JP2004317529A - Black-and-white silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a black-and-white silver halide photographic sensitive material which ensures a small dot % variation in running even under a small replenishment quantity of a developing solution when the sensitive material having a reduced silver amount is processed with an automatic processing machine after passing through an image setter or a laser plotter. <P>SOLUTION: In the black-and-white silver halide photographic sensitive material including at least one hydrophilic colloidal layer on a support, the at least one hydrophilic colloidal layer is a silver halide emulsion layer and at least one hydrazine derivative is contained in the hydrophilic colloidal layer. When the black-and-white silver halide photographic sensitive material is processed with a developing solution containing a hydroquinone developing principal agent and it is processed with a developing solution containing a hydroquinone monosulfonate developing principal agent in an amount equimolar to that of the hydroquinone developing principal agent, the difference in dot % is within 15%, and γ which is the inclination of a characteristic curve giving an optical density of 0.1 and an optical density of 1.5 ((difference between optical densities)/(difference between logarithms of light exposures)) is ≥10. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００４８】
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。
【００４９】
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。
【００５０】
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、クロロ原子、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。
【００５１】
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。
【００５２】
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。
【００５３】
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から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から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もしく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。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、飽和もしくは不飽和の、単環もしく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。
【００５４】
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。
【００５５】
Ｒ^１０で表される基は置換されていても良く、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。
【００５６】
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。
【００５７】
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４３８５１０８号、同第４４５９３４７号、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あげられる。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。
【００５８】
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。
【００５９】
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。
【００６０】
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、独特許第４，００６，０３２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。
【００６１】
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。
【００６２】
次に本発明において、特に好ましい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、置換基としてはアルキル基、（アルキル、アリールまたはヘテロ環）オキシ基、（アルキル、アリール、またはヘテロ環）チオ基、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好ましく、アルキル基、（アルキル、アリールまたはヘテロ環）オキシ基、（アルキル、アリール、またはヘテロ環）チオ基、アシルアミノ基、スルホンアミド基、ウレイド基がさらに好ましく、アルキル基、スルホンアミド基が最も好ましい。
【００６３】
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がアルキル基または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またはアルキル基上の置換基として、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。
【００６４】
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。
【００６５】
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。
【００６６】
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、本発明は以下の化合物に限定されるものではない。
【００６７】
【化２】

【００６８】
【化３】

【００６９】
【化４】

【００７０】
【化５】

【００７１】
【化６】

【００７２】
【化７】

【００７３】
【化８】

【００７４】
【化９】

【００７５】
【化１０】

【００７６】
【化１１】

【００７７】
【化１２】

【００７８】
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、下記の特許に記載された種々の方法により、合成することができる。
【００７９】
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；特開平１０−２３２４５６号公報に記載の一般式（Ｉ）で表される化合物で、具体的には同公報に記載の化合物Ｎ−Ｉ〜Ｎ−ＸＶＩＩＩ、特開平１１−１９０８８７号公報に記載の一般式（Ｉ）で表される化合物で、具体的には同公報に記載の化合物Ｎ−Ｉ〜Ｎ−ＸＩ、特開２００１−１０９０９４号公報に記載の一般式（Ｉ）で表される化合物で、具体的には同公報に記載の化合物ＩＩ〜Ｘ、特開２００１−１００３５１号公報に記載の一般式（Ｉ）で表される化合物で、具体的には同公報に記載の化合物ＩＩ〜ＸＶ；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を挙げることができる。
【００８０】
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用いることができる。
【００８１】
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の該ハロゲン化銀乳剤層、あるいは他の親水性コロイド層のどの層に添加してもよいが、該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。
本発明において造核剤添加量はハロゲン化銀１モルに対し１×１０^−４以上が好ましく、１×１０^−４〜１×１０^−２モルがより好ましく、１×１０^−４〜５×１０^−３モルが最も好ましい。
【００８２】
本発明のヒドラジンの添加量は、本発明の処理方法と組み合わせた時の網％変化が１５％以下でγ値が１０以上であることが必要である。
【００８３】
本発明においては、感光材料中に造核促進剤としてアミン誘導体、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を内蔵しても良い。本発明に用いられる造核促進剤の例として、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、具体的には同明細書に記載の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。
【００８４】
本発明に用いられる造核促進剤の具体例を以下に示す。但し、本発明で用いることができる造核促進剤は以下の化合物に限定されるものではない。
【００８５】
【化１３】

【００８６】
【化１４】

【００８７】
本発明の造核促進剤は、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。
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。
【００８８】
本発明の造核促進剤は、支持体に対してハロゲン化銀乳剤層側の該ハロゲン化銀乳剤層、あるいは他の親水性コロイド層のどの層に添加してもよいが、該ハロゲン化銀乳剤層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。
本発明の造核促進剤の添加量（ｍｏｌ／ｍｏｌＡｇ）は、造核剤の添加量（ｍｏｌ／ｍｏｌＡｇ）に対して１〜８倍が好ましく、より好ましくは１〜６倍である。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。
【００８９】
本発明の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、例えば下記箇所に記載されたものを好ましく用いることができる。
すなわち、特開平３−３９９４８号公報第１０頁右下１１行目から同公報第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行目から同公報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行目から同頁左下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で、具体的には同明細書に記載の化合物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で、具体的には同明細書に記載の化合物Ｐ−１〜Ｐ−５５；特開平７−１０４４１３号公報第１４頁左１行目から同頁右３０行目に記載の酸性ポリマーラテックスで、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行目から同公報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行目から同頁右上１７行目に記載の硬膜剤；特開平２ー１０３５３６号公報第１８頁右下６行目から同公報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行目から同公報第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行目から同頁右下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行目から同頁右上１８行目に記載の水溶性染料；特開平７−１７９２４３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２−１２２３６号公報第９頁右上７行目から同頁右下３行目に記載の界面活性剤．特開平２−１０３５３６号公報第１８頁左下４行目から同頁左下７行目に記載のＰＥＧ系界面活性剤；特開平３−３９９４８号公報第１２頁左下６行目から同公報第１３頁右下５行目に記載の含フッ素界面活性剤、具体的には、同公報に記載の化合物Ｉ−１〜Ｉ−１５の化合物；特開平５−２７４８１６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行目から２０行目に記載のバインダーを挙げることができる。
【００９０】
本発明の現像処理方法では、ベンゾトリアゾール系化合物の存在下で現像処理することが好ましい。ベンゾトリアゾール系化合物は感光材料中に添加してもよいし現像液中に添加してもよい。感光材料中に添加する場合は、ハロゲン化銀乳剤層側や支持体を挟んでハロゲン化銀乳剤層との反対側に添加してもよい。好ましくはハロゲン化銀乳剤層側がよい。
【００９１】
本発明に用いられるベンゾトリアゾール系化合物は、いかなる構造の物を用いてもよいが下記に示す構造の物が好ましい。
（１）５，６−ジメチルベンゾトリアゾール
（２）５−ブチルベンゾトリアゾール
（３）５−メチルベンゾトリアゾール
（４）５−クロロベンゾトリアゾール
（５）５−ブロモベンゾトリアゾール
（６）５，６−ジクロロベンゾトリアゾール
（７）４，６−ジクロロベンゾトリアゾール
（８）５−ニトロベンゾトリアゾール
（９）４−ニトロ−６−クロロベンゾトリアゾール
（１０）４，５，６−トリクロロベンゾトリアゾール
（１１）５−カルボキシベンゾトリアゾール
（１２）５−スルホベンゾトリアゾール
（１３）５−メトキシカルボニルベンゾトリアゾール
（１４）５−アミノベンゾトリアゾール
（１５）５−ブトキシベンゾトリアゾール
（１６）５−ウレイドベンゾトリアゾール
（１７）ベンゾトリアゾール
【００９２】
本発明のベンゾトリアゾール系化合物で特に好ましいものは、ベンゾトリアゾールまたは５−メチルベンゾトリアゾールである。
本発明のベンゾトリアゾール系化合物の添加量は、ハロゲン化銀写真感光材料の場合ハロゲン化銀１ｍｏｌに対して１×１０^−４〜１×１０^−１ｍｏｌが好ましく、１×１０^−３〜７×１０^−２ｍｏｌが特に好ましい。
現像液に添加する場合は、７．５×１０^−５〜７．５×１０^−３ｍｏｌ／Ｌが好ましく、７．５×１０^−５〜５．０×１０^−３ｍｏｌ／Ｌが特に好ましい。
また、ベンゾトリアゾール系化合物は２種以上併用して使用してもよいし、ハロゲン化銀写真感光材料と現像液添加を併用してもよい。
【００９３】
以下に本発明における現像液、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。
【００９４】
本発明の現像処理には、公知の方法のいずれを用いることもできるし、現像処理液には公知のものを用いることができる。
【００９５】
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。
【００９６】
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。
【００９７】
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。
【００９８】
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。
【００９９】
本発明で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（たとえば現像主薬、アルカリ剤、ｐＨ緩衝剤、保恒剤、キレート剤等）を含有することができる。以下にこれらの具体例を示すが、本発明はこれらに限定されるものではない。
本発明で感光材料を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（たとえばサッカロース）、オキシム類（たとえばアセトオキシム）、フェノール類（たとえば５−スルホサリチル酸）、第３リン酸塩（たとえばナトリウム塩、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。
【０１００】
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、モル比で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。
【０１０１】
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（たとえば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。
【０１０２】
さらに本発明の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たとえば、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たとえば、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。
【０１０３】
アミノポリカルボン酸としてはたとえば、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。
【０１０４】
有機ホスホン酸としては、たとえば米国特許第３，２１４，４５４号明細書、同３，７９４，５９１号明細書および西独特許公開２，２２７，３６９号明細書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、たとえばアミノトリス（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を挙げることができる。
【０１０５】
有機ホスホノカルボン酸としては、たとえば特開昭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。
【０１０６】
これらのキレート剤の中で特にジエチレントリアミン類が好ましい。ジエチレントリアミン類の中でもジエチレントリアミン五酢酸およびその金属塩がより好ましい。
【０１０７】
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。
【０１０８】
さらに、現像液中に銀汚れ防止剤として、たとえば特開昭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（たとえば特公平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）、同ピリミジン（たとえば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）、同ピリジン（たとえば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）、同ピラジン（たとえば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）、同ピリダジン（たとえば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。
【０１０９】
現像液の好ましいｐＨは９．０〜１１．０であり、特に好ましくは９．２〜１１．０、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（たと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。
【０１１０】
使用される現像液１Ｌに０．１ｍｏｌの水酸化ナトリウムを加えたときのｐＨ上昇が０．４以上であることがこのましく、さらに好ましくは０．４〜１．０である。
【０１１１】
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、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モル比率は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。
【０１１２】
現像液の補充量は、感光材料１ｍ^２につき３２３ｍｌ以下であり、３２３〜３０ｍｌが好ましく、３２３〜１２０ｍｌが最も好ましい。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。
【０１１３】
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かえることができるが、一般には約０．７〜約３．０ｍｏｌ／Ｌである。
【０１１４】
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。それにはたと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。
【０１１５】
定着処理剤には所望により保恒剤（たとえば亜硫酸塩、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（たとえば酢酸、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（たとえばグルコン酸、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）を含むことができるが、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。
【０１１６】
このほか、特開昭６２−７８５５１号公報に記載の化合物、ｐＨ調整剤（たと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、たと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４１２６４５９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。
【０１１７】
本発明における定着液のｐＨは、４．０以上が好ましく、より好ましくは４．５〜６．０を有する。定着液は処理により現像液が混入してｐＨが上昇するが、この場合、硬膜定着液では６．０以下好ましくは５．７以下であり、無硬膜定着液においては７．０以下好ましくは６．７以下である。
【０１１８】
定着液の補充量は、感光材料１ｍ^２につき５００ｍｌ以下であり、３９０ｍｌ以下が好ましく、３２０〜８０ｍｌがより好ましい。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。
【０１１９】
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、たとえば富士写真フイルム社製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。
【０１２０】
本発明における現像および定着処理剤が液剤の場合、たとえば特開昭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。
【０１２１】
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が、保存安定性等の観点からは、固形処理剤が好ましい。以下に固形処理剤に関する記述を行う。
本発明における固形剤は、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）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。
【０１２２】
被覆剤、造粒助剤に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行目が参考にできる。
【０１２３】
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、たとえば特開昭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。
【０１２４】
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。
【０１２５】
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。たとえば、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、特開平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。
【０１２６】
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。
【０１２７】
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。
【０１２８】
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。
【０１２９】
本発明の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たとえば、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。
【０１３０】
現像、定着処理が済んだ感光材料は、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、一般的には感光材料１ｍ^２あたり約１７Ｌ〜約８Ｌ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（たとえばオゾン、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。
【０１３１】
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（たとえば２段、３段等）が知られており、水洗補充量は感光材料１ｍ^２あたり２００〜５０ｍｌ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。
【０１３２】
さらに、本発明の方法で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、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。
【０１３３】
節水水垢防止装置としては、富士写真フイルム社製装置ＡＣ−１０００と水垢防止剤として富士写真フイルム社製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。前述の酸化剤の他たと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（たとえば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。
【０１３４】
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、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。
【０１３５】
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（たとえば硫黄酸化菌、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。
【０１３６】
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。
【０１３７】
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。
【０１３８】
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、これらの廃液はたとえば特公平７−８３８６７号公報、米国特許第５４３９５６０号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。
【０１３９】
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号明細書、同３，５４５，９７１号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、本発明の方法も、他の工程（たとえば停止工程）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（洗浄槽）を設けてもよい。
【０１４０】
本発明の現像処理では、処理開始から乾燥後まで（ｄｒｙ ｔｏ ｄｒｙ）で２５〜１６０秒が好ましく、現像および定着時間が４０秒以下、好ましくは６〜３５秒、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。本発明の方法によれば、現像、定着および水洗された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かえられる。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。
【０１４１】
本発明に用いられるイメージセッタ−と自動現像機は搬送性に問題が無ければ、いかなる組み合わせを用いてもよい。イメージセッターとしては富士写真フイルム（株）製のＦ９０００やラックスセッターＲＣ−５６００Ｖ、大日本スクリーン（株）製のイメージセッターＦＴ−Ｒ５０５５アグファゲバルト（株）製のセレクトセット５０００、アバントラ２５、もしくはアキュセット１０００、サイテックス（株）製のドレブ４５０、もしくはドレブ８００、ハイデル（株）製のライノ６３０、クエーサー、ハーキュレスエリート、もしくはシグナセッター、もしくはラクセルＦ−９０００、またはプレプレス（株）製のパンサープロ６２のいずれか１機種を用いてもよい。
本発明に用いられる工業分野（ＰＣＢ，ＰＷＢ）のフォトマスク用プロッターとしては、大日本スクリーン製造（株）製のＲＧ−７０００、ＲＧ−７５００、ＲＧ−４０００、ＲＧ−４５００、ＲＧ−８０００、Ｏｒｂｏｔｅｃｈ（株）製ＬＰ−５００８、ＬＰ−７００８、Ｄｙｎａｔｒｏｎ（株）製ＲＰ２０８ＮＴ、ＲＰ２１２ＮＴ、ＲＰ３０８ＮＴ、ＲＰ−３１２ＮＴ、ＲＰ５０８ＮＴ、ＲＰ５１２ＮＴ、旭光学工業（株）製ＬＰＰ３６５５、ＬＰＰ３６７７、ＬＰＰ３７００、ＬＰＰ３６９０などが挙げられる。
【０１４２】
【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。
【０１４３】
《実施例１》
［塗布液の調製］
＜乳剤Ａ＞
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
２液
水 ３００ｍｌ
硝酸銀 １５０ｇ
３液
水 ３００ｍｌ
塩化ナトリウム ３８ｇ
臭化カリウム ３２ｇ
ヘキサクロロイリジウム（ＩＩＩ）酸カリウム ５ｍｌ
（０．００５質量％、ＫＣｌの２０質量％水溶液）
ヘキサクロロロジウム酸アンモニウム ７ｍｌ
（０．００１質量％、ＮａＣｌの２０質量％水溶液）
【０１４４】
３液に用いるヘキサクロロイリジウム（ＩＩＩ）酸カリウム（０．００５質量％、ＫＣｌの２０質量％水溶液）およびヘキサクロロロジウム酸アンモニウム（０．００１質量％、ＮａＣｌの２０質量％水溶液）は、粉末をそれぞれＫＣｌの２０質量％水溶液、ＮａＣｌの２０質量％水溶液に溶解し、４０℃で１２０分間加熱して調製した。
【０１４５】
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、０．１６μｍ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、０．２１μｍ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。
【０１４６】
４液
水 １００ｍｌ
硝酸銀 ５０ｇ
５液
水 １００ｍｌ
塩化ナトリウム １３ｇ
臭化カリウム １１ｇ
黄血塩 ５０ｍｇ
【０１４７】
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１５ｍｇと塩化金酸１０ｍｇ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、防腐剤としてプロキセル（商品名、ＩＣＩ Ｃｏ．，Ｌｔｄ．製）１００ｍｇを加えた。
【０１４８】
最終的に臭化銀を３０ｍｏｌ％、沃化銀を０．０８ｍｏｌ％含む平均粒子サイズ０．２２μｍ、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＝１．２ｘ１０^３ｋｇ／ｍ^３、粘度＝５０ｍＰａ・ｓとなった。
【０１４９】
【化１５】

