JP3689189B2 - Image forming method - Google Patents

Description

【００５０】
前記添加剤のうちカブリ防止剤、安定化剤としてはアゾール類（例えば、ベンゾチアゾリム塩、ニトロイミダゾール類、ニトロベンズイミダゾール類、クロロベンズイミダゾール類、ブロモベンズイミダゾール類、ニトロインダゾール類、ベンズトリアゾール類、アミノトリアゾール類など）；メルカプト化合物類｛例えば、メルカプトチアゾール類、メルカプトベンゾチアゾール類、メルカプトベンズイミダゾール類、メルカプトチアジアゾール類、メルカプトテトラゾール類（特に、１−フェニル−５−メルカプトテトラゾールおよびその誘導体）、メルカプトピリミジン類、メルカプトトリアジン類など）；例えばオキサドリンチオンのようなチオケト化合物；アザインデン類｛例えば、トリアザインデン類、テトラアザインデン類（特に、４−ヒドロキシ−６−メチル（１，３，３ａ，７）テトラアザインデン）、ペンタアザインデン類など）；ベンゼンチオスルホン類、ベンゼンスルフィン酸；ベンゼンスルホン酸アミド等を好ましく用いることができる。
【００５１】
熱現像感光材料や錯化剤シートの構成層のバインダーには親水性のものが好ましく用いられる。その例としては前記のリサーチ・ディスクロージャーおよび特開昭６４−１３，５４６号の(71)頁〜(75)頁に記載されたものが挙げられる。具体的には、透明か半透明の親水性バインダーが好ましく、例えばゼラチン、ゼラチン誘導体等の蛋白質またはセルロース誘導体、寒天、澱粉、アラビアゴム、デキストラン、プルラン、ファーセレラン、欧州公開特許４４３，５２９号記載のカラギナン、ローカストビーンガム、キサンタンガム、ペクチン等の多糖類、特開平１−２２１７３６号記載の多糖類のような天然化合物やポリビニルアルコール、特願平５−３３９１５５号記載の変成アルキルポリビニルアルコール、ポリビニルピロリドン、アクリルアミド重合体等の合成高分子化合物が挙げられる。また、米国特許第４，９６０，６８１号、特開昭６２−２４５，２６０号等に記載の高吸水性ポリマー、すなわち−ＣＯＯＭまたは−ＳＯ₃ Ｍ（Ｍは水素原子またはアルカリ金属）を有するビニルモノマーの単独重合体またはこのビニルモノマー同士、もしくは他のビニルモノマーとの共重合体（例えばメタクリル酸ナトリウム、メタクリル酸アンモニウム、住友化学（株）製のスミカゲルＬ−５Ｈ）も使用される。これらのバインダーは２種以上組み合わせて用いることもできる。ゼラチンと上記バインダーの組み合わせが好ましい。またゼラチンは、種々の目的に応じて石灰処理ゼラチン、酸処理ゼラチン、カルシウムなどの含有量を減らしたいわゆる脱灰ゼラチンから選択すれば良く、組み合わせて用いることも好ましい。
【００５２】
微量の水を供給して熱現像を行うシステムを採用する場合、上記の高吸水性ポリマーを用いることにより、水の吸収を迅速に行うことが可能となる。
【００５３】
バインダーとしては、ゼラチンが好ましく使用されるが、ゼラチン含有率の少ない場合、ゼラチン以外の親水性ポリマーは、塗布時のセット性の点で、欧州公開特許４４３，５２９号記載のカラギナンや特願平５−３３９１５５号記載の変成アルキルポリビニルアルコールや特開平６−６７３３０号記載の多糖類が好ましく用いられる。
【００５４】
感光材料の感光性ハロゲン化銀乳剤層を含む側の全バインダーの塗布量は、１２ｇ／m²以下が好ましく、特に５ｇ／m²以下、更には４ｇ／m²以下にするのが適当である。また、感光性ハロゲン化銀乳剤層を含む側に対して反対側に塗布された全バインダー量は、感光性ハロゲン化銀乳剤層を含む側の全バインダーの塗布量の５０〜１００％の範囲内に入っていることが好ましい。より好ましくは、７０％付近である。
【００５５】
本発明に用いる還元剤としては、熱現像感光材料の分野で知られているものを用いることができる。また、後述する還元性を有する色素供与性化合物も含まれる（この場合、その他の還元剤を併用することもできる）。また、それ自身は還元性を持たないが現像過程で求核試薬や熱の作用により還元性を発現する還元剤プレカーサーも用いることができる。
本発明に用いられる還元剤の例としては、米国特許第４，５００，６２６号の第４９〜５０欄、同４，８３９，２７２号、同４，３３０，６１７号、同４，５９０，１５２号、同５，０１７，４５４号、同５，１３９，９１９号、特開昭６０−１４０，３３５号の第(17)〜(18)頁、同５７−４０，２４５号、同５６−１３８，７３６号、同５９−１７８，４５８号、同５９−５３，８３１号、同５９−１８２，４４９号、同５９−１８２，４５０号、同６０−１１９，５５５号、同６０−１２８，４３６号、同６０−１２８，４３９号、同６０−１９８，５４０号、同６０−１８１，７４２号、同６１−２５９，２５３号、同６２−２０１，４３４号、同６２−２４４，０４４号、同６２−１３１，２５３号、同６２−１３１，２５６号、同６３−１０，１５１号、同６４−１３，５４６号の第(40)〜(57)頁、特開平１−１２０，５５３号、同２−３２，３３８号、同２−３５，４５１号、同２−２３４，１５８号、同３−１６０，４４３号、欧州特許第２２０，７４６号の第７８〜９６頁等に記載の還元剤や還元剤プレカーサーがある。米国特許第３，０３９，８６９号に開示されているもののような種々の還元剤の組合せも用いることができる。
【００５６】
耐拡散性の還元剤を使用する場合には、耐拡散性還元剤と現像可能なハロゲン化銀との間の電子移動を促進するために、必要に応じて電子伝達剤および／または電子伝達剤プレカーサーを組合せて用いることができる。特に好ましくは、前記米国特許第５，１３９，９１９号、欧州特許公開第４１８，７４３号、特開平１−１３８，５５６号、同３−１０２，３４５号記載のものが用いられる。また特開平２−２３０，１４３号、同２−２３５，０４４号記載のように安定に層中に導入する方法が好ましく用いられる。
電子伝達剤またはそのプレカーサーは、前記した還元剤またはそのプレカーサーの中から選ぶことができる。電子伝達剤またはそのプレカーサーはその移動性が耐拡散性の還元剤（電子供与体）より大きいことが望ましい。特に有用な電子伝達剤は１−フェニル−３−ピラゾリドン類又はアミノフェノール類である。
電子伝達剤と組合せて用いる耐拡散性の還元剤（電子供与体）としては、前記した還元剤の中で感光材料の層中で実質的に移動しないものであればよく、好ましくはハイドロキノン類、スルホンアミドフェノール類、スルホンアミドナフトール類、特開昭５３−１１０８２７号、米国特許第５，０３２，４８７号、同５，０２６，６３４号、同４，８３９，２７２号に電子供与体として記載されている化合物および後述する耐拡散性で還元性を有する色素供与性化合物等が挙げられる。
また特開平３−１６０，４４３号記載のような電子供与体プレカーサーも好ましく用いられる。
さらに中間層や保護層に混色防止、色再現改善、白地改善、色素固定材料への銀移り防止など種々の目的で上記還元剤を用いることができる。具体的には、欧州特許公開第５２４，６４９号、同３５７，０４０号、特開平４−２４９，２４５号、同２−６４，６３３号、同２−４６，４５０号、特開昭６３−１８６，２４０号記載の還元剤が好ましく用いられる。また特公平３−６３，７３３号、特開平１−１５０，１３５号、同２−１１０，５５７号、同２−４６，６３４号、同３−４３，７３５号、欧州特許公開第４５１，８３３号記載のような現像抑制剤放出還元性化合物も用いられる。
本発明に於いては還元剤の総添加量は銀１モルに対して０．０１〜２０モル、特に好ましくは０．１〜１０モルである。
【００５７】
本発明においては、感光性ハロゲン化銀乳剤と共に、有機金属塩を酸化剤として併用することもできる。このような有機金属塩の中で、有機銀塩は、特に好ましく用いられる。
上記の有機銀塩酸化剤を形成するのに使用し得る有機化合物としては、米国特許第４，５００，６２６号第５２〜５３欄等に記載のベンゾトリアゾール類、脂肪酸その他の化合物がある。また米国特許第４，７７５，６１３号記載のアセチレン銀も有用である。有機銀塩は、２種以上を併用してもよい。
以上の有機銀塩は、感光性ハロゲン化銀１モルあたり、０．０１〜１０モル、好ましくは０．０１〜１モルを併用することができる。感光性ハロゲン化銀乳剤と有機銀塩の塗布量合計は銀換算で０．０５〜１０ｇ／m²、好ましくは０．４ｇ／m²が適当である。
【００５８】
本発明の熱現像感光材料の構成層にはハレーション防止やイラジエーション防止などの目的で、種々の染料を用いることができる。染料は、特開平３−７９３１号や同２−３０８２４２号に開示されているように、固体状態の微粒子として分散し、感光材料に組み込むのが好ましい。具体的には前記リサーチ・ディスクロージャー記載の化合物や、特願平６−２５９９０５号等に記載の化合物を用いることができる。
【００５９】
本発明の熱現像感光材料には、現像の活性化と同時に画像の安定化を図る化合物を用いることができる。好ましく用いられる具体的化合物については米国特許第４，５００，６２６号の第５１〜５２欄に記載されている。
【００６０】
本発明においては、画像形成物質は、主として感光材料中の現像銀である。必要に応じて、色素（色素供与性化合物）を画像形成物質に利用してもよい。ＰＳ版への焼き付け原稿となる印刷製版用感光材料において、ＰＳ版は、紫外線カットの明室で取り扱えるように３００nm〜５００nmの間の波長域に分光感度を有しているので、その画像がこの波長域でディスクリミネーションを有していればよく、銀画像とともにこの波長域に吸収を持つ色素（色素供与性化合物）を画像にすることができる。また、互いに実質的に異なる色調を有する色素を形成または放出する少なくとも２種類の色素供与性化合物を用いて、または、互いに実質的に異なる色調を有する少なくとも２種類の色素を形成または放出する色素供与性化合物を用いて銀と共に色素による白黒画像を得ることができる。
【００６１】
本発明で使用しうる色素供与性化合物の例としてはまず、酸化カップリング反応によって色素を形成する化合物（カプラー）を挙げることができる。このカプラーは４当量カプラーでも、２当量カプラーでもよい。また、耐拡散性基を脱離基に持ち、酸化カップリング反応により拡散性色素を形成する２当量カプラーも好ましい。この耐拡散性基はポリマー鎖をなしていてもよい。カラー現像薬およびカプラーの具体例は、米国特許第３，５３１，２８６号にパラフェニレンジアミン系還元剤とフェノール性または活性メチレンカプラーが、同３，７６１，２７０号にパラアミノフェノール系還元剤が、ベルギー特許８０２，５１９号およびリサーチ・ディスクロージャー誌１９７５年９月３１日、３２頁にスルホンアミドフェノール系還元剤が米国特許第４，０２１，２４０号に、スルホンアミドフェノール系還元剤と４当量カプラーとの組み合わせが提案されている。その他のカラー現像薬およびカプラーの具体例は、T.H.James 著“The Theory of the Photographic Process”第４版２９１〜３３４頁および３５４〜３６１頁にも記載されいてる。カップリング反応において、カプラーと反応しうる還元剤としては、ヒドラゾン化合物やヒドラジン化合物も好ましく使用できる。
【００６２】
別の色素供与性化合物の例としては、特開昭５９−１８０５４８号等に記載のように銀イオンまたは可溶性銀錯体の存在下で、窒素原子およびイオウ原子またはセレン原子を含む複素環の開裂反応を起こして可動性色素を放出する前記複素環を有する対拡散性色素供与性化合物（チアゾリジン系化合物）も使用できる。また、別の色素供与性化合物の例として、画像状に拡散性色素を放出乃至拡散する機能を持つ化合物を挙げることができる。この型の化合物は次の一般式〔ＬＩ〕で表わすることができる。
（（Ｄｙｅ）_m −Ｙ）_n −Ｚ 〔ＬＩ〕
Ｄｙｅは色素基、一時的に短波化された色素基または色素前駆体基を表わし、Ｙは単なる結合又は連結基を表わし、Ｚは画像状に潜像を有する感光性銀塩に対応又は逆対応して（（Ｄｙｅ）_m −Ｙ）_n −Ｚで表わされる化合物の拡散性に差を生じさせるか、または、（Ｄｙｅ）_m −Ｙを放出し、放出された（Ｄｙｅ）_m −Ｙと（（Ｄｙｅ）_m −Ｙ）_n −Ｚとの間に拡散性において差を生じさせるような性質を有する基を表わし、ｍは１〜５の整数を表わし、ｎは１または２を表わし、ｍ、ｎのいずれかが１でない時、複数のＤｙｅは同一でも異なっていてもよい。
一般式〔ＬＩ〕で表わされる色素供与性化合物の具体例としては下記の１〜３のハロゲン化銀の現像に逆対応して拡散性の色素像を形成するものである。
【００６３】
１．米国特許第３，１３４，７６４号、同３，３６２，８１９号、同３，５９７，２００号、同３，５４４，５４５号、同３，４８２，９７２号、特公平３−６８，３８７号等に記載されている、ハイドロキノン系現像薬と色素形成分を連結した色素現像薬。この色素現像薬はアルカリ性の環境下で拡散性であるが、ハロゲン化銀と反応すると非拡散性になるものである。
【００６４】
２．米国特許第４，５０３，１３７号等に記されている通り、アルカリ性の環境下で拡散性色素を放出するがハロゲン化銀と反応するとその能力を失う非拡散性の化合物も使用できる。その例としては、米国特許第３，９８０，４７９号等に記載された分子内求核置換反応により拡散性色素を放出する化合物、米国特許第４，１９９，３５４号等に記載されたイソオキサゾロン環の分子内巻き換え反応により拡散性色素を放出する化合物が挙げられる。
【００６５】
３．米国特許第４，５５９，２９０号、欧州特許第２２０，７４６Ａ２号、米国特許第４，７８３，３９６号、公開技報８７−６，１９９、特開昭６４−１３，５４６号等に記されている通り、現像によって酸化されずに残った還元剤と反応して拡散性色素を放出する非拡散性の化合物も使用できる。
その例としては、米国特許第４，１３９，３８９号、同４，１３９，３７９号、特開昭５９−１８５，３３３号、同５７−８４，４５３号等に記載されている還元された後に分子内の求核置換反応により拡散性の色素を放出する化合物、米国特許第４，２３２，１０７号、特開昭５９−１０１，６４９号、同６１−８８，２５７号、ＲＤ２４，０２５（１９８４年）等に記載された還元された後に分子内の電子移動反応により拡散性の色素を放出する化合物、西独特許第３，００８，５８８Ａ号、特開昭５６−１４２，５３０号、米国特許第４，３４３，８９３号、同４，６１９，８８４号等に記載されている還元後に一重結合が開裂して拡散性の色素を放出する化合物、米国特許第４，４５０，２２３号等に記載されている電子受容後に拡散性色素を放出するニトロ化合物、米国特許第４，６０９，６１０号等に記載されている電子受容後に拡散性色素を放出する化合物等が挙げられる。
【００６６】
また、より好ましいものとして、欧州特許第２２０，７４６号、公開技報８７−６，１９９、米国特許第４，７８３，３９６号、特開昭６３−２０１，６５３号、同６３−２０１，６５４号、同６４−１３，５４６号等に記載された一分子内にＮ−Ｘ結合（Ｘは酸素、硫黄または窒素原子を表す）と電子吸引性基を有する化合物、特開平１−２６，８４２号に記載された一分子内にＳＯ₂ −Ｘ（Ｘは上記と同義）と電子吸引性基を有する化合物、特開昭６３−２７１，３４４号に記載された一分子内にＰＯ−Ｘ結合（Ｘは上記と同義）と電子吸引性基を有する化合物、特開昭６３−２７１，３４１号に記載された一分子内にＣ−Ｘ′結合（Ｘ′はＸと同義か又は−ＳＯ₂ −を表す）と電子吸引性基を有する化合物が挙げられる。また、特開平１−１６１，２３７号、同１−１６１，３４２号に記載されている電子受容性基と共役するπ結合により還元後に一重結合が開裂し拡散性色素を放出する化合物も利用できる。
この中でも特に一分子内にＮ−Ｘ結合と電子吸引性基を有する化合物が好ましい。
【００６７】
着色している色素供与性化合物は、感光性ハロゲン化銀乳剤層の下層に存在させると、感度の低下を防ぐことができる。
【００６８】
色素供与性化合物、耐拡散性還元剤などの疎水性添加剤は米国特許第２，３２２，０２７号記載の方法などの公知の方法により熱現像感光材料の層中に導入することができる。この場合には、米国特許第４，５５５，４７０号、同４，５３６，４６６号、同４，５３６，４６７号、同４，５８７，２０６号、同４，５５５，４７６号、同４，５９９，２９６号、特開昭６３−３０６４３９号、同６２−８１４５号、同６２−３０２４７号、特公平３−６２，２５６号などに記載のような高沸点有機溶媒を、必要に応じて沸点５０℃〜１６０℃の低沸点有機溶媒と併用して、用いることがてきる。またこれら色素供与性化合物、耐拡散性還元剤、高沸点有機溶媒などは２種以上併用することができる。
高沸点有機溶媒の量は用いられる疎水性添加剤１ｇに対して１０ｇ以下、好ましくは５ｇ以下、より好ましくは１ｇ〜０．１ｇである。また、バインダー１ｇに対して１cc以下、更には０．５cc以下、特に０．３cc以下が適当である。
また特公昭５１−３９，８５３号、特開昭５１−５９，９４３号に記載されている重合物による分散法や特開昭６２−３０，２４２号等に記載されいてる微粒子分散物にして添加する方法も使用できる。
水に実質的に不溶な化合物の場合には、前記方法以外にバインダー中に微粒子にして分散含有させることができる。
疎水性化合物を親水性コロイドに分散する際には、種々の界面活性剤を用いることができる。例えば特開昭５９−１５７，６３６号の第(37)〜(38)頁、前記のリサーチ・ディスクロージャー記載の界面活性剤として挙げたものを使うことができる。
また、特開平７−０５６２６７号、特願平６−１９２４７号、西独公開特許第１，９３２，２９９Ａ号記載のリン酸エステル型界面活性剤も使用できる。
【００６９】
錯化剤シートに色素像を併用する場合、媒染剤として写真分野で公知のものを用いることができ、その具体例としては米国特許第４，５００，６２６号第５８〜５９欄、特開昭６１−８８，２５６号第(32)〜(41)頁や特開平１−１６１，２３６号第(4) 〜(7) 頁に記載の媒染剤、米国特許第４，７７４，１６２号、同４，６１９，８８３号、同４，５９４，３０８号等に記載のものを挙げることができる。また、米国特許第４，４６３，０７９号に記載されているような色素受容性の高分子化合物を用いてもよい。
