JPH0560580B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel pyrazoloazole magenta coupler. Known couplers commonly used in silver halide color photographic materials include yellow couplers made of open-chain ketomethylene compounds, magenta couplers made of pyrazolone compounds and pyrazoloazole compounds, and cyan couplers made of phenol compounds and naphthol compounds. . Conventionally, pyrazolone compounds have been frequently used as magenta couplers. Known pyrazolone magenta couplers include <U.S. Patent No. 2600788
No. 3519429, Published Patent Publication No. 111631/1983,
It is described in No. 57-35858, etc. However, The theory of the photographic process
process.) Macmillan 4th edition (1977) 356 pages -
358 pages, manufactured by Huain Chemical CMC 14
Volume 8, pp. 38-41, Photographic Society of Japan 1985 Annual Conference (May 23 and 24, 1985, at a private institute building)
As stated on pages 108-110 of the lecture abstract collection,
A dye formed from a magenta coupler consisting of a pyrazolone compound has undesirable side absorption, and improvement thereof is desired. As described in the previous literature, dyes formed from magenta couplers made of pyrazoloazole compounds have no side absorption. This coupler is known to be a good coupler in addition to the documents mentioned above, such as U.S. Pat. No. 3,810,761, U.S. Pat.
It is also described in published patents Sho 59-171956 and Sho 60-97353. However, this excellent coupler also has serious drawbacks, and improvements are desired. A drawback that must be remedied as soon as possible is that the dyes formed from this coupler deteriorate significantly during storage, especially under exposure to light. As a method of preventing the deterioration of pigments, it is known to use UV inhibitors, antioxidants, etc. in combination. For example, published patents No. 125732/1986 and 60-
It is described in issues such as No. 97353. However, the use of these additives is still not sufficient for pyrazoloazole magenta couplers, and improvements are desired. An object of the present invention is to provide a pyrrolotriazole coupler with excellent color-forming properties and a pyrrolotriazole coupler in which the dye formed therefrom has improved light fastness. Another object of the present invention is to have good color reproducibility and
Another object of the present invention is to provide a silver halide color photographic light-sensitive material which also has excellent light fastness. The coupler used in the present invention has the general formula []
It is expressed as General formula [] In the formula, R ₁ is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkylamino group, an anilino group, an acylamino group, a sulfonamide group, a ureido group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group ,
Represents a sulfonyl group, an alkoxy group, an aryloxy group, and _R2 is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carbamoyl group, a thiocarbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group, a cyano group, represents a nitro group or a heterocyclic group; R ₃ represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or an alkoxy group; X represents a hydrogen atom or a coupling reaction with an oxidized color developing agent; represents a group that can be General formula [] In the formula, R ₁ , R ₃ and X represent the same as in the general formula [], and R ₄ is a hydrogen atom, an alkyl group,
Represents an aryl group, acyl group, carbamoyl group, or thiocarbamoyl group. To explain the general formulas [] and [] in more detail, R ₁ is a hydrogen atom, a halogen atom (for example,
