JPS6395451A - Bleach-fix bath excellent in rapid processing - Google Patents

Abstract

PURPOSE:To enable 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, (n1-3) are each an integer of 0-3. In formula II, R2 and R3 are each alkyl group or hydrogen atom, but, both R2 and R3 are not simultaneously hydrogen atom, and R2 and R3 together with each other may form a ring. Thus, the titled bath is applied to the photosensitive material for 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 [Industrial Application Field] 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 a 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, No. 60-130738, No. 60-136
No. 744, etc.) The above-mentioned DTPA-Fe complex salt can satisfy the above characteristics in a high pI-1 range, specifically in a pH range of about 7 to 9, but ammonia gas is generated in such a pH range. However, when developing in a narrow space, it is unfavorable 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 further investigation, the present inventors discovered that a specific low p
By using a specific aminopolycarboxylic acid iron complex in the H range, the decrease in desilvering ability and poor color restoration, which are thought to be caused by the accumulation of ferrous ions, can be solved at the same time, and the generation of ammonia gas can also be solved. I found out that it can be done.

In addition, when putting this bleach-fix solution into practical use, by using a specific preservative, it is possible to improve the deterioration of the storage stability of the bleach-fix solution over time during continuous processing without adversely affecting the improvement effect of the above problems. We have discovered that this can be prevented and have come up with the present invention.

[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 R shadows, in which the pH of the solution is 3.0 to 3.0.
6.8 and which has a compound represented by the following general formula [I] as a ligand, and a ferric complex salt having the following general formula [I] as a ligand.
This was achieved using a bleach-fixing solution containing the compound shown in [I].

General formula [Ico (wherein R1 represents a hydrogen atom or a lower alkyl group, nl, n2 and n3 each represent an integer of O to 3. However, the sum of nl, n2 and n3 is an integer of 3 or 4. and the sum of the numbers is 3 or more.) General formula [II] -OH (In the formula, R2 and R3 each represent an alkyl group or a hydrogen atom. However, R2 and R3 are hydrogen atoms at the same time.) (In addition, R2 and R3 may be combined to form a ring.) [Specific constitution of the invention] The bleach-fixing solution of the present invention contains a compound represented by the general formula [I] as a ligand. A ferric complex salt is used.

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

Hereinafter, preferred example compounds of the compound represented by the general formula [I] -2 A second compound having the compound represented by the above general formula [I] as a ligand
The iron complex salt (hereinafter referred to as the ferric complex salt of the present invention) is a free 1! Although it is also used as I (hydrogen salt), it can also be used as an alkali metal salt such as sodium salt, potassium salt, lithium salt, ammonium salt, or water-soluble amine salt such as triethanolamine salt as the opposite end. .

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. Furthermore, 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, ferric complex salts using exemplified compounds (1-1), (I-2) and (I-3) as ligands are preferred. Further, among the exemplified compounds N01 (I-1), (I-2) and (I-3), it is particularly preferable to use (I-1) and (I-2) from the viewpoint of solubility. In view of various points such as the desired effect, 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 as long as the effect of the present invention can be obtained in the bleach-fix solution of the present invention, but if the ferric complex salt concentration becomes too high, the shelf life of the bleach-fix solution may be On the other hand, if the concentration of the ferric complex salt is too low, the desilvering performance and color recovery performance will deteriorate. Therefore, usually 0.02 to 1.3
It is preferable to use it in the range of 0 mol/1, and from 0.10 to
It is more preferable to use it in a range of 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 pH range of pt-+3.0 to pt-+3.0 because sulfur dioxide gas is generated if the pH is less than 3.0, and the effect of the present invention is insufficient if the pH is higher than pt-16.8.
6.8, and it can be used at any pH within this l) H range, but in addition to desilvering and recoloring properties, it also has low temperature solubility of various iron salts, and sulfur dioxide gas generated from sulfite ions. Considering odor, it is preferable to use it at a pH of 4.0 to 6.7, most preferably at a pH of 5.0 to 6.5.

The bleach-fix solution of the present invention contains a compound represented by the general formula [T[].

