page 19, upper right line 15 A hardening agent described in JP-A-2-103536, page 18, upper right line 5 to page 17, upper-right line 17; JP-A-2-103536, page 18, lower right line 6-page 19 Compound having an acid group described in the upper left first line JP-A-2-18542, page 2, lower left line 13 to the upper right line, page 7, upper right line 7 (specifically, the second page, lower right line, page 2, right side of the same publication) Metal oxide described in the lower line 10 and conductive polymer compounds of the compounds P-1 to P-7 described in the same publication); JP-A-2-103536, page 17, lower right, the first line to the same Water-soluble dyes described in the upper right line on page 18; solid dispersion represented by general formula (FA), general formula (FA1), general formula (FA2), and general formula (FA3) described in JP-A-9-179243 Dyes (specifically, compounds F1 to F34 described in the publication, (II-2) to (II-24) described in JP-A-7-152112, and (III-5) described in JP-A-7-152112 To (III-18), (IV-2) to (IV-7) described in JP-A-7-152112 ), Solid disperse dyes described in JP-A-2-294638 and JP-A-5-11382); redox compounds capable of releasing a development inhibitor by being oxidized as described in JP-A-5-274816, Preferably, a redox compound represented by general formula (R-1), general formula (R-2), or general formula (R-3) described in the publication (specifically, compound R- 1-R-68 compounds); JP-A-2-18542, page 3, lower right, lines 1 to 20 can be mentioned.
[0146]
The swelling ratio of the hydrophilic colloid layer including the emulsion layer and protective layer of the silver halide photographic light-sensitive material of the present invention is preferably in the range of 80 to 150%, more preferably in the range of 90 to 140%. The swelling ratio of the hydrophilic colloid layer is determined by the thickness of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic material (d₀), The silver halide photographic light-sensitive material was immersed in distilled water at 25 ° C. for 1 minute, the swelled thickness (Δd) was measured, and the swelling ratio (%) = (Δd ÷ d₀) X100.
[0147]
The film surface pH on the side on which the silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention is coated is preferably 7.5 or less, more preferably 4.5 to 6.0, More preferably, it is 4.8 to 6.0. If it is less than 4.5, the hardening of the emulsion layer tends to slow.
[0148]
Examples of the support that can be used in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected according to the intended use of the silver halide photographic material.
A support made of a styrene polymer having a syndiotactic structure described in JP-A-7-234478 and US Pat. No. 5,558,979 is also preferably used.
[0149]
The processing agents and processing methods such as developer and fixing solution that can be used in the silver halide photographic light-sensitive material of the present invention will be described below, but it goes without saying that the present invention is not limited to the following descriptions and specific examples. Absent.
[0150]
For the development processing of the silver halide photographic light-sensitive material of the present invention, any known method can be used. A known developing solution can be used.
[0151]
There are no particular limitations on the developing agent used in the developer used in the present invention (hereinafter, both development initiator and developer replenisher are collectively referred to as developer), but dihydroxybenzenes, ascorbic acid derivatives, hydroquinone, etc. Monosulfonates are preferably included, and may be used alone or in combination. In particular, it is preferable to contain a dihydroxybenzene-based developing agent and an auxiliary developing agent that exhibits superadditivity with this, and a combination of dihydroxybenzenes or ascorbic acid derivatives and 1-phenyl-3-pyrazolidones, or dihydroxybenzenes or Examples include combinations of ascorbic acid derivatives and p-aminophenols.
Among the developing agents used in the present invention, examples of the dihydroxybenzene developing agent include hydroquinone, chlorohydroquinone, isopropyl hydroquinone, and methyl hydroquinone. Hydroquinone is particularly preferable. As the ascorbic acid derivative developing agent, there are ascorbic acid and isoascorbic acid and their salts. Sodium erythorbate is particularly preferable from the viewpoint of material cost.
[0152]
As developing agents for 1-phenyl-3-pyrazolidone or its derivatives used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl- 4-hydroxymethyl-3-pyrazolidone and the like.
As p-aminophenol developers used in the present invention, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, There are o-methoxy-p- (N, N-dimethylamino) phenol, o-methoxy-p- (N-methylamino) phenol, among others, N-methyl-p-aminophenol, Aminophenols described in JP-A No. 297377 and JP-A-9-297378 are preferred.
[0153]
It is preferable that the dihydroxybenzene developing agent is usually used in an amount of 0.05 mol / L to 0.8 mol / L. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 mol / L to 0.6 mol / L, preferably 0.10 mol / L to 0.00. It is preferable to use 5 mol / L and the latter in an amount of 0.06 mol / L or less, preferably 0.03 mol / L to 0.003 mol / L.