【０１５０】
＜乳剤層塗布液＞
乳剤Ａに、増感色素（ＳＤ−１）５．７×１０^−４ｍｏｌ／ｍｏｌＡｇを加えて分光増感を施した。さらにＫＢｒ３．４×１０^−４ｍｏｌ／ｍｏｌＡｇ、化合物（Ｃｐｄ−１）２．０×１０^−４ｍｏｌ／ｍｏｌＡｇ、化合物（Ｃｐｄ−２）２．０×１０^−４ｍｏｌ／ｍｏｌＡｇ、化合物（Ｃｐｄ−３）８．０×１０^−４ｍｏｌ／ｍｏｌＡｇを加え、良く混合した。次いで４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラアザインデン１．２×１０^−４ｍｏｌ／ｍｏｌＡｇ、ハイドロキノン１．２×１０^−２ｍｏｌ／ｍｏｌＡｇ、５−メチルベンゾトリアゾール８×１０^−４ｍｏｌ／ｍｏｌＡｇ、クエン酸３．０×１０^−４ｍｏｌ／ｍｏｌＡｇ、表１に記載される種類のヒドラジン系造核剤を表１に記載される量、２，４−ジクロロ−６−ヒドロキシ−１，３，５−トリアジンナトリウム塩を９０ｍｇ／ｍ^２、ゼラチンに対して１５質量％の粒子サイズ１０μｍのコロイダルシリカ、水性ラテックス（ａｑＬ−６）を１００ｍｇ／ｍ^２、ポリエチルアクリレートラテックスを１５０ｍｇ／ｍ^２、メチルアクリレートと２−アクリルアミド−２−メチルプロパンスルホン酸ナトリウム塩と２−アセトキシエチルメタクリレートのラテックス共重合体（質量比８８：５：７）を１５０ｍｇ／ｍ^２、コアシェル型ラテックス（コア：スチレン／ブタジエン共重合体（質量比３７／６３）、シェル：スチレン／２−アセトキシエチルアクリレート（質量比８４／１６）、コア／シェル比＝５０／５０）を１５０ｍｇ／ｍ^２、ゼラチンに対し４質量％の化合物（Ｃｐｄ−７）を添加し、クエン酸を用いてｐＨを５．６に調整して乳剤層塗布液とした。
【０１５１】
＜保護層上層塗布液＞
ゼラチン ０．３ｇ／ｍ^２
平均粒子サイズ３．５μｍの不定形シリカマット剤 ２５ｍｇ／ｍ^２
化合物（Ｃｐｄ−８）（ゼラチン分散物） ２０ｍｇ／ｍ^２
粒子サイズ１０〜２０μｍのコロイダルシリカ ３０ｍｇ／ｍ^２
（日産化学製スノーテックスＣ）
化合物（Ｃｐｄ−９） ５０ｍｇ／ｍ^２
ドデシルベンゼンスルホン酸ナトリウム ２０ｍｇ／ｍ^２
化合物（Ｃｐｄ−１０） ２０ｍｇ／ｍ^２
化合物（Ｃｐｄ−１１） ２０ｍｇ／ｍ^２
防腐剤 １ｍｇ／ｍ^２
（プロキセル（商品名、ＩＣＩ Ｃｏ．，Ｌｔｄ．製））
【０１５２】
＜保護層下層塗布液＞
ゼラチン ０．５ｇ／ｍ^２
造核促進剤（Ｃｐｄ−１２） 表１に示す量
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
防腐剤（プロキセル） １．５ｍｇ／ｍ^２
【０１５３】
＜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
防腐剤（プロキセル） １．５ｍｇ／ｍ^２
なお、各層の塗布液の粘度調整は、下記の構造を有する増粘剤Ｚを添加することにより行った。
【０１５４】
【化１６】

【０１５５】
【化１７】

【０１５６】
＜バック層塗布液＞
ゼラチン ３．３ｇ／ｍ^２
化合物（Ｃｐｄ−１５） ４０ｍｇ／ｍ^２
化合物（Ｃｐｄ−１６） ２０ｍｇ／ｍ^２
化合物（Ｃｐｄ−１７） ９０ｍｇ／ｍ^２
化合物（Ｃｐｄ−１８） ４０ｍｇ／ｍ^２
化合物（Ｃｐｄ−１９） ２６ｍｇ／ｍ^２
化合物（Ｃｐｄ−２２） ５ｍｇ／ｍ^２
化合物（Ｃｐｄ−９） １０ｍｇ／ｍ^２
１，３−ジビニルスルホニル−２−プロパノール ６０ｍｇ／ｍ^２
ポリメチルメタクリレート微粒子 ３０ｍｇ／ｍ^２
（平均粒子サイズ６．５μｍ）
流動パラフィン ７８ｍｇ／ｍ^２
化合物（Ｃｐｄ−７） １２０ｍｇ／ｍ^２
硝酸カルシウム ２０ｍｇ／ｍ^２
防腐剤（プロキセル） １２ｍｇ／ｍ^２
【０１５７】
＜導電層塗布液＞
ゼラチン ０．１ｇ／ｍ^２
ドデシルベンゼンスルホン酸ナトリウム ２０ｍｇ／ｍ^２
ＳｎＯ_２／Ｓｂ ２００ｍｇ／ｍ^２
（９／１質量比、平均粒子サイズ０．２５μｍ）
防腐剤（プロキセル） ０．３ｍｇ／ｍ^２
【０１５８】
【化１８】

【０１５９】
［下塗層を有する支持体の調製］
二軸延伸したポリエチレンテレフタレート支持体（厚み１００μｍ）の両面の下記組成の下塗層第１層および第２層を塗布した。
【０１６０】
＜下塗層１層＞
コア−シェル型塩化ビニリデン共重合体▲１▼ １５ｇ
２，４−ジクロロ−６−ヒドロキシ−ｓ−トリアジン ０．２５ｇ
ポリスチレン微粒子（平均粒子サイズ３μｍ） ０．０５ｇ
化合物（Ｃｐｄ−２０） ０．２０ｇ
コロイダルシリカ ０．１２ｇ
（スノーテックスＺＬ：粒子サイズ７０〜１００μｍ、日産化学（株）製）
水 全体量が１００ｇとなる量
さらに、１０質量％のＫＯＨを加えてｐＨ＝６に調整して塗布液とした。この塗布液をポリエチレンテレフタレート支持体上に塗布して、１８０℃で２分間乾燥して、乾燥膜厚が０．９μｍの下塗層第１層を形成した。
【０１６１】
＜下塗層第２層＞
ゼラチン １ｇ
メチルセルロース ０．０５ｇ
化合物（Ｃｐｄ−２１） ０．０２ｇ
Ｃ_１２Ｈ_２５Ｏ（ＣＨ_２ＣＨ_２Ｏ）_１０Ｈ ０．０３ｇ
プロキセル ３．５×１０^−３ｇ
酢酸 ０．２ｇ
水 全体量が１００ｇとなる量
この塗布液を下塗層第１層の上に塗布して１７０℃で２分間乾燥し、乾燥膜厚が０．１μｍの下塗層第２層を形成した。
【０１６２】
【化１９】

