JP3662082B2 - Processing member and heat-developable image forming method using the same - Google Patents

Description

【００３０】
本発明においては、感光性ハロゲン化銀と共に、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類も有用である。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０．１〜４ｇ／m²が適当である。
本発明の感光材料のバインダー種、量としては処理部材と同様である。
【００３１】
本発明において、カップリングで発色画像を得る場合、感光材料にはカプラーが含まれる。
本発明に使用できるカプラーは４当量カプラーでも、２当量カプラーでもよい。また、耐拡散性基がポリマー鎖をなしていてもよい。カプラーの具体例はT.H.James 「The Theory of the Photographic Process」第４版２９１〜３３４頁、および３５４〜３６１頁、５８−１２３５３３号、同５８−１４９０４６号、同５８−１４９０４７号、同５９−１１１１４８号、同５９−１２４３９９号、同５９−１７４８３５号、同５９−２３１５３９号、同５９−２３１５４０号、同６０−２９５０号、同６０−２９５１号、同６０−１４２４２号、同６０−２３４７４号、同６０−６６２４９号、同８−１１０６０８号、同８−１４６５５２号、同８−１４６５７８号等に詳しく記載されている。
【００３２】
また、以下のようなカプラーを用いることが好ましい。
イエローカプラー：EP502,424Aの式(I) 、(II)で表わされるカプラー；EP513,496Aの式(1) 、(2) で表わされるカプラー、特願平４−１３４５２３の請求項１の一般式（Ｉ）で表わされるカプラー；US5,066,576 のカラム1 の45、55行の一般式Ｄで表わされるカプラー、特開平４−２７４４２５の段落０００８の一般式Ｄで表わされるカプラー；EP498,381A1 の40頁のクレーム１に記載のカプラー、EP447,969A1 の４頁の式（Ｙ）で表わされるカプラー、US4,476,219 のカラム７の36、58行の式（Ｉ）〜（IV) で表わされるカプラー、
マゼンタカプラー：特開平３−３９７３７、特願平４−２３４１２０、特願平４−３６９１７、特開平４−３６２６に記載のカプラー。
シアンカプラー：特開平４−２０４８４３、特開平４−４３３４５、特願平４−２３６３３
ポリマーカプラー：特開平２−４４３４５。
【００３３】
発色色素が適度な拡散性を有するカプラーとしては、US4,366,237 、GB2,125,570 、EP96,570、DE3,234,533 に記載のものが好ましい。
【００３４】
また、感光材料には、以下のような機能性カプラーを含有しても良い。発色色素の不要な吸収を補正するためのカプラーは、EP456,257A1 に記載のイエローカラードシアンカプラー、該EPに記載のイエローカラードマゼンタカプラー、US4,833,069 に記載のマゼンタカラードシアンカプラー、US4,837,136 の(2) 、WO92/11575のクレーム１の式(A) で表わされる無色のマスキングカプラー（特に36−45頁の例示化合物) 。
現像主薬酸化体と反応して写真的に有用な化合物残基を放出する化合物（カプラーを含む）としては、以下のものが挙げられる。現像抑制剤放出化合物：EP378,236A1 の11頁に記載の式(I) 〜(IV)で表わされる化合物、EP436,938A2 の７頁に記載の式(I) で表わされる化合物、特願平４−１３４５２３の式（１）で表わされる化合物、EP440,195A2 の５、６頁に記載の式（I)、(II)、(III) で表わされる化合物、特願平４−３２５５６４の請求項１の式(I) で表わされる化合物−リガンド放出化合物、US4,555,478 のクレーム１に記載のLIG-X で表わされる化合物。
【００３５】
本発明に用いる感光材料では、現像時間の短縮、感度の向上、画像濃度の向上等の目的で、銀現像によって生成した酸化体が前述のカプラーとカップリングして色素を生成する事の出来る発色現像主薬を内蔵する態様が好ましい。
この場合、米国特許第３，５３１，２５６号の、ｐ−フェニレンジアミン現像主薬としてフェノールまたは活性メチレンカプラー、同第３，７６１，２７０号の、ｐ−アミノフェノール系現像主薬と活性メチレンカプラーの組合せを使用することが出来る。
米国特許第４，０２１，２４０号、特開昭６０−１２８４３８号等に記載されているようなスルホンアミドフェノールと４当量カプラーの組合せは、感光材料に内蔵する場合、生保存に優れており、好ましい組合せである。
発色現像主薬を内蔵する場合は、発色現像主薬のプレカーサーを用いても良い。たとえば、US３，３４２，５９７号記載のインドアニリン系化合物、US３，３４２，５９９号、リサーチディスクロージャーNo. １４，８５０及び同No. １５，１５９に記載のシッフ塩基型化合物、同１３，９２４記載のアルドール化合物、US３，７１９，４９２号記載の金属塩錯体、特開昭５３−１３５６２８号記載のウレタン系化合物を挙げることができる。
【００３６】
また、特願平７−１８０，５６８号に記載のスルホンアミドフェノール系主薬、特願平７−４９２８７号、同７−６３５７２号に記載のヒドラジン系主薬とカプラーの組合せも、本発明の感光材料に使用するのに好ましい。
【００３７】
耐拡散性の現像主薬を使用する場合には、耐拡散性現像主薬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、前記した現像主薬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現像主薬（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。
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、色再現改善など種々の目的で種々の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２−４６，４５０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２−４６，４５０号、同２−６４，６３４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剤化合物も用いられる。
【００３８】
その他、下記の様な還元剤を感材に内蔵してもよい。
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６２−２４４，０４４号、同６２−１３１，２５３号、同６２−１３１，２５６号、同６４−１３，５４６号の第(40)〜(57)頁、特開平１−１２０，５５３号、欧州特許第２２０，７４６Ａ２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。
また、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。
【００３９】
現像主薬あるいは、還元剤は、処理部材に内蔵しても良いが、感光材料に内蔵するのが好ましい。
【００４０】
本発明に於いては現像主薬および、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。
【００４１】
次に、画像状に拡散性色素を放出する場合について述べる。
本発明においては銀現像に対応または逆対応して拡散性色素を放出する非拡散性色材を使用する。この型の化合物は次の一般式〔Ｌ１〕で表すことができる。
（（Ｄｙｅ）_m −Ｙ）_n −Ｚ 〔Ｌ１〕
Ｄｙｅは拡散性の色素基を表し、Ｙは単なる連結基を表し、Ｚは画像状に潜像を有する感光性銀塩に対応または逆対応して拡散性の（Ｄｙｅ）_m −Ｙを放出し、かつＬ１自体は非拡散性となるような性質を有する基を表し、ｍは１〜５の整数を表し、ｎは１または２を表し、ｍ、ｎが共に１でない時、複数のＤｙｅは同一でも異なっていても良い。
一般式〔Ｌ１〕で表される色材の具体例としては下記の▲１▼〜▲４▼の化合物を挙げることができる。尚、下記の▲１▼〜▲３▼はハロゲン化銀の現像に逆対応して拡散性色素を放出するものであり、▲４▼はハロゲン化銀の現像に対応して拡散性色素を放出するものである。
▲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。
▲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。
【００４２】
▲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。
【００４３】
また、より好ましいものとして、欧州特許第２２０，７４６Ａ２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、特開昭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。その具体例は欧州特許第２２０，７４６Ａ２号または米国特許第４，７８３，３９６号に記載された化合物（１）〜（３）、（７）〜（１０）、（１２）、（１３）、（１５）、（２３）〜（２６）、（３１）、（３２）、（３５）、（３６）、（４０）、（４１）、（４４）、（５３）〜（５９）、（６４）、（７０）、公開技報８７−６，１９９に記載された化合物（１１）〜（２３）、特開昭６４−１３，５４６号に記載された化合物（１）〜（８４）などである。
【００４４】
▲４▼ハロゲン化銀または有機銀塩に対して還元性であり、相手を還元すると拡散性の色素を放出する化合物（ＤＲＲ化合物）。この化合物は他の還元剤を用いなくてもよいので、還元剤の酸化分解物による画像の汚染という問題がなく好ましい。その代表例は、米国特許第３，９２８，３１２号、同４，０５３，３１２号、同４，０５５，４２８号、同４，３３６，３２２号、特開昭５９−６５，８３９号、同５９−６９，８３９号、同５３−３，８１９号、同５１−１０４，３４３号、ＲＤ１７，４６５号、米国特許第３，７２５，０６２号、同３，７２８，１１３号、同３，４４３，９３９号、特開昭５８−１１６，５３７号、同５７−１７９，８４０号、米国特許第４，５００，６２６号等に記載されている。ＤＲＲ化合物の具体例としては前述の米国特許第４，５００，６２６号の第２２欄〜第４４欄に記載の化合物を挙げることができるが、なかでも前記米国特許に記載の化合物（１）〜（３）、（１０）〜（１３）、（１６）〜（１９）、（２８）〜（３０）、（３３）〜（３５）、（３８）〜（４０）、（４２）〜（６４）が好ましい。また米国特許第４，６３９，４０８号第３７〜３９欄に記載の化合物も有用である。
【００４５】
画像状に拡散性色素を放出し、処理部材に拡散転写させる系では、処理層に媒染剤を含ませるのが好ましい。媒染剤としては、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ＵＳ４，５００，６２６号第５８〜５９欄や特開昭６１−８８２５６号３２〜４１ページに記載の媒染剤、特開昭６２−２４４０４３号、同６２−２４４０３６号等に記載のものを挙げることができる。また、ＵＳ４，４６３，０７９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。
【００４６】
色材、カプラー、発色現像主薬、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、用いることができる。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色素供与性化合物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。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号等に記載されてい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、特願平５−２０４３２５号、同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。
本発明においては感光材料に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。
【００４７】
撮影用感光材料は、分光感度及び色材の色相が互いに異なる少なくとも３種の感光層を含む。それぞれの感光層は、実質的に感色性は同じであるが感光度の異なる複数のハロゲン化銀乳剤層に分けられていても良い。また、上記３種の感光層は好ましくは青色光、緑色光、及び赤色光のいずれかに感光する層である。この配列順は、一般的には支持体側から順に赤色感光性層、緑色感光性層、青色感光性層の順である。ただし、目的に応じ、これとは別の配列をとっても良い。例えば特開平７−１５２１２９号の１６２欄に記載されているような配列でも良い。
本発明においては、ハロゲン化銀と色材は同一層に含まれていても良いが、反応可能な状態であれば別層に分割して添加することもできる。例えば元々着色している色材を含む層をハロゲン化銀を含む層の下部に配置すると感度の低下を防げる。
各層の分光感度及び色材の色相の関係は任意であるが、赤色感光性層にシアン色材、緑色感光性層にマゼンタ色材、青色感光性層にイエロー色材を用いると、従来のカラーペーパー等に直接投影露光できる。
【００４８】
感光材料には、上記のハロゲン化銀乳剤層の間および最上層、最下層には、保護層、下塗り層、中間層、黄色フィルター層、アンチハレーション層などの各種の非感光性層を設けても良く、支持体の反対側にはバック層などの種々の補助層を設けることができる。具体的には、上記特許記載のような層構成、米国特許第５，０５１，３３５号記載のような下塗り層、特開平１−１６７，８３８号、特開昭６１−２０，９４３号記載のような固体顔料を有する中間層、特開平１−１２０，５５３号、同５−３４，８８４号、同２−６４，６３４号記載のような還元剤やＤＩＲ化合物を有する中間層、米国特許第５，０１７，４５４号、同５，１３９，９１９号、特開平２−２３５，０４４号記載のような電子伝達剤を有する中間層、特開平４−２４９，２４５号記載のような還元剤を有する保護層またはこれらを組み合わせた層などを設けることができる。
【００４９】
感光材料には、熱現像を促進する目的で熱溶剤を添加しても良い。その例としては、米国特許第３，３４７，６７５号および同第３，６６７，９５９号に記載されているような極性を有する有機化合物があげられる。具体的にはアミド誘導体（ベンズアミド等）、尿素誘導体（メチル尿素、エチレン尿素等）、スルホンアミド誘導体（特公平１−４０９７４号および特公平４−１３７０１号に記載されている化合物等）、ポリオール化合物（ソルビトール等）、およびポリエチレングリコール類があげられる。
熱溶剤が水不溶性の場合は、固体分散物として用いることが好ましい。添加する層は目的に応じ、感光層、非感光性層のいずれでも良い。
熱溶剤の添加量は、添加する層のバインダーの１０重量％〜５００重量％、好ましくは２０重量％〜３００重量％である。
【００５０】
本発明で用いる感光材料および処理部材は硬膜剤で硬膜されていることが好ましい。
硬膜剤の例としては米国特許第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）、ほう酸、メタほう酸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）があげられる。
これらの硬膜剤は、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。
【００５１】
感光材料には、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６４−１３，５６４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、特開平１−１５０，１３５号、同２−１１０，５５７号、同２−１７８，６５０号、ＲＤ１７，６４３（１９７８年）（２４）〜（２５）頁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。
【００５２】
感光材料および処理部材には、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公知技術第５号（１９９１年３月２２日、アズテック有限会社発行）の１３６〜１３８ページ、特開昭６２−１７３，４６３号、同６２−１８３，４５７号等に記載されている。
感光材料および処理部材には、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しく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。
【００５３】
感光材料にはマット剤を用いることができる。マット剤としては二酸化ケイ素、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、同６３−２７４９５２号記載の化合物がある。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。
本発明において感光材料の支持体としては、前述の処理部材に用いるものと同様のものが好ましく用いられる。
【００５４】
特に、感光材料用の支持体として巻きぐせのつきにくい特開平６−４１２８１号、同６−４３５８１号、同６−５１４２６号、同６−５１４３７号、同６−５１４４２号、特願平４−２５１８４５号、同４−２３１８２５号、同４−２５３５４５号、同４−２５８８２８号、同４−２４０１２２号、同４−２２１５３８号、同５−２１６２５号、同５−１５９２６号、同４−３３１９２８号、同５−１９９７０４号、同６−１３４５５号、同６−１４６６６号各公報に記載の支持体が好ましく用いることができる。
また、主としてシンジオタクチック構造を有するスチレン系重合体である支持体も好ましく用いることができる。
また、特開平４−１２４６４５号、同５−４０３２１号、同６−３５０９２号、特願平５−５８２２１号、同５−１０６９７９号記載の磁性体層を有する支持体を用い、撮影情報などを記録することが好ましい。
【００５５】
本発明で用いる撮影用感光材料は、通常のカラーネガと同様の加工を施し、カメラに装填して直接撮影できる。特公平２−３２６１５号、実公平３−３９７８４号に記載されているレンズ付フィルムユニットにも好ましく用いることができる。
【００５６】
感光材料および／または処理部材は、加熱現像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。
【００５７】
熱現像工程での加熱温度は、約５０℃〜２５０℃であるが、特に約６０℃〜１８０℃が有用である。拡散性色素の放出を用いる系で、色素の拡散転写工程は熱現像と同時に行っても良いし、熱現像工程終了後に行っても良い。後者の場合、転写工程での加熱温度は、熱現像工程における温度から室温の範囲で転写可能であるが、特に５０℃以上で、熱現像工程の温度より約１０℃低い温度までが好ましい。
拡散性色素の放出を利用する系で、色素の移動は熱のみによっても生じるが、色素移動を促進するために前記の熱溶剤やその他の溶媒を用いてもよい。
【００５８】
本発明では少量の湿し水の存在下で加熱し現像を行う方法が有用である。この方式においては、加熱温度は５０℃以上で水の沸点以下が好ましい。
現像の促進および／または色素の拡散転写のために用いる湿し水の例としては、水、無機のアルカリ金属塩や有機の塩基を含む塩基性の水溶液（これらの塩基としては画像形成促進剤の項で記載したものが用いられる）、低沸点溶媒または低沸点溶媒と水もしくは前記塩基性水溶液との混合溶液が挙げられる。また界面活性剤、かぶり防止剤、難溶性金属塩との錯形成化合物、防黴剤、防菌剤を溶媒中に含ませてもよい。
これらの熱現像および／または拡散転写の工程で用いられる湿し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ができる。また本発明の感光材料および受像要素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。
【００５９】
本発明において、感光材料に付与する湿し水の使用量は感光材料と処理部材の全塗布膜の最大膨潤体積に相当する水の重量以下でよい。
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。
【００６０】
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。
感光材料と処理部材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。
【００６１】
本発明の熱現像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、同６−１６４４２１号、同６−１６４４２２号等に記載されている装置等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。
【００６２】
本発明においては、現像処理後、付加的な現像停止処理は不要である。ただし、処理部材に現像停止剤を含ませておき、現像と同時に現像停止剤を働かせても良い。
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。
また、特願平６−１９０５２９号等に記載のメルカプトカルボン酸の亜鉛塩を感光要素に含有させ、前記を錯形成化合物を処理部材に含有させた組合せは有利である。
また、同様にハロゲン化銀のプリントアウト防止剤を処理シートに含ませておき、現像と同時にその機能を発現させても良い。プリントアウト防止剤の例としては特公昭５４−１６４号記載のモノハロゲン化合物、特開昭５３−４６０２０号記載のトリハロゲン化合物、特開昭４８−４５２２８号記載のハロゲンが脂肪族炭素原子に結合する化合物、特公昭５７−８４５４号に記載のテトラブロムキシレンに代表されるポリハロゲン化合物が挙げられる。また、英国特許第１，００５，１４４号に記載されている１−フェニル−５−メルカプトテトラゾールのような現像抑制剤も有効である。
また、特願平６−３３７５３１号に記載されているビオローゲン化合物も有効である。
プリントアウト防止剤の使用量は好ましくは１０^-4〜１モル／Ａｇ１モル、特に好ましくは１０^-3〜１０^-1モル／Ａｇ１モルである。
【００６３】
【実施例】
以下に実施例を持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。
まず、カラーネガフィルム感材（Ｋ０１）の作製について述べる。
水酸化亜鉛の分散物の調整法について述べる。
【００６４】
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１００mlに加え、ミルで平均粒径０．７５mmのガラスビーズを用いて３０分間粉砕した。ガラスビーズを分離し、水酸化亜鉛の分散物を得た。
【００６５】
次に電子伝達剤の分散物の調整法について述べる。
【００６６】
下記の電子伝達剤１０ｇ、分散剤としてポリエチレングリコールノニルフェニルエーテル０．５ｇ、下記の界面活性剤（１）０．５ｇを５％ゼラチン水溶液に加え、ミルで平均粒径０．７５mmのガラスビーズを用いて６０分間粉砕した。ガラスビーズを分離し、平均粒径０．３５μｍの電子伝達剤の分散物を得た。
【００６７】
【化１】