In general formula [II], R2 and R3 are not hydrogen atoms, but each represents an alkyl group or a hydrogen atom, but the alkyl groups represented by R2 and R3 may be the same or different, and each has 1 to 3 carbon atoms. Alkyl groups are preferred. The alkyl groups of R2 and R3 include those having substituents, such as amino groups, alkoxy groups (such as methoxy groups), sulfonic acid groups, carboxylic acid groups,
Examples include hydroxyl groups, etc., and these include, for example, U.S. Patent No. 3.287.125, U.S. Pat.
Examples include hydroxyamines described in No. 1, No. 3,281,124, and the like.

Further, R2 and R3 may be combined to form a ring,
For example, it may constitute a heterocyclic ring such as piperidine or morpholine.

Below, preferred specific It-1 represented by the general formula [nl]
90H3-N N-U V-) The compound represented by the general formula [I[] (hereinafter referred to as the compound of the present invention) is a hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphoric acid It can also be used in the form of salts such as salts and acetates.

The above compounds of the present invention may be used alone or in combination of two or more, and the amount added varies depending on the type of the compound of the present invention and other compounds used in combination, but per 12 of the bleach-fix solution of the present invention. It is preferable that it is 0.1 to 50 g,
More preferably it is 1-20i7.

The compound of the present invention represented by the general formula [II] of the present invention is:
It is a derivative of hydroxylamine that is widely used as a preservative for color developing solutions, and some of these compounds are used as preservatives for so-called external color film color developing solutions that contain couplers in color developing solutions Special Public Service No. 45-22198
JP-A-53-32035, JP-A-52-15343, preservatives for black and white developing agents added to color developing solutions.
It is only known to be used as No. 7).

Hydroxylamine acts as a good preservative for color developing agents in color developing solutions, but it is known that in bleach-fixing solutions it rather promotes the oxidation of thiosulfate ions, and therefore the bleach-fixing solution of the present invention It is a totally unknown and surprising fact that the hydroxylamine derivative, which is the compound of the present invention represented by the general formula [II], has good effects as a preservative.

In order to improve storage stability, the bleach-fix solution of the present invention preferably further contains a compound capable of releasing sulfite M salt and/or sulfite ion. Such compounds include ammonium sulfite, 1t[sodium]
Potassium sulfite, sodium hydrogen sulfite, 1 alt [potassium hydrogen, 1 alt! Examples include sodium, formaldehyde bisulfite adducts, and the like.

These compounds contain o, o per bleach-fix solution 11 of the present invention.
ooi moles to 2.0 moles, preferably 0.001 moles to 1.3 moles, most preferably 0.01 moles to 0
．． It is used in an amount of 9 moles or less.

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 thereof include thiosulfates such as thiolad ammonium, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. These fixing agents can be used in an amount of 5 g/2 or more, preferably 50 (]/ffi or more, more preferably 70 a/Q or more.

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 V5M! , 1ffi sand, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid,
pH buffering agents consisting of various salts such as sodium acetate and ammonium hydroxide may be contained alone or in combination of two or more. 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 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 following general formulas [A~Engineering 1~
It is preferable to use the compounds shown in [A to IV] because they exhibit the effects of the present invention well.

General formula [Δ-I] In the formula, Ql represents an atomic group necessary to form a nitrogen-containing heterocycle (including one in which a 5- to 6-membered unf triad ring or saturated ring is condensed), R1 does not represent a hydrogen atom or an alkyl group. However, Q' has the same meaning as Ql.

General formula [Δ-1[] In the formula, R2j7 and R3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group,
It represents an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group or an alkenyl group.

A represents or n1-valent heterocyclic residue W (including those in which 5- to 6-membered unsaturated rings are condensed), and X represents -S, -0 or -NR''. Here, R and R' are synonymous with R2 and R3, respectively, X' is synonymous with X, Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, an alkyl group, or an atom , R" is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocycle P
U group (including those with fused 5- to 6-membered unsaturated rings)
or represents an amine group, n1 to n6 and m1 to m5
each represents an integer from 1 to 6. B has 1 or more carbon atoms
6, R4 and R5 are each R2Lt
3 and R3. However, Rye and R5 may each represent -B-8Z, and R2 and R3, R
and R', R4 and R5 may be bonded to each other 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.

