JP3729375B2 - Color image forming method and silver halide color photographic material - Google Patents

Description

【００８１】
【表２】

【００８２】
出力用感光材料（カラーペーパー）に用いうるシアン、マゼンタおよびイエローカプラーとしては、その他、特開昭６２−２１５２７２号の第９１頁右上欄４行目〜１２１頁左上欄６行目、特開平２−３３１４４号の第３頁右上欄１４行目〜１８頁左上欄末行目と第３０頁右上欄６行目〜３５頁右下欄１１行目、やＥＰ０３５５，６６０Ａ２号の第４頁１５行目〜２７行目、５頁３０行目〜２８頁末行目、４５頁２９行目〜３１行目、４７頁２３行目〜６３頁５０行目に記載のカプラーも有用である。
出力用カラー感光材料に用いうる防菌・防黴剤としては特開昭６３−２７１２４７号に記載のものが有用である。
本発明の画像再生システムをコンパクトで、安価なものにするために半導体レーザーあるいは固体レーザーと非線形光学結晶を組合わせた第二高調波発生光源（ＳＨＧ）を使用することが好ましい。特にコンパクトで、安価、更に寿命が長く安定性が高い装置を設計するためには半導体レーザーの使用が好ましく、露光光源の少なくとも一つは半導体レーザーを使用することが好ましい。
【００８３】
このような走査露光光源を使用する場合、出力用カラー感光材料の分光感度極大波長は使用する走査露光用光源の波長により任意に設定することができる。半導体レーザーを励起光源に用いた固体レーザーあるいは半導体レーザーと非線形光学結晶を組合わせて得られるＳＨＧ光源では、レーザーの発振波長を半分にできるので、青色光、緑色光が得られる。従って、感光材料の分光感度極大は通常の青、緑、赤の３つの波長領域に持たせることが可能である。
このような走査露光における露光時間は、画素密度を４００dpiとした場合の画素サイズを露光する時間として定義すると、好ましい露光時間としては１０^-4秒以下、更に好ましくは１０^-6秒以下である。
本発明に適用できる好ましい走査露光方式については、前記の表に掲示した特許に詳しく記載されている。
また出力用カラー感光材料を処理するには、特開平２−２０７２５０号の第２６頁右下欄１行目〜３４頁右上欄９行目、及び特開平４−９７３５５号の第５頁左上欄１７行目〜１８頁右下欄２０行目に記載の処理素材や処理方法が好ましく適用できる。また、この現像液に使用する保恒剤としては、前記の表に掲示した特許に記載の化合物が好ましく用いられる。
【００８４】
６．本発明の補足的説明
６．１ 現像処理について
【００８５】
本発明において、現像処理に用いる発色現像液は、好ましくは芳香族第一級アミン系発色現像主薬を主成分とするアルカリ性水溶夜である。この発色現像主薬としては、アミノフェノール系化合物も有用であるが、ｐ−フェニレンジアミン系化合物が好ましく使用され、その代表例としては３−メチル−４−アミノ−Ｎ，Ｎ−ジエチルアニリン、３−メチル−４−アミノ−Ｎ−エチル−Ｎ−β−ヒドロキシエチルアニリン、３−メチル−４−アミノ−Ｎ−エチル−Ｎ−β−メタンスルホンアミドエチルアニリン、３−メチル−４−アミノ−Ｎ−エチル−β−メトキシエチルアニリン、４−アミノ−３−メチル−Ｎ−メチル−Ｎ−（３−ヒドロキシプロピル）アニリン、４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（３−ヒドロキシプロピル）アニリン、４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（２−ヒドロキシプロピル）アニリン、４−アミノ−３−エチル−Ｎ−エチル−Ｎ−（３−ヒドロキシプロピル）アニリン、４−アミノ−３−メチル−Ｎ−プロピル−Ｎ−（３−ヒドロキシプロピル）アニリン、４−アミノ−３−プロピル−Ｎ−メチル−Ｎ−（３−ヒドロキシプロピル）アニリン、４−アミノ−３−メチル−Ｎ−メチル−Ｎ−（４−ヒドロキシブチル）アニリン、４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（４−ヒドロキシブチル）アニリン、４−アミノ−３−メチル−Ｎ−プロピル−Ｎ−（４−ヒドロキシブチル）アニリン、４−アミノ−３−エチル−Ｎ−エチル−Ｎ−（３−ヒドロキシ−２−メチルプロピル）アニリン、４−アミノ−３−メチル−Ｎ，Ｎ−ビス（４−ヒドロキシブチル）アニリン、４−アミノ−３−メチル−Ｎ，Ｎ−ビス（５−ヒドロキシペンチル）アニリン、４−アミノ−３−メチル−Ｎ−（５−ヒドロキシペンチル）−Ｎ−（４−ヒドロキシブチル）アニリン、４−アミノ−３−メトキシ−Ｎ−エチル−Ｎ−（４−ヒドロキシブチル）アニリン、４−アミノ−３−エトキシ−Ｎ，Ｎ−ビス（５−ヒドロキシペンチル）アニリン、４−アミノ−３−プロピル−Ｎ−（４−ヒドロキシブチル）アニリン、及びこれらの硫酸塩、塩酸塩もしくはｐ−トルエンスルホン酸塩などが挙げられる。これらの中で、特に、３−メチル４−アミノ−Ｎ−エチル−Ｎ−β−ヒドロキシエチルアニリン、４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（３−ヒドロキシプロピル）アニリン、４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（４−ヒドロキシブチル）アニリン、３−メチル−４−アミノ−Ｎ−エチル−Ｎ−β−メタンスルホンアミドエチルアニリン及びこれらの塩酸塩、ｐ−トルエンスルホン酸塩もしくは硫酸塩が好ましい。これらの化合物は目的に応じ２種以上併用することもできる。
【００８６】
芳香族第一級アミン現像主薬の使用量はカラー現像液１リットル当たり好ましくは０．０００２モル〜０．２モル、さらに好ましくは０．００１モル〜０．１モルである。
【００８７】
発色現像液は、アルカリ金属の炭酸塩、ホウ酸塩もしくはリン酸塩５−スルフォサリチル酸塩のようなｐＨ緩衝剤、塩化物塩、臭化物塩、沃化物塩、ベンズイミダゾール類、ベンゾチアゾール類もしくはメルカプト化合物のような現像抑制剤またはカブリ防止剤などを含むのが一般的である。また必要に応じて、ヒドロキシルアミン、ジエチルヒドロキシルアミンの他特開平３−１４４４４６号の一般式（Ｉ）で表されるヒドロキシルアミン類、亜硫酸塩、Ｎ，Ｎ−ビスカルボキシメチルヒドラジンの如きヒドラジン類、フェニルセミカルバジド類、トリエタノールアミン、カテコールスルホン酸類の如き各種保恒剤、エチレングリコール、ジエチレングリコールのような有機溶剤、ベンジルアルコール、ポリエチレングリコール、四級アンモニウム塩、アミン類のような現像促進剤、色素形成カプラー、競争カプラー、１−フェニル−３−ピラゾリドンのような補助現像主薬、粘性付与剤、アミノポリカルボン酸、アミノポリホスホン酸、アルキルホスホン酸、ホスホノカルボン酸に代表されるような各種キレート剤、例えば、エチレンジアミン四酢酸、ニトリロ三酢酸、ジエチレントリアミン五酢酸、シクロヘキサンジアミン四酢酸、ヒドロキシエチルイミノジ酢酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、ニトリロ−Ｎ，Ｎ，Ｎ−トリメチレンホスホン酸、エチレンジアミン−Ｎ，Ｎ，Ｎ，Ｎ−テトラメチレンホスホン酸、エチレンジアミン−ジ（ｏ−ヒドロキシフェニル酢酸）及びそれらの塩を代表例として挙げることができる。
【００８８】
上記の内、保恒剤としては置換ヒドロキシルアミンが最も好ましく、中でもジエチルヒドロキシルアミン、モノメチルヒドロキシルアミン或いはスルホ基やカルボキシ基、水酸基などの水溶性基で置換されたアルキル基を置換基として有するものが好ましい。最も好ましい例としては、Ｎ，Ｎ−ビス（２−スルホエチル）ヒドロキシルアミン及びそのアルカリ金属塩である。
【００８９】
また、キレート剤としては生分解性を有する化合物が好ましい。この例としては、特開昭６３−１４６９９８号、特開昭６３−１９９２９５号、特開昭６３−２６７７５０号、特開昭６３−２６７７５１号、特開平２−２２９１４６号、特開平３−１８６８４１号、独国特許３７３９６１０、欧州特許４６８３２５号等に記載のキレート剤を挙げることができる。発色現像液の補充タンクや処理槽中の処理液は高沸点有機溶剤などの液剤でシールドし、空気との接触面積を減少させることが好ましい。この液体シールド剤としては流動パラフィンが最も好ましい。また、補充液に用いるのが特に好ましい。本発明における発色現像液での処理温度は２０〜５５℃、好ましくは３０〜５５℃である。処理時間は撮影用感材においては２０秒〜５分、好ましくは３０秒〜３分２０秒である。更に好ましくは４０秒〜１分３０秒である。
【００９０】
処理槽での写真処理液と空気との接触面積は、以下に定義する開口率で表わすことができる。即ち、
開口率＝〔処理液と空気との接触面積（cm²）〕÷〔処理液の容量（cm³）〕
上記の開口率は、０．１以下であることが好ましく、より好ましくは０．００１〜０．０５である。このように開口率を低減させる方法としては、処理槽の写真処理液面に浮き蓋等の遮蔽物を設けるほかに、特開平１−８２０３３号に記載された可動蓋を用いる方法、特開昭６３−２１６０５０号に記載されたスリット現像処理方法を挙げることができる。開口率を低減させることは、発色現像及び黒白現像（カラーリバーサル処理など）の両工程のみならず、後続の諸工程、例えば、漂白、水洗、安定化（以上は基準処理も含めて述べた）、などの全ての工程において適用することが好ましい。また、現像液中の臭化物イオンや塩化物イオンの蓄積を抑える手段を用いることにより補充量を低減することもできる。
【００９１】
本発明の処理装置において、フィルムの保存を行う必要がなく後続処理を行わない場合を別にすれば、脱銀処理後、水洗、画像安定化工程を経るのが一般的である。水洗工程での水洗水量は、感光材料の特性（例えばカプラー等使用素材による）、用途、更には水洗水温、水洗タンクの数（段数）、向流、順流等の補充方式、その他種々の条件によって広範囲に設定し得る。このうち、多段向流方式における水洗タンク数と水量の関係は、Journal of the Society of Motion Picture and Television Engineers第６４巻、Ｐ．２４８〜２５３（１９５５年５月号）に記載の方法で、求めることができる。前記文献に記載の多段向流方式によれば水洗水量を大幅に減少し得るが、タンク内における水の滞留時間の増加により、バクテリアが繁殖し、生成した浮遊物が感光材料に付着する等の問題が生じる。本発明のカラー感光材料の処理において、このような問題が解決策として、特開昭６２−２８８，８３８号に記載のカルシウムイオン、マグネシウムイオンを低減させる方法を極めて有効に用いることができる。また、特開昭５７−８，５４２号に記載のイソチアゾロン化合物やサイアベンダゾール類、塩素化イソシアヌール酸ナトリウム等の塩素系殺菌剤、その他ベンゾトリアゾール等、堀口博著「防菌防黴剤の化学」（１９８６年）三共出版、衛生技術会編「微生物の滅菌、殺菌、防黴技術」（１９８２年）工業技術会、日本防菌防黴学会編「防菌防黴剤事典」（１９８６年）に記載の殺菌剤を用いることもできる。
【００９２】
本発明の対象となる感光材料の処理における水洗水のｐＨは、４〜９であり、好ましくは５〜８である。水洗水温、水洗時間も、感光材料の特性、用途等で種々設定し得るが、一般には、１５〜４５℃で２０秒〜１０分、好ましくは２５〜４０℃で３０秒〜５分の範囲が選択される。更に、本発明の感光材料は、上記水洗に代り、直接安定化液によって処理することもできる。このような安定化処理においては、特開昭５７−８５４３号、同５８−１４８３４号、同６０−２２０３４５号に記載の公知の方法はすべて用いることができる。
【００９３】
また、画像安定化液には色素画像を安定化させる化合物、例えばホルマリン、ｍ−ヒドロキシベンズアルデヒド等のベンズアルデヒド類、ホルムアルデヒド重亜硫酸付加物、へキサメチレンテトラミン及びその誘導体、ヘキサヒドロトリアジン及びその誘導体、ジメチロール尿素、Ｎ−メチロールピラゾールなどのＮ−メチロール化合物、有機酸やｐＨ緩衝剤等が含まれる。これらの化合物の好ましい添加量は安定液１リットルあたり０．００１〜０．０２モルであるが、安定液中の遊離ホルムアルデヒド濃度は低い方がホルムアルデヒドガスの飛散が少なくなるため好ましい。このような点から色素画像安定化剤としては、ｍ−ヒドロキシベンズアルデヒド、ヘキサメチレンテトラミン、Ｎ−メチロールピラゾールなどの特開平４−２７０３４４号記載のＮ−メチロールアゾール類、Ｎ，Ｎ’−ビス（１，２，４−トリアゾール−１−イルメチル）ピペラジン等の特開平４−３１３７５３号記載のアゾリルメチルアミン類が好ましい。特に特開平４−３５９２４９号（対応、欧州特許公開第５１９１９０Ａ２号）に記載の１，２，４−トリアゾールの如きアゾール類と、１，４−ビス（ｌ，２，４−トリアゾール−１−イルメチル）ピペラジンの如きアゾリルメチルアミン及びその誘導体の併用が、画像安定性が高く、且つホルムアルデヒド蒸気圧が少なく好ましい。また、その他必要に応じて塩化アンモニウムや亜硫酸アンモニウム等のアンモニウム化合物、Ｂｉ、Ａｌなどの金属化合物、蛍光増白剤、硬膜剤、米国特許４，７８６，５８３号に記載のアルカノールアミンや、前記の定着液や漂白定着液に含有することができる保恒剤、例えば、特開平１−２３１０５１号公報に記載のスルフィン酸化合物を含有させることも好ましい。
【００９４】
水洗水及び／又は水洗代替安定化浴、及び画像安定化液には処理後の感光材料の乾燥時の水滴ムラを防止するため、種々の界面活性剤を含有することができる。中でもノニオン性界面活性剤を用いるのが好ましく、特にアルキルフェノールエチレンオキサイド付加物が好ましい。アルキルフェノールとしては特にオクチル、ノニル、ドデシル、ジノニルフェノールが好ましく、またエチレンオキサイドの付加モル数としては特に８〜１４が好ましい。さらに消泡効果の高いシリコン系界面活性剤を用いることも好ましい。
【００９５】
水洗水及び／又は安定化液、及び画像安定化液には、各種キレート剤を含有させることが好ましい。好ましいキレート剤としては、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸などのアミノポリカルボン酸や１−ヒドロキシエチリデン−１，１−ジホスホン酸、Ｎ，Ｎ，Ｎ’−トリメチレンホスホン酸、ジエチレントリアミン−Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチレンホスホン酸などの有機ホスホン酸、あるいは、欧州特許３４５，１７２Ａ１号に記載の無水マレイン酸ポリマーの加水分解物などをあげることができる。
【００９６】
上記水洗水及び／又は安定化液の補充に伴うオーバーフロー液は脱銀工程等他の工程において再利用することもできる。本発明の処理機について、駆動以外の部分について記述する。カラー現像液、カラー現像補充液は、処理槽及び補充液槽で、液が空気と接触する面積（開口面積）はできるだけ小さい方が好ましい。例えば開口面積（cm²）を槽中の液体槽（cm³）で割った値を開口率とすると、開口率は、０．０１（cm^-1）以下が好ましく、０．００５以下がより好ましく、特に０．００１以下が最も好ましい。
【００９７】
本発明においては、迅速に処理を行うために、各処理液間を感光材料が移動する際の空中時間、即ちクロスオーバー時間は短い程良く、好ましくは２０秒以下、より好ましくは１０秒以下、更に好ましくは５秒以下である。上記の様な短時のクロスオーバーを達成するため、本発明はシネ型の自動現像機を用いるのが好ましく、特にリーダー搬送方式やローラー搬送方式が好ましい。このような方式は、富士写真フイルム（株）製自動現像機ＦＰー５６０Ｂや同ＰＰ１８２０Ｖに用いられている。また、搬送の線速度は大きい方が好ましいが、毎分３０cm〜３０ｍが一般的であり、好ましくは５０cm〜１０ｍである。リーダーや感光材料の搬送手段としては、特開昭６０−１９１２５７号、同６０−１９１２５８号、同６０−１９１２５９号に記載のベルト搬送方式が好ましい。また、クロスオーバー時間を短縮し、かつ処理液の混入を防止するため、混入防止板を有するクロスオーバーラックの構造が好ましい。
【００９８】
本発明における各処理液には、処理液の蒸発分に相当する水を供給する、いわゆる蒸発補正を行うことが好ましい。特に、発色現像液において好ましい。このような水の補充を行う具体的方法としては、液レベルセンサーやオーバーフローセンサーを用いた蒸発補正方法が好ましい。最も好ましい蒸発補正方式は、蒸発分に相当する水を予想して加えるもので、自動現像機の運転時間、停止時間及び温調時間の情報に基づいて予め求められた係数により計算された加水量を添加するものである。
【００９９】
また、蒸発量を減少させる工夫も必要であり、開口面積を少なくしたり、排気ファンの風量を調節することが要求される。例えば、発色現像液の好ましい開口率は前記した通りであるが、他の処理液においても同様に開口面積を低下させることが好ましい。排気ファンは、温調時の結露防止のために取付けられているが、好ましい排気量としては、毎分０．１m³〜１m³であり、特に好ましい排気量としては、０．２m³〜０．４m³である。また、感光材料の乾燥条件も処理液の蒸発に影響する。乾燥方式としては、セラミック温風ヒーターを用いるのが好ましく、供給風量としては毎分４m³〜２０m³が好ましく、特に６m³〜１０m³が好ましい。セラミック温風ヒーターの加熱防止用サーモスタットは、伝熱によって動作させる方式が好ましく、取付け位置は、放熱フィンや伝熱部を通じて風下または風上に取りつけるのが好ましい。乾燥温度は、処理される感光材料の含水量によって調整することが好ましく、３５mm幅のフィルムでは４５〜５５℃、ブローニーフィルムでは５５〜６５℃、プリント材料では６０〜９０℃が最適である。処理液の補充に際しては補充ポンプが用いられるが、ベローズ式の補充ポンプが好ましい。また、補充精度を向上させる方法としては、ポンプ停止時の逆流を防止するため、補充ノズルヘの送液チューブの径を細くしておくことが有効である。好ましい内径としては１〜８mm、特に好ましい内径としては２から５mmである。
【０１００】
自動現像機には前述した駆動部以外にも種々の部品材料が用いられるが、好ましい材料を以下に記載する。処理槽及び温調槽等のタンク材質は、変性ＰＰＯ（変性ポリフェニレンオキサイド）、変性ＰＰＥ（変性ポリフェニレンエーテル）樹脂が好ましい。変性ＰＰＯは、日本ジーイープラスチック社製「ノリル」、変性ＰＰＥは、旭化成工業製「ザイロン」、三菱瓦斯化学製「ユピエース」等が挙げられる。また、これらの材質は、処理ラック、クロスオーバー等の処理液に接触する可能性のある部位に適している。
【０１０１】
乾燥時間は１０秒〜２分が好ましく、特に２０秒〜８０秒がより好ましい。以上、主として補充方式による連続処理について述べてきたが、本発明においては一定量の処理液で補充を行わずに処理を行い、その後処理液の全量あるいは一部を新液に交換し再び処理を行うバッチ処理方式も好ましく用いることができる。
【０１０２】
６．２ 本発明に用いられるカラーネガフィルム
次に本発明に使用される感光材料（カラーネガフィルム）について詳細を説明する。
【０１０３】
本発明に係わるカラーネガフィルムは、支持体上に少なくとも１層の感光性層が設けられていればよい。典型的な例としては支持体上に、実質的に感色性は同じであるが感光度の異なる複数のハロゲン化銀乳剤層から成る感光性層を少なくとも１つ有するハロゲン化銀写真感光材料である。該感光性層は青色光、緑色光、および赤色光の何れかに感色性を有する単位感光性層であり、多層ハロゲン化銀カラー写真感光材料においては、一般に単位感光性層の配列が、支持体側から順に赤感色性層、緑感色性層、青感色性層の順に設置される。しかし、目的に応じて上記設置順が逆であっても、また同一感色性層中に異なる感光性層が挟まれたような設置順をもとり得る。上記のハロゲン化銀感光性層の間および最上層、最下層には非感光性層を設けてもよい。
【０１０４】
これらには、後述のカプラー、ＤＩＲ化合物、混色防止剤等が含まれていてもよい。各単位感光性層を構成する複数のハロゲン化銀乳剤層はＤＥ１，１２１，４７０あるいはＧＢ９２３，０４５に記載されているように高感度乳剤層、低感度乳剤層の２層を、支持体に向かって順次感光度が低くなる様に配列するのが好ましい。また、特開昭５７−１１２７５１、同６２−２００３５０、同６２−２０６５４１、６２−２０６５４３に記載されているように支持体より離れた側に低感度乳剤層、支持体に近い側に高感度乳剤層を設置してもよい。具体例として支持体から最も遠い側から、低感度青感光性層（ＢＬ）／高感度青感光性層（ＢＨ）／高感度緑感光性層（ＧＨ）／低感度緑感光性層（ＧＬ）／高感度赤感光性層（ＲＨ）／低感度赤感光性層（ＲＬ）の順、またはＢＨ／ＢＬ／ＧＬ／ＧＨ／ＲＨ／ＲＬの順、またはＢＨ／ＢＬ／ＧＨ／ＧＬ／ＲＬ／ＲＨの順等に設置することができる。また特公昭５５−３４９３２公報に記載されているように、支持体から最も遠い側から青感光性層／ＧＨ／ＲＨ／ＧＬ／ＲＬの順に配列することもできる。また特開昭５６−２５７３８、同６２−６３９３６に記載されているように、支持体から最も遠い側から青感光性層／ＧＬ／ＲＬ／ＧＨ／ＲＨの順に配列することもできる。
【０１０５】
また特公昭４９−１５４９５に記載されているように上層を最も感光度の高いハロゲン化銀乳剤層、中層をそれよりも低い感光度のハロゲン化銀乳剤層、下層を中層よりも更に感光度の低いハロゲン化銀乳剤層を配置し、支持体に向かって感光度が順次低められた感光度の異なる３層から構成される配列が挙げられる。このような感光度の異なる３層から構成される場合でも、特開昭５９−２０２４６４に記載されているように、同一感色性層中において支持体より離れた側から中感度乳剤層／高感度乳剤層／低感度乳剤層の順に配置されてもよい。その他、高感度乳剤層／低感度乳剤層／中感度乳剤層、あるいは低感度乳剤層／中感度乳剤層／高感度乳剤層の順に配置されていてもよい。また、４層以上の場合にも、上記の如く配列を変えてよい。色再現性を改良するために、ＵＳ４，６６３，２７１、同４，７０５，７４４、同４，７０７，４３６、特開昭６２−１６０４４８、同６３−８９８５０の明細書に記載の、ＢＬ，ＧＬ，ＲＬなどの主感光層と分光感度分布が異なる重層効果のドナー層（ＣＬ）を主感光層に隣接もしくは近接して配置することが好ましい。
【０１０６】
本発明に用いられる好ましいハロゲン化銀は約３０モル％以下のヨウ化銀を含む、ヨウ臭化銀、ヨウ塩化銀、もしくはヨウ塩臭化銀である。特に好ましいのは約２モル％から約１０モル％までのヨウ化銀を含むヨウ臭化銀もしくはヨウ塩臭化銀である。写真乳剤中のハロゲン化銀粒子は、立方体、八面体、十四面体のような規則的な結晶を有するもの、球状、板状のような変則的な結晶形を有するもの、双晶面などの結晶欠陥を有するもの、あるいはそれらの複合形でもよい。ハロゲン化銀の粒径は、約０．２μｍ以下の微粒子でも投影面積直径が約１０μｍに至るまでの大サイズ粒子でもよく、多分散乳剤でも単分散乳剤でもよい。本発明に使用できるハロゲン化銀写真乳剤は例えばリサーチ・ディスクロージャー（以下、ＲＤと略す）Ｎｏ．１７６４３（１９７８年１２月），２２〜２３頁，“Ｉ．乳剤製造（Emulsion preparation and types）”、および同Ｎｏ．１８７１６（１９７９年１１月），６４８頁、同Ｎｏ．３０７１０５（１９８９年ｌｌ月），８６３〜８６５頁、およびグラフキデ著「写真の物理と化学」、ポールモンテル社刊（P.Glafkides, Chemie et Phisique Photographique, Paul Montel、１９６７）、ダフィン著「写真乳剤化学」、フォーカルプレス社刊（G.F.Duffin, Photographic Emulsion Chemistry, Focal Press，１９６６）、ゼリグマンら著「写真乳剤の製造と塗布」フォーカルプレス社刊（V.L.Zelikman,et al., Making and Coating Photographic Emulsion, Focal Press，１９６４）などに記載された方法を用いて調製することができる。
【０１０７】
ＵＳ３，５７４，６２８、同３，６５５，３９４およびＧＢ１，４１３，７４８に記載された単分散乳剤も好ましい。また、アスペクト比が約３以上であるような平板状粒子も本発明に使用できる。平板状粒子はガトフ著、フォトグラフィック・サイエンス・アンド・エンジニアリング（Gutoff, Photographic Science and Engineering）、第１４巻２４８〜２５７頁（１９７０年）；ＵＳ４，４３４，２２６、同４，４１４，３１０、同４，４３３，０４８、同４，４３９，５２０およびＧＢ２，１１２，１５７に記載の方法により簡単に調製することができる。結晶構造は一様なものでも、内部と外部とが異質なハロゲン組成からなるものでもよく、層状構造をなしていてもよい。エピタキシャル接合によって組成の異なるハロゲン化銀が接合されていてもよく、例えばロダン銀、酸化鉛などのハロゲン化銀以外の化合物と接合されていてもよい。また種々の結晶形の粒子の混合物を用いてもよい。上記の乳剤は潜像を主として表面に形成する表面潜像型でも、粒子内部に形成する内部潜像型でも表面と内部のいずれにも潜像を有する型のいずれでもよいが、ネガ型の乳剤であることが必要である。内部潜像型のうち、特開昭６３−２６４７４０に記載のコア／シェル型内部潜像型乳剤であってもよく、この調製方法は特開昭５９−１３３５４２に記載されている。この乳剤のシェルの厚みは現像処理等によって異なるが、３〜４０nmが好ましく、５〜２０nmが特に好ましい。
【０１０８】
ハロゲン化銀乳剤は通常、物理熟成、化学熟成および分光増感を行ったものを使用する。このような工程で使用される添加剤はＲＤ Ｎｏ．１７６４３、同Ｎｏ．１８７１６および同Ｎｏ．３０７１０５に記載されており、その該当箇所を後掲の表にまとめた。本発明の感光材料には感光性ハロゲン化銀乳剤の粒子サイズ、粒子サイズ分布、ハロゲン組成、粒子の形状、感度の少なくとも１つの特性の異なる２種類以上の乳剤を、同一層中に混合して使用することができる。ＵＳ４，０８２，５５３に記載の粒子表面をかぶらせたハロゲン化銀粒子、ＵＳ４，６２６，４９８、特開昭５９−２１４８５２に記載の粒子内部をかぶらせたハロゲン化銀粒子、コロイド銀を感光性ハロゲン化銀乳剤層および／または実質的に非感光性の親水性コロイド層に適用することが好ましい。粒子内部または表面をかぶらせたハロゲン化銀粒子とは感光材料の未露光部および露光部を問わず一様に（非像様に）現像が可能となるハロゲン化銀粒子のことをいい、その調製法はＵＳ４，６２６，４９８、特開昭５９−２１４８５２に記載されている。粒子内部がかぶらされたコア／シェル型ハロゲン化銀粒子の内部核を形成するハロゲン化銀は、ハロゲン組成が異なっていてもよい。粒子内部または表面をかぶらせたハロゲン化銀としては塩化銀、塩臭化銀、沃臭化銀、塩沃臭化銀のいずれをも用いることができる。これらのかぶらされたハロゲン化銀粒子の平均粒子サイズとしては０．０１〜０．７５μｍ、特に０．０５〜０．６μｍが好ましい。また、粒子形状は規則的な粒子でもよく、多分散乳剤でもよいが、単分散性（ハロゲン化銀粒子の重量または粒子数の少なくとも９５％が平均粒子径の±４０％以内の粒子径を有するもの）であることが好ましい。
【０１０９】
本発明には非感光性微粒子ハロゲン化銀を使用することが好ましい。非感光性微粒子ハロゲン化銀とは色素画像を得るための像様露光時においては感光せずに、その現像処理において実質的に現像されないハロゲン化銀微粒子であり、あらかじめカブラされていないほうが好ましい。微粒子ハロゲン化銀は、臭化銀の含有率が０〜１００モル％であり、必要に応じて塩化銀および／または沃化銀を含有してもよい。好ましくは沃化銀を０．５〜１０モル％含有するものである。微粒子ハロゲン化銀は平均粒径（投影面積の円相当直径の平均値）が０．０１〜０．５μｍが好ましく、０．０２〜０．２μｍがより好ましい。微粒子ハロゲン化銀は通常の感光性ハロゲン化銀と同様の方法で調製できる。ハロゲン化銀粒子の表面は、光学的に増感される必要はなく、また分光増感も不要である。ただし、これを塗布液に添加するのに先立ち、あらかじめトリアゾール系、アザインデン系、ベンゾチアゾリウム系、もしくはメルカプト系化合物または亜鉛化合物などの公知の安定剤を添加しておくことが好ましい。この微粒子ハロゲン化銀粒子含有層に、コロイド銀を含有させることができる。本発明の感光材料の塗布銀量は８．０g/m²以下が好ましく、６．０g/m²以下が最も好ましい。
【０１１０】
本発明に使用できる写真用添加剤もＲＤに記載されており、下記の表に関連する記載箇所を示した。
【０１１１】
【表３】

