JPS6173151A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To form a silver halide color photographic sensitive material superior in graininess by using a specified 2-equiv. yellow dye-foaming polymer coupler latex. CONSTITUTION:A silver halide emulsion layer formed on a support contains the yellow dye-forming polymer coupler latex capable of forming a dye with an alkaline color developing soln. and having repeating units each represented by formula 1 in which R1 is alkyl or aryl, R2 is a monovalent group, Q is a group having an ethylenically unsatd. group and releasable on the coupling reaction with the oxidation product of a color developing agent, and l is an integer of 0-5. The monomer of the coupler of formula 1 is typically embodied by formula 2.

Description

DETAILED DESCRIPTION OF THE INVENTION 10. Background of the Invention (Technical Field) The present invention relates to a silver halide photographic light-sensitive material containing a novel 2-modomer rho dye-forming polymer coupler latex.

(Prior art and its problems) As is well known, in subtractive color photography, oxidation products of a color developing agent are produced when an aromatic primary amine color developing agent reduces exposed silver halide grains. A dye image is formed by oxidative coupling of a yellow, cyan, and magenta dye-forming coupler in a silver halide emulsion. In these cases, as a yellow coupler to form a yellow dye, a compound having an open-chain active methylene group is generally used, and as a 7-zenta coupler to form a magenta dye, a pyrazolone type, pyrazolotriazole type, or pyrazolone type is used. Compounds such as zolobenzimidazole and indacylon are used, and cyan couplers for forming cyan dyes include:
Phenolic and naphthol compounds have been used.

Each coupler is dissolved in a substantially water-insoluble high-boiling organic solvent.
Alternatively, if necessary, dissolve it in combination with an auxiliary solvent,
It is added to the silver halide emulsion, or dissolved in an aqueous alkaline solution and added to the silver halide emulsion. The former is an oil droplet dispersion method, and the latter is an alkali dispersion method.
Generally, the former has better light resistance, heat resistance, moisture resistance, and
It is said to be excellent in terms of color sharpness, etc.

The basic properties required of each coupler include not only the ability to simply form a dye, but also high solubility in high-boiling organic solvents or alkalis, as well as dispersibility and stability in silver halide photographic emulsions. The dyes formed by the dyes should have fastness to light, heat, moisture, etc., good spectral absorption characteristics, good transparency, high color development sensitivity, and It is rare for the images to have various characteristics such as excellent sharpness and graininess.

However, to the best of the knowledge of the present inventors, no conventionally known yellow coupler has yet been found that satisfies all of the above-mentioned required properties.

Conventionally, various 7-syl acetanilide or benzoylmethane couplers have been known as yellow couplers, but so-called 4-equivalent couplers in which the coupling active position is unsubstituted have poor coloring efficiency.

As a method for improving the coloring efficiency, a so-called 2-color yellow coupler is known, in which a substituent capable of simultaneously leaving the color-forming yjl is introduced into the active position of the coupler. These 2
As the leaving group of the equivalent yellow coupler, for example, a coupler having an aryloxy group is disclosed in JP-A-50-8765.
No. 0, U.S. Pat. No. 3,408,194 discloses a coupler having an oxacylyloxy group in JP-A-51-131325.
A coupler having a chroman-4-oxy group is disclosed in JP-A-51-139333, a coupler having a tetrazolyloxy group is disclosed in JP-A-52-43426, and a coupler having a nitrogen-containing heterocyclic group is disclosed in JP-A-52-43426. A coupler having a urazole group and a hydantoin group is disclosed in Japanese Patent Publication No. 49-43576, and a coupler having a tetrazolone group is disclosed in JP-A No. 51-53825 and 50-288.
No. 34, couplers having an arylthio group are described in US Pat. No. 3,227,554, and some of them have already been put into practical use.

However, although this 2-equivalent yellow coupler has high sensitivity and excellent color development, it has the drawback of poor graininess.

JP-A-59-9657 describes a dye-diffusing coupler for the purpose of improving graininess. Although these dye-diffusion type couplers have improved graininess, they have new problems such as deterioration of sharpness and increase in capri due to dye diffusion, and discoloration of dye images due to the influence of residual 11 radicals. Was.

By the way, in a silver halide color photographic light-sensitive material having a multi-H structure, it is necessary to fix each coupler in a separate layer in order to reduce color mixture of each dye and improve color reproducibility.

Various methods are known for preventing coupler diffusion.

One method is to introduce a long-chain aliphatic group (diffusion-inhibiting group) into the coupler molecule to prevent diffusion. Couplers made using this method are not miscible with gelatin aqueous solutions, so they must be solubilized in alkali and added to the gelatin aqueous solution, or they can be used as oil-soluble ballasts! ! (diffusion prevention group)
It is necessary to disperse the coupler having the following properties in the form of colloidal particles in an aqueous gelatin solution together with a high boiling point organic solvent with the help of a surfactant. In such couplers, the hydrophilic groups in the coupler interact with gelatin, causing a thickening phenomenon, especially during the coating process, which impedes high-speed uniform coating, or causes crystal precipitation in the emulsion. do. Furthermore, when an organic solvent with a high boiling point is used, multiple layers of gelatin are required to soften the emulsion layer, and as a result, it is difficult to make the emulsion layer thin.

On the other hand, another method for making a coupler resistant to diffusion is to use a polymer coupler obtained by polymerizing a monomeric coupler in which a group containing a polymerizable unsaturated bond is introduced into the coupler molecule.

The polymer coupler is added to the woody colloid composition in the form of a terrax in the following manner. One is to directly polymerize the coupler monomer with other copolymerization components by emulsion polymerization to form a latex, which is then added to the silver halide emulsion. In this method, a polymer coupler is polymerized by solution polymerization together with a copolymer component, and the resulting polymer coupler is dissolved in a solvent, and then dispersed in an aqueous gelatin solution to form a latex. Regarding the former emulsion polymerization method, U.S. Pat. Nos. 3,370,952 and 4,080.21
1% respectively. The latter method is described, for example, in US Pat. No. 3,451,820. The method of adding such polymer couplers in latex form to the hydrophilic Coro 6 composition has the following advantages over other methods.

That is, the latex of the polymer coupler can contain a high concentration of one coupler unit and does not contain a high boiling point organic solvent, so it can be formed into a thin film and the sharpness can be improved. Furthermore, since the aqueous gelatin solution does not thicken much, high-speed uniform coating is possible. Furthermore, since the polymer coupler is made into latex, the strength of the formed film will not deteriorate.

There are several types of tsuba in which a polymer coupler is added to a silver halide emulsion in the form of a latex. For example, US Patent No. 4,080,211, US Patent No. 3,451,820, British Patent No. 1,247.68
No. 8 describes a method for making a 4-equivalent magenta dye-forming polymer coupler latex, and U.S. Pat. γ6
γ, No. 412 describes latexes of cyan dye-forming polymer couplers, and U.S. Pat. No. 3,926,436
Copolymerized latexes with competing couplers are described in German Patent No. 2,725,591 and German Patent No. 2,725,591.

Furthermore, U.S. Patent Nos. 4,080,211 and 3,926
, No. 43G, Unpublished Il! ? 52-153737, U.S. Patent No. 2,976.294, U.S. Patent No. 3,370,952
No. 3,515,557, No. 3,451,82
No. 0 contains a 4-equivalent dye-forming polymer coupler latex, as disclosed in JP-A-58-42044 and JP-A-59-362.
No. 49 and No. 59-42543 describe a 2-equivalent dye-forming polymer coupler latex.