[0154]
The ascorbic acid derivative developing agent is usually preferably used in an amount of 0.01 mol / L to 0.5 mol / L, more preferably 0.05 mol / L to 0.3 mol / L. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the ascorbic acid derivative is added in an amount of 0.01 mol / L to 0.5 mol / L, 1-phenyl-3-pyrazolidones. Alternatively, p-aminophenols are preferably used in an amount of 0.005 mol / L to 0.2 mol / L.
[0155]
The developer used for processing the silver halide photographic light-sensitive material of the present invention can contain commonly used additives (for example, developing agents, alkali agents, pH buffering agents, preservatives, chelating agents, etc.). . Specific examples of these are shown below, but what can be used in the present invention is not limited thereto.
Examples of the buffer used in the developing solution during development processing include carbonates, boric acid described in JP-A-62-286259, saccharides (for example, saccharose) described in JP-A-60-93433, and oximes. (For example, acetoxime), phenols (for example, 5-sulfosalicylic acid), tertiary phosphate (for example, sodium salt, potassium salt) and the like are used, and carbonate is preferably used. The amount of the buffer, particularly carbonate used is preferably 0.05 mol / L or more, particularly 0.08 to 1.0 mol / L.
[0156]
In the present invention, it is preferable that both the development starter and the development replenisher have a pH increase of 0.8 or less when 0.1 mol of sodium hydroxide is added to 1 L of the solution. As a method for confirming that the development starting solution or development replenisher used has this property, the pH of the development starting solution or development replenisher to be tested is adjusted to 10.5, and then sodium hydroxide is added to 0.1 L of this solution. 1 mol is added, and the pH value of the liquid at this time is measured. If the increase in pH value is 0.8 or less, it is determined that the liquid has the properties defined above. In the present invention, it is particularly preferable to use a development starter and a development replenisher that have a pH value increase of 0.7 or less when the above test is performed.
[0157]
Examples of the preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Sulphite is preferably used in an amount of 0.2 mol / L or more, particularly 0.3 mol / L or more. However, if added too much, it causes silver stains in the developer, so the upper limit should be 1.2 mol / L. desirable. Most preferably, it is 0.35-0.7 mol / L.
As a preservative for a dihydroxybenzene developing agent, a small amount of the ascorbic acid derivative may be used in combination with sulfite. Of these, sodium erythorbate is preferably used from the viewpoint of material cost. The addition amount is preferably in the range of 0.03 to 0.12, and particularly preferably in the range of 0.05 to 0.10, in terms of molar ratio with respect to the dihydroxybenzene developing agent. When using an ascorbic acid derivative as a preservative, it is preferable that the developer does not contain a boron compound.
[0158]
Additives used other than the above include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide, and alkanolamines such as diethanolamine and triethanolamine. , Development accelerators such as imidazole or derivatives thereof, heterocyclic mercapto compounds (for example, sodium 3- (5-mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercaptotetrazole, etc.), JP-A-62-2 The compounds described in JP-A-221651 can also be added as a physical development unevenness inhibitor.
Further, a mercapto compound, an indazole compound, a benzotriazole compound, or a benzimidazole compound may be included as an antifoggant or a black pepper inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole, 2- Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4, thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4 -Thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like. The amount of these additives is usually from 0.01 to 10 mmol, and more preferably from 0.1 to 2 mmol, per liter of the developing solution.
[0159]
Furthermore, various organic and inorganic chelating agents can be used alone or in combination in the developer used in the present invention.
Examples of the inorganic chelating agent that can be used include sodium tetrapolyphosphate and sodium hexametaphosphate.
On the other hand, as organic chelating agents, organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be mainly used.
Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, malein Examples include acid, itaconic acid, malic acid, citric acid, and tartaric acid.
[0160]
Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, Triethylenetetramine hexaacetic acid, 1,3-diamino-2-propanol tetraacetic acid, glycol ether diamine tetraacetic acid, other JP-A Nos. 52-25632, 55-67747, 57-102624, and special Mention may be made of the compounds described in JP-A-53-40900.
[0161]
Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acid and research disclosure described in, for example, US Pat. Nos. 3,214,454, 3,794,591 and German Patent Publication No. 2227369. 181 volume, Item 18170 (May 1979 issue) etc. are mentioned.
Examples of aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like. In addition, Research Disclosure 18170, JP-A-57-208554, 54. -61125 gazette, 55-29883 gazette, 56-97347 gazette etc. can also be mentioned.
[0162]
Examples of the organic phosphonocarboxylic acid include JP-A Nos. 52-102726, 53-42730, 54-121127, 55-4024, 55-4025, and 55-126241. And JP-A-55-65955, 55-65956, and Research Disclosure 18170 described above.
[0163]
These organic and / or inorganic chelating agents are not limited to those described above. Moreover, you may use in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 5 per liter of the developer.^-4~ 1x10^-1mol, more preferably 1 × 10^-3~ 1x10^-2mol.
