JPH0576023B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic material, and particularly to a photographic material that improves image stability. More specifically, the present invention relates to a photographic material with improved mold resistance of photographic images. (Background Art) In general, there are a large number of sterilizing and antifungal agents used for sterilizing and preventing fungi, and many of them have been put into practical use (for example, "Mold-proofing Technology" edited by Sanitation Technology Society, published in 1982). However, in the field of silver halide photography, there are not necessarily many things known, and there are many ways to prevent mold and mildew without having any negative effects (image fading, staining, etc.) on silver halide photographic materials or silver halide photographic images. At present, it is difficult to achieve a satisfactory effect. In addition, if processed photosensitive materials are to be used and stored by pasting them on a paper album, a paper mount, or even a paper mount, use adhesive or paper fibers. Mold bacteria adheres to the surface of processed photographic light-sensitive materials, and under storage conditions such as high temperature and high humidity, the mold grows significantly, causing holes in the gelatin in the emulsion, mold color adhesion, and further color development. Another problem was that the image changed color or faded. Formalin, benzoic acid, citric acid, and the like have long been known to have antifungal effects on silver halide photographic images, but these have not always been satisfactory. Also, “Photographic Science &
Engineering Vol.3 May−June 1959 Page
132”, out of about 10 types of anti-mold agents, only pentachlorophenol is said to have an anti-mold effect on color photographic images.However, this compound is harmful to the human body, so it should not be used on processed color prints, etc. Its presence is undesirable for use.Other known antifungal agents for photographic systems include mucochromium compounds (U.S. Pat. No. 2,226,183) and Pyridyl mercuric acetate (U.S. Pat. No. 2,663,639).
No.) Hydantoin and its derivatives (U.S. Patent No.
No. 2762708) Carboxyalkylpentahalobenzenethiol (U.S. Pat. No. 2897081) Chlorine salts or nitrates such as cerium (U.S. Pat. No. 2762708)
No. 3185571) Tosylamido-2-Phenyl-1-
Chloromethyl-ketone (U.S. Patent No. 3503746) Acetal-2-norbornel compound (U.S. Patent No. 3542810) Benzoloxycarbonylphenylalanine and chloromethylketone (U.S. Patent No. 3778276) Antibiotics such as neomycin and kanamycin (UK Patent No. 987010) and benzquidinone (British Patent No. 1065920). However, some of these compounds are expensive and difficult to put into practice, cannot be added directly to photographic processing solutions, are harmful, or are ineffective against some types of mold. It was not put into practical use. Recently, it has been discovered that by adding a 2-thiazolylbenzimidazole compound to a processing solution for silver halide photographic materials, it is possible to suppress the growth of mold on images without adversely affecting the photographic images. 1983-157244, 58-105145). However, this type of compound is generally sparingly soluble in water; for example, 2(-4-thiazolyl)benzimidazole, which has a remarkable antifungal effect, dissolves only 0.003% in water (room temperature), It is not possible to add enough to the processing solution to completely suppress the occurrence of . In some cases, there is also the problem that this fungicide precipitates in the processing solution and adheres to the surface of the photographic light-sensitive material, so the method of adding a fungicide to the processing solution is not always recommended as an anti-mold technology. It wasn't satisfying either. Further, although a certain degree of anti-mold effect can be expected by using a method in which an anti-mold agent is incorporated into a processing solution, problems such as fading of images and generation of stains occur as the photographic light-sensitive material ages. (Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide photographic material having a sufficient anti-mold effect without adversely affecting the silver halide photographic material or the silver halide photographic image. The aim is to prevent the deterioration of photographic images due to mold growth. Furthermore, it is an object of the present invention to provide a silver halide photographic material in which image fading and staining are improved over time. (Means for Solving the Problems) As a result of various studies, the present inventors have determined that at least one of the 2-thiazolylbenzimidazole compound and/or the 2-thiazolylmethylbenzimidazole compound has the following general formula ( )or()
It has been found that the above object can be achieved by incorporating at least one cyan coupler represented by the following into a silver halide photographic light-sensitive material. The details of the present invention will be explained below. We investigated the image stability and mold resistance of silver halide photographic materials by adding various mold inhibitors, including those that showed good performance when added to processing solutions, and found that the following general formula () was obtained. It has been found that the expressed compound exhibits good antifungal effects without adversely affecting photographic images.

