JP3776546B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

【００３９】
本発明の第一及び第二の形態の感光材料は、支持体上に感光性ハロゲン化銀、現像主薬の酸化体とのカップリング反応によって色素を形成する化合物（以下、カプラー）、およびバインダーよりなる少なくとも一層の写真感光性層を含む写真構成層を塗設して構成する。
【００４０】
本発明においてオリジナルのシーンを記録し、カラー画像として再現するのに用いる感光材料を構成するには、基本的に減色法の色再現を用いることができる。すなわち、青、緑そして赤の領域に感光性を有する少なくとも３種の感光層を設置し、各感光層には自身の感光波長領域とは補色の関係であるイエロー、マゼンタそしてシアンの色素を形成しうるカラーカプラーを含有させることで原シーンのカラー情報を記録することができる。このようにして得られた色素画像を通して同様の感光波長と発色色相の関係を有するカラー印画紙に露光することでオリジナルのシーンを再現することができる。また、オリジナルのシーンの撮影によって得られた色素画像の情報をスキャナー等によって読み取り、この情報を基に観賞用の画像を再現することもできる。
【００４１】
本発明の感光材料として、３種以上の波長領域に感光度を有する感光層を設けることも可能である。
また、感光波長領域と発色色相との間に上記のような補色以外の関係を持たせることも可能である。このような場合には、上述のように画像情報を取り込んだ後、色相変換等の画像処理を施すことでオリジナルの色情報を再現することができる。
【００４２】
本発明においては、同一の波長領域に感光性を有しかつ平均粒子投影面積の異なる少なくとも二種類のハロゲン化銀乳剤を含有させることが好ましい。本発明にいう同一の波長領域に感光性を有するというのは、実効的に同一の波長領域に感光度を有することを指す。従って、分光感度分布が微妙に異なる乳剤であっても主たる感光領域が重なっている場合には同一の波長領域に感光性を有する乳剤と見なす。
【００４３】
このとき、乳剤間の平均粒子投影面積の差は少なくとも１．２５倍の差を有するように使用することが好ましい。さらに好ましくは１．４倍以上である。最も好ましくは１．６倍以上である。用いる乳剤が３種類以上の場合は、最も平均粒子投影面積の小さい乳剤と最も大きい乳剤との間で上記の関係を満足することが好ましい。
【００４４】
本発明においてこれらの同一の波長領域に感光性を有し、かつ平均粒子投影面積の異なる複数の乳剤を含有させるには、乳剤ごとに別個の感光層を設けてもよいし、一つの感光層に上記複数の乳剤を混合して含有せしめてもよい。
【００４５】
これらの乳剤を別個の層に含有させた場合は、平均粒子投影面積の大きい乳剤を上層（光の入射方向に近い位置）に配置することが好ましい。
【００４６】
これらの乳剤を別個の感光層中に含有させた場合、組み合せるカラーカプラーは同一の色相を有するものを用いるのが好ましいが、異なる色相に発色するカプラーを混合して感光層ごとの発色色相を異なるものとしたり、それぞれの感光層に発色色相の吸収プロファイルの異なるカプラーを用いることもできる。
【００４７】
本発明においては、これらの同一の波長領域に感光性を有する乳剤を塗布するに当たって、これらの乳剤の感光材料の単位面積当たりのハロゲン化銀粒子個数の比が、平均粒子投影面積の大きい乳剤ほど、乳剤の塗布銀量をその乳剤に含まれるハロゲン化銀粒子の平均粒子投影面積の３／２乗で除した値の比よりも大きくなるように構成することが好ましい。こうした構成をとることで高温に加熱した現像条件においても良好な粒状性を有する画像を得ることができる。また、高い現像性と広い露光ラチチュードを同時に満足することもできる。
【００４８】
本発明を構成する、現像処理時に求核剤との反応により消色する色素について説明する。
本発明を構成する色素は、現像処理時に求核剤との反応で消色するものであり、かつ耐拡散性を有するものである。さらに本発明を構成する色素は、現像処理後、消色した際にも、少なくとも一部が耐拡散性を有するものである。この様な色素を用いることにより、保存性、シャープネスおよび粒状性に優れ、かつ簡易、迅速処理が可能な感光材料を提供することができる。また、感光材料から不要なものを外に出すことがないため、環境面からも好ましい。
この様な色素としては、具体的にはシアニン類、メロシアニン類、オキソノール類、アリーリデン類（ヘテロアリーリデン類を含む）、アントラキノン類、トリフェニルメタン類、アゾ色素類、アゾメチン色素類等を挙げることができる。
【００４９】
本発明で用いる色素として好ましいものは、下記一般式（Ｉ）〜（ＩＶ）で表されるものである。
一般式（Ｉ）
Ａ５１ ＝ Ｌ５１ −（Ｌ５２ ＝ Ｌ５３）_m51 − Ｑ５１
一般式（ＩＩ）
Ａ５１ ＝ Ｌ５１ −（Ｌ５２ ＝ Ｌ５３）_n51 − Ａ５２
一般式（ＩＩＩ）
Ａ５１ （＝ Ｌ５１ − Ｌ５２ ）_p51 ＝ Ｂ５１
一般式（ＩＶ）
（ＮＣ）₂ Ｃ＝Ｃ（ＣＮ）−Ｑ５１
式中、Ａ５１、Ａ５２はそれぞれ酸性核を表し、Ｂ５１は塩基性核を表し、Ｑ５１はアリール基または複素環基を表す。Ｌ５１、Ｌ５２、Ｌ５３はそれぞれメチン基を表し、ｍ５１は０、１または２を表し、ｎ５１、ｐ５１はそれぞれ０、１、２または３を表す。但し、一般式（Ｉ）〜（ＩＶ）で表される化合物はカルボキシル基、スルホ基を持たない。また一般式（Ｉ）〜（ＩＶ）で表される化合物は耐拡散性基を有しており、しかも処理（消色）後の生成物も耐拡散的で感光材料から実質的に溶出しないものである。更に一般式（Ｉ）〜（ＩＶ）で表される化合物は処理時に酸化還元反応を起こし、それに続いて結合の切断を起こし複数の分子に分裂するような基を持たない。
【００５０】
Ａ５１またはＡ５２で表される酸性核は環状のケトメチレン化合物または電子吸引性基によって挟まれたメチレン基を有する化合物が好ましい。環状のケトメチレン化合物の例としては、２−ピラゾリン−５−オン、ロダニン、ヒダントイン、チオヒダントイン、２，４−オキサゾリジンジオン、イソオキサゾロン、バルビツール酸、チオバルビツール酸、インダンジオン、ジオキソピラゾロピリジン、ヒドロキシピリジン、ピラゾリジンジオン、２，５−ジヒドロフラン−２−オン、ピロリン−２−オンを挙げることができる。これらは置換基を有していても良い。これらの中で好ましい化合物は２−ピラゾリン−５−オン、イソオキサゾロン、ジオキソピラゾロピリジン、ヒドロキシピリジン、ピラゾリジンジオンであり、特に好ましくは２−ピラゾリン−５−オン、イソオキサゾロン、ヒドロキシピリジンである。
【００５１】
電子吸引性基によって挟まれたメチレン基を有する化合物はＺ５１−ＣＨ₂ −Ｚ５２と表すことができ、ここでＺ５１、Ｚ５２はそれぞれ−ＣＮ、−ＳＯ₂ Ｒ５１、−ＣＯＲ５１、−ＣＯＯＲ５１、−ＣＯＮ（Ｒ５２）₂ 、−ＳＯ₂ Ｎ（Ｒ５２）₂ 、−Ｃ［＝Ｃ（ＣＮ）₂ ］Ｒ５１、−Ｃ［＝Ｃ（ＣＮ）₂ ］Ｎ（Ｒ５１）₂ を表し、Ｒ５１はアルキル基、アリール基、複素環基を表し、Ｒ５２は水素原子またはＲ５１で挙げた基を表す。Ｒ５１、Ｒ５２はそれぞれ置換基を有していても良く、分子内に複数のＲ５１もしくはＲ５２が有る場合、それらは同じであっても異なっていても良い。Ｚ５１とＺ５２は同じであっても良い。
【００５２】
Ｂ５１で表される塩基性核の例としては、ピリジン、キノリン、インドレニン、オキサゾール、イミダゾール、チアゾール、ベンゾオキサゾール、ベンゾイミダゾール、ベンゾチアゾール、オキサゾリン、ナフトオキサゾール、ピロールを挙げることができる。これらはそれぞれ置換基を有していても良い。これらの中で好ましい化合物はインドレニン、ベンゾオキサゾール、ベンゾイミダゾール、ベンゾチアゾール、ピロールであり、特に好ましくはインドレニン、ベンゾオキサゾールである。
Ｑ５１で表されるアリール基の例としては、フェニル基、ナフチル基を挙げることができ、それぞれ置換基（電子供与性基が好ましい）を有していても良い。これらのうちで好ましくはジアルキルアミノ基、水酸基、アルコキシ基、アルキル基が置換したフェニル基であり、特に好ましくはジアルキルアミノ基で置換されたフェニル基である。
Ｑ５１で表される複素環基の例としては、ピロール、インドール、フラン、チオフェン、イミダゾール、ピラゾール、インドリジン、キノリン、カルバゾール、フェノチアジン、フェノキサジン、インドリン、チアゾール、ピリジン、ピリダジン、チアジアジン、ピラン、チオピラン、オキサジアゾール、ベンゾキノリン、チアジアゾール、ピロロチアゾール、ピロロピリダジン、テトラゾール、オキサゾール、クマリン、およびクロマンを挙げることができ、それぞれ置換基を有していても良い。これらの中で好ましくはピロール、インドールである。
【００５３】
Ｌ５１、Ｌ５２、Ｌ５３で表されるメチン基は置換基を有していても良く、その置換基同士が連結して５または６員環（例えばシクロペンテン、シクロヘキセン）を形成しても良い。
上述の基が有しても良い置換基としてはスルホンアミド基（例えばメタンスルホンアミド、ベンゼンスルホンアミド、オクタンスルホンアミド）、スルファモイル基（例えばスルファモイル、メチルスルファモイル、フェニルスルファモイル、ブチルスルファモイル）、スルホニルカルバモイル基（例えばメタンスルホニルカルバモイル、ベンゼンスルホニルカルバモイル）、アシルスルファモイル基（例えばアセチルスルファモイル、ピバロイルスルファモイル、ベンゾイルスルファモイル）、鎖状または環状のアルキル基（例えばメチル、イソプロピル、シクロプロピル、シクロヘキシル、２−エチルヘキシル、ドデシル、オクタデシル、２−フェネチル、ベンジル）、アルケニル基（例えばビニル、アリル）、アルコキシ基（例えばメトキシ、オクチルオキシ、ドデシルオキシ、２−メトキシエトキシ）、アリールオキシ基（例えばフェノキシ）、ハロゲン原子（例えばＦ、Ｃｌ、Ｂｒ）、アミノ基（例えばアミノ、ジエチルアミノ、エチルドデシルアミノ）、エステル基（例えばエトキシカルボニル、オクチルオキシカルボニル、２−ヘキシルデシルオキシカルボニル）、アシルアミノ基（例えばアセチルアミノ、ピバロイルアミノ、ベンゾイルアミノ）、カルバモイル基（例えば無置換のカルバモイル、エチルカルバモイル、ジエチルカルバモイル、フェニルエチルカルバモイル）、アリール基（例えばフェニル、ナフチル）、アルキルチオ基（例えばメチルチオ、オクチルチオ）、アリールチオ基（例えばフェニルチオ、ナフチルチオ）、アシル基（例えばアセチル、ベンゾイル、ピバロイル）、スルホニル基（例えばメタンスルホニル、ベンゼンスルホニル）、ウレイド基（例えば３−プロピルウレイド、３，３−ジメチルウレイド）、ウレタン基（例えばメトキシカルボニル、ブトキシカルボニル）、シアノ基、水酸基、ニトロ基、複素環基（例えばベンゾオキサゾール環、ピリジン環、スルホラン環、フラン環、ピロール環、ピロリジン環、モルホリン環、ピペラジン環、ピリミジン環）等を挙げることができる。
【００５４】
本発明に用いられる色素として、好ましくは一般式（Ｉ）、（ＩＩ）または（ＩＩＩ）で表されるものであり、より好ましくは一般式（Ｉ）または（ＩＩＩ）で表されるものであり、特に好ましくは一般式（Ｉ）で表されるものである。
以下に本発明に用いられる色素の具体例を示すが、本発明はこれらに限定されるものではない。
【００５５】
【化１】

【００５６】
【化２】

【００５７】
【化３】

【００５８】
【化４】

【００５９】
【化５】

【００６０】
【化６】

【００６１】
【化７】

【００６２】
【化８】

【００６３】
【化９】

【００６４】
【化１０】

【００６５】
【化１１】

【００６６】
【化１２】

【００６７】
【化１３】

【００６８】
【化１４】

【００６９】
本発明に用いられる色素は、国際特許ＷＯ８８／０４７９４号、欧州特許ＥＰ２７４７２３号、同２７６，５５６号、同２９９，４３５号、米国特許２，５２７，５８３号、同３，４８６，８９７号、同３，７４６，５３９号、同３，９３３，７９８号、同４，１３０，４２９号、同４，０４０，８４１号、特開昭４８−６８，６２３号、同５２−９２，７１６号、同５５−１５５，３５０号、同５５−１５５，３５１号、同６１−２０５，９３４号、特開平２−１７３，６３０号、同２−２３０，１３５号、同２−２７７，０４４号、同２−２８２，２４４号、同３−７，９３１号、同３−１６７，５４６号、同３−１３，９３７号、同３−２０６，４４３号、同３−２０８，０４７号、同３−１９２，１５７号、同３−２１６，６４５号、同３−２７４，０４３号、同４−３７，８４１号、同４−４５，４３６号、同４−１３８，４４９号、同５−１９７，０７７号、特願平５−２７３，８１１号、同６−７，７６１号、同６−１５５，７２７号等に記載されている方法またはそれに準じて合成することができる。
【００７０】
本発明における上述の色素は、イエローフィルター層、マゼンタフィルター層、およびアンチハレーション層に使用することができる。それにより、例えば感光層が支持体に最も近い側から赤色感光層、緑色感光層、青色感光層の順に設けられている場合は、青色感光層と緑色感光層の間にイエローフィルター層、緑色感光層と赤色感光層の間にマゼンタ色フィルター層、赤色感光層と支持体の間にシアン色フィルター層（アンチハレーション層）を設けることができる。色素の使用量は、それぞれの層の透過濃度が各々青、緑、赤光に対し、０．０３〜３．０、より好ましくは０．１〜２．０になるように用いる。具体的には、色素のεおよび分子量にもよるが、０．００５〜２ミリモル／ｍ² 用いればよく、より好ましくは０．０５〜１ミリモル／ｍ² である。
【００７１】
本発明の感光材料は一つの層に二つ以上の色素を混合して用いてもよい。例えば上述のアンチハレーション層にイエロー、マゼンタ、シアンの３種の色素を混合して用いることもできる。
本発明の感光材料は、消色性色素をオイルおよび／または油溶性ポリマーに溶解させた油滴を親水性バインダー中に分散させた状態で用いる。その調製法としては乳化分散法が好ましく、例えば米国特許２，３２２，０２７号記載の方法によることができる。この場合には米国特許４，５５５，４７０号、同４，５３６，４６６号、同４，５８７，２０６号、同４，５５５，４７６号、同４，５９９，２９６号、特公平３−６２，２５６号等に記載のような高沸点オイルを、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、高沸点オイルは２種以上併用することができる。また、油溶性ポリマーをオイルの代わりに、または、併用して用いることができるが、その例はＰＣＴ国際公開番号ＷＯ８８／００７２３号明細書に記載されている。高沸点オイルおよび／またはポリマーの量は、用いられる色素１ｇに対して０．０１ｇ〜１０ｇ、好ましくは０．１ｇ〜５ｇを用いる。
また、色素をポリマーに溶解させる方法として、ラテックス分散法によることも可能であり、その工程、含漬用のラテックスの具体例は、米国特許４，１９９，３６３号、西独特許公開（ＯＬＳ）２，５４１，２７４号、同第２，５４１，２３０号、特公昭５３−４１，０９１号および欧州特許公開第０２９，１０４号等に記載されている。
【００７２】
油滴を親水性バインダーに分散させる際には、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３７〜３８ページ、公知技術第５号（１９９１年３月２２日、アズテック有限会社発行）１３６〜１３８ページに記載の界面活性剤を用いることができる。また、特願平５−２０４，３２５号、同６−１９，２４７号、西ドイツ公開特許第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。
親水性バインダーとしては、水溶性ポリマーが好ましい。例としてはゼラチン、ゼラチン誘導体の蛋白質、またはセルロース誘導体、澱粉、アラビアゴム、デキストリン、プルラン等の多糖類のような天然化合物とポリビニルアルコール、ポリビニルピロリドン、アクリルアミド重合体等の合成高分子化合物が挙げられる。これら水溶性ポリマーは２種以上組み合わせて用いることもできる。特にゼラチンとの組み合わせが好ましい。ゼラチンは、種々の目的に応じて石灰処理ゼラチン、酸処理ゼラチン、カルシウム等の含有量を減らしたいわゆる脱灰ゼラチンから選択すればよく、組み合わせて用いることもできる。
【００７３】
本発明において色素は、求核剤との反応により処理時に消色する。
求核剤としては、アルコールもしくはフェノール類（Ｒ５１ＯＨ）、アミンもしくはアニリン類（（Ｒ５２）₃ Ｎ）、ヒドロキシルアミン類（（Ｒ５２）₂ ＮＯＲ５２）、スルフィン酸類（Ｒ５１ＳＯ₂ Ｈ）、亜硫酸、チオ硫酸、カルボン酸類（Ｒ５１ＣＯ₂ Ｈ）、ヒドラジン類（（Ｒ５２）₂ ＮＮ（Ｒ５２）₂ ）、グアニジン類（［（Ｒ５２）₂ Ｎ］₂ Ｃ＝ＮＨ）、アミノグアニジン類（（Ｒ５２）₂ ＮＲ５２Ｎ（Ｒ５２Ｎ）Ｃ＝ＮＨ）、アミジン類、チオール類（Ｒ５１ＳＨ）、環状または鎖状の活性メチレン化合物（Ｚ５３−ＣＨ₂ −Ｚ５４、ここでＺ５３、Ｚ５４はＺ５１、Ｚ５２と同義であり、かつ、Ｚ５３とＺ５４は結合して環を形成しても良い）、環状または鎖状の活性メチン化合物（Ｚ５３−ＣＨ（Ｒ５１）−Ｚ５４またはＺ５３−ＣＨ（Ｚ５４）−Ｚ５５、ここでＺ５５はＺ５３と同義であり、Ｚ５３、Ｚ５４、Ｚ５５（またはＲ５１）はそれぞれ結合して環を形成しても良い）、およびこれら化合物から生じるアニオン種等が挙げられる。
これらのうちで好ましくはヒドロキシルアミン類、スルフィン酸類、亜硫酸、グアニジン類、アミノグアニジン類、ヘテロ環チオール類、環状または鎖状の活性メチレン、活性メチン化合物類であり、特に好ましくはグアニジン類、アミノグアニジン類である。
これら求核剤は最初から感光材料中に添加しておいても良いし、また処理時に何らかの方法で感光材料中に添加しても良い。また添加する際の求核剤の形態としてプレカーサー化したものを添加しても良い。
【００７４】
上述の求核剤は処理時に色素と接触、反応し、色素を消色させる。好ましくは色素を含有するハロゲン化銀感光材料を像様露光後、または像様露光と同時に色素消色剤プレカーサーを含有する処理部材と水の存在下で加熱し、その後両者を剥離することにより、該ハロゲン化銀感光材料上に発色画像を得ると同時に色素を消色させる。この場合、消色させる割合は、元の濃度の１／３以下、好ましくは１／５以下である。求核剤の使用量は、色素の０．１倍から２００倍モル、好ましくは０．５倍から１００倍モルである。
【００７５】
従来写真撮影に用いられてきたカラーネガティブフィルムにおいては、目的の粒状度を達成するためにハロゲン化銀乳剤の改良もさることながら、現像主薬の酸化体とのカップリング反応に際して現像抑制性の化合物を放出する所謂ＤＩＲカプラーを用いるなどの技術を組み込んできた。本発明の感光材料においては、ＤＩＲカプラーを用いない場合でも優れた粒状度が得られる。さらにＤＩＲ化合物を組み合わせるならば粒状度はますます優れたものになる。
【００７６】
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銀も有用である。有機銀塩は、２種以上を併用してもよい。
以上の有機銀塩は、感光性ハロゲン化銀１モルあたり０．０１〜１０モル、好ましくは０．０１〜１モルを併用することができる。感光性ハロゲン化銀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。
【００７７】
本発明の感光材料の構成層のバインダーには親水性のものが好ましく用いられる。その例としては前記のリサーチ・ディスクロージャーおよび特開昭６４−１３，５４６号の(71)頁〜(75)頁に記載されたものが挙げられる。具体的には、透明か半透明の親水性バインダーが好ましく、例えばゼラチン、ゼラチン誘導体等の蛋白質またはセルロース誘導体、澱粉、アラビアゴム、デキストラン、プルラン等の多糖類のような天然化合物とポリビニールアルコール、ポリビニルピロリドン、アクリルアミド重合体等の合成高分子化合物が挙げられる。また、米国特許第４，９６０，６８１号、特開昭６２−２４５，２６０号等に記載の高吸水性ポリマー、すなわち−ＣＯＯＭまたは−ＳＯ₃ Ｍ（Ｍは水素原子またはアルカリ金属）を有するビニルモノマーの単独重合体またはこのビニルモノマー同士もしくは他のビニルモノマーとの共重合体（例えばメタクリル酸ナトリウム、メタクリル酸アンモニウム、住友化学（株）製のスミタゲルＬ−５Ｈ）も使用される。これらのバインダーは２種以上組み合わせて用いることもてきる。特にゼラチンと上記バインダーの組み合わせが好ましい。またゼラチンは、種々の目的に応じて石灰処理ゼラチン、酸処理ゼラチン、カルシウムなどの含有量を減らしたいわゆる脱灰ゼラチンから選択すれば良く、組み合わせて用いる事も好ましい。
本発明において、バインダーの塗布量は１ｍ² あたり１ｇ以上２０ｇ以下が好ましく、特に２ｇ以上１０ｇ以下にするのが適当である。
【００７８】
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、特開昭５８−１２３，５３３号、同５８−１４９，０４６号、同５８−１４９，０４７号、同５９−１１１，１４８号、同５９−１２４，３９９号、同５９−１７４，８３５号、同５９−２３１，５３９号、同５９−２３１，５４０号、同６０−２，９５０号、同６０−２，９５１号、同６０−１４，２４２号、同６０−２３，４７４号、同６０−６６，２４９号、同８−１１０，６０８号、同８−１４６，５５２号、同８−１４６，５７８号等に詳しく記載されている。
【００７９】
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号の式（Ｉ）、（II）で表わされるカプラー：ＥＰ５１３，４９６Ａ号の式（1)、(2) で表わされるカプラー、特願平４−１３４５２３号の請求項１の一般式（Ｉ）で表わされるカプラー：ＵＳ５，０６６，５７６号のカラム１の４５、５５行の一般式Ｄで表わされるカプラー、特開平４−２７４，４２５号の段落０００８の一般式Ｄで表わされるカプラー：ＥＰ４９８，３８１Ａ１号の４０頁のクレーム１に記載のカプラー、ＥＰ４４７，９６９Ａ１号の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３−３９，７３７号、同６−４３，６１１号、同５−２０４，１０６号、特開平４−３，６２６号に記載のカプラー。
シアンカプラー：特開平４−２０４，８４３号、特開平４−４３，３４５号、特願平４−２３，６３３号。
ポリマーカプラー：特開平２−４４，３４５号。
【００８０】
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号、ＧＢ２，１２５，５７０号、ＥＰ９６，５７０号、ＤＥ３，２３４，５３３号に記載のものが好ましい。
【００８１】
また、本発明の感光材料には、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号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号に記載のマゼンタカラードシアンカプラー、ＵＳ４，８３７，１３６号の（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）。
【００８２】
本発明には現像主薬の酸化体との反応により、写真的に有用な化合物を放出するカプラーあるいは他の化合物を用いるのが好ましい。
現像主薬酸化体と反応して写真的に有用な化合物残査を放出する化合物（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号の１１頁に記載の式（Ｉ）〜（IV）で表わされる化合物、ＥＰ４３６，９３８Ａ２号の７頁に記載の式（Ｉ）で表わされる化合物、特開平５−３０７２４８号の式（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、特開平６−５９４１１号の請求項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号のクレーム１に記載のＬＩＧ−Ｘで表わされる化合物。
【００８３】
本発明において、カプラーの使用量としては、ハロゲン化銀１モルあたり１／１０００モル〜１モルが好ましく、１／５００モル〜１／５モルがより好ましい。
【００８４】
本発明の感光材料では、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現像主薬を内蔵することが必要である。
この場合、米国特許第３，５３１，２５６号の、ｐ−フェニレンジアミン類現像主薬と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６０−１２８，４３８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。
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。例えば、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５３−１３５，６２８号記載のウレタン系化合物を挙げることができる。
【００８５】
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７−４９，２８７号、同７−６３，５７２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。
【００８６】
本発明においては、感光材料に含有させる現像主薬として一般式ＩＤ、IIＤ、III ＤあるいはIVＤで表される化合物を用いることが好ましい。これらの中でも特に一般式ＩＤあるいはIIＤの化合物が好ましく用いられる。
以下にこれらの現像主薬について詳細に説明する。
【００８７】
【化１５】

