JPH0577060B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for forming a novel indonaphthol photographic dye image. (Prior Art) When a silver halide photographic material is exposed to light and then subjected to color development, an oxidized aromatic primary amine developer and a dye-forming coupler react to form a color image. Generally, in this method, a subtractive color reproduction method is used, and in order to reproduce blue, green, and red, images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively. Phenol derivatives or naphthol derivatives are often used as couplers to form cyan images. In color photography,
Color-forming couplers are added to the developer solution or incorporated into the light-sensitive photographic emulsion layer or other color image-forming layer, and are rendered non-active by reacting with the oxidized form of the color developer formed during development. Forms a diffusible pigment. The reaction between the coupler and the color developing agent takes place at the active site of the coupler, and a coupler having a hydrogen atom at this active site is a 4-equivalent coupler, i.e., stoichiometrically, 4 moles of developing agent are required to form 1 mole of dye. It requires silver halide with a nucleus.
On the other hand, those having a group capable of leaving as an anion at the active site are 2-equivalent couplers, that is, couplers that require only 2 stoichiometric moles of silver halide having development nuclei to form 1 mole of dye. Therefore, compared to a 4-equivalent coupler, the amount of silver halide in the photosensitive layer can be generally reduced and the film thickness can be made thinner, making it possible to shorten the processing time of the photosensitive material and further improving the sharpness of the color image formed. degree will improve. Phenol couplers or naphthol couplers, which are known as cyan dye-forming couplers, have low fastness to heat or light of color images produced by color development, or are used in bleaching solutions with weak oxidizing power or exhausted bleaching solutions. It has been pointed out that there is a drawback in that the color density decreases when development is carried out using . In order to improve these shortcomings, 2
A phenolic cyan coupler having a phenylureido group at the 5th position and a carbonamide group at the 5th position was proposed. These couplers are disclosed in, for example, Japanese Patent Application Publication Nos. 56-65134, 57-204543, and 57-
No. 204544, No. 57-204545, No. 58-33249, No. 58-33249, No.
No. 58-33250, etc. It is true that the 2-position phenylureido substituent coupler is superior to the conventionally known phenolic cyan couplers and naphthol cyan couplers, but as described in JP-A-59-46644, for example, However, it has the disadvantage that the spectral absorption of the color image varies greatly between short-wave absorption and long-wave absorption depending on the color density. (Problems to be Solved by the Invention) The first object of the present invention is to form a photographic dye image in which the color density decreases little even when developed using a bleaching solution with weak oxidizing power or a bleaching solution that is exhausted. Our goal is to provide the following. A second object of the present invention is to provide a method for forming a photographic dye image in which the developed color image has excellent heat and light fastness. (Means for Solving the Problems) These objects of the present invention are achieved by a silver halide color photographic light-sensitive material containing a cyan dye-forming coupler represented by the following general formula (). That is, the present invention comprises the following steps a) and b).
A method for forming an indonaphthol-based photographic dye image, characterized in that it does not include step c); The process of forming. b. A step of reacting this oxidized color developing agent with a coupler represented by the following general formula () to form an indonaphthol dye image. However, the indonaphthol dye formed here does not have a metal chelation site that can form a tridentate or higher metallized dye. c. Contacting this dye image with polyvalent metal ions to form a metallized dye image. It provides: General formula ()