【０１１２】
本発明の感光材料には種々の色素形成カプラーを使用することができるが、以下のカプラーが特に好ましい。
イエローカプラー：ＥＰ５０２，４２４Ａの式（Ｉ), (II）で表わされるカプラー；ＥＰ５１３，４９６Ａの式（１), (２）で表わされるカプラー（特に１８頁のＹ−２８）；ＥＰ５６８，０３７Ａのクレーム１の式（Ｉ）で表わされるカプラー；ＵＳ５，０６６，５７６のカラム１の４５〜５５行の一般式（Ｉ）で表わされるカプラー；特開平４−２７４４２５の段落０００８の一般式（Ｉ）で表わされるカプラー；ＥＰ４９８，３８１Ａ１の４０頁のクレーム１に記載のカプラー（特に１８頁のＤ−３５）；ＥＰ４４７，９６９Ａ１の４頁の式（Ｙ）で表わされるカプラー（特にＹ−１（１７頁），Ｙ−５４（４１頁））；ＵＳ４，４７６，２１９のカラム７の３６〜５８行の式（II）〜（IV）で表わされるカプラー（特にII−１７，１９（カラム１７），II−２４（カラム１９））。
マゼンタカプラー；特開平３−３９７３７（Ｌ−５７（１１頁右下），Ｌ−６８（１２頁右下），Ｌ−７７（１３頁右下）；ＥＰ４５６，２５７のＡ−４−６３（１３４頁），Ａ−４−７３，−７５（１３９頁）；ＥＰ４８６，９６５のＭ−４，−６（２６頁），Ｍ−７（２７頁）；ＥＰ５７１，９５９ＡのＭ−４５（１９頁）；特開平５−２０４１０６の（Ｍ−１)(６頁）；特開平４−３６２６３１の段落０２３７のＭ−２２。
【０１１３】
シアンカプラー：特開平４−２０４８４３のＣＸ−１，３，４，５，１１，１２，１４，１５（１４〜１６頁）；特開平４−４３３４５のＣ−７，１０（３５頁），３４，３５（３７頁), (Ｉ−１), (Ｉ−１７）（４２〜４３頁）；特開平６−６７３８５の請求項１の一般式（Ｉａ）または（Ｉｂ）で表わされるカプラー。
ポリマーカプラー：特開平２−４４３４５のＰ−１，Ｐ−５（１１頁）。
【０１１４】
発色色素が適度な拡散性を有するカプラーとしては、ＵＳ４，３６６，２３７、ＧＢ２，１２５，５７０、ＥＰ９６，８７３Ｂ、ＤＥ３，２３４，５３３に記載のものが好好ましい。発色色素の不要吸収を補正するためのカプラーはＥＰ４５６，２５７Ａ１の５頁に記載の式（ＣＩ), (ＣII), (ＣIII), (ＣIV）で表わされるイエローカラードシアンカプラー（特に８４頁のＹＣ−８６）、該ＥＰに記載のイエローカラードマゼンタカプラーＥｘＭ−７（２０２頁）、ＥＸ−１（２４９頁）、ＥＸ−７（２５１頁）、ＵＳ４，８３３，０６９に記載のマゼンタカラードシアンカプラーＣＣ−９（カラム８）、ＣＣ−１３（カラム１０）、ＵＳ４，８３７，１３６の（２）（カラム８）、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）が好ましい。
【０１１５】
現像主薬酸化体と反応して写真的に有用な化合物残基を放出する化合物（カプラーを含む）としては以下のものが挙げられる。現像抑制剤放出化合物：ＥＰ３７８，２３６Ａ１の１１頁に記載の式（Ｉ), (II), (III), (IV）で表わされる化合物（特にＴ−１０１（３０頁），Ｔ−１０４（３１頁），Ｔ−１１３（３６頁），Ｔ−１３１（４５頁），Ｔ−１４４（５１頁），Ｔ−１５８（５８頁）），ＥＰ４３６，９３８Ａ２の７頁に記載の式（Ｉ）で表わされる化合物（特にＤ−４９（５１頁））、ＥＰ５６８，０３７Ａの式（１）で表わされる化合物（特に（２３）（１１頁））、ＥＰ４４０，１９５Ａ２の５〜６頁に記載の式（Ｉ), (II), (III）で表わされる化合物（特に２９頁のＩ−（１））；
【０１１６】
漂白促進剤放出化合物：ＥＰ３１０，１２５Ａ２の５頁の式（Ｉ), (Ｉ′）で表わされる化合物（特に６１頁の（６０), (６１））及び特開平６−５９４１１の請求項１の式（Ｉ）で表わされる化合物（特に（７）（７頁）；リガンド放出化合物：ＵＳ４，５５５，４７８のクレーム１に記載のＬＩＧ−Ｘで表わされる化合物（特にカラム１２の２１〜４１行目の化合物）；ロイコ色素放出化合物：ＵＳ４，７４９，６４１のカラム３〜８の化合物１〜６；蛍光色素放出化合物：ＵＳ４，７７４，１８１のクレーム１のＣ０ＵＰ−ＤＹＥで表わされる化合物（特にカラム７−１０の化合物１−１１）；現像促進剤又はカブラセ剤放出化合物：ＵＳ４，６５６，１２３のカラム３の式（１）、（２）、（３）で表わされる化合物（特にカラム２５の（Ｉ−２２））及びＥＰ４５０，６３７Ａ２の７５頁３６〜３８行目のＥｘＺＫ−２；離脱して初めて色素となる基を放出する化合物：ＵＳ４，８５７，４４７のクレーム１の式（Ｉ）で表わされる化合物（特にカラム２５〜３６のＹ−１〜Ｙ−１９）。
【０１１７】
カプラー以外の添加剤としては以下のものが好ましい。
油溶性有機化合物の分散媒：特開昭６２−２１５２７２のＰ−３，５，１６，１９，２５，３０，４２，４９，５４，５５，６６，８１，８５，８６，９３（１４０〜１４４頁）；油溶性有機化合物の含浸用ラテックス：ＵＳ４，１９９，３６３に記載のラテックス；現像主薬酸化体スカベンジャー：ＵＳ４，９７８，６０６のカラム２の５４〜６２行の式（Ｉ）で表わされる化合物（特にＩ−，（１), (２), (６), (１２）（カラム４〜５）、ＵＳ４，９２３，７８７のカラム２の５〜１０行の式（特に化合物１（カラム３）；ステイン防止剤：ＥＰ２９８３２１Ａの４頁３０〜３３行の式（Ｉ）〜（III），特にＩ−４７，７２，III−ｌ，２７（２４〜４８頁）；褪色防止剤：ＥＰ２９８３２１ＡのＡ−６，７，２０，２１，２３，２４，２５，２６，３０，３７，４０，４２，４８，６３，９０，９２，９４，１６４（６９〜１１８頁），ＵＳ５，１２２，４４４のカラム２５〜３８のII−１〜III−２３，特にIII−１０，ＥＰ４７１３４７Ａの８〜１２頁のＩ−１〜III−４，特にII−２，ＵＳ５，１３９，９３１のカラム３２〜４０のＡ−１〜４８，特にＡ−３９，４２；発色増強剤または混色防止剤の使用量を低減させる素材：ＥＰ４１１３２４Ａの５〜２４頁のＩ−１〜II−１５，特にＩ−４６；ホルマリンスカベンジャー：ＥＰ４７７９３２Ａの２４〜２９頁のＳＣＶ−１〜２８，特にＳＣＶ−８；
【０１１８】
硬膜剤：特開平１−２１４８４５の１７頁のＨ−１，４，６，８，１４，ＵＳ４，６１８，５７３のカラム１３〜２３の式（VII）〜（XII）で表わされる化合物（Ｈ−１〜５４），特開平２−２１４８５２の８頁右下の式（６）で表わされる化合物（Ｈ−１〜７６），特にＨ−１４，ＵＳ３，３２５，２８７のクレーム１に記載の化合物；現像抑制剤プレカーサー：特開昭６２−１６８１３９のＰ−２４，３７，３９（６〜７頁）；ＵＳ５，０１９，４９２のクレーム１に記載の化合物，特にカラム７の２８，２９；防腐剤、防黴剤：ＵＳ４，９２３，７９０のカラム３〜１５のＩ−１〜III−４３，特にII−１，９，１０，１８，III−２５；安定剤、かぶり防止剤：ＵＳ４，９２３，７９３のカラム６〜１６のＩ−１〜（１４），特にＩ−１，６０，（２), (１３），ＵＳ４，９５２，４８３のカラム２５〜３２の化合物１〜６５，特に３６：化学増感剤：トリフェニルホスフィン セレニド，特開平５−４０３２４の化合物５０；
【０１１９】
染料：特開平３−１５６４５０の１５〜１８頁のａ−１〜ｂ−２０，特にａ−１，１２，１８，２７，３５，３６，ｂ−５，２７〜２９頁のＶ−１〜２３，特にＶ−１，ＥＰ４４５６２７Ａの３３〜５５頁のＦ−Ｉ−１〜Ｆ−II−４３，特にＦ−Ｉ−１１，Ｆ−II−８，ＥＰ４５７１５３Ａの１７〜２８頁のIII−１〜３６，特にIII−１，３，ＷＯ８８／０４７９４の８〜２６のＤｙｅ−１〜１２４の微結晶分散体，ＥＰ３１９９９９Ａの６〜１１頁の化合物１〜２２，特に化合物ｌ，ＥＰ５１９３０６Ａの式（１）ないし（３）で表わされる化合物Ｄ−１〜８７（３〜２８頁），ＵＳ４，２６８，６２２の式（Ｉ）で表わされる化合物１〜２２（カラム３〜１０），ＵＳ４，９２３，７８８の式（Ｉ）で表わされる化合物（１）〜（３１）（カラム２〜９）；ＵＶ吸収剤：特開昭４６−３３３５の式（１）で表わされる化合物（１８ｂ）〜（１８ｒ），１０１〜４２７（６〜９頁），ＥＰ５２０９３８Ａの式（Ｉ）で表わされる化合物（３）〜（６６）（１０〜４４頁）及び式（III）で表わされる化合物ＨＢＴ−１〜１０（１４頁），ＥＰ５２１８２３Ａの式（１）で表わされる化合物（１）〜（３１）（カラム２−９）。
【０１２０】
本発明は一般用もしくは映画用の汎用のカラーネガフイルムに適用することができる。また、特公平２−３２６１５、実公平３−３９７８４に記載されているレンズ付きフィルムユニット用に好適である。本発明に使用できる適当な支持体は、例えば前述のＲＤ．Ｎｏ．１７６４３の２８頁、同Ｎｏ．１８７１６の６４７頁右欄から６４８頁左欄、および同Ｎｏ．３０７１０５の８７９頁に記載されているが、ポリエステル支持体を用いるのが好ましい。
【０１２１】
本発明に使用されるカラーネガフィルムは、磁気記録層を有する場合が好ましい。本発明に用いられる磁気記録層について説明する。本発明に用いられる磁気記録層とは、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。本発明で用いられる磁性体粒子は、γＦｅ₂Ｏ₃などの強磁性酸化鉄、Ｃｏ被着γＦｅ₂Ｏ₃、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γＦｅ₂Ｏ₃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Ｓ_BET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３．０×１０⁴〜３．０×１０⁵Ａ／ｍであり、特に好ましくは４．０×１０⁴〜２．５×１０⁵Ａ／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６−１６１０３２に記載された如くその表面に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。又特開平４−２５９９１１、同５−８１６５２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。
【０１２２】
磁性体粒子に用いられるバインダーは、特開平４−２１９５６９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あげられ、例えば特開平６−５９３５７に記載されている。
【０１２３】
前述の磁性体を上記バインダー中に分散する方法は、特開平６−３５０９２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に記載の分散剤や、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。磁性体粒子の塗布量は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、トランスファーロール、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５−３４１４３６等に記載の塗布液が好ましい。
【０１２４】
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合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、二酸化珪素、二酸化チタン、シリコンカーバイト等の酸化物、炭化珪素、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材についてはＵＳ５，３３６，５８９、同５，２５０，４０４、同５，２２９，２５９、同５，２１５，８７４、ＥＰ４６６，１３０に記載されている。
【０１２５】
本発明に用いられるポリエステル支持体について記すが、後述する感材、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報、公技番号９４−６０２３（発明協会；１９９４．３．１５．）に記載されている。本発明に用いられ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。本発明のポリエステルのＴｇは５０℃以上であり、さらに９０℃以上が好ましい。
【０１２６】
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Ｓｂ₂Ｏ₅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。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。又ライトパイピング防止のため、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練り込むことにより目的を達成することが可能である。
【０１２７】
次に、本発明では支持体と感材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。
【０１２８】
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、Ａｌ₂Ｏ₃、Ｉｎ₂Ｏ₃、ＳｉＯ₂、ＭｇＯ、ＢａＯ、ＭｏＯ₃、Ｖ₂Ｏ₅の中から選ばれた少くとも１種の体積抵抗率が１０⁷Ω・cm以下、より好ましくは１０⁵Ω・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、更にはゾル状の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。感材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。
【０１２９】
本発明の感材には滑り性がある事が好ましい。滑り剤含有層は感光層面、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％ＰＨ）。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。本発明に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。
【０１３０】
本発明の感材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、バック面とどちらでもよいが、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ほうが好ましく、平均粒径の０．９〜１．１倍の間に全粒子数の９０％以上が含有されることが好ましい。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。
【０１３１】
次に本発明で用いられ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。更に本発明の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出来る。これらの帯電防止されたパトローネは特開平１−３１２５３７、同１−３１２５３８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のカートリツジの径を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以下好ましくは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。
【０１３２】
更に本発明で用いられる、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。またフイ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、同５，２２６，６１３に開示されている。本発明に用いられる写真フィルムは現像前のいわゆる生フィルムでもよいし、現像処理された写真フィルムでもよい。又、生フィルムと現像済みの写真フィルムが同じ新パトローネに収納されていてもよいし、異なるパトローネでもよい。
【０１３３】
本発明の感光材料は、乳剤層を有する側の全親水性コロイド層の膜厚の総和が２８μｍ以下であることが好ましく、２３μｍ以下がより好ましく、１８μｍ以下が更に好ましく、１６μｍ以下が特に好ましい。また膜膨潤速度Ｔ_1/2は３０秒以下が好ましく、２０秒以下がより好ましい。Ｔ_1/2は発色現像液で３０℃、３分１５秒処理した時に到達する最大膨潤膜厚の９０％を飽和膜厚としたとき、膜厚そのものが１／２に到達するまでの時間と定義する。膜厚は２５℃相対湿度５５％調湿下（２日）で測定した膜厚を意味し、Ｔ_1/2は、エー・グリーン（A.Green）らのフォトグラフィック・サイエンス・アンド・エンジニアリング（Photogr.Sci.Eng.），１９巻、２，１２４〜１２９頁に記載の型のスエロメーター（膨潤計）を使用することにより測定できる。Ｔ_1/2は、バインダーとしてのゼラチンに硬膜剤を加えること、あるいは塗布後の経時条件を変えることによって調整することができる。また、膨潤率は１５０〜４００％が好ましい。膨潤率とはさきに述べた条件下での最大膨潤膜厚から、式：（最大膨潤膜厚−膜厚）／膜厚により計算できる。本発明の感光材料は、乳剤層を有する側の反対側に、乾燥膜厚の総和が２μｍ〜２０μｍの親水性コロイド層（バック層と称す）を設けることが好ましい。このバック層には、前述の光吸収剤、フィルター染料、紫外線吸収剤、スタチック防止剤、硬膜剤、バインダー、可塑剤、潤滑剤、塗布助剤、表面活性剤を含有させることが好ましい。このバック層の膨潤率は１５０〜５００％が好ましい。
【０１３４】
【実施例】
以下に、本発明を実施例により、更に詳細に説明するが、本発明はこれらに限定されるものではない。
【０１３５】
実施例１
１．試験したカラーネガフィルム
下記のように２種類のカラーネガフィルム試料１０１と１０２を作製した。
【０１３６】
下塗りを施した三酢酸セルロースフィルム支持体上に、下記に示すような組成の各層を重層塗布し、撮影用ネガ型多層カラー感光材料を作製した。
（感光層組成）
各層に使用する素材の主なものは下記のように分類されている；
ＥｘＣ：シアンカプラー ＵＶ ：紫外線吸収剤
ＥｘＭ：マゼンタカプラー ＨＢＳ：高沸点有機溶剤
ＥｘＹ：イエローカプラー Ｈ ：ゼラチン硬化剤
ＥｘＳ：増感色素
各成分に対応する数字し、g/m²単位で表した塗布量を示し、ハロゲン化銀については、銀換算の塗布量を示す。ただし増感色素については、同一層のハロゲン化銀１モルに対する塗布量をモル単位で示す。
【０１３７】
〔試料１０１〕
第１層（ハレーション防止層）
黒色コロイド銀 銀 ０．０９
ゼラチン １．６０
ＥｘＭ−１ ０．１２
ＥｘＦ−１ ２．０×１０^-3
固体分散染料ＥｘＦ−２ ０．０３０
固体分散染料ＥｘＦ−３ ０．０４０
ＨＢＳ−１ ０．１５
ＨＢＳ−２ ０．０２
【０１３８】
第２層（中間層）
沃臭化銀乳剤Ｍ 銀 ０．０６５
ＥｘＣ−２ ０．０４
ポリエチルアクリレートラテックス ０．２０
ゼラチン １．０４
【０１３９】
第３層（低感度赤感乳剤層）
沃臭化銀乳剤Ａ 銀 ０．２５
沃臭化銀乳剤Ｂ 銀 ０．２５
ＥｘＳ−１ ６．９×１０^-5
ＥｘＳ−２ １．８×１０^-5
ＥｘＳ−３ ３．１×１０^-4
ＥｘＣ−１ ０．１７
ＥｘＣ−３ ０．０３０
ＥｘＣ−４ ０．１０
ＥｘＣ−５ ０．０２０
ＥｘＣ−６ ０．０１０
Ｃｐｄ−２ ０．０２５
ＨＢＳ−１ ０．１０
ゼラチン ０．８７
【０１４０】
第４層（中感度赤感乳剤層）
沃臭化銀乳剤Ｃ 銀 ０．７０
ＥｘＳ−１ ３．５×１０^-4
ＥｘＳ−２ １．６×１０^-5
ＥｘＳ−３ ５．１×１０^-4
ＥｘＣ−１ ０．１３
ＥｘＣ−２ ０．０６０
ＥｘＣ−３ ０．００７０
ＥｘＣ−４ ０．０９０
ＥｘＣ−５ ０．０１５
ＥｘＣ−６ ０．００７０
Ｃｐｄ−２ ０．０２３
ＨＢＳ−１ ０．１０
ゼラチン ０．７５
【０１４１】
第５層（高感度赤感乳剤層）
沃臭化銀乳剤Ｄ 銀 １．４０
ＥｘＳ−１ ２．４×１０^-4
ＥｘＳ−２ １．０×１０^-4
ＥｘＳ−３ ３．４×１０^-4
ＥｘＣ−１ ０．１０
ＥｘＣ−３ ０．０４５
ＥｘＣ−６ ０．０２０
ＥｘＣ−７ ０．０１０
Ｃｐｄ−２ ０．０５０
ＨＢＳ−１ ０．２２
ＨＢＳ−２ ０．０５０
ゼラチン １．１０
【０１４２】
第６層（中間層）
Ｃｐｄ−１ ０．０９０
固体分散染料ＥｘＦ−４ ０．０３０
ＨＢＳ−１ ０．０５０
ポリエチルアクリレートラテックス ０．１５
ゼラチン １．１０
【０１４３】
第７層（低感度緑感乳剤層）
沃臭化銀乳剤Ｅ 銀 ０．１５
沃臭化銀乳剤Ｆ 銀 ０．１０
沃臭化銀乳剤Ｇ 銀 ０．１０
ＥｘＳ−４ ３．０×１０^-5
ＥｘＳ−５ ２．１×１０^-4
ＥｘＳ−６ ８．０×１０^-4
ＥｘＭ−２ ０．３３
ＥｘＭ−３ ０．０８６
ＥｘＹ−１ ０．０１５
ＨＢＳ−１ ０．３０
ＨＢＳ−３ ０．０１０
ゼラチン ０．７３
【０１４４】
第８層（中感度緑感乳剤層）
沃臭化銀乳剤Ｈ 銀 ０．８０
ＥｘＳ−４ ３．２×１０^-5
ＥｘＳ−５ ２．２×１０^-4
ＥｘＳ−６ ８．４×１０^-4
ＥｘＣ−８ ０．０１０
ＥｘＭ−２ ０．１０
ＥｘＭ−３ ０．０２５
ＥｘＹ−１ ０．０１８
ＥｘＹ−４ ０．０１０
ＥｘＹ−５ ０．０４０
ＨＢＳ−１ ０．１３
ＨＢＳ−３ ４．０×１０^-3
ゼラチン ０．８０
【０１４５】
第９層（高感度緑感乳剤層）
沃臭化銀乳剤Ｉ 銀 １．２５
ＥｘＳ−４ ３．７×１０^-5
ＥｘＳ−５ ８．１×１０^-5
ＥｘＳ−６ ３．２×１０^-4
ＥｘＣ−１ ０．１０
ＥｘＭ−１ ０．０２０
ＥｘＭ−４ ０．０２５
ＥｘＭ−５ ０．０４０
Ｃｐｄ−３ ０．０４０
ＨＢＳ−１ ０．２５
ポリエチルアクリレートラテックス ０．１５
ゼラチン １．３３
【０１４６】
第１０層（イエローフィルター層）
黄色コロイド銀 銀 ０．０１５
Ｃｐｄ−１ ０．１６
固体分散染料ＥｘＦ−５ ０．０６０
固体分散染料ＥｘＦ−６ ０．０６０
油溶性染料ＥｘＦ−７ ０．０１０
ＨＢＳ−１ ０．６０
ゼラチン ０．６０
【０１４７】
第１１層（低感度青感乳剤層）
沃臭化銀乳剤Ｊ 銀 ０．０９
沃臭化銀乳剤Ｋ 銀 ０．０９
ＥｘＳ−７ ８．６×１０^-4
ＥｘＣ−８ ７．０×１０^-3
ＥｘＹ−１ ０．０５０
ＥｘＹ−２ ０．２２
ＥｘＹ−３ ０．５０
ＥｘＹ−４ ０．０２０
Ｃｐｄ−２ ０．１０
Ｃｐｄ−３ ４．０×１０^-3
ＨＢＳ−１ ０．２８
ゼラチン １．２０
【０１４８】
第１２層（高感度青感乳剤層）
沃臭化銀乳剤Ｌ 銀 １．００
ＥｘＳ−７ ４．０×１０^-4
ＥｘＹ−２ ０．１０
ＥｘＹ−３ ０．１０
ＥｘＹ−４ ０．０１０
Ｃｐｄ−２ ０．１０
Ｃｐｄ−３ １．０×１０^-3
ＨＢＳ−１ ０．０７０
ゼラチン ０．７０
【０１４９】
第１３層（第１保護層）
ＵＶ−１ ０．１９
ＵＶ−２ ０．０７５
ＵＶ−３ ０．０６５
ＨＢＳ−１ ５．０×１０^-2
ＨＢＳ−４ ５．０×１０^-2
ゼラチン １．８
【０１５０】
第１４層（第２保護層）
沃臭化銀乳剤Ｍ 銀 ０．１０
Ｈ−１ ０．４０
Ｂ−１（直径１．７μｍ） ５．０×１０^-2
Ｂ−２（直径１．７μｍ） ０．１５
Ｂ−３ ０．０５
Ｓ−１ ０．２０
ゼラチン ０．７０
【０１５１】
更に、各層に適宜、保存性、処理性、圧力耐性、防黴・防菌性、帯電防止性及び塗布性をよくするためにＷ−１ないしＷ−３、Ｂ−４ないしＢ−６、Ｆ−１ないしＦ−１７及び、鉄塩、鉛塩、金塩、白金塩、パラジウム塩、イリジウム塩、ロジウム塩が含有されている。
【０１５２】
【表４】

