JPH0417420B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and in particular, to prevent mold from adhering to and multiplying on processed photographic light-sensitive materials, and preventing discoloration of attached areas. The present invention relates to a method for processing a silver halide color photographic light-sensitive material. (Prior Art) In many cases, processed photosensitive materials are used and stored by pasting them on paper albums, paper mounts, or paper mounts. In this case, mold adheres to the surface of the processed photographic light-sensitive material from the adhesive and paper fibers, and under storage conditions such as high temperature and humidity, the mold grows significantly and the gelatin film on the surface of the photographic light-sensitive material deteriorates, causing the image to deteriorate. There were problems such as deterioration or discoloration of mold-attached areas. Generally, silver halide color photographic light-sensitive materials are stored for a long period of time, and if mold grows during the storage period, this will be a fatal drawback. In order to eliminate these drawbacks, techniques for adding benzoic acid, formalin, citric acid, etc. to photographic light-sensitive material processing solutions have been known, but the results have not been sufficiently satisfactory for practical use. Known antifungal agents for photography include mucochromium compounds (U.S. Patent No. 2,226,183) and pyridyl marquelacetate (U.S. Pat. No. 2,226,183).
No. 2,663,639), hydantoins and their derivatives (US Pat. No. 2,762,708), carboxyalkylpentahalobenzenethiol (US Pat. No. 2,897,081), cerium hydrochlorides or nitrates (US Pat. No.
3185571), tosylamide-2-phenyl-1-
Chloromethyl ketone (U.S. Patent No. 3503746), acetal-2-norbornel compound (U.S. Patent No.
3542810), benzoxycarbonylphenylalanine and chloromethyl ketone (US Pat. No. 3778276)
), antibiotics such as neomycin and kanamycin (British Patent No. 987010), and benzquidinones (British Patent No. 1065920). However, some of these compounds have not been put into practical use because they are expensive, harmful, or ineffective. Recently, a technique for adding a 2-thiazolylbenzimidazole compound to a processing solution has been developed in JP-A-57-
157244, disclosed in Japanese Patent Application Laid-Open No. 58-105145. Although this technology was certainly superior to previously known technology in terms of suppressing the growth of mold, it had no effect on the discoloration of mold-adhered areas and was completely inadequate for practical use. It was hot. The present inventors have conducted various tests to determine how to prevent images on color photographic materials from deteriorating due to mold, and have found that in order to obtain results that are fully satisfactory in practice, it is necessary to prevent the growth of mold after it has adhered. We have come to the conclusion that it is necessary to achieve two points: preventing discoloration of mold-adhered areas.

[Problem to be solved by the invention]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is, first, to provide a method for processing silver halide photographic materials that suppresses image deterioration due to light, heat, and humidity. A second object is to provide a method for processing silver halide photographic materials that prevents mold from attaching and growing during storage. A third object is to provide a method for processing silver halide photographic materials that prevents mold from attaching and discoloring the moldy areas during storage.

[Means to solve the problem]

