JPH0558186B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to the processing of silver halide color photographic materials (hereinafter referred to as color photographic materials), and more specifically, the present invention relates to the processing of silver halide color photographic materials (hereinafter referred to as color photographic materials), and more specifically, the present invention relates to the processing of silver halide color photographic materials (hereinafter referred to as color photographic materials). The present invention also relates to a treatment method using a treatment liquid containing peroxide. [Prior Art] Conventionally, the following methods have generally been used to process color photosensitive materials. After the color photosensitive material is subjected to imagewise exposure, it is treated with a color developing solution containing an aromatic primary amine developing agent, whereby the silver halide is reduced to metallic silver, and the aromatic primary amine is It is oxidized and undergoes a coupling reaction with the coupler to produce a dye image. The metallic silver is oxidized to soluble silver halide by a bleaching agent (oxidizing agent) in a bleaching process. Thereafter, by treatment with a fixing solution (eg, thiosulfate, thiocyanate, etc.), the silver complex ions are converted into silver complex ions and removed from the photographic material, leaving only the color image. In addition to the basic steps of color development, bleaching, and fixing, the actual development process includes auxiliary steps for physical photographic image preservation and quality preservation. There is also a method of processing with a bleach-fix solution that performs bleaching and fixing steps in one bath. As bleaching agents used in the bleaching process, red blood salts, ferric chloride, aminopolycarboxylic acid-metal complex salts, and peroxides are generally used. Both red blood salt and ferric chloride are good bleaching agents because they have a strong bleaching power and a fast bleaching rate (oxidation rate). However, since bleaching solutions using red blood salt liberate cyan ions through photolysis and cause environmental pollution, it is necessary to detoxify the treated waste liquid. In addition, bleaching solutions using ferric chloride have a pH of
Since the oxidizing power is very low and the oxidizing power is extremely high, the processing machine equipment that contains it is easily corroded, and iron hydroxide is precipitated in the emulsion layer during the water washing process after bleaching, producing so-called stains. There are drawbacks. For this reason, a cleaning step using an organic chelating agent is required for the bleaching solution, which is not suitable for the purpose of speedy processing and labor saving, and is also undesirable due to the risk of generating chlorine gas in terms of environmental pollution. It has been proposed to use an aminopolycarboxylic acid-metal complex salt as a bleaching agent that causes less environmental pollution than the red blood salt and ferric chloride. however,
The bleaching solution of the aminopolycarboxylic acid-metal complex salt has low oxidizing power and has insufficient bleaching power. For example, when bleaching a low-sensitivity color light-sensitive material that is mainly composed of a silver chlorobromide emulsion, it is possible to achieve the desired purpose, but if the material is mainly composed of silver chlorobromoiodide or silver iodobromide and the color When processing sensitized high-sensitivity color light-sensitive materials, especially color light-sensitive materials using high-silver emulsions, the bleaching effect may be insufficient and desilvering may be insufficient, or oxidation products of color developing agents and couplers may The dye produced by oxidative coupling remains in the state of a leuco dye, which is a reaction intermediate, even after bleaching, and the dye is not completely formed, resulting in so-called poor color recovery. In any case, bleaching agents (oxidizing agents) such as red blood salts, ferric chloride salts, or aminopolycarboxylic acid metal complex salts have problems such as environmental pollution due to the pollution burden of waste liquid, so the treated waste liquid is completely harmless. Measures and other measures must be taken to ensure that metal ion-free peroxides, specifically persulfate ions and/or hydrogen peroxide or compounds that release hydrogen peroxide, are recommended. preferable. Peroxide used as a bleaching agent decomposes into water and oxygen or sulfate, so it does not increase biological oxygen demand (BOD) or chemical oxygen demand (COD), which is advantageous in terms of pollution control. However, for example, persulfate ions have stronger oxidizing power than the red blood salts, ferric chloride, and metal complex salts of organic acids, and have a high redox potential, but their bleaching power against silver is weak, and bleaching takes an extremely long time. It takes.
For this reason, it is known that various bleach accelerators are used in combination, and these bleach accelerators can be added to a solution containing persulfate ions or to a prebath prior to a bleach bath, for example, U.S. Pat. No. 3,707,374; 3722020
No. 3893858, Special Publication No. 51-28227, Japanese Patent Publication No. 1973
-94927, 53-95631, 55-25064, same
No. 55-26506, Research Disclosure No. 15704 (May 1977)
A method using a bleaching accelerator such as a mercapto compound or a diothyl carbamate compound described in JP-A-55-149944, JP-A No. 58-8352
No. 58-95347, a method has been proposed in which an amino compound is incorporated into a sensitive material, and this technique improves the bleaching power and makes it possible to speed up the bleaching time. However, even with these accelerators,
Such a processing solution with bleaching ability using peroxide as a bleaching agent has a black colloidal silver antihalation layer and a silver halide layer containing 3 mol% or more of silver iodide as the closest layer. It has been found that in high-sensitivity photographic materials such as those having a large film thickness, desilvering defects rapidly occur when continuous processing is performed. Therefore, the present inventor has previously discovered and proposed that the desilvering property of the above-mentioned light-sensitive material can be significantly improved by reducing the total thickness of the photographic constituent layers to 25 μm or less. However, when the film thickness of the color light-sensitive material is reduced in this manner and the material is processed with the processing liquid having bleaching ability of the present invention, an unexpected problem arises in that the storage stability of the magenta dye deteriorates. This was a completely unexpected phenomenon since it does not occur at all in ordinary color light-sensitive materials in which the total thickness of the photographic constituent layers is 25 μm or more. In particular, if the treatment time with a treatment solution with bleaching ability is 3 minutes or more,
It has been found that the magenta dye deteriorates significantly under storage conditions of high temperature and high humidity such as 80% relative humidity and 80% relative humidity, and this is a serious problem in practical use. Therefore, in order to process color light-sensitive materials with the processing solution having bleaching ability of the present invention, it is desired to develop a technique that prevents deterioration of magenta dyes due to storage and does not impair silver bleaching ability. [Object of the Invention] Accordingly, the first object of the present invention is to provide an excellent bleach-fixing method for highly sensitive silver iodide-containing color light-sensitive materials in the processing of color light-sensitive materials. A second object is to provide a method for processing color light-sensitive materials in which the storage stability of the produced magenta dye is improved. A third object is to provide a method for processing color photosensitive materials that has a low risk of environmental pollution and meets the requirements for pollution prevention. [Structure of the Invention] As a result of extensive research, the present inventor has developed a photographic constituent layer comprising a black colloidal silver-containing antihalation layer and blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers on a support. the layer closest to the antihalation layer among the silver halide emulsion layers contains silver halide grains containing silver iodide, the total thickness of the photographic constituent layers is 25 μm or less, and the layer has the following general formula: The object of the present invention can be achieved by subjecting a color light-sensitive material containing the compound represented by [C] to imagewise exposure, developing it, and processing it with a processing solution having silver bleaching ability and containing peroxide as a bleaching agent. was found to be achieved. General formula [C] In the formula, R and R ₁ represent a hydrogen atom or a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. The photographic constituent layer herein refers to all the hydrophilic layers that are on the same side as the support surface coated with the black colloidal silver-containing antihalation layer of the present invention and at least three silver halide emulsion layers and that participate in image formation. In addition to the antihalation layer and the silver halide emulsion layer, it also includes a subbing layer, an intermediate layer (a mere intermediate layer, a filter layer, an ultraviolet absorbing layer, etc.),
It includes a protective layer and the like. The most preferred embodiment of the present invention is at least one of the compounds represented by the general formulas [] to [].
The present inventor has found that the purpose of the present invention can be achieved more effectively by containing seeds. General formula []

[Formula] General formula []

[Formula] General formula [] General formula [] General formula [] General formula [] In the above general formula, Q represents an atomic group necessary to form a heterocycle containing one or more N atoms (including those to which at least one 5- to 6-membered unsaturated ring is fused), A is -SZ' or n _Monovalent heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused)
, B represents an alkylene group having 1 to 6 carbon atoms, M represents a divalent metal atom, and X and X' are =
S, =O or =NR'', R'' represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (a 5- to 6-membered unsaturated ring is at least (including one fused to this) or an amino group, and Y is

