JPH0574811B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION (Technical Field) The present invention relates to silver halide photographic materials containing a novel 2-equivalent yellow dye-forming polymer coupler latex. (Prior art and its problems) As is well known, in subtractive color photography, oxidation products of a color developing agent are produced when an aromatic primary amine color developing agent reduces exposed silver halide grains. Dye images are formed by oxidative coupling of yellow, cyan, and magenta dye-forming couplers in a silver halide emulsion. In these cases, as a yellow coupler to form a yellow dye, a compound having an open-chain active methylene group is generally used, and as a magenta coupler to form a magenta dye, pyrazolone, pyrazolotriazole, and pyrazolo Compounds such as benzimidazole and indazolone are used, and phenol and naphthol compounds are used as cyan couplers to form cyan dyes. Each coupler is dissolved in a substantially water-insoluble high-boiling organic solvent, or optionally in combination with an auxiliary solvent, and added to the silver halide emulsion, or dissolved in an aqueous alkaline solution. Added to silver halide emulsions. The former is an oil droplet dispersion method, and the latter is an alkali dispersion method, but the former is generally considered to be superior to the latter in terms of light resistance, heat resistance, moisture resistance, color sharpness, etc. The basic properties required for each coupler are:
In addition to simply forming dyes, the dyes must first have high solubility in high-boiling organic solvents or alkalis, and have good dispersibility and stability in silver halide photographic emulsions. It should have fastness to light, heat, moisture, etc., good spectral absorption characteristics, good transparency, high color density, and excellent sharpness and graininess of the image obtained. It is desired to have various characteristics such as the ability to However, to the best of the knowledge of the present inventors, no conventionally known yellow coupler has yet been found that satisfies all of the above-mentioned required properties. Conventionally, various acylacetanilide or benzoylmethane couplers have been known as yellow couplers, but so-called 4-equivalent couplers in which the coupling active position is unsubstituted have poor coloring efficiency. As a method for improving this color development efficiency, a so-called 2-equivalent yellow coupler is known in which a substituent that can be removed during color development is introduced into the active position of the coupler. As for the leaving groups of these two-equivalent yellow couplers, for example, couplers having an aryloxy group are disclosed in JP-A-50-87650 and U.S. Pat. In addition, a coupler having a chroman-4-oxy group is disclosed in JP-A-51-139333, and a coupler having a tetrazolyloxy group is disclosed in JP-A-52-1989.
43426, a coupler having a nitrogen-containing heterocyclic group in JP-A-52-115219, a coupler having a urazole group and a hydantoin group in JP-A-49-13576,
A coupler having a tetrazolone group was published in Japanese Patent Application Laid-Open No. 1986-
Couplers having an arylthio group are described in US Pat. No. 53825 and US Pat. No. 50-28834, and some of them have already been put into practical use. However, although this 2-equivalent yellow coupler has high sensitivity and excellent color development, it has the drawback of poor graininess. JP-A-59-9657 describes a dye-diffusing coupler for the purpose of improving graininess. Although these dye-diffusion type couplers have improved graininess, they have new problems such as poor sharpness and increased fog due to dye diffusion, and furthermore, discoloration and discoloration of dye images due to the influence of residual leaving groups. was. Incidentally, in a silver halide color photographic light-sensitive material having a multilayer structure, it is necessary to fix each coupler in a separate layer in order to reduce color mixture of each dye and improve color reproducibility. Various methods are known for preventing coupler diffusion. One method is to introduce a long-chain aliphatic group (diffusion-inhibiting group) into the coupler molecule to prevent diffusion. Couplers produced by this method are immiscible with aqueous gelatin solutions, so they are either solubilized in alkali and added to the aqueous gelatin solution, or couplers with oil-soluble ballast groups (diffusion-inhibiting groups) are used with the help of surfactants. It is necessary to disperse it as colloidal particles in an aqueous gelatin solution together with an organic solvent at a boiling point. In such couplers, the hydrophilic groups in the couplers interact with gelatin, causing a thickening phenomenon, especially during the coating process, which impedes high-speed uniform coating, or causes crystal precipitation in the emulsion. do. Also,
When an organic solvent with a high boiling point is used, a large amount of gelatin is required to soften the emulsion layer, and as a result, it is difficult to make the emulsion layer thin. On the other hand, another method for making a coupler resistant to diffusion is to use a polymer coupler obtained by polymerizing a monomeric coupler in which a group containing a polymerizable unsaturated bond is introduced into the coupler molecule. The polymer coupler can be added to the hydrophilic colloid composition in the form of terraces by the following methods. One is to directly polymerize the coupler monomer with other copolymerization components by emulsion polymerization to form a latex, which is then added to the silver halide emulsion. In this method, a polymer coupler is polymerized by solution polymerization together with a copolymer component, and the resulting polymer coupler is dissolved in a solvent, and then dispersed in an aqueous gelatin solution to form a latex. The former emulsion polymerization method is described in US Pat. No. 3,370,952 and US Pat. No. 4,080,211, respectively. The latter method is described, for example, in US Pat. No. 3,451,820. The method of adding such polymer couplers in latex form to hydrophilic colloid compositions has the following advantages over other methods. That is, the polymer coupler latex can contain a high concentration of coupler units and does not contain a high boiling point organic solvent, so it can be made into a thin film and the sharpness can be improved. Furthermore, since the aqueous gelatin solution does not thicken much, high-speed uniform coating is possible. Furthermore, since the polymer coupler is made into a latex, it does not deteriorate the strength of the formed film. Several examples can be given of such polymer couplers added to silver halide emulsions in the form of latexes. For example, US patent
No. 4080211, No. 3451820, and British Patent No. 1247688 describe a method for making a 4-equivalent magenta dye-forming polymer coupler latex;
No. 3,767,412 describes a cyan dye-forming polymer coupler latex, and U.S. Pat. No. 3,926,436
No. 1, as well as German Patent No. 2725591, describe copolymerized latexes with competitive couplers. Furthermore, U.S. Patent No. 4080211, U.S. Patent No. 3926436, JP-A-52-153737, U.S. Patent No. 2976294, U.S. Pat.
3370952, 3515557, and 3451820 disclose 4-equivalent yellow dye-forming polymer coupler latexes;
No. 42,543 describes a 2-equivalent yellow dye-forming polymeric coupler latex. The above-mentioned 2-equivalent yellow dye-forming polymer coupler latex is a polymer derived from a 2-equivalent yellow coupler monomer having a polymerizable group in the coupler moiety, and the granularity has not been improved in any way. The 2-equivalent yellow dye-forming polymer coupler latex of the present invention is a polymer derived from a 2-equivalent yellow coupler monomer having a polymerizable group at the substituent moiety from which the active position of the coupler can be removed, and it has not only granularity but also granularity. It had a great effect on sharpness, fog, and even discoloration of pigmented images. OBJECTS OF THE INVENTION A first object of the present invention is to provide a silver halide color photographic light-sensitive material with excellent graininess using a novel 2-equivalent yellow dye-forming polymer coupler latex. A second object of the present invention is to provide a novel 2-equivalent yellow dye-forming polymeric coupler latex containing a novel 2-equivalent yellow dye-forming polymeric coupler latex with sufficient reactivity to form dyes in high yields without unnecessary fog or stain. An object of the present invention is to provide a silver color photographic material. A third object of the present invention is to provide a silver halide color photographic light-sensitive material containing a 2-equivalent yellow dye-forming polymer coupler latex which has excellent film strength and improved image sharpness by thinning the film. A fourth object of the present invention is to provide a silver halide color photographic light-sensitive material that uses a novel 2-equivalent yellow dye-forming polymer coupler latex and has a robust dye image with excellent light fastness, heat resistance, and moisture resistance. It is to be. A fifth object of the present invention is to use a novel 2-equivalent yellow dye-forming polymer coupler latex to reduce the amount of silver halide and the amount of coupler used in a photographic emulsion layer containing the same. The purpose of this invention is to provide photosensitive materials. Structure of the Invention As a result of research on various yellow couplers, the present inventors have discovered a yellow dye-forming polymer coupler latte having a repeating unit represented by the following general formula [] that can form a dye on a support using an alkaline color developer. It has been found that the above object can be achieved by a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing Tx. General formula []

