JPS63226644A - Bleach-fixing solution having superior suitability to rapid processing - Google Patents

Abstract

PURPOSE:To enable rapid bleach-fixing in good working environment without generating gaseous NH3 by keeping a bleach-fixing soln. for a silver halide photographic sensitive material at a specified pH and incorporating a specified ferric complex salt and a specified compd. into the soln. CONSTITUTION:A bleach-fixing soln. for a silver halide photographic sensitive material for photographing is kept at 3.0-6.0 pH and a ferric complex salt having a compd. represented by formula I as a ligand and at least one kind of compd. represented by formula II or III are incorporated into the soln. In the formula I, R1 is H or lower alkyl, each of n1-n3 is 0-3, (n1+n2+n3)=2-4 and the total number of C atoms in -(CH2)n1-(CHR1)n2-(CH2)n3- is >=3. In the formulae II, III, each of R2-R5 is H or 1-8C alkyl, M is an alkali metal atom or ammonium group and (n) is 0-6. When the bleach-fixing soln. is used, processing is accelerated and no gaseous ammonia is generated. The soln. maintains satisfactory desilvering and recoloring properties and high shelf stability during storage and the bleach-fixing performance is not deteriorated.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to bleaching windows Wi'l! More specifically, the present invention relates to a bleach-fix solution that can be applied to photosensitive materials for photographic use to achieve rapid processing.

[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.

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.

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. 1) As a result of searching for bleaching agents with excellent desilvering ability in the H region, the present inventors found that among various aminopolycarboxylic acid iron complexes, diethylenetriaminepentaacetic acid ferric complex salt (DTPA-Fe complex salt) has the highest desilvering ability. It has been proposed to be satisfactory in terms of speed, recoloring properties of the dye image obtained, and storage stability of the bleach-fix solution over time. (Unexamined Japanese Patent Publication No. 60-1342
No. 38, Go-130738, Go-60-136
744, etc.) The above-mentioned DTPA-Fe 81 salt can satisfy the above characteristics in a high pH range, specifically in the range of about pH 7 to 9, but ammonia gas is generated in such a pH range. Easy and narrow! When carrying out development processing inside the machine, there were disadvantages in terms of the working environment. 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.

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.

As a result of extensive studies, the present inventors found that a specific low p
By using HIR 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 at the same time.
It has also been found that the generation of ammonia gas can also be eliminated.

Conventionally, bleach-fix solutions using sulfite at low concentrations have generated precipitation in a relatively short period of time when stored, but from the compounds represented by the general formulas [II] and [I[[] of the present invention, respectively, It has been found that when at least one selected compound is used, precipitation becomes less likely to occur and storage stability is improved.

Regarding some of the compounds represented by the general formulas [I[] and [II[] of the present invention, for example, iron ethylenediaminetetraacetate ([[) 31 It is known to use EDTA-Fe as a bleaching agent in bleach-fix solutions.

However, such compounds gradually release sulfite ions in the bleach-fix solution containing EDTA-Fe, resulting in the accumulation of aldehydes or ketones.
It became clear that the desilvering rate gradually decreased.

On the other hand, when a specific aminopolycarboxylic acid iron complex salt is used in a bleach-fix solution used in a specific low I)H range,
The present invention was developed based on the discovery that the storage stability can be dramatically improved without deteriorating the excellent desilvering and recoloring performance of the bleach-fix solution.

[Object of the Invention] Accordingly, the first object of the present invention is to provide a bleach-fixing solution which can be applied to photographic light-sensitive materials to solve the above-mentioned drawbacks and enable rapid processing. The second object of the present invention is to
To provide a bleach-fixing solution that does not generate ammonia gas and is favorable in terms of working environment.

[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, which has a pH of 3.0 to 6.
．． 8, and contains a ferric complex salt having a compound represented by the following general formula [I] as a ligand, and further contains a ferric complex salt having a compound represented by the following general formula [I] and the following general formula [I[[], respectively. This was achieved with a bleach-fix solution containing at least one compound selected from the compounds shown.

General formula CI] (In the formula, R1 represents a hydrogen atom or a lower alkyl group, and n, R2 and II: 3 each represent an integer of O to 3. However, the total of nl, R2 and R3 is 2 to 4. (In the formula, R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R3 is Hydrogen atom or carbon atom number 1~
8 represents an alkyl group, and M represents an alkali gold atom or an ammonium group. ) General formula [1 [[] (wherein R4 and R5 each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, M represents an alkali metal atom or an ammonium group, and n is an integer of O to 6) ) [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 [II as a ligand.