[0164]
Further, as a silver stain preventing agent in the developer, for example, JP-A-56-24347, JP-B-56-46585, JP-B-62-2849, JP-A-4-362294, JP-A-8- In addition to the compounds described in JP 6215 A, triazines having one or more mercapto groups (for example, compounds described in JP-B-6-23830, JP-A-3-282457, JP-A-7-175178), mercapto Pyrimidines having one or more groups (for example 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2, 4, 6- Trimercaptopyrimidine, compounds described in JP-A-9-274289, etc.), pyridine having one or more mercapto groups ( For example, 2-mercaptopyridine, 2,6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,4,6-trimercaptopyridine, compounds described in JP-A-7-24887), and a mercapto group 1 Two or more pyrazines (for example, 2-mercaptopyrazine, 2,6-dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, etc.), pyridazines having one or more mercapto groups (for example, 3 -Mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimercaptopyridazine, 3,4,6-trimercaptopyridazine, etc.), compounds described in JP-A-7-175177, US Pat. No. 5,457 , 011 polyoxyalkyl phosphonic acid ester etc. used It can be. These silver stain preventing agents can be used singly or in combination, and the addition amount is preferably 0.05 to 10 mmol, more preferably 0.1 to 5 mmol per liter of the developer.
Moreover, the compound of Unexamined-Japanese-Patent No. 61-267759 can be used as a solubilizing agent.
Furthermore, a color toning agent, a surfactant, an antifoaming agent, a hardening agent, etc. may be included as necessary.
[0165]
The preferred pH of the developer is 9.0 to 12.0, particularly preferably 9.0 to 11.0, and further preferably 9.5 to 11.0. As the alkali agent used for pH adjustment, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.
[0166]
As cations in the developer, potassium ions do not suppress development more than sodium ions, and there are fewer jagged edges around the blackened portion called fringe. Furthermore, when it is stored as a concentrated solution, generally potassium salts are preferred because of their high solubility. However, in the fixing solution, potassium ions inhibit fixing to the same extent as silver ions. Therefore, when the potassium ion concentration of the developer is high, the developer is brought into the fixing solution by the silver halide photographic material. A potassium ion concentration becomes high and is not preferable. From the above, the molar ratio of potassium ions to sodium ions in the developer is preferably between 20:80 and 80:20. The ratio of potassium ion to sodium ion can be arbitrarily adjusted within the above range by a counter cation such as a pH buffer, a pH adjuster, a preservative, and a chelating agent.
[0167]
Developer replenishment amount is 1m of silver halide photographic material.²470 ml or less, preferably 30 to 325 ml. The development replenisher may have the same composition and / or concentration as the development starter, or may have a composition and / or concentration different from that of the starter.
[0168]
As the fixing agent of the fixing processing agent in the present invention, ammonium thiosulfate, sodium thiosulfate, and sodium ammonium thiosulfate can be used. The amount of the fixing agent used can be appropriately changed, but is generally about 0.7 to about 3.0 mol / L.
[0169]
The fixing solution in the present invention may contain a water-soluble aluminum salt and a water-soluble chromium salt that act as a hardening agent, and a water-soluble aluminum salt is preferable. Examples include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are preferably contained at 0.01 to 0.15 mol / L as the aluminum ion concentration in the working solution.
In the case where the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts with a hardener or the like as a separate part, or may be a one-part type composition including all components.
[0170]
As a fixing treatment agent, a preservative (for example, 0.015 mol / L or more, preferably 0.02 mol / L to 0.3 mol / L, for example, sulfite, bisulfite, metabisulfite, etc.), pH buffering agent, if desired. (For example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogen carbonate, phosphoric acid, succinic acid, adipic acid, etc. are 0.1 mol / L to 1 mol / L, preferably 0.2 mol / L to 0.7 mol / L), aluminum Compounds with stabilizing ability and water softening ability (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid, benzoic acid, salicylic acid, tyrone , Ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and These derivatives and their salts, saccharides and the like can be contained in 0.001 mol / L to 0.5 mol / L, preferably 0.005 mol / L to 0.3 mol / L). From the point of view, it is better not to contain boron compounds.
[0171]
In addition, compounds described in JP-A No. 62-78551, pH adjusters (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can also be included. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene surfactants, and amphoteric surfactants described in JP-A No. 57-6840. A known antifoaming agent is used. You can also Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include alkyl and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681, JP-B Nos. 45-35754, 58-122535, and 58-122536. Thiourea derivatives described above, alcohols having triple bonds in the molecule, thioether compounds described in US Pat. No. 4,126,459, JP-A-64-4739, JP-A-1-4739, Mercapto compounds described in JP-A-1-159645 and JP-A-3-101728, mesoionic compounds described in JP-A-4-170539, and thiocyanate can be included.
