JPS6041043A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To enhance sharpness and coloring performance by incorporating a specified magenta-dye forming polymer coupler in a silver halide emulsion layer formed on a support. CONSTITUTION:A silver halide emulsion layer formed on a support contains a magneta dye-forming polymer coupler having repeating units each represented by formula I in which Q is an ethylenically unsatd. group and, preferably one represented by formula II; R1, R2 are each a univalent group; X is halogen; Z is H or a group releasable on the coupling reaction with the oxidized product of a color developing agent; (l) is 0, 1, 2 or 3, and when it is >=2, each of plural (R2)s may be the same or different; R3 is H, Cl, or alkyl; and J is a bivalent group. An image obtained by using the latex of said polymer coupler is excellent in coloring performance and has less fogging.

Description

Detailed Description of the Invention ■Background of the Invention Technical Field The present invention contains a novel magenta dye-forming polymer coupler that can couple with an oxidized product of an aromatic primary amine color developing agent to form a dye. This invention relates to silver halide color photographic materials.

In the formation of color photographic images based on the subtractive color process, it is generally known that after imagewise exposure of a halogenated color photographic photosensitive material, aromatic This is done by color development treatment using a primary amine color developing agent.At this time, the silver halide grains of the exposed silver halide photographic material are reduced by the first color developing agent, and a color developing agent is simultaneously produced. The oxidized form of the main drug undergoes a coupling reaction with the coupler to form a color photographic image consisting of a cyan dye, a magenta dye, and a yellow dye.

These couplers are contained in the silver halide emulsion in the internal color development method, or in the color developing solution in the external color development method.Currently, these couplers are contained in a simple internal color development solution that requires only one color development. Many methods are 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 indacylon coupler is mainly used. In order to form cyan dye 1Ii11 images, phenolic couplers such as phenols and naphthols are mainly used.

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 have the advantage that the preformed dye image is It must meet strict requirements, such as having a high degree of stability against heat, moisture, etc. over a long period of time, and having a light absorption wavelength range within a desirable range.

By the way, in silver halide color photographic light-sensitive materials having a multilayer structure, it is essential to fix each first coupler in a separate layer in order to reduce color mixture of each dye and improve color reproducibility. Deru・ru.

As a method for preventing diffusion of this coupler, the method described in Section II is known.

One method is to introduce a long-chain aliphatic group into the coupler molecule as a diffusion-inhibiting group. Since the coupler produced by this method is immiscible with an aqueous gelatin solution, it is either OJ-solubilized in an alkali and added to the aqueous gelatin solution, or a coupler with an oil-bathable ballast group (diffusion prevention group) is used with the help of a surfactant. It is necessary to disperse it as colloidal particles in an aqueous gelatin solution together with an organic solvent at a boiling point. In such a coupler, the hydrophilic group in the coupler interacts with gelatin, causing thickening phenomenon especially during the fabric process, which hinders high-speed uniform coating, or causes precipitation of crystals in the emulsion. do.

In addition, when a high boiling point organic solvent is used, a large amount of gelatin is required to soften the milk layer, and as a result,
It was difficult to make the emulsion layer thin.

Another method for making a coupler resistant to diffusion is to use a polymeric coupler obtained by polymerizing a monovalent coupler into which a group containing a conjugable unsaturated bond is introduced into the coupler molecule.

The polymer cuffler can be added to the hydrophilic colloid composition in the form of a latex in the following manner. One is to directly polymerize the coupler monomer together with other copolymerization components by emulsion polymerization to form a latex, and add this to a silver halide emulsion.
This is a method in which a polymer coupler obtained by polymerizing a coupler monomer together with other copolymerization components if necessary by seedling polymerization is dissolved in a solvent, and then dispersed in a gelatin water bath to form a latex.

Regarding the former emulsion polymerization method, U.S. Patent No. 3.37095
No. 2 and No. 4,080,211, respectively.

For the latter method, for example, 1 city permit 3,451
, No. 820. The method of adding such polymeric couplers in latex form to hydrophilic colloid compositions has many advantages over other methods, including:

First, since the latex polymer cuffler can contain one unit of coupler at a high concentration, it is easy to incorporate a high concentration of coupler into the emulsion, and it also contains a high boiling point organic solvent to disperse the coupler. Since there is no need to make the film thinner, the sharpness of the image can be improved.
Moreover, since there is little thickening phenomenon of the aqueous gelatin solution, high-speed uniform coating is possible. 4] Since the polymer coupler is made into latex, it may deteriorate the strength of the formed film.

Furthermore, since polymer couplers have one plastic unit incorporated into the polymer, 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. There is little precipitation.

British patent 1,247.688 remaining US patent 3,451,8
No. 20 describes an example in which a latex of a 4-magenta polymer coupler is added to a silver halide emulsion, and West German Patent No. 2,725,591 and U.S. Pat.
．． No. 926,436 describes examples of copolymeric latexes with competing couplers. Also.

U.S. Pat. No. 3,767,4.12 describes a cyan coupler latex.

However, although these polymer coupler latexes have the above-mentioned excellent advantages, they also have the following problems that need to be improved, and improvements are desired.

(1) Sufficient dye concentration cannot be obtained because the coupling reaction rate is slow.

(2) Color development tends to cause unnecessary capri.

(3) The Kabukyu monomer is poorly understood and has extremely low polymerizability.

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

Object of the Invention Accordingly, the first object of the present invention is to provide a silver halogenide color photographic light-sensitive material containing a novel magenta polymer coupler which eliminates the above-mentioned conventional drawbacks and has excellent coloring properties. There is a particular thing.

A second object of the present invention is to provide a silver halide color photographic photosensitive compound in which the coating layer is thinned and dye images with improved sharpness can be obtained.

A third object of the present invention is to provide a silver halide color photographic photosensitive paulownia material having 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.

The present inventors have conducted various studies, and as a result 1. These objects of the present invention are as follows. This is achieved by a silver halide color photographic light-sensitive material having a silver emulsion layer.

(In the formula, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, the turtle carries a monovalent group, and the above-k
Ni α 蟇奢cloud 4, the bird represents a monovalent group, X represents a halogen atom, and Z represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized product of a color developing agent.

l represents an integer from 0 to 3, and when l is 12 or more, two or more numbers may be the same or different. ) Below blank space ■ Specific constitution of the invention The group having an ethylenically unsaturated group Q represented by the general formula (1) is preferably represented by the following general formula [Touge].

In the general formula [Touge 3 CHx = C-J, R3 represents a hydrogen atom, a chlorine atom or an alkyl group, and J represents a divalent linking group.

The alkyl group R3 represented by general formula (1) is preferably a lower alkyl group having 1 to 4 carbon atoms, such as a methyl group.