In the general formula [II, R1 is preferably a hydrogen atom. Moreover, the most preferable sum of the numbers is 3.

Preferred specific examples of the compound represented by the general formula [II are shown below.

Exemplary Compound A compound represented by the above general formula [II] 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 acid (hydrogen salt), but as a counter salt, it may be an alkali metal salt such as a sodium salt, a potassium salt, a lithium salt, or an ammonium salt, Alternatively, it can also be used as a water-soluble amine salt, such as a triethanolamine salt.

Preferably potassium, sodium and ammonium salts are used. At least one type of these ferric complex salts of the present invention may be used, but two or more types can also be used in combination. It can also be used in combination with ferric iron iii, which is outside the scope of the present invention.

Among the ferric salts of the present invention exemplified above, ferric complex salts using exemplified compounds (I-1), (I-2) and (I-3) as ligands are preferred. In general, it is particularly preferable to use <l-1) and (I-2) from the viewpoint of solubility among the exemplified compounds No., (I-1), (1-2) and (I-3), and the present invention In view of the effects of the object of the invention, it is most preferable to use (I-1) in the present invention.

The ferric complex salt of the present invention can be used in any amount in the bleach-fixing solution of the present invention as long as the effect of the present invention can be obtained. If the concentration becomes too high, the storage stability of the bleach-fix solution will deteriorate, while if the concentration of the ferric complex salt is too low, the desilvering performance and color restoration performance will deteriorate. Therefore, it is usually 0.02 to 1.
It is preferable to use it in the range of 30 mol/l, and 0.10
It is more preferable to use it in a range of 1.20 mol/2 to 1.20 mol/2. In particular, it is preferable to use it in a range of 0.20 to 0.80 mol/2 because the effects of the present invention can be achieved well.

The bleach-fix solution of the present invention has a f)H range of I)R3, because if it is less than p)-13.0, it will generate sulfur dioxide gas, and if it is higher than I)H6,8, the effect of the present invention will be insufficient. ,0
~6.8, and can be used at any pH in this DH region, but in addition to desilvering and recoloring properties, the solubility of various iron salts at low temperatures, and the odor of sulfite gas generated from sulfite ions. Considering this, it is preferable to use I) 84.0 to 6.7, and most preferably I) R 5,0 to 6.5.

The bleach-fix solution of the present invention contains at least one compound (hereinafter referred to as the bisulfite adduct of the present invention) selected from the compounds represented by the general formula [II] and the general formula [I]. Used as an agent□.

In the general formula [I], the alkyl group having 1 to 8 carbon atoms respectively represented by R2 and R3 is preferably an alkyl group having 1 to 4 carbon atoms.

One of the preferable carbonyl bisulfite adducts represented by the general formula [II] is one in which R2 is a hydrogen atom and R3
is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the other one is one in which R2 and R3 are each an alkyl group having 1 to 4 carbon atoms.

In general formula [111], the alkyl group having 1 to 8 carbon atoms represented by R4 and R5 is preferably an alkyl group having 1 to 2 carbon atoms.

n represents an integer of 0 to 6, preferably an integer of 1 to 4.

One of the preferable carbonyl bis-bisulfite adducts represented by the general formula [111] is one in which R+ and R5 are each a hydrogen atom, and n is 1 to 4,
The other one is that R+ and R5 each have 1 to 2 carbon atoms.
is an alkyl group in which n is an integer of 1 to 4.

Specific examples of the bisulfite adduct of the present invention are shown below, but the present invention is not limited thereto.

Exemplary bisulfite liquid salt adduct -1 Acetaldehyde Sodium bisulfite 1 cum I-2 Propionaldehyde Bisulfite 1 [1 Sodium ll-3 Butyraldehyde Sodium bisulfite ll-4
Acetone Sodium sulfite It-5 Butanone Sodium bisulfite I [-6 Pentanone Sodium bisulfite 1-1 Succinic aldehyde Sodium bis bisulfite m-2 Glutaraldehyde Sodium bis bisulfite lll-3 β-Methylglutaraldehyde Bis bisulfite Sodium I [-4 maleic acid dialdehyde Sodium bis bisulfite I [[-52,4-pentanedione Sodium bis bisulfite 1ili of the above bisulfite of the present invention! The salt adducts may be used alone or in combination of two or more, and can be used in an amount of 0.01 to 2 mol per bleach-fix solution 11 of the present invention, preferably 0.01 to 2 mol per 11 of the bleach-fixing solution of the present invention. 02 to 1 mol, more preferably 0.05 to 0.5 mol.