[Formula] (In the formula, R ₁ represents an alkyl group or an aryl group, R ₂ represents a monovalent group, and Q has an ethylenically unsaturated group and is released by a coupling reaction with an oxidized form of a color developing agent. represents a possible group, l is 0 to
Represents an integer of 5. ) Hereinafter, the present invention will be explained in more detail. R ₁ in the general formula [] is an alkyl group or an aryl group. The alkyl group is preferably a straight-chain or branched alkyl group having 3 to 20 carbon atoms, more preferably a straight-chain or branched alkyl group having 4 to 8 carbon atoms (e.g., tert-butyl group, n-butyl group, n- amyl group, tert-amyl group, sec-amyl group, n-octyl group, tert-octyl group, etc.)
and particularly preferably a tert-butyl group. Further, this alkyl group includes a cycloalkyl group (for example, a cyclohexyl group), and can further have a substituent. The aryl group represented by R ₁ is preferably a phenyl group, and this aryl group may have a substituent. Substituents for aryl groups include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), carbon atoms 1
to 8 alkyl groups (methyl group, ethyl group, iso
-propyl group, tert-butyl group, sec-amyl group,
tert-octyl group, etc.), alkoxy group (e.g.,
methoxy group, ethoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.), alkylsulfonamide group (e.g., methanesulfonamide group, ethanesulfonamide group, etc.), arylsulfonamide group (e.g., phenylsulfonamide group, etc.) ), alkoxycarbonyl groups (e.g., methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl groups (e.g., phenyloxycarbonyl group, etc.), acylamino groups (e.g., acetylamino group, pivaloylamino group, etc.), alkylsulfur moyl group (e.g., methylsulfamoyl group, dimethylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkylcarbamoyl group (e.g.,
methylcarbamoyl group, etc.), arylcarbamoyl group (e.g., phenylcarbamoyl group, etc.), alkyl or arylsulfonyl group (e.g.,
methylsulfonyl group, phenylsulfonyl group, etc.)
Nitro group, cyano group, these substituents are 2
The number may be two or more, and in the case of two or more, they may be the same or different. When R ₁ in the above general formula is a phenyl group, the substituent is preferably an alkoxy group, a halogen atom, an alkyl group, or an alkylsulfonamide group. Examples of the monovalent group represented by R ₂ in the general formula [] include a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an aryloxy group, an alkylsulfonamide group, an arylsulfonamide group, and an alkoxycarbonyl group. group, aryloxycarbonyl group, acylamino group, alkylsulfamoyl group, arylsulfamoyl group,
Examples include an alkylcarbamoyl group, an arylcarbamoyl group, a sulfonyl group, a nitro group, and a cyano group. Among these, preferred are a halogen atom, an alkoxy group, an alkylsulfonamide group, an acylamino group, and an alkoxycarbonyl group. l represents an integer of 0 to 5, and when l is 2 or more, R ₂ may be the same or different. Q has an ethylenically unsaturated group and is a group that can be separated by a coupling reaction with an oxidized color developing agent, and is preferably represented by the following general formula []. General formula []

embedded image In the formula, R ₃ is a hydrogen atom, a halogen atom, or an alkyl group, preferably an alkyl group, particularly a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, etc.). This alkyl group may have a substituent. R ₄ , R ₅ and R ₆ represented by the general formula [] are:
Each represents an alkylene group, arylene group or aralkylene group having 1 to 20 carbon atoms. The alkylene group may be linear or branched. Examples of such an alkylene group include a methylene group, a methylmethylene group, a dimethylene group, and a decamethylene group. Examples of the arylene group include a phenylene group and a naphthylene group. Examples of the aralkylene group represented by R ₄ , R ₅ and R ₆ include a benzylene group. The alkylene group, arylene group or aralkylene group represented by R ₄ , R ₅ and R ₆ may have a substituent, for example,
These include an alkyl group, a halogen atom, an alkoxy group, and the like. X represented by the above general formula [] is -CONH
−, −NHCO−, −NHCONH−, −COO−, −
OCO-, _-SO2- , -S-, -CO-, -SO-, -O
- represents a bonding group, among which preferred are:
−CONH−, −NHCONH−, −COO−, −SO ₂
-, -S-, -O-. Y represented by the above general formula [] is -CONH
−, −NHCO−, −NHCONH−, −COO−, −
2 of OCO−, −SO ₂ NH−, −NHSO ₂ −, −SO ₂ −
represents a valent bonding group, among which preferable ones are -
CONH−, −OCO−, −SO ₂ NH−, and −SO ₂ −. m, n, o, p, and q represent 0 or 1. Z is a group that can be separated by a coupling reaction with an oxidized color developing agent, and can be represented by the following general formulas [] and []. General formula [] General formula []

