JP2646208B2 - Prevention method for precipitation of silver sulfide generated in washing substitute liquid - Google Patents

Description

Description: 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 sulfuration generated in a water washing substitute solution based on processing with an improved water washing substitute solution. It relates to a method for preventing silver precipitation.

BACKGROUND OF THE INVENTION Generally, photographic materials are subjected to color development after image exposure,
A process having a fixing ability such as bleaching, fixing or bleach-fixing is performed and then processed in a processing step such as stabilization and washing with water.In the washing step following the processing with a processing solution having the fixing ability, silver halide is used. Thiosulfate, a compound that reacts with water to form a water-soluble complex salt, and other water-soluble silver complex salts, as well as sulfites and metabisulfites as preservatives are contained in and adhered to photosensitive materials. It is known that a small amount of washing water has a bad effect on image storability. Therefore, in order to solve such a drawback, in practice, the salt is washed out of the photographic material using a large amount of running water after washing with a processing solution having a fixing ability. However, in recent years, for economic reasons such as shortage of water resources, soaring sewage charges and utility costs, and for pollution reasons, there is a demand for a treatment step in which the amount of washing water is reduced and pollution measures are taken.

Conventionally, as a countermeasure against such a problem, for example, a method in which a washing tank is configured in a multi-stage structure to counterflow water is disclosed in West German Patent No. 2,920,222 and S. R. Goldwasser.
er), "Water Flow Rate in Immersion-Washing of Motion Picture Film"
otion-picture Film) "SMPTE.Vol.64,248-253, Ma
y, (1955).

There is also known a processing method in which a preliminary washing is provided immediately after the fixing bath to reduce polluting components contained in and adhered to the photosensitive material and entering the washing step, and to reduce the amount of washing water.

However, these techniques are not treatment methods that do not use washing water at all. Therefore, under the situation where water resources have been depleted in recent years and costs have increased due to washing by increasing the price of crude oil, it has become an increasingly serious problem.

On the other hand, there is a processing method in which stabilization processing is performed immediately after photographic processing without washing with water. For example, a silver stabilization treatment with a thiocyanate described in US Pat. No. 3,335,004 is known. However, this method has a drawback in that the stabilizing bath contains a large amount of inorganic salt, so that the surface of the photographic material is stained after drying. In addition, it has been found that when these stabilizing treatments are performed, there is another disadvantage that the dye image is deteriorated during long-term storage.

As a method for preventing deterioration of a dye image during long-term storage, it has been conventionally known to use formalin. The use of a processing solution containing formalin can effectively prevent the generation of stains and a decrease in the density of dye images during long-term storage, but on the other hand, formalin is a harmful substance and is not preferable in terms of reducing pollution and environmental protection. When used in a large amount, there is a problem that the liquid preservability is greatly deteriorated.

On the other hand, recently, color photographic material processing has been gradually distributed from large labs to small labs called mini-labs represented by camera shops and film handling shops. It is being processed. Therefore, in reality, there is a growing demand for a system that can reduce pollution by minimizing the amount of replenishment as much as possible and that can be processed easily and stably without specialized knowledge.

(Object of the Invention) Accordingly, an object of the present invention is to provide a simple method for processing a silver halide color photographic light-sensitive material with low pollution.
A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material which is excellent in stability over time of a liquid and storage stability of a dye image.

(Constitution of the Invention) The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support after imagewise exposing it to at least a step of color development and a fixing ability. A method for processing a silver halide color photographic light-sensitive material, comprising a step of processing with a liquid and a step of processing with a washing substitute liquid as a final processing step, wherein the silver halide color photographic light-sensitive material is a magenta compound represented by the general formula [I] The substitute washing solution containing a coupler has a general formula [II] in the range of 2.0 × 10 ^{−5 to} 8.0 × 10 ⁻² mol per 1 substitute solution.
I] and 2.0 × per alternative solution
It contains at least one compound selected from the compounds represented by the following general formula [IV] in the range of 10 ^{-5 to} 8.0 × 10 ^-2 mol, and the replenishment amount of the washing substitute solution is at least the above-mentioned solution having fixing ability. By the photographic light-sensitive material processed in the step of carrying out, the processing liquid of the processing step before the step of processing with the water-washing alternative liquid, which is brought into the washing alternative liquid, is 2 to 50 times the carry-in amount of the photographic light-sensitive material. This is achieved by a method for processing a silver halide color photographic light-sensitive material.

General formula [I] (In the formula, Z represents a group of nonmetal atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a substituent which can be eliminated by reaction with an oxidized form of a color developing agent.

R represents a hydrogen atom or a substituent. ) General formula [III] (In the formula, A ₂ and A ₃ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group, and M represents an alkali metal.) General formula [IV] (Wherein A ₄ and A ₅ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group, M represents an alkali metal, and n represents an integer of 0 to 4) [Specific Structure of the Invention] The present invention will be described in detail below. It is well known that processing is performed using a processing solution containing formalin, which is a stabilizing processing solution generally used in the final step of a color negative film for photography. Japanese Patent Application Laid-Open No. 59-126533 discloses that instead of treating with a processing solution having a fixing ability, a washing step and a stabilization treatment containing formalin are replaced with a treatment step with a washing substitute solution. As described above, the stabilizing solution containing formalin and the washing substitute solution are separated, and the stabilizing solution is prohibited from flowing into the washing substitute solution. However, as described above, by treating with a processing solution containing formalin, there is an effect of preventing a decrease in yellow stain and density after storage of a dye image, and formalin is an important technology as a technology for improving image storability. is there. However, formalin itself has high harmfulness and is not preferable in terms of low pollution.In addition, when treated with a processing solution having a fixing ability and then treated with a washing substitute solution containing formalin, the liquid preservability, particularly sulfide is easily generated. There is a problem, and it has been very difficult to improve the liquid preservability, improve the image preservability, and reduce the pollution. As a result of intensive studies, the present inventors have found the following.

Sulfidation in the water washing substitute solution by treating with a processing solution containing formalin is caused by the reaction of formalin with the prebath components brought from the photographic material by continuous processing, such as the sulfite ions in the bleach-fixing solution and fixing solution components. It is considered that the preservability is reduced, the silver thiosulfate complex is decomposed, and sulfuration occurs. However, the above-mentioned sulfuration largely depends on the concentration of formalin, and it is possible to prevent sulfidation by lowering the concentration of formalin.Moreover, unexpectedly, even when a bisulfite adduct of an acetaldehyde derivative is used as a substitute for formalin, it is remarkable. It was found that there was an effect of preventing sulfuration. However, when the concentration of formalin was reduced, the effect on image storability was considered, and the present inventors faced new difficulties.

The present inventors have conducted further intensive studies. As a result, the use of the magenta coupler represented by the general formula (I) reduced the concentration of formalin to improve image storability, and surprisingly, the general formula (III) or It was found that even when a large amount of the bisulfite adduct of the aldehyde derivative represented by (IV) was used in a large amount, sulfuration did not occur at all and the image preservability was improved.

Here, “rinse substitute liquid” and “treatment with a rinse substitute liquid” used in the present specification will be described.

The washing substitute liquid and the treatment with the washing substitute liquid of the present invention refer to a treatment and a treatment liquid which are performed in place of the washing treatment performed after the fixing step or the bleach-fixing step.

As described above, the conventional rinsing treatment is a treatment solution of the prebath contained in the constituent film of the photosensitive material, specifically, a large amount of thiosulfate, a chemical in a fixing or bleach-fixing solution, a silver complex salt or Washing off the chemicals in the developer with water
The processing method is to apply a large amount of running water to the surface of the photosensitive film and immerse the photosensitive material in a rinsing bath so that the rinsing water flows off as quickly as possible. There is a replacement water washing method etc. that repeatedly exchanges with
Usually, it is treated only with water, but a method of performing a water washing treatment after immersing in a bath containing salts such as sodium sulfite for several minutes before performing the above-described water washing treatment to increase the treatment speed may be adopted. In any case, the washing process is performed with water. Therefore, an extremely large amount of washing water is required in order not to cause troubles such as stains, discoloration or fading of the image at the time of drying and storage of the light-sensitive material due to chemicals such as thiosulfate remaining in the light-sensitive material. Further, a facility for discarding water after the water washing treatment is required, which is not favorable in terms of space and economy. The treatment with the washing substitute liquid and the washing substitute liquid of the present invention has improved these disadvantages, and the treatment liquid used is not simply water but an aqueous solution having fungicide, antiseptic, and sterilization means, Further, if necessary, an aqueous solution containing a compound such as a chelating agent having a chelate stability number of 8 or more with respect to ferric ion, an ammonia compound, an organic acid salt, a pH adjuster, a surfactant, a sulfite, and an optical brightener. It is.

Unit area of photosensitive material processed in conventional water washing process is 1m
Attached to the light-sensitive material by supplementing the ² per about 5 to 150 of water, had flushed the compound of thiosulfate or the like has penetrated, unit area 1 m ² in the process according to the water washing substitute solution of the present invention
Compounds adhering and permeating the light-sensitive material can be washed away with a replenishment amount of about 0.01 to 2.5 per unit. Further, in the processing method of the present invention, as described above, the replenishment amount is very small as compared with the conventional water washing treatment, so that the water supply / discharge pipe facility for the automatic developing machine which is indispensable in the conventional water washing treatment process is required. Is no longer necessary, and the equipment can be reduced in size.

