JPH0467180B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION Technical Field The present invention relates to a novel magenta dye-forming polymeric coupler containing a novel magenta dye-forming polymer coupler capable of coupling with an oxidized product of an aromatic primary amine color developing agent to form a dye. This invention relates to silver color photographic materials. In the formation of color photographic images based on the subtractive color method, generally, after imagewise exposure of a silver halide color photographic light-sensitive material, an aromatic primary amine color developing agent is added in the presence of a cyan coupler, a magenta coupler, and a yellow coupler. This is done by color development using. At that time, the exposed silver halide grains of the silver halide color photographic light-sensitive material are reduced to silver by the color developing agent.
The oxidized color developing agent produced at the same time undergoes a coupling reaction with the coupler to form a color photographic image consisting of cyan, magenta and yellow dyes. These couplers are contained in the silver halide emulsion in the internal color development method, and in the color developing solution in the external color development method.Currently, the internal color method is a simple method that requires only one color development. is often used. To form a yellow dye image, for example, an acylacetanilide or benzoylmethane coupler is used, and to form a magenta dye image, a pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or indazolone coupler is used. Couplers are used, primarily phenolic couplers, such as phenols and naphthols, to form cyan dye images. Couplers not only form a dye image through color development, but also have good color developability, good dispersibility and stability in silver halide emulsions, and also the fact that the formed dye image is ,
Requirements such as having a high degree of stability against heat, humidity, etc. over a long period of time, and having a light absorption wavelength range within a desirable range must be met. By the way, in silver halide color photographic light-sensitive materials having a multilayer structure, mixing of each dye is reduced,
In order to improve color reproduction, it is necessary to fix each coupler in a separate layer. 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 gelatin aqueous solutions, so they are either solubilized in alkali and added to the gelatin aqueous solution, or couplers with oil-soluble ballast groups (diffusion-inhibiting groups) are used with the help of surfactants. It is necessary to disperse them as colloidal particles in an aqueous gelatin solution together with an organic solvent. Such a coupler is
The hydrophilic groups in the coupler 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. Furthermore, 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 a latex in the following manner. One method is to polymerize the coupler monomer together with other copolymerization components (comonomers) if necessary by emulsion polymerization to form a latex directly, and add this to the silver halide emulsion.The other method requires the coupler monomer. In this method, a polymer coupler obtained by solution polymerization together with other copolymerizations (comonomers) is dissolved in a solvent, and then dispersed in an aqueous gelatin solution to form a latex. The former emulsion polymerization method has a US patent.
No. 3370952 and No. 4080211, respectively. The latter method is described, for example, in US Pat. No. 3,451,820. The method of adding such polymeric couplers to hydrophilic colloid compositions in the form of a latex has many advantages over other methods, including: First, (1) the latex polymer coupler can contain a high concentration of coupler units, so that a high concentration of the coupler can be easily incorporated into the emulsion. (2) Moreover, since it is not necessary to include a high boiling point organic solvent for dispersing the coupler, it is possible to form a thin film. (3) Image sharpness can be improved. (4) Since there is little thickening phenomenon of the gelatin aqueous solution, high-speed uniform coating is possible. (5) Since the polymer coupler is made into a latex, it does not deteriorate the strength of the formed film. (6) In addition, polymer couplers have coupler units incorporated into the polymer, so they remain in the desired layer and do not migrate to other layers, so there is no need to worry about color mixing of dyes.
Moreover, precipitation of coupler in the emulsion film is small. British Patent No. 1247688 and US Patent No. 3451820 include
An example is described in which a latex of a 4-equivalent magenta polymer coupler is added to a silver halide emulsion.
Further, examples of copolymer latexes with competing couplers are described in German Patent No. 2725591 and US Pat. No. 3926436. Also, US patent
