JP2004325860A - Thermally developable photosensitive material and image forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermally developable photosensitive material and an image forming method using this having suitability for a sensor in a plate making machine as those for a photomechanical process, particularly for a scanner or an image setter. <P>SOLUTION: In the thermally developable photosensitive material containing an organic silver salt, a silver halide, a developer and a vinyl compound on a support, when density of blacked portions and reflected light intensity of a background after heat development are measured with an FSV1 amplifier by KEYENCE Corp., the values are 50-150 in the blackening portion and 430-620 in the background. The thermally developable photosensitive material and the image forming method using this have suitability for a sensor in a plate making machine as those for a photomechanical process, particularly for a scanner or an image setter and have excellent effects. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

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ビニル化合物の添加層は、ハロゲン化銀を含む感光層及び／又は感光層に隣接した層である。また添加量はハロゲン化銀粒子の粒径、ハロゲン組成、化学増感の程度、抑制剤の種類等により最適量は一様ではないが、ハロゲン化銀１モル当たり１０^−６モル〜１０^−１モル程度、特に１０^−５モル〜１０^−２モルの範囲が好ましい。これらはハロゲン化銀粒子形成時から塗布までの任意の時期に感光材料中に添加できる。
【００９１】
これらビニル化合物は、適当な有機溶媒、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、既に良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、ビニル化合物の粉末を水の中にボールミル、コロイドミル、あるいは超音波によって分散して用いることもできる。
【００９２】
本発明の熱現像感光材料には、上記ビニル化合物に加えて、ヒドラジン誘導体を含有させてもよく、その効果を高めることができる。
【００９３】
ヒドラジン誘導体としては、下記一般式〔Ｈ〕で表される化合物が好ましい。
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【化３０】

【００９５】
式中、Ａ_０はそれぞれ置換基を有してもよい脂肪族基、芳香族基、複素環基又は−Ｇ_０−Ｄ_０基を、Ｂ０はブロッキング基を表し、Ａ_１、Ａ_２はともに水素原子、又は一方が水素原子で他方はアシル基、スルホニル基又はオキザリル基を表す。ここで、Ｇ_０は−ＣＯ−基、−ＣＯＣＯ−基、−ＣＳ−基、−Ｃ（＝ＮＧ_１Ｄ_１）−基、−ＳＯ−基、−ＳＯ_２−基又は−Ｐ（Ｏ）（Ｇ_１Ｄ_１）−基を表し、Ｇ_１は単なる結合手、−Ｏ−基、−Ｓ−基又は−Ｎ（Ｄ_１）−基を表し、Ｄ_１は脂肪族基、芳香族基、複素環基又は水素原子を表し、分子内に複数のＤ_１が存在する場合、それらは同じであっても異なってもよい。Ｄ_０は水素原子、脂肪族基、芳香族基、複素環基、アミノ基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基を表す。
【００９６】
一般式〔Ｈ〕において、Ａ_０で表される脂肪族基は好ましくは炭素数１〜３０のものであり、特に炭素数１〜２０の直鎖、分岐又は環状のアルキル基が好ましく、例えばメチル基、エチル基、ｔ−ブチル基、オクチル基、シクロヘキシル基、ベンジル基が挙げられ、これらは更に適当な置換基（例えばアリール基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、スルホキシ基、スルホンアミド基、スルファモイル基、アシルアミノ基、ウレイド基等）で置換されていてもよい。
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一般式〔Ｈ〕において、Ａ_０で表される芳香族基は、単環又は縮合環のアリール基が好ましく、例えばベンゼン環又はナフタレン環が挙げられ、Ａ_０で表される複素環基としては、単環又は縮合環で窒素、硫黄、酸素原子から選ばれる少なくとも一つのヘテロ原子を含む複素環が好ましく、例えばピロリジン環、イミダゾール環、テトラヒドロフラン環、モルホリン環、ピリジン環、ピリミジン環、キノリン環、チアゾール環、ベンゾチアゾール環、チオフェン環、フラン環が挙げられ、Ａ_０で表される−Ｇ_０−Ｄ_０基において、Ｇ_０は−ＣＯ−基、−ＣＯＣＯ−基、−ＣＳ−基、−Ｃ（＝ＮＧ_１Ｄ_１）−基、−ＳＯ−基、−ＳＯ_２−基又は−Ｐ（Ｏ）（Ｇ_１Ｄ_１）−基を表す。Ｇ１は単なる結合手、−Ｏ−基、−Ｓ−基又は−Ｎ（Ｄ_１）−基を表し、Ｄ_１は脂肪族基、芳香族基、複素環基又は水素原子を表し、分子内に複数のＤ_１が存在する場合、それらは同じであっても異なってもよい。Ｄ_０は水素原子、脂肪族基、芳香族基、複素環基、アミノ基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基を表し、好ましいＤ_０としては水素原子、アルキル基、アルコキシ基、アミノ基等が挙げられる。
【００９８】
Ａ_０の芳香族基、複素環基及び−Ｇ_０−Ｄ_０基は置換基を有していてもよい。
Ａ_０として特に好ましいものはアリール基及び−Ｇ_０−Ｄ_０基である。
【００９９】
又、一般式〔Ｈ〕において、Ａ_０は耐拡散基又はハロゲン化銀吸着基を少なくとも一つ含むことが好ましい。耐拡散基としてはカプラー等の不動性写真用添加剤にて常用されるバラスト基が好ましく、バラスト基としては写真的に不活性であるアルキル基、アルケニル基、アルキニル基、アルコキシ基、フェニル基、フェノキシ基、アルキルフェノキシ基等が挙げられ、置換基部分の炭素数の合計は８以上であることが好ましい。
【０１００】
一般式〔Ｈ〕において、ハロゲン化銀吸着促進基としてはチオ尿素、チオウレタン基、メルカプト基、チオエーテル基、チオン基、複素環基、チオアミド複素環基、メルカプト複素環基、或いは特開昭６４−９０４３９号に記載の吸着基等が挙げられる。
【０１０１】
一般式〔Ｈ〕において、Ｂ_０はブロッキング基を表し、好ましくは−Ｇ_０−Ｄ_０基であり、Ｇ_０は−ＣＯ−基、−ＣＯＣＯ−基、−ＣＳ−基、−Ｃ（＝ＮＧ_１Ｄ１）−基、−ＳＯ−基、−ＳＯ_２−基又は−Ｐ（Ｏ）（Ｇ_１Ｄ_１）−基を表す。好ましいＧ_０としては−ＣＯ−基、−ＣＯＣＯ−基が挙げられ、Ｇ_１は単なる結合手、−Ｏ−基、−Ｓ−基又は−Ｎ（Ｄ_１）−基を表し、Ｄ_１は脂肪族基、芳香族基、複素環基又は水素原子を表し、分子内に複数のＤ_１が存在する場合、それらは同じであっても異なってもよい。Ｄ_０は水素原子、脂肪族基、芳香族基、複素環基、アミノ基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基を表し、好ましいＤ_０としては水素原子、アルキル基、アルコキシ基、アミノ基等が挙げられる。Ａ_１、Ａ_２はともに水素原子又は一方が水素原子で他方はアシル基（アセチル基、トリフルオロアセチル基、ベンゾイル基等）、スルホニル基（メタンスルホニル基、トルエンスルホニル基等）又はオキザリル基（エトキザリル基等）を表す。
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以下に一般式〔Ｈ〕で表される化合物の具体例を示す。
【０１０３】
【化３１】

【０１０４】
【化３２】

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【０１０９】
その他に好ましく用いることのできるヒドラジン誘導体は、米国特許第５，５４５，５０５号カラム１１〜カラム２０に記載の化合物Ｈ−１〜Ｈ−２９、米国特許第５，４６４，７３８号カラム９〜カラム１１に記載の化合物１〜１２である。
【０１１０】
これらのヒドラジン誘導体は公知の方法で合成することができる。ヒドラジン誘導体を使用する場合、その添加層は、ハロゲン化銀乳剤を含む感光層及び／又は感光層に隣接した層である。また添加量はハロゲン化銀粒子の粒径、ハロゲン組成、化学増感の程度、抑制剤の種類等により最適量は一様ではないが、ハロゲン化銀１モル当たり１０^−６モル〜１０^−１モル程度、特に１０^−５モル〜１０^−２モルの範囲が好ましい。
【０１１１】
本発明においてはまた、下記一般式（Ｈ−１）〜（Ｈ−４）で表されるヒドラジン誘導体を一般式（Ｇ）と共に用いることも有効である。
【０１１２】
【化３７】

【０１１３】
Ｒ_１１、Ｒ_１２及びＲ_１３はそれぞれ独立に置換もしくは無置換のアリール基またはヘテロアリール基を表す。Ｒ_１４はヘテロアリールオキシ基、ヘテロアリールチオ基を表す。Ａ_１、Ａ_２はともに水素原子或いは一方が水素原子で他方がアルキルスルホニル基、オキザリル基又はアシル基を表す。
【０１１４】
Ｒ_１１、Ｒ_１２及びＲ_１３はそれぞれ独立に置換もしくは無置換のアリール基またはヘテロアリール基を表すが、アリール基として具体的には、例えばフェニル、ｐ−メチルフェニル、ナフチルなどが挙げられる。ヘテロアリール基として具体的には、例えばトリアゾール残基、イミダゾール残基、ピリジン残基、フラン残基、チオフェン残基などがあげられる。
【０１１５】
また、Ｒ_１１、Ｒ_１２及びＲ_１３はそれぞれ任意の連結基を介して結合しても良い。Ｒ_１１、Ｒ_１２及びＲ_１３が置換基を有する場合、その置換基としては例えばアルキル基、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）、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、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、ウレタン基、カルボキシル基、イミド基、アミノ基、カルボンアミド基、スルホンアミド基、ウレイド基、チオウレイド基、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、（アルキル、アリール、またはヘテロ環）チオ基、メルカプト基、（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、スルファモイル基、アシルスルファモイル基、（アルキルもしくはアリール）スルホニルウレイド基、（アルキルもしくはアリール）スルホニルカルバモイル基、ハロゲン原子、シアノ基、ニトロ基、リン酸アミド基などが挙げられる。Ｒ_１１、Ｒ_１２及びＲ_１３として好ましくはいずれもが置換もしくは無置換のフェニル基であり、より好ましくはＲ_１１、Ｒ_１２及びＲ_１３のいずれもが無置換のフェニル基である。
【０１１６】
Ｒ_１４はヘテロアリールオキシ基、ヘテロアリールチオ基を表すが、ヘテロアリールオキシ基として具体的には、ピリジルオキシ基、ピリミジルオキシ基、インドリルオキシ基、ベンゾチアゾリルオキシ基、ベンズイミダゾリルオキシ基、フリルオキシ基、チエニルオキシ基、ピラゾリルオキシ基、イミダゾリルオキシ基等が挙げられる。ヘテロアリールチオ基として具体的にはピリジルチオ基、ピリミジルチオ基、インドリルチオ基、ベンゾチアゾリルチオ基、ベンズイミダゾリルチオ基、フリルチオ基、チエニルチオ基、ピラゾリルチオ基、イミダゾリルチオ基等が挙げられる。Ｒ_１４として好ましくはピリジルオキシ基、チエニルオキシ基である。
【０１１７】
Ａ_１、Ａ_２は、ともに水素原子、又は一方が水素原子で他方はアシル基（アセチル、トリフルオロアセチル、ベンゾイル等）、スルホニル基（メタンスルホニル、トルエンスルホニル等）、又はオキザリル基（エトキザリル等）を表す。好ましくはＡ_１、Ａ_２ともに水素原子の場合である。
【０１１８】
【化３８】

【０１１９】
Ｒ_２１は置換もしくは無置換のアルキル基、アリール基またはヘテロアリール基を表す。Ｒ_２２は水素原子、アルキルアミノ基、アリールアミノ基、ヘテロアリールアミノ基を表す。
【０１２０】
Ｒ_２１は置換もしくは無置換のアルキル基、アリール基またはヘテロアリール基を表すが、アルキル基として具体的には、メチル基、エチル基、ｔ−ブチル基、２−オクチル基、シクロヘキシル基、ベンジル基、ジフェニルメチル基等が挙げられる。アリール基及びヘテロアリール基として具体的には、Ｒ_１１、Ｒ_１２及びＲ_１３と同様のものが挙げられる。また、Ｒ_２１が置換基を有する場合の置換基の具体的な例としては、Ｒ_１１、Ｒ_１２及びＲ_１３の置換基と同様のものが挙げられる。Ｒ_２１として好ましくはアリール基またはヘテロアリール基であり、特に好ましくは置換もしくは無置換のフェニル基である。
【０１２１】
Ｒ_２２は水素原子、アルキルアミノ基、アリールアミノ基、ヘテロアリールアミノ基を表すが、アルキルアミノ基として具体的には、メチルアミノ基、エチルアミノ基、プロピルアミノ基、ブチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、エチルメチルアミノ基等が挙げられる。アリールアミノ基としてはアニリノ基、ヘテロアリール基としてはチアゾリルアミノ基、ベンズイミダゾリルアミノ基、ベンズチアゾリルアミノ基等が挙げられる。Ｒ_２２として好ましくはジメチルアミノ基またはジエチルアミノ基である。
【０１２２】
Ａ_１、Ａ_２は一般式（Ｈ−１）で記載したＡ_１、Ａ_２と同様である。
【０１２３】
【化３９】

【０１２４】
Ｒ_３１、Ｒ_３２は一価の置換基を表すが、一価の置換基としては、Ｒ_１１、Ｒ_１２及びＲ_１３の置換基として挙げられた基が挙げられるが、好ましくは、アルキル基、アリール基、ヘテロアリール基、アルコキシ基、アミノ基が挙げられる。更に好ましくはアリール基またはアルコキシ基である。特に好ましいのは、Ｒ_３１とＲ_３２の少なくとも一つがｔｅｒｔ−ブトキシ基であるものであり、別の好ましい構造は、Ｒ_３１がフェニル基のとき、Ｒ_３２がｔｅｒｔ−ブトキシ基である。
【０１２５】
Ｇ_３１、Ｇ_３２は−（ＣＯ）ｐ−基、−Ｃ（＝Ｓ）−、スルホニル基、スルホキシ基、−Ｐ（＝Ｏ）Ｒ_３３−基又はイミノメチレン基を表し、ｐは１又は２の整数を表し、Ｒ_３３はアルキル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アルケニルオキシ基、アルキニルオキシ基、アリールオキシ基、アミノ基を表す。但し、Ｇ_３１がスルホニル基のとき、Ｇ_３２はカルボニル基ではない。Ｇ_３１、Ｇ_３２として好ましくは−ＣＯ−基、−ＣＯＣＯ−基、スルホニル基または−ＣＳ−であり、より好ましくは互いに−ＣＯ−基または互いにスルホニル基である。
【０１２６】
Ａ_１、Ａ_２は一般式（Ｈ−１）で記載したＡ_１、Ａ_２と同様である。一般式（Ｈ−３）において、Ｇ_３１とＧ_３２がいずれもカルボニル基、またはいずれもスルホニル基であることが特に好ましい。
【０１２７】
一般式（Ｈ−３）において、Ｒ_３１、Ｒ_３２のすくなくとも一つが以下に示す構造であることが特に好ましい。
【０１２８】
−Ｏ−Ｃ（ＣＨ_３）_３
【０１２９】
【化４０】

【０１３０】
Ｒ_４１、Ｒ_４２及びＲ_４３はそれぞれ独立に置換もしくは無置換のアリール基またはヘテロアリール基を表す。Ｒ_４４、Ｒ_４５は無置換または置換アルキル基を表す。Ａ_１、Ａ_２はともに水素原子或いは一方が水素原子で他方がアルキルスルホニル基、オキザリル基又はアシル基を表す。
【０１３１】
Ｒ_４１、Ｒ_４２およびＲ_４３は一般式（Ｈ−１）におけるＲ_１１、Ｒ_１２およびＲ_１３と同義である。Ｒ_４１、Ｒ_４２およびＲ_４３として好ましくはいずれもが置換もしくは無置換のフェニル基であり、より好ましくはＲ_４１、Ｒ_４２及びＲ_４３のいずれもが無置換のフェニル基である。Ｒ_４４、Ｒ_４５は無置換または置換アルキル基を表すが、具体的な例としては、メチル基、エチル基、ｔ−ブチル基、２−オクチル基、シクロヘキシル基、ベンジル基、ジフェニルメチル基等が挙げられる。Ｒ_４４、Ｒ_４５として好ましくは互いにエチル基である。
【０１３２】
Ａ_１、Ａ_２は一般式（Ｈ−１）で記載したＡ_１、Ａ_２と同様である。以下にこれら一般式（Ｈ−１）〜（Ｈ−４）で表される化合物の具体的代表例を挙げる。
【０１３３】
【化４１】