 Next, the present invention will be described specifically.

General formula [I] according to the present invention General formula [I] Wherein Z represents a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a substituent which can be eliminated by reaction with an oxidized form of a color developing agent.

 R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom,
Alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heterocyclic, acyl, sulfonyl, sulfinyl, phosphonyl, carbamoyl, carbamoyl, sulfamoyl, cyano, spiro compound residues, Bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group,
Ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Examples include an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and a heterocyclic thio group.

Examples of the halogen atom include a chlorine atom and a bromine atom, and a chlorine atom is particularly preferable.

The alkyl group represented by R has 1 to 32 carbon atoms, and the alkenyl group and the alkynyl group have 2 to 32 carbon atoms.
, A cycloalkyl group and a cycloalkenyl group are preferably those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The alkyl group, alkenyl group and alkynyl group may be linear or branched.

Further, these alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and cycloalkenyl group may have a substituent [for example, aryl, cyano, halogen atom, hetero ring,
In addition to cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon compound residue, acyl, carboxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl and the like which are substituted through a carbonyl group, further via a hetero atom Those specifically substituted through an oxygen atom such as hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.), sulfa Moylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, those substituted via a nitrogen atom such as ureido, alkylthio, arylthio, heterocyclic thio, sulfonyl,
Those substituted through a sulfur atom, such as sulfinyl and sulfamoyl, and those substituted through a phosphorus atom, such as phosphonyl, etc.] may be included.

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group,
1-hexylnonyl group, 1,1′-dipentylnonyl group,
2-chloro-t-butyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3-4 ′-{α- [4 ″ (p-hydroxybenzenesulfonyl) phenoxy] dodecanoylamino}
Phenylpropyl group, 3- {4'-α- [2 ", 4" -di-t-amylphenoxy) butanamido] phenyl}-
Propyl group, 4- [α- (o-chlorophenoxy) tetradecanamidophenoxy] propyl group, allyl group, cyclopentyl group, cyclohexyl group and the like.

The aryl group represented by R is preferably a phenyl group, and may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, a phenyl group, a 4-t-butylphenyl group, a 2,4-di-t-amylphenyl group, a 4-tetradecanamidophenyl group, a hexadecyloxyphenyl group,
And a 4 '-[α- (4 "-t-butylphenoxy) tetradecanamido] phenyl group.

The heterocyclic group represented by R is preferably a 5- to 7-membered heterocyclic group, which may be substituted or condensed. Specific examples include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.

Examples of the acyl group represented by R include an acetyl group,
Phenylacetyl group, dodecanoyl group, α-2,4-di-
Examples thereof include an alkylcarbonyl group such as a t-amylphenoxybutanoyl group, an arylcarbonyl group such as a benzoyl group, a 3-pentadecyloxybenzoyl group, and a p-chlorobenzoyl group.

Examples of the sulfonyl group represented by R include an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group, and an arylsulfonyl group such as a benzenesulfonyl group and a p-toluenesulfonyl group.

Examples of the sulfinyl group represented by R include an alkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group, and a 3-phenoxybutylsulfinyl group, an arylsulfinyl group such as a phenylsulfinyl group, and an m-pentadecylphenylsulfinyl group. .

Examples of the phosphonyl group represented by R include an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group,
And an arylphosphonyl group such as a phenylphosphonyl group.

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) and the like, for example, an N-methylcarbamoyl group, an N, N-dibutylcarbamoyl group, an N- (2-pentane (Decyloctylethyl) carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl group and the like.

The sulfamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), and the like. For example, an N-propylsulfamoyl group, an N, N-diethylsulfamoyl group, an N- ( 2-pentadecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group and the like.

Examples of the spiro compound residue represented by R include spiro [3.3] heptan-1-yl and the like.

Examples of the bridged carbonized compound residue represented by R include bicyclo [2.2.1] heptane-1-yl and tricyclo [3.3.
1.1] Decan-1-yl, 7,7-dimethyl-bicyclo [2.
2.1] Heptane-1-yl and the like.

The alkoxy group represented by R may further have the same substituents as those described above for the alkyl group, for example, a methoxy group, a propoxy group, a 2-ethoxyethoxy group,
Examples include a pentadecyloxy group, a 2-dodecyloxyethoxy group, and a phenethyloxyethoxy group.

The aryloxy group represented by R is preferably phenyloxy, and the aryl nucleus may be further substituted by the substituents or atoms described above for the aryl group. For example, a phenoxy group, pt-butylphenoxy And m-pentadecylphenoxy group.

As the heterocyclic oxy group represented by R, those having a 5- to 7-membered hetero ring are preferable, and the hetero ring may further have a substituent, for example, 3,4,5,6-tetrahydropyranyl. Ru-2-oxy group, 1-phenyltetrazole-
A 5-oxy group.

The siloxy group represented by R may be further substituted with an alkyl group or the like, and examples include a trimethylsiloxy group, a triethylsiloxy group, and a dimethylbutylsiloxy group.

Examples of the acyloxy group represented by R include an alkylcarbonyloxy group and an arylcarbonyloxy group, and may further have a substituent, specifically, an acetyloxy group and an α-chloroacetyloxy group. And a benzoyloxy group.

The carbamoyloxy group represented by R is an alkyl group,
An aryl group or the like may be substituted, and examples thereof include an N-ethylcarbamoyloxy group, an N, N-diethylcarbamoyloxy group, and an N-phenylcarbamoyloxy group.

The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) and the like, for example, an ethylamino group, an anilino group, an m-chloroanilino group, a 3-pentadecyloxycarbonylanilino group , 2
-Chloro-5-hexadecanamidanilino group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group) and the like, and may further have a substituent.
Examples thereof include an ethylpropanamide group, an N-phenylacetamide group, a dodecaneamide group, a 2,4-di-5-aminophenoxyacetamide group, and an α-3-t-butyl-4-hydroxyphenoxybutanamide group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, and may further have a substituent. Specific examples include a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a p-toluenesulfonamide group, and a 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group represented by R may be open-chain or cyclic, and may have a substituent, for example, succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutar And imide groups.

The ureido group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), and the like, for example, an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group , Np-triureido group and the like.

The sulfamoylamino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), and the like. For example, an N, N-dibutylsulfamoylamino group, an N-methylsulfamoyl Amino group, N-
And a phenylsulfamoylamino group.

The alkoxycarbonylamino group represented by R may further have a substituent, and examples thereof include a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, and an octadecyloxycarbonylamino group.

An aryloxycarbonylamino group represented by R is
It may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group.

The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group,
Examples include an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, and a benzyloxycarbonyl group.

The aryloxycarbonyl group represented by R may further have a substituent, for example, a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, an m-pentadecyloxyphenoxycarbonyl group and the like.

The alkylthio group represented by R may further have a substituent, for example, an ethylthio group, a dodecylthio group,
Examples include an octadecylthio group, a phenethylthio group, and a 3-phenoxypropylthio group.

The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group, a p-methoxyphenylthio group, a 2-t-octylphenylthio group, a 3-octadecylphenylthio group, −
Examples thereof include a carboxyphenylthio group and a p-acetoaminophenylthio group.

The heterocyclic thio group represented by R is preferably a 5- to 7-membered heterocyclic thio group, and may further have a condensed ring;
It may have a substituent. Examples include a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-diphenoxy-1,3,5-triazole-6-thio group.

Examples of the substituent capable of leaving by reaction with an oxidized form of the color developing agent represented by X include a halogen atom (a chlorine atom,
And a group substituted through a carbon atom, an oxygen atom, a sulfur atom or a nitrogen atom in addition to a bromine atom and a fluorine atom.

Examples of the group substituted through a carbon atom include a carboxyl group, for example, a compound represented by the general formula (R ₁ ′ has the same meaning as R, Z ′ has the same meaning as Z, and R ₂ ′ and R ₃ ′ represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.) , A hydroxymethyl group and a triphenylmethyl group.

Examples of the group substituted through an oxygen atom include an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a sulfonyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyloxalyloxy group, and an alkoxyoxalyloxy group Is mentioned.

The alkoxy group may further have a substituent, and examples thereof include an ethoxy group, a 2-phenoxyethoxy group, a 2-cyanoethoxy group, a phenethyloxy group, and a p-chlorobenzyloxy group.

As the aryloxy group, a phenoxy group is preferable, and the aryl group may further have a substituent.
Specifically, a phenoxy group, a 3-methylphenoxy group, 3
-Dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4- [α- (3′-pentadecylphenoxy) butanamide] phenoxy group, hexadecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthyloxy group, p
-Methoxyphenoxy group and the like.

The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, and may be a condensed ring or may have a substituent. Specific examples include a 1-phenyltetrazolyloxy group and a 2-benzothiazolyloxy group.

Examples of the acyloxy group include an alkylcarbonyloxy group such as an acetoxy group and a butanoloxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group, and an arylcarbonyloxy group such as a benzoyloxy group.

Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group.

Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group.

Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group.

Examples of the alkyl oxalyloxy group include a methyl oxalyloxy group.

Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group.

Examples of the group substituted through a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group.

Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a phenethylthio group, and a benzylthio group.

Examples of the arylthio group include phenylthio, 4-methanesulfonamidophenylthio, 4-dodecylphenethylthio, 4-nonafluoropentanamidophenethylthio, 4-carboxyphenylthio, and 2-ethoxy-5-t-butyl. A phenylthio group and the like.

