JPS6395452A - Bleach-fix bath excellent in rapid processing - Google Patents

Bleach-fix bath excellent in rapid processing

Info

Publication number
JPS6395452A
JPS6395452A JP24174886A JP24174886A JPS6395452A JP S6395452 A JPS6395452 A JP S6395452A JP 24174886 A JP24174886 A JP 24174886A JP 24174886 A JP24174886 A JP 24174886A JP S6395452 A JPS6395452 A JP S6395452A
Authority
JP
Japan
Prior art keywords
bleach
hydrogen atom
group
solution
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP24174886A
Other languages
Japanese (ja)
Inventor
Satoru Kuze
哲 久世
Shigeharu Koboshi
重治 小星
Naoki Takabayashi
高林 直樹
Kazuhiro Kobayashi
一博 小林
Moeko Higuchi
茂枝子 樋口
Hiroaki Kobayashi
弘明 小林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Priority to JP24174886A priority Critical patent/JPS6395452A/en
Publication of JPS6395452A publication Critical patent/JPS6395452A/en
Pending legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421Additives other than bleaching or fixing agents

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

PURPOSE:To enable to rapid processing, and to obtain the titled bath suitable for work environment by controlling pH value of a processing solution to a range of 3.0-6.8, and by incorporating a ferric complex salt contg. a specific compd. as a ligant and a specific compd. to the titled bath. CONSTITUTION:The pH value of the processing solution which effects the bleach-fix of a silver halide photographic sensitive material for photographing lies in the range of 3.0-6.8. The titled bath contains the ferric complex salt contg. the compd. shown by formula I as the ligant, and the compd. shown by formula II. In formula I, R1 is hydrogen atom or a lower alkyl group, (n1)-(n3) are each an integer of 0-3. In formula II, R2 and R3 are each hydro gen atom, alkyl, acyl, or carbamoyl group, R4-R6 are each hydrogen atom or alkyl group, (m) is 0, 1 or 2. M is hydrogen atom or a cation. Thus, the titled bath is applied to the photosensitive material for the photographing, and enable rapid processing. As ammonia gas does not generate in the processing, the titled bath is preferable in the work environment.

Description

【発明の詳細な説明】 U産業上の利用分野1 本発明は漂白定着液に関し、詳しくは撮影用感光材料に
適用して迅速処理化を達成できる漂白定着液に関する。
DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application 1 The present invention relates to a bleach-fix solution, and more particularly to a bleach-fix solution that can be applied to photosensitive materials for rapid processing.

[発明の背景] 現在、高感度高沃臭化銀乳剤を用いた撮影用感光材料の
脱銀処理は漂白工程と定着工程が別々に行われている。
[Background of the Invention] Currently, in the desilvering treatment of photosensitive materials for photography using high-sensitivity silver iodobromide emulsions, a bleaching step and a fixing step are performed separately.

本発明者等は上記撮影用感光材料の脱銀処理の簡略化お
よび迅速化を図るため、漂白と定着を一浴で処理する漂
白定着処理化を検討してきた。
In order to simplify and speed up the desilvering process of the photographic light-sensitive materials, the present inventors have investigated a bleach-fixing process in which bleaching and fixing are performed in one bath.

その検討の中で、上記漂白定着液としては、液保存性お
よび得られる色素画像の復色不良の発生等の観点から従
来からpHが高い領域で使用することが有利であるとさ
れ、その高pH領域で浸れた脱銀能力を有する漂白剤を
探索した結果、本発明者等は種々のアミノポリカルボン
酸鉄錯体の中 ′でもジエチレントリアミン五酢酸第2
鉄錯塩(DTPA −Fe錯塩)が脱銀速度、得られる
色素画像の復色性および漂白定着液の経時保存性を満足
できるものとして提案してきた。(特開昭60−134
238号、同 60−130738号、同 60−13
6744号等) 上記DTPA−FeIil塩は、pHが高い領域、具体
的には約pH7〜9という範囲で上記の如くの特性を満
足できるものであるが、かかるpH領域ではアンモニア
ガスが発生し易く、狭い空白で現像処理を行う際には作
業環境上好ましくない点を有していた。さらに、感光材
料を長期にわたり処理した際の経時において、漂白定着
液中に第1鉄イオンの蓄積に起因すると考えられる脱銀
能力の低下と復色不良が発生することがわかってきた。
During the study, it was found that it is advantageous to use the above bleach-fix solution in a high pH range from the viewpoint of solution storage stability and the occurrence of poor color recovery of the obtained dye image. As a result of searching for bleaching agents with desilvering ability in the pH range, the present inventors found that among various aminopolycarboxylic acid iron complexes, diethylenetriaminepentaacetic acid
Iron complex salts (DTPA-Fe complex salts) have been proposed as being able to satisfy the desilvering speed, the recoloring properties of the resulting dye images, and the shelf life of bleach-fix solutions over time. (Unexamined Japanese Patent Publication No. 60-134
No. 238, No. 60-130738, No. 60-13
6744, etc.) The above-mentioned DTPA-FeIil salt can satisfy the above characteristics in a high pH range, specifically in the range of approximately pH 7 to 9, but ammonia gas is likely to be generated in such a pH range. However, when developing in a narrow space, the work environment is unfavorable. Furthermore, it has been found that when photographic materials are processed over a long period of time, desilvering ability decreases and color restoration failure occurs, which is thought to be due to the accumulation of ferrous ions in the bleach-fix solution.

上記の欠点について詳細に検討を加えた結果、第1鉄イ
オンの蓄積は、漂白定着液のpHに大きく依存し、さら
に一定のpH以上では処理した際の経時において、通常
漂白剤として用いられているアミノポリカルボン酸鉄錯
塩に共通して起こる問題点であることがわかった。
A detailed study of the above disadvantages revealed that the accumulation of ferrous ions is highly dependent on the pH of the bleach-fix solution, and that above a certain pH, the accumulation of ferrous ions over time during processing is not normally used as a bleaching agent. This problem was found to be common to iron complex salts of aminopolycarboxylic acids.

本発明者等は、さらに検討を続けた結果、特定の低いp
H[でかつ特定のアミノポリカルボン酸鉄錯塩を用いる
ことにより、上記第1鉄イオンの蓄積に起因すると考え
られる脱銀能力の低下と復色不良が同時に解決され、か
つアンモニアガスの発生も解消されることを見い出した
As a result of further investigation, the present inventors discovered that a specific low p
By using H[and a specific aminopolycarboxylic acid iron complex salt, the decrease in desilvering ability and poor color recovery, which are thought to be caused by the accumulation of ferrous ions, can be solved simultaneously, and the generation of ammonia gas can also be solved. I found out that it can be done.

また、該漂白定着液の実用化に際して、特定のアミノア
ルキレンスルホン酸誘導体を用いることにより、上記問
題点の改良効果に悪影響を与えることなく、連続処理時
における漂白定着液の経時保存性の劣化を良好に防止で
きることを見い出し本発明を為すに到ったものである。
In addition, when putting the bleach-fix solution into practical use, by using a specific aminoalkylene sulfonic acid derivative, the deterioration of the storage stability of the bleach-fix solution over time during continuous processing can be prevented without adversely affecting the improvement effect of the above problems. We have discovered that this can be effectively prevented and have come up with the present invention.