[Chemical formula] In the formula, R ₁ represents a hydrogen atom, an alkyl group, or an aryl group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, a nitro group, a carboxyl group, a sulfo group,
Represents a sulfamoyl group, hydroxy group, halogen atom, alkoxy group or thiazolyl group. In the formula, n represents 0 or 1. In the formula, Z represents an atomic group constituting a thiazolyl ring. R ₁ is preferably a hydrogen atom, R ₂ is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an amino group,
A nitro group, a sulfonic acid group, a halogen atom, a hydroxy group, n is 0, and the thiazolyl ring represented by Z is preferably

[Formula]. 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.

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[Chemical formula] Among these specific compounds, Compound-1 is particularly excellent in both image stability and mold resistance. The photographic materials used in the present invention include:
Examples include color photographic paper, color negative film, color reversal film, color reversal photographic paper, black and white photographic paper, micro film, black and white film, lithographic film, and X-ray film. Even if the compound represented by the general formula () is added to any of the silver halide emulsion layer, gelatin intermediate layer, or protective colloid layer of these sensitive materials, or to multiple of these layers, an antifungal effect can be observed. It is desirable to add it to the top protective colloid layer (including the adjacent UV absorbing layer) that has the opportunity to come into direct contact with mold. When it is included in the protective layer including the adjacent ultraviolet absorbing layer, it is preferable in terms of suppressing the increase in yellow stain due to long-term light irradiation and further preventing fading of the image. The amount of the compound represented by the general formula () added to the photosensitive material is preferably 0.1 [mg/m ² ].
~300 [mg/ ^m2 ], particularly preferably 1 [mg/ ^m2 ]~
50 [mg/m ² ]. When incorporating the mold inhibitor represented by the general formula () into a photographic light-sensitive material, methanol,
It is preferable to add the compound dissolved in an organic solvent such as ethanol, ethylene glycol, diethylene glycol, triethylene glycol, benzyl alcohol, ethanolamine, diethanolamine, triethanolamine, or in the form of an emulsion (as an emulsion). 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. Namely, Aspergillus niger, Aspergillus
gracilis, Aspergillus penicilloides, Pullularia
pullulans, Chaetomium globosum,
Cladosporium resinae, Aspergillus flavus,
Aspergillus oryzac, Penicillium citrinum,
Penicillium luteum，Trichoderma uiride，
Aspergillus restrictus, Aspergillus glaucus,
Chrysosporium，Aspergillus versirolor，
Eurotium rubrum，Eurotium tonophilum，
Such as Arthrium Pestalotia. In the present invention, the compound of the general formula () is contained in a photographic light-sensitive material, but when the photographic light-sensitive material is a color photographic light-sensitive material containing a coupler, the stability of the image dye differs depending on the coupler used. Using a coupler of general formula () or () below as a cyan dye-forming coupler
This is particularly preferred since the stability of the image is further improved.