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, thiocyanine W1 salts such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromide and iodide. These fixatives are 5g#! above, preferably 50 flll/ffi or more, more preferably 70 g/ffi or more
Can be used in

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, sodium iodide, ammonium iodide, and the like.

The bleach-fix solution of the present invention contains IFI! 1. II. DH'am agents consisting of various salts such as sand, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. alone or in combination A combination of the above may be contained. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifoaming agents can be contained.

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 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.

It is preferable to use a bleach accelerator in the bleach-fixing solution of the present invention, and for example, compounds described in Japanese Patent Application No. 160943/1988 can be used, and the following general formulas [A to ■] to
It is preferable to use the compounds shown in [A to ■] because they can better achieve the effects of the present invention.

General formula [A-r] In the formula, Ql represents an atomic group necessary to form an N-containing heterocycle (including those in which 5- to 6-membered unsaturated rings or saturated rings are condensed), R1 represents a hydrogen atom or an alkyl group. Generally speaking, Q' has the same meaning as Ql.

General formula [A-IIJ 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 acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group. represents a group.

X・　R′.

or represents an n1-valent heterocyclic residue (including those in which 5- to 6-membered unsaturated rings are condensed), and X represents -S10 or -NR". Here, R and R' are R each
2 and R3, X' is synonymous with X, 2 is a hydrogen atom,
It represents an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, an alkyl group, or an atom, and R" is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, or a heterocyclic ring. Remainder!! (including those in which 5- to 6-membered unsaturated rings are fused)
or represents an amino group, 01-n6 and 11-15
each represents an integer from 1 to 6. B has 1 or more carbon atoms
6 represents an alkylene group, Y represents -N or -cH, R4 and R5 are R2F3 and R3, respectively.
is synonymous with However, R4 and R5 are each -B-
8z may also be represented, and R2 and R3, R and R',
R4 and R5 may each be combined to form a ring.

In addition, the compound represented by the cough formula also includes enolized products and salts thereof.

General formula [A-III] r? + [(1 In the formula, R6 and R7 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group, or - B + -S -Z + woRf)
V. However, R6 and R7 represent /CH-, 8+ represents an alkylene group having 1 to 6 carbon atoms, and Zl represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group,
Represents an N-containing hetero-O ring residue or an integer of.

(G')z In the formula, Ar represents an aryl group of 261& or an organic group of 2111i which is a combination of an aryl group and an oxygen atom and/or an alkylene group, B2 and B3 each represent a lower alkylene group, R8, Rs, Rlo and R1+ each represent a hydroxy-dimethylated lower alkyl group, and X and y each represent 0 or 1. G
' represents an anion, and 2 represents Oll or 2.

Specific details of the bleach accelerator preferably used in the present invention are shown below.

Exemplary compounds <A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) H,N-C3NHNHC3-NH2 (A-9) Bleaching The amount of accelerator added is approximately 0 per 12 of the bleach-fix solution of the present invention.
．． It is preferable to use it in the range of 01 to 10013, more preferably 0.05 to 50g, particularly preferably 0,
05-150.

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 1112 silver speed, but in the bleach-fix solution of the present invention,
Not only does the desilvering property not substantially deteriorate due to the accumulation of iodine ions, but surprisingly, the desilvering property remains unexposed even when immersed in a bleach-fix solution without going through a washing process such as a water washing process after color development. It has become clear that there is almost no increase in concentration (so-called fog).

At this time, iodine ions are added to the bleach-fix solution at 0.0005 mol/
It is preferable that the bleach-fixing solution contains at least 0.001 mol/mol of the bleach-fixing solution.

The processing time using the bleach-fixing solution of the present invention is not particularly limited, but it is preferably 10 minutes or less in order to shorten the processing time, and in particular, the present invention allows rapid processing of 7 minutes or less.

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.

The above bleach-fix solution of the present invention can be applied to any silver halide photographic material as long as it is a silver halide photographic material for photographing. Specifically, the silver iodide content is preferably 0.5.
A photosensitive material using a high-sensitivity silver iodobromide emulsion containing at least mol %, preferably at least 1 mol % is preferable.

The bleach-fix solution of the present invention may be used as a processing solution for bleaching and fixing the silver halide photographic light-sensitive material for shadows immediately after color development, or may be used as a processing solution for washing, rinsing, stopping, etc. after color development. Bleaching and fixing after cleaning! It may be used as a processing solution or as a bleach-fixing processing solution after performing a pre-fixing treatment 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, color development, bleach fixing,
In addition to the steps such as washing with water, various auxiliary steps such as hardening, neutralization, black and white development, reversal, receiving and washing with water may be added as necessary.

