JPH06258806A - Stabilizing processing solution for silver halide color photographic sensitive material and processing method using the same - Google Patents

Abstract

PURPOSE:To prevent occurrence of stains in continuous processing and to enhance storage stability of images after processing by processing the color photographic sensitive material with a stabilizing processing solution containing a monobasic organic acid having at least one hydroxyl group. CONSTITUTION:The silver halide color photographic sensitive material is processed with the stabilizing processing solution containing the monobasic organic acid having at least one hydroxyl group. This stabilizing processing solution has an effect of stabilizing a dye image formed by color development, especially, effect of preventing discoloration of a magenta dye and contains the replenishing solution to be used for maintaining the composition of the processing solution at the time of continuous processing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizing processing solution used for processing a silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as a light-sensitive material) and a processing method using the same. is there.

[0002]

2. Description of the Related Art Generally, the basic steps of processing a silver halide color photographic light-sensitive material are a color development step and a desilvering step.
In the color developing step, the silver halide exposed by the color developing agent is reduced to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image. General silver halide color photographic light-sensitive materials undergo a color development process after imagewise exposure, whereas silver halide color reversal photographic light-sensitive materials develop color after imagewise exposure and after black and white development and reversal processes. A developing process is performed. In the next desilvering step, the silver generated in the color developing step is oxidized by the action of an oxidizing agent commonly referred to as a bleaching agent, and then dissolved by a complex ion forming agent of silver ion commonly referred to as a fixing agent. It Through this desilvering process, only the dye image is formed on the color light-sensitive material. The desilvering process thus generally consists of a bleaching process and a fixing process. Here, when the bleaching step and the fixing step are bleach-fixing steps performed in one bath, the bleach-fixing step may be performed after the bleaching step, or the bleach-fixing step may be performed between the bleaching step and the fixing step.

A light-sensitive material on which a dye image is formed is processed with a stabilizing solution after desilvering in order to preserve the dye image obtained. The treatment with the stabilizing solution is performed after the washing step or directly after the desilvering treatment. In the processing of color reversal light-sensitive materials, there is also known a method of stabilizing a dye image by incorporating an image stabilizer in an adjusting solution instead of using the stabilizing solution in the final bath. The stabilizing solution contains various compounds in order to improve the stability of the stabilizing solution itself, in addition to the image stabilizer which stabilizes the dye image of the light-sensitive material. For example, U.S. Pat.No. 3,140,177 describes stabilizing images by using a stabilizing solution containing a polybasic organic acid such as citric acid or succinic acid. There is also a problem that stains frequently adhere to the light-sensitive material during processing and that a stable replenisher for these replenishers produces precipitates in the solution over time.

[0004]

SUMMARY OF THE INVENTION Therefore, a first object of the present invention is to provide a stabilizing treatment liquid which prevents the generation of precipitates in the liquid over time and a treatment method using the same. . A second object is to provide a stabilizing treatment liquid which prevents adhesion of stains to a light-sensitive material in continuous treatment, and a treatment method using the same. A third object is to provide a stabilizing treatment liquid having excellent image stability and a treatment method using the same.

[0005]

As a result of studying the above problems, the present inventor has found that the object can be achieved by the following stabilizing treatment liquid and treatment method using the same. That is, (1) A stabilizing treatment liquid for a silver halide color photographic light-sensitive material containing at least one monobasic organic acid having at least one hydroxy group.

The present invention will be described in detail below. The stabilizing treatment liquid of the present invention means a treatment liquid having an effect of stabilizing a dye image formed by color development (in particular, an effect of preventing fading of a magenta dye over time), and also includes a replenisher. Is. A processing solution used after color development is preferable, a stabilizing solution and an adjusting solution are preferable, and a stabilizing solution is particularly preferable. The compounds of the present invention are
It may be added to the replenisher of each step and is a preferred embodiment of the present invention. The replenisher used in the present invention is a replenisher that is replenished in order to maintain the composition of the treatment solution during continuous processing. The stabilizing solution in the present invention is a stabilizing solution or a stabilizing solution as a substitute for washing with water, which is conventionally used in the final processing step of a color negative film or a color reversal film, and when the final step is a washing step or a rinsing step, stabilization of the prebath The stabilizing solution used in the chemical conversion step is included, but it is preferably used in the final step.

The monobasic organic acid having a hydroxy group contained in the stabilizing solution of the present invention will be described in detail below. The monobasic organic acid having a hydroxy group of the present invention is
It is composed of a linear or branched alkyl group having a hydroxy group moiety and an organic acid moiety. The carbon number of the compound is preferably 2 to 6, more preferably 2 to 4. As the organic acid moiety, carboxylic acid, sulfonic acid and phosphoric acid are preferable, and carboxylic acid is particularly preferable. That is, those represented by the following general formula (I) are preferable. General formula (I) HO-L-COOH L represents a linear or branched alkyl group having 1 to 5 carbon atoms. Next, specific examples of the monobasic organic acid having a hydroxy group of the present invention are shown below, but the present invention is not limited thereto.