【０１３４】
【化４２】

【０１３５】
【化４３】

【０１３６】
【化４４】

【０１３７】
【化４５】

【０１３８】
【化４６】

【０１３９】
【化４７】

【０１４０】
【化４８】

【０１４１】
これらの一般式（Ｈ−１）〜（Ｈ−４）で表される化合物は、公知の方法により容易に合成することができる。例えば米国特許第５，４６４，７３８号または米国特許第５，４９６，６９５号を参考にして合成することができる。
【０１４２】
これらヒドラジン誘導体を使用する場合、添加層は、ハロゲン化銀乳剤を含む感光層及び／又は感光層に隣接した層である。また添加量はハロゲン化銀粒子の粒径、ハロゲン組成、化学増感の程度、抑制剤の種類等により最適量が違い、一様ではないが、ハロゲン化銀１モル当たり１０^−６モル〜１０^−１モル程度、特に１０^−５モル〜１０^−２モルの範囲が好ましい。
【０１４３】
ヒドラジン誘導体は、適当な有機溶媒に溶解したり、乳化分散物を形成した後、添加したりあるいは固体分散法として知られている方法によって添加することができる。
【０１４４】
また本発明の熱現像感光材料には、米国特許第５，５４５，５０５号に記載のヒドロキシルアミン化合物、アルカノールアミン化合物やフタル酸アンモニウム化合物、米国特許第５，５４５，５０７号に記載のヒドロキサム酸化合物、米国特許第５，５５８，９８３号に記載のＮ−アシル−ヒドラジン化合物、米国特許第５，５４５，５１５号に記載のアクリロニトリロ化合物、米国特許第５，９３７，４４９号に記載のベンズヒドロールやジフェニルフォスフィンやジアルキルピペリジンやアルキル−β−ケトエステルなどの水素原子ドナー化合物、などの硬調化促進剤を添加することが好ましい。その中でも下記一般式（Ｐ）で表される４級オニウム化合物及び一般式〔Ｎａ〕で表されるアミノ化合物が好ましく用いられる。
【０１４５】
【化４９】

【０１４６】
式中、Ｑは窒素原子又は燐原子を表し、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は各々、水素原子又は置換基を表し、Ｘ⁻はアニオンを表す。尚、Ｒ_１〜Ｒ_４は互いに連結して環を形成してもよい。
【０１４７】
【化５０】

【０１４８】
一般式〔Ｎａ〕において、Ｒ_１１、Ｒ_１２及びＲ_１３は各々水素原子、アルキル基、置換アルキル基、アルケニル基、置換アルケニル基、アルキニル基、アリール基、置換アリール基、又は飽和若しくは不飽和のヘテロ環を表す。Ｒ_１１、Ｒ_１２及びＲ_１３で環を形成してもよい。特に好ましくは脂肪族の３級アミン化合物である。
【０１４９】
これらの化合物は分子中に耐拡散性基又はハロゲン化銀吸着基を有するものが好ましい。耐拡散性を有するためには分子量１００以上の化合物が好ましく、さらに好ましくは分子量３００以上であり、前記一般式〔Ｈ〕におけるＡ_０における耐拡散基と同義のものが挙げられる。また、好ましい吸着基としては複素環、メルカプト基、チオエーテル基、チオン基、チオウレア基等が挙げられる。
【０１５０】
一般式〔Ｎａ〕で表される造核促進剤より更に好ましい造核促進剤として下記一般式〔Ｎａ２〕で表される化合物が挙げられる。
【０１５１】
【化５１】

【０１５２】
一般式〔Ｎａ２〕において、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、各々水素原子、アルキル基、置換アルキル基、アルケニル基、置換アルケニル基、アルキニル基、置換アルキニル基、アリール基、置換アリール基又は飽和若しくは不飽和のヘテロ環を表す。これらは互いに連結して環を形成することができる。又、Ｒ_１とＲ_２、Ｒ_３とＲ_４が同時に水素原子であることはない。ＸはＳ、Ｓｅ又はＴｅ原子を表す。Ｌ_１及びＬ_２は各々２価の連結基を表す。具体的には以下に示す基又はその組み合わせ及びそれらに適当な置換基（例えばアルキレン基、アルケニレン基、アリーレン基、アシルアミノ基、スルホンアミド基等）を有する基が挙げられる。
【０１５３】
−ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ_２Ｈ_４−、ピリジンジイル、−Ｎ（Ｚ_１）−（Ｚ_１は水素原子、アルキル基又はアリール基を表す）、−Ｏ−、−Ｓ−、−（ＣＯ）−、−（ＳＯ_２）−、−ＣＨ_２Ｎ−。
【０１５４】
又、Ｌ_１又はＬ_２で表される連結基は、該連結基中に少なくとも１つ以上の以下の構造を含むことが好ましい。
【０１５５】
−［ＣＨ_２ＣＨ_２Ｏ］−、−［Ｃ（ＣＨ_３）ＨＣＨ_２Ｏ］−、−［ＯＣ（ＣＨ_３）ＨＣＨ_２Ｏ］−、−［ＯＣＨ_２Ｃ（ＯＨ）ＨＣＨ_２］−。
【０１５６】
以下に一般式〔Ｎａ〕又は〔Ｎａ２〕で表される造核促進剤の具体例を挙げる。
【０１５７】
【化５２】

【０１５８】
【化５３】

【０１５９】
【化５４】

【０１６０】
【化５５】

【０１６１】
一般式（Ｐ）において、Ｒ_１〜Ｒ_４で表される置換基としては、アルキル基（メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、シクロヘキシル基等）、アルケニル基（アリル基、ブテニル基等）、アルキニル基（プロパルギル基、ブチニル基等）、アリール基（フェニル基、ナフチル基等）、複素環基（ピペリジニル基、ピペラジニル基、モルホリニル基、ピリジル基、フリル基、チエニル基、テトラヒドロフリル基、テトラヒドロチエニル基、スルホラニル基等）、アミノ基等が挙げられる。
【０１６２】
Ｒ_１〜Ｒ_４が互いに連結して形成しうる環としては、ピペリジン環、モルホリン環、ピペラジン環、キヌクリジン環、ピリジン環、ピロール環、イミダゾール環、トリアゾール環、テトラゾール環等が挙げられる。
【０１６３】
Ｒ_１〜Ｒ_４で表される基はヒドロキシル基、アルコキシ基、アリールオキシ基、カルボキシル基、スルホ基、アルキル基、アリール基等の置換基を有してもよい。
【０１６４】
Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４としては、水素原子及びアルキル基が好ましい。Ｘ−が表すアニオンとしては、ハロゲンイオン、硫酸イオン、硝酸イオン、酢酸イオン、ｐ−トルエンスルホン酸イオン等の無機及び有機のアニオンが挙げられる。
【０１６５】
更に好ましくは下記一般式（Ｐａ）、（Ｐｂ）又は（Ｐｃ）で表される化合物、及び下記一般式〔Ｔ〕で表される化合物である。
【０１６６】
【化５６】

【０１６７】
式中、Ａ_１、Ａ_２、Ａ_３、Ａ_４及びＡ_５は、含窒素複素環を完成させるための非金属原子群を表し、酸素原子、窒素原子、硫黄原子を含んでもよく、ベンゼン環が縮合しても構わない。Ａ_１、Ａ_２、Ａ_３、Ａ_４及びＡ_５で構成される複素環は置換基を有してもよく、それぞれ同一でも異なっていてもよい。
【０１６８】
置換基としては、アルキル基、アリール基、アラルキル基、アルケニル基、アルキニル基、ハロゲン原子、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、スルホ基、カルボキシ基、ヒドロキシル基、アルコキシ基、アリールオキシ基、アミド基、スルファモイル基、カルバモイル基、ウレイド基、アミノ基、スルホンアミド基、スルホニル基、シアノ基、ニトロ基、メルカプト基、アルキルチオ基、アリールチオ基を表す。Ａ_１、Ａ_２、Ａ_３、Ａ_４及びＡ_５の好ましい例としては、５〜６員環（ピリジン、イミダゾール、チオゾール、オキサゾール、ピラジン、ピリミジン等の各環）を挙げることができ、更に好ましい例としてピリジン環が挙げられる。
【０１６９】
ＢＰは２価の連結基を表し、ｍは０又は１を表す。２価の連結基としては、アルキレン基、アリーレン基、アルケニレン基、−ＳＯ_２−、−ＳＯ−、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｎ（Ｒ_６）−（Ｒ_６はアルキル基、アリール基、水素原子を表す）を単独又は組み合わせて構成されるものを表す。Ｂｐとして好ましくは、アルキレン基、アルケニレン基を挙げることができる。
【０１７０】
Ｒ_１、Ｒ_２及びＲ_５は各々、炭素数１〜２０のアルキル基を表す。又、Ｒ_１及びＲ_２は同一でも異っていてもよい。アルキル基とは、置換或いは無置換のアルキル基を表し、置換基としては、Ａ_１、Ａ_２、Ａ_３、Ａ_４及びＡ_５の置換基として挙げた置換基と同様である。
【０１７１】
Ｒ_１、Ｒ_２及びＲ_５の好ましい例としては、それぞれ炭素数４〜１０のアルキル基である。更に好ましい例としては、置換或いは無置換のアリール置換アルキル基が挙げられる。
【０１７２】
Ｘｐ⁻は分子全体の電荷を均衡さすに必要な対イオンを表し、例えば塩素イオン、臭素イオン、沃素イオン、硝酸イオン、硫酸イオン、ｐ−トルエンスルホナート、オキザラート等を表す。ｎｐは分子全体の電荷を均衡さすに必要な対イオンの数を表し、分子内塩の場合にはｎｐは０である。
【０１７３】
【化５７】

【０１７４】
上記一般式〔Ｔ〕で表されるトリフェニルテトラゾリウム化合物のフェニル基の置換基Ｒ_５、Ｒ_６、Ｒ_７は水素原子もしくは電子吸引性度を示すハメットのシグマ値（σＰ）が負のものが好ましい。
【０１７５】
フェニル基におけるハメットのシグマ値は多くの文献、例えばジャーナル・オブ・メディカルケミストリー（Ｊｏｕｒｎａｌ ｏｆ Ｍｅｄｉｃａｌ Ｃｈｅｍｉｓｔｒｙ）２０巻、３０４頁、１９７７年記載のＣ．ハンシュ（Ｃ．Ｈａｎｓｃｈ）等の報文等に見ることが出来、特に好ましい負のシグマ値を有する基としては、例えばメチル基（σＰ＝−０．１７以下何れもσＰ値）、エチル基（−０．１５）、シクロプロピル基（−０．２１）、ｎ−プロピル基（−０．１３）、ｉｓｏ−プロピル基（−０．１５）、シクロブチル基（−０．１５）、ｎ−ブチル基（−０．１６）、ｉｓｏ−ブチル基（−０．２０）、ｎ−ペンチル基（−０．１５）、シクロヘキシル基（−０．２２）、アミノ基（−０．６６）、アセチルアミノ基（−０．１５）、ヒドロキシル基（−０．３７）、メトキシ基（−０．２７）、エトキシ基（−０．２４）、プロポキシ基（−０．２５）、ブトキシ基（−０．３２）、ペントキシ基（−０．３４）等が挙げられ、これらは何れも一般式〔Ｔ〕の化合物の置換基として有用である。
【０１７６】
ｎは１或いは２を表し、ＸＴｎ⁻で表されるアニオンとしては、例えば塩化物イオン、臭化物イオン、ヨウ化物イオン等のハロゲンイオン、硝酸、硫酸、過塩素酸等の無機酸の酸根、スルホン酸、カルボン酸等の有機酸の酸根、アニオン系の活性剤、具体的にはｐ−トルエンスルホン酸アニオン等の低級アルキルベンゼンスルホン酸アニオン、ｐ−ドデシルベンゼンスルホン酸アニオン等の高級アルキルベンゼンスルホン酸アニオン、ラウリルスルフェートアニオン等の高級アルキル硫酸エステルアニオン、テトラフェニルボロン等の硼酸系アニオン、ジ−２−エチルヘキシルスルホサクシネートアニオン等のジアルキルスルホサクシネートアニオン、セチルポリエテノキシサルフェートアニオン等の高級脂肪酸アニオン、ポリアクリル酸アニオン等のポリマーに酸根のついたもの等を挙げることができる。
【０１７７】
以下、４級オニウム化合物の具体例を下記に挙げるが、これらに限定されるものではない。
【０１７８】
【化５８】

【０１７９】
【化５９】

【０１８０】
【化６０】

【０１８１】
【化６１】

【０１８２】
【化６２】

【０１８３】
【化６３】

【０１８４】
【化６４】

【０１８５】
【化６５】

【０１８６】
【化６６】

【０１８７】
【化６７】

【０１８８】
上記４級オニウム化合物は公知の方法に従って容易に合成でき、例えば上記テトラゾリウム化合物はＣｈｅｍｉｃａｌ Ｒｅｖｉｅｗｓ ５５ ｐ．３３５〜４８３に記載の方法を参考にできる。
【０１８９】
これら４級オニウム化合物の添加量は、ハロゲン化銀１モル当たり１×１０^−８〜１モル程度、好ましくは１×１０^−７〜１×１０^−１モルである。これらはハロゲン化銀粒子形成時から塗布までの任意の時期に感光材料中に添加できる。
【０１９０】
また、本発明においては以下の下記一般式（Ａ−１）〜（Ａ−４）で表される化合物を現像促進剤として用いることが出来る。
【０１９１】
【化６８】

