JP2004151544A - Processing method for silver halide color photographic sensitive material and color developing solution used for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a high quality image by enhancing the permeating power of a color developing solution to a photosensitive material and thoroughly carrying out a color development reaction, in a step of color-developing a silver halide color photographic sensitive material. <P>SOLUTION: A surface of a photosensitive material containing deionized water or a very small amount of a color developing agent or an alkali agent is coated with a preprocessing solution, coated with a developing agent part processing solution and then coated with an alkali part processing solution to carry out a color developing step. <P>COPYRIGHT: (C)2004,JPO

Description

【０１１４】
この化合物は特開２０００−１６２７５０にて開示されているヒドロキシルアミン誘導体であり、処理液の酸化を効率良く防止することができる。
【０１１５】
この場合添加量は０．０００５〜０．０８ｍｏｌ／ｌが好ましく、また０．０１〜０．０６ｍｏｌ／ｌがより好ましい。
【０１１６】
また、主薬パート液及びアルカリパート液共通に、ポリオキシエチレンアルキルフェニルエーテル等の界面活性剤や、トリアジニルスチルベン系の蛍光増白剤を添加することもできる。
【０１１７】
この場合添加量は０．０００５〜０．０８ｍｏｌ／ｌが好ましく、また０．０１〜０．０６ｍｏｌ／ｌがより好ましい。
【０１１８】
＜処理方法＞
次に、本発明の処理方法について説明する。
【０１１９】
本発明の処理方法は、発色現像工程を含むハロゲン化銀カラー写真感光材料の処理方法であって、発色現像工程が前処理液で処理する前処理工程と、発色現像主薬液で処理する主薬液工程と、アルカリ液で処理するアルカリ液工程とを含むことを特徴とする。
【０１２０】
以下、図を用いて本発明の発色現像液と従来の発色現像液とを比較しつつ概略を説明する。図１は従来の処理方法における２液塗布法の発色現像工程の概略図であり、図２は本発明の処理方法における本発明の発色現像液を用いた発色現像工程の概略を示す図である。
【０１２１】
図１に示すように、従来の発色現像液では、主薬液を塗布後、アルカリ液を塗布するという２段階の処理だけであったため、主薬が感材表面近くにとどまって主薬濃度が表面近くで濃くなり底部では低くなるため、画像ムラの原因となっていた。特に高濃度処理液を用いるドライ処理では問題が多かったが、本発明の発色現像液の構成によればそのような浸透ムラを防止し、発色や写真特性を向上させることが可能となる。
【０１２２】
図２に示すように、本発明の発色現像液では主薬液を塗布する前に予め前処理液を塗布、浸透させることにより、主薬液を塗布したときに感材内部まで主薬液を引き込むことが可能となり、それによりアルカリ液を塗布後、内部までムラなく発色反応が起こるため発色性を向上させることができる。
【０１２３】
すなわち、前処理工程で感材に予め前処理液を塗布することにより、次の主薬液塗布工程で主薬の浸透を高め、それによりアルカリ液塗布工程で生じる発色反応が感材の各色層でバランス良く行われるため、画像の品質が向上することが可能となる。また、感材への処理液の浸透が早まるため、処理時間も短縮することができ、処理効率も向上する。
【０１２４】
次に、発色現像工程以降の工程（以下後処理工程ともいう）も含めた全体構成について説明する。
【０１２５】
後処理工程では、発色現像工程において本発明の発色現像液を使用して現像された感材上に生じた銀を脱銀工程において酸化・溶解し、さらに水洗工程にて水洗除去または防黴剤や色素の安定化剤を含む安定化工程にて洗浄することにより一連の処理が行われる。また、通常は水洗／安定化工程の後に、処理を終えた感光材料を乾燥させる乾燥工程を設けることもできる。
【０１２６】
ここで、脱銀処理工程は、基本的には、現像で生じた銀を漂白液により酸化する漂白工程と、酸化された銀を定着液により溶解可能な銀塩に変える定着工程とから構成されている。ただし、漂白工程と定着工程は、各々漂白液と定着液とを用いて別工程として処理することもできるが、漂白液と定着液とを混合し漂白と定着を同時に行うことができるようにした漂白定着液を用い、漂白工程と定着工程とを一体化して行うこともできる（漂白定着工程）。また、処理工程によっては、漂白工程、定着工程及び漂白定着工程を各々適宜組み合わせることができ、例えば漂白又は定着を行った後にさらに漂白定着液による漂白定着工程を設けることもできる。すなわち、本発明の処理方法については、具体的には次のような手順を例示することができる。ただし、本発明の処理方法は、これらに限定されるものではない。
１）発色現像−漂白−定着−水洗（安定）−乾燥−スキャン
２）発色現像−漂白−定着−水洗（安定）−スキャン
３）発色現像−漂白−定着−乾燥−スキャン
４）発色現像−漂白−定着−スキャン
５）発色現像−定着−水洗（安定）−乾燥−スキャン
６）発色現像−定着−水洗（安定）−スキャン
７）発色現像−定着−乾燥−スキャン
８）発色現像−定着−スキャン
９）発色現像−漂白−水洗（安定）−乾燥−スキャン
１０）発色現像−漂白−水洗（安定）−スキャン
１１）発色現像−漂白−乾燥−スキャン
１２）発色現像−漂白−スキャン
１３）発色現像−漂白定着−水洗（安定）−乾燥−スキャン
１４）発色現像−漂白定着−水洗（安定）−スキャン
１５）発色現像−漂白定着−乾燥−スキャン
１６）発色現像−漂白定着−スキャン
１７）発色現像−水洗（安定）−乾燥−スキャン
１８）発色現像−水洗（安定）−スキャン
１９）発色現像−乾燥−スキャン
２０）発色現像−スキャン
この中でも、好ましくは１〜１６の工程が良く、より好ましくは１、２、４〜６及び８の工程が良い。
【０１２７】
このように、発色現像工程の後に後処理工程を設けた方が、感材の透過率が向上するため、短時間でスキャンが完了するという、いわゆるスキャン適性が向上する。
【０１２８】
本発明の処理方法においては、発色現像工程は浸漬処理を行っても、感材上に処理液を直接と付しても良く、またこれらの処理を併用しても良い。発色現像工程以降の処理についても同様に浸漬処理でも直接塗布でも併用でも良い。
【０１２９】
また、各工程間で、感材上に残った処理液を掻き取るスクイーズ処理を行っても良い（スクイーズ工程）。これにより次の塗布する処理液の浸透率を高めることができる。また、含浸処理の場合には次槽に持ちこまれることを防止できるので、処理効率も向上する。
【０１３０】
次に、各工程について順次説明していく。
【０１３１】
＜発色現像工程＞
本発明に係る発色現像工程は、上述した本発明の発色現像液を用いて処理を行う。すなわち、予め前処理液を感材に塗布した後に主薬液を塗布し、その後アルカリパート処理液を塗布するという構成となっている。
【０１３２】
ここで、上記方法では、前処理液−主薬パート処理液−アルカリパート処理液を各一回塗布するという構成だけでなく、各処理液をそれぞれ複数回塗布あるいは一回塗布との組み合わせという構成であっても良い。例としては、以下の工程が上げられる。
１．前処理−主薬液−アルカリ
２．前処理−主薬液複数回−アルカリ
３．前処理−主薬液−アルカリ複数回
４．前処理−主薬液複数回−アルカリ複数回
５．（前処理−主薬液）複数回−アルカリ複数回
６．（前処理−主薬−アルカリ）複数回
上記の中でも好ましくは１、３、５が良い。
【０１３３】
従来の塗布方法では、発色現像液及びアルカリ液をそれぞれ一回塗布するだけであったので、感度の異なる感材を処理する場合は必要となる主薬の量が異なるにもかかわらず、一つの装置では対応できないという問題があるが、このような構成によれば、各感材が必要とする主薬の量を複数回に分けて塗布することができるので、各色層が充分に発色することが可能となり、画像の写真特性も良好なものとなる。
【０１３４】
また、上記３つの工程の間にはスクイーズ工程を設けることもできる。これにより、次処理への持ちこみ成分が現象するため、処理の効率化が図れる。この場合、スクイーズ材としてはローラー、スポンジ、スクイーズブレードを用いることができ、これにより感材表面に付着した塗布液を除去する。このうち、ローラーは吸水性であっても非吸水性であっても構わない。
【０１３５】
このように、本発明の処理方法では、発色現像工程において発色現像主薬液を塗布する前に前処理液を事前に感材へ塗布することにより、その後塗布する発色現像主薬液及びアルカリ液の浸透性を高めることが可能となり、得られる画質も向上し、写真特性も良好となる。
【０１３６】
前処理液としてはハロゲン化銀カラー写真感光材料に対して１〜３０００ｍｌ／ｍ^２供給するようにする。好ましくは５〜１０００ｍｌ／ｍ^２、より好ましくは１０〜５００ｍｌ／ｍ^２供給されること望ましい。
【０１３７】
ここで、主薬液に含まれる前記発色現像主薬は前記ハロゲン化銀カラー写真感光材料に対して０．０１〜０．５ｍｏｌ／ｍ^２供給されるようにする。供給量をこの範囲とすると、感材に必要な主薬量を供給する場合でも、塗布した液が感材から流れ落ちて無駄になるといった事が無く、しかも塗布装置のノズルに析出物が出るといった問題がでないという利点がある。また、０．０１５〜０．３５ｍｏｌ／ｍ^２供給されるのが好ましく、０．０２５〜０．１７ｍｏｌ／ｍ^２供給されるのがより好ましい。
【０１３８】
次いで塗布されるアルカリ液に含まれる前記アルカリ剤はハロゲン化銀カラー写真感光材料に対して０．００５〜１ｍｏｌ／ｍ^２供給されるようにする。この範囲の供給量とすると、感材に必要なアルカリ量を供給する場合でも、塗布した液が感材から流れ落ちて無駄になるといった事が無く、しかも塗布装置のノズルに析出物が出るといった問題がでないという利点がある。この場合は、０．００７〜０．３３ｍｏｌ／ｍ^２供給するのが好ましく、０．００７〜０．０７ｍｏｌ／ｍ^２がより好ましい。
【０１３９】
どちらの処理液も、感材への塗布量は、１〜３０００ｍｌ／ｍ^２の範囲であり、好ましくは５〜１０００ｍｌ／ｍ^２、より好ましくは１０〜５００ｍｌ／ｍ^２の量が好ましい。
【０１４０】
これにより感材の色素層全てに適切な量の処理液が浸透し、適度な反応により品質の高い画像を得ることができる。
【０１４１】
また塗布時の温度はともに２５〜７０℃の範囲であり、３０〜６５℃が好ましく、４０〜６０℃がより好ましい。
【０１４２】
また、塗布時間はどちらも３秒〜５分の範囲で処理され、好ましくは５秒〜２分３０秒、より好ましくは５秒〜２分の範囲が良い。
【０１４３】
また、塗布回数は、どちらも１〜２０回の間であれば複数回塗布することともできる。好ましくは１〜１２回、より好ましくは１〜５回が良い。
【０１４４】
また、上述したように主薬液のみを上記範囲内で複数塗布することも可能であるし、主薬液−アルカリ液塗布を複数行うことも可能である。
【０１４５】
感度が異なる感材を一つの装置で処理しようとすると、従来の方法では塗布は一度だけなので、各感材が必要とする主薬液を供給することができず、発色不十分になったり、画像ムラが生じたりするという問題があったが、本発明の処理方法では、各感材が必要とする液の量を複数回塗布することにより供給できるので、どのような感材であっても十分に写真特性を得ることが可能となり、画質も向上するという効果がある。
【０１４６】
このように、塗布方法による発色現像処理において、主薬液を塗布する前に前処理液を塗布することにより、感材内部への処理液の浸透を向上させることができ、それにより画像の向上を可能とすることができる。また、処理時間そのものも従来と比較して大幅に短縮することが可能となる。
【０１４７】
＜後処理工程＞
次に発色現像工程後の後処理工程について説明する。
【０１４８】
本発明の処理方法は、ドライ方法で処理を行うため、後処理工程もそれぞれ塗布処理で行うことができるが、もちろん従来通り処理槽で含浸処理を行うことも可能である。
【０１４９】
＜漂白工程＞
まず、漂白工程に用いられる処理液の組成について説明する。
【０１５０】
本発明に係る漂白工程では、後述するような漂白主薬、漂白促進剤、再ハロゲン化剤、ｐＨ緩衝剤及びその他の添加剤を含む漂白液を使用することができる。
【０１５１】
漂白主薬としてはアミノポリカルボン酸鉄（ＩＩＩ）塩や過硫酸等が使用される。具体的には、エチレンジアミン四酢酸、１，３−プロパンジアミン四酢酸、ジエチレントリアミン五酢酸、１，２−シクロヘキサンジアミン四酢酸、イミノ二酢酸、メチルイミノ二酢酸、ニトリロ三酢酸、ヒドロキシメチルイミノ二酢酸、Ｎ−（２−カルボキシエチル）イミノ二酢酸、Ｎ−（２−カルボキシメチル）イミノ二酢酸、β−アラニン二酢酸、エチレンジアミン−Ｎ，Ｎ’−ジコハク酸、１，３−プロパンジアミンーＮ，Ｎ’−ジコハク酸、エチレンジアミン−Ｎ，Ｎ’−ジマロン酸、１，３−プロパンジアミンーＮ，Ｎ’−ジマロン酸等の鉄（ＩＩＩ）塩を使用することができる。
【０１５２】
漂白主薬の添加量としては、０．００５〜２ｍｏｌ／ｌが好ましく、０．０１〜１．０ｍｏｌ／ｌがより好ましい。
【０１５３】
また、本発明の漂白液には、例えばメルカプト化合物や、ジスルフィド化合物、チオール化合物等の漂白促進剤を使用することができる。
【０１５４】
更に再ハロゲン化剤を付加しても良い。例えばアルカリ金属の塩化物塩、臭化物塩、沃化物塩及び塩化アンモニウム、臭化アンモニウム、沃化アンモニウム塩等のアンモニウム塩を使用することができる。
【０１５５】
上記再ハロゲン化剤の添加量は、５ｍｏｌ／ｌ以下が良い。好ましくは０．５〜３．０ｍｏｌ／ｌ、より好ましくは１．０〜２．０ｍｏｌ／ｌが良い。
【０１５６】
また、キレート剤を添加することもできる。例としては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及びホスホノカルボン酸等を使用することができる。具体的には、エチレンジアミン四酢酸、１，２−プロピレンジアミン四酢酸、ジエチレントリアミン五酢酸、１，２−シクロヘキサンジアミン四酢酸、イミノ二酢酸、メチルイミノ二酢酸、ニトリロ三酢酸、ヒドロキシメチルイミノ二酢酸、Ｎ−（２−カルボキシエチル）イミノ二酢酸、Ｎ−（２−カルボキシメチル）イミノ二酢酸、β−アラニン二酢酸、ヒドロキシエチルイミノ二酢酸、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、エチレンジアミンテトラメチレンホスホン酸、等をあげることができる。
【０１５７】
キレート剤の添加量は漂白主薬の２０ｍｏｌ％以下が良い。
【０１５８】
また、ｐＨ緩衝剤として、例えば酢酸、コハク酸、マロン酸、マレイン酸、グルタル酸、シュウ酸等の有機酸を使用することができる。添加量としては０〜５ｍｏｌ／ｌであり、好ましくは０．１〜２ｍｏｌ／ｌが良い。
【０１５９】
また、処理槽のステンレスの腐食を防止するために、腐食防止剤として硝酸アンモニウムや硝酸ナトリウム等の硝酸塩を使用する。硝酸化合物の濃度は、０．３〜４．０ｍｏｌ／ｌが好ましく、より好ましくは０．５〜３．５ｍｏｌ／ｌの範囲が良い。
【０１６０】
漂白工程に用いられる処理液（漂白液）のｐＨは２〜６の範囲が良く、好ましくは３〜５の範囲が良い。
【０１６１】
含浸処理の場合には、連続処理における漂白液の補充量は感光材料１ｍ^２あたり２５〜２００ｍｌが好ましい。
【０１６２】
処理温度は３０〜６０℃が良く、好ましくは３０〜５０℃、より好ましくは３５〜４５℃が良い。
【０１６３】
また、処理時間は、２０秒〜３分の範囲であり、好ましくは２０秒〜１分３０秒、より好ましくは２０秒〜１分の範囲が良い。
【０１６４】
塗布処理の場合には、塗布量は１〜３０００ｍｌ／ｍ^２の範囲であり、好ましくは５〜１０００ｍｌ／ｍ^２、より好ましくは１０〜５００ｍｌ／ｍ^２が良い。
【０１６５】
また、塗布処理の処理温度は２５〜７０℃であり、好ましくは３０〜６５℃、より好ましくは４０〜６０℃が良い。
【０１６６】
また、処理時間は含浸処理と同じとして良い。
【０１６７】
塗布処理の場合、複数塗布を行っても良く、塗布回数としては１〜２０回の範囲であれば良い。好ましくは１〜１２回が良く、より好ましくは１〜５回が良い。
【０１６８】
また、塗布処理の場合、非塗布時に塗布ノズル、塗布ヘッドにおいて塗布液の結晶化、乾固により、その後塗布再開時の塗布不良を防止するために、上記発色現像工程で用いた乾燥防止剤を用いることもできる。
【０１６９】
この場合添加量は１〜５０ｗ／ｖ％の範囲であり、好ましくは１〜４０ｗ／ｖ％、より好ましくは２〜３０ｗ／ｖ％が良い。
【０１７０】
また、感材上に均一に塗布するために、発色現像液に添加したものと同じ表面張力調整剤を添加することもできる。この場合、該調整剤添加後の処理液の表面張力は好ましくは２５〜７２ｍＮ／ｍ（測定温度２０〜５０℃）であり、より好ましくは２５〜５５ｍＮ／ｍ（測定温度２０〜５０℃）である。
【０１７１】
更に感材に塗布後処理液が流れ出さないように、発色現像液に添加したものと同じ粘度調整剤を添加することができる。この場合は、該調整剤添加後の処理液の粘度は１〜２０００ｍＰａ・ｓ（測定温度２０〜５０℃）が好ましく、１〜５００ｍＰａ・ｓ（測定温度２０〜５０℃）がより好ましい。
【０１７２】
＜定着工程＞
次に、本発明の定着工程に係る処理液について説明する。
【０１７３】
本発明に係る定着工程には以下に示す定着主薬や分解防止剤、キレート剤及びその他の添加剤を含む定着液を使用する。
【０１７４】
定着主薬にはチオ硫酸アンモニウムやチオ硫酸ナトリウム等のチオ硫酸塩が好ましく用いられる。また、その他公知の定着剤であるチオシアン酸ナトリウム、チオシアン酸カリウム、チオシアン酸アンモニウム等のチオシアン酸塩、エチレンビスチオグリコール等のチオエーテル化合物及びチオ尿素を２種以上併用しても良い。
【０１７５】
定着主薬の添加量は０．０１〜５．０ｍｏｌ／ｌであり、好ましくは０．１〜３．０ｍｏｌ／ｌ、より好ましくは０．５〜２．０ｍｏｌ／ｌが良い。
【０１７６】
分解防止剤としては、亜硫酸アンモニウム、亜硫酸カリウム及び亜硫酸ナトリウム等の亜硫酸塩、重亜硫酸アンモニウム、重亜硫酸カリウム及び重亜硫酸ナトリウム等の重亜硫酸塩、メタ重亜硫酸アンモニウム、メタ重亜硫酸カリウム、メタ重亜硫酸ナトリウム等のメタ重亜硫酸塩、ヒドロキシルアミン類、アスコルビン酸等のレダクトン類及びスルフィン酸等を必要に応じて使用することができる。
【０１７７】
これら分解防止剤は０．００１〜１．５ｍｏｌ／ｌの範囲で使用するが、好ましくは０．０〜０．５ｍｏｌ／ｌ、より好ましくは０．０〜０．２５ｍｏｌ／ｌが良い。
【０１７８】
キレート剤としては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及びホスホノカルボン酸等を使用することができる。
【０１７９】
具体的には、エチレンジアミン四酢酸、１，２−プロピレンジアミン四酢酸、ジエチレントリアミン五酢酸、１，２−シクロヘキサンジアミン四酢酸、イミノ二酢酸、メチルイミノ二酢酸、ニトリロ三酢酸、ヒドロキシメチルイミノ二酢酸、Ｎ−（２−カルボキシエチル）イミノ二酢酸、Ｎ−（２−カルボキシメチル）イミノ二酢酸、β−アラニン二酢酸、ヒドロキシエチルイミノ二酢酸、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、エチレンジアミンテトラメチレンホスホン酸等をあげることができる。
【０１８０】
また、キレート剤の使用量は０．１〜５ｇ／ｌが好ましい。
【０１８１】
また、ｐＫａが５〜９のｐＨ緩衝剤を添加することも好ましい。これにより定着主薬分解防止及び硫化防止が可能となる。
【０１８２】
このような化合物の例としては、以下の化合物があげられる。
エチレンジアミン（ｐＫａ７．４７）、Ｎ−メチルエチレンジアミン（ｐＫａ７．５６）、Ｎ−エチルエチレンジアミン（ｐＫａ７．６３）、Ｎ−ｎ−プロピルエチレンジアミン（ｐＫａ７．５４）、Ｎ−イソプロピルエチレンジアミン（ｐＫａ７．７０）、Ｎ−（２−ヒドロキシルエチル）エチレンジアミン（ｐＫａ７．２１）
Ｎ，Ｎ−ジメチルエチレンジアミン（ｐＫａ６．７９）、Ｎ，Ｎ−ジエチルエチレンジアミン（ｐＫａ７．０７）、Ｎ，Ｎ’−ジメチルエチレンジアミン（ｐＫａ７．４７）、Ｎ，Ｎ’−ジエチルエチレンジアミン（ｐＫａ７．７７）、Ｎ，Ｎ’−ジ−ｎ−プロピルエチレンジアミン（ｐＫａ７．５３）、Ｎ，Ｎ’−ジ（２−ヒドロキシルエチル）エチレンジアミン（ｐＫａ７．１８）、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン（ｐＫａ６．５６）、１，２−ジアミノプロパン（ｐＫａ７．１３）、ｍｅｓｏ−２，３−ジアミノプロパン（ｐＫａ６．９２）トリエチレンテトラミン（ｐＫａ６．６７）、１，２，３−トリアミノプロパン（ｐＫａ７．９５）、１，３−ジアミノ−２−アミノメチルプロパン（ｐＫａ６．４４）等。
【０１８３】
また、酸解離定数（ｐＫａ）が５．５〜８．５の範囲にあるアミノピリジン系化合物を用いても良い。好ましくはｐＫａが６．３〜７．８の範囲のものが良い。ｐＫａが５．５以下であると処理液のｐＨを低下させて、チオ硫酸塩の分解を促進してしまい、また、８．５以上となると、漂白能力が低下してしまうからである。具体的には、２−アミノピリジン（ｐＫａ６．７８）、３−アミノピリジン（ｐＫａ６．０６）等の化合物があげられる。
【０１８４】
また、下記一般式［ＩＩ］［ＩＩＩ］［ＩＶ］の構造を有する化合物を用いることも好ましい。
【０１８５】
【化２】

