JPH0516577B2 - - Google Patents

Description

[Detailed description of the invention]

<<Industrial Application Field>> The present invention relates to a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a silver halide color photographic material containing a development inhibitor-releasing coupler. <<Prior Art>> In recent years, with the spread of small cameras, there has been a demand for image quality enlarged from a small size screen to be equivalent to image quality enlarged from a larger normal size screen. In order to satisfy these needs, it is necessary to develop a color photographic material that has enough graininess and sharpness that the printed image quality is not impaired even when the enlargement magnification is increased. Various methods have been known to improve the sharpness of images, but it is widely known that great effects can be obtained by increasing the edge effect and reducing light scattering in photographic materials. . Among these, the edge effect utilizes the concentration gradient of a development inhibiting substance present during development. Examples of the development inhibiting substance in this case include iodide ions and bromide ions released when silver halide is developed in a developer, and substances produced by oxidation of the developing agent. Effects similar to the effects of these development inhibitors are disclosed in U.S. Patent No. 3,227,554, U.S. Pat. No. 3,616,506, U.S. Pat. No. 3,617,291,
Compounds described in the same No. 3701783, etc., or Special Publication No. 1983
It is also known that it can be actively enhanced by using further improved so-called DIR compounds and DIR couplers as described in US Pat. It is being However, even when using the DIR coupler mentioned above, if it is necessary to produce a strong edge effect, a large amount of DIR coupler must be used, which inevitably greatly inhibits development. Therefore, there is a limit to the amount of DIR coupler that can be used, and there is also a limit to the edge effect caused by the above-mentioned DIR coupler. There was a drawback that there was no. Increasing the coating amount of silver to solve this problem not only increases product cost but also increases light scattering due to silver halide, which causes problems in high spatial frequency regions.
The MTF curve decreases, resulting in deterioration of the sharpness of not only the DIR coupler-added layer but also the underlying layer (for the MTF curve, see "The
Theory of Photographic Process”, 3rd
Edition, published by Macmillan). The present inventors have developed a DIR coupler that can improve the conventional drawbacks and particularly enhance the edge effect while ensuring a constant maximum image density, and have already filed an application (Japanese Patent Application No. 7150/1982). This invention is a diffusible development inhibitor-releasing coupler (hereinafter referred to as a diffusible DIR coupler) that can react with the oxidation product of a developing agent during development and release a development inhibitor with a diffusivity of 0.4 or more. The invention relates to a silver halide color photographic light-sensitive material characterized by containing. The present invention relates to an improvement of the above invention.
That is, the above-mentioned diffusive DIR coupler certainly has a remarkable effect on improving sharpness due to the edge effect, but on the other hand, it tends to slightly worsen graininess. For this purpose, a diffusive DIR coupler is contained in both the highest sensitivity layer (hereinafter referred to as O layer) and the lowest sensitivity layer (hereinafter referred to as U layer) with the same color sensitivity. In this case, the graininess of the portions where the exposure amount is small will deteriorate. As a result of intensive research to eliminate such drawbacks, the present inventors have found that when the ratio of diffusive DIR coupler to the normal DIR coupler added to the O layer is lower than the ratio when added to the U layer, a high The present invention was achieved by discovering that graininess in low exposure areas can be improved while maintaining image sharpness. <<Object of the Invention>> Therefore, the object of the present invention is to provide a silver halide color photographic light-sensitive material that does not impair the image quality of prints even when the enlargement magnification increases, has good graininess, and has extremely excellent image sharpness. Our goal is to provide the following. <<Structure of the Invention>> That is, the present invention provides a silver halide color photographic light-sensitive material containing a development inhibitor-releasing coupler capable of releasing a development inhibitor by reacting with an oxidation product of a developing agent during development. In a silver halide color photographic light-sensitive material containing a diffusive development inhibitor-releasing coupler with a degree of diffusion of 0.4 or more as a development inhibitor-releasing coupler, and a development inhibitor-releasing coupler with a degree of diffusion of less than 0.4, the development inhibitor This silver halide color photographic light-sensitive material is characterized in that the proportion of the diffusible development inhibitor-releasing coupler in the releasing coupler is lower in the highest-speed layer than in the lower-speed layer. <<Disclosure of the Invention>> The degree of diffusivity of the development inhibiting substance as used in the present invention can be measured by the following method. A multilayer color photosensitive material having the following composition was prepared on a transparent support and designated as Sample B. 1st layer: Red-sensitive silver halide emulsion layer Sensitizing dye I of Example 1 was added to a silver iodobromide emulsion (silver iodide 5 mol %, average grain size 0.4 μ) at 6 × 10 ^-5 per mol of silver. Emulsion that gives red sensitivity using moles,
A gelatin coating solution containing 0.0015 mol of coupler F per mol of silver was coated so that the amount of coated silver was 1.8 g/m ² (film thickness: 2 μm). Coupler F 2nd layer: Silver iodobromide emulsion used in the 1st layer (no red color) polymethyl methacrylate grains (diameter approx.