【０１５３】
表４において、
（１）乳剤Ｊ〜Ｌは特開平２−１９１９３８号の実施例に従い、二酸化チオ尿素とチオスルフォン酸を用いて粒子調製時に還元増感されている。
（２）乳剤Ａ〜Ｉは特開平３−２３７４５０号の実施例に従い、各感光層に記載の分光増感色素とチオシアン酸ナトリウムの存在下に金増感、硫黄増感とセレン増感が施されている。
（３）平板状粒子の調製には特開平１−１５８４２６号の実施例に従い、低分子量ゼラチンを使用している。
（４）平板状粒子には特開平３−２３７４５０号に記載されているような転位線が高圧電子顕微鏡を用いて観察されている。
（５）乳剤Ｌは特開昭６０−１４３３３１号に記載されている内部高ヨードコアーを含有する二重構造粒子である。
【０１５４】
（有機固体分散染料の分散物の調製）
下記、ＥｘＦ−２を次の方法で分散した。即ち、水２１．７ミリリットル及び５％水溶液のｐ−オクチルフェノキシエトキシエトキシエタンスルホン酸ソーダ３ミリリットル並びに５％水溶液のｐ−オクチルフェノキシポリオキシエチレンエーテル（重合度１０）０．５ｇとを７００ミリリットルのポットミルに入れ、染料ＥｘＦ−２を５．０ｇと酸化ジルコニウムビーズ（直径１mm）５００ミリリットルを添加して内容物を２時間分散した。この分散には中央工機製のＢＯ型振動ボールミルを用いた。分散後、内容物を取り出し、１２．５％ゼラチン水溶液８ｇに添加し、ビーズを濾過して除き、染料のゼラチン分散物を得た。染料微粒子の平均粒径は０．４４μｍであった。
【０１５５】
同様にして、ＥｘＦ−３、ＥｘＦ−４及びＥｘＦ−６の固体分散物を得た。染料微粒子の平均粒径はそれぞれ、０．２４μｍ、０．４５μｍ、０．５２μｍであった。ＥｘＦ−５は欧州特許出願公開（ＥＰ）第５４９，４８９Ａ号明細書の実施例１に記載の微小析出（Microprecipitation）分散方法により分散した。平均粒径は０．０６μｍであった。
【０１５６】
【化１】

【０１５７】
【化２】

【０１５８】
【化３】

【０１５９】
【化４】

【０１６０】
【化５】

【０１６１】
【化６】

【０１６２】
【化７】

【０１６３】
【化８】

【０１６４】
【化９】

【０１６５】
【化１０】

【０１６６】
【化１１】

【０１６７】
【化１２】

【０１６８】
【化１３】

【０１６９】
【化１４】

【０１７０】
【化１５】

【０１７１】
【化１６】

【０１７２】
〔試料１０２〕
次に試料１０１の第１層から第１４層までの全ての塗布層のと塗布量を２分の１に下げて低銀カラーネガフィルムを作成して試料１０２とした。すなわち、試料１０１の総塗布銀量は６．４５ｇ／ｍ² であるが、試料１０２では乳剤組成を変えることなく塗布量調節のみによって３．２２５ｇ／ｍ² に変更した。
【０１７３】
２．写真特性試験の方法
各試験用フィルムにＩＳＯ５８００（カラーネガフィルムの感度測定法）記載の標準Ｃ光源による照明のもとで標準露光量、その１／２のアンダー露光及び標準の４倍のオーバー露光の３水準の露光量で、グレーの壁を背景に人物のスナップ撮影をし、現像処理条件は下記のように変更して行い、入力用画像の写真原稿を作成した。
こうして得られた入力用画像を発明の形態の項で説明した画像読み取り装置を用い画像信号に変換した。発明の形態４．２項の手順に従い、階調補正処理と色補正処理を組み合わせた画像処理を行い、この画像信号に基づき前記の図１０で示されるレーザー走査露光装置で下記に示すカラーペーパーに露光を施し、以下に示す所定の現像処理を行い評価用の画像を得た。この評価用画像の粒状のなめらかさを重点に総合画質を、写真評価を専門とする１０人に下記５点法で採点してもらい平均点で評価した。
非常に劣り、許容できない。・・・・１点
やや劣り、許容できない。・・・・・２点
比較的に劣るが許容できる。・・・・３点
比較的に優れ、好ましい。・・・・・４点
非常に好ましい。・・・・・・・・・５点
【０１７４】
３．入力用画像の現像処理
下記のカラーネガ用現像処理仕様に従った。
処理機としては、富士写真フイルム（株）製自動現像機ＦＰ−５６０Ｂを用いて以下に示す処理工程及び処理液で処理した。
また、本発明の処理工程である定着工程省略処理は、発色現像及び漂白工程の後、試料を２つの定着ラックを飛ばして直ちに水洗浴へ送られるように処理機のフィルム搬送系を改造して行った。
【０１７５】

安定液は（２）から（１）への向流方式であり、水洗水のオーバーフロー液は全て定着（２）へ導入した。また、定着液も（２）から（１）へ向流配管で接続されている。尚、現像液の漂白工程への持ち込み量、漂白液の定着工程への持ち込み量及び定着液の水洗工程への持ち込み量は感光材料３５ｍｍ巾１．１ｍ当たりそれぞれ２．５ミリリットル、２．０ミリリットル、２．０ミリリットルであった。また、クロスオーバーの時間はいずれも６秒であり、この時間は前工程の処理時間に包含される。
【０１７６】
以下に処理液の組成を示す。

【０１７７】

【０１７８】

【０１７９】
（水洗水）
水道水をＨ型強酸性カチオン交換樹脂（ロームアンドハース社製アンバーライトＩＲ−１２０Ｂ）と、ＯＨ型強塩基性アニオン交換樹脂（同アンバーライトＩＲ−４００）を充填した混床式カラムに通水してカルシウム及びマグネシウムイオン濃度を３mg／リットル以下に処理し、続いて二塩化イソシアヌール酸ナトリウム２０mg／リットルと硫酸ナトリウム１５０mg／リットルを添加した。この液のｐＨは６．５〜７．５の範囲にあった。
【０１８０】

【０１８１】
４．評価用画像の画像処理
上記の構成で制作された入力用画像を電気的画像信号に変換し、その信号を入力してポジ画像を作ることができる市販の入力機の例として高速スキャナー／画像処理ワークステーションＳＰ−１０００（富士写真フイルム（株）製）、市販の出力機の例としてレーザープリンター／ペーパープロセサーＬＰ−１０００Ｐ（富士写真フイルム（株）製）を使用した。また、ＳＰ−１０００に関しては、前記画像処理が行えるようにプログラムソフトを変更して使用した。
また、比較試料用には、現在一般的な面露光方式の富士写真フイルム（株）製ミニラボＰＰ−１２５７Ｖを使用した。この装置のプリンターは現像処理済みカラーネガを透過してカラーペーパー上に焼き付けが行われる同時全面露光方式で、フィルターの制御でカラーバランスを制御する現在の市場で普通に行われている方式のものである。
いずれもカラーペーパーは、市販のフジカラーレーザーペーパーを使用し、現像処理は一般用のカラーペーパー処理処方ＣＰ−４７Ｌとその処理剤（いずれも富士写真フイルム（株）製）にしたがって行った。
【０１８２】
５．試験
次の各試験を行った。
▲１▼比較実験−１：上記したカラーネガ用現像処理処方と工程によって基準現像処理した試料１０１及び１０２をＳＰ−１０００で前記画像処理を行い、ＬＰ−１０００Ｐで焼き付けとポジ現像処理を行い比較用カラープリントを得た。
▲２▼比較実験−２：上記したカラーネガ用現像処理処方と工程によって基準現像処理した試料１０１及び１０２を面露光方式のＰＰ−１２５７Ｖで焼き付けとポジ現像処理を行い比較用カラープリントを得た。
▲３▼比較実験−３：定着工程省略処理の試料１０１及び１０２をＰＰ−１２５７Ｖで焼き付けとポジ現像処理を行い比較用カラープリントを得た。
▲４▼本発明実験−１：比較実験−３と同様の定着工程省略処理した試料１０１及び１０２をＳＰ−１０００で前記画像処理を行い、ＬＰ−１０００Ｐで焼き付けとポジ現像処理を行い、本発明の方法と装置によるカラープリントを得た。画像処理条件は、前記４．２に説明した画像処理装置（すなわちＳＰ−１０００）において、定着工程が省略された現像処理で得た現像濃度が入力されることに伴う条件設定の修正がされている以外は、ＳＰ−１０００の通常条件通りである。
【０１８３】
６．試験結果
試験結果を表５に記載した。
【０１８４】
【表５】