【０１８６】
式［ＩＩ］中、Ｒ１、Ｒ２はそれぞれ直鎖又は分岐アルキレン基を示し、アミノ基、アルキルアミノ基、スルホ基、又はヒドロキシル基に置換されても良い。ｎは０〜８である。Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４及びＲ１５は各々水素原子若しくは炭素数１〜４の直鎖もしくは分岐アルキル基（ただしアミノ基、アルキルアミノ基、スルホ基又はヒドロキシル基に置換されても良い）、アシル基、アリール基またはヒドロキシル基からなる。また、Ｒ１１とＲ１２、Ｒ１２とＲ１５、Ｒ１５とＲ１４、Ｒ１４とＲ１３、Ｒ１１とＲ１３及びＲ１２とＲ１４はそれぞれ共同してヘテロ環を形成しても良いし、連結されたビス体を形成しても良い。また、式［ＩＩ］に含まれるアミノ基は全てが３級アミンであることはない。
【０１８７】
式［ＩＶ］中、Ａは水素原子、アルキル基若しくはヒドロキシル基のいずれかを示し、アルキル基はヒドロキシル基若しくはアミノ基のいずれか又は両方で置換されたアルキル基であっても良い。また、一分子中のＡは全て同一でも、これら置換基の組み合わせであっても良い。また、ｍは１１〜１７００である。
【０１８８】
上記化合物以外にもイミダゾ−ル及びイミダゾ−ル誘導体を添加しても良い。
【０１８９】
これらｐＨ緩衝剤の添加量は、０．０００１〜５ｍｏｌ／ｌが好ましい。
【０１９０】
こうしてｐＨ調整を行うことにより、定着処理液のｐＨは５〜１０の範囲が好ましく、より好ましくはｐＨ６〜９が良い。
【０１９１】
また、現像停止剤を添加することもできる。こうすることにより、発色現像工程後速やかに現像処理を停止できるため、処理の迅速化が可能となる。
【０１９２】
添加する化合物としては、ベンゾトリアゾール、６−ニトロベンズイミダゾール、５−ニトロイソインダゾール、５−メチルベンゾトリアゾール、５−ニトロベンゾトリアゾール、５−クロロ−ベンゾトリアゾール、２−チアゾリル−ベンズイミダゾール、２−チアゾリルメチル−ベンズイミダゾール、インダゾール、ヒドロキシアザインドリジン、アデニン等の含窒素ヘテロ環化合物、１−フェニル−５−メルカプトテトラゾール、また、アルカリ金属の塩化物塩，臭化物塩、ヨウ化物塩及び塩化アンモニウム、臭化アンモニウム、ヨウ化アンモニウム塩等のアンモニウム塩を使用することが出来るが、好ましくはアルカリ金属の臭化物塩、ヨウ化物塩及び臭化アンモニウム、ヨウ化アンモニウム塩等のアンモニウム塩、１−フェニル−５−メルカプトテトラゾール等が良い。
【０１９３】
添加量としては０．００１〜１ｍｏｌ／ｌであり、好ましくは０．００５〜０．５ｍｏｌ／ｌが良い。
【０１９４】
含浸処理の場合の補充量は、２５０〜１４００ｍｌ／ｍ^２で行い、処理温度は３０〜６０℃であり、好ましくは３０から５０℃、より好ましくは３５〜５０℃が良い。
【０１９５】
処理時間は５秒〜５分の範囲であればよく、好ましくは１０秒〜２分３０秒、より好ましくは１０秒〜２分が良い。
【０１９６】
塗布処理の場合、塗布量はとして１〜３０００ｍｌ／ｍ^２がよく、好ましくは５〜１０００ｍｌ／ｍ^２、より好ましくは１０〜５００ｍｌ／ｍ^２が良い。
【０１９７】
また、処理温度は２５〜７０℃の範囲であり、３０〜６５℃が好ましい。また、４０〜６０℃がより好ましい。
【０１９８】
塗布回数は複数行っても良く、好ましくは１〜１２回、より好ましくは１〜
５回が良い。
【０１９９】
また、塗布処理の場合には、処理停止中に塗布ノズルやヘッドでの塗布液の結晶化，乾固による塗布不良を防止するため、乾燥防止剤として発色現像工程で用いた乾燥防止剤を添加しても良い。この場合２種類以上添加しても良い。これにより塗布再開時の塗布ムラを防止することができる。
【０２００】
添加量としては１〜５０ｗ／ｖ％であればよく、１〜４０ｗ／ｖ％が好ましく、２〜３０ｗ／ｖ％がより好ましい。
【０２０１】
更に感材表面に塗布した処理液の均一性を向上するため界面活性剤を添加して、表面張力の調整を行っても良い。用いる粘度調整剤は発色現像工程で用いたものと同じであり、添加後の処理液の粘度は１〜２０００ｍＰａ・ｓが好ましく、１〜５００ｍＰａ・ｓがより好ましい。
【０２０２】
＜漂白定着工程＞
漂白定着工程は、上述した漂白工程と定着工程とを１つの処理で行うものである。
【０２０３】
漂白定着処理液中、漂白主薬には、アミノポリカルボン酸鉄（ＩＩＩ）塩や過硫酸などを使用することができる。漂白液には、第二鉄錯塩として予め錯形成された鉄錯塩を使用しても良く、また、硫酸第二鉄塩、硝酸鉄（ＩＩＩ）、塩化第二鉄等と錯形成化合物を漂白液に共存させて溶液内で錯形成させても良い。
【０２０４】
アミノポリカルボン酸の具体例としては、エチレンジアミン四酢酸、１，３−プロパンジアミン四酢酸、ジエチレントリアミン五酢酸、１，２−シクロヘキサンジアミン四酢酸、イミノ二酢酸、メチルイミノ二酢酸、ニトリロ三酢酸、ヒドロキシメチルイミノ二酢酸、Ｎ−（２−カルボキシエチル）イミノ二酢酸、Ｎ−（２−カルボキシメチル）イミノ二酢酸、β−アラニン二酢酸、エチレンジアミン−Ｎ，Ｎ’−ジコハク酸、１，３−プロパンジアミン−Ｎ，Ｎ’−ジコハク酸、エチレンジアミン−Ｎ，Ｎ’−ジマロン酸、１，３−プロパンジアミン−Ｎ，Ｎ’−ジマロン酸等が挙げられる。
【０２０５】
次に、漂白定着処理液中の定着主薬としてはチオ硫酸アンモニウム、チオ硫酸ナトリウム等のチオ硫酸塩が好ましく用いられる。また、その他公知の定着剤であるチオシアン酸ナトリウム、チオシアン酸カリウム、チオシアン酸アンモニウム等のチオシアン酸塩、エチレンビスチオグリコール酸等のチオエーテル化合物及びチオ尿素を２種類以上併用しても良い。
【０２０６】
添加量としては０．１〜５ｍｏｌ／ｌの範囲が良く、０．１〜３ｍｏｌ／ｌが好ましい。また、０．５〜２ｍｏｌ／ｌがより好ましい。
【０２０７】
漂白定着液に使用される漂白定着促進剤には、例えば、メルカプト化合物や、その他ジスルフィド化合物及びチオール化合物などが挙げられる。
【０２０８】
具体的には３−メルカプト−１，２，４−トリアゾール、ジエチルアミノエタンチオール等をあげることができる。
【０２０９】
また、分解防止剤としては、亜硫酸アンモニウム、亜硫酸ナトリウム等の亜硫酸塩、重亜硫酸アンモニウム、重亜硫酸カリウム等の重亜硫酸塩、メタ重亜硫酸アンモニウム、メタ重亜硫酸カリウム等のメタ重亜硫酸塩、ヒドロキシルアミン類、アスコルビン酸等のレダクトン類及びスルフィン酸等を必要に応じて使用することができる。
【０２１０】
分解防止剤の使用量は、０．００５〜３．０ｍｏｌ／ｌの範囲で使用できるが、好ましくは０．００５〜２．０ｍｏｌ／ｌ、より好ましくは０．００５〜１．０ｍｏｌ／ｌの範囲が良い。
【０２１１】
キレート剤としては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及びホスホノカルボン酸等を使用することができる。
【０２１２】
具体的には、エチレンジアミン四酢酸、１，２−プロピレンジアミン四酢酸、ジエチレントリアミン五酢酸、１，２−シクロヘキサンジアミン四酢酸、イミノ二酢酸、メチルイミノ二酢酸、ニトリロ三酢酸、ヒドロキシメチルイミノ二酢酸、Ｎ−（２−カルボキシエチル）イミノ二酢酸、Ｎ−（２−カルボキシメチル）イミノ二酢酸、β−アラニン二酢酸、ヒドロキシエチルイミノ二酢酸、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、エチレンジアミンテトラメチレンホスホン酸等を挙げることができる。
【０２１３】
キレート剤の添加量としては０．０００１〜５ｍｏｌ／ｌが良い。
【０２１４】
また、定着主薬の分解防止及び硫化防止のためにｐＨ緩衝剤を添加しても良い。
【０２１５】
このような化合物の例としては、以下の化合物があげられる。
エチレンジアミン（ｐＫａ７．４７）、Ｎ−メチルエチレンジアミン（ｐＫａ７．５６）、Ｎ−エチルエチレンジアミン（ｐＫａ７．６３）、Ｎ−ｎ−プロピルエチレンジアミン（ｐＫａ７．５４）、Ｎ−イソプロピルエチレンジアミン（ｐＫａ７．７０）、Ｎ−（２−ヒドロキシルエチル）エチレンジアミン（ｐＫａ７．２１）
Ｎ，Ｎ−ジメチルエチレンジアミン（ｐＫａ６．７９）、Ｎ，Ｎ−ジエチルエチレンジアミン（ｐＫａ７．０７）、Ｎ，Ｎ’−ジメチルエチレンジアミン（ｐＫａ７．４７）、Ｎ，Ｎ’−ジエチルエチレンジアミン（ｐＫａ７．７７）、Ｎ，Ｎ’−ジ−ｎ−プロピルエチレンジアミン（ｐＫａ７．５３）、Ｎ，Ｎ’−ジ（２−ヒドロキシルエチル）エチレンジアミン（ｐＫａ７．１８）、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン（ｐＫａ６．５６）、１，２−ジアミノプロパン（ｐＫａ７．１３）、ｍｅｓｏ−２，３−ジアミノプロパン（ｐＫａ６．９２）、トリエチレンテトラミン（ｐＫａ６．６７）、１，２，３−トリアミノプロパン（ｐＫａ７．９５）、１，３−ジアミノ−２−アミノメチルプロパン（ｐＫａ６．４４）等。
【０２１６】
また、酸解離定数（ｐＫａ）が５．５〜８．５の範囲にあるアミノピリジン系化合物を用いることができる。好ましくはｐＫａが６．３〜７．８の範囲のものが良い。ｐＫａが５．５以下であると処理液のｐＨを低下させて、チオ硫酸塩の分解を促進してしまい、また、８．５以上となると、漂白能力が低下してしまうからである。具体的には、２−アミノピリジン（ｐＫａ６．７８）、３−アミノピリジン（ｐＫａ６．０６）等の化合物があげられる。
【０２１７】
また、定着工程に記載されている一般式［ＩＩ］［ＩＩＩ］［ＩＶ］の構造を有する化合物を用いても良い。
【０２１８】
また、イミダゾ−ル、イミダゾ−ル誘導体、あるいは酢酸、コハク酸、マロン酸、マレイン酸、グルタル酸及びシュウ酸等の有機酸を使用することもできる。
【０２１９】
これらｐＨ緩衝剤の添加量は０．０００１〜５ｍｏｌ／ｌが好ましい。
【０２２０】
また、このようにして得られた漂白定着処理液のｐＨは４〜９が好ましい。
【０２２１】
本発明の漂白定着処理も含浸処理若しくは塗布処理どちらの方法をとっても良い。
【０２２２】
含浸処理の場合、漂白定着液の補充量は５〜２１６ｍｌ／ｍ^２であれば良く、好ましくは５〜７０ｍｌ／ｍ^２、より好ましくは５〜３５ｍｌ／ｍ^２が良い。
【０２２３】
処理温度は３０〜６０℃の範囲であり、好ましくは３０〜５０℃、より好ましくは３５〜４５℃が良い。
【０２２４】
処理時間は２０秒〜３分の範囲であればよく、２０秒〜２分３０秒が好ましく、２０秒〜２分がより好ましい。
【０２２５】
塗布処理の場合は、漂白定着液の塗布量は１〜３０００ｍｌ／ｍ^２であり、５〜１０００ｍｌ／ｍ^２が好ましく、１０〜５００ｍｌ／ｍ^２がより好ましい。
【０２２６】
また、処理温度は２５〜７０℃であり、好ましくは３０〜６５℃、より好ましくは４０〜６０℃が良い。
【０２２７】
処理時間は３秒〜５分の間で任意に行えるが、好ましくは５秒〜２分、より好ましくは５秒〜１分２０秒間処理するのが良い。
【０２２８】
また塗布回数は複数回行っても良く、好ましくは１〜１２回、より好ましくは１〜５回が良い。
【０２２９】
更に、発色現像工程等と同様に、塗布処理の場合は乾燥防止剤、表面張力調整剤及び粘度調整剤を添加することができる。これらの添加量も発色現像工程と同様にして良い。
【０２３０】
＜水洗及び／又は安定化工程＞
本発明の水洗及び／又は安定化工程は大量の水洗水に代わってケミカルリンス剤、水滴防止剤、防菌防黴剤、キレート剤、色素安定化剤等を含む水洗代替目的でのリンス液を使用することができる。水洗水とリンス液とを併用しても良いし、リンス液のみで処理を行っても良い。
【０２３１】
水滴防止剤としては界面活性剤を使用することができる。特にノニオン系界面活性剤が好ましい。
【０２３２】
また、本発明の処理方法では、処理槽中でのバイオスライムの発生防止及び処理後の感光材料に発生する黴の防止のため、防菌防黴剤を含有することができる。通常、防菌防黴剤の添加量は、０．０１〜０．１ｇ／ｌの範囲であるが、本発明の処理剤を水洗及び／又は安定化工程の処理液に添加することにより、各防菌防黴剤の通常使用量の１０倍量まで防菌防黴剤の添加量を増量することが可能となる。
【０２３３】
具体的な防菌防黴剤としては、以下のようなものが挙げられる。
【０２３４】
エタノール、プロパノール、イソプロピルアルコール、２‐ブロモ−２‐ニトロ−プロパノール、Ｎ−（２−ヒドロキシプロピル）−アミノエタノール等のアルコール系防黴剤。ピオゾール、チモール、о−フェニルフェノール、メチルフェノール、パラクロルフェノール、クロロフェン、２，４，６−トリブロモフェノール等のフェノール系防黴剤。ホルムアルデヒド、グルタールアルデヒド、ベンズアルデヒド、αブロムシンナムアルデヒド等のアルデヒド系防黴剤。安息香酸及びその誘導体、ウンデシレン酸金属錯体、ウンデシレン酸エタノールアミド、プロピオン酸、カプリル酸、ソルビン酸等のカルボン酸系防黴剤。ｐ−ヒドロキシ安息香酸エステル類（パラベン）、脂肪酸モノグリセライド類等のエステル系防黴剤。２，４，４’−トリクロロ−２’−ヒドロキシジフェニルエステル等のエーテル系防黴剤。テトラクロロイソフタロニトリル等のニトリル系防黴剤。過酸化水素、過酢酸、エチレンオキサイド、プロピレンオキサイド等の過酸化物系防黴剤。パラクロロフェニル−３−ヨードプロパギルフォルマールジクロフルアミド、塩素化イソシアヌル酸、２−ブロモ−２−ニトロ−１，３−プロパンジオール等のハロゲン系防黴剤。８−オキシキノリン、２，３，５，６−テトラクロロピリジン誘導体等のピリジン及びキノリン系防黴剤。Ｎ，Ｎ’，Ｎ’’−トリスヒドロキシメチルヘキサヒドロ−Ｓ−トリアジン等のトリアジン系防黴剤。５‐クロロ−２−メチル−４−イソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３‐オン、ベンゾイソチアゾリン誘導体等のイソチアゾリン系防黴剤。チオベンダゾール誘導体、ベンゾチアゾール誘導体等のイミダゾール／チアゾール系防黴剤。クロロカルバニリド誘導体等のアニリド系防黴剤。グルコン酸シクロヘキシジン、塩酸クロルヘキシジン、塩酸ポリヘキサメチレンビグアニジン等のビグアナイド系防黴剤。アルキルジチオカーバメイト誘導体等のジチオカーバメイト系防黴剤。ジチオ−２−２’−ビスベンズアミド等のジスルフィド系防黴剤。キトサン、ポリグルコサミン、アミノグリコシド等の糖質系防黴剤。天然のヒノキチオール等のトロポロン系防黴剤。オクタデシルアミン酢酸塩、アルキルジアミノエチルグリシン、ポリオキシアルキレンアンモニウム、塩化ベンザルコニウム等の界面活性剤系防黴剤。８−オキシキノリン金属錯体、グルタミン酸誘導体の金属錯体、ナフテン酸金属錯体等の有機金属系防黴剤。
【０２３５】
上記化合物の中でも、アルコール系防黴剤、カルボン酸系防黴剤、エステル系防黴剤、ハロゲン系防黴剤、イソチアゾリン系防黴剤、ジスルフィド防黴剤、界面活性剤系防黴剤、パラクロロフェニル−３−ヨードプロパギルフォルマールジクロフルアミド及び２‐ブロモ−２‐ニトロ−１，３−プロパンジオール等の防菌防黴剤等が、バイオスライム抑制、イエローステイン（Ｓｔａｉｎ）上昇抑制及び画像保存性への影響等の点から好ましい。さらに好ましくはホルムアルデヒド、エステル系防黴剤、パラクロロフェニル−３−ヨードプロパギルフォルマールジクロフルアミド、２‐ブロモ−２‐ニトロ−１，３−プロパンジオール、ジスルフィド系防黴剤等の防菌防黴剤が良い。
【０２３６】
上記防菌防黴剤は、安定化処理工程において２種類以上を併用しても良い。
【０２３７】
また、上記防黴剤と共に以下に示す抗菌、除菌方法を併用しても良い。
【０２３８】
不溶性のリン酸ジルコニウム系化合物や銀を無機化合物に担持した銀系化合物、銅、亜鉛、銀等の金属イオンをゼオライトに担持した抗菌性ゼオライト、抗菌セラミックス等を使用した処理槽、ローラー又はフィルター等を併用しても良い。
【０２３９】
また、紫外線ランプ、超音波振動、通電処理などの一般的な抗菌方法を併用しても良い。また、抗菌フィルターなどを使用した除菌方法を併用しても良い。
【０２４０】
画像安定化剤としてはホルマリン、アルデヒド類あるいはメチロール尿素、又はヘキサメチレンテトラミンなどのホルマリン放出化合物を使用することができる。
【０２４１】
画像安定化剤の添加量は０．０００１〜０．０１ｍｏｌ／ｌが好ましい。
【０２４２】
また、乾燥後の感光材料への静電気によるゴミの付着防止のために、スルホコハク酸ジオクチルエーテル、ラウロイルサルコシンナトリウム、塩化ジステアリルジメチルアンモニウム等の帯電防止剤や、トリアジニルスチルベン系の蛍光増白剤等を含有することもできる。
【０２４３】
また、ジエチレングリコール、エタノール、エチレングリコール、Ｎ−メチル−２−ピロリドン、ブチルセルソルブ、γ−ブチロラクトン、トリエタノールアミン等の有機溶剤を使用できる。
【０２４４】
また、キレート剤として、アミノポリカルボン酸、アルキルホスホン酸、アルキルスルホン酸及びホスホノカルボン酸等を添加することもできる。
【０２４５】
キレート剤の添加量は０．００００１〜０．２ｍｏｌ／ｌ、好ましくは０．００００１〜０．０２ｍｏｌ／ｌが良い。
【０２４６】
更に、上述した工程において用いられた定着主薬の分解を防止するために、定着工程に記載されている一般式［ＩＩ］［ＩＩＩ］［ＩＶ］で表される化合物（ａ）（ｂ）（ｃ）のうち少なくとも一種類以上、または亜硫酸塩や重亜硫酸塩を分解防止剤として含むことが好ましい。
（ａ）下記一般式で表される化合物 ［ＩＩ］
（ｂ）下記一般式で表されるアミノピリジン系化合物 ［ＩＩＩ］
（ｃ）下記一般式で表されるポリエチレンイミン ［ＩＶ］。
【０２４７】
ここで、化合物（ａ）又は（ｂ）を用いる時は、水洗及び／又は安定化工程の処理液中各々０．０００１〜１ｍｏｌ／ｌの範囲で用いられることが好ましく、より好ましくは０．０００２〜０．１ｍｏｌ／ｌの範囲が良い。
【０２４８】
また、化合物（ｃ）を用いる時は水洗及び／又は安定化工程の処理液中０．００００１〜０．３ｍｏｌ／ｌの範囲で用いられることが好ましく、より好ましくは０．００００５〜０．１ｍｏｌ／ｌの範囲が良い。
【０２４９】
また亜硫酸塩若しくは重亜硫酸塩を添加する場合の添加量は０．０００４〜２ｍｏｌ／ｌの範囲で用いられることが好ましく、より好ましくは０．０００８〜０．１６ｍｏｌ／ｌの範囲が良い。
【０２５０】
また、ｐＨを調整するためのｐＨ緩衝剤を添加しても良い。
【０２５１】
安定化処理液のｐＨを一定の範囲内に保つために、酢酸、プロピオン酸、コハク酸、マレイン酸、グリシン、タウリン、グリコール酸等の有機酸をｐＨ緩衝剤として使用しても良い。特に、ｐＨ４〜８の範囲に緩衝能を有する緩衝剤（ｐＫａ＝４〜８の化合物）が好ましい。
【０２５２】
また、リンス液のｐＨは３〜９が好ましく、より好ましくは４〜８が良い。
【０２５３】
処理方法としては、上述した処理工程同様、含浸処理でも塗布処理であっても良い。
【０２５４】
含浸処理の場合、連続処理における安定化処理液槽の補充量は感光材料１ｍ^２当り２５〜２５００ｍｌが好ましく、１５０〜１８００ｍｌがより好ましい。
【０２５５】
処理温度としては３０〜４５℃が好ましい。また、処理時間は１５秒〜１０分が好ましく、特に３０秒〜５分が好ましい。
【０２５６】
本発明に係る安定化処理液槽については、単槽、多段向流カスケード方式、多段並流方式など任意の方式を採用することができるが、多段向流カスケード方式が好ましい。
【０２５７】
多段向流カスケード方式では、安定化処理液槽が通常２槽以上あり、この最終槽に補充された液がオーバーフローすることにより順次前槽に流れ込む構造になっており、最前の槽から廃液を排出する構成となっている。この場合、感光材料の処理方向と逆の方向から処理液を流すことになるので最終槽の塩類濃度が最も低い構造となり、感光材料の塩類を段々と清浄な処理液で水洗することができる。このため、少量の処理液で流水水洗同様に感光材料の塩類を除去することができる。また、処理槽の数は３〜８が好ましい。
【０２５８】
次に塗布処理の場合、塗布量は１〜３０００ｍｌ／ｍ^２であれば良く、好ましくは５〜５００ｍｌ／ｍ^２、より好ましくは１０〜３００ｍｌ／ｍ^２が良い。
【０２５９】
処理温度は１０〜７０℃であれば良いが、３０〜６５℃が好ましく、４０〜６０℃がより好ましい。
【０２６０】
また、処理時間は１０秒〜５分、好ましくは１０秒〜２分、より好ましくは１０秒〜１分２０秒が良い。
【０２６１】
塗布回数は１〜２０回行うことができ、好ましくは１〜１２回、より好ましくは１〜５回行うことが望ましい。
【０２６２】
また、塗布処理の場合には、塗布ノズルやヘッドでの処理液の乾固、結晶化を防ぎ、感材上へ均一に塗布するため、上述した処理工程同様に、乾燥防止剤、表面張力調整剤及び粘度調整剤を添加することが好ましい。
【０２６３】
この場合、それぞれの添加量は上記各処理工程と同じである。
【０２６４】
＜スクイーズ工程＞
上述した各工程の間には、感材上の余分な処理液を掻き取るためのスクイーズ工程を設けても良い。そうすることにより最後に洗浄するときに洗浄効率が向上する。また、本発明の処理方法では、感材上に処理液を塗布しても反応による結晶化はおこらないため、スクイーズ工程を取り入れても感材を傷つける恐れはない。
【０２６５】
スクイーズ方法としては、ローラー、スポンジ、スクイーズブレード等で感材表面に付着した塗布液を除去すれば良い。
【０２６６】
スクイーズ材としては、ウレタンなどを用いることができる。
【０２６７】
＜画像処理工程＞
本発明の処理方法では、このようにして現像した感材を用いて、画像をデジタル化することができる。
【０２６８】
例えば発色現像後感材が湿った状態でスキャンして画像をデジタル処理することも可能であり、また、感材を一旦乾燥させてからスキャンしても良い。
【０２６９】
また、目的又は用いる感材により適宜後処理工程を選択して行うこともできる。
【０２７０】
この場合、水洗処理を終えて感材が濡れた状態で処理することも可能であり、水洗処理後に乾燥処理を行ってから処理することもできる。
【０２７１】
本発明に用いる画像処理装置は従来公知のスキャナ等を用いることができる。
【０２７２】
また、画像処理のアプリケーションも従来公知の画像処理ソフトを用いることができる。
【０２７３】
＜処理装置＞
次に、本発明の処理方法を行うための処理装置について図面を用いて説明する。本発明の処理方法においては、発色現像工程以外の工程は塗布方法若しくは従来通りの含浸方法どちらの方法を用いることができるが、ドライ処理とするためには、全てを塗布方法にて行うことが好ましい。塗布方法によるドライ処理では、処理液を直接感材表面に塗布することにより現像処理を行うので、少量かつ高濃度の処理液を直接感材に塗布することができ、処理効率も上がり、廃液もほとんど出ないという効果がある。
【０２７４】
まず、このドライ処理による本発明の処理方法を説明していく。
【０２７５】
図３はドライ処理全体の処理工程を説明する工程図である。
【０２７６】
前処理としてプレソーキング液を感材に塗布する（ステップ１）。本発明の前処理液（プレソーキング液）を塗布することで、後述する処理液の感材への浸透性を高めることができるので、従来と比較して高濃度の処理液を塗布することが可能となり、処理効率を向上させることができる。次いで、発色現像液を塗布するが、本発明に係る発色現像液では主薬パート処理液（主薬液）とアルカリパート処理液（アルカリ液）とを２部構成として塗布している（ステップ２及び３）。
【０２７７】
このように発色現像工程に係る一連の処理が終わると、次に脱銀工程として、漂白液を塗布し（ステップ４）、次いで定着液を塗布する（ステップ５）。もしくは漂白液や定着液の代わりに漂白定着液を塗布しても良い（ステップ６）。これにより感材上に析出した銀を溶解除去する。その後、水洗／安定化処理液を塗布することにより感材上に残留した処理液を洗浄除去する（ステップ７）。このようにして処理を終えた感材は、乾燥処理を行う（ステップ８）か、あるいは乾燥処理を行わずにスキャナでスキャンして画像処理を行い画像のデジタルデータ化を行う（ステップ９）。
【０２７８】
このようにして、本発明の処理方法では、高濃度の処理液を少量塗布することにより、画像の質を向上しつつ処理時間を短縮することが可能となる。
【０２７９】
なお、上記例では、全ての処理を行うようになっているが、これに限定されるものではなく、使用する感材や目的に応じて随時必要な処理のみを行うことも可能である。
【０２８０】
次に、上記ドライ処理に用いられる処理装置について説明する。
【０２８１】
図４は、本発明に係るドライフィルムプロセス（Ｄｒｙ Ｆｉｌｍ Ｐｒｏｃｅｓｓ：以下ＤＦＰともいう）装置１００（以下、本発明の装置ともいう）の概略模式図である。
【０２８２】
装置１００では、ＤＦＰ処理に係る処理全てを連続して行う構成となっている。以下、装置構成概要を説明する。
【０２８３】
まず、本発明に係るＤＦＰ装置１００には、感光材料（感材）１０５を載置して各処理部へ搬送するためのコンベアベルト１０１、コンベアベルト１０１を回転させるためのローラー１０２、ローラー１０２を駆動するための駆動部（図示せず）が設けられている。
【０２８４】
また、装置１００には、発色現像液塗布前の処理を行うプレソーキング部１１０、発色現像液を塗布する発色現像液塗布部１２０、発色現像液を感材内の色素層に均等に拡散するための拡散処理を行う拡散部１３０、発色現像液中の銀を漂白液により酸化させて析出させる漂白部１４０、析出した銀を溶解除去する定着液を塗布する定着部１５０、漂白及び定着処理を一つの処理液で行う漂白定着部１６０、これら各処理液を感材表面から洗い流すための水洗／安定化部１７０、感材を劣化させずに保存するための処理をするオーバーコート部１８０、乾燥部（図示せず）及び処理を終えた感材から画像をスキャンするスキャン部１０７の各処理部及び処理済感材を回収する感材回収部１０３が設けられている。
【０２８５】
このように、本実施形態の構成によれば、感材１０５は上述したコンベアベルト１０１により順次各処理部まで自動に搬送され、各処理部でそれぞれの処理液を塗布されることにより一連の現像処理が自動に行えるようになっている。
【０２８６】
図５に示すようにこれら各処理部には、各処理液を感材１０５上に塗布するための塗布ノズル２１０、補充処理液を充填しておく補充処理液槽２０１、該補充処理液を塗布ノズル２１０に供給するため、補充処理液槽２０１から塗布ノズル２１０へ処理液を供給する配管２０３とからなる塗布ユニット２００が設けられている。
【０２８７】
また、該塗布ノズル２１０先端にはカーテンコーターのヘッド２１１が設けられており、このヘッドを通じて処理液を塗布するようになっている。
【０２８８】
また、この塗布ユニット２００には、更に処理液を温調するための温調機構（図示せず）を設けているので、適切な処理温度として処理液を塗布することが可能とである。
【０２８９】
本発明の実施形態においては、感材１０５はベルトコンベア上に載置された後、発色現像部１２０、漂白部１４０、定着部１５０、漂白定着部１６０、水洗／安定化部１７０まで搬送されながら各処理液を塗布された後、水洗／安定化部１７０に設けられ、吸水性材料からなる吸水ローラー１８１で感材表面を吸水後ウェットな状態でスキャン部１０７へ搬送され、画像処理されるようになっている。そして、処理を終えた感材は感材回収部１０３で巻き取られて回収されるようになっている。あるいは、例えばスキャナが装置内に設置されておらず、別置きのスキャナを用いる場合には、乾燥部にて感材を乾燥させた後、スキャンすることにより画像処理が行われるようになっている。
【０２９０】
ここで、発色現像部１２０では、発色現像主薬液パート部１２１とアルカリ液パート部１２２とがそれぞれ独立した塗布ユニット２００を有し、個別に処理液を塗布するようになっている。感材１０５が該処理部に搬送されると、まず主薬液が塗布されてから３０秒程度浸透させた後、アルカリ剤を塗布して５秒〜２分程度浸透させて発色現像反応を起こさせる。このような構成とすることにより、感材全体に発色現像主薬を浸透させて発色ムラを防止できるので、現像画像の画質を向上させることが可能になる。
【０２９１】
また、浸透させる時間の変更については、処理剤の吐出位置の変更や、感光材料の搬送速度を変更することによって可変することができる。フィルム処理の場合は、多種多様な感材を混処理することが一般的であるため、自動現像機に感材を挿入の際、感材のパトローネのバーコードから感度等の情報を読み込んで、自動的に感材処理時間の変更を行うこともできる。
【０２９２】
また、本発明の発色現像液は、主薬液のｐＨが７を超えているので、アルカリ液を重ねて塗布した場合に過剰な反応を起こすこともなくなり、それにより生じる現像ムラもなくすこともできる。さらに、それにより処理効率も向上することができ、処理時間も従来と比較して大幅に短縮することができる。
【０２９３】
更に、本発明に係る装置１００では、主薬液パート部１２１で主薬液を塗布後、スクイーズローラー１２３により感材１０５表面をならして、塗布した主薬液を均一な状態とするようになっている。
【０２９４】
ここでは、このスクイーズローラー１２３は非吸水性材テフロン（登録商標）からなり、発色現像液を塗布後、感材表面を一定方向にならすようになっている。ローラー１２３は非吸水性材を用いているので、ローラー表面に薬液が付着せず、ゴミの付着もないので、連続して感材を処理しても、後続の感材に前の感材のゴミや液が付着することもなく、常に一定の厚さに塗布液を調整することが可能となる。
【０２９５】
ここで、従来の塗布処理においては、最初の処理液を塗布した時に塗布ムラが生じると、その後の処理液塗布においてもそのムラを解消できずに悪化させる一方なので、その結果画像ムラとなってしまい画質が悪化してしまうという問題があった。しかしながら本発明に係る塗布処理装置１００ではこのようにローラー１２３を用いて感材表面を均一にならすので、主薬液は感材上に均一に塗布されることになり、その後の処理においても各処理液を均一に塗布することが可能となり、画像ムラを防止して画質を向上させることができる。
【０２９６】
また、他の処理部においても、塗布処理では直接感材表面に処理液を必要量のみ塗布することが可能となるので、使用量を低減することができる。また、廃液もほとんど生じることがないので、環境面からも好ましい。
【０２９７】
塗布処理は、含浸処理と異なり、高濃度の処理液を使用した場合に、感材によって前槽から次槽への処理液の持ち込みがないため、処理量が多くなっても、新液と同じ状態で処理が可能となり、感材での反応速度も上がるため、処理時間も短縮して処理効率も向上できる。
【０２９８】
以上の構成により、本発明に係るＤＦＰ装置１００では様々な処理を感材に対して行うことが可能であり、感材に応じて不要な処理は行わずにその処理部を通過することもできる。これにより様々な感材に柔軟に対応して幅広い処理を行うことができる。
【０２９９】
次にＤＦＰ装置１００の塗布ノズル２１０に用いられる塗布ヘッド２１１について詳細に説明する。図６塗布ノズル２１０及び塗布ヘッド２１１の外観模式図であり、図７は塗布ヘッド内部を示す縦断面図である。
【０３００】
本実施形態に用いられる塗布ノズル２１０のヘッド２１１は、一般的にはスリットオリフィスコーターと言われるものであり、その材質としては、ステンレス、アルミ、チタンが用いられ、好ましくはチタンが良い。このような材質を用いることにより耐酸性、耐アルカリ性が向上して様々なｐＨ範囲を有する各処理液に対応することができる。
【０３０１】
図６に示すように、テーパー状に隆起したヘッド２１１の底面中央部には各処理液を吐出するためのスリット２１２が設けられている。このスリット２１２は、幅がおよそ０．０５〜０．３ｍｍであり、０．０５〜０．２ｍｍが好ましい。また塗布幅（ノズル幅）はおよそ１５〜８０ｍｍであり、１５〜６０ｍｍが好ましい。このようなスリットであれば、濃縮された発色現像主薬パート液もアルカリパート液も効率良く均一に塗布することが可能となる。
【０３０２】
スリット２１２を中心として、隆起したヘッド底部には、ステンレス、アルミ、チタンからなり堰となって処理液の流れを調整する整流板２１３が等間隔に複数設けられている。本発明に係る塗布処理では、濃縮した高濃度の処理液を用いるため、スリット２１２から吐出しても一定方向で所定の範囲に塗布することが困難であるが、この整流板を設けることにより処理液の逆流や偏りを防止して感材の塗布範囲全てに適切に塗布することができる。
【０３０３】
また、図７に示すように、本実施形態に係る塗布ヘッド２１１の内部は処理液をまっすぐにカーテン状にして感材１０５に均一に塗布できるように、櫛歯状の塗布ガイド２１４を設けている。該ガイド２１４は中央が一番長く、左右両端が一番短くなるように長さが調節されている。これにより、従来の処理液よりも濃度の高い処理液を塗布しても、処理液が感材１０５の中央に集中することなく、シート幅全体に均一に処理液を塗布することが可能となる。
【０３０４】
このように、本発明の処理方法は上述した本発明に係る装置１００を用いることにより、従来の含浸処理と比べて使用する処理液の量も少なく、処理時間も大幅に短縮できるものである。具体的には、従来の含浸処理では感材（３５ｍｍフィルム）１ｍ当り１８ｍｌの発色現像補充液が必要であるが、本発明に係る処理方法では、１ｍ当り５ｍｌ以下で処理が可能になり、また処理時間も従来３分以上かけて発色現像処理を行っているが、本発明に係る処理方法ではおよそ１２０秒以内で発色現像工程を行うこともできる。
【０３０５】
なお、本実施形態では、上述した塗布ノズルを用いて処理を行うが、これに限定されるものではなく、例えばインクジェットノズルを用いることも可能である。ただし、発色現像液のアルカリ剤を塗布する発色現像液塗布部１２０のアルカリ剤塗布部１２２は、用いる処理液が強アルカリ性であり、通常のインクジェットノズルでは処理に耐えられないため、本発明に係る塗布ヘッドを用いることが好ましい。また、上記整流板２１３は、本実施形態では外に設ける構成となっているがこれに限られるものではなく、例えばヘッドのスリット内部に設けても効率良く処理液の流量や方向性を調整して塗布することができる。
【０３０６】
なお、本発明は上記実施形態に限定されるものではない。たとえば、各塗布ユニット間にスクイーズローラーを設ける構成としても良く、このローラーを吸水性部材としても良い。
【０３０７】
【実施例】
以下、実施例をあげて本発明の詳細に説明する。ただし、本実施例に限定されないのは言うまでもない。
【０３０８】
＜製造例１＞
発色現像液の製造
以下に示す各方法で、発色現像主液であるＣＤ−４（４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アニリン１硫酸塩を製造した。
【０３０９】
なお、実施例中使用機器、分析条件等は以下に示す共通のものを用いた
分析条件
１）イオンクロマトグラフィー
・ＨＰＬＣ 日本分光（株）製
ＤＧ−９８０−５０ デガッサ
ＰＵ−９８０ インテリジェントＨＰＬＣポンプ
ＬＧ−９８０−０２ 低圧グラジエントオートサンプラ
ＣＯ−９６０ カラムオーブン
ＬＣＳＳ−９０５ システムステーション
・検出器 昭和電工（株）
ＳＨｏｄｅｘ ＩＣＩ−５２４Ａ
・溶離液 ２．５ｍＭ＊ｏ−フタル酸（東京化成（株）製）水溶液ｐＨ４．０（０．１Ｍ＊トリス（ヒドロキシメチル）アミノメタン（東京化成（株）製）水溶液で調整）
・流量 ２ｍｌ／ｍｉｎ
・温度 ４０℃
２）液体クロマトグラフィー
・ＨＰＬＣ 日本分光（株）製
ＤＧ−９８０−５０ デガッサ
ＰＵ−９８０ インテリジェントＨＰＬＣポンプ
ＬＧ−９８０−０２ 低圧グラジエントユニット
ＡＳ−９５０ インテリジェントオートサンプラ
ＣＯ−９６０ カラムオーブン
ＬＣＳＳ−９０５ システムステーション
・検出器 日本分光（株）製Ｆｉｎｅｐａｃｋ ＳＩＬ Ｃ１８Ｓ
・溶離液 ３．７５ｍＭ燐酸（関東化学（株）製）ｐＨ４．０（水酸化カリウム（関東化学（株）製）で調整）：アセトニトリル（関東化学（株）製）＝１：１・流量 ０ｍｌ／ｍｉｎ
・温度 ４０℃
３）表面張力：ＫＲＵＳＳ製 Ｂｕｂｂｌｅ Ｐｒｅｓｓｕｒｅ Ｔｅｎｓｉｏｍｅｔｅｒ ＢＰ２（表面ができてから１秒後を測定）
４）粘度測定：芝浦システム株式会社製単一円筒型回転粘度計ビスメトロンＶＧ４
製造方法１
室温下、マグネチックスターラーで攪拌しながら、４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アニリン１硫酸塩１．６９ｍｏｌ、重亜硫酸カリウム１．１４ｍｏｌを純水４９４ｍｌに溶解し、更にＮ−メチル−２−ピロリドン１．１９ｍｏｌ及びジエチレングリコール１．１１ｍｏｌを添加する。
【０３１０】
上記混合物の仕上り液量を１０７７ｍｌに調整する。
【０３１１】
次いで、水浴で温度を４０度以下に制御しながら水酸化カリウム（フレーク）３．２４ｍｏｌを上記混合液に徐々に添加して中和する。
【０３１２】
その後、１５℃以下で１５分以上放置し、５Ｃの濾紙（保持粒径１μ）で吸引濾過して硫酸カリウムを除去する。そして、除去後の液量を１０００ｍｌ、仕上りｐＨ７．２とする。
【０３１３】
このように製造した主薬液中、ＣＤ−４含有量は１．６９ｍｏｌ／ｌである。ＣＤ−４濃度の確認は液体クロマトグラフィーで分析を行い、上記値になることを確認した。
【０３１４】
また、上記硫酸カリウムとして除去した後の硫酸イオン濃度は、イオンクロマトグラフィーで確認を行い、該イオンが主薬液中から検出されないことを確認した。（除去率１００％。主薬とのモル比０）
製造方法２
室温下、４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アニリン１硫酸塩１．０７ｍｏｌを純水７３７ｍｌに溶解し、次いで重亜硫酸カリウム０．９ｍｏｌ、Ｎ−メチル−２ピロリドン０．９４ｍｏｌ及びジエチレングリコール０．８８ｍｏｌを加え、混合容器中マグネチックスターラーにより充分攪拌した。仕上り量は１３６０ｍｌとした。
【０３１５】
次いで水浴で温度４０℃以下に制御しながら水酸化カリウム（フレーク）１．８４ｍｏｌを徐々に添加して中和を行った。更に、製造方法１と同様に硫酸カリウムを析出させて除去した。
【０３１６】
最後に仕上り量を１０００ｍｌに調整した。
【０３１７】
このようにして得られた主薬液の硫酸イオン濃度をイオンクロマトグラフィーで分析、確認したところ、主薬液中の硫酸イオンは０．２５ｍｏｌ／ｌであり、除去率は７７％、主薬とのモル比０．７７であることが確認された。
【０３１８】
また、ＣＤ−４濃度の確認を液体クロマトグラフィーで行い、ＣＤ−４は１．０７ｍｏｌ／ｌであることを確認した。
【０３１９】
次に比較試験用の主薬液を製造した。比較例用としては、主薬液及びアルカリ液を混合した１液組成物と、主薬液パート及びアルカリ液パートをわけた２液組成物の２通り作製した。以下に製造処方を示す。
【０３２０】
試験処方
製造方法比較１ １液組成
溶解水 ＋
臭化ナトリウム ０．０１３ｍｏｌ
ヒドロキシルアミン硫酸塩 ０．０３ｍｏｌ
重亜硫酸ソーダ ０．０１４ｍｏｌ
炭酸カリウム ０．２８ｍｏｌ
４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アニリン１硫酸塩 ０．０１５ｍｏｌ
上記組成を純水中に添加し、更に純水を加えて１Ｌとした
ｐＨは水酸化カリウム、硫酸でｐＨを１２．５に調整した。
【０３２１】
製造方法比較２
主薬パート
４−アミノ−３−メチル−Ｎ−エチル−Ｎ−（β−ヒドロキシエチル）アニリン１硫酸塩
１．５０ｍｏｌ、重亜硫酸ナトリウム０．２４ｍｏｌを純水に加えて１Ｌとした。
【０３２２】
ｐＨ＝２．０
以上のようにして得られた各主薬液を用いて、以下の試験を行った。
【０３２３】
＜実施例１＞
前処理（プレソーキング）工程の有無による現像活性への影響試験
以下の条件で現像処理を行い、プレソーキング処理の有無で現像活性の影響を試験した。
【０３２４】
・試験条件
塗布装置：本発明に係るスリットオリフィスコーター（ノズル幅２５ｍｍ、奥行き０．１ｍｍ）を使用。
【０３２５】
感光材料：富士写真フィルム（株）ＳＵＰＥＲＩＡ４００
試験ピース：上記感光材料を、（株）メステック製ＪＩＳＩＩＩ型感光計を使用して色温度５５００°でウェッジ露光したもの
塗布液：以下に示した主薬パート液及び比較処方に記載したアルカリパート液を使用した。プレソーキング液には純水を用いた。
【０３２６】
塗布方法：上記コーターを各処理液毎に感材搬送方向に対して垂直に配置し、５ｍｍ／秒で感材を搬送しながら、上記コーターのスリットから塗布液を感材表面に塗布する。
【０３２７】
試験方法
１：各処理液を塗布しながら、各ノズル間を５秒で搬送処理を行う。
２：処理後感材を取りだして１分水洗する。
３：感材をノーリツ鋼機（株）製ＱＳＦ−Ｖ５０自現機を用いて発色現像工程を経ずに後処理工程（漂白−定着−安定化−乾燥）を行う。後処理工程の処方は以下の通りである。
【０３２８】
＜処理液の調整＞
＜発色現像液＞
発色現像液については、上記製造例の主薬を用いて以下の通り調整した。
【０３２９】
主薬１：主薬パートの製造方法に記載した、製造方法に記載した、製造方法１の組成に純水を加え、主薬濃度が１ｍｏｌ／ｌになるように調整して作製した。
【０３３０】
主薬２：比較処方に記載した、比較２の組成に純水を加え、主薬濃度が１ｍｏｌ／ｌになるように調整して作製した。
【０３３１】
アルカリ液の調整（Ｂ１〜Ｂ３）
下記化合物を攪拌しながら純水に溶解し、１０００ｍｌにした。
【０３３２】
ＫＨ_２ＰＯ_４ ０．１５ｍｏｌ
ＫＯＨ 表３記載ｍｏｌ
界面活性剤
Ｔｒｉｔｏｎ Ｈ−６６ ３０ｇ
（Ｕｎｉｏｎ Ｃａｒｂａｉｄｅ Ｌｉｍｉｔｅｄ製）
メガファックＦ−１２０ １ｇ
（大日本インキ製）
ＰＨ＝表３記載 とした。
＜漂白補充液＞
酢酸 １．２ｍｏｌ
１，３−ＰＤＴＡ第二鉄塩 ０．４５ｍｏｌ
臭化アンモニウム １００ｇ
硝酸アンモニウム １００ｇ
水を加えて１Ｌ
ｐＨ３．５に調整
＜漂白液＞
漂白補充液を７０％希釈したものをｐＨ４．５に調整した。
【０３３３】
＜定着補充液＞
チオ硫酸アンモニウム塩 １．２２ｍｏｌ
重亜硫酸アンモニウム ０．５２ｍｏｌ
トリエチレンテトラミン ０．３５ｍｏｌ
エチレンジアミン四酢酸 ０．０４ｍｏｌ
水を加えて１Ｌ
ｐＨ６．８５に調整
＜定着液＞
定着補充液を５０％希釈したものをｐＨ６．８５に調整して使用した。
【０３３４】
評価基準
塗布した時の感材表面の状態を目視で評価した。
【０３３５】
現像主薬濃度が高い処理液は、感材に浸透しづらいため、写真濃度が上がりづらくなる。そこで、最大濃度値を比較して評価を行った。
【０３３６】
評価には、Ｘ−Ｒｉｔｅ３１０ＴＲ濃度計を用いて、ＳｔａｔｕｓＭで測定を行った。
【０３３７】
合否判定
シアンのＤｍａｘ濃度とステインの濃度差が
１．０以上 ○
１．０未満〜０．９以上 △
０．９未満 ×
と判定した。
【０３３８】
以下、本試験の結果を下記に示す
【表１】