The above-mentioned 2-equivalent yellow dye-forming polymer coupler latex is a polymer derived from a 2-equivalent yellow coupler monomer having a polymerizable group in a portion of the coupler, and the granularity has not been improved in any way.

The 2-functional yellow dye-forming polymer coupler latex of the present invention is a polymer derived from a 2-functional yellow coupler monomer having a polymerizable group in the releasable substituent moiety at the active position of the coupler. It also had great effects on sharpness, fogging, roughness, and discoloration of pigmented images.

(2) Object of the Invention The first object of the present invention is to provide a silver halide color photographic light-sensitive material with excellent graininess using a novel 2-equivalent yellow dye-forming polymer coupler latex.

A second object of the present invention is to provide a novel 2-E dye-forming polymer coupler latex which has sufficient reactivity and forms dyes in high yields without producing unnecessary capri or stain. An object of the present invention is to provide a silver halide color photographic material.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material containing a 2-equivalent yellow dye-forming polymer coupler latex which has excellent film strength and improved image sharpness by forming an S film. .

A fourth object of the present invention is to provide a silver halide color photographic light-sensitive material having a robust dye image with excellent light fastness, heat resistance, and moisture resistance using a novel 2-equil dye-forming polymer coupler latex. The goal is to provide the following.

A fifth object of the present invention is to reduce the amount of silver halide and the amount of coupler used in photographic emulsion layers containing the novel 2-equivalent yellow dye-forming polymer coupler latex. An object of the present invention is to provide photographic materials.

■ Structure of the Invention As a result of research on various yellow couplers, the present inventors have discovered that a yellow dye-forming polymer marker having a repeating unit represented by the following general formula [IF] can form a dye on a support using an alkaline color developer. It has been found that the above object can be achieved by a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a blur latex.

General formula [I] (wherein, RL represents an alkyl group or an aryl group, R2 represents a -valent group, Q has an ethylenically unsaturated group, and a coupling reaction with an oxidized product of a color developing agent (12 represents an integer of O to 5) Hereinafter, the present invention will be explained in more detail.

R1 in the general formula [I] is an alkyl group or an aryl group. This alkyl group has 3 carbon atoms
to 20 straight-chain or branched alkyl groups are preferred, more preferably 4 to 8 straight-chain or branched alkyl groups (e.g.
tert-butyl group, n-butyl group, n-amyl group, t
ert-amyl group, sea-amyl group, n-octyl group, tert-octyl group, etc.), particularly preferably tart-butyl group.

This alkyl group also includes a cycloalkyl group (for example,
cyclohexyl group), and may further have a substituent. As shown in Rt above, this aryl group may have a substituent.

Substituents for the aryl group include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), alkyl groups having 1 to 8 carbon atoms (methyl group, ethyl group, 1so-propyl group, te
rt-butyl group, 5ea-amyl group, tert-octyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.), aryloxy groups (e.g., phenoxy group, etc.), alkylsulfonamide groups (e.g., methane sulfonamide group, ethanesulfonamide group, etc.), arylsulfonamide group (e.g., phenylsulfonamide, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyl oxycarbonyl group, etc.), acylamino group (e.g., acetylamino group, pivaloylamino group, etc.), alkylsulfamoyl group (e.g., methylsulfamoyl group, dimethylsulfamoyl group, etc.), arylsulfamoyl group (e.g., phenylsulfamoyl group, etc.), alkylcarbamoyl group (e.g., methylcarbamoyl group, etc.), arylcarbamoyl group (e.g., phenylcarbamoyl group, etc.), alkyl or arylsulfonyl group (e.g., methylsulfonyl group, phenylsulfonyl group, etc.) These are a nitro group and a cyano group, and the number of these substituents may be two or more, and 2(l1
In the above cases, they may be the same or different. R1 in the general formula
When is a phenyl group, substituents include an alkoxy group,
Preferred are halogen atoms, alkyl groups and alkylsulfonamide groups.

Examples of the monovalent group represented by R2 in general formula [I] include a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an aryloxy group, an alkylsulfonamide group, an arylsulfonamide group, and an alkoxycarbonyl group. group, aryloxycarbonyl group, acylamino group, alkylsulfamoyl group, arylsulfamoyl group, alkylcarbamoyl group, sulfonyl group, nitro group, cyano group and the like. Among these, preferred are a halogen atom, an alkoxy group, an alkylsulfonamide group, an acylamino group, and an alkoxycarbonyl group. Friend represents an integer from 0 to 5, and when p is 2 or more, RZ may be the same or different.

Q has an ethylenically unsaturated group, and due to the coupling reaction with the oxidized product of the color developing agent! ! It is a removable group, preferably represented by the following general formula CI].

General formula [II] R.

CH, = C- + R4 te group (eg, methyl group, ethyl group, etc.). This alkyl group may have a substituent.

R4, R5 and R6 represented by the general formula [I[] are
Each represents an alkylene group, an arylene group, or an aralkylene group having 1 to 20 carbon atoms. The alkylene group may be linear or branched. Examples of such an alkylene group include a methylene group, a methylmethylene group, a dimethylene group, and a decamethylene group. Examples of the arylene group include a phenylene group and a naphthylene group. Examples of the aralkylene group represented by R4, R5 and R6 include a benzylene group.

The alkylene group, arylene group, or aralkylene group represented by R4, RS, and R6 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 [I] is 100N) (-1-
NHCO-1-NHCONI-1-1-COO-1-〇〇〇-1-8O2-1-S-1-CO-1-SO-1-
0- represents a bonding group, among which preferred is -C
ONH-1-N) (CONH-1-COO=, -8O2
-1-S-1-〇-.

Y represented by the general formula [I[] is 100NH-1-
NHCO-1-NHCONH-1-COO-1-〇C〇-1-8O2NH-1-N l-I S O2-1-8
02- represents a divalent bonding group, among which preferred ones are -CONH-1-〇C〇-1-8○2 NH-1-
502-tet6Z+.

mS n, o, p, and q represent O or 1.

2 is a group that can be separated by a coupling reaction with an oxidized product of a color developing agent, and can be represented by the following general formulas [[] and [IV].

In the formula, * represents the active position of the coupler, A represents an M elementary atom or a sulfur atom, B represents a group of nonmetallic atoms necessary to form an aryl ring or a heterocycle, and E represents a group of atoms together with an arsenic atom. Represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle. These rings may further be fused with an aryl ring or a heterocycle.

2 represented by the general formula [I1[] is a divalent group derived from an aryloxy group, an oxacylyloxy group, a chroman-4-oxy group, a tetrazolyloxy group, an arylthio group, etc. 2 represented by [IV] includes a urazole group, a hydantoin group, a tetrazolone group, a triazole group, a diazole group, a succinimide group, a saccharin group, a pyridone group, a ridazone group, an oxazolidinedione group, and a thiosilydinedione group. It is a divalent group derived from a group, etc., and preferably a divalent group derived from an aryloxy group, a urazole group, a hydantoin group, a tetrazolone group, and a razole group.

Groups 2 represented by general formulas [III] and [rV] are
It can have a substituent, and examples of the substituent include an alkyl group, an aryl group, an aralkylene group, a halogen atom,
Examples include alkoxy groups, hydroxy groups, nitro groups, amine groups, carboxylic acid ester groups, carboxylic acid groups, and sulfonic acid groups.

In the following, typical examples of the coupler monomer represented by the general formula CI) will be described, but the present invention is not limited thereto.

Former α) C, H, fυ Typical production examples of the coupler monomer according to the present invention are shown below.