1.5 μ) gelatin layer (applied silver amount 2 g/m ² , film thickness
1.5μ). In addition to the above composition, each layer contains a gelatin hardening agent and a surfactant. A photosensitive material was prepared as Sample A, which did not contain the silver iodobromide emulsion in the second layer of Sample B, but had the same structure as Sample B except for this. The obtained samples A and B were subjected to wedge exposure and then processed according to certain conditions. A development inhibitor was added to the developer until the concentration of Sample A was reduced to 1/2. The degree of decrease in density of Sample B at this time was used as a measure of the diffusivity in the silver halide emulsion film. The results are shown in Table ().

【table】

[Table] The development inhibitor-releasing couplers with a diffusivity of less than 0.4 (hereinafter referred to as ordinary DIR couplers) used in the present invention are selected from known and commonly used DIR couplers with a diffusivity of less than 0.4. It can be selected and used arbitrarily, but especially when using one with a diffusivity of 0.3 or less, it is possible to improve the graininess in low-exposed areas while maintaining a high sharpness diffusivity. Therefore, it is preferable. The diffusive DIR coupler used in the present invention is the one described in Japanese Patent Application No. 171193/1983,
It is expressed by the following general formula []. like this
Among DIR couplers, those having a degree of diffusivity of 0.95 or less are particularly preferred in the present invention. General formula [] A-(-Y)m In the formula, A represents a coupler component, and m is 1 or 2
Y represents a group that binds to the coupling position of the coupler component A and leaves upon reaction with the oxidized product of the color developing agent, and represents a highly diffusible development inhibitor or a compound capable of releasing a development inhibitor. Such Y is represented by the following general formulas [] to []. General formula [] General formula [] General formula [] General formula [] In the present invention, among these, couplers and naphthotriazolyl groups (e.g.
Couplers having a 1H-naphtho[1,2-d]triazolyl group as a leaving group are preferred. In the formula, n represents 1 or 2, and when n is 1,
R ₁ represents a pentanamide group, hexaneamide group, propoxy group, N-butylcarbamoyl group, N-petylcarbamoyl group, N-hexylcarbamoyl group, N-butylcarbamoyl group, butoxy group, pentyloxy group or ethyl group, n is 2
In the case of , R ₁ represents a methyl group. R ₂ is a propyl group or a substituted phenyl group (the substituent is selected from N-methylsulfamoyl group, ureido group, carbamoyl group, N-methylcarbamoyl group, methanesulfonamide group or acetamide group, alkoxyacylamono group) .When the substituent contains an alkyl group, it preferably has 1 or 2 carbon atoms. These DIR couplers having a highly diffusible leaving group are represented by the following general formulas [], [] and []. General formula [] Or General formula [] General formula [] In the formula, A ₁ represents the residue excluding one hydrogen atom at the coupling position of the yellow coupler and magenta coupler, A ₂ represents the residue excluding one hydrogen atom at the coupling position of the cyan coupler, and A ₃ represents the yellow coupler. It represents a residue excluding one hydrogen atom at the coupling position of a coupler, magenta coupler, or cyan coupler, and R ₁ , R ₂ and n are the same as defined above. In general formulas [] and [], A ₁ and A ₃
When represents a residue obtained by removing one of the hydrogen atoms at the coupling position of a yellow coupler, those represented by the following general formulas [] and [] are particularly preferred. General formula [] General formula [] In the formula, R ₄ represents an aliphatic group or an aromatic group, and R ₅
and R ₆ each represent an aromatic group. In general formulas [] and [], A ₁ and A ₃
When represents a residue obtained by removing one of the hydrogen atoms at the coupling position of a magenta coupler, those represented by the following general formula [ ] are particularly preferred. General formula [] In the formula, R ₇ represents an aliphatic group, an amino group, an alkylamino group, a dialkylamino group, a cyclic amino group, or an acylamino group, and R ₈ represents an aliphatic group or an aromatic group. In general formulas [] and [], A ₂ and A ₃
When represents a residue obtained by removing one of the hydrogen atoms at the coupling position of a cyan coupler, those represented by the following general formula [ ] are particularly preferred. General formula [] In the formula, R ₉ and R ₁₀ each represent a hydrogen atom, an aliphatic group, or an aromatic group. When R ₄ , R ₇ , R ₈ , R ₉ or R ₁₀ represents an aliphatic group, the number of carbon atoms is preferably 1 to 22. In this case, the aliphatic group may be substituted or unsubstituted, chain or cyclic, or unsaturated. Preferred substituents are an alkoxy group, an aryloxy group, an acylamino group, a halogen atom, an alkylthio group, etc., and these may further have a substituent. Specific examples of useful aliphatic groups include, for example, methyl, tert-butyl, isoamyl, butyl, hexyl, dodecyl, hexadecyl, cyclohexyl, 3-(2,4-
di-tert-amylphenoxy)propyl group, 3-
Examples include dodecyloxypropyl group and α-(saxinimido)isopropyl group. When R ₄ , R ₅ , R ₆ , R ₈ , R ₉ or R ₁₀ represents an aromatic group, the aromatic group may be substituted.