【０３３９】
なお、本試験では、発色現像工程以降は既存の自動現像機を使用し、発色現像工程が終了した時点で、３ｗ／ｗ％酢酸水溶液で現像反応を停止（ＳＴＯＰ）させるようにした。
【０３４０】
上記表中、主薬１及び主薬２については上述した通りである。
【０３４１】
上記の結果から、プレソーキング工程を行うことにより写真濃度が向上することがわかった。
【０３４２】
＜実施例２＞
プレソーキング液塗布の有無による画像のデジタル処理試験
・試験条件
主薬液の塗布はバブルジェット（登録商標）プリンターを改良したものを用い、それ以外の塗布装置、感光材料ともに実施例１と同様のコーターを用いた。試験ピースも実施例１と同様にして作製した。
【０３４３】
塗布方法
前処理、アルカリ液、定着液、水洗水は塗布処理とした。
【０３４４】
主薬液の塗布は、キャノンＢＪプリンターを用いて、ＢＸ−３インクカートリッジに主薬パート液を詰めて塗布を行った。このとき、塗布媒体をＢＪクロスに設定し、印刷品位ファインとして、誤差拡散モードで液を吐出した。塗布量は３７ｍｌ／ｍ^２とした。
【０３４５】
塗布液の調整
プレソーキング液：純水を使用した。
【０３４６】
Ａ１〜４：比較処方で作製した主薬２の液を下記表２に記載した主薬モル濃度になるように純水で希釈して比較例の主薬液を作製した。
【０３４７】
Ａ５〜７：製造例１で作製した主薬パート液を下記表２に記載した主薬モル濃度になるように純水で希釈して本発明に係る主薬液を作製した。
【０３４８】
Ｂ１〜３：表３に記載したアルカリパート液（水酸化カリウム １．０６ｍｏｌ／ｌ）１を使用した。
【０３４９】
【表２】