chloro atom, bromine atom, etc.), a straight chain or branched alkyl group having 1 to 18 carbon atoms (e.g. methyl group,
iso-propyl group, t-butyl group, dodecyl group, etc.), cycloalkyl group (e.g., cyclopentyl group, cyclohexyl group, etc.), aryl group (e.g., phenyl group, naphthyl group, etc.), alkylamino group (e.g., methylamino group, etc.) group, tetradecylamino group, etc.), anilino group, acylamino group (e.g., acetylamino group, benzamide group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, etc.), ureido group (e.g., methyl ureido group, phenylureido group, etc.), alkoxycarbonylamino group (e.g.
methoxycarbonylamino group, phenoxycarbonylamino group, etc.), alkylthio group (e.g., methylthio group, dodecylthio group, etc.), arylthio group (e.g., phenylthio group, etc.), sulfonyl group (e.g., methanesulfonyl group, benzenesulfonyl group, etc.) ), alkoxy groups (e.g. methoxy groups,
(tetradecyloxy group, etc.), aryloxy group (eg, phenoxy group, etc.), and preferably a hydrogen atom, an alkyl group, or an aryl group. To explain R ₂ in more detail, R ₂ is a hydrogen atom,
Straight-chain or branched alkyl groups having 1 to 18 carbon atoms (e.g., methyl group, dodecyl group, etc.), aryl groups (e.g., phenyl group, naphthyl group, etc.), acyl groups (e.g., acetyl group, benzoyl group, etc.), Carbamoyl groups (e.g., methylcarbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, etc.), thiocarbamoyl groups (e.g., methylthiocarbamoyl group, phenylthiocarbamoyl group, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl group, ethoxycarbonyl group) ), aryloxycarbonyl groups (e.g., phenoxycarbonyl groups, etc.), sulfonyl groups (e.g., methanesulfonyl groups, benzenesulfonyl groups, etc.), cyano groups, nitro groups, heterocyclic groups (e.g., pyridyl groups, triazolyl groups, etc.) quinolyl group, etc.), preferably an acyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonyl group, or cyano group. To describe R ₃ in more detail, R ₃ is a linear or branched alkyl group having 1 to 18 carbon atoms (e.g., methyl group, t-butyl group, pentadecyl group, etc.), a cycloalkyl group (e.g., cyclopropyl group, cyclohexyl group, etc.), aryl group (e.g., phenyl group, naphthyl group, etc.), heterocyclic group (e.g.,
Pyrazolyl group, imidazolyl group, pyrimidyl group,
represents an indolyl group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, etc.), and preferably,
They are an alkyl group and an aryl group. To explain R ₄ in more detail, R ₄ is a hydrogen atom,
Straight-chain or branched alkyl groups having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, etc.), aryl groups (e.g., phenyl group, naphthyl group, etc.), acyl groups (e.g., acetyl group, benzoyl group, etc.), It represents a carbamoyl group (e.g., methylcarbamoyl group, phenylcarbamoyl group, etc.), a thiocarbamoyl group (e.g., methylthiocarbamoyl group, phenylthiocarbamoyl group, etc.), and preferably,
They are an acyl group and a carbamoyl group. _R1 , _R2 , _R3
The _group represented by
dodecyl group, etc.), halogen atoms (e.g., fluorine atom, chlorine atom, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, 2-ethoxyethoxy group, dodecyloxy group, etc.), aryloxy groups (e.g., phenoxy group) , 2,5-di-tert-aminophenoxy group, etc.), alkylthio group (e.g.,
methylthio group, ethylthio group, dodecylthio group, etc.), arylthio group (e.g., phenylthio group,
4-dodecyloxyphenylthio group, etc.), aryl group (for example, phenyl group, 4-dodecylphenyl group, etc.), hydroxy group, carboxy group, sulfo group, etc. Examples of the group that can be separated by a coupling reaction with the oxidized color developing agent represented by X include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group,