Examples of substituents include halogen atoms (e.g. chlorine atoms, fluorine atoms, etc.), alkoxy groups having 32 or less carbon atoms,
Examples of substituents include alkyl groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkanesulfone groups, nitro groups, hydroxy groups, cyano groups, and ureido groups. When contains an alkyl group, the alkyl group may further have a substituent. Specific examples of useful aromatic groups include, for example, 2-chlorophenyl group, 2-methoxyphenyl group, 4-[2-(2,4-di-tert-amylphenoxy)butanamido]phenyl group, 2-chlorophenyl group, −
5-[2-(2,4-di-tert-amylphenoxy)butanamide] phenyl group, 2-tetradecyloxyphenyl group, 2,4,6-trichlorophenyl group, 4-methoxyphenyl group, phenyl group , 2,5-dichlorophenyl group, and the like. When R ₇ represents an aniline group, R ₇ may be substituted, and examples of the substituent in this case include a halogen atom, hydroxy group, cyano group, alkoxy group, alkyl group, alkoxycarbonyl group, aliphatic Examples include an amide group, an aromatic amide group, an alkylsulfamoyl group, an alkanesulfonamide group, and the like. When these substituents include an alkyl group or a phenyl group, they may further have a substituent. Useful anilino groups include, for example, anilino group, 4-methoxyanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-methoxy-5-tetradecyloxyanilino group, 2-chloro-5-octaanilino group. Examples include decenylsuccinimidoanilino group. When R ₇ represents an alkylamino group or a dialkylamino group, each alkyl group may be chain or cyclic, substituted or unsubstituted, saturated or unsaturated. The number of carbon atoms contained in R ₇ is preferably 32 or less, and the substituent contained in R ₇ is preferably selected from an alkoxy group, an aryloxy group, an aryl group, a hydroxyl group, and the like. Preferred alkylamino or dialkylamino groups include, for example, dibutylamino group, bis(2-hydroxyethyl)amino group, dibenzylamino group, octadecylamino group, dodecylamino group, 3-(2,4-di-tert -amylphenoxy)propylamino group and the like. When R ₇ represents a cyclic amino group, R ₇ is preferably a 5- or 6-membered ring, and useful cyclic amino groups include, for example, a pyrrolidinyl group, a piperazinyl group, a morpholinyl group, and the like. When R ₇ represents an acylamino group, it may be either an aliphatic amide group or an aromatic amide group. When representing an aliphatic amide group, it preferably has 1 to 22 carbon atoms, but it may be substituted or unsubstituted, chain or cyclic, saturated or unsaturated. Preferred substituents include, for example, an aryloxy group, an acylamino group, a halogen atom, and an aniline group. Useful aliphatic amide groups include, for example, tetradecanamide group, tert-butylamide group, acetamido group, 3-(2,4-di-tert-amylphenoxy)butyramide group, 2
-(3-pentadecylphenoxy)butyramide group, etc. can be mentioned. When R ₇ represents an aromatic amide group, the aromatic group (especially phenyl group) may be substituted. Examples of the substituent in this case include a halogen atom, an acylamino group, an alkoxy group, an alkyl group, and a hydroxy group. Useful aromatic amide groups include, for example, benzamide groups, 4-methoxybenzamide groups, 5
-[2-(2,4-di-tert-amylphenoxy)
Butyramide] benzamide group, 4-methoxy-
Examples include 5-[2-(2,4-di-tert-amylphenoxy)butyramide]benzamide group. These compounds according to the present invention are disclosed in U.S. Pat.
No. 3227554, No. 3617291, No. 3933500, No. 3958993, No. 4149886, No. 4234678,
JP-A-51-13239, 57-56837, British Patent No.
It can be easily synthesized by the methods described in Research Disclosure No. 2070266, No. 2072363, Research Disclosure No. 21228, December 1981, etc. Synthesis Example 1 (Synthesis of Compound Example (1)) 23.5g of 2-pivaloyl-2'-chloro-5'-[4
-(2,4-di-tert-amylphenoxy)butyramide]acetanilide in chloroform 100ml
and 6.6 g of bromine was added dropwise. After washing with water, this solution was mixed with 12.1 g of 5,6-dimethylbenzotriazole and 8.3 g of triethylamine in N,N-
It was added dropwise to a solution dissolved in 500 ml of dimethylformamide at room temperature. After stirring at room temperature for 2 hours, the mixture was washed with 500 ml of water. After separating the oil layer and washing with dilute hydrochloric acid,
Water washing was repeated until neutral. After separating the oil layer, it was concentrated under reduced pressure, and the residue was recrystallized from hexane and isopropanol to obtain 16 g of the desired coupler (1).
