JPS6235355A - Photosensitive silver halide color photographic material - Google Patents

Abstract

PURPOSE:To obtain an image having improved sharpness by incorporating a compound which is converted into a colored compound having the principal absorption in the principal absorption wavelength range of a dye produced by the reaction of a diffusion resistant coupler with the oxidized product of a color developing agent in a developing stage, diffuses moderately and can react with the oxidized product of the developing agent. CONSTITUTION:This color photographic material contains a compound which is converted into a colored compound having the principal absorption in the principal absorption wavelength range of a dye produced by the reaction of a diffusion resistant coupler with the oxidized product of a color developing agent, diffuses moderately and can react with the oxidized product of the developing agent. The compound in the color photographic material is converted into the colored compound in a developing stage. The maximum absorption wavelength is preferably changed by >=10nm by the conversion. The color tone is preferably changed by hydrolysis. The compound in the color photographic material may be represented by formula I, II or III.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a photosensitive silver halide color photographic material (hereinafter referred to as
It is simply called photographic material. ), and in particular to photographic materials in which color images and unsharp masks can be automatically formed. (Prior art) As a photographic material capable of forming color images and unsharp masks to obtain color images with excellent sharpness, a physical development nucleus-containing layer containing a diffusion-resistant coupler and a scavenger for oxidized color developing agents are used. A photographic material is disclosed in French Patent No. 2,260,124 in which a light-sensitive silver halide emulsion layer containing a diffusion-resistant coupler and a light-sensitive silver halide emulsion layer are laminated in sequence. A preferred method for obtaining a color negative image and an unsharp positive image using the photographic material is to perform color development after exposure using a first color developer containing no silver halide solvent to obtain a color negative image, and then to obtain a color negative image using a silver halide solvent. A method for obtaining an unsharp positive image by performing physical color development using a second Ih developer containing the following is disclosed. However, in order to obtain a color negative image, this photographic material undergoes a color development reaction in the exposed area, and in order to obtain an unsharp positive image, it undergoes a physical color development reaction using dissolved silver halide in the unexposed area. It is necessary to make this happen. Therefore, in order to prevent the color developing agent co-oxidant generated during the formation of a color negative image from diffusing into the layer containing physical development nuclei, a scavenger for the color developing agent oxidized product is placed between the two layers containing the diffusion-resistant coupler. It is essential that it exists. That is, in the absence of the scavenger, some of the oxidized color developing agent produced in the exposed region will diffuse into the physical development nucleus-containing layer, where a color development reaction will produce an unsharp negative image, resulting in the formation of a desired color negative image and an unsharp positive image. I can't get the image. Furthermore, since three layers including the scavenger content are essential, it is difficult to make the film thin, and from this point of view as well, it is difficult to improve sharpness. Further, as disclosed above, this method requires that color development be performed twice using two color developing solutions. If color development is carried out only once using only a color developer containing a silver halide solvent, color development is required to obtain a color negative image and silver halide complex is used to supply silver ions to the physical development nucleus-containing layer. It is difficult to control the generation of If this control breaks down and the complex is produced in excess, fewer color negative images will be produced, and as a result, the complex will diffuse excessively into the physical development nucleus layer, resulting in areas where color negative images should originally be produced. Since an unsharp positive image is generated, the desired color negative image and unsharp mask image cannot be obtained, and the objective cannot be achieved. (Object of the Invention) An object of the present invention is to solve the drawbacks of the above-mentioned prior art. That is, a first object of the present invention is to provide a photographic material capable of obtaining an image with improved sharpness by producing a color negative image and an unsharp positive image. A second object of the present invention is to provide a photographic material that provides images with excellent sharpness and requires fewer layers for improving sharpness. A third object of the present invention is to provide a photographic material capable of forming good color negative images and unsharp positive images through one-time color development. (Structure of the Invention) As a result of intensive research to achieve the above object, we have discovered that the object of the present invention can be achieved with a photographic material having the following structure. That is, the photographic material of the present invention comprises a diffusion-resistant coupler combined with a light-sensitive silver halide emulsion and, during the development process, (i) a dye formed by the reaction of the diffusion-resistant coupler with an oxidized form of a color developing agent; It changes color to a colored compound with main absorption in the main absorption wavelength range, and O) moderately diffuses.