[Formula] (Z represents a group of atoms necessary to form a 5- or 6-membered ring with a nitrogen atom and an atom selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom.) Represents a heterocyclic oxy group . Specific examples are given below. Halogen atoms: chlorine, bromine, fluorine alkoxy groups: ethoxy group, benzyloxy group,
Methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group, etc. Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group, etc. Acyloxy group: acetoxy group, myristoyloxy group, benzoyloxy group, etc. Arylthio group: phenylthio Alkylthio groups such as 2-butoxy-5-octylphenylthio group, 2,5-dihexyloxyphenylthio group: methylthio group, octylthio group, hexadecylthio group, benzylthio group, 2
-(diethylamino)ethylthio group, ethoxycarbonylmethylthio group, ethoxyethylthio group, phenoxyethylthio group, etc.

[Formula] Pyrazolyl group, imidazolyl group, triazole group, tetrazolyl group

【formula】

【formula】

【formula】 【formula】

【formula】 Examples of the heterocyclic oxy group include a 1-phenyl-5-tetrazolyloxy group, an isoxazolyloxy group, and a 4-pyridinyloxy group. Representative examples of the compounds of the present invention are shown below. (1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) Y＝NHCOC ₁₃ H ₂₇ (18) (19) (20) (twenty one) (22) Z=SCH ₂ COOH (23) (twenty four) (25) Z=OCH ₂ CONHCH ₂ CH ₂ OCH ₃ (26) Z=OCH ₂ CH ₂ SO ₂ CH ₃ (27) (28) (29) Z=OCOC(CH ₃ ) ₃ (30) (31) (32) (33) (34) W=Cl (35) W=F (36) (37) W=SCH ₂ CH ₂ OH (38) (39) (40) (41) (42) The compounds of the invention are described in UKr.Khim.Zh., 38, 1142.
(1972), 41181 (1975), 41252 (1975), 41181 (1975), 41252 (1975),
411053 (1975), Synthesis, 414 (1973), etc., from intermediate compounds obtained by the methods described. Typical synthesis examples of the compounds of the present invention are shown below. <Synthesis of compound (1)> 1-benzyl-2-methyl-6-(4-
bromophenyl)-1H-pyrrolo[1,2-b]-
s-Triazole 1 was synthesized. Next, dissolve 36.6g of 1 in 360ml of ethyl acetate,
4 g of 5% palladium on carbon was added to this, and catalytic hydrogenation was performed. When the theoretical amount of hydrogen had been absorbed, palladium on carbon was removed by filtration, and the liquid was concentrated under reduced pressure. The residue was recrystallized from ethanol to obtain 20.1 g of compound (1). Yield 73%. Elemental analysis value C (%) H (%) N (%) Cl (%) Theoretical value 52.19 3.65 15.22 28.94 Measured value 52.03 3.83 15.22 28.89 <Synthesis of compounds (2) and (3)> 13.8 g of compound (1) Dissolve in 70ml of ethyl acetate,
7.0 g of N-chlorsuccinimide was added little by little to this. After stirring for 30 minutes, the reaction solution was diluted with water.
Pour into 140ml and take the separated ethyl acetate layer.
It was concentrated under reduced pressure. The residue was purified by a silica gel column in a solvent system of ethyl acetate-n-hexane, and
5.4g (yield 35%) of compound (2) and compound (3)
3.7 g (yield 24%) was obtained. It was identified using various spectral data. Compound (2) Elemental analysis value C (%) H (%) N (%) Br (%) Theoretical value 46.41 2.92 13.53 25.73 Measured value 46.48 3.00 13.51 25.61 Cl (%) Theoretical value 11.41 Measured value 11.40 Compound (3) Element Analytical value C(%) H(%) N(%) Br(%) Theoretical value 46.41 2.92 13.53 25.73 Measured value 46.56 2.88 13.43 25.75 Cl(%) Theoretical value 11.41 Measured value 11.38 Silver halide used in the photosensitive material of the present invention In the emulsion, any silver halide used in ordinary silver halide emulsions can be used, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different. In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into consideration the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling the pH and pAg in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, a convergence method may be used to change the halogen composition of the particles. During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( Metal ions can be added using at least one selected from the group consisting of complex salts) to contain these metal elements inside the particles and/or on the particle surfaces,
Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces. Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. Even if a silver halide grain has a uniform silver halide composition distribution within the grain, the core/silver halide composition differs between the inside and surface layer of the grain.
They may also be shell particles. The silver halide grains may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of {110} planes to {111} planes can be used. or,
The particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). When divided by the average particle size, the value is
0.20 or less. In the case of spherical silver halide, the particle size is the diameter thereof, and in the case of particles having a shape other than spherical, the particle size is the diameter when its projected image is converted into a circular image of the same area. ) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used. Two or more types of silver halide emulsions formed separately may be used in combination. Silver halide emulsions can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination. Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes, hexoxanol dyes, etc. are used. Particularly useful dyes are cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Silver halide emulsions are used in the manufacturing process of photosensitive materials,
Silver halide emulsions are applied during chemical heat formation, at the end of chemical ripening, and/or after chemical ripening for the purpose of preventing fog during storage or photographic processing, or to keep photographic performance stable. By now, compounds known in the photographic industry as antifoggants or stabilizers can be added. It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used. Photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials using silver halide emulsions are hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be filmed. The hardening agent can be added to the processing solution in an amount sufficient to harden the photosensitive material to the extent that it is not necessary to add the hardening agent, but it is also possible to add the hardening agent to the processing solution. A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability. The emulsion layer of the photosensitive material contains a dye-forming compound that undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) to form a dye during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above. These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are tetraequivalent, which requires reduction of four molecules of silver ions in order to form one molecule of dye, only two molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. The dye-forming coupler has a color correction effect and, by coupling with an oxidized form of a developing agent, can be used as a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, and a toning agent. agent, hardening agent, fogging agent, antifogging agent, chemical sensitizer, spectral sensitizer,