【０３５０】
【表３】

【０３５１】
処理方法：各処理液は以下の通り塗布を行った。
【０３５２】
前処理液 ５秒／１回塗布、２５℃
主薬パート液 ３１秒／１回塗布、２５℃
アルカリパート液 ２０秒／１回塗布、４５℃
定着液 ７０秒、４５℃
水洗水 ５秒、４５℃
乾燥 ５秒、６０℃
評価方法
１：従来の塗布現像処理ではシアン濃度が上がりにくく、画質が軟調化するため、シアンＤｍａｘとシアンＤｍｉｎの濃度差ΔＤの測定をして処理後の画質を評価した。
【０３５３】
２：処理後の感材を、ミノルタ（株）Ｑｕｉｃｋ Ｓｃａｎ３５でデータスキャンし、ＡｄｏｂｅフォトショップＶｅｒ．６．０で画像調整後、ノーリツ鋼機（株）製ＱＳＳ３００１Ｄｉｇｉｔａｌ自現機でプリント出力を行い、Ｃ４１プロセスと同等の仕上がりが得られるか否かを評価した。
【０３５４】
評価基準
１：シアンΔＤ＞１．００を実用可能とした。
２：プリント条件を調整して、Ｃ４１プロセスと同等な実画像が得られた場合は、本塗布処理で得たデジタルデータを通常処理と同等の画像になるように変換が可能である。このため、ＱＳ３００１Ｄｉｇｉｔａｌ自現機の露光条件を調整し、Ｃ４１プロセスと同等な仕上がり画像が得られたものを実用可能とした。
【０３５５】
結果
本試験の結果を下記表に示す。
【０３５６】
【表４】

【０３５７】
＜実施例３：前処理液の物性による効果の違い＞
前処理液の粘度、表面張力塩類濃度が前処理工程においてどのように影響を及ぼすか確認するために以下の試験を行った。
【０３５８】
試験条件
塗布装置：実施例１、２に準じて使用した。
【０３５９】
感光材料：実施例１、２と同じ物を使用し、試験ピースも上記試験と同様にして作製した。
【０３６０】
塗布液
主薬パート液：比較処方で作製した比較２の液を主薬１ｍｏｌ／ｌとなるように純水で希釈して作製。
【０３６１】
アルカリパート液：比較処方に記載したアルカリパート液（水酸化カリウム１．０６ｍｏｌ／ｌ）を使用した。
【０３６２】
前処理液：下記表に示す前処理液（ＰＳ（プレソーキング）液）を使用した
粘度による浸透効果の確認試験：下記表５に示す組成の前処理液を用いた。
【０３６３】
【表５】

【０３６４】
なお、増粘剤としては、アルギン酸ナトリウムを使用した。
【０３６５】
表面張力による浸透効率の確認試験：下記表６に示す前処理液を用いた。
【０３６６】
【表６】

【０３６７】
なお、表面張力調整剤としては、Ｆ−１２０（メガファック）、Ｈ−６６を用いた。
【０３６８】
電導度（塩類濃度）による浸透効率の確認：下記表７に示すように、電導度が以下の通りになるようにＮａ_２ＳＯ_４を攪拌しながら純水に溶解し、各前処理液とした。
【０３６９】
【表７】

【０３７０】
各試験方法は以下の通りとした。
１：各塗布液を供給しながら、各ノズル間を５秒で搬送処理を行う。
２：スリットオリフィスコーターから感材を取り出して１分水洗する。
３：感材をノーリツ鋼機（株）製ＱＳＦ−Ｖ５０自現機を用いて発色現像工程を経ずに、漂白−定着−安定化−乾燥処理を実施する。
【０３７１】
上記漂白工程以降の処理液組成については実施例１に準じた
評価基準
プレソーキング液の粘度や表面張力を変えることにより、主薬の浸透速度を向上する効果が弱まるためプレソーキング液の粘度を変化させたときの最大写真濃度を比較した。
【０３７２】
濃度は濃度計Ｘ−Ｒｉｔｅ３１０ＴＲを用いてＳｔａｔｕｓＭで測定した。
【０３７３】
また、塗布したときの感材表面の状態（処理液が感材上から流れ出していないか）を目視で評価した。
【０３７４】
合否判定
プレソーキング工程を行わない処理と比較し、写真濃度や現像ムラの程度が優れていた場合、効果ありと評価した。
【０３７５】
・濃度評価：プレソーキング工程の有無でシアンのＤｍａｘ濃度とステイン濃度の差が１以上であれば効果ありと評価した。
【０３７６】
濃度評価：シアンのＤｍａｘ濃度とステインの濃度差が
○：１．０以上
△：１．０未満〜０・９以上
×：０．９未満
と判定した。
【０３７７】
・ムラ評価：以下の通り評価した。
○：現像ムラがない状態
△：現像ムラがプレソーキング工程無しと同じ状態
×：現像ムラがひどい状態
結果
試験結果を下記表８に示す
【表８】

【０３７８】
＜実施例４：前処理工程の組成による効果の違い＞
前処理工程において、前処理液がどれだけ現像主薬量、アルカリ量、を含有しても主薬パートの浸透を妨げないか確認を行った。
【０３７９】
塗布装置、感光材料、試験ピースは実施例１と同様にした。
【０３８０】
塗布液：以下の表９に示すように、実施例１で使用した主薬工程液（主薬１）と実施例１で使用したアルカリ工程液（Ｂ３、ＫＯＨ １．０６ｍｏｌ／ｌの物）をそれぞれ希釈して使用した。
【０３８１】
【表９】

【０３８２】
試験方法：実施例１と同様に行った。
【０３８３】
評価方法：現像主薬濃度を変化させたときに一番影響の大きい感材最上層の最大写真濃度値を比較した。濃度値は濃度計Ｘ−Ｒｉｔｅ３１０ＴＲを用いてＳｔａｔｕｓＭで測定した。
【０３８４】
合否判定：各主薬濃度処理でのイエローＤｍａｘを純水処理と比較した値ΔＤｍａｘが±０．０３以内について現像反応に関与しないと評価した。
【０３８５】
結果：上記試験の結果を下記表１０に示す。
【０３８６】
【表１０】