[0172]
The pH of the fixing solution in the present invention is preferably 4.0 or more, and more preferably 4.5 to 6.0. The pH of the fixing solution rises due to the mixing of the developer by the processing. In this case, the pH of the fixing solution is preferably 6.0 or less, more preferably 5.7 or less, In the non-hard film fixing solution, it is preferably 7.0 or less, and more preferably 6.7 or less.
[0173]
The replenishment amount of the fixing solution is 1 m of silver halide photographic light-sensitive material.²It is preferably 500 ml or less, more preferably 390 ml or less, particularly preferably 80 to 325 ml. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.
[0174]
The fixing solution can be regenerated and reused by a known fixing solution regeneration method such as electrolytic silver recovery. An example of the playback apparatus is FS-2000 manufactured by Fuji Photo Film Co., Ltd.
Moreover, it is also preferable to remove pigment | dyes etc. using adsorption filters, such as activated carbon.
[0175]
When the developing and fixing treatment agent in the present invention is a liquid agent, it is preferably stored in a packaging material having low oxygen permeability as described in, for example, JP-A-61-73147. Furthermore, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water with respect to 1 part of the concentrated liquid so as to have a predetermined concentration.
[0176]
Even if the development processing agent and the fixing processing agent in the present invention are solid, the same result as the liquid agent can be obtained. The solid processing agent will be described below.
In the present invention, a solid agent having a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste, etc.) can be used. These solid agents may be coated with a water-soluble coating agent or film in order to separate components that react with each other upon contact, or components that react with each other may be separated in a plurality of layers. These may be used in combination.
[0177]
Known coating agents and granulation aids can be used, but polyvinyl pyrrolidone, polyethylene glycol, polystyrene sulfonic acid, and vinyl compounds are preferably used. In addition, JP-A-5-45805, column 2, line 48 to column 3, line 13 can be referred to.
[0178]
In the case of a plurality of layers, a component that does not react even when contacted may be sandwiched between components that react with each other, and processed into tablets, briquettes, etc. It may be configured and packaged. These methods are disclosed in, for example, JP-A Nos. 61-259921, 4-16841, 4-78848, and 5-93991.
[0179]
The bulk density of the solid processing agent is 0.5 to 6.0 g / cm.³In particular, tablets are 1.0-5.0 g / cm³And the granule is 0.5 to 1.5 g / cm.³Is preferred.
[0180]
Any known method can be used for producing the solid processing agent in the present invention. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, 4-32837, 4-78848, 5-93991, 4 -85533, 4-85534, 4-85535, 5-134362, 5-197070, 5-204098, 5-224361, 6- Reference can be made to JP-A-138604, JP-A-6-138605, and 8-286329.
[0181]
More specifically, rolling granulation method, extrusion granulation method, compression granulation method, pulverization granulation method, stirring granulation method, spray drying method, dissolution coagulation method, briquetting method, roller compacting method, etc. Can be used.
[0182]
The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smooth, porous, etc.), partially changing the thickness, or making it into a hollow donut shape. Furthermore, it is also possible to take a plurality of shapes in order to give different solubility to a plurality of granulated products or to match the solubility of materials having different solubility. Moreover, the multilayer granulated material from which a composition differs in the surface and an inside may be sufficient.
[0183]
The packaging material of the solid agent is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known material such as a bag shape, a cylindrical shape, or a box shape. JP-A-6-242585 to JP-A-6-242588, JP-A-6-247432, JP-A-6-247448, JP-A-6-301189, JP-A-7-5664, JP-A-7-5666. In order to reduce the storage space for the waste packaging material, it is also preferable to use a foldable shape as disclosed in JP-A-7-5669. These packaging materials may have a screw cap, a pull top, an aluminum seal attached to the processing agent outlet, or heat-sealing the packaging material, but other known materials may be used, and there is no particular limitation. do not do. Furthermore, it is preferable to recycle or reuse waste packaging materials for environmental conservation.
[0184]
The method for dissolving and replenishing the solid processing agent is not particularly limited, and a known method can be used. These methods include, for example, a method in which a fixed amount is dissolved and replenished with a dissolution apparatus having a stirring function, a dissolution having a dissolution part and a part for stocking a finished liquid as described in JP-A-9-80718. A processing agent is supplied to the circulation system of an automatic processor as described in a method of dissolving in an apparatus and replenishing from a stock section, JP-A-5-119454, JP-A-6-19102, and JP-A-7-261357. There are a method of charging and dissolving / replenishing, a method of charging and dissolving a processing agent according to the processing of the silver halide photographic light-sensitive material with an automatic processor having a dissolution tank, and any other known method. Can also be used. In addition, the processing agent may be input manually, or may be automatically opened and automatically input by a dissolution apparatus or an automatic developing machine having an opening mechanism as described in JP-A-9-138495, The latter is preferable from the viewpoint of the working environment. Specifically, there are a method of breaking through the take-out port, a method of peeling, a method of cutting, a method of cutting out, and methods described in JP-A-6-19102 and JP-A-6-95331.