【０１９２】
一般式（Ａ−１）において、Ｒ_５１はアルキル基、アルケニル基、アルコキシ基、アルキルチオ基、アミド基、アリール基、アラルキル基、アリールオキシ基、アリールチオ基、アニリノ基またはヘテロ環基を表す。一般式（Ａ−２）において、Ｒ_６１、Ｒ_６２は水素原子、アルキル基、アルケニル基、アリール基、アラルキル基、脂肪族または芳香族ヘテロ環基、環状脂肪族基を表す。一般式（Ａ−３）において、Ｒ_７１はヒドロキシアルキル基を表し、Ｒ_７２、Ｒ_７３はそれぞれ独立に、水素原子、アルキル基、−（ＣＨ_２）ｎ−Ｎ−Ｒ_７４（Ｒ_７５）（ｎは１〜１０の整数、Ｒ_７４、Ｒ_７５はそれぞれ独立に水素原子、アルキル基）を表す。一般式（Ａ−４）において、Ｒ_８１はヒドラジノ基、アルキルアミノ基、スルホニルアミノ基、ウレイド基、オキシカルボニルアミノ基、アルキニル基または無置換のアミノ基を表す。Ｒ_８２は水素原子、アルキル基、アリール基またはヘテロ環基を表し、Ｘは水素原子、アルキル基、カルバモイル基またはオキシカルボニル基を表す。Ｒ_８１とＲ_８２とが結合して５員から７員の環を形成してもよい。
【０１９３】
これらの化合物の添加量は、ハロゲン化銀１モル当たり１×１０^−８〜１モル程度、好ましくは１×１０^−７〜１×１０^−１モルである。これらはハロゲン化銀粒子形成時から塗布までの任意の時期に感光材料中に添加できる。
【０１９４】
また、本発明の熱現像感光材料には、現像促進剤として、下記化合物を含有することが出来る。
【０１９５】
２−メルカプトベンズイミダゾール、２−メルカプトベンズオキサゾール、２−メルカプトベンゾチアゾール、２−メルカプト−５−メチルベンズイミダゾール、６−エトキシ−２−メルカプトベンゾチアゾール、２，２′−ジチオビス−ベンゾチアゾール、３−メルカプト−１，２，４−トリアゾール、４，５−ジフェニル−２−イミダゾールチオール、２−メルカプトイミダゾール、１−エチル−２−メルカプトベンズイミダゾール、２−メルカプトキノリン、８−メルカプトプリン、２−メルカプト−４（３Ｈ）−キナゾリノン、７−トリフルオロメチル−４−キノリンチオール、２，３，５，６−テトラクロロ−４−ピリジンチオール、４−アミノ−６−ヒドロキシ−２−メルカプトピリミジンモノヒドレート、２−アミノ−５−メルカプト−１，３，４−チアジアゾール、３−アミノ−５−メルカプト−１，２，４−トリアゾール、４−ヒドキロシ−２−メルカプトピリミジン、２−メルカプトピリミジン、４，６−ジアミノ−２−メルカプトピリミジン、２−メルカプト−４−メチルピリミジンヒドロクロリド、３−メルカプト−５−フェニル−１，２，４−トリアゾール、２−メルカプト−４−フェニルオキサゾールなど。
【０１９６】
フタルイミドおよびＮ−ヒドロキシフタルイミド；スクシンイミド、ピラゾリン−５−オン、ならびにキナゾリノン、３−フェニル−２−ピラゾリン−５−オン、１−フェニルウラゾール、キナゾリンおよび２，４−チアゾリジンジオンのような環状イミド；ナフタルイミド（例えば、Ｎ−ヒドロキシ−１，８−ナフタルイミド）；コバルト錯体（例えば、コバルトヘキサミントリフルオロアセテート）；３−メルカプト−１，２，４−トリアゾール、２，４−ジメルカプトピリミジン、３−メルカプト−４，５−ジフェニル−１，２，４−トリアゾールおよび２，５−ジメルカプト−１，３，４−チアジアゾールに例示されるメルカプタン；Ｎ−（アミノメチル）アリールジカルボキシイミド、（例えば、（Ｎ，Ｎ−ジメチルアミノメチル）フタルイミドおよびＮ，Ｎ−（ジメチルアミノメチル）−ナフタレン−２，３−ジカルボキシイミド）；ならびにブロック化ピラゾール、イソチウロニウム誘導体およびある種の光退色剤（例えば、Ｎ，Ｎ′−ヘキサメチレンビス（１−カルバモイル−３，５−ジメチルピラゾール）、１，８−（３，６−ジアザオクタン）ビス（イソチウロニウムトリフルオロアセテート）および（２−トリブロモメチルスルホニル）−（ベンゾチアゾール））；ならびに３−エチル−５−［（３−エチル−２−ベンゾチアゾリニリデン）−１−メチルエチリデン］−２−チオ−２，４−オキサゾリジンジオン；フタラジノン、フタラジノン誘導体もしくは金属塩、または４−（１−ナフチル）フタラジノン、６−クロロフタラジノン、５，７−ジメトキシフタラジノンおよび２，３−ジヒドロ−１，４−フタラジンジオンなどの誘導体；フタラジノンとフタル酸誘導体（例えば、フタル酸、４−メチルフタル酸、４−ニトロフタル酸およびテトラクロロ無水フタル酸など）との組合せ；フタラジン、フタラジン誘導体もしくは金属塩、または４−（１−ナフチル）フタラジン、６−クロロフタラジン、５，７−ジメトキシフタラジンおよび２，３−ジヒドロフタラジンなどの誘導体；フタラジンとフタル酸誘導体（例えば、フタル酸、４−メチルフタル酸、４−ニトロフタル酸およびテトラクロロ無水フタル酸など）との組合せ；キナゾリンジオン、ベンズオキサジンまたはナフトオキサジン誘導体；色調調節剤としてだけでなくその場でハロゲン化銀生成のためのハライドイオンの源としても機能するロジウム錯体、例えばヘキサクロロロジウム（ＩＩＩ）酸アンモニウム、臭化ロジウム、硝酸ロジウムおよびヘキサクロロロジウム（ＩＩＩ）酸カリウムなど；無機過酸化物および過硫酸塩、例えば、過酸化二硫化アンモニウムおよび過酸化水素；１，３−ベンズオキサジン−２，４−ジオン、８−メチル−１，３−ベンズオキサジン−２，４−ジオンおよび６−ニトロ−１，３−ベンズオキサジン−２，４−ジオンなどのベンズオキサジン−２，４−ジオン；ピリミジンおよび不斉−トリアジン（例えば、２，４−ジヒドロキシピリミジン、２−ヒドロキシ−４−アミノピリミジンなど）、アザウラシル、およびテトラアザペンタレン誘導体（例えば、３，６−ジメルカプト−１，４−ジフェニル−１Ｈ，４Ｈ−２，３ａ，５，６ａ−テトラアザペンタレン、および１，４−ジ（ｏ−クロロフェニル）−３，６−ジメルカプト−１Ｈ，４Ｈ−２，３ａ，５，６ａ−テトラアザペンタレン）など。
【０１９７】
これらのうち、本発明には酸無水物が好ましく用いられる。本発明に特に好ましく使用できる酸無水物は、モノカルボン酸が２分子脱水縮合してＡ−ＣＯ−Ｏ−ＣＯ−Ｂ構造を分子内に有するものを含み、式中Ａ及びＢは直鎖状の分子構造を有する置換基でも、環状の構造を有する置換基でもよい。又これらＡ及びＢの一部が結合した環状の構造を有していても良い。また、スルホン酸が脱水縮合したＡ−ＳＯ_２−Ｏ−ＣＯ−Ｂ，Ａ−ＳＯ_２−Ｏ−ＳＯ_２−Ｂでも良い。直鎖状のものは２分子の脂肪族モノカルボン酸が脱水して形成されるもので、例えば、無水酢酸、無水プロパン酸、無水ブタン酸、無水ペンタン酸、無水カプロン酸、無水ラウリン酸、無水ステアリン酸、無水セバシン酸、無水アラキジン酸、無水ベヘン酸等が挙げられ、脂肪族カルボン酸の炭素数は１〜３０までが好ましい。又、環状の構造を有する置換基としてはアリール基、ヘテロアリール基等があげられ、芳香族カルボン酸、例えば、無水安息香酸、ピリジンカルボン酸無水物、或いはこれらの誘導体等が含まれる。又、Ａ及びＢの一部が結合した環状の構造を有するものとしては、無水フタル酸、無水ナフタル酸等の様な２塩基酸の酸無水物等があげられる。
【０１９８】
以下に一般例を示すがこれに限定されることはない。
【０１９９】
【化６９】

【０２００】
本発明においては、感光層の上に少なくとも一層の非感光層が形成されていることが好ましい。また、感光層に通過する光の量または波長分布を制御するために感光層と同じ側または反対側にフィルター層を形成しても良いし、感光層に染料または顔料を含ませても良い。
【０２０１】
また、感光層は、階調の調節のため高感度層／低感度層または低感度層／高感度層等の複数層構成にしてもよい。
【０２０２】
本発明の熱現像感光材料には例えば、界面活性剤、酸化防止剤、安定化剤、可塑剤、紫外線吸収剤、被覆助剤等を含有していてもよく、これら各種の添加剤は感光層、非感光層、またはその他の形成層のいずれに含有されていても良い。
【０２０３】
本発明の熱現像感光材料に用いる好適なバインダーは透明又は半透明で、一般に無色であり、天然ポリマー合成樹脂やポリマー及びコポリマー、その他フィルムを形成する媒体、例えば、ゼラチン、アラビアゴム、ポリ（ビニルアルコール）、ヒドロキシエチルセルロース、セルロースアセテート、セルロースアセテートブチレート、ポリ（ビニルピロリドン）、カゼイン、デンプン、ポリ（アクリル酸）、ポリ（メチルメタクリル酸）、ポリ（塩化ビニル）、ポリ（メタクリル酸）、コポリ（スチレン−無水マレイン酸）、コポリ（スチレン−アクリロニトリル）、コポリ（スチレン−ブタジエン）、ポリ（ビニルアセタール）類（例えば、ポリ（ビニルホルマール）及びポリ（ビニルブチラール））、ポリ（エステル）類、ポリ（ウレタン）類、フェノキシ樹脂、ポリ（塩化ビニリデン）、ポリ（エポキシド）類、ポリ（カーボネート）類、ポリ（ビニルアセテート）、セルロースエステル類、ポリ（アミド）類がある。バインダーは水又は有機溶媒に溶解して、またはエマルジョンの形で熱現像感光層、非感光層等を被覆形成してもよい。
【０２０４】
このような熱現像感光材料中にはカブリ防止剤が含まれて良い。カブリ防止剤としては例えば米国特許第４，５４６，０７５号及び同４，４５２，８８５号及び特開昭５９−５７２３４号に開示されているようなカブリ防止剤が好ましい。
【０２０５】
本発明の熱現像感光材料の露光は、レーザーイメージセッターに使用する場合、Ｈｅ−Ｎｅレーザー（６３３ｎｍ）、赤色半導体レーザー（６７０ｎｍ）、赤外半導体レーザー（７８０ｎｍ、８３０ｎｍ）などにより行うことが好ましい。
【０２０６】
本発明の熱現像感光材料にはハレーション防止層として、染料を含有する層を設ける事ができる。Ｈｅ−Ｎｅレーザー、赤色半導体レーザー用には４００ｎｍ〜７５０ｎｍの範囲で、露光波長に少なくとも０．３以上、好ましくは０．８以上の吸収となるように染料を添加する。赤外半導体レーザー用には７５０ｎｍ〜１５００ｎｍの範囲で、露光波長に少なくとも０．３以上、好ましくは０．８以上の吸収となるように染料を添加する。染料は１種でも数種を組み合わせても良い。これらの染料は感光層と同じ側の支持体に近い染料層あるいは、感光層と反対側の染料層に添加する事ができる。また、光、熱消色型の染料を用いてもよい。
【０２０７】
本発明において使用される支持体は熱寸法変化率が、露光部の最大濃度が４．０以上、且つ、未露光部の濃度が０．２以下になる熱現像条件において、０．０４％未満の支持体である。より好ましくは０．０３％以下であり、さらに好ましくは０．０２％以下の支持体である。この変化率は、低ければ低いほどよいが、その下限値は、０．００１％である。この範囲を上回る支持体は支持体上の画像形成層との密着が悪化しやすく好ましくない。
【０２０８】
好ましい支持体の例としては、ポリカーボネート（ＰＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエーテルスルフォン（ＰＥＳ）、ポリアリレート（ＰＡｒ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリサルフォン（ＰＳＯ）、シンジオタクチックポリスチレン（ＳＰＳ）等の支持体およびこれらの支持体を熱処理したもの、また、ポリエチレンナフタレート（ＰＥＮ）を熱処理したものが挙げられる。なかでもＰＣ、ＰＥＴおよびこれらを熱処理したものまたはＰＥＮを熱処理したものが好ましく、特にＰＣと熱処理したＰＥＴが好ましい。
【０２０９】
なお、熱寸法率は、通常、長手方向（ＭＤ）と幅方向（ＴＤ）とについてのものであり、両方向とも０．０４％未満であることが好ましいが、いずれか一方が０．０４％未満である場合も本発明に包含される。
【０２１０】
これらの支持体は有機、無機の微粒子を含んでいても良く、好ましい微粒子として、シリカ、アルミナ、炭酸カルシウム、チタニア、塩化カルシウム、架橋ポリメチルメタクリレート粒子、架橋ポリスチレン粒子、等が挙げられ、好ましい粒子サイズは０．０２〜３μｍ以下、好ましい添加量は１０〜１０００ｐｐｍである。またこれらの支持体のヤング率は、その取扱性から２０００〜８０００Ｎ／ｍｍ^２、より好ましくは３０００〜６０００Ｎ／ｍｍ^２である。
【０２１１】
支持体の熱処理については感光層を塗布する前に行う。このような熱処理は８０〜２００℃、より好ましくは１００〜１８０℃、さらに好ましくは１１０〜１６０℃で実施するのが好ましく、熱処理はこの温度範囲内の一定温度で実施してもよく、昇温あるいは冷却しながらの熱処理でもよい。なかでも好ましいのが、一定温度あるいは、冷却しながらの熱処理である。この熱処理時間は、１分〜２００時間である。１分未満では充分な効果を得ることができず、２００時間を超えると効果が飽和すると共に、支持体が着色したり、脆化が起こり易くなり、また、作業効率が低下する。
【０２１２】
支持体の熱処理は、ロール状で、またウエブ状で搬送しなが実施してもよい。ロール状で熱処理する場合、１．ロールを室温から恒温槽中で熱処理する方法（低温巻き取り法）、２．ウエブ搬送中に所定温度にした後ロール状に巻き取り熱処理する方法（高温巻き取り法）のいずれの方法で実施しても良い、１．の方法は昇温、降温に時間を要するが、設備投資が少なくて済む利点があり、２．の方法は高温での巻き取り設備が必要だが昇温時間を省略できる利点がある。
【０２１３】
ロール状での熱処理では、熱処理中の熱収縮応力のため、巻き締まりによるしわ、巻き芯部の切り口写り等の面状故障が発生し易い。このため、支持体の両端にローレットを付与し端部のみ少し高くすることで巻き芯部の切り口写りを防止するなどの工夫を行うことが望ましい。ローレットの巾は２〜５０ｍｍ、より好ましくは５〜３０ｍｍさらに好ましくは、７〜２０ｍｍであり、高さは、０．５〜１００μｍが好ましく、さらに１〜５０μｍが好ましく、２〜２０μｍが最も好ましい。ローレットは片押しでも両押しでもかまわず、付与時の温度は、Ｔｇ以上が好ましい。またこのような熱処理を実施するときの雰囲気の絶対湿度は、熱処理中のブロッキングの観点から空気１ｋｇ当たり、水の含量が２２ｇ以下、より好ましくは１６ｇ以下、さらに好ましくは８ｇ以下で行なうのが良い。この絶対湿度に特に下限値はないが、通常空気１ｋｇ当たりの水の含量が０．１ｇ程度である。
【０２１４】
ロールの単位巾当たりの巻き張力が初期張力が３００〜７５００ｋＰａ、巻き終わりの張力が３００〜７５００ｋＰａが好ましい。この範囲以下では、緩巻きのため熱処理中にロールが自重でたるみ変形が発生しやすく、一方、この値以上は、巻き締まりによるしわが発生しやすい。初期張力のより好ましい範囲は、５００〜４０００ｋＰａ、巻き終わりのより好ましい範囲は、２００〜３５００ｋＰａである。初期張力を巻き終わり張力より大きくしながら巻き取った方がより好ましい。
【０２１５】
本発明では、熱処理時の支持体の搬送張力を１３００ｋＰａ以下、さらには１０００ｋＰａ以下、特には４００ｋＰａ以下にすることが好ましい。そうすると支持体の熱寸法変化率が飛躍的に小さくなり、感光材料と支持体との密着性も向上する。
【０２１６】
また、本発明の巻き芯の直径は、１００〜６００ｍｍであることが好ましい。これよりも直径が小さくなると加熱処理によりベコやシワが発生する。６００ｍｍを超えるとかさ高くなり貯蔵および搬送において不便であり現実的でない。好ましくは、直径が１５０〜４５０ｍｍ、さらに好ましくは２００〜４００ｍｍである。巻き芯の断面は真円であることが好ましい。
【０２１７】
これらの巻き芯の材質は熱処理中に充分な弾性率を有し、支持体の熱収縮応力によって変形しにくいものが好ましく、セラミック、金属、樹脂、ＦＲＰ（繊維強化プラスチック）でできた巻き芯が好ましい。
【０２１８】
一方、ウエブ状で熱処理する場合、熱処理ゾーンを必要とするが、ロール状での熱処理に比べて良好な支持体面状が得られ、より好ましい。この時の搬送張力は１０〜１３００ｋＰａが好ましく、より好ましくは３０〜１０００ｋＰａ、さらに好ましくは５０〜４００ｋＰａである。このような低い張力は特に熱処理ゾーンで達成する必要があり、熱処理ゾーンの前後にサクションドラムを設定し、この間だけ弱い張力で搬送し、その後の巻き取り工程はこれより高い張力で巻き取るのがより好ましい。巻き取りはチリングロール等で充分に冷却してから巻き取るのが寸法変化を小さくする上で好ましい。さらに支持体に加わる力は巻き取り張力以外にもそれ自身が生ずる熱収縮に伴う応力もある。このため、あらかじめこの熱収縮分を測定しておき、この分だけ送り出し量が巻き取り量より多くなるように、制御するのがより好ましい。このような熱処理には１分以上６０分以下、より好ましくは３分以上３０分以下、さらに好ましくは５分以上１５分以下で行うのが好ましい。熱処理時間を長く取るには長い熱処理ゾーンを必要とするため、２度以上に分割して熱処理するのも好ましい。
【０２１９】
これらの熱処理は下塗り後に実施することが好ましい。これは下塗り工程の張力で寸法変化率が増大しやすいためである。またそれに加えて下塗り層中にマット粒子を含ませることでロール状熱処理の際の平面性をあげることができる。
【０２２０】
【実施例】
以下、実施例を挙げて本発明を具体的に説明するが、本発明の実施態様はこれらに限定されるものではない。
【０２２１】
支持体はＰＥＴベース１２５μｍを熱処理しないものと、熱処理をしたものを用いた。ここでＰＥＴは搬送時の搬送張力を１５００ｋＰａ、１０００ｋＰａ、４００ｋＰａと、変えたものをつくった。そして、それぞれ２０ｍ／分で搬送しながら１３０℃で１５分間熱処理を行った。
【０２２２】
実施例１
（ハロゲン化銀乳剤Ａの調製）
水９００ｍｌ中にイナートゼラチン７．５ｇ及び臭化カリウム１０ｍｇを溶解して温度３５℃、ｐＨを３．０に合わせた後、硝酸銀７４ｇを含む水溶液３７０ｍｌと（６０／３８／２）のモル比の塩化ナトリウムと臭化カリウムと沃化カリウム及び〔Ｉｒ（ＮＯ）Ｃｌ_５〕塩を銀１モル当たり１×１０^−６モル及び塩化ロジウム塩を銀１モル当たり１×１０^−６モルを含む水溶液３７０ｍｌを、ｐＡｇ７．７に保ちながらコントロールドダブルジェット法で添加した。
【０２２３】
その後４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを添加しＮａＯＨでｐＨを８、ｐＡｇ６．５に調整することで還元増感を行い平均粒子サイズ０．０６μｍ、単分散度１０％の投影直径面積の変動係数８％、〔１００〕面比率８７％の立方体沃臭化銀粒子を得た。この乳剤にゼラチン凝集剤を用いて凝集沈降させ脱塩処理を行いハロゲン化銀乳剤Ａを調製した。
【０２２４】
（ベヘン酸Ｎａ溶液の調製）
９４５ｍｌの純水にベヘン酸３２．４ｇ、アラキジン酸９．９ｇ、ステアリン酸５．６ｇを９０℃で溶解した。次に高速で攪拌しながら１．５ｍｏｌ／Ｌの水酸化ナトリウム水溶液９８ｍｌを添加した。次に濃硝酸０．９３ｍｌを加えた後、５５℃に冷却して３０分攪拌させてベヘン酸Ｎａ溶液を得た。
【０２２５】
（ベヘン酸銀とハロゲン化銀乳剤Ａのプレフォーム乳剤の調製）
上記のベヘン酸Ｎａ溶液に前記ハロゲン化銀乳剤Ａを１．５１ｇ添加し水酸化ナトリウム溶液でｐＨ８．１に調整した後に１ｍｏｌ／Ｌのアルカリの硝酸銀溶液１４７ｍｌを７分間かけて加え、さらに２０分攪拌し限外濾過により水溶性塩類を除去した。できたベヘン酸銀は平均粒子サイズ０．８μｍ、単分散度８％の粒子であった。分散物のフロックを形成後、水を取り除き、更に６回の水洗と水の除去を行った後乾燥させた。
【０２２６】
（感光性乳剤の調製）
できあがったプレフォーム乳剤を分割し、それにポリビニルブチラール（平均分子量３０００）のメチルエチルケトン溶液（１７質量％）５４４ｇとトルエン１０７ｇを徐々に添加して混合した後に、０．５ｍｍ径のＺｒＯ_２のビーズミルを用いたメディア分散機により２７．５８ＭＰａで３０℃、１０分間の分散を行った。
【０２２７】
（熱現像感光材料の作製）
前記支持体上に以下の各層を両面同時塗布し、熱現像感光材料試料を作製した。尚、乾燥は６０℃、１５分間で行った。
【０２２８】
〈バック面側塗布〉
前記支持体上に以下の組成の液を乾燥膜厚が２．５μｍになるよう塗布した。
【０２２９】
セルロースアセテートブチレート ９０ｇ
染料 Ｄ２−１ ０．４２ｇ
染料 Ｄ３−５ ０．４２ｇ
マット剤：単分散度１５％平均粒子サイズ８μｍ単分散シリカ ５．４ｇ
Ｃ_８Ｆ_１７（ＣＨ_２ＣＨ_２Ｏ）_１２Ｃ_８Ｆ_１７ ３ｇ
Ｃ_９Ｆ_１７−Ｃ_６Ｈ_４−ＳＯ_３Ｎａ １ｇ
メチルエチルケトン ９００ｇ
【０２３０】
【化７０】