No. 3767412 describes a cyan coupler latex. However, although these latexes of polymer couplers have many excellent advantages as described above, they also have the following problems that should be improved, and improvements are desired. (1) Sufficient dye concentration cannot be obtained due to the slow reaction rate of coupling. (2) Color development tends to cause unnecessary fogging. (3) The coupler monomer has low solubility and extremely low polymerizability. (4) The color fastness of the formed dye image is poor. OBJECTS OF THE INVENTION Accordingly, the first object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel magenta polymer coupler which eliminates such conventional drawbacks and has excellent coloring properties. It is in. A second object of the present invention is that the coating layer is thinned,
An object of the present invention is to provide a silver halide color photographic material capable of obtaining dye images with improved sharpness. A third object of the present invention is to provide a silver halide color photographic material with high film strength. A fourth object of the present invention is to provide a silver halide color photographic light-sensitive material that forms a dye image that is robust against light, heat, and moist heat in a color photograph after color development processing. As a result of various studies, the present inventors have found that the objects of the present invention are to provide a silver halide material containing a magenta dye-forming polymer coupler having a repeating unit represented by the following general formula [] on a support. This is achieved using a silver halide color photographic light-sensitive material having an emulsion layer. General formula [] (In the formula, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, Z represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized color developing agent, and X represents an electron-withdrawing group. (l represents an integer from 0 to 3, and when l is 2 or more, X may be the same or different.) Specific constitution of the invention Q represented by the above general formula [] is, It is an ethylenically unsaturated group or a group having an ethylenically unsaturated group, and is more preferably represented by the following general formula []. General formula [] In the formula, R represents a hydrogen atom, a halogen atom, or an alkyl group, preferably a lower alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a t-butyl group, etc.), and this alkyl group is a substituent. It may have. L is -CONH- (However, the nitrogen atom is bonded to the pyrazolone ring.) -NHCONH-
Alternatively, it represents a divalent group of -NH-, and P is -
CONH- (however, the nitrogen atom is bonded to A in the general formula []), -SO ₂ - or -COO- (however,
The oxygen atom is bonded to A in the general formula []. )
represents a divalent group, preferably -CONH-,
or a divalent group of -COO-. A represents an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms) or a divalent group such as a phenylene group,
The alkylene group may be linear or branched, such as a methylene group, methylmethylene group, dimethylene group, decamethylene group, etc., and the alkylene group and phenylene group may have a substituent. m and n each represent 0 or 1. In the general formula [], preferably L is -
CONH- or -NH-, when n is 1, A is m-phenylene, m is 1 and P
is -CONH-, and R is a lower alkyl group. Even more preferably, L is -CONH-,
This is the case when m and n are 0 and R is a lower alkyl group, especially a methyl group. Substituents for the alkylene group or phenylene group represented by A include aryl group (e.g. phenyl group), nitro group, hydroxyl group, cyano group, sulfo group,
Alkoxy groups (e.g. ethoxy groups), acyloxy groups (e.g. acetoxy groups), acylamino groups (e.g. acetylamino groups), sulfonamide groups (e.g. methanesulfonamide groups), sulfamoyl groups (e.g. methylsulfamoyl groups), halogen atoms ( Examples include fluorine atom, chlorine atom, bromine atom, etc.), carboxyl group, carbamoyl group (e.g. methylcarbamoyl group), alkoxycarbamoyl group (e.g. methoxycarbamoyl group, etc.), sulfonyl group (e.g. methylsulfonyl group, etc.). . Two or more of these substituents may be present, and in that case, these substituents may be the same or different. In the general formula [], the group represented by Z that can be separated during the coupling reaction with the oxidized color developing agent is represented by the following general formula [a],
It is represented by [b] and [c]. General formula [a] -O-R ₁ General formula [b] -S-R ₂ General formula [c] In the formula, R ₁ and R ₂ represent an alkyl group, an aryl group, an acyl group, etc., and R ₃ represents a 5- or 6-membered heterocycle (for example, an imidazole ring, a pyrazole ring, a piperidine ring, a morpholine ring, a succinimide ring, a triazole ring, etc.). Represents a group of nonmetallic atoms necessary to form a ring, etc.). Next, preferred specific examples of Z represented by the general formulas [a], [b] and [c] are shown below, but the present invention is not limited thereto. (1) Specific examples corresponding to -O-R ₁ in general formula [a] -O-C ₁₂ H ₂₅ ,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] (2) Specific example corresponding to -S-R ₂ in general formula [b]