[発明の目的〕 従って、本発明の第一の目的は撮影用写真感光材料に適
用して前記欠点を解決し、迅速処理化を可能にした漂白
定着液を提供することにある。本発明の第二の目的は、
アンモニアガスの発生がなく、作業環境上好ましい漂白
・定着液の提供にある。
[Object of the Invention] Therefore, the first object of the present invention is to provide a bleach-fixing solution which can be applied to photographic light-sensitive materials for use in photography, solving the above-mentioned drawbacks, and enabling rapid processing. The second object of the present invention is to
The purpose of the present invention is to provide a bleaching/fixing solution that does not generate ammonia gas and is favorable for the working environment.

[発明の構成] 本発明の上記目的は撮影用ハロゲン化銀写真感光材料を
漂白定着する処理液において、該液のpHが3.0〜6
.8の範囲にあり、かつ下記一般式[I]で示される化
合物を配位子とする第2鉄錯塩を含有し、さらに下記一
般式[I[]で示される化合物を含有する漂白定着液に
より達成された。
[Structure of the Invention] The above object of the present invention is to provide a processing solution for bleaching and fixing a silver halide photographic light-sensitive material for photographing, the pH of which is 3.0 to 6.
.. 8 and containing a ferric complex salt having a compound represented by the following general formula [I] as a ligand, and further containing a compound represented by the following general formula [I]. achieved.

一般式[I] (式中、R1は水素原子または低級アルキル基を表わし
、nl、n2およびn3はそれぞれ0〜3の整数を表わ
す。但し、n+ 、n2eよびn3の合計は3または4
の整数であり、 数の総和は3以上である。) 一般式[II] (式中、R2およびR3はそれぞれ水素原子、アルキル
基、アシル基またはカルバモイル基を表わす。R4、R
sおよびR6はそれぞれ水素原子またはアルキル基を表
わし、mは0.1または2を表わす。Mは水素原子また
はカチオンを表わす。) [発明の具体的構成] 本発明の漂白定着液には、一般式[I]で示される化合
物を配位子とする第2鉄錯塩が用いられる。
General formula [I] (In the formula, R1 represents a hydrogen atom or a lower alkyl group, and nl, n2 and n3 each represent an integer of 0 to 3. However, the sum of n+, n2e and n3 is 3 or 4.
is an integer, and the sum of the numbers is 3 or more. ) General formula [II] (wherein R2 and R3 each represent a hydrogen atom, an alkyl group, an acyl group or a carbamoyl group. R4, R
s and R6 each represent a hydrogen atom or an alkyl group, and m represents 0.1 or 2. M represents a hydrogen atom or a cation. ) [Specific Structure of the Invention] The bleach-fix solution of the present invention uses a ferric complex salt having a compound represented by the general formula [I] as a ligand.

一般式[I]において、R+ としては好ましくは水素
原子である。また、 数の総和の最も好ましくは3である。
In general formula [I], R+ is preferably a hydrogen atom. Moreover, the most preferable sum of the numbers is 3.

以下、一般式[I]で示される化合物の好ましい具体例
を示す。
Preferred specific examples of the compound represented by the general formula [I] are shown below.

例示化合物 上記一般式[1]で示される化合物を配位子とする第2
鉄錯塩(以下、本発明の第2鉄錯塩という)は、フリー
のM(水素塩)としても用いられるが、対温としてナト
リウム塩、カリウム塩、リチウム塩等のアルカリ金B塩
、もしくはアンモニウム塩、または水溶性アミン塩、例
えばトリエタノールアミン塩等としても用いることがで
きる。
Exemplary Compound A second compound having the compound represented by the above general formula [1] as a ligand
The iron complex salt (hereinafter referred to as the ferric complex salt of the present invention) is also used as a free M (hydrogen salt), but as a counter temperature, it can be used as an alkali gold B salt such as sodium salt, potassium salt, lithium salt, or ammonium salt. Alternatively, it can also be used as a water-soluble amine salt, such as a triethanolamine salt.

好ましくはカリウム塩、ナトリウム塩及びアンモニウム
塩が使われる。これらの本発明の第2鉄錯塩は少なくと
も1種用いればよいが、2種以Fを併用することもでき
る。ざらに本発明外の第2鉄錯塩と併用とすることもで
きる。
Preferably potassium, sodium and ammonium salts are used. At least one kind of these ferric complex salts of the present invention may be used, but two or more kinds thereof can also be used in combination. It can also be used in combination with ferric complex salts other than those of the present invention.

上記例示の本発明の第2鉄錯塩の中では好ましくは、例
示化合物(I−1)、(I−2>および(ニー3ンを配
位子として用いる第2鉄錯塩である。ざらに、例示化合
物No、<l−1)、(I−2)および(I−3)の中
でも溶解性の点から(ニー1)、(I−2>を用いるこ
とが特に好ましく、本発明の目的の効果等種々の点を鑑
みると、<I−1>を用いることが本発明において最も
好ましい。
Among the ferric complex salts of the present invention exemplified above, preferred are ferric complex salts using exemplified compounds (I-1), (I-2> and (I-2) as ligands. Among the exemplified compounds No., <l-1), (I-2) and (I-3), it is particularly preferable to use (nee 1) and (I-2> from the viewpoint of solubility, and for the purpose of the present invention. Considering various points such as effects, it is most preferable to use <I-1> in the present invention.

本発明の第2鉄錯塩は、本発明の漂白定着液中本発明の
効果を得る足であればいかなる足でも用いられるが、第
2鉄錯塩濃度が高くなりすぎると、漂白定着液の保存性
が劣化し、一方、第2鉄鉗塩の濃度が低すぎると脱銀性
能と復色性能が劣化する。従って通常0.02〜1.3
00モル/の範囲で用いることが好ましく、0.10〜
1.20モル/りの範囲で用いることがより好ましい。
The ferric complex salt of the present invention can be used in any type of bleach-fix solution as long as it achieves the effects of the present invention, but if the concentration of the ferric complex salt becomes too high, the shelf life of the bleach-fix solution may be On the other hand, if the concentration of ferric salt is too low, the desilvering performance and color restoration performance will deteriorate. Therefore, usually 0.02 to 1.3
It is preferable to use it in the range of 0.00 mol/
It is more preferable to use it in a range of 1.20 mol/liter.

特に0,20〜0.800モル/の範囲で用いると本発
明の効果を良好に秦し好ましい。
In particular, it is preferable to use it in a range of 0.20 to 0.800 mol/mole since the effect of the present invention can be achieved well.

