JPH06324448A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve desilverability and to prevent precipitation of a ferric complex by processing the silver halide color photographic sensitive material with a bleach-fixing solution containing the ferric complex of a specified compound but substantially no sulfite ion. CONSTITUTION:The silver halide photographic sensitive material is color developed and processed with the bleach-fixing solution containing substantially no sulfite ion and the ferric complex of the compound represented by the formula in which each of R1-R6 is H, an aliphatic or aromatic group, or hydroxy; W is a bonding group represented by-(W1-Z)n-W2-; each of M1-M4 is H or a cation; W1 is alkylene or a simple bond; W2 is alkylene or -CO-; Z is a simple bond or -O-, -S-, -CO-, or -N(Rw)-; Rw is H or alkyl, but both of Z and W1 are not simple bond at the same time; and n is 1, 2, or 3.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a bleaching solution or a bleach-fixing solution which is excellent in desilvering property, stability and biodegradability.

[0002]

2. Description of the Related Art In the photographic industry, with the widespread use and simplicity of photographs, photographers are increasingly demanding that they see the photograph as soon as possible, resulting in faster processing, that is, shorter processing time. There is a strong demand, and in particular, reduction of the desilvering process time, which occupies almost half of the processing time, is a major issue.

Conventionally, as means for accelerating the desilvering process,
Described in West German Patent No. 866,605,
A bleach-fixing solution containing a ferric aminopolycarboxylic acid complex salt and a thiosulfate in one solution is known, but originally, a ferric aminopolycarboxylic acid complex salt having a weak oxidizing power (bleaching power) is used. Since it coexists with a thiosulfate having a reducing power, its bleaching power is remarkably weakened, and it is extremely difficult to sufficiently desilver a color light-sensitive material in a short time, and there is a drawback that it cannot be put to practical use. Therefore, as a method of increasing the bleaching power, a method of adding various bleaching accelerators to a bleaching bath, a bleach-fixing bath, or a prebath thereof has been proposed. Examples of such a bleaching accelerator include, for example, JP-A-51-87036.
Ammonium bromide described in British Patent No. 926,56
No. 9 water-soluble iodide salt, and JP-B-53-118
The halide salts described in No. 54 and the like are known.

Further, in recent years, from the viewpoint of protecting the global environment, it has been desired to use a material having good biodegradability as a photographic material. By the way, both the ethylenediaminetetraacetic acid iron (III) complex and the 1,3-propylenediaminetetraacetic acid iron (III) complex, which are mainly used as conventional bleaching agents, are not biodegraded, and in the former case, the regulatory function in some areas Therefore, a bleaching agent having good biodegradability is desired.

[0005]

The compound represented by the general formula (I) is known to have good biodegradability, and its iron (III) complex is a bleaching agent excellent in desilvering property. is there. However, this compound is a stain (Dm
It has been found that there is a drawback that the iron complex precipitates when the (in) is increased and the bleach-fix solution is aged, and its solution has been long awaited. In particular, it has been found that the above stain becomes worse as the rapid processing is performed, and particularly when the washing and / or stabilizing step performed in the final step of the processing is short.

[0006]

The present invention has achieved the above object by the following means. [Item 1] In the method for processing a silver halide color photographic light-sensitive material, after the silver halide color photographic light-sensitive material is color-developed, iron (II) which is a compound represented by the following general formula (I) is used.
I) A processing method of a silver halide color photographic light-sensitive material, which comprises processing with a bleach-fixing solution containing at least one kind of complex and containing substantially no sulfite ion.

[0007]

[Chemical 4]

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group. W represents the following general formula (W). M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation General formula (W)-(W ₁ -Z) _n -W ₂ -General formula (W ), W ₁ represents an alkylene group or a single bond, W ₂ represents an alkylene group or —CO—, Z is a single bond, —O—, —S—, —CO— or —N (R _w ) —.
(R _w represents a hydrogen atom or an optionally substituted alkyl group). However, Z and W ₁ are not a single bond at the same time. n represents an integer of 1 to 3. [Item 2] The processing method for a silver halide color photographic light-sensitive material according to item 1, wherein the bleach-fixing solution contains at least one sulfinic acid represented by the following general formula (II).

[0009]

[Chemical 5]

(In the formula, Ra ₁ represents an alkyl group or an aryl group, X represents a hydrogen atom, ammonium, an alkali metal atom or an alkaline earth atom.) [Claim 3] The bleach-fixing solution has the following general formula (III) ) A method for processing a silver halide color photographic light-sensitive material according to item 1, which contains at least one adduct of a carbonyl compound represented by the formula (1) and a bisulfite.

[0011]

[Chemical 6]

(In the formula, Rb ₁ and Rb ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an aryl group or a heterocycle).

According to the present invention, a silver halide color photographic light-sensitive material is treated with a bleach-fixing solution containing an iron (trivalent) complex of a specific compound and containing substantially no sulfite ion. It is effective.