[Formula] Also teeth

[Formula], Z is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, or

[Formula], Z′ represents Z or an alkyl group, and R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (a 5- to 6-membered unaltered R ₂ , R ₃ , R ₄ , R ₅ , R and
R' each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group. However, R ₄ and R ₅ may represent -B-SZ, and R and R', R ₂ and R ₃ , and R ₄ and R ₅ may each be cyclized to form a heterocyclic residue (5- to 6-membered (including those in which at least one unsaturated ring is fused thereto). R ₆ and R ₇ are each

【formula】

【Formula】Also teeth

[Formula], R ₉ is an alkyl group or -(CH ₂ ) n ₈ SO ₃
(however, when R ₈ is −(CH ₂ ) n ₈ SO ₃ , l
represents 0 or 1. ) G is an anion, m ₁ or
m ₄ and n ₁ to n ₈ are each an integer of 1 to 6, m ₅
represents an integer from 0 to 6. _R8 is a hydrogen atom, an alkali metal atom,

[Formula] or represents an alkyl group. However, Q' has the same meaning as Q above. D represents a simple bond, an alkylene group or vinylene group having 1 to 8 single primes, and q represents an integer of 1 to 10. A plurality of D's may be the same or different, and the ring formed together with the sulfur atom may be further condensed with a 5- to 6-membered unsaturated ring. Note that the compound represented by the above general formula includes enolized compounds and salts thereof. That is, the present inventor continuously processed a high-sensitivity fine-grain color light-sensitive material having black colloidal silver as an antihalation layer and at least three silver halide emulsion layers containing a silver iodide-containing emulsion adjacent to the black colloidal silver layer. We have focused on the phenomenon that the desilvering properties of silver sensitizers deteriorate significantly when using silver iodide, and as a result of extensive research, we have found that when processed with a processing solution containing a bleaching agent containing peroxide, color sensitizers containing silver iodide to be processed are It has been discovered that when the photographic constituent layers of the material are thinned below a certain value, the bleach-fixing properties are significantly improved and desilvering defects are improved. Furthermore, this phenomenon is caused by the fact that when the thickness of the photographic constituent layer of a silver iodide-containing color light-sensitive material increases, significant desilvering failure occurs at the boundary between the black colloidal silver-containing antihalation layer and the silver iodide-containing silver halide emulsion layer. It was found that there was a significant increase in Furthermore, the present inventor has found that when a specific bleaching accelerator is added to a bleach-fixing solution containing peroxide as a bleaching agent, the film thickness of the photographic constituent layer including the colloidal silver-containing antihalation layer and the silver halide emulsion layer (gelatin film If the thickness (thickness) exceeds a certain value, a good bleaching accelerating effect cannot be obtained, but if the thickness of the photographic constituent layer (gelatin film thickness) of the color photosensitive material is below a certain value, the bleaching accelerating effect of the specific bleaching accelerator will be improved. We discovered the surprising fact that this significantly increases the According to a preferred embodiment of the present invention, the thickness of the photographic constituent layer of the color photographic light-sensitive material is 22 μm or less, more preferably 20 μm or less, particularly 18 μm or less. It has been found that the first object of the present invention can be achieved more effectively by this. In addition, the unexpected phenomenon of deterioration of storage stability of magenta dye that occurs when the film thickness of the photographic constituent layer becomes 25 μm or less can be solved by using a specific magenta coupler, which is the second object of the present invention. I discovered that it is possible to achieve this. Next, the present invention will be specifically explained. The above general formula [C] according to the present invention General formula [C] In the formula, R and R ₁ represent a hydrogen atom or a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Note that R ₁ has the same meaning as R described later. Examples of the substituent represented by R include 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,
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, alkoxycarbonyl group,
Aryloxycarbonyl group, alkylthio group,
Examples include arylthio group and heterocyclic thio group. Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred. The alkyl group represented by R has 1 to 1 carbon atoms.
32, alkenyl groups, alkynyl groups with 2 to 32 carbon atoms, cycloalkyl groups, cycloalkenyl groups with 3 to 12 carbon atoms, especially 5 to 7 carbon atoms
Preferred are alkyl groups, alkenyl groups,
Alkynyl groups may be linear or branched. In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents (e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds) In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a hetero atom {specifically, hydroxy, alkoxy, aryloxy, heterocycles substituted via an oxygen atom such as oxy, siloxy, acyloxy, carbamoyloxy;
Nitro, amino (including dialkylamino, etc.),
Those substituted through a nitrogen atom such as sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, alkylthio,
Those substituted via a sulfur atom such as arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl, and those substituted via a phosphorus atom such as phosphonyl. Specifically, for example, methyl group, ethyl group, isoprobyl 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, metalsulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3- m-butanesulfonaminophenoxypropyl group, 3-4'-{a-[4''(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenylpropyl group, 3-{4'-a-
(2″,4″-di-t-amylphenoxy)butanamide]phenyl}-propyl group, 4-[a-(o-
chlorophenoxy) tetradecaneamide phenoxy] propyl group, allyl group, cyclopentyl group,
Examples include cyclohexyl group. 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, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amyl phenyl group, 4
-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'-[a-(4''-t-butylphenoxy)tetradecanamido]phenyl group, etc. The heterocyclic group represented by R is 5- A 7-membered group is preferred, and may be substituted or condensed.Specific examples include 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, and 2-benzothiazonyl group. Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, a
-2,4-di-t-amylphenoxybutanoyl group and other alkylcarbonyl groups, benzoyl groups, 3
Examples include arylcarbonyl groups such as -pentadecyloxybenzoyl group and p-chlorobenzoyl group. Examples of the sulfonyl group represented by R include a methylsulfonyl group, an alkylsulfonyl group such as a dodecylsulfonyl group, an arylsulfonyl group such as a benzenesulfonyl group, and a p-toluenesulfonyl group. Examples of the sulfinyl group represented by R include ethylsulfinyl group, octylsulfinyl group, 3-
Alkylsulfinyl group such as phenoxybutylsulfinyl group, phenylsulfinyl group, m-
Examples include arylsulfinyl groups such as pentadecyl phenylsulfinyl groups. The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group,
Examples thereof include alkoxyphosphonyl groups such as octyloxyphosphonyl groups, aryloxyphosphonyl groups such as phenoxyphosphonyl groups, and arylphosphonyl groups such as phenylphosphonyl groups. The carbamoyl group represented by R is an alkyl group,
Aryl groups (preferably phenyl groups) may be substituted, for example, N-methylcarbamoyl groups, N,N-dibutylcarbamoyl groups, N-(2
-pentadecyloctylethyl)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 is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as N-propylsulfamoyl group, N,N-diethylsulfamoyl group, N-
Examples include (2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, and N-phenylsulfamoyl group. Examples of the spiro compound residue represented by R include spiro[3.3]heptan-1-yl. Examples of the bridged carbonized compound residue represented by R include bicyclo[2.2.1]heptan-1-yl, tricyclo[3.3.1.1 ^3,7 ]decane-1-yl, 7,7-
Examples include dimethyl-bicyclo[2.2.1]heptane-1-yl. The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as methoxy group, propoxy group, 2-
Ethoxyethoxy group, pentadecyloxy group, 2
-dodecyloxyethoxy group, phenethyloxyethoxy group and the like. The aryloxy group represented by R is preferably phenyloxy, and the aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group, such as phenoxy group, p-
Examples include t-butylphenoxy group and m-pentadecylphenoxy group. The heterocyclic oxy group represented by R is 5 to 7
It is preferable that the heterocycle has a member heterocycle, and the heterocycle may further have a substituent, for example, 3,
Examples include 4,5,6-tetrahydropyranyl-2-oxy group and 1-phenyltetrazole-5-oxy group. The siloxy group represented by R may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like. The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-chloroacetyloxy group, etc. , benzoyloxy group, and the like. The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, an N-phenylcarbamoyloxy group, etc. Can be mentioned. The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamino group, anilino group, m
-chloroanilino group, 3-pentadecyloxycarbonylanilino group, 2-chloro-5-hexadecaneamideanilino group, and the like. As the acylamino group represented by R, an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group)
etc., which may further have a substituent, specifically an acetamide group, an α-ethylpropanamide group, an N-phenylacetamide group, a dodecanamide group, a 2,4-di-t-amylphenoxylene group, etc. Examples include cyacetamide group, α-3-t-butyl 4-hydroxyphenoxybutanamide group, and the like. Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specifically, methylsulfonylamino group, pentadecylsulfonylamino group, benzenesulfonamide group, p-toluenesulfonamide group, 2-
Examples include methoxy-5-t-amylbenzenesulfonamide group. The imide group represented by R may be an open-chain one,
It may be cyclic and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutarimide group, and the like. The ureido group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group,
Examples include N-methyl-N-decylureido group, N-phenylureido group, and Np-tolylureido group. The sulfamoylamino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoyl Examples include an amino group and an N-phenylsulfamoylamino group. The alkoxycarbonylamino group represented by R may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like. The aryloxycarbonylamino group represented by R 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, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. etc. The aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group, etc. It will be done. The alkylthio group represented by R may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, 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, such as a phenylthio group, p-methoxyphenylthio group, 2
-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, p-acetaminophenylthio group and the like. The heterocyclic thio group represented by R is 5 to 7
A membered heterocyclic thio group is preferable, and may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-triazole-6-thio group. Examples of substituents that can be separated by reaction with the oxidized product of the color developing agent represented by and substituent groups. In addition to carboxyl groups, examples of groups substituted via a carbon atom include, for example, the general formula (R ₁ ' has the same meaning as the above R, Z' has the same meaning as the above Z, and R ₂ ' and R ₃ ' represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.) ,
Examples include hydroxymethyl group and triphenylmethyl group. Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups,
Examples include alkoxyoxalyloxy groups. The alkoxy group may further have a substituent,
Examples include ethoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, phenethyloxy group, p-chlorobenzyloxy group, and the like. The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-dodecylphenoxy group, 4
-methanesulfonamidophenoxy group, 4-[α
-(3′-pentadecylphenoxy)butanamide]
Phenoxy group, hexidecylcarbamoylmethoxy 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, which may be a condensed ring or may have a substituent. in particular,
Examples include 1-phenyltetrazolyloxy group and 2-benzothiazolyloxy group. Examples of the acyloxy group include acetoxy groups, alkylcarbonyloxy groups such as butanoloxy groups, alkenylcarbonyloxy groups such as cinnamoyloxy groups, and arylcarbonyloxy groups such as benzoyloxy groups. 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 alkyloxalyloxy group include a methyloxalyloxy group. Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group. Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group. As the alkylthio group, butylthio group, 2
-cyanoethylthio group, phenethylthio group, benzylthio group, etc. The arylthio group includes phenylthio group, 4
-Methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butylphenylthio group, etc. can be mentioned. Examples of the heterocyclic thio group include 1-phenyl-1,2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. Examples of the group substituting via the nitrogen atom include the general formula