[0008]

[Chemical 1]

Of the above organic acids, 1-1 and 1-2 are preferable, and 1-1 is particularly preferable. The content of these organic acids is 0.00 per 1 liter of the stabilization treatment liquid.
001 to 0.5 mol is preferable, and 0.0001 to 0.1
Molar is more preferred.

In the stabilizing solution of the present invention, a compound that stabilizes a dye image (hereinafter referred to as an image stabilizer), for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, a formaldehyde bisulfite adduct, and hexamethylene are used. Tetramine and its derivatives, hexahydrotriazine and its derivatives, dimethylol urea,
Although an N-methylol compound such as N-methylolpyrazole can be added, in the present invention, when the free formaldehyde concentration in the liquid is 0 to 0.01%,
Further, when it is 0 to 0.005%, the effect is large and it is preferable. Examples of the image stabilizer for controlling the concentration of free formaldehyde include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bis. (1,2,4-triazol-1-ylmethyl) piperazine etc. JP-A-4-3137
Azolylmethylamines described in No. 53 are preferable. In particular, JP-A-4-359249 (corresponding to European Patent Publication No. 51
9190A2) and azoles such as 1,2,4-triazole and azolylmethylamine and its derivatives such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine. , Particularly preferred.

[0011]

[Chemical 2]

[0012]

[Chemical 3]

A-23 hexamethylenetetramine A-24 N-methylol urea

The content of these image stabilizers is as follows:
It is preferably 0.001 to 0.1 mol, and more preferably 0.001 to 0.05 mol, per liter of the stabilizing treatment liquid.

The stabilizing solution of the present invention preferably contains various surfactants in order to prevent water droplet unevenness during drying of the processed light-sensitive material. As such a surfactant, a polyethylene glycol type nonionic surfactant,
Polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant, alkylnaphthalene sulfonate type anionic surfactant, quaternary ammonium salt Type cationic surfactants, amine salt type cationic surfactants, amino salt type amphoteric surfactants, betaine type amphoteric surfactants, and nonionic surfactants are preferably used, and particularly the following general formula ( Nonionic surfactants of alkylphenoxy polyethylene oxides and alkylphenoxy polyhydroxypropylene oxides represented by W) are preferable.

[0016]

[Chemical 4]

(W is -CH₂CH₂O- or -CH₂CH (O
H) CH₂Represents O-, R₁And R₂Are each alkyl
Represents a group, and n represents 0 or 1. m is -CH₂CH₂O-
Or -CH ₂CH (OH) CH₂Represents the number of moles of O- added. ) R₁
And R₂The alkyl group of has 3 to 20 carbon atoms, preferably
C6-12, especially octyl, nonyl, dodecyl
Is preferred, and m as the number of added moles is particularly 6 to 1.
4 is preferable. Especially when the free formaldehyde concentration is low
In case of W, -CH₂CH (OH) CH₂O- is preferred
Yes. Examples of preferable surfactants are shown below, but the present invention is
It is not limited to this.

[0018]

[Chemical 5]

It is also preferable to use a silicon-based surfactant having a high defoaming effect. The addition amount of the surfactant is 0.005 g to 3 g, preferably 0.02 to 0.3 g, per liter of the stabilizing treatment liquid. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, alkanolamines described in U.S. Pat. It is also preferable to contain the sulfinic acid compound described in Japanese Patent No. 231051.

The stabilization treatment liquid of the present invention contains various chelating agents to improve the stability of the stabilization treatment liquid,
It can be preferably used in order to reduce the generation of dirt. Preferred chelating agents include organic carboxylic acid type chelating agents, organic phosphoric acid type chelating agents, inorganic phosphoric acid type chelating agents, and polyhydroxy compounds. Particularly preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N,
Organic phosphonic acids such as N'-trimethylenephosphonic acid and diethylenetriamine-N, N, N ', N'-tetramethylenephosphonic acid, or European Patent 345,172.
Examples thereof include hydrolyzates of maleic anhydride polymers described in A1. The preferable addition amount of these chelating agents is 0.000 per liter of the stabilizing treatment liquid.
It is from 01 to 0.01 mol.

The stabilizing solution of the present invention is preferably added with an antibacterial / antifungal agent for the purpose of preventing the generation of fungi and mildew, and these may be commercially available products. Antibacterial
Examples of the fungicide include thiazolylbenzimidazole compounds as shown in JP-A-57-157244 and JP-A-58-105145, isothiazolone compounds as shown in JP-A-57-8542, and trichloro. Chlorophenol compounds such as phenol
Bromophenol compounds, organic tin and organic zinc compounds, acid amide compounds, diazine and triazine compounds, thiourea compounds, benzotriazole compounds,
Alkylguanidine compounds, quaternary ammonium salts typified by benzalkonium chloride, penicillin, antibiotics typified by aminoglycosides, etc., Journal Antibacterial & Antifungus Agent (J. Antibact. Antifung.
Agents) Vol 1. No. 5, p. 207-223 (198
Examples include general-purpose antifungal agents described in 3). Also, various fungicides described in JP-A-48-83820, chlorine-based fungicides such as chlorinated sodium isocyanurate, Hiroshi Horiguchi, "Chemistry of antibacterial and antifungal agents" (1986) Sankyo Publishing, Sanitary Technology Organized by "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, Japan Society of Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986
The disinfectants described in 1) can also be used. These are 2
You may use together 1 or more types. Examples of the preservatives / antibacterial agents in the stabilizing treatment liquid of the present invention include The Merck Index Eleventh Edition (1989) Merk & Co. , INC.
The aminoglycosides described are preferred, and gentamicin is particularly preferred among the aminoglycosides. In particular, in a stabilizing solution having a low free formaldehyde concentration as described above, it prevents the floating substances produced from adhering to the light-sensitive material. The addition amount of these antibacterial / antifungal agents is preferably 0.001 to 1 g, and more preferably 0.005 to 0.5 g, per liter of the stabilizing treatment liquid.

