JP3605779B2 - Automatic processor for silver halide photographic materials - Google Patents

Description

【００５６】
一般式〔Ｈ〕において、Ｒ_１及びＲ_２は同時に水素原子ではないそれぞれアルキル基、アリール基、Ｒ′−ＣＯ−基又は水素原子を表すが、Ｒ_１及びＲ_２で表されるアルキル基は、同一でも異なってもよく、それぞれ炭素数１〜３のアルキル基が好ましい。更にこれらアルキル基はカルボン酸基、リン酸基、スルホン酸基、又は水酸基を有してもよい。Ｒ′はアルコキシ基、アルキル基又はアリール基を表す。Ｒ_１，Ｒ_２及びＲ′のアルキル基及びアリール基は置換基を有するものも含み、また、Ｒ_１及びＲ_２は結合して環を構成してもよく、例えばピペリジン、ピリジン、トリアジンやモルホリンの如き複素環を構成してもよい。
【００５７】
【化２】

【００５８】
一般式〔Ｂ〕において、Ｒ_１１，Ｒ_１２，Ｒ_１３は水素原子、置換又は無置換の、アルキル基、アリール基、又はヘテロ環基を表し、Ｒ_１４はヒドロキシ基、ヒドロキシアミノ基、置換又は無置換の、アルキル基、アリール基、ヘテロ環基、アルコキシ基、アリールオキシ基、カルバモイル基、アミノ基を表す。ヘテロ環基としては、５〜６員環であり、Ｃ，Ｈ，Ｏ，Ｎ，Ｓ及びハロゲン原子から構成され飽和でも不飽和でもよい。Ｒ_１５は−ＣＯ−，−ＳＯ_２−又は−Ｃ（＝ＮＨ）−から選ばれる２価の基を表し、ｎは０又は１である。特にｎ＝０の時Ｒ_１４はアルキル基、アリール基、ヘテロ環基から選ばれる基を表し、Ｒ_１３とＲ_１４は共同してヘテロ環基を形成してもよい。
【００５９】
一般式〔Ｈ〕の化合物のうち、下記一般式〔Ｄ〕で示される化合物が特に好ましい。
【００６０】
【化３】

【００６１】
一般式〔Ｄ〕において、Ｌはアルキレン基を表し、Ａはカルボキシル基、スルホ基、ホスホノ基、ホスフィン酸基、ヒドロキシル基、アミノ基、アンモニオ基、カルバモイル基又はスルファモイル基を表し、Ｒは水素原子又はアルキル基を表す。Ｌ，Ａ，Ｒはいずれも、直鎖も分岐鎖も含み、無置換でも置換されていてもよい。ＬとＲが連結して環を形成してもよい。
【００６２】
一般式〔Ｄ〕で示される化合物について更に詳細に説明する。式中、Ｌは炭素数１〜１０の直鎖又は分岐鎖の置換してもよいアルキレン基を表し、炭素数１〜５が好ましい。具体的には、メチレン、エチレン、トリメチレン、プロピレン等の基が好ましい例として挙げられる。置換基としては、カルボキシル基、スルホ基、ホスホノ基、ホスフィン酸基、ヒドロキシル基、アルキル置換してもよいアンモニオ基を表し、カルボキシル基、スルホ基、ホスホノ基、ヒドロキシル基が好ましい例として挙げられる。Ａはカルボキシル基、スルホ基、ホスホノ基、ホスフィン酸基、ヒドロキシル基、又は、アルキル置換してもよいアミノ基、アンモニオ基、カルバモイル基又はスルファモイル基を表し、カルボキシル基、スルホ基、ヒドロキシル基、ホスホノ基、アルキル置換してもよいカルバモイル基が好ましい例として挙げられる。−Ｌ−Ａの例として、カルボキシメチル基、カルボキシエチル基、カルボキシプロピル基、スルホエチル基、スルホプロピル基、スルホブチル基、ホスホノメチル基、ホスホノエチル基、ヒドロキシエチル基が好ましい例として挙げることができ、カルボキシメチル基、カルボキシエチル基、スルホエチル基、スルホプロピル基、ホスホノメチル基、ホスホノエチル基が特に好ましい例として挙げることができる。Ｒは水素原子、炭素数１〜１０の直鎖又は分岐鎖の置換してもよいアルキル基を表し、炭素数１〜５が好ましい。置換基としては、カルボキシル基、スルホ基、ホスホノ基、ホスフィン酸基、ヒドロキシル基、又は、アルキル置換してもよいアミノ基、アンモニオ基、カルバモイル基又はスルファモイル基を表す。置換基は二つ以上あってもよい。Ｒとして水素原子、カルボキシメチル基、カルボキシエチル基、カルボキシプロピル基、スルホエチル基、スルホプロピル基、スルホブチル基、ホスホノメチル基、ホスホノエチル基、ヒドロキシエチル基が好ましい例として挙げることができ、水素原子、カルボキシメチル基、カルボキシエチル基、スルホエチル基、スルホプロピル基、ホスホノメチル基、ホスホノエチル基が特に好ましい例として挙げることができる。ＬとＲが連結して環を形成してもよい。
【００６３】
これら一般式〔Ｈ〕又は一般式〔Ｂ〕で示される化合物は、通常遊離のアミン、塩酸塩、硫酸塩、ｐ−トルエンスルホン酸塩、シュウ酸塩、リン酸塩、酢酸塩等の形で用いられる。
【００６４】
発色現像処理液には、保恒剤として亜硫酸塩を微量用いることができる。該亜硫酸塩としては、亜硫酸ナトリウム、亜硫酸カリウム、重亜硫酸ナトリウム、重亜硫酸カリウム等が挙げられる。
【００６５】
発色現像処理液には、緩衝剤を用いることができ、緩衝剤としては、炭酸カリウム、炭酸ナトリウム、重炭酸ナトリウム、重炭酸カリウム、リン酸三ナトリウム、リン酸三カリウム、リン酸二カリウム、ホウ酸ナトリウム、ホウ酸カリウム、四ホウ酸ナトリウム（ホウ酸）、四ホウ酸カリウム、ｏ−ヒドロキシ安息香酸ナトリウム（サリチル酸ナトリウム）、ｏ−ヒドロキシ安息香酸カリウム、５−スルホ−２−ヒドロキシ安息香酸ナトリウム（５−スルホサリチル酸ナトリウム）、５−スルホ−２−ヒドロキシ安息香酸カリウム（５−スルホサリチル酸カリウム）が好ましい。
【００６６】
発色現像処理液には、現像促進剤を用いることができ、現像促進剤としては、チオエーテル系化合物、ｐ−フェニレンジアミン系化合物、４級アンモニウム塩類、ｐ−アミノフェノール類、アミン系化合物、ポリアルキレンオキサイド、１−フェニル−３−ピラゾリドン類、ヒドロジン類、メソイオン型化合物、イオン型化合物、イミダゾール類等を必要に応じて添加することができる。
【００６７】
発色現像液はベンジルアルコールを実質的に含有しないものが好ましい。
【００６８】
発色現像処理液には、カブリ防止等の目的で塩素イオン及び臭素イオンを添加することができる。発色現像液に直接添加される場合、塩素イオン供給物質として、ナトリウム、カリウム、アンモニウム、ニッケル、マグネシウム、マンガン、カルシウム又はカドミウムの塩化物が挙げられるが、そのうち好ましいものは塩化ナトリウム、塩化カリウムである。また、発色現像液に添加される蛍光増白剤の対塩の形態で供給されてもよい。臭素イオンの供給物質として、ナトリウム、カリウム、アンモニウム、リチウム、カルシウム、マグネシウム、マンガン、ニッケル、カドミウム、セリウム又はタリウムの臭化物が挙げられるが、そのうち好ましいものは臭化カリウム、臭化ナトリウムである。
【００６９】
〔漂白能を有する処理液〕
本発明では公知の漂白液を用いることができる。漂白液には、漂白剤又は過酸化物、漂白カブリ防止剤、ハロゲン化剤などが含有されてよい。
【００７０】
特に特願平７−２９６８９９号に記載されている漂白液を用いるのが好ましい。
【００７１】
具体的には、下記の〔化４〕〔化５〕に記載されているアミノポリカルボン酸化合物の第２鉄錯塩から成る漂白剤もしくは過酸化物（過硫酸塩、過酸化水素等）が好ましい。
【００７２】
【化４】

【００７３】
【化５】

【００７４】
これらの漂白剤の中で特に好ましいのは、１，３−プロピレンジアミン４酢酸鉄系化合物（以下、ＰＤＴＡ−Ｆｅとも記載する。）で、ナトリウム、カリウム、アンモニウム等の塩で用いる。
【００７５】
本発明の処理液においては、これらの漂白の濃度は０．２〜０．４モル／ｌと高濃度で用いて迅速化の効果を遺憾なく発揮できる。
【００７６】
また、漂白カブリを押さえるために、下記の有機カルボン酸を用いて、ハロゲン化剤としての臭化物が含有される漂白液が好ましい。
【００７７】
ここに用いる好ましい有機カルボン酸化合物は下記一般式で表される。
【００７８】
一般式 Ａ−（ＣＯＯＭ）ｎ
〔式中、ｎ＝２のとき、Ａは単結合又は２価の基を表し、ｎ＝３のとき、Ａは３価の基を表す。Ｍは水素原子、アルカリ金属又はアンモニウム基を表す。ｎ個のＭは同一でも異なっていてもよい。〕
以下に有機カルボン酸化合物の具体例を示す。
【００７９】
（Ｂ−１） ＨＯＯＣＣＨ_２Ｃ（ＯＨ）（ＣＯＯＨ）ＣＨ_２ＣＯＯＨ
（Ｂ−２） ＨＯＯＣ（ＣＨＯＨ）_２ＣＯＯＨ
（Ｂ−３） ＨＯＯＣＣＨ_２ＣＯＯＨ
（Ｂ−４） ＨＯＯＣＣＨ（ＯＨ）ＣＨ_２ＣＯＯＨ
（Ｂ−５） ＨＯＯＣＣＨ＝ＣＨＣＯＯＨ
（Ｂ−６） ＨＯＯＣＣＨ_２ＣＨ_２ＣＯＯＨ
（Ｂ−７） （ＣＯＯＨ）_２
【００８０】
【化６】