【formula】

[Formula] In the formula, * represents the active position of the coupler, A represents an oxygen atom or a sulfur atom, B represents a group of nonmetallic atoms necessary to form an aryl ring or a heterocycle, and E represents a nitrogen atom together with a nitrogen atom. 5 members or 6 members
Represents a group of nonmetallic atoms necessary to form a member heterocycle. These rings may further be fused with an aryl ring or a heterocycle. Z represented by the general formula [] is an aryloxy group, an oxazolyloxy group, a chroman-
Z, which is a divalent group derived from a 4-oxy group, a tetrazolyloxy group, an arylthio group, etc. and is represented by the general formula [], includes a urazole group,
A divalent group derived from a hydantoin group, a tetrazolone group, a triazole group, a diazole group, a succinimide group, a saccharin group, a pyridone group, a pyridazone group, an oxazolidinedione group, a thiazolidinedione group, etc., and is preferably an aryl group. It is a divalent group derived from an oxy group, a urazole group, a hydantoin group, a tetrazolone group, and a pyrazole group. Group Z represented by general formulas [] and []
may further have a substituent, and examples of the substituent include an alkyl group, an aryl group, an aralkylene group, a halogen atom, an alkoxy group, a hydroxy group, a nitro group, an amino group, a carboxylic acid ester group, a carboxylic acid group, or a sulfonic acid group. Examples include groups. Next, typical examples of the coupler monomer represented by the general formula [] will be described, but the present invention is not limited thereto. (1)

[ka] (2)

[ka] (3)

[ka] (Four)

[ka] (Five)

[ka] (6)

[ka] (7)

[ka] (8)

[ka] (9)

[ka] (Ten)

[ka] (11)

[ka] (12)

【formula】 (13)

[ka] (14)

[ka] (15)

[ka] (16)

[ka] (17)

[ka] (18)

[ka] (19)

[ka] (20)

[ka] (twenty one)

[ka] (twenty two)

[ka] (twenty three)

[ka] (twenty four)

[ka] (twenty five)

[ka] (26)

[ka] (27)

[ka] (28)

[ka] (29)

[ka] (30)

[ka] (31)