In the present invention, the desilvering treatment may be followed by a washing treatment followed by a stabilizing treatment, or the stabilizing treatment may be carried out directly without performing a washing treatment.
The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in Jour.
n-al of the Society of Motion Picture and Tele- vis
ion Engineers Volume 64, pp. 248-253 (May 1955 issue)
It can be determined by the method described in. According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the treatment of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-8,5
No. 42, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, Use of bactericides described in "Technology for Sterilization, Sterilization, and Antifungal of Microorganisms" (1982) edited by Sanitary Technology Society, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Antibacterial and Antifungal Society Is preferred.

The pH of the stabilizing solution and the washing water of the present invention is 4-9.
And preferably 5-8. The processing temperature and processing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds.
Seconds to 2 minutes. Further, the stabilizing solution of the present invention has a remarkable effect of preventing stains when it is directly treated with the stabilizing solution after desilvering without washing with water. Further, the treatment with the stabilizing solution of the present invention, JP-A-57-8543, 58-14834,
All the known methods described in No. 60-220345 can be used. The replenishing amount of the stabilizing solution of the present invention is preferably 200 to 2000 ml per 1 m ² of the light-sensitive material. Washing with water and /
Alternatively, the overflow solution due to the replenishment of the stabilizing solution can be reused in other steps such as the desilvering step.

The present invention is applied to Research Disclosure No. 17643, pages 28 to 29, except for the stabilizing solution.
No. 18716, 651 left column to right column, and No. 307105
The development processing can be carried out by a usual method described on pages 880 to 881. The color developing solution used in the developing treatment of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful,
A p-phenylenediamine compound is preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-Methyl-4-amino-N-ethyl-N-
β-methanesulfonamide ethylaniline, 3-methyl-4-
Amino-N-ethyl-β-methoxyethylaniline, 4-
Amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl- N-
Ethyl-N- (2-hydroxypropyl) aniline, 4-amino
-3-Ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N -Methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-
Methyl-N-methyl-N- (4-hydroxybutyl) aniline,
4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-
Hydroxybutyl) aniline, 4-amino-3-ethyl-N-
Ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl-N- (5-
Hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N-bis ( Five
-Hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 4-amino
-3-Methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluene Sulfonates or sulfates are preferred. Two or more of these compounds can be used in combination depending on the purpose.

The amount of the aromatic primary amine developing agent used is preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol to 0.1 mol per liter of the color developing solution.
It is 1 mol.

The color developing solution contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor such as bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, hydroxylamines represented by the general formula (I) of JP-A-3-144446, sulfite, N,
Hydrazines such as N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, Development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos. Various chelating agents represented by carboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonone. , Nitrilo -N, N, N-
Trimethylenephosphonic acid, ethylenediamine-N, N, N, N-
Tetramethylenephosphonic acid, ethylenediamine-di (o
-Hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples. The processing temperature of the color developer in the present invention is 20 to 55 ° C, preferably 30 to 55 ° C. The processing time is 20 seconds to 5 minutes for the light-sensitive material for photography,
It is preferably 30 seconds to 3 minutes and 20 seconds. It is more preferably 1 minute to 2 minutes and 30 seconds, and in the printing material,
0 seconds to 1 minute 20 seconds, preferably 10 seconds to 60 seconds,
More preferably, it is 10 seconds to 40 seconds.

When the reversal process is performed, black and white development is usually performed before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = [contact area between processing liquid and air (cm ² )] ÷
[Volume of Treatment Liquid (cm ³ )] The aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank,
Examples thereof include a method using a movable lid described in JP-A-1-82033 and a slit development processing method described in JP-A-63-216050. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps,
For example, it is preferably applied in all steps of bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid, JP-A-4
No. 121739, a bleaching agent including a 1,3-propylenediaminetetraacetic acid iron complex salt in the lower right column of the fourth page to the upper left column of the fourth page, and a carbamoyl-based bleaching agent described in JP-A-4-73647. Bleaching agents, bleaching agents having a heterocycle described in JP-A-4-174432, bleaching agents described in European Patent Publication No. 520457, including N- (2-carboxyphenyl) iminodiacetic acid ferric complex salts. Japanese Patent Application No. 3-252775 including ethylenediamine-N-2-carboxyphenyl-N, N ', N'-ferric acetic acid
Bleaching agent, bleaching agent described in EP-A-501479, bleaching agent described in JP-A-4-127145,
The ferric aminopolycarboxylic acid salts or salts thereof described on page (11) of JP-A-3-144446 are preferably used. The organic aminocarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution.
The pH of the bleaching solution or bleach-fixing solution using these organic aminocarboxylic acid iron (III) complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH for speeding up the processing.