[0185]
The silver halide photographic light-sensitive material that has been developed and fixed is then washed with water or stabilized (hereinafter referred to as water washing, including stabilization, unless otherwise specified). Called water). The water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing solution. These replenishing amounts are generally 1 m of silver halide photographic light-sensitive material.²Although it is about 8L to about 17L per, it can also carry out with the replenishment amount below it. In particular, a replenishment amount of 3 L or less (including 0, that is, rinsing with water) not only enables water-saving processing, but also eliminates the need for piping for installing an automatic processor. When washing with a low replenishing amount, it is more preferable to provide a squeeze roller and crossover roller washing tank described in JP-A-63-18350 and JP-A-62-287252. In addition, various oxidants (such as ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) are used to reduce pollution load, which is a problem when washing with small amounts of water, and to prevent scaling. Addition and filter filtration may be combined.
[0186]
As a method for reducing the replenishment amount of washing with water, a multi-stage counter-current method (for example, 2 steps, 3 steps, etc.) has been known for a long time.²50 to 200 ml per unit is preferred. This effect can be obtained in the same manner even in an independent multi-stage system (a method in which a new liquid is individually replenished in a multi-stage washing tank without using a countercurrent flow).
[0187]
Furthermore, you may give a scale prevention means to the washing process. As the scale preventing means, known means can be used, although not particularly limited, a method of adding an antifungal agent (so-called scale preventing agent), a method of energizing, a method of irradiating ultraviolet rays, infrared rays or far infrared rays, There are a method of applying a magnetic field, a method of ultrasonic treatment, a method of applying heat, and a method of emptying the tank when not in use. These scales may be used in accordance with the processing of the silver halide photographic light-sensitive material, may be performed at regular intervals regardless of the usage status, or only during periods when processing is not performed, such as at night. Also good. Alternatively, it may be preliminarily applied to washing water and replenished. Furthermore, it is also preferable to perform different scale prevention means for each fixed period in order to suppress the generation of resistant bacteria.
As the water-saving water scale prevention device, Fujifilm Corporation AC-1000 and Fuji Film Corporation AB-5 may be used as the water scale prevention agent, or the method disclosed in JP-A-11-231485 may be used.
There are no particular limitations on the antifungal agent, and known ones can be used. In addition to the above-mentioned oxidizing agents, there are chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxide (for example, 2-mercaptopyridine-N-oxide, etc.), etc., alone or in combination. But you can.
As a method of energizing, the methods described in JP-A-3-224855, JP-A-3-224687, JP-A-4-16280, JP-A-4-18980 and the like can be used.
[0188]
In addition, a known water-soluble surfactant or antifoaming agent may be added for preventing water bubble unevenness and dirt transfer. Further, a dye adsorbent described in JP-A-63-163456 may be installed in a washing system in order to prevent contamination with dyes eluted from the silver halide photographic light-sensitive material.
[0189]
A part or all of the overflow solution from the washing step can be mixed and used in a processing solution having fixing ability as described in JP-A-60-235133. In addition, biochemical oxygen demand by microbial treatment (eg, sulfur-oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramic), oxidation treatment with electricity or oxidant, etc. Drainage after reducing the amount (BOD), chemical oxygen demand (COD), iodine consumption, etc., and forming a slightly soluble silver complex such as a filter using a polymer with affinity for silver or trimercaptotriazine It is also preferable from the viewpoint of conservation of the natural environment to add a compound to be added, to precipitate silver and to filter it, and to reduce the silver concentration in the waste water.
[0190]
Further, there is a case where a stabilization treatment is performed following the water washing treatment, and examples thereof are described in JP-A-2-2013357, JP-A-2-132435, JP-A-1-102553, and JP-A-46-44446. A bath containing the above compound may be used as the final bath of the silver halide photographic material. In this stabilizing bath, metal compounds such as ammonium compounds, Bi and Al, fluorescent brighteners, various chelating agents, film pH regulators, hardeners, bactericides, antifungal agents, alkanolamines and surfactants as necessary Agents can also be added.
[0191]
Additives and stabilizers such as an anti-bacterial agent added to the water-washing and stabilizing bath can be made into solid agents as in the above-described development and fixing treatment agents.
[0192]
The developer, fixing solution, washing water, and stabilizing solution waste solution used in the present invention are preferably disposed of by incineration. Further, these waste liquids can be disposed of after being concentrated or liquefied by a concentrating device as described in, for example, Japanese Patent Publication No. 7-83867 and US Pat. No. 5,439,560. .