【０２３１】
〈感光層面側塗布〉
（感光層下層）
バック層を塗布した面とは反対側の面上に以下の組成の液を２μｍの膜厚になるように塗布した。
【０２３２】
ブチラール樹脂（積水化成ＢＭ１） １０ｇ
メチルエチルケトン ９０ｇ
（感光層）
感光層下層の上に以下の組成の液を１０μｍの膜厚になるように塗布した。
【０２３３】

【０２３４】
【化７１】

【０２３５】
（保護層）
以下の組成の液を感光層の上層にドライ膜厚が２μｍになるよう同時塗布した。
【０２３６】

《写真性能の評価》
（露光処理）
得られた熱現像感光材料を、ビーム径（ビーム強度の１／２のＦＷＨＭ）１２．５６μｍ、レーザー出力５０ｍＷ、出力波長７８３ｎｍの半導体レーザーを搭載した単チャンネル円筒内面方式のレーザー露光装置を使用し、ミラーの回転数を変化させることにより露光時間を、出力値を変えることにより露光量を調整し、２×１０^−８秒でトンボ画像を露光した。この時のオーバーラップ係数は０．４４９にした。
【０２３７】
（熱現像処理）
露光済みの熱現像感光材料を図１の熱現像機を用いて、熱現像処理部のローラー表面材質はシリコーンゴム、平滑面はテフロン（Ｒ）不織布にして予備加熱部９０〜１００℃で５秒、熱現像処理部１２０℃で２０秒間熱現像処理を行った。
【０２３８】
なお、幅方向の温度精度は±１℃であった。
（製版機によるトンボ検出の評価）
富士写真フイルム社製 製版機Ｓ−ＦＮＲＩＩＩ（トンボ検出器、バーコードリーダーの光源波長６７０ｎｍ）を用いフィルム、ＰＳ版の搬送、ＰＳ版の露光が正しく行えるかどうか各サンプルにつき５回テストを行い搬送、露光が正しく行えた回数で得られたトンボ画像の評価を行った。結果を表１に示す。ＰＳ版は富士写真フイルム社製のＶＮＮを用いた。
【０２３９】
【表１】

【０２４０】
実施例２
実施例１において、ビニル化合物を（２７）に変更した以外は全く同様にして試料を作製し、実施例１と同様の評価を行った結果、本発明の試料が優れていた。
【０２４１】
実施例３
実施例１で作製した試料１０１〜１０５を用いて、図１のプレヒート部１の温度を変化させ現像し、実施例１と同様な評価を行った。
【０２４２】
【表２】