embedded image Typical production examples of the coupler monomer according to the present invention are shown below. Synthesis Example 1 [Exemplary Coupler Monomer (1)] 22.8 g of α-chloro-α-pivaloyl-2-chloroacetanilide and 23.5 g of 1-(p-nitrophenylmethyl)hydantoin were dissolved in 1 part acetonitrile. 20.2 g of triethylamine was added to this solution, and the mixture was heated under reflux for 8 hours. Acetonitrile was concentrated under reduced pressure, poured into water from step 1, and neutralized with acetic acid. The precipitated crystals were filtered, washed with water, and dried to obtain 35.5 g of α-pivaloyl-α-[1-(p-nitrophenylmethyl)-hydantoin-3-yl]-2-chloroacetanilide. 21.3 g of the above nitro compound was dissolved in 250 ml of acetone, and 23.7 g of powdered tin was added. While vigorously stirring at room temperature, 37.5 ml of concentrated hydrochloric acid was added dropwise over 30 minutes. After further stirring for 1 hour, the mixture was poured with water, neutralized with sodium bicarbonate, and extracted with ethyl acetate.
After drying over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure to obtain α-pivaloyl-α-1-(p-aminophenylmethyl)hydantoin-3-yl)-
10.2 g of 2-chloroacetanilide was obtained. The above amino compound was dissolved in 100 ml of tetrahydrofuran, and 2.8 g of pyridine was added. This solution was heated at 5°C.
Methacrylic acid chloride while keeping below 3.2
g was added dropwise. After dropping, stir at room temperature for 1 hour,
poured into the water. The precipitated crystals were filtered, washed with water, dried, and then recrystallized from acetonitrile to obtain 6.8 g of exemplified coupler (1). mp168~171℃, structure is
Determined using NMR, Mass and IR. Synthesis Example 2 [Exemplary coupler monomer (4)] 29.5 g of α-bromo-α-benzoyl-2chloroacetanilide and 25.0 g of 1-(p-nitrophenylmethyl)-2-phenylurazole were dissolved in 200 ml of chloroform. Then, 16.2 g of triethylamine was added, and the mixture was left at room temperature overnight. The chloroform solution was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was recrystallized from toluene to obtain 29.8 g of α-benzoyl-α-[1-(p-nitrophenylmethyl)-2-phenylurazol-4-yl]-2-chloroaceanilide. 20.0 g of the above nitro compound was dissolved in 170 ml of acetone, and 16.1 g of tin powder was added. At room temperature, 25.6 ml of concentrated hydrochloric acid was added dropwise over 30 minutes while stirring vigorously. After further stirring for 1 hour, the mixture was poured with water, neutralized with sodium bicarbonate, and extracted with ethyl acetate. After drying over anhydrous sodium sulfate, it was distilled off with ethyl acetate under reduced pressure to give α-benzoyl-α-[1-(p-aminophenylmethyl)-2-phenylurazol-4-
10.8 g of yl]-2-chloroacetanilide was obtained. The above amino compound was dissolved in 100 ml of acetonitrile, and 2.0 ml of pyridine was added. This solution was heated at 5°C.
Methacrylic acid chloride while keeping below 2.3
g was added dropwise. After dropping, stir at room temperature for 1 hour,
poured into the water. The precipitated crystals were filtered, washed with water, dried, and then recrystallized from acetonitrile to obtain 6.2 g of exemplified coupler (4). mp196-199℃, structure is NMR,
Determined using Mass and IR. Synthesis Example 3 [Exemplary coupler monomer (11)] 72.1 g of α-chloro-α-pivaloyl-2-chloroacetanilide and 4-(p-aminophenyl)-
45.2 g of 1H-tetrazolone was dissolved in 270 ml of acetone, 34.6 g of potassium carbonate was added, and the mixture was heated under reflux for 2 hours. After cooling, 35 ml of acetic acid was added and poured into 1 water. The precipitated crystals were filtered, washed, dried, and then recrystallized from ethanol to give α-pivaloyl-α-[4(p-aminophenyl)tetrazolon-1-yl]-2-chloroacetanilide with a mp of 159 to 160°C93.5
I got g. 200ml of the above amino compound, 21.4g and pyridine 5.5g
was dissolved in acetonitrile, and 6.3 g of methacrylic acid chloride was added dropwise to the solution while keeping the temperature below 5°C. After the dropwise addition, the mixture was stirred at room temperature for 1 hour and poured into 1 water. The precipitated crystals were filtered, washed with water, dried, and then recrystallized from acetonitrile to obtain 17.5 g of exemplified coupler (11). mp202~205℃, structure is NMR,
Determined using Mass and IR. Synthesis Example 4 [Exemplary coupler monomer (16)] α-pivaloyl-α-[4-(4-hydroxybenzenesulfonyl)phenoxy]2-chloroacetanilide 10.0 g, chloromethylstyrene (mp mixture) 3.4 g and p-methoxyphenol 0.5g
Dissolve in 50 ml of dimethylformamide. Add 1.7 g of potassium carbonate to this solution, stir at room temperature overnight, stir at 50°C for 1 hour, and pour into 500 ml of water. Neutralize with acetic acid, filter the precipitated crystals, wash with water,
Dry. Purification by silica gel column chromatography gave 5.2 g of exemplary coupler (16). mp135
~139°C, structure determined using NMR, Mass and IR. Synthesis Example 5 [Exemplary Coupler Monomer (21)] α-benzoyl-α-[1-(p-aminophenylmethyl)-2-phenylurazol-4-yl]-2-chloroacetanilide of Synthesis Example 2 27.7 g
Dissolve 5.5 g of pyridine in 200 ml of acetonitrile, and while keeping this solution below 5°C, 12.2 g of 6-acryloylamino-n-caproic acid chloride.
was dripped. After the dropwise addition, the mixture was stirred at room temperature for 1 hour and poured into 1 water. The precipitated crystals were filtered, washed with water, dried, and then recrystallized from acetonitrile to obtain 15.3 g of exemplified coupler (21). mp148~151℃, structure is
Determined using NMR, Mass and IR. The polymer coupler according to the present invention has the general formula []
It may be a so-called homopolymer consisting only of repeating units represented by, or it may be a so-called copolymer with other copolymerizable comonomers, but in the present invention, preferably,
It is a copolymerized polymer coupler. Examples of comonomers that can be copolymerized include acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes, crotonic acid esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, and the like. More specifically, these comonomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec.
-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate,
2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2
-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate,
Methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,
2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2-(2
-methoxyethoxy)ethyl acrylate, 2-
(2-butoxyethoxy)ethyl acrylate,
ω-methoxypolyethylene glycol acrylate (additional mole number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2
-ethoxyethyl acrylate and the like. Examples of methacrylic acid esters include ethyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate. , octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)
Ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate,
Phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3
-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate,
Examples include 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (number of moles added = 6), etc. be able to. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, etc. can be mentioned. Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene,
1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-
Dimethyl butadiene and the like can be mentioned. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene,
Examples include chloromethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromustyrene, and vinylbenzoic acid methyl ester. Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like. Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate,
Examples include dibutyl itaconate. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like. Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of other comonomers include: Acrylamides, e.g. acrylamide,
Methylacrylamide, ethyl acrylamide,
Propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, etc.; Allyl compounds, e.g. , allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc.; Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.; Vinyl ketones, such as methyl vinyl ketone, Phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc.; Glycidyl esters, such as glycidyl Acrylates, glycicyl methacrylate, etc.; Unsaturated nitriles, such as acrylonitrile, methacrylonitrile, etc.; Multifunctional monomers, such as divinylbenzene, methylene bisacrylamide, ethylene glycol dimethacrylate, etc. Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates, such as monomethyl itaconate; monoalkyl maleates, such as monomethyl maleate;
Citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, acryloyloxyalkyl sulfonic acid, such as acryloyloxymethylsulfonic acid; methacryloyloxyalkyl sulfonic acid, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropyl Sulfonic acid, etc.; Acrylamidoalkylsulfonic acid, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; Methacrylamide alkylsulfonic acid , for example, 2-methacrylamide-
2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.; acryloyloxyalkyl phosphate,
Examples include acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc.; methacryloyloxyalkyl phosphate, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc. These acids are alkali metals (e.g. Na, K, etc.)
Alternatively, it may be a salt of ammonium ion.
Additionally, other comonomers include U.S. Pat.
No. 3459790, No. 3438708, No. 3554987, No. 4215195, No. 4247673, JP-A-57-205735
Crosslinkable monomers described in the specification of the above publication and the like can be used. Examples of such crosslinking monomers include N-(2-acetoacetoxyethyl)acrylamide, N-{2-(2