[Formula] (In the formula, R ₁ is −CONR ₃ R ₄ , −NHCOR ₃ , −
NHCOOR ₅ , -NHSO ₂ R ₅ , -NHCONR ₃ R ₄ or -NHSO ₂ NR ₃ R ₄ , R ₂ is a group that can be substituted with naphthol, m is an integer from 0 to 3, X is an oxygen atom,
Sulfur atom, HN, R ₆ N or R ₆ OCON
, Y represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized aromatic primary amine developer. However, R ₃ and R ₄ are hydrogen atoms, aliphatic groups, aromatic groups, or heterocyclic groups, R ₅ and R ₆ are aliphatic groups,
Indicates an aromatic group or a heterocyclic group. Here, the aliphatic group refers to a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be substituted. The aromatic group refers to a substituted or unsubstituted monocyclic or condensed ring aryl group.
The term "heterocyclic group" refers to a substituted or unsubstituted monocyclic or condensed ring heterocyclic group. ) The substituents R ₁ , R ₂ , X and Y in the general formula () will be described in more detail below. That is, R ₁ is −CONR ₃ R ₄ , −NHCOR ₃ , −
NHCOOR ₅ , -NHSO ₂ R ₅ , -NHCONR ₃ R ₄ or -NHSO ₂ R ₃ R ₄ , and R ₃ and R ₄ are hydrogen atoms, aliphatic groups having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, butyl group, methoxyethyl group, n
-decyl group, n-dodecyl group, n-hexadecyl group, trifluoromethyl group, heptafluoropropyl group, dodecyloxypropyl group, 2,4-di-tert-amylphenoxypropyl group, 2,4-
di-tert-amylphenoxybutyl group, etc.), aromatic groups having 6 to 30 carbon atoms (e.g., phenyl group, tolyl group, 2-tetradecyloxyphenyl group, pentafluorophenyl group, 2-chloro- 5-dodecyloxycarbonyl group, etc.), a heterocyclic group having 2 to 30 carbon atoms (for example, 2-pyridyl group, 4-pyridyl group, 2-furyl group, 2-thienyl group, etc.), R ₅ has 1 to 30 carbon atoms 30 aliphatic groups (e.g., methyl group, ethyl group, butyl group, dodecyl group, hexadecyl group, etc.), 6 to 30 aromatic groups (e.g., phenyl group, tolyl group, 4-chlorophenyl group, naphthyl group, etc.),
Represents a heterocyclic group (eg, 4-pyridyl group, quinolyl group, 2-furyl group, etc.). R ₃ and R ₄ may be bonded to each other to form a heterocycle (eg, morpholine ring, piperidine ring, pyrrolidine ring, etc.). R ₂ represents a group that can be substituted with naphthol,
Examples include halogen atom, hydroxy group, amino group, carboxy group, sulfo group, cyano group, aliphatic group, aromatic group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyloxy group, acyl group,
Examples include an aliphatic oxy group, an aliphatic thio group, an aliphatic sulfonyl group, an aromatic oxy group, an aromatic thio group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, and an imide group. The number of carbon atoms in R ₂ is 0 to 30. When m is plural, R ₂ may be the same or different. X represents an oxygen atom, a sulfur atom, HN, R ₆ N or R ₆ OCON, and R ₆ represents an aliphatic group, an aromatic group or a heterocyclic group. Examples of R ₆ include aliphatic groups having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, benzyl group, methoxyethyl group, chloroethyl group, dodecyl group, cyanoethyl group, etc.), and 6 carbon atoms. -30 aromatic groups (e.g. phenyl group, naphthyl group, 4-chlorophenyl group, etc.) and C1-C30 heterocyclic groups (e.g. 2-pyridyl group, 4-pyridyl group, 2-furyl group, 2 -pyrimidyl group, triazolyl group, etc.). Y represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Examples of groups that can be separated include halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), aliphatic oxy groups having 1 to 30 carbon atoms (e.g., methoxy group, ethoxy group, 2-hydroxyethoxy group, carboxymethyloxy group, 3
-carboxypropyloxy group, 2-methoxyethoxycarbamoylmethyloxy group, 2-methanesulfonylethoxy group, 2-carboxymethylthioethoxy group, triazolylmethyloxy group, etc.),
Aromatic oxy groups having 6 to 30 carbon atoms (e.g. phenoxy group, 4-hydroxyphenoxy group, 2-acetamidophenoxy group, 2,4-dibenzenesulfonamidophenoxy group, 4-phenylazophenoxy group) enoxy group, etc.), heterocyclic oxy group having 2 to 30 carbon atoms (e.g., 4-pyridyloxy, 1-phenyl-
5-tetrazolyloxy group, etc.), aliphatic thio group having 1 to 30 carbon atoms (e.g., dodecylthio group, etc.), aromatic thio group having 6 to 30 carbon atoms (e.g., 4-dodecyl phenylthio group, etc.) , a heterocyclic thio group having 2 to 30 carbon atoms (e.g. 4-pyridylthio group, 1-phenyltetrazol-5-ylthio group, etc.), 2 to 30 carbon atoms
30 acyloxy groups (e.g. acetoxy group, benzoyloxy group, lauroyloxy group, etc.), carbon amide groups having 1 to 30 carbon atoms (e.g. dichloroacetylamide group, trifluoroacetamide group, heptafluorobutanamide group, pentafluorobenzamide group) group), a sulfonamide group having 1 to 30 carbon atoms (e.g., methanesulfonamide group,
toluenesulfonamide group, etc.), aromatic azo groups having 6 to 30 carbon atoms (e.g., phenylazo group, 4-chlorophenylazo group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, etc.) ,
Aliphatic oxycarbonyloxy group having 1 to 30 carbon atoms (e.g., ethoxycarbonyloxy group, dodecyloxycarbonyloxy group, etc.), 6 to 30 carbon atoms
aromatic oxycarbonyloxy group (e.g., phenoxycarbonyloxy group, etc.), carbon number 1 to 30
carbamoyloxy group (e.g., methylcarbamoyloxy group, dodecylcarbamoyloxy group, phenylcarbamoyloxy group, etc.), a heterocyclic group having 1 to 30 carbon atoms and having a nitrogen atom connected to the active position of the coupler (e.g., succinic acid imide group, phthalimide group, hydantoinyl group, pyrazolyl group,
2-benzotriazolyl group, etc.). Next, examples of substituents preferably used in the present invention are listed below. In the present invention, it is more preferable that R ₁ is -CONR ₃ R ₄ , R ₃ is a substituted alkyl group, and R ₄ is a hydrogen atom, and among these, those in which the alkyl group of R ₃ is an alkoxyalkyl group are more preferable. preferable. Preferred as R ₁ - CONR ₃
Examples of _R4 include carbamoyl group, ethylcarbamoyl group, morpholinocarbonyl group, dodecylcarbamoyl group, hexadecylcarbamoyl group, decyloxypropylcarbamoyl group, dodecyloxypropylcarbamoyl group, 2,4-di-tert
-amylphenoxypropylcarbamoyl group,
Examples include 2,4-di-tert-amylphenoxybutylcarbamoyl group. Preferred examples of R ₂ are halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), aliphatic groups (e.g. methyl group, ethyl group, isopropyl group, etc.), carbonamide groups (e.g. acetamide group, benzamide group, etc.) , a sulfonamide group (eg, methanesulfonamide group, toluenesulfonamide group, etc.). However, as a coupler, one having no substituent R ₂ is more preferable. A preferred group as X is R ₆ OCON, -
Examples of XH include a methoxycarbonylamino group, an ethoxycarbonylamino group, a butoxycarbonylamino group, a methoxyethoxycarbonylamino group, a phenoxycarbonylamino group, a dodecyloxycarbonylamino group, and the like. Preferred groups as Y are a hydrogen atom, a halogen atom, an aliphatic oxy group, an aromatic oxy group, a heterocyclic thio group, and an aromatic azo group. When m is plural, R ₂ may be bonded to each other to form a ring, or R ₂ , X, and Y may be bonded to each other to form a ring. The coupler represented by the general formula [ ] has its substituents
R ₁ , R ₂ , X or Y may be a dimer or a multimer of more than two valents bonded to each other via a divalent or more polyvalent linking group. In this case, the limitations on the number of carbon atoms shown in each of the above substituents are not limited to this. Next, specific examples of the coupler represented by the general formula [] will be shown, but the coupler used in the present invention is not limited to these. In the following structural formula _, (t) _{C5H11 represents -C} ( _CH3 ) _2CH2CH3 .