That is, the iron (III) complex represented by the general formula (I) has extremely high reactivity with sulfite ion (or bisulfite ion) and can be easily reduced to the iron (II) complex.
The stability of the iron (II) complex is extremely low and precipitates occur in the bleach-fixing solution, and iron (II) is easily incorporated into the light-sensitive material during the bleach-fixing process. It was found that the stain was not sufficiently washed in the oxidization step and was likely to cause residual stain. Furthermore, it has been found that the above problems occur more prominently when the treatment time of the desilvering process and the subsequent washing and / or stabilizing process is short. This problem becomes more significant when the processing time of the bleach-fixing solution is shortened and the time of the subsequent washing and / or stabilizing step is shortened. Further, sulfite has hitherto been generally used as a stabilizer for a bleach-fixing solution, but, surprisingly, when the bleaching agent of the present invention is used, it is better not to contain a sulfite salt. Of the general formula (II) and / or (II
It was found that the inclusion of the compound of I) further improved the stain. The above effects are obtained by rapid processing, particularly during short-time processing of about 10 to 30 seconds for the bleach-fixing solution, and subsequent washing and / or stabilization processing time of 1
It is particularly effective in rapid processing for about 0 to 50 seconds. In particular, if the processing time of the bleach-fixing solution is long, the amount of the iron complex incorporated into the light-sensitive material increases, and the stain increases, which is not preferable in many cases.

Next, the bleach-fixing solution used in the processing method of the present invention will be described. The present invention has one of the characteristics of the compound used as the iron (trivalent) complex in the bleach-fixing solution. Hereinafter, this compound will be described in detail. Therefore, the compound of the general formula (I) used for forming the iron (trivalent) complex in the present invention will be described in more detail. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ The aliphatic group is a linear, branched or cyclic alkyl group,
An alkenyl group or an alkynyl group having 1 to 10 carbon atoms is preferable. The aliphatic group is more preferably an alkyl group, further preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

The aromatic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. ,
A phenyl group is more preferred. R ₁ , R ₂ , R ₃ , R ₄ ,
The aliphatic group and aromatic group represented by R ₅ and R ₆ may have a substituent, for example, an alkyl group (for example, methyl,
Ethyl), aralkyl groups (eg phenylmethyl), alkenyl groups (eg allyl), alkynyl groups, alkoxy groups (eg methoxy, ethoxy), aryl groups (eg phenyl, p-methylphenyl), amino groups (eg dimethylamino), Acylamino group (eg acetylamino), sulfonylamino group (eg methanesulfonylamino), ureido group, urethane group, aryloxy group (eg phenyloxy), sulfamoyl (eg methylsulfamoyl), carbamoyl group (eg carbamoyl, methylcarbamoyl) ), Alkylthio groups (eg methylthio), arylthio groups (eg phenylthio), sulfonyl groups (eg methanesulfonyl), sulfinyl groups (eg methanesulfinyl), hydroxy groups, halogen atoms ( For example, chlorine atom, bromine atom, fluorine atom, cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group (eg phenyloxycarbonyl), acyl group (eg acetyl, benzoyl), alkoxycarbonyl group (eg methoxycarbonyl). ), An acyloxy group (eg acetoxy), a carbonamido group, a sulfonamide group, a nitro group, a hydroxamic acid group, and the like, and if possible, a dissociation product or a salt thereof. When the above substituent has a carbon atom, it preferably has 1 to 4 carbon atoms. R ₁ ,
R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are preferably hydrogen atoms or hydroxy groups, and more preferably hydrogen atoms.

The linking group represented by W is represented by the following general formula (W). Formula _{(W) - (W 1 -Z} ) n -W 2 - W 1 represents an alkyl group or a single bond. The alkylene group represented by W ₁ is preferably a linear or branched alkylene group having 1 to 8 carbon atoms (for example, a methylene group, an ethylene group,
A propylene group) and a cycloalkylene group having 5 to 10 carbon atoms (for example, a 1,2-cyclohexylene group). W ₂ represents an alkylene group or -CO-. The alkylene group represented by W ₂ has the same meaning as the alkylene group represented by W ₁ .
The alkylene groups represented by W ₁ and W ₂ may be the same or different from each other, or may have a substituent.
As the substituent, those mentioned as the substituent for R ₁ are applicable, but an alkyl group, a hydroxy group or a carboxy group is preferable. W ₁ and W ₂ are more preferably an alkyl group having 1 to 3 carbon atoms, and a methylene group or an ethylene group is particularly preferable. Z is a single bond, -O-, -S-,
_{-CO -, - N (R W} ) - represents a. R _W represents a hydrogen atom or an optionally substituted alkyl group. R as a substituent
_Although those mentioned as the substituent of ₁ can be applied, it is preferably a carboxy group, a phosphono group, a sulfo group, a hydroxy group or an amino group. Z is preferably a single bond. n is preferably 1 or 2, and more preferably 1. Specific examples of W include the following.

[0018]

[Chemical 7]

[0019]

[Chemical 8]

Examples of the cation represented by M ₁ , M ₂ , M ₃ and M ₄ include alkali metals (eg lithium, sodium, potassium), ammonium (eg ammonium, tetraethylammonium) and pyridinium. it can.

In the present invention, specific examples of the compound represented by the above general formula (I) are shown below, but the present invention is not limited thereto.