【０１６３】
［塗布・乾燥］
＜塗布条件＞
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。このとき、乳剤層塗布液をＡｇ２．９ｇ／ｍ^２、ゼラチン１．５ｇ／ｍ^２になるように塗布した。その後、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。
【０１６４】
＜乾燥条件＞
セット後、水／ゼラチンの質量比が８００％となるまで３０℃の乾燥風で乾燥し、８００％から２００％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）より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。
【０１６５】
得られた感光材料を２５℃相対湿度５５％で巻き取り、３５℃相対湿度３０％において７２時間熱処理を行なった。次いで２５℃相対湿度５５％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、試料を作製した。
バリアー袋内の相対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。
以上の手順により、白黒ハロゲン化銀写真感光材料Ｎｏ．１〜１４を作製した。
【０１６６】
［評価］
作製した各白黒ハロゲン化銀写真感光材料について、以下の評価を行った。
１）フレッシュ現像液を用いた試験
＜現像液と定着液＞
フレッシュ現像液を用いた試験では、以下の現像液１、現像液２および定着液（Ｂ）を用いた。定着液（Ｂ）は後述する自動現像機で用いた。
現像液１
水 ６００ｍｌ
水酸化カリウム ２９ｇ
ジエチレントリアミン−五酢酸 ２ｇ
メタ重亜硫酸ナトリウム ４０ｇ
炭酸カリウム ４０ｇ
臭化カリウム ３．２ｇ
ハイドロキノン ２３ｇ
４−ヒドロキシメチル−４−メチル−
１−フェニル−３−ピラゾリドン ０．４ｇ
エリソルビン酸ナトリウム ３ｇ
ジエチレングリコール ２０ｇ
水を加えて１ＬとしｐＨを１０．４５に合わせた。
現像液２
上記現像液１の処方におけるハイドロキノンをハイドロキノンと当モル量のハイドロキノンモノスルホン酸カリウム塩（４７．７ｇ）に変更した以外は、現像液１と同じ処方である。現像液２のｐＨは１０．４５であった。
【０１６７】
定着液（Ｂ）処方 濃縮液１Ｌあたりの処方を示す。
チオ硫酸アンモニウム ３６０ｇ
エチレンジアミン・四酢酸・２Ｎａ・２水塩 ０．０９ｇ
チオ硫酸ナトリウム・５水塩 ３３．０ｇ
メタ亜硫酸ナトリウム ５７．０ｇ
水酸化ナトリウム ３７．２ｇ
酢酸（１００％） ９０．０ｇ
酒石酸 ８．７ｇ
グルコン酸ナトリウム ５．１ｇ
硫酸アルミニウム ２５．２ｇ
ｐＨ ４．８５
使用にあたっては、上記濃縮液１体積部に対して水２体積部の割合で希釈した。使用液のｐＨは４．８であった。
【０１６８】
＜網％変化の測定＞
各白黒ハロゲン化銀写真感光材料を、富士写真フイルム（株）製のイメージセッターＲＣ５６００Ｖと自動現像機であるＡＰ−５６０を使用して、１７５線／インチで光量を変えながらテストステップを出力し、現像液１を用いて現像温度３５℃で３０秒間現像処理し、中間網点が５０％になるＬＶ値を求めた。この後，現像液２を用いて同ＬＶ値での網％を測定した。なお、網％はＭａｃｂｅｔｈＴＤ９０４を用いて測定した。網％の差は１５％以内であることが好ましく、１０％以内であることがより好ましい。
【０１６９】
＜γの測定＞
以下の手順によりγを測定することによって、写真性を評価した。
６３３ｎｍにピークを持つ干渉フィルターを介し、ステップウェッジを通して発光時間１０^−５秒のキセノンフラッシュ光で露光した。画像のコントラストを示す指標（階調）としては、特性曲線のｆｏｇ＋濃度０．１の点からｆｏｇ＋濃度１．５の点を直線で結び、この直線の傾きをγ値として表した。すなわち、γ（階調）＝（１．５−０．１）／〔ｌｏｇ（濃度１．５を与える露光量）−（濃度０．１を与える露光量）〕であり、γは大きいほど硬調な写真特性であることを示している。グラフィックアーツ用感光材料としては、γは１０以上であることが好ましい。
【０１７０】
＜結果＞
表１に各白黒ハロゲン化銀写真感光材料の網％変化とγ値を示す。
【０１７１】
【表１】

【０１７２】
２）ランニング試験
＜現像液と定着液＞
ランニング試験では、以下の現像液（Ａ）と上記の定着液（Ｂ）を用いた。
現像液（Ａ）処方 濃縮液１Ｌあたりの処方を示す

水酸化カリウムを加えて、水を加えて１Ｌとし、ｐＨを１０．７に合わせた。
上記の濃縮液１体積部に対して水３体積部を加えたものをスタート液（母液）とした（ｐＨは１０．４）。また、上記の濃縮液１体積部に対して水２体積部を加えたものを補充液とした（ｐＨは１０．４５）。
補充量は大全（５０．８×６１．０ｃｍ）１枚当たり１００ｍｌ、または、１ｍ^２当たり３２３ｍｌとした。
【０１７３】
＜フレッシュ液を用いた測定＞
各白黒ハロゲン化銀写真感光材料を、富士写真フイルム（株）製のイメージセッターＲＣ５６００Ｖと自動現像機であるＡＰ−５６０を使用して、１７５線／インチで光量を変えながらテストステップを出力し、現像液（Ａ）を使用して現像温度３５℃で３０秒間処理した。中間網点が５０％になるＬＶ値で露光した際のＤｍａｘ部を測定し、実技濃度（実技Ｄｍ）とした。なお、網％および実技濃度はＭａｃｂｅｔｈ ＴＤ９０４を用いて測定した。実技濃度は後工程を考慮すると４．０以上が必要で、好ましくは４．０〜５．０である。
【０１７４】
＜ランニング後の測定＞
実技濃度評価で用いた中間網点が５０％になる露光量を与えた感光材料を、１日当り５ｍ^２処理し、その時の現像液と定着液の補充量が３２３ｍｌ／ｍ^２で１ヶ月ランニングを行った時の実技Ｄｍと網％の評価を行った。網％はフレッシュ液５０％に対してランニング後網％変化が±３％以内であることが好ましい。
【０１７５】
＜結果＞
実験結果を表２に示す。
【０１７６】
【表２】

【０１７７】
表２より本発明の白黒ハロゲン化銀写真感光材料は、ランニング後の写真性（実技Ｄｍと網％変化）が良好であることが分かった。
なお、自動現像機の水洗工程において、水垢防止節水装置として富士写真フイルム社製ＡＣ−１０００を用い、薬剤として富士写真フイルム社製ＡＢ−５を組み合わせて使用した。補充量は、大全サイズ（６１．０ｃｍ×５０．８ｃｍ）１枚当たり１Ｌで行った。
【０１７８】
《実施例２》
実施例１と同様の実験を、フレッシュ液（スタート液）として実施例１の液剤を用い、補充液として実施例１のジエチレングリコールを除いた処方を用いて、下記積層の順序でポリエチレン容器に細密充填した固形現像剤と固形定着剤を用いて行った。その結果、実施例１と同様に本発明の白黒ハロゲン化銀写真感光材料が良好な性能を示した。
【０１７９】
現像剤
第一層 ハイドロキノン
第二層 その他成分
第三層 ＫＢｒ
第四層 Ｎａ_２Ｓ_２Ｏ_５
第五層 炭酸カリウム
第六層 ＫＯＨペレット
この処方を溶解して３Ｌにして使用した。
【０１８０】
定着剤は、下記処方を現像剤と同様に充填したものを使用した。

【０１８１】
《実施例３》
実施例１の白黒ハロゲン化銀写真感光材料Ｎｏ．２およびＮｏ．６と、下記現像液（Ｂ），（Ｃ），（Ｄ），（Ｅ）を用いて実施例１と同様の実験を行った。
【０１８２】
現像液（Ｂ）
水 ６００ｍｌ
水酸化カリウム ９６．０ｇ
ジエチレントリアミン−五酢酸 ６．０ｇ
炭酸カリウム ４８．０ｇ
メタ重亜硫酸ナトリウム １２０．０ｇ
臭化カリウム ９．０ｇ
ハイドロキノン ７０．０ｇ
５−メチルベンゾトリアゾール ０．２４ｇ
１−フェニル−３−ピラゾリドン １．７ｇ
２−メルカプトベンツチアゾール ０．１８ｇ
１−フェニル−５−メルカプトテトラゾール ０．０６ｇ
エリソルビン酸ナトリウム ９．０ｇ
ジエチレングリコール ４０．０ｇ
水酸化カリウムを加えて、水を加えて１Ｌとし、ｐＨを１０．８に合わせた。
上記の濃縮液１体積部に対して水２体積部を加えたものを現像液として使用した（ｐＨは１０．４５）。補充量は大全（５０．８×６１．０ｃｍ）１枚当たり１００ｍｌ、または、１ｍ^２当たり３２３ｍｌとした。
【０１８３】

水を加えて１ＬとしｐＨを１０．４８に合わせた。
【０１８４】

水を加えて１ＬとしｐＨを１０．４１に合わせた。
【０１８５】
現像液（Ｅ）
水 ６００ｍｌ
水酸化カリウム １７．０ｇ
エチレンジアン４酢酸２Ｎａ_２Ｈ_２Ｏ ２．０ｇ
炭酸カリウム １５．０ｇ
メタ重亜硫酸カリウム ２５．０ｇ
臭化カリウム ５．０ｇ
ハイドロキノン １２．０ｇ
１−フェニル−３−ピラゾリドン ０．２ｇ
水を加えて１ＬとしｐＨを１０．０５に合わせた。
実験結果を表３に示す。
【０１８６】
【表３】

【０１８７】
表３より、本発明の白黒ハロゲン化銀写真感光材料は、ランニング後の写真性（実技Ｄｍと網％変化）が良好であることが分かった。
【０１８８】
《実施例４》
実施例１〜３において現像温度３８℃、定着温度３７℃、現像時間２０秒に設定して処理を行ったところ、実施例１〜３と同様の結果となり、本発明の効果は失われることはなかった。
【０１８９】
《実施例５》
実施例１〜４において自動現像機を同社製ＦＧ−６８０ＡＳを用い、白黒ハロゲン化銀写真感光材料の搬送速度を線速１５００ｍｍ／分に設定して同様の処理をしても、同様の結果を得た。
【０１９０】
《実施例６》
上記ランニング方法の実技評価の際に、富士写真フイルム（株）製のラックスセッターＲＣ−５６００Ｖを使用するかわりに、大日本スクリーン（株）製のイメージセッターＦＴ−Ｒ５０５５アグファゲバルト（株）製のセレクトセット５０００、アバントラ２５、もしくはアキュセット１０００、サイテックス（株）製のドレブ４５０、もしくはドレブ８００、ハイデル（株）製のライノ６３０、クエーサー、ハーキュレスエリート、もしくはシグナセッター、もしくはラクセルＦ−９０００、またはプレプレス（株）製のパンサープロ６２のいずれか１機種を用いて実施例１〜５と同様の評価を行なったところ、本発明の白黒ハロゲン化銀写真感光材料に同様の効果が認められた。
【０１９１】
《実施例７》
以下の方法でハロゲン化銀写真感光材料を調製した。
【０１９２】
＜乳剤Ａの調製＞
１液
水 ６５０ｍｌ
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
【０１９３】
２液
水 ３００ｍｌ
硝酸銀 １５０ｇ
【０１９４】

【０１９５】
３液に用いる（ＮＨ_４）_３［ＲｈＣｌ_５（Ｈ_２Ｏ）］（０．００１質量％）は、粉末をそれぞれＫＣｌの２０質量％水溶液、ＮａＣｌの２０質量％水溶液に溶解し、４０℃で１２０分間加熱して調製した。
【０１９６】
４１℃、ｐＨ４．５に保たれた１液に、２液と３液の各々６７％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、０．１９μｍ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３３％の量を２分間にわたって加え、０．２１μｍ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。
【０１９７】
４液
水 １００ｍｌ
硝酸銀 ５０ｇ
【０１９８】
５液
水 １００ｍｌ
塩化ナトリウム ８．６ｇ
臭化カリウム １９．２ｇ
Ｋ_４［Ｆｅ（ＣＮ）_６］・３Ｈ_２Ｏ（黄血塩） ２０ｍｇ
【０１９９】
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、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２Ｌ除去した（第一水洗）。さらに２Ｌ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２Ｌ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６．０ｍｇ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。
【０２００】
最終的に臭化銀を５５ｍｏｌ％、沃化銀を０．０８ｍｏｌ％含む平均粒子サイズ０．２２μｍ、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。
【０２０１】
＜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。
【０２０２】
ＵＬ層塗布液
ゼラチン ０．８ｇ／ｍ^２
ポリエチルアクリレートラテックス ２６０ｍｇ／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
【０２０３】