【０３８７】
このように、前処理液は、水だけでなく、所定量の主薬、アルカリ、を含んでいる場合でも、主薬の浸透速度を低下させることはなく、良好に発色現像工程を行うことができるということが示された。
【０３８８】
なお、本実施形態は塗布による方法に限定されるものではなく、含浸による方法に使用してもよい。
【０３８９】
【発明の効果】
以上説明したように、本発明の処理方法及びそれに用いる発色現像液によれば、主薬液を塗布する前に前処理液を感材へ塗布・浸透させることにより、主薬液の浸透性を向上することが可能となり、それによりアルカリ液を塗布したときに感材底部の色層であっても充分な発色反応を得ることができ、画像品質が向上する。また、主薬液の浸透速度も向上するため、処理効率も向上することが可能となる。
【図面の簡単な説明】
【図１】従来の２液塗布法を説明する概略図である。
【図２】本発明に係る塗布方法を説明する概略図である。
【図３】本発明に係る塗布処理工程を示す工程図である。
【図４】本発明にかかる塗布処理装置の全体構成図である。
【図５】本発明の処理方法を行う塗布ユニットの概略図である。
【図６】本発明の処理方法を行う塗布ノズルの概略模式図である。
【図７】本発明に係る塗布ノズルに用いられるヘッド内部を示す断面図である。
【符号の説明】
１００…ＤＦＰ装置
１０５…感材
１１０…プレソーキング部
２００…塗布ユニット
２１０…塗布ノズル
２１１…塗布ヘッド[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for processing a silver halide color photographic light-sensitive material and a color developer used for the method. More specifically, the present invention relates to a processing method characterized by improving the permeability of a color developing solution and thereby improving image quality, and a color developing solution used therefor.
[0002]
[Prior art]
In recent years, along with the improvement in image quality of ink jet printers, in the development processing of silver halide color photographic light-sensitive materials (hereinafter also referred to as photosensitive materials), digital data is printed on silver halide photographic paper (silver halide paper) and from silver halide film. Digital data conversion to various media is becoming possible.
[0003]
In recent years, digital minilabs have become widespread in order to perform various development processes such as digitization of developed images of prints or photographic materials from such digital data. There are demands for speeding up and reducing the amount of waste liquid after treatment.
[0004]
Generally, the development step of a silver halide color photographic light-sensitive material comprises a color development step, a bleaching step, a bleach-fixing or fixing step, a rinsing step and a drying step. At present, various photosensitive materials have been developed, and various automatic developing machines (hereinafter, also referred to as self-developing machines) are used. The method used there is a tank filled with each processing solution and a processing layer. In general, the processing is performed in each processing tank while the photosensitive material is transported by the transport means.
[0005]
Of these, in the color developing step, processing is performed using a color developing solution mainly comprising a color developing agent and an alkali agent. That is, the silver in the photosensitive material is reduced and precipitated by the color developing agent, and at the same time, the color developing solution is oxidized, thereby reacting with the coupler in the photosensitive material to form a dye to obtain an image. it can. At this time, a color developing agent and an alkali agent are often mixed and used in one liquid. (Single liquid treatment)
However, in such a method, in order to speed up the color development processing, it is necessary to highly activate the color development processing solution, but in order to do so, the processing solution must be highly alkalinized. There is a problem that the liquid is susceptible to air oxidation and cannot maintain the stability of the liquid. Further, since the amount of the color developing solution to be used is large, the amount of waste liquid is also large, which is also an environmental problem.
[0006]
Various processing methods have been proposed to solve such various problems, but a particularly demanding method is to directly develop a color on the image forming surface (also referred to as an emulsion surface) of the photosensitive material by a coating apparatus. An application method of applying a liquid is exemplified. In particular, in the method of supplying the minimum amount of the color developing solution to be used in order to rapidly perform the color developing process (hereinafter also referred to as a dry method), the amount of waste liquid can be greatly reduced, so that cost and environmental aspects are reduced. Is also preferred.
[0007]
In order to solve such a problem, Japanese Patent Application Laid-Open No. 2-203338 discloses a method in which a color developing agent and an alkaline agent are used to carry out impregnation in a processing tank (two-component impregnation method). Japanese Patent Application Laid-Open Nos. 9-90579, 90580, and 90581 disclose a method in which a liquid containing a low pH color developing agent and an alkaline agent are divided into two liquids, and each liquid is individually coated on the emulsion surface of a light-sensitive material. (Two-liquid coating method).
[0008]
[Problems to be solved by the invention]
However, in the above-mentioned method, for example, in the above-described one-liquid coating method, although the stability of the liquid can be maintained, it is difficult to increase the concentration of the developing agent, and it is difficult to obtain a sufficient image. Can not. In order to obtain a sufficient image density, it is necessary to apply a large amount of liquid, and a large amount of waste liquid is discharged, which cannot be said to be a dry treatment.
[0009]
In the two-liquid impregnation method, the main agent and the alkali agent are separately processed, so that there is an effect that the development efficiency is slightly improved. However, since the processing method is a method of impregnating the same processing tank as the conventional one, The method also produces a large amount of waste liquid as described above.
[0010]
Next, in the two-liquid coating method, the amount of waste liquid can be reduced as compared with the above method, but a sufficient concentration cannot be obtained.
[0011]
Also, when applying a low pH color developing agent solution, unless the concentration of the high pH alkaline solution to be applied next is set to a considerably high level, the developing activity cannot be improved after the color developing solution has penetrated the photosensitive material. .
[0012]
Further, if the treatment is carried out with a high pH alkaline solution in order to improve the developing activity, a neutralization reaction occurs violently with the previously applied low pH color developing solution, and the development reaction is slowed down, so that the rapidity is impaired. In addition, strong acid ions and salt crystals in the main ingredient precipitate on the surface of the photosensitive material, and the image density cannot be increased.
[0013]
In addition, bubbles due to the reaction remain on the photosensitive material, causing uneven development and deteriorating the image quality. Also, a low pH color developer contains a large amount of strong acid ions such as sulfuric acid, and reacts with an alkali agent to form sulfates, hydrochlorides, nitrates, p-toluenesulfonates, sulfonates, etc. as crystals. Precipitated crystals need to be removed (squeezed) in a subsequent step. At that time, however, the crystals adhere to the squeezed portion over time and damage the surface of the photosensitive material.
[0014]
Although this method can be called a dry method, there is a problem that it is environmentally unfavorable because the crystals thus precipitated must be removed and discarded.
[0015]
In addition, the content of the conventional color developing agent is generally 0.005 to 0.3 mol / l, and since the content is small, the coating amount must be increased, and the amount of waste liquid naturally increases. Therefore, when the amount of the color developing agent in the color developing agent solution is large, the permeation rate of the color developing agent decreases, and the amount of permeation differs between the upper layer and the lower layer of the photographic material. There is a problem that is caused.
[0016]
The present invention has been made in view of the above circumstances, while responding to the digitalization of the photosensitive material, even if a high-concentration main chemical solution is used, enhance the permeability of the color developing solution to the photosensitive material, A color developing method for a silver halide color light-sensitive material, which enables rapid development processing, reduction (drying) of processing replenishers and waste liquids, and improvement of development image quality to obtain sufficient photographic characteristics, silver halide color It is an object of the present invention to provide a color developing solution for a light-sensitive material and a method for processing a silver halide color photographic light-sensitive material.
[0017]
[Means for Solving the Problems]
The object of the present invention has been achieved by the following means.
[0018]
That is, the processing method of the present invention is a processing method of a silver halide color photographic light-sensitive material including a color development step, wherein the color development step includes a pre-processing step of processing a surface of the photosensitive material with a pre-processing solution, and a color development step. It is characterized by comprising a main chemical solution process for treating the main chemical solution and an alkali solution process for treating the alkaline solution.
[0019]
The pre-processing step is performed before the main chemical solution step to swell the emulsion layer of the photosensitive material.
[0020]
Further, the color forming step is characterized in that an alkali liquid applying step is performed after repeating the pretreatment step and the main chemical liquid step a plurality of times.
The pretreatment liquid contains the color developing agent, and the content of the color developing agent is 2/5 or less of the amount of the color developing agent contained in the color developing agent.
[0021]
The pretreatment liquid contains the alkaline agent, and the content of the alkaline agent is 1/10 or less of the amount of the alkaline agent contained in the alkaline liquid.
[0022]
The pretreatment liquid is water.
[0023]
The surface tension of the pretreatment liquid is 25 to 70 mN / m.
[0024]
The viscosity of the pretreatment liquid is not more than 25 mPa · s.
[0025]
The main drug solution has a pH> 7 and contains at least one selected from the following compound group [A] in a molar ratio to the main drug of less than 1.
[0026]
Compound group [A]
Sulfate ion
Chloride ion
Nitrate ion
p-toluenesulfonic acid ion
Sulfonate ion
The alkaline liquid has a pH of 12.5 or more.
[0027]
The image processing apparatus further includes an image processing step of converting an image obtained by the color development step into digital data.
[0028]
The color developing solution of the present invention contains a pre-processing solution for swelling the photosensitive material and at least 1 to 2 mol / l of a color developing agent, has a pH> 7.0, and has at least one kind selected from the following compound group (A). It is characterized by comprising a color developing agent solution having a strong acid ion in a ratio of less than 1 to the main agent, and an alkali solution having a pH of 12.5 or more.
[0029]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0030]
<Treatment Liquid> First, the treatment liquid of the present invention will be described.
[0031]
The processing solution of the present invention is a processing solution used in the color development step of the color development processing method for a silver halide color photographic light-sensitive material, and (1) a preprocessing solution containing water or a low-concentration base agent or alkali agent (presoaking). Liquid), (2) a main part processing liquid containing a color developing agent, and (3) an alkali part processing liquid containing an alkali agent.
[0032]
In the processing method of the present invention, which will be described later, the color developing solution is first applied to the photosensitive material before (2) to penetrate the photosensitive material, then (2) is applied, and then (3) is applied. It is used in a configuration of coating.
[0033]
According to such a configuration, the pretreatment liquid, which is a low-concentration solution (or water), is infiltrated into the photosensitive material before the high-concentration main chemical solution is applied, so that the photosensitive material swells, Since the color developing agent permeates quickly, the reactivity with the alkaline solution in the lower layer of the light-sensitive material is also improved, thereby making it possible to prevent uneven color formation.
[0034]
Hereinafter, each processing liquid will be described.
[0035]
<Pretreatment liquid>
The pre-processing solution according to the present invention is a processing solution containing water or a trace amount of a color developing agent or an alkali agent. When the salt concentration of the pretreatment liquid is high, there is a problem that penetration into the photographic material is deteriorated. The conductivity of the pretreatment liquid may be in the range of 80 mS / m or less.
[0036]
Here, specifically, the conductivity may be 80 mS / m or less, preferably 60 mS / m or less, and more preferably 40 mS / m or less. According to such a configuration, it is possible to quickly penetrate the photosensitive material.
[0037]
Here, tap water can be used as the water, but it is preferable to use water purified by filtration, distillation, reverse osmosis membrane, ion exchange membrane, or the like, or a combination thereof, so-called pure water.
[0038]
When a processing solution containing the above-described main agent or alkaline agent is used, the concentration thereof is 2/5 or less of the amount contained in a color developing agent solution described later when a color developing agent is included, and preferably 1%. / 5, more preferably 1/10 or less. When an alkali agent is contained, the concentration is preferably 1/10 or less of the amount contained in the alkaline solution described below, preferably 1/20 or less, more preferably 1/50 or less.
[0039]
When the content is in such a range, the emulsion can be swollen in a short time, and the permeability of the main chemical solution and the alkali solution to be subsequently applied can be increased.
[0040]
In conventional color developing solutions, a high-concentration main chemical solution with poor permeability is applied first, so that the permeation into the photosensitive material is not uniform, and the distribution of the main drug amount is unbalanced inside the photosensitive material, In the color developing solution of the present invention, by applying a low-concentration solution or pure water as a pre-processing solution to the photosensitive material in advance before applying the main chemical solution, it easily permeates even if the concentration of the subsequent processing solution is high. There is. That is, the low-concentration pretreatment liquid quickly permeates into the photosensitive material, and the permeated pretreatment liquid becomes priming water, and even if a high-concentration processing liquid (a color developing agent solution and an alkaline solution) is applied, the surface of the photosensitive material is not affected. Since it penetrates quickly without being repelled, it is possible to improve the color developability of the light-sensitive material. In addition, since it can uniformly penetrate the photosensitive material, it is possible to prevent uneven coloring. As a result, the photographic characteristics of each light-sensitive material can be sufficiently exhibited.
[0041]
In addition, the pretreatment liquid of the present invention has a surface tension of 70 mN / m or less in order to uniformly coat the surface of the photosensitive material. Preferably, it is 50 mN / m or less.
[0042]
By reducing the surface tension in this way, the speed of penetration into the emulsion can be increased, and the photographic material can be swelled in a short time. In this case, if the surface tension is 25 mN / m or more, the spreading speed of the processing liquid on the surface of the light-sensitive material does not increase, so that the amount of liquid spilling from the surface of the light-sensitive material is suppressed, and it can be avoided from saying that the waste liquid increases. .
[0043]
In order to obtain such a surface tension, it is preferable to add an organic solvent or a surfactant.
[0044]
Examples of the organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, Examples include propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol butyl ether and the like.
[0045]
Further, the following compounds can be suitably used as the surfactant.
[0046]
Fatty acid salts, hydroxyalkanesulfonates, alkanesulfonates, dialkylsulfosuccinates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene alkylsulfenyl ether salts, alkyl sulfate salts, polyoxyethylene alkyl ether phosphate Ester salts, perfluoroalkyl carboxylic acids, perfluoroalkyl sulfonic acids, perfluoroalkyl phosphates, and the like.
[0047]
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and polyethylene glycol fatty acid. Esters, perfluoroalkylethylene oxide adducts, poly (oxyethylene, oxypropylene) methylpolysiloxane copolymers, polyoxyethylene / methylpolysiloxane copolymers, acetylene glycol ethylene oxide adducts, and the like.
[0048]
Of these, preferably, ethylene glycol and ethylene glycol butyl ether are used as the organic solvent, and dialkyl sulfosuccinates, polyoxyethylene alkyl ether phosphates, perfluoroalkyl carboxylic acid, and perfluoroalkyl sulfonic acid are used as the surfactant. Polyoxyethylene / methylpolysiloxane copolymers and acetylene glycol ethylene oxide adducts are preferably used.
[0049]
The addition amount of the organic solvent is 0 to 50 w / v%, preferably 0 to 30 w / v%.
[0050]
The addition amount of the surfactant is 0 to 20 w / v%, preferably 0 to 5 w / v%.
[0051]
Further, the viscosity of the pretreatment liquid is 25 mPa · s (measuring temperature 45 ° C.) or less, and preferably 2.5 mPa · s (measuring temperature 45 ° C.) or less.
[0052]
If the viscosity of the pretreatment liquid is high, it is preferable in that the thickness of the coating liquid can be maintained, but if the squeeze step is not performed thereafter, the gelled pretreatment liquid covers the photosensitive material surface, and then There is a problem that the main chemical solution to be applied does not penetrate sufficiently and does not function as a pre-treatment solution, and there is a problem that the squeezed processing solution becomes waste liquid. It is desirable to have
[0053]
The following compounds can be added as viscosity modifiers.
[0054]
Cellulose derivatives such as carboxymethylcellulose and hydroxypropylmethylcellulose, alginates, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, polyethylene glycol, polyacrylamide, methacrylic acid copolymer and the like.
[0055]
Of these, preferred are alginates, hydroxypropyl methylcellulose and the like.
[0056]
As a chelating agent, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid and the like can be used.
[0057]
Specifically, ethylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, nitrilotriacetic acid, hydroxymethyliminodiacetic acid, N -(2-carboxyethyl) iminodiacetic acid, N- (2-carboxymethyl) iminodiacetic acid, β-alaninediacetate, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N , N, N-trimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, and the like.
[0058]
The amount of the chelating agent used is preferably 0.1 to 5 g / l.
[0059]
Further, an anti-drying agent may be added to the pre-treatment liquid so that the pre-treatment liquid applied before moving to the main agent application step is not dried on the light-sensitive material and its effect is not weakened.
[0060]
Examples include the following compounds.
[0061]
Oxyethylene or oxypropylene addition polymers such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol and polypropylene glycol; Alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, 1,2,6-hexanetriol and hexylene glycol; Lower alkyl ethers of polyhydric alcohols such as thiodiglycol, glycerin, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, and triethylene glycol monoalkyl ether. Nitrogen-containing heterocyclic ketones such as N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone.
[0062]
Among these, diethylene glycol, triethylene glycol, polyethylene glycol, ethylene glycol, propylene glycol, thiodiglycol, glycerin and the like are preferable, and diethylene glycol, triethylene glycol, glycerin and the like are more preferable.
[0063]
With the configuration described above, the pretreatment liquid can quickly and uniformly penetrate into the light-sensitive material, and the permeability of the treatment liquid also increases thereafter.
[0064]
Next, the main part treatment liquid will be described.
[0065]
<Main agent part treatment liquid>
As the color developing agent used in the main part processing solution (hereinafter also referred to as the main part), a p-phenylenediamine-based compound or a sulfate, hydrochloride, nitrate, p-toluenesulfonate, or a sulfonate thereof is appropriately used. They can be used, and two or more kinds may be used in combination according to the application.
[0066]
Examples 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- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino- -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-hydr (Xybutyl) aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates and hydrochloric acid Salts, nitrates, p-toluenesulfonates or sulfonates are exemplified.
[0067]
Also preferably, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-3-methyl-N- (β-hydroxyethyl) aniline, 4-amino-3-methyl-N-ethyl-N -(Β-methanesulfonamidoethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline, 4-amino-3- (β-methanesulfonamidoethyl) aniline, Compounds such as -amino-3-methyl-N (β-methoxyethyl) aniline, 4-amino-3-butyl-N (β-butylsulfonate) aniline and their sulfates, hydrochlorides, nitrates, p-toluene Sulfonates, and sulfonates.
[0068]
The content of the color developing agent in the main solution of the present invention is 1 to 2 mol / l. It is preferably from 1 to 1.7 mol / l, more preferably from 1.05 to 1.4 mol / l.
[0069]
In the case of the main chemical solution conventionally used, a severe reaction occurs when mixing or applying the part with the alkali part solution, and therefore, it was not possible to apply uniformly. Since the pH is adjusted as described later, it is possible to contain the above-mentioned amount, thereby improving the color developing activity.
[0070]
Further, the treatment solution for the base drug part of the present invention has a pH exceeding 7.0. Preferably, it is preferably 7.0 to 10, more preferably 7.0 to 8.0.
[0071]
When the pH is lower than 7.0, the reaction when the alkaline part solution is applied becomes violent, and when the pH is higher than 10, a highly concentrated solution cannot be produced (the color developing agent has a high pH due to a weak base). This causes a problem that the amount of waste liquid cannot be reduced.
[0072]
In addition, in the main chemical solution of the present invention in order to achieve the above-mentioned pH value, the concentration of the strongly acidic ion is controlled in order to precipitate a strong acid salt in the production process of the present main chemical solution described later. That is, in order to adjust the pH of the main chemical solution to the above value, a neutralizing agent such as sodium hydroxide, potassium hydroxide, lithium hydroxide or the like can be added as a pH adjuster.
[0073]
The concentration of sulfate ion, chloride ion, nitrate ion, p-toluenesulfonic acid ion and sulfonate ion in the main chemical solution thus adjusted is 1.0 mol / l in molar ratio with the color developing agent. Less is better.
[0074]
The molar ratio is preferably 0 to 0.8 mol / l, more preferably 0 to 0.5 mol / l.
[0075]
By lowering the concentration of strong acid ions in the color developing solution, it is possible to prevent a reaction product of the ions and the alkali agent from depositing on the surface when the alkali agent is applied. In addition, this makes it possible to contain the color developing agent in a larger amount than the normal content, and even if the amount of the main agent solution applied to the light-sensitive material is reduced, a sufficient amount of the color developing agent is added to the light-sensitive material. And a necessary and sufficient image density can be obtained.
[0076]
In addition, with such a configuration, when the liquid is stored in a cold region, precipitation of crystals can be suppressed particularly at low temperatures, which is convenient for maintaining the quality of the main chemical liquid.
[0077]
Sulfurous acid can be added to the main chemical solution as an antioxidant.
[0078]
For example, sulfites such as ammonium sulfite, potassium sulfite or sodium sulfite, bisulfites such as ammonium bisulfite, potassium bisulfite or sodium bisulfite, and metabisulfites such as ammonium metabisulfite, potassium metabisulfite or sodium metabisulfite. Examples include sulfites, hydroxylamines, reductones, and sulfinic acids.
[0079]
The sulfite concentration of the treatment solution for the main drug part is in the range of 0.0001 to 1.5 mol / l. It is preferably from 0.001 to 1.2 mol / l, more preferably from 0.005 to 1.0 mol / l.
[0080]
Since the pH of the main part processing solution relating to the color developing solution of the present invention is near neutral, a large amount of sulfurous acid can be added, and the storage stability of the solution can be improved.
[0081]
Further, according to the present invention, when a strongly acidic ion is removed in the form of a salt in a method for producing a treatment solution for a main drug part described below, it can be efficiently removed by appropriately adding a conventionally known compound. In that case, two or more types may be used in combination.
[0082]
Further, by adding these solvents, it is possible to prevent precipitation of the color developing agent even if the main agent part has a highly concentrated composition.
[0083]
Examples include, for example, alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, benzyl alcohol, cyclohexanol, and the like. Halogenated derivatives of, dimethylformamide, amides such as dimethylacetamide, acetone, ketone or keto alcohols such as diacetone alcohol, tetrahydrofuran, ethers such as dioxane, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, Oxyethylene or oxypropylene such as tripropylene glycol, polyethylene glycol and polypropylene glycol Addition polymers, alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, 1,2,6-hexanetriol, hexylene glycol, thiodiglycol, glycerin, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl Lower alkyl ethers of polyhydric alcohols such as ether and triethylene glycol monoalkyl ether; and heterocyclic ketones such as sulfolane, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone. Can be
[0084]
Among them, methyl alcohol, ethyl alcohol, tert-butyl alcohol, diethylene glycol, triethylene glycol, polyethylene glycol, ethylene glycol, propylene glycol, thiodiglycol, glycerin, N-methyl-2-pyrrolidone, 1,3-dimethyl-2 -Imidazolidinones are preferred. Among them, methyl alcohol, diethylene glycol and N-methyl-2-pyrrolidone are more preferred.
[0085]
The addition amount is in the range of 0 to 50 w / v%, preferably 0 to 40 w / v%, and more preferably 0 to 30 w / v%.
[0086]
In addition, during the stoppage of application, in a coating apparatus using the processing method of the present invention, a drying inhibitor may be added in order to prevent application failure due to crystallization or drying of the coating liquid at the coating nozzle or the head.
[0087]
Examples of the anti-drying agent include oxyethylene or oxypropylene addition polymers such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polypropylene glycol, ethylene glycol, propylene glycol, and trimethylene. Alkylene glycols such as glycol, butylene glycol, 1,2,6-hexanetriol and hexylene glycol; polyvalent such as thiodiglycol, glycerin, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether and triethylene glycol monoalkyl ether Lower alkyl ethers of alcohol, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazo Heterocyclic ketones such as Zinon like.
[0088]
Preferred are polyhydric alcohols such as diethylene glycol, triethylene glycol, polyethylene glycol, ethylene glycol, propylene glycol, thiodiglycol, and glycerin. Further, more preferably, diethylene glycol, triethylene glycol, and glycerin are preferable.
[0089]
When the present processing liquid is applied to the surface of the light-sensitive material, an organic solvent or a surfactant may be added to adjust the surface tension of the processing liquid so that the processing liquid can be uniformly applied. In this case, two or more types may be used in combination.
[0090]
Examples of organic solvents include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, and diethylene glycol. Ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene B propylene glycol propyl ether, a lower alcohol ether of polyhydric alcohol such as dipropylene glycol butyl ether, and the like.
[0091]
Surfactants include fatty acid salts, hydroxyalkane sulfonates, alkane sulfonates, dialkyl sulfosuccinates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl sulfenyl ether salts, alkyl sulfate esters , Polyoxyethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkyl ether phosphates, perfluoroalkyl carboxylic acids, perfluoroalkyl sulfonic acids, anionic surfactants such as perfluoroalkyl phosphates, Polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, Lioxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, perfluoroalkylethylene oxide adduct, poly (oxyethylene, oxypropylene) methylpolysiloxane copolymer, polyoxyethylene / methylpolysiloxane copolymer And nonionic surfactants such as acetylene glycol ethylene oxide adduct and the like.
[0092]
Of these, preferably anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether phosphate salts and perfluoroalkyl carboxylic acids, polyoxyethylene methylpolysiloxane copolymers and Nonionic surfactants of acetylene glycol ethylene oxide adduct are preferred.
[0093]
The amount of the organic solvent added is preferably 0 to 30 w / v%, and more preferably 0 to 20 w / v%.
[0094]
The addition amount of the surfactant is preferably from 0 to 20 w / v%, more preferably from 0 to 5 w / v%.
[0095]
The surface tension of the main chemical solution adjusted by adding these additives is preferably from 24 to 72 mN / m (measuring temperature 20 to 60 ° C), and more preferably from 25 to 55 mN / m (measuring temperature 20 to 60 ° C). .
[0096]
The thus-prepared main solution can appropriately penetrate into the light-sensitive material without being repelled when applied on the light-sensitive material.
[0097]
The processing liquid of the present invention may contain a viscosity modifier to prevent the processing liquid from flowing out at the time of application to the surface of the light-sensitive material and to uniformly apply the liquid onto the light-sensitive material.
[0098]
As the viscosity modifier, for example, cellulose derivatives such as carboxymethylcellulose and hydroxypropylmethylcellulose, alginates, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, polyethylene glycol, polyacrylamide, methacrylic acid copolymer, and the like are used. Can be.
[0099]
The addition amount of the viscosity modifier is 0 to 10 w / v%, preferably 0 to 5 w / v%, and more preferably 0 to 3 w / v%.
[0100]
The viscosity of the main part treatment liquid obtained by adding the viscosity modifier is preferably 1 to 10 mPa · s (measurement temperature 20 to 50 ° C.), more preferably 1 to 1.5 mPa · s (measurement temperature 20 -50 ° C).
[0101]
<Alkali part treatment liquid>
Next, an alkali part treatment liquid (hereinafter also referred to as an alkali liquid) will be described.
[0102]
As the alkaline agent contained in the alkaline solution, a compound such as potassium hydroxide, sodium hydroxide or lithium hydroxide can be used.
[0103]
The addition amount of the alkali agent is preferably from 0.1 to 5 mol / l, more preferably from 0.1 to 3 mol / l, other than those present as salts of the buffering agent for the alkali agent.
[0104]
Further, as the pH buffer, borate, carbonate, bicarbonate and phosphate of an alkali metal can be used. Preferably, carbonate, phosphate, borate and silicic acid of an alkali metal are used. Salt is good.
[0105]
The addition amount is 0.005 to 2 mol / l, preferably 0.05 to 1.0 mol / l. Thereby, the pH of the alkaline part solution can be maintained in an appropriate range. The pH of the alkali part solution is 12.5 or more, preferably 12.8, and more preferably 13.3.
[0106]
Further, a development inhibitor can be added to prevent fog. Examples include chloride salts, bromide salts, iodide salts, benzimidazoles and benzothiazoles of alkali metals. Among them, iodide salts are preferred. The addition amount may be in the range of 0 to 1.0 mol / l, preferably 0 to 0.5 mol / l, and more preferably 0 to 0.3 mol / l.
[0107]
Further, in order to prevent coating failure after application is resumed due to crystallization of the coating nozzle or head during drying while the application of the alkali part liquid is stopped, the same anti-drying agent as the main part treatment liquid may be added. . In this case, as the applicable compound, the same compound as the compound used in the above-mentioned main part treatment liquid can be used. The amount of the anti-drying agent is 0 to 50 w / v%, preferably 0 to 40 w / v%, more preferably 0 to 30 w / v%.
[0108]
Further, in order to improve the penetration when applied on the light-sensitive material, the same surface tension adjusting agent as the main part treatment liquid may be added. The surface tension of the alkali part liquid after the addition is preferably 20 to 72 mN / m (measurement temperature 20 to 50 ° C), more preferably 25 to 50 mN / m (measurement temperature 20 to 50 ° C).
[0109]
Further, in order to prevent the treatment liquid from flowing out at the time of application and to enable uniform application to the photosensitive material, the same viscosity adjusting agent as that of the main chemical may be added. The viscosity of the treatment liquid after addition is preferably from 0.6 to 1.0 mPa · s (measurement temperature of 20 to 50 ° C.), more preferably from 0.8 to 1.5 mPa · s (measurement temperature of 20 to 50 ° C.).
[0110]
As described above, by using the processing solution (pre-processing solution, main agent part processing solution, alkali part processing solution) of the present invention prepared as described above in the color development step, the accuracy of the color development processing is improved, and a high-quality image is obtained. It is possible to obtain.
[0111]
In addition, an organic preservative and a fluorescent whitening agent may be appropriately added to the treatment liquid of the present invention.
[0112]
For example, as the organic preservative, hydroxylamine and hydroxylamine derivatives, for example, organic preservatives represented by the following general formula [I], which are common to the above-mentioned main part solution and alkali part solution, are preferable.
[0113]
Embedded image