【formula】

[Formula] − SC ₁₂ H ₂₅ ,

[Formula] SC ₁₃ H ₃₇ , −SC ₂ H ₅ , −SCH ₂ C ₂ OH,

【formula】

【formula】 (3) General formula [c]

Corresponds to [formula] Specific example

【formula】 【formula】

【formula】

【formula】 【formula】

【formula】

[Formula] The -CF ₃ group represented by the general formula [] may be substituted at any position of the phenyl group bonded to the 1-position of the pyrazolone ring in the general formula [], but it is particularly preferably substituted at the 2-position. , 3rd place and 5th place. The electron-withdrawing group X represented by the general formula [] is
Although the phenyl group may be substituted at any position, it is particularly preferably substituted at a position selected from the 2-position, the 4-position and the 6-position. l represents an integer from 0 to 3 as described above, preferably from 0 to 2. Further, when l is 2 or more, X may be the same or different types of electron-withdrawing. Here, the electron-withdrawing group is “Physical Organic Chemistry” McGraw
- the σ value defined by Hammett et al. or J. Amer. Chem. Soc., as described in Hill Book Co., New York (1940);
90, 4328 (1968), it is defined as a substituent whose F value is greater than zero, as derived by Swain and Lupton et al. Specific electron-withdrawing properties include halogen atoms, halogenoalkyl groups, carboxyl groups,
Sulfo group, nitro group, cyano group, alkylsulfonyl group, alkylcarbonyl group, alkoxycarbonyl group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonamide group,
Examples include arylsulfonamide groups, and J.Med.Chem.16, 1207 (1973), 20, 304
(1977) may also be used. Among the electron-withdrawing groups used in the present invention, preferred are alkylsulfamoyl groups in which the alkyl moiety has 1 to 4 carbon atoms, such as dimethylsulfamoyl group and ethylsulfamoyl group. A halogenoalkyl group, such as a group, in which the alkyl portion has 1 to 2 carbon atoms.
halogen atom, such as trifluoromethyl or trichloromethyl; an alkoxycarbonyl group in which the alkyl moiety has 1 to 4 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, propoxycarbonyl group; group, butoxycarbonyl group, etc., and particularly preferred is a halogen atom. A particularly preferred halogen atom is a chlorine atom. Next, preferred specific examples of monomers (hereinafter referred to as coupler monomers) corresponding to the general formula [] of the present invention are listed below, but the present invention is not limited thereto. Typical synthesis examples of coupler monomers used in the present invention are shown below, but the present invention is not limited thereto. Synthesis of coupler monomer Synthesis example 1 1-(2-trifluoromethylphenyl)-3-
Methacryloylamino-2-pyrazoline-5-
(Synthesis of Exemplary Compound (6)) Orthotrifluoromethylaniline 50g
(0.310 mol) was suspended in 116 g of 36% concentrated hydrochloric acid,
The mixture was stirred under ice cooling. Dissolve 22.5 g of sodium nitrite in 63 ml of water while maintaining the liquid temperature between 3°C and 5°C.
(0.326 mol) was added dropwise little by little over 1 hour.
After the completion of the reaction after addition was confirmed using potassium iodide starch paper, impurities were removed by filtration. The obtained liquid was mixed with 1300 g of 36% concentrated hydrochloric acid and 217 g of stannous chloride dihydrate.
It was added dropwise to an aqueous solution in which g (0.96 mol) had been dissolved while cooling with ice and maintaining the liquid temperature at 7°C to 10°C. After this dropwise addition was carried out over 1 hour, the mixture was further stirred at room temperature for 30 minutes. After the reaction was completed, the precipitate was separated and dried. Next, this precipitate was dissolved in 1 part of water, 20 g of diatomaceous earth was added thereto, stirred, and filtered to separate the diatomaceous earth. The resulting liquid was cooled on ice, and 50% sodium hydroxide was added to adjust the pH of the liquid to 10. The precipitate was separated and 51 g (0.29 mol) of orthotrifluoromethylphenylhydrazine was obtained (yield:
93%). Next, 50 g (0.28 mol) of this hydrazine was added to β-
Ethyl ethoxy-β-iminopropionate hydrochloride 83g (0.426mol) and anhydrous sodium acetate 38g
(0.454 mol) was added to a solution of 400 ml of methanol, and the mixture was stirred at room temperature for 4 hours to react.
Next, 70.4 g (1.0 mol) of potassium hydroxide dissolved in 180 ml of methanol was added little by little under ice cooling. The reaction solution turned from yellow-orange to deep red. After the reaction was completed, the reaction solution was poured into 2250 ml of water, and 6N hydrochloric acid aqueous solution was added under ice cooling to adjust the pH to 4 to 5.
Next, extraction with ethyl acetate and washing with water were performed twice, followed by drying over anhydrous sodium sulfate, and ethyl acetate was distilled off to give an oily 1-(2-trifluoromethylphenyl-3-amino- 40.5 g (0.17 mol) of 2-pyrazolin-5-one was obtained (yield 60