クエン酸を用いて塗布液ｐＨを５．６に調整した。
【０２０４】

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。
【０２０６】

【０２０７】

【０２０８】
＜支持体上への塗布方法＞
両面に下塗層を施し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）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（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。
【０２０９】
＜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。
【０２１０】
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、ハロゲン化銀写真感光材料を作製した。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。
【０２１１】
＜試験＞
調製したハロゲン化銀写真感光材料を用いて実施例１，２と同様の試験を行ったところ、実施例１，２と同様に本発明の条件を満たすハロゲン化銀写真感光材料が良好な効果を示すことが確認された。なお、実技濃度の測定には下記の方法を用いた。
（実技濃度）
工業分野のフォトマスク用プロッタとして大日本スクリーン製造（株）製のＲＧ−７５００を使用して５０μｍの線を抽画し、実施例１の処理方法にしたがって処理した後の線巾が５０μｍになるように露光量を設定した時の濃度を測定して実技濃度とした。濃度の測定は、実施例１と同じ方法で行った。
【０２１２】
【発明の効果】
銀量を下げた本発明の白黒ハロゲン化銀写真感光材料を用いれば、イメージセッターに続いて自動現像機で処理する時に現像液の補充量が少なくても、ランニングでの網％変動を小さく抑えることができる。[0001]
BACKGROUND OF THE INVENTION
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black and white silver halide photographic light-sensitive material, and in particular, an ultrahigh-contrast silver halide photographic light-sensitive material processed using an image setter or a laser plotter and an automatic processor used for photolithography or industrial photomasks. About.
[0002]
[Prior art]
In the graphic arts field and the industrial field, an image forming system showing photographic characteristics of super high contrast (especially γ is 10 or more) in order to improve the reproduction of continuous tone images or line images by halftone images. is necessary.
On the other hand, silver halide photographic light-sensitive materials for photoengraving and industrial photomasks are increasingly processed by an automatic processor connected to a laser output device called an image setter or a laser plotter.
[0003]
There is a demand for an image forming system that can be developed with a processing solution having good storage stability and obtain ultra-high contrast photographic characteristics. The surface latent image type silver halide photographic light-sensitive material to which a specific acyl hydrazine compound is added is treated with a developer having a pH of 11.0 to 12.3 containing 0.15 mol / L or more of a sulfite preservative, so that γ is 10. A system for forming a super-high contrast negative image has been proposed. This new image forming system can be used with silver iodobromide and silver iodochlorobromide, whereas the conventional ultra-high contrast image forming system can only use silver chlorobromide with a high silver chloride content. There are features. In addition, the conventional lith developer can contain only a very small amount of a sulfite preservative, whereas it can contain a large amount of a sulfite preservative, so that it has a relatively good storage stability.
In this new image forming system, since the pH of the developer is high, the developer is easily affected by air oxidation, and the storage stability of the developer is not sufficient. For this reason, Patent Documents 8 and 9 describe highly active hydrazine compounds that achieve high contrast even with a developer having a pH of about 10.5.
[0004]
In recent years, it has been desired to further reduce the replenishment amount of the developing solution. However, it is conceivable to reduce the amount of silver in the photosensitive material as a method for reducing the processing load due to the low replenishment. However, when running for a long time in a low replenishment state, the amount of hydroquinone monosulfonate developing agent in which sulfite is added to the hydroquinone developing agent increases. As a result, there is a problem that the net% change becomes large, the image is crushed, and the commercial value is lost. The halftone dot mentioned here is a halftone dot percentage when the test step is output while changing the light amount at 175 lines / inch by the image setter.
[0005]
[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. 4,272,606
[Patent Document 7] US Pat. No. 4,311,781
[Patent Document 8] US Pat. No. 4,988,604
[Patent Document 9] US Pat. No. 4,994,346
[0006]
[Problems to be solved by the invention]
Accordingly, the problem to be solved by the present invention is that when a photosensitive material with a reduced amount of silver is used and processed with an automatic processor following an image setter or a laser plotter, even if the replenishment amount of the developer is small, the running can be performed. It is an object of the present invention to provide a black and white silver halide photographic light-sensitive material having a small net% variation.
[0007]
[Means for Solving the Problems]
As a result of intensive studies, the present inventor has found that the above problems can be solved by the present invention having the following configuration.
The present invention relates to a black-and-white silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers is a silver halide emulsion layer, and the hydrophilic When the colloidal layer contains at least one hydrazine derivative and the black and white silver halide photographic light-sensitive material is processed with a developer containing a hydroquinone developing agent, an equimolar amount of hydroquinone monosulfonate with the hydroquinone developing agent When processed with a developer containing a developing agent, the difference in net% is within 15%, and the slope of the characteristic curve giving optical density 0.1 and optical density 1.5 (optical density difference / logarithm of exposure amount) A black-and-white silver halide photographic light-sensitive material is provided, wherein γ which is a difference) is 10 or more.
In the black and white silver halide photographic light-sensitive material of the present invention, the hydrophilic colloid layer preferably contains 1 to 8 mole times the nucleation accelerator with respect to the hydrazine derivative. The content of hydrazine is 1.0 × 10^-4It is preferably at least mol / mol Ag. Further, it is preferable to have a gelatin layer between the emulsion layer and the support. The coated silver amount of the silver halide photographic material is 3.3 g / m.²Or less, preferably 3.0 g / m²The following is more preferable. Further, the black and white silver halide photographic light-sensitive material of the present invention preferably contains a benzotriazole compound.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The black and white silver halide photographic light-sensitive material of the present invention will be described in detail below. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
[0009]
The black and white silver halide photographic light-sensitive material of the present invention is processed with a developer containing a hydroquinone developing agent and when processed with a developer containing an equimolar amount of a hydroquinone monosulfonate developing agent. There is one feature in that the difference in the net% is within 15%.
In the present specification, “difference in mesh%” means the difference between the net% measured using the following developer 1 and the net% measured using the following developer 2. Net% is a value measured by the following procedure. In other words, using a black and white silver halide photographic light-sensitive material, an image setter RC5600V manufactured by Fuji Photo Film Co., Ltd. and an automatic processor AP-560, a test step is output while changing the light intensity at 175 lines / inch. Then, development is performed for 30 seconds at a development temperature of 35 ° C. using the developer 1 or the developer 2, and an LV value at which the halftone dot is 50% is obtained and set as halftone. Net% is measured using Macbeth TD904. The difference in mesh percentage is preferably within 15%, and more preferably within 10%.
Developer 1
600 ml of water
Potassium hydroxide 29g
Diethylenetriamine-pentaacetic acid 2g
Sodium metabisulfite 40g
40g potassium carbonate
Potassium bromide 3.2g
Hydroquinone 23g
4-hydroxymethyl-4-methyl-
0.4 g of 1-phenyl-3-pyrazolidone
Sodium erythorbate 3g
Diethylene glycol 20g
Water was added to 1 L and the pH was adjusted to 10.45.
Developer 2
This is the same formulation as Developer 1 except that the hydroquinone in the formulation of Developer 1 is changed to hydroquinone and an equimolar amount of potassium hydroquinone monosulfonate (47.7 g).
[0010]
The silver halide for the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention may have any composition, but preferably contains 20 to 90 mol% of silver bromide, particularly silver bromide. It is preferable to use silver chlorobromide or silver iodochlorobromide containing 20 to 90 mol% of chlorobenzene. A more preferable silver bromide content is 20 to 75 mol%. 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 uniform phase or a different surface layer. Moreover, you may have the localized layer from which a halogen composition differs in the inside or the surface of a particle | grain.
[0011]
The photographic emulsion used in the present invention is P.I. By Glafkides Chimie et Physique Photographic (published by Paul Montel, 1967), G. 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, any of an acidic method, a neutral method, etc. may be sufficient, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-side mixing method, a simultaneous mixing method, a combination thereof, etc. 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.
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. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, tetrasubstituted thiourea and the like. 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.
[0012]
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.
In order to make the grain size uniform, as described in British Patent No. 153516, Japanese Patent Publication Nos. 48-36890 and 52-16364, the addition rate of silver nitrate or alkali halide is described. The critical saturation can be adjusted using a method of changing the concentration of the aqueous solution as described in British Patent No. 4242445 and JP-A-55-158124. It is preferable to grow quickly in a range not exceeding.
[0013]
The silver halide emulsion used in the present invention may contain a metal belonging to Group VIII. In particular, in order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, or the like. In addition, for higher sensitivity, K₄[Fe (CN)₆] Or K₄[Ru (CN)₆], K₃[Cr (CN)₆It is effective to dope with a metal hexacyanide complex such as
[0014]
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.
[0015]
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. Preferable ligands include a halide ligand, a cyanide ligand, a cyan oxide ligand, a nitrosyl ligand, a thionitrosyl ligand, 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.
[0016]
[ReCl₆]^3-                [ReBr₆]^3-
[ReCl₅(NO)]^2-        [Re (NS) Br₅]^2-
[Re (NO) (CN)₅]^2-    [Re (O)₂(CN)₄]^3-
[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 (NO) (CN)₅]^2-
[Os (NS) Br₅]^2-        [Os (CN)₆]^4-
[Os (O)₂(CN)₄]^4-
[0017]
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. Examples of the iron compound used in the present invention include potassium hexacyanoferrate (II) and ferrous thiocyanate.
[0018]
The silver halide emulsion used in the present invention is preferably chemically sensitized. As a method of chemical sensitization, known methods such as sulfur sensitization method, selenium sensitization method, tellurium sensitization method and noble metal sensitization 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.
[0019]
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 tetrasubstituted 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.
[0020]
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.
[0021]
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, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211, U.S. Pat. Patent Nos. 1,121,496, 1,295,462, 1,396,696, Canadian Patent 800,958, Japanese Patent Laid-Open No. 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); Compounds described in The Chemistry of Organic Selenium and Tellunium Compounds, Vol 1 (1986), Vol 2 (1987), edited by S. Patai, The Chemistry of Organic Selenium and Tellurium Companies Can be used. In particular, compounds represented by general formulas (II), (III) and (IV) in JP-A-4-324855 are preferred.
[0022]
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.
[0023]
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 of the present invention by the method described in European Patent Publication No. EP 293917A.
It is preferable to use one to three types of silver halide emulsions in the silver halide photographic light-sensitive material used in the present invention. When two or more kinds are used in combination, those having different average particle sizes, those having different halogen compositions, those containing different metal complexes, different types, those having different crystal habits, those having different conditions for chemical sensitization, It is preferable to use those having different sensitivities. 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.
The silver coating amount in the silver halide photographic light-sensitive material of the present invention is 3.3 g / m.²Or less, preferably 3.0 g / m²The following is more preferable.
[0024]
The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to a relatively long wavelength blue light, green light, red light or infrared light with a sensitizing dye in accordance with the use of the light-sensitive material. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a hoholor cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, or the like can be used.
Useful sensitizing dyes used in the present invention are described in, for example, the literature described or cited in RESEARCH DISCLOSURE Item 17643IV-A (December 1978, p.23) and Item 18341X (August 1979, p.437). Has been.
In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light sources of various scanners, imagesetters and plate-making cameras can be advantageously selected.
[0025]
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, U.S. Pat. No. 2,161,331, Examples 1 to Example 14, compounds, West German Patent No. Compounds 1 to 7 described in the specification of 936,071; B) Compounds of I-1 to I-38 described in JP 54-18726 A for helium-neon laser and red laser diode light sources Compounds of I-1 to I-35 described in JP-A-6-75322 and compounds of I-1 to I-34 described in JP-A-7-287338, Japanese Patent No. 28 Japanese Patent Publication No. 55-39818 for compounds 2-1 to 2-14, 3- (1) to 3- (14), 4-1 to 4-6, and LED light sources described in Japanese Patent No. 2138 Dyes 1 to 20 described in the publication, 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, Japanese Patent Laid-Open No. 2822138 discloses compounds 2-1 to 2-14, 3- (1) to 3- (14), 4-1 to 4-6, and D) semiconductor laser light source. I-1 to I-12 compounds described in Japanese Patent Application Laid-Open No. 59-191032, I-1 to I-22 compounds described in Japanese Patent Application Laid-Open No. 60-80841, and I described in Japanese Patent Application Laid-Open No. 4-335342. -1 to I-29 and JP-A 59-1922 The compound of I-1 to I-18 described in No. 2 and E) The tungsten and xenon light sources of the plate-making camera are represented by the general formula [I] described in JP-A-55-45015 ( 1) to (19) compounds, compounds of 4-A to 4-S, compounds of 5-A to 5-Q, compounds of 6-A to 6-T, and compounds described in JP-A-6-242547 The compounds I-1 to I-97 and the like described in Kaihei 9-160185 are advantageously selected, but the sensitizing dye that can be used in the present invention is not limited thereto.
[0026]
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.
[0027]
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.
[0028]
The time when the sensitizing dye used in the present invention is added to the silver halide emulsion of the present invention may be during any step of emulsion preparation that has been found useful. 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 specifications such as JP-184142 and JP-A-60-196749, the silver halide grain forming step or / and the time before desalting, during the desalting step and / or after desalting. As disclosed in the specification of Japanese Patent Application Laid-Open No. 58-113920, the emulsion before the start of chemical ripening, just before chemical ripening or during the process, after chemical ripening and before coating, It may be added in the process at any time before it is applied. Further, as disclosed in US Pat. No. 4,225,666, JP-A-58-7629, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle formation step. 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 add and change the kind of.
[0029]
The addition amount of the sensitizing dye of the present invention varies depending on the shape, size, halogen composition, chemical sensitization method and degree of silver halide grains, type of antifoggant, etc.^-6~ 8x10^-3It can be used in mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, the surface area of the silver halide grain is 1 m.²Per 2 × 10^-7~ 3.5 × 10^-6mol addition amount is preferable, 6.5 × 10^-7~ 2.0 × 10^-6The addition amount of mol is more preferable.
[0030]
The support used in the present invention is, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, polyester film such as cellulose nitrate, for example, polyethylene terephthalate, JP-A-7-234478, and US Patent A support comprising a styrenic polymer having a syndiotactic structure described in US Pat. No. 5,558,979, JP-A No. 64-538, US Pat. No. 4,645,731, The support body which coat | covered the polyester film as described in 4,933,267 specification and 4,954,430 specification with the vinylidene chloride copolymer can be mentioned. These supports are appropriately selected according to the intended use of the silver halide photographic material.
[0031]
As the silver halide emulsion layer and other hydrophilic colloid layer binder of the present invention, gelatin is preferably used, but polymers described in paragraph [0025] of JP-A-10-268464 can also be used. The coating amount of the binder is 3 g / m for the total hydrophilic colloid layer on the side having the silver halide emulsion layer.²(Preferably 1.0 to 3.0 g / m²) And the total hydrophilic colloid layer on the side having the silver halide emulsion layer and the total hydrophilic colloid layer on the opposite side have a total binder amount of 7.0 g / m²Or less, preferably 2.0 to 7.0 g / m²It is.
[0032]
In the present invention, for the purpose of controlling the surface roughness of the outermost layer surface of the silver halide light-sensitive material, fine particles of inorganic and / or organic polymer (hereinafter referred to as matting agent) are preferably used in the hydrophilic colloid layer. Can be used. The surface roughness of the surface of the light-sensitive material having the silver halide emulsion layer and the surface of the outermost layer opposite to the emulsion layer should be controlled by varying the average grain size and addition amount of the matting agent. Can do. The layer containing the matting agent may be any layer constituting the light-sensitive material, but the side having the silver halide emulsion layer is preferably contained in a layer far from the support in order to prevent pinholes. The outermost layer is preferred.
[0033]
The matting agent used in the present invention may be any solid particles that do not adversely affect photographic characteristics. Specific examples include those described in paragraph numbers [0009] to [0013] of JP-A No. 10-268464.
The average particle size of the matting agent preferable in the present invention is 20 μm or less, and particularly in the range of 1 to 10 μm. In the present invention, a preferable amount of matting agent is 5 to 400 mg / m.², Especially 10-200 mg / m²Range.
The surface roughness of the light-sensitive material of the present invention is such that at least one of the surface having an emulsion layer and the surface of the outermost layer on the opposite side, preferably both have Beck smoothness of 4000 seconds or less, more preferably from 10 seconds to 4000. Seconds. The Beck smoothness can be easily obtained by Japanese Industrial Standard (JIS) P8119 and TAPPI standard method T479.
[0034]
In the present invention, sinking of the matting agent at the time of coating and drying of the silver halide photosensitive material, or pressure increase / decrease in handling during automatic conveyance / exposure / development, curl balance, scratch resistance improvement, adhesion resistance improvement, etc. For the purpose, colloidal inorganic grains can be used for silver halide emulsion layers, intermediate layers, protective layers, back layers, back protective layers and the like. Preferred colloidal inorganic particles include elongated silica particles described in paragraphs [0008] and [0014] of JP-A No. 10-268464, colloidal silica, and pearl like (pearl necklace shape) manufactured by Nissan Chemical Industries, Ltd. ) Colloidal silica: “Snowtex-PS” and the like.
[0035]
The amount of the colloidal inorganic particles used in the present invention is preferably 0.01 to 2.0 by dry mass ratio with respect to the binder (eg, gelatin) of the layer to be added, More preferably, it is 0.6.
[0036]
In the present invention, it is preferable to use a polyhydroxybenzene compound described in JP-A-3-39948, page 10, lower right line 11 to page 12, lower left line 5, for the purpose of improving pressure increase / decrease. . Specific examples include compounds (III) -1 to 25 described in the publication.
[0037]
In the present invention, a polymer latex can be used for the purpose of improving brittleness, dimensional stability, pressure fluctuation, and the like. As the polymer latex, U.S. Pat. Nos. 2,763,652, 2,852,382, JP-A-64-538, 62-115152, JP-A-5-66512. No. 5-80449, JP-B-60-15935, JP-B-6-64058, JP-A-5-45014, etc., polymer latex composed of various monomers such as alkyl acrylate and alkyl methacrylate, A monomer having an active methylene group described in JP-B Nos. 45-5819, 46-22507, JP-A-50-73625, JP-A-7-152112, JP-A-8-137060, and the like; Examples thereof include polymer latexes copolymerized with monomers such as alkyl acrylate. Particularly preferably, a repeating unit composed of an ethylenically unsaturated monomer containing an active methylene group in the shell part described in JP-A-8-248548, JP-A-8-208767, JP-A-8-220669 and the like is used. It is a polymer latex having a core / shell structure. The core / shell structure polymer latex having an active methylene group in the shell portion does not decrease the wet film strength of the photographic photosensitive material, and is brittle, dimensional stability, difficulty in adhesion of photosensitive materials, etc. This improves the properties of the latex and improves the shear stability of the latex itself.
The amount of the polymer latex used is preferably 0.01 to 4.0, more preferably 0.1 to 2.0, in terms of dry mass ratio with respect to the binder (eg, gelatin) of the layer to be added. preferable.
[0038]
In the present invention, in order to lower the pH of the coating film for the purpose of improving the storage stability of the silver halide light-sensitive material and the pressure increase / decrease, etc., JP-A-7-104413, page 14, left line 1, to page right 30 It is preferable to use the acidic polymer latex described in the row. Specifically, compounds II-1) to II-9) described on page 15 of the same gazette, and acids described in JP-A-2-103536, page 18, lower right 6th line to page 19, upper left first line. The compound which has group can be mentioned.
The pH of the coating film on the side having the silver halide emulsion layer is preferably 6-4.
[0039]
In the present invention, at least one of the constituent layers of the silver halide photosensitive material is 10 in an atmosphere having a surface resistivity of 25 ° C. and a relative humidity of 25%.¹²It can have a conductive layer of Ω or less.
Examples of the conductive material used in the present invention include those described in JP-A-2-18542, page 2, lower left line 13 to page 3, upper right line 7, line 7, specifically, Metal oxides described in page 2, lower right line 2 to page lower right line 10, and conductive polymer compounds of compounds P-1 to P-7 described in the publication, US Pat. No. 5,575, No. 957, paragraphs [0034] to [0043] of JP-A-10-142738, paragraphs [0013] to [0019] of JP-A-11-223901, and the like are used. be able to.
[0040]
In the present invention, in addition to the conductive material, JP-A-2-18542, page 4, upper right 2nd line, page 4 lower-right lower 3rd line, JP-A-3-39948, page 12, lower left 6 By using together the fluorine-containing surfactant described in the lower right line on page 13, page 13 of the same publication, even better antistatic properties can be obtained.
[0041]
In the present invention, the silver halide emulsion layer or other hydrophilic colloid layer is coated with coating aids, additive dispersing / solubilizing agents, lubricity improvement, adhesion prevention and photographic property improvement (for example, development acceleration, high contrast). , Sensitization, storage stability) and the like, various surfactants can be used. For example, the surfactants described in JP-A-2-12236, page 9, upper right 7th line to the lower-right third line, JP-A-2-103536, page 18, lower-left 4th line, page 7 lower-left 7 PEG-based surfactants described in the row, specifically, compounds VI-1 to VI-15 described in the same publication, JP-A-2-18542, page 4, upper right 2nd page to page 4 Examples thereof include the fluorine-containing surfactants described in the third line from the lower right and from the lower left line of page 12 of JP-A-3-39948 to the lower right line of page 13 of the same publication.
[0042]
In the present invention, various slipping agents can be used for the purpose of improving the transportability, scratch resistance, pressure increase / decrease sensitivity characteristics, etc. of the silver halide photosensitive material in an automatic transport machine. For example, the lubricants described in JP-A-2-103536, page 19, upper left 15 line to page 19, upper right line 15, JP-A-4-214551, paragraph numbers [0006] to [0031] can be mentioned. it can.
[0043]
In the present invention, compounds described in JP-A-2-103536, page 19, upper left line 12 to page 19, upper right line 15 can be contained as a plasticizer for the coating film of the silver halide photosensitive material. .
[0044]
In the present invention, the crosslinking agent for the hydrophilic binder is disclosed in JP-A-2-103536, page 18, upper right line 5 to page 17, upper right line, JP-A-5-297508, paragraph numbers [0008] to [0011]. Can be used. The swelling ratio of the hydrophilic colloid layer including the emulsion layer and protective layer of the silver halide photographic material of the present invention is preferably in the range of 50 to 200%, more preferably in the range of 70 to 180%. The swelling ratio of the hydrophilic colloid layer was determined by measuring the thickness (d0) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic light-sensitive material. And then swelled thickness (Δd) is measured, and the swelling ratio (%) = Δd ÷ d0 × 100 is calculated.
[0045]
In the present invention, drying at the time of drying after coating of the silver halide light-sensitive material, environment, processing, heat treatment, etc. when wound into a roll after drying are described in paragraph numbers [0026] to [0026] of JP-A-10-268464. [0032] The method described in [0032] is preferable.
[0046]
In the present invention, it is preferable that the photosensitive material after coating is subjected to heat treatment at any time from coating to development. The heat treatment may be performed immediately after the application or may be performed after a certain period of time has elapsed, but it is preferable to start the heat treatment within a short period of time, for example, within one day. The heat treatment is mainly for promoting the hardening reaction to obtain a film strength that can withstand the development processing. The heat treatment conditions are appropriately determined depending on the type of hardener, the amount added, the film pH, the required film strength, etc. Although it must be determined, it is preferably 30 to 60 ° C, more preferably 35 to 50 ° C. The period of the heat treatment is preferably 30 minutes to 10 days.
[0047]
The silver halide photographic light-sensitive material of the present invention contains a hydrazine compound as a nucleating agent. In particular, it is preferable to contain at least one hydrazine derivative represented by the following general formula (D).
Formula (D)
[Chemical 1]

