JPH03135550A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance image sharpness, maximum density, and sensitivity by incorporating a magenta dye-forming polymer coupler having specified repeating units and a specified coupler capable of releasing a development inhibitor. CONSTITUTION:The silver halide emulsion layer contains at least one of the magenta bye-forming polymer couplers having the repeating units each represented by formula I and/or II and at least one of the development inhibitor releasing coupler represented by formulae III and IV. In formulae I-IV, R1 is H, halogen, or the like; R2 is alkyl, or the like; J is a divalent organic group; Z is H or a group to be released by the coupling with the oxidation product of a color developing agent; Cp is a coupler component; INH is a development inhibiting group; TIME is a group combined with the coupling site of the Cp and it is to be released by the coupling with the oxidation product of a color developing agent, and later releasing the INH at the properly controlled time, thus permitting image sharpness, maximum density, and sensitivity to be enhanced and fogging to be prevented.

Description

[Detailed description of the invention] [The field of industrial application relates to silver halide color photographic light-sensitive materials, and more specifically, silver halide color photographic materials having high maximum density, high sensitivity, no side absorption, and sharpness. The present invention relates to a silver halide color photographic light-sensitive material containing a magenta dye image-forming polymer coupler and a development inhibitor-releasing coupler having excellent properties.

[Prior Art] Formation of color photographic images based on the subtractive color method generally involves color development processing of a silver halide photographic light-sensitive material using an aromatic primary amine developing agent in the presence of a cyan coupler, a magenta coupler, and a yellow coupler. The silver halide grains of the exposed silver halide photographic light-sensitive material are reduced by the developing agent, and the oxidized product of the developing agent produced at the same time undergoes a coupling reaction with the coupler to form cyan, magenta, and yellow dyes. A color photographic image consisting of each image is formed respectively.

Each of the above couplers can be contained either in the silver halide emulsion or in the color developing solution.

Usually, to form a yellow dye, for example, an acylacetanilide or benzoylmethane coupler is used, and to form a magenta dye, a pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, or Cyanoacetophenone-based or indacylon-based couplers are used, and phenol-based or naphthol-based couplers are mainly used to form cyan dyes. The couplers used must not only form a dye through color development, but also have good color developability, good dispersibility and stability in silver halide emulsions, and the ability of the formed dye to be sensitive to light.
It is necessary to have various properties such as being robust against heat, moisture, etc., and having a light absorption wavelength range within a desirable range.

The coupler that has been practically used to form the magenta dye is the pyrazolone type magenta coupler, but this coupler has low maximum color density and sensitivity, has unfavorable side absorption, and has poor storage stability. In particular, it had the disadvantage of poor formalin resistance, resulting in significant changes in color tone and a significant decrease in color development.

Many proposals have been made in the past to improve these drawbacks. For example, Japanese Patent Publication No. 48-30895 describes IH-pyrazolone [
A magenta coupler of the 3,2-C]-3-triazole type has been disclosed, but this coupler has little improvement in maximum color density and sensitivity, and formalin resistance.

Further, Japanese Patent Publication No. 16058/1983 discloses a screw type pyrazolone type magenta coupler. Although this coupler offers some improvement in sensitivity and formalin resistance, it is insufficient in terms of maximum color density.

Further, JP-A-56-135841 discloses an IH-pyrazolo[3,2-C3-8-triazole type magenta coupler in which the 1st position is substituted with the active site of a compound having an active methylene group. Although this coupler has somewhat improved formalin resistance, maximum color density and sensitivity are inadequate.

In addition, JP-A-58-42045 discloses a ballast group containing a hydroxyphenylenesulfonyl group at the end as a ballast group of a coupler for the purpose of improving the maximum color density and sensitivity. It is still insufficient in this respect.

Furthermore, these pyrazolotriazole type magenta couplers have poor dispersion stability and crystals of the coupler precipitate, making it difficult to add them to silver halide emulsions and making them impractical in the production process. Further, there was a drawback that the spectral absorption of the dye image obtained from this coupler was short-wavelength compared to the desired wavelength.

By the way, in multilayer color photographic materials, in order to eliminate color mixing of each dye and improve color reproducibility, it is necessary to fix each coupler in each separate layer.

Various methods have been known for providing diffusion resistance to couplers for this purpose.

One method is to introduce a long-chain aliphatic group into the coupler molecule, and the coupler is either alkali-soluble and added to an aqueous gelatin solution, or dissolved in a high-boiling organic solvent and emulsified and dispersed in an aqueous gelatin solution. . However, 1,
These couplers have the disadvantage of significantly increasing the viscosity of aqueous gelatin solutions or causing crystal precipitation in emulsions. Also, high i! Organic solvents at the Iti point require a large amount of gelatin to soften the emulsion layer, making it difficult to make the emulsion layer thin. On the other hand, there is a method using a latex of a polymer coupler obtained by polymerizing a monomeric coupler in which the coupler is made diffusion resistant and a group containing polymerizable unsaturation is introduced into the coupler molecule.

The polymer coupler can be added to the hydrophilic colloid composition in the form of a latex in one of two ways. One is to directly polymerize the coupler monomer together with other copolymerizable components by emulsion polymerization to form a latex, which is then added to a silver halide emulsion. Another method is to polymerize the coupler monomer, if necessary, with other copolymerizable components by solution polymerization, dissolve the resulting polymer coupler in a solvent, and then disperse it in an aqueous gelatin solution to form a latex. It is.

Regarding the former emulsion polymerization method, for example, US Pat.
70.952 and 4,080,211, etc., respectively. The latter solution polymerization 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, (1) the polymer coupler latex can contain a high concentration of coupler units.