[0022]

[Chemical 9]

[0023]

[Chemical 10]

[0024]

[Chemical 11]

[0025]

[Chemical 12]

[0026]

[Chemical 13]

The compounds represented by formula (I) of the present invention are disclosed in JP-A-63-199295 and JP-A-3-17.
It can be synthesized according to the description in Japanese Patent No. 3857 or the like. As described in these documents, the compound represented by the general formula (I) of the present invention includes optical isomers ([R, R], [S, S], [S, R] , [R, S])
Exists. For example, the exemplary compound (I-1) of the compound represented by formula (I) of the present invention has three optical isomers ([R, R], [S, S], [S, R]). Exist and these can be synthesized individually or as a mixture. It goes without saying that the present invention includes these individual optical isomers and mixtures thereof. In the present invention, a compound synthesized from an L-amino acid such as [S, S] -form as a starting material is more preferable than other optical isomers. These compounds are Springer and Copekka's Che
m. Zvesti. 20 (6): 414-422 (19)
66) and the method described in JP-A-3-173857.

The iron (III) complex of the compound represented by the general formula (I) of the present invention can be prepared by mixing a trivalent iron ion with the compound of the general formula (I). When used as a bleaching agent, it may be isolated and used as a chelating agent iron (III) complex. In this case, it can be isolated, for example, as an ammonium salt, a sodium salt, or a potassium salt. The amount of these iron (III) complexes used is 0.02 mol / liter per liter of a bleaching bath.
It is about 1.0 mol, preferably about 0.04 mol to 0.5 mol. In addition to the iron (III) complex, 10 to 2 free compounds are used.
It is preferable to make it exist in an excess of about 0%. In the compound of the general formula (I), I-1, I-2, I-3, I-15,
The compounds of I-16 and I-17 are particularly preferable.

Next, the concentration of sulfite ion of the present invention will be described. The sulfite ion means a sulfite ion or a bisulfite ion liberated in the bleach-fixing solution, which reacts by an iodometry method. As a result of being analyzed by an iodometry method or the like, it is determined that the substance does not contain substantially, sulfite ion is 0.04 mol / liter or less, preferably 0.02 mol / liter or less.
It means less than mol / liter. The lesser one may be zero.

In order to use the bleach-fixing solution in such a state, the bleach-fixing solution may be contacted with air as much as possible or used immediately after preparation. In order to collect air, for example, the area of the gas-liquid interface may be reduced by a floating pig.

Next, the compound of the general formula (II) which is a preferred embodiment of the present invention will be described in detail. Where R
When a ₁ is an alkyl group, it has 1 to 50 carbon atoms, preferably about 3 to 30 carbon atoms, and the alkyl group may be branched. Further, examples of the substituent include a phenyl group, a halogen atom, an amino group, a sulfonic acid group, a carboxyl group, a nitro group, a hydroxy group, a cyano group, an acyl group and a sulfonamide group.

When Ra ₁ is an aryl group, it preferably has about 6 to 30 carbon atoms. Preferred aryl groups include a phenyl group and a naphthyl group, which may have the above-mentioned substituents. In the present invention, Ra ₁
Is most preferably a substituted or unsubstituted phenyl group. Hereinafter, preferable sulfinic acids used in the present invention will be described, but the present invention is not limited thereto.

[0033]

[Chemical 14]

[0034]

[Chemical 15]

[0035]

[Chemical 16]

[0036]

[Chemical 17]

[0037]

[Chemical 18]

The above compounds may be used alone or 2
You may use together more than one kind. The above compound can be obtained as a commercially available product, or can be synthesized by, for example, the method described in JP-A-62-143048 or a method analogous thereto. The amount of the above compound added is preferably about 0.001 mol to 1 mol, and more preferably about 0.01 mol to 0.5 mol, per liter of the bleach-fixing solution.

Next, the general formula (I
The compound of II) will be described in detail. The compound of the general formula (III) is a compound that forms an adduct with sulfite or bisulfite, and plays a role of substantially reducing the concentration of sulfite ion or bisulfite ion. Addition of the additive is
The isolated product may be added as an adduct, or an equimolar or more compound of the general formula (III) may be added in the presence of sulfite or bisulfite. The details of the compound represented by formula (III) are described below.

When Rb ₁ and Rb ₂ are an alkyl group, an alkenyl group or an araalkyl group, it preferably has about 1 to 10 carbon atoms. In the case of a cycloalkyl group, an aryl group, or a heterocyclic group, it preferably has 6 to 30 carbon atoms, and more preferably about 6 to 20 carbon atoms. These groups may have a substituent, and are specifically the same as the above-mentioned substituents of Ra ₁ .
In the present invention, the case where Ra ₁ is a hydrogen atom and Rb ₁ is an aryl group which may have a substituent, particularly a phenyl group which may have a substituent is most preferable. The specific compounds of the present invention are shown below, but the invention is not limited thereto.

[0041]

[Chemical 19]

[0042]

[Chemical 20]

[0043]

[Chemical 21]

[0044]

[Chemical formula 22]

[0045]

[Chemical formula 23]

Many of these compounds are commercially available and can be used as they are. Further, other compounds can also be synthesized using a known organic synthesis reaction. For example, Organic Synthesis (Org.Syn.)
Collective Vol.I 537 (1941), Collective Vol.I
564 (1955), Organic Reaction (Org.Rractio
n) 16, 1 (1968), SR Sandler, W. Kalaw, Volume 2 of Organic Functional Group Preparations
291 (1986), Vol. 3, p. 205 (197)
It can be synthesized according to the method described in 2) and the like. The addition amount of this compound is preferably 0.0 per liter of the bleach-fixing solution.
The amount is 1 to 1.0 mol, more preferably 0.03 to 0.5 mol.