【０２４３】
【発明の効果】
実施例で実証した如く、本発明による熱現像感光材料およびこれを用いた画像形成方法は、写真製版用、特にスキャナー、イメージセッター用として、製版機でのセンサー適性があり優れた効果を有する。
【図面の簡単な説明】
【図１】本発明に用いられる熱現像機の一例を示す断面概略図である。
【符号の説明】
１ プレヒート部
２ 本現像部
３ 除冷部
４ ハロゲンランプヒーター内蔵ローラー
５ 搬送ローラー
６ アルミのパネルヒーター
７ 温度センサー[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a photothermographic material (hereinafter, also referred to as a “photosensitive material”) and an image forming method using the same, and particularly to a photothermographic material used for photoengraving and an image forming method using the same. More particularly, the present invention relates to a photosensitive material for a scanner and an image setter and an image forming method using the same, and more particularly, to a photothermographic material suitable for a plate making machine and an image forming method using the same.
[0002]
[Prior art]
There are many known photosensitive materials having a photosensitive layer on a support and forming an image by exposing the image. Among them, a technology for forming an image by thermal development is a system that can simplify environmental conservation and image forming means.
[0003]
In recent years, in the field of photoengraving, it has been strongly desired to reduce the amount of processing waste liquid from the viewpoint of environmental conservation and space saving. Therefore, there is a need for a technique relating to a photothermographic material for photolithography, which can be efficiently exposed by a laser scanner or a laser imagesetter, and can form a clear black image having high resolution and sharpness. Have been. These photothermographic materials eliminate the use of solution processing chemicals and can provide customers with a simpler and more environmentally friendly photothermographic processing system.
[0004]
Methods for forming an image by thermal development are described in, for example, U.S. Pat. Nos. 3,152,904 and 3,457,075; Morgan and B.M. "Thermally Processed Silver Systems" A by Shelly (Imaging Processes and Materials, Nebulette, 8th Edition, Sturge, Wall. Sturge, England). Walworth, edited by A. Shepp, page 2, 1969). Such photosensitive materials are prepared by dispersing a non-photosensitive reducible silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, silver halide), and a silver reducing agent, usually in an organic binder matrix. It is contained in. The photosensitive material is stable at room temperature, but when heated to a high temperature (for example, 80 ° C. or higher) after exposure, silver is reduced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. Generate This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the reducible silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, where the image is formed.
[0005]
On the other hand, semiconductor laser technology, which has been rapidly advanced in recent years, has made it possible to reduce the size of medical image output devices. Naturally, a technique of an infrared-sensitive photothermographic silver halide photographic material in which a semiconductor laser can be used as a light source has also been developed, and a spectral sensitization technique is disclosed in US Pat. No. 5,380,635. Sensitizing dyes for infrared-sensitive light-sensitive materials are disclosed to significantly reduce the visible absorption of antihalation dyes.Moreover, antihalation technology makes it possible to easily produce a substantially colorless light-sensitive material. it can. (See, for example, Patent Documents 1 to 6)
These photosensitive materials are used as an intermediate material in a printing process and used as a mask for producing a printing plate. In recent years, digitization and automation of work have become widespread throughout the printing process, and in the plate making process, exposure and development on a PS plate are automated by introducing a plate making machine. The plate making machine is a system which operates by reading a photosensitive material on which information (barcode or register mark) necessary for automatic conveyance or automatic exposure is written by a sensor of the plate making machine.
[0006]
These sensors use a laser diode near 670 nm.
That is, it is essential that the information written on the photosensitive material can be read at 670 nm, and it is preferable that the photosensitive material has a low Dmin (minimum density) around 670 nm, and particularly uses an antihalation dye having a small visible absorption. Become.
[0007]
Therefore, it is desired to provide a heat-developable photosensitive material having high contrast and high Dmax (highest density Dmax) photographic performance, which is substantially colorless and which is suitable for a sensor in a plate making machine. I was
[0008]
[Patent Document 1]
Japanese Patent Publication No. 3-10391
[0009]
[Patent Document 2]
Japanese Patent Publication No. 6-52387
[0010]
[Patent Document 3]
JP-A-5-341432
[0011]
[Patent Document 4]
JP-A-6-194787
[0012]
[Patent Document 5]
JP-A-6-301141
[0013]
[Patent Document 6]
JP-A-7-13295
[0014]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photothermographic material suitable for photoengraving, particularly for a scanner or an image setter, which is suitable for a sensor in a plate making machine, and an image forming method using the same. .
[0015]
[Means for Solving the Problems]
The above object of the present invention is achieved by the following configurations.
[0016]
1. In a photothermographic material containing an organic silver salt, a silver halide, a developer and a vinyl compound on a support, the density of the blackened portion and the amount of reflected light of the bare portion after the thermal development processing were measured using a Keyence FSV1 amplifier. A photothermographic material characterized in that the measured value is 50 to 150 in the blackened portion and 430 to 620 in the uncoated portion.
[0017]
2. 2. The photothermographic material according to item 1, wherein the high contrast agent is a vinyl compound represented by the general formula (G).
[0018]
3. 3. The photothermographic material according to the above item 1 or 2, further comprising a preheating section in front of the heat development section of the automatic heat development apparatus, wherein an image can be obtained by setting the temperature of the preheating section to 80 to 120 ° C. Image forming method.
[0019]
Hereinafter, the present invention will be described in detail.
The heat-developable photosensitive material of the present invention is used when a printing plate is produced by using a PS plate after thermal development.In a plate making machine, information for setting exposure conditions for the PS plate, a photographic film original, Information for setting plate making conditions such as PS plate transport conditions is held as image information and used for setting plate making conditions.
[0020]
In this case, the reading of the image information is performed by a sensor provided in the plate making machine, and the detection light of the sensor is mainly 650 to 680 nm, for example, 670 nm is used. By using the photothermographic material of the present invention, image information can be accurately read by a sensor. For this reason, appropriate plate making conditions can be reliably set, and a good printing plate can be obtained.
[0021]
The photothermographic material of the invention has an image forming layer containing an organic silver salt and a binder, and the image forming layer is preferably a photosensitive layer (emulsion layer) containing photosensitive silver halide grains. In the photothermographic material containing a reducing agent and a contrast agent, the value obtained by measuring the density of the blackened portion after the heat development process and the amount of reflected light of the actual portion using a FSV1 amplifier manufactured by KEYENCE CORPORATION was black. It is characterized by the fact that the number is 50 to 150 in the modified part and 430 to 620 in the actual part, so that the object of the present application can be achieved.
[0022]
Further, the invention of claim 3 develops the photothermographic material of the present invention by using a heat development automatic machine having a preheating section in front of the heat development section, setting the temperature of the preheating section to 80 to 120 ° C. And an image forming method for photoengraving, particularly for a scanner or an image setter, wherein an image excellent in sensor suitability in a plate making machine is obtained.
[0023]
If it is lower than 80 ° C., Dmax is insufficient, and if it is higher than 120 ° C., fog increases.
[0024]
The photothermographic material of the present invention is used when preparing a printing plate using a PS plate after heat development, and includes information for setting exposure conditions for the PS plate in a plate making machine, and a photographic film original. Information for setting plate making conditions such as PS plate transfer conditions is carried as image information, and is used for setting plate making conditions. In this case, the reading of the image information is performed by a sensor provided in the plate making machine. The detection light of the sensor is mainly 650 to 680 nm, and for example, 670 nm is used as described below. By using the photothermographic material of the present invention, image information can be accurately read by a sensor as described below. For this reason, appropriate plate-making conditions can be reliably set, and the printing process following plate-making can be smoothly performed. Therefore, good printed matter is obtained.
[0025]
The PS plate used in the present invention can be selected from a negative type, a positive type, and a negative / positive type depending on the purpose and application. Specifically, any known materials can be used. Also, the plate making method and the printing method can be appropriately selected according to the PS plate to be used and the like. Specifically, a known method is used.
The photothermographic material of the invention contains an organic silver salt. The organic silver salt is a reducible silver source, and is a silver salt of an organic acid and a hetero organic acid, particularly a long-chain (10 to 30, preferably 15 to 25) aliphatic carboxylic acid and a nitrogen-containing heterocyclic ring. Silver salts of the compounds are preferred. Organic or inorganic complexes in which the ligand has a value of 4.0 to 10.0 as the total stability constant for silver ions are also preferred. Examples of these suitable silver salts are described in RD 17029 and 29963, and include the following.
[0026]
Silver salts of organic acids, for example, silver salts of gallic acid, oxalic acid, behenic acid, stearic acid, arachidic acid, palmitic acid, lauric acid and the like. Silver carboxyalkylthiourea salts, for example, silver salts such as 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, and aldehydes with hydroxy-substituted aromatic carboxylic acids A silver salt or complex of a polymer reaction product, for example, a silver salt or complex of a reaction product of an aldehyde (formaldehyde, acetaldehyde, butyraldehyde, etc.) and a hydroxy-substituted acid (eg, salicylic acid, 3,5-dihydroxybenzoic acid); Silver salts or complexes of thiones, such as silver salts such as 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thione and 3-carboxymethyl-4-thiazoline-2-thione; Complexes, imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazo , A complex or salt of a nitrogen acid and silver selected from 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole, silver salts such as saccharin and 5-chlorosalicylaldoxime, and silver mercaptide Kind. Among them, preferred silver salts include silver behenate, silver arachidate and silver stearate.
[0027]
The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and can be obtained by a forward mixing method, a reverse mixing method, a simultaneous mixing method, or a method described in JP-A No. 9-127643. A controlled double jet method or the like is preferably used. For example, after adding an alkali metal salt (eg, sodium hydroxide, potassium hydroxide, etc.) to an organic acid to produce an organic acid alkali metal salt soap (eg, sodium behenate, sodium arachidate, etc.), a controlled double jet According to the method, the soap and silver nitrate are mixed to prepare a crystal of an organic silver salt. At that time, silver halide grains may be mixed.
[0028]
In the present invention, the organic silver salt preferably has an average particle size of 10 μm or less and is monodispersed. The average particle size of the organic silver salt refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles when the organic silver salt particles are, for example, spherical, rod-shaped, or tabular particles. The average particle size is 0.05 μm to 10 μm, preferably 0.05 μm to 5 μm, particularly preferably 0.05 μm to 1.0 μm. The monodispersion has the same meaning as that of silver halide, and preferably has a monodispersity of 1 to 30.
[0029]
In the present invention, the tabular grains of the organic silver salt preferably have 60% or more of the total organic silver. In the present invention, the tabular grains refer to those having an aspect ratio (abbreviated as AR) of 3 or more, which is a ratio between an average particle diameter and a thickness, which is represented by the following formula.
[0030]
AR = average particle size (μm) / thickness (μm)
In order to make the organic silver salt into such a shape, the crystal of the organic silver salt is obtained by dispersing and pulverizing a binder, a surfactant and the like with a ball mill or the like. Within this range, a photosensitive material having a high density and excellent image storability can be obtained.
[0031]
In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is 1 m in terms of silver amount.²It is preferably 0.5 g to 2.2 g per unit. With this range, a high-contrast image can be obtained.
[0032]
The light-sensitive silver halide used in the photothermographic material of the present invention can be produced by, for example, ammonia in the presence of a protective colloid such as gelatin by any method known in the field of photographic technology such as a single jet or double jet method. It can be prepared by any method such as a method emulsion, a neutral method and an acidic method. Thus, it can be prepared in advance and then mixed with other components of the present invention and introduced into the composition used in the present invention.
[0033]
In this case, in order to sufficiently contact the photosensitive silver halide with the organic silver salt, for example, US Pat. Nos. 3,706,564 and 3,706 as protective polymers for preparing photosensitive silver halide. No. 3,565,143, 3,748,143, and British Patent No. 1,362,970, which use polymers other than gelatin, such as polyvinyl acetal. A means for enzymatically decomposing gelatin in a light-sensitive silver halide emulsion as described in British Patent No. 1,354,186; or US Pat. No. 4,076,539. As described above, by preparing photosensitive silver halide grains in the presence of a surfactant, various means such as a means for omitting the use of a protective polymer can be applied.
[0034]
The silver halide grains function as an optical sensor, and the shape of the silver halide is not particularly limited, and may be cubic, octahedral, so-called normal crystals, non-normal crystals such as spheres, rods, and tabular grains. The silver halide composition is not particularly limited, and the halide composition may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide. In order to suppress white turbidity after image formation and obtain good image quality, the average particle size is preferably small, and the average particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.1 μm, and particularly preferably 0.1 μm to 0.1 μm. It is preferably from 02 μm to 0.08 μm. When the silver halide grains are so-called normal crystals having a cubic or octahedral shape, the grain size refers to the length of the edge of the silver halide grains.
[0035]
In the case of non-normal crystals, for example, in the case of spherical, rod-shaped, or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains. Further, the silver halide is preferably monodispersed. The term “monodispersion” as used herein means that the degree of monodispersion determined by the following equation is 40% or less. The particles are more preferably 30% or less, and particularly preferably 0.1% to 20%.
[0036]
Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The amount of silver halide is 50% or less, preferably 25% to 0.1%, based on the total amount of silver halide and an organic silver salt described below. 1%, more preferably between 15% and 0.1%.
[0037]
The photosensitive silver halide used in the photothermographic material of the present invention may also contain halide ions or the like when preparing an organic silver salt, as described in British Patent 1,447,454. By causing a halogen component to coexist with an organic silver salt forming component and injecting silver ions into the component, it is possible to generate the organic silver salt almost simultaneously.
[0038]
As still another method, a silver halide forming component is allowed to act on a previously prepared solution or dispersion of an organic silver salt or a sheet material containing the organic silver salt, so that a part of the organic silver salt is subjected to photosensitive halogenation. It can also be converted to silver. The silver halide thus formed is in effective contact with the organic silver salt and exhibits a preferable action. A silver halide-forming component is a compound capable of forming a photosensitive silver halide by reacting with an organic silver salt, and which compound is applicable and effective is determined by the following simple test. Can do things. That is, an organic silver salt is mixed with a compound to be tested, and if necessary, after heating, it is examined by an X-ray diffraction method whether there is a peak peculiar to silver halide. Silver halide-forming components confirmed to be effective by such tests include inorganic halogen compounds, onium halides, halogenated hydrocarbons, N-halogen compounds, and other halogen-containing compounds. Are U.S. Pat. Nos. 4,009,039, 3,457,075, 4,003,749, British Patent 1,498,956, and JP-A-53-27027; The details are described in JP-B Nos. 53-25420, and one example is shown below.
[0039]
(1) Inorganic halide: For example, a halide represented by MXn (where M is H, NH₄And n represents a metal atom, and n represents M is H and NH₄Represents 1 when M is a metal atom, and represents the same numerical value as its valence when M is a metal atom. Examples of the metal atom include lithium, sodium, potassium, cesium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, tin, antimony, chromium, manganese, iron, cobalt, nickel, rhodium, and cerium. Further, halogen molecules such as bromine water are also effective.
[0040]
(2) Onium halides: quaternary ammonium halides such as trimethylphenylammonium bromide, cetylethyldimethylammonium bromide and trimethylbenzylammonium bromide; quaternary phosphonium halides such as tetraethylphosphonium bromide; There are tertiary sulfonium halides such as phonium iodides.
[0041]
(3) Halogenated hydrocarbons: for example, iodoform, bromoform, carbon tetrachloride, 2-bromo-2-methylpropane and the like.
[0042]
(4) N-halogen compounds: For example, N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-bromo Oxazolinone, N-chlorophthalazinone, N-bromoacetanilide, N, N-dibromobenzenesulfonamide, N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, N- Bromourazole and the like.
[0043]
(5) Other halogen-containing compounds: for example, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromoacetic acid, 2-bromoethanol, dichlorobenzophenone and the like.
[0044]
These silver halide forming components are used in a small amount stoichiometrically with respect to the organic silver salt. Usually, the range is from 0.001 mol to 0.7 mol, preferably from 0.03 mol to 0.5 mol, per 1 mol of the organic silver salt. Two or more silver halide forming components may be used in combination within the above range. Various conditions such as a reaction temperature, a reaction time, and a reaction pressure in the step of converting a part of the organic silver salt into silver halide using the above-mentioned silver halide forming component can be appropriately set according to the purpose of production. Usually, the reaction temperature is −20 ° C. to 70 ° C., the reaction time is 0.1 second to 72 hours, and the reaction pressure is preferably set to the atmospheric pressure. This reaction is also preferably performed in the presence of a polymer used as a binder described below. The amount of the polymer used at this time is 0.01 to 100 parts by mass, preferably 0.1 to 10 parts by mass per 1 part by mass of the organic silver salt.
[0045]
The photosensitive silver halide prepared by the various methods described above can be chemically sensitized by, for example, a sulfur-containing compound, a gold compound, a platinum compound, a palladium compound, a silver compound, a tin compound, a chromium compound, or a combination thereof. . The method and procedure of this chemical sensitization are described in, for example, U.S. Pat. No. 4,036,650, British Patent 1,518,850, JP-A-51-2430, JP-A-51-78319, and JP-A-51-78319. 51-81124. Also, when a part of the organic silver salt is converted into a photosensitive silver halide by a silver halide forming component, as described in US Pat. No. 3,980,482, sensitization is achieved. May be coexisted with a low molecular weight amide compound.
[0046]
These photosensitive silver halides include illuminance failure and metals belonging to Groups 6 to 10 of the Periodic Table of the Elements, such as Rh, Ru, Re, Ir, Os, and Fe, for adjusting the gradation. An ion, a complex thereof, or a complex ion can be contained. It is particularly preferable to add as a complex ion.₆ ^2-And the like may be added.
[0047]
Examples of the reducing agent used in the photothermographic material of the present invention include generally known reducing agents, such as phenols, polyphenols having two or more phenol groups, naphthols, bisnaphthols, Polyhydroxybenzenes having the above hydroxyl groups, polyhydroxynaphthalenes having two or more hydroxyl groups, ascorbic acids, 3-pyrazolidones, pyrazolin-5-ones, pyrazolines, phenylenediamines, hydroxylamines, hydroquinone mono Examples include ethers, hydroxamic acids, hydrazides, amide oximes, N-hydroxyureas, and the like. More specifically, for example, U.S. Patent Nos. 3,615,533, 3,679,426, and No. 3,672,904, No. 3,751,252, No. 3,78 No. 3,949, No. 3,801,321, No. 3,794,488, No. 3,893,863, No. 3,887,376, No. 3,770,448, No. No. 3,819,382, No. 3,773,512, No. 3,839,048, No. 3,887,378, No. 4,009,039, No. 4,021, No. 240, British Patent No. 1,486,148 or Belgian Patent No. 786,086 and JP-A-50-36143, JP-A-50-36110, JP-A-50-116023, JP-A-50-99719, No. 50-140113, No. 51-51933, No. 51-23721, No. 52-84727 or JP-B-51-35851, and there are reducing agents specifically exemplified. Of known reducing agents It can be appropriately selected for use from. As a selection method, the simplest method is to actually prepare a photothermographic material and evaluate the photographic performance to determine the superiority of the reducing agent used.
[0048]
Among the above reducing agents, when a silver aliphatic carboxylate is used as the organic silver salt, preferred reducing agents include polyphenols in which two or more phenol groups are linked by an alkylene group or sulfur, particularly a phenol group. At least one of the positions adjacent to the hydroxy-substituted position is substituted with an alkyl group (eg, methyl group, ethyl group, propyl group, t-butyl group, cyclohexyl group, etc.) or an acyl group (eg, acetyl group, propionyl group, etc.) Polyphenols in which two or more phenol groups are linked by an alkylene group or sulfur, for example, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane, 1,1- Bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane, 1,1-bis (2-hydroxy- , 5-Di-tert-butylphenyl) methane, 2-hydroxy-3-tert-butyl-5-methylphenyl- (2-hydroxy-5-methylphenyl) methane, 6,6'-benzylidene-bis (2, 4-di-t-butylphenol), 6,6'-benzylidene-bis (2-t-butyl-4-methylphenol), 6,6'-benzylidene-bis (2,4-dimethylphenol), 1,1 -Bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1,1,5,5-tetrakis (2-hydroxy-3,5-dimethylphenyl) -2,4-ethylpentane, U.S. Pat. No. 3,582, such as 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-di-tert-butylphenyl) propane and the like. , 903, 4,021,249 or British Patent 1,486,148, and JP-A-51-51933, JP-A-50-36110, JP-A-50-116023, JP-A-52-84727. Or the bisphenols described in U.S. Pat. No. 3,672,904, for example, 2,2'-dihydroxy-1,1'-binaphthyl , 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6'-dinitro-2,2'-dihydroxy-1,1'-binaphthyl, bis (2-hydroxy-1 -Naphthyl) methane, 4,4'-dimethoxy-1,1'-dihydroxy-2,2'-binaphthyl and the like, further described in U.S. Pat. No. 3,801,321. Sulfonamidophenol or sulfonamidonaphthols, for example, 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 4-benzenesulfonamidonaphthol and the like. I can do it.
[0049]
The amount of the reducing agent used in the photothermographic material of the present invention varies depending on the type of the organic silver salt and the reducing agent, and other additives. 10 mol, preferably 0.1 mol to 3 mol is appropriate. Further, within this range, two or more of the above-mentioned reducing agents may be used in combination. In the present invention, it is sometimes preferable to add and mix the reducing agent to the photosensitive solution immediately before the coating, since the photographic performance fluctuation due to the stagnation time of the photosensitive solution is small.
[0050]
The photothermographic material of the invention contains the vinyl compound as a contrast agent. As the vinyl compound, a compound represented by the general formula (G) is preferable. These vinyl compounds are preferable because they exhibit a greater effect as a high contrast agent in a heat development system than hydrazine derivatives known as high contrast agents.
[0051]
In the general formula (G), the electron-withdrawing group represented by X is a substituent whose Hammett's substituent constant σp can take a positive value.