【００８８】
【化１６】

【００８９】
【化１７】

【００９０】
【化１８】

【００９１】
式中、Ｒ₁ 〜Ｒ₄ は水素原子、ハロゲン原子、アルキル基、アリール基、アルキルカルボンアミド基、アリールカルボンアミド基、アルキルスルホンアミド基、アリールスルホンアミド基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキルカルバモイル基、アリールカルバモイル基、カルバモイル基、アルキルスルファモイル基、アリールスルファモイル基、スルファモイル基、シアノ基、アルキルスルホニル基、アリールスルホニル基、アルコキシカルボニル基、アリールオキシカルボニル基、アルキルカルボニル基、アリールカルボニル基またはアシルオキシ基を表し、Ｒ₅ はアルキル基、アリール基または複素環基を表す。Ｚは（複素）芳香環を形成する原子群を表し、Ｚがベンゼン環である場合、その置換基のハメット定数（σ）の合計値は１以上であることが好ましい。Ｒ₆ はアルキル基を表す。Ｘは酸素原子、硫黄原子、セレン原子またはアルキル置換もしくはアリール置換の３級窒素原子を表す。Ｒ₇ 、Ｒ₈ は水素原子または置換基を表し、Ｒ₇ 、Ｒ₈ が互いに結合して２重結合または環を形成してもよい。さらに、一般式ＩＤ〜IVＤの各々には分子に油溶性を付与するため、炭素数８以上のバラスト基を少なくとも１つ含む。
【００９２】
一般式ＩＤで表される化合物はスルホンアミドフェノールと総称される化合物であり、当該分野では公知の化合物である。本発明に使用する場合、置換基Ｒ₁ 〜Ｒ₅ の少なくとも１つに炭素数８以上のバラスト基を有するものが好ましい。
【００９３】
式中、Ｒ₁ 〜Ｒ₄ は水素原子、ハロゲン原子（例えばクロル基、ブロム基）、アルキル基（例えばメチル基、エチル基、イソプロピル基、ｎ−ブチル基、ｔ−ブチル基）、アリール基（例えばフェニル基、トリル基、キシリル基）、アルキルカルボンアミド基（例えばアセチルアミノ基、プロピオニルアミノ基、ブチロイルアミノ基）、アリールカルボンアミド基（例えばベンゾイルアミノ基）、アルキルスルホンアミド基（例えばメタンスルホニルアミノ基、エタンスルホニルアミノ基）、アリールスルホンアミド基（例えばベンゼンスルホニルアミノ基、トルエンスルホニルアミノ基）、アルコキシ基（例えばメトキシ基、エトキシ基、ブトキシ基）、アリールオキシ基（例えばフェノキシ基）、アルキルチオ基（例えばメチルチオ基、エチルチオ基、ブチルチオ基）、アリールチオ基（例えばフェニルチオ基、トリルチオ基）、アルキルカルバモイル基（例えばメチルカルバモイル基、ジメチルカルバモイル基、エチルカルバモイル基、ジエチルカルバモイル基、ジブチルカルバモイル基、ピペリジルカルバモイル基、モルホリルカルバモイル基）、アリールカルバモイル基（例えばフェニルカルバモイル基、メチルフェニルカルバモイル基、エチルフェニルカルバモイル基、ベンジルフェニルカルバモイル基）、カルバモイル基、アルキルスルファモイル基（例えばメチルスルファモイル基、ジメチルスルファモイル基、エチルスルファモイル基、ジエチルスルファモイル基、ジブチルスルファモイル基、ピペリジルスルファモイル基、モルホリルスルファモイル基）、アリールスルファモイル基（例えばフェニルスルファモイル基、メチルフェニルスルファモイル基、エチルフェニルスルファモイル基、ベンジルフェニルスルファモイル基）、スルファモイル基、シアノ基、アルキルスルホニル基（例えばメタンスルホニル基、エタンスルホニル基）、アリールスルホニル基（例えばフェニルスルホニル基、４−クロロフェニルスルホニル基、ｐ−トルエンスルホニル基）、アルコキシカルボニル基（例えばメトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基）、アリールオキシカルボニル基（例えばフェノキシカルボニル基）、アルキルカルボニル基（例えばアセチル基、プロピオニル基、ブチロイル基）、アリールカルボニル基（例えばベンゾイル基、アルキルベンゾイル基）、またはアシルオキシ基（例えばアセチルオキシ基、プロピオニルオキシ基、ブチロイルオキシ基）を表す。Ｒ₁ 〜Ｒ₄ の中で、Ｒ₂ およびＲ₄ は好ましくは水素原子である。また、Ｒ₁ 〜Ｒ₄ のハメット定数σｐ値の合計は、０以上となることが好ましい。Ｒ₅ はアルキル基（例えばメチル基、エチル基、ブチル基、オクチル基、ラウリル基、セチル基、ステアリル基）、アリール基（例えばフェニル基、トリル基、キシリル基、４−メトキシフェニル基、ドデシルフェニル基、クロロフェニル基、トリクロロフェニル基、ニトロクロロフェニル基、トリイソプロピルフェニル基、４−ドデシルオキシフェニル基、３，５−ジ−（メトキシカルボニル）基）、または複素環基（例えばピリジル基）を表す。
【００９４】
一般式IIＤで表される化合物はカルバモイルヒドラジンと総称される化合物である。両者とも、当該分野では公知の化合物である。本発明に使用する場合、Ｒ₅ 又は環の置換基に炭素数８以上のバラスト基を有するものが好ましい。
【００９５】
式中、Ｚは（複素）芳香環を形成する原子群を表す。Ｚによって形成される（複素）芳香環は、本化合物に銀現像活性を付与するため、十分に電子吸引的であることが必要である。このため、含窒素芳香環を形成するか、或いはベンゼン環に電子吸引性基を導入したような芳香環が好ましく使用される。このような芳香環としては、ピリジン環、ピラジン環、ピリミジン環、キノリン環、キノキサリン環等が好ましい。ベンゼン環の場合、その置換基としては、アルキルスルホニル基（例えばメタンスルホニル基、エタンスルホニル基）、ハロゲン原子（例えばクロル基、ブロム基）、アルキルカルバモイル基（例えばメチルカルバモイル基、ジメチルカルバモイル基、エチルカルバモイル基、ジエチルカルバモイル基、ジブチルカルバモイル基、ピペリジンカルバモイル基、モルホリノカルバモイル基）、アリールカルバモイル基（例えばフェニルカルバモイル基、メチルフェニルカルバモイル基、エチルフェニルカルバモイル基、ベンジルフェニルカルバモイル基）、カルバモイル基、アルキルスルファモイル基（例えばメチルスルファモイル基、ジメチルスルファモイル基、エチルスルファモイル基、ジエチルスルファモイル基、ジブチルスルファモイル基、ピペリジルスルファモイル基、モリホリルスルファモイル基）、アリールスルファモイル基（例えばフェニルスルファモイル基、メチルフェニルスルファモイル基、エチルフェニルスルファモイル基、ベンジルフェニルスルファモイル基）、スルファモイル基、シアノ基、アルキルスルホニル基（例えばメタンスルホニル基、エタンスルホニル基）、アリールスルホニル基（例えばフェニルスルホニル基、４−クロロフェニルスルホニル基、ｐ−トルエンスルホニル基）、アルコキシカルボニル基（例えばメトキシカルボニル基、エトキシカルボニル基、ブトキシカルボニル基）、アリールオキシカルボニル基（例えばフェノキシカルボニル基）、アルキルカルボニル基（例えばアセチル基、プロピオニル基、ブチロイル基）、またはアリールカルボニル基（例えばベンゾイル基、アルキルベンゾイル基）等が挙げられるが、上記置換基のハメット定数σ値の合計は、１以上となることが好ましい。
【００９６】
一般式III Ｄで表される化合物はカルバモイルヒドラゾンと総称される化合物である。一般式IVＤで表される化合物はスルホニルヒドラジンと総称される化合物である。両者とも、当該分野では公知の化合物である。本発明に使用する場合、Ｒ₅ 〜Ｒ₈ の少なくとも１つに炭素数８以上のバラスト基を有するものが好ましい。
【００９７】
式中、Ｒ₆ はアルキル基（例えばメチル基、エチル基）を表す。Ｘは酸素原子、硫黄原子、セレン原子、またはアルキル置換もしくはアリール置換の３級窒素原子を表すが、アルキル置換の３級窒素原子が好ましい。Ｒ₇ 、Ｒ₈ は水素原子、または置換基（上記Ｚのベンゼン環の置換基として挙げたものをその例として挙げることができる）を表し、Ｒ₇ 、Ｒ₈ が互いに結合して２重結合または環を形成してもよい。
なお、一般式ＩＤ〜IVＤの化合物の中でも、特に生保存性の観点から本発明ではＩＤ、IIＤの化合物が好ましい。
【００９８】
上記においてＲ₁ 〜Ｒ₈ の各基は可能な置換基を有しているものを含み、置換基としては上記Ｚのベンゼン環の置換基として列挙したものが挙げられる。
以下に、一般式ＩＤ〜IVＤで表される化合物の具体例を示すが、本発明の化合物はもちろんこれによって限定されるものではない。
【００９９】
【化１９】