and compounds that release photographically useful fragments, such as desensitizers. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. Instead of the DIR coupler, a DIR compound that undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used. The DIR couplers and DIR compounds used include:
one in which an inhibitor is directly bound to the coupling position;
The inhibitor is bonded to the coupling position via a divalent group, and the inhibitor is bonded in such a way that it is released by an intramolecular nucleophilic reaction within the group separated by the coupling reaction, an intramolecular electron transfer reaction, etc. (referred to as timing DIR couplers and timing DIR compounds). Furthermore, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination depending on the purpose. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler. As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. As a magenta dye-forming coupler, known 5
- Pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indazolone couplers, etc. can be used with the couplers of the present invention. Phenol or naphthol couplers are generally used as cyan dye-forming couplers. Among dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. that do not need to be adsorbed on the silver halide crystal surface, hydrophobic compounds are solids. Dispersion can be carried out using various methods such as a dispersion method, a latex dispersion method, and an oil-in-water emulsion dispersion method, which can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler.
The oil-in-water type emulsification dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers. Usually, a high-boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low-boiling point and/or water-soluble additive as necessary. The mixture is dissolved in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, and a dispersion method such as a stirrer, homogenizer, colloid mill, flow mixer, or ultrasonic device is used. After emulsification and dispersion, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included after or simultaneously with the dispersion. Examples of high-boiling point solvents include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used. Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl astate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and water-soluble organic solvents include acetone. , methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, phenoxyethanol, etc. Can be mentioned. Dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. are carboxylic acids,
When it has an acid group such as sulfonic acid, it can also be introduced into the hydrophilic colloid as an alkaline aqueous solution. Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used. The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity, deterioration of sharpness, and graininess. A color antifoggant can be used to prevent the color from becoming noticeable. The color antifoggant may be contained in the emulsion layer itself, or may be contained in an intermediate layer provided between adjacent emulsion layers. An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. A hydrophilic colloid layer such as a protective layer or an intermediate layer of a photosensitive material may contain an ultraviolet absorber in order to prevent fogging caused by discharge caused by charging of the photosensitive material due to friction, etc., and deterioration of images due to ultraviolet rays. . In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material. When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer. Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. The emulsion layer of the light-sensitive material contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development.
It may also contain quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and the like. A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.
Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Reducing the gloss of the photosensitive material in the silver halide emulsion layer and/or other hydrophilic colloid layer of the photosensitive material;
A matting agent can be added for the purpose of improving the ease of writing and preventing the light-sensitive materials from sticking to each other. A lubricant can be added to the photosensitive material to reduce sliding friction. An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material has various properties such as improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and photographic properties (promoting development,
Various surfactants can be used for the purpose of improving (hardening, sensitization, etc.). The support used in the photosensitive material of the present invention includes α
- Flexible reflective supports such as paper laminated with olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymer), synthetic paper, etc., cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, Films made of semi-synthetic or synthetic polymers such as polyamide, flexible supports with reflective layers on these films, glass,
Includes metals, ceramics, etc. After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface. It may be applied through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties. When coating the photosensitive material, a thickener may be used to improve coating properties. Furthermore, for substances such as hardeners, which have quick reactivity and may cause gelation before coating if added to the coating solution in advance, it is recommended to mix them using a static mixer or the like immediately before coating. preferable. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.
Depending on the purpose, packet application may also be used. or,
The coating speed can be selected arbitrarily. To obtain a dye image using the light-sensitive material of the present invention, color photographic processing is performed after exposure. Color processing is
A color development process, a bleaching process, a fixing process, a water washing process and, if necessary, a stabilizing process are performed, but instead of the process using a bleaching solution and the process using a fixing solution, a one-bath process is performed. A bleach-fix treatment process can also be performed using a bleach-fix solution,