【００８１】
（Ｂ−１０）ＮａＯＯＣＣＨ＝ＣＨＣＯＯＮａ
（Ｂ−１１）ＫＯＯＣＣＨ＝ＣＨＣＯＯＫ
（Ｂ−１２）Ｈ_４ＮＯＯＣＣＨ＝ＣＨＣＯＯＮＨ_４
【００８２】
【化７】

【００８３】
（Ｂ−１６）ＨＯＯＣ（ＣＨ_２）_４ＣＯＯＨ
（Ｂ−１７）ＨＯＣＨ_２ＣＯＯＨ
（Ｂ−１８）ＨＯＯＣＣＨ_２ＣＨ_２ＣＨ_２ＣＯＯＨ
これらのうち本発明の処理液に用いて好ましいのは、（Ｂ−１）、（Ｂ−３）、（Ｂ−４）、（Ｂ−５）、（Ｂ−６）、（Ｂ−１６）〜（Ｂ−１８）であり、特に（Ｂ−５）及び（Ｂ−６）である。
【００８４】
これらの化合物の添加量は、好ましくは０．４モル／ｌ以下、更には０．０５〜０．３モル／ｌである。
【００８５】
また、チオ硫酸塩を含有させた漂白定着液であってもよい。
【００８６】
漂白能を有する処理液での処理時間は３秒から３０秒が好ましく、５秒から１５秒がさらに好ましい。
【００８７】
〔ハロゲン化銀写真感光材料〕
本発明で用いられる感材の例として、塩化銀乳剤を含有するハロゲン化銀カラー写真感光材料や沃臭化銀または臭化銀乳剤を含有するハロゲン化銀カラー写真感光材料が挙げられる。
【００８８】
【発明の実施の形態】
以下、本発明の実施の形態について説明する。これら実施の形態は本発明の具体例を示すものであり、本発明を限定するものではない。また、断定的な記述もあるが、これらも実施の形態として好ましい例を示すものであり、本発明を限定するものではない。
【００８９】
実施例１
図１は、実施例１の自動現像機の主要部の概略構成図である。図２は実施例１の自動現像機の発色現像部の斜視図である。図３は実施例１の自動現像機の処理液供給口乾燥防止手段近傍の斜視図である。
【００９０】
〔自動現像機〕
ハロゲン化銀写真感光材料（感材）Ｐを所定の搬送速度で搬送する搬送手段として、図示しない搬送ローラの他、加熱ドラム１１、圧着ベルト１５、加熱ベルト３３や漂白定着処理槽以降の搬送ローラなどがある。そして、処理液供給手段５２が処理液を供給する先よりも搬送手段の搬送方向上流側の所定位置に、感材Ｐの存在を検出する感材検出手段７０を有する。そして、感材検出手段７０の感材Ｐの搬送経路下流には、感材Ｐを加熱する加熱手段１０がある。加熱手段１０には、加熱ドラム１１がある。また、加熱ドラム１１の上側に出口側ローラ１２がある。加熱ドラム１１の左側に入口側ローラ１３がある。出口側ローラ１２の左側で入口側ローラ１３の上側に圧着ベルト駆動ローラ１４がある。圧着ベルト１５が、出口側ローラ１２、入口側ローラ１３及び圧着ベルト駆動ローラ１４に架け渡され、加熱ドラム１１の周面の約９０°の区間に渡って加熱ドラム１１に圧接されながら回動することにより、加熱ドラム１１に感材Ｐを圧着して搬送させる。これらにより、感材Ｐは加熱される。
【００９１】
加熱ドラム１１の感材Ｐの搬送経路下流に現像処理手段５０がある。現像処理手段５０は、感材Ｐを処理する処理液（発色現像液）を収容する処理液収納容器として、処理液容器５１と処理液補給容器５６を有する。該処理液容器５１と処理液補給容器５６は外気に対して密閉されている。処理液供給手段５２としては後述する供給ヘッドを使用する。これにより、処理液供給手段５２が、加熱手段１０により加熱された感材Ｐの乳剤面に気相を介して処理液（発色現像液）を供給する。また、処理液容器５１の上方で処理液補給容器５６の左方には循環ポンプ５４が有り、処理液容器５１と処理液補給容器５６との隔壁にフィルタ５５が有り、循環ポンプ５４が作動させることにより、図１の矢印に示す方向に、発色現像液を処理液容器５１から循環ポンプ５４、処理液補給容器５６、フィルタ５５の順に循環させる。また、回転子５７が処理液補給容器５６の中で回転して処理液補給容器５６内の処理液を攪拌する。
【００９２】
これにより、処理液補給容器５６から処理液供給手段５２の間に設けられ、処理液補給容器５６からの処理液を濾過する濾過手段（フィルタ５５）を有することになり、循環手段（循環ポンプ５４）により循環する処理液の循環経路の固体処理剤供給手段４０により固体処理剤が供給される領域（処理液補給容器５６）の循環経路下流側で、処理液供給手段５２により供給される処理液が存在する領域（処理液容器５１）の循環経路上流側に、処理液を濾過する循環濾過手段（フィルタ５５）を有することになる。
【００９３】
また、処理液補給容器５６には図示しない補充水供給手段から補充水Ｗを供給される。また、処理液補給容器５６にハロゲン化銀写真感光材料用固体処理剤Ｊを供給する固体処理剤供給手段４０が処理液補給容器５６の処理液面５３上方に設けられている。固体処理剤供給手段４０は、固体処理剤容器４９から固体処理剤を一定量づつ供給する定量供給部４１と、定量供給部４１から供給された固体処理剤を処理液に導く誘導部４４を有する。固体処理剤Ｊとしては錠剤等を用いることで、定量性を向上させ、処理液容器内の処理剤成分の変動を低減できる。固体処理剤容器４９の内部は隔壁により４行４列の１６の部屋（複数の部屋）に分割されており、それぞれの部屋に固体処理剤Ｊを実質的に点接触又は線接触で一列に収容できるようになっている。これにより、固体処理剤Ｊ同士が固着したりすることを防止できる。特に、本発明の場合、処理液容器の容量を小さくでき、そのためには固体処理剤Ｊの大きさも従来のものよりも小さくするため、固体処理剤Ｊ同士が固着しやすいので、特に有用である。定量供給部４１はその内部に回転する回転ロータ４２が設けられている。そして、固体処理剤容器４９の部屋の２行づつに対応して受容部４３が設けられており、回転ロータ４２が１８０度回転する毎に固体処理剤Ｊが２個づつ受容部４３に受容され、受容部４３から誘導部４４へ錠剤Ｊが２個づつ供給される。この際、固体処理剤供給時以外は、回転ロータ４２は受容部４３がない所が誘導部４４に面しているので、この回転ロータ４２で処理液からの湿気が固体処理剤容器４９側に来ることを防止ししている。誘導部４４は、ほぼＳ字の形状になっており、固体処理剤Ｊが勢いよく処理液面５３に落下して液をはね上げることを防止すると同時に、処理液からの湿気が直接多量に回転ロータ４２に来ることを防止している。特に、本発明の場合、処理液容器５１，５６の容量を小さくでき、そのためには固体処理剤Ｊの大きさも従来のものよりも小さくするため、固体処理剤Ｊと回転ロータ４２などが固着しやすいので、特に有用である。
【００９４】
処理液供給手段５２には、供給ヘッドへの処理液の供給を感材Ｐの幅方向の途中でストップする第一シャッタ６２と第二シャッタ６４が設けられている。第一シャッタ６２は第一シャッタ駆動部６１により供給ヘッドへの処理液の供給路に挿入離脱自在に駆動され、第二シャッタ６４は第二シャッタ駆動部６３により供給ヘッドへの処理液の供給路に挿入離脱自在に駆動される。図２では、第二シャッタ６４が供給ヘッドへの処理液の供給路に挿入された状態を示す。
【００９５】
処理液供給手段５２の下には、処理液供給手段５２の供給ヘッドの供給口にある処理液の乾燥を防止するために、処理液を感材Ｐに供給しない時に供給ヘッドの供給口を蓋する供給口乾燥防止手段８０がある。供給口乾燥防止手段８０は、可動蓋８１と、可動蓋８１を支える支持棒８２と、支持棒８２を上下に移動させるモータ８３がある。支持棒８２にはラックギヤを、モータ８３にはピニオンギヤを設けるなどにより、モータ８３により支持棒８２を上下に駆動する。可動蓋８１は断面凹形状であり、後述するように、感材Ｐの処理を行わない待機稼働状態においても、処理液供給手段５２は定期的に処理液を供給するが、この際に若干可動蓋８１が下に移動し、処理液供給手段５２から供給された処理液を受け、支持棒８２の中に設けられた図示しない孔を通して、廃液部に処理液を排出することにより、この処理液で周辺の装置が汚れることを防止する。
【００９６】
処理液供給手段５２により気相を介して処理液を供給される所の感材Ｐの搬送経路下流側に感材Ｐを加熱する第二加熱手段３０がある。第二加熱手段３０には、加熱ローラ３１、駆動ローラ３２、加熱ベルト３３がある。加熱ベルト３３は加熱ローラ３１と駆動ローラ３２に掛け渡されている。加熱ローラ３１は、処理液供給手段２２により気相を介して処理液を供給される先の感材Ｐの搬送経路下流側にあり、加熱ベルト３３を加熱する。加熱ローラ３１より感材Ｐの搬送経路下流側にある駆動ローラ３２は加熱ベルト３３を駆動させる。これにより、加熱ベルト３３が加熱された状態で感材Ｐを加熱する。そして、処理液供給手段５２により気相を介して処理液をその乳剤面に供給されたハロゲン化銀写真感光材料を、第二加熱手段３０が加熱することになる。
【００９７】
その後、現像処理手段２０により発色現像処理された感材Ｐは漂白定着処理液槽ＢＦで漂白定着処理され、安定化処理槽ＳＴで安定化処理される。
【００９８】
〔処理液量調整手段〕
露光量より得られる濃度を計算しておき、未露光部即ちＤｍｉｎ部への処理液の滴下量は、０ｍｌ／ｍ^２とし、Ｂ，Ｇ，Ｒの濃度値の中で最大値濃度に対応して滴下量を決める。即ち下記の表１に示すように濃度値に対して滴下量を段階的に変えた。また、比較例として、Ｂ，Ｇ，Ｒの濃度値によらず、一定量８０ｍｌ／ｍ^２を滴下した。
【００９９】
【表１】