Synthesis Example 1 [Exemplary coupler monomer (1) 22.8 g of coα-chloroα-pivaloyl-2-chloroacetanilide
and 1-(p-nitrophenylmethyl)hydantoin 23
．． 50 was dissolved in 1 volume of acetonitrile. 20.2Q of triethylamine was added to this solution, and the mixture was heated under reflux for 8 hours. Acetonitrile was concentrated under reduced pressure, poured into 1Ω water, and neutralized with acetic acid.

The precipitated crystals were filtered, washed with water, dried, and α-pivaloyl-
α-[I-(1)-nitrophenylmethyl)-hydantoin-3-yl2-chloroacetanilide 35,5
1; l was obtained.

The above nitro compound, 21.3σ, was dissolved in 2 sod of acetone, and powdered tin 23.7Q was added. Under air conditioning and stirring vigorously, add 37% of concentrated hydrochloric acid. sJ was added dropwise over 30 minutes. After roughly stirring for 1 hour, the mixture was poured with water, neutralized with sodium bicarbonate, and extracted with ethyl acetate.

After drying over anhydrous sodium sulfate, the ethyl acetate was distilled off under reduced pressure to obtain 10.2 g of α-pivaloyl-α-1-(p-aminophenylmethyl)hydantoin-3-yl)-2-chloroacetanilide.

The above amine compound was dissolved in 10011i of tetrahydrofuran, and 2.8 g of pyridine was added. While keeping this solution at 5° C. or lower, 3.29 g of methacrylic acid chloride was added dropwise. After the addition, the mixture was stirred at room temperature for 1 hour and poured into 1 glass of water.

The precipitated crystals were filtered, washed with water, dried, and then recrystallized from acetonitrile to obtain 6.8 g of exemplified coupler (1). m
p168-171℃, structure is NMR, Mass and r
It was determined using R.

Synthesis Example 2 [Exemplary coupler monomer (4) 1α-bromo-
α-benzoyl-2chloroacetanilide 29.5Q and 1-(p-nitrophenylmethyl)-2-phenylurazole 25. Dissolve OQ in 200t of chloroform,
16.2 g of triethylamine was added, and the mixture was left at room temperature day and night. The chloroform solution was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was recrystallized from toluene to give 29.8 g of α-benzoyl-α-[I
-(p-nitrophenylmethyl)-2-phenylurazol-4-yl-2-chloroaceanilide was obtained.

20.0 g of the above nitro compound was dissolved in 17 od of acetone, and 16.1 g of powdered tin was added. At room temperature, 2 seconds of concentrated hydrochloric acid ad was added dropwise over 30 minutes while stirring vigorously.

After further stirring for 1 hour, the mixture was poured with water, neutralized with sodium bicarbonate, and extracted with ethyl acetate.

After drying over anhydrous sodium sulfate, distillation was performed under reduced pressure with ethyl acetate to give α-benzoyl-α-N-(1)-aminophenylmethyl)-2-phenylurazol-4-yl]-2-
10.8 g of chloroacetanilide was obtained.

The above amino compound was dissolved in 1001 U of acetonitrile, and 2. Oa+ fl was added. Add this solution to 5
Methacrylic acid chloride 2.39 while keeping the temperature below ℃.
was dripped. After the dropwise addition, the mixture was stirred at room temperature for 1 hour and poured into 1 cup of water. The precipitated crystals were filtered, washed with water, dried, and then recrystallized from acetonitrile to obtain 6.29 exemplified coupler (4). mp196-199°C, structure was determined using NMR, Mass and IR.

Synthesis Example 3 [Exemplary coupler monomer (11)] α-chloroα-pivaloyl-2chloroacetanilide 72.
1 flI and 45.2Q of 4-(p-aminophenyl)-1H-tetrazolone were dissolved in 27011IN of acetone, 34.6Q of potassium carbonate was added, and the mixture was heated under reflux for 2 hours. After cooling, vinegar u3smu was added and poured into 1 g of water. The precipitated crystals were filtered, washed, dried, and then recrystallized from ethanol.
93.5 g of -[4(p-7minophenyl)tetrazolon-1-yl]-2-chloroOacetanilide was obtained.

21.41;l of the above amino compound and 5.5g of pyridine
oomQ was dissolved in acetonitrile, and 6.3 g of methacrylic acid chloride was added dropwise to this solution while keeping the temperature below 5°C. After the dropwise addition, the mixture was stirred at air temperature for 1 hour, and poured into one drop of water.

The precipitated crystals were filtered, washed with water, dried, and then recrystallized from acetonitrile to obtain 17.59 exemplified coupler (11).

mp202-205℃, structure is NMR.

Determined using Mass and IR.

Synthesis Example 4 [Exemplary coupler monomer <16) rα-pivaloyl-α-(4-(4-hydroxybenzenesulfonyl)
[phenoxy]2-chloroacetanilide 10.0 G
, chloromethylstyrene (Illp mixture >3.4g#
Dissolve 0.5 g of Tjp-methoxyphenol in some dimethylformamide. 1.7 g of potassium charcoal was added to this solution, and the mixture was stirred at the lowest temperature all day and night, then stirred at 50° C. for 1 hour, and then poured into 500 IllN water. It was neutralized with acetic acid, and the newly formed crystals were filtered, washed with water, and dried. The product was purified using silica gel column chromatography to obtain 5.2 g of exemplified coupler (16).

lll0135~139℃, structure is NMR, Mas
Determined using s and IR.

Synthesis Example 5 [Illustrative coupler monomer (21>F α-benzoyl-α-[I-(1)-aminophenylmethicin-2-phenylurazol-4-yl]-2-chloroacetanilide of Synthesis Example 2) 27. Dissolve 5.5 g of 71;l pyridine in 200111.Q 7cetonitrile, and while keeping this solution below 5°C, dissolve 6-7 chloroylamino-
12.2 (l) of caproyl chloride was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 1 hour and poured into 1 cup of water. The precipitated crystals were filtered, washed with water, dried, and then recrystallized from acetonitrile.
An exemplary coupler (21) of i5,3Q was obtained. mp14
8-151°C, structure determined using NMRXMass and IR.

The polymer coupler according to the present invention may be a so-called homopolymer consisting only of repeating units represented by the general formula [I], or a so-called copolymer with other copolymerizable comonomers, In the present invention, copolymerized polymer couplers are preferred. Examples of comonomers that can be copolymerized include acrylic esters, methacrylic esters, vinyl esters, olefins, styrenes, croton esters, itaconic diesters, maleic diesters, fumaric diesters, and the like.

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-chlorobuty.

acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate,
Cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5- and droxypentyl acrylate, 2.
2-dimethyl-3-hydroxypropyl acrylate,
2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-
iso-propoxy acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of moles added n-9), 1- Examples include 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, isoprogol acrylate, n-butyl methacrylate, isobutyl methacrylate, 5ea-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate. , chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N
-ethyl-N-phenylaminoethyl methacrylate,
2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, talesyl methacrylate, naphthyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, Ethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2
-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2- Examples include (2-butoxyethoxy)ethyl methacrylate and ω-methoxypolyethylene glycol methacrylate (additional mole number n-6).