【０１００】
【化２０】

【０１０１】
【化２１】

【０１０２】
【化２２】

【０１０３】
【化２３】

【０１０４】
【化２４】

【０１０５】
【化２５】

【０１０６】
【化２６】

【０１０７】
【化２７】

【０１０８】
【化２８】

【０１０９】
【化２９】

【０１１０】
上記の化合物は、一般的に公知の方法で合成することが可能である。以下に簡単な合成ルートを列挙する。
【０１１１】
【化３０】

【０１１２】
【化３１】

【０１１３】
【化３２】

【０１１４】
本発明において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。
さらに本発明において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。
【０１１５】
また、本発明においてそれ自身は還元性を持たないが現像過程で求核試薬や熱の作用により還元性を発現する現像主薬プレカーサーも用いることができる。
その他、下記の様な還元剤を感光材料に内蔵しても良い。
本発明に用いることのでき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。
現像主薬あるいは還元剤は、後述する処理シートに内蔵しても良いが、感光材料に内蔵しても良い。
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０．０１〜１０モルである。
【０１１６】
本発明においてはカプラーとして、４当量カプラーと２当量カプラーを主薬の種類によって使い分けることができる。まず、一般式ＩＤの現像主薬に対しては４当量カプラーを使用する。一般式ＩＤの現像主薬は、カップリング部位がスルホニル基によって置換されており、カップリング時に、このスルホニル基がスルフィン酸として離脱するため、カプラー側の離脱基はカチオンとして離脱しなければならない。このため、カップリング時にプロトンを離脱基として放出可能な４当量カプラーとは反応するが、離脱基がアニオンである２当量カプラーとは反応しない。逆に、一般式IIＤ、III Ｄの現像主薬に対しては２当量カプラーを使用する。一般式IIＤ、III Ｄの現像主薬は、カップリング部位がカルバモイル基によって置換されており、カップリング時に窒素原子上の水素原子がプロトンとして離脱するため、カプラー側の離脱基はアニオンとして離脱しなければならない。このため、カップリング時にアニオンを離脱基として放出可能な２当量カプラーとは反応するが、離脱基がプロトンである４当量カプラーとは反応しない。この組合せを用いることによって、現像主薬の酸化体の層間移動に由来する色にごりを防止することができる。カプラーの具体例は、４当量、２当量の両者ともセオリー・オブ・ザ・フォトグラフィック・プロセス（4th Ed. T.H.James 編集、Macmillan,1977) ２９１頁〜３３４頁、および３５４頁〜３６１頁、特開昭５８−１２，３５３号、同５８−１４９，０４６号、同５８−１４９，０４７号、同５９−１１，１１４号、同５９−１２４，３９９号、同５９−１７４，８３５号、同５９−２３１，５３９号、同５９−２３１，５４０号、同６０−２，９５１号、同６０−１４，２４２号、同６０−２３，４７４号、同６０−６６，２４９号及び前掲した文献・公報に詳しく記載されている。
【０１１７】
カプラー、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疎水性添加剤１ｇに対して１０ｇ以下、好ましくは５ｇ以下、より好ましくは１ｇ〜０．１ｇである。また、バインダー１ｇに対して１cc以下、更には０．５cc以下、特に０．３cc以下が適当である。
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、特開平７−５６，２６７号、同７−２２８，５８９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。
【０１１８】
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。
【０１１９】
黄色フィルター層、アンチハレーション層に用いる事の出来る染料としては、現像時に消色、あるいは溶出し、処理後の濃度に寄与しないものが好ましい。
黄色フィルター層、アンチハレーション層の染料が現像時に消色あるいは除去されるとは、処理後に残存する染料の量が、塗布直前の１／３以下、好ましくは１／１０以下となることであり、現像時に染料の成分が感光材料から溶出あるいは処理材料中に転写しても良いし、現像時に反応して無色の化合物に変わっても良い。
【０１２０】
本発明の感光材料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）が挙げられる。 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。
【０１２１】
本発明の感光材料には、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号（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。
【０１２２】
本発明の感光材料は、像様に露光した後、画像を形成するには、露光後の感光材料と、支持体上に塩基および／または塩基プレカーサーを含有する処理材料とを、感光材料の感光性層面と処理材料の処理層面で貼り合わせて熱現像し、画像形成する。現像時に感光材料および処理材料を構成する全塗布膜の最大膨潤に要する水の１／１０から１倍に相当する水を感光材料または処理材料に供給後、貼り合わせて加熱することにより発色現像を行う方法は好ましく用いられるが、本発明はこれによって限定されるものではない。また、現像主薬を必要に応じて感光材料または処理材料に内蔵する方法が好ましく用いられるが、本発明はこれによって限定されるものではない。
【０１２３】
本発明の感光材料は、処理時に未反応のハロゲン化銀を定着しないで使用することも可能である。その場合、感光材料側は、カラー画像が形成されるが、ハロゲン化銀が残存したままである。つまり残存するハロゲン化銀を残したまま感光材料を使用する場合において、本発明の（１００）面または（１１１）面で構成された平板状の高塩化銀乳剤を含む感光材料は、その他のハロゲン化銀を含む感光材料に比較してそれだけでもシャープネスに優れる画質が得られるが、本発明の特定の構造の着色染料を組み合わせて使用するとさらに優れたシャープネスが得られる。
【０１２４】
本発明は、上記のような熱現像において良好な粒状性と露光ラチチュードとシャープネスの向上を達成する目的でなされたものであり、液現像を行うことによる環境負荷を軽減することを目指すものであるが、本発明の感光材料をアルカリ処理液を用いたアクチベーター処理あるいは現像主薬／塩基を含む処理液で現像することで画像を形成することも可能である。
【０１２５】
本発明の感光材料の加熱処理は当該技術分野では公知であり、熱現像感光材料とそのプロセスについては、例えば、写真工学の基礎（１９７０年、コロナ社発行）の５５３頁〜５５５頁、１９７８年４月発行映像情報４０頁、Nabletts Handbook ofPhotography and Reprography 7th Ed.(Vna Nostrand and Reinhold Company)の３２〜３３頁、米国特許第３，１５２，９０４号、同第３，３０１，６７８号、同第３，３９２，０２０号、同第３，４５７，０７５号、英国特許第１，１３１，１０８号、同第１，１６７，７７７号およびリサーチ・ディスクロージャー誌１９７８年６月号９〜１５頁（ＲＤ−１７０２９）に記載されている。
【０１２６】
アクチベーター処理とは、発色現像主薬を感光材料の中に内蔵させておき、発色現像主薬を含まない処理液で現像処理を行う処理方法をさしている。この場合の処理液は通常の現像処理液成分に含まれている発色現像主薬を含まないことが特徴で、その他の成分（例えばアルカリ、補助現像主薬など）を含んでいても良い。アクチベーター処理については欧州特許第５４５，４９１Ａ１号、同第５６５，１６５Ａ１号などの公知文献に例示されている。
【０１２７】
現像主薬／塩基を含む処理液で現像する方法は、ＲＤ．No. １７，６４３の２８〜２９頁、同No. １８，７１６の６５１左欄〜右欄、および同No. ３０７，１０５の８８０〜８８１頁に記載されている。
次に、本発明において、熱現像処理の場合に用いられる処理素材及び処理方法について詳細に説明する。
【０１２８】
本発明の感光材料には銀現像及び色素形成反応を促進する目的で塩基又は塩基プレカーサーを用いることが好ましい。塩基プレカーサーとしては、熱により脱炭酸する有機酸と塩基の塩、分子内求核置換反応、ロッセン転移またはベックマン転移によりアミン類を放出する化合物などがある。その具体例は、米国特許第４，５１４，４９３号、同４，６５７，８４８号および公知技術第５号（１９９１年３月２２日、アズテック有限会社発行）の５５頁から８６頁等に記載されている。また、後述する欧州特許公開２１０，６６０号、米国特許第４，７４０，４４５号に記載されているような、水に難溶な塩基性金属化合物およびこの塩基性金属化合物を構成する金属イオンと水を媒体として錯形成反応しうる化合物（錯形成化合物という）の組合せで塩基を発生させる方法でも良い。
塩基又は塩基プレカーサーの使用量は０．１〜２０ｇ／ｍ² 、好ましくは１〜１０ｇ／ｍ² である。
【０１２９】
本発明の感光材料には、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挙げられる。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類）、およびポリエチレングリコール類が挙げられる。
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か好ましい。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。
熱現像工程の加熱温度は、約５０℃から２５０℃であるが、特に６０℃から１５０℃が有用である。
【０１３０】
熱現像工程において必要とされる塩基を供給するために、塩基又は塩基プレカーサーを含有する処理層を有する処理材料が用いられる。該処理材料にはこの他に加熱現像時に空気を遮断したり、感光材料からの素材の揮散を防止したり、塩基以外の処理用の素材を感光材料に供給したり、現像後に不要になる感光材料中の素材（ＹＦ染料、ＡＨ染料等）あるいは現像時に生成する不要成分を除去したりする機能を持たせても良い。上記処理材料の支持体とバインダーには、感光材料と同様のものを用いることが出来る。
上記処理材料には、前述の染料の除去その他の目的で、媒染剤を添加しても良い。媒染剤は写真分野で公知のものを用いることが出来、ＵＳ４，５００，６２６号第５８〜５９欄や、特開昭６１−８８，２５６号３２〜４１頁、特開昭６２−２４４，０４３号、特開昭６２−２４４，０３６号等に記載の媒染剤を挙げることが出来る。また、ＵＳ４，４６３，０７９号記載の色素受容性の高分子化合物を用いても良い。また前記した熱溶剤を含有させてもよい。
【０１３１】
上記処理材料の処理層には、塩基又は塩基プレカーサーを含有させる。塩基としては有機塩基、無機塩基のいずれでもよく、塩基プレカーサーとしては前述したものが使用しうる。塩基又は塩基プレカーサーの使用量は０．１〜２０ｇ／ｍ² 、好ましくは１〜１０ｇ／ｍ² である。
【０１３２】
上記処理材料を用いて熱現像するに際し、現像促進あるいは、処理用素材の転写促進、不要物の拡散促進の目的で少量の水を用いる。具体的には、米国特許第４，７０４，２４５号、同４，４７０，４４５号、特開昭６１−２３８，０５６号等に記載されている。水には無機のアルカリ金属塩や有機の塩基、低沸点溶媒、界面活性剤、かぶり防止剤、難溶性金属塩との錯形成化合物、防黴剤、防菌剤を含ませてもよい。
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処理材料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。
水は感光材料、処理材料またはその両者に付与する方法を用いることができる。その使用量は感光材料および処理材料の（バック層を除く）全塗布膜を最大膨潤させるに要する量の１／１０〜１倍に相当する量である。
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くしは処理材料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。
【０１３３】
少量の水の存在下に熱現像を行う場合、欧州特許公開２１０，６６０号、米国特許第４，７４０，４４５号に記載されているように、水に難溶な塩基性金属化合物およびこの塩基性金属化合物を構成する金属イオンと水を媒体として錯形成反応しうる化合物（錯形成化合物という）の組合せで塩基を発生させる方法を採用するのが効果的である。この場合、水に難溶な塩基性金属化合物は感光材料に、錯形成化合物は処理材料に添加するのが、生保存性の点で望ましい。
【０１３４】
現像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。
感光材料と処理材料を感光層と処理層が向かい合う形で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。加熱温度としては７０℃〜１００℃が好ましい。
【０１３５】
本発明の感光材料よりなる写真要素の処理には種々の熱現像装置のいずれもが使用できる。例えば、特開昭５９−７５，２４７号、同５９−１７７，５４７号、同５９−１８１，３５３号、同６０−１８，９５１号、実開昭６２−２５，９４４号、特願平４−２７７，５１７号、同４−２４３，０７２号、同４−２４４，６９３号、同６−１６４，４２１号、同６−１６４，４２２号等に記載されている装置などが好ましく用いられる。
また市販の装置としては富士写真フイルム（株）製ピクトロスタット１００、同ピクトロスタット２００、同ピクトロスタット３００、同ピクトロスタット３３０、同ピクトロスタット５０、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。
【０１３６】
本発明の感光材料および／または処理シートは加熱現像のための加熱手段としての導電性の発熱体層を有する形態であっても良い。この発熱の発熱要素には、特開昭６１−１４５，５４４号等に記載のものを利用できる。
【０１３７】
本発明の感光材料は現像と同時に感光材料中の現像銀を除去したり、処理材料に漂白剤として作用する銀の酸化剤を含有させておき、熱現像時にこれらの反応を生じさせることができる。
また、画像形成の現像終了後に銀の酸化剤を含有させた第二の材料を感光材料と貼り合わせて現像銀の除去を行うこともできる。
しかしながら、処理時に現像銀を漂白しない方が、処理が簡易であり好ましい。
【０１３８】
上記処理材料において使用できる漂白剤としては、常用されている銀漂白剤を任意に使用できる。このような漂白剤は米国特許第１，３１５，４６４号および同１，９４６，６４０号、およびPhotographic Chemistry ol2,chapter30,Foundation Press London England に記載されている。これらの漂白剤は写真銀像を効果的に酸化しそして可溶化する。有用な銀漂白剤の例には、アルカリ金属重クロム酸塩、アルカリ金属フェリシアン化物がある。
好ましい漂白剤は水に可溶な物であり、そしてニンヒドリン、インダンジオン、ヘキサケトシキロヘキサン、２，４−ジニトロ安息香酸、ベンゾキノン、ベンゼンスルホン酸、２，５−ジニトロ安息香酸を包含する。また、金属有機錯体、たとえばシキロヘキシルジアルキルアミノ４酢酸の第２鉄塩およびエチレンジアミン４酢酸の第２鉄塩、クエン酸の第２鉄塩がある。第二の処理材料に用いうるバインダー、支持体、その他の添加剤に関しても、前記の感光材料を現像する処理材料（第一の処理材料）と同じ物を用いることが出来る。
漂白剤の塗布量は、貼り合わせられる感光材料の含有銀量に応じて変えられ
るべきであるが、感光材料の単位面積当たりの塗布銀量の０．０１モル〜１０モル／感光材料の塗布銀モルの範囲で使用される。好ましくは０．１から３モル／感光材料の塗布銀モルであり、さらに好ましくは０．１〜２モル／感光材料の塗布銀モルである。
【０１３９】
第一の処理材料、第二の処理材料ともに、最低一つの重合性タイミング層を有することが出来る。この重合性タイミング層は、所望とするハロゲン化銀と色素供与性化合物、あるいは現像主薬の反応が実質的に完了するまでの間、漂白反応を一時的に遅延させることが可能である。タイミング層は、ゼラチン、ポリビニルアルコール、または、ポリビニルアルコール−ポリビニルアセテートからなることが出来る。この層はまた、例えば米国特許第４，０５６，３９４号、同第４，０６１，４９６号および、同第４，２２９，５１６号に記載されているようなバリアータイミング層であっても良い。
このタイミング層を塗布する場合、５〜５０ミクロン、好ましくは１０〜３０ミクロンの膜厚で塗布される。
【０１４０】
本発明においては、現像後の感光材料を第２の処理材料を用いて漂白する方法として、感光材料及び第２の処理材料双方のバック層を除く全塗布膜を最大膨潤させるに要する量の０．１から１倍に相当する水を感光材料または第２の処理材料に与えた後、感光材料と第２の処理材料を感光層と処理層が向かい合う形で重ね合わせ、４０℃から１００℃の温度で５秒から６０秒間加熱する。
水の量、水の種類、水の付与方法、および感光材料と処理材料を重ね合わせる方法については第一の処理材料と同様のものを用いることができる。
【０１４１】
より具体的には特開昭５９−１３６，７３３号、米国特許第４，１２４，３９８号、特開昭５５−２８，０９８号に記載されている漂白シートを用いることが出来る。
本発明の感光材料は、熱現像の後、未反応のハロゲン化銀を定着せず、未反応のハロゲン化銀を実質的に感光材料側に残存させたままネガ原稿として使用し、ペーパー等への画像を形成するために用いられる。
本発明において、「未反応のハロゲン化銀を定着せず」とは、熱現像のあと付加的工程として、定着工程を有しないことをいう。
本発明において、未反応のハロゲン化銀を「実質的に残存させたまま」とは、未反応のハロゲン化銀の５０モル％以上、好ましくは７０モル％以上、より好ましくは８０モル％以上残存させたままをいう。
【０１４２】
本発明においては、水の存在下で処理シートと感光材料の膜面同士を重ね合わせてから両者を剥離するまでの処理時間が３０秒以内であることが好ましい。
【０１４３】
本発明の感光材料には、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頁、特開昭６２−１７３，４６３号、同６２−１８３，４５７号等に記載されている。
本発明の感光材料には、スベリ性防止、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。有機フロオロ化合物の代表例としては、特公昭５７−９，０５３号第８〜１７欄、特開昭６１−２０，９４４号、同６２−１３５，８２６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。
【０１４４】
本発明の感光材料には滑り性がある事が好ましい。滑り剤は感光層面、バック面ともに用いることが好ましい。好ましい滑り性としては動摩擦係数で０．２５以下０．０１以上である。この時の測定は直径５mmのステンレス球に対し、６０cm／分で搬送した時の値を表す（２５℃、６０％ＲＨ）。この評価において相手材として感光層面に置き換えてもほぼ同レベルの値となる。
使用可能な滑り剤としては、ポリオルガノシロキサン、高級脂肪酸アミド、高級脂肪酸金属塩、高級脂肪酸と高級アルコールのエステル等であり、ポリオルガノシロキサンとしては、ポリジメチルシロキサン、ポリジエチルシロキサン、ポリスチリルメチルシロキサン、ポリメチルフェニルシロキサン等を用いることができる。添加層としては乳剤層の最外層やバック層が好ましい。特にポリジメチルシロキサンや長鎖アルキル基を有するエステルが好ましい。
【０１４５】
また本発明においては、帯電防止剤が好ましく用いられる。それらの帯電防止剤としては、カルボン酸及びカルボン酸塩、スルホン酸塩を含む高分子、カチオン性高分子、イオン性界面活性剤化合物を挙げることができる。
帯電防止剤として最も好ましいものは、ＺｎＯ、ＴｉＯ₂ 、ＳｎＯ₂ 、Ａｌ₂ Ｏ₃ 、Ｉｎ₂ Ｏ₃ 、ＳｉＯ₂ 、ＭｇＯ、ＢａＯ、ＭｏＯ₃ 、Ｖ₂ Ｏ₅ の中から選ばれた少くとも１種の体積抵抗率が１０⁷ Ω・cm以下、より好ましくは１０⁵ Ω・cm以下である粒子サイズ０．００１〜１．０μm 結晶性の金属酸化物あるいはこれらの複合酸化物（Ｓｂ，Ｐ，Ｂ，Ｉｎ，Ｓ，Ｓｉ，Ｃなど）の微粒子、更にはゾル状や金属酸化物あるいはこれらの複合酸化物の微粒子である。感光材料への含有量としては５〜５００mg／ｍ² が好ましく、特に好ましくは１０〜３５０mg／ｍ² である。導電性の結晶性酸化物又はその複合酸化物とバインダーの量の比は１／３００〜１００／１が好ましく、より好ましくは１／１００〜１００／５である。
【０１４６】
感光材料または処理シートの構成（バック層を含む）には、寸度安定化、カール防止、接着防止、膜のヒビ割れ防止、圧力増減感防止等の膜物性改良の目的で種々のポリマーラテックスを含有させることができる。具体的には、特開昭６２−２４５，２５８号、同６２−１３６，６４８号、同６２−１１０，０６６号等に記載のポリマーラテックスのいずれも使用できる。特に、ガラス転移点の低い（４０℃以下）ポリマーラテックスを媒染層に用いると媒染層のヒビ割れを防止することができ、またガラス転移点が高いポリマーラテックスをバック層に用いるとカール防止効果が得られる。
【０１４７】
本発明の感光材料にはマット剤が有る事が好ましい。マット剤としては乳剤面とバック面のどちらでもよいが、乳剤側の最外層に添加するのが特に好ましい。マット剤は処理液可溶性でも処理液不溶性でもよく、好ましくは両者を併用することである。例えばポリメチルメタクリレート、ポリ（メチルメタクリレート／メタクリル酸＝９／１又は５／５（モル比））、ポリスチレン粒子などが好ましい。粒径としては０．８〜１０μm が好ましく、その粒径分布も狭い方が好ましく、平均粒径の０．９〜１．１倍の間に全粒子数の９０％以上が含有させることが好ましい。又、マット性を高めるために０．８μm 以下の微粒子を同時に添加することも好ましく、例えばポリメチルメタクリレート（０．２μm ）、ポリ（メチルメタクリレート／メタクリル酸＝９／１（モル比））（０．３μm ）、ポリスチレン粒子（０．２５μm ）、コロイダルシリカ（０．０３μm ）が挙げられる。具体的には特開昭６１−８８，２５６号(29)頁に記載されている。その他、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樹脂ビーズ等の特開昭６３−２７４，９４４号、同６３−２７４，９５２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。
【０１４８】
本発明において感光材料および処理シートの支持体としては、処理温度に耐えることのできるものが用いられる。一般的には、日本写真学会編「写真工学の基礎−銀塩写真編−」、（株）コロナ社刊（昭和５４年）(223) 〜(240) 頁記載の紙、合成高分子（フィルム）等の写真用支持体が挙げられる。具体的には、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネート、ポリ塩化ビニル、ポリスチレン、ポリプロピレン、ポリイミド、セルロース類（例えばトリアセチルセルロース）等が挙げられる。
これらは、単独で用いることもできるし、ポリエチレン等の合成高分子で片面または両面をラミネートされた支持体として用いることもできる。
この他に、特開昭６２−２５３，１５９号(29)〜(31)頁、特開平１−１６１，２３６号(14)〜(17)頁、特開昭６３−３１６，８４８号、特開平２−２２，６５１号、同３−５６，９５５号、米国特許第５，００１，０３３号等に記載の支持体を用いることができる。
【０１４９】
特に耐熱性やカール特性の要求が厳しい場合、感光材料用の支持体として特開平６−４１，２８１号、同６−４３，５８１号、同６−５１，４２６号、同６−５１，４３７号、同６−５１，４４２号、同６−８２，９６１号、同６−８２，９６０号、同６−１２３，９３７号、同６−８２，９５９号、同６−６７，３４６号、同６−１１８，５６１号、同６−２６６，０５０号、同６−２０２，２７７号、同６−１７５，２８２号、同６−１１８，５６１号、同７−２１９，１２９号、同７−２１９，１４４号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。
【０１５０】
また、支持体と感光材料構成層を接着させるために、表面処理することが好ましい。薬品処理、機械的処理、コロナ放電処理、火焔処理、紫外線処理、高周波処理、グロー放電処理、活性プラズマ処理、レーザー処理、混酸処理、オゾン酸化処理、などの表面活性化処理が挙げられる。表面処理の中でも好ましいのは、紫外線照射処理、火焔処理、コロナ処理、グロー処理である。
次に下塗法について述べると、単層でもよく２層以上でもよい。下塗層用バインダーとしては、塩化ビニル、塩化ビニリデン、ブタジエン、メタクリル酸、アクリル酸、イタコン酸、無水マレイン酸などの中から選ばれた単量体を出発原料とする共重合体を始めとして、ポリエチレンイミン、エポキシ樹脂、グラフト化ゼラチン、ニトロセルロース、ゼラチンが挙げられる。支持体を膨潤させる化合物としてレゾルシンとｐ−クロルフェノールがある。下塗層にはゼラチン硬化剤としてはクロム塩（クロム明ばんなど）、アルデヒド類（ホルムアルデヒド、グルタールアルデヒドなど）、イソシアネート類、活性ハロゲン化合物（２，４−ジクロロ−６−ヒドロキシ−ｓ−トリアジンなど）、エピクロルヒドリン樹脂、活性ビニルスルホン化合物などを挙げることができる。ＳｉＯ₂ 、ＴｉＯ₂ 、無機物微粒子又はポリメチルメタクリレート共重合体微粒子（０．０１〜１０μm ）をマット剤として含有させてもよい。
【０１５１】
また、支持体として例えば、特開平４−１２４，６４５号、同５−４０，３２１号、同６−３５，０９２号、特願平５−５８，２２１号、同６−３１７，８７５号記載の磁気記録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。
【０１５２】
磁気記録層とは、磁性体粒子をバインダー中に分散した水性もしくは有機溶媒系塗布液を支持体上に塗設したものである。
磁性体粒子は、γＦｅ₂ Ｏ₃ などの強磁性酸化鉄、Ｃｏ被着γＦｅ₂ Ｏ₃ 、Ｃｏ被着マグネタイト、Ｃｏ含有マグネタイト、強磁性二酸化クロム、強磁性金属、強磁性合金、六方晶系のＢａフェライト、Ｓｒフェライト、Ｐｂフェライト、Ｃａフェライトなどを使用できる。Ｃｏ被着γＦｅ₂ Ｏ₃ などのＣｏ被着強磁性酸化鉄が好ましい。形状としては針状、米粒状、球状、立方体状、板状等いずれでもよい。比表面積ではＳＢＥＴ で２０m²／ｇ以上が好ましく、３０m²／ｇ以上が特に好ましい。強磁性体の飽和磁化（σｓ）は、好ましくは３．０×１０⁴ 〜３．０×１０⁵ A/m であり、特に好ましくは４．０×１０⁴ 〜２．５×１０⁵ A/m である。強磁性体粒子を、シリカおよび／またはアルミナや有機素材による表面処理を施してもよい。さらに、磁性体粒子は特開平６−１６１，０３２号に記載された如くその表面にシランカップリング剤またはチタンカップリング剤で処理されてもよい。又特開平４−２５９，９１１号、同５−８１，６５２号に記載の表面に無機、有機物を被覆した磁性体粒子も使用できる。
【０１５３】
磁性体粒子に用いられるバインダーは、特開平４−２１９，５６９号に記載の熱可塑性樹脂、熱硬化性樹脂、放射線硬化性樹脂、反応型樹脂、酸、アルカリ又は生分解性ポリマー、天然物重合体（セルロース誘導体、糖誘導体など）およびそれらの混合物を使用することができる。上記の樹脂のＴｇは−４０℃〜３００℃、重量平均分子量は０．２万〜１００万である。例えばビニル系共重合体、セルロースジアセテート、セルローストリアセテート、セルロースアセテートプロピオネート、セルロースアセテートブチレート、セルローストリプロピオネートなどのセルロース誘導体、アクリル樹脂、ポリビニルアセタール樹脂を挙げることができ、ゼラチンも好ましい。特にセルロースジ（トリ）アセテートが好ましい。バインダーは、エポキシ系、アジリジン系、イソシアネート系の架橋剤を添加して硬化処理することができる。イソシアネート系の架橋剤としては、トリレンジイソシアネート、４，４′−ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、などのイソシアネート類、これらのイソシアネート類とポリアルコールとの反応生成物（例えば、トリレンジイソシアナート３mol とトリメチロールプロパン１mol の反応生成物）、及びこれらのイソシアネート類の縮合により生成したポリイソシアネートなどが挙げられ、例えば特開平６−５９，３５７号に記載されている。
【０１５４】
前述の磁性体粒子を上記バインダー中に分散する方法は、特開平６−３５０９２号に記載されている方法のように、ニーダー、ピン型ミル、アニュラー型ミルなどが好ましく併用も好ましい。特開平５−０８８２８３号記載の分散剤や、その他の公知の分散剤が使用できる。磁気記録層の厚みは０．１μm 〜１０μm 、好ましくは０．２μm 〜５μm 、より好ましくは０．３μm 〜３μm である。磁性体粒子とバインダーの重量比は好ましくは０．５：１００〜６０：１００からなり、より好ましくは１：１００〜３０：１００である。磁性体粒子分散塗布液の塗布量は、磁性体粒子の重量として０．００５〜３ｇ／ｍ² 、好ましくは０．０１〜２ｇ／ｍ² 、さらに好ましくは０．０２〜０．５ｇ／ｍ² である。磁気記録層の透過イエロー濃度は、０．０１〜０．５０が好ましく、０．０３〜０．２０がより好ましく、０．０４〜０．１５が特に好ましい。磁気記録層は、写真用支持体の裏面に塗布又は印刷によって全面またはストライプ状に設けることができる。磁気記録層を塗布する方法としてはエアードクター、ブレード、エアナイフ、スクイズ、含浸、リバースロール、トランスファロール、グラビヤ、キス、キャスト、スプレイ、ディップ、バー、エクストリュージョン等が利用でき、特開平５−３４１，４３６号等に記載の塗布液が好ましい。
【０１５５】
磁気記録層に、潤滑性向上、カール調節、帯電防止、接着防止、ヘッド研磨などの機能を併せ持たせてもよいし、別の機能性層を設けて、これらの機能を付与させてもよく、粒子の少なくとも１種以上がモース硬度が５以上の非球形無機粒子の研磨剤であることが好ましい。非球形無機粒子の組成としては、酸化アルミニウム、酸化クロム、二酸化硅素、二酸化チタン、シリコンカーバイト等の酸化物、炭化硅素、炭化チタン等の炭化物、ダイアモンド等の微粉末が好ましい。これらの研磨剤は、その表面をシランカップリング剤又はチタンカップリング剤で処理されてもよい。これらの粒子は磁気記録層に添加してもよく、また磁気記録層上にオーバーコート（例えば保護層、潤滑剤層など）しても良い。この時使用するバインダーは前述のものが使用でき、好ましくは磁気記録層のバインダーと同じものがよい。磁気記録層を有する感光材料については、ＵＳ５，３３６，５８９号、同５，２５０，４０４号、同５，２２９，２５９号、同５，２１５，８７４号、ＥＰ４６６，１３０号に記載されている。
【０１５６】
上述の磁気記録層を有する感光材料に好ましく用いられるポリエステル支持体について更に記すが、感光材料、処理、カートリッジ及び実施例なども含め詳細については、公開技術、公技番号９４−６０２３（発明協会；１９９４．３．１５）に記載されている。ポリエステルはジオールと芳香族ジカルボン酸を必須成分として形成され、芳香族ジカルボン酸として２，６−、１，５−、１，４−、及び２，７−ナフタレンジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、ジオールとしてジエチレングリコール、トリエチレングリコール、シクロヘキサンジメタノール、ビスフェノールＡ、ビスフェノールが挙げられる。この重合ポリマーとしては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリシクロヘキサンジメタノールテレフタレート等のホモポリマーを挙げることができる。特に好ましいのは２，６−ナフタレンジカルボン酸を５０モル％〜１００モル％含むポリエステルである。中でも特に好ましいのはポリエチレン−２，６−ナフタレートである。平均分子量の範囲は約５，０００ないし２００，０００である。ポリエステルのＴｇは５０℃以上であり、さらに９０℃以上が好ましい。
【０１５７】
次にポリエステル支持体は、巻き癖をつきにくくするために熱処理温度は４０℃以上Ｔｇ未満、より好ましくはＴｇ−２０℃以上Ｔｇ未満で熱処理を行う。熱処理はこの温度範囲内の一定温度で実施してもよく、冷却しながら熱処理してもよい。この熱処理時間は、０．１時間以上１５００時間以下、さらに好ましくは０．５時間以上２００時間以下である。支持体の熱処理は、ロール状で実施してもよく、またウェブ状で搬送しながら実施してもよい。表面に凹凸を付与し（例えばＳｎＯ₂ やＳｂ₂ Ｏ₅ 等）の導電性無機微粒子を塗布する）、面状改良を図ってもよい。又端部にローレットを付与し端部のみ少し高くすることで巻芯部の切り口写りを防止するなどの工夫を行うことが望ましい。これらの熱処理は支持体製膜後、表面処理後、バック層塗布後（帯電防止剤、滑り剤等）、下塗り塗布後のどこの段階で実施してもよいが、好ましいのは帯電防止剤塗布後である。
このポリエステルには紫外線吸収剤を練り込んでも良い。又ライトパンピング防止のため、三菱化成製のDiaresin、日本化薬製のKayaset 等ポリエステル用として市販されている染料または顔料を塗り込むことにより目的を達成することが可能である。
【０１５８】
次に、感光材料を装填することのできるフィルムパトローネについて記す。本発明で使用されるパトローネの主材料は金属でも合成プラスチックでもよい。
好ましいプラスチック材料はポリスチレン、ポリエチレン、ポリプロピレン、ポリフェニルエーテルなどである。更にパトローネは、各種の帯電防止剤を含有してもよくカーボンブラック、金属酸化物粒子、ノニオン、アニオン、カチオン及びベタイン系界面活性剤又はポリマー等を好ましく用いることができる。これらの帯電防止されたパトローネは特開平１−３１２，５３７号、同１−３１２，５３８号に記載されている。特に２５℃、２５％ＲＨでの抵抗が１０¹²Ω／□以下が好ましい。通常プラスチックパトローネは、遮光性を付与するためにカーボンブラックや顔料などを練り込んだプラスチックを使って製作される。パトローネのサイズは現在１３５サイズのままでもよいし、カメラの小型化には、現在の１３５サイズの２５mmのカートリッジの径を２２mm以下とすることも有効である。パトローネのケースの容積は、３０cm³ 以下、さらには２５cm³ 以下とすることが好ましい。パトローネおよびパトローネケースに使用されるプラスチックの重量は５ｇ〜１５ｇが好ましい。
【０１５９】
更にスプールを回転してフィルムを送り出すパトローネでもよい。またフィルム先端がパトローネ本体内に収納され、スプール軸をフィルム送り出し方向に回転させることによってフィルム先端をパトローネのポート部から外部に送り出す構造でもよい。これらはＵＳ４，８３４，３０６号、同５，２２６，６１３号に開示されている。
【０１６０】
本発明においては、現像によって生じた現像銀や未現像のハロゲン化銀はこれらを除去することなくスキャナー等により画像情報をデジタルデータとして取り込むことを主な目的としているが、従来の方法である撮影した情報をカラーペーパーのようなプリント材料にアナログ的に光学露光して使用することもできる。
【０１６１】
本発明においては、撮影とそれに続く画像形成現像の後で画像情報を読み取る障害を低減するその他の方法を組み合わせることができる。特に未現像のハロゲン化銀は、ゼラチン膜中では高いヘイズを生じ画像のバックグラウンドの濃度を上昇させるため、本発明に用いられるハロゲン化銀はその効果を減少させる効果が顕著であると考えられるが、 その作用の詳細な機構は今後の研究により明らかになるであろう。
【０１６２】
このカラー撮影材料を用いてカラーペーパーや熱現像感光材料にプリントを作製する方法として、特開平５−２４１，２５１号、同５−１９，３６４号、同５−１９，３６３号記載の方法を用いることができる。
【０１６３】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
【０１６４】
実施例１
【０１６５】
沃臭化銀平板乳剤（比較）Ｍ−１、Ｍ−２、Ｍ−３の調製方法について述べる。
平均分子量１５，０００のゼラチン０．７４ｇ及び臭化カリウム０．７ｇを含む蒸留水９３０mlを反応容器中に入れ、４２℃に昇温した。この溶液に強く攪拌しながら硝酸銀１．２ｇを含む水溶液３０mlと臭化カリウム０．８２ｇを含む水溶液３０mlとを３０秒間で添加した。添加終了後１分間４０℃に保った後、反応溶液の温度を７５℃に上昇させた。ゼラチン２７．５ｇを蒸留水２００mlと共に加えた後、硝酸銀２２．５ｇを含む水溶液１００mlと臭化カリウム１５．４３ｇを含む水溶液８０mlとを添加流量を加速しながら１１分間にわたって添加した。
【０１６６】
次いで硝酸銀７５．１ｇを含む水溶液２５０mlと沃化カリウムを臭化カリウムとのモル比３：９７で含む水溶液（臭化カリウムの濃度２６％）とを添加流量を加速しながら、かつ反応液の銀電位が飽和カロメル電極に対して２mVとなるように２０分間で添加した。さらに硝酸銀１８．７ｇを含む水溶液７５mlと臭化カリウムの２１．９％水溶液とを４分間にわたって、かつ反応液の銀電位が飽和カロメル電極に対して０mVとなるように添加した。添加終了後１分間７３℃に保った後、反応液の温度を５５℃に下降させた。次いで、硝酸銀８．１ｇを含む水溶液１２０mlと沃化カリウム７．２６ｇを含む水溶液３２０mlとを５分間にわたって添加した。添加終了後臭化カリウム５．５ｇおよび六塩化イリジウム酸カリウム０．０４mgを加え、５５℃で１分間保った後、さらに硝酸銀４４．３ｇを含む水溶液１８０mlと臭化カリウム３４．０ｇを含む水溶液１６０mlとを１０分間にわたって添加した。温度を下げ、定法に従って脱塩を行った。
【０１６７】
得られた乳剤は円相当の直径で表した平均等価円直径１．８１μm 、平均粒子直径を平均粒子厚みで除した比（アスペクト比）が３．８の六角平板状粒子よりなる沃臭化銀乳剤（沃化銀含有率５．７モル％）であった。この乳剤を乳剤Ｍ−１とした。
乳剤Ｍ−１とは、最初のゼラチン量及び臭化カリウムの量を変えることで粒子等価円直径１．２１μ及び０．７６μの粒子を調製し、乳剤Ｍ−２およびＭ−３とした。乳剤Ｍ−２およびＭ−３は実施例２で使用する。
【０１６８】
次に立方体塩化銀乳剤（比較）Ｒ−１、Ｒ−２、Ｒ−３の調製方法について説明する。
脱カルシウムゼラチン（カルシウム含有率２，０００ｐｐｍ以下）３０．０ｇ、塩化ナトリウム２．４ｇおよび硫酸（１Ｎ）１５．０ｍｌを含む蒸留水１０００ｍｌを反応容器中に入れ、５９℃に昇温した。この溶液にＮ，Ｎ’−ジメチルイミダゾリジン−２−チオン（１％）水溶液１．９ｍｌを加え、強く攪拌しながら硝酸銀７．１ｇを含む水溶液２０００ｍｌと塩化ナトリウム２．４１ｇを含む水溶液２００ｍｌとを２４分間で添加した。次いで硝酸銀１６２．８ｇを含む水溶液５００ｍｌと塩化ナトリウム５９．８８ｇを含む水溶液５００ｍｌとを添加流量を加速しながら、８０分間にわたって添加した。これらの反応液の添加開始から６０分経過した時点で六塩化イリジウム酸カリウム０．０４ｍｇを添加した。反応液添加終了から５分間５５℃で保った後、温度を下げ、定法に従って脱塩を行った。
【０１６９】
得られた乳剤は円相当の直径で表した平均粒子サイズ０．７３μｍの立方体粒子よりなる乳剤であった。この乳剤を乳剤Ｒ−１とした。
また、反応容器の温度をそれぞれ４５℃、４０℃にした以外は乳剤Ｒ−１と全く同様にして乳剤Ｒ−２およびＲ−３を作製した。 得られた乳剤の平均粒子サイズはそれぞれ０．５４μｍおよび０．２９μｍであった。乳剤Ｒ−２およびＲ−３は実施例２で使用する。
【０１７０】
次に、（１００）面からなる高塩化銀平板乳剤（本発明）Ｈ−１、Ｈ−２，Ｈ−３の調製方法について述べる。
平均分子量１５，０００のゼラチン２０．２ｇ、塩化ナトリウム０．８１ｇ、および硫酸（１Ｎ）８．８ｍｌを含む蒸留水１，０００ｍｌを反応容器中に入れ、３５℃に昇温した。この溶液に強く攪拌しながら硝酸銀６．１ｇを含む水溶液３０ｍｌと塩化ナトリウム２．００ｇおよび臭化カリウム０．２１ｇを含む水溶液３０ｍｌとを４５秒間で添加した。次いで平均重合度３００〜７００のポリビニールアルコール（株式会社クラレ製クラレポバール１０５）５．０ｇを含むの水溶液を添加した。次いで臭化カリウム０．５５ｇを含む水溶液４０ｍｌを添加した。さらに硝酸銀１８．３ｇを含む水溶液１００ｍｌと塩化ナトリウム６．３０ｇを含む水溶液１００ｍｌとを３分間で添加した。水酸化ナトリウム（１Ｎ）６．０ｍｌを添加し、反応溶液の温度を７５℃に上昇させた。ゼラチン１０．０ｇを蒸留水１００ｍｌと共に加えた後、硝酸銀１４５．４ｇを含む水溶液７５０ｍｌと塩化ナトリウムの７．０％水溶液とを添加流量を加速しながら、かつ反応液の銀電位が飽和カロメル電極に対して１００ｍＶとなるように４５分間にわたって添加した。六塩化イリジウム酸カリウム０．０４ｍｇを添加し、７５℃で３０分間保った後、温度を下げ、定法に従って脱塩を行った。
【０１７１】
得られた乳剤は臭化銀含率０．６４モル％の塩臭化銀よりなり、円相当の直径で表した平均粒子サイズ０．６７μｍ、平均の粒子投影面積と等価な円の直径を平均粒子厚みで除した比（アスペクト比）が７．１、投影面は平均縦横比が１：１．２５の矩形である平板状粒子よりなる（１００）塩臭化銀乳剤であった。この乳剤を乳剤Ｈ−１とした。また、反応の最初に用いるゼラチンの分子量およびゼラチン量を調節して球相当平均粒子サイズがそれぞれ０．５０μｍおよび０．３１μｍである乳剤Ｈ−２およびＨ−３を調製した。得られた乳剤Ｈ−２およびＨ−３は実施例２で使用する。
【０１７２】
乳剤Ｍ−１、Ｍ−２、Ｍ−３、Ｒ−１、Ｒ−２、Ｒ−３、Ｈ−１、Ｈ−２、Ｈ−３に対する分光増感および化学増感について述べる。これらの乳剤には下記の分光増感色素Ｉ、IIおよびIII 、化合物Ｉ、チオシアン酸カリウム、塩化金酸およびチオ硫酸ナトリウムを添加して分光増感および化学増感を施した。このとき、分光増感色素は各乳剤の粒子表面積に比例させて変化させた。また、化学増感時のｐＡｇおよび化学増感剤の量は各々の乳剤の化学増感の程度が最適になるように調節した。
こうして調製した緑感性乳剤はＭ−１ｇのようにｇの添え字を付けて表した。
【０１７３】
【化３３】