【０１００】
〔処理液供給ヘッド〕
図４は前記処理液供給手段（処理液供給ヘッド）５２のオリフィス前面の拡大図である。前記処理液供給ヘッド５２には、各オリフィス毎に処理液室５８と、該処理液室から液滴を噴射させる液滴発生手段が設けてある。該液滴発生手段は、▲１▼ピエゾ電気素子等の電気機械変換手段により処理液室（圧力室）５８内の容積を変化させてオリフィス５９から液滴を噴射させるもの、▲２▼加熱素子により処理液室５８内に気泡（バブル）を発生膨張させて処理液圧を高めてオリフィス５９から液滴を噴射させるもの、等があり、これらの技術はインクジェットプリンター等で実用化されている。オリフィス５９から噴射されて気中を飛翔する液滴は、感材Ｐの乳剤面の所定位置に付着して、露光手段により形成された潜像を発色現像して顕像を形成する。
【０１０１】
前記複数のオリフィス５９は少なくとも２列配置されていて、この第１のオリフィス列と第２のオリフィス列とを半ピッチずらせることにより、感材搬送方向と直交する方向の感材の幅方向の液滴密度を高めている。複数のオリフィス５９の幅方向の密度は、必要とする発色現像密度により定められる。なお、複数のオリフィス５９は、上記の２列配置に限定されず、３列以上の配置でも良い。また、前記液滴発生手段は、オリフィス５９に連通する処理液室５８の側面又はオリフィス５９に対向する面に設けてある。
【０１０２】
本発明の実施例では、バブルジェット方式の複数オリフィス５９をライン状配列した供給ヘッドを使用する。この供給ヘッドの複数オリフィス５９は４列の千鳥配列である。各オリフィス５９の間隔は最近接するオリフィス５９との縁間距離で１００μｍである。オリフィス５９の直径は５０μｍ、１秒間の処理液供給回数（液滴噴射回数）は５０００回であり、１回当たりの処理液供給量（１個の液滴体積）は０．３ｐｌである。オリフィス列の投影線密度は６２４ｄｐｉである。
【０１０３】
投影線密度は複数のオリフィス列のオリフィス数を合計して１列とみなした場合の単位長さ（１インチ）当たりのオリフィス数である。
【０１０４】
比較の処理液供給ヘッドとして、１列のオリフィス列のものを用意した。オリフィスの直径、間隔は上記実施例１と同様である。
【０１０５】
〔感光材料〕
通常の方法でウエッジ露光されたコニカ（株）製のＱＡ−Ａ６印画紙を使用して以下の現像処理を行う。
【０１０６】
〔発色現像処理液容器内の処理液処方〕
１リットル当たり
亜硫酸ナトリウム ０．０５ｇ
ジエチレントリアミン５酢酸５ナトリウム ３．０ｇ
ポリエチレングリコール＃４０００ １０．０ｇ
ビス（スルホエチル）ヒドロキシルアミンジナトリウム １２．０ｇ
チノパールＳＦＰ ２．０ｇ
炭酸カリウム ３３．０ｇ
ｐ−トルエンスルホン酸ナトリウム ２０．０ｇ
ＣＤ−３ １０．０ｇ
水酸化カリウム ５．０ｇ
水酸化カリウム又は硫酸を用いてｐＨを１１．０に調整する。
【０１０７】
〔漂白定着・安定化処理工程〕
コニカ株式会社ＣＰＫ−２−２８プロセスの処理条件で、同プロセス用処理液により処理する。
【０１０８】
〔結果〕
複数のオリフィス列を有する処理液供給ヘッドを用いて処理した感材は、現像ムラの発生がなく、液滴下に要する時間が短時間で処理を終了することができる。また、画像濃度に応じて、液滴量を変化させることで、感材の白地におけるステインの発生が少なく、現像安定性が改良された。更に、処理液の消費液量を低く押さえることができる。
【０１０９】
実施例２
〔自動現像機〕
図５は、実施例２の自現機の主要部の概略構成図である。処理液により処理されるハロゲン化銀写真感光材料Ｐの搬送経路上流には、ハロゲン化銀写真感光材料Ｐを加熱する加熱手段１０がある。加熱手段１０には、感材Ｐの乳剤面から加熱する加熱ドラム１１がある。また、加熱ドラム１１の下側に出口側ローラ１２がある。加熱ドラム１１の左側に入口側ローラ１３がある。出口側ローラ１２の左側で入口側ローラ１３の下側に圧着ベルト駆動ローラ１４がある。圧着ベルト１５が、出口側ローラ１２、入口側ローラ１３及び圧着ベルト駆動ローラ１４に架け渡され、加熱ドラム１１の周面の９０°の区間に渡って加熱ドラム１１に圧接されながら動くことにより、加熱ドラム１１に感材Ｐを圧着して搬送させる。これらにより、感材Ｐは加熱される。
【０１１０】
加熱ドラム１１の感材Ｐの搬送経路下流に現像処理手段２０がある。現像処理手段２０は、感材Ｐを処理する処理液を収容する処理液容器として、感材Ｐを処理するための低ｐＨ発色現像主薬液を収容する第一の処理液容器２５と感材Ｐを処理するための高ｐＨ液を収容する第二の処理液容器２７を有する。第一の処理液容器２５に収容されている処理液を感材Ｐに供給する第一の処理液供給手段２６と、第二の処理液容器２７に収容されている処理液を感材Ｐに供給する第二の処理液供給手段２８としては後述する供給ヘッドを使用する。これにより、第一の処理液供給手段２６と第二の処理液供給手段２８が、加熱手段１０により加熱された感材Ｐの乳剤面に気相を介して発色現像液を供給する。感材Ｐから溢れた処理液は受け皿２９により、図示しない廃液部に出される。
【０１１１】
現像処理手段２０により発色現像処理された感材Ｐは漂白定着処理液槽ＢＦで漂白定着処理され、安定化処理槽ＳＴで安定化処理され、乾燥部Ｄｒｙで乾燥される。
【０１１２】
〔加熱条件・供給ヘッド〕
実施例１と同じ。
【０１１３】
〔感材〕
通常の方法で露光されたコニカ株式会社製ＱＡ−Ａ６印画紙を処理する。
【０１１４】
〔第一処理液容器内の処理液処方〕
１リットル当り
亜硫酸ナトリウム １．０ｇ
ビス（スルホエチル）ヒドロキシルアミンジナトリウム １２．０ｇ
ＣＤ−３ ３０．０ｇ
水酸化カリウム又は硫酸を用いてｐＨを２〜３に調整する。
【０１１５】
〔第二処理液容器内の処理液処方〕
１リットル当り
亜硫酸ナトリウム ０．０５ｇ
炭酸カリウム １００．０ｇ
ジエチレントリアミン５酢酸５ナトリウム ３．０ｇ
ポリエチレングリコール＃４０００ １０．０ｇ
ビス（スルホエチル）ヒドロキシルアミンジナトリウム １２．０ｇ
チノパールＳＦＰ ２．０ｇ
ｐ−トルエンスルホン酸ナトリウム ２０．０ｇ
水酸化カリウム ５．０ｇ
水酸化カリウム又は硫酸を用いてｐＨを１１．０に調整する。
【０１１６】
〔漂白定着・安定化処理工程〕
コニカ株式会社ＣＰＫ−２−２８プロセスの処理条件で、同プロセス用処理液により処理する。
【０１１７】
〔処理液調整手段〕
実施例１と同様にして行うが、滴下量は以下の表２に示すように、第１現像液、第２現像液ともに変える。また比較例としてＢ，Ｇ，Ｒの濃度によらず、一定量４０ｍｌ／ｍ^２を滴下する。処理液供給手段２６，２８は、実施例１の処理液供給ヘッド５２と同様の構造のものを用いた。
【０１１８】
【表２】

【０１１９】
〔結果〕
複数のオリフィス列を有する処理液供給手段２６，２８を用いて処理した感材Ｐは、現像ムラの発生がなく、液滴下に要する処理時間が短縮できる。
【０１２０】
実施例３
実施例２の処理液量調整手段において、液滴の重なり度を下記の表３のように変化させ、濃度のムラを観察した。またこのとき、使用された感材Ｐには、濃度が０．３になるようなグレーのベタ露光をしておく。
【０１２１】
感材Ｐの搬送方向（長手方向）の液滴の重なり度について説明すると、例えば、前列のオリフィス列が先に噴射して形成した前列の液滴列が搬送されて後列のオリフィス列付近の到達した時に後列のオリフィスを噴射させることにより後列の液滴列を前列の液滴列に重ならせることができる。重なり度とは、１ドットの液滴の面積をＳ，該液滴の周囲の各液滴と重なっている部分の面積をＳ_Ｄとすると、液滴の重なり度＝Ｓ_Ｄ／Ｓであり、前列のオリフィス列に対する後列のオリフィス列の噴射タイミングを変えることにより調整できる。
【０１２２】
感材Ｐの幅手方向の液滴の重なり度は複数のオリフィス列のピッチを変えて千鳥配列とし、かつ１ドット液滴の面積をＳを変えることにより調整できる。
【０１２３】
【表３】

【０１２４】
表３から分かるように、液滴の重なり度を０．２以上にすることで、所定の現像濃度を形成することができ、現像ムラを押さえることができる。
【０１２５】
実施例４
実施例２の処理液供給手段２６，２８で、オリフィス列の投影線密度を以下の表４のように変えて、実施例２と同様の評価を行った。なお、上記処理液供給手段２６，２８による感材Ｐの搬送方向のドット線密度は、最低滴下量時で、１５６ｄｐｉである。
【０１２６】
【表４】

【０１２７】
表４より分かるように、オリフィス列の投影線密度を、処理液供給手段２６，２８による感材Ｐの搬送方向のドット線密度より大きくすることで、現像ムラを改良することができる。
【０１２８】
実施例５
実施例２において、発色現像処理後に、漂白定着処理液槽ＢＦで行われ、漂白定着処理工程を本実施では発色現像処理に用いたと同様の供給ヘッドに下記の組成の漂白液ＢＬ供給して、下記の条件で滴下して漂白工程を行い、その後に定着処理槽Ｆｉｘで定着処理工程、安定化処理槽ＳＴで安定化処理工程、乾燥部Ｄｒｙで乾燥工程を行った。
【０１２９】
〔加熱条件・供給ヘッド〕
図６は本発明による自現機の主要部の他の実施の形態を示す概略構成図である。
【０１３０】
図６に示す自現機で処理を行った。処理時間および処理温度は以下に示す通りである。
【０１３１】

漂白処理手段９０の処理液供給ヘッド９２は実施例２と同様のものを使用した。
【０１３２】
漂白用処理液容器９１内の処理液処方
１ｌ当たり
ＰＤＴＡ−Ｆｅ １００ｇ
ＮＨ_４Ｂｒ ４０ｇ
コハク酸 ６０ｇ
ＰＤＴＡ−４Ｈ ６ｇ
炭酸カリウムと硫酸を用いてｐＨ４．０に調整する。
【０１３３】
定着液アンク液
チオ硫酸アンモニウム １００ｇ
亜硫酸アンモニウム １０ｇ
イミダゾール １０ｇ
ＥＤＴＡ−２Ｎａ １ｇ
水酸化カリウム又は硫酸を用いてｐＨを７．０に調整する。
【０１３４】
処理液調整手段
実施例２と同様に行うのが、重なり度０．５のときの漂白液の滴下量は表５に示す。また、発色現像液の滴下量は実施例２と同様である。
【０１３５】
【表５】