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[Chemical formula] Next, a synthesis example is shown. Synthesis Example 1 Synthesis of Coupler (1) 42 g of p-nitrophenyl-5-trifluoroacetamide-1-hydroxynaphthoate was dispersed in 200 ml of tetrahydrofuran and stirred at room temperature.
To this was added 29 g of 3-(2,4-di-tert-amylphenoxy)propylamine, and after stirring for 1.5 hours, the mixture was poured into 500 ml of water. The supernatant liquid was discarded, the remaining oily substance was dissolved in 200 ml of methanol under heating, and after filtering off insoluble substances, the filtrate was cooled. The precipitated crystals were collected by filtration, and 2-{N-[3-(2,4-di-tert-amylphenoxy)propyl]carbamoyl}-5-
Trifluoroacetamido-1-naphthol 61
I got g. Melting point: 151.5℃ - 152.2℃ Furthermore, 61g of crystals were dispersed in 400ml of ethanol, and aqueous sodium hydroxide solution (30g of sodium hydroxide, 100ml of water) was added to this.
was added and stirred for 2 hours at 60°C under a nitrogen stream. After cooling to room temperature, 500 ml of water was added and neutralized with hydrochloric acid.
Extract with 300ml of ethyl acetate, and dilute the ethyl acetate layer with 300ml of ethyl acetate.
After washing twice with ml of water, it was dried with sodium sulfate. After filtering off the sodium sulfate, the ethyl acetate solution was concentrated. Ethyl acetate from the residue
By recrystallizing with a mixed solvent of n-hexane, 42 g of crystals of the desired coupler (1) were obtained. Melting point: 151°C to 153°C Elemental analysis results are shown below. Elemental analysis value HCN Calculated value (%) 8.46 75.60 5.88 Measured value (%) 8.43 75.69 5.84 Synthesis example 2 Synthesis of coupler (2) 5-amino-1-hydroxy-2-naphthoic acid
71g and 85g of dodecyloxypropylamine.
Dissolved in 300ml dimethylformamide, 60-70
C. While stirring, a solution of 72 g of dicyclohexylcarbodiimide in dimethylformamide was added dropwise over 1 hour. After heating and stirring for 3 hours, the mixture was cooled on ice to remove precipitated crystals of dicyclohexyl urea. 500 ml of ethyl acetate was added to the filtrate, and the mixture was washed three times with water from step 1. The ethyl acetate solution was separated, dried over sodium sulfate, and concentrated. Next, the concentrate was developed and purified using chloroform in a chromatography column using silica gel as a packing material, to obtain 100 g of oily coupler (2). Synthesis Example 3 Synthesis of Coupler (6) 11.9 g of the coupler (1) obtained in Synthesis Example 1) and 2 ml of pyridine were dissolved in 50 ml of acetonitrile, and 3 g of ethyl chlorocarbonate was added dropwise thereto while stirring at room temperature. After stirring for 3 hours, add 80 ml of ethyl acetate.
It was washed three times with 100 ml of water to obtain an ethyl acetate solution.
After drying with sodium sulfate, it was concentrated, and the concentrate was crystallized from a methanol-acetonitrile mixed solvent to obtain 11.9 g of the target coupler (6).
Melting point: 135-137℃ Synthesis Example 4 Synthesis of Coupler (8) 37.8 g of coupler (2) obtained in Synthesis Example 2) and 7.8 ml of pyridine were dissolved in 200 ml of acetonitrile, and 10.8 g of ethyl chlorocarbonate was added thereto while stirring at room temperature. was dripped. After stirring for 3 hours, 200 ml of ethyl acetate was added and washed three times with 500 ml of water to obtain an ethyl acetate solution. After drying over sodium sulfate, the mixture was concentrated, and the concentrate was crystallized from acetonitrile to obtain 34 g of the desired coupler (8). Melting point: 79 DEG -81 DEG C. The coupler represented by the above general formula () is usually contained in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.002 to 1.0 mol, preferably 0.005 to 0.3 mol, per mol of silver halide. In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, and examples include phthalic acid esters such as dibutyl phthalate and dioctyl phthalate, and phosphoric acid esters such as tricresyl phosphate and trinonyl phosphate. After dissolving in a high boiling point organic solvent such as ethyl acetate or a low boiling point organic solvent such as ethyl acetate alone or in a mixed solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. The low-boiling organic solvent may be removed from the coupler dispersion by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion. Various silver halides can be used in the silver halide emulsion layer according to the present invention. Examples include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Silver iodobromide containing 2 to 20 mol % silver iodide and silver chlorobromide containing 10 to 50 mol % silver bromide are preferred. There are no limitations on the crystal form, crystal structure, grain size, grain size distribution, etc. of the silver halide grains. Silver halide crystals may be normal crystals or twin crystals, and may be hexahedral, octahedral, or tetradecahedral. They may be tabular grains having a thickness of 0.5 microns or less, a diameter of at least 0.6 microns, and an average aspect ratio of 5 or more, as described in Research Disclosure No. 22534. The crystal structure may be uniform, the inside and outside may have different compositions, it may have a layered structure, or silver halides of different compositions may be joined by epitaxial bonding. , may consist of a mixture of particles of various crystalline forms. Further, the latent image may be formed mainly on the surface of the particle or may be formed inside the particle. The grain size of the silver halide may be fine grains of 0.1 micron or less or large grains with a projected area diameter of up to 3 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. These silver halide grains can be produced by known methods commonly used in the art. The silver halide emulsion can be sensitized by conventional chemical sensitization, such as sulfur sensitization, noble metal sensitization, or a combination thereof. Furthermore, the silver halide emulsion according to the present invention can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye. The pigments advantageously used in the present invention include cyanine,
There are methine dyes and styryl dyes such as hemicyanine, rhodacyanine, merocyanine, oxonol, and hemioxonol, and one type or a combination of two or more types can be used. Furthermore, in some cases, a fine-grain silver halide emulsion having substantially no photosensitivity (for example, silver chloride, silver bromide, silver silver bromide emulsion)
may be added. The cyan coupler according to the invention can be used in conjunction with magenta and yellow couplers to produce natural color materials or these couplers may be selected to give a neutral gray color to produce black and white materials based on dye images. Can be used for The cyan coupler of the present invention may be used in combination with a conventionally known cyan coupler in an equimolar amount or less. These couplers that can be used in combination may be either 4-equivalent or 2-equivalent to silver ions. Further, a colored coupler having a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler) may be used in combination. In addition to the DIR coupler, a colorless DIR coupling compound whose coupling reaction product is colorless and releases a development inhibitor may be added. Various color couplers can be used in combination in the present invention. The term "color coupler" as used herein refers to a compound capable of producing a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer. Useful color couplers are cyan, magenta and yellow colored couplers, typical examples of which are naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds, respectively. Specific examples of these cyan, magenta and yellow couplers that can be used in combination in the present invention are provided by research and research.
Disc closure (RD) 17643 (December 1978)
- D and the patent cited in No. 18717 (November 1979). The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce the amount of coated silver and provide higher sensitivity than a four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the coloring dye has adequate diffusivity, colorless couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used. A representative example of the yellow coupler that can be used in combination with the present invention is an oil-protected acylacetamide coupler. Specific examples thereof are described in US Pat. No. 2,407,210, US Pat. No. 2,875,057, and US Pat. No. 3,265,506. The use of two-equivalent yellow couplers is preferred for the present invention;
U.S. Patent No. 3408194, U.S. Patent No. 3447928, U.S. Patent No.
Oxygen atom separation type yellow couplers described in No. 3933501 and No. 4022620, Japanese Patent Publication No. 58-10739, U.S. Patent No. 4401752, U.S. Pat.
No. 4326024, RD18053 (April 1979), British Patent No.
No. 1425020, West German Published Application No. 2219917, same no.
Typical examples thereof include nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 2261361, 2329587, and 2433812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density. Magenta couplers that can be used in combination with the present invention include oil-protected indazolone or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include U.S. Pat.
Same No. 2600788, Same No. 2908573, Same No. 3062653,
It is described in the same No. 3152896 and the same No. 3936015. Particularly preferred as the leaving group for the two-equivalent 5-pyrazolone coupler are the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73636 provides high color density. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat. No. 3,369,879, preferably pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Pat. No. 3,725,067; Research Disclosure
24220 (June 1984) and Research Disclosure 24230
(June 1984). Imidazo[1,2-b]pyrazoles described in European Patent No. 119741 are preferable from the viewpoint of low yellow side absorption of coloring dyes and light fastness, and pyrazolo[1,2-b]pyrazoles described in European Patent No. 119860 are preferable.
5-b][1,2,4]triazole is particularly preferred. Cyan couplers that can be used in the present invention include:
There are oil-protected naphthol-based and phenolic couplers, preferably the naphthol-based couplers described in U.S. Pat. No. 2,474,293, U.S. Pat. No. 4,052,212, U.S. Pat.
Typical examples include two-equivalent naphthol couplers of the oxygen atom dissociation type described in No. 1 and No. 4,296,200. Specific examples of phenolic couplers are described in US Pat. No. 2,369,929, US Pat. No. 2,801,171, US Pat. No. 2,772,162, and US Pat. Humidity and temperature robust cyan couplers are preferably used in the present invention, typical examples being the phenolic cyan couplers described in U.S. Pat. No. 3,772,002;
No. 2772162, No. 3758308, No. 4126396, No. 4334011, No. 4327173, West German Patent Publication No.
2,5-diacylamino-substituted phenolic couplers described in No. 3329729 and Japanese Patent Application No. 58-42671, and U.S. Pat. Nos. 3446622 and 4333999.
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in Japanese Patent No. 4451559 and No. 4427767. In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for photographing. Yellow-colored magenta coupler described in U.S. Patent No. 4163670 and Japanese Patent Publication No. 57-39413, etc. or U.S. Patent No. 4004929
Typical examples include magenta-colored cyan couplers described in No. 4,138,258 and British Patent No. 1,146,368. Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such blur couplers include magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570, and examples of yellow, magenta or cyan couplers in European Patent No. 96,570 and German Published Application No. 3,234,533. is listed. The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in US Pat. No. 3,451,820 and US Pat. No. 4,080,211. Specific examples of polymerized magenta couplers are given in UK Patent No. 2102173 and US Patent No.
Described in No. 4367282. The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in two or more layers in which the same compound is used in different layers. It can also be introduced into Typical amounts of color couplers used range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.5 mole for yellow couplers and from 0.01 to 0.5 mole for magenta couplers.
The cyan coupler of the present invention and the cyan coupler used in combination, if any, are in a total amount of 0.005 to 0.3 mole. The support used in the present invention may be either a transparent support such as polyethylene terephthalate or cellulose triacetate, or a reflective support described below. Examples of the reflective support include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyethylene terephthalate, cellulose triacetate, and cellulose nitrate. There are polyester films, polyamide films, polycarbonate films, polystyrene films, etc., and these supports can be appropriately selected depending on the purpose of use. In addition to the silver halide emulsion layer, the color photographic light-sensitive material of the present invention may be provided with auxiliary layers such as an undercoat layer, an intermediate layer, and a protective layer. Further, if necessary, an ultraviolet absorbing layer may be provided at a position farther from the support than the emulsion layer or between the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer. Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. In addition to lime-processed gelatin, acid-processed gelatin, Bull.Soc.Sci.Phot.Japan.No.16,
Enzyme-treated gelatin as described on page 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. In the color photographic light-sensitive material used in 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. Specific examples of optical brighteners are given in U.S. Patent No. 2632701, U.S. Patent No.
3359102, British Patent No. 852075, British Patent No. 1319763, Research Disclosure Vol. 176 17643 (1978)
Brighteners on page 24, left column, lines 9 to 36 of December issue)
It is written in the description etc. In the photosensitive material of the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc.
They may be mordanted, such as by cationic polymers. The photosensitive material of the present invention has the following properties as a color antifoggant:
It may contain hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc., specific examples of which are disclosed in the US patent
No. 2360290, No. 2336327, No. 2403721, No. 2360290, No. 2336327, No. 2403721, No.
No. 2418613, No. 2675314, No. 2701197, No.
No. 2704713, No. 2728659, No. 2732300, No.
No. 2735765, Japanese Patent Application Publication No. 50-92988, No. 50-92989,
No. 50-93928, No. 50-110337, No. 52-146235
No., Special Publication No. 50-23813, etc. In addition to the above, the color photographic material used in the present invention includes various photographic additives known in this field,
For example, stabilizers, antifoggants, surfactants, couplers other than those of the present invention, filter dyes, anti-irradiation dyes, developing agents, etc. can be added as necessary.A typical example is Research Disclosure 17643 (1978 (December). The color developing solution used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but
P-phenylenediamine compounds are preferably used. Examples of this color developing agent include those represented by the following formula.