R1 represented by the general formula (1) is an alkyl group (e.g., methyl group, etc.), an aryl group (e.g., phenyl group, etc.), an acylamino group (e.g., acetylamino group, pivaloylamino group, penzoylaminodi-N, etc.), an arylamino group (
anilino group, 0-chloroanilino group, etc.), carbamoyl group (e.g., methylcalcimimoyl group, dimethylcarbamoyl group, etc.), alkoxycarno(moyl group (e.g., methoxycarpamoyl group, ethoxycarbamoyl group, etc.), sulfonamide group (e.g., methane sulfonamide group, dimethylaminosulfonamide group, etc.), cyan group, etc. Among the above-mentioned -valent groups, preferred are acylamino group, anilino group, and alkyl group.

R2 represented by general formula (1) is an alkyl group (e.g. methyl group, etc.), an alkoxy group (e.g. methoxy group, ethoxy group, etc.), a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), an acylamino group (e.g. acetylamino group, pivaloylamino group, etc.), carbamoyl group (e.g., methylcarbamoyl group, dimethylcalcimimoyl group, etc.), alkoxycarbamoyl group (e.g., methoxycarbamoyl group, ethoxycarbamoyl group, etc.), sulfonamide group (e.g., methanesulfonamide group, (dimethylaminosulfonamide group, etc.), sulfamoyl group (methylsulfamoyl group, dimethylsulfamoyl group, etc.), sulfonyl group (e.g. methylsulfony/l/group, etc.), cyano group, etc.; Among the valent groups, particularly preferred are a methyl group or a halogen atom.

l represents an integer from 0 to 3.

, Z is a hydrogen atom or a group that can be separated during a coupling reaction, and examples of such groups include those in which a halogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom is directly bonded to a carbon atom at the coupling position. Aryloxy group, acyloxy group, alkoxy group, oxalate group, 'Pl ringoxy group, phosphate group, thiophosphate group, carbamoyloxy group, thiocarbamoyloxy group, oxamoyloxy group, thioxamoyloxy group, Thiocyano group, alkylthio group, arylthio group.

Heterocyclic thio group, alkylsulfinyl f, 71J-rusulfinyl group, aim sulfinyl group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group,
Sulfonyl group, sulfo group, alkylsulfonylthio group,
Arylsulfonylthio group, disulfide group, sulfide group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, lathiocarbonate group, acylamino group, diacylamino group, sulfonamide group, sulfinamide 8 group, alkylamino group, arylamino group Cali,
5 ureido groups, thioureido groups, phosphoric acid amide groups, urethane groups 1, thioacylamino groups, inthiocyanate groups, or cycloamino groups such as pyrrolidino, morpholino, tAradino, indolino, piperidino, phthalimide, succinimit 9, saccharin, Cyclic diacylamino groups such as oxazolidione, thiohydantoin, and hydantoin, cycloamide groups such as pyridone, oxazolidone, phthalide, and valerolactam, or 5- or 6-membered heterocyclic groups such as imidazolyl, pyrrolyl, and benzotriazolyl groups. can be given. In addition, U.S. Patent No. 3.471
, No. 563, Japanese Patent Publication No. 1973-36894, Japanese Patent Publication No. 1973-
No. 37425, No. 50-10135, No. 50-117
No. 422, No. 50-130441, No. 51-1088
No. 41, No. 50-120334, No. 52-18315
You may use the leaving group described in No. 1, No. 53-52423, No. 53-105226, etc.

X represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), and a chlorine atom is particularly preferred.

The general formula (1) is preferably represented by the following general formula (nQ).

General formula [■] In the formula, ns represents a hydrogen atom, a halogen atom, or an alkyl group, preferably a lower argyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a t-methyl group, etc.), and this alkyl The group may have a substituent. L is 100NH-1, -Nl (CONT+- or -NH- (however, the nitrogen atom is bonded to the pyrazolone ring) or -NHCOO- (however, the oxygen atom is bonded to the pyrazolone ring) ), P represents a divalent group of -001(H-
(However, the nitrogen atom is bonded to A in the general formula (Ill).), -802- (However, the oxygen atom is bonded to A in the general formula (Ill).)
) is associated with a person. ) or -coo- (however, the oxygen atom is bonded to A in the general formula [■]);
~10 alkylene groups), or a divalent group of a phenylene group, and the alkylene group may be linear or branched, such as a methylene group, a methylmethylene group, a dimethylene group, a decamethylene group, and The above alkylene group and phenylene group may have a substituent.

m and ru represent O or 1.

In the general formula (III) described in 1jjJ, preferred is L car cONI← or -NH-, where L is 1, A is m-phenylene, m is 1, and P is -(:
0NH-, and Rs is a lower alkyl group.

Even more preferably, L is -c ON H- and m
and L is 00, and loss is a lower alkyl group,
This is especially the case for methyl groups.

Substituents for the alkylene group or phenylene group represented by human include aryol group (e.g. phenyl group), 2) a
group, hydroxyl group, cyano group, sulfur group, alkoxy group (
For example, ethoxy group), acyloxy group (for example, acetoxy group), acylamino group (for example, acetylamino group),
8 sulfonamide groups (e.g. methanesulfonamide group)
, sulfamoyl group (e.g. methylsulfamoy/l/
group), halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), carboxyl group, carbamoyl group (e.g. methylcarbamoyl group), alkoxycarbamoyl group (
Examples include methoxycarbamoyl group, etc.), sulfonyl group (eg, methylsulfonyl group, etc.). There may be two or more of these substituents. In that case, these substituents may be the same or different.

Bonding position 1r of Q in general formula (1) is preferably 3
, 4th, or 5th place. Further, the bonding position of R snow is preferably selected from the 3rd, 4th, or 5th position, regardless of whether l is 1 to 3.

Next, preferred specific examples of the coupler monomer used in the present invention will be shown, but the present invention is not limited thereto.

OCH3 Nil-C-CH=CH2 6 CH3 The monomer of the present invention forms a homopolymer coupler or a copolymer coupler in the presence of a polymerization initiator or under irradiation with radiation, electron beam, etc.

The polymer cassillator 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 other copolymerizable comonomers, In the present invention, preferred are copolymerized polymer couplers. Examples of comonomers that may be used when synthesizing copolymer couplers include: However, the comonomers used in the present invention are not limited to these. Acrylic acid esters, methacrylic acid esters, crotonic acid esters, hinyl esters, maleic acid diesters, fumaric acid esters, itaconic acid esters, olefins, styrenes, etc.

More specifically, these comonomers include methyl acrylate, ethyl acrylate, n-propyl 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, methoxyindyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate v-1-, fluor Furyl acrylate, tetrahuman 90 furfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2
-:) Methyl-3-hydroxypropyl acrylate,
2-methoxyethyl acrylate, 3-methoxymethyl 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 -Fushimo 2-methoxyethyl 7-diylsilane, 1,1-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isozorobyl methacrylate, n-butyl methacrylate, inbutyl methacrylate, 5ec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, Chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate,
N-ethyl-N-phenylaminoethyl metap+)re-
), 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-methoxynotyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2- Examples include methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, and ω-methoxypolyethylene glycol methacrylate (number of moles added = 6).