Obtained. The melting point was 141-142°C. Synthesis Example 2 (Synthesis of Compound Example (2)) 25 g of 3-{3-[2-(2,4-di-tert-amylphenoxy)butyramide]benzamide}-
1-(2,4,6-trichlorophenyl)-2-pyrazolin-5-one is dissolved in chloroform,
5.4g of bromine was added dropwise. This solution was transferred to a separating funnel, washed with water, and then the solvent was distilled off under reduced pressure. residue
The mixture was mixed with 15.7 g of 5,6-dimethylbenzotoluazole and 15 ml of sulfolane and stirred at 100°C for 10 hours. After cooling to room temperature and adding 200 ml of chloroform, the mixture was washed with water. The oil layer was concentrated under reduced pressure, and the residue was subjected to column chromatography using silica gel as a packing material. Fractions containing the desired product were eluted with ethyl acetate and concentrated to obtain 11 g of the desired coupler. Synthesis Example 3 (Synthesis of Compound Example (3)) Step Synthesis of 4-(5,6-dimethylbenzotriazol-1-yl)methoxy-2-naphthoic acid Add 4-hydroxy-2- to 200 ml of N,N-dimethylformamide. 50ml methanol solution containing 20.4g naphthoic acid and 12g sodium methoxide
A solution prepared by dissolving 20 g of 1-chloromethyl-5,6-dimethylbenzotriazole in 50 ml of acetonitrile was added dropwise at 40°C. After reacting for 1 hour, the mixture was poured into an aqueous hydrochloric acid solution, and the precipitated crystals were collected by filtration. 22g of the target product was obtained. Step 4-(5,6-Dimethylbenzotriazol-1-yl)methoxy-2-naphthoic acid phenyl ester synthesis 4-(5,6-dimethylbenzotriazol-1-yl)methoxy-2- obtained in step 10.9 g of naphthoic acid and 3.4 g of phenol in 120 g of acetonitrile
mixed in ml. Add 5.4g of thionyl chloride 3
The mixture was heated to reflux for an hour. The solvent was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile to obtain 11 g of the desired product. Step Synthesis of Compound Example (3) 11 g of 4-(5,6-dimethylbenzotriazol-1-yl)methoxy-2-naphthoic acid phenyl ester obtained in step and 3-(2,4-di-
6.6 g of tert-amylphenoxy) propylamine was dissolved in 50 ml of tetrahydrofuran and heated under reflux for 8 hours. The solvent was distilled off under reduced pressure, and the residue was recrystallized from ethyl acetate to obtain 5 g of the desired coupler. The melting point was 184-185°C. Synthesis Example 4 (Synthesis of Compound Example (6)) 22.4g of N,N'-bis(2-chloro-5-dodecyloxycarbonylphenyl)malondiamide was mixed with 100ml of chloroform, and 4.8g of bromine was added at room temperature.
was dripped. After washing the reaction solution with water, this solution was mixed with 5-
13.9 g of hexaneamide benzotriazole and 3 g of triethylamine were added dropwise to a solution of 50 ml of N,N'-dimethylformamide. After reacting at room temperature for 2 hours, the mixture was transferred to a separatory funnel and washed with water. Furthermore, after washing with diluted hydrochloric acid, washing with water was repeated until the mixture became neutral. After separating the oil layer, it was concentrated under reduced pressure and the residue was recrystallized from ethyl acetate and acetonitrile to obtain 14 g of the desired coupler. Melting point is 150-153
It was warm at ℃. Next, specific examples of the diffusible DIR coupler used in the present invention will be given. In the present invention, the ratio of the diffusive DIR coupler and the normal DI coupler introduced into the U layer and the O layer is adjusted by selecting (diffusive DIR coupler/total DIR coupler). In the present invention, the above ratio is 20 to 100% by weight for the U layer,
For the O layer, it is preferably 0 to 80%. In particular, the difference in the proportions of the U layer and the O layer is important when considering the balance of both image sharpness and graininess in low exposure areas. Therefore, in the present invention, the difference between the U layer and the O layer in the above ratio is preferably 20% to 100%, more preferably 50% to 100%,
Particularly preferably 100%. In the present invention, the sharpness of the image is determined by the so-called MTF.
Also, the graininess is determined by RMS (Root Mean
Measured by the Square method. Determination of graininess by the RMS method is well known in the industry, but “RMS
Granuslality；Determination of Just
It is described under the title "Noticeable Difference". The measurement aperture was 48μ. or,
Regarding MTF, the MTF value of the cyan image was measured at a frequency of 7 lines per 1 mm. A known method, such as the method described in US Pat. No. 2,322,027, can be used to introduce the coupler used in the present invention into the silver halide emulsion layer.
For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate) alkylamide (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate) or organic solvents with a boiling point of about 30 to 150 degrees, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-
After dissolving in ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Also, special public service in 1977-
The dispersion method using a polymer described in No. 39853 and JP-A No. 51-59943 can also be 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. As an engaging agent or protective colloid for photographic emulsion,
Although gelatin is advantageously used, other hydrophilic colloids can also be used. For example, derivatives of gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. Gelatin includes lime-processed gelatin, acid-processed gelatin, Bu11.Soc.Sci.Phot.Japan.No.16,
Enzyme-treated gelatin as described on page 30 (1966) may be used, and hydrolyzed or enzymatically decomposed products of gelatin may also be used. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. A specific example is U.S. Patent No.