As a result of various studies, the present inventors have found that a silver halide color light-sensitive material containing at least one coupler represented by the general formula [] can be used in a photographic processing solution containing at least one compound represented by the general formula [] It has been found that the above objective can be achieved by treating with. General formula [] In the formula, R ¹ represents a substituted or unsubstituted aliphatic group or aryl group, R ³ represents a hydrogen atom, a halogen atom, an aliphatic group, an aryl group, or an acylamino group, and R ² represents a group having at least 2 or more carbon atoms. It represents an alkyl group that may be substituted, and Z ₁ represents a hydrogen atom or a group that can be separated during an oxidative coupling reaction with a developing agent. The aliphatic group mentioned herein refers to a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. In the general formula [], R ¹ is an aliphatic group having 1 to 32 carbon atoms (e.g., methyl group, butyl group, tridecyl group, cyclohexane group, allyl group, etc.) or an aryl group (e.g., phenyl group, naphthyl group, etc.)
represents an alkyl group, an aryl group,
Heterocyclic groups, alkoxy groups (e.g. methoxy groups,
2-methoxyethoxy group, etc.), aryloxy group (e.g., 2,4-di-tert-amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, etc.), alkenyloxy group (e.g.,
2-propenyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group) group, etc.), amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g.,
dipropylsulfamoylamino group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (e.g., methanesulfonyl group, (e.g., phenylsulfonyl group), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroxyl group, cyano group, carboxy group, nitro group, sulfo group, halogen atom, etc. You may do so. In the general formula [], R ² is an optionally substituted alkyl group having at least 2 carbon atoms (e.g., ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenylthiomethyl group,
dodecyloxyphenylthiomethyl group, butanamidomethyl group, methoxymethyl group, etc.). In the general formula [], Z ₁ each represents a hydrogen atom or a coupling-off group, examples of which include halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, etc.), alkoxy groups (e.g., ethoxy group, dodecyl group, etc.) oxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy group (e.g., 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.) ), acyloxy groups (e.g.
acetoxy group, tetradecanoyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (e.g., dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.),
Aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy groups, etc.), fatty acid or aromatic thio groups (e.g., ethylthio groups, phenylthio groups, tetrazolylthio groups, etc.), imide groups (e.g., succinimide groups, hydantoinyl groups, etc.), Examples include aromatic azo groups (for example, phenylazo groups, etc.). These leaving groups may include photographically useful groups. In the general formula [], R ¹ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group. In the general formula [], preferable R ² has 2 carbon atoms
A methyl group having an alkyl group of from 15 to 1 and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group. In the general formula [], R ² is more preferably an alkyl group having 2 to 15 carbon atoms, and particularly preferably an alkyl group having 2 to 4 carbon atoms. In the general formula [], preferred R ³ is a hydrogen atom,
Among the halogen atoms, chlorine atoms and fluorine atoms are particularly preferred. Preferable Z ₁ in [] is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, or a sulfonamide group, respectively. In the general formula [], Z ₁ is preferably a halogen atom, and particularly preferably a chlorine atom or a fluorine atom. General formula [] In the formula, R ₄ represents a hydrogen atom or an alkyl group, and R ₅ represents a hydrogen atom, an alkyl group, a nitro group, or a halogen atom. m represents 0 or 1. Q represents an atomic group constituting a thiazolyl ring. R ₄ is preferably a hydrogen atom, R ₅ is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a nitro group,
The halogen atom, m is preferably 0, and the thiazolyl ring represented by Q is preferably