and (III) a compound that reacts with the oxidized form of a developing agent. The present invention will be explained in more detail. First, during the development process, (i) the color changes to a colored compound having a main absorption in the main absorption wavelength range of the dye produced by the reaction between the diffusion-resistant coupler and the oxidized color developing agent; , and (ffi) a compound that can react with the oxidized form of a developing agent (
Hereinafter, it will be referred to as the compound of the present invention. ) will be explained. The compound of the present invention changes color into a colored compound having a main absorption in the main absorption wavelength range of the dye produced by the reaction between the diffusion-resistant coupler and the oxidized color developing agent during the development process, but the degree of color change is The change in maximum absorption wavelength is 10
It is preferable that it is at least nm. As such a discoloration mechanism, a preferred example is one in which the compound of the present invention changes in color tone by undergoing hydrolysis. In addition, although the compound of the present invention diffuses moderately during development processing,
Appropriately diffusing means that, in the development process using the photographic material of the present invention, in particular, in the development process, particles of 1 μm or more,
It preferably diffuses over 5 μm, but this means that at least 30 wt% of the added amount remains in the photographic material even after the processing step. Here, diffusion includes not only diffusion before the compound of the present invention causes discoloration, but also diffusion after discoloration. Furthermore, the compound of the present invention can react with the oxidized form of the developing agent in the presence of the oxidized form of the developing agent during the development process;
The reaction referred to here includes not only the reaction carried out before the compound of the present invention undergoes the above-mentioned color change, but also the reaction carried out after the compound changes color. The compounds of this invention yield colored or colorless products upon reaction with oxidized developing agents. If the reaction product has a color tone that is undesirable in terms of image formation, the reaction product flows out of the photographic material. Therefore, in the area where a color image is produced by the reaction between the oxidized form of the color developing agent and the diffusion-resistant coupler, the compound of the present invention will also react with the oxidized form of the developing agent, producing a compound that becomes colorless or flows out of the system. ,
It is supported by one of these characteristics. Further, in areas where no color image is produced by the diffusion-resistant coupler, the compound of the present invention does not react with the oxidized form of the developing agent, but changes color during the development process as described above. As a result, the color image produced by the diffusion-resistant coupler and the compound of the present invention have an inverse relationship, i.e.,
If the former is a negative image, the latter will form a positive image. Moreover, since the compound of the present invention has appropriate diffusivity, it forms an unsharp image, that is, an unsharp mask image. The compounds of the present invention include, for example, the following general formula:

Examples include compounds represented by [1]. General formula (i) %Formula % The compound in the formula is an organic residue that can react with the oxidized developing agent and release the Link-8 moiety according to the amount of the oxidized developing agent, and Link connects A and B. The group B represents an organic residue. In addition, in the case where the product produced due to A and Link-B by the reaction between the compound represented by the general formula [1] and the oxidized form of the developing agent is a compound that exhibits a color tone that is undesirable in terms of image formation, After the reaction, the product is attached with a substituent that balances hydrophilicity or lipophilicity so that it flows out of the photographic material. Examples of A in general formula [1] include the residue of a coupler that produces a colored or colorless product through a coupling reaction with an oxidized form of a color developing agent, or a component that undergoes a cross-oxidation reaction with an oxidized form of a developing agent. It will be done. Specific examples of the former include phenols, naphthols, 5-pyrazolones, pyrazolotriazoles, pyrazolobenzimidazoles, indasilones, acylacetanilides, RCOCT (where R is, for example, alkyl, aryl, hetero ring group), O
Residues of NOHN-N1 (R' (2 is, for example, an atomic group completing a 5- to 8-membered saturated or unsaturated alicyclic ring or heterocycle, and R' represents an aryl residue) are listed. A specific example of the latter is, for example, after being oxidized,
) rjFJ rift niyo'l Link -B トL, TB -
Indanones and indoles that release SO and NHe,
After oxidation, residues of phenols, naphthols, and hydroquinones undergo an intramolecular ring-closing reaction, forming Link-
Phenols that release B-8o2e as B (for details, see U.S. Pat. No. 3,443,939, U.S. Pat. No. 3,443,
No. 940, No. 3,443,941, etc. ) residues are mentioned. For example, the link may be: For example, phthalic imidoyl, phthalic acid imidoyl, pyridoyl, imidazolyl, imidasilonyl, benzimidazolyl, hydantoyl, thiohydantoyl, triazolyl, benztriazolyl, urazolyl, 2,4-dioxyoxacylyl, 2゜4-dioxothiazolyl. Examples include ru, thiadiazolyl, and tetrazolyl. Further, R is alkyl, aryl, etc., each of which may have a substituent. As B, when Link is a chromophore such as -N=N-, -C1(=, for example, an aryl group or a heterocyclic group is preferable, and an auxochromic group in the A part and the B part, such as a hydroxyl group, an ami7 It is possible to change color during the development process by protecting groups (including substituted amino groups such as alkylamino and anilino) with a hydrolyzable group, such as an acyl group, or by protecting them with an intramolecular cyclized lactone. In addition, B may be a dye precursor described below. In addition, when Link is not a chromophore, B is a dye precursor,
Preferably, it is an organic residue that is hydrolyzed to give a pigment matrix, for example, at least one of the auxochromes of an azo dye, such as a hydroxyl group or an amino group (including a substituent mino), is hydrolyzed. Color change in the development process can be made possible by protecting the dye with a group such as an acyl group or by converting the ketone at the 5-position of the pyrazolone azo dye into an intramolecular cyclized lactone. Provides the compound represented by the general formula (i3) or the compound after color change with the property of moderate diffusion during development processing, and provides the property of diffusibility to flow out undesired products after the reaction out of the system. For example, carboxyl group, sulfo group,
The diffusivity before and after the reaction may be balanced by appropriately introducing an alkali-soluble group such as a hydroxyl group or a sulfamoyl group and a group that reduces diffusivity such as an alkyl group. When the compounds of the present invention are classified based on their properties, for example, the following classifications can be mentioned. CLASS I: Coloring dye-forming type Compounds belonging to this category have the general formula (The A part of i1 is a coupler residue, and the Link part is bonded to the active point of the coupler. However, Link is -NH8O□- (nitrogen atom is Co
In the case of binding to the up region), it may be adjacent to the active site. The photographic material preferably contains an alkali-soluble group and, for example, an alkyl group having 16 or less carbon atoms so as to have appropriate diffusion. If the coloring dye produced by the coupling of the A part with the oxidized product of the color developing agent is undesirable for image formation, the A part is added so that the coloring dye flows out of the system during processing.