It is also possible to perform a monobath processing step using a one-bath development, bleach-fix processing solution that allows color development, bleaching, and fixing to be performed in one bath. In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator process may be performed in which the monobath process is performed using an activator solution. Processing can be applied. Among these processes, typical processes are shown below. (These treatments are performed as the final step, which is either a water washing process, a water washing process, or a stabilization process.) ●Color development process - Bleach process - Fixing process ● Color development process - Bleach-fixing process Process ● Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleaching process - Fixing process - Washing process - Post-hardening process - Color development process - Washing process - Supplementary information Color development process - Stop process - Bleach process - Fixing process ● Activator process - Bleach-fixing process ● Activator process - Bleach process - Fixing process ● Monobath process Processing temperature is usually 10℃ The temperature is selected to be in the range of ~65°C, but the temperature may be higher than 65°C. Preferably
Processed at 25°C to 45°C. A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenyrezine amine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids; for example, hydrochloric acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. can be used. can. These compounds are generally used in a concentration of preferably 0.1 to 30 g per color developer 1, more preferably,
Use at a concentration of 1 to 15 g. Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-hydroxytoluene, 2
-amino-3-hydroxy-toluene, 2-hydroxy-3-amino-1,4-dimethyl-benzene, and the like. Particularly useful primary aromatic amine color developers are N,N'-dialkyl-p-phenylenediamine compounds, in which the alkyl and phenyl groups may be substituted or unsubstituted. good. Among them, examples of particularly useful compounds include N,
N'-dimethyl-p-phenylenediamine hydrochloride,
N-methyl-p-phenylenediamine hydrochloride,
N,N'-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-
Methanesulfonamidoethyl-3-methyl-4-
Aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3
-Methyl-N,N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-
Examples include 3-methylaniline-p-toluenesulfonate. Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.
In this case, it is also possible to process the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment. The color developing solution may contain an alkaline agent commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. may contain additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites. . Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained. The pH of the color developer is usually 7 or more, preferably about 9-13. In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or Hexose, pyrogallol-1,3-dimethyl ether, etc. may be contained. The color developer contains metal ion sequestering agents.
Various chelating agents can be used in combination. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,
Organic phosphonic acids such as 1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid Examples include phosphonocarboxylic acids such as acids, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds. The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately. As a bleaching agent, a metal complex salt of an organic acid is used, for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, citric acid, etc., coordinated with a metal ion such as iron, cobalt, copper, etc. is used. . Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, and iminodiacetic acid. , dihydroxyethylglycine citric acid (or tartaric acid),
Examples include ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, and phenylenediaminetetraacetic acid. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaching agents are preferably 5 to 450 g/,
More preferably, it is used in an amount of 20 to 250g/. In addition to the above bleaching agents, the bleaching solution may contain a sulfite salt as a preservative, if necessary. Further, the bleaching solution may be a solution containing an ethylenediaminetetraacetic acid iron() complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. Various bleach accelerators can be added to the bleach solution. The pH of the bleaching solution used is 2.0 or higher, generally 4.0 to 9.5, preferably 4.5 to 8.0, and most preferably 5.0 to 7.0. A fixer having a commonly used composition can be used. As a fixing agent, compounds that react with silver halide to form water-soluble complex salts, such as those used in ordinary fixing processes, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, and potassium thiocyanate are used. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixing agents are used in an amount of 5 g/or more, within the range that can be dissolved, but are generally used in an amount of 70 to 250 g//.
Incidentally, a part of the fixing agent can be contained in the bleaching solution, or conversely, a part of the bleaching agent can also be contained in the fixing solution. In addition, the bleaching solution and/or fixing solution contains boric acid, borax,
Various PH buffers such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be contained alone or in combination of two or more. . Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, hardening agents such as water-soluble aluminum salts, Organic solvents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. can be appropriately contained. Fixer is used at a pH of 3.0 or above, but generally
It is used between 4.5 and 10, preferably between 5 and 9.5, most preferably between 6 and 9. Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fixing solution consisting of an ethylenediaminetetraacetic acid iron () complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely, a halide such as ammonium bromide may be used. It is also possible to use a special bleach-fixing solution containing a large amount of .
In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide,
Potassium iodide, ammonium iodide, etc. can also be used. Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as in the above-mentioned fixing process. The pH of the bleach-fix solution is 4.0 or higher, but it is generally used between 5.0 and 9.5, preferably between 6.0 and 8.5.
most preferably between 6.5 and 8.5.