No. 2614928, No. 3132945, No. 3186846, No. 3312553, British Patent No. 861414, No. 1005784
No. 1033189, Special Publication No. 42-26845, etc. The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, their esters, derivatives such as amides, acrylonitrile, styrene, etc. can be used. In particular, polymers which are compatible to some extent with gelatin, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide,
Graft polymers with polymers such as hydroxyalkyl methacrylates are preferred. These examples are:
U.S. Patent No. 2763625, U.S. Patent No. 2831767, U.S. Patent No.
It is described in No. 2956884 etc. Typical synthetic hydrophilic polymer substances include, for example, West German Patent Application (OLS) No. 2312708 and U.S. Patent No.
It is described in No. 3620751, No. 3879205, and Japanese Patent Publication No. 43-7561. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferable is 2
Silver iodobromide containing from mol% to 12 mol% silver iodide. The average grain size of the silver halide grains in the photographic emulsion (grain diameter in the case of spherical or approximately spherical grains,
In the case of cubic particles, the particle size is defined as the edge length and is expressed as an average based on the projected area), but there is no particular restriction on the particle size.
It is preferably 3μ or less. The particle size distribution may be narrow or wide. Silver halide grains in photographic emulsions may have regular crystal shapes such as cubic or octahedral shapes, or irregular crystal shapes such as spherical or plate shapes. or a composite form of these crystal forms.
It may also consist of a mixture of particles of various crystalline forms. The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.
Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. The photographic emulsion used in the present invention is P. Glafkides
Author “Chimie et Physique Photographique” (Paul Montel, 1967), GFDuffin
Author “Photographic Emulsion Chemistry” (The
Focal Press, 1966), VLZelikman et al.
by al “Making and Coating Photographic
Emulsion" (The Focal Press, 1964). In other words, any of the acid method, neutral method, ammonia method, etc. may be used, and soluble silver salt and soluble halogen As a method for reacting the salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used. A method in which particles are formed in an excess of silver ions (so-called back mixing method) may also be used.
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. In order to remove soluble salts from the emulsion after precipitation or physical ripening, a nude water washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants, anionic polymers (e.g. A precipitation method (flocculation) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may also be used. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see, for example, H. Frieser, ed.
Die Grundlagen der Photographischen
Prozessmit Silberhalogeniden” (Akademische
Verlagsgesellschft. 1968) pages 675-734 can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, Reduction sensitization method using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); using noble metal compounds (e.g., gold complex salts and complex salts of metals from group 3 of the periodic table such as Pt, It, and Pd) A noble metal sensitization method or the like can be used alone or in combination. Specific examples of these include U.S. Patent No. 1574944, U.S. Pat.
No. 2728668, No. 3656955, etc., and U.S. Pat.
The precious metal sensitization method is described in US Pat. No. 2,399,083, US Pat. No. 2,448,060, British Patent No. 618,061, etc. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. i.e. azoles, such as benzothiazolium salts, nitroimidazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds, such as mercaptothiazoles, mercaptobenzos; Thiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group ; thioketo compounds, such as oxadolinthione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-
Many compounds known as antifoggants or stabilizers can be added, such as hydroxy-substituted (1,3,3a,7)tetraazaindenes); benzenethiosulfonic acids; benzenesulfuric acid; can. For more detailed examples of these and how to use them, see, for example, U.S. Patent No.
Reference may be made to the specifications of No. 3954474, No. 3982947, and No. 4021248, or Japanese Patent Publication No. 52-28660. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention contains a coating aid, antistatic agent, slippery improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). ) may contain various surfactants for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates Anions containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters Surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, Cationic surfactants such as heterocyclic quaternary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. For the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salt compounds are added to the photographic emulsion layer of the photographic light-sensitive material of the present invention. , urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US Patent No. 2400532,
Same No. 2423549, Same No. 2716062, Same No. 3617280,
No. 3772021, No. 3808003, British Patent No.
Those described in No. 1488991 etc. can be used. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarboxylic acid, Hydroxyalkyl (meth)
Polymers containing a combination of acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as monomer components can be used. For example, US Patent No. 2376005, US Patent No. 2739137, US Patent No.
No. 2853457, No. 3062674, No. 3411911, No. 3488708, No. 3525620, No. 3607290,
No. 3635715, No. 3645740, British Patent No.
Those described in No. 1186699 and No. 1307373 can be used. For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure No. 176, pages 28-30 (RD-
17643), any of the known methods and known treatment solutions can be used. This photographic processing may be either a development processing for forming a silver image (black and white photographic processing) or a photographic processing for forming a dye image (color photographic processing), depending on the purpose. Further, the treatment temperature is usually selected between 18°C and 50°C, but it may be lower than 18°C or higher than 50°C. As a special type of development processing, a method may be used in which a developing agent is contained in the light-sensitive material, for example, in an emulsion layer, and the light-sensitive material is processed in an aqueous alkaline solution to perform development. Among the developing agents, hydrophobic ones are used in Research Disclosure No. 169 (RD-
16928), US Patent No. 2739890, UK Patent No.