【００６８】
【化２】

【００６９】
次に疎水性添加剤のゼラチン分散物の調整法について述べる。
【００７０】
シアン、マゼンタ、イエローの色素供与化合物、電子供与体のゼラチン分散物を、それぞれ表Ｋ１の処方どうり調整した。即ち各油相成分を、約６０℃に加熱溶解させ均一な溶液とし、この溶液と約６０℃に加温した水相成分を加え、攪拌混合した後ホモジナイザーで１３分間、１２０００rpm で分散した。これに加水し、攪拌して均一な分散物を得た。
【００７１】
【表１】

【００７２】
【化３】

【００７３】
【化４】

【００７４】
【化５】

【００７５】
【化６】

【００７６】
【化７】

【００７７】
【化８】

【００７８】
【化９】

【００７９】
【化１０】

【００８０】
【化１１】

【００８１】
【化１２】

【００８２】
【化１３】

【００８３】
【化１４】

【００８４】
【化１５】

【００８５】
【化１６】

【００８６】
次に、感光性ハロゲン化銀乳剤の作り方について述べる。
【００８７】
感光性ハロゲン化銀乳剤(1) 〔赤感乳剤層用〕
良く攪拌しているゼラチン水溶液（水７００ml中にゼラチン２０ｇ、臭化カリウム０．５ｇ、塩化ナトリウム２．５ｇおよび下記の薬品（Ａ）１５mgを加えて４２℃に保温したもの）に、表Ｋ２の（Ｉ）液と（II）液を同時に８分間等流量で添加した。次いで(I) 、（II）液の添加終了８分後に色素のゼラチン分散物の水溶液（水１６０ml中にゼラチン１．９ｇ、下記の色素（ａ）１２７mg、下記の色素（ｂ）２５３mg、下記の色素（ｃ）８mgを含み３５℃に保温したもの）を添加した。２分後からさらに表２の(III) 液と（IV）液を同時に３２分間等流量で添加した。
【００８８】
常法により水洗、脱塩した後石灰処理オセインゼラチン２２ｇ、下記の薬品（Ｂ）５０mgを加えて、ｐＨを６．２、ｐＡｇを７．８に調整し４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを加え、次にチオ硫酸ナトリウムと塩化金酸を加えて６８℃で最適に化学増感し、次いで後述するカブリ防止剤（１）、下記の薬品（Ｃ）８０mg、薬品（Ｄ）３ｇを加えた後冷却した。このようにして平均粒子サイズ０．２１μｍの単分散立方体塩臭化銀乳剤６３５ｇを得た。
【００８９】
【表２】

【００９０】
【化１７】

【００９１】
【化１８】

【００９２】
【化１９】

【００９３】
感光性ハロゲン化銀乳剤(2) 〔赤感乳剤層用〕
良く攪拌しているゼラチン水溶液（水７００ml中にゼラチン２０ｇ、臭化カリウム０．３ｇ、塩化ナトリウム９ｇおよび前記薬品（Ａ）１５mgを加えて５３℃に保温したもの）に、表Ｋ３の（Ｉ）液と（II）液を同時に１０分間等流量で添加した。次いで(I) 、（II）液の添加終了６分後に色素のゼラチン分散物の水溶液（水１１５ml中にゼラチン１．２ｇ、前記の色素（ａ）７７mg、前記の色素（ｂ）１５３mg、前記の色素（ｃ）５mgを含み４５℃に保温したもの）を添加した。４分後からさらに表Ｋ２の(III) 液と（IV）液を同時に３０分間等流量で添加した。
【００９４】
常法により水洗、脱塩した後石灰処理オセインゼラチン３３ｇ、前記の薬品（Ｂ）５０mgを加えて、ｐＨを６．２、ｐＡｇを７．８に調整し４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを加え、次にチオ硫酸ナトリウムと塩化金酸を加えて６８℃で最適に化学増感し、次いで後述するカブリ防止剤（１）、前記の薬品（Ｃ）８０mg、薬品（Ｄ）３ｇを加えた後冷却した。このようにして平均粒子サイズ０．４５μｍの単分散立方体塩臭化銀乳剤６３５ｇを得た。
【００９５】
【表３】

【００９６】
感光性ハロゲン化銀乳剤(3) 〔緑感乳剤層用〕
良く攪拌しているゼラチン水溶液（水６９０ml中にゼラチン２０ｇ、臭化カリウム０．５ｇ、塩化ナトリウム５ｇおよび前記の薬品（Ａ）１５mgを加えて４１℃に保温したもの）に、表Ｋ４の（Ｉ）液と（II）液を同時に８分間等流量で添加した。１０分後さらに表Ｋ４の(III) 液と（IV）液を同時に３２分間等流量で添加した。また(III) 、（IV）液の添加終了１分後に色素のメタノール溶液（メタノール４７ml中に下記の色素（ｄ）２８０mgを含み３０℃に保温したもの）を一括して添加した。
【００９７】
常法により水洗、脱塩した後石灰処理オセインゼラチン２２ｇ、前記の薬品（Ｂ）５０mg、薬品（Ｄ）３ｇを加えて、ｐＨを６．０、ｐＡｇを７．１に調整し４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを加え、次にチオ硫酸ナトリウムを加えて６０℃で最適に化学増感し、次いで後述するカブリ防止剤（１）を加えた後冷却した。このようにして平均粒子サイズ０．２３μｍの単分散立方体塩臭化銀乳剤６３５ｇを得た。
【００９８】
【表４】

【００９９】
【化２０】

【０１００】
感光性ハロゲン化銀乳剤（４）〔緑感乳剤層用〕
良く攪拌しているゼラチン水溶液（水７１０ml中にゼラチン２０ｇ、臭化カリウム０．３ｇ、塩化ナトリウム９ｇおよび前記の薬品（Ａ）７．５mgを加えて６３℃に保温したもの）に表Ｋ５の（Ｉ）液と（II) 液を同時に１０分間等流量で添加した。１０分後さらに表Ｋ５の(III) 液と（IV) 液を同時に２０分間等流量で添加した。また(III) 、（IV) 液の添加終了１分後に色素のメタノール溶液（メタノール３５ml中に下記の色素（ｄ−１）２１０mg、（ｄ−２）４２．７mgを含み４６℃に保温したもの）を一括して添加した。
【０１０１】
常法により水洗、脱塩した後石灰処理オセインゼラチン３３ｇ、前記の薬品（Ｂ）５０mg、薬品（Ｄ）３ｇを加えて、ｐＨを６．０、ｐＡｇを７．２に調整し４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを加え、次にチオ硫酸ナトリウムと塩化金酸を加えて６０℃で最適に化学増感し、次いで下記カブリ防止剤（１）を加えた後冷却した。このようにして平均粒子サイズ０．４５μｍの単分散立方体塩臭化銀乳剤６３５ｇを得た。
【０１０２】
【表５】

【０１０３】
【化２１】

【０１０４】
感光性ハロゲン化銀乳剤（５）〔青感乳剤層用〕
良く攪拌しているゼラチン水溶液（水６９０ml中にゼラチン２０ｇ、臭化カリウム０．５ｇ、塩化ナトリウム５ｇおよび前記の薬品（Ａ）１５mgを加えて４６℃に保温したもの）に、表Ｋ６の（Ｉ）液と（II) 液を同時に８分間等流量で添加した。１０分後さらに表Ｋ６の(III) 液と（IV) 液を同時に１８分間等流量で添加した。また(III) 、（IV) 液の添加終了１分後に色素の水溶液（水９５mlとメタノール５ml中に、下記の色素（ｅ）２２５mgと下記の色素（ｆ）２２５mgを含み３０℃に保温したもの）を一括して添加した。
【０１０５】
常法により水洗、脱塩した後石灰処理オセインゼラチン２２ｇ、前記の薬品（Ｂ）５０mg、薬品（Ｄ）３ｇを加えて、ｐＨを６．０、ｐＡｇを７．７に調整し４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを加え、次にチオ硫酸ナトリウムを加えて６５℃で最適に化学増感し、次いで、後述するカブリ防止剤（１）を加えた後冷却した。このようにして平均粒子サイズ０．２７μｍの単分散立方体塩臭化銀乳剤６３５ｇを得た。
【０１０６】
【表６】

【０１０７】
【化２２】

【０１０８】
感光性ハロゲン化銀乳剤（６）〔青感乳剤層用〕
良く攪拌しているゼラチン水溶液（水７１０ml中にゼラチン２０ｇ、臭化カリウム０．３ｇ、塩化ナトリウム９ｇおよび前記の薬品（Ａ）１５mgを加えて５９℃に保温したもの）に、表Ｋ７の（Ｉ）液と（II) 液を同時に８分間等流量で添加した。１０分後さらに表Ｋ７の(III) 液と（IV) 液を同時に１８分間等流量で添加した。また（III)、（IV) 液の添加終了１分後に色素の水溶液（水８２mlとメタノール６ml中に、前記の色素（ｅ）１１３mgと前記の色素（ｆ）１１３mgを含み４０℃に保温したもの）を一括して添加した。
【０１０９】
常法により水洗、脱塩した後石灰処理オセインゼラチン３３ｇ、前記の薬品（Ｂ）５０mg、薬品（Ｄ）３ｇを加えて、ｐＨを６．０、ｐＡｇを７．７に調整し４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを加え、次にチオ硫酸ナトリウムと塩化金酸を加えて６５℃で最適に化学増感し、次いで下記カブリ防止剤（１）を加えた後冷却した。このようにして平均粒子サイズ０．４７μｍの単分散立方体塩臭化銀乳剤６３５ｇを得た。
【０１１０】
【表７】

【０１１１】
以上のものを用いて第Ｋ８表に示す感光材料Ｋ０１作った。
【０１１２】
【表８】

【０１１３】
【表９】

【０１１４】
【表１０】

【０１１５】
【化２３】

【０１１６】
次に、上記感材と組み合わせて処理することにより、感材上に画像を形成するために用いる処理部材の作製について述べる。
【０１１７】
添加剤（２）の分散物の作成方法について述べる。
【０１１８】
【化２４】

【０１１９】
添加物（２）１ｇおよびアニオン界面活性剤（３）１．２ｇを高沸点溶媒（４）１００ｇに５０℃にて加熱溶解する。別に石灰処理ゼラチン６０ｇを３００ｃｃのイオン交換水に膨潤した後、７０℃にて溶解し、防腐剤を添加しておく。両者を４０℃にて混合したのち、超音波分散装置にて乳化分散する。この操作により、添加物（２）の平均粒径０．１μから１μの乳化分散物を得る。
【０１２０】
【化２５】

【０１２１】
上記の分散物、および表Ｒ１に記載の原材料を用い、表Ｒ１に記載の構成にしたがって表Ａ１（但しポリマー層厚みは、６μｍ）の構成の支持体上に塗布し処理部材Ｒ１０１を作製した。
【０１２２】
【表１１】

【０１２３】
【表１２】

【０１２４】
【化２６】

【０１２５】
【化２７】

【０１２６】
【化２８】

【０１２７】
【化２９】

【０１２８】
同様に表Ｖ１に示したポリマー厚みもしくはパルプ厚みの支持体（表Ａ２〜４）の支持体を用い、Ｒ１０１と同様にして処理部材Ｒ１０２〜１１０を作成した。
【０１２９】
【表１３】