-acetoacetoxyethoxy)ethyl}acrylamide, and the like. Among these comonomers, acrylic esters and methacrylic esters are preferably used in view of the hydrophilicity and lipophilicity of the comonomers, the copolymerizability of the comonomers, the coloring properties of the produced polymer couplers, and the color tone of the produced dyes. , maleic esters, acrylamide, and methacrylamide. Two or more of these comonomers may be used in combination. Examples of combinations when two or more types are used together include n-butyl acrylate and methyl acrylate, styrene and N-[2-(2-acetoacetoxyethoxy)ethyl]acrylamide,
Examples include tert-butyl acrylate and methyl methacrylate. The polymer coupler according to the present invention is preferably a so-called copolymer, in which case it preferably contains 30 to 80% by weight of the repeating unit represented by the general formula
~70% is preferred. The yellow dye-forming polymer coupler latex of the present invention may be prepared directly by emulsion polymerization or by dissolving a lipophilic polymer coupler obtained by polymerizing coupler monomers in an organic solvent and forming a latex in an aqueous gelatin solution. You can also make it distributed. Regarding the emulsion polymerization method, U.S. Patent No.
No. 4,080,211, No. 3,370,952, and U.S. Pat.
The method described in this issue can be used. These methods can also be applied to the formation of homopolymers and copolymers; in the latter case the comonomer may be a liquid comonomer, which in the case of emulsion polymerization also acts as a solvent for the normally solid monomer. . As the polymerization initiator used in the emulsion polymerization method and solution polymerization method of the yellow dye-forming polymer coupler latex of the present invention, a water-soluble polymerization initiator and a lipophilic polymerization initiator are used. Examples of water-soluble polymerization initiators include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate;
Sodium 4,4'-azobis-4-cyanovalerate, 2,2'-azobis(2-amidinopropane)
Water-soluble azo compounds such as hydrochloride and hydrogen peroxide can be used. In addition, examples of the lipophilic polymerization initiator used in the solution polymerization method include azobisisobutyronitrile, 2,2'-azobis-(2,4
-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexanone-1
-carbonitrile), lipophilic azo compounds such as dimethyl 2,2'-azobisisobutyrate, diethyl 2,2'-azobisisobutyrate, benzoyl peroxide,
Examples include lauryl peroxide, diisopropyl peroxydicarbonate, and di-tert-butyl peroxide. Examples of emulsifiers used in the emulsion polymerization method include surfactants, polymeric protective colloids, and copolymer emulsifiers. Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants known in the art. Examples of anionic activators include soaps, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium dioctylsulfosuccinate, and sulfates of nonionic activators. Examples of nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene-polyoxypropylene block copolymer, and the like. Examples of cationic activators include alkylpyridium salts and tertiary amines. Furthermore, examples of amphoteric surfactants include dimethylalkylbetaines, alkylglycines, and the like. Examples of the polymeric protective colloid include polyvinyl alcohol and hydroxyethyl cellulose. These protective colloids may be used alone as emulsifiers or in combination with other surfactants. For information on the types of these activators and their effects, see Belgische
Chemische Industrie, vol. 28, pp. 16-20 (1963)
It is described in. To disperse a lipophilic polymer coupler synthesized by a solution polymerization method in the form of a latex in an aqueous gelatin solution, first dissolve the lipophilic polymer in an organic solvent, and then add a dispersant to the gelatin aqueous solution. With the help of ultrasonic waves, colloid mills, etc., it is dispersed into a latex form. A method of dispersing lipophilic polymeric couplers in aqueous gelatin solution in the form of a latex is described in US Pat. No. 3,451,820. As the organic solvent for dissolving the lipophilic polymer coupler, esters such as methyl acetate, ethyl acetate, propyl acetate, etc., alcohols, ketones, halogenated hydrocarbons, ethers, etc. can be used. Moreover, these organic solvents can be used alone or in combination of two or more. Next, the production of the polymer coupler of the present invention will be specifically described below, but the present invention is not limited thereto. Production method example of yellow dye-forming polymer coupler latex (1) Production of lipophilic polymer coupler latex (A) of exemplary coupler monomer (4) and n-butyl acrylate 10 g of exemplary polylar coupler (4) and n-butyl acrylate A mixture of 10g and 120ml of dioxane at 80℃
After stirring in a nitrogen stream and adding 0.36 g of azobisisobutyronitrile dissolved in 4 ml of dioxane, the mixture was reacted for 6 hours. A dioxane solution was added dropwise to water 2, and the precipitated solid was filtered off, washed with water, and dried to obtain 17.5 g (88%) of a lipophilic polymer coupler. The copolymer composition of this polymer coupler was determined by elemental analysis (nitrogen analysis) to have a content of coupler monomer (4) of 52.1%. Dissolve 10 g of the above polymer coupler in 30 ml of ethyl acetate, and add 10 g of sodium lauryl sulfate to this solution.
% aqueous solution and 100 ml of a 5 wt % gelatin aqueous solution were added and ultrasonic dispersion was performed. Thereafter, ethyl acetate was removed by vacuum distillation to obtain a polymer coupler latex (A). Production method example (2) Production of new oil-based polymer coupler latex (B) of exemplified coupler monomer (11) and methyl acrylate A mixture of 10 g of exemplified coupler monomer (11), 10 g of methyl acrylate, and 120 ml of dioxane was heated at 80°C in a nitrogen stream. After stirring and adding 0.36 g of azobisisobutyronitrile dissolved in 4 ml of dioxane,
It reacted for 6 hours. A dioxane solution was added dropwise to water 2, and the precipitated solid was filtered off, washed with water, and dried to obtain 18.0 g (90%) of a polymer coupler.
The copolymer composition of this polymer coupler was determined by elemental analysis (nitrogen analysis).
It was 50.8%. The above polymer coupler was treated in the same manner as in Production Example (1) to obtain a polymer coupler latex (B). Production Example (3) Production of lipophilic polymer coupler latex (C) of exemplified coupler monomer (16), n-butyl acrylate and methyl acrylate. Exemplary coupler monomer (16) 10g, n-butyl acrylate 5g, methyl acrylate 5g and tert-
A mixture of 200 ml of butanol was stirred under reflux in a nitrogen atmosphere, 0.36 g of azobisisobutyronitrile dissolved in 10 ml of tert-butanol was added, and the mixture was reacted for 6 hours. A tert-butanol solution was added dropwise to Water 2, and the precipitated solid was filtered off, washed with water, and dried to obtain 17.6 g (88%) of a lipophilic polymer coupler. The copolymer composition of this polymer coupler was found to have a coupler monomer (16) content of 51.8% by elemental analysis (nitrogen analysis). The above polymer coupler was treated in the same manner as in Production Example (1) to obtain a polymer coupler latex (C). Production Example (4) Production of polymer coupler latex (A') of exemplified coupler monomer (1) and n-butyl acrylate. 10 g of the exemplary coupler monomer (1) and 10 g of n-butyl acrylate were heated and dissolved in 200 ml of ethanol.
800 ml of an aqueous solution in which 2 g of sodium salt of oleyl methyltauride was dissolved was heated to 95°C in a nitrogen stream and stirred, and then 20 ml of 140 mg of potassium persulfate was added.
Aqueous solution was added. Next, the above-mentioned ethanol solution was added dropwise over a period of 1 hour. After dropping, heat and stir at 95-85℃, and after 3 hours add 20ml of 60mg of potassium persulfate.
An aqueous solution was added and the mixture was further stirred at the same temperature for 3 hours, after which ethanol and unreacted n-butyl acrylate were distilled off as an azeotropic mixture of water. The solid content concentration of the formed latex is 10.2wt.
%, and the copolymer composition was found to have a coupler monomer (1) content of 52.8% by elemental analysis. Production Example (5) Production of polymer coupler latex (B') of exemplified coupler monomer (21) and ethyl acrylate. 15 g of exemplified coupler monomer (21) and 5 g of ethyl acrylate were heated and dissolved in 200 ml of ethanol.
800 ml of an aqueous solution in which 2 g of sodium salt of oleyl methyltauride was dissolved was heated to 95°C in a nitrogen stream and stirred, and then 20 ml of 140 mg of potassium persulfate was added.
Aqueous solution was added. Next, the above-mentioned ethanol solution was added dropwise over a period of 1 hour. After dropping, heat and stir at 95-85℃, and after 3 hours add 20ml of 60mg of potassium persulfate.
An aqueous solution was added and the mixture was further stirred at the same temperature for 3 hours, after which ethanol and unreacted ethyl acrylate were distilled off as an azeotrope of water. The solid content concentration of the formed latex is 12.5wt.
%, and the copolymer composition was found to have a coupler monomer (21) content of 76.1% by elemental analysis. Production method examples (6) to (40) Production method examples (1), (2), using the above coupler monomer,
The following polymer coupler latex was obtained in the same manner as the copolymers of (3) (Production Example) and Production Examples (4) and (5) (Production Process).