本発明の漂白定着液は、pH3,0未満では亜硫酸ガス
発生のため、またpH6,8より高ければ本発明の効果
が不充分のため、そのpH範囲はpH3,0〜6.8で
あり、このpH領域であればいかなるpHでも用いるこ
とができるが脱銀性と復色性の他に、各種鉄塩の低温時
の溶解性、亜硫酸イオンより発生する亜1[Qガス臭気
を考えるとI)84.0〜6.7で用いることが好まし
く、特に pH5,0〜6.5で用いることが最も好ま
しい。
The bleach-fix solution of the present invention has a pH range of 3.0 to 6.8, because if the pH is less than 3.0, sulfur dioxide gas is generated, and if the pH is higher than 6.8, the effect of the present invention is insufficient. It can be used at any pH within this pH range, but in addition to its desilvering and recoloring properties, it is also important to consider the solubility of various iron salts at low temperatures, and the odor of nitrogen gas generated from sulfite ions. ) 84.0 to 6.7, most preferably pH 5.0 to 6.5.

本発明の漂白定着液には、一般式[II]で示される化
合物を用いる。
A compound represented by the general formula [II] is used in the bleach-fix solution of the present invention.

一般式[ffl]において、R2およびR3はそれぞれ
水素原子、アルキル基、アシル基またはカルバモイル基
を表わすが、R2およびR3で表わされるアルキル基は
好ましくは炭素数1〜6のアルキル基であり、置換基(
例えばヒドロキシ基、メトキシ基等のアルコキシ基等)
を有するものも含む。アシル基としては、置換基(例え
ばアミン基等)を有するものも含み、例えばアセチル基
、アミノアセチル基等が挙げられる。
In the general formula [ffl], R2 and R3 each represent a hydrogen atom, an alkyl group, an acyl group, or a carbamoyl group, and the alkyl group represented by R2 and R3 is preferably an alkyl group having 1 to 6 carbon atoms, and is substituted with Group (
For example, alkoxy groups such as hydroxy groups and methoxy groups)
Including those with. Examples of the acyl group include those having a substituent (for example, an amine group, etc.), such as an acetyl group and an aminoacetyl group.

R4、R5およびR6は水素原子またはアルキル基を表
わすが、R4、RsおよびR6で表わされるアルキル基
は、好ましくは炭素数1〜5のアルキル基であり、置換
基(例えばヒドロキシ基、カルボキシ基等)を有するも
のも含む。
R4, R5, and R6 represent a hydrogen atom or an alkyl group, and the alkyl group represented by R4, Rs, and R6 is preferably an alkyl group having 1 to 5 carbon atoms, and a substituent (e.g., hydroxy group, carboxy group, etc.). ).

mは011または2を表わすが、好ましくはOまたは1
であり、特に好ましくはOである。
m represents 011 or 2, preferably O or 1
and O is particularly preferred.

Mは水素原子またはカチオンを表わすが、カチオンとし
ては、例えばカリウム、ナトリウム、アンモニウム等が
挙げられる。
M represents a hydrogen atom or a cation, and examples of the cation include potassium, sodium, and ammonium.

上記R2およびR3において、好ましくは水素原子、メ
チル基、エチル基であり、特に好ましくは共に水素原子
の場合である。
The above R2 and R3 are preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom.

R4、RsおよびR6において、好ましくは水素原子、
メチル基、エチル基、ヒドロキシメチル基であり、特に
好ましくは、すべてが水素原子である場合である。
In R4, Rs and R6, preferably a hydrogen atom,
These include a methyl group, an ethyl group, and a hydroxymethyl group, particularly preferably when all of them are hydrogen atoms.

以下、一般式[II]で示される化合物の代表的具体例
を示すが、これらに限定されない。
Hereinafter, typical examples of the compound represented by the general formula [II] will be shown, but the invention is not limited thereto.

これら前記一般式[I[]で示される化合物は、単独で
用いても2種以上併用してもよく、漂白定着液11あた
り、0.1〜200gの範囲で使用され、より好ましく
は0.3〜50oの範囲で使用される。
These compounds represented by the general formula [I[] may be used alone or in combination of two or more, and are used in an amount of 0.1 to 200 g per bleach-fixer 11, more preferably 0.1 to 200 g. It is used in the range of 3 to 50 degrees.

本発明では、前記一般式[I[]で示される化合物とと
もに亜硫酸塩又は亜硫酸放出化合物(例えば、特公昭5
4−38895号明細書中のカルボニル重亜硫酸塩付加
物等)を併用する際に漂白定着液の経時保存性がより改
良されるために、本発明においてはより好ましく用いら
れる。
In the present invention, a sulfite or a sulfite-releasing compound (for example,
4-38895)) is more preferably used in the present invention because the storage stability of the bleach-fix solution over time is further improved when it is used in combination with carbonyl bisulfite adducts (such as the carbonyl bisulfite adduct described in No. 4-38895).

本発明では、亜硫酸塩又は亜硫酸放出化合物を本発明の
漂白定着液1fl当り1 X 10−3モル以上含有す
るのが好ましく、より好ましくは0.02モル以上2.
0モル以下であり、さらにより好ましくは0.05モル
以上1.3モル以下、最も好ましくは0.09モル以上
0.9モル以下で使用される。
In the present invention, the content of the sulfite or sulfite-releasing compound is preferably 1.
It is used in an amount of 0 mol or less, even more preferably 0.05 mol or more and 1.3 mol or less, most preferably 0.09 mol or more and 0.9 mol or less.

上記亜硫M塩としては、亜硫酸アンモニウム、亜硫酸ナ
トリウム、亜硫酸カリウム、亜硫酸水素ナトリウム、亜
硫酸水素カリウム、メタ重亜硫酸ナトリウム等があげら
れる。
Examples of the sulfite M salt include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium metabisulfite, and the like.

本発明の漂白定着液に含ませるハロゲン化銀定着剤とし
ては通常の定着処理に用いられるようなハロゲン化銀と
反応して水溶性の錯塩を形成する化合物、例えばチオ硫
酸カリウム、チオ硫酸ナトリウム、チオ硫酸アンモニウ
ムの如きチオ硫酸塩、チオシアン酸カリウム、チオシア
ン酸ナトリウム、チオシアン酸アンモニウムの如きチオ
シアン酸塩、チオ尿素、チオエーテル、高濃度の臭化物
、ヨウ化物等がその代表的なものである。これらの定着
剤は5g/2以上、好ましくは50g/ffi以上、よ
り好ましくは70g#!以上溶解できる範囲のaで使用
できる。
The silver halide fixing agent to be included in the bleach-fixing solution of the present invention is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. These fixing agents are 5g/2 or more, preferably 50g/ffi or more, more preferably 70g#! It can be used in a range where it can be dissolved.

本発明の漂白定着液は、種々の添加剤を含むことができ
る。添加剤としては、特にアルカリハライドまたはアン
モニウムハライド、例えば臭化カリウム、臭化ナトリウ
ム、塩化ナトリウム、臭化アンモニウム、沃化カリウム
、沃化すI〜ツリウム沃化アンモニウム等を含有させる
ことが望ましい。
The bleach-fix solution of the present invention can contain various additives. As additives, it is particularly desirable to include alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, I-thulium iodide, and ammonium iodide.

本発明の漂白定着液には硼酸、硼砂、水酸化ナトリウム
、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、重
炭酸ナトリウム、重炭酸カリウム、酢酸、酢酸ナトリウ
ム、水酸化アンモニウム等の各種の塩からなるpHMW
iJ剤を単独であるいは2種以上組合せて含有せしめる
ことができる。さらにまた、各種の蛍光増白剤や消泡剤
あるいは界面活性剤や防ばい剤を含有せしめることもで
きる。
The bleach-fix solution of the present invention contains pHMW containing various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide.
The iJ agent may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained.