【０１３０】
【表１４】

【０１３１】
【表１５】

【０１３２】
【表１６】

【０１３３】
前記の感光要素（Ｋ０１）を通常の３５ｍｍカラーネガフィルム３６枚撮りのサイズに裁断、穿孔しカメラに装填し標準的な画像を接写にて撮影した。別に幅４０ｍｍ、長さ２ｍのシート状に裁断した上記処理部材（Ｒ１０１）を１インチ径のロール状巻き芯（送り出し側）に，塗布面が外向きになるように巻き込んだ。その後、処理部材の先端を、別の巻き芯（巻取り側）に一部巻き付けた。
【０１３４】
送り出しと、巻取りの間の処理部材の膜面がドラムヒータ外面に接する向きに処理部材をセットした。次に、露光済の感光材料面上に、４０℃に保温した湿し水を１３ml／m²の割合で展開した。感光材料膜面と処理部材膜面が均一に重なるように、処理部材がドラムヒーターと接する所で貼り合わせ、処理部材と感光材料をドラムヒーターの回転速度と同速度で移動させながら、感光材料が処理部材と剥離されるまでに８０℃にて２０秒間加熱されるよう、速度およびヒーター温度を調製し、処理を行った。次に処理部材がヒータードラムから、離れる位置で感材から剥離した。この操作により、貼り合わせおよび剥離も問題なく、感光材料上に銀および色素による画像が形成され、取扱い性も良好であった。
【０１３５】
この画像形成の取扱の優位性は、支持体の厚みが４μｍ以上、４０μｍ以下の場合（Ｒ１０１〜１０３、Ｒ１０６）に顕著であった。また、支持体がＰＥＴである場合（Ｒ１０１〜１０６）、両面ラミ紙支持体の場合（Ｒ１０７〜１１０）共に取扱性は良好であった。
また、処理部材を膜面を内巻に巻き込んだ場合、巻き込み時のカールが付きにくく良好な取扱性を示した。
さらに、上記のようなドラムヒーターではなく、平面状あるいは曲面状のヒーター上に搬送部材を設け、その上を前記の感光材料および処理部材が移動する形態で処理した場合も取扱性が良好であった。
【０１３６】
実施例２
以下に、カラーポジ感材（Ｋ０３）の作製について述べる。
【０１３７】
次に化合物（ｄ）のゼラチン分散物の作り方について述べる。
化合物（ｄ）を０．４ｇ、高沸点有機溶剤（１）を１．２ｇ、化合物（ｆ）を０．１２ｇ、化合物（ｇ）を０．２５ｇ、化合物（ｈ）を０．０５ｇ、界面活性剤（１）を０．２ｇ秤量し、酢酸エチルを９．５cc加え、約６０℃で加熱溶解し、均一な溶液とした。この溶液と石灰処理ゼラチンの１８％溶液２９．１ｇを攪拌混合した後、ホモジナイザーで１０分間１００００rpm で分散した。分散後、希釈用の水を１８．５cc加えた。この分散液を化合物（ｄ）の分散物と言う。
【０１３８】
【化３０】

【０１３９】
次に色素供与性化合物のゼラチン分散物の作り方について述べる。
シアンの色素供与性化合物（Ａ１）を７．３ｇ、シアンの色素供与性化合物（Ａ２）を１１．０ｇ、界面活性剤（１）を０．８ｇ、化合物（ｈ）を１ｇ、化合物（ｉ）を２．２ｇ、高沸点有機溶剤（１）を７ｇ、高沸点有機溶剤（２）を３ｇ秤量し、酢酸エチル２６ml、水１．２mlを加え、約６０℃で加熱溶解し、均一な溶液とした。この溶液と石灰処理ゼラチンの１６％溶液６５ｇと水８７ccを攪拌混合した後、ホモジナイザーで１０分間１００００rpm で分散した。分散後、希釈用の水を２１６cc加えた。この分散液をシアンの色素供与性化合物の分散物と言う。
【０１４０】
【化３１】

【０１４１】
【化３２】

【０１４２】
マゼンタの色素供与性化合物（Ｂ）を４．５０ｇ、化合物（ｍ）を０．０５ｇ、化合物（ｈ）を０．０５ｇ、界面活性剤（１）を０．０９４ｇ、高沸点有機溶剤（２）を２．２５ｇ秤量し、酢酸エチル１０mlを加え、約６０℃で加熱溶解し、均一な溶液とした。この溶液と石灰処理ゼラチンの１６％溶液１５．２ｇと水２３．５ccを攪拌混合した後、ホモジナイザーで１０分間、１００００rpm で分散した。その後希釈用水を４２cc加えた。この分散液をマゼンタの色素供与性化合物の分散物と言う。
【０１４３】
【化３３】

【０１４４】
イエローの色素供与性化合物（Ｃ）を１５ｇ、化合物（ｄ）を２．３ｇ、化合物（ｈ）を０．９ｇ、界面活性剤（１）を０．８８ｇ、化合物（ｊ）を３．９ｇ、化合物（ｋ）を１．９ｇ、高沸点有機溶剤（１）を１６．９ｇ秤量し、酢酸エチル４９mlを加え、約６０℃で加熱溶解し、均一溶液とした。この溶液と石灰処理ゼラチンの１６％溶液６３．５ｇと水１０３ccを攪拌混合した後、ホモジナイザーで１０分間、１００００rpm で分散した。その後希釈用水を９４cc加えた。この分散液をイエローの色素供与性化合物の分散物と言う。
これらにより、表Ｌ１のような熱現像感光材料Ｋ０２を構成した。
【０１４５】
【表１７】

【０１４６】
【表１８】

【０１４７】
【化３４】

【０１４８】
実施例１で用いた処理部材Ｒ１０１〜１１０を用い、実施例１で行ったのと同様の部材の準備、処理、評価を行ったところ、全く同様に良好な取扱性で画像を得ることができた。
【０１４９】
ただし、処理時の温度は８３℃で、処理時間は３５秒にて行った。
また、処理部材を幅１６０ｍｍ、長さ２ｍに加工し、３５ｍｍ幅に加工した感光要素Ｋ０２を４本同時に並列に並べ処理を行ったところ、Dmax、Dmin、階調、感度等の写真性についてほぼ同様な結果を得ることができた。
【０１５０】
実施例３
まず、感光要素（Ｋ０３）について述べる。
【０１５１】
染料組成物は以下のように乳化分散物として調製し添加した。
ロイコ染料と顕色剤および必要に応じて高沸点有機溶媒を秤量し、酢酸エチルを加え、約６０℃に加熱溶解させ均一な溶液とし、こめ溶液１００ccに対し、界面活性剤（１）を１．０ｇ、約６０℃に加熱した石灰処理ゼラチンの６．６％水溶液１９０ccを加え、ホモジナイザーで１０分間１００００ppm で分散した。
表Ｍ１に示した、２種類の染料分散物を作成した。
【０１５２】
【表１９】

【０１５３】
【化３５】

【０１５４】
感光性ハロゲン化銀乳剤の作り方について述べる。
【０１５５】
感光性ハロゲン化銀乳剤（１）〔赤感乳剤層用〕
良く攪拌しているゼラチン水溶液（水７００ml中にゼラチン２０ｇ、臭化カリウム０．５ｇ、塩化ナトリウム２．５ｇおよび下記の薬品（Ａ）１５mgを加えて４２℃に保温したもの）に、表Ｍ２の（Ｉ）液と（II) 液を同時に８分間等流量で添加した。次いで（Ｉ）、（II) 液の添加終了８分後に色素のゼラチン分散物の水溶液（水１６０ml中にゼラチン１．９ｇ、下記の色素（a)１２７mg、下記の色素(b) ２５３mg、下記の色素(c) ８mbを含み３５℃に保温したもの）を添加した。２分後からさらに表Ｍ２の（III)液と（IV) 液を同時に３２分間等流量で添加した。
【０１５６】
常法により水洗、脱塩した後石灰処理オセインゼラチン２２ｇ、下記の薬品（Ｂ）５０mgを加えて、ｐＨを６．２、ｐＡｇを７．８に調整し４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを加え、次にチオ硫酸ナトリウムと塩化金酸を加えて６８℃で最適に化学増感し、次いでカブリ防止剤（１）、薬品（Ｃ）８０mg、薬品（Ｄ）３ｇを加えた後冷却した。このようにして平均粒子サイズ０．２１μｍの単分散立方体塩臭化銀乳剤６３５ｇを得た。
【０１５７】
【表２０】

【０１５８】
【化３６】

【０１５９】
【化３７】

【０１６０】
【化３８】

【０１６１】
感光性ハロゲン化銀乳剤（２）〔赤感乳剤層用〕
良く攪拌しているゼラチン水溶液（水７００ml中にゼラチン２０ｇ、臭化カリウム０．３ｇ、塩化ナトリウム９ｇおよび前記薬品（Ａ）１５mgを加えて５３℃に保温したもの）に、表Ｍ３の（Ｉ）液と（II) 液を同時に１０分間等流量で添加した。ついで（Ｉ）、（II）液の添加終了６分後に色素のゼラチン分散物の水溶液（水１１５ml中にゼラチン１．２ｇ、前記の色素(a) ７７mg、前記の色素(b) １５３mg、前記の色素(c) ５mgを含み４５℃に保温したもの）を添加した。４分後からさらに表Ｍ３の(III) 液と（IV) 液を同時に３０分間等流量で添加した。
【０１６２】
常法により水洗、脱塩した後石灰処理オセインゼラチン３３ｇ、前記の薬品（Ｂ）５０mgを加えて、ｐＨを６．２、ｐＡｇを７．８に調整した４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを加え、次にチオ硫酸ナトリウムと塩化金酸を加えて６８℃で最適に化学増感し、次いでカブリ防止剤（１）、薬品（Ｃ）８０mg、薬品（Ｄ）３ｇを加えた後冷却した。このようにして平均粒子サイズ０．４５μｍの単分散立方体塩臭化銀乳剤６３５ｇを得た。
【０１６３】
【表２１】

【０１６４】
感光性ハロゲン化銀乳剤（３）〔緑感乳剤層用〕
良く攪拌しているゼラチン水溶液（水６９０ml中にゼラチン２０ｇ、臭化カリウム０．５ｇ、塩化ナトリウム５ｇおよび前記の薬品（Ａ）１５mgを加えて４１℃に保温したもの）に、表Ｍ４の（Ｉ）液と（II) 液を同時に８分間等流量で添加した。１０分後さらに表Ｍ４の（III)液と（IV) 液を同時に３２分間等流量で添加した。また（III)、（IV) 液の添加終了１分後に色素のメタノール溶液（メタノール４７mlに下記の色素（ｄ−１）２８１０mgと（ｄ−２）５７．３mgを含み３０℃に保温したもの）を一括して添加した。
【０１６５】
常法により水洗、脱塩した後石灰処理オセインゼラチン前記の薬品（Ｂ）５０mg、薬品（Ｄ）３ｇを加えて、ｐＨを６．２、ｐＡｇを７．８に調整し４−ヒドロキシ−６−メチル１，３，３ａ，７−テトラザインデンを加え、次にチオ硫酸ナトリウムを加えて６０℃で最適に化学増感し、次いでカブリ防止剤（１）を加えた後冷却した。このようにして平均粒子サイズ０．２３μｍの単分散立方体塩臭化銀乳剤６３５ｇ得た。
【０１６６】
【表２２】

【０１６７】
【化３９】

【０１６８】
感光性ハロゲン化銀乳剤（４）〔緑感乳剤層用〕
良く攪拌しているゼラチン水溶液（水７１０ml中にゼラチン２０ｇ、臭化カリウム０．３ｇ、塩化ナトリウム９ｇおよび前記の薬品（Ａ）７．５mgを加えて６３℃に保温したもの）に、表Ｍ５の（Ｉ）液と（II) 液を同時に１０分間等流量で添加した。１０分後さらに表Ｍ５の（III)液と（IV) 液を同時に２０分間等流量で添加した。また（III ) 、（IV) 液の添加終了１分後に色素のメタノール溶液（メタノール３５ml中に前記の色素（ｄ−１）２１０mgと（ｄ−２）４２．７mgを含み４６℃に保温したもの）を一括して添加した。
【０１６９】
常法により水洗、脱塩した後石灰処理オセインゼラチン３３ｇ、前記の薬品（Ｂ）５０mg、薬品（Ｄ）３ｇを加えて、ｐＨを６．０、ｐＡｇを７．２に調製し、４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを加え、次にチオ硫酸ナトリウムと塩化金酸を加えて６０℃で最適に化学増感し、次いでカブリ防止剤（１）を加えた後冷却した。このようにして平均粒子サイズ０．４５μｍの単分散立方体塩臭化銀乳剤６３５ｇを得た。
【０１７０】
【表２３】

【０１７１】
感光性ハロゲン化銀乳剤（５）〔青感乳剤層用〕
良く攪拌しているゼラチン水溶液（水６９０ml中にゼラチン２０ｇ、臭化カリウム０．５ｇ、塩化ナトリウム５ｇおよび前記の薬品（Ａ）１５mgを加えて４６℃に保温したもの）に、表Ｍ６の（Ｉ）液と（II) 液を同時に８分間等流量で添加した。１０分後さらに表Ｍ６の（III)液と（IV) 液を同時に１８分間等流量で添加した。また（III)、（IV) 液の添加終了１分後に色素の水溶液（水９５mlとメタノール５ml中に、下記の色素(e) ２２５mgと下記の色素（f)２２５mgを含み３０℃に保温したもの）を一括して添加した。
【０１７２】
常法により水洗、脱塩した後石灰処理オセインゼラチン２２ｇ、前記の薬品（Ｂ）５０mg、薬品（Ｄ）３ｇを加えて、ｐＨを６．０、ｐＡｇを７．７に調整し４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを加え、次にチオ硫酸ナトリウムを加えて６５℃で最適に化学増感し、次いでカブリ防止剤（１）を加えた後冷却した。このようにして平均粒子サイズ０．２７μｍの単分散立方体塩臭化銀乳剤６３５ｇを得た。
【０１７３】
【表２４】

【０１７４】
感光性ハロゲン化銀乳剤（６）〔青感乳剤層用〕
良く攪拌しているゼラチン水溶液（水７１０ml中にゼラチン２０ｇ、臭化カリウム０．３ｇ、塩化ナトリウム９ｇおよび前記の薬品（Ａ）１５mgを加えて５９℃に保温したもの）に、表Ｍ７の（Ｉ）液と（II) 液を同時に８分間等流量で添加した。１０分後さらに表Ｍ７の（III)液と（IV) 液を同時に１８分間等流量で添加した。また（III)、（IV) 液の添加終了１分後に色素の水溶液（水８２mlとメタノール６ml中に、下記の色素(e) １１３mgと前記の色素（f)１１３mgを含み４０℃に保温したもの）を一括して添加した。
【０１７５】
常法により水洗、脱塩した後石灰処理オセインゼラチン３３ｇ、前記の薬品（Ｂ）５０mg、薬品（Ｄ）３ｇを加えて、ｐＨを６．０、ｐＡｇを７．７に調整し４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラザインデンを加え、次にチオ硫酸ナトリウムと塩化金酸を加えて６５℃で最適に化学増感し、次いでカブリ防止剤（１）を加えた後冷却した。このようにして、平均粒子サイズ０．４７μｍの単分散立方体塩臭化銀乳剤６３５ｇを得た。
【０１７６】
【表２５】