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[Chemical formula] In the formula, R ¹ , R ² and R ⁴ represent a substituted or unsubstituted aliphatic, aryl, or heterocyclic group, and R ³ and R ⁶ represent a hydrogen atom, a halogen atom, an aliphatic group, an aryl group, or an acylamino group. group or R ³ represents a nonmetallic atom group forming a nitrogen-containing 5- to 6-membered ring together with R ² , R ⁵ represents an optionally substituted alkyl group having at least 2 carbon atoms, and Z ₁ and Z ₂ represents a hydrogen atom or a group capable of leaving during an oxidative coupling reaction with a developing agent, and n is 0
Or represents 1. The aliphatic group mentioned herein refers to a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group. In general formula () and general formula (), R ¹ ,
R ² and R ⁴ are aliphatic groups having 1 to 32 carbon atoms (e.g.
methyl group, butyl group, tridecyl group, cyclohexyl group, allyl group, etc.), aryl group (e.g.
phenyl group, naphthyl group), or heterocycle (e.g. 2-pyridyl group, 2-imidazolyl group, 2
-furyl group, 6-quinolyl group, etc.);
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 groups (e.g.
butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy 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 groups (e.g., phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl groups (e.g., methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio groups (e.g., ethylthio group, phenylthio group, etc.) ), hydroxy group, cyano group, carboxy group,
It may be substituted with a group selected from a nitro group, a sulfo group, a halogen atom, etc. In the general formula (), R ³ represents a hydrogen atom, a halogen atom, an aliphatic group, an aryl group, an acylamino group, or a group of nonmetallic atoms that together with R ² form a nitrogen-containing 5- to 6-membered ring. The substituents that can be substituted here may be substituted with the optional substituents described for R ¹ . In the general formula (), n represents 0 or 1. In the general formula (), R ⁵ 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 (), R ⁶ represents a hydrogen atom, a halogen atom, an aliphatic group, an aryl group, or an acylamino group. In general formula () and general formula (), Z ₁ and Z ₂ each represent a hydrogen atom or a coupling-off group, examples of which include halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkoxy groups (e.g., ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy group (e.g., 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group,
Tetradecanoyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (e.g., dichloroacetylamino group, heptafluorobutylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (e.g.,
ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, tetrazolylthio group, etc.) , an imide group (eg, succinimide group, hydantoinyl group, etc.), an aromatic azo group (eg, phenylazo group, etc.), and the like.
These leaving groups may include photographically useful groups. In the general formula (), R ¹ is preferably an aryl group or a heterocyclic group, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, More preferably, it is an aryl group substituted with a sulfamide group, an oxycarbonyl group, or a cyano group. In the general formula (), when R ³ and R ² do not form a ring, R ² is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group,
R ³ is preferably a hydrogen atom. In the general formula (), R ⁴ 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 ⁵ 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 ⁵ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms. In the general formula (), preferred R ⁶ is a hydrogen atom,
Among the halogen atoms, chlorine atoms and fluorine atoms are particularly preferred. Preferred Z ₁ in general formulas () and ()
and Z ₂ are hydrogen atom, halogen atom,
They are an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group. In the general formula (), Z ₂ is preferably a halogen atom, and particularly preferably a chlorine atom or a fluorine atom. In general formula (), when n=0, Z ₂ is more preferably a halogen atom, a chlorine atom,
Fluorine atoms are particularly preferred. Specific compounds included in general formula () or () are listed below, but the present invention is not limited thereto.

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##STR1## The coupler represented by the general formula () or () is usually used in a silver halide emulsion layer, especially in a red-sensitive emulsion layer. In addition, the amount added is 5×10 ^-4
It is preferable to set the amount to 12×10 ⁻⁴ mol/m ² .
Examples of the light-sensitive material used in the present invention include color negative film, color reversal film, color photographic paper, 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. 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 may have regular crystal structures such as cubes, octahedrons, tetradecahedrons, and rhombidodecahedrons, or may have irregular crystal structures such as spherical, plate-like, etc. (irregular) crystals, or a composite form of these crystal forms. 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 the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. 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
Grundlagen der Photographischen Prozesse
mit Silberhalogeniden” (Ak9demische
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, Ir,
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 specific 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, high contrast , 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 alkylaryl 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 esters 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 surfactant; amino acids,
Aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines,
Amphoteric surfactants such as amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphoniums or sulfoniums containing aliphatic or heterocyclic rings. Cationic surfactants such as salts 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 accelerating development. compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. 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., US Pat. No. 2,933,390
No. 3,635,721), aromatic organic acid formaldehyde condensates (e.g., US Pat.
3743510), cadmium salts, azaindene compounds, etc. US patent
No. 3615613, No. 3615641, No. 3617295, No. 3615613, 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, pyrazolone benzimidazole couplers, cyanoacetylcoumaron couplers, open-chain acylacetonitrile couplers, etc., and yellow couplers include,
Examples include acylacetamide couplers (eg, benzoylacetanilides, pivaloylacetanilides), and cyan couplers such as 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. It may also be a colored coupler that has a color correction effect, or a coupler that releases a development inhibitor or development accelerator during development (so-called DIR coupler or DAR coupler). 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-).