[0114]
This compound is a hydroxylamine derivative disclosed in JP-A-2000-162750, and can efficiently prevent the oxidation of the processing solution.
[0115]
In this case, the addition amount is preferably 0.0005 to 0.08 mol / l, and more preferably 0.01 to 0.06 mol / l.
[0116]
In addition, a surfactant such as polyoxyethylene alkylphenyl ether or a triazinylstilbene-based fluorescent whitening agent can be added to both the main part liquid and the alkaline part liquid.
[0117]
In this case, the addition amount is preferably 0.0005 to 0.08 mol / l, and more preferably 0.01 to 0.06 mol / l.
[0118]
<Processing method>
Next, the processing method of the present invention will be described.
[0119]
The processing method of the present invention is a processing method for a silver halide color photographic light-sensitive material including a color developing step, wherein the color developing step is a pre-processing step of processing with a pre-processing solution, and a main chemical solution processed with a color developing agent solution. And a step of treating with an alkaline solution.
[0120]
The outline will be described below with reference to the drawings while comparing the color developing solution of the present invention with a conventional color developing solution. FIG. 1 is a schematic view of a color developing step of a two-liquid coating method in a conventional processing method, and FIG. 2 is a view schematically showing a color developing step using a color developing solution of the present invention in a processing method of the present invention. .
[0121]
As shown in FIG. 1, in the conventional color developing solution, only a two-step process of applying a base solution and then applying an alkali solution is performed. Since it becomes darker and lower at the bottom, it causes image unevenness. In particular, there were many problems in the dry processing using a high-concentration processing solution, but according to the constitution of the color developing solution of the present invention, it is possible to prevent such permeation unevenness and to improve the color development and photographic characteristics.
[0122]
As shown in FIG. 2, in the color developing solution of the present invention, a pretreatment liquid is applied and penetrated in advance before applying the main chemical solution, so that the main chemical solution can be drawn into the photosensitive material when the main chemical solution is applied. Thus, after the application of the alkali solution, the color development reaction occurs evenly to the inside, so that the color developability can be improved.
[0123]
In other words, the pretreatment liquid is applied to the photosensitive material in advance in the pretreatment step, so that the penetration of the main drug is increased in the next main chemical liquid coating step, so that the coloring reaction generated in the alkali liquid coating step is balanced in each color layer of the light sensitive material. Because it is performed well, the quality of the image can be improved. Further, since the penetration of the processing solution into the photosensitive material is accelerated, the processing time can be shortened, and the processing efficiency is improved.
[0124]
Next, the overall configuration including the steps after the color development step (hereinafter also referred to as post-processing steps) will be described.
[0125]
In the post-processing step, silver generated on the light-sensitive material developed using the color developing solution of the present invention in the color developing step is oxidized and dissolved in the desilvering step, and further washed with water in the washing step, or a fungicide. A series of treatments are performed by washing in a stabilization step containing a dye or a dye stabilizer. Further, a drying step for drying the processed photosensitive material can be usually provided after the washing / stabilizing step.
[0126]
Here, the desilvering step basically includes a bleaching step of oxidizing silver generated in the development with a bleaching solution, and a fixing step of converting oxidized silver into a silver salt soluble in a fixing solution. ing. However, the bleaching step and the fixing step can be processed as separate steps using a bleaching solution and a fixing solution, respectively.However, the bleaching solution and the fixing solution are mixed so that bleaching and fixing can be performed simultaneously. The bleaching step and the fixing step can be performed integrally by using a bleach-fixing solution (bleach-fixing step). Depending on the processing step, the bleaching step, the fixing step, and the bleach-fixing step can be appropriately combined. For example, after bleaching or fixing, a bleach-fixing step using a bleach-fix solution can be further provided. That is, the following procedure can be specifically exemplified as the processing method of the present invention. However, the processing method of the present invention is not limited to these.
1) Color development-Bleaching-Fixing-Washing (stable) -Drying-Scan
2) Color development-Bleaching-Fixing-Rinse (stable)-Scan
3) Color development-bleach-fix-dry-scan
4) Color development-bleaching-fixing-scan
5) Color development-fixing-washing with water (stable)-drying-scanning
6) Color development-fixing-washing with water (stable)-scanning
7) Color development-fixing-drying-scan
8) Color development-fixing-scan
9) Color development-Bleaching-Washing (stable) -Dry-Scan
10) Color development-Bleaching-Rinse (stable)-Scan
11) Color development-bleach-dry-scan
12) Color development-bleach-scan
13) Color development-Bleach-fix-Rinse (stable)-Dry-Scan
14) Color development-Bleach-fix-Rinse (stable)-Scan
15) Color development-bleach-fix-dry-scan
16) Color development-bleach-fix-scan
17) Color development-washing with water (stable)-drying-scanning
18) Color development-Rinse (stable)-Scan
19) Color development-drying-scanning
20) Color development-scan
Among these, steps 1 to 16 are preferable, and steps 1, 2, 4 to 6 and 8 are more preferable.
[0127]
As described above, when the post-processing step is provided after the color development step, the transmittance of the light-sensitive material is improved, so that scanning is completed in a short time, that is, so-called scan suitability is improved.
[0128]
In the processing method of the present invention, in the color development step, immersion processing may be performed, a processing solution may be directly applied to the light-sensitive material, or these processings may be used in combination. Similarly, the treatment after the color development step may be immersion treatment, direct application, or combined use.
[0129]
Further, a squeezing process for scraping the processing solution remaining on the light-sensitive material may be performed between the respective steps (squeezing step). Thereby, the permeability of the next processing liquid to be applied can be increased. In addition, in the case of the impregnation treatment, it can be prevented from being carried into the next tank, so that the treatment efficiency is improved.
[0130]
Next, each step will be described sequentially.
[0131]
<Color development process>
In the color developing step according to the present invention, processing is performed using the above-described color developing solution of the present invention. That is, the pretreatment liquid is applied to the photosensitive material in advance, then the main chemical liquid is applied, and then the alkali part processing liquid is applied.
[0132]
Here, in the above-described method, not only the configuration of applying the pretreatment liquid-the main agent part treatment solution-the alkali part treatment solution once each, but also the configuration of applying each treatment solution plural times or in combination with the single application. There may be. As an example, the following steps are raised.
1. Pretreatment-main chemical-alkali
2. Pretreatment-multiple times of main chemical-alkali
3. Pretreatment-main chemical-alkali multiple times
4. Pretreatment-multiple times of main chemical-multiple times of alkali
5. (Pretreatment-main chemical) multiple times-alkali multiple times
6. (Pretreatment-main drug-alkali) multiple times
Among these, 1, 3, and 5 are preferable.
[0133]
In the conventional coating method, the color developing solution and the alkali solution were each applied only once. Therefore, when processing photographic materials having different sensitivities, the amount of the main agent required was different, but one apparatus was used. However, according to such a configuration, the amount of the active ingredient required for each photosensitive material can be applied in a plurality of times, so that each color layer can sufficiently develop color. And the photographic characteristics of the image are also good.
[0134]
Further, a squeezing step may be provided between the above three steps. As a result, the carry-on component to the next process occurs, so that the efficiency of the process can be improved. In this case, a roller, a sponge, or a squeeze blade can be used as the squeeze material, and thereby the coating liquid adhering to the surface of the photosensitive material is removed. Among these, the roller may be water-absorbing or non-water-absorbing.
[0135]
As described above, in the processing method of the present invention, the pre-processing solution is applied to the photosensitive material in advance before the application of the color developing agent solution in the color developing step, so that the penetration of the color developing agent solution and the alkali solution to be subsequently applied is performed. The image quality can be improved, the obtained image quality can be improved, and the photographic characteristics can be improved.
[0136]
The pretreatment liquid may be 1 to 3000 ml / m2 for a silver halide color photographic light-sensitive material. ² To supply. Preferably 5 to 1000 ml / m ² , More preferably 10 to 500 ml / m ² Desirably supplied.
[0137]
Here, the color developing agent contained in the main solution is 0.01 to 0.5 mol / m 2 based on the silver halide color photographic light-sensitive material. ² To be supplied. When the supply amount is in this range, even when supplying the necessary amount of the main drug to the photosensitive material, there is no problem that the applied liquid flows down from the photosensitive material and is wasted, and a precipitate is generated at the nozzle of the coating device. There is an advantage that is not. In addition, 0.015 to 0.35 mol / m ² Preferably supplied, 0.025-0.17 mol / m ² More preferably, it is supplied.
[0138]
Next, the alkali agent contained in the alkali solution to be applied is 0.005 to 1 mol / m with respect to the silver halide color photographic light-sensitive material. ² To be supplied. When the supply amount is within this range, even when supplying the necessary amount of alkali to the photosensitive material, there is no problem that the applied liquid flows down from the photosensitive material and is wasted, and a precipitate is generated at the nozzle of the coating device. There is an advantage that is not. In this case, 0.007 to 0.33 mol / m ² Preferably supplied, 0.007 to 0.07 mol / m ² Is more preferred.
[0139]
Both processing solutions have a coating amount of 1 to 3000 ml / m on the light-sensitive material. ² And preferably 5 to 1000 ml / m ² , More preferably 10 to 500 ml / m ² Is preferred.
[0140]
As a result, an appropriate amount of the processing liquid permeates all the dye layers of the photosensitive material, and a high-quality image can be obtained by an appropriate reaction.
[0141]
The temperature at the time of application is in the range of 25 to 70C, preferably 30 to 65C, more preferably 40 to 60C.
[0142]
In addition, the coating time is set in the range of 3 seconds to 5 minutes, preferably 5 seconds to 2 minutes 30 seconds, more preferably 5 seconds to 2 minutes.
[0143]
Further, the number of times of application may be a plurality of times as long as it is between 1 and 20 times. Preferably 1 to 12 times, more preferably 1 to 5 times.
[0144]
Further, as described above, it is possible to apply a plurality of main chemicals alone within the above range, or to apply a plurality of main chemicals-alkali liquids.
[0145]
When processing photosensitive materials with different sensitivities in one apparatus, the conventional method requires only one application, so the main chemical solution required by each photosensitive material cannot be supplied, resulting in insufficient color development or image quality. Although there was a problem of causing unevenness, in the processing method of the present invention, the amount of liquid required for each photosensitive material can be supplied by applying a plurality of times. It is possible to obtain photographic characteristics and to improve the image quality.
[0146]
As described above, in the color development processing by the coating method, by applying the pretreatment liquid before applying the main chemical liquid, it is possible to improve the penetration of the processing liquid into the inside of the photosensitive material, thereby improving the image. Can be possible. Further, the processing time itself can be significantly reduced as compared with the related art.
[0147]
<Post-processing step>
Next, a post-processing step after the color development step will be described.
[0148]
In the treatment method of the present invention, since the treatment is carried out by a dry method, each of the post-treatment steps can also be carried out by a coating treatment, but of course, it is also possible to carry out the impregnation treatment in a treatment tank as before.
[0149]
<Bleaching process>
First, the composition of the processing solution used in the bleaching step will be described.
[0150]
In the bleaching step according to the present invention, a bleaching solution containing a bleaching agent, a bleaching accelerator, a rehalogenating agent, a pH buffer, and other additives as described below can be used.
[0151]
As the bleaching agent, iron (III) aminopolycarboxylate, persulfuric acid or the like is used. Specifically, ethylenediaminetetraacetic acid, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, nitrilotriacetic acid, hydroxymethyliminodiacetic acid, N -(2-carboxyethyl) iminodiacetic acid, N- (2-carboxymethyl) iminodiacetic acid, β-alanine diacetate, ethylenediamine-N, N′-disuccinic acid, 1,3-propanediamine-N, N ′ Iron (III) salts such as disuccinic acid, ethylenediamine-N, N'-dimalonic acid, and 1,3-propanediamine-N, N'-dimalonic acid can be used.
[0152]
The amount of the bleaching agent added is preferably 0.005 to 2 mol / l, more preferably 0.01 to 1.0 mol / l.
[0153]
In the bleaching solution of the present invention, a bleaching accelerator such as a mercapto compound, a disulfide compound, and a thiol compound can be used.
[0154]
Further, a rehalogenating agent may be added. For example, alkali metal chlorides, bromides, iodides, and ammonium salts such as ammonium chloride, ammonium bromide, and ammonium iodide can be used.
[0155]
The addition amount of the rehalogenating agent is preferably 5 mol / l or less. It is preferably from 0.5 to 3.0 mol / l, more preferably from 1.0 to 2.0 mol / l.
[0156]
Further, a chelating agent can be added. By way of example, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids can be used. Specifically, ethylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, nitrilotriacetic acid, hydroxymethyliminodiacetic acid, N -(2-carboxyethyl) iminodiacetic acid, N- (2-carboxymethyl) iminodiacetic acid, β-alaninediacetate, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N , N, N-trimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, and the like.
[0157]
The amount of the chelating agent is preferably 20 mol% or less of the bleaching agent.
[0158]
Further, as the pH buffer, for example, organic acids such as acetic acid, succinic acid, malonic acid, maleic acid, glutaric acid, and oxalic acid can be used. The addition amount is 0 to 5 mol / l, preferably 0.1 to 2 mol / l.
[0159]
In order to prevent corrosion of the stainless steel in the treatment tank, a nitrate such as ammonium nitrate or sodium nitrate is used as a corrosion inhibitor. The concentration of the nitric acid compound is preferably from 0.3 to 4.0 mol / l, more preferably from 0.5 to 3.5 mol / l.
[0160]
The pH of the processing solution (bleaching solution) used in the bleaching step is preferably in the range of 2 to 6, and more preferably in the range of 3 to 5.
[0161]
In the case of the impregnation process, the replenishment amount of the bleaching solution in the continuous process is 1 m of the photosensitive material. ² Per volume is preferably 25 to 200 ml.
[0162]
The treatment temperature is preferably 30 to 60 ° C, preferably 30 to 50 ° C, and more preferably 35 to 45 ° C.
[0163]
The processing time is in the range of 20 seconds to 3 minutes, preferably in the range of 20 seconds to 1 minute 30 seconds, and more preferably in the range of 20 seconds to 1 minute.
[0164]
In the case of the coating treatment, the coating amount is 1 to 3000 ml / m ² And preferably 5 to 1000 ml / m ² , More preferably 10 to 500 ml / m ² Is good.
[0165]
The treatment temperature of the coating treatment is 25 to 70 ° C, preferably 30 to 65 ° C, and more preferably 40 to 60 ° C.
[0166]
Further, the processing time may be the same as the impregnation processing.
[0167]
In the case of the coating treatment, a plurality of coatings may be performed, and the number of coatings may be in the range of 1 to 20 times. Preferably 1 to 12 times, more preferably 1 to 5 times.
[0168]
In addition, in the case of the coating treatment, the drying agent used in the above color development step is used in order to prevent coating defects at the time of non-coating by crystallization and drying of the coating liquid in a coating nozzle and a coating head, and thereafter, when coating is resumed. It can also be used.
[0169]
In this case, the amount of addition is in the range of 1 to 50 w / v%, preferably 1 to 40 w / v%, more preferably 2 to 30 w / v%.
[0170]
Further, in order to uniformly apply the composition on the light-sensitive material, the same surface tension adjusting agent as that added to the color developing solution can be added. In this case, the surface tension of the treatment liquid after the addition of the modifier is preferably 25 to 72 mN / m (measurement temperature 20 to 50 ° C), more preferably 25 to 55 mN / m (measurement temperature 20 to 50 ° C). is there.
[0171]
Further, the same viscosity modifier as that added to the color developing solution can be added so that the processing solution does not flow out after application to the light-sensitive material. In this case, the viscosity of the treatment liquid after the addition of the modifier is preferably 1 to 2000 mPa · s (measurement temperature 20 to 50 ° C.), and more preferably 1 to 500 mPa · s (measurement temperature 20 to 50 ° C.).
[0172]
<Fixing step>
Next, the processing liquid relating to the fixing step of the present invention will be described.
[0173]
In the fixing step according to the present invention, a fixing solution containing the following fixing agent, decomposition inhibitor, chelating agent and other additives is used.
[0174]
As the fixing agent, thiosulfates such as ammonium thiosulfate and sodium thiosulfate are preferably used. Further, two or more known fixing agents such as thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, thioether compounds such as ethylenebisthioglycol, and thiourea may be used in combination.
[0175]
The addition amount of the fixing agent is 0.01 to 5.0 mol / l, preferably 0.1 to 3.0 mol / l, and more preferably 0.5 to 2.0 mol / l.
[0176]
Examples of the decomposition inhibitor include sulfites such as ammonium sulfite, potassium sulfite and sodium sulfite, bisulfites such as ammonium bisulfite, potassium bisulfite and sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite. Metabisulfites, hydroxylamines, reductones such as ascorbic acid, and sulfinic acid can be used as necessary.
[0177]
These decomposition inhibitors are used in the range of 0.001 to 1.5 mol / l, preferably 0.0 to 0.5 mol / l, more preferably 0.0 to 0.25 mol / l.
[0178]
As a chelating agent, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid and the like can be used.
[0179]
Specifically, ethylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, nitrilotriacetic acid, hydroxymethyliminodiacetic acid, N -(2-carboxyethyl) iminodiacetic acid, N- (2-carboxymethyl) iminodiacetic acid, β-alaninediacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N , N, N-trimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid and the like.
[0180]
The amount of the chelating agent used is preferably 0.1 to 5 g / l.
[0181]
It is also preferable to add a pH buffer having a pKa of 5 to 9. This makes it possible to prevent the decomposition of the fixing agent and the sulfidation.
[0182]
Examples of such compounds include the following compounds.
Ethylenediamine (pKa7.47), N-methylethylenediamine (pKa7.56), N-ethylethylenediamine (pKa7.63), Nn-propylethylenediamine (pKa7.54), N-isopropylethylenediamine (pKa7.70), N -(2-hydroxylethyl) ethylenediamine (pKa7.21)
N, N-dimethylethylenediamine (pKa6.79), N, N-diethylethylenediamine (pKa7.07), N, N′-dimethylethylenediamine (pKa7.47), N, N′-diethylethylenediamine (pKa7.77), N, N′-di-n-propylethylenediamine (pKa7.53), N, N′-di (2-hydroxylethyl) ethylenediamine (pKa7.18), N, N, N ′, N′-tetramethylethylenediamine ( pKa 6.56), 1,2-diaminopropane (pKa 7.13), meso-2,3-diaminopropane (pKa 6.92) triethylenetetramine (pKa 6.67), 1,2,3-triaminopropane (pKa7 .95), 1,3-diamino-2-aminomethylpropane (pKa6.44) and the like.
[0183]
Further, an aminopyridine-based compound having an acid dissociation constant (pKa) in the range of 5.5 to 8.5 may be used. Preferably, the pKa is in the range of 6.3 to 7.8. If the pKa is 5.5 or less, the pH of the processing solution is lowered to promote the decomposition of thiosulfate, and if the pKa is 8.5 or more, the bleaching ability is reduced. Specific examples include compounds such as 2-aminopyridine (pKa 6.78) and 3-aminopyridine (pKa 6.06).
[0184]
It is also preferable to use a compound having a structure represented by the following general formulas [II], [III], and [IV].
[0185]
Embedded image