These bleaching processes are preferably carried out immediately after color development, but in the case of reversal processes, they are generally carried out via a conditioning bath (which may be a bleaching promoting bath) or the like. It is preferable to use the organic acid of the present invention in combination in these adjusting baths when the stabilizing solution is prepared by using the above-mentioned image stabilizer (adjusting stabilizer) because the image stability is improved. As the adjusting liquid, in addition to the image stabilizer and the organic acid of the present invention, an aminopolycarboxylic acid chelating agent such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, and cyclohexanediaminetetraacetic acid; Sulfites such as sodium sulfite, ammonium sulfite and thioglycerin, aminoethanethiol,
Various bleaching accelerators described later such as sulfoethanethiol can be contained. For the purpose of preventing scum, sorbitan esters of fatty acids substituted with ethylene oxide described in U.S. Pat. No. 4,839,262, U.S. Pat. No. 4,059,446 and Research Disclosure 191, 19104 (1980). It is preferable to contain the described polyoxyethylene compound and the like. These compounds are used in an amount of 0.1
It can be used in the range of g to 20 g, but is preferably in the range of 1 g to 5 g. The pH of the adjusting bath is usually 3 to
It is used in the range of 11, but is preferably 4 to 9, and more preferably 4.5 to 7. Processing time in the conditioning bath is 2
It is preferably 0 seconds to 5 minutes. More preferably 20
Seconds to 100 seconds, most preferably 20 seconds to 60 seconds. The replenishing amount of the adjusting bath is preferably 30 ml to 3000 ml per 1 m ² of the light-sensitive material, but particularly 50 ml to 150 ml.
It is preferably 0 ml. Treatment temperature of conditioning bath is 20 ℃
˜50 ° C. is preferable, but 30 ° C. to 40 ° C. is particularly preferable.

In the present invention, in the desilvering bath, in addition to the bleaching agent, the rehalogenating agent, pH buffering agent and known additives described on page (12) of the above-mentioned JP-A-3-144446 are known. Carboxylic acids and organic phosphonic acids can be used. Further, in the present invention, various bleaching accelerators can be added to the bleaching solution or its prebath. For such a bleaching accelerator, for example, US Pat.
893,858, German Patent 1,290,8
21, British Patent No. 1,138,842, JP-A No. 53-95630, and Research Disclosure No. 17129 (July 1978), which have a mercapto group or a disulfide group. , Thiazolidine derivatives described in JP-A-50-140129, thiourea derivatives described in U.S. Pat. No. 3,706,561, iodides described in JP-A-58-16235, German Patent No. Polyethylene oxides described in 2,748,430, JP-B-45-
The polyamine compounds described in JP-A-8836 can be used. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. Particularly preferably, British Patent No. 1,138,842 and JP-A-2
Mercapto compounds such as those described in -190856 are preferred. In the bleaching solution and bleach-fixing solution, in addition to the above compounds,
It is preferable to contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (pKa)
Is a compound of 2 to 5, and specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

The light-sensitive material processed with a processing solution having a bleaching ability is subjected to fixing or bleach-fixing processing. As such fixing solution or bleach-fixing solution, those described in JP-A-3-33847, page 6, lower right column, line 16 to page 8, upper left column, line 15 are also preferable. Incidentally, ammonium thiosulfate has been generally used as the fixing agent in the desilvering process, but other known fixing agents such as mesoionic compounds,
It may be replaced with a thioether compound, thioureas, a large amount of iodide, hypo, or the like. Regarding these, JP-A-60-61749, JP-A-60-147735, and JP-A-60-147735.
No. 21444, JP-A Nos. 1-2201659 and 1-2.
10951, 2-44355, U.S. Pat.
78,424 and the like. For example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, ammonium thiocyanate,
Sodium thiocyanate, potassium thiocyanate, dihydroxyethyl-thioether, 3,6-dithia-1,
8-octanediol, imidazole and the like can be mentioned.
Of these, thiosulfates and mesoions are preferable. Ammonium thiosulfate is preferable from the viewpoint of quick fixability, but sodium thiosulfate and mesoions are more preferable from the viewpoint of preventing the treatment liquid from substantially containing ammonium ions due to environmental problems as described above. Further, by using two or more fixing agents in combination, more rapid fixing can be performed. For example, in addition to ammonium thiosulfate or sodium thiosulfate, it is also preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether, etc. in this case. 01-10
It is preferably added in the range of 0 mol%. The amount of the fixing agent is 0.1 to 3 per liter of the bleach-fixing solution or the fixing solution.
It is 0 mol, preferably 0.5 to 2.0 mol. The pH of the fixing solution depends on the type of the fixing agent, but is generally 3.0 to
9.0, especially when thiosulfate is used.
8 to 8.0 is preferable for obtaining stable fixing performance.