[Formula] (In the formula, R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, or an alkyl group substituted with at least one of a hydroxyl group, an alkoxy group, an alkoxyalkoxy group, or an alkylsulfonamide group, and R ₉ represents an alkyl group, an alkoxy group, or a halogen atom, and n is a substituent
R is the replacement number of ₉ and represents an integer from 0 to 4,
When n is 2 or more, R ₉ may be the same or different. ) The color developing agent represented by () will be explained in detail. The alkyl group, alkoxy group, and alkyl residue of the alkoxy group or alkylsulfonamide group allowed as a substituent for the alkyl group in R ₇ , R ₈ or R ₉ in () are preferably linear chains having 1 to 10 carbon atoms. and a branched alkyl group. Examples of these alkyl groups are methyl, ethyl, n
-propyl, iso-propyl, n-butyl, iso-
Butyl, sec-butyl, t-butyl, n-amyl,
dl-2-methyl, 1-butyl, iso-amyl, sec
-amyl, n-amyl, t-amyl, n-hexyl, 2-ethylbutyl, n-octyl, 2-ethylhexyl, etc., with methyl and ethyl groups being particularly preferred. Further, examples of the alkoxy group include ethoxyethoxy group and the like. As the halogen atom, chlorine, bromine, and iodine are preferred. A typical example of a color developing agent is 3-methyl-4-
Amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates. It will be done. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used. The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, bromides,
It is common to include development inhibitors or antifoggants such as iodides, benzimidazoles, benzothiazoles or mercapto compounds. In addition, if necessary, preservatives such as hydroxylamine or sulfites, organic solvents such as triethanolamine and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, and dyes may be added. Forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, tackifying agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphono Various chelating agents such as carboxylic acids, antioxidants described in West German Patent Application (OLS) No. 2622950, and the like may be added to the color developer. In the development process for reversal color photosensitive materials, color development is usually performed after black and white development. This black-and-white developer contains dihydroxybenzenes such as hydroquinone, 3-phenyl-3-pyrazolidone, etc.
Known black and white developers such as pyrazolidones or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As the bleaching agent, for example, compounds of polyvalent metals such as iron (), cobalt (), chromium (), copper (), peracids, quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron () or cobalt (); amino acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid; Complex salts of polycarboxylic acids or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; manganates; nitrosophyls, and the like can be used. Among these, ethylenediaminetetraacetic acid iron (acid) salt and persulfate are preferred from the viewpoint of rapid treatment and prevention of environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron() complex salt is particularly useful in both stand-alone bleach solutions and monobath bleach-fix solutions. If necessary, various accelerators may be used in combination with the bleaching solution and bleach-fixing solution. For example, in addition to bromide ion and iodide ion, U.S. Patent No. 3706561,
No. 8506, No. 49-26586, JP-A-53-32735, No.
Thiourea compounds as shown in Nos. 53-36233 and 53-37016; JP-A-53-124424, 53
-95631, 53-57831, 53-32736, same
53-65732, 54-52534 and U.S. Pat.
Thiol compounds as shown in JP-A-49-59644, JP-A No. 50-140129, JP-A-53
-28426, 53-141623, 53-104232, and 54-35727, etc.;
Thioether compounds described in JP-A No. 55-26506; tertiary amines described in JP-A-48-84440;
Compounds such as thiocarbamoyls described in JP-A-49-42349 may be used alone or in combination of two or more. Bromine ions, iodide ions, thiol-based or disulfide-based compounds are preferred bleach accelerators. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography. As a fixing agent, thiosulfate, thiocyanate,
Examples include thioether compounds, thioureas, and large amounts of iodides, but thiosulfates are commonly used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred. After the bleach-fixing process or the fixing process, a washing process is usually performed. Various known compounds may be added to the water washing process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, disinfectants and anti-microbial agents that prevent the growth of various bacteria, algae, and mold, magnesium salts, and aluminum. A hardening agent typified by salt or a surfactant for preventing drying load and unevenness may be added as necessary. Or LE West, “Water Quality Standards” Photographic Science Engineering Magazine (LEWest,
Compounds described in "Water Quality Criteria", Phot.Sci.Eng.) Volume 6, pages 344-359 (1965) may be added. The addition of chelating agents and anti-bacterial agents is particularly effective. In the washing process, two or more tanks are generally used for countercurrent washing to save water. Furthermore, instead of the water washing step, a multistage countercurrent stabilization treatment step as described in JP-A-57-8543 may be performed. In the case of this step, 2 to 9 countercurrent baths are required. Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, various buffers (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, Typical examples include carboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. (used in combination) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (benzisothiazolinone, isothiazolone, 4-thiazoline benzimidazole, etc.), as necessary. , halogenated phenols, etc.), surfactants,
Various additives such as optical brighteners and hardeners may be used, and two or more compounds for the same or different purposes may be used in combination. Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as membrane PH regulators after treatment. Preferred processing modes after the color development step in the method of the present invention will be described below. After color-developing the exposed color photographic material of the present invention, a bath having mainly bleaching ability, preferably containing 0.5 to 1.3 mol/water-soluble bromide;
The desilvering speed can be accelerated by subsequent treatment with a bath having bleach-fixing ability.
Processing time can be shortened. Further, it is also possible to eliminate the disadvantage that the maximum image density of cyan dye decreases. The above-mentioned bath mainly having bleaching ability (hereinafter simply referred to as "bleaching bath") is a bath whose purpose is to bleach developed silver by containing a bleaching component. That is, this bath is a bath capable of bleaching at least 1/2 or more, preferably 2/3 or more, more preferably 4/5 or more of the maximum amount of developed silver contained in the color photosensitive material. However, it may have desilvering ability in addition to bleaching ability, but in that case, the desilvering ability is less than 1/2, preferably less than 1/3, more preferably less than 1/3 of the total amount of silver coated in the color photosensitive material. is less than 1/5. In addition, a bath having bleach-fixing ability (hereinafter simply referred to as a "bleach-fixing bath") is a bath that bleaches less than 1/2 of the maximum amount of developing silver contained in a color photosensitive material,
Preferably it is a bath that bleaches less than 1/3, more preferably less than 1/5. Further, this bath is a processing bath capable of desilvering at least 1/2 or more, preferably 2/3 or more, more preferably 4/5 or more of the total amount of silver coated on the color light-sensitive material. The above-mentioned bleaching baths and bleach-fixing baths may be used in a total of four baths or less, and each bath may be composed of two or more baths. Further, a washing step (including a small washing bath in which the amount of washing water is reduced) may be included between the bleaching bath and the bleach-fixing bath. Furthermore, the overflow liquid resulting from replenishment from the bleach bath can be introduced directly or indirectly, preferably directly into the subsequent bleach-fix bath. This allows some or all of the bleach to be replenished into the bleach-fixing bath to be removed. The water-soluble bromides mentioned above are compounds that release bromide ions when dissolved in bleach baths and bleach-fix baths, and specifically include potassium bromide, sodium bromide,
Examples include alkali metal bromides such as lithium bromide, ammonium bromide, hydrobromic acid, and alkaline earth metal bromides such as magnesium bromide, calcium bromide, and strontium bromide.