Examples of the heterocyclic thio group include 1-phenyl-1,
Examples include a 2,3,4-tetrazolyl-5-thio group and a 2-benzothiazolylthio group.

Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group.

As the group substituted through the nitrogen atom, for example, a general formula Are shown. Here, R ₄ ′ and R ₅ ′ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and R ₄ ′ And R ₅ 'may combine to form a heterocycle. However, R ₄ ′ and R ₅ ′ are not both hydrogen atoms.

The alkyl group may be linear or branched, preferably,
It has 1 to 22 carbon atoms. The alkyl group may have a substituent. Examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an acylamino group, and a sulfonamide. Group, imino group,
Acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamino group, aryloxycarbonylamino group, hydroxyl group, carboxyl group, cyano group,
A halogen atom. Specific examples of the alkyl group include ethyl, octyl, 2-ethylhexyl, and 2-chloroethyl.

The aryl group represented by R ₄ ′ or R ₅ ′ is preferably an aryl group having 6 to 32 carbon atoms, particularly preferably a phenyl group or a naphthyl group, and the aryl group may have a substituent, and
The substituents to the alkyl group represented by R ₄ ′ or R ₅ ′ and the alkyl group are exemplified. Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 4-methylsulfonylphenyl group.

The heterocyclic group represented by R ₄ ′ or R ₅ ′ is preferably a 5- to 6-membered heterocyclic group, and may be a condensed ring or may have a substituent. Specific examples include a 2-furyl group, a 2-quinolyl group, a 2-pyrimidyl group, a 2-benzothiazolyl group,
A 2-pyridyl group and the like.

As the sulfamoyl group represented by R ₄ ′ or R ₅ ′,
N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-
Examples thereof include diarylsulfamoyl groups, and these alkyl groups and aryl groups may have the substituents described for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include, for example, N, N-diethylsulfamoyl group, N-methylsulfamoyl group, N-dodecylsulfamoyl group, and Np-tolylsulfamoyl group.

As the carbamoyl group represented by R ₄ ′ or R ₅ ′,
-Alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, and the like.These alkyl groups and aryl groups are the substituents described for the alkyl group and the aryl group. May be provided. Specific examples of the carbamoyl group include, for example, N, N-diethylcarbamoyl group, N
-Methylcarbamoyl group, N-dodecylcarbamoyl group, Np-cyanophenylcarbamoyl group, Np-
And a tolylcarbamoyl group.

Examples of the acyl group represented by R ₄ ′ or R ₅ ′ include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, the aryl group,
The heterocyclic group may have a substituent. Specific examples of the acyl group include, for example, a hexafluorobutanoyl group, a 2,3,4,5,6-pentafluorobenzoyl group,
Examples include an acetyl group, a benzoyl group, a naphthyl group, a 2-furylcarbonyl group, and the like.

Examples of the sulfonyl group represented by R ₄ ′ or R ₅ ′ include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent.Specific examples include ethanesulfonyl. Group, benzenesulfonyl group, octanesulfonyl group, naphthalenesulfonyl group, p-chlorobenzenesulfonyl group and the like.

The aryloxycarbonyl group represented by R ₄ ′ or R ₅ ′ may have the substituent described for the aryl group as a substituent, and specific examples include a phenoxycarbonyl group.

An alkoxycarbonyl group represented by R ₄ ′ or R ₅ ′
It may have the substituents mentioned for the alkyl group,
Specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group and the like.

The hetero ring formed by combining R ₄ ′ and R ₅ ′ is 5
6 to 6 members are preferred, and may be saturated or unsaturated,
It may or may not have aromaticity, and may be a condensed ring. Examples of the hetero ring include an N-phthalimido group, an N-succinimide group, a 4-N-urazolyl group, a 1-N-hydantonyl group, a 3-N-2,4-dioxooxazolidinyl group, N-1,1-dioxo-3-
(2-H) -oxo-1,2-benzthiazolyl group, 1-
A pyrrolyl group, a 1-pyrrolidinyl group, a 1-pyrazolyl group,
1-pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group, 1-isoindolinyl group, 2-
Isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-benzimidazolyl group, 1-
(1,2,4-triazolyl) group, 1- (1,2,3-triazolyl) group, 1- (1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3, 4-tetrahydroquinolyl group, 2-
Oxo-1-pyrrolidinyl group, 2-1H-pyridone group, phthaladion group, 2-oxo-1-piperidinyl group and the like, and these heterocyclic groups are an alkyl group, an aryl group,
Alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkylamino group, arylamino group, acylamino group, sulfonamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxy It may be substituted by a carbonyl group, an imide group, a nitro group, a cyano group, a carboxyl group, a halogen atom, or the like.

Examples of the nitrogen-containing heterocyclic ring formed by Z or Z ′ include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Examples of the substituent that the ring may have include those described for R above. Is mentioned.

In addition, the general formula [I] and the following general formulas [I-1] to [I]
-7] (for example, R, R ₁ to
R ₈ ) Moieties (where R ", X and Z" are R, R in the general formula [I]
Synonymous with X and Z. ) Is included in the present invention as a matter of course to form a so-called bis-type coupler. Also, Z, Z ',
The ring formed by Z ″ and Z ₁ described below may be further condensed with another ring (for example, a 5- to 7-membered cycloalkene). For example, in the general formula [I-4], R ₅ and R _{5 In} formula (I-5), R ₇ and R ₈ may combine with each other to form a ring (for example, a 5- to 7-membered cycloalkene or benzene).

More specifically, those represented by the general formula [I] are represented by the following general formulas [I-1] to [I-6].

General formula [I-1] General formula [I-2] General formula [I-3] General formula [I-4] General formula [I-5] General formula [I-6] In the general formulas [I-1] to [I-6], R _{1 to} R ₈ and X have the same meanings as R and X.

Among the general formulas [I], preferred are those represented by the following general formula [I-7].

General formula [I-7] In the formula, R ₁ , X and Z ₁ have the same meanings as R, X and Z in the general formula [I].

Among the magenta couplers represented by the general formulas [I-1] to [I-6], particularly preferred are those represented by the general formula [I-1]
Is a magenta coupler represented by

As for the substituents on the heterocyclic ring in the general formulas [I] to [I-7], R is in the general formula [I], and in general formulas [I-1] to [I-7], R ₁ preferably satisfies the following condition 1, more preferably the following conditions 1 and 2, and particularly preferably the following conditions 1, 2 and 3.

Condition 1 A root atom directly connected to a heterocyclic ring is a carbon atom.

Condition 2 Only one hydrogen atom is bonded to the carbon atom. Or not at all.

Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.

The most preferred as substituents R and R ₁ on the heterocyclic, those represented by the following general formula [I-8].

General formula [I-8] In the formula, R ₉ , R ₁₀ and R ₁₁ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, and a sulfinyl group. , Phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group , Acylamino group, sulfonamide group, imide group,
Ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Represents an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group, and at least two of R ₉ , R _10, and R ₁₁ are not hydrogen atoms.

And two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀ may combine to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocycle), Further, R ₁₁ may be bonded to the ring to form a bridged hydrocarbon compound residue.

The group represented by R _{9 to} R ₁₁ may have a substituent,
₉ Examples and the substituent which may be the base has a group represented by to R _11, include specific examples and substituents of the group represented by R in the above general formula [I].

Also, for example, a ring formed by the combination of R ₉ and R ₁₀ and R _{9 to} R ₁₁
Specific examples of the bridged hydrocarbon compound residue formed by the formula (I) and the substituents that may be possessed include the aforementioned general formula [I]
Cycloalkyl, cycloalkenyl represented by R in
Specific examples of the heterocyclic group bridged hydrocarbon compound residue and its substituents are given.

Among the general formula [I-8], preferred are (i) when two of R _{9 to} R ₁₁ are alkyl groups, and (ii) one of R _{9 to} R ₁₁ , for example, R ₁₁ is a hydrogen atom And where the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom.

Further, among (i), preferred are two of R _{9 to} R _11.
One is an alkyl group and the other is a hydrogen atom or an alkyl group.

Here, the alkyl and the cycloalkyl may further have a substituent. Specific examples of the alkyl, the cycloalkyl and the substituent include the alkyl, cycloalkyl and the substituted alkyl represented by R in the above general formula [I]. Specific examples of the group are given.

The synthesis of the coupler is described in the Journal of the Chemical
Society, Parkin I (1977), 2047-2052, U.S. Pat.
Synthesis was carried out with reference to JP-A No. 25,067, JP-A-59-99437 and JP-A-58-42045.

The coupler of the present invention usually contains 1 × / mol of silver halide.
It can be used in the range of 10 ^-3 mol to 5 × 10 ^-1 mol, preferably 1 × 10 ^-3 mol to 5 × 10 ^-1 mol.

The aldehyde derivative used in the present invention is a compound represented by the following general formulas (III) to (IV).

General formula (III) General formula (IV) A ₁ , A ₂ , A ₃ , A ₄ and A ₅ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group.

Examples of the alkyl group having 1 to 6 carbon atoms include straight-chain or branched ones, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, n-barrel and iso-barrel. And a hexane group, an isohexane group and the like, and may be substituted. Specifically, a formyl group (for example, each group such as formylmethyl and 2-formylethyl) and an amino group (for example, aminomethyl, aminoethyl and the like) ), A hydroxyl group (for example, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, etc.), an alkoxy group (for example, methoxy, ethoxy, etc.), a halogen atom (for example, chloromethyl, trichloromethyl, Substituents such as dibromomethyl).