【０１３６】
液滴の重なり度を下記の表６のように変化させＤｍａｘ部の残留銀量を蛍光Ｘ線法で測定した。
【０１３７】
【表６】

【０１３８】
表６よりわかるように、漂白工程においても、液滴の重なり度を０．２以上にすることで、良好な漂白性能を示すことがわかる。
【０１３９】
【発明の効果】
以上に述べたように、感材に記録する画像信号に応じて処理液供給量を調整する場合、（特に低濃度に対応する画像信号）複数のオリフィス列を備え、処理液の単位面積当たりの滴下量を不連続な変化量とし、その滴下量を画像信号に対応させることで、低濃度部での処理液量を低減できるとともに、現像ムラが発生しないようにすることができる。
【０１４０】
また、白地部分に処理液を供給する必要がなくなるため、発色現像主薬の酸化物によるステイン発生も完全防止することが可能となる。
【０１４１】
請求項４により、低濃度と高濃度ともに現像ムラがより防止され、処理温度が変動しても安定した現像性を得ることができる。
【図面の簡単な説明】
【図１】本発明の実施例１による自動現像機の主要部の概略構成図。
【図２】上記自動現像機の発色現像部の斜視図。
【図３】上記自動現像機の処理液供給口の乾燥防止手段近傍の斜視図。
【図４】前記処理液供給手段（処理液供給ヘッド）のオリフィス前面の拡大図。
【図５】本発明の実施例２による自動現像機の主要部の概略構成図。
【図６】本発明の自動現像機の主要部の他の実施の形態を示す概略構成図。
【符号の説明】
１０ 加熱手段
２０ 現像処理手段
２５，２７，９１ 処理液容器
２６，２８，９２ 処理液供給手段（処理液供給ヘッド）
３０ 第二加熱手段
４０ 固体処理剤供給手段
５０ 現像処理手段
５１ 処理液容器
５２ 処理液供給手段（処理液供給ヘッド）
５４ 循環ポンプ
５５ フィルタ
５６ 処理液補給容器
５７ 回転子
５８ 処理液室
５９ オリフィス（処理液供給口）
７０ 感材検出手段
８０ 供給口乾燥防止手段
Ｐ ハロゲン化銀写真感光材料（感材）[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an automatic developing machine for a silver halide photographic light-sensitive material, which processes a silver halide photographic light-sensitive material with a processing solution (hereinafter, may be simply referred to as an automatic developing machine).
[0002]
[Prior art]
2. Description of the Related Art In recent years, environmental regulations have been in full swing, and in the photographic industry, how to reduce photographic processing waste liquid has become a serious issue.
[0003]
In addition, due to the rapid incorporation of minilabs in recent years, the amount of silver halide photosensitive material processed per store per minilab tends to decrease, and therefore the renewal rate of the processing tank liquid per day tends to decrease. is there. In particular, in the case of a processing solution for development, when the renewal rate of the processing tank solution is reduced, the deterioration of the processing tank solution due to air oxidation or the like becomes severe, and a problem that stable processing performance cannot be maintained tends to occur.
[0004]
As a means for solving such a problem, Japanese Patent Application Laid-Open No. 6-324455 discloses a method in which a sealed processing solution container is used to remove the emulsion surface of a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material). A method of directly supplying a large amount of processing liquid is disclosed.
[0005]
[Problems to be solved by the invention]
Indeed, by supplying the processing solution for processing the light-sensitive material described in JP-A-6-324455 from a processing solution container that hermetically accommodates the same to the emulsion surface of the light-sensitive material via a gas phase, Compared with the conventional method, the preservability of the processing solution (especially in the case of a color developing solution) can be improved. However, it has been found that the above technique has problems to be improved in practical use.
[0006]
This is because the amount of the processing solution used by the above technique is smaller than that of the conventional method (processing solution immersion method), but the processing solution supplied to the emulsion surface of the light-sensitive material is all in the next tank (for example, a bleach-fixing tank). ). In some cases, the amount of developer brought into the next tank is larger than that in the conventional tank development. As a matter of course, if the amount of the processing liquid supplied is large, the carry-in of the processing liquid causes a reduction in the processing performance of the next tank.
[0007]
Normally, the gradation of an image formed by an ink jet recording apparatus is determined by the dot density, and in many cases, droplets do not adhere between dots. In particular, when the density is low, a considerable gap is formed between dots. When an image is formed by developing a processing solution by dropping a processing solution onto a photosensitive material, the conventional method does not allow any drop or a small portion to occur, and when the drop amount is small, the processing solution permeates between dots. There is a problem that a gap that does not occur is generated and uneven development occurs. In order to prevent this, it was found that even if an excessive amount of liquid was dropped, the droplets joined together and approached, and development unevenness still occurred. In addition, it was found that the amount brought into the next tank was not good either.
[0008]
Further, one dot of the ink dropped on the recording surface by the ink jet recording apparatus is designed so as to have a diameter that is two to four times larger than the diameter of the ink droplet. However, when a developer is dropped on a photosensitive material, the spread of the droplet on the photosensitive material is almost the same as the size of the droplet, and the gap between dots is more likely to be generated. There is a problem that unevenness occurs on the top.
[0009]
In addition, it has been newly found that, when the processing liquid is supplied via a gas phase, a problem that the temperature of the processing liquid easily fluctuates in the ink jet recording apparatus. In other words, it is known that the temperature and humidity change even near the processing liquid at the start of the automatic processing machine and after sufficient operation, but the system of the present invention is particularly susceptible to influences through the gas phase. all right. In addition, since the actual market environment where the automatic developing machine is placed is placed under various temperature and humidity environments, it is essential to solve this problem.
[0010]
Accordingly, an object of the present invention is to firstly minimize the consumption of processing agent components used for development, secondly to improve the occurrence of uneven development, and thirdly to change the external environment. To provide an automatic developing machine capable of stabilizing process fluctuations caused by the image processing.
[0011]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, it has been found that the above-described problem can be solved by the configuration described below.
[0012]
The object is to supply a processing solution for processing a silver halide photographic light-sensitive material onto the emulsion surface of the silver halide photographic light-sensitive material via a gas phase, and to supply the processing solution to the emulsion surface of the silver halide photographic light-sensitive material. Adjusting means for adjusting the amount of processing liquid to be processed, the adjusting means comprisingMinimum dripping amountIs adjusted to 0.2 or more in the degree of overlap of droplets, wherein the supply meansIn the transport direction of silver halide photographic materialHaving a plurality of orifice rows,pluralThe projected line density of the orifice row isBy the supply meansProcessing liquidAt the minimum drop amount of the dot linear density in the photosensitive material transport directionThis is achieved by an automatic developing machine for a silver halide photographic light-sensitive material, characterized in that it is larger than the above (Constitution 1).
[0013]
According to the configuration 1, by setting the minimum value of the drop amount of the processing liquid per unit area to 0.2 or more in terms of the degree of overlap of the droplets, it is possible to reduce the processing liquid amount and to prevent development unevenness from occurring. it can. Here, the area of a droplet of one dot of the processing liquid supplied from the orifice onto the silver halide photographic material is S, and the area of a portion of the liquid droplet surrounding the droplet and overlapping each other is S._DThen, the degree of overlap of droplets = S / S_DIt is.
[0014]
Further, the above object is to provide a supply means for supplying a processing solution for processing a silver halide photographic light-sensitive material onto the emulsion surface of the silver halide photographic light-sensitive material via a gas phase, Adjusting means for adjusting the amount of processing liquid supplied to the nozzle, wherein the supplying means has a plurality of orifice rows, and the adjusting means changes the drop amount of the processing liquid per unit area discontinuously. This is achieved by an automatic developing machine for silver halide photographic light-sensitive materials, characterized in that the amount is changed according to the image signal (configuration 2).
[0015]
According to the second aspect, when adjusting the supply amount of the processing liquid according to the image signal to be recorded on the photosensitive material, a plurality of orifice rows (particularly, image signals corresponding to a low density) are provided, and the drop amount of the processing liquid per unit area is reduced. By setting the amount of discontinuous change and making the amount of drop correspond to the image signal, it is possible to reduce the amount of the processing liquid in the low-density portion and to prevent development unevenness from occurring.
[0016]
According to the method of the present invention, in which the drop amount per unit area of the processing liquid is changed discontinuously, the output signal from the image reading device is taken into the processing liquid supply means adjusting means, and the predetermined liquid amount is exposed by the processing liquid adjusting means. Although the material is supplied through the gas phase, in the present invention, the position of the photosensitive material is detected by an infrared sensor or the like, the image part and the non-image part are recognized, and the liquid part is not dropped on the non-image part. The image portion may be dropped at least in a fixed amount. Preferably, the supply liquid amount is changed stepwise according to the image signal.
[0017]
That is, in the present invention, instead of making the image density correspond to the processing liquid volume in a one-to-one correspondence, the sensitometric density region is divided into one or a plurality of regions, and the maximum density of the divided region is determined. Be sure to supply the amount of active substance needed to obtain it. The number of regions to be divided is preferably 1 to 20 steps, more preferably 3 to 10 steps. Further, a predetermined main drug amount and a processing liquid amount can be calculated from the maximum density value among the image densities B, G, and R.
[0018]
Further, since the processing solution for the silver halide photographic light-sensitive material is a color developing solution or a bleaching solution, it is not necessary to supply a processing solution to a white background portion, so that generation of stains due to oxides of the color developing agent is completely prevented. It is possible to do.
[0019]
Further, it is effective from the viewpoint of development processing that the processing solution for a silver halide photographic light-sensitive material is particularly for color development.
[0020]
Furthermore, since the projection line densities of the plurality of orifice rows are larger than the dot line densities in the head advancing direction at the time of the minimum dropping amount of the processing liquid, uneven development at both low and high densities is further prevented, and the processing temperature is reduced. Even if it fluctuates, stable developability can be obtained.
[0021]
The orifice rows of the present invention are at least two rows, preferably two to six rows. The rows are preferably staggered.
[0022]
The degree of overlap of the droplets is preferably 0.2 or more and 4 or less, more preferably 0.3 or more and 3 or less.
[0023]
The image signal shown in the present invention may be an input signal such as a photometric density (integrated density) read by a generally used image reading device or a digital image signal stored in a photo CD or the like. An output signal such as the amount of exposure to the already-performed photosensitive material is also included.
[0024]
In the present invention, when the image signal is an input signal such as the photometric density (integrated density), a means for converting the integrated density into the density (analytical density) of each of the yellow, magenta, and cyan color materials alone is required ( For example, it is described in JP-A-4-88344. Further, a means for converting the analysis densities of Y, M, and C into B, G, and R exposure amounts to the light-sensitive material is required. As a method of converting the analysis densities into the exposure amounts, there is a method for each of R, G, and B. The conversion may be based on a characteristic curve between the exposure amount and the analytical density (color density) of the Pan layer, the Orthoc layer, and the Regular layer, or the exposure amount and the developed photosensitive material are measured by a densitometer. The measured concentration may be used as the analysis concentration and converted from the relationship between the measurement results.
[0025]
Specific means for adjusting the color developing agent supply amount in the present invention includes:
(A) The supply amount is adjusted by adjusting the number of ejection dots per unit area in the same manner as in a normal inkjet method.
(B) adjusting the supply amount by adjusting the number of injections (frequency) of the processing liquid per unit time;
Any means of (C) adjusting the supply amount by adjusting the unit injection amount of the processing liquid may be used.
[0026]
Hereinafter, preferred embodiments of the present invention will be described.
[0027]
(Treatment liquid supply means)
In the present invention, the processing liquid supply means for supplying the processing liquid to the emulsion surface of the light-sensitive material via the gas phase includes a processing liquid flying means for flying the processing liquid to the light-sensitive material via the gas phase, and a curtain coater. And a processing liquid application unit for applying a processing liquid to the photosensitive material via a gas phase. As a processing liquid flying means for flying the processing liquid to the light-sensitive material via the gas phase, a processing liquid having a structure similar to that of an ink jet head of an ink jet printer or a liquid discharging means having a structure described in JP-A-6-324455 is used. A processing liquid flying means that generates pressure by a processing liquid flying means through a gas phase with a processing liquid to a photosensitive material and actively sprays the processing liquid through a gas phase, such as a spray bar. And the like which are caused to fly by the liquid pressure applied to the substrate. As a processing liquid flying means for flying a processing liquid having a structure similar to that of an ink jet head of an ink jet printer to a photosensitive material via a gas phase, a processing liquid is supplied by vibration, or a processing liquid is supplied by bumping. It is preferable because the supply amount of the processing liquid can be controlled and the processing position of the photosensitive material can be selected.
[0028]