(2) Since it is not necessary to contain a high boiling point organic solvent for dispersing the coupler in the emulsion, the layer can be made thinner. (
3) Since the film can be made thinner, image sharpness can be improved. (4) In addition, since the aqueous gelatin solution does not thicken much, high-speed uniform coating is possible and mass production is excellent. (5) Furthermore, since the polymer coupler is made into latex, the strength of the formed film will not deteriorate.

There are several examples of such polymer couplers added to silver halide emulsions in the form of latexes. For example, U.S. Patent No. 4,080.211;
, 451,820 and British Patent No. 1,247,688 describe the preparation of a 4-equivalent magenta polymer coupler latex. Also, U.S. Patent Nos. 3 and 7
No. 67.412 describes a latex of cyan polymer couplers. Also, U.S. Patent No. 3.926,4
No. 36 as well as German Patent No. 2,725,591 describe copolymerized latexes with competing couplers. However, although these polymer coupler latexes have many excellent advantages as described above, they also have the following problems that should be improved, and solutions are desired.

(1) The coupling reaction rate is slow and sufficient dye concentration cannot be obtained.

(2) Color development tends to cause unnecessary fogging.

(3) The coupler monomer has low solubility and extremely low polymerizability.

(4) The wet heat fastness of the formed dye image is poor.

[Object of the Invention] The first object of the present invention is to provide an image with exceptionally high sharpness.
The object of the present invention is to provide a silver halide color photographic material containing a specific magenta polymer coupler latex and a specific development inhibitor-releasing coupler. The second object of the present invention is that the maximum density is high and the sensitivity and fog are improved; the third object is that there is no undesirable side absorption and the color reproducibility is excellent; and the fourth object is that the storage stability is improved. The fifth purpose is to have excellent dispersion stability for photographic magenta couplers.The sixth purpose is to have strong film strength and to improve image sharpness by thinning the film. An object of the present invention is to provide a silver halide color photographic material containing an advantageous specific magenta polymer coupler latex and a specific development inhibitor-releasing coupler.

[Structure of the invention]

In particular, the first object of the present invention is to provide at least one magenta dye-forming polymer coupler having a repeating unit represented by the following general formula [I] and/or [n] on a support and It has been found that this can be achieved with a silver halide color photographic material having a silver halide 7L agent layer containing at least one development inhibitor releasing coupler represented by [III] and/or [IV].

General formula [11 General formula [IT] [In the formula, R4 represents a hydrogen atom, a halogen atom, or an alkyl group, R2 represents an alkyl group, an aryl group, or an alkylthio group, J represents a divalent organic group, and Z represents a divalent organic group. Represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidation product of a color developing agent. ] General formula [III] Cp-INH General formula [RJ Cp-T IME-INH [wherein,
Cp represents a coupler component, INH is a development inhibitor group, TIME is bonded to the coupling position of the coupler,
Represents a group that is released by reaction with an oxidized product of a color developing agent and can then release an INH group in an appropriately controlled manner. ] Hereinafter, the present invention will be explained in more detail.

First, the specific magenta dye-forming polymer couplers that form part of the present invention will be described.

R8 represented by the general formula [I] and/or [IT]
is a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, fluorine atom, etc.) or an alkyl group, preferably a straight or branched lower alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, t -butyl group, etc.), and this alkyl group may have a substituent. Particularly preferred R is a hydrogen atom or a methyl group.

In the general formulas [1] and [ff], R2 represents an alkyl group, an aryl group, or an alkylthio group, and among these, an alkyl group is preferred. The alkyl group is preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, Examples include ethyl group, propyl group, butyl group, and t-butyl group. These alkyl groups may have a substituent.

The aryl group represented by R7 is preferably a phenyl group, and this phenyl group may have a substituent, and examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, etc. Can be done. Specific examples of phenyl groups having substituents include p-methoxyphenyl group, m-chlorophenyl group, p-(t)-butylphenyl group, and the like.

Examples of the alkylthio group represented by R2 include linear or branched alkylthio groups having 1 to 6 carbon atoms, such as methylthio group, ethylthio group, propylthio group, and isopropylthio group. The alkyl component of this alkylthio group may further have a substituent.

In general formulas [I] and [II], J is a divalent organic group, but this organic group is preferably a divalent organic group,
V].

General formula [V co-(R1 soup → X soup → R4 product Y → R6 product In the formula, the R3 side is bonded to the polymer main chain, and the R6 side is bonded to the pyrazolotriazole ring.

Rs, R4, and R6 in the general formula [V] each represent an alkylene group, an arylene group, or an aralkylene group having 1 to 12 carbon atoms, and the alkylene group may be linear or branched. .

Examples of the alkylene group include methylene group, methylmethylene group, dimethylene group, decamethylene group, etc.; examples of the arylene group include phenylene group, naphthylene group, etc.;
The alkylene group, arylene group, or aralkylene group represented by may have a substituent, and examples of the substituent include an alkyl group, a halogen atom, and an alkoxy group.

X represented by the general formula [V] is -CON H--N HCO--COO--oco--
so□--S--CO- -SO--O-, among which preferred is -C
ONH--COO--3O2--S--O-.

Y represented by the general formula [V] is Ro -C0NH--NHCO-1-CON--NHCONH
--8O,NH- --NH3Os-, where R6 represents an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, isopropyl group, butyl group, etc.). The preferred Y is -NHCONH--8o, tNH-
There are 4'.

p%QSr and S represent 0 or 1.

In the general formula [I] or [R1, Z represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidation product of a color developing agent.