It is preferable to have an alkali-soluble group present in a portion thereof or to use a color developing agent having an alkali-soluble group. Moreover, when the B part forms a dye precursor, it is preferable that the B part has an alkali-soluble group so that the components originating from the B part after the reaction flow out of the system. In compounds belonging to this category, part A forms a negative colored dye image in the exposed area, but flows out of the system, and if part B is a dye precursor, the part originating from B also forms after separation from part A. Since it flows out of the thread, a positive image is created by the compound represented by the general formula group remaining in the non-exposed area. Moreover, since this compound has moderate diffusivity, it moves slightly through the layer during the development process to form an unsharp positive image. Next, a group of compounds that do not produce a color image after a color reaction will be explained. CLASS I: Colorless coupling product forming type Compounds belonging to this category have general formula [1] where A part is CLASS
It reacts in the same manner as compound I, but since the reactive component is colorless, it may remain in the layer after the coupling reaction. CLASS I Niredox reaction type Compounds belonging to this category do not undergo coupling reactions like CLASS I or ■. Instead, it reacts with the oxidized developing agent to produce quinone, quinoid, etc., but the dye or its precursor is released only after this product reacts with an alkali in the developer or undergoes an intramolecular ring-closing reaction. Next, specific examples of compounds layered in each of these classes will be given, but the present invention is not limited to these compounds. C1ass 1 C1ass 1 H In the case of C1ass I, these compounds are acylated in the final step to obtain the target product, but in the case of C1ass 11 and ■
In this case, it is appropriate to acylate the dye moiety (B moiety in general formula (i)) when it is synthesized and then bond it to the A-Link moiety. Synthesis Example 1 (Synthesis of Compound Example (2)) 1- obtained by diazo coupling of l-hydroxy-4-aminophenoxy-2-1-propylnaphthamide with diazoniem chloride and N-acetyl-H acid.
Hydroxy-4-(4-(2(l-hydroxy-8-acetylamino-3-6-cissulfonaphthylazo)phenoxy)]2-1-propylnaphthamide 7 g and 3 o m
Isopropenyl acetate (e) was dissolved in 1001 ethyl acetate, 2 drops of concentrated sulfuric acid were added, and the mixture was heated under reflux for 2 hours. After the reaction solution was cooled to room temperature, 19% of sodium carbonate was added to neutralize the sulfuric acid melting medium, and then separated, ethyl acetate and excess isopropenyl acetate were distilled off under reduced pressure, and then crystallized with n-hexane. The raw material azo compound is an orange powder, but the compound (2) thus obtained is a yellow powder.Synthesis Example 2 (Synthesis of compound example (4) t2.) 3-(4-amino) 2-5-dioxoimidacillin 38I Dissolve in 2 oruts of acetonitrile,
Add pyridine α511t to this. While stirring at 20'C, 2-ethylaminosulfanyl-5 synthesized according to the synthesis example D-1 of JP-A-55-33141 was added.
-methylsulfonylamino-4-(2-(2-(4
Chlorsulfonylphenyl)ethylsulfonyl)4
-Nitrophenylazo-1-naphthoyltrifluoroacetate) 4.39 is gradually added. After all the addition was completed, the mixture was stirred at room temperature for about 2 hours, and then boiled and refluxed for 9 minutes. water 20
The oily product was collected by decantation and washed several times with hot hexane to give an orange powder 6I. The photographic material of the invention comprises a diffusion-resistant coupler and a compound of the invention in combination with a light-sensitive silver halide emulsion as described above. Here, the diffusion-resistant coupler is preferably contained in the photosensitive silver halide emulsion layer. Further, the compound of the present invention is contained in the silver halide emulsion layer and/or in a photographic constituent layer separate from the silver halide emulsion layer. The above-mentioned another photographic constituent layer does not need to be an adjacent layer to the above-mentioned silver halide emulsion layer, but is preferably an adjacent layer,
Further, it is preferable to position the silver halide emulsion layer on the side opposite to the light incident side during exposure. Further, the other photographic constituent layer may be a light-sensitive silver halide emulsion layer having the same color sensitivity as the light-sensitive silver halide emulsion layer, or may be a non-light-sensitive layer. When the compound of the present invention is contained in the non-photosensitive layer, the compound of the present invention reacts with the developing agent that has been diffused into the non-photosensitive layer among the developing agents generated by development in the photosensitive silver halide emulsion layer. As a result, an unsharp mask image is formed. The amount of the compound of the present invention to be used is 0.01 to 1 mole of the diffusion-resistant coupler used in combination with the compound.