Further, as the processing liquid supply means, a processing liquid is supplied from the linear supply head to the photosensitive material via the gas phase, or a processing liquid is supplied from the planar supply head to the photosensitive material via the gas phase. Or a method in which a processing liquid is supplied from a point-like supply head to a light-sensitive material via a gas phase, or another method. Further, when the photosensitive material is a sheet, the processing liquid is sensed from the supply head using a planar supply head corresponding to the size of the photosensitive material in a state where the positional relationship between the photosensitive material and the supply head is fixed. Although the supply of the processing liquid from the supply head to the photosensitive material via the gas phase while shifting the positional relationship between the supply head and the photosensitive material may be possible, the supply head is smaller. However, it is preferable because the processing solution can be sufficiently supplied to the photosensitive material. When a linear supply head is used, the supply head may move.However, in order to quickly supply the processing liquid to the photosensitive material, a linear supply head and a linear supply head are used. It is preferable to move the photosensitive material in directions other than the parallel direction. In particular, in order to keep the processing time constant, it is preferable to move the photosensitive material in a direction perpendicular to the linear supply head. When the processing liquid is jetted from the supply head to the photosensitive material via the gas phase while the positional relationship between the supply head and the photosensitive material is shifted as the processing liquid flying means, Is preferably one or more times, particularly preferably ten or more times, in order to sufficiently supply the processing liquid to the surface of the light-sensitive material. Also, to fly from the supply head, 1 × 10⁶Times or less, preferably 1 × 10⁵It is preferably less than or equal to the number of times.
[0029]
When the processing liquid supply means supplies the processing liquid to the photosensitive material through the supply port, the supply port may have any shape such as a circle, a square, and an ellipse. The area of each supply port is 1 × 10 to prevent the processing liquid from being clogged when it is slightly dried.^-11m²More preferably, especially 1 × 10^-10m²The above is preferable. In addition, the area of each supply port is 1 × 10 so as to uniformly supply the processing liquid to the photosensitive material.^-8m²The following is preferable, especially 1 × 10^-6m²The following is preferred. The interval between the supply ports is 5 × 10 from the average of the distance between the edges of the supply ports and the strength of the supply ports.^-6m²The above is preferable, and in order to sufficiently supply the processing solution to the surface of the light-sensitive material, 1 × 10^-3m²The following is preferred.
[0030]
Further, the distance between the supply port after processing and the photosensitive material emulsion surface is preferably 50 μm or more (especially 1 mm or more) in order to easily control this distance, and more preferably 10 mm or less (especially 5 mm or less).
[0031]
(Heating means)
The temperature of the photosensitive material heated by the heating means may be about 40 ° C. or lower, but is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, and particularly preferably 50 ° C. or higher. The temperature is preferably 150 ° C. or lower from the viewpoint of heat resistance of the photographic material and ease of processing control, and further preferably 100 ° C. or lower, particularly 90 ° C. or lower, in order to prevent boiling of the processing solution.
[0032]
Examples of the heating means for heating the photosensitive material include a conduction heating means for heating by conduction in contact with the photosensitive material such as a heat drum and a heat belt, a convection heating means for heating by convection such as a dryer, and infrared and high-frequency electromagnetic waves. Radiant heating means for heating by the radiation of light.
[0033]
It is preferable to have a heating control means for controlling the heating means to heat when the silver halide photographic material is present before the heating means heats, because unnecessary heating can be prevented. This is because the conveying means for conveying the silver halide photographic material at a predetermined conveying speed, and the presence of the silver halide photographic light-sensitive material at a predetermined position on the upstream side in the conveying direction of the conveying means from the destination heated by the heating means. And a light-sensitive material detecting means for detecting the temperature, and the heating control means controls the heat based on the detection of the light-sensitive material detecting means. In this case, the control is performed such that the photosensitive material detecting means detects the presence of the silver halide photographic light-sensitive material at the predetermined position from the absence of the silver halide photographic material at a predetermined time, and then the photosensitive material detecting means detects the silver halide at the predetermined position. It is preferable to control the heating means to perform a predetermined heating until a predetermined time elapses after detecting the presence or absence of the photographic light-sensitive material.
[0034]
(Stirring means)
Examples of the stirring means include a rotor that is rotated by an induction magnetic field, and a propeller provided on a rotating shaft that is rotated by a motor or the like.
[0035]
(Circulation means)
The circulating means may be a circulating pump used in a general automatic developing machine.
[0036]
The silver halide photographic light-sensitive material is provided with a silver halide emulsion layer on a support, and may be provided on one side of the support or on both sides. The emulsion surface of the silver halide photographic light-sensitive material is the surface on the side where the silver halide emulsion layer is provided, and in the case where it is provided on both surfaces, it may be the front surface or the back surface.
[0037]
(Solid processing agent supply means)
Hereinafter, the supply of the solid processing agent will be described, but a known liquid replenishment processing liquid can also be used in the present invention.
[0038]
As the solid processing agent supply means for supplying the solid processing agent to the processing liquid container, for example, when the solid processing agent is a tablet, JP-A-63-137783, JP-A-63-97522, and JP-A-1-85732. There is a known method such as that described in Japanese Patent Application Laid-Open Publication No. H10-209, but any means may be used as long as the tablet is supplied to the processing liquid container. When the solid processing agent is granules or powder, the method of gravity drop method described in Japanese Utility Model Application Laid-Open Nos. 62-81964 and 63-84151 and Japanese Patent Application Laid-Open No. 1-292375, and Japanese Utility Model Application Laid-Open No. And a method using a screw or a screw described in JP-A-63-195345, but the invention is not limited thereto.
[0039]
The amount of the solid processing agent supplied at one time is preferably 0.1 g or more from the viewpoint of the durability of the solid processing agent supply means and the accuracy of the amount of one injection, and 50 g from the dissolution time point. The following is preferred.
[0040]
(Refill water)
The replenishing water is a liquid having an action of dissolving the solid processing agent supplied to the processing liquid container, and is usually water.
[0041]
(Solid processing agent)
The solid processing agent is a solid processing agent containing a processing agent component of a processing solution for processing a light-sensitive material. Solid processing agents include powders, tablets, pills, granules, and the like. Further, the surface may be provided with a water-soluble coating such as a water-soluble polymer as needed. The term "powder" as used in the present invention refers to an aggregate of fine crystals. The granules referred to in the present invention are obtained by granulating powder, and are preferably granules having a particle size of 50 to 5000 μm. The tablet in the present invention refers to a tablet obtained by compression-molding a powder or granules into a certain shape. The pills referred to in the present invention are those formed into a rounded shape (including a potato shape and a spherical shape) by granulation or tableting. Among the solid processing agents, granules, tablets, or pills are more preferable because they generate less dust during handling and have a better dosing accuracy. Among them, the tablet form is preferably used because the replenishment accuracy is high and the handling property is simple, the concentration is not rapidly changed due to rapid dissolution, and the effect of the present invention is favorably exhibited.
[0042]
To solidify the photographic processing agent, a concentrated solution, a fine powder or a granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is sprayed on the surface of the temporarily formed photographic processing agent. Then, any means such as forming a coating layer can be adopted (see JP-A-4-29136, JP-A-4-85533 to JP-A-4-85536, and JP-A-4-172341).
[0043]
A preferred tablet production method is a method in which a powdery solid processing agent is granulated and then subjected to a tableting step to form the tablet. Compared to a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet, there is an advantage that solubility and storage stability are improved, and as a result, photographic performance is stabilized. Granulation methods for forming tablets, granules or pills use known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation. I can do it. It is preferable to add a water-soluble binder in an amount of 0.01 to 20% by weight during granulation. As the water-soluble binder, celluloses, dextrins, sugar alcohols, polyethylene glycols, cyclodextrins and the like are preferable.
[0044]
These materials are preferably 0.5% or more and 20% or less based on the weight of the solid processing agent.
[0045]
Next, when forming a tablet by compressing the obtained granules under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, a briquetting machine is used. Can be done. More preferably, at the time of granulation, it is preferable to separate and granulate each component, for example, an alkali agent, a preservative, and the like.
[0046]
The method for producing a tablet processing agent is described in, for example, general methods described in the specifications such as JP-A-51-61837, JP-A-54-155038, JP-A-52-88025 and British Patent 1,213,808. The granulating agent can be produced by a general method described in the specification such as JP-A-2-10942, JP-A-2-109043, JP-A-3-39735 and JP-A-3-39939. it can. Further, powder processing agents are described in, for example, JP-A-54-133332, British Patent Nos. 725,892 and 729,862, and German Patent No. 3,733,861. Manufacturing method.
[0047]
[Treatment process]
Each of the means characteristic of the present invention may be used in any processing step of processing a light-sensitive material with a processing solution, but it is not a desilvering processing step (bleaching processing step) or a processing step of removing unnecessary substances, but a dye. It is preferably used in a processing step in which generation or an oxidation reaction is caused, and in particular, a developing step, a color developing step, and a bleaching step are preferable.
[0048]
(Color development processing)
The time of the color developing process is the time until the portion of the photosensitive material to which the color developing solution is first supplied is supplied with the processing solution of the next step or immersed in the processing solution of the next step. The time of the color development process is preferably 5 seconds or more, particularly 8 seconds or more, from the viewpoint of sufficiently stably performing the color development process, and 180 seconds or less, particularly 60 seconds or less is supplied to the photosensitive material. It is possible to prevent the color developing solution from deteriorating or drying and adversely affecting the light-sensitive material, which is preferable.
[0049]
Further, in the color development processing step, a plurality of processing liquid supply means is provided, a processing liquid is supplied to the photosensitive material from the first processing liquid supply means, and to the photosensitive material supplied with the processing liquid from the first processing liquid supply means, The processing liquid may be supplied from the second processing liquid supply unit. In this case, the following three preferable embodiments are mentioned.
[0050]
First, in the case of performing color development processing of a light-sensitive material with a color developing agent that is active at a pH of 7 or more, the first processing liquid supply means converts a processing solution containing a color developing agent having a pH of 6 or less into a light-sensitive material. In this embodiment, the second processing liquid supply means supplies a color developing solution having a pH of 7 or more. As a result, the color developing agent having a low diffusion rate sufficiently diffuses in the thickness direction of the photosensitive material, and then an alkali component having a high diffusion rate is supplied and diffused. It is possible to prevent problems such as uneven development due to the difference. When the light-sensitive material is a multi-layer type color photographic light-sensitive material, it is particularly useful if the development start time greatly differs in the thickness direction of the light-sensitive layer, because the color-developing characteristics between the primary colors are degraded. In particular, it is effective in the case of a multi-layer structure of 5 layers or more, further 10 layers or more.
[0051]
Second, the first processing liquid supply means supplies water to the light-sensitive material, and the second processing liquid supply means supplies a color development processing liquid. As a result, the color developing solution is supplied after the photographic material is supplied with water and swells sufficiently, so that components having a low diffusion speed in the hardened photographic material are diffused at a sufficiently high speed. Problems such as uneven development due to a large difference in the development start time in the thickness direction of the layer can be reduced.
[0052]
Third, an embodiment in which the first processing liquid supply means supplies water containing an oxidizing agent such as hydrogen peroxide to the photosensitive material, and the second processing liquid supply means supplies a color developing processing liquid. It is.
[0053]
The color developing agent is preferably a p-phenylenediamine compound having a water-soluble group. Examples of the water-soluble group include those having at least one amino group on the amino group or benzene nucleus of the p-phenylenediamine compound, and specific water-soluble groups include-(CH₂)_n-CH₂OH,-(CH₂)_m-NHSO₂− (CH₂)_nCH₃,-(CH₂)_m-O- (CH₂)_n-CH₃,-(CH₂CH₂O)_nC_mH_{2m + 1}, (M and n each represent an integer of 0 or more) -COOH group, -SO₃H groups and the like are preferred. Specific examples of preferably used color developing agents include compounds (C-1) to (C-16) described on pages 7 to 9 of JP-A-4-86674.
[0054]
When a color developing agent contains a compound represented by the following general formula [H] or [B], there is an advantage that photographic performance is stable and fog generated in an unexposed portion is small, and in addition, in the case of a solid processing agent, In addition, the storage stability of the solid processing agent is improved as compared with other compounds.
[0055]
Embedded image