The group represented by Z that can be separated by the coupling reaction of the oxidized color developing agent means a group conventionally known as a so-called split-off group of a two-equivalent coupler.
Specifically, halogen atoms (e.g., chlorine atom, fluorine atom, etc.), aryloxy groups (e.g., phenoxy group, p-methoxyphenoxy group, p-butanesulfonamidophenoxy group, p-tert-butylcarboamidophenoxy group) etc.), arylthio groups (e.g., phenylthio group), heterocyclic thio groups (e.g., 1-ethyltetrazole-5-thioyl group), etc., preferably a halogen atom, particularly preferably a chloro atom.

The magenta dye-forming polymer coupler having a repeating unit represented by the general formula [I] or [II] can be obtained by polymerizing a coupler monomer represented by the following general formula [VT] or [■] as a main monomer.

General formula [VI] General formula [■] Exemplary force R, , R2, Z and J in general formula [VI] and [■]
are R1 represented by general formulas [I] and [II], respectively
, R2, Z and J.

Next, typical examples of the coupler monomer represented by the general formula [VI] or [■] will be described, but the present invention is not limited thereto.

Below is the margin l (11) (12) (13) (16) Below is the margin (19) (20) (24) (26) (22) (27) 1'l C1 General formula [VI] or [■ Coupler monomers represented by
No. 4-145135, Research Disclosure 1
2443, JChem, Soc, Perking,
Pyrazolotriazole compound, acrylic acid halide, and methacrylic acid halide synthesized by the method described in p. 2047 (1977) etc.
It can be synthesized by reaction with an acid halide described in No. 120252 and No. 58-211756.

Typical production examples of the coupler monomer according to the present invention are shown below.

Production example 1゜3-(4-acryloylamino-2-chlorophenyl)
~7-chloro6-methyl-IH-pyrazolo[3,2-
CI-3-) Riazole (Exemplary coupler monomer (1)
) (a) 3-(4-amino-2-chlorophenyl)7-chloro-6-methyl-IH-pyrazolo[3°2-CI-
24.8 g (0.1 mol) of S-triazole 3-(4-amino-2-chlorophenyl)-6-methyl-IH-pyrazolo[3,2-CI-3-triazole are dissolved in 1 part of tetrahydrofuran, Cool to below 5° C. and add 13.4 g (0.1 mol) of N-thalolsuccinimide little by little. After the addition, tetrahydrofuran was distilled off under reduced pressure, the residue was poured into water, and the precipitated crystals were filtered off.

Recrystallization from acetonitrile yielded 21.5 g (76%) of crystals. m p 145-147°C, structure is IR.

Confirmed by NMR and Mass.

(b) Exemplary coupler monomer (1) 3-(4-amino-2-chlorophenyl)-7-chloro-6-methyl-IH-pyrazolo[3,2-CI-8-triazole 14.2 g (0.05 mol) ), pyridine 4
．． 7 g (0.06 mol) and 1 m of diI-lobenzene
g was added to 200 ml of tetrahydrofuran, and 5.4 g (0.06 mol) of acrylic acid chloride was added dropwise under water cooling. After stirring for 30 minutes, the mixture was poured into 22 ml of water, and the precipitated crystals were filtered off. Recrystallized from ethanol, 10.4g
(62%) of exemplary coupler monomer (1) was obtained. m
p210-213°C. The structure is IR, NMR.

Confirmed by mass and elemental analysis.

Elemental analysis value (C□, 2 for HttNsOC) Theoretical value C:
50.02% H: 3.30% N: 20.83% Experimental value C: 50.28% H: 3.15% N: 20
．． 85% Production Example 2゜3-[3-(4-methacryloylaminophenyl)propyl]-6-methyl-IH-pyrazolo[3,2-C]
-3-triazole (exemplary coupler monomer (4)) 3-(3-(4-aminophenyl)-propyl]-6
-Methyl-IH-pyrazolo[3,2-C]-5-) 25.5 g (0.1 mol) of lyazole, 9.8 g (0.12 mol) of anhydrous sodium acetate and 0.3 g of p-methoxyphenol were added in 250 mQ In addition to glacial acetic acid, 12.5 g (0.12 mol) of methacrylic acid chloride was added dropwise at 15° C. or lower. After stirring for 30 minutes, the precipitated crystals were filtered out and recrystallized from ethanol.
．． 4 g (51%) of exemplary coupler monomer (1) were obtained. mp172-174°C. The structure is IR.

Confirmed by NMR, Ma, ss and elemental analysis.

Elemental analysis (C1a Hx h N s O) theoretical value C
:66.85% H:6.55% N:21.66%
Experimental values C: 66.57% H: 6.72% N: 2
1.51% Production Example 3゜7-chloro-3-[3-(4-methacryloylaminophenyl)propyl]-6-methyl-L H-pyrazolo[
3,2-C] -3-Triazole (Exemplary coupler monomer (5)) (a) 3-[3-(4-aminophenyl)propyl]-7-chloro-6-methyl-IH-pyrazolo[3,2
-C] -5-1 Riazole 3- [3-(4-aminophenyl)propyl]-6-
Methyl-IH-pyrazolo[3,2-C1-8-triazole 25.5 g (0.1 mol) was dissolved in 1 g of tetrahydrofuran, cooled to below 5°C, and N-chlorosuccinimide 13.4 g (0.1 mol) was dissolved in 1 g of tetrahydrofuran. 1 mol) little by little. After the addition, tetrahydrofuran was distilled off under reduced pressure, the residue was poured into water, and the precipitated crystals were filtered off. Recrystallization from acetonitrile yielded 19.7 g (68%) of crystals. m
p 136-138°C. The structure is [RNMR and Mas
Confirmed by s.