The silver halide emulsion applicable 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.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer, the hydrophilic colloid layer thereof, can be hardened and can contain a plasticizer, a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of a light-sensitive material for color photography.

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 into photographically useful fragments 1 such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

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.

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.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Practical 1M Example-1 (Experiment 1) An antihalation layer and a gelatin layer are provided on a triacetate film base, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a gelatin layer are formed on the triacetate film base. A blue-sensitive silver halide emulsion layer was coated to give a total silver content of 88I1g per 100cf. The emulsion layer described above is silver iodobromide with a molar percentage of silver iodide of about 4.3%. 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.
The following (C-1) was used as a cyan coupler in the red-sensitive silver halide emulsion layer, and conventional additives such as a sensitizing dye, a hardener, and a spreading agent were added to each emulsion layer. The silver halide color negative light-sensitive material thus obtained was used as a sample.

Yellow coupler (Y-1) Magenta coupler (M-1) Cyan coupler (C-1) This sample was cut into pieces, horizontally exposed according to the usual method, and then processed using a piece processing device according to the following steps. Processing (hereinafter referred to as manual processing) was performed using the following methods.

Processing process Processing temperature ('C) Number of tanks Processing time 1 Color development 37.8 1 tank 3915 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.

[Color developer] Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite
5.0g sodium bromide
1.2g potassium iodide
2mg hydroxyamine sulfate 2.5
g Sodium chloride 0.6 g Sodium diethylenetriaminepentaacetate 2.0 g N-ethyl-N-β-hydroxyethyl-3-methyl-4-amine aniline sulfate 4.5 g Potassium hydroxide 1.2 g Add water to make 11. Sodium hydroxide or 20% l1iI! The pH was adjusted to 10.06 using acid.

[Bleach-fix solution] Ferric ammonium complex salt of ceric acid shown in Table 1 0.25 mol ammonium thiosulfate (70% solution) 30 On Preservative shown in Table 1 Amounts listed in Table 1 Silver powder
2. Oil water was added to bring the total volume to 12, and the pH was adjusted as shown in Table 1 with acetic acid and aqueous ammonia.

[Stabilizer] Formalin (37% aqueous solution) 2Konidax (Konishi Roku Photo Industries Co., Ltd. IJ) Add 5d water to make 1l
And so.

The bleach-fix solution after the above treatment has an aperture ratio of 10 cf/l (an opening condition equivalent to that of a general automatic processor, meaning that the bleach-fix solution of 111 has an air contact area of 10 cf/l). ) at 38° C. for one week, and the above treatment was performed again using the bleach-fix solution after storage. The residual silver 1 (intestinal g/df) in the highest density area of the processed film sample (before and after storage of the bleach-fix solution over time) was measured using the fluorescence Xa method, and the cyan dye concentration was measured using a Sakura photoelectric densitometer PDA. -65 (Konishi Roku Photo Industry @ J made)
The color recovery rate was measured using

The results are summarized in Table 2.

From Table 2 above, when using the organic acid ferric complex salt according to the present invention and using the bleaching window 1'fl in the pH range of 3.0 to 6.8, no residual It can be seen that there is little silver and the color restoration rate is also good. In particular, pH
It is better when the pH is 4.0 to 6.7, and the pH is 5.0 to 6.
．． 5 is particularly good.

However, it can be seen that the comparative bleach-fixing solution using EDTA as the organic acid has insufficient desilvering performance and recoloring performance, regardless of storage over time.

In addition, in the above bleach-fix solution Nos. 1-1 to 8 to 9,
Similar effects were also confirmed when I-2 to m-6 and lll-2 to I[[-5 were used as preservatives in place of Exemplary Nos., ll-1, and I[[-1, respectively.

(Experiment 2) In the bleach windows @1EN0.1-1 and 2-1 used in (Example 11) above, the type and concentration of preservatives in the bleach-fix solution were as shown in Table 3 below, and 1) Bleach-fix solution No. 9-1 to 9-3 and 10-1 to H with 6.0
10-3 was prepared. The photosensitive material of Experiment 1 was processed using the bleach-fix solution, the bleach-fix solution obtained after processing was stored over time in the same manner as in Experiment 1, and the desilvering performance and recovery were evaluated using this bleach-fix solution stored over time. Color performance was measured in the same manner as in Experiment 1 and is also shown in Table 3.

After one week of storage, the opening ratio was further increased to 10 times and storage was continued, and the number of days until precipitation occurred was visually observed.

The above results are summarized in Table 3.