Examples of the alkenyl group include substituted and unsubstituted groups, examples of the unsubstituted group include vinyl, 2-propenyl, and the like. Examples of the substituted group include 1,2-dichloro-2.
-Carboxyvinyl, 2-phenylvinyl and the like.

Hereinafter, specific examples of the compound represented by the above general formula will be described, but the present invention is not limited thereto.

[Example compounds] III-1 Sodium formaldehyde bisulfite III-2 Sodium acetaldehyde bisulfite III-3 Sodium propionaldehyde bisulfite III-4 Sodium butyraldehyde bisulfite IV-1 Sodium succinate bisulfite IV-2 Glutaraldehyde bis-bisulfate Sodium sulfite IV-3 β-Methylglutaraldehyde sodium bisulfite IV-4 Maleic dialdehyde bissodium bisulfite In the present invention, the general formulas (III) and (IV) are preferably used. General formula (III) and general formula (IV)
The compound represented by the formula (1) is excellent in that even when added in a large amount, the storage stability of the solution is improved rather than deteriorated. Specifically, 2.0 × 10 ^{-5 to} 8.0 × per washing substitute liquid
It is added in an amount of 10 ^-2 mol, preferably from 1.0 × 10 ^{-4 to} 4.0 × 10 ^-2 mol.

The replenishment amount of the washing substitute liquid of the present invention is required to be 2 to 50 times the carry-in amount from the previous bath per unit area of the color photographic material to be processed. The concentration of the (bleach-fixing solution or fixing solution) is 1/50 or less, preferably 1/100 or less in the final tank of the washing alternative liquid tank, but from the viewpoint of low pollution and solution storability, it is 1/50 to 1/100000. It is necessary to configure the treatment tank for the washing substitute liquid so as to be preferably 1/100 to 1 / 50,000.

The treatment tank is composed of a plurality of tanks, and it is preferable for the present invention that the plurality of tanks include two or more and six or less tanks.

In the present invention, the number of tanks is not less than 2 and not more than 6, and the effect of the present invention, particularly low pollution and image preservation, is to use a counter-current method (a method of supplying to a post-bath and overflowing from a pre-bath). It is particularly preferable also from the viewpoint of improvement of.

The carry-in amount varies depending on the type of photosensitive material, the traveling speed of the automatic developing machine, the carrying method, the squeezing method of the photosensitive material surface, and the like.
Was ^{10ml / m 2 ~150ml / m 2} , replenishment rate of the washing alternative solution of the present invention for this amount carried is in the range of ^{100ml / m 2 ~4 / m 2} . For example, in the case of a color photographic material for photography, in the case of a normal color film (roll film), the carry-in
ml / m is ^{2 ~150ml} / m ^2, replenishment rate effect is more pronounced in the present invention for this amount carried is 100ml / m ² ~4.0 / m ²
The replenishment rate, which is particularly effective, is 200 ml / m ² -15
In the range of 100 ml / m ^2.

In the case of color paper, the carry-in amount is usually 10 / m ² -1
Was 00ml / m ^2, replenishment rate effect is more pronounced in the present invention for this amount carried is in the range of ^{20ml / m 2 ~1.5 / m 2} .

The treatment temperature of the treatment with the washing substitute solution is in the range of 15 to 60 ° C, preferably 20 to 45 ° C.

The water washing substitute liquid of the present invention employs the general formulas (V) and (VI) and the water-soluble organic siloxane-based compound, and has particularly good effects on the improvement of surface physical properties and the liquid preservability.

In the formula [V] R ₁ ′ -OR ₂ ′ -O _m X ₁ , R ₁ ′ is a monovalent organic group, for example, having 6 to 6 carbon atoms.
20, preferably 6-12 alkyl groups, hexyl,
Represents heptyl, octyl, nonyl, decyl, undecyl or dodecyl. Or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, preferably an alkyl group having 3 to 12 carbon atoms as a substituent, propyl, butyl, pentyl, hexyl, heptyl, octyl, Represents nonyl, decyl, undecyl or dodecyl; Aryl groups include phenyl, tolyl, xinyl,
Biphenyl or naphthyl, and preferably phenyl or tolyl. The position at which the alkyl group is bonded to the aryl group may be any of the ortho, meta, and para positions.
R ₂ 'represents an ethylene group or a propylene group;
Represents an integer of 5050. X ₁ is a hydrogen atom, -SO ₃ M or -PO ₃ M
₂ shows a, M ₂ is a hydrogen atom, an alkali metal (Na, K or Li
Etc.) or represent -NH _4.

General formula [VI] In the formula, R ₃ ′, R ₄ ′, R ₅ ′ and R ₆ ′ are each a hydrogen atom,
Represents an alkyl group or a phenyl group, but R ₃ ′, R ₄ ′, R ₅ ′
And the total number of carbon atoms of R ₆ 'is 3-50. X ₂ represents a halogen atom, a hydroxyl group, sulfuric acid group, carbonic acid group, nitric acid group, an acid group or a p- toluenesulfonic acid anion.

Next, specific representative examples of the compounds represented by the general formulas [V] and [VI] and the water-soluble organic siloxane-based compound of the present invention will be given, but the present invention according to the present invention is not limited thereto.

(Example Compound represented by the general formula _{[V]) V-1 C 12 H 23} O (C 2 H 4 O) 10 H V-2 C 8 H 17 O (C 13 H 6 O) 15 H V-3 C ₉ H ₁₉ O (C ₂ H ₄ O) ₄ SO ₃ Na V-4 C ₁₀ H ₂₁ O (C ₂ H ₄ O) ₁₅ PO ₃ Na ₂ (Example of compound represented by general formula [VI]) The water-soluble organic siloxane compound of the present invention includes, for example,
JP-A-47-18333, JP-B-55-51172, JP-B-51-37
No. 538, JP-A-49-62128 and U.S. Pat.
It means a general water-soluble organic siloxane-based compound as described in, for example, JP-A-970.

Among the water-soluble organic siloxane-based compounds, a compound represented by the following general formula [VII] is preferably used.

General formula [VII] (Wherein A ₁₂ is a hydrogen atom, a hydroxy group, a lower alkyl group, an alkoxy group, Or Represents A ₁₃ , A ₁₄ and A ₁₅ each represent a lower alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, propyl, etc.);
_13, A ₁₄ and A ₁₅ may have respectively the same or different. l represents an integer of 1 to 4, and p and q represent an integer of 1 to 15. Hereinafter, specific examples of the compound represented by the general formula [VII] will be shown.

(Water-soluble organic siloxane compound) These compounds represented by the general formulas [V] and [VI] and the water-soluble organic siloxane-based compound may be used alone or in combination. Further, when the amount of the stabilizer added is in the range of 0.01 to 20 g per 1 stabilizing solution, a good effect is obtained in terms of soiling.

Among the compounds represented by the above general formulas [V] and [VI] and the water-soluble organic siloxane-based compounds, the compounds preferably used in the present invention are the compounds represented by the above general formula [V]. Great effect on prevention.

In the washing substitute liquid of the present invention, the following general formula [1]
It is preferable to include the chelating agent represented by any one of [3] to [3] for improving the white background of the unexposed portion.

General formula [1] (Wherein, E is an alkylene group, a cycloalkylene group, a phenylene _{group, -B 5 -O-B 5 -} , - B 5 -O-B 5 -O-B 5 - or -B ₅ -Z-B ₅ - Z is B _{1 to} B ₆ each represent an alkylene group.

A ₁ ′ to A ₃ ′ each represent —COOM ′ or —PO ₃ M ₂ ′, and A ₄ ′ and A ₅ ′ each represent a hydrogen atom, a hydroxyl group,
Represent COOM ', or -PO ₃ M _2'. M 'represents a hydrogen atom or an alkali metal atom. ) General formula [2] (In the formula, B ₇ represents an alkyl group, an aryl group or a nitrogen-containing 6-membered ring group; M ′ represents a hydrogen atom or an alkali metal atom.) General formula [3] (Wherein B ₈ , B ₉ and B ₁₀ are each a hydrogen atom, a hydroxyl group,
_{-COOM ', - PO 3 M 2} ' or an alkyl group, L _1, L ₂
And L ₃ are a hydrogen atom, a hydroxyl group, -COOM ', -PO
₃ M ₂ ′ or Represents J represents a hydrogen atom, an alkyl group, -C ₂ H ₄ OH or -PO ₃ M ₂ '. M 'represents a hydrogen atom or an alkali metal atom, and n and m each represent 0 or 1.

Some specific examples of the chelating agents represented by the general formulas [1], [2] and [3] are shown below. The chelating agent used in the present invention is not limited to the following specific examples.

(Example chelating agent)

The chelating agent preferably used in the present invention is preferably used in an amount of 0.01 to 100 g, more preferably 0.05 to 50 g, and particularly preferably 0.1 to 20 g, per one washing substitute liquid of the present invention.

Further, the pH value of the washing substitute solution of the present invention is preferably in the range of 5.0 to 9.0, more preferably in the range of 5.5 to 9.0 for the purpose of improving the effect of the present invention, i.e., image storability. The pH is preferably in the range of 6.0 to 8.5.