[0048]
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.
[0049]
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.
[0050]
R²⁰The group represented by may be substituted. Typical examples of the substituent include a halogen atom (fluorine atom, chloro 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 , Including groups that repeatedly contain Ruoxy 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, sulfonamido 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) Group, (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 Examples thereof include a group containing an ester structure.
These substituents may be further substituted with these substituents.
[0051]
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.
[0052]
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.
[0053]
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 preferred, and those containing a benzene ring are particularly preferred. 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. 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, a piperidino group (N-substituted), a piperazino group, an imidazolyl group, an indazolyl group (such as 4-nitroindazolyl group), a pyrazolyl group, a triazolyl group, a 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.
[0054]
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.
[0055]
R¹⁰The group represented by may be substituted, and preferred substituents are R²⁰Examples of the substituents in FIG.
[0056]
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.
[0057]
The hydrazine derivative represented by the general formula (D) may incorporate an adsorptive group that adsorbs to silver halide. Examples of such adsorbing groups include alkylthio groups, arylthio groups, thiourea groups, thioamide groups, mercaptoheterocyclic groups, triazole groups, and the like, U.S. Pat. No. 202031, No. 59-201045, No. 59-201046, No. 59-201047, No. 59-201048, No. 59-201049, JP-A-61-170733, Examples thereof include groups described in JP-A Nos. 61-270744, 62-948, 63-234244, 63-234245, and 63-234246. 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.
[0058]
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.
[0059]
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 / 324252, 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.
[0060]
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, an (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, carboxy group / -COOH, sulfo group / -SO₃H, 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 contained. Examples of these groups include, for example, 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. 4,006,032 and JP-A No. 11-7093.
[0061]
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.
[0062]
Next, particularly preferred hydrazine derivatives in the present invention will be described.
R²⁰Is particularly preferably a substituted phenyl group, and the substituent is an alkyl group, (alkyl, aryl or heterocyclic) oxy group, (alkyl, aryl or heterocyclic) thio group, sulfonamido group, acylamino group, ureido group, carbamoyl group. , A thioureido group, an isothioureido group, a sulfamoylamino group, an N-acylsulfamoylamino group and the like, preferably an alkyl group, an (alkyl, aryl or heterocyclic) oxy group, an (alkyl, aryl or heterocyclic) thio group An acylamino group, a sulfonamide group, and a ureido group are more preferable, and an alkyl group and a sulfonamide group are most preferable.
[0063]
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 an alkyl group or a benzenesulfonamide group, and as a substituent on the benzene ring of the benzenesulfonamide group or a substituent on the alkyl group, either directly or indirectly, This is the case with a group.
[0064]
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.
[0065]
In general formula (D), G¹⁰Is preferably a —CO— group or a —COCO— group, particularly preferably a —CO— group.
[0066]
Next, specific examples of the compound represented by the general formula (D) are shown below. However, the present invention is not limited to the following compounds.
[0067]
[Chemical 2]

[0068]
[Chemical 3]

[0069]
[Formula 4]

[0070]
[Chemical formula 5]

[0071]
[Chemical 6]

[0072]
[Chemical 7]

[0073]
[Chemical 8]

[0074]
[Chemical 9]

[0075]
Embedded image

[0076]
Embedded image

[0077]
Embedded image

[0078]
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 patents.
[0079]
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; 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, and in particular, the general formula (A), the general formula (B), C), compounds represented by general formula (D), general formula (E), and general formula (F), specifically, compounds N-1 to N-30 described in the publication; Compounds represented by the general formula (1) described in Japanese Patent Publication No. JP-A-10-232456; specifically, the compounds represented by the general formula (1) described in the Japanese Patent Publication; Specifically, compounds N-I to N-XVIII described in the publication, compounds represented by the general formula (I) described in JP-A-11-190887, specifically Are the compounds NI to N-XI described in the publication, JP-A-2001-109094 A compound represented by the general formula (I) described in the above, specifically, compounds II to X described in the publication, and a compound represented by the general formula (I) described in JP-A No. 2001-100351 Specifically, compounds II to XV described in the same publication: International Publication No. WO95 / 32452, International Publication No. WO95 / 32453, JP-A-9-179229, JP-A-9-235264, JP-A-9 JP-A-235265, JP-A-9-235266, JP-A-9-235267, JP-A-9-319019, JP-A-9-319020, JP-A-10-130275, JP-A-11-7093. No. 6, JP-A-6-332096, JP-A-7-209789, JP-A-8-6193, JP-A-8-248549, JP-A-8-24. No. 550, JP-A-8-262609, JP-A-8-314044, JP-A-8-328184, JP-A-9-80667, JP-A-9-127632, JP-A-9-146208 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 JP-A-8-36235, JP-A-8-272202, JP-A-9-22083, JP-A-9-22084 Distribution, JP 9-54381 and JP Hei 10-175946 discloses, can be mentioned hydrazine derivative according.
[0080]
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, a hydrazine derivative 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.
[0081]
In the present invention, the hydrazine nucleating agent may be added to the silver halide emulsion layer on the side of the silver halide emulsion layer relative to the support, or any other hydrophilic colloid layer. It is preferably added to the silver emulsion layer or the hydrophilic colloid layer adjacent thereto. Two or more hydrazine nucleating agents can be used in combination.
In the present invention, the amount of nucleating agent added is 1 × 10 to 1 mol of silver halide.^-4Or more, preferably 1 × 10^-4~ 1x10^-2Mole is more preferred, 1 × 10^-4~ 5x10^-3Mole is most preferred.
[0082]
The addition amount of the hydrazine of the present invention needs to have a net% change of 15% or less and a γ value of 10 or more when combined with the treatment method of the present invention.
[0083]
In the present invention, an amine derivative, onium salt, disulfide derivative or hydroxymethyl derivative may be incorporated as a nucleation accelerator in the photosensitive material. Examples of the nucleation accelerator used in the present invention are the compounds described in JP-A-7-77783, page 48, lines 2 to 37, specifically, compound A-1 described on pages 49 to 58). -A-73); compounds represented by (Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 23) described in JP-A-7-84331, specifically, pages 6-8 Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, Na-1 to Na described on pages 16 to 20 of the same publication -22 compound and Nb-1 to Nb-12 compound; general formula (1), general formula (2), general formula (3), general formula (4), general formula described in JP-A-8-272023 Compounds represented by formula (5), general formula (6) and general formula (7), specifically described in the same specification 1-1 to 1-19, 2-1 to 2-22, 3-1 to 3-36, 4-1 to 4-5, 5-1 to 5-41 6-1 to 6-58, and 7-1 to 7-38; the structures described in JP-A-9-297377, p55, column 108, line 8 to p69, column 136, line 44. Mention may be made of nuclear promoters.
[0084]
Specific examples of the nucleation promoter used in the present invention are shown below. However, the nucleation accelerator that can be used in the present invention is not limited to the following compounds.
[0085]
Embedded image