[Formula]. Specific compounds included in the general formula [] of the present invention are listed below, but the present invention is not limited thereto. The coupler represented by the general formula [] is usually used in silver halide emulsion layers, especially in red-sensitive emulsion layers. In addition, the amount added is 5×10 ^-4 to 12×10 ^-4
Preferably it is set at mol/m ² . Specific examples of compounds represented by the general formula [] included in the present invention are shown below, but the present invention is not limited thereto. As the processing solution to which the compound represented by the general formula [] is added, any processing solution (processing bath) commonly used in the processing of silver halide light-sensitive materials can be used. liquid (hereinafter referred to as anti-mold treatment liquid)
It may be. Usually, processing solutions for silver halide photosensitive materials include, for example, a developer (black and white developer, color developer, etc.), a fixer, a bleach solution, a bleach-fix solution, a stop solution,
Examples include a washing liquid, a stabilizing liquid, a neutralizing liquid, a pre-hardening liquid, and a post-development hardening liquid. Considering the adhesion efficiency to silver halide photographic materials, the liquid to which the above compound is added may be a stabilizing liquid, a washing liquid, or a processing liquid used in the final bath or a bath near the end (e.g., a washing liquid, a stabilizing liquid, etc.). It is preferable to use it in an anti-fungal treatment solution provided at the end of a conventional treatment process. The amount of the compound represented by the general formula () to be added to these processing solutions is preferably
0.1mg to 300mg, particularly preferably 1mg to 100mg
mg. When adding the mold inhibitor represented by the general formula () to various treatment solutions, organic solvents such as methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, benzyl alcohol, ethanolamine, diethanolamine, triethanolamine, etc. It is preferable to add it by dissolving it in. The compound represented by the general formula [] of the present invention is
Although it is effective against all mold species that occur in silver halide photographic images, it is particularly effective against the following mold species. i.e. Aspergillus niger, Pullularia
pullulans, Chaetomium globosum,
Cladosporium resinae, Aspergillus flavus,
Aspergillus oryzae, Penicillium citrinum,
Penicllium iuteum, Trichoderma uiride,
Aspergillus restrictus, Aspergillus glaucus,
Chrysosporium, Aspergillus versirolor,
Eurotium rubrum, Eurotium tonophilum,
Such as Arthrium Pestalotia. Any known method can be used for the photographic processing of the present invention. A known treatment liquid can be used. For example, Research Disclosure No. 176 No. 28~
What is described on page 30 (RD-17643). Processing temperatures are usually carried out between 18°C and 50°C, but temperatures below 18°C or above 50°C may be used. Conventional methods for forming dye images can be applied. Negative-positive method (e.g. “Journal of the Society
of Motion Picture and Television Engineers
61 (1953), pp. 667-701);
A color system in which a negative silver image is produced by development with a developer containing a black and white developing agent, followed by at least one uniform exposure or other suitable fogging treatment, followed by color development to produce a dye-positive image. Reversal method: A silver dye bleaching method is used in which a photographic emulsion layer containing a dye is exposed and developed to form a silver image, and this is used as a bleaching catalyst to bleach the dye. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino- N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamide ethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966)
pages 226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or antifoggants such as bromides, iodides and organic antifoggants. can. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium borohydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, US Pat. No. 4,083,723
It may also contain a polycarboxylic acid chelating agent described in No. 1, an antioxidant described in OLS No. 2622950, and the like. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (), cobalt (), chromium (), and torso ().
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used. For example, ferrician compounds, dichromates, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid. , complex salts of organic acids such as malic acid; persulfates, permanganates; nitrosophenols, and the like can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solutions include
U.S. Patent No. 3042520, U.S. Patent No. 3241966, Special Publication No. 1977-
In addition to the bleaching accelerators described in Japanese Patent Publication No. 8506 and Japanese Patent Publication No. 45-8836, and the thiol compounds described in Japanese Patent Application Laid-Open No. 53-65732, various additives can also be added. The developer used when subjecting the color reversal light-sensitive material to black-and-white photographic processing may contain known developing agents. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3
-pyrazolidones (e.g. 1-phenyl-3-
pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid, and the 1,2,3,4-tetrahydroquinoline ring and indolene described in U.S. Pat. No. 4,067,872. Heterocyclic compounds in which rings are condensed can be used alone or in combination. The developer generally contains other known preservatives, alkaline agents, PH buffers, antifoggants, etc., and if necessary, a solubilizing agent,
It may also contain a toning agent, a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, and the like. Usually washed with water after bleach-fixing or fixing.
Processes such as stabilization-drying, water washing-drying, and stabilization-drying are performed. Here, in the water washing and stabilization steps, by using a multi-stage countercurrent method (for example, 2 to 5 stages) as necessary, the amount of liquid can be reduced and the pollution load can be reduced. The water used in the washing step may be running water, and may contain known additives. For example, inorganic phosphoric acid, aminopolycarboxylic acid,
Chelating agents such as organic phosphoric acid, various bacteria,
It may contain a bactericide or fungicide to prevent the growth of algae, mold, etc., a hardening agent such as magnesium salt or aluminum salt, a surfactant, a buffering agent, etc. to prevent drying load and unevenness. can. Furthermore, “Water Quality” by LEWest
Criteria “Phot.sci, and Eng., Vol.9, No.6
(1965) and others can be used. The stabilizing solution generally consists of a low PH (eg PH 3-5) buffer. As the buffer solution, citrate buffer, acetate buffer, etc. are usually used. Such stabilizers usually contain surfactants, organic solvents (e.g.
A chelating agent (diethanolamine, methanol, ethanol, etc.) is added, and if necessary, a fluorescent brightener, a hardening agent (eg, potash alum, etc.), etc. are added. This treatment liquid is normally used at a treatment temperature of 20 to 60°C and a treatment time of 3 seconds to 2 minutes. The British Journal of Photography, September 27, No. 838 (1968) or Journal of the SMPTE, Vol. 61, No. 12,