As the pH adjuster that can be contained in the washing substitute liquid of the present invention, any commonly known alkali agent or acid agent can be used.

The water washing substitute liquid used in the present invention includes an organic acid salt (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), a pH adjuster (phosphate, borate, hydrochloric acid, sulfate, etc.), an interface Activators, preservatives, and metal salts such as Bi, Mg, Zn, Ni, Al, Sn, Ti, and Zr can be added. These compounds are used in any combination in an amount that is necessary to maintain the pH of the washing substitute liquid according to the present invention and that does not adversely affect the stability during storage of color photographic images and the occurrence of precipitation. I can do it.

The antifungal agent preferably used in each of the stabilizing solution or the washing substitute solution of the present invention includes a hydroxybenzoic acid ester compound, a phenolic compound, a thiazole compound, a pyridine compound, a guanidine compound, a carbamate compound, a morpholine compound, Class phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, amino acid compounds, and benztriazole compounds.

The hydroxybenzoic acid ester compound includes hydroxybenzoic acid methyl ester, ethyl ester, propyl ester, butyl ester and the like, preferably hydroxybenzoic acid n-butyl ester, isobutyl ester, propyl ester, more preferably It is a mixture of the three hydroxybenzoic esters.

The phenolic compound preferably used as the fungicide of the present invention is a compound which may have an alkyl group, a halogen group, a nitro group, a hydroxyl group, a carboxylic acid group, an amino group, a phenyl group or the like as a substituent, and is preferably Orthophenylphenol, orthocyclohexylphenol, phenol, nitrophenol, chlorophenol, cresol, guaiacol and aminophenol. Particularly preferably, orthophenylphenol exhibits remarkable anti-bism property in combination with the aldehyde derivative of the present invention.

The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, preferably 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazoline-3-one, 2-octyl-4-isothiazoline. 3-one, 5-chloro-2-methyl-4-isothiazoline 3-
On, 2-chloro-4-thiazolyl-benzimidazole.

Specific examples of the pyridine-based compound include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, sodium-2-pyridinethiol-1-oxide and the like, and preferably sodium-2-pyridinethiol-1-oxide. It is an oxide.

Guanidine compounds are specifically cyclohexidine,
There are polyhexamethylene, biguanidine hydrochloride and dodecylguanidine hydrochloride, preferably dodecylguanidine and its salts.

Specific examples of the carbamate-based compound include methyl-1- (butylcarbamoyl) -2-benzimidazole carbamate and methylimidazole carbamate.

Specific examples of the morpholine-based compound include 4- (2-nitrobutyl) morpholine and 4- (3-nitrobutyl) morpholine.

Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc.
Preferred are tetraalkylphosphonium salts, and more specific preferred compounds are tri-n-butyl-tetradecylphosphonium chloride and tri-phenylnitrophenylphosphonium chloride.

Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, and alkylpyridinium salts, and specific examples include dodecyldimethylbenzylammonium chloride, didecyldimethylammonium chloride, laurylpyridinium chloride, and the like. .

The urea compounds are specifically N- (3,4-dichlorophenyl) -N '-(4-chlorophenyl) urea, N- (3
-Trifluoromethyl-4-chlorophenyl) -N'-
(4-chlorophenyl) urea and the like.

Specific examples of the isoxazole-based compound include 3-hydroxy-5-methyl-isoxazole.

The propanolamine compounds include n-propanols and isopropanols, and specifically, DL-2-benzylamino-1-propanol, 3-diethylamino-
1-propanol, 2-dimethylamino-2-methyl-
1-propanol, 3-amino-1-propanol, isopropanolamine, diisopropanolamine, N,
N-dimethyl-isopropanolamine and the like.

Examples of the sulfamide-based compound include o-nitrobenzenesulfamide, p-aminobenzenesulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, and α-amino-p-toluenesulfamide.

The amino acid-based compound specifically includes N-lauryl-β-alanine.

The following are specific examples of the benztriazole-based compound.

(A) Benztriador Among the fungicides, the compounds preferably used in the present invention are phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, quaternary ammonium compounds, and benztriazole compounds. Furthermore, a phenol compound, a thiazole compound and a benztriazole compound are particularly preferable from the viewpoint of liquid preservation.

The addition amount of the anti-bubble agent to the washing substitute liquid is preferably used in the range of 0.001 g to 50 g per liter of the washing substitute liquid in view of the effect and cost of the present invention and the storage stability of the image, more preferably 0.005 g. Used in the range of ~ 10g.

In the processing of the present invention, silver may be recovered by various methods from a processing solution containing a soluble silver salt such as a fixing solution and a bleach-fixing solution, as well as a washing substitute solution. For example, an electrolysis method (described in French Patent No. 2,299,667), a precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, a German Patent No. 2,331,220), and an ion exchange method (described in Japanese Patent Application Laid-Open No. 51-220). No. 17114, German Patent No. 2,548,237, and metal replacement method (UK Patent No. 1,353,805) can be effectively used.

Further, upon silver recovery, the soluble silver salt is recovered as an overflow solution of the processing solution, silver is recovered by the above method, and the remaining solution may be disposed of as a waste solution, or a regenerant may be added, and a replenisher or a tank processing solution may be used. May be used. It is particularly preferable to recover the silver after mixing the stabilizing solution or the washing substitute solution with the fixing solution or the bleach-fixing solution.

Further, a treatment in which the washing substitute liquid of the present invention is brought into contact with an ion exchange resin, an electrodialysis treatment (see JP-A-61-28949), a reverse osmosis treatment (see JP-A-61-28949), and the like can also be used. .

In the present invention, the thiosulfate concentration in the washing substitute solution is
In the range of 0.7 × 10 ^{−5 to} 1500 × 10 ⁻⁵ mol /, the above-mentioned range is obtained in order that the effects of the present invention can be obtained more favorably and the long-term preservability of the dye image can be further improved. More preferably, it is used.

Particularly good results are obtained, especially when used in the range from 2 × 10 ⁻⁵ to 200 × 10 ⁻⁵ mol /. The thiosulfate concentration in the washing substitute liquid of the present invention is as follows.
When it consists of more than a tank, it refers to the concentration of thiosulfate in the tank closest to the drying step.

The washing substitute tank is optional for disposing a circulation pump and a filter device.

The aromatic primary amine color developing agent used in the color developing solution used in the color developing process in the present invention includes known ones widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. These compounds are generally used in the form of a salt, for example, the hydrochloride or sulfate, for stability in the free state. These compounds are generally used in color developer 1 in an amount of about
It is used at a concentration of 0.1 g to about 30 g, preferably about 1 g to about 1.5 g for the color developing solution 1.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, and 5-amino-2.
-Oxytoluene, 2-amino-3-oxytoluene,
2-oxy-3-amino-1,4-dimethylbenzene and the like.

Particularly useful primary aromatic amino color developing agents are N, N '
-Dialkyl-p-phenylenediamine compound, wherein the alkyl group and the phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N, N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride,
N'-dimethyl-p-phenylenediamine hydrochloride, 2-
Amino-5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-N, N'-diethylaniline, 4-
Amino-N- (2-methoxyethyl) -N-ethyl-3
-Methylaniline-P-toluenesulfonate;

In the color developer used in the processing of the present invention, in addition to the primary aromatic amine-based color developer, various components that are usually added to the color developer, such as sodium hydroxide, sodium carbonate, An alkali agent such as potassium carbonate, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softening agent and a thickening agent can be optionally contained. The pH value of this color developing solution is usually 7 or more, and most commonly about 10 to 10 or more.
It is about 13.

In the present invention, after the color development processing, processing is performed with a processing liquid having a fixing ability. When the processing liquid having the fixing ability is a fixing liquid, a bleaching processing is performed before that. As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the bleaching step, a metal complex salt of an organic acid is used, and the metal complex salt oxidizes metal silver produced by development to silver halide, and The coloring agent has an action of coloring uncolored portions of the coloring agent, and has a structure in which a metal ion such as iron, cobalt, or copper is coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. Most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The following can be mentioned as specific representative examples of these.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetic acid [4] propylenediaminetetraacetic acid [5] nitrilotriacetic acid [6] cyclohexanediaminetetraacetic acid [7] iminodiacetic acid [8] dihydroxyethylglycine citric acid (or tartaric acid) [9] ethyl Etherdiaminetetraacetic acid [10] glycol etherdiaminetetraacetic acid [11] ethylenediaminetetrapropionic acid [12] phenylenediaminetetraacetic acid [13] ethylenediaminetetraacetic acid disodium salt [14] ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ', N'-triacetate sodium salt [18] Propylenediaminetetraacetate sodium salt [19] Nitriloacetate sodium salt [20] Cyclohexanediaminetetraacetate sodium salt In addition to containing a metal complex salt as a bleaching agent, various additives can be included. As the additive, it is desirable to include an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, or ammonium bromide, a metal salt, and a chelating agent. Borate, oxalate, acetate, carbonate,
PH buffers such as phosphates, alkylamines, polyethylene oxides and the like which are known to be usually added to bleaching solutions can be added as appropriate.

Further, fixing solutions and bleach-fixing solutions include sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, and borax. PH buffer consisting of various salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, alone or in combination of two or more. it can.

In the present invention, when speeding up the processing and miniaturization of the automatic developing machine are considered, it is preferable that the pre-bath of the alternative bath for washing is a bleach-fix bath, and as another effect, there is an advantage that image preservability is improved. is there.