【００７０】
錯化剤シートは、必要に応じて保護層、剥離層、下塗り層、中間層、バック層、カール防止層などの補助層を設けることができる。特に保護層を設けるのは有用である。
【００７１】
本発明の錯化剤シートに用いられるバインダーは、前記の親水性バインダーが好ましい。さらに欧州公開特許第４４３，５２９号記載のようなカラギナン類、デキストランのような多糖類の併用や、特公平３−７４，８２０号記載のようなガラス転移温度４０℃以下のラテックス類を併用することが望ましい。また、写真分野で公知の媒染剤のポリマーや米国特許第４，９６０，６８１号、特開昭６２−２４５２６０号等記載の高吸水性ポリマーを併用することが好ましく用いられる。さらに、ポリビニルピロリドン、ポリビニルイミダゾール、ピロリドンとイミダゾールの共重合体のようなポリマーも好ましく使用できる。
バインダーの全塗布量は、２０ｇ／m²以下が好ましく、特に１０ｇ／m²以下、さらには７ｇ／m²以下にするのが適当である。
【００７２】
熱現像感光材料および錯化剤シートの構成層には、可塑剤、スベリ剤あるいは感光材料と錯化剤シートとの剥離性改良剤として高沸点有機溶媒を用いることができる。具体的には、前記リサーチ・ディスクロージャーや特開昭６２−２４５，２５３号などに記載されたものがある。
更に、上記の目的のために、各種のシリコーンオイル（ジメチルシリコーンオイルからジメチルシロキサンに各種の有機基を導入した変成シリコーンオイルまでの総てのシリコーンオイル）を使用できる。その例としては、信越シリコーン（株）発行の「変成シリコーンオイル」技術資料Ｐ６〜１８Ｂに記載の各種変成シリコーンオイル、特にカルボキシ変成シリコーン（商品名Ｘ−２２−３７１０）などが有効である。
また特開昭６２−２１５，９５３号、同６３−４６，４４９号に記載のシリコーンオイルも有効である。
熱現像感光材料や錯化剤シートの構成層に用いる硬膜剤としては、前記リサーチ・ディスクロージャー、米国特許第４，６７８，７３９号第４１欄、同４，７９１，０４２号、特開昭５９−１１６，６５５号、同６２−２４５，２６１号、同６１−１８，９４２号、特開平４−２１８，０４４号等に記載の硬膜剤が挙げられる。より具体的には、アルデヒド系硬膜剤（ホルムアルデヒドなど）、アジリジン系硬膜剤、エポキシ系硬膜剤、ビニルスルホン系硬膜剤（Ｎ，Ｎ′−エチレン−ビス（ビニルスルホニルアセタミド）エタンなど）、Ｎ−メチロール系硬膜剤（ジメチロール尿素など）、あるいは高分子硬膜剤（特開昭６２−２３４，１５７号などに記載の化合物）が挙げられる。
これらの硬膜剤は、塗布された親水性バインダー１ｇあたり０．００１〜１ｇ、好ましくは０．００５〜０．５ｇが用いられる。また添加する層は、感光材料や錯化剤シートの構成層のいずれの層でも良いし、２層以上に分割して添加しても良い。
【００７３】
熱現像感光材料や錯化剤シートの構成層には、種々のカブリ防止剤または写真安定剤およびそれらのプレカーサーを使用することができる。その具体例としては、前記リサーチ・ディスクロージャー、米国特許第５，０８９，３７８号、同４，５００，６２７号、同４，６１４，７０２号、特開昭６４−１３，５４６号(7) 〜(9) 頁、(57)〜(71)頁および(81)〜(97)頁、米国特許第４，７７５，６１０号、同４，６２６，５００号、同４，９８３，４９４号、特開昭６２−１７４，７４７号、同６２−２３９，１４８号、同６３−２６４，７４７号、特開平１−１５０，１３５号、同２−１１０，５５７号、同２−１７８，６５０号、ＲＤ１７，６４３（１９７８年）(24)〜(25)頁、特願平６−１９０５２９号等記載の化合物が挙げられる。
これらの化合物は、銀１モルあたり５×１０^-6〜１×１０^-1モルが好ましく、さらに１×１０^-5〜１×１０^-2モルが好ましく用いられる。
【００７４】
熱現像感光材料や錯化剤シートの構成層には、塗布助剤、剥離性改良、スベリ性改良、帯電防止、現像促進等の目的で種々の界面活性剤を使用することができる。界面活性剤の具体例は前記リサーチ・ディスクロージャー、特開昭６２−１７３，４６３号、同６２−１８３，４５７号等に記載されている。
熱現像感光材料や錯化剤シートの構成層には、スベリ性改良、帯電防止、剥離性改良等の目的で有機フルオロ化合物を含ませてもよい。有機フルオロ化合物の代表例としては、特公昭５７−９０５３号第８〜１７欄、特開昭６１−２０９４４号、同６２−１３５８２６号等に記載されているフッ素系界面活性剤、またはフッ素油などのオイル状フッ素系化合物もくしは四フッ化エチレン樹脂などの固体状フッ素化合物樹脂などの疎水性フッ素化合物が挙げられる。
【００７５】
熱現像感光材料や錯化剤シートには、接着防止、スベリ性改良、非光沢面化などの目的でマット剤を用いることができる。マット剤としては種々の無機化合物、有機化合物粒子特にポリマー粒子が用いられる。無機のマット剤としては、二酸化珪素、コロイダルシリカ、酸化チタン、酸化アルミニウム等の酸化物、硫酸バリウム、炭酸カルシウム、硫酸マグネシウム等のアルカリ土類金属塩および珪酸塩、リン酸塩やホウ酸塩等のガラス粒子が挙げられる。有機のマット剤としては、コーンスターチ、セルロースエステル、セルロースエーテル等の天然物およびその改質品、アルキルアクリレート類、アルキルメタクリレート類、アクリルアミド類、ビニルエステル類、スチレン類の合成樹脂等、ポリオレフィンまたはポリメタクリレートなどの特開昭６１−８８２５６号(29)頁記載の化合物の他に、ベンゾグアナミン樹脂ビーズ、ポリカーボネート樹脂ビーズ、ＡＳ樹脂ビーズなどの特開昭６３−２７４９４４号、その他前記リサーチ・ディスクロージャー記載の化合物が使用できる。これらのマット剤は、最上層（保護層）のみならず必要に応じて下層に添加することもできる。
【００７６】
本発明において、マット剤は、単独で使用してもよいし、２種以上併用してもよい。本発明に用いるマット剤の平均粒径が０．１μm から２０μm のものを用いるのが好ましい。マット剤の添加量は、バインダーに対し、重量比で１ないし４０％が好ましく、更に好ましくは２ないし２０％である。
【００７７】
特開平３−１０９５４２号や特開昭６４−３１１４９号や特開昭６２−１６３０４７号記載のように、空洞を有するものや、表面に多孔性のものを使用してもよい。
【００７８】
その他、熱現像感光材料および非感光性錯化剤シートの構成層には、熱溶剤、消泡剤、防菌防バイ剤等を含ませてもよい。これらの添加剤の具体例は特開昭６１−８８２５６号第(26)〜(32)頁、特開平３−１１，３３８号、特公平２−５１，４９６号等に記載されている。
【００７９】
本発明において熱現像感光材料及び／又は錯化剤シートには画像形成促進剤を用いることができる。画像形成促進剤には、物理化学的な機能からは塩基または前述の塩基プレカーサー、求核性化合物、高沸点有機溶媒（オイル）、熱溶剤、界面活性剤、銀または銀イオンと相互作用を持つ化合物等に分類される。ただし、これらの物質群は一般に複合機能を有しており、上記の促進効果のいくつかを合せ持つのが常である。これらの詳細については米国特許第４，６７８，７３９号第３８〜４０欄に記載されている。
【００８０】
本発明において熱現像感光材料及び／又は錯化剤シートには、現像時の処理温度および処理時間の変動に対し、常に一定の画像を得る目的で種々の現像停止剤を用いることができる。
ここでいう現像停止剤とは、適正現像後、速やかに塩基を中和または塩基と反応して膜中の塩基濃度を下げ現像を停止する化合物または銀および銀塩と相互作用して現像を抑制する化合物である。具体的には、加熱により酸を放出する酸プレカーサー、加熱により共存する塩基と置換反応を起す親電子化合物、または含窒素ヘテロ環化合物、メルカプト化合物及びその前駆体等が挙げられる。更に詳しくは特開昭６２−２５３，１５９号(31)〜(32)頁に記載されている。
【００８１】
本発明において熱現像感光材料や錯化剤シートの支持体としては、処理温度に耐えることのできるものが用いられる。一般的には、日本写真学会編「写真工学の基礎−銀塩写真編−」、株コロナ社刊（昭和５４年）(223) 〜(240) 頁記載の紙、合成高分子（フィルム）等の写真用支持体が挙げられる。具体的には、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、ポエ塩化ビニル、ポリスチレン、ポリプロピレン、ポリイミド、ポリアリレート、セルロース類（例えばトリアセチルセルロース）またはこれらのフィルム中へ酸化チタンなどの顔料を含有させたもの、更にポリプロピレンなどから作られるフィルム法合成紙、ポリエチレン等の合成樹脂パルプと天然パルプとから作られる混抄紙、ヤンキー紙、バライタ紙、コーティッドペーパー（特にキャストコート紙）、金属、布類、ガラス類等が用いられる。支持体の厚みは、１０μm 〜２００μm が好ましく用いられる
これらは、単独で用いることもできるし、ポリエチレン等の合成高分子で片面または両面をラミネートされた支持体として用いることができる。このラミネート層には、酸化チタン、群青、カーボンブラックなどの顔料や染料を必要に応じて含有させておくことができる。
この他に、特開昭６２−２５３，１５９号(29)〜(31)頁、特開平１−１６１，２３６号(14)〜(17)頁、特開昭６３−３１６，８４８号、特開平２−２２，６５１号、同３−５６，９５５号、米国特許第５，００１，０３３号等に記載の支持体を用いることかできる。
これらの支持体の裏面は、親水性バインダーとアルミナゾルや酸化スズのような半導性金属酸化物、カーボンブラックその他の帯電防止剤を塗布してもよい。具体的には、特開昭６３−２２０，２４６号などに記載の支持体を使用できる。
感光材料の支持体の裏面には、耐水性のポリマーを塗布することも、処理後の接着性改善の点で好ましい。
表面抵抗率が１０¹²Ω・cm以下になるように設計することが望ましい。
また支持体の表面は親水性バインダーとの密着性を改良する目的で種々の表面処理や下塗りを施すことが好ましく用いられる。
【００８２】
本発明の感光材料は、印刷用感光材料の種々の用途、即ち、スキャナ用フィルムのみならず、網撮り用フィルム、線画用フィルム、密着用（ネガ−ポジ・タイプ）フィルム、密着用（反転ポジ−ポジ・タイプ）フィルム、あるいは、明室用フィルムとして利用できる。
【００８３】
本発明の熱現像感光材料に画像を露光し記録する方法としては、例えば製版カメラを用いてリバーサルフィルムのような印刷原稿を、コンタクトスクリーンや色分解フィルターで露光する方法、製版用プリンターを用いる方法、スキャナ、イメージセッタやファクシミリ等を用いて、画像情報を電気信号を経由してキセノンランプ、発光ダイオード、各種レーザー（レーザーダイオード、ガスレーザーなど）などを発光させ走査露光する方法（特開平２−１２９，６２５号、特願平３−３３８，１８２号、同４−９，３８８号、同４−２８１，４４２号等に記載の方法）がある。
【００８４】
熱現像感光材料へ画像を記録する光源としては、キセノンランプ、タングステンランプ、ハロゲンランプ、メタルハライドランプ、石英ランプ、発光ダイオード、レーザー光源等を用いることができる。
【００８５】
本発明における、露光装置の例を次に挙げる。市販のＡｒレーザーの露光装置である Linotype-Hell社のＤＣシリーズ、Crosfield 社のMagnascan シリーズ、市販のＨｅ−Ｎｅレーザーの露光装置である大日本スクリーン社のＳＧシリーズ及び市販のレーザーの露光装置である富士写真フイルム社のLux Scan、大日本スクリーン社のＭＴＲなどのカラースキャナー及び、Agfa-Gevaert社のSelectset （Ｈｅ−Ｎｅ）、Avantra(Red-LD) 、Linotype-Hell 社のHerkules(Red-LD)、Scitex社のDolev （Ｈｅ−Ｎｅ）、Agfa-Gevaert社のAccuset(Red-LD) 、富士写真フイルム社のLux Setter 5600 等のイメージセッター、ＮＥＣ社のＦＴ２４０ＲやＦＴ２６０Ｒのファクシミリ用露光装置を用いることができる。
【００８６】
本発明の露光において、利用できる製版用プリンターの例を次に挙げる。富士写真フイルムのＦＰＡ７４０、ＦＰＡ８００、ＦＰＡ８００Ｘ、ＦＰＡ８００Ｈｇ、ＦＰＡ８００ＦＸ、大日本スクリーン社のＰ６０７シリーズ、Ｐ６１７シリーズ、Ｐ６２７シリーズ、Ｐ６４７シリーズ、Ｐ６４８シリーズ、Ｐ６０７シリーズ、アイグラフィクス社のＩＰＢ−１０００ＳＨ、ウシオ社のＦＬ２Ｍ、ＦＬ３Ｍ、倉並社のＳＫ−１６、Eastman-Kodak 社のVersalite Contact Printer 840H、Contact 2200 Printer、Agfa-Gevaert社のＣＤＬ２００２Ｒｉ、キタムラ社のＰ−６、Ｐ−４、Ｐ−２、Ｐ−８、ＳＡＣＫ社のＯＲ３０、THIEMER 社のＶＤＭ５、CONVAC社のＲＤ７０８７Ｄを用いることができる。
【００８７】
本発明の露光において、利用できる製版用カメラの例を次に挙げる。富士写真フイルムのＦＣＳ８２０、ＦＣＳ８２０Ｓ、ＦＧＣ１００、ＦＧＣ２００、ＦＧＣ３００、大日本スクリーン社のＦＩＮＥ ＺＯＯＭ８８０、ＺＯＯＭＡＣＥ８００、コンパニカＣ−６８０、コンパニカＣ−６９０、Ｐ６４８シリーズ、Ｐ６０７シリーズ、アイテックグラフィクス社のImagemaker５４０、Eastman-Kodak 社のOpti-Copy ３２、Opti-Copy ４２、Opti-Copy ２３、イメージメーカー５０６０Ａ、イメージメーカーＩＭ２００、イメージメーカーＩＭ４００、イメージメーカーＩＭ６００、イメージメーカーＩＭ８００、Agfa-Gevaert社のＲＰＳカメラ、リプロマスターシリーズ、イズミヤ社のリニアス２０００、デザインスコープシリーズ、三菱製紙のリプロカメラシリーズを用いることかできる。
【００８８】
本発明の熱現像感光材料および／または錯化剤シートは、加熱現像および銀塩拡散転写のための加熱手段として導電性の発熱体層を有する形態であっても良い。この場合の発熱要素には、特開昭６１−１４５，５４４号等に記載のものを利用できる。
本発明において、米国特許第４，７０４，３４５号、同４，７４０，４４５号、特開昭６１−２３８，０５６号等に記載されている、少量の水の存在下で加熱し現像と転写を同時または連続して行うのが好ましい。この方式においては、加熱温度は、５０℃〜１００℃が好ましい。
【００８９】
本発明に用いられる水としては、一般に用いられる水であれば何を用いても良い。具体的には蒸留水、水道水、井戸水、ミネラルウォーター等を用いることかできる。また本発明の熱現像感光材料および錯化剤シートを用いる熱現像装置においては水を使い切りで使用しても良いし、循環し繰り返し使用してもよい。後者の場合、材料から溶出した成分を含む水を使用することになる。また特開昭６３−１４４，３５４号、同６３−１４４，３５５号、同６２−３８，４６０号、特開平３−２１０，５５５号等に記載の装置や水を用いても良い。さらに、水に溶解する低沸点溶媒、界面活性剤、かぶり防止剤、難溶性金属塩との錯形成化合物、防黴剤、防菌剤を含有させてもよい。
【００９０】
これらの溶媒は熱現像感光材料、錯化剤シートまたはその両者に付与する方法を用いることができるが、好ましくは、感材に付与する。その使用量は全塗布膜の最大膨潤体積に相当する溶媒の重量以下でよい。
この水を付与する方法としては、例えば特開昭６２−２５３，１５９号(5) 頁、特開昭６３−８５，５４４号等に記載の方法が好ましく用いられる。また、溶媒をマイクロカプセルに閉じ込めたり、水和物の形で予め熱現像感光材料もしくは色素固定要素またはその両者に内蔵させて用いることもできる。
付与する水の温度は前記特開昭６３−８５，５４４号等に記載のように３０℃〜６０℃であれば良い。特に水中での雑菌類の繁殖を防ぐ目的で４５℃以上にすることは有用である。
【００９１】
常温で固体であり高温では溶解する親水性熱溶剤を熱現像感光材料および／または錯化剤シートに内蔵させることができる。内蔵させる層は感光材料の感光性ハロゲン化銀乳剤層、中間層、保護層のいずれか、錯化剤シートのいずれの層でも良い。親水性熱溶剤の例としては、尿素類、ピリジン類、アミド類、スルホンアミド類、イミド類、アルコール類、オキシム類その他の複素環類がある。
【００９２】
現像および／または転写工程における加熱方法としては、加熱されたブロックやプレートに接触させたり、熱板、ホットプレッサー、熱ローラー、熱ドラム、ハロゲンランプヒーター、赤外および遠赤外ランプヒーターなどに接触させたり、高温の雰囲気中を通過させる方法などがある。
【００９３】
熱現像感光材料と錯化剤シートを重ね合わせる方法は特開昭６２−２５３，１５９号、特開昭６１−１４７，２４４号(27)頁記載の方法が適用できる。
【００９４】
本発明の写真要素の処理には種々の熱現像装置のいずれもが使用できる。例えば、特開昭５９−７５，２４７号、同５９−１７７，５４７号、同５９−１８１，３５３号、同６０−１８，９５１号、実開昭６２−２５，９４４号、特願平４−２７７，５１７号、同４−２４３，０７２号、同４−２４４，６９３号等に記載されている装置などが好ましく用いられる。また市販の装置としては富士写真フイルム株製ピクトロスタット１００、同ピクトロスタット２００、同ピクトロスタット３００、同ピクトログラフィー３０００、同ピクトログラフィー２０００などが使用できる。
【００９５】
【実施例】
以下実施例をもって本発明の説明を行うが、本発明はこれらに限定されるものではない。
【００９６】
実施例１
感光性ハロゲン化銀乳剤（Ｉ）の調製法について述べる。
良く攪拌している第１表に示す組成のｐＨ４のゼラチン水溶液を、第２表に示す（Ｉ）液と（II）液を同時に９分間かけて添加し、その５分後、(III) 液と(IV)液を１０分かけて同時に添加した。
【００９７】
【表１】