【０１７４】
次に、（１１１）面よりなる高塩化銀平板乳剤（本発明）Ｂ−１、Ｂ−２、Ｂ−３の調製方法について述べる。
【０１７５】
脱イオンアルカリ処理骨ゼラチン２．１ｇおよび塩化ナトリウム２ｇを含むゼラチン水溶液１，２００ｍｌを反応容器中に入れ、３５℃に保持し、この溶液に強く攪拌しながら硝酸銀１６５ｇを含む水溶液１，１００ｍｌの（Ａ）液と、塩化ナトリウム５９．１ｇを含む水溶液１，１００ｍｌの（Ｂ）液とを、６０ｍｌずつ、１分間かけて同時に添加し混合した。化合物（３）０．２８５ｇを含む水溶液（Ｃ）液を５０ｍｌ作り、そのうち４０ｍｌを添加し、添加混合の終了１分後に塩化ナトリウム１０％水溶液３０ｍｌを添加した。その後２５分かけて、６０℃に昇温し、その１６分後にフタル化ゼラチン２９ｇを含むゼラチン水溶液２６０ｍｌを添加し、３分後に（Ｃ）液１０ｍｌを添加した。その１分後に、（Ａ）液と（Ｂ）液とを、７６８ｍｌずつ、初速２．８５ｍｌ／分で、加速度０．８１８ｍｌ／（分）² で同時に添加した。（Ａ）液および（Ｂ）液の添加混合の終了１０分前から、塩化ナトリウム３．９ｇと黄血塩０．１ｇとを含む水溶液２７０ｍｌである（Ｄ）液を、１０分かけて添加した。さらに、（Ａ）液と（Ｂ）液の添加終了２分前に臭化カリウム１０％水溶液３４ｍｌを３秒で添加した。（Ａ）液と（Ｂ）液添加終了３分後に、チオシアン酸カリウム１％２７ｍｌを添加し、前記の緑感性乳剤用増感色素Ｉを５７０ｍｇ、緑感性乳剤用増感色素IIを６０ｍｇ、緑感性乳剤用増感色素III を１２０ｍｇ含む、１００ｇのゼラチン分散物の溶解物４５ｍｌを添加１分後に７５℃に昇温し、１０分間保持した。次に温度を４０℃に下げ、沈降剤（１）を用いて定法に従って脱塩を行った。分散は、脱イオンアルカリ処理骨ゼラチン６７ｇ、硝酸亜鉛およびフェノキシエタノールを用いて分散した。そして、ｐＨ６．３、ｐＡｇ７．７になるように調整した。
得られた乳剤中に含まれる粒子は、球相当の直径で表した平均粒子サイズ０．７４μｍ、平均アスペクト比が８．７であり、投影面の隣接辺の比の平均が１：１．６であり、臭化銀の含有率が５モル％の塩臭化銀（１１１）平板状粒子であった。この乳剤をＢ−１とした。
この乳剤（Ｂ−１）の化学増感は、６０℃で行った。４−ヒドロキシ−６−メチル−１，３，３ａ，７−テトラアザインデン、チオ硫酸ナトリウム、セレン増感剤、塩化金酸、ベンゼンチオスルホン酸ナトリウムを順次添加して化学増感し最高感度になるようにした。化学増感の停止は、化合物（４）を用いて行った。この様にして調製した緑感応性乳剤はＢ−１ｇの様に添え字を付けて表した。
【０１７６】
【化３４】

【０１７７】
また最初のゼラチン量および（Ａ）液に含まれる硝酸銀量と（Ｂ）液に含まれる塩化ナトリウム量を調節して、乳剤Ｂ−１ｇとは粒子サイズが異なる（１１１）面からなる乳剤Ｂ−２ｇおよびＢ−３ｇを作製した。Ｂ−２ｇおよびＢ−３ｇの粒子サイズは、それぞれ０．５１μｍ、０．３７μｍであった。乳剤Ｂ−２ｇおよびＢ−３ｇは実施例２で使用する。
【０１７８】
次に塩基プレカーサーとして用いる水酸化亜鉛の分散物を調製した。
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】
さらに、マゼンタカプラーの乳化分散物を調製した。
マゼンタカプラー（ａ）７．８０ｇ、現像主薬（ｂ）５．４５ｇ、被り防止剤（ｃ）２mg、高沸点有機溶媒（ｄ）８．２１ｇおよび酢酸エチル２４．０mlを６０℃で溶解した。石灰処理ゼラチン１２．０ｇおよびドデシルベンゼンスルホン酸ナトリウム０．６ｇを溶解した水溶液１５０ｇ中に先の溶液を混合し温度を５０℃に保って、ディゾルバー攪拌機を用いて１０，０００回転で２０分間かけて乳化分散した。分散後、全量が３００ｇとなるように蒸留水を加え、２，０００回転で１０分間混合した。
【０１８０】
また、マゼンタ層用染料分散物（本発明）を以下のように乳化分散して調製した。つまり、前記のマゼンタ染料Ａ１０を２．０ｇ、トリクレジルフォスフェート２．０ｇ、シクロヘキサン２２ｃｃを溶解した油層成分と石灰処理ゼラチン３．５ｇ、界面活性剤（ｅ）０．２６ｇおよび水３７ｃｃを含む水層成分を混合して、ホモジナイザーを用いて４０℃で１０，０００ｒｐｍで３分間分散し、さらに水４４ｃｃを加えて２，０００ｒｐｍで１０分間混合して均一な分散物とした。得られた分散物は、平均粒子サイズ０．１８μｍであった。
上記染料の比較のために、マゼンタのロイコ色素と亜鉛を組み合わせて熱現像処理時に脱色可能な着色層を形成する層に用いるための着色剤の分散物を作製した。
【０１８１】
これらの分散物と、先に調製したハロゲン化銀乳剤とを組み合わせて表１に示す構成の試料１０１から１０６の６種類の熱現像カラー写真感光材料を作製した。
【０１８２】
【表１】

【０１８３】
【化３５】

【０１８４】
【化３６】

【０１８５】
【化３７】

【０１８６】
さらに、表２〜表４のような処理材料Ｐ−１、Ｐ−２を作製した。
【０１８７】
【表２】

【０１８８】
【表３】

【０１８９】
【表４】

【０１９０】
【化３８】

【０１９１】
【化３９】

【０１９２】
これらの感光材料に、光学楔と緑フィルターを介して１，０００lux で１／１００秒の露光を施した。
露光後の感光材料の表面に４０℃の温水を１８ｍｌ／ｍ² 付与し、処理材料Ｐ−１と互いの膜面同士を重ね合わせた後、ヒートドラムを用いて８３℃で１５秒間熱現像した。処理後感光材料を剥離するとマゼンタ発色の楔形画像が得られた。
【０１９３】
さらに、定着するために、処理材料Ｐ−２を用いて第二工程の処理を施した。第二工程の処理は、処理材料Ｐ−２に１２cc／ｍ² の水を塗布し、第一の処理を施した後の感光材料と貼り合わせ、７０℃で２０秒加熱した。
【０１９４】
得られた試料の未露光部分を観察すると着色層は全て消色していることがわかった。また、得られた発色試料の透過濃度を測定し、所謂特性曲線でそれぞれの感光材料の感度を測定したところ、被り濃度よりも０．１５高い濃度に対応する露光量の逆数をもって相対感度としたときに、感光材料１０１〜１０６はいずれも±０．１以内で一致した。従って、これらの感光材料はほぼ等しい感度であることがわかる。
【０１９５】
これらの試料の最高濃度を測定した。いずれの場合もハロゲン化銀の漂白は行わなかった。定着を行った場合と行わなかった場合で結果の傾向は変化しなかった。定着無の結果を表５にまとめた。
【０１９６】
【表５】

【０１９７】
表５の結果から、本発明の感光材料は最高濃度が高く優れた感光材料であることがわかる。また、処理後の感光材料および処理材料をそれぞれ液クロで抽出したところ、染料の消色物は全て感光材料中にとどまっており、処理材料には転写していないことがわかった。
【０１９８】
実施例２
実施例１で作製したハロゲン化銀乳剤の分光増感に使用する分光増感色素を以下に示すものに変更することで青感性および赤感性の乳剤を調製した。青感性の乳剤にはｂの添え字を付して、例えばＭ−１ｂのように、また、赤感性の乳剤にはｒの添え字を付して、例えばＭ−１ｒのように表した。
【０１９９】
【化４０】

【０２００】
【化４１】

【０２０１】
また、実施例１のカプラー分散物の調製方法に従ってシアンおよびイエローのカプラー分散物も調製した。
実施例１の本発明の染料分散物の調製方法に従ってシアンおよびイエローの染料分散物を調製した。さらに比較のために、熱現像処理時に脱色可能な着色層を形成する目的で下記のイエロー、マゼンタそしてシアンのロイコ色素と亜鉛錯体とを組合せて着色剤の分散物も調製した。
このようにして得られたハロゲン化銀乳剤、カプラー分散物および着色剤分散物を使用して表６に示す多層構成の熱現像カラー感光材料（２１１、２１３、２１４、２２３、２２４）を作製した。
【０２０２】
【表６】

【０２０３】
【表７】

【０２０４】
【表８】

【０２０５】
【表９】

【０２０６】
【化４２】

【０２０７】
【化４３】

【０２０８】
【化４４】

【０２０９】
【化４５】

【０２１０】
ここで、各層に使用する乳剤を表７にまとめた。
【０２１１】
【表１０】

【０２１２】
これらの感光材料の写真特性を実施例１と同様に試験した。まず、各感光材料に光学楔と青、緑そして赤フィルターを介して１，０００lux で１／１００秒の露光を施した。
露光後の感光材料の表面に４０℃の温水を１６ml／ｍ² 付与し、実施例１で用いた処理材料Ｐ−１と互いの膜面同士を重ね合わせながら、ヒートドラムを用いて８０℃で２５秒間（重ね合わせてから、剥離するまでの時間である）熱現像した。第２処理シートによる定着処理は行わなかった。 熱現像処理後に感光材料を剥離すると青フィルターを用いて露光した試料ではイエロー発色の楔形画像が、緑フィルターを用いて露光した試料ではマゼンタ発色の楔形画像が、そして赤フィルターを用いて露光した試料ではシアン発色の楔形画像が得られた。さらに、これらの試料から青光に対する緑感層および赤感層の色分離性の評価を目視判断した。
また、これらの試料の最高濃度を測定した。なお定着は行わなかった。結果を表８にまとめた。
【０２１３】
【表１１】