When the process of the present invention is carried out while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate or sulfite, or the like. These salts may be contained in the bleach-fix replenisher and replenished in the processing bath.

In the present invention, air or oxygen may be blown in the bleach-fix bath and in the storage tank of the bleach-fix replenisher, if desired, in order to increase the activity of the bleach-fix solution. For example, hydrogen peroxide, bromate, persulfate and the like may be appropriately added.

The silver halide of the silver halide of the color photographic material for photography used in the present invention may be a normal crystal, a twin crystal or any other crystal. Any ratio can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure (core-shell type) in which the inside and the outside are different. These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Further, tabular silver halide grains (JP-A-58-113934, Japanese Patent Application No. 59-113934)
No. 170070) can also be used.

Tabular silver halide emulsions have been reported by Cugnac and Chateau and by Duffin in "Photographic Emulsion Chemistry" (Fo
cal Press, New York 1966) 66-72, and APO
Trivelli, WFSmith ed. “Phot.Journal” 80 (1940) 285
Page, JP-A-58-113927 and JP-A-58-11
They can be easily prepared by referring to the methods described in JP-A-3928 and JP-A-58-127921.

To the photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention, a dye (AI dye) capable of decolorizing with a water-soluble or color developing solution can be added. Examples of the AI dye include an oxonol dye and a hemioxonol. Dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes,
Hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include GB 584,60
No. 9, No. 1,277,429, JP-A-48-85130, No. 49-9
No. 9620, No. 49-114420, No. 49-129537, No. 52
No. 108115, No. 59-25845, No. 59-111640, No. 59-111641, U.S. Pat.Nos. 2,274,782, 2,533,4
No. 72, No. 2,956,079, No. 3,125,448, No. 3,148,
No. 187, No. 3,177,078, No. 3,247,127, No. 3,26
0,601, 3,540,887, 3,575,704, 3,6
No. 53,905, No. 3,718,472, No. 4,071,312, No. 4,
No. 070,352 can be mentioned.

These AI dyes are generally used in two moles per mole of silver in the emulsion layer.
It is preferable to use from 10 ^{-3 to} 5 x 10 ^-1 mol, more preferably from 1 x 10 ^-2 to 1 x 10 ^-1 mol.

The silver halide grains particularly preferably used in the present invention are substantially monodisperse, which is obtained by an acid method,
It may be obtained by any preparation method such as a neutral method or an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing silver halide grains, controlling the pH, pAg, etc. in the reaction vessel, for example, an amount of silver ion corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521. And halide ions are preferably sequentially and simultaneously injected and mixed.

A known silver halide solvent can be used. Examples of frequently used silver halide solvents include ammonia, thioethers, thioureas, thiocyanate salts, and thiazolinedione. Regarding thioethers, U.S. Pat.
Nos. 3,574,628 and 3,790,387 can be referred to. For thioureas, JP-A-53-82408,
No. 55-77737, regarding thiocyanate salts, U.S. Pat.Nos. 2,222,264, 2,448,534, 3,320,069,
Regarding thiazolinedione, reference can be made to JP-A-53-144319.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allyl thiocarbamide, thiourea, and cystine; selenium sensitizers; reduction sensitizers such as stannous salts and thiodioxide. Urea, polyamines and the like; noble metal sensitizers such as gold sensitizers, specifically, potassium aurithiocyanate, potassium chlororoolate, 2-aurothio-3-methylbenzothiazolium chloride and the like, or ruthenium, palladium, platinum and the like ,rhodium,
Sensitizers of water-soluble salts such as iridium, such as ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these may be sensitizers or fog inhibitors depending on the amount of these substances) ) Alone or in combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, or a combination of a gold sensitizer and a selenium sensitizer). Good.

These examples are described in U.S. Pat.
No. 1,574,944, No. 2,278,947, No. 2,410,689, No. 2,728,668, No. 3,656,955, etc., for reduction sensitization methods, U.S. Pat.
No. 2,39,054, No. 2,39
No. 9,083, No. 2,448,060 and British Patent No. 618,061.

The silver halide emulsion according to the present invention is subjected to chemical ripening by adding a sulfur-containing compound, and before, during or after the chemical ripening, a nitrogen-containing heteroatom having at least one hydroxytetrazaindene and a mercapto group. At least one kind of a ring compound may be contained.

The silver halide used in the present invention may contain an appropriate sensitizing dye in an amount of from 5 × 10 ^{−8 to} 3 × 10 ⁻³ per mole of silver halide in order to impart photosensitivity to a desired photosensitive wavelength range. Optical sensitization may be performed by adding a mole. Various sensitizing dyes may be used, and one or two sensitizing dyes may be used.
It can be used in combination of more than one species. Examples of the sensitizing dye advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in blue-sensitive silver halide emulsions include, for example, West German Patent 929,080 and U.S. Pat.
No. 58, No. 2,493,748, No. 2,503,776, No. 2,519,001
Nos. 2,912,329, 3,656,959, 3,672,897,
Nos. 3,694,217, 4,025,349, 4,046,572, British Patent 1,242,588, Japanese Patent Publication Nos. 4414030 and 52-24844, and the like. As sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.Nos. 1,939,201, 2,072,908, and 2,739,149
No. 2,945,763, British Patent No. 505,979, and the like, there can be mentioned cyanine dyes, merocyanine dyes or complex cyanine dyes as typical examples. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Patent Nos. 2,269,234 and 2,270,3
No. 78, No. 2,442,710, No. 2,454,629, No. 2,776,280 and the like can be cited as typical examples of cyanine dyes, merocyanine dyes and composite cyanine dyes. Furthermore, U.S. Pat.No.2,213,995,
Cyanine dyes, merocyanine dyes or complex cyanine dyes as described in 2,493,748, 2,519,001, West German Patent 929,080 and the like can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.

These sensitizing dyes may be used alone or in combination.

The photographic light-sensitive material of the present invention may be optically sensitized to a desired wavelength region by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination, if necessary.

Representative examples of particularly preferred spectral sensitization methods include, for example, JP-B-43-4936, which relates to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 43-22884, No. 45-18433, No. 47-37443,
Nos. 48-28293, 49-6209, 53-12375, JP
52-23931, 52-51932, 54-80118, 58-1
Nos. 53926, 59-116646, 59-116647 and the like.

Examples of a combination of a carbocyanine having a benzimidazole nucleus and another cyanine or merocyanine include, for example, JP-B-45-25831 and JP-B-47-11114.
47-25379, 48-38406, 48-38407, 54
No. 34535, No. 55-1569, JP-A No. 50-33220, No. 50-
38526, 51-107127, 51-115820, 51-135
No. 528, No. 52-104916, and No. 52-104917.

Further, as regards the combination of benzoxazolocarbocyanine (oxa carbocyanine) with other carbocyanines, see, for example, JP-B-44-32753 and JP-B-46-11627.
And JP-A-57-1483 and those relating to merocyanine are described, for example, in JP-B-48-38408, JP-B-48-41204, and JP-B-50-41204.
No. 40662, JP-A-56-25728, JP-A-58-10753, JP-A-58-9
Nos. 1445, 59-116645 and 50-33828.

As regards the combination of thiacarbocyanine with another carbocyanine, for example, JP-B-43-4932,
43-4933, 45-26470, 46-18107, 47-87
No. 41, JP-A-59-114533 and the like, and the method described in JP-B-49-6207 using zero-methine or dimethine merocyanine, monomethine or trimethine cyanine and a styryl dye can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in JP-B-50-40659 is used in advance. Used by dissolving in a hydrophilic organic solvent.

The timing of addition may be at any time at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening. In some cases, it may be added to the step immediately before the emulsion coating.

Each of the silver halide emulsion layers according to the present invention may contain a coupler, that is, a compound capable of forming a dye by reacting with an oxidized form of a color developing agent.

As the couplers usable in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without any particular limitation. These couplers may be so-called two-equivalent type or four-equivalent type couplers, and it is also possible to use a diffusible dye-releasing type coupler in combination with these couplers.

Examples of the yellow coupler include an open-chain ketomethylene compound, a so-called 2-equivalent coupler, an active site-o-aryl-substituted coupler, an active site-o-acyl-substituted coupler, an active site hydantoin compound-substituted coupler, and an active site urazole compound-substituted coupler. And active site succinimide compound substituted coupler, active site fluorine substituted coupler, active site chlorine or bromine substituted coupler, active site -o
-Sulfonyl substituted couplers and the like can be used as effective yellow couplers. Specific examples of the yellow coupler that can be used include U.S. Patent Nos. 2,875,057 and 3,265,506.
Nos. 3,408,194, 3,551,155, 3,582,322,
3,725,072, 3,891,445, West German Patent 1,457,868
No. 2,219,917, West German Application No. 2,261,361, West German Application No. 2,41
4,006, British Patent 1,425,020, JP-B-51-10783,
JP-A-47-26133, JP-A-48-73147, JP-A-51-102636,
No. 50-6341, No. 50-123342, No. 50-130442, No. 51
-21827, 50-87650, 52-82424, 52-115
Nos. 219 and 58-95346.

Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. These magenta couplers may be not only 4-equivalent couplers but also 2-equivalent couplers like the yellow couplers. Specific examples of magenta couplers include U.S. Patents 2,600,788, 2,983,608,
062,653, 3,127,269, 3,369,897, 3,311,4
No. 76, 3,419,391, 3,519,429, 3,558,319
Nos. 3,582,322, 3,615,506, 3,834,908,
3,891,445, West German Patent 1,810,464, West German Patent Application (OLS) 2,408,665, 2,417,945, 2,418,959,
No. 2,424,467, JP-B-40-6031, JP-A-51-20826
No. 52-58922, No. 49-129538, No. 49-74027,
Nos. 50-159336, 52-42121, 49-74028, 50
Nos. -60233, 51-26541, 53-55122, JP-A-57
-35858 and the like.

Further, examples of useful cyan couplers used in the present invention include phenol couplers and naphthol couplers. These cyan couplers may be not only 4-equivalent couplers but also 2-equivalent couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Pat.Nos. 2,369,929 and 2,434,272.
No. 2,474,293, 2,521,908, 2,772,162,
2,895,826, 3,034,892, 3,311,476, 3,4
No. 58,315, No. 3,476,563, No. 3,583,971, No. 3,591,38
No. 3, No. 3,758,308, No. 3,767,411, No. 3,772,002,
3,993,494, 4,004,929, 4,126,396, 4,3
No. 34,011, No. 4,327,173, West German Patent Application (OLS) 2,414,
No. 830, No. 2,454,329, No. 3,329,729, JP-A-48-598
No. 38, No. 51-26034, No. 48-5055, No. 51-146827
No. 52-69624, No. 52-90932, No. 58-95346,
Examples described in JP-B-49-11572 can be mentioned.

Further, in the present invention, Japanese Patent Application Laid-Open No.
The polymer coupler described in No. 1 is also preferably used.

The couplers used in the present invention can be used in combination of two or more in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound to two or more different layers. Absent.

In order to correct unnecessary absorption in the short wavelength region of the coloring dyes of the magenta and cyan couplers, it is preferable to use a colored coupler together with the color photographic material for photography.
Yellow-colored magenta couplers described in U.S. Pat.No. 4,163,670 and JP-B-57-39413 or U.S. Pat.
004,929, 4,138,258 and British Patent 1,146,36
Examples thereof include magenta-colored cyan couplers described in No. 8 and the like.

Further, as a coloring dye diffusion type coupler, U.S. Pat.
Specific examples of magenta couplers are described in 366,237 and British Patent 2,125,570, and specific examples of yellow, magenta and cyan are described in EP 96,873 and German Offenlegungsschrift (OLS) 3,324,533.

The DIR coupler that can be used in the present invention will be described below.

DIR couplers which release heterocyclic mercapto-based development inhibitors described in, for example, U.S. Pat. No. 3,227,554; those which release benzotriazole derivatives described in JP-B-58-9942 as development inhibitors: 51-1614
No. 1 colorless DIR couplers described in JP-A No. 59-59
No. 90932, which releases a nitrogen-containing heterocyclic development inhibitor with the decomposition of methylol after the dissociation described in US Pat.
No. 248,962 and JP-A-57-56837, which release a development inhibitor with an intramolecular nucleophilic reaction after release.
56-114946, 57-154234, 57-188035, 58-9872
JP-A-58-209736, JP-A-58-209737, JP-A-58-209738, JP-A-58-209739 and JP-A-58-209740, which release a development inhibitor by electron transfer via a conjugated system after release. 57-151944, 58-217932, etc., which release a diffusible development inhibitor whose development inhibiting ability is inactivated in a developer:
Those which release the reactive compounds described in Japanese Patent Application Nos. 59-38263 and 59-39653 and generate a development inhibitor or deactivate the development inhibitor by a reaction in the film during development. Can be mentioned.

In the present invention, a compound capable of forming a development accelerator or fogging agent with silver development can be used. Specific examples include compounds described in JP-A-57-150845.

The color photographic light-sensitive material of the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants described in Research Disclosure No. 17643 , A plasticizer, a wetting agent and the like can be used.

In the color photographic light-sensitive material of the present invention, hydrophilic colloids used for preparing an emulsion include gelatin, derivative gelatin, a graft polymer of gelatin and another polymer, albumin, proteins such as casein, hydroxyethyl cellulose derivatives, Any one of cellulose derivatives such as carboxymethylcellulose, starch derivatives, mono- or copolymerized synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl imidazole and polyacrylamide is included.

As the support of the color photographic light-sensitive material of the present invention, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and a reflective layer were provided. Alternatively, a transparent support in combination with a reflector, for example, a glass plate, a polyester film such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and the like can be given. These supports are appropriately selected according to the purpose of use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Patent 2,761,79
A simultaneous coating method of two or more layers according to the method described in JP-A Nos. 1 and 2,941,898 can also be used.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose. Further, various layers such as a filter layer, an anti-curl layer, a protective layer, and an antihalation layer may be appropriately used as constituent layers. It can be used in combination. In these constituent layers, a hydrophilic colloid which can be used in the above-mentioned emulsion layer can be similarly used as a binder, and various layers which can be contained in the above-mentioned emulsion layer can be contained in the layer. Photographic additives.

The photosensitive material applicable to the present invention may be any of a color reversal film for slides, a color reversal film for movies, a color reversal film for TV, a color reversal photographic paper for printing, a color reversal photographic paper for photography, a color negative film, a color photographic paper and the like. May be used.

[Specific Examples of the Invention] Hereinafter, the present invention will be described specifically with reference to Examples, but embodiments of the present invention are not limited thereto.

Example (1) The following washing substitute liquid was prepared.

(Washing substitute solution) Aldehyde derivative (described in Table (1)) 5-chloro-2-methyl-4-isothiazolin-3-one 0.1 g A running bleach-fixing solution (0.
02g) was added, and the mixture was adjusted to pH 1 and adjusted to pH 7.5 with ammonium hydroxide or sulfuric acid.

The above alternative washing solution was stored at room temperature (about 25 ° C.), and the formation state of silver sulfide was observed.

 The results are shown in Table (1).

As is clear from the results in Table (1), under the conditions of Example (1), when the concentration was higher than that of the present invention (treatment liquid No.
8) It can be seen that silver sulfide was generated after 3 days with lapse of time, and it was highly dependent on the concentration of the aldehyde derivative.

Example (2) On a paper support laminated with polyethylene, the following layers were sequentially applied from the support side to prepare a photosensitive material sample.

Layer 1: 1.3 g / m ² gelatin, 0.42 g / m ² (silver equivalent, the same applies hereinafter) blue-sensitive silver chlorobromide emulsion (95 mol% as AgCl) and
A layer containing 1 × 10 ⁻³ mol / m ² of the following yellow coupler (Y-1) dissolved in 0.50 g / m ² of dioctyl phthalate.

Layer 2: an intermediate layer made of 0.68 g / m ² gelatin.

Layer 3 ... 1.20 g / m ² of gelatin, 0.25 g / m ² green-sensitive silver chlorobromide emulsion (98 mol% as AgCl) and 0.28 g / m ² of dioctyl was dissolved phthalate 1 × 10 ^-3 mol / m ² a layer containing the magenta coupler of the present invention or the following comparative magenta coupler Mc-1 (described in Table (2)).

Layer 4: an intermediate layer composed of 1.1 g / m ² gelatin.

Layer 5: 1.5 × 10 ⁻³ dissolved in 1.4 g / m ² gelatin, 0.25 g / m ² red-sensitive silver chlorobromide emulsion (98 mol% as silver bromide) and 0.20 g / m ² dibutyl phthalate Layer containing mol / m ² of the following comparative cyan coupler Cc-1.

Layer 6: 0.31 g / m ² of the following structural formula dissolved in 1.0 g / m ² gelatin and 0.20 g / m ² dioctyl phthalate: A layer containing the compound of

Layer 7: Layer containing 0.48 g / m ² of gelatin.

In addition, as a hardening agent, sodium 2,4-dichloro-6-hydroxy-s-triazine was added to the layers 2, 4, and 7,
Each was added in an amount of 0.017 g per 1 g of gelatin.

Next, these samples were subjected to wedge-shaped exposure by a conventional method, and then subjected to the following development processing.

Processing step Processing temperature Processing time [1] Color development 35 ° C 45 seconds [2] Bleaching and fixing 35 ° C 45 seconds [3] * Processing with a washing substitute solution 30 ° C 90 seconds [4] Drying 60 to 80 ° C 60 seconds * 3 A tank cascade was used, and the processing time for one tank was 30 seconds.

 The treatment liquid used had the following composition.

(Color developing solution) Potassium chloride 2.0 g Potassium sulfite (50% solution) 0.6 ml Potassium carbonate 30.0 g Color developing agent (3-methyl-4-amino-N-ethyl-
N- (β-methanesulfonamidoethyl) -aniline sulfate 5.0 g Diethylhydroxylamine 5.0 g Triethanolamine 10 g Water was added to adjust the total amount to 1, and the pH was adjusted to 10.15 with potassium hydroxide or sulfuric acid.

 The bleach-fix solution had the following composition.

[Bleach-fixing solution] Ferric ammonium ethylenediaminetetraacetate dihydrate
60.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 100.0 ml Ammonium sulfite (40% solution) 27.5 ml Water was added to make the total amount 1 and adjusted to pH 7.1 with ammonium hydroxide or glacial acetic acid.

The processing solution used in Example (1) (described in Table (2)) was used as the water washing substitute solution.