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[Chemical Formula] In the formula, R ⁷ and R ⁸ represent a substituted or unsubstituted phenyl group, R ⁹ represents a hydrogen atom, an acyl group, or an aliphatic or aromatic sulfonyl group, and R ¹⁰ represents hydrogen or a substituent. where 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 ⁷ , R ⁸ or Y ₁ , R ¹⁰ , 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-) will be shown.

【formula】

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embedded image The yellow coupler used in the present invention is preferably one represented by the following general formula (Y).

embedded image In the formula, R ¹¹ represents an N-phenylcarbamoyl group which may have a substituent, and X represents a coupling-off group. The substituents for R ¹¹ (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, alkylureido group, alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamido group, arylsulfamoyl group group, arylsulfonamide group, arylureido group, carboxy group, sulfo group, nitro group, cyano group, 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, for example,
-), (Y-), (Y-) or (Y-).

embedded image R ₂₀ represents an optionally substituted aryl group or heterocyclic group.

【formula】

[Formula] R ¹³ and R ¹⁴ 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.

[C] 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-).

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[Chemical formula] In the formula, R ¹⁵ and R ¹⁶ are each a hydrogen atom, an alkyl group,
Represents an aryl group, alkoxy group, aryloxy group or hydroxy group, R ¹⁷ , R ¹⁸ and R ¹⁹
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.

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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, dioctyl butyl 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. di- butoxyethyl succinate, dioctyl azelate), phenols (e.g. 2,
High boiling point organic solvents with a boiling point of 160°C or higher such as (4-di(t)amylphenol), lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl Boiling point of acetate, methyl cellosolve acetate, etc. 30℃
After dissolving in a low boiling point organic solvent of ~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. In the present invention, when using a magenta coupler and a cyan coupler, the amount of high boiling point solvent is determined from the viewpoint of solubility or 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 at 10 ^-4 mol/m ² to 6 x 10 ^-4 mol/m, and for cyan couplers to 5 x 10 ^-4 mol/m to 12 x 10 ^-4 mol/m ² . The photographic light-sensitive 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 (such as 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 dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, 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 coupler 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.

[Chemical formula] In the formula, R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ 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 containing at least one of substituted or nitrogen represents a 6-membered heterocyclic group,
R ²³ and R ²⁴ may be ring-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.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[ka]

[ka]

【formula】

[ka]

[ka]

[ka]