Next, the processing method of the present invention will be described. The color developing solution used for developing the photosensitive material is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Although aminophenol compounds are also useful, p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 4-amino-N-ethyl-N. -Β-hydroxyethylaniline, 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-N-β-methoxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N- [delta] -hydroxybutylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include agents or antifoggants. Also, if necessary, various preservatives such as hydroxylamine, N, N-di (sulfoethyl) hydroxylamine, diethylhydroxylamine, sulfite, hydrazines, phenylsemicarbazides, triethanolamine, and catecholdisulfonic acids, ethylene glycol. , Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Various chelating agents represented by viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid. , Hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine Add di (o-hydroxyphenylacetic acid) and their salts. The pH of these color developing solutions is generally 9-12.

The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 1 liter or less per 1 m 2 of the light-sensitive material, and the bromide ion concentration in the replenishing solution can be reduced. It can be 300 ml or less. Preferably 30 ml to 150 ml
/ M ² . 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. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution. Also, the processing time for color development is 5
Second to 3 minutes and 30 seconds, preferably about 10 to 60 seconds.

The photographic emulsion layer after color development is usually subsequently bleach-fixed. 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 described above, it is necessary to use the iron (trivalent) complex of the compound represented by the general formula (I) as the bleaching agent, but other bleaching agents may be used in combination as necessary.
Representative bleaching agents that can be used together are ferricyanide; dichromate; organic complex salts of iron (trivalent) or cobalt (trivalent), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, ethyliminodiacetic acid. Aminopolycarboxylic acids such as 1,3-diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes, etc. Can be used together.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and its prebath. Specific examples of useful bleach accelerators are described in the following specifications:
US Patent 3,893,858, West German Patent 1,29
0,812, JP-A-53-95,630, Research Disclosure No. No. 17,129 (1978
, Etc.) compounds having a mercapto group or a disulfide bond; thiazolidine derivatives described in JP-A-50-140,129; US Pat. No. 3,706,5.
61, thiourea derivatives; JP-A-58-16,2;
35, iodide salt; West German Patent 2,748,43
Polyoxyethylene compounds described in No. 0; JP-B-45
A polyamine compound described in -8836; bromide ion or the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and are particularly described in US Pat. No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95,630. The compounds mentioned are preferred. Further, US Pat. No. 4,55
The compounds described in No. 2,834 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. The processing time of the bleach-fix bath is generally 10 seconds to 12 seconds.
It is about 0 seconds. 10 seconds to 30 seconds is preferable in the sense that the effect of the present invention is sufficiently exhibited. When the length is short, desilvering failure occurs, and when the length is long, the effect of the present invention cannot be sufficiently obtained.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. The use of thiosulfates is common, especially ammonium thiosulfate. Is the most widely used. The addition amount is 0.01 mol to 3 mol / liter, preferably about 0.5 mol to 2 mol / liter. The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
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.
nal of the Society of Motion Picture and Televisio
n Engineers Volume 64, P. 248-253 (1955
May May issue).

According to the multistage countercurrent system described in the above-mentioned document,
Although the amount of water to be washed can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and the resulting suspended matter adhering to the photosensitive material. In the processing of the color light-sensitive material 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, the antibacterial agents and antifungal agents described below can be used, and Horiguchi Hiroshi "Chemistry of antibacterial and antifungal agents", Hygiene Engineering Society "Sterilization of microorganisms, sterilization, antifungal technology", Japan The bactericide described in "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Antifungal Society can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set according to the characteristics and uses of the light-sensitive material, but in the present invention, it is about 15 seconds to 45 ° C. and about 5 seconds to 2 minutes. Further, in order to fully exert the effects of the present invention, 1
The range of 0 to 50 seconds is the most preferable. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilization treatment, all known methods described in JP-A-57-8,543, JP-A-58-14,834 and JP-A-60-220,345 can be used.

It is preferable that the washing water and the stabilizing solution contain various surfactants in order to prevent unevenness of water droplets when the photosensitive material after processing is dried. As these surfactants, polyethylene glycol type nonionic surfactants,
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 are preferred, but it is preferable to use nonionic surfactants, especially alkylphenol ethylene oxide addition. The thing is preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

In addition, it is preferable that the washing water and the stabilizing solution contain various antibacterial agents and fungicides in order to prevent water stains and molds generated on the processed light-sensitive material. Examples of these antibacterial agents and antifungal agents are shown in JP-A Nos. 57-157244 and 58-105145, which are thiazolylbenzimidazole compounds, and JP-A-57-8542. Such isothiazolone compounds, chlorophenol compounds represented by trichlorophenol, bromophenol compounds, organotin and organozinc compounds, acid amide compounds,
Diazine and triazine compounds, thiourea compounds,
Benzotriazole compounds, alkyl guanidine compounds, quaternary ammonium salts such as benzalkonium chloride, antibiotics such as penicillin, Journal Antibacterial &
Antifungus Agent (J. Antibact. Ant
Ifung. Agents) vol 1. No. 5, p.207 to 223 (1983), general-purpose antifungal agents and the like can be mentioned. You may use these 2 or more types together. Further, various bactericides described in JP-A-48-83820 can also be used.