When the compound represented by the general formula () of the present invention is added to a stabilizing solution used in a stabilizing bath as described on page 667 (1963), the light fastness and mold resistance of color photographic images are particularly improved. The stability of color photographic images is significantly improved. As the antifungal treatment liquid, any solution can be used as long as it contains a compound represented by the general formula [] and does not contain any compounds that would adversely affect photographic performance. The pH of such a solution is preferably about 3.5 to 8.
The processing temperature of this processing liquid is usually 20 to 60℃.
The processing time used is 3 seconds to 2 minutes. The photographic materials used in the present invention include:
Examples include color photographic paper, color negative film, color reversal film, and color reversal photographic paper. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the photosensitive silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. Preferred silver halide is 15 mol%
Contains the following silver iodide. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
Expressed as an average based on projected area. ) is not particularly limited, but is preferably 3μ or less. The particle size distribution may be narrow (so-called "monodisperse") or broad. Silver halide grains in photographic emulsions are cubic,
They may have regular crystal bodies such as octahedrons, tetradecahedrons, and rhombic dodecahedrons, or may have irregular crystal bodies such as spherical, plate-shaped, etc. It may be a composite form of crystalline form. It may also consist of a mixture of particles of various crystalline forms. Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area. Details are described in the specifications of JP-A-58-127921 and JP-A-58-113927. The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.
Further, the particles may be particles in which a latent image is formed as a seed on the surface, or may be particles in which a latent image is mainly formed inside the particle. The photographic emulsion used in the present invention is written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include one-sided mixing method, simultaneous mixing method,
Any combination thereof may be used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example “Die
Grundlagender Photogra−phischen Prozesse
mit Silber−halogeniden” (Akademische
Verlagsgesellschaft, 1968) pages 675-734 can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) reduction sensitization method;
Noble metal compounds (e.g., gold complex salts, Pt, It, etc.)
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,
3a, 7) tetraazaindenes), pentaazaindenes, etc.; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. can be added. For more detailed examples of these and how to use them, see, for example, U.S. Pat. No. 3,954,474;
Those described in No. 3982947 and Japanese Patent Publication No. 52-28660 can be used. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, hard contrast control). , sensitization)
Various surfactants may be included for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid ester acids of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinic acid Contains acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Anionic surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts Cationic surfactants such as heterocyclic quaternary ammonium salts such as , pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or promoting development. compounds, urethane derivatives, urea derivatives,
It may also contain imidazole derivatives, 3-pyrazolidones, and the like. For example, U.S. Patent No. 2400532,
No. 2423549, No. 2716062, No. 3617280, No.
Those described in No. 3772021, No. 3808003, British Patent No. 1488991, etc. can be used. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, Hydroxyalkyl (meth)
Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied.
These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. US patent
No. 3615615, No. 3615641, No. 3617295, No. 3615615, No. 3615641, No. 3617295, No.
The combination described in No. 3635721 is particularly useful. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. The photographic emulsion layer of the photographic light-sensitive material prepared using the present invention contains a dye-forming coupler, that is, an aromatic primary amine developer (e.g., phenylene diamine derivative, aminophenol derivative, etc.) in the color development process. A compound capable of developing color through oxidative coupling may also be used. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides),
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions. In addition, colored couplers have the effect of color correction,
Alternatively, it may be a coupler (so-called DIR coupler or DAR coupler) that releases a development inhibitor or development accelerator during development. In addition to the DIR coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development. Of course, two or more types of the above-mentioned couplers and the like can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers. The magenta coupler used in the present invention is preferably one represented by the following general formula [M-] or [M-]. In the formula, R ⁹ and R ¹⁰ represent a substituted or unsubstituted phenyl group, R ¹¹ represents a hydrogen atom, an acyl group, or an aliphatic or aromatic sulfonyl group, R ¹² represents hydrogen or a substituent, and Za , Zb and Zc are methine, substituted methine, =N- or -NH
-, and Y ₁ and Y ₂ represent a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized developing agent. Furthermore, R ⁹ , R ¹⁰ or Y ₁ , R ¹² , Y ₂ or a substituted methine such as Za, Zb or Zc may form a dimer or more multimer, and the above aliphatic group , may be branched or cyclic, and may be saturated or unsaturated. Next, typical examples of compounds represented by the general formula [M-] or [M-] are shown. The yellow coupler used in the present invention is preferably one represented by the following general formula (Y). In the formula, R ¹³ represents an N-phenylcarbamoyl group which may have a substituent, and X represents a coupling-off group. Substituents for R ¹³ (N-phenylcarbamoyl group) include well-known substituents for yellow couplers, such as alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, halogen atoms,
Alkoxycarbamoyl group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylurenoide group, alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamido group, arylsulfonamide group It represents a moyl group, an arylsulfonamide group, an arylureido group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, etc. There may be two or more substituents, and in that case they may be the same or different from each other. The coupling-off group of X may be a hydrogen atom, but preferably a coupling-off group forming a 2-equivalent yellow coupler, such as the following general formula
-], [Y-], [Y-] or [Y-]. R ₁₄ represents an optionally substituted aryl group or heterocyclic group. R ¹⁵ and R ¹⁶ are each a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group,
It represents a sulfonic acid group, an unsubstituted or substituted phenyl group, or a heterocycle, and these groups may be the same or different. W ₁ is in the formula