[0186]
In Formula [II], R1 and R2 each represent a linear or branched alkylene group, and may be substituted with an amino group, an alkylamino group, a sulfo group, or a hydroxyl group. n is 0-8. R11, R12, R13, R14 and R15 each represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms (however, may be substituted with an amino group, an alkylamino group, a sulfo group or a hydroxyl group), an acyl group , An aryl group or a hydroxyl group. R11 and R12, R12 and R15, R15 and R14, R14 and R13, R11 and R13, and R12 and R14 each may form a heterocyclic ring, or may form a connected bis-form. good. Further, not all amino groups contained in the formula [II] are tertiary amines.
[0187]
In Formula [IV], A represents any one of a hydrogen atom, an alkyl group, and a hydroxyl group, and the alkyl group may be an alkyl group substituted with one or both of a hydroxyl group and an amino group. A in one molecule may be all the same or a combination of these substituents. M is 11 to 1700.
[0188]
In addition to the above compounds, imidazole and imidazole derivatives may be added.
[0189]
The addition amount of these pH buffers is preferably 0.0001 to 5 mol / l.
[0190]
By adjusting the pH in this manner, the pH of the fixing solution is preferably in the range of 5 to 10, more preferably 6 to 9.
[0191]
Further, a development terminator can be added. By doing so, the development processing can be stopped immediately after the color development step, so that the processing can be sped up.
[0192]
Compounds to be added include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl -Nitrogen-containing heterocyclic compounds such as benzimidazole, indazole, hydroxyazaindolizine and adenine, 1-phenyl-5-mercaptotetrazole, and alkali metal chloride salts, bromide salts, iodide salts and ammonium chloride, and bromide. Ammonium salts such as ammonium and ammonium iodide salts can be used, preferably, alkali metal bromide salts, iodide salts and ammonium salts such as ammonium bromide and ammonium iodide salts, 1-phenyl-5 Mercaptotetrazole, etc. is good.
[0193]
The addition amount is 0.001 to 1 mol / l, preferably 0.005 to 0.5 mol / l.
[0194]
The replenishment amount in the case of the impregnation treatment is 250 to 1400 ml / m ² The treatment temperature is 30 to 60 ° C., preferably 30 to 50 ° C., and more preferably 35 to 50 ° C.
[0195]
The processing time may be in the range of 5 seconds to 5 minutes, preferably 10 seconds to 2 minutes 30 seconds, more preferably 10 seconds to 2 minutes.
[0196]
In the case of the coating treatment, the coating amount is 1 to 3000 ml / m ² But preferably 5 to 1000 ml / m ² , More preferably 10 to 500 ml / m ² Is good.
[0197]
Further, the processing temperature is in the range of 25 to 70C, preferably 30 to 65C. Moreover, 40-60 degreeC is more preferable.
[0198]
The number of times of application may be plural, preferably 1 to 12 times, more preferably 1 to 12.
Five times is good.
[0199]
In addition, in the case of the coating treatment, a drying inhibitor used in the color development process is added as a drying inhibitor in order to prevent application failure due to crystallization and drying of the coating solution at the coating nozzle or the head while the processing is stopped. You may. In this case, two or more kinds may be added. Thereby, coating unevenness at the time of restarting coating can be prevented.
[0200]
The amount of addition may be 1 to 50 w / v%, preferably 1 to 40 w / v%, more preferably 2 to 30 w / v%.
[0201]
Further, in order to improve the uniformity of the processing solution applied to the surface of the photosensitive material, a surfactant may be added to adjust the surface tension. The viscosity modifier used is the same as that used in the color development step, and the viscosity of the processing solution after addition is preferably from 1 to 2000 mPa · s, more preferably from 1 to 500 mPa · s.
[0202]
<Bleaching and fixing process>
In the bleach-fixing step, the above-described bleaching step and fixing step are performed in one process.
[0203]
In the bleach-fixing solution, aminopolycarboxylic acid iron (III) salt, persulfuric acid and the like can be used as the bleaching agent. For the bleaching solution, an iron complex salt which has been complexed in advance as a ferric complex salt may be used, or a complexing compound with a ferric sulfate salt, iron (III) nitrate, ferric chloride or the like may be used. To form a complex in the solution.
[0204]
Specific examples of aminopolycarboxylic acids include ethylenediaminetetraacetic acid, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, nitrilotriacetic acid, and hydroxymethyl Iminodiacetic acid, N- (2-carboxyethyl) iminodiacetic acid, N- (2-carboxymethyl) iminodiacetic acid, β-alanine diacetate, ethylenediamine-N, N′-disuccinic acid, 1,3-propanediamine —N, N′-disuccinic acid, ethylenediamine-N, N′-dimalonic acid, 1,3-propanediamine-N, N′-dimalonic acid and the like.
[0205]
Next, thiosulfates such as ammonium thiosulfate and sodium thiosulfate are preferably used as the fixing agent in the bleach-fix processing solution. Further, two or more kinds of other known fixing agents such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, thioether compounds such as ethylenebisthioglycolic acid and thiourea may be used in combination.
[0206]
The addition amount is preferably in the range of 0.1 to 5 mol / l, and more preferably 0.1 to 3 mol / l. Moreover, 0.5-2 mol / l is more preferable.
[0207]
Examples of the bleach-fix accelerator used in the bleach-fix solution include a mercapto compound, and other disulfide compounds and thiol compounds.
[0208]
Specific examples include 3-mercapto-1,2,4-triazole, diethylaminoethanethiol, and the like.
[0209]
Examples of the decomposition inhibitor include sulfites such as ammonium sulfite and sodium sulfite, bisulfites such as ammonium bisulfite and potassium bisulfite, metabisulfites such as ammonium metabisulfite and potassium metabisulfite, and hydroxylamines. And reductones such as ascorbic acid and sulfinic acid can be used as needed.
[0210]
The amount of the decomposition inhibitor can be used in the range of 0.005 to 3.0 mol / l, preferably in the range of 0.005 to 2.0 mol / l, more preferably in the range of 0.005 to 1.0 mol / l. Is good.
[0211]
As a chelating agent, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid and the like can be used.
[0212]
Specifically, ethylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, nitrilotriacetic acid, hydroxymethyliminodiacetic acid, N -(2-carboxyethyl) iminodiacetic acid, N- (2-carboxymethyl) iminodiacetic acid, β-alaninediacetate, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N , N, N-trimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid and the like.
[0213]
The addition amount of the chelating agent is preferably 0.0001 to 5 mol / l.
[0214]
Further, a pH buffering agent may be added for preventing the decomposition and fixing of the fixing agent.
[0215]
Examples of such compounds include the following compounds.
Ethylenediamine (pKa7.47), N-methylethylenediamine (pKa7.56), N-ethylethylenediamine (pKa7.63), Nn-propylethylenediamine (pKa7.54), N-isopropylethylenediamine (pKa7.70), N -(2-hydroxylethyl) ethylenediamine (pKa7.21)
N, N-dimethylethylenediamine (pKa6.79), N, N-diethylethylenediamine (pKa7.07), N, N′-dimethylethylenediamine (pKa7.47), N, N′-diethylethylenediamine (pKa7.77), N, N'-di-n-propylethylenediamine (pKa7.53), N, N'-di (2-hydroxylethyl) ethylenediamine (pKa7.18), N, N, N ', N'-tetramethylethylenediamine ( pKa 6.56), 1,2-diaminopropane (pKa 7.13), meso-2,3-diaminopropane (pKa 6.92), triethylenetetramine (pKa 6.67), 1,2,3-triaminopropane (pKa pKa 7.95), 1,3-diamino-2-aminomethylpropane (pKa 6.44) and the like.
[0216]
Further, an aminopyridine-based compound having an acid dissociation constant (pKa) in the range of 5.5 to 8.5 can be used. Preferably, the pKa is in the range of 6.3 to 7.8. If the pKa is 5.5 or less, the pH of the processing solution is lowered to promote the decomposition of thiosulfate, and if the pKa is 8.5 or more, the bleaching ability is reduced. Specific examples include compounds such as 2-aminopyridine (pKa 6.78) and 3-aminopyridine (pKa 6.06).
[0217]
Further, a compound having a structure represented by the general formulas [II], [III], and [IV] described in the fixing step may be used.
[0218]
Further, imidazole, imidazole derivatives, or organic acids such as acetic acid, succinic acid, malonic acid, maleic acid, glutaric acid, and oxalic acid can also be used.
[0219]
The addition amount of these pH buffers is preferably 0.0001 to 5 mol / l.
[0220]
Further, the pH of the bleach-fix solution thus obtained is preferably 4 to 9.
[0221]
In the bleach-fixing process of the present invention, either the impregnation process or the coating process may be used.
[0222]
In the case of the impregnation treatment, the replenishment amount of the bleach-fixing solution is 5 to 216 ml / m ² As long as it is preferably 5-70 ml / m ² , More preferably 5-35 ml / m ² Is good.
[0223]
The treatment temperature is in the range of 30 to 60C, preferably 30 to 50C, more preferably 35 to 45C.
[0224]
The processing time may be in the range of 20 seconds to 3 minutes, preferably 20 seconds to 2 minutes 30 seconds, and more preferably 20 seconds to 2 minutes.
[0225]
In the case of the coating treatment, the coating amount of the bleach-fixing solution is 1 to 3000 ml / m ² And 5 to 1000 ml / m ² Is preferably 10 to 500 ml / m ² Is more preferred.
[0226]
The processing temperature is 25 to 70 ° C, preferably 30 to 65 ° C, more preferably 40 to 60 ° C.
[0227]
The processing time can be arbitrarily set in the range of 3 seconds to 5 minutes, but preferably 5 seconds to 2 minutes, more preferably 5 seconds to 1 minute and 20 seconds.
[0228]
The application may be performed a plurality of times, preferably 1 to 12 times, more preferably 1 to 5 times.
[0229]
Further, in the case of a coating treatment, a drying inhibitor, a surface tension adjuster and a viscosity adjuster can be added in the same manner as in the color development step. The amounts of these additions may be the same as in the color development step.
[0230]
<Washing and / or stabilizing step>
In the washing and / or stabilizing step of the present invention, instead of a large amount of washing water, a rinsing liquid containing a chemical rinsing agent, an anti-dropping agent, a fungicide / antifungal agent, a chelating agent, a dye stabilizer, etc. Can be used. The washing water and the rinsing liquid may be used in combination, or the treatment may be performed using only the rinsing liquid.
[0231]
A surfactant can be used as the water droplet preventing agent. Particularly, a nonionic surfactant is preferable.
[0232]
Further, in the processing method of the present invention, a fungicide / antifungal agent can be contained in order to prevent the generation of bioslime in the processing tank and the mold generated in the processed photographic material. Usually, the amount of the fungicide / fungicide added is in the range of 0.01 to 0.1 g / l, but by adding the treating agent of the present invention to the treating solution in the washing and / or stabilizing step, It is possible to increase the amount of the fungicide / fungicide to be added up to 10 times the usual amount of the fungicide / fungicide.
[0233]
Specific examples of the antibacterial and antifungal agents include the following.
[0234]
Alcohol-based fungicides such as ethanol, propanol, isopropyl alcohol, 2-bromo-2-nitro-propanol and N- (2-hydroxypropyl) -aminoethanol. Phenol fungicides such as piosol, thymol, о-phenylphenol, methylphenol, parachlorophenol, chlorophen, and 2,4,6-tribromophenol. Aldehyde-based fungicides such as formaldehyde, glutaraldehyde, benzaldehyde and α-bromocinnamaldehyde. Carboxylic acid-based fungicides such as benzoic acid and its derivatives, undecylenic acid metal complex, undecylenic acid ethanolamide, propionic acid, caprylic acid, and sorbic acid. ester-based fungicides such as p-hydroxybenzoic esters (parabens) and fatty acid monoglycerides. Ether-based fungicides such as 2,4,4'-trichloro-2'-hydroxydiphenyl ester; Nitrile-based fungicides such as tetrachloroisophthalonitrile. Peroxide-based fungicides such as hydrogen peroxide, peracetic acid, ethylene oxide and propylene oxide. Halogen-based fungicides such as parachlorophenyl-3-iodopropargyl formal diclofluamide, chlorinated isocyanuric acid, and 2-bromo-2-nitro-1,3-propanediol. Pyridine and quinoline fungicides such as 8-oxyquinoline and 2,3,5,6-tetrachloropyridine derivatives. Triazine-based fungicides such as N, N ', N "-trishydroxymethylhexahydro-S-triazine; Isothiazoline fungicides such as 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and benzoisothiazoline derivatives. Imidazole / thiazole fungicides such as thiobendazole derivatives and benzothiazole derivatives; Anilide-based fungicides such as chlorocarbanilide derivatives. Biguanide fungicides such as cyclohexidine gluconate, chlorhexidine hydrochloride, polyhexamethylene biguanidine hydrochloride. Dithiocarbamate-based fungicides such as alkyldithiocarbamate derivatives. Disulfide-based fungicides such as dithio-2-2'-bisbenzamide. Carbohydrate-based fungicides such as chitosan, polyglucosamine and aminoglycoside. Tropolone-based fungicides such as natural hinokitiol. Surfactant-based fungicides such as octadecylamine acetate, alkyldiaminoethylglycine, polyoxyalkyleneammonium, and benzalkonium chloride. Organometallic fungicides such as 8-oxyquinoline metal complexes, glutamic acid derivative metal complexes, and naphthenic acid metal complexes.
[0235]
Among the above compounds, alcohol-based antifungal agents, carboxylic acid-based antifungal agents, ester-based antifungal agents, halogen-based antifungal agents, isothiazoline-based antifungal agents, disulfide antifungal agents, surfactant-based antifungal agents, Antibacterial and antifungal agents such as chlorophenyl-3-iodopropargyl formal diclofluamide and 2-bromo-2-nitro-1,3-propanediol suppress bioslime, suppress yellow stain (Stain) increase, and image It is preferable from the viewpoint of the influence on storage stability and the like. More preferably, antibacterial and protective agents such as formaldehyde, ester-based fungicides, parachlorophenyl-3-iodopropargyl-formal diclofluamide, 2-bromo-2-nitro-1,3-propanediol, and disulfide-based fungicides. Fungicides are good.
[0236]
Two or more of the above-mentioned antibacterial and fungicidal agents may be used in combination in the stabilization step.
[0237]
Further, the following antibacterial and bacteria-eliminating methods may be used in combination with the above fungicide.
[0238]
Treatment tanks, rollers, filters, etc. using antibacterial zeolites in which metal ions such as copper, zinc and silver are supported on zeolites, antibacterial ceramics, etc. May be used together.
[0239]
Further, a general antibacterial method such as an ultraviolet lamp, an ultrasonic vibration, and an energizing treatment may be used together. Also, a disinfection method using an antibacterial filter or the like may be used in combination.
[0240]
As the image stabilizer, formalin, aldehydes or methylol urea, or a formalin releasing compound such as hexamethylenetetramine can be used.
[0241]
The amount of the image stabilizer added is preferably 0.0001 to 0.01 mol / l.
[0242]
In addition, antistatic agents such as dioctyl ether sulfosuccinate, sodium lauroyl sarcosine, distearyl dimethyl ammonium chloride, and triazinyl stilbene-based fluorescent whitening agents are used to prevent adhesion of dust due to static electricity to the dried photosensitive material. And the like.
[0243]
Further, organic solvents such as diethylene glycol, ethanol, ethylene glycol, N-methyl-2-pyrrolidone, butylcellosolve, γ-butyrolactone, and triethanolamine can be used.
[0244]
Further, as a chelating agent, aminopolycarboxylic acid, alkylphosphonic acid, alkylsulfonic acid, phosphonocarboxylic acid and the like can be added.
[0245]
The addition amount of the chelating agent is preferably 0.00001 to 0.2 mol / l, and more preferably 0.00001 to 0.02 mol / l.
[0246]
Furthermore, in order to prevent the decomposition of the fixing agent used in the above-mentioned step, the compounds (a), (b) and (c) represented by the general formulas [II], [III] and [IV] described in the fixing step are used. ), Or a sulfite or a bisulfite as a decomposition inhibitor.
(A) Compound [II] represented by the following general formula
(B) Aminopyridine compound represented by the following general formula [III]
(C) Polyethyleneimine [IV] represented by the following general formula.
[0247]
Here, when the compound (a) or (b) is used, it is preferably used in the treatment solution of the washing and / or stabilization step in the range of 0.0001 to 1 mol / l, more preferably 0.0002 to 1 mol / l. The range of -0.1 mol / l is good.
[0248]
When the compound (c) is used, it is preferably used in the treatment solution of the water washing and / or stabilizing step in the range of 0.00001 to 0.3 mol / l, more preferably 0.00005 to 0.1 mol / l. The range of l is good.
[0249]
When sulfite or bisulfite is added, it is preferably used in the range of 0.0004 to 2 mol / l, more preferably 0.0008 to 0.16 mol / l.
[0250]
Further, a pH buffer for adjusting the pH may be added.
[0251]
Organic acids such as acetic acid, propionic acid, succinic acid, maleic acid, glycine, taurine and glycolic acid may be used as the pH buffer in order to keep the pH of the stabilizing solution within a certain range. In particular, a buffer (pKa = 4 to 8) having a buffering ability in a pH range of 4 to 8 is preferable.
[0252]
Further, the pH of the rinsing liquid is preferably from 3 to 9, and more preferably from 4 to 8.
[0253]
As a processing method, as in the above-described processing steps, impregnation processing or coating processing may be used.
[0254]
In the case of the impregnation process, the replenishment amount of the stabilization processing solution tank in the continuous process is 1 m ² The volume is preferably 25 to 2500 ml, more preferably 150 to 1800 ml.
[0255]
The processing temperature is preferably from 30 to 45 ° C. The processing time is preferably from 15 seconds to 10 minutes, particularly preferably from 30 seconds to 5 minutes.
[0256]
As the stabilization processing liquid tank according to the present invention, any method such as a single tank, a multi-stage counter-current cascade system, and a multi-stage parallel flow system can be adopted, but the multi-stage counter-current cascade system is preferable.
[0257]
In the multi-stage countercurrent cascade system, there are usually two or more stabilization processing liquid tanks, and the liquid replenished in the final tank overflows and flows into the previous tank sequentially, and waste liquid is discharged from the foremost tank. Configuration. In this case, since the processing liquid flows from the direction opposite to the processing direction of the photosensitive material, the final tank has a structure in which the salt concentration is the lowest, and the salts of the photosensitive material can be gradually washed with a clean processing liquid. Therefore, the salts of the photosensitive material can be removed with a small amount of processing liquid as in the case of running water. Further, the number of processing tanks is preferably 3 to 8.
[0258]
Next, in the case of the coating treatment, the coating amount is 1 to 3000 ml / m ² And preferably 5 to 500 ml / m. ² , More preferably 10 to 300 ml / m ² Is good.
[0259]
The treatment temperature may be from 10 to 70 ° C, preferably from 30 to 65 ° C, more preferably from 40 to 60 ° C.
[0260]
The processing time is 10 seconds to 5 minutes, preferably 10 seconds to 2 minutes, and more preferably 10 seconds to 1 minute and 20 seconds.
[0261]
The number of times of application can be 1 to 20 times, preferably 1 to 12 times, more preferably 1 to 5 times.
[0262]
In the case of the coating treatment, in order to prevent the treatment liquid from being dried and crystallized at the coating nozzle and the head and to uniformly apply the coating on the photosensitive material, as in the above-described processing steps, a drying inhibitor, a surface tension adjusting agent, It is preferable to add an agent and a viscosity modifier.
[0263]
In this case, the amount of each addition is the same as in each of the above processing steps.
[0264]
<Squeeze process>
A squeezing step may be provided between each of the above-described steps to scrape excess processing liquid on the photosensitive material. By doing so, the cleaning efficiency is improved at the last cleaning. In addition, in the processing method of the present invention, crystallization does not occur by a reaction even when a processing solution is applied on the light-sensitive material.
[0265]
As a squeezing method, a coating solution adhering to the surface of the photosensitive material may be removed with a roller, a sponge, a squeeze blade, or the like.
[0266]
Urethane or the like can be used as the squeeze material.
[0267]
<Image processing step>
In the processing method of the present invention, an image can be digitized using the photosensitive material thus developed.
[0268]
For example, it is possible to digitally process an image by scanning the photosensitive material in a wet state after color development, or to scan after the photosensitive material is once dried.
[0269]
In addition, the post-processing step can be appropriately selected and performed depending on the purpose or the photosensitive material to be used.
[0270]
In this case, it is also possible to perform the processing in a state where the photosensitive material is wet after the water washing processing, or to perform the processing after performing the drying processing after the water washing processing.
[0271]
As the image processing apparatus used in the present invention, a conventionally known scanner or the like can be used.
[0272]
In addition, a conventionally known image processing software can be used as an image processing application.
[0273]
<Processing device>
Next, a processing apparatus for performing the processing method of the present invention will be described with reference to the drawings. In the processing method of the present invention, any of the steps other than the color development step can be performed by a coating method or a conventional impregnation method. preferable. In the dry processing by the coating method, since the development processing is performed by directly applying the processing liquid to the surface of the photosensitive material, a small amount and high concentration of the processing liquid can be directly applied to the photosensitive material, thereby increasing the processing efficiency and reducing waste liquid. There is an effect that hardly appears.
[0274]
First, the processing method of the present invention using this dry processing will be described.
[0275]
FIG. 3 is a process chart for explaining the processing steps of the entire dry processing.
[0276]
As a pretreatment, a presoaking liquid is applied to the photosensitive material (step 1). By applying the pretreatment liquid (presoaking liquid) of the present invention, it is possible to enhance the permeability of the processing liquid described below to the light-sensitive material. It becomes possible and the processing efficiency can be improved. Next, a color developing solution is applied. In the color developing solution according to the present invention, a main part processing solution (main solution) and an alkali part processing solution (alkaline solution) are applied in two parts (steps 2 and 3). ).
[0277]
After a series of processes relating to the color development process is completed, a bleaching solution is applied as a desilvering process (step 4), and then a fixing solution is applied (step 5). Alternatively, a bleach-fix solution may be applied instead of the bleach solution or the fix solution (step 6). This dissolves and removes silver deposited on the light-sensitive material. Then, the processing solution remaining on the light-sensitive material is washed and removed by applying a washing / stabilizing processing solution (step 7). The sensitized material that has been processed in this manner is subjected to a drying process (step 8), or is scanned by a scanner without performing the drying process to perform image processing to convert the image into digital data (step 9).
[0278]
In this way, in the processing method of the present invention, it is possible to shorten the processing time while improving the quality of the image by applying a small amount of the high-concentration processing liquid.
[0279]
In the above example, all the processing is performed, but the present invention is not limited to this, and it is also possible to perform only necessary processing at any time according to the photographic material used and the purpose.
[0280]
Next, a processing apparatus used for the dry processing will be described.
[0281]
FIG. 4 is a schematic diagram of a dry film process (hereinafter, also referred to as DFP) apparatus 100 (hereinafter, also referred to as an apparatus of the present invention) according to the present invention.
[0282]
The apparatus 100 has a configuration in which all processes related to the DFP process are continuously performed. Hereinafter, an outline of the device configuration will be described.
[0283]
First, the DFP apparatus 100 according to the present invention includes a conveyor belt 101 for mounting a photosensitive material (sensitive material) 105 and transporting the photosensitive material 105 to each processing unit, a roller 102 for rotating the conveyor belt 101, and a roller 102. A drive unit (not shown) for driving is provided.
[0284]
The apparatus 100 also includes a pre-soaking unit 110 for performing a process before applying the color developing solution, a color developing solution applying unit 120 for applying the color developing solution, and a device for uniformly dispersing the color developing solution to the dye layer in the photosensitive material. , A bleaching unit 140 for oxidizing and depositing silver in a color developing solution with a bleaching solution, a fixing unit 150 for applying a fixing solution for dissolving and removing the deposited silver, and a bleaching and fixing process. A bleach-fixing unit 160 using one processing solution, a washing / stabilizing unit 170 for washing out each of these processing solutions from the surface of the photosensitive material, an overcoating unit 180 for performing processing for preserving the photosensitive material without deteriorating, and a drying unit (Not shown) and each processing unit of the scanning unit 107 for scanning an image from the processed photosensitive material and a photosensitive material collecting unit 103 for collecting processed photosensitive material are provided.
[0285]
As described above, according to the configuration of the present embodiment, the photosensitive material 105 is automatically conveyed sequentially to each processing unit by the above-described conveyor belt 101, and the processing liquid is applied to each processing unit, thereby performing a series of development. Processing can be performed automatically.
[0286]
As shown in FIG. 5, each of these processing units is provided with an application nozzle 210 for applying each processing solution onto the photosensitive material 105, a replenishment processing solution tank 201 in which a replenishment processing solution is filled, and an application of the replenishment processing solution. An application unit 200 including a pipe 203 for supplying a processing liquid from the replenishment processing liquid tank 201 to the application nozzle 210 is provided to supply the processing liquid to the nozzle 210.
[0287]
A curtain coater head 211 is provided at the tip of the application nozzle 210, and the treatment liquid is applied through the head.
[0288]
In addition, since the coating unit 200 is further provided with a temperature control mechanism (not shown) for controlling the temperature of the processing liquid, it is possible to apply the processing liquid at an appropriate processing temperature.
[0289]
In the embodiment of the present invention, after the photosensitive material 105 is placed on the belt conveyor, the photosensitive material 105 is transported to the color developing unit 120, the bleaching unit 140, the fixing unit 150, the bleach-fixing unit 160, and the washing / stabilizing unit 170. After the respective treatment liquids are applied, they are provided in the washing / stabilizing unit 170, and the photosensitive material surface is absorbed by a water absorbing roller 181 made of a water absorbing material, and then conveyed to the scanning unit 107 in a wet state to be subjected to image processing. It has become. The processed photosensitive material is wound up and collected by the photosensitive material collection unit 103. Alternatively, for example, when the scanner is not installed in the apparatus and a separate scanner is used, the image processing is performed by scanning the photosensitive material after drying the photosensitive material in the drying unit. .
[0290]
Here, in the color developing section 120, the color developing agent liquid part 121 and the alkaline liquid part 122 have independent coating units 200, respectively, and apply the processing liquid individually. When the photosensitive material 105 is conveyed to the processing section, the main chemical solution is first applied and then allowed to permeate for about 30 seconds, and then an alkaline agent is applied and permeated for about 5 seconds to 2 minutes to cause a color development reaction. . With such a configuration, the color developing agent can be permeated into the entire photosensitive material to prevent color unevenness, so that the quality of a developed image can be improved.
[0291]
Further, the change of the permeation time can be changed by changing the discharge position of the processing agent or changing the conveying speed of the photosensitive material. In the case of film processing, it is common to mix a wide variety of photosensitive materials, so when inserting a photosensitive material into an automatic processor, read information such as sensitivity from the barcode of the patrone of the photosensitive material, The processing time of the photosensitive material can be automatically changed.
[0292]
Further, since the pH of the main chemical solution of the color developing solution of the present invention exceeds 7, an excessive reaction does not occur when an alkali solution is applied repeatedly, and the resulting development unevenness can be prevented. . Further, thereby, the processing efficiency can be improved, and the processing time can be significantly reduced as compared with the related art.
[0293]
Further, in the device 100 according to the present invention, after the main chemical solution is applied in the main chemical solution part 121, the surface of the photosensitive material 105 is leveled by the squeeze roller 123 so that the applied main chemical solution is made uniform. .
[0294]
Here, the squeeze roller 123 is made of non-water-absorbing material Teflon (registered trademark), and after applying a color developing solution, the photosensitive material surface is leveled in a certain direction. Since the roller 123 is made of a non-water-absorbing material, no chemical solution adheres to the roller surface and no dust adheres. Therefore, even if the photosensitive material is continuously processed, It is possible to always adjust the coating liquid to a constant thickness without attaching dust or liquid.
[0295]
Here, in the conventional coating process, if the coating unevenness occurs when the first processing liquid is applied, the unevenness cannot be eliminated even in the subsequent processing liquid application, and the deterioration is worsened. As a result, image unevenness occurs. As a result, there is a problem that the image quality deteriorates. However, in the coating processing apparatus 100 according to the present invention, since the surface of the photosensitive material is made uniform by using the rollers 123 in this manner, the main chemical solution is uniformly applied on the photosensitive material, and each processing is performed in the subsequent processing. The liquid can be applied uniformly, and image quality can be improved by preventing image unevenness.
[0296]
Also, in other processing units, it is possible to apply only a required amount of the processing liquid to the surface of the light-sensitive material in the coating processing, so that the amount used can be reduced. Further, since almost no waste liquid is generated, it is preferable from an environmental point of view.
[0297]
The coating process differs from the impregnation process in that when a high-concentration processing solution is used, the processing solution is not brought in from the previous tank to the next tank depending on the photosensitive material. Processing can be performed in the state, and the reaction speed of the photosensitive material is increased, so that the processing time can be shortened and the processing efficiency can be improved.
[0298]
With the above configuration, the DFP device 100 according to the present invention can perform various processes on the photosensitive material, and can pass through the processing unit without performing unnecessary processing according to the photosensitive material. . As a result, a wide range of processing can be performed flexibly corresponding to various photosensitive materials.
[0299]
Next, the coating head 211 used for the coating nozzle 210 of the DFP device 100 will be described in detail. 6 is a schematic external view of the coating nozzle 210 and the coating head 211, and FIG. 7 is a longitudinal sectional view showing the inside of the coating head.
[0300]
The head 211 of the coating nozzle 210 used in the present embodiment is generally called a slit orifice coater, and the material is stainless steel, aluminum, or titanium, and preferably titanium. By using such a material, acid resistance and alkali resistance are improved, and it is possible to cope with various processing solutions having various pH ranges.
[0301]
As shown in FIG. 6, a slit 212 for discharging each processing liquid is provided at the center of the bottom surface of the head 211 that is tapered and raised. This slit 212 has a width of about 0.05 to 0.3 mm, preferably 0.05 to 0.2 mm. The coating width (nozzle width) is approximately 15 to 80 mm, preferably 15 to 60 mm. With such a slit, it is possible to efficiently and uniformly apply both the concentrated color developing agent part solution and the concentrated part solution.
[0302]
A plurality of rectifying plates 213 made of stainless steel, aluminum, or titanium and serving as weirs to adjust the flow of the processing liquid are provided at equal intervals on the raised bottom of the head with the slit 212 as the center. In the coating process according to the present invention, since a concentrated and high-concentration processing solution is used, it is difficult to apply a predetermined range in a certain direction even when discharged from the slit 212. It is possible to prevent the liquid from flowing backward and bias, and to appropriately apply the photosensitive material to the entire application range.
[0303]
As shown in FIG. 7, the inside of the coating head 211 according to the present embodiment is provided with a comb-shaped coating guide 214 so that the processing liquid can be straightened into a curtain and uniformly applied to the photosensitive material 105. I have. The length of the guide 214 is adjusted so that the center is longest and the left and right ends are shortest. Accordingly, even when a processing solution having a higher concentration than the conventional processing solution is applied, the processing solution can be uniformly applied to the entire sheet width without the processing solution being concentrated at the center of the photosensitive material 105. .
[0304]
As described above, the processing method of the present invention uses the apparatus 100 according to the present invention described above, so that the amount of the processing liquid used is small and the processing time can be significantly reduced as compared with the conventional impregnation processing. Specifically, in the conventional impregnation process, 18 ml of the color developing replenisher is required per 1 m of the light-sensitive material (35 mm film), but in the processing method according to the present invention, the processing can be performed at 5 ml or less per 1 m. Conventionally, the color developing process is performed over 3 minutes or more, but the color developing process can be performed within about 120 seconds in the processing method according to the present invention.
[0305]
In the present embodiment, the processing is performed using the above-described application nozzle, but the present invention is not limited to this. For example, an inkjet nozzle may be used. However, since the processing solution used in the alkali developing agent application section 122 of the color developing solution applying section 120 for applying the alkali agent of the color developing solution is strongly alkaline and cannot be processed by a normal inkjet nozzle, the present invention relates to the present invention. It is preferable to use a coating head. In the present embodiment, the rectifying plate 213 is provided outside, but is not limited to this. For example, even if provided inside the slit of the head, the flow rate and directionality of the processing liquid can be adjusted efficiently. Can be applied.
[0306]
Note that the present invention is not limited to the above embodiment. For example, a squeeze roller may be provided between each application unit, and this roller may be used as a water absorbing member.
[0307]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. However, it is needless to say that the present invention is not limited to this embodiment.
[0308]
<Production Example 1>
Manufacture of color developer
CD-4 (4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline monosulfate as a color developing main solution was produced by the following methods.
[0309]
In addition, in the examples, the equipment used, the analysis conditions, etc. used the following common ones.
Analysis conditions
1) Ion chromatography
・ HPLC manufactured by JASCO Corporation
DG-980-50 Degasser
PU-980 Intelligent HPLC pump
LG-980-02 Low pressure gradient autosampler
CO-960 column oven
LCSS-905 system station
・ Detector Showa Denko KK
SHodex ICI-524A
Eluent 2.5 mM * o-phthalic acid (Tokyo Kasei Co., Ltd.) aqueous solution pH 4.0 (adjusted with 0.1 M * Tris (hydroxymethyl) aminomethane (Tokyo Kasei Co., Ltd.) aqueous solution)
・ Flow rate 2ml / min
・ Temperature 40 ℃
2) Liquid chromatography
・ HPLC manufactured by JASCO Corporation
DG-980-50 Degasser
PU-980 Intelligent HPLC pump
LG-980-02 Low pressure gradient unit
AS-950 Intelligent Autosampler
CO-960 column oven
LCSS-905 system station
・ Detector Finepack SIL C18S manufactured by JASCO Corporation
・ Eluent 3.75 mM phosphoric acid (Kanto Chemical Co., Ltd.) pH 4.0 (adjusted with potassium hydroxide (Kanto Chemical Co., Ltd.)): acetonitrile (Kanto Chemical Co., Ltd.) = 1: 1, flow rate 0 ml / Min
・ Temperature 40 ℃
3) Surface tension: KRUSS Bubble Pressure Tensiometer BP2 (measured 1 second after the surface is formed)
4) Viscosity measurement: Single cylindrical rotary viscometer Bismetron VG4 manufactured by Shibaura System Co., Ltd.
Manufacturing method 1
While stirring with a magnetic stirrer at room temperature, 1.69 mol of 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline monosulfate and 1.14 mol of potassium bisulfite were added to 494 ml of pure water. After dissolution, 1.19 mol of N-methyl-2-pyrrolidone and 1.11 mol of diethylene glycol are added.
[0310]
The finished liquid volume of the above mixture is adjusted to 1077 ml.
[0311]
Next, 3.24 mol of potassium hydroxide (flakes) is gradually added to the above-mentioned mixed solution while controlling the temperature to 40 ° C. or lower in a water bath to neutralize the mixture.
[0312]
Thereafter, the mixture is allowed to stand at 15 ° C. or lower for 15 minutes or more, and suction filtration is performed using 5C filter paper (retained particle size: 1 μm) to remove potassium sulfate. Then, the liquid volume after the removal is set to 1000 ml, and the finished pH is set to 7.2.
[0313]
The content of CD-4 in the thus prepared main drug solution is 1.69 mol / l. The concentration of CD-4 was analyzed by liquid chromatography, and it was confirmed that the above value was obtained.
[0314]
The sulfate ion concentration after the removal as potassium sulfate was confirmed by ion chromatography, and it was confirmed that the ion was not detected in the main drug solution. (Removal rate 100%; molar ratio with the main drug 0)
Manufacturing method 2
At room temperature, 1.07 mol of 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline monosulfate was dissolved in 737 ml of pure water, and then 0.9 mol of potassium bisulfite and N-methyl- 0.94 mol of 2-pyrrolidone and 0.88 mol of diethylene glycol were added, and the mixture was sufficiently stirred with a magnetic stirrer in a mixing vessel. The finished amount was 1360 ml.
[0315]
Next, 1.84 mol of potassium hydroxide (flakes) was gradually added while controlling the temperature to 40 ° C. or lower in a water bath to perform neutralization. Further, potassium sulfate was precipitated and removed in the same manner as in Production Method 1.
[0316]
Finally, the finished volume was adjusted to 1000 ml.
[0317]
The sulfate ion concentration of the main drug solution thus obtained was analyzed and confirmed by ion chromatography. As a result, the sulfate ion in the main drug solution was 0.25 mol / l, the removal rate was 77%, and the molar ratio to the main drug was 77%. It was confirmed to be 0.77.
[0318]
The concentration of CD-4 was confirmed by liquid chromatography, and it was confirmed that CD-4 was 1.07 mol / l.
[0319]
Next, a main drug solution for a comparative test was produced. For the comparative example, two types of compositions were prepared: a one-component composition in which a main chemical solution and an alkaline solution were mixed, and a two-component composition in which a main chemical solution part and an alkaline solution part were separated. The production formula is shown below.
[0320]
Test prescription
Manufacturing method comparison 1 one-component composition
Dissolved water +
Sodium bromide 0.013mol
Hydroxylamine sulfate 0.03mol
Sodium bisulfite 0.014mol
Potassium carbonate 0.28mol
4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline monosulfate 0.015 mol
The above composition was added to pure water, and pure water was further added to make 1 L.
The pH was adjusted to 12.5 with potassium hydroxide and sulfuric acid.
[0321]
Manufacturing method comparison 2
Active drug part
4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline monosulfate
1.50 mol and 0.24 mol of sodium bisulfite were added to pure water to make 1 L.
[0322]
pH = 2.0
The following tests were performed using each of the main chemical solutions obtained as described above.
[0323]
<Example 1>
Influence test on development activity with and without pre-treatment (pre-soaking) process
Development was performed under the following conditions, and the effect of development activity was tested with and without the presoaking treatment.
[0324]
·Test condition
Coating device: The slit orifice coater according to the present invention (nozzle width 25 mm, depth 0.1 mm) is used.
[0325]
Photosensitive material: SUPERIA400, Fuji Photo Film Co., Ltd.
Test piece: The above photosensitive material was subjected to wedge exposure at a color temperature of 5500 ° using a JIS III type sensitometer manufactured by Mestec Co., Ltd.
Coating solution: The main agent part solution shown below and the alkali part solution described in the comparative prescription were used. Pure water was used as the presoaking liquid.
[0326]
Coating method: The above-mentioned coater is arranged perpendicularly to the direction of transport of the photosensitive material for each treatment liquid, and the coating solution is applied to the surface of the photosensitive material from the slit of the coater while transporting the photosensitive material at 5 mm / sec.
[0327]
Test method
1: The transfer processing is performed in 5 seconds between the nozzles while applying each processing liquid.
2: After processing, remove the photosensitive material and wash it for 1 minute.
3: The post-processing step (bleaching-fixing-stabilizing-drying) is performed on the photographic material using a QSF-V50 automatic developing machine manufactured by Noritsu Koki Co., Ltd. without passing through the color developing step. The recipe of the post-treatment step is as follows.
[0328]
<Adjustment of treatment liquid>
<Color developer>
The color developing solution was adjusted as follows using the main agent of the above Production Example.
[0329]
Active agent 1: Pure water was added to the composition of manufacturing method 1 described in the manufacturing method described in the manufacturing method of the active agent part to adjust the active agent concentration to 1 mol / l.
[0330]
Main drug 2: Pure water was added to the composition of Comparative 2 described in Comparative prescription, and the main drug concentration was adjusted to 1 mol / l.
[0331]
Adjustment of alkaline solution (B1 to B3)
The following compound was dissolved in pure water with stirring to make up to 1000 ml.
[0332]
KH ₂ PO ₄ 0.15mol
KOH described in Table 3 mol
Surfactant
Triton H-66 30g
(Manufactured by Union Carbide Limited)
Megafac F-120 1g
(Dai Nippon Ink)
PH = described in Table 3.
<Bleach replenisher>
Acetic acid 1.2 mol
1,3-PDTA ferric salt 0.45mol
Ammonium bromide 100g
Ammonium nitrate 100g
Add water and 1L
Adjusted to pH 3.5
<Bleach>
A 70% dilution of the bleaching replenisher was adjusted to pH 4.5.
[0333]
<Fixing replenisher>
Ammonium thiosulfate 1.22mol
Ammonium bisulfite 0.52mol
0.35 mol of triethylenetetramine
0.04 mol of ethylenediaminetetraacetic acid
Add water and 1L
Adjusted to pH 6.85
<Fixer>
A 50% dilution of the fixing replenisher was adjusted to pH 6.85 before use.
[0334]
Evaluation criteria
The state of the surface of the light-sensitive material at the time of application was visually evaluated.
[0335]
A processing solution having a high concentration of the developing agent hardly permeates the light-sensitive material, so that the photographic density hardly increases. Therefore, evaluation was performed by comparing the maximum density values.
[0336]
For the evaluation, measurement was performed with StatusM using an X-Rite310TR densitometer.
[0337]
Admission decision
The difference between the Dmax density of cyan and the density of stain is
1.0 or more ○
Less than 1.0 to 0.9 or more △
Less than 0.9 ×
It was determined.
[0338]
The results of this test are shown below.
[Table 1]