Further, it is preferable that the washing water and the stabilizing solution contain various chelating agents. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid and diethylenetriamine-N, N, N ', N'-tetramethylene. Examples thereof include organic phosphonic acids such as phosphonic acid, and hydrolysis products of maleic anhydride polymers described in European Patent 345172A1.

In the stabilizing solution, compounds that stabilize the dye image, such as formalin, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, N-methylol compounds such as dimethylolurea and N-methylolpyrazole, and organic compounds are used. Acids, pH buffers, etc. are included. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the concentration of free formaldehyde in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include hexamethylenetetramine and N-methylolpyrazole.
N-methylolazoles described in 318644, N,
Azolylmethylamines described in Japanese Patent Application No. 3-142708 such as N'-bis (1,2,4-triazol-1-yl) piperazine are preferable. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners,
It is also preferable to contain a hardening agent, an alkanolamine described in U.S. Pat. No. 4,786,583, and a preservative that can be contained in the fixing solution or the bleach-fixing solution. Among these, the sulfinic acid compounds described in JP-A-1-231510 (for example, benzenesulfinic acid, toluenesulfinic acid, or salts thereof such as sodium and potassium) are preferable, and the addition amount of these is a stabilizing solution. 1
1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol per liter is preferable, and 3 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol is particularly preferable.

Various treatment liquids in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Normally, a temperature of 33 ° C. to 42 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, the processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.
It is preferable that the amount of replenishment in each processing step is small. The amount of replenisher is preferably 0.1 to 50 times, more preferably 3 to 50 times the carry-in amount of the pre-bath per unit area of the light-sensitive material.
30 times. Further, the developing solution used for developing the black-and-white light-sensitive material in the present invention is described in Japanese Patent Application No. 61-22.
6292 (JP-A-63-81337), specification 66
Pp. Line 7-68.

In the processing method of the present invention, any developing processing method can be used as the processing method in the developing processing. Specifically, batch processing (for details, see “Photo Industry” November 1974, page 98, etc.), drum processing (for details, “Photo industry” December 1974, page 45, etc.), hanger treatment (For details, see "Photo Industry" 19
(January 1975, page 80, etc.) and the like. Further, there can be mentioned a continuous process which is carried out while replenishing the replenisher according to the processing amount of the light-sensitive material.

The silver halide emulsion and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) used in the light-sensitive material of the present invention, and the processing method applied for processing the light-sensitive material, As the processing additive, those described in the following patent publications, particularly European Patent EP0,355,660A2 (Japanese Patent Application No. 1-107011) are preferably used. The places where the photographic components are described in the above patent publications are shown as a list.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

[Table 5]

Among these photographic constituents, as the cyan coupler, in addition to the diphenylimidazole type cyan coupler described in JP-A-2-33144, the 3-hydroxy group described in European Patent EP0,333,185A2. Pyridine cyan couplers (among these, couplers (42) listed as specific examples, which are 4-equivalent couplers having a chlorine leaving group to make them 2 equivalents, and couplers (6) and (9) are particularly preferable) and JP It is also preferable to use the cyclic active methylene cyan couplers described in JP-A-64-32260 (specifically, coupler examples 3, 8, and 34 listed as specific examples).

Further, in the present invention, the use of a pyrazoloazole type magenta coupler represented by the following general formula (M) is particularly preferable from the viewpoint of reducing stain after the treatment. General formula (M)

[0069]

[Chemical formula 24]

In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

In the present invention, when the magenta coupler of the general formula (M) is used, the uptake of the iron (trivalent) complex in the bath having a bleaching ability is reduced and the stain after the treatment is improved. It is estimated that

Next, the coupler represented by formula (M) will be described in detail. Among the coupler skeletons represented by the formula (M), a preferable skeleton is 1H-imidazo [1,2-b] pyrazole,
1H-pyrazolo [1,5-b] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4] triazole, 1H-pyrazolo [1,5-d] tetrazole and 1H-pyrazolo [1,5-a] benzimidazole.

Among the pyrazoloazole-based couplers represented by the formula [M], the imidazo [1,2-
b] pyrazoles, pyrazolo [1,5-b] [1,2,4] triazoles described in U.S. Pat. No. 4,540,654, and pyrazolo [[3,25,067] described in U.S. Pat. No. 3,725,067. 5,1-c] [1,2,4] triazole is preferable, and from the viewpoint of light fastness, pyrazolo [1,5-b] [1,2,4] triazoles are particularly preferable.