Examples include those represented by the formula. Here, R ₄ ′ and R ₅ ′ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group,
It represents an aryloxycarbonyl group or an alkoxycarbonyl group, and R ₄ ' and R ₅ ' may be combined to form a heterocycle. However, R ₄ ′ and R ₅ ′ are not both hydrogen atoms. The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and 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. 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, and a halogen atom.
Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-ethylhexyl group.
-chloroethyl group. The aryl group represented by R ₄ ' or R ₅ ' has 6 to 32 carbon atoms, and is particularly preferably a phenyl group or a naphthyl group, and the aryl group may have a substituent. Examples of substituents for the alkyl group represented by ₄ ' or _R5 ' include those listed above and an alkyl group. Specific examples of the aryl group include phenyl group, 1-naphthyl group, 4
-methylsulfonylphenyl group. The heterocyclic group represented by R ₄ ′ or R ₅ ′ is 5 to
A 6-membered ring is preferred, and may be a fused ring,
It may have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-furyl group, 2-quinolyl group, 2-pyrimidyl group,
-benzothiazolyl group, 2-pyridyl group, etc. The sulfamoyl group represented by R ₄ ' or R ₅ ' includes N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, These alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group, N
-dodecylsulfamoyl group and N-p-tolylsulfamoyl group. Examples of the carbamoyl group represented by R ₄ ' or R ₅ ' include N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc. The alkyl group and aryl group may have the substituents listed for the alkyl group and aryl group. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, Np-cyanophenylcarbamoyl group, and Np-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, aryl group, and heterocyclic group have a substituent. You may do so. Specific examples of the acyl group include hexafluorobutanoyl group,
2,3,4,5,6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthoyl group,
Examples include 2-furylcarbonyl group. The sulfonyl group represented by R ₄ ′ or R ₅ ′ is
Alkylsulfonyl group, arylsulfonyl group,
A heterocyclic sulfonyl group may be mentioned, which may have a substituent, and specific examples include an ethanesulfonyl group, a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, a p-chlorobenzenesulfonyl group, etc. . The aryloxycarbonyl group represented by R ₄ ' or R ₅ ' may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like. The alkoxycarbonyl group represented by R ₄ ' or R ₅ ' may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, and a benzyloxycarbonyl group. etc. The heterocycle formed by combining R ₄ ' and R ₅ ' is preferably a 5- to 6-membered ring, and may be saturated or unsaturated, and may or may not have aromaticity. It may also be a fused ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxoxazolidinyl group, 2- N-1,1-dioxo-3-
(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, 1-pyrrolidinyl group, 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-tetrahydroquinoline group, 2-oxo-
Examples include 1-pyrrolidinyl group, 2-1H-pyridone group, phthaladione group, 2-oxo-1-piperidinyl group, and these heterocyclic groups include alkyl groups,
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 , an aryloxycarbonyl group, an imide group, a nitro group, a cyano group, a carboxyl group, a halogen atom, or the like. Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned. In addition, in photosensitive materials for positive pictures, general formula [C]
It is preferable that R satisfies the following condition 1, more preferable is the case that R satisfies the following conditions 1 and 2, and particularly preferable is the case that R satisfies the following conditions 1, 2, and 3. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds. The most preferred substituent on the heterocycle is one represented by the following general formula [C]. General formula [C] 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, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group represents,
At least two of R ₉ , R ₁₀ and R ₁₁ are not hydrogen atoms. Also, two of the above R ₉ , R ₁₀ and R ₁₁ , for example R ₉
and R ₁₀ may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R ₁₁ may be further bonded to the ring to form a bridged hydrocarbon compound residue. You may. The group represented by R ₉ to _{R 11} may have a substituent, and specific examples of the group represented by R ₉ to R ₁₁ and the substituents that the group may have include the above-mentioned general formula Specific examples of the group represented by R in [C] and substituents are listed. Also, for example, a ring formed by combining R ₉ and R ₁₀ and
Specific examples of the bridged hydrocarbon compound residue formed by R ₉ to _{R 11} and its optional substituents include cycloalkyl, cycloalkenyl, and heterocycle represented by R in the above general formula [C]. Specific examples of the radical-bridged hydrocarbon compound residues and their substituents are listed. Among the general formula [C], (i) two of R ₉ to R ₁₁ are alkyl groups, (ii) one of R ₉ to R ₁₁ , for example R ₁₁ , is a hydrogen atom. Then, when the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom, then. Further preferred among (i) is the case where two of R ₉ to _{R 11} are alkyl groups and the other one is a hydrogen atom or an alkyl group. Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its substitution represented by R in the general formula [C]. Specific examples of the group are listed below. Furthermore, R ₁ in general formula [C] is preferably represented by the following general formula [C]. General formula [C] −R ¹ −SO ₂ −
In the R ² formula, R ¹ represents alkylene, and R ² represents alkyl, cycloalkyl or aryl. The alkylene represented by R ¹ preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms.
It does not matter whether it is straight chain or branched. Moreover, this alkylene may have a substituent. Examples of the substituent include the above-mentioned general formula [C]
When R in is an alkyl group, the substituents that the alkyl group may have include those shown below. Preferred substituents include phenyl. Preferred specific examples of alkylene represented by R ¹ are shown below. −CH ₂ CH ₂ CH ₂ −,