Among these water-soluble aggregates, ammonium bromide is particularly preferred. Regarding the bleaching solution mentioned above, per bleaching solution,
Bleach from 0.1 mol to 1 mol, preferably from 0.2 mol
Use 0.5 mol. Further, the pH of the bleaching solution is preferably 4.0 to 8.0 during use. For bleach-fix solution, per bleach-fix solution,
The bleaching agent is used in an amount of 0.05 mol to 0.5 mol, preferably 0.1 mol to 0.3 mol, and the fixing agent is used in an amount of 0.3 mol to 3 mol, preferably 0.5 mol to 2.5 mol. Moreover, PH is 5-8. If the amount of bleaching agent is less than 0.05 mol/mol, neither the purpose of speeding up the process nor improving the restoration of cyan dye can be achieved. In the desilvering process, a bleach accelerator can be added to accelerate bleaching. These bleach accelerators can be added to either the bleach bath or the bleach-fix bath, or to both.
It is preferable to add a bleach accelerator to the bleach bath, and any bleach accelerator can be selected from known bleach accelerators. However, in particular, when a mercapto group is used as a bleaching accelerator, at least one selected from a compound having a disulfide bond, a thiazolidine derivative, a thiourea derivative, and an isothiourea derivative, conventional bleaching , compared to the case where these bleach accelerators are included in the bleach bath during the fixing process,
This is preferred because not only can the bleaching accelerating effect be significantly enhanced, but also a significantly superior bleaching accelerating effect can be obtained than is known in conventional bleaching baths and desilvering methods. In particular, if there is a mercapto group in the molecule or
When adding a compound having a disulfide bond, a thiazoline derivative, or an isothiourea derivative described in Publication No. 95630 to a bleaching solution as a bleaching accelerator, the amount to be added depends on the type of photographic material to be processed, the processing temperature, and the intended processing. Although it varies depending on the time required, etc., the amount is suitably 1 x 10 ^-5 to 10 ^-1 mol, preferably 1 x 10 ^-4 to 10 ^-2 mol per treatment solution. In the method for developing silver halide color photographic materials of the present invention, the water washing bath following the desilvering step is selected from sodium salts or potassium salts of aminocarboxylic acids, aminophosphonic acids, phosphonic acids, and phosphonocarboxylic acids. A processing method is adopted in which the amount of replenishment of the solution in the washing bath is 3 to 50 times the amount brought in from the previous bath per unit area of the photosensitive material to be processed. It's okay. The bath having the fixing ability described above may be composed of a plurality of baths. That is, the bath having fixing ability may be provided independently after the bleach bath, may be provided as a bleach-fix bath, or may be provided as a bleach-fix bath after the bleach bath. In other words, after the fixing step or bleach-fixing step, processing steps such as water washing and stabilization are generally performed, but it is also common to perform only water washing or, conversely, to perform only stabilization processing without any actual washing step. It is also possible to use a simple processing method such as performing the following. It is also possible to apply a water-saving type of washing process that reduces the use of washing water and stably performs the entire development process without special drainage equipment. This water-saving washing bath may contain a chelating agent such as a sodium salt or potassium salt of aminopolycarboxylic acid, aminopolyphosphonic acid, polyphosphonic acid, phosphonocarboxylic acid, or the like. These chelating agents not only have a bactericidal effect against bacteria and contribute to stabilizing the washing water, but also have the unexpected effect of preventing fading of cyan images by using sodium and potassium salts in particular. can be obtained. Next, specific examples of chelating agents that can be included in the washing water to achieve the above effects include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-
hydroxyethylidene-1,1-diphosphonic acid,
Examples include phosphonic acids such as ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid. The amount added to the washing water of the sodium salt or potassium salt of aminopolycarboxylic acid used in the present invention is 1 x 10 ^-4 to 1 x 10 ^-1 mol/, preferably 5 x
10 ⁻⁴ to 2×10 ⁻² mol/, particularly preferably 1×
10 ⁻³ to 1×10 ⁻² mol/. 1×10 ^-4 mol/
If the amount is less, the addition of these chelating agents will have no effect, and if the amount is more than 10 ^-1 mole, salt will precipitate on the film surface of the photosensitive material after drying, or scum will adhere to the back side or emulsion side. This is not preferable since it may cause problems such as yellow staining or an increase in yellow stain. Various compounds can be added to the above-mentioned washing process for the purpose of preventing precipitation and stabilizing the washing water. For example, disinfectants and antibacterial agents that prevent the growth of various bacteria, algae, or molds (e.g., Journal of Antibacterial and Antifungal Agents (J. Antibact.
Antifung.Agents) Vol. 11, No. 5, pp. 207-223 (1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal"), magnesium salts and aluminum salts. Metal salts, alkali metal and ammonium salts, surfactants for preventing drying load and unevenness, etc. can be added as necessary. Examples of fungicides that can be used in combination include thiazole, isothiazole, halogenated phenols, sulfanilamide, and benzotriazole. The silver halide color light-sensitive material used in the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate
Preferably, various precursors of color developing agents are used. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, Schiff base-type compounds described in U.S. Pat. Metal salt complexes of
−16133, No. 56-59232, No. 56-67842, No.
No. 56-83734, No. 56-83735, No. 56-83736,
No. 56-89735, No. 56-81837, No. 56-54430,
No. 56-106241, No. 56-107236, No. 57-97531
Examples include various salt-type precursors described in No. 57-83565 and No. 57-83565. The silver halide color photosensitive material used in the present invention may contain various 1-phenyl-3-pyrazolidones, if necessary, for the purpose of promoting color development. A typical compound is published in Japanese Patent Application Publication No. 1986-
No. 64339, No. 57-144547, No. 57-211147, No. 64339, No. 57-144547, No. 57-211147, No.
No. 58-50532, No. 58-50536, No. 58-50533,
58-50534, 58-50535 and 58-115438
It is written in the number etc. Various treatment liquids in the present invention are used at 10°C to 50°C. A temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed. A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary. (Effects of the Invention) According to the method for forming an indonaphthol-based photographic dye image of the present invention, even when a halogen silver color photographic light-sensitive material is developed using a bleaching solution with weak oxidizing power or a bleaching solution that is tired, the color density decreases little. , and has the excellent effect that the dependence of its spectral absorption on color density is also small. Furthermore, the photographic dye image formed in this manner exhibits an excellent effect of being excellent in heat and light fastness. (Examples) Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 Photosensitive materials Samples 101 to 105 were prepared on a cellulose triacetate film support, each layer having the composition shown below. (Sample 101) 1st layer: Red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 5 mol%, average grain size
0.4μ） Silver coating amount 1.79g/m ² Sensitizing dye 4.5×10 ^-4 mol per mol of silver Sensitizing dye 1.5×10 ^-4 mol per mol of silver Coupler EX-1 per mol of silver 0.06mol Second layer: Protective layer polymethyl methacrylate particles (approx. 1.5μ in diameter)
In addition to the above composition, each layer contains a gelatin hardening agent H.
-1 and a surfactant were added. The sample prepared as described above was designated as sample 101. Samples 102 to 105 use coupler EX-2 and coupler EX, respectively, instead of coupler EX-1 in sample 101.
Sample 101 was prepared in the same manner as Sample 101 except that Coupler (1), Coupler (6), and Coupler (8) were added in equimolar amounts as EX-1. Compound used to prepare the sample Sensitizing dye: anhydro-5,5'-dichloro-
3,3'-di-(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide.
Pyridinium salt Sensitizing dye: anhydro-9-ethyl-3,
3'-di-(γ-sulfopropyl)-4,5,
4′,5′-dibenzothiacarbocyanine hydroxide triethylamine salt