[0193]
When reducing the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent liquid evaporation and air oxidation. The roller-conveying type automatic developing machine is described in US Pat. Nos. 3,025,779 and 3,545,971. In this specification, it is simply referred to as a roller-conveying type automatic developing machine. To do. This automatic machine is composed of four steps of development, fixing, washing and drying. When processing the silver halide photographic light-sensitive material of the present invention, other steps (for example, a stop step) are not excluded, but these four steps are not excluded. Most preferably, the process is followed. Further, a rinsing bath, a water washing tank or a washing tank may be provided between the development fixing and / or the fixing water washing.
[0194]
When developing the silver halide photographic light-sensitive material of the present invention, it is preferable to carry out from 25 to 160 seconds from the start of processing to after drying (development and fixing time is 40 seconds or less). It is more preferable that it is 6 to 35 seconds, and the temperature of each solution is preferably 25 to 50 ° C, more preferably 30 to 40 ° C. The washing temperature and time are preferably 0 to 50 ° C. and 40 seconds or less. According to this method, the silver halide photographic light-sensitive material that has been developed, fixed and washed with water may be dried by squeezing the washing water, that is, through a squeeze roller. Drying is performed at about 40 to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. Any known drying method can be used, and is not particularly limited. However, the drying method is disclosed in Japanese Patent Application Laid-Open Nos. 4-15534, 5-2256, and 5-289294. Heat roller drying, drying by far infrared rays, etc., and a plurality of methods may be used in combination.
[0195]
【Example】
The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. Further, “parts” in the examples indicate parts by mass unless otherwise specified.
[0196]
<Example 1>
<< Preparation of Emulsion A >>
1 liquid
750 ml of water
20g gelatin
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
[0197]
2 liquids
300 ml of water
150g silver nitrate
[0198]

[0199]
K used for 3 liquids₃IrCl₆(0.005%), (NH₄)₃[RhCl₅(H₂O)] (0.001%) was prepared by dissolving the powder in a 20% aqueous solution of KCl and a 20% aqueous solution of NaCl, respectively, and heating at 40 ° C. for 120 minutes.
[0200]
To 1 liquid maintained at 38 ° C. and pH 4.5, an amount corresponding to 90% of 2 liquid and 3 liquid was simultaneously added over 20 minutes with stirring to form 0.21 μm core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 10% of the 2nd and 3rd liquids were further added over 2 minutes to grow to 0.23 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete grain formation.
[0201]
4 liquids
100ml water
Silver nitrate 50g
[0202]
5 liquids
100ml water
Sodium chloride 13g
Potassium bromide 11g
K₄[Fe (CN)₆] 3H₂O (yellow blood salt) 8.0 × 10^-7mol / Agmol
[0203]
Then, it washed with water by the flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of anionic precipitating agent-1 shown below was added, and the pH was lowered using sulfuric acid until the silver halide was precipitated (in the range of pH 3.2 ± 0.2). Met). Next, about 3 L of the supernatant was removed (first water washing). Further, 3 L of distilled water was added, and sulfuric acid was added until silver halide precipitated. 3 L of the supernatant was removed again (second water washing). The same operation as the second water washing was further repeated once (third water washing) to complete the water washing / desalting process. Gelatin 45g was added to the emulsion after washing and desalting, adjusted to pH 5.6, pAg 7.5, sodium benzenethiosulfonate 10mg, sodium benzenethiosulfinate 3mg, sodium thiosulfate pentahydrate 15mg and chloroauric acid 4.0 mg was added and chemical sensitization was performed to obtain an optimum sensitivity at 55 ° C., and 100 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and an antiseptic (ICI ( Co., Ltd., Proxel) 100 mg was added.
Finally, a silver iodochlorobromide cubic grain emulsion containing 30 mol% of silver bromide and 0.08 mol% of silver iodide and having an average grain size of 0.24 μm and a coefficient of variation of 9% was obtained. Finally as an emulsion, pH = 5.7, pAg = 7.5, conductivity = 40 μS / m, density = 1.2 to 1.25 × 10³kg / m³Viscosity = 50 mPa · s. Further, the molar amount of silver inside the metal complex was 92.5% of the total silver amount.
[0204]
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[0205]
<< Preparation of Emulsion B >>
With respect to Emulsion A, 55 mol% of silver bromide, average grain size of 0.21 μm, K₄[Fe (CN)₆] 3H₂The dope amount of O (yellow blood salt) is 3.0 × 10^-5It was prepared in the same manner as Emulsion A except that the amount was changed to mol / Agmol. The halogen composition was adjusted by changing the addition amounts of the third and fifth solutions of sodium chloride and potassium bromide, and the particle size was adjusted by changing the addition amount of sodium chloride of one solution and the preparation temperature.