【０１８５】
表５から判るように、基準現像処理を行った比較実験−１と２では、いづれも標準的な画質を示し、画像処理の有無とそれに伴う出力装置の差つまり比較実験−１と２の間の画質の差は小さい。一方、定着工程省略処理ののち画像再生のための画像処理を行わない比較実験−３では、画質の再現は不十分であり、特にオーバー露光の時にそれが著しい。定着工程省略処理ののち画像処理を行った本発明実験−１は、基準現像処理を施した上に画像処理も施した比較実験−１と同等の画質であり、画質の再現は満足されている。
また、本発明の現像処理工程からの廃液量は、基準現像処理に対して１７％減少した。さらに低銀の感光材料である試料１０２の方がその効果が顕著に現れた。
一方、この実施例では、水洗代替安定液を使用したが、水洗方式を採用した場合は、排水中の窒素化合物の量が８５％減少することは、上記の各工程の処方値と補充量から求められる。
また、本実施例におけるカラーネガフィルムの現像開始からカラープリントを得る全工程の時間短縮は、１００秒（定着工程相当分）であった。
【０１８６】
実施例２
実施例１で行った試験を繰り返して行った。ただし、今回は現像処理済み試料からの画像読み取りを図１１に示し、本明細書の４．１項で述べた反射型濃度読み取り方式で行った。実施例１で使用した市販の画像処理装置（ＳＰ−１０００）には、透過型及び反射型画像読み取り装置が装着されているので、これを使用した。
画像読み取りは、円滑に行われ、画像処理及びカラーペーパーへの出力も実施例１と同様に行われ、その結果実施１と同じく基準現像処理で得られた画像と同等の画質のプリントが得られた。
【０１８７】
【発明の効果】
撮影済みカラーフィルムを現像処理するに際して、定着工程を省略した簡略現像処理を行っても、得られた画像情報に画像処理を施すことによって、基準現像処理（つまり標準的な現像処理）を行う場合と実質的に同画質の画像情報を得ることができる。さらには、それによって簡略化した現像処置から正常な画質のカラープリントを提供できる。
カラーフィルムのハロゲン化銀乳剤塗布量を低減させることにより、本発明の効果を維持し、かつカラーフィルムの原料コストを下げることが可能となる。
【図面の簡単な説明】
【図１】本発明に係わる画像形成方法と装置の基本構成と全体の流れを示すブロックダイアグラム
【図２】本発明に係わる画像再生システムの基本構成を示すブロックダイアグラム
【図３】本発明に係わる画像再生システムの一実施形態における外観を示す図
【図４】透過型画像読み取り装置の概略を示す図
【図５】図２に示される画像処理装置５の構成の一部を示すブロックダイアグラム
【図６】図２に示される画像処理装置５の構成の図５に示されない他の部分を示すブロックダイアグラム
【図７】図５に示される第１のフレームメモリユニット、第２のフレームメモリユニット及び第３のフレームメモリユニットの詳細を示すブロックダイアグラム
【図８】図６に示される第１の画像処理手段の詳細を示すブロックダイアグラム
【図９】図２に示される画像出力装置の概略を示す図
【図１０】図９に示される画像出力装置のレーザー光照射手段
【図１１】反射型画像読み取り装置の概略を示す図
【符号の説明】
図１〜１１における符号の説明
Ｆ フィルム
Ｐ カラープリント又はカラーペーパー
０１ ＤＸコード
０２ 現像選択指示部
０３ 基準現像過程
０３Ａ非基準現像過程
０４ マニユアル現像選択
１ 画像読み取り装置
５ 画像処理装置
８ 画像出力装置
１０ 透過型画像読み取り装置
１１ 光源
１２ 光量調節ユニット
１３ 色分解ユニット
１４ 拡散ユニット
１５ ＣＣＤエリアセンサー
１６ レンズ
１７ 増幅器
１８ Ａ／Ｄ変換器
１９ ＣＣＤ補正手段
２０ ログ変換器
２１ インターフェイス
２２ キヤリア
２３ モーター
２４ 駆動ローラ
２５ 画面検出センサー
２６ ＣＰＵ
３０ 反射型画像読み取り装置
３１ 光源
３２ ミラー
３３ カラーバランスフィルタ
３４ 光量調節ユニット
３５ ＣＣＤエリアセンサー
３６ レンズ
３７ 増幅器
３８ Ａ／Ｄ変換器
３９ ＣＣＤ補正手段
４０ ログ変換器
４８ インターフェイス
４９ 加算平均演算手段
５０ａ第１のラインバッファ
５０ｂ第２のラインバッファ
５１ 第１のフレームメモリユニット
５１Ｒ Ｒデータメモリ
５１Ｇ Ｇデータメモリ
５１Ｂ Ｂデータメモリ
５２ 第２のフレームメモリユニット
５２Ｒ Ｒデータメモリ
５２Ｇ Ｇデータメモリ
５２Ｂ Ｂデータメモリ
５３ 第３のフレームメモリユニット
５３Ｒ Ｒデータメモリ
５３Ｇ Ｇデータメモリ
５３Ｂ Ｂデータメモリ
５５ セレクタ
６０ ＣＰＵ
６１ 第１の画像処理手段
６２ 第２の画像処理手段
６３ 入力バス
６４ 出力バス
６５ データバス
６６ メモリ
６７ ハードデイスク
６８ ＣＲＴ
６９ キーボード
７０ 通信ポート
７５ データ合成手段
７６ 合成データメモリ
７６Ｒ Ｒデータメモリ
７６Ｇ Ｇデータメモリ
７６Ｂ Ｂデータメモリ
７７ インターフェイス
７８ インターフェイス
７９ ＣＰＵ
８０ 画像データメモリ
８１ Ｄ／Ａ変換器
８２ レーザー光照射手段
８３ 変調器駆動手段
８４ａ，ｂ，ｃ 半導体レーザー光源
８５ 波長変換手段
８６ 波長変換手段
８７Ｒ，Ｇ，Ｂ 光変調器
８８Ｒ，Ｇ，Ｂ 反射ミラー
８９ ポリゴンミラー
９０ カラーペーパー
９１ マガジン
９２ 穿孔手段
９４ 発色現像槽
９５ 漂白定着槽
９６ 水洗槽
９７ 乾燥部
９８ カッター
９９ ソータ
１００ 色濃度階調変換手段
１０１ 彩度変換手段
１０２ デジタル倍率変換手段
１０３ 周波数処理手段
１０４ ダイナミックレンジ変換手段[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photographic system for obtaining a positive image such as a color print by developing a general color film, and particularly for obtaining a high-quality color print in a short time from a photographed silver halide color photographic light-sensitive material. The present invention relates to a color image forming method.
In particular, the present invention relates to a photographic processing system based on a new technical idea in which a part of the processing process of a photographed photosensitive material is omitted to speed up the process and the resulting deterioration in photographic characteristics is compensated by image processing.
[0002]
[Prior art]
Currently, the most common form of color photography is the development of processed silver halide color photographic materials (hereinafter referred to as color films) at a laboratory, and printing the resulting images on photographic paper. This is a so-called negative paper system (referred to as N / P system) for obtaining color prints. The finishing time from the receipt of the photographed color film from the customer to the delivery of the color print to the customer is one day (finishing the next day) when using a large lab, but between the photographic shop and the lab. Stores that do not require delivery time are becoming popular. In this case, the finishing time is about 30 minutes to 1 hour. This type of shop is commonly referred to as a minilab for a large laboratory. Finishing a print in a minilab greatly reduces the finishing time and is welcomed by customers. Nonetheless, the time required to finish is far from the customer who requested development and printing of the photographed film waiting for the finish at the store to receive the print and return.
[0003]
Although it is difficult to reduce the finishing time to such an extent that the customer can finish the print while in the store, it is also highly desirable. However, the time required for color negative film development processing in the finishing time is 10 to 15 minutes even if it is cut off, and occupies a particularly large portion of the total work time until the color print can be delivered to the customer. ing.
Therefore, it is particularly desired to shorten the development time of the color negative film. By the way, many types of color negative films are sold by each photographic material manufacturer, and each of them takes on all of them, but due to the cost of developing machines and the required floor space, these various types The actual situation is that the color negative film is developed in the same processing step with the same processing liquid by one developing machine. Therefore, the development processing time of the negative film is determined in accordance with the product having the longest time required for the development processing among various negative films.
[0004]
In other words, in the development laboratory, the most economical method of performing various color negative films using the same photographic processing solution in the same developing machine is selected, and there is almost no service for performing short-time processing according to the photosensitive material. is the current situation.
In Japanese Patent Publication No. 7-52287, the bleaching process is omitted when developing a color negative film that has already been photographed, and the process of shortening the process is accompanied by the disadvantage that the density of the dye image and the density of the silver image overlap with each other. A method is disclosed in which a density value is read and the respective density values of a color image and a silver image are separately obtained by using a calculation method for obtaining an analysis density of a dye image from the value. However, even if the analysis density of the three colors of cyan, yellow and magenta and neutral silver is determined by the disclosed method, the quality of the resulting positive image is inferior to the standard quality. That is, it is estimated that image quality factors other than the analysis density are present. Therefore, this disclosed technology has not yet been put into practical use.
[0005]
Another problem at commercial laboratories centering on mini-labs is environmental measures for waste liquid and waste water from development processing. Since nitrogen compounds contained in wastewater discharged into sewage and the like are subject to wastewater regulation, wastewater containing such compounds increases the processing burden in many areas. Further, when consigning waste liquid such as used processing liquid, the smaller the amount of waste liquid, the lower the waste liquid consignment processing cost. Therefore, in the development facility, a development processing method with a small amount of waste liquid is desired, and in the case of processing for discharging wastewater, wastewater with less nitrogen components in addition to COD components is desired. From this point of view, the general development process uses water-saving water washing (also referred to as water-washing alternative stabilizing liquid; hereinafter referred to collectively as low-replenishment water washing) to stop discharge as washing waste water and classify it as waste liquid. Further reduction of weight is planned. Waste liquids are also thoroughly reduced in volume by reducing the amount of replenishment, but further reduction in both waste water and waste liquids is always desired.
[0006]
Another issue that needs to be solved at commercial laboratories around the mini-lab is securing development quality in the off-season. In the off-season, because the amount of development processing is small, the amount of replenisher added each time film or photographic paper is processed in the developing machine is small, and therefore the processing liquid in the processing tank is not changed (replacement speed). Thus, deterioration associated with extension of the residence time of the treatment liquid in the tank, for example, precipitation of sulfide or silver compound occurs. Therefore, it is strongly desired to take measures to keep the liquid in the treatment tank stable even in the off-season.
[0007]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to solve the above-mentioned problems of the color processing laboratory. Specifically, the first object of the present invention is to shoot without deteriorating the photographic quality. It is to establish a color image forming method capable of shortening the time from the start of a developing machine to the development of a color photographic material through a development and printing process to obtain a positive image and ensuring the quality of the image.
The second object of the present invention is to establish a color image forming method incorporating a developing process in which the amount of photographic processing waste liquid accompanying the developing process is reduced and the discharge amount of nitrogen compounds is reduced.
A third object of the present invention is to establish a color image forming method incorporating a stable development processing method that does not cause deterioration of the developing processing solution, sulfidation, or silver-containing precipitates in the low season.
[0008]
[Means for Solving the Problems]
In order to achieve the above object, the present inventors
(1) Possibility of omitting processing steps with a large environmental load,
(2) Possibility of omitting development processing steps that lead to faster processing, and
(3) As a result of earnest examination of the image forming method from the three viewpoints of studying the method for relieving the deterioration in development processing quality associated with the above item 2, the rational construction of the development processing step and the image processing to the developed image are performed. It has been found that the purpose can be achieved by applying, and the present invention has been achieved.
That is, the present invention is as follows.
[0009]
1. The photographed silver halide color photographic material is subjected to (1) a development process including a color development step and a bleaching step and not including a fixing step, and (2) image information is read photoelectrically from the developed image. It is converted into electrical digital information, and (3) the electrical digital information is subjected to image processing to correct the image quality characteristics to be obtained when the color photographic material is developed under standard development processing conditions. To obtain image information having the same image quality as that obtained when the color photographic material is subjected to a standard development process.
2. 2. The color image forming method according to 1 above, wherein image information is photoelectrically read from reflected developed light-sensitive silver halide color photographic material and converted into electrical digital information.
3. The amount of silver halide applied to the photographed silver halide color photographic material is 1.0 to 4.0 g / m.² (3) The color image forming method according to the above (1) or (2), wherein the color image forming method is silver equivalent.
4). The color image formation according to any one of 1 to 3 above, wherein the replenishing amount in the bleaching step and the final bath step is 30 ml or less per 35 mm 24 film (135-24 format) film. Method.
5. 5. The color according to any one of 1 to 4 above, wherein the total amount of the development processing waste discharged from the development processing step is 50 milliliters or less per 35 mm / 24 film (135-24 format) film. Image forming method.
6). The photographed silver halide color photographic material is subjected to (1) a development process including a color development process and a bleaching process and not including a fixing process, and (2) image information is photoelectrically read from the developed image. (3) image processing of the electrical digital information to correct the image quality characteristics to be obtained when the color photographic material is developed under the standard development processing conditions. , A material used in a color image forming method comprising obtaining image information having the same image quality as that obtained when the color photographic material is subjected to a standard development process, and the coating amount of silver halide is 1.0 to 4.0 g. / m² (Silver equivalent amount) Silver halide color photographic material.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail. Before that, some explanations of terms used in the present invention are added.
In the present invention, the “type” of a photographed color photographic material (hereinafter simply referred to as a color film) is used for both manufacturers and varieties supplying the photographic material. That is, if a certain manufacturer manufactures the same product recipe and has the same product name, they are the same “type”. However, if the sensitivity display and product name are different even for products of the same manufacturer, they are different “types”.
The color photographic material of the present invention includes a color negative film and a color reversal film. Among them, a color negative film is the main object. Note that the color diffusion transfer method (color instant photo) and the heat development type color diffusion transfer method are also systems including a color photographing material. However, the system in which this kind of photographing material and positive material are simultaneously developed is described in the present invention. Is out of range.
[0011]
Also, in the present invention, what is called a standard development process refers to a development process that is performed as a standard development by the developer. This processing generally conforms to a substantially international common processing that is generally used in most developing laboratories worldwide. This international common processing is specifically a development processing prescription called a color negative film development process called CN16 series (Fuji Photo Film Co., Ltd.), C41 series (Eastman Kodak, USA), etc. Even though they are named differently, they are substantially common and most commonly used. However, if the processing at each laboratory is completely the same by this common processing, there are differences in the technical contents of the manufacturers of photosensitive materials and developing chemicals and differences in customer preferences depending on the region. There are some differences. Therefore, in the present invention, the development processing performed by each development laboratory as the standard of the development laboratory is referred to as the standard development processing. However, due to the above relationship, this is a globally common within a certain tolerance or freedom. It is also a standard process.
[0012]
In the present invention, the standard development process and the global standard process that forms the basis thereof are composed of development, bleaching, fixing, rinsing, image stabilization, drying processes and, in some cases, a slight rinsing process (color reversal film). In this case, a few more steps are added). For the following explanation of the present invention, if the waste liquid and waste water from the development processing step are mentioned, the used processing solution, ie, the waste liquid, from the color development, bleaching and fixing steps, and the washing step, Flushing wastewater is discharged and both waste liquid and wastewater are treated according to local environmental regulations. As described above, the water washing process may take the form of low replenishment type water washing, in which case it is treated as waste liquid without draining.
[0013]
In the present invention, the term “development process” refers to the entire process starting from the development process and completed in the drying process, and the term “development” or “bleaching” specifically refers to the “development” process or “bleaching” process. .
[0014]
Furthermore, in the following description, there are two operations that are completely different even though the common terms “processing”, “development processing” and “image processing” are attached. "And" image processing ".
[0015]
Now, with the above as a prelude, the present invention will be described in detail in the following order.
In the present invention, a photographed silver halide color photographic material is subjected to (1) a color development step and a bleaching step, and a development process not including a fixing step, and (2) photoelectrically converting image information from the developed image. Read and convert it into electrical digital information, and (3) image-process it to correct the image quality characteristics to be obtained when developing the color photographic material under standard development processing conditions. Thus, image information having the same image quality as that obtained when the color photographic material is subjected to the standard development processing is obtained.
[0016]
Here, the “image quality characteristics” are the characteristics that constitute the image quality, and include gradation, color balance, maximum density (Dmax), white background density (Dmin), sharpness, and graininess. It consists of various characteristics. Therefore, in the above description, “obtaining image information having the same image quality as that obtained when the reference development is performed by correcting the image quality characteristic” means that the image information obtained by performing the developing process without the fixing step is described above. The image quality is the same as the image quality of the image information obtained by modifying the characteristics of the image quality element and the standard development is performed. This is a case where the characteristics are matched and the density difference is within ± 10% when expressed using photographic characteristic values expressed based on the measured density value.
[0017]
The common development process that accepts color negative films from commercial companies consists of color development, bleaching, fixing, image stabilization bath, and some rinsing and washing steps as described above. It is intended to speed up by omitting. By omitting the fixing process, the process time is generally shortened by 1.5 to 5 minutes. For example, the first generation C41 formulation used by a large-scale developer can reduce the process time by 4 minutes and 20 seconds. However, unfixed films have opaque haze due to silver halide grains and cannot be printed as they are. In the present invention, the unfixed film is extracted as image information that also includes noise information photoelectrically using an image reading device, and then image information components are extracted by image processing, and the image information is subjected to image processing. The gist of the invention is to perform an operation of converting the image information to the image quality equivalent to that obtained when the reference development processing is performed, and to output the converted image information to a positive image medium.
[0018]
Although it has been disclosed in the above prior art that an image can be read even if the bleaching step is omitted, according to the study of the present inventor, the reading accuracy of the image is that bleaching is performed and fixing is omitted. The method is better. Although the covering power or opacity of developed silver has been found to be higher than that of silver halide, this difference is the prior art in which developed silver remains unconverted to silver halide (US Pat. No. 5,011,286). The bleached non-fixed film of the present invention, which has been converted to silver halide by bleaching, seems to be the cause of better reading accuracy. Another reason that the present invention obtains a high-quality positive image is that, in the prior art, the image density is higher because the dye density and the silver density overlap on the high density side, and the image information reading ability is high. In contrast, the reading accuracy is lowered due to this limit, but in the present invention, it is considered that there is a margin of reading density as much as there is no overlap of developed silver. None of these are the reasons for explaining the results of the implementation and are not proven facts, but the present invention is clearly superior to the conventionally disclosed technique in both the low density and high density of the reading range.
[0019]
Image reading from the developed color negative film is not necessarily performed after completion of the development process, but can be performed at any time after the completion of the development and bleaching processes and before entering the drying process. The time until obtaining a color positive image is further shortened. As the shortest example, an image may be read at the end of the bleaching process. In that case, the fixing, washing, image stabilization, and drying process times can be shortened. Although the shortening time also varies depending on the conditions of the developer, it is generally about 2 to 11 minutes in total. Depending on the developer, the development process time of the color negative film is shortened to almost the same as that of the color printing process. .
[0020]
In addition, since the present inventors oxidize developed silver to silver halide relatively quickly in the bleaching step, the effect of the present invention, that is, the reduction in opacity is reduced when half of the bleaching step time has elapsed. May improve the reading accuracy. The scope of the present invention includes image reading in such a state during the bleaching process as long as the effects of the invention are exhibited.
In the present invention, further advantages arise by omitting the fixing step and not the bleaching step. That is to improve the reading accuracy of the image density due to the reflection density. Since developed silver is converted into silver halide having a high reflectance by bleaching, image information can be obtained with high reading accuracy when image reading is performed with reflected light. In general, image reading from a color negative film is performed with transmitted light, but in the present invention, sufficient reading accuracy can be obtained with reflected light, and either method may be selected. Details of the reading apparatus using transmitted light and reflected light will be described later together with specific examples of the apparatus. In addition, the image processing of the image information of the reflected light is performed by the same operation except that the conversion coefficient value when converting the read value into the characteristic value in the case of performing the reference processing is different. It will be explained together.
[0021]
A dual advantage is obtained by reducing the silver halide emulsion coverage of the color negative film used in the present invention. One is a reduction in weight loss due to silver halide savings, and the other is a reduction in the amount of coating, which reduces the transmission density of the developed film. As a result, the quality of the output positive image is improved. On the other hand, the reduction in the amount of silver halide is directly related to the reduction in the amount of image information. In the present invention, however, the image processing function is combined. Considerable compensation is provided by image enhancement effects such as enhancement and contrast enhancement of image details, and saturation enhancement. These will be supplemented later along with specific examples of the apparatus.
As a result of adopting the image reading method, in the present invention, the amount of silver halide applied is reduced to 1 m of color negative film.²1.0 to 4.0 g per unit, preferably 1.5 to 4.0 g, and more preferably 2.0 to 3.5 g (all are expressed in terms of silver). According to another scale, a commercially available normal color film has a silver halide coating amount of 4 to 8 g / m in terms of silver.²However, it can be reduced by 20 to 70%.
[0022]
The story goes back to image reading accuracy, but the transmission density of the color negative film after bleaching with silver halide is between 0.5 and 1.5, depending on the type of color negative film. It can be reduced in a proportional way. Thus, a 50% reduction in coating amount reduces the opacity by 0.3 to 0.7 and increases the amount of light entering the reader by 2 to 4 times.
In the present invention, it is also a great advantage that no fixing liquid is required and no fixing waste liquid is generated by not performing fixing. If a color negative film having a small silver halide emulsion coating amount is used in the present invention, the amount of waste liquid can be further reduced. In standard common representative color negative film development formulas, the replenishment amount in the bleaching process, low replenishment water washing and image stabilization process is 5, 37, and 15 milliliters per film, each of which is 35 milliliters and 37 milliliters in total. However, in the present invention, the amount of waste liquid can be reduced to a total amount of 20 ml or less, preferably 15 ml or less, by reducing the amount of silver.
Similarly, the amount of waste liquid generated from the entire development processing step of the above representative processing is 60 ml per one film of 35 mm 24 sheets. In the present invention, the total amount is 50 ml or less, preferably 35 ml or less. It is possible to reduce the amount of waste liquid.
[0023]
The film after obtaining a color print image often does not need to be stored. In that case, waste water and waste liquid can be reduced more thoroughly not only in the fixing step but also in the water washing step and the image stabilization step. For example, when applied to an undrained minilab processing machine, only the amount of bleaching waste generated even after oxidation regeneration and the amount of developing waste corresponding to the development replenishment exceeding the color development carry-over (carrying out to the next process) becomes waste. The amount of reduction is more than 90% of the amount of waste liquid from normal processing.
[0024]
Another meaning of not fixing is the absence of ammonium salt discharge. Although the regulation of nitrogen content in wastewater is carried out worldwide, in photographic processing, ammonium thiosulfate in the fixer is the source of ammonium, that is, the nitrogen content, and nitrogen compounds are discharged by not fixing. 80% to 85% of the amount can be reduced, and in many laboratories the amount of exhausted nitrogen can be reduced below the local regulation value.
[0025]
Further, the COD value of the fixing solution is higher than the COD value of the color developer, and therefore the present invention has a great effect of reducing the COD value.
[0026]
A further advantage of the present invention that omits the fixing step is to ensure development quality in the off-season, particularly in small scale laboratories. As mentioned before, during the off season, the amount of development processing is small, so the amount of replenisher added to the developing tank each time film or photographic paper is processed is small. As the retention time of the processing solution in the tank increases, sulfur compounds and dissolved silver salts decompose, and precipitation of sulfides and silver compounds occurs in the water washing tank and image stabilization tank. , It adheres to the roller and developing film and induces serious quality failure. In the development processing according to the present invention, the process is freed from sulfide and silver salt precipitation in order to omit the fixing step.
[0027]
In the above, the basic technical idea of this invention, the outline | summary of a component requirement, a preferable aspect, and the advantage accompanying them were demonstrated. Hereinafter, the present invention will be further described in the following order using specific examples as materials.
1. Overall flow of basic steps of image forming method of invention
2. Pre-development process
3. Development process
4). Image reproduction process
4.1 Reading image information from developed film
4.2 Image processing of scanned image information
4.3 Output of processed image information to printer
5. Printer output process
6). Supplementary explanation of the present invention
[0028]
1. Overall flow of basic process
The basic technology of the present invention is to read a developed silver halide color photographic material (hereinafter referred to as a color film), which is subjected to a simple development process without a fixing step, and then reads the developed image information. The digital information is converted into electrical digital information, and the digital information is subjected to image processing to correct the image quality characteristics of the wrinkles obtained when the color photographing material is developed under the standard development processing conditions. Is output to a printer to obtain a positive image having the same image quality as that obtained when the reference development processing is performed.
[0029]
FIG. 1 shows the overall flow of a typical laboratory process according to the method of the present invention. The photographed color film has a film type determination process (01) at the first stage of the development process. Although this step is not essential to the present invention, the type can be known by a perforation symbol for identification called a DX code of each film. Based on this “type” information, image processing condition setting to be described later is selected, and in some cases, whether to perform the reference process (03) or the fixing process omission process (03A) of the present invention is also selected (02). ). The selection of the standard process or the fixing process omission process may be selected according to a predetermined standard by the operator's operation regardless of what the DX code is (04). In the present invention, the fixing process omission process is performed, but in some cases, it may be necessary to perform a reference process, so this DX code discrimination process is meaningful. In addition to the above, it is needless to say that a dedicated developing machine that performs only the fixing process omission processing may be used.
[0030]
After selection of the development conditions, the film is conveyed through a series of processing tanks in the developing machine. The standard development process for color negatives comprises color development, bleaching, fixing, rinsing, image stabilization and drying, and some rinsing or rinsing processes between them. In the present invention, the fixing process is omitted from these processes. The color development process has a great effect on photographic quality, but in the fixing process, the necessary dye image has already been formed, and the silver image that interferes with the dye image has been removed. Therefore, the effect of shortening the development processing time is small and the effect of shortening the development processing time is particularly large in the present invention. The film that has been subjected to development processing including color development, bleaching, washing with water or stabilization is then transferred to image information reading step 1.
[0031]
In this step, the transmission density for each minute area unit (hereinafter referred to as a pixel) constituting the image of the developed film is measured, and the image information is read as the density for each pixel. As a result of the reading, the image information is converted into an electrical image signal based on the density value, and is converted into a digital signal by an A / D (analog / digital) converter 18 through an amplifying device 17. This information signal is sent to the image processing apparatus 5 through the log converter 20 after correction 19 of the CCD function such as sensitivity variation for each pixel and correction of dark current.
[0032]
In the image processing apparatus, electrical processing is applied to the image information converted into a digital signal to convert it into a digital image signal that is obtained when a reference development process is performed. When standard development is performed on film, this image processing simply means correcting corrections such as shooting conditions, development processing, or film characteristics, and correcting them to a statistical center value. Importantly, it is not the subject of the present invention. As described above, the developed film in the case where the fixing process omission processing is selected has silver halide remaining, and the gradation, color balance, or Dmin (density value of the unexposed area) is determined based on the standard development value. There is a bias. In the present invention, as will be described later, this bias correction is performed by image processing. The above-described image processing operation can be performed by the method and the arithmetic unit which are pending in Japanese Patent Application No. Hei. Although the following description will be made with these two examples as materials, the image forming method of the present invention is not limited to using the apparatuses described therein.
[0033]
The image signal of the film subjected to the fixing process omission processing converted into the normal photographic characteristic value at the time of the standard development is output to the printer 8, and as a result, a normal positive image is obtained. The printer may be any printer that inputs electrical image signals or photoelectric image signals, but particularly preferred printers are color prints, instant photographs, silver salt color prints such as dye thermal transfer type, ink jet, sublimation type thermal transfer, wax. It is a printer for positive images such as mold thermal transfer and color electrophotography.
The outline of the apparatus and method of the present invention for obtaining a normal positive image obtained by the standard process from a photographic image of a film having a non-normal photographic characteristic subjected to the fixing process omission processing will be described in more detail below.
[0034]
In the present invention, even if processing (ie, non-reference processing) in which the fixing step is omitted is performed, a photographic characteristic value almost equal to that obtained when the same quality image information or the same quality positive image as that obtained by the reference processing can be obtained. This can be typically determined by image density. In that case, it means that the density value is within ± 10% of the reference value. More directly, it is determined by an unbiased observer (approximate by the average of the observation results of many observers).
[0035]
2. Pre-development process
In the block diagram showing the development processing apparatus of the present invention in FIG. 1 and the flow of operations therein, the film is taken into the development processing apparatus from the left end of the digram, but first the type of film is read. This reading is performed in order to know the type of photographic film indicated on the identification perforation symbol called DX code on the film. You can also. That is, as described above, in the image processing step, the image information of the developed film is read and the read information is processed, but depending on the type of film known by the DX code, before or after the image processing. If the set processing conditions are further corrected, there may be a better finished quality as a result. In such a case, correction according to the type of film can be added to the set image processing conditions. Further, depending on the case, it is also possible to select whether to perform a reference process or a fixing process omission process. Such correction particularly increases the difference in photographic characteristics from the standard development process, such as when the development progress is slow as in a film having an ISO sensitivity of 1800, or when the amount of coated silver is large, and omission of the bleaching step causes insufficient fixing. Sometimes effective. The selection of the reference process or the fixing process omission process may be selected regardless of what the DX code is by the operation of the operator.
Of course, there is also a dedicated machine that can perform only the fixing process omission processing.
[0036]
3. Development process
After selection of development conditions, the film is conveyed to a developing machine. A developing machine of the roller conveyance type is preferable because it has good connection with the preceding and following processes, but is not limited thereto. Since the necessity of performing the standard processing may occur, it is practical to omit the fixing step using a standard developing processing machine. That is, the film is subjected to development processing including color development, bleaching, washing with water, and image stabilization, and then proceeds to an image information reading step. Alternatively, as described above, image reading may be performed during the development processing step. Alternatively, as described above, when it is not necessary to store the color film, the water washing and the image stabilization bath can be omitted, and the environmental load can be greatly reduced.