【formula】

【formula】

【formula】

[Formula] −CH ₂ CH ₂ CH ₂ CH ₂ −,

【formula】

【formula】

[Exemplary compounds]

(-1) (-2) (-3) (-4) (-5) (-6) (-7) (-8) (-9) (-10) (−11) (-12) (-13) (-14) (-15) (-16) (-17) (-18) (-19) (-20) (-21) (−22) (−23) (-24) (-25) (-26) (-27) (-28) (-29) (-30) (-31) (−32) (−33) (-34) (-35) (−36) (-37) (-38) (-1) (-2) (-3) (-4) (-5) (-6) (-7) (-8) (-9) (-10) (-11) (-12) (-13) (-14) (-15) (-16) (-17) (-18) (-19) (-20) (-21) (-22) (−23) (-24) (-25) (-26) (-27) (−28) H ₂ N−CSNHNHCS−NH ₂ (−29) (-30) (-31) (−32) (−33) (−34)H ₂ N−CSNH(CH ₂ ) ₂ NHCS−NH ₂ (−35)H ₂ N−CSNH(CH ₂ ) ₄ NHCS−NH ₂ (−36)H ₂ N−CSNH(CH ₂ ) ₅ NHCS− _NH2 (−37) (-38) (-39) (-40) (−41) (−42) (−43) (−44) (−45) (−46) (−47) (−48) (-49) (-50) (-51) (−52) (-53) (-54) (-55) (-56) (-57) (-58) (-59) (-60) (−61) (−62) (−63) (−64) (−65) (-66) (−67) (−68) (-69) (-70) (−71) (−72) (−73) (−74) (−75) (-76) (-77) (-78) (-79) (-80) (−81) (-82) (-83) (-84) (-85) (−86) (−87) (−88) (-89) (-90) (-91) (-92) (-93) (-94) (-95) (-96) (-97) (-98) (-99) (-100) (-101) (−102) (−103) (−104) (−105) (-106) (−107) (−108) (-109) (-110) (−111) (-112) (-113) (-114) (-115) (−116) (-117) (-118) (-119) (-120) (−121) (-122) (−123) (-124) (-125) (−126) (−127) (-128) (-129) (-130) (-131) (-132) (-133) (−134) (-135) (-136) (-137) (-138) (-139) (-140) (-141) (−142) (−143) (−144) (-145) (−146) (−147) (-148) (−149) (-150) (-151) (-152) (-153) (-154) (-155) (-156) (-157) (-158) (-1) _H2N - _{CH2CH2 -} SH (-2) (-3) (-4) (-5) HOOC・CH ₂ CH ₂・SH (-6) (-7) (-8) (-9) (-10) (−11) (−12) (-13) (-14) (-15) (-16) (-17) (-18) (-19) (-20) (-21) (-22) (−23) (-24) (-25) (-26) (-27) (-28) (-29) (-30) (-31) (−32) (-33) (−34) (-35) (−36) (-37) (-1) (-2) (-3) (-4) (-5) (-1) (-2) (-3) (-4) (-5) (-6) (-7) (-8) (-9) (-10) (−11) (−12) (-13) (-14) (-15) (-16) (-17) (-18) (-19) (-20) (-21) (-22) (−23) (-24) (-25) (-28) (-27) (-28) (-29) (-30) (-31) (-32) (-33) (-34) (-35) (-36) (-37) (-38) (-39) (-40) (-41) (-42) (-43) (-44) (-45) (−46) (-47) (-48) (-49) (-50) (-51) (−52) (-53) (-54) (-55) (-56) (-57) (-58) (-59) (-60) (−61) (−62) (−63) (−64) (−65) (−66) (−67) (−68) (-69) (-70) (−71) (−72) (−73) (−74) (−75) (-76) (-77) (-78) (-79) (-80) (−81) (-82) (-83) (-84) (-85) (−86) (-87) (−88) (−89) (-90) (-91) (-92) (-93) (-94) (-95) (-96) (-97) (-98) (-99) (-100) (-101) (−102) (−103) (−104) (−105) (−106) (−107) (−108) (-109) (-110) (−111) (-112) (-113) (-114) (-115) (−116) (-117) (-118) (-119) (-120) (-121) (-122) (−123) (-124) (-125) (-126) (−127) (-128) (-129) (-130) (-131) (-132) (-133) (−134) (-135) (-136) (-137) (-138) (-139) (-140) (-141) (−142) (−143) (−144) (-145) (−146) (−147) (-148) (−149) (-150) (-151) (-152) (-153) (-154) (-155) (-156) (-157) (-158) (-159) (-160) (-161) (−162) (−163) (-164) (-165) (-166) (-167) (-168) (-169) (-170) (-171) (-172) (-173) (-174) (-175) (-176) (-177) (-178) (-179) (-180) (-181) (-182) (-183) (-184) (-1) (-2) (-3) (-4) (-5) (-6) (-7) (-8) (-9) (-10) (−11) (-12) (-13) (-14) (-15) (-16) (-17) (-18) (-19) (-20) (-21) (−22) (−23) (-24) (-25) (-26) (-27) (-28) (-29) (-30) (-31) (−32) (-33) (−34) (-35) (−36) The above compounds are, for example, British Patent No. 1138842,
JP-A-52-20832, JP-A No. 53-28426, JP-A No. 53-
No. 95630, No. 53-104232, No. 53-141623, No. 53-141623, No. 53-141623, No.
It can be easily synthesized by the known techniques described in US Pat. No. 55-17123, US Pat. No. 3,772,020, and US Pat. The bleaching accelerator of the present invention only needs to be present when bleaching the silver image obtained by development, and is preferably added to a processing bath having bleaching ability, and is preferably added to a processing bath having bleaching ability. It is also preferable to add it to a pretreatment solution and bring it into the bleach-fixing bath by bringing it into the color photosensitive material.
Alternatively, a method may be used in which the compound is incorporated into the color photosensitive material in advance during production, and the compound is eluted into the bleach-fixing bath. These bleach accelerators of the present invention may be used alone or in combination of two or more. Good results can generally be obtained when the amount added is in the range of about 0.01 to 100 g per 1 treatment liquid. However, in general, if the amount added is too small, the effect of promoting bleaching will be small, and if the amount added is too large, precipitation may occur and contaminate the color photosensitive material being processed.
The amount is preferably 0.05 to 50 g per treatment liquid, and more preferably 0.05 to 15 g per treatment liquid. When the bleach accelerator of the present invention is added to a treatment bath having bleaching ability and/or a bath (pretreatment bath) that precedes a treatment bath having bleaching ability, it may be added and dissolved as is, but water, alkali, Generally, it is added after being dissolved in an organic acid, etc. If necessary, it may be added after being dissolved in an organic solvent such as methanol, ethanol, acetone, etc., without any effect on the bleach-fixing effect. . The bleaching accelerator of the present invention has the general formula [] to
It is represented by [], among which R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ , R ₈ , R ₉ , A, B, D, Z, Z', R, R',
and R and R′, R ₂ and R ₃ , R ₄ and R ₅ ,
The heterocyclic residue, amino group, aryl group, alkenyl group, and alkylene group formed by Q and Q' may each be substituted. Substituents include alkyl groups, aryl groups, alkenyl groups, cyclic alkyl groups, aralkyl groups, cyclic alkenyl groups, halogen atoms, nitro groups, cyano groups, alkoxy groups, aryloxy groups, carboxy groups, alkoxycarbonyl groups, and aryloxy groups. Carbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, heterocyclic residue, arylsulfonyl group, alkylsulfonyl group, alkylamino group, dialkylamino group, anilino group, N-
Alkylanilino group, N-arylanilino group,
Examples include N-acylanilino group and hydroxy group. In addition, the above R ₁ to R ₅ , R ₈ , R ₉ , Z′,
The alkyl group represented by R and R' may also have a substituent, and examples of the substituent include all those listed above except for the alkyl group. As peroxides according to the present invention, hydrogen peroxide, percarbonates, perborates, and persulfates are preferably used.
Further, examples of these salts include potassium salts, sodium salts, ammonium salts, and the like. The preferred amount of these used is in the range of 0.01 to 6.0 mol/, more preferably in the range of 0.05 to 3.0 mol/. The pH of the processing solution containing peroxide used in the present invention is
It is necessary to adjust it to a range of 0.1 to 8.0, particularly preferably a range of 0.5 to 5.5. When the peroxide according to the present invention is decomposed, it easily becomes water and oxygen or sulfate, and can be easily and completely rendered harmless. Furthermore, the materials used in the treatment solution according to the present invention are inexpensive and have excellent bleaching ability even when used at low concentrations.This advantage is directly reflected in terms of resources, with a low pollution burden. This makes it possible to easily supply an inexpensive bleaching solution or bleach-fixing solution. The treatment solution having bleaching ability of the present invention can also contain organic acid ferric complex salt, ferric chloride, red blood salt, etc. for the purpose of further increasing the bleaching power. Representative examples of organic acids that form organic acid ferric complex salts include the following. (1) Ethylenediaminetetraacetic acid (2) Ethylenediaminetetramethylenephosphonic acid (3) Diethylenediaminepentaacetic acid (4) Diethylenetriaminepentamethylphosphonic acid (5) Cyclohexanediaminetetraacetic acid (6) Cyclohexanediaminetetramethylenephosphonic acid (7) Triethylene Tetramine hexaacetic acid (8) Triethylenetetramine hexamethylenephosphonic acid (9) Glycol ether diamine tetraacetic acid (10) Glycol ether diamine tetramethylene phosphonic acid (11) 1,2-diaminopropane tetraacetic acid (12) 1,2-diamino Propane tetramethylenephosphonic acid (13) 1,3-diaminopropan-2-ol tetraacetic acid (14) 1,3-diaminopropan-2-ol tetramethylenephosphonic acid (15) Ethylenediaminedi-o-hydroxyphenylacetic acid ( 16) Ethylenediaminedi-o-hydroxyphenylmethylenephosphonic acid (17) Iminodiacetic acid (18) Iminodimethylenephosphonic acid (19) Methyliminodiacetic acid (20) Methyliminodimethylenephosphonic acid (21) Nitrilotriacetic acid (22) Nitrilo trimethylene phosphonic acid (23) Hydroxyethylethylenediaminetetraacetic acid (24) Hydroxyethylethylenediamine tetramethylenephosphonic acid (25) Nitrilotripropionic acid (26) Hydroxyethylglycine (27) Hydroxyethyliminodiacetic acid (28) Hydroxyethyliminodiacetic acid Methylenephosphonic acid (29) Ethylenediaminediacetic acid (30) Ethylenediaminedipropionic acid Among the organic acids that form ferric complex salts of these organic acids, the following are particularly preferred. (3) Diethylenetriaminepentaacetic acid (5) Cyclohexanediaminetetraacetic acid (7) Triethylenetetraminehexaacetic acid (1) Ethylenediaminetetraacetic acid (11) 1,2-diaminopropanetetraacetic acid (9) Glycol ether diamine tetraacetic acid These organic acids Ferric complex salts are used as free acids (hydrogen salts), alkali metal salts such as sodium salts, potassium salts, lithium salts, ammonium salts, or water-soluble amine salts such as triethanolamine salts, but preferably potassium salts are used. salt,