【table】

[Table] Furthermore, the yellow dye-forming polymer coupler latex of the present invention is preferably used in combination with DIR compounds represented by the general formulas [] and []. General formula [] Cp-INH General formula [] Cp-TIME-INH In the formula, Cp represents a coupler component, and this coupler may or may not form a dye by coupling. INH is a development inhibitor group and is a compound that inhibits the development of silver halide. In the general formula [], INH binds to the coupling position of the coupler component and is released by reaction with the oxidized form of the color developing agent. The TIME group in the general formula [ ] is bonded to the coupling position of the coupler, released by reaction with the oxidized form of the color developing agent, and then
This is a group that can release INH groups in a moderately controlled manner. Coupler components represented by Cp include pigment-forming compounds such as acylacetanilides, malondiesters, malondiamides, benzoylmethanes, pyrazolones, pyrazolotriazoles, pyrozolobenzimidazoles, indazolones, phenols, and naphthols. Couplers and coupler components that do not substantially form dyes, such as acetophenones, indanones, and oxazolones. Preferred coupler components include the general formula [],
Examples include [] and []. General formula []

[ka] General formula []

[ka] General formula []

embedded image In the formula, R ₇ represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R ₈ and R ₉ each represent an aromatic group or a heterocyclic group. The aliphatic group represented by R ₇ preferably has 1 to 20 carbon atoms and may be substituted or unsubstituted, linear or cyclic. Preferred substituents for the alkyl group include alkoxy, aryloxy, and acylamino groups. Especially preferred as R ₇ is a tert-butyl group. When R ₇ , R ₈ or R ₉ is an aromatic group, it represents a phenyl group, a naphthyl group, etc., and a phenyl group is particularly useful.
This phenyl group may have a substituent. Examples of the substituent include alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, and alkylamido groups having 30 or less carbon atoms. moreover
The phenyl group represented by R ₇ , R ₈ and R ₉ may be substituted with an alkyl group, an alkoxy group, a cyano group or a halogen atom. R ₁₀ represents a hydrogen atom, an alkyl group, a halogen atom, etc., and l ₂ is an integer of 1 to 5, preferably a hydrogen atom. R ₁₁ and R ₁₂ represent a hydrogen atom, an alkyl group, or an aryl group, and the aryl group is preferably a phenyl group. The alkyl group and aryl group may have a substituent, and examples of the substituent include an alkoxy group, an aryloxy group, a halogen atom, and a carboxyl group. R ₁₁ and R ₁₂ may be the same or different. As INH, those represented by the following general formulas [] and [] are particularly preferred. General formula []

[ka] General formula []

[Chemical formula] R ₁₃ is an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, a halogen atom,
It represents a carbamoyl group, nitro group, cyano group, sulfamoyl group, hydroxy group, etc., and l ₃ is 1 or 2. R ₁₄ represents an alkyl group or an aryl group having 1 to 6 carbon atoms, and the aryl group is particularly preferably a phenyl group, and this phenyl group may have a substituent, and the substituent is an alkyl group. , alkoxy groups, halogen atoms, hydroxy groups, etc. As TIME, in particular, the general formula [], [
] and [ ] are preferable, but there are also others such as -OCH ₂ -INH ₃ -OCO-INH. General formula []

[ka] General formula []

[ka] General formula []

[Chemical formula] R ₁₅ is a hydrogen atom, an alkyl group, an alkoxy group,
It represents an anilino group, a nitro group, an aryl group, a carboxy group, a cyano group, etc., and l ₄ is an integer of 1 or 2. R ₁₆ represents an alkyl group, alkenyl group, aralkyl group, cycloalkyl group or aryl group. When R ₁₅ and R ₁₆ represent an aryl group, the aryl group may have a substituent, and examples of the substituent include an alkyl group, a halogen atom, and an alkoxy group. Next, preferred DIR compounds used in the present invention are shown below, but the present invention is not limited thereto.