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 and Bull.Soc.Sci.Phot.Japan, No. 16,
Enzyme-treated gelatin as described in P30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. For photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. Further, the treatment temperature is usually selected between 18°C and 50°C, but it may be lower than 18°C or higher than 50°C. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied. The black and white developer contains known developing agents such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), and aminophenols (e.g. N-methyl-p-aminophenol). They can be used alone or in combination. 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. In addition, LFA Meson's “Photography
"Processin Chemistry", Focal Press (1966), pp. 226-229, U.S. Patent 2193015
No. 2,592,364, JP-A-48-64933, etc. may be used. The developer may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates;
Development inhibitors or antifoggants such as bromides, iodides, and antifoggants can be included. If necessary, water softeners, preservatives such as hydroxylamine, benzyl alcohol,
Organic solvents such as diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone. , a viscosity imparting agent, a polycarboxylic acid chelating agent as described in US Pat. No. 4,083,723, an antioxidant as described in OLS No. 2,622,950, and the like. When color photographic processing is performed, the photographic light-sensitive material after color development is usually bleached. The bleaching process is
The fixing process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (),
Compounds of polyvalent metals such as cobalt (), chromium (), copper (), peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-
Aminopolycarboxylic acids such as propanoltetraacetic acid; complex salts of organic acids such as citric acid, tartaric acid, and 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 solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
- Bleaching accelerator described in No. 8836, etc., JP-A-53-
In addition to the thiol compound described in No. 65732, various additives can also be added. 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 liquid used in the stabilization process generally has a pH of 3.
-7 (preferably 3-5) buffer solutions.
As the buffer, citrate buffer, acetate buffer, etc. are usually used. The stabilizing solution may contain formalin, organic solvents, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, etc., and disinfectants or preventive agents to prevent the growth of various bacteria, algae, mold, etc. It may contain a bactericide, a hardening agent such as a magnesium salt or an aluminum salt, a surfactant, a fluorescent whitening agent, etc. to prevent drying load and unevenness. Furthermore, “Water Quality Criteria” by LE West, Phot.Sci.and Eng.
The additives described in Vol. 9, No. 6 (1965) and the like can be used. (Effect of the invention) By incorporating the compound represented by the general formula () into photographic light-sensitive materials, it has become possible not only to significantly prevent the growth of mold, but also to reduce the yellow stain caused by long-term light irradiation. It was possible to obtain excellent effects that cannot be seen with the processing liquid addition method, such as prevention of color increase and fading of image dyes. Further, when cyan couplers of general formula () or () are used as cyan couplers used in photographic light-sensitive materials, image stability can be significantly improved. The present invention will be explained in more detail with reference to Examples below. Example 1 A color photographic material (Sample A) was prepared by coating the first layer (lowest layer) to the seventh layer (top layer) on polyethylene laminated paper as shown in Table 1. The coating solution for the first layer was prepared as follows. In other words, 100 g of yellow coupler (Y) shown in Table 1 was mixed with 166.7 g of dibutyl phthalate (DBP).
ml and 200 ml of ethyl acetate, and this solution was dissolved in 1
% sodium dodecylbenzenesulfonate aqueous solution
This emulsified dispersion was then mixed with 1450 g of a blue-sensitive silver chlorobromide emulsion (80 mol% Br) (containing 66.7 g of Ag) to prepare a coating solution. Coating solutions for the other layers were prepared in the same manner.
As a hardening agent for each layer, 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 x 10 ^-4 mol per mol of silver halide) ×
(10 ^-4 mol) The following dyes were used as anti-irradiation dyes in each emulsion layer. Green-sensitive emulsion layer;

[ka] red-sensitive emulsion layer;

Chemical structures of the color-forming coupler C-a, anti-fading agents A and B, and solvent names of each color-sensitive layer in Table 1 are as follows. C-a;

[ka] (Cyan coupler) A;

[ka] (Anti-fading agent) B;

[ka] (Anti-fading agent) DBP;

[C] TOP; (C ₈ H ₁₇ O) ₃ −P=O

[Table] Next, samples B, C, and D are the same as sample A in which the fungicide I-1 according to the present invention is added to the seventh protective layer, and sample E is the same as sample A in which the fungicidal agent I-1 according to the present invention is added to the protective layer. −
Sample F contains I-4 in the fifth red-sensitive layer.
1 was added. As a comparative example, a conventionally known fungicide, pentachlorophenol, was
-17.5 mg/m ² A sample prepared by adding it to the protective layer in an equimolar amount is designated G, and a sample prepared similarly using butyl p-hydroxybenzoate is designated H. Table 2 shows the amount of each antifungal agent added. After exposing these samples A to H using a Fuji Color Head 690 enlarger (manufactured by Fuji Photo Film Co., Ltd.) (so that the color density after development becomes gray 1.0), the following processing step (I) was carried out. The film was developed using the following methods. At the same time, a sample was also prepared which was subjected to the same development process without being exposed to light. Next, in the same way as sample A, I-1 was added to the bleach-fix solution in processing step (I) for 30 minutes, either after being exposed to light or unexposed.
ml/added and treated is designated as Sample I. Processing process Temperature 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 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 1000ml PH (25℃) 10.00 Bleach-fix 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

[Table] Among the samples thus prepared, unexposed samples A to I were subjected to a mold resistance test. The mold that grows on color paper is cultured on potato dextrose agar medium, and the spores are collected and
A spore suspension with a concentration of 10 ⁶ spores/ml was prepared. Drop 0.5 ml of this spore suspension onto the sample and heat at 28°C with humidity.
It was maintained at 95% and the state of mold growth was observed. The observation results are shown in Table 3. The criteria for evaluation were as shown in Table 4.