．． 00 mol is preferable, and 0.05 to 0.60 mol is particularly preferable. Further, as the method for adding it, the same method as that for the diffusion-resistant coupler described later can be used. As the silver halide used in the photosensitive silver halide emulsion used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. 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. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. Furthermore, the interior and surface of the silver halide grains may be composed of a uniform phase, or may be composed of different phases. The silver halide grains used in the silver halide emulsion of the present invention 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 grains. The silver halide emulsion of the present invention may have any grain size distribution. 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) may be used. The term "monodisperse emulsion" as used herein refers to one in which the standard deviation of grain size distribution divided by the average grain size is 0.15 or less. Here, in the case of spherical silver halide, the grain size is the diameter thereof, and in the case of grains having a shape other than spherical, it is the diameter when the projected image is converted into a circular image of the same area. Further, polydisperse emulsions and monodisperse emulsions may be used alone or in combination. The silver halide emulsion may be chemically enlarged 118. Additionally, dyes known in the photographic industry as sensitizing dyes can be used to optically sensitize to a desired wavelength range. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, a supersensitizer, which is a dye that itself does not have a spectral sensitizing effect or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye, is included in the emulsion. Also good. As the binder for the silver halide emulsion according to the present invention, gelatin and various hydrophilic Freud's polymers are used. Gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes a reaction product of gelatin acid anhydride, a reaction product of gelatin and isocyanate, or a reaction product of gelatin and a compound having an active halogen atom. Things, etc. are included. Examples of the acid anhydride used in the reaction with gelatin include maleic anhydride, phthalic anhydride, benzoic anhydride, acetic anhydride, isatoic anhydride, and succinic anhydride, and examples of the isocyanate compound include, for example, phenyl anhydride. isocyanate, p-chlorophenylisocyanate), p-chlorophenylisocyanate, p-)lylisocyanate, p-nitrophenyl isocyanate, naphthylisocyanate, and the like. Furthermore, examples of compounds having an active halogen atom include benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-7 enoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride);', p-)luenesulfonyl chloride, m -Nitrobenzenesulfonyl chloride, m-sulfobenzoyl dichloride, naphthalene-β-sulfonyl chloride, p-chlorobenzenesulfonyl chloride, 3-
Nitro-4-aminebenzenesulfonyl chloride, 2
-carboxy-4-bromobenzenesulfonyl chloride, m-carboxybenzenesulfonyl chloride, 2
-amino-5-methylbenzenesulfonyl chloride,
Phthalyl chloride, p-nitrobenzoyl chloride, benzoyl chloride, ethyl chlorocarbonate,
Furoyl chloride and the like are included. In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, as needed hydrophilic colloids for preparing silver halide emulsions include colloidal al-pumin, agar, gum arabic, dextran, alkynic acid, etc. Cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 19 to 26%, polyacrylamide, imidized polyacrylamide, casein, urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinyl cyanoacetate copolymers, etc. Vinyl alcohol polymers containing, polyvinyl alcohol-orivinyl pyrolidone, hydrolyzed polyvinyl acetenide, polymers obtained by weight of proteins or saturated acylated proteins and monomers having vinyl groups, polypynylhy”lysine, polyvinylamine, polyaminoethyl methacrylate , polyethyleneimine, etc. The silver halide emulsion of the present invention may contain coating aids, antistatic agents,
Improved slipperiness, emulsification and dispersion, adhesive prevention and photographic properties (
For example, various known surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization. That is, U.S. Patent Nos. 2,240,472, 2,831°766, 3,158.484, and 3,210.1
No. 91, No. 3,294,540, No. 3,507,66
No. 0, British Patent No. 1,012,495, British Patent No. 1,022,
No. 878, No. 1,179.290, No. 1,198,4
No. 50, U.S. Patent No. 2,739,891, U.S. Patent No. 2,823
, No. 123, No. 1.179, 290, No. 1,198.