またアセチルアセトン、ホスホノカルボン酸、ポリリン
酸、有機ホスホン酸、オキシカルボン酸、ポリカルボン
酸、ジカルボン酸及びアミノポリカルボン酸等の有機キ
レート剤あるいはニトロアルコール、硝酸塩等の安定剤
、アルカノールアミン等の可溶化剤、有機アミン等のス
ティン防止剤、その他の添加物や、メタノール、ジメチ
ルホルムアミド、ジメチルスルホキシド等の有機溶媒を
適宜含有せしめることができる。
In addition, organic chelating agents such as acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid and aminopolycarboxylic acid, stabilizers such as nitroalcohol and nitrate, and stabilizers such as alkanolamines, etc. A solubilizing agent, an anti-staining agent such as an organic amine, other additives, and an organic solvent such as methanol, dimethylformamide, dimethyl sulfoxide, etc. can be appropriately contained.

本発明の漂白定着液には漂白促進剤を用いることが好ま
しく、例えば特願昭60−160943号等に記載され
る化合物を用いることができ、下記一般式[A〜工]〜
[A〜TV ]に示される化合物を用いることが本発明
の効果を良好に秦し好ましい。
It is preferable to use a bleaching accelerator in the bleach-fixing solution of the present invention, and for example, compounds described in Japanese Patent Application No. 160943/1983 can be used, and the compounds of the following general formulas [A~E] ~
It is preferable to use the compounds shown in [A to TV] because the effects of the present invention can be obtained satisfactorily.

一般式[A−II 式中、Qlは含窒素へテロ環(5〜6員の不飽和環また
は飽和環が縮合しているものも含む)を形成するに必要
な原子群を表わし、R1は水素原またはアルキル基を表
わづ−0但し、Q′はQlと同義である。
General formula [A-II In the formula, Ql represents an atomic group necessary to form a nitrogen-containing heterocycle (including those in which 5- to 6-membered unsaturated rings or saturated rings are condensed), and R1 is Represents a hydrogen atom or an alkyl group -0 However, Q' has the same meaning as Ql.

一般式[A−II] 式中、R2およびR3はそれぞれ水素原子、炭素原子数
1〜6のアルキル基、ヒドロキシ基、カルボキシ基、ア
ミノ基、炭素原子数1〜3のアシル基、アリール基また
はアルケニル基を表わす。
General formula [A-II] In the formula, R2 and R3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or Represents an alkenyl group.

Aは 又はn1価のへテロ環残基(5〜6員の不飽和環が縮合
しているものも含む)を表わし、Xは=$1−〇または
= N R″を表わす。ここで、RおよびR′はそれぞ
れR2J5よびR3と同義、X′はXと同義、2は水素
原子、アルカリ金層原子、アンモニウム基、アミノ基、
含窒素へテロ環残基、アルキル基、または 原子を表わし、Rnは水素原子、炭素原子数1〜6のア
ルキル基、シクロアルギル基、アリール基、ヘテロ環残
W(5〜6員の不飽和環が縮合しているものも含む)ま
たはアミノ基を表わし、01〜o6およびm1〜15は
それぞれ1〜6の整数を表わす。Bは炭素原子数1〜G
のアルキレン基を表わし、Yは−Nにまたは−CH/を
表わし、R4およびR5はそれぞれR2およびR3と同
義である。但し、R4およびR5はそれぞれ−B−8Z
を表わしてもよく、またR2とR3、RとR′、R4と
R5はそれぞれ結合して環を形成してもよい。
A represents or n1-valent heterocyclic residue (including those in which 5- to 6-membered unsaturated rings are condensed), and X represents = $1-〇 or = N R''. Here, R and R' are synonymous with R2J5 and R3, respectively, X' is synonymous with X, 2 is a hydrogen atom, an alkali gold layer atom, an ammonium group, an amino group,
Represents a nitrogen-containing heterocyclic residue, an alkyl group, or an atom; Rn represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloargyl group, an aryl group, a heterocyclic residue W (a 5- to 6-membered unsaturated ring); ) or an amino group, and 01 to o6 and m1 to 15 each represent an integer of 1 to 6. B has 1 to G carbon atoms
represents an alkylene group, Y represents -N or -CH/, and R4 and R5 have the same meanings as R2 and R3, respectively. However, R4 and R5 are each -B-8Z
or R2 and R3, R and R', and R4 and R5 may be bonded to each other to form a ring.

なあ、該式で表わされる化合物はエノール化体およびそ
の塩も含む。
Incidentally, the compound represented by the above formula also includes enolated products and salts thereof.

一般式[Δ−■] R+ 式中、R6d3よびR7はそれぞれ水M原子、炭素原子
数1〜6のアルキル基、ヒドロキシ基、カルボキシ基、
アミン基、炭素原子数1〜3のアシル基、アリール基、
アルケニル基または−B+ −3Z+ を表わす。但し
、1で6とR7は結合して環を形成してもよい。Ylは
≧N−またはゝCH−を表わし、B1は炭素原子数1〜
6のアルキレン基を表わし、71 は水素原子、アルカ
リ全屈原子、アンモニウム基、アミLL含窒素へテロ環
残Mまたは の整数を表わす。] 一般式[A −IV ] R2I(IQ (G’ )z 式中、Arは211iのアリール基またはアリール基と
酸素原子および/もしくはアルキレン基とを組みあわせ
た2価の有機基を表わし、B2およびB3はそれぞれ低
級アルキレン基を表わし、R8、Rs、RloおよびR
11はそれぞれヒドロキシM換低級アルキル基を表わし
、XおよびyはそれぞれOまたは1を表わす。G′はア
ニオンを表わし、2は0,1または2を表わす。
General formula [Δ-■] R+ In the formula, R6d3 and R7 are respectively a water M atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group,
Amine group, acyl group having 1 to 3 carbon atoms, aryl group,
Represents an alkenyl group or -B+ -3Z+. However, in 1, 6 and R7 may be combined to form a ring. Yl represents ≧N- or CH-, and B1 has 1 to 1 carbon atoms.
6 represents an alkylene group, and 71 represents a hydrogen atom, a fully alkali atom, an ammonium group, an ami LL nitrogen-containing heterocyclic residue M, or an integer of the same. ] General formula [A-IV] R2I(IQ (G')z In the formula, Ar represents the aryl group of 211i or a divalent organic group combining an aryl group with an oxygen atom and/or an alkylene group, and B2 and B3 each represent a lower alkylene group, R8, Rs, Rlo and R
11 each represents a hydroxy M-substituted lower alkyl group, and X and y each represent O or 1. G' represents an anion, and 2 represents 0, 1 or 2.

以下、本発明に好ましく用いられる漂白促進剤の具体例
を示す。
Specific examples of bleach accelerators preferably used in the present invention are shown below.