【０１７７】
＜水酸化亜鉛分散物の調製方法＞
【０１７８】
一次粒子の粒子サイズが０．２μｍの水酸化亜鉛の粉末３１ｇ、分散剤としてカルボキシメチルセルロース１．６ｇおよびポリアクリル酸ソーダ０．４ｇ、石灰処理オセインゼラチン８．５ｇ、水１５８．５mlを混合し、この混合物をガラスビーズを用いたミルで１時間分散した。分散後、ガラスビーズを濾別し、水酸化亜鉛の分散物１８８ｇを得た。
【０１７９】
次に電子伝達剤の分散物の調製法について述べる。
【０１８０】
下記の電子伝達剤の（ア）１０ｇ、分散剤としてポリエチレングリコールノニルフェニルエーテル０．５ｇ、下記のアニオン性界面活性剤（ア）０．５ｇを５％ゼラチン水溶液に加え、ミルで平均粒径０．７５mmのガラスビーズを用いて６０分間粉砕した。ガラスビーズを分離し、平均粒径０．３５μｍの電子伝達剤の分散物を得た。
【０１８１】
【化４０】

【０１８２】
＜カプラーの乳化分散物の調製方法＞
【０１８３】
表Ｍ８に示す組成の油相成分、水相成分それぞれ溶解し、６０℃の均一な溶液とする。油相成分と水相成分を合わせ、１リットルのステンレス容器中で、直径５cmのディスパーサーのついたディゾルバーにより、１００００rpm で２０分間分散した。これに、後加水として、表Ｍ８に示す量の加水（温水）を加え、２０００rpm で１０分間混合した。このようにして、シアン、マゼンタ、イエロー３色のカプラーの乳化分散物を調製した。
【０１８４】
【表２６】

【０１８５】
【化４１】

【０１８６】
このようにして得られた素材を用いて、表Ｎ１に示す多層構成の熱現像カラー感光材料Ｋ０３を作製した。
【０１８７】
【表２７】

【０１８８】
【表２８】

【０１８９】
【化４２】

【０１９０】
次に処理部材の作成について述べる。表Ｒ２に記載の構成にしたがって表Ａ１（但しポリマー層厚みは、６μｍ）の構成の支持体上に塗布し処理材料Ｒ２０１を作製した。
【０１９１】
【表２９】

【０１９２】
同様に表Ｖ１に示したポリマー厚みもしくはパルプ厚みの支持体（表Ａ２〜４）の支持体を用い、Ｒ２０１と同様にして処理要素Ｒ２０２〜２１０を作成した。
実施例１で行ったのと同様の部材の準備、処理、評価を行ったところ、全く同様に良好な取扱性で画像を得ることができた。
ただし、現像温度８３℃かつ現像時間は３０秒でおこなった。
また、処理部材を幅４０ｍｍ、長さ６ｍに加工し、幅３５ｍ長さ１．５ｍに加工した感光要素Ｋ０３を長手方向に３本直列につなげたものを、１回の連続した現像にて処理したところ、同様に画像が得られ、良好な取扱性を示した。
【０１９３】
実施例４
感光性ハロゲン化銀乳剤の製法について述べる。
十分に攪拌されている表Ｂ１に示す組成のゼラチン水溶液に、表Ｂ２に示す（Ｉ）液と、（II) 液とを同時に１０分間で添加し、その２分後に（III)液と（IV) 液とを同時に１８分間で添加した。
【０１９４】
【表３０】

【０１９５】
【表３１】

【０１９６】
【化４３】

【０１９７】
常法により化合物（ア）を用いてｐＨ３．０で沈降させ脱塩を行った後、脱灰処理ゼラチン５０ｇを加えて、ｐＨ５．７、ｐＡｇ７．５に調整し、カブリ防止剤（ア）を０．１ｇ加えた後６０℃で化学増感を行った。化学増感にはイオウ増感剤としてハイポを０．００３ｇ、金増感剤として塩化金酸を０．０１５ｇそれぞれ加え６０分後に防腐剤（ア）を０．１ｇ、安定化剤（ア）を０．０２ｇ加え塩臭化銀乳剤を得た。得られたハロゲン化銀の平均粒子サイズは０．２０μｍであった。
【０１９８】
この乳剤１００ｇに増感色素（ア）を１８．０ｇ加え、化合物（イ）の１％メタノール溶液を１．２５ml、化合物（ウ）の０．８％メタノール溶液を７．５及び界面活性剤（ア）を１６０mg、水溶性ポリマー（ア）を１５０mgをそれぞれ加えて乳剤層の溶液を得、銀量で１．４ｇ／m²となるように塗布を行った。
【０１９９】
【化４４】

【０２００】
【化４５】

【０２０１】
次に還元剤１，５−ジフェニル−３−ピラゾリドン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。
【０２０２】
次にハレーション防止染料（ア）の固体状態の分散物も上記の方法に準じて調製し、ハレーション防止染料のゼラチン分散物を得た。
【０２０３】
【化４６】

【０２０４】
次に、水酸化亜鉛の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。
【０２０５】
以下のものを用いて、表Ｂ３に示す感光材料Ｋ０４を作成した。
【０２０６】
【表３２】