[0086]
Embedded image

[0087]
The nucleation accelerator of the present invention 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, etc. It can be dissolved 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 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.
[0088]
The nucleation accelerator of the present invention may be added to the silver halide emulsion layer on the side of the silver halide emulsion layer with respect to the support or any other hydrophilic colloid layer. It is preferable to add to the hydrophilic colloid layer adjacent to the emulsion layer.
The addition amount (mol / mol Ag) of the nucleation accelerator of the present invention is preferably 1 to 8 times, more preferably 1 to 6 times the addition amount (mol / mol Ag) of the nucleation agent. Two or more kinds of nucleation accelerators can be used in combination.
[0089]
Various additives used in the light-sensitive material of the present invention are not particularly limited, and for example, those described in the following locations can be preferably used.
That is, the polyhydroxybenzene compound described in JP-A-3-39948, page 10, lower right line 11 to page 12, page 12, lower left line 5, specifically, compound (III)- Compounds of 1 to 25; compounds represented by the general formula (I) described in JP-A No. 1-181832 and having substantially no absorption maximum in the visible range, specifically, compounds described in the same publication Compounds of I-1 to I-26; antifoggants described in JP-A-2-103536, page 17, lower right line 19 to page 18, upper-right line 4: JP-A-2-103536, page 18 Polymer latex described in the lower left line on page 12 to the lower left line on page 20; a polymer latex having an active methylene group represented by formula (I) described in JP-A-9-179228, specifically, Compound described in the specification I-1 to I-16; polymer latex having a core / shell structure described in JP-A-9-179228, specifically, compounds P-1 to P-55 described in the same specification; No. 104413, page 14, left line 1 to right line 30; specifically, compounds II-1) to II-9) described on page 15 of the same publication; No. 2-103536, page 19, upper left line 15 to page 19, upper right line 15, matting agent, slip agent, plasticizer; JP-A-2-103536, page 18, upper right line, line 5 Hardener described in the upper right 17th line; JP-A-2-103536, page 18, lower right 6th line to page 19, upper left 1st line compound; JP-A-2-18542 From the 13th line on the lower left of the second page of the gazette to the upper right side of the third page of the gazette. Conductive substances described in the eyes, specifically, metal oxides described in the second lower right line on page 2 to the lower right tenth line of the same publication, and compounds P-1 to P described in the same publication A conductive polymer compound of -7; a water-soluble dye as described in JP-A-2-103536, page 17, lower right, line 1 to upper right, line 18; JP-A-7-179243, general formula ( FA), general formula (FA1), general formula (FA2), solid disperse dyes represented by general formula (FA3), specifically compounds F1 to F34 described in the publication, and JP-A-7-152112 (II-2) to (II-24), (III-5) to (III-18) described in JP-A-7-152112, (IV-2) to (IV) described in JP-A-7-152112 -7). Solid disperse dyes described in JP-A-2-294638 and JP-A-5-11382; Surfactants described in JP-A-2-12236, page 9, upper right 7th line to page 3 lower right line . JP-A-2-103536, page 18, lower left line, line 4 to page 7, lower left line, PEG-based surfactant; JP-A-3-39948, page 12, lower left line, line 6, page 13 The fluorine-containing surfactant described in the lower right 5th line, specifically, compounds I-1 to I-15 described in the same publication; by being oxidized as described in JP-A-5-274816 A redox compound capable of releasing a development inhibitor, preferably a redox compound represented by general formula (R-1), general formula (R-2), or general formula (R-3) described in the publication; Can be mentioned compounds R-1 to R-68 described in the same publication; binders described in the first lower right line to the 20th line of page 3 of JP-A-2-18542.
[0090]
In the development processing method of the present invention, the development processing is preferably performed in the presence of a benzotriazole compound. The benzotriazole-based compound may be added to the light-sensitive material or may be added to the developer. When added to the light-sensitive material, it may be added to the silver halide emulsion layer side or the opposite side of the silver halide emulsion layer across the support. The silver halide emulsion layer side is preferable.
[0091]
The benzotriazole-based compound used in the present invention may have any structure, but preferably has the structure shown below.
(1) 5,6-dimethylbenzotriazole
(2) 5-Butylbenzotriazole
(3) 5-methylbenzotriazole
(4) 5-chlorobenzotriazole
(5) 5-Bromobenzotriazole
(6) 5,6-dichlorobenzotriazole
(7) 4,6-dichlorobenzotriazole
(8) 5-Nitrobenzotriazole
(9) 4-Nitro-6-chlorobenzotriazole
(10) 4,5,6-trichlorobenzotriazole
(11) 5-Carboxybenzotriazole
(12) 5-sulfobenzotriazole
(13) 5-methoxycarbonylbenzotriazole
(14) 5-Aminobenzotriazole
(15) 5-Butoxybenzotriazole
(16) 5-Ureidobenzotriazole
(17) Benzotriazole
[0092]
Particularly preferred among the benzotriazole compounds of the present invention are benzotriazole and 5-methylbenzotriazole.
In the case of a silver halide photographic material, the amount of the benzotriazole compound of the present invention is 1 × 10 with respect to 1 mol of silver halide.^-4~ 1x10^-1mol is preferred, 1 × 10^-3~ 7 × 10^-2Mol is particularly preferred.
7.5 × 10 when added to developer^-5~ 7.5 × 10^-3mol / L is preferred, 7.5 × 10^-5~ 5.0 × 10^-3Particularly preferred is mol / L.
Two or more kinds of benzotriazole compounds may be used in combination, or a silver halide photographic material and developer may be used in combination.
[0093]
The processing agents and processing methods such as developer and fixing solution in 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.
[0094]
For the development processing of the present invention, any of the known methods can be used, and known processing solutions can be used.
[0095]
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.
[0096]
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.
[0097]
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.
[0098]
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.
[0099]
The developer used for processing the light-sensitive material in the present invention may contain commonly used additives (for example, developing agents, alkali agents, pH buffering agents, preservatives, chelating agents, etc.). Although these specific examples are shown below, this invention is not limited to these.
Examples of the buffer used in the developing solution for developing the light-sensitive material in the present invention include carbonates, boric acid described in JP-A No. 62-186259, and sugars described in JP-A No. 60-93433. For example, saccharose), oximes (for example, acetoxime), phenols (for example, 5-sulfosalicylic acid), triphosphate (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.
[0100]
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, with respect to the dihydroxybenzene-based developing agent. When using an ascorbic acid derivative as a preservative, it is preferable that the developer does not contain a boron compound.
[0101]
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, 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 and the like can be mentioned. 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.
[0102]
Furthermore, various organic and inorganic chelating agents can be used alone or in combination in the developer of 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.
[0103]
Examples of aminopolycarboxylic acids include iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyl triacetic 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.
[0104]
Examples of the organic phosphonic acid include hydroxyalkylidene-diphosphonic acids described in, for example, US Pat. Nos. 3,214,454, 3,794,591, and German Patent 2,227,369. Examples include compounds described in Research Disclosure Vol. 181, Item 18170 (May 1979).
Examples of the 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 be mentioned.
[0105]
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.
[0106]
Of these chelating agents, diethylenetriamines are particularly preferred. Among diethylenetriamines, diethylenetriaminepentaacetic acid and its metal salt are more preferable.
[0107]
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.
[0108]
Further, as silver stain preventing agents in the developer, for example, JP-A-56-24347, JP-B-56-46585, JP-B-62-2849, JP-A-4-362294 and 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), Pyrimidines (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), pyridine (for example, 2-mercaptopyridine, 2,6-dimer) Ptopyridine, 3,5-dimercaptopyridine, 2,4,6-trimercaptopyridine, compounds described in JP-A-7-24887, etc., and pyrazines (for example, 2-mercaptopyrazine, 2,6-dimercaptopyrazine) 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine, etc.) and the same pyridazine (for example, 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimercaptopyridazine, 3, 4, 6-trimercaptopyridazine, etc.), compounds described in JP-A-7-175177, polyoxyalkylphosphonic acid esters described in US Pat. No. 5,457,011, and the like can be used. 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.
[0109]
The preferred pH of the developer is 9.0 to 11.0, particularly preferably 9.2 to 11.0, and more preferably 9.5 to 11.0. As the alkali agent used for pH adjustment, a normal water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.
[0110]
The pH increase when 0.1 mol of sodium hydroxide is added to 1 L of the developer to be used is preferably 0.4 or more, more preferably 0.4 to 1.0.
[0111]
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 in by the photosensitive material, so that the potassium ion concentration in the fixing solution is reduced. It becomes high and is not preferable. From the above, the molar ratio of potassium ion to sodium ion 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.
[0112]
Developer replenishment amount is 1m of photosensitive material²323 ml or less, preferably 323-30 ml, most preferably 323-120 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.
[0113]
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 changed as appropriate, but is generally about 0.7 to about 3.0 mol / L.
[0114]
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.
[0115]
As a fixing treatment agent, a preservative (eg, sulfite, bisulfite, metabisulfite, etc. is 0.015 mol / L or more, preferably 0.02 mol / L to 0.3 mol / L), a 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, nitrilotri Acid, derivatives thereof, salts thereof, saccharides and the like can be contained in an amount of 0.001 mol / L to 0.5 mol / L, preferably 0.005 mol / L to 0.3 mol / L). From this point, it is better not to contain a boron compound.
[0116]
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, 1-159645 A mercapto compound described in JP-A-3-101728 and a mesoionic compound described in JP-A-4-170539, and a thiocyanate can be included.
[0117]
The pH of the fixing solution in the present invention is preferably 4.0 or more, more preferably 4.5 to 6.0. The fixing solution is mixed with a developing solution by processing to increase the pH. In this case, it is 6.0 or less, preferably 5.7 or less for a hard-fixing solution, and 7.0 or less for an uncured fixing solution. Is 6.7 or less.
[0118]
The replenishment amount of the fixing solution is 1 m of photosensitive material.²500 ml or less, preferably 390 ml or less, more preferably 320 to 80 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.
[0119]
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.
[0120]
When the developing and fixing treatment agent in the present invention is a liquid agent, it is preferably stored in a packaging material having a 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.
[0121]
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, but from the viewpoint of storage stability and the like, the solid processing agent is preferable. The following describes the solid processing agent.
As the solid preparation in the present invention, known forms (powder, granules, granules, lumps, tablets, compactors, briquettes, plates, rods, pastes, 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.
[0122]
Known coating materials and granulation aids can be used, but polyvinyl pyrrolidone, polyethylene glycol, polystyrene sulfonic acid, and vinyl compounds are preferred. In addition, JP-A-5-45805, column 2, line 48 to column 3, line 13 can be referred to.
[0123]
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-61-259921, JP-A-4-16841, JP-A-4-78848, and JP-A-5-93991.
[0124]
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.
[0125]
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, 5-2029898, 5-224361, 6 Nos. 138604, 6-138605, and 8-286329 can be referred to.
[0126]
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.
[0127]
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.
[0128]
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.
[0129]
The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, a dissolution having a dissolution part as described in JP-A-9-80718 and a part for stocking the finished liquid. 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 photosensitive material by an automatic developing machine incorporating a dissolution tank, etc., but any other known method can be used. it can. 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.
[0130]
The light-sensitive material that has been developed and fixed is then washed or stabilized (hereinafter, unless otherwise specified, referred to as washing including stabilization, and the liquid used for these is referred to as water or washing water). The water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing solution. These replenishment amounts are generally 1 m of photosensitive material.²It is about 17L to about 8L per, but can be carried out with a replenishment amount below that. 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. Various oxidants (such as ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) can be used to reduce pollution load, which is a problem when washing with small amounts of water, and to prevent scale contamination. Addition and filter filtration may be combined.
[0131]
As a method for reducing the replenishment amount of washing with water, a multi-stage countercurrent system (for example, 2 steps, 3 steps, etc.) has been known for a long time.²200 to 50 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).
[0132]
Furthermore, a water scale preventing means may be applied to the water washing step by the method of the present invention. 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 scale prevention means may be performed according to the processing of the light-sensitive material, may be performed at regular intervals regardless of the usage status, or may be performed only during a period when the processing is not performed, such as at night. 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.
[0133]
As a water-saving water scale prevention device, Fuji Photo Film Co., Ltd. apparatus AC-1000 and Fuji Photo Film Co., Ltd. AB-5 may be used, and the method of Unexamined-Japanese-Patent No. 11-231485 may be used.
There are no particular limitations on the antifungal agent, and known ones can be used. In addition to the aforementioned oxidizing agents, there are chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxide (eg 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.
[0134]
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 No. 63-163456 may be installed in a water washing system in order to prevent contamination with a dye eluted from the photosensitive material.
[0135]
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 an oxidizing agent, 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.
[0136]
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 light-sensitive material. As needed for 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 Agents can also be added.
[0137]
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.
[0138]
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. 5,349,560.
[0139]
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, as a roller-conveying type automatic developing machine, Mention. This automatic machine is composed of four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stop step), but it is most preferable to follow these four steps. Further, a rinsing bath (washing tank) may be provided between the developing and fixing and / or between the fixing water washings.
[0140]
In the development processing of the present invention, 25 to 160 seconds are preferable from the start of processing to after drying (dry to dry), development and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each solution is 25 to 50. ° C is preferred, and 30 to 40 ° C is preferred. The washing temperature and time are preferably 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, the photosensitive material that has been developed, fixed, and washed 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.
[0141]
Any combination of the image setter and the automatic processor used in the present invention may be used as long as there is no problem in transportability. As an image setter, F9000 manufactured by Fuji Photo Film Co., Ltd., Lux Setter RC-5600V, Image Setter FT-R5055 manufactured by Dainippon Screen Co., Ltd., Select Set 5000, Avantla 25, or Accuset manufactured by Agfa Gebalt Co., Ltd. 1000, Dreb 450 or Dreb 800 manufactured by Cytex Co., Ltd., Rhino 630 manufactured by Heidel Co., Ltd., Quasar, Hercules Elite, or Signal Setter, or Laxel F-9000, or Panther Pro 62 manufactured by Prepress Co., Ltd. Any one of these may be used.
As a photomask plotter for the industrial field (PCB, PWB) used in the present invention, RG-7000, RG-7500, RG-4000, RG-4500, RG-8000, Orbotech made by Dainippon Screen Mfg. Co., Ltd. LP-5008, LP-7008, RP208NT, RP212NT, RP308NT, RP-312NT, RP508NT, RP512NT, RP512NT, LPP3655, LPP3777, LPP3690, etc. manufactured by Asahi Optical Industry Co., Ltd. are available.
[0142]
【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.
[0143]
Example 1
[Preparation of coating solution]
<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
2 liquids
300 ml of water
150 g silver nitrate
3 liquids
300 ml of water
Sodium chloride 38g
Potassium bromide 32g
Hexachloroiridium (III) potassium 5ml
(0.005 mass%, 20 mass% aqueous solution of KCl)
7ml ammonium hexachlororhodate
(0.001 mass%, 20 mass% NaCl aqueous solution)
[0144]
Potassium hexachloroiridium (III) (0.005 mass%, 20 mass% aqueous solution of KCl) and ammonium hexachlororhodate (0.001 mass%, 20 mass% aqueous solution of NaCl) used in the three liquids were respectively mixed with KCl. And dissolved in a 20% by weight aqueous solution of NaCl and a 20% by weight aqueous solution of NaCl and heated at 40 ° C. for 120 minutes.
[0145]
To 1 liquid maintained at 38 ° C. and pH 4.5, 90% of the 2 and 3 liquids were simultaneously added over 20 minutes while stirring to form 0.16 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 added over 2 minutes to grow to 0.21 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete grain formation.
[0146]
4 liquids
100ml water
Silver nitrate 50g
5 liquids
100ml water
Sodium chloride 13g
Potassium bromide 11g
Yellow blood salt 50mg
[0147]
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. To the emulsion after washing with water and desalting, 45 g of gelatin was added to adjust the pH to 5.6 and pAg 7.5. Chemical sensitization was performed to obtain an optimum sensitivity at 0 ° C., 100 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene was used as a stabilizer, and Proxel (trade name, ICI Co. , Ltd.) 100 mg was added.
[0148]
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 0.22 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 × 10³kg / m³Viscosity = 50 mPa · s.
[0149]
Embedded image