[0339]
In this test, an existing automatic developing machine was used after the color development step, and when the color development step was completed, the development reaction was stopped (STOP) with a 3 w / w% aqueous acetic acid solution.
[0340]
In the above table, the main drug 1 and the main drug 2 are as described above.
[0341]
From the above results, it was found that the photographic density was improved by performing the presoaking step.
[0342]
<Example 2>
Digital processing test of images with and without presoaking liquid application
·Test condition
For the application of the main chemical, a modified version of a bubble jet (registered trademark) printer was used, and the same coater as in Example 1 was used for the other coating devices and photosensitive materials. A test piece was produced in the same manner as in Example 1.
[0343]
Application method
The pretreatment, the alkali solution, the fixing solution, and the washing water were applied.
[0344]
The main solution was applied by filling the BX-3 ink cartridge with the main solution using a Canon BJ printer. At this time, the coating medium was set to a BJ cloth, and the liquid was discharged in an error diffusion mode as print quality fine. The coating amount is 37ml / m ² And
[0345]
Adjustment of coating liquid
Presoaking liquid: pure water was used.
[0346]
A1-4: The liquid of the main drug 2 prepared by the comparative prescription was diluted with pure water so as to have the molar concentration of the main drug shown in Table 2 below to prepare the main drug liquid of the comparative example.
[0347]
A5-7: The main drug solution according to the present invention was prepared by diluting the main drug part solution prepared in Production Example 1 with pure water so as to have the molar concentration of the main drug shown in Table 2 below.
[0348]
B1-3: The alkali part solution (potassium hydroxide 1.06 mol / l) 1 shown in Table 3 was used.
[0349]
[Table 2]

[0350]
[Table 3]

[0351]
Treatment method: Each treatment solution was applied as follows.
[0352]
Pretreatment liquid 5 seconds / 1 time application, 25 ° C
Main drug part solution 31 seconds / one application, 25 ° C
Alkali part solution 20 seconds / one application, 45 ° C
Fixing solution 70 seconds, 45 ° C
Rinse water 5 seconds, 45 ° C
Drying 5 seconds, 60 ℃
Evaluation method
1: In the conventional coating and developing treatment, since the cyan density is hardly increased and the image quality is softened, the density difference ΔD between cyan Dmax and cyan Dmin was measured to evaluate the image quality after the processing.
[0353]
2: The processed light-sensitive material was data scanned by Quick Scan 35 of Minolta Co., Ltd., and was processed by Adobe Photoshop Ver. After adjusting the image at 6.0, print output was performed using a QSS3001 Digital automatic machine manufactured by Noritsu Koki Co., Ltd., and it was evaluated whether a finish equivalent to the C41 process was obtained.
[0354]
Evaluation criteria
1: Cyan ΔD> 1.00 was made practical.
2: When an actual image equivalent to the C41 process is obtained by adjusting the printing conditions, the digital data obtained by the main coating process can be converted to an image equivalent to the normal process. For this reason, the exposure condition of the QS3001 Digital automatic machine was adjusted, and the image having a finished image equivalent to that of the C41 process was made practical.
[0355]
result
The results of this test are shown in the table below.
[0356]
[Table 4]

[0357]
<Example 3: Difference in effect due to physical properties of pretreatment liquid>
The following test was conducted to confirm how the viscosity of the pretreatment liquid and the surface tension salt concentration affect the pretreatment step.
[0358]
Test condition
Coating device: Used according to Examples 1 and 2.
[0359]
Photosensitive material: The same test pieces as in Examples 1 and 2 were used, and test pieces were prepared in the same manner as in the above test.
[0360]
Coating liquid
Main drug part liquid: prepared by diluting the liquid of Comparative 2 prepared by the comparative prescription with pure water so as to be 1 mol / l of the main drug.
[0361]
Alkaline part solution: The alkali part solution (potassium hydroxide 1.06 mol / l) described in the comparative formulation was used.
[0362]
Pretreatment liquid: The pretreatment liquid (PS (presoaking) liquid) shown in the following table was used.
Confirmation test of penetration effect by viscosity: A pretreatment liquid having the composition shown in Table 5 below was used.
[0363]
[Table 5]

[0364]
In addition, sodium alginate was used as a thickener.
[0365]
Confirmation test of penetration efficiency by surface tension: Pretreatment liquids shown in Table 6 below were used.
[0366]
[Table 6]

[0367]
In addition, F-120 (megafac) and H-66 were used as surface tension adjusters.
[0368]
Confirmation of penetration efficiency by electric conductivity (salt concentration): As shown in Table 7 below, Na was so adjusted that electric conductivity was as follows. ₂ SO ₄ Was dissolved in pure water while stirring to obtain each pretreatment liquid.
[0369]
[Table 7]

[0370]
Each test method was as follows.
1: Conveying processing is performed between nozzles in 5 seconds while supplying each coating liquid.
2: Remove the photosensitive material from the slit orifice coater and wash for 1 minute.
3: A bleaching-fixing-stabilizing-drying process is performed without using a color developing step by using a QSF-V50 automatic developing machine manufactured by Noritsu Kogyo Kiki Co., Ltd.
[0371]
The composition of the processing solution after the bleaching step was the same as in Example 1.
Evaluation criteria
By changing the viscosity and surface tension of the presoaking solution, the effect of improving the penetration rate of the main drug was weakened. Therefore, the maximum photographic densities when the viscosity of the presoaking solution was changed were compared.
[0372]
The concentration was measured with StatusM using a densitometer X-Rite310TR.
[0373]
In addition, the state of the surface of the light-sensitive material at the time of application (whether or not the treatment liquid has flowed out of the light-sensitive material) was visually evaluated.
[0374]
Admission decision
When the photographic density and the degree of development unevenness were superior to the processing without the presoaking step, it was evaluated as effective.
[0375]
-Density evaluation: An effect was evaluated as being effective if the difference between the Dmax density and the stain density of cyan was 1 or more with or without the presoaking step.
[0376]
Density evaluation: Difference between Dmax density of cyan and density of stain
：: 1.0 or more
Δ: less than 1.0 to 0.9 or more
×: less than 0.9
It was determined.
[0377]
-Unevenness evaluation: It evaluated as follows.
：: No development unevenness
Δ: Development unevenness in the same state as without pre-soaking step
X: A state where development unevenness is severe.
result
The test results are shown in Table 8 below.
[Table 8]

[0378]
<Example 4: Difference in effect due to composition of pretreatment step>
In the pre-processing step, it was confirmed how much the pre-processing solution contained the amount of the developing agent and the amount of alkali did not prevent the penetration of the main agent part.
[0379]
The coating device, photosensitive material and test piece were the same as in Example 1.
[0380]
Coating solution: As shown in Table 9 below, the main agent process liquid (main agent 1) used in Example 1 and the alkali process solution (B3, KOH 1.06 mol / l) used in Example 1 were each diluted. Used.
[0381]
[Table 9]

[0382]
Test method: Performed in the same manner as in Example 1.
[0383]
Evaluation method: The maximum photographic density values of the uppermost layer of the photographic material, which had the greatest effect when the developer concentration was changed, were compared. The density value was measured with StatusM using a densitometer X-Rite310TR.
[0384]
Pass / Fail Judgment: When the value ΔDmax obtained by comparing the yellow Dmax in each main agent concentration treatment with the pure water treatment was within ± 0.03, it was evaluated that it was not involved in the development reaction.
[0385]
Results: The results of the above test are shown in Table 10 below.
[0386]
[Table 10]

[0387]
As described above, even when the pretreatment liquid contains not only water but also a predetermined amount of the main agent and the alkali, the color development step can be favorably performed without lowering the penetration rate of the main agent. It was shown.
[0388]
In addition, this embodiment is not limited to the method by application, and may be used for the method by impregnation.
[0389]
【The invention's effect】
As described above, according to the processing method of the present invention and the color developing solution used therein, the pretreatment liquid is applied and permeated to the photosensitive material before the main chemical liquid is applied, thereby improving the permeability of the main chemical liquid. As a result, when an alkaline solution is applied, a sufficient color-forming reaction can be obtained even in the color layer at the bottom of the light-sensitive material, and the image quality is improved. In addition, since the penetration rate of the main chemical solution is improved, the processing efficiency can be improved.
[Brief description of the drawings]
FIG. 1 is a schematic diagram illustrating a conventional two-liquid coating method.
FIG. 2 is a schematic diagram illustrating a coating method according to the present invention.
FIG. 3 is a process chart showing a coating process according to the present invention.
FIG. 4 is an overall configuration diagram of a coating processing apparatus according to the present invention.
FIG. 5 is a schematic view of a coating unit for performing the processing method of the present invention.
FIG. 6 is a schematic diagram of a coating nozzle for performing the processing method of the present invention.
FIG. 7 is a cross-sectional view showing the inside of a head used for a coating nozzle according to the present invention.
[Explanation of symbols]
100 ... DFP device
105 ... sensitive material
110 ... Pre-soaking part
200 ... Coating unit
210 ... Coating nozzle
211 ... Coating head

Claims (19)

A method for processing a silver halide color photographic light-sensitive material including a color development step, wherein the color development step comprises:
A pretreatment step of applying a pretreatment liquid to the photosensitive material surface,
A main chemical solution process for applying a color developing main chemical solution,
A method of processing a silver halide color photographic light-sensitive material, comprising an alkali solution step of applying an alkali solution. 2. The method according to claim 1, wherein the pre-processing step is performed before the main chemical solution step to swell the emulsion layer of the light-sensitive material. 3. The method according to claim 1, wherein the color developing step is performed by repeating the preprocessing step and the main chemical liquid step a plurality of times, and then performing an alkali liquid coating step. . The pretreatment liquid contains the color developing agent,
The silver halide color according to any one of claims 1 to 3, wherein the content of the color developing agent is 2/5 or less of the amount of the color developing agent contained in the color developing agent solution. Processing method of photographic photosensitive material. The pretreatment liquid contains the alkaline agent,
The silver halide color photographic light-sensitive material according to any one of claims 1 to 3, wherein the content of the alkaline agent is 1/10 or less of the amount of the alkaline agent contained in the alkaline solution. Processing method. The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 5, wherein the conductivity of the preprocessing solution is 80 mS / m or less. The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 3, wherein the pretreatment liquid is water. The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 5, wherein the surface tension of the pretreatment liquid is 25 to 70 mN / m. 8. The method according to claim 1, wherein the viscosity of the pretreatment liquid is 25 mPas or less. 10. The method according to claim 1, wherein the main drug solution has a pH> 7 and contains at least one selected from the following compound group (A) in a molar ratio of less than 1 to the main compound. The method for processing a silver halide color photographic light-sensitive material described in the above item.
Compound group (A)
Sulfate ion chloride ion nitrate ion p-toluenesulfonic acid ion sulfonate ion 11. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the alkaline solution has a pH of 12.5 or more. A method for processing a silver halide color photographic light-sensitive material including a color development step,
The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 11, wherein the method is immersed and / or coated in the pretreatment liquid, the main chemical liquid, or the alkali liquid. A method for processing a silver halide color photographic light-sensitive material, further comprising an image processing step of converting an image obtained by the processing method according to claim 1 into digital data. A pretreatment liquid for swelling the photosensitive material,
A color developing agent solution containing at least 1 to 2 mol / l of a color developing agent, having a pH> 7.0, and having at least one kind of strong acid ion selected from the following compound group (A) in a ratio to the main agent of less than 1;
A processing agent for a silver halide color photographic light-sensitive material, comprising an alkaline solution having a pH of 12.5 or more.
Compound group (A)
Sulfate ion chloride ion nitrate ion p-toluenesulfonic acid ion sulfonate ion The pretreatment liquid contains the color developing agent,
15. The processing solution for a silver halide color photographic light-sensitive material according to claim 14, wherein the content of the color developing agent is 2/5 or less of the amount of the color developing agent contained in the color developing agent solution. The pretreatment liquid contains the alkaline agent,
The processing solution for a silver halide color photographic light-sensitive material according to claim 14, wherein the amount of the alkali agent contained in the alkali solution is 1/10 or less. 15. The processing solution for a silver halide color photographic light-sensitive material according to claim 14, wherein the preprocessing solution is water. 18. The processing solution for a silver halide color photographic material according to claim 14, wherein the surface tension of the preprocessing solution is 25 to 70 mN / m. 19. The processing solution for a silver halide color photographic light-sensitive material according to claim 14, wherein the viscosity of the preprocessing solution is 25 mPa · s or less.

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