(b) Exemplary coupler monomer (5) 3-[3=(4-aminophenyl)probylcomber-chloro-6-methyl-IH-pyrazolo[3°2-C]
-8-) Riazole 14.5g (0.05 mol),
4.9 g (0.06 mol) of anhydrous sodium acetate and 0.15 g of p-methoxyphenol are added to 125 m, e of glacial acetic acid, and methacrylic acid chloride 6.
3 g (0.06 mol) was added dropwise. After stirring for 30 minutes, the mixture was poured into 1.5p water, the precipitated crystals were separated by filtration, and recrystallized from ethanol.13. An exemplary coupler monomer (5) of Ig (73%) was obtained. m p 201-203°C. The structure was confirmed by IR, NMR, mass and elemental analysis.

Elemental analysis (CIIH2ON go CQ) theoretical value C
:60.42% H:5.63% N:19.57%
Experimental values C: 60.16% H: 5.49% N: 1
9.71% 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 13 and/or [ff], and
Although it may be a so-called copolymer with other copolymerizable comonomers, in the present invention, it is preferably a copolymerized polymer coupler.

Examples of comonomers that can be copolymerized include acrylic acid esters, methacrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, olefins, styrenes, and the like.

More specifically, these comonomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2
-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydro Furfuryl acrylate, phenyl acrylate, 5-hydroxybenzyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-Lso
-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 methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5ec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chloro Benzyl 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-t-, naphthyl Methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate-1.
, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2
-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate), 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxy Examples include ethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (additional mole number n=6), and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate-1-, vinyl phenylacetate, vinyl benzoate, salicylic acid. Examples include vinyl.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, and vinylbenzoic acid methyl ester. .

Examples of crotonate esters include butyl crotonate,
Examples include hexyl crotonate.

Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and 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, such as acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide , β-cyanoethyl 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 ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc. Vinyl heterocyclic compounds, such as vinyl pyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc. ; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; Unsaturated nitriles, such as acrylonitrile, methacrylaterile, etc.; Polyfunctional monomers, such as divinylbenzene, methylene bisacrylamide, ethylene glycol dimethacrylate, etc.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, such as monomethyl itaconate; monoalkyl maleate, such as monomethyl maleate; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, Acryloyloxyalkylsulfonic acids, such as acryloyloxymethylsulfonic acid; methacryloyloxyalkylsulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; Acrylamidoalkylsulfonic acids, such as 2-acrylamide -2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.: Methacrylamide alkylsulfonic acid, such as 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.; acryloyloxyalkyl phosphates, such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc.; methacryloyloxy Alkyl phosphates, such as methacryloyloxyethyl phosphate,
Examples include 3-methacryloyloxypropyl-2-phosphate and the like. These acids contain alkali metals (
For example, it may be a salt of Na, di, etc.) or an ammonium ion. Furthermore, other comonomers include
U.S. Patent No. 3,459,790, U.S. Patent No. 3.438,7
No. 08, No. 3,554,987, No. 4゜215.
No. 195, No. 4,247,673, JP-A-57-2
Crosslinkable monomers described in the specification of JP 05735 and the like can be used. Specific examples of such crosslinking monomers include N-(2-acetoacetoxyethyl)acrylamide, N-[2-(2-acetoacetoxyethoxy)ethylcoacrylamide, 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. 2
Examples of combinations when using more than one species include, for example, n
-butyl acrylate and methyl acrylate, styrene and N-[2-(2-acetoacetoxyethoxy)ethylcoacrylamide, tert-butyl acrylate and methyl methacrylate, and the like.

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 general formula [I] or [II]. , especially 40-70
% is preferred.

The magenta polymer coupler of the present invention may be prepared by emulsion polymerization, 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 it. U.S. Pat. No. 4,080,211 for the emulsion polymerization method
No. 3,370,952 and U.S. Pat. No. 3,451,820 for dispersing lipophilic polymer couplers in aqueous gelatin solution in latex form. can.

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 solid monomer at room temperature. .

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;
-Sodium azobis-4-cyanovalerate, 2,2'-
Water-soluble azo compounds such as azobis(2-amidinopropane) hydrochloride and hydrogen peroxide can be used. In addition, examples of lipophilic polymerization initiators 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), 2.2'-dimethyl azobisisobutyrate,
2. Lipophilic azo compounds such as diethyl 2'-azobisisobutyrate, benzoyl peroxide, lauryl peroxide, diisopropyl peroxydicarbonate, dite
Mention may be made of lipophilic peroxides such as rt-butyl peroxide.

Examples of emulsifiers used in the emulsion polymerization method include surfactants, polymeric protective colloids, and copolymer emulsifiers. Surfactants include anionic surfactants, wanionic surfactants, cationic surfactants, and amphoteric surfactants known in the art.

Examples of anionic activators include soaps, sodium dodecylbenzenesulfonate, sodium lauryl sulfate,
Examples include sodium dioctyl sulfosuccinate and sulfates of nonionic surfactants. Examples of nonionic activators include:
Examples 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 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 Chemi.
Scheindustrie, vol. 28, 16-2
It is described on page 0 (1963).

The group that can be separated by the coupling reaction with the oxidation product of the color developing agent represented by Z in the above general formulas [I] and [II] is the stage of the coupler monomer represented by the general formula [VI] or [■]. It can be introduced with. or Z
A coupler monomer represented by the general formula [VI] or [■], in which is a hydrogen atom, can also be introduced by a conventional method after polymerization.

In this case, in the repeating unit represented by the general formula [I] or [II], 2 becomes a mixture of groups that can be separated by a coupling reaction between a hydrogen atom and an oxidation product of the color developing herbal medicine.