[0052]
Specifically, a substituted alkyl group (eg, halogen-substituted alkyl), a substituted alkenyl group (eg, cyanovinyl), a substituted / unsubstituted alkynyl group (eg, trifluoromethylacetylenyl, cyanoacetylenyl), and a substituted aryl group (eg, cyanovinyl) Phenyl, etc.), substituted / unsubstituted heterocyclic groups (pyridyl, triazinyl, benzoxazolyl, etc.), halogen atoms, acyl groups (acetyl, trifluoroacetyl, formyl, etc.), thioacetyl groups (thioacetyl, thioformyl, etc.), oxalyl Group (eg, methyl oxalyl), oxyoxalyl group (eg, ethoxyl), thiooxalyl group (eg, ethylthiooxalyl), oxamoyl group (eg, methyl oxamoyl), oxycarbonyl group (eg, ethoxycarbonyl), carboxyl group, thiocarbonyl group (eg, Ethylthiocarbonyl, etc.) Bamoyl group (methylcarbamoyl, phenylcarbamoyl, etc.), thiocarbamoyl group (ethylthiocarbamoyl, phenylthiocarbamoyl, etc.), sulfonyl group (methanesulfonyl, etc.), sulfinyl group (methanesulfinyl, etc.), oxysulfonyl group (ethoxysulfonyl, etc.), A thiosulfonyl group (such as ethylthiosulfonyl), a sulfamoyl group (such as sulfamoyl and methylsulfamoyl), an oxysulfinyl group (such as methoxysulfinyl), a thiosulfinyl group (such as methylthiosulfinyl), a sulfinamoyl group (such as methylsulfinamoyl), Sphinamoyl group (eg, methylsulfinamoyl), phosphoryl group (eg, bis (ethoxy) -phosphoryl), cyano group, nitro group, imidoyl group (acetimidoyl, N-phenylacetyl) Imidoyl, etc.), N-acyl imidoyl group (N-acetyl imidoyl, etc.), N-sulfonylimidoyl group (N-methanesulfonyl imidoyl, etc.), dicyanoethylene group (2,2-dicyanoethylene, etc.), ammonium group , A sulfonium group, a phosphonium group, a pyrylium group, and an immonium group, and a heterocyclic group in which an ammonium group, a sulfonium group, a phosphonium group, an immonium group, and the like form a ring is also included. A substituent having a σp value of 0.30 or more is particularly preferred.
[0053]
Examples of the alkyl group represented by W include methyl, ethyl, trifluoromethyl and the like, examples of the alkenyl group include vinyl, halogen-substituted vinyl and cyanovinyl, and examples of the alkynyl group include acetylenyl and cyanoacetylenyl. Examples of the heterocyclic group include nitrophenyl, cyanophenyl, and pentafluorophenyl, and examples of the heterocyclic group include pyridyl, pyrimidyl, triazinyl, succinimide, tetrazolyl, triazolyl, imidazolyl, and benzoxazolyl.
[0054]
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.Examples of the acyl group include unsubstituted alkanoyl such as formyl, acetyl, propionyl and cyclohexanecarbonyl, and trichloroacetyl, trifluoroacetyl and methylthioacetyl. Substituted benzoyls such as substituted alkanoyl, benzoyl, tolyl, and dicyanobenzoyl; thioacyl groups such as thioacetyl; oxalyl groups such as ethyl oxalyl, methyl oxalyl, and butyl oxalyl; and oxyoxalyl groups such as ethoxy. Groups such as oxalyl, methoxyethoxyoxalyl, and 2,2,3,3-tetrafluoropropoxyoxalyl; thiooxalyl groups such as ethylthiooxalyl; and oxamoyl groups such as ethyl oxalyl. Yl, a substituted or unsubstituted oxamoyl group such as methylthioethyl oxamoyl, an oxycarbonyl group is ethoxycarbonyl, a substituted or unsubstituted group such as methylthioethoxycarbonyl group, and a thiocarbonyl group is methylthiocarbonyl or ethyl. And groups such as thiocarbonyl.
[0055]
Examples of the carbamoyl group represented by W include optionally substituted groups such as methylcarbamoyl, ethylcarbamoyl, phenylcarbamoyl, pyridylcarbamoyl, and piperidinylcarbamoyl; and thiocarbamoyl groups include ethylthiocarbamoyl and phenylthio. Carbamoyl, piperidinyl thiocarbamoyl, etc., as a sulfonyl group, methanesulfonyl, ethanesulfonyl, butanesulfonyl, trifluoromethanesulfonyl, etc., as a sulfinyl group, methanesulfinyl, etc., as an oxysulfonyl group Methoxysulfinyl, ethoxysulfinyl, etc., thiosulfonyl, ethylthiosulfinyl, etc., and sulfamoyl, sulfamoyl, methylsulfamoyl, etc. When the group is an oxysulfinyl group, a group such as methoxysulfinyl, the thiosulfinyl group is a group such as methylthiosulfinyl, the sulfinamoyl group is a group such as methylsulfinamoyl, and the phosphoryl group is bis ( And groups such as alkoxyphosphoryl such as ethoxy) -phosphoryl.
[0056]
Further, as an alkoxy group represented by W, a group such as ethoxy and cyclohexyloxy, a group such as phenoxy as an aryloxy group, a group such as pyridyloxy as a heterocyclic oxy group, a mercapto group, and an alkylthio group Is a group such as ethylthio, cyclohexylthio, etc., an arylthio group is a group such as phenylthio, a heterocyclic thio group is a group such as pyridylthio, an amino group, an alkylamino group is dimethylamino, 2-chloroethylamino, Groups such as morpholino and pyrrolidinyl; arylamino groups such as anilino groups; heteroarylamino groups such as pyridylamino groups and benzimidazolylamino groups; acylamino groups such as acetamido, trifluoroacetamide and heptafluorobutanamide Base, As the oxycarbonylamino group, a group such as ethoxycarbonylamino, as the ureido group, a group such as methylureide, phenylureide, p-cyanophenylureide, and as the sulfonamide group, methanesulfonamide, trifluoromethanesulfonamide, or the like. Examples of the group and the oxysulfonylamino group include groups such as ethoxysulfonylamino, and examples of the sulfamoylamino group include groups such as methylsulfamoyl, phenylsulfamoyl, and 3-cyano-4-chlorophenylsulfamoyl. Can be
[0057]
Examples of the imidoyl group represented by W include groups such as acetimidoyl and N-phenylacetimidoyl, and examples of the N-acyl imidoyl group include N-acetyl-acetimidoyl and N-formyl-formimidoyl. , N-trifluoroacetyl-trifluoroacetimidoyl and the like; N-sulfonylimidoyl groups such as N-methanesulfonylacetoimidoyl, N-trifluoromethylsulfonyl-formimidoyl and the like; dicyanoethylene group A group such as 2,2-dicyanoethylene, 2,2-dicyano-1-methylethylene, 2,2-dicyano-1-trifluoromethylethylene, 1,2,2-tricyanoethylene, and an ammonium group Is a group such as trimethylammonio or pyridinio, and a 2-pyridinio group or 2-imidazoly Groups such as the sulfonium group, groups such as dimethylsulfoxide niobium group, a phosphonium group, groups such as triphenylphosphonio group, the pyrylium group include groups such as 2-Piranio group. Among them, W is preferably an electron-withdrawing group having a positive σp value, more preferably 0.30 or more.
[0058]
R represents a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxy group, alkoxy group (methoxy group, ethoxy group, etc.), aryloxy group (phenoxy group, p-methoxyphenoxy group, o-chlorophenoxy group, etc.) , A heterocyclic oxy group (such as a pyridyloxy group), an alkenyloxy group (such as an allyloxy group), an acyloxy group (such as an acetoxy group, a propionyloxy group, and a benzoyloxy group), and an alkoxycarbonyloxy group (an ethoxycarbonyloxy group and a butoxycarbonyloxy group). Group), aminocarbonyloxy group (ethylcarbamoyloxy group, propylcarbamoyloxy group, phenylcarbamoyloxy group, etc.), mercapto group, alkylthio group (methylthio group, butylthio group, etc.), arylthio group (phenylthio group, p-methoxyphenyl group). Nilthio group, p-chlorophenyl group, etc.), heterocyclic thio group (pyridylthio group, etc.), alkenylthio group (allylthio group, etc.), acylthio group (acetylacetyl group, etc.), alkoxycarbonylthio group (methoxycarbonylthio group, ethoxycarbonyl) Thio group), aminocarbonyl thio group (ethyl carbamoyl thio group, propyl carbamoyl thio group, phenyl carbamoyl thio group, etc.), organic or inorganic salt of hydroxy group or mercapto group (eg, sodium salt, potassium salt, silver salt, etc.) ), Amino group, alkylamino group (group such as dimethylamino, 2-chloroethylamino, morpholino, pyrrolidinyl), cyclic amino group (for example, pyrrolidino group), acylamino group (acetamide, trifluoroacetamide, heptafluorobutanamide, etc.) ), Oxy A rubonylamino group (such as ethoxycarbonylamino), a heterocyclic group (such as a 5- to 6-membered nitrogen-containing heterocyclic ring such as a benztriazolyl group, an imidazolyl group, a triazolyl group, or a tetrazolyl group); and a ureido group (methylureido or phenylureido) , P-cyanophenylureido, etc.) and a sulfonamide group (methanesulfonamide, trifluoromethanesulfonamide, etc.). X and W, and X and R may be bonded to each other to form a cyclic structure (for example, the ring formed by X and W includes pyrazolone, pyrazolidinone, cyclopentanedione, β-ketolactone, β-ketolactam, etc. Is included).
[0059]
Further, among the substituents of R, a hydroxy group, a mercapto group, an alkoxy group, an alkylthio group, a halogen atom, an organic or inorganic salt of a hydroxy group or a mercapto group, for example, a sodium salt, a potassium salt, a silver salt, Further, among the heterocyclic groups, preferably include a 5- to 6-membered nitrogen-containing heterocyclic ring such as a benztriazolyl group, an imidazolyl group, a triazolyl group, a tetrazolyl group, and more preferably a hydroxy group, an alkoxy group, An organic or inorganic salt of a hydroxy group or a mercapto group and a heterocyclic group are exemplified, and an organic or inorganic salt of a hydroxy group, a hydroxy group or a mercapto group is particularly preferred.
[0060]
Further, among the substituents of X and W, those having a thioether bond in the substituent are preferable.
[0061]
Next, specific examples of the compound represented by the general formula will be shown below, but it should not be construed that the invention is limited thereto.
[0062]
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[0063]
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[0064]
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[0065]
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[0066]
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[0067]
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[0068]
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[0069]
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[0070]
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[0071]
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[0072]
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[0073]
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[0074]
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[0075]
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[0076]
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[0077]
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[0078]
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[0079]
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[0080]
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[0081]
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[0082]
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[0083]
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[0084]
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[0085]
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[0086]
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[0087]
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[0088]
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[0089]
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[0090]
The layer to which the vinyl compound is added is a photosensitive layer containing silver halide and / or a layer adjacent to the photosensitive layer. The optimum amount is not uniform depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, and the like.^-6Mol-10^-1About 10 moles, especially 10^-5Mol-10^-2A molar range is preferred. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating.
[0091]
These vinyl compounds can be used by dissolving them in a suitable organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, and the like. it can. Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a powder of a vinyl compound can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and used.
[0092]
The photothermographic material of the present invention may contain a hydrazine derivative in addition to the vinyl compound, and its effect can be enhanced.
[0093]
As the hydrazine derivative, a compound represented by the following general formula [H] is preferable.
[0094]
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[0095]
Where A₀Is an aliphatic group, an aromatic group, a heterocyclic group or -G which may have a substituent.₀-D₀And B0 represents a blocking group;₁, A₂Each represents a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. Where G₀Is -CO-, -COCO-, -CS-, -C (= NG₁D₁) -Group, -SO-group, -SO₂-Group or -P (O) (G₁D₁)-Group;₁Is a mere bond, -O- group, -S- group or -N (D₁)-Group;₁Represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and a plurality of D₁If they are present, they can be the same or different. D₀Represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.
[0096]
In the general formula [H], A₀The aliphatic group represented by preferably has 1 to 30 carbon atoms, particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, a t-butyl group Octyl group, cyclohexyl group and benzyl group, which are further substituted (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group). Ureido group).
[0097]
In the general formula [H], A₀The aromatic group represented by is preferably a monocyclic or condensed-ring aryl group, such as a benzene ring or a naphthalene ring.₀The heterocyclic group represented by is preferably a heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur, and oxygen atom in a single ring or a condensed ring, for example, a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, A pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, a furan ring;₀-G represented by₀-D₀In the group, G₀Is -CO-, -COCO-, -CS-, -C (= NG₁D₁) -Group, -SO-group, -SO₂-Group or -P (O) (G₁D₁)-Represents a group. G1 is a mere bond, -O- group, -S- group or -N (D₁)-Group;₁Represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and a plurality of D₁If they are present, they can be the same or different. D₀Represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.₀Examples thereof include a hydrogen atom, an alkyl group, an alkoxy group, an amino group and the like.
[0098]
A₀An aromatic group, a heterocyclic group and -G₀-D₀The group may have a substituent.
A₀Are particularly preferably an aryl group and -G₀-D₀Group.
[0099]
In the general formula [H], A₀Preferably contains at least one diffusion-resistant group or silver halide-adsorbing group. As the anti-diffusion group, a ballast group commonly used in immobile photographic additives such as couplers is preferable, and the ballast group is a photographically inert alkyl group, alkenyl group, alkynyl group, alkoxy group, phenyl group, Examples thereof include a phenoxy group and an alkylphenoxy group, and the total number of carbon atoms in the substituent is preferably 8 or more.
[0100]
In the general formula [H], examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, and And the adsorbing group described in JP-A-90439.
[0101]
In the general formula [H], B₀Represents a blocking group, preferably -G₀-D₀Group, G₀Is -CO-, -COCO-, -CS-, -C (= NG₁D1) -group, -SO- group, -SO₂-Group or -P (O) (G₁D₁)-Represents a group. Preferred G₀Include a -CO- group and a -COCO- group.₁Is a mere bond, -O- group, -S- group or -N (D₁)-Group;₁Represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and a plurality of D₁If they are present, they can be the same or different. D₀Represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.₀Examples thereof include a hydrogen atom, an alkyl group, an alkoxy group, an amino group and the like. A₁, A₂Each represents a hydrogen atom or one is a hydrogen atom and the other is an acyl group (acetyl group, trifluoroacetyl group, benzoyl group, etc.), a sulfonyl group (methanesulfonyl group, toluenesulfonyl group, etc.) or an oxalyl group (ethoxalyl group, etc.) .
[0102]
Specific examples of the compound represented by the general formula [H] are shown below.
[0103]
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[0104]
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[0105]
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[0106]
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[0107]
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[0108]
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[0109]
Other hydrazine derivatives that can be preferably used include compounds H-1 to H-29 described in U.S. Pat. No. 5,545,505, columns 11 to 20, and U.S. Pat. No. 5,464,738, columns 9 to 9. Compounds 1 to 12 described in 11.
[0110]
These hydrazine derivatives can be synthesized by a known method. When a hydrazine derivative is used, the added layer is a photosensitive layer containing a silver halide emulsion and / or a layer adjacent to the photosensitive layer. The optimum amount is not uniform depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, and the like.^-6Mol-10^-1About 10 moles, especially 10^-5Mol-10^-2A molar range is preferred.
[0111]
In the present invention, it is also effective to use hydrazine derivatives represented by the following formulas (H-1) to (H-4) together with the formula (G).
[0112]
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[0113]
R₁₁, R₁₂And R_ThirteenEach independently represents a substituted or unsubstituted aryl group or heteroaryl group. R₁₄Represents a heteroaryloxy group or a heteroarylthio group. A₁, A₂Represents a hydrogen atom or one of them represents a hydrogen atom and the other represents an alkylsulfonyl group, an oxalyl group or an acyl group.
[0114]
R₁₁, R₁₂And R_ThirteenEach independently represents a substituted or unsubstituted aryl group or heteroaryl group, and specific examples of the aryl group include phenyl, p-methylphenyl, and naphthyl. Specific examples of the heteroaryl group include a triazole residue, an imidazole residue, a pyridine residue, a furan residue, and a thiophene residue.
[0115]
Also, R₁₁, R₁₂And R_ThirteenMay be bonded via an arbitrary linking group. R₁₁, R₁₂And R_ThirteenHas a substituent, examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (eg, a pyridinio group), a hydroxy group, An alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a urethane group, a carboxyl group, an imide group, Amino group, carbonamido group, sulfonamido group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, (alkyl, aryl or heterocyclic) thio group , A mercapto group, (alkyl or Reel) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group, sulfamoyl group, acylsulfamoyl group, (alkyl or aryl) sulfonyluleido group, (alkyl or aryl) sulfonylcarbamoyl group, halogen atom, cyano group, nitro And phosphoric acid amide groups. R₁₁, R₁₂And R_ThirteenAre preferably substituted or unsubstituted phenyl groups, and more preferably₁₁, R₁₂And R_ThirteenIs an unsubstituted phenyl group.
[0116]
R₁₄Represents a heteroaryloxy group or a heteroarylthio group. Specific examples of the heteroaryloxy group include a pyridyloxy group, a pyrimidyloxy group, an indolyloxy group, a benzothiazolyloxy group, a benzimidazolyloxy group, and a furyloxy group. Group, thienyloxy group, pyrazolyloxy group, imidazolyloxy group and the like. Specific examples of the heteroarylthio group include a pyridylthio group, a pyrimidylthio group, an indolylthio group, a benzothiazolylthio group, a benzimidazolylthio group, a furylthio group, a thienylthio group, a pyrazolylthio group, and an imidazolylthio group. R₁₄Are preferably a pyridyloxy group and a thienyloxy group.
[0117]
A₁, A₂Represents a hydrogen atom, or one of them is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group (ethoxalyl, etc.). Preferably A₁, A₂Both cases are hydrogen atoms.
[0118]
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[0119]
R₂₁Represents a substituted or unsubstituted alkyl group, aryl group or heteroaryl group. R₂₂Represents a hydrogen atom, an alkylamino group, an arylamino group, or a heteroarylamino group.
[0120]
R₂₁Represents a substituted or unsubstituted alkyl group, aryl group or heteroaryl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a t-butyl group, a 2-octyl group, a cyclohexyl group, a benzyl group, and a diphenyl group. And a methyl group. Specific examples of the aryl group and the heteroaryl group include R₁₁, R₁₂And R_ThirteenAnd the same. Also, R₂₁Has a substituent, specific examples of the substituent include R₁₁, R₁₂And R_ThirteenAnd the same substituents as mentioned above. R₂₁Is preferably an aryl group or a heteroaryl group, and particularly preferably a substituted or unsubstituted phenyl group.
[0121]
R₂₂Represents a hydrogen atom, an alkylamino group, an arylamino group, or a heteroarylamino group. Specific examples of the alkylamino group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a dimethylamino group, and a diethylamino group. And an ethylmethylamino group. Examples of the arylamino group include an anilino group, and examples of the heteroaryl group include a thiazolylamino group, a benzimidazolylamino group, and a benzthiazolylamino group. R₂₂Is preferably a dimethylamino group or a diethylamino group.
[0122]
A₁, A₂Is A described in the general formula (H-1)₁, A₂Is the same as
[0123]
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[0124]
R₃₁, R₃₂Represents a monovalent substituent, and the monovalent substituent is represented by R₁₁, R₁₂And R_ThirteenExamples of the substituent include, but preferably, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, and an amino group. More preferably, it is an aryl group or an alkoxy group. Particularly preferred is R₃₁And R₃₂Is at least one tert-butoxy group, and another preferred structure is R₃₁Is a phenyl group,₃₂Is a tert-butoxy group.
[0125]
G₃₁, G₃₂Is-(CO) p-, -C (= S)-, sulfonyl, sulfoxy, -P (= O) R₃₃-P or an iminomethylene group; p represents an integer of 1 or 2;₃₃Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or an amino group. Where G₃₁Is a sulfonyl group, G₃₂Is not a carbonyl group. G₃₁, G₃₂Is preferably a -CO- group, a -COCO- group, a sulfonyl group or -CS-, and more preferably a -CO- group or a sulfonyl group.
[0126]
A₁, A₂Is A described in the general formula (H-1)₁, A₂Is the same as In the general formula (H-3), G₃₁And G₃₂Is particularly preferably a carbonyl group or a sulfonyl group.
[0127]
In the general formula (H-3), R₃₁, R₃₂It is particularly preferred that at least one has the structure shown below.
[0128]
-OC (CH₃)₃
[0129]
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[0130]
R₄₁, R₄₂And R₄₃Each independently represents a substituted or unsubstituted aryl group or heteroaryl group. R₄₄, R₄₅Represents an unsubstituted or substituted alkyl group. A₁, A₂Represents a hydrogen atom or one of them represents a hydrogen atom and the other represents an alkylsulfonyl group, an oxalyl group or an acyl group.
[0131]
R₄₁, R₄₂And R₄₃Is R in general formula (H-1)₁₁, R₁₂And R_ThirteenIs synonymous with R₄₁, R₄₂And R₄₃Are preferably substituted or unsubstituted phenyl groups, and more preferably₄₁, R₄₂And R₄₃Is an unsubstituted phenyl group. R₄₄, R₄₅Represents an unsubstituted or substituted alkyl group, and specific examples include a methyl group, an ethyl group, a t-butyl group, a 2-octyl group, a cyclohexyl group, a benzyl group, and a diphenylmethyl group. R₄₄, R₄₅Are preferably ethyl groups.
[0132]
A₁, A₂Is A described in the general formula (H-1)₁, A₂Is the same as Specific representative examples of the compounds represented by formulas (H-1) to (H-4) are shown below.
[0133]
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[0134]
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[0135]
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[0136]
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[0137]
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[0138]
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[0139]
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[0140]
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[0141]
The compounds represented by these general formulas (H-1) to (H-4) can be easily synthesized by a known method. For example, it can be synthesized with reference to US Pat. No. 5,464,738 or US Pat. No. 5,496,695.
[0142]
When these hydrazine derivatives are used, the added layer is a photosensitive layer containing a silver halide emulsion and / or a layer adjacent to the photosensitive layer. The optimum amount varies depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., and is not uniform.^-6Mol-10^-1About 10 moles, especially 10^-5Mol-10^-2A molar range is preferred.
[0143]
The hydrazine derivative can be dissolved in a suitable organic solvent, or formed after forming an emulsified dispersion, or added by a method known as a solid dispersion method.
[0144]
The photothermographic material of the present invention includes a hydroxylamine compound, an alkanolamine compound and an ammonium phthalate compound described in US Pat. No. 5,545,505, and a hydroxamic acid described in US Pat. No. 5,545,507. Compounds, N-acyl-hydrazine compounds described in U.S. Pat. No. 5,558,983, acrylonitrilo compounds described in U.S. Pat. No. 5,545,515, and benzhydrides described in U.S. Pat. No. 5,937,449. It is preferable to add a high contrast accelerator such as a roll, a hydrogen atom donor compound such as diphenylphosphine, dialkylpiperidine, or alkyl-β-ketoester. Among them, a quaternary onium compound represented by the following general formula (P) and an amino compound represented by the general formula [Na] are preferably used.
[0145]
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[0146]
In the formula, Q represents a nitrogen atom or a phosphorus atom;₁, R₂, R₃And R₄Each represents a hydrogen atom or a substituent;⁻Represents an anion. Note that R₁~ R₄May be connected to each other to form a ring.
[0147]
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[0148]
In the general formula [Na], R₁₁, R₁₂And R_ThirteenRepresents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group, a substituted aryl group, or a saturated or unsaturated heterocyclic ring. R₁₁, R₁₂And R_ThirteenMay form a ring. Particularly preferred are aliphatic tertiary amine compounds.
[0149]
These compounds preferably have a diffusion-resistant group or a silver halide adsorbing group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable.₀And those having the same meanings as those of the diffusion-resistant group in the above. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group.
[0150]
More preferred nucleation accelerators than the nucleation accelerator represented by the general formula [Na] include compounds represented by the following general formula [Na2].
[0151]