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 dicyclo, phtadiene, ethylene, furopylene, 1-butene, 1-butene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chloroprene, phtadiene, and 2.3-1 methylbutadiene.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, fromstyrene, vinylbenzoic acid methyl ester, etc. can be mentioned.

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

Further, examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, diptyl itaconate, and the like.

Examples of the maleic acid diesters include diethyl maleate, dimethyl maleate, diptyl maleate, and the like.

Examples of the fumaric acid diesters include diethyl fumarate, diptyl fumarate, and diptyl fumarate.

Examples of other comonomers include:

Acrylamides, such as acrylamide, methylacrylamide, ethyl acrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenyl acrylamide, dimethyl Acrylamide, 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, phthyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethyl Aminoethyl vinyl ether, etc.; Vinyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N- Vinylpyrrolidone, etc.; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; Unsaturated nitriles,
For example, acrylonitrile, methacrylate trile, etc.; polyfunctional monomers such as divinyl inzene, methylene bisacrylamide, ethylene glycol dimethacrylate.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates such as monomethyl itaconate, monoethyl itaconate, motuptil itaconate, etc.; monoalkyl maleates such as monomethyl maleate, monoethyl maleate, maleic acid, etc. Acid motuptil, etc.; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.; methacryloyloxyalkyl Sulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid; acrylamide alkylsulfonic acid,
For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido9-2-methylzoronosenesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acid, such as 2-methacrylate Amido-2,-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylmethanesulfonic acid, etc.; acryloyloxyalkyl phosphates, e.g. eva, acryloyloxyethyl phosphate,
3-acryloyloxypropyl-2-phosphate, etc.; methacryloyloxyalkyl phosphates, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl 2-phosphate, etc.;
Examples include. These acids may be salts of alkali metals (eg, Na, etc.) or ammonium ions.

Furthermore, other comonomers include U.S. Patent No. 3.45
No. 9,790, No. 3,488,708, No. 3,554
, No. 987, No. 4,215,195, No. 4,247,
673, JP-A-57-205735, and the like can be used.

Examples of such crosslinking monomers include N-(2-acetoacetoxyethyl)acrylamide, N-(2-(
Examples include 2-7 setoxyethyl) acrylamide.

Among these comonomers, acrylic esters, methacrylic acid, etc. 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 cassillars, and the color tone of the produced dyes. These include esters, maleic esters, acrylamides, and methacrylamides.

Two or more of these comonomers may be used in combination. 2
Examples of combinations in which vi or more are used together include n-methyl acrylate and methyl methacrylate, styrene and N=(2-(2-acetoacetoxyethoxy)ethyl)acrylamide, and tert-butyl acrylate and methyl acrylate. Re, Ru.

The polymer coupler according to the present invention is preferably a so-called copolymer, in which case the repeating unit represented by the general formula preferably accounts for 40 to 70% of the total by weight.
In particular, it is preferable that the ratio of the repeating unit represented by the general formula [Iris] to the comonomer is approximately 1:1 by weight.

The magenta polymer coupler of the present invention may be made by an emulsion polymerization method, or may be obtained by polymerization of a monomeric coupler and contains a lipophilic polymer coupler (1) dissolved in a solvent and placed in an aqueous gelatin solution in the form of a latex. It can also be made in a distributed manner. U.S. Pat. No. 4,080,21 for the emulsion polymerization method
No. 1, No. 3,370,952 K, and the method described in U.S. Pat. No. 3,451,820 for dispersing a lipophilic polymer coupler in an aqueous gelatin solution in the form of latex can be used. .

These methods are also applicable to the formation of homopolymers and copolymers, in the latter case the comonomer may be a liquid comonomer, which in the case of emulsion polymerization also acts as a solvent for the normally solid monomer. .

As the polymerization initiator used in the emulsion polymerization method and solution polymerization method of the 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;
This can be achieved by using water-soluble azo compounds such as sodium azobis-4-cyanovalerate, 2,2'-azobis(2-amidinopropane) hydrochloride, and hydrogen peroxide. In addition, examples of lipophilic polymerization initiators used in the solution polymerization method include azobisisobutyronitrile, 2,2'-azobis-(2
,4-)methylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
1. Lipophilic azo compounds such as 1'-azobis(cyclohexanone-1-carbonitrile), benzoyl peroxide, lauryl peroxide, diisopropyl peroxydicarbonate, di-tcrt-butyl peroxyl
Lipophilic peroxides such as -9 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, sodium 1-denorbanzenesulfonate, sodium lauryl sulfonate, sodium dioctylsulfosuccinate, and sulfates of nonionic activators. , polyoxyethylene nonylphenyl ether, holoxyethylene sedearic acid ester, polyoxyethylene sorbicun monolauric acid ester, polyoxyethylene-polyoxypropylene block copolymer, and the like. Examples of cationic activators include:
Examples include alkylpyridium salts and tertiary amines.

Examples of amphoteric active agents include dimethylargylbetaines, alkylglycines, etc.

Polyvinyl alcohol, polyvinyl alcohol,
Hydroxyethyl cellulose etc. are highly praised. These protective colloids may be used alone as emulsifiers or in combination with other surfactants. Regarding the types of these activators and their effects, please refer to Be1g1sc.
he Chemistry Industry.

28, 16-20 (1963) K.

To disperse a lipophilic polymer coupler synthesized by a solution polymerization method or the like in the form of a latex in an aqueous gelatin solution, first dissolve the lipophilic polymer coupler in an O-containing solvent, and then add a dispersing agent to the gelatin aqueous solution. With the help of ultrasonic waves, colloid mills, etc., it is dispersed into a latex form. U.S. Pat. No. 3,455 for a method for dispersing lipophilic polymeric couplers in latex form in aqueous gelatin solutions.
No. 1,820. As the organic solvent for dissolving the lipophilic polymer coupler, esters such as methyl acetate, ethyl acetate, propyl acetate, etc., alcohols, ketones, halogenated hydrocarbons, ether fields, etc. can be used. Further, these organic solvents can be used alone or in combination of 2fffi or more.

A typical method for producing the compound used in the present invention is shown below.

8 Coupler monomer production method example (1) 1-(2-chloro-5-methacryloylaminophenyl)-3-acetylamino-2-villazolin-5-one (
Exemplary compound (1)) (a) 1-(2-chloro-5-nitrophenyl)-3-
Amino-2-pyrazolin-5-one 2-chloro-5-nitrohibirazine20. Of (0,1,1 mol), sodium acetate 13.2 y (0,16 mol) and β-
31.4 ft (0.1'6 mol) of imino-β-ethoxypropionic acid ethyl ester hydrochloride was added to 200=7 methanol, stirred at room temperature for 2 hours, and then 26.4 ft (0.1'6 mol) of imino-β-ethoxypropionic acid ethyl ester hydrochloride was added to 26.4 ft (0.1'6 mol) of imino-β-ethoxypropionic acid ethyl ester hydrochloride. Or (0.40 mol) in methanol 80
7rLl! A solution dissolved in was added to the mixture, and the mixture was further stirred at room temperature for 1 hour. After the reaction, 26 ml of acetic acid was added, methanol was distilled off under reduced pressure, and the precipitated crystals were filtered and washed with methanol and then water.