The processing solution having a fixing ability contains a sulfite as a preservative (for example, sodium sulfite, potassium sulfite,
Ammonium sulfite), hydroxylamines, hydrazines, bisulfite adducts of aldehyde compounds (eg sodium acetaldehyde sodium bisulfite, particularly preferably compounds described in JP-A-3-158848) or JP-A-1.
The sulfinic acid compound etc. described in the specification of No. 231051 can be contained. Further, various fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like can be contained. Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids to the processing solution having fixing ability for the purpose of stabilizing the processing solution. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, Cyclohexanediaminetetraacetic acid, 1,
2-Propylenediaminetetraacetic acid may be mentioned.
It is also preferable to add a buffer to the bleach-fixing solution and the fixing solution in order to keep the pH of the solution constant. For example, phosphates, imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine,
Examples thereof include N-allylmorpholine and N-benzoylpiperazine.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Eastman Kodak Company's Z-121, Eusing Process C-41 3rd edition (1982), BL-1 to BL
-The items described on page 2 can be used. In the processing using the processing solution having a bleaching ability of the present invention, it is preferable that the stirring is intensified, and the practice thereof is JP-A-3-3384.
The contents described on page 8, upper right column, line 6 to lower left column, line 2 of Japanese Patent Publication No. 7 can be used as they are.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic processor used in the present invention is disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-19125.
It is preferable to have the photosensitive material conveying means described in No. 9. As described in JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the deterioration of the performance of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The processing solution having bleaching ability of the present invention is
The overflow solution after use in the treatment can be recovered, the components can be added to modify the composition, and then the overflow solution can be reused. Such usage is usually called regeneration, but the present invention can also favor such regeneration. For details of the reproduction, see Fuji Photo Film Co., Ltd., Fuji Film Processing Manual, Fuji Color Negative Film, CN-16 processing (revised August 1990), pp. 39-.
The matters described on page 40 can be applied. The kit for adjusting the processing solution having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied as a powder, and since the hygroscopicity is low,
Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be added directly without using excess water.

Regarding the regeneration of the processing solution having the bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to electric field regeneration, there is a method of regenerating bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In the electrolytic regeneration, the cathode and the anode are put in the same bleaching bath, or the anode bath and the cathode bath are regenerated in separate baths by using a diaphragm. The fixing solution can be reprocessed at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. Ion exchange or ultrafiltration is used to reduce the amount of washing water used, and it is particularly preferable to use ultrafiltration.

Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. In the processing using an automatic processor, etc., when each processing solution described above is concentrated by evaporation, in order to correct the concentration by evaporation, it is necessary to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. preferable. The specific method for replenishing water is not particularly limited, but among them, JP-A-1-254959 and 1-25.
A monitor water tank different from the bleaching tank described in Japanese Patent No. 4960 is installed, the evaporation amount of water in the monitor water tank is obtained, and the evaporation amount of water in the bleaching tank is calculated from the evaporation amount of this water. Method for replenishing bleaching tank with water in proportion 1
No. 248155, No. 3-249644, No. 3-249.
The evaporation correction method using a liquid level sensor or an overflow sensor described in Japanese Patent Nos. 645 and 3-249646 is preferable. The water to correct the evaporation of each treatment liquid is
Although tap water may be used, deionized water or sterilized water which is preferably used in the above washing step is preferably used.

Next, a photosensitive material applicable to the present invention will be described. The stabilizing treatment liquid of the present invention and the treatment using the same can be applied to any photosensitive material, but in the present invention, a photosensitive material using various plastic films as the material of the support, for example, photographing The effect is greatly exerted when applied to a color negative photographic light-sensitive material or a color reversal photographic light-sensitive material. Regarding these photosensitive materials, JP-A-3-46654 and 2-85 are available.
4, No. 2-90151, No. 4-270344, No. 5-34889, European Patent Publication 0504609A2.
No. 519190A2 and the like. In particular, silver iodobromide containing 0.2 to 20 mol% of silver iodide is preferable as the silver halide used in the color negative photographic light-sensitive material for photography or the color reversal photographic light-sensitive material.

Known photographic additives that can be used in the present invention are described in the following three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, 648, right column, page 866 2. Sensitivity enhancer, page 678, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, strong Color sensitizers-p. 649, right column 4. Whitening agent, p. 24, 647, p. Right column, p. 868, 5. Fog prevention, p. 24-25, p. 649, right column, p. 868-870, stabilizers, 6. light absorbers, 25- Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page right column 650 Page left column 872 Inhibitor ~ Right column 8. Dye image page 25 650 Page left column 872 Stabilizer 9. Hardener page 26 651 page left column 874 to 875 page 10. Binder page 26 page 651 page left column 873 page 874 page 11. Plasticizer, page 27 650 page right column page 876 Lubricant 12. Coating aid , Pages 26-27 pages 650 right column 875-876 pages surfactant 13. static page 27 pages 650 pages right column 876-877 pages inhibitors 14. matting agents pages 878-879 pages