【００９８】
【表２】

【００９９】
【化１】

【０１００】
常法により、水洗、脱塩（沈降剤(1) を用い、硫酸でｐＨ３に調整して行った）後、石灰処理ゼラチン２２ｇを加えてｐＨ６．１、ｐＡｇ７．１に調節した後、防腐剤(1) を加え、６０℃で化学増感した。化学増感に用いた化合物は、第３表に示す通りに順次添加した。粒子サイズは、平均辺長０．１９μm で、標準偏差０．０１９μm の臭化銀含有率１．７モルの塩化銀立方体乳剤であった。この乳剤の収量は６３５ｇである。防腐剤(2) はフェノキシエタノールである。
【０１０１】
【表３】

【０１０２】
【化２】

【０１０３】
【化３】

【０１０４】
表３記載の臭化銀微粒子乳剤(2) の調製法について述べる。
良く攪拌している第４表に示す組成のゼラチン水溶液を、３０℃に降温し、第５表に示す（Ｉ）液と（II）液を同時に３分４０秒間かけて添加し、その５分後、(III) 液と(IV)液を２分かけて同時に銀電位を５０mVになるように(IV)液の流量を制御して添加した。
【０１０５】
【表４】

【０１０６】
【表５】

【０１０７】
常法により、水洗、脱塩（沈降剤１を用いてリン酸でｐＨ４．１に調整して行った）後、石灰処理ゼラチン２２ｇを加えてｐＨ６．１、ｐＡｇ７．８（ＫＢｒにより）調節した。防腐剤として、防腐剤(2) を用いた。粒子サイズ０．０５μm の臭化銀立方体乳剤であった。収量は６３０ｇである。
【０１０８】
この乳剤(1) １００ｇに、増感色素(3) を１０mgを含むメタノール溶液３ccを加え、４，４′−ビス〔４，６−ジ（ナフチル−２−オキシ）ピリミジン−２−イルアミノ〕スチルベン−２，２′−ジスルホン酸ジナトリウム塩の１％メタノール溶液０．２５ccを加え、カブリ防止剤(2) の０．８％メタノール水溶液６ccを加え、界面活性剤(1) ０．２ｇを、水溶性ポリマー(1) ０．２５ｇを加えて、乳剤層の塗布液を調製した。銀量１．４ｇ／m²のように塗布を行った。
パラターシャルブチルカテコールの１０％水メタノール混合溶液（体積比で水／メタノール＝７／３）を１５ccをさらに添加して、感光材料１０１の乳剤層の塗布液を作成した。
【０１０９】
【化４】

【０１１０】
【化５】

【０１１１】
【化６】

【０１１２】
次に還元剤１，５−ジフェニル−３−ピラゾリドンの固体状微粒子の分散物の調製法について述べる。１，５−ジフェニル−３−ピラゾリドン１０ｇ、花王製デモール０．２ｇを５．７％石灰処理ゼラチン９０ccを加えて、平均粒径０．７５mmのガラスビーズを用いてミルで３０分間分散した。ガラスビーズを分離して還元剤のゼラチン分散物を得た。
【０１１３】
次に、水酸化亜鉛の固体状微粒子分散物の調製法について述べる。
平均粒子サイズが０．２μm の水酸化亜鉛１２．５ｇ、分散剤としてカルボキシルメチルセルロース１ｇ、ポリアクリル酸ソーダ０．１ｇを４％ゼラチン水溶液１００ccに加えて、平均粒径０．７５mmのガラスビーズを用いてミルで３０分間分散した。ガラスビーズを分離して水酸化亜鉛のゼラチン分散物を得た。
【０１１４】
ロイコ染料と顕色剤の分散物の表６のように調製した。約６０℃に加熱溶解された油相成分を、６０℃に加温した水相成分に加え、攪拌混合したのち、ホモジナイザーで１０分間、１００００rpm にて分散した後、加水して均一な分散物を得た。
【０１１５】
【表６】

【０１１６】
【化７】

【０１１７】
以上のものを用いて、第６表に示す感光材料１０１を作成した。
【０１１８】
【表７】

【０１１９】
【化８】

【０１２０】
【化９】

【０１２１】
次に、感光材料１０１と同様の材料を用いて、同一の塗布銀量で、表８に示す感光材料１０２〜１１１を作成した。最上の感光性ハロゲン化銀乳剤層より上層の非感光性のゼラチン量は、保護層の酸処理ゼラチンの量で調整した。感光材料１１２は、感光材料１０５の第一層、第二層を入れ替えたものであり、感光材料１１３も同様に、感光材料１０９の第一層、第二層を入れ替えて作成した。
【０１２２】
【表８】

【０１２３】
Ａｇコロイド分散物を下記のように調製した。よく攪拌された第９表に示す溶液に、硝酸銀１７ｇを含む水溶液１７０ccを２５分かけて添加し、ゼラチンを添加し、常法により、水洗、脱塩（沈降剤(1) を用いて、硫酸でｐＨ３に調整して行った）後、石灰処理ゼラチンを加えてｐＨ６．１に調節した後、防腐剤(1) を加えて分散した。粒子サイズは、平均粒径０．０２μm で、濃度は、Ａｇ４％、ゼラチン濃度２％で、収量は２６３ｇである。
【０１２４】
【表９】