Although any of the materials and processes described in the section of development processing applicable to the present invention described later can be applied to the development processing, the CN16 series, C41 series, and CNK4 series, which are the most widely used and internationally common processes, can be applied. Development processing is desirable. In the present invention, the fixing step is omitted from the development processing step.
[0037]
4). Image reproduction process
FIG. 2 is a block diagram showing the basic configuration of the image reproduction system according to the present invention. As shown in FIG. 2, the image reproduction system reads a color image from a developed film and generates digitized image data. The image data generated by the image reading device 1 has a predetermined value. An image processing device 5 that performs image processing, and an image output device 8 that reproduces a color image based on image data that has been subjected to image processing by the image processing device 5 are provided.
[0038]
4.1 Reading image information from developed film
Image reading can be performed mainly by the following three methods.
(I) A film is wound around a rotating drum and irradiated with measuring light combined with a color separation filter, while rotating the drum and simultaneously performing sub-scanning in the drum direction to photoelectrically convert the reflection density of each pixel with a photomultiplier tube Then read and amplify it as a time-series electrical signal,
(Ii) Using a line CCD in which light receiving elements are arranged one-dimensionally, the transmission or reflection density is received by the line CCD while sub-scanning the image on the developed film, and it is electrically scanned in time series. Line CCD-scanning system to convert to
(iii) Any one of the area CCD systems is used in which the density of the pixels is read in two dimensions using an area CCD and converted into electrical signals rearranged in time series by electrical scanning from the area CCD. Also good.
The area CCD system is particularly preferable, and the following description will be made on the premise of this system, but the present invention can be implemented without any trouble with the other two systems.
[0039]
The external appearance of the image reproduction system of FIG. 2 is shown in FIG. 3, but for the sake of easy understanding, FIG. 3 shows a conventional type independent from the developing machine. In the image reproduction system of FIG. 3, as the image reading device 1, a transmissive image reading device 10 that photoelectrically reads a developed color image and a reflective image reading device 30 that photoelectrically reads a color image are selectively used. In addition, it is configured to be connected to the image processing apparatus 5, so that both a color image recorded on the film and a color image recorded on the color print can be reproduced. The image reading apparatus according to the present invention may optionally include this type of apparatus, but at least one of the image readers is incorporated in a developing machine as shown in FIG. The image information can be read from the developed film after the completion and before entering the drying step. In FIG. 12, the image reading apparatus 10 is provided between the bleaching process and the fixing process, but can be moved to another place depending on the purpose.
[0040]
FIG. 4 is a schematic diagram of a transmissive image reading apparatus 10 for a color image reproduction system that generates image data based on a color image. As shown in FIG. 4, the transmissive image reading device 10 irradiates the color image recorded on the film F with light and detects the light transmitted through the film, thereby photoelectrically reading the color image. The light source 11, the light amount adjustment unit 12 that can adjust the amount of light emitted from the light source 11, and the light emitted from the light source 11 are R (red), G (green), and B (blue) ), The color separation unit 13 for separating the light into three colors, and the light emitted from the light source 11 so that the light emitted from the light source 11 is uniformly irradiated to the film F. A CCD area sensor 15 that detects photoelectrically and an electric zoom lens 16 that forms an image of light transmitted through the film F on the CCD area sensor 15 are provided. The transmissive image reading apparatus 10 can read various films such as a 135 negative film, a 135 positive film, and an advanced photo system (APS) film by exchanging a film carrier (not shown).
[0041]
A halogen lamp is used as the light source 11, and the light amount adjustment unit 12 is configured such that the light amount changes exponentially with respect to the moving distance by the movement of the two diaphragm plates. The color separation unit 13 color-separates into three colors in the surface order by rotating a disk having three R, G, and B filters. The CCD area sensor 15 has a light receiving element of 920 pixels and 1380 pixels horizontally, and can read image information on the film with high resolution. When reading the color image, the CCD area sensor 15 sequentially reads the odd-field image data composed of the odd-numbered image data of the photoelectrically read image and the even-field image data composed of the even-numbered image data. Configured to forward.
[0042]
The transmissive image reading apparatus 10 further includes an amplifier 17 that amplifies the R, G, and B image signals photoelectrically detected and generated by the CCD area sensor 15, and an A / D converter 18 that digitizes the image signals. The image data of the CCD correction means 19 and R, G, B for correcting the sensitivity variation for each pixel and the dark current for the image signal digitized by the A / D converter 18 are converted into density data. The log converter 20 is provided. The log converter 20 is connected to the interface 21.
[0043]
The film F is held by the carrier 22, and the film F held by the carrier 22 is sent to a predetermined position by a driving roller 24 driven by a motor 23, and is pressed and held in a stopped state. When reading of the image is completed, one frame is sent. As an auto carrier for handling a negative film, one used in a conventional minilab such as NC135S (Fuji Photo Film) is used. Images in a range corresponding to the print form such as full size, panorama size, and force size can be read. In addition, when a trimming carrier used in a conventional minilab is used, the magnification can be increased by about 1.4 times around the center.
[0044]
The screen detection sensor 25 detects the density distribution of the color image recorded on the film F, and outputs the detected density signal to the CPU 26 that controls the transmissive image reading apparatus 10. Based on this density signal, The CPU 26 is configured to calculate the screen position of the color image recorded on the film F and stop the driving of the motor 23 when determining that the screen position of the color image has reached a predetermined position.
The image reading apparatus may be at any place such as an entrance or exit of the drying unit of the developing machine, an independent reading / image processing apparatus or a printer unit.
[0045]
On the other hand, FIG. 11 shows a case of reading with reflection density, which is an advantageous aspect of the present invention. The reflection-type image reading device 30 is configured to detect a reflected light image having a high contrast from a silver halide having a high reflectance and a dye image having a large light absorption by bleaching, and to read the light photoelectrically. A mirror 32 that reflects light emitted from a light source and reflected by the film surface, a color balance filter 33 that adjusts R, G, and B sensitivity of the reflected light, a light amount adjustment unit 34, and a CCD line sensor that photoelectrically detects reflected light 35 and a lens 36 for forming an image of the reflected light on the licensor.
[0046]
The CCD line sensor 35 is constituted by a three-line sensor corresponding to three colors of R, G, and B. The CCD line sensor 35 detects reflected light while moving the light source 31 and the mirror 32 in the direction of the arrow. Read image information two-dimensionally.
[0047]
The reflection-type image reading device 30 further includes an amplifier 37 that amplifies the detected R, G, and B image signals, an A / D converter 38 that digitizes the image signal, and a pixel for the digitized image signal. CCD correction means 39 for correcting variations in sensitivity and dark current, and a log converter 40 for converting into R, G, B image data density data. The log converter is connected to the interface 41. This reflection type image reading apparatus is controlled by the CPU 46.
[0048]
4.2 Image processing of scanned image information
The image reading apparatus 1 shown in FIGS. 2 and 3 has been described in detail above. Next, the image processing apparatus 5 shown in FIGS. 2 and 3 will be described next.
[0049]
5 and 6 are block diagrams showing the configuration of the image processing apparatus 5 divided into two diagrams. As shown in these drawings, the image processing device 5 is generated by the image reading device 1 and the interface 48 that can be connected to the interface 21 of the transmissive image reading device 10 or the interface 41 of the reflective image reading device 30. The values of two adjacent pixel data of the image data sent for each line are added and averaged to obtain one pixel data, and the image sent from the addition average computing means 49 The first line buffer 50a and the second line buffer 50b that alternately store pixel data in each line of data, and the line data stored in the line buffers 50a and 50b are transferred to the film F (FIG. 3). ) Corresponding to a color image recorded on one frame or color image recorded on one color print P (FIG. 4) That the first frame memory unit 51 for storing image data, and a second frame memory unit 52 and the third frame memory unit Bok 53. Here, the first line buffer 50a and the second line buffer 50b alternately store odd-numbered pixel data of each line of image data in one line buffer and even-numbered pixel data in the other line buffer. It is configured as follows.
[0050]
In the present embodiment, first, with respect to one color image recorded on the film F, first reading by the image reading device 1 (hereinafter referred to as pre-reading), and reading of the read image into digital image data is performed. Conversion is performed. At this time, based on the image data obtained by this pre-reading, the image processing apparatus 5 sets image reading conditions for the second reading (hereinafter referred to as “main reading”) to be performed next. Then, based on the set reading conditions, the color image is read again, that is, the main reading is performed again, thereby generating digital image data to be subjected to image processing for reproduction. In order to perform such processing, the image processing apparatus 5 stores the image data obtained by the pre-reading in the first frame memory unit 51, and the image data obtained by the main reading is stored in the second frame memory unit 52 and The third frame memory unit 53 is configured to store each.
[0051]
Before describing the other components shown in FIGS. 5 and 6, these frame memory units will be described in detail. FIG. 7 is a block diagram showing details of the first frame memory unit 51, the second frame memory unit 52, and the third frame memory unit 53. As shown in FIG. 7, the image processing apparatus 5 reads the color image and processes the image data generated, so that the first frame memory unit 51, the second frame memory unit 52, and the third frame memory are processed. The unit 53 includes an R data memory 51R, a G data memory 51G, a B data memory 51B, an R data memory 52R, and G data that store image data corresponding to R (red), G (green), and B (blue), respectively. A memory 52G, a B data memory 52B, an R data memory 53R, a G data memory 53G, and a B data memory 53B are provided. As described above, the first frame memory unit 51 stores image data obtained by pre-reading, and the second and third frame memory units 52 store image data that has been read and stored. However, in FIG. 7, image data obtained by prefetching is input from the input bus 63 to the first frame memory unit 51, and image data stored in the second frame memory unit 52 is output to the output bus 64. The state is shown.
[0052]
The configuration of the image processing apparatus 5 will be described with reference to FIGS. 5 and 6 again. The image processing apparatus 5 includes a CPU 60 that controls the entire image processing apparatus 5. The CPU 60 can communicate with a CPU 26 (FIG. 4) that controls the transmissive image reading apparatus 10 via a communication line (not shown), and also communicates with a CPU that controls an image output apparatus 8 (not shown). ) To communicate with each other. With this configuration, the CPU 60 changes the image reading conditions for performing the main reading of the color image based on the image data obtained by the pre-reading stored in the first frame memory unit 51, and further reads it as necessary. It is possible to change image processing conditions for image processing to be applied to a subsequent image.
[0053]
That is, the CPU 60 determines image reading conditions for the main reading so that the dynamic range of the CCD area sensor 15 or the CCD line sensor 35 can be efficiently used during the main reading based on the image data obtained by the pre-reading. Then, the reading control signal is output to the CPU 26 of the transmissive image reading device 10 or the CPU 46 of the reflective image reading device 30. At this time, when the CPU 26 of the transmissive image reading apparatus 10 or the CPU 46 of the reflective image reading apparatus 30 receives this reading control signal, the light quantity adjusted by the light quantity adjusting unit 12 or the light quantity adjusting unit 34 and the CCD area sensor. 15 or the accumulation time of the CCD line sensor 35 is controlled. At the same time, based on the obtained image data, the CPU 60 allows the first image processing means and the second image processing unit to be described later so that a color image having the optimum density, gradation and tone can be reproduced on the color paper. A control signal for changing image processing conditions such as parameters of image processing by the image processing means is output to the first image processing means and the second image processing means as necessary. At this time, the image reading condition or the image processing condition determined by the CPU 60 is stored in the memory 66.
[0054]
When the CPU 60 performs the above control, if the image reading condition or the image processing condition is held by an operator instruction, the CPU 60 does not determine the condition based on the pre-read image data as described above and holds it. Various control signals are output based on the conditions. When the operator sets various conditions using an input device such as the keyboard 69 and further instructs the holding of these conditions, these conditions are stored in the memory 66, and when the operator subsequently instructs the release of the holding of these conditions, The conditions stored in the memory 66 are invalid. Therefore, the CPU 60 first refers to the conditions stored in the memory 66 when performing the control as described above. If the conditions are stored, the CPU 60 follows the conditions. If the conditions are not stored, the CPU 60 reads the prefetched image. These conditions are determined based on the data. Therefore, the operator can read from the DX code or instruct the condition setting according to the type of each film according to the customer's special order, or set the conditions for each film type in advance and automatically It is also possible to enable processing according to the instructions. It is not always necessary to hold such conditions in large units such as image reading conditions or image processing conditions. More detailed conditions such as storage when the above conditions are stored in the memory 66 or their reference are referred to. For example, the saturation setting may be retained, and the sharpness may be determined automatically using the condition.
[0055]
The configuration of the image processing apparatus 5 in the range shown in FIG. 5 has been described above. Here, the image data generated in the image reading apparatus 1 is input to the image processing apparatus 5 through the interface 48, and the first to third A process performed on the image data before it is stored in the frame memory unit will be described in detail.
[0056]
Next, as described above, the configuration of the image processing apparatus 5 for performing image processing on the image data stored in the second frame memory unit 52 and the third frame memory unit 53 as a result of the actual reading. Will be described.
[0057]
The image processing apparatus 5 can reproduce a color image on the color paper with desired density, gradation, and color tone from the image data stored in the second frame memory unit 52 and the third frame memory unit 53. As described above, the image stored in the first image processing means 61 (FIG. 6) and the first frame memory unit 51 that performs image processing such as gradation correction, color conversion, and density conversion by a look-up table or matrix calculation. Second, the data is subjected to image processing such as gradation correction, color conversion, and density conversion by a look-up table and matrix calculation so that a color image can be reproduced on a CRT screen described later with a desired image quality. Image processing means 62 (FIG. 6). Outputs of the second frame memory unit 52 and the third frame memory unit 53 are connected to a selector 55, and are stored in either the second frame memory unit 52 or the second frame memory unit 53 by the selector 55. The image data is selectively input to the first image processing means 61.
[0058]
FIG. 8 is a block diagram showing details of the first image processing means 61. As shown in FIG. 8, the first image processing means 61 includes color density gradation conversion means 100 that converts density data of image data, color data, and gradation data, and saturation that converts saturation data of image data. Degree conversion means 101, digital magnification conversion means 102 for converting the number of pixel data of the image data, frequency processing means 103 for performing frequency processing on the image data, and dynamic range conversion means 104 for converting the dynamic range of the image data. Yes. Each of these conversion means is configured so that the respective processing means operate simultaneously and the next processing is performed after the operation ends, as is usually called pipeline processing, so that high-speed processing is possible. Yes.
[0059]
The image processing means shown in FIG. 8 can not only perform gradation correction, color conversion, density conversion, and the like, but also suppress sharpness of the film while simultaneously suppressing the graininess of the film as shown in JP-A-2-02460. Improvement processing can also be performed. Furthermore, an automatic dodging process can be applied to an image with a high contrast between light and dark as shown in Japanese Patent Laid-Open No. 9-018704, which brings about good image reproduction.
The film subjected to the development processing of the present invention, in which the fixing step is omitted, is (i) gradation shift due to overlapping of a dye image and silver halide, and (ii) reading due to an increase in Dmin (minimum density value). There are a decrease in the possible range and a decrease in saturation, and (iii) a decrease in reading accuracy in the high exposure area due to an increase in Dmax (maximum density value), and the degree of the above three factors varies depending on the type of film. Therefore, the CPU 60 is set with conversion processing condition settings for correcting the image quality when the reference processing is performed from the read image information digitized with respect to the above three photographic characteristic factors. As can be seen from the foregoing, the items of image processing conditions for image quality correction that should be particularly set for the fixing skip processing are as follows.
[0060]
1) Correction processing of gradation shifted from the gradation of the reference development processing,
2) Processing to convert color balance data into color balance values when processed under reference processing conditions;
3) Processing that corrects the non-linearity of the exposure amount vs. density relationship caused by the development process omitting the development process and corrects the exposure material to the density relationship when the photographic material is processed under the standard processing conditions (particularly the high density portion and Low concentration part), and
4) There is a correction process for the influence of Dmin (so-called clogs), which is significantly higher than the standard development process.
[0061]
The correction by the image processing of the four characteristic factors is largely corrected by two methods. One is the image reproduction operation by directly performing the above-described image processing operation on the density value information of the read image, and the other is the arithmetic processing for converting the read image information into the analysis density. This is a method for performing the above-described image reproduction processing on the analysis density information obtained later. Although it is considered that the image is more accurately grasped by converting to the analysis density, in the present invention, it was found that the former method is sufficient, so the following is the image reading density information without using the analysis density. A method for directly inputting to the image processing apparatus will be described.
[0062]
In this series of image processing for image reproduction, the correction of the softened gradation described in (i) to the gradation when the standard development is performed is the most important image processing for image reproduction. That is, the gradation converting means 100 has a function of correcting the gradient of the input density value versus the exposure amount to an appropriate value obtained by the standard development process. At the same time, the major part of the correction of the color balance described in (ii) is performed by adjustment for each color of this high contrast, and is further finely adjusted by combining the following image processing functions. The further softness of the high density portion and the extension of the low density portion described in (iii) set the saturation enhancement level of the saturation conversion means 101 high, and the dynamic range conversion means 104 and the gradation conversion means 100. In addition, the shape of the characteristic curve of the leg portion and the high concentration portion is corrected by a combination of changes in the density amplification degree according to the spatial frequency described below. In this case, it goes without saying that conditions are set so that the correction processing to the reference value of saturation is also performed at the same time.
Since the increase in Dmin due to residual silver or the like is erased by being included in the background level at the so-called clogged portion in the image processing process, the influence on the output image characteristics does not appear unless the reading area is extremely high.
The operation contents of the device of the image processing apparatus used for the above image processing are pending as Japanese Patent Application Nos. H8-174022 and H8-182551.
[0063]
In the case of performing image information processing after conversion to analysis density (filed in Japanese Patent Application No. 9-135154), an arithmetic circuit is added to the CPU 60 of FIG. In the present invention, the analytical density of each of the yellow, magenta, and cyan dyes is obtained by calculation from the blue, green, and red filter light density values read from the developed film.
[0064]
The accuracy of the image quality correction by the image processing of the image information of the developed film described above is within 10% of the image quality characteristic value value of the reference developed image when each of the image quality characteristics is expressed by the density value as described above. It is sufficient that it is 8% or less. The image quality characteristics that are impaired by the fixing omission processing are mainly color balance, gradation characteristics, and graininess. If these are in the above range as density values, it is determined that the image can be reproduced.
Conversion to the characteristic value when performing standard development processing may be performed by setting conversion conditions for each type of film and automatically selecting the conditions by reading the type of film to be processed. The operator may specify conversion process conditions for each film processed.
[0065]
The information obtained by converting the image information read from the film that has been subjected to the development process without the fixing process into the characteristic value when the standard development process is performed by the image process is stored once, and then the printer to the positive image The process will proceed to the output stage.
[0066]
In addition, the image processing apparatus 5 is provided with a data bus 65 separately from the input bus 63 and the output bus 64 of the first frame memory unit 51, the second frame memory unit 52, and the third frame memory unit 53. The data bus 65 includes a CPU 60 that controls the entire color image reproduction system, a memory 66 that stores data relating to an operation program of the CPU 60 or image processing conditions, a hard disk 67 that can store and store image data, A CRT 68, a keyboard 69, a communication port 70 connected to another color image reproduction system via a communication line, a communication line with the CPU 26 of the transmissive image reading apparatus 10, and the like are connected.
[0067]
4.3 Output of Image Processed Image Signal to Printer The configuration of the image processing apparatus 5 shown in FIGS. 2 and 3 has been described in detail. Next, the image output apparatus 8 shown in FIGS. 2 and 3 will be described. FIG. 9 is a schematic diagram of an image output apparatus 8 for a color image reproduction system for reproducing a color image on a color paper based on image data processed by the image processing apparatus according to the preferred embodiment of the present invention. is there.
[0068]
In FIG. 9, the image output device 8 includes an interface 78 that can be connected to the interface 77 of the image processing device 5, a CPU 79 that controls the image output device 8, and a plurality of image data input from the image processing device 5. An image data memory 80 composed of a frame memory, a D / A converter 81 that converts image data into an analog signal, a laser beam irradiation unit 82, and a modulator drive unit 83 that outputs a modulation signal that modulates the intensity of the laser beam. It has. The CPU 79 is configured to be able to communicate with the CPU 60 of the image processing apparatus 5 via a communication line (not shown).
[0069]
FIG. 10 is a schematic diagram of the laser light irradiation means 82 shown in FIG. 9, and the laser light irradiation means 82 includes semiconductor laser light sources 84a, 84b, 84c, and the laser light emitted by the semiconductor laser light source 84b is The laser light converted by the wavelength conversion means 85 into green laser light having a wavelength of 532 nm and emitted from the semiconductor laser light source 84c is converted by the wavelength conversion means 86 into blue laser light having a wavelength of 473 nm.
[0070]
Red laser light having an arbitrary wavelength between 670 nm and 690 nm emitted from the semiconductor laser light source 84a, green laser light whose wavelength has been converted by the wavelength converting means 85, and blue laser whose wavelength has been converted by the wavelength converting means 86 The light is configured to enter light modulators 87R, 87G, and 87B such as acousto-optic modulators (AOM), and each of the light modulators 87R, 87G, and 87B includes a modulator driving unit 83. The modulation signal is input from, and the intensity of the laser beam is modulated in accordance with the modulation signal. At this time, if the semiconductor laser light source 84a can operate at high speed, the optical modulator 87R can be omitted by directly modulating the semiconductor laser light source 84a.
[0071]
The laser light whose intensity is modulated by the light modulators 87R, 87G, 87B is reflected by the reflection mirrors 88R, 88G, 88B and enters the polygon mirror 89. Here, the paper is conveyed at a speed of about 75 mm per second, the scanning line density is 600 lines per inch, and each pixel is modulated every 100 nsec.
[0072]
The image output device 8 includes a magazine 91 in which color paper 90 is stored in a roll shape, and the paper paper color paper 90 is conveyed at a speed of about 110 mm per second in the sub-scanning direction along a predetermined conveyance path. It is configured. Color paper with a width of 89 mm to 210 mm can be used, and it may be a color paper used in ordinary mini-labs, etc., or a dedicated color suitable for high-illumination short-time exposure unique to laser exposure Paper may be used. As the magazine 91, one used in a normal minilab, for example, one described in JP-A-6-161650 is used. The conveyance path of the color paper 90 is provided with a punching means 92 for making a reference hole at the side edge of the color paper 90 at intervals corresponding to the length of one color print. In the apparatus 8, the conveyance of the color paper 90 and the driving of other means are synchronized according to the reference hole. As the conveying means, the one disclosed in JP-A-4-147259 is used. As the processing tank, the one shown in JP-A-4-155333 is used.
[0073]
The laser beams modulated by the light modulators 87R, 87G, and 87B are scanned in the main scanning direction by the polygon mirror 89, and the color paper 90 is exposed through the fθ lens 93. Here, since the color paper 90 is conveyed in the sub-scanning direction, the entire surface is exposed by the laser beam. Here, the conveyance speed of the color paper 90 in the sub-scanning direction is controlled by the CPU 79 so as to be synchronized with the main scanning speed of the laser beam, that is, the rotational speed of the polygon mirror 89.
[0074]
The color paper 90 exposed by the laser beam is sent to the development processing unit 94 at a speed of about 29 mm per second, subjected to predetermined color development processing, bleach-fixing processing, and water washing processing, and image processing is performed by the image processing device 5. A color image is reproduced on the color paper 90 based on the obtained image data. The color paper 90 which has been subjected to the color development processing, the bleach-fixing processing, and the water-washing processing by the color developing tank 94, the bleach-fixing tank 95, and the water washing tank 96 is sent to the drying unit 97 and dried. Corresponding to a color image recorded on one frame of film F or one color paper P by a cutter 98 driven in synchronism with the conveyance of the color paper 90 based on the reference hole drilled in the side edge. It is cut into a length to be sent, sent to the sorter 99, and stacked so as to correspond to one film F or for each customer. As the sorter, the one shown in Japanese Patent Laid-Open No. 4-199052 is used.
[0075]
Here, as the color developing tank 94, the bleach-fixing tank 95, the water washing tank 96, the drying unit 97, the cutter 98, and the sorter 99, those used in an ordinary minilab automatic developing machine can be used. In this embodiment, color paper processing prescription CP47L (Fuji Photo Film Co., Ltd.) is adopted, but it can also be applied to CP40FA and CP43FA (both are general photo prescriptions of Fuji Photo Film Co., Ltd.). It is.
[0076]
5. Positive image material for output
The image characteristic value equivalent to the reference process obtained by the method of the present invention is output to the positive material and obtained in the form of a positive image.
As described above, output materials for obtaining positive images include inkjet, sublimation type thermal transfer, color diffusion transfer, heat development type silver salt color diffusion transfer, heat development type multilayer color diazo, silver salt color paper, etc. Any signal can be input as long as the signal is a time-series electric or optical signal.
Among them, color paper is particularly preferable. Each of the light-sensitive silver halide emulsions in the light-sensitive material preferably comprises silver halide grains having a silver chloride content of at least 95 mol% and the remainder being silver bromide and substantially free of silver iodide. Here, “substantially free of silver iodide” means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less, more preferably 0 mol%. The above silver halide emulsion is particularly preferably a silver halide emulsion having a silver chloride content of 98 mol% or more from the viewpoint of rapid processability. Among such silver halides, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferred because high sensitivity can be obtained and photographic performance can be stabilized.
[0077]
The silver halide emulsion contained in at least one light-sensitive silver halide emulsion layer has a coefficient of variation in grain size distribution (standard deviation of grain size distribution divided by average grain size) of 15% or less. A 10% or less monodispersed emulsion is more preferable. For the purpose of obtaining a wide latitude, it is preferable to use a mixture of two or more of the above monodispersed emulsions in the same layer. At this time, the average grain size of each monodispersed emulsion is preferably different by 15% or more, more preferably 20 to 60%, and even more preferably 25 to 50%. The sensitivity difference between the monodisperse emulsions is preferably 0.15 to 0.50 logE, more preferably 0.20 to 0.40 logE, and still more preferably 0.25 to 0.35 logE. .
[0078]
In order to obtain a positive image for the purpose of the present invention, an iron and / or ruthenium and / or osmium compound is added to silver chlorobromide having a silver chloride content of 95 mol% or more which does not substantially contain silver iodide. 1 x 10 per mole^-Five~ 1x10^-31 x 10 per mole of silver halide in the silver bromide localized phase.^-7~ 1x10^-FiveIt is effective to use a silver halide emulsion containing a molar amount of an iridium compound.
Conventional silver photographic materials and additives can be used for the silver halide photographic light-sensitive material for output used in the present invention.
For example, a transmissive support or a reflective support can be used as the photographic support. As the transparent support, transparent films such as cellulose nitrate film and polyethylene terephthalate, polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), and polyester of NDCA, terephthalic acid and EG For example, an information recording layer such as a magnetic layer is preferably used. For the purposes of the present invention, a reflective support is preferred, particularly laminated with a plurality of polyethylene layers or polyester layers, and at least one layer of such a water-resistant resin layer (laminate layer) contains a white pigment such as titanium oxide. A reflective support is preferred.
[0079]
Furthermore, it is preferable to contain a fluorescent brightening agent in the water-resistant resin layer. The fluorescent brightening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the optical brightener, benzoxazole-based, coumarin-based, and pyrazoline-based compounds can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based fluorescent whitening agents are more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m.²It is. The mixing ratio in the case of mixing with a water resistant resin is preferably 0.0005 to 3% by weight, more preferably 0.001 to 0.5% by weight, based on the resin.
A hydrophilic colloid layer containing a white pigment may be coated on the body.
Further, the reflective support may be a support having a specular reflective or second-type diffuse reflective metallic surface.
Reflective support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer or antifoggant for silver halide emulsion, chemical sensitization method (sensitizer) , Spectral sensitization (spectral sensitizer), cyan, magenta, yellow coupler and emulsion dispersion method thereof, color image preservability improver (stain inhibitor and anti-fading agent), dye (colored layer), gelatin species, sensitization Regarding the layer structure of the material and the coating film pH of the light-sensitive material, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.
[0080]
[Table 1]