Suitable supports that can be used in the light-sensitive material of the present invention are, for example, those described in RD. No. 17643, page 28, same No. 187
16 pages 647 right column to 648 left column, and No. 307105
It is described on page 879. As the material for the support, various plastic films described in JP-A-4-124636, page 5, upper right column, line 1 to page 6, upper right column, line 5 can be used, and preferable examples thereof include cellulose derivatives (for example, diacetyl). -, Triacetyl-, propionyl-, butanoyl-, acetylpropionyl-acetate) and polyesters described in JP-B-48-40414 (for example, polyethylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene naphthalate). To be Since the support of the film used in the present invention can obtain higher effects with the constitution of the present invention, polyethylene terephthalate, functional materials, 199
The polyethylene naphthalate described in the January, February issue, pages 20 to 28 is preferable. When the light-sensitive material of the present invention is used as a color negative film, the thickness of the support is 70 to 13
0 μm is preferable, and 80 to 120 μm is particularly preferable.

The support used when the light-sensitive material of the present invention is used as a color film is described in International Publication WO90 / 04.
205 publication, FIG. Those having the magnetic recording layer described in 1A are preferable. The support having such a magnetic recording layer preferably has a conductive layer containing zinc, titanium, tin or the like on one surface as described in JP-A-4-62543. In addition, JP-A-4-12462
A device having the striped magnetic recording layer described in No. 8 and a transparent magnetic recording layer adjacent to the striped magnetic recording layer can also be used. On the magnetic recording layer, Japanese Patent Laid-Open No. 4-73
A protective layer described in No. 737 may be provided.

In the case where the light-sensitive material of the present invention is used as a color film, the package (patrone) for storing the color film may be any existing or known one, and in particular, US Pat. No. 4,834,306. , F
IG. 1-FIG. 3 and U.S. Pat. No. 4,846,418, FIG. 1-FIG. Those described in 3 are preferable. The color film format used in the present invention is based on the Japanese Industrial Standard "JIS. K-75".
19 (1982) ”, and any known format other than the format described in JP-A-4-287040 can be used.

[0044]

The present invention is described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

Second layer (intermediate layer) Silver iodobromide emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

6th layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10

7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

9th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

Twelfth layer (medium-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

14th layer (first protective layer) Silver iodobromide emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, W-1 to W-3, B-4 to B- are added to each layer in order to improve storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0061]

[Table 1]

In Table 1, (1) Silver iodobromide emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) The silver iodobromide emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. It is sensitized. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0063]

[Chemical 6]

[0064]

[Chemical 7]

[0065]

[Chemical 8]

[0066]

[Chemical 9]

[0067]

[Chemical 10]

[0068]

[Chemical 11]

[0069]

[Chemical 12]

[0070]

[Chemical 13]

[0071]

[Chemical 14]

[0072]

[Chemical 15]

[0073]

[Chemical 16]

[0074]

[Chemical 17]

[0075]

[Chemical 18]

[0076]

[Chemical 19]

[0077]

[Chemical 20]

After exposing the color photographic light-sensitive material as described above, the color photographic light-sensitive material was processed by the following method (until the cumulative replenishment amount of the stabilizing solution became 3 times the tank capacity) using the automatic developing machine.

(Processing method) Process processing time processing temperature replenishment amount tank capacity color development 3 minutes 15 seconds 38 ° C 22ml 20 liters bleaching 3 minutes 00 seconds 38 ° C 25ml 40 liters water washing (1) 15 seconds 24 ° C (2) 10 liters countercurrent piping method to (1) Washing with water (2) 15 seconds 24 ℃ 15ml 10 liters fixed 3 minutes 00 seconds 38 ℃ 15ml 30 liters Washing with water (3) 30 seconds 24 ℃ From (4) to (3) 10 liters Countercurrent piping system Washing (4) 30 seconds 24 ℃ 1200ml 10 liters Stability 30 seconds 38 ℃ 20ml 10 liters Dry 4 minutes 20 seconds 55 ℃ Replenishment amount is 35mm width 1m Water washing (1) ~ (4 ) Use water

Next, the composition of the treatment liquid will be described. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.2 Sodium sulfite 4.0 4.8 Potassium carbonate 30.0 39.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 3.1 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 6.0 Water was added to 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 3-Mercapto-1,2,4-triazole 0.03 0.08 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Add water 1.0 liter 1.0 liter pH (adjusted with ammonia water and HNO ₃ ) 6.0 5.7

(Fixer) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Sodium sulfite 20.0 22.0 Sodium thiosulfate aqueous solution (700 g / liter) 295.0 ml 320.0 ml Acetic acid (90%) 3.3 4.0 Water 1.0 liter 1.0 liter pH 6.7 6.8

(Stabilizer) Common tank / replenisher (g) Image stabilizer (see Table 2) 0.006 mol ethylenediaminetetraacetic acid 0.03 Surfactant W-8 (50% aqueous solution) 0.7 Gentamicin 0.01 acid (see Table 2) ) See Table 2 Add water 1.0 liter pH 7.0 pH was finely adjusted using sodium hydroxide.