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[Image Omitted] When the yellow dye-forming polymer coupler of the present invention is used in combination with the DIR coupler described above, it is particularly preferable to contain them in the same layer. In this case, the DIR coupler is contained in an amount of 0.0001 to 0.5 mol, preferably 0.001 to 0.05 mol, per mol of silver. The yellow dye-forming polymeric coupler latex of the present invention is preferably used in combination with an oxidized developing agent scavenger along with the DIR compound described above. Preferred examples of such oxidized developing agent scavengers include the following general formulas [] to []
It is expressed as General formula []

[ka] General formula []

embedded image In the formula, X ₂ represents a hydrogen atom, an alkyl group, an alkoxy group or a -OY ₂ group. Y ₂ is preferably a hydrogen atom, an acyl group, or an alkoxycarbonyl group, and particularly preferably a hydrogen atom. R ₁₇ , R ₁₈ and R ₁₉ are
Each hydrogen atom, alkyl group, halogen atom, -
SO ₂ R ₂₁ , -COR ₂₁ represents an alkoxy group, an alkylthio group or an aryl group. R ₂₁ represents an alkyl group, an alkyloxy group, an alkylamino group, an aryl group, an aryloxy group, an arylamino group, etc., and each of these may have a substituent. Q ₂ represents a sulfonyl group, acyl group, carboxyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfinyl group or cyano group. R ₂₀ represents the same group as R ₁₇ to R ₁₉ , l ₅ represents an integer from 0 to 2, and when l ₅ is 2, R ₂₀
may be the same or different. General formula []

[C] In the formula, Y ₃ is Y ₂ of the general formula [], []
, and R ₂₂ is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, which may further have a substituent. R ₂₃ , R ₂₄ and R ₂₅ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, etc., with a hydrogen atom being particularly preferred. General formula []

[C] In the formula, Cp is represented by the above general formula [], []
It is the same as Cp and represents a coupler component. SOL
is a dye formed by a coupling reaction of a compound represented by the general formula [] with an oxidized form of a color developing agent, and can flow out from a silver halide photographic light-sensitive material in an alkaline environment that exists during photographic processing. It is a solubilizing group that confers properties.
SOL includes carboxyl group, sulfonyl group,
Hydroxy group, etc. B ₂ is a group that binds to the coupling position of the coupler component and leaves by reaction with the oxidized product of the color developing agent, and has 8 to 8 carbon atoms.
It is a component containing 32 ballast groups. Specific examples of oxidized developing agent scavengers that can be used in combination with the yellow dye-forming polymer coupler latex in the present invention are shown below, but the present invention is not limited thereto.

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[Fixer composition]

Ammonium thiosulfate 50% aqueous solution 162ml Anhydrous sodium sulfite 12.4g Add water to make 1, and adjust the pH to 6.5 using acetic acid. [Stable bath composition] Formalin 37% aqueous solution 5.0ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. The graininess of the obtained yellow dye image was
Measured using the RMS (Root Mean Square) method. RMS
The value used was 1000 times the standard deviation of density value fluctuations that occur when scanning with a microdensitometer with a circular scanning aperture of 25 μm. RMS at concentration 0.7
The granularity results are shown in Table 1. In addition, the storage stability of dye images is 2 at 60℃ and 80%RH.
It was expressed as the residual rate of maximum concentration (Dmax) after weekly storage, and the values are shown in Table 1. Image storage property = Dmax after storage / Dmax before storage x 100 (%) Comparative couplers (1), (2), (3) and (4) have the following structures. Comparative coupler (1) (compound described in JP-A-50-87650)

[C] Comparative coupler (2) (compound described in JP-A-50-132926)

[C] Comparative coupler (3) (compound described in JP-A-59-42543)

[C] Comparative coupler (4) (compound described in JP-A-58-250989)

[ka]

[Table] As shown in Table 1, comparative couplers
(1), (2) and (3) showed good values in image storage stability, but were considerably poor in graininess (RMS value).
Comparative coupler (4) had significantly improved graininess, but had a significant deterioration in image storage stability. In contrast, the yellow dye-forming polymer coupler latexes (A), (D), (M), (T), (A'), (F') of the present invention
,
All samples using (I') and (L') had excellent performance satisfying both graininess and image preservation. Example 2 Latex (O) of the polymer coupler of the present invention,
For (S), (E') and (N') and the comparison coupler (4), amounts containing 7.5 x 10 ^-3 mol of yellow dye-forming coupler monomer units each were 5 x 10 ^-2 mol of silver chlorobromide. Mixed with 100g of photographic emulsion containing 10g of gelatin,
10 ml of 0.2% aqueous solution of 2-hydroxy-4,6-dichloro-S-triazine sodium salt as a hardening agent.
The mixture was coated on a polyethylene-coated support at a silver coating amount of 0.5 g/m ² and dried to obtain silver halide color photographic materials (Samples Nos. 13 to 17). These samples were wedge exposed in the usual way,
Processing was performed according to the following steps and processing methods. Processing process Color development 3 minutes 30 seconds Bleach fixing 1 minute 30 seconds Water washing 2 minutes 0 seconds [Color developer] Benzyl alcohol 15.0ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 18.5g Potassium bromide 0.60g Borax (Na ₂ B ₄ O ₇・10H ₂ O) 39.10g N-ethyl-N-{2-(methanesulfonamidoethyl)}-3-methyl-4-aminoanilinosulfate
Add 5.0g water to make up to 1, and add sodium hydroxide.
Adjusted to PH10.3. [Bleach-fix solution] Iron ammonium ethylenediaminetetraacetate 61.0g Diammonium ethylenediaminetetraacetate
5.0g Ammonium thiosulfate 124.5g Sodium metabisulfite 13.3g Sodium sulfite 2.7g Water was added to bring the mixture to 1, and the pH was adjusted to 6.5. The image storage stability of the yellow dye image obtained by developing each sample under the above conditions was measured in the same manner as in Example 1, and the results are shown in Table 2.