They can be incorporated into the emulsion layer by various methods such as those described in US Pat. No. 813,253 or West German Patent No. 1,547,763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. When forming a dye image, conventional methods can be applied.
For example, negative-positive method (e.g. “Journal of the
Society of Motion Picture and Television
Engineers, Vol. 61 (1953), pp. 667-701); color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer. , for example phenylene diamines (e.g. 4-amino-N,
N-diethylaniline, 3-methyl-amino-
N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamidoethylaniline, 4-amino-3-methyl-N- ethyl-N-β-methoxyethylaniline, etc.) can be used. In addition, “Photographic” by LFA Mason
“Processing Chemistry” (The Focal Press
(1966) pp. 226-229, U.S. Patent No. 2193015,
Those described in JP-A No. 2592364, JP-A-48-64933, etc. may be used. The color developer may also contain a PH buffer, a development inhibitor, an antifoggant, and the like.
Also, if necessary, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity imparting agents, polycarboxylic acid chelating agents, and antioxidants. It may also include. Specific examples of these additives include Research Disclosure (RD-17643),
It is described in US Pat. No. 4,083,723, West German Publication No. 2,622,950, etc. The photographic emulsion layer of a color developer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleach,
For example, iron (), cobalt (), chromium (),
Compounds of polyvalent metals such as copper, peracids, quinones, nitroso compounds, etc. are used. for example,
Ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, tartaric acid, Complex salts of organic acids such as malic acid; persulfates, permanganates; nitrosophenols, etc. can be used. Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solutions are manufactured by U.S. Patent No.
No. 3042520, No. 3241966, Special Publication No. 45-8506,
Bleaching accelerator described in JP-A No. 45-8836, etc., JP-A-53
In addition to the thiol compound described in No.-65732, various additives can also be added. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Useful sensitizing dyes include, for example, German patent no.
929080, US Patent No. 2493748, US Patent No. 2503776
No. 2519001, No. 2912329, No. 2912329, No. 2519001, No. 2912329, No.
Examples include those described in No. 3656959, No. 3672897, No. 4025349, British Patent No. 1242588, and Japanese Patent Publication No. 44-14030. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.
Representative examples are U.S. Patent No. 2688545 and U.S. Patent No. 2977229.
No. 3397060, No. 3522052, No. 3522052, No. 3397060, No. 3522052, No.
No. 3527641, No. 3617283, No. 3628964, No. 3666480, No. 3672898, No. 3679428,
No. 3814609, No. 4026707, British Patent No.
No. 1344281, Special Publication No. 43-4936, No. 53-12375,
It is described in JP-A-52-109925 and JP-A-52-110618. The invention is also applicable to multilayer color photographic materials having at least two different spectral sensitivities on the support. Multilayer color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. The photographic emulsion layer of the photographic light-sensitive material produced using the present invention contains a color-forming coupler, that is, an aromatic primary amine developer (e.g., phenylene diamine derivative, aminophenol derivative, etc.) in the color development process. Compounds capable of developing color by oxidative coupling may be used in conjunction with the polymeric coupler latex, or alone in layers without the polymeric coupler latex. For example, as a magenta coupler, a 5-pyrazolone coupler,
There are pyrazolone benzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc., and cyan couplers include naphthol couplers and There are phenol couplers, etc. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule.
The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor. Specific examples of magenta coloring couplers are shown in U.S. Patent No.
No. 2600789, No. 2983608, No. 3062653, No. 3127269, No. 3311476, No. 3419391,
Same No. 3519429, Same No. 355819, Same No. 3582322,
Same No. 3615506, Same No. 3834908, Same No. 3891445,
West German Patent No. 1810464, West German Patent Application (OLS) No.
No. 2408665, No. 2417945, No. 2418959, No. 2424467, Japanese Patent Publication No. 1973-6031, Japanese Patent Publication No. 1973-49-
No. 74027, No. 49-74028, No. 49-129538, No. 50
-60233, 50-159336, 51-20826, same
No. 51-26541, No. 52-42121, No. 52-58922,
This is described in No. 53-55122. A specific example of yellow coloring is U.S. Patent No. 2875057.
No. 3265506, No. 3408194, No. 3408194, No. 3265506, No. 3408194, No.
3551155, 3582322, 3725072, 3891445, West German Patent No. 1547868, West German Published Application No. 2219917, 2261361, 2414006,
British Patent No. 1425020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133, Japanese Patent Publication No. 48-73147, Japanese Patent Publication No. 50-6341,
No. 50-87650, No. 50-123342, No. 50-130442
No. 51-21827, No. 51-102636, No. 52-
It is described in No. 82424, No. 52-115219, etc. A specific example of a cyan coupler is described in U.S. Patent No.