Recrystallized from ethanol to give 1.4.3 ft' (539
5) crystals were obtained. mp205-207C8 (b) 1-(2-chloro-5-nitrophenyl)-3-
Acetylamino-2-pyrazolin-5-one 1-(2-chloro-5-nitrophenyl)-3-amino-2-pyrazolin-5-one25. Of (0,10 mol) and pyridy 21mt (o, 26 mol) of 500
m1! of tetrahydrofuran, and 18.6 mt (0.26 moA/) of acetyl chloride was added dropwise under water cooling. After dropping, stir at room source for 2 hours and add 5J? The precipitated crystals were filtered and washed with water. 100 ml of this crystal
Dispersed in ethanol and further added 100ml of water and 12.5ml of water.
A solution containing 7 (0.31 moy) of sodium hydroxide was added and stirred for 30 minutes at room temperature. After neutralization with acetic acid, extraction with ethyl acetate, drying over anhydrous sodium sulfate, and distilling off the solvent under reduced pressure, the remaining oil was recrystallized from ethanol.
．． 5t (42'g) of crystals were obtained. ip 225-23
0 C0(C)1-(2-chloro-5-aminophenyl)-3-acetylamino-2-pyrazolin-5-one 1-(2-chloro-5-nitrophenyl)-3-acetylamino-2 -pyrazolin-5-one 12.02 (0,
04 mo/l/) was added to 240 ml of 90% acetic acid, stirred vigorously and heated to 70C. Reduced iron content 12F was added little by little, and the mixture was further heated for 15 minutes. After cooling, it was filtered, and the filtrate was poured into saline solution, and the precipitated crystals were filtered and washed with water.
(38%) of crystals were obtained. mp 162-165C0
(d) Exemplary compound (1) 1-(2-chloro-5-aminophenyl)-3-nacetylamino-2-pyrazoline-5-mene 10.6? (0
,04 mol), pyridy 8 ml (0,10 mol/l
/) and 1 mJ of nitrobenzene were added to 200 ml of tetrahydrofuran 80 furan and mixed with methacrylic acid chloride+ under water cooling.
:"to, 4r (0.10 mol) was added dropwise, stirred for 30 minutes, poured into 2I! water, extracted with ethyl acetate,
After drying over anhydrous sodium sulfate, the solvent was distilled off at 25-35C under reduced pressure. Add 507 rLl of ethanol and 5Q+++4 of water to the residual oil, and add 4.8 liters of sodium hydroxide.
A solution of t (0.12 mol) was added and stirred at room temperature for 30 minutes.

After neutralization with acetic acid, the precipitated crystals were filtered and recrystallized from ethanol to obtain 5.8f (44%) coupler monomer (1). rip 212-215C.

Elemental analysis value ((+aH+5N40s(J') Theoretical value C: 53.82 嗟H: 4.52%N: 16.74
% Experimental value C: 54.06 H: 4.38 N: 16.8
1 Manufacturing method example (2) 1-(2-chloro-5-acryloylaminophenyl)
-3-acetylamino-2-pyrazolin-5-one (exemplified compound (2)) 1-(2-chloro-5-aminophenyl)-3-acetylamino-2-pyrazolin-5-one 16, Of (0
,06 mo#), pyridy 10 ml (0,15 mo+) and nitrobenzene 1.577 Lj? 30θ
ml! In addition to tetrahydrofuran, acrylic acid chloride 913.69 (0.15 mol) was added dropwise under water cooling.
31 after stirring for 30 minutes! of water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and heated under reduced pressure for 25~
The solvent was distilled off at 35c. Add ethanol to the residual oil
T and 50m1 of water! and then add sodium hydroxide 7,
A solution containing 0.18 mol of 1:1 (0.18 mol) was added and stirred for 30 minutes at room temperature. After neutralization with acetic acid, the precipitated crystals were filtered and recrystallized from ethanol to obtain 7.2t (37.4%) of coupler monomer (2). mp227-230c
.

Elemental analysis value (C14H1sN403C1) Theoretical value C:
52.43 section H: 4.09 section N: 17.47 section experimental value C
:52.21H: 4.25HN:17.2G Production method example (3) 1-(2-chloro-5-methacryloylaminophenyl)-3-pivaloylamino-2-pyrazolin-5-one (exemplary compound (3)) (a) 1-(2-chloro-5-nitrophenyl)-3-
Pivaloylamino-2-pyrazolin-5-one 1-(2-chloro-5-nitrophenyl)-3-amino-2-pyrazolin-5-one 25.0f (0.1.0 mol) and pivaloyl chloride 12 .1 f (0,10
mol) was added to 500 mJ of acetonitrile, heated under reflux for 1 hour, cooled, and the precipitated crystals were filtered. 19.
Crystals of 5f (5996) were obtained. 7Fip153-15
9tll'.

(b) 1-(2-chloro-5-aminophenyl)-3-
Pinoloylamino-2-pyrazolin-5-one 1-(2-chloro-5-nitrophenyl)-3-pivaloylamino-2-pyrazolin-5-one 17, Of (
0.05 mol) to 300 ml of 90-thiacetic acid, stir vigorously and heat to 70C. 15 g of reduced iron powder was added little by little and heated for an additional 15 minutes. After cooling, the filtrate was poured into saline solution, and the precipitated crystals were filtered and washed with water to a temperature of 7.7F (
5.0) crystals were obtained. 77Lp142-147C
.

(C) Exemplary compound (3) 1-(2-chloro-5-aminophenyl)-3-hyvaloylamino-2-pyrazolin-5-one 15.45'
(0,05 mo#), Pirijiy 9.6 ml (0,
12 mo#) and nitrobenzene 1.2 mJ at 200
ml of tetrahydrofuran, and dropwise added 12.4 M (0.12 mol) of methacrylic acid chloride under water cooling.
After stirring for 0 minutes, 21! of water, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and heated under reduced pressure for 25~
The solvent was distilled off at 35C. Add ethanol 607 to the residual oil.
71J? and 60 ml of water were added thereto, followed by a solution containing 5.8ii' (0.15 mol) of sodium hydroxide, and the mixture was stirred at room temperature for 30 minutes. Neutralize with acetic acid, filter the precipitated crystals, and recrystallize from ethanol to obtain a crystal of 8.35' (44
%) of coupler monomer (3) was obtained. mp 193
~1961; 0 theoretical value C: 57.37%) (: 5.6
2 Chi N: 14.87 Experimental value c: 57.54 H:
5.60 N: 14.71 or less Margin B0 Polymer compound manufacturing method example (4) 1-(2-chloro-5-methacryloylaminophenyl)-3-acetylamino-2-pyrazolin-5-one (
1) and n-butyl acrylate, a lipophilic polymer Cassilla latex (A). After adding 0.36 f of azobisinobutyronitrile dissolved in water, the reaction was carried out for 6 hours. The dioxane solution was added dropwise into 2 water, and the precipitated solid was filtered, washed with water, and dried to give 17.5 f ( 88%)
A lipophilic polymer coupler was obtained. The copolymer composition of this polymer coupler was found to have a coupler monomer (1) content of 538 by elemental analysis (nitrogen analysis).