【０１２５】
高沸点溶媒(1) の分散物の表１０のように調製した。約６０℃に加熱溶解された油相成分を、６０℃に加温した水相成分に加え、攪拌混合したのち、ホモジナイザーで１０分間、１００００rpm にて分散した後、加水して均一な分散物を得た。高沸点有機溶媒の粒径は０．３μm であった。
【０１２６】
【表１０】

【０１２７】
【化１０】

【０１２８】
次に表１１に示すような処理シートＲ１を作成した。
【０１２９】
【表１１】

【０１３０】
【化１１】

【０１３１】
【化１２】

【０１３２】
Ｒ−１の吸水量は、４０℃で１３cc／m²であった。
【０１３３】
上記のように得られた感光材料１０１〜１１４を、露光を６７０nmにピークを持つ半導体レーザーで、１画素（１００μm²）あたり１０００万分の１秒で光量を変化させて露光した。露光済の感光材料は４０℃に保温した水に２．５秒浸したのち、ローラーで絞り、直ちに錯化剤シートと膜面が接するように重ね合わせた。次いで吸水した膜面の温度が８０℃となるように温度調整したヒートドラムを用い、２２秒間加熱し錯化剤シートＲ１を引きはがすと、感光材料に白黒銀画像が得られた
自動濃度測定器を用いて、透過画像の青色濃度と露光量の関係である特性曲線を得た。この特性曲線より最高濃度Ｄmax と最低濃度Ｄmin を測定した。また、製造直後の感光材料のＤmin から、経時した感光材料から得られたＤmin の値を差し引き変動幅を比較した。またＩＳＯ６０７７に記載の脆性のためのウェッジテストを行い、脆性の差を比較した。
これらの結果を表１２に示す。以上の結果より、本発明においては、Ｄmin が低く、かつＤmax が高く、しかも、足階調が高く、処理ムラの少ない高画質の画像が得られ、中間層の設置により、経時によるＤmin 上昇が抑えられ、膜の脆性が良化していることが分かった。
【０１３４】
【表１２】