No. 450, No. 2゜739.891, No. 2,823.1
No. 23, No. 3,058゜101, No. 3,415,64
No. 9, No. 3, 666, 478, No. 3,756, 8
No. 28, British Patent No. 1,397,218, British Patent No. 3,113
, No. 816, No. 3,411.413, No. 3,473,
No. 174, No. 3,345,974, No. 3.726,6
No. 83, No. 3,843,368, Belgian Patent No. 731
, No. 126, British Patent No. 1,138,514, No. 1,1
No. 59,825, No. 1,374,780, U.S. Patent 2
, No. 271,623, No. 2,288,226, No. 2
, 944, 900, 3,235,919, 3.671,247, 3,772.021, 3
゜589.906, 3,666.478, 3,
No. 754°924, West German patent application OL81,961,6
No. 83 and JP-A-50-117414, JP-A No. 50-59
No. 025, Special Publication No. 40-378, No. 40-379,
It is described in No. 43-13822. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ether polyethylene glycols, e.g., ethitane glycol sorbitan esters, polyalkylene gelyl alkyl amines) or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. artenylsuccinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, urethanes or ethers, etc. nonionic surfactants, tritinopenoid sulfonine, alkyl carboxylates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl tauric acid, Anions containing acidic groups such as carboxy, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene titanium alkyl phosphates, etc. surfactant,
Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, amphoteric surfactants such as alkyl betaines, amine imides, amine oxides, alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridium Cationic surfactants such as heterocyclic quaternary ammonium salts such as , imidazolium, and sulfonium or sulfonium salts containing aliphatic or heterocycles can be used. In addition to the above-mentioned surfactants, the silver halide emulsion contains, as a development accelerator, West German Patent Application (OLS) 2.002,87
No. 1, No. 2,445,611, No. 2 360.878
It may contain imidazoles, thioethers, selenoethers, etc., which are described in British Patent No. 1,352,196 and the like. It is preferable to include the diffusion-resistant coupler in the above-mentioned light-sensitive silver halide emulsion layer. For example, a combination of the diffusion-resistant coupler and the diffusion-resistant coupler of yellow, magenta, and cyan may be used in blue-sensitive, green-sensitive, and red-sensitive silver halide emulsions. sexual couplers are applied respectively. Diffusion-resistant couplers contain lipophilic groups (for example, 2,4-
(di-t-amylphenoxyalkanamide group). The coupler may be either 4-equivalent or 2-equivalent to silver ion. It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). Further, some couplers may be used in which the product of the coupling reaction is colorless. As the yellow coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds can be advantageously used. Specific examples of yellow couplers that can be used include U.S. Pat.
No. 17438, No. 51-102636, Special Publication No. 1977-
No. 19956, No. 51-33410, No. 51-107
Although it is described in No. 83, No. 47-19031, etc.,
Particularly preferred yellow couplers include the following compounds. lI C00CHC00CI2H2゜C1 (i]) CI! t As magenta coloring couplers, pyrazolone compounds,
Indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. Specific examples of magenta color-forming couplers that can be used include U.S. Pat.
, No. 519,429, JP-A-49-111631, JP-A No. 56-29236, JP-A No. 57-94752.
No. 8-27930 and the like, particularly preferred couplers include the following compounds. CI! and n -Polymer latex made of a 20:80 copolymer of butyl acrylate impregnated with the above magenta coupler (2) As the cyan coloring coupler, phenolic compounds, naphthol compounds, etc. can be used, and specific examples thereof are as follows: is U.S. Pat. No. 2,423,730, 2.
No. 474,293, No. 2,895,826, Japanese Unexamined Patent Publication No. 1973
No. 0-117422, Japanese Patent Registration No. 127513
Particularly preferred cyan couplers include the following compounds. (X) C, H. Shit p H OCI(2CONHCH2CT(20CH3T4 ([H (i)) H Colored magenta couplers include, for example, U.S. Pat.
, No. 801,171, No. 3,519,429, and Japanese Patent Publication No. 48-27930, particularly preferred colored magenta couplers are as follows [1) C/C/p (5)
CHsCI! Colored cyan couplers are described, for example, in British Patent No. 1,084,480, Japanese Patent Publication No. 55-32461, etc., and particularly preferred colored cyan couplers include the following compounds. H H Two or more of the above various couplers can be contained in the same layer. Further, the same compound may be contained in two or more different layers. In order to introduce the coupler r into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.)
, phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate,
Dioctyl butyl phosphate), citric acid ester (e.g. acetyl tributyl citrate), Sabbath 1? esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), etc., or with a boiling point of about 30
℃ to 150℃, such as lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then hydrophilic. Dispersed into sex colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. These couplers are generally added in amounts of 2 X IF3 moles to 5 X l (r' moles, preferably IXI (r moles to 5 X1 moles) per mole of silver in the silver halide emulsion layer. A DIR compound can be used as the material, and examples of the DIR compound include those described in U.S. Pat. No. 2,327,554, U.S. Pat.