%). Next, 40 g (0.165 mol) of this amino compound was dissolved in 300 ml of tetrahydrofuran together with 40 ml (0.49 mol) of pyridine and 4 ml of nitrobenzene, and the mixture was stirred under ice cooling. While maintaining the liquid temperature at 0 to 3°C, 39.5 g (0.378 mol) of methacrylic acid chloride was added dropwise to react. After the dropwise addition was completed, the reaction solution was stirred at room temperature for 30 minutes, poured into 300 ml of water, extracted with ethyl acetate, washed twice with water, dried over anhydrous sodium sulfate, and ethyl acetate was distilled off. . Next, add 250% ethanol to the resulting viscous residual oil.
ml and stirred under ice cooling. Next, 20 g of sodium hydroxide was dissolved in 60 ml of water to this solution.
Add aqueous sodium hydroxide solution of 10 to 15% by weight.
Stir for a minute, then pour the reaction solution into 400 ml of water, add 100 c.c. of 6N hydrochloric acid to adjust the reaction solution to pH 4-5, then extract with ethyl acetate, wash with water, and dry with anhydrous sodium sulfate. After adding a small amount of hydroquinone monomethyl ether, ethyl acetate was distilled off. The obtained viscous oil was mixed with toluene/n
- After solidifying by adding hexane mixed solvent, 24.7g (0.082 mol, yield 50
%, mp 85-88°C) was obtained. The structure of this coupler monomer is IR, NMR, FD-
This was confirmed using mass spectra. Synthesis Example 2 1-(2-chloro-5-trifluoromethylphenyl)-3-methacryloylamino-2-pyrazolin-5-one (synthesis of exemplified compound (8)) 2-chloro-5-trifluoromethylphenyl 15 g (0.07 mol) of enylhydrazine to β-ethoxy-β
- ethyl iminopropionate hydrochloride 21g (0.107
mol) and 9 g (0.107 mol) of anhydrous sodium acetate
was added to 150 ml of methanol in which the mixture was suspended, and reacted with stirring at room temperature for 3 hours. Next, add 17.5 g (0.27 mol) of potassium hydroxide to 55 ml of methanol.
A solution containing dissolved was added little by little under ice-cooling to obtain a deep red reaction solution. After the reaction was completed, 17.5 ml of glacial acetic acid was added, then the reaction solution was added to 600 ml of water, extracted with ethyl acetate, washed with water, dried with anhydrous sodium sulfate, and the ethyl acetate was distilled off. candy-like 1-(2-chloro-5-trifluoromethylphenyl)-3-amino-2-pyrazoline-
5-one was obtained. 18g (0.056 mol) of this amino form
was dissolved in 270 ml of tetrahydrofuran along with 10.5 ml of pyridine and 1 ml of nitrobenzene, and the mixture was stirred under ice-cooling. While maintaining the liquid temperature at 0° C. to 3° C., 13.6 g (0.130 mol) of methacrylic acid chloride was added dropwise to react. After the reaction was completed, the reaction solution was poured into 600 ml of water, extracted with ethyl acetate, washed twice with water, dried over anhydrous sodium sulfate, and the ethyl acetate was distilled off. Beige crystals with a melting point of 115-116°C were obtained. I got it. The crystals were suspended in a mixture of 40 ml of ethanol and 40 ml of water. Next, 8.8 g (0.22 mol) of sodium hydroxide dissolved in 30 ml of water was added little by little under ice cooling. After the hydrolysis reaction is completed, add the reaction solution to 300ml of water,
Extract with ethyl acetate, wash twice with water,
It was then dried with anhydrous sodium sulfate. After distilling off ethyl acetate, the resulting caramel-like substance was recrystallized using methanol to give 20 g (0.06 mol, yield 82
%, mp 80-85°C) was obtained. The structure of this coupler monomer is IR, NMR, FD-
This was confirmed using mass spectra. The polymer coupler according to the present invention may be a so-called homopolymer consisting only of repeating units represented by the general formula [], or a so-called copolymer with one or more other copolymerizable comonomers. However, in the present invention, it is preferably a copolymerized polymer coupler. Examples of comonomers that can be copolymerized include acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, olefins, styrenes, 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, tert-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-hydroxybenzyl 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 esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert.
-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-proboxyethyl methacrylate, 2
-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-
(2-ethoxyethoxy)ethyl methacrylate,
Examples include 2-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (additional mole number n=6), allyl methacrylate, and dimethylaminoethyl methacrylate methyl chloride salt. 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, acetoxystyrene, chlorstyrene, 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, and dibutyl maleate. Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of other comonomers include: Acrylamides, such as acrylamide, methylacrylamide, ethyl acrylamide, propylacrylamide, butylacrylamide,
tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide N-(2-acetoacetoxyethyl)acrylamide, etc.; Allyl compounds, such as 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 Ketones, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc.; Glycidyl esters, e.g. , glycidyl acrylate, glycidyl methacrylate, etc.; unsaturated nitriles, such as acrylonitrile, methacrylonitrile, etc.; polyfunctional 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, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates such as monomethyl maleate, monoethyl maleate, maleic acid, etc. monobutyl acid, etc.;
Citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.; methacryloyloxyalkylsulfonic acid, such as Methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; acrylamide alkylsulfonic acids, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamide -2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acid, such as 2-methacrylamide-2
-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.;
Acryloyloxyalkyl phosphate, e.g. acryloyloxyethyl phosphate, 3
-acryloyloxypropyl-2-phosphate, etc.; methacryloyloxyalkyl phosphate, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2
-phosphate, etc.; sodium 3-acryloxy-2-hydroxypropanesulfonate having two hydrophilic groups, and the like. These acids may be salts of acrylic metals (eg, Na, K, etc.) or ammonium ions. Other comonomers include U.S. Pat. No. 3,459,790;
Same No. 3438708, Same No. 3554987, Same No. 4215195,
Crosslinkable monomers described in JP-A No. 4247673, JP-A-57-205735, etc. can be used. Specific examples of such crosslinkable 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. Typical combinations of two or more types include n-butyl acrylate and methyl acrylate, and n-butyl acrylate and 2-butyl acrylate.
Examples include sodium acrylamide-2-methylpropanesulfonate, n-butyl acrylate and methyl methacrylate. The polymer coupler according to the present invention is preferably a so-called copolymer, and in that case, it is preferable that the repeating unit represented by the general formula [] contains 5 to 95% by weight of the total, especially the general formula [ The ratio of the repeating unit represented by ] to the comonomer is approximately 1:1.5 to 1:0.40 by weight, preferably 1:1. The magenta polymer coupler of the present invention may be prepared by an emulsion polymerization method, or by dissolving a lipophilic polymer coupler obtained by polymerizing a monomeric coupler in an organic solvent and dispersing it in the form of a latex in an aqueous gelatin solution. You can make one. For the emulsion polymerization method, use the method described in U.S. Pat. I can do it. 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 normally also acts as a solvent for the immobilized monomer. . As the polymerization initiator used in the emulsion polymerization method and solution polymerization method of the magenta polymer coupler 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, 4,4'-azobis-4-
Sodium cyanovalerate, 2,2'-azobis(2
Water-soluble azo compounds such as -amidinopropane) hydrochloride and hydrogen peroxide can be used. In addition, as a lipophilic polymerization initiator used in solution polymerization method,
For example, azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile),
Lipophilic azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexanone-1-carbonitrile), benzoyl peroxide, lauryl peroxide, diisopropyl Lipophilic peroxides such as peroxydicarbonate and di-tert-butyl peroxide can be mentioned. 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,
Examples include sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium dioctylsulfosuccinate, and sulfates of nonionic active agents. 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. 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 are
It may be used alone as an emulsifier or in combination with other surfactants. For information on the types of these activators and their effects, see Belgische
Chemische Industrie, 28, 16-20 (1963). In order to disperse a lipophilic polymer coupler synthesized by a solution polymerization method in the form of a latex in an aqueous gelatin solution, the lipophilic polymer coupler is first dissolved in an organic solvent and then mixed with a dispersing agent in an aqueous gelatin solution. With the help of ultrasonic waves, colloid mills, etc., it is dispersed into a latex form. U.S. Pat.
Described in No. 3451820. 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 synthesis of the polymer coupler of the present invention will be specifically described below, but the present invention is not limited thereto. Production example of magenta polymer coupler 1 [1-(2-trifluoromethylphenyl-3