[0206]
<< Preparation of coating liquid >>
The silver halide photographic light-sensitive material prepared in this example is composed of a UL layer / emulsion layer / lower protective layer / upper protective layer on one side of a polyethylene terephthalate film support having a moisture-proof layer undercoat containing vinylidene chloride on both sides as shown below. And a conductive layer / back layer formed on the opposite surface.
The composition of the coating solution used for forming each layer is shown below.
[0207]
UL layer coating solution
Gelatin 0.5g / m²
Polyethyl acrylate latex 150mg / m²
Compound (Cpd-7) 40 mg / m²
Compound (Cpd-14) 10 mg / m²
5-methylbenzotriazole 20mg / m²
Preservative (ICI, Proxel) 1.5mg / m²
[0208]

The coating solution pH was adjusted to 5.6 using citric acid.
The emulsion layer coating solution prepared in this manner was subjected to a silver amount of 2.9 g / m on the following support.²Gelatin amount 1.2g / m²It applied so that it might become.
[0209]
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[0210]
Protective layer lower layer coating solution
Gelatin 0.5g / m²
Compound (Cpd-12) 15 mg / m²
1,5-dihydroxy-2-benzaldoxime 10 mg / m²
Polyethyl acrylate latex 150mg / m²
Compound (Cpd-13) 3 mg / m²
Compound (Cpd-20) 5 mg / m²
Preservative (ICI, Proxel) 1.5mg / m²
[0211]

In addition, the following thickener Z was added to the coating liquid of each layer, and viscosity was adjusted.
[0212]
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[0213]

[0214]

[0215]
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[0216]
<Support>
On both sides of a biaxially stretched polyethylene terephthalate support (thickness: 175 μm), the undercoat layer first layer coating solution, the undercoat layer second layer coating solution and the undercoat layer third layer coating solution having the following composition are close to the support. The first layer, the second layer, and the third layer were applied in this order.
[0217]
Undercoat layer 1 layer coating solution
4 parts of montmorillonite (Kunimine Industry Co., Ltd. Kunipia G) was dispersed in 200 parts of water, 2.5 parts of n-dodecyltrimethylammonium chloride was added thereto, and the mixture was stirred at room temperature for 1 hour. This was suction filtered using a membrane filter while thoroughly washing with water, and vacuum dried at 100 ° C. for 24 hours to obtain organic montmorillonite coated with an organic ammonium salt. Further, 2 parts of the obtained organic montmorillonite and 100 parts of a water-dispersible polyester resin (2,6-naphthalenedicarboxylic acid / ethylene glycol / sodium sulfoterephthalate copolymer) were dispersed in water so as to be 10% by mass, A coating solution for forming an undercoat layer was obtained.
The undercoat layer forming coating solution was applied so that the thickness after drying was 0.5 μm (sample No. 1).
[0218]

Further, 10% by mass of KOH was added, and the coating solution adjusted to pH = 6 was applied so that the dry film thickness after drying for 2 minutes at a drying temperature of 180 ° C. was 0.9 μm.
[0219]
Undercoat layer 3rd layer coating solution
1g of gelatin
Methylcellulose 0.05g
Compound (Cpd-22) 0.02 g
C₁₂H₂₅O (CH₂CH₂O)₁₀H 0.03g
Preservative (manufactured by ICI, Proxel) 3.5 × 10^-3g
Acetic acid 0.2g
Amount of water totaling 100g
This coating solution was applied so that the dry film thickness after drying at a drying temperature of 170 ° C. for 2 minutes was 0.1 μm.
[0220]
Sample No. In Nos. 2 to 6, the dispersion time and coating thickness of the filler added to the first undercoat layer to be coated on the support were changed as shown in Table 1, and other than that, Sample No. It was produced by the same method as 1.
[0221]
Sample No. No. 7 is a sample No. 7 except that the filler contained in the undercoat layer was changed to aerosil having an average primary particle size of 5 nm. It was produced by the same method as 1.
[0222]
Sample No. No. 8 is Sample No. except that the first undercoat layer is not provided. It was produced by the same method as 1.
[0223]
Sample No. No. 9 is a sample No. 1 except that the first primer layer does not contain a filler. It was produced by the same method as 1.
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[0224]
<Method of coating on support>
A slide bead coater is maintained on the support with the above subbing layer on the emulsion layer side, starting from the side closer to the support, in the order of the UL layer, emulsion layer, protective layer lower layer and protective layer upper layer at 35 ° C. Apply a multilayer coating while adding a hardener solution according to the method, and after passing through a cold air set zone (5 ° C), in the order of the conductive layer and back layer from the side closer to the support on the side opposite to the emulsion surface, While adding a hardener solution by a coater method, simultaneous multilayer coating was performed, and the solution was passed through a cold air set zone (5 ° C.). When passing through each set zone, the coating solution showed a sufficient setting property. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions. In addition, after apply | coating the back surface side, it conveyed in the state without contact at all to a roller and others until winding up. The coating speed at this time was 200 m / min.