【０２１４】
結果から、本発明の効果が顕著であることがわかる。即ち、イエロー、マゼンタ、シアンがそれぞれＢ、Ｇ、Ｒ光に対応するそれぞれＯ，Ｍ，Ｕ層の３層ずつの構成からなる本発明のカラー撮影用感光材料としたときでも、実施例１と同様、最高濃度が高いという効果が見られた。また、本実施例のように青感層、緑感層及び赤感層を組み合わせたカラー撮影材料を作製したところ、青光に対する色分離性が良く、優れた感光材料であることが判る。
【０２１５】
【発明の効果】
以上の如く本発明によれば、簡易、迅速で環境に対する負荷の少ない画像形成が可能な高画質の撮影用ハロゲン化銀カラー写真感光材料を提供することができる。
さらに、本発明によれば、簡易、迅速な処理であっても良好な粒状性と露光ラチチュードを与えることのできる優れた撮影用ハロゲン化銀カラー写真感光材料を提供すること、特に、シャープネスの優れた高画質な撮影用ハロゲン化銀カラー写真感光材料を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel silver halide color photographic light-sensitive material for recording an image.
[0002]
[Prior art]
In recent years, photographic light-sensitive materials using silver halide have been further developed, and it is now possible to easily obtain high-quality color images. For example, in a method generally called color photography, a color negative film is used for photographing, and a color print is obtained by optically printing image information recorded on the developed color negative film on color photographic paper. In recent years, this process has been highly developed, and everyone has become popular because of the popularization of color laboratories that are large-scale centralized bases that produce large amounts of color prints with high efficiency or so-called minilabs that are small, simple printer processors installed in stores. Can enjoy color photos easily.
[0003]
The principle of color photography that is widely used now employs color reproduction by the subtractive color method. In general color negatives, a light-sensitive layer using a silver halide emulsion, which is a light-sensitive element imparting photosensitivity to blue, green, and red regions, is provided on a transparent support, and each of these light-sensitive layers has a photosensitive layer. A combination of so-called color couplers that form yellow, magenta, and cyan dyes that are complementary colors is included. The color negative film that has been image-wise exposed by photography is developed in a color developer containing an aromatic primary amine developing agent. At this time, the exposed silver halide grains are developed or reduced by the developing agent, and each dye is formed by a coupling reaction between the oxidized oxidized developing agent and the color coupler. Dye images are obtained by removing metallic silver (developed silver) produced by development and unreacted silver halide by bleaching and fixing processes, respectively. A color photographic paper, which is a color photosensitive material coated with a photosensitive layer having a similar photosensitive wavelength range and color development hue on a reflective support, is subjected to optical exposure through a color negative film after development processing. By performing color development, bleaching and fixing processes, a color print made of a dye image that reproduces the original scene can be obtained.
[0004]
While these systems are now widespread, there is an increasing demand for greater simplicity. First, it is necessary to precisely control the composition and temperature of the processing bath for performing the color development, bleaching and fixing processes described above, and requires specialized knowledge and skilled operations. Secondly, these processing solutions contain substances that require environmental regulations such as color developing agents and iron chelate compounds that are bleaching agents. Is often required. Thirdly, although it has been shortened by recent technological development, it takes time for these development processes, and it must be said that it is still inadequate for the requirement to quickly reproduce a recorded image.
[0005]
In view of these viewpoints, many improvements have been proposed. Various techniques using so-called high silver chloride milk having a high silver chloride content have been proposed, particularly for the purpose of simple and rapid development processing. By using a high silver chloride emulsion, advantages such as an increase in development speed and an increase in reusability of the processing solution can be obtained. For this reason, in recent years, a type using a high silver chloride emulsion has become the mainstream of photosensitive materials for printing such as color photographic paper.
[0006]
In addition to these efforts, we have also reported a technology that reduces environmental burden and improves simplicity by building a system that does not use color developing agents and bleach used in existing color image forming systems. Has been. For example, on page 180 of IS &T's 48th Annual Conference Proceedings, the developed silver and unreacted silver halide are removed by moving the dye produced in the development reaction to the mordant layer and then peeling off. A system is disclosed that eliminates the need for an essential bleach-fixing bath. However, the technique proposed here still requires development processing in a processing bath containing a color developing agent, and it is difficult to say that environmental problems have been solved.
[0007]
As a system that does not require a processing solution containing a color developing agent, Fuji Photo Film Co., Ltd. provides a pictography system and a pictostat system. In this system, a small amount of water is supplied to a photosensitive material containing a base precursor, bonded to an image receiving material, and heated to cause a development reaction. This method is environmentally advantageous in that it does not use the treatment bath described above. However, since this method is used for fixing the formed dye to the dye fixing layer and viewing it as a dye image, it has been desired to develop a system that can be used as a recording material for photographing.
[0008]
The present inventor has proposed a method of using a photosensitive material that has been photographed as unfixed for the purpose of reducing the use of a processing solution as much as possible as a recording material for photographing, simply and quickly. investigated. As a result, the difference between the sensitivity of the blue-sensitive layer and the intrinsic sensitivity of the silver halide in the green-sensitive layer and the red-sensitive layer is insufficient, resulting in insufficient color separation with respect to blue light, and sharpness due to light halation during shooting. It became clear that degradation and image quality degradation due to optical scattering of the remaining silver halide was a problem. As means for solving this problem, a silver halide emulsion containing a high silver chloride tabular grain mainly composed of (100) face and (111) face is introduced as a silver halide having a specific structure having a specific structure. I came up with a method to use in combination.
[0009]
A silver halide photosensitive material for photographing needs high sensitivity. In order to increase the sensitivity, it is effective to increase the sensitivity of silver halide grains and increase the coating amount of silver halide.
US 5,264,337, US 5,292,632, US 5,310,635 or WO 94 / 22,054 are techniques for applying the advantages of rapid development properties of high silver chloride emulsions to photographic materials. Discloses a technique of using a tabular high silver chloride emulsion having a (100) plane as a photographic light-sensitive material for photographing. By using a high silver chloride emulsion, a high development speed can be obtained, and there can be obtained an advantage that the photographic photosensitive material and the printing photosensitive material can be processed using the same processing solution. However, these documents do not describe introduction of a specific colored dye into the light-sensitive material.
Further, silver halide grains having a (100) plane having a length of one side which is not less than 2 times or not more than 0.5 times the arithmetic average of the lengths of the other two sides are highly sensitive and fogging in the photothermographic material. Japanese Patent Publication No. 7-12014 describes that low performance can be obtained. However, these methods are still insufficient in terms of image quality, particularly sharpness.
[0010]
In addition, many reports have been made on silver chloride tabular grains having (100) faces. For example, US-5,314,798, EP-534,395A, EP-617,321A, EP-617,317A, EP-617,318A, EP-617,325A, WO94 / 22,051, EP-616 255A, US-5,356,764, US-5,320,938, US-5,275,930, and the like.
[0011]
Further, various reports have been made on tabular grains mainly composed of (111) planes, and are described in detail in, for example, US Pat. No. 4,439,520. US Pat. No. 5,250,403 describes so-called ultrathin tabular grains having an equivalent circle equivalent diameter of 0.7 μm or more and a thickness of 0.07 μm or less. Further, US Pat. No. 4,435,501 discloses a technique for epitaxially growing a silver salt on the surface of a tabular grain. Recently, in order to improve the performance of tabular grains, EP0,699,947A, EP0,699,951A, EP0,699,945A, EP0,701,164A, EP0,699,944A, EP0,701,165A, EP0,699 , 948A, EP0,699,946A, EP0,699,949A, EP0,699,950A and the like. These are technical disclosures relating to silver bromide and silver iodobromide, but do not describe silver halide of silver chloride comprising (111) face. Also, these documents do not describe any action or effect when a coloring dye having a specific structure is used in the photosensitive material.
[0012]
On the other hand, in the photographic material in which the processing agent as in the present invention is incorporated in the photosensitive material, it is observed that the development time is slowed by containing the coloring dye. This is thought to be because the dye consumes alkali for its dissociation. Therefore, it may be difficult to incorporate a sufficient amount of dye.
[0013]
[Problems to be solved by the invention]
As is apparent from what has been described so far, an object of the present invention is to provide a high-quality silver halide color photographic light-sensitive material for photographing capable of forming an image that is simple, quick and less burdensome on the environment. is there.
It is another object of the present invention to provide an excellent silver halide color photographic light-sensitive material for photographing which can give good graininess and exposure latitude even with simple and rapid processing. In particular, it is to provide a silver halide color photographic light-sensitive material with excellent sharpness and high image quality.
[0014]
[Means for Solving the Problems]
The above object of the present invention is achieved by the following present invention. That is, the present invention comprises at least one photosensitive layer comprising a photosensitive silver halide grain, a compound that forms a dye by a coupling reaction with an oxidized form of a developing agent, and a binder on a support. In the silver halide color photographic light-sensitive material in which a color image is formed by laminating the light-sensitive layer surface of the light-sensitive layer on the processing layer surface of the processing material containing a nucleophilic agent and heat-developing, at least one photosensitive layer is (1) A silver halide grain comprising 50 mol% or more of silver chloride, wherein the main outer surface of the grain is a (100) plane, and the projection plane has an aspect ratio of 1: 1 to 1: 2. An emulsion in which 50% or more of the total projected area is occupied by tabular grains having an aspect ratio of 2 or more, or (2) silver halide grains comprising 50 mol% or more of silver chloride. The total projected area is a tabular grain having an aspect ratio of 2 or more such that the main outer surface of the grain is a (111) plane and the ratio of adjacent sides of the projection plane is a hexagon of 1: 1 to 1:10. And the photosensitive material contains a dye that is decolored by reaction with a nucleophile during development processing, and the dye is diffusion-resistant and further develops. A silver halide color photographic light-sensitive material characterized in that at least a part of the dye that has been decolored after processing is diffusion-resistant, preferably the following general formulas (I) to (I) A silver halide color photographic light-sensitive material characterized by being any one of the dyes represented by IV).
Formula (I)
A51 = L51− (L52 = L53) _m51 -Q51
Formula (II)
A51 = L51− (L52 = L53) _n51 -A52
Formula (III)
A51 (= L51-L52) _p51 = B51
Formula (IV)
(NC) ₂ C = C (CN) -Q51
(In the formula, = represents a double bond,-represents a single bond, A51 and A52 each represent an acidic nucleus, B51 represents a basic nucleus, and Q51 represents an aryl group or a heterocyclic group. L51 and L52) , L53 each represents a methine group, m51 represents 0, 1 or 2. n51 and p51 each represents 0, 1, 2 or 3, provided that the compounds represented by the general formulas (I) to (IV) Does not have a carboxyl group or a sulfo group, and the compounds represented by the general formulas (I) to (IV) have a non-diffusible group, and the product after treatment (decoloration) is also resistant to (It is diffusive and does not substantially elute from the photosensitive material.)
[0015]
DETAILED DESCRIPTION OF THE INVENTION
First, the silver halide grains constituting the present invention will be described.
In the present invention, (1) silver halide grains comprising 50 mol% or more of silver chloride in at least one photosensitive layer, the main outer surface of the grains being constituted by (100) planes, An emulsion in which 50% or more of the total projected area is occupied by tabular grains having an aspect ratio of 2 or more such that the aspect ratio of the projection surface is a rectangle of 1: 1 to 1: 2, or (2) 50 mol% Silver halide grains made of the above silver chloride, wherein the main outer surface of the grains is a (111) plane, and the ratio of adjacent sides of the projection plane is a hexagon with a ratio of 1: 1 to 1:10 An emulsion in which tabular grains having an aspect ratio of 2 or more occupy 50% or more of the total projected area is used, but 50% or more of the projected area of the silver halide grains contained in the emulsion satisfies the above-mentioned definition. That's fine. Furthermore, it is preferable that 70% or more of the projected area satisfies the above-mentioned definition.
[0016]
The aspect ratio in the present invention refers to a value obtained by dividing the diameter of a circle equivalent to the projected area by the particle thickness.
In the first embodiment ((1)) of the present invention, the silver halide grains have a (100) plane as the main outer surface of the grains, so that the projection plane has a rectangular shape. At this time, it is also necessary that the ratio of the vertical and horizontal sides of the rectangle that is the projection plane is in the range of 1: 1 to 1: 2. That is, the effect of the present invention cannot be obtained if an emulsion composed of rod-like or cubical grains close to a cube is used. In the present invention, tabular grains in which the projection plane is close to a square and the ratio of the vertical and horizontal sides of the rectangular projection plane is from 1: 1 to 1: 1.5 are preferred.
In the second embodiment ((2)) of the present invention, the silver halide grains have a hexagonal projection plane because the main outer surface of the grains is a (111) plane. At this time, it is also necessary that the ratio of the adjacent sides of the hexagon that is the projection surface is in the range of 1: 1 to 1:10. That is, the effect of the present invention cannot be obtained when an emulsion composed of grains having a shape close to a triangle is used. In the present invention, tabular grains having a projection plane close to a regular hexagon and a ratio of adjacent sides of the hexagonal projection plane in the range of 1: 1 to 1: 5 are preferred.
[0017]
The shape of these silver halide grains can be measured by observing the silver halide grains and a reference latex sphere used as a standard of size simultaneously with an electron microscope by a carbon replica method in which heavy metals are shadowed.
[0018]
As the halogen composition of the silver halide grains constituting the present invention, silver chlorobromide, silver chloroiodide, silver chloroiodobromide or silver chloride containing 50 mol% or more of silver chloride is used. The emulsion in the present invention may contain silver iodide, but the silver iodide content is preferably 2 mol% or less, more preferably 1 mol% or less. It is also preferable to use a silver halide emulsion composed of grains having a laminated structure composed of a plurality of layers having different halogen compositions inside the silver halide grains. The size of the silver halide grains used in the embodiment of the present invention is preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm, particularly preferably 0. 0 when expressed by the diameter of a circle equal to the projected area. 5 to 4 μm.
[0019]
A silver halide grain comprising 50 mol% or more of silver chloride used in the present invention, wherein (1) the main outer surface of the grain is composed of (100) planes, and the aspect ratio of the projection plane is 1: 1. To an emulsion in which 50% or more of the total projected area is occupied by tabular grains having an aspect ratio of 2 or more, such as a rectangle of 1: 2, or (2) the main outer surface of the grains is the (111) plane In addition, an emulsion in which 50% or more of the total projected area is occupied by tabular grains having an aspect ratio of 2 or more such that the ratio of adjacent sides of the projection surface is a hexagon with a ratio of 1: 1 to 1:10. For this purpose, various methods including a known production method can be used.
[0020]
In the case of producing a high silver chloride tabular emulsion (1) whose main outer surface is a (100) plane, for example, JP-A-5-204,073, JP-A-51-88,017, The methods described in JP-A-63-24, 238 and JP-A-7-146,522 can be arbitrarily used.
[0021]
The method for producing a high silver chloride tabular emulsion (2) whose main outer surface is a (111) plane is disclosed in, for example, US Pat. Nos. 4,399,215 and 4,400,463. , No. 5,217,858, JP-A-2-32 and the like. In the case of high silver chloride, since the (100) plane is usually the outer surface under the condition that there is no adsorbent, after using the adsorbent having surface selectivity on the (111) plane and forming twin nuclei, In the physical ripening process, normal crystal nuclei, single twin nuclei, and non-parallel multiple twin nuclei disappear, selectively obtain parallel multiple twin nuclei, and then grow grains to include tabular grains Photosensitive silver halide is prepared. An empirical rule for producing silver chloride tabular grains composed of (111) faces is reported in Journal of Photographic Science, Vol. 36, page 182 (1988).
[0022]
In preparing the tabular grains used in the present invention, the point is the method of generating nuclei for tabular growth, and iodide ions and bromide ions are added at the initial stage of grain formation as described in the above-mentioned production method. It is useful to add a compound exhibiting selective adsorption to a specific surface.
[0023]
The average grain thickness of the tabular grains used in the present invention is preferably 0.01 to 0.5 μm, more preferably 0.01 to 0.4 μm, and particularly preferably 0.05 to 0.4 μm.
The average grain thickness is the arithmetic average of the grain thicknesses of all tabular grains in the emulsion.
[0024]
In order to form high aspect ratio tabular grains, it is important to generate small twin nuclei. Therefore, at low temperature, high pBr, and low pH, the amount of gelatin can be reduced to use less methionine, low molecular weight, phthalated gelatin derivatives, or shorten nucleation time. Nucleation is preferably performed.
After nucleation, only tabular grains (parallel multiple twin nuclei) are grown by physical ripening, and the other normal crystal nuclei, single twin nuclei, and non-parallel multiple twin nuclei disappear, and the parallel multiple twins selectively. Crystal nuclei are formed. Thereafter, a soluble silver salt and a soluble halogen salt are added and grain growth is performed to prepare an emulsion composed of tabular grains.
[0025]
The emulsion used in the present invention is preferably monodispersed.
The variation coefficient of the equivalent circle diameter of the projected area of all silver halide grains of the emulsion used in the present invention is preferably 30 to 3%, more preferably 25 to 3%, particularly preferably 20 to 3%. . If it exceeds 30%, it is not so preferable in terms of homogeneity between particles, but the present invention is not limited thereto.
The variation coefficient of the equivalent circle diameter is a value obtained by dividing the standard deviation of the equivalent circle diameter of each silver halide grain by the average equivalent circle diameter.
[0026]
In the case of having a phase containing iodide or chloride, these phases may be uniformly distributed or localized in the grains.
Other silver salts such as rhodan silver, silver sulfide, silver selenide, silver carbonate, silver phosphate,
Organic acid silver may be contained as separate grains or as part of silver halide grains.
[0027]
The tabular grains constituting the present invention may have dislocation lines.
A dislocation line is a linear lattice defect at the boundary between a region that has already slipped and a region that has not yet slipped on the slip plane of the crystal.
Regarding dislocation lines of silver halide crystals, 1) C.I. R. Berry, J .; Appl. Phys. 27, 636 (1956), 2) C.I. R. Berry, D.C. C. Skilman, J.M. Appl. Phys. , 35, 2165 (1964), 3) J. et al. F. Hamilton, Photo. Sci. Eng. 11, 57 (1967), 4) T .; Shiozawa, J. et al. Soc. Photo. Sci. Jap. 34, 16 (1971), 5) T .; Shiozawa, J. et al. Soc. Photo. Sci. Jap. 35, 213 (1972) and the like, and can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope.
[0028]
When observing dislocation lines directly using a transmission electron microscope, the silver halide grains taken out from the emulsion are placed on a mesh for electron microscope observation, taking care not to apply such a pressure that the dislocation lines are generated on the grains. Observation is performed by the transmission method in a state where the sample is cooled so as to prevent damage (for example, printout) by the electron beam.
In this case, since the electron beam is less likely to be transmitted as the particle thickness is thicker, it is possible to observe more clearly by using an electron microscope of a high pressure type (200 kV or more with respect to a thickness of 0.25 μm).
[0029]
Japanese Patent Laid-Open No. 63-220,238 describes a technique for controlling the introduction of dislocation lines into silver halide grains.
It has been shown that tabular grains introduced with dislocation lines are superior in photographic characteristics such as sensitivity and reciprocity, compared with tabular grains without dislocation lines.
In the case of tabular grains, the position and number of dislocation lines for each grain when viewed from a direction perpendicular to the main plane can be determined from a photograph of the grain taken using an electron microscope as described above.
[0030]
Descriptions of the emulsion used in the present invention and the photographic emulsion other than the present invention used in combination with the emulsion are described below.
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-A-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 Phisque Photographique, Paul Montel 1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (GFDuffin Photographic Emulsion Chemistry, Focal Press 1966) Inc. published (VLZelikman et al., Making and Coating Photographic EmulusionFocal Press, 1964) can be selected from among silver halide emulsion prepared using methods described in the like.
[0031]
In the process of preparing the photosensitive silver halide emulsion in the present invention, it is preferable to carry out 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.
[0032]
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 purpose of use, but is generally 10 per mole of silver halide. ^-9 -10 ^-3 It is about a mole. Moreover, when making it contain, particle | grains may be put 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, JP-A-5-181,246 and the like are preferably used.
[0033]
In the grain formation stage of the photosensitive silver halide emulsion used in the present invention, rhodan salts, ammonia, tetrasubstituted thiourea compounds, organic thioether derivatives described in JP-B No. 47-11386, or JP-A The sulfur-containing compound described in 53-144,319 can be used.
[0034]
For other conditions, see Grafkide's "Physics and Chemistry of Photography" published by P.Glafkides (P.Glafkides, Chemie et Phisque Photographique, Paul Montel1967), Duffin's "Photoemulsion Chemistry", Focal Press (GFDuffin) Photographic Emulsion Chemistry, Focal Press 1966), “Production and Coating of Photographic Emulsions” by Zerikman et al., VLZelikman et al., Making and Coating Photographic Emulusion Focal Press, 1964, etc. 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.
[0035]
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 selected according to the purpose. The preferred pH range is 2.2 to 7.0, more preferably 2.5 to 6.0.
[0036]
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 sensitization method using palladium or the like, a reduction sensitization method, or the like can be used alone or in combination (for example, JP-A-3-110,555 and JP-A-5-241,267). 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 total coating amount of the photosensitive silver halide used in the present invention is 100 mg / m in terms of silver. ² 10g / m ² The range is preferably 1 g / m ² Or 5g / m ² The range of is more preferable.
[0037]
In order to give the photosensitive silver halide used in the present invention color sensitivity such as green sensitivity and red 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. .
Along with the sensitizing dye, a dye which itself does not have spectral sensitizing action or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3, 615, 641, JP-A-63-23,145, etc.).
These sensitizing dyes may be added to the emulsion before 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. ^-8 10 ^-2 It is about a mole.
[0038]
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.

[0039]
The light-sensitive material of the first and second embodiments of the present invention comprises a photosensitive silver halide, a compound that forms a dye by a coupling reaction with an oxidized form of a developing agent (hereinafter referred to as a coupler), and a binder on a support. A photographic constituent layer including at least one photographic photosensitive layer is applied.
[0040]
In the present invention, in order to construct a photosensitive material used for recording an original scene and reproducing it as a color image, color reproduction by a subtractive color method can be basically used. That is, at least three photosensitive layers having photosensitivity are installed in the blue, green, and red regions, and yellow, magenta, and cyan dyes that are complementary to the photosensitive wavelength region are formed on each photosensitive layer. By including a possible color coupler, the color information of the original scene can be recorded. The original scene can be reproduced by exposing the color photographic paper having the same relationship between the photosensitive wavelength and the developed hue through the dye image thus obtained. It is also possible to read information of a dye image obtained by photographing an original scene with a scanner or the like and reproduce an ornamental image based on this information.
[0041]
As the photosensitive material of the present invention, a photosensitive layer having photosensitivity in three or more wavelength regions can be provided.
It is also possible to have a relationship other than the complementary color as described above between the photosensitive wavelength region and the colored hue. In such a case, the original color information can be reproduced by performing image processing such as hue conversion after capturing the image information as described above.
[0042]
In the present invention, it is preferable to contain at least two types of silver halide emulsions having photosensitivity in the same wavelength region and different average grain projected areas. In the present invention, having the photosensitivity in the same wavelength region means that the photosensitivity is effectively in the same wavelength region. Therefore, even if the emulsions have slightly different spectral sensitivity distributions, if the main photosensitive regions overlap, they are regarded as emulsions having photosensitivity in the same wavelength region.
[0043]
At this time, it is preferable that the difference in average grain projected area between emulsions is at least 1.25 times. More preferably, it is 1.4 times or more. Most preferably, it is 1.6 times or more. When three or more emulsions are used, it is preferable that the above relationship is satisfied between the emulsion having the smallest average grain projected area and the emulsion having the largest average grain projected area.
[0044]
In the present invention, in order to contain a plurality of emulsions having photosensitivity in these same wavelength regions and different average grain projected areas, a separate photosensitive layer may be provided for each emulsion, or one photosensitive layer. The above emulsions may be mixed and contained.
[0045]
When these emulsions are contained in separate layers, it is preferable to arrange an emulsion having a large average grain projected area in the upper layer (position close to the light incident direction).
[0046]
When these emulsions are contained in separate photosensitive layers, it is preferable to use color couplers having the same hue as the color couplers to be combined. It is also possible to use different couplers, or to use couplers having different absorption profiles of color hues for the respective photosensitive layers.
[0047]
In the present invention, when coating emulsions having photosensitivity in these same wavelength regions, emulsions having a larger average grain projected area in the ratio of the number of silver halide grains per unit area of the photosensitive material of these emulsions. It is preferable that the coating silver amount of the emulsion be larger than the ratio of the value obtained by dividing the silver halide grains contained in the emulsion by the 3/2 power of the average grain projected area. By adopting such a configuration, an image having good graininess can be obtained even under development conditions heated to a high temperature. Moreover, high developability and a wide exposure latitude can be satisfied at the same time.
[0048]
The dye constituting the present invention and decolorized by reaction with a nucleophile during development processing will be described.
The dye constituting the present invention is decolored by reaction with a nucleophile during development processing, and has diffusion resistance. Further, the dye constituting the present invention has at least a part of diffusion resistance even when the color is erased after the development processing. By using such a dye, it is possible to provide a photosensitive material which is excellent in storage stability, sharpness and graininess, and which can be easily and rapidly processed. Moreover, since unnecessary things are not taken out from the photosensitive material, it is preferable from the viewpoint of environment.
Specific examples of such dyes include cyanines, merocyanines, oxonols, arylidenes (including heteroarylidenes), anthraquinones, triphenylmethanes, azo dyes, azomethine dyes, and the like. Can do.
[0049]
Preferable dyes used in the present invention are those represented by the following general formulas (I) to (IV).
Formula (I)
A51 = L51− (L52 = L53) _m51 -Q51
Formula (II)
A51 = L51− (L52 = L53) _n51 -A52
Formula (III)
A51 (= L51-L52) _p51 = B51
Formula (IV)
(NC) ₂ C = C (CN) -Q51
In the formula, A51 and A52 each represent an acidic nucleus, B51 represents a basic nucleus, and Q51 represents an aryl group or a heterocyclic group. L51, L52, and L53 each represent a methine group, m51 represents 0, 1 or 2, and n51 and p51 each represents 0, 1, 2 or 3. However, the compounds represented by the general formulas (I) to (IV) do not have a carboxyl group or a sulfo group. The compounds represented by the general formulas (I) to (IV) have a diffusion-resistant group, and the processed (decolored) product is also diffusion-resistant and does not substantially elute from the photosensitive material. It is. Furthermore, the compounds represented by the general formulas (I) to (IV) do not have a group that causes an oxidation-reduction reaction at the time of treatment and subsequently breaks the bond and splits into a plurality of molecules.
[0050]
The acidic nucleus represented by A51 or A52 is preferably a cyclic ketomethylene compound or a compound having a methylene group sandwiched between electron-withdrawing groups. Examples of cyclic ketomethylene compounds include 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolo Examples include pyridine, hydroxypyridine, pyrazolidinedione, 2,5-dihydrofuran-2-one, and pyrrolin-2-one. These may have a substituent. Among these, preferred compounds are 2-pyrazolin-5-one, isoxazolone, dioxopyrazolopyridine, hydroxypyridine and pyrazolidinedione, and particularly preferred are 2-pyrazolin-5-one, isoxazolone and hydroxypyridine. It is.
[0051]
A compound having a methylene group sandwiched between electron-withdrawing groups is Z51-CH. ₂ -Z52, where Z51 and Z52 are -CN and -SO, respectively. ₂ R51, -COR51, -COOR51, -CON (R52) ₂ , -SO ₂ N (R52) ₂ , -C [= C (CN) ₂ ] R51, -C [= C (CN) ₂ ] N (R51) ₂ R51 represents an alkyl group, an aryl group, or a heterocyclic group, and R52 represents a hydrogen atom or a group exemplified for R51. R51 and R52 may each have a substituent, and when there are a plurality of R51 or R52 in the molecule, they may be the same or different. Z51 and Z52 may be the same.
[0052]
Examples of the basic nucleus represented by B51 include pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole, benzimidazole, benzothiazole, oxazoline, naphthoxazole, and pyrrole. Each of these may have a substituent. Among these, preferred compounds are indolenine, benzoxazole, benzimidazole, benzothiazole, and pyrrole, and particularly preferred are indolenine and benzoxazole.
Examples of the aryl group represented by Q51 include a phenyl group and a naphthyl group, each of which may have a substituent (preferably an electron donating group). Of these, a dialkylamino group, a hydroxyl group, an alkoxy group, and a phenyl group substituted with an alkyl group are preferred, and a phenyl group substituted with a dialkylamino group is particularly preferred.
Examples of the heterocyclic group represented by Q51 include pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran. Oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, and chroman, each of which may have a substituent. Of these, pyrrole and indole are preferred.
[0053]
The methine group represented by L51, L52, or L53 may have a substituent, and the substituents may be linked to each other to form a 5- or 6-membered ring (for example, cyclopentene, cyclohexene).
Substituents that the above-mentioned groups may have include sulfonamide groups (eg methanesulfonamide, benzenesulfonamide, octanesulfonamide), sulfamoyl groups (eg sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl). Moyl), sulfonylcarbamoyl groups (eg methanesulfonylcarbamoyl, benzenesulfonylcarbamoyl), acylsulfamoyl groups (eg acetylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), chain or cyclic alkyl groups (eg Methyl, isopropyl, cyclopropyl, cyclohexyl, 2-ethylhexyl, dodecyl, octadecyl, 2-phenethyl, benzyl), alkenyl groups (eg vinyl, allyl), alkoxy groups (eg Xyl, octyloxy, dodecyloxy, 2-methoxyethoxy), aryloxy groups (eg phenoxy), halogen atoms (eg F, Cl, Br), amino groups (eg amino, diethylamino, ethyldodecylamino), ester groups (eg Ethoxycarbonyl, octyloxycarbonyl, 2-hexyldecyloxycarbonyl), acylamino groups (eg acetylamino, pivaloylamino, benzoylamino), carbamoyl groups (eg unsubstituted carbamoyl, ethylcarbamoyl, diethylcarbamoyl, phenylethylcarbamoyl), aryl groups (Eg phenyl, naphthyl), alkylthio groups (eg methylthio, octylthio), arylthio groups (eg phenylthio, naphthylthio), acyl groups (eg acetyl, Azoyl, pivaloyl), sulfonyl groups (eg methanesulfonyl, benzenesulfonyl), ureido groups (eg 3-propylureido, 3,3-dimethylureido), urethane groups (eg methoxycarbonyl, butoxycarbonyl), cyano groups, hydroxyl groups, nitro Group, heterocyclic group (for example, benzoxazole ring, pyridine ring, sulfolane ring, furan ring, pyrrole ring, pyrrolidine ring, morpholine ring, piperazine ring, pyrimidine ring) and the like.
[0054]
The dye used in the present invention is preferably one represented by the general formula (I), (II) or (III), more preferably one represented by the general formula (I) or (III). Particularly preferred are those represented by the general formula (I).
Although the specific example of the pigment | dye used for this invention below is shown, this invention is not limited to these.
[0055]
[Chemical 1]