【０２０７】
【化４７】

【０２０８】
上記の感光要素（Ｋ０３）を幅５５０ｍｍ、長さ７６０ｍｍに加工した。この感光要素を、６７０ｎｍに出力ピーク波長を持つ半導体レーザーを用い、１画素（１００μｍ²)当たり１０００万分の１秒で光量を変化させて露光した。別に幅５８０ｍｍ、長さ２１ｍのシート状に裁断した上記処理要素（Ｒ１０１）を２インチ径のロール状巻き芯（送り出し側）に、塗布面が内向きになるように巻き込んだ。その後、処理要素の先端を、別の巻き芯（巻取り側）に一部巻き付けた。
【０２０９】
送り出しと、巻取りの間の処理要素の膜面がドラムヒータ外面に接する向きに処理部材をセットした。次に、露光済の感光要素を、４０℃に保温した水に２．５秒浸したのち、ローラーで絞り、感光要素上の水量を凡そ１２ml／m²にした。感光要素膜面と処理要素膜面が均一に重なるように貼り合わせた後、処理部材と感光要素をドラムヒーターの回転速度と同速度で移動させながら、感光要素が処理要素と剥離されるまでに８０℃にて１８秒間加熱されるよう、速度およびヒーター温度を調製し、処理を行った。次に処理部材がヒータードラムから、離れる位置で感材から剥離し、つづいて感光要素をドラムから剥離した。この操作により、貼り合わせおよび剥離も問題なく、感光要素上に銀による画像が形成され、取扱い性も良好であった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a processing member and a heat-developable image forming method using the same. Furthermore, it is related with the process member which improved the handleability.
[0002]
[Prior art]
Photothermographic materials containing silver halide are known, and the photothermographic materials and processes thereof are described in, for example, “Basics of Photographic Engineering”, Non-Silver Salt Photo Edition (published by Corona, 1982), pages 242 to 255. U.S. Pat. No. 4,500,626.
[0003]
In addition, for example, methods for forming a dye image by a coupling reaction between an oxidized oxidant of a developing agent and a coupler are described in U.S. Pat. Nos. 3,761,270 and 4,021,240. A method for forming a positive color image by a photosensitive silver dye bleaching method is described in US Pat. No. 4,235,957.
[0004]
Recently, a method of releasing or forming a diffusible dye in an image form by heat development and transferring the diffusible dye to a dye fixing element has been proposed. In this method, a negative dye image and a positive dye image can be obtained by changing the kind of dye-donating compound used or the kind of silver halide used. More specifically, U.S. Pat. Nos. 4,500,626, 4,483,914, 4,503,137, 4,559,290, JP 58-149046, JP 60- No. 133449, No. 59-218443, No. 61-238056, European Patent Publication No. 220746A, Japanese Patent Publication No. 87-6199, European Patent Publication No. 210660A2, and the like.
[0005]
Many methods have been proposed for obtaining a positive color image by thermal development. For example, in US Pat. No. 4,559,290, a compound obtained by converting a so-called DRR compound into an oxidized form having no color image releasing ability coexists with a reducing agent or a precursor thereof, and depending on the exposure amount of silver halide by heat development. Thus, a method has been proposed in which a reducing agent is oxidized and reduced with a reducing agent remaining unoxidized to release a diffusible dye. In addition, in European Patent Publication No. 220746A and Published Technical Report 87-6199 (Vol. 12, No. 22), as a compound that releases a diffusible dye by the same mechanism, an NX bond (X is an oxygen atom, a nitrogen atom or a sulfur atom). A heat-developable color light-sensitive material using a compound that releases a diffusible dye by reductive cleavage of (representing an atom) is described.
[0006]
In the above example, when the photosensitive material is subjected to heat development processing, the image receiving sheets are superposed and heated to transfer the diffusible dye, thereby obtaining a dye image on the image receiving sheet. In this case, images opposite to both the photosensitive material and the image receiving sheet are formed. When an image on the photosensitive material side is used, the image receiving sheet can be considered as a processing member. It is desirable that the processing member is a material with excellent handling properties.
[0007]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to improve the handling of a processing member in a system using a photothermographic material and a processing member and utilizing an image formed on the photosensitive material.
[0008]
[Means for Solving the Problems]
  The above object has been achieved by the following means.
(1) In a processing member used to form an image on a photosensitive material by superimposing it on a photothermographic material containing silver halide and heating it, the processing member is a continuous web.With a support and containing a binderProcessing layerIs coated on the support.The processing member characterized by the above-mentioned.
(2) The processing member according to (1), wherein the support has a thickness of 4 μm or more and 40 μm or less.
(3) The processing member according to (1) or (2), wherein the processing layer contains a base or a base precursor.
(4) After applying dampening water to the photothermographic material containing silver halide, an image is formed on the photosensitive material by superimposing and heating with a processing member provided with a processing layer on a continuous web. And a heat-developable image forming method.
(5) After applying dampening water to the photothermographic material containing silver halide, the substrate is heated with being superimposed on a processing member provided with a processing layer containing a base or a base precursor on a continuous web. A heat-developable image forming method comprising forming an image on a photosensitive material.
(6) The heat-developable image forming method as described in (5) above, wherein the photosensitive material contains a basic metal compound hardly soluble in water and the processing member contains a complex-forming compound.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The continuous web of the processing member referred to in the present invention is the length of the processing member is sufficiently longer than the long side of the photosensitive material corresponding to the processing, and it is used without cutting a part thereof when used for processing. A form having a length capable of processing a plurality of photosensitive materials. In general, the length of the processing member is 5 to 1000 times the width. Although the width of the treatment member is arbitrary, it is preferably equal to or greater than the width of the corresponding photosensitive material.
[0010]
Further, a mode in which a plurality of photosensitive materials are processed in parallel, that is, a plurality of photosensitive materials are arranged side by side is also preferable. In this case, the width of the processing member is preferably equal to or greater than the width of the light-sensitive material × the number of simultaneous processes.
Such a continuous web processing member is particularly effective when the length of the photosensitive material is 50 cm or more and when a plurality of photosensitive materials are continuously processed.
Further, when such a continuous web processing member is used, it becomes easy to peel the photosensitive material from the processing member after development.
The continuous web processing member of the present invention is preferably supplied from a feed roll, wound on a take-up roll and discarded. In particular, disposal of light-sensitive materials having a large size is easy.
As described above, the handling property of the continuous web processing member of the present invention is remarkably improved as compared with the conventional sheet-like member.
[0011]
Although the thickness of the support used for the treatment member of the present invention is arbitrary, it is preferably thinner, particularly preferably 4 μm or more and 40 μm or less. In this case, since the quantity of the processing member per unit volume increases, said roll for processing members can be made compact.
The material of the support is not particularly limited, and a material that can withstand the processing temperature is used. Generally, papers and synthetic polymers (films) described in “Photographic Engineering Fundamentals-Silver Salt Photo Edition” edited by the Japan Photography Society, Corona Publishing Co., Ltd. (Showa 54) (pp. 223)-(240) ) And the like. Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetylcellulose) or those containing pigments such as titanium oxide in these films, Synthetic paper made from polypropylene or the like, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), or the like is used.
[0012]
These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene.
In addition, JP-A-62-253,159 (29) to (31), JP-A-1-161,236 (14) to (17), JP-A-63-316,848, Supports described in Kaihei 2-22,651, 3-56,955, U.S. Pat. No. 5,001,033 and the like can be used.
Further, a support which is a styrene polymer mainly having a syndiotactic structure can also be preferably used.
[0013]
A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black or other antistatic agents may be applied to the surface of these supports.
In addition to the purpose of transferring the diffusible dye listed in the previous example, the processing member of the present invention blocks air during heat development, prevents volatilization of the material from the photosensitive material, and sensitizes the processing material. It is used to supply to the material, or to remove a raw material in the photosensitive material which becomes unnecessary after development or an unnecessary component generated during development.
In the present invention, it is preferable to use a base or a base precursor for promoting image formation, but from the viewpoint of storage stability, it is preferable to include them in the processing layer of the processing member. In the case where a base is generated by reaction of two or more substances, an embodiment in which only one of them is included in the treatment layer is also included in the present invention.
[0014]
In the present invention, as the base and the base precursor, known compounds used during the development processing of the photothermographic material can be used.
Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Lossen transfer or Beckmann transfer. Specific examples thereof are described in US Pat. Nos. 4,514,493, 4,657,848, and publicly known technology No. 5 (published on March 22, 1991, issued by Aztec Co., Ltd.), pages 55 to 86. . In addition, as described in EP210,660, US Pat. No. 4,740,445, and JP-A-62-129848, a basic metal compound hardly soluble in water and a metal ion constituting the basic metal compound, When a combination of compounds capable of forming a complex (referred to as complex forming compounds) is used as a base precursor, it is preferable to add a basic metal compound that is hardly soluble in water to the photosensitive material and a complex forming compound to the processing layer of the processing member. .
The amount of base or base precursor used is 0.1-20 g / m.², Preferably 1-10 g / m²It is.
[0015]
In the present invention, it is preferable that after dampening water is applied to the photothermographic material, it is heat-developed with a processing member provided with a processing layer on a continuous web. In particular, it is effective when a combination of a basic metal compound and a complex-forming compound that are hardly soluble in water is used as the base precursor.
Preferable poorly water-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 / m²~ 8g / m²Preferably 0.05 to 5 g / m²It is.
A complex-forming compound for a metal ion of a basic metal compound which is hardly soluble in water is known as a chelating agent in analytical chemistry and a hard water softening agent in photographic chemistry. 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, quinolinic acid, and 5-ethyl-2-picolinic acid. Among these, pyridinecarboxylic acid (salt) is particularly preferable.
[0016]
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 in the complex-forming compound is 0.1 to 20 g / m.²Preferably, 0.1 to 10 g / m²It is.
As the binder for the treatment layer, a hydrophilic one is preferably used. Examples thereof include those described in Research Disclosure Magazine 17, 643, 18, 716, 307, 105 and pages (71) to (75) of JP-A No. 64-13,546. Specifically, transparent or translucent hydrophilic binders are preferable, for example, proteins such as gelatin and gelatin derivatives or cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran and pullulan, and polyvinyl alcohol, Examples thereof include synthetic polymer compounds such as polyvinyl pyrrolidone and 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. In particular, a combination of gelatin and the above binder is preferable, and gelatin may be selected from so-called demineralized gelatin with a reduced content of lime-processed gelatin, acid-processed gelatin, calcium, etc., depending on various purposes. Is also preferable.
The amount of binder is 1m²20 g or less per unit is preferable, and 10 g or less is particularly suitable.
[0017]
Further, it is useful to provide a protective layer on the processing member.
As a photothermographic material containing silver halide, preferably used in the present invention, a material for obtaining a black and white silver image as described in Japanese Patent Application No. 7-45018, which has been mentioned in the publicly known examples above. There are those that obtain a color image by such coupling, and those that release a diffusible dye in the form of an image.
When obtaining a black and white silver image, it is preferable to use silver halide having a silver chloride content of 80 mol% or more, and the processing layer contains physical development nuclei and a silver halide solvent.
[0018]
The physical development nucleus reduces the soluble silver salt diffused from the photosensitive material, converts it into physical development silver, and fixes it to the processing layer. Physical development nuclei include heavy metals such as zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt, copper, ruthenium, or precious metals such as palladium, platinum, silver, 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 to form a metal colloidal dispersion, or soluble sulfides, selenides or tellurides. It is obtained by mixing the solution to form a colloidal dispersion of water-insoluble metal sulfide, metal selenide or metal telluride. 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 the silver halide emulsion preparation method may be performed.
These physical development nuclei preferably have a particle size of 2 to 200 nm.
These physical development nuclei are usually 10^-3~ 100mg / m², Preferably 10^-2-10 mg / m²Contain.
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 using physically developed silver transferred to a complexing agent sheet as an image, palladium sulfide, silver sulfide and the like are preferably used in that they have a low minimum density (Dmin) and a high maximum density (Dmax).
[0019]
A well-known thing can be used for a silver halide solvent. 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, described in JP-A-8-179458 And compounds having a 5- to 6-membered imide ring such as uracil and hydantoin, and compounds of the following general formula (I) described in JP-A No. 53-144319 can be used. A meso ion thiolate compound is also preferable to the trimethyltriazolium thiolate described in Analytica Chemica Acta 248, 604-614 (1991). A compound capable of fixing and stabilizing silver halide described in JP-A-8-69097 can also be used as a silver halide solvent.
[0020]
Formula (I) N (R¹) (R²) -C (= S) -X-R^Three
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. R^Three Represents an aliphatic or aryl group. R¹ And R² Or R² And R^Three May combine with each other to form a 5- or 6-membered heterocycle. You may use together said silver halide solvent.
Among the above compounds, compounds having a 5- to 6-membered imide ring such as sulfite, uracil and hydantoin are particularly preferable. In particular, it is preferable to add uracil or hydantoin as a potassium salt in that the gloss reduction during storage of the treated member can be improved.
[0021]
The total silver halide solvent content in the treatment layer is 0.01 to 50 mmol / m.²Preferably, 0.1-30 mmol / m²It is. More preferably, 1-20 mmol / m²It 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.
[0022]
In addition, it is possible to increase the density of the silver image in the light-sensitive material by adding a polymer having as a constituent component a vinylimidazole and / or vinylpyrrolidone repeating unit described in Japanese Patent Application No. 6-325350. is there.
The following is a description of the photothermographic material used mainly for color image formation, particularly for photographing.
[0023]
The silver halide that can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide.
The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. 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 so-called core-shell emulsion in which the inside of the grain and the grain surface layer have different phases, and silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed, and a method of adjusting the gradation by mixing monodispersed emulsions as described in JP-A-1-167,743 and 4-223,463 is preferably used. . The particle size is preferably 0.1 to 2 μm, particularly preferably 0.2 to 1.5 μm. The crystal habits of silver halide grains are those having regular crystals such as cubes, octahedrons, and tetrahedrons, those having irregular crystal systems such as spherical and high aspect ratio flat plate shapes, and those having twin planes. Any of those having such crystal defects or a composite system thereof may be used.
Specifically, U.S. Pat. No. 4,500,626, column 50, 4,628,021, Research Disclosure (hereinafter abbreviated as RD) No. 17,029 (1978), ibid. 17, 643 (December 1978) 22-23, No. 18,716 (November 1979), 648, No. 307,105 (November 1989) 863-865, JP 62-253,159, 64-133,546, JP-A-2-236,546, 3-110,555, and Grafkide, "Physics and Chemistry of Photography", published by Paul Monte (P. Glafkides, Chemie et Phisique Photographique, Paul Montel, 1967), “Photoemulsion Chemistry” by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry, Focal Press, 1966), “Production and Coating of Photoemulsions” , Focal Press published by (V.L.Zelikman et al., Making and Coating Photographic Emalusion, Focal Press, 1964) none of the silver halide emulsion prepared using methods described in the like can be used.
[0024]
In the process of preparing a photosensitive silver halide emulsion, it is preferable to perform so-called desalting to remove excess salt. As a means for this, a Nudell water washing method in which gelatin is gelled may be used, and inorganic salts (for example, sodium sulfate) composed of polyvalent anions, anionic surfactants, anionic polymers (for example, polystyrene sulfonic acid) Sodium), or a precipitation method using gelatin derivatives (eg, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. A sedimentation method is preferably used.
[0025]
The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The amount added depends on the intended use, but is generally 10 per mole of silver halide.^-9-10^-3It is about a mole. Moreover, when making it contain, you may put in a particle | grain uniformly and you may make it local in the inside and surface of particle | grains. Specifically, emulsions described in JP-A-2-236542, 1-116,637 and Japanese Patent Application 4-126,629 are preferably used.
In the grain formation stage of the photosensitive silver halide emulsion, rhodan salts, ammonia, tetrasubstituted thiourea compounds, organic thioether derivatives described in JP-B No. 47-11,386, or JP-A No. 53-144,319 are used as silver halide solvents. Sulfur-containing compounds described in No. can be used.
[0026]
For other conditions, Grafkide's "Physics and Chemistry of Photography" published by Paul Monte (P.Glafkides, Chemie et Phisique Photographique, Paul Montel, 1697), Duffin's "Photoemulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chemistry, Focal Press, 1966), “Production and coating of photographic emulsion” by Zerikman et al., Published by Focal Press (VLZelikman et al., Making and Coating Photographic Emulsion, Focal Press, 1964), etc. Please refer to the description. That is, any of an acidic method, a neutral method, and an ammonia method may be used, and any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used as a form for reacting a soluble silver salt and a soluble halogen salt. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used.
A backmixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the simultaneous mixing method, a so-called controlled double jet method in which pAg in a liquid phase in which silver halide is generated is kept constant can be used.
[0027]
Further, in order to accelerate grain growth, the addition concentration, addition amount, and addition rate of silver salt and halogen salt to be added may be increased (Japanese Patent Laid-Open Nos. 55-142,329 and 55-158,124, U.S. Pat. No. 3,650,757).
Furthermore, the stirring method of the reaction solution may be any known stirring method. Further, the temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner according to the purpose. The preferred pH range is 2.2 to 7.0, more preferably 2.5 to 6.0.
The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, known chalcogen sensitizing methods such as sulfur sensitizing method, selenium sensitizing method, tellurium sensitizing method, gold, platinum, A noble metal sensitizing method using palladium or the like, a reduction sensitizing method, or the like can be used alone or in combination (for example, Japanese Patent Application Laid-Open No. 3-110,555, Japanese Patent Application No. 4-75,798). These chemical sensitizations can also be performed in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Laid-Open No. 62-253,159). Further, the antifoggant described later can be added after the chemical sensitization is completed. Specifically, the methods described in JP-A-5-45,833 and JP-A-62-2040,446 can be used. .
The pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0 to 10.5, more preferably 6.8 to 9 .0.
The coating amount of the photosensitive silver halide emulsion used in the present invention is preferably 1 mg to 10 g / m2 in terms of silver.²In the range of 100 mg to 5 g / m.²Range.
[0028]
In order to give the photosensitive silver halide used in the present invention green sensitivity, red sensitivity, and infrared sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with methine dyes and the like. 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.
Specifically, US Pat. No. 4,617,257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828, JP-A-5-45,834, etc. And sensitizing dyes described in the above.
These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used for the purpose of supersensitization or spectral sensitization wavelength adjustment. .
In addition to the sensitizing dye, a dye that does not itself have spectral sensitizing action or a compound that does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615,641, JP-A-63-23,145, etc.).
These sensitizing dyes may be added to the emulsion during or after chemical ripening, or before or after nucleation of silver halide grains according to US Pat. Nos. 4,183,756 and 4,225,666. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion such as gelatin, or a surfactant. The amount added is generally 10 per mole of silver halide.^-810^-2It is about a mole.
[0029]
Additives used in such processes and known photographic additives that can be used in the present invention are described in RD No. 17,643, No. 18,716, and No. 307,105. The relevant parts are summarized in the following table.