Sodium and ammonium salts are used. At least one type of these ferric complex salts may be used, but two or more types can also be used in combination. The amount used can be arbitrarily selected and needs to be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but it is generally lower than other aminopolycarboxylate salts because of its high oxidizing power. Can be used in concentrations. That is, it is preferably used in an amount of 0.01 mol or more, more preferably 0.05 to 0.6 mol per liquid used. In addition, it is desirable to use the replenisher after concentrating it to maximize its solubility in order to achieve high concentration and low replenishment. It is desirable that metal ions be supplied to the treatment liquid having bleaching ability of the present invention by any method in order to improve the bleaching ability. For example, it can be supplied in any form such as a halide, hydroxide, sulfate, phosphate, acetate, etc., but it is preferable to supply it as a complex salt of the chelating agent using the following compounds (hereinafter, these A metal compound that supplies metal ions is referred to as a metal compound of the present invention). but,
It is not limited to these supply methods.
The chelating agent may be any organic polyphosphoric acid, aminopolycarboxylic acid, or the like. [Exemplary compounds] (A-1) Nickel chloride (A-2) Nickel nitrate (A-3) Nickel sulfate (A-4) Nickel acetate (A-5) Nickel bromide (A-6) Nickel iodide (A -7) Nickel phosphate (A-8) Bismuth chloride (A-9) Bismuth nitrate (A-10) Bismuth sulfate (A-11) Bismuth acetate (A-12) Zinc chloride (A-13) Zinc bromide ( A-14) Zinc sulfate (A-15) Zinc nitrate (A-16) Cobalt chloride (A-17) Cobalt nitrate (A-18) Cobalt sulfate (A-19) Cobalt acetate (A-20) Cerium sulfate (A -21) Magnesium chloride (A-22) Magnesium sulfate (A-23) Magnesium acetate (A-24) Calcium chloride (A-25) Calcium nitrate (A-26) Barium chloride (A-27) Barium acetate (A- 28) Barium nitrate (A-29) Strontium chloride (A-30) Strontium acetate (A-31) Strontium nitrate (A-32) Manganese chloride (A-33) Manganese sulfate (A-34) Manganese acetate (A-35) ) Lead acetate (A-36) Lead nitrate (A-37) Titanium chloride (A-38) Stannous chloride (A-39) Zirconium sulfate (A-40) Zirconium nitrate (A-41) Ammonium vanadate (A -42) Ammonium metavanadate (A-43) Sodium tungstate (A-44) Ammonium tungstate (A-45) Aluminum chloride (A-46) Aluminum sulfate (A-47) Aluminum nitrate (A-48) Yttrium sulfate (A-49) Yttrium nitrate (A-50) Yttrium chloride (A-51) Samarium chloride (A-52) Samarium bromide (A-53) Samarium sulfate (A-54) Samarium acetate (A-55) Ruthenium sulfate (A-56) Ruthenium chloride These metal compounds of the present invention may be used alone or in combination of two or more. The amount used is 0.0001 metal ions per liquid used.
Preferably from mol to 2 mol, particularly preferably 0.001
It ranges from 1 mole to 1 mole. The processing liquid having bleaching ability of the present invention can contain various additives together with the peroxide of the present invention as a bleaching agent as described above. As additives for the bleach-fixing properties, in particular alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide,
It is desirable to contain potassium iodide, sodium iodide, ammonium iodide, etc. Also borate,
PH buffers such as oxalate, acetate, carbonate, phosphate,
Solubilizers such as triethanolamine, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, alkylamines, polyethylene oxides, etc. are known to be added to ordinary bleaching solutions. It is possible to add as appropriate. The processing liquid having bleaching ability of the present invention includes a bleach-fixing liquid having a composition in which a small amount of a halide such as potassium bromide is added, or conversely, a composition having a composition in which a large amount of a halide such as potassium bromide or ammonium bromide is added. It is also possible to use a special bleach-fix solution having a composition consisting of a combination of the bleaching agent of the present invention and a large amount of a halide such as potassium bromide. Silver halide fixing agents to be included in the bleach-fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. thiosulfates, potassium thiocyanate, sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate, thioureas, thioethers, high concentrations of bromides,
Typical examples include iodides. These fixing agents are 5g/or more, preferably 50g/or more,
More preferably, it can be used in an amount that can dissolve 70 g/or more. In addition, various pH buffering agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be used alone in the bleach-fix solution. Alternatively, a combination of two or more types may be contained. Furthermore, various optical brighteners, antifoaming agents, or antifungal agents can be contained. Preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds,
Other additives and organic solvents such as methanol, dimethylformamide, dimethyl sulfoxide, etc. can be included as appropriate. Other desirable compounds that can be added to the bleaching solution of the present invention to promote bleaching properties include tetramethylurea, trisdimethylamide phosphate, ε-caprolactam, N-methylpyrrolidone, N-methylmorpholine, and tetraethylene glycol. Examples include monophenyl ether, acetonitrile, glycol monomethyl ether, and the like. In the processing method of the present invention, it is preferable to carry out the bleaching of the present invention immediately after color development; It's okay. The method of the present invention includes independent steps of development, bleaching, and bleach-fixing, but here, development means black-and-white development and color development, and a method involving only color development or a method including both black-and-white development and color development is also used. . The above steps do not necessarily have to be consecutive, and various processing steps can be included before and after each of the above steps. Such a step is called an auxiliary step, and the auxiliary steps include a stop bath, a stop fixing bath, a hardening bath, a neutralization bath, a water wash, a rinse, an image stabilizing bath, and the like. From the viewpoint of simplifying the processing steps, the bleaching solution or bleach-fixing solution according to the present invention is preferably applied to a processing process in which bleaching or bleach-fixing is carried out immediately after color development. However, in the bleach-fix solution of the present invention, it may be more preferable that no developing agent or halogen ions are mixed into the bleach-fix solution.
Also, depending on the type of color photosensitive material to be processed and other requirements, water washing treatment, rinsing treatment, stop treatment, bleach-fixing treatment, pre-bleach-fixing bath (so-called conditioner for efficient bleach-fixing) or hardening treatment after color development, depending on the type of color photosensitive material to be processed and other requirements. It is more desirable to carry out bleach-fixing after suitably undergoing one or more treatments such as the following. Further, for a special purpose, after the bleach-fixing process, it is optional to perform a separate process with a bleach-fixing solution or a fixing solution that is not according to the present invention. That is, it is optional to place a bleach or bleach-fix solution according to the present invention at any processing process location to remove image silver. Next, specific examples of treatment processes will be shown, but the present invention is not limited to the following process examples. Dural mater - Neutralization - Development - Stop - Washing - Color development -
Stop - Bleaching - Fixing - Water washing - Final treatment - Drying Development - Water washing - Reversal - Color development - Adjustment - Bleaching -
Fixing - Washing - Final treatment - Drying Color development - Bleaching - Fixing - Washing - Final treatment - Drying Color development - Bleaching - Small amount of water washing - Fixing - Pre-washing - Washing - Final treatment - Drying Color development - Bleach-fixing - Pre-washing - Washing - Final processing - Drying Color development - Bleach-fixing - Final processing - Drying Color development - Bleaching - Fixing - Final processing - Drying Final processing means washing with water or JP-A No. 57-8543, No. 58
−57903 etc. is to perform waterless washing treatment,