[Specific embodiments of the invention]

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 A magenta coupler of the present invention and a comparative coupler as shown in Table 1 were each used at a concentration of 0.15% per mole of silver.
Take mole by mole, add dibutyl phthalate in an amount of 1 time the coupler weight and ethyl acetate in an amount 3 times the weight of the coupler, and add 60
It was completely dissolved by heating to ℃. This solution was mixed with 1200 ml of a 5% aqueous gelatin solution containing 120 ml of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont) and emulsified and dispersed using an ultrasonic disperser to obtain an emulsion. After that, this dispersion was converted into a green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide).
4 kg, 120 ml of a 2% aqueous solution of 1,2-bis(vinylsulfonyl)ethane (water: methanol = 1:1) as a hardening agent, and coated on a paper support laminated on both sides with polyethylene and dried. , Samples 1 to 8 were created. (Amount of coated silver: 5 mg/100 cm ² ) The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment. Table 1 shows the results. [Development process] Temperature Time Color development 38℃ 3 minutes 30 seconds Bleach fixing 33℃ 1 minute 30 seconds Stabilization treatment or 25-30℃ 3 minutes Washing treatment Drying 75-80℃ approx. 2 minutes In each processing step, The composition of the treatment liquid is as follows. [Color developer] Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-methyl-4-amino-N -ethyl-N-(β
-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to bring the total volume to 1 and adjust the pH to 10.20 . [Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust to PH7.1 with potassium carbonate or glacial acetic acid,
Add water to make total volume 1. [Stabilizing liquid] 5-chloro-2-methyl-4-isothiazoline-
3-one 1.0g Ethylene glycol 10g 1-hydroxyethylidene-1,1'-diphosphonic acid 2.5g Bismuth chloride 0.2g Magnesium chloride 0.1g Ammonium hydroxide (28% aqueous solution) 2.0g Sodium nitrilotriacetate 1.0g Add water to total volume 1 and adjust the pH to 7.0 with ammonium hydroxide or sulfuric acid.

[Table] (1) Specific sensitivity is the reciprocal of the exposure amount that gives a density of fog density + 0.1 Sample-1 using comparative coupler 1
was set as 100. (2) The sample after color development was exposed to a xenon fade meter for 5 days, and the percentage of dye remaining after processing at the initial density D=1.0 was shown. That is, Light resistance = Density after 5 days of xenon fade meter irradiation / 1.0 x 100 Comparative coupler 1 Comparison coupler 2 As is clear from the results in Table 1, the coupler of the present invention is a coupler with excellent color development and light resistance with little fading of the magenta color image. Example 2 As shown in Table 2, the magenta coupler of the present invention and the comparative coupler were each added at a concentration of 0.1 to 1 mole of silver.
One mole of tricresyl phosphate and three times the amount of ethyl acetate were added to the coupler weight, and the mixture was heated to 60° C. to completely dissolve. This solution was added to a solution containing 120 ml of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by Dupont).
% gelatin aqueous solution and emulsified and dispersed using an ultrasonic disperser to obtain an emulsion. Thereafter, this dispersion was added to 4 kg of green-sensitive silver iodobromide (containing 6 mol% silver iodide), and a 2% aqueous solution of 1,2-bis(vinylsulfonyl)ethane (water:
Samples 9 to 16 were prepared by adding 120 ml of methanol (1:1), coating and drying on a subbed transparent polyester base. (Amount of coated silver: 20 mg/100 cm ² ) The sample thus obtained was subjected to wedge exposure according to a conventional method, and then subjected to the following development treatment. The results are shown in Table 2. [Development process] 1 Color development 38℃ 3 minutes 15 seconds 2 Bleaching 38℃ 6 minutes 30 seconds 3 Washing with water 38℃ 3 minutes 15 seconds 4 Fixing 38℃ 6 minutes 30 seconds 5 Washing with water 38℃ 3 minutes 15 seconds 6 Stability 38℃ 3 minutes 15 seconds The composition of the processing liquid used in each step is as follows. [Color developer composition] Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.5g Hydroxylamine sulfate 2.5g 4-(N-ethyl-N-(3-hydroxyethylamino)-2- Methyl-aniline sulfate 4.5g Add water 1 PH 10.02 [Bleach solution composition] Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt 130g Glacial acetic acid 14ml Add water 1 [Fixing] Liquid composition] Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 160ml Sodium bisulfite 5.0g Add water 1 [Stable liquid composition] Formalin 10.0ml Add water 1

【table】

[Table] As is clear from Table 2, the coupler of the present invention is a coupler with excellent coloring properties.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide photographic material comprises an oxidized product of an aromatic primary amine color developing agent. A silver halide photographic material comprising a 1H-pyrrolo[1,2-b]imidazole coupler that undergoes a coupling reaction at the 3-position.