Stabilizer Nos. 1 to 13 using formaldehyde as an image stabilizer were prepared using formalin. In the stabilizers Nos. 1 to 13, the free formaldehyde concentration was 0.2%, and in the stabilizers Nos. 14 to 26 using A-14 as the image stabilizer, 0.007 was obtained.
%Met. Regarding the light-sensitive material processed by the above method,
The stain on the back surface of the light-sensitive material and the change with time in stain were determined by the method described below. Contamination: At the end of running, the surface of Sample 101 not coated with emulsion was observed to confirm the presence or absence of contamination. Evaluation: Good: No stain is generated. Δ: Staining is slightly generated, but there is no problem in practical use. X: There is stain.

Stain change with time: The density of the light-sensitive material processed by the above method was measured, and Dmin measured with blue light (B light) was read from the characteristic curve. Then, the sample after the measurement was stored under the following conditions, and the Dmin after the lapse of time was similarly measured. Then, the change with time of the stain of the yellow dye was determined as follows. Storage conditions: 70 ° C., 70%, 4 weeks Change in stain over time (ΔD) = (Dmin after storage) −
(Dmin before storage) Furthermore, the stability of the above-mentioned stabilizer in an unused state was evaluated by the following method. Stability: 1 liter to 10 ml of stabilizing water
The concentrated liquid changed to was prepared, filled in a bottle made of vinyl chloride, and stored in a sealed stopper at 40 ° C. for 7 weeks. At this time, the presence or absence of precipitate spots was visually confirmed. Evaluation: ◯: No precipitation occurred. Δ: Some turbidity occurred, but no precipitation occurred. X: Precipitation occurred. The results obtained by the above method are shown in Table 2.

[0086]

[Table 2]

From the results of Table 2, it can be seen that only in the embodiment of the present invention, no stain is generated, and at the same time, an excellent effect is obtained with respect to the stain at the time of storing a color image after processing. Further, regarding the stability of the liquid, it can be seen that the formation of the precipitate can be improved by the embodiment of the present invention. It can be seen that all the effects are particularly large and preferable when an image stabilizer having a low free formaldehyde concentration is used. still,
The fading of magenta dye (60 ℃
Relative humidity 20%, aged for 2 weeks, magenta density 1.5
There was no difference in the fading).

Example 2 The same treatment as in Example 1 was carried out by using the sample 201 prepared in the same manner as in Example 1 except that the support of the sample 101 in Example 1 of the present application was replaced with the one shown below. went. As a result, similar to Example 1, it was found that only the aspect of the present invention did not generate stains and showed an excellent effect.

(2-1) Preparation of Support Polyethylene terephthalate was uniaxially stretched and poly (vinylidene / acrylonitrile / itaconic acid; molar ratio 92: 5: 3) aqueous dispersion (content after stretching: 1.5 g /
m ² ), sodium dodecylbenzene sulfonate (2 mg /
m ² ), silica particles (average particle size 0.3 μm; 20 mg /
m ² ), polystyrene particles (average particle size 1.0 μm; 2 mg /
m ² ), 2-hydroxy-4,6-dichloro-1,3,5
-Triazine (35 mg / m ² ) and trimethylolprovantriaziridine (10 mg / m ² ) were applied and stretched again during drying to undercoat the support to form the first vinylidene chloride layer. At this time, the thickness of polyethylene terephthalate was 90 μm. After further corona discharge treatment on both sides, gelatin (0.2 g / m ² ) poly (degree of polymerization 10) oxyethylene dodecyl ether (2 mg / m ² ),
Compound WA (10 mg / m ² ) was applied to prepare a support as the second undercoat layer.

(2-2) Preparation of Back Surface The following back layer was applied to one side of the undercoated support prepared in (2-1) (the numbers corresponding to the respective components are g / m ² Indicates the coating amount expressed in units)

A) Back first layer Cobalt-doped iron oxide fine powder (included as gelatin dispersion; average particle size 0.08 μm) 0.2 gelatin 3.0 poly (ethyl acrylate) (average diameter 0.08 μm) 1.0 Compound WB 0.1 Compound WC 0.02

(B) Back second layer Gelatin 0.05 Conductive material SnO ₂ / Sb ₂ O ₃ (9: 1) (particle size 0.15 μm) 0.16 mg Sodium dodecylbenzenesulfonate 0.05 0.05

C) Back third layer Gelatin 0.5 Polymethylmethacrylate (average particle size 1.5 μm) 0.02 Cetyl stearate (sodium dodecylbenzenesulfonate dispersion) 0.01 Sodium di (2-ethylhexyl) sulfosuccinate 0.01 A fluorine-containing surfactant was used for the back third layer. The structural formulas of the above compounds WA, WB, WC and the fluorine-containing surfactant are shown below.

[0094]

[Chemical 21]

The coercive force of the back layer of the support obtained here was 960 Oe.

Example 3 After exposing the multilayer color reversal light-sensitive material sample 401 described in Example 4 of JP-A-4-359249, to the following method using an automatic processor (the cumulative replenishment amount of the stabilizing solution is Processed to 3 times the tank capacity).