For details of the substituents on the azole ring represented by the substituents R ₁ , X and Z, see, for example, US Pat. No. 4,540,654, column 2, line 41 to column 8, line 27. It is described in. Pyrazoloazole couplers in which a branched alkyl group is directly bonded to the 2, 3 or 6-position of a pyrazolotriazole ring as described in JP-A-61-265167 and JP-A-61-265167. No. 65246, a pyrazoloazole coupler containing a sulfonamide group in the molecule,
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group described in JP-A-61-147254, JP-A-62-209457 or JP-A-6-209457.
JP-A-3-307453, a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position, a pyrazolotriazole coupler having a phenylene group at the 2-position described in JP-A-63-41851, and Japanese Patent Application No. It is a pyrazolotriazole coupler having a carbonamide group in the molecule described in JP-A 1-222279.

Among these couplers, specific examples of the pyrazolotriazole coupler are listed below.

[0076]

[Chemical 25]

[0077]

[Chemical formula 26]

[0078]

[Chemical 27]

[0079]

[Chemical 28]

[0080]

[Chemical 29]

[0081]

[Chemical 30]

[0082]

[Chemical 31]

[0083]

[Chemical 32]

[0084]

[Chemical 33]

[0085]

[Chemical 34]

[0086]

[Chemical 35]

[0087]

[Chemical 36]

The coupler represented by the formula [M] is represented by US Pat. Nos. 4,540,654 and 4,705,863,
JP-A-61-65245, JP-A-62-209457,
62-249155, Japanese Examined Patent Publication No. 47-27411,
It can be synthesized by the method described in US Pat. No. 3,725,067.

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide and the like can be used, but especially for the purpose of the present invention. It is preferable to use a silver chlorobromide or silver chloride emulsion having a silver chloride content of 90 mol% or more, further 95% or more, and particularly 98% or more, which is substantially free of silver iodide.

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is added to the photosensitive colloid layer for the purpose of improving the sharpness of an image, etc., in EP No. 0,337,490A2, No. 27-No.
A dye which can be decolorized by treatment (among others, an oxonol dye) described on page 76 is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more,
It is preferable that the water-resistant resin layer of the support contains 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a divalent to tetravalent alcohol (eg, trimethylolethane).

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, the compound (F) and // which chemically bond with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing. Further, in the light-sensitive material according to the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, JP-A-63-271 is used.
It is preferable to add an antifungal agent as described in No. 247.

As a support used in the light-sensitive material of the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. In particular, the transmission density of the support is 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferably set in the range of 5 to 0.8.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, upon exposure, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved.

[0095]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these. Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and a magenta coupler was further changed to obtain a multi-layered structure shown below. Color photographic papers A to F were produced. The coating liquid was prepared as follows.

Preparation of coating solution for fifth layer Cyan coupler (ExC) 32.0 g, color image stabilizer (C
pd-2) 3.0 g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.0 g and color image stabilizer (Cpd-).
8) To 5.0 g, 50.0 cc of ethyl acetate and 14.0 g of a solvent (Solv-6) were added and dissolved, and this solution was added with 2 cc of sodium dodecylbenzenesulfonate (8 cc).
After adding to 500 cc of 0% gelatin aqueous solution, it was emulsified and dispersed by an ultrasonic homogenizer to prepare an emulsified dispersion. On the other hand, silver chlorobromide emulsion (cube, average grain size of 0.
1: 4 mixture of 58 μm large size emulsion and 0.45 μm small size emulsion (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively, and 0.6 mol% of AgBr was locally contained in a part of the grain surface in each size emulsion). In this emulsion, the red sensitizing dye E shown below was added to the emulsion of large size per mol of silver in an amount of 0.2.
9 × 10 ^-4 mol, or 1.1 × for small emulsions
10 ⁻⁴ mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the fifth layer having the composition shown below.

Coating solutions for the first to fourth layers, the sixth layer and the seventh layer were prepared in the same manner as the fifth layer coating solution. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The amount of gelatin hardener used was 3% (weight) based on gelatin. Further, Cpd-10 and Cpd-11 were added to each layer so that the total amounts were 25.0 mg / m ² and 50.0 mg / m ² , respectively. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. [Blue-sensitive emulsion layer] Sensitizing dye A

[0098]

[Chemical 37]

And sensitizing dye B

[0100]

[Chemical 38]

(2.0 × 10 ⁻⁴ mol for large size emulsion and 2.5 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) [Green-sensitive emulsion] Layer] Sensitizing dye C

[0102]

[Chemical Formula 39]

(Per mol of silver halide, 4.0 × 10 ^-4 mol for large size emulsion, 5.6 × 10 ^-4 mol for small size emulsion) and sensitizing dye D

[0104]

[Chemical 40]

(1 mol of silver halide: 7.0 × 10 ^-5 mol for large size emulsion and 1.0 × 10 ^-5 mol for small size emulsion) [Red-sensitive emulsion layer] Sensitizing dye E

[0106]

[Chemical 41]

(0.9 × 10 ⁻⁴ mol for large size emulsion and 1.1 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) Further, the following compounds were halogenated. 2.6 × per mol of silver halide
10 ⁻³ mol was added.

[0108]

[Chemical 42]

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 8.5 × 10 ⁻ per mol of silver halide. ⁵ mol, 7.7 × 10 ^-4
Mol, 2.5 × 10 ⁻⁴ mol. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ⁻⁴ mol and 2 mol, respectively, per mol of silver halide. × 10 ^-4
Mol added. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer in order to prevent irradiation.