No. 2369929, No. 2434272, No. 2474293, No. 2521908, No. 2895826, No. 3034892,
Same No. 3311476, Same No. 3458315, Same No. 3476563,
Same No. 3583971, Same No. 3591383, Same No. 3767411,
No. 4004929, West German Patent Application (OLS) No.
No. 2414830, No. 2454329, JP-A-48-5055,
No. 48-59838, No. 51-26034, No. 51-146828
No. 52-69624 and No. 52-90932. Examples of colored couplers include US Pat.
No. 44-32461, JP-A No. 51-26034, No. 52-
42121, those described in West German Patent Application (OLS) No. 2418959 can be used. As a DIR coupler, for example, the US patent
3227554, 3617291, 3632345, 3701783, 3790384, West German Patent Application (OLS) No. 2414006, 2454301,
No. 2454329, British Patent No. 953454, Japanese Unexamined Patent Publication No. 1973-
Those described in No. 122335, No. 52-69624, and Japanese Patent Publication No. 51-16141 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor upon development; for example, U.S. Pat. No. 3,297,445, U.S. Pat.
No., West German Patent Application (OLS) No. 2417914, JP-A-Sho
Those described in No. 52-15271 and No. 53-9116 can be used. The photographic light-sensitive material may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,
3-vinylsulfonyl-2-propanol, etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. For example, British patent no.
685475, U.S. Patent No. 2675316, U.S. Patent No. 2839401
No. 2882156, No. 3048487, No.
3184309, 3445231, West German Patent Application (OLS) No. 1914362, JP-A-50-47624, 50
Polymers described in No.-71332 and the like can be used. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photographic light-sensitive material may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer. Specific examples of ultraviolet absorbers include U.S. Patent No. 3314794.
No. 3352681, No. 3499762, No. 3499762, No. 3352681, No. 3499762, No.
No. 3533794, No. 3700455, No. 3705805, No. 3707375, No. 4045229, JP-A-46-2784
No. 1, West German Patent Application Publication No. 1547863, etc. The silver halide color photographic light-sensitive material prepared according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include, for example:
U.S. Patent No. 2360290, U.S. Patent No. 2418613, U.S. Patent No.
No. 2675314, No. 2701197, No. 2704713, No. 2710801, No. 2728659, No. 2732300,
No. 2735765, No. 2816028, British Patent No.
Hydroquinone derivatives described in No. 1363921 etc.
Gallic acid derivatives described in U.S. Patent Nos. 3,069,262 and 3,457,079, p-alkoxyphenols described in U.S. Pat. U.S. Patent No. 3432300, U.S. Patent No. 3573050, U.S. Patent No. 3574627
No. 3764337, JP-A No. 52-35633, No. 52-
Examples include p-oxyphenol derivatives described in No. 147434 and No. 52-152225, and bisphenols described in US Pat. No. 3,700,455. The photographic support used in the present invention includes cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, and polyethylene terephthalate film, which are usually used in photographic light-sensitive materials. , polycarbonate film,
Other materials include laminates of these materials, thin glass, and paper.
Baryta or paper coated or laminated with an α-olefin polymer, especially a polymer of α-olefin having 2 to 10 carbon atoms, such as polyethylene, polypropylene, ethylene butene copolymer, etc.; Supports such as plastic films whose surfaces are roughened to improve adhesion to other polymeric substances give good results. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like.
The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. In the photographic light-sensitive material, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These water-soluble brighteners may be used, or water-insoluble brighteners may be used in the form of a dispersion. In photographic materials, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. The photosensitive material may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The following known antifading agents can be used in the photographic material used in the present invention, and color image stabilizers can be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. When exposing the silver halide color photographic light-sensitive material produced according to the present invention, exposure times of 1/1000 seconds to 1 second, which are used in cameras, as well as exposure times of 1/10
Exposures shorter than 0.00 seconds can be used, such as exposures of ^1/104 to ^1/106 seconds using a xenon flashlamp or cathode ray tube, or exposures longer than 1 second can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Alternatively, it may be exposed to light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like. Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited thereby. Example As a sample, a multilayer color photosensitive material consisting of each layer having the composition shown below was prepared on a cellulose triacetate film support. 1st layer; antihalation layer; gelatin layer containing black colloidal silver; 2nd layer; intermediate layer; gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone; 3rd layer; 1st red-sensitive emulsion layer; odor Silver emulsion (silver iodide 5 mol%)... Silver coating amount 1.6 g/m ² Sensitizing dye... 4.5 x 10 ^-4 mol per 1 mol of silver Sensitizing dye... per 1 mol of silver 1.5×10 ^-4 mol Coupler EX-1...0.04 mol per mol of silver Coupler EX-3...0.003 mol per mol of silver Coupler EX-9...0.0006 mol per mol of silver 4 layers; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%)... Silver coating amount 1.4 g/m ² Sensitizing dye... 3 x 10 ^-4 per mol of silver Mol Sensitizing dye...1 x 10 ^-4 mol per mol of silver Coupler EX-1...0.002 mol per mol of silver Coupler EX-2...0.02 mol per mol of silver Coupler EX-3 ...