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[0152]
In the general formula [Na2], R₁, R₂, R₃And R₄Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group, a substituted aryl group, or a saturated or unsaturated heterocyclic ring. These can be linked to each other to form a ring. Also, R₁And R₂, R₃And R₄Are not simultaneously hydrogen atoms. X represents an S, Se or Te atom. L₁And L₂Each represents a divalent linking group. Specific examples include the following groups or combinations thereof and groups having appropriate substituents (for example, an alkylene group, an alkenylene group, an arylene group, an acylamino group, a sulfonamide group, and the like).
[0153]
-CH₂-, -CH = CH-, -C₂H₄-, Pyridinediyl, -N (Z₁)-(Z₁Represents a hydrogen atom, an alkyl group or an aryl group), -O-, -S-,-(CO)-,-(SO₂)-, -CH₂N-.
[0154]
Also, L₁Or L₂The linking group represented by preferably contains at least one or more of the following structures in the linking group.
[0155]
-[CH₂CH₂O]-,-[C (CH₃) HCH₂O]-,-[OC (CH₃) HCH₂O]-,-[OCH₂C (OH) HCH₂]-.
[0156]
Specific examples of the nucleation accelerator represented by the general formula [Na] or [Na2] are shown below.
[0157]
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[0158]
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[0159]
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[0160]
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[0161]
In the general formula (P), R₁~ R₄Examples of the substituent represented by are an alkyl group (methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, etc.), an alkenyl group (allyl group, butenyl group, etc.), an alkynyl group (propargyl group, butynyl group). Group), an aryl group (phenyl group, naphthyl group, etc.), a heterocyclic group (piperidinyl group, piperazinyl group, morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group, sulfolanyl group, etc.), And an amino group.
[0162]
R₁~ R₄Can be formed by connecting to each other a piperidine ring, a morpholine ring, a piperazine ring, a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring and the like.
[0163]
R₁~ R₄The group represented by may have a substituent such as a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group, and an aryl group.
[0164]
R₁, R₂, R₃And R₄Are preferably a hydrogen atom and an alkyl group. Examples of the anion represented by X- include inorganic and organic anions such as a halogen ion, a sulfate ion, a nitrate ion, an acetate ion, and a p-toluenesulfonic acid ion.
[0165]
More preferred are a compound represented by the following formula (Pa), (Pb) or (Pc), and a compound represented by the following formula [T].
[0166]
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[0167]
Where A₁, A₂, A₃, A₄And A₅Represents a group of nonmetallic atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom, and a sulfur atom, and may be condensed with a benzene ring. A₁, A₂, A₃, A₄And A₅May have a substituent and may be the same or different.
[0168]
Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. A₁, A₂, A₃, A₄And A₅Preferred examples include a 5- to 6-membered ring (each ring of pyridine, imidazole, thiozole, oxazole, pyrazine, pyrimidine and the like), and more preferred examples include a pyridine ring.
[0169]
BP represents a divalent linking group, and m represents 0 or 1. Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene group, and -SO₂-, -SO-, -O-, -S-, -CO-, -N (R₆)-(R₆Represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferably, Bp is an alkylene group or an alkenylene group.
[0170]
R₁, R₂And R₅Each represents an alkyl group having 1 to 20 carbon atoms. Also, R₁And R₂May be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group.₁, A₂, A₃, A₄And A₅Are the same as the substituents exemplified as the substituent for.
[0171]
R₁, R₂And R₅Is preferably an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.
[0172]
Xp⁻Represents a counter ion necessary for balancing the charge of the whole molecule, for example, chloride ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate and the like. np represents the number of counter ions required to balance the charge of the entire molecule, and np is 0 in the case of an internal salt.
[0173]
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[0174]
The substituent R of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T]₅, R₆, R₇Is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property.
[0175]
The Hammett's sigma value in the phenyl group is described in many literatures, for example, C.I., described in Journal of Medical Chemistry, Vol. 20, p. 304, 1977. The group having a particularly preferable negative sigma value is, for example, a methyl group (σP = −0.17 or less, σP value in any case), an ethyl group (− 0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), iso-propyl group (-0.15), cyclobutyl group (-0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.15), cyclohexyl group (-0.22), amino group (-0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27), ethoxy group (-0.24), propoxy group (-0.25), butoxy group (-0.32 ), A pentoxy group (-0.34) and the like. Is also useful as a substituent of the compound of the general formula [T].
[0176]
n represents 1 or 2, and XTn⁻As the anion represented by, for example, chloride ions, bromide ions, halide ions such as iodide ions, nitric acid, sulfuric acid, acid radicals of inorganic acids such as perchloric acid, sulfonic acid, acid radicals of organic acids such as carboxylic acid, Anionic activators, specifically, lower alkylbenzene sulfonic acid anions such as p-toluene sulfonic acid anion, higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion, and higher alkyl sulfate anions such as lauryl sulfate anion Boric acid-based anions such as tetraphenylboron, dialkylsulfosuccinate anions such as di-2-ethylhexylsulfosuccinate anion, higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers such as polyacrylate anions. Mention may be made of things like.
[0177]
Hereinafter, specific examples of the quaternary onium compound will be given below, but it should not be construed that the invention is limited thereto.
[0178]
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[0179]
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[0180]
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[0181]
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[0182]
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[0183]
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[0184]
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[0185]
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[0186]
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[0187]
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[0188]
The quaternary onium compound can be easily synthesized according to a known method. For example, the tetrazolium compound can be synthesized according to Chemical Reviews 55 p. 335-483 can be referred to.
[0189]
The addition amount of these quaternary onium compounds is 1 × 10 5 per mole of silver halide.^-8About 1 mol, preferably 1 × 10^-7~ 1 × 10^-1Is a mole. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating.
[0190]
In the present invention, compounds represented by the following formulas (A-1) to (A-4) can be used as a development accelerator.
[0191]
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[0192]
In the general formula (A-1), R₅₁Represents an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amide group, an aryl group, an aralkyl group, an aryloxy group, an arylthio group, an anilino group or a heterocyclic group. In the general formula (A-2), R₆₁, R₆₂Represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an aliphatic or aromatic heterocyclic group, or a cycloaliphatic group. In the general formula (A-3), R₇₁Represents a hydroxyalkyl group;₇₂, R₇₃Are each independently a hydrogen atom, an alkyl group,-(CH₂) N-N-R₇₄(R₇₅) (N is an integer of 1 to 10, R₇₄, R₇₅Each independently represents a hydrogen atom or an alkyl group). In the general formula (A-4), R₈₁Represents a hydrazino group, an alkylamino group, a sulfonylamino group, a ureido group, an oxycarbonylamino group, an alkynyl group or an unsubstituted amino group. R₈₂Represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and X represents a hydrogen atom, an alkyl group, a carbamoyl group or an oxycarbonyl group. R₈₁And R₈₂And may combine with each other to form a 5- to 7-membered ring.
[0193]
The addition amount of these compounds is 1 × 10 5 per mole of silver halide.^-8About 1 mol, preferably 1 × 10^-7~ 1 × 10^-1Is a mole. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating.
[0194]
Further, the photothermographic material of the invention may contain the following compounds as development accelerators.
[0195]
2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2,2'-dithiobis-benzothiazole, 3- Mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto- 4 (3H) -quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-me Capto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 4-hydrokilocy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine , 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 2-mercapto-4-phenyloxazole and the like.
[0196]
Phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, and cyclic imides such as quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione; Naphthalimide (for example, N-hydroxy-1,8-naphthalimide); cobalt complex (for example, cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, Mercaptans exemplified by -mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole; N- (aminomethyl) aryldicarboximides (for example, (N, N-dimethylaminomethyl Phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives and certain photobleaching agents such as N, N'-hexamethylenebis (1 -Carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-diazaoctane) bis (isothiuronium trifluoroacetate) and (2-tribromomethylsulfonyl)-(benzothiazole)); Ethyl-5-[(3-ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, a phthalazinone derivative or a metal salt, or 4- (1- Naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxy Derivatives such as phthalazinone and 2,3-dihydro-1,4-phthalazinedione; combinations of phthalazinone with phthalic acid derivatives (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride) Phthalazine, phthalazine derivatives or metal salts, or derivatives such as 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine and 2,3-dihydrophthalazine; phthalazine and phthalic acid derivatives ( For example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazolinedione, benzoxazine or naphthoxazine derivatives; silver halide formation in situ as well as color tone regulator Source of halide ions for Functional rhodium complexes such as ammonium hexachlororhodate (III), rhodium bromide, rhodium nitrate and potassium hexachlororhodium (III); inorganic peroxides and persulfates such as ammonium disulfide and hydrogen peroxide Benzenes such as 1,3-benzoxazine-2,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione; Oxazine-2,4-dione; pyrimidine and asymmetric-triazine (eg, 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (eg, 3,6- Dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6 - tetraazapentalene, and 1,4-di (o-chlorophenyl) -3,6-dimercapto -1H, 4H-2,3a, 5,6a- tetraazapentalene) like.
[0197]
Of these, acid anhydrides are preferably used in the present invention. Acid anhydrides that can be particularly preferably used in the present invention include those in which two molecules of a monocarboxylic acid are dehydrated and condensed to have an A-CO-O-CO-B structure in the molecule, wherein A and B are linear. Or a substituent having a cyclic structure. Further, it may have a cyclic structure in which a part of these A and B are bonded. Also, A-SO in which sulfonic acid is dehydrated and condensed₂-O-CO-B, A-SO₂-O-SO₂-B may be used. The linear one is formed by dehydration of two molecules of aliphatic monocarboxylic acid. For example, acetic anhydride, propanoic anhydride, butanoic anhydride, pentanoic anhydride, caproic anhydride, lauric anhydride, anhydride Examples thereof include stearic acid, sebacic anhydride, arachidic anhydride, and behenic anhydride, and the aliphatic carboxylic acid preferably has 1 to 30 carbon atoms. Examples of the substituent having a cyclic structure include an aryl group and a heteroaryl group, and include aromatic carboxylic acids, for example, benzoic anhydride, pyridine carboxylic anhydride, and derivatives thereof. Examples of the compound having a cyclic structure in which A and B are partially bonded include dibasic acid anhydrides such as phthalic anhydride and naphthalic anhydride.
[0198]
A general example is shown below, but the present invention is not limited to this.
[0199]
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[0200]
In the present invention, it is preferable that at least one non-photosensitive layer is formed on the photosensitive layer. In addition, a filter layer may be formed on the same side as or opposite to the photosensitive layer to control the amount or wavelength distribution of light passing through the photosensitive layer, or a dye or pigment may be included in the photosensitive layer.
[0201]
The photosensitive layer may have a multi-layer structure of a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation.
[0202]
The photothermographic material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid, and the like. , A non-photosensitive layer, or another forming layer.
[0203]
Suitable binders for use in the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic, and poly (vinyl). Alcohol), hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (Styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), Poly (ureta ), Phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and polyamides. The binder may be dissolved in water or an organic solvent or in the form of an emulsion to cover and form the photothermographic layer, the non-photosensitive layer, and the like.
[0204]
Such a photothermographic material may contain an antifoggant. As the antifoggant, for example, those described in U.S. Pat. Nos. 4,546,075 and 4,452,885 and JP-A-59-57234 are preferable.
[0205]
When the photothermographic material of the present invention is used for a laser image setter, it is preferable to use a He-Ne laser (633 nm), a red semiconductor laser (670 nm), an infrared semiconductor laser (780 nm, 830 nm) or the like.
[0206]
The photothermographic material of the present invention can be provided with a dye-containing layer as an antihalation layer. For He-Ne lasers and red semiconductor lasers, dyes are added so as to absorb at least 0.3 or more, preferably 0.8 or more at the exposure wavelength in the range of 400 nm to 750 nm. For an infrared semiconductor laser, a dye is added so as to absorb at least 0.3 or more, preferably 0.8 or more at an exposure wavelength within a range of 750 nm to 1500 nm. One or more dyes may be used in combination. These dyes can be added to the dye layer near the support on the same side as the photosensitive layer or to the dye layer on the side opposite to the photosensitive layer. Further, a light or heat decolorable dye may be used.
[0207]
The support used in the present invention has a thermal dimensional change rate of less than 0.04% under thermal development conditions in which the maximum density of the exposed portion is 4.0 or more and the density of the unexposed portion is 0.2 or less. Support. The support is more preferably at most 0.03%, even more preferably at most 0.02%. The lower the rate of change, the better, but the lower limit is 0.001%. A support exceeding this range is not preferred because the adhesion to the image forming layer on the support tends to deteriorate.
[0208]
Examples of preferred supports include polycarbonate (PC), polyethylene terephthalate (PET), polyethersulfone (PES), polyarylate (PAr), polyetheretherketone (PEEK), polysulfone (PSO), syndiotactic polystyrene ( (SPS) and those obtained by heat-treating these supports, and those obtained by heat-treating polyethylene naphthalate (PEN). Among them, PC, PET, and those obtained by heat-treating them or those obtained by heat-treating PEN are preferable, and PET obtained by heat-treating PC is particularly preferable.
[0209]
The thermal dimensional ratio is usually measured in the longitudinal direction (MD) and the width direction (TD), and is preferably less than 0.04% in both directions, but either one is less than 0.04%. Is also included in the present invention.
[0210]
These supports may contain organic and inorganic fine particles, and preferable fine particles include silica, alumina, calcium carbonate, titania, calcium chloride, cross-linked polymethyl methacrylate particles, cross-linked polystyrene particles, and the like, and preferable particles. The size is 0.02 to 3 μm or less, and the preferable addition amount is 10 to 1000 ppm. The Young's modulus of these supports is 2,000 N / mm to 8000 N / mm in view of their handleability.², More preferably 3000-6000 N / mm²It is.
[0211]
The heat treatment of the support is performed before applying the photosensitive layer. Such heat treatment is preferably performed at 80 to 200 ° C, more preferably 100 to 180 ° C, and still more preferably 110 to 160 ° C. The heat treatment may be performed at a constant temperature within this temperature range. Alternatively, heat treatment while cooling may be used. Of these, heat treatment at a constant temperature or while cooling is preferable. This heat treatment time is 1 minute to 200 hours. If the time is less than 1 minute, a sufficient effect cannot be obtained. If the time exceeds 200 hours, the effect is saturated, and the support is likely to be colored or embrittled, and the working efficiency is reduced.
[0212]
The heat treatment of the support may be carried out while being transported in the form of a roll or a web. When heat treatment is performed in a roll form, 1. A method in which the roll is heat-treated in a thermostat from room temperature (low-temperature winding method); Any method may be used, such as a method in which a web is heated to a predetermined temperature during web transport and then heat-treated in a roll shape (high-temperature winding method). The method of (1) requires time to raise and lower the temperature, but has the advantage of requiring less capital investment. The method (1) requires a high-temperature winding facility, but has the advantage of eliminating the time required for heating.
[0213]
In the heat treatment in the form of a roll, due to the heat shrinkage stress during the heat treatment, surface defects such as wrinkles due to tightening of the winding and a cut edge of the winding core are likely to occur. For this reason, it is desirable to take measures such as applying knurls to both ends of the support and slightly raising only the ends so as to prevent the cut end of the winding core from appearing. The width of the knurl is 2 to 50 mm, more preferably 5 to 30 mm, still more preferably 7 to 20 mm, and the height is preferably 0.5 to 100 μm, more preferably 1 to 50 μm, and most preferably 2 to 20 μm. The knurl may be pressed in one direction or in both directions, and the temperature during application is preferably Tg or more. Further, the absolute humidity of the atmosphere at the time of performing such a heat treatment is preferably 22 g or less, more preferably 16 g or less, and still more preferably 8 g or less per kg of air, from the viewpoint of blocking during the heat treatment. . Although there is no particular lower limit for the absolute humidity, the content of water per kg of air is usually about 0.1 g.
[0214]
Preferably, the winding tension per unit width of the roll is 300 to 7500 kPa for the initial tension and 300 to 7500 kPa for the winding end. Below this range, the roll is apt to undergo slack deformation due to its own weight during heat treatment due to gentle winding, while above this value, wrinkles due to tight tightening are likely to occur. A more preferred range for the initial tension is 500 to 4000 kPa, and a more preferred range for the end of winding is 200 to 3500 kPa. It is more preferable that the winding is performed while the initial tension is larger than the winding end tension.
[0215]
In the present invention, the transfer tension of the support during the heat treatment is preferably 1300 kPa or less, more preferably 1000 kPa or less, and particularly preferably 400 kPa or less. As a result, the thermal dimensional change rate of the support is dramatically reduced, and the adhesion between the photosensitive material and the support is also improved.
[0216]
Further, the diameter of the winding core of the present invention is preferably 100 to 600 mm. If the diameter is smaller than this, the heat treatment generates spots and wrinkles. If it exceeds 600 mm, it becomes bulky and inconvenient and unrealistic in storage and transportation. Preferably, the diameter is between 150 and 450 mm, more preferably between 200 and 400 mm. The cross section of the winding core is preferably a perfect circle.
[0217]
The material of these cores preferably has a sufficient elastic modulus during heat treatment and is not easily deformed by the heat shrinkage stress of the support. Cores made of ceramic, metal, resin, FRP (fiber reinforced plastic) are preferable. preferable.
[0218]
On the other hand, when heat treatment is performed in the form of a web, a heat treatment zone is required, but a better surface state of the support can be obtained as compared with heat treatment in the form of a roll, which is more preferable. The transport tension at this time is preferably 10 to 1300 kPa, more preferably 30 to 1000 kPa, and still more preferably 50 to 400 kPa. Such a low tension needs to be achieved especially in the heat treatment zone, and a suction drum is set before and after the heat treatment zone, and during this time, it is conveyed with a weak tension, and the subsequent winding step is to be wound with a higher tension. More preferred. Winding is preferably performed after sufficiently cooling with a chilling roll or the like in order to reduce dimensional change. Further, the force applied to the support includes not only the winding tension but also a stress accompanying thermal contraction generated by itself. For this reason, it is more preferable to measure the amount of heat shrinkage in advance, and to control so that the feeding amount is larger than the winding amount by this amount. Such heat treatment is preferably performed for 1 minute to 60 minutes, more preferably 3 minutes to 30 minutes, still more preferably 5 minutes to 15 minutes. Since a long heat treatment zone is required to take a long heat treatment time, it is preferable that the heat treatment is performed twice or more.
[0219]
These heat treatments are preferably performed after the undercoating. This is because the dimensional change rate tends to increase due to the tension in the undercoating step. In addition, by including the matting particles in the undercoat layer, the flatness at the time of the roll-shaped heat treatment can be improved.
[0220]
【Example】
Hereinafter, the present invention will be described specifically with reference to examples, but embodiments of the present invention are not limited thereto.
[0221]
As a support, a PET base having a heat treatment of 125 μm and a heat-treated support were used. Here, PET was prepared by changing the transport tension during transport to 1500 kPa, 1000 kPa, and 400 kPa. Then, a heat treatment was performed at 130 ° C. for 15 minutes while transporting each at 20 m / min.
[0222]
Example 1
(Preparation of silver halide emulsion A)
After dissolving 7.5 g of inert gelatin and 10 mg of potassium bromide in 900 ml of water and adjusting the temperature to 35 ° C. and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and the molar ratio of (60/38/2) are obtained. Sodium chloride, potassium bromide, potassium iodide and [Ir (NO) Cl₅1 × 10 9 salt per mole of silver^-6Moles and rhodium chloride at 1 × 10^-6370 ml of an aqueous solution containing mol was added by a controlled double jet method while maintaining pAg at 7.7.
[0223]
Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 8 with NaOH, and the pAg was adjusted to 6.5 to perform reduction sensitization, and the average particle size was 0.06 μm, and Cubic silver iodobromide grains having a dispersion coefficient of 10%, a variation coefficient of the projected diameter area of 8%, and a [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment to prepare a silver halide emulsion A.
[0224]
(Preparation of sodium behenate solution)
In 945 ml of pure water, 32.4 g of behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid were dissolved at 90 ° C. Next, 98 ml of a 1.5 mol / L aqueous sodium hydroxide solution was added while stirring at a high speed. Next, after adding 0.93 ml of concentrated nitric acid, the mixture was cooled to 55 ° C. and stirred for 30 minutes to obtain a sodium behenate solution.
[0225]
(Preparation of preform emulsion of silver behenate and silver halide emulsion A)
1.51 g of the silver halide emulsion A was added to the above-mentioned sodium behenate solution, and the pH was adjusted to 8.1 with a sodium hydroxide solution. Stirring and ultrafiltration removed water-soluble salts. The resulting silver behenate was grains having an average grain size of 0.8 μm and a monodispersity of 8%. After the floc of the dispersion was formed, the water was removed, washed six times with water and removed, and then dried.
[0226]
(Preparation of photosensitive emulsion)
The preform emulsion thus obtained was divided, and 544 g of a methyl ethyl ketone solution (17% by mass) of polyvinyl butyral (average molecular weight: 3000) and 107 g of toluene were gradually added and mixed.₂Was dispersed at 27.58 MPa at 30 ° C. for 10 minutes using a media disperser using a bead mill.
[0227]
(Preparation of photothermographic material)
The following layers were simultaneously coated on both sides of the support to prepare a photothermographic material sample. The drying was performed at 60 ° C. for 15 minutes.
[0228]
<Back side coating>
A liquid having the following composition was applied on the support so that the dry film thickness was 2.5 μm.
[0229]
Cellulose acetate butyrate 90g
Dye D2-1 0.42 g
Dye D3-5 0.42 g
Matting agent: monodispersity 15%, average particle size 8 μm, monodisperse silica 5.4 g
C₈F₁₇(CH₂CH₂O)₁₂C₈F₁₇                                3g
C₉F₁₇-C₆H₄-SO₃Na 1g
900 g of methyl ethyl ketone
[0230]
Embedded image