[0110]

[Chemical 43]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)]

First Layer (Blue Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large size emulsion having average grain size of 0.88 μm and small size emulsion of 0.70 μm (silver molar ratio)) Coefficients of variation of grain size distribution are 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide is locally contained in a part of grain surface in each size emulsion.) 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06

Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention layer (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitivity) Emulsion layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion having an average grain size of 0.55 μm and small size emulsion of 0.39 μm (Ag molar ratio). Coefficients of variation of grain size distribution are respectively 0.10 and 0.08, 0.8 mol% of AgBr was locally included in a part of the grain surface in each size emulsion) 0.12 Gelatin 1.24 Magenta coupler (M-6) 0.23 Color image stability Agent (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) ) 0.40

Fourth Layer (UV Absorbing Layer) Gelatin 1.58 UV Absorbing Agent (UV-1) 0.47 Color Mixing Inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion with average grain size 0.58 μm and small size emulsion with 0.45 μm (Ag mole ratio)) The coefficient of variation of the grain size distribution is 0.09 and 0.11, and AgBr 0.6 mol% was locally contained in a part of the grain surface in each size emulsion.) 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 0. 40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14

Sixth Layer (UV Absorbing Layer) Gelatin 0.53 UV Absorbing Agent (UV-1) 0.16 Color Mixing Preventing Agent (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh Layer ( Protective Layer) Gelatin 1.33 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.17 Liquid paraffin 0.33 The chemical formulas and the like of the compounds used in each layer are described below.

[0117]

[Chemical 44]

[0118]

[Chemical formula 45]

[0119]

[Chemical formula 46]

[0120]

[Chemical 47]

[0121]

[Chemical 48]

[0122]

[Chemical 49]

The sample thus obtained was designated as sample A. Next, Samples B to F were prepared by changing the magenta coupler of Sample A by equimolar amounts as follows.

Sample B M-4 Sample C M-24 Sample D M-A Sample E M-B Sample F M-C Incidentally, M-A, M-B and M-C are the following compounds.

[0125]

[Chemical 50]

Samples A to F obtained as described above are
It was exposed to 10 CMS through a wedge wedge and processed using the following processing steps and the following processing solutions. However, the composition of the bleach-fixing solution was changed as shown in Table 6 and each of them was processed. Processing step Temperature Time (second) Color development 40.0 ° C. 22.5 Bleach fixing 30-35 ° C. 22.5 Rinse 30-35 ° C. 10 Rinse 30-35 ° C. 10 Rinse 30-35 ° C. 10 Rinse 30-35 ° C. 10 Rinse Is a 4-tank countercurrent system of →→→.

The composition of each processing solution is as follows.

(Color developer) Tank liquid water 800 ml β-alanine-diacetic acid 3 g sodium catechol-3,5-disulfonate 0.3 g triethanolamine 11 g potassium bromide 0.05 g sodium chloride 5.0 g diethylhydroxylamine 5 0.0 g N, N-di (sulfoethyl) hydroxylamine 5.0 g Optical brightener (UVITEX CK Ciba-Geigy Co., Ltd.) 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4 -Aminoalinine sulfate 10.0 g Water was added to 1000 ml pH 10.30

(Bleaching Fixing Solution) Water 800 ml Ammonium thiosulfate (50% by weight) 150 ml Ammonium sulfite (see Table 6) General formula (I) Compound Iron (III) ammonium (see Table 6) 0.15 mol General formula (II) Compound (see Table 6) 0.20 mol Compound of general formula (III) (see Table 6) 0.20 mol Water added 1000 ml pH (25 ° C) acetic acid, ammonia water pH 5.30

(Rinse Solution) Ion-exchanged water (3 ppm each for calcium and magnesium)
The treated sample was measured for the amount of residual silver by fluorescent X-ray at the maximum density part. For the unexposed area, the minimum density (D _Bmin ) of yellow was measured with a Macbeth densitometer. Each bleach-fix solution was placed in a 100 ml beaker, and the solution was allowed to stand at room temperature for the number of days until precipitation occurred. The results are shown in Table 6.

[0131]

[Table 6]

According to the present invention, the desilvering performance is excellent, and the yellow stain is No. 1 or No. 1 which is a conventional bleach-fixing solution.
It has recovered to a level equivalent to 2. Especially the general formula (II)
The effect is remarkable when the compound of (III) is used in combination. Further, in Samples A, B and C using the preferred magenta coupler represented by the general formula [M], the increase in yellow stain was particularly reduced, and favorable results were obtained.
Also, the number of days until precipitation occurs was better in Nos. 6 to 8 containing less sulfite than in Nos. 3 to 5, and the formula (II)
It was significantly improved by the addition of the compound of (III).

Example 2 In the same manner as in the treatment liquid of Example 1, No. 9, except that instead of the compound II-5, II-2,
II-3, II-6, II-9, II-11, II-13, II-1
The same processing was performed using 9, II-22, and II-23, respectively, and excellent results in desilvering performance and stain were obtained.

Example 3 As in the treatment liquid of Example 1, No. 13, except that compound III-2 was used instead of compound III-2.
-3, III-6, III-7, III-12, III-15,
When the same processing was performed using III-30 and III-34, excellent results were obtained in desilvering performance and stain.