Particularly, in terms of resource saving and image preservation, the waterless washing process has favorable effects. The thickness of the photographic constituent layers (gelatin film thickness) of the color light-sensitive material of the present invention refers to the photographic constituent layers excluding the support, that is, the subbing layer, antihalation layer, intermediate layer, at least three emulsion layers, filter layer, and protective layer. This is the total thickness of all hydrophilic colloid layers, such as a layer, and the thickness of a dried photographic constituent layer. The thickness is measured with a micrometer, and in the present invention the total thickness of the photographic constituent layers is 25 μm or less, preferably 22 μm or less, particularly preferably 20 μm or less, and most preferably 18 μm or less. The silver halide of the silver halide emulsion layer used in the present invention contains at least 0.5 mol% of silver iodide grains, but in order to maximize the sensitivity and photographic properties of the color light-sensitive material and the bleach-fixing performance of the present invention. teeth,
Silver iodide is preferably used in an amount of 3 mol % to 25 mol % from the viewpoint of photographic properties and bleach-fixing properties. In the present invention, if the content exceeds 25 mol%, the photographic properties are more preferable, but the bleach-fixing properties are significantly reduced. In the present invention, it is more preferable that silver iodide be contained in an amount of 3 mol % to 20 mol %. The black colloidal silver dispersion layer for preventing halation used in the present invention has a sufficiently high optical density in the visible region (especially red light) for light incident from the support surface or emulsion surface of the color photosensitive material. It is necessary to have it. Further, it is necessary that the color light-sensitive material has a sufficiently low reflectance for light incident on the emulsion surface. From the viewpoint of reflectance and bleach-fixing properties, colloidal silver with sufficiently fine particles is desirable, but colloidal silver with absorption of yellow to yellow is preferable.
Since the color becomes yellow-brown and the optical density against red light does not increase, the grains must be coarse to some extent.Therefore, physical development using these silver grains as nuclei is likely to occur, and the bleach-fixability of the boundary with the silver halide emulsion layer is reduced. It is thought that it will get worse. Bleach-fixability is particularly important when the silver halide emulsion layer contains at least 3 mol % of silver iodide grains, especially when the silver halide emulsion layer closest to the support contains at least 3 mol % of silver iodide grains. The phenomenon of decrease in
It can be seen that the method of the present invention is effective because it is noticeable in multilayer color light-sensitive materials having three or more silver iodide-containing emulsion layers. The photosensitive silver halide emulsion used in the present invention may be doped with various metal salts or metal complex salts during silver halide precipitation, during grain growth, or after grain growth. For example, gold, platinum, palladium, iridium, rhodium,
Metal salts or complex salts such as bismuth, cadmium, copper, etc., and combinations thereof can be applied. Excess halogen compounds generated during the preparation of the emulsion or by-products or unnecessary salts and compounds such as nitrates and ammonium may be removed. As a method for removal, a nude washing method, a dialysis method, a coagulation precipitation method, etc., which are commonly used in general emulsions, can be used as appropriate. Further, the emulsion used in the present invention can be subjected to various chemical sensitization methods that are applied to general emulsions. Namely, activated gelatin; noble metal sensitizers such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, and water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; polyamines, primary chloride Chemical sensitization can be carried out using a chemical sensitizer such as a reduction sensitizer such as tin alone or in combination. Furthermore, this silver halide can be optically sensitized to a desired wavelength range. There are no particular limitations on the method for optically sensitizing the emulsion of the present invention. ) can be optically sensitized. These technologies are described in U.S. Patent No. 2688545, U.S. Patent No. 2912329, U.S. Patent No. 3397060, U.S. Pat.
No. 3615635, No. 3628964, British Patent No. 1195302,
No. 1242588, No. 1293862, West German patent (OLS)
No. 2030326, No. 2121780, Special Publication No. 43-4396, No.
44-14030 etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, the sensitivity, the purpose of the photosensitive material, and the use. The average grain size of the silver halide grains used in the present invention is preferably 0.5 μm to 3 μm, and can be grown using a solvent such as ammonia, thioether, thiourea, etc., if necessary. In addition, the emulsion used in the present invention is
It is also preferable to include epitaxy-junctioned silver halide grains described in No. 103725, No. 59-133540, No. 59-162540, and the like. The silver halide emulsion can contain various commonly used additives depending on the purpose. For example, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazoliums, tetrazolium salts, polyhydroxy compounds; aldehyde-based, aziridine-based, isoxazole-based, vinylsulfone-based, acryloyl-based, carbodiimide-based, maleimide-based Hardening agents such as chroman, methanesulfonic acid ester, and triazine; Development accelerators such as benzyl alcohol and polyoxyethylene compounds; Image stabilizers such as chroman, claman, bisphenol, and phosphite esters; Lubricants include waxes, glycerides of higher fatty acids, and higher alcohol esters of higher fatty acids. In addition, anionic, cationic, nonionic, or A variety of both sexes can be used. In particular, it is preferable that these surfactants are eluted into a processing solution having bleaching ability. As the antistatic agent, diacetyl cellulose, styrene perfluoroalkyl sodium maleate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective.
Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc. and other monomers having ethylene groups. Gelatin plasticizers include glycerin and glycol compounds, and thickeners include styrene-sodium maleate copolymer and alkyl vinyl ether.
Examples include maleic acid copolymers. In the color light-sensitive material of the present invention, hydrophilic colloids used to prepare emulsions and other hydrophilic colloid layer coating solutions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, albumin, casein, etc. , cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide. Examples of the support for the color light-sensitive material of the present invention include 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 furthermore, a conventional reflective support. (For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material) may be used, and these supports are appropriately selected depending on the intended use of the photosensitive material. Various coating methods such as dip coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. Further, simultaneous coating of two or more layers by the methods described in US Pat. No. 2,761,791 and US Pat. No. 2,941,898 can also be used. The silver halide emulsion of the present invention is a combination of cyan, magenta, and yellow couplers with the silver halide emulsion of the present invention, which has been color-sensitized and adjusted to have red sensitivity, green sensitivity, and blue sensitivity, in order to be applied to color light-sensitive materials. The method and material used for color photosensitive materials may be used, such as the method and material used for color photosensitive materials. The color photosensitive material to which the bleach-fix solution of the present invention can be applied is an internal development method in which a coloring agent is contained in the photosensitive material (see U.S. Pat. Nos. 2,376,679 and 2,801,171).
In addition to external development methods (U.S. Pat. No. 2252718, U.S. Pat. No. 2592243, U.S. Pat.
2590970). Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, cyan color formers are those based on a naphthol or phenol structure and form indoaniline dyes through coupling, magenta color formers are those whose skeleton structure is a 5-pyrazolone ring with an active methylene group, and yellow color formers are As such, those having an acylacetanilide structure such as benzoylacetanilide and pivallylacetanilide having an active methylene chain, with or without a substituent at the coupling position can be used. Thus, as the color former, both so-called 2-equivalent couplers and 4-equivalent couplers can be used. The black-and-white developer that can be used in the processing of the present invention is a commonly known black-and-white first developer used in processing color photographic materials, or a developer used in processing black-and-white photographic materials. It can contain various additives that are generally added to black and white developers. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds, etc. can be mentioned. The aromatic primary amine color developing agent used in the color developing solution used before processing with the bleach-fix solution of the present invention includes a variety of aromatic primary amine color developing agents that are widely used in various color photographic processes. . These developers are aminophenolic and p