The above polymer coupler 102f was dissolved in 30 ml of ethyl acetate, and to this solution was added a mixed solution of 6 ml of a 10-polymer aqueous solution of sodium lauryl sulfate and 100 ml of a 5 wt % aqueous solution of seratin, followed by ultrasonic dispersion. After that, ethyl acetate was removed by vacuum distillation to form the polymer coupler latex (A).
I got it.

Production example (5) Latex of lipophilic polymer coupler of 1-(2-chloro-5-methacryloylaminophenyl)-3-pivaloylamino-2-birazolin-5-one (3) and n-butyl acrylate and methyl acrylate (B ) Coupler monomer (3) 10fX n-butyl acrylate 52, methyl acrylate 57 and dioxane 120
The mixture of - was stirred at 80°C in a stream of dioxane, and dioxane 4tnI! Azobisisobutyronitrile dissolved in 0
．． After adding 36f, the mixture was reacted for 6 hours. A dioxane solution was added dropwise into water 2, and the precipitated solid 7 was filtered out, washed with water and dried to obtain a polymer coupler of 16.25' (sis). The copolymer composition of this polymer coupler was determined by elemental analysis (nitrogen analysis) to have a coupler monomer (3) content of 52.3%.

The above polymer coupler was treated in the same manner as in Production Example (4),
A polymer coupler latex (B) was obtained.

Production method example (6) 1'-(2-chloro-5-methacryloylaminophenyl)-3-methanesulfonamide-2-pyrazoline-5
-one (8) and n-butyl acrylate lipophilic polymer coupler latex (C) coupler monomer (B)
i or r and n-butyl acrylate 102 and ter
A mixture of 200% of tert-butanol was stirred under a nitrogen stream, and azobisisobutyronitrile 036f dissolved in 10% of tert-butanol was added, followed by reaction for 6 hours. A tert-butanol solution was added dropwise into water 2, and the precipitated solid was filtered, washed with water, and dried.
A lipophilic polymer coupler of F (78%) was obtained. The copolymer composition of this polymer coupler was determined by elemental analysis (nitrogen analysis).
The content of coupler monomer (8) was 54.0%.

The above polymer coupler was treated in the same manner as in Production Example (4) to obtain a polymer coupler latex (C).

Production method example (7) 1-(2-chloro-5-methacryloylaminophenyl)-3-acetylamino-2-pyrazolin-5-one (
Polymer coupler latex (A') of 1) and n-butyl acrylate Coupler monomer (1) 10 f and n-butyl acrylate 10 f were heated and dissolved in 200 ml of ethanol. 800ml of an aqueous solution containing 2t of sodium salt of oleyl methyltauride dissolved therein was heated to 95°C and stirred in a nitrogen stream, and 20ml of an aqueous solution of 140ml of potassium persulfate was added. Next, the above-mentioned ethanol solution was added dropwise over 1 hour. After the completion of the dropwise addition, the mixture was heated and stirred at 95 to 85°C, and after 3 hours, a 20% water-resistant solution of potassium persulfate 60119 was added, and the mixture was further stirred at the same temperature for 3 hours. After that, ethanol and unreacted n-butyl acrylate were azeotroped with water. It was distilled off as a mixture.

The solid content concentration of the formed latex was 10.8 wt.
The copolymer composition was found to have a couplernomer fl) content of 48.7% by elemental analysis.

Manufacturing method example (8) 1-(2-chloro-5-acryloylaminophenyl)
-3-acetylamino-2-pyrazolin-5-one (2
) Polymer coupler latex of toethyl acrylate (B') Coupler monomer (2) 10f and ethyl acrylate 1
oi was heated and dissolved in 200 ml of ethanol.

An aqueous solution 800- in which sodium salt 22 of oleyl methyltauride was dissolved was heated to 95°C in a nitrogen stream),
(The mixture was stirred, and a 20-aqueous solution of 140 q of potassium persulfate was added. Then, the above-mentioned ethanol solution was added dropwise over 1 hour. After the addition was completed, the mixture was heated and stirred at -95 to 85°C,
After 3 hours, 20 ml of an aqueous solution of 60 rq of potassium persulfate was added, and the mixture was stirred at the same temperature for another 3 hours, and then ethanol and unreacted ethyl acrylate were distilled off as a mixture of water.

The solid content concentration of the latex formed was 9.8 wt%,
The copolymer composition was found to have a coupler monomer (2) content of 54.3% by elemental analysis.

Production method example (9) Production method example +41 using the above coupler monomer, (5),
(6) (Production method I) and production method examples (7), (8) (Production method ■)
The following polymer coupler latex was obtained in the same manner as the copolymer.

Manufacturing method l Manufacturing method ■ u) Mh: Methyl acrylate BMA: n-butyl methacrylate EA: Ethyl acrylate) AA
Niacrylic acid BA: n-butyl acrylate St:
Styreno HA: n-hequinol acrylate Eight M niacrylamide MMA: Methyl methacrylate The latex of the magenta polymer coupler in the present invention can be used alone or in combination with generally well-known couplers. It may be the same dye image-forming coupler as the latex of the magenta polymer coupler of this invention, or it may be a different dye image-forming coupler. Colored couplers or development inhibitor releasing (DIR) couplers with color-correcting effects and (Weiss) nol couplers in which the products formed by the coupling reaction are colorless may also be used in conjunction with the magenta polymer couplers of the present invention. can do. The mixed coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in the molecule; No. 451.820, same 4
, No. 215,195, British Patent No. 1,247,688,
JP-A No. 57-94752, JP-A No. 58-2ε Near No. 45,
No. 58-42044, No. 58-43955 A magenta dye image-forming coupler that may be a polymer coupler or a water-soluble polymer coupler having a sulfonic acid group or a carboxylic acid group described in the specifications of each publication. Examples include U.S. Patent No. 2,600,788;
No. 83,608, No. 3,062,653, No. 3,12
No. 7,269, No. 3,311.47 (No. 5, No. 3, 4)
No. 19,391, No. 3,519,429, No. 3,55
8,31.9, 3,5 s 2.322, 3
, No. 615,506, No. 3,834,908, No. 3,
891,445, West German Patent No. 1.810,464, West German Patent Application (OI, S) No. 2,408,665,
No. 417,945, No. 2,418.959, No. 2,4
No. 24,467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 51
-20826, 52-58922, 49-12
No. 9538, No. 49-74027-1 No. 50-159
336 Post, No. 52-42121, No. 49-74028
Examples include couplers described in No. 50-60233, No. 51-26541, and No. 53-35122.