As is clear from the results in Table 3, compared to the comparative bleach-fixing solution using an organic acid and preservative that form a comparative ferric complex salt, the The bleach-fix solution of the present invention using a bisulfite adduct exhibits slow precipitation even when stored over time and has excellent storage stability, and also has excellent desilvering and recoloring properties of dye images obtained by transfer. I understand that.

From the results of Actual M1 and Experiment 2 above, it was found that the bleach-fixing solution of the present invention, i.e., the one-prong type II with a pH in the range of 3.0 to 6.8]
Contains a ferric bell salt having a compound represented by as a ligand,
Furthermore, the bleach-fixing solution containing the bisulfite adduct of the present invention has excellent desilvering performance, especially 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.

Example 2 A bleach-fix solution was stored over time in the same manner as in Experiment 1 of Example 1. However, here, the bisulfite adduct in the bleach-fix solution, Example No. I [-4, was used at a concentration of 0.25 mol/liter,
The types of bleaching agents were as shown in Table 4, and the concentrations of the bleaching agents were varied as shown in Table 4.

Further, the IIH of the bleach-fix solution was set to 6.0.

After storage over time, the same evaluation as in Experiment 1 of Example-1 was performed, and the results are shown in Table 4.

Next, all the bleach-fix solutions were continuously stored in the same manner as in Experiment 2 of Example-1, and the number of days until sulfurization was measured. The results are shown in Table 4.

Table 4 Table 4 (Continued) As is clear from Table 4, the bleach-fixing solution of the present invention particularly contains a bleaching agent of 0.02 mol/y to 1.30 mol/y. If it is preferably in the range of 0.10 to 1.200 mol/l, more preferably 0.20 to 0.8 mol/l, the desilvering and restoring ability will be high even after storage over time, and the number of days until sulfurization will be high. It can be seen that it is a good bleach-fix solution for a long time.

Example 3 A bleach-fix solution was stored over time in the same manner as in Experiment 1 of Example 1. However, here, the bleach-fix solution No. of Experiment 1 and the preservative of 1-1 are used as exemplified compound No. and I[
-6 (11 degrees, 0.2 mol/liter), and the bleaching agent and its addition amount as shown in Table 5, K I in the bleach-fix solution was used.
The concentration of p in the bleach fixing solution was changed as shown in Table 5.
H was set to 6.0.

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.

In addition, the processed sample was bleached and fixed according to the CNK-4 standard processing (Konishi Roku Photo Industry Color Negative Processing) to completely remove residual silver, and the permeation moisture level of the macenta dye was measured and this value was calculated. Dc + binding 6 Next, after performing color development in the same manner as in Experiment 1 of Example-1, the transmittance of the magenta dye of the sample bleached and fixed according to the CNK-4 standard process was measured at 111 degrees, and this value was calculated as DG2. And so. D.G.I.
By calculating the difference between and DG2 (△DG), as is clear from Table 5, in the comparative bleach-fix solution, Kl
By adding , the magentastin becomes smaller, but the desilvering ability is greatly reduced. However, in the bleach-fix solution of the present invention, magentastin was suppressed to a low level by the addition of KI, while good results were obtained with little decrease in desilvering ability.

Example-4 Bleach-fix solution N0 prepared by GL in Experiment 1 of Example-1
．． 1-1 and 2-1, the pH was set to 6.0 and the preservative was exemplified compound N01I-4 (11110, 1 mol/l).
Bleach-fix solution No. was prepared in the same manner except that the bleach accelerator was added as shown in Table 6 below.

1-11 to 1-16 and 2-21 to 2-26 were produced by rA.

Example 1 except that the bleach-fixing time in Experiment 1 was changed from 4 minutes 20 seconds to 3 minutes 15 seconds using the obtained bleach-fix solution.
The same evaluation as in Experiments 1 and 2 was performed.

The results are shown in Table 6.

Table 6 shows that when a bleach accelerator is added, the bleach-fix solution of the present invention can maintain good effects in terms of desilvering properties, recoloring properties, and preservability even after storage, whereas bleaching solutions other than those of the present invention Although the fixing solutions were all effective immediately after preparation, it became clear that the desilvering properties, restoring properties, and preservability deteriorate further when stored.

Claims (1)

[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;
and contains a ferric complex salt having a compound represented by the following general formula [I] as a ligand, and further contains at least one compound selected from the compounds represented by the following general formula [II] and the following general formula [III], respectively. A bleach-fixing solution characterized by containing a compound. 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 from 2 to 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 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R_3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and M represents an alkali metal atom or an ammonium group. ) General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. , n represents an integer from 0 to 6.)