[0030]
In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. 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. Also useful are acetylenes described in US Pat. No. 4,775,613. 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 and organic silver salt is 0.05 to 10 g / m in terms of silver.², Preferably 0.1 to 4 g / m²Is appropriate.
The binder type and amount of the photosensitive material of the present invention are the same as those of the processing member.
[0031]
In the present invention, when a color image is obtained by coupling, the photosensitive material contains a coupler.
The coupler that can be used in the present invention may be a 4-equivalent coupler or a 2-equivalent coupler. Further, the diffusion-resistant group may form a polymer chain. Specific examples of the coupler are THJames “The Theory of the Photographic Process”, 4th edition, pages 291 to 334, and pages 354 to 361, 58 to 123533, 58 to 149046, 58 to 149047, and 59 to 111148. 59-124399, 59-174835, 59-231539, 59-231540, 60-2950, 60-2951, 60-14242, 60-23474, No. 60-66249, No. 8-110608, No. 8-146552, No. 8-146578, and the like.
[0032]
Moreover, it is preferable to use the following couplers.
Yellow coupler: coupler represented by formulas (I) and (II) of EP502,424A; coupler represented by formulas (1) and (2) of EP513,496A, general formula of claim 1 of Japanese Patent Application No. 4-134523 A coupler represented by formula (I); a coupler represented by general formula D on lines 45 and 55 in column 1 of US 5,066,576; a coupler represented by general formula D in paragraph 0008 of JP-A-4-274425; 40 of EP498,381A1 Couplers according to claim 1 on page 4, couplers represented by formula (Y) on page 4 of EP447,969A1, couplers represented by formulas (I) to (IV) on lines 36, 58 of column 7, US 4,476,219,
Magenta couplers: couplers described in JP-A-3-39737, Japanese Patent Application 4-234120, Japanese Patent Application 4-36917, and JP-A-4-3626.
Cyan coupler: JP-A-4-204843, JP-A-4-43345, JP-A-4-23633
Polymer coupler: JP-A-2-44345.
[0033]
As couplers in which the coloring dye has an appropriate diffusibility, those described in US 4,366,237, GB 2,125,570, EP 96,570, DE 3,234,533 are preferable.
[0034]
The photosensitive material may contain the following functional coupler. Couplers for correcting unnecessary absorption of the coloring dye include yellow colored cyan couplers described in EP456,257A1, yellow colored magenta couplers described in EP, magenta colored cyan couplers described in US4,833,069, and US4,837,136. (2) A colorless masking coupler represented by the formula (A) of claim 1 of WO 92/11575 (particularly, exemplified compounds on pages 36 to 45).
Examples of the compounds (including couplers) that release a photographically useful compound residue by reacting with oxidized developing agent include the following. Development inhibitor releasing compounds: compounds represented by formulas (I) to (IV) described on page 11 of EP378,236A1, compounds represented by formula (I) described on page 7 of EP436,938A2, and Japanese Patent Application No. 4 A compound represented by formula (1) of -134523, a compound represented by formulas (I), (II) and (III) described on pages 5 and 6 of EP440,195A2, and claim 1 of Japanese Patent Application No. 4-325564 A compound represented by the formula (I): a ligand-releasing compound, a compound represented by LIG-X described in claim 1 of US 4,555,478.
[0035]
In the light-sensitive material used in the present invention, for the purpose of shortening the development time, improving the sensitivity, improving the image density, etc., the oxidant produced by silver development can be coupled with the above-mentioned coupler to form a dye. An embodiment in which a developing agent is incorporated is preferable.
In this case, phenol or an active methylene coupler as a p-phenylenediamine developing agent in US Pat. No. 3,531,256, a combination of a p-aminophenol developing agent and an active methylene coupler as described in US Pat. No. 3,761,270. Can be used.
A combination of a sulfonamide phenol and a 4-equivalent coupler as described in U.S. Pat. No. 4,021,240 and JP-A-60-128438 is excellent in raw storage when incorporated in a photosensitive material, A preferred combination.
When a color developing agent is incorporated, a color developing agent precursor may be used. For example, an indoaniline compound described in US Pat. No. 3,342,597, a Schiff base type compound described in US Pat. No. 3,342,599, Research Disclosure No. 14,850 and No. 15,159, Examples include aldol compounds, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A No. 53-135628.
[0036]
Further, the sulfonamide phenolic main agent described in Japanese Patent Application No. 7-180,568 and the combination of a hydrazine main agent and a coupler described in Japanese Patent Application Nos. 7-49287 and 7-63572 are also used in the light-sensitive material of the present invention. Preferred for use in.
[0037]
In the case of using a non-diffusible developing agent, an electron transfer agent and / or an electron transfer agent may be used as necessary to promote electron transfer between the non-diffusible developing agent and the developable silver halide. A precursor can be used in combination. Particularly preferably, those described in US Pat. No. 5,139,919 and European Patent Publication No. 418,743 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 developing agents or their precursors. It is desirable that the electron transfer agent or its precursor has a higher mobility than the non-diffusible developing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.
An electron donor precursor as described in JP-A-3-160,443 is also preferably used.
Furthermore, various reducing agents can be used in the intermediate layer and the protective layer for various purposes such as preventing color mixing and improving color reproduction. Specifically, reducing agents described in European Patent Publication Nos. 524,649, 357,040, JP-A-4-249,245, 2-46,450 and JP-A-63-186,240. Is preferably used. JP-B-3-63,733, JP-A-1-150,135, 2-46,450, 2-64,634, 3-43,735, European Patent Publication 451,833. A development inhibitor releasing reductant compound as described in US Pat.
[0038]
In addition, the following reducing agent may be incorporated in the photosensitive material.
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, 62-244,044, 62-131,253, Nos. (40) to (40) of (62-131,256) and (64-13,546). 57), JP-A-1-120,553, European Patent 220,746A2, pages 78-96, and the like.
Also, combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can be used.
[0039]
The developing agent or the reducing agent may be incorporated in the processing member, but is preferably incorporated in the photosensitive material.
[0040]
In the present invention, the total amount of the developing agent and the reducing agent is 0.01 to 20 mol, particularly preferably 0.1 to 10 mol, per 1 mol of silver.
[0041]
Next, a case where a diffusible dye is released in an image form will be described.
In the present invention, a non-diffusible colorant that releases a diffusible dye corresponding to or oppositely corresponding to silver development is used. This type of compound can be represented by the following general formula [L1].
((Dye)_m-Y)_n-Z [L1]
Dye represents a diffusible dye group, Y represents a simple linking group, and Z represents a diffusible (Dye) corresponding to or inversely corresponding to a photosensitive silver salt having a latent image in an image form_mWhen -Y is released and L1 itself is non-diffusible, m represents an integer of 1 to 5, n represents 1 or 2, and m and n are not 1. The plurality of Dye may be the same or different.
Specific examples of the colorant represented by the general formula [L1] include the following compounds (1) to (4). The following (1) to (3) release diffusible dyes correspondingly to the development of silver halide, and (4) releases diffusible dyes corresponding to the development of silver halide. To do.
(1) U.S. Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, 3,482,972, JP 3-68 , No. 387, etc., a dye developer obtained by linking a hydroquinone developer and a dye component. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide.
(2) As described in US 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 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.
[0042]
(3) U.S. Pat. No. 4,559,290, European Patent 220,746 A2, U.S. Pat. No. 4,783,396, Published Technical Report 87-6, 199, JP-A-64-13546, etc. As described above, a non-diffusible compound that reacts with a reducing agent remaining unoxidized by development to release a diffusible dye 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 described in U.S. Pat. No. 4,450,223. 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.
[0043]
More preferable are European Patent No. 220,746A2, 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 issue₂ -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. Also used are compounds described in JP-A-1-161,237 and 1-161,342 that release a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated with an electron accepting group. it can.
Among these, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include compounds (1) to (3), (7) to (10), (12), (13), described in European Patent 220,746 A2 or US Pat. No. 4,783,396. (15), (23)-(26), (31), (32), (35), (36), (40), (41), (44), (53)-(59), (64 ), (70), compounds (11) to (23) described in published technical reports 87-6 and 199, compounds (1) to (84) described in JP-A No. 64-13,546, etc. is there.
[0044]
(4) A compound (DRR compound) that is reducible to silver halide or organic silver salt and releases a diffusible dye when the partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to the oxidative decomposition product of the reducing agent. Typical examples thereof are U.S. Pat. Nos. 3,928,312, 4,053,312, 4,055,428, 4,336,322, and JP-A-59-65,839. 59-69,839, 53-3,819, 51-104,343, RD17,465, US Pat. Nos. 3,725,062, 3,728,113, 3,443 939, JP-A-58-116,537, JP-A-57-179,840, US Pat. No. 4,500,626, and the like. Specific examples of DRR compounds include the compounds described in columns 22 to 44 of the aforementioned U.S. Pat. No. 4,500,626. Among them, compounds (1) to (3), (10) to (13), (16) to (19), (28) to (30), (33) to (35), (38) to (40), (42) to (64) ) Is preferred. Also useful are the compounds described in US Pat. No. 4,639,408, columns 37-39.
[0045]
In a system in which a diffusible dye is released in an image form and diffused and transferred to a processing member, a mordant is preferably contained in the processing layer. As the mordant, those known in the photographic field can be used. Specific examples thereof include a mordant described in US Pat. No. 4,500,626, columns 58 to 59 and JP-A 61-88256, pages 32 to 41, and Examples thereof include those described in Kaikai 62-244043 and 62-244036. Further, a dye-accepting polymer compound as described in US Pat. No. 4,463,079 may be used.
[0046]
Hydrophobic additives such as coloring materials, couplers, color developing agents and diffusion-resistant reducing agents can be introduced into the layer of the photosensitive material by known methods 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, High-boiling organic solvents such as those described in Nos. 599, 296 and 3-62, 256 can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C as necessary. 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 dye-donating compound 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. Addition as a dispersion method using a polymer described in JP-B-51-39,853 and JP-A-51-59,943 or a fine particle dispersion described in JP-A-62-30,242 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 the above-mentioned Research Disclosure can be used. Further, phosphate ester type surfactants described in Japanese Patent Application Nos. 5-204325 and 6-19247 and West German Patent No. 1,932,299A can also be used.
In the present invention, a compound capable of stabilizing the image simultaneously with activation of development can be used in the photosensitive material. Specific compounds preferably used are described in columns 51 to 52 of US Pat. No. 4,500,626.
[0047]
The photographic photosensitive material includes at least three types of photosensitive layers having different spectral sensitivities and hues of color materials. Each photosensitive layer may be divided into a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The three types of photosensitive layers are preferably layers that are sensitive to any of blue light, green light, and red light. This arrangement order is generally the order of the red photosensitive layer, the green photosensitive layer, and the blue photosensitive layer in order from the support side. However, other arrangements may be used depending on the purpose. For example, an arrangement as described in column 162 of JP-A-7-152129 may be used.
In the present invention, the silver halide and the color material may be contained in the same layer, but can be added separately in separate layers as long as they can react. For example, if a layer containing a coloring material that is originally colored is disposed below the layer containing silver halide, the sensitivity can be prevented from being lowered.
The relationship between the spectral sensitivity of each layer and the hue of the color material is arbitrary, but if a cyan color material is used for the red photosensitive layer, a magenta color material is used for the green photosensitive layer, and a yellow color material is used for the blue photosensitive layer, the conventional color Projection exposure can be performed directly on paper.
[0048]
The light-sensitive material is provided with various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer between and above the silver halide emulsion layers. In addition, various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, the layer structure as described in the above patent, the undercoat layer as described in US Pat. No. 5,051,335, and those described in JP-A-1-167,838 and JP-A-61-2943 An intermediate layer having such a solid pigment, an intermediate layer having a reducing agent or DIR compound as described in JP-A-1-120,553, JP-A-5-34,884 and JP-A-2-64634, U.S. Pat. 5,017,454, 5,139,919, an intermediate layer having an electron transfer agent as described in JP-A-2-235044, and a reducing agent as described in JP-A-4-249,245. The protective layer which has or a layer which combined these can be provided.
[0049]
A thermal solvent may be added to the photosensitive material for the purpose of promoting thermal development. Examples thereof include organic compounds having polarity as described in US Pat. Nos. 3,347,675 and 3,667,959. Specifically, amide derivatives (benzamide, etc.), urea derivatives (methylurea, ethyleneurea, etc.), sulfonamide derivatives (compounds described in JP-B-1-40974 and JP-B-4-13701), polyol compounds (Such as sorbitol) and polyethylene glycols.
When the hot solvent is insoluble in water, it is preferably used as a solid dispersion. The layer to be added may be either a photosensitive layer or a non-photosensitive layer depending on the purpose.
The amount of the hot solvent added is 10% to 500% by weight, preferably 20% to 300% by weight, based on the binder of the layer to be added.
[0050]
The photosensitive material and the processing member used in the present invention are preferably hardened with a hardener.
Examples of hardeners include U.S. Pat. No. 4,678,739, column 41, 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, etc.), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid or polymer hardeners (compounds described in JP-A-62-234157).
These hardeners are used in an amount of 0.001-1 g, preferably 0.005-0.5 g, per 1 g of hydrophilic binder.
[0051]
Various antifoggants or photographic stabilizers and precursors thereof can be used for the light-sensitive material. Specific examples thereof include the Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A-64-13564 (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, JP-A-1-150,135, 2-110,557, 2-178,650, RD17,643 (1978) ( Examples thereof include compounds described on pages 24) to (25).
These compounds are 5 × 10 5 per mole of silver.^-6~ 1x10^-1Moles are preferred, further 1 × 10^-Five~ 1x10^-2Mole is preferably used.
[0052]
In the photosensitive material and the processing member, various surfactants can be used for the purpose of coating aid, improvement of peelability, improvement of sliding property, antistatic, development promotion and the like. Specific examples of the surfactant are disclosed in the known technology No. 5 (March 22, 1991, issued by Aztec Co., Ltd.), pages 136-138, JP-A-62-173463, 62-183,457, etc. Has been described.
The photosensitive material and the processing member may contain an organic fluoro compound for the purpose of improving smoothness, 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. And hydrophobic fluorine compounds such as oily fluorine compounds or solid fluorine compound resins such as tetrafluoroethylene resin.
[0053]
A matting agent can be used for the photosensitive material. As the matting agent, in addition to the compounds described on page 29 of JP-A-61-88256 such as silicon dioxide, polyolefin or polymethacrylate, JP-A-63-274944 such as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads. No. 63-274922. In addition, the compounds described in Research Disclosure can be used.
In the present invention, the support for the photosensitive material is preferably the same as that used for the above-mentioned processing member.
[0054]
In particular, as a support for a light-sensitive material, Japanese Patent Application Laid-Open No. 6-41281, No. 6-43581, No. 6-51426, No. 6-51437, No. 6-51442, and Japanese Patent Application No. 4-51442 are disclosed. No. 251845, No. 4-218325, No. 4-253545, No. 4-258828, No. 4-240122, No. 4-221538, No. 5-21625, No. 5-15926, No. 4-331828 The supports described in JP-A-5-199704, JP-A-6-13455, and JP-A-6-14666 can be preferably used.
Further, a support which is a styrene polymer mainly having a syndiotactic structure can also be preferably used.
Further, using a support having a magnetic material layer described in JP-A-4-124645, JP-A-5-40321, JP-A-6-35092, Japanese Patent Application Nos. 5-58221 and 5-106979, photographing information and the like can be obtained. It is preferable to record.
[0055]
The photographic light-sensitive material used in the present invention is processed in the same manner as a normal color negative and can be directly photographed by being loaded into a camera. The film unit with a lens described in JP-B-2-32615 and JP-B-3-39784 can be preferably used.
[0056]
The photosensitive material and / or the processing member may have a conductive heating element layer as a heating means for heat development. As the heat generating element in this case, those described in JP-A No. 61-145,544 can be used.
[0057]
The heating temperature in the heat development step is about 50 ° C. to 250 ° C., but about 60 ° C. to 180 ° C. is particularly useful. In a system using release of a diffusible dye, the dye diffusion transfer process may be performed simultaneously with the heat development or after the heat development process is completed. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but is preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.
In a system that utilizes the release of a diffusible dye, the movement of the dye is caused only by heat, but the above-described thermal solvent and other solvents may be used to promote the movement of the dye.
[0058]
In the present invention, a method of developing by heating in the presence of a small amount of dampening water is useful. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of water or lower.
Examples of the fountain solution used for accelerating development and / or dye diffusion transfer include water, a basic aqueous solution containing an inorganic alkali metal salt and an organic base (these bases include an image forming accelerator). Or a mixed solution of a low-boiling solvent or a low-boiling solvent and water or the basic aqueous solution. Further, a surfactant, an antifoggant, a complex-forming compound with a hardly soluble metal salt, an antifungal agent, and an antifungal agent may be contained in the solvent.
Any fountain solution used in these heat development and / or diffusion transfer processes may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water, or the like can be used. In the heat development apparatus using the light-sensitive material and the image receiving element 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.
[0059]
In the present invention, the amount of dampening water used for the photosensitive material may be equal to or less than the weight of water corresponding to the maximum swelling volume of the entire coating film of the photosensitive material and the processing member.
As a method for applying this water, for example, methods described in JP-A-62-253159 (page 5), JP-A-63-85544, etc. are preferably used. Further, the solvent can be confined in a microcapsule, or can be used in the form of a hydrate in advance in a photosensitive material or a dye-fixing element or both.
The temperature of water to be applied may be 30 ° to 60 ° as described in JP-A-63-85,544.
[0060]
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.
The method described in JP-A-62-253,159 and JP-A-61-147,244 (27) can be applied as a method for superimposing the photosensitive material and the processing member.
[0061]
Any of various heat development apparatuses can be used for the heat development treatment 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, 6-164421, 6-164422, etc. are preferably used. Moreover, as a commercially available apparatus, the Pictorostat 100, the Pictorostat 200, the Pictorostat 300, the Pictography 3000, the Pictography 2000, etc. manufactured by Fuji Photo Film Co., Ltd. can be used.
[0062]
In the present invention, an additional development stop process is unnecessary after the development process. However, a development stopper may be included in the processing member, and the development stopper may be used simultaneously with 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).
Further, a combination in which a zinc salt of mercaptocarboxylic acid described in Japanese Patent Application No. 6-190529 is contained in a photosensitive element and a complexing compound is contained in a processing member is advantageous.
Similarly, a silver halide printout preventing agent may be included in the processing sheet, and its function may be developed simultaneously with development. Examples of printout inhibitors include monohalogen compounds described in JP-B-54-164, trihalogen compounds described in JP-A-53-46020, and halogens described in JP-A-48-45228 bonded to an aliphatic carbon atom. And a polyhalogen compound typified by tetrabromoxylene described in JP-B-57-8454. Development inhibitors such as 1-phenyl-5-mercaptotetrazole described in British Patent 1,005,144 are also effective.
A viologen compound described in Japanese Patent Application No. 6-337531 is also effective.
The amount of printout inhibitor used is preferably 10^-Four˜1 mol / Ag 1 mol, particularly preferably 10^-3-10^-1Mol / Ag 1 mol.
[0063]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
First, production of a color negative film photosensitive material (K01) will be described.
A method for preparing a dispersion of zinc hydroxide will be described.
[0064]
Add 12.5 g of zinc hydroxide with an average particle size of 0.2 μm, 1 g of carboxymethylcellulose as a dispersant and 0.1 g of sodium polyacrylate to 100 ml of 4% gelatin aqueous solution, and use a mill to add glass beads with an average particle size of 0.75 mm. And ground for 30 minutes. The glass beads were separated to obtain a dispersion of zinc hydroxide.
[0065]
Next, a method for adjusting the dispersion of the electron transfer agent will be described.
[0066]
10 g of the following electron transfer agent, 0.5 g of polyethylene glycol nonylphenyl ether as a dispersing agent, 0.5 g of the following surfactant (1) are added to a 5% gelatin aqueous solution, and glass beads having an average particle diameter of 0.75 mm are obtained with a mill. And ground for 60 minutes. The glass beads were separated to obtain a dispersion of an electron transfer agent having an average particle size of 0.35 μm.
[0067]
[Chemical 1]

[0068]
[Chemical 2]