No. 424, No. 54-145135, No. 57-1519
Compounds described in Japanese Patent Publication No. 44, Japanese Patent Publication No. 51-16141, etc. can be preferably used. Particularly preferable DIR compounds include the following compounds, y"' ■ (2)'CH1 N=N (6) ('I! 辅C2H. CI! Also, those compounds that can be effectively used in the photographic materials of the present invention) The anti-staining agent obtained is described in, for example, U.S. Pat. H H The antistatic agent used in the present invention is a reaction product of diacetylcellulose, styrene perfluoroalkylridium maleate [i-form, a combination of styrene-maleic anhydride m, and p-aminobenzenesulfonic acid] Alkali salts, etc. are effective. Examples of matting agents include polymethyl methacrylate, polystyrene, and alkali-soluble polymers. Furthermore, colloidal silicon oxide can also be used. Also, in order to improve the physical properties of the film, Examples of the latex to be added include copolymers of acrylic esters, vinyl esters, etc. and other single fft bodies having ethylene groups. Examples of gelatin plasticizers include glycerin and glyfur-based compounds. Examples of thickeners include styrene-sodium maleate copolymers, alkyl vinyl ether-maleic acid copolymers, etc. Support for photographic materials made using silver halide emulsions prepared as described above Examples of the support include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, and polystyrene. It is selected as appropriate depending on the purpose of use of the photographic material. These supports are subjected to subbing processing as necessary. After exposure to the photographic material made using the silver halide emulsion according to the present invention, Development processing can be carried out by any known method used. Typical methods include a method in which a bleach-fixing treatment is performed after color development, and further washing and stabilization treatment as necessary; It is possible to apply a method in which fixing is carried out separately and, if necessary, further washing with water and stabilization treatment are carried out.As the color developing agent, various aromatic agents such as p-phenylene diamine type and p-amine phenol type can be used. Group primary amine developing agents are preferably used. (Examples) Next, the present invention will be specifically explained with reference to Examples. Example 1 A multilayer color photographic material consisting of each layer having the composition shown below was prepared on a cellulose triacetate film support. 1st layer: anti-halation layer 2nd F5 layer coated with gelatin solution containing black colloidal silver at #50~/m' gelatin o, 5 g/m'
: Intermediate layer: 2-3 gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone: Red-sensitive emulsion layer: Silver iodobromide emulsion containing 4 mol% of silver iodide and having an average grain size of 0.7 μm. Anhydro-5,5'-dikuoo-3゜3'-
C-γ-sulfoprobyl-9-ethyl-thiacarbocyanine hydroxide pyridium salt and anhydro-9-
ethyl-3,3-di-γ-sulfoprovir-4,5,
4-Hydroxy-6-methyl-1,3,3a in a high-speed red-sensitive emulsion color sensitized with a 4:1 mixture of 4',5'-dibenzochloride lupocyanine hydroxide triethylamine salt. A diffusion-resistant cyan coupler, 1-hydroxy-N-(α
-(2,4-di-t-amylphenoxy)buthyl]-2
- 0.07 mol of naphthamide per 1 mol of silver was dissolved in tricresyl phosphate by a conventional method, and then emulsified and dispersed in a gelatin solution, which was then added to yield 3.1 mol of silver.
9/m' A layer coated with gelatin of 5.0 g/m1. Fourth layer: Intermediate layer 2-gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone. 5th layer: Green-sensitive emulsion layer A silver iodobromide emulsion containing 5 mol% of silver iodide and having an average grain size of 0.75 μm was mixed with anhydro-9-ethyl-5,5'-dichloro-3,3'-di( γ-sulfopropyl) oxacarbocyanine sodium salt and anhydro-5,6,5',
6'-tetrachloro-1,1'-diethyl-3,3'
- 4-hydroxy-
The diffusion-resistant magenta coupler 1-(2°4.6-trichlorophenyl)-3-(3
-(α-(2,4-di-t-amylphenoxy)acetamide)-benzamide]-5-pyrazolone with an emulsified dispersion containing 0.08 mol per mol of silver was added, and this Further, the corresponding products of the present invention were added with an emulsified dispersion containing 0,000 mol of Exemplary Compound (2) per 1 mol of silver at a concentration of 2.3 mol of silver/2.79 mol of gelatin/m, respectively.
A layer coated so that it looks like this. 6th layer: yellow filter layer containing yellow colloidal silver and 2-5-di-t-octylhydroquinone dispersion (silver 0.19/m" gelatin 1.2.9/m'). 7th layer: blue Sensitive Emulsion Layer 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added as a stabilizer to a highly sensitive silver iodobromide gelatin solution containing 6 mol % of silver iodide and having an average grain size of 0.8 t+m. α is a diffusion-resistant yellow coupler after adding suitable charge
-C4-(i-benzyl-2-)uni-3,5-dioxo-1,2,4-)riazolidinyl)]-]〇-pivalyl-2-chloro5[γ-(2,4-di-t-amyl A comparison object to which an emulsified dispersion containing 0.22 mol of phenoxy)butyramide]acetanilide per 1 mol of silver was added, and an emulsified dispersion further containing 0607 mol of exemplified compound (3) per 1 mol of silver. Each added counterpart of the present invention was silver 1.09/rr? Gelatin 3 g/m'
A layer coated so that 8th layer: Protective layer polymethyl methacrylate particles (average diameter 1.5tim
) containing a gelatin layer. Each layer contains 2-hydroxy-4,6 gelatin as a hardening agent.