[0001]
BACKGROUND OF THE INVENTION
The present invention uses a silver halide and can obtain a black and white image in a short time without using a developer, has a low Dmin, a high gradation, a high sharpness, and particularly excellent in preservability and brittleness. The present invention relates to an image forming method using a photothermographic material.
[0002]
[Prior art]
A photographic method using silver halide has been used most widely since it has superior photographic characteristics such as sensitivity, gradation adjustment, and resolving power compared to other photographic methods such as electrophotography and diazo photography. .
[0003]
At present, as image information, the amount of information and ease of expression have shifted greatly from black and white images to color images, but black and white images are preferred and used in certain fields, for example, in medical fields. Yes. Or, in printing, character information or the like is usually used as a monochrome image.
[0004]
In recent years, image forming processing methods for photosensitive materials using silver halide have been changed from conventional wet processing to instant systems incorporating a developing solution, and further, dry thermal development processing by heating, etc. Systems that can easily and quickly obtain images without using them have been developed from the viewpoint of environmental protection. Such photothermographic materials are described in “Photographic Fundamentals (Non-Silver Photo Edition) Corona Publishing” pages 242 to 255, Japanese Patent Publication Nos. 43-4922, 43-4924, etc. Yes.
In terms of products, 3M's dry silver sensitive materials are on sale for black and white systems.
[0005]
As with dry silver, monosheet sensitive materials consisting of silver halide, organic silver salt, and reducing agent have unused silver halide and organic silver salt remaining in the heat-developed image. . For this reason, when exposed to intense light or stored for a long period of time, the remaining silver halide or organic silver salt is printed out and the white background is colored, and the contrast is lost.
[0006]
Further, a method for obtaining a black color image by dry processing is described in Research Disclosure (hereinafter abbreviated as RD) September 1978, pages 49-51 (RD17326). Since it is an unfixed type containing a silver salt therein, it has the same disadvantages as described above.
[0007]
In order to remedy these drawbacks, a movable (diffusible) dye is formed or released in an image form by heating, and then the movable dye is converted into a dye-accepting substance such as a mordant, using various transfer solvents. Japanese Patent Publication Nos. 3-78617 and 3-45820 describe methods for forming black and white images having improved storage stability by transferring to a dye-fixing material containing a heat-resistant organic polymer substance. However, since these methods are methods of transferring after heat development, the number of steps is large and the processing time is long.
[0008]
Further, JP-A-3-260645 discloses a method for transferring a dye formed by coupling after development and a method for simultaneously developing and transferring a heat development transfer type black and white image forming method utilizing a coupling reaction. Has been. However, since this method does not have an effective development transfer accelerator, the processing requires a long time at a high temperature.
[0009]
Japanese Patent Application Laid-Open No. 62-121848 discloses that a black and white image can be formed with a transfer dye image by heat development using a small amount of water. However, in order to obtain an image having a transmission density of 2 or more required for many black-and-white images in a short time by the dye transfer method, the film thickness of the photosensitive material, especially the binder amount, is reduced as much as possible, or the use of a dye-donating compound is used. It is necessary to increase the amount. For this reason, there arises a problem that the film quality deteriorates and the manufacturing cost increases. Further, there is a problem that the application is limited due to a decrease in sharpness due to transfer. Furthermore, it is difficult to synthesize a black dye-donating compound, and it is also difficult to obtain a desired neutral gray color image by mixing yellow, magenta, and cyan dye-donating compounds.
[0010]
On the other hand, JP-A-62-283332, JP-A-63-198050, JP-A-60-194448, etc. disclose a method for forming a silver image on an image-receiving sheet by heat development silver salt diffusion transfer using a silver halide photosensitive material. Although disclosed, these methods are also methods using a transferred silver image, and it is difficult to obtain an image having a transmission density of 2 or more and high sharpness in a short time, and improvement has been required.
[0011]
The heat-developed silver image formed in the light-sensitive material is expected to have high sharpness, but due to undeveloped remaining silver halide, the Dmin is high and the remaining silver halide is printed out. Therefore, there is a problem that the image after processing is extremely unstable.
[0012]
On the other hand, after exposing a photosensitive material containing a photosensitive silver halide, a hydrophilic binder, and a reducing agent on a support, a processed sheet containing a complexing agent is bonded and heat-developed, and then black and white silver is formed on the photosensitive material. A method for obtaining an image is described in JP-A-8-54705 and JP-A-8-101487. In this method, a light-sensitive material contains a basic metal compound that is hardly soluble in water, and a compound capable of undergoing a complex-forming reaction in a processing sheet using a metal ion constituting the basic metal compound and water as a medium ( Complexing agent) is contained, and an alkaline atmosphere is realized by complex formation reaction of both compounds during heat development.
In this image forming method, when a reducing agent or a basic metal compound is introduced into a photosensitive material, it is often used as a solid fine particle dispersion for the purpose of improving storage stability. However, when such a solid dispersion is used (particularly when it is provided in a hydrophilic colloid layer provided between the photosensitive silver halide emulsion layer and the support), the brittleness of the entire coating film is deteriorated. was there. Further, even when a reducing agent or a basic metal compound is used as a solid fine particle dispersion, the storage stability of the photosensitive material is not sufficient, and further improvement has been desired.
[0013]
[Problems to be solved by the invention]
An object of the present invention is to produce a photosensitive material for use in an image forming method that provides a high-quality black-and-white image having a low Dmin, a high density, a high gradation, and an excellent sharpness without using a developer. The purpose is to improve storage stability and film quality.
[0014]
[Means for Solving the Problems]
The above object is to provide a silver halide photosensitive material containing at least a photosensitive silver halide emulsion, a hydrophilic binder, and a water-insoluble basic metal compound on a support after imagewise exposure or simultaneously with imagewise exposure. The photosensitive material is obtained by superimposing a complex-forming compound for a metal ion constituting the basic metal compound, a sheet containing a physical development nucleus and a silver halide solvent, and thermally developing in the presence of a reducing agent and water. In the method for forming a silver image, a hydrophilic binder layer not containing a solid fine particle dispersion is provided on the support side below the photosensitive silver halide emulsion layer of the silver halide photosensitive material, and the hydrophilic binder Amount 0.1g / m ² 2g / m or more ² An image forming method characterized in that the binder amount of the non-photosensitive layer above the photosensitive silver halide emulsion layer is 0.1 g / m ² 1g / m or more ² This is achieved by the above-described image thermal development forming method, which is characterized by the following.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the image forming system described above has a hydrophilic binder layer not containing solid fine particle dispersion on the support side below the photosensitive silver halide emulsion layer, and the amount of hydrophilic binder is 0.1 g / M ² 2g / m or more ² Or less, preferably 0.35 g / m ² 1g / m or more ² Or less, more preferably 0.5 g / m ² 0.75g / m or more ² The film quality and raw storage stability of the photosensitive material could be improved by installing the following.
It has also been found that the amount of binder above the photosensitive layer affects the fixing speed of undeveloped silver halide, and the smaller the amount of binder, the faster the fixing speed and the greater the influence on Dmin on the photosensitive material. Specifically, the binder amount of the non-photosensitive layer above the uppermost photosensitive silver halide emulsion layer is preferably 0.1 g / m. ² 1g / m or more ² Or less, more preferably 0.15 g / m ² 0.5 g / m ² The fixing speed can be increased and Dmin can be lowered by the following.
In the present invention, the non-photosensitive layer above the uppermost photosensitive silver halide emulsion layer is preferably a protective layer. Furthermore, it is more preferable that the non-photosensitive hydrophilic binder layer not containing the solid fine particle dispersion according to the present invention is adjacent to the emulsion layer. The layer containing a basic metal compound hardly soluble in water and the layer containing a reducing agent are preferably provided between the emulsion layer and the support. In the present invention, since the non-photosensitive hydrophilic binder layer is provided, the brittleness of the film of the photosensitive material is not deteriorated even when a basic metal compound or a reducing agent is added as a solid fine particle dispersion. Stability is further improved.
When there are two or more photosensitive silver halide emulsion layers, a plurality of hydrophilic binder layers can be provided between the emulsion layers and the support side layer. When the photosensitive silver halide emulsion layers are adjacent to each other, it is preferably disposed between the emulsion layer closer to the support and the layer on the support side.
The amount of binder in the non-photosensitive layer above the uppermost photosensitive silver halide emulsion layer can be changed by the amount of binder added when preparing the coating solution or the amount of binder brought in when other compounds are binder dispersions. .
[0016]
The binder used in the present invention will be described in detail later, but mainly gelatin is preferably used. The inventor found that the amount of binder in the non-light-sensitive layer above the uppermost light-sensitive silver halide emulsion layer and the amount of binder in the intermediate layer containing no solid fine particle dispersion on the support side of the light-sensitive silver halide emulsion layer In the case of the above combination, it has been found that Dmin is low without decreasing Dmax, the gradation of the foot portion of the characteristic curve becomes stiff, the raw preservation property is remarkably improved, and the brittleness is further improved. Such an effect was new and unexpected.
[0017]
In the present invention, regarding a combination of a water-insoluble basic metal compound used as a base precursor and a compound (referred to as a complex-forming compound or a complexing agent) capable of complexing with a metal ion constituting the hardly-soluble metal compound JP-A-62-129848, European Patent Publication No. 210,660A2, US Pat. No. 4,740,445, and the like.
[0018]
Preferable poorly soluble basic metal compounds are zinc or aluminum oxides, hydroxides and basic carbonates, particularly preferably zinc oxide, zinc hydroxide and basic zinc carbonate.
A metal compound that is hardly soluble in water is used by dispersing fine particles in a hydrophilic binder as described in JP-A-59-174830. The average particle diameter of the fine particles is 0.001 to 5 μm, preferably 0.01 to 2 μm. The content in the photosensitive material is 0.01 g / m ² ~ 5g / m ² Preferably 0.05 to 2 g / m ² It is.
[0019]
Complex-forming compounds used in sheets containing complex-forming compounds for metal ions of basic metal compounds that are hardly soluble in water (hereinafter referred to as complexing agent sheets) are known as chelating agents in analytical chemistry and hard water softening agents in photographic chemistry. belongs to. Details thereof are described in addition to the aforementioned patent specifications, as well as A. Written by Ringbom, Nobuyuki Tanaka, Haruko Sugi, "Complex Formation Reaction" (Industry Books). Preferred complex-forming compounds for the present invention are water-soluble compounds such as aminopolycarboxylic acids (including salts) such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, aminotris (methylenephosphonic acid), ethylenediamine, and the like. Examples thereof include aminophosphonic acid (salt) such as tetramethylenephosphonic acid, pyridinecarboxylic acid (salt) such as 2-picolinic acid, pyridine-2,6-dicarboxylic acid, and 5-ethyl-2-picolinic acid. Among these, pyridinecarboxylic acid (salt) is particularly preferable.
[0020]
In the present invention, the complex-forming compound is preferably used as a salt neutralized with a base. Particularly preferred are salts with organic bases such as guanidines, amidines, tetraalkylammonium hydroxide, and salts with alkali metals such as sodium, potassium and lithium. A mixture thereof may be used. Specific examples of preferable complex-forming compounds are described in JP-A-62-2129848, European Patent Publication 210,660A2, and the like. The content of the complex-forming compound in the complexing agent sheet is 0.01 to 10 g / m. ² Preferably 0.05 to 5 g / m ² It is.
[0021]
In the present invention, the complexing agent sheet contains physical development nuclei, but the physical development nuclei reduce soluble silver salt diffused from the light-sensitive material to convert it into physical development silver and fix it to the complexing agent sheet. It is something to be made. Physical development nuclei include heavy metals such as zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt, copper, ruthenium, noble metals such as palladium, platinum, silver and gold, or their sulfur, selenium. Any known physical development nuclei such as colloidal particles of chalcogen compounds such as tellurium can be used. These physical development nuclei are prepared by reducing the corresponding metal ions with a reducing agent such as ascorbic acid, sodium borohydride, hydroquinone, etc. to form a metal colloidal dispersion, or soluble sulfides, selenides or tellurides. It is obtained by mixing the solution to form a water-soluble metal sulfide, metal selenide or metal telluride colloidal dispersion. These dispersions are preferably formed in a hydrophilic binder such as gelatin. A method for preparing colloidal silver particles is described in US Pat. No. 2,688,601. If necessary, a desalting method for removing excess salts known in silver halide emulsion preparation methods may be performed.
These physical development nuclei preferably have a particle size of 2 to 200 nm.
These physical development nuclei are usually 10% on the complexing agent sheet. ^-3 ~ 100mg / m ² , Preferably 10 ^-2 -10 mg / m ² Contain.
The physical development nuclei can be prepared separately and added to the coating solution. In the coating solution containing a hydrophilic binder, for example, silver nitrate and sodium sulfide, or gold chloride and a reducing agent are reacted. You may create it.
As the physical development nucleus, silver, silver sulfide, palladium sulfide or the like is preferably used. When physically developed silver transferred to a complexing agent sheet is used as an image, palladium sulfide, silver sulfide or the like is preferably used in that Dmin is cut and Dmax is high.
[0022]
A well-known thing can also be used for the silver halide solvent used by this invention. Examples thereof include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, sulfites such as sodium sulfite and sodium hydrogen sulfite, thiocyanates such as potassium thiocyanate and ammonium thiocyanate, and those described in JP-B-47-11386. Thioether compounds such as 8-di-3,6-dithiaoctane, 2,2'-thiodiethanol, 6,9-dioxa-3,12-dithiatetradecane-1,14-diol, Japanese Patent Application No. 6-325350 A compound having a 5- to 6-membered imide ring such as uracil and hydantoin described above, and a compound having the following general formula described in JP-A No. 53-144319 can be used. Analytica Chemica Acta 248: 604-614 (1991) as described in trimethyltriazolium thiolate is also preferred meso-ion thiolate compound. A compound capable of fixing and stabilizing silver halide described in Japanese Patent Application No. 6-206331 can also be used as a silver halide solvent.
N (R1) (R2) -C (-S) -X-R3
In the formula, X represents a sulfur atom or an oxygen atom. R1 and R2 may be the same or different and each represents an aliphatic group, an aryl group, a heterocyclic residue or an amino group. R3 represents an aliphatic or aryl group. R1 and R2 or R2 and R3 may be bonded to each other to form a 5-membered or 6-membered heterocycle. You may use together said silver halide solvent.
In the present invention, among the above compounds, compounds having a 5- to 6-membered imide ring such as sulfite, uracil and hydantoin are particularly preferable.
[0023]
The total silver halide solvent content in the complexing agent sheet of the present invention is 0.01 to 50 mmol / m. ² Preferably 0.1 to 30 mmol / m ² It is. More preferably 1 to 20 mmol / m ² It is. The molar ratio is 1/20 to 20 times, preferably 1/10 to 10 times, and more preferably 1/3 to 3 times the molar amount of silver applied to the photosensitive material. The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide, or methylpropyl glycol, or an alkali or acidic aqueous solution, or may be dispersed in solid fine particles and added to the coating solution.
[0024]
In the present invention, the concentration of the silver image in the light-sensitive material is controlled by incorporating a polymer having vinyl imidazole and / or vinyl pyrrolidone repeating units described in Japanese Patent Application No. 6-325350 as a constituent component in the complexing agent sheet. It is possible to increase.
[0025]
The photothermographic material used in the present invention basically has a photosensitive silver halide emulsion, a hydrophilic binder, a reducing agent, and a basic metal compound hardly soluble in water on a support. Accordingly, an organic metal salt oxidizing agent, a dye donating compound and the like can be contained.
These components are often added to the same layer, but can also be added separately in separate layers. The reducing agent is incorporated in the photothermographic material, but may also be supplied from the outside, for example, by diffusing from a complexing agent sheet. The silver halide emulsion photosensitive layer may be divided into two or more layers as necessary.
[0026]
The photothermographic material is provided with various non-photosensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a filter layer, and an antihalation layer between the above-mentioned silver halide emulsion layers and the uppermost layer and the lowermost layer. Alternatively, various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, an undercoat layer as described in US Pat. No. 5,051,335, a reduction as described in JP-A-1-120,553, 5-34,884 and 2-64,634. An intermediate layer having an agent and a DIR compound, an intermediate layer having an electron transfer agent as described in US Pat. Nos. 5,017,454, 5,139,919, and JP-A-2-235044, JP-A-4 A protective layer having a reducing agent as described in No. -249,245 or a combination of these layers can be provided.
When the support is a polyethylene laminated paper containing a white pigment such as titanium oxide, the back layer has an antistatic function and a surface resistivity of 10 ¹² It is preferable to design so as to be Ω · cm or less.
[0027]
Silver halide grains that can be used in the present invention are silver chloride, silver iodochloride, silver chlorobromide, silver iodochlorobromide, silver iodobromide, and silver bromide. The silver iodide content is preferably 10 mol% or less, more preferably 1 mol% or less. More preferably, it is 0.5 mol% or less.