[0056]
In the general formula [H], R₁And R₂Represents an alkyl group, an aryl group, an R′—CO— group or a hydrogen atom which is not a hydrogen atom at the same time,₁And R₂The alkyl groups represented by may be the same or different, and are each preferably an alkyl group having 1 to 3 carbon atoms. Further, these alkyl groups may have a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, or a hydroxyl group. R 'represents an alkoxy group, an alkyl group or an aryl group. R₁, R₂And the alkyl group and the aryl group represented by R ′ include those having a substituent,₁And R₂May combine to form a ring, for example, a heterocyclic ring such as piperidine, pyridine, triazine or morpholine.
[0057]
Embedded image

[0058]
In the general formula [B], R₁₁, R₁₂, R_ThirteenRepresents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group;₁₄Represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, and an amino group. The heterocyclic group is a 5- to 6-membered ring and is composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. R_FifteenIs -CO-, -SO₂Represents a divalent group selected from-or -C (= NH)-, and n is 0 or 1. Especially when n = 0, R₁₄Represents a group selected from an alkyl group, an aryl group and a heterocyclic group;_ThirteenAnd R₁₄May together form a heterocyclic group.
[0059]
Among the compounds represented by the general formula [H], compounds represented by the following general formula [D] are particularly preferred.
[0060]
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[0061]
In the general formula [D], L represents an alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group or a sulfamoyl group, and R represents a hydrogen atom. Or an alkyl group. Each of L, A, and R includes both linear and branched chains, and may be unsubstituted or substituted. L and R may combine to form a ring.
[0062]
The compound represented by formula (D) will be described in more detail. In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, groups such as methylene, ethylene, trimethylene, and propylene are preferred examples. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, and an ammonio group which may be alkyl-substituted. Preferred examples include a carboxyl group, a sulfo group, a phosphono group, and a hydroxyl group. A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group or a sulfamoyl group which may be alkyl-substituted, and a carboxyl group, a sulfo group, a hydroxyl group, And a carbamoyl group which may be alkyl-substituted. Examples of -LA include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group. Groups, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group and a phosphonoethyl group can be mentioned as particularly preferred examples. R represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, or a sulfamoyl group which may be alkyl-substituted. There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Groups, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group and a phosphonoethyl group can be mentioned as particularly preferred examples. L and R may combine to form a ring.
[0063]
These compounds represented by the general formula [H] or the general formula [B] are usually in the form of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate, etc. Used.
[0064]
In the color developing solution, a slight amount of sulfite can be used as a preservative. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.
[0065]
Buffers can be used in the color developing solution, and the buffers include potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, and borane. Sodium silicate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate ( Preferred are sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
[0066]
A development accelerator can be used in the color developing solution, and examples of the development accelerator include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, and polyalkylenes. Oxides, 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles and the like can be added as necessary.
[0067]
The color developing solution preferably does not substantially contain benzyl alcohol.
[0068]
Chloride ions and bromine ions can be added to the color developing solution for the purpose of preventing fog and the like. When directly added to the color developing solution, the chloride ion supplying material includes sodium, potassium, ammonium, nickel, magnesium, manganese, calcium or cadmium chloride, and preferred are sodium chloride and potassium chloride. . Further, it may be supplied in the form of a salt of a fluorescent whitening agent added to the color developing solution. Examples of the bromine ion supplying material include sodium, potassium, ammonium, lithium, calcium, magnesium, manganese, nickel, cadmium, cerium and thallium bromides, of which potassium bromide and sodium bromide are preferred.
[0069]
(Processing solution having bleaching ability)
In the present invention, a known bleaching solution can be used. The bleaching solution may contain a bleaching agent or peroxide, a bleaching inhibitor, a halogenating agent, and the like.
[0070]
It is particularly preferable to use the bleaching solution described in Japanese Patent Application No. 7-296899.
[0071]
Specifically, bleaching agents or peroxides (persulfates, hydrogen peroxide, etc.) comprising a ferric complex salt of an aminopolycarboxylic acid compound described in the following [Chemical Formula 4] and [Chemical Formula 5] are preferable. .
[0072]
Embedded image

[0073]
Embedded image

[0074]
Among these bleaching agents, particularly preferred are 1,3-propylenediaminetetraacetate-based compounds (hereinafter also referred to as PDTA-Fe), which are used in the form of salts such as sodium, potassium and ammonium.
[0075]
In the processing solution of the present invention, the bleaching concentration is as high as 0.2 to 0.4 mol / l, so that the effect of speeding up can be satisfactorily exhibited.
[0076]
Further, in order to suppress bleaching fog, a bleaching solution containing bromide as a halogenating agent using the following organic carboxylic acid is preferable.
[0077]
The preferred organic carboxylic acid compound used here is represented by the following general formula.
[0078]
General formula A- (COOM) n
[Wherein, when n = 2, A represents a single bond or a divalent group, and when n = 3, A represents a trivalent group. M represents a hydrogen atom, an alkali metal or an ammonium group. The n Ms may be the same or different. ]
Hereinafter, specific examples of the organic carboxylic acid compound will be shown.
[0079]
(B-1) HOOCCH₂C (OH) (COOH) CH₂COOH
(B-2) HOOC (CHOH)₂COOH
(B-3) HOOCCH₂COOH
(B-4) HOOCCH (OH) CH₂COOH
(B-5) HOOCCH = CHCOOH
(B-6) HOOCCH₂CH₂COOH
(B-7) (COOH)₂
[0080]
Embedded image

[0081]
(B-10) NaOOCH = CHCOONa
(B-11) KOOCCH = CHCOOK
(B-12) H₄NOOCCH = CHCOONH₄
[0082]
Embedded image