-Dichloro-s-triazine sodium salt or Habis-(
Vinylsulfonyl)ethane and a surfactant were added. After drying the target photographic material and the photographic material of the present invention obtained as described above, they were exposed to light for MTF measurement and sensitivity measurement through a single layer of B, G, and R filters, and then developed as described below. processed. Processing step (38°C) Processing time "Color development 3 minutes 15 seconds The composition of each processing solution that can be used in the above processing step is as follows, for example. [Color developer composition] " (Sodium chloride 0.149 [ Bleach solution composition] [Fixer composition] [Stabilizing solution composition] The image sharpness thus obtained is shown in Table 1 (MTF' at a frequency of 20 lines per i head) Table 1 There is a clear improvement effect In addition, the specific sensitivity varied within ±3% compared to the comparison, and no desensitizing effect by the compound of the present invention was observed.Example 2 Example 10 In between, an emulsified dispersion in which the same red-sensitive emulsion as in Example 1 was made to contain 0.25 mol of Exemplary Compound (4) per 1 mol of silver was mixed with gelatin at 2.080/m' and silver at 0.723/m'. Example 10 A red-sensitive mask layer was coated to give a red-sensitive mask layer, and 1 mol of silver of the exemplary compound (5) was added to the same green-sensitive emulsion as in Example 1 between the fourth and fifth layers of the sample of the present invention in Example 10. An emulsified dispersion containing 0.25 mol of gelatin and 0.41/d of silver
．． A green mask layer coated to give a thickness of 3&/m' is provided,
Further, between the 6th R and 7th layers of the sample of the present invention in Example 1, an emulsion dispersion was prepared in which the same blue-sensitive emulsion as in Example 1 contained 0.25 mol of exemplified compound (i) per 1 mol of silver. Things to gelatin 0.6g/♂, silver 2,! Example 1 except that a blue-sensitive mask layer coated to give i'/m' was provided.
A sample of the present invention was prepared in the same manner as the sample of the present invention, and when exposed and developed in the same manner as in Example 1, a clear color image was obtained. Example 3 A Nagai color photographic material consisting of each layer having the composition shown below on a cellulose triacetate film support was prepared. 1st layer: Antihalation layer Black gelatin solution containing colloidal silver was added at 50 g/'-
, a layer coated with gelatin of 0.5#/rr7'. Second layer: Intermediate layer 2. Gelatin layer containing an emulsified dispersion of 5-di-t-oxytylhydroquinone. Third layer: Red-sensitive mask layer A silver iodobromide emulsion containing 4 mol % of silver iodide and having an average grain size of 0.7 μm was mixed with anhydro-5,5'-dichloro-3°31-
Cy-gamma-sulfoprobyl-9-ethyl thiamine hydroxide viridylium salt and anhydro-9
-ethyl-3,3'-di-γ-sulfoprovir-4,
4-Hydroxy-6-methyl-1,313a,7-thitrazaindene was added to a highly sensitive red-sensitive emulsion color sensitized with a mixture of 5,4',5'-dibenzothousacarbocyanine hydroxide triethylamine salt. Exemplified compound (4) was dissolved in tricresyl phosphate at 0.25 mol per mol of silver, and then emulsified and dispersed in gelatin solution was added to stabilize the mixture. 0.72.9/m', gelatin 2.0.9/m'
A layer painted with compassion. Fourth layer: low-sensitivity red-sensitive emulsion layer In place of the silver iodobromide emulsion in the third layer, a silver iodobromide emulsion containing 5 mol % of silver iodide and having an average grain size of 0.4 μm was used, and exemplified compound (4) was used. In place of the diffusion-resistant cyan coupler, 1-hydroxy-N-(α-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide, 0% per mole of silver was added.
．． 07 mol, colored cyan coupler, 1-hydroxy-4-(2-carboethoxyphenylazo)-N-
α-(2,4-di-t-amylphenoxy)butyl]-
0.007 mol of 2-naphthamide° per mol of silver and 2-(i-phenyl-5-tetrazolylthio)-
Gelatin 21/rr? was prepared in the same manner as in the third layer except that 0.003 mol of 6-[α-(2,4-di-t-amylphenoxy)acetamide]indanone was used per mol of silver.