[Formula] represents a nonmetallic atom required to form a 4-, 5-, or 6-membered ring. In the general formula [Y-], preferably [Y-
] to [Y-]. In the formula, R ¹⁷ and R ¹⁸ are each a hydrogen atom, an alkyl group,
Represents an aryl group, alkoxy group, aryloxy group or hydroxy group, R ¹⁹ , R ²⁰ and R ²¹
each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group, and W ₂ represents an oxygen or sulfur atom. Next, typical examples of compounds represented by the general formula [Y] will be shown. In the present invention, in order to introduce the couplers of the present invention into the emulsion layer, for example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, etc.) are used. oxphate, dioctylbutyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate). , dioctyl acelate), phenolic agents (e.g. 2,
Boiling point of 4-di(t)amylphenol) 160
High boiling point organic solvents above °C, such as ethyl acetate,
Boiling points of lower alkyl acetates such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. 30
After dissolving in a low-boiling organic solvent at a temperature of 150°C to 150°C, it is dispersed in a hydrophilic colloid, and this is mixed with a silver halide emulsion. At this time, a mixture of a high boiling point organic solvent and a low boiling point organic solvent may be used. When using a yellow coupler in the present invention, it is preferable to adjust the weight ratio of the high boiling point organic solvent to the yellow coupler to 1.0 or less, particularly 0.1 to 0.8. When a magenta coupler and a cyan coupler are used in the present invention, the amount of high boiling point solvent is determined from viewpoints such as solubility and developability. Usually, the high boiling point organic solvent is set in a range of 10% to 300% based on the weight of the magenta coupler or cyan coupler. In the color photographic light-sensitive material of the present invention, the coating amount of the silver halide emulsion can be freely set depending on the purpose, but it is preferably 200 mg/m 2 to 500 mg/m 2 in the blue-sensitive emulsion layer and 200 mg/m ² to 500 mg/m ² in the green-sensitive emulsion layer in terms of Ag. 100 mg/m ² to 300 mg/m ² in the sensitive emulsion layer, 150 mg/m 2 in the red sensitive emulsion layer
Usually set at ~400mg/ ^m2 . Also, the amount of coupler applied is 5 x 10 ^-4 mol/m ² ~ for yellow coupler.
12×10 ^-4 mol/m ² , 2× for magenta coupler
It is preferably set to 10 ⁻⁴ mol/m ² to 6×10 ⁻⁴ mol/m ² , and for cyan couplers to 5×10 ⁻⁴ mol/m ² to 12×10 ⁻⁴ mol/m ² . The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,3-dihydroxydioxane, etc.), (4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. In the photosensitive material produced using the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc., they may be mordanted with a cationic polymer or the like. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those described in U.S. Pat.
3314794 and 3352681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat. No. 3705805 and 3707375), butadiene Compounds such as those described in US Pat. No. 4,045,229 or benzoxide compounds (such as those described in US Pat. No. 3,700,455) can be used. Additionally, U.S. Patent 3499762
The material described in JP-A-54-48535 can also be used. UV-absorbing couplers (e.g. α
- naphthol-based cyan dye-forming couplers),
A UV-absorbing polymer or the like may also be used. These ultraviolet absorbers may be mordanted in specific layers. In the color photographic material used in the present invention, it is particularly preferable to use at least one ultraviolet absorber represented by the following general formula (UV) on the red-sensitive silver halide emulsion layer. In the formula, R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ may be the same or different, and each represents a hydrogen atom, a halogen atom,
Nitro group, hydroxy group, alkyl group, alkenyl group, aryl group, alkoxy group, acyloxy group, aryloxy group, alkylthio group, arylthio group, mono- or dialkylamino group, acylamino group, or 5 or 5 containing at least one of oxygen or nitrogen represents a 6-membered heterocyclic group,
R ²⁵ and R ²⁶ may be closed to form a 5- or 6-membered aromatic ring consisting of carbon atoms. Among these groups, those that can have a substituent may be substituted. Representative examples of ultraviolet absorbers used in the present invention are shown below. In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include
Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. As the binder or protective colloid that can be used in the emulsion layer or hydrophilic colloid layer (e.g., protective layer, intermediate layer) of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic Colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. In addition to lime-processed gelatin, acid-processed gelatin, Bull.Soc.Sci.Phot.Japan, No. 16,
Oxygen-treated gelatin as described in P30 (1966) may be used, and gelatin hydrolysates and oxygen-decomposed products may also be used. The present invention will be explained in more detail with reference to Examples below. Example 1 A color photographic material was prepared by coating the first layer (lowest layer) to the seventh layer (top layer) on double-sided polyethylene laminated paper as shown in the table. (Sample A~
G) The coating solution for the first layer was prepared as follows. i.e. the yellow coupler 100 shown in the table
g was dissolved in 70 ml of trinonyl phosphate (TNP) and 200 ml of ethyl acetate, and this solution was emulsified and dispersed in 800 g of a 10% gelatin aqueous solution containing 80 ml of a 1% aqueous solution of sodium dodecylbenzenesulfonate.
Next, this emulsified dispersion was mixed with 1450 g of blue-sensitive silver chlorobromide emulsion (Br 80 mol %) (containing 66.7 g of Ag) to prepare a coating solution. Coating solutions for the other layers were prepared in the same manner. The hardening agent for each layer is 2,
4-dichloro-6-hydroxy-s-triazine sodium salt was used. The following spectral sensitizers were used for each emulsion. Blue-sensitive emulsion layer: 3,3'-di-(γ-sulfopropyl)-selenacyanine sodium salt (2×10 ^-4 mol per mol of silver halide) Green-sensitive emulsion layer: 3,3'-di-( γ-sulfopropyl)-5,5'-diphenyl-9-ethyloxacarbocyanine sodium salt (silver halide 1
Red-sensitive emulsion layer; 3,3'-di-(γ- ^sulfopropyl )-9-methyl-thiadicarbocyanine sodium salt (2.5×10 ^-4 per mole of silver halide)
(mol) The following dyes were used as anti-irradiation dyes in each emulsion layer. Green-sensitive emulsion layer; red-sensitive emulsion layer; a to h in the table and solvent names (TNP, DBP,
The chemical structure of DOP, TCP) is as follows. TNP; ( _C9H19O ) ₃ -P= _O DBP; DOP; TCP; (CH ₃ C ₆ H ₄ O) ₃ -P=O These samples were exposed to light using a Fuji Color Head 690 enlarger (manufactured by Fuji Photo Film Co., Ltd.) (exposure so that the color density after development was gray and 1.0). do)
After that, the film was developed by the following processing steps based on the processing conditions shown in the table. Processing process Density Time Color development 33°C 3 minutes 30 seconds Bleach-fixing 33°C 1 minute 30 seconds Washing 24-34°C 3 minutes Drying 80°C 1 minute The components of each processing solution are as follows. (Color developer; CD-) Water 800ml Sodium tetrapolyphosphate 2.0g Benzyl alcohol 15.0ml Diethylene glycol 10.0ml Sodium sulfite 2.0g Potassium bromide 0.5g Sodium carbonate 30.0g N-ethyl-N-(β-methanesulfonamidoethyl) -3-Methyl-4-aminoaniline sulfonate 5.0g Hydroxylamine sulfate 4.0g Add water to 1000ml PH (25℃) 10.00 (bleach-fix solution; BF-) Water 400ml Ammonium thiosulfate (70% solution) 150ml Sodium sulfite 18g Iron()ammonium ethylenediaminetetraacetate
55g Ethylenediaminetetraacetic acid/2Na 5g Add water 1000ml PH (25℃) 6.70 (Bleach-fix solution; BF-) Water 400ml Ammonium thiosulfate (70% solution) 150ml Sodium sulfite 18g Iron () ammonium ethylenediaminetetraacetate
55g Ethylenediaminetetraacetic acid/2Na 5g Compound (A-1) (Thiabendazole, manufactured by Merck & Co.) 30mg Add water to 1000ml PH (25℃) 6.70 (Stable bath; ST-) Glacial acetic acid 1g 1-hydroxyethylidene -1,1-diphosphonic acid 1g Compound (A-1) (thiabendazole, manufactured by Merck & Co.) 15mg Add water to 1 and pH with acetic acid and potassium hydroxide
Adjusted to 4.20. (Stable bath; ST-) It was prepared in the same manner as ST- except that 30 mg of thiabendazole was added. (Stable bath; ST-) It was prepared in the same manner except that 15 mg of thiabendazole and 15 mg of proxel were mixed and added to ST-. (Stable bath; ST-) A- in place of compound (A-1) in ST-
It was prepared in the same manner except that 32 mg of No. 3 was added.