[0081]
[Table 2]

[0082]
Other examples of cyan, magenta and yellow couplers that can be used for the light-sensitive material for output (color paper) include those described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; No. 33144, page 3, upper right column, line 14 to page 18, upper left column, last line, page 30, upper right column, line 6 to page 35, lower right column, line 11, and EP0355,660A2, page 4, line 15 Also useful are couplers described in the 1st to the 27th lines, the 5th page, the 30th line to the 28th page, the 45th page, the 29th line to the 31st line, the 47th page, the 23rd line to the 63rd line, the 50th line.
As the antibacterial and antifungal agents that can be used for the color photographic material for output, those described in JP-A-63-271247 are useful.
In order to make the image reproduction system of the present invention compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) in which a semiconductor laser or a solid laser and a nonlinear optical crystal are combined. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.
[0083]
When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the output color light-sensitive material can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green, and red.
When the exposure time in such scanning exposure is defined as the exposure time of the pixel size when the pixel density is 400 dpi, a preferable exposure time is 10^-FourSeconds or less, more preferably 10^-6Less than a second.
Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above.
Further, for processing the color photographic material for output, page 26, lower right column, line 1 to page 34, upper right column, line 9 of JP-A-2-207250, and page 5, upper left column of JP-A-4-97355. The processing materials and processing methods described in the 17th line to the 18th page, lower right column, 20th line are preferably applicable. Further, as the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.
[0084]
6). Supplementary explanation of the present invention
6.1 About development processing
[0085]
In the present invention, the color developer used for the development treatment is preferably an alkaline water-soluble night mainly composed of an aromatic primary amine color developing agent. As this color developing agent, an aminophenol compound is also useful, but a p-phenylenediamine compound is preferably used, and representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N- Ethyl-β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) Aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- ( -Hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3- Methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl- N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N , N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, in particular 3-methyl 4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4- Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline and their hydrochlorides, p-toluene Sulfonate or sulfate is preferred. These compounds may be used in combination of two or more depending on the purpose.
[0086]
The amount of the aromatic primary amine developing agent used is preferably 0.0002 mol to 0.2 mol, more preferably 0.001 mol to 0.1 mol, per liter of the color developer.
[0087]
The color developer is a pH buffer such as an alkali metal carbonate, borate or phosphate 5-sulfosalicylate, chloride salt, bromide salt, iodide salt, benzimidazoles, benzothiazoles or Generally, it contains a development inhibitor such as a mercapto compound or an antifoggant. If necessary, other than hydroxylamine, diethylhydroxylamine, hydroxylamines represented by the general formula (I) of JP-A-3-144446, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, Various preservatives such as phenyl semicarbazides, triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, and dye formation Couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid For example, Range amine tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine Representative examples include -N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.
[0088]
Among the above, substituted hydroxylamine is most preferable as a preservative, and among them, one having diethylhydroxylamine, monomethylhydroxylamine or an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group, or a hydroxyl group as a substituent. preferable. The most preferred example is N, N-bis (2-sulfoethyl) hydroxylamine and its alkali metal salts.
[0089]
The chelating agent is preferably a biodegradable compound. Examples thereof include JP-A-63-146998, JP-A-63-199295, JP-A-63-267750, JP-A-63-267775, JP-A-2-229146, JP-A-3-186411. And chelating agents described in German Patent 3739610, European Patent 468325 and the like. The processing solution in the color developer replenishing tank or processing tank is preferably shielded with a liquid agent such as a high boiling point organic solvent to reduce the contact area with air. The liquid shielding agent is most preferably liquid paraffin. It is particularly preferable to use it as a replenisher. The processing temperature with the color developer in the present invention is 20 to 55 ° C, preferably 30 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds for the photographic material. More preferably, it is 40 seconds to 1 minute 30 seconds.
[0090]
The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is,
Opening ratio = [contact area between treatment liquid and air (cm²)] ÷ [Volume of processing solution (cm^Three)]
The opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a floating lid and other shielding objects on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, The slit development processing method described in 63-2160050 can be mentioned. To reduce the aperture ratio, not only both color development and black-and-white development (color reversal processing, etc.), but also the subsequent steps such as bleaching, washing with water, stabilization (the above is described including the standard processing). It is preferable to apply in all steps such as. Further, the replenishment amount can be reduced by using means for suppressing the accumulation of bromide ions and chloride ions in the developer.
[0091]
In the processing apparatus of the present invention, except for the case where it is not necessary to store the film and the subsequent processing is not performed, it is general that the desilvering process is followed by water washing and an image stabilization process. The amount of water to be washed in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as coupler), the application, the washing water temperature, the number of washing tanks (number of washing tanks), the replenishment method such as countercurrent and forward flow, and various other conditions. A wide range can be set. Among these, the relationship between the number of flush tanks and the amount of water in the multistage countercurrent system is described in Journal of the Society of Motion Picture and Television Engineers Vol. 64, p. It can be determined by the method described in 248-253 (May 1955). According to the multi-stage countercurrent system described in the above-mentioned document, the amount of water to be washed can be significantly reduced. However, the increase of the residence time of water in the tank causes bacteria to propagate and the generated suspended matter adheres to the photosensitive material. Problems arise. In the processing of the color photographic material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, the isothiazolone compounds and cyabendazoles described in JP-A-57-8542, chlorinated fungicides such as chlorinated sodium isocyanurate, benzotriazole, etc. "Chemistry" (1986) Sankyo Publishing, Hygiene Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japanese Society for Antibacterial and Antifungal Studies, "Environmental Antifungal Agent" (1986) ) Can also be used.
[0092]
The pH of the washing water in the processing of the light-sensitive material that is the subject of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be variously set depending on the characteristics and use of the photosensitive material. Generally, the washing water temperature and washing time are 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. Selected. Furthermore, the light-sensitive material of the present invention can be directly processed with a stabilizing solution in place of the water washing. In such stabilization treatment, all known methods described in JP-A-57-8543, 58-14834, and 60-220345 can be used.
[0093]
Further, the image stabilizing solution includes compounds that stabilize dye images, such as benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adducts, hexamethylenetetramine and derivatives thereof, hexahydrotriazine and derivatives thereof, and dimethylol. N-methylol compounds such as urea and N-methylolpyrazole, organic acids and pH buffering agents are included. The preferred addition amount of these compounds is 0.001 to 0.02 mol per liter of the stabilizing solution, but a lower free formaldehyde concentration in the stabilizing solution is preferable because of less scattering of formaldehyde gas. From these points, as the dye image stabilizer, N-methylolazoles described in JP-A-4-270344 such as m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N, N′-bis (1 , 2,4-Triazol-1-ylmethyl) piperazine and the like, azolylmethylamines described in JP-A-4-313753 are preferred. In particular, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding, European Patent Publication No. 519190A2) and 1,4-bis (l, 2,4-triazol-1-ylmethyl) ) A combination of azolylmethylamine and its derivatives such as piperazine is preferred because of high image stability and low formaldehyde vapor pressure. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, fluorescent brighteners, hardeners, alkanolamines described in US Pat. No. 4,786,583, It is also preferable to contain a preservative that can be contained in the fixing solution and the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-2311051.
[0094]
The washing water and / or the washing alternative stabilizing bath and the image stabilizing solution may contain various surfactants in order to prevent water droplet unevenness when the photosensitive material after processing is dried. Of these, nonionic surfactants are preferably used, and alkylphenol ethylene oxide adducts are particularly preferable. As the alkylphenol, octyl, nonyl, dodecyl, and dinonylphenol are particularly preferable, and the number of moles of ethylene oxide added is particularly preferably 8 to 14. It is also preferable to use a silicon surfactant having a high defoaming effect.
[0095]
It is preferable to contain various chelating agents in the washing water and / or the stabilizing solution and the image stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N′-trimethylenephosphonic acid, diethylenetriamine-N, N, Examples thereof include organic phosphonic acids such as N ′, N′-tetramethylenephosphonic acid, and maleic anhydride polymer hydrolysates described in European Patent 345,172A1.
[0096]
The overflow liquid accompanying replenishment of the washing water and / or the stabilizing liquid can be reused in other processes such as a desilvering process. About the processor of this invention, parts other than a drive are described. The color developer and the color developer replenisher are preferably as small as possible in the processing tank and the replenisher tank. For example, opening area (cm²) Liquid tank in the tank (cm^Three), The aperture ratio is 0.01 (cm^-1) Or less, more preferably 0.005 or less, and most preferably 0.001 or less.
[0097]
In the present invention, in order to perform processing quickly, the air time when the photosensitive material moves between the processing solutions, that is, the crossover time is preferably as short as possible, preferably 20 seconds or less, more preferably 10 seconds or less, More preferably, it is 5 seconds or less. In order to achieve the above-described short-time crossover, the present invention preferably uses a cine type automatic developing machine, particularly preferably a leader conveyance system or a roller conveyance system. Such a system is used in an automatic processor FP-560B or PP1820V manufactured by Fuji Photo Film Co., Ltd. Moreover, although the one where the linear velocity of conveyance is larger is preferable, 30 cm-30 m / min is common, Preferably it is 50 cm-10 m. As the reader or photosensitive material conveying means, the belt conveying systems described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259 are preferable. In order to shorten the crossover time and prevent the processing liquid from being mixed, a crossover rack structure having a mixing prevention plate is preferable.
[0098]
It is preferable to perform so-called evaporation correction in which water corresponding to the evaporation amount of the processing liquid is supplied to each processing liquid in the present invention. In particular, it is preferable in a color developer. As a specific method for replenishing such water, an evaporation correction method using a liquid level sensor or an overflow sensor is preferable. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation, and the amount of water calculated by a coefficient determined in advance based on information on the operation time, stop time and temperature control time of the automatic processor. Is added.
[0099]
Further, a device for reducing the evaporation amount is also required, and it is required to reduce the opening area and adjust the air volume of the exhaust fan. For example, the preferred aperture ratio of the color developer is as described above, but it is preferable to reduce the aperture area in the other processing solutions as well. The exhaust fan is attached to prevent dew condensation during temperature control, but a preferable exhaust rate is 0.1 m / min.^Three~ 1m^ThreeThe particularly preferable displacement is 0.2 m.^Three~ 0.4m^ThreeIt is. The drying conditions of the photosensitive material also affect the evaporation of the processing solution. It is preferable to use a ceramic warm air heater as the drying method, and the supply air volume is 4 m / min.^Three~ 20m^ThreeIs preferred, especially 6m^Three-10m^ThreeIs preferred. The thermostat for preventing the heating of the ceramic warm air heater is preferably operated by heat transfer, and the mounting position is preferably attached leeward or upwind through the radiating fin or the heat transfer portion. The drying temperature is preferably adjusted according to the water content of the light-sensitive material to be processed. The optimum temperature is 45 to 55 ° C. for a 35 mm wide film, 55 to 65 ° C. for a brownie film, and 60 to 90 ° C. for a print material. A replenishment pump is used for replenishing the treatment liquid, but a bellows type replenishment pump is preferable. As a method for improving the replenishment accuracy, it is effective to reduce the diameter of the liquid feeding tube to the replenishing nozzle in order to prevent backflow when the pump is stopped. A preferable inner diameter is 1 to 8 mm, and a particularly preferable inner diameter is 2 to 5 mm.
[0100]
Various parts materials are used in the automatic developing machine in addition to the drive unit described above. Preferred materials are described below. The tank material such as the treatment tank and the temperature control tank is preferably modified PPO (modified polyphenylene oxide) or modified PPE (modified polyphenylene ether) resin. Examples of the modified PPO include “Noryl” manufactured by GE Plastics Japan, and the modified PPE includes “Zylon” manufactured by Asahi Kasei Kogyo, “Iupiace” manufactured by Mitsubishi Gas Chemical, and the like. Moreover, these materials are suitable for parts that may come into contact with the processing liquid such as processing racks and crossovers.
[0101]
The drying time is preferably 10 seconds to 2 minutes, and more preferably 20 seconds to 80 seconds. As mentioned above, the continuous processing by the replenishing method has been mainly described. However, in the present invention, the processing is performed without replenishing with a certain amount of processing liquid, and then the whole or a part of the processing liquid is replaced with a new liquid and the processing is performed again. The batch processing method to be performed can also be preferably used.
[0102]
6.2 Color negative film used in the present invention
Next, details of the photosensitive material (color negative film) used in the present invention will be described.
[0103]
The color negative film according to the present invention may be provided with at least one photosensitive layer on the support. A typical example is a silver halide photographic light-sensitive material having at least one photosensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. is there. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this order from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A light-insensitive layer may be provided between the above-described silver halide light-sensitive layers, and in the uppermost layer and the lowermost layer.
[0104]
These may contain couplers, DIR compounds, color mixing inhibitors and the like described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are two layers, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, as described in DE 1,121,470 or GB 923,045, and are directed to the support. It is preferable to arrange them so that the photosensitivity decreases sequentially. Further, as described in JP-A-57-112751, 62-200350, 62-206541 and 62-206543, a low-sensitivity emulsion layer is provided on the side away from the support, and a high-sensitivity emulsion is provided on the side close to the support. Layers may be installed. As a specific example, from the side farthest from the support, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH It can be installed in the order of. Further, as described in JP-B-55-34932, the light-sensitive layer can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and 62-63936, the layers can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.
[0105]
Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest photosensitivity, the middle layer is a silver halide emulsion layer having a lower photosensitivity, and the lower layer is more sensitive than the middle layer. Examples include an arrangement composed of three layers having different sensitivities in which a low silver halide emulsion layer is arranged and the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitive emulsion layer / high in the same color-sensitive layer from the side away from the support. They may be arranged in the order of sensitive emulsion layer / low sensitive emulsion layer. In addition, they may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer, or low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer. Further, the arrangement may be changed as described above even when there are four or more layers. In order to improve the color reproducibility, BL, GL described in the specifications of US Pat. No. 4,663,271, US Pat. No. 4,705,744, US Pat. No. 4,707,436, JP-A Nos. 62-160448 and 63-89850 It is preferable that a donor layer (CL) having a multi-layer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as RL and RL is disposed adjacent to or close to the main photosensitive layer.
[0106]
A preferred silver halide used in the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing about 2 mol% to about 10 mol% of silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedrons, tetradecahedrons, irregular crystal shapes such as spheres and plates, twin planes, etc. Those having crystal defects of the above or a composite form thereof may be used. The grain size of the silver halide may be fine grains of about 0.2 μm or less or large size grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pp. 22-23, “I. Emulsion preparation and types”, and ibid. 18716 (November 1979), page 648, ibid. 307105 (November 1989), 863-865, and Grafkide, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkides, Chemie et Phisique Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" ”Published by Focal Press (GFDuffin, Photographic Emulsion Chemistry, Focal Press, 1966),“ Production and coating of photographic emulsions ”by Zeligman et al. (VLZelikman, et al., Making and Coating Photographic Emulsion, Focal Press, 1964) and the like.
[0107]
Monodisperse emulsions described in US Pat. Nos. 3,574,628, 3,655,394 and GB 1,413,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are written by Gatov, Photographic Science and Engineering, Vol. 14, pages 248-257 (1970); US 4,434,226, 4,414,310, 4,433,048, 4,439,520 and GB2,112,157. The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, or a layered structure may be formed. Silver halides having different compositions may be bonded by epitaxial bonding, and may be bonded to a compound other than silver halide, such as rhodium silver or lead oxide. A mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image types, the core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-133542. Although the thickness of the shell of this emulsion varies depending on the development processing or the like, it is preferably 3 to 40 nm, and particularly preferably 5 to 20 nm.
[0108]
As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are usually used. The additive used in such a process is RD No. 17643, ibid. 18716 and No. 1 307105, and the corresponding sections are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having at least one characteristic of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. Photosensitive silver halide grains with fogged grain surfaces as described in US Pat. No. 4,082,553, silver halide grains with fogged grains as described in US Pat. No. 4,626,498 and JP-A-59-214852, and colloidal silver. It is preferably applied to the silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The silver halide grains fogged inside or on the surface of the grains are silver halide grains that can be developed uniformly (non-imagewise) regardless of the unexposed and exposed areas of the photosensitive material. The preparation method is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of the core / shell type silver halide grain in which the inside of the grain is fogged may have a different halogen composition. As the silver halide fogged inside or on the surface, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape may be a regular grain or a polydisperse emulsion, but it is monodisperse (at least 95% of the weight or number of grains of silver halide grains has a grain size within ± 40% of the average grain size). Are preferred).
[0109]
In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain that is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing process, and is preferably not fogged in advance. The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average particle size (average value of equivalent circle diameter of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized and does not require spectral sensitization. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as triazole, azaindene, benzothiazolium, mercapto compound or zinc compound in advance. This fine grain silver halide grain-containing layer can contain colloidal silver. The silver coating amount of the light-sensitive material of the present invention is 8.0 g / m.²The following is preferred, 6.0 g / m²The following are most preferred.
[0110]
Photographic additives that can be used in the present invention are also described in the RD, and the relevant locations are shown in the following table.
[0111]
[Table 3]