[0083]
(B-16) HOOC (CH₂)₄COOH
(B-17) HOCH₂COOH
(B-18) HOOCCH₂CH₂CH₂COOH
Among these, those which are preferably used for the treatment liquid of the present invention include (B-1), (B-3), (B-4), (B-5), (B-6), and (B-16). To (B-18), particularly (B-5) and (B-6).
[0084]
The addition amount of these compounds is preferably 0.4 mol / l or less, and more preferably 0.05 to 0.3 mol / l.
[0085]
Further, a bleach-fixing solution containing a thiosulfate may be used.
[0086]
The processing time with a processing solution having bleaching ability is preferably from 3 seconds to 30 seconds, more preferably from 5 seconds to 15 seconds.
[0087]
[Silver halide photographic material]
Examples of the light-sensitive material used in the present invention include a silver halide color photographic light-sensitive material containing a silver chloride emulsion and a silver halide color photographic light-sensitive material containing a silver iodobromide or silver bromide emulsion.
[0088]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described. These embodiments show specific examples of the present invention and do not limit the present invention. In addition, there are certain statements, but these also show preferred examples as embodiments and do not limit the present invention.
[0089]
Example 1
FIG. 1 is a schematic configuration diagram of a main part of the automatic developing machine of the first embodiment. FIG. 2 is a perspective view of the color developing section of the automatic developing machine of the first embodiment. FIG. 3 is a perspective view of the vicinity of the processing liquid supply port drying prevention means of the automatic developing machine of the first embodiment.
[0090]
(Automatic processor)
Conveying means for conveying the silver halide photographic light-sensitive material (sensitive material) P at a predetermined conveying speed include conveying rollers (not shown), a heating drum 11, a pressure belt 15, a heating belt 33, and conveying rollers after the bleach-fixing processing tank. and so on. The photosensitive material detecting means 70 for detecting the presence of the photosensitive material P is provided at a predetermined position on the upstream side in the transport direction of the transport means from the destination where the processing liquid supply means 52 supplies the processing liquid. A heating unit 10 for heating the photosensitive material P is provided downstream of the photosensitive material P in the photosensitive material detection unit 70 in the transport path. The heating means 10 includes a heating drum 11. An outlet-side roller 12 is provided above the heating drum 11. On the left side of the heating drum 11 is an inlet roller 13. A pressure belt drive roller 14 is provided on the left side of the exit roller 12 and above the entrance roller 13. The pressure belt 15 is stretched over the outlet roller 12, the inlet roller 13, and the pressure roller drive roller 14, and rotates while being pressed against the heating drum 11 over a section of about 90 ° on the peripheral surface of the heating drum 11. Thus, the photosensitive material P is conveyed by being pressed against the heating drum 11. Thus, the photosensitive material P is heated.
[0091]
Downstream of the heating drum 11 in the conveying path of the photosensitive material P, there is a developing means 50. The development processing means 50 has a processing liquid container 51 and a processing liquid replenishing container 56 as processing liquid storage containers for storing a processing liquid (color developing solution) for processing the photosensitive material P. The processing liquid container 51 and the processing liquid supply container 56 are sealed from the outside air. As the processing liquid supply means 52, a supply head described later is used. Thus, the processing liquid supply unit 52 supplies the processing liquid (color developing solution) to the emulsion surface of the photosensitive material P heated by the heating unit 10 via the gas phase. A circulation pump 54 is provided above the processing liquid container 51 and to the left of the processing liquid supply container 56, and a filter 55 is provided on a partition wall between the processing liquid container 51 and the processing liquid supply container 56, and the circulation pump 54 is operated. Thus, the color developing solution is circulated from the processing liquid container 51 to the circulation pump 54, the processing liquid supply container 56, and the filter 55 in the direction indicated by the arrow in FIG. Further, the rotator 57 rotates in the processing liquid supply container 56 to stir the processing liquid in the processing liquid supply container 56.
[0092]
Accordingly, a filtering means (filter 55) provided between the processing liquid supply container 56 and the processing liquid supply means 52 and filtering the processing liquid from the processing liquid supply container 56 is provided. The processing liquid supplied by the processing liquid supply means 52 is provided on the downstream side of the circulation path downstream of the region (processing liquid supply container 56) where the solid processing agent is supplied by the solid processing agent supply means 40 in the circulation path of the processing liquid circulated. A circulation filtering means (filter 55) for filtering the processing liquid is provided on the upstream side of the circulation path of the region where the water exists (the processing liquid container 51).
[0093]
Further, the replenishing water W is supplied to the processing liquid replenishing container 56 from a replenishing water supplying means (not shown). Further, a solid processing agent supply means 40 for supplying a solid processing agent J for a silver halide photographic light-sensitive material to the processing liquid supply container 56 is provided above the processing liquid surface 53 of the processing liquid supply container 56. The solid processing agent supply means 40 includes a fixed amount supply unit 41 that supplies a fixed amount of the solid processing agent from the solid processing agent container 49 by a fixed amount, and a guiding unit 44 that guides the solid processing agent supplied from the fixed amount supply unit 41 to the processing liquid. . By using a tablet or the like as the solid processing agent J, the quantitative property can be improved, and the fluctuation of the processing agent component in the processing liquid container can be reduced. The inside of the solid processing agent container 49 is divided into 16 rooms (a plurality of rooms) of 4 rows and 4 columns by partition walls, and the solid processing agents J are stored in each room substantially in a line by point contact or line contact. I can do it. This can prevent the solid processing agents J from sticking to each other. In particular, in the case of the present invention, the capacity of the processing liquid container can be reduced, and the size of the solid processing agents J is also made smaller than that of the conventional one, so that the solid processing agents J are easily fixed to each other, which is particularly useful. . The fixed amount supply unit 41 is provided with a rotating rotor 42 that rotates therein. The receiving portions 43 are provided corresponding to every two rows of the room of the solid processing agent container 49, and each time the rotary rotor 42 rotates 180 degrees, two solid processing agents J are received by the receiving portion 43. The tablets J are supplied two by two from the receiving section 43 to the guiding section 44. At this time, except when the solid processing agent is supplied, the rotary rotor 42 has no receiving portion 43 facing the guide portion 44, so that moisture from the processing liquid is supplied to the solid processing agent container 49 by the rotary rotor 42. Prevent coming. The guide portion 44 has a substantially S-shape to prevent the solid processing agent J from vigorously dropping onto the processing liquid surface 53 and splashing up the liquid, and at the same time, a large amount of moisture from the processing liquid is directly generated. It is prevented from coming to the rotating rotor 42. In particular, in the case of the present invention, the capacity of the processing liquid containers 51 and 56 can be reduced, and the size of the solid processing agent J is also made smaller than that of the conventional one. It is particularly useful because it is easy.
[0094]
The processing liquid supply means 52 is provided with a first shutter 62 and a second shutter 64 for stopping the supply of the processing liquid to the supply head in the middle of the photosensitive material P in the width direction. The first shutter 62 is driven by a first shutter driving unit 61 so as to be freely inserted into and removed from a supply path of the processing liquid to the supply head, and the second shutter 64 is driven by a second shutter driving unit 63 to supply a processing liquid to the supply head. It is driven so that it can be inserted and removed. FIG. 2 shows a state where the second shutter 64 is inserted into the supply path of the processing liquid to the supply head.
[0095]
Under the processing liquid supply means 52, in order to prevent drying of the processing liquid at the supply port of the supply head of the processing liquid supply means 52, the supply port of the supply head is closed when the processing liquid is not supplied to the photosensitive material P. There is a supply port drying prevention means 80 to be used. The supply port drying prevention means 80 includes a movable lid 81, a support rod 82 supporting the movable lid 81, and a motor 83 for moving the support rod 82 up and down. By providing a rack gear on the support rod 82 and a pinion gear on the motor 83, the motor 83 drives the support rod 82 up and down. The movable lid 81 has a concave cross section. As will be described later, the processing liquid supply unit 52 periodically supplies the processing liquid even in a standby operation state in which the processing of the photosensitive material P is not performed. The cover 81 is moved downward, receives the processing liquid supplied from the processing liquid supply means 52, and discharges the processing liquid to a waste liquid portion through a hole (not shown) provided in the support rod 82, whereby the processing liquid is discharged. To prevent peripheral devices from becoming dirty.
[0096]
The second heating means 30 for heating the photosensitive material P is provided downstream of the transport path of the photosensitive material P where the processing liquid is supplied via the gas phase by the processing liquid supply means 52. The second heating means 30 includes a heating roller 31, a driving roller 32, and a heating belt 33. The heating belt 33 is stretched over the heating roller 31 and the driving roller 32. The heating roller 31 is located downstream of the transport path of the photosensitive material P to which the processing liquid is supplied via the gas phase by the processing liquid supply unit 22, and heats the heating belt 33. A driving roller 32 located downstream of the heating roller 31 in the conveyance path of the photosensitive material P drives a heating belt 33. Thus, the photosensitive material P is heated in a state where the heating belt 33 is heated. And a processing liquid supply means.52Thus, the second heating means 30 heats the silver halide photographic light-sensitive material in which the processing solution has been supplied to the emulsion surface via the gas phase.
[0097]
Thereafter, the photosensitive material P that has been color-developed by the developing means 20 is bleach-fixed in a bleach-fix processing solution tank BF, and is stabilized in a stabilization tank ST.
[0098]
(Treatment liquid amount adjusting means)
The concentration obtained from the exposure amount is calculated in advance, and the amount of the treatment liquid dropped to the unexposed part, that is, the Dmin part is 0 ml / m²And the drop amount is determined corresponding to the maximum concentration among the B, G, and R concentration values. That is, as shown in Table 1 below, the drop amount was changed stepwise with respect to the concentration value. In addition, as a comparative example, a constant amount of 80 ml / m2 was used regardless of the B, G, and R concentration values.²Was dropped.
[0099]
[Table 1]