[ka]

[Chemical formula] H-1 (CH ₂ = CHSO ₂ CH ₂ CONHCH ₂ ) _-2 After exposing the obtained samples 101 to 105 to light for sensitometry, the following development treatment [A] was carried out at 38°C. I did it. 1 Color development 3 minutes 15 seconds 2 Bleaching 6 minutes 30 seconds 3 Washing 3 minutes 15 seconds 4 Fixing 4 minutes 20 seconds 5 Washing 3 minutes 15 seconds 6 Stability 1 minute 5 seconds The composition of the processing solution used in each processing step is as follows. It is. Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate Add 4.5g water 1 Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml Ethylenediaminetetraacetic acid sodium iron salt
130.0g Glacial acetic acid 14.0ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium biphosphite 4.6g Add water 1 Stabilizer Formalin 8.0ml Add water 1 Next, development processing [B] was carried out in the same manner as development processing [A] except that the bleaching processing solution in development processing [A] was changed to the following processing solution formulation. This bleaching solution is a schematic reproduction of the state in which a large amount of photosensitive material has been processed and has become fatigued. Treatment process [B] Bleach solution composition (D-1) Ammonium bromide 160.0g Aqueous ammonia (28%) 7.1ml Ethylenediaminetetraacetic acid sodium iron salt 117g Glacial acetic acid 14ml Add water to 900ml (D-2) Sodium ethylenediaminetetraacetate Add 130g of iron salt and water. 1. Pour steel wool into (D-2) and seal it.
After leaving to stand to convert Fe()-EDTA to Fe()-EDTA, 100 ml of this was added to (D-1) to make the bleaching solution for processing step [B].
processed in the same way. The concentrations of samples 101 to 105 treated in treatment steps [A] and [B] were measured using red light. The results are shown in Table 1. Couplers (3), (4), (9), (10), (28) of the present invention, and
Samples 106 to 113 were prepared in the same manner as sample 101, except that (29), (31), or (32) was substituted with an equimolar amount. These samples were subjected to the same exposure as sample 101,
Development processing and density measurement were performed. The results are also shown in Table 1.