[0056]
[Chemical 2]

[0057]
[Chemical 3]

[0058]
[Formula 4]

[0059]
[Chemical formula 5]

[0060]
[Chemical 6]

[0061]
[Chemical 7]

[0062]
[Chemical 8]

[0063]
[Chemical 9]

[0064]
[Chemical Formula 10]

[0065]
Embedded image

[0066]
Embedded image

[0067]
Embedded image

[0068]
Embedded image

[0069]
Examples of the dye used in the present invention include International Patents WO88 / 04794, European Patents EP274723, 276,556, 299,435, U.S. Patents 2,527,583, 3,486,897, 3,746,539, 3,933,798, 4,130,429, 4,040,841, JP-A-48-68,623, 52-92,716, 55-155,350, 55-155,351, 61-205,934, JP-A-2-173,630, 2-230,135, 2-277,044, 2 -282,244, 3-7,931, 3-167,546, 3-13,937, 3-206,443, 3-208,047, 3-192 No. 157, No. 3-216,645 3-274,043, 4-37,841, 4-45,436, 4-138,449, 5-197,077, Japanese Patent Application No. 5-273,811 It can be synthesized according to the method described in JP-A-6-7,761 and JP-A-6-155,727 or the like.
[0070]
The above-mentioned dyes in the present invention can be used in a yellow filter layer, a magenta filter layer, and an antihalation layer. Accordingly, for example, when the photosensitive layer is provided in the order of the red photosensitive layer, the green photosensitive layer, and the blue photosensitive layer from the side closest to the support, the yellow filter layer and the green photosensitive layer are interposed between the blue photosensitive layer and the green photosensitive layer. A magenta filter layer can be provided between the layer and the red photosensitive layer, and a cyan filter layer (antihalation layer) can be provided between the red photosensitive layer and the support. The amount of the dye used is such that the transmission density of each layer is 0.03 to 3.0, more preferably 0.1 to 2.0 with respect to blue, green and red light, respectively. Specifically, depending on the ε and molecular weight of the dye, 0.005 to 2 mmol / m. ² May be used, and more preferably 0.05 to 1 mmol / m. ² It is.
[0071]
The light-sensitive material of the present invention may be used by mixing two or more dyes in one layer. For example, three kinds of dyes of yellow, magenta and cyan can be mixed and used in the above-mentioned antihalation layer.
The light-sensitive material of the present invention is used in a state where oil droplets obtained by dissolving a decolorable dye in oil and / or an oil-soluble polymer are dispersed in a hydrophilic binder. As the preparation method, an emulsification dispersion method is preferable, and for example, a method described in US Pat. No. 2,322,027 can be used. In this case, U.S. Pat. Nos. 4,555,470, 4,536,466, 4,587,206, 4,555,476, 4,599,296, and JP-B 3-62. , 256 and the like can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. Two or more high boiling point oils can be used in combination. In addition, an oil-soluble polymer can be used in place of or in combination with oil, and an example thereof is described in PCT International Publication No. WO 88/00723. The amount of the high-boiling oil and / or polymer is 0.01 g to 10 g, preferably 0.1 g to 5 g, based on 1 g of the dye used.
In addition, as a method of dissolving the dye in the polymer, a latex dispersion method can be used. Specific examples of the process and latex for impregnation include US Pat. No. 4,199,363, West German Patent Publication (OLS) 2 No. 5,541,274, No. 2,541,230, Japanese Examined Patent Publication No. 53-41,091 and European Patent Publication No. 029,104.
[0072]
When dispersing oil droplets in a hydrophilic binder, various surfactants can be used. For example, the surfactants described in JP-A-59-157,636, pages 37 to 38, and publicly known technology No. 5 (published on March 22, 1991, Aztec Co., Ltd.) pages 136 to 138 can be used. Further, phosphate ester type surfactants described in Japanese Patent Application Nos. 5-204,325 and 6-19,247 and West German Published Patent No. 932,299A can also be used.
As the hydrophilic binder, a water-soluble polymer is preferable. Examples include gelatin, proteins of gelatin derivatives, or natural compounds such as polysaccharides such as cellulose derivatives, starch, gum arabic, dextrin, pullulan, and synthetic polymer compounds such as polyvinyl alcohol, polyvinyl pyrrolidone, and acrylamide polymers. . Two or more of these water-soluble polymers can be used in combination. A combination with gelatin is particularly preferred. The gelatin may be selected from so-called demineralized gelatin with a reduced content of lime-processed gelatin, acid-processed gelatin, calcium and the like according to various purposes, and can also be used in combination.
[0073]
In the present invention, the dye is decolorized during processing by reaction with a nucleophile.
Nucleophiles include alcohols or phenols (R51OH), amines or anilines ((R52) _Three N), hydroxylamines ((R52) ₂ NOR52), sulfinic acids (R51SO) ₂ H), sulfurous acid, thiosulfuric acid, carboxylic acids (R51CO ₂ H), hydrazines ((R52) ₂ NN (R52) ₂ ), Guanidines ([(R52) ₂ N] ₂ C = NH), aminoguanidines ((R52) ₂ NR52N (R52N) C = NH), amidines, thiols (R51SH), cyclic or chain active methylene compounds (Z53-CH ₂ -Z54, wherein Z53 and Z54 have the same meanings as Z51 and Z52, and Z53 and Z54 may combine to form a ring), a cyclic or chain active methine compound (Z53-CH (R51) -Z54 or Z53-CH (Z54) -Z55, wherein Z55 is synonymous with Z53, and Z53, Z54 and Z55 (or R51) may be bonded to each other to form a ring), and these compounds And anionic species.
Of these, hydroxylamines, sulfinic acids, sulfurous acid, guanidines, aminoguanidines, heterocyclic thiols, cyclic or chain-like active methylene, and active methine compounds are preferred, and guanidines and aminoguanidines are particularly preferred. It is kind.
These nucleophiles may be added to the photosensitive material from the beginning, or may be added to the photosensitive material by any method during processing. Moreover, you may add what was made into the precursor as a form of the nucleophile at the time of addition.
[0074]
The above nucleophile contacts and reacts with the dye during processing to decolorize the dye. Preferably, the silver halide photosensitive material containing a dye is heated in the presence of water and a processing member containing a dye decolorizer precursor after imagewise exposure or simultaneously with the imagewise exposure, and then both are peeled off, A color image is obtained on the silver halide light-sensitive material, and at the same time, the dye is decolored. In this case, the decoloring ratio is 1/3 or less of the original density, preferably 1/5 or less. The amount of the nucleophile used is 0.1 to 200 times mol, preferably 0.5 to 100 times mol of the dye.
[0075]
In a color negative film that has been used in conventional photography, a compound that inhibits development during a coupling reaction with an oxidizing agent of a developing agent while improving the silver halide emulsion to achieve the desired granularity. Technology such as the use of so-called DIR couplers that release benzene has been incorporated. In the light-sensitive material of the present invention, excellent granularity can be obtained even when no DIR coupler is used. Furthermore, if a DIR compound is combined, the granularity becomes more and more excellent.
[0076]
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. Acetylene silver described in US Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination.
The above organic silver salt can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of photosensitive silver halide. The total coating amount of photosensitive silver halide and organic silver salt is 0.05 to 10 g / m in terms of silver. ² , Preferably 0.1 to 4 g / m ² Is appropriate.
[0077]
A hydrophilic material is preferably used for the binder of the constituent layer of the light-sensitive material of the present invention. Examples thereof include the research disclosure described above and those described in 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.) Sumitagel 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. The gelatin may be selected from so-called demineralized gelatin with a reduced content of lime-processed gelatin, acid-processed gelatin, calcium and the like according to various purposes, and is preferably used in combination.
In the present invention, the amount of binder applied is 1 m. ² It is preferably 1 g or more and 20 g or less, and particularly preferably 2 g or more and 10 g or less.
[0078]
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, JP-A-58-123,533, 58-149,046, 58-. 149,047, 59-111,148, 59-124,399, 59-174,835, 59-231,539, 59-231,540, 60-2, No. 950, No. 60-2,951, No. 60-14,242, No. 60-23,474, No. 60-66,249, No. 8-110,608, No. 8-146,552 No. 8-146,578 and the like.
[0079]
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, claim 1 of Japanese Patent Application No. 4-134523 Couplers represented by general formula (I): couplers represented by general formula D in lines 45 and 55 in column 1 of US Pat. No. 5,066,576, and general formula D in paragraph 0008 of JP-A-4-274,425. Coupler represented: coupler of claim 1 on page 40 of EP498,381A1, coupler of formula (Y) on page 4 of EP447,969A1, columns 7, 36, 58 of US Pat. No. 4,476,219 Couplers represented by formulas (I) to (IV).
Magenta couplers: couplers described in JP-A-3-39,737, JP-A-6-43,611, JP-A-5-204,106, and JP-A-4-3,626.
Cyan couplers: JP-A-4-204,843, JP-A-4-43,345, and Japanese Patent Application No. 4-23,633.
Polymer coupler: JP-A-2-44,345.
[0080]
As couplers in which the coloring dye has an appropriate diffusibility, those described in US Pat. No. 4,366,237, GB 2,125,570, EP 96,570, DE 3,234,533 are preferable.
[0081]
Further, the photosensitive material of the present invention may contain the following functional coupler. Couplers for correcting unwanted 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 US Pat. No. 4,833,069, US Pat. No. 4,837,136 (2), colorless masking coupler represented by formula (A) in claim 1 of WO 92/11575 (especially exemplary compounds on pages 36 to 45).
[0082]
In the present invention, it is preferable to use a coupler or other compound that releases a photographically useful compound by reaction with an oxidized form of a developing agent.
Examples of compounds (including couplers) that react with oxidized developing agent to release a photographically useful compound residue include the following. Development inhibitor releasing compounds: compounds represented by formulas (I) to (IV) described on page 11 of EP 378,236A1, compounds represented by formula (I) described on page 7 of EP 436,938A2, Compounds represented by formula (1) of No. 5-307248, compounds represented by formulas (I), (II) and (III) described on pages 5 and 6 of EP440, 195A2, and claims of JP-A-6-59411 Compound represented by formula (I) of item 1-ligand releasing compound, compound represented by LIG-X according to claim 1 of US 4,555,478.
[0083]
In the present invention, the amount of coupler used is preferably 1/1000 mol to 1 mol, more preferably 1/500 mol to 1/5 mol, per mol of silver halide.
[0084]
In the light-sensitive material of the present invention, it is necessary to incorporate a developing agent capable of forming a dye by coupling an oxidant produced by silver development with the above-mentioned coupler.
In this case, US Pat. No. 3,531,256 includes a p-phenylenediamine developing agent and a phenol or active methylene coupler, and US Pat. No. 3,761,270 includes a p-aminophenol developing agent and an active methylene coupler. Combinations can be used.
A combination of a sulfonamide phenol and a 4-equivalent coupler as described in U.S. Pat. No. 4,021,240, JP-A-60-128,438 is excellent in raw storage when incorporated in a photosensitive material. This is a preferable combination.
When a developing agent is incorporated, a color developing agent precursor may be used. For example, indoaniline compounds described in US Pat. No. 3,342,597, Schiff base compounds described in US Pat. No. 3,342,599, Research Disclosure No. 14,850 and No. 15,159, and 13,924 And alkane compounds of the above, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135,628.
[0085]
In addition, the sulfonamide phenol main agent described in Japanese Patent Application No. 7-180,568, and the combination of a hydrazine main agent described in Japanese Patent Application Nos. 7-49,287 and 7-63,572 and a coupler are also present. Preferred for use in the light-sensitive material of the invention.
[0086]
In the present invention, it is preferable to use a compound represented by the general formula ID, IID, IIID or IVD as a developing agent to be contained in the photosensitive material. Of these, compounds of general formula ID or IID are particularly preferably used.
These developing agents will be described in detail below.
[0087]
Embedded image

[0088]
Embedded image

[0089]
Embedded image

[0090]
Embedded image

[0091]
Where R ₁ ~ R _Four Is a hydrogen atom, halogen atom, alkyl group, aryl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylcarbamoyl group, Arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyl group, arylcarbonyl group or Represents an acyloxy group, R _Five Represents an alkyl group, an aryl group or a heterocyclic group. Z represents an atomic group forming a (hetero) aromatic ring. When Z is a benzene ring, the total value of Hammett constants (σ) of the substituents is preferably 1 or more. R ₆ Represents an alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom, or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ₇ , R ₈ Represents a hydrogen atom or a substituent, and R ₇ , R ₈ May be bonded to each other to form a double bond or a ring. Further, each of the general formulas ID to IVD includes at least one ballast group having 8 or more carbon atoms in order to impart oil solubility to the molecule.
[0092]
The compound represented by the general formula ID is a compound generically called sulfonamidophenol, and is a compound known in the art. When used in the present invention, the substituent R ₁ ~ R _Five Those having at least one ballast group having 8 or more carbon atoms are preferred.
[0093]
Where R ₁ ~ R _Four Is a hydrogen atom, halogen atom (eg, chloro group, bromine group), alkyl group (eg, methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group), aryl group (eg, phenyl group, tolyl group, xylyl group) Group), alkylcarbonamide group (eg acetylamino group, propionylamino group, butyroylamino group), arylcarbonamide group (eg benzoylamino group), alkylsulfonamide group (eg methanesulfonylamino group, ethanesulfonylamino group) , Arylsulfonamide groups (eg benzenesulfonylamino group, toluenesulfonylamino group), alkoxy groups (eg methoxy group, ethoxy group, butoxy group), aryloxy groups (eg phenoxy group), alkylthio groups (eg methylthio group, ethylthio group) The Ruthio group), arylthio group (for example, phenylthio group, tolylthio group), alkylcarbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), Arylcarbamoyl groups (eg, phenylcarbamoyl groups, methylphenylcarbamoyl groups, ethylphenylcarbamoyl groups, benzylphenylcarbamoyl groups), carbamoyl groups, alkylsulfamoyl groups (eg, methylsulfamoyl groups, dimethylsulfamoyl groups, ethylsulfamoyl groups) Moyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamo Group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group) ), Arylsulfonyl groups (for example, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl groups (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl groups (for example, phenoxycarbonyl group) Group), alkylcarbonyl group (for example, acetyl group, propionyl group, butyroyl group), arylcarbonyl group (for example, benzoyl group, alkylbenzoyl group), or acyloxy group (for example, For example, acetyloxy group, propionyloxy group, butyroyloxy group). R ₁ ~ R _Four In R ₂ And R _Four Is preferably a hydrogen atom. R ₁ ~ R _Four The sum of the Hammett constant σp values is preferably 0 or more. R _Five Is an alkyl group (for example, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group, stearyl group), aryl group (for example, phenyl group, tolyl group, xylyl group, 4-methoxyphenyl group, dodecylphenyl group, It represents a chlorophenyl group, a trichlorophenyl group, a nitrochlorophenyl group, a triisopropylphenyl group, a 4-dodecyloxyphenyl group, a 3,5-di- (methoxycarbonyl) group, or a heterocyclic group (for example, a pyridyl group).
[0094]
The compound represented by the general formula IID is a compound generically called carbamoyl hydrazine. Both are known compounds in the art. When used in the present invention, R _Five Or what has a C8 or more ballast group in the substituent of a ring is preferable.
[0095]
In the formula, Z represents an atomic group forming a (hetero) aromatic ring. The (hetero) aromatic ring formed by Z is required to be sufficiently electron withdrawing in order to impart silver developing activity to the present compound. For this reason, an aromatic ring in which a nitrogen-containing aromatic ring is formed or an electron-withdrawing group is introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring and the like are preferable. In the case of a benzene ring, examples of the substituent include alkylsulfonyl groups (for example, methanesulfonyl group and ethanesulfonyl group), halogen atoms (for example, chloro group and bromo group), alkylcarbamoyl groups (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethyl). Carbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidinecarbamoyl group, morpholinocarbamoyl group), arylcarbamoyl group (eg phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfuryl group Famoyl group (eg methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group) Group, piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group) , Sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (for example, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl) Group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, propionyl group, butyroyl group), or Reel carbonyl group (e.g. a benzoyl group, an alkyl benzoyl group), but like the sum of the Hammett constants σ values of the substituents is preferably of 1 or more.
[0096]
The compounds represented by the general formula IIID are compounds collectively called carbamoylhydrazone. The compound represented by the general formula IVD is a compound generically called sulfonylhydrazine. Both are known compounds in the art. When used in the present invention, R _Five ~ R ₈ Those having at least one ballast group having 8 or more carbon atoms are preferred.
[0097]
Where R ₆ Represents an alkyl group (for example, a methyl group or an ethyl group). X represents an oxygen atom, a sulfur atom, a selenium atom, or an alkyl-substituted or aryl-substituted tertiary nitrogen atom, preferably an alkyl-substituted tertiary nitrogen atom. R ₇ , R ₈ Represents a hydrogen atom or a substituent (those exemplified as the substituent of the benzene ring of Z can be exemplified as the above), R ₇ , R ₈ May be bonded to each other to form a double bond or a ring.
Of the compounds represented by the general formulas ID to IVD, ID and IID compounds are particularly preferred in the present invention from the viewpoint of raw preservation.
[0098]
R in the above ₁ ~ R ₈ Each of the groups includes those having possible substituents, and examples of the substituent include those listed as substituents on the benzene ring of Z.
Specific examples of the compounds represented by the general formulas ID to IVD are shown below, but the compounds of the present invention are not limited thereto.
[0099]
Embedded image

[0100]
Embedded image

[0101]
Embedded image

[0102]
Embedded image

[0103]
Embedded image

[0104]
Embedded image

[0105]
Embedded image

[0106]
Embedded image

[0107]
Embedded image

[0108]
Embedded image

[0109]
Embedded image

[0110]
The above compounds can be synthesized by generally known methods. The following is a list of simple synthesis routes.
[0111]
Embedded image