【table】

[Table] Further, the exposed and unexposed samples A to I, which had been developed as described above, were irradiated with light for 6 weeks using a fluorescent lamp to perform a color fading test. Macbeth concentration meter is used to measure concentration.
The experiment was conducted using RD-514 model under blue light, green light, and red light, and the density change of the initial density of 1.0 and the density change of unexposed white fruit were determined. The results are shown in Table-5.

[Table] Wasu.
As is clear from the results in Table 3, compared to conventional fungicides, by incorporating the compound of the general formula () into the silver halide photographic light-sensitive material according to the present invention, silver halide photographic light-sensitive materials The mold resistance of the material has been greatly enhanced. In particular, in samples C and D, no mycelial growth was observed. Moreover, the anti-mold effect of the present invention is remarkable even when compared to a treatment solution added based on a known method. It can be said that it was possible to provide a photosensitive material having satisfactory mold resistance only by incorporating the antifungal agent represented by the general formula () into the photosensitive material. Furthermore, the photofading test results in Table 5 show the extent of fading or the rate of increase in stain for the sample containing a moldproofing agent according to the present invention compared to the comparative sample (A) in which no moldproofing agent was used. No difference was observed in the treatment solution, and the increase in fading and staining was small compared to those in which Compound-1 was added to the treatment solution and in those in which a known antifungal agent was used. As shown in the results in Tables 3 and 5, by incorporating a fungicide represented by the general formula () into a silver halide photographic light-sensitive material, a light-sensitive material with a sufficient fungicidal effect can be produced. I can do it.
Furthermore, according to the method of the present invention, it is possible to greatly improve the mold resistance of silver halide color photographic materials, where fading and increased staining are particularly problematic, without adversely affecting image storage stability. I can do it. In the above sample C, cyan coupler C-a
Sample J was prepared in the same manner except that cyan coupler C-5 was used instead of. The previously prepared samples A and C and sample J were exposed and developed in the same manner as in I) so that the developed cyan density was 1.0.
After that, 1.0ml of mold spore suspension was added dropwise and heated to 28℃.
A mold resistance test was conducted for an even longer period (50 days) in an environment with 95% humidity. Table 6 shows the results of mold resistance and cyanide concentration changes. Changes in cyan concentration were determined using a Macbek densitometer by measuring the area where mycelia grew from the area where the mold spore suspension was dropped under red light. Furthermore, mold resistance was evaluated in the same manner as above.

[Table] As is clear from Table 6, for Comparative Example A
Sample C in which TBZ was added to the photosensitive material had a large antifungal effect, and as a result, the decrease in cyan concentration was small. Furthermore, in sample J in which cyan coupler C-5 was introduced, the change in cyan concentration was even smaller. As described above, silver halide photographs with excellent mold resistance and image storage stability are more preferably obtained by incorporating a fungicide into a light-sensitive material according to the present invention and further introducing a cyan coupler represented by the general formula or formula of the present invention. It became clear that photosensitive materials could be provided.

Claims (1)

[Scope of Claims] 1 At least one 2-thiazolylbenzimidazole compound and/or 2-thiazolylmethylbenzimidazole compound and the following general formula ()
A silver halide photographic material containing at least one cyan coupler represented by: [Formula] In the formula, R ⁴ represents a substituted or unsubstituted alkyl or aryl group, R ⁵ represents an alkyl group having 2 to 15 carbon atoms, R ⁶ represents a hydrogen atom or a halogen atom, and Z ₂ represents hydrogen Represents a group that can be separated during an oxidative coupling reaction with an atom or a developing agent.