The silver halide emulsion used in the present invention may be a surface latent image type or an internal latent image type. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent and optical fogging. Further, it may be a multi-structure particle having a different halogen composition inside the particle and on the particle surface. Further, silver halide emulsions having different compositions may be joined by epitaxial joining.
In particular, in a silver chlorobromide emulsion having a silver chloride content of 80 mol% or more, the silver bromide localized phase has a layered or non-layered silver halide inside and / or on the surface as described above. Structures can also be used. The halogen composition of the localized phase preferably has a silver bromide content of at least 20 mol%, and more preferably exceeds 30 mol%. The silver bromide content of the silver bromide localized phase is analyzed by an X-ray diffraction method or the like. For example, Photographic Science and Technology, Volume 2 pages 149 (1955) and Volume 4 pages 22 (1957) by C. Berry, SJMarion, to X-ray diffraction silver halide. The application method of is described. The silver bromide localized phase can be inside the grain, at the edge, corner, or face of the grain surface, and a preferable example is one that is epitaxially bonded to the corner of the grain.
[0028]
The shape of the silver halide grains is a normal crystal containing no twin plane, a single twin containing one twin plane, a parallel multiple twin containing two or more parallel twin planes, and a non-parallel twin plane. It can be used according to the purpose from non-parallel multiple twins including two or more, spherical shape, potato shape, flat plate shape with high aspect ratio, and a composite system thereof. The shape of the twin grains is described in the Photographic Society of Japan, Basics of Photographic Industry-Silver Salt Photo Edition (Corona), page 163.
In the case of a normal crystal, a cube having a (100) plane, an octahedron having a (111) plane, or a dodecahedron particle having a (110) plane can be used. The dodecahedron particles are described in JP-B-55-42737 and JP-A-60-222842. Furthermore, it is reported in Journal of Imaging Science 30: 247 (1986). (H11) face, (hh1) face, (hk0) face, and (hk1) face particles can also be used according to the purpose. A tetrahedron having (111) and (100) faces and particles having (111) and (110) faces can also be used. If necessary, polyhedral particles such as a 38-hedron, rhomboid 24-hedron, 46-hedron, and 68-hedron can be used.
High aspect ratio flat plates can also be preferably used. Tabular grains of high silver chloride emulsion grains comprising (111) faces are described in U.S. Pat. Nos. 4,399,215, 4,400,463, 5,217,858, JP-A-2-32 and the like. Has been. Furthermore, Journal of Photographic Science 36: 182 (1988) also reports an empirical rule for the formation of silver chloride tabular grains. Tabular grains of high silver chloride emulsion grains comprising (100) planes are U.S. Pat. Nos. 4,946,772, 5,275,930, 5,264,337, Japanese Patent Application No. 4-214109, These are described in Japanese Patent Application No. 5-96250, European Patent No. 0534395A1, and the like.
[0029]
Such tabular grains having a high aspect ratio are advantageous in terms of color sensitization sensitivity because they can increase the adsorption amount of the sensitizing dye because they have a larger surface area than normal crystals of the same volume. Further, since it is advantageous in terms of covering power, a high Dmax can be achieved with a low silver amount. Since the specific surface area is large, the development activity is also high.
[0030]
The average grain size of the silver halide grains may be any size from fine grains having a diameter of 0.05 μm or less to large grains having a projected area diameter exceeding 10 μm. The thickness is preferably 0.1 to 2 μm, particularly preferably 0.1 to 0.9 μm.
Monodispersed emulsions having a narrow grain size distribution may be used. The monodispersed emulsion is, for example, a silver halide emulsion having a grain size distribution in which 80% or more of all grains fall within ± 30% of the average grain size in terms of the number of grains or weight.
Polydisperse emulsions having a wide grain size distribution may be used.
In addition, as disclosed in JP-A-1-167743 and 4-223463, two or more kinds of monodispersed silver halides having substantially the same color sensitivity and different grain sizes are used for the purpose of adjusting the gradation. An emulsion may be used in combination. Two or more types of emulsions may be mixed in the same layer or may constitute separate layers. Two or more types of polydispersed silver halide emulsions or a combination of a monodispersed emulsion and a polydispersed emulsion can also be used.
[0031]
In the process of preparing the silver halide emulsion in the present invention, it is preferable to carry out a desalting step for removing excess salts. You may use the noodle washing method performed by gelatinizing gelatin, and also inorganic salt (for example, sodium sulfate) which consists of a polyvalent anion, anionic surfactant, anionic polymer (for example, sodium polystyrene sulfonate), A precipitation method (flocculation) using a gelatin derivative (aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. Alternatively, an ultrafiltration device shown in US Pat. No. 4,758,505, JP-A-62-113137, JP-B-59-43727, US Pat. No. 4,334,012 may be used, A natural sedimentation method or a centrifugal separation method may be used. Usually, a sedimentation method is preferably used.
[0032]
The method of preparing silver halide emulsions is described in “Photophysics and Chemistry” by Grafkide, published by Paul Monter (P. Glafkides, Chimie et Physique Photographique Paul Montel, 1967) GFDuffin, Photographic Emulsion Chemistry (Focal Press, 1966), “Production and coating of photographic emulsion” by Zerikman et al., Published by Focal Press (VLZelikman et al.
The preparation method may be any of an acidic method, a neutral method, and an ammonia method. You may make it high pH to the extent that covering does not generate | occur | produce. As a form for reacting the soluble silver salt and the soluble halogen salt, a one-side mixing method, a simultaneous mixing method, or a combination thereof can be used. A method (so-called back mixing method) in which particles are formed in a state of excessive silver ions can also be used. As one of the simultaneous mixing methods, a method of keeping pAg in a liquid layer in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal system and a nearly uniform grain size can be obtained.
[0033]
In preparing a silver halide emulsion, it is preferable to adjust the pAg and pH during grain formation. For adjustment of pAg and pH, see Photographic Science and Engineering, Vol. 6, pp. 159-165 (1962); Journal of Photographic Science, 12 Vol. 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748.
[0034]
As the protective colloid used in preparing the emulsion in the present invention, gelatin is preferably used, but other hydrophilic binders can also be used. The hydrophilic binder can be used alone or in combination with gelatin. Examples of hydrophilic binders include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose and cellulose sulfates, sodium alginate, starch derivatives, polysaccharides Synthetic hydrophilic polymers such as carrageenan, polyvinyl alcohol, modified alkyl polyvinyl alcohol, polyvinyl-N-pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, or a single or copolymer, A thioether polymer described in US Pat. No. 3,615,624 can also be preferably used.
In addition to lime-processed gelatin, gelatin derivatives such as acid-processed gelatin, decalcified gelatin, and phthalated gelatin, and low-molecular gelatin can also be used. Gelatin oxidized with an oxidizing agent such as hydrogen peroxide or gelatin treated with an enzyme can also be used. A hydrolyzate or enzyme degradation product of gelatin can also be used.
[0035]
Examples of the silver halide solvent include thiocyanate (described in U.S. Pat. Nos. 2,222,264, 2,448,534 and 3,320,069), thioether compound (U.S. Pat. 3,271,157, 3,574,628, 3,704,130, 4,297,439, and 4,276,347), thione compounds (special Nos. 53-144319, 53-82408, and 55-77737) and imidazole compounds (described in JP-A-54-100717), benzimidazole (JP-B-60-54662), and amines Examples thereof include compounds (described in JP-A-54-100717). Ammonia can be used in combination with a silver halide solvent as long as it does not cause adverse effects. Nitrogen-containing compounds as described in JP-B-46-7781, JP-A-60-222842, JP-A-60-122935 and the like can be added to the silver halide grain forming stage. Details of specific examples of the silver halide solvent are described on pages 12 to 18 of JP-A-62-215272.
[0036]
Metal salts (including complex salts) may coexist in the process of silver halide grain formation or physical ripening. Examples of metal salts include salts or complex salts of noble metals or heavy metals such as cadmium, zinc, lead, thallium, iridium, platinum, palladium, osmium, rhodium, chromium, ruthenium, rhenium. These compounds may be used alone or in combination of two or more. As complex ions and coordination compounds, bromine ions, chlorine ions, cyan ions, nitrosyl ions, thionitrosyl ions, water, ammonia and the like and combinations thereof are preferably used. For example, yellow blood salt, K ₂ IrCl ₆ , K _Three IrCl ₆ , (NH _Four ) ₂ RhCl _Five (H ₂ OK ₂ RuCl _Five (NO), K _Three Cr (CN) ₆ Etc. are preferably used. The amount added depends on the purpose of use, but is 10 per mole of silver halide. ^-9 -10 ^-2 It is about the molar range. The position incorporated in the silver halide grain may be uniform within the grain, or may be a localized position on the surface or inside of the grain, a silver bromide localized phase, or a high silver chloride grain base. These compounds can be added by mixing the metal salt solution with the aqueous halide solution at the time of grain formation, adding silver halide emulsion fine grains doped with the metal ions, or adding the metal salt solution to the grains. During the formation, the addition can be performed directly after the formation of the particles.
[0037]
In order to increase the sensitivity and density of high-illuminance exposure, metal complex salts such as iridium and cyanide ions such as yellow blood salt, lead chloride, cadmium chloride, and zinc chloride can be preferably used. In the case of spectral sensitization in the red or infrared region, it is preferable to use a metal complex salt such as yellow blood salt having a cyanide ion as a ligand, lead chloride, cadmium chloride, or zinc chloride. For the purpose of high contrast, rhodium salts, ruthenium salts, and chromium salts are preferably used.
[0038]
A silver salt solution (for example, AgNO) to be added during the formation of silver halide grains _Three The particle formation rate may be increased by increasing the addition rate, addition amount or addition concentration of the aqueous solution) and the halogen compound solution (for example, KBr aqueous solution). Thus, methods for rapidly forming silver halide grains are described in British Patent No. 1,335,925, US Pat. Nos. 3,672,900, 3,650,757, and 4,242,445. Nos. 55-142329, 55-158124, 58-113927, 58-113928, 58-11934, and 58-11936.
[0039]
During or after the grain formation, the surface of the silver halide grain may be substituted with a halogen that forms a hardly soluble silver halide grain (halogen conversion). This halogen conversion process is described in "Die Grundlagen der Photographischen Prozesse mit Silverhalogeniden" pages 662-669 and "The Theory of Photography". The Theory of Photographic Process, 4th edition, pages 97-98, etc. In this method, the solution may be added in the form of a soluble halide, or may be added in the form of fine grain silver halide.
[0040]
During and / or after grain formation, thiosulfonates, dichalcogen compounds described in US Pat. Nos. 5,219,721 and 5,364,754, lipoic acid, cysteine, elemental sulfur, cobalt ammonia complex Such an inorganic metal complex may be added.
The silver halide emulsion of the present invention can be used as it is without chemical sensitization, but is usually used after chemical sensitization. The chemical sensitizing method used in the present invention includes sulfur sensitizing method, selenium sensitizing method, chalcogen sensitizing method such as tellurium sensitizing method, noble metal sensitizing method using gold, platinum, palladium, etc. and reduction sensitizing method. Can be used alone or in combination (for example, JP-A-3-110555, Japanese Patent Application No. 4-75798). Such chemical sensitization can be performed in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-Open No. 62-253159). Further, an antifoggant described later can be added after completion of chemical sensitization. Specifically, the methods described in JP-A-5-45833 and JP-A-62-240446 can be used.
[0041]
As the sulfur sensitizer, an unstable sulfur compound is used. Specifically, thiosulfate (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, allylthiourea, etc.), allyliso A known sulfur compound such as thiocyanate, cystine, p-toluenethiosulfonate, rhodanine, or mercapto may be used. The amount of sulfur sensitizer added may be an amount sufficient to effectively increase the sensitivity of the emulsion, and the appropriate amount is pH, temperature, balance with other sensitizers, the size of silver halide grains, etc. Varies depending on various conditions. As a guideline, it should be 10 per mole of silver halide. ^-9 -10 ^-1 It is preferably used in the molar range.
[0042]
In selenium sensitization, a known unstable selenium compound is used. Specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone , Selenamides, aliphatic isoselenocyanates (eg, allyl isoselenocyanate), selenocarboxylic acids and esters, selenophosphates, diethyl selenides, diethyl diselenides, etc. it can. The addition amount varies depending on various conditions as in the case of the sulfur sensitizer. ^-Ten -10 ^-1 It is preferably used in the molar range.
[0043]
In the present invention, in addition to the above chalcogen sensitization, sensitization with a noble metal can also be performed. First, in gold sensitization, the gold valence may be either +1 or +3, and various gold compounds are used. Typical examples include chloroauric acids, potassium chloroaurate, auric trichloride, potassium aurithiocyanate, potassium iodoaurate, tetraauric acid, ammonium aurothiocyanate, pyridyltrichlorogold, gold sulfide, gold selenide, gold telluride. Etc.
The amount of the gold sensitizer added varies depending on various conditions, but as a guideline, it is 10 per silver halide. ^-Ten -10 ^-1 It is preferably used in the molar range.
The gold sensitizer may be added at the same time as sulfur sensitization, selenium sensitization, or tellurium sensitization, or before, during, or after sulfur, selenium, or tellurium sensitization. It is also possible to use it.
There is no particular limitation on the pAg and pH of the emulsion to be subjected to sulfur sensitization, selenium sensitization, tellurium sensitization or gold sensitization in the present invention, but it is preferable to use pAg in the range of 5 to 11 and pH in the range of 3 to 10. . Further preferably, the pAg is in the range of 6.8 to 9.0 and the pH is in the range of 5.5 to 8.5.
In the present invention, noble metals other than gold can also be used as chemical sensitizers. As noble metals other than gold, for example, sensitizers using metal salts such as platinum, palladium, iridium and rhodium or complex salts thereof can be used.
[0044]
In the present invention, reduction sensitization can be further performed. Known reduction sensitizers used in the present invention include sulfites, ascorbic acid, stannous salts, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds, and the like. In the present invention, one of these known compounds can be selected and used, or two or more compounds can be used in combination. As a reduction sensitizer, stannous chloride, thiourea dioxide, dimethylamine borane, L-ascorbic acid, and aminoiminomethanesulfinic acid are preferable compounds. Since the addition amount of the reduction sensitizer depends on the emulsion conditions, it is necessary to select the addition amount, but it is 10 per mol of silver halide. ^-9 -10 ^-2 A molar range is suitable.
In addition to the above-described method of adding the reduction sensitizer, growth is performed in a low pAg atmosphere of pAg 1 to 7 called gold ripening, or a method of ripening, growth in a high pH atmosphere of pH 8 to 11 called high pH ripening, Alternatively, a method of aging, a method of reducing sensitization with hydrogen in the nascent stage through hydrogen gas or electrolysis can be selected. Furthermore, two or more methods can be used in combination.
Although this reduction sensitization can be used alone, it can also be used in combination with the above chalcogen sensitization or noble metal sensitization.
[0045]
In order to give the silver halide used in the present invention green sensitivity, red sensitivity, and infrared sensitivity, the photosensitive silver halide emulsion may be spectrally sensitized with nuclei of methine dyes. If necessary, the blue-sensitive emulsion may be spectrally sensitized in the blue region.
The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A renin nucleus, indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.
The merocyanine dye or the complex merocyanine dye includes a pyrazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanine nucleus as a nucleus having a ketomethylene structure. 5-6 membered heterocycle nuclei such as thiobarbituric acid nuclei can be applied.
Specific examples include sensitizing dyes described in U.S. Pat. No. 4,617,257, JP-A-59-180550, JP-A-64-13546, JP-A-5-45828, and 5-45834. It is done.
These sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used for the purpose of adjusting the wavelength of supersensitization or spectral sensitization.
Along with the sensitizing dye, the dye itself does not have a spectral sensitizing action or a compound that does not substantially absorb visible light, or a compound exhibiting supersensitization may be contained in the emulsion (for example, the US No. 36156641, JP-A-59-192242, JP-A-59-191032, and JP-A-63-23145). In particular, those described in JP-A-59-191032 and 59-192242 are preferably used when a sensitizing dye having spectral sensitization sensitivity from the red region to the infrared region is used.
[0046]
The timing of adding the dye to the emulsion may be at any stage of the emulsion preparation. Most commonly, it is performed during the period after completion of chemical sensitization and before application, but as described in US Pat. Nos. 3,628,969 and 4,225,666. Spectral sensitization can be performed simultaneously with chemical sensitization by adding at the same time as the sensitizer, or can be performed prior to chemical sensitization as described in JP-A-58-113928. It can also be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, as taught in U.S. Pat. No. 4,225,666, adding these compounds separately, i.e., adding a portion of these compounds prior to chemical sensitization, It is possible to add the remainder after chemical sensitization and any time during the formation of silver halide grains, including the method taught in US Pat. No. 4,183,756. .
The amount added is 9 x 10 per mole of silver halide. ^-9 ~ 9x10 ^-3 Can be used in moles.
These sensitizing dyes and supersensitizers can be used in solutions of hydrophilic organic solvents such as methanol, aqueous solutions (which may be alkaline or acidic to increase solubility), dispersions of gelatin, or surfactants. What is necessary is just to add with a solution.
[0047]
In order to enhance the adsorption of the sensitizing dye, a soluble Ca compound, a soluble Br compound, a soluble I compound, a soluble Cl compound, and a soluble SCN compound may be added before, during and after the addition of the sensitizing dye. These compounds may be used in combination. Preferably, CaCl ₂ , KI, KCl, KBr, KSCN. Further, it may be in the form of fine silver bromide, silver chlorobromide, silver iodobromide, silver iodide, or rhodan silver emulsion grains.
[0048]
There are no particular restrictions on the other additives of the photographic material to which the emulsion of the present invention is applied. For example, Research Disclosure, Vol. 176, Item 17643 (RD-17643), Vol. 187, Item 18716 ( RD-18716), 307 volumes, item 307105, etc. can be referred to.
[0049]
Descriptions of various additives in RD-17743, RD-18716, and RD-307105 include additives used in such a process and known photographic additives that can be used in the photosensitive material and complexing agent sheet of the present invention. Listed below.