Polymer coupler latex (A) consisting of -(3-methacryloylamino)-2-pyrazolin-5-one (6) and n-butyl acrylate] Exemplary compound (6)
A mixture of 20 g of coupler monomer, 20 g of n-butyl acrylate and 150 ml of dioxane was stirred.
While heating to 80°C, 350 mg of azobisisobutyronitrile dissolved in 10 ml of dioxane was added, and the mixture was reacted for about 5 hours. Next, this reaction product was poured into ice water 2 containing 10% by weight of sodium chloride to separate the precipitated solid and thoroughly washed with water. By drying this reaction product, 36.8 g of polymer coupler was obtained.
Elemental analysis revealed that this polymer coupler had a monomeric coupler content of 49.8%. Note that the monomeric coupler content herein refers to the weight percent of monomeric coupler units contained in the polymer solid content. Next, two types of solutions (a) and (b) below were prepared. Solution (a) 5% by weight aqueous gelatin solution (PH5.7, 35℃) 300
Heat 10 g of sodium lauryl sulfate to 32°C.
Added 10ml of wt% aqueous solution. Solution (b) 20g of the above polymer coupler was dissolved in 100g of ethyl acetate at 38°C. Next, the solution (B) was put into an anti-aeration mixer that was being stirred at high speed, and after the solution (A) was suddenly added thereto, the mixer was stopped for 1 minute and ethyl acetate was distilled off under reduced pressure. In this way, a polymer coupler latex (A) was prepared by dispersing the polymer coupler in a dilute gelatin solution and dispersing the polymer coupler in the dilute gelatin solution. Production Example 2 1-(2-chloro-5-trifluoromethylphenyl)-3-(3-methacryloylamino)-
Latex of polymer coupler of 2-pyrazolin-5-one and n-butyl acrylate (B) Coupler monomer (8) shown in exemplified compound (8)20
A mixture of 20 g of g, n-butyl acrylate and 150 ml of dioxane was heated to 80 DEG C. with stirring, and 350 mg of azobisisobutyronitrile dissolved in 10 ml of dioxane was added thereto, followed by reaction for about 4 hours. Next, this product was poured into ice water 2 containing 10% by weight of sodium chloride to separate the precipitated solid, which was then thoroughly washed with water. By drying this product, 38.0 g of polymer coupler was obtained. The monomer coupler content of this polymer coupler was found to be 50.8% by elemental analysis. Next, a polymer coupler latex (B) was prepared in the same manner as the polymer coupler in Production Example (1). Production example 3 1-(2-trifluoromethylphenyl)-3-
Polymer latex of (3-methacryloylamino)-2-pyrazolin-5-one (1) and n-butyl acrylate (latex coupler (A')) 2 g of sodium salt of oleylmethyltauride
An aqueous solution of 2 was heated to 95° C. under a nitrogen stream. To this mixture was added a 40 ml aqueous solution of 280 mg of potassium persulfate. Then n-butyl acrylate 20
g and 20 g of coupler monomer (1) in 200 ml of ethanol.
The mixture was heated to dissolve and added dropwise for 1 hour while preventing precipitation of crystals. After dropping, react for 1 hour and add 120 mg of potassium persulfate.
After adding 40 ml of aqueous solution and reacting for an additional hour, ethanol and unreacted n-butyl acrylate were distilled off as an azeotrope of water. The formed latex was cooled, the pH was adjusted to 6.0 with a 5% aqueous sodium carbonate solution, and then vortexed. The solid content concentration of latex is 12.3
%, the coupler content was 48.3%. The coupler content herein refers to the weight percent of coupler units contained in the latex solid content, and was determined from the nitrogen atom content obtained by elemental analysis. Production example 4 1-(2-chloro-5-trifluoromethylphenyl)-3-(3-methacryloylamino)-
Latex of copolymer of 2-pyrazolin-5-one (8) and n-butyl acrylate (latex coupler (B')) 2 g of sodium salt of oleyl methyl tauride
The aqueous solution of No. 2 was heated to 95° C. while passing through a nitrogen stream. 40ml of potassium persulfate 280mg to this mixture
An aqueous solution of was added. Next, 20 g of n-butyl acrylate and 20 g of coupler monomer (8) were mixed with ethanol.
The solution was heated to dissolve in 200 ml and added dropwise over 1 hour while preventing precipitation of crystals. After the dropwise addition, the mixture was reacted for 1 hour, and then ethanol and unreacted n-butyl acrylate were distilled off as an azeotrope of water. The formed latex was cooled and the pH was adjusted to 6.0 with a 5% aqueous sodium carbonate solution. The solid content concentration of latex is
14.2%, and the monomeric coupler content was 48.3%. Polymer coupler latexes (c) to (z) were produced according to the same method as in Production Examples 1 and 2 by changing the monomer coupler represented by the general formula [] of the present invention and the types and amounts of comonomers. Shown in Table 1. Table 2 shows latexes (C') to (W') of polymer couplers synthesized according to Production Examples 3 and 4.