例示化合物 (A−1)       (A−2) (A−3) (A−4) (A−5> (A−6) (A−7) )(、N−C5NHNHC5−NH。Exemplary compound (A-1) (A-2) (A-3) (A-4) (A-5> (A-6) (A-7) )(, N-C5NHNHC5-NH.

(A−9) 漂白促進剤の添加量は本発明の漂白定着液11当り約0
.01〜100gの範囲で用いるのが好ましく、さらに
、0.05〜50gが好ましく、特に好ましくは0.0
5〜15gである。
(A-9) The amount of bleach accelerator added is approximately 0 per 11 bleach-fixing solutions of the present invention.
.. It is preferably used in the range of 0.01 to 100 g, more preferably 0.05 to 50 g, particularly preferably 0.0 g.
It is 5-15g.

近年、公害負荷低減及び処理液コストの低減の目的から
低補充化が行なわれるが、本発明の漂白定着液も低補充
化に適用して好ましい。この時、本発明の漂白定着液中
にヨウ素イオンの蓄積が起こることが予想される。従来
、ヨウ素イオンの蓄積は、脱銀速度の低下をもたらすこ
とが知られているが、本発明の漂白定着液では、ヨウ素
イオンの蓄積によっても脱銀性が実質的に低下しないば
かりか、驚くべきことに、発色現像処理後水洗工程等洗
浄工程を経ることなく、漂白定着液に浸漬される場合に
も未露光部の濃度上昇(いわゆるカブリ)がほとんど起
こらないことが明らかとなった。
In recent years, low replenishment has been carried out for the purpose of reducing pollution load and processing solution cost, and the bleach-fixing solution of the present invention is also preferably applied to low replenishment. At this time, it is expected that iodine ions will accumulate in the bleach-fix solution of the present invention. Conventionally, it has been known that the accumulation of iodine ions causes a decrease in the desilvering rate, but in the bleach-fix solution of the present invention, not only does the accumulation of iodine ions not substantially reduce the desilvering performance, but surprisingly Interestingly, it has become clear that even when the film is immersed in a bleach-fix solution without going through a washing process such as a water washing process after color development, there is almost no increase in density in the unexposed area (so-called fog).

この時ヨウ素イオンは漂白定着液に0.0005モル/
2以上含有することが好ましく、より好ましくは、漂白
定着液に0.001モル/2以上含有することが好まし
い。
At this time, iodine ions are added to the bleach-fix solution at 0.0005 mol/
It is preferable to contain 2 or more, more preferably 0.001 mol/2 or more in the bleach-fix solution.

本発明の漂白定着液による処理時間は3分30秒以下で
あれば良いが、好ましくは3分以下、より好ましくは2
分30秒以内で用いることである。
The processing time with the bleach-fix solution of the present invention may be 3 minutes and 30 seconds or less, preferably 3 minutes or less, more preferably 2 minutes or less.
It should be used within minutes and 30 seconds.

本発明の漂白定着液の温度は80℃以下で使用されるが
、望ましくは55℃以下、最も好ましくは45℃以下で
使用される。又蒸発等を抑えて使用するのが望ましい。
The bleach-fix solution of the present invention is used at a temperature of 80°C or lower, preferably 55°C or lower, most preferably 45°C or lower. It is also desirable to use it while suppressing evaporation.

上記本発明の漂白定着液は、1ltlll用ハロゲン化
銀写真感光拐料であればいかなるハロゲン化銀写真感光
材料でも適用できる。具体的に好ましくは沃化銀含有率
が0.5モル%以上、さらに好ましくは1モル%以上含
有する高感度沃臭化銀乳剤を用いた感光材料であること
が好ましい。
The above-mentioned bleach-fix solution of the present invention can be applied to any silver halide photographic light-sensitive material as long as it is a 1ltlll silver halide photographic light-sensitive material. Specifically, a photosensitive material using a high-sensitivity silver iodobromide emulsion having a silver iodide content of 0.5 mol % or more, more preferably 1 mol % or more is preferable.

本発明の漂白定着液は、上記撮影用ハロゲン化銀写真感
光材料を発色現像後、直ちに漂白定着する処理液として
用いてもよいし、発色現像後、水洗又はリンス又は停止
等の処理を行った後の漂白定着処理液として用いてもよ
く、さらに発色現像後に前定着処理を行った後の漂白定
着処理液として用いてもよい。また、本発明の漂白定着
液による処理の後、水洗処理し、その後安定化処理して
もよいし、水洗処理工程を省略もしくは水洗水量を極端
に低減する特開昭57−8543号に記載の多段向流安
定化処理技術や、特開昭58−14834号公報に記載
されているような水洗代替処理液による処理技術に適用
することもできる。また、発色現像、漂白定着、水洗等
の工程の他に硬膜、中和、黒白現像、反転、少量水洗工
程等、必要に応じて各種 ′の補助工程が付加されても
よい。
The bleach-fixing solution of the present invention may be used as a processing solution for bleaching and fixing the silver halide photographic light-sensitive material for photography immediately after color development, or it may be used as a processing solution for washing, rinsing, stopping, etc. after color development. It may be used as a subsequent bleach-fixing treatment solution, or may be used as a bleach-fixing treatment solution after pre-fixing treatment is performed after color development. Furthermore, after the treatment with the bleach-fixing solution of the present invention, washing with water and then stabilization may be performed, or the washing process may be omitted or the amount of washing water may be extremely reduced as described in JP-A-57-8543. It can also be applied to a multi-stage countercurrent stabilization treatment technique and a treatment technique using a washing alternative treatment liquid as described in Japanese Patent Application Laid-Open No. 14834/1983. In addition to the steps of color development, bleach-fixing, and washing with water, various auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary.

本発明に適用できるR彩用ハロゲン化銀乳剤は、常法に
より化学増感することができ、増感色素を用いて、所望
の波長域に光学的に増感できる。
The silver halide emulsion for R color that can be applied to the present invention can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

ハロゲン化銀乳剤には、カブリ防止剤、安定剤等を加え
ることができる。該乳剤のバインダーとしては、ゼラチ
ンを用いるのが有利である。
Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

乳剤層、その他の親水性コロイド層は、lji!膜する
ことができ、又、可塑剤、水不溶性又は難溶性合成ポリ
マーの分散物(ラテックス)を含有させることができる
The emulsion layer and other hydrophilic colloid layers are lji! It can also contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

カラー写真用感光材料の乳剤層には、カプラーが用いら
れる。
A coupler is used in the emulsion layer of a light-sensitive material for color photography.

更に色補正の効果を有しているカラードカプラー、競合
カプラー及び現像主薬の酸化体とのカップリングによっ
て現像促進剤、漂白促進剤、現像剤、ハロゲン化銀溶剤
、調色剤、硬膜剤、カブリ剤、カブリ防止剤、化学増感
剤、分光増感剤、及び減感剤のような写真的に有用なフ
ラグメントを放出する化合物が用いることができる。
Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, Compounds that release photographically useful fragments such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

感光材料には、フィルタ一層、ハレーション防止層、イ
ラジェーション防止層等の補助層を設けることができる
。これらの層中及び/又は乳剤層中には現像処理中に感
光材料から流出するかもしくは漂白される染料が含有さ
せられてもよい。
The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

感光材料には、マット剤、滑剤、画像安定剤、界面活性
剤、色カブリ防止剤、現像促進剤、現像遅延剤や漂白促
進剤を添加できる。
A matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.