[Table] From Table 1, sample 101 using coupler EX-1 shows a significant decrease in color density when treated with a tired bleaching solution, whereas coupler EX-2 and couplers (1), ( 6), Sample 102 using (8)
It can be seen that with 105, there is almost no decrease in color density. In addition, when we investigated the changes in spectral absorption of the developed color images of samples 101 to 105 treated with [A], we found that the samples
Sample No. 102 had a significantly large change in spectral absorption depending on the color density, while Sample No. 101 and Samples 103 to 105 had almost no noticeable change. Furthermore, samples of the present invention
It can be seen that in samples Nos. 106 to 113, there is almost no decrease in color density even when bleaching is performed using a tired bleaching solution. From the above results, it can be concluded that the cyan coupler of the present invention is an excellent product that hardly causes a decrease in color density even when treated with a fatigue bleaching solution, and that the dependence of its spectral absorption on color density is small. it is obvious. Example 2 Coupler EX- of sample 101 produced in Example 1
Coupler EX-3, coupler each instead of 1
Samples 201, 202, and 203 were prepared in the same manner as sample 101 except that coupler (12) and coupler (12) were added in the same mole as coupler EX-1. Compound used to prepare the sample

[Formula] After exposing samples 201 to 203 and samples 101, 104, and 105 obtained in Example 1 to light for sensitometry, the same development process as in Example 1 [A]
(1) At 100℃ using the developed sample obtained.
Color image fastness was tested under two conditions: 14 days left in the dark, and 7 days light exposure using a xenon tester (100,000 lux). The results are shown in Table 2.