[0069]
Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.
[0070]
Cyan, magenta and yellow dye-donating compounds and electron donor gelatin dispersions were respectively prepared according to the formulations in Table K1. That is, each oil phase component was dissolved by heating at about 60 ° C. to obtain a uniform solution, and this solution and an aqueous phase component heated to about 60 ° C. were added, stirred and mixed, and then dispersed with a homogenizer at 12000 rpm for 13 minutes. Water was added thereto and stirred to obtain a uniform dispersion.
[0071]
[Table 1]

[0072]
[Chemical 3]

[0073]
[Formula 4]

[0074]
[Chemical formula 5]

[0075]
[Chemical 6]

[0076]
[Chemical 7]

[0077]
[Chemical 8]

[0078]
[Chemical 9]

[0079]
[Chemical Formula 10]

[0080]
Embedded image

[0081]
Embedded image

[0082]
Embedded image

[0083]
Embedded image

[0084]
Embedded image

[0085]
Embedded image

[0086]
Next, how to prepare a photosensitive silver halide emulsion will be described.
[0087]
Photosensitive silver halide emulsion (1) (for red-sensitive emulsion layer)
To a well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 2.5 g of sodium chloride and 15 mg of the following chemical (A) in 700 ml of water and kept warm at 42 ° C.), Solution (I) and solution (II) were added simultaneously at an equal flow rate for 8 minutes. Next, 8 minutes after the completion of the addition of the liquids (I) and (II), an aqueous solution of gelatin dispersion of the dye (1.9 g of gelatin in 160 ml of water, 127 mg of the following dye (a), 253 mg of the following dye (b), Dye (c) containing 8 mg and kept at 35 ° C.) was added. After 2 minutes, the liquids (III) and (IV) in Table 2 were added simultaneously at an equal flow rate for 32 minutes.
[0088]
After washing with water and desalting by a conventional method, 22 g of lime-processed ossein gelatin and 50 mg of the following chemical (B) were added to adjust pH to 6.2 and pAg to 7.8 to give 4-hydroxy-6-methyl-1 , 3,3a, 7-tetrazaindene, then sodium thiosulfate and chloroauric acid and optimally chemical sensitization at 68 ° C., followed by antifoggant (1) described below, ) 80 mg and chemical (D) 3 g were added and cooled. In this way, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.21 μm was obtained.
[0089]
[Table 2]

[0090]
Embedded image

[0091]
Embedded image

[0092]
Embedded image

[0093]
Photosensitive silver halide emulsion (2) (for red-sensitive emulsion layers)
Table K3 (I) was added to a well-stirred gelatin aqueous solution (20 g gelatin, 0.3 g potassium bromide, 9 g sodium chloride and 15 mg of the above-mentioned chemical (A) in 700 ml water and kept at 53 ° C.). Liquid and liquid (II) were added simultaneously at an equal flow rate for 10 minutes. Next, 6 minutes after the end of the addition of the liquids (I) and (II), an aqueous solution of a gelatin dispersion of the dye (1.2 g of gelatin in 115 ml of water, 77 mg of the dye (a), 153 mg of the dye (b), Dye (c) containing 5 mg and kept at 45 ° C.) was added. After 4 minutes, the liquids (III) and (IV) in Table K2 were added simultaneously at an equal flow rate for 30 minutes.
[0094]
After washing with water and desalting by a conventional method, 33 g of lime-processed ossein gelatin and 50 mg of the above chemical (B) were added to adjust pH to 6.2 and pAg to 7.8 to give 4-hydroxy-6-methyl-1 , 3,3a, 7-tetrazaindene, then sodium thiosulfate and chloroauric acid, and optimum chemical sensitization at 68 ° C., followed by antifoggant (1) described above, ) 80 mg and chemical (D) 3 g were added and cooled. In this way, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.
[0095]
[Table 3]

[0096]
Photosensitive silver halide emulsion (3) [For green-sensitive emulsion layers]
Table K4 (I Solution) and solution (II) were added simultaneously at an equal flow rate for 8 minutes. Ten minutes later, the liquids (III) and (IV) in Table K4 were further added at the same flow rate for 32 minutes. Further, 1 minute after completion of the addition of the liquids (III) and (IV), a methanol solution of the dye (containing 280 mg of the following dye (d) in 47 ml of methanol and kept at 30 ° C.) was added all at once.
[0097]
After washing with water and desalting by a conventional method, 22 g of lime-processed ossein gelatin, 50 mg of the above-mentioned medicine (B) and 3 g of medicine (D) are added to adjust pH to 6.0 and pAg to 7.1 to give 4-hydroxy After adding -6-methyl-1,3,3a, 7-tetrazaindene, then adding sodium thiosulfate to optimal chemical sensitization at 60 ° C., and then adding antifoggant (1) described below Cooled down. In this way, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.23 μm was obtained.
[0098]
[Table 4]

[0099]
Embedded image

[0100]
Photosensitive silver halide emulsion (4) [for green-sensitive emulsion layers]
Table K5 (Table K5) shows a well-stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride and 7.5 mg of the above-mentioned chemical (A) in 710 ml of water and kept at 63 ° C.). Solution I) and solution (II) were added simultaneously at an equal flow rate for 10 minutes. Ten minutes later, the liquids (III) and (IV) in Table K5 were added simultaneously at an equal flow rate for 20 minutes. Also, 1 minute after the end of the addition of the liquids (III) and (IV), a methanol solution of the dye (containing 210 mg of the following dye (d-1) and 42.7 mg of (d-2) in 35 ml of methanol and kept at 46 ° C.) ) Was added all at once.
[0101]
After washing with water and desalting by a conventional method, 33 g of lime-processed ossein gelatin, 50 mg of the above-mentioned medicine (B) and 3 g of medicine (D) are added to adjust pH to 6.0 and pAg to 7.2. -6-methyl-1,3,3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimal chemical sensitization at 60 ° C. Then, the antifoggant (1) shown below was added. Cooled after addition. In this way, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.
[0102]
[Table 5]

[0103]
Embedded image

[0104]
Photosensitive silver halide emulsion (5) [for blue-sensitive emulsion layer]
To a well-stirred aqueous gelatin solution (20 g gelatin, 0.5 g potassium bromide, 5 g sodium chloride and 15 mg of the above-mentioned chemical (A) in 690 ml water and kept at 46 ° C.), the mixture of (I ) Solution and (II) solution were added simultaneously at an equal flow rate for 8 minutes. Ten minutes later, the liquids (III) and (IV) in Table K6 were added simultaneously at an equal flow rate for 18 minutes. In addition, 1 minute after the completion of addition of the liquids (III) and (IV), an aqueous dye solution (containing 225 mg of the following dye (e) and 225 mg of the following dye (f) in 95 ml of water and 5 ml of methanol and kept at 30 ° C. ) Was added all at once.
[0105]
After washing with water and desalting by a conventional method, 22 g of lime-processed ossein gelatin, 50 mg of the above-mentioned medicine (B) and 3 g of medicine (D) are added to adjust pH to 6.0 and pAg to 7.7 to 4-hydroxy -6-methyl-1,3,3a, 7-tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 65 ° C, and then antifoggant (1) described later was added. After cooling. In this manner, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.
[0106]
[Table 6]

[0107]
Embedded image

[0108]
Photosensitive silver halide emulsion (6) [Blue sensitive emulsion layer]
In a well-stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride and 15 mg of the above-mentioned chemical (A) in 710 ml of water and kept warm at 59 ° C.), ) Solution and (II) solution were added simultaneously at an equal flow rate for 8 minutes. Ten minutes later, the liquids (III) and (IV) in Table K7 were added simultaneously at an equal flow rate for 18 minutes. Also, 1 minute after the completion of addition of the liquids (III) and (IV), an aqueous dye solution (113 mg of the dye (e) and 113 mg of the dye (f) in 82 ml of water and 6 ml of methanol was kept at 40 ° C.) ) Was added all at once.
[0109]
After washing with water and desalting by a conventional method, 33 g of lime-processed ossein gelatin, 50 mg of the above-mentioned medicine (B) and 3 g of medicine (D) are added, and the pH is adjusted to 6.0 and pAg is adjusted to 7.7. -6-methyl-1,3,3a, 7-tetrazaindene was added, then sodium thiosulfate and chloroauric acid were added to perform optimum chemical sensitization at 65 ° C, and then antifoggant (1) shown below was added. Cooled after addition. In this way, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.47 μm was obtained.
[0110]
[Table 7]

[0111]
The photosensitive material K01 shown in Table K8 was produced using the above.
[0112]
[Table 8]

[0113]
[Table 9]

[0114]
[Table 10]

[0115]
Embedded image

[0116]
Next, preparation of a processing member used for forming an image on the photosensitive material by processing in combination with the photosensitive material will be described.
[0117]
A method for preparing a dispersion of additive (2) will be described.
[0118]
Embedded image

[0119]
1 g of additive (2) and 1.2 g of anionic surfactant (3) are dissolved in 100 g of high boiling point solvent (4) by heating at 50 ° C. Separately, 60 g of lime-processed gelatin is swollen in 300 cc of ion-exchanged water, dissolved at 70 ° C., and a preservative is added. After mixing both at 40 degreeC, it emulsifies and disperses with an ultrasonic dispersing device. By this operation, an emulsified dispersion having an average particle size of 0.1 to 1 μm of the additive (2) is obtained.
[0120]
Embedded image

[0121]
Using the above dispersion and the raw materials shown in Table R1, a treatment member R101 was produced by applying the mixture onto a support having the structure shown in Table A1 (however, the polymer layer thickness was 6 μm) according to the structure shown in Table R1.
[0122]
[Table 11]

[0123]
[Table 12]

[0124]
Embedded image

[0125]
Embedded image

[0126]
Embedded image

[0127]
Embedded image

[0128]
Similarly, processing members R102 to 110 were prepared in the same manner as R101, using the support of the support of the polymer thickness or pulp thickness (Tables A2 to 4) shown in Table V1.
[0129]
[Table 13]

[0130]
[Table 14]

[0131]
[Table 15]

[0132]
[Table 16]

[0133]
The photosensitive element (K01) was cut into a size of 36 normal 35 mm color negative film, punched and loaded into a camera, and a standard image was taken by close-up. Separately, the processing member (R101) cut into a sheet having a width of 40 mm and a length of 2 m was wound around a roll core (feeding side) having a diameter of 1 inch so that the coated surface faced outward. Thereafter, the tip of the processing member was partially wound around another winding core (winding side).
[0134]
The processing member was set in such a direction that the film surface of the processing member during feeding and winding contacted the outer surface of the drum heater. Next, 13 ml / m of dampening water kept at 40 ° C. is applied onto the exposed photosensitive material surface.²Deployed at a rate of. The photosensitive material film surface and the processing member film surface are laminated so that the processing member is in contact with the drum heater, and the photosensitive material is moved while moving the processing member and the photosensitive material at the same speed as the rotation speed of the drum heater. The speed and the heater temperature were adjusted and processed so as to be heated at 80 ° C. for 20 seconds before being peeled off from the processing member. Next, the treatment member was peeled from the photosensitive material at a position away from the heater drum. By this operation, there was no problem in bonding and peeling, and an image of silver and a dye was formed on the photosensitive material, and the handleability was good.
[0135]
The superiority in handling image formation was significant when the thickness of the support was 4 μm or more and 40 μm or less (R101 to 103, R106). In addition, in the case where the support was PET (R101 to 106) and the double-sided laminated paper support (R107 to 110), the handleability was good.
Further, when the processing member was wound around the inner surface of the film, curling at the time of winding was less likely to occur, and good handleability was exhibited.
Furthermore, the handling property is also good when the conveying member is provided on a flat or curved heater instead of the drum heater as described above, and the photosensitive material and the processing member are moved on the conveying member. It was.
[0136]
Example 2
The production of the color positive photosensitive material (K03) will be described below.
[0137]
Next, how to make a gelatin dispersion of compound (d) is described.
Compound (d) 0.4g, high boiling point organic solvent (1) 1.2g, compound (f) 0.12g, compound (g) 0.25g, compound (h) 0.05g, surface activity 0.2 g of the agent (1) was weighed, 9.5 cc of ethyl acetate was added and dissolved by heating at about 60 ° C. to obtain a uniform solution. This solution and 29.1 g of a 18% solution of lime-processed gelatin were mixed with stirring, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. After dispersion, 18.5 cc of dilution water was added. This dispersion is referred to as a dispersion of compound (d).
[0138]
Embedded image

[0139]
Next, how to make a gelatin dispersion of the dye-donating compound is described.
7.3 g of cyan dye-donating compound (A1), 11.0 g of cyan dye-donating compound (A2), 0.8 g of surfactant (1), 1 g of compound (h), compound (i) 2 g, 7 g of high boiling point organic solvent (1) and 3 g of high boiling point organic solvent (2), add 26 ml of ethyl acetate and 1.2 ml of water, heat and dissolve at about 60 ° C. to obtain a homogeneous solution. did. This solution, 65 g of a 16% solution of lime-processed gelatin, and 87 cc of water were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. After dispersion, 216 cc of dilution water was added. This dispersion is referred to as a dispersion of cyan dye-donating compound.
[0140]
Embedded image

[0141]
Embedded image

[0142]
4.50 g of magenta dye-donating compound (B), 0.05 g of compound (m), 0.05 g of compound (h), 0.094 g of surfactant (1), high-boiling organic solvent (2) 2.25 g was weighed, 10 ml of ethyl acetate was added and dissolved by heating at about 60 ° C. to obtain a uniform solution. This solution, 15.2 g of a 16% solution of lime-processed gelatin, and 23.5 cc of water were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. Thereafter, 42 cc of dilution water was added. This dispersion is referred to as a magenta dye-donating compound dispersion.
[0143]
Embedded image

[0144]
15 g of yellow dye-donating compound (C), 2.3 g of compound (d), 0.9 g of compound (h), 0.88 g of surfactant (1), 3.9 g of compound (j), 1.9 g of compound (k) and 16.9 g of high-boiling organic solvent (1) were weighed, 49 ml of ethyl acetate was added, and heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 63.5 g of a 16% solution of lime-processed gelatin, and 103 cc of water were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. Thereafter, 94 cc of dilution water was added. This dispersion is referred to as a yellow dye-donating compound dispersion.
Thus, a photothermographic material K02 as shown in Table L1 was constituted.
[0145]
[Table 17]

[0146]
[Table 18]

[0147]
Embedded image

[0148]
When processing members R101 to 110 used in Example 1 were used to prepare, process, and evaluate the same members as in Example 1, images could be obtained with exactly the same handleability. It was.
[0149]
However, the processing temperature was 83 ° C. and the processing time was 35 seconds.
In addition, when the processing member was processed to a width of 160 mm and a length of 2 m, and four photosensitive elements K02 processed to a width of 35 mm were arranged in parallel at the same time, the photographic properties such as Dmax, Dmin, gradation, sensitivity, etc. were almost equal. Similar results could be obtained.
[0150]
Example 3
First, the photosensitive element (K03) will be described.
[0151]
The dye composition was prepared and added as an emulsified dispersion as follows.
Weigh leuco dye, developer and high-boiling organic solvent if necessary, add ethyl acetate, heat and dissolve at about 60 ° C. to make a uniform solution, and add 100% of surfactant (1) to rice cake solution 100 cc. 190 g of a 6.6% aqueous solution of lime-processed gelatin heated to about 60 ° C. was added and dispersed with a homogenizer at 10,000 ppm for 10 minutes.
Two types of dye dispersions shown in Table M1 were prepared.
[0152]
[Table 19]