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 coupler 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 for dispersing lipophilic polymeric couplers in latex form in aqueous gelatin solutions is described in U.S. Pat.
No. 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.

Example of manufacturing method for latex of magenta polymer coupler (
1) Production of lipophilic polymer coupler latex (A) of exemplary coupler monomer (5) and n-butyl acrylate A mixture of 14 g of exemplary coupler monomer (5), 6 g of n-butyl acrylate, and 120 J of dioxane was heated at 80°C in a nitrogen stream. After stirring, 0.36 g of azobisisobutyronitrile dissolved in 4 ml of dioxane was added, and the mixture was reacted for 6 hours. A dioxane solution was added dropwise over two evenings of water, and the precipitated solid was separated by filtration, washed with water, and dried to yield 18.4 g (92%
) was obtained. The copolymer composition of this polymer coupler was found to have a coupler monomer (5) content of 708% by elemental analysis (nitrogen analysis).

10 g of the above polymer coupler was dissolved in 30 ml of ethyl acetate, and to this solution was added a mixed solution of 6 m 2 of a 10% aqueous solution of sodium lauryl sulfate and 100 fl of a 5 wt % aqueous solution of gelatin, followed by ultrasonic dispersion. After that, ethyl acetate was removed by vacuum distillation, and the polymer coupler latex (A
) was obtained.

Production method example (2) Production of lipophilic polymer coupler latex (B) of exemplary coupler monomer (4) and methyl acrylate. Exemplary coupler monomer (4) Log, a mixture of 10 g of methyl acrylate and 120 J of dioxane was heated at 80'C in a nitrogen stream. After stirring, 0.36 g of azobisisobutyronitrile dissolved in 4 m, 9 dioxane was added, and the mixture was reacted for 6 hours. A dioxane solution was added dropwise to 2/l of water, and the precipitated solid was filtered out, washed with water, and dried. 17.6 g
(88%) of polymer coupler was obtained. The copolymer composition of this polymer coupler was determined by elemental analysis (nitrogen analysis) to have a coupler monomer (4) content of 52.3%.

The above polymer coupler was treated in the same manner as in Production Example (1),
A polymer coupler latex (B) was obtained.

Production method example (3) Chlorination of the lipophilic polymer coupler of production method example (2) and production of latex (C) 15 g of the lipophilic polymer coupler produced in production method example (2)
Dissolve in 150 J of tetrahydrofuran and add 3.2 g under ice cooling.
(0,024 mol) of N-chlorosuccinimide was added in portions. A tetrahydrofuran solution was added dropwise to water 1, and the precipitated solid was filtered off, washed with water, and dried. 15.
2g (96%) of polymer cuffler was obtained. This polymer coupler has 95% pyrazolo[3,2-C]-8-triazole at the 7-position according to elemental analysis (chlorine analysis) and NMR.
It was confirmed that it was chlorinated.

The above polymer coupler was treated in the same manner as in Production Example (1),
A polymer coupler latex (C) was obtained.

Production Example (4) Production of lipophilic polymer coupler latex (D) of exemplified coupler monomer (6), n-butyl acrylate and methyl acrylate.

A mixture of exemplary coupler monomer (6) Log, 5 g of n-butyl acrylate, 5 g of methyl acrylate, and 200 mQ of tert-butanol was stirred under a high-speed nitrogen stream,
After adding 0.36 g of azobisisobutyronitrile dissolved in 10 mp of tert-butanol, the mixture was reacted for 6 hours. A tert-butanol solution was dropped into 2y of water, the precipitated solid was filtered, washed with water and dried, 17.0g
(85%) of a lipophilic polymer coupler was obtained. The copolymer composition of this polymer coupler was determined by elemental analysis (nitrogen analysis) to have a coupler monomer (6) content of 48.8%.

The above polymer coupler was treated in the same manner as in Production Example (1) to obtain a polymer coupler latex (D).

Production Example (5) Production of polymer coupler latex (A') of exemplified coupler monomer (5) and n-butyl acrylate.

Exemplary coupler monomer (5) Log and 10 g of n-butyl acrylate were heated and dissolved in 200 mQ of ethanol.

800 ml of an aqueous solution in which 2 g of thorium salt of oleyl methyltauride was dissolved was heated to 95° C. and stirred in a nitrogen stream, and 20 ml of an aqueous solution of 140 mg of potassium persulfate was added. Next, the above-mentioned ethanol solution was added dropwise over 1 hour. After completing the dropwise addition, heat and stir at 95 to 85°C,
After an hour, a 20ml aqueous solution of 60 mg of potassium persulfate 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 azeotrope of water.

The solid content concentration of the formed latex was 9.8 wt%, and the copolymer composition was found to have a coupler monomer (5) content of 53.5% by elemental analysis.

Production Example (6) Production of polymer coupler latex (B') of exemplified coupler monomer (7) and ethyl acrylate.

15 g of exemplified coupler monomer (7) and 5 g of ethyl acrylate were heated and dissolved in 200 mJ2 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 and stirred in a nitrogen stream, and the aqueous solution was added to 20 ml of 140 mg of potassium persulfate.Then, the above ethanol solution was heated for 1 hour. After the dropwise addition was completed, the mixture was heated and stirred at 95-85°C, and after 3 hours, a 20 m2 aqueous solution of 60 mg of potassium persulfate was added, and the mixture was further stirred at the same temperature for 3 hours. It was distilled off as a boiling mixture.

The solid content concentration of the formed latex was 11.8 wt%, and elemental analysis of the copolymer composition revealed that the coupler monomer (7) content was 74.2%.