[0150]
<Emulsion layer coating solution>
To emulsion A, sensitizing dye (SD-1) 5.7 × 10^-4Mol / mol Ag was added to perform spectral sensitization. Furthermore KBr3.4 × 10^-4mol / mol Ag, Compound (Cpd-1) 2.0 × 10^-4mol / mol Ag, Compound (Cpd-2) 2.0 × 10^-4mol / mol Ag, Compound (Cpd-3) 8.0 × 10^-4Mol / mol Ag was added and mixed well. Then 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 1.2 × 10^-4mol / molAg, Hydroquinone 1.2 × 10^-2mol / molAg, 5-methylbenzotriazole 8 × 10^-4mol / molAg, citric acid 3.0 × 10^-4mol / mol Ag, hydrazine-based nucleating agent of the type described in Table 1 in the amount described in Table 1, 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt in 90 mg / m²100 mg / m of colloidal silica having a particle size of 10 μm and an aqueous latex (aqL-6) of 15% by mass with respect to gelatin², 150 mg / m of polyethyl acrylate latex²150 mg / m of a latex copolymer (mass ratio 88: 5: 7) of methyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoxyethyl methacrylate²150 mg / core-shell latex (core: styrene / butadiene copolymer (mass ratio 37/63), shell: styrene / 2-acetoxyethyl acrylate (mass ratio 84/16), core / shell ratio = 50/50) m²Then, 4% by mass of the compound (Cpd-7) was added to gelatin, and the pH was adjusted to 5.6 with citric acid to obtain an emulsion layer coating solution.
[0151]
<Protective layer upper layer coating solution>
Gelatin 0.3g / m²
Amorphous silica matting agent with an average particle size of 3.5 μm 25 mg / m²
Compound (Cpd-8) (gelatin dispersion) 20 mg / m²
Colloidal silica with a particle size of 10-20 μm 30 mg / m²
(Nissan Snowtex C)
Compound (Cpd-9) 50 mg / m²
Sodium dodecylbenzenesulfonate 20mg / m²
Compound (Cpd-10) 20 mg / m²
Compound (Cpd-11) 20 mg / m²
Preservative 1mg / m²
(Proxel (trade name, manufactured by ICI Co., Ltd.))
[0152]
<Protective layer lower layer coating solution>
Gelatin 0.5g / m²
Nucleation promoter (Cpd-12) Amount shown in Table 1
1,5-dihydroxy-2-benzaldoxime 10 mg / m²
Polyethyl acrylate latex 150mg / m²
Compound (Cpd-13) 3 mg / m²
Preservative (Proxel) 1.5mg / m²
[0153]
<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
Preservative (Proxel) 1.5mg / m²
In addition, viscosity adjustment of the coating liquid of each layer was performed by adding the thickener Z which has the following structure.
[0154]
Embedded image

[0155]
Embedded image

[0156]
<Back layer coating solution>
Gelatin 3.3g / m²
Compound (Cpd-15) 40 mg / m²
Compound (Cpd-16) 20 mg / m²
Compound (Cpd-17) 90 mg / m²
Compound (Cpd-18) 40 mg / m²
Compound (Cpd-19) 26 mg / m²
Compound (Cpd-22) 5 mg / m²
Compound (Cpd-9) 10 mg / m²
1,3-divinylsulfonyl-2-propanol 60 mg / m²
Polymethylmethacrylate fine particles 30mg / m²
(Average particle size 6.5 μm)
Liquid paraffin 78mg / m²
Compound (Cpd-7) 120 mg / m²
Calcium nitrate 20mg / m²
Preservative (Proxel) 12mg / m²
[0157]
<Conductive layer coating solution>
Gelatin 0.1g / m²
Sodium dodecylbenzenesulfonate 20mg / m²
SnO₂/ Sb 200mg / m²
(9/1 mass ratio, average particle size 0.25 μm)
Preservative (Proxel) 0.3mg / m²
[0158]
Embedded image

[0159]
[Preparation of support having subbing layer]
Undercoat layers of the following composition on both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm) were coated with a first layer and a second layer.
[0160]
<Undercoat layer 1>
Core-shell type vinylidene chloride copolymer (1) 15 g
2,4-dichloro-6-hydroxy-s-triazine 0.25 g
Polystyrene fine particles (average particle size 3 μm) 0.05 g
Compound (Cpd-20) 0.20 g
Colloidal silica 0.12g
(Snowtex ZL: particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd.)
Amount of water to be 100g
Further, 10% by mass of KOH was added to adjust pH = 6 to obtain a coating solution. This coating solution was applied onto a polyethylene terephthalate support and dried at 180 ° C. for 2 minutes to form a first undercoat layer having a dry film thickness of 0.9 μm.
[0161]
<2nd undercoat layer>
1g of gelatin
Methylcellulose 0.05g
Compound (Cpd-21) 0.02 g
C₁₂H₂₅O (CH₂CH₂O)₁₀H 0.03g
Proxel 3.5 × 10^-3g
Acetic acid 0.2g
Amount of water to be 100g
This coating solution was applied onto the first undercoat layer and dried at 170 ° C. for 2 minutes to form a second undercoat layer having a dry film thickness of 0.1 μm.
[0162]
Embedded image

[0163]
[Coating / Drying]
<Application conditions>
A slide bead coater on the support having the above-mentioned subbing layer is first maintained on the emulsion layer side from the side closer to the support in the order of the UL layer, the emulsion layer, the protective layer lower layer and the protective layer upper layer at 35 ° C. While adding the hardener solution according to the method, simultaneous multilayer coating was performed, and the solution was passed through a cold air set zone (5 ° C.). At this time, the emulsion layer coating solution was Ag 2.9 g / m 2.², Gelatin 1.5 g / m²It applied so that it might become. Then, from the side closer to the support on the side opposite to the emulsion surface, apply the multilayer coating in the order of the conductive layer and back layer in the order of the curtain coater method while adding the hardener solution, and let it pass through the cold air set zone (5 ° C). It was. 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.
[0164]
<Drying conditions>
After setting, dry with dry air at 30 ° C. until the mass ratio of water / gelatin becomes 800%, dry from 800% to 200% with dry air at 35 ° C. and 30% relative humidity, apply wind as it is, surface temperature Thirty seconds after the time when the temperature reached 34 ° C. (considering the completion of drying), drying was performed for 1 minute with air at 48 ° C. and 2% relative humidity. 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.
[0165]
The resulting photosensitive material was wound at 25 ° C. and 55% relative humidity, and heat-treated at 35 ° C. and 30% relative humidity for 72 hours. Next, with a cardboard that was cut at 25 ° C. and 55% relative humidity and conditioned for 6 hours, and then conditioned for 8 hours at 25 ° C. and 50% relative humidity for 2 hours. Sealed to prepare a sample.
The relative humidity in the barrier bag was measured and found to be 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.
By the above procedure, the black and white silver halide photographic light-sensitive material No. 1-14 were produced.
[0166]
[Evaluation]
Each black and white silver halide photographic light-sensitive material produced was evaluated as follows.
1) Test using fresh developer
<Developer and fixer>
In the test using a fresh developer, the following developer 1, developer 2, and fixing solution (B) were used. The fixer (B) was used in an automatic processor described later.
Developer 1
600 ml of water
Potassium hydroxide 29g
Diethylenetriamine-pentaacetic acid 2g
Sodium metabisulfite 40g
40g potassium carbonate
Potassium bromide 3.2g
Hydroquinone 23g
4-hydroxymethyl-4-methyl-
0.4 g of 1-phenyl-3-pyrazolidone
Sodium erythorbate 3g
Diethylene glycol 20g
Water was added to 1 L and the pH was adjusted to 10.45.
Developer 2
The same formulation as Developer 1 except that the hydroquinone in the formulation of Developer 1 was changed to hydroquinone and an equimolar amount of potassium hydroquinone monosulfonate (47.7 g). The pH of Developer 2 was 10.45.
[0167]
Fixing solution (B) formulation The formulation per liter of concentrated solution is shown.
360g ammonium thiosulfate
Ethylenediamine ・ tetraacetic acid ・ 2Na ・ dihydrate 0.09g
Sodium thiosulfate pentahydrate 33.0g
Sodium metasulfite 57.0g
Sodium hydroxide 37.2g
Acetic acid (100%) 90.0g
Tartaric acid 8.7g
Sodium gluconate 5.1g
Aluminum sulfate 25.2g
pH 4.85
In use, it was diluted at a ratio of 2 parts by volume of water to 1 part by volume of the concentrated liquid. The pH of the working solution was 4.8.
[0168]
<Measurement of net change>
Each black-and-white silver halide photographic light-sensitive material is output with a test step while changing the amount of light at 175 lines / inch using an image setter RC5600V manufactured by Fuji Photo Film Co., Ltd. and an AP-560 automatic processor. The developer 1 was used for development for 30 seconds at a development temperature of 35 ° C., and the LV value at which the halftone dot was 50% was determined. Thereafter, using the developing solution 2, the net% at the same LV value was measured. The net percentage was measured using Macbeth TD904. The difference in mesh percentage is preferably within 15%, and more preferably within 10%.
[0169]
<Measurement of γ>
The photographic properties were evaluated by measuring γ according to the following procedure.
Emission time 10 through the step wedge through an interference filter with a peak at 633 nm^-5Exposed with a second xenon flash light. As an index (gradation) indicating the contrast of the image, a point of fog + density 0.1 to a point of fog + density 1.5 of the characteristic curve is connected by a straight line, and the slope of this line is expressed as a γ value. That is, γ (gradation) = (1.5−0.1) / [log (exposure amount giving a density of 1.5) − (exposure amount giving a density of 0.1)]. It shows that the photographic characteristics. As the photosensitive material for graphic arts, γ is preferably 10 or more.
[0170]
<Result>
Table 1 shows the net percentage change and γ value of each black and white silver halide photographic light-sensitive material.
[0171]
[Table 1]

[0172]
2) Running test
<Developer and fixer>
In the running test, the following developer (A) and the above fixer (B) were used.
Developer (A) formulation The formulation per liter of concentrate is shown.