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, etc. Can be mentioned.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, nylidene 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 the itacon diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

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

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

Examples of other comonomers include:

Acrylamides, such as acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Methoxyethyl acrylamide, dimethylaminoethyl acrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethyl acrylamide, etc. Allyl compounds, such as allyl acetate, allyl capron, allyl laurate, allyl benzoate, etc. Vinyl ethers, e.g. Methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyedyl vinyl ether, dimethylaminoethyl vinyl ether, etc. Nyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc. Vinyl heterocyclic compounds, such as: Niglycidyl esters such as vinyl and lysine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, and N-vinylpyrrolidone, such as glycidyl acrylate, glycidyl methacrylate, etc.; unsaturated nitriles, such as acrylonitrile, methacrylateril, 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, ditraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, acryloyl Oxyalkylsulfonic acids, such as acryloyloxymethylsulfonic acid; methacryloyloxyalkylsulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; acrylamide alkylsulfonic acids, such as 2- Acrylamide-2
-methylethanesulfonic acid, 2-acrylamide-2-
Methylpropanesulfonic acid, 2-acrylamide-2-
Methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acids, 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-
Phosphates, etc.: Methacryloyloxyalkyl phosphates, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, and the like. These Shun are alkali gold i
(eg, Na, Ni, etc.) or ammonium ion salts. Furthermore, other comonomers include U.S. Pat. No. 3,459,790 and U.S. Pat.
No. 8.708, No. 3,554,987, No. 4, 2
No. 15.195, No. 4,247,673, Japanese Unexamined Patent Publication No. 1973
Crosslinkable monomers described in JP 7-205735 and the like can be used. Specific examples of such crosslinkable monomers include N-(2-7cetoacetoxyethyl)acrylamide, N-(2-(2-acetoacetoxyethoxy)ethyl)acrylamide, and the like.

Among these comonomers, acrylic esters and methacrylic esters are preferably used in view of the hydrophilicity and lipophilicity of the comonomers, the copolymerizability of the comonomers, the coloring properties of the produced polymer couplers, and the color tone of the produced dyes. , maleic esters, acrylamide, and methacrylamide.

Two or more of these comonomers may be used in combination. 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, and in that case, preferably the repeating unit represented by general formula [I] is 30 to 30% of the total by weight.
This is the case where the content is 80%, particularly preferably 40 to 10%.

The yellow dye-forming polymer coupler latex of the present invention may be prepared directly by an emulsion polymerization method, or a lipophilic polymer coupler obtained by polymerization of coupler monomers may be dissolved in an aqueous solvent, and the latex may be prepared in an aqueous gelatin solution. It can be made in a distributed manner. Regarding the emulsion polymerization method, U.S. Patent No. 4.080211 and U.S. Pat.
No. 52 and US Pat. No. 3,451,820 for dispersing lipophilic polymer couplers in latex form in aqueous gelatin solutions 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 yellow dye-forming polymer coupler latex of the present invention, a water-soluble polymerization initiator and a lipophilic polymerization initiator are used. Examples of water-soluble polymerization initiators include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, 4°4'-7zobis-4-cyanosodium oxygen, 2,2'-azobis(2 Water-soluble azo compounds such as -amidinopropane) hydrochloride and hydrogen peroxide can be used. In addition, examples of the lipophilic polymerization initiator used in the solution polymerization method include azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis(4 -methoxy-2,
4-dimethylvaleronitrile), 1,1'-azobis(
Lipophilic azo compounds such as cyclohexanone-1-carbonitrile dimethyl sobutyrate, diethyl 2,2'-azobisisobutyrate, benzoyl peroxide, lauryl peroxide, diisobrobyl peroxydicarbonate, and di-tert-butyl peroxide. be able to.

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

Examples of anionic activators include soaps, sodium dodecylbenzenesulfonate, sodium lauryl sulfate,
Examples include sodium dioctyl sulfosuccinate and sulfates of nonionic surfactants.

Examples of nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene stearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene-polyoxybrobylene block copolymer, and the like. Examples of cationic activators include alkylpyridium salts and tertiary amines.

Furthermore, examples of amphoteric surfactants include dimethylalkylbetaines, alkylglycines, and the like. Further, examples of the polymeric protective colloid include polyvinyl alcohol, droxyethyl cellulose, and the like. 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, please refer to 3e1gisch.
eChemische Industries, 2
8, pp. 16-20 (1963).

In order to disperse a lipophilic polymer coupler synthesized by a solution polymerization method in the form of a latex in an aqueous gelatin solution, the lipophilic polymer is first dissolved in a specific solvent, and then dissolved in an aqueous gelatin solution with the help of a dispersant. Then, it is dispersed into a latex form using ultrasonic waves, a colloid mill, etc. For a method of dispersing lipophilic polymer couplers in latex form in aqueous gelatin solutions, U.S. Pat.
No. 820. As the solvent for dissolving the lipophilic polymer coupler, esters such as methyl acetate, ethyl acetate, propyl acetate, alcohols, ketones, halogenated hydrocarbons, ethers, etc. can be used. Moreover, these organic solvents can be used alone or in combination of two or more.

Next, the production of the polymer coupler of the present invention will be specifically described below, but the present invention is not limited thereto.

Production method example (1) of yellow dye-forming polymer coupler latex Production of lipophilic polymer coupler latex (A) of exemplary coupler monomer (4) and n-butyl acrylate 10 g of exemplary coupler monomer (4), 10 g of lobethyl acrylate, and dioxane 12011IN a mixture of 8
Azobisisobutyronitrile dissolved in dioxane (4 mJ) was stirred at 0°C in a nitrogen stream. 36! I+
was added, and the mixture was reacted for 6 hours. A dioxane solution was added dropwise into two glasses of water, and the precipitated solid was filtered out, washed with water, and dried to obtain a lipophilic polymer coupler of 17.5 (1 (88%). Copolymer composition of this polymer coupler. According to elemental analysis (nitrogen analysis), the content of coupler monomer (4) was 52.1%.

10 g of the above polymer coupler was dissolved in 30 d of ethyl acetate, and to this solution was added a mixed solution of 6 ml of a 10% aqueous solution of sodium lauryl sulfate and 1 oomu of a 5 wt % aqueous solution of gelatin, followed by ultrasonic dispersion. Thereafter, ethyl acetate was removed by vacuum distillation to obtain a polymer coupler latex (A).

Production Example (2) Production of a coupler latex (B) in which the lipophilicity of the exemplified coupler monomer (11) and methyl acrylate is polymeric.

A mixture of 10 g of exemplary coupler monomer (11), 10 g of methyl acrylate, and 120 + nΩ of dioxane was heated to 80°C.
After stirring in a nitrogen stream and adding 0.36 g of azobisisobutyronitrile dissolved in 4 n+Jl of dioxane, the mixture was reacted for 6 hours. A dioxane solution was added dropwise to 2 ml of water, the precipitated solid was filtered out, washed with water and dried.
,01;l (90%) of the polymer coupler was obtained.

The copolymer composition of this polymer coupler was determined by elemental analysis (nitrogen analysis) to show that the content of coupler monomer (11) was 50.8.
%Met.

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

Production Example (3) Production of lipophilic polymer coupler latex (C) of exemplified coupler monomer (16), n-butyl acrylate and methyl acrylate.

Exemplary coupler monomer (16) 10q, 5 n-butyl acrylate, 5g methyl acrylate, and 2oom tert-butanol! The mixture of 2 was stirred under reflux in a nitrogen atmosphere, and 0.36 (] of azobisisobutyronitrile dissolved in 10 d of tert-butanol was added, followed by a reaction for 6 hours. The tert-butanol solution was added dropwise to 2 g of water. The precipitated solid was filtered, washed with water and dried,
g (88%) of the lipophilic polymer coupler was obtained. The copolymer composition of this polymer coupler was determined by elemental analysis (nitrogen analysis).
The coupler monomer (16) content was 51.8%.

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

Production Example (4) Production of polymer coupler latex (A') of exemplified coupler monomer (1) and n-butyl acrylate.

Exemplary coupler monomer (1) 10a and 10 g of lobethyl acrylate were heated and dissolved in 200111 (l) of ethanol. Sodium salt of oleyl methyl tauride 2
The aqueous solution aoomU in which Q was dissolved was heated to 95°C and stirred in a nitrogen stream, and then potassium persulfate + 40 mg of 2
0 mM aqueous solution was added. Next, the above-mentioned ethanol solution was added dropwise over 1 hour. After completion of the dropwise addition, heat and stir at 95 to 85°C, and after 3 hours, add 60 mg of potassium persulfate to 201
An aqueous solution was added and the mixture was further stirred at the same temperature for 3 hours, after which ethanol and unreacted n-butyl 7-acrylate were distilled off as an azeotropic mixture of water.

The solid content concentration of the formed latex was 10.2 wt%,
The copolymer composition was found to have a coupler monomer (1) content of 52.8% by elemental analysis.

Production Example (5) Production of polymer coupler latex (B') of exemplified coupler monomer (21) and ethyl acrylate.

15 g of the exemplary coupler monomer (21) and 5 g of ethyl acrylate were heated and dissolved in ethanol zoomU. 800 mΩ 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 then 140 m of potassium persulfate (20 Il19 of 1
Aqueous solution was added. Next, the above-mentioned ethanol solution was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was heated and stirred at 95 to 85°C, and after 3 hours, a 20 mM aqueous solution of 60 mg of potassium persulfate was added, and the mixture was stirred at the same temperature for an additional 3 hours. After that, ethanol and unreacted ethyl acrylate were distilled off as an azeotrope of water. I left.

The solid content concentration of the formed latex was 12.5 wt%,
The copolymer composition was determined by elemental analysis of the coupler monomer (21)
The content was 76.1%.

Production method examples (6) to (40) Production method examples (1), (2) using the coupler monomers,
(3) (Manufacturing method example) and Manufacturing method example (4), (5) (Manufacturing method ■
) The following polymer coupler latex was obtained in the same manner as the copolymer.

Manufacturing method I Manufacturing method ■ Ne1 BA: n-butyl acrylate t -BA: tert-7 chill 7';y'J rate E
A: ethyl acrylate MA: methyl acrylate BMA: n-butyl methacrylate MMA: methyl methacrylate HA: n-hexyl acrylate)-IEMA:
2-Hydroxyethyl methacrylate AAM Niacrylamide DAAM Nidiacetone Acrylamide St: Styrene AA Niacrylic acid AMPS: 2-Acrylamide-2-methylpropane sulfone The yellow dye-forming polymer coupler latex of the present invention also has the general formula [V] and DI represented by [■]
It is preferable to use it together with R compound.

General formula [V] Cp-IN5 General formula [VI] Cp-TIME-INH where G
o 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 [V], INH binds to the coupling position of the coupler component and is released from ffi by reaction with the oxidized product of the color developing agent. TI of general formula [VI]
The ME group is bonded to the coupling position of the coupler, desorbed by reaction with the oxidized form of the color developing agent, and then INH
This is a group that can be released in a moderately controlled manner.

Coupler components represented by Co 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 [■, [■]
, [rX].

-Q2 Formula [■ In the formula, R9 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R8 and R9 each represent an aromatic group or a heterocyclic group.

The aliphatic group represented by R7 preferably has 1 to 20 carbon atoms and may be either a substituted or unsubstituted chain or cyclic group. Preferred substituents for the alkyl group include alkoxy, aryloxy, and acylamino groups. Especially preferred as R7 is a tert-butyl group. When R9, R8 or R9 is an aromatic group, it represents a phenyl group, a naphthyl group, etc., and a phenyl group is particularly useful, and 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.

The phenyl group represented by RFI, Rg and R9 may be substituted with an alkyl group, an alkoxy group, a cyano group or a halogen atom.

Rho represents a hydrogen atom, an alkyl group, a halogen atom, etc., and 92 is an integer of 1 to 5, preferably a hydrogen atom. R++ and R+2 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. R1
+ and R+2 may be the same or different.

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

General formula [X] General formula [XI] ■ R1゜RlB is an alkyl group, alkoxy group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, halogen atom, carbamoyl group, nitro group, cyan group, sulfamoyl group , hydroxy group, etc., and ρ3 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 the substituent is an alkyl group. , an alkoxy group, a halogen atom, a human oxy group, etc.

TIME! :Lri;t, especially -122 formula [XU]
.

Those represented by rxmi and [XI%rj are preferred, but others such as -0CH2-1NH-OCO-I NH are also available.

General formula [XIt] Blue 16 General formula [Xii[] R+q represents a hydrogen atom, an alkyl group, an alkoxy group, anilino group, a nitro group, an aryl group, a carboxy group, a cyan group, etc., and Ω4 is an integer of 1 or 2. be. RI6 represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, or an aryl group;
When I6 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.

Next, preferred DIR compounds used in the present invention are shown below, but the present invention is not limited thereto.

Margin below - I ]) -5 D - 8 QH ]) -9 Shidan. N-N The yellow dye-forming polymer coupler of the present invention is
When used together with an R coupler, it is particularly preferable to contain them in the same layer. In this case, the DIR coupler is contained in an amount of o,oooi to 0.5 mol, preferably o,ooi to 0.05 mol, per mol of silver.

The yellow dye-forming polymer coupler latex of the present invention is preferably used in combination with an oxidized developing agent scavenger along with the DIR compound. Preferred oxidized developing agent scavengers are represented by the following general formulas [XV] to [X■].

General formula [XV] &6 In the formula, x2 represents a hydrogen atom, an alkyl group, an alkoxy group or a 10Y2 group. Y2 is preferably a hydrogen atom, an acyl group, or an alkoxycarbonyl group, and particularly preferably a hydrogen atom. R1-1, RI, 9 and RIq are each a hydrogen atom, an alkyl group, a halogen atom, -802R2
1, -COR2+, 7) Lr co*cy group, 7/L.

Represents a kylthio group or an aryl group. R21 represents an alkyl group, an alkyloxy group, an alkylamino group, an aryl group, an aryloxy group, an arylamino group, etc.
Each of these may have a substituent. Q2 represents a sulfonyl group, acyl group, carboxyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfinyl group or cyano group. R2o is Rn-R
Represents the same group as Iq, and Ds is O~2! 1! represents a number, and when p is 2, R20 may be the same or different.

NH30,R,.

In the formula, Y3 f, t are the same as Y2 in the general formula EXvJ, [XVI, and R22 each has 1 to 1 carbon atoms.
These are 30 alkyl groups and aryl groups having 6 to 30 carbon atoms, and these may optionally have a substitute.

R23, R24 and R2r each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, etc., with a hydrogen atom being particularly preferred.

General formula [X■] C, -8QL "In the formula, Cρ is the same as Co shown in the general formulas [VJ and [VN], and represents a coupler component.

SQL is a dye formed by a coupling reaction of a compound represented by the general formula [X] with an oxidized form of a color developing agent. It is a solubilizing group that gives it the property of being able to flow out of the material.

Examples of SQL include a carboxyl group, a sulfonyl group, and a hydroxy group. B2 is a group that binds to the coupling position of the coupler component and leaves by reaction with the oxidized product of the color developing agent, and is a component containing a ballast group having 8 to 32 carbon atoms.

Specific examples of oxidized developing agent scavengers that can be used in combination with the yellow dye-forming polymer coupler latex in the present invention are shown below, but the present invention is not limited thereto.

Below, the margin S -2 S -, 4 -5 C, H ! The content is 1 to 3 per mole of coupler component.
00 mol%, preferably 5.

~HIO mol%. By using such a W developing agent scavenger in combination, the oxidation products of the one-color developing agent are captured, the overlap between the dye cloud sludge and the dye cloud becomes smaller, and the graininess can be improved.

The yellow dye-forming polymer coupler latex of the present invention can be used alone or in combination with other couplers.

The miscible couplers are preferably non-diffusible couplers that have a hydrophobic group called a ballast group in the molecule, but U.S. Pat.
No. 4,215,195, British Patent No. 1,247,688
Polymer couplers described in JP-A-59-36249, JP-A-59-42044, and JP-A-59-42543 and water-soluble polymer couplers having a sulfonic acid group or a carboxylic acid group may be used.

Furthermore, VivaCyl7ceto7nilide couplers, benzoylacetanilide couplers, etc. may be used in combination as appropriate.

Specific examples of yellow dye-forming couplers that can be used in combination are U.S. Patent No. 2,875,057 and British Patent No. 1,077.87.
No. 4, U.S. W. Patent No. 3,408,194, Japanese Patent Application Publication No. 1983-1
No. 23342, ash-87650 1 lap 54-133
329@, Special Publication No. 46-19031, Special H [4B-2
No. 9432, @4&-66834, No. 48-668
No. 35, No. 48-94432, No. 5G-28834, No. 54-99433, JII No. 55-70841, No. 56-74249, Special Publication No. 19956-197,
This is described in Japanese Patent Application Laid-Open No. 51-102636, Volume 1, No. 56-8704i, etc.

The above coupler is US 5I ¥1 permit No. 2,269,158,
2.304,940, 2,322,027,
No. 2,772,163, No. 2,801,171,
Dispersed in hydrophilic colloid by the method described in British Patent No. 1,151,590@ etc., and the dispersion was
It can also be used by impregnating (loading) it into the yellow dye-forming polymer coupler latex of the present invention by the method described in No. 4, No. 51-39853. Here, impregnation (loading) means a state in which the hydrophobic yellow coupler is contained inside the latex of the yellow polymer coupler or a state in which the hydrophobic yellow coupler is deposited on the surface of the latex of the yellow coupler. However, the exact mechanism by which impregnation (loading) occurs is not known.

The yellow dye-forming polymer coupler latex of the present invention is disclosed in U.S. Pat.
No. 9, No. 2,336,327, No. 2,403,721, No. 2,701,197, No. 3,700,453, etc., British Patent No. 1,326,88
No. 9, U.S. Patent No. 3,432,300, U.S. Patent No. 3,698,
No. 909, No. 3,574,627, No. 3,573.0
50, No. 3,764,337, etc., may also be used in combination.

To introduce the above couplers into the silver halide emulsion layer,
For example, high-boiling point solvents such as tricresyl phosphate and dibutyl phthalate with a boiling point of 175°C or higher or low-boiling point solvents such as butyl acetate and butyl propionate can be used alone or as necessary, in the heated S*. After the above coupler is dissolved, it is mixed with an aqueous gelatin solution containing a surfactant, then emulsified in a high-speed rotating mixer or colloid mill, and then added to silver halide to prepare the silver halide emulsion used in the present invention. You can.

The yellow dye-forming polymer coupler latex of the present invention can be used as a color photographic light-sensitive material consisting of a blue-sensitive silver halide emulsion layer or a color photographic material consisting of a blue-sensitive silver halide emulsion layer consisting of two or more layers, a high-speed layer and a low-speed layer. Used in photosensitive materials. A color photographic light-sensitive material consisting of three layers, with an intermediate layer or an intermediate layer not containing silver halide emulsion inserted between the high-speed layer and the low-speed layer of the blue-sensitive silver halide emulsion layer consisting of the above two layers. 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 green-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.

Furthermore, the silver halide color photographic light-sensitive material of the present invention may contain a magenta coupler.

Examples of magenta couplers that can be used include U.S. Pat.
No. 8, No. 3,062,653, No. 3,127,2
No. 69, No. 3,311,476, No. 3,419,
No. 391, No. 3,519,429, No. 3,558
, No. 319, No. 3,582,322, No. 3,61
No. 5,506, No. 3,834,908, No. 3,8
No. 91.445, West German Patent No. 1,810,464, West German Patent Application (OL S) No. 2,408,665,
JP 2,417,945, JP 2,418,059, JP 2,424,467, JP 40-6031, JP 51-20826, JP 52-58922,
No. 49-129538, No. 49-74027, No. 49-74027, No. 49-129538, No. 49-74027, No.
No. 50-159336, No. 52-42121, No. 49
-74028, 5G-60233, 51-26
No. 541, No. 53-35122, No. 57-35858
Examples include couplers described in No. 58-217932.

Furthermore, the color photographic material of the present invention can also be used in combination with generally well-known colored couplers.

Examples of colored couplers used in combination include U.S. Pat. No. 3,148,062, U.S. Pat. No. 3,227,554, U.S. Pat.
Same No. 3,703,375, Same No. 3,815,506, Same No. 3,265,506, Same No. 3,620.745
No. 3,632,345, No. 3,869.29
No. 1, No. 3,642,485, No. 3,770,4
No. 36, No. 3,808,945, British Patent Nos. 1 and 2
Colored couplers described in Japanese Patent No. 01,110 and Japanese Patent No. 1,236,767 are mentioned.

Additionally, a cyan coupler can be used in the silver halide color photographic light-sensitive material of the present invention.

Examples of such cyan couplers include phenol compounds and naphthol compounds.

Furthermore, either a low molecular weight cyan coupler or a cyan polymer coupler can be used.

Specific examples include U.S. Patent No. 2,369,929;
2,434,272, 2,423,730, 2,474,293, 2,521,908, 2
, No. 895,826, No. 3,034.892, No. 3
, No. 227,554, No. 3,311,476, No. 3
．． No. 458,315, No. 3,476.563, No. 3,
No. 583,971, No. 3,591,383, No. 3,7
No. 67.411, No. 4,004,929, West German Patent Application No. 2,414,830, No. 2,454,329, JP-A-48-59838, No. 51-26034, No. 4
L5055, L51-146828, L53-7
No. 3050, No. 53-109630, No. 55-32
No. 071, British Patent No. 1,543,040, Special Publication No. 1971
-36837, JP-A No. 56-65134, JP-A No. 58-
No. 118643, No. 56-1938, No. 56-271
No. 43, Special Publication No. 49-8228, No. 58-42044
No. 58-211756, No. 59-36249, No. 59-40643, No. 59-65844, No. 5
No. 9-86048, No. 55-85549, U.S. Patent 4
, No. 080,211, No. 3,767.412, No. 3
, No. 926,436, No. 56-161541, No. 926,436, No. 56-161541, No.
Examples include those described in No. 3,211.552.

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 the [I00] plane to the [I11] 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.

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 No. 58-10852 (No. 3, No. 58-1139)
No. 26, No. 58-113927, No. 58-1139
No. 28, No. 58-113934, No. 59-5542
It may also be a tabular grain silver halide emulsion described in No. 6, No. 59-90841.

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 silver halide emulsions of 2ff or more prepared separately.

Various binders can be used for the silver halide emulsion layer according to the present invention, such as gelatin, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin, polyvinyl alcohol, polyvinyl and lolidone, Non-electrolyte polymers such as polyacrylic acid amide, acidic polymer substances such as alginates and polyacrylates, polyacrylamide treated by Hofmann rearrangement reaction, and amphoteric polymers such as copolymers of acrylic acid and N-vinylimidazole. Electrolyte, U.S. Patent 4,215.1
Examples include the crosslinkable polymer described in No. 95.

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 41m: 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, activated gelatin powder and sulfur compounds can be used.

As the selenium layer sensitizer, active and inactive selenium compounds can be used.

Cyclic sensitizers include stannous salts, polyamines, alkylaminosulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and dorazine derivatives! In addition, this silver halide can be optically sensitized to a desired wavelength range, for example by using an optical sensitizer such as a cyanine dye such as a monomethine dye or a trimethine dye or a merocyanine dye alone or in combination. Can be optically sensitized.

In addition to the above-mentioned additives, the silver halide color photographic material of the present invention contains stabilizers, development accelerators, hardeners, surfactants, anti-staining agents, lubricants, ultraviolet absorbers, and formalin scavengers. Various other additives useful for photographic materials may also be 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.

The support may be appropriately selected from plastic film, plastic laminated paper, baryta paper, synthetic paper, etc. depending on the intended use of the photographic material. These supports are generally preferably subjected to a subbing process to enhance adhesion with the photographic emulsion layer.

The silver halide color photographic material of the present invention is useful in various forms. For example, color negative film,
Color positive film, color reversal film, color photographic paper, color reversal photographic paper, etc.

The silver halide color photographic material of the present invention requires development treatment after exposure in order to obtain a dye image. The development process basically includes color development, bleaching, and fixing steps.

Each process may be independent, or two or more of the processes may be performed in one process using processing liquids having those functions. Further, each step can be divided into two or more times as necessary. moreover,
Various steps such as pre-hardening, neutralization, first development (black and white development), stabilization, and water washing are combined as necessary in the processing steps.

The processing temperature is set within a preferable range depending on the photosensitive material and processing recipe, but is generally set between 18°C and 60°C. Note that the temperature settings for each series of treatment steps do not need to be the same.

After the silver halide color photosensitive material of the present invention is exposed to light, an alkaline color developer is 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. Typical examples of the main agent for this coloring phenomenon include p-phenylenediamine-based agents, such as diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, and dimethyl-p-phenylenediamine hydrochloride. salt, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, 2-amino-5-(N-ethyl-N-β-methanesulfonamide ethyl)amine toluene sulfate, 4-(N-ethyl-N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N
-β-hydroxyethylamino)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 hydroquinone and phenidone. Further, the color developing solution generally contains an alkaline agent such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfite, etc., and is an aqueous alkaline solution having I)H of 8 or more, preferably 9 to 12. Additionally, various additives may be included, such as alkali metal halides, such as potassium bromide, or development regulators, such as citrazine.

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, phthalate 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 described, for example, in U.S. Pat.
, No. 599, No. 2,507,114, No. 2,69
No. 5,234, No. 3,719,492, British Patent No. 303,783 Mei IB Zhan, JP 53-135628
No. 54-79035, Research Disclosure Magazine 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 photosensitive material, such as Kashihara, 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 Magazine 1485
It can also be added by impregnating it into a latex polymer, such as No. 2 softened.

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 iron (1), cobalt (■), and tin (■
), in particular complex salts of these polyvalent metal cations and organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-dooxyethylethylenediaminediacetic 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.

Example 1 Yellow dye-forming polymeric coupler latex of the present invention (A), (D), (M), (T), (A'), (L')
, (■') and (L') and comparative coupler (1), (
2), (3) and (4), each of silver iodobromide 5x1 in an amount containing 5x10 mol of one coupler monomer unit
High-sensitivity silver iodobromide emulsion 100 containing 0 mol and gelatin 10Q! The silver halide color photographic materials (Samples 1 to 12) having stable coating films were prepared by coating and drying on a triacetate support using a coated silver plate of 1.5 (J 7 m2).

For comparison couplers (1), (2), and (4), 1/2 times the coupler weight of tricresyl phosphate and 3 times the amount of ethyl acetate were added, and the mixture was heated to 60°C to completely dissolve. . This solution was mixed with a 5% gelatin aqueous solution containing Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and emulsified and dispersed using an ultrasonic disperser to obtain an emulsion.

Photographic materials were prepared in the same manner as Samples 1 to 12 above.

These samples F41 to F12 were each subjected to wedge exposure in a conventional manner and then subjected to the following development treatment.

Processing process (38℃) Processing time Color development phenomenon
Drifting for 3 minutes and 15 seconds Reason: Washing with water for 6 minutes and 30 seconds 3 minutes and 15 seconds
Fix in seconds 6 minutes 30 seconds Wash with water 3 minutes 15
Stabilizing bath for 1 minute and 30 seconds The composition of the treatment solution used in each treatment step was as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-(β- and droxyethyl)-aniline sulfate 4.75Q anhydrous sodium sulfite
4.250 hydroxylamine 1/
2TiA salt 2.0g anhydrous potassium carbonate
37.5g sodium bromide
1.3 g Nitrilotriacetic acid R3 sodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make a solution, and use potassium hydroxide to make 1) H10.0
Adjust to.

[Bleaching solution composition] Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Regarding the obtained yellow dye image, the graininess was measured by RMS
(Root Iaear Isqtre) method. R.M.

The S value is 1 standard deviation of the variation in the intensity value that occurs when scanning with a microdensitometer with a circular scanning aperture of $25μ.
000 times the value was used. The RMS granularity results at concentration 04 are shown in Table 1.

Also, dye ii! The storage stability of W@ was expressed as the residual rate of the highest concentration ([)max) after storage at 60° C. and 80% RH for 2 weeks, and the values are shown in Table 111.

Comparison couplers (1), (2), (3) and (4)
has the following structure.

The following margin comparison coupler (1) (JP-A-59-87650 number compound) Comparison coupler (3) (JP-A-59-425
Compound described in Publication No. 43) Comparative coupler (4) (Patent application No. 5
Compounds described in No. 8-250989) Margin table below 1 As shown in Table 1, comparative couplers (1), (
2) and (3) showed good values in image storage stability, but were considerably poor in graininess (RMS value). Comparative coupler (4) had significantly improved graininess, but
There was a significant deterioration in image storage stability. In contrast, the yellow dye-forming polymer coupler latex (A) of the present invention,
(D), (M), (T>, (A'), (E'), (
All the samples using 1') and (E') had excellent performance satisfying both graininess and image storage stability.

Example 2 Latex (○), (S) of the polymer coupler of the present invention
, (E') and (N') and comparative coupler (4), each containing 7 units of yellow dye-forming coupler monomer.
．． A base containing 5 x 10 moles of silver chloride bromide was mixed with 100 g of a photographic emulsion containing 5 x 10 moles of silver chlorobromide and 10 g of gelatin, and a 0.2% aqueous solution of 2-hydroxy-4,6-dichloro-s-triazine sodium salt was added as a hardening agent. 10 mρ was added to give a coated silver amount of 0.50 on a polyethylene-coated support.
/I2 and dried to obtain silver halide color photographic materials (samples Nos. 0.13 to 17).

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

Processing process color development 3 minutes 30 reasons white fixing
Wash with water for 1 minute and 30 seconds
2 minutes 0 seconds [Color developer] Benzyl alcohol 15.0 d Sodium hexametaphosphate 2.5 g Anhydrous sodium sulfite 18.5 g Potassium bromide
0.60g borax (NazB40q 1O
Hz ○) 39.10gN-ethyl-N-(2-(methanesulfonamidoethyl))-3-methyl-4-aminoaniline sulfate 5.0g Add water to make up to 11, and dilute with sodium hydroxide t)H10 , adjusted to 3.

[Bleach-fix solution] Ethylenediaminetetraacetate iron ammonium G1. OG ethylenediaminetetra-acetic acid diammonium 5.0 g Thiosorum acid-resistant ammonium 124.5 g Sodium metabisulfite 13.3Ω Thorium
Add 2.1g water to make 1p, I)H
was adjusted to 6.5.

The image storage properties of the yellow dye images obtained by developing the six samples under the above conditions were measured in the same manner as in Example 1, and the results are shown in Table 2.

As shown in Table 2 below, the image storage stability of the yellow dye-forming polymer coupler latex of the present invention was better than that of the comparative couplers.

Margin Example 3 A multilayer color photosensitive material consisting of each layer having the composition shown below (
Sample 18) was prepared.

1st layer: Antihalation layer Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer 2. Gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone 3rd layer: Red-sensitive low-sensitivity emulsion layer Silver iodide emulsion (silver iodide: 4 mol%) Silver coating (average grain size 0.5 μ) 1.79 g/m2 Sensitizing dye processing: 6 x 10 per mole of silver Molar sensitizing dye ■・・・1.5X 1 per mole of silver
0 mole Coupler A: 0.06 mol per mol of silver Coupler C: 0.003 mol per mol of silver DIR compound D-7: 1 mol of silver 0 for
, 003 Moltricresyl phosphate coating In 0.3cc/m
"4th layer: Red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol%...Silver coating 5 (average grain size 0.7u) 1.4a 7m" Sensitizing dye processing. ...3 x 10 moles per mole of silver Sensitizing dye ■...1.2X 1 per mole of silver
0 mole coupler F...0.0120 per mole of silver
Molar coupler C...0.0020 per mole of silver
Moltricresyl phosphate coating amount 0.2cc/a+2
5th layer: Intermediate layer Same as 2nd layer 6th layer: Green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol%...Amount of coated silver (average grain size 0.5u) 1. Og/m2 Sensitizing dye ■・・・3×10 mol per mol of m Sensitizing dye ■・・・1×10 mol per mol of silver Coupler B・・・・・・1 mol of silver 0.08 mole for Coupler M...O, ooa mole for 1 mole of silver DIR Compound D-7...0 for 1 mole of silver
．． 0015 Moltricresyl phosphate coating ti 1.4cc/
m" 7th layer: Green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide niamol%...Amount of coated silver (average grain size 1.2μ) 1.6g 7m" Sensitizing dye... ...2.5x 10 per mole of silver
Molar sensitizing dye ■---o, ax i per mole of silver
o Molar coupler B...0.02 moles per mole of silver Coupler M...0.003 moles per mole of silver Tricresyl phosphate coating ffi 0.8cc
/m2 8th house: Yellow filter store gelatin yellow color in clear water. idosilver and 2.5-di-t
- an emulsified dispersion of octylhydroquinone.

9th layer: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide 26 mol%...Amount of coated silver (average grain size 0.8μ>0.5a/m''L coupler Y... ...0.125 for 11 moles of ff
Malt υ cresyl phosphate coating ji 013cc
/ TO2 10th layer: Blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 6 mol%...Amount of coated silver (average grain size 0.8μ) 0.60 /m2 Coupler Y... ...0.04 mole tricresyl phosphate coating per mole of silver10. icc/m”11th
Layer: Protective layer Apply a gelatin layer containing polymethyl methacrylate particles (diameter approx. 1.5μ).

To prepare the coupler for each layer, add the coupler to a solution of tricresyl sulfate and ethyl acetate, add sodium P-dodecylbenzenesulfonate as an emulsifier, dissolve by heating, mix with a heated 10% gelatin solution, and use a colloid mill. I used an emulsified version.

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 13.

Compound dye used to make the sample: Ann and Draw 5,5'-dichloro-3,3
'-Di(7-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye ■: Anhydro-9-ethyl-3,3'-di(7-sulfopropyl) 4.5.4' .

5'-dibenzothi7carpocyanine hydroxide/triethylamine salt sensitizing dye■: Anhydro9-ethyl-5,5'-dichloroO-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 coupler A coupler B t Coupler C Coupler F Coupler M Coupler Y Coupler Y in the 9th and 10th layers of Sample 18 was changed as shown in Table 3. In addition, a sample was prepared in the same manner as Sample 18, in which the DIR compound shown in Table N3 and an oxidized developing agent scavenger were added to No. 9m.

For samples using polymer coupler latex, add tricresyl phosphate to 1/1 of sample 18.
I set it to 0.

These samples were subjected to the same phenomenon treatment as in Example 1, and the graininess and image storage stability were measured.

Furthermore, in order to evaluate the 3V sharpness, these samples were exposed through a wedge whose spatial frequency was varied in the range of 3 lines/mm to 100 lines/mm, and developed in the same manner as in Example 1. M T F
(ModulationTransfer l"u
ncti-on) was determined. A comparison was made at a spatial frequency of 5 lines/+nm to examine the sharpness improvement effect. MTFf [
The density was measured using a slitter with a slit width of 300 μm and a width of 2 μm, and the WI image power relative to the input was expressed as a percentage. The results are shown in Table 3.

As shown in Table 3, comparative coupler Y showed good values for image storage stability and sharpness (MTFII[), but was considerably inferior in graininess (RMS value).

Comparative coupler (4) had significantly improved graininess, but had a large deterioration in image storage stability.

Deterioration in sharpness was also observed. In contrast, samples using the yellow dye-forming polymer coupler latexes (M) and (L') of the present invention had excellent graininess and image storage stability, and improved sharpness was also observed. Roughly,
Significant sharpness improvements were made using DIR compounds and oxidized developer scavengers.

Preferred Embodiment 1) A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow dye-forming polymer coupler latex having a repeating unit represented by the following general formula [2].

General formula [I] 2-A silver halide color photographic light-sensitive material, characterized in that in the general formula [I], the leaving group in Q is a group of 2(il[i) derived from an aryloxy group.

3) A silver halide color photographic material characterized in that the wi leaving group in Q in the general formula [CI] is a divalent group derived from a urazole group.4) The leaving group in Q in the general formula [I] A silver halide color photographic material characterized in that the group is a divalent group derived from a hydantoin group.

5) A silver halide color photographic light-sensitive material, characterized in that in the general formula [I], the leaving group in Q is a group 25 derived from a tetrazolone group.

6) A silver halide color photographic material characterized in that the yellow dye-forming polymer coupler latex of the present invention and a DIR compound are used together.

7) A silver halide color photographic material characterized in that the yellow dye-forming polymer coupler latex of the present invention and an oxidized developing agent scavenger are used together.

8) A silver halide color photographic material characterized in that the yellow dye-forming polymer coupler latex of the present invention is used in combination with a DIR compound and an oxidized developing agent scavenger.

Claims (1)

[Scope of Claims] A halogen halogen compound having a silver halide emulsion layer containing a yellow dye-forming polymer coupler latex having a repeating unit represented by the following general formula [I] capable of forming a dye using an alkaline color developer on a support. Silver chemical color photographic material. [General Formula I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (In the formula, R_1 represents an alkyl group or an aryl group,
R_2 represents a monovalent group, Q represents a group having an ethylenically unsaturated group and can be separated by a coupling reaction with an oxidized product of a color developing agent, and l represents an integer of 0 to 5. )