[0050]
Among the additives, antifoggants and stabilizers include azoles (for example, benzothiazolim salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benztriazoles, amino Triazoles, etc.); mercapto compounds (eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole and derivatives thereof), mercaptopyrimidines Thioketo compounds such as oxadrine thione; azaindenes {eg triazaindenes, tetraazaindenes ( 4-hydroxy-6-methyl (1,3,3a, 7) tetraazaindene), pentaazaindenes, etc.); benzenethiosulfones, benzenesulfinic acid; benzenesulfonic amide, etc. can be preferably used. .
[0051]
A hydrophilic material is preferably used for the binder of the constituent layer of the photothermographic material or the complexing agent sheet. Examples thereof include those described in Research Disclosure and pages (71) to (75) of JP-A No. 64-13,546. Specifically, a transparent or translucent hydrophilic binder is preferable. For example, proteins such as gelatin and gelatin derivatives, or cellulose derivatives, agar, starch, gum arabic, dextran, pullulan, farcelan, and European published patent 443,529 Polysaccharides such as carrageenan, locust bean gum, xanthan gum, pectin, natural compounds such as polysaccharides described in JP-A-1-221336, polyvinyl alcohol, modified alkyl polyvinyl alcohol described in Japanese Patent Application No. 5-339155, polyvinylpyrrolidone, Examples include synthetic polymer compounds such as acrylamide polymers. Also, superabsorbent polymers described in US Pat. No. 4,960,681, JP-A-62-245260, etc., that is, —COOM or —SO. _Three Homopolymers of vinyl monomers having M (M is a hydrogen atom or an alkali metal) or copolymers of these vinyl monomers with each other or with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, manufactured by Sumitomo Chemical Co., Ltd.) Sumikagel L-5H) is also used. Two or more of these binders can be used in combination. A combination of gelatin and the above binder is preferred. The gelatin may be selected from so-called demineralized gelatin in which the content of lime-processed gelatin, acid-processed gelatin, calcium, etc. is reduced according to various purposes, and is preferably used in combination.
[0052]
In the case of employing a system in which a very small amount of water is supplied for thermal development, it is possible to quickly absorb water by using the above super absorbent polymer.
[0053]
As the binder, gelatin is preferably used. However, when the gelatin content is low, hydrophilic polymers other than gelatin are carrageenan described in European Patent No. 443,529 and Japanese Patent Application No. Hei. Modified alkyl polyvinyl alcohol described in JP-A-5-339155 and polysaccharide described in JP-A-6-67330 are preferably used.
[0054]
The coating amount of all binders on the side containing the light-sensitive silver halide emulsion layer of the light-sensitive material is 12 g / m. ² The following is preferred, especially 5 g / m ² Below, further 4g / m ² The following is appropriate. The total amount of binder applied on the side opposite to the side containing the photosensitive silver halide emulsion layer is within the range of 50 to 100% of the coating amount of all binders on the side containing the photosensitive silver halide emulsion layer. Preferably. More preferably, it is around 70%.
[0055]
As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Moreover, the dye-donating compound which has the reducing property mentioned later is also contained (in this case, another reducing agent can also be used together). In addition, a reducing agent precursor that does not itself have a reducing property but develops a reducing property by the action of a nucleophile or heat during the development process can also be used.
Examples of the reducing agent used in the present invention include U.S. Pat. No. 4,500,626, columns 49 to 50, 4,839,272, 4,330,617, and 4,590,152. No. 5,017,454, No. 5,139,919, JP-A-60-140,335, pages (17)-(18), No. 57-40,245, No. 56-138. 736, 59-178,458, 59-53,831, 59-182,449, 59-182,450, 60-119,555, 60-128,436 60-128,439, 60-198,540, 60-181,742, 61-259,253, 62-201,434, 62-244,044, 62-131,253, 62-131,256, 6 Nos. 10,151 and 64-13,546, pages 40 to 57, JP-A-1-120,553, 2-32,338, 2-35,451, There are reducing agents and reducing agent precursors described in 2-234,158, 3-160,443, European Patent 220,746, pages 78-96, and the like. Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.
[0056]
When a diffusion-resistant reducing agent is used, an electron transfer agent and / or electron transfer agent is used as necessary to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide. A precursor can be used in combination. Particularly preferably, those described in US Pat. No. 5,139,919, European Patent Publication No. 418,743, Japanese Patent Application Laid-Open Nos. 1-138,556 and 3-102,345 are used. Further, a method of stably introducing into the layer as described in JP-A-2-230,143 and JP-A-2-235044 is preferably used.
The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or their precursors. It is desirable that the electron transfer agent or its precursor has a higher mobility than the non-diffusible reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.
The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent is not particularly limited as long as it does not substantially move in the layer of the photosensitive material among the reducing agents described above, preferably hydroquinones, Sulfonamide phenols, sulfonamide naphthols, described as electron donors in JP-A-53-110827, US Pat. Nos. 5,032,487, 5,026,634, and 4,839,272 And a dye-donating compound having a diffusion resistance and a reducing property described later.
An electron donor precursor as described in JP-A-3-160,443 is also preferably used.
Further, the reducing agent can be used for various purposes such as prevention of color mixing, improvement of color reproduction, improvement of white background, prevention of silver migration to the dye fixing material in the intermediate layer and protective layer. Specifically, European Patent Publication Nos. 524,649, 357,040, JP-A-4-249,245, 2-64,633, 2-46,450, JP-A-63- The reducing agent described in No. 186,240 is preferably used. JP-B-3-63,733, JP-A-1-150,135, 2-110,557, 2-46,634, 3-43,735, European Patent Publication 451,833. Development inhibitor releasing reducing compounds as described in US Pat.
In the present invention, the total amount of reducing agent added is 0.01 to 20 mol, particularly preferably 0.1 to 10 mol, per 1 mol of silver.
[0057]
In the present invention, an organic metal salt can be used as an oxidizing agent in combination with the photosensitive silver halide emulsion. Among such organometallic salts, organic silver salts are particularly preferably used.
Organic compounds that can be used to form the organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compounds described in US Pat. No. 4,500,626, columns 52-53. Acetylene silver described in US Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination.
The above organic silver salt can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of photosensitive silver halide. The total coating amount of photosensitive silver halide emulsion and organic silver salt is 0.05 to 10 g / m in terms of silver. ² , Preferably 0.4 g / m ² Is appropriate.
[0058]
Various dyes can be used in the constituent layer of the photothermographic material of the present invention for the purpose of preventing halation and irradiation. As disclosed in JP-A-3-7931 and JP-A-2-308242, the dye is preferably dispersed as fine particles in a solid state and incorporated in a photosensitive material. Specifically, the compounds described in Research Disclosure or the compounds described in Japanese Patent Application No. 6-259905 can be used.
[0059]
In the photothermographic material of the present invention, a compound capable of stabilizing the image simultaneously with activation of development can be used. Specific compounds preferably used are described in columns 51 to 52 of US Pat. No. 4,500,626.
[0060]
In the present invention, the image forming substance is mainly developed silver in a photosensitive material. If necessary, a dye (dye-donating compound) may be used as an image forming substance. In the photosensitive material for printing plate making used as an original to be printed on the PS plate, the PS plate has a spectral sensitivity in a wavelength region between 300 nm and 500 nm so that it can be handled in an ultraviolet cut light room. It is only necessary to have discrimination in the wavelength range, and a dye (dye-donating compound) having absorption in this wavelength range can be formed into an image together with the silver image. Also, at least two dye-donating compounds that form or release dyes having substantially different color tones, or dye donation that forms or releases at least two dyes having substantially different color tones. A black-and-white image by a pigment can be obtained together with silver using a functional compound.
[0061]
Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. This coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a non-diffusible group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion-resistant group may form a polymer chain. Specific examples of color developers and couplers include paraphenylenediamine reducing agents and phenolic or active methylene couplers in US Pat. No. 3,531,286, and paraaminophenol reducing agents in US Pat. No. 3,761,270. Belgian Patent No. 802,519 and Research Disclosure Journal, September 31, 1975, page 32, sulfonamidophenol-based reducing agents, US Pat. No. 4,021,240, sulfonamidophenol-based reducing agents and 4-equivalent couplers A combination of has been proposed. Specific examples of other color developers and couplers are also described in TH James's "The Theory of the Photographic Process", 4th edition, pages 291-334 and pages 354-361. As the reducing agent capable of reacting with the coupler in the coupling reaction, a hydrazone compound or a hydrazine compound can also be preferably used.
[0062]
Examples of another dye-donating compound include a cleavage reaction of a heterocyclic ring containing a nitrogen atom and a sulfur atom or selenium atom in the presence of a silver ion or a soluble silver complex as described in JP-A-59-180548 and the like. It is also possible to use a counter-diffusible dye-donating compound (thiazolidine-based compound) having the above-mentioned heterocyclic ring which causes a mobile dye to be released. Another example of the dye-donating compound is a compound having a function of releasing or diffusing a diffusible dye in an image form. This type of compound can be represented by the following general formula [LI].
((Dye) _m -Y) _n -Z [LI]
Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z corresponds to or corresponds to a photosensitive silver salt having a latent image in an image form. ((Dye) _m -Y) _n -Difference in the diffusivity of the compound represented by -Z or (Dye) _m -Y released, released (Dye) _m -Y and ((Dye) _m -Y) _n Represents a group having a property of causing a difference in diffusibility with -Z, m represents an integer of 1 to 5, n represents 1 or 2, and either m or n is not 1 The plurality of Dye may be the same or different.
Specific examples of the dye-donating compound represented by the general formula [LI] are those which form a diffusible dye image correspondingly to the development of the following silver halides 1 to 3.
[0063]
1. U.S. Pat.Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, 3,482,972, 3-68,387 A dye developer in which a hydroquinone developer and a dye-forming component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide.
[0064]
2. As described in U.S. Pat. No. 4,503,137, a non-diffusible compound that releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can also be used. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, and isoxazolones described in US Pat. No. 4,199,354. Examples thereof include compounds that release a diffusible dye by a ring intramolecular reversion reaction.
[0065]
3. U.S. Pat. No. 4,559,290, European Patent No. 220,746 A2, U.S. Pat. No. 4,783,396, Published Technical Report 87-6, 199, JP-A No. 64-13,546, etc. As can be seen, non-diffusible compounds that react with the reducing agent remaining unoxidized by development to release diffusible dyes can also be used.
For example, after the reduction described in US Pat. Nos. 4,139,389, 4,139,379, JP-A-59-185,333, and 57-84,453, etc. Compounds releasing diffusible dyes by intramolecular nucleophilic substitution reaction, US Pat. No. 4,232,107, JP-A-59-101,649, 61-88,257, RD24,025 (1984) Compounds that release a diffusible dye by intramolecular electron transfer reaction described in JP-A-56-142,530, US Pat. Compounds described in U.S. Pat. No. 4,450,223 and the like, which are described in U.S. Pat. No. 4,450,223, which are disclosed in U.S. Pat. Nos. 4,450,223 and 4,343,893 and 4,619,884 Expanded after electron acceptance Nitro compounds which release a sex dye, U.S. compounds release a diffusible dye after the electron acceptor that is described in Patent No. 4,609,610 and the like, and the like.
[0066]
More preferable are European Patent No. 220,746, Published Technical Report 87-6,199, US Pat. No. 4,783,396, Japanese Patent Laid-Open Nos. 63-201,653, 63-201,654. Compounds having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in JP-A Nos. 64-13,546, JP-A-1-26,842 In one molecule described in the issue ₂ -X (X is as defined above) and a compound having an electron-withdrawing group, PO-X bond (X is as defined above) and electron-withdrawing in one molecule described in JP-A-63-271,344 A compound having a group, a C—X ′ bond (X ′ is the same as X or —SO 2) in one molecule described in JP-A-63-271,341; ₂ -Represents a compound having an electron-withdrawing group. Moreover, the compound which a single bond cleaves after a reduction | restoration by the (pi) bond conjugate | bonded with the electron-accepting group described in Unexamined-Japanese-Patent No. 1-161,237, 1-161,342 can also be utilized. .
Among these, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable.
[0067]
When the colored dye-donating compound is present in the lower layer of the light-sensitive silver halide emulsion layer, it is possible to prevent a decrease in sensitivity.
[0068]
Hydrophobic additives such as a dye-donating compound and a diffusion-resistant reducing agent can be introduced into the layer of the photothermographic material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476, No. 599,296, JP-A-63-306439, 62-8145, 62-30247, JP-B-3-62,256, etc. It can be used in combination with a low boiling point organic solvent at 50 ° C to 160 ° C. Two or more of these dye-donating compounds, diffusion-resistant reducing agents, high boiling point organic solvents and the like can be used in combination.
The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g based on 1 g of the hydrophobic additive used. Further, 1 cc or less, further 0.5 cc or less, particularly 0.3 cc or less is appropriate for 1 g of binder.
Also added as a dispersion method with a polymer described in JP-B-51-39,853 and JP-A-51-59,943 or a fine particle dispersion described in JP-A-62-30242 You can also use this method.
In the case of a compound that is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder other than the above method.
In dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, the surfactants described in JP-A-59-157,636, pages (37) to (38), described in Research Disclosure, can be used.
Further, phosphate ester type surfactants described in JP-A-7-05267, Japanese Patent Application No. 6-19247, and West German Patent 1,932,299A can also be used.
[0069]
When a dye image is used in combination with a complexing agent sheet, a mordant known in the photographic field can be used. Specific examples thereof include US Pat. No. 4,500,626, columns 58 to 59, and JP-A-61. No. 88-256, pages (32)-(41) and JP-A-1-161,236, pages (4)-(7), mordants described in U.S. Pat. Nos. 4,774,162, 4, 619,883, 4,594,308 etc. can be mentioned. Further, a dye-accepting polymer compound as described in US Pat. No. 4,463,079 may be used.
[0070]
The complexing agent sheet may be provided with auxiliary layers such as a protective layer, a release layer, an undercoat layer, an intermediate layer, a back layer, and an anti-curl layer as necessary. In particular, it is useful to provide a protective layer.
[0071]
The hydrophilic binder is preferably used as the binder used in the complexing agent sheet of the present invention. Further, carrageenans as described in European Patent No. 443,529 and polysaccharides such as dextran are used in combination, and latexes having a glass transition temperature of 40 ° C. or less as described in JP-B-3-74,820 are used in combination. It is desirable. Further, it is preferable to use a mordant polymer known in the photographic field or a superabsorbent polymer described in US Pat. No. 4,960,681, JP-A-62-245260, etc. Furthermore, a polymer such as polyvinylpyrrolidone, polyvinylimidazole, or a copolymer of pyrrolidone and imidazole can be preferably used.
The total amount of binder applied is 20 g / m ² The following is preferred, especially 10 g / m ² Below, further 7 g / m ² The following is appropriate.
[0072]
In the constituent layers of the photothermographic material and the complexing agent sheet, a high-boiling organic solvent can be used as a plasticizer, a sliding agent or an agent for improving the peelability between the photosensitive material and the complexing agent sheet. Specific examples include those described in the Research Disclosure and JP-A-62-245253.
Furthermore, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil in which various organic groups are introduced into dimethylsiloxane) can be used. For example, various modified silicone oils described in “Modified Silicone Oil” technical materials P6 to 18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective.
In addition, silicone oils described in JP-A Nos. 62-215,953 and 63-46,449 are also effective.
As the hardener used in the constituent layer of the photothermographic material or the complexing agent sheet, Research Disclosure, U.S. Pat. No. 4,678,739, column 41, U.S. Pat. No. 4,791,042, JP-A-59. -116,655, 62-245,261, 61-18,942, JP-A-4-218044, and the like. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide) Ethane), N-methylol hardeners (dimethylolurea, etc.), or polymer hardeners (compounds described in JP-A-62-234157, etc.).
These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of the applied hydrophilic binder. Further, the layer to be added may be any of the constituent layers of the photosensitive material and the complexing agent sheet, or may be added in two or more layers.
[0073]
Various anti-fogging agents or photographic stabilizers and precursors thereof can be used in the constituent layers of the photothermographic material and the complexing agent sheet. Specific examples thereof include the Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A Nos. 64-13,546 (7)- (9), (57) to (71) and (81) to (97), U.S. Pat.Nos. 4,775,610, 4,626,500, 4,983,494, Kaisho 62-174,747, 62-239,148, 63-264,747, JP-A-1-150,135, 2-110,557, 2-178,650, RD17,643 (1978) (24)-(25) pages, Japanese Patent Application No. 6-190529, etc. are mentioned.
These compounds are 5 × 10 5 per mole of silver. ^-6 ~ 1x10 ^-1 Moles are preferred, further 1 × 10 ^-Five ~ 1x10 ^-2 Mole is preferably used.
[0074]
In the photothermographic material or the constituent layers of the complexing agent sheet, various surfactants can be used for the purpose of coating aid, improvement of peelability, improvement of slipperiness, antistatic, and development promotion. Specific examples of the surfactant are described in Research Disclosure, JP-A Nos. 62-173,463 and 62-183,457.
The constituent layers of the photothermographic material and the complexing agent sheet may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge and improving peelability. Representative examples of organic fluoro compounds include fluorine surfactants described in JP-B-57-9053, columns 8 to 17, JP-A-61-20944, 62-135826, and fluorine oil. Examples of the oily fluorine-based compound include hydrophobic fluorine compounds such as solid fluorine compound resins such as tetrafluoroethylene resin.
[0075]
In the photothermographic material and the complexing agent sheet, a matting agent can be used for the purpose of preventing adhesion, improving slipperiness, and making it non-glossy. As the matting agent, various inorganic compounds, organic compound particles, particularly polymer particles are used. Examples of inorganic matting agents include silicon dioxide, colloidal silica, oxides such as titanium oxide and aluminum oxide, alkaline earth metal salts such as barium sulfate, calcium carbonate and magnesium sulfate, and silicates, phosphates and borates. Glass particles. Organic matting agents include natural products such as corn starch, cellulose esters, and cellulose ethers and modified products thereof, alkyl acrylates, alkyl methacrylates, acrylamides, vinyl esters, synthetic resins of styrenes, polyolefins or polymethacrylates In addition to the compounds described in JP-A-61-88256 (page 29) such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, etc. Can be used. These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer as necessary.
[0076]
In the present invention, the matting agents may be used alone or in combination of two or more. The matting agent used in the present invention preferably has an average particle size of 0.1 μm to 20 μm. The addition amount of the matting agent is preferably 1 to 40%, more preferably 2 to 20% by weight with respect to the binder.
[0077]
As described in JP-A-3-109542, JP-A-64-31149, and JP-A-62-163047, those having cavities and those having a porous surface may be used.
[0078]
In addition, the constituent layers of the photothermographic material and the non-photosensitive complexing agent sheet may contain a thermal solvent, an antifoaming agent, an antibacterial and antibacterial agent, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32), JP-A-3-11,338, JP-B-2-51,496, and the like.
[0079]
In the present invention, an image formation accelerator can be used for the photothermographic material and / or the complexing agent sheet. The image formation accelerator interacts with a base or the above-mentioned base precursor, a nucleophilic compound, a high-boiling organic solvent (oil), a thermal solvent, a surfactant, silver or silver ion because of its physicochemical function. It is classified as a compound. However, these substance groups generally have a composite function, and usually have some of the above-mentioned promoting effects. Details thereof are described in US Pat. No. 4,678,739, columns 38-40.
[0080]
In the present invention, various development stoppers can be used in the photothermographic material and / or complexing agent sheet for the purpose of always obtaining a constant image with respect to variations in processing temperature and processing time during development.
A development terminator here means that after proper development, the base is quickly neutralized or reacted with the base to lower the base concentration in the film and to interact with a compound that stops development, or silver and silver salts to suppress development. It is a compound. Specific examples include an acid precursor that releases an acid upon heating, an electrophilic compound that causes a substitution reaction with a base that coexists upon heating, a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. Further details are described in JP-A-62-253159, pages (31) to (32).
[0081]
In the present invention, as the support for the photothermographic material and the complexing agent sheet, those capable of withstanding the processing temperature are used. Generally, papers, synthetic polymers (films), etc., edited by the Japan Photography Society, “Basics of Photographic Engineering-Silver Salt Photo Edition”, Corona Publishing Co., Ltd. (Showa 54) (223)-(240) And a photographic support. Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, polyarylate, celluloses (for example, triacetylcellulose), or pigments such as titanium oxide were contained in these films. Synthetic film made from polypropylene, etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast coated paper), metal, cloth, Glasses and the like are used. The thickness of the support is preferably 10 μm to 200 μm.
These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In this laminate layer, pigments and dyes such as titanium oxide, ultramarine, and carbon black can be contained as necessary.
In addition, JP-A-62-253,159 (29) to (31), JP-A-1-161,236 (14) to (17), JP-A-63-3316,848, Supports described in Kaihei 2-22,651, 3-56,955, U.S. Pat. No. 5,001,033 and the like can be used.
The back surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or other antistatic agents. Specifically, a support described in JP-A-63-220,246 can be used.
It is also preferable to apply a water-resistant polymer to the back surface of the support of the light-sensitive material from the viewpoint of improving adhesion after processing.
Surface resistivity is 10 ¹² It is desirable to design so that it is less than Ω · cm.
The surface of the support is preferably subjected to various surface treatments and undercoating for the purpose of improving the adhesion with the hydrophilic binder.
[0082]
The light-sensitive material of the present invention can be used for various purposes of printing light-sensitive materials, that is, not only for scanner films, but also for half-shot film, line drawing film, adhesion (negative-positive type) film, adhesion (reversal positive). -It can be used as a positive type film or a film for a bright room.
[0083]
As a method of exposing and recording an image on the photothermographic material of the present invention, for example, a method of exposing a printing document such as a reversal film using a plate-making camera with a contact screen or a color separation filter, a method of using a plate-making printer A scanning exposure method using a scanner, an image setter, a facsimile or the like to emit image information by emitting light from a xenon lamp, a light emitting diode, various lasers (laser diode, gas laser, etc.) via an electrical signal No. 129,625, Japanese Patent Application Nos. 3-338,182, 4-9,388, and 4-281,442).
[0084]
As a light source for recording an image on the photothermographic material, a xenon lamp, a tungsten lamp, a halogen lamp, a metal halide lamp, a quartz lamp, a light emitting diode, a laser light source, or the like can be used.
[0085]
Examples of the exposure apparatus in the present invention will be given below. Linotype-Hell DC series, commercially available Ar laser exposure equipment, Crosfield Magnascan series, Dainippon Screen SG series, commercial He-Ne laser exposure equipment, and commercial laser exposure equipment. Fuji Photo Film Lux Scan, Dainippon Screen MTR and other color scanners, Agfa-Gevaert Selectset (He-Ne), Avantra (Red-LD), Linotype-Hell Herkules (Red-LD) , Scitex Dolev (He-Ne), Agfa-Gevaert Accuset (Red-LD), Fuji Photo Film Lux Setter 5600 and other image setters, NEC FT240R and FT260R facsimile exposure equipment Can do.
[0086]
Examples of the plate-making printer that can be used in the exposure of the present invention are given below. Fuji Photo Film's FPA740, FPA800, FPA800X, FPA800Hg, FPA800FX, Dainippon Screen's P607 series, P617 series, P627 series, P647 series, P648 series, P607 series, IPG-IPSH-1000SH, USHIO's FL2M, FL3M, Kuraminami SK-16, Eastman-Kodak Versalite Contact Printer 840H, Contact 2200 Printer, Agfa-Gevaert CDL2002Ri, Kitamura P-6, P-4, P-2, P-8, SACK OR30 from the company, VDM5 from THIEMER, and RD7087D from CONVAC can be used.
[0087]
Examples of plate-making cameras that can be used in the exposure of the present invention will be given below. Fuji Photo Film's FCS820, FCS820S, FGC100, FGC200, FGC300, Dainippon Screen's FINE ZOOM880, ZOOMACE800, Companica C-680, Companica C-690, P648 Series, P607 Series, Image Tech-Koda, Eastman Graphics Corporation Opti-Copy 32, Opti-Copy 42, Opti-Copy 23, Image Maker 5060A, Image Maker IM200, Image Maker IM400, Image Maker IM600, Image Maker IM800, Agfa-Gevaert RPS Camera, Repro Master Series, Izumiya LINEAS 2000, design scope series, Mitsubishi Paper Industries' repro camera series can be used.
[0088]
The photothermographic material and / or complexing agent sheet of the present invention may have a form having a conductive heating element layer as a heating means for heat development and silver salt diffusion transfer. As the heat generating element in this case, those described in JP-A No. 61-145,544 can be used.
In the present invention, development and transfer are carried out by heating in the presence of a small amount of water as described in US Pat. Nos. 4,704,345, 4,740,445, and JP-A-61-238,056. Are preferably carried out simultaneously or sequentially. In this method, the heating temperature is preferably 50 ° C to 100 ° C.
[0089]
As water used in the present invention, any water that is generally used may be used. Specifically, distilled water, tap water, well water, mineral water, or the like can be used. In the heat development apparatus using the photothermographic material and the complexing agent sheet of the present invention, water may be used up, or it may be circulated and used repeatedly. In the latter case, water containing components eluted from the material is used. Also, the apparatus and water described in JP-A-63-144,354, JP-A-63-144,355, JP-A-62-38,460, JP-A-3-210,555 and the like may be used. Further, a low-boiling solvent that dissolves in water, a surfactant, an antifoggant, a complex-forming compound with a hardly soluble metal salt, an antifungal agent, and an antibacterial agent may be contained.
[0090]
These solvents can be applied to the photothermographic material, the complexing agent sheet, or both, but are preferably applied to the light-sensitive material. The amount used may be equal to or less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film.
As a method for imparting water, for example, methods described in JP-A-62-253159, page 5 and JP-A-63-85544 are preferably used. Further, the solvent can be confined in a microcapsule, or can be used in the form of a hydrate in advance incorporated in a photothermographic material or a dye fixing element or both.
The temperature of water to be applied may be 30 ° C. to 60 ° C. as described in JP-A-63-85,544. In particular, it is useful to set the temperature to 45 ° C. or higher for the purpose of preventing the propagation of miscellaneous bacteria in water.
[0091]
A hydrophilic thermal solvent that is solid at normal temperature and dissolves at high temperature can be incorporated in the photothermographic material and / or complexing agent sheet. The layer to be incorporated may be any of a light-sensitive silver halide emulsion layer, an intermediate layer and a protective layer of the light-sensitive material, and any layer of a complexing agent sheet. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles.
[0092]
As a heating method in the development and / or transfer process, contact with a heated block or plate, contact with a hot plate, hot press, heat roller, heat drum, halogen lamp heater, infrared and far infrared lamp heater, etc. Or let it pass through a high-temperature atmosphere.
[0093]
The method described in JP-A-62-253,159 and JP-A-61-147,244 (page 27) can be applied to superimpose the photothermographic material and the complexing agent sheet.
[0094]
Any of a variety of thermal development apparatus can be used to process the photographic elements of the present invention. For example, JP-A-59-75,247, 59-177,547, 59-181,353, 60-18,951, JP-A-62-25,944, Japanese Patent Application No. 4 -277,517, 4-243,072, 4-244,693 and the like are preferably used. Moreover, as a commercially available apparatus, the Pictorostat 100, the Pictorostat 200, the Pictorostat 300, the Pictography 3000, the Pictography 2000, and the like manufactured by Fuji Photo Film Co., Ltd. can be used.
[0095]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
[0096]
Example 1
A method for preparing the photosensitive silver halide emulsion (I) will be described.
A gelatin aqueous solution having a composition shown in Table 1 and having a pH of 4 and well-stirred is added to (I) solution and (II) solution shown in Table 2 simultaneously over 9 minutes, and after 5 minutes, solution (III) And (IV) solution were added simultaneously over 10 minutes.
[0097]
[Table 1]