Production method examples (7) to (42) Production method examples (1), (2) using the coupler monomers,
(4) (Production method I) and production method examples (5), (6) (Production method ■)
The following polymer coupler latex was obtained in the same manner as the copolymer.

Manufacturing method I Manufacturing method ■ *l BA: n-butyl acrylate EA: ethyl acrylate MA: methyl acrylate BMA: n-butyl methacrylate MMA/methyl methacrylate HA: n-hexyl acrylate EHA: 2-ethylhexyl acrylate!・AAM
Niacrylamide St: Styrene and other residual colors Next, it is another part of the structure of the present invention, and is used in combination with the magenta polymer coupler latex, and is of the following general formula [1
The development inhibitor releasing (DIR) coupler represented by [11] and/or [IV] will be explained.

General formula [■Cp-INH] General formula [IV] Cp-TIME-INH In the formula, C
p represents a coupler component, and this coupler may or may not form a dye upon coupling. INH is a development inhibitor group and is a compound that inhibits the development of silver halide. In the general formula [ml, INH binds to the coupling position of the coupler component and is released by reaction with the oxidized product of the color developing agent. The TIME group of the general formula [IV] is a group that is capable of bonding to the coupling position of the coupler, being released by reaction with the oxidized product of the color developing agent, and then releasing the INH group in an appropriately controlled manner.

Coupler components represented by Cp include pigment-forming compounds such as acylacetanilides, malondiesters, malondiamides, benzoylmethanes, pyrazolones, pyrazolotriazoles, pyrazolobenzimidazoles, indasilones, phenols, and naphthols. Couplers and coupler components that do not substantially form dyes, such as acetophenones, indanones, and oxacilones.

Preferred coupler components include general formulas [■], [IX
], [X].

General formula [■] General formula [■ General formula [X] In the formula, R1□ represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and RLI and R14 each represent an aromatic group or a heterocyclic group. represents.

R1! The aliphatic group represented by is preferably a substituted or unsubstituted chain or cyclic group having 1 to 20 carbon atoms. Preferred substituents for the alkyl group include alkoxy, aryloxy, and acylamino groups. Especially preferred as Rlx is a tert-butyl group. R.

When RLI or R14 is an aromatic group, a phenyl group,
It represents a naphthyl group, etc., but 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.

Furthermore, the phenyl groups represented by R, 2, R, and R14 may be substituted with an alkyl group, an alkoxy group, a cyano group, or a halogen atom.

Rts represents a hydrogen atom, an alkyl group, a halogen atom, etc., and R2 is an integer of 1 to 5, preferably a hydrogen atom. RL6 and R 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 work 6
, R□7 may be the same or different.

As INH, in particular, the following general formulas [XI] and [X
n] is preferable.

General formula [XI represents a cosyloxy group, an acylamino group, a halogen atom, a carbamoyl group, a nitro group, a cyano group, a sulfamoyl group, a hydroxy group, etc., and m□ is 1 or 2. R1
, 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 examples of the substituent include an alkyl group, Examples include alkoxy groups, halogen atoms, and hydroxy groups.

As TIME, in particular, the general formula [Xm, [XIV]
and [X V] are preferable.

General formula [X] General formula [Xn] General formula [XIV] R1, is an alkyl group, alkoxy group, alkoxycarbonyl group, aryloxycarbonyl group, a general formula [X V] -1 R1 R8゜ is a hydrogen atom, alkyl group, alkoxy group, anilino group, nitro group, aryl group, carboxy group, cyano group, etc., and nL is an integer of 1 or 2. Rffi
l represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group or an aryl group. R2° and R
When 21 represents 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.

Representative examples of development inhibitor releasing couplers according to the present invention will be given below.

-2 N=N space below 1') -4 When the magenta dye-forming polymer coupler and the development inhibitor-releasing coupler are used in combination in the present invention, it is particularly preferable to contain them in the same layer. In this case, the development inhibitor releasing coupler is from 0.0001 to 0.0001 per mole of silver.
It is contained in an amount of 0.5 mol, preferably in the range of 0.001 to 0.05 mol.

Next, the polymer coupler latex in the present invention is
It is used in a color photographic light-sensitive material consisting of a green-sensitive silver halide emulsion layer or a color photographic light-sensitive material consisting of two layers, a high-speed layer and a low-speed layer, and a green-sensitive silver halide emulsion layer. A color photographic light-sensitive material consisting of three layers, with a medium-speed layer or an intermediate layer containing no silver halide emulsion inserted between the high-speed layer and the low-speed layer of the green-sensitive silver halide emulsion layer consisting of the two layers described above. is also used. In addition, there is a reverse layer structure in which the low-speed layer of the green-sensitive silver halide emulsion and the high-speed layer of the red-sensitive silver halide emulsion are reversed, and the high-speed layer of the blue-, green-, and red-sensitive silver halide emulsions is placed on top and the low-speed layer is placed on top. It is also used in color photographic materials that have a reverse layer structure with a sensitive layer as the lower layer.

Preferably, the emulsion has a three-layer structure, and particularly preferably, the green-sensitive silver halide emulsion has a three-layer structure consisting of a high-speed layer, a medium-speed layer, and a low-speed layer.

As the silver halide used in the silver halide emulsion layer according to the present invention, common silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. Any used in photographic emulsions is included.

These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [100] planes to [111] planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside.

Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. These silver halide grains can be prepared by known methods commonly used in the art.

Also, JP-A-58-113926, JP-A No. 58-11392
No. 7, No. 58-113928, No. 58-113934
It may also be a tabular grain silver halide emulsion described in No.

