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

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

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.

[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. 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.

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 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.

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.

[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.

[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.

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.

In general formula [I], R+ 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 [I] are shown below.

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.

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.

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.

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.

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.

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.

A compound represented by the general formula [II] is used in the bleach-fix solution of the present invention.

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, 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 represents 011 or 2, preferably O or 1
and O is particularly preferred.

M represents a hydrogen atom or a cation, and examples of the cation include potassium, sodium, and ammonium.

The above R2 and R3 are preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom.

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.

Hereinafter, typical examples of the compound represented by the general formula [II] will be shown, but the invention is not limited thereto.

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.

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).

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.

Examples of the sulfite M salt include ammonium sulfite, sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium metabisulfite, and the like.

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.

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.

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.

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.

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.

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.

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 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.

Incidentally, the compound represented by the above formula also includes enolated products and salts thereof.

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.

Specific examples of bleach accelerators preferably used in the present invention are shown below.

Exemplary compound (A-1) (A-2) (A-3) (A-4) (A-5> (A-6) (A-7) )(, N-C5NHNHC5-NH.

(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.

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).

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.

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.

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-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.

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.

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.

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

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.

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 photographically useful fragments 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.

[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.

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.

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).

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.

[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.

[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.

[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.

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.

The results are summarized in Table 2.

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

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.

(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.

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.

The above results are summarized in Table 3.

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.

In addition, the exemplified compounds used in Experiment 2 above (II-14), respectively <I[-9).

(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).

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.

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.

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

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 .

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.

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.

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, 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.

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.

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.

The results are shown in Table 6.

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)

[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. )