【table】

【table】

【table】

【table】

[Color developer]

4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniphosphate salt
4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid sodium salt (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1, and use potassium hydroxide to
Adjust to PH10.0. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g ammonium bromide 150.0g glacial acetic acid
Add 10.0ml of water to bring the pH to 1, and adjust the pH to 6.0 using ammonia water. [Fixer composition] Ammonium thiosulfate 50% aqueous solution 162ml Anhydrous sodium sulfite 12.4g Add water to make 1, and adjust to PH6.5 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 density of the obtained magenta dye image is measured through a magenta filter, and fog and relative sensitivity (S) are measured.
and the maximum concentration (Dmax) were calculated and the obtained results are shown in Table 3. In addition, the latex of the polymer coupler for comparison
(1), (2), and (3) have the following compositions. Comparative example 1 Comparative example 2 Comparative example 3

[Table] Relative values of the reciprocal of the exposure amount required for Each sample (1) to (5) is a latex of a comparative polymer coupler.
It was found that the color development was superior to that of samples (6) to (8) obtained using (1), (2), and (3), and there was less fog. Example 2 Latexes (A'), (B'), (I') and (U') of polymer couplers of the present invention and latexes (1'), (2') and (3') of polymer couplers for comparison. For each, an amount containing 5 x 10 ^-3 moles of coupler monomer units was added to 100 g of a high-sensitivity silver iodobromide emulsion containing 5 x 10 ^-2 moles of silver halide and 10 g of gelatin, and coated on a triacetate support in an amount of 2.4 silver. g/ ^m2
Silver halide color photographic materials (Samples Nos. 9 to 15) having stable coating films were obtained by coating and drying. These photosensitive materials were wedge exposed in the same manner as in Example 1 and then developed. The results are shown in Table 4. The latexes (1'), (2') and (3') of the comparative polymer couplers had the following compositions. Comparative example 1′ Comparative example 2′ Comparative example 3′

[Color developer]

Benzyl alcohol 15.0ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.85g Potassium bromide 0.60g Borax (Na ₂ B ₄ O ₇・10H ₂ O) 39.10 g N-ethyl-N-{2-(methanesulfonamidoethyl) }-3-Methyl-4-aminoaniline sulfate 5.0 Add water to make up to 1, and dilute with sodium hydroxide.
Adjusted to PH10.3. [Bleach-fix solution] Ethylenediaminetetraacetate iron ammonium
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 density of the magenta dye image obtained by developing each sample under the above conditions was measured, and the fog, relative sensitivity (S) and maximum density (Dmax) were calculated, and the obtained results are shown in Table 5. Shown below. In addition, the latex of the polymer coupler for comparison
The compositions of (1), (2) and (3) are the same as in Example 1.