支持体としては、ポリエチレン等をラミネートした紙、
ポリエチレンテレフタレートフィルム、バライタ紙、三
酢酸セルロース等を用いることができる。
As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

[実施例1 以下、実施例によって本発明の詳細な説明するが、これ
により本発明の実施!i!様が限定されるものではない
[Example 1] Hereinafter, the present invention will be explained in detail with reference to Examples, and the present invention will now be put into practice! i! There are no restrictions on who you are.

実施例−1 (実験1) トリアセテートフィルムベース上にハレーション防止層
及びゼラチン層を設けこの上に赤感性ハロゲン化銀乳剤
層、緑感性ハロゲン化銀乳剤層、黄色コロイド銀を含有
するフィルタ一層及び青感性ハロゲン化銀乳剤壱を総体
の銀量が100 c 1z当り92mgになるよう塗布
した。上記の乳剤層は沃化銀のモル%が約4.5%の沃
臭化銀であり。この際、青感性ハロゲン化銀乳剤層には
イエローカプラーとして下記(Y−1)、緑感性ハロゲ
ン化銀乳剤層には、マゼンタカプラーとして下記(M−
1)、赤感性ハロゲン化銀乳剤層にはシアンカプラーと
して下記(C−1>を用い、各乳剤層にはそれぞれ増感
色素、硬膜剤及び延展開環通常の添加剤を加えた。この
ようにして得られたハロゲン化銀カラーネガ感光材料を
試料として用いた。
Example-1 (Experiment 1) An antihalation layer and a gelatin layer were provided on a triacetate film base, and on top of this, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive silver halide emulsion layer. Sensitive silver halide emulsion 1 was coated so that the total amount of silver was 92 mg per 100 c. The emulsion layer described above is silver iodobromide with a mole percent silver iodide of about 4.5%. At this time, the following yellow coupler (Y-1) is used in the blue-sensitive silver halide emulsion layer, and the following magenta coupler (M-1) is used in the green-sensitive silver halide emulsion layer.
1) The following (C-1>) was used as a cyan coupler in the red-sensitive silver halide emulsion layer, and a sensitizing dye, a hardening agent, and an ordinary additive for ring extension were added to each emulsion layer. The silver halide color negative light-sensitive material thus obtained was used as a sample.

イエローカプラー(Y−1> マゼンタカプラー(M−1) I シアンカプラー(C−1) この試料をピースに裁断し、常法に従って模型露光を与
えたものを用い、次の工程に従ってピース用処理装置を
用いて処理(以下、手用処理と称する)を行った。
Yellow coupler (Y-1> Magenta coupler (M-1) I Cyan coupler (C-1) This sample was cut into pieces and subjected to model exposure according to a conventional method. (hereinafter referred to as manual processing).

処理工程 処理温度(”C)槽数  処理時間1発色現
像  37.8    1槽  3分15秒2漂白定着
  37.8    1槽  4分20秒3水  洗 
30〜34    2槽   4分20秒4安  定 
30〜34    1槽   2分10秒5乾  燥 発色現像液、漂白定着液及び安定液は以下のものを使用
した。
Processing process Processing temperature ("C) Number of tanks Processing time 1 Color development 37.8 1 tank 3 minutes 15 seconds 2 Bleach fixing 37.8 1 tank 4 minutes 20 seconds 3 Washing
30-34 2 tanks 4 minutes 20 seconds 4 stable
30-34 1 tank 2 minutes 10 seconds 5 drying The following color developing solution, bleach-fixing solution and stabilizing solution were used.

[発色現像液] 炭酸カリウム            30 (1炭酸
水素ナトリウム         2.5g亜硫酸カリ
ウム           5.OQ臭化ナトリウム 
         1.2g沃化カリウム      
      2 mgヒドロキシアミン硫酸塩    
   2.5g塩化ナトリウム           
o、6gジエチレントリアミン五酢酸 ナトリウム             2.09N−エ
チル−N−β−ヒドロ キシエチル−3−メチル−4− アミンアニリン硫酸塩       45g水酸化カリ
ウム          1.2g水を加えて1iに仕
上げ、水酸化ナトリウム又は20%硫酸を用いて1)H
lo、06に調整した。
[Color developer] Potassium carbonate 30 (1 Sodium bicarbonate 2.5 g Potassium sulfite 5. OQ Sodium bromide
1.2g potassium iodide
2 mg hydroxyamine sulfate
2.5g sodium chloride
o, 6g sodium diethylenetriaminepentaacetate 2.09N-ethyl-N-β-hydroxyethyl-3-methyl-4-amine aniline sulfate 45g potassium hydroxide 1.2g Add water to make up to 1i, sodium hydroxide or 20g 1) H using % sulfuric acid
Adjusted to lo, 06.

[漂白定着液コ 表1に示す有機酸の第2鉄 アンモニウム錯塩       0.26モルチオ硫硫
酸アンモニウムクツ%溶液)   300d亜硫酸アン
モニウム         10 g例示化合物(It
−1>          5 a銀粉末      
         2.09水を加えて全はを1りとし
、酢酸とアンモニア水でpHを表1に示す様に調整した
[Bleach-fix solution: 0.26 mol ammonium thiosulfate % solution of ferric ammonium complex salt of organic acid shown in Table 1] 300d Ammonium sulfite 10g Exemplary compound (It
-1>5 a silver powder
2.09 Water was added to bring the total volume to 1, and the pH was adjusted as shown in Table 1 with acetic acid and aqueous ammonia.

[安定液] ホルマリン(37%水溶液)21g コニダックス(小西六写真工業社tJ)5d水を加えて
11とした。
[Stabilizing solution] 21 g of formalin (37% aqueous solution), 5 d of Conidax (Konishi Roku Photo Industries Co., Ltd. tJ), and 5 d of water were added to make 11.

表  1 表 1  (続き) 上記処理後の漂白定着液を開口比率10Ct”/!(一
般の自動現像機に相当する開口条件であり、1にの漂白
定着液に対して、10Cfの空気接触面積を有している
事を意味する。)で、38℃、1週間の経時保存し、保
存後の漂白定着液を用いて上記処理を再び行なった。処
理後のフィルム試料(漂白定着液の経時保存前後のそれ
ぞれ)の最、 高濃度部の残留銀fl 〈mo/dv2
>を蛍光X線法により、測定し、さらに、シアン色素濃
度をサクラ光電濃度計PDA−65(小西六写真工業(
(3)製)を用いて復色率を測定した。
Table 1 Table 1 (Continued) The bleach-fix solution after the above treatment has an aperture ratio of 10 Ct"/! (This is an opening condition equivalent to a general automatic processor, and the air contact area is 10 Cf for the bleach-fix solution in step 1. The film sample was stored at 38°C for one week, and the above process was carried out again using the bleach-fix solution after storage. Residual silver fl in the highest and highest concentration areas (before and after storage) <mo/dv2
> was measured by the fluorescent X-ray method, and the cyan dye concentration was measured using a Sakura photoelectric densitometer PDA-65 (Konishi Roku Photo Industry Co., Ltd.).
(3)) was used to measure the color restoration rate.