An example of a Norard coupler that can be used in combination with 1 is US 1.
．． ! ! l Patent: U,] No. 48,062, 3,22
7.55 l1 No. 1, No. 3,733,201, No. 3,
No. 617,291, No. 3,703,375, No. 3,6
No. 15,506, No. 3,265,506, No. 3.62
1J, No. 745, No. 3,632,345, No. 3,8
No. 69,291, No. 3,642.4 g No. 5, No. 3,
Examples include colored couplers described in British Patent No. 770,436, British Patent No. 3,808,945, British Patent No. 1.201,110, and British Patent No. 1,236,767.

As a DIR coupler, U.S. Patent 3.14)t, 06
No. 2, No. 3,227,554, No. 3,733,201
No. 3,617,291, No. 3,703,375, No. 3,615,506, No. 3,265.50 b, No. 3,620,745, No. 3,632,345 ,
No. 3,8641,291, No. 3,642, 4.85, No. 3.77 (No. 1,436, No. 3,8 (18,
945-, British Patent No. 1,201,110, British Patent No. 1,2
Examples include those described in No. 36.767.

Furthermore, as a Wise coupler, we are in the United States! rjγ1'
3.876,428, 3,580,722, 2
, 998.3[, No. 1-, No. 2,808,329, No. 2,742.832, No. 2,689.793-, and the like.

The above couplers are used in U.S. Patent Nos. 2.26 (1,1,58;
2,772.163yy, 2,801,171,
Dispersed in hydrophilic colloid by the method described in British Patent No. 1,151,590 etc.
30494, No. 51-:39853, and can also be used by impregnating (loading) into the latex of the Magenta 71 (Remarker Duller) of the present invention. Here, impregnation (loading) means This means that the hydrophobic magenta coupler is contained inside the latex of the magenta polymer cover, or is deposited on the latex surface of the magenta coupler. However, the exact mechanism by which impregnation (loading) occurs is not known. Not yet.

The magenta polymer coupler of the present invention is disclosed in U.S. Pat.
No. 36,327, No. 2,728,659, No. 2,33
No. 6,327, No. 2,403,721, No. 2,701
, No. 197, No. 3,700,453, British Patent No. 1,326,889, U.S. Patent No. 3,432,300, No. 3,698,909,
'No. 3,574,627, No. 3,573,050,
Dye image stabilizers described in West German Publication No. 3,764,337, West German Publication No. 2,529,350, West German Publication No. 2,448,063
No. 2,610,546, U.S. Patent No. 3.928,
No. 041, No. 3,958,993, No. 3,961,9
No. 59, No. 4,0491455, No. 4,052,21
No. 3, No. 3,379,529, No. 3, No. 3,379,529, No. 043,69
No. 0, No. 3,364,022, No. 3,297,445
No. 3,287,129, etc. can also be used in combination.

Conventionally known methods can be used to introduce the above-mentioned well-known couplers into the silver halide emulsion layer. For example, high-boiling organic solvents with a boiling point of 175°C or higher such as tricresyl, cyphytyl phthalate, or butyl acetate,
After dissolving the coupler in a low boiling point solvent such as butyl propionate alone or optionally in a mixture thereof, it was mixed with an aqueous gelatin solution containing a surfactant, and then shaken in a high to moderately rotating mixer. After being emulsified in a colloid mill, it can be added to silver halide to prepare the silver halide emulsion used in the present invention.

When added to the silver halide emulsion used in the present invention, it is usually 0.07 to 0.0 per mole of silver halide.
It is added in an amount of 7 mol, preferably 0.1 to 0.4 mol. When the coupler has an acid group such as sulfone or bunorbonic acid, it is added to the hydrophilic colloid as an alkaline solution.

The silver chloride used in the silver chloride emulsion layer according to the present invention includes conventional silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. Any of those used in silver halogenide photographic emulsions are included.

These silver halide grains, even those with coarse grains w, KM
The particle size distribution may be narrow or wide.

The crystals of these silver grains are normal crystals,
It may be double-sided, and any ratio between the [100] plane and the (111) plane 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.

Furthermore, these silver halogenides 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 halogenide grains can be prepared by known methods commonly used in the art.

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

As the inder of the silver halide emulsion layer according to the present invention, conventionally known inders can be used, such as gelatin, gelatin derivatives such as phenylcarbamylated seratin, acylated gelatin, and phthalated seratin, polyvinyl alcohol, polyvinyl Polymer non-Wf such as pyrrolidone, polyacrylic acid amide, IQT' quality, alginate, polyacrylic acid-based 1.
Polymer amphoteric materials such as copolymers of vinylimidazole,
Examples include crosslinkable polymers described in US Pat. No. 4,215,195. It may also contain a dispersed hydrophobic polymeric substance, such as a latex such as butyl Nisder 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.

Examples of 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 above-mentioned additives, the silver halide photographic material of the present invention contains stabilizers, development accelerators, hardeners, surfactants, anti-staining agents, lubricants, ultraviolet absorbers, formalin scavengers, and other photographic sensitizers. A variety of additives are used that are useful in stimulants.

In addition to the silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention, auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, and a back layer can be provided as appropriate.

The support may be appropriately selected from conventionally known supports such as plastic film, plastic laminated paper, baryta paper, synthetic paper, etc., 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 photographic material of the present invention thus constructed 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. Specific examples of this color developing agent include p
-Phenylenediamine-based ones are typical, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, and 2-amino-5-diethylaminotoluene hydrochloride. , 2-7mi/-5-(N-ethyl-
N-dodecylamino)-)luene, 2-amino-5-(
N-Ethyl-N-β-methanesulfonamidoethyl)amine toluene sulfate, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-.(N
-ethyl-N-β-hydroxy-thylamino)aniline, 2-amino-5-(N-ethyl-β-methoxyethyl)amine toluene, and the like. 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 no-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 various additives such as an alkali metal chloride such as potassium bromide, or a development regulator such as It may also contain cytodisic acid and the like.

The silver halide photographic material of the present invention may contain the above-mentioned color developing agent in the hydrophilic colloid layer, either as the color developing agent itself or as its flarer. Recursors for color developing agents are compounds that can produce color developing agents under alkaline conditions, and include Schiff base type precursors with aromatic aldehyde derivatives, polyvalent metal ion complex precursors, phthalic acid imide d4 precursors, and phosphoric acid amide precursors. Examples include 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. 3,342,5
No. 99, No. 2,507,114, No. 2,695,
No. 234, No. 3,719,492, British Time 8' [Specification No. 803,783, JP 53-135628-
Publications No. 54-79035, Research Disclosure No. 15159, No. 12146, No. 1
No. 3924.