[Table] This is the relative value of the reciprocal of the exposure amount required.
As is clear from Table 5, the silver halide color photographic materials (Samples 16 to 20) obtained using the polymer couplers of the present invention are different from those of the comparative polymer couplers (1), (2) and (3). ) It can be seen that the color development properties are very excellent compared to the silver halide color photographic light-sensitive materials (Samples 21 to 23) obtained using the above methods, and there is less fog. Example 4 Latices (A'), (B'), (I'), (U') of polymer couplers of the present invention and latexes (1'), (2'), (3') of polymer couplers for comparison. For each solution, each magenta dye-forming coupler unit is
An amount containing 7.5×10 ^-3 mol was mixed with 100 g of a photographic emulsion containing 5×10 ^-2 mol of silver halide and 10 g of gelatin,
10 ml of a 2% aqueous solution of 2-hydroxy-4,6-dichloro-S-triazine sodium salt as a hardening agent.
was added, coated on a support coated with polyethylene, and dried to prepare a silver halide color photographic material. The amount of silver coated in these samples was 0.5
g/ ^m2 . These samples were wedge exposed in a conventional manner and developed in the same manner as in Example 3. Measure the density of the obtained magenta dye image, and calculate fog (Fog), relative sensitivity (S) and maximum density (Dmax).
was calculated, and the obtained results are shown in Table 6. In addition,
Comparative polymer coupler latex (1′),
The compositions of (2') and (3') are the same as in Example 2.

[First developer]

Pentasodium nitro-N,N,N-trimethylenephosphonate aqueous solution (45%) 1.0ml Potassium sulfite dihydrate 35.0g Sodium bromide 2.2g Sodium thiocyanate 1.0g Potassium iodide 4.5mg Potassium hydroxide 4.5g Diethylene glycol 12.0ml 1-phenyl-4-hydroxymethyl-3
-Pyrazolidone 1.5g Anhydrous potassium carbonate 14.0g Sodium bicarbonate 12.0g Potassium hydroquinone sulfonate 22.0g Add water and adjust the pH to 9.6 [Reversal solution] Propionic acid 12.0ml Anhydrous stannous chloride 1.5g Para-aminophenol 0.5 mg Sodium hydroxide 5.0g Nitrilo-N,NN-trimethyleneosphonate pentasodium aqueous solution (45%) 15.0ml Add water to make 1. Adjust to PH5.8 [Color developer] Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium aqueous solution 45%) 5.0ml Phosphoric acid (85%) 7.0ml Sodium bromide 0.7g Potassium iodide 30.0mg Hydroxide Potassium 20.0g Citrazic acid 1.3g 4-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate 11.0g 1,8-hydroxy-3,6-dithiaoctane
1.0g Add water to adjust the pH to 1 to 11.7 [Adjustment solution] Potassium sulfite 15.0g Ethylenediaminetetraacetic acid 8.0g α-monothioglycerol 0.5ml Add water to adjust the pH to 1 to 6.2 [Bleaching solution] Potassium sulfate 25.0g Potassium bromide 80.0g Iron()ammonium ethylenediaminetetraacetate
110.0g Hydrobromic acid (48%) 30.0ml Ethylenediaminetetraacetic acid 4.0g Add water to make 1. Adjust the pH to 5.7 [Fixer] Ammonium thiosulfate 55.0g Disodium ethylenediaminetetraacetate 0.8g Sodium metabisulfite 7.5g Sodium hydroxide 1.5g Add water to make 1. Adjust to PH6.6 [Stabilizer] Formalin (35%) 6.0ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. The density of the Zenta dye image obtained by developing under the above conditions was measured, and the fog, relative sensitivity (S), and maximum density (Dmax) were calculated, and the obtained results are shown in Table 7. It was shown to. The compositions of comparative polymer coupler latexes (1), (2), (1') and (2') are the same as in Examples 1 and 2.

【table】

[Table] Relative value of the reciprocal of the exposure amount required for.
As is clear from Table 7, the samples obtained using the latex of the polymer coupler of the present invention have much better color development and less fog than the samples obtained using the latex of the comparative polymer coupler. I found out.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material having, on a support, a silver halide emulsion layer containing a magenta dye-forming polymer coupler having a repeating unit represented by the following general formula []. General formula [] (In the formula, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, Z represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized color developing agent, and X represents an electron-withdrawing group. 1 represents an integer from 0 to 3, and when 1 is 2 or more, X may be the same or different.)