結果をまとめて表2に示す。The results are summarized in Table 2.

上記表2より、本発明に係わる有灘酸第2鉄錯塩を用い
て、pH3,0〜6.8の領域の漂白定着液を使用する
際には、経時保存の如何にかかわらず、残留銀も少なく
、かつ復色率も良好であることが判る。特に、pHが4
.0〜6.7の時がより良好で、pHが5.0〜6.5
の際にとりわけ特に良好であることが判る。
From Table 2 above, when using the ferric acid complex salt of the present invention and a bleach-fixing solution with a pH in the range of 3.0 to 6.8, it is possible to remove residual silver regardless of storage over time. It can be seen that the amount of color is small and the color recovery rate is also good. Especially when the pH is 4
.. It is better when the pH is 0 to 6.7, and the pH is 5.0 to 6.5.
It turns out that it is particularly good when

しかるに、比較のDTPAを有機酸として用いた比較の
漂白定着液によればM7〜8で経時保存前は脱銀性能及
び復色性能は極めて良好であるが、1週間の保存後には
不充分なる性能となってしまう。さらに、EDT△は、
経時保存の如何にかかわらず、脱銀性能及び復色性能が
不充分なものであることが判る。
However, according to a comparative bleach-fix solution using comparative DTPA as an organic acid, the desilvering performance and recoloring performance were extremely good at M7-8 before storage over time, but became insufficient after storage for one week. It becomes performance. Furthermore, EDT△ is
It can be seen that the desilvering performance and color restoration performance are insufficient regardless of the storage over time.

(実験2) 前記(実験1)で用いた漂白定着液No、3の亜例示化
合物(If−1>を、未添加のもの、ざらに6−1〜6
−5を調製した。該漂白定着液を用いた実験1の感材を
処理し、得られた処理後の漂白定着液を実験1と同様に
経時保存し、この経時保存漂白定着液を用いて、脱銀性
能及び復色性能を実験1と同様に測定し表3に併せて示
した。
(Experiment 2) The sub-exemplified compound (If-1> of bleach-fix solution No. 3 used in the above (Experiment 1) was not added, and Zarani 6-1 to 6
-5 was prepared. The photosensitive material of Experiment 1 using the bleach-fix solution was processed, and the bleach-fix solution obtained after treatment was stored over time in the same manner as in Experiment 1. Using this bleach-fix solution stored over time, desilvering performance and recovery were evaluated. Color performance was measured in the same manner as in Experiment 1 and is also shown in Table 3.

また1週間保存後、ざらに開口比率を10倍にして保存
をつづけ沈澱の発生が生じるまでの日数を目視にて観察
した。
After one week of storage, the opening ratio was roughly increased to 10 times and storage was continued, and the number of days until precipitation occurred was visually observed.

以上の結果をまとめて表3に示す。The above results are summarized in Table 3.

上記表3より、明らかな様に、本発明に係わる一般式[
II]で表わされる化合物の種類を代えて用いても沈澱
発生までの日数が大巾に延びるばかりでなく、残留銀但
及び復色率もより良好となることが判る。
As is clear from Table 3 above, the general formula [
It can be seen that even if the type of compound represented by [II] is used in a different manner, not only the number of days until precipitation occurs is greatly extended, but also the residual silver and the rate of color recovery become better.

なお、前記実験2で用いた例示化合物 (II−14)の代わりに、それぞれ<I[−9) 。In addition, the exemplified compounds used in Experiment 2 above (II-14), respectively <I[-9).

(If−16)、(II−19)、(I[−3)、(I
I=15)、(II−7>を用いて、他は実験2と同じ
実験を行なったところ、実験2の(If−14)と、は
ぼ同じ結果を得た。
(If-16), (II-19), (I[-3), (I
When the same experiment as Experiment 2 was conducted using I=15) and (II-7>, the results were almost the same as those in Experiment 2 (If-14).

以上の実験1および実験2の結果より、本発明の漂白定
着液、即ちDHが3.0〜6.8の範囲で一般式[II
で示される化合物を配位子とする第2鉄錯塩を含有し、
ざらに一般式[IIで示される化合物を含有する漂白定
着処理液は、特に経時保存後においても優れた脱銀性能
を有し、復色不良の発生も良好に防止され、さらに保存
安定性も良好であることがわかる。なお、本発明の漂白
定着液はアンモニア臭は全くないものであった。
From the results of Experiment 1 and Experiment 2 above, it was found that the bleach-fix solution of the present invention, that is, the DH of the general formula [II
Contains a ferric complex salt having a compound represented by as a ligand,
A bleach-fixing solution containing a compound represented by the general formula [II] has excellent desilvering performance, particularly after storage over time, prevents the occurrence of poor recoloring, and has excellent storage stability. It can be seen that it is in good condition. The bleach-fix solution of the present invention had no ammonia odor at all.

実施例−2 実施例−1の実験1と同様に漂白定着液を経保存させた
。ただし、ここでは漂白定着液中の硫酸アンモニウムの
濃度を12(1/1、漂白剤種類を表4に記載した如く
とし、漂白剤の温度表4の如く変化させた。また漂白定
着液のpH6,0とした。
Example 2 A bleach-fix solution was stored in the same manner as in Experiment 1 of Example 1. However, here, the concentration of ammonium sulfate in the bleach-fix solution was 12 (1/1), the type of bleach was as shown in Table 4, and the temperature of the bleach was varied as shown in Table 4. Also, the pH of the bleach-fix solution was 6, It was set to 0.

経時保存後、実施例−1の実験1と同様の評を行ない、
結果を表4に示した。
After storage over time, the same evaluation as in Experiment 1 of Example-1 was performed,
The results are shown in Table 4.

次にすべての漂白定着液を実施例−1の実験と同様に継
続して保存し、硫化するまでの日数測定し、結果を表4
に併せて示した。
Next, all the bleach-fix solutions were continuously stored in the same manner as in the experiment of Example-1, and the number of days until sulfurization was measured, and the results are shown in Table 4.
It is also shown in .

表4より明らかなように、本発明の漂白定着液の中でも
、特に漂白剤の含有量が0.02モル/i〜1.30モ
ル/l、好ましくは0.10〜1.20モル/l、さら
に好ましくは020〜0.8モル/yの範囲であれば、
経時保存しても脱銀及び復色能力は高くかつ硫化までの
日数が長い良好な漂白定着液であることがわかる。
As is clear from Table 4, the bleach-fixing solution of the present invention has a bleaching agent content of 0.02 mol/i to 1.30 mol/l, preferably 0.10 to 1.20 mol/l. , more preferably in the range of 0.20 to 0.8 mol/y,
It can be seen that this is a good bleach-fix solution that has high desilvering and recoloring ability even after storage over time, and takes a long time to sulfurize.