[0098]
[Table 2]

[0099]
[Chemical 1]

[0100]
After washing with water and desalting (adjusted to pH 3 with sulfuric acid using a precipitating agent (1)) by conventional methods, 22 g of lime-processed gelatin was added to adjust the pH to 6.1 and pAg 7.1, followed by preservative. (1) was added and chemically sensitized at 60 ° C. The compounds used for chemical sensitization were added sequentially as shown in Table 3. The grain size was a silver chloride cubic emulsion having an average side length of 0.19 μm and a standard deviation of 0.019 μm and a silver bromide content of 1.7 mol. The yield of this emulsion is 635 g. Preservative (2) is phenoxyethanol.
[0101]
[Table 3]

[0102]
[Chemical formula 2]

[0103]
[Chemical 3]

[0104]
The method for preparing the silver bromide fine grain emulsion (2) shown in Table 3 will be described.
A well-stirred gelatin aqueous solution having the composition shown in Table 4 is cooled to 30 ° C., and the solutions (I) and (II) shown in Table 5 are added simultaneously over 3 minutes and 40 seconds. Thereafter, the liquid (III) and the liquid (IV) were simultaneously added over 2 minutes while controlling the flow rate of the liquid (IV) so that the silver potential was 50 mV.
[0105]
[Table 4]

[0106]
[Table 5]

[0107]
After usual washing and desalting (adjusted to pH 4.1 with phosphoric acid using precipitation agent 1), 22 g of lime-processed gelatin was added to adjust pH 6.1 and pAg 7.8 (by KBr). . Preservative (2) was used as a preservative. It was a silver bromide cubic emulsion having a grain size of 0.05 μm. Yield is 630 g.
[0108]
To 100 g of this emulsion (1) was added 3 cc of a methanol solution containing 10 mg of sensitizing dye (3), and 4,4′-bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] stilbene Add 0.25 cc of 1% methanol solution of -2,2'-disulfonic acid disodium salt, add 6 cc of 0.8% aqueous solution of antifoggant (2), and add 0.2 g of surfactant (1), A coating solution for the emulsion layer was prepared by adding 0.25 g of the water-soluble polymer (1). Silver amount 1.4g / m ² Application was carried out as follows.
15 cc of a 10% aqueous methanol mixed solution of para-tert-butylcatechol (volume ratio of water / methanol = 7/3) was further added to prepare a coating solution for the emulsion layer of the photosensitive material 101.
[0109]
[Formula 4]

[0110]
[Chemical formula 5]

[0111]
[Chemical 6]

[0112]
Next, a method for preparing a dispersion of solid fine particles of the reducing agent 1,5-diphenyl-3-pyrazolidone will be described. To 10 g of 1,5-diphenyl-3-pyrazolidone and 0.2 g of Kamol demole was added 90 cc of 5.7% lime-treated gelatin, and the mixture was dispersed in a mill for 30 minutes using glass beads having an average particle diameter of 0.75 mm. The glass beads were separated to obtain a gelatin dispersion of the reducing agent.
[0113]
Next, a method for preparing a solid fine particle dispersion of zinc hydroxide will be described.
Add 12.5 g of zinc hydroxide with an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant and 0.1 g of sodium polyacrylate to 100 cc of 4% gelatin aqueous solution, and use glass beads with an average particle size of 0.75 mm. For 30 minutes. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.
[0114]
It was prepared as shown in Table 6 of the dispersion of leuco dye and developer. The oil phase component heated and dissolved at about 60 ° C. is added to the aqueous phase component heated to 60 ° C., stirred and mixed, then dispersed with a homogenizer for 10 minutes at 10,000 rpm, and then added to form a uniform dispersion. Obtained.
[0115]
[Table 6]

[0116]
[Chemical 7]

[0117]
Using the above, photosensitive material 101 shown in Table 6 was prepared.
[0118]
[Table 7]

[0119]
[Chemical 8]

[0120]
[Chemical 9]

[0121]
Next, using the same material as the photosensitive material 101, photosensitive materials 102 to 111 shown in Table 8 were prepared with the same silver coating amount. The amount of non-photosensitive gelatin above the uppermost photosensitive silver halide emulsion layer was adjusted by the amount of acid-treated gelatin in the protective layer. The photosensitive material 112 is obtained by replacing the first layer and the second layer of the photosensitive material 105. Similarly, the photosensitive material 113 is prepared by replacing the first layer and the second layer of the photosensitive material 109.
[0122]
[Table 8]

[0123]
An Ag colloidal dispersion was prepared as follows. To the well-stirred solution shown in Table 9, 170 cc of an aqueous solution containing 17 g of silver nitrate is added over 25 minutes, gelatin is added, and water washing and desalting (using a precipitating agent (1) are performed in sulfuric acid by a conventional method. After adjusting to pH 3), lime-treated gelatin was added to adjust to pH 6.1, and then antiseptic (1) was added and dispersed. The particle size is an average particle size of 0.02 μm, the concentration is 4% Ag, the gelatin concentration is 2%, and the yield is 263 g.
[0124]
[Table 9]

[0125]
It was prepared as shown in Table 10 of the dispersion of the high boiling point solvent (1). The oil phase component heated and dissolved at about 60 ° C. is added to the aqueous phase component heated to 60 ° C., stirred and mixed, then dispersed with a homogenizer for 10 minutes at 10,000 rpm, and then added to form a uniform dispersion. Obtained. The particle size of the high boiling organic solvent was 0.3 μm.
[0126]
[Table 10]

[0127]
[Chemical Formula 10]

[0128]
Next, a processing sheet R1 as shown in Table 11 was prepared.
[0129]
[Table 11]

[0130]
Embedded image

[0131]
Embedded image

[0132]
The water absorption of R-1 is 13cc / m at 40 ° C. ² Met.
[0133]
The photosensitive materials 101 to 114 obtained as described above were exposed to one pixel (100 μm) with a semiconductor laser having a peak at 670 nm. ² ) And changed the amount of light at 1 / 10,000,000 seconds. The exposed photosensitive material was immersed in water kept at 40 ° C. for 2.5 seconds, then squeezed with a roller, and immediately superimposed so that the complexing agent sheet and the film surface were in contact with each other. Next, using a heat drum whose temperature was adjusted so that the temperature of the absorbed film surface was 80 ° C., the complexing agent sheet R1 was peeled off by heating for 22 seconds, and a black and white silver image was obtained on the photosensitive material.
Using an automatic densitometer, a characteristic curve representing the relationship between the blue density of the transmission image and the exposure amount was obtained. From this characteristic curve, the maximum density Dmax and the minimum density Dmin were measured. Further, the value of Dmin obtained from the light-sensitive material with the lapse of time was subtracted from the value Dmin of the light-sensitive material immediately after production, and the fluctuation range was compared. In addition, a wedge test for brittleness described in ISO 6077 was performed, and the difference in brittleness was compared.
These results are shown in Table 12. From the above results, in the present invention, a high-quality image having a low Dmin and a high Dmax and a high foot gradation and little processing unevenness can be obtained. It was confirmed that the brittleness of the film was improved.
[0134]
[Table 12]

Claims (2)

A silver halide light-sensitive material having at least a light-sensitive silver halide emulsion, a hydrophilic binder, and a water-insoluble basic metal compound on a support, the basic metal compound after imagewise exposure or simultaneously with imagewise exposure. For forming a silver image on the photosensitive material by superimposing a complex-forming compound for the metal ions constituting the film, a physical development nucleus, and a sheet having a silver halide solvent, followed by thermal development in the presence of a reducing agent and water And a hydrophilic binder layer containing no solid fine particle dispersion on the support side below the photosensitive silver halide emulsion layer of the silver halide photosensitive material, and the amount of the hydrophilic binder is 0.1 g / m 2. image forming method which is characterized in that ^two or more 2 g / m ² or less. ^2. The image forming method according to claim 1, wherein the amount of the binder contained in the non-photosensitive layer above the photosensitive silver halide emulsion layer is 0.1 g / m ² or more and 1 g / m ² or less.