It is preferable that soluble salts be removed from the silver halide emulsion used in the present invention, but those in which soluble salts have not been removed can also be used. It is also possible to use a mixture of two or more silver halide emulsions prepared separately.

As the binder for the silver halide emulsion layer according to the present invention, conventionally known binders can be used, such as gelatin, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin, polyvinyl alcohol, polyvinylpyrrolidone, etc. , polymeric non-electrolytic alkynates such as polyacrylic acid amide, acidic polymeric substances such as polyacrylates, polyacrylamide treated by Hoffmann rearrangement reaction, polymers such as copolymers of acrylic acid and N-vinylimidazole, etc. Ampholyte, U.S. Patent 4,215
, No. 195, and the like. It may also contain a dispersed hydrophobic polymer substance, such as a latex such as butyl polyacrylate or ethyl polyacrylate. These binders can be used as a compatible mixture of two or more if desired.

A silver halide photographic emulsion in which the above-mentioned silver halide grains are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitizers that can be advantageously used in combination in the present invention are roughly classified into four types: noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers.

As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium, and platinum can be used.

In addition, when using a gold compound, ammonium thiocyanate and sodium thiocyanate can be used in combination.

As the sulfur sensitizer, in addition to activated gelatin, sulfur compounds can be used.

As selenium sensitizers, active and inactive selenium compounds can be used.

Reduction sensitizers include stannous salts, polyamines, bisalkylaminosulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives.

Furthermore, this silver halide can be optically sensitized to a desired wavelength range, for example, by using optical sensitizers such as cyanine dyes such as monomethine dyes and trimethine dyes or merocyanine dyes alone or in combination. can be sensitized.

In addition to the additives mentioned above, the silver halide color photographic material of the present invention contains stabilizers, development accelerators, hardeners, surfactants, anti-staining agents, lubricants, ultraviolet absorbers, formalin scavengers, etc. Various additives useful in photographic materials are used.

In addition to the silver halide emulsion layer, the silver halide color photographic light-sensitive material of the present invention may optionally be provided with auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, and a backing layer.

As the support, conventionally known supports such as plastic film, plastic laminated paper, baryta paper, synthetic paper, etc. may be appropriately selected depending on the intended use of the photographic material.

These supports are generally subjected to a subbing process to enhance adhesion with the photographic emulsion layer.

After the silver halide color photographic material of the present invention thus produced is exposed to light, various photographic processing methods are used for color development. A preferred color developing solution used in the present invention is one containing an aromatic primary amine color developing agent as a main component.

As a specific example of this color developing agent, p-phenylenediamine type is typical, such as diethyl-p-
Phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino) -Toluene, 2-amino-5-(N-ethyl-N-
β-methanesulfonamidoethyl)aminotoluene sulfate, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N-
β-hydroxyethylamino)aniline, 2-amino-
Examples include 5-(N-ethyl-β-methoxyethyl)aminotoluene. These color developing agents may be used alone or in combination of two or more, and if necessary, in combination with black and white developing agents such as hydroquinone and phenidone. Furthermore, the color developing solution generally contains an alkaline agent such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfite, etc., and also various additives,
For example, alkali metal halides, such as potassium bromide,
Alternatively, it may contain a development regulator such as citradinic acid.

The silver halide color photographic light-sensitive material of the present invention may contain the above color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its precursor. A color developing agent precursor is a compound that can form a color developing agent under alkaline conditions;
Examples include Schiff base type precursors with aromatic aldehyde derivatives, polyvalent metal ion complex precursors, phthalic acid imide derivative precursors, phosphoric acid amide derivative precursors, sugar amine reactant precursors, and urethane type precursors. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat.
No. 2,599, No. 2,507,114, No. 2,6
No. 95,234, No. 3,719,492, British Patent Box No. 303.783, JP-A-53-135628
No. 54-79035, Research Disclosure Magazine No. 15159, No. 12146, No. 139
It is described in No. 24.

These aromatic primary amine color developing agents or their precursors need to be added in amounts that will provide sufficient color development during development. This amount varies depending on the type of photosensitive material, but it is generally photosensitive silver halide 1
Between 0.1 and 5 mol per mole, preferably 0.5
It is used in a range of mol to 3 mol. These color developing agents or their precursors can be used alone or in combination. To incorporate additives such as these developing agents or their precursors into photographic light-sensitive materials, they can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc. and added. It can also be added as an emulsified dispersion using a high boiling point organic solvent such as tricresyl phosphate, Research Disclosure Journal 14850.
They can also be added by impregnation into latex polymers, as described in the above.

The silver halide color photographic material of the present invention is usually subjected to bleaching and fixing, or bleach-fixing and washing with water after color development. Many compounds are used as bleaching agents, among them polyvalent metal compounds such as iron (III), cobalt (m), and tin (II), especially complex salts of these polyvalent metal cations and organic acids, such as , aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid,
Metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, ferricyanates, dichromates, etc. are used alone or in appropriate combinations.

The present invention will be described in more detail with reference to Examples below.