After the development processing, the density Dmin of the unexposed portion was measured using a Sakura photoelectric densitometer PDA-65 (manufactured by Konishi Roku Photographic Industry Co., Ltd.).
(Minimum density of magenta dye density), then 75 ℃
After storing for 7 days under the condition of 80% RH (relative humidity), the minimum density of the magenta dye in the unexposed area after storage was measured, and the difference was shown in Table (2).

As is clear from Table (2), even when the water washing substitute liquid of the present invention was used, the yellow stain was large, but the combination with the magenta coupler of the present invention significantly prevented yellow stain.

In place of the magenta coupler M-18 of the present invention, M-
5, M-7, M-44, M-59, M-104, M-182 and M
The same evaluation was performed for -202, but almost the same results as for M-18 were obtained.

Comparative Example (1) On a cellulose triacetate film support, a multilayer color light-sensitive material comprising the respective layers having the following compositions was prepared.

First layer: Antihalation layer Gelatin layer containing black colloidal silver Second layer: Intermediate layer (gelatin layer) Third layer: First red-sensitive emulsion layer Silver iodobromide (silver iodide: 3.5 mol%, average grain size) Monodisperse spherical particles of 0.5 μm) Silver coating amount 0.8 g / m ² Silver iodobromide (silver iodide: 3 mol%, monodisperse spherical particles of average particle size 0.5 μm) Silver coating amount 0.8 g / m ² Sensitizing dye I (described below): 6 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II (described below): 1.5 × 10 ⁻⁵ mol per mol of silver Cyan coupler (described below) 0.044 mol per mol of silver Fourth layer: second red-sensitive emulsion layer Silver iodobromide (silver iodide: 5 mol%, monodisperse spherical particles having an average particle diameter of 1.0 μm) Silver coating amount 2.0 g / m ² sensitizing dye I (described below): 3.5 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II (described below): 1.0 × 10 ⁻⁵ mol per mol of silver Cyan coupler (described below) ... 0.020 mol per mol of silver Fifth layer: The same sixth layer and between layers the second layer: first green-sensitive emulsion layer silver halide emulsion (silver iodide: 4.0 mol%, average particle size 0.5μ
Monodisperse spherical particles) ...... silver coverage 1.8 g / m ² sensitizing dye III (below) .... 1 mol of silver relative to 3.3 × 10 ^-5 mol sensitizing dye IV (below) .... silver mole of m 1.1 × 10 ^-5 mol / magenta coupler (described below) 12 g / mol of silver 7th layer: second green-sensitive emulsion layer Silver halide emulsion (silver iodide: 5.0 mol%, average grain size 1.0 μ
monodisperse spherical particles having a particle size of 1.8 m) Silver coating amount 1.8 g / m ² Sensitizing dye III 2.65 × 10 ⁻⁵ mol per mol of silver Sensitizing dye IV 0.89 × 10 ⁵ per mol of silver ^-5 mol Magenta coupler (described below) 0.02 mol per mol of silver 8th layer: yellow filter layer Gelatin layer containing yellow colloidal silver in gelatin aqueous solution 9th layer: 1st blue-sensitive emulsion layer Silver iodobromide (Silver iodide: 5.6 mol%, monodisperse spherical particles having an average particle diameter of 0.4 μm) ...... Silver coating amount 1.5 g / m ² Yellow coupler (described below) ...... 0.25 mol per mol of silver 10th layer: 2 Blue-sensitive emulsion layer Silver iodobromide (silver iodide: 6 mol%, monodisperse spherical particles having an average particle diameter of 0.90 μm)... Silver coating amount 1.21 g / m ² Yellow coupler (below) ... 1 mol of silver 0.06 mol based on the eleventh layer: first protective layer Silver iodobromide (silver iodide: 1 mol%, monodisperse spherical particles having an average particle size of 0.70 μm)... Silver coating amount 0.5 g Emulsified amount of ultraviolet absorber Gelatin layer 12th layer containing things: Gelatin layer each comprising a second protective layer trimethyl methacrylate particles (diameter 1.5 [mu] m) in addition to the above composition, were added a gelatin hardener and a surfactant.

Sensitizing dye I: anhydro-5,5'-dichloro-3,3 '-(γ
-Sulfopropyl) -9-ethyl-thiacarbonianin hydroxide pyridium salt Sensitizing dye II: anhydro-9-ethyl-3,3'-di- (γ
-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide triethylamine salt Sensitizing dye III: anhydro-9-ethyl-5,5'-dichloro-3,3'-di- ( γ-sulfopropyl) oxacarbocyanine sodium salt Sensitizing dye IV: anhydro-5,6,5 ′, 6′-tetradichloro-1,1′-diethyl-3,3′-di-Δβ- [β -(Γ-sulfopropoxyethoxy)} ethylimidazolocarbocyanine hydroxide sodium salt The photographic material was processed by an automatic developing machine according to the following steps. The automatic developing machine used was a modified version of CL-NP34 (manufactured by Konishi Roku Photo Industry Co., Ltd.).

 Processing process (38 ° C) Number of tanks Processing time Color development 1 tank 3 minutes 15 seconds Bleaching 1 tank 3 minutes 15 seconds Fixing 1 tank 3 minutes 15 seconds Processing with alternative washing solution 3 tanks 2 minutes 30 seconds Used (cascade method) The composition of the color developing solution thus obtained is as follows.

The composition of the color developing replenisher used was as follows.

The composition of the bleaching solution used is as follows.

The composition of the bleach replenisher used was as follows.

The composition of the fixing solution used is as follows.

The composition of the fixing replenisher used was as follows.

The compositions of the washing substitute liquid and the replenisher used are as follows.

The color developing replenisher is replenished to 1450 ml of color developing bath per m ² of the light-sensitive material, the bleach replenisher is replenished to 925 ml of bleaching bath per m ² , and the fixing replenisher is replenished to 925 ml fixing bath per m ² . The washing substitute liquid is cascaded in three tanks, and the replenishment amount is shown in Table (4).
The replenisher was treated to the amount described, until the volume of the washing-replacement liquid reached three tanks, and then the formation of silver sulfide was observed in the same manner as in Example (1) for one week in the storage period. The maximum density of the magenta dye was measured in the same manner as in Example (2), and the decrease in density after storage was measured. (However, the transmission density)
A 50ml / m ^2.

 The results are shown in Table 3.

As is clear from Table (3), as the concentration of the aldehyde derivative decreases, silver sulfide hardly occurs, but on the contrary, the image storability deteriorates. Also, when the replenishment amount of the washing substitute solution is extremely low (50 ml / m ² ), silver sulfide tends to be generated, but the image preservability is good. On the other hand, when it is extremely large (5000 ml / m ² ), silver sulfide is generated. although hard to, image storability there is a problem that decreases, the replenishing amount is 100~2500ml / m ² washing substitute solution at a concentration of the aldehyde derivative of the present invention, silver is particularly sulfide in the case of 500 ml / m ² or more Less likely to occur and good image storability.

The comparative couplers Mc-2 to Mc-5 were used and evaluated based on Comparative Example (1). The magenta concentration was 0.10 to 0.15 lower than the magenta coupler of the present invention.
The image storability was deteriorated.

Example (3) Acetaldehyde, glutaraldehyde, (III-2) and (IV-2) were evaluated in the same manner as in Comparative Example (1) in place of formaldehyde. Obtained. Also, with respect to (III-2) and (IV-2), sulfurization did not occur even when 8.0 × 10 ^-2 mol was added, and the image storability was good.

Further, instead of the magenta coupler M-5 of the present invention, M-7,
M-11, M-22 and M-127 were evaluated in the same manner as in Comparative Example (1), but the same effects as in M-5 could be obtained.

Continuation of front page (56) References JP-A-61-61160 (JP, A) JP-A-57-97530 (JP, A) JP-A-62-196660 (JP, A)

Claims (1)

(57) [Claims] A step of subjecting a silver halide color photographic material having at least one silver halide emulsion layer on a support to imagewise exposure, followed by at least a step of color development, a step of processing with a solution having a fixing ability, and A final processing step is a processing of a silver halide color photographic light-sensitive material including a step of processing with a washing substitute liquid, wherein the silver halide color photographic light-sensitive material contains a magenta coupler represented by the general formula (I),
The washing substitute liquid is 2.0 × 10 ^{−5 to} 8.0 per substitute liquid.
The compound represented by the following general formula [III] in the range of × 10 ^-2 mol and the compound represented by the following general formula [IV] in the range of 2.0 × 10 ^{-5 to} 8.0 × 10 ^-2 mol per substitution liquid 1 Wherein the replenishing amount of the washing substitute solution is at least one selected from the group consisting of: 2 to 50 of the carry-in amount of the photographic light-sensitive material of the processing solution of the processing step prior to the step of processing.
A method for preventing precipitation of silver sulfide generated in a water-wash alternative liquid, wherein the method prevents the precipitation of silver sulfide generated in the water-wash alternative liquid. General formula [I] (Wherein, Z represents a group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent. X is a hydrogen atom or a color developing agent. R represents a hydrogen atom or a substituent which can be eliminated by a reaction with an oxidized form.) General formula [III] (In the formula, A ₂ and A ₃ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group, and M represents an alkali metal.) General formula [IV] (Wherein A ₄ and A ₅ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group, M represents an alkali metal, and n represents an integer of 0 to 4) .)