[0112]
Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable.
Yellow couplers: couplers represented by formulas (I) and (II) of EP502,424A; couplers represented by formulas (1) and (2) of EP513,496A (especially Y-28 on page 18); EP568,037A A coupler represented by the formula (I) of claim 1; a coupler represented by the general formula (I) of lines 45 to 55 of column 1 of US Pat. No. 5,066,576; and a general formula (I) of paragraph 0008 of JP-A-4-274425. A coupler according to claim 1 on page 40 of EP498,381A1 (especially D-35 on page 18); a coupler represented by formula (Y) on page 4 of EP447,969A1 (especially Y-1 (17 Page), Y-54 (page 41)); couplers represented by formulas (II) to (IV) in columns 7 to 58 of column 7 of US Pat. No. 4,476,219 (particularly II-17, 19 Ram 17), II-24 (column 19)).
Magenta coupler; JP-A-3-39737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13); A-4-63 (134 of EP456,257) Page), A-4-73, -75 (page 139); EP-4,965, M-4, -6 (page 26), M-7 (page 27); EP571, 959A, M-45 (page 19) JP-A-5-204106, (M-1) (page 6); JP-A-4-36263, paragraph 0237, M-22.
[0113]
Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14-16) of JP-A-4-204843; C-7,10 (page 35), 34 of JP-A-4-43345 35 (page 37), (I-1), (I-17) (pages 42 to 43); a coupler represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385.
Polymer coupler: P-1, P-5 (page 11) of JP-A-2-44345.
[0114]
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 96,873B, DE 3,234,533 are preferred. A coupler for correcting unwanted absorption of the coloring dye is a yellow colored cyan coupler represented by the formula (CI), (CII), (CIII), (CIV) described on page 5 of EP456,257A1 (especially YC on page 84). -86), yellow colored magenta coupler ExM-7 (page 202), EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler CC described in US 4,833,069 -9 (column 8), CC-13 (column 10), US 4,837, 136 (2) (column 8), colorless masking coupler represented by formula (A) of claim 1 of WO 92/11575 (particularly 36 (Exemplary compounds on page 45) are preferred.
[0115]
Examples of compounds (including couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compounds: compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of EP378, 236A1 (especially T-101 (page 30), T-104 (31 Page), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP436, 938A2, page 7; Compounds represented by formula (1) of EP568,037A (especially (23) (page 11)), EP440,195A2 Compounds represented by I), (II), (III) (especially I- (1) on page 29);
[0116]
Bleach accelerator releasing compounds: compounds represented by formulas (I) and (I ') on page 5 of EP310, 125A2 (especially (60) and (61) on page 61) and claim 1 of JP-A-6-59411 Compound represented by formula (I) (particularly (7) (page 7)); Ligand-releasing compound: Compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478 (particularly column 12, lines 21 to 41) Leuco dye-releasing compound: compounds 1-6 of columns 3-8 of US 4,749,641; fluorescent dye releasing compound: compound represented by C0UP-DYE of claim 1 of US 4,774,181 (particularly column 7) -10 compound 1-11); development accelerator or fogging agent releasing compound: compound represented by formulas (1), (2) and (3) of column 3 of US 4,656,123 (particularly column 25) ExZK-2 on page 75, lines 36-38 of EP450, 637A2; a compound that releases a group that becomes a dye only after leaving: in formula (I) of claim 1 of US 4,857,447 The compound represented (especially Y-1 to Y-19 in columns 25 to 36).
[0117]
As additives other than couplers, the following are preferable.
Oil-soluble organic compound dispersion medium: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 of JP-A-62-215272 (140-144) Page); Latex for impregnation of oil-soluble organic compound: Latex described in US Pat. No. 4,199,363; Oxidant scavenger of developing agent: Compound represented by formula (I) in columns 2 to 54 of US Pat. No. 4,978,606 (Especially I-, (1), (2), (6), (12) (columns 4-5), US Pat. No. 4,923,787, column 2, line 5-10 (especially compound 1 (column 3) Stain inhibitor: Formula 298321A, page 4, lines 30 to 33, formulas (I) to (III), especially I-47, 72, III-1, 27 (pages 24 to 48); Antifading agent: EP-298321A, A- 6, 7, 20, 21, 23, 24, 25 26, 30, 37, 40, 42, 48, 63, 90, 92, 94, 164 (pages 69 to 118), US Pat. No. 5,122,444, columns 25 to 38, II-1 to III-23, especially III- 10, EP 471347A, pages 8-12, I-1 to III-4, particularly II-2, US 5,139, 931, columns 32 to 40, A-1 to 48, especially A-39, 42; Materials for reducing the amount of color mixing inhibitor used: EP411324A, pages 5 to 24, I-1 to II-15, especially I-46; Formalin scavenger: EP477932A, pages 24 to 29, SCV-1 to 28, especially SCV- 8;
[0118]
Hardener: Compounds represented by formulas (VII) to (XII) in columns 13 to 23 of H-1, 4, 6, 8, 14, US 4,618, 573 on page 17 of JP-A-1-214845 -1 to 54), compound (H-1 to 76) represented by formula (6) at the lower right of page 8 of JP-A-2-214852, particularly the compound described in claim 1 of H-14, US 3,325,287. Development inhibitor precursor: JP-A 62-168139, P-24, 37, 39 (pages 6-7); US 5,019,492 claim 1, compound 28, 29 of column 7; Antifungal agents: US Pat. No. 4,923,790 columns 3-15 I-1 to III-43, especially II-1,9,10,18, III-25; Stabilizers, antifoggants US Pat. 793, columns 6-16, I-1 to (14), especially I-1, 0, (2), (13), compound 1-65 of the column 25 to 32 of US4,952,483, especially 36: Chemical sensitizers: triphenylphosphine selenide, compounds described in JP-5-40324 50;
[0119]
Dyes: a-1 to b-20 on pages 15 to 18 of JP-A-3-156450, especially a-1, 12, 18, 27, 35, 36, b-5, pages V to 1 to 23 to 29 In particular, V-1, EP445627A, pages 33-55, F-1 to F-II-43, especially FI-11, F-II-8, EP457153A, pages 17-28, III-1 to 36. In particular, III-1,3, WO88 / 04794, 8-26, Dye-1 to 124 microcrystalline dispersion, EP319999A, pages 6 to 11, compounds 1 to 22, especially compound 1, EP519306A, formula (1) to Compounds D-1 to 87 represented by (3) (pages 3 to 28), compounds 1 to 22 represented by formula (I) of US 4,268,622 (columns 3 to 10), formulas of US 4,923,788 Compounds (1) to (31) represented by (I) Ram 2-9); UV absorber: compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by formula (1) of JP-A-46-3335, and formula (I) of EP520938A Compounds (3) to (66) (pages 10 to 44) and compounds HBT-1 to 10 (page 14) represented by formula (III), and compounds (1) to (1) represented by formula (1) of EP521823A 31) (columns 2-9).
[0120]
The present invention can be applied to general-purpose or negative-use color negative films for movies. Moreover, it is suitable for the film unit with a lens described in Japanese Patent Publication No. 2-32615 and Japanese Utility Model Publication No. 3-39784. Suitable supports that can be used in the present invention include, for example, the aforementioned RD. No. 17643, page 28, ibid. No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879, it is preferred to use a polyester support.
[0121]
The color negative film used in the present invention preferably has a magnetic recording layer. The magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention 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 used in the present invention are γFe₂O_ThreeFerromagnetic iron oxide such as Co-coated γFe₂O_ThreeCo-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 γFe₂O_ThreeCo-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. S in specific surface area_BET20m²/ g or more, preferably 30m²Particularly preferred is / g or more. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10^Four~ 3.0 × 10^FiveA / m, particularly preferably 4.0 × 10^Four~ 2.5 × 10^FiveA / 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-6-161032. Magnetic particles having a surface coated with an inorganic or organic material as described in JP-A-4-259911 and 5-81652 can also be used.
[0122]
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 polymer (cellulose) described in JP-A-4-219469. Derivatives, sugar derivatives and the like) and mixtures thereof. 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. 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 polyalcohols (for example, tolylene diisocyanate). A reaction product of 3 mol of narate and 1 mol of trimethylolpropane), polyisocyanates produced by condensation of these isocyanates, and the like, for example, described in JP-A-6-59357.
[0123]
As a method of dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill, etc. are preferable, as in the method described in JP-A-6-35092. Dispersants 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 magnetic particles is 0.005 to 3 g / m², Preferably 0.01-2 g / m²More preferably, 0.02 to 0.5 g / m²It 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, extrusion, etc. can be used. The coating solution described in 341436 is preferable.
[0124]
The magnetic recording layer may have functions such as lubricity improvement, curling adjustment, antistatic, adhesion prevention, head polishing, etc., or another functional layer may be provided to give these functions. A polishing agent for non-spherical inorganic particles in which at least one of the particles has a Mohs hardness of 5 or more is preferable. 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. The binder used at this time can use the above-mentioned binders, and preferably the same binder as that of the magnetic recording layer. Photosensitive materials having a magnetic recording layer are described in US Pat. No. 5,336,589, 5,250,404, 5,229,259, 5,215,874, EP466,130.
[0125]
The polyester support used in the present invention will be described, but the details including the photosensitive materials, treatments, cartridges and examples described later are disclosed in the published technical report, public technical number 94-6023 (Invention Association; 1994. 3.15.). It is described in. The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, terephthalic as aromatic dicarboxylic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymerized 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 of the present invention is 50 ° C. or higher, more preferably 90 ° C. or higher.
[0126]
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, SnO₂And Sb₂O_FiveThe surface shape may be improved). 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 forming the support, after the surface treatment, after applying the back layer (antistatic agent, slip agent, etc.), and after applying the undercoat. Preferred is after application of the antistatic agent. This polyester may be kneaded with an ultraviolet absorber. In order to prevent light piping, the purpose can be achieved by kneading commercially available dyes or pigments for polyester such as Mitsubishi Kasei's Diaresin and Nippon Kayaku's Kayaset.
[0127]
Next, in the present invention, a surface treatment is preferably performed in order to bond the support and the light-sensitive 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, it may be a single layer or two or more layers. 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. SiO₂TiO₂In addition, inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.
[0128]
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, SnO₂, Al₂O_Three, In₂O_Three, SiO₂, MgO, BaO, MoO_Three, V₂O_FiveA volume resistivity of at least one selected from⁷Ω · cm or less, more preferably 10^FiveParticle size of Ω · cm or less 0.001-1.0 μm Crystalline metal oxide or composite oxide of these (Sb, P, B, In, S, Si, C, etc.), and sol These metal oxides or fine particles of these composite oxides. The content in the sensitive material is 5 to 500 mg / m.²Is particularly preferred, 10 to 350 mg / m²It 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.
[0129]
The light-sensitive material of the present invention preferably has slipperiness. The slip agent-containing layer is preferably used for 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 the value when transported at 60 cm / min with respect to a stainless steel ball having a diameter of 5 mm (25 ° C., 60% PH). In this evaluation, even if the counterpart material is replaced with the photosensitive layer surface, the value is almost the same. Examples of slip agents that can be used in the present invention 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 polystyrylmethyl. Siloxane, 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.
[0130]
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 narrower, and preferably 90% or more of the total number of particles is 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 matting properties, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm) ), Polystyrene particles (0.25 μm), and colloidal silica (0.03 μm).
[0131]
Next, the film cartridge used in the present invention 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. Furthermore, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations, betaine surfactants, polymers, and the like can be preferably used. These antistatic cartridges are described in JP-A Nos. 1-312537 and 1-312538. Especially, the resistance at 25 ° C. and 25% RH is 10¹²Ω or less is preferable. Usually, plastic patrone is manufactured using a plastic kneaded with carbon black or pigment to provide light shielding. The size of the cartridge may be the current 135 size, and it is also effective to reduce the diameter of the 25 mm cartridge of the current 135 size to 22 mm or less in order to reduce the size of the camera. Patrone case volume is 30cm^ThreeBelow preferably 25cm^ThreeThe following is preferable. The weight of the plastic used for the cartridge and the cartridge case is preferably 5 to 15 g.
[0132]
Further, a patrone for feeding a film by rotating a spool may be used in the present invention. Further, 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. No. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a photographic film that has been developed. Further, the raw film and the developed photographic film may be stored in the same new cartridge, or may be different cartridges.
[0133]
In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the side having an emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and particularly preferably 16 μm or less. In addition, membrane swelling speed_1/2Is preferably 30 seconds or shorter, and more preferably 20 seconds or shorter. T_1/2Is defined as the time until the film thickness itself reaches ½ when 90% of the maximum swollen film thickness reached when processed at 30 ° C. for 3 minutes and 15 seconds with a color developer is defined as the saturated film thickness. The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days)._1/2Is a spherometer of the type described in A. Green et al., Photographic Science and Engineering (Photogr. Sci. Eng.), Vol. 19, pp. 2,124-129. Can be measured. T_1/2Can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. This back layer preferably contains the aforementioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably 150 to 500%.
[0134]
【Example】
EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
[0135]
Example 1
1. Color negative film tested
Two types of color negative film samples 101 and 102 were prepared as follows.
[0136]
Each layer of the composition as shown below was applied on the undercoated cellulose triacetate film support to produce a negative type multilayer color photosensitive material for photographing.
(Photosensitive layer composition)
The main materials used in each layer are classified as follows:
ExC: Cyan coupler UV: UV absorber
ExM: Magenta coupler HBS: High boiling point organic solvent
ExY: Yellow coupler H: Gelatin hardener
ExS: Sensitizing dye
Number corresponding to each component, g / m²The coating amount expressed in units is shown. For silver halide, the coating amount in terms of silver is shown. However, for the sensitizing dye, the coating amount with respect to 1 mol of silver halide in the same layer is shown in mol units.
[0137]
[Sample 101]
First layer (antihalation layer)
Black colloidal silver Silver 0.09
Gelatin 1.60
ExM-1 0.12
ExF-1 2.0 × 10^-3
Solid disperse dye ExF-2 0.030
Solid disperse dye ExF-3 0.040
HBS-1 0.15
HBS-2 0.02
[0138]
Second layer (intermediate layer)
Silver iodobromide emulsion M Silver 0.065
ExC-2 0.04
Polyethyl acrylate latex 0.20
Gelatin 1.04
[0139]
3rd layer (low sensitivity red sensitive emulsion layer)
Silver iodobromide emulsion A Silver 0.25
Silver iodobromide emulsion B Silver 0.25
ExS-1 6.9 × 10^-Five
ExS-2 1.8 × 10^-Five
ExS-3 3.1 × 10^-Four
ExC-1 0.17
ExC-3 0.030
ExC-4 0.10
ExC-5 0.020
ExC-6 0.010
Cpd-2 0.025
HBS-1 0.10
Gelatin 0.87
[0140]
Fourth layer (medium sensitivity red emulsion layer)
Silver iodobromide emulsion C Silver 0.70
ExS-1 3.5 × 10^-Four
ExS-2 1.6 × 10^-Five
ExS-3 5.1 × 10^-Four
ExC-1 0.13
ExC-2 0.060
ExC-3 0.0070
ExC-4 0.090
ExC-5 0.015
ExC-6 0.0070
Cpd-2 0.023
HBS-1 0.10
Gelatin 0.75
[0141]
5th layer (High sensitivity red emulsion layer)
Silver iodobromide emulsion D Silver 1.40
ExS-1 2.4 × 10^-Four
ExS-2 1.0 × 10^-Four
ExS-3 3.4 × 10^-Four
ExC-1 0.10
ExC-3 0.045
ExC-6 0.020
ExC-7 0.010
Cpd-2 0.050
HBS-1 0.22
HBS-2 0.050
Gelatin 1.10
[0142]
6th layer (intermediate layer)
Cpd-1 0.090
Solid disperse dye ExF-4 0.030
HBS-1 0.050
Polyethyl acrylate latex 0.15
Gelatin 1.10
[0143]
7th layer (low sensitivity green emulsion layer)
Silver iodobromide emulsion E Silver 0.15
Silver iodobromide emulsion F Silver 0.10
Silver iodobromide emulsion G Silver 0.10
ExS-4 3.0 × 10^-Five
ExS-5 2.1 × 10^-Four
ExS-6 8.0 × 10^-Four
ExM-2 0.33
ExM-3 0.086
ExY-1 0.015
HBS-1 0.30
HBS-3 0.010
Gelatin 0.73
[0144]
8th layer (medium sensitive green emulsion layer)
Silver iodobromide emulsion H Silver 0.80
ExS-4 3.2 × 10^-Five
ExS-5 2.2 × 10^-Four
ExS-6 8.4 × 10^-Four
ExC-8 0.010
ExM-2 0.10
ExM-3 0.025
ExY-1 0.018
ExY-4 0.010
ExY-5 0.040
HBS-1 0.13
HBS-3 4.0 × 10^-3
Gelatin 0.80
[0145]
9th layer (high-sensitivity green-sensitive emulsion layer)
Silver iodobromide emulsion I Silver 1.25
ExS-4 3.7 × 10^-Five
ExS-5 8.1 × 10^-Five
ExS-6 3.2 × 10^-Four
ExC-1 0.10
ExM-1 0.020
ExM-4 0.025
ExM-5 0.040
Cpd-3 0.040
HBS-1 0.25
Polyethyl acrylate latex 0.15
Gelatin 1.33
[0146]
10th layer (yellow filter layer)
Yellow colloidal silver silver 0.015
Cpd-1 0.16
Solid disperse dye ExF-5 0.060
Solid disperse dye ExF-6 0.060
Oil-soluble dye ExF-7 0.010
HBS-1 0.60
Gelatin 0.60
[0147]
11th layer (low sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion J Silver 0.09
Silver iodobromide emulsion K Silver 0.09
ExS-7 8.6 × 10^-Four
ExC-8 7.0 × 10^-3
ExY-1 0.050
ExY-2 0.22
ExY-3 0.50
ExY-4 0.020
Cpd-2 0.10
Cpd-3 4.0 × 10^-3
HBS-1 0.28
Gelatin 1.20
[0148]
12th layer (high sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion L Silver 1.00
ExS-7 4.0 × 10^-Four
ExY-2 0.10
ExY-3 0.10
ExY-4 0.010
Cpd-2 0.10
Cpd-3 1.0 × 10^-3
HBS-1 0.070
Gelatin 0.70
[0149]
13th layer (first protective layer)
UV-1 0.19
UV-2 0.075
UV-3 0.065
HBS-1 5.0 × 10^-2
HBS-4 5.0 × 10^-2
Gelatin 1.8
[0150]
14th layer (second protective layer)
Silver iodobromide emulsion M Silver 0.10
H-1 0.40
B-1 (diameter 1.7 μm) 5.0 × 10^-2
B-2 (diameter 1.7 μm) 0.15
B-3 0.05
S-1 0.20
Gelatin 0.70
[0151]
Furthermore, W-1 to W-3, B-4 to B-6, F in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial properties, antistatic properties and coatability as appropriate for each layer. -1 to F-17 and iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt, rhodium salt.
[0152]
[Table 4]