Potassium hydroxide was added, water was added to 1 L, and the pH was adjusted to 10.7.
A solution obtained by adding 3 parts by volume of water to 1 part by volume of the concentrated liquid was used as a start liquid (mother liquid) (pH was 10.4). Moreover, what added 2 volume parts of water with respect to 1 volume part of said concentrate was used as the replenisher (pH is 10.45).
The replenishment amount is 100ml per piece (50.8 x 61.0cm) or 1m²The amount was 323 ml.
[0173]
<Measurement using fresh liquid>
Each black-and-white silver halide photographic light-sensitive material is output with a test step while changing the amount of light at 175 lines / inch using an image setter RC5600V manufactured by Fuji Photo Film Co., Ltd. and an AP-560 automatic processor. The developer (A) was used and processed at a development temperature of 35 ° C. for 30 seconds. The Dmax portion when exposed at an LV value at which the intermediate halftone dot is 50% was measured and used as the practical density (actual skill Dm). The net% and practical concentration were measured using Macbeth TD904. In consideration of the post-process, the actual skill density is required to be 4.0 or more, preferably 4.0 to 5.0.
[0174]
<Measurement after running>
A photosensitive material given an exposure amount at which the halftone dot used in practical density evaluation is 50% is 5 m per day.²The replenishment amount of the developer and the fixing solution at that time is 323 ml / m²Evaluation of actual skill Dm and net% when running for 1 month. The net percentage is preferably within ± 3% of the net percentage after running with respect to 50% of the fresh liquid.
[0175]
<Result>
The experimental results are shown in Table 2.
[0176]
[Table 2]

[0177]
From Table 2, it was found that the black and white silver halide photographic light-sensitive material of the present invention has good photographic properties after running (actual Dm and half-tone change).
In the water washing step of the automatic developing machine, Fuji Photo Film AC-1000 was used as a water-prevention water-saving device, and Fuji Photo Film AB-5 was used in combination as a drug. The replenishment amount was 1 L per large size (61.0 cm × 50.8 cm).
[0178]
Example 2
The same experiment as in Example 1 was carried out by using the liquid preparation of Example 1 as a fresh liquid (starting liquid) and the formulation excluding the diethylene glycol of Example 1 as a replenisher, and finely filling a polyethylene container in the following order of lamination. The solid developer and the solid fixing agent were used. As a result, similar to Example 1, the black and white silver halide photographic light-sensitive material of the present invention showed good performance.
[0179]
Developer
First layer hydroquinone
Second layer Other ingredients
Third layer KBr
Fourth layer Na₂S₂O₅
5th layer potassium carbonate
6th layer KOH pellets
This formulation was dissolved to 3 L and used.
[0180]
The fixing agent used was filled with the following formulation in the same manner as the developer.

[0181]
Example 3
Black and white silver halide photographic light-sensitive material No. 1 of Example 1 2 and no. 6 and the following developers (B), (C), (D), and (E) were used for the same experiment as in Example 1.
[0182]
Developer (B)
600 ml of water
Potassium hydroxide 96.0g
Diethylenetriamine-pentaacetic acid 6.0g
Potassium carbonate 48.0g
Sodium metabisulfite 120.0g
Potassium bromide 9.0g
Hydroquinone 70.0g
5-methylbenzotriazole 0.24 g
1-phenyl-3-pyrazolidone 1.7 g
2-mercaptobenzthiazole 0.18 g
1-Phenyl-5-mercaptotetrazole 0.06g
Sodium erythorbate 9.0g
Diethylene glycol 40.0g
Potassium hydroxide was added, water was added to 1 L, and the pH was adjusted to 10.8.
What added 2 volume parts of water with respect to 1 volume part of said concentrate was used as a developing solution (pH is 10.45). The replenishment amount is 100ml per piece (50.8 x 61.0cm) or 1m²The amount was 323 ml.
[0183]

Water was added to 1 L and the pH was adjusted to 10.48.
[0184]

Water was added to 1 L and the pH was adjusted to 10.41.
[0185]
Developer (E)
600 ml of water
Potassium hydroxide 17.0g
Ethylenediantetraacetic acid 2Na₂H₂O 2.0g
Potassium carbonate 15.0g
Potassium metabisulfite 25.0g
Potassium bromide 5.0g
Hydroquinone 12.0g
1-Phenyl-3-pyrazolidone 0.2g
Water was added to 1 L and the pH was adjusted to 10.05.
The experimental results are shown in Table 3.
[0186]
[Table 3]

[0187]
From Table 3, it was found that the black and white silver halide photographic light-sensitive material of the present invention had good photographic properties after running (actual skill Dm and change in halftone percentage).
[0188]
Example 4
In Examples 1 to 3, processing was carried out at a development temperature of 38 ° C., a fixing temperature of 37 ° C., and a development time of 20 seconds. The results were the same as in Examples 1 to 3, and the effects of the present invention were lost. There wasn't.
[0189]
Example 5
In Examples 1 to 4, the same results were obtained even if the same processing was carried out by using the FG-680AS manufactured by the same company as the automatic processor and setting the conveyance speed of the black and white silver halide photographic light-sensitive material to a linear speed of 1500 mm / min. Obtained.
[0190]
Example 6
In the practical evaluation of the above running method, instead of using the Luxsetter RC-5600V made by Fuji Photo Film Co., Ltd., the image setter FT-R5055 made by Dainippon Screen Co., Ltd. Select made by Agfagebalt Co., Ltd. Set 5000, Avantla 25, or Accuset 1000, Drex 450 or Dreb 800 from Cytex, Rhino 630 from Heidel, Quasar, Hercules Elite, or Signala Setter, or Luxel F-9000, or When the same evaluation as in Examples 1 to 5 was performed using any one model of Panther Pro 62 manufactured by Prepress Co., Ltd., the same effect was observed in the black and white silver halide photographic light-sensitive material of the present invention.
[0191]
Example 7
A silver halide photographic light-sensitive material was prepared by the following method.
[0192]
<Preparation of emulsion A>
1 liquid
650 ml of water
20g gelatin
Sodium chloride 3g
1,3-Dimethylimidazolidine-2-thione 20mg
Sodium benzenethiosulfonate 10mg
Citric acid 0.7g
[0193]
2 liquids
300 ml of water
150g silver nitrate
[0194]

[0195]
Used for 3 liquids (NH₄)₃[RhCl₅(H₂O)] (0.001 mass%) was prepared by dissolving the powder in a 20 mass% aqueous solution of KCl and a 20 mass% aqueous solution of NaCl, respectively, and heating at 40 ° C. for 120 minutes.
[0196]
To 1 liquid maintained at 41 ° C. and pH 4.5, amounts corresponding to 67% of 2 liquid and 3 liquid were simultaneously added over 20 minutes with stirring to form 0.19 μm core particles. Subsequently, the following 4th and 5th liquids were added over 8 minutes, and the remaining 33% of the 2nd and 3rd liquids were added over 2 minutes to grow to 0.21 μm. Further, 0.15 g of potassium iodide was added and ripened for 5 minutes to complete grain formation.
[0197]
4 liquids
100ml water
Silver nitrate 50g
[0198]
5 liquids
100ml water
Sodium chloride 8.6g
Potassium bromide 19.2g
K₄[Fe (CN)₆] 3H₂O (yellow blood salt) 20mg
[0199]
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 precipitant 1 was added, and the pH was lowered using sulfuric acid until the silver halide was precipitated (the range was pH 3.2 ± 0.2). ). Next, about 2 L of the supernatant was removed (first water washing). Further, 2 L of distilled water was added, and sulfuric acid was added until silver halide precipitated. 2 L of the supernatant was again removed (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 6.0mg 4.0 mg of gold acid was added and chemically sensitized so as to obtain an optimum sensitivity at 55 ° C., and 100 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene as a stabilizer and an antiseptic ( 100 mg of ICI (Proxel) was added.
[0200]
Finally, a silver iodochlorobromide cubic grain emulsion containing 55 mol% of silver bromide and 0.08 mol% of silver iodide and having an average grain size of 0.22 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.
[0201]
<Preparation of coating solution>
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.
[0202]
UL layer coating solution
Gelatin 0.8g / m²
Polyethyl acrylate latex 260mg / m²
Compound (Cpd-7) 40 mg / m²
Compound (Cpd-14) 10 mg / m²
5-methylbenzotriazole 20mg / m²
Preservative (ICI, Proxel) 1.5mg / m²
[0203]

The coating solution pH was adjusted to 5.6 using citric acid.
[0204]

In addition, the following thickener Z was added to the coating liquid of each layer, and viscosity was adjusted.
[0206]

[0207]

[0208]
<Coating method on support>
On a polyethylene terephthalate support (thickness: 175 μm) biaxially stretched with an undercoat layer on both sides, the emulsion layer is first composed of four layers in this order: the UL layer, the emulsion layer, the protective layer lower layer, and the protective layer upper layer from the side closer to the support. While maintaining the temperature at 35 ° C., apply a multilayer coating while adding a hardener solution by a slide bead coater method, and after passing through a cold air set zone (5 ° C.), from the side close to the support on the side opposite to the emulsion surface The conductive layer and the back layer were applied simultaneously in the order of the curtain coater method while adding a hardener solution and 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.
[0209]
<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.
[0210]
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. A silver halide photographic light-sensitive material was prepared by sealing with cardboard that had been conditioned for 2 hours at a relative humidity of 50%. 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.
[0211]
<Test>
The same test as in Examples 1 and 2 was performed using the prepared silver halide photographic light-sensitive material. As in Examples 1 and 2, the silver halide photographic light-sensitive material satisfying the conditions of the present invention had a good effect. It was confirmed to show. In addition, the following method was used for the measurement of practical concentration.
(Practical concentration)
Using a RG-7500 made by Dainippon Screen Mfg. Co., Ltd. as a photomask plotter in the industrial field, a 50 μm line was drawn, and the line width after processing according to the processing method of Example 1 was 50 μm. Thus, the actual density was measured by measuring the density when the exposure amount was set. The concentration was measured by the same method as in Example 1.
[0212]
【The invention's effect】
When the black and white silver halide photographic light-sensitive material of the present invention with a reduced amount of silver is used, even if the replenishment amount of the developing solution is small when processing with an automatic processor following the imagesetter, the fluctuation in net% in running is suppressed to a minimum. be able to.

Claims (7)

A black-and-white silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers is a silver halide emulsion layer, and the hydrophilic colloid layer includes Contains at least one hydrazine derivative, and contains the black and white silver halide photographic light-sensitive material treated with a developer containing a hydroquinone developing agent and an equimolar amount of a hydroquinone monosulfonate developing agent with the hydroquinone developing agent. The difference between halftone% when processed with the developing solution is within 15%, and is the slope of the characteristic curve giving the optical density of 0.1 and the optical density of 1.5 (optical density difference / logarithm of exposure amount). A black-and-white silver halide photographic light-sensitive material, wherein γ is 10 or more. 2. The black and white silver halide photographic light-sensitive material according to claim 1, wherein the hydrophilic colloid layer of the silver halide photographic light-sensitive material contains 1 to 8 moles of a nucleation accelerator with respect to the hydrazine derivative. material. The black-and-white silver halide photographic light-sensitive material according to claim 2, wherein the content of the hydrazine is 1.0 x ^10-4 mol / mol Ag or more. 4. The black and white silver halide photographic material according to claim 1, further comprising a gelatin layer between the emulsion layer and the support. The black-and-white silver halide photographic light-sensitive material according to any one of claims 1 to 4, wherein a silver coating amount of the silver halide photographic light-sensitive material is 3.3 g / m ² or less. The black-and-white silver halide photographic light-sensitive material according to any one of claims 1 to 4, wherein a silver coating amount of the silver halide photographic light-sensitive material is 3.0 g / m ² or less. 7. The black and white silver halide photographic material according to claim 1, wherein the silver halide photographic material contains a benzotriazole compound.