【table】

【table】

[Table] The stability of the samples obtained by the above treatment over time was investigated in the following manner. That is, after transplanting the mold that had grown on each sample onto various types of wedding photographs with mounts, the samples were aged for 28 days at 40°C and 90% RH.
The status of mold growth was investigated. The results are shown in the table. Also, for each sample, the gray image area (Do=
The storage stability of the cyan dye was determined by measuring the cyan concentration in the red spot, which is the mold-attached area that occurred in 1.0), and the obtained results are shown in the table.

【table】

【table】
Kimono red spot

As shown in the table, the general formula of the present invention []
By including the compound in the processing solution (Processes B to F), the occurrence of mold on prints can be significantly suppressed, and furthermore, the coupler represented by the general formula [] can be incorporated into the color photographic material as a coupler. By using it (Samples C and D), it was possible to significantly improve the problems such as the decrease in cyanide concentration that had occurred in the mold-attached areas. Example 2 In Sample A, which is the photosensitive material of Example 1, C-2, C-10, and C were used instead of cyan couplers a/b.
Sample E using 600 mg/m ² of -4 and C-6 each;
F, G and H were created. Samples E to H thus obtained and Example 1
Samples A and C prepared in Example 1 were exposed and developed in the same manner as in Example 1, and the mold growth and cyan dye storage stability were investigated, and the results are shown in the table. However, the processing conditions were as follows.

[Table] Here, the following stabilizing baths were used. (Stable bath; ST-) ST- was prepared in the same manner except that 32 mg of compound (A-4) was added instead of compound (A-1). (Stable bath; ST-) ST- was prepared in the same manner except that 32 mg of compound (A-5) was added instead of compound (A-1). (Stable bath; ST-) ST- was prepared in the same manner except that 32 mg of compound (A-6) was added instead of compound (A-1). (Stable bath; ST-) ST- was prepared in the same manner except that 32 mg of (A-8) was added instead of compound (A-1).

【table】
Cyan concentration
As is clear from the results shown in the table, by using the cyan coupler represented by the general formula () related to the present invention in combination with the compound represented by the general formula (), the growth of mold can be greatly suppressed. We were able to greatly improve the storage stability of cyan images.

Claims (1)

[Claims] 1. A silver halide color photosensitive material containing at least one coupler represented by the general formula [] is processed with a photographic processing solution containing at least one compound represented by the general formula [] A method for processing a silver halide color photosensitive material, characterized in that: General formula [] (In the formula, R ¹ represents a substituted or unsubstituted aliphatic group or aryl group, R ³ represents a hydrogen atom, halogen atom, aliphatic group, aryl group, or acylamino group, and R ² has at least 2 carbon atoms. represents an optionally substituted alkyl group, and Z ₁ represents a hydrogen atom or a group that can be separated during an oxidative coupling reaction with a developing agent.) General formula [] (In the formula, R ₄ represents a hydrogen atom or an alkyl group. R ₅ represents a hydrogen atom, an alkyl group, a nitro group, or a halogen atom. m represents 0 or 1. Q is an atomic group constituting a thiazolyl ring )