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 amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group, or -81-3 -Z+. however,
R6 and R7 represent X:'c H-, 81 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, a nitrogen-containing heterocyclic residue or \8, represents an integer. ] (G')z In the formula, Ar is a divalent aryl group or a combination of an aryl group and an oxygen atom and/or an alkylene group.
B2 and R3 each represent a lower alkylene group, R8, Rs, R1o and R1
1 each represents a hydroxy-substituted lower alkyl group,
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-43 (A-5) (A-6) (A-7) H,N-C5NHNHC8-NH.

(A-9) The amount of bleach accelerator added is approximately 0 per 12 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 material as long as it is a silver halide photographic material for withdrawal. Specifically, the silver iodide content is preferably 0.5.
It is preferable that the light-sensitive material uses a high-sensitivity silver iodobromide emulsion containing at least mol %, more preferably at least 1 mol %.

The bleach-fix solution of the present invention may be used as a processing solution for bleaching and fixing the above-mentioned original and shadow silver halide photographic light-sensitive material immediately after color development, or after color development, it may be used for processing such as washing with water, rinsing, or stopping. It may be used as a bleach-fixing solution after color development, or as a bleach-fixing solution after pre-fixing 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 method described in JP-A-57-8543, which omit the washing process or extremely reduces the amount of washing water, may be used. 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. Further, in addition to the steps such as color development, bleach-fixing, and washing with water, six auxiliary steps may be added as necessary, such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water.

The photographic silver halide emulsion applicable to the present invention can be chemically sensitized by conventional methods, 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 can be hardened and can 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.

[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.

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. A sensitive silver halide emulsion layer was coated to give a total silver density of 88 ma per 100 clz. 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.
In the red-sensitive silver halide emulsion layer, the following (C-1) was used as a cyan coupler, and in each emulsion layer, a sensitizing dye, a hardening agent, and a conventional additive for ring expansion were added. 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 and subjected to cherry blossom exposure according to the usual method, and then processed using a piece processing device according to the following steps. (hereinafter referred to as manual processing).

Processing process Processing temperature (°C) Pa number Processing time 1 Color development 37.8 1M 13915 seconds 2 Bleach fixing
37.8 1 tank 4 minutes 20 seconds 3 washes
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
2 IQ Hydroxyamine Sulfate
2.5g sodium chloride
0.69 Sodium diethylenetriaminepentaacetate 2.0 g N-ethyl-N-β-hydroxyethyl-3-methyl-4-aminoaniline sulfate 4.5 g Potassium hydroxide 1.2 g Add water to 11
1 using sodium hydroxide or 20% sulfuric acid.
) Hlo, adjusted to 06.

[Bleach-fix solution] Ferric ammonium complex salt of organic acid shown in Table 1 0.25 mol Ammonium thiosulfate (10% solution) 300d Ammonium sulfite 5g Exemplary compound (I[-
1) 5a Silver powder 2.0g water was added to make the total number 12, and I]H was adjusted as shown in Table 1 with acetic acid and aqueous ammonia.

[Stabilizing solution] 21 g of formalin (37% aqueous solution) Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 5 nN water was added to prepare 1i.

Table 1 Table 1 (Continued) The bleach-fix solution after the above treatment was mixed with an aperture ratio of 10 Ci"/2 (this is an opening condition equivalent to a general automatic processor, and an air contact area of 1 ocf was applied to 11 bleach-fix solutions. 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. The residual silver ffi (m(1/a,
= ) was measured using a fluorescent X-ray method, and the cyan dye concentration was measured using a Sakura Photoelectric Power Meter PDA-65 (manufactured by Konishiroku Photo Industries) to measure the recoloring rate.

From Table 2 above, when using the paid ferric acid complex salt according to the present invention and a bleach-fixing solution in the pf range of -13.0 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, according to a comparative bleach-fixing solution using comparative DTPA as a specific acid, the desilvering performance and recoloring performance were extremely good at pH 7 to 8 before storage over time, but were insufficient after storage for one week. The performance will be as follows. Furthermore, it is found that EDTA has insufficient desilvering performance and color restoration performance regardless of storage over time.