[0225]
《Drying conditions》
After setting, dry with dry air at 30 ° C until the water / gelatin mass ratio reaches 800%, dry with 800% to 200% with dry air at 35 ° C and 30% relative humidity, and apply wind as it is. After 30 seconds from the time when the surface temperature reached 34 ° C. (deemed to be the end of drying), the substrate was dried with air at 48 ° C. and 2% relative humidity for 1 minute. At this time, the drying time was 50 seconds from the start of drying to 800% water / gelatin ratio, 35 seconds from 800% to 200%, and 5 seconds from 200% to the end of drying.
[0226]
This silver halide photographic light-sensitive material was wound up at 25 ° C. and 55% relative humidity, then cut in the same environment, and conditioned for 6 hours at 25 ° C. and 50% relative humidity for 8 hours. Sealed with cardboard that had been conditioned for 2 hours at a relative humidity of 50%. 1-9 were produced.
When the humidity in the barrier bag was measured, it was 45%. The film surface pH of the obtained sample on the emulsion layer side was 5.5 to 5.8, and the film surface pH on the back side was 6.0 to 6.5. The absorption spectra on the emulsion layer side and the back layer side were as shown in FIG.
[0227]
<Evaluation>
<Measurement of filler thickness and aspect ratio in undercoat layer>
A film containing particles to be measured and stretched 3.2 times or more in at least one of the vertical and horizontal directions is sliced with a microtome, and the section is 20,000 to 30,000 times with a transmission electron microscope (TEM H-800 type) manufactured by Hitachi, Ltd. Observing and measuring the plate diameter and thickness of at least 30 particles visible in the section, the ratio was taken as the aspect ratio.
[0228]
<Measurement of dimensional change rate>
About the obtained sample, the dimensional change when the environmental humidity of a room changed was measured with the following method. Two holes with a diameter of 8 mm were formed in the sample with an interval of 200 mm, and the following development processing was performed. After the treated sample is left in a room at 25 ° C. and a relative humidity of 60% for 24 hours, the interval between two holes is accurately measured in a room at 25 ° C. and a relative humidity of 60% using a pin gauge method with an accuracy of 1/1000 mm. did. The length at this time was X mm. The treated sample was then immediately transferred to a room at 25 ° C. and a relative humidity of 40%, and the length after 15 minutes and after standing for 4 hours was defined as Ymm. The dimensional change rate (%) when the environmental humidity of the room was changed was evaluated by (Y-X) × 100/200 (%).
[0229]
<Development processing method>
A developer (Fuji Photo Film Co., Ltd., QR-D1) and a fixing solution (Fuji Photo Film Co., Ltd., NF-1) are used, and an automatic processor (Fuji Photo Film Co., Ltd., FG-680AG) is used. ) And developed at 35 ° C. for 30 seconds. The drying temperature at that time was 45 ° C.
[0230]
[Table 1]

[0231]
<Evaluation results>
Sample No. having an undercoat layer containing a clay compound coated with organic matter. 1-7 had excellent dimensional stability. In particular, Sample No. containing a clay compound coated with an organic material having a thickness of 0.5 to 5 nm and an aspect ratio in the range of 50 to 10,000. 1-6 were excellent.
Sample No. having no first undercoat layer 7. Sample No. containing no filler in the undercoat layer No. 8 was inferior in dimensional stability.
[0232]
【The invention's effect】
According to the present invention, a silver halide photographic material excellent in dimensional stability can be provided.
[Brief description of the drawings]
FIG. 1 shows absorption spectra of an emulsion layer side and a back layer side of a silver halide photographic light-sensitive material according to one embodiment of the present invention.
[Explanation of sign]
The vertical axis represents absorbance (0.1 interval), and the horizontal axis represents wavelengths from 350 nm to 900 nm. The solid line shows the absorption spectrum on the emulsion layer side, and the broken line shows the absorption spectrum on the back layer side.

Claims (3)

In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and a back layer on the side opposite to the surface having the emulsion layer, between the support and the emulsion layer or the support A silver halide photographic light-sensitive material having an undercoat layer containing a clay compound coated with an organic substance between the substrate and the back layer. The silver halide photographic light-sensitive material according to claim 1, wherein the clay compound coated with the organic material has a thickness of 0.5 to 5 nm and an aspect ratio of 50 to 10,000. In the characteristic curve shown on the orthogonal coordinate axis where the unit length of the logarithmic exposure amount (x axis) and the optical density (y axis) are equal, the characteristic curve in which the gamma at the optical density of 0.1 to 1.5 is 4.0 or more. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein

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