【table】

Table 2 As shown in Table 2, the image preservation properties of the yellow dye-forming polymer coupler latex of the present invention were better than the comparative couplers. Example 3 A multilayer color light-sensitive material (sample 18) was prepared using a cellulose triacetate film as a support and each layer had the composition shown below. 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: red-sensitive low-sensitivity emulsion layer Silver bromide emulsion (silver iodide: 4 mol%)... Silver coating amount (average grain size 0.5 μ) 1.79 g/m ² Sensitizing dye... 6 x 10 ^-5 mol per 1 mol of silver Sensitizing dye... ...for 1 mole of silver
1.5×10 ^-5 mol Coupler A: 0.06 mol per mol of silver Coupler C: 0.003 mol per mol of silver DIR compound D-7: per mol of silver
0.003 mol Tricresyl phosphate coating amount 0.3 cc/m ² 4th layer: Red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol%...Silver coating amount
(Average particle size 0.7μ) 1.4 g/m ² Sensitizing dye... 3 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...... per 1 mol of silver
1.2×10 ^-5 mol Coupler F...0.0120 mol per 1 mol of silver Coupler C...0.0020 mol per 1 mol of silver Tricresyl phosphate coating amount 0.2cc/m ² 5th layer: Intermediate layer 6th layer same as 2nd layer: Green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol%...Amount of coated silver
(Average particle size 0.5 μ) 1.0 g/m ² Sensitizing dye...3 x 10 ^-5 mol per mol of silver Sensitizing dye... 1 x 10 ^-5 mol per mol of silver Coupler B... 0.08 mol per 1 mol of silver Coupler M...0.008 mol per 1 mol of silver DIR Compound D-7... per 1 mol of silver
0.0015 mol Tricresyl phosphate coating amount 1.4 cc/m ² 7th layer: Green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 7 mol%...Amount of coated silver
(Average particle size 1.2μ) 1.6g/ ^m2 Sensitizing dye...for 1 mole of silver
2.5×10 ^-5 mol Sensitizing dye...for 1 mol of silver
0.8×10 ^-5 mol Coupler B...0.02 mol per 1 mol of silver Coupler M...0.003 mol per 1 mol of silver Tricresyl phosphate coating amount 0.8cc/m ² 8th layer: Yellow filter layer Yellow colloidal silver and 2,5-
and an emulsified dispersion of di-t-octylhydroquinone. 9th layer: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 6 mol%...Amount of coated silver
(Average grain size 0.6 μ) 0.5 g/m ² Coupler Y...0.125 mol per 1 mol of silver Tricresyl phosphate coating amount 0.3 cc/m ² 10th layer: Blue-sensitive high-sensitivity emulsion layer Iodobromide Silver emulsion Silver iodide: 6 mol%...Amount of coated silver
(Average particle size 0.8 μ) 0.6 g/m ² Coupler Y...0.04 mol per 1 mol of silver Tricresyl phosphate coating amount 0.1 cc/m ² 11th layer: Protective layer Polymethyl methacrylate particles (diameter approx. 1.5μ)
Apply a gelatin layer containing. The couplers in each layer are prepared by adding the coupler to a solution of tricresyl phosphate and ethyl acetate, adding sodium P-dodecylbenzenesulfonate as an emulsifier, dissolving it by heating, and mixing it with a heated 10% gelatin solution to form a colloid. It was emulsified in a mill and used. In each layer, a gelatin hardener and a surfactant were added to the above composition. The sample prepared as described above was designated as sample 13. Compound sensitizing dye used to prepare the sample: anhydro-5,5'-dichloro-
3,3'-di-(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye: anhydro-9-ethyl-3,3'-
Di-(γ-sulfopropyl)4,5,4',5'-
Dibenzothiacarbocyanine hydroxide
Triethylamine salt sensitizing dye: anhydro-9-ethyl-5,5'-
Dichloro-3,3'-di-(γ-sulfopropyl)
Oxacarbocyanine sodium salt sensitizing dye: anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-di-
(γ-Sulfopropyl)imidazolocarbocyanine hydroxide sodium salt

[ka]

[ka]

[ka]

[ka]

[ka]

[C] The coupler Y in the 9th and 10th layers of Sample 18 was changed as shown in Table 3. In addition, the DIR in Table 3 is added to the 9th layer.
A sample containing the compound and an oxidized developing agent scavenger was prepared in the same manner as Sample 18. For samples using polymer coupler latex, use tricresyl phosphate as the sample.
I made it 1/10 of 18. These samples were subjected to the same development process as in Example 1, and measurements of graininess and image storage stability were carried out. Furthermore, in order to evaluate the sharpness, these samples were exposed to light through a wedge whose spatial frequency was varied in the range of 3 lines/mm to 100 lines/mm, and developed in the same manner as in Example 1. The obtained dye is subjected to MTF (Modulation Transfer Function) using blue light.
I asked for Compare the values at a spatial frequency of 5 lines/mm,
The effect of improving sharpness was investigated. The MTF value was determined by measuring the density using a slitter with a slit width of 300μ in length and 2μ in width, and expressed the resolution as a percentage of the input.
The results are shown in Table 3.

【table】

[Table] As shown in Table 3, comparative coupler Y
showed good values for image storage stability and sharpness (MTF value), but was considerably inferior in graininess (RMS value). Comparative coupler (4) had significantly improved graininess, but had a large deterioration in image storage stability. Deterioration in sharpness was also observed. In contrast, samples using the yellow dye-forming polymer coupler latexes (M) and (L') of the present invention had excellent graininess and image storage stability, and improved sharpness was also observed. Furthermore, significant sharpness improvements were made by using DIR compounds and oxidized developer scavengers. Preferred Embodiment (1) A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow dye-forming polymer coupler latex having a repeating unit represented by the following general formula []. General formula []

[Formula] (2) A silver halide color photographic material characterized in that in the general formula [], the leaving group in Q is a divalent group derived from an aryloxy group. (3) A silver halide color photographic light-sensitive material, characterized in that the leaving group in Q in the general formula [] is a divalent group derived from a urazole group. (4) A silver halide color photographic light-sensitive material, characterized in that in the general formula [], the leaving group in Q is a divalent group derived from a hydantoin group. (5) A silver halide color photographic light-sensitive material, characterized in that in the general formula [], the leaving group in Q is a divalent group derived from a tetrazolone group. (6) A silver halide color photographic light-sensitive material characterized in that the yellow dye-forming polymer coupler latex of the present invention and a DIR compound are used together. (7) A silver halide color photographic light-sensitive material characterized in that the yellow dye-forming polymer coupler latex of the present invention and an oxidized developing agent scavenger are used together. (8) A silver halide color photographic material characterized in that the yellow dye-forming polymer coupler latex of the present invention is used in combination with a DIR compound and an oxidized developing agent scavenger.

Claims (1)

[Scope of Claims] 1. A silver halide emulsion layer containing a yellow dye-forming polymer coupler latex having a repeating unit represented by the following general formula [] capable of forming a dye with an alkaline color developer on a support. Silver halide color photographic material. [General formula] [Formula] (In the formula, R ₁ represents an alkyl group or an aryl group, R ₂ represents a monovalent group, and Q has an ethylenically unsaturated group and is a oxidized product of a color developing agent. Represents a group that can be separated by a coupling reaction, l is 0 to
Represents an integer of 5. )