-Includes phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, because they are more stable than the free state. Further, it is generally preferable to use these compounds at a concentration of about 0.1 g to about 30 g per 1 part of the color developer, more preferably about 1 g per 1 part of the color developer.
It is used at a concentration of about 15 g to about 15 g. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3
-amino-1,4-dimethylbenzene and the like. Particularly useful aromatic primary amine color developers are N,N-dialkyl-p-phenylenediamine compounds, in which the alkyl and phenyl groups may be substituted or unsubstituted. Among them, particularly useful compounds are N, N
-diethyl-p-phenylenediamine hydrochloride, N
-methyl-p-phenylenediamine hydrochloride, N,
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 -Hydroxyethylaminoaniline sulfate, 4-amino-3
-Methyl-N,N-diethylaniline sulfate, 4
-amino-N-(methoxyethyl)-N-ethyl-
Examples include 3-methylaniline-p-toluenesulfonate. The paraphenylenediamine color developing agent is preferably mixed into the bleach-fix solution of the present invention. The alkaline color developing solution used before the treatment with the processing solution having bleaching ability of the present invention contains, in addition to the above-mentioned aromatic primary amine color developing agent, various types of color developing solutions that are usually added to color developing solutions. Ingredients, such as alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene Water softeners and thickeners such as -1,1-diphosphonic acid can optionally be included. The pH of this color developer is usually 7 or higher,
Most commonly from about 10 to about 13. The processing solution having bleaching ability according to the present invention can be used for color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, reversal color paper, etc. Although the present invention can be applied to color light-sensitive materials, it is particularly suitable for processing high-sensitivity color light-sensitive materials in which the total amount of coated silver is 20 mg/dm ² or more. [Example] The details of the present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Reference example: Following the layer structure adopted in the industry for high-sensitivity silver halide color photographic light-sensitive materials, a black colloidal silver antihalation layer, a red-sensitive halogen layer, and a red-sensitive halogen layer are added from the support side, with various auxiliary layers interposed. A silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, and a monodisperse high-sensitivity silver halide emulsion layer was arranged on the outermost side of the blue-sensitive silver halide emulsion layer. . That is, samples were prepared according to the following procedure, but the film thickness was adjusted and the dry film thickness was varied while keeping the amount of coated silver constant. However, the following are standard coating conditions, and each formulation was adjusted to account for changes in film thickness. Layer 1: 0.8 g of black colloidal silver, which is highly absorbent to light in the wavelength range of 400 to 700 nm, is reduced using hydroquinone using silver nitrate as a reducing agent, and 3 g of gelatin.
A dispersion liquid was prepared using a method and an antihalation layer was applied. (Dry film thickness 2.0 μm) Layer 2: Intermediate layer made of gelatin. (Dry film thickness 0.8μ
m) Layer 3...1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion (AgI; 8 mol%), 1.6 g of gelatin and 0.80
g of 1-hydroxy-4-(β-methoxyethylaminocarbonylmethoxy)-N-[δ-(2,
4-di-t-amylphenoxy)butyl]-2
- Naphthamide (hereinafter referred to as cyan coupler (C-
1)), 0.028 g of 1-hydroxy-4-
[4-(1-hydroxy-8-acetamide-
3,3-disulfo-2-naphthylazo)phenoxy]-N-[δ-(2,4-di-amylphenoxy)butyl]-2-naphthamide disodium (hereinafter referred to as colored cyan coupler (CC-
A low-sensitivity red-sensitive silver halide emulsion layer containing 0.4 g of tricresyl phosphate (hereinafter referred to as TCP) dissolved in 1). Layer 4...1.1 g of highly sensitive red-sensitive silver iodobromide emulsion (AgI; 7 mol%), 1.2 g of gelatin and 0.23
g of cyan coupler (C-1) and 0.020 g of colored cyan coupler (CC-1) were dissolved.
Highly sensitive red-sensitive silver halide emulsion layer containing 0.15g of TCP. Layer 5...0.04g of dibutyl phthalate (hereinafter referred to as DBP) in which 0.07g of 2,5-di-t-octylhydroquinone (hereinafter referred to as antifouling agent (HQ-1)) was dissolved and 1.2g of gelatin. An intermediate layer containing. Layer 6...1.6 g of low-speed green-sensitive silver iodobromide emulsion (AgI; 15 mol%), 1.7 g of gelatin and 0.30
g of 1-(2,4,6-trichlorophenyl)-
3-[3-(2,4-di-t-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler (M-a)), 0.20 g of 4,4-methylenebis- 11−
(2,4,6-trichlorophenyl)-3-[3
-(2,4-di-t-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler (M-b)),
0.066 g of 1-(2,4,6-trichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone (hereinafter referred to as colored A low-sensitivity green-sensitive silver halide emulsion layer containing 0.3 g of TCP in which three types of couplers, a magenta coupler (referred to as CM-1), were dissolved. Layer 7...1.5g of highly sensitive green-sensitive silver iodobromide emulsion (AgI; 11 mol%), 1.9g of gelatin and
0.093g magenta coupler (M-a), 0.094
A high-sensitivity green-sensitive silver halide emulsion layer containing 0.12 g of TCP in which g of magenta coupler (M-b) and 0.049 g of colored magenta coupler (CM-1) were dissolved. Layer 8...0.2g yellow colloidal silver, 0.11g DBP dissolved in 0.2g antifouling agent (HQ-1) and 2.1
Yellow filter layer containing g of gelatin. (Dry film thickness 1.2 μm) Layer 9...0.95 g of low-sensitivity blue-sensitive silver iodobromide emulsion (AgI; 6 mol%), 1.9 g of gelatin and 1.84
g of α-[4-(1-benzyl-2-phenyl-
3,5-dioxo-1,2,4-triazolidinyl)]-α-pivaloyl-2-chloro-5-
0.93 g of [γ-(2,4-di-t-amylphenoxy)butanamide] acetanilide (hereinafter referred to as yellow coupler (Y-1)) dissolved
A low-speed blue-sensitive silver halide emulsion layer containing DBP. Layer 10...1.2g of highly sensitive monodisperse blue-sensitive silver iodobromide emulsion (AgI; 7 mol%), 2.0g of gelatin and
A highly sensitive blue-sensitive silver halide emulsion layer containing 0.23 g of DBP in which 0.46 g of yellow coupler (Y-1) was dissolved. Layer 11...Second protective layer made of gelatin. Layer 12...first protective layer containing 2.3 g of gelatin. The dry film thickness of the photographic constituent layers of each finished sample is
35μm, 30μm, 27μm, 25μm, 22μm, 20μm,
There were eight types, 18 μm and 15 μm. This is sample No.
It was set as 1 to 8. However, the film thickness and black colloidal silver content of the antihalation layer and the film thicknesses of the gelatin intermediate layer and yellow filter layer were not changed at all. Another sample was prepared by coating the same emulsion on a transparent polyethylene terephthalate film base without the bottom colloidal silver antihalation layer. These samples are numbered in descending order of film thickness.
It was set as 9 to 16. Average coated silver amount for all samples is 50-58
It was adjusted to be mg/ ^dm2 . Each sample was treated using a treatment solution prepared according to the following treatment steps and the following formulation. Processing process Temperature Time Color development 41℃ 3 minutes Pre-bleaching bath 38℃ 30 seconds Bleaching bath 38℃ 10 seconds to 5 minutes Washing with water 33℃ 1 minute Fixing 33℃ 3 minutes Washing with water 33℃ 2 minutes Stability 33℃ 30 Second [Color developer] Potassium carbonate 30g Sodium sulfite 2.0g Hydroxylamine sulfate 2.0g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0g Potassium bromide 1.2g Magnesium chloride 0.6g Sodium hydroxide 3.4g N-ethyl- N-β-hydroxyethyl-3-methyl-4-aminoaniline sulfate 4.6g Add water to make 1, then PH with sodium hydroxide
Adjusted to 10.1. [Pre-bleaching bath] Sodium sulfite 10.0g Sodium acetate 8.0g Glacial acetic acid 23ml Water was added to bring the solution to 1, and the pH was adjusted to 3.8 with sodium hydroxide or acetic acid. [Bleach solution] Sodium persulfate 60g Sodium chloride 20g Sodium dihydrogen phosphate (anhydrous) 9.0g Phosphoric acid (85%) 2.5ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 1.0g Gelatin 0.5g Water was added to make 1, and the pH was adjusted to 2.3 with sodium hydroxide or phosphoric acid. [Fixer] Sodium thiosulfate 150g Sodium sulfite 12g Add water to make 1. [Stabilizing solution] Formalin (37% solution) 10ml Add water to make 1. The exemplified compounds of the present invention were added to the pre-bleaching bath in an amount of 1.5 g as shown in Table 1, and the bleaching time was varied in two steps of 1 minute and 3 minutes, and the bleaching ability was compared based on the amount of residual silver. did. The results are shown in Table 1.