Example 4 Example 1, No. 1, No. 4,
Sample A was processed in the same manner as in Example 1 except that the bleach-fix solutions of No. 10, No. 13, and No. 16 were used, except that the processing time of the bleach-fix solution was 10 ″, 30 ″, and 45 ″. Then, the amount of residual silver and D _Bmin were obtained, and the results are shown in Table 7.

[0136]

[Table 7]

In the present invention, the amount of residual silver and the yellow stain are improved.
0 ″ and 30 ″ have good yellow stain.

[Embodiment 5] Japanese Patent Application Laid-Open No. 3-150563,
A color negative film (Sample 101) was prepared by the same method as described in Example 1 (pp667).
The prepared sample was cut into a width of 35 mm, processed, exposed to a white (color density 4800 ° K) wedge exposure, and processed in the processing steps shown below. However, the bleach-fix solution was processed for each of which the composition was changed.

Step Processing time Processing temperature Color development 2 minutes 15 seconds 37.8 ° C Bleach-fix solution 2 minutes 38 ° C Washing with water (1) 15 seconds 38.0 ° C Washing with water (2) 15 seconds 38.0 ° C Stability 10 seconds 38.0 ° C Also, crossover time Is 5 seconds, and this time is included in the above processing time.

The composition of the processing liquid is shown below. (Color developer) Mother liquor (g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.5 Potassium iodide 1. 5 ml hydroxylamine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 7.0 Water was added to 1.0 liter pH 10.25

(Bleach-fixing solution) Compound Iron (III) complex / ammonium salt (see Table 8) 0.25 mol Ethylenediaminetetraacetic acid 0.01 mol Ammonium bromide 100 g Ammonium nitrate 100 g Ammonium sulfite See Table 8 Ammonium thiosulfate (50% by weight) ) 250 g Compound of general formula (II) (see Table 8) 0.2 mol Compound of general formula (III) (see table 8) 0.2 mol Water added 1 liter pH (with ammonia water, acetic acid) pH 6 .00

(Stabilizer) Formalin (37%) 2.0 ml Surfactant C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₅ -H 0.4 g Ethylene glycol 1.0 g Water was added to 1.0 Liter pH 5.0-7.0

Obtained as described above. The amount of residual silver and the concentration of yellow stain of each treated sample were measured in the same manner as in Example 1. The results are shown in Table 8.

[0144]

[Table 8]

From Table 8, it can be seen that according to the present invention, the desilvering property is improved and the yellow stain level is also reduced.

Example 6 In place of the negative film of Sample 101 of Example 5, the following commercial color negative film was obtained and similarly processed, and good results were obtained in the present invention. The color negative film used is as follows.

Fuji Photo Film Co., Ltd. Super G 100 Batch No. S06214 Super G 400 〃 V06252 REALA 〃 877004 Super HG 200 〃 528528 Super HG 1600 〃 761004 Kodack Super Gold 100 Batch No. 077 G09C Super Gold 200 〃 119 L07A Super Gold 400 〃 794 L14A Super Gold 1600 〃 134 L20B Made by Konica Mommy batch No. 209009 Super DD 100 〃 507811 Super DD 200 〃 108005 Super XG 400 〃 620006 Scotch Scotch Color 100 Batch No. NG8377 Scotch Color EXL200 〃 HJ1834 Scotch Color 400 〃 GJ0637 Agfa Color XRG100 Batch No. 8399 Agfa Color XRS200 〃 9793 Agfa Color XRS400 〃 798

[0148]

INDUSTRIAL APPLICABILITY According to the method of the present invention, the desilvering property is good even when the color photographic material is bleached by using the iron (III) complex of the compound represented by the general formula (I) which is biodegradable. The iron complex with the passage of time can prevent precipitation. Further, it is possible to suppress an increase in stain of the processed color light-sensitive material.

Claims (3)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material, which comprises subjecting an exposed silver halide color photographic light-sensitive material to color development, followed by iron (III) complex of a compound represented by the following general formula (I). A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a bleach-fixing solution containing at least one of the above and substantially containing no sulfite ion. [Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group. W is represented by the following general formula (W). Represents a linking group.
M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. Formula _{(W) - (W 1 -Z} ) n -W 2 - In the general formula (W), W ₁ represents an alkylene group or a single bond. W ₂ represents an alkylene group or -CO-. Z is a single bond, -O -, - S -, - CO- or -N (R _w) -
(R _w represents a hydrogen atom or an optionally substituted alkyl group). However, Z and W ₁ are not a single bond at the same time. n represents an integer of 1 to 3. ) 2. The method of processing a silver halide color photographic light-sensitive material according to claim 1, wherein the bleach-fixing solution contains at least one sulfinic acid represented by the following general formula (II). [Chemical 2] (In the formula, Ra ₁ represents an alkyl group or an aryl group, X represents a hydrogen atom, ammonium, an alkali metal atom or an alkaline earth atom.) 3. The silver halide color according to claim 1, wherein the bleach-fixing solution contains at least one adduct of a carbonyl compound represented by the following general formula (III) and a bisulfite. Processing method of photographic light-sensitive material. [Chemical 3] (In the formula, Rb ₁ and Rb ₂ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an aryl group or a heterocycle).