[Example] A multilayer color photosensitive material (sample 1) was prepared on a cellulose triacetate film support, each layer having 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 Silver bromide emulsion (silver iodide: 4 mol %) (average grain size 0.5 μ) ... Silver coating amount 1.79 g / sensitizing dye I ... 6X 10-' mol per 1 mol of silver Sensitizing dye ■...1.5X per mole of silver 10-
'Mole coupler A...006 per mole of silver
Molar coupler C...0.003 per mole of silver
Moltricresyl phosphate coating amount 0.3cc/m
'4th layer: Red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion (silver iodide: 4 mol%) (average grain size 0.7μ) ...Silver coating @ 1.4g/rr? Sensitizing dye I... 3X 10-' mol per mol of silver Sensitizing dye ■... 1.2X 10-' per mol of silver
Molar coupler F...0.012 per mole of silver
0 mole coupler C...0.00 per mole of silver
20 mol tricresyl phosphate coating @0.2cc
/rd 5th layer: Intermediate layer Same as 2nd layer 6th layer: Green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion (silver iodide: 4 mol%) (average grain size 05 μ) ...Coated silver amount 1 ．． Og/rrt" Sensitizing dye ■... 3X 10-' mole for 1 mole of silver Sensitizing dye ■... LX 10-' for 1 mole of silver
Molar coupler B...0.08 per mole of silver
Molar coupler M...0.008 per mole of silver
Moltricresyl phosphate coating f11.4cc/
rr? 7th layer: Green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion (silver iodide niamol %) (average grain size 1.2μ) ...Coated silver amount 1.6g/rr? Sensitizing dye ■...2.5X 10-' per mole of silver
Molar sensitizing dye■...0.8X per mole of silver 10
-'Mole coupler B...0 for 1 mole of silver.
02 mole coupler M...0.0 per mole of silver
03 mol tricresyl phosphate application amount 0.8cc
/ rrr 8th layer: yellow filter layer yellow colloidal silver and 2.5-di-t- in gelatin aqueous solution
and an emulsified dispersion of octylhydroquinone.

9th layer: blue-sensitive, low-sensitivity emulsion layer Silver iodobromide emulsion (silver iodide; 6 mol%) (average grain size 0.6 μ) ... Coating silver fi 0.5 g / Go coupler Y ... 1 mol silver For 0.125 mole tricresyl phosphate application amount 0.3cc/rrr
10th layer: Blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion (silver iodide 26 mol%) (average grain size 0.8 μ) ... Coated silver amount 0, 6 g / Ikabura-Y ... 1 mol of silver For 0.04mol tricresyl phosphate coating ft O, 1cc/r
r? Layer 11: Protective layer Apply a gelatin layer containing polymethyl methacrylate particles (about 15 μm in diameter).

The coupler in each layer was 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. The emulsified product was used.

In addition to the above composition, a gelatin hardener and a surfactant were added to each layer.

The sample prepared as described above was designated as Sample 1.

Compound sensitizing dye used to make sample 1 ■: Anhydro 5.5'-dichloro-3,3
'-Di(γ-sulfopropyl)-〇-ethylthiacarbocyanine 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 enhancement Sensitive dye ■: Anhydro 5.6.5', 6'tetrachloro-1,1'-diethyl-3,3'-di(γ-sulfopropyl) imidazolocarbocyanine hydroxide sodium salt with 5 margins below B Coupler M [Bleach solution composition] Same as sample 1 except that the coupler M in the 6th and 7th layers of sample 1 was changed as shown in Table 1, and the DIR coupler in Table 1 was added to the 6th layer. Samples 2 to 5 were prepared. For samples 2 to 5 using polymer couplers, the amount of tricresyl phosphate was reduced to 1/10 that of sample 1.

The obtained samples 1 to 5 have spatial frequencies ranging from 3 lines/mm to 10 lines/mm.
After exposure through a sea urchin/soji film varying in the range of up to 0 lines/mm, the following development process was performed.

Processing process (38℃) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water
Fixed for 3 minutes and 15 seconds 6
Water washing for 3 minutes and 15 seconds Stabilizing bath for 1 minute and 30 seconds The composition of the treatment solution used in each treatment step was as follows.

[Color developing solution] "4-amino-3-methyl-N-ethyl-N- [Fixer composition] [Stable bath composition] Transfer Function) was determined, and the values at a spatial frequency of 5 lines/mm were compared, The effect of improving sharpness was investigated.

The MTF value was determined by measuring the density using a slitter with a slit width of 300 μm in length and 2 μm in width, and the resolution relative to the input was expressed as a percentage value. The results are shown in Table 1. --Less than 113 margins,
: From Table 1, DI for the polymer coupler latex of the present invention
Sharpness was significantly improved by adding R coupler.

[Effects of the Invention] As is clear from the above description and examples, a silver halide emulsion layer containing a specific magenta polymer coupler of the present invention and a specific development inhibitor-releasing (DIR) coupler has a silver halide emulsion layer. Silver chemical color photographic materials have exceptionally improved image sharpness, high maximum density, improved sensitivity and fog, no side absorption, excellent color reproducibility, and excellent preservability, especially formalin resistance. In addition, it is useful because it has excellent effects such as good dispersion stability of magenta couplers.

Claims (2)

[Claims] (1) At least one magenta dye-forming polymer coupler having a repeating unit represented by the following general formula [I] and/or [II] and the following general formula [III] and/or [
IV]
A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing seeds. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents a hydrogen atom, a halogen atom, or an alkyl group, and R_2 represents an alkyl group. , represents an aryl group or an alkylthio group, J represents a divalent organic group, Z
represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidation product of a color developing agent. ] General formula [I
II] Cp-INH General formula [IV] Cp-TIME-INH [In the formula, Cp represents a coupler component, INH is a development inhibitor group, TIME is bonded to the coupling position of the coupler, and the color developing agent is Represents a group that can be released by reaction with an oxidant and then release an INH group in an appropriately controlled manner. ] (2) The magenta dye-forming polymer coupler and the development inhibitor-releasing coupler are contained in the same layer of a silver halide emulsion, and the development inhibitor-releasing coupler is 0.0001 to 0.5 mol per mol of silver. 2. The silver halide color photographic material according to claim 1, wherein the silver halide color photographic material is within the range of .