【table】

[Comparative bleaching solution]

Ethylenediaminetetratetraacetic acid ammonium dihydrate 90g Ammonium bromide 150g Ethylenediaminetetraacetic acid 20g Acetic acid (90%) 20ml Water was added to make 1, and the pH was adjusted to 6.0 with aqueous ammonia. The results are shown in Table 2.

Table 2 As shown in Table 2, the decrease in magenta dye density (fading) due to storage does not occur at all in the comparative bleaching solution, but in the bleaching solution of the present invention, it increases markedly as the photographic constituent layers become thinner. However, it can be seen that by using the magenta coupler of the present invention, the decrease in the density of the magenta dye can be suppressed at the film thickness of the present invention. Example 2 The magenta coupler M-44 (coupler of the present invention) of Example 1 was converted into M-5, M-6, M-7, M-15,
M-18, M-22, M-41, M-59, M-100, M
The example was repeated using -104, M-116, M-117 and M-142, but in all cases, fading of the magenta dye after storage was significantly suppressed and good results were obtained. Example 3 Using the multilayer color photosensitive material samples (No. 18 and No. 22) containing the magenta coupler M-44 of the present invention prepared in Example 1 and having film thicknesses of 30 μm and 20 μm, the same treatment as in Example 1 was carried out. The maximum density of the magenta dye obtained by processing according to the steps before and after storage was measured. However, the bleaching treatment time was varied as shown in Table 3. The results are shown in Table 3.

[Table] As is clear from Table 3, the fading rate of magenta dye due to storage is almost independent of the bleaching time when the film thickness is 30 μm, but when the film thickness is as thin as 20 μm, the bleaching time is 3 minutes or more. increases rapidly. However, by reducing the bleaching time to 3 minutes or less, the rate of discoloration could be significantly reduced.

Claims (1)

[Scope of Claims] 1. A photographic constituent layer comprising a black colloidal silver-containing antihalation layer and a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer on a support; A compound in which the emulsion layer closest to the antihalation layer contains silver halide grains containing silver iodide, the total thickness of the photographic constituent layers is 25 μm or less, and is represented by the following general formula [C] A silver halide color photographic light-sensitive material, which is characterized in that the silver halide color photographic light-sensitive material is developed after imagewise exposure, and processed with a processing solution having a silver bleaching ability and containing peroxide as a bleaching agent. processing method. General formula [C] [In the formula, X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, R and R ₁ represent a hydrogen atom or a substituent. 2. The treatment bath according to claim 1, characterized in that the treatment bath having bleaching ability and/or the bath preceding the bath contains at least one compound represented by the following general formulas [] to []. A method for processing silver halide color photographic materials. General formula [] [formula] General formula [] [formula] General formula [] General formula [] General formula [] General formula [] [In the above general formula, Q represents an atomic group necessary to form a heterocycle containing one or more N atoms (including those in which at least one 5- to 6-membered unsaturated ring is fused to this) , A is -SZ' or n _Monovalent heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused)
, B represents an alkylene group having 1 to 6 carbon atoms, M represents a divalent metal atom, and X and X' are =
S, =O or =NR'', R'' represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (a 5- to 6-membered unsaturated ring is at least Y represents [Formula] or [Formula], Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue. group or [Formula], Z' represents Z or an alkyl group, and R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (5 to 6 membered (including _those in _which at _least one _unsaturated ring of
R' each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group. However, R ₄ and R ₅ may represent -B-SZ, and R and R', R ₂ and R ₃ , and R ₄ and R ₅ may each be cyclized to form a heterocyclic residue (5- to 6-membered (including those in which at least one unsaturated ring is fused thereto). R ₆ and R ₇ each represent [Formula] [Formula] or [Formula], and R ₉ is an alkyl group or -(CH ₂ ) n ₈ SO ₃
(however, when R ₈ is −(CH ₂ ) n ₈ SO ₃ , l
represents 0 or 1. ) G is an anion, m ₁ or
m ₄ and n ₁ to n ₈ are each an integer of 1 to 6, m ₅
represents an integer from 0 to 6. R ₈ represents a hydrogen atom, an alkali metal atom, [Formula] or an alkyl group. However, Q' has the same meaning as Q above. D represents a simple bond, an alkylene group or vinylene group having 1 to 8 single primes, and q represents an integer of 1 to 10. A plurality of D's may be the same or different, and the ring formed together with the sulfur atom may be further fused with a 5- to 6-membered unsaturated ring. Note that the compound represented by the above general formula includes enolized compounds and salts thereof. 3. The method for processing a silver halide color photographic light-sensitive material according to claim 2, wherein the compounds represented by the general formulas [] to [] are the following compounds. (a) (b) (c) (d) (e) HS−CH ₂ CH ₂ −COOH (f) (g) (h) (i) (j) (k) (l) (m) (n) (o) (p) (q) (r) (s) (t) (u) or (v) 4. The silver halide color photographic light-sensitive material according to claim 1, 2 or 3, wherein the thickness of the photographic constituent layer of the silver halide color photographic light-sensitive material is 22 μm or less. Processing method. 5. The method for processing a silver halide color photographic material according to claim 4, wherein the thickness of the photographic constituent layer of the silver halide color photographic material is 20 μm or less. 6. The method for processing a silver halide color photographic material according to claim 5, wherein the thickness of the photographic constituent layer of the silver halide color photographic material is 18 μm or less. 7 Each of the silver halide emulsion layers contains 3 mol% to
Claims 1 to 2 are characterized in that they contain silver halide grains containing 25 mol% of silver iodide.
7. The method for processing a silver halide color photographic material according to any one of Item 6. 8. Processing of a silver halide color photographic light-sensitive material according to any one of claims 1 to 7, characterized in that a bleach-fixing process is carried out after color development and after a fixing process. Method.