[0153]
Embedded image

[0154]
How to make a photosensitive silver halide emulsion is described.
[0155]
Photosensitive silver halide emulsion (1) [for red-sensitive emulsion layer]
To a well-stirred aqueous gelatin solution (20 g gelatin, 0.5 g potassium bromide, 2.5 g sodium chloride and 15 mg of the following chemical (A) in 700 ml water and kept warm at 42 ° C.), The liquid (I) and the liquid (II) were simultaneously added at an equal flow rate for 8 minutes. Next, 8 minutes after completion of the addition of the liquids (I) and (II), an aqueous solution of gelatin dispersion of the dye (1.9 g of gelatin in 160 ml of water, 127 mg of the following dye (a), 253 mg of the following dye (b), Dye (c) containing 8 mb and kept at 35 ° C.) was added. After 2 minutes, liquids (III) and (IV) in Table M2 were further added at the same flow rate for 32 minutes.
[0156]
After washing with water and desalting by a conventional method, 22 g of lime-processed ossein gelatin and 50 mg of the following chemical (B) were added to adjust pH to 6.2 and pAg to 7.8 to give 4-hydroxy-6-methyl-1 , 3,3a, 7-tetrazaindene, then sodium thiosulfate and chloroauric acid and optimally chemical sensitization at 68 ° C., followed by antifoggant (1), chemical (C) 80 mg, chemical (D) It cooled after adding 3g. In this way, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.21 μm was obtained.
[0157]
[Table 20]

[0158]
Embedded image

[0159]
Embedded image

[0160]
Embedded image

[0161]
Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer]
To a well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride and 15 mg of the above-mentioned chemical (A) in 700 ml of water and kept warm at 53 ° C.), The liquid and the liquid (II) were simultaneously added at an equal flow rate for 10 minutes. Then, 6 minutes after completion of the addition of the liquids (I) and (II), an aqueous solution of a gelatin dispersion of the dye (1.2 g of gelatin in 115 ml of water, 77 mg of the dye (a), 153 mg of the dye (b), Dye (c) containing 5 mg and kept at 45 ° C.) was added. After 4 minutes, the liquids (III) and (IV) in Table M3 were added simultaneously at an equal flow rate for 30 minutes.
[0162]
4-hydroxy-6-methyl-1 adjusted to pH 6.2 and pAg adjusted to 7.8 by adding 33 mg of lime-processed ossein gelatin and 50 mg of the above-mentioned chemical (B) after washing and desalting with ordinary methods. , 3,3a, 7-tetrazaindene, then sodium thiosulfate and chloroauric acid and optimally chemical sensitization at 68 ° C., followed by antifoggant (1), chemical (C) 80 mg, chemical (D) It cooled after adding 3g. In this way, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.
[0163]
[Table 21]

[0164]
Photosensitive silver halide emulsion (3) [for green-sensitive emulsion layers]
To a well-stirred gelatin aqueous solution (20 g gelatin, 0.5 g potassium bromide, 5 g sodium chloride and 15 mg of the above-mentioned chemical (A) in 690 ml water and kept warm at 41 ° C.), (I ) Solution and (II) solution were added simultaneously at an equal flow rate for 8 minutes. Ten minutes later, the liquids (III) and (IV) in Table M4 were further added at the same flow rate for 32 minutes. 1 minute after completion of addition of the liquids (III) and (IV), a methanol solution of the dye (containing 2810 mg of the following dye (d-1) and 57.3 mg of (d-2) in 47 ml of methanol and kept at 30 ° C.) Were added all at once.
[0165]
After washing with water and desalting by a conventional method, 50 mg of lime-processed ossein gelatin and 3 g of drug (D) were added to adjust pH to 6.2 and pAg to 7.8 to give 4-hydroxy-6 -Methyl 1,3,3a, 7-tetrazaindene was added, then sodium thiosulfate was added for optimum chemical sensitization at 60 ° C., followed by addition of antifoggant (1) and cooling. In this way, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.23 μm was obtained.
[0166]
[Table 22]

[0167]
Embedded image

[0168]
Photosensitive silver halide emulsion (4) [for green-sensitive emulsion layers]
To a well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride and 7.5 mg of the above-mentioned chemical (A) in 710 ml of water and kept at 63 ° C.), The liquid (I) and liquid (II) were added simultaneously at an equal flow rate for 10 minutes. Ten minutes later, the liquids (III) and (IV) in Table M5 were added simultaneously at an equal flow rate for 20 minutes. Also, 1 minute after the end of addition of the liquids (III) and (IV), a methanol solution of the dye (containing 210 mg of the dye (d-1) and 42.7 mg of (d-2) in 35 ml of methanol and kept at 46 ° C.) ) Was added all at once.
[0169]
After washing with water and desalting by a conventional method, 33 g of lime-processed ossein gelatin, 50 mg of the above-mentioned medicine (B) and 3 g of medicine (D) were added to adjust pH to 6.0 and pAg to 7.2. Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is added, then sodium thiosulfate and chloroauric acid are added for optimal chemical sensitization at 60 ° C., and then antifoggant (1) is added. Cooled after addition. In this way, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.
[0170]
[Table 23]

[0171]
Photosensitive silver halide emulsion (5) [for blue-sensitive emulsion layer]
To a well-stirred gelatin aqueous solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride and 15 mg of the above-mentioned chemical (A) in 690 ml of water and kept at 46 ° C.), (I ) Solution and (II) solution were added simultaneously at an equal flow rate for 8 minutes. Ten minutes later, the solutions (III) and (IV) in Table M6 were added simultaneously at an equal flow rate for 18 minutes. Also, 1 minute after the end of the addition of the liquids (III) and (IV), an aqueous dye solution (containing 225 mg of the following dye (e) and 225 mg of the following dye (f) in 95 ml of water and 5 ml of methanol and kept at 30 ° C.) ) Was added all at once.
[0172]
After washing with water and desalting by a conventional method, 22 g of lime-processed ossein gelatin, 50 mg of the above-mentioned medicine (B) and 3 g of medicine (D) are added to adjust pH to 6.0 and pAg to 7.7 to 4-hydroxy -6-methyl-1,3,3a, 7-tetrazaindene was added, then sodium thiosulfate was added for optimum chemical sensitization at 65 ° C., followed by addition of antifoggant (1) and cooling. . In this manner, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.
[0173]
[Table 24]

[0174]
Photosensitive silver halide emulsion (6) [Blue sensitive emulsion layer]
To a well-stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride and 15 mg of the above-mentioned chemical (A) in 710 ml of water and kept warm at 59 ° C.), (I ) Solution and (II) solution were added simultaneously at an equal flow rate for 8 minutes. Ten minutes later, the solutions (III) and (IV) in Table M7 were added simultaneously at an equal flow rate for 18 minutes. Also, 1 minute after the end of the addition of the liquids (III) and (IV), an aqueous dye solution (113 mg of the following dye (e) and 113 mg of the above dye (f) in 82 ml of water and 6 ml of methanol and kept at 40 ° C.) ) Was added all at once.
[0175]
After washing with water and desalting by a conventional method, 33 g of lime-processed ossein gelatin, 50 mg of the above-mentioned medicine (B) and 3 g of medicine (D) are added, and the pH is adjusted to 6.0 and pAg is adjusted to 7.7. -6-Methyl-1,3,3a, 7-tetrazaindene is added, then sodium thiosulfate and chloroauric acid are added to perform optimum chemical sensitization at 65 ° C, and then antifoggant (1) is added. After cooling. In this way, 635 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.47 μm was obtained.
[0176]
[Table 25]

[0177]
<Method for preparing zinc hydroxide dispersion>
[0178]
Mix 31 g of zinc hydroxide powder with a primary particle size of 0.2 μm, 1.6 g of carboxymethylcellulose and 0.4 g of sodium polyacrylate as a dispersant, 8.5 g of lime-processed ossein gelatin, and 158.5 ml of water. This mixture was dispersed for 1 hour in a mill using glass beads. After the dispersion, the glass beads were separated by filtration to obtain 188 g of a dispersion of zinc hydroxide.
[0179]
Next, a method for preparing a dispersion of an electron transfer agent will be described.
[0180]
10 g of the following electron transfer agent (a), 0.5 g of polyethylene glycol nonylphenyl ether as a dispersant and 0.5 g of the following anionic surfactant (a) were added to a 5% gelatin aqueous solution, and the average particle size was reduced to 0 with a mill. Milled for 60 minutes using 75 mm glass beads. The glass beads were separated to obtain a dispersion of an electron transfer agent having an average particle size of 0.35 μm.
[0181]
Embedded image

[0182]
<Method for preparing emulsified dispersion of coupler>
[0183]
Each of the oil phase component and the aqueous phase component having the composition shown in Table M8 is dissolved to obtain a uniform solution at 60 ° C. The oil phase component and the aqueous phase component were combined and dispersed in a 1 liter stainless steel container at 10,000 rpm for 20 minutes using a dissolver with a 5 cm diameter disperser. To this, the amount of water (warm water) shown in Table M8 was added as post-water and mixed for 10 minutes at 2000 rpm. Thus, an emulsified dispersion of couplers of three colors, cyan, magenta and yellow, was prepared.
[0184]
[Table 26]

[0185]
Embedded image

[0186]
Using the material thus obtained, a heat-developable color photosensitive material K03 having a multilayer structure shown in Table N1 was produced.
[0187]
[Table 27]

[0188]
[Table 28]

[0189]
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[0190]
Next, creation of a processing member will be described. According to the structure described in Table R2, it apply | coated on the support body of the structure of Table A1 (however, polymer layer thickness is 6 micrometers), and produced processing material R201.
[0191]
[Table 29]

[0192]
Similarly, processing elements R202 to 210 were prepared in the same manner as R201, using the support of the support of the polymer thickness or pulp thickness (Tables A2 to 4) shown in Table V1.
When the same members as in Example 1 were prepared, processed, and evaluated, an image could be obtained with exactly the same good handleability.
However, the development temperature was 83 ° C. and the development time was 30 seconds.
In addition, a processing member is processed to a width of 40 mm and a length of 6 m, and three photosensitive elements K03 processed to a width of 35 m and a length of 1.5 m are connected in series in the longitudinal direction, and processed in one continuous development. As a result, an image was obtained in the same manner and showed good handleability.
[0193]
Example 4
A method for producing a photosensitive silver halide emulsion will be described.
The solution (I) shown in Table B2 and the solution (II) shown in Table B2 are simultaneously added to the well-stirred gelatin aqueous solution shown in Table B1 over 10 minutes, and two minutes later, the solutions (III) and (IV The solution was added simultaneously with 18 minutes.
[0194]
[Table 30]

[0195]
[Table 31]

[0196]
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[0197]
After desalting by precipitation at pH 3.0 using compound (a) by a conventional method, 50 g of decalcified gelatin is added to adjust to pH 5.7 and pAg 7.5, and antifoggant (a) is added. After adding 0.1 g, chemical sensitization was performed at 60 ° C. For chemical sensitization, 0.003 g of hypo as a sulfur sensitizer and 0.015 g of chloroauric acid as a gold sensitizer were added, and after 60 minutes, 0.1 g of preservative (A) and stabilizer (A) were added. 0.02 g was added to obtain a silver chlorobromide emulsion. The average grain size of the obtained silver halide was 0.20 μm.
[0198]
18.0 g of sensitizing dye (a) was added to 100 g of this emulsion, 1.25 ml of 1% methanol solution of compound (a), 7.5 and 0.8% methanol solution of compound (c) and surfactant ( 160 mg of water-soluble polymer (a) and 150 mg of water-soluble polymer (a) were added to obtain an emulsion layer solution, and the amount of silver was 1.4 g / m.²Application was performed so that
[0199]
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[0200]
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[0201]
Next, a method for preparing a dispersion 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.
[0202]
Next, a solid state dispersion of the antihalation dye (a) was also prepared in accordance with the above-described method to obtain a gelatin dispersion of the antihalation dye.
[0203]
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[0204]
Next, a method for preparing a 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 carboxymethylcellulose 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.
[0205]
Photosensitive material K04 shown in Table B3 was prepared using the following.
[0206]
[Table 32]

[0207]
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[0208]
The photosensitive element (K03) was processed to a width of 550 mm and a length of 760 mm. For this photosensitive element, a semiconductor laser having an output peak wavelength at 670 nm is used, and one pixel (100 μm²) The exposure was carried out by changing the amount of light at 1 / 10,000,000 second. Separately, the processing element (R101) cut into a sheet having a width of 580 mm and a length of 21 m was wound around a 2-inch roll core (feeding side) with the coating surface facing inward. Thereafter, the tip of the processing element was partially wound around another winding core (winding side).
[0209]
The processing member was set in such a direction that the film surface of the processing element during feeding and winding contacted the outer surface of the drum heater. Next, the exposed photosensitive element is immersed in water kept at 40 ° C. for 2.5 seconds and then squeezed with a roller to reduce the amount of water on the photosensitive element to about 12 ml / m 2.²I made it. After the photosensitive element film surface and the processing element film surface are uniformly laminated, the photosensitive member is peeled off from the processing element while moving the processing member and the photosensitive element at the same speed as the rotation speed of the drum heater. The speed and heater temperature were adjusted and heated to be heated at 80 ° C. for 18 seconds. Next, the processing member was peeled from the photosensitive material at a position away from the heater drum, and then the photosensitive element was peeled from the drum. By this operation, there was no problem in bonding and peeling, and an image of silver was formed on the photosensitive element, and the handleability was good.

Claims (6)

A processing member used for forming an image on a photosensitive material by heating the photosensitive layer containing the silver halide containing the photothermographic material, the processing member having a continuous web support, and a binder A treatment member comprising a treatment layer containing a coating layer on the support .   The processing member according to claim 1, wherein the support has a thickness of 4 μm or more and 40 μm or less.   The processing member according to claim 1, wherein the processing layer contains a base or a base precursor.   Forming an image on the photosensitive material by applying dampening water to the photothermographic material containing silver halide and then superimposing and heating with a processing member provided with a processing layer on a continuous web. A heat-developable image forming method.   After applying dampening water to the heat-developable photosensitive material containing silver halide, the photosensitive member is heated on the continuous web by superimposing it with a processing member provided with a processing layer containing a base or a base precursor. An image is formed on the heat-developable image forming method.   6. The heat-developable image forming method according to claim 5, wherein the photosensitive material contains a basic metal compound hardly soluble in water, and the processing member contains a complex-forming compound.