[0112]
Embedded image

[0113]
Embedded image

[0114]
When a diffusion-resistant developing agent is used in the present invention, an electron transfer agent and / or an optional agent may be used to promote electron transfer between the diffusion-resistant developing agent and the developable silver halide. An electron transfer agent 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, in the present invention, various reducing agents can be used for various purposes such as prevention of color mixing and improvement of color reproduction in the intermediate layer and the protective layer. 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.
[0115]
In the present invention, it is also possible to use a developing agent precursor which does not itself have a reducing property but develops a reducing property by the action of a nucleophile or heat in the development process.
In addition, the following reducing agent may be incorporated in the photosensitive material.
Examples of the reducing agent that can be used in the present invention include U.S. Pat. No. 4,500,626, columns 49-50, 4,839,272, 4,330,617, and 4,590. , 152, 5,017,454, 5,139,919, JP-A-60-140,335, pages (17)-(18), 57-40,245, 56 -138,736, 59-178,458, 59-53,831, 59-182,449, 59-182,450, 60-119,555, 60-128 No. 436, No. 60-128,439, No. 60-198,540, No. 60-181,742, No. 61-259,253, No. 62-244,044, No. 62-131,253 No. 62-131,256, No. 64-13,546 The (40) - (57) pages, JP 1-120,553, a reducing agent or a reducing agent precursor of pp 78-96, etc. European Patent No. 220,746A2.
Also, combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can be used.
The developing agent or the reducing agent may be incorporated in a processing sheet described later, or may be incorporated in the photosensitive material.
In the present invention, the total amount of the developing agent and the reducing agent is 0.01 to 20 mol, particularly preferably 0.01 to 10 mol, per 1 mol of silver.
[0116]
In the present invention, as the coupler, a 4-equivalent coupler and a 2-equivalent coupler can be properly used depending on the kind of the main agent. First, a 4-equivalent coupler is used for the developing agent of the general formula ID. In the developing agent of the general formula ID, the coupling site is substituted with a sulfonyl group, and this sulfonyl group is released as sulfinic acid at the time of coupling. Therefore, the leaving group on the coupler side must be removed as a cation. Therefore, it reacts with a 4-equivalent coupler capable of releasing a proton as a leaving group during coupling, but does not react with a 2-equivalent coupler in which the leaving group is an anion. Conversely, 2-equivalent couplers are used for developing agents of general formulas IID and IIID. In the developing agents of the general formulas IID and IIID, the coupling site is substituted by a carbamoyl group, and the hydrogen atom on the nitrogen atom is released as a proton during coupling, so the leaving group on the coupler side must be released as an anion. I must. Therefore, it reacts with a 2-equivalent coupler capable of releasing an anion as a leaving group during coupling, but does not react with a 4-equivalent coupler whose leaving group is a proton. By using this combination, it is possible to prevent the color from being blurred due to the interlayer movement of the oxidized oxidant of the developing agent. Specific examples of couplers include both 4-equivalent and 2-equivalent theories of the photographic process (edited by 4th Ed. THJames, Macmillan, 1977), pages 291 to 334, and pages 354 to 361. Sho 58-12,353, 58-149,046, 58-149,047, 59-11,114, 59-124,399, 59-174,835, 59 -231,539, 59-231,540, 60-2,951, 60-14,242, 60-23,474, 60-66,249 and the above-mentioned references It is described in detail in the publication.
[0117]
Hydrophobic additives such as couplers, 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 hydrophobic additive used. Further, 1 cc or less, further 0.5 cc or less, particularly 0.3 cc or less is appropriate for 1 g of binder.
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.
Various surfactants are used to disperse hydrophobic compounds in hydrophilic colloids.
Can. For example, the surfactants described in Research Disclosure, pages (37) to (38) of JP-A-59-157636 can be used. Further, phosphate ester type surfactants described in JP-A Nos. 7-56,267 and 7-228,589 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.
[0118]
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, etc. can be provided.
[0119]
As the dye that can be used in the yellow filter layer and the antihalation layer, dyes that are decolored or eluted during development and do not contribute to the density after processing are preferable.
The fact that the dye of the yellow filter layer and the antihalation layer is decolored or removed during development means that the amount of the dye remaining after processing is 1/3 or less immediately before coating, preferably 1/10 or less, The dye component may be eluted from the light-sensitive material or transferred into the processing material during development, or may be changed to a colorless compound upon reaction during development.
[0120]
The light-sensitive material of the present invention is 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), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid or polymer hardeners (compounds described in JP-A-62-234157, etc.). These hardeners are used in an amount of 0.001-1 g, preferably 0.005-0.5 g, per 1 g of hydrophilic binder.
[0121]
In the light-sensitive material of the present invention, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples thereof include the Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A Nos. 64-13,564 (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 ^-1 Moles are preferred, further 1 × 10 ^-Five ~ 1x10 ^-2 Mole is preferably used.
[0122]
In the photosensitive material of the present invention, in order to form an image after imagewise exposure, the exposed photosensitive material and a processing material containing a base and / or a base precursor on a support are mixed with the photosensitive material. The photosensitive layer surface and the processing layer surface of the processing material are bonded together and thermally developed to form an image. Color development is performed by supplying water equivalent to 1/10 to 1 times the water required for maximum swelling of all coating films constituting the photosensitive material and processing material during development to the photosensitive material or processing material, followed by heating. Although the method to perform is used preferably, this invention is not limited by this. Further, a method of incorporating a developing agent in a photosensitive material or a processing material as required is preferably used, but the present invention is not limited thereto.
[0123]
The light-sensitive material of the present invention can be used without fixing unreacted silver halide during processing. In this case, a color image is formed on the photosensitive material side, but the silver halide remains. In other words, when the photosensitive material is used while leaving the remaining silver halide, the photosensitive material containing the tabular high silver chloride emulsion composed of the (100) plane or the (111) plane of the present invention is used for other halogens. An image quality excellent in sharpness can be obtained by itself as compared with a light-sensitive material containing silver halide, but further excellent sharpness can be obtained when used in combination with a coloring dye having a specific structure of the present invention.
[0124]
The present invention was made for the purpose of achieving good graininess, exposure latitude and improvement in sharpness in the thermal development as described above, and aims to reduce the environmental burden caused by liquid development. However, it is also possible to form an image by developing the photosensitive material of the present invention with an activator processing using an alkaline processing solution or a processing solution containing a developing agent / base.
[0125]
The heat treatment of the light-sensitive material of the present invention is known in the art, and the heat-developable light-sensitive material and the process thereof are described, for example, in photographic engineering basics (1970, issued by Corona), pages 553 to 555, 1978. April issue video information 40 pages, Nabletts Handbook of Photography and Reprography 7th Ed. (Vna Nostrand and Reinhold Company) pages 32 to 33, US Pat. Nos. 3,152,904, 3,301,678, 3,392,020, 3,457,075, British Patents 1,131,108, 1,167,777, and Research Disclosure, June 1978, pages 9-15 (RD) -17029).
[0126]
Activator processing refers to a processing method in which a color developing agent is incorporated in a photosensitive material, and development processing is performed with a processing solution that does not contain a color developing agent. The processing solution in this case is characterized by not containing the color developing agent contained in the usual developing processing solution components, and may contain other components (for example, alkali, auxiliary developing agent, etc.). The activator treatment is exemplified in known documents such as European Patent Nos. 545,491A1 and 565,165A1.
[0127]
A method of developing with a processing solution containing a developing agent / base is described in RD. No. 17, 643, pages 28-29, No. 18, 716, left column to right column, and No. 307, 105, pages 880-881.
Next, a processing material and a processing method used in the case of heat development processing in the present invention will be described in detail.
[0128]
In the light-sensitive material of the present invention, a base or a base precursor is preferably used for the purpose of accelerating silver development and a dye-forming reaction. 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, Rossen 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, etc. Has been. Further, as described in European Patent Publication No. 210,660 and U.S. Pat. No. 4,740,445, which will be described later, a basic metal compound hardly soluble in water and a metal ion constituting the basic metal compound, A method may be used in which a base is generated by a combination of compounds capable of complex-forming reaction using water as a medium (referred to as complex-forming compounds).
The amount of base or base precursor used is 0.1 to 20 g / m. ² , Preferably 1-10 g / m ² It is.
[0129]
A thermal solvent may be added to the light-sensitive material of the present invention 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 Sorbitols) 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.
The heating temperature in the heat development step is about 50 ° C. to 250 ° C., but 60 ° C. to 150 ° C. is particularly useful.
[0130]
In order to supply the base required in the heat development process, a processing material having a processing layer containing a base or a base precursor is used. In addition to these processing materials, air is shut off during heat development, volatilization of materials from the photosensitive material is prevented, processing materials other than bases are supplied to the photosensitive material, and photosensitive materials that become unnecessary after development. A material (YF dye, AH dye, etc.) in the material or an unnecessary component generated during development may be removed. As the support and binder for the processing material, those similar to the photosensitive material can be used.
A mordant may be added to the treatment material for the purpose of removing the above-mentioned dye and other purposes. As the mordant, those known in the photographic field can be used. US Pat. No. 4,500,626, columns 58 to 59, JP-A-61-88,256, pages 32-41, JP-A-62-244,043 And mordants described in JP-A-62-244,036. Further, a dye-accepting polymer compound described in US Pat. No. 4,463,079 may be used. Moreover, you may contain an above described thermal solvent.
[0131]
The treatment layer of the treatment material contains a base or a base precursor. As the base, either an organic base or an inorganic base may be used, and those described above may be used as the base precursor. The amount of base or base precursor used is 0.1 to 20 g / m. ² , Preferably 1-10 g / m ² It is.
[0132]
When heat development is performed using the processing material, a small amount of water is used for the purpose of promoting development, promoting transfer of the processing material, and promoting diffusion of unnecessary materials. Specific examples are described in U.S. Pat. Nos. 4,704,245, 4,470,445, and JP-A-61-238,056. Water may contain an inorganic alkali metal salt or organic base, a low-boiling solvent, a surfactant, an antifoggant, a complex-forming compound with a hardly soluble metal salt, an antifungal agent, or an antibacterial agent.
Any water can 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 processing material 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.
Water can be applied to the photosensitive material, the processing material, or both. The amount used is equivalent to 1/10 to 1 times the amount required to swell the entire coating film (excluding the back layer) of the photosensitive material and processing material.
As a method for imparting 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 the photosensitive material or the processing material or both of them can be incorporated in advance in the form of a hydrate.
The temperature of water to be applied may be 30 ° C. to 60 ° C. as described in JP-A-63-85,544.
[0133]
When heat development is performed in the presence of a small amount of water, as described in European Patent Publication 210,660 and US Pat. No. 4,740,445, a basic metal compound hardly soluble in water and its base It is effective to employ a method in which a base is generated by a combination of a metal ion constituting a conductive metal compound and a compound capable of complexing with water as a medium (referred to as a complex-forming compound). In this case, it is desirable in terms of raw storage stability to add a basic metal compound hardly soluble in water to the photosensitive material and a complex-forming compound to the processing material.
[0134]
Heating methods in the development process include contact with heated blocks and plates, contact with hot plates, hot presses, heat rollers, heat drums, halogen lamp heaters, infrared and far infrared lamp heaters, etc. There is a method of passing through the atmosphere.
The method described in JP-A-62-253,159 and JP-A-61-147,244 (27) can be applied as a method of superposing the photosensitive material and the processing material in such a manner that the photosensitive layer and the processing layer face each other. The heating temperature is preferably 70 ° C to 100 ° C.
[0135]
Any of various heat developing apparatuses can be used for processing a photographic element comprising the light-sensitive material 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, 6-164,421, 6-164,422 and the like are preferably used.
Moreover, as a commercially available apparatus, the Pictorostat 100 manufactured by Fuji Photo Film Co., Ltd., the same Pictrostat 200, the same Pictrostat 300, the same Pictrostat 330, the same Pictrostat 50, the same Pictography 3000, the same Pictography 2000, and the like can be used. .
[0136]
The photosensitive material and / or processing sheet of the present invention may have a form having a conductive heating element layer as a heating means for heat development. As the heat generating element of this heat generation, those described in JP-A-61-145,544 and the like can be used.
[0137]
The light-sensitive material of the present invention can remove developed silver in the light-sensitive material simultaneously with development, or can contain a silver oxidizing agent that acts as a bleaching agent in the processing material to cause these reactions during heat development. .
Further, the developed silver can be removed by laminating a second material containing a silver oxidant with the photosensitive material after completion of the image formation development.
However, it is preferable that the developed silver is not bleached during processing because the processing is simple.
[0138]
As a bleaching agent that can be used in the treatment material, a commonly used silver bleaching agent can be arbitrarily used. Such bleaches are described in US Pat. Nos. 1,315,464 and 1,946,640, and Photographic Chemistry ol2, chapter 30, Foundation Press London England. These bleaches effectively oxidize and solubilize photographic silver images. Examples of useful silver bleaches include alkali metal dichromates and alkali metal ferricyanides.
Preferred bleaching agents are those that are soluble in water and include ninhydrin, indandione, hexaketo chlorohexane, 2,4-dinitrobenzoic acid, benzoquinone, benzenesulfonic acid, 2,5-dinitrobenzoic acid. Also, there are metal organic complexes such as ferric salt of cyclohexyldialkylaminotetraacetic acid, ferric salt of ethylenediaminetetraacetic acid, and ferric salt of citric acid. Regarding the binder, support, and other additives that can be used for the second processing material, the same materials as the processing material (first processing material) for developing the photosensitive material can be used.
The amount of bleaching agent applied can be changed according to the amount of silver contained in the photosensitive material to be bonded.
Although it should be used, it is used in the range of 0.01 mol to 10 mol of the coated silver amount per unit area of the photosensitive material / the coated silver mol of the photosensitive material. Preferred is 0.1 to 3 mol / silver mole of coated photosensitive material, and more preferred is 0.1 to 2 mole / silver mole of coated photosensitive material.
[0139]
Both the first processing material and the second processing material can have at least one polymerizable timing layer. This polymerizable timing layer can temporarily delay the bleaching reaction until the desired reaction between the silver halide and the dye-donating compound or the developing agent is substantially completed. The timing layer can be made of gelatin, polyvinyl alcohol, or polyvinyl alcohol-polyvinyl acetate. This layer can also be a barrier timing layer as described, for example, in U.S. Pat. Nos. 4,056,394, 4,061,496, and 4,229,516.
When this timing layer is applied, it is applied with a film thickness of 5 to 50 microns, preferably 10 to 30 microns.
[0140]
In the present invention, as a method of bleaching the developed photosensitive material using the second processing material, the amount of 0 required to swell the entire coating film excluding the back layer of both the photosensitive material and the second processing material is maximized. After water equivalent to 1 to 1 time is given to the photosensitive material or the second processing material, the photosensitive material and the second processing material are overlapped with each other so that the photosensitive layer and the processing layer face each other. Heat at temperature for 5 to 60 seconds.
As for the amount of water, the type of water, the method for applying water, and the method for superposing the photosensitive material and the processing material, the same materials as those for the first processing material can be used.
[0141]
More specifically, bleaching sheets described in JP-A-59-136,733, US Pat. No. 4,124,398, and JP-A-55-28,098 can be used.
The light-sensitive material of the present invention does not fix unreacted silver halide after heat development, and uses it as a negative original while leaving unreacted silver halide substantially remaining on the light-sensitive material side, to a paper or the like. Is used to form an image.
In the present invention, “not fixing unreacted silver halide” means not having a fixing step as an additional step after heat development.
In the present invention, “substantially remaining unreacted silver halide” means that 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more of unreacted silver halide remains. Say letting go.
[0142]
In the present invention, it is preferable that the processing time from when the processing sheet and the film surface of the photosensitive material are superposed in the presence of water to when the both are peeled is within 30 seconds.
[0143]
In the light-sensitive material of the present invention, various surfactants can be used for the purpose of coating aids, peelability improvement, smoothness improvement, antistatic, development promotion and the like. Specific examples of the surfactant are disclosed in JP-A 62-173,463, 62-183,457, etc., in pages 136 to 138 of publicly known technology No. 5 (March 22, 1991, issued by Aztec Co., Ltd.). Are listed.
The photosensitive material of the present invention may contain an organic fluoro compound for the purpose of preventing slipping, preventing static charge, improving peelability, and the like. Representative examples of organic fluoro compounds include fluorine-based surface activity described in JP-B-57-9,053, columns 8 to 17, JP-A-61-20944, and 62-135,826. Or a hydrophobic fluorine compound such as an oily fluorine-based compound such as fluorine oil or a solid fluorine compound resin such as tetrafluoroethylene resin.
[0144]
The light-sensitive material of the present invention preferably has a slip property. The slip agent is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is 0.25 or less and 0.01 or more in terms of dynamic friction coefficient. The measurement at this time represents a value when transported at 60 cm / min for a stainless steel ball having a diameter of 5 mm (25 ° C., 60% RH). In this evaluation, even if the counterpart material is replaced with the photosensitive layer surface, the value is almost the same.
Usable slip agents include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, and polystyrylmethylsiloxane. Polymethylphenylsiloxane and the like can be used. As the additive layer, the outermost layer of the emulsion layer or the back layer is preferable. In particular, polydimethylsiloxane and esters having a long chain alkyl group are preferred.
[0145]
In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids, carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds.
The most preferable antistatic agents are ZnO and TiO. ₂ , SnO ₂ , Al ₂ O _Three , In ₂ O _Three , SiO ₂ , MgO, BaO, MoO _Three , V ₂ O _Five A volume resistivity of at least one selected from ⁷ Ω · cm or less, more preferably 10 ^Five Particle size of Ω · cm or less 0.001 to 1.0 μm Fine particles of crystalline metal oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.), and sol-like And metal oxides or composite oxides of these. The content in the photosensitive material is 5 to 500 mg / m. ² Is particularly preferable, 10 to 350 mg / m ² It is. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably 1/300 to 100/1, more preferably 1/100 to 100/5.
[0146]
The composition of the photosensitive material or processing sheet (including the back layer) contains various polymer latexes for the purpose of improving film physical properties such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention, pressure increase / decrease prevention, etc. It can be included. Specifically, any of polymer latexes described in JP-A Nos. 62-245,258, 62-136,648 and 62-110,066 can be used. In particular, if a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordanting layer, cracking of the mordanting layer can be prevented, and if a polymer latex having a high glass transition point is used for the back layer, an anti-curling effect can be obtained. can get.
[0147]
The light-sensitive material of the present invention preferably has a matting agent. The matting agent may be either the emulsion surface or the back surface, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and is preferably a combination of both. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, the particle size distribution is preferably narrow, and 90% or more of the total number of particles is preferably contained between 0.9 and 1.1 times the average particle size. . It is also preferable to add fine particles of 0.8 μm or less at the same time in order to improve the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio)) (0 0.3 μm), polystyrene particles (0.25 μm), and colloidal silica (0.03 μm). Specifically, it is described in JP-A 61-88,256 (page 29). In addition, there are compounds described in JP-A-63-274,944 and 63-274,952, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads. In addition, the compounds described in Research Disclosure can be used.
[0148]
In the present invention, as the support for the photosensitive material and the processing sheet, those capable of withstanding the processing temperature are used. Generally, papers and synthetic polymers (films) described in “Photographic Engineering Fundamentals-Silver Salt Photography Edition” edited by the Japan Photography Society, Corona Publishing Co., Ltd. (Showa 54) (223)-(240) ) And the like. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, and celluloses (for example, triacetyl cellulose).
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-63-3316,848, Supports described in Kaihei 2-22,651, 3-56,955, U.S. Pat. No. 5,001,033 and the like can be used.
[0149]
In particular, when the requirements for heat resistance and curl characteristics are severe, JP-A-6-41,281, 6-43,581, 6-51,426 and 6-51,437 are used as supports for photosensitive materials. 6-51,442, 6-82,961, 6-82,960, 6-123,937, 6-82,959, 6-67,346, 6-118,561, 6-266,050, 6-202,277, 6-175,282, 6-118,561, 7-219,129, 7 -219,144 can preferably be used. Further, a support which is a styrene polymer mainly having a syndiotactic structure can also be preferably used.
[0150]
Further, it is preferable to perform a surface treatment in order to bond the support and the photosensitive material constituting layer. Examples of the surface activation treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.
Next, regarding the undercoating method, a single layer or two or more layers may be used. As a binder for the undercoat layer, starting from a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Examples of compounds that swell the support include resorcin and p-chlorophenol. As the gelatin hardener for the undercoat layer, chromium salts (such as chromium alum), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine) Etc.), epichlorohydrin resins, active vinyl sulfone compounds and the like. SiO ₂ TiO ₂ Further, inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.
[0151]
Further, as the support, for example, JP-A-4-124,645, JP-A-5-40,321, JP-A-6-35,092, JP-A-5-58,221 and JP-A-6-317,875 are described. It is preferable to record photographic information and the like using a support having a magnetic recording layer.
[0152]
The magnetic recording layer is obtained by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder.
The magnetic particles are γFe ₂ O _Three Ferromagnetic iron oxide such as Co-coated γFe ₂ O _Three Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co-coated γFe ₂ O _Three Co-coated ferromagnetic iron oxide such as The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. SBET 20m in specific surface area ² / G or more is preferable, 30 m ² / G or more is particularly preferable. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ^Four ~ 3.0 × 10 ^Five A / m 2, particularly preferably 4.0 × 10 ^Four ~ 2.5 × 10 ^Five A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the magnetic particles may be treated on the surface with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161,032. Also, magnetic particles having a surface coated with inorganic or organic substances as described in JP-A-4-259,911 and 5-81,652 can be used.
[0153]
The binder used for the magnetic particles is a thermoplastic resin, thermosetting resin, radiation curable resin, reactive resin, acid, alkali or biodegradable polymer, natural product weight described in JP-A-4-219569. Combinations (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The Tg of the resin is -40 ° C to 300 ° C, and the weight average molecular weight is 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose derivatives such as cellulose acetate butyrate, cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of isocyanate-based crosslinking agents include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the like, and reaction products of these isocyanates with polyalcohol (for example, tolylene diene). Reaction products of 3 mol of isocyanate and 1 mol of trimethylolpropane) and polyisocyanates formed by condensation of these isocyanates are mentioned, for example, as described in JP-A-6-59,357.
[0154]
As a method for dispersing the above-mentioned magnetic particles in the binder, a kneader, a pin-type mill, an annular mill, etc. are preferable, as in the method described in JP-A-6-35092. A dispersant described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to 3 μm. The weight ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of the magnetic particle dispersion coating solution is 0.005 to 3 g / m as the weight of the magnetic particles. ² , Preferably 0.01-2 g / m ² More preferably, 0.02 to 0.5 g / m ² It is. The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50, more preferably 0.03 to 0.20, and particularly preferably 0.04 to 0.15. The magnetic recording layer can be provided on the entire surface or in a stripe shape on the back surface of the photographic support by coating or printing. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extraction, etc. can be used. The coating liquid described in 341,436 etc. is preferable.
[0155]
The magnetic recording layer may be provided with functions such as lubricity improvement, curling control, antistatic, adhesion prevention, head polishing, etc., or another functional layer may be provided to give these functions. It is preferable that at least one of the particles is an abrasive of non-spherical inorganic particles having a Mohs hardness of 5 or more. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as that for the magnetic recording layer is preferable. Photosensitive materials having a magnetic recording layer are described in US Pat. Nos. 5,336,589, 5,250,404, 5,229,259, 5,215,874, and EP466,130. .
[0156]
The polyester support preferably used for the photosensitive material having the magnetic recording layer described above will be further described. For details including photosensitive materials, processing, cartridges, and examples, publicly available technology, public technical number 94-6023 (Invention Association; 1994. 3.15). Polyester is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, as aromatic dicarboxylic acid, Examples of phthalic acid and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of this polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 mol% to 100 mol% of 2,6-naphthalenedicarboxylic acid. Of these, polyethylene-2,6-naphthalate is particularly preferred. The average molecular weight range is about 5,000 to 200,000. The Tg of the polyester is 50 ° C. or higher, more preferably 90 ° C. or higher.
[0157]
Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg, in order to make it difficult to cause curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 hours to 1500 hours, more preferably 0.5 hours to 200 hours. The heat treatment of the support may be performed in a roll shape or may be performed while being conveyed in a web shape. Provide unevenness on the surface (for example, SnO ₂ And Sb ₂ O _Five Or the like) may be applied to improve the surface condition. It is also desirable to devise measures such as preventing knurling of the core part by imparting knurls to the end part and slightly raising only the end part. These heat treatments may be carried out at any stage after the support film is formed, after the surface treatment, after the back layer is applied (antistatic agent, slip agent, etc.) and after the undercoat is applied, but preferably the antistatic agent is applied. Later.
This polyester may be kneaded with an ultraviolet absorber. In order to prevent light pumping, the purpose can be achieved by applying a dye or pigment commercially available for polyester, such as Mitsubishi Chemical's Diaresin or Nippon Kayaku's Kayaset.
[0158]
Next, a film cartridge that can be loaded with a photosensitive material will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic.
Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the cartridge may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations, and betaine surfactants or polymers can be preferably used. These antistatic cartridges are described in JP-A-1-312,537 and 1-312,538. Especially, the resistance at 25 ° C. and 25% RH is 10 ¹² Ω / □ or less is preferable. Usually, plastic patrone is manufactured using a plastic kneaded with carbon black or pigment to provide light shielding properties. The size of the cartridge may be the current 135 size, and it is also effective to reduce the diameter of a 25 mm cartridge of the current 135 size to 22 mm or less in order to reduce the size of the camera. The volume of the patrone case is 30cm. ^Three Below, further 25cm ^Three The following is preferable. The weight of the plastic used for the cartridge and the cartridge case is preferably 5 to 15 g.
[0159]
Further, a cartridge that feeds a film by rotating a spool may be used. Alternatively, the film leading end may be housed in the cartridge main body, and the film leading end may be sent out from the port portion of the cartridge by rotating the spool shaft in the film feeding direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613.
[0160]
In the present invention, developed silver and undeveloped silver halide produced by development are mainly intended to capture image information as digital data by a scanner or the like without removing them, but this is a conventional method. It is also possible to use the information obtained by optically exposing the printed information on a printing material such as color paper in an analog manner.
[0161]
In the present invention, it is possible to combine other methods for reducing the trouble of reading image information after photographing and subsequent image forming development. In particular, undeveloped silver halide causes high haze in the gelatin film and increases the background density of the image. Therefore, the silver halide used in the present invention is considered to have a remarkable effect of reducing the effect. However, the detailed mechanism of its action will be clarified in future studies.
[0162]
As methods for producing prints on color paper or photothermographic material using this color photographing material, the methods described in JP-A Nos. 5-241,251, 5-19,364 and 5-19,363 are used. Can be used.
[0163]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[0164]
Example 1
[0165]
A method for preparing silver iodobromide tabular emulsions (comparative) M-1, M-2 and M-3 will be described.
930 ml of distilled water containing 0.74 g of gelatin having an average molecular weight of 15,000 and 0.7 g of potassium bromide was placed in the reaction vessel, and the temperature was raised to 42 ° C. While stirring vigorously, 30 ml of an aqueous solution containing 1.2 g of silver nitrate and 30 ml of an aqueous solution containing 0.82 g of potassium bromide were added over 30 seconds. After maintaining the addition at 40 ° C. for 1 minute after the addition was completed, the temperature of the reaction solution was raised to 75 ° C. After adding 27.5 g of gelatin together with 200 ml of distilled water, 100 ml of an aqueous solution containing 22.5 g of silver nitrate and 80 ml of an aqueous solution containing 15.43 g of potassium bromide were added over 11 minutes while accelerating the addition flow rate.
[0166]
Next, 250 ml of an aqueous solution containing 75.1 g of silver nitrate and an aqueous solution containing potassium iodide in a molar ratio of 3:97 (potassium bromide concentration of 26%) were added while accelerating the flow rate and silver in the reaction solution. It added in 20 minutes so that an electric potential might be 2 mV with respect to a saturated calomel electrode. Further, 75 ml of an aqueous solution containing 18.7 g of silver nitrate and 21.9% aqueous solution of potassium bromide were added over 4 minutes so that the silver potential of the reaction solution was 0 mV with respect to the saturated calomel electrode. After maintaining the addition at 73 ° C. for 1 minute after the addition was completed, the temperature of the reaction solution was lowered to 55 ° C. Next, 120 ml of an aqueous solution containing 8.1 g of silver nitrate and 320 ml of an aqueous solution containing 7.26 g of potassium iodide were added over 5 minutes. After the addition was completed, 5.5 g of potassium bromide and 0.04 mg of potassium hexachloroiridate were added and kept at 55 ° C. for 1 minute. Further, 180 ml of an aqueous solution containing 44.3 g of silver nitrate and 160 ml of an aqueous solution containing 34.0 g of potassium bromide. Were added over 10 minutes. The temperature was lowered and desalting was performed according to a conventional method.
[0167]
The obtained emulsion was silver iodobromide composed of hexagonal tabular grains having an average equivalent circular diameter of 1.81 μm expressed by a circle-equivalent diameter and a ratio (aspect ratio) of the average grain diameter divided by the average grain thickness of 3.8. It was an emulsion (silver iodide content 5.7 mol%). This emulsion was designated as Emulsion M-1.
Emulsion M-1 was prepared by changing the initial amount of gelatin and the amount of potassium bromide to prepare grains having equivalent grain diameters of 1.21 μm and 0.76 μm, and were designated as emulsions M-2 and M-3. Emulsions M-2 and M-3 are used in Example 2.
[0168]
Next, a method for preparing cubic silver chloride emulsions (comparative) R-1, R-2 and R-3 will be described.
1000 ml of distilled water containing 30.0 g of decalcified gelatin (calcium content of 2,000 ppm or less), 2.4 g of sodium chloride and 15.0 ml of sulfuric acid (1N) was placed in a reaction vessel, and the temperature was raised to 59 ° C. To this solution, 1.9 ml of an aqueous solution of N, N′-dimethylimidazolidine-2-thione (1%) was added, and 2000 ml of an aqueous solution containing 7.1 g of silver nitrate and 200 ml of an aqueous solution containing 2.41 g of sodium chloride were vigorously stirred. Added in 24 minutes. Next, 500 ml of an aqueous solution containing 162.8 g of silver nitrate and 500 ml of an aqueous solution containing 59.88 g of sodium chloride were added over 80 minutes while accelerating the addition flow rate. When 60 minutes passed from the start of the addition of these reaction solutions, 0.04 mg of potassium hexachloroiridate was added. After maintaining the reaction solution for 5 minutes at 55 ° C., the temperature was lowered and desalting was performed according to a conventional method.
[0169]
The obtained emulsion was an emulsion composed of cubic grains having an average grain size of 0.73 μm represented by a diameter corresponding to a circle. This emulsion was designated as Emulsion R-1.
Emulsions R-2 and R-3 were prepared in exactly the same manner as Emulsion R-1, except that the temperature in the reaction vessel was 45 ° C. and 40 ° C., respectively. The average grain size of the obtained emulsion was 0.54 μm and 0.29 μm, respectively. Emulsions R-2 and R-3 are used in Example 2.
[0170]
Next, a method for preparing a high silver chloride tabular emulsion (invention) H-1, H-2, H-3 having a (100) plane will be described.
1,000 ml of distilled water containing 20.2 g of gelatin having an average molecular weight of 15,000, 0.81 g of sodium chloride and 8.8 ml of sulfuric acid (1N) was placed in a reaction vessel, and the temperature was raised to 35 ° C. While stirring vigorously, 30 ml of an aqueous solution containing 6.1 g of silver nitrate and 30 ml of an aqueous solution containing 2.00 g of sodium chloride and 0.21 g of potassium bromide were added over 45 seconds. Then, an aqueous solution containing 5.0 g of polyvinyl alcohol having an average degree of polymerization of 300 to 700 (Kuraray Co., Ltd. Kuraray Poval 105) was added. Next, 40 ml of an aqueous solution containing 0.55 g of potassium bromide was added. Further, 100 ml of an aqueous solution containing 18.3 g of silver nitrate and 100 ml of an aqueous solution containing 6.30 g of sodium chloride were added over 3 minutes. 6.0 ml of sodium hydroxide (1N) was added and the temperature of the reaction solution was raised to 75 ° C. After adding 10.0 g of gelatin together with 100 ml of distilled water, 750 ml of an aqueous solution containing 145.4 g of silver nitrate and a 7.0% aqueous solution of sodium chloride were added, and the silver potential of the reaction solution was adjusted to a saturated calomel electrode while accelerating the flow rate. It added over 45 minutes so that it might become 100 mV with respect to. After adding 0.04 mg of potassium hexachloroiridate and maintaining at 75 ° C. for 30 minutes, the temperature was lowered and desalting was performed according to a conventional method.
[0171]
The obtained emulsion was made of silver chlorobromide having a silver bromide content of 0.64 mol%, and had an average grain size of 0.67 μm expressed by a circle-equivalent diameter and an average diameter of a circle equivalent to the average grain projected area. It was a (100) silver chlorobromide emulsion composed of tabular grains having a ratio (aspect ratio) divided by the grain thickness of 7.1 and a projection plane having an average aspect ratio of 1: 1.25. This emulsion was designated as Emulsion H-1. Also, emulsions H-2 and H-3 having sphere equivalent average particle sizes of 0.50 μm and 0.31 μm, respectively, were prepared by adjusting the molecular weight and gelatin amount of gelatin used at the beginning of the reaction. The resulting emulsions H-2 and H-3 are used in Example 2.
[0172]
The spectral sensitization and chemical sensitization for emulsions M-1, M-2, M-3, R-1, R-2, R-3, H-1, H-2, and H-3 will be described. The following spectral sensitizing dyes I, II and III, Compound I, potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to these emulsions for spectral and chemical sensitization. At this time, the spectral sensitizing dye was changed in proportion to the grain surface area of each emulsion. The amounts of pAg and chemical sensitizer during chemical sensitization were adjusted so that the degree of chemical sensitization of each emulsion was optimized.
The green-sensitive emulsion thus prepared was expressed with a subscript g such as M-1g.
[0173]
Embedded image