[Table] It is clear from Table 2 that the color image formed by the coupler of the present invention has excellent fastness. Example 3 Multilayer color photosensitive material samples 301 to 303 were prepared on a cellulose triacetate film support, each layer having the composition shown below. (Sample 301) 1st layer: Antihalation layer Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer Gelatin layer containing an emulsified dispersion of 2,5-di-tert-octylhydroquinone 3rd layer: First red sensation Emulsion layer Silver iodobromide emulsion (silver iodide 5 mol%) Silver coating amount 1.6 g/ ^m2 Sensitizing dye 4.5 x 10 ^-4 mol per mol of silver Sensitizing dye 1.5 x 10 per mol of silver ^-4 mol Coupler EX-1 0.03 mol per mol of silver Coupler EX-4 0.003 mol per mol of silver Coupler EX-5 0.0008 mol per mol of silver 4th layer: 2nd red-sensitive emulsion layer Silver bromide emulsion (silver iodide 10 mol%) Silver coating amount 1.4 g/m ² Sensitizing dye 3 x 10 ^-4 mol per mol of silver Sensitizing dye 1 x 10 ^-4 mol per mol of silver Coupler EX-6 0.005 mol per mol of silver Coupler EX-7 0.017 mol per mol of silver Coupler EX-4 0.0016 mol per mol of silver 5th layer: Intermediate layer 6th layer same as the 2nd layer :1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide ⁴ mol%) Silver coating amount 1.2 g/m2 Sensitizing dye 5 x 10 ^-4 mol per mol of silver Sensitizing dye per mol of silver Coupler EX- ⁸ 0.05 mole per mole of silver Coupler EX-9 0.008 mole per mole of silver Coupler EX-10 0.0018 mole per mole of silver 7th layer: 2nd layer Green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 8 mol%) Silver coating amount 1.3 g/m ² Sensitizing dye 3 x 10 ^-4 mol per mol of silver Sensitizing dye 1.2 per mol of silver ×10 ^-4 mol Coupler EX-11 0.017 mol per mol of silver Coupler EX-12 0.003 mol per mol of silver 8th layer: Yellow filter layer Yellow colloidal silver and 2,5-
Gelatin layer containing emulsified dispersion of di-tert-octylhydroquinone Ninth layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 mol%) Silver coating amount 0.7 g/m ² Coupler EX-13 0.25 mol per mol of silver Coupler EX-14 0.015 mol per mol of silver 10th layer: 2nd blue-sensitive emulsion layer Silver iodobromide (6 mol% silver iodide) Silver coating amount 0.6 g/m ² Coupler EX-13 0.06 mol per mol of silver 11th layer: 1st protective layer Silver iodobromide (silver iodide 1 mol%, average grain size 0.07 μ) Silver coating amount 0.5 g/m ² Ultraviolet absorber UV Gelatin layer containing the emulsified dispersion of -1 Twelfth layer: Second protective layer Gelatin layer containing polymethyl methacrylate particles (diameter 1.5μ) In addition to the above composition, each layer contains a gelatin hardening agent H
-1 and a surfactant were added. The sample prepared as described above was designated as sample 301. Samples 302 and 303
were prepared in the same manner as sample 301 except that coupler (6) and coupler (8) were added in equimolar amounts as coupler EX-1 instead of coupler EX-1 in the third layer of sample 301. Compounds used to prepare the sample Sensitizing dye: anhydro-9-ethyl-5,
5'-dichloro-3,3'-di-(γ-sulfopropyl)oxacarbocyanine sodium salt Sensitizing dye: anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl- 3,3'-di{β-[β-(γ-sulfopropoxy)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt

[ka]

[ka]

【formula】

[ka]

[ka]

[ka]

[ka]

【formula】

[ka]

[ka]

[ka]

[C] After exposing the obtained samples 301 to 303 to light for sensitometry, two types of development processing [A] and [B] were performed as in Example 1, and the processed samples were exposed to red light. The concentration was measured using The results are shown in Table 3.

[Table] From Table 3, sample 301 in which coupler EX-1 was used in the third layer showed a remarkable decrease in concentration in the treatment [B] using fatigue bleaching solution, whereas the coupler of the present invention (6)
In Samples 302 and 303 using (8), almost no decrease in concentration was observed in treatment [B].

Claims (1)

[Scope of Claims] 1. A method for forming an indonaphthol-based photographic dye image, which comprises the following steps a) and b) but does not include step c); a. Developing an imagewise exposed photographic light-sensitive material; forming an image-like distribution of the oxidized color developing agent. b. A step of reacting this oxidized color developing agent with a coupler represented by the following general formula () to form an indonaphthol dye image. However, the indonaphthol dye formed here does not have a metal chelation site that can form a tridentate or higher metallized dye. c. Contacting this dye image with polyvalent metal ions to form a metallized dye image. General formula () [Formula] (In the formula, R ₁ is −CONR ₃ R ₄ , −NHCOR ₃ , −
NHCOOR ₅ , -NHSO ₂ R ₅ , -NHCONR ₃ R ₄ or -NHSO ₂ NR ₃ R ₄ , R ₂ is a group that can be substituted with naphthol, m is an integer of 0 to 3, X is HN, R ₆
N or R ₆ OCON, and Y represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized aromatic primary amine developer. However, R ₃ and R ₄ are hydrogen atoms, aliphatic groups, aromatic groups, or heterocyclic groups, R ₅ and R ₆ are aliphatic groups,
Indicates an aromatic group or a heterocyclic group. Here, the aliphatic group refers to a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be substituted. The aromatic group refers to a substituted or unsubstituted monocyclic or condensed ring aryl group.
The term "heterocyclic group" refers to a substituted or unsubstituted monocyclic or condensed ring heterocyclic group. ) 2 The method according to claim 1, wherein the color developing agent is represented by the following general formula (); [Formula] (wherein R ₇ and R ₈ are each independently a hydrogen atom, an alkyl group or a hydroxyl group, represents an alkyl group substituted with at least one of an alkoxy group, an alkoxyalkoxy group, or an alkylsulfonamide group, R ₉ represents an alkyl group, an alkoxy group, or a halogen atom, and n is a substituent
R is the replacement number of ₉ and represents an integer from 0 to 4,
When n is 2 or more, R ₉ may be the same or different. ) 3 The method according to claim 1, wherein in the general formula (), R ₁ represents CONR ₃ R ₄ , R ₃ is a substituted alkyl group, and R ₄ is a hydrogen atom. 4. The method according to claim 3, wherein in the general formula (), the substituted alkyl group of R ₃ is an alkoxyalkyl group. 5. The method according to claim 1, wherein in the general formula (), X is R ₆ OCON. 6. The method according to claim 5, wherein in the general formula (), X is R ₆ OCON and R ₆ is an alkyl group. 7 In the general formula (), X is R ₆ N,
The method according to claim 1, wherein R ₆ is an alkyl group.