(Treatment Method) Process Treatment time Treatment temperature Replenishment amount Tank capacity First development 6 minutes 38 ° C. 2200 ml 12 liters First water washing 2 minutes 38 ° C. 7500 ml 4 liters Inversion 2 minutes 38 ° C. 1100 ml 4 liters Color development 6 minutes 38 ℃ 2200ml 12 liters Pre-bleaching 2 minutes 38 ℃ 1100ml 4 liters Bleaching 6 minutes 38 ℃ 220ml 12 liters Settling 4 minutes 38 ℃ 1100ml 8 liters Second washing 4 minutes 38 ℃ 7500ml 8 liters Stability 1 minute 38 ℃ 1100ml 2 liters Dry 2 minutes 55 ℃ Replenishment amount per 1 m ² of light-sensitive material

Next, the composition of the treatment liquid will be described. (First developer) Tank solution (g) Replenisher solution (g) Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 1.5 1.5 Diethylenetriamine pentaacetic acid-5 sodium salt 2.0 2.0 Sodium sulfite 30.0 30.0 Hydroquinone mono Potassium sulfonate 20.0 20.0 Potassium carbonate 15.0 20.0 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 2.0 Potassium bromide 2.5 1.4 Potassium thiocyanate 1.2 1.2 Potassium iodide 2.0 mg-Ethylene glycol 13.0 15.0 Add water 1.0 liter 1.0 liter pH 9.60 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide.

(Reversal liquid) Tank liquid (g) Replenishing liquid (g) Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 Same as tank liquid Stannous chloride dihydrate 1.0 p-amino Phenol 0.1 sodium hydroxide 8.0 glacial acetic acid 15 ml Water was added to 1.0 liter pH 6.00 pH was adjusted with acetic acid or sodium hydroxide.

(Color developer) Tank liquid (g) Replenisher (g) Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 2.0 Sodium sulfite 7.0 7.0 Trisodium phosphate dodecahydrate 36.0 36.0 Potassium bromide 1.0-Potassium iodide 90 mg-Sodium hydroxide 3.0 3.0 Citrazinate 1.5 1.5 N-Ethyl-N- (β-methanesulfoamidoethyl) -3-methyl 4-aminoaniline / 3/2 sulfuric acid monohydrate 11.0 11.0 3,6-dithiaoctane-1,8-diol 1.0 1.0 Water was added to 1.0 liter 1.0 liter pH 11.80 12.00 pH was adjusted with sulfuric acid or potassium hydroxide.

(Pre-bleaching solution) Tank solution (g) Replenisher solution (g) Ethylenediaminetetraacetic acid ・ disodium ・ dihydrate 8.0 Same as tank solution Sodium sulfite 6.0 1-Thioglycerol 0.4 Water 1.0 liter pH 6.20 pH Was prepared with acetic acid or sodium hydroxide.

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid / sodium dihydrate 2.0 4.0 Ethylenediaminetetraacetic acid / Fe / (III) / ammonium / dihydrate 120.0 240.0 Potassium bromide 100.0 200.0 Ammonium nitrate 10.0 20.0 Water was added to 1.0 liter 1.0 liter pH 5.65 5.45 pH was adjusted with nitric acid or sodium hydroxide.

(Fixer) Tank solution (g) Replenisher solution (g) Ammonium thiosulfate 80.0 The same sodium sulfite 5.0 sodium bisulfite 5.0 water was added to the tank solution and 1.0 liter pH 6.60 pH was adjusted with acetic acid or aqueous ammonia.

(Stabilizer) Tank / replenisher common (g) Image stabilizer (see Table 3) 0.01 mol Ethylenediaminetetraacetic acid 0.03 Surfactant W-7 (50% aqueous solution) 0.7 Gentamicin 0.01 Add water 1.0 L Acid (see Table 3) See Table 3 pH 6.0 pH was fine adjusted using sodium hydroxide.

(First Washing, Second Washing) Tank water and replenisher common water were used.

Regarding the light-sensitive material processed by the above method,
Similar to Example 1 of the present application, the change with time of stain and stain was obtained. The results are shown in Table 3.

[0107]

[Table 3]

From the results shown in Table 3, the acid of the present invention did not stain the light-sensitive material as compared with the comparative compound in the color reversal film for photographing as in Example 1 of the present application, and the stain during storage of color images was also improved. It can be seen that the excellent effect is exhibited. No difference was found in the fading of the magenta dye in any of the stabilizing solutions.

[0109]

EFFECTS OF THE INVENTION According to the present invention, it becomes possible to perform processing using a processing agent which is excellent in liquid stability, prevents adhesion of stains in continuous processing, and has excellent image storability after processing.

Claims (4)

[Claims] 1. A stabilizing solution for a silver halide color photographic light-sensitive material, which contains at least one monobasic organic acid having at least one hydroxy group. 2. A silver halide color photographic light-sensitive material characterized by being treated with a stabilizing treatment liquid for a silver halide color photographic light-sensitive material containing at least one monobasic organic acid having at least one hydroxy group. Processing method. 3. The stabilizing treatment liquid has a free formaldehyde concentration of 0 to 0.01%.
The stabilizing treatment liquid described. 4. The free formaldehyde concentration of the stabilizing solution is 0 to 0.01%.
A method for processing a silver halide color photographic light-sensitive material as described above.