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/m ² Sensitizing dye... 5 x 10 ^-4 mol per 1 mol of silver Sensitizing dye... 2 x 10 ^-4 mol per 1 mol of silver Coupler EX-4... Per 1 mol of silver 0.05 mol Coupler EX-5...0.008 mol per mol of silver Coupler EX-9...0.0015 mol per mol of silver 7th layer; 1st 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 x 10 ^-4 mol per mol of silver Coupler EX- 7...0.003 mol per mol of silver Coupler EX-6...0.0003 mol per mol of silver Coupler EX-10...0.0015 mol per mol of silver 8th layer; Yellow filter layer Yellow in gelatin aqueous solution Colloidal silver and 2,5
- Gelatin layer 9th layer containing an emulsified dispersion of di-t-octylhydroquinone; First blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 mol%)... Silver coating amount 0.7 g/m ² coupler EX-8...0.25 mol per mol of silver Coupler EX-9...0.015 mol per mol of silver 10th layer; 2nd blue-sensitive emulsion layer Silver iodobromide (6 mol% silver iodide)... ... Silver coating amount 0.6g/m ² Coupler EX-8...0.06 mol per mol of silver 11th layer; 1st protective layer Silver iodobromide (silver iodide 1 mol%, average grain size 0.07μ)
... Silver coating amount 0.5 g/m ² 12th layer of gelatin layer containing an emulsified dispersion of ultraviolet absorber UV-1; 2nd protective layer Polymethyl methanoacrylate particles (diameter approx.
Apply a gelatin layer containing 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 101. The compounds used to prepare the samples are shown below. Preparation of comparative samples 102 to 104 Completely the same as sample 101 except that a non-diffusive coupler EX-10 with a diffusivity of 0.3 was used in place of the diffusive coupler EX-9 with a diffusivity of 0.7 used in the sixth layer of sample 101. Sample 102 was prepared in the same manner. Next, sample 103 was prepared in exactly the same manner as sample 101 except that diffusive coupler EX-9 was used in place of non-diffusive coupler EX-10 used in the seventh layer of sample 101. Also, the diffusive coupler EX-9 in the 6th layer of sample 101
Instead of 95% of EX-9 and a non-diffusive coupler
A coupler mixed with 5% of EX-10 was used, and the non-diffusive coupler EX-10 was used in the seventh layer of sample 101.
Sample 104 was prepared in exactly the same manner as sample 101 except that a mixed coupler of 35% EX-9 and 65% EX-10 was used instead of sample 10. Table 1 shows the results of processing the sample thus obtained by a conventional method. The development process in this case was carried out at 38°C as described below. 1 Color development... 3 minutes 15 seconds 2 Bleaching... 6 minutes 30 seconds 3 Washing... 3 minutes 15 seconds 4 Fixing... 6 minutes 30 seconds 5 Washing... 3 minutes 15 seconds 6 Stabilization... 3 minutes 15 seconds each The composition of the treatment liquid used in the process is as follows. 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-hydroxy Ethylamino)-2-methylaniline sulfate...4.5g Add water...1.0 Bleach solution Ammonium bromide...160.0g Aqueous ammonia (28%)...25.0cc Ethylenediamine-tetraacetic acid sodium iron salt
…130.0g Glacial acetic acid …14.0cc Add water …1.0 Fixer Sodium tetrapolyphosphate …2.0g Sodium sulfite …4.0g Ammonium thiosulfate (70%) …175.0cc Sodium bisulfite …4.6g Add water...1.0g Stabilizing liquid Formalin...8.0cc Add water...1.0 The results in Table 1 show that a diffusive coupler was used in the U layer (corresponding to the 6th layer) of the sample, and the O layer ( (corresponds to layer 7)
This demonstrates that in the case of Sample 101 of the present invention using a non-diffusive coupler, both image sharpness and graininess are extremely good.

[Table] Furthermore, the results in Table 1 show that in the case of sample 102, in which non-diffusive couplers were used in both the U and O layers, image sharpness and graininess were poor; In the case of sample 103, which uses a diffusive coupler, the image sharpness is improved, but the graininess is poor, and the disadvantages of sample 102 and sample 103 are as follows.
As in sample 104, the proportion of diffusive coupler in the O layer is
It also demonstrates that there is an improvement when the proportion of diffusive coupler in the layer is reduced.

Claims (1)

[Claims] 1. Reacts with the oxidation product of the developing agent during development,
A silver halide color photographic light-sensitive material containing a development inhibitor-releasing coupler capable of releasing a development inhibitor, wherein the development inhibitor-releasing coupler is a diffusible development inhibitor-releasing coupler having a degree of diffusivity of 0.4 or more, and a diffusion inhibitor-releasing coupler. In a silver halide color photographic light-sensitive material containing a development inhibitor-releasing coupler with a degree of less than 0.4, the ratio of the diffusive development inhibitor-releasing coupler to the development inhibitor-releasing coupler is higher than that of the low-speed layer. A silver halide color photographic material characterized by a lower layer.