(Experiment 2) Bleach-fix solution N013, N014 used in the above (Experiment 1)
and 5 g of the compound (I[-1) of the general formula [■] of N095
, without addition, (I[-1>3(1, (I-2) 3g
, (II-3)3(1, (I[-10)3g, (n-2
1) Bleach-fix solutions Nos. 3-11 to 5-16 were prepared in the same manner except that the solution was changed to 313 and pl-16 and 0, respectively. 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, storage was continued, and the number of days until precipitation occurred was visually observed.

The above results are summarized in Table 3.

Hereafter, phase removal 161L number Mi: Table 3 Indicates the number of days until precipitation occurs.

As is clear from Table 3 above, the general formula [II] of the present invention
It can be seen that by adding the compound represented by the above, storage stability can be greatly improved without adversely affecting desilvering and recoloring properties.

Furthermore, the compound of general formula [II is I[-4, ll-8, l
Similar experiments were repeated using 1-9, 1-11, and 13, but similar results were obtained.

From the results of Experiment 1 and Experiment 2 above, it was found that the bleach-fixing solution of the present invention, that is, the pH range of 3.0 to 6.8, was obtained by using the general formula [II
Contains a ferric complex salt having a compound represented by as a ligand,
Furthermore, the bleach-fixing solution containing the compound represented by the general formula [II] has excellent desilvering performance, especially after storage over time, prevents the occurrence of poor color recovery, 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 2 of Example 1. However, here, the type and concentration of bleach in the bleach-fix solution were varied as shown in Table 4.

In addition, as a compound of general formula [n], exemplified compound (II-1
> was set to 5 g/2, and the pH 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 also shown in Table 4.

As is clear from Table 4, the bleach-fixing solution of the present invention has a bleach content of 0.02 mol/y to 1,30 mol/ffi, preferably 0.10 to 1.0 mol/y. 20 mol/ff
11 More preferably, if the content is in the range of 0.20 to 0.8 mol/2, it can be seen that the bleach-fixing solution is a good one with high desilvering and restoring ability even after storage over time and a long period of time until sulfurization. .

In addition, instead of the compound (It-1) of the general formula [nl, (I
I-5), (II-6), (II-12), (■-16
), (n-18) and (■-29) were repeated, and similar results were obtained.

Example 3 A bleach-fix solution was stored over time in the same manner as in Experiment 1 of Working Example 1. However, here, as the bleach-fix solution, the amounts of bleach added in bleach-fix solutions No. 1, 3. 4, and 5 of Experiment 1 are as shown in Table 5, and the concentrations of KI in the bleach-fix solutions are as shown in Table 5. I changed it like that. Further, the pH of the bleach-fix solution 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 is subjected to bleaching and fixing according to the CNK-4 standard processing (Konishi Roku Photo Industries Color Negative Processing) to completely remove residual silver, and then the transmission density of the magenta dye is measured and this value is calculated using the DRI. And so. Next, color development 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 subjected to bleaching and fixing according to the CNK-4 standard process was measured, and this value was defined as DR2. DRI and DR
Magentastin was evaluated by determining the difference between 2 (ΔDR).

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,
The addition of KI suppressed magentastin to a low level, while reducing the desilvering ability to a small extent, giving good results.

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.
~3-36 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.

Table 6J: When a bleach accelerator is added, even if the bleaching time is short, the bleach-fix solution of the present invention can be used directly after preparation or after storage. On the other hand, bleach-fixing solutions other than those of the present invention were effective immediately after preparation, but desilvering properties, restoring properties, and preservability further deteriorated with storage. It became clear that it was deteriorating.

In addition, bleach accelerators are A-3, A-5, 8-7, and A-8.
, A-10 and A-11 were also subjected to similar experiments, and 19 had similar results.

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 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 an alkyl group or a hydrogen atom. However, R_2 and R_3 are not hydrogen atoms at the same time.
3 may be combined to form a ring. )