実施例−3 実施例−1の実験1と同様に漂白定着液を経時保存させ
た。ただし、ここでは漂白定着液として、実験1の漂白
定着液No、1−1の漂白剤及びその添加量を表5の如
くとし、漂白定着液中のKIの濃度を表5の如く変化さ
せ、さらに漂白定着液中のpHを60とした。
Example 3 A bleach-fix solution was stored over time in the same manner as in Experiment 1 of Example 1. However, here, as the bleach-fix solution, the bleach-fix solution No. of Experiment 1, the bleaching agent of 1-1 and its addition amount were as shown in Table 5, and the concentration of KI in the bleach-fix solution was changed as shown in Table 5. Further, the pH of the bleach-fix solution was set to 60.

経時保存後実施例−1の実験1と同様に脱銀能力の評価
を行ない結果を表5に記載した。
After storage over time, the desilvering ability was evaluated in the same manner as in Experiment 1 of Example-1, and the results are listed in Table 5.

また処理後の試料を、CNK−4基準処理(小西六写真
工業カラーネガ処理)に従って漂白及び定着処理を施こ
し残存銀を完全に除いた後に、マゼンタ色素の透過濃度
を測定してこの値をDR+ とした。次に実施例−1の
実験1と同様に発色現象を行った後、CNK−4基準処
理に従って漂白及び定着処理した試料のマゼンタ色素の
透過濃度を測定し、この値を眼、とした。DRI とD
I2□の差を求める(△D、)ことにより、マゼンタス
テイン表5から明らかなように、比較の漂白定着液では
、KIの添加によってマゼンタスティンは小さくなるが
脱銀能力が大きく低下する。しかし本発明の漂白定着液
では、Klの添加によりマゼンタスティンが低く押えら
れる一方、脱銀能力の低下が小ざく良好な結果が得られ
た。
In addition, after bleaching and fixing the processed sample according to CNK-4 standard processing (Konishi Roku Photo Industries Color Negative Processing) to completely remove residual silver, the transmission density of the magenta dye was measured and this value was calculated as DR+. And so. Next, a color development phenomenon was carried out in the same manner as in Experiment 1 of Example-1, and then the transmittance density of the magenta dye of the sample bleached and fixed according to the CNK-4 standard process was measured, and this value was defined as the eye value. DRI and D
By determining the difference in I2□ (ΔD,), magenta stain As is clear from Table 5, in the comparative bleach-fix solution, the addition of KI reduces magenta stain, but the desilvering ability is greatly reduced. However, in the bleach-fix solution of the present invention, good results were obtained in which magentastin was suppressed to a low level by the addition of Kl, and the desilvering ability was only slightly reduced.

実施例−4 実施例−1の実験1において調製した漂白定着液N0.
1−1および3−1において、pHを6,0とし漂白促
進剤を下記表6に示す如くに添加した以外は同様にして
、漂白定着液No、1−11〜1−16および3−32
〜3−37を調製した。
Example-4 Bleach-fix solution N0. prepared in Experiment 1 of Example-1.
1-1 and 3-1, except that the pH was adjusted to 6.0 and the bleach accelerator was added as shown in Table 6 below.
~3-37 was prepared.

得られた漂白定着液を用いて、実験1における漂白定着
時4分20秒を3分15秒とした以外は、実施例−1の
実験1および2と同様の評価を行った。
Using the obtained bleach-fixing solution, the same evaluation as in Experiments 1 and 2 of Example-1 was performed, except that the bleach-fixing time in Experiment 1 was changed from 4 minutes and 20 seconds to 3 minutes and 15 seconds.

結果を表6に示す。The results are shown in Table 6.

以T1江、−白 表6より、漂白促進剤を添加した時には本発明のぶ白定
着液は保存によっても脱銀性、復色性および保存性のい
ずれも良好な効果を維持できるのに対して、本発明外の
漂白定着液は、調製直後の場合にはいずれも効果があっ
たが、保存により脱銀性と塩性性および保存性が更に劣
化することが明らかとなった。
From Table 6, it can be seen that when a bleaching accelerator is added, the bleaching fixer of the present invention can maintain good effects in terms of desilvering properties, recoloring properties, and preservability even after storage. It has become clear that, although bleach-fix solutions other than those of the present invention were effective immediately after preparation, their desilvering properties, saltiness, and preservability further deteriorated upon storage.

Claims (1)

【特許請求の範囲】 撮影用ハロゲン化銀写真感光材料を漂白定着する処理液
において、該液のpHが3.0〜6.8の範囲にあり、
かつ下記一般式[ I ]で示される化合物を配位子とす
る第2鉄錯塩を含有し、さらに下記一般式[II]で示さ
れる化合物を含有することを特徴とする漂白定着液。 一般式[ I ] ▲数式、化学式、表等があります▼ (式中、R_1は水素原子または低級アルキル基を表わ
し、n_1、n_2およびn_3はそれぞれ0〜3の整
数を表わす。但し、n_1、n_2およびn_3の合計
は3または4の整数であり、 ▲数式、化学式、表等があります▼における炭素原子数
の総和は3以上である。) 一般式[II] ▲数式、化学式、表等があります▼ (式中、R_2およびR_3はそれぞれ水素原子、アル
キル基、アシル基またはカルバモイル基を表わす。R_
4、R_5およびR_6はそれぞれ水素原子またはアル
キル基を表わし、mは0、1または2を表わす。Mは水
素原子またはカチオンを表わす。)
[Scope of Claims] A processing solution for bleaching and fixing silver halide photographic light-sensitive materials, the pH of which is in the range of 3.0 to 6.8;
A bleach-fixing solution comprising a ferric complex salt having a compound represented by the following general formula [I] as a ligand, and further containing a compound represented by the following general formula [II]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a hydrogen atom or a lower alkyl group, and n_1, n_2 and n_3 each represent an integer from 0 to 3. The sum of and n_3 is an integer of 3 or 4, and the total number of carbon atoms in ▲There are mathematical formulas, chemical formulas, tables, etc. is 3 or more.) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_2 and R_3 each represent a hydrogen atom, an alkyl group, an acyl group, or a carbamoyl group. R_
4, R_5 and R_6 each represent a hydrogen atom or an alkyl group, and m represents 0, 1 or 2. M represents a hydrogen atom or a cation. )
JP24174886A 1986-10-11 1986-10-11 Bleach-fix bath excellent in rapid processing Pending JPS6395452A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP24174886A JPS6395452A (en) 1986-10-11 1986-10-11 Bleach-fix bath excellent in rapid processing

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP24174886A JPS6395452A (en) 1986-10-11 1986-10-11 Bleach-fix bath excellent in rapid processing

Publications (1)

Publication Number Publication Date
JPS6395452A true JPS6395452A (en) 1988-04-26

Family

ID=17078951

Family Applications (1)

Application Number Title Priority Date Filing Date
JP24174886A Pending JPS6395452A (en) 1986-10-11 1986-10-11 Bleach-fix bath excellent in rapid processing

Country Status (1)

Country Link
JP (1) JPS6395452A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5582958A (en) * 1995-01-10 1996-12-10 Eastman Kodak Company Photographic bleaching composition and processing method using ternary iron carboxylate complexes as bleaching agents

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5582958A (en) * 1995-01-10 1996-12-10 Eastman Kodak Company Photographic bleaching composition and processing method using ternary iron carboxylate complexes as bleaching agents

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