These aromatic primary amine color developing agents or their precursors need to be added in amounts that will provide sufficient color development during development. Although this amount varies considerably depending on the type of photosensitive material, it is generally photosensitive silver halide 1
The amount used per mole is between 0.1 and 5 moles, preferably between 0.5 and 3 moles. These color developing agents or their precursors can be used alone or in combination. In order to incorporate additives such as these developing agents and their precursors into photographic materials,
It can be added by dissolving it in an appropriate solvent such as water, methanol, ethanol, or acetone, or it can be added as an emulsified dispersion using a high boiling point organic solvent such as dibutyl phthalate, dioctyl phthalate, or tricresyl phosphate. Deki, Research Disclosure Magazine 14850
They can also be added by impregnation into latex polymers as described in the above issue.

The silver halide photographic material of the present invention is usually subjected to bleaching and fixing, bleach-fixing, and washing with water after color development. As a bleaching agent, many compounds are used, among them iron (formerly Kobal) (III),
Polyvalent metal compounds such as tin (■), in particular complex salts of these polyvalent metal cations and organic acids, such as ethylenediaminetetraacetic acid, nitriloter('p acid, N-hydroxyethylethylenediaminodiacetic acid) Metal complex salts such as aminopolycarboxylic acid, malonic acid, silicic acid, malic acid, diglycolic acid, dithioglycolic acid, ferricyan r1/2 salts, dichromate, etc. are used alone or in appropriate combinations. .

■Specific embodiments of the invention Example l.

Latex (A), (B) of the polymer coupler of the present invention
, (C), (L) and (T) and the latex fl), +21 and R() of the comparative polymer couplers described below.
5×113′ coupler monomer units for each
mol of silver iodobromide was added to 100 t of a high-sensitivity silver iodobromide emulsion containing 5×10 −2 mol of silver iodobromide and 10 r of gelatin and deposited on a triacetate support at 2.4 f/n? Silver halide color photographic materials (Samples 1 to 8) having stable coating films were prepared by coating and drying the coating silver in an amount of .

These samples 1 to 8 were each subjected to wedge exposure using a conventional method and then subjected to the following development treatment.

Processing process (38°C) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds Used in each processing step The composition of the treatment liquid was as follows.

[Color developer]

[Bleaching solution composition] [Fixing solution composition] [Stabilizing bath composition] r Formalin 37% aqueous solution 5.0 me The density of the obtained magenta colored image was measured through a magenta filter, and fog, relative sensitivity (S) and maximum Extreme concentration (I) ma
x) was calculated, and the results obtained are shown in Table 3.

In addition, latex (1), (
2) and (3) have the following compositions.

Comparative Example (11 Below, Margin Comparative Example (2) Comparative Example (3) From Table 1-an vs. sensitivity (S), phase 2j value of the reciprocal of the exposure amount required to obtain a density of fog+02, Inventive polymer turnip sea latex (
Each sample (1) to (5) obtained using A), (1]), (C>, (T, ) and (T) is a latex of a specific axis polymer coupler]1), (2) and It was found that the color development was more immediate and less foggy than the samples (6) to (8) obtained using -C using (3).

Example 2 Latex (A') and (B) of polymer couplers of the present invention
(11 and (M')) and the comparative polymer coupler latex (1'), (2 and (3')) each containing 5XlO'' moles of turnip monomer units.
・It is added to 1 oor of a high-sensitivity silver iodobromide emulsion containing 5xlO" moles of silver halide and 101 moles of gelatin, coated on a triacetate support at a silver i2.4 t/n? and dried to form a stable coating film. ...A silver halide color photographic material (sample Nt19-15) was obtained.

These photosensitive materials were subjected to wedge exposure in the same manner as in Example 1, and then developed.

In addition, latex (1') (2) of polymer couplers for comparison
') and (3') have the following compositions.

Comparative Example (Circle Comparative Example (2') Comparative Example (3') Table 2 From Table 2, the latex of the polymer coupler of the present invention (
Each sample (9) to (12) obtained using A'), (B'), (H') and (M') was compared with the comparative polymer couplers DiFux (1'), (2') and (2'). It was found that the color development was superior to that of Samples (13) to (15) obtained using Sample No. 3'), and there was less fog.

Example 3 Latex (A) and (B) of the polymer coupler of the present invention
, (C), (L), and (T) and the comparative polymer coupler latex (IL (21), and (3), each containing 7 magenta dye-forming coupler monomer units.
．． Silver chlorobromide 5X1 (1-2
2-hydroxy% 4.6-dichloro-
10 i of a 0.2% aqueous solution of 8-triazine sodium salt was added to the polyethylene-coated support with a coated silver amount of 0.
．． A sample of a silver halide color photographic light-sensitive material was prepared by coating and drying to a thickness of 5 f/m'.

These samples were conventionally wedge exposed and processed according to the steps and processing steps described below.

Processing process [Color developer] [Bleach-fix solution] Darken the magenta dye image obtained by developing each sample under the above conditions! Set a+1+, fog,
The relative sensitivity (S) and maximum density (Dmax) were calculated and the obtained results are shown in Table 3.

In addition, latex (1), (
The compositions of 2) and (3) are the same as in Example 1.

Table 3 It is.

As is clear from Table 3, the silver halide color photographic light-sensitive materials (Samples 16 to 20) obtained using the polymer coupler latex of the present invention are different from the comparative polymer coupler latexes (1) and (2). ) and (3)/ It can be seen that the coloring properties are very excellent compared to the silver halide color photographic light-sensitive materials (samples 21 to 23), and there is less fog.

Example 4 Latex (A'), CB of the polymer coupler of the present invention
For the latexes (1'), (2'), and (3') of the latexes (1'), (■i, (M), and the comparative polymer Cubsy), one unit of the magenta dye-forming coupler was added to 7. 5
Photographic emulsion 1 containing 5x silver halide, 10-2 mol of gelatin and 102 mol of gelatin was mixed with 10 ml of hard (2-hydroxy-4,6-dichloro-8-) as a percentage agent. 2 ml aqueous solution of gin sodium salt 10+
++/! A silver halide color photographic material was prepared by coating on a support coated with polyethylene and drying.
It was +++'. These samples were subjected to wedge exposure in a conventional manner and developed in the same manner as in Example 3.

The density of the obtained magenta dye image was measured, and the fogging relative sensitivity (S) and maximum density (Dmax) were calculated, and the obtained results are shown in Table 4. The composition of the comparative polymer coupler latex (1x, (2'), shibi (, 3x) was the same as in Example 2.

The fourth expression relative FB+(S) is the relative value of the reciprocal of the exposure amount required to obtain a density of fog+02.

As is clear from Table 4, the silver halide color photographic light-sensitive materials (Samples N124 to 27) obtained using the latex of the polymer Kagura of the present invention were obtained using the latex of the polymer Kagura for comparison. It was found that the color development was always superior to that of photographic photosensitive material N (sample Nα28 to 30), and there was less fog.

Implemented 1j5゜Honkomei's polymer coupler latex (A), (j3
), (C), (A, (B'), (H') and JtJ
2 E') -r-Coupler latex (1), (2
), (1') and (2'), a latex solution containing 7.5 x 10'' moles of one unit of each magenta dye-forming coupler, 8.4 x 10' moles of silver iodobromide and 1 o gelatin.
A silver halide color photographic light-sensitive material (sample height 31-3) was obtained by mixing 100 f of an emulsion containing T and coating it on a triacetate support and drying it.