[0100]
[Treatment liquid supply head]
FIG. 4 is an enlarged view of the front surface of the orifice of the processing liquid supply means (processing liquid supply head) 52. The processing liquid supply head 52 is provided with a processing liquid chamber 58 for each orifice and a droplet generating means for ejecting liquid droplets from the processing liquid chamber. The droplet generating means is: (1) a means for changing the volume in the processing liquid chamber (pressure chamber) 58 by means of an electromechanical conversion means such as a piezoelectric element to eject droplets from the orifice 59; and (2) a heating element. And the like, which generates and expands bubbles in the processing liquid chamber 58 to increase the processing liquid pressure and eject droplets from the orifice 59. These techniques have been put to practical use in ink jet printers and the like. The droplets ejected from the orifice 59 and flying in the air adhere to predetermined positions on the emulsion surface of the photosensitive material P, and develop a latent image formed by the exposure means to form a visible image.
[0101]
The plurality of orifices 59 are arranged in at least two rows. By shifting the first orifice row and the second orifice row by a half pitch, the width in the width direction of the photosensitive material in the direction orthogonal to the photosensitive material transport direction is shifted. Increases droplet density. The density in the width direction of the plurality of orifices 59 is determined by the required color development density. The plurality of orifices 59 are not limited to the above-described two-row arrangement, but may be arranged in three or more rows. The droplet generating means is provided on a side surface of the processing liquid chamber 58 communicating with the orifice 59 or on a surface facing the orifice 59.
[0102]
In the embodiment of the present invention, a supply head in which a plurality of bubble jet type orifices 59 are arranged in a line is used. The plurality of orifices 59 of the supply head are in a four-row staggered arrangement. The distance between the orifices 59 is 100 μm, which is the distance between the edges of the orifice 59 and the nearest orifice 59. The diameter of the orifice 59 is 50 μm, the number of treatment liquid supply times (number of droplet ejections) per second is 5,000, and the amount of treatment liquid supply per one time (volume of one droplet) is 0.3 pl. The projected line density of the orifice array is 624 dpi.
[0103]
The projection line density is the number of orifices per unit length (1 inch) when the number of orifices in a plurality of orifice rows is summed and regarded as one row.
[0104]
One orifice row was prepared as a comparative processing liquid supply head. The diameter and spacing of the orifices are the same as in the first embodiment.
[0105]
(Photosensitive material)
The following development processing is carried out using a wedge-exposed QA-A6 photographic paper manufactured by Konica Corporation in a usual manner.
[0106]
(Processing solution formulation in color developing solution container)
Per liter
Sodium sulfite 0.05g
Diethylenetriaminepentaacetic acid pentasodium 3.0 g
Polyethylene glycol # 4000 10.0g
Bis (sulfoethyl) hydroxylamine disodium 12.0g
Chino Pearl SFP 2.0g
Potassium carbonate 33.0 g
Sodium p-toluenesulfonate 20.0 g
CD-3 10.0g
Potassium hydroxide 5.0g
Adjust the pH to 11.0 with potassium hydroxide or sulfuric acid.
[0107]
(Bleach-fixing / stabilization process)
The treatment is performed with the treatment liquid for the process under the processing conditions of the Konica Corporation CPK-2-28 process.
[0108]
〔result〕
The photosensitive material processed using the processing liquid supply head having a plurality of orifice rows does not cause unevenness in development, and the processing can be completed in a short time required for dropping the droplets. Further, by changing the amount of liquid droplets in accordance with the image density, generation of stain on a white background of the photosensitive material was reduced, and development stability was improved. Further, the consumption amount of the processing liquid can be kept low.
[0109]
Example 2
(Automatic processor)
FIG. 5 is a schematic configuration diagram of a main part of the automatic processing machine according to the second embodiment. A heating means 10 for heating the silver halide photographic light-sensitive material P is provided upstream of the transport path of the silver halide photographic light-sensitive material P to be processed by the processing liquid. The heating means 10 includes a heating drum 11 for heating the photosensitive material P from the emulsion side. An outlet roller 12 is provided below the heating drum 11. On the left side of the heating drum 11 is an inlet roller 13. A pressure belt drive roller 14 is provided on the left side of the exit roller 12 and below the entrance roller 13. The pressure belt 15 is stretched over the outlet roller 12, the inlet roller 13, and the pressure belt drive roller 14, and moves while being pressed against the heating drum 11 over a 90 ° section of the peripheral surface of the heating drum 11. The photosensitive material P is pressed onto the heating drum 11 and transported. Thus, the photosensitive material P is heated.
[0110]
Downstream of the heating drum 11 in the conveying path of the photosensitive material P, there is a developing means 20. The development processing means 20 includes a first processing solution container 25 containing a low pH color developing agent solution for processing the photosensitive material P and a photosensitive solution P as a processing solution container containing a processing solution for processing the photosensitive material P. And a second processing liquid container 27 for storing a high pH liquid for processing the liquid. The first processing liquid supply means 26 for supplying the processing liquid contained in the first processing liquid container 25 to the photosensitive material P and the processing liquid contained in the second processing liquid container 27 are supplied to the photosensitive material P. A supply head described later is used as the second processing liquid supply means 28 for supplying. Thus, the first processing liquid supply means 26 and the second processing liquid supply means 28 supply the color developing solution to the emulsion surface of the photosensitive material P heated by the heating means 10 via the gas phase. The processing liquid overflowing from the photosensitive material P is discharged to a waste liquid part (not shown) by the receiving tray 29.
[0111]
The light-sensitive material P that has been color-developed by the developing means 20 is bleach-fixed in a bleach-fixing solution tank BF, stabilized in a stabilization tank ST, and dried in a drying unit Dry.
[0112]
[Heating conditions / supply head]
Same as Example 1.
[0113]
(Sensitive materials)
The Konica Corporation's QA-A6 photographic paper that has been exposed in the usual manner is processed.
[0114]
(Processing liquid formulation in first processing liquid container)
Per liter
Sodium sulfite 1.0g
Bis (sulfoethyl) hydroxylamine disodium 12.0g
CD-3 30.0g
Adjust the pH to 2-3 with potassium hydroxide or sulfuric acid.
[0115]
(Processing liquid formulation in second processing liquid container)
Per liter
Sodium sulfite 0.05g
Potassium carbonate 100.0g
Diethylenetriaminepentaacetic acid pentasodium 3.0 g
Polyethylene glycol # 4000 10.0g
Bis (sulfoethyl) hydroxylamine disodium 12.0g
Chino Pearl SFP 2.0g
Sodium p-toluenesulfonate 20.0 g
Potassium hydroxide 5.0g
Adjust the pH to 11.0 with potassium hydroxide or sulfuric acid.
[0116]
(Bleach-fixing / stabilization process)
The treatment is performed with the treatment liquid for the process under the processing conditions of the Konica Corporation CPK-2-28 process.
[0117]
(Treatment liquid adjusting means)
This is carried out in the same manner as in Example 1, but the amount of drop is changed for both the first developer and the second developer as shown in Table 2 below. As a comparative example, a constant amount of 40 ml / m irrespective of the concentrations of B, G, and R.²Is dropped. The processing liquid supply means 26 and 28 used had the same structure as the processing liquid supply head 52 of the first embodiment.
[0118]
[Table 2]

[0119]
〔result〕
The photosensitive material P processed using the processing liquid supply means 26 and 28 having a plurality of orifice rows does not cause development unevenness, and the processing time required for dropping the liquid droplets can be reduced.
[0120]
Example 3
In the treatment liquid amount adjusting means of Example 2, the degree of overlap of the droplets was changed as shown in Table 3 below, and the unevenness of the density was observed. At this time, the used photosensitive material P is subjected to solid gray exposure so that the density becomes 0.3.
[0121]
The overlapping degree of the droplets in the transport direction (longitudinal direction) of the photosensitive material P will be described. By ejecting the rear orifice at this time, the rear droplet row can be overlapped with the front droplet row. The degree of overlap means that the area of one dot droplet is S, and the area of a portion surrounding each droplet surrounding the droplet is S._DThen, the degree of overlap of droplets = S_D/ S, which can be adjusted by changing the injection timing of the rear orifice row relative to the front orifice row.
[0122]
The overlapping degree of the droplets in the width direction of the photosensitive material P can be adjusted by changing the pitch of the plurality of orifice rows so as to form a staggered arrangement and changing the area of one dot droplet by changing S.
[0123]
[Table 3]

[0124]
As can be seen from Table 3, by setting the degree of overlap of the droplets to 0.2 or more, a predetermined development density can be formed, and development unevenness can be suppressed.
[0125]
Example 4
The same evaluation as in Example 2 was performed by changing the projected line densities of the orifice rows by the processing liquid supply units 26 and 28 of Example 2 as shown in Table 4 below. The dot linear density in the transport direction of the photosensitive material P by the processing liquid supply means 26, 28 is 156 dpi at the time of the minimum drop amount.
[0126]
[Table 4]

[0127]
As can be seen from Table 4, development unevenness can be improved by making the projected line density of the orifice row larger than the dot line density of the photosensitive material P in the transport direction of the processing liquid supply means 26, 28.
[0128]
Example 5
In Example 2, after the color development processing, the bleach-fix processing step is performed in a bleach-fix processing liquid tank BF. In the bleach-fix processing step, a bleaching liquid BL having the following composition is supplied to a supply head similar to that used in the color development processing. The bleaching step was performed by dripping under the following conditions, and then the fixing step in the fixing tank Fix, the stabilizing step in the stabilizing tank ST, and the drying step in the drying unit Dry.
[0129]
[Heating conditions / supply head]
FIG. 6 is a schematic configuration diagram showing another embodiment of a main part of the automatic machine according to the present invention.
[0130]
The processing was performed by the automatic processing machine shown in FIG. The processing time and the processing temperature are as shown below.
[0131]

The processing liquid supply head 92 of the bleaching processing means 90 used was the same as in Example 2.
[0132]
Formulation of processing solution in bleaching solution container 91
Per liter
PDTA-Fe 100g
NH₄40 g of Br
60 g of succinic acid
PDTA-4H 6g
The pH is adjusted to 4.0 using potassium carbonate and sulfuric acid.
[0133]
Fixing solution Anch solution
Ammonium thiosulfate 100g
Ammonium sulfite 10g
10 g of imidazole
EDTA-2Na 1g
Adjust the pH to 7.0 with potassium hydroxide or sulfuric acid.
[0134]
Treatment liquid adjustment means
Table 5 shows the amount of the bleaching solution dropped when the overlap was 0.5 in the same manner as in Example 2. The drop amount of the color developing solution is the same as in Example 2.
[0135]
[Table 5]

[0136]
The degree of overlap of the droplets was changed as shown in Table 6 below, and the amount of residual silver in the Dmax portion was measured by a fluorescent X-ray method.
[0137]
[Table 6]

[0138]
As can be seen from Table 6, also in the bleaching step, good bleaching performance is exhibited when the degree of overlap of the droplets is 0.2 or more.
[0139]
【The invention's effect】
As described above, when adjusting the supply amount of the processing liquid in accordance with the image signal to be recorded on the light-sensitive material, a plurality of orifice rows (particularly, image signals corresponding to low density) are provided, and the per unit area of the processing liquid is provided. By making the drop amount a discontinuous change amount and making the drop amount correspond to the image signal, it is possible to reduce the amount of the processing liquid in the low-density portion and prevent development unevenness from occurring.
[0140]
Further, since there is no need to supply the processing liquid to the white background, it is possible to completely prevent the generation of stain due to the oxide of the color developing agent.
[0141]
According to the fourth aspect, development unevenness is further prevented at both low and high densities, and stable developability can be obtained even when the processing temperature varies.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram of a main part of an automatic developing machine according to a first embodiment of the present invention.
FIG. 2 is a perspective view of a color developing section of the automatic developing machine.
FIG. 3 is a perspective view of a processing liquid supply port of the automatic developing machine near a drying prevention unit.
FIG. 4 is an enlarged view of a front surface of an orifice of the processing liquid supply means (processing liquid supply head).
FIG. 5 is a schematic configuration diagram of a main part of an automatic developing machine according to a second embodiment of the present invention.
FIG. 6 is a schematic configuration diagram showing another embodiment of a main part of the automatic developing machine of the present invention.
[Explanation of symbols]
10 heating means
20 Developing means
25, 27, 91 Processing liquid container
26, 28, 92 Processing liquid supply means (processing liquid supply head)
30 Second heating means
40 Solid processing agent supply means
50 developing means
51 Processing liquid container
52 Treatment liquid supply means (treatment liquid supply head)
54 Circulation pump
55 filters
56 Treatment liquid supply container
57 Rotor
58 Processing liquid chamber
59 Orifice (treatment liquid supply port)
70 Sensitive material detection means
80 Supply port drying prevention means
P Silver halide photographic material (sensitive material)

Claims (4)

Supply means for supplying the processing solution for processing the silver halide photographic material onto the emulsion surface of the silver halide photographic material via the gas phase, and the amount of processing solution supplied to the emulsion surface of the silver halide photographic material Adjusting means for adjusting the
The adjusting means is characterized in that the minimum drop amount per unit area of the processing liquid is adjusted to 0.2 or more in the degree of overlap of the droplets,
Said supply means has a plurality of orifice arrays with respect to the conveying direction of the silver halide photographic light-sensitive material, the projection line density of said plurality of orifice arrays is, the dot line density of the photosensitive material conveyance direction of the process liquid by said supply means An automatic developing machine for silver halide photographic light-sensitive materials, characterized in that it is larger than the minimum drop amount . 2. The automatic processor according to claim 1, wherein the processing solution for a silver halide photographic material is a color developing solution or a solution having a bleaching ability. 3. The automatic developing machine for a silver halide photographic light-sensitive material according to claim 1, wherein the processing solution for the silver halide photographic light-sensitive material is for color development. 2. The automatic development for a silver halide photographic material according to claim 1, wherein said adjusting means makes a drop amount per unit area of the processing solution a discontinuous change amount and makes the drop amount correspond to an image signal. Machine.

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