, silver 1.8. ! ? /rrio layer. 5th layer: High-sensitivity red-sensitive emulsion layer In place of the exemplary compound (4) in the 3rd layer, a diffusion-resistant cyan coupler, 1-hydroxy-4-ethoxycarbonylmethyloxy-N-[α-(2,4-di -t-amylphenoxy)butylene]-2-naphthamide per mole of silver and 2-(i-phenyl-5-tetrazolylthio)-6-[α-(2,4-di- Gelatin 3.0.9/m', silver 2.0.9/m' in the same manner as in the third layer except that 0.001 mol of t-amylphenoxy)acetamide]indanone was used per 1 mol of silver. A layer coated to achieve og/m'. 6th layer: Intermediate layer "gelatin layer containing an emulsified dispersion of 2.5-di-t-octhyl-hy-V quinone. 7th layer: Green-sensitive mask layer containing 5 mol% silver iodide with an average grain size of 0. A 75 μm silver iodobromide emulsion was mixed with anhydro-9-ethyl-5,5'-dichloro-3,3'-di(γ-sulfopropyl)oxacarbocyanine sodium salt and anhydro-5,6,5',6
High density green emulsion color sensitized with a 3:1 mixture of '-tetrachloro-1,1'-diethyl-3,3'-di(γ-sulfoprobyl) imidazolocarbocyanine hydroxide triethylamine salt 4-hydroxy-
An emulsified dispersion containing 0.25 mol of exemplified compound (2) per mol of silver is added to the stabilized product by adding an appropriate amount of 6-methyl-1゜3,3a,7-chitrazaindene,
A layer coated with mN of 0.397♂ and gelatin of 0.4.9/m'. 8th layer: low-sensitivity green-sensitive emulsion layer In place of the silver iodobromide emulsion in the 7th layer, a silver iodobromide emulsion containing 4 mol % of silver iodide and having an average grain size of 0.35 μm was used, and exemplified compound (2) was used. Instead of wave resistant 1 aggressive magenta coupler, 1-
(2,4,6-)dichlorophenyl)-3-(3-(α
-(2,4-di-t-amylphenoxy)acetamide 0)-benzamide]-5-pyrazolo, 0.08 mol per mol of silver, colored coupler, 1-(2,4,
6-trichlorophenyl)-3-(3-(α-2,4-
di-t-amylphenoxy)acetamido)penzamide]-4-(4-methoxyphenylazo)-5-pyrazolone per mol of silver and 0.015 mol and 2-(i
-phenyl-5-tetrazolylthio)-6-[α-(2
Gelatin 1.1. ! 7/nr, silver 1
．． 09/m". 9th layer: high-sensitivity green-sensitive emulsion layer Instead of the exemplary compound (2) of the 7th layer, a diffusion-resistant magenta coupler, 4,4-bismethylene (i-(2゜4.6-
) dichlorophenyl)-3-(3-(α-(2,4-di-1-amylphenoxy)acetamido)-benzamide)-5-pyrazolone] per mol of silver and 0.01 mol and 2-(i -7enyl-5-tetrazolylthio)
-6-[α-(2,4-di-t-amylphenoxy)acetamide]indanone was used in the same manner as P;7 except that 002 mol of 00000 was used for 1 mol of ff1lJ, and gelatin was prepared at 1.659/m. , silver 1. s9/m". 10th layer: yellow filter layer containing yellow colloidal silver and 2,5-di-t-octylhydroquine compound (silver 0.1 E/m"). gelatin 1.2.9/go). 11th layer: Blue-sensitive mask layer Containing 6 mol% of silver iodide and having an average grain size of 0.8 μm, 4-hydroxy-bromide gelatin solution is added as a stabilizer.
After adding an appropriate amount of 6-methyl-1,3,3a,7-chitrazaindene, an emulsified dispersion containing 0.25 mol of exemplified compound (3) per mol of silver was added to gelatin o, 6 g/ m o, silver 0.2. ! A layer coated to give 9/rris. 12th layer: Blue-sensitive emulsion layer Yellow cabrateal α-(4-(i-benzyl-2-7enyl-3.5
-dioxo-1,2,4-)riazolidinyl)]-]α
-biparyl-2-chloro-5-γ-(2,4-di-t-
An emulsified dispersion containing 0.22 mol of amylphenoxy)butyranamide] acetanilide per 1 mol of silver was added at a ratio of silver 1.0.9/m' gelatin 3,! i' /
13th layer: Protective layer polymethyl methacrylate particles (average diameter 1.5 μm)
gelatin layer containing. Each layer contains 2-hydroxy-4, gelatin hardener,
6-dichloro-5-) riazine sodium salt was added with bis-(vinylsulfonyl)ethane and a surfactant. When the photographic material thus obtained was exposed and developed in the same manner as in Example 1, a clear color image was obtained. (Effects of the Invention) In addition to achieving the object of the present invention, it is possible to provide a color photographic material with a thin film and good sharpness, which reduces the number of coated photographic layers, and it has also become possible to reduce production costs and processing costs at the same time. Furthermore, since the compound of the present invention has a different color tone from the dye produced by the reaction between the diffusion-resistant coupler and the color developing agent, it is possible to reduce the decrease in sensitivity even when it is added to the light-sensitive silver halide emulsion layer. .

Claims (1)

[Claims] A diffusion-resistant coupler combined with a light-sensitive silver halide emulsion and, during the development process, (i) a reaction between the diffusion-resistant coupler and an oxidized form of a color-forming developing agent, which produces a main absorption in the main absorption wavelength range of the dye; It changes color to a colored compound with (
A light-sensitive silver halide color photographic material characterized in that it contains a compound that (ii) diffuses appropriately and (iii) can react with an oxidized form of a developing agent.