These light-sensitive materials were each subjected to wedge exposure using a conventional method and then subjected to the following development treatment.

Treatment process (38℃) 1"-1 during treatment First development: 6 minutes 1st water wash 2 minutes Reversal 2 minutes Color development 6 minutes Adjustment 2 minutes Bleaching 6 minutes Fixed arrival time: 4 minutes Final washing: 4 minutes Stability 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[First developer].

Nitrilo-N, N, N, N-) IJ Methylenephosphonate Pentasodium Aqueous Solution (45T) 1.0-Ni44e (
(J Potassium Dihydrate 35.Or Sodium Bromide
2.2f Sodium thiocyanate tof, (j Potassium iodide
4.5 potassium hydroxide, 4.5F diethylene glycol 12.0 mA l-phenyl-4-hydroxymenal=3-pyrazolidone 1.5 r i anhydrous potassium carbonate 14.09 sodium bicarbonate 120 t potassium hydroquinone sulfonate 22. Add or water to make 1 t.

Adjust the pH to 9.6 [Reversal solution] Propion fR 12.0ml Anhydrous stannous chloride 1.5f Peraminophenol 05 ■ Sodium oxide 5.01 = trilo N, N, N, N-) rimethylene phosphonic acid 5
Sodium aqueous solution (45%) 15.0m6 1t Light color developer adjusted to pH 5.8 Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium aqueous solution (45%) 50-phosphoric acid (85%) 7
．． 0 me Sodium 072 Tenka Potassium 300 Potassium Hydroxide 20. Of Citrazic acid 13g4-7mi/-N-ethyl-N-(β-methanesulinamidoethyl) m) Luidine sesquisal 7ate 1
Hydrate 1], Of l, 8-hydroxy-3,6-cythiaoctane 1. O
Adjust IL pHll to 7 with water [adjustment solution] Potassium sulfite 15. (1 Ethylenediaminetetraacetic acid 8.Of α-monothioglycerol 1t with 0.5mA water Adjust to pH 6.2 [bleach solution] Potassium nitrate 25.Of potassium bromide 80.Of ethylenediaminetetraacetic acid (former ammonium) 110.
Of hydrobromic acid (48%) 30.0m ethylenediaminetetraacetic acid 4. Of water 1t p) Adjust to I5.7 [Fixer] Ammonium thiosulfate 55. (1 Disodium ethylenediaminetetraacetic acid 08t Sodium metabiite 7.5f Sodium hydroxide 1.5f Adjust to pH 6.6 with water [stabilizing solution] Formalin (35%) 6. +1 +++/Konidax (Konishiroku Photo Industry) Co., Ltd.) 1 with 7.5 mg water under the above conditions, and the density of the magenta dye image obtained was measured, and the fog, phase correspondence 1 river (S), and maximum density (1) max were measured. ) was calculated, and the results are shown in Table 5. The compositions of the latexes (1), +21, (1'), and (2') of the comparative polymer Kagura were the same as in Examples 1 and 2.

As is clear from Table 5 (Table 5), the color development of the sample obtained using the latex of the polymer coupler of the present invention is much higher than that of the sample obtained using the latex of the comparative polymer coupler. It was found that there was a good amount of water and less capri.

Applicant Konishi Roku Photo Industry Co., Ltd. Procedural Loss 1 Seishi 11f41158 Own weight August 2311 Commissioner of the Patent Office Kazuo Wakasugi Tono.
1. Name of the invention Silver halide color photograph 16 Kozuki 3. Relationship with the case of the person making the amendment Patent publication p, 91 people Address 1 Ke 1 Inn 1 Ti, Obosuku-ku, Tokyo: ] 2 T; I! 12V; Name (4a;) (127) Elementary School 46 Tame J'j
:IJ':tJjtAJ-lE (1 person 31ν Itoki 1 month Igi IL service 4・Agent 〒102 Detailed description of the invention 6, Contents of detention 6, N}: 1 positive Contents (1) Akira.!jtl borrowed from page 14, 5th line from the bottom to page 15 Bp, 4th line ``L k'r.-CONH
-, -NI-ICONH1 or -NH1 (however, the hydrogen atom is bonded to the virazolone ring) or -NI
．． lCOO-... bivalent NOG. represents,”
"L is 100NI-1-, -NHCO-, -NHCO
NII. -, -NIiCOO-, -OCONI-1-,
-COO-.

-OCO-, -CO-, -SO2NH-, -NHSO2
-, -SO2-.

Represents a group of 21 pieces of Δtake 101, preferably 1CO
NH-, -Nl-ICO-, -SO,N}{-, -Nl
-ISO2- or -NIICONI-1-. P is 1 COI LT- (However, Akuun. Tou Aiko is - {
, l, + formula [11J] is introduced. )-COO
- (I1shi, 醐shi},, the atom has the general formula [fil]
It matches A of e'l'. )-1, tah-SO,-
represents a divalent group, preferably 100NH- or 1COO-. ” and stopped.

{2} Bright part, -4. et al., p. 1315, et al., page 2] lines 2 to 18 [in the general formula [111], ρ1 or L is
This is the xA combination of...

In the general formula [ol], it is even more preferable that L is one CONH-, and In and This is the case when +1 is 00, and R is the case when it is an alkyl group, especially a methyl group.''

(3) "...l is 1" on page 16, line 17, 1 of the detailed description
B. ``In which case of Ishi 3...'' is supplemented with 1...l or +7, (Ishi 2, in which case...'').

2 Procedures Sleeves (Voluntary) 1. Indication of ηj patent application 2 filed on August 15, 1980, title of invention Silver halide color photographic light-sensitive material 3, j:y:I section with outside the person making the amendment Person who issued the patent Location Tokyo t ``ll + Shinjuku-ku Nishi-Shinjuku 1-26 Kaori 2 Name (Name) (127) Konishiroku Photo Industry Co., Ltd. Nobuhiko Kawamoto 4 Agent Address 10'2 Address Chiyoda-ku, Tokyo Kudanminami 2-chome 2 No. 8 11fJ
J ss August 23, 2016 Procedure for submission; ri + i positive i1
4 “Amendment 6, Contents of the amendment (1) Procedural amendment record 3 lines from the bottom of page 1 [I r [Ill
], preferably L...'' is r [III]
So, if it is correct, L is corrected as...j.

that's all

Claims (1)

[Scope of Claims] A silver halide color photograph having, on a support, a silver halide emulsion layer containing a magenta dye-forming polymer coupler having the 43rd repeating position represented by the following general formula [■] Photosensitive material. General formula [I] (wherein, Q represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group, ya represents a monovalent group, bird represents a monovalent group, and X represents)- It represents a rogene atom, and Z represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized product of a color developing agent. 1 represents an integer from 0 to 3. When l is 12 or more, two or more birds may be the same or different. )