[0153]
In Table 4,
(1) Emulsions J to L were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.
(2) Emulsions A to I were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been.
(3) In preparation of tabular grains, low molecular weight gelatin is used according to the example of JP-A-1-158426.
(4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high-voltage electron microscope.
(5) Emulsion L is a double-structured grain containing an internal high iodine core as described in JP-A-60-143331.
[0154]
(Preparation of dispersion of organic solid disperse dye)
The following ExF-2 was dispersed by the following method. That is, 21.7 ml of water and 3 ml of p-octylphenoxyethoxyethoxyethane sulfonic acid soda in 5% aqueous solution and 0.5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) in 700 ml In a pot mill, 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. A BO-type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After dispersion, the contents were taken out and added to 8 g of a 12.5% aqueous gelatin solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles was 0.44 μm.
[0155]
Similarly, solid dispersions of ExF-3, ExF-4, and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of European Patent Application (EP) No. 549,489A. The average particle size was 0.06 μm.
[0156]
[Chemical 1]

[0157]
[Chemical 2]

[0158]
[Chemical Formula 3]

[0159]
[Formula 4]

[0160]
[Chemical formula 5]

[0161]
[Chemical 6]

[0162]
[Chemical 7]

[0163]
[Chemical 8]

[0164]
[Chemical 9]

[0165]
[Chemical Formula 10]

[0166]
Embedded image

[0167]
Embedded image

[0168]
Embedded image

[0169]
Embedded image

[0170]
Embedded image

[0171]
Embedded image

[0172]
[Sample 102]
Next, a low silver color negative film was prepared by reducing the coating amount of all the coating layers from the first layer to the fourteenth layer of the sample 101 to one half to obtain a sample 102. That is, the total coated silver amount of the sample 101 is 6.45 g / m.²However, in Sample 102, it was 3.225 g / m only by adjusting the coating amount without changing the emulsion composition.²Changed to
[0173]
2. Photographic property test method
Each test film is exposed to a standard C light source as described in ISO 5800 (sensitivity measurement method for color negative film) and is exposed to three levels: standard exposure, half underexposure and overexposure four times the standard. Then, a snapshot of a person was taken against a gray wall, and the development processing conditions were changed as follows to create a photo manuscript for the input image.
The input image thus obtained was converted into an image signal using the image reading apparatus described in the section of the invention. In accordance with the procedure of paragraph 4.2 of the invention, image processing combining tone correction processing and color correction processing is performed, and based on this image signal, the laser scanning exposure apparatus shown in FIG. Exposure was performed, and the following predetermined development processing was performed to obtain an image for evaluation. The overall image quality was evaluated with an average score by 10 persons who specialized in photographic evaluation, scoring by the following five-point method, with emphasis on the granular smoothness of the image for evaluation.
Very poor and unacceptable. ... 1 point
Somewhat inferior and unacceptable. 2 points
Relatively inferior but acceptable. ... 3 points
It is relatively excellent and preferable. ... 4 points
Highly preferred. ..... 5 points
[0174]
3. Processing for input image
The following color negative development processing specifications were followed.
As a processing machine, it processed with the processing process and processing liquid which are shown below using the Fuji Photo Film Co., Ltd. automatic processor FP-560B.
In addition, the fixing step omission processing which is the processing step of the present invention is a modification of the film transport system of the processor so that after the color development and bleaching step, the sample is sent to the washing bath immediately after skipping the two fixing racks. went.
[0175]

The stabilizing liquid was a counter-current system from (2) to (1), and all the overflow water of the washing water was introduced into the fixing (2). The fixer is also connected from (2) to (1) by counterflow piping. The amount of developer brought into the bleaching process, the amount of bleaching solution brought into the fixing step, and the amount of fixing solution brought into the water washing step were 2.5 ml and 2.0 ml per 1.1 mm width of the photosensitive material 35 mm, respectively. 2.0 milliliters. In addition, the crossover time is 6 seconds, and this time is included in the processing time of the previous process.
[0176]
The composition of the treatment liquid is shown below.

[0177]

[0178]

[0179]
(Washing water)
Tap water is passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IR-400). Then, the calcium and magnesium ion concentrations were adjusted to 3 mg / liter or less, and then sodium isocyanurate dichloride 20 mg / liter and sodium sulfate 150 mg / liter were added. The pH of this solution was in the range of 6.5 to 7.5.
[0180]

[0181]
4). Image processing for evaluation images
A high-speed scanner / image processing workstation SP-1000 is an example of a commercially available input machine that can convert an input image produced in the above configuration into an electrical image signal and input the signal to create a positive image. A laser printer / paper processor LP-1000P (manufactured by Fuji Photo Film Co., Ltd.) was used as an example of a commercially available output machine manufactured by Fuji Photo Film Co., Ltd. For SP-1000, the program software was changed so that the image processing could be performed.
For the comparative sample, a minilab PP-1257V manufactured by Fuji Photo Film Co., Ltd., which is currently a common surface exposure method, was used. The printer of this device is a simultaneous overall exposure method that passes through the developed color negative and prints on the color paper, and is a method commonly used in the current market that controls the color balance by controlling the filter. is there.
In both cases, commercially available Fuji color laser paper was used as the color paper, and the development processing was performed according to a general color paper processing formulation CP-47L and its processing agent (both manufactured by Fuji Photo Film Co., Ltd.).
[0182]
5. test
The following tests were conducted.
(1) Comparative experiment-1: Sample 101 and 102 subjected to standard development processing according to the above-mentioned color negative development processing formulation and process are subjected to the above-mentioned image processing with SP-1000, and subjected to printing and positive development processing with LP-1000P for comparison. A color print was obtained.
(2) Comparative experiment-2: Samples 101 and 102 subjected to the standard development processing according to the above-described color negative development processing formulation and process were baked and positively developed with a surface exposure type PP-1257V to obtain a comparative color print.
(3) Comparative experiment-3: Samples 101 and 102 for which the fixing step was omitted were printed with PP-1257V and subjected to positive development to obtain a comparative color print.
(4) Invention Experiment-1: Sample 101 and 102 subjected to the fixing process omission processing similar to Comparative Experiment-3 are subjected to the above-mentioned image processing with SP-1000, and are subjected to printing and positive development processing with LP-1000P. A color print was obtained by the method and apparatus. The image processing conditions are corrected in the image processing apparatus (that is, SP-1000) described in 4.2 above when the development density obtained in the development process in which the fixing process is omitted is input. Except for this, it is as normal conditions of SP-1000.
[0183]
6). Test results
The test results are shown in Table 5.
[0184]
[Table 5]

[0185]
As can be seen from Table 5, in Comparative Experiments 1 and 2 in which the standard development process was performed, both showed standard image quality, and the presence or absence of image processing and the resulting difference in output device, that is, between Comparative Experiments 1 and 2 The difference in image quality is small. On the other hand, in Comparative Experiment 3 in which image processing for image reproduction is not performed after the fixing step omission processing, the image quality is not sufficiently reproduced, particularly in the case of overexposure. The present invention experiment-1 in which the image processing was performed after the fixing step omission processing had the same image quality as the comparative experiment-1 in which the image processing was performed in addition to the reference development processing, and the reproduction of the image quality was satisfied. .
Further, the amount of waste liquid from the development process of the present invention was reduced by 17% with respect to the standard development process. Further, the effect of the sample 102, which is a low silver photosensitive material, was more remarkable.
On the other hand, in this example, the water washing alternative stabilizer was used. However, when the water washing method is adopted, the amount of nitrogen compounds in the waste water is reduced by 85% from the prescription value and the replenishment amount in each of the above steps. Desired.
In addition, the time reduction of all processes for obtaining a color print from the start of development of the color negative film in this example was 100 seconds (corresponding to the fixing process).
[0186]
Example 2
The test performed in Example 1 was repeated. However, this time, the image reading from the developed sample was shown in FIG. 11, and the reflection type density reading method described in the section 4.1 of this specification was performed. The commercially available image processing apparatus (SP-1000) used in Example 1 is equipped with a transmission type and a reflection type image reading apparatus.
Image reading is performed smoothly, and image processing and output to color paper are performed in the same manner as in the first embodiment. As a result, a print having the same image quality as the image obtained by the standard development processing as in the first embodiment is obtained. It was.
[0187]
【The invention's effect】
When developing a photographed color film, a standard development process (that is, a standard development process) is performed by performing an image process on the obtained image information even if a simple development process without a fixing process is performed. Image information with substantially the same image quality can be obtained. Furthermore, it is possible to provide a color print with a normal image quality by a simplified development process.
By reducing the coating amount of the silver halide emulsion on the color film, the effect of the present invention can be maintained and the raw material cost of the color film can be reduced.
[Brief description of the drawings]
FIG. 1 is a block diagram showing the basic configuration and overall flow of an image forming method and apparatus according to the present invention.
FIG. 2 is a block diagram showing a basic configuration of an image reproduction system according to the present invention.
FIG. 3 is a diagram showing an external appearance in an embodiment of an image reproduction system according to the present invention.
FIG. 4 is a diagram showing an outline of a transmissive image reading apparatus.
5 is a block diagram showing a part of the configuration of the image processing apparatus 5 shown in FIG.
6 is a block diagram showing another part of the configuration of the image processing apparatus 5 shown in FIG. 2 that is not shown in FIG. 5;
7 is a block diagram showing details of the first frame memory unit, the second frame memory unit, and the third frame memory unit shown in FIG. 5;
8 is a block diagram showing details of the first image processing means shown in FIG. 6;
FIG. 9 is a diagram showing an outline of the image output apparatus shown in FIG. 2;
10 is a laser beam irradiation means of the image output device shown in FIG. 9;
FIG. 11 is a diagram showing an outline of a reflective image reading apparatus.
[Explanation of symbols]
Explanation of reference numerals in FIGS.
F film
P Color print or color paper
01 DX code
02 Development selection instruction section
03 Standard development process
03A non-standard development process
04 Manual development selection
1 Image reading device
5 Image processing device
8 Image output device
10 Transmission type image reading device
11 Light source
12 Light control unit
13 color separation unit
14 Diffusion unit
15 CCD area sensor
16 lenses
17 Amplifier
18 A / D converter
19 CCD correction means
20 Log converter
21 interface
22 Carrier
23 Motor
24 Drive roller
25 Screen detection sensor
26 CPU
30 Reflective image reader
31 Light source
32 mirror
33 Color balance filter
34 Light intensity adjustment unit
35 CCD area sensor
36 lenses
37 Amplifier
38 A / D converter
39 CCD correction means
40 Log converter
48 interface
49 Mean arithmetic means
50a first line buffer
50b second line buffer
51 First frame memory unit
51R R data memory
51G G data memory
51B B data memory
52 Second frame memory unit
52R R data memory
52G G data memory
52B B data memory
53 Third frame memory unit
53R R data memory
53G G data memory
53B B data memory
55 selector
60 CPU
61 First image processing means
62 Second image processing means
63 Input bus
64 output bus
65 Data bus
66 memory
67 Hard Disk
68 CRT
69 keyboard
70 Communication port
75 Data composition means
76 Composite data memory
76R R data memory
76G G data memory
76B B data memory
77 interface
78 interface
79 CPU
80 Image data memory
81 D / A converter
82 Laser light irradiation means
83 Modulator drive means
84a, b, c Semiconductor laser light source
85 Wavelength conversion means
86 Wavelength conversion means
87R, G, B optical modulator
88R, G, B Reflection mirror
89 Polygon mirror
90 color paper
91 magazine
92 Drilling means
94 Color developer tank
95 Bleach fixing tank
96 Flush tank
97 Drying section
98 cutter
99 Sorter
100 color density gradation conversion means
101 Saturation conversion means
102 Digital magnification conversion means
103 Frequency processing means
104 Dynamic range conversion means

Claims (6)

The photographed silver halide color photographic material is subjected to a development process that includes 1) a color development process and a bleaching process, and no fixing process.
2) photoelectrically reading image information from the developed image and converting it into electrical digital information;
3) Image processing of electrical digital information to correct the image quality characteristics to be obtained when developing the color photographic material under the standard development processing conditions,
A color image forming method characterized in that image information having the same image quality as that obtained when the color photographic material is subjected to a standard development process is obtained. 2. The color image forming method according to claim 1, wherein the image information is photoelectrically read by reflected light. 3. Color image formation according to claim 1 or 2, characterized in that the silver halide coating amount of the photographed silver halide color photographic material is 1.0 to 4.0 g / m ² (silver equivalent amount). Method. The color image according to any one of claims 1 to 3, wherein the replenishing amount in the bleaching step and the final bath step is 30 ml or less per 35 mm 24 film (135-24 format) film. Forming method. 5. The total amount of development processing waste discharged from the development processing step is 50 milliliters or less per film of 35 mm / 24 film (135-24 format). Color image forming method. The photographed silver halide color photographic material is subjected to (1) a development process including a color development process and a bleaching process and not including a fixing process, and (2) image information is photoelectrically read from the developed image. (3) image processing of the electrical digital information to correct the image quality characteristics to be obtained when the color photographic material is developed under the standard development processing conditions. , A material for use in an image forming method comprising obtaining image information of the same image quality as that obtained when the color photographic material is subjected to a standard development process, wherein the silver halide coating amount is 1.0 to 4.0 g / Silver halide color photographic material characterized by m ² (silver equivalent).

Images