[0231]
<Coating on photosensitive layer side>
(Under the photosensitive layer)
A solution having the following composition was applied to a surface opposite to the surface to which the back layer was applied so as to have a thickness of 2 μm.
[0232]
Butyral resin (Sekisui Chemical BM1) 10g
90 g of methyl ethyl ketone
(Photosensitive layer)
A liquid having the following composition was applied on the lower layer of the photosensitive layer so as to have a thickness of 10 μm.
[0233]

[0234]
Embedded image

[0235]
(Protective layer)
A solution having the following composition was simultaneously applied to the upper layer of the photosensitive layer so that the dry film thickness became 2 μm.
[0236]

《Evaluation of photographic performance》
(Exposure processing)
The obtained photothermographic material was subjected to a laser exposure apparatus of a single-channel cylindrical inner surface type equipped with a semiconductor laser having a beam diameter (FWHM of ビ ー ム of the beam intensity) of 12.56 μm, a laser output of 50 mW, and an output wavelength of 783 nm. The exposure time is adjusted by changing the number of rotations of the mirror, and the exposure amount is adjusted by changing the output value.^-8The dragonfly image was exposed in seconds. The overlap coefficient at this time was set to 0.449.
[0237]
(Heat development processing)
The exposed heat-developable photosensitive material is subjected to the heat-development machine shown in FIG. 1, the roller surface material of the heat-development processing portion is made of silicone rubber, and the smooth surface is made of Teflon (R) non-woven fabric. The heat development was performed at 120 ° C. for 20 seconds.
[0238]
The temperature accuracy in the width direction was ± 1 ° C.
(Evaluation of registration mark detection by plate making machine)
Using a plate making machine S-FNRIII manufactured by Fuji Photo Film Co., Ltd. (marker detector, light source wavelength of bar code reader: 670 nm), transport the film and PS plate and test each sample five times to see if the exposure of the PS plate can be performed correctly. The registration mark images obtained by the number of times the exposure was correctly performed were evaluated. Table 1 shows the results. The PS plate used was VNN manufactured by Fuji Photo Film Co., Ltd.
[0239]
[Table 1]

[0240]
Example 2
A sample was prepared in exactly the same manner as in Example 1 except that the vinyl compound was changed to (27), and the same evaluation as in Example 1 was performed. As a result, the sample of the present invention was excellent.
[0241]
Example 3
Using the samples 101 to 105 manufactured in Example 1, development was performed while changing the temperature of the preheating unit 1 in FIG. 1, and the same evaluation as in Example 1 was performed.
[0242]
[Table 2]

[0243]
【The invention's effect】
As demonstrated in the Examples, the photothermographic material according to the present invention and the image forming method using the same have excellent sensor suitability in a plate making machine for photoengraving, particularly for scanners and imagesetters, and have excellent effects.
[Brief description of the drawings]
FIG. 1 is a schematic sectional view showing an example of a heat developing machine used in the present invention.
[Explanation of symbols]
1 Preheating section
2 development unit
3 Cooling section
4 Roller with built-in halogen lamp heater
5 Transport rollers
6 Aluminum panel heater
7 Temperature sensor

Claims (3)

In a photothermographic material containing an organic silver salt, a silver halide, a developer and a vinyl compound on a support, the density of the blackened portion and the amount of reflected light of the bare portion after the thermal development processing were measured using a Keyence FSV1 amplifier. A photothermographic material characterized in that the measured value is 50 to 150 in the blackened portion and 430 to 620 in the uncoated portion. The photothermographic material according to claim 1, wherein the high contrast agent is a vinyl compound represented by the following general formula (G).

[Wherein, X represents an electron-withdrawing group. W represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an acyl group, a thioacyl group, an oxalyl group, an oxyoxalyl group, a thiooxalyl group, an oxamoyl group, an oxycarbonyl group, and a thiocarbonyl group. Group, carbamoyl group, thiocarbamoyl group, sulfonyl group, sulfinyl group, oxysulfonyl group, thiosulfonyl group, sulfamoyl group, oxysulfinyl group, thiosulfinyl group, sulfinamoyl group, phosphoryl group, hydroxy group, alkoxy group, aryloxy group, Heterocyclic oxy group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, arylamino group, heteroarylamino group, acylamino group, oxycarbonylamino group, sulfone Amide group, oxysulfonylamino group, ureido group, sulfamoylamino group, nitro group, imidoyl group, N-acylimidoyl group, N-sulfonylimidoyl group, dicyanoethylene group, ammonium group, sulfonium group, phosphonium group, Represents a pyrylium group. R is a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkenyloxy group, an acyloxy group, an alkoxycarbonyloxy group, an aminocarbonyloxy group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group , Alkenylthio, acylthio, alkoxycarbonylthio, aminocarbonylthio, organic or inorganic salts of hydroxy or mercapto, amino, alkylamino, cyclic amino, acylamino, oxycarbonylamino, hetero Represents a ring group, a ureido group, or a sulfonamide group. X and W, and X and R may be bonded to each other to form a cyclic structure. ] 3. The photothermographic material according to claim 1, further comprising a preheat section in front of the heat development section of the automatic heat development apparatus, wherein an image is obtained by setting the temperature of the preheat section to 80 to 120 ° C. Image forming method.

Images