[0174]
Next, a method for preparing high silver chloride tabular emulsions (invention) B-1, B-2, and B-3 comprising the (111) plane will be described.
[0175]
1,200 ml of an aqueous gelatin solution containing 2.1 g of deionized alkali-treated bone gelatin and 2 g of sodium chloride was placed in a reaction vessel, kept at 35 ° C., and intensively stirred into this solution, 1,100 ml of an aqueous solution containing 165 g of silver nitrate ( Solution A) and 1,100 ml of solution (B) containing 19.1 ml of an aqueous solution containing 59.1 g of sodium chloride were simultaneously added and mixed in 60 ml portions over 1 minute. 50 ml of an aqueous solution (C) containing 0.285 g of compound (3) was prepared, 40 ml of which was added, and 30 ml of a 10% aqueous sodium chloride solution was added 1 minute after the completion of the addition and mixing. Thereafter, the temperature was raised to 60 ° C. over 25 minutes, and after 16 minutes, 260 ml of an aqueous gelatin solution containing 29 g of phthalated gelatin was added, and after 3 minutes, 10 ml of solution (C) was added. 1 minute later, liquids (A) and (B) were 768 ml each, at an initial speed of 2.85 ml / min, and an acceleration of 0.818 ml / (min) ² At the same time. From 10 minutes before the end of addition and mixing of the liquid (A) and the liquid (B), the liquid (D), which is 270 ml of an aqueous solution containing 3.9 g of sodium chloride and 0.1 g of yellow blood salt, was added over 10 minutes. . Further, 34 ml of a 10% aqueous solution of potassium bromide was added in 3 seconds 2 minutes before the end of the addition of the liquids (A) and (B). Three minutes after the addition of the liquids (A) and (B), 27 ml of potassium thiocyanate was added, 570 mg of sensitizing dye I for green sensitive emulsion, 60 mg of sensitizing dye II for green sensitive emulsion, green 45 ml of a solution of 100 g of gelatin dispersion containing 120 mg of sensitizing dye III for sensitive emulsion was added 1 minute after the addition, the temperature was raised to 75 ° C. and held for 10 minutes. Next, the temperature was lowered to 40 ° C., and desalting was performed according to a conventional method using a precipitating agent (1). Dispersion was performed using 67 g of deionized alkali-treated bone gelatin, zinc nitrate, and phenoxyethanol. And it adjusted so that it might become pH6.3 and pAg7.7.
The grains contained in the resulting emulsion had an average grain size of 0.74 μm expressed in diameter equivalent to a sphere, an average aspect ratio of 8.7, and an average ratio of adjacent sides of the projection plane of 1: 1.6. And silver chlorobromide (111) tabular grains having a silver bromide content of 5 mol%. This emulsion was designated B-1.
This emulsion (B-1) was chemically sensitized at 60 ° C. 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, sodium thiosulfate, selenium sensitizer, chloroauric acid, sodium benzenethiosulfonate are added in sequence to achieve maximum sensitivity. It was made to become. The chemical sensitization was stopped using Compound (4). The green sensitive emulsion prepared in this way was represented with a subscript such as B-1g.
[0176]
Embedded image

[0177]
Also, by adjusting the initial gelatin amount and the amount of silver nitrate contained in the solution (A) and the amount of sodium chloride contained in the solution (B), the emulsion B- comprising the (111) plane having a grain size different from that of the emulsion B-1g. 2g and B-3g were produced. The particle sizes of B-2g and B-3g were 0.51 μm and 0.37 μm, respectively. Emulsions B-2g and B-3g are used in Example 2.
[0178]
Next, a dispersion of zinc hydroxide used as a base precursor was prepared.
31 g of zinc hydroxide powder with a primary particle size of 0.2 μm, 1.6 g of carboxymethyl cellulose and 0.4 g of sodium polyacrylate as a dispersing agent, 8.5 g of lime-processed ossein gelatin, and 158.5 ml of water are mixed. 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]
Further, an emulsified dispersion of magenta coupler was prepared.
7.80 g of magenta coupler (a), 5.45 g of developing agent (b), 2 mg of anti-fogging agent (c), 8.21 g of high-boiling organic solvent (d) and 24.0 ml of ethyl acetate were dissolved at 60 ° C. The above solution was mixed in 150 g of an aqueous solution in which 12.0 g of lime-processed gelatin and 0.6 g of sodium dodecylbenzenesulfonate were dissolved, and the temperature was maintained at 50 ° C., and the mixture was stirred at 10,000 rpm for 20 minutes using a dissolver stirrer. Emulsified and dispersed. After dispersion, distilled water was added so that the total amount was 300 g, and the mixture was mixed at 2,000 rpm for 10 minutes.
[0180]
A dye dispersion for the magenta layer (present invention) was prepared by emulsifying and dispersing as follows. That is, 2.0 g of the magenta dye A10, 2.0 g of tricresyl phosphate, 3.5 g of oil layer component dissolved with 22 cc of cyclohexane, 3.5 g of lime-processed gelatin, 0.26 g of the surfactant (e) and 37 cc of water are included. The aqueous layer components were mixed and dispersed using a homogenizer at 40 ° C. and 10,000 rpm for 3 minutes. Further, 44 cc of water was added and mixed at 2,000 rpm for 10 minutes to obtain a uniform dispersion. The resulting dispersion had an average particle size of 0.18 μm.
For comparison of the above dyes, a magenta leuco dye and zinc were combined to produce a colorant dispersion for use in a layer that forms a decolorable colored layer during heat development.
[0181]
These dispersions and the previously prepared silver halide emulsion were combined to prepare six types of heat-developable color photographic materials of Samples 101 to 106 having the constitution shown in Table 1.
[0182]
[Table 1]

[0183]
Embedded image

[0184]
Embedded image

[0185]
Embedded image

[0186]
Furthermore, treatment materials P-1 and P-2 as shown in Tables 2 to 4 were produced.
[0187]
[Table 2]

[0188]
[Table 3]

[0189]
[Table 4]

[0190]
Embedded image

[0191]
Embedded image

[0192]
These photosensitive materials were exposed to 1/100 second at 1,000 lux through an optical wedge and a green filter.
18 ml / m of 40 ° C. warm water is applied to the surface of the photosensitive material after exposure. ² After applying and superimposing the processing material P-1 and the film surfaces of each other, heat development was performed at 83 ° C. for 15 seconds using a heat drum. When the photosensitive material was peeled off after processing, a magenta colored wedge-shaped image was obtained.
[0193]
Furthermore, in order to fix, processing of the 2nd process was performed using the processing material P-2. The treatment of the second step is 12 cc / m on the treatment material P-2. ² Was applied to the photosensitive material after the first treatment and heated at 70 ° C. for 20 seconds.
[0194]
When the unexposed part of the obtained sample was observed, it was found that all the colored layers were decolored. Further, when the transmission density of the obtained color sample was measured and the sensitivity of each photosensitive material was measured with a so-called characteristic curve, the relative sensitivity was determined by the reciprocal of the exposure amount corresponding to a density higher by 0.15 than the fog density. Occasionally, the photosensitive materials 101 to 106 all matched within ± 0.1. Therefore, it can be seen that these photosensitive materials have almost equal sensitivity.
[0195]
The highest concentration of these samples was measured. In either case, the silver halide was not bleached. The tendency of the results did not change with and without fixing. The results without fixing are summarized in Table 5.
[0196]
[Table 5]

[0197]
From the results of Table 5, it can be seen that the photosensitive material of the present invention is an excellent photosensitive material having a high maximum density. Further, when the processed photosensitive material and the processed material were each extracted by liquid chromatography, it was found that all the decolored dyes remained in the photosensitive material and were not transferred to the processed material.
[0198]
Example 2
Blue-sensitive and red-sensitive emulsions were prepared by changing the spectral sensitizing dyes used for spectral sensitization of the silver halide emulsion prepared in Example 1 to those shown below. The blue-sensitive emulsion is given a subscript b, for example, M-1b, and the red-sensitive emulsion is given a subscript r, for example, M-1r.
[0199]
Embedded image

[0200]
Embedded image

[0201]
Cyan and yellow coupler dispersions were also prepared according to the method for preparing coupler dispersions of Example 1.
Cyan and yellow dye dispersions were prepared according to the method of preparing the dye dispersion of the invention of Example 1. For comparison, a dispersion of a colorant was also prepared by combining the following yellow, magenta and cyan leuco dyes with a zinc complex for the purpose of forming a colored layer that can be decolored during heat development.
Using the thus obtained silver halide emulsion, coupler dispersion, and colorant dispersion, heat-developable color photosensitive materials (211 213 214 214 224) shown in Table 6 were prepared. .
[0202]
[Table 6]

[0203]
[Table 7]

[0204]
[Table 8]

[0205]
[Table 9]

[0206]
Embedded image

[0207]
Embedded image

[0208]
Embedded image

[0209]
Embedded image

[0210]
Here, the emulsions used in each layer are summarized in Table 7.
[0211]
[Table 10]

[0212]
The photographic characteristics of these photosensitive materials were tested in the same manner as in Example 1. First, each photosensitive material was exposed to 1/100 second at 1,000 lux through an optical wedge and blue, green and red filters.
Hot water at 40 ° C. is applied to the surface of the photosensitive material after exposure at 16 ml / m ² Heat applied to the processing material P-1 used in Example 1 and the film surfaces of each other while superimposing each other at 80 ° C. for 25 seconds (the time from stacking to peeling) Developed. The fixing process using the second processing sheet was not performed. When the photosensitive material is peeled off after heat development, a yellow-shaped wedge-shaped image is exposed using the blue filter, a magenta-colored wedge-shaped image is exposed using the green filter, and a sample is exposed using the red filter. Then, a wedge-shaped image with cyan color was obtained. Furthermore, the evaluation of the color separation property of the green-sensitive layer and the red-sensitive layer with respect to blue light was visually judged from these samples.
In addition, the maximum concentration of these samples was measured. Fixing was not performed. The results are summarized in Table 8.
[0213]
[Table 11]

[0214]
From the results, it can be seen that the effect of the present invention is remarkable. That is, even when the light-sensitive material for color photography according to the present invention comprising three layers of O, M, and U layers corresponding to B, G, and R light respectively for yellow, magenta, and cyan is used as in Example 1. Similarly, the effect of high maximum density was observed. Further, when a color photographing material in which a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer are combined as in this example is produced, it can be seen that the color-sensitive material is excellent in blue light and is an excellent photosensitive material.
[0215]
【The invention's effect】
As described above, according to the present invention, it is possible to provide a high-quality silver halide color photographic light-sensitive material for photographing capable of forming an image easily, quickly and with less environmental burden.
Furthermore, according to the present invention, it is possible to provide an excellent silver halide color photographic light-sensitive material for photographing that can provide good graininess and exposure latitude even with simple and rapid processing, in particular, excellent sharpness. A high-quality silver halide color photographic light-sensitive material for photographing can be provided.

Claims (3)

It includes at least one photosensitive layer comprising a photosensitive silver halide grain, a compound that forms a dye by a coupling reaction with an oxidized form of a developing agent, and a binder on a support, and after exposure, the photosensitive layer surface of the photosensitive material is formed. In the silver halide color photographic light-sensitive material in which a color image is formed by laminating on a processing layer surface of a processing material containing a nucleophile and heat development, at least one photosensitive layer is (1) 50 mol% or more. Silver halide grains made of silver chloride, wherein the main outer surface of the grains is a (100) plane, and the aspect ratio of the aspect ratio of the projection plane is 1: 1 to 1: 2 An emulsion in which 50% or more of the total projected area is occupied by the above tabular grains, or (2) a silver halide grain comprising 50 mol% or more of silver chloride, the main of the grains The tabular grains having an aspect ratio of 2 or more such that the surface is a (111) plane and the ratio of adjacent sides of the projection plane is a hexagon having a ratio of 1: 1 to 1:10 is 50% or more of the total projected area. The photosensitive material contains a dye that is decolored by reaction with a nucleophile during development processing, the dye is non-diffusible, and further decolored after development processing A silver halide color photographic light-sensitive material characterized in that at least a part of a dye is diffusion-resistant. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the dye is any one of the dyes represented by the following general formulas (I) to (IV) that decolorize during processing.
Formula (I)
A51 = L51− (L52 = L53) _m51 −Q51
Formula (II)
A51 = L51− (L52 = L53) _n51 −A52
Formula (III)
A51 (= L51-L52) _p51 = B51
Formula (IV)
_{(NC) 2 C = C (} CN) -Q51
(In the formula, = represents a double bond,-represents a single bond, A51 and A52 each represent an acidic nucleus, and B51 represents a basic nucleus. Q51 represents an aryl group or a heterocyclic group. L51 and L52) , L53 each represents a methine group, m51 represents 0, 1 or 2. n51 and p51 each represents 0, 1, 2 or 3. However, compounds represented by general formulas (I) to (IV) Does not have a carboxyl group or a sulfo group, and the compounds represented by the general formulas (I) to (IV) have a non-diffusible group, and the product after treatment (decoloration) is also resistant to (It is diffusive and does not substantially elute from the photosensitive material.) When the photosensitive layer of the photosensitive material contains a developing agent and the processing layer of the processing material contains a base and / or a base precursor, the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material are bonded together. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein water is applied to the photosensitive layer surface of the